WO2000015667A1 - Microfibrilles de cellulose a surface modifiee, leur procede de preparation, et leur utilisation - Google Patents
Microfibrilles de cellulose a surface modifiee, leur procede de preparation, et leur utilisation Download PDFInfo
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- WO2000015667A1 WO2000015667A1 PCT/FR1999/002148 FR9902148W WO0015667A1 WO 2000015667 A1 WO2000015667 A1 WO 2000015667A1 FR 9902148 W FR9902148 W FR 9902148W WO 0015667 A1 WO0015667 A1 WO 0015667A1
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- microfibrils
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- microfibnlles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
Definitions
- the present invention relates to surface-modified cellulose microfibrils, their process of preparation, and their use. It also relates to compositions comprising microfibrils of cellulose with modified surface.
- native cellulose is a chain of D-anhydroglucopyranose units linked together in positions ⁇ -1, 4.
- the degree of polymerization (DP) of said chain can vary from a few hundred to several thousand monomer units depending on the source used.
- the intermolecular hydrogen bonds promote a parallel association of the cellulose chains with one another to form microfibrils of more or less crystalline structures and whose diameter can vary from 10 ⁇ to 500 A.
- microfibrils are well known materials which are already proposed, in general, to modify the rheology of the environments in which they are introduced.
- the microfibrils can modify the viscosity and / or the texture of the medium, even its rheological profile.
- microfibrils can modify the mechanical properties and in particular serve as a reinforcing filler.
- microfibrils are attributed to their particular structure; they have an important hydrophilic nature due to the presence of hydroxyl functions on the surface of the microfibrill.
- hydrophilic nature which may be desirable for certain applications, for example in aqueous and / or hydrophilic media, can constitute an obstacle to the various desired applications in organic and / or hydrophobic media.
- the microfibrils do not disperse and there are agglomeration and flocculation phenomena, due to the incompatibility of the latter with the organic medium in which they are found; microfibrils having a highly hydrophilic character will naturally tend to flocculate and agglomerate in an organic medium with hydrophobic character. As a result of these phenomena, more particularly in an organic medium, the microfibers will no longer be able to exercise their function of viscous texturing agent and / or reinforcing filler.
- the object of the present invention is to propose microfibials of cellulose which, while having retained their initial molecular and crystalline aspects and therefore all the advantageous mechanical properties which result therefrom, have a markedly attenuated hydrophilic character.
- the object of the invention is also to provide microfibils which are dispersible in an organic medium.
- the present invention which relates to surface-modified cellulose microfibils, characterized in that the hydroxyl functions present on the surface of the microfibers are ethe ⁇ fiés by at least one organic compound comprising at least one function capable of reacting with said hydroxyl functions, and in that the degree of surface substitution (DSs) is at least 0.05 organic residues from organic compounds ethenfiants fixed in surface of the microfibnlles ensure better compatibility of the microfibnlle with the organic medium in which it is dispersed
- the hydrophilic character of the microfibnlles is consequently markedly attenuated, and they can therefore control the rheological properties of the medium At this stage, it is important to define the term "dispersibility"
- the term “dispersibility” designates surface-modified microfibils, which, once introduced into an organic medium, are capable of dispersing under low shear, and of forming a non-flocculating dispersion.
- the microfibnlles of the invention are made dispersible by a superficial hydrophobisation of the hydroxyl functions their initial morphology is preserved and a crystalline arrangement is always observed
- an "organic medium” means a medium consisting of a liquid or a mixture of inert organic and or hydrophobic liquids, in which the "unmodified" microfibrils do not disperse. of a mixture of liquids, they will preferably be miscible.
- ° alcohols such as ethanol, isopropa ⁇ ol, butanol, hexanol, octanol, ° aldehydes and ketones such as butyraldehyde, acetone, methylethyl ketone, 4-methyl-2-pentanone, ° cyclic or acyclic ethers such as diethyl ether and its higher counterparts, dioxane, tetrahydrofuran,
- ° halogenated solvents such as dichloro-, dibromo-, dnodomethane, chloroform, bromoform, carbon tetrachloride, has cyclic or acychque alkanes such as pentane, hexane, octane, dodecane, cyclopentane, cyclohexane, ⁇ optionally substituted aromatic solvents such as benzene, toluene, chlorobenzene, bromobenzene, ° acetates d alkyl such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, ⁇ fatty acid esters such as isopropyl my ⁇ state, esters methyl palmitic acid, steanic acid, arachidic acid, soybean oil fatty acid, rapeseed, corn, sunflower, peanut
- the cellulose microfibrils can be
- animal sources of cellulose mention may be made of animals of the tunicate family.
