WO2021182980A1 - Method of manufacturing polyurethane materials from reactive polyols and polyols obtainable from waste after processing wood or wood-like waste - Google Patents

Method of manufacturing polyurethane materials from reactive polyols and polyols obtainable from waste after processing wood or wood-like waste Download PDF

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WO2021182980A1
WO2021182980A1 PCT/PL2021/000011 PL2021000011W WO2021182980A1 WO 2021182980 A1 WO2021182980 A1 WO 2021182980A1 PL 2021000011 W PL2021000011 W PL 2021000011W WO 2021182980 A1 WO2021182980 A1 WO 2021182980A1
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parts
wood
mass
waste
mixture
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PCT/PL2021/000011
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French (fr)
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Łukasz PISZCZYK
Paulina Kosmela
Józef Haponiuk
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Politechnika Gdanska
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Priority to EP21768868.8A priority Critical patent/EP4118129A4/en
Publication of WO2021182980A1 publication Critical patent/WO2021182980A1/en

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    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/16Catalysts
    • C08G18/161Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
    • C08G18/163Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
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    • C08G18/18Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/20Heterocyclic amines; Salts thereof
    • C08G18/2009Heterocyclic amines; Salts thereof containing one heterocyclic ring
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    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/4009Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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    • C08G18/40High-molecular-weight compounds
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    • C08G18/00Polymeric products of isocyanates or isothiocyanates
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    • C08G18/40High-molecular-weight compounds
    • C08G18/64Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6492Lignin containing materials; Wood resins; Wood tars; Derivatives thereof
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    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
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    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143Halogen containing compounds
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    • C08L97/02Lignocellulosic material, e.g. wood, straw or bagasse
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    • C08J2203/00Foams characterized by the expanding agent
    • C08J2203/14Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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    • C08J2203/00Foams characterized by the expanding agent
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    • C08J2375/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04Polyurethanes
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    • C08J2497/00Characterised by the use of lignin-containing materials
    • C08J2497/02Lignocellulosic material, e.g. wood, straw or bagasse

Definitions

  • the invention refers to a method of obtaining new polyurethane materials, especially binders, polyurethane foams, or resins from reactive polyols.
  • These polyols are synthesized from wood processing waste such as: bark, wood chips, sawdust, wood dust, or wood-like waste from wood processing such as: waste fibreboards, waste MDF boards, waste HDF boards, waste chipboards, waste OSB boards and waste plywood boards or petrochemical polyols and waste mentioned above - milled wooden waste after wood processing and wood-like waste.
  • the invention is used in the construction, furniture, and automotive industries.
  • Wood-based panels are a group of composite materials, which are a type of construction wood materials. These materials are made using hot-pressing, where high temperature combined with pressure causes the resin to harden and forms the shape of the material.
  • the process involves ligno-cellulose particles in the form of veneer sheets, shavings, sawdust, fibers, and woody parts of annual plants.
  • the types of wood- based panels are divided depending on the type of lignocellulosic particles used in their production. Boards made of wood shavings are called particle boards, boards made of wood fibers - fibreboards, and made of veneer sheet - plywood.
  • the basic recovery processes include thermal transformation of waste, in which heat plays an important role in the physical or chemical transformation of waste.
  • the most popular thermal conversion methods are: combustion, pyrolysis, and gasification.
  • combustion, pyrolysis, and gasification The main advantage of these processes is the ability to transform waste into a harmless material with a significant weight and volume reduction.
  • a beneficial side effect of thermal conversion is the transformation of chemical energy from waste and its conversion into thermal energy.
  • the use of the generated heat stream as a recycled energy enables reduction in the consumption of nonrenewable fossil fuels.
  • the final method of thermal transformation of waste may include incineration of waste.
  • the following parameters have been selected: the compositions of materials (petrochemical polyols, and / or reactive polyols obtained from wood-based and / or wood-like waste, catalysts, auxiliary compounds (blowing agents, surfactants, anti-foaming agents), shredded wood waste or wood-like waste of a certain size grains, isocyanates and the optimal NCO / OH ratio), as well as processing parameters - forming time, temperature and process pressure.
  • materials petrochemical polyols, and / or reactive polyols obtained from wood-based and / or wood-like waste
  • catalysts auxiliary compounds (blowing agents, surfactants, anti-foaming agents), shredded wood waste or wood-like waste of a certain size grains, isocyanates and the optimal NCO / OH ratio)
  • auxiliary compounds blowwing agents, surfactants, anti-foaming agents
  • shredded wood waste or wood-like waste of a certain size grains isocyanates and the optimal NCO / OH ratio
  • the subject matter of the invention is to provide material from reactive or petrochemical polyols and / or polyols obtained from wood waste or similar waste, while as a filler shredded wood waste and / or wood-like waste have been introduced.
  • Reactive polyols are obtained in the thermochemical solvolysis - liquefaction reaction in the presence of a solvent such as alcohols, glycols, and reaction catalysts - acid or basic, acidic and then basic or basic and then acidic catalysts.
  • Reactive polyols are obtainable from waste that appeared after processing wood or woodlike waste.
  • the following parameters were specified: application of a thermochemical solvolysis process at a temperature of 80 to 300 ° C, a time of 60 to 600 min, waste content of 1 to 50% by weight, in relation to the solvent and the grain size of the waste from 1 pm to 500 pm.
  • the catalyst is used in an amount of 0.01 to 20% by weight, with respect to the solvent used.
  • the catalyst is acid or base, or both together.
  • Polyols are obtained from milled wood waste and / or wood-like waste with a grain size of 0.1 pm to 500 pm.
  • waste from wood processing such as: bark, wood chips, sawdust, wood dust, wood shavings and waste from fibreboards, MDF boards (Medium- Density Fibreboard), HDF boards (High Density). Fiberboard, particle boards, OSB (Oriented Strand Board) can be used.
  • the polyols are obtained according to the method described above from wood-like waste and have physical properties such as hydroxyl number from 50 to 800 mg KOH/g, acid number from 0.1 to 20 mg KOH / g, molecular weight from 30 g / mol. up to 7,000 g / mol and functionality from 1 to 6.
  • new polyurethane materials are obtained from polyols synthesized from waste after processing wood or wood-like waste and / or petrochemical polyols.
  • a filler milled wood waste and/or milled wood-like waste is introduced into this polyurethane system.
  • a polyol mixture is prepared by mixing 1-100 parts by mass of polyols obtained from wood waste or 1-100 parts by mass of polyols obtained from wood-like waste and 1-100 parts by mass of petrochemical oligomerols and 0.01-10 parts by mass of catalysts (amine catalyst and/or organometallic catalyst and / or metal salts), 0-20 parts by mass of surfactants, 0-20 parts by mass of anti-foaming agents, 0-20 parts by mass of blowing agents, 0-900 parts by mass of milled waste after wood processing and/or 0-900 parts of millrd wood-like waste. This is then mixed with the isocyanate with an NCO / OH molar ratio of 0.5 to 4.
  • the method of obtaining new polyurethane materials consists of cross-linking and curing at room temperature and normal pressure and / or at a temperature below the degradation temperature and increased pressure. Forming at a temperature of 20 °C to 180°C and a pressure of 0.9 to 50 bar is preferred.
  • waste after wood processing such as: bark, wood chips, sawdust, wood dust, wood shavings and/or waste from fibreboards, MDF (Medium-Density Fibreboard), HDF (High Density Fibreboard), particle board, OSB (Oriented Strand Board), which are milled to a certain size.
  • MDF Medium-Density Fibreboard
  • HDF High Density Fibreboard
  • OSB Oriented Strand Board
  • petrochemical polyols such as: polyethers and polyesterrols, with molecular weights from 200 to 7000 g / mol and hydroxyl number from 28 to 600 mgKOH / g and functionality from 1 to 6 can be used.
  • isocyanate in the form of an aromatic, an aliphatic compound and/or a prepolymer with a concentration of unbound isocyanate groups from 5% to 48% and a functionality from 0.5 to 6.
