US 2015O152196A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2015/0152196A1 Phanopoulos et al. (43) Pub. Date: Jun. 4, 2015

(54) PROCESS FOR PREPARING DERVATIZED Publication Classification POLYSACCHARDES (51) Int. Cl. (71) Applicant: Huntsman International LLC. The C08B I5/06 (2006.01) Woodlands, TX (US) D6M I3/395 (2006.01) D6M 5/564 (2006.01) (72) Inventors: Christopher Phanopoulos, Moorsel C08B3L/00 (2006.01) (BE); Servaas Holvoet, Veltem-Beisem (52) U.S. Cl. (BE); Tugba Vardareli, Evere (BE): CPC ...... C08B 15/06 (2013.01); C08B31/00 Steve Diamanti, Pleasanton, CA (US) (2013.01): D06M 13/395 (2013.01): D06M (21) Appl. No.: 14/411,928 15/564 (2013.01): D06M 2101/06 (2013.01) PCT Fled: Jun. 5, 2013 (22) (57) ABSTRACT (86) PCT NO.: PCT/EP2013/061543 S371 (c)(1), The invention relates to a process for preparing a polysaccha (2) Date: Dec. 30, 2014 ride derivative, comprising the steps of: (a) contacting at least one with at least one polysaccharide Swelling (30) Foreign Application Priority Data agentata temperature of at most 70° C.; and (b) Subsequently, contacting the product of step (a) with at least one aromatic Jul. 5, 2012 (EP) ...... 12175126.7 isocyanate; thereby preparing a polysaccharide derivative. Patent Application Publication Jun. 4, 2015 US 201S/O15219.6 A1

10 15 20 25 30 35 40 2 theta FIG. 1

s e

888

FIG. 2 US 2015/O1521.96 A1 Jun. 4, 2015

PROCESS FOR PREPARING DERVATIZED damage the cellulosic bulk structure, which in turn may nega POLYSACCHARDES tively affect molecular weight, fiber strength and stiffness, etc. 0001. The present invention relates to processes for pre 0011 Alternatively, steam explosion can be applied to paring polysaccharide derivatives and to the thus obtained break down the cellulosic substrate in harsh pressure and polysaccharide derivatives. temperature conditions. This procedure requires an extra dry 0002 is a fibrous, tough, water-insoluble sub ing step and, in addition, is known to reduce the crystalline stance which can be found in the protective (cell) wall of content of the substrates. plants. It is a polysaccharide that is mainly composed of 0012. Therefore, there remains a need for processes for beta-D-gluco- units linked by 1-4 glycosidic preparing functionalized that overcome one bonds. From a structural perspective, cellulosic chains are or more of the aforementioned issues. It is an object of the arranged into microfibrils during crystallization with the for present invention to provide a process for preparing a func mation of chain-stiffening inter-molecular hydrogen bonds. tionalized polysaccharide. It is also an object of the invention Different crystalline allomorphs of cellulose are known. to provide a functionalized polysaccharide while maintain 0003. The hydroxyl groups in cellulosic substrates are ing, or only minimally reducing, the polysaccharide bulk involved in a number of intra- and intermolecular hydrogen properties, such as crystallinity. bonds and generally show limited reactivity as nucleophilic 0013 The present inventors have now surprisingly found moieties. As a consequence, chemical derivatization of these that one or more of these objects can be obtained by a process hydroxyl groups is extremely difficult. Even towards highly for preparing a polysaccharide derivative according to the reactive molecules (such as e.g. isocyanates), these hydroxyl invention. The polysaccharide derivative is obtained by pre groups show no or very little reactivity. Another disadvantage contacting the polysaccharide with a compound, before add of these cellulosic materials is their high melting point, usu ing an aromatic isocyanate for functionalization, said pre ally higher than the thermal decomposition temperature, contacting step being performed at a temperature of at most which limits their derivatization potential in liquid phase. 70° C. The polysaccharide derivative can comprise pendant 0004 Traditional approaches in chemical derivatization of free isocyanate groups which enable the polysaccharide to be cellulose make use of chemically and/or physically harsh further derivatized, and/or to improve the compatibility of the conditions (chemicals, temperature, pressure, pH. . . . ) to polysaccharide particles with isocyanate based liquids. The dissolve or derivatize cellulose. This impacts the bulk struc polysaccharide derivatives can Subsequently be used in dif ture and related properties (such as crystallinity) of the Sub ferent applications by further reaction/derivatization with strates. These current solutions have mainly focused on other isocyanate-reactive functionalities, such as Substrates, decreasing or eliminating the hydrogen bonding pattern in the specialty chemicals, and polyurethane components. 0014. The present invention encompasses a process for cellulosic Substrate, as discussed below. preparing a polysaccharide derivative, the process compris 0005. Sometimes, the problem is merely ignored. In these ing the steps of cases, the cellulose may act as a non-reactive filler. (a) contacting at least one polysaccharide with at least one 0006. One option is to alkoxylate the cellulosic substrate polysaccharide Swelling agent, preferably selected from the in order to increase its solubility and compatibility with the group comprising Sulfoxides, formamides, acetamides, pyr derivatization agent. Alkoxylation impacts crystallinity, adds rolidones, pyridines, imidazoles and mixtures thereof, at a capital costs and moreover, is associated with EHS risks. temperature of at most 70° C.; and 0007 Another possibility is the use of mono-, di- and/or (b) Subsequently, contacting the product of step (a) with at which possess different solubility charac least one aromatic isocyanate; teristics. However, such use is limited in Some applications thereby preparing a polysaccharide derivative when the bulk properties of the cellulosic substrates are 00.15 Preferably, the polysaccharide derivative prepared required (e.g. composites). according to the present invention comprises the reaction 0008 Another option is to breakdown the hydrogenbond product of: ing network. a) at least one polysaccharide with a degree of polymerization 0009 Frequently applied methods chemically digest the of at least 5; and cellulosic Substrates by Sulfite or alkali processes (caustic b) at least one aromatic isocyanate; soda, dilute NaOH) at elevated temperatures in pressure ves and the crystallinity index CI of the polysaccharide deriva sels (degradation, lower molecular weight, decreased crystal tive, as measured by XRD, is at least 5%. linity). However, the aqueous medium or residual moisture, 0016. The independent and dependent claims set out par which is often bound into the hydrogen network, is incom ticular and preferred features of the invention. Features from patible with isocyanate chemistry and causes side reactions. the dependent claims may be combined with features of the In addition, residues of the digesting medium (e.g. Na and/or independent or other dependent claims as appropriate. Kcations) can be released and can cause side reactions with 0017. The above and other characteristics, features and isocyanates (e.g. isocyanurates). Furthermore, the degrada advantages of the present invention will become apparent tion of the structure leads to a deterioration of the cellulosic from the following detailed description, which illustrates, by properties. way of example, the principles of the invention. 0010. The hydrogenbond network may also be partially or 0018 FIG. 1 represents an X-ray diffraction spectrum of completely destroyed by using mechanical treatments (for cellulose (Avicel PH-101). example: grinding, milling, etc), wherein mechanical energy 0019 FIG. 2 represents an X-ray diffraction spectrum of may tear apart the microfibrils in order to degrade the cellu corn . losic Substrate. This leads to a reduced molecular weight and 0020. It is to be understood that this invention is not lim higher amorphous content. However, mechanical treatments ited to particular embodiments described, since such embodi US 2015/O1521.96 A1 Jun. 4, 2015

