Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
  • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/0895—Manufacture of polymers by continuous processes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
  • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
  • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
  • C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
  • C08G18/3844—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing one nitrogen atom in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
  • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
  • C08G18/3863—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms
  • C08G18/3865—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
  • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures

Definitions

• the present invention relates to the preparation of isocyanate-terminated polyurethane prepolymers having a content of less than or equal to 0.1% by weight of free diisocyanate monomers.
• isocyanate-terminated polyurethane prepolymers are useful for preparing polyurethanes, polyurethanes urea or thermoplastic polyurethane granules.
• Polyurethanes are among the most versatile commercial materials. Thermosetting or thermoplastic, polyurethanes are used in a variety of industries. Thus, they can be used to form flexible foams used in furniture and particularly in the automotive industry or rigid foams used as an insulation in the building or appliances. Polyurethanes are also used in many glues, lacquers, varnishes, paints, etc. Many methods of preparing polyurethanes have been developed. Thus, the polyurethanes can be prepared in a single step by mixing the various constituents of the polymer, generally in the absence of a solvent. They can also be prepared from isocyanate-terminated prepolymers formed by reaction between an isocyanate, typically employed in large excess, and a polyol.
• Isocyanates are toxic compounds. At high concentrations they can be irritating to the skin and mucous membranes. Continuous exposure to low concentrations may, in turn, cause sensitization causing skin or respiratory allergies. Some isocyanates are even found to be carcinogenic. Their penetration into the body is mainly by respiratory way in vapor or aerosol form. Toluene diisocyanate (TDI), diphenylmethylene diisocyanate (MDI) and p-phenyl diisocyanate (PPDI) are particularly harmful because of their high volatility. Since the entry into force of the European REACH Regulation, certain substances or groups of chemical substances are subject to marketing and use restrictions for certain uses. In particular, since December 2010, the marketing of products containing more than 0.1% of MDI or free TDI is strictly regulated.
• TDI Toluene diisocyanate
• MDI diphenylmethylene diisocyanate
• PPDI p-phenyl diisocyanate
• the free isocyanates present in the isocyanate-terminated prepolymers may alter the properties of the polyurethanes formed from these prepolymers. Indeed, free isocyanates can react with chain extenders creating isolated rigid segments causing phase separation problems.
• the present invention relates to a process for the preparation of an isocyanate-terminated polyurethane prepolymer comprising a content of less than or equal to 0.1% by weight of free diisocyanate monomers relative to the total weight of the prepolymer and exhibiting a NCO index ranging from 2 to 6, said process comprising the following steps:
• diisocyanate monomers selected from diisocyanates having two NCO functions having a reactivity difference greater than 6, said difference in reactivity resulting from the dissymmetry of the monomers and / or a substitution effect;
• polyols of functionality 2 having a molar mass ranging from 150 to 3000 g / mol;
• the diisocyanate monomers and the polyols being in such a quantity that the ratio "number of NCO functions" / "number of OH functions” varies from 1.4 to 2; b) degassing and stabilizing the reaction medium obtained in step a) at a temperature ranging from 50 ° C to 1 10 ° C;
• the present invention also relates to the use of an isocyanate-terminated polyurethane prepolymer obtained according to the preceding process for the preparation of polyurethanes by low-pressure or high-pressure casting, or by means of a liquid injection machine.
• the present invention also relates to the use of an isocyanate-terminated polyurethane prepolymer obtained according to the preceding process for the preparation of thermoplastic granules, in particular by means of an extruder with head cut under water and then injection in press.
• the present invention relates to a process for preparing a polyurethane, polyurethane urea or thermoplastic polyurethane (PTU) granules, comprising the following steps: iv) preparing an isocyanate-terminated polyurethane prepolymer having a content of less than or equal to 0.1% in mass of free diisocyanate monomers relative to the total weight of the prepolymer and having an NCO value ranging from 2 to 6 according to the preceding method;
• step iv) reacting the prepolymer obtained in step iv) with polyols and / or polyamines, said polyols and polyamines having an average molecular weight ranging from 50 to 4000 g / mol and an average functionality equal to or greater than 2;
• the terms "degassing” or “degassing” refer to all techniques known to those skilled in the art to eliminate the gases enclosed in the chamber where the process for preparing a polyurethane prepolymer according to the present invention is carried out.