  • amine catalysts mainly tertiary amines
  • organometallic mainly organotin
  • metal mainly sodium and potassium
  • the following catalysts are preferably used: potassium acetate solution in ethylene glycol, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine, 2- [2-
  • blowing agents are preferably used: 1,1,1,3,3-pentafluorobutane, n-pentane, cyclopentane, cyclohexane, dichloromethane, water.
  • the following surfactants are preferably used: polysiloxane-modified polyethers (trade name Tegostab 8537, Tegostab 8465, Tegostab 8460), polysiloxanes, silicone oils, silicone glycol copolymer.
  • anti-foaming agents are preferably used: mixtures of different agents (trade name: Chemax DF -10A, Chemax DFO-400, EXOantifoam CPD3), EO / PO block copolymers (ethylene oxide / propylene oxide) (trade name: ROKAmer 2000, ROKAmer 2000S, ROKAmer 2600S ), mixtures of mineral oils (trade name: HE®-COAT-DF 691, CHE®-COAT-DF 581B), mixtures of silicone oils (trade name: CHE DF 9022).
  • Preference to use as a filler is given to the milled waste after wood processing, such as: bark, wood chips, sawdust, wood dust, wood shavings, and wood-like waste from wood processing, such as: fibreboard waste, MDF board waste, HDF board waste, chipboard waste, waste OSB boards or waste plywood boards with grain size from 0.1 mpi-500 pm.
  • isocyanates are preferred to use: 4,4-diphenylmethane diisocyanate (MDI), 2,4-toluene diisocyanate (TDI), 1,6-hexamethylene diisocyanate (HDI), polymeric 4,4-diphenylmethane diisocyanate (pMDI).
  • MDI 4,4-diphenylmethane diisocyanate
  • TDI 2,4-toluene diisocyanate
  • HDI 1,6-hexamethylene diisocyanate
  • pMDI polymeric 4,4-diphenylmethane diisocyanate
  • the advantage of new polyurethane materials obtained from wood waste and wood-like waste is a competitive price and a less harmful production process compared to petrochemical oligomerols.
  • the advantage of the new polyurethane materials is the possibility of foaming the polyurethane composition with water, which reacts with the isocyanate group to form carbon dioxide, or foaming by hydrophobic blowing agents, pentane and its derivatives, as well as mixtures of the above- mentioned blowing agents.
  • the advantage of such a mixture is the reduction of the amount of flammable pentane by replacing it with water.
  • the example describes the production of polyurethane materials using synthesized polyols from wood waste and / or wood-like waste containing milled waste and / or petrochemical polyols.
  • auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 1.5 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 1.5 parts by mass; surfactant (Tegostab 8460 - polysiloxane modified polyester) and whole mixture was homogenized.
  • the filler was added to the mixture in the form of milled waste (bark) with a grain size of 0.1 pm (0.1 parts by mass) and a foaming agent in the form of: 1,1,1,3,3-pentafluorobutane (10 parts by mass) and water (2 parts by mass).
  • catalysts 33% solution of potassium acetate in ethylene glycol ( 2.5 parts by mass), 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 5 parts by
  • the filler was added to the mixture in the form of milled waste (bark) with a grain size of 60-150 mpi (40 parts by mass) and a foaming agent in the form of: 1 ,1 ,1 ,3,3-pentafluorobutane (10 parts by mass) and water (2 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 3/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 21 °C and a pressure of 1.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane foam. The characteristics were checked and its receipt was confirmed - the foam has a density of 60 kg / m3.
  • auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol (10 parts by mass); surfactant (20 parts by mass Tegostab 8460 - polysiloxane modified polyester) and the whole mixture was homogenized.
  • the filler was added to the mixture in the form of milled waste (wood shavings) with a grain size of 160-240 pm (30 parts by mass) and a foaming agent in the form of: 1,1,1,3,3-pentafluorobutane (10 parts by mass) and water (2 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 2,5/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 21 °C and a pressure of 1.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane foam. The characteristics were checked and its receipt was confirmed - the foam has a density of 70 kg / m3.
  • Example 4 The material was made similarly to example 1, except that no reactive polyol from a wood-based or wood-like material was used.
  • petrochemical polyol sorbitol oxypropoxylation product - Rokopol RF 551
  • catalysts 33% solution of potassium acetate in ethylene glycol (1,5 parts by mass), 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine (1,5 parts by mass); surfactant (4 parts by mass Tegostab 8460 - polysiloxane modified polyester) and whole mixture was homogenized.
  • the filler was added to the mixture in the form of milled waste (wood shavings) with a grain size of 50-160 pm (10 parts by mass) and a foaming agent in the form of: 1,1,1,3,3-pentafluorobutane (10 parts by mass) and water (2 parts by mass).
  • a foaming agent in the form of: 1,1,1,3,3-pentafluorobutane (10 parts by mass) and water (2 parts by mass).
  • isocyanate pMDI
  • isocyanate was added in an amount that the molar ratio of NCO / OH groups was 3/1.
  • Premix with isocyanate was mixed for 10 seconds.
  • the cross-linking and curing process was carried out at a temperature of 22 °C and a pressure of 1.0 bar.
  • a polyurethane material was obtained in the form of polyurethane foam. The characteristics were checked and its receipt was confirmed - the foam has a density of 45 kg /m3.
  • Example 5 The material was prepared as follows: 70 parts by mass of a petrochemical polyol - sorbitol oxypropoxylation product (Rokopol RF 551) and 30 parts of petrochemical polyol (Rokopol M6000) were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 1.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-1,3,5- triazine in an amount of 2.5 parts by mass; surfactant (Tegostab 8460 - polysiloxane modified polyester) in an amount of 4.0 parts and whole mixture was homogenized.
  • auxiliary compounds 33% solution of potassium acetate in ethylene glycol in the amount of 1.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-1,3,5- triazine in an amount of 2.5 parts by
  • the filler was added to the mixture in the form of wood-like waste (MDF board ) with a grain size of 160-240 pm (40 parts by mass) and a foaming agent in the form of: 1, 1,1, 3,3- pentafluorobutane (10 parts by mass) and water (2 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 3/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 22 °C and a pressure of 1.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane foam. The characteristics were checked and its receipt was confirmed - the foam has a density of 70 kg / m3.
  • MDF board wood-like waste
  • a foaming agent in the form of: 1, 1,1, 3,3- pentafluorobutane (10 parts by mass) and water
  • Example 6 The material was prepared as follows: 70 parts by mass of a petrochemical polyol - sorbitol oxypropoxylation product (Rokopol RF 551) and 30 parts of petrochemical polyol (Rokopol M6000) were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 1.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro- 1,3,5 - triazine in an amount of 2.5 parts by mass and whole mixture was homogenized.
  • the filler was added to the mixture in the form of wood-like waste (MDF board ) with a grain size of 160-240 pm (40 parts by mass) and a foaming agent in the form of: 1, 1,1, 3,3- pentafluorobutane (10 parts by mass) and water (2 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 3/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 22 °C and a pressure of 1.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane foam. The characteristics were checked and its receipt was confirmed - the foam has a density of 80 kg / m3.
  • MDF board wood-like waste
  • a foaming agent in the form of: 1, 1,1, 3,3- pentafluorobutane (10 parts by mass) and water
  • Example 7 The material was prepared as follows: 50 parts by mass of a petrochemical polyol - sorbitol oxypropoxylation product (Rokopol RF 551) and 50 parts of petrochemical polyol (Rokopol M6000) were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 1.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-1,3,5- triazine in an amount of 2.5 parts by mass; surfactant (Tegostab 8460 - polysiloxane modified polyester) in an amount of 5.0 parts and whole mixture was homogenized.
  • auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 1.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-1,3,5- tria
  • the filler was added to the mixture in the form of wood-like waste (OSB board) with a grain size of 160-240 pm (40 parts by mass) and a foaming agent in the form of: 1, 1,1, 3,3- pentafluorobutane (10 parts by mass) and water (2 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 2.5/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 22 °C and a pressure of 1.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane foam. The characteristics were checked and its receipt was confirmed - the foam has a density of 50 kg / m3.