ments may, of course, vary. It is also to be understood that the 0030. As used herein, the term “C cycloalkyl, by itself terminology used herein is not intended to be limiting, since or as part of another Substituent, refers to a saturated or the scope of the present invention will be limited only by the partially saturated cyclic alkyl radical containing from about appended claims. 3 to about 6 carbon atoms. Examples of C. cycloalkyl 0021. As used herein, the singular forms “a”, “an', and include cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl. “the include both singular and plural referents unless the 0031. As used herein, the term “Co aryl', by itself or as context clearly dictates otherwise. By way of example, “an part of another Substituent, refers to a polyunsaturated, aro isocyanate group” means one isocyanate group or more than matic hydrocarbyl group having a single ring (i.e. phenyl) or one isocyanate groups. multiple aromatic rings fused together (e.g. naphthyl) or 0022. The terms “comprising”, “comprises” and “com linked covalently, typically containing from 6 to 10 carbon prised of as used herein are synonymous with “including. atoms, wherein at least one ring is aromatic. Co aryl is also “includes” or “containing”, “contains, and are inclusive or intended to include the partially hydrogenated derivatives of open-ended and do not exclude additional, non-recited mem the carbocyclic systems enumerated herein. Non-limiting bers, elements or method steps. It will be appreciated that the examples of aryl comprise phenyl, naphthyl, indanyl, or 1.2, terms “comprising”, “comprises” and “comprised of as used 3,4-tetrahydro-naphthyl. herein comprise the terms “consisting of, “consists' and 0032. As used herein, the term “Co aryl C alkyl', by “consists of. itself or as part of another Substituent, refers to a C- alkyl 0023 Throughout this application, the term “about is group as defined herein, wherein a hydrogenatom is replaced used to indicate that a value includes the standard deviation or by a Co aryl as defined herein. Examples of Cao aryl C. error for the device or method being employed to determine alkyl radicals include benzyl, phenethyl, dibenzylmethyl, the value. methylphenylmethyl, 3-(2-naphthyl)-butyl, and the like. 0024. As used herein, the terms “% by weight”, “wt %', 0033. In the following passages, different aspects of the “weight percentage', or “percentage by weight’ are used invention are defined in more detail. Each aspect so defined interchangeably. may be combined with any other aspect or aspects unless 0025. The recitation of numerical ranges by endpoints clearly indicated to the contrary. In particular, any feature includes all integer numbers and, where appropriate, frac indicated as being preferred or advantageous may be com tions subsumed within that range (e.g. 1 to 5 can include 1, 2, bined with any other feature or features indicated as being 3, 4 when referring to, for example, a number of elements, and preferred or advantageous. can also include 1.5, 2, 2.75 and 3.80, when referring to, for 0034 Reference throughout this specification to “one example, measurements). The recitation of end points also embodiment' or “an embodiment’ means that a particular includes the endpoint values themselves (e.g. from 1.0 to 5.0 feature, structure or characteristic described in connection includes both 1.0 and 5.0). Any numerical range recited with the embodiment is included in at least one embodiment herein is intended to include all Sub-ranges subsumed therein. of the present invention. Thus, appearances of the phrases "in 0026. All references cited in the present specification are one embodiment' or “in an embodiment” in various places hereby incorporated by reference in their entirety. In particu throughout this specification are not necessarily all referring lar, the teachings of all references herein specifically referred to the same embodiment, but may. Furthermore, the particular to are incorporated by reference. features, structures or characteristics may be combined in any 0027. Unless otherwise defined, all terms used in disclos Suitable manner, as would be apparent to a person skilled in ing the invention, including technical and Scientific terms, the art from this disclosure, in one or more embodiments. have the meaning as commonly understood by one of ordi Furthermore, while some embodiments described herein nary skill in the art to which this invention belongs. By means include some but not other features included in other embodi of further guidance, term definitions are included to better ments, combinations offeatures of different embodiments are appreciate the teaching of the present invention. meant to be within the scope of the invention, and form 0028. The term “alkyl as a group or part of a group as used different embodiments, as would be understood by those in herein refers to branched or straight (linear) or cyclic hydro the art. For example, in the appended claims, any of the carbon with no site of unsaturation, preferably having at least claimed embodiments can be used in any combination. 4 carbon atoms in the chain. When a subscript is used herein 0035. The present invention encompasses a process for following a carbon atom, the subscript refers to the number of preparing a polysaccharide derivative, the process compris carbon atoms that the named group may contain. Thus, for ing the steps of example, Co alkyl means an alkyl of 1 to 20 carbon atoms. (a) contacting at least one polysaccharide with at least one Examples of alkyl groups are methyl, ethyl, propyl, isopro compound, at a temperature of at most 70° C., preferably at pyl, butyl, isobutyl, sec-butyl, tert-butyl, penty1 and its chain room temperature; and isomers, hexyl and its chain isomers, heptyl and its chain isomers, octyl and its chain isomers, nonyl and its chain (b) Subsequently, contacting the product of step (a) with at isomers, decyl and its chain isomers, undecyl and its chain least one aromatic isocyanate; isomers, dodecyl and its chain isomers. thereby preparing a polysaccharide derivative. 0029. The term “alkenyl as a group or part of a group as 0036. The at least one compound may be any polysaccha used herein refers to a branched or straight or cyclic hydro ride Swelling agent essentially in the absence of water. The at carbon with at least one site (usually 1 to 3, preferably 1) of least one compound may be any polysaccharide Swelling unsaturation, namely a carbon-carbon, sp2 double bond, pref agent that is not isocyanate reactive. Preferably, the at least erably having at least 4 carbonatoms in the chain. The double one compound is selected from the group comprising Sulfox bond may be in the cis or trans configuration. Coalkenyl ides, formamides, acetamides, pyrrolidones, pyridines, imi means an alkenyl of 1 to 20 carbon atoms. dazoles and mixtures thereof. US 2015/O1521.96 A1 Jun. 4, 2015