- the vegetable sources of cellulose can be wood, cotton, linen, ramie, certain algae, jute, sugar beet pulp, citrus ( lemons, orange, grapefruit), or the like
- microfibles advantageously have an L / D ratio greater than 15, advantageously greater than 50, more particularly greater than 100, and preferably greater than 500 and an average diameter (D) of between 10 A and 500 A, advantageously between 15 A and 200 ⁇ more particularly between 15 A and 70 A, preferably between 18 A and 40 A, L representing the length of the microfibles and D their average diameter
- Microfibrils can be obtained from the cellulosic sources mentioned above by various methods already described in the literature. Among these methods, reference may be made, for example, to the methods described in European patent applications EP 0726356, EP 0102829, or the American patent. US 4481076, the teachings of which are incorporated HERE
- microfibnlles are obtained by implementing the method which will be described below
- this process is carried out on the pulp of plants with primary walls, such as for example beet pulp after it has undergone a step of prior sucrose extraction, according to the methods known in the art.
- the method includes the following steps
- step (d) optionally bleaching the washed residue, (e) diluting the third solid residue obtained at the end of step (d) so as to obtain a dry matter content of between 2 and 10% by weight, (f) homogenization of the diluted suspension
- step (a) the term "pulp” means moist, dehydrated pulp, preserved by silage or partially depected.
- the extraction step (a) can be carried out in an acid medium or in a basic medium.
- the pulp is suspended in a solution of water for a few minutes so as to homogenize the acidified suspension at a pH between 1 and 3, preferably between 1, 5 and 2.5
- This operation is carried out with a concentrated solution of an acid such as hydrochloric acid or sulfu ⁇ que acid
- This step can be advantageous for removing the calcium oxalate crystals which may be present in the pulp, and which, because of their significant abrasive nature, can cause difficulties in the homogenization step.
- the pulp is added to an alkaline solution of a base, for example soda or potash, of concentration less than 9% by weight, more particularly less than 6% by weight
- a base for example soda or potash
- concentration of the base is between 1 and 2% by weight
- a small amount of a water-soluble antioxidant may be added, such as sodium sulfite Na2S patented3, in order to limit the oxidation reactions of the cellulose.
- Step (a) is generally carried out at a temperature between about 60 ° C and 100 ° C, preferably between about 70 ° C and 95 ° C
- stage (a) The duration of stage (a) is between approximately 1 hour and approximately 4 hours.
- stage (a) there occurs a partial hydrolysis with release and solubi sation of the major part of pectins and hemicelluloses, all preserving the molecular weight of cellulose
- the solid residue is recovered from the suspension originating from step (a) using known methods.
- the first solid residue obtained is optionally subjected to a second extraction step, carried out under alkaline conditions.
- a second extraction step, step (b), is carried out when the first has been carried out under acidic conditions. If the first extraction was carried out under alkaline conditions, the second step is only optional.
- this second extraction is carried out with a base, preferably chosen from soda and potash, the concentration of which is less than about 9% by weight, preferably between about 1% and about 6% by weight.
- the duration of the alkaline extraction step is between approximately 1 and approximately 4 hours. It is preferably equal to approximately 2 hours. At the end of this second extraction, if it takes place, a second solid residue is recovered.
- step (c) the residue from step (a) or (b) is washed thoroughly with water in order to recover the residue of cellulosic material.
- step (c) The cellulosic material of step (c) is then optionally bleached, in step (d), according to conventional methods.
- treatment can be carried out with sodium chlorite, sodium hypochlorite, hydrogen peroxide at a rate of 5-20% relative to the amount of dry matter treated.
- Different concentrations of bleach can be used, at temperatures between about 18 ° C and 80 ° C, preferably between about 50 ° C and 70 ° C.
- the duration of this step (d) is between approximately 1 hour and approximately 4 hours, preferably between approximately 1 and approximately 2 hours.
- a cellulosic material is then obtained containing between 85 and 95% by weight of cellulose. At the end of this bleaching step, it may be preferable to wash the cellulose thoroughly with water.
