EP2496647A1 - Matériaux lignocellulosiques présentant de bonnes propriétés mécaniques - Google Patents
Matériaux lignocellulosiques présentant de bonnes propriétés mécaniquesInfo
- Publication number
- EP2496647A1 EP2496647A1 EP10774200A EP10774200A EP2496647A1 EP 2496647 A1 EP2496647 A1 EP 2496647A1 EP 10774200 A EP10774200 A EP 10774200A EP 10774200 A EP10774200 A EP 10774200A EP 2496647 A1 EP2496647 A1 EP 2496647A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- particles
- wood
- lignocellulose
- expanded
- lignocellulosic
- 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- Withdrawn
Links
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- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
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- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
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- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
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- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 1
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
- B27N3/02—Manufacture of substantially flat articles, e.g. boards, from particles or fibres from particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
- B27N3/005—Manufacture of substantially flat articles, e.g. boards, from particles or fibres and foam
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31942—Of aldehyde or ketone condensation product
- Y10T428/31949—Next to cellulosic
- Y10T428/31957—Wood
Definitions
- the present invention relates to a process for the preparation of a lignocellulose-containing substance having an average density in the range of more than 600 to 900 kg / m 3 , in which, in each case based on the lignocellulose-containing substance:
- a binder selected from the group consisting of aminoplast resin, phenol-formaldehyde resin, and organic isocyanate having at least two isocyanate groups and optionally
- the present invention relates to a process for producing a multilayered lignocellulosic material, the lignocellulosic material, a multilayered lignocellulosic material and the use of a lignocellulosic material or a multilayer lignocellulosic material, each as defined in the claims.
- Lignocellulosic materials for example wood-based materials, in particular multilayer wood-based materials, are a cost-effective and resource-saving alternative to solid wood and have great significance, in particular in furniture construction
- Laminate flooring and obtained as building materials are usually wood particles of different strengths, eg. As wood chips or wood fibers from different woods. Such wood particles are usually pressed with natural and / or synthetic binders and optionally with the addition of further additives to plate or strand-shaped wood materials.
- Such lignocellulosic materials such as wood materials, have
- Such lignocellulosic materials usually have not yet fully satisfactory transverse tensile strengths or swelling or water absorption and are therefore only for less
- the resulting molding materials have a low density (below 600 kg / m 3 ).
- WO 02/38676 describes a process for the preparation of filled lignocellulose products, in which 5 to 40 wt .-% foamable or already foamed polystyrene having a particle size of less than 1 mm, 60 to 95 wt .-% lignocellulose-containing material and binder mixed and pressed at elevated temperature and pressure to the finished product.
- the polystyrene transforms into a melt and penetrates into the wood fibers (page 4, paragraph 2).
- the product described in the example therefore has a relatively high density of 1.2 g / cm 3 (1200 kg / m 3 ).
- wood-containing substances containing, for example, wood chips or fibers, a binder and a porous porous plastic serving as a filler.
- wood-containing substances are, for example, the wood chips or fibers with binder and
- WO 2008 / 046890A, WO 2008/046891 A and WO 2008/046892 A describe densities of light wood-containing substances of 600 kg / m 3 and less.
- the object of the present invention was lignocellulose-containing, preferably wood-containing, substances and lignocellulosic materials, preferably
- the mechanical strength can be determined by measuring the transverse tensile strength according to EN 319. Furthermore, the swelling value (determinable according to EN 317) of the lignocellulosic materials, preferably wood-based materials, should not be adversely affected.
- the problem was solved by a method for producing a
- lignocellulosic material having an average density in the range of more than 600 to 900 kg / m 3 , in which, in each case based on the lignocellulosic substance:
- a binder selected from the group consisting of aminoplast resin, phenol-formaldehyde resin, and organic isocyanate having at least two isocyanate groups and optionally
- lignocellulose lignocellulose particles or lignocellulose-containing substance are known in the art.
- Lignocellulosic material, lignocellulosic particles or lignocellulosic particles are, for example, straw or wood parts such as wood plies, wood strips, wood chips, wood fibers or wood dust, with wood chips, wood fibers and wood dust being preferred.
- the lignocellulose-containing particles or lignocellulose particles may also be derived from wood fiber-containing plants, such as flax, hemp.
- Thinning wood, industrial lumber and used wood as well as wood fiber plants are important
- Preferred lignocellulose-containing particles are wood particles, particularly preferably wood chips and wood fibers, as used for the production of MDF and HDF boards.
- Highly suitable lignocellulose-containing particles are also flax or hemp particles, particularly preferably flax or hemp fibers, as can be used for the production of MDF and HDF boards.
- the lignocellulosic, preferably wood-containing substance may contain the usual small amounts of water (in a usual small fluctuation range); This water is not included in the weight of the present application.
- the weight specification of the lignocellulose particles, preferably wood particles refers to lignocellulose particles dried in a conventional manner known to the person skilled in the art, preferably wood particles.
- the weight of the binder refers to the
- Aminoplastkomponente in the binder on the solids content of the corresponding component (determined by evaporation of water at 120 ° C, within 2 h after, for example, Günter Zeppenfeld, Dirk Grunwald, adhesives in the wood and furniture industry, 2nd edition, DRW-Verlag , Page 268) and with regard to the isocyanate, in particular the PMDI, to the isocyanate component per se, that is, for example, without a solvent or emulsifier.
- the lignocellulose-containing, preferably wood-containing substances according to the invention have an average density in the range of at least 600 to 900 kg / m 3 , preferably 600 to 850 kg / m 3 , particularly preferably 600 to 800 kg / m 3 .
