Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
• • 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
  • B27N3/04—Manufacture of substantially flat articles, e.g. boards, from particles or fibres from fibres
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/22—Catalysts containing metal compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/22—Catalysts containing metal compounds
  • C08G18/24—Catalysts containing metal compounds of tin
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/22—Catalysts containing metal compounds
  • C08G18/24—Catalysts containing metal compounds of tin
  • C08G18/242—Catalysts containing metal compounds of tin organometallic compounds containing tin-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/71—Monoisocyanates or monoisothiocyanates
  • C08G18/715—Monoisocyanates or monoisothiocyanates containing sulfur in addition to isothiocyanate sulfur
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
  • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
• • 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

Definitions

• the present invention relates to a highly reactive isocyanate component containing an organic isocyanate having at least two isocyanate groups, an organic metal compound-based catalyst and a compound containing an aromatic sulfonylisocyanate group. Furthermore, the present invention relates to a process for producing lignocellulose-containing materials using the highly reactive isocyanate component, such lignocellulose-containing materials and a sealant containing the highly reactive isocyanate component.
• lignocellulose-containing substances wood parts, such as wood layers, wood strips, wood chips, or wood fibers, wherein the wood fibers may possibly also originate from wood fiber-containing plants, such as flax, hemp, sunflowers, Jerusalem artichoke or rapeseed. Starting materials for such wood parts or wood particles are usually thinning wood, industrial wood and used wood as well as wood fiber-containing plants.
• the preparation of the desired lignocellulose-containing materials, such as wood particles by known methods, see, for example, M. Dunky, P. Niemt, wood materials and glues, pp. 91-156, Springer Verlag Heidelberg, 2002.
• Lignocellulose-containing moldings in the case of wood as lignocellulose here also called wood materials, are a cost-effective and resource-saving alternative to solid wood and have great importance, especially in furniture and as building materials obtained.
• wood materials are usually used wood layers of different thickness, wood strips, wood chips or wood fibers from different woods.
• wood parts or wood particles are usually pressed at elevated temperature with natural and / or synthetic binders and optionally with the addition of further additives to plate or strand-shaped wood materials.
• lignocellulose-containing moldings or wood-based materials examples include medium-density fiberboard (MDF), wood chip materials - such as chipboard and chipboard (OSB, oriented starnd board) -, plywood - such as veneer plywood - and glued timber.
• MDF medium-density fiberboard
• OSB chipboard and chipboard
• plywood such as veneer plywood - and glued timber.
• binders usually formaldehyde-containing binders are used, for example urea-formaldehyde resins or melamine-containing urea-formaldehyde resins.
• the resins are prepared by polycondensation of formaldehyde with urea and / or melamine.
• the use of such formaldehyde resins can lead to free formaldehyde being present in the finished wood material.
• By hydrolysis of the polycondensates additional formaldehyde can be released. The contained in the wood material free formaldehyde and during the life of the Wood material released by hydrolysis formaldehyde can be released to the environment.
• Formaldehyde may cause allergies, skin, respiratory or eye irritation above certain limits in humans. Reducing formaldehyde emissions in building components, especially indoors, is therefore an important challenge.
• DE-A 2 306771 German Novopan GmbH describes a process for the production of chipboard from, for example, binder added wood shavings which are at least three layers scattered and then hot pressed, wherein for
• Topcoat is a particular phenolic resin used as a binder and in the middle layer, for example, isocyanate is used as a binder.
• isocyanate as a binder are the high resistance to hydrolysis of the resulting lignocellulose-containing material.
• a disadvantage of the use of isocyanates as a binder is their relatively high price. The economy of use of isocytes could be increased by shortening residence times in the hot press. It was therefore an object of the present invention to provide an even more highly reactive isocyanate component which can be used as a binder for the production of lignocellulose-containing Materials is suitable, reacted quickly in the hot pressing and yet long shelf life at room temperature.
• the object of the present invention is achieved by a highly reactive isocyanate component containing an organic isocyanate having at least two isocyanate groups, an organic metal compound-based catalyst and a compound containing an aromatic sulfonylisocyanate group.
• organic isocyanate having at least two isocyanate groups it is possible to use all organic isocyanates and prepolymers known to the person skilled in the art, preferably those known for the production of wood-based materials or polyurethanes. Such 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 having 2 to 10, preferably 2 to 8 monomer units and an average of at least one isocyanate group per monomer unit.
• a particularly preferred organic isocyanate is the oligomeric organic isocyanate PMDI ("polymeric methylenediphenylene diisocyanate") which is obtainable by condensation of formaldehyde with aniline and phosgenation of the isomers and oligomers formed in the condensation (see, for example, Becker / Braun, Kunststoff Handbuch, 3rd revised Edition, Volume 7 "Polyurethane", Hanser 1993, pages 18 last paragraph to page 19, second paragraph and page 76, fifth paragraph).
