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
  • C08G18/70—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
  • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
  • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
  • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
  • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
  • C07D498/04—Ortho-condensed systems
• • 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
  • C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
  • C08G18/3825—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing amide groups
  • C08G18/3827—Bicyclic amide acetals and derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
  • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
  • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
  • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
  • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes

Definitions

• the invention relates to a process for preparing bicyclic amide acetals from N-acyl dialkanol amines and/or O-acyl dialkanol amines.
• the bicyclic amide acetals can be used in coating compositions and crosslinked by hydrolyzing the amide acetal groups, and subsequently reacting the hydroxyl groups or amine groups that are formed with crosslinking agents.
• 4,652,655 describes a process for preparation of bicyclic amide acetals by the reaction of organic nitriles with dialkanol amines wherein the reaction temperature is maintained below about 140°C and the bicyclic amide acetal is removed from the reaction mixtures by extraction in a hydrocarbon solvent.
• European Patent application EP 171 811 describes a process for preparing bicyclic amide acetals by reacting diethanolamine and an alkyl nitrile in the presence of an alkali metal or an alkaline earth metal catalyst in a temperature range of 80°C to 120°C. Ammonia is formed as a by-product in this reaction and needs to be removed, e.g., by purging with an inert gas.
• bicyclic orthoester amides (bicyclic amide acetals) which are prepared by heating N-acyldialkanolamine-bis-alkyl carbonates in the presence of a catalyst, such as, sodium hydroxide followed by distillation of the reaction mixture.
• the invention relates to a new process for preparing bicyclic amide acetals of the following formula I in a direct dehydration of a reactant mixture comprising N-acyl dialkanol amines and/or O-acyl dialkanol amines
• n and m are independently 2 or 3; p is 1 ,2 or 3;
• R1 and R2 can be the same or different and are each independently hydrogen, a linear or branched alkyl, cycloalkyl or aryl group with 1-20 C atoms;
• R represents hydrogen, a branched or linear alkyl, cycloalkyl, aryl or an alkenyl group with 1-20 C-atoms, each may have one or more substituents.
• n is 2, and R is an alkyl, aryl or cycloalkyl group up to 20 C atoms.
• the reactant mixture comprising N-acyl dialkanol amines and/or O-acyl dialkanol amines used in this invention to prepare the bicyclic amide acetals can be provided by following one of the following different strategies: A) The reactant mixture comprising N-acyl dialkanol amines and/or O- acyl dialkanol amines is formed by reacting at least one carboxylic acid and/or carboxylic acid ester and/or carboxylic acid anhydride and at least one dialkanol amine, optionally in the presence of a catalyst.
• N-acyl dialkanol amines are commercially available or can be prepared using methods known in the art (see for example J. of the American Oil Chemists' Society (1962), 39, 213-15). Certain N-acyl dialkanol amines used as reactants can be prepared by reacting carboxylic amides and at least two equivalents of an epoxide, optionally in the presence of a catalyst. Compounds such as N-acyl alkanol amines and/or oxazolines are potential intermediates in this process and are within the scope of this invention.
• bicyclic amide acetals can be prepared in a direct dehydration reaction of a mixture comprising N-acyl dialkanol amines and/or O-acyl dialkanol amines to form the bicyclic amide acetals and water as by-product.
• the use of a catalyst in this transformation is optional.
• the process for preparing the bicyclic amide acetals of this invention can include any of the strategies A and/or B followed by a dehydration reaction to form the desired bicyclic amide acetals. These reactions can be separated into different process steps or carried out in one process step.
• the bicyclic amide acetals of formula I are prepared according to the invention by reaction of carboxylic acids and/or carboxylic acid esters and/or carboxylic acid anhydrides with dialkanol amines.
• carboxylic acids which may be used are saturated or unsaturated carboxylic acids with at least one acid group, preferably one or two acid groups, and with 4 to 54 carbon atoms.
• Suitable monocarboxylic acids are formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, pivalic acid, valeric acid, caproic acid, lauric acid, stearic acid, isononanoic acid, oleic acid, acrylic acid, methacrylic acid, crotonic acid and benzoic acid.
• di- or tricarboxylic acids examples include maleic acid, phthalic acid, isophthalic acid, trimellitic acid, dodecanedicarboxylic acid, norbonane dicarboxylic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexane-1 ,2- and - 1 ,4-dicarboxylic acid, sebacic acid, and adipic acid.