- the transverse tensile strength of the lignocellulose-containing, preferably wood-containing materials or preferably multi-layer lignocellulose materials according to the invention, more preferably multilayer wood materials, is usually more than 10% higher, preferably more than 20% higher, more preferably more than 30% higher than the transverse tensile strength of an analog
- lignocellulose-containing substance of the same constituents the same density, the same thickness and the same method of preparation, but without component B).
- the determination of the transverse tensile strength is in accordance with EN 319.
- the swelling value of the lignocellulose-containing preferably
- Wood-containing substances or preferably the multilayered lignocellulosic materials according to the invention, more preferably multilayer wood-based materials, is usually more than 10% less, preferably more than 20% less, more preferably more than 30% less than the swelling value of an analogous lignocellulose-containing substance from the same constituents, same density , same thickness and same method of preparation, but without component B).
- the determination of the source values is in accordance with EN 317.
- wood-containing materials or preferably the multilayer lignocellulose materials according to the invention is usually more than 10% less, preferably more than 20% less, more preferably more than 30% less than the water absorption (value) of an analogous lignocellulosic material from the same constituents, the same density, the same thickness and the same method of preparation, but without Component B).
- multilayered lignocellulosic materials preferably multilayered
- Wood-based materials are all materials that are made of wood veneers
- preferably with an average density of the wood veneer of 0.4 to 0.85 g / cm 3 are made, for example, veneer or plywood boards or Laminated Veneer Lumber (LVL).
- multilayered lignocellulosic materials preferably multilayered
- Wood materials are preferably all materials into consideration, the
- Lignocelluloses Georgosakukan preferably wood chips, preferably with an average density of the wood chips from 0.4 to 0.85 g / cm 3 are made, for example, chipboard or OSB boards, and wood fiber materials such as LDF, MDF and HDF boards.
- Particleboard and fiberboard, in particular chipboard, are preferred.
- the average density of the lignocellulose particles is generally 0.4 to 0.85 g / cm 3 , preferably 0.4 to 0.75 g / cm 3 , in particular 0.4 to 0.6 g / cm 3 .
- any wood species comes into question; For example, spruce, beech, pine, larch, linden, poplar, ash, chestnut or fir wood are very suitable; spruce and / or beech wood, in particular spruce wood, are preferred.
- the dimensions of the lignocellulose particles are not critical and, as usual, depend on the lignocellulose material to be produced, preferably wood-based material, for example the abovementioned wood-based materials, such as chipboard, MDF, HDF or OSB.
- Component B) are expanded plastic particles, preferably expanded thermoplastic plastic particles.
- Such expanded plastic particles are usually obtained as follows: Compact plastic particles containing an expansible medium (also called “propellant”) are expanded by the action of heat energy or pressure change (often referred to as “foamed”). Here, the propellant expands, the particles increase in size and cell structures arise. This expansion is generally carried out in conventional frothing devices, often referred to as “prefoamers.” Such prefouchers may be stationary or mobile, and expansion may be single-stage or multi-stage expanded to the desired final size.
- Plastic particles initially expanded to an intermediate size and then expanded in one or more further stages over a corresponding number of intermediate sizes to the desired final size.
- Plastic particles usually no cell structures.
- the resulting expanded plastic particles can be stored temporarily or used further without further intermediate steps for the preparation of the lignocellulose-containing substance.
- Usual measures to ensure production such as feeding the expanded plastic particles in so-called buffer tank, which compensate for example Dosticiansschwankungen the expanded plastic particles, or caching for propellant reduction of the expanded plastic particles and the mixing of component B) with other additives, for example
- Components A), C) or optionally D) are not intermediate steps in the sense of this invention.
- Typical measures for propellant reduction of expanded plastic particles are, for example, prolonged storage, generally 12 hours to several days, of the expanded plastic particles in open vessels or in vessels with, for the propellant, permeable walls. This storage generally takes place at ambient temperature, for example 20 to 30 ° C.
- Propellant reduction is herein with conventional analytical methods (for example, gas chromatography) detectable reduction of the blowing agent concentration in the collective of freshly expanded plastic particles with
- the term "propellant reduction” is intended to include here also the other changes of the expanded plastic particles occurring during prolonged storage of the expanded plastic particles, for example shrinkage or aging
- the expanded plastic particles are continuously used for the production of the lignocellulosic material means that the foaming of the expandable plastic particles and their further use, preferably promotion in the plant for the production of the lignocellulose-containing substance, in a temporally practically uninterrupted
- Plastic particles have one or more buffer container in the main or shunt.
- the plant for producing the lignocellulose-containing substance usually also comprises a mixing device in which the component B) with the other
- the above-described expanding ("foaming") of the expandable plastic particles is carried out at the site of production of the lignocellulose-containing, preferably wood-containing material and the resulting expanded plastic particles, for example, without further measures for propellant reduction, directly reused, for example directly in the apparatus for producing the lignocellulosic material, preferably wood-containing material fed.
- “Locally” herein means nearby, for example within a radius of about 200 meters, or adjacent to the device in which the wood-containing material is produced and optionally further processed.
- Expanding of the expandable plastic particles carried out at the place of manufacture of the lignocellulose-containing, preferably wood-containing substance in a mobile foaming and the resulting expanded plastic particles, for example, without further measures
- Propellant reduction directly reused, for example, fed directly into the apparatus for producing the lignocellulosic material, preferably wood-containing material.
- “Locally” means nearby, for example, within a radius of about 200 Meters, or in the vicinity of the device in which the wood-containing material is produced and optionally further processed.
- Mobile frothing device herein means that the frothing device can be easily assembled and disassembled, or, preferably, is mobile, for example, mounted on a wheeled vehicle (eg truck) or railcar Mobile frothing devices as a truck body are used, for example, by HIRSCH Servo AG, Glanegg 58, A-9555 Glanegg Suitable polymers which are based on the expandable or expanded plastic particles are all polymers, preferably thermoplastic polymers, which can be foamed, which are known to the person skilled in the art.
