US20070106048A1 - Synthesis of acylureas and composition comprising acylureas - Google Patents

Synthesis of acylureas and composition comprising acylureas Download PDF

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Publication number
US20070106048A1
US20070106048A1 US10/582,438 US58243804A US2007106048A1 US 20070106048 A1 US20070106048 A1 US 20070106048A1 US 58243804 A US58243804 A US 58243804A US 2007106048 A1 US2007106048 A1 US 2007106048A1
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acid
optionally
composition
moderate
functional groups
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Jean-Marie Bernard
Denis Revelant
Cedric Amouyal
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Rhodia Chimie SAS
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Rhodia Chimie SAS
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Publication of US20070106048A1 publication Critical patent/US20070106048A1/en
Priority to US12/714,873 priority Critical patent/US8158817B2/en
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    • 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
    • C08G18/16—Catalysts
    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
    • C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret groups
    • 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
    • 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
    • C08G18/16—Catalysts
    • C08G18/166—Catalysts not provided for in the groups C08G18/18 - C08G18/26
    • C08G18/168—Organic 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
    • C08G18/28—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
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl 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
    • C08G18/28—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
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen

Definitions

  • compositions comprising acylureas and a process for producing such compositions: an improved process resulting in biuret-based oligomers is also targeted.
  • polyisocyanate compositions are generally formed from derivatives resulting from the oligocondensation of individual di-, tri- or indeed even tetraisocyanate molecule(s).
  • Such a type of molecule is described as “monomers” and is capable of being obtained by phosgenation of a di(primary amine), optionally carrying one, indeed even two, other primary amine functional groups.
  • a molecule comprises a unit composed of a carbon chain carrying at least two nitrogens (originating from the diamine to be phosgenated), which unit will be denoted by “diamino unit” in the continuation of the description.
  • the diamino unit serves here as vestiges or mark of the existence, past or present, of an isocyanate monomer: thus, the diamino unit has the structure >N—R—N ⁇
  • R represents a hydrocarbon radical which is the residue of an isocyanate monomer, after ignoring two isocyanate functional groups.
  • R does not exhibit any of the functional groups created during the oligomerization of an isocyanate functional group, namely the carbamate, urea (including biuret), allophanate or biuret functional groups and those which are mentioned on the occasion of the description of the oligocondensation (including oligomerization).
  • the molecular weight of —R— is at most equal to 200.
  • R can comprise another “amino” group in the case of the trifunctional monomers, such as LTI, NTI and UTI.
  • amino symbols N ⁇ and >N mean that the nitrogen can be inserted into any functional group, such as isocyanate, amine, amide, imide or urea functional group, and in particular the functional groups generated by the oligomerization reactions.
  • diamino units are found in virtually all of the oligocondensations and in the vast majority of the conversions of the isocyanate functional groups. This observation makes it possible to refer to the number of diamino units in order to indicate in particular the state of condensation of the oligocondensates (including oligomers), indeed even of the. polycondensates, and even in the case of heterocondensates (in which cases it is possible to have several types of diamino units).
  • the isocyanate monomers can be:
  • the molecular weight of a monomer does not exceed 300 and is at least equal to 100.
  • linear aliphatic monomers it is desirable for linear aliphatic monomers to be used at least partially for the implementation of the present invention.
  • lysine derivatives and in particular LDI (Lysine DiIsocyanate, resulting from ester of lysine) or LTI (Lysine TriIsocyanate, resulting from the ester of lysine with ethanolamine), NTI (Nonyl TriIsocyanate OCN—(CH 2 ) 4 —CH(CH 2 —NCO)—(CH 2 ) 3 —NCO) or UTI (Undecyl TriIsocyanate OCN—(CH 2 ) 5 —CH(—NCO)—(CH 2 ) 5 —NCO).
  • condensations involve the isocyanate functional groups.
  • “monomers” are polyfunctional with regard to isocyanate, these condensations can take place on two or more isocyanate functional groups of the same molecule. It follows that these reactions can result in oligomers which are smaller or bigger in size depending on the degree of conversion of the isocyanates.
  • the main units, functional groups or rings liable to be formed on the occasion of the trimerization may be restated:
  • oligomeric polyisocyanate compositions Mention may in particular be made, among the most widely used oligomeric polyisocyanate compositions, of the oligomer mixture exhibiting a biuret unit and familiarly denoted by “biuret”.
