WO2007147428A1 - Copolymer, modified polymer carbohydrate material, modified bulk polymer, composite material, and methods of preparation - Google Patents

Copolymer, modified polymer carbohydrate material, modified bulk polymer, composite material, and methods of preparation Download PDF

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WO2007147428A1
WO2007147428A1 PCT/EP2006/006099 EP2006006099W WO2007147428A1 WO 2007147428 A1 WO2007147428 A1 WO 2007147428A1 EP 2006006099 W EP2006006099 W EP 2006006099W WO 2007147428 A1 WO2007147428 A1 WO 2007147428A1
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copolymer
polymer
scp
range
poly
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PCT/EP2006/006099
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French (fr)
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Qi Zhou
Harry Brumer
Tuula Tellervo Teeri
Johan Patrik Stolt
Lars Göran ÖDBERG
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Swetree Technologies Ab
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    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66Polyesters containing oxygen in the form of ether groups
    • C08G63/664Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
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    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0057Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Xylans, i.e. xylosaccharide, e.g. arabinoxylan, arabinofuronan, pentosans; (beta-1,3)(beta-1,4)-D-Xylans, e.g. rhodymenans; Hemicellulose; Derivatives thereof
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    • C08F293/00Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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    • C08G61/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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    • C08G61/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/124Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
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    • C08G61/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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    • C08G64/00Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
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    • C08G81/00Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/021Block or graft polymers containing only sequences of polymers of C08C or C08F
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    • C08L65/00Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
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    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00Preparation of compounds containing saccharide radicals
    • C12P19/04Polysaccharides, i.e. compounds containing more than five saccharide radicals attached to each other by glycosidic bonds
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    • C08F2438/01Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
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    • C08G2261/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10Definition of the polymer structure
    • C08G2261/12Copolymers
    • C08G2261/126Copolymers block
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    • C08G2261/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/314Condensed aromatic systems, e.g. perylene, anthracene or pyrene
    • C08G2261/3142Condensed aromatic systems, e.g. perylene, anthracene or pyrene fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene
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    • C08G2261/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3221Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
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    • C08G2261/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
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    • C08G2261/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/34Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
    • C08G2261/342Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3422Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing only carbon atoms conjugated, e.g. PPV-type
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    • C08G2261/50Physical properties
    • C08G2261/51Charge transport
    • C08G2261/514Electron transport

Abstract

The present invention relates to a novel group of copolymers comprising a soluble carbohydrate polymer (SCP), which typically is a non-starch carbohydrate, and a macromolecule covalently attached to the SCP. The macromolecule may e.g. be a hydrophobic copolymer, a polyelectrolyte polymer or a biodegradable polymer. The present invention furthermore relates to a method of preparing the copolymer, products comprising the copolymer, and to methods of preparing the products comprising the copolymer. The products comprising a copolymer are for example a polymeric carbohydrate material (PCM) modified by attachment of a copolymer, and a composite material comprising the modified PCM.

Description

COPOLYMER, MODIFIED POLYMER CARBOHYDRATE MATERIAL, MODIFIED BULK POLYMER, COMPOSITE MATERIAL, AND METHODS OF PREPARATION

FIELD OF THE INVENTION The present invention relates to a novel group of copolymers comprising a soluble carbohydrate polymer (SCP) and a macromolecule covalently attached to the SCP. The macromolecule may e.g. be a hydrophobic polymer, a biodegradable polymer, a water- soluble polymer, a polyelectrolyte polymer, a electrically conducting polymer, or a signal- responsive polymer. The present invention furthermore relates to a method of preparing the copolymer, products comprising the copolymer, and to methods of preparing the products comprising the copolymer. The products comprising a copolymer are for example a polymeric carbohydrate material (PCM) modified by attachment of a copolymer, and a composite material comprising the modified PCM.

BACKGROUND

Multifunctional compounds play important roles in medical products and in the material sciences. For example, polymeric carbohydrate materials such as cellulose fibers may advantageously be mixed into plastics. The resulting composite material has improved mechanical properties, such as improved strength. Cellulose fibers are seen as an interesting substitute to carbon fibers in fiber reinforced plastic composite materials. The major drawback of the use of cellulose fibers in plastic composite materials is the poor compatibility between cellulose and the organic polymers from which the composite material contains.

A solution to this problem has been disclosed in U.S. Patent No. 6,967,027, where the cellulose fibers have been added significant amount of emulsifier in order to increase the compatibility between cellulose and a plastic. This approach has several disadvantages. The emulsifier may, over time, migrate from the modified cellulose into the plastic material. This may change the mechanical and physio-chemical properties of the composite material and thus significantly reduce its overall quality. Furthermore, the emulsifiers may leak from the composite material into the surrounding environment, particularly if the composite material is in frequent contact with water. This is unacceptable in many applications, for example in the biomedical products such as prosthesises or implants. Consequently, there is a need for improved multifunctional compounds, e.g. for improving the compatibility of PCMs and plastics.

SUMMARY OF THE INVENTION Thus, an object of the present invention is to provide and improve multifunctional compounds.

Another object of the present invention is to provide new compounds for improving the compatibility of PCMs and plastics, preferably without the drawbacks of the prior art.

Other objects of the invention will become apparent when reading the description and the examples.

An aspect of the present invention relates to a copolymer comprising an SCP and a macromolecule covalently attached to the SCP.

Another aspect of the present invention relates to a method of preparing the copolymer. The method of preparing a copolymer comprises the steps of a) providing an SCP and a macromolecule, such as a hydrophobic polymer, and b) attaching the macromolecule covalently to the SCP.

Yet another aspect of the invention relates to a modified PCM comprising the copolymer.

An additional aspect of the invention relates to modified bulk polymer comprising the copolymer.

Still a further aspect of the invention relates to a method of preparing the modified bulk polymer.

Another aspect of the invention relates to a composite materiel comprising the copolymer.

Yet a further aspect of the invention relates to methods of preparing the composite material.

Additional aspects of the invention relate to various uses of the copolymer of the invention. BRIEF DESCRIPTION OF THE FIGURES

In the following some embodiments of the present invention will be described with reference to the figures, wherein

Figure 1 shows schematic illustrations of some of the structural embodiments of the copolymer,

Figure 2 shows schematic illustrations of some of the structural embodiments of the copolymer,

Figure 3 shows the plot for determining the maximum absorbable concentration of copolymer,

Figure 4 shows copolymer modified cellulose microcrystals dispersed in different non-polar solvents and with different amounts of copolymer bound to the cellulose,

Figure 5 shows the XGOs which are commonly isolated after endoglucanase digestion of tamarind xyloglucan, and

Figure 6 shows visual observation of cellulose nanocrystal suspensions in water and toluene between crossed polars.

DETAILED DESCRIPTION OF THE INVENTION

A broad aspect of the present invention relates to a copolymer comprising an SCP and a macromolecule covalently attached to the SCP.

In some preferred embodiment of the invention, the copolymer is capable of binding to cellulose by means of hydrogen bonds in an aqueous environment.

In some preferred embodiment of the invention, the copolymer of the invention is an isolated copolymer, that is to say, a copolymer which is not bound to cellulose.

In the present context, the term "copolymer" relates to a polymer molecule comprising at least two types of polymers which are covalently attached, i.e. linked by one or more covalent bond(s). When the copolymer of the present invention is said to contain, comprise, or consist of components such as e.g. the SCP and the macromolecule, it should be understood that mentioned components are covalently attached to each other to form part of the copolymer. The copolymer comprises at least one macromolecule which is covalently attached to an SCP. The term "copolymer" should be broadly interpreted and encompasses e.g. di-block copolymer, tri-block copolymers, ter-polymers, graft polymers, and dendrimers.

In the present context, the term "macromolecule" relates to a large molecule preferably having a molar weight of at least 1000 g/mol, such as at least 2500 g/mol, preferably at least 5000 g/mol.

The term "polymer" should be broadly interpreted and also encompasses oligomers. In a preferred embodiment of the invention a polymer comprises at least 5 monomers of same or similar type, such as at least 10 monomers of same or similar type, and preferably at least 15 monomers of same or similar type.

A polymer may e.g. consist essentially of a number of identical, polymerised monomers. Poly(methyl methacrylate) is an example of such a polymer consisting of polymerised methyl methacrylate monomer molecules. Alternatively, the polymer may consist essentially of a number of monomers of a similar type polymerised to form the polymer. Examples of monomers of a similar type are e.g. amino acids which are the building blocks of peptide and proteins, and nucleotides which are the building blocks of nucleic acid molecules. Polymers consisting essentially of monomers of different type are also envisioned.

The term "covalently attached" both encompasses embodiments where the SCP are linked directly to the macromolecule by a covalent bond and embodiments where the SCP are indirectly linked to the macromolecule by means of a linking group.

Thus, in some embodiments of the invention, the macromolecule is covalently attached to the SCP by means of a direct covalent bond between the macromolecule and the SCP. An example of this is the copolymer resulting from coupling the aldehyde group of a xyloglucan molecule to the N-terminal amino group of a peptide.

In other embodiments of the invention, the macromolecule is covalently attached to the SCP by means of a linking group which links the macromolecule to the SCP via a chain of covalent bonds. An example of this is the di-block copolymer of Example 5, where arπino- modified xyloglucan is coupled with carboxylic acid-terminated polystyrene. The linking group is the part of the copolymer which is not macromolecule and not SCP, i.e. the parts of the di-block copolymer of Example 5 which contains the reacted amino group and the reacted carboxylic acid group.

The linking group is typically relatively short. In some embodiments of the invention, the chain of covalent bonds of the linking group, i.e. not including any side groups or hydrogen atoms, contains at most 200 atoms, such at most 150 atoms, preferably at most 100 atoms, and even more preferred at most 50 atoms, such as at most 25 atoms. For some embodiments the chain of covalent bonds of the linking group contains at most 20 atoms and preferably at most 10 atoms.

For some applications very short linking groups are preferred. In this case, the chain of covalent bonds of the linking group in the range of 1-25 atoms, and preferably in the range of 2-20 atoms, such as in the range of 5-15 atoms. Without being bound by theory, the very short chain of covalent bonds is believed to reduce the impact of the linking group on the properties of the copolymer.

For other applications, longer linking groups are preferred. In this case, the chain of covalent bonds of the linking group in the range of 25-200 atoms, and preferably in the range of 50-150 atoms, such as in the range of 75-125 atoms. With out being bound by theory, the very short chain of covalent bonds is believed to result in an improved intramolecular mobility or flexibility, which can be advantageous.

In some embodiments of the invention, the linking does not contain a polymer. In other embodiments the linking group contains at most 10 polymerised monomers, preferably at most 6 polymerised monomers, and even more preferred at most 3 polymerised monomers, such as two linked monomers.

Normally, the macromolecule comprises either no carbohydrate or only small amounts of carbohydrate.

In an embodiment of the invention, the macromolecule comprises at most 10% carbohydrate by weight, preferably at most 2% carbohydrate by weight, and even more preferably at most 2% carbohydrate by weight.

In an embodiment of the invention, the macromolecule is not an enzyme. In another embodiment of the invention, the macromolecule is not a protein. In yet another embodiment of the invention, the macromolecule is not a peptide. In a preferred embodiment of the invention, the macromolecule comprises a hydrophobic polymer. The macromolecule may e.g. consist essentially of a hydrophobic polymer.

A "hydrophobic polymer" may e.g. be a polymer having a high solubility in a hydrophobic solvent and a low solubility in water.

In preferred embodiments of the invention, a polymer is defined as hydrophobic if a test specimen, i.e. a disk consisting of the polymer, has a relative water absorption within 24 hours as set out in ASTM D570-98 (standard method to measure water absorption by polymers) under point 7.1 of at most 0.5% by weight of the test specimen.

The test specimen, i.e. the bulk polymer for determining hydrophobicity must be in the form of a disk of 50.8 mm in diameter and 3.2 mm in thickness. Permissible variations in thickness of the test specimen are ±0.3 mm.

Useful hydrophobic polymers may e.g. be selected from the group consisting of polystyrene, poly(acrylic acid), poly(methyl methacrylate), polypropylene, polyethylene, polycarbonate, poly(lactic acid), and poly(caprolactone).

The hydrophobic polymer may comprise polymerised monomers selected from the group consisting of styrene, acrylic acid, methyl methacrylate, propylene, ethylene, lactic acid, lactide, and ε-caprolactone.

The hydrophobic polymer may be a non-branched polymer or it may be a branched polymer.

In the present context, the term "the macromolecule consists essentially of means that the macromolecule primary contains the specified type of polymer, but that it may contain minor amounts of other chemical groups which are inessential for the function of the copolymer.

In another preferred embodiment of the invention, the macromolecule comprises a biodegradable polymer. The macromolecule may e.g. consist essentially of a biodegradable polymer.

In the context of the present invention, the term "biodegradable polymer" relates to a polymer which is capable of undergoing a chemical and/or biological degradation. The degradation or disintegration of polymers can be effected or induced by physical factors such as temperature, light, moisture or by chemical factors such as hydrolysis caused by a change in pH or by the action of appropriate enzymes capable of degrading the polymers.

The biodegradable polymer may e.g. be selected from the group consisting of a polyester, a polycarbonate, a polyether, a polyamide, a polyurethane, a peptide, and a protein, as well as combinations thereof.

A presently preferred biodegradable polymer is a polyester.

An important feature of the biodegradable polymers as used herein is that they contain chemical unstable bonds that can be broken under environmental conditions. In the present context, the term "environmental condition" denotes indoor and outdoor locations and the temperature, light and humidity conditions prevailing in such environments. It will be appreciated that the rate of degradation of the biodegradable polymer will depend on the above physical conditions. In preferred embodiments, the degradable polymer is one where, under any given environmental conditions except extreme cold temperature conditions, i.e. at temperatures below 0° C, at least 5% of unstable bonds, preferably at least 10%, more preferably at least 15% including at least 25% of unstable bonds are broken after one month to 12 months under environmental conditions.

The biodegradability of a polymer may e.g. be determined according to ASTM D5338-93 - a test developed by the American Society for Testing and Materials (ASTM). This is a standard test method for determining aerobic biodegradation of plastic materials, i.e. the polymer, under controlled composting conditions. In this method the polymer is mixed with stabilised and mature compost derived from the organic fraction of municipal solid waste. The net production of CO2 is recorded relative to a control containing only mature compost. After determining the carbon content of the test polymer, the percentage biodegradation can be calculated as the percentage of solid carbon of the test substance which has been converted to gaseous carbon in the form of CO2. In addition to carbon conversion, disintegration and weight loss can be evaluated.

When using ASTM D5338-93, a polymer is deemed a biodegradable polymer, according to the present invention, if at least 25% by weight of the polymer, more preferably at least 50% by weight of the polymer, such as at least 60% by weight of the polymer, and most preferably at least 80% by weight of the polymer mineralise in six months.

In presently preferred embodiments, the biodegradable polymer either comprises or consists essentially of a polyester polymer made from a cyclic ester selected from the group of lactide, glycolide, trimethylene carbonate, vinyl alcohol, ε-valerolactone, β- propiolactone and ε-caprolactone. Such polyester polymers may be homopolymers, co- or ter-polymers, including block or graft co-polymers.

Useful biodegradable polymers may e.g. be selected from the group consisting of poly(lactide), po)y(glycolide), poly(trimethylene carbonate), poly(valerolactone), poly(propiolactone), polyCcaprolactone), a poly(hydroxyalkanoate) such as poly(hydroxybutyrate), poly(hydroxyvalerate), poly(hydroxybutyrate-co- polyhydroxyhexanoate), poly(butylene succinate), poly(butylene succinate adipate), poly(vinyl alcohol), poly(ethylene tetraphalate), poly(butylene adipate-co-terephthalate), poly(tetramethylene adipate-co-terephthalate, poly(ethylene vinyl alcohol).

Hydrophobic, biodegradable polymers may e.g. be selected from the group consisting of poly(lactide), poly(glycolide), poly(trimethylene carbonate), poly(valerolactone), poly(propiolactone), poly(caprolactone), a poly(hydroxyalkanoate) such as poly(hydroxybutyrate), poly(hydroxyvalerate), poly(hydroxybutyrate-co- polyhydroxyhexanoate), poly(butylene succinate), poiy(butylene succinate adipate), poly(vinyl alcohol), poly(ethylene tetraphalate), poly(butylene adipate-co-terephthalate), poly(tetramethylene adipate-co-terephthalate.

Water-soluble, biodegradable polymers may e.g. be selected from the group consisting of polyvinyl alcohol), and poly(ethylene vinyl alcohol).

In yet a preferred embodiment of the invention, the macromolecule comprises a water- soluble polymer. For example, the macromolecule may consist essentially of a water- soluble polymer.

In the present context, the term "water-soluble polymer" relates to a polymer which has a high solubility in water.

