EP2464681A1 - Fibres cellulosiques modifiées, fabrication et utilisation - Google Patents

Fibres cellulosiques modifiées, fabrication et utilisation

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Publication number
EP2464681A1
EP2464681A1 EP10739925A EP10739925A EP2464681A1 EP 2464681 A1 EP2464681 A1 EP 2464681A1 EP 10739925 A EP10739925 A EP 10739925A EP 10739925 A EP10739925 A EP 10739925A EP 2464681 A1 EP2464681 A1 EP 2464681A1
Authority
EP
European Patent Office
Prior art keywords
cellulose fibers
weight
composite materials
modified cellulose
hydrogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP10739925A
Other languages
German (de)
English (en)
Inventor
Thomas Pfeiffer
Heike Pfistner
Szilard Csihony
Ivette Garcia Castro
Michael Neuss
Thomas Zelinski
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mondi Frantschach GmbH
BASF SE
Original Assignee
Mondi Frantschach GmbH
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mondi Frantschach GmbH, BASF SE filed Critical Mondi Frantschach GmbH
Priority to EP10739925A priority Critical patent/EP2464681A1/fr
Publication of EP2464681A1 publication Critical patent/EP2464681A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/04—Homopolymers or copolymers of ethene
    • C09D123/08—Copolymers of ethene
    • C09D123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09D123/0892—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms containing monomers with other atoms than carbon, hydrogen or oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0892—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms containing monomers with other atoms than carbon, hydrogen or oxygen atoms

Definitions

  • Modified cellulose fibers their preparation and use
  • the present invention relates to a process for the production of composite materials, characterized in that one produces modified cellulose fibers in one step by
  • thermoplastic resin (C) at least one thermoplastic
  • the present application relates to cellulose fibers treated with at least one aqueous emulsion of
  • the present invention relates to the use of cellulose fibers according to the invention for the production of composite materials.
  • Wood as a material has been known to civilization for several millennia. It is characterized by a good availability in most parts of the world. Also, wood is versatile to use by numerous processing techniques. In many countries, wood is still used outdoors in buildings, for example in the production of roofs, facades, window frames, verandas, and for the production of benches such as park benches, and for the production of hollow bodies such as hollow profiles for decking or window sills ,
  • a serious disadvantage of using exterior wood of buildings is its lack of weatherability. In particular, humid-warm weather can lead to rotting. Attempts to protect wood by coating, for example by paint layers against the weather, while slowing down rotting, but not completely prevent. Paint finishes also have the disadvantage that they have to be renewed at regular intervals. In addition, many coatings are sensitive to mechanical stress and damage, which can lead to, for example, a peeling of the paint.
  • the shaping of wood is only possible by consuming procedures that cause a lot of waste.
  • Plastics such as polyvinyl chloride or polyolefins such as polyethylene or polypropylene, however, have thermal expansion coefficients that turn out to be too large in many outdoor applications. Also, the stiffness is too low in many cases.
  • composites made of wood and plastic also called: natural-fiber-reinforced plastics, in short: WPC
  • WPC natural-fiber-reinforced plastics
  • Such composites show a significantly higher weathering stability than pure wood and better mechanical properties than some pure plastics, for example polyethylene or polypropylene.
  • WO 2008/101937 discloses composites of natural fibers, for example wood, and thermoplastic polymers and optionally further substances.
  • natural fibers, thermoplastics and certain ethylene copolymer waxes and optionally other substances are mixed.
  • the processing takes a relatively long time, which is technically unfavorable.
  • some of the mechanical properties such as tensile strength, flexural strength, impact strength, breaking stress, elongation at break and / or elongation at break can still be improved.
  • WO 2007/1 18264 a process for the treatment of cellulosic fiber material is known in which treated with magnesium ion-containing solutions. Treated materials which are well suited for packaging are obtained on the basis of but not for composite materials. Also, in many cases, the water-repellent properties can be improved.
