Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
  • C07C271/06—Esters of carbamic acids
  • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
  • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
  • C07C271/16—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
  • C07C271/62—Compounds containing any of the groups, X being a hetero atom, Y being any atom, e.g. N-acylcarbamates
  • C07C271/64—Y being a hydrogen or a carbon atom, e.g. benzoylcarbamates

Definitions

• Nonlimiting examples of compounds having groups (I) include carbamate ethyl (meth)acrylate, carbamate propyl (meth)acrylate, l-carbamate-2- ethylhexane, dicarbamate,diethyloctane, and the dicarbamate of dimerized fatty acid.
• (meth)acrylate refers to both the acrylate and methacrylate compounds.
• the compound having group (I) has a polymerizable group or polymerizable groups, for example a compound prepared using carbamate ethyl (meth)acrylate or carbamate propyl (meth)acrylate having structures
• An oligomer or polymer comprising a functional group of formula (I) can comprise one or more types of repeating structural units. Exemplary repeating structural units include urethanes, amides, esters, aliphatic, aromatic ethers, and combinations comprising one or more of the foregoing.
• Nonlimiting examples of oligomers and polymers having functional groups (I) include vinyl polymers such as acrylic polymers, polyurethanes, polyesters, polyethers, epoxies, polyamides, polycarbonates, and so on, as well as graft and block polymers having combinations of these.
• One type of oligomer is a so-called "star" polymer prepared using a hyperbranched core.
• the oligomer or polymer comprising a functional group of formula (I) can be prepared by adducting an oligomer or polymer having primary carbamate groups (II) to convert those groups to groups (III).
• Carbamate-functional ethylenically unsaturated monomers, cyclic carbonate functional ethylenically unsaturated monomers, and/or isocyanate functional ethylenically unsaturated monomers may also be used, most preferably in combination with other ethylenically unsaturated monomers.
• Cyclic carbonate ethylenically unsaturated monomers are well-known in the art and include (2-oxo-l,3-dioxolan-4- yl)methyl methacrylate.
• Representative examples of other ethylenically unsaturated polymerizable monomers include, without limitation, such compounds as fumaric, maleic, and itaconic anhydrides, monoesters, and diesters with alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, and tert-butanol.
• polymerizable vinyl monomers include, without limitation, such compounds as vinyl acetate, vinyl propionate, vinyl ethers such as vinyl ethyl ether, vinyl and vinylidene halides, and vinyl ethyl ketone.
• aromatic or heterocylic aliphatic vinyl compounds include, without limitation, such compounds as styrene, alpha-methyl styrene, vinyl toluene, tert-butyl styrene, and 2- vinyl pyrrolidone.
• Representative examples include acrylic and methacrylic acid amides and aminoalkyl amides, acrylonitrile, and methacrylonitriles.
• Another method of synthesis reacts an alpha,beta-unsaturated acid ester with a hydroxy carbamate ester to form the carbamyloxy carboxylate.
• Yet another technique involves formation of a hydroxyalkyl carbamate by reacting a primary or secondary amine or diamine with a cyclic carbonate such as ethylene carbonate. The hydroxyl group on the hydroxyalkyl carbamate is then esterif ⁇ ed by reaction with acrylic or methacrylic acid to form the monomer.
• Other methods of preparing carbamate-modif ⁇ ed acrylic monomers are described in the art, and can be utilized as well. The acrylic monomer can then be polymerized along with other ethylenically-unsaturated monomers, if desired, by techniques well-known in the art.
• An alternative route for preparing a carbamate-functional acrylic polymer is to react an already- formed polymer such as an acrylic polymer with another component to form a carbamate-functional group appended to the polymer backbone, as described in U.S. Pat. No. 4,758,632, the disclosure of which is incorporated herein by reference.
• One technique for preparing acrylic polymers useful as the second component involves thermally decomposing urea (to give off ammonia and HNCO) in the presence of a hydroxy- functional acrylic polymer to form a carbamate-functional acrylic polymer.
• the first compound can suitably be an aliphatic, a cycloaliphatic, or an aromatic diol, triol, or tetrol, a sugar alcohol such as sorbitol and mannitol, dipentaerythritol, an . alpha. -alkylglucoside such as .alpha.-methylglucoside, or an alkoxylate polymer having a molecular weight of at most about 8,000 that is produced by a reaction between an alkylene oxide or a derivative thereof and one or more hydroxyl groups from any of the alcohols mentioned above. Mixtures of these can also be used as the first compound.
• Diols suitable as the first compound include straight diols with 2-18 carbon atoms.
• the epoxide group of the epoxide- containing compound reacts faster with the carboxyl group than with any primary or secondary hydroxyl groups that may be present on the first intermediate. Therefore, a relatively clean chain extension is achieved to form a second intermediate that contains secondary hydroxyl groups resulting from ring opening of the epoxide, as well as any primary or secondary hydroxyl groups that remained unreacted in the formation of the first intermediate.
• Reaction conditions are selected to allow the epoxide group to open in either direction, resulting in a mixture of products, following reaction conditions known in the art.
• the epoxy containing compound is reacted in a molar ratio of about 1 : 1 with respect to carboxyl groups on the first intermediate.
