US20170058074A1 - Post-modified polycarbodiimides - Google Patents

Post-modified polycarbodiimides Download PDF

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US20170058074A1
US20170058074A1 US15/120,279 US201515120279A US2017058074A1 US 20170058074 A1 US20170058074 A1 US 20170058074A1 US 201515120279 A US201515120279 A US 201515120279A US 2017058074 A1 US2017058074 A1 US 2017058074A1
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isocyanate
acid
alkyl
set forth
polycarbodiimide
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Rajesh Kumar
Nikolay Lebedinski
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BASF SE
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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
    • C08G18/09—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture
    • C08G18/095—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture oligomerisation to carbodiimide or uretone