- polymers for example, polyketones, polysulfones, polyoxymethylene, PVC (hard and soft), polycarbonates, polyisocyanurates,
- Polycarbodiimides polyacrylimides and polymethacrylimides, polyamides, polyurethanes, aminoplast resins and phenolic resins, styrene homopolymers (hereinafter also referred to as "polystyrene” or “styrene polymer”), styrene copolymers, C 2 -C 10 -olefin homopolymers, C 2 -C 10 -olefin copolymers and polyesters.
- 1-alkenes for example ethylene, propylene, 1-butene, 1-hexene, 1-octene.
- the expanded plastic particles of component B) have a bulk density of from 10 to 100 kg / m 3 , preferably from 45 to 100 kg / m 3 , particularly preferably from 45 to 80 kg / m 3 , in particular from 50 to 70 kg / m 3 .
- the bulk density is usually determined by weighing a volume filled with the bulk material.
- Expanded plastic particles B) are generally used in the form of spheres or beads having an average diameter of advantageously 0.25 to 10 mm, preferably 0.4 to 8.5 mm, in particular 0.4 to 7 mm.
- Expanded plastic particle balls B) advantageously have a small surface area per volume, for example in the form of a spherical or elliptical particle.
- the expanded plastic particle balls B) are advantageously closed-cell.
- the off-set to DIN-ISO 4590 is usually less than 30%.
- component B) consists of different types of polymers, ie polymer types which are based on different monomers (for example polystyrene and polyethylene or polystyrene and homopolypropylene or polyethylene and homo-polypropylene), these may be present in different weight ratios, which, however, according to the current state of knowledge, are not critical.
- the polymers preferably the thermoplastics which underlie the expandable or expanded plastic particles B), may contain additives, for example UV stabilizers, antioxidants, coating compositions,
- Water repellents nucleating agents, plasticizers, flame retardants, soluble and insoluble inorganic and / or organic dyes, pigments, and athermane particles such as carbon black, graphite or aluminum powder, are added together or spatially separated as additives.
- Hydrocarbons such as propane, n-butane, isobutane, n-pentane, isopentane, neopentane cyclo-pentane and / or hexane and its isomers, alcohols, ketones, esters, ethers or halogenated hydrocarbons.
- the content of blowing agent in the expandable plastic particles is in the range of 0.01 to 7 wt .-%, preferably 0.01 to 4 wt .-%, particularly preferably 0.1 to 4 wt .-%, in each case based on the blowing agent-containing expandable plastic particles.
- styrene homopolymer also referred to herein simply as “polystyrene”
- polystyrene styrene copolymer
- Such polystyrene and / or styrene copolymer can be prepared by all known in the art polymerization process, see, for. Ullmann's Encyclopedia, Sixth Edition, 2000 Electronic Release or Plastics Handbook 1996, Volume 4 "Polystyrene", pages 567 to 598.
- the production of the expandable polystyrene and / or styrene copolymer is generally carried out in a conventional manner by suspension polymerization or by extrusion.
- blowing agent for example via an extruder in the polymer, conveyed through a nozzle plate and granulated under pressure to particles or strands.
- Styrene copolymer can be used all blowing agents known to those skilled in the art and already mentioned above, for example aliphatic C3 to C10 hydrocarbons, such as propane, n-butane, isobutane, n-pentane, isopentane, neopentane cyclo-pentane and / or hexane and its isomers, Alcohols, ketones, esters, ethers or halogenated hydrocarbons.
- aliphatic C3 to C10 hydrocarbons such as propane, n-butane, isobutane, n-pentane, isopentane, neopentane cyclo-pentane and / or hexane and its isomers, Alcohols, ketones, esters, ethers or halogenated hydrocarbons.
- the propellant is selected from the group consisting of n-pentane, isopentane, neopentane and cyclopentane. Particularly preferred is
- the content of blowing agent in the expandable polystyrene or styrene copolymer is in the range of 0.01 to 7 wt .-%, preferably 0.01 to 4 wt .-%, preferably 0.1 to 4 wt .-%, particularly preferably 0.5 to 3.5 wt .-%, each based on the propellant-containing expandable polystyrene or styrene copolymer.
- the content of C3 to Cio hydrocarbons as blowing agent in the expandable polystyrene or styrene copolymer is in the range of 0.01 to 7 wt .-%, preferably 0.01 to 4 wt .-%, preferably 0.1 to 4 wt .-% , Particularly preferably 0.5 to 3.5 wt .-%, each based on the propellant-containing expandable polystyrene or styrene copolymer.
- blowing agent selected from the group consisting of n-pentane, isopentane, neopentane and cyclopentane, in expandable polystyrene or
- Styrene copolymer is in the range from 0.01 to 7 wt .-%, preferably 0.01 to 4 wt .-%, preferably 0.1 to 4 wt .-%, particularly preferably 0.5 to 3.5 wt .-%, in each case, based on the propellant-containing expandable polystyrene or styrene copolymer.
- the content of blowing agent selected from the group consisting of n-pentane, isopentane, neopentane and cyclopentane in the expandable polystyrene is in the range of 0.01 to 7 wt .-%, preferably 0.01 to 4 wt .-%, preferably 0 , 1 to 4 wt .-%, particularly preferably 0.5 to 3.5 wt .-%, each, based on the propellant-containing expandable polystyrene.
- the preferred or particularly preferred expandable styrene polymers or expandable styrene copolymers described above have a relatively low content of blowing agent.
