WO2014044234A1 - A method of preparation of polyurethane materials containing lignin, a polyurethane material prepared according to this method - Google Patents

A method of preparation of polyurethane materials containing lignin, a polyurethane material prepared according to this method Download PDF

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Publication number
WO2014044234A1
WO2014044234A1 PCT/CZ2013/000111 CZ2013000111W WO2014044234A1 WO 2014044234 A1 WO2014044234 A1 WO 2014044234A1 CZ 2013000111 W CZ2013000111 W CZ 2013000111W WO 2014044234 A1 WO2014044234 A1 WO 2014044234A1
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Prior art keywords
lignin
component
polyurethane
dispersion
polyol
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PCT/CZ2013/000111
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French (fr)
Inventor
Tomáš VLČEK
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SYNPO, akciová společnost
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Publication of WO2014044234A1 publication Critical patent/WO2014044234A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
    • C07G1/00—Lignin; Lignin derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/36—Hydroxylated esters of higher fatty acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6492—Lignin containing materials; Wood resins; Wood tars; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/6547—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/005—Lignin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/005—< 50kg/m3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2190/00—Compositions for sealing or packing joints

Definitions

  • the invention concerns chemical industry, specifically a method of preparation of single-component and double-component polyurethane materials with addition of lignin, generated as a by-product of cellulose production.
  • Lignin is an important building component of wood, functioning as a binder for long cellulose fibres securing thus the strength of wood.
  • lignin is the second most common substance forming wood. It is a high molecular weight amorphous substance that has a complex polyphenolic structure. The irregular structure of lignin is a mixture of physical and chemically heterogeneous materials. Lignin accounts for approximately 20 to 35% of the mass of soft and hard wood, and in the concentration of 8% it is present for example in corn. Lignin is isolated from the woody biomass through two basic chemical processes of delignification, which involve the formation of sulphite and alkali "kraft" lignin.
  • the sulphite type is prepared through a process of pulping by boiling the wood biomass in a solution of various salts of sulfuric acid.
  • the alkaline process involves pulping by boiling the wood mass in a solution of sodium hydroxide and sodium sulphide. These processes result in a sulphite and "black" leachate.
  • a newer method to obtain lignin from wood is the "organosolv” process, which is based on pulping with acetic acid and formic acid and hydrogen peroxide where the end product is a dark brown solution of lignin in water.
  • these three types of lignin differ from each other by the molecular weight, as well as by the number and type of functional groups.
  • lignin is a by-product in the production of cellulose for the paper industry
  • lignin is usually seen as a waste material. Although it is a readily available natural resource, its industrial use is currently limited mostly due to its physical and chemical properties.
  • the sulphite type of lignin for example, is used for the manufacture of dispersants, emulsifiers or phenol adhesives.
  • Lignin has a low thermal stability and begins to decompose at a temperature of approximately 140°C. It has a low water resistance and its low molecular weight fractions are biodegradable. After drying in its unprocessed form, lignin is a dark brown powder with a very specific odour.
  • Lignin is composed of carbon, hydrogen and oxygen, and its structure contains hydroxyl, methoxy, carbonyl and carboxyl groups.
  • the primary and secondary hydroxyl groups of lignin may react with isocyanate to form urethane bonds.
  • lignin can be applied in the preparation of polyurethane materials.
  • lignin is usable as a natural renewable raw material replacing i
  • the fundamental problem of the applicability of lignin in the preparation of polyurethane materials is its insolubility in polyols, which prevents the reaction of hydroxyl groups of lignin with isocyanate leading to the formation of a polymer network. Miscibility of lignin with this polyol component can be achieved either by dissolving lignin in a suitable organic solvent or through a chemical modification.
  • Patent no. JP63182327 shows the preparation of polyurethanes containing lignin in which lignin from the organosolv process is used in a solution form in organic solvents such as tetrahydrofuran or dioxin.
  • organic solvents such as tetrahydrofuran or dioxin.
  • the major disadvantage of this process is primarily the high toxicity of such solvents.
  • Another disadvantage is only partial solubility of only the low molecular weight fractions, which make up approximately 30-
  • Patent no. US4017474(A) claims preparation of polycarboxy-oxyalkylene polyester- polyether polyol as a liquid intermediate product based on lignin suitable for production of polyurethane materials.
  • This is the chemical modification of sulphite or alkaline as well as organosolv lignin, in which during the first phase lignin reacts through a radical reaction with maleic anhydride. By subsequent hydrolysis the anhydride ring opens to form carboxyl groups, which are alkoxylated during the last phase. Through alkoxylation sections of linear polyether chains of terminal primary or secondary hydroxyl groups are created.
  • This process however, has the disadvantage of complicated process technological and expensiveness of chemical modification of lignin.
  • a disadvantage of the existing procedures is either insufficient dispersion of lignin in polyols or lignin dispersion in polyols by means of toxic solvents. This fact limits the use of lignin to produce polyurethane materials or the production of the same is toxic and represents a burden for the environment.
  • the preparation comprises reaction of polyol with an isocyanate, with the addition of lignin at least in one reaction component.
  • the invention is based in the reduction of the powder lignin particles in a dispersion device to the size of nanometres to micrometers and simultaneously they are dispersed without the use of solvents in a pre-polymer terminated by reactive isocyanate groups upon preparation of single-component polyurethane materials or in a polyol reaction component and/or W m isocyanate reaction component upon preparation of two-component polyurethane materials.
  • the dispersion preparation is carried out in dispersion devices characterised with a balanced grinding effect, sheer and dispersion phase circulation in the continual phase.
  • These devices can comprise for example a pearl mill, a colloidal mill for wet grinding with a cone-shaped rotor, an attritor, a five-cylinder friction device or another device.
  • the particular type of the dispersion device is selected according to the continuous phase viscosity, the size of the dispersion phase particles and the final dispersion viscosity.
  • a sufficient grinding effect enables an effective crushing of agglomerates and aggregates of the powder lignin.
  • the shear stress in the range of 10 3 - 10 5 s ' will ensure sufficient exfoliation of micro and nano particles of lignin in the dispersion.