  • a further object was to provide composite materials which have particularly good mechanical properties, such as tensile strength, flexural strength, impact strength, breaking stress, elongation at break and / or elongation at yield and lower water absorption.
  • Another object was to provide uses for composites.
  • the inventive method is based on cellulose fibers (A).
  • Cellulosic fibers in the present invention also include lignocellulosic fibers.
  • cellulose fibers (A) are fibers of flax, sisal, hemp, coconut, abaca (so-called manila hemp), but also rice husks, bamboo, straw and peanut shells.
  • Preferred examples of cellulose fibers (A) are wood fibers.
  • Wood fibers may be fibers of freshly obtained wood or old wood.
  • wood fibers may be fibers of different types of wood such as softwoods of e.g.
  • wood waste such as wood shavings, sawdust or sawdust are suitable.
  • the wood composition may vary in its constituents such as cellulose, hemicellulose and lignin.
  • cellulosic fibers (A) are pulp. Pulp may be unbleached or bleached pulp. Pulp in the sense of the present invention can be obtained by alkaline or acid pulping process.
  • Pulp in the sense of the present invention may have a lignin content in the range of zero to 20 wt .-%.
  • cellulosic fibers (A) have a kappa number in the range of zero to 100.
  • cellulose fibers (A) have an average length in the range of 0.1 to 100 mm, preferably 1 to 10 mm.
  • cellulosic fibers (A) are long fiber pulp.
  • Long fiber pulp in the context of the present invention may have a length in the range of 1 to 7 mm.
  • Long fiber pulp in the context of the present invention may have a particle width in the range of 10 to 50 microns.
  • Long fiber pulp in the sense of the present invention may have a coarseness in the range from 100 to 500 mg / m.
  • the length / thickness ratio of cellulose fibers (A) is in the range of 500 to 1 to 50 to 1, especially when selecting cellulose fibers (A) from long fiber pulp.
  • one selects cellulose fibers (A) from short fiber pulps which may for example have a length of 0.2 to 1, 5 mm and a length / diameter ratio in the range of 200: 1 to 40: 1.
  • the method according to the invention comprises at least two steps, in particular at least two separate steps. In a step which is also referred to as the first step in the context of the present invention, cellulose fibers are treated with at least one aqueous emulsion of
  • (B) at least one ethylene copolymer, in the context of the present application also briefly called ethylene copolymer (B), having a molecular weight M n to a maximum of 20,000 g / mol, preferably from 1,000 to 15,000 g / mol, which contains einpolyme- rcard as comonomers
  • cyclic or linear organic groups are suitable which comprise 1 to 20 C atoms and optionally at least one heteroatom. sen. Heteroatoms are sulfur and in particular nitrogen and oxygen.
  • ethylene copolymer (B) has a kinematic viscosity v in the melting range of 60 to 150,000mm 2 / s, preferably 300 to 90,000 mm 2 / s, measured at 120 0 C according to DIN 51,562th
  • the density of ethylene copolymer (B) is in the range of 0.85 to 0.99 g / cm 3 , preferably to 0.97 g / cm 3 , determined according to DIN 53479.
  • comonomer (b) is a compound of general formula I or Ia
  • R 1 and R 2 are the same or different; R 1 is selected from hydrogen and
  • Ci-Cio-alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl; particularly preferably C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, in particular methyl;
  • R 3 are different or preferably identical and selected from hydrogen and branched and preferably unbranched Ci-Cio-alkyl, for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert.
  • C 3 -C 12 -cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preferred are cyclopentyl, cyclohexyl and cycloheptyl.
  • two radicals R 3 may be linked to one another to form a 3 to 10-membered, preferably 5 to 7-membered ring optionally substituted by C 1 -C 4 -alkyl radicals,
  • an N (R 3 ) 2 group can be selected from
  • radicals R 3 are different, one of the radicals R 3 may preferably be hydrogen.
  • X is selected from sulfur, NR 4 and especially oxygen.