0037. In an embodiment, the present invention encom 0044 As used herein, the term “acetamide' refers to com passes a process for preparing a polysaccharide derivative, pounds comprising the —NC(O)CH functional group. Pre the process comprising the steps of ferred acetamides have the general structure of formula (3): (a) contacting at least one polysaccharide with at least one compound selected from the group comprising Sulfoxides, HC(O)NRR (3) formamides, acetamides, pyrrolidones, pyridines, imidazoles wherein R and R are independently selected from the and mixtures thereof, at a temperature of at most 70° C. group comprising hydrogen or preferably at room temperature; and 0045 Coalkyl. In an embodiment, the at least one com (b) Subsequently, reacting the product of step (a) with at least pound is N,N-dimethyl acetamide (DMAc). one aromatic isocyanate; 0046. As used herein, the term "pyrrolidones' refers to the thereby preparing a polysaccharide derivative. compound with the CH-NO, optionally 0038 Preferably, the at least one compound is present in Substituted with Coalkyl and/or halogens. an amount of at least 25% by weight, preferably at least 50%, 0047. As used herein, the term "pyridines' refers to the preferably at least 75%, for example at least 90%, for example compound with the chemical formula C5H5N. optionally sub at least 95%, based on the total weight of the polysaccharide stituted with Coalkyl and/or halogens. and the compound combined. 0048. As used herein, the term “imidazole' refers to the 0039. In a preferred embodiment, the at least one polysac compound with the chemical formula CHN, optionally charide in step (a) is present in an amount ranging from 0.5 to Substituted with Coalkyl and/or halogens. 99.0% by weight, based on the total weight of the at least one 0049. In a preferred embodiment, the at least one com polysaccharide and the at least one compound combined. pound is selected from the group comprising: dimethyl Sul Preferably, the at least one polysaccharide in step (a) is foxide, diethyl sulfoxide, ethylmethyl sulfoxide, N,N-dim present in an amount ranging from 2.0 to 70.0 by weight, even ethyl formamide, N,N-diethyl formamide, N.N-ethylmethyl more preferably ranging from 5.0 to 50.0% by weight, based formamide, N-methyl-pyrrolidone, pyridine, bromo-pyri on the total weight of the at least one polysaccharide and the dine, chloro-pyridine, N,N-dimethyl acetamide. N,N-diethyl at least one compound combined. acetamide, N,N-ethylmethyl acetamide, 1,3-dimethyl-2-imi 0040 Step (a) of the process according to the invention dazolidinone, imidazolidinone, 1-methyl-2-imidazolidinone, comprises contacting at least one polysaccharide with at least 1-ethyl-2-imidazolidinone, 1-allyl-3-methylimidazolium one compound which cause Swelling but which do not react chloride, 1-butyl-3-methylimidazolium chloride, 1-ethyl-3- with isocyanates, preferably said compound being selected methylimidazolium chloride, and mixtures thereof. In a pre from the group comprising Sulfoxides, formamides, aceta ferred embodiment, the compound is dimethyl sulfoxide mides, pyrrolidones, pyridines, imidazoles, and mixtures (DMSO). thereof. Said step is performed at a temperature below 70° C. 0050. In an alternative embodiment, the at least one com preferably at a temperature below 60° C., preferably at a pound may be any compound that is not isocyanate reactive. temperature below 50° C., preferably at a temperature below Preferably, the at least one compound may be any compound 40°C., preferably at room temperature. As used herein, the that does not break strong hydrogen bonds. For example, the term “room temperature” refers to a temperature of from 15 to at least one compound may be an ionic liquid. Preferably, the 35o C. at least one compound is essentially free of any compounds 0041 Step (a) may cause swelling of the at least one that are isocyanate reactive. Preferably, the at least one com polysaccharide. Without being bound to the theory, swelling pound is essentially free of any compounds that break strong can make the Surface hydroxyl moieties more accessible for hydrogenbonds. For example, the at least one compound may reaction with derivatization agents. Preferably, such a swell be essentially free of LiCl. ing procedure is a reversible step and enables full regenera 0051. In a preferred embodiment, the at least one com tion of the crystalline structure. pound is anhydrous. Preferably, the at least one compound is 0042. As used herein, the term “sulfoxide” refers to com anhydrous DMSO. In a preferred embodiment, the water pounds comprising a Sulfur atom covalently linked to three content in the at least one polysaccharide, the at least one atoms, at least one of which is an oxygen atom; the formal isocyanate and the at least one compound is at most 0.5% by oxidation state of said sulfur atom is (IV). Preferred sulfox weight, preferably at most 0.4% by weight, more preferably ides have the general structure of formula (1): at most 0.2% by weight. S(O)RR2 (1) 0052. In a preferred embodiment, step (a) is preceded by wherein RandR are independently selected from the group the step of drying the polysaccharide, preferably under comprising hydrogen, Co alkyl, C-2 alkenyl, Coo aryl, WaCUU. C. cycloalkyl, and Co aryl C. alkyl, optionally Substi 0053. In some embodiments, this drying step is performed tuted with heteroatoms. Examples of preferred R and R at a temperature ranging from 40 to 100° C., preferably about include Coalkyl, phenyland benzyl. Preferably, the at least 60° C. one compound is dimethyl sulfoxide (DMSO). 0054. In some embodiments, this drying step is performed 0043. As used herein, the term “formamide' refers to com for at least 0.5 hrs, preferably at least 1 hr., preferably at least pounds comprising the NC(O)H formamide group. Pre 2 hrs, preferably at least 6 hrs, preferably about 12 hrs. ferred formamides have the general structure of formula (2): 0055. In a preferred embodiment, step (a) is performed for a time period of at least 30 minutes before step (b). Preferably, HC(O)NR2 R22 (2) step (a) comprises contacting the least one polysaccharide wherein R and R are independently selected from the with the at least one compound for at least 3 hours, more group comprising hydrogen or Coalkyl. In an embodiment, preferably for at least 2 hours, more preferably for at least 1 the at least one compound is N,N-dimethyl formamide hour. In some embodiments, step (a) comprises contacting the (DMF). at least one polysaccharide with the at least one compound for US 2015/O1521.96 A1 Jun. 4, 2015 a time ranging from 0.5 to 24 hrs, preferably from 0.5 to 12 ide and potassium isopropoxide; and alkali metal salts of hrs, preferably from 0.5 to 3 hrs. The aforementioned times long-chain fatty acids having from 10 to 20 carbon atoms are preferred times for temperatures of at most 50° C. For and/or lateral OH groups; triethylamine, N.N.N',N'-tetram higher temperatures, step (a) may be shorter. It is preferred ethylethylenediamine, N,N-dimethylaminopropylamine, that the time and temperature in step (a) does not result in N.N.N',N',N'-pentamethyldipropylenetriamine, tris(dim complete dissolution of the polysaccharide. For example, at a ethylaminopropyl)amine, N.N-dimethylpiperazine, tetram temperature of from 50° C. to 60°C., step (a) is performed for ethylimino-bis(propylamine), dimethylbenzylamine, trim a time period of at most 