  • the particular type of the dispersion device is selected according to the continuous phase viscosity, the size of the dispersion phase particles and the final dispersion viscosity.
  • the size of the dispersed lignin particles ranges from 1.10 "9 m to 999.10 "6 m.
  • At least one substance to adjust chemical or physical characteristics of the dispersion achieved is added to the lignin dispersion in the polymer and/or polyol reaction component and/or in the isocyanate reaction component.
  • This substance can comprise an additive or another portion of one of the reaction components.
  • the polyol component comprises at least one substance or a combination of substances containing two or more hydroxyl groups.
  • substances can comprise for example glycols, carbohydrates, polyesterpolyols, oily polyols and/or their combination.
  • At least one additive or a combination of additives is added in any polyurethane system component. Adding of an additive depends on the particular final application of the produced polyurethane material. Additives improve the processing characteristics or the final product characteristics. For example in certain procedures catalysts are necessary to activate the reaction. It is advantageous when the additive is composed of at lest one substance from the following group or their combination: catalysts, blowing agents, defoamers, emulsifiers, dispersion agents, humidity absorbents, pigments, filling materials, stabilizers, or flame retardants.
  • the isocyanate component comprises at least one substance (or their combination) from the polyisocyanate or isocyanate group with blocked reactive groups or monomer isocyanates, such as: toluylene diisocyanate (TDI), isophorone diisocyanate (IPDI), hexamethylendiisocyanate (HMDI), diphenylmethaneisocyanate (HDI).
  • TDI toluylene diisocyanate
  • IPDI isophorone diisocyanate
  • HMDI hexamethylendiisocyanate
  • HDI diphenylmethaneisocyanate
  • the subject of invention is also a polyurethane material prepared by the aforementioned method.
  • the invention is based on the content of a powder lignin with the particle size reduced to nanometres and micrometers and dispersed in a pre-polymer terminated by at least one of the reactive isocyanate groups for single- component polyurethane materials or in a polyol reaction component and/or an isocyanate reaction component for two-component polyurethane materials.
  • the polyurethane material is created as a polyurethane casting resin containing lignin in the range from 0.1 to 60% by weight.
  • the polyurethane casting resin containing lignin is characterized with an increased electric resistance and improved thermal and mechanical features.
  • the polyurethane material is created as a polyurethane paint coat containing lignin in the range from 0.1 to 30% by weight.
  • the polyurethane material is created as a polyurethane foam material containing lignin in the range from 0.1 to 10% by weight.
  • This design comprises soft, semi-hard, hard and other polyurethane foams.
  • the polyurethane material is created as an adhesive or sealant containing pre-dried lignin in the range from 0.1 to 60% by weight.
  • the method of preparation of polyurethane materials according to the invention are based on the fact that the method of preparation comprises a solvent- free high efficient dispersion of lignin in polyurethanes, which is technically easily realised and environmentally friendly.
  • the procedure can be used to prepare a wide range of polyurethane materials.
  • the polyurethane materials produced in compliance with the invention feature a range of improved physical characteristics, such as for example: an increased tensile strength, an elastic modules, toughness, electric characteristics, etc.
  • Example 1 PU casting resin synthesis on the basis of castor oil and cured with
  • Preparation of the PU casting resin is based on the reaction of the polyol component A and the isocyanate component B in a reaction mixture.
  • a source of vacuum an oil pump
  • the component A is heated up to the temperature of 90°C. Distillation under the pressure of ⁇ 0.1 mbar during approximately 1 hour the water content in the polyol component A is decreased to ⁇ 0.05% by weight.
  • the component A is cooled to the ambient temperature and after elimination of vacuum an inert gas, pre-dried nitrogen or argon is brought in the reactor.
  • a source of vacuum is reconnected to the reactor (an oil pump). The reaction mixture under ambient temperature and decreased pressure ⁇ 0.1mbar is homogenized by intense stirring during approximately 30 minutes.
  • the reactor After termination of homogenization the reactor is disconnected from the source of vacuum.
  • the reaction mixture is removed from the reactor by casting in a prepared metal form sized 0.2 x 15 x 20cm. Curing of the polyurethane mixture is carried out in the metal form under ambient temperature during 24 hours and subsequently under the temperature of 80°C during 1 hour when polyurethane networking is finished.
  • Example 2 PU cas ing resin synthesis on the base of castor oil and cured with MDI and with the lignin content of 15% by weight
  • the component A is cooled to the ambient temperature and after elimination of vacuum an inert gas, pre-dried nitrogen or argon is brought in the reactor.
  • a source of vacuum is reconnected to the reactor (an oil pump).
  • the reaction mixture under ambient temperature and decreased pressure ⁇ 0.1mbar is homogenized by intense stirring during approximately 30 minutes. After termination of homogenization the reactor is disconnected from the source of vacuum.
  • the reaction mixture is removed from the reactor by casting in a prepared metal form sized 0.2 x 15 x 20cm.
  • Curing of the polyurethane mixture with the content of the "organosolv” lignin of 15% by weight is carried out in the metal form under ambient temperature during 24 hours and subsequently under the temperature of 80°C during 1 hour when polyurethane networking is finished.
  • Preparation of the PU feasting resin is based on the reaction of the polyol component A and the isocyanate component B in a reaction mixture.
  • the polyol component A is dosed in the reactor, i.e. 10. Og of castor j
  • Curing of the poiyurethane film is carried out first by free drying under ambient temperature during 24 hours and subsequently under the temperature of 70°C during further 24 hours. The film curing is finished under 120°C during 1 hour.
  • Example 4 Synthesis of solvent-free PU paint coat based on castor oil and cured with TDI and with the lignin content of 15% of the weigh.
  • dispersion from theticianorganosolv" lignin in castor oil is prepared.
  • a baker with the volume of 100ml we mix 25. Og of castor oil with 25. Og of lignin.
  • the mixture is ten times repeatedly dispersed with high shear forces under the temperature of 25°C in a shear device to reduce the size and dispersion of the particles (Three Roll Mill EXAKT 80 E, by EXAKT technologies, Inc.).
