WO2021173018A1

WO2021173018A1 - The method of obtaining reactive polyols from wood-based waste, the method of manufacturing polyurethane materials from the obtained reactive polyols and reactive polyols obtained from wood-based materials

Info

Publication number: WO2021173018A1
Application number: PCT/PL2021/000009
Authority: WO
Inventors: Lukasz Piszczyk; Paulina Kosmela; Jozef Haponiuk
Original assignee: Politechnika Gdanska
Priority date: 2020-02-24
Filing date: 2021-02-18
Publication date: 2021-09-02
Also published as: PL433009A1; EP4110856A4; EP4110856A1; PL244152B1

Abstract

The invention relates to a process for the production of reactive polyols from wood-like waste materials on the fact that the wood-like waste material is used as a wood-like material, which is chipped to a grain size of 1 to 500 pm, and this material is subjected to a solvolysis process in the presence of a solvent or mixture of solvents with the amount of biomass from 1-50% of the weight of the solvent with the catalyst at the temperature from 80 to 300 ° C and the obtained polyol raw material is neutralized with an acid or a base.

Description

The method of obtaining reactive polyols from wood-based waste, the method of manufacturing polyurethane materials from the obtained reactive polyols and reactive polyols obtained from wood-based materials

The invention refers to a method of obtaining new reactive polyols from wood- based waste from wood processing, such as: fiberboard waste, MDF board waste, HDF board waste, chipboard waste, OSB waste, and plywood waste, and polyols obtained from wood-based materials. The invention also refers to a method of producing - manufacturing of polyurethane materials using obtained polyols. The invention can be used in the construction, furniture, and automotive industries.

Wood materials is one of the oldest materials used by humans, originally used as a source of energy and a valuable building material. For centuries, wood as a valuable raw material has been widely used in the industry, e.g., in construction. Excellent properties give the wood high popularity and various uses. The advantages of wood, such as renewability, excellent properties to use as a construction material, good thermal insulation properties, a beneficial effect on the energy balance, and low environmental impact make the wood industry increasingly important in economic and social terms. This is positively influenced by the size of the country and the high level of development of wood-based industries. Large exports of processed wood, high quality of production, and modem products make Polish products attractive for foreign investors. As a consequence of the development of the wood industry, an increase can also be noted in the amount of wood waste, which has been used for many years for industrial production and as the energy carrier. The dynamic development of the fibreboard and wood-based industry as well as the pulp and paper industry made wood waste a full- value industrial raw material. The amount of waste generated during mechanical processing is very large and, in many cases, exceeds the weight of the finished product components. Therefore, part of the wood waste from wood industry is used for the production of board materials, and the rest is used in agriculture and horticulture and as fuel for energy purposes.

The processing and processing of wood in the factories makes it possible to use the raw material for the production of wood-based panels. Such boards include: fibreboards, chipboards, OSB, and plywood. Wood-based panels are a group of composite products, which are a type of structural wood materials. They are made using a combination of pressure and high temperature during hot pressing of wood waste and different kinds of resins. The process involves ligno-cellulose particles in the form of veneer sheets, shavings, sawdust, shavings, 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 fiber - fibre boards, and made of veneer sheet - plywood.

Due to the excessive amount of waste produced, many wood industry plants use practices related to the 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 substrate with a specific grain size (wood-based waste/wood-like waste), type of catalyst, time, and temperature of the process were selected. These parameters make the process effective and make it possible to obtain valuable materials that can be further used in industry.

The best results are obtained when using shredded wood-like waste from 1 pm to 500 pm. Preferably, waste from fibreboards, MDF (Medium-Density Fibreboard), HDF (High Density Fibreboard), particle board, OSB (Oriented Strand Board), which are crushed to a certain size. The material is subjected to a solvolysis/liquefaction reaction in the presence of a solvent such as alcohols, glycols, and catalysts (1. acidic; 2. basic, 3. acidic and then basic; 4. basic and then acidic).

According to the invention to obtain new raw materials, a thermochemical solvolysis process is used in the presence of solvents and a catalyst.

Importantly, in the solvolysis process of wood-like waste, acid catalysis, base, acid-base or base-acid catalysis are used.

According to the invention, 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.

It is preferred to use a solvent or mixture of solvents such as methanol, ethanol, propanol, butanol, pentanol, hexanol, diols such as ethane- 1,2-diol, propane- 1, 3 -diol, propane- 1,2- diol, butane -1,3-diol, butane- 1,4-diol, butane-2, 3-diol, 2,2'-oxydiethanol, and propane- 1, 2,3 -triol, butane- 1,2, 3, 4 - tetraol (erythritol), pentane-l,2,3,4,5-pentaol (ribitol), poly (ethylene oxide) with a molecular weight of 200 to 6000 g / mol, ethylene carbonate, waste glycerol, crude glycerol, water and phenol and their mixtures.

It is preferred to use concentrated catalysts such as: potassium hydroxide, sodium hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, trihydridonitrogen (ammonia), sulfuric acid (IV), sulfuric acid (VI), orthophosphoric acid, hydrochloric acid, nitric acid (III %), nitric acid (V), chloric acid (III), chloric acid (V), chloric acid (VII) in an amount from 0.01 to 10% by weight, with respect to the solvent used.

The new polyols according to the invention 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.

The advantage of the new polyols according to the invention is the possibility of obtaining them in the thermochemical liquefaction process in the presence of basic catalysts or acidic, acidic and then basic or basic and then acidic catalysts, which allows for high waste conversion.

The advantage of the invention is also the elimination of the final stage of purification of new raw materials from solid residues of solvolysis reaction products using low-molecular alcohols, which significantly affects the economics of the solvolysis process.

The advantage of the invention 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, the new polyurethane materials are based on a polyol mixture component, which is a polyol obtained in the solvolysis process of wood-like waste. The polyols obtained according to the above-described method are used in the production of polyurethane materials. According to this invention, a polyol mixture is prepared by mixing 1-99 parts by mass of polyols obtained from wood-like waste, and 1- 99 parts by the mass of petrochemical oligomerols, and 0.01-10 parts by mass of catalysts in the form of amine and organometallic catalysts and / or metal salts and 0.1-20 parts by mass of surfactants and 1-20 parts by mass of blowing agents. Then it is mixed with 1-90 parts by a mass of the isocyanate.