  • R 4 is selected from hydrogen and unbranched and branched C 1 -C 10 -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n- Nonyl, n-decyl; particularly preferably C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-but
  • C 1 -C 10 -alkylene such as -CH 2 -, -CH (CH 3 ) -, - (CH 2 J 2 -, -CH 2 -CH (CH 3 ) -, cis- and trans -CH (CH 3 ) -CH (CH 3 ) -, - (CH 2 J 3 -, -CH 2 -CH (C 2 H 5 ) -, - (CH 2 J 4 -, - (CH 2 J 5 -, - (CH 2 J 6 -,
  • Phenylene for example ortho-phenylene, meta-phenylene and most preferably para-phenylene.
  • Y- is an anion of an inorganic or organic acid, for example sulfate or phosphate, preferably a singly negatively charged anion, for example halide, in particular chloride or bromide, furthermore hydrogensulfate, C 1 -C 4 -alkyl, especially methylsulfate, dihydrogenphosphate , Formate, acetate, propionate, stearate, palmitate, citrate, tartrate.
  • an anion Y can serve for the electrical neutralization of more than one equivalent of comonomer (b).
  • R 1 is hydrogen or methyl. Most preferably, R 1 is methyl.
  • R 1 is hydrogen or methyl and R 2 is hydrogen.
  • R 1 is hydrogen or methyl and R 2 is hydrogen, both groups R 3 are the same and are each methyl or ethyl.
  • XA 1 -N (R 3 ) 2 represents
  • XA 1 -N (R 3 ) 2 represents
  • XA 1 is -N (R 3 ) 3 Y "
  • XA 1 is -N (R 3 ) 3 Y "
  • ethylene copolymer (B) contains no further comonomers (c) in copolymerized form.
  • ethylene copolymer (B) contains at least one further copolymerized comonomer selected from
  • Ci-C2o-alkyl esters of ethylenically unsaturated C 3 -Cio-monocarboxylic acids, short-ethylenically unsaturated C 3 -Cio-Carbonklareester called, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, n-decyl (meth) acrylate, 2-propylheptyl (meth) acrylate,
  • Mono- and di-C 1 -C 10 -alkyl esters of ethylenically unsaturated C 4 -C 10 -dicarboxylic acids for example monomethyl and dimethyl esters of maleic acid, monomethyl and diethyl esters, fumaric acid and dimethyl esters, monomethyl fumarates and diethyl esters, itaconic acid mono- and dimethyl esters, Maleic acid mono- and di-n-butyl esters and maleic mono and di-2-ethylhexyl esters,
  • Vinyl esters or allyl esters of C 1 -C 10 -carboxylic acids preferably vinyl esters or allyl esters of acetic acid or propionic acid, particular preference is given to vinyl propionate and very particularly preferably to vinyl acetate.
  • comonomer (b) is in protonated form.
  • ethylene copolymer (B) can be carried out by conventional processes for the copolymerization of ethylene (a), comonomer (b) and optionally other comonomers (c) in stirred high-pressure autoclaves or in high-pressure tubular reactors. Production in stirred high pressure autoclave is preferred. stirred High-pressure autoclaves are known, a description can be found for example in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, keywords: Waxes, Vol. A 28, p 146 ff., Verlag Chemie Weinheim, Basel, Cambridge, New York, Tokyo, 1996. In their case, the ratio length / diameter predominantly behaves at intervals of 5: 1 to 30: 1, preferably 10: 1 to 20: 1.
  • aqueous emulsions of ethylene copolymer (B) is known per se.
  • one proceeds by placing one or more ethylene copolymers (B) in a vessel, such as a flask, autoclave or kettle, and heating the ethylene copolymer (B) and one or more Br ⁇ nsted acids and optionally other substances ,
  • a vessel such as a flask, autoclave or kettle
  • Br ⁇ nsted acids and optionally other substances for example, water, wherein the order of addition of Br ⁇ nsted acid or Br ⁇ nsted acids and optionally other substances is arbitrary.