2 hours, for example of from 0.5 to 2 ethyl amine, triethanolamine, N,N-diethyl ethanolamine, hours. Preferably, at a temperature of from 60° C. to 70° C., N-methylpyrrolidone, N-methylmorpholine, N-ethylmor step (a) is performed for a time period of at most 1 hour, for pholine, bis(2-dimethylamino-ethyl)ether, N,N-dimethylcy example of from 0.5 to 1 hour. clohexylamine (DMCHA), N.N.N',N',N'-pentamethyldieth 0056 Step (b) of the process according to the invention ylenetriamine, 1,2-dimethylimidazole, 3-(dimethylamino) comprises reacting the product of step (a) with at least one propylimidazole, N.N.N-dimethylaminopropylhexahy aromatic isocyanate. For example, step (b) of the process drotriazine, potassium acetate, N.N.N-trimethyl isopropyl according to the invention comprises contacting or mixing the amine/formate, and combinations thereof. It is to be appreci product of step (a) with at least one aromatic isocyanate. ated that the catalyst component may include any combina 0057 Preferably, step (b) is performed in contact with the tion of two or more of the aforementioned catalysts. same at least one compound as step (a). 0064 Preferably, the catalyst is present in an amount of at 0058. In some embodiments, step (b) comprises contact least 10 ppm, for example at least 0.01% by weight, for ing, mixing and/or reacting the product of step (a) with at least example at least 0.20% by weight, with% by weight based on one aromatic isocyanate for at least 15 minutes, more prefer the total weight of the isocyanate. ably for at least 30 minutes, more preferably for at least 1 0065. In some embodiments the catalyst is present in at hour, most preferably for about 4 hours. In some embodi most 5% by weight, based on the weight of the isocyanate. ments, step (b) comprises contacting, mixing and/or reacting 0066. In some embodiments of the invention, the process the product of step (a) with at least one aromatic isocyanate according to the invention comprises one or more additional for a time ranging from 15 minutes to 24 hrs, preferably from steps, such as washing steps, drying steps or flushing steps. 30 minutes to 12 hrs, more preferably from 1 to 12 hrs. 0067. The process of the present invention provides a 0059. In some embodiments, the temperature in step (b) polysaccharide derivative comprising the reaction product of ranges from 25 to 125°C., more preferably from 25 to 80°C., at least one polysaccharide with at least one aromatic isocy most preferably from 25 to 50° C. anate, wherein the at least one polysaccharide preferably has 0060. In a preferred embodiment, the mixture in step (b) is a degree of polymerization of at least 5, and the polysaccha agitated, for example stirred or shaken. ride derivative preferably has a crystallinity index (CI) as 0061. In some embodiments, step (b) comprises mixing measured by XRD, of at least 5%. the product of step (a) with at least one catalyst. Preferably, 0068. As used herein the terms “polysaccharide deriva the catalyst is an organometallic catalyst. Any other step can tive'. “modified polysaccharide' and “functionalized also be performed in the presence of a catalyst. polysaccharide' are synonymous and used interchangeably 0062. In some embodiments, the catalyst is an organome and refer to an isocyanate functionalized polysaccharide. The tallic catalyst. In these embodiments, the catalyst comprises reaction product may be obtained by adding, reacting, con an element selected from the group comprising tin, iron, lead, tacting or mixing the different components. bismuth, mercury, titanium, hafnium, Zirconium, and combi 0069. According to one embodiment the polysaccharide nations thereof. In certain embodiments, the catalyst com derivative, obtained by the process of the present invention, prises a tin catalyst. Suitable tin catalysts, for purposes of the comprises a polysaccharide backbone and one or more pen present invention, may be selected from tin(II) salts of dant groups attached to the polysaccharide backbone via a organic carboxylic acids, e.g. tin(II) acetate, tin(II) octoate, carbamate —O—C(=O)—NH link. Such a carbamate tin(II) ethylhexanoate and tin(II) laurate. In an embodiment, link may be formed by the reaction of a free isocyanate the organometallic catalyst comprises dibutyltin dilaurate, —N=C=O group with a hydroxyl group of a polysaccha which is a dialkyltin(IV) salt of an organic carboxylic acid. ride backbone. The organometallic catalyst can also comprise other dialky 0070 According to another embodiment the polysaccha ltin(IV) salts of organic carboxylic acids, such as dibutyltin ride derivative, obtained by the process of the present inven diacetate, dibutyltin maleate and dioctyltin diacetate. Specific tion, comprises a polysaccharide backbone and one or more examples of Suitable organometallic catalyst, e.g. dibutyltin pendant groups attached to the polysaccharide backbone via dilaurates, for purposes of the present invention, are commer an urea —NH CO =O) NH link. Such an urea link may cially available from Air Products and Chemicals, Inc. under be formed by the reaction of a free isocyanate —N=C=O the trademark of DABCOR). Preferred catalysts according to group with an amine group of a polysaccharide backbone. the invention are dibutyl tin dilaurate, dibutyl tin diacetate, 0071. According to yet another embodiment the polysac dioctyl tin diacetate, and tin octoate. charide derivative, obtained by the process of the present 0063) Non-limiting examples of other suitable catalysts, invention, comprises a polysaccharide backbone and one or may be selected from the group comprising iron(II) chloride; more pendant groups attached to the polysaccharide back Zinc chloride; lead octoate; tris(dialkylaminoalkyl)-S- bone via an allophanate —NH CO =O) N(—C(=O) hexahydrotriazines including tris(N,N-dimethylaminopro O—)—link. Such an allophanate link may be formed by the pyl)-s-hexahydrotriazine; tetraalkylammonium hydroxides reaction of a free isocyanate —N=C=O group with a ure including tetramethylammonium hydroxide; alkali metal thane group of a polysaccharide backbone. hydroxides including Sodium hydroxide and potassium 0072 According to yet another embodiment the polysac hydroxide; alkali metal alkoxides including sodium methox charide derivative, obtained by the process of the present US 2015/O1521.96 A1 Jun. 4, 2015 invention, comprises a polysaccharide backbone and one or ride peptide; porphyran: pullulan; ; Sepharose; more pendant groups attached to the polysaccharide back ; sizofiran, Sugammadex; welan gum, , bone via abiuret-NH C(=O) N(-C(=O) NH ) Xylan, Xyloglucan, , such as link. Suchabiuret link may beformed by the reaction of a free , chondroitin, chondroitin Sulfate, derma isocyanate —N=C=O group with an urea group of a tan Sulfate, heparan Sulfate, heparin, heparinoid, hyaluronan, polysaccharide backbone. keratan Sulfate, restylane, sodium hyaluronate, and Sulodex 0073 Preferably the one or more pendant groups comprise ide; and mixtures thereof. In preferred embodiments, the at at least one free isocyanate—N=C=O group, which may be least one polysaccharide is selected from the group compris used for further functionalization. Preferably, the degree of ing cellulosic compounds and , polymerization of the polysaccharide backbone is at least 5. I0081. In an embodiment, the at least one polysaccharide is Preferably, the crystallinity index CI of the polysaccharide a starch selected from the group comprising: corn starch, derivative, as measured by XRD, is at least 5%. , acetylated distarch adipate, amylomaize, amy 0074 The NCO content of the polysaccharide derivative lopectin, cyclodextrin, , dialdehyde starch, erythro can be ranging from 0% to 10% as measured according to nium japonicum, high- corn syrup, hydrogenated DIN 53185. In some embodiments, the NCO content of the starch hydrosylate, hydroxyethyl starch, hydroxypropyl dis polysaccharide derivative is at least 0.2%, For example, the tarch phosphate, maltitol, , , pentastarch, NCO content can be ranging from 0.2% to 5.0%, for example phosphated distarch phosphate, potato starch, starch, waxy from 0.2% to 3.0%. corn, waxy potato starch, and mixtures thereof. 