  • This biuret is currently produced by the action of water on isocyanate monomers in the presence of a very small amount of acid.
  • the degree of conversion of the monomer is of the order of 45%.
  • the viscosity of the product resulting from the synthesis after distillation of the monomer is of the order of 9000 mPa ⁇ s.
  • compositions exhibiting a high functionality Furthermore, the market requires compositions exhibiting a high functionality.
  • one of the aims of the present invention is to provide a process which reduces or eliminates the formation of insoluble ureides.
  • Another aim of the present invention is to provide isocyanate compositions in which the isocyanate comprises a biuret group.
  • Another aim of the present invention is to provide a process which makes it possible to reduce the viscosity of the final composition for the same degree of conversion of the monomer(s), the measurement of the viscosity being carried out under “standard” conditions, after removal of the residual monomer(s) (the compositions targeted exhibit, by weight, at most 1%, advantageously at most 0.5%, preferably at most 0.2%, more preferably at most 0.1%).
  • the measurement of the viscosity see Standard NFT 30-029 (October 1980).
  • Another aim of the present invention is to provide compositions comprising a biuret group which exhibit a reduced viscosity.
  • Another aim of the present invention is to provide polyisocyanate compositions of high functionality which can be used alone or as a mixture with others.
  • a “starting” composition comprising derivatives comprising at least two isocyanate functional groups is subjected to the action of at least two acids, one at least of which is a strong acid (pKa ⁇ 3) and another at least of which is an acid of moderate strength (3 ⁇ pKa ⁇ 6), at a temperature at least equal to 50° C.
  • Highacids such as triflic acid or bistrifluoromethylsulfonimide, are not preferred.
  • the strong or weak acids can be introduced (completely or partially) in the form of a precursor capable of releasing the acid by thermolysis (such as, for example, acid iodoniums according to one of the above definitions) or by hydrolysis (such as symmetrical or unsymmetrical acid anhydrides, including acid halides when the halide anions do not cause trouble).
  • thermolysis such as, for example, acid iodoniums according to one of the above definitions
  • hydrolysis such as symmetrical or unsymmetrical acid anhydrides, including acid halides when the halide anions do not cause trouble.
  • the temperature is a temperature at least equal to 50° C. and even at least equal to 100° C.
  • temperatures equal to at least 110° C. and even 130° C. are preferred.
  • the reaction is generally carried out at a temperature of at most 200° C., advantageously of at most 180° C., preferably of at most 160° C.
  • R 2 and R 1 which are identical or different, represent the residue of an isocyanate, generally of a monomer, after ignoring an isocyanate functional group (of course, that which has reacted), and R′ is the residue of a carboxylic acid, after ignoring a carboxyl functional group (of course, that which has reacted).
  • At least one of the isocyanate derivatives prefferably be a monomer (that is to say, for it to comprise only one diamino unit as defined above). It is also desirable, not taking into account possible solvents, for said starting mixture to comprise, by weight, at least one third and even half, advantageously 2 ⁇ 3, preferably 3 ⁇ 4, of monomer(s).
  • the starting mixture is composed solely of monomer (apart from the impurities and solvent). In the latter case, the monomer derivative or the monomer derivatives represent at least 90%, advantageously 95%, by weight of said starting composition.
  • the monomer derivative or, when there is more than one of them, at least one of the monomer derivatives is at least partially aliphatic, that is to say that at least one, advantageously two, preferably all, of the amine functional groups of the diamino unit is/are carried by a carbon of sp 3 hybridization.
  • the synthesis of the acylureas can be carried out in the same reaction medium as the synthesis of biuret.
  • said polyisocyanate composition comprises derivatives comprising a biuret functional group.
  • said starting composition is additionally brought into contact with an amine or an amine-generating reactant, advantageously water in the form of a fluid (that is to say, in the vapor or liquid form).
  • said starting composition is additionally brought into contact with an amine or an amine-generating reactant, the molar ratio of the amine (generated or introduced) to the sum of the monomers, expressed in moles, being chosen within the closed range (that is to say, comprising the limits) extending from 1 ⁇ 2 to 1/50, advantageously within that extending from 1 ⁇ 3 to 1/25.