  • OSB board wood-like waste
  • a foaming agent in the form of: 1, 1,1, 3,3- pentafluorobutane (10 parts by mass) and water (2
  • Example 8 The material was prepared as follows: 50 parts by mass of a petrochemical polyol - sorbitol oxypropoxylation product (Rokopol RF 551) and 50 parts of petrochemical polyol (Rokopol M6000) were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 1.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-1,3,5- triazine in an amount of 2.5 parts by mass and whole mixture was homogenized.
  • the filler was added to the mixture in the form of wood-like waste (OSB board ) with a grain size of 160-240 pm (20 parts by mass) and a foaming agent in the form of: 1,1, 1,3 ,3- pentafluorobutane (10 parts by mass) and water (2 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 2.5/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 22 °C and a pressure of 1.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane foam. The characteristics were checked and its receipt was confirmed - the foam has a density of 70 kg / m3.
  • OSB board wood-like waste
  • a foaming agent in the form of: 1,1, 1,3 ,3- pentafluorobutane (10 parts by mass
  • auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 2.5 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 2.5 parts by mass; surfactant (Tegostab 8460 - polysiloxane modified polyester) in an amount of 15.0 parts and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood dust with a grain size of 0.1-50 pm (40 parts by mass) and a foaming agent in the form of: n-pentane (10 parts by mass).
  • auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 3.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 4.0 parts by mass; surfactant (Tegostab 8460 - polysiloxane modified polyester) in an amount of 18.0 parts and whole mixture was homogenized. Then, the filler was added to the mixture in the form of chipboard with a grain size of 360-500 pm (60 parts by mass) and a foaming agent in the form of: n-pentane (10 parts by mass) and water (5 parts by mass).
  • auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 3.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 4.0 parts by mass; surfactant (Tegostab 8460 - polysiloxane modified polyester) in an amount of 18.0 parts and whole mixture was homogenized. Then, the foaming agent in the form: n- pentane (10 parts by mass) and water (5 parts by mass) were added.
  • catalysts 33% solution of potassium acetate in ethylene glycol in the amount of 1.5 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 1.5 parts by mass; surfactant (Tegostab 8460 - polysiloxane modified polyester) in an amount of 4.0 parts and whole mixture was homogenized.
  • the filler was added to the mixture in the form of wood-like waste (MDF board ) with a grain size of 50-160 pm (50 parts by mass) and a foaming agent in the form of: 1,1,1,3,3-pentafluorobutane (10 parts by mass) and water (2 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 2.5/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 22 °C and a pressure of 1.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane foam.
  • MDF board wood-like waste
  • a foaming agent in the form of: 1,1,1,3,3-pentafluorobutane (10 parts by mass) and water (2 parts by mass).
  • pMDI isocyanate
  • Premix with isocyanate was
  • the foam has a density of 41 kg / m3. It is a material obtained from petrochemical and reactive polyols nto which shredded wood waste or wood-like waste was introduced as a filler.
  • catalysts 33% solution of potassium acetate in ethylene glycol in the amount of 1.5 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 1.5 parts by mass; surfactant (Tegostab 8460 - polysiloxane modified polyester) in an amount of 4.0 parts and whole mixture was homogenized.
  • the filler was added to the mixture in the form of wood-like waste (HDF board ) with a grain size of 50-160 pm (20 parts by mass) and a foaming agent in the form of: 1,1,1,3,3-pentafluorobutane (10 parts by mass) and water (2 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 2.2/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 22 °C and a pressure of 1.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane foam. The characteristics were checked and its receipt was confirmed - the foam has a density of 48 kg / m3. It is a material obtained from petrochemical and reactive polyols nto which shredded wood waste or wood-like waste was introduced as a filler.
  • the filler was added to the mixture in the form of wood-like waste (OSB board ) with a grain size of 240-360 pm (100 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.1/1. Premix with isocyanate was mixed for 10 seconds. The cross- linking and curing process was carried out at a temperature of 110 °C and a pressure of 30.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin.
  • auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 5.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 5.0 parts by mass, flame retardants (copolymer EO/PO) in an amount of 0.5 parts of mass and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood waste (bark) with a grain size of 360- 500 pm (200 parts by mass).
  • Example 18 The material was prepared as follows: 100 parts by mass of a petrochemical polyol - (Rokopol M6000) and catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 5.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 5.0 parts by mass, flame retardants (copolymer EO/PO) in an amount of 0.5 parts of mass and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood waste (bark) with a grain size of 60- 150 pm (200 parts by mass).
  • catalysts 33% solution of potassium acetate in ethylene glycol in the amount of 5.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine
  • the filler was added to the mixture in the form of wood -like waste (beaverboard) with a grain size of 1-50 pm (200 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.3/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 120 °C and a pressure of 20.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 13.3 MPa Example 20.
  • pMDI isocyanate
  • the cross-linking and curing process was carried out at a temperature of 120 °C and a pressure of 20.0 bar.
  • a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 17.3 MPa Example 21.
  • auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 5.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 5.0 parts by mass, flame retardants (copolymer EO/PO) in an amount of 5.0 parts of mass and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood waste (wood dust) with a grain size of 1-50 pm (400 parts by mass).
  • auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 5.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,
  • the filler was added to the mixture in the form of wood-like waste (MDF board) with a grain size of 50-160 pm (400 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.1/1. Premix with isocyanate was mixed for 10 seconds. The cross- linking and curing process was carried out at a temperature of 160 °C and a pressure of 25.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 11.3 MPa
  • auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 5.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,
  • the filler was added to the mixture in the form of wood waste (wood dust) with a grain size of 0.1-50 pm (900 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.1/1. Premix with isocyanate was mixed for 10 seconds. The cross- linking and curing process was carried out at a temperature of 160 °C and a pressure of 25.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 1.3 MPa Example 24.
  • the filler was added to the mixture in the form of wood waste (wood shavings) with a grain size of 50-150 pm (800 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.1/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 150 °C and a pressure of 25.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 2.3 MPa
  • Example 25 The material was prepared as follows: 100 parts by mass of a petrochemical polyol - (Rokopol RF 551) and catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 2.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 1.5 parts by mass and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood-like waste (OSB board) with a grain size of 150-240 pm (500 parts by mass).
  • OSB board wood-like waste
  • Example 26 The material was prepared as follows: 50 parts by mass of a petrochemical polyol - (Rokopol M6000) and 50 parts of a petrochemical polyol - (Rokopol RF 551) were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 2.0 parts by mass, 1,3,5- tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 1.5 parts by mass; flame retardants (copolymer EO/PO) in the amount 1.5 parts by mass and whole mixture was homogenized.
  • catalysts 33% solution of potassium acetate in ethylene glycol in the amount of 2.0 parts by mass, 1,3,5- tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 1.5 parts by mass
  • flame retardants copolymer EO/PO
  • the filler was added to the mixture in the form of woodlike waste (plywood panels) with a grain size of 250-360 pm (400 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.1/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 100 °C and a pressure of 15.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 10.3 MPa
  • auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 1.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydr
  • the filler was added to the mixture in the form of wood-like waste (HDF board) with a grain size of 360- 500 pm (900 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.5/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 180 °C and a pressure of 35.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 1.3 MPa
  • auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 4.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 2.0 parts by mass and whole mixture was homo
  • the filler was added to the mixture in the form of wood-like waste (HDF board) with a grain size of 360-500 pm (200 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.5/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 120 °C and a pressure of 35.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 9.3 MPa
  • the filler was added to the mixture in the form of wood-like waste (MDF board) with a grain size of 240-350 pm (100 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.7/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 140 °C and a pressure of 35.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 10.3 MPa Example 30.
  • the filler was added to the mixture in the form of wood-like waste (MDF board) with a grain size of 240-350 pm (50 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.4/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 60 °C and a pressure of 35.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 16.3 MPa Example 31.
  • the filler was added to the mixture in the form of wood-like waste (chipboard) with a grain size of 240-350 pm (100 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.4/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 21 °C and a pressure of 1.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 14.3 MPa.
