WO2023166036A1 - Polyurethane (pu) composition and method of producing pu composition - Google Patents

Polyurethane (pu) composition and method of producing pu composition Download PDF

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Publication number
WO2023166036A1
WO2023166036A1 PCT/EP2023/055148 EP2023055148W WO2023166036A1 WO 2023166036 A1 WO2023166036 A1 WO 2023166036A1 EP 2023055148 W EP2023055148 W EP 2023055148W WO 2023166036 A1 WO2023166036 A1 WO 2023166036A1
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composition
graphene
component
isocyanate
range
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PCT/EP2023/055148
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French (fr)
Inventor
Ali ZOLALI
Jinghang Wu
Sergio Franyutti
Pavlinac JON P
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Basf Se
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Publication of WO2023166036A1 publication Critical patent/WO2023166036A1/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/32Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203Polyhydroxy compounds
    • C08G18/3206Polyhydroxy compounds aliphatic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/32Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271Hydroxyamines
    • C08G18/3278Hydroxyamines containing at least three hydroxy groups
    • C08G18/3284Hydroxyamines containing at least three hydroxy groups containing four hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4804Two or more polyethers of different physical or chemical nature
    • C08G18/4816Two or more polyethers of different physical or chemical nature mixtures of two or more polyetherpolyols having at least three hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4833Polyethers containing oxyethylene units
    • C08G18/4837Polyethers containing oxyethylene units and other oxyalkylene units
    • C08G18/4841Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666Compounds of group C08G18/48 or C08G18/52
    • C08G18/667Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666Compounds of group C08G18/48 or C08G18/52
    • C08G18/667Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6677Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666Compounds of group C08G18/48 or C08G18/52
    • C08G18/667Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6688Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • C08K3/042Graphene or derivatives, e.g. graphene oxides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04Polyurethanes

Definitions

  • the present invention relates to a polyurethane (PU) composition, a method of producing the PU composition, and uses of the PU composition.
  • PU polyurethane
  • Polyurethane (PU) compositions are widely used for the physical properties of flexibility, ability to form variety of shapes, molding. However, many PU compositions do not have suitable electrical and thermal properties. Adding fillers for improving some electrical and thermal properties require higher loading and result in change in other physical properties.
  • the PU composition is associated with low coefficient of friction CoF, improved surface resistivity and fire resistance performance with no dripping requirement.
  • the presently claimed invention is directed to a polyurethane (PU) composition prepared from a reaction mixture comprising: a. Part A with at least one isocyanate reactive component; b. Part B with at least one isocyanate; wherein the reaction mixture includes at least one graphene component and at least one carbon black (CB) component; wherein graphene component is present in Part A and/ or Part B; and wherein carbon black (CB) component is present in Part A and/ or Part B.
  • PU polyurethane
  • the presently claimed invention is directed to a method of obtaining a polyurethane (PU), the method comprising: a. providing the Part A and the Part B of the reaction mixture for the composition; b. mixing the Part A and the Part B; c. optionally heating the reaction mixture.
  • PU polyurethane
  • the presently claimed invention is directed to an electrically semi -conductive system based on the PU composition.
  • the presently claimed invention is directed to the use of the PU composition in electrostatic discharge (ESD) applications.
  • steps of a method or use or assay there is no time or time interval coherence between the steps, that is, the steps may be carried out simultaneously or there may be time intervals of seconds, minutes, hours, days, weeks, months or even years between such steps, unless otherwise indicated in the application as set forth herein above or below.
  • An aspect of the present invention is an embodiment, directed towards a polyurethane (PU) composition prepared from a reaction mixture comprising: a. Part A with at least one isocyanate reactive component; b. Part B with at least one isocyanate; wherein the reaction mixture includes at least one graphene component and at least one carbon black (CB) component; wherein graphene component is present in Part A and/ or Part B; and wherein carbon black (CB) component is present in Part A and/ or Part B.
  • PU polyurethane
  • the PU composition is prepared from a reaction mixture.
  • the reaction mixture comprises the Part A and Part B.
  • the PU composition is formed as a product of reaction mixture of Part A with at least one isocyanate reactive component and Part B with at least one isocyanate.
  • the reaction mixture includes at least one graphene component and at least one carbon black (CB) component.
  • the graphene component is present in Part A and/ or Part B; and the carbon black (CB) component is present in Part A and/ or Part B.
  • At least one graphene component and/ or the at least one carbon black (CB) component is added to the Part A.
  • the at least one graphene component and/ or the at least one carbon black (CB) component is added to the Part B.
  • the at least one graphene component and the at least one carbon black (CB) component is added to the Part B.
  • the at least one graphene component is added to the Part A and the at least one carbon black (CB) component is added to the Part B.
  • the at least one graphene component is added to the Part B and the at least one carbon black (CB) component is added to the Part A.
  • both the at least one graphene component and the at least one carbon black (CB) component is added to the Part A.
  • the isocyanate reactive component of the PU composition comprises at least one polyol.
  • Part A further comprises optionally an additive that includes a chain extender, a cross linker, a catalyst, an antistatic agent, a flame retardant, at least one reaction mixture additives, and at least one reaction mixture filler, or any combination thereof.
  • the polyols include poly ether polyols, polyester polyols, poly etherester polyols, and a combination thereof.
  • the polyether polyols are obtainable by known methods, for example by anionic polymerization with alkali metal hydroxides, e.g., sodium hydroxide or potassium hydroxide, or alkali metal alkoxides, e.g., sodium methoxide, sodium ethoxide, potassium ethoxide or potassium isopropoxide, as catalysts and by adding at least one amine- containing starter molecule, or by cationic polymerization with Lewis acids, such as antimony pentachloride, boron fluoride etherate and so on, or fuller’s earth, as catalysts from one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene moiety.
  • alkali metal hydroxides e.g., sodium hydroxide or potassium hydroxide
  • alkali metal alkoxides e.g., sodium methoxide, sodium ethoxide, potassium ethoxide or potassium isopropoxide
  • Lewis acids such as antimony
  • Starter molecules are generally selected such that their average functionality is preferably in the range of 2.0 to 8.0, and more preferably in the range of 3.0 to 8.0. Optionally, a mixture of suitable starter molecules is used.
  • Starter molecules for polyether polyols include amine containing and hydroxylcontaining starter molecules. Suitable amine containing starter molecules include, for example, aliphatic and aromatic diamines such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, phenylenediamines, toluenediamine, diaminodiphenylmethane and isomers thereof.
  • Other suitable starter molecules further include alkanolamines, e.g. ethanolamine, N-m ethylethanolamine and N-ethylethanolamine, dialkanolamines, e.g., diethanolamine, N- methyldiethanolamine and N-ethyldi ethanolamine, and trialkanolamines, e.g., triethanolamine, and ammonia.
  • alkanolamines e.g. ethanolamine, N-m ethylethanolamine and N-ethylethanolamine
  • dialkanolamines e.g., diethanolamine, N- methyldiethanolamine and N-ethyldi ethanolamine
  • trialkanolamines e.g., triethanolamine, and ammonia.
  • Suitable amine containing starter molecules are selected from ethylenediamine, phenylenediamines, toluenediamine or isomers thereof. In one embodiment, it is ethylenediamine.
  • Hydroxyl-containing starter molecules are selected from sugars, sugar alcohols, for e.g. glucose, mannitol, sucrose, pentaerythritol, sorbitol; polyhydric phenols, resols, e.g., oligomeric condensation products formed from phenol and formaldehyde, trimethylolpropane, glycerol, glycols such as ethylene glycol, propylene glycol and their condensation products such as polyethylene glycols and polypropylene glycols, e.g., diethylene glycol, triethylene glycol, dipropylene glycol, and water or a combination thereof.
  • sugars e.g. glucose, mannitol, sucrose, pentaerythritol, sorbitol
  • polyhydric phenols, resols e.g., oligomeric condensation products formed from phenol and formaldehyde, trimethylolpropane, glycerol
  • glycols
  • Suitable hydroxyl containing starter molecules are selected from sugar and sugar alcohols such as sucrose, sorbitol, glycerol, pentaerythritol, trimethylolpropane or mixtures thereof. In some embodiments the hydroxyl containing starter molecules are selected from sucrose, glycerol, pentaerythritol or trimethylolpropane.
  • Suitable alkylene oxides having 2 to 4 carbon atoms are, for example, ethylene oxide, propylene oxide, tetrahydrofuran, 1,2-butylene oxide, 2,3-butylene oxide, and styrene oxide.
  • Alkylene oxides can be used singly, alternatingly in succession or as mixtures.
  • the alkylene oxides are propylene oxide and/or ethylene oxide.
  • the alkylene oxides are mixtures of ethylene oxide and propylene oxide that comprise more than 50 wt.-% of propylene oxide.
  • the polyester polyols are based on the reaction product of carboxylic acids or anhydrides with hydroxy group containing compounds.
  • Suitable carboxylic acids or anhydrides have preferably from 2 to 20 carbon atoms, or from 4 to 18 carbon atoms, for example succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, oleic acid, phthalic anhydride. Particularly comprising of phthalic acid, isophthalic acid, terephthalic acid, oleic acid and phthalic anhydride or a combination thereof.
  • Suitable hydroxyl containing compounds are selected from ethanol, ethylene glycol, propylene- 1,2-gly col, propylene-l,3-glycol, butyl-ene-l,4-glycol, bu-tylene-2,3- glycol, hexane-l,6-diol, octane- 1,8 -diol, neopentyl glycol, cyclohexane dimethanol (1,4-bis- hydroxy-methylcyclohexane), 2-methyl-propane-l,3-diol, glycerol, trimethylolpropane, hexane-l,2,6-triol, butane -1,2,4-triol, trimethylolethane, pentaerythritol, quinitol, mannitol, sorbitol, methyl glycoside, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene
  • the hydroxyl containing compound is selected from ethylene glycol, propylene- 1,2-gly col, propylene-l,3-glycol, butylene- 1,4-gly col, butylene-2,3-glycol, hexane-l,6-diol, octane- 1,8 -diol, neopentyl glycol, cyclohexane dimethanol (1,4-bis-hydroxy-methylcyclohexane), 2-methyl-propane-l,3-diol, glycerol, trimethylolpropane, hexane-l,2,6-triol, butane -1,2,4-triol, trimethylolethane, pentaerythritol, quinitol, mannitol, sorbitol, methyl glycoside or di ethylene glycol.
  • the hydroxyl containing compound is selected from ethylene glycol, propylene- 1,2-glycol, pro-pylene-l,3-glycol, butyl-ene- 1,4-gly col, butylene-2,3-glycol, hexane-l,6-diol, octane- 1,8 -diol, neopentyl glycol or di ethylene glycol.
  • the hydroxyl containing compound is selected from hexane-l,6-diol, neopentyl glycol and di ethylene glycol.
  • Such polyetherester polyols are obtainable as a reaction product of i) at least one hydroxyl-containing starter molecule; ii) of one or more fatty acids, fatty acid monoesters or mixtures thereof; iii) of one or more alkylene oxides having 2 to 4 carbon atoms.
  • the starter molecules of component i) are generally selected such that the average functionality of component i) is preferably 3.8 to 4.8, or from 4.0 to 4.7, or even from 4.2 to 4.6.
  • a mixture of suitable starter molecules is used.
  • Suitable hydroxyl containing starter molecules of component i) are selected from sugars, sugar alcohols (glucose, mannitol, sucrose, pentaerythritol, sorbitol), polyhydric phenols, resols, e.g., oligomeric condensation products formed from phenol and formaldehyde, trimethylolpropane, glycerol, glycols such as ethylene glycol, propylene glycol and their condensation products such as polyethylene glycols and polypropylene glycols, e.g., diethylene glycol, triethylene glycol, dipropylene glycol, and water or a combination thereof.
  • the hydroxyl containing starter molecules of component i) are selected from sugars and sugar alcohols such as sucrose and sorbitol, glycerol, and mixtures of said sugars and/or sugar alcohols with glycerol, water and/or glycols such as, for example, diethylene glycol, dipropylene glycol or combination thereof.
  • sugars and sugar alcohols such as sucrose and sorbitol, glycerol, and mixtures of said sugars and/or sugar alcohols with glycerol, water and/or glycols such as, for example, diethylene glycol, dipropylene glycol or combination thereof.
  • Said fatty acid or fatty acid monoester ii) is selected from polyhydroxy fatty acids, ricinoleic acid, hydroxyl-modified oils, hydroxyl-modified fatty acids and fatty acid esters based in myristoleic acid, palmitoleic acid, oleic acid, stearic acid, palmitic acid, vaccenic acid, petroselic acid, gadoleic acid, erucic acid, nervonic acid, linoleic acid, a- and g-linolenic acid, stearidonic acid, arachidonic acid, timnodonic acid, clupanodonic acid and cervonic acid or a combination thereof.
  • Fatty acids can be used as purely fatty acids. In this regard, preference is given to using fatty acid methyl esters such as, for example, biodiesel or methyl oleate.
  • Biodiesel is to be understood as meaning fatty acid methyl esters within the meaning of the EN 14214 standard from 2010. Principal constituents of biodiesel, which is generally produced from rapeseed oil, soybean oil or palm oil, are methyl esters of saturated C16 to C18 fatty acids and methyl esters of mono- or pol-yunsaturated Cl 8 fatty acids such as oleic acid, linoleic acid and linolenic acid.
  • Suitable alkylene oxides iii) having 2 to 4 carbon atoms are, for example, ethylene oxide, propylene oxide, tetrahydrofuran, 1,2-butylene oxide, 2,3 -butylene oxide and/or styrene oxide.
  • Alkylene oxides can be used singly, alternatingly in succession or as mixtures.
  • the alkylene oxides comprise propylene oxide and ethylene oxide.
  • the alkylene oxide is a mixture of ethylene oxide and propylene oxide comprising more than 50 wt.-% of propylene oxide.
  • the alkylene oxide comprises purely propylene oxide.
  • the at least one polyol has an average functionality in the range of 2.0 to 8.0, the hydroxyl number in the range of 20 mg KOH/g to 800 mg KOH/g and the nominal molecular weight in the range of 200 g/ mole to 6000 g/ mole.
  • the polyol has OH value ranging from 20 mg KOH/g to 800 mg KOH/g, or from 20 mg KOH/g to 750 mg KOH/g, or from 20 mg KOH/g to 700 mg KOH/g, or from 20 mg KOH/g to 650 mg KOH/g, or from 20 mg KOH/g to 600 mg KOH/g.
  • the polyol has OH value ranging from 25 mg KOH/g to 600 mg KOH/g, or from 30 mg KOH/g to 600 mg KOH/g, or from 40 mg KOH/g to 600 mg KOH/g, 50 mg KOH/g to 600 mg KOH/g.
  • the polyol has OH value ranging from 100 mg KOH/g to 600 mg KOH/g, or from 200 mg KOH/g to 600 mg KOH/g, or from 300 mg KOH/g to 600 mg KOH/g, or from 350 mg KOH/g to 600 mg KOH/g
  • Preferred polyol used are with the molecular weight distribution from 100 g/ mol to 6000 g/ mol, or from 200 g/ mol to 6000 g/ mol, or from 300 g/ mol to 6000 g/ mol, or from 350 g/ mol to 6000 g/ mol.
  • the polyol used are with the molecular weight distribution from 350g/ mol to 4500 g/ mol, or from 350 g/ mol to 4000 g/ mol, or from 350 g/ mol to 3500 g/ mol, or from 350 g/ mol to 3000 g/ mol, or from 350 g/ mol to 3000 g/ mol, or from 350 g/ mol to 2500 g/ mol, or from 350 g/ mol to 2450 g/ mol, or from 350 g/ mol to 2400 g/ mol, or from 350 g/ mol to 2350 g/ mol.
  • Suitable polyols in the polyol composition are preferably selected from Polytetrahydrofurane (PolyTHF), polyether polyols, polyester polyols, or polycarbonate polyols.
  • the polyol comprises a PolyTHF.
  • the at least one polyol is polyether polyols, polyester polyols, polyetherester polyols, polytetrahydrofuran, or a combination thereof.
  • the polyol composition is a polyol mixture (i) based on the mixture of at least two, preferably separately prepared polyol.
  • at least two polyol it is meant that two different polyols are used, which have different mean molecular weight data.
  • the polyol composition is a polyol mixture (i) based on the mixture of at least three, preferably separately prepared polyol.
  • at least three polyol it is meant that three different polyols are used, which have different mean molecular weight data.
  • the combination of more than one polyol is associated with obtaining a lower Coefficient of Friction (CoF) value.
  • the PU Composition with polyol/s having an average functionality of about 3.5 to 4.0 are associated with the lowest CoF. Using a polyol with lower functionality resulted in higher CoF.
  • the reaction mixture for the PU Composition includes the graphene.
  • the graphene is added either in the Part A or the Part B or both part of the reaction mixture.
  • the graphene component is present in Part A and/ or Part B.