It is preferred to use the isocyanate in the form of an aromatic, 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.

The method of obtaining new polyurethane materials consists in cross-linking and curing the materials 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 advantage of new polyurethane materials obtained from wood-like waste is a competitive price and a less harmful production process in comparison to production of materials using petrochemical oligomerols.

The advantage of the new polyurethane materials according to the invention is the possibility of foaming the polyurethane composition with water, which reacts with the isocyanate group to form carbon dioxide, or hydrophobic blowing agents, pentane and its derivatives, as well as mixtures of the above-mentioned blowing agents.

The advantage of such a mixture is reduction of the amount of flammable pentane by partially replacing it with water.

It is preferable to use amine catalysts (mainly tertiary amines), organometallic (mainly organotin) and metal salts (mainly sodium and potassium) or mixtures of these substances.

The following catalysts are preferably used: potassium acetate solution in ethylene glycol, 1,3,5-tris [3- (dimethylamino) propyl] hexahydro- 1 ,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 isocyanates are preferred: 4,4-diphenylmethane diisocyanate (MDI), 2,4-toluene diisocyanate (TDI), 1 ,6-hexamethylene diisocyanate (HDI), polymeric 4,4- diphenylmethane diisocyanate (pMDI). The invention is described in more detail in the examples.

Example 1. To 1000 g of crude glycerol, 100 g of milled wood-like waste (fibreboard) with a grain size of 60-150 pm and 30 g of H₃PO₄ are added, followed by heating, and stirring, gradually to 170 °C in a reactor equipped with a condenser (distillation). The process is carried out until the formation of distillate condensation ceases (reaction time 240 min), then the mixture is cooled to 50 °C and 2 M aqueous solution of KOH solution is added until the mixture reaches the pH value of 7. Then the whole mixture is heated to the temperature of 120 °C under reduced pressure to remove excess water. This process is continued until the mixture stabilizes. According to the example, 1000 g of polyol with a hydroxyl number of 855 ± 10 mgKOH / g, and an acid number of 1.2 mg of KOH / g, and a functionality of 4 are obtained.

Example 2. To 1000 g of poly(ethylene oxide) with a molecular weight of 400 g/mol 300 g of milled wood-like waste (chipboard) with a grain size of 60-150 pm and 20 g of H₂SO₄ are added, followed by heating, and stirring, gradually to 170 °C in a reactor equipped with a condenser (distillation). The process is carried out until the formation of distillate condensation ceases (reaction time 240 min), then the mixture is cooled to 50 °C and 2 M aqueous solution of KOH solution is added until the mixture reaches the pH value of 7. Then the whole mixture is heated to the temperature of 120 °C under reduced pressure to remove excess water. This process is continued until the mixture stabilizes. According to the example, 1000 g of polyol with a hydroxyl number of 450 ±10 mgKOH/g, and an acid number of 3.3 mg of KOH / g, and a functionality of 2.4 are obtained.

Example 3. To 1000 g of poly(ethylene oxide) with a molecular weight of 400 g/mol, 200 g of milled wood-like waste (chipboard) with a grain size of 60-150 pm and 20 g of H₃PO₄ are added, followed by heating, and stirring, gradually to 80 °C in a reactor equipped with a condenser (distillation). The process is carried out until the formation of distillate condensation ceases (reaction time 600 min), then the mixture is cooled to 50 °C and 2 M aqueous solution of KOH solution is added until the mixture reaches the pH value of 7. Then the whole mixture is heated to the temperature of 120 °C under reduced pressure to remove excess water. This process is continued until the mixture stabilizes. According to the example, 1000 g of polyol with a hydroxyl number of 600 ±10 mgKOH/g, and an acid number of 2.3 mg of KOH / g, and a functionality of 3.4 are obtained.

Example 4. To 1000 g of crude glycerol, 100 g of milled wood-like waste (MDF board) with a grain size of 240-360 pm and 20 g of H3PO4 are added, followed by heating, and stirring, gradually to 150 °C in a reactor equipped with a condenser (distillation). The process is carried out until the formation of distillate condensation ceases (reaction time 360 min), then the mixture is cooled to 50 °C and 2 M aqueous solution of KOH solution is added until the mixture reaches the pH value of 7. Then the whole mixture is heated to the temperature of 120 °C under reduced pressure to remove excess water. This process is continued until the mixture stabilizes. According to the example, 900 g of polyol with a hydroxyl number of 750 ±10 mgKOH/g, and an acid number of 13 mg of KOH / g, and a functionality of 2.4 are obtained.

Example 5. To 1000 g of crude glycerol, 100 g of milled wood-like waste (MDF board) with a grain size of 1-60 pm and 20 g of H3PO4 are added, followed by heating, and stirring, gradually to 240 °C in a reactor equipped with a condenser (distillation). The process is carried out until the formation of distillate condensation ceases (reaction time 120 min), then the mixture is cooled to 50 °C and 2 M aqueous solution of KOH solution is added until the mixture reaches the pH value of 7. Then the whole mixture is heated to the temperature of 120 °C under reduced pressure to remove excess water. This process is continued until the mixture stabilizes. According to the example, 900 g of polyol with a hydroxyl number of 640 ±10 mgKOH/g, and an acid number of 5,0 mg of KOH / g, and a functionality of 4.0 are obtained.

Example 6. To 1000 g of polyethylene oxide) with a molecular weight of 400 g/mol, 200 g of milled wood-like waste (MDF board) with a grain size of 150-2400 pm and 20 g of H2SO4 are added, followed by heating, and stirring, gradually to 170 °C in a reactor equipped with a condenser (distillation). The process is carried out until the formation of distillate condensation ceases (reaction time 240 min), then the mixture is cooled to 50 °C and 2 M aqueous solution of KOH solution is added until the mixture reaches the pH value of 7. Then the whole mixture is heated to the temperature of 120 °C under reduced pressure to remove excess water. This process is continued until the mixture stabilizes. According to the example, 1100 g of polyol with a hydroxyl number of 550 ±10 mgKOH/g, and an acid number of 12 mg of KOH / g, and a functionality of 2.4 are obtained.