  • the filler was added to the mixture in the form of wood-like waste (chipboard) with a grain size of 240-350 pm (0.5 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.4/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 21 °C and a pressure of 1.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 16.3 MPa Example 33.
  • catalysts 33% solution of potassium acetate in ethylene glycol in the amount of 2.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 1.5 parts by mass; flame retardanst
  • the filler was added to the mixture in the form of wood-like waste (MDF board) with a grain size of 60-150 mpi (1.0 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.4/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 21 °C and a pressure of 1.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 15.3 MPa
  • the filler was added to the mixture in the form of wood-like waste (MDF board) with a grain size of 60-150 mih (10.0 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.2/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 21 °C and a pressure of 1.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 8.3 MPa Example 35.
  • the filler was added to the mixture in the form of wood- like waste (MDF board) with a grain size of 150-240 pm (300.0 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.5/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 10O °C and a pressure of 5.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 12.3 MPa.
  • the filler was added to the mixture in the form of wood-like waste (beaverboard) with a grain size of 150-240 pm (400.0 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.2/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 100 °C and a pressure of 50.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 18.3 MPa. Example 37.
  • the filler was added to the mixture in the form of wood-like waste (HDF board) with a grain size of 250-360 pm (300.0 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.1/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 100 °C and a pressure of 50.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 17.3 MPa. Example 38.
  • the filler was added to the mixture in the form of wood waste (wood shavings) with a grain size of 150-240 pm (800.0 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.3/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 150 °C and a pressure of 50.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 1.3 MPa. Example 39.
  • the filler was added to the mixture in the form of wood waste (bark) with a grain size of 60-150 pm (500.0 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.2/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 100 °C and a pressure of 50.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 3.3 MPa.
  • the filler was added to the mixture in the form of wood waste (wood chips) with a grain size of 150-240 pm (150.0 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.2/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 23 °C and a pressure of 1.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 11.3 MPa.
  • the filler was added to the mixture in the form of wood-like waste (plywood board) with a grain size of 150-240 pm (200.0 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 2.0/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 70 °C and a pressure of 3.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 11.3 MPa.

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Abstract

The invention relates to a process for the production of new polyurethane materials from polyols and wood waste and / or wood-like waste. This method is characterized by the use of polyol synthesized from wood waste and / or wood-like waste polyols or petrochemical polyols are used. A polyol mixture is prepared by mixing 1-100 parts by mass of polyols obtained from wood waste and/or 1-100 parts by mass of polyols obtained from wood-like waste and/or 1-100 parts by mass of petrochemical oligomerols and 0.01-10 parts by mass catalysts. Moreover, surfactants, anti-foaming agents, blowing agents and milled waste after wood processing or milled wood-like waste can be used. The resulting polyol mixture is then mixed with the isocyanate in an NCO / OH molar ratio ranging from 0.5 to 4.

Description

Method of manufacturing polyurethane materials from reactive polyols and polyols obtainable from waste after processing wood or wood-like waste
The invention refers to a method of obtaining new polyurethane materials, especially binders, polyurethane foams, or resins from reactive polyols. These polyols are synthesized from wood processing waste such as: bark, wood chips, sawdust, wood dust, or wood-like waste from wood processing such as: waste fibreboards, waste MDF boards, waste HDF boards, waste chipboards, waste OSB boards and waste plywood boards or petrochemical polyols and waste mentioned above - milled wooden waste after wood processing and wood-like waste. The invention is used in the construction, furniture, and automotive industries.
The wood processing industry gives the opportunity to use wooden raw materials for the production of wood-based panels. These panels include: fiberboard, particle board, plywood, and OSB panels. Wood-based panels are a group of composite materials, which are a type of construction wood materials. These materials are made using hot-pressing, where high temperature combined with pressure causes the resin to harden and forms the shape of the material. The process involves ligno-cellulose particles in the form of veneer sheets, shavings, sawdust, fibers, and woody parts of annual plants. The types of wood- based panels are divided depending on the type of lignocellulosic particles used in their production. Boards made of wood shavings are called particle boards, boards made of wood fibers - fibreboards, and made of veneer sheet - plywood.
Due to the excessive amount of waste produced, many wood industry plants use practices related to the energy recovery process, i.e., the use of the generated waste to obtain useful substances for energy purposes. The basic recovery processes include thermal transformation of waste, in which heat plays an important role in the physical or chemical transformation of waste. The most popular thermal conversion methods are: combustion, pyrolysis, and gasification. The main advantage of these processes is the ability to transform waste into a harmless material with a significant weight and volume reduction. A beneficial side effect of thermal conversion is the transformation of chemical energy from waste and its conversion into thermal energy. The use of the generated heat stream as a recycled energy enables reduction in the consumption of nonrenewable fossil fuels. The final method of thermal transformation of waste may include incineration of waste. Other methods, i.e., pyrolysis and gasification, are intermediate steps which are leading to incineration in further steps. The combustion process should be distinguished from the simultaneous processes of pyrolysis and gasification of fuel. However, researchers are still looking for more efficient methods of using wood and wood-like waste to obtain valuable new raw materials, intermediates, and final products.
According to the invention, the following parameters have been selected: the compositions of materials (petrochemical polyols, and / or reactive polyols obtained from wood-based and / or wood-like waste, catalysts, auxiliary compounds (blowing agents, surfactants, anti-foaming agents), shredded wood waste or wood-like waste of a certain size grains, isocyanates and the optimal NCO / OH ratio), as well as processing parameters - forming time, temperature and process pressure. These parameters determine that the method is efficient and enables to obtain a valuable material that can be further used in industry.
The subject matter of the invention is to provide material from reactive or petrochemical polyols and / or polyols obtained from wood waste or similar waste, while as a filler shredded wood waste and / or wood-like waste have been introduced. Reactive polyols are obtained in the thermochemical solvolysis - liquefaction reaction in the presence of a solvent such as alcohols, glycols, and reaction catalysts - acid or basic, acidic and then basic or basic and then acidic catalysts.
Reactive polyols are obtainable from waste that appeared after processing wood or woodlike waste. The following parameters were specified: application of a thermochemical solvolysis process at a temperature of 80 to 300 ° C, a time of 60 to 600 min, waste content of 1 to 50% by weight, in relation to the solvent and the grain size of the waste from 1 pm to 500 pm. The catalyst is used in an amount of 0.01 to 20% by weight, with respect to the solvent used. The catalyst is acid or base, or both together.
Polyols are obtained from milled wood waste and / or wood-like waste with a grain size of 0.1 pm to 500 pm. Preferably, waste from wood processing, such as: bark, wood chips, sawdust, wood dust, wood shavings and waste from fibreboards, MDF boards (Medium- Density Fibreboard), HDF boards (High Density). Fiberboard, particle boards, OSB (Oriented Strand Board) can be used.
The polyols are obtained according to the method described above from wood-like waste and have physical properties such as hydroxyl number from 50 to 800 mg KOH/g, acid number from 0.1 to 20 mg KOH / g, molecular weight from 30 g / mol. up to 7,000 g / mol and functionality from 1 to 6.
The advantage of new polyols obtained from wood-like waste is a competitive price compared to petrochemical raw materials and a less environmentally harmful process of production. Moreover, there is also the possibility of using new reactive polyols for the production of polyurethane materials in the form of rigid PUR foams, rigid PIR-PUR foams, as well as polyurethane adhesives and binders.
According to the invention, new polyurethane materials are obtained from polyols synthesized from waste after processing wood or wood-like waste and / or petrochemical polyols. In this composition, a filler (milled wood waste and/or milled wood-like waste) is introduced into this polyurethane system. According to this invention, a polyol mixture is prepared by mixing 1-100 parts by mass of polyols obtained from wood waste or 1-100 parts by mass of polyols obtained from wood-like waste and 1-100 parts by mass of petrochemical oligomerols and 0.01-10 parts by mass of catalysts (amine catalyst and/or organometallic catalyst and / or metal salts), 0-20 parts by mass of surfactants, 0-20 parts by mass of anti-foaming agents, 0-20 parts by mass of blowing agents, 0-900 parts by mass of milled waste after wood processing and/or 0-900 parts of millrd wood-like waste. This is then mixed with the isocyanate with an NCO / OH molar ratio of 0.5 to 4.