• a simple pump can be connected to evacuate the gas from the enclosure and thus lower the gas pressure thereof.
• the pressure of the chamber is close to 0.5 atmosphere ( ⁇ 0.1 atmosphere), more preferably close to 0.25 atmosphere ( ⁇ 0.1 atmosphere), more preferably still close to 0.1 atmosphere ( ⁇ 0.1 atmosphere), and in particular 0 atmosphere.
• ratio "number of NCO functions" / "number of OH functions" can be determined theoretically on the basis of the structure and the amount of the diisocyanates and polyols involved. Alternatively, any assay technique that makes it possible to determine the number of one and the other of the NCO and OH functions is applicable.
• stabilization or “stabilize” for example in the expression “stabilize the reaction medium obtained in step a) at a temperature ranging from 50 ° C to 1 10 ° C
• the temperature is fixed value for a fixed time, which is the generally accepted definition of this term.
• this temperature value may nevertheless have small variations of the order of ⁇ 10 ° C, see ⁇ 5 ° C.
• the stabilized temperature values can be between 60 and 100 ° C, between 70 and 90 ° C, between 75 and 85 ° C, preferably 80 ° C.
• the time determined in the context of the present invention may vary from a few minutes (for example 10 minutes, 20 minutes, 30 minutes or 45 minutes) to a few hours (hence from one hour, or even 2 hours, 3 hours, hours, 10 hours or 15 hours).
• This time is a function of the technical effect demonstrated in the present patent application, which is to limit the content of free isocyanates.
• This time is also a function of the desired yield, that is to say the optimum performance of the reaction. Those skilled in the art will therefore adapt this time value to the desired technical effect.
• the expression "molar mass" in the context of the present invention relates to the average molecular weight by mass (or so-called "by weight”) according to the general definition that a person skilled in the art can make of it:
• any technique known in the art for determining this average molar mass is applicable to the present invention, for example by dynamic light scattering, ultracentrifugation, mass spectrometry (eg MALDI-TOF), or by any applicable chromatography such as exclusion (also called “steric exclusion”) or permeable gel.
• Viscosity translates, in short, the resistance of a fluid to the flow.
• the viscosity can be measured by any technique known to those skilled in the art at the chosen temperature.
• the viscosity of the isocyanate-terminated polyurethane prepolymer is less than 6000 mPa.s at a temperature between 85 ° C and 105 ° C, preferably 95 ° C.
• isocyanate-terminated polyurethane prepolymers comprising a content of less than or equal to 0.1% by weight of free diisocyanate monomers relative to the total weight of the prepolymer and having an NCO value ranging from 2 to 6 could be prepared. by a method comprising the following steps:
• diisocyanate monomers chosen from diisocyanates having two NCO functions having a reactivity difference of greater than 6, the difference in reactivity resulting from the asymmetry of the monomers and / or from a substitution effect;
• polyols of functionality 2 having a molar mass ranging from 150 to 3000 g / mol;
• the diisocyanate monomers and the polyols being in such a quantity that the ratio "number of NCO functions" / "number of OH functions" varies from 1.4 to 2;
• step b) degassing and stabilizing the reaction medium obtained in step a) at a temperature ranging from 50 ° C to 1 10 ° C;
• the process developed by the inventors does not include a distillation step.
• the isocyanate-terminated polyurethane prepolymer is recovered directly after the implementation of steps a) and b).
• the NCO index of the isocyanate-terminated polyurethane prepolymers is a measured index. It can be determined by assay according to standard NF T52 132.
• the NCO value of the isocyanate-terminated polyurethane prepolymers ranges from 2 to 6. More particularly, the NCO value of the isocyanate-terminated polyurethane prepolymers may range from 2.2 to 5.3.
• the content of free diisocyanate monomers in the isocyanate-terminated polyurethane prepolymers can be determined by gas chromatography according to standard NF EN ISO 10283.
• the diisocyanate monomers are chosen from diisocyanates having two NCO groups having a difference of reactivity greater than 6, the difference in reactivity resulting from the asymmetry of the monomers and / or from a substitution effect. This difference in reactivity is given in the scientific literature (Pascault et al, "Thermosetting Polymers” Ed M.
• diisocyanates are well documented in the literature.