Example 7. To 1000 g of crude glycerol, 100 g of milled wood-like waste (OSB board) with a grain size of 60-150 pm and 30 g of H3PO4 are added, followed by heating, and stirring, gradually to 120 °C in a reactor equipped with a condenser (distillation). The process is carried out until the formation of distillate condensation ceases (reaction time 120 min), then the mixture is cooled to 50 °C and 2 M aqueous solution of KOH solution is added until the mixture reaches the pH value of 7. Then the whole mixture is heated to the temperature of 120 °C under reduced pressure to remove excess water. This process is continued until the mixture stabilizes. According to the example, 1000 g of polyol with a hydroxyl number of 813 ±10 mgKOH/g, and an acid number of 18.0 mg of KOH / g, and a functionality of 5.4 are obtained.

Example 8. To 1000 g of the mixture formed by mixing 500 g of crude glycerine and 500 g of polyethylene oxide) of molecular weight 400 g/mol, 200 g of milled woodlike waste (plywood panel) with a grain size of 160-240 pm and 40 g of H2SO4 are added, followed by heating, and stirring, gradually to 120 °C in a reactor equipped with a condenser (distillation). The process is carried out until the formation of distillate condensation ceases (reaction time 360 min), then the mixture is cooled to 50 °C and 2 M aqueous solution of KOH solution is added until the mixture reaches the pH value of 7. Then the whole mixture is heated to the temperature of 120 °C under reduced pressure to remove excess water. This process is continued until the mixture stabilizes. According to the example, 1100 g of polyol with a hydroxyl number of 630 ±10 mgKOH/g, and an acid number of 14.0 mg of KOH / g, and a functionality of 4.8 are obtained.

Example 9. To 1000 g of the mixture formed by mixing 250 g of crude glycerine and 750 g of polyethylene oxide) of molecular weight 400 g/mol, 200 g of milled woodlike waste (chipboard) with a grain size of 160-240 pm and 40 g of H2SO4 are added, followed by heating, and stirring, gradually to 120 °C in a reactor equipped with a condenser (distillation). The process is carried out until the formation of distillate condensation ceases (reaction time 360 min), then the mixture is cooled to 50 °C and 2 M aqueous solution of KOH solution is added until the mixture reaches the pH value of 7. Then the whole mixture is heated to the temperature of 120 °C under reduced pressure to remove excess water. This process is continued until the mixture stabilizes. According to the example, 1100 g of polyol with a hydroxyl number of 520 ±10 mgKOH/g, and an acid number of 11.0 mg of KOH / g, and a functionality of 2.6 are obtained.

Example 10. To 1000 g of the mixture formed by mixing 250 g of crude glycerine and 750 g of poly(ethylene oxide) of molecular weight 400 g/mol, 200 g of milled woodlike waste (chipboard) with a grain size of 360-500 pm and 40 g of H2SO4 are added, followed by heating, and stirring, gradually to 120 °C in a reactor equipped with a condenser (distillation). The process is carried out until the formation of distillate condensation ceases (reaction time 240 min), then the mixture is cooled to 50 °C and 2 M aqueous solution of KOH solution is added until the mixture reaches the pH value of 7. Then the whole mixture is heated to the temperature of 120 °C under reduced pressure to remove excess water. This process is continued until the mixture stabilizes. According to the example, 1100 g of polyol with a hydroxyl number of 420 ±10 mgKOH/g, and an acid number of 16.0 mg of KOH / g, and a functionality of 4.2 are obtained.

Example 11. To 1000 g of polyethylene oxide) of molecular weight 400 g/mol, 100 g of milled wood-like waste (OSB boards) with a grain size of 60-150 pm and 30 g of ortho-phosphoric acid are added, followed by heating, and stirring, gradually to 120 °C in a reactor equipped with a condenser (distillation). The process is carried out until the formation of distillate condensation ceases (reaction time 240 min), then the mixture is cooled to 50 °C and 2 M aqueous solution of KOH solution is added until the mixture reaches the pH value of 7. Then the whole mixture is heated to the temperature of 120 °C under reduced pressure to remove excess water. This process is continued until the mixture stabilizes. According to the example, 1000 g of polyol with a hydroxyl number of 510 ±10 mgKOH/g, and an acid number of 6.0 mg of KOH / g, and a functionality of 3.3 are obtained.

Example 12. To 1000 g of polyethylene oxide) of molecular weight 1000 g/mol, 500 g of milled wood-like waste (OSB boards) with a grain size of 60-150 pm and 30 g of ortho-phosphoric acid are added, followed by heating, and stirring, gradually to 180 °C in a reactor equipped with a condenser (distillation). The process is carried out until the formation of distillate condensation ceases (reaction time 240 min), then the mixture is cooled to 50 °C and 2 M aqueous solution of KOH solution is added until the mixture reaches the pH value of 7. Then the whole mixture is heated to the temperature of 120 °C under reduced pressure to remove excess water. This process is continued until the mixture stabilizes. According to the example, 1000 g of polyol with a hydroxyl number of 480 ±10 mgKOH/g, and an acid number of 9.0 mg of KOH / g, and a functionality of 4.3 are obtained.

Example 13. To 1000 g of crude glycerol, 100 g of milled wood-like waste (MDF boards) with a grain size of 60-150 pm and 30 g of ortho-phosphoric acid are added, followed by heating, and stirring, gradually to 150 °C in a reactor equipped with a condenser (distillation). The process is carried out until the formation of distillate condensation ceases (reaction time 360 min), then the mixture is cooled to 50 °C and 2 M aqueous solution of KOH solution is added until the mixture reaches the pH value of 7. Then the whole mixture is heated to the temperature of 120 °C under reduced pressure to remove excess water. This process is continued until the mixture stabilizes. According to the example, 1000 g of polyol with a hydroxyl number of 750±10 mgKOH/g, and an acid number of 14.0 mg of KOH / g, and a functionality of 5.6 are obtained.