The method of obtaining new polyurethane materials consists of cross-linking and curing at room temperature and normal pressure and / or at a temperature below the degradation temperature and increased pressure. Forming at a temperature of 20 °C to 180°C and a pressure of 0.9 to 50 bar is preferred.
The best results are obtained when using milled wood-like waste from 1 pm to 500 pm. Preferably, waste after wood processing, such as: bark, wood chips, sawdust, wood dust, wood shavings and/or waste from fibreboards, MDF (Medium-Density Fibreboard), HDF (High Density Fibreboard), particle board, OSB (Oriented Strand Board), which are milled to a certain size.
Preferably, petrochemical polyols (oligomerols) such as: polyethers and polyesterrols, with molecular weights from 200 to 7000 g / mol and hydroxyl number from 28 to 600 mgKOH / g and functionality from 1 to 6 can be used. It is preferred to use the isocyanate in the form of an aromatic, an aliphatic compound and/or a prepolymer with a concentration of unbound isocyanate groups from 5% to 48% and a functionality from 0.5 to 6.
Preferably, amine catalysts (mainly tertiary amines), organometallic (mainly organotin), and metal (mainly sodium and potassium) catalysts or mixtures of catalysts can be used. The following catalysts are preferably used: potassium acetate solution in ethylene glycol, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine, 2- [2-
(dimethylamino) ethoxy] ethanol, Dabco 33 LV (solution of 1 ,4-diazabicyclo [2.2.2] octane in ethylene glycol), tin 2-ethylhexanoate, N, N-dimethylcyclohexylamine (DMCHA), dibutyltin dilaurate or mixture of these substances. The following blowing agents are preferably used: 1,1,1,3,3-pentafluorobutane, n-pentane, cyclopentane, cyclohexane, dichloromethane, water.
The following surfactants are preferably used: polysiloxane-modified polyethers (trade name Tegostab 8537, Tegostab 8465, Tegostab 8460), polysiloxanes, silicone oils, silicone glycol copolymer.
The following anti-foaming agents are preferably used: mixtures of different agents (trade name: Chemax DF -10A, Chemax DFO-400, EXOantifoam CPD3), EO / PO block copolymers (ethylene oxide / propylene oxide) (trade name: ROKAmer 2000, ROKAmer 2000S, ROKAmer 2600S ), mixtures of mineral oils (trade name: HE®-COAT-DF 691, CHE®-COAT-DF 581B), mixtures of silicone oils (trade name: CHE DF 9022).
Preference to use as a filler is given to the milled waste after wood processing, such as: bark, wood chips, sawdust, wood dust, wood shavings, and wood-like waste from wood processing, such as: fibreboard waste, MDF board waste, HDF board waste, chipboard waste, waste OSB boards or waste plywood boards with grain size from 0.1 mpi-500 pm.
The following isocyanates are preferred to use: 4,4-diphenylmethane diisocyanate (MDI), 2,4-toluene diisocyanate (TDI), 1,6-hexamethylene diisocyanate (HDI), polymeric 4,4-diphenylmethane diisocyanate (pMDI).
The advantage of new polyurethane materials obtained from wood waste and wood-like waste is a competitive price and a less harmful production process compared to petrochemical oligomerols. According to the invention, the advantage of the new polyurethane materials is the possibility of foaming the polyurethane composition with water, which reacts with the isocyanate group to form carbon dioxide, or foaming by hydrophobic blowing agents, pentane and its derivatives, as well as mixtures of the above- mentioned blowing agents. The advantage of such a mixture is the reduction of the amount of flammable pentane by replacing it with water.
The example describes the production of polyurethane materials using synthesized polyols from wood waste and / or wood-like waste containing milled waste and / or petrochemical polyols.
Example 1. The material was prepared as follows: 70 parts by mass of a petrochemical polyol - sorbitol oxypropoxylation product (Rokopol RF 551) and 30 parts of a reactive polyol obtained from a liquefaction of particle board with a hydroxyl number LOH = 530 mg KOH / g were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 1.5 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 1.5 parts by mass; surfactant (Tegostab 8460 - polysiloxane modified polyester) and whole mixture was homogenized. Then, the filler was added to the mixture in the form of milled waste (bark) with a grain size of 0.1 pm (0.1 parts by mass) and a foaming agent in the form of: 1,1,1,3,3-pentafluorobutane (10 parts by mass) and water (2 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 2/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 22 °C and a pressure of 1.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane foam. The characteristics were checked and its receipt was confirmed - the foam has a density of 50 kg / m3.
Example 2. The material was made similarly to example 1, except that 70 parts by mass of petrochemical polyol, sorbitol oxypropoxylation product (Rokopol RF 551) and 30 parts of reactive polyolobtained from MDF board with a hydroxyl number LOH = 750 mg KOH / g were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol ( 2.5 parts by mass), 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 5 parts by mass; surfactant (Tegostab 8460 - polysiloxane modified polyester) and whole mixture was homogenized. Then, the filler was added to the mixture in the form of milled waste (bark) with a grain size of 60-150 mpi (40 parts by mass) and a foaming agent in the form of: 1 ,1 ,1 ,3,3-pentafluorobutane (10 parts by mass) and water (2 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 3/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 21 °C and a pressure of 1.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane foam. The characteristics were checked and its receipt was confirmed - the foam has a density of 60 kg / m3.
Example 3. The material was made similarly to example 1, except that 90 parts by mass of petrochemical polyol, sorbitol oxypropoxylation product (Rokopol RF 551) and 10 parts of reactive polyol which were obtained from MDF board with a hydroxyl number LOH = 750 mg KOH / g were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol (10 parts by mass); surfactant (20 parts by mass Tegostab 8460 - polysiloxane modified polyester) and the whole mixture was homogenized. Then, the filler was added to the mixture in the form of milled waste (wood shavings) with a grain size of 160-240 pm (30 parts by mass) and a foaming agent in the form of: 1,1,1,3,3-pentafluorobutane (10 parts by mass) and water (2 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 2,5/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 21 °C and a pressure of 1.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane foam. The characteristics were checked and its receipt was confirmed - the foam has a density of 70 kg / m3.
Example 4. The material was made similarly to example 1, except that no reactive polyol from a wood-based or wood-like material was used. To the 100 parts by mass petrochemical polyol (sorbitol oxypropoxylation product - Rokopol RF 551) auxiliary compounds were added: catalysts: 33% solution of potassium acetate in ethylene glycol (1,5 parts by mass), 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine (1,5 parts by mass); surfactant (4 parts by mass Tegostab 8460 - polysiloxane modified polyester) and whole mixture was homogenized. Then, the filler was added to the mixture in the form of milled waste (wood shavings) with a grain size of 50-160 pm (10 parts by mass) and a foaming agent in the form of: 1,1,1,3,3-pentafluorobutane (10 parts by mass) and water (2 parts by mass). The obtained premix was thoroughly homogenized. Then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 3/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 22 °C and a pressure of 1.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane foam. The characteristics were checked and its receipt was confirmed - the foam has a density of 45 kg /m3.
Example 5. The material was prepared as follows: 70 parts by mass of a petrochemical polyol - sorbitol oxypropoxylation product (Rokopol RF 551) and 30 parts of petrochemical polyol (Rokopol M6000) were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 1.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-1,3,5- triazine in an amount of 2.5 parts by mass; surfactant (Tegostab 8460 - polysiloxane modified polyester) in an amount of 4.0 parts and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood-like waste (MDF board ) with a grain size of 160-240 pm (40 parts by mass) and a foaming agent in the form of: 1, 1,1, 3,3- pentafluorobutane (10 parts by mass) and water (2 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 3/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 22 °C and a pressure of 1.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane foam. The characteristics were checked and its receipt was confirmed - the foam has a density of 70 kg / m3.