- the resulting suspension optionally bleached, is then rediluted in water at a rate of 2 to 10% of dry matter (step (e)). before undergoing a homogenization step (step (f)), comprising at least one cycle.
- the homogenization step corresponds to a mixing, grinding or any high mechanical shearing operation, followed by one or more passages of the cell suspension through a small diameter orifice, subjecting the suspension to a pressure drop of at least 20 mPa and a high speed shearing action followed by a high speed deceleration impact.
- the mixing or grinding is, for example, carried out by passage (s) in the mixer or grinder for a period ranging from a few minutes to about an hour, in a device of the type such as a WARING BLENDOR equipped with a four-blade propeller or grinder grinding wheel or any other type of grinder, such as a colloid mill.
- a homogenizer of the MANTON GAULIN type in which the suspension is subjected to a shearing action at high speed and pressure in a narrow passage and against a shock ring.
- the MICRO FLUIDIZER is a homogenizer mainly consisting of a compressed air motor which will create very high pressures, an interaction chamber in which the homogenization operation will be carried out (elongational shearing, shocks and cavitations) and a low pressure chamber which allows the depressurization of the dispersion
- the suspension is introduced into the homogenizer preferably after preheating at a temperature between 40 and 120 ° C, preferably between 85 and 95 ° C
- the temperature of the homogenization operation is maintained between 95 and 120 ° C, preferably above 100 ° C.
- the suspension is subjected in the homogenizer to pressures between 20 and 100 mPa, and preferably greater than 50 mPa
- the homogenization of the cellulosic suspension is obtained by a number of passages which can vary between 1 and 20, preferably between 2 and 5, until a stable suspension is obtained.
- the homogenization operation can advantageously be followed by '' a high mechanical shear operation, for example in a device such as the ULTRA TURRAX from SYLVERSON
- the microfibnlles will undergo an ethenfication reaction
- ethenfication is used in the broad sense and designates the reactions in which the hydroxyl functions O-H can be transformed into O-Y, in particular
- organic compound comprising at least one function capable of reacting with the hydroxyl functions found on the surface of the microfibils, will also be called in the remainder of the description, organic ethenfiant compound or ethenfication agent
- the ethenfication agent is advantageously chosen from silylating agents, isocyanates, halogenated alkylating agents, alkylene oxides and / or glycidyls
- the silylation agents can be chosen from D the haloalkylsilanes of formula R 3 R 2 R 1 S ⁇ -X, R 2 R 1 S ⁇ (X) 2 , R 1 S ⁇ (X) 3
- the radicals R, R ⁇ , R 2 and R 3 can be chosen from methyl, ethyl propyl, isopropyl, butyie, sec-butyl, tert-butyl pentenyl, hexyl cyclohexyl , octyl, nonyl, decyl, dodecyl, undecyle, nonadecyle, eicosyle (C-20), docosyle (C-22), octacosyl (C-28), triacontanyl ( C-30) vinyl, allyl, phenyl, styryl, naphthyl
- silylating agent there may be mentioned more particularly ° among the haloalkylsilanes chlorodimethylisopropyl silane chlorodimethylbutyl silane, chlorodimethyloctyl silane chlorodimethyldodecyl silane, chlorodimethyloctadecyl silane chlorodimethylphenyl silane, chlorohexylmethylane methylenichlorohexylane hexane dichloroheptylmethyl silane, trichlorooctyle silane, ⁇ among disilazanes, hexamethyl disilazane, 1, 3-d ⁇ v ⁇ nyl-1, 1 3 3- tetramethyl disilazane, 1, 3-d ⁇ v ⁇ nyl-1, 3-d ⁇ phenyl-1, 3-d ⁇ m disilazane, 1, 3-N-d ⁇ octyltetramethyl disilazane, dusobutyltetramethyl dis
- etherification of the hydroxyl functions of the microfibrils can also be done by halogenated alkylating agents of formula R -X, in which X is a halogen atom chosen from chlorine, bromine, and iodine, and R 4 is a hydrocarbon
- the ethenfication agent may, in addition, be an isocyanate of formula R 5 -NCO, in which R 5 is a hydrocarbon radical corresponding to the same definition as R,
- the isocyanate is advantageously chosen from, buty isocyanate, tert-butyl isocyanate, pentyl isocyanate, octyl isocyanate, dodecyl isocyanate, octadecyl isocyanate, phenylisocyanate .