Example 14. To 1000 g of crude glycerol, 100 g of milled wood-like waste (MDF boards) with a grain size of 60-150 pm and 30 g of ortho-phosphoric acid are added, followed by heating, and stirring, gradually to 80 °C in a reactor equipped with a condenser (distillation). The process is carried out until the formation of distillate condensation ceases (reaction time 360 min), then the mixture is cooled to 50 °C and 2 M aqueous solution of KOH solution is added until the mixture reaches the pH value of 7. Then the whole mixture is heated to the temperature of 120 °C under reduced pressure to remove excess water. This process is continued until the mixture stabilizes. According to the example, 1000 g of polyol with a hydroxyl number of 760±10 mgKOH/g, and an acid number of 14.0 mg of KOH / g, and a functionality of 5.7 are obtained.

Example 15. To 1000 g of crude glycerol, 10 g of milled wood-like waste (MDF boards) with a grain size of 360-500 pm and 10 g of ortho-phosphoric acid are added, followed by heating, and stirring, gradually to 120 °C in a reactor equipped with a condenser (distillation). The process is carried out until the formation of distillate condensation ceases (reaction time 360 min), then the mixture is cooled to 50 °C and 2 M aqueous solution of KOH solution is added until the mixture reaches the pH value of 7. Then the whole mixture is heated to the temperature of 120 °C under reduced pressure to remove excess water. This process is continued until the mixture stabilizes. According to the example, 960 g of polyol with a hydroxyl number of 760±10 mgKOH/g, and an acid number of 20.0 mg of KOH / g, and a functionality of 5.6 are obtained.

Example 16. To 1000 g of the mixture formed by mixing 500 g of crude glycerine and 500 g of poly(ethylene oxide) of molecular weight 400 g/mol, 200 g of milled woodlike waste (HDF board) with a grain size of 160-240 pm and 40 g of H2SO4 are added, followed by heating, and stirring, gradually to 150 °C in a reactor equipped with a condenser (distillation). The process is carried out until the formation of distillate condensation ceases (reaction time 360 min), then the mixture is cooled to 50 °C and 2 M aqueous solution of KOH solution is added until the mixture reaches the pH value of 7. Then the whole mixture is heated to the temperature of 120 °C under reduced pressure to remove excess water. This process is continued until the mixture stabilizes. According to the example, 1100 g of polyol with a hydroxyl number of 630 ±10 mgKOH/g, and an acid number of 15.0 mg of KOH / g, and a functionality of 4.7 are obtained.

Example 17. To 1000 g of the mixture formed by mixing 500 g of crude glycerine and 500 g of poly(ethylene oxide) of molecular weight 400 g/mol, 500 g of milled woodlike waste (HDF board) with a grain size of 160-240 pm and 40 g of H2SO4 are added, followed by heating, and stirring, gradually to 200 °C in a reactor equipped with a condenser (distillation). The process is carried out until the formation of distillate condensation ceases (reaction time 360 min), then the mixture is cooled to 50 °C and 2 M aqueous solution of KOH solution is added until the mixture reaches the pH value of 7. Then the whole mixture is heated to the temperature of 120 °C under reduced pressure to remove excess water. This process is continued until the mixture stabilizes. According to the example, 1380 g of polyol with a hydroxyl number of 670 ±10 mgKOH/g, and an acid number of 20.0 mg of KOH / g, and a functionality of 4.7 are obtained.

Example 18. To 1000 g of the mixture formed by mixing 500 g of crude glycerine and 500 g of polyethylene oxide) of molecular weight 400 g/mol, 200 g of milled woodlike waste (chipboard) with a grain size of 240-360 pm and 40 g of H₂SO₄ are added, followed by heating, and stirring, gradually to 170 °C in a reactor equipped with a condenser (distillation). The process is carried out until the formation of distillate condensation ceases (reaction time 240 min), then the mixture is cooled to 50 °C and 2 M aqueous solution of KOH solution is added until the mixture reaches the pH value of 7. Then the whole mixture is heated to the temperature of 120 °C under reduced pressure to remove excess water. This process is continued until the mixture stabilizes. According to the example, 1100 g of polyol with a hydroxyl number of 630 ±10 mgKOH/g, and an acid number of 9.0 mg of KOH / g, and a functionality of 4.0 are obtained.

Example 19. To 1000 g of the mixture formed by mixing 750 g of crude glycerine and 250 g of poly(ethylene oxide) of molecular weight 400 g/mol, 300 g of milled woodlike waste (chipboard) with a grain size of 360-500 pm and 40 g of H2SO4 are added, followed by heating, and stirring, gradually to 300 °C in a reactor equipped with a condenser (distillation). The process is carried out until the formation of distillate condensation ceases (reaction time 240 min), then the mixture is cooled to 50 °C and 2 M aqueous solution of KOH solution is added until the mixture reaches the pH value of 7. Then the whole mixture is heated to the temperature of 120 °C under reduced pressure to remove excess water. This process is continued until the mixture stabilizes. According to the example, 1180 g of polyol with a hydroxyl number of 580 ±10 mgKOH/g, and an acid number of 19.1 mg of KOH / g, and a functionality of 4.9 are obtained

A method of making polyurethane materials from the resulting polyols is described below.

Example 20. The material was produced as follows: 70 mass parts of sorbitol oxypropylation product (Rokopol RF 551) and 30 mass parts of reactive raw material obtained from chipboard with hydroxyl number LOH = 530 mg KOH/g were mixed, then added of 1.5 mass parts of 33% solution of potassium acetate in ethylene glycol as catalyst, 1.5 mass parts of l,3,5-tris[3-(dimethylamino)propyl]hexahydro-l,3,5-triazines catalyst, and 4 mass parts of surfactant (Tegostab 8460) and mixed well. Then, 10 mass parts of 1,1,1,3,3-pentafluorobutane were added to the mixture as a foaming agent, and water was added in the amount of 2 mass parts in relation to the polyol premix. The polyols mixture thus prepared was thoroughly homogenized, then mixed for 10 seconds with isocyanate agent (pMDI) in such an amount that the molar ratio of NCO/OH groups was 2/1. The crosslinking and gelation process was carried out at a temperature of 22 °C and a pressure of 1.0 bar According to the example, a polyurethane material characterized by a density of 50 kg/m3 was obtained.