• diisocyanates such as diphenylmethane-4,4'-diisocyanate (MDI) or para-phenylene-4,4'-diisocyanate (PPDI)
• MDI diphenylmethane-4,4'-diisocyanate
• PPDI para-phenylene-4,4'-diisocyanate
• the two NCO groups have the same initial reactivity, but since the NCO group itself activation on isocyanate reactivity, in that an NCO group reacted, introduced a substitution effect generally reduces the reactivity of the second NCO group.
• Asymmetric diisocyanates such as 2,4-TDI is more complex because the initial reactivity of the two isocyanate groups is not equivalent and the substitution effect which amplifies the difference.
• 4-NCO is about 10 to 20 times more reactive than 2-NCO, but the reactivity ratio also depends on the temperature (see Chapter 5). This difference also explains why the TDI dimer can be prepared quantitatively (Eq.2.28) ").
• the term "reactivity" employed in the present invention corresponds to the reaction rate of an NCO group with an OH group and the “reactivity difference” is the ratio of the reaction rates between the first group NCO and the second NCO group that react with a polyol.
• V2 k2 [NC0 2 ] [OH]
• V 1 / V 2 k 1 / k 2 .
• the difference in reactivity is greater than 8.
• the monomers of diisocyanates may be symmetrical molecules having two NCO groups of the same reactivity. When one of these NCO groups reacts, a substitution effect occurs which generally decreases the reactivity of the second NCO group.
• the diisocyanate monomers can be aliphatic, aromatic or cycloaliphatic. Preferably, the diisocyanate monomers are aromatic. More particularly, the diisocyanate monomers may be selected from the group consisting of toluene-2,4-diisocyanate (2,4 TDI), 1,4-phenylene diisocyanate (PPDI) and mixtures thereof.
• the polyols used in the process for preparing the prepolymers have a functionality 2 and have a molar mass ranging from 150 to 3000 g / mol, preferably ranging from 250 to 3000 g / mol or from 250 to 2000 g / mol.
• the functionality of the polyol refers to the number of hydroxyl groups per molecule. Such polyols are well known to those skilled in the art.
• the polyols may be selected from the group consisting of polyesters, polyethers, polycarbonates, polyolefins and mixtures thereof.
• the polyols may be selected from the group comprising polymers of 1-2 propylene glycol, 1-3 propylene glycol, ethylene glycol, butylene glycol, polycaprolactones, polytetramethylene glycols, polyolefins of polybutadiene type and hydrogenated polybutadiene, polyols derived from fatty acids and vegetable oils, such as oils derived from rapeseed, castor bean, soybean, and mixtures thereof.
• the diisocyanate and polyol monomers are selected from the following combinations:
• 1,4-phenylene diisocyanate and / or toluene-2,4-diisocyanate and polyolefins of plant origin 1,4-phenylene diisocyanate and / or toluene-2,4-diisocyanate and polyolefins of plant origin.
• the diisocyanate monomers and the polyols are in such a quantity that the ratio "number of NCO functions" / "number of OH functions” varies from 1.4 to 2, preferably from 1.45 to 1.65.
• the reaction between the diisocyanate monomers and the polyols according to step a) of the process of the present invention is typically carried out in the absence of catalyst and / or under vacuum. Step a) is carried out at a temperature ranging from 20 to 70 ° C, or even from 20 ° C to 60 ° C.
• the viscosity of the product of the reaction between the diisocyanate monomers and the polyols is controlled by the temperature, the NCO / OH ratio and the molar masses of the polyols. Those skilled in the art will be able to adapt these parameters so that the viscosity of the product obtained in step a) does not exceed 6000 mPa.s at the chosen temperature.
• Stabilization of the product resulting from step a) is carried out at a temperature of from 50 ° C to 110 ° C, preferably from 65 ° C to 100 ° C. Stabilization is preferably carried out under vacuum.
• steps a) and b) (combined) are carried out with stirring for at least 15 hours.
• the isocyanate-terminated polyurethane prepolymers obtained by the process of the present invention can be used to prepare polyurethanes or polyurethanes urea. They can also be used to prepare TPU granules.
• the polyurethanes or polyurethanes urea can be prepared by low pressure or high pressure casting or by means of a liquid injection machine.
• the TPU granules can be prepared by means of an extruder, in particular an extruder with head cut under water and then injection in press.