- Such polymers are also known as
- a "low-blowing agent” is a well-suited process for the production of Low blowing expandable polystyrene or expandable styrene copolymer is described in US 5,112,875, which is incorporated herein by reference.
- styrene polymers or styrene copolymers additives for example, UV stabilizers, antioxidants, coating compositions,
- Water repellents nucleating agents, plasticizers, flame retardants, soluble and insoluble inorganic and / or organic dyes, pigments, and athermane particles such as carbon black, graphite or aluminum powder, are added together or spatially separated as additives.
- styrene copolymers can also be used. These styrene copolymers advantageously have at least 50% by weight, preferably at least 80% by weight, of copolymerized styrene.
- comonomers come z. B. oc-methyl-styrene, ring-halogenated styrenes, acrylonitrile, esters of acrylic or methacrylic acid of alcohols having 1 to 8 carbon atoms, N-vinylcarbazole, maleic acid (anhydride),
- the polystyrene and / or Styrolcopolymensat contain a small amount of a chain branched polymerized, d. H. a compound having more than one, preferably two, double bonds, such as divinylbenzene, butadiene and / or butanediol diacrylate.
- the branching agent is generally used in amounts of from 0.0005 to 0.5 mol%, based on styrene.
- Mixtures of different styrene (co) polymers can also be used.
- styrene homopolymers or styrene copolymers are glass-clear polystyrene (GPPS), impact polystyrene (Hl PS), anionically polymerized polystyrene or impact polystyrene (A-IPS), styrene- ⁇ -methylstyrene copolymers, acrylonitrile-butadiene-styrene polymers (ABS), styrene-acrylonitrile (SAN), acrylonitrile-styrene-acrylic esters (ASA), methyl acrylate-butadiene-styrene (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene (MABS) polymers or mixtures thereof or with polyphenylene ether (PPE).
- GPPS glass-clear polystyrene
- Hl PS impact polystyrene
- A-IPS anionically polymerized polysty
- styrene homopolymer having a molecular weight in the range from 70,000 to 400,000 g / mol, particularly preferably 190,000 to 400,000 g / mol, very particularly preferably 210,000 to 400,000 g / mol.
- the expandable styrene homopolymers or expandable styrene copolymers are expanded by heating to temperatures above their softening point, for example with hot air or preferably with steam and / or pressure change ( often also referred to as "foamed"), as described, for example, in Kunststoff Handbuch 1996, Volume 4 "Polystyrene", Hanser 1996, pages 640 to 673 or US 5,112,875
- Styrene copolymer is usually in a conventional manner
- the propellant expands, the polymer particles increase in size and cell structures are formed.
- Such expansion is generally carried out in conventional frothing devices, often referred to as "pre-expanders.” Such prefouchers may be fixed in place or mobile.
- the expansion may be carried out in one or more stages Typically, in the one-step process, the expandable polystyrene particles or expandable ones As a rule, in the multistage process, the polystyrene particles or expandable styrene copolymer particles are first expanded to an intermediate size and then, in one or more further stages, over a corresponding number of additional styrene copolymer particles
- the expandable polystyrene particles styrene homopolymer particles or expandable styrene copolymer particles, unlike the expanded polystyrene particles or expanded styrene copolymer particles, generally do not contain cell structures.
- Styrene copolymer preferably styrene homopolymer
- Styrene copolymer is in the range of 0 to 5.5 wt .-%, preferably 0 to 3 wt .-%, preferably 0 to 2.5 wt .-%, particularly preferably 0 to 2 wt .-%, respectively based on the expanded polystyrene or expanded styrene copolymer.
- 0 wt .-% means herein that no propellant can be detected by the usual detection methods.
- These expanded polystyrene particles or expanded Styrolcopolymerteilchen can with or without further measures for propellant reduction
- Styrolcopolymerteilchen be used preferably without further intermediate steps for the preparation of the lignocellulose-containing substance.
- Styrolcopolymerteilchen with other additives for example, components A), C) or optionally D) are not intermediate steps in the context of this invention.
- Propellant concentration in the collective of the freshly expanded polystyrene particles or expanded styrene copolymer particles with time
- Polystyrene particles or expanded styrene copolymer particles for example
- the expanded polystyrene particles or expanded styrene copolymer particles are used continuously to prepare the
- the plant for producing the lignocellulose-containing substance usually also comprises a mixing device in which the component B) is mixed with the other components.
- “Locally” herein means nearby, for example within a radius of about 200 meters, or adjacent to the device in which the wood-containing material is produced and optionally further processed.
- Expanding the expandable polystyrene particles or
- “Locally” herein means nearby, for example within a radius of about 200 meters, or adjacent to the device in which the wood-containing material is produced and optionally further processed.
- Mobile frothing device herein means that the frothing device can be easily assembled and disassembled, or, preferably, is mobile, for example, mounted on a wheeled vehicle (eg, truck) or railcar.
- Mobile foaming devices as a truck body are described for example by the company HIRSCH Servo AG, Glanegg 58, A-9555 Glanegg.
- the expanded polystyrene or expanded styrene copolymer advantageously has a bulk density of from 10 to 100 kg / m 3 , preferably from 45 to 100 kg / m 3 , particularly preferably from 45 to 80 kg / m 3 , in particular from 50 to 70 kg / m 3 .
- the expanded polystyrene or expanded styrene copolymer is advantageously used in the form of spheres or beads having an average diameter in the range of 0.25 to 10 mm, preferably in the range of 1 to 8.5 mm, in particular in the range of 1, 2 to 7 mm ..
- the expanded polystyrene or expanded styrene copolymer spheres advantageously have a small surface area per volume, for example in the form of a spherical or elliptical particle.