Example 21. The material was produced as follows: 70 mass parts of sorbitol oxypropylation product (Rokopol RF 551) and 30 mass parts of reactive raw material obtained from MDF board with hydroxyl number LOH = 750 mg KOH/g were mixed, then added of 1.5 mass parts of 33% solution of potassium acetate in ethylene glycol as catalyst, 1.5 mass parts of l,3,5-tris[3-(dimethylamino)propyl]hexahydro-l,3,5-triazines catalyst, and 4 mass parts of surfactant (Tegostab 8460) and mixed well. Then, 10 mass parts of 1,1,1,3,3-pentafluorobutane were added to the mixture as a foaming agent, and water was added in the amount of 2 mass parts in relation to the polyol premix. The polyols mixture thus prepared was thoroughly homogenized, then mixed for 10 seconds with isocyanate agent (pMDI) in such an amount that the molar ratio of NCO/OH groups was 3/1. The crosslinking and gelation process was carried out at a temperature of 21 °C and a pressure of 1.0 bar According to the example, a polyurethane material characterized by a density of 50 kg/m3 was obtained.

Example 22. The material was produced as follows: 90 mass parts of sorbitol oxypropylation product (Rokopol RF 551) and 10 mass parts of reactive raw material obtained from MDF board with hydroxyl number LOH = 750 mg KOH/g were mixed, then added of 10.0 mass parts of 33% solution of potassium acetate in ethylene glycol as catalyst, 20 mass parts of surfactant (Tegostab 8460) and mixed well. Then, 10 mass parts of 1,1,1,3,3-pentafluorobutane were added to the mixture as a foaming agent, and water was added in the amount of 2 mass parts in relation to the polyol premix. The polyols mixture thus prepared was thoroughly homogenized, then mixed for 10 seconds with isocyanate agent (pMDI) in such an amount that the molar ratio of NCO/OH groups was 2.5/1. The crosslinking and gelation process was carried out at a temperature of 21 °C and a pressure of 1.0 bar According to the example, a polyurethane material characterized by a density of 60 kg/m3 was obtained.

Example 23. The material was produced as follows: 60 mass parts of sorbitol oxypropylation product (Rokopol RF 551) and 40 mass parts of reactive raw material obtained from HDF board with hydroxyl number LOH = 630 mg KOH/g were mixed, then added of 1.5 mass parts of 33% solution of potassium acetate in ethylene glycol as catalyst, 1.5 mass parts of l,3,5-tris[3-(dimethylamino)propyl]hexahydro-l,3,5-triazines catalyst, 4.0 mass parts of surfactant (Tegostab 8460) and mixed well. Then, 10 mass parts of 1,1,1,3,3-pentafluorobutane were added to the mixture as a foaming agent, and water was added in the amount of 2 mass parts in relation to the polyol premix. The polyols mixture thus prepared was thoroughly homogenized, then mixed for 10 seconds with isocyanate agent (pMDI) in such an amount that the molar ratio of NCO/OH groups was 3/1. The crosslinking and gelation process was carried out at a temperature of 22 °C and a pressure of 1.0 bar According to the example, a polyurethane material characterized by a density of 45 kg/m3 was obtained.

Example 24. The material was produced as follows: 1 mass parts of sorbitol oxypropylation product (Rokopol RF 551) and 99 mass parts of reactive raw material obtained from HDF board with hydroxyl number LOH = 630 mg KOH/g were mixed, then added of 2.5 mass parts of 33% solution of potassium acetate in ethylene glycol as catalyst,

2.5 mass parts of l,3,5-tris[3-(dimethylamino)propyl]hexahydro-l,3,5-triazines catalyst, 15.0 mass parts of surfactant (Tegostab 8460) and mixed well. Then, 8 mass parts of n- pentane were added to the mixture as a foaming agent, and water was added in the amount of 10 mass parts in relation to the polyol premix. The polyols mixture thus prepared was thoroughly homogenized, then mixed for 10 seconds with isocyanate agent (pMDI) in such an amount that the molar ratio of NCO/OH groups was 1.5/1. The crosslinking and gelation process was carried out at a temperature of 22 °C and a pressure of 1.0 bar According to the example, a polyurethane material characterized by a density of 35 kg/m3 was obtained.

Example 25. The material was produced as follows: 10 mass parts of sorbitol oxypropylation product (Rokopol RF 551) and 90 mass parts of reactive raw material obtained from plywood panel with hydroxyl number LOH = 630 mg KOH/g were mixed, then added of 3.0 mass parts of 33% solution of potassium acetate in ethylene glycol as catalyst, 4.0 mass parts of l,3,5-tris[3-(dimethylamino)propyl]hexahydro-l,3,5-triazines catalyst, 18.0 mass parts of surfactant (Tegostab 8460) and mixed well. Then, 10 mass parts of n-pentane were added to the mixture as a foaming agent, and water was added in the amount of 5 mass parts in relation to the polyol premix. The polyols mixture thus prepared was thoroughly homogenized, then mixed for 10 seconds with isocyanate agent (pMDI) in such an amount that the molar ratio of NCO/OH groups was 2.5/1. The crosslinking and gelation process was carried out at a temperature of 22 °C and a pressure of 1.0 bar According to the example, a polyurethane material characterized by a density of 45 kg/m3 was obtained.