- the alkylene oxides can also be used as a wetting agent. In the alkylene oxides of formula:
- R 6 can represent a hydrocarbon radical corresponding to the same definition as R, R 1 , R 2 , and R 3 .
- the etherification agent can also be a glycidyl of formula: CH 2 -CH 2 -CH 2 -OR 7
- R 7 can represent a hydrocarbon radical corresponding to the same definition as R, R ⁇ , R 2 , and R 3 .
- the glycidyl can be chosen from methyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, methyl-2-butyl glycidyl ether. ethylhexyl glycidyle ether, octylglycidyle ether, laurylglycidyle ether, allylglycidyle ether, benzylglycidyle ether.
- the hydroxyl functions of the microfibrils can be etherified with only one type of etherification agent among those mentioned below, or with etherification agents of different nature.
- etherification can take place either in one or in several successive reaction (s), which would lead to obtaining microfibrilies comprising on the surface different organic residues.
- DSs degree of surface substitution
- the degree of surface substitution is generally defined as the number of surface substituted hydroxyl functions per unit of glucose II is obtained from the overall average degree of substitution DS, from the general formula
- the overall average DS is obtained by determining the weight concentration of all or part of the group grafted by etherification reaction, and by applying the following general formula •
- ° Y represents the percentage by weight relative to the total weight of the grafted product of the analyzed part (this can be thus, the% w / w of a heteroatom measured by elementary analysis, or even the% w / w of a group measured by a chromatographic technique),
- ° g represents the molecular weight of the analyzed part (in the case of a heteroatom, it will be the molecular weight of this heteroatom, in the case of a given group, it will be the molecular weight of the group),
- ° G represents the total molecular weight of the group grafted by ethenfication
- a silylating agent for example a haloalkylsilane, in particular chlorodimethylisopropyl silane
- n hydrogen by n alkylsilane groups in particular dimethylisopropylesilyl
- the degree of substitution (DSs) is then obtained from the ratio of Cs (number of surface chains) and Ct (total number of chains)
- the degree of substitution is then obtained from the ratio of C s (number of chains on the surface) and Ct (total number of chains) which is 0.77 in the case of beet microfibnlles
- the degree of surface substitution can be determined by conventional elemental analysis.
- the (DSs) can be determined by assaying the alkyl groups advantageously according to the Zeisel method, described in Analytical Chemistry No. 13, p. 2172, 1979. This method consists in degrading the ether bond at 140 ° C. in the presence of hydrogen iodide (Hl), and in determining the corresponding iodides by gas chromatography.
- the alkyl groups can also be determined by the 13 C nuclear magnetic resonance, according to the method described by Y. Tezuka: Determination of substitute distribution in cellulose ether by mean of 13 C NMR study on their acetylated derivatives, Makromol. Chem. 191, p. 681, 1990.
- the degree of surface substitution (DSs) is at least 0.05, advantageously between 0.1 and 1, and more particularly between 0.2 and 0.7.
- a subject of the invention is also a method for manufacturing surface-modified cellulose microfibrils, as described above, from cellulose microfibrils obtained by fibrillation of a material containing cellulose fibers, characterized in that it consists at :
- DSs degree of substitution
- non-destructuring medium of the cellulose microfibrill means a medium in which the microfibrill retains its native crystalline character.
- this liquid must not dissolve the cellulose, nor have a negative effect on the structure of the cellulose microfibrils.
- ahphatic and / or cyclic ethers in particular ethyl ether and tetrahydrofuran, optionally halogenated ahphatic hydrocarbons, in particular hexane, xylene, perchlorethylene, optionally halogenated aromatic hydrocarbons, in particular toluene, pyridine.
- alcohols in particular isopropanol, butanol, and water, these liquids being able to be alone or as a mixture
- an etherification agent or a mixture of etherification agents is added to the medium, advantageously with a catalyst and / or an etherification activator
- the etherification agents are chosen from those described above.