Example 6. The material was prepared as follows: 70 parts by mass of a petrochemical polyol - sorbitol oxypropoxylation product (Rokopol RF 551) and 30 parts of petrochemical polyol (Rokopol M6000) were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 1.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro- 1,3,5 - triazine in an amount of 2.5 parts by mass and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood-like waste (MDF board ) with a grain size of 160-240 pm (40 parts by mass) and a foaming agent in the form of: 1, 1,1, 3,3- pentafluorobutane (10 parts by mass) and water (2 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 3/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 22 °C and a pressure of 1.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane foam. The characteristics were checked and its receipt was confirmed - the foam has a density of 80 kg / m3.
Example 7. The material was prepared as follows: 50 parts by mass of a petrochemical polyol - sorbitol oxypropoxylation product (Rokopol RF 551) and 50 parts of petrochemical polyol (Rokopol M6000) were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 1.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-1,3,5- triazine in an amount of 2.5 parts by mass; surfactant (Tegostab 8460 - polysiloxane modified polyester) in an amount of 5.0 parts and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood-like waste (OSB board) with a grain size of 160-240 pm (40 parts by mass) and a foaming agent in the form of: 1, 1,1, 3,3- pentafluorobutane (10 parts by mass) and water (2 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 2.5/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 22 °C and a pressure of 1.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane foam. The characteristics were checked and its receipt was confirmed - the foam has a density of 50 kg / m3.
Example 8. The material was prepared as follows: 50 parts by mass of a petrochemical polyol - sorbitol oxypropoxylation product (Rokopol RF 551) and 50 parts of petrochemical polyol (Rokopol M6000) were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 1.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-1,3,5- triazine in an amount of 2.5 parts by mass and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood-like waste (OSB board ) with a grain size of 160-240 pm (20 parts by mass) and a foaming agent in the form of: 1,1, 1,3 ,3- pentafluorobutane (10 parts by mass) and water (2 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 2.5/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 22 °C and a pressure of 1.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane foam. The characteristics were checked and its receipt was confirmed - the foam has a density of 70 kg / m3.
Example 9. The material was prepared as follows: 100 parts of a reactive polyol obtained from a liquefaction of MDF board with a hydroxyl number LOH = 750 mg KOH / g: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 10.0 parts by mass, surfactant (Tegostab 8460 - polysiloxane modified polyester) in an amount of 20.0 parts and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood shavings with a grain size of 60-150 pm (15 parts by mass) and a foaming agent in the form of: 1,1,1,3,3-pentafluorobutane (10 parts by mass) and water (2 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 2.5/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 22 °C and a pressure of 1.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane foam. The characteristics were checked and its receipt was confirmed - the foam has a density of 65 kg / m3.
Example 10. The material was prepared as follows: 100 parts of a reactive polyol obtained from a liquefaction of MDF board with a hydroxyl number LOH = 750 mg KOH / g: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 10.0 parts by mass, surfactant (Tegostab 8460 - polysiloxane modified polyester) in an amount of 20.0 parts and whole mixture was homogenized. Then, foaming agent in the form of: 1,1,1,3,3-pentafluorobutane (10 parts by mass) and water (2 parts by mass) were added. Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 2.5/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 21 °C and a pressure of 1.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane foam. The characteristics were checked and its receipt was confirmed - the foam has a density of 35 kg / m3.
Example 11. The material was prepared as follows: 1 parts by mass of a petrochemical polyol - sorbitol oxypropoxylation product (Rokopol RF 551) and 99 parts of a reactive polyol obtained from a liquefaction of HDF board with a hydroxyl number LOH = 630 mg KOH / g were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 2.5 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 2.5 parts by mass; surfactant (Tegostab 8460 - polysiloxane modified polyester) in an amount of 15.0 parts and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood dust with a grain size of 0.1-50 pm (40 parts by mass) and a foaming agent in the form of: n-pentane (10 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.5/1. Premix with isocyanate was mixed for 10 seconds. The cross- linking and curing process was carried out at a temperature of 22 °C and a pressure of 1.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane foam. The characteristics were checked and its receipt was confirmed - the foam has a density of 60 kg / m3.
Example 12. The material was prepared as follows: 10 parts by mass of a petrochemical polyol - sorbitol oxypropoxylation product (Rokopol RF 551) and 90 parts of a reactive polyol obtained from a liquefaction of plywood panel with a hydroxyl number LOH = 630 mg KOH / g were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 3.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 4.0 parts by mass; surfactant (Tegostab 8460 - polysiloxane modified polyester) in an amount of 18.0 parts and whole mixture was homogenized. Then, the filler was added to the mixture in the form of chipboard with a grain size of 360-500 pm (60 parts by mass) and a foaming agent in the form of: n-pentane (10 parts by mass) and water (5 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 2.5/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 22 °C and a pressure of 1.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane foam. The characteristics were checked and its receipt was confirmed - the foam has a density of 65 kg / m3.
Example 13. The material was prepared as follows: 10 parts by mass of a petrochemical polyol - sorbitol oxypropoxylation product (Rokopol RF 551) and 90 parts of a reactive polyol obtained from a liquefaction of plywood panel with a hydroxyl number LOH = 630 mg KOH / g were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 3.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 4.0 parts by mass; surfactant (Tegostab 8460 - polysiloxane modified polyester) in an amount of 18.0 parts and whole mixture was homogenized. Then, the foaming agent in the form: n- pentane (10 parts by mass) and water (5 parts by mass) were added. Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 2.5/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 22 °C and a pressure of 1.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane foam. The characteristics were checked and its receipt was confirmed - the foam has a density of 35 kg / m3.
Example 14. The material was prepared as follows: 1 parts by mass of a petrochemical polyol - sorbitol oxypropoxylation product (Rokopol RF 551) and 99 parts of a reactive polyol obtained from a liquefaction of plywood panel with a hydroxyl number LOH = 630 mg KOH / g were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 1.5 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 1.5 parts by mass; surfactant (Tegostab 8460 - polysiloxane modified polyester) in an amount of 4.0 parts and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood-like waste (MDF board ) with a grain size of 50-160 pm (50 parts by mass) and a foaming agent in the form of: 1,1,1,3,3-pentafluorobutane (10 parts by mass) and water (2 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 2.5/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 22 °C and a pressure of 1.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane foam. The characteristics were checked and its receipt was confirmed - the foam has a density of 41 kg / m3. It is a material obtained from petrochemical and reactive polyols nto which shredded wood waste or wood-like waste was introduced as a filler. Example 15. The material was prepared as follows: 50 parts by mass of a petrochemical polyol - sorbitol oxypropoxylation product (Rokopol RF 551) and 50 parts of a reactive polyol obtained from a liquefaction of OSB board with a hydroxyl number LOH = 510 mg KOH / g were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 1.5 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 1.5 parts by mass; surfactant (Tegostab 8460 - polysiloxane modified polyester) in an amount of 4.0 parts and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood-like waste (HDF board ) with a grain size of 50-160 pm (20 parts by mass) and a foaming agent in the form of: 1,1,1,3,3-pentafluorobutane (10 parts by mass) and water (2 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 2.2/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 22 °C and a pressure of 1.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane foam. The characteristics were checked and its receipt was confirmed - the foam has a density of 48 kg / m3. It is a material obtained from petrochemical and reactive polyols nto which shredded wood waste or wood-like waste was introduced as a filler.