Example 26. The material was produced as follows: 70 mass parts of sorbitol oxypropylation product (Rokopol RF 551) and 30 mass parts of reactive raw material obtained from plywood panel with hydroxyl number LOH = 630 mg KOH/g were mixed, then added of 1.5 mass parts of 33% solution of potassium acetate in ethylene glycol as catalyst, 1.5 mass parts of l,3,5-tris[3-(dimethylamino)propyl]hexahydro-l,3,5-triazines catalyst, 4.0 mass parts of surfactant (Tegostab 8460) and mixed well. Then, 10 mass parts of 1,1,1,3,3-pentafluorobutane were added to the mixture as a foaming agent, and water was added in the amount of 2 mass parts in relation to the polyol premix. The polyols mixture thus prepared was thoroughly homogenized, then mixed for 10 seconds with isocyanate agent (pMDI) in such an amount that the molar ratio of NCO/OH groups was 2.5/1. The crosslinking and gelation process was carried out at a temperature of 22 °C and a pressure of 1.0 bar According to the example, a polyurethane material characterized by a density of 41 kg/m3 was obtained.

Example 27. The material was produced as follows: 50 mass parts of sorbitol oxypropylation product (Rokopol RF 551) and 50 mass parts of reactive raw material obtained from OSB board with hydroxyl number LOH = 510 mg KOH/g were mixed, then added of 1.5 mass parts of 33% solution of potassium acetate in ethylene glycol as catalyst, 1.5 mass parts of l,3,5-tris[3-(dimethylamino)propyl]hexahydro-l,3,5-triazines catalyst, 4.0 mass parts of surfactant (Tegostab 8460) and mixed well. Then, 10 mass parts of 1,1,1,3,3-pentafluorobutane were added to the mixture as a foaming agent, and water was added in the amount of 2 mass parts in relation to the polyol premix. The polyols mixture thus prepared was thoroughly homogenized, then mixed for 10 seconds with isocyanate agent (pMDI) in such an amount that the molar ratio of NCO/OH groups was 2.2/1. The crosslinking and gelation process was carried out at a temperature of 22 °C and a pressure of 1.0 bar According to the example, a polyurethane material characterized by a density of 48 kg/m3 was obtained. Example 28. The material was produced as follows: 5 mass parts of polyether (Rokopol M 6000) and 95 mass parts of reactive raw material obtained from chipboardwith hydroxyl number LOH = 520 mg KOH/g were mixed, then added of 1.0 mass parts of 33% solution of potassium acetate in ethylene glycol as catalyst, 1.5 mass parts of l,3,5-tris[3- (dimethylamino)propyl]hexahydro-l,3,5-triazines catalyst. The polyols mixture thus prepared was thoroughly homogenized, then mixed for 10 seconds with isocyanate agent (pMDI) in such an amount that the molar ratio of NCO/OH groups was 1.1/1. The crosslinking and gelation process was carried out at a temperature of 110 °C and a pressure of 30.0 bar According to the example, a polyurethane material characterized by a bending strength of 13.3 MPa was obtained.

Example 29. The material was produced as follows: 1 mass parts of polyether (Rokopol M 6000) and 99 mass parts of reactive raw material obtained from chipboard with hydroxyl number LOH = 520 mg KOH/g were mixed, then added of 5.0 mass parts of 33% solution of potassium acetate in ethylene glycol as catalyst, 5.0 mass parts of 1,3,5- tris[3-(dimethylamino)propyl]hexahydro-l,3,5-triazines catalyst. The polyols mixture thus prepared was thoroughly homogenized, then mixed for 10 seconds with isocyanate agent (pMDI) in such an amount that the molar ratio of NCO/OH groups was 1.1/1. The crosslinking and gelation process was carried out at a temperature of 110 °C and a pressure of 30.0 bar According to the example, a polyurethane material characterized by a bending strength of 14.3 MPa was obtained.

Example 30. The material was produced as follows: 5 mass parts of polyether (Rokopol M 6000) and 95 mass parts of reactive raw material obtained from chipboard with hydroxyl number LOH = 520 mg KOH/g were mixed, then added of 2.0 mass parts of 33% solution of potassium acetate in ethylene glycol as catalyst, 1.5 mass parts of 1,3,5- tris[3-(dimethylamino)propyl]hexahydro-l,3,5-triazines catalyst. The polyols mixture thus prepared was thoroughly homogenized, then mixed for 10 seconds with isocyanate agent (pMDI) in such an amount that the molar ratio of NCO/OH groups was 1.1/1. The crosslinking and gelation process was carried out at a temperature of 20 °C and a pressure of 10.0 bar According to the example, a polyurethane material characterized by a bending strength of 14.3 MPa was obtained. Example 31. The material was produced as follows: 5 mass parts of polyether (Rokopol M 6000) and 95 mass parts of reactive raw material obtained from OSB board with hydroxyl number LOH = 510 mg KOH/g were mixed, then added of 1.0 mass parts of 33% solution of potassium acetate in ethylene glycol as catalyst, 1.0 mass parts of 1,3,5- tris[3-(dimethylamino)propyl]hexahydro-l,3,5-triazines catalyst. The polyols mixture thus prepared was thoroughly homogenized, then mixed for 10 seconds with isocyanate agent (pMDI) in such an amount that the molar ratio of NCO/OH groups was 1.5/1. The crosslinking and gelation process was carried out at a temperature of 180 °C and a pressure of 35.0 bar According to the example, a polyurethane material characterized by a bending strength of 18.3 MPa was obtained.

Example 32. The material was produced as follows: 99 mass parts of polyether (Rokopol M 6000) and 1 mass parts of reactive raw material obtained from OSB board with hydroxyl number LOH = 510 mg KOH/g were mixed, then added of 4.0 mass parts of 33% solution of potassium acetate in ethylene glycol as catalyst, 2.0 mass parts of 1,3,5- tris[3-(dimethylamino)propyl]hexahydro-l,3,5-triazines catalyst. The polyols mixture thus prepared was thoroughly homogenized, then mixed for 10 seconds with isocyanate agent (pMDI) in such an amount that the molar ratio of NCO/OH groups was 1.5/1. The crosslinking and gelation process was carried out at a temperature of 120 °C and a pressure of 35.0 bar According to the example, a polyurethane material characterized by a bending strength of 19.3 MPa was obtained.