• the present invention also relates to a process for preparing a polyurethane, polyurethane urea or TPU granules comprising the following steps:
• step iv) reacting the prepolymer obtained in step iv) with polyols and / or polyamines of average molar mass ranging from 50 to 4000 g / mol, and of average functionality equal to or greater than 2;
• polyurethane, polyurethane urea or TPU granules are generally referred to as "chain extenders".
• the chain extenders may be aliphatic or aromatic.
• chain extenders include diols, such as, for example, ethylene glycol, 1,4-butanediol, 1,3-propanediol, hydroquinone bis (2-hydroxyethyl) ether, isosorbide and its isomers or also polyethers, polycaprolactones, polyesters, polycarbonates, polyolefins and polyols derived from fatty acids or vegetable oils as described above and mixtures thereof.
• diols such as, for example, ethylene glycol, 1,4-butanediol, 1,3-propanediol, hydroquinone bis (2-hydroxyethyl) ether, isosorbide and its isomers or also polyethers, polycaprolactones, polyesters, polycarbonates, polyolefins and polyols derived from fatty acids or vegetable oils as described above and mixtures thereof.
• chain extenders include diamines, such as, for example, 6-methyl-2,4-bis (methylthio) phenylene-1,3-diamine, 3,5-diethyltoluene-2,4-diamine, 4 4-Methylene bis (3-chloro-2,6-diethylaniline) and mixtures thereof.
• crosslinking agents Polyols or amines of average functionality greater than 2 are generally referred to as "crosslinking agents".
• crosslinking agent examples include glycerol, sorbitol, trimethylolpropane and castor oil.
• the polyols and / or polyamines useful in step v) of the process have an average molar mass ranging from 50 to 4000 g / mol, preferably ranging from 50 to 500 g / mol and even more preferentially ranging from 50 to 250 g / mol. mol.
• Monoalcohols and / or monoamines acting as a chain limiter may also be added to the polyols and / or polyamines of step v).
• chain restrictors include 1- (2-aminoethyl) -2-imidazolidinone or UDETA (Reverlink®FA from Arkema) and 2-morpholinoethylamine.
• Polyurethanes obtained by the process described above are devoid of isolated rigid segments.
• isolated rigid segments makes it possible to use monofunctional chain limiters which are capable of creating supramolecular bonds.
• the prepolymer is obtained by reaction between 1,4-phenylene diisocyanate and a polycaprolactone, and the chain extender is hydroquinone bis (2-hydroxyethyl) ether or 1,4-butanediol.
• the prepolymer is obtained by reaction between 1,4-phenylene diisocyanate and a polyether, and the chain extender is 1,4-butanediol.
• the components required in step iv) and v) can be introduced into an extruder, such as a twin-screw extruder, to prepare thermoplastic polyurethane (TPU) granules.
• TPU thermoplastic polyurethane
• the present invention also relates to a method for preparing thermoplastic polyurethane granules comprising mixing an isocyanate-terminated polyurethane prepolymer obtained according to the process described above with a functional chain extender 2 in an extruder coupled to a granulator under water.
• polyurethane elastomers and the TPUs obtained by the process of the present invention have properties at least equivalent to, if not superior to, polyurethanes prepared from isocyanate-terminated polyurethane prepolymer whose preparation comprises a distillation step.
• polyurethanes have excellent mechanical and chemical properties:
• TDI 100 and PPDI are as supplied by VENCOREX, France and DKSH, France, respectively.
• the polyols used are provided by:
• the TERATHANE 250 and the TERATHANE 650 are loaded into a tank.
• the mixture is placed at 100 ° C with vigorous stirring (195 rpm) under vacuum.
• the mixture is then stabilized for 17 hours under vacuum at 41 ° C with stirring at 70 rpm.
• the liquid TDI is introduced from the top into the reactor vessel at 27 +/- 3 ° C.
• the homogeneous mixture of polyols at 41 ° C ⁇ 1 is pumped from below under stirring at 70 rpm. When all the polyol mixture is pumped, stirring is increased to 235 rpm.
• the whole is then evacuated. During the exothermic phase, the set temperature of the tank is controlled to follow the temperature of the mixture without exceeding 60 - 0 / + 5 ° C and then the product is stabilized at 65 -0 / + 2 ° C. The whole is then stirred for at least 15 hours under vacuum at 215 rpm at 65 ° C. The product obtained is then stabilized 2H to
• the liquid TDI is introduced from the top into the reactor vessel at 27 +/- 3 ° C.