- the expanded polystyrene or expanded styrene copolymer spheres are advantageously closed-cell.
- the off-set to DIN-ISO 4590 is usually less than 30%.
- the expandable polystyrene or expandable styrene copolymer or the expanded polystyrene or expanded styrene copolymer has an antistatic coating.
- antistatic agents the usual and common in the art substances can be used. Examples are N, N-bis (2-hydroxyethyl) -Ci 2 -C 18 -alkylamines, fatty acid diethanolamides, choline ester chlorides of fatty acids, C 12 -C 20 -alkyl sulfonates, ammonium salts. Suitable ammonium salts contain on nitrogen in addition to alkyl groups 1 to 3 hydroxyl-containing organic radicals.
- Suitable quaternary ammonium salts are, for example, those having on the nitrogen cation 1 to 3, preferably 2, identical or different alkyl radicals having 1 to 12, preferably 1 to 10 carbon atoms, and 1 to 3, preferably 2, the same or
- the hydroxyalkyl and hydroxyalkyl-polyoxyalkylene radicals are those which are formed by oxyalkylation of a nitrogen-bonded hydrogen atom and are derived from 1 to 10 oxyalkylene radicals, in particular oxyethylene and oxypropylene radicals.
- Particular preference is given to using as antistatic agent a quaternary ammonium salt or an alkali metal salt, in particular the sodium salt of a C 12 -C 20 alkanesulfonate or mixtures thereof.
- the antistatic agents can generally be added both as a pure substance and in the form of an aqueous solution.
- the antistatic agent can be used in the process of producing polystyrene or
- Styrene copolymer be added analogously to the usual additives or applied after the preparation of the polystyrene particles as a coating.
- the antistatic agent is advantageously used in an amount of 0.05 to 6 wt .-%, preferably 0.1 to 4 wt .-%, based on the polystyrene or styrene copolymer.
- the expanded plastic particles B) are usually after pressing to the lignocellulosic material, preferably wood material, preferably
- multilayered lignocellulosic material more preferably multilayered
- Wood material in a practically unmelted state before.
- the plastic particles B) have generally not penetrated into the lignocellulosic particles or have impregnated them, but are distributed between the lignocellulosic particles.
- the plastic particles B) can be separated from the lignocellulose by physical processes, for example after comminution of the lignocellulose material.
- the total amount of expanded plastic particles B), based on the lignocellulose-containing, preferably wood-containing material, is in the range of 1 to 25 wt .-%, preferably 3 to 20 wt .-%, particularly preferably 5 to 15 wt .-%.
- the total amount of the expanded plastic particles B) with polystyrene and / or styrene copolymer as sole plastic particle component, based on the lignocellulose-containing, preferably wood-containing material, is in the range of 1 to 25 wt .-%, preferably 3 to 20 wt .-%, especially preferably 5 to 15 wt .-%.
- the Rossin-Rammler-Sperling-Bennet function is described for example in DIN 66145.
- sieve analyzes are first carried out to determine the particle size distribution of the expanded plastic particles B) and
- Lignocellulose particles preferably wood particles A
- DIN 66165 Lignocellulose particles, preferably wood particles A
- Highly suitable lignocellulose particles preferably wood particles A
- lignocellulose-containing, preferably wood-containing materials or multilayer lignocellulosic materials, preferably multilayer wood-based materials are obtained if, for the d'values according to Rosin-Rammler-Sperling-Bennet
- Lignocellulose particles, preferably wood particles A) and the particles of the expanded plastic particles B) the following relationship applies: d 'of the particles A) ⁇ 2.5 ⁇ d' of the particles B), preferably d 'of the particles A) ⁇ 2.0 ⁇ d' the particle B), particularly preferably d 'of the particles A) ⁇ 1, 5 * d' of the particles B), very particularly preferably d 'of the particles A) ⁇ d' of the particles B).
- the binder C) is selected from the group consisting of aminoplast resin, phenol-formaldehyde resin and organic isocyanate having at least two
- the binder C) contains the substances known to the person skilled in the art for aminoplasts or phenolformaldehyde resins and commonly referred to as hardeners, such as ammonium sulfate or ammonium nitrate or inorganic or organic acids, for example sulfuric acid, formic acid or acid regenerating substances, such as aluminum chloride, aluminum sulfate , in each case in the usual, small amounts, for example in the range of 0.1 wt .-% to 3 wt .-%, based on the total amount of aminoplast resin in the binder C).
- hardeners such as ammonium sulfate or ammonium nitrate or inorganic or organic acids, for example sulfuric acid, formic acid or acid regenerating substances, such as aluminum chloride, aluminum sulfate , in each case in the usual, small amounts, for example in the range of 0.1 wt .-% to 3 wt .-%, based on the total amount of aminoplast resin
- Phenol formaldehyde resins also called PF resins are known to the person skilled in the art, see for example Kunststoff-Handbuch, 2nd edition, Hanser 1988, Volume 10
- aminoplast resin polycondensation of compounds with at least one, optionally partially substituted with organic radicals, carbamide group (the carbamide group is also called carboxamide) and an aldehyde, preferably formaldehyde, understood.
- aminoplast resins As a suitable aminoplast resin, all of the specialist, preferably known for the production of wood materials, aminoplast resins can be used. Such resins and their preparation are described, for example, in Ullmann's Enzyklopadie der ischen Chemie, 4th, revised and expanded edition, Verlag Chemie, 1973, pages 403 to 424 "Aminoplasts” and Ullmann's Encyclopedia of Industrial Chemistry, Vol. A2, VCH Verlagsgesellschaft, 1985, Pages 1 15 to 141 "Amino Resins” as well as in M. Dunky, P. Niemz, wood materials and glues, Springer 2002, pages 251 to 259 (UF resins) and pages 303 to 313 (MUF and UF with a small amount of melamine) ,
- Preferred aminoplast resins are polycondensation products of compounds having at least one, also partially substituted by organic radicals,
- aminoplast resins are urea-formaldehyde resins (UF resins), melamine-formaldehyde resins (MF resins) or melamine-containing urea-formaldehyde resins (MUF resins).