In an embodiment of the invention, a polymer is a water-soluble polymer if it has a solubility in at least one of three aqueous solutions at 300C of at least 0.5 g polymer per 100 g aqueous solution, such as at least 1 g polymer per 100 g aqueous solution, more preferably at least 2 g polymer per 100 g aqueous solution, and most preferably at least 5 g polymer per 100 g aqueous solution; said three aqueous solutions are water, 0.1 M HCI in water, and 0.1 M NaOH in water.

In another embodiment of the invention, a polymer is a water-soluble polymer if it has a solubility in water at 300C of at least 0.5 g polymer per 100 g water, such as at least 1 g polymer per 100 g water, more preferably at least 2 g polymer per 100 g water, and most preferably at least 5 g polymer per 100 g water.

A water-soluble polymer may e.g. comprise or consist essentially of monomers selected from the group consisting of monomers comprising an acidic group, monomers comprising a basic group, monomers comprising a heterocyclic group, and monomers comprising a neutral hydroxyl group.

Useful monomers comprising an acidic group are e.g. acrylic acid, methacrylic acid, itaconic acid, allenesulfonic acid, ethylenesulfonic acid, styrenesulfonic acid, and 2- sulfoethyl methacrylate.

Monomers comprising a basic group are for example acrylamide, methacrylamide, N- hydroxymethylacrylamide, N,N-dimethylacry!amide, N-isopropylacrylamide, N- acetamidoacrylamide, 2-aminoethyl methacrylate, and N,N-dimethylaminoethyl methacrylate.

Preferred monomers comprising a heterocyclic structure are e.g. N-vinyl-2-pyrrolidone, 2- vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 4-methylenehydantoin, 4-vinyl-3- morpholine, and l-vinyl-2-methyl-2-imidazo!ine.

Useful monomers comprising a neutral hydroxyl group are e.g. allyl alcohol, 2- hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate.

Useful water-soluble polymers may e.g. be selected from the group consisting of polyvinyl alcohol), poly(ethylene vinyl alcohol), DNA, RNA, protein, poly(acryϋc acid), poly(methacrylic acid), poly(itaconic acid), poly(allenesulfonic acid), poly(ethylenesulfonic acid), poly(styrenesulfonic acid), poly(2-sulfoethyl methacrylate), poly(acrylamide), poly(methacrylamide), poly(N-hydroxymethylacrylamide), poly(IM,N-dimethylacrylamide), poly(N- isopropylacrylamide), polyCN-acetamidoacrylamide), poly(2-aminoethyl methacrylate), poly(N,N-dimethylaminoethyl methacrylate), poly(N-vinyl-2-pyrrolidone), poly(2-vinylpyridine), poly(3-vinylpyridine), poly(4-vinylpyridine), poly(4- methylenehydantoin), poly(4-vinyl-3- morpholine), poly(l-vinyl-2-methyl-2-imidazoline), poly(allyl alcohol), poly(2-hydroxyethyl acrylate), poly(2-hydroxyethyl methacrylate), and poly(2-hydroxypropyl methacrylate).

In a further preferred embodiment of the invention, the macromolecule comprises a polyelectrolyte polymer. It is envisioned that the macromolecule e.g. may consist essentially of a polyelectrolyte polymer. In the present context, the term "polyelectrolyte polymer" relates to any polymeric ionic material having a plurality of functional groups capable of holding a positive and/or negative charge, i.e., polycationic and/or polyanionic materials capable of forming salts. The term "polyelectrolyte polymer" is used to refer to such a polycationic and polyanionic materials in both charged form (i.e. salts) as well as neutralized form.

In an embodiment of the invention, the polyelectrolyte polymer comprises a polycationic polymer, such as e.g. poly(L-lysine), poly(L-glutamine), polyvinylamide, polyethylenimine, other polymeric primary or secondary amines, or copolymers, functionalized derivates, or blends or combinations hereof, as well as various salts thereof.

In another embodiment of the invention, polyelectrolyte polymer comprises a polyanionic polymer, such as e.g. polyacrylic acid, poly(L-glutamic acid), poly(L-aspartic acid) and other polycarboxylic acids, polysulfonates, or blends or mixtures thereof, as well as various salts thereof.

Thus, the polyelectrolyte polymer may for example be selected from the group consisting of poly(L-lysine), poly(L-glutamine), polyvinylamide, polyethylenimine, polyacrylic acid, poly(L-glutamic acid), poly(L-aspartic acid), polycarboxylic acids, polysulfonates, and mixtures thereof, as well as various salts thereof.

In another preferred embodiment of the invention, the macromolecule comprises an electrically conducting polymer, and in some embodiments the macromolecule consists essentially of an electrically conducting polymer.

In the present context, the term "electrically conducting polymer" relates to conductive polymers, which are almost always organic, and which may have extended delocalized bonds, often comprised of aromatic units that creates a band structure similar to silicon, but with localized states. When charge carriers, from the addition or removal of electrons, are introduced into the conduction or valence bands the electrical conductivity increases dramatically.

Useful electrically conducting polymers may e.g. be selected from the group consisting of poly(acetylene)s, poly(pyrrole)s, poly(thiophene)s, poly(aniline)s, poly(fluorene)s, polynaphthalenes, poly(p-phenylene sulfide), and poly(para-phenylene vinylene)s. These compounds are known as polyacetylene, polyaniline, etc. "blacks" or "melanins". The melanin pigment in animals is generally a mixed copolymer of polyacetylene, polypyrrole, and polyaniline. In yet a preferred embodiment of the invention, the macromolecule comprises a signal- responsive polymer. In some embodiments of the invention, the macromolecule consists essentially of the signal-responsive polymer.

In the present context, the term "signal-responsive polymer" relates to a polymer that contract or expand (or say undergo conformational changes) in response to environmental conditions such as pH, ionic strength, temperature, redox reaction, photo-irradiation, the nature of solvent, and added chemicals.

In an embodiment of the invention, the signal-responsive polymer responds to a pH change.

In an embodiment of the invention, the signal-responsive polymer responds to a change in the ionic strength.

In an embodiment of the invention, the signal-responsive polymer responds to a temperature change.

In an embodiment of the invention, the signal-responsive polymer responds to a redox reaction.

In an embodiment of the invention, the signal-responsive polymer responds to photo- irradiation.

Useful signal-responsive polymer may e.g. be selected from the group consisting of acrylic acid, methacrylic acid, L-glutamic acid, γ-benzyl L-glutamate, (pH- and ionic strength- sensitive); spiropyran-containing methacrylate, methacrylate, spiropyran-containing styrene (photo sensitive); 3-carbamoyl-l-(p-vinylbenzyl)pyridinium chloride (oxidoreduction-sensitive); N-isopropylacrylamide-co-acrylic acid (thermo-senstive).

Several other types of macromolecules are envisioned and the macromolecule may e.g. comprise or consist essentially of a polymer selected from the group consisting of a semiconducting polymer, an electroluminescent polymer, a ferroelectric polymer, a ferromagnetic polymer, a nucleic acid, a impact-modified polymer, a liquid-crystalline polymer, a nonlinear optical polymer, an optically active polymer, a photoelastic polymer, a photoluminescent polymer, a piezoelectric polymer, a resist polymer, a shape-memory polymer, a superabsorbent polymer, a telechelic polymer, a redox polymer, a photosensitive polymer, and a metal chelating polymer. It should be noted that some other above properties are bulk properties that are primarily observed in compositions containing a plurality of the polymers. The individual polymer molecule or the resulting copolymer containing the individual polymer molecule need not have the same property.

Useful semiconducting polymers are e.g. thiophene polymers. Useful thiophene polymers are described in U.S. Patent No. 6,608,323, the contents of which are incorporated herein by reference.

In an embodiment of the invention, polymers of isocyanates and/or polymers of isocyanate derivatives are not desired in the copolymer. For example, the macromolecules of the copolymer may comprise an amount of polymerised isocyanates and/or polymerised isocyanate derivatives of at most 50% by weight, preferable of at most 25% by weight, and most preferably of at most 5% by weight. In some embodiments of the invention, no macromolecule of the copolymer consists essentially of or comprises a polymer of an isocyanate or a polymer of an isocyanate derivative.

The copolymer may have many different structures, some of which are shown as schematic illustrations in Figures 1 and 2.

In a preferred embodiment of the invention, the copolymer is a block copolymer. The copolymer may e.g. be a di-block copolymer, the first block comprising the SCP and the second comprising a macromolecule. In a more specific embodiment, the di-block copolymer consists essentially of the first block consisting of the SCP and the second consisting of the macromolecule. An example of this is shown in Figure 1 A) wherein the copolymer (1) contains an SCP (3) and a macromolecule (2) covalently attached to the SCP (3).

In another preferred embodiment of the invention, the copolymer is a tri-block copolymer. In an embodiment of the invention, the tri-block copolymer contains a first block comprising the SCP, the second block comprising the macromolecule, and the third block comprising an SCP or a macromolecule. For example, the tri-block copolymer may consist essentially of a first block consisting of the SCP, the second block consisting of the macromolecule, and the third block consisting of an SCP or a macromolecule. An example of this is shown in Figure 1 B) wherein the copolymer (1) contains a first SCP (3) covalently attached to a macromolecule (2) covalently attached to a second SCP (3). Alternatively, tri-block copolymer may comprise the first block containing of the macromolecule, the second block containing the SCP, and the third block containing an SCP or a macromolecule. For example, the tri-block copolymer may consist essentially of the first block consisting of the macromolecule, the second block consisting of the SCP, and the third block consisting of an SCP or a macromolecule. An example of this is shown in Figure 1 C) wherein the copolymer (1) contains a first macromolecule (2) covalently attached to a SCP (3) covalently attached to a second macromolecule (2).

In yet another preferred embodiment of the invention, the copolymer comprises a backbone comprising the SCP, and one or more macromolecules grafted to the SCP.

Several macromolecules may be grafted to the SCP, such as at least 2, at least 3, at least 4, at least 5, or at least 10 macromolecules, such as at least 25 macromolecules. An example of this is shown in Figure 1 E), where the copolymer (1) consists of 12 macromolecules (black lines) which are covalently grafted to an SCP (the grey line).

Alternatively, the copolymer may comprise a backbone comprising the macromolecule, and one or more SCPs grafted to the macromolecule. Several SCPs may be grafted to the macromolecule, such as at least 2, at least 3, at least 4, at least 5, or at least 10 SCPs, such as at least 25 SCPs. Such a copolymer is schematically illustrated in Figure 1 D) where the copolymer (1) consists of 12 SCPs (grey lines) which are covalently grafted to a macromolecule (the black line).

The copolymer of the invention may also has a graft copolymer structure, e.g. as exemplified schematically in Figure 2 A), where the copolymer (1) contains a tri-block copolymer main chain containing two macromolecules and an SCP as well as SCPs grafted to the main chain.

It is furthermore envisioned that the copolymer may have a dendrimer structure, that is to say, a star-like structure. A copolymer which is a dendrimer typically comprises a branched or star-like macromolecule having at least 3 end groups, and at least one SCP covalently attached to one of the at least 3 end groups of the branched or star-like macromolecule.

For example, at least two SCPs may each be attached to an end group of the at least 3 end groups of the branched or star-like macromolecule. In a preferred embodiment of the invention, SCPs are attached to all of the at least 3 end groups of the branched or star-like macromolecule.

An example of this is shown in Figure 2 B), where the copolymer (1) contains a or star-like macromolecule (2) having 5 end groups which each are covalently attached to a SCP. The branched macromolecule may e.g. be a polyamidoamine (PAMAM), which typically is a dendrimer having a tree-like branching structure. Alternatively, the macromolecule could be a star-like polymer polymerized from multifunctional initiators, such as e.g. 1,1,1- tris(bromoisobutyryloxy) phenylethane; l,3,5-(2'-Bromo-2'-methylpropionato)benzene; 1,3,5- (2'-Chloro-2'-methylpropionato)benzene; 1,1, 3,3,5, 5-hexakis(4-(2- bromopropionyloxymethyl)phenoxy)cyclotriphosphazene; calix[n]arene cores (n=4,6,8).

Generally, the SCPs of a copolymer may be of the same type or of different types.

In an embodiment of the invention, at least one SCP of a copolymer is of a different type than the other SCPs of the copolymer.

For example, all the SCPs of the copolymer may be of different types.

In a preferred embodiment of the invention, the copolymer comprises more than one type of macromolecule. The copolymer may e.g. comprises at least two types of macromolecules, e.g. a hydrophobic polymer and a biodegradable polymer, a hydrophobic polymer and a water-soluble polymer, a hydrophobic polymer and a electrically conducting polymer, a hydrophobic polymer and a signal-responsive polymer. It is also envisioned that the copolymer may comprise e.g. 3, 4, 5, 6, 10, 20, or even 50 different types of macromolecules.

The copolymer may comprise a one, few, or multiple macromolecules. In an embodiment of the invention, the copolymer comprises in the range of 1-500 macromolecules covalently attached to the SCP, preferably in the range of 2-100 macromolecules covalently attached to the SCP, such as in the range of 3-50 macromolecules, or in the range of 5-10 macromolecules.

The copolymer may also comprise several SCPs, and in an embodiment of the invention, the copolymer comprises in the range of 1-500 SCPs covalently attached to the macromolecule, preferably in the range of 2-100 SCP covalently attached to the macromolecule, such as in the range of 3-50 SCPs, or in the range of 5-10 SCPs.

In preferred embodiments of the invention, the copolymer contains several types of macromolecules. For example the copolymer may comprise one or more hydrophobic polymers and one or more water-soluble polymers. Also the copolymer may comprise one or more hydrophobic polymers and one or more polyelectrolyte polymers. The copolymer may e.g. comprise one or more hydrophobic polymers and one or more electrically conducting polymers. The copolymer may even comprise one or more hydrophobic polymers and one or more signal responsive polymers. It is also envisioned that the copolymer may comprise one or more hydrophobic polymers and one or more biodegradable polymers.

The same goes for the copolymers comprising one or more water-soluble polymers. Such a copolymer may comprise one or more water-soluble polymers and one or more polyelectrolyte polymers. The copolymer may comprise one or more water-soluble polymers and one or more electrically conducting polymers. The copolymer may even comprise one or more water-soluble polymers and one or more signal responsive polymers. It is also envisioned that the copolymer may comprise one or more water- soluble polymers and one or more biodegradable polymers.

In some embodiments of the invention, the copolymer comprises one or more polyelectrolyte polymers and one or more electrically conducting polymers. The copolymer may even comprise one or more polyelectrolyte polymers and one or more signal responsive polymers. It is also envisioned that the copolymer may comprise one or more polyelectrolyte polymers and one or more biodegradable polymers.

In other embodiments of the invention, the copolymer comprises one or more electrically conducting polymers and one or more signal responsive polymers. It is also envisioned that the copolymer may comprise one or more electrically conducting polymers and one or more biodegradable polymers.

In further embodiments of the invention, the copolymer comprises one or more signal responsive polymers and one or more biodegradable polymers.

It is furthermore envisioned that the copolymer may contain a higher number of difference types of macromolecules such as at least 3 different types of macromolecules, e.g. at least 4 different types of macromolecules.

The copolymer of the invention is preferably either water-soluble and/or capable of forming micelles in water.

In embodiments of the invention, the copolymer has a solubility in water at 80 0C of at least 0.1 g/L, preferably of at least 1 g/L, even more preferred of at least 5 g/L such as at least 10 g/L. In other embodiments of the invention, the copolymer has an extended solubility in water at 80 0C of at least 0.1 g/L, preferably of at least 1 g/L, even more preferred of at least 5 g/L such as at least 10 g/L. The extended solubility covers both dissolved copolymer and copolymer which is present as micelles in the water.

The macromolecule may be attached to the SCP at different sites of the SCP. In an embodiment of the invention, one or more macromolecules are covalently attached to a natural reducing end of the SCP.

Also, one or more macromolecules may be covalently attached to the carbohydrate backbone of the SCP.

It is also possible that one or more macromolecules are covalently attached one or more side-chains of the SCP.

Typically, the SCP comprises a reducing end, that is, an aldehyde group, at one of the ends of its carbohydrate backbone. More aldehyde groups may be formed by reacting the SCP with the enzyme galactose oxidase, which results in the formation aldehyde groups in the galactose-containing side chain of the SCP. Generally, the aldehyde groups are useful for attaching macromolecules to the SCP. In a preferred embodiment of the invention, a macromolecule is covalently attached to the SCP, preferably comprising xyloglucan, via its natural reducing end, and one or more macromolecules are covalently attached to the SCP via one or more aldehyde groups in the side chain(s).