  • it is desired to prepare the relevant emulsion at a temperature above 100 ° C. it is advantageous to work under elevated pressure and to select the vessel accordingly. Homogenize the resulting emulsion, for example by mechanical or pneumatic stirring or by shaking.
  • heating to a temperature which is at least 10 0 C is particularly advantageous to a temperature which is at least 30 0 C above the melting point of ethylene copolymer (B).
  • ethylene copolymer (B) is present in partially or preferably completely neutralized form. In one embodiment of the present invention, an excess of Br ⁇ nsted acid is employed. If ethylene copolymer (B) is a compound of general formula I a, it is possible to dispense with the addition of Br ⁇ nsted acid.
  • the aqueous emulsion used in the first step has a solids content in the range of 1 to 40 wt .-%, preferably 10 to 30 wt .-%, particularly preferably 15 to 25 wt .-%.
  • the treatment of cellulose fibers (A) with aqueous emulsion of ethylene copolymer (B) can be carried out at temperatures in the range of 10 to 70 ° C, preferably 20 to 60 ° C.
  • one or more adjuvants may be added, for example, water repellents or sizing agents.
  • no adjuvants are added to the aqueous emulsion of ethylene copolymer (B).
  • the treatment of cellulose fibers (A) with aqueous emulsion of ethylene copolymer (B) can be carried out with homogenization, for example by or with the aid of static mixers or by pumping.
  • In one embodiment of the present invention is homogenized with relatively low energy input, for example, 0.2 to 5.0 kWh / t.
  • the pH in the first step of the process according to the invention is in the range from 4 to 10, preferably 6 to 9.
  • the first step of the process according to the invention is carried out under atmospheric pressure.
  • the first step of the process according to the invention can be carried out in a stirred tank.
  • the cellulose fibers treated according to the invention are dried.
  • water is separated at least to a certain extent and possibly waste. Modified cellulose fibers are obtained.
  • the cellulose fibers treated according to the invention can be separated from the water and any wastes by mechanical methods, for example by pressing or filtering.
  • In one embodiment of the present invention can remove water by thermal ULTRASONIC drying, for example at temperatures in the range of 100 to 300 0 C.
  • cellulose fibers treated according to the invention are dried thermally to a residual moisture content in the range from zero to 20% by weight, preferably at least 0.1% by weight, particularly preferably from 5 to 10
  • the residual moisture content is determined, for example, by IR spectroscopy.
  • the drying is carried out by a combination of at least two operations, for example by a combination of a mechanical method followed by thermal drying. To remove water you can use filters or presses, for example.
  • separated water which still contains residues of ethylene copolymer (B) can be recycled and used, for example, to treat a further portion of cellulose fibers (A).
  • modified cellulose fibers ie cellulose fibers, obtained by treating cellulose fibers (A) according to the invention with aqueous emulsion of ethylene copolymer (B) are mixed with (C) at least one thermoplastic
  • Thermoplastics (C) are understood to mean any thermoplastically deformable polymers which may be new or recycled from old thermoplastic polymers. Preference is given to choosing thermoplastic (C) from polyolefins, preferably polyethylene, in particular HDPE, polypropylene, in particular isotactic polypropylene, and polyvinyl chloride (PVC), for example flexible PVC and in particular rigid PVC, furthermore polyvinyl acetate or mixtures of polyethylene and polypropylene.
  • polyethylene in particular HDPE
  • polypropylene in particular isotactic polypropylene
  • PVC polyvinyl chloride
  • thermoplastic (C) from polyethylene, polypropylene, polyvinyl chloride, polystyrene and polyester.
  • Polyethylene and polypropylene also each include copolymers of ethylene or propylene with one or more alpha-olefin or styrene.
  • polyethylene also includes copolymers which, in addition to ethylene as the main monomer (at least 50% by weight) comprise one or more monomers in copolymerized form, selected from styrene or ⁇ -olefins such as, for example, propylene, 1-butene , 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, n- ⁇ -C22H44, n- ⁇ -C24H48 and n- ⁇ -C2oH4o.