  • the prepared dispersion is a highly viscose paste without presence of any lignin aggregates.
  • a source of vacuum an oil pump
  • the component A is heated up to the temperature of 90°C. Distillation under the pressure of ⁇ 0.1mbar during approximately 1 hour the water content in the polyol component A is decreased to ⁇ 0.05% by weight.
  • the component A is cooled to the ambient temperature and after elimination of vacuum an inert gas, pre- dried nitrogen or argon is brought in the reactor.
  • reaction mixture After termination of homogenisation the reaction mixture is drawdowned on a glass plate and on a polypropylene substrate by wire-wound rod 200 ⁇ .
  • Curing of the polyurethane film is carried out first by free drying under ambient temperature during 24 hours and subsequently under the temperature of 70°C during further 24 hours. The film curing is finished under 120°C during 1 hour.
  • Preparation of the soft PU foam is based on the reaction of the polyol component A and the isocyanate component B in a reaction mixture.
  • a baker with the volume of 100ml we mix 25. Og of castor oil with 25. Og of lignin.
  • the mixture is ten times repeatedly dispersed with high shear forces under the temperature of 25°C in a shear device to reduce the size and dispersion of the particles (Three Roll Mill EXAKT 80 E, by EXAKT technologies, Inc.).
  • the prepared dispersion is a highly viscose paste without presence of any lignin aggregates.
  • component A of the reaction mixture composed of 3.04g of 50% lignin dispersion in polyol, 48.48g of polyol Slovaprop ® G-48 S, 0.08g of promoter of the creation of urethane bonds Dabco ® 33LV (Air Products), 0.50g of the silicon surfactant Dabco ® DC5906 (Air Products), 0.10 g of the networked catalyst based on tin Kosmos® 29 (Evonik), and 1.78g of distilled water used as a blowing agent. Ingredients of component A are homogenized during 30 seconds under the intense stirring of 2,000 turns/min.
  • 100g of pre-dried lignin (60°C, 24 hours) is stirred in a slow-running stirrer in the polyurethane pre-polymer with the content of 12.6% of free isocyanate groups.
  • the pre-mixture is subsequently repeatedly dispersed on a five-cylinder friction device to create a perfectly smooth paste with the viscosity of 65Pa.s.
  • the prepared dispersion is used as a structural adhesive to bond together ABS substrates. Shear strength of the adhesive on the pre-treated surface of the plastic substrate is 6-8MPa.
  • IFD 65 the strength necessary to compress the sample to 65% of the original height
  • the method of preparation of polyurethane materials according to the invention can be used for industrial production and industrial applications of polyurethane materials containing Iignin in various areas, for example in electrical engineering, construction industry, chemical and consumer goods industry.

Abstract

The method of preparation of polyurethane materials through the reaction of polyol with isocyanate with lignin added in at least one reaction component according to the invention is based in the reduction of the powder lignin particles in a dispersion device to the size of nanometres to micrometers and simultaneously they are dispersed without the use of solvents in at least on component for preparation of single-component or two-component polyurethane materials. The method of preparation according to the invention does not present a load for the environment and enables production without the use of organic solvents. Polyurethane materials containing lignin and prepared according to the invention have a homogenous structure and modified characteristics. Polyurethane casting resins according to the invention feature a significantly increased electrical resistance and improved thermo- mechanical characteristics for use in the electrical industry.

Description

A method of preparation of polyurethane materials containing lignin; a polyurethane material prepared according to this method
Field of the invention
The invention concerns chemical industry, specifically a method of preparation of single-component and double-component polyurethane materials with addition of lignin, generated as a by-product of cellulose production.
Background of the invention
Lignin is an important building component of wood, functioning as a binder for long cellulose fibres securing thus the strength of wood. Next to cellulose, lignin is the second most common substance forming wood. It is a high molecular weight amorphous substance that has a complex polyphenolic structure. The irregular structure of lignin is a mixture of physical and chemically heterogeneous materials. Lignin accounts for approximately 20 to 35% of the mass of soft and hard wood, and in the concentration of 8% it is present for example in corn. Lignin is isolated from the woody biomass through two basic chemical processes of delignification, which involve the formation of sulphite and alkali "kraft" lignin. The sulphite type is prepared through a process of pulping by boiling the wood biomass in a solution of various salts of sulfuric acid. The alkaline process involves pulping by boiling the wood mass in a solution of sodium hydroxide and sodium sulphide. These processes result in a sulphite and "black" leachate. A newer method to obtain lignin from wood is the "organosolv" process, which is based on pulping with acetic acid and formic acid and hydrogen peroxide where the end product is a dark brown solution of lignin in water. Depending on the delignification process used and on the plant origin, these three types of lignin differ from each other by the molecular weight, as well as by the number and type of functional groups.
With view to the fact that lignin is a by-product in the production of cellulose for the paper industry, lignin is usually seen as a waste material. Although it is a readily available natural resource, its industrial use is currently limited mostly due to its physical and chemical properties. The sulphite type of lignin, for example, is used for the manufacture of dispersants, emulsifiers or phenol adhesives.
Lignin has a low thermal stability and begins to decompose at a temperature of approximately 140°C. It has a low water resistance and its low molecular weight fractions are biodegradable. After drying in its unprocessed form, lignin is a dark brown powder with a very specific odour.
Lignin is composed of carbon, hydrogen and oxygen, and its structure contains hydroxyl, methoxy, carbonyl and carboxyl groups. The primary and secondary hydroxyl groups of lignin may react with isocyanate to form urethane bonds. Through this addition reaction lignin can be applied in the preparation of polyurethane materials. In this case lignin is usable as a natural renewable raw material replacing i
petrochemical polyols.
The fundamental problem of the applicability of lignin in the preparation of polyurethane materials is its insolubility in polyols, which prevents the reaction of hydroxyl groups of lignin with isocyanate leading to the formation of a polymer network. Miscibility of lignin with this polyol component can be achieved either by dissolving lignin in a suitable organic solvent or through a chemical modification.