Additional aldehyde and/or carboxylic acid groups may be introduced into the SCP, e.g. xyloglucan (which is not known to contain aldehyde groups other than the reducing end of the molecule), by direct reaction with oxidizing agents such as e.g. 2,2,6,6- tetramethylpiperidine-1-oxyl (TEMPO) or the periodate anion. Freitas et al., the contents of which are incorporated herein by reference, describes TEMPO oxidation of xyloglucan. Furthermore, reactive groups for attachment of macromolecules to the SCP may be introduced onto the SCP structure by activating reagents such as epichlorohydrine (epoxychloropropane). Sharma et al., the contents of which are incorporated herein by reference, describes epichlorohydrin activation of xyloglucan.

The molecular weight of a macromolecule is typically in the range 1,000-1,000,000 g/mol, preferably in the range 5,000-500,000 g/mol, and even more preferable, in the range 20,000-200,000 g/mol. Preferably, molecular weights are determined as weight average molecular weights, e g. by light scattering measurements.

The weight average molecular weight may be determined according the formula:

Figure imgf000018_0001

where M1 is the molecular weight of the ιth type of molecule and N1 is the number of molecules having the molecular weight M1.

Typically, the molecular weight of the SCP is in the range 5,000-2,000,000 g/mol, preferably in the range about 10,000-500,000 g/mol, and even more preferable in the range about 10,000-200,000 g/mol.

The SCP may have a relatively low molecular weight, e.g. when only a single macromolecule is attached to the SCP. In an embodiment of the invention, the molecular weight of the SCP is in the range 5,000-200,000 g/mol, preferably in the range about 8,000-100,000 g/mol, and even more preferable, in the range about 10,000-60,000 g/mol.

High molecular weight SCPs are also envisioned, e.g. in the case of attachment of multiple macromolecules to the side-chains of a SCP. In an embodiment of the invention, the molecular weight of the SCP is in the range 20,000-2,000,000 g/mol, preferably in the range 50,000-1,000,000 g/mol, and even more preferable, in the range 100,000-900,000 g/mol, such as in the range 300,000-900,000 g/mol.

In some embodiments, the molecular weight of the SCP is in the range 5,000-200,000 g/mol and the molecular weight of a macromolecule is in the range 1,000-1,000,000 g/mol, preferably in the range 10,000-50O7OOO g/mol, and even more preferable, in the range 20,000-200,000 g/mol.

In some embodiments, the molecular weight of the SCP is in the range 8,000-100,000 g/mol and the molecular weight of a macromolecule is in the range 1,000-1000,000 g/mol, preferably in the range 10,000-500,000 g/mol, and even more preferable, in the range 20,000-200,000 g/mol. In some embodiments, the molecular weight of the SCP is in the range 10,000-60,000 g/mol, and the molecular weight of a macromolecule is in the range 1,000-1,000,000 g/mol, preferably in the range 10,000-500,000 g/mol, and even more preferable, in the range 20,000-200,000 g/mol.

Normally, the molecular weight of the copolymer is in the range of 10,000-3,000,000 g/mol, preferably in the range of 10,000-1,000,000 g/mol, and even more preferred in the range of 10,000-500,000 g/mol.

For example, the molecular weight of the copolymer may be in the range of 10,000- 200,000 g/mol, preferably in the range of 10,000-100,000 g/mol, and even more preferred in the range of 10,000-50,000 g/mol.

The weight ratios between the SCP and the macromolecule are important for some of the functionalities of the copolymer. In an embodiment of the invention, the weight ratio between SCP and macromolecule of the copolymer is in the range of 10: 1 - 1: 15, preferably in the range of 5: 1 - 1:10, such as in the range of 2: 1 - 1:7 and even more preferably in the range of 1 : 1 - 1:4.

In preferred embodiments of the invention relating to copolymers comprising macromolecules grafted to the SCP7 the degree of substitution of the copolymer is in the range of 0.01-2, and preferably in the range 0.1-0.5.

In the present context, the term "degree of substitution" or "DS value" is defined as the average number of modified hydroxyl groups in a repeating unit of SCP

Taking the SCP xyloglucan, e.g. from Tamarind Kernel Powder, as example, the molar degree of substitution indicates the average number of modified hydroxyl groups per xyloglucan oligosaccharides (XGO) unit. According to the composition of xyloglucan oligosaccharides (XGO, XXXG/XLXG/XXLG/XLLG ratio 15:7:32:46), there are average 22 hydroxyl groups per XGO unit available for conversion, the maximum obtainable degree of substitution DS = 22.

If the SCP contains or consists essentially of xyloglucan, the degree of substitution of the copolymer is normally in the range of 0.01 to 1, preferably in the range 0.05-0.5, and even more preferred in the range of 0.07-0.2. When dealing with copolymers comprising macromolecules grafted to the SCP, the above- mentioned ranges for the degree of substitution are envisioned to result in copolymers having a high density of macromolecules while maintaining the ability of the SCP, e.g. xyloglucan, to bind to cellulose.

An important property of the copolymer is that it is capable of binding to cellulose in an aqueous environment. The SCP of the copolymer is partly or fully responsible for this capability, and care should be taken not to modify the SCP so much that its inherent chemical nature, i.e. its ability to bind to cellulose, is significantly reduced or even lost.

It is preferred that the copolymer is binds strongly, and preferably irreversibly, to cellulose in aqueous solutions having a pH in the range of pH 5-9 and containg at least 10% water by weight. In embodiments of the invention, the may be possible to dissociate the copolymer from cellulose by using highly basic aqueous solutions such as 2 M NaOH (aq).

A useful measure of the binding strength of the copolymer relative to cellulose is the R0 value which is determined according to Example 24. The R0 value is the ratio between a) the amount of copolymer which has been released from the modified cellulose nanocrystals during a wash step, and b) the total amount of copolymer bound to the modified cellulose nanocrystals before the wash.

An RD value near 1 means that most of the copolymer is washing off and indicates a poor binding strength. An RD value near 0 indicates that most of copolymer stays on the cellulose and indicates a high binding strength.

In a preferred embodiment of the invention, the R0 value of a copolymer is at most 0.1, such as at most 0.05, preferably at most 0.01, such as at most 0.005, and even more preferred at most 0.001, such as at most 0.0001. Even lower R0 values are envisioned such as at most 0.00001, at most 0.00000001, or at most 0.00000000001.

In an embodiment of the invention, the macromolecule is a non-branched polymer. In another embodiment of the invention, the macromolecule is a branched polymer.

The term "soluble carbohydrate polymer" which is abbreviated (SCP), relates to a polymer comprising one or more different monosaccharides or their derivatives, which can be dissolved in aqueous or organic solvents. Examples include polysaccharides classified as hemicelluloses (those carbohydrate polymers which are not composed only of β(l-4)- linked glucose units, i.e., cellulose), pectins (polyuronic acids and esters). Xyloglucan, which is a polysaccharide composed of a β(l-4)-linked polyglucose backbone decorated with α(l-6) xylose residues, which themselves can be further substituted with other saccharides such as fucose and arabinose, is an example of such a SCP, specifically a 5 hemicellulose.

In a preferred embodiment the SCP is capable of binding to the PCM via one or more hydrogen bonds.

10 The SCP is preferably a non-starch carbohydrate. The SCP will typically comprise a component selected from the group consisting of a hemicelluiose, and a pectin.

For example, the SCP may comprise components selected from the group consisting of hemicelluloses and pectins, e.g., glucuronoxylans, xylans, mannans, glucomannans, 15 galactoglucomannans, arabinoxylans, galacturonans, rhamnogalacturonan, especially rhamnogalacturonan II and xyloglucan.

In a preferred embodiment of the invention, the SCP comprises a hemicellulose, e.g. at least 1% hemicellulose, such as at least 2%, 5%, 10%, 20%, 30, 40%, 50%, 60%, 70%, 20 80%, 95%, or 99%, such as at least 99.9% hemicellulose, such as e.g. 100% hemicellulose.

In an especially preferred embodiment of the invention, the SCP comprises xyloglucan.

25 The SCP may e.g. comprise at least 1% xyloglucan, such as at least 2%, 5%, 10%, 20%, 30, 40%, 50%, 60%, 70%, 80%, 95%, or 99%, such as at least 99.9% xyloglucan, such as e.g. 100% xyloglucan. The SCP may consist essentially of xyloglucan.

Xyloglucan from many different sources may be used. For example, the source of 30 xyloglucan may be cell walls of various plants, such as e.g. pea or nasturtium, or it may be seeds of various plants, such as e.g., Tamarindus sp. or Brassica sp. Other useful sources may e.g. be found in Zhou et al., the contents of which are incorporated by reference. Further useful xyloglucan sources may be found in the references mentioned in Zhou et al. Xyloglucan from tamarind seeds is presently preferred. 35

XGOs are commonly named according to the nomenclature system outlined in Fry et al. where G represents an unsubstituted beta-glucopyranosyl residue, X represents a xylopyranosyl-alpha(l-6)-glucopyranosyl unit, L represents a galactopyranosyl-beta(l-2)- xylopyranosyl-alpha(l-6)-glucosyl unit, F represents a fucopyranosyl-alpha(l-2)- galactopyranosyl-beta(l-2)-xylopyranosyl-alpha(l-6)-glucosyl unit, among others. These various units may be connected via a beta(l-4) linkage between the glucopyranosyl units to form a beta(l-4)-glucan polysaccharide backbone. Using this nomenclature, the XGOs which are commonly isolated after endoglucanase digestion of tamarind xyloglucan are XXXG, XLXG, XXLG, and XLLG (see Figure 5).

The copolymer typically comprises in the range of 1-500 hydrophobic polymers covalently attached to the SCP, such as in the range of 2-100 hydrophobic polymers or in the range of 3-50 hydrophobic polymers, e.g. in the range of 5-10 hydrophobic polymers.

Normally, the molecular weight of a hydrophobic polymer is in the range 1,000-1,000,000 g/mol, preferably in the range 5,000-500,000 g/mol, and even more preferable, in the range 20,000-200,000 g/mol.

In some embodiments of the invention, the molecular weight of the SCP may be in the range 5,000-2,000,000 g/mol, preferably in the range about 10,000-500,000 g/mol, and even more preferable, in the range about 10,000-200,000 g/mol.

In some embodiments of the invention, the molecular weight of the SCP is in the range 5,000-200,000 g/mol, preferably in the range about 8,000-100,000 g/mol, and even more preferable, in the range about 10,000-60,000 g/mol.

In some embodiments of the invention, the molecular weight of the SCP is in the range 20,000-2,000,000 g/mol, preferably in the range 50,000-1,000,000 g/mol, and even more preferable, in the range 100,000-900,000 g/mol, such as in the range 300,000-900,000 g/mol.

In some embodiments of the invention, the molecular weight of the SCP is in the range 5,000-200,000 g/mol and the molecular weight of a hydrophobic polymer is in the range 1,000-1,000,000 g/mol, preferably in the range 10,000-500,000 g/mol, and even more preferable, in the range 20,000-200,000 g/mol.

In some embodiments of the invention, the molecular weight of the SCP is in the range 8,000-100,000 g/mol and the molecular weight of a hydrophobic polymer is in the range 1,000-1000,000 g/mol, preferably in the range 10,000-500,000 g/mol, and even more preferable, in the range 20,000-200,000 g/mol.

In some embodiments of the invention, the molecular weight of the SCP is in the range 10,000-60,000 g/mol, and the molecular weight of a hydrophobic polymer is in the range 1,000-1,000,000 g/mol, preferably in the range 10,000-500,000 g/mol, and even more preferable, in the range 20,000-200,000 g/mol.

In some embodiments of the invention, the molecular weight of the copolymer is in the range of 10,000-3,000,000 g/mol, preferably in the range of 10,000-1,000,000 g/mol, and even more preferred in the range of 10,000-500,000 g/mol.

In some embodiments of the invention, the molecular weight of the copolymer is in the range of 10,000-200,000 g/mol, preferably in the range of 10,000-100,000 g/mol, and even more preferred in the range of 10,000-50,000 g/mol.

The weight ratio between SCP and hydrophobic polymer of the copolymer is usually in the range of 10: 1 - 1: 15, preferably in the range of 5: 1 - 1: 10, such as in the range of 2: 1 - 1:7 and even more preferably in the range of 1: 1 - 1:4.

An aspect of the invention relates to an aqueous formulation of the copolymer as defined herein, and e.g. of the copolymer wherein the macromolecule is a hydrophobic polymer.

Typically, the aqueous formulation comprises copolymer in an amount in the range of 0.1- 80% by weight, and water in an amount in the range of 10-99.9% by weight. For example, the aqueous formulation may comprise copolymer in an amount in the range of 1-50% by weight, and water in an amount in the range of 30-99% by weight.

Concentrated aqueous formulations may be useful for storage or transportation of the copolymer. Such concentrated aqueous formulations may comprise copolymer in an amount in the range of 10-80% by weight and water in an amount in the range of 10-90% by weight. For example, the aqueous formulation may comprise copolymer in an amount in the range of 20-70% by weight, and water in an amount in the range of 20-80% by weight, such as copolymer in an amount in the range of 30-60% by weight, and water in an amount in the range of 30-70% by weight.

The aqueous formulation may furthermore comprise an organic, water soluble solvent, e.g. in an amount in the range of 1-50%.

For example, the aqueous formulation may comprise the organic, water soluble solvent in an amount in the range of 5-45% by weight, preferably in the range of 10-40% by weight, and even more preferred in the range of 15-30% by weight. In the context of the present invention, the "organic, water soluble solvent" is deemed water soluble if it has a water solubility of at least 1 g solvent per 100 g water at 25°C.

The organic, water soluble solvent may e.g. comprise an alcohol. The alcohol may e.g., be selected from the group consisting of methanol, ethanol, propanol, and butanol, and a mixture thereof.

The organic, water soluble solvent may e.g. comprise acetone, propylene glycol, or glycerol, or a mixture thereof.

The aqueous formulation may furthermore comprise an emulsifier.

For example, the aqueous formulation may comprise the emulsifier in an amount in the range of 0.1-10% by weight, preferably in the range of 0.3-7% by weight, and even more preferred in the range of 1-5% by weight.

A number of different emulsifiers may be used in the context of the present invention. For example, anionic, cationic, amphoteric or non-ionic emulsifiers can be used. Suitable emulsifiers include lecithins, polyoxyethylene stearate, polyoxyethylene sorbitan fatty acid esters, fatty acid salts, mono and diacetyl tartaric acid esters of mono and diglycerides of edible fatty acids, citric acid esters of mono and diglycerides of edible fatty acids, saccharose esters of fatty acids, polyglycerol esters of fatty acids, polyglycerol esters of interesterified castor oil acid, sodium stearoyllatylate, sodium lauryl sulfate and sorbitan esters of fatty acids and polyoxyethylated hydrogenated castor oil (e.g. the product sold under the trade name CREMOPHOR), block copolymers of ethylene oxide and propylene oxide (e.g. products sold under trade names PLURONIC and POLOXAMER), polyoxyethylene fatty alcohol ethers, polyoxyethylene sorbitan fatty acid esters, sorbitan esters of fatty acids and polyoxyethylene steraric acid esters.

Particularly suitable emulsifiers are polyoxyethylene stearates, such as for instance polyoxyethylene (8) stearate and polyoxyethylene (40) stearate, the polyoxyethylene sorbitan fatty acid esters sold under the trade name TWEEN, for instance TWEEN 20 (monolaurate), TWEEN 80 (monooleate), TWEEN 40 (monopalmitate), TWEEN 60 (monostearate) or TWEEN 65 (tristearate), mono and diacetyl tartaric acid esters of mono and diglycerides of edible fatty acids, citric acid esters of mono and diglycerides of edible fatty acids, sodium stearoyllactylate, sodium laurylsulfate, polyoxyethylated hydrogenated castor oil, blockcopolymers of ethylene oxide and propyleneoxide and polyoxyethylene fatty alcohol ether. The emulsifiers may either be a single compound or a combination of several compounds. A further aspect of the invention relates to a hydrophobic formulation of the copolymer as defined herein, and e.g. of the copolymer wherein the macromolecule is a hydrophobic polymer. Typically, the hydrophobic formulation comprises copolymer in an amount in the range of 0.1-80% by weight, and hydrophobic solvent in an amount in the range of 10- 99.9% by weight. For example, the hydrophobic formulation may comprise copolymer in an amount in the range of 1-50% by weight, and hydrophobic solvent in an amount in the range of 30-99% by weight.

Concentrated hydrophobic formulations may be useful for storage or transportation of the copolymer. Such concentrated hydrophobic formulations may comprise copolymer in an amount in the range of 10-80% by weight, and hydrophobic solvent in an amount in the range of 10-90% by weight. For example, the hydrophobic formulation may comprise copolymer in an amount in the range of 20-70% by weight, and hydrophobic solvent in an amount in the range of 20-80% by weight, such as copolymer in an amount in the range of 30-60% by weight, and hydrophobic solvent in an amount in the range of 30-70% by weight.