  • acylureas can be carried out before the, after the or jointly with the preparation of the derivatives comprising a biuret functional group.
  • said starting composition is brought into contact with water in the presence of said moderate and strong acid(s).
  • the strong acid is advantageously chosen from organic acids and in particular aliphatic or aromatic sulfonic, phosphonic, including carboxylic-phosphonic, ester phosphoric or perhaloalkanoic acids.
  • carboxylic-phosphonic acid is an acid which combines together, in the same molecule, a strong acid and a moderate acid according to the present invention.
  • said strong acid exhibits, in addition to its strong acidity, another acidity, generally a moderate acidity.
  • the acid hydrogens it is preferable for the acid hydrogens to be separated by 3 atoms (such as, for example, in an unesterified phosphonic acid) or 4 atoms (such as, for example, in oxalic acid, but the latter is not preferred as there is a risk of it being unstable at the operating temperature).
  • the moderate acids are chosen from aliphatic or aromatic carboxylic acids.
  • these acids can comprise ether or thioether functional groups.
  • they can comprise “alkene oxide” and in particular “ethylene oxide” fragments.
  • the compounds carrying at least one carboxylic acid functional group are aliphatic, cycloaliphatic, aromatic or heterocyclic compounds. They comprise at least one carboxylic acid functional group and at most 6, preferably at most 2.
  • the carbon number is between 2 and 20, preferably between 2 and 12.
  • They can comprise heteroatoms or functional groups, such as esters or carbonates or ethers, and the like.
  • Unsaturated acids can also be used, in particular if a twofold crosslinking operation is envisaged on the composition. Acids such as acrylic, methacrylic or fumaric acids can be used. However, it is then advisable to add radical scavengers which inhibit the vinyl polymerization. Such scavengers are well known to a person skilled in the art.
  • aliphatic or aromatic monoacids of at most 15, advantageously of at most 12, preferably of at most 10, carbon atoms. These monoacids advantageously have at least two carbons, advantageously at least 3, preferably at least 4. It is also preferable for these acids to exhibit at least one secondary carbon.
  • the moderate acids can be di- or triacids. In this case, it is generally advisable to choose such a polyacid so that the formation of the cyclic imides is not promoted.
  • the molecule can be chosen so that the distance between two carboxyl functional groups is sufficient and/or so that the geometry of the molecule is such that the formation of the cyclic imides is not favored.
  • the number of carbons (or of chain atoms, if the chain is not purely of carbon) between two carboxyl functional groups is at- least equal to 5 or else the geometry is not favorable thereto, as in the case of terephthalic acid or meta- or para-phenylenediacetic acid; or else both these conditions are met.
  • the diacylurea (simple) corresponds to the formula:
  • R 1 , R 2 , R 3 and R 4 which are identical or different, represent the residue of an isocyanate, generally of a monomer (cf. those which are mentioned in the present description and the preferences which are established), after ignoring an isocyanate functional group (of course, that which has reacted), and R′′ is the residue of a dicarboxylic acid, after ignoring two carboxyl functional groups (of course, those which have reacted).
  • the moderate acids can be replaced, completely or partially, by carboxamides carrying at least one hydrogen on the nitrogen in order to produce acylureas.
  • these acylureas react only once with a dimer, which renders them less advantageous than those resulting from the carboxylic acids.
  • the dividing line between strong acids and moderate acids makes it possible for the acidities to be close (indeed even for there to be a slight overlap) but the system operates best when at least one of the moderate acids exhibits an acidity which is significantly lower than that of at least one of the strong acids.
  • the pKa of the strong acid it is desirable for the pKa of the strong acid to differ from that of the moderate acid by at least one unit, advantageously 2.
  • the rule is set out as below. It is desirable for the pKa of at least one of the strong acids to differ by at least one pK unit, advantageously 2 pK units, from that of at least one of the moderate acids, advantageously from all those of the moderate acids.
  • the content of strong acid(s) is chosen so that the molar ratio of the sum of the strong acid functional groups, expressed as equivalents, to the sum of the monomers, expressed as moles, is at least equal to 0.1%, advantageously to 0.5% , preferably to 1%.
  • the content of strong acid(s) is chosen so that the molar ratio of the sum of the strong acid functional groups, expressed as equivalents, to the sum of the monomers, expressed as moles, is at most equal to 2%, advantageously to 1%.