• the polyol at 55 ° C ⁇ 1 is pumped from below under stirring at 70 rpm. When all the polyol mixture is pumped, stirring is increased to 235 rpm. The whole is evacuated. During the exothermic phase, the set temperature of the tank is controlled to follow the temperature of the mixture without exceeding 60 -0 / + 5 ° C and the product is then stabilized at 65 - 0 / + 2 ° C. The whole is stirred at 215 rpm under vacuum for at least 15 hours. The product is then stabilized 2H at 80 ° C and degassed.
• PRIPOL 2033 and then RADIA 7282 are charged to a tank at 90 ° C-100 ° C.
• the mixture is mounted at 100 ° C with stirring at 195 rpm under vacuum.
• the mixture is stabilized for 12 hours to maintain the polyols at 53 ⁇ 1 ° C.
• the liquid TDI is introduced from the top into the reactor vessel at 27 +/- 3 ° C.
• the homogeneous mixture of polyols at 53 ⁇ 1 ° C. is pumped from below under stirring at 70 rpm. When all the polyol mixture is pumped, stirring is increased to 235 rpm. The whole is evacuated. During the exothermic phase, the set temperature of the tank is controlled to follow the temperature of the mixture without exceeding 60 -0 / + 5 ° C and then the product is stabilized at 65 -0 / + 2 ° C. The whole is stirred at 215 rpm under vacuum for at least 15 hours. The product is then stabilized 2H at 80 ° C and degassed.
• the flaky PPDI is introduced from the top into the reactor vessel at 45 +/- 1 ° C.
• the homogeneous polyol mixture at 45 ⁇ 1 ° C is pumped from above with stirring at 70 rpm. When all the polyol mixture is pumped and all the PPDI wet, stirring is increased to 230 rpm. The whole is evacuated. After the exothermic phase, the product is stabilized at -0 / + 2 ° C. The whole is stirred at 195 rpm under vacuum for at least 15 hours. The product is then stabilized 2H at 80 ° C, and mounted at 100 ° C under vacuum to degas it.
• CAPA 2101 A and then CAPA 2201 A are charged to a tank at 90 ° C-100 ° C.
• the mixture is mounted at 100 ° C with stirring at 195 rpm under vacuum.
• the mixture is stabilized for 12 hours to maintain the polyols at 46 ⁇ 1 ° C.
• the flake PPDI is introduced from the top into the reactor vessel at 46 +/- 1 ° C.
• the homogeneous mixture of polyols at 46 ⁇ 1 ° C is pumped from above with stirring at 70 rpm.
• stirring is increased to 150 rpm and the whole is evacuated.
• the product is stabilized at -0 / + 2 ° C.
• the whole is stirred at 215 rev / min under vacuum during the at least 15 hours.
• the product is then stabilized 2H at 80 ° C, and mounted at 100 ° C under vacuum to degas it.
• Polyurethanes are prepared by methods well known to those skilled in the art.
• the chain extenders used are provided by:
• the prepolymer at 80 ° C and the chain extender at 40 ° C are mixed.
• the cooking time and temperature are as indicated in the table above.
• the prepolymer at 85 ° C and the elongators at 95 ° C are mixed.
• the cooking time and temperature are as indicated in the table above.
• the prepolymer at 80-85 ° C and the extender at 40 ° C are mixed.
• the prepolymer at 95-100 ° C and the extenders at 95-100 ° C are mixed.
• the cooking time and temperature are as indicated in the table above.
• the prepolymer at 85-90 ° C and the extender at room temperature are mixed.
• the cooking time and temperature are as indicated in the table above.
• the prepolymer at 90 ° C-130 ° C and the chain extender at 130 ° C are mixed in a bis-screw extruder comprising several heating zones at temperatures between 200 ° C and 280 ° C.
• the TPU granules are obtained by granulation under water with knives.
• the granules are dried 2H at 80-110 ° C.

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• 2013
  • 2013-12-05 FR FR1362130A patent/FR3014441B1/fr not_active Expired - Fee Related
• 2014
  • 2014-12-05 CN CN201480071822.7A patent/CN106133019A/zh active Pending
  • 2014-12-05 US US15/101,681 patent/US20160304658A1/en not_active Abandoned
  • 2014-12-05 WO PCT/EP2014/076790 patent/WO2015082712A1/fr not_active Ceased
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