Example 16. The material was prepared as follows: 5 parts by mass of a petrochemical polyol - (Rokopol M6000) and 95 parts of a reactive polyol obtained from a liquefaction of chipboard with a hydroxyl number LOH = 520 mg KOH / g were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 1.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 1.0 parts and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood-like waste (OSB board ) with a grain size of 240-360 pm (100 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.1/1. Premix with isocyanate was mixed for 10 seconds. The cross- linking and curing process was carried out at a temperature of 110 °C and a pressure of 30.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 13.3 MPa Example 17 The material was prepared as follows: 1 parts by mass of a petrochemical polyol - (Rokopol M6000) and 99 parts of a reactive polyol obtained from a liquefaction of chipboard with a hydroxyl number LOH = 520 mg KOH / g were mixed. Them, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 5.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 5.0 parts by mass, flame retardants (copolymer EO/PO) in an amount of 0.5 parts of mass and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood waste (bark) with a grain size of 360- 500 pm (200 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.1/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 110 °C and a pressure of 30.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 14.3 MPa
Example 18 The material was prepared as follows: 100 parts by mass of a petrochemical polyol - (Rokopol M6000) and catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 5.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 5.0 parts by mass, flame retardants (copolymer EO/PO) in an amount of 0.5 parts of mass and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood waste (bark) with a grain size of 60- 150 pm (200 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.1/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 110 °C and a pressure of 30.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 14.3 MPa
Example 19. The material was prepared as follows: 100 parts of a reactive polyol obtained from a liquefaction of chipboard with a hydroxyl number LOH = 520 mg KOH / g; catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 5.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 5.0 parts by mass, flame retardants (copolymer EO/PO) in an amount of 0.5 parts of mass and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood -like waste (beaverboard) with a grain size of 1-50 pm (200 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.3/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 120 °C and a pressure of 20.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 13.3 MPa Example 20. The material was prepared as follows: 100 parts of a reactive polyol obtained from a liquefaction of chipboard with a hydroxyl number LOH = 520 mg KOH / g; catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 5.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 5.0 parts by mass, and whole mixture was homogenized, Then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.3/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 120 °C and a pressure of 20.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 17.3 MPa Example 21. The material was prepared as follows: 1 parts by mass of a petrochemical polyol - (Rokopol M6000) and 99 parts of a reactive polyol obtained from a liquefaction of bark with a hydroxyl number LOH = 780 mg KOH / g were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 5.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 5.0 parts by mass, flame retardants (copolymer EO/PO) in an amount of 5.0 parts of mass and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood waste (wood dust) with a grain size of 1-50 pm (400 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.1/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 110 °C and a pressure of 30.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 19.3 MPa.
Example 22. The material was prepared as follows: 2 parts by mass of a petrochemical polyol - (Rokopol M6000) and 98 parts of a reactive polyol obtained from a liquefaction of wood chips with a hydroxyl number LOH = 640 mg KOH / g were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 5.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 5.0 parts by mass, flame retardants (mixture of mineral oils) in an amount of 2.5 parts of mass and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood-like waste (MDF board) with a grain size of 50-160 pm (400 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.1/1. Premix with isocyanate was mixed for 10 seconds. The cross- linking and curing process was carried out at a temperature of 160 °C and a pressure of 25.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 11.3 MPa
Example 23. The material was prepared as follows: 5 parts by mass of a petrochemical polyol - (Rokopol M6000) and 95 parts of a reactive polyol obtained from a liquefaction of wood dust with a hydroxyl number LOH = 515 mg KOH / g were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 5.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 5.0 parts by mass, flame retardants (mixture of mineral oils) in an amount of 2.5 parts of mass and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood waste (wood dust) with a grain size of 0.1-50 pm (900 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.1/1. Premix with isocyanate was mixed for 10 seconds. The cross- linking and curing process was carried out at a temperature of 160 °C and a pressure of 25.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 1.3 MPa Example 24. The material was prepared as follows: 90 parts by mass of a petrochemical polyol - (Rokopol M6000) and 10 parts of a reactive polyol obtained from a liquefaction of wood shavings with a hydroxyl number LOH = 650 mg KOH / g were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 1.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 2.0 parts by mass and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood waste (wood shavings) with a grain size of 50-150 pm (800 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.1/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 150 °C and a pressure of 25.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 2.3 MPa
Example 25. The material was prepared as follows: 100 parts by mass of a petrochemical polyol - (Rokopol RF 551) and catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 2.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 1.5 parts by mass and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood-like waste (OSB board) with a grain size of 150-240 pm (500 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.1/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 20 °C and a pressure of 10.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 9.3 MPa
Example 26. The material was prepared as follows: 50 parts by mass of a petrochemical polyol - (Rokopol M6000) and 50 parts of a petrochemical polyol - (Rokopol RF 551) were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 2.0 parts by mass, 1,3,5- tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 1.5 parts by mass; flame retardants (copolymer EO/PO) in the amount 1.5 parts by mass and whole mixture was homogenized. Then, the filler was added to the mixture in the form of woodlike waste (plywood panels) with a grain size of 250-360 pm (400 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.1/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 100 °C and a pressure of 15.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 10.3 MPa
Example 27. The material was prepared as follows: 5 parts by mass of a petrochemical polyol - (Rokopol M6000) and 20 parts of a petrochemical polyol - (Rokopol RF 551) and 75 parts of a reactive polyol obtained from a liquefaction of OSB board with a hydroxyl number LOH = 510 mg KOH / g were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 1.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 1.0 parts by mass and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood-like waste (HDF board) with a grain size of 360- 500 pm (900 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.5/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 180 °C and a pressure of 35.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 1.3 MPa
Example 28. The material was prepared as follows: 99 parts by mass of a petrochemical polyol - (Rokopol M6000) and 1 parts of a reactive polyol obtained from a liquefaction of OSB board with a hydroxyl number LOH = 510 mg KOH / g were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 4.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 2.0 parts by mass and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood-like waste (HDF board) with a grain size of 360-500 pm (200 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.5/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 120 °C and a pressure of 35.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 9.3 MPa
Example 29. The material was prepared as follows: 10 parts by mass of a petrochemical polyol - (Rokopol M 6000) and 90 parts of a reactive polyol obtained from a liquefaction of OSB board with a hydroxyl number LOH = 510 mg KOH / g were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 4.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 2.0 parts by mass and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood-like waste (MDF board) with a grain size of 240-350 pm (100 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.7/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 140 °C and a pressure of 35.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 10.3 MPa Example 30. The material was prepared as follows: 5 parts by mass of a petrochemical polyol - (Rokopol M6000) and 95 parts of a reactive polyol obtained from a liquefaction of OSB board with a hydroxyl number LOH = 510 mg KOH / g were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 2.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 1.5 parts by mass and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood-like waste (MDF board) with a grain size of 240-350 pm (50 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.4/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 60 °C and a pressure of 35.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 16.3 MPa Example 31. The material was prepared as follows: 3 parts by mass of a petrochemical polyol - (Rokopol M6000) and 97 parts of a reactive polyol obtained from a liquefaction of OSB board with a hydroxyl number LOH = 510 mg KOH / g were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 1.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 1.5 parts by mass and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood-like waste (chipboard) with a grain size of 240-350 pm (100 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.4/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 21 °C and a pressure of 1.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 14.3 MPa.
Example 32. The material was prepared as follows: 3 parts by mass of a petrochemical polyol - (Rokopol M6000) and 97 parts of a reactive polyol obtained from a liquefaction of OSB board with a hydroxyl number LOH = 510 mg KOH / g were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 1.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 1.5 parts by mass and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood-like waste (chipboard) with a grain size of 240-350 pm (0.5 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.4/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 21 °C and a pressure of 1.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 16.3 MPa Example 33. The material was prepared as follows: 1 parts by mass of a petrochemical polyol - (Rokopol M6000) and 99 parts of a reactive polyol obtained from a liquefaction of MDF board with a hydroxyl number LOH = 750 mg KOH / g were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 2.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 1.5 parts by mass; flame retardansts in an amount 3.5 parts of mass and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood-like waste (MDF board) with a grain size of 60-150 mpi (1.0 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.4/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 21 °C and a pressure of 1.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 15.3 MPa
Example 34. The material was prepared as follows: 50 parts by mass of a petrochemical polyol - (Rokopol M6000) and 50 parts of a reactive polyol obtained from a liquefaction of MDF board with a hydroxyl number LOH = 750 mg KOH / g were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 1.5 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 1.5 parts by mass and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood-like waste (MDF board) with a grain size of 60-150 mih (10.0 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.2/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 21 °C and a pressure of 1.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 8.3 MPa Example 35. The material was prepared as follows: 50 parts by mass of a petrochemical polyol - (Rokopol M6000) and 50 parts of a reactive polyol obtained from a liquefaction of chipboard with a hydroxyl number LOH = 450 mg KOH / g were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 7.5 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro- 1 ,3 ,5 -triazine in an amount of 3.5 parts by mass and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood- like waste (MDF board) with a grain size of 150-240 pm (300.0 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.5/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 10O °C and a pressure of 5.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 12.3 MPa.