Example 33. The material was produced as follows: 5 mass parts of polyether (Rokopol M 6000) and 95 mass parts of reactive raw material obtained from OSB board with hydroxyl number LOH = 510 mg KOH/g were mixed, then added of 2.0 mass parts of 33% solution of potassium acetate in ethylene glycol as catalyst, 1.5 mass parts of 1,3,5- tris[3-(dimethylamino)propyl]hexahydro-l,3,5-triazines catalyst. The polyols mixture thus prepared was thoroughly homogenized, then mixed for 10 seconds with isocyanate agent (pMDI) in such an amount that the molar ratio of NCO/OH groups was 1.4/1. The crosslinking and gelation process was carried out at a temperature of 60 °C and a pressure of 35.0 bar According to the example, a polyurethane material characterized by a bending strength of 16.3 MPa was obtained. Example 34. The material was produced as follows: 3 mass parts of poly ether (Rokopol M 6000) and 97 mass parts of reactive raw material obtained from OSB board with hydroxyl number LOH = 510 mg KOH/g were mixed, then added of 1.0 mass parts of 33% solution of potassium acetate in ethylene glycol as catalyst, 1.5 mass parts of 1,3,5- tris[3-(dimethylamino)propyl]hexahydro-l,3,5-triazines catalyst. The polyols mixture thus prepared was thoroughly homogenized, then mixed for 10 seconds with isocyanate agent (pMDI) in such an amount that the molar ratio of NCO/OH groups was 1.4/1. The crosslinking and gelation process was carried out at a temperature of 21 °C and a pressure of 1.0 bar According to the example, a polyurethane material characterized by a bending strength of 9.3 MPa was obtained.

Example 35. The material was produced as follows: 5 mass parts of polyether (Rokopol M 6000) and 95 mass parts of reactive raw material obtained from MDF board with hydroxyl number LOH = 750 mg KOH/g were mixed, then added of 1.5 mass parts of 33% solution of potassium acetate in ethylene glycol as catalyst, 1.5 mass parts of 1,3,5- tris[3-(dimethylamino)propyl]hexahydro-l,3,5-triazines catalyst. The polyols mixture thus prepared was thoroughly homogenized, then mixed for 10 seconds with isocyanate agent (pMDI) in such an amount that the molar ratio of NCO/OH groups was 1.2/1. The crosslinking and gelation process was carried out at a temperature of 21 °C and a pressure of 1.0 bar According to the example, a polyurethane material characterized by a bending strength of 8.3 MPa was obtained.

Example 36. The material was produced as follows: 50 mass parts of polyether (Rokopol M 6000) and 50 mass parts of reactive raw material obtained from MDF board with hydroxyl number LOH = 750 mg KOH/g were mixed, then added of 7.5 mass parts of 33% solution of potassium acetate in ethylene glycol as catalyst, 3.5 mass parts of 1,3,5- tris[3-(dimethylamino)propyl]hexahydro-l,3,5-triazines catalyst. The polyols mixture thus prepared was thoroughly homogenized, then mixed for 10 seconds with isocyanate agent (pMDI) in such an amount that the molar ratio of NCO/OH groups was 1.5/1. The crosslinking and gelation process was carried out at a temperature of 50 °C and a pressure of 5.0 bar According to the example, a polyurethane material characterized by a bending strength of 11.3 MPa was obtained. Example 37. The material was produced as follows: 5 mass parts of polyether (Rokopol M 6000) and 95 mass parts of reactive raw material obtained from MDF board with hydroxyl number LOH = 750 mg KOH/g were mixed, then added of 1.5 mass parts of 33% solution of potassium acetate in ethylene glycol as catalyst, 1.5 mass parts of 1,3,5- tris[3-(dimethylamino)propyl]hexahydro-l,3,5-triazines catalyst. The polyols mixture thus prepared was thoroughly homogenized, then mixed for 10 seconds with isocyanate agent (pMDI) in such an amount that the molar ratio of NCO/OH groups was 1.2/1. The crosslinking and gelation process was carried out at a temperature of 100 °C and a pressure of 50.0 bar According to the example, a polyurethane material characterized by a bending strength of 18.3 MPa was obtained.

Example 38. The material was produced as follows: 5 mass parts of polyether (Rokopol M 6000) and 95 mass parts of reactive raw material obtained from HDF board with hydroxyl number LOH = 630 mg KOH/g were mixed, then added of 1.0 mass parts of 33% solution of potassium acetate in ethylene glycol as catalyst, 1.0 mass parts of 1,3,5- tris[3-(dimethylamino)propyl]hexahydro-l,3,5-triazines catalyst. The polyols mixture thus prepared was thoroughly homogenized, then mixed for 10 seconds with isocyanate agent (pMDI) in such an amount that the molar ratio of NCO/OH groups was 1.1/1. The crosslinking and gelation process was carried out at a temperature of 100 °C and a pressure of 50.0 bar According to the example, a polyurethane material characterized by a bending strength of 17.3 MPa was obtained.

Example 39. The material was produced as follows: 5 mass parts of polyether (Rokopol M 6000) and 95 mass parts of reactive raw material obtained from HDF board with hydroxyl number LOH = 630 mg KOH/g were mixed, then added of 1.0 mass parts of 33% solution of potassium acetate in ethylene glycol as catalyst, 1.0 mass parts of 1,3,5- tris[3-(dimethylamino)propyl]hexahydro-l,3,5-triazines catalyst. The polyols mixture thus prepared was thoroughly homogenized, then mixed for 10 seconds with isocyanate agent (pMDI) in such an amount that the molar ratio of NCO/OH groups was 1.3/1. The crosslinking and gelation process was carried out at a temperature of 150 °C and a pressure of 50.0 bar According to the example, a polyurethane material characterized by a bending strength of 19.3 MPa was obtained. Example 40. The material was produced as follows: 2 mass parts of polyether (Rokopol M 6000) and 98 mass parts of reactive raw material obtained from plywood panel with hydroxyl number LOH = 630 mg KOH/g were mixed, then added of 1.5 mass parts of 33% solution of potassium acetate in ethylene glycol as catalyst, 1.5 mass parts of l,3,5-tris[3-(dimethylamino)propyl]hexahydro-l,3,5-triazines catalyst. The polyols mixture thus prepared was thoroughly homogenized, then mixed for 10 seconds with isocyanate agent (pMDI) in such an amount that the molar ratio of NCO/OH groups was 1.2/1. The crosslinking and gelation process was carried out at a temperature of 100 °C and a pressure of 50.0 bar According to the example, a polyurethane material characterized by a bending strength of 17.3 MPa was obtained.