  • the content of moderate acid(s) is chosen so that the molar ratio of the sum (numerator) of the moderate acid functional groups, expressed as equivalents, to the sum (denominator) of the monomers, expressed as moles, is at least equal to 2%, advantageously to 5%, preferably to 1%.
  • the amount of the moderate acids involved in the reaction is a content when all the acids and monomer(s) are introduced from the beginning.
  • the amount of moderate acid(s) is chosen so that the molar ratio of the sum of the moderate acid functional groups, expressed as equivalents, to the sum of the monomers, expressed as moles, is at most equal to 10%, advantageously to 5%. In the case of the viscosity not being favored, it is possible to rise to 20%.
  • said strong acid or the mixture of strong acids it is generally introduced before the heating of the reaction mixture is begun.
  • a dilute form advantageously a form diluted with at most 50 times, preferably with 1 to 20 times, its weight of diluent.
  • said strong acid is diluted in water; in other words, the diluent is water or an aqueous mixture.
  • said strong acid is diluted in a C 1 to C 14 alcohol, advantageously a C 3 to C 10 alcohol.
  • said strong acid is diluted in said moderate acid or a mixture of said moderate acids.
  • the synthetic process comprises the series of following operations:
  • Another aim of the present invention is to provide polyisocyanate compositions having a reduced viscosity and/or a high functionality.
  • compositions can be obtained either by the process which cosynthesizes the acylureas and the nonacylated oligomers (such as biuret) and which has just been set out, or by mixing acylureas prepared in isolation.
  • the second route is more expensive but more effective for lowering viscosity.
  • acylureas according to the present invention make it possible to modify the properties of the polyisocyanate compositions conventionally marketed (cf. the introduction).
  • acylureas it is preferable for the acylureas to be as light as possible, that is to say for them to be advantageously composed of at most 5 diamino units.
  • the monoacylurea (corresponding to one monocarboxylic acid) comprises only two diamino units,
  • the bisacylurea corresponds to three monomers (and two monocarboxylic acids) and thus exhibits three diamino units
  • diacylureas resulting from the diacids comprise 4 diamino units
  • acylurea of a true trimer or of a true biuret exhibits 4 diamino units.
  • acylureas of at most 5 diamino units and even of at most 3 diamino units.
  • such a composition comprises at least 1% (weight), preferably at least 1.5%, more preferably at least 2%, of monoacylurea.
  • compositions according to the present invention are also targeted at increasing the functionality.
  • they can comprise, by weight, at least 2% of diacylurea corresponding to an at least bifunctional acid, such as adipic acid, advantageously at least 5%, preferably at least 10%.
  • compositions according to the present invention can comprise both monoacylureas and diacylureas and meet the constraints of the two preceding paragraphs.
  • the present invention is particularly well suited to compositions based on a biuret functional group.
  • compositions comprise, by weight, at least 10%, advantageously 15%, preferably 25%, of true biuret (that is to say, comprising only a single biuret functional group and three diamino units).
  • the present invention is especially advantageous for highly condensed compositions comprising a relatively high content of heavy oligocondensates. It is consequently desirable for such a composition to comprise, by weight, at most 4 ⁇ 5, advantageously 2 ⁇ 3, preferably at most half, of true biuret (three biuret units).
  • the ratio by weight of the sum of the monoacylureas (numerator) to the sum of the oligomers of at least six diamino units is at least equal to 2%, advantageously to 5%, preferably to 7%.
  • the ratio by weight of the sum of the monoacylureas (numerator) to the sum of the oligomers of at least six diamino units is at most equal to 50%, advantageously to 40%, preferably to 20%.
  • the degree of conversion of the isocyanate monomers depends on the NCO/biuretization agent and NCO/carboxyl and/or amide functional groups ratios.
  • the NCO/nucleophiles (compounds comprising mobile hydrogen) ratio which determines the degree of conversion of the isocyanate functional groups or the degree of conversion of the isocyanate monomers, is set according to the polyisocyanate compositions to be obtained.
  • the degree of conversion of the monomers is between 5 and 90%, preferably between 10 and 60%.
  • the compounds which are subject matters of the invention are characterized by a lower viscosity, which is advantageous in reducing the volatile organic compounds discharged to the atmosphere.