• the carboxylic acid esters of the carboxylic acids mentioned above can be used. Examples are carboxylic acid esters or carboxylic acid half esters of the carboxylic acids mentioned above with linear or branched alcohols with 1-20 C-atoms in the molecule.
• methyl, ethyl, isopropyl, n-butyl, isobutyl alcohol esters are used.
• carboxylic acid anhydrides of the carboxylic acids mentioned above can be used; these anhydrides can be based on monocarboxylic acids or dicarboxylic acids, which may form intramolecular anhydrides. Examples are acetic acid anhydride, caproic acid anhydride, succinic anhydride, and lauric acid anhydride.
• the dialkanol amines useful in the process of this invention include substituted and unsubstituted dialkanol amines having the general formula
• R1 , R2, n and m have the meaning as defined above.
• m and n are 2 and R1 and R2 can be the same or different and are each independently represented by hydrogen and a linear or branched alkyl group with 1-10 carbon atoms.
• Most preferred dialkanol amines are diethanol amine, di-n-propanol amine, and diisopropanol amine. These dialkanol amines are commercially available or can be prepared in an additional reaction step. Dialkanol amines with n and m equal to 2 can also be prepared in a reaction of an alkanol amine with an oxirane.
• oxiranes useful in this invention can be substituted with linear or branched alkyl, cycloalkyl or aryl groups; oxiranes based on glycidyl ethers are also useful compounds.
• Typical oxiranes include ethyleneoxide, propyleneoxide, butyleneoxide, phenyl glycidyl ether, and butylglycidyl ether.
• Typical alkanol amines are ethanolamine, 2- amino-propanol, and 1-amino-2-propanol.
• the process of this invention is based on the reaction of the carboxylic acids and/or carboxylic acid esters and/or carboxylic acid anhydrides with the dialkanol amine to form a reaction mixture which contains N-acyl dialkanol amine and O-acyl dialkanol amine and a by-product derived from the used carboxylic acid derivative (water, alcohol).
• This by-product is removed from the reaction mixture using methods known in the art, such as, the use of a water separation funnel.
• This mixture is further reacted to effect cyclization to form the bicyclic amide acetal of the invention along with water as by-product.
• a carboxylic acid may react with dialkanol amine to form a bicyclic amide acetal.
• the process of the present invention can be carried out, for example, by charging a suitable vessel, such as, a reactor, with the carboxylic acids and/or carboxylic acid esters and/or carboxylic acid anhydrides, the dialkanol amine and optionally, a solvent, to form the reaction mixture.
• the reaction mixture is agitated, for example, by stirring or shaking.
• the present bicyclic amide acetal derivatives can be individually isolated from the reaction mixture, using known conventional methods, such as, chromatography or fractional distillation or crystallization; the preferred method is distillation.
• the process of this invention can be carried out with or without a solvent.
• the solvent if used, can be liquid at the reaction temperature and pressure and inert towards the substrates and products of the process.
• suitable solvents include hydrocarbons, such as, benzene, xylene, decaline or combinations thereof; or combinations of two or more thereof.
• the charged reagents can themselves serve as the solvent.
• the pressure range is about 13,000 to 150,000 Pa, preferably 27,000 to 110,000 Pa.
• the subsequent dehydration step is run at a pressure of about 13 to 101 ,325 Pa, preferably 133 to 1333 Pa.
• the processing temperatures may be from 80 to 250°C and preferably from 140-230°C.
• the process may be carried out in batch, sequential batch (i.e., a series of batch reactors) or in continuous mode in any of the equipment customarily employed for continuous processes.
• the bicyclic amide acetals can be prepared directly according to the invention by dehydration of N-acyl dialkanol amines, i.e., starting with an intermediate product contained in the reaction mixture of the reaction described above.
• the N-acyl dialkanol amines can be prepared as known in the art (see for example J. of the American Oil Chemists' Society (1962), 39, 213-15).
• N-acyl dialkanol amines are commercially available (for example, Naxamide®-CD140 from Rutgers Organics) and/or can be prepared through alternative routes, for example in the reaction of carboxylic acid chlorides with the dialkanol amine.
• These N-acyl dialkanol amines can be dehydrated using the process of this invention to bicyclic amide acetals.
• the process of the present invention can be carried out, for example, by charging a suitable vessel, such as a reactor, with the N-acyl dialkanol amines and optionally a solvent, to form the reaction mixture.
• the reaction mixture is agitated, for example, by stirring or shaking.
• the pressure range for the reaction is about 13 Pa to 101325 Pa, and preferably, 133 to 1333 Pa.