• the PMDI preferably has a viscosity at 25 ° C of 100 to 600, particularly preferably 150 to 300 mPas. It is also possible to use mixtures of organic isocyanates.
• very suitable PMDI- products are the products of LUPRANAT ® type series of BASF SE, in particular LUPRANAT ® M 20 FB of BASF SE.
• organic metal compounds which accelerate the reaction of isocyanates with compounds containing hydroxyl groups, in particular with lignocellulose-containing substances.
• organic metal compounds are organic tin compounds, such as tin (II) salts of organic carboxylic acids, such as tin (II) acetate, tin (II) octoate, tin (II) ethyl hexoate and tin (II).
• (II) laurate and the Dialkylzinn- (IV) salts of organic carboxylic acids such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate, and bismuth carboxylates such as bismuth (III) neodecanoate, bismuth-2 ethylhexanoate and bismuth octanoate or alkali metal salts of carboxylic acids such as potassium acetate or potassium formate and mixtures thereof Connections with each other.
• organic carboxylic acids such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate
• bismuth carboxylates such as bismuth (III) neodecanoate, bismuth-2 ethylhexanoate and bismuth octan
• the proportion of the catalyst based on an organic metal compound in the total weight of the highly reactive isocyanate component is preferably 0.01 to 0.3, more preferably 0.01 to 0.15 wt .-% and in particular 0.01 to 0.08 wt .-% ,
• the highly reactive isocyanate component according to the invention also contains a compound which contains an aromatic sulfonyl isocyanate group.
• the sulfonyl isocyanate group to an aromatic system, for example on a Phe- nylring.
• the aromatic system preferably contains no further isocyanate groups.
• compounds containing an aromatic sulfonyl group paratoluene sulfonyl isocyanate can be used.
• the proportion of the compound containing an aromatic sulfonyl isocyanate group in the total weight of the highly reactive isocyanate component is preferably 0.01 to 2.0 wt%, more preferably 0.01 to 0.5 wt%, still more preferably 1 to 5 times, more preferably 2 to 4 times and especially 2.5 to 3.5 times the content of catalyst based on an organic metal compound.
• the highly reactive isocyanate component may contain further compounds which are usually contained in an isocyanate component which is used as a binder for the production of lignocellulose-containing materials.
• these may be, for example, conventional additives, such as iron compounds, for example iron (III) chloride.
• iron (III) chloride is used, the iron content, based on the total weight of the organic isocyanate, is usually 10 to 100 mg / kg, preferably 40 to 70 mg / kg. In a further preferred embodiment, the iron content, based on the total weight of the organic isocyanate 10 to 30 mg / kg.
• lignocellulose-containing substances are compressed with a highly reactive isocyanate component according to the invention and then in a mold at molding temperatures of 40 to 250.degree. C., preferably 100 to 240.degree. C. and more preferably 150 to 230.degree.
• lignocellulose-containing materials preferably those in which the lignocellulose-containing particles are wood particles, takes place in the usual way, as described in "Taschenbuch der Spanplattentechnik" H.-J. Deppe, K. Ernst, 4th ed., 2000, DRW - Verlag Weinbrenner GmbH & Co., Leinfelden-Echterdingen, chapter 3.5 described.
• the term lignocellulose is known to the person skilled in the art.
• ligno-cellulose-containing particles are wood parts, such as wood layers, wood strips, wood chips, or wood fibers, wherein the wood fibers may optionally also be derived from wood fiber-containing plants, such as flax, hemp, sunflowers, Jerusalem artichoke or rapeseed.
• Preferred lignocellulose-containing substances are wood particles, in particular wood fibers or wood chips.
• binders customarily used for the production of such materials.
• These include, for example, conventional binders produced on the basis of polycondensates of formaldehyde and phenols, ureas or melamine.
• Such resins and their preparation are described, for example, in Ullmanns 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 15 to 141 "Amino Resins” and 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 ).
• additives can be used. These include all additives known to the skilled worker, for example waxes, paraffin emulsion, flame retardant additives, wetting agents, salts, but also inorganic or organic acids and bases, for example mineral acids such as sulfuric acid, nitric acid, organic sulfonic acids, carboxylic acids such as formic acid or acetic acid or inorganic o -
• the organic bases for example, sodium hydroxide (aqueous or in substance), calcium oxide or calcium carbonate (each aqueous or in substance) or ammonia, aqueous or as a substance.
• additives can be added in an amount of 0 to 20% by weight, preferably 0 to 5% by weight, in particular 0 to 1% by weight, based on the dry weight of the lignocellulose-containing substances.
• the proportion of water is particularly preferably minimized.
• the proportion of water is preferably less than 2 wt .-%, more preferably less than 1 wt .-% and in particular less than 0.5 wt .-%, each based on the total weight of all starting materials used for the production of lignocellulose-containing materials - lent in the lignocellulosic substances contained residual moisture.