0075. As used herein, the term “polysaccharide' refers to I0082 In an embodiment, the at least one polysaccharide is compounds comprising at least 5 monomer Saccharide Sub a cellulosic compound selected from the group comprising: units joined together by glycosidic bonds. cellulose, nanocellulose, art silk, bacterial cellulose, bamboo 0076 Preferably, the at least one polysaccharide has a fibre, carboxymethyl cellulose, cellodextrin, cellophane, cel degree of polymerization of at least 10, more preferably of at luloid, cellulose acetate, cellulose acetate phthalate, cellulose least 20, more preferably of at least 50, for example of at least triacetate, cellulosome, cotton, croScarmellose Sodium, crys 100, for example of at least 150, for example of at least 200, talate, ciethylaminoethyl cellulose, dissolving pulp, ethulose, for example of at least 500. ethyl cellulose, fique, hydroxyethyl cellulose, hydroxyethyl 0077. The at least one polysaccharide may be natural or methyl cellulose, hydroxypropyl cellulose, hypromellose, synthetic. The at least one polysaccharide may be crude or lyocell, mercerised pulp, methyl cellulose, microbial cellu purified. The at least one polysaccharide may be original or lose, microcrystalline cellulose, modal (textile), nitrocellu (partially) pre-derivatized or modified. The at least one lose, parkesine, pearloid, pulp, paper, rayon, sodium cellulose polysaccharide may be linear, branched or cyclic. The at least phosphate, Supima, Viscose, Vulcanized fibre, wood fibre, and one polysaccharide may be a homopolysaccharide (also mixtures thereof. referred to as homoglycan) or a heteropolysaccharide (also I0083. In a preferred embodiment, the polysaccharide is referred to as heteroglycan). cellulose or starch. As used herein, the term 'cellulose' refers 0078 Preferably, the at least one polysaccharide is to a polysaccharide comprising a linear chain of several hun based, i.e. the at least one polysaccharide comprises at least dred to over ten thousand B(1->4) linked D- units. one hexose sub-unit. Preferably the at least one polysaccha I0084. The polysaccharide derivative, obtained by the pro ride comprises at least 50% by weight of hexose sub-units, cess of the present invention, comprises the reaction product based on the total weight of the polysaccharide, more prefer of the at least one polysaccharide with at least one aromatic ably at least 75% by weight, more preferably at least 90% by isocyanate. weight. Preferably the at least one polysaccharide is cyclic I0085. As used herein, the term isocyanate comprises any hexose based. compound comprising at least one isocyanate —N=C=O 0079. In a preferred embodiment, the at least one polysac group, whereby the isocyanate group may be a terminating charide comprises at least one glucose sub-unit. Preferably group. Preferably, the isocyanate group is a terminating the at least one polysaccharide comprises at least 50% by group. Isocyanate compounds are preferably polyisocyanate weight of glucose Sub-units, based on the total weight of the compounds. Suitable polyisocyanates used may be polysaccharide, more preferably at least 75% by weight, araliphatic and/or aromatic polyisocyanates, typically of the more preferably at least 90% by weight. The glucose sub type R (NCO), with X being at least 1, preferably at least 2, units may be modified glucose sub-units, for example amino and R being an aromatic or combined aromatic/aliphatic glucose sub-units, with a substituent on the C2 or C3 position. group. Examples of R are diphenylmethane, toluene, or 0080. In some embodiments, the at least one polysaccha groups providing a similar polyisocyanate. ride is selected from the group comprising: cellulosic com I0086. In a preferred embodiment, the isocyanate is a poly pounds; starches (such as amylose or or mix isocyanate. Due to partial Surface crosslinking (intra and tures thereof); agarose; alginic acid; alguronic acid; alpha interstrand crosslinking between cellulosic chains) by the , amylopectin; amylose; arabinoxylan; beta-glucan: polyisocyanate, the bulk of the cellulosic substrate may be callose; capsulan; carrageenan; cellodextrin; cellulin; ; protected against further derivatization. In this way, the crys , chrysolaminarin; curdlan; cyclodextrin; DEAE talline, stiff nature of the cellulosic backbone may be pre Sepharose; ; dextrin; alpha-cyclodextrin; ficoll; fruc served for furtherapplications, in which the bulk properties of tan; fucoidan; galactoglucomannan; galactomannan; gellan the cellulosic are required (e.g. for composites). Free isocy gum, glucan, glucomannan; glycocalyx; ; hemicel anate groups may also be used for further functionalization or lulose; hypromellose; icodextrin; kefiran, laminarin; len derivatization. The free isocyanate groups of polyisocyanates tinan; levan, lichenin; maltodextrin; mixed-linkage glucan: may also trimerize to form isocyanurates groups. mucilage; natural gum; oxidized cellulose; paramylon; pectic I0087. In a preferred embodiment, the at least one isocyan acid; ; pentastarch; pleuran, polydextrose; polysaccha ate is a polyisocyanate selected from the group comprising: US 2015/O1521.96 A1 Jun. 4, 2015 methylene diphenyl diisocyanate in the form of its 2,4'-, 2,2'- I0089. In a preferred embodiment, the isocyanate com and 4,4'-isomers and mixtures thereof, the mixtures of meth prises MDI. Preferably, the MDI is in the form of its 2,4'-, 2,2'- ylene diphenyl diisocyanates and oligomers thereof, or their and 4,4'-isomers and mixtures thereof, or in the form of the derivatives having a urethane, isocyanurate, allophonate, mixtures of diphenylmethane diisocyanates (MDI) and oli biuret, uretonimine, uretdione and/or iminooxadiazinedione gomers thereof. In some embodiments, the MDI is in the form groups and mixtures thereof, toluene diisocyanates and iso of its 2,4' and 4,4'-isomers and mixtures thereof, or in the form mer mixtures thereof; tetramethylxylene diisocyanate; 1.5- of the mixtures of these diphenylmethane diisocyanates naphtalenediisocyanate; p-phenylenediisocyanate; tolidine (MDI) and oligomers thereof. In some embodiments, the diisocyanate; or mixtures of these organic polyisocyanates, MDI is in the form of its 2,4' isomer, or in the form of the and mixtures of one or more of these organic polyisocyanates mixtures of the 2.4 isomer and oligomers thereof. The use of with methylene diphenyl diisocyanate in the form of 2,4'- 2.4-MDI containing isocyanates partially inhibits crosslink 2,2'- and 4,4'-isomers and mixtures thereof, the mixtures of ing between two cellulosic chains compared to the use of pure methylene diphenyl diisocyanate and oligomers thereof. 