- UF resins urea-formaldehyde resins
- MF resins melamine-formaldehyde resins
- UMF resins melamine-containing urea-formaldehyde resins
- urea-formaldehyde resins for example Kaurit ® glue types from BASF Aktiengesellschaft.
- amino resins are polycondensation products of compounds having at least one, and partly with organic radicals
- organic radicals amino group in Range of 0.3 to 1, 0, preferably 0.3 to 0.60, particularly preferably 0.3 to 0.45, most preferably 0.30 to 0.40.
- very preferred aminoplast resins are polycondensation products of compounds having at least one amino group -NH 2 and formaldehyde, wherein the molar ratio of formaldehyde: -Nh group in the range of 0.3 to 1, preferably 0.3 to 0.60, particularly preferably 0 , 3 to 0.45, most preferably 0.30 to 0.40.
- aminoplast resins are urea-formaldehyde resins (UF resins), melamine-formaldehyde resins (MF resins) or melamine-containing urea-formaldehyde resins (MUF resins), wherein the molar ratio of formaldehyde: -IMH2 group in the range of 0.3 to 1, 0, preferably 0.3 to 0.60, particularly preferably 0.3 to 0.45, very particularly preferably 0.30 to 0.40.
- UF resins urea-formaldehyde resins
- MF resins melamine-formaldehyde resins
- MMF resins melamine-containing urea-formaldehyde resins
- very preferred aminoplast resins are urea-formaldehyde resins (UF resins), wherein the molar ratio of formaldehyde: -NH2 group in the range of 0.3 to 1, preferably 0.3 to 0.60, particularly preferably 0.3 to 0.45, most preferably 0.30 to 0.40.
- UF resins urea-formaldehyde resins
- the said aminoplast resins are usually used in liquid form, usually suspended in a liquid suspending agent, preferably in aqueous suspension, but may also be used as a solid.
- the solids content of the aminoplast resin suspensions, preferably aqueous suspension is usually from 25 to 90% by weight, preferably from 50 to 70% by weight.
- the solids content of the aminoplast resin in aqueous suspension can be determined according to Günter Zeppenfeld, Dirk Grunwald, adhesives in the wood and furniture industry, 2nd edition, DRW-Verlag, page 268.
- To determine the solids content of aminoplast glues 1 g of aminoplast glue is weighed exactly into a weighing dish, finely distributed on the bottom and dried for 2 hours at 120 ° C. in a drying oven. After tempering to room temperature in a desiccator, the residue is weighed and calculated as a percentage of the initial weight.
- aminoplast resins are prepared by known processes (see above Ullmann-Literatur “Aminoplasts” and “Amino Resins”, as well as literature Dunky et al.) By reacting the carbamido-containing compounds, preferably urea and / or melamine, with the aldehydes, preferably
- Formaldehyde in the desired molar ratios Carbamidoli: aldehyde, preferably in water as a solvent.
- the setting of the desired molar ratio of aldehyde, preferably formaldehyde: optionally partially substituted with organic radicals amino group can also happen by addition of -Nh group-carrying monomers to formaldehyde-rich finished, preferably commercial, Aminoplastharzen.
- Nh group-bearing monomers are preferably urea, melamine, more preferably urea.
- the further component of the binder C) may be an organic isocyanate having at least two isocyanate groups.
- organic isocyanate all known to those skilled in the art, preferably the known for the production of wood materials or polyurethanes, organic isocyanates can be used.
- organic isocyanates and their preparation and use are described, for example, in Becker / Braun, Kunststoff Handbuch, 3rd revised edition, Volume 7 "Polyurethane", Hanser 1993, pages 17 to 21, pages 76 to 88 and pages 665 to 671.
- Preferred organic isocyanates are oligomeric isocyanates of 2 to 10,
- a particularly preferred organic isocyanate is the oligomeric organic isocyanate PMDI ("polymeric methylene diphenylene diisocyanate") obtainable by condensation of formaldehyde with aniline and phosgenation of the in the
- the resin components of the binder C) can be used alone, for example, aminoplast resin as the sole resin component of the binder C) or organic isocyanate as the sole resin component of the binder C) or PF resin as the sole component of the binder C). However, the resin components of the binder C) can also be used as a combination of two or more resin components of the binder C).
- the total amount of the binder C), based on the wood-containing material, is in the range of 3 to 50 wt .-%, preferably 5 to 15 wt .-%, particularly preferably 7 to 10 wt .-%.
- Solid preferably of the urea-formaldehyde resin and / or melamine-urea-formaldehyde resin and / or melamine-formaldehyde resin, more preferably urea-formaldehyde resin, in the binder C), based on the lignocellulose-containing, preferably wood-containing material in the range of 1 to 45 wt. -%, preferably 4 to 14 wt .-%, particularly preferably 6 to 9 wt .-%.
- the total amount of the organic isocyanate preferably of the oligomeric isocyanate with 2 to 10, preferably 2 to 8 monomer units and an average of at least one isocyanate group per monomer unit, more preferably PMDI, in the binder C), based on the lignocellulose-containing, preferably wood-containing material in the range from 0 to 5 wt .-%, preferably 0.1 to 3.5 wt .-%, particularly preferably 0.5 to 1, 5 wt .-%.