Example 41. The material was produced as follows: 3 mass parts of polyether (Rokopol M 6000) and 97 mass parts of reactive raw material obtained from plywood panel with hydroxyl number LOH = 630 mg KOH/g were mixed, then added of 2.5 mass parts of 33% solution of potassium acetate in ethylene glycol as catalyst, 2.5 mass parts of l,3,5-tris[3-(dimethylamino)propyl]hexahydro-l,3,5-triazines catalyst. The polyols mixture thus prepared was thoroughly homogenized, then mixed for 10 seconds with isocyanate agent (pMDI) in such an amount that the molar ratio of NCO/OH groups was 1.2/1. The crosslinking and gelation process was carried out at a temperature of 23 °C and a pressure of 1.0 bar According to the example, a polyurethane material characterized by a bending strength of 10.3 MPa was obtained.

Example 42. The material was produced as follows: 99 mass parts of polyether (Rokopol M 6000) and 1 mass parts of reactive raw material obtained from plywood panel with hydroxyl number LOH = 630 mg KOH/g were mixed, then added of 1.5 mass parts of 33% solution of potassium acetate in ethylene glycol as catalyst, 4.5 mass parts of 1,3,5- tris[3-(dimethylamino)propyl]hexahydro-l,3,5-triazines catalyst. The polyols mixture thus prepared was thoroughly homogenized, then mixed for 10 seconds with isocyanate agent (pMDI) in such an amount that the molar ratio of NCO/OH groups was 2.0/1. The crosslinking and gelation process was carried out at a temperature of 70°C and a pressure of 3.0 bar According to the example, a polyurethane material characterized by a bending strength of 11.3 MPa was obtained

Claims

1. Method of obtaining reactive polyol from wood-waste materials, based on the liquefaction of the wastes in the presence of solvent excess, characterized in that, the wood- waste material used in the process is a wood-waste material grinded to the grain size from 1 to 500 pm, preferably 10 to 360 pm, which is subjected to the solvolysis process in the presence of solvent or mixture of solvents with the biomass content of 1-50% of the solvent mass, preferably 10-30%, in the presence of catalyst in form of acid or base or acid and base in the amount of 0,01 to 20% by weight, preferably 1 to 10% by weight relating to the solvent, in the temperature from 80 to 300°C, preferably from 120 to 170°C, in the time of 60 to 600 min, preferably 60 to 360 min, and next obtained polyol is neutralized with the use of acid or base.

2. Method according to claim 1, wherein fibreboards, MDF boards, HDF boards, chipboards, oriented chipboards are used as a wood-waste for grinding in order to obtain grains with proper size.

3. Method according to claim 1, wherein as solvents the following are used: methanol, ethanol, propanol, hexanol, diols such as 1,2-ethanediol, 1,3 -propanediol, 1,2-propanediol, 1,3-butanediol, 1 ,4-butanediol, 2,3-butanediol, 2,2'-oxydiethanol, and 1,2,3-propanetriol, 1,2,3,4-butanetetrol (erythritol), pentane-1, 2, 3, 4, 5-pentol (ribitol), polyethylene oxide), ethylene carbonate, glycerine flow, crude glycerine, water or phenol and their mixtures.

4. Method according to claim 1, wherein as catalysts following are used: potassium hydroxide, sodium hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, iron hydroxide, nitrogen trihydride (ammonia), sulphurous acid, sulphuric acid, orthophosphoric acid, hydrochloric acid, nitrous acid, nitric acid, chlorous acid, chloric acid, or perchloric acid.

5. New polyols wherein the polyols are obtainable according to methods described in claim 1-4 and obtained polyols have physical properties such as hydroxyl value from 50 to 800 mg KOH/g, acid number from 0,1 to 20 mg KOH/g, molecular weight from 30 g/mol to 7000 g/mol, and functionality from 1 to 4.

6. Method of manufacturing polyurethane material with the use of polyols obtainable according to method of claims 1-4, characterized in that, said polyol is obtained in the solvolysis process of wood- waste materials and polyol mixture contains 1-99 parts by mass of polyol obtained from wood- wastes, and 0,01-10 parts by mass of catalysts in form of amine catalysts, organometallic catalysts, metal salts catalysts, and 0,1-20 parts by mass surface agents, and 1-20 parts by mass of blowing agents, and 1-90 parts by mass of isocyanate substance, and cross-linking and gelation of the material is conducted in the room temperature, and standard pressure, and/or in the temperature below degradation, and under elevated pressure.

7. Method according to claim 6, wherein cross-linking and gelation processes are performed in the temperature of 20 to 180oC and pressure of 0,9 to 50 Ba.

8. Method according to claim 6, wherein as a catalyst the following is used: amine catalysts, organometallic catalysts and/or metal salts or their mixtures.

9. Method according to claim 6, wherein, as catalyst the following is used: solution of potassium acetate in ethylene glycol, l,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 (II) 2-ethylhexanoate, N,N- dimethylcyclohexylamine (DMCHA), dilaurate or their mixtures.

10. Method according to claim 6, wherein as blowing agent following is used: 1,1,1,3,3-pentafluorobutane, n-pentane, cyclopentane, cyclohexane, dichloromethane, and/or water.

11. Method according to claim 6, wherein as surfactants the following is used: polyethers modified with polysiloxanes, polysiloxanes, silicone oils, and/or copolymer silicone-glycol.

12. Method according to claim 6, wherein as isocyanates the following are used: 4,4'- diphenylmethane diisocyanate (MDI), 2,4-toluene diisocyanate (TDI), 1,6-hexamethylene diisocyanate (HDI) or polymeric diphenylmethane diisocyanate (pMDI).