Another aspect of the invention relates to a dry formulation of the copolymer as defined herein, wherein the dry formulation comprises copolymer in an amount in the range of 5- 99.9% by weight, and water in an amount in the range of 0.1-10% by weight, preferably in the range of 0.1-5% by weight, and even more preferably in the range of 0.1-2% by weight.

The dry formulation may furthermore comprise a wetting agent. The wetting agent may be an emulsifier, e.g. one of the emulsifiers described herein.

The dry formulation may furthermore comprise a dispersion agent. Suitable dispersing agents include lecithin, polyoxyethylene esters of fatty acids such as stearic acid, polyoxyethylene sorbitol mono- or di-oleate, -stearate or -laurate, polyoxyethylene sorbitan mono- or di-oleate, -stearate or -laurate and the like.

The dry formulation may furthermore comprise a humectant. Useful humectants may e.g. be selected from the group consisting of glycerine, propylene glycol, glyceryl triacetate, polyols such as e.g. sorbitol or maltitol, polymeric polyols such as e.g. polydextrose, lactic acid and urea. The dry formulation may furthermore comprise an anti-agglomation agent. Useful anti- agglomeration agents may e.g. be selected from the group consisting of calcium carbonate, talc, magnesium aluminum silicates, and silicon dioxide.

The copolymers according to the present invention can be prepared in many different ways. However, three schemes of preparation are presently preferred:

(A) Couple different small oligomers and then to grow the chains by polymerization.

(B) First synthesize one of the blocks and then couple it to another type of monomer and polymerize the second block. (C) Polymerize blocks separately and then perform a coupling reaction between them.

Scheme (C) is presently preferred, thus an aspect of the present invention relates to a method of preparing a copolymer comprising the steps of: a) providing an SCP and a macromolecule, such as the hydrophobic polymer, and b) attaching the macromolecule, such as the hydrophobic polymer, covalently to the SCP.

The attachment of step b) may be performed by a number of difference linking techniques which are available to the person skilled in the art via Handbooks such as March, Smith et al., and Collins et al., and are thus readily available for the person skilled in the art. The contents of March, Smith et al., and Collins et al. are incorporated herein by reference for all purposes.

Step b) may involve one or more processes. It may e.g. involve one or more processes of modifying the SCP and macromolecule prior to the covalent attachment. Step b) always involves a process step where the SCP is covalently attached to the macromolecule.

Step b) may involve one or more processes selected from the group consisting of:

- reacting the SCP with galactose oxidase, - reacting the SCP with an oxidizing agent,

- oxidizing of a primary alcohol group to obtain an aldehyde group, and

- reacting an aldehyde group with a primary amino group.

For example, step b) may involve reductive amination of the SCP.

Additional aldehyde and/or carboxylic acid groups may be introduced into the SCP, e.g. xyloglucan (which is not known to contain aldehyde groups other than the reducing end of the molecule), by direct reaction with oxidizing agents such as e.g. 2,2,6,6- tetramethylpiperidine-1-oxyl (TEMPO) or the periodate anion. Freitas et al., the contents of which are incorporated herein by reference, describes TEMPO oxidation of xyloglucan. Furthermore, reactive groups for attachment of macromolecules to the SCP may be introduced onto the SCP structure by activating reagents such as epichlorohydrine (epoxychloropropane). Sharma et a/., the contents of which are incorporated herein by reference, describes epichlorohydrin activation of xyloglucan.

In embodiments of the invention, the SCP comprises an amino group and the macromolecule, such as the hydrophobic polymer, comprises an aldehyde group, and step b) involves reacting the aldehyde group with the amino group.

The SCP may for example comprise an aldehyde group and the macromolecule, such as the hydrophobic polymer, comprises an amino group, and step b) involves reacting the aldehyde group with the amino group.

In an embodiment of the invention, the macromolecule, such as the hydrophobic polymer, comprises an aldehyde group and step b) involves reacting a SCP with a diamine compound and an reducing agent to obtain an aminated SCP and to react the aminated SCP with macromolecule, such as the hydrophobic polymer, comprising the aldehyde group to obtain the copolymer.

The reducing agent may e.g. be a salt of cyanoborohydride, e.g. a sodium salt.

The process step of attaching the macromolecule to the SCP is typically performed in an aqueous solution. Normally the SCP is present in the aqueous solution in an amount of 0.1 to 100 mg SCP per 1 mL aqueous solution, preferably in the range of 0.5 - 30 mg SCP per 1 mL aqueous solution, even more preferred in the range of 1-10 mg SCP per 1 mL aqueous solution. The macromolecule is typically present in the aqueous solution in an amount of 0.1 to 100 mg macromolecule per 1 mL aqueous solution, preferably in the range of 0.5 - 30 mg macromolecule per 1 mL aqueous solution, even more preferred in the range of 1-10 mg macromolecule per 1 mL aqueous solution. The aqueous solution may furthermore contain useful coupling agents such as carbodiimides, e.g. N-Ethγl-N'-(3- dimethylaminopropyl)carbodiimide. Other useful coupling agents or additives may be found in March, Collins et al., or Smith et al. or in the present examples.

It is presently preferred that the aqueous solution contains an amount of water in the range of 2-99.9% by weight, preferably in the range of 5-95% by weight, and even more preferred in the range of 10-80% by weight. For attachment of hydrophobic macromolecules, such as hydrophobic polymers, to the SCP it is preferred that the aqueous solution contains in the range of 1-95% water by weight and in the range of 1-99% aprotic, water-miscible solvent by weight, preferably in the range of 2-20% water by weight and in the range of 80-98% aprotic, water-miscible solvent by weight, and even more preferred in the range of 3-10% water by weight and in the range of 90-97% aprotic, water-miscible solvent by weight.

In preferred embodiments of the invention, the aqueous solution used for the process of attaching the SCP to a hydrophobic molecule comprises 1-10 mg SCP per 1 ml. aqueous solution,

1-10 mg hydrophobic polymer per 1 mL aqueous solution,

3-10% water by weight of the aqueous solution,

90-97% water-miscible solvent by weight of the aqueous solution.

The water-miscible solvent may e.g. be an alcohol, e.g. such as methanol or ethanol, and it may be an aprotic, water-miscible solvents, e.g. such as dimethyl dulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide, tetrahydrofuran (THF) or acetone. Additionally, the water-miscible solvent may be a mixture of any of the above-mentioned water-miscible solvents.

The attachment is typically performed at a temperature in the range 5-100 0C, preferably in the range 25-80 0C, and even more preferred in the range 50-70 0C.

The pH of the aqueous solution is normally in the range of pH 4-10, preferably in the range pH 5-9, and even more preferably in the range of pH 6-8.

Alternatively, the pH of the aqueous solution may be in the range of pH 1-6, preferably in the range pH 2-5, and even more preferably in the range of pH 3-4. A low pH is particularly preferred for attachment of macromolecules which are poorly soluble in pH neutral or basic aqueous solutions.

Also, the pH of the aqueous solution may be in the range of pH 8-14, preferably in the range pH 9-13, and even more preferably in the range of 10-12. A high pH is particularly preferred for attachment of macromolecules which are poorly soluble in pH neutral or acidic aqueous solutions.

The unreacted macromolecules and SCPs may be removed e.g. by filtration and/or dialysis. The resulting copolymer is typically dried or freeze-dried. Another aspect of the invention relates to an alternative method of preparing the copolymer, the method comprising the steps of a) providing an SCP, b) attaching covalently a polymerisation initiator to the SCP, c) polymerising onto the SCP via the polymerisation initiator.

Preferably, at least 2 polymerisation initiators are attached to the SCP in step b).

Useful polymerisation initiators are e.g. acid containing initiators, allyl bromides, allyl chlorides, phenolic ester based monofunctional initiators

Useful acid containing initiator may e.g. be selected from the group consisting of alpha- halocarboxylic acids, 2-bromoisobutyric acid, 2-bromobutyric acid, bromoacetic acid, 2- chloropropionic acid, trimethylsilyl 2-bromobutyrate, t-butyldimethyl 2-bromobutyrate, t- butyl 2-bromobutyrate, 4-(l-bromoethyl)benzoic acid, and 4-(2-(2- bromopropionyloxy )ethoxy)benzoic acid .

Useful phenolic ester based monofunctional initiators may e.g. be selected from the group consisting 2- bromo-2-methylpropionic acid 4-aminophenyl ester, 2-bromo-2- methylpropionic acid 4-formyl-phenyl ester, l-(2'-Bromo-2'- methylpropionato)-4-(2",2"- dimethyl-propionato)benzene, and 1- (2'-Chloro-2'-methylpropionato)-4-(2", 2"- dimethyl- propionato)benzene.

Others useful polymerisation initiators are e.g. 2-(2,4-dinitrophenylthio)ethyl 2- bromo-2- methylpropionate, 2-bromo-propanoic acid oxiranylmethyl ester, 2-Hydroxyethyl 2- bromopropionate, and 2-chloro-acetamide.

An additional aspect of the invention relates to a method of preparing a modified PCM, the method comprising the steps of

1) providing a copolymer comprising an SCP and a macromolecule, such as a hydrophobic polymer,

2) binding the copolymer to a PCM under suitable conditions, thus obtaining the modified PCM,

3) optionally washing, and/or drying the modified PCM In a preferred embodiment of the invention, the copolymer is bound to the PCM in aqueous solution.

The process step of binding the copolymer to the PCM is typically performed in an aqueous solution. Normally the copolymer is present in the aqueous solution in an amount of 0.01 to 100 mg copolymer per 1 mL aqueous solution, preferably in the range of 0.1 - 30 mg copolymer per 1 mL aqueous solution, even more preferred in the range of 1-10 mg copolymer per 1 mL aqueous solution. The PCM is typically present in the aqueous solution in an amount of 0.1 to 500 mg PCM per 1 mL aqueous solution, preferably in the range of 0.5 - 100 mg PCM per 1 mL aqueous solution, even more preferred in the range of 1-50 mg PCM per 1 mL aqueous solution.

It is presently preferred that the aqueous solution contains an amount of water in the range of 1-99.9% by weight, preferably in the range of 5-95% by weight, and even more preferred in the range of 10-80% by weight.

For attachment of hydrophobic macromolecules, such as hydrophobic polymers, to the SCP it is preferred that the aqueous solution contains in the range of 1-95% water by weight and in the range of 1-99% aprotic, water-miscible solvent by weight, preferably in the range of 2-20% water by weight and in the range of 80-98% aprotic, water-miscible solvent by weight, and even more preferred in the range of 3-10% water by weight and in the range of 90-97% aprotic, water-miscible solvent by weight.

The pH of the aqueous solution is normally in the range of pH 4-10, preferably in the range pH 5-9, and even more preferably in the range of 6-8. Suitable buffers

The reaction time for the attachment reaction is typically in the range of 0.1 hours to 100 hours, even though both short and longer reaction time. For example, the reaction time may be in the range 1 hour - 50 hours, such as in range 5 hours - 30 hours, and in the range 10 hours - 20 hours.

In preferred embodiments of the invention, the aqueous solution used for the process of attaching the SCP to a hydrophobic molecule comprises 1-10 mg SCP per 1 mL aqueous solution, 1-10 mg hydrophobic polymer per 1 mL aqueous solution, 3-10% water by weight of the aqueous solution, 90-97% aprotic, water-miscible solvent by weight of the aqueous solution. The water-miscible solvent may e.g. be an alcohol, e.g. such as methanol or ethanol, and it may be an aprotic, water-miscible solvents, e.g. such as dimethyl dulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide, tetrahydrofuran (THF) or acetone. Additionally, the water-miscible solvent may be a mixture of any of the above-mentioned water-miscible solvents.

The pH of the aqueous solution is normally in the range of pH 4-10, preferably in the range pH 5-9, and even more preferably in the range of 6-8.

The attachment is typically performed at a temperature in the range 5-100 0C, preferably in the range 25-85 0C, and even more preferred in the range 50-70 0C.

The unreacted macromolecules or SCPs may be removed e.g. by filtration and/or dialysis. The resulting copolymer is typically dried or freeze-dried.

The term "polymeric carbohydrate material", which is abbreviated "PCM", relates to a material that comprises a water-insoluble polymeric carbohydrate material and/or a water- soluble polymeric carbohydrate material. The PCM may be any material, which wholly or partly is made up of repeating units of one or more monosaccharides. Such PCMs are often composites with two or more different types of polymeric carbohydrates or a carbohydrate polymer and another polymers such as protein. The PCM may comprise a chitin (poly(/V- acetylglucosamine)) or chitosan (poly(glucosamine)), which often forms complexes with proteins or other polysaccharides such as mannan.

The PCM may comprise cellulose, which is a homopolymer of β-l,4-linked glucose units. The long homopolymers of glucose (e.g. 8-15000 glucose units) stack onto one another by hydrogen bonds, thus forming an insoluble material. Such cellulose materials may be completely crystalline, or they may occur in disordered, amorphous form or they may be a mixture of the two. They may also be produced by first solubilizing the insoluble cellulose material and then regenerating it to form insoluble cellulose material of the same or different chain organization (cellulose II).

The first and/or the second PCM may be derived from a source selected from the group consisting of a plant, a bacterium, an algea and an animal.

The plant may comprise a gymnosperm (non-flowering plant) or an angiosperm (flowering plant). Also, the angiosperm plant may be monocotyledonous or dicotyledonous. The plant may be perennial, bi-annual or annual. In preferred embodiments, a perennial plant is a woody plant which has hard lignified tissues and forms a bush or tree. Preferred perennial plants are woody perennial plants such as trees, i.e. plants of tree forming species. 5

Examples of woody perennial plants include conifers such as cypress, fir, sequoia, hemlock, cedar, juniper, larch, pine, redwood, spruce and yew; hardwoods such as acacia, eucalyptus, hornbeam, beech, mahogany, walnut, oak, ash, willow, hickory, birch, chestnut, poplar, alder, maple and sycamore, and other commercially significant plants, 10 such as cotton, bamboo and rubber.

In another preferred embodiment, the plant may be a moncotyledonous grass.

Other examples of plants are barley, hemp, flax, wheat, maize or palms. 15

Thus, in an embodiment of the invention, the PCM comprises a water-insoluble polysaccharide.

The PCM may comprise at least 5% cellulose, such as at least 10%, 20%, 30, 40%, 50%, 20 60%, 70%, 80%, 95%, or 99%, such as at least 99.9% cellulose, such as e.g. 100% cellulose.

Thus, the PCM typically comprises a structure selected from the group consisting of i) microcrystalline cellulose, e.g. wherein the microcrystals have been prepared by 25 chemical or enzymatic hydrolysis of cellulose, ii) cellulose microfibrils, for example prepared from plant fibres, animal sources or produced by cultivation of cellulose producing bacteria such as for example Acetobacter spp., iii) regenerated cellulose, e.g. prepared by regeneration of solvent solubilized cellulose by 30 removal of the solvent, iv) plant fibers such as fibers extracted from plants, v) partially defibrillated wood, vi) wood, vii) a fibre network. 35

The term "cellulose microfibrils" relates to the elementrary units of cellulose crystals produced by plants or other organisms. Cellulose microfibrils can be prepared from cellulosic plant fibres, or more easily from cultures of cellulose synthesizing bacteria such as Acetobacter spp. The plant fibre may for example be a wood fibre or a pulp fibre and may form part of a bleached or nonbleached chemical pulp, mechanical pulp, thermomechanical pulp, chemomechanical pulp, fluff pulp, a wood pulp, or a paper pulp. The plant fibre may be prepared from any of the plants e.g. the plant mentioned herein

The fibre network may e.g. comprise paper or paperboards, cardboards, a thread such as a cotton thread, woven or non-woven fabric, filter papers, fine papers, newsprint, liner boards, tissue and other hygiene products, sack and Kraft papers.

The woven or non-woven fabric, may e.g. be any cellulose-containing fabric known in the art, such as cotton, viscose, cupro, acetate and triacetate fibres, modal, rayon, ramie, linen, Tencel® etc., or mixtures thereof, or mixtures of any of these fibres, or mixtures of any of these fibres together with synthetic fibres or wool such as mixtures of cotton and spandex (stretch-denim), Tencel® and wool, viscose and polyester, cotton and polyester, and cotton and wool.

A PCM may also be a more complex material such as a packaging materials, e.g. for liquids and foodstuff; particle boards and fibre boards, fibre composites comprising other natural or synthetic polymers or materials as well as those which may be considered electrical conductors, semi-conductors, or insulators. A PCM may comprise or consist of paper, cardboard, which are often laminated with a thermoplastic, such as polyethylene to provide an impermeable barrier to aqueous solutions, security papers, bank notes, or a wood-polymer composite.