• carboxyl groups are desired in the final product (for example for salting with amines to provide a water dispersible coating)
• an excess of carboxyl functional first intermediate may be used.
• a carbamate group may be added to the second intermediate by reacting the second intermediate with phosgene and then ammonia to form a compound having primary carbamate groups, or by reaction of the second intermediate with phosgene and then a primary amine to form a compound having secondary carbamate groups.
• the second intermediate may be reacted with one or more ureas to form a compound with secondary carbamate groups (i.e., N-alkyl carbamates). This reaction is accomplished by heating a mixture of the second intermediate and urea.
• Another technique is the reaction of the second intermediate with a monoisocyanate, for example methylisocyanate, to form a compound with secondary carbamate groups.
• bonds include carbon-hydrogen single bonds or carbon-carbon, carbon-oxygen, carbon-nitrogen, carbon-phosphorus or carbon- silicon single bonds or double bonds.
• carbon-carbon double bonds are particularly advantageous.
• double bonds If more than one double bond is used, the double bonds may be conjugated but in some embodiments it is of advantage if the double bonds are present in isolation, in particular each being present terminally, in the group in question.
• Suitable groups include (meth)acrylate, ethacrylate, crotonate, cinnamate, vinyl ether, vinyl ester, dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl groups; dicyclopentadienyl ether, norbornenyl ether, isoprenyl ether, isopropenyl ether, allyl ether or butenyl ether groups; or dicyclopentadienyl ester, norbornenyl ester, isoprenyl ester, isopropenyl ester, allyl ester or butenyl ester groups, but especially acrylate groups.
• Curable compositions particularly coating compositions, include a material comprising functional groups of formula (I) with either the same material or a second material comprising functional groups reactive under curing conditions with the functional groups of formula (I).
• the same material comprises both the functional groups of formula (I) and those groups reactive under cure conditions with the groups of formula (I)
• the material is said to be self-crosslinking.
• the functional groups reactive under curing conditions with the functional groups of formula (I) are active hydrogen groups.
• the material having an active hydrogen groups functions as a cross linking agent.
• the curable material comprises functional groups of formula (III) having a hydroxyl group on a carbon atom beta to the carbon atom to which the group of formula (III) is attached.
• the crosslinkable materials having such active hydrogen groups may be compounds, oligomers, or polymers. In certain embodiments, at least one of (a) the material having groups (I) and (b) the crosslinkable materials having such active hydrogen groups has least three of such functional groups and the other one (a) and (b) has at least two of such functional groups, on average, per molecule.
• Nonlimiting examples of materials that having active hydrogen groups include vinyl polymers such as acrylic polymers, polyesters, polyurethanes, polyethers, and nonpolymeric materials such as esters, functional alkanes, dimmer fatty acids and derivatives of dimer fatty acid, and the like having any of the active hydrogen- containing functional groups already mentioned.
• the coating compositions may further include other customary materials, including pigments, fillers, solvents, catalysts, stabilizers, slip aids, rheology control agents, dispersing agents, adhesion promoters, UV absorbers, hindered amine light stabilizers, and so on.
• the pigment or filler may be any organic or inorganic compounds or colored materials, metallic or other inorganic flake materials such as pearlescent mica flake pigments or metallic flake pigments such as aluminum flake, and other materials of kind that the art normally includes in such coatings.
• aliphatic bismuth carboxylates such as bismuth ethylhexanoate, bismuth subsalicylate (having an empirical formula CyHsO
• Color-plus-clear topcoats are usually applied wet-on-wet.
• the compositions are applied in coats separated by a flash, as described above, with a flash also between the last coat of the color composition and the first coat the clear.
• the two coating layers are then cured simultaneously.
• the cured basecoat layer is 0.5 to 1.5 mils thick
• the cured clear coat layer is 1 to 3 mils, more preferably 1.6 to 2.2 mils, thick.
• the primer layer and the topcoat can be applied "wet-on- wet.”
• the primer composition can be applied, then the applied layer flashed; then the topcoat can be applied and flashed; then the primer and the topcoat can be cured at the same time.
• the topcoat can include a basecoat layer and a clearcoat layer applied wet-on-wet.
• the primer layer can also be applied to an uncured electrocoat coating layer, and all layers cured together.
• Example One Di-functional alkoxycarbonylamino material.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Paints Or Removers (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
• Polyurethanes Or Polyureas (AREA)

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• 2008
  • 2008-12-29 US US12/345,237 patent/US8008416B2/en not_active Expired - Fee Related
  • 2008-12-29 EP EP08869968A patent/EP2227451A2/en not_active Withdrawn
  • 2008-12-29 CN CN200880113319.8A patent/CN101835744B/zh not_active Expired - Fee Related
  • 2008-12-29 KR KR1020107017137A patent/KR101586763B1/ko not_active Expired - Fee Related
  • 2008-12-29 JP JP2010541513A patent/JP5677851B2/ja not_active Expired - Fee Related
  • 2008-12-29 WO PCT/US2008/088460 patent/WO2009088834A2/en not_active Ceased

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