Example 36. The material was prepared as follows: 5 parts by mass of a petrochemical polyol - (Rokopol M6000) and 95 parts of a reactive polyol obtained from a liquefaction of plywood panel with a hydroxyl number LOH = 630 mg KOH / g were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 1.5 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 1.5 parts by mass and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood-like waste (beaverboard) with a grain size of 150-240 pm (400.0 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.2/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 100 °C and a pressure of 50.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 18.3 MPa. Example 37. The material was prepared as follows: 5 parts by mass of a petrochemical polyol - (Rokopol M6000) and 95 parts of a reactive polyol obtained from a liquefaction of HDF board with a hydroxyl number LOH = 630 mg KOH / g were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 1.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 1.0 parts by mass and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood-like waste (HDF board) with a grain size of 250-360 pm (300.0 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.1/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 100 °C and a pressure of 50.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 17.3 MPa. Example 38. The material was prepared as follows: 5 parts by mass of a petrochemical polyol - (Rokopol M6000) and 95 parts of a reactive polyol obtained from a liquefaction of MDF board with a hydroxyl number LOH = 550 mg KOH / g were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 1.0 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 1.0 parts by mass and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood waste (wood shavings) with a grain size of 150-240 pm (800.0 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.3/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 150 °C and a pressure of 50.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 1.3 MPa. Example 39. The material was prepared as follows: 2 parts by mass of a petrochemical polyol - (Rokopol M6000) and 98 parts of a reactive polyol obtained from a liquefaction of plywood board with a hydroxyl number LOH = 630 mg KOH / g were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 1.5 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 1.5 parts by mass and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood waste (bark) with a grain size of 60-150 pm (500.0 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.2/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 100 °C and a pressure of 50.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 3.3 MPa.
Example 40. The material was prepared as follows: 3 parts by mass of a petrochemical polyol - (Rokopol M6000) and 97 parts of a reactive polyol obtained from a liquefaction of plywood board with a hydroxyl number LOH = 630 mg KOH / g were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 2.5 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 2.5 parts by mass and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood waste (wood chips) with a grain size of 150-240 pm (150.0 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 1.2/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 23 °C and a pressure of 1.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 11.3 MPa.
Example 41. The material was prepared as follows: 40 parts by mass of a petrochemical polyol - (Rokopol M6000) and 60 parts of a reactive polyol obtained from a liquefaction of plywood board with a hydroxyl number LOH = 630 mg KOH / g were mixed. Then, auxiliary compounds were added to the mixture: catalysts: 33% solution of potassium acetate in ethylene glycol in the amount of 1.5 parts by mass, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine in an amount of 4.5 parts by mass and whole mixture was homogenized. Then, the filler was added to the mixture in the form of wood-like waste (plywood board) with a grain size of 150-240 pm (200.0 parts by mass). Obtained premix was thoroughly homogenized, then isocyanate (pMDI) was added in an amount that the molar ratio of NCO / OH groups was 2.0/1. Premix with isocyanate was mixed for 10 seconds. The cross-linking and curing process was carried out at a temperature of 70 °C and a pressure of 3.0 bar. According to the example, a polyurethane material was obtained in the form of polyurethane resin. The characteristics were checked and its receipt was confirmed - the resin has a flexural strength of 11.3 MPa.

Claims

Claims
1. Method of manufacturing new polyurethane materials from reactive polyols obtained from wood and / or wood-like waste, characterized in that the polyols are synthesized from wood waste, and/or polyols synthesized from wood-like waste, and/or petrochemical polyols are used, while the polyol mixture is being prepared by mixing 1-100 parts by mass of polyols obtained from wood waste, and/or 1-100 parts by mass of polyols obtained from wood-like waste and/or 1-100 parts by mass of petrochemical oligomerols and moreover 0.01-10 parts by mass of catalysts, and 0-20 parts by mass of surfactants, and 0-20 parts by mass of anti-foaming agent, and 0-20 parts by mass of blowing agents and 0-900 parts by mass of milled waste after wood processing or 0-900 parts by mass of shredded waste wood-like, after that the obtained polyol mixture is mixed with isocyanate, molar ratio of NCO / OH ranging from 0.5 to 4, and then wood waste and/or wood-like waste are introduced into the polyurethane system.
2. Method according to claim 1, wherein polyols obtained from wood-like and / or wood-based waste are used, which have physical properties such as hydroxyl number from 50 to 800 mg KOH / g, acid number from 0.1 to 20 mg KOH / g, molecular weight from 30 g / mol to 7,000 g / mol and functionality from 1 to 4, then cross-linking and gelation of the material are carried out at room temperature and normal pressure and / or at a temperature below the degradation temperature and elevated pressure.
3. Method according to claims 1-2, wherein the reactive polyols obtained from wood waste and / or wood-like waste are used, the polyols are obtained in the thermochemical liquefaction process using a temperature of 80 to 300 °C, time from 60 to 600 min, and from 1 to 50 wt.% of waste to the total mass of the solvent.
4. Method according to claim 1, wherein wood-based waste is used while wood- based waste is in a form of bark or wood chips or sawdust or wood dust or wood shavings, which are milled to a specific grain size.
5. Methods according to claim 1, wherein wood-like waste is used in the form of fibreboards, MDF board, HDF boards, particle boards, oriented chipboards, which are milled to a specific size.
6. Method according to claims 1-5, wherein waste with the grain size from 0.1 mhi to 500 mih is used.
7. Method according to claim 1, wherein as polyols petrochemical oligomerols (polyether and / or polyester polyols) with molecular weight from 200 to 7000 g / mol and a hydroxyl number of 28 to 600 mgKOH / g and a functionality of from 1 to 6 are used.
8. Method according to claim 1, wherein cross-linking and gelling process is performed at a temperature from 20 °C to 180 °C and pressure from 0.9 to 50 bar.
9. Method according to claim 1, wherein an amine catalyst and/or organometallic and/or metal salt catalyst, or a mixture of different catalysts is used.
10. Method according to claim 1, wherein the following substance or their mixture as a catalyst is used: solution of potassium acetate in ethylene glycol, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro-l,3,5-triazine, 2- [2 - (dimethylamino) ethoxy] ethanol, Dabco 33 LV (1,4-diazabicyclo [2.2.2] octane solution in ethylene glycol), tin 2-ethylhexanoate, N, N-dimethylcyclohexylamine (DMCHA), dibutytin dilaurate.
11. Method according to claim 1, wherein the following substance or their mixture as the blowing agent is used: 1,1,1,3,3-pentafluorobutane, n-pentane, cyclopentane, cyclohexane, dichloromethane and / or water.
12. Method according to claim 1, wherein polysiloxane-modified poly ether, polysiloxanes, silicone oils, and / or a silicone glycol copolymer is as surfactant.
13. Method according to claim 1, wherein block copolymer of ethylene oxide and/or propylene oxide, a mixture of mineral oils, a mixture of silicone oils and/or mixture of abovementioned compounds is used as antifoaming agents.
14. Method according to claim 1, wherein the following substance or their mixture as the isocyanates is used: 4,4-diphenylmethane diisocyanate (MDI), 2,4-toluene diisocyanate (TDI), 1,6-hexamethylene diisocyanate (HDI) and/or polymeric 4,4- diphenylmethane diisocyanate (pMDI).
PCT/PL2021/000011 2020-03-10 2021-02-25 Method of manufacturing polyurethane materials from reactive polyols and polyols obtainable from waste after processing wood or wood-like waste WO2021182980A1 (en)

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