As will be apparent from the description and the examples, the PCM may comprise structures in small polymers (e.g. dimensions less than one nm), large polymers (e.g. dimensions of 0.1 - 1000 nm), aggregates of polymers (e.g. dimensions of 1 - 10.000 nm), fibres (e.g. dimensions of 0.1-100.000 μm), aggregates of fibres and composites (e.g. dimensions of 0.00001 - 1000 m).

The weight ratio between the PCM and the copolymer depends on the effective surface area of the PCM, as well as the size of the copolymer. In a preferred embodiment of the invention the copolymer is applied in an amount that exceeds the maximum absorbable concentration of the specific copolymer relative to the concentration of the specific PCM. However, in a embodiment of the invention, the effect of the copolymer with respect to modified PCM may be obtain if the copolymer is applied in an amount of at least 20% of the maximum absorbable concentration of the specific copolymer, preferably at least 50%, even more preferably at least 80% of the maximum absorbable concentration of the specific copolymer, such as at least 90%.

The "maximum absorbable concentration of the specific copolymer" is a parameter which can be determined experimentally by treating samples of a fixed amount of the specific PCM with increasing concentrations of the specific copolymer. By measuring the concentration of unbound copolymer after the treatment of the specific PCM with the copolymer and plotting the resulting data as shown in Figure 3, the "maximum absorbable concentration of the specific copolymer" can be determined on the X-axis as the copolymer concentration where the line starts to rise (marked with "Maximum" in Figure 3), i.e. the initial concentration of copolymer where unbound copolymer can measured after treating the specific PCM with the copolymer.

Typically, the weight ratio between copolymer and PCM is in the range of 100: 1 - 1: 100, preferably in the range of 25: 1 - 1:25, such as in the range of 10: 1 - 1 : 10 and even more preferably in the range of 5: 1 - 1:5.

For example, the weight ratio between copolymer and PCM may be in the range of 100: 1 - 1: 1, preferably in the range of 100: 1 - 10: 1, such as in the range of 100: 1 - 20: 1 and even more preferably in the range of 100: 1 - 50: 1.

Alternatively, the weight ratio between copolymer and PCM may be in the range of 1:1 - 1: 100, preferably in the range of 1: 10 - 1: 100, such as in the range of 1:25 - 1: 100 and even more preferably in the range of 1:25 - 1: 100.

In a preferred embodiment of the invention, step 2) of the method of preparing the modified PCM is performed in an aqueous solution. Besides PCM and copolymer, the aqueous solution may furthermore comprise a buffer.

Useful buffers are e.g. a phosphate buffer, a borate buffer, a citrate buffer, an acetate buffer, an adipate buffer, a triethanolamine buffer, a monoethanolamine buffer, a diethanolamine buffer, a carbonate buffer (especially alkali metal or alkaline earth metal, in particular sodium or potassium carbonate buffer, or ammonium and HCI salts), a diamine buffer, especially diaminoethane buffer, imidazole buffer, a Tris buffer, or and amino acid buffer.

In step 2) the PCM and the copolymer are typically allowed to react for a period of at least a one minute, depending on the reaction conditions. For example, the reaction time may be in the range 1 minute - 5 days such as, 1 minute - 30 minutes, 30 minutes - 1 hour, 1 hour - 5 hours, 5 hours - 12 hours, 12 hours - 24 hours, 1 day - 5 days. Even reaction time longer than 5 days may be used.

The temperature of the aqueous solution is typically in the range of -5 - 100 0C, preferably in the range of 1 - 900C, such as in the range of 10 - 800C, and even more preferred in the range of 20 - 700C.

The pH of the aqueous solution is normally in the range pH 2-11, preferably pH 5-8. The concentration of the buffer in the aqueous solution may e.g. be in the range of 0.01-5 M, preferably in the range of 0.01-0.1 M.

An aspect of the present invention relates to a modified PCM comprising the copolymer as defined herein bound to a PCM. The modified PCM may be a modified PCM obtainable by the method of preparing a modified PCM.

In some embodiments of the invention, the weight ratio between copolymer and PCM in the modified PCM is typically in the range of 100: 1 - 1: 100, preferably in the range of 25: 1 - 1:25, such as in the range of 10: 1 - 1: 10 and even more preferably in the range of 5: 1 - 1:5.

In some embodiments of the invention, the weight ratio between copolymer and PCM of the modified PCM is in the range of 100: 1 - 1: 1, preferably in the range of 100: 1 - 10: 1, such as in the range of 100: 1 - 20: 1 and even more preferably in the range of 100: 1 - 50: 1.

In some embodiments of the invention, the weight ratio between copolymer and PCM in the modified PCM is in the range of 1: 1 - 1: 100, preferably in the range of 1: 10 - 1: 100, such as in the range of 1 :25 - 1: 100 and even more preferably in the range of 1:25 - 1: 100.

In an embodiment of the invention, the modified PCM comprises at least two different types of copolymers, such as at least 3, 4, 5, or 6 different types of copolymers. The modified PCM may e.g. comprise copolymers comprising hydrophobic polymers and copolymers comprising electrically conducting polymers. Also, the modified PCM may e.g. comprise copolymers comprising hydrophobic polymers and copolymers comprising polyelectrolyte polymers.

It is envisioned that the present invention may be use to prepare aggregates or assemblies of different macromolecules. An aspect the invention relates to a surface comprising PCM and at least two different types of copolymers bound to the surface. The at least two different types of copolymers may be located at discrete spot, so as to provide the surface with different functionalities. In this way, some parts of the surface may be rendered hydrophobic, some parts may be rendered electrically conducting, etc.

A further aspect of the present invention relates to a method of preparing a modified bulk polymer, the method comprising the steps of

1) providing a copolymer as defined herein, said copolymer comprising an SCP and a hydrophobic polymer,

2) binding the copolymer to the bulk polymer under suitable conditions, e.g. in the presence of an organic solvent, thus obtaining the modified bulk polymer.

In the context of the present invention, the term "bulk polymer" relates to the polymeric matrix materials which hold the PCM fibers in place in the composites. Use thermoset matrices for composites include polyesters, polyvinylesters, epoxy resins, bismaleimide, polyimide, cyanate ester, and phenolic triazine, etc.

A number of useful bulk polymers are listed in Peters et a/., the contents of which are incorporated herein by reference for all purposes.

The weight ratio between copolymer and bulk polymer typically is in the range of 1: 1 - 1: 1000, preferably in the range of 1:4 - 1: 500, such as in the range of 1 :5 - 1 :250 and even more preferably in the range of 1: 10 - 1:200, such as in the range of 1:25 - 1: 100.

Another aspect of the invention relates to modified bulk polymer comprising a copolymer as defined herein, and preferably a copolymer wherein the macromolecule is a hydrophobic polymer.

The modified bulk polymer may e.g. be a modified bulk polymer obtainable by the method of preparing a modified bulk polymer according to the present invention.

The weight ratio between copolymer and bulk polymer typically is in the range of 10: 1 - 1: 1000, preferably in the range of 1:4 - 1:500, such as in the range of 1:5 - 1:250 and even more preferably in the range of 1: 10 - 1:200, such as in the range of 1:25 - 1: 100.

An aspect of the invention relates to methods of preparing the composite material according to the present invention. The composite material can be prepared in a number of different ways as described in Peters et al., the contents of which are incorporated herein by reference. However, four methods are presently preferred.

A specific aspect of the invention relates to a first method of preparing a composite material, the method comprising the steps of: i) providing a bulk polymer and a modified PCM as defined herein, and ii) mixing the bulk polymer and the modified PCM.

Preferred PCMs for composite materials are e.g. microcrystalline cellulose, cellulose microfibrils, cellulose fibers, regenerated cellulose, plant fibers, fibre networks, or mixtures thereof.

Another specific aspect of the invention relates to second method of preparing a composite material, the method comprising the steps of: i) providing a PCM and a modified bulk polymer as defined herein,

ii) mixing the modified bulk polymer and the PCM.

Yet a specific aspect of the invention relates to third method of preparing a composite material, the method comprising the steps of: i) providing a PCM, a bulk polymer, and a copolymer as defined herein, preferably a copolymer wherein the macromolecule is a hydrophobic polymer, and

ii) mixing the modified bulk polymer and the PCM.

The mixing step of first, second, and third method of preparing a composite material may involve processes such as extrusion or solvent casting. Useful mixing techniques are wellknown to the person skilled in the art and may e.g. be found in handbooks such as Peters et al., and Rauwendaal et al., the contents of which are incorporated herein by referenece.

In the mixing step of first, second, and third method of preparing a composite material the mixing is typically performed at an elevated temperature, an typically above the softening point or glass transition temperature of the bulk polymer.

In preferred embodiments of the invention, the hydrophobic polymer of the copolymer comprises polymerised monomers that are either similar or of the same type as the monomers polymerised to form the bulk polymer. A further specific aspect of the invention relates to a fourth method of preparing a composite material, the method comprising the steps of: i) providing a mixture comprising - a modified PCM,

- monomers which can be polymerised into a bulk polymer, and

- optionally, a polymerisation initiator and/or a catalyst, and

U) polymerising the monomers of the mixture, thus obtaining a presence of the modified PCM.

Monomers which are useful for preparing polyester polymers are e.g. different combinations of diacids and glycols, e.g. acids like phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, maleic anhydride, fumaric acid, HET acid (hexachlorocyclopentadiene) or anhydride, etc., and glycols like ethylene glycol, propylene glycol, neopentyl glycol, diethylene glycol, bisphenol A, etc.

Monomers useful for preparing polyviny esters include an unsaturated carboxylic acid, e.g. methacrylic acid, and an epoxy, e.g. bisphenol A.

Monomers useful for preparing epoxy resins are molecules containing one of more epoxide groups with or without a curing agent, e.g. amine or anhydride, and / or a catalysis, e.g. Lewis acids or bases.

Monomers useful for preparing a polyimide are e.g. a mixture of a dianhydride and a diamine.

Yet an aspect of the present invention relates to a composite material obtainable from the first, second, and third method of preparing a composite material according to the present invention.

The composite material typically comprises a bulk polymer, a PCM, and a copolymer as described herein, preferably a copolymer wherein the macromolecule is a hydrophobic molecule.

In a preferred embodiment of the invention, the copolymer is bound to the PCM via hydrogen bonds between the SCP of the copolymer and the PCM.

In an embodiment of the invention, the composite material comprises PCM or modified PCM in an amount in the range of 0.01-50% by weight composite material, such as in an amount in the range of 1-40% by weight, e.g. in an amount in the range of 5-30% by weight.

For example, the composite material may comprise PCM or modified PCM in an amount in the range of 0.01-20% by weight composite material, such as in an amount in the range of 0.1-10% by weight, e.g. in an amount in the range of 1-5% by weight.

Alternatively, the composite material may comprise PCM or modified PCM in an amount in the range of 10-50% by weight composite material, such as in an amount in the range of 15-45% by weight, e.g. in an amount in the range of 20-40% by weight.

In an embodiment of the invention, the composite material comprises bulk polymer in an amount in the range of 50-100% by weight composite material, such as in an amount in the range of 60-100% by weight, e.g. in an amount in the range of 80-100% by weight.

For example, the composite material may comprise bulk polymer in an amount in the range of 50-90% by weight composite material, and PCM or modified PCM in an amount in the range of 10-50% by weight composite material, such as in an amount in the range of 15-45% by weight, e.g. in an amount in the range of 20-40% by weight. The composite materials according to the present invention may for example be used for preparing packaging materials, e.g. for liquids and foodstuff; particle boards and fibre boards, fibre composites comprising other natural or synthetic polymers or materials as well as those which may be considered electrical conductors, semi-conductors, or insulators.

The composite materials according to the present invention be use for preparing laminated paper and cardboard, which are often laminated with a thermoplastic, such as polyethylene to provide an impermeable barrier to aqueous solutions, security papers, bank notes.

An additional aspect of the invention relates to a pellet comprising the modified bulk polymer or the composite material comprising a hydrophobic bulk polymer, a copolymer, and a PCM. The pellets have typically a diameter in the range 0.1 mm-10 mm, preferably in the range 1 mm-7 mm, and even more preferred in the range of 2 mm-5 mm, such as about 3 mm. Having the modified bulk polymer or the composite material in the form a pellets makes them useful for and compatible with injection moulding techniques and standard injection moulding equipment. Yet an aspect of the invention relates to use of the copolymer, wherein a macromolecule is a hydrophobic polymer, as a compatibiliser for mixing one or more PCMs and a hydrophobic material. The hydrophobic material could e.g. be a hydrophobic polymer or a hydrophobic liquid. Compared to prior art compatibilisers the present copolymer has the advantage that it is tightly bound to the PCM, and it therefore has a very low rate of leakage from the compatibilised mixture.

The copolymer, wherein a macromolecule is hydrophobic polymer, may be use as an emulsifier and is believed to have superior emulsifying effects in many applications.

A PCM, e.g. cellulose nanocrystals, modified by binding of one or more copolymer, wherein a macromolecule is hydrophobic polymer, may also be use as an emulsifier and is believed to have superior emulsifying effects in many applications.

Additionally, it is envisioned that the copolymer, wherein a macromolecule is hydrophobic polymer as well as PCMs modified with the copolymer may be used as a carrier of hydrophobic ingredients in medical, cosmetic, and food applications.

Ingredients such as fat soluble vitamins, flavouring agents, and hydrophobic pharmaceutical may be adsorbed to the copolymer, wherein a macromolecule is hydrophobic polymer, or to the PCMs modified with said copolymer.

An additional aspect of the invention, thus relates to a composition comprising the copolymer, wherein a macromolecule is hydrophobic polymer, to which a hydrophobic active agent is adsorbed. The hydrophobic active agent may e.g. be selected from the group consisting of a pharmaceutical, a flavouring agent, a vitamin, and a biocide.

A further aspect of the invention relates to the use of the copolymer, wherein a macromolecule is a water-soluble polymer, as paper additive.

A further aspect of the invention relates to the use of the copolymer, wherein a macromolecule is a biodegradable polymer, as a biodegradable functional molecule. Most SCPs are inherently biodegradable and biodegradable polymers are used in the copolymer, the entire copolymers will be biodegradable.

Most PCMs, particularly cellulose, are biodegradable, thus a modified, biodegradable PCM to which a biodegradable copolymer is bound, will be biodegradable as well. Biodegradable composite materials are envisioned, e.g. composite materials comprising a biodegradable PCM a biodegradable, hydrophobic bulk polymer, and a biodegradable copolymer. Such biodegradable composite materials may be used as coated paper, agricultural Mulch film, shopping bags, food waste film/bags, consumer packaging materials, landfill cover film, bait bags, fishing line and nets, silage wrap, body bags and coffin liners, nappy backing sheet, sanitary product applications; and cling wrap.

Another aspect of the invention relates to the use of the copolymer, wherein a macromolecule is a polyelectrolyte polymer, as an additive in papermaking.

In some cases it is desirable to attach a copolymer comprising one or more anionic polymers to the surface of cellulosic fibers. This gives the fibers some desirable properties, such as improved retention of e.g. fiber, fines and filler minerals, in papermaking. Since the fibers are naturally anionically charged the adsorption is not spontanous.

This use corresponds to a method of preparing an improved paper, the method comprising the steps of a) providing a PCM related to papermaking, e.g. a wood pulp or a paper pulp, and a copolymer, wherein a macromolecule is a polyelectrolyte polymer and preferably an anionic a polyelectrolyte polymer, b) modifying the PCM related to papermaking, e.g. the wood pulp or the paper pulp by the method described herein, and c) preparing paper from the modified PCM.

An aspect of the invention relating to this use is a modified PCM comprising one or more copolymers, which comprises one or more anionically charged polyelectrolyte polymers, which copolymer is bound to the PCM.

It should be noted that, according to the present invention, embodiments and features described in the context of one of the aspects of the present invention also apply to the other aspects of the invention.

EXAMPLES

Example 1 Preparation with a xyloglucan endotransglycosylase (XET)

Xyloglucan (XG) from tamarind seed (Xγl:Glc:Gal:Ara = 35:45: 16:4) was purchased from Megazyme (Bray, Ireland). XET was obtained by heterologous expression of Populus tremula x tremuloides PttXETlβA in Pichia pastoris according to Kallasl, Kallas2 and Bollok et al. A mixture of xyloglucan oligosaccharides (XGO, XXXG/XLXG/XXLG/XLLG ratio 15:7:32:46) was prepared from deoiled tamarind kernel powder (300 Mesh, Maharashtra Traders, India) using endoglucanase digestion as described in Brumer et al. The aminoalditol derivatives of XGO (XGO-NH2) were prepared by reductive amination as described by Brumer et al.