Patent no. JP63182327 (A) shows the preparation of polyurethanes containing lignin in which lignin from the organosolv process is used in a solution form in organic solvents such as tetrahydrofuran or dioxin. The major disadvantage of this process is primarily the high toxicity of such solvents. Another disadvantage is only partial solubility of only the low molecular weight fractions, which make up approximately 30-
I
40% of lignin. The presence of high molecular weight fractions is the reason why lignin in generally very poorly solvable in organic solvents.
Patent no. US4017474(A) claims preparation of polycarboxy-oxyalkylene polyester- polyether polyol as a liquid intermediate product based on lignin suitable for production of polyurethane materials. This is the chemical modification of sulphite or alkaline as well as organosolv lignin, in which during the first phase lignin reacts through a radical reaction with maleic anhydride. By subsequent hydrolysis the anhydride ring opens to form carboxyl groups, which are alkoxylated during the last phase. Through alkoxylation sections of linear polyether chains of terminal primary or secondary hydroxyl groups are created. This creates a liquid polyol based on lignin capable of reacting with isocyanates to form polyurethanes. This process, however, has the disadvantage of complicated process technological and expensiveness of chemical modification of lignin.
Another way of chemical modification to ensure miscibility of lignin with the polyol component is specified in patent no.US2005/0014919A1. Solubility of the sulphite type of lignin in polyols is partly ensured by sulphuric salts neutralisation resulting in sulphuric acid. The neutralisation can be executed through hydrolysis by acids or with use of a cation exchanger for cation exchange. Lignin bringing on the surface groups of sulphuric acid is miscible with polyols and according to the patent it is usable for the preparation of biodegradable reinforced polyurethane materials with the content of 1 to 40% of lignin. However, this efficient chemical modification procedure is only limited to the sulphite type of lignin.
A disadvantage of the existing procedures is either insufficient dispersion of lignin in polyols or lignin dispersion in polyols by means of toxic solvents. This fact limits the use of lignin to produce polyurethane materials or the production of the same is toxic and represents a burden for the environment.
Summary of the invention
This task is resolved by means of preparation of polyurethane materials according to the invention. The preparation comprises reaction of polyol with an isocyanate, with the addition of lignin at least in one reaction component. The invention is based in the reduction of the powder lignin particles in a dispersion device to the size of nanometres to micrometers and simultaneously they are dispersed without the use of solvents in a pre-polymer terminated by reactive isocyanate groups upon preparation of single-component polyurethane materials or in a polyol reaction component and/or W m isocyanate reaction component upon preparation of two-component polyurethane materials.
The dispersion preparation is carried out in dispersion devices characterised with a balanced grinding effect, sheer and dispersion phase circulation in the continual phase. These devices can comprise for example a pearl mill, a colloidal mill for wet grinding with a cone-shaped rotor, an attritor, a five-cylinder friction device or another device. The particular type of the dispersion device is selected according to the continuous phase viscosity, the size of the dispersion phase particles and the final dispersion viscosity. A sufficient grinding effect enables an effective crushing of agglomerates and aggregates of the powder lignin. The shear stress in the range of 103 - 105 s' will ensure sufficient exfoliation of micro and nano particles of lignin in the dispersion. For the given purpose it is necessary to combine the aforementioned stresses with a sufficient circulation to ensure equal disposition of the dispersed lignin particles in the reaction component. Using of an optimal dispersion device enables exclusion of volatile and often also toxic organic solvents or technologically or economically demanding chemical p re-modifications of lignin. The particular type of the dispersion device is selected according to the continuous phase viscosity, the size of the dispersion phase particles and the final dispersion viscosity. The size of the dispersed lignin particles ranges from 1.10"9m to 999.10"6m.
In an advantageous embodiment of the invention at least one substance to adjust chemical or physical characteristics of the dispersion achieved, mainly of the viscosity, is added to the lignin dispersion in the polymer and/or polyol reaction component and/or in the isocyanate reaction component. This substance can comprise an additive or another portion of one of the reaction components.
It is useful upon preparation of two-component polyurethane materials to first create a lignin dispersion in the first part of the polyol reaction component and subsequently to mix the dispersion with the second part of the polyol reaction component to homogenize it; the occurring mixture reacts with the isocyanate reaction component. However, it is also possible to disperse the lignin particles in the entire content of the polyol component, which is not further diluted and reacts directly with the isocyanate component. In a similar way we can carry out the dispersion of lignin in the isocyanate component or in case of single-component polyurethanes in the pre- polymer.
In an advantageous embodiment the polyol component comprises at least one substance or a combination of substances containing two or more hydroxyl groups. These substances can comprise for example glycols, carbohydrates, polyesterpolyols, oily polyols and/or their combination.
In another advantageous embodiment at least one additive or a combination of additives is added in any polyurethane system component. Adding of an additive depends on the particular final application of the produced polyurethane material. Additives improve the processing characteristics or the final product characteristics. For example in certain procedures catalysts are necessary to activate the reaction. It is advantageous when the additive is composed of at lest one substance from the following group or their combination: catalysts, blowing agents, defoamers, emulsifiers, dispersion agents, humidity absorbents, pigments, filling materials, stabilizers, or flame retardants.
Finally it is advantageous if the isocyanate component comprises at least one substance (or their combination) from the polyisocyanate or isocyanate group with blocked reactive groups or monomer isocyanates, such as: toluylene diisocyanate (TDI), isophorone diisocyanate (IPDI), hexamethylendiisocyanate (HMDI), diphenylmethaneisocyanate (HDI).
The subject of invention is also a polyurethane material prepared by the aforementioned method. The invention is based on the content of a powder lignin with the particle size reduced to nanometres and micrometers and dispersed in a pre-polymer terminated by at least one of the reactive isocyanate groups for single- component polyurethane materials or in a polyol reaction component and/or an isocyanate reaction component for two-component polyurethane materials. In an advantageous embodiment the polyurethane material is created as a polyurethane casting resin containing lignin in the range from 0.1 to 60% by weight. The polyurethane casting resin containing lignin is characterized with an increased electric resistance and improved thermal and mechanical features.