4,4'-MDI, which results in more crosslinking. So by the choice of the initial MDI type, the amount of pendant isocy 0088. In an embodiment, the at least one isocyanate is the anates and extent of crosslinking can be tailored. Preferably, reaction product of polyisocyanates (e.g. polyisocyanates as the at least one isocyanate is a mixture of 2,4'- or 4,4'-MDI. In set out above), with components containing isocyanate-reac Some embodiments, the polyisocyanate comprises a poly tive hydrogen atoms forming polymeric polyisocyanates or meric polyisocyanate. In some embodiments, the polyisocy so-called prepolymers. The prepolymer can be generally pre anate comprises a high functionality polymeric polyisocyan pared by reacting a polyisocyanate with isocyanate reactive ate, with a functionality of at least 2.5, preferably at least 2.7. components which are typically components containing iso As used herein, the term “functionality” refers to the average cyanate-reactive hydrogen atoms, such as a hydroxyl termi number of isocyanate groups per molecule, averaged over a nated polyether (polyether polyols), a hydroxyl terminated statistically relevant number of molecules present in the iso polycarbonate or mixture thereof, and hydroxyl terminated cyanate. polyesters (polyester polyol). Non-limiting examples of suit 0090. In some embodiments, the at least one isocyanate able polyether polyols are preferably polyether polyols comprises a polymeric methylene diphenyl diisocyanate. derived from a diol or polyol having a total of from 2 to 15 carbon atoms, preferably an alkyl diol or glycol which is 0091. The polymeric methylene diphenyl diisocyanate reacted with an ether comprising an alkylene oxide having can be any mixture of pure MDI (2,4'-, 2,2'- and 4,4'-methyl from 2 to 6 carbon atoms, typically ethylene oxide or propy ene diphenyl diisocyanate) and higher homologues thereof. lene oxide or mixtures thereof, preferably having a function 0092. The polysaccharide derivative obtained by the pro ality of at least 2, for example from 2 to 6. Hydroxyl func cess of the present invention may be used in fillers, fibers, tional polyether can be produced by first reacting propylene packaging, films, foams, composites, adhesives, coatings, glycol with propylene oxide followed by Subsequent reaction textiles, Sealants, rheology modifiers, paints, chromatogra with ethylene oxide. Primary hydroxyl groups resulting from phy packing (Solid phase) etc. For example, the polysaccha ethylene oxide are more reactive than secondary hydroxyl ride derivative may be used in fillers (as granules), fibers, or groups and thus are preferred. Useful commercial polyether textiles. polyols include poly(ethylene glycol) comprising ethylene 0093. In a preferred embodiment, the polysaccharide oxide reacted with ethylene glycol, polypropylene glycol) derivative is in the form of granules, wherein the granules comprising propylene oxide reacted with propylene glycol, have a particle size distribution wherein the D50 is at most 1.0 poly(tetramethyl glycol) (PTMG) comprising water reacted mm, preferably at most 200 micron, more preferably at most with tetrahydrofuran (THF). Polyether polyols can further 100 micron and in the most preferred embodiment at most 50 include polyamide adducts of an alkylene oxide and can micron, wherein D50 is defined as the particle size for which include, for example, ethylenediamine adduct comprising the fifty percent by weight of the particles has a size lower than reaction product of ethylenediamine and propylene oxide, the D50. For example, the D50 (and/or D90 or D95) can be diethylenetriamine adduct comprising the reaction product of measured by sieving, by BET surface measurement, or by diethylenetriamine with propylene oxide, and similar polya laser diffraction analysis, for example according to standard mide type polyether polyols. Copolyethers can also be uti ISO 1332O:2009. lized in the current invention. Typical copolyethers include 0094. In a preferred embodiment, the polysaccharide the reaction product of glycerol and ethylene oxide or glyc derivative is in the form of a yarn or fiber, with a linear mass erol and propylene oxide. The various polyether intermedi density of at most 2000 denier, preferably between 5 and 2000 ates generally have a number average molecular weight (Mn), denier, preferably between 5 and 500 denier, and in the most as determined by assay of the terminal functional groups preferred embodiment between 5 and 200 denier. which is an average molecular weight, of from about 200 to 0095. In a preferred embodiment, the polysaccharide about 10000, desirably from about 200 to about 5000, and derivative is in the form of a textile or fabric, wherein the preferably from about 200 to about 3000. According to textile or fabric may be woven or unwoven. embodiments, the polyether polyols are EO-tipped polyether 0096. The crystallinity of the polysaccharide derivative, as polyol. Suitable EO-tipped polyether polyol comprises poly measured by XRD, is preferably at least 5%. Preferably, the ether polyol having a structure I-R-(CH2CH2O)H). crystallinity of the polysaccharide derivative, as measured by wherein X is an integer equal or more than 1. p is a number XRD, is at least 10%, preferably at least 20%, preferably at varying from 1 to 100, I is an initiator and R represents a series least 30%. The crystallinity index (CI) of the at least one of epoxides, the (CH2CH2O).H groups being bound to R via polysaccharide may beat least 10%, for example at least 20%, an ether bond. The initiator I may be an alcohol, an amine, a for example at least 30%, for example at least 40%, for polyalcohol, a polyamine or a component comprising one or example at least 50%, for example at least 60%, for example more alcohol groups and one of more amine groups. at least 70%, for example at least 80%. US 2015/O1521.96 A1 Jun. 4, 2015

0097. In an embodiment, the at least one polysaccharide is was stirred at room temperature for 1 hour. Isocyanate (a cellulose and the crystallinity of the polysaccharide deriva mixture of 50% 4,4'-MDI and 50% 2,4'-MDI) was added to tive, as measured by XRD, is at least 10%, preferably at least the reaction flask while blanketing with nitrogen and stirring 20%, preferably at least 30%, preferably at least 40%, pref vigorously at room temperature (1.05 mole of MDI per mole erably at least 50%, preferably at least 60%. of OH) for 1 hour. The polysaccharide derivative was filtered 0098. In an embodiment, the at least one polysaccharide is off and washed with dry acetonitrile. The polysaccharide a starch and the crystallinity of the polysaccharide derivative, derivative was then dried under vacuum and filled into con as measured by XRD, is at least 5%, preferably at least 10%, tainers flushed with nitrogen. preferably at least 15%, preferably at least 20%. 0110 FT-IR analysis of the derivative exhibited aurethane 0099. In some embodiments, the crystallinity index of the stretch at 1730 cm and an isocyanate stretch at 2275 cm. polysaccharide derivative is at least 50% that of the at least 0111. The NCO content of the polysaccharide derivative one polysaccharide, preferably at least 60%, preferably at was NCOv=1.7+/-0.1 w %. least 70%, preferably at least 80%. 