- the proportions of the amino resin to the organic isocyanate result from the above-described ratios of the binder aminoplast resin to lignocellulose-containing, preferably wood-containing material or the binder organic isocyanate to lignocellulose, preferably
- Preferred embodiments of the wood-containing substance contain 55 to 92.5 wt .-%, preferably 60 to 90 wt .-%, in particular 70 to 88 wt .-%, based on the wood-containing material, wood particles, wherein the wood particles have an average density of 0 , 4 to 0.85 g / cm 3 , preferably 0.4 to 0.75 g / cm 3 , in particular 0.4 to 0.6 g / cm 3 , 1 to 25 wt .-%, preferably 3 to 20 Wt .-%, in particular 5 to 15 wt .-% based on the wood-containing material, polystyrene and / or styrene copolymer as component B) having a bulk density of 10 to 100 kg / m 3 , preferably 20 to 80 kg / m 3 , in particular 30 to 60 kg / m 3 and 3 to 40 wt .-%, preferably 5 to 25 wt .-%, in particular
- wood-containing material in the range of more than 600 to 900 kg / m 3 , preferably in the range of more than 600 to 850 kg / m 3 , is located.
- lignocellulose-containing, preferably wood-containing material or multilayer lignocellulosic material according to the invention preferably multilayer wood material further commercially available additives known to those skilled in the art as component D), for example water repellents, such as paraffin emulsions, fungicides, formaldehyde scavengers, for example urea or polyamines , and flame retardants.
- the present invention further relates to a process for producing a multi-layered lignocellulosic material containing at least three layers, wherein either only the middle layer or at least a portion of the middle
- the average density of the multilayer, preferably of the three-layer, lignocellulose material according to the invention preferably
- Wood material is in the range of more than 600 kg / m 3 to 900 kg / m 3 , preferably in the range of more than 600 kg / m 3 to 850 kg / m 3 , particularly preferably in the range of more than 600 kg / m 3 800 kg / m 3 .
- Preferred parameter ranges and preferred embodiments with regard to the average density of the lignocellulose-containing, preferably wood-containing substance and with regard to the components and their preparation processes A), B), C) and D) and the combination of the features correspond to those described above.
- the expanded polystyrene particles or expanded styrene copolymer particles are used continuously to prepare the
- promotion in the plant for the production of the lignocellulosic material and / or multilayer lignocellulose material proceed in a temporally practical uninterrupted process chain.
- Lignocellulose material the expandable plastic particles, as described in more detail above, foamed at the site of manufacture of the lignocellulose-containing material to expandable plastic particles.
- the expandable plastic particles are as above described in more detail foamed at the site of manufacture of the lignocellulosic material in a mobile foaming to expanded plastic particles.
- Middle layers in the sense of the invention are all layers that are not the outer layers.
- At least one of the outer layers contains
- top layer (s) plastic particles B
- top layer (s) plastic particles B
- at least one of the outer layers contains no expanded plastic particles B).
- the outer layers (usually called “top layer (s)" contain no expanded plastic particles B).
- the multilayer lignocellulose material according to the invention preferably multilayer wood material, contains three lignocellulosic layers,
- the binder used for the outer layers is usually an aminoplast resin, for example urea-formaldehyde resin (UF), melamine-formaldehyde resin (MF), melamine-urea-formaldehyde resin (MUF) or the invention
- aminoplast resin for example urea-formaldehyde resin (UF), melamine-formaldehyde resin (MF), melamine-urea-formaldehyde resin (MUF) or the invention
- the binder used for the outer layers is an aminoplast resin, more preferably a urea-formaldehyde resin, most preferably an aminoplast resin wherein the molar formaldehyde: -NH 2 - group ratio is in the range of 0.3 to 1.0.
- the thickness of the multilayered lignocellulosic material according to the invention preferably multilayer wood material varies with the field of application and is generally in the range of 0.5 to 100 mm; preferably in the range of 10 to 40 mm, in particular 15 to 20 mm.
- multilayer wood material is described below.
- the chips After cutting the wood, the chips are dried. Thereafter, if necessary, coarse and fines are removed. The remaining chips are going through Seven or views sorted in the air stream. The coarser material is used for the
- Middle layer the finer used for the cover layers.
- Middle layer and outer layer chips are separated from each other respectively with the components B) (only middle layer (s) or middle layer (s) and at least one outer layer), C) (same or different for middle layer (s) and
- Top layer (s)) and optionally D) (middle layer and / or outer layers) glued, or mixed and then scattered.
- Component B) is obtained by expanding the expandable plastic particles and mixing them directly or after interim storage and preferably continuously with the other components to form the middle layer.
- the cover layer material is scattered on the forming belt, then the middle layer material - containing the components B), C) and optionally D) - and finally once more cover layer material.
- the three-layered so produced is scattered on the forming belt, then the middle layer material - containing the components B), C) and optionally D) - and finally once more cover layer material.
- Chip cake is cold pre-compressed (usually at room temperature) and then hot pressed.
- the pressing can be carried out by all methods known to the person skilled in the art.
- the wood particle cake is pressed at a press temperature of 150 ° C to 230 ° C to the desired thickness.
- the pressing time is normally 3 to 15 seconds per mm plate thickness. This gives a three-layer chipboard. Examples
- Neopor ® 2400 (neopor ® is a commercial product and the brand of BASF SE) was treated with steam in a continuous prefoamer.
- the bulk density of 50 kg / m 3 of the prefoamed polystyrene beads was determined by varying the
- Vapor pressure and the steaming time set.
- the gluing and pressing of the wood shavings are analogous to conventional processes for the production of chipboard.
- Coarse spruce chips, optionally expanded polystyrene (prepared according to A) above) were mixed in a mixer with the middle layer size liquor (according to Table 1 above) so that the amount of glue (as a solid) was 8.5% by weight, based on atro wood plus expanded polystyrene, amounted to.