  • the viscosity of the compounds which are subject matters of the invention depends very obviously on the isocyanate monomer involved, cycloaliphatic compounds giving generally higher viscosities than aliphatic isocyanate derivatives (called “linear” in the present description) with a short chain (4 to 10 chain members).
  • compositions of the invention obtained by the process are characterized by:
  • the compounds which are subject matters of the invention can be used for the synthesis of functional derivatives or the preparation of compositions for coatings applied to organic or inorganic surfaces (metal, plastics, wood, cloth, leather, concrete, and the like) for decorative, functional and/or protective purposes.
  • the compounds of the present invention can also be incorporated in the manufacture of materials based on polyurethanes (foams), on elastomers, on fibers or on rubbers.
  • the fields of application are therefore highly diverse (paints, varnishes, adhesives, tires, and the like) and relate equally well to interior applications as to exterior applications or applications exposed to particular media (materials immersed in water, and the like).
  • the compounds of the invention exhibit low coloring indices of less than 200 hazen.
  • the isocyanate functional groups carried by the compounds of the invention of the final mixture can be definitively or temporarily and completely or partially functionalized by various nucleophilic components which can be chosen from:
  • the coreactants of the compounds of the invention can be:
  • Compounds such as various fillers, catalysts, rheology additives or pigments can be added to the formulations to introduce the desired properties.
  • Quantitative determination of the isocyanate functional groups The standardized method for the quantitative determination of isocyanate functional groups by the “dibutylamine” method is used. Back titration with a standard HCl solution of the N,N-dibutylamine not consumed by the reaction with the isocyanate functional groups of the mixture to be quantitatively determined. The difference between the N,N-dibutylamine which has reacted and the amount introduced makes it possible to measure the content of isocyanate functional groups in the mixture to be quantitatively determined.
  • Gel permeation chromatography is used as method for determining the number-average and weight-average molecular weights.
  • Polystyrene standards of known molecular weight are used to calibrate the gel permeation columns.
  • the elution solvent used is a good solvent for the standard polymers and for the polymers to be analyzed. It is chosen taking into account the restrictions introduced by the method for detecting the polymers (refractometry or analysis by ultraviolet absorption or analysis by infrared). This solvent is chosen from ethers, such as tetrahydrofuran, chlorinated derivatives, such as dichloromethane, and the like.
  • the elution volume of the polymers to be analyzed is compared with the elution volumes of the standard polymers and the molecular weight is thus deduced therefrom.
  • the constituent eluted oligomers of the mixture to be analyzed can also be recovered separately for analysis and characterization by various structural analytical techniques, such as 1 H NMR, 13 C NMR, infrared, and the like.
  • the first method is based on Standard NFT 30-029 of October 1980: operating method for a rotary viscometer for measuring the apparent dynamic viscosity of varnishes, paints and associated preparations.
  • a rheometer with the Rheovisco LV8 brand name is used to do this.
  • the operating temperature is 25° C.
  • the choice of the equipment and the operating conditions selected depend on the viscosity range. Thus, for a viscosity range of between 0 and 5000 mPa ⁇ s, use is made of the L2 cylinder with a speed of 6 revolutions/minute, for a viscosity range of between 0 and 20 000 mPa ⁇ s, use is made of the L3 cylinder with a speed of 6 revolutions/minute and, for a viscosity range of between 0 and 1000 mPa ⁇ s, use is made of the L1 cylinder with a speed of 6 revolutions/minute.
  • a second method used to measure the viscosity is the “ball drop” method.
  • the value measured is very close to the value given by the preceding method.
  • the polyisocyanate of unknown viscosity is introduced into a test tube with a diameter of 20 mm and a height of 20 cm.
  • the tube has two marks separated by 10 cm. It is conditioned at the measuring temperature (25° C.) by immersing in a thermostatically controlled and regulated bath.
  • a ball is placed on the top of the liquid and the time which it takes to cover the distance between the marks is measured.
  • the value of the viscosity is obtained by application of the following formula and is expressed in mPa ⁇ s at 25° C.
  • Viscosity at 25° C. 1.11 ⁇ t ⁇ 100 with t the ball drop time in seconds for a distance of 10 cm between the marks.