  • polypropylene also includes copolymers which, in addition to propylene as principal monomer (at least 50% by weight) comprise one or more comonomers in copolymerized form, selected from styrene, ethylene, 1-butene, 1-hexene, 4 -Methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, n- ⁇ -C22H44, n- ⁇ -C24H48 and n- ⁇ -C2oH4o.
  • comonomers in copolymerized form selected from styrene, ethylene, 1-butene, 1-hexene, 4 -Methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, n- ⁇ -C22H44, n- ⁇ -C24H48 and n- ⁇ -C2oH4o.
  • thermoplastic (C) has an average molecular weight M w in the range from 50,000 to 1,000,000 g / mol.
  • additives (D) are compatibilizers (English: coupling agents), for example maleated polyethylenes or polypropylenes, or copolymers of ethylene or propylene and acrylic acid or methacrylic acid.
  • suitable additives (D) are stabilizers, in particular light stabilizers and UV stabilizers, for example sterically hindered amines (HALS), 2,2,6,6-tetramethylmorpholine-N-oxides or 2,2,6,6-tetramethylpiperidine -N-oxides (TEMPO) and other N-oxide derivatives such as NOR.
  • suitable additives (D) are UV absorbers such as, for example, benzophenone or benzotriazole.
  • suitable additives (D) are pigments which can likewise bring about stabilization against UV light, for example titanium dioxide, carbon black, iron oxide, other metal oxides and organic pigments, for example azo and phthalocyanine pigments.
  • suitable additives (D) are biocides, in particular fungicides.
  • suitable additives (D) are acid scavengers, for example alkaline earth metal hydroxides or alkaline earth metal oxides or fatty acid salts of metals, in particular metal stearates, particularly preferably zinc stearate and calcium stearate, and furthermore chalk and hydrotalcites.
  • metal stearates particularly preferably zinc stearate and calcium stearate
  • chalk and hydrotalcites for example alkaline earth metal hydroxides or alkaline earth metal oxides or fatty acid salts of metals, in particular metal stearates, particularly preferably zinc stearate and calcium stearate, and furthermore chalk and hydrotalcites.
  • some fatty acid salts of metals especially zinc stearate and calcium stearate, also act as a lubricant in the processing.
  • additives (D) are antioxidants, such as those based on phenols, such as alkylated phenols, bisphenols, bicyclic phenols or antioxidants based on benzofuranones, organic sulfides and / or diphenylamines.
  • suitable additives (D) are plasticizers. Esters of dicarboxylic acids such as phthalates, organic phosphates, polyesters and polyglycol derivatives.
  • suitable additives (D) are impact modifiers and flame retardants.
  • the mixing is carried out in an extruder, for example in a co-rotating or counter-rotating twin-screw extruder.
  • modified cellulose fibers, thermoplastic (C) and optionally one or more additives (D) are fed to the extruder in a direct extrusion, melted, mixed and processed into the finished composite composite.
  • modified fibers (A), thermoplastic (C) and optionally one or more additives (D) are first processed by mixing into a composite material, for example obtained in granular form, and then processed, for example, to one or more semi-finished products ,
  • the temperature at which the mixture is mixed is chosen, preferably such that it is at least 10.degree. C., preferably at least 20.degree. C. above the melting point of thermoplastic (C).
  • thermoplastic 10 to 40% by weight of thermoplastic (C), based on the respective weight.
  • Another object of the present invention are cellulose fibers treated with at least one emulsion of
  • Modified cellulosic fibers according to the invention are very easy to separate, and the tensile strength of a sheet formed from such fibers is 30 to 80% lower than that of a sheet of untreated fibers.
  • the separability concerns neither the single fiber strength nor the fiber matrix bond.
  • modified cellulosic fibers according to the invention are free of thermoplastic (C), ie the proportion of thermoplastic is in the range of zero to 0.5% by weight, based on the dry weight, of modified cellulose fibers according to the invention.
  • the weight ratio of cellulose fibers (A) to ethylene copolymers (B) is in the range from 1000: 1 to 20: 1, preferably 500: 1 to 50: 1.