- the amount of expanded polystyrene is based on the total amount of dry wood plus expanded polystyrene and is shown in Table 2.
- the material for the production of a three-layer chipboard was spread in a 30 x 30 cm mold. First, the cover layer material, then the
- Overcoat material Middle Layer Material: Overcoat material was 17: 66: 17 in all runs.
- the cover layer material used was the mixture described above under B2.2).
- the middle layer material used was the mixture described above under B2.1).
- precompression was carried out at room temperature, ie "cold”, and then pressed in a hot press (pressing temperature 210 ° C., pressing time 210 s) .
- the nominal thickness of the plate was 16 mm in each case C) Investigation of the wood-containing substance
- the density was determined 24 hours after preparation according to DIN EN 1058.
- the transverse tensile strength was determined in accordance with DIN EN 319. C 3) Swelling values and water absorption
- the quantities always refer to the dry matter.
- the dry wood or the sum of the dry wood and the filler is set to 100 parts.
- the wt .-% the sum of all dry constituents of the wood-containing material is equal to 100%.
- MS Middle layer
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Forests & Forestry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dry Formation Of Fiberboard And The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
La présente invention a pour objet un procédé de fabrication d'un matériau contenant de la lignocellulose et présentant une densité moyenne comprise dans la plage allant de plus de 600 à 900 kg/m3. Selon l'invention, respectivement rapporté au matériau contenant de la lignocellulose : A) de 30 à 95 % en poids de particules de lignocellulose ; B) de 1 à 25 % en poids de particules de plastique expansées possédant une densité apparente comprise dans la plage allant de 10 à 100 kg/m3 ; C) de 3 à 50 % en poids d'un liant, choisi dans le groupe comprenant une résine aminoplaste, une résine phénol formaldéhyde et un isocyanate organique contenant au moins deux groupes isocyanate et le cas échéant D) des additifs, sont mélangés et ensuite comprimés à une température augmentée et à une pression augmentée.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US25861409P | 2009-11-06 | 2009-11-06 | |
| PCT/EP2010/066586 WO2011054790A1 (fr) | 2009-11-06 | 2010-11-02 | Matériaux lignocellulosiques présentant de bonnes propriétés mécaniques |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP2496647A1 true EP2496647A1 (fr) | 2012-09-12 |
Family
ID=43500425
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP10774200A Withdrawn EP2496647A1 (fr) | 2009-11-06 | 2010-11-02 | Matériaux lignocellulosiques présentant de bonnes propriétés mécaniques |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20120219815A1 (fr) |
| EP (1) | EP2496647A1 (fr) |
| CA (1) | CA2779362A1 (fr) |
| WO (1) | WO2011054790A1 (fr) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9005472B2 (en) | 2010-02-24 | 2015-04-14 | Basf Se | Aqueous polishing agent and graft copolymers and their use in a process for polishing patterned and unstructured metal surfaces |
| JP6173343B2 (ja) * | 2011-12-23 | 2017-08-02 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | 不均一にコア中に分布して存在する発泡プラスチック粒子を有するリグノセルロース材料 |
| US9499980B2 (en) | 2013-09-16 | 2016-11-22 | National Gypsum Properties, Llc | Lightweight cementitious panel possessing high durability background |
| US20150076726A1 (en) * | 2013-09-16 | 2015-03-19 | National Gypsum Company | Process for expanding small diameter polystyrene beads for use in cementitious board |
| ES2727141T3 (es) * | 2014-12-09 | 2019-10-14 | Basf Se | Procedimiento para producir materiales lignocelulósicos multicapa con un núcleo y al menos una capa de revestimiento superior e inferior y características especiales del núcleo |
| EP3405476B1 (fr) | 2016-01-20 | 2022-05-18 | Polypeptide Laboratories Holding (PPL) AB | Procédé de préparation de peptides avec un lieur pswang |
| CN114290471B (zh) * | 2021-11-17 | 2023-04-07 | 濮阳绿宇新材料科技股份有限公司 | 一种轻质蜜胺级阻燃泡沫木屑板及其制备方法 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1192402B (de) | 1956-12-17 | 1965-05-06 | Max Himmelheber Dipl Ing | Verfahren zur Herstellung von Spanplatten und Spanholzkoerpern vornehmlich niedrigen spezifischen Gewichts |
| US5112875A (en) | 1990-11-26 | 1992-05-12 | Basf Corporation | Polystyrene having high degree of expandability, and formulation having a highly-expandable polymer therein |
| AU2002214183A1 (en) | 2000-11-10 | 2002-05-21 | Symons, Michael Windsor | Method of making a finished product |
| PT1914052T (pt) * | 2006-10-19 | 2017-10-04 | Basf Se | Materiais leves à base de madeira |
| EP2042560A1 (fr) * | 2007-09-19 | 2009-04-01 | Basf Se | Matériaux légers dérivés du bois dotés de bonnes propriétés mécaniques et d'émissions réduites de formaldéhyde |
-
2010
- 2010-11-02 CA CA 2779362 patent/CA2779362A1/fr not_active Abandoned
- 2010-11-02 EP EP10774200A patent/EP2496647A1/fr not_active Withdrawn
- 2010-11-02 WO PCT/EP2010/066586 patent/WO2011054790A1/fr not_active Ceased
- 2010-11-02 US US13/508,237 patent/US20120219815A1/en not_active Abandoned
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2011054790A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| US20120219815A1 (en) | 2012-08-30 |
| WO2011054790A1 (fr) | 2011-05-12 |
| CA2779362A1 (fr) | 2011-05-12 |
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