  • Polyisocyanate Composition Comprising Biuret and Acylurea Units
  • the equipment used comprises a 2 l reactor rendered inert with nitrogen and equipped with a mechanical stirrer, a reflux condenser, gas discharge valves and a dip pipe connected to a second vertical tubular reactor with a length of 40 cm and a diameter of 1 cm preheated to approximately 200° C. and swept with nitrogen, this tubular reactor being itself connected to a device for feeding liquid water.
  • hexamethylene diisocyanate 1000 g of hexamethylene diisocyanate (HDI) are introduced into the 2 liter reactor.
  • the starting NCO content is 1.19.
  • the temperature of the reaction medium is 21° C.
  • 2.58 g of a 50% by weight solution of dibutyl phosphate (DBP) in 2-ethylhexanol and 0.89 g of propionic acid are added.
  • the respective DBP/HDI and propionic acid/HDI molar ratios are 1 ⁇ 10 ⁇ 3 and 2 ⁇ 10 ⁇ 3 .
  • the reaction medium is stirred at 250 revolutions per minute.
  • the temperature of the reaction medium is brought to 140° C.
  • 19 g of water i.e. an HDI/H 2 O molar ratio of 5.65, are introduced into the device for feeding water.
  • the 19 g of water are injected over 1 hour, the water changing from the liquid state to the vapor state in the tubular reactor swept with nitrogen (120 l/hour). The reaction begins immediately and evolution of carbon dioxide is observed. The temperature of the reactor is maintained at 140° C.
  • the NCO content of the reaction medium after injecting water for 20 minutes is 1.138. After 35 minutes, it is 1.060.
  • the NCO content is 0.961 mol per 100 g.
  • the reaction mixture is left stirring for a further 2 hours, at the end of which time the NCO content of the reaction medium stabilizes at 0.901 mol per 100 g.
  • the degree of conversion of HDI is of the order of 48.7%.
  • reaction medium is then filtered through a No. 1 sintered glass funnel to give a level of insolubles of 20.5 mg for a weight of reaction medium recovered of 961 g.
  • 860 g of the reaction medium are subsequently purified by 2 successive distillations of HDI monomer on a thin film device under a vacuum of 0.2 mbar and at 160° C. with a throughput of 400 g/hour for the first pass and 200 g/hour for the second pass.
  • 310 g of a polyisocyanate composition comprising biuret and acylurea units are recovered, the NCO content of which composition is 22.5% and the viscosity of which composition at 25° C. is 4850 mPa ⁇ s.
  • the level of HDI monomer is less than 0.5%.
  • Polyisocyanate Composition Comprising Biuret and Acylurea Units
  • the amount of water is 25 g.
  • the respective molar ratios are: pTSA/HDI: 3 ⁇ 10 ⁇ 3 ; propionic acid/HDI: 5.2 ⁇ 10 ⁇ 3 ; HDI/H 2 O: 6.4.
  • the content of the reaction medium after addition of the propionic acid and of the pTSA catalyst solution is 1.146.
  • the NCO content of the reaction medium after injecting water for 45 minutes is 0.950.
  • the NCO content is 0.871 mol per 100 g.
  • the reaction mixture is left stirring for a further 2 hours, at the end of which time the NCO content of the reaction medium stabilizes at 0.834 mol per 100 g.
  • the degree of conversion of HDI is of the order of 55%.
  • reaction medium is then filtered through a No. 1 sintered glass funnel to give a level of insolubles of 38 mg for a weight of reaction medium recovered of 1430 g.
  • the polyisocyanate composition comprising biuret and acylurea units obtained after distillation exhibits an NCO content of 21.8%.
  • the level of HDI monomer is less than 0.5%.
  • the level of acylurea of HDI and of propionic acid is 2.3%.
  • the content of HDI dimer is 4%.
  • the content of true biuret is 40%.