• the lignocellulose-containing substances preferably wood particles, particularly preferably wood chips or fibers
• the highly reactive isocyanate component preferably wood particles, particularly preferably wood chips or fibers
• gluing process are known for the production of conventional wood materials with conventional aminoplast resins and, for example, in "paperback the chipboard technology" H.-J. Deppe, K. Ernst, 4th ed., 2000, DRW - Verlag Weinbrenner GmbH & Co., Leinfelden- Echterdingen, Chapter 3.3 described.
• the highly reactive isocyanate component and any other further binders and / or customary additives are preferably not mixed before being brought into contact with the lignocellulose-containing substances. All components can be added simultaneously to the lignocellulose-containing substances. In a preferred embodiment, the highly reactive isocyanate component according to the invention is added as the last component to the lignocellulose-containing substances.
• the thickness of the multilayered lignocellulose-containing materials according to the invention varies with the field of application and is generally in the range of 0.5 to 300 mm, preferably in the range of 10 to 200 mm, in particular 12 to 100 mm.
• the thickness ratios of the layers of the multilayer lignocellulose-containing moldings according to the invention, preferably the plate-shaped moldings are variable.
• the outer layers also called cover layers, taken alone or in total thinner than the layer or layers of the middle layers).
• the mass of a single cover layer is usually in the range of 5 to 30 wt .-%, preferably 10 to 25 wt .-% of the total mass of the multilayer lignocellulose-containing molding according to the invention.
• Another object of the invention is a lignocellulos termer material, obtainable by a method according to the invention.
• Such a lignocellulose-containing material according to the invention can be used, for example, for the production of furniture and furniture parts, packaging materials, in building construction or in vehicles such as cars, buses, trucks, boats and aircraft. It shows low formaldehyde emission and is especially stable against hydrolysis.
• the highly reactive isocyanate component according to the invention is characterized by good shelf life at room temperature and rapid curing in contact with isocyanate-reactive groups or moisture, for example at elevated temperature.
• the highly reactive isocyanate component according to the invention can also be used for other purposes, for example as a sealant.
• sealants may be used, inter alia, as moisture-curing sealants, for example used in the construction industry.
• the curing time can be significantly reduced even at room temperature compared to known sealants.
• the shelf life of a polymer MDI isocyanate component having a viscosity of 260 mPas at 20 ° C and an iron content of 25 mg / kg and a content of 0.04 wt .-% of the tin catalyst Fomrez®.UL32 from Witco is tested.
• the viscosity of the mixtures in mPas as a function of the storage time is given in Table 1 and FIG.
• Table 1 shows that the viscosity of the isocyanate component without paratoluene sulfonyl isocyanate also increases at 25 ° C within a few days.
• the viscosity of the isocyanate component with paratoluene sulfonyl isocyanate which was stored at 25 ° C even after 100 days storage nor the initial viscosity and also the viscosity increase of stored at 50 ° C isocyanate component with paratoluene sulfonylisocyanate is significantly slowed compared to the comparative example at 25 ° C.
• the reactivity of the isocyanate component as a function of the catalyst concentration is given in Table 2.
• Table 2 shows that a high transverse tensile strength when using Example 1 is already achieved after pressing times of 7 seconds per mm thickness, while corresponding values of the transverse tensile strength for Comparative Example 2 are reached only after 8.5 seconds / mm.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Materials Engineering (AREA)
• Inorganic Chemistry (AREA)
• Manufacturing & Machinery (AREA)
• Forests & Forestry (AREA)
• Dry Formation Of Fiberboard And The Like (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Polyurethanes Or Polyureas (AREA)
• Sealing Material Composition (AREA)

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• 2010
  • 2010-12-08 MX MX2012006471A patent/MX2012006471A/es active IP Right Grant
  • 2010-12-08 EP EP10787463A patent/EP2510032A1/de not_active Withdrawn
  • 2010-12-08 CN CN2010800557299A patent/CN102648224A/zh active Pending
  • 2010-12-08 BR BR112012013895A patent/BR112012013895A2/pt not_active Application Discontinuation
  • 2010-12-08 WO PCT/EP2010/069112 patent/WO2011070040A1/de not_active Ceased
  • 2010-12-08 AU AU2010329950A patent/AU2010329950B2/en not_active Ceased
  • 2010-12-08 CA CA2782695A patent/CA2782695A1/en not_active Abandoned
  • 2010-12-08 NZ NZ601031A patent/NZ601031A/xx not_active IP Right Cessation
  • 2010-12-08 MY MYPI2012002508A patent/MY155981A/en unknown
  • 2010-12-08 JP JP2012542527A patent/JP5837505B2/ja not_active Expired - Fee Related
  • 2010-12-08 US US13/514,428 patent/US20120245258A1/en not_active Abandoned
  • 2010-12-08 KR KR1020127017571A patent/KR20120107985A/ko not_active Ceased

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