- the etherification catalysts can be chosen from the group comprising, for example, imidazole, pyridine, tnethylamine, tetrabutylammonium fluoride hydrate, t ⁇ methylsilyl chloride, soda , potash, tin derivatives such as for example tin octaonate, tin dilaureate
- sodium hydroxide, potassium hydroxide, pyridium can be cited by way of example
- the person skilled in the art will know how to choose the most suitable catalyst and / or activator (s), as well as their concentration (s) both with respect to the dispersing liquid medium and with respect to the microfibers
- the nature and concentration of the catalyst and or of the activator will be chosen so as to avoid destruction of the microfibril
- steps (i) and (n) may possibly be concomitant
- the etherification reaction is advantageously carried out with stirring and optionally in an inert atmosphere
- the etherification reaction is carried out at the appropriate temperature for a period determined according to the degree of surface substitution (DSs) desired
- the temperature will be chosen taking into account the nature of the etherification agent and its reactivity
- the etherification stop - step (m) - is obtained, for example, either by the addition of a compound, advantageously water, rendering the ethenfication agent inactive, or by cooling and / or dilution of the medium, either by exhaustion of the etherification agent (s)
- the partially etherified microfibrils are then extracted from the medium - step (iv) - by any appropriate means, in particular by lyophilization, centrifugation, filtration, or precipitation.
- microfibrils are then advantageously washed and dried.
- steps (i) and (ii) are concomitant.
- the surface modification of the microfibrils therefore makes it possible to obtain very good dispersibility and compatibility with organic media, whether they are fluid, highly viscous or solid.
- Another subject of the invention relates to the use of surface-modified microfibrils according to the invention, as viscosifying and / or texturing agents for fluid media and / or as texturing agent and / or reinforcing filler for highly viscous or solid media .
- the present invention also relates to compositions comprising surface-modified cellulose microfibrils as described above or as obtained according to the above method.
- microfibrils of the invention can exercise their function as viscosity agents in cosmetic formulations, drilling fluids, paints, varnishes, glues, inks, and as a reinforcing filler in polymers, especially in materials. thermoplastics, thermosets, crosslinked or non-crosslinked elastomers, and sealants.
- the present invention also relates to compositions comprising surface-modified microfibrils as described above or as obtained according to the above-mentioned method.
- compositions in addition to the microfibrils, it is possible to add the usual additives necessary for their use according to the field of application such as, for example, vulcanization ingredients in the particular case of elastomers, coupling agents, plasticizers, stabilizers , lubricants, pigments, etc.
- vulcanization ingredients in the particular case of elastomers, coupling agents, plasticizers, stabilizers , lubricants, pigments, etc.
- compositions can be used for example as floor coverings, engine supports, parts of vehicle tracks, shoe soles, cable car rollers, electrical appliance seals, cable sheaths, transmission belts
- compositions according to the invention can find applications as a battery separator.
- the present invention makes it possible to obtain compositions based on elastomer or an alloy or mixture of elastomers, and preferably vulcanized, which can be used in any part of the tire
- the content of combination according to the invention is such that the content of microfibils in the part concerned of the tire can range up to 80% by weight, more particularly can be between 0.1 and 50% by weight relative to the total weight of the composition
- compositions comprising at most 10% by weight, advantageously at most 5% by weight, and preferably at most 2% by total weight relative to the total weight of the composition
- the dry matter content is determined on the one hand by drying and weighing and on the other hand the residual water content by Karl Fischer assay (device fitted with a Buchi oven heated to 150 ° C. for 1 hour under nitrogen sweep)
- the amount of cellulose is 0.158 g (0.975 10 ⁇ 3 moles) anhydroglucose equivalent
- the water content is 0.0181 g (1.0 10 "3 moles)
- the suspension is then placed in a reactor and the desired quantity of reagent is added so as to have 2 moles of silane for 1 surface anhydroglucose group.
- the mixture is then stirred in the closed reactor, at room temperature for 16 hours.
- the viscosity () is measured on an RFS 8400 rheometer in Duvet geometry (scanning in shear gradient between 0.1 and 100 s -1 )
- suspensions of microfibials of Example 1 in THF exhibit high viscosities, and a behavior of pseudo plastic type (decrease in viscosity when the shear gradient increases) This type of behavior is comparable to that of non-microfibials. surface modified in water
- the amount of dry matter is 19.5 g (0.120 moles) and the amount of residual water is 0.195 (0.0108 moles)
- the suspension is then placed in a reactor and the desired amount of reagents is added so as to have 1.74 moles of silane for 1 surface anhydroglucose group
- the cake is placed in water, passed through a rotary evaporator to remove the residual acetone and lyophilized
- microfibrils thus modified form dispersions at room temperature for a concentration of 0.05% w / w, obtained directly by mixing between the powder and the liquid and then treated for 2 minutes in an ultrasonic tank, which dispersions do not flocculate in the solvents.