  • the graphene includes monolayer graphene, few-layer graphene (FLG), multi-layer graphene (MLG), graphene nano-platelets (GNP), graphite oxides (GO), graphite ore, reduced graphene oxides (rGO), graphene quantum dots, graphene ribbons, suspended graphene particles or membranes thereof, graphene master batches thereof, or combination thereof.
  • the graphene component in the PU composition is in range from 0.01 wt.% to 10.0 wt.%, or 0.01 to 9.5 wt.% or, from 0.01 wt.% to 9.0 wt.%, or from 0.01 wt.% to 8.5 wt.%, or from 0.01 wt.% to 8.0.0 wt.%, or from 0.01 wt.% to 7.5 wt.%, or from 0.01 wt.% to 7.0 wt.%, or from 0.01 wt.% to 6.5 wt.%, or from 0.01 wt.% to 6.0 wt.%, or from 0.01 wt.% to 5.5 wt.%, or from 0.01 wt.% to 5.0 wt.% of the PU composition.
  • the graphene component is in range from 0.05 wt.% to 5.0 wt.%, or from 0.10 wt.% to 5.0 wt.%, or from 0.15 wt.% to 5.0 wt.%, or from 0.20 wt.% to 5.0 wt.%, or from 0.25 wt.% to 5.0 wt.%, or from 0.30 wt.% to 5.0 wt.%, or from 0.35 wt.% to 5.0 wt.%, or from 0.40 wt.% to 5.0 wt.% of the PU composition.
  • the graphene is in form of the GNP, an oxidized form of graphene, functionalized with oxygen-containing groups.
  • the GNP is described to have a single platelet structure, i.e., single atomic layer structure or as having a multi -platelet structure.
  • the GNP has layer structure with layers in range from
  • the GNP has a layer structure with layers in from
  • the GNP has a layer structure with layers in range from 4 to 15 layers or from 1 to 10 layers.
  • the GNP has a particle size in range of 0.5 pm to 200 pm or from 0.5 pm to 150 pm or from 0.5 pm to 100 pm, or from 0.5 pm to 90 pm.
  • the particle size is in range from 0.5 pm to 80 pm, or from 0.5 pm to 70 pm, or from 0.5 pm to 60 pm, or from 0.5 pm to 50 pm, or from 0.5 pm to 40 pm, or from 0.5 pm to 30 pm, or from 0.5 pm to 20 pm.
  • the particle size is in range from 0.5 pm to 10 pm, or from 0.5 pm to 5 pm.
  • the graphene has an agglomeration size in range from 1 pm to 100 pm.
  • the graphene has an agglomeration size distribution of DIO (from 1.0 to 4.0 pm), D50 (from 6.0 to 14.0 pm), and D90 (30.0 to 36 pm).
  • D10, D50 and D90 denote percentage of particles (10%, 50% and 90%) in a size range.
  • the GNP has a short stack of graphene sheets having a platelet shape.
  • the GNP has an average thickness of approximately 6 to 8 nanometres.
  • the GNP has a typical surface area in range from 100 to 500 m 2 /g, or from 100 to 450 m 2 /g, or from 100 to 400 m 2 /g. In a more preferred embodiment, the typical surface area of the GNP is in range of 100 to 350 m 2 /g,
  • CARBON BLACK [0064]
  • the reaction mixture for the PU Composition includes the carbon black.
  • the carbon black is added either in the Part A or the Part B or both part of the reaction mixture.
  • the carbon black (CB) component is present in Part A and/ or Part B.
  • the carbon black includes acetylene black, furnace black, gas black, lamp black, thermal black, conductive black, HNO3-treated CB, ammonia treated CB, doped CB, CB mixed with iron phthalocyanine, or combination thereof.
  • the carbon black includes a conductive black, with a sieve residue (325 mesh) calculated by ASTM D 1514 in range from 0.01 to 200 ppm, or from 0.01 to 150 ppm, or from 0.01 to 100 ppm, or from 0.01 to 90 ppm, or from 0.01 to 80 ppm, or from 0.01 to 70 ppm, or from 0.01 to 60 ppm.
  • the carbon black has a sulphur content measured by ASTM D 1506 in range from 0.001 to 5.0 %, or from 0.001 to 4.0 %, , or from 0.001 to 3.0 %, or from 0.001 to 2.0%, or from 0.001 to 1.0 % of the carbon black component.
  • the carbon black has a total surface area measured by ASTM D 6556 in range from 50 to 2000 m 2 /g, or from 50 to 1900 m 2 /g, or from 50 to 1800 m 2 /g, or from 50 to 1700 m 2 /g, or from 50 to 1600 m 2 /g, or from 50 to 1500 m 2 /g, from 50 to 1400 m 2 /g, or from 50 to 1300 m 2 /g, or from 50 to 1200 m 2 /g.
  • the carbon black has total surface area in range from 60 to 1200 m 2 /g, or from 70 to 1200 m 2 /g, or from 80 to 1200 m 2 /g, or from 90 to 1200 m 2 /g, or from 100 to 1200 m 2 /g.
  • the ASTM D 6556 for total surface are determined by Brunauer, Emmett, and Teller (B.E.T. NS A) theory of multilayer gas adsorption behavior using multipoint determinations.
  • the carbon black includes a conductive black, with a sieve residue (45 mesh) calculated by ISO 787 18, in range from 0.01 to 200 ppm, or from 0.01 to 150 ppm, or from 0.01 to 100 ppm, or from 0.01 to 90 ppm, or from 0.01 to 80 ppm, or from 0.01 to 70 ppm, or from 0.01 to 60 ppm.
  • a sieve residue 45 mesh
  • the carbon black has a sulphur content measured by ASTM D 1619 in range from 0.001 to 5.0 %, or from 0.001 to 4.0 %, , or from 0.001 to 3.0 %, or from 0.001 to 2.0%, or from 0.001 to 1.0 % of the carbon black component.
  • the carbon black component in the PU composition is in range from 0.01 to 10.0 wt.%, or from 0.01 to 9.5 wt.%, or from 0.01 to 8.5 wt.%, or from 0.01 to 8.0 wt.% of the PU composition.
  • the carbon black component in the PU composition is in range from 0.01 to 7.5 wt.%, or from 0.01 to 7.0 wt.% or from 0.01 to 6.0 wt.%, or from 0.01 to 5.5 wt.% or from 0.01 to 5.0 wt.% or from 0.01 to 4.5 wt.% or from 0.01 to 4.0 wt.% of the PU composition.
  • the reaction mixture used to prepare the PU composition includes both carbon black and graphene.
  • the reaction mixture used to prepare the PU composition includes both carbon black and graphene in Part A.
  • the reaction mixture used to prepare the PU composition includes both carbon black and graphene in Part B.
  • the reaction mixture used to prepare the PU composition includes both carbon black and graphene in Part A and Part B.
  • both the at least one graphene component and the at least one carbon black (CB) component is added to the Part A.
  • the combination of CB and graphene is in range from 0.5 wt. % to 30.0 wt. %, or from 0.5 wt.% to 28.0 wt.%, or from 0.5 wt.% to 26.0 wt.%, or from 0.5 wt.% to 24.0 wt.%, or from 0.5 wt.% to 22.0 wt.%, or from 0.5 wt.% to 20.0 wt.%, or from 0.5 wt.% to 18.0 wt.%, or from 0.5 wt.% to 16.0 wt.%, or from 0.5 wt.% to 14.0 wt.%, or from 0.5 wt.% to 12.0 wt.%, or from 0.5 wt.% to 10.0 wt.%, or from 0.5 wt.% to 8.0 wt.% of the PU composition.
  • the combination of CB is in range from 0.5 wt. % to
  • the ratio of the graphene component to the carbon black component is in range from 10: 1 to 1 : 10, or from 10: 1 to 1 :9, or from 10:1 to 1 :8, or from 10: 1 to 1 :7, or from 10: 1 to 1 :6, or from 10: 1 to 1 :5, or from 10: 1 to 1 :4, or from 10: 1 to 1 :3, or from 10: 1 to 1 :2, or from 10: 1 to 1 : 1.
  • the ratio of graphene component to carbon black component is in range from 9: 1 to 1 : 1, or from 8: 1 to 1 : 1, or from 7: 1 to 1 :1, or from 6: 1 to 1 : 1..
  • the additives in the mixture can be selected from surface-active substances, flame retardants, nucleating agents, oxidation stabilizers, lubricants, mold release agents, dyes, pigments, dyes, flame retardants, hindered amine light stabilizers, ultraviolet light absorbers, stabilizers, ultra violet stabilizers, hydroxy stabilizers, plasticizers, epoxy plasticizers, chain regulator, polyethylene wax, antioxidants, defoamers, internal release agents, desiccants, blowing agents and anti-static agents or combinations thereof.
  • additives can be found, for example, in the Kunststoffhandbuch, Volume 7, “Polyurethane” Carl-Hanser-Verlag Kunststoff, 1st edition, 1966 2nd edition, 1983 and 3rd edition, 1993. Suitable amounts of these additives are well known to the person skilled in the art. However, for instance, the additives can be present in amounts up to 20 wt.-% based on the total weight of the polyurethane resin composition.
  • the at least one additional additive includes a catalyst, a chain extender, a flame retardant, a mold release agent, a rheology additive, a defoamer, a friction reducer, a non-sticky agent, an antistatic agent, a surfactant, a cross linker, or any combination thereof.
  • the chain extender has a molecular weight of less than 499 g/mol.
  • the chain extender is understood to mean a compound having at least two functional groups reactive toward isocyanates, for example hydroxyl groups, amino groups or thiol groups, and a molecular weight Mw of less than 499 g/mol.
  • the polyol composition is also free of compounds of this kind.
  • the chain extenders have a molecular weight less than 300 g/mol, or from 10 g/mol to 210 g/mol.
  • Another preferred chain extender has a molecular weight from 50 g/mol to 150 g/mol, or from 50 g/mol to 120 g/mol, or from 60 g/mol to 120 g/mol.
  • Suitable chain extenders can be selected from ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1-5 pentanediol, 1,6-hexanediol, 1,10-decanediol, 1,2- dihydroxycyclohexane, 1,3-dihydroxycyclohexane, 1,4-dihydroxy cyclohexane, diethylene glycol, 1,4-butanediol, bi s(2 -hydroxy-ethyl) hydroquinone, dipropylene glycol, glycerol, diethanolamine, and triethanolamine.
  • the chain extender can be selected from 1,2- ethylene glycol, 1,3-propylene glycol, 1,4 butane diol, 1,5-pentane diol, 1,6-hexane diol, Hydroquinone Bis (2 -hydroxyethyl) Ether (HQEE), or/ and hydroxyethylether of resorcinol or 1,3-Bis (2-hydroxyethyl) resorcinol (HER).
  • HQEE Hydroquinone Bis (2 -hydroxyethyl) Ether
  • HER hydroxyethylether of resorcinol or 1,3-Bis (2-hydroxyethyl) resorcinol
  • suitable chain extenders and/or cross linkers present in the polyurethane resin composition is further described.
  • Chain extenders and/or cross linkers used are preferably alkanol amines and in particular diols and/or triols having molecular weights preferably in between 60 g/mol to 300 g/mol. Suitable amounts of these chain extenders and/or cross linkers can be added and are known to the person skilled in the art. For instance, chain extenders and/or cross linkers can be present in an amount up to 99 wt.-%, or up to 20 wt.-%, based on the total weight of the polyurethane resin composition.
  • the reaction mixture includes a catalyst.
  • Catalysts in the reaction mixture include tertiary amine and phosphine compounds, metal catalysts such as chelates of various metals, acidic metal salts of strong acids; strong bases, alcoholates and phenolates of various metals, salts of organic acids with a variety of metals, organometallic derivatives of tetravalent tin, trivalent and pentavalent As, Sb and Bi and metal carbonyls of iron and cobalt and mixtures thereof.
  • the amine catalyst include tertiary amines selected from triethylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, N,N, N', N'- tetramethylethylenediamine, pentamethyl-diethylenetriamine and higher homologues (as described in, for example, DE-A 2,624,527 and 2,624,528), l,4-diazabicyclo(2.2.2)octane, N- methyl-N'-dimethyl -aminoethylpiperazine, bis-(dimethylaminoalkyl)piperazines, tris(dimethylaminopropyl)hexahydro-l,3,5-triazin, N,N-dimethylbenzylamine, N,N- dimethylcyclohexylamine, N,N-diethyl-benzylamine, bis-(N,N-diethylaminoethyl)
  • Suitable catalysts are likewise known in principle from the prior art.
  • Suitable catalysts are, for example, organic metal compounds selected from the group consisting of tin organyls, titanium organyls, zirconium organyls, hafnium organyls, bismuth organyls, zinc organyls, aluminum organyls and iron organyls, for example tin organyl compounds, preferably tin dialkyls such as dimethyltin or diethyltin, or tin organyl compounds of aliphatic carboxylic acids, preferably tin diacetate, tin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, bismuth compounds such as bismuth alkyl compounds or the like, or iron compounds, preferably iron(Ml) acetylacetonate, or the metal salts of the carboxylic acids, for example tin(II) isooctoate, tin
  • the catalysts as described hereinabove, can be present in amounts preferably up to 20 wt.-% based on the total weight of the PU composition.
  • the composite structure is produced by resin transfer molding (RTM) technique.
  • reaction mixture as described hereinabove, can also comprise a reinforcing agent.
  • Suitable reinforcing agents refer to fillers in the present context.
  • Suitable fillers include, such as, but not limited to, silicatic minerals, examples being finely ground quartzes, phyllosilicates, such as antigorite, serpentine, hornblendes, amphibols, chrysotile, and talc; metal oxides, such as kaolin, aluminum oxides, aluminium hydroxides, magnesium hydroxides, hydromagnesite, titanium oxides and iron oxides, metal salts such as chalk, heavy spar and inorganic pigments, such as cadmium sulfide, zinc sulfide, and also glass and others. Preference is given to using kaolin (china clay), finely ground quartzes, aluminum silicate, and coprecipitates of barium sulfate and aluminum silicate.
  • silicatic minerals examples being finely ground quartzes, phyllosilicates, such as antigorite, serpentine, hornblendes, amphibols, chrysotile, and talc
  • metal oxides such as ka
  • Suitable fillers have an average particle diameter in the range of 0.1 pm to 500 pm, more preferably in the range of 1 pm to 100 pm, and most preferably in the range of 1 pm to 10 pm. Diameter in this context, in the case of non-spherical particles, refers to their extent along the shortest axis in space.
  • Suitable amounts of the fillers can be present in the polyurethane resin composition which are known to the person skilled in the art.
  • fillers can be present in an amount up to 50 wt.-%, based on the total weight of the polyurethane resin composition.
  • Suitable flame retardants are tetrabromobisphenol A, brominated polystyrene oligomers, brominated butadiene-polystyrene copolymers in accordance with WO 2007/058736, tetrabromobisphenol A diallyl ether, and hexabromocyclododecane (HBCD), in particular the industrial products, where these in essence comprise the a-, P-, and y-isomer with added synergists, such as dicumyl.
  • HBCD hexabromocyclododecane
  • Preference is given to brominated aromatics, such as tetrabromobisphenol A, and to brominated styrene oligomers.
  • halogen- free flame retardants are expandable graphite, red phosphorus, and phosphorus compounds, such as triphenyl phosphate and 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide.
  • the flame retardant is graphite.
  • the graphite includes graphite ore treated with sulfuric acid by intercalation process.
  • the graphite ore has bulk density in range of 0.45 to 0.60 g/cm 3 .
  • Preferred phosphorus compounds are tris(2-chloroisopropyl) phosphate, triethyl phosphate, diethyl ethylphosphonate, cresyl diphenyl phosphate, Exolit OP560, diphenyl 6- (diphenoxyphosphoryloxy)hexahydrofuro[3,2-b]furan-3-yl phosphate, 9, 10-dihydro-9-oxa- 10-phosphaphenanthrene 10-oxide, and 6H-dibenzo[c,e][l,2]oxaphosphorine 6-oxide.
  • Antistatic additives and antistatic polymers are known.
  • DE 3531660 describes antistatic polyurethane shoe soles.
  • the antistatic effect is achieved via from 0.01 to 0.3% by weight of chemically bonded sulfonate groups.
  • the volume resistivities achieved are ⁇ 10 8 Q/cm.
  • the use of various quaternary ammonium salts for increasing the conductivity of polymers is described in EP 1134268. This involves modifications of commercially available antistatic agents, such as Catafor F® or Catafor PU® from Rhodia. For example, volume resistivities of about 107 Q/cm are achieved at high concentrations.
  • Antistatic additives include ethylmethylimidazole ethyl sulfate.
  • Ethylmethylimidazole ethyl sulfate can be used here alone or in a mixture, for example together with other antistatic additives. It is preferable that ethylmethylimidazole ethyl sulfate is used as sole antistatic additive.
  • the antistatic agent is selected from Soyabean oil with CIO to C16 Carbon chains, l-Ethyl-3 -methyl imidazolium dicyanamide, alkali metal salts in solvent, phosphoric acid and triethyl ether, metallic salt and polyether.