  • modified cellulosic fibers according to the invention have a residual moisture content in the range of zero to 20% by weight, preferably 5 to 10% by weight.
  • the residual moisture content is determined, for example, by IR spectroscopy or by storing for several hours in a drying oven.
  • Another object of the present invention is the use of modified cellulose fibers according to the invention for the production of composite materials, preferably of those containing at least one thermoplastic (C).
  • Another object of the present invention is a process for the production of composite materials using modified cellulose fibers according to the invention.
  • Composite materials according to the invention are outstandingly suitable as or for the production of building interior or exterior parts or of profile parts.
  • building interior parts are railings, for example for stairs in the interior, and panels.
  • building exterior parts are roofs, facades, roof structures, window frames, porches, railings for external stairs, decking and cladding, for example for buildings or parts of buildings.
  • profile parts are technical profiles, connecting hinge, moldings for interior applications such as shaped parts with complex geometries, multifunctional profiles or packaging parts and decorative parts, furniture profiles and floor profiles.
  • composite materials according to the invention are suitable for packaging, for example for boxes and boxes.
  • Another object of the present invention is the use of composite materials according to the invention as or for the production of furniture, such as tables, chairs, especially garden furniture and benches such as park benches, for the production of profile parts and for the production of hollow bodies such as hollow sections for decking or windowsills.
  • Another object of the present invention is a method for producing building exterior parts, furniture, profile parts or hollow bodies using at least one composite material according to the invention.
  • Another object of the present invention are interior building parts and building exterior parts, profile parts, furniture and hollow body, produced using at least one composite material according to the invention.
  • Exterior building parts and benches according to the invention exhibit excellent weather resistance, furthermore excellent grip and very good mechanical properties such as impact strength, good bending modulus and low water absorption, which leads to a good weather dependence.
  • the thermal properties are very good.
  • they have a wood-like, aesthetic appearance.
  • reactor is meant the maximum internal temperature of the high-pressure autoclave.
  • DMAEMA N, N-dimethylaminoethyl methacrylate
  • PA propionaldehyde
  • ID isododecane (2,2,4,6,6-pentamethylheptane)
  • PA in ID solution of propionaldehyde in isododecane, total volume of solution.
  • the conversion refers to ethylene and is given in% by weight
  • the term "content" is the proportion of polymerized ethylene or DMAEMA is to be understood in the respective ethylene copolymer ⁇ .
  • Dynamic melt viscosity measured at 120 0 C in a plate / cone viscometer (PP 35 Ti) 1, 0 mm column, and D 10 [1 / s] according to DIN 53018-1
  • the content of ethylene and N, N-dimethylaminoethyl methacrylate in the ethylene copolymers was determined by 1 H-NMR spectroscopy.
  • the density was determined according to DIN 53479.
  • the melting point T me ⁇ t or melting range was determined by DSC (differential scanning calorimetry, Differentialthermo- analysis) determined according to DIN 51,007th
  • Example 3 In a 2 liter autoclave with anchor stirrer, the amount of ethylene copolymer (B) indicated in Table 3 was charged according to Example 1. The mixture was heated with stirring to 130 0 C and then added dropwise within 15 minutes the amount indicated in Table 3 37 wt .-% aqueous acetic acid according to table, feed 1. Thereafter, within 30 minutes, the remaining amount of water was added, feed 2, and stirred for a further 15 minutes at 130 0 C (ambient temperature). Thereafter, the outside temperature was lowered to 100 ° C, stirred for one hour at 100 0 C and then cooled to room temperature within 15 minutes. It was filtered with a Perlon filter (100 microns) and received the relevant aqueous emulsions. Details and properties of the emulsions obtained are summarized in Table 3.
  • 225 g of ethylene copolymer (B.2) according to Example 1 and phosphoric acid and water according to Table 4 were initially charged in a 2 liter autoclave with anchor stirrer. The mixture was heated with stirring to 130 0 C and then the mixture was allowed to stir for 2 hours. Then the emulsion is cooled to room temperature within 15 minutes. It was filtered with a Perlon filter (100 microns) and received the relevant aqueous emulsions.