Preparation of amino-terminated xyloglucan (XG-NH2) with XET technique was performed as follows. A sample containing a 1 L mixture of XG (1 g/L), XGO-NH2 (0.5 g/L) and XET (100 units) in NaOAc buffer (20 mM, pH 5.5) was incubated at 30 0C with stirring for 24 h. The reaction was terminated by heating at 90 0C for 60 min, and the denatured XET was removed by centrifugation at 12000 g for 30 min. The reaction mixture was concentrated to 200 mL by rotavapor. Then, 2 L of ethanol was added to precipitate XG-NH2, with the XGO-NH2 in the supernatant. After filtration over a Whatman GF/A glass microfibre filter, the precipitated XG-NH2 was dried under vacuum, redissolved in water and lyophilised. The XG-NH2 produced in this manner had a Mw value of 1.7 x 104 (PDI = 1.6).

Example 2 Preparation with a cellulase

A Trichoderma reβsei cellulase mixture was obtained from a commercial source (Fluka). Cellulase activity was generally assayed using the method of Garcia et al. Cellulase activity toward xyloglucan was assayed using an adaptation of the tri-iodide binding assay described by Sulova et al. (Anal. Biochem. 1995, 229, 80-85).

A sample containing a 1 L mixture of XG (5 g/L) and cellulase (50 units) in NaOAC buffer (10 mM, pH 4.5) was incubated at 37 0C with stirring for 1 h. The reaction was terminated by heating at 95 0C for 60 min, and the denatured cellulase was removed by filtration over a Whatman GF/A glass mirofibre filter. After the solution was concentrated to 200 mL, 2 L of ethanol was added to precipitate XG and remove the buffer. The precipitated XG was filtered and dried under vacuum. The XG produced in this manner had a Mw value of 2.0 x 104 (PDI = 1.5). PDI is the polydispersity index.

XG (1 g) prepared by cellulase degradation and 40 g ammonium hydrogen carbonated (NH4HCO3) was dissolved in 50 mL water and stirred at room temperature for 4 h, sodium cyanoborohydride (2 g) were then added. After the mixture was stirred at room temperature for 7 days, hydrochloric acid (HCI) was added until the solution reached pH 2. Followed by addition of 1 L ethanol, the crude product was precipitated on Whatman GF/A glass microfiber filters, vacuum dried and redissolved in 100 mL water. After dialysis against deionized water for 3 days, the pure products were freeze-dired to give XGNH2 as white power. Example 3 Preparation with a galactose oxidase

Dactylium dendroides galactose oxidase was obtained from Sigma; activity was monitored according to a published method (Sun, et al. Protein Eng. 2001, 14, 699-704).

Following oxidation of galactosyl hydroxymethyl groups to formyl groups with galactose oxidase/catalase, a reductive amination reaction can be used to introduce amino groups on C-6 of galactose residues along the backbone of xyloglucan. The preparation procedure adopted was based on methods developed for other polysaccharides and involved the enzymic oxidation of galactosyl C-6 hydroxymethyl groups to formyl groups using galactose oxidase/catalase.

To a solution of cellulase degraded xyloglcuan (50 mg, Mw = 2.0 x 104, PDI = 1.5) in 50 mL 10 mM phosphate buffer (pH 7), 1200 Units of catalase in 0.1 M phosphate buffer and 2.2 units of galactose oxidase in 0.1 M phosphate buffer are added. The reaction mixture was kept at 27 0C for 24 h, ammonium hydrogen carbonate (NH4HCO3, 20 g) was then added. After the mixture was stirred at 20 0C for 4 h, 10 molar equivalent amount of sodium cyanoborohydride with respect to the aldehyde groups was added and the mixture was kept at 20 0C for 7 days. The products were precipitated in ethanol, redissolved in water, dialyzed exhaustively against distilled water and lyophilized.

Example 4 and 5 demonstrate how a SCP-polystyrene conjugate may be prepared. Copolymers can be synthesized in number of different ways, e.g. by:

(A) Couple different small oligomers and then to grow the chains by polymerization.

(B) First synthesize one of the blocks and then couple it to another type of monomer and polymerize the second block.

(C) Polymerize blocks separately and then perform a coupling reaction between them.

In the present experiment, the approach C, i.e. coupling of prefabricated blocks, was used to couple amino-terminated xyloglucan to carboxylic acid-terminated polystyrene.

Figure imgf000044_0001

Example 4 Preparation of carboxylic acid-terminated polystyrene

A dry round-bottom flask was charged with CuBr (391 mg, 2.7 mmol), N,N,N',N",N"- pentamethyldiethylenetriamine (PMDETA, 563 μL, 2.7 mmol), styrene (90 mL, 786 mmol), and a magnetic stir bar. The flask was sealed with a rubber septum and degassed by three freeze-pumpthaw cycles. The flask was immersed in an oil bath thermostated at 110 0C, and 4-(l-bromoethyl)benzoic acid (2.7 mmol) was added dropwise. The product was precipitated into methanol after 5 h reaction. The molecular mass of the product is 30,000 as determined by SEC. 1H NMR (CDCI3; end groups only): d = 0.92-1.12, HOOC-C6H4- CH(CW3)-; 4.34-4.60, -CH(C6H5)Br; 7.89, HOOC-C6H4-CH(CH3)-.

Example 5 Preparation of di-block copolymers of xyloglucan and polystyrene (XG- A-PS) XGNH2 (0.50 g) from Example 1, carboxylic acid-terminated polystyrene (0.25 g) from Example 4, 4,4-dimethylaminopyridine (DMAP, 80 mg) and N-Ethyl-N'-(3- dimethylaminopropyl)carbodiimide (EDC, 500 μL) were mixed in /V/ZV-dimethylformamide (DMF, 200 mL) and water (10 mL) and stirred at 60 0C for 20 h. Subsequently, the mixture was cooled to room temperature and diluted with methanol (1 L) to form a precipitate. The precipitate was filtered and washed several times with methanol and redissolved in hot water. The unreacted PS were removed by filtration, the resulting filtrate (aqueous colloidal solution of XG-ύ-PS) were dialyzed against deionized water and freeze-dried (ca. 300 mg, yield in 60%).

Example 6 Preparation of cellulose nanocrystals

Suspensions of cellulose nanocrystals were prepared as follows. Whatman No. 1 filter paper was ground with a kitchen coffee mill for 30 min. The ground paper (20 g) was mixed with sulfuric acid (175 mL, 64 wt%) and stirred at 45 0C for 1 h. Immediately following hydrolysis, suspensions were diluted 10-fold to stop the reaction. The suspensions were then centrifuged, washed once with water, and recentrifuged. The resulting precipitate was placed in regenerated cellulose dialysis membranes having a molecular weight cutoff of 12 000-14 000 and dialyzed against water for several days until the water pH remained constant. To achieve colloidal cellulose particles, suspensions were sonicated for 7 min using a Branson sonifier, while cooling in an ice bath to avoid overheating. Finally, suspensions were allowed to stand over a mixed bed resin (Sigma- Aldrich) for 24-48 h and then filtered. The final aqueous suspensions were approximately 1 5 wt% concentration by weight.

Example 7 Adsorption of XG-b-PS onto cellulose nanocrystals

To measure the adsorption of XG-ZP-PS to cellulose nanocrystals, 10, 25, 50, 100, 200, 10 300, and 500 mg of XG-i>-PS were added into glass vials containing 10 mL of cellulose suspensions (0.5 wt%) and incubated at 20 0C with orbital shaking for 24 h. The cellulose nanocrystals were then separated by centrifugation at 12000 g for 30 min. The adsorbed amount of XG-ύ-PS onto cellulose in each sample was measure by thermal gravity analysis (TGA). 15

Example 8 Suspension of XG-b-PS adsorbed cellulose nanocrystals in non-polar organic solvents.

5 mL (0.2 wt%) cellulose nanocrystal suspensions were mixed with 0, 20 and 30 mg of XG-d-PS di-block copolymer obtained from Example 5 and incubated at 20 0C with orbital 0 shaking for 24 h. The mixtures were then freeze dried on a Christ Alpha 2-4 LDplus freeze dryer, and resuspended in 4 mL toluene. To achieve colloidal cellulose particles in toluene, suspensions were sonicated for 2 min using a Branson sonifier, while cooling in an ice bath to avoid overheating.

5 After adsorbed with XG-t»-PS copolymer, the modified cellulose nanocrystals can be dispersed in nonpolar organic solvents such as toluene, THF and chloroform. 10 mg cellulose nanocrystals were dispersed in 4 mL non-polar solution with addition of varying amounts of XG-t»-PS copolymer. The amount of copolymer and the solvent type for tests A-E were: 0

A: 0 mg copolymer/Toluene B: 20 mg copolymer/Toluene C: 30 mg copolymer/Toluene D: 20 mg copolymer/THF 5 E: 20 mg copolymer/CHCI3 The results are shown in Figure 4. After 1 h of suspension, in the vial A, corresponding to the untreated initial sample, the flocculation is so strong that a total phase separation has occurred. In the vial B and C7 stable and slightly cloudy suspensions are observed. Since the density of cellulose nanocrystals is approx. 1.6, precipitation occurred in Toluene and THF after 72 h. However, cellulose nanocrystals can be suspended again in Toluene and THF after precipitation. Stable suspensions were found in the chloroform.

The suspensions were observed between crossed polars as shown in Figure 6. The homogeneous suspension in toluene is as birefringent as the suspension in water, indicating that the cellulose microcrystals are individualized in the organic solvent when XG-ύ-PS copolymer was adsorbed on their surfaces.

Example 9 Preparation of cellulose / PLLA nanocomposite films

The cellulose / polylactic acid (PLLA) nanocomposite films may be prepared by solvent casting in chloroform. The suspension of cellulose nanocrystals and PLLA is mixed in chloroform in various proportions in order to obtain final dry composite films ranging between 0.5 and 1 mm in thickness and with 0-20% weight fractions of cellulose nanocrystals in PLLA matrix. After the samples are stirred for 6 h, the mixture is cast in a glass Petri dish and evaporated at 20 0C and after that at 80 0C for 1 h.

Example 10 Preparation of poly (lactic acid)-g rafted xyloglucan

The cellulase degraded xyloglucan from Example 2 (1.00 g, Mw = 2.0 x 104, PDI = 1.5) may be suspended in pyridine (50 mL). Chlorotrimethylsilane (TMS-CI, 7.03 mL, 56.4 mmol) is dissolved in n-hexane (20 mL), and the solution is added to the xyloglcuan suspension. After 3 h of stirring, the reaction mixture is washed with saturated NaCI aqueous solution to remove pyridine hydrochloride. After reprecipitation with n-hexane and evaporation under reduced pressure, mostly trimethylsilylated xyloglucan (TMS-XG) will be obtained. 1H NMR spectra, GPC for Mw, the degree of trimethylsilylation (DTMS), and Yield may be determined.

The following procedures may be performed under argon atmosphere. TMS-XG (500 mg) is dissolved in dry HF (5.0 mL). Potassium te/t-butoxide (t-BuOK, 33.7 mg, 0.30 mmol) is dissolved in dry THF (5.0 mL), and the resulting solution is added to the TMS-XG solution. After stirring for 1 h, L-lactide (3.60 g, 25 mmol) in THF (10 mL) is added. The reaction is carried out at room temperature for 5 h. The obtained products are precipitated twice with ethyl ether. Characterization of the TMS-protected graft copolymer is performed by 1H NMR. The obtained TMS-protected graft copolymer is dissolved in 50 mL of CHCI3, 250 mL of methanol is added, and the mixture is stirred for 2 days to deprotect the TMS groups. The deprotection of TMS groups may be confirmed by the disappearance of the methyl proton signal at δ = 0.10 ppm by 1H NMR. The product PLA-g-XG may be measured by GPC.

Example 11 Preparation of di-block copolymers of xyloglucan and polylactic acid

XGNH2 (0.50 g) from Example 1, polylactic acid (PLLA, Biomer, 0.25 g), 4,4- dimethylaminopyridine (DMAP, 80 mg) and N-Ethyl-N'-(3- dimethylaminopropyl)carbodiimide hydrochloride (EDCHCL, 50 mg) are mixed in N, N- dimethylformamide (DMF, 200 mL) and water (10 mL) and stirred at 60 0C for 20 h. Subsequently, the mixture is cooled to room temperature and diluted with methanol (1 L) to form a precipitate. The precipitate is filtered and washed several times with methanol and redissolved in hot water, then filtrate to remove unreacted PLLA. The filtrate solution containing the product XG-d-PLLA is dialyzed against deionized water and freeze-dried.

Example 12 Adsorption of XG-ύ-PLLA onto cellulose nanocrystals

To measure the adsorption of XG-ZJ-PLLA to cellulose nanocrystals, 10, 25, 50, 100, 200, 300, and 500 mg of XG-ό-PLLA are added into glass vials containing 10 mL of cellulose suspensions (0.5 wt%) and incubated at 20 0C with orbital shaking for 24 h. The cellulose nanocrystals are then separated by centrifugation at 12000 g for 30 min. The adsorbed amount of XG-ύ-PLLA onto cellulose in each sample may be measured by thermal gravity analysis (TGA).

Example 13 Preparation of an initiator-terminated xyloglucan

4-(2-(2-Bromopropionyloxy)ethoxy)benzoic acid (synthesized according to Zhang et al., 267 mg, 0.84 mmol) and N-Ethyl-N'-(3-dimethylaminopropyl)carbodiimide (EDC, 149 μl, 0.84 mmol), are dissolved in N,N-dimethylformamide (DMF, 2 mL) and stirred at room temperature for 15 min. A solution of XGO-NH2 (500 mg, 0.4 mmol) and 4,4- dimethylaminopyridine (5 mg, 0.04 mmol) in DMF (5 mL) is then added. The mixture is stirred at room temperature for 4 h, followed by the addition of acetone. The resulting precipitate is collected on Whatman GF/A glass microfibre filters, vacuum dried and purified on a C18 reversed phase column (Silica 6OA 40 - 63 μm C18, SDS, France, 2.6 cm x 10 cm) by stepwise elution with increasing concentrations Of CH3CN in water. Fractions containing pure products (TLC, 70:30 acetonitrile: water) are pooled and freeze-dried to give XGO-INI as a white powder (272 mg, yield in 44%). A sample containing a 1 L mixture of XG (1 g/L), XGO-INI (0.5 g/L) and XET (100 units) in NaOAc buffer (20 mM, pH 5.5) is incubated at 30 0C for 24 h. The reaction is terminated by heating at 90 0C for 60 min, and the denatured XET is removed by centrifugation at 12000 g for 30 min. The reaction mixture is concentrated to 200 mL by rotavapor. Then, 2 L of 5 ethanol is added to precipitate XG-INI, with the XGO-INI in the supernatant. After filtration over a Whatman GF/A glass microfibre filter, the precipitated XG-INI is dried under vacuum, redissolve in water and lyophilised. The initiator-modified XG (XG-INI) produced in this manner has a Mw of 2.2 x 104 (PDI = 1.6).

10

Example 14 Preparation of di-block copolymers of xyloglucan and polyacrylamides

A single-neck round-bottom flask equipped with a stir bar is charged with N1N- dimethylacrylamide (DMA, 50 mL), N,N-dimethylformamide (DMF, 10 mL), water (90 mL)

15 and l^^ll-Tetramethyl-lAS^l-tetraazacyclotetradecane (Me4Cyclam, 10 mg). After degassing with argon for 30 min, CuBr (5 mg) and initiator-terminated xyloglucan (XG- INI) prepared in Example 12 (0.50 g) is added. The reaction is carried out at room temperature for 1 h. The resulting copolymer is precipitated into 1-butanol, filtered, washed with diethyl ether, and dried in a vacuum oven at 40 0C. The copolymer XG-ό-

20 PDMA is then dissolved in water, dialyzed (Fisher, cellulose tubing, cutoff 12 000-14 000 g mol-1), and freeze dried.

Example 15 Adsorption of XG-6-PDMA onto standard commercial pulp

To measure the adsorption of XG-ύ-PDMA to standard commercial pulp, 25, 50, 100, 200, 25 300, and 500 mg of XG-t>-PS are added into glass vials containing 10 mL of pulp suspensions (1 wt%) and incubated at 20 0C with orbital shaking for 24 h. The pulps are then separated by centrifugation at 12000 g for 30 min. The adsorbed amount of XG-ύ-PS onto cellulose in each sample may be measured by thermal gravity analysis (TGA).