• the processing temperatures may be from 80 to 250°C, preferably, 140 to 230°C.
• the process may be carried out in batch, sequential batch (i.e., a series of batch reactors) or in continuous mode in any of the equipment customarily employed for continuous processes.
• the bicyclic amide acetals can also be prepared by reacting carboxylic amides with oxiranes to form reaction mixtures containing N-acyl alkanol amines and/or N-acyl dialkanol amines and which may contain oxazolines. These reaction mixtures can be dehydrated to generate the bicyclic amide acetals of this invention.
• Typical carboxylic amides are lauramide, acetamide, caproic amide, valeric amide.
• Typical oxiranes useful in this invention can be substituted with linear or branched alkyl, cycloalkyl or aryl groups; oxiranes based on glycidyl ethers are also substrates.
• Typical oxiranes include, ethyleneoxide, propyleneoxide, butyleneoxide, phenyl glycidyl ether, and butylglycidyl ether.
• the process can be carried out, for example, by charging a suitable vessel, such as a reactor, with the carboxylic amide and the oxirane in a ratio of 1 to 10, with a preferred ratio of 1 to 2.5 and optionally, a solvent to form the reaction mixture.
• a suitable vessel such as a reactor
• the reaction mixture is agitated, for example, by stirring or shaking.
• the pressure range for the reaction is 6666 to 202650 Pa, preferably 40000 to 101325 Pa.
• the processing temperatures may be from 80 to 250°C, preferably 140 to 230°C.
• the process may be carried out in batch, sequential batch (i.e. a series of batch reactors) or in continuous mode in any of the equipment customarily employed for continuous processes.
• water scavengers are optional in the process of the invention and can aid in the removal of the by-product water.
• the presence of a water scavenger can improve the process regarding speed of reaction, conversion and reaction temperature.
• Suitable water scavengers are, for example, orthoesters, orthoformates, orthoketals, orthocarbonates, alkoxysilanes and inorganic compounds e.g. Na 2 SO 4 , MgO, CaO, P2O5, molecular sieves.
• common methods applied to separate water from such reaction mixtures can also be used (for example, a water separation device such as a Dean Stark Trap).
• the process of the present invention may be carried out in the presence of a catalyst.
• Suitable catalysts include, metal oxides, hydroxides, carbonates, silicates, phosphates, aluminates, tertiary amines, pyridine and pyridine derivatives and combinations thereof.
• Suitable catalysts are also, for example, salts of metals, wherein the metal is selected from the group consisting of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, and cadmium.
• the bicyclic amide acetals prepared according to the present invention can be used as latent hydroxyl compounds in coating compositions comprising compounds reactive with hydroxyl groups or amine groups, such as, poiyisocyanates, epoxy-functional compounds, acetals, anhydrides and alkoxysilanes.
• the bicyclic amide acetals are stable under anhydrous conditions and hydrolyze in the presence of moisture, e.g., in the presence of atmospheric moisture, under formation of free hydroxyl groups or amine groups.
• the hydrolysis occurs without a catalyst, but the speed of hydrolysis can be increased by the addition of catalysts.
• Suitable catalysts are acids, e.g., acetic acid and sulfonic acids, such as p-toluenesulfonic acid.
• Coating compositions based on bicyclic amide acetals dry and cure rapidly without the potential problems created by VOC (Volatile Organic Content) emissions.
• the coating compositions based on bicyclic amide acetals may comprise further hydroxy-functional binders, which are able to react with the crosslinkers mentioned above.
• Such coating compositions can be very useful, for example, in automotive coating, particularly, in the refinish area. They can be used as clear coats or pigmented coating compositions, e.g., solid-color top coats or primers.
• a "clear coating composition” for automotive use is a composition that forms a transparent finish upon curing and has a DO I (distinctness of image) of more than 70 and a 20° gloss of more than 70.
• DO I distinctness of image
• These clear coatings provide a glossy in depth appearance to the finish on the automobile or truck and therefore, are required to have good gloss and distinctness of image. Also, the clear finish provides resistance to weathering, in particular to U.V. degradation and photo- oxidation.
• Coating compositions based on bicyclic amide acetals prepared according to the present invention show a better initial color and a better color stability than coating compositions based on bicyclic amide acetals prepared according to known methods.
• Coating compositions based on bicyclic amide acetals prepared according to the present invention also have a long potlife and a high initial hardness. Coating compositions can be formulated with a low VOC of, e.g., 1.6 lbs/gal (192g/l).