  • a twin-screw extruder were polyethylene (C.1), a HDPE with a MFR of 31 g / 10 min, measured at 190 0 C and a load of 2.16 kg according to ISO 1 133 and inventive modified cellulose fibers according to Example 3 in a weight ratio 7 : 3 at and 1 wt .-% ethylene-methacrylic acid copolymer (D.1), based on the sum of polyethylene (C.1) and inventive modified cellulose fibers according to Example 3 at 200 0 C extruded together.
  • a composite material VWS.1 according to the invention was obtained, which had threefold stiffness (modulus of elasticity) and twice the tensile strength in comparison to the relevant unreinforced HDPE.

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Abstract

La présente invention a pour objet un procédé de fabrication de matériaux composites, caractérisé en ce qu'au cours d'une étape, des fibres cellulosiques modifiées sont produites, ce qui consiste à traiter des fibres cellulosiques (A) au moyen d'une émulsion aqueuse comprenant (B) au moins un copolymère d'éthylène ayant un poids moléculaire Mn maximum de 20 000 g/mol et contenant comme comonomères constitutifs (a) entre 50 et 95 % en poids d'éthylène, (b) entre 5 et 50 % en poids d'au moins un comonomère qui comporte au moins un groupe amino alkylé ou cycloalkylé qui est relié par un espaceur à un groupe polymérisable, (c) entre 0 et 30 % en poids d'autres comonomères. Le procédé est également caractérisé en ce qu'au cours d'une autre étape des fibres cellulosiques modifiées sont mélangées avec au moins un thermoplastique (C) et éventuellement un ou plusieurs adjuvants (D).
EP10739925A 2009-08-10 2010-08-03 Fibres cellulosiques modifiées, fabrication et utilisation Withdrawn EP2464681A1 (fr)

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PCT/EP2010/061241 WO2011018383A1 (fr) 2009-08-10 2010-08-03 Fibres cellulosiques modifiées, fabrication et utilisation
EP10739925A EP2464681A1 (fr) 2009-08-10 2010-08-03 Fibres cellulosiques modifiées, fabrication et utilisation

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US8721744B2 (en) 2010-07-06 2014-05-13 Basf Se Copolymer with high chemical homogeneity and use thereof for improving the cold flow properties of fuel oils
JP2016532662A (ja) 2013-10-09 2016-10-20 ビーエイエスエフ・ソシエタス・エウロパエアＢａｓｆ Ｓｅ ボディケア組成物

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US4457970A (en) * 1982-06-21 1984-07-03 Ppg Industries, Inc. Glass fiber reinforced thermoplastics
CA1322806C (fr) * 1986-11-11 1993-10-05 Noboru Yamaguchi Dispersion aqueuse de polymere cationique
DE10345798A1 (de) * 2003-09-30 2005-04-14 Basf Ag Aminogruppenhaltige Ethylencopolymerwachse und ihre Verwendung
DE102005047461A1 (de) * 2005-09-30 2007-04-05 Basf Ag Gemische von Ethylencopolymeren und ihre Verwendung
AT503613A1 (de) 2006-04-19 2007-11-15 Mondi Packaging Frantschach Gm Verfahren zur behandlung eines cellulosischen fasermaterials
JP2009537354A (ja) * 2006-05-24 2009-10-29 ビーエーエスエフ ソシエタス・ヨーロピア 電子写真印刷法用のオレフィンポリマーで被覆された基材
WO2007141199A2 (fr) * 2006-06-09 2007-12-13 Basf Se Procédé de protection de surfaces métalliques de la corrosion par des milieux liquides par utilisation de copolymères comprenant de l'éthylène et des groupements amino
CN101616984B (zh) * 2007-02-23 2012-10-03 巴斯夫欧洲公司 复合材料及其制备方法

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