0112 The crystallinity index (CI) of neat microcrystalline 0100. The polysaccharide derivative obtained by the pro Avicel(R) and of the polysaccharide derivative was measured. cess of the present invention can be further reacted into a The CI of cellulose was 85%, and the CI of the polysaccharide prepolymer. The prepolymer can be generally prepared by derivative prepared in this example was 82%. This shows that reacting the polysaccharide derivative with isocyanate reac this process for preparing the polysaccharide derivative had tive components which are typically components containing limited effects on the bulk crystallinity and related bulk prop isocyanate-reactive hydrogen atoms, such as a hydroxyl ter erties of the polysaccharide. minated polyether (polyether polyols), a hydroxyl terminated polycarbonate or mixture thereof, and hydroxyl terminated Comparative Example 2 polyesters (polyester polyol). 0113 Microcrystalline cellulose (Avicel(R) was dried EXAMPLES under vacuum at 60° C. for 12 hours and weighted into a reaction flask. Isocyanate (a mixture of 50% 4,4'-MDI and 0101 The examples described hereunder illustrate the 50%. 2,4'-MDI) was added to the reaction flask while blan properties of the processes and polysaccharide derivatives keting with nitrogen and stirring vigorously at room tempera according to embodiments of the present invention. Unless ture (1.05 mole of MDI per mole of OH) for 1 hour. The otherwise indicated, all parts and all percentages in the fol material was filtered off and washed with dry acetonitrile. The lowing examples, as well as throughout the specification, are material was then dried under Vacuum and filled into contain parts by weight or percentages by weight respectively. ers flushed with nitrogen. 0114. The NCO content was NCOv=0.1 w %, FT-IR Methods analysis (in ATR mode) exhibited a spectrum identical to the 0102 The following methods were used in the examples: cellulose reference spectrum, showing that the cellulose was 0103 FT-IR analysis (in ATR mode) was used to identify not derivatized with the process of the comparative example. urethane stretch modes and isocyanate stretch modes. 0104. The NCO content of the polysaccharide derivative Comparative Example 3 was determined by titration according to DIN 53185. 0115 Microcrystalline cellulose (Avicel(R) was dried 0105. The crystallinity index (CI) was measured by XRD under vacuum at 60° C. for 12 hours and weighted into a analysis as described below: reaction flask. A 1 wt % solution of microcrystalline cellulose 0106 The crystallinity was measured by X-Ray Diffrac was made by adding 4 wt % lithium chloride in 1,3-dimethyl tion, using CuKO. radiation generated at 45 kV and 36 m.A. 2-imidazolidinone to the reaction flask, and heating the mix The CuKO. radiation consists of KC. 1 (0.15406 mm) and KO.2 ture for 1 hour at 140°C. while blanketing with nitrogen and (0.1544.4 nm) components. stirring vigorously. After dissolution, the mixture was let to 0107 For the cellulose based derivative of example 1 (and cool downto room temperature. Isocyanate (a mixture of 50% comparative examples 2-3), the CI was calculated from the 4,4'-MDI and 50%. 2,4'-MDI) was added to the reaction flask height ratio between the intensity of the crystalline peak while blanketing with nitrogen and stirring vigorously (1.05 (IO02-IAM) and total intensity (IO02) after subtraction of the mole of MDI per mole of OH). The reaction mixture gelled background signal measured without cellulose. The X-ray instantaneously, and yielded a brittle material. The material diffraction spectrum of Avicel PH-101 is given in FIG. 1. was washed with dry acetonitrile. The material was then dried 0108 For the starch based derivative of example 4 (and under vacuum and filled into containers flushed with nitro comparative example 5), crystallinity was quantified by fit gen. XRD analysis of the material indicated a complete amor ting a smooth curve under the main minima of diffractograms phous structure, without any residual crystalline signals (see line i). The area above the smooth curve was taken to (CI=0%). correspond to the crystalline portion. The ratio of upper area to total diffraction area was taken as the degree of crystallin Example 4 ity. The X-ray diffraction spectrum of starch is given in FIG. 0116 Corn starch (Sigma-Aldrich) was dried under 2. vacuum at 80° C. for 6 hours and weighted into a reaction Example 1 flask Anhydrous DMSO was added and the mixture (10 wt % corn starch) was stirred at room temperature for 1 hour. Iso 0109 Microcrystalline cellulose (Avicel(R) was dried cyanate (a mixture of 50% 4,4'-MDI and 50% 2,4'-MDI) was under vacuum at 60° C. for 12 hours and weighted into a added to the reaction flask while blanketing with nitrogen and reaction flask Anhydrous dimethyl sulfoxide (DMSO) was stirring vigorously at room temperature (1.05 mole of MDI added and the mixture (20 wt % microcrystalline cellulose) per mole of OH) for 1 hour. The polysaccharide derivative US 2015/O1521.96 A1 Jun. 4, 2015

was filtered off and washed with dry acetonitrile. The material Comparative Example 8 was then dried under vacuum and filled into containers flushed with nitrogen. 0.125 Microcrystalline cellulose (Neat Avicel) was dis 0117 FT-IR analysis of the polysaccharide derivative persed in SUPRASEC S2020 (uretonimine-enriched MDI), exhibited a urethane stretch at 1730 cm and an isocyanate yielding a 10 w % dispersion, by high shear blade mixing stretch at 2275 cm. (3000 rpm, 4 hours). The dispersion showed a poor stability, 0118. The crystallinity index (CI) of neat semicrystalline and full sedimentation was observed after 2 hours. corn starch and of the polysaccharide derivative was mea sured. The CI of semicrystalline corn starch was 30%, after Example 9 modification the CI was 30%. This shows that this process for 0.126 The polysaccharide derivative prepared in Example preparing the starch derivative had limited effects on the bulk 1 was dispersed in SUPRASEC S2144 (MDI prepolymer), crystallinity and related bulk properties of the corn starch. yielding a 10 wt % dispersion, by high shear blade mixing (3000 rpm, 4 hours). The material was poured into a mould Comparative Example 5 and cured by moisture at room temperature for 2 days. Tensile 0119 Corn starch was dried under vacuum at 80°C. for 6 strength was measured from dogbones at 50mm/min at room hours and weighted into a reaction flask. A 10 wt % solution temperature according to DIN 53504. The results are shown of corn starch was made by adding DMSO to the reaction in Table 1. flask, and heating the mixture to 75° C. for 1 hour while blanketing with nitrogen and stirring vigorously. This solu TABLE 1 tion was added to isocyanate (a mixture of 50% 4,4'-MDI and Crystallinity Stress at break 50%. 2,4'-MDI) while blanketing with nitrogen and stirring PU Polysaccharide polysaccharide (%) (MPa) vigorously at room temperature (1 mole of MDI per mole of OH). The starch was filtered, and washed with dry acetoni S2144 17.6 trile. The material was then dried under vacuum and filled into S2144 Example 1 83 26.9 containers flushed with nitrogen. XRD analysis indicated a complete amorphous structure, without any residual crystal line signals (CI-0%). Example 10 0120 FT-IR analysis of the polysaccharide derivative exhibited a urethane stretch at 1730 cm and an isocyanate I0127. The polysaccharide derivative prepared in Example stretch at 2275 cm. 4 and Comparative example 5 (Comp example 5) were dis persed in SUPRASEC 52144 (MDI prepolymer), yielding a Comparative Example 6 10 wt % dispersion, by high shear blade mixing (3000 rpm, 4 hours). The materials were poured into a mould and cured by 0121 D-glucose was dried under vacuum at 60° C. for 12 moisture at room temperature for 2 days. Tensile strength was hours and weighted into a reaction flask. 