In another advantageous embodiment the polyurethane material is created as a polyurethane paint coat containing lignin in the range from 0.1 to 30% by weight.
In another advantageous embodiment the polyurethane material is created as a polyurethane foam material containing lignin in the range from 0.1 to 10% by weight. This design comprises soft, semi-hard, hard and other polyurethane foams.
In the last advantageous embodiment the polyurethane material is created as an adhesive or sealant containing pre-dried lignin in the range from 0.1 to 60% by weight.
Advantages of the method of preparation of polyurethane materials according to the invention are based on the fact that the method of preparation comprises a solvent- free high efficient dispersion of lignin in polyurethanes, which is technically easily realised and environmentally friendly. By modification of the operating conditions the procedure can be used to prepare a wide range of polyurethane materials. The polyurethane materials produced in compliance with the invention feature a range of improved physical characteristics, such as for example: an increased tensile strength, an elastic modules, toughness, electric characteristics, etc.
Examples of the preferred embodiments of the invention
It is understood that the examples of the invention's application as described and illustrated below are presented for illustration purposes and not as a limitation of examples of the invention's application for the cases given. The experts skilled in the art will find or will be able to find, with the use of routine experimentation, either higher or lower number of equivalents to specific embodiments of the invention specifically described herein. Even these equivalents shall be comprised in the scope of the following claims.
To compare the method of production and improvement of characteristics common production processes and common polyurethane materials are indicated with odd numbers (e.g. 1 , 3 and 5) and procedures and polyurethane materials created according to the invention are indicated with even numbers (e.g. 2, 4, 6 and 7).
Example 1 PU casting resin synthesis on the basis of castor oil and cured with
MDI (Standard No. 1)
Preparation of the PU casting resin is based on the reaction of the polyol component A and the isocyanate component B in a reaction mixture.
In the first phase the polyol component A is dosed in the reactor, i.e. 126.1g of castor oil (no. OH = 165mg KOH/g). A source of vacuum (an oil pump) is subsequently fixed to the reactor and under intense mixing the component A is heated up to the temperature of 90°C. Distillation under the pressure of <0.1 mbar during approximately 1 hour the water content in the polyol component A is decreased to <0.05% by weight. After termination of distillation the component A is cooled to the ambient temperature and after elimination of vacuum an inert gas, pre-dried nitrogen or argon is brought in the reactor.
During the second phase under intense stirring and upon ambient temperature 50, Og of component B (NCO index = 105) is added to component A. The isocyanate component B comprises Suprasec® 2642 (medium functional polymerized hexamethylene diisocyanate, NCO = 32.7%, by Huntsman). A source of vacuum is reconnected to the reactor (an oil pump). The reaction mixture under ambient temperature and decreased pressure <0.1mbar is homogenized by intense stirring during approximately 30 minutes.
After termination of homogenization the reactor is disconnected from the source of vacuum. The reaction mixture is removed from the reactor by casting in a prepared metal form sized 0.2 x 15 x 20cm. Curing of the polyurethane mixture is carried out in the metal form under ambient temperature during 24 hours and subsequently under the temperature of 80°C during 1 hour when polyurethane networking is finished.
Characteristics of the PL) elastomer (Standard No. 1) are provided in Table 1.
Example 2 PU cas ing resin synthesis on the base of castor oil and cured with MDI and with the lignin content of 15% by weight
Figure imgf000009_0001
lignin aggregates.
Figure imgf000009_0002
termination of distillation the component A is cooled to the ambient temperature and after elimination of vacuum an inert gas, pre-dried nitrogen or argon is brought in the reactor.
During the third phase under intense stirring and upon ambient temperature 50, Og of component B (NCO index = 105) is added to component A. The isocyanate component B is composed of Suprasec® 2642 (medium functional polymerized hexamethylene diisocyanate, NCO = 32.7%, by Huntsman). A source of vacuum is reconnected to the reactor (an oil pump). The reaction mixture under ambient temperature and decreased pressure <0.1mbar is homogenized by intense stirring during approximately 30 minutes. After termination of homogenization the reactor is disconnected from the source of vacuum. The reaction mixture is removed from the reactor by casting in a prepared metal form sized 0.2 x 15 x 20cm.
Curing of the polyurethane mixture with the content of the "organosolv" lignin of 15% by weight is carried out in the metal form under ambient temperature during 24 hours and subsequently under the temperature of 80°C during 1 hour when polyurethane networking is finished.
Characteristics of the PU elastomer with the content of "organosolv" lignin of 15% by weight are provided in Table 1.
Example 3 Synthesis of solvent-free PU paint coat based on castor oil and cured with TOI (Standard No. 2)
Preparation of the PU feasting resin is based on the reaction of the polyol component A and the isocyanate component B in a reaction mixture.
In the first phase the polyol component A is dosed in the reactor, i.e. 10. Og of castor j
oil (no. OH = 165mg KOH/g). A source of vacuum (an oil pump) is subsequently fixed to the reactor and under intense mixing the component A is heated up to the temperature of 90°C. By means of distillation under the pressure of <0.1mbar during approximately 1 hour the water content in the polyol component A is decreased to <0.05% by weight. After termination of distillation the component A is cooled to the ambient temperature and after elimination of vacuum an inert gas, pre-dried nitrogen or argon, is brought in the reactor.
In the third phase under intense stirring and under ambient temperature catalyst DABCO 33-LV® Catalyst (tertiary amine, by Air Products) with the concentration of 0.1% by weight is added to component A on the reaction mixture mass. Subsequently component A is mixed with 2.4g of component B (NCO index = 105). The isocyanate component B is composed of Scuranate® TDI 80 (toluylene diisocyanate, NCO = 48.2%, by Perstorp). After termination of homogenisation the reaction mixture is drawdowned on a glass plate and on a polypropylene substrate by wire-wound rod 200μπι.