30 Example 16. Retention properties of the XG-6-PDMA adsorbed standard commercial pulp

To measure the retention ability, 0.1 g standard commercial pulp with 20 mg adsorbed XG-ό-PDMA are suspended in 10 mL of an aqueous solution containing 50, 100, 250, and 500 mg anionic starch in glass vials and incubated at 20 0C with orbital shaking for 10 min. 35 The pulps are then separated by filtration over a Whatman GF/A galss microfibres filter. The anionic starch adsorbed onto the XG-ύ-PDMA modified pulp may be measured by the loss of anionic starch in solution by means of a colorimetric assay. Example 17 Preparation of pyrrole-terminated xyloglucan oligosaccharides (XGO- pyrrole)

XGO-NH2 (500 mg, 0.4 mmol) and triethylamine (TEA, 167 μL 1.2 mmol) are dissolved in 5 N,N-dimethylformamide (DMF, 5 mL) and stirred at room temperature for 15 min. A solution of Succinic anyhydride (80 mg, 0.8 mmol) in DMF (2 mL) is then added dropwise. The mixture is stirred at room temperature for 4 h, followed by the addition of acetone. The resulting precipitate is collected on Whatman GF/A glass microfibre filters, vacuum dried and purified on a C18 reversed phase column (Silica 6OA 40 - 63 μm C18, SDS, 10 France, 2.6 cm x 10 cm) by stepwise elution with increasing concentrations of CH3CN in water. Fractions containing pure products (TLC, 70:30 acetonitrile:water) are pooled and freeze-dried to give carboxylic acid terminated XGO.

8-pyrrol-l-aminooctane (0.500 g, 2.57 mmol) is added to a solution of carboxylic acid 15 terminated XGO (2 g, 2.57 mmol) in 100 ml of mixture of methanol and water (9: 1). The mixture is stirred under reflux in methanol for 24 h. The solvent is evaporated under vacuum and, after freeze-drying, the product is obtained which may be characterized by 1H NMR, and mass spectroscopy.

20

Example 18 Preparation of pyrrole-terminated xyloglucan

A sample containing a 1 L mixture of XG (1 g/L), XGO-pyrrole (0.5 g/L) and XET (100 units) in NaOAc buffer (20 mM, pH 5.5) is incubated at 30 0C for 24 h. The reaction is terminated by heating at 90 0C for 60 min, and the denatured XET is removed by

25 centrifugation at 12000 g for 30 min. The reaction mixture is concentrated to 200 mL by rotavapor. Then, 2 L of ethanol is added to precipitate XG-pyrrole, with the XGO-pyrrole in the supernatant. After filtration over a Whatman GF/A glass microfibre filter, the precipitated XG- pyrrole is dried under vacuum, redissolve in water and lyophilised. The initiator-modified XG (XG- pyrrole) produced in this manner had a Λfw of 1.8 x 104 (PDI =

30 1.5).

Example 19 Preparation of copolymers from xyloglucan and polypyrrole

Pyrrole-terminated xyloglucan (1 g) is dissolved in 100 mL of distilled water and stirred for 35 30 min; then an oxidant, ferric chloride (FeCI3), is added and the mixture is stirred for 1 h. Pyrrole is dissolved in 100 mL of water and introduced dropwise into thereaction mixture, which is then stirred for a further 30 min. The molar ratio [FeCI3]/[pyrrole] is 5.0. After 15 h the mixture is transferred into dialysis tube (Fisher, cellulose tubing, cutoff 12 000-14 000 g mol-1) and dialyzed against deionized water for 2 days, then freeze dried.

Example 20 Preparation of carboxylic acid-terminated polymethyl methcarylate with pendant spirobenzopyran groups (SP) l'-(2-Methacryloxyethyl)-3',3'-dimethyl-6-nitrospiro(2H-l-benzopyran-2,2'-indoline) (SP monomer) is prepared as follows: A solution of SP alcohol (15.0 g, 42.6 mmol) and triphenylphosphine (20.1 g, 76.7 mmol) in THF (640 mL) is cooled to 0 0C under Argon. Diethylazodicarboxylate (13.2 g, 75.8 mmol) is then added, and the mixture is stirred for 10 min. Following the addition of methacrylic acid (6.6 g, 75.8 mmol) and after removal of cooling, the solution is stirred for 24 h at room temperature. The solvent is dried using a rotary evaporator and the product passed through the silica gel column to remove oxyphosphonium salts. The crude product (21.9 g) is recrystallized from hexanes to give 14.8 g (35.1 mmol) of pale green crystals in 82.5% yield.

Preparation of acid-terminated poly(SP-co-MMA) containing 30 mol % SP (pSP0.3-co- MMAO.7) is as follows: A dry round-bottom flask is charged with CuBr (163 mg, 0.73 mmol), CuCI2 (4.86 mg, 0.035 mmol), ty/V^/V^W^pentamethyldiethylenetriamine (PMDETA, 0.90 mL, 4.31 mmol), 4-(2-(2-Bromopropionyloxy)ethoxy)benzoic acid (2.0 mmol), SP (24 g, 57 mmol), MMA (13.3 g, 133 mmol), THF (5 mL) and a magnetic stir bar. The flask is sealed with a rubber septum and degassed by three freeze-pumpthaw cycles. The flask is immersed in an oil bath thermostated at 65 0C. The product is precipitated into methanol after 24 h reaction, and recovered and dissolved in N, N- dimethylformamide (DMF). The solution is added into methanol again to precipitate the product. The product is dried in vacuum and used for further experiments. The content of SP in the copolymer may be determined by ultraviolet absorption. The molecular weight of copolymers may be estimated by gel permeation chromatography.

Example 21 Preparation of graft copolymers of xyloglucan and poly(SP-co-MMA)

XGNH2 (1.0 g) from Example 3, carboxylic acid-terminated poly(SP-co-MMA) (0.25 g) from Example 4, 4,4-dimethylaminopyridine (DMAP, 80 mg) and N-Ethyl-N'-(3- dimethylaminopropyl)carbodiimide (EDC, 500 μL) are mixed in Dimethyl Sulfoxide (DMSO, 200 mL) and stirred at 60 0C for 20 h. Subsequently, the mixture is cooled to room temperature and diluted with methanol (1 L) to form a precipitate. The precipitate is filtered and washed several times with methanol and redissolved in water, dialyzed against deionized water (Fisher, cellulose tubing, cutoff 12 000-14 000 g mol-1), and freeze-dried.

Example 22 Preparation of regenerated cellulose membrane a. Preparation of regenerated cellulose membrane from cuprammonium solution According to the method of Okajima [Okajima, K. (1995) Polymer Journal, 27(11), 1113- 1122], 1Og cellulose (Whatman No. 1 filter paper, UK) is dissolved in a mixture of 65g NH4OH (20%), 12g freshly prepared Cu(OH)2, 8g 10% (w/v) NaOH and 30g water to give a clear blue viscous solution at 4 0C. The solution is cast on a glass plate to give a thickness of 0.3 mm and then placed in coagulation baths maintained at 4 0C of 10% aqueous NaOH followed by 4% aqueous H2SO4 for 5 min each, respectively. The regenerated cellulose films obtained are washed in running water and dried on a glass plate at room temperature.

b. Preparation of regenerated cellulose membrane from aqueous NaOH/urea solution. Bemliese® nonwoven cloth made from cotton linters in curprammonium solution (DP= 650, Asahi Chemical Industry Co. Ltd., Japan) is used as the source of cellulose. 10 g Bemliese® nonwoven cloth is dissolved in 200 ml 6 wt % NaOH / 4 wt % urea aqueous solution to obtain a clear cellulose solution at 4 0C. The solution is cast on a glass plate to give a thickness of 0.5 mm, then immediately immersed into 5 wt % H2SO4 aqueous solution to allow coagulatation for 5 min at 4 0C. The transparent membranes obtained are washed by running water and dried in air on a glass plate at room temperature.

Example 23 Adsorption of poly(SP-co-MMA)-g-XG onto regenerated cellulose film and UV-vis absorption measurement

2 x 4 cm2 Regenerated cellulose film are immersed in 10 ml of (2 mg/mL) XG-g-poly(SP- co-MMA) (from Example 20) in an aqueous solution with mild shaking for 24 h. The film is then withdrawn and washed extensively with deionized water and dried in vacuum. The film is then soaked in toluene before the UV-vis absorption measurement.

Example 24 Measurement of the binding strength between cellulose and copolymer. To quantify the binding strength between cellulose and a copolymer the following assay may be employed. 5000 mg of the copolymer is mixed with a 100 mL suspension of cellulose nanocrystals (0.5 wt% in water) obtainable via Example 6 and transferred in 10 mL aliquots to glass vials and incubated at 20 0C with orbital shaking for 24 h. The now modified cellulose nanocrystals are then separated by centrifugation at 12000 g for 30 min.

The modified cellulose nanocrystals are washed twice by resuspending each aliquot of the cellulose nanocrystals in 10 mL water, and separating them again by centrifugation at 12000 g for 30 min. The resulting modified cellulose nanocrystals are finally dried and stored at 5 0C.

The amount of copolymer adsorbed to 0.05 g of dry, modified cellulose nanocrystals is measured by thermal gravity analysis (TGA) according to the standard ASTM 1131-03, and the amount of bound copolymer per 1 g of dry, modified cellulose nanocrystals, A0, is determined.

The "dissociation" or release of the copolymer from the copolymer-cellulose complex is determined by suspending 0.05 g of dry, modified cellulose nanocrystals in 10 mL water in a glass vial and incubating the suspension at 20 0C with orbital shaking for 24 h. The suspension of modified cellulose nanocrystals are then centrifuged at 12000 g for 30 min. to separate the nanocrystals from the supernatant, and the total amount of copolymer in the supernatant is determined e.g. by thermogravimetry or by other suitable methods known to the person skilled in the art, such as spectroscopy or fluorometry. Useful methods of analysis may be found in Settle et al., the contents of which are incorporated herein by reference for all purposes.

Based on this data, the amount of released copolymer per 1 g of dry, modified cellulose nanocrystals, A1, is determined.

The ratio, R0, between the amount of copolymer which has been washed of and released from the modified cellulose nanocrystals during the incubation (A1) and the total amount of copolymer bound to the modified cellulose nanocrystals before the wash (A0) is a measure of how strongly the copolymer binds to the cellulose, and is determined as

R - 4

An RD value near 1 means that most of the copolymer is washed off and indicates a poor binding strength. An RD value near 0 indicates that most of copolymer stays on the cellulose and indicates a high binding strength. REFERENCES

ASTM D5338-98 ASTM D5338-98, Standard Test Method for Determining Aerobic Biodegradation of Plastic Materials Under Controlled Composting Conditions; ASTM International, USA.

ASTM D570-98 ASTM D570-98, Standard Test Method for

Water Absorption of Plastics; ASTM International, USA.

ASTM E1131-03 ASTM El 131-03, Standard Test Method for Compositional Analysis by Thermogravimetry; ASTM International, USA.

Bollok et al. Production of Poplar Xyloglucan Endotransglycosylase Using the Methylotrophic Yeast Pichia pastoris; Bollok et al.; Applied Biochemistry and Biotechnology Vol. 126, 2005, 61-77

Brumer et al. Brumer, H.; Zhou, Q.; Baumann, M. J.; Carlsson, K.; Teeri, T. T. J Am Chem Soc 2004, 126, 5715.

Collins et al. Collins, P.; Ferrier, R. Monosaccharides, John Wiley & Sons, 1995

Freitas et al. Freitas, et al., 2004, Thermochimica Acta, 409, 41-47.

Fry et al. Fry, S. C ; York, W. S.; Albersheim, P.; Darvill, A.; Hayashi, T.; Joseleau, J. P.; Kato, Y.; Lorences, E. P.; Maclachlan, G. A.; Mcneil, M.; Mort, A. J.; Reid, J. S. G.; Seitz, H. U.; Selvendran, R. R.; Voragen, A. G. J1; White, A. R. Physiol. Plant. 1993, 89, 1.

Garcia et al. Garcia et al.; J. Food Biochem.; 1993; 17; 135-145

Kallasl Asa Kallas, Licentiate thesis, 2004, Royal Institute of Technology (KTH), Stockholm, Sweden, http://media.lib.kth. se/licenqrefhit.asp?licnr= 1703)

Kallas2 Enzymatic properties of native and deglycosylated hybrid aspen (Populus tremula xtremuloides) xyloglucan endotransglycosylase 16A expressed in Pichia pastoris; Kallas et al. ; Biochem. J. (2005) 390, 105-113

MaIz et al. MaIz, H.; Komber, H.; Voigt, D.; Hopfe, I.; Pionteck, J. Macromolecules, 1999, 200, 642.

March Jerry March, Advanced Organic Chemistry, 4th ed., John Wiley & Sons, New York, 1992.

Peters et al. S. T. Peters, Handbook of Composites, Second edition, 1998, Chapman & Hall

Rauwendaal et al. Polymer Extrusion; Chris Rauwendaal; Hanser Gardner

Publications; 4th edition (October 1, 2001); ISBN: 1569903212

Revol et al. Revol, J. -F.; Godbout, L.; Dong, X. -M.; Gray, D. G. Liq. Cry St., 1994, 16, 127.

Settle et al. Handbook of Instrumental Techniques for Analytical Chemistry, Editor: Frank Settle, Prentice Hall, 1997

Sharma et al. Sharma & Singh, 2005, Desalination, 186, 21-27.

Smith et al. Michael B. Smith and Jerry March, March's Advanced Organic Chemistry: Reactions, Mechanisms, and Structure, 5th ed., John Wiley & Sons, New York, 2001.

Sulova et al. Anal. Biochem.; 1995; 229; 80-85

U.S. Patent No. 6,608,323

Zhang et al. Zhang, X.; Matyjaszewski, K. Macromolecules 1999, 32, 7349. Zhou et al. Xyloglυcan and xyloglucan endo-transglycosylases

(XET): Tools for ex vivo cellulose surface modification; Qi Zhou, Martin J. Baumann, Peter S. Piispanen, Tuula T. Teeri, Harry Brumer; Biocatalysis and Biotransformation; 2006; Vol. 24; No. 1-2; Pages 107- 120