- the amount of cellulose in this example is 0.115 g (0.709 10 "3 moles) anhydroglucose equivalent (AHGU), and the water content is 0.0096 g (0.533 10 " 3 moles)
- the amount of chlorodimethylbutyl silane is 0, 18 ml, and that of imidazole is 0.074 g (1.08 10 "3 moles)
- the molecular weight of chlorodimethyloctyl silane is 206.8 and its density of 0.873
- the amount of cellulose in this example is 0 213 g (1, 315 10 "3 moles) anhydroglucose equivalent (AHGU), and the water content is 0.017 g (0.944 10 " 3 moles)
- the amount of chlorodimethyloctyl silane is 0.70 ml, and that of imidazole is 0.202 mg (3 10 "3 moles)
- the desired quantity of silylating agent is added so as to have 2 moles of silane for 1 surface anhydroglucose group
- microfibnlles thus "ethe ⁇ fiees" are always in the form of fibers
- the molecular weight of chlorodimethyldodecyl silane is 262.9 and its density is 0.865
- the amount of cellulose in this example is 0.177 g (1,092 10 "3 moles) anhydroglucose equivalent (AHGU), and the water content is 0.02 g (1,111 10 " 3 moles)
- the quantity of chlorodimethyldodecyl silane is 0.85 ml, and that of imidazole is 0.190 mg (2.8 ⁇ 10 ⁇ 3 moles)
- the desired quantity of silylating agent is added so as to have 2 moles of silane for 1 surface anhydroglucose group
- the surface of the microfibers is modified by reacting the surface hydroxyls with octyl isocyanate.
- microfibril suspension in anhydrous toluene contains 0.167 g of cellulose (1.03 10 ⁇ 3 ). It is then placed in a reactor and 1.2 ml of octyl isocyanate of molecular weight equal to 155.2 is added and with a density equal to 0.88
- composition B modified microfibrils derived from example 3
- composition A modified microfibrils
- the amounts are expressed in percent by weight relative to the total weight of the composition.
- Each composition is produced by thermo-mechanical work in an internal Brabender mixer of 70 cm 3 , in one step, for an average speed of the pallets of 50 revolutions per minute, until reaching a temperature of 100 ° C. at the end of step, and followed by an acceleration and finishing step on an external mixer.
- the vulcanization of the compositions is adapted to the vulcanization kinetics of each mixture.
- traction the modules are measured on the vulcanizates according to standard NF T46002. It should be noted that the 10%, 100%, 300% modulus in the rubber trades, refers to the stress measured respectively at 10%, 100% or 300% of tensile deformation.
- Shore A 15s hardness Shore A 15s hardness is measured according to standard ASTM D2240, the value considered is determined 15 seconds after the application of the force.
- composition B the composition containing the surface-modified microfibrils leads to mechanical stresses and to significantly higher hardness compared to the reference composition (composition A). It is remarkable to note that the gain in modulus of the composition comprising the microfibnlles of the invention occurs without harming the resistance to breakage and the elongation at break of the vulcanized composition. On the contrary, in the presence of microfibnlles, there is a significant increase in the deformation at break
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Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU55233/99A AU5523399A (en) | 1998-09-15 | 1999-09-09 | Cellulose microfibrils with modified surface, preparation method and use thereof |
EP99941729A EP1114065A1 (fr) | 1998-09-15 | 1999-09-09 | Microfibrilles de cellulose a surface modifiee, leur procede de preparation, et leur utilisation |
BR9913767-4A BR9913767A (pt) | 1998-09-15 | 1999-09-09 | Microfibrilas de celulose com superfìcie modificada, processo de fabricação das mesmas, utilização das microfibrilas, e, composição |
US09/787,272 US6703497B1 (en) | 1998-09-15 | 1999-09-09 | Cellulose microfibrils with modified surface, preparation method and use thereof |