Curing of the poiyurethane film is carried out first by free drying under ambient temperature during 24 hours and subsequently under the temperature of 70°C during further 24 hours. The film curing is finished under 120°C during 1 hour.
Characteristics of the high dry mass PU paint coat (Standard No. 2) are provided in Table 2.
Example 4 Synthesis of solvent-free PU paint coat based on castor oil and cured with TDI and with the lignin content of 15% of the weigh.
In the first phase 50% dispersion from the „organosolv" lignin in castor oil is prepared. In a baker with the volume of 100ml we mix 25. Og of castor oil with 25. Og of lignin. Subsequently the mixture is ten times repeatedly dispersed with high shear forces under the temperature of 25°C in a shear device to reduce the size and dispersion of the particles (Three Roll Mill EXAKT 80 E, by EXAKT technologies, Inc.). The prepared dispersion is a highly viscose paste without presence of any lignin aggregates.
In the second phase the polyol component A is dosed in the reactor, i.e. a mixture of 7.4g of castor oil (no. OH = 165 mg KOH/g) and 2.6g of 50% dispersion of the „organosolv" lignin in the castor oil. A source of vacuum (an oil pump) is subsequently fixed to the reactor and under intense mixing the component A is heated up to the temperature of 90°C. Distillation under the pressure of <0.1mbar during approximately 1 hour the water content in the polyol component A is decreased to <0.05% by weight. After termination of distillation the component A is cooled to the ambient temperature and after elimination of vacuum an inert gas, pre- dried nitrogen or argon is brought in the reactor.
In the third phase upon intense stirring and under ambient temperature catalyst DABCO 33-LV® Catalyst (tertiary amine, by Air Products) with the concentration of 0.1% by weight is added to component A upon the reaction mixture mass. Subsequently component A is mixed with 2.3g of component B (NCO index = 105). The isocyanate component B is composed of Scuranate® TDI 80 (toluylene diisocyanate, NCO = 48.2%, by Perstorp).
After termination of homogenisation the reaction mixture is drawdowned on a glass plate and on a polypropylene substrate by wire-wound rod 200μιη.
Curing of the polyurethane film is carried out first by free drying under ambient temperature during 24 hours and subsequently under the temperature of 70°C during further 24 hours. The film curing is finished under 120°C during 1 hour.
Characteristics of the solvent-free PL) paint coat with the lignin content of 0% by weight are provided in Table 2.
Example 5 Synthesis of the soft PU foam standard
Preparation of the soft PU foam is based on the reaction of the polyol component A and the isocyanate component B in a reaction mixture.
In the first phase we take a waxed paper crucible with the volume of 11 to dose the component A of the reaction mixture composed of 50.00g of polyol Slovaprop® G-48 S (copolymer of propylene and ethylene oxide, no. OH = 48 mg KOH/g, Novacke chemicke zavody), 0.08g of promoter of the creation of urethane bonds Dabco® 33LV (Air Products), 0.50g of the silicon surfactant Dabco® DC5906 (Air Products), 0.10 g of the networked catalyst based on tin Kosmos® 29 (Evonik), and 1.78g of distilled water used as a blowing agent. Ingredients of component A are homogenized during 30 seconds under the intense stirring of 2,000 turns/min.
One dose of the isocyanate component B composed of 23.48g of Scuranate® TDI 80 (toluylene diisocyanate, NCO = 48.2%, by Perstorp) is added to component A in the second phase. Subsequently the reaction mixture is homogenized during 30 seconds under the stirrer speed of 2,000 turns/min. After the stirring termination the mixture foams up. The created polyurethane foam is subsequently placed in the dryer pre-heated to 100°C for 15 minutes. Curing of the soft polyurethane foam is terminated with 24-hour curing under the temperature of 25°C.
Characteristics of the soft polyurethane foam standard with the theoretical density of 30kg/m3 are provided in Table 3.
Example 6 Synthesis of the soft PU foam with the lignin content of 1% by weight
In the first phase we prepare a 50% dispersion of the„organosolv" lignin in polyol Slovaprop® G-48 S (copolymer of propylene and ethylene oxide, no. OH = 48 mg KOH/g, Novacke chemicke zavody). In a baker with the volume of 100ml we mix 25. Og of castor oil with 25. Og of lignin. Subsequently the mixture is ten times repeatedly dispersed with high shear forces under the temperature of 25°C in a shear device to reduce the size and dispersion of the particles (Three Roll Mill EXAKT 80 E, by EXAKT technologies, Inc.). The prepared dispersion is a highly viscose paste without presence of any lignin aggregates.
In the second phase we take a waxed paper crucible with the volume of 11 to dose the component A of the reaction mixture composed of 3.04g of 50% lignin dispersion in polyol, 48.48g of polyol Slovaprop® G-48 S, 0.08g of promoter of the creation of urethane bonds Dabco® 33LV (Air Products), 0.50g of the silicon surfactant Dabco® DC5906 (Air Products), 0.10 g of the networked catalyst based on tin Kosmos® 29 (Evonik), and 1.78g of distilled water used as a blowing agent. Ingredients of component A are homogenized during 30 seconds under the intense stirring of 2,000 turns/min.
One dose of the isocyanate component B composed of 23.48g of Scuranate® TDI 80 (toluylene diisocyanate, NCO = 48.2%, by Perstorp) is added to component A in the third phase. Subsequently the reaction mixture is homogenized during 30 seconds under the stirrer speed of 2,000 turns/min. After the stirring termination the mixture foams up. The created polyurethane foam is subsequently placed in the dryer pre-heated to 100°C for 15 minutes. Curing of the soft polyurethane foam is terminated with 24-hour curing under the temperature of 25°C.
Characteristics of the soft polyurethane foam with the lignin consent of 1 % by weight and the theoretical density of 30kg/m3 are provided in Table 3.
Example 7 Preparation of PU adhesive with the lignin content
100g of pre-dried lignin (60°C, 24 hours) is stirred in a slow-running stirrer in the polyurethane pre-polymer with the content of 12.6% of free isocyanate groups. The pre-mixture is subsequently repeatedly dispersed on a five-cylinder friction device to create a perfectly smooth paste with the viscosity of 65Pa.s. The prepared dispersion is used as a structural adhesive to bond together ABS substrates. Shear strength of the adhesive on the pre-treated surface of the plastic substrate is 6-8MPa.