• the batch temperature was then raised to 195°C. During the pressure reduction and heat-up, unreacted DIPA (60 g) came overhead. A total of 199.4 g of amide acetal derived from lauric acid was then collected while the temperature was raised from 195 to 222°C at a pressure of 320-466 Pa. This represents a 66.7 % conversion of the lauric acid.
• GC Gas chromatography
• DIPA diisopropanol amine
• amide acetal content in the liquid samples.
• Liquid samples from the reactor and from the overhead receiver were analyzed for the presence of DIPA and amide acetal product using an internal standard GC method.
• the GC was calibrated using pure DIPA and amide acetal. Samples were removed, weighed, diluted with known amount of internal standard in methylene chloride, and then injected into the GC.
• the batch temperature was slowly raised to 220°C while the batch pressure was increased to 19,800 Pa. An additional 13 ml of a mixture of water and DIPA came overhead. The temperature was then allowed to drop to 182°C while the pressure was dropped to 280 Pa. During the pressure reduction, 31.2 g of DIPA came overhead. As the pressure was dropped to 227 Pa and the temperature increased to 221 °C, a total of 93.4 g of the amide acetal of lauric acid was collected.
• Example 5 Preparation of 7a-butyl-2-hexyl-6-methyl-tetrahydro-2H-oxazolo[2,3-b]oxazole Under atmospheric nitrogen, 30.79g of 1-amino-2-propanol was added drop-wise to a solution of 52.59g of 1 ,2-epoxyoctane (in a ratio of 1 :1 mol) in acetonitrile (100g). The mixture was stirred and eventually solidified followed by the removal of acetonitrile in vacuum.
• the comparative amide acetal has been prepared by reacting dodecane nitrile and diisopropanol amine.
• the comparative amide acetal has been prepared by reacting dodecane nitrile and diisopropanol amine (with Na catalyst).
• Clear coat formulations (CC A and CC B) based on amide acetals have been prepared by mixing the following constituents, whereas CC A is based on amide acetal of example 1 according to the invention and CC B is based on comparative amide acetal (1):
• Byk 358 (acrylic leveling agent from Byk Chemie) 0,2 0,2 Byk 310 (silicon surface additive from Byk Chemie) 0,2 0,2 diisobutylketone 5,05 5,05 acetic acid 0,58 0,58
• Solvesso - hydrocarbon solvent A usual two-component high solid clearcoat (based on hydroxy functional acrylic binder and polyisocyanate activator) has been used as solventborne comparative clear coat (comparative CC; 3800S HS Chromaclear (DuPont) + high solid activator XK205 (DuPont)).
• the clearcoats have been applied over usual solventborne basecoats (Centari 6000 silver metallic basecoat) and cured 30 minutes at 6O°C.
• the clear coat based on the amide acetal prepared according to the present invention shows the advantage of a very low VOC value (1.6 lbs/gal) compared with a usual high solid clearcoat at a comparable spray viscosity. Furthermore said clearcoat gives an improved potlife of more than 6 hours. The clearcoat is still easy to spray 6 hours after activation and the drying - appearance (gloss, DOI) is still the same like for the composition that is sprayed directly after activation.
• the amide acetals prepared according to the present invention show less color and a better color stability compared with the amide acetal prepared according to the prior art process (via nitrile route). Color and color stability are important issues especially in formulating high-quality clearcoats. Test Methods
• a film is considered to have dried tack-free when the tack tester tips over immediately on removing a 300 g weight allowed to act for 5 seconds on the counter-weighted metal square based fitted with masking tape and aluminum foil.
• “Tape free time” is the time after which the recovery has the rating "good”.
• the recovery is the re-evaluation that is done 30 minutes after the tape is removed. When the tape recovery has a rating good, there is almost no mark left.
• a rating good means also commercially acceptable.

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• 2004
  • 2004-12-02 US US11/002,747 patent/US7439354B2/en not_active Expired - Fee Related
  • 2004-12-08 EP EP04813956A patent/EP1692142A1/en not_active Withdrawn
  • 2004-12-08 JP JP2006544083A patent/JP2007522103A/ja not_active Withdrawn
  • 2004-12-08 AU AU2004298510A patent/AU2004298510A1/en not_active Abandoned
  • 2004-12-08 CA CA002547519A patent/CA2547519A1/en not_active Abandoned
  • 2004-12-08 WO PCT/US2004/041709 patent/WO2005058912A1/en not_active Ceased

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