Claims

1. A copolymer comprising an SCP and a macromolecule (PM) covalently attached to the SCP.
2. The copolymer according to claim I1 wherein the macromolecule comprises a hydrophobic polymer.
3. The copolymer according to any of the preceding claims, wherein the macromolecule consists essentially of a hydrophobic polymer.
4. The copolymer according to claim 2 or 3, wherein the hydrophobic polymer is selected from the group consisting of polystyrene, poly(acrylic acid), poly(methyl methacrylate), polypropylene, polyethylene, polycarbonate, poly(lactic acid), and poly(caprolactone).
5. The copolymer according to any of the preceding claims, wherein the macromolecule comprises a biodegradable polymer.
6. The copolymer according to any of the preceding claims, wherein the macromolecule consists essentially of a biodegradable polymer.
7. The copolymer according to claim 5 or 6, wherein the biodegradable polymer is selected from the group consisting of poly(lactide), poly(glycolide), poly(trimethylene carbonate), poly(valerolactone), poly(propiolactone), poly(caprolactone), a poly(hydroxyalkanoate) such as poly(hydroxybutyrate), poly(hydroxyvalerate), poly(hydroxybutyrate-co- polyhγdroxyhexanoate), poly(butylene succinate), poly(butylene succinate adipate), poly(vinyl alcohol), poly(ethylene tetraphalate), poly(butylene adipate-co-terephthalate), poly(tetramethylene adipate-co-terephthalate, poly(ethylene vinyl alcohol).
8. The copolymer according to any of the preceding claims, wherein the macromolecule comprises a water-soluble polymer.
9. The copolymer according to any of the preceding claims, wherein the macromolecule consists essentially of a water-soluble polymer.
10. The copolymer according to claim 8 or 9, wherein the water-soluble polymer is selected from the group consisting of poly(vinyl alcohol), poly(ethylene vinyl alcohol), DNA, RNA, protein, poly(acrylic acid), poly(methacrylic acid), poly(itaconic acid), poly(allenesulfonic acid), poly(ethylenesulfonic acid), poly(styrenesulfonic acid), poly(2- sulfoethyl methacrylate), poly(acrylamide), poly(methacrylamide), poly(N- hydroxymethylacrylamide), poly(N,N-dimethylacrylamide), poly(N- isopropylacrylamide), polyCN-acetamidoacrylamide), poly(2-aminoethyl methacrylate), poly(N,N- dimethylaminoethyl methacrylate), poly(N-vinyl-2-pyrrolidone), poly(2-vinylpyridine), poly(3-vinylpyridine), poly(4-vinylpyridine), poly(4-methylenehydantoin), poly(4-vinyl-3- morpholine), poly(l-vinyl-2-methyl-2-imidazoline), poly(allyl alcohol), poly(2-hydroxyethyl acrylate), poly(2- hydroxyethyl methacrylate), and poly(2-hydroxypropyl methacrylate).
11. The copolymer according to any of the preceding claims wherein the macromolecule comprises a polyelectrolyte polymer.
12 The copolymer according to any of the preceding claims, wherein the macromolecule consists essentially of a polyeleectrolyte polymer.
13. The copolymer according to claim 11 or 12, wherein the polyelectrolyte polymer is selected from the group consisting of a polycationic polymer, such as e.g. poly(L-lysine), poly(L-glutamine), polyvinylamide, polyethylenimine, other polymeric primary or secondary amines, or copolymers, functionalized derivates, or blends or combinations hereof, as well as various salts thereof.
14. The copolymer according to any of the preceding claims wherein the macromolecule comprises an electrically conducting polymer polymer.
15. The copolymer according to any of the preceding claims, wherein the macromolecule consists essentially of an electrically conducting polymer.
16. The copolymer according to claim 14 or 15, wherein the electrically conducting polymer is selected from the group consisting of poly(acetylene)s, poly(pyrrole)s, poly(thiophene)s, poly(aniline)s, poly(fluorene)s, polynaphthalenes, poly(p-phenylene sulfide), and poly(para-phenylene vinylene)s.
17. The copolymer according to any of the preceding claims wherein the macromolecule comprises a signal-responsive polymer.
18. The copolymer according to any of the preceding claims, wherein the macromolecule consists essentially of a signal-responsive polymer.
19. The copolymer according to claim 17 or 18, wherein the signal-responsive polymer is selected from the group consisting of acrylic acid, methacrylic acid, L-glutamic acid, gama- benzyl L-glutamate, (pH- and ionic strength-sensitive); spiropyran- containing methacrylate, methacrylate, spiropyran-containing styrene (photo sensitive); 3-carbamoyl-
5 l-(p-vinylbenzyl)pyridinium chloride (oxidoreduction-sensitive); N-isopropylacrylamide-co- acrylic acid (thermo-senstive).
20. The copolymer according to any of the preceding claims wherein the macromolecule comprises a polymer selected from the group consisting of a semiconducting polymer, an
10 electroluminescent polymer, a ferroelectric polymer, a ferromagnetic polymer, a nucleic acid, a impact-modified polymer, a liquid-crystalline polymer, a nonlinear optical polymer, an optically active polymer, a photoelastic polymer, a photoluminescent polymer, a piezoelectric polymer, a resist polymer, a shape-memory polymer, a superabsorbent polymer, a telechelic polymer, a redox polymer, and a metal chelating polymer.
15
21. The copolymer according to any of the preceding claims, wherein the copolymer is a block copolymer.
22. The copolymer according to claim 21, wherein the copolymer is a di-block polymer, the 20 first block comprising the SCP and the second comprising a macromolecule.
23. The copolymer according to claim 21, wherein the copolymer is a tri-block polymer, the first block comprising the SCP, the second block comprising the macromolecule, and the third block comprising an SCP or a macromolecule.
25
24. The copolymer according to claim 21, wherein the copolymer is a tri-block polymer, the first block comprising the macromolecule, the second block comprising the SCP, and the third block comprising an SCP or a macromolecule.
30 25. The copolymer according to any of the claims 1-24, wherein the copolymer comprises: a backbone comprising the SCP, and one or more macromolecules grafted to the SCP.
26. The copolymer according to any of the claims 1-24, wherein the copolymer comprises: 35 a backbone comprising the SCP, and at least two macromolecules grafted to the SCP.
27. The copolymer according to any of the claims 1-24, wherein the copolymer comprises: a backbone comprising the macromolecule, and one or more SCPs grafted to the macromolecule.
28. The copolymer according to any of the claims 1-24, wherein the copolymer comprises: a backbone comprising the macromolecule, and
5 at least two SCPs grafted to the macromolecule.
29. The copolymer according to any of the claims 1-24, wherein the copolymer is a dendrimer comprising: a branched macromolecule having at least 3 end groups, and
10 at least one SCP covalently attached to one of the at least 3 end groups of the branched macromolecule.
30. The copolymer according to claim 29, wherein at least two SCPs each are attached to an end group of the at least 3 end groups of the branched macromolecule.
15
31. The copolymer according to claim 29, wherein SCPs are attached to all of the at least 3 end groups of the branched macromolecule.
32. The copolymer according to claim 30-31, wherein the SCPs are of the same type. 20
33. The copolymer according to claim 29, wherein at least one SCP is of a different type than the other SCPs of the copolymer.
34. The copolymer according to claim 33, wherein all the SCPs of the copolymer are of 25 different types.
35. The copolymer according to any of the preceding claimscomprising in the range of 1- 500 macromolecules covalently attached to the SCP.
30 36. The copolymer according to any of the preceding claims comprising in the range of 1- 500 SCPs covalently attached to the macromolecule.
37. The copolymer according to any of the preceding claims, wherein one or more macromolecules are covalently attached to a natural reducing end of an SCP.
35
38. The copolymer according to any of the preceding claims, wherein one or more macromolecules are covalently attached to the back-bone of the SCP.
39. The copolymer according to any of the preceding claims, wherein one or more macromolecules are covalently attached to side-chains of the SCP.
40. The copolymer according to any of the preceding claims, wherein the molecular weight 5 of a macromolecule is in the range 1,000-1,000,000 g/mol.
41. The copolymer according to any of the preceding claims, wherein the molecular weight of the SCP is in the range 5,000-2,000,000 g/mol.
10 42. The copolymer according to any of the preceding claims, wherein the molecular weight of the SCP is in the range 5,000-200,000 g/mol.
43. The copolymer according to any of the preceding claims, wherein the molecular weight of the SCP is in the range 20,000-2,000,000 g/mol.
15
44. The copolymer according to any of the preceding claims, wherein the molecular weight of the SCP is in the range 5,000-200,000 g/mol and the molecular weight of a macromolecule is in the range 1,000-1,000,000 g/mol.
20 45. The copolymer according to any of the preceding claims, wherein the molecular weight of the SCP is in the range 8,000-100,000 g/mol and the molecular weight of a macromolecule is in the range 1,000-1000,000 g/mol.
46. The copolymer according to any of the preceding claims, wherein the molecular weight 25 of the SCP is in the range 10,000-60,000 g/mol, and the molecular weight of a macromolecule is in the range 1,000-1,000,000 g/mol.
47. The copolymer according to any of the preceding claims, wherein the molecular weight of the copolymer is in the range of 10,000-3,000,000 g/mol.
30
48. The copolymer according to any of the preceding claims wherein the molecular weight of the copolymer is in the range of 10,000-200,000 g/mol.
49. The copolymer according to any of the preceding claims, wherein the weight ratio 35 between SCP and macromolecule of the copolymer is in the range of 10: 1 - 1: 15.
50. The copolymer according to any of the preceding claims, wherein the copolymer is capable of binding to cellulose.
51. The copolymer according to any of the preceding claims, wherein the macromolecule is a non-branched polymer.
52. The copolymer according to any of the preceding claims, wherein the macromolecule is 5 a branched polymer.
53. The copolymer according to any of the preceding claims, wherein the SCP is a non- starch carbohydrate polymer.
10 54. The copolymer according to any of the preceding claims, wherein the SCP comprising a component selected from the group consisting of a hemicellulose, and a pectin.
55. The copolymer according to any of the preceding claims, wherein the SCP comprises xyloglucan.
15
56. The copolymer according to any of the preceding claims, wherein the SCP consists essentially of xyloglucan.
57. The copolymer according to any of the preceding claims, wherein the SCP comprises at 20 least 1% xyloglucan by weight.
58. The copolymer according to any of the preceding claims, wherein the SCP comprises at most 100% xyloglucan by weight.
25 59. A copolymer according to any of the preceding claims comprising an SCP and a hydrophobic polymer covalently attached to the SCP.
60. The copolymer of claim according to any of the preceding claims, comprising in the range of 1-500 hydrophobic polymers covalently attached to the SCP. 0
61. The copolymer according to any of the preceding claims, wherein one or more hydrophobic polymers are covalently attached to a natural reducing end of an SCP.
62. The copolymer according to any of the preceding claims, wherein one or more 5 hydrophobic polymers are covalently attached to the back-bone of the SCP.
63. The copolymer according to any of the preceding claims, wherein one or more hydrophobic polymers are covalently attached to side-chains of the SCP.
64. The copolymer according to any of the preceding claims, wherein the molecular weight of a hydrophobic polymer is in the range of 1,000-1,000,000 g.
65. The copolymer according to any of the preceding claims, wherein the molecular weight 5 of the SCP is in the range of 5,000-2,000,000 g/mol.
66. The copolymer according to any of the preceding claims, wherein the molecular weight of the SCP is in the range of 5,000-200,000 g/mol.
10 67. The copolymer according to any of the preceding claims, wherein the molecular weight of the SCP is in the range of 20,000-2,000,000 g/mol.
68. The copolymer according to any of the preceding claims, wherein the molecular weight of the SCP is in the range 5,000-200,000 g/mol and the molecular weight of a hydrophobic
15 polymer is in the range of 1,000-1,000,000 g/mol.
69. The copolymer according to any of the preceding claims, wherein the molecular weight of the SCP is in the range of 8,000-100,000 g/mol and the molecular weight of a hydrophobic polymer is in the range of 1,000-1000,000 g/mol.
20
70. The copolymer according to any of the preceding claims, wherein the molecular weight of the SCP is in the range of 10,000-60,000 g/mol, and the molecular weight of a hydrophobic polymer is in the range of 1,000-1,000,000 g/mol.
25 71. The copolymer according to any of the claims 59-70, wherein the molecular weight of the copolymer is in the range of 10,000-3,000,000 g/mol
72. The copolymer according to any of the claims 59-70, wherein the molecular weight of the copolymer is in the range of 10,000-200,000 g/mol.
30
73. The copolymer according to any of the claims 59-72, wherein the weight ratio between SCP and hydrophobic polymer of the copolymer is in the range of 10: 1 - 1: 15.
74. The copolymer according to any of the preceding claims, wherein the copolymer is 35 capable of binding to cellulose.
75. An aqueous formulation of the copolymer according to any of the preceding claims, wherein the aqueous formulation comprises copolymer in an amount in the range of 0.1- 80% by weight, and water in an amount in the range of 20-99.9% by weight.
5 76. The aqueous formulation according to claim 75, furthermore comprising an organic, water soluble solvent.
77. The aqueous formulation according to claim 75 or 76, wherein the aqueous formulation comprises the organic, water soluble solvent in an amount in the range of 5-45% by
10 weight.
78. The aqueous formulation according to any of the claims 75-77, wherein the organic, water soluble solvent comprises an alcohol.
15 79. The aqueous formulation according any of the claims 75-78, wherein the organic, water soluble solvent comprises acetone, propylene glycol, or glycerol, or a mixture thereof.
80. The aqueous formulation according to any of the claims 75-79, furthermore comprising 20 an emulsifier.
81. The aqueous formulation according to claim 80, wherein the aqueous formulation comprises comprise the emulsifier in an amount in the range of 0.1-10% by weight.
25 82. A hydrophobic formulation of the copolymer according to any of the claims 1-74, wherein the hydrophobic formulation comprises copolymer in an amount in the range of 0.1-80% by weight, and a hydrophobic solvent in an amount in the range of 20-99.9% by weight.
30 83. A dry formulation of the copolymer according to any of the claims 1-74, wherein the dry formulation comprises copolymer in an amount in the range of 5-99.9% by weight, and water in an amount in the range of 0.1-10% by weight, preferably in the range of 0.1- 5% by weight, and even more preferably in the range of 0.1-2% by weight.
35 84. The dry formulation according to claim 83, furthermore comprising a wetting agent.
85. The dry formulation according to claim 83 or 84, furthermore comprising a humectant.
86. The dry formulation according to any of claims 83-85, furthermore comprising an anti- agglomeration agent.
87. A method of preparing a copolymer according to any of the preceding claims, the 5 method comprising the steps of a) providing an SCP and a macromolecule, and b) attaching the macromolecule covalently to the SCP.
88. The method according to claim 87, wherein step b) involves one or more processes 10 selected from the group consisting of:
- reacting the SCP with galactose oxidase;
- reacting the SCP with an oxidizing agent,
- oxidizing of a primary alcohol group to obtain an aldehyde group; and
- reacting an aldehyde group with a primary amino group. 15
89. The method according to any of the preceding claims, wherein step b) involves reductive amination of the SCP.
90. The method according to any of the claims 87-89, wherein the SCP comprises an 20 amino group and the macromolecule, such as the hydrophobic polymer, comprises an aldehyde group, and step b) involves reacting the aldehyde group with the amino group.
91. The method according to any of the claims 87-90, wherein the SCP comprises an aldehyde group and the macromolecule comprises an amino group, and step b) involves
25 reacting the aldehyde group with the amino group.
92. The method according to any of the claims 87-91, wherein the macromolecule comprises an aldehyde group and step b) involves reacting a SCP with a diamine compound and a reducing agent to obtain an aminated SCP and to react the aminated SCP
30 with macromolecule comprising the aldehyde group to obtain the copolymer.
93. The method according to claim 92, wherein the reducing agent is a salt of cyanoborohydride.
35 94. A method of preparing a copolymer according to any of the preceding claims, the method comprising the steps of a) providing an SCP, b) attaching covalently a polymerisation initiator to the SCP, and c) polymerising onto the SCP via the polymerisation initiator.
95. The method according to claim 94, wherein at least 2 polymerisation initiators are attached to the SCP in step b).
5 96. The method according to claim 94 or 95, wherein the polymerisation initiator is selected from the group consisting of an acid-containing initiator, an allyl bromide, an allyl chloride, and a phenolic ester based monofunctional initiators.
97. A method of preparing a modified PCM, the method comprising the steps of 10
1) providing a copolymer according to any of the claims 1-74, said copolymer comprising an SCP and a macromolecule,
2) binding the copolymer to the PCM under suitable conditions, thus obtaining the modified PCM,
15 3) optionally washing, and/or drying the modified PCM
98. The method according to claim 97, wherein the PCM is a water-insoluble polysaccharide.
20 99. The method according to any of the claims 97-98, wherein the PCM comprises at least 5% cellulose by weight.
Ratio between the PCM and the copolymer in the modified PCM
100. The method according to any of the claims 97-99, wherein the weight ratio between 25 copolymer and PCM is in the range of 100: 1 - 1: 100.
101. The method according to any of the claims 97-100, wherein the weight ratio between copolymer and PCM is in the range of 100: 1 - 1: 1.
30 102. The method according to any of the claims 97-100, wherein the weight ratio between copolymer and PCM is in the range of 1: 1 - 1: 100.
103. A modified PCM comprising a copolymer according to any of the claims 1-74 bound to a PCM.
35
104. A modified PCM obtainable by the method according to any of claims 97-102.
105. The modified PCM according to any of the claims 103-104, wherein the weight ratio between copolymer and PCM is in the range of 100: 1 - 1: 100.
106. The modified PCM according to any of the claims 103-104, wherein the weight ratio 5 between copolymer and PCM is in the range of 100:1 - 1: 1.
107. The modified PCM according to any of the claims 103-104, wherein the weight ratio between copolymer and PCM is in the range of 1: 1 - 1: 100.
10 108. A method of preparing a modified hydrophobic bulk polymer, the method comprising the steps of
1) providing a copolymer according to any of the preceding claims ..., said copolymer comprising an SCP and a hydrophobic polymer,
15
2) binding the copolymer to a hydrophobic bulk polymer under suitable conditions, thus obtaining the modified hydrophobic bulk polymer.
109. A modified hydrophobic bulk polymer comprising a hydrophobic bulk polymer and a 20 copolymer according to any of the claims 1-74.
110. The modified hydrophobic bulk polymer according to claim 109, wherein the weight ratio between copolymer and hydrophobic bulk polymer is in the range of 10: 1 - 1: 1000.
25 111. A method of preparing a composite material comprising a hydrophobic bulk polymer and PCM, the method comprising the steps of: i) providing a hydrophobic bulk polymer and a modified PCM according to any of claims 103-107, and ii) mixing the hydrophobic bulk polymer and the modified PCM. 30
112. A method of preparing a composite material comprising a hydrophobic bulk polymer and PCM, the method comprising the steps of: i) providing a PCM and a modified hydrophobic bulk polymer according to any of claims 109-110, 35 ii) mixing the modified hydrophobic bulk polymer and the PCM.
113. A method of preparing a composite material comprising a hydrophobic bulk polymer and PCM, the method comprising the steps of: i) providing a PCM, a hydrophobic bulk polymer, and a copolymer according to any of claims 1-74,
ii) mixing the modified hydrophobic bulk polymer and the PCM. 5
114. A composite material comprising a PCM, a hydrophobic bulk polymer, and the copolymer according to any of claims 1-74.
115. A composite material comprising the modified PCM according to any of claims 103- 10 107 and a hydrophobic bulk polymer.
116. A composite material comprising a PCM and the modified hydrophobic bulk polymer according to any of claims 109-110.
15 117. A composite material obtainable by a method according to any of the claims 111-13.
118. Use of the copolymer according to any of the claims 1-74 as a compatibiliser.
119. Use according to claim 118, wherein the at least one macromolecule of the copolymer 20 is a hydrophobic polymer.
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