Table 1 Characteristics of polyurethane casting resins
Figure imgf000015_0001
Rv ... electrical resistance
P ... electrical resistivity
σ ... tensile strength
ε ... elongation at break
E ... elastic modulus
W ... work to break
HD ... surface hardness (Durometer)
Tg ... glass transition temperature (DMA)
WA ... water absorption
Table 2 Characteristics of solvent-free polyurethane paint coats
Figure imgf000015_0002
σ ... tensile strength
ε ... elongation at break
Ε ... elastic modulus
W ... work to break
Tg ... glass transition temperature (DMA)
Table 3 Characteristics of soft polyurethane foams
Figure imgf000016_0001
pv ... volume density
IFD 25 ... the strength necessary to compress the sample to 25% of the original height
IFD 65 ... the strength necessary to compress the sample to 65% of the original height
Tg ... glass transition temperature (DSC)
Industrial applicability
The method of preparation of polyurethane materials according to the invention can be used for industrial production and industrial applications of polyurethane materials containing Iignin in various areas, for example in electrical engineering, construction industry, chemical and consumer goods industry.

Claims

The method of preparation of polyurethane materials in the reaction of polyol with isocyanate with lignin added in at least one reaction component characterised by that the powder lignin particles are reduced in the dispersion facility to the size of nanometres and to micrometers and they are simultaneously dispersed without the use of solvents in a pre-polymer terminated by reactive isocyanate groups upon preparation of single- component polyurethane materials or in a polyol reaction component and/or in an isocyanate reaction component upon preparation of two-component polyurethane materials.
The method according to claim 1 characterised by that at least one substance to adjust chemical or physical characteristics of the originated dispersion, mainly of the viscosity, is added to the lignin dispersion in the prepolymer and/or polyol reaction component and/or isocyanate reaction component; this substance is an additive or another portion of one of the reaction components.
The method according to claim 2 characterised by that when preparing two- component polyurethane materials in the first step a lignin dispersion in the first part of the polyol reaction component is created and subsequently the dispersion is mixed with the second part of the polyol reaction component to homogenize it; the mixture created is reacted with the isocyanate reaction component.
The method according to claim 2 characterised by that to the lignin dispersion in the pre-polymer and/or polyol reaction component and/or isocyanate reaction component at least one additive is added composed of at least one substance or a combination of substances from the following groups: catalysts, blowing agents, defoamers, emulsifiers, dispersion agents, humidity absorbents, pigments, filling materials, stabilizers, or flame retardants.
5. The method according to at least one of the claims 1 to 4 characterised by that the polyol component comprises at least one substance or a combination of substances containing two or more hydroxyl groups from the group of glycols, carbohydrates, polyesterpolyols, oily polyols and/or their combinations.
6. The method according to at least one of the claims 1 to 5 characterised by that the isocyanate reaction component comprises at least one substance or a combination of substances from the group of polyisocyanates or monomer isocyanates: toluylene diisocyanate (TDI), isophorone diisocyanate (IPDI), hexamethylendiisocyanate (HMDI), diphenylmethaneisocyanate (HDI).
7. Polyurethane material prepared according to at least one of the claims 1 to 6 characterised by that it contains powder lignin with the particles size reduced to nanometres and micrometers and dispersed in a pre-polymer terminated by reactive isocyanate groups for single-component polyurethane materials or in a polyol reaction component and/or an isocyanate reaction component for two- component polyurethane materials.
8. Polyurethane material according to the claim 7 characterised by that it is created as a polyurethane casting resin containing lignin in the range from 0.1 to 60% by weight.
9. Polyurethane material according to the claim 7 characterised by that it is created as a polyurethane paint coat containing lignin in the range from 0.1 to 30% by weight.
10. Polyurethane material according to the claim 7 characterised by that it is created as a polyurethane foam material containing lignin in the range from 0.1 to 10% by weight.
11. Poiyurethane material according to the claim 7 characterised by that it is created as a poiyurethane adhesive containing pre-dried lignin in the range from 0.1 to 60% by weight.
12. Poiyurethane material according to the claim 7 characterised by that it is created as a poiyurethane sealant containing pre-dried lignin in the range from 0.1 to 60% by weight.j
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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015021541A1 (en) * 2013-08-13 2015-02-19 Enerlab 2000 Inc. Process for the preparation of lignin based polyurethane products
CN104559907A (en) * 2014-12-26 2015-04-29 邢柯君 Environment-friendly composite adhesive as well as preparation method and application thereof
WO2015083092A1 (en) * 2013-12-05 2015-06-11 Stora Enso Oyj A composition in the form of a lignin polyol, a method for the production thereof and use thereof
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US10087298B2 (en) 2013-12-27 2018-10-02 Industrial Technology Research Institute Bio-polyol composition and bio-polyurethane foam material
US10323115B2 (en) * 2015-12-07 2019-06-18 Industrial Technology Research Institute Bio-polyol composition and bio-polyurethane foam
EP3549968A1 (en) * 2018-04-06 2019-10-09 RAMPF Holding GmbH & Co. KG Lignin-containing polyurethanes
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CN111454465A (en) * 2020-04-15 2020-07-28 黎明化工研究设计院有限责任公司 Modified lignin, full-water-based low-density flame-retardant flexible polyurethane foam composition and preparation method thereof
CN113201112A (en) * 2021-04-06 2021-08-03 华南理工大学 Waterborne polyurethane with lignin as chain extender and preparation method and application thereof
CN113980289A (en) * 2020-07-01 2022-01-28 长春工业大学 Nitrogen and phosphorus-containing lignin-based flame retardant, and preparation method and application thereof
CN114773564A (en) * 2022-05-05 2022-07-22 浙江科技学院 Self-adhesive polyurethane for dialysis functional paper and preparation method and application thereof
CN115449329A (en) * 2022-09-22 2022-12-09 广西科学院 Method for modifying adhesive by lignin
EP4311837A1 (en) 2022-07-28 2024-01-31 Raiz - Instituto De Investigação Da Floresta E Papel Process for incorporating lignin into liquid lignin-based polyols and use of the resulting product for the preparation of polyurethanes

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114808475A (en) * 2022-04-23 2022-07-29 苏州瑞高新材料有限公司 Dry-type foamed PU sun-shading curtain leather and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4017474A (en) 1975-08-15 1977-04-12 Research Corporation Polyurethane intermediates and products and methods of producing same from lignin
JPS63182327A (en) 1987-01-23 1988-07-27 Agency Of Ind Science & Technol Production of polyurethane containing lignin
FR2689366A1 (en) * 1992-04-02 1993-10-08 Bono Pierre Bio:destructible cellular support for soilless - made from powdered pure lignin and polyurethane binder
US6025452A (en) * 1996-12-27 2000-02-15 Kurple; Kenneth R. Lignin based polyols
US20050014919A1 (en) 2001-06-15 2005-01-20 Hyoe Hatakeyama Lignin-based polyurethane and process for producing the same

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2657353B1 (en) * 1990-01-23 1993-07-02 Bono Pierre DEGRADABLE PLASTIC FILM COMPRISING AN ACTIVE VEGETABLE LOAD, LIGNIN.