CA002344201A CA2344201C (fr) | 1998-09-15 | 1999-09-09 | Microfibrilles de cellulose a surface modifiee, leur procede de preparation, et leur utilisation |
JP2000570205A JP3548120B2 (ja) | 1998-09-15 | 1999-09-09 | 変性表面を持つセルロースミクロフィブリル、それらの製造方法およびそれらの用途 |
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FR98/11507 | 1998-09-15 | ||
FR9811507A FR2784107B1 (fr) | 1998-09-15 | 1998-09-15 | Microfibrilles de cellulose a surface modifiee, leur procede de preparation, et leur utilisation |
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WO2000015667A1 true WO2000015667A1 (fr) | 2000-03-23 |
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PCT/FR1999/002148 WO2000015667A1 (fr) | 1998-09-15 | 1999-09-09 | Microfibrilles de cellulose a surface modifiee, leur procede de preparation, et leur utilisation |
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US (1) | US6703497B1 (fr) |
EP (1) | EP1114065A1 (fr) |
JP (1) | JP3548120B2 (fr) |
AU (1) | AU5523399A (fr) |
BR (1) | BR9913767A (fr) |
CA (1) | CA2344201C (fr) |
FR (1) | FR2784107B1 (fr) |
WO (1) | WO2000015667A1 (fr) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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FR2800378A1 (fr) * | 1999-11-03 | 2001-05-04 | Saint Louis Sucre Sa | Microfibrilles de cellulose i comportant des groupements ethers substitues en surface a des groupements hydroxyles, leur procede de preparation et leur utilisation |
WO2006056737A1 (fr) * | 2004-11-23 | 2006-06-01 | Cellucomp Limited | Matiere biocomposite amelioree |
EP2196478A1 (fr) | 2008-12-12 | 2010-06-16 | EMPA Eidgenössische Materialprüfungs- und Forschungsanstalt | Nanofibrilles de cellulose modifiées en surface |
US7989110B2 (en) * | 2002-06-21 | 2011-08-02 | Institut National Polytechnique De Grenoble | Reinforced ionic conducting material, use thereof in electrodes and electrolytes |
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- 1999-09-09 BR BR9913767-4A patent/BR9913767A/pt not_active Application Discontinuation
- 1999-09-09 CA CA002344201A patent/CA2344201C/fr not_active Expired - Fee Related
- 1999-09-09 EP EP99941729A patent/EP1114065A1/fr not_active Withdrawn
- 1999-09-09 US US09/787,272 patent/US6703497B1/en not_active Expired - Fee Related
- 1999-09-09 AU AU55233/99A patent/AU5523399A/en not_active Abandoned
- 1999-09-09 JP JP2000570205A patent/JP3548120B2/ja not_active Expired - Fee Related
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2800378A1 (fr) * | 1999-11-03 | 2001-05-04 | Saint Louis Sucre Sa | Microfibrilles de cellulose i comportant des groupements ethers substitues en surface a des groupements hydroxyles, leur procede de preparation et leur utilisation |
ES2177425A1 (es) * | 1999-11-03 | 2002-12-01 | Saint Louis Sucre S A | Microfibrillas de celulosa i que comprenden unos grupos eteres que sustituyen en superficie a unos grupos hidroxilos, su procedimiento de preparacion y su utilizacion. |
US7989110B2 (en) * | 2002-06-21 | 2011-08-02 | Institut National Polytechnique De Grenoble | Reinforced ionic conducting material, use thereof in electrodes and electrolytes |
WO2006056737A1 (fr) * | 2004-11-23 | 2006-06-01 | Cellucomp Limited | Matiere biocomposite amelioree |
US8834980B2 (en) | 2004-11-23 | 2014-09-16 | Cellucomp Limited | Biocomposite material |
EP2196478A1 (fr) | 2008-12-12 | 2010-06-16 | EMPA Eidgenössische Materialprüfungs- und Forschungsanstalt | Nanofibrilles de cellulose modifiées en surface |
Also Published As
Publication number | Publication date |
---|---|
FR2784107A1 (fr) | 2000-04-07 |
JP3548120B2 (ja) | 2004-07-28 |
AU5523399A (en) | 2000-04-03 |
CA2344201A1 (fr) | 2000-03-23 |
EP1114065A1 (fr) | 2001-07-11 |
US6703497B1 (en) | 2004-03-09 |
FR2784107B1 (fr) | 2005-12-09 |
CA2344201C (fr) | 2006-01-10 |
JP2002524618A (ja) | 2002-08-06 |
BR9913767A (pt) | 2002-01-15 |
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