4,4'-MDI (1.05 mole measured on dogbones at 50 mm/min at room temperature of MDI per mole of OH) was added to the reaction flask while according to DIN 53504. The results are shown in Table 2. blanketing with nitrogen and the mixture was heated up to 200° C. for 2 hours. Thereafter, the mixture was allowed to TABLE 2 slowly cool to room temperature over a 12 hour period. The resultant material was then ground to a fine powder, dispersed Crystallinity Stress at break in dry KBr and the IR spectrum recorded (transmission PU Polysaccharide polysaccharide (%) (MPa) mode). S2144 17.6 0122) IR showed a large consumption of the NCO func S2144 Corn starch 30 16.0 tionality (loss of absorption band at 2275 cm). However, no S2144 Comp example 5 O 6.5 urethane peak at 1730 cm' was observed, indicating that the S2144 Example 4 30 23.6 loss of NCO is not due to reaction with glucosic OH groups. Urea formation is however seen. Heat and MDI drove a dehy 0128. These results demonstrate that both derivatization dration condensation of the glucose generating and with isocyanate and crystallinity are important requirements the liberated water reacted with the MDI to generate urea. for the derivatized polysaccharide to yield improved proper ties. Examples on Applications I0129. It is to be understood that although preferred 0123. Following examples demonstrate that polysaccha embodiments have been discussed for providing embodi ride derivatives prepared according to the invention are much ments according to the present invention, various modifica more compatible with polyurethane (PU) components upon tions or changes may be made without departing from the dispersion. Furthermore, it is shown that retention of the Scope and spirit of this invention. crystallinity gives improved properties to the PU system. 1. A process for preparing a polysaccharide derivative, comprising the steps of: (a) contacting at least one polysac Example 7 charide having a crystallinity index (CI) of at least 20% as 0.124. The polysaccharide derivative prepared in Example measured by XRD with at least one compound at a tempera 1 was dispersed in SUPRASEC S2020 (uretonimine-en ture of at most 70° C.; and (b) subsequently, contacting the riched MDI), yielding a 10 w % dispersion, by high shear product of step (a) with at least one aromatic isocyanate; blade mixing (3000 rpm, 4 hours). A stable dispersion was thereby preparing a polysaccharide derivative whereby the observed, displaying no noticeable sedimentation after 24 crystallinity index of the polysaccharide derivative is at least hours. 50% that of the at least one polysaccharide. US 2015/O1521.96 A1 Jun. 4, 2015

2. The process according to claim 1 wherein said at least lomaize, amylopectin, cyclodextrin, dextrin, dialdehyde one compound is a polysaccharide Swelling agent preferably starch, erythronium japonicum, high-fructose corn Syrup, a non isocyanate reactive polysaccharide Swelling agent. hydrogenated Starch hydrosylate, hydroxyethyl starch, 3. The process according to claim 1 wherein said com hydroxypropyl distarch phosphate, maltitol, maltodextrin, pound is selected from the group comprising Sulfoxides, for maltose, pentastarch, phosphated distarch phosphate, potato mamides, acetamides, pyrrolidones, pyridines, imidazoles starch, starch, waxy corn, waxy potato starch, and mixtures and mixtures thereof. thereof. 4. The process according to claim 1 wherein the at least one 8. (canceled) polysaccharide comprises at least one glucose sub-unit. 9. (canceled) 5. The according to claim 1 wherein the at least one 10. The process according to claim 1 wherein the NCO polysaccharide is selected from the group comprising: cellu content of the polysaccharide derivative is at least 0.2%, as losic compounds; starches; agarose; alginic acid; alguronic measured according to DIN 53185. acid; alpha glucan: amylose, amylopectin: arabinoxylan; 11. The process according to claim 1 wherein the polysac beta-glucan, callose; capsulan; carrageenan; cellodextrin; charide derivative is in the form of granules, wherein the cellulin; chitin; chitosan; chrysolaminarin; curdlan; cyclo granules have a particle size distribution wherein the D50 is at dextrin; DEAE-sepharose; dextran; dextrin; alpha-cyclodex most 1.0 mm, wherein D50 is defined as the particle size for trin; ficoll; ; fucoidan; galactoglucomannan; galacto which fifty percent by weight of the particles has a size lower mannan; gellan gum, glucan, glucomannan, glycocalyx; than the D50 according to standard ISO 13320:2009. glycogen; ; hypromellose; icodextrin; kefiran; 12. The process according to claim 1 wherein the polysac laminarin; ; levan; lichenin; maltodextrin; mixed charide derivative is in the form of ayarn or fiber, with a linear linkage glucan; mucilage; natural gum; oxidized cellulose; mass density of at most 2000 denier. paramylon; pectic acid; pectin; pentastarch; pleuran; poly 13. The process according to claim 1 wherein the polysac dextrose; polysaccharide peptide; porphyran; pullulan; charide derivative is in the form of a textile or fabric, wherein Schizophyllan; Sepharose; sinistrin; sizofiran, Sugammadex: the textile or fabric may be woven or unwoven. Welangum, Xanthan gum, Xylan, Xyloglucan, Zymosan, gly 14. The process according to claim 1 wherein the at least cosaminoglycans such as glycosaminoglycan, chondroitin, one compound is selected from the group comprising: dim chondroitin Sulfate, dermatan Sulfate, heparan Sulfate, hep ethyl sulfoxide, diethyl sulfoxide, ethylmethyl sulfoxide, arin, heparinoid, hyaluronan, keratan Sulfate, restylane, N,N-dimethyl formamide, N,N-diethyl formamide, N.N-eth Sodium hyaluronate, and Sulodexide; and mixtures thereof. ylmethyl formamide, N-methyl-pyrrolidone, pyridine, 6. The process according to claim 1 wherein the at least one bromo-pyridine, chloro-pyridine, N,N-dimethyl acetamide. polysaccharide is a cellulosic compound selected from the N,N-diethyl acetamide, N.N-ethylmethyl acetamide, 1,3- group comprising: cellulose, nanocellulose, art silk, bacterial dimethyl-2-imidazolidinone, imidazolidinone, 1-methyl-2- cellulose, bamboo fibre, carboxymethyl cellulose, cellodex imidazolidinone, 1-ethyl-2-imidazolidinone, 1-allyl-3-meth trin, cellophane, celluloid, cellulose acetate, cellulose acetate ylimidazolium chloride, 1-butyl-3-methylimidazolium phthalate, cellulose triacetate, cellulosome, cotton, croscar chloride, 1-ethyl-3-methylimidazolium chloride, and mix mellose Sodium, crystalate, ciethylaminoethyl cellulose, dis tures thereof. Solving pulp, ethulose, ethyl cellulose, fique, hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl cel 15. The process according to claim 1 wherein step (a) is lulose, hypromellose, lyocell, mercerised pulp, methyl cellu performed for a time period of at least 30 minutes before step lose, microbial cellulose, microcrystalline cellulose, modal (b). (textile), nitrocellulose, parkesine, pearloid, pulp, paper, 16. The process according to claim 1 wherein the water rayon, sodium cellulose phosphate, Supima, Viscose, Vulca content in the at least one polysaccharide, the at least one nized fibre, wood fibre, and mixtures thereof. aromatic isocyanate and the at least one compound is at most 7. The process according to claim 1 wherein the at least one 0.5% by weight. polysaccharide is a starch selected from the group compris 17. (canceled) ing: corn starch, amylose, acetylated distarch adipate, amy