ES2150825B1 (en) * 1996-09-25 2001-07-01 Univ Oviedo PROCEDURE AND FORMULATIONS FOR OBTAINING THERMOPLASTIC / LIGNIN COMPOUND MATERIALS IN A THERMOCINETIC MIXER IN MINIMUM CONDITIONS OF THERMAL DEGRADATION.
CN102093574A (en) * 2009-12-14 2011-06-15 延边大学 Water dispersed lignin polyurethane material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4017474A (en) 1975-08-15 1977-04-12 Research Corporation Polyurethane intermediates and products and methods of producing same from lignin
JPS63182327A (en) 1987-01-23 1988-07-27 Agency Of Ind Science & Technol Production of polyurethane containing lignin
FR2689366A1 (en) * 1992-04-02 1993-10-08 Bono Pierre Bio:destructible cellular support for soilless - made from powdered pure lignin and polyurethane binder
US6025452A (en) * 1996-12-27 2000-02-15 Kurple; Kenneth R. Lignin based polyols
US20050014919A1 (en) 2001-06-15 2005-01-20 Hyoe Hatakeyama Lignin-based polyurethane and process for producing the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
R.W. THRING ET AL.: "Polyurethanes from ALCELL LIGNIN", BIOMASS AND BIOENERGY, vol. 13, no. 3, 25 February 1997 (1997-02-25), Elsevier, pages 125 - 132, XP002720465, ISSN: 0961-9534 *

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Publication number Priority date Publication date Assignee Title
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WO2015021541A1 (en) * 2013-08-13 2015-02-19 Enerlab 2000 Inc. Process for the preparation of lignin based polyurethane products
US10196478B2 (en) 2013-12-05 2019-02-05 Stora Enso Oyj Composition in the form of a lignin polyol, a method for the production thereof and use thereof
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CN108473646A (en) * 2015-10-21 2018-08-31 亨茨曼国际有限公司 Lignin is incorporated in polyurethane products
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RU2715702C2 (en) * 2015-10-21 2020-03-03 ХАНТСМЭН ИНТЕРНЭШНЛ ЭлЭлСи Introducing lignin into polyurethane products
US10604616B2 (en) 2015-10-21 2020-03-31 Huntsman International Llc Incorporation of lignin in polyurethane products
WO2017067769A1 (en) 2015-10-21 2017-04-27 Huntsman International Llc Incorporation of lignin in polyurethane products
US10323115B2 (en) * 2015-12-07 2019-06-18 Industrial Technology Research Institute Bio-polyol composition and bio-polyurethane foam
RU2720508C1 (en) * 2016-10-04 2020-04-30 Аркема Франс Method of producing alkoxylated polyphenols
KR101831737B1 (en) * 2017-03-02 2018-02-23 씨제이제일제당 주식회사 Rigid polyurethane foam and preparation method thereof
EP3549968A1 (en) * 2018-04-06 2019-10-09 RAMPF Holding GmbH & Co. KG Lignin-containing polyurethanes
WO2019193142A1 (en) * 2018-04-06 2019-10-10 Rampf Holding Gmbh & Co. Kg Lignin-containing polyurethanes
CN111454465A (en) * 2020-04-15 2020-07-28 黎明化工研究设计院有限责任公司 Modified lignin, full-water-based low-density flame-retardant flexible polyurethane foam composition and preparation method thereof
CN113980289A (en) * 2020-07-01 2022-01-28 长春工业大学 Nitrogen and phosphorus-containing lignin-based flame retardant, and preparation method and application thereof
CN113980289B (en) * 2020-07-01 2024-01-26 长春工业大学 Nitrogen and phosphorus-containing lignin-based flame retardant, preparation method and application thereof
CN113201112A (en) * 2021-04-06 2021-08-03 华南理工大学 Waterborne polyurethane with lignin as chain extender and preparation method and application thereof
CN113201112B (en) * 2021-04-06 2022-06-14 华南理工大学 Waterborne polyurethane with lignin as chain extender and preparation method and application thereof
CN114773564A (en) * 2022-05-05 2022-07-22 浙江科技学院 Self-adhesive polyurethane for dialysis functional paper and preparation method and application thereof
CN114773564B (en) * 2022-05-05 2023-09-26 浙江科技学院 Self-adhesive polyurethane for dialysis functional paper, and preparation method and application thereof
EP4311837A1 (en) 2022-07-28 2024-01-31 Raiz - Instituto De Investigação Da Floresta E Papel Process for incorporating lignin into liquid lignin-based polyols and use of the resulting product for the preparation of polyurethanes
CN115449329A (en) * 2022-09-22 2022-12-09 广西科学院 Method for modifying adhesive by lignin

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