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8158817B2 (en) 2003-12-24 2012-04-17 Perstorp France Synthesis of acylureas and composition comprising acylureas
US10590227B2 (en) * 2014-09-17 2020-03-17 Construction Research & Technology Gmbh Curable organic polymer comprising at least one acylurea unit, its preparation and use
CN112250835A (zh) * 2020-09-14 2021-01-22 万华化学（宁波）有限公司 一种制备无色多异氰酸酯组合物的方法

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FR2750308A1 (fr) * 1996-04-11 1998-01-02 Exal Diffusion Verre a degustation pour alcools tels que les eaux de vie, les spiritueux et les liqueurs
DE10110437A1 (de) * 2001-03-05 2002-09-19 Bayer Ag Verfahren zur Herstellung von Polyisocyanaten durch Umsetzung von Carbonsäuren mit Isocyanaten, die nach diesem Verfahren hergestellten Produkte und deren Verwendung in Polyurethankunststoffen
JP5476962B2 (ja) * 2009-12-09 2014-04-23 日本ポリウレタン工業株式会社 アシルウレア変性ポリイソシアネート組成物の製造方法
JP2011136912A (ja) * 2009-12-25 2011-07-14 Nippon Polyurethane Ind Co Ltd アシルウレア変性ポリイソシアネート組成物の製造方法
WO2021142570A1 (zh) * 2020-01-13 2021-07-22 万华化学集团股份有限公司 一种储存稳定的缩二脲多异氰酸酯的制备方法
CN114539508B (zh) * 2020-11-25 2023-05-30 万华化学集团股份有限公司 一种改善水分散性的低粘多异氰酸酯组合物

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US3383400A (en) * 1964-01-11 1968-05-14 Bayer Ag Acylated urea polyisocyanates and process for the preparation thereof
US3517039A (en) * 1965-05-24 1970-06-23 Bayer Ag Process for preparing acylated urea diisocyanates
US4077989A (en) * 1974-07-30 1978-03-07 Bayer Aktiengesellschaft Process for the production of modified polyisocyanates
US4124569A (en) * 1976-09-15 1978-11-07 Bayer Aktiengesellschaft Process for the preparation of polyisocyanates containing urethane and biuret groups
US4517353A (en) * 1982-12-22 1985-05-14 Bayer Aktiengesellschaft Process for preparation of hydantoin esters through a masked polyisocyanate-carbodiimide route
US4625052A (en) * 1984-01-31 1986-11-25 Bayer Aktiengesellschaft Process for the production of polyisocyanates which have a biuret structure
US20020123596A1 (en) * 2001-03-05 2002-09-05 Christoph Gurtler Polyisocyanates containing acylurea groups, a process for their production and their use

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DE2436741A1 (de) * 1974-07-30 1976-02-12 Bayer Ag Verfahren zur herstellung modifizierter polyisocyanate
DE10007820A1 (de) * 2000-02-21 2001-08-23 Bayer Ag Acylharnstoffgruppen enthaltende Polyisocyanatgemische
FR2864534B1 (fr) 2003-12-24 2006-02-17 Rhodia Chimie Sa Synthese d'acylurees et composition comportant des acylurees

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US3383400A (en) * 1964-01-11 1968-05-14 Bayer Ag Acylated urea polyisocyanates and process for the preparation thereof
US3517039A (en) * 1965-05-24 1970-06-23 Bayer Ag Process for preparing acylated urea diisocyanates
US4077989A (en) * 1974-07-30 1978-03-07 Bayer Aktiengesellschaft Process for the production of modified polyisocyanates
US4124569A (en) * 1976-09-15 1978-11-07 Bayer Aktiengesellschaft Process for the preparation of polyisocyanates containing urethane and biuret groups
US4517353A (en) * 1982-12-22 1985-05-14 Bayer Aktiengesellschaft Process for preparation of hydantoin esters through a masked polyisocyanate-carbodiimide route
US4625052A (en) * 1984-01-31 1986-11-25 Bayer Aktiengesellschaft Process for the production of polyisocyanates which have a biuret structure
US20020123596A1 (en) * 2001-03-05 2002-09-05 Christoph Gurtler Polyisocyanates containing acylurea groups, a process for their production and their use

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8158817B2 (en) 2003-12-24 2012-04-17 Perstorp France Synthesis of acylureas and composition comprising acylureas
US10590227B2 (en) * 2014-09-17 2020-03-17 Construction Research & Technology Gmbh Curable organic polymer comprising at least one acylurea unit, its preparation and use
CN112250835A (zh) * 2020-09-14 2021-01-22 万华化学（宁波）有限公司 一种制备无色多异氰酸酯组合物的方法

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US20100216966A1 (en) 2010-08-26
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ATE500286T1 (de) 2011-03-15
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KR20060108730A (ko) 2006-10-18
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