  • Hydrolysis stabilizers used preferably comprise oligomeric and/or polymeric aliphatic or aromatic carbodiimides.
  • stabilizers are added to the PU composition.
  • stabilizers are additives which protect a plastic or a plastics mixture from damaging environmental effects. Examples are primary and secondary antioxidants, hindered amine light stabilizer, UV absorber, hydrolysis stabilizer, quencher, and flame retardant. Examples of commercial stabilizers are given in Plastics Additive Handbook, 5th Edition, H. Zweifel, ed., Hanser Publishers, Kunststoff, 2001 ([1]), pp. 98-136.
  • antioxidants can be added. It is preferable to use phenolic antioxidants. Examples of phenolic antioxidants are given in Plastics Additive Handbook, 5th edition, H. Zweifel, ed, Hanser Publishers, Kunststoff, 2001, pp. 98-107 and pp. 116-121. Preference is given to those phenolic antioxidants whose molar mass is greater than 700 g/mol.
  • phenolic antioxidant whose use is preferred is pentaerythrityl tetrakis(3-(3,5-bis(l,l-dimethylethyl)-4- hydroxyphenyl)propionate) (Irganox® 1010).
  • concentrations generally used of the phenolic antioxidants are from 0.1 to 5% by weight, preferably from 0.1 to 2% by weight, in particular from 0.5 to 1.5% by weight, based in each case on the total weight of the PU.
  • the PU composition may optionally include a UV absorber.
  • UV absorbers are molecules which absorb high-energy UV light and dissipate the energy. Familiar UV absorbers used industrially are, for example, members of the group of cinnamic esters, of diphenylcyanoacrylates, of the formamidines, of the benzylidenemalonates, of the diarylbutadienes, or triazines, or of the benzotriazoles. Examples of commercial UV absorbers are found in Plastics Additive Handbook, 5th edition, H. Zweifel, ed, Hanser Publishers, Kunststoff, 2001, pp. 116-122.
  • the number-average molar mass of the UV absorbers is greater than 300 g/mol, in particular greater than 390 g/mol.
  • the UV absorbers preferably used should moreover have molar mass no greater than 5000 g/mol, particularly preferably no greater than 2000 g/mol.
  • the benzotriazoles group is particularly suitable as UV absorber. Examples of particularly suitable benzotriazoles are Tinuvin® 213, Tinuvin® 328, Tinuvin® 571, and also Tinuvin® 384, and Eversorb®82.
  • the amounts preferably added of the UV absorbers are from 0.01 to 5% by weight, based on the total weight of antistatic, polyurethane, particularly preferably from 0.1 to 2.0% by weight, in particular from 0.2 to 0.5% by weight, based in each case on the total weight of the antistatic polyurethane.
  • the UV absorbers have a number average molecular weight of greater than 0.3x103 g/mol, in particular greater than 0.39x103 g/mol. Furthermore, the UV absorbers which are preferably used should have a molecular weight of not greater than 5cl03 g/mol, particularly preferably not greater than 2cl03 g/mol.
  • Particularly suitable UV absorbers are from the group of benzotriazoles.
  • Particularly suitable benzotriazoles are Tinuvin® 213, Tinuvin® 234, Tinuvin® 571 and Tinuvin® 384 and Ever- sorb®82.
  • the UV absorbers are usually added in amounts of from 0.01 to 5% by weight, based on the total mass of the PU, preferably 0.1-2.0% by weight, in particular 0.2-0.5% by weight.
  • a UV stabilization as described above based on an antioxidant and a UV absorber is often still not sufficient to ensure good stability of the film against the damaging influence of UV rays.
  • a hindered amine light stabilizer HALS
  • HALSs are highly efficient UV stabilizers for most polymers.
  • HALS compounds are generally known and commercially available. Examples of commercially available HALSs may be found in Plastics Additive Handbook, 5th edition, H. Zweifel, Hanser Publishers, Kunststoff, 2001, pp. 123-136.
  • hindered amine light stabilizers preference is given to employing hindered amine light stabilizers in which the number average molecular weight is greater than 500 g/mol. Furthermore, the molecular weight of the preferred HALS compounds should be not greater than 10 000 g/mol, particularly preferably not greater than 5000 g/mol.
  • Particularly preferred hindered amine light stabilizers are bis(l , 2, 2,6,6- pentamethylpiperidyl) se- bacate (Tinuvin® 765, Ciba Spezialitatenchemie AG) and the condensation product of 1-hydrox- yethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid (Tinuvin® 622).
  • the condensation product of 1- hydroxyethyl-2,2,6,6-tetramethyl-4-hydrox- ypiperidine and succinic acid (Tinuvin® 622) when the titanium content of the product is ⁇ 150 ppm, preferably ⁇ 50 ppm, in particular ⁇ 10 ppm.
  • HALS compounds are preferably used in a concentration of from 0.01 to 5% by weight, particularly preferably from 0.1 to 1% by weight, in particular from 0.15 to 0.3% by weight referring to the total weight of the film.
  • hydrolysis inhibitors are comprised in the PU composition as auxiliaries; preference is given here to oligomeric and/or polymeric aliphatic or aromatic carbodiimides.
  • auxiliaries and additives may be found in the specialist literature, for example in Plastics Additive Handbook, 5th edition, H. Zweifel, ed., Hanser Publishers, Kunststoff, 2001.
  • Mold release agents include release agents based on wax or silicon, mold release agents based on salts of aliphatic mono- or polycarboxylic acids having at least 25 carbon atoms, and primary mono-, di-, or polyamines having two or more carbon atoms, or amide or ester group-containing amines, which have at least one primary, secondary or tertiary amino group, release agents based on mixtures of at least two compounds from the group of aminecarboxylic acid-salts, saturated or unsaturated CeOH- and/or OH group-containing esters from mono- and/or poly carboxylic acids, and multivalent alcohols or natural and/or synthetic oils, fats or waxes, mold release agents based on ketimines, aldimines, enamines or cyclic Schiff bases.
  • FRICTION REDUCERS FRICTION REDUCERS:
  • the friction reducers include polyethylene and polytetrafluoroethylene (PTFE) powders.
  • Polyethylene includes crosslinked and non-crosslinked polyethylene.
  • the friction reducer is a non-cross-linked polyethylene.
  • the non-cross-linked polyethylene includes high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE- HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low-density polyethylene (LLDPE), (VLDPE) and (ULDPE)
  • the non-crosslinked polyethylene is an Ultra-high molecular weight polyethylene (UHMWPE) powder.
  • UHMWPE Ultra-high molecular weight polyethylene
  • the UHMWPE has d50 average particle size in range from 0.01 pm to 500pm.
  • the UHMWPE has the average particle size less than from 0.01 pm to 400pm or from 0.01 pm to 300pm, or from 0.01 pm to 200pm or from 0.01 pm to 100pm.
  • the molecular weight in range of 0.5 Mio g/ mol to 20 Mio g/ mol.
  • the UHMWPE has a molecular weight in range of 1.0 Mio g/ mol to 20 Mio g/ mol or in range of 1 Mio g/ mol to 15 Mio g/ mol, or in range of 1.0 Mio g/ mol to 10 Mio g/ mol.
  • the friction reducer is a polytetrafluoroethylene (PTFE) powder.
  • the friction reducer is in range from 0.1 to 10.0 wt.%. In a preferred embodiment the friction reducer is in range from 1.0 to 9.0 wt.%, or from 1.0 to 8.0 wt.%, or from 1.0 to 7.0 wt.%, or from 1.0 to 6.0 wt.%, or from 1.0 to 5.0 wt.%. In a more preferred embodiment, the friction reducer is in range of 1.0 to 5.0 wt.%. [00132] In another preferred embodiment, the at least one friction reducer is selected from UHMWPE and PTFE or combination thereof. In a further embodiment the at least one friction reducer is in range of 0 to 30.0 wt. %.
  • the PART B includes at least one isocyanate.
  • the isocyanates can be selected from aliphatic isocyanates, aromatic isocyanates, and a combination thereof.
  • aromatic isocyanate it is referred to molecules having two or more isocyanate groups attached directly and/or indirectly to the aromatic ring. Further, it is to be understood that the isocyanate includes both monomeric and polymeric forms of the aliphatic and aromatic isocyanate.
  • polymeric it is referred to the polymeric grade of the aliphatic and/or aromatic isocyanate comprising, independently of each other, different oligomers, and homologues.
  • the isocyanate comprises an aromatic isocyanate selected from toluene diisocyanate; polymeric toluene diisocyanate, methylene diphenyl diisocyanate; polymeric methylene diphenyl diisocyanate; m-phenylene diisocyanate; 1,5 -naphthalene diisocyanate; 4-chloro-l; 3-phenylene diisocyanate; 2,4,6-toluylene triisocyanate, 1,3- diisopropylphenylene-2,4-diisocyanate; l-methyl-3,5-diethylphenylene-2,4-diisocyanate;
  • the aromatic isocyanate is selected from toluene diisocyanate; polymeric toluene diisocyanate, methylene diphenyl diisocyanate; polymeric methylene diphenyl diisocyanate, m-phenylene diisocyanate; 1,5 -naphthalene diisocyanate; 4- chloro-1; 3-phenylene diisocyanate; 2,4,6-toluylene triisocyanate, 1,3-diisopropylphenylene- 2,4-diisocyanate and l-methyl-3,5-diethylphenylene-2,4-diisocyanate.
  • the aromatic isocyanate is selected from toluene diisocyanate; polymeric toluene diisocyanate, methylene diphenyl diisocyanate; polymeric methylene diphenyl diisocyanate, m-phenylene diisocyanate and 1,5 -naphthalene diisocyanate or a combination thereof.
  • the aromatic isocyanate is selected from toluene diisocyanate; polymeric toluene diisocyanate, methylene diphenyl diisocyanate and polymeric methylene diphenyl diisocyanate or mixture thereof.
  • the aromatic isocyanate is selected from methylene diphenyl diisocyanate, polymeric methylene diphenyl diisocyanate or combination thereof.
  • the methylene diphenyl diisocyanate is exists in three different isomeric forms, namely 2,2'-methylene diphenyl diisocyanate (2,2'-MDI), 2, d'methylene diphenyl diisocyanate (2,4'-MDI) and 4,4'-methylene diphenyl diisocyanate (4,4'- MDI).
  • Methylene diphenyl diisocyanate can be classified into monomeric methylene diphenyl diisocyanate and polymeric methylene di-phenyl diisocyanate referred to as technical methylene diphenyl diisocyanate.
  • Polymeric methylene diphenyl diisocyanate includes oligomeric species and methylene diphenyl diisocyanate isomers.
  • polymeric methylene diphenyl diisocyanate may contain a single methylene diphenyl diisocyanate isomer or isomer mixtures of two or three methylene diphenyl diisocyanate isomers, the balance being oligomeric species.
  • Polymeric methylene diphenyl diisocyanate tends to have isocyanate functionalities of higher than 2. The isomeric ratio as well as the amount of oligomeric species can vary in wide ranges in these products.
  • polymeric methylene diphenyl diisocyanate may typically contain 30 wt.-% to 80 wt.-% of methylene diphenyl diisocyanate isomers, the balance being said oligomeric species.
  • the methylene diphenyl diisocyanate isomers are often a mixture of 4,4'-methylene diphenyl diisocyanate, 2,4'-methylene diphenyl diisocyanate and low levels of 2,2'-methylene di-phenyl diisocyanate.
  • the isocyanate comprises a polymeric methylene diphenyl diisocyanate.
  • Commercially available isocyanates available under the tradename, such as, but not limited to, Lupranate® from BASF can also be used for the purpose of the present invention.
  • the aliphatic isocyanate is selected from isophorone diisocyanate, propylene-l,2-diisocyanate, propylene-l,3-diisocyanate, butylene-
  • aliphatic isocyanate selected from isophorone diisocyanate, hexamethylene-l,6-diisocyanate, 2-methylpentamethylene-l,5- diisocyanatel,5-pentamethylene diisocyanate, 1,6,11-triisocyanatoundecane, methyl-2,6- diisocyanate caproate, octamethlyene-l,8-diisocyanate, 2,4,4-trimethylhexamethylene-l,6- diisocyanate, nonamethylene diisocyanate, 2,2,4-trimethylhexamethylene-l,6-diisocyanate, decamethylene-1, 10-diisocyanate, 2,11-diisocyanato-dodecane or polymeric forms of diisocyanates; and most preferably the aliphatic isocyanate selected from isophorone diisocyanate, hexamethylene-l,6-diisocyanate, 2-
  • 1,5-pentamethylene diisocyanate 1 octamethly ene- 1 , 8-dii socy anate, 2.4.4- trimethylhexamethylene-l,6-diisocyanate, nonamethylene diisocyanate, 2.2.4- trimethylhexamethylene-l,6-diisocyanate, decam ethyl ene- 1 , 10 -di i socy anate.
  • the isocyanate reactive component is a polyol having an average functionality in the range of 2.0 to 8.0 and the hydroxyl number in the range of 15 mg KOH/g to 1800 mg KOH/g.
  • the compounds that are reactive towards isocyanate can be present in an amount in the range of 1 wt.-% to 99 wt.-%, based on the total weight of the reaction mixture.
  • the at least one isocyanate is with an isocyanate functionality ranging from 2.0 to 4.0.
  • the isocyanate composition comprises an isocyanate having an isocyanate functionality ranging from 1.5 to 3.0.
  • the isocyanate functionality of the first isocyanate ranges from 1.6 to 3.0, or from 1.7 to 3.0, or from 1.8 to 3.0, or from 1.9 to 3.0. More preferably, the isocyanate functionality of the isocyanate ranges from 1.9 to 2.9, or from 1.9 to 2.8, or from 1.9 to 2. 7.
  • the isocyanate content is in an amount from 1 wt.-% to 60 wt.-%.
  • the isocyanate component of the isocyanate is from 1 wt.-% to 55 wt.-%, or from 5 wt.-% to 55 wt.-%, or from 10 wt.-% to 55 wt.-%, or from 15 wt.-% to 55 wt.-%.
  • the isocyanate component of the first isocyanate is from 20 wt.-% to 55 wt.-%, or from 23 wt.-% to 55 wt.-%, or from 25 wt.-% to 55 wt.-% (29.5, 31.5, 33.5).
  • the isocyanate is selected from a 2,2'-, 2,4'- and/or 4,4'-diisocyanate, a hexamethylene diisocyanate (HDI), or Hydrogenated MDI or a carbodiimide modified MDI.
  • the isocyanate has an isocyanate content in range from 25 wt.% to 55 wt.%.
  • the at least one isocyanate is selected from 4, d'diphenylmethane diisocyanate, polymeric MDI, carbodiimide modified MDI, MDI prepolymer or combination thereof.
  • the Part B comprises at least two isocyanates, the first isocyanate and the second isocyanate.
  • the first isocyanate is as described hereinabove.
  • the second isocyanate has an isocyanate functionality of at least 2.0, said second isocyanate being different than the first isocyanate.
  • Suitable second isocyanates have an isocyanate content of at least 5.0 wt.-%.
  • the second isocyanate in the isocyanate composition have an isocyanate content in range from 5 wt.% to 40 wt.%, or in range from 6 wt.% to 30 wt.%, or in range from 7 wt.% to 20 wt.%, the said second isocyanates being different than the first isocyanate.
  • the second isocyanate in the isocyanate composition is selected from a prepolymer based on carbodiimide-modified diphenylmethane 2,2'-, 2,4'- and/or 4,4'- diisocyanate.
  • the isocyanate composition comprises a mixture of the first isocyanate and the second isocyanate.
  • the weight ratio between the first isocyanate and the second isocyanate in the isocyanate composition is in a range from 2.0: 1.0 to 1.0: 2.0.
  • the weight ratio between the first isocyanate and the second isocyanate in the isocyanate composition is in a range from 2.0: 1.0 to 1.0: 1.5 or from 2.0: 1.0 to 1.0: 1.3, or from 2.0:1.0 to 1.0: 1.0.
  • the weight ratio between the first isocyanate and the second isocyanate in the isocyanate composition is in a range from 1.9: 1.0 to 1.0: 1.0, or from 1.8: 1.0 to 1.0: 1.01, or from 1.7: 1.0 to 1.0:1.0.
  • Another aspect of the present invention is an embodiment, directed towards a method of obtaining a polyurethane (PU), the method comprising the steps of: a. providing the Part A and the Part B of the reaction mixture for the composition ; b. mixing the Part A and the Part B; c. optionally heating the reaction mixture.
  • PU polyurethane
  • the mixing is performed by a mixing device.
  • the mixing device can be a low pressure or high-pressure mixing device comprising: pumps to feed the streams, a high-pressure mixing head in which the Part A and Part B, as described hereinabove, are mixed, a feed line A fitted to the high-pressure mixing head through which the Part A stream is introduced into the mixing head, and a feed line B fitted to the high-pressure mixing head through which the Part B is introduced into the mixing head.
  • the mixing device can further comprise at least one measurement and control unit for establishing the pressures of each feed lines in the mixing head.
  • low pressure here refers to a pressure in between 0.1 MPa to 5 MPa
  • high pressure refers to pressure above 5 MPa.
  • Suitable temperatures for processing the reaction mixture are well known to the person skilled in the art. In an embodiment the mixing is performed at a temperature from 40°C to 85°C.
  • the Part A and the Part B of the reaction mixture are passed from the same or separate mixing head into the mixing device with or without pressure.
  • a solid/gas mixture can be added through additional inlets.
  • solid it is referred to the fillers, as described hereinabove, which are in a solid state of matter.
  • Suitable temperatures for processing the reaction mixture are well known to the person skilled in the art.
  • the Part A and Part B are pre-mixed in suitable mixing means, such as, but not limited to, a static mixer.
  • the method of obtaining the PU composition includes premixing the Part A (having the graphene and CB) with high shear force before mixing with the Part B.
  • the mixing is performed at a temperature from 40°C to 85°C.
  • the reaction mixture obtained from the mixing device is fed to a means to provide shape to the PU composition.
  • the means to provide shape includes but is not limited to spraying, spray molding, and injection molding.
  • the reaction mixture is poured in a mold and cured at temperature between 60°C to 85°C.
  • the reaction mixture is Injection molded.
  • the injection-molding machine is used specified to be a 10 cc micro-injection molding machine to give tensile specimens (temperature of tensile-specimen mold: 40° C to 85° C; temperature of melt accumulator: up to 190° C).
  • the mold temperature is 60°C, with fill time of 5 to 20 seconds and demold time in range of 1 to 15 mins.
  • the high-speed mixer is used to mix Part A components at room temperature. Then, the components of Part A and Part B are mixed at defined ratio. The mixture is then poured in a plaque mold and cured at 60°C for 5 mins in a pre-heated oven.
  • the components of Part A and Part B are loaded in a heated day tanks at 45°C. The components are mixed and injected into a RIM mold at 60 to 80 °C.
  • Another aspect of the present invention is directed to the uses of the PU composition.
  • Another aspect of the present invention is directed to an electrically semi- conductive system obtained by the PU composition.
  • Another aspect of the present invention is directed to the uses of the PU composition in electrostatic discharge (ESD) related applications.
  • the applications include control the electrical resistance of the material by using the PU composition in preparation of the same.
  • ESD application includes making surface covering, flooring, coatings that help control ESD events including sparks.
  • Yet another aspect of the present invention is directed towards an electrically semi- conductive system obtained by the PU composition.
  • the composition is used in an Electrostatic Discharge (ESD) application.
  • ESD Electrostatic Discharge
  • the PU composition and articles made thereof are associated with an exceptionally low coefficient of friction CoF (about 0.1-0.15 similar to UHMWPE, a surface resistivity in the range of l.OxlO 6 to 9.0xl0 n ohm and successful fire resistance performance as per Method A, i.e., UL94 HB with no dripping are required.
  • the PU composition is associated with low coefficient of friction (COF) and antistatic properties.
  • COF coefficient of friction
  • the combination of graphene and carbon black results in a durable antistatic characteristic that is stable and does not change with ambient conditions. This is not achievable using either of them alone or liquid Antistats.
  • the addition of graphene improves the durability of coefficient of friction due to its multi-layered structure.
  • the PU Composition provides a viable alternative to the usage of liquid Antistats in applications requiring a surface resistivity between 10 8 and 10 11 ohms per square.
  • the PU composition is associated with rigid and possesses high thermal and mechanical properties.
  • the use of graphene improves both mechanical properties and the flame resistance of the system.
  • the modulus increased slightly when graphene is used.
  • heat deflection temperature increased at least by 10 °C.
  • the PU Composition as disclosed out-perform when compared to with PU composition with liquid Antistats commonly used for ESD applications. Most importantly, the PU Composition has longer shelf life and does not change with ambient conditions, i.e., temperature and humidity. On the contrary, liquid Antistats depend on both temperature and humidity and the effectiveness will fade by time.
  • the flammability rating is measured by METHOD A.
  • the flammability rating is calculated for test specimen prepared by the PU Composition and the method as described hereinabove.
  • the Rating is calculated as a function of the burning rate and taking account of the material thickness.
  • the method A includes a pretreatment for 48 hours at 23 °C and relative humidity.
  • the flame application is done for 20 mm high Trill burner flame for 30 seconds.
  • the flame application is stopped if the flame front reaches the first mark within 30 seconds.
  • the flammability rating is passed if the a. Test specimen of 3 to 13 mm bums at rate of less than or equal to 40 mm/ min. b. Test specimen of less than 3 mm burns at rate of less than or equal to 75 mm/ mm. c. Flam is extinguished before the first mark, bum rate being 0 mm/ min.
  • a polyurethane (PU) composition prepared from a reaction mixture comprising: a. Part A with at least one isocyanate reactive component; b. Part B with at least one isocyanate; wherein the reaction mixture includes at least one graphene component and/ or at least one carbon black (CB) component; wherein graphene component is present in Part A and/ or Part B; and wherein carbon black (CB) component is present in Part A and/ or Part B.
  • PU polyurethane
  • composition of embodiment I, wherein the at least one isocyanate reactive component comprises at least one polyol.
  • composition of embodiment II, wherein the at least one polyol has an average functionality in the range of 2.0 to 8.0, the hydroxyl number in the range of 20 mg KOH/g to 800 mg KOH/g and the nominal molecular weight in the range of 200 g/ mole to 6000 g/ mole.
  • composition of any one of embodiment I to III, wherein the at least one polyol is poly ether polyols, polyester polyols, poly etherester polyols, Polytetrahydrofurane, or a combination thereof.
  • composition of any one of embodiment I to IV, wherein the at least one isocyanate is with an isocyanate functionality ranging from 2.0 to 4.0.
  • VI. The composition of any one of embodiment I to V, wherein the at least one isocyanate is 4,4 '-diphenylmethane diisocyanate, polymeric MDI, carbodiimide modified MDI, an Elastoflex 2500U, MDI prepolymer or combination thereof.
  • any one of embodiment I to VII, wherein the graphene includes monolayer graphene, few-layer graphene (FLG), multi-layer graphene (MLG), graphene nano-platelets (GNP), graphite oxides (GO), reduced graphene oxides (rGO), graphene quantum dots, graphene ribbons, suspended graphene particles or membranes thereof, graphene master batches thereof, or combination thereof.
  • the carbon black (CB) component includes acetylene black, furnace black, gas black, lamp black, thermal black, conductive black, HNO3-treated CB, ammonia treated CB, doped CB, CB mixed with iron phthalocyanine, or combination thereof.
  • XIII The composition of any one of embodiment I to XII, wherein the at least one additive includes from a catalyst, a chain extender, a flame retardant, a mold release agent, a rheology additive, a defoamer, a friction reducer, a non-sticky agent, an antistatic agent, a surfactant, a cross linker, or any combination thereof.
  • the friction reducer is a polyethylene including an ultra-high molecular weight polyethylene (UHMWPE) powder, high molecular weight polyethylene (HMWPE) powder or a polytetrafluoroethylene or a combination thereof.
  • UHMWPE ultra-high molecular weight polyethylene
  • HMWPE high molecular weight polyethylene
  • the at least one other antistatic agent is selected from Soyabean oil with CIO to C16 Carbon chains, 1-Ethyl- 3 -methyl imidazolium di cyanamide, alkali metal salts in solvent, phosphoric acid and triethyl ether, metallic salt and polyether, or combination thereof.
  • a method of obtaining a polyurethane (PU) composition comprising: c. providing the Part A and the Part B of the reaction mixture for the composition of one of embodiment I to XVII; d. mixing the Part A and the Part B; e. optionally heating the reaction mixture.
  • PU polyurethane
  • XXI The method of any one of embodiment XIX or XX, wherein the reaction mixture is poured in a mold and cured at temperature between 60°C to 85°C.
  • XXII An electrically semi -conductive system obtained by the composition of any one of embodiment I or XVII, or by the method of any one of embodiment XVIII to XXI.
  • Table A List of raw materials with the abbreviations used.
  • Tables 1 to 3 provide weight % of the components present in the Part A and the Part B along with the Ratio of Part A: Part B. Each component of both Part A and Part B in Tables 1 to 3 are in wt.% of total PU composition. The process employed to form PU as per compositions of Tables 1 to 3 ae same and is described below.
  • the high-speed mixer was used to mix Part A components at room temperature. Then, the components of Part A and Part B were mixed at defined ratio. The mixture was then poured in a plaque mold and cured at 60°C for 5 mins in a pre-heated oven.
  • the PU composition formed were tested based on the standard methods to determine the Shore D Hardness, Coefficient of Friction, Antistatic Resistivity, Surface Resistivity, Flame Retardance and optionally the Flexural Modulus, Flexural Stress, Flexural Strain, Tensile Modulus, Tensile Stress, Tensile Strain. as indicated in Table B and Method A (for flammability rating).
  • the PU composition is associated with a surface resistivity in range of l.OxlO 6 to 9.0xl0 n ohm in an electrically semi-conductive system.
  • the surface resistivity is suitable for electrostatic discharge applications.
  • the electrical results are associated with presence of graphene and carbon black in the PU composition.
  • the viscosity of such a system can go above 5000 cP while the viscosity of the system containing both graphene (2-3 wt.%) and carbon black (0.25-0.5 wt.%) is below 2000 cP suitable for most low pressure and high-pressure applications.

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Abstract

A polyurethane (PU) composition prepared from a reaction mixture comprising a. Part A with at least one isocyanate reactive component and optionaly at least one additive; b.Part B with at least one isocyanate. The reaction mixture includes at least one graphene component and at least one carbon black (CB) component. The graphene component is present in Part A and/ or Part B. The carbon black (CB) component is present in Part A and/ or Part B.

Description

POLYURETHANE (PU) COMPOSITION AND METHOD OF PRODUCING PU COMPOSITION
FIELD OF INVENTION
[0001] The present invention relates to a polyurethane (PU) composition, a method of producing the PU composition, and uses of the PU composition.
BACKGROUND OF THE INVENTION
[0002] Polyurethane (PU) compositions are widely used for the physical properties of flexibility, ability to form variety of shapes, molding. However, many PU compositions do not have suitable electrical and thermal properties. Adding fillers for improving some electrical and thermal properties require higher loading and result in change in other physical properties.
[0003] Polyurethane systems are inherently insulative and does not provide a low coefficient of friction. It was, therefore, an object of the present invention to provide for a PU composition such that the PU composition is associated with improved surface resistivity, flame resistance performance with no dripping requirement.
SUMMARY OF THE INVENTION
[0004] Surprisingly, it has been found that the above identified object is met by providing a PU composition of the presently claimed invention, The PU composition is associated with low coefficient of friction CoF, improved surface resistivity and fire resistance performance with no dripping requirement.
[0005] Accordingly, in one aspect, the presently claimed invention is directed to a polyurethane (PU) composition prepared from a reaction mixture comprising: a. Part A with at least one isocyanate reactive component; b. Part B with at least one isocyanate; wherein the reaction mixture includes at least one graphene component and at least one carbon black (CB) component; wherein graphene component is present in Part A and/ or Part B; and wherein carbon black (CB) component is present in Part A and/ or Part B.
[0006] In another aspect, the presently claimed invention is directed to a method of obtaining a polyurethane (PU), the method comprising: a. providing the Part A and the Part B of the reaction mixture for the composition; b. mixing the Part A and the Part B; c. optionally heating the reaction mixture.
[0007] In another aspect, the presently claimed invention is directed to an electrically semi -conductive system based on the PU composition.
[0008] In another aspect, the presently claimed invention is directed to the use of the PU composition in electrostatic discharge (ESD) applications.
DETAILED DESCRIPTION OF THE INVENTION
[0009] Before the present compositions and formulations of the invention are described, it is to be understood that this invention is not limited to particular compositions and formulations described, since such compositions and formulation may, of course, vary. It is also to be understood that the terminology used herein is not intended to be limiting, since the scope of the present invention will be limited only by the appended claims.
[0010] The terms "comprising", "comprises" and "comprised of' as used herein are synonymous with "including", "includes" or "containing", "contains", and are inclusive or open ended and do not exclude additional, non-recited members, elements or method steps. It will be appreciated that the terms "comprising", "comprises" and "comprised of' as used herein comprise the terms "consisting of', "consists" and "consists of'.
[0011] Furthermore, the terms "first", "second", "third" or "(a)", "(b)", "(c)", "(d)" etc., and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of operation in other sequences than described or illustrated herein. In case the terms "first", "second", "third" or “(A)”, “(B)” and “(C)” or "(a)", "(b)", "(c)", "(d)", "i", "ii" etc. relate to steps of a method or use or assay there is no time or time interval coherence between the steps, that is, the steps may be carried out simultaneously or there may be time intervals of seconds, minutes, hours, days, weeks, months or even years between such steps, unless otherwise indicated in the application as set forth herein above or below.
[0012] In the following passages, different aspects of the invention are defined in more detail. Each aspect so defined may be combined with any other aspect or aspects unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous.
[0013] Reference throughout this specification to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, appearances of the phrases "in one embodiment" or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment but may. Furthermore, the features, structures or characteristics may be combined in any suitable manner, as would be apparent to a person skilled in the art from this disclosure, in one or more embodiments. Furthermore, while some embodiments described herein include some, but not other features included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the invention, and form different embodiments, as would be understood by those in the art. For example, in the appended claims, any of the claimed embodiments can be used in any combination.
[0014] Furthermore, the ranges defined throughout the specification include the end values as well, i.e. a range of 1 to 10 implies that both 1 and 10 are included in the range. For the avoidance of doubt, the applicant shall be entitled to any equivalents according to applicable law.
[0015] An aspect of the present invention is an embodiment, directed towards a polyurethane (PU) composition prepared from a reaction mixture comprising: a. Part A with at least one isocyanate reactive component; b. Part B with at least one isocyanate; wherein the reaction mixture includes at least one graphene component and at least one carbon black (CB) component; wherein graphene component is present in Part A and/ or Part B; and wherein carbon black (CB) component is present in Part A and/ or Part B.
[0016] PU COMPOSITION
[0017] In an embodiment, the PU composition is prepared from a reaction mixture. The reaction mixture comprises the Part A and Part B.
[0018] In an embodiment, the PU composition is formed as a product of reaction mixture of Part A with at least one isocyanate reactive component and Part B with at least one isocyanate. The reaction mixture includes at least one graphene component and at least one carbon black (CB) component. The graphene component is present in Part A and/ or Part B; and the carbon black (CB) component is present in Part A and/ or Part B.
[0019] In a preferred embodiment, at least one graphene component and/ or the at least one carbon black (CB) component is added to the Part A.
[0020] In another preferred embodiment, the at least one graphene component and/ or the at least one carbon black (CB) component is added to the Part B.
[0021] In another preferred embodiment, the at least one graphene component and the at least one carbon black (CB) component is added to the Part B. [0022] In another preferred embodiment, the at least one graphene component is added to the Part A and the at least one carbon black (CB) component is added to the Part B.
[0023] In another preferred embodiment, the at least one graphene component is added to the Part B and the at least one carbon black (CB) component is added to the Part A.
In a most preferred embodiment, both the at least one graphene component and the at least one carbon black (CB) component is added to the Part A.
[0024] PART A: ISOCYANATE REACTIVE COMPONENT
[0025] In a preferred embodiment, the isocyanate reactive component of the PU composition comprises at least one polyol. Part A further comprises optionally an additive that includes a chain extender, a cross linker, a catalyst, an antistatic agent, a flame retardant, at least one reaction mixture additives, and at least one reaction mixture filler, or any combination thereof.
[0026] POLYOL
[0027] The polyols include poly ether polyols, polyester polyols, poly etherester polyols, and a combination thereof.
[0028] In another embodiment, the polyether polyols are obtainable by known methods, for example by anionic polymerization with alkali metal hydroxides, e.g., sodium hydroxide or potassium hydroxide, or alkali metal alkoxides, e.g., sodium methoxide, sodium ethoxide, potassium ethoxide or potassium isopropoxide, as catalysts and by adding at least one amine- containing starter molecule, or by cationic polymerization with Lewis acids, such as antimony pentachloride, boron fluoride etherate and so on, or fuller’s earth, as catalysts from one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene moiety.
[0029] Starter molecules are generally selected such that their average functionality is preferably in the range of 2.0 to 8.0, and more preferably in the range of 3.0 to 8.0. Optionally, a mixture of suitable starter molecules is used. [0030] Starter molecules for polyether polyols include amine containing and hydroxylcontaining starter molecules. Suitable amine containing starter molecules include, for example, aliphatic and aromatic diamines such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, phenylenediamines, toluenediamine, diaminodiphenylmethane and isomers thereof.
[0031] Other suitable starter molecules further include alkanolamines, e.g. ethanolamine, N-m ethylethanolamine and N-ethylethanolamine, dialkanolamines, e.g., diethanolamine, N- methyldiethanolamine and N-ethyldi ethanolamine, and trialkanolamines, e.g., triethanolamine, and ammonia.
[0032] Suitable amine containing starter molecules are selected from ethylenediamine, phenylenediamines, toluenediamine or isomers thereof. In one embodiment, it is ethylenediamine.
[0033] Hydroxyl-containing starter molecules are selected from sugars, sugar alcohols, for e.g. glucose, mannitol, sucrose, pentaerythritol, sorbitol; polyhydric phenols, resols, e.g., oligomeric condensation products formed from phenol and formaldehyde, trimethylolpropane, glycerol, glycols such as ethylene glycol, propylene glycol and their condensation products such as polyethylene glycols and polypropylene glycols, e.g., diethylene glycol, triethylene glycol, dipropylene glycol, and water or a combination thereof.
[0034] Suitable hydroxyl containing starter molecules are selected from sugar and sugar alcohols such as sucrose, sorbitol, glycerol, pentaerythritol, trimethylolpropane or mixtures thereof. In some embodiments the hydroxyl containing starter molecules are selected from sucrose, glycerol, pentaerythritol or trimethylolpropane.
[0035] Suitable alkylene oxides having 2 to 4 carbon atoms are, for example, ethylene oxide, propylene oxide, tetrahydrofuran, 1,2-butylene oxide, 2,3-butylene oxide, and styrene oxide. Alkylene oxides can be used singly, alternatingly in succession or as mixtures. In one embodiment, the alkylene oxides are propylene oxide and/or ethylene oxide. In some embodiments, the alkylene oxides are mixtures of ethylene oxide and propylene oxide that comprise more than 50 wt.-% of propylene oxide.
[0036] In another preferred embodiment, the polyester polyols are based on the reaction product of carboxylic acids or anhydrides with hydroxy group containing compounds. Suitable carboxylic acids or anhydrides have preferably from 2 to 20 carbon atoms, or from 4 to 18 carbon atoms, for example succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, oleic acid, phthalic anhydride. Particularly comprising of phthalic acid, isophthalic acid, terephthalic acid, oleic acid and phthalic anhydride or a combination thereof.
[0037] Suitable hydroxyl containing compounds are selected from ethanol, ethylene glycol, propylene- 1,2-gly col, propylene-l,3-glycol, butyl-ene-l,4-glycol, bu-tylene-2,3- glycol, hexane-l,6-diol, octane- 1,8 -diol, neopentyl glycol, cyclohexane dimethanol (1,4-bis- hydroxy-methylcyclohexane), 2-methyl-propane-l,3-diol, glycerol, trimethylolpropane, hexane-l,2,6-triol, butane -1,2,4-triol, trimethylolethane, pentaerythritol, quinitol, mannitol, sorbitol, methyl glycoside, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, polyethylenepropylene glycol, dibutylene glycol or polybutylene glycol. In one embodiment, the hydroxyl containing compound is selected from ethylene glycol, propylene- 1,2-gly col, propylene-l,3-glycol, butylene- 1,4-gly col, butylene-2,3-glycol, hexane-l,6-diol, octane- 1,8 -diol, neopentyl glycol, cyclohexane dimethanol (1,4-bis-hydroxy-methylcyclohexane), 2-methyl-propane-l,3-diol, glycerol, trimethylolpropane, hexane-l,2,6-triol, butane -1,2,4-triol, trimethylolethane, pentaerythritol, quinitol, mannitol, sorbitol, methyl glycoside or di ethylene glycol. In another embodiment, the hydroxyl containing compound is selected from ethylene glycol, propylene- 1,2-glycol, pro-pylene-l,3-glycol, butyl-ene- 1,4-gly col, butylene-2,3-glycol, hexane-l,6-diol, octane- 1,8 -diol, neopentyl glycol or di ethylene glycol. In still another embodiment, the hydroxyl containing compound is selected from hexane-l,6-diol, neopentyl glycol and di ethylene glycol. [0038] Such polyetherester polyols are obtainable as a reaction product of i) at least one hydroxyl-containing starter molecule; ii) of one or more fatty acids, fatty acid monoesters or mixtures thereof; iii) of one or more alkylene oxides having 2 to 4 carbon atoms.
[0039] The starter molecules of component i) are generally selected such that the average functionality of component i) is preferably 3.8 to 4.8, or from 4.0 to 4.7, or even from 4.2 to 4.6. Optionally, a mixture of suitable starter molecules is used.
[0040] Suitable hydroxyl containing starter molecules of component i) are selected from sugars, sugar alcohols (glucose, mannitol, sucrose, pentaerythritol, sorbitol), polyhydric phenols, resols, e.g., oligomeric condensation products formed from phenol and formaldehyde, trimethylolpropane, glycerol, glycols such as ethylene glycol, propylene glycol and their condensation products such as polyethylene glycols and polypropylene glycols, e.g., diethylene glycol, triethylene glycol, dipropylene glycol, and water or a combination thereof.
[0041] In another preferred embodiment, the hydroxyl containing starter molecules of component i) are selected from sugars and sugar alcohols such as sucrose and sorbitol, glycerol, and mixtures of said sugars and/or sugar alcohols with glycerol, water and/or glycols such as, for example, diethylene glycol, dipropylene glycol or combination thereof.
[0042] Said fatty acid or fatty acid monoester ii) is selected from polyhydroxy fatty acids, ricinoleic acid, hydroxyl-modified oils, hydroxyl-modified fatty acids and fatty acid esters based in myristoleic acid, palmitoleic acid, oleic acid, stearic acid, palmitic acid, vaccenic acid, petroselic acid, gadoleic acid, erucic acid, nervonic acid, linoleic acid, a- and g-linolenic acid, stearidonic acid, arachidonic acid, timnodonic acid, clupanodonic acid and cervonic acid or a combination thereof. Fatty acids can be used as purely fatty acids. In this regard, preference is given to using fatty acid methyl esters such as, for example, biodiesel or methyl oleate.
[0043] Biodiesel is to be understood as meaning fatty acid methyl esters within the meaning of the EN 14214 standard from 2010. Principal constituents of biodiesel, which is generally produced from rapeseed oil, soybean oil or palm oil, are methyl esters of saturated C16 to C18 fatty acids and methyl esters of mono- or pol-yunsaturated Cl 8 fatty acids such as oleic acid, linoleic acid and linolenic acid.
[0044] Suitable alkylene oxides iii) having 2 to 4 carbon atoms are, for example, ethylene oxide, propylene oxide, tetrahydrofuran, 1,2-butylene oxide, 2,3 -butylene oxide and/or styrene oxide. Alkylene oxides can be used singly, alternatingly in succession or as mixtures.
[0045] In another preferred embodiment, the alkylene oxides comprise propylene oxide and ethylene oxide. In another preferred embodiment, the alkylene oxide is a mixture of ethylene oxide and propylene oxide comprising more than 50 wt.-% of propylene oxide. In another embodiment, the alkylene oxide comprises purely propylene oxide.
[0046] In another preferred embodiment, the at least one polyol has an average functionality in the range of 2.0 to 8.0, the hydroxyl number in the range of 20 mg KOH/g to 800 mg KOH/g and the nominal molecular weight in the range of 200 g/ mole to 6000 g/ mole.
[0047] Preferably, the polyol has OH value ranging from 20 mg KOH/g to 800 mg KOH/g, or from 20 mg KOH/g to 750 mg KOH/g, or from 20 mg KOH/g to 700 mg KOH/g, or from 20 mg KOH/g to 650 mg KOH/g, or from 20 mg KOH/g to 600 mg KOH/g. In another preferred embodiment, the polyol has OH value ranging from 25 mg KOH/g to 600 mg KOH/g, or from 30 mg KOH/g to 600 mg KOH/g, or from 40 mg KOH/g to 600 mg KOH/g, 50 mg KOH/g to 600 mg KOH/g. In another preferred embodiment, the polyol has OH value ranging from 100 mg KOH/g to 600 mg KOH/g, or from 200 mg KOH/g to 600 mg KOH/g, or from 300 mg KOH/g to 600 mg KOH/g, or from 350 mg KOH/g to 600 mg KOH/g
[0048] Preferred polyol used are with the molecular weight distribution from 100 g/ mol to 6000 g/ mol, or from 200 g/ mol to 6000 g/ mol, or from 300 g/ mol to 6000 g/ mol, or from 350 g/ mol to 6000 g/ mol. In yet another embodiment, the polyol used are with the molecular weight distribution from 350g/ mol to 4500 g/ mol, or from 350 g/ mol to 4000 g/ mol, or from 350 g/ mol to 3500 g/ mol, or from 350 g/ mol to 3000 g/ mol, or from 350 g/ mol to 3000 g/ mol, or from 350 g/ mol to 2500 g/ mol, or from 350 g/ mol to 2450 g/ mol, or from 350 g/ mol to 2400 g/ mol, or from 350 g/ mol to 2350 g/ mol.
[0049] Suitable polyols in the polyol composition are preferably selected from Polytetrahydrofurane (PolyTHF), polyether polyols, polyester polyols, or polycarbonate polyols. In one embodiment, the polyol comprises a PolyTHF.
[0050] In another preferred embodiment, the at least one polyol is polyether polyols, polyester polyols, polyetherester polyols, polytetrahydrofuran, or a combination thereof.
[0051] In another preferred the polyol composition is a polyol mixture (i) based on the mixture of at least two, preferably separately prepared polyol. By the expression "at least two polyol" it is meant that two different polyols are used, which have different mean molecular weight data.
[0052] In another preferred the polyol composition is a polyol mixture (i) based on the mixture of at least three, preferably separately prepared polyol. By the expression "at least three polyol" it is meant that three different polyols are used, which have different mean molecular weight data.
[0053] The combination of more than one polyol is associated with obtaining a lower Coefficient of Friction (CoF) value. The PU Composition with polyol/s having an average functionality of about 3.5 to 4.0 are associated with the lowest CoF. Using a polyol with lower functionality resulted in higher CoF.
[0054] GRAPHENE:
[0055] The reaction mixture for the PU Composition includes the graphene. The graphene is added either in the Part A or the Part B or both part of the reaction mixture. The graphene component is present in Part A and/ or Part B. [0056] In an embodiment, the graphene includes monolayer graphene, few-layer graphene (FLG), multi-layer graphene (MLG), graphene nano-platelets (GNP), graphite oxides (GO), graphite ore, reduced graphene oxides (rGO), graphene quantum dots, graphene ribbons, suspended graphene particles or membranes thereof, graphene master batches thereof, or combination thereof.
[0057] In a preferred embodiment, the graphene component in the PU composition is in range from 0.01 wt.% to 10.0 wt.%, or 0.01 to 9.5 wt.% or, from 0.01 wt.% to 9.0 wt.%, or from 0.01 wt.% to 8.5 wt.%, or from 0.01 wt.% to 8.0.0 wt.%, or from 0.01 wt.% to 7.5 wt.%, or from 0.01 wt.% to 7.0 wt.%, or from 0.01 wt.% to 6.5 wt.%, or from 0.01 wt.% to 6.0 wt.%, or from 0.01 wt.% to 5.5 wt.%, or from 0.01 wt.% to 5.0 wt.% of the PU composition. In a more preferred embodiment, the graphene component is in range from 0.05 wt.% to 5.0 wt.%, or from 0.10 wt.% to 5.0 wt.%, or from 0.15 wt.% to 5.0 wt.%, or from 0.20 wt.% to 5.0 wt.%, or from 0.25 wt.% to 5.0 wt.%, or from 0.30 wt.% to 5.0 wt.%, or from 0.35 wt.% to 5.0 wt.%, or from 0.40 wt.% to 5.0 wt.% of the PU composition.
[0058] In a preferred embodiment, the graphene is in form of the GNP, an oxidized form of graphene, functionalized with oxygen-containing groups. The GNP is described to have a single platelet structure, i.e., single atomic layer structure or as having a multi -platelet structure.
[0059] In a preferred embodiment, the GNP has layer structure with layers in range from
1 to 40 layers, or from 1 to 35 layers, or from 1 to 30 layers, or from 1 to 25 layers, or from 1 to 20 layers. In a more preferred embodiment, the GNP has a layer structure with layers in from
2 to 20 layers, or from 3 to 20 layers, or from 4 to 20 layers. In a more preferred embodiment, the GNP has a layer structure with layers in range from 4 to 15 layers or from 1 to 10 layers.
[0060] In another preferred embodiment, the GNP has a particle size in range of 0.5 pm to 200 pm or from 0.5 pm to 150 pm or from 0.5 pm to 100 pm, or from 0.5 pm to 90 pm. In a more preferred embodiment the particle size is in range from 0.5 pm to 80 pm, or from 0.5 pm to 70 pm, or from 0.5 pm to 60 pm, or from 0.5 pm to 50 pm, or from 0.5 pm to 40 pm, or from 0.5 pm to 30 pm, or from 0.5 pm to 20 pm. In a furthermore preferred embodiment, the particle size is in range from 0.5 pm to 10 pm, or from 0.5 pm to 5 pm.
[0061] In another preferred embodiment, the graphene has an agglomeration size in range from 1 pm to 100 pm. In further preferred embodiment, the graphene has an agglomeration size distribution of DIO (from 1.0 to 4.0 pm), D50 (from 6.0 to 14.0 pm), and D90 (30.0 to 36 pm). D10, D50 and D90 denote percentage of particles (10%, 50% and 90%) in a size range.
[0062] In a preferred embodiment, the GNP has a short stack of graphene sheets having a platelet shape. The GNP has an average thickness of approximately 6 to 8 nanometres.
[0063] In another preferred embodiment, the GNP has a typical surface area in range from 100 to 500 m2/g, or from 100 to 450 m2/g, or from 100 to 400 m2/g. In a more preferred embodiment, the typical surface area of the GNP is in range of 100 to 350 m2/g,
[0064] CARBON BLACK:
[0065] The reaction mixture for the PU Composition includes the carbon black. The carbon black is added either in the Part A or the Part B or both part of the reaction mixture. The carbon black (CB) component is present in Part A and/ or Part B.
[0066] In an embodiment, the carbon black includes acetylene black, furnace black, gas black, lamp black, thermal black, conductive black, HNO3-treated CB, ammonia treated CB, doped CB, CB mixed with iron phthalocyanine, or combination thereof.
[0067] In a preferred embodiment, the carbon black includes a conductive black, with a sieve residue (325 mesh) calculated by ASTM D 1514 in range from 0.01 to 200 ppm, or from 0.01 to 150 ppm, or from 0.01 to 100 ppm, or from 0.01 to 90 ppm, or from 0.01 to 80 ppm, or from 0.01 to 70 ppm, or from 0.01 to 60 ppm. [0068] In another preferred embodiment the carbon black has a sulphur content measured by ASTM D 1506 in range from 0.001 to 5.0 %, or from 0.001 to 4.0 %, , or from 0.001 to 3.0 %, or from 0.001 to 2.0%, or from 0.001 to 1.0 % of the carbon black component.
[0069] In yet another preferred embodiment, the carbon black has a total surface area measured by ASTM D 6556 in range from 50 to 2000 m2/g, or from 50 to 1900 m2/g, or from 50 to 1800 m2/g, or from 50 to 1700 m2/g, or from 50 to 1600 m2/g, or from 50 to 1500 m2/g, from 50 to 1400 m2/g, or from 50 to 1300 m2/g, or from 50 to 1200 m2/g. In a more preferred embodiment, the carbon black has total surface area in range from 60 to 1200 m2/g, or from 70 to 1200 m2/g, or from 80 to 1200 m2/g, or from 90 to 1200 m2/g, or from 100 to 1200 m2/g. The ASTM D 6556 for total surface are determined by Brunauer, Emmett, and Teller (B.E.T. NS A) theory of multilayer gas adsorption behavior using multipoint determinations.
[0070] In a preferred embodiment, the carbon black includes a conductive black, with a sieve residue (45 mesh) calculated by ISO 787 18, in range from 0.01 to 200 ppm, or from 0.01 to 150 ppm, or from 0.01 to 100 ppm, or from 0.01 to 90 ppm, or from 0.01 to 80 ppm, or from 0.01 to 70 ppm, or from 0.01 to 60 ppm.
[0071] In another preferred embodiment the carbon black has a sulphur content measured by ASTM D 1619 in range from 0.001 to 5.0 %, or from 0.001 to 4.0 %, , or from 0.001 to 3.0 %, or from 0.001 to 2.0%, or from 0.001 to 1.0 % of the carbon black component.
[0072] In a preferred embodiment, the carbon black component in the PU composition is in range from 0.01 to 10.0 wt.%, or from 0.01 to 9.5 wt.%, or from 0.01 to 8.5 wt.%, or from 0.01 to 8.0 wt.% of the PU composition.
[0073] In a more preferred embodiment, the carbon black component in the PU composition is in range from 0.01 to 7.5 wt.%, or from 0.01 to 7.0 wt.% or from 0.01 to 6.0 wt.%, or from 0.01 to 5.5 wt.% or from 0.01 to 5.0 wt.% or from 0.01 to 4.5 wt.% or from 0.01 to 4.0 wt.% of the PU composition. [0074] In another embodiment, the reaction mixture used to prepare the PU composition includes both carbon black and graphene. In a preferred embodiment, the reaction mixture used to prepare the PU composition includes both carbon black and graphene in Part A. In another preferred embodiment, the reaction mixture used to prepare the PU composition includes both carbon black and graphene in Part B. In yet another preferred embodiment, the reaction mixture used to prepare the PU composition includes both carbon black and graphene in Part A and Part B.
[0075] In a most preferred embodiment, both the at least one graphene component and the at least one carbon black (CB) component is added to the Part A.
[0076] In yet another preferred embodiment, the combination of CB and graphene is in range from 0.5 wt. % to 30.0 wt. %, or from 0.5 wt.% to 28.0 wt.%, or from 0.5 wt.% to 26.0 wt.%, or from 0.5 wt.% to 24.0 wt.%, or from 0.5 wt.% to 22.0 wt.%, or from 0.5 wt.% to 20.0 wt.%, or from 0.5 wt.% to 18.0 wt.%, or from 0.5 wt.% to 16.0 wt.%, or from 0.5 wt.% to 14.0 wt.%, or from 0.5 wt.% to 12.0 wt.%, or from 0.5 wt.% to 10.0 wt.%, or from 0.5 wt.% to 8.0 wt.% of the PU composition. In a more preferred embodiment the combination of CB and graphene is in range from 1.0 wt.% to 8.0 wt.%, or from 1.5 wt.% to 8.0 wt.% of the PU composition.
[0077] In yet another preferred embodiment, the ratio of the graphene component to the carbon black component is in range from 10: 1 to 1 : 10, or from 10: 1 to 1 :9, or from 10:1 to 1 :8, or from 10: 1 to 1 :7, or from 10: 1 to 1 :6, or from 10: 1 to 1 :5, or from 10: 1 to 1 :4, or from 10: 1 to 1 :3, or from 10: 1 to 1 :2, or from 10: 1 to 1 : 1. In a more preferred embodiment, the ratio of graphene component to carbon black component is in range from 9: 1 to 1 : 1, or from 8: 1 to 1 : 1, or from 7: 1 to 1 :1, or from 6: 1 to 1 : 1..
[0078] ADDITIVES:
[0079] In an embodiment, the additives in the mixture can be selected from surface-active substances, flame retardants, nucleating agents, oxidation stabilizers, lubricants, mold release agents, dyes, pigments, dyes, flame retardants, hindered amine light stabilizers, ultraviolet light absorbers, stabilizers, ultra violet stabilizers, hydroxy stabilizers, plasticizers, epoxy plasticizers, chain regulator, polyethylene wax, antioxidants, defoamers, internal release agents, desiccants, blowing agents and anti-static agents or combinations thereof. Further details regarding additives can be found, for example, in the Kunststoffhandbuch, Volume 7, “Polyurethane” Carl-Hanser-Verlag Munich, 1st edition, 1966 2nd edition, 1983 and 3rd edition, 1993. Suitable amounts of these additives are well known to the person skilled in the art. However, for instance, the additives can be present in amounts up to 20 wt.-% based on the total weight of the polyurethane resin composition.
[0080] In another preferred embodiment, the at least one additional additive includes a catalyst, a chain extender, a flame retardant, a mold release agent, a rheology additive, a defoamer, a friction reducer, a non-sticky agent, an antistatic agent, a surfactant, a cross linker, or any combination thereof.
[0081] CHAIN EXTENDER
[0082] In an embodiment, the chain extender has a molecular weight of less than 499 g/mol. In the context of the present invention, the chain extender is understood to mean a compound having at least two functional groups reactive toward isocyanates, for example hydroxyl groups, amino groups or thiol groups, and a molecular weight Mw of less than 499 g/mol. At the same time, in the context of the present invention, the polyol composition is also free of compounds of this kind.
[0083] Preferably, the chain extenders have a molecular weight less than 300 g/mol, or from 10 g/mol to 210 g/mol. Another preferred chain extender has a molecular weight from 50 g/mol to 150 g/mol, or from 50 g/mol to 120 g/mol, or from 60 g/mol to 120 g/mol.
[0084] Suitable chain extenders can be selected from ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1-5 pentanediol, 1,6-hexanediol, 1,10-decanediol, 1,2- dihydroxycyclohexane, 1,3-dihydroxycyclohexane, 1,4-dihydroxy cyclohexane, diethylene glycol, 1,4-butanediol, bi s(2 -hydroxy-ethyl) hydroquinone, dipropylene glycol, glycerol, diethanolamine, and triethanolamine. Preferably, the chain extender can be selected from 1,2- ethylene glycol, 1,3-propylene glycol, 1,4 butane diol, 1,5-pentane diol, 1,6-hexane diol, Hydroquinone Bis (2 -hydroxyethyl) Ether (HQEE), or/ and hydroxyethylether of resorcinol or 1,3-Bis (2-hydroxyethyl) resorcinol (HER).
[0085] In one embodiment, suitable chain extenders and/or cross linkers present in the polyurethane resin composition is further described. The addition of bifunctional chain extenders, trifunctional and higher-functional cross linkers or, if appropriate, mixtures thereof might be added. Chain extenders and/or cross linkers used are preferably alkanol amines and in particular diols and/or triols having molecular weights preferably in between 60 g/mol to 300 g/mol. Suitable amounts of these chain extenders and/or cross linkers can be added and are known to the person skilled in the art. For instance, chain extenders and/or cross linkers can be present in an amount up to 99 wt.-%, or up to 20 wt.-%, based on the total weight of the polyurethane resin composition.
[0086] In another embodiment, commercially available compounds that are reactive towards isocyanate can also be employed, for e.g. Sovermol®, Pluracol® and Quadrol® from
BASF.
[0087] CATALYST:
[0088] In an embodiment, the reaction mixture includes a catalyst.
[0089] Suitable catalysts are well known to the person skilled in the art. Catalysts in the reaction mixture include tertiary amine and phosphine compounds, metal catalysts such as chelates of various metals, acidic metal salts of strong acids; strong bases, alcoholates and phenolates of various metals, salts of organic acids with a variety of metals, organometallic derivatives of tetravalent tin, trivalent and pentavalent As, Sb and Bi and metal carbonyls of iron and cobalt and mixtures thereof.
[0090] The amine catalyst include tertiary amines selected from triethylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, N,N, N', N'- tetramethylethylenediamine, pentamethyl-diethylenetriamine and higher homologues (as described in, for example, DE-A 2,624,527 and 2,624,528), l,4-diazabicyclo(2.2.2)octane, N- methyl-N'-dimethyl -aminoethylpiperazine, bis-(dimethylaminoalkyl)piperazines, tris(dimethylaminopropyl)hexahydro-l,3,5-triazin, N,N-dimethylbenzylamine, N,N- dimethylcyclohexylamine, N,N-diethyl-benzylamine, bis-(N,N-diethylaminoethyl) adipate, N,N,N',N'-tetramethyl-l,3-butanediamine, N,N-dimethyl-p-phenylethylamine, 1 ,2- dimethylimidazole, 2-methylimidazole, monocyclic and bicyclic amines together with bis- (dialkylamino)alkyl ethers, such as 2,2-bis-(dimethylaminoethyl)ether. Triazine compounds, such as, but not limited to, tris(dimethylaminopropyl)hexahydro-l,3,5-triazin can also be used.
[0091] Suitable catalysts are likewise known in principle from the prior art. Suitable catalysts are, for example, organic metal compounds selected from the group consisting of tin organyls, titanium organyls, zirconium organyls, hafnium organyls, bismuth organyls, zinc organyls, aluminum organyls and iron organyls, for example tin organyl compounds, preferably tin dialkyls such as dimethyltin or diethyltin, or tin organyl compounds of aliphatic carboxylic acids, preferably tin diacetate, tin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, bismuth compounds such as bismuth alkyl compounds or the like, or iron compounds, preferably iron(Ml) acetylacetonate, or the metal salts of the carboxylic acids, for example tin(II) isooctoate, tin dioctoate, titanic esters or bismuth(III) neodecanoate.
[0092] The catalysts, as described hereinabove, can be present in amounts preferably up to 20 wt.-% based on the total weight of the PU composition.
[0093] OTHER ADDITIVES:
[0094] In a preferred embodiment the composite structure is produced by resin transfer molding (RTM) technique.
[0095] In another preferred embodiment, the reaction mixture, as described hereinabove, can also comprise a reinforcing agent. Suitable reinforcing agents refer to fillers in the present context. [0096] FILLERS:
[0097] Suitable fillers include, such as, but not limited to, silicatic minerals, examples being finely ground quartzes, phyllosilicates, such as antigorite, serpentine, hornblendes, amphibols, chrysotile, and talc; metal oxides, such as kaolin, aluminum oxides, aluminium hydroxides, magnesium hydroxides, hydromagnesite, titanium oxides and iron oxides, metal salts such as chalk, heavy spar and inorganic pigments, such as cadmium sulfide, zinc sulfide, and also glass and others. Preference is given to using kaolin (china clay), finely ground quartzes, aluminum silicate, and coprecipitates of barium sulfate and aluminum silicate.
[0098] Suitable fillers have an average particle diameter in the range of 0.1 pm to 500 pm, more preferably in the range of 1 pm to 100 pm, and most preferably in the range of 1 pm to 10 pm. Diameter in this context, in the case of non-spherical particles, refers to their extent along the shortest axis in space.
[0099] Suitable amounts of the fillers can be present in the polyurethane resin composition which are known to the person skilled in the art. For instance, fillers can be present in an amount up to 50 wt.-%, based on the total weight of the polyurethane resin composition.
[00100] FLAME RETARDANTS:
[00101] Suitable flame retardants are tetrabromobisphenol A, brominated polystyrene oligomers, brominated butadiene-polystyrene copolymers in accordance with WO 2007/058736, tetrabromobisphenol A diallyl ether, and hexabromocyclododecane (HBCD), in particular the industrial products, where these in essence comprise the a-, P-, and y-isomer with added synergists, such as dicumyl. Preference is given to brominated aromatics, such as tetrabromobisphenol A, and to brominated styrene oligomers. Examples of suitable halogen- free flame retardants are expandable graphite, red phosphorus, and phosphorus compounds, such as triphenyl phosphate and 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide.
[00102] In a preferred embodiment, the flame retardant is graphite. The graphite includes graphite ore treated with sulfuric acid by intercalation process. The graphite ore has bulk density in range of 0.45 to 0.60 g/cm3. [00103] Preferred phosphorus compounds are tris(2-chloroisopropyl) phosphate, triethyl phosphate, diethyl ethylphosphonate, cresyl diphenyl phosphate, Exolit OP560, diphenyl 6- (diphenoxyphosphoryloxy)hexahydrofuro[3,2-b]furan-3-yl phosphate, 9, 10-dihydro-9-oxa- 10-phosphaphenanthrene 10-oxide, and 6H-dibenzo[c,e][l,2]oxaphosphorine 6-oxide.
[00104] Preference is moreover given to organic peroxides (dicumyl peroxide), sulfur, and disulfides as synergists. The abovementioned flame retardants can either be dissolved in the monomers before the polymerization reaction starts or incorporated in the PU by extrusion.
[00105] ANTISTATIC AGENTS:
[00106] Antistatic additives and antistatic polymers are known. By way of example, DE 3531660 describes antistatic polyurethane shoe soles. The antistatic effect is achieved via from 0.01 to 0.3% by weight of chemically bonded sulfonate groups. The volume resistivities achieved are <108 Q/cm. The use of various quaternary ammonium salts for increasing the conductivity of polymers is described in EP 1134268. This involves modifications of commercially available antistatic agents, such as Catafor F® or Catafor PU® from Rhodia. For example, volume resistivities of about 107 Q/cm are achieved at high concentrations.
[00107] Antistatic additives include ethylmethylimidazole ethyl sulfate. Ethylmethylimidazole ethyl sulfate can be used here alone or in a mixture, for example together with other antistatic additives. It is preferable that ethylmethylimidazole ethyl sulfate is used as sole antistatic additive.
[00108] In an embodiment, the antistatic agent is selected from Soyabean oil with CIO to C16 Carbon chains, l-Ethyl-3 -methyl imidazolium dicyanamide, alkali metal salts in solvent, phosphoric acid and triethyl ether, metallic salt and polyether.
[00109] STABILIZERS
[00110] Hydrolysis stabilizers used preferably comprise oligomeric and/or polymeric aliphatic or aromatic carbodiimides. [00111] In order to stabilize the PU composition, with respect to aging, it is preferable that stabilizers are added to the PU composition. For the purposes of the present invention, stabilizers are additives which protect a plastic or a plastics mixture from damaging environmental effects. Examples are primary and secondary antioxidants, hindered amine light stabilizer, UV absorber, hydrolysis stabilizer, quencher, and flame retardant. Examples of commercial stabilizers are given in Plastics Additive Handbook, 5th Edition, H. Zweifel, ed., Hanser Publishers, Munich, 2001 ([1]), pp. 98-136.
[00112] If the PU composition has exposure to thermoxi dative degradation during its use, antioxidants can be added. It is preferable to use phenolic antioxidants. Examples of phenolic antioxidants are given in Plastics Additive Handbook, 5th edition, H. Zweifel, ed, Hanser Publishers, Munich, 2001, pp. 98-107 and pp. 116-121. Preference is given to those phenolic antioxidants whose molar mass is greater than 700 g/mol. An example of a phenolic antioxidant whose use is preferred is pentaerythrityl tetrakis(3-(3,5-bis(l,l-dimethylethyl)-4- hydroxyphenyl)propionate) (Irganox® 1010). The concentrations generally used of the phenolic antioxidants are from 0.1 to 5% by weight, preferably from 0.1 to 2% by weight, in particular from 0.5 to 1.5% by weight, based in each case on the total weight of the PU.
[00113] If the PU composition may optionally include a UV absorber. UV absorbers are molecules which absorb high-energy UV light and dissipate the energy. Familiar UV absorbers used industrially are, for example, members of the group of cinnamic esters, of diphenylcyanoacrylates, of the formamidines, of the benzylidenemalonates, of the diarylbutadienes, or triazines, or of the benzotriazoles. Examples of commercial UV absorbers are found in Plastics Additive Handbook, 5th edition, H. Zweifel, ed, Hanser Publishers, Munich, 2001, pp. 116-122. In one preferred embodiment, the number-average molar mass of the UV absorbers is greater than 300 g/mol, in particular greater than 390 g/mol. The UV absorbers preferably used should moreover have molar mass no greater than 5000 g/mol, particularly preferably no greater than 2000 g/mol. The benzotriazoles group is particularly suitable as UV absorber. Examples of particularly suitable benzotriazoles are Tinuvin® 213, Tinuvin® 328, Tinuvin® 571, and also Tinuvin® 384, and Eversorb®82. The amounts preferably added of the UV absorbers are from 0.01 to 5% by weight, based on the total weight of antistatic, polyurethane, particularly preferably from 0.1 to 2.0% by weight, in particular from 0.2 to 0.5% by weight, based in each case on the total weight of the antistatic polyurethane.
[00114] In a preferred embodiment, the UV absorbers have a number average molecular weight of greater than 0.3x103 g/mol, in particular greater than 0.39x103 g/mol. Furthermore, the UV absorbers which are preferably used should have a molecular weight of not greater than 5cl03 g/mol, particularly preferably not greater than 2cl03 g/mol.
[00115] Particularly suitable UV absorbers are from the group of benzotriazoles. Examples of particularly suitable benzotriazoles are Tinuvin® 213, Tinuvin® 234, Tinuvin® 571 and Tinuvin® 384 and Ever- sorb®82. The UV absorbers are usually added in amounts of from 0.01 to 5% by weight, based on the total mass of the PU, preferably 0.1-2.0% by weight, in particular 0.2-0.5% by weight.
[00116] A UV stabilization as described above based on an antioxidant and a UV absorber is often still not sufficient to ensure good stability of the film against the damaging influence of UV rays. In this case, a hindered amine light stabilizer (HALS) can be added in addition to the antioxidant and the UV absorber to the film. HALSs are highly efficient UV stabilizers for most polymers.
[00117] HALS compounds are generally known and commercially available. Examples of commercially available HALSs may be found in Plastics Additive Handbook, 5th edition, H. Zweifel, Hanser Publishers, Munich, 2001, pp. 123-136.
[00118] As hindered amine light stabilizers, preference is given to employing hindered amine light stabilizers in which the number average molecular weight is greater than 500 g/mol. Furthermore, the molecular weight of the preferred HALS compounds should be not greater than 10 000 g/mol, particularly preferably not greater than 5000 g/mol. [00119] Particularly preferred hindered amine light stabilizers are bis(l , 2, 2,6,6- pentamethylpiperidyl) se- bacate (Tinuvin® 765, Ciba Spezialitatenchemie AG) and the condensation product of 1-hydrox- yethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid (Tinuvin® 622). Particular preference is given to the condensation product of 1- hydroxyethyl-2,2,6,6-tetramethyl-4-hydrox- ypiperidine and succinic acid (Tinuvin® 622) when the titanium content of the product is <150 ppm, preferably <50 ppm, in particular <10 ppm. HALS compounds are preferably used in a concentration of from 0.01 to 5% by weight, particularly preferably from 0.1 to 1% by weight, in particular from 0.15 to 0.3% by weight referring to the total weight of the film.
[00120] In a preferred embodiment of the film, hydrolysis inhibitors are comprised in the PU composition as auxiliaries; preference is given here to oligomeric and/or polymeric aliphatic or aromatic carbodiimides.
[00121] Further details regarding the abovementioned auxiliaries and additives may be found in the specialist literature, for example in Plastics Additive Handbook, 5th edition, H. Zweifel, ed., Hanser Publishers, Munich, 2001.
[00122] MOLD RELEASE AGENTS:
[00123] Mold release agents include release agents based on wax or silicon, mold release agents based on salts of aliphatic mono- or polycarboxylic acids having at least 25 carbon atoms, and primary mono-, di-, or polyamines having two or more carbon atoms, or amide or ester group-containing amines, which have at least one primary, secondary or tertiary amino group, release agents based on mixtures of at least two compounds from the group of aminecarboxylic acid-salts, saturated or unsaturated CeOH- and/or OH group-containing esters from mono- and/or poly carboxylic acids, and multivalent alcohols or natural and/or synthetic oils, fats or waxes, mold release agents based on ketimines, aldimines, enamines or cyclic Schiff bases. [00124] FRICTION REDUCERS:
[00125] The friction reducers include polyethylene and polytetrafluoroethylene (PTFE) powders. Polyethylene includes crosslinked and non-crosslinked polyethylene.
[00126] In an embodiment the friction reducer is a non-cross-linked polyethylene.
[00127] In an embodiment, the non-cross-linked polyethylene includes high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE- HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low-density polyethylene (LLDPE), (VLDPE) and (ULDPE)
[00128] In a preferred embodiment the non-crosslinked polyethylene is an Ultra-high molecular weight polyethylene (UHMWPE) powder. In another preferred embodiment, the UHMWPE has d50 average particle size in range from 0.01 pm to 500pm. In a more preferred embodiment the UHMWPE has the average particle size less than from 0.01 pm to 400pm or from 0.01 pm to 300pm, or from 0.01 pm to 200pm or from 0.01 pm to 100pm.
[00129] In another preferred embodiment the molecular weight in range of 0.5 Mio g/ mol to 20 Mio g/ mol. In a more preferred embodiment the UHMWPE has a molecular weight in range of 1.0 Mio g/ mol to 20 Mio g/ mol or in range of 1 Mio g/ mol to 15 Mio g/ mol, or in range of 1.0 Mio g/ mol to 10 Mio g/ mol.
[00130] In another embodiment, the friction reducer is a polytetrafluoroethylene (PTFE) powder.
[00131] In yet another embodiment the friction reducer is in range from 0.1 to 10.0 wt.%. In a preferred embodiment the friction reducer is in range from 1.0 to 9.0 wt.%, or from 1.0 to 8.0 wt.%, or from 1.0 to 7.0 wt.%, or from 1.0 to 6.0 wt.%, or from 1.0 to 5.0 wt.%. In a more preferred embodiment, the friction reducer is in range of 1.0 to 5.0 wt.%. [00132] In another preferred embodiment, the at least one friction reducer is selected from UHMWPE and PTFE or combination thereof. In a further embodiment the at least one friction reducer is in range of 0 to 30.0 wt. %.
[00133] PART B
[00134] In another embodiment, the PART B includes at least one isocyanate.
[00135] The isocyanates can be selected from aliphatic isocyanates, aromatic isocyanates, and a combination thereof. By the term “aromatic isocyanate”, it is referred to molecules having two or more isocyanate groups attached directly and/or indirectly to the aromatic ring. Further, it is to be understood that the isocyanate includes both monomeric and polymeric forms of the aliphatic and aromatic isocyanate. By the term “polymeric”, it is referred to the polymeric grade of the aliphatic and/or aromatic isocyanate comprising, independently of each other, different oligomers, and homologues.
[00136] In another embodiment, the isocyanate comprises an aromatic isocyanate selected from toluene diisocyanate; polymeric toluene diisocyanate, methylene diphenyl diisocyanate; polymeric methylene diphenyl diisocyanate; m-phenylene diisocyanate; 1,5 -naphthalene diisocyanate; 4-chloro-l; 3-phenylene diisocyanate; 2,4,6-toluylene triisocyanate, 1,3- diisopropylphenylene-2,4-diisocyanate; l-methyl-3,5-diethylphenylene-2,4-diisocyanate;
1.3.5-triethylphenylene-2,4-diisocyanate; l,3,5-triisoproply-phenylene-2,4-diisocyanate; 3,3'- diethyl-bisphenyl-4,4'-diisocyanate; 3,5,3',5'-tetraethyl-diphenylmethane-4,4'-diisocyanate; 3,5,3',5'-tetraisopropyldiphenylmethane-4,4'-diisocyanate; l-ethyl-4-ethoxy-phenyl-2,5- diisocyanate; 1,3, 5 -tri ethyl benzene-2,4,6-triisocyanate; l-ethyl-3,5-diisopropyl benzene-
2.4.6-triisocyanate, tolidine diisocyanate, 1,3, 5 -triisopropyl benzene-2,4,6-triisocyanate and mixtures thereof. In other embodiment, the aromatic isocyanate is selected from toluene diisocyanate; polymeric toluene diisocyanate, methylene diphenyl diisocyanate; polymeric methylene diphenyl diisocyanate, m-phenylene diisocyanate; 1,5 -naphthalene diisocyanate; 4- chloro-1; 3-phenylene diisocyanate; 2,4,6-toluylene triisocyanate, 1,3-diisopropylphenylene- 2,4-diisocyanate and l-methyl-3,5-diethylphenylene-2,4-diisocyanate. In other embodiments, the aromatic isocyanate is selected from toluene diisocyanate; polymeric toluene diisocyanate, methylene diphenyl diisocyanate; polymeric methylene diphenyl diisocyanate, m-phenylene diisocyanate and 1,5 -naphthalene diisocyanate or a combination thereof. In still other embodiment, the aromatic isocyanate is selected from toluene diisocyanate; polymeric toluene diisocyanate, methylene diphenyl diisocyanate and polymeric methylene diphenyl diisocyanate or mixture thereof.
[00137] In another preferred embodiment, the aromatic isocyanate is selected from methylene diphenyl diisocyanate, polymeric methylene diphenyl diisocyanate or combination thereof.
[00138] In another preferred embodiment, the methylene diphenyl diisocyanate is exists in three different isomeric forms, namely 2,2'-methylene diphenyl diisocyanate (2,2'-MDI), 2, d'methylene diphenyl diisocyanate (2,4'-MDI) and 4,4'-methylene diphenyl diisocyanate (4,4'- MDI). Methylene diphenyl diisocyanate can be classified into monomeric methylene diphenyl diisocyanate and polymeric methylene di-phenyl diisocyanate referred to as technical methylene diphenyl diisocyanate. Polymeric methylene diphenyl diisocyanate includes oligomeric species and methylene diphenyl diisocyanate isomers. Thus, polymeric methylene diphenyl diisocyanate may contain a single methylene diphenyl diisocyanate isomer or isomer mixtures of two or three methylene diphenyl diisocyanate isomers, the balance being oligomeric species. Polymeric methylene diphenyl diisocyanate tends to have isocyanate functionalities of higher than 2. The isomeric ratio as well as the amount of oligomeric species can vary in wide ranges in these products. For instance, polymeric methylene diphenyl diisocyanate may typically contain 30 wt.-% to 80 wt.-% of methylene diphenyl diisocyanate isomers, the balance being said oligomeric species. The methylene diphenyl diisocyanate isomers are often a mixture of 4,4'-methylene diphenyl diisocyanate, 2,4'-methylene diphenyl diisocyanate and low levels of 2,2'-methylene di-phenyl diisocyanate.
[00139] In another preferred embodiment, the isocyanate comprises a polymeric methylene diphenyl diisocyanate. Commercially available isocyanates available under the tradename, such as, but not limited to, Lupranate® from BASF can also be used for the purpose of the present invention. [00140] In another preferred embodiment, the aliphatic isocyanate is selected from isophorone diisocyanate, propylene-l,2-diisocyanate, propylene-l,3-diisocyanate, butylene-
1.2-diisocyanate, butylene-l,3-diisocyanate, hexamethylene-l,6-diisocyanate, 2- methylpentamethylene-l,5-diisocyanate, 2-ethylbutylene-l,4-diisocyanate, 1,5- pentamethylene diisocyanate, ethyl ester 1-lysine triisocyanate, 1,6,11-triisocyanatoundecane, (2,4,6-trioxotriazine-l,3,5(2h,4h,6h)-triyl)tris(hexamethylene) isocyanate, methyl-2,6- diisocyanate caproate, octamethlyene-l,8-diisocyanate, 2,4,4-trimethylhexamethylene-l,6- diisocyanate, nonamethylene diisocyanate, 2,2,4-trimethylhexamethylene-l,6-diisocyanate, decamethylene-1, 10-diisocyanate, 2,11-diisocyanato-dodecane, triphe-nylmethane-4,4’,4”- triisocyanate, toluene-2,4,6-triyl triisocyanate, tris(isocyanatohexyl)biuret, trimethylcyclohexyl] triisocyanate, 2,4,4'-triisocyanato-dicyclohexylmethane, 2,2,-methylene- bis(cyclohexyl isocyanate), 3,3'-methylene-bis(cyclohexyl isocyanate), 4,4'-methylene- bis(cyclohexyl isocyanate), 4,4'-ethylene-bis(cyclohexyl isocyanate), 4,4'-propylene-bis- (cyclohexyl isocyanate), bis(paraisocyano-cyclohexyl)sulfide, bis(para-isocyanato- cyclohexyl)sulfone, bis(para-isocyano-cyclohexyl)ether, bis(para-isocyanato- cyclohexyl)diethyl silane, bis(para-isocyanato-cyclohexyl)diphenyl silane, bis(para- isocyanato-cyclohexyl)ethyl phosphine oxide, bis(para-isocyanato-cyclohexyl)phenyl phosphine oxide, bis(para-isocyanato-cyclohexyl)N-phenyl amine, bis(para-isocyanato- cyclohexyl)N-methyl amine,3,3-diisocyanato adamantane, 3, 3 -diisocyano biadamantane, 3,3- diiso-cyanatoethyl-l'-biadamantane, 1,2-bis (3-isocyanato-propoxy)ethane, 2,2-dimethyl propylene diisocyanate, 3-methoxy hexamethylene-l,6-diisocyanate, 2,5-dimethyl heptamethylene diisocyanate, 5-methyl nonamethylene-l,9-diisocyanate, 1,4-diisocyanato cyclo-hexane, 1,2-diisocyanato octadecane, 2,5-diisocyanato-l,3,4-oxadiazole, OCN(CH2)3O(CH2)2O(CH2)3NCO and OCN(CH2)3N(CH3)(CH2)3NCO or polymeric forms of diisocyanates.; more preferably the aliphatic isocyanate selected from isophorone diisocyanate, propylene-l,2-diisocyanate, propylene-l,3-diisocyanate, butylene-l,2-diisocyanate, butylene-
1.3 -diisocyanate, hexamethylene-l,6-diisocyanate, 2-methylpentamethylene-l,5- diisocyanatel,5-pentamethylene diisocyanate, 1,6,11-triisocyanatoundecane, methyl-2,6- diisocyanate caproate, octamethlyene-l,8-diisocyanate, 2,4,4-trimethylhexamethylene-l,6- diisocyanate, nonamethylene diisocyanate, 2,2,4-trimethylhexamethylene-l,6-diisocyanate, decamethylene-1, 10-diisocyanate, 2,11-diisocyanato-dodecane or polymeric forms of diisocyanates; and most preferably the aliphatic isocyanate selected from isophorone diisocyanate, hexamethylene-l,6-diisocyanate, 2-methylpentamethylene-l,5-diisocyanate,
1,5-pentamethylene diisocyanate, 1 octamethly ene- 1 , 8-dii socy anate, 2.4.4- trimethylhexamethylene-l,6-diisocyanate, nonamethylene diisocyanate, 2.2.4- trimethylhexamethylene-l,6-diisocyanate, decam ethyl ene- 1 , 10 -di i socy anate. 2, H- diisocyanato-dodecane and polymeric forms of diisocyanates or mixtures thereof.
[00141] In another preferred embodiment, the isocyanate reactive component is a polyol having an average functionality in the range of 2.0 to 8.0 and the hydroxyl number in the range of 15 mg KOH/g to 1800 mg KOH/g. The compounds that are reactive towards isocyanate can be present in an amount in the range of 1 wt.-% to 99 wt.-%, based on the total weight of the reaction mixture.
[00142] In another embodiment, the at least one isocyanate is with an isocyanate functionality ranging from 2.0 to 4.0.
[00143] In one embodiment, the isocyanate composition comprises an isocyanate having an isocyanate functionality ranging from 1.5 to 3.0. Preferably, the isocyanate functionality of the first isocyanate ranges from 1.6 to 3.0, or from 1.7 to 3.0, or from 1.8 to 3.0, or from 1.9 to 3.0. More preferably, the isocyanate functionality of the isocyanate ranges from 1.9 to 2.9, or from 1.9 to 2.8, or from 1.9 to 2. 7.
[00144] The isocyanate content is in an amount from 1 wt.-% to 60 wt.-%. Preferably, the isocyanate component of the isocyanate is from 1 wt.-% to 55 wt.-%, or from 5 wt.-% to 55 wt.-%, or from 10 wt.-% to 55 wt.-%, or from 15 wt.-% to 55 wt.-%. More preferably, the isocyanate component of the first isocyanate is from 20 wt.-% to 55 wt.-%, or from 23 wt.-% to 55 wt.-%, or from 25 wt.-% to 55 wt.-% (29.5, 31.5, 33.5).
[00145] Preferably, the isocyanate is selected from a 2,2'-, 2,4'- and/or 4,4'-diisocyanate, a hexamethylene diisocyanate (HDI), or Hydrogenated MDI or a carbodiimide modified MDI. [00146] Preferably, the isocyanate has an isocyanate content in range from 25 wt.% to 55 wt.%.
[00147] In another preferred embodiment, the at least one isocyanate is selected from 4, d'diphenylmethane diisocyanate, polymeric MDI, carbodiimide modified MDI, MDI prepolymer or combination thereof.
[00148] In another embodiment, the Part B comprises at least two isocyanates, the first isocyanate and the second isocyanate. The first isocyanate is as described hereinabove. The second isocyanate has an isocyanate functionality of at least 2.0, said second isocyanate being different than the first isocyanate. Suitable second isocyanates have an isocyanate content of at least 5.0 wt.-%. Preferably, the second isocyanate in the isocyanate composition have an isocyanate content in range from 5 wt.% to 40 wt.%, or in range from 6 wt.% to 30 wt.%, or in range from 7 wt.% to 20 wt.%, the said second isocyanates being different than the first isocyanate.
[00149] Preferably, the second isocyanate in the isocyanate composition is selected from a prepolymer based on carbodiimide-modified diphenylmethane 2,2'-, 2,4'- and/or 4,4'- diisocyanate.
[00150] In one embodiment, the isocyanate composition comprises a mixture of the first isocyanate and the second isocyanate. The weight ratio between the first isocyanate and the second isocyanate in the isocyanate composition is in a range from 2.0: 1.0 to 1.0: 2.0. Preferably, the weight ratio between the first isocyanate and the second isocyanate in the isocyanate composition is in a range from 2.0: 1.0 to 1.0: 1.5 or from 2.0: 1.0 to 1.0: 1.3, or from 2.0:1.0 to 1.0: 1.0. More preferably, the weight ratio between the first isocyanate and the second isocyanate in the isocyanate composition is in a range from 1.9: 1.0 to 1.0: 1.0, or from 1.8: 1.0 to 1.0: 1.01, or from 1.7: 1.0 to 1.0:1.0. [00151] METHOD OF OBTAINING PU COMPOSITION:
[00152] Another aspect of the present invention is an embodiment, directed towards a method of obtaining a polyurethane (PU), the method comprising the steps of: a. providing the Part A and the Part B of the reaction mixture for the composition ; b. mixing the Part A and the Part B; c. optionally heating the reaction mixture.
[00153] In an embodiment, the mixing is performed by a mixing device. The mixing device can be a low pressure or high-pressure mixing device comprising: pumps to feed the streams, a high-pressure mixing head in which the Part A and Part B, as described hereinabove, are mixed, a feed line A fitted to the high-pressure mixing head through which the Part A stream is introduced into the mixing head, and a feed line B fitted to the high-pressure mixing head through which the Part B is introduced into the mixing head.
[00154] Optionally, the mixing device, as described hereinabove, can further comprise at least one measurement and control unit for establishing the pressures of each feed lines in the mixing head. Also, the term “low pressure” here refers to a pressure in between 0.1 MPa to 5 MPa, while the term “high pressure” refers to pressure above 5 MPa.
[00155] Suitable temperatures for processing the reaction mixture are well known to the person skilled in the art. In an embodiment the mixing is performed at a temperature from 40°C to 85°C.
[00156] In another embodiment, the Part A and the Part B of the reaction mixture are passed from the same or separate mixing head into the mixing device with or without pressure. A solid/gas mixture can be added through additional inlets. By “solid”, it is referred to the fillers, as described hereinabove, which are in a solid state of matter. [00157] Suitable temperatures for processing the reaction mixture are well known to the person skilled in the art.
[00158] In one embodiment, before mixing into the mixing device, the Part A and Part B, independent of each other, are pre-mixed in suitable mixing means, such as, but not limited to, a static mixer.
[00159] In an embodiment, the method of obtaining the PU composition includes premixing the Part A (having the graphene and CB) with high shear force before mixing with the Part B.
[00160] In another embodiment, the mixing is performed at a temperature from 40°C to 85°C.
[00161] The reaction mixture obtained from the mixing device is fed to a means to provide shape to the PU composition. The means to provide shape includes but is not limited to spraying, spray molding, and injection molding.
[00162] In another embodiment, the reaction mixture is poured in a mold and cured at temperature between 60°C to 85°C. In a preferred embodiment, the reaction mixture is Injection molded. In a further preferred embodiment, the injection-molding machine is used specified to be a 10 cc micro-injection molding machine to give tensile specimens (temperature of tensile-specimen mold: 40° C to 85° C; temperature of melt accumulator: up to 190° C).
[00163] In another embodiment, the mold temperature is 60°C, with fill time of 5 to 20 seconds and demold time in range of 1 to 15 mins.
[00164] In a more preferred embodiment, for lab scale preparation, the high-speed mixer is used to mix Part A components at room temperature. Then, the components of Part A and Part B are mixed at defined ratio. The mixture is then poured in a plaque mold and cured at 60°C for 5 mins in a pre-heated oven. [00165] In another more preferred embodiment, for the pilot scale preparation, the components of Part A and Part B are loaded in a heated day tanks at 45°C. The components are mixed and injected into a RIM mold at 60 to 80 °C.
[00166] USE
[00167] Another aspect of the present invention is directed to the uses of the PU composition.
[00168] Another aspect of the present invention is directed to an electrically semi- conductive system obtained by the PU composition.
[00169] Another aspect of the present invention is directed to the uses of the PU composition in electrostatic discharge (ESD) related applications. The applications include control the electrical resistance of the material by using the PU composition in preparation of the same. ESD application includes making surface covering, flooring, coatings that help control ESD events including sparks.
[00170] Yet another aspect of the present invention is directed towards an electrically semi- conductive system obtained by the PU composition. In an embodiment, the composition is used in an Electrostatic Discharge (ESD) application.
[00171] The PU composition and articles made thereof are associated with an exceptionally low coefficient of friction CoF (about 0.1-0.15 similar to UHMWPE, a surface resistivity in the range of l.OxlO6 to 9.0xl0n ohm and successful fire resistance performance as per Method A, i.e., UL94 HB with no dripping are required.
[00172] The PU composition is associated with low coefficient of friction (COF) and antistatic properties. The combination of graphene and carbon black results in a durable antistatic characteristic that is stable and does not change with ambient conditions. This is not achievable using either of them alone or liquid Antistats. Furthermore, the addition of graphene improves the durability of coefficient of friction due to its multi-layered structure. The PU Composition provides a viable alternative to the usage of liquid Antistats in applications requiring a surface resistivity between 108 and 1011 ohms per square.
[00173] The viscosity of reaction mixture of the PU composition with combination of graphene/ carb on black is still low enough and suitable for many low-pressure and high- pressure processes.
[00174] The PU composition is associated with rigid and possesses high thermal and mechanical properties. The use of graphene improves both mechanical properties and the flame resistance of the system. The modulus increased slightly when graphene is used. Also, heat deflection temperature increased at least by 10 °C.
[00175] The PU Composition as disclosed out-perform when compared to with PU composition with liquid Antistats commonly used for ESD applications. Most importantly, the PU Composition has longer shelf life and does not change with ambient conditions, i.e., temperature and humidity. On the contrary, liquid Antistats depend on both temperature and humidity and the effectiveness will fade by time.
[00176] The flammability rating is measured by METHOD A.
[00177] METHOD A
[00178] The flammability rating is calculated for test specimen prepared by the PU Composition and the method as described hereinabove. The Rating is calculated as a function of the burning rate and taking account of the material thickness.
[00179] The method A includes a pretreatment for 48 hours at 23 °C and relative humidity. The flame application is done for 20 mm high Trill burner flame for 30 seconds. The flame application is stopped if the flame front reaches the first mark within 30 seconds.
[00180] The flammability rating is passed if the a. Test specimen of 3 to 13 mm bums at rate of less than or equal to 40 mm/ min. b. Test specimen of less than 3 mm burns at rate of less than or equal to 75 mm/ mm. c. Flam is extinguished before the first mark, bum rate being 0 mm/ min.
[00181] The presently claimed invention is illustrated in more detail by the following embodiments and combinations of embodiments which results from the corresponding dependency references and links:
I. A polyurethane (PU) composition prepared from a reaction mixture comprising: a. Part A with at least one isocyanate reactive component; b. Part B with at least one isocyanate; wherein the reaction mixture includes at least one graphene component and/ or at least one carbon black (CB) component; wherein graphene component is present in Part A and/ or Part B; and wherein carbon black (CB) component is present in Part A and/ or Part B.
II. The composition of embodiment I, wherein the at least one isocyanate reactive component comprises at least one polyol.
III. The composition of embodiment II, wherein the at least one polyol has an average functionality in the range of 2.0 to 8.0, the hydroxyl number in the range of 20 mg KOH/g to 800 mg KOH/g and the nominal molecular weight in the range of 200 g/ mole to 6000 g/ mole.
IV. The composition of any one of embodiment I to III, wherein the at least one polyol is poly ether polyols, polyester polyols, poly etherester polyols, Polytetrahydrofurane, or a combination thereof.
V. The composition of any one of embodiment I to IV, wherein the at least one isocyanate is with an isocyanate functionality ranging from 2.0 to 4.0. VI. The composition of any one of embodiment I to V, wherein the at least one isocyanate is 4,4 '-diphenylmethane diisocyanate, polymeric MDI, carbodiimide modified MDI, an Elastoflex 2500U, MDI prepolymer or combination thereof.
VII. The composition of any one of embodiment I to VI, wherein the graphene component is in range of 0.01 to 8.0 wt.%.
VIII. The composition of any one of embodiment I to VII, wherein the graphene includes monolayer graphene, few-layer graphene (FLG), multi-layer graphene (MLG), graphene nano-platelets (GNP), graphite oxides (GO), reduced graphene oxides (rGO), graphene quantum dots, graphene ribbons, suspended graphene particles or membranes thereof, graphene master batches thereof, or combination thereof.
IX. The composition of any one of embodiment I to VIII, wherein the carbon black (CB) component is in range of 0.01 to 8.0 wt. %.
X. The composition of any one of embodiment I to IX, wherein the carbon black (CB) component includes acetylene black, furnace black, gas black, lamp black, thermal black, conductive black, HNO3-treated CB, ammonia treated CB, doped CB, CB mixed with iron phthalocyanine, or combination thereof.
XI. The composition of any one of embodiment I to X, wherein the ratio of the graphene component to the carbon black component is in range from 10: 1 to 1 : 10.
XII. The composition of any one of embodiment I to XI, wherein combination of CB and graphene is in range of 1 % to 30 wt. %.
XIII. The composition of any one of embodiment I to XII, wherein the at least one additive includes from a catalyst, a chain extender, a flame retardant, a mold release agent, a rheology additive, a defoamer, a friction reducer, a non-sticky agent, an antistatic agent, a surfactant, a cross linker, or any combination thereof. XIV. The composition of any one of embodiment I to XIII, wherein the friction reducer is a polyethylene including an ultra-high molecular weight polyethylene (UHMWPE) powder, high molecular weight polyethylene (HMWPE) powder or a polytetrafluoroethylene or a combination thereof.
XV. The composition of any one of embodiment I to XIV wherein the friction reducer is in range of 1.0 to 10.0 wt.%.
XVI. The composition of any one of embodiment I to XV, wherein the at least one other antistatic agent is selected from Soyabean oil with CIO to C16 Carbon chains, 1-Ethyl- 3 -methyl imidazolium di cyanamide, alkali metal salts in solvent, phosphoric acid and triethyl ether, metallic salt and polyether, or combination thereof.
XVII. The composition of any one of embodiment I to XVI, wherein the at least one antistatic agent is in range of 0 to 15.0 wt.%.
XVIII. A method of obtaining a polyurethane (PU) composition, the method comprising: c. providing the Part A and the Part B of the reaction mixture for the composition of one of embodiment I to XVII; d. mixing the Part A and the Part B; e. optionally heating the reaction mixture.
XIX. The method of embodiment XVIII, wherein the Part A (having the graphene and CB) is pre-mixed with high shear force before mixing with the Part B.
XX. The method of any one of embodiment XVIII or XIX, wherein the mixing is performed at a temperature from 40°C to 85°C.
XXI. The method of any one of embodiment XIX or XX, wherein the reaction mixture is poured in a mold and cured at temperature between 60°C to 85°C. XXII. An electrically semi -conductive system obtained by the composition of any one of embodiment I or XVII, or by the method of any one of embodiment XVIII to XXI.
XXIII. Use of the composition in any one of embodiment I or XVII, in ESD application.
[00182] EXAMPLES: The presently claimed invention is illustrated by the non-restrictive examples which are as follows:
RAW MATERIALS
The raw materials used in the reactions are listed in the below table A
Table A: List of raw materials with the abbreviations used.
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001
STANDARD METHODS:
The following standard methods listed in table B were employed for the measurements of various parameters
Table B:
Figure imgf000040_0002
Figure imgf000041_0001
[00183] PROCESS FOR FORMING THE PU
[00184] Tables 1 to 3 provide weight % of the components present in the Part A and the Part B along with the Ratio of Part A: Part B. Each component of both Part A and Part B in Tables 1 to 3 are in wt.% of total PU composition. The process employed to form PU as per compositions of Tables 1 to 3 ae same and is described below.
[00185] The high-speed mixer was used to mix Part A components at room temperature. Then, the components of Part A and Part B were mixed at defined ratio. The mixture was then poured in a plaque mold and cured at 60°C for 5 mins in a pre-heated oven.
TABLE 1 : COMPOSITION OF PU IN EXAMPLES 1 TO 10.
Figure imgf000041_0002
Figure imgf000042_0001
TABLE 2: COMPOSITION OF PU IN EXAMPLES 11 TO 20:
Figure imgf000042_0002
Figure imgf000043_0001
TABLE 3: COMPOSITION OF PU IN EXAMPLES 21 TO 29.
Figure imgf000043_0002
Figure imgf000044_0001
Figure imgf000045_0001
[00186] TESTING OF PU COMPOSITION
[00187] The PU composition formed were tested based on the standard methods to determine the Shore D Hardness, Coefficient of Friction, Antistatic Resistivity, Surface Resistivity, Flame Retardance and optionally the Flexural Modulus, Flexural Stress, Flexural Strain, Tensile Modulus, Tensile Stress, Tensile Strain. as indicated in Table B and Method A (for flammability rating).
[00188] The test results for Examples mentioned in Table 1 to 3 are provided in Tables 4 and 5.
[00189] The PU composition is associated with a surface resistivity in range of l.OxlO6 to 9.0xl0n ohm in an electrically semi-conductive system. The surface resistivity is suitable for electrostatic discharge applications. The electrical results are associated with presence of graphene and carbon black in the PU composition.
[00190] The electrical results show that there is a synergy between graphene and carbon black. Graphene alone results in electrical conductivity of above l.OxlO11 ohm at loadings above 1.5 wt.% (See Examples E6). Carbon black alone also renders electrically conductive system at loadings above 1 wt. % (See Examples El l, E12, E27), but results in a significant viscosity increase that make the processing difficult or not possible for many applications requiring low viscosity. The viscosity of such a system can go above 5000 cP while the viscosity of the system containing both graphene (2-3 wt.%) and carbon black (0.25-0.5 wt.%) is below 2000 cP suitable for most low pressure and high-pressure applications.
[00191] The graphene 1.5 wt.% and carbon black 0.25 wt.% combination gives the best overall performance. The viscosity of this system is below 2000 cP which is typical for mold PU processing equipment.
TABLE 4: PROPERTIES OF PU IN EXAMPLES 1 TO 15:
Figure imgf000046_0001
# OL - Over limit
TABLE 5: PROPERTIES OF PU IN EXAMPLES 16 TO 29:
Figure imgf000047_0001

Claims

CLAIMS:
1. A polyurethane (PU) composition prepared from a reaction mixture comprising: a. Part A with at least one isocyanate reactive component and optionally at least one additive; b. Part B with at least one isocyanate; wherein the reaction mixture includes at least one graphene component and at least one carbon black (CB) component; wherein graphene component is present in Part A and/ or Part B; and wherein carbon black (CB) component is present in Part A and/ or Part B.
2. The composition of claim 1, wherein the graphene component and the carbon black (CB) component is present in Part A.
3. The composition of claim 1 or 2, wherein the at least one isocyanate reactive component comprises at least one polyol.
4. The composition of any one of claims 1 to 3, wherein the at least one polyol has an average functionality in the range of 2.0 to 8.0, the hydroxyl number in the range of 20 mg KOH/g to 800 mg KOH/g and the nominal molecular weight in the range of 200 g/ mole to 6000 g/ mole.
5. The composition of any one of claims 3 and 4, wherein the at least one polyol is poly ether polyols, polyester polyols, polyetherester polyols, Polytetrahydrofurane, or a combination thereof.
6. The composition of any one of claims 1 to 5, wherein the at least one isocyanate is with an isocyanate functionality in a range from 2.0 to 4.0.
7. The composition of any one of claims 1 to 6, wherein the at least one isocyanate is 4,4'- diphenylmethane diisocyanate, polymeric MDI, carbodiimide modified MDI, an Elastoflex 2500U, MDI prepolymer or combination thereof. The composition of any one of claims 1 to 7, wherein the graphene component is in range of O.Olwt. % to 8.0 wt.%. The composition of any one of claims 1 to 8, wherein the graphene is selected from monolayer graphene, few-layer graphene (FLG), multi-layer graphene (MLG), graphene nano-platelets (GNP), graphite oxides (GO), reduced graphene oxides (rGO), graphene quantum dots, graphene ribbons, suspended graphene particles or membranes thereof, graphene master batches thereof, or combination thereof. The composition of any one of claims 1 to 9, wherein the carbon black (CB) component is selected from acetylene black, furnace black, gas black, lamp black, thermal black, conductive black, HN03 -treated CB, ammonia treated CB, doped CB, CB mixed with iron phthalocyanine, or combination thereof. The composition of any one of claims 1 to 10, wherein the carbon black (CB) component is in range of 0.01 to 8.0 wt. %. The composition of any one of claims 1 to 11, wherein the ratio of the graphene component to the carbon black component is in range from 10: 1 to 1 : 10. . The composition of any one of claims 1 to 12, wherein combination of CB and graphene is in range of 1 % to 30 wt. %. The composition of any one of claims 1 to 13, wherein the at least one additive is selected from a catalyst, a chain extender, a flame retardant, a mold release agent, a rheology additive, a defoamer, a friction reducer, a non-sticky agent, an antistatic agent, a surfactant, a cross linker, or any combination thereof. The composition of claims 14, wherein the friction reducer is a polyethylene including an ultra-high molecular weight polyethylene (UHMWPE) or a polytetrafluoroethylene or a combination thereof. The composition of claims 15 wherein the friction reducer is in range of 0.1 to 10.0 wt.%. A method of obtaining a polyurethane (PU) composition, the method comprising the steps of: a. providing the Part A and the Part B of the reaction mixture for the composition of any one of claim 1 to 16; b. mixing the Part A and the Part B; c. optionally heating the reaction mixture. The method of claim 17, wherein the Part A (having the graphene and CB) is pre-mixed with high shear force before mixing with the Part B. The method of any one of claims 17 or 18, wherein the mixing is performed at a temperature from 40°C to 85°C. The method of any one of claims 17 to 19, wherein the reaction mixture is optionally heated and is poured in a mold and cured at temperature between 60°C to 85°C. An electrically semi-conductive system obtained by the composition of any one of claims 1 to 15, or by the method of any one of claims 17 to 20. Use of the composition of any one of claims 1 to 20, in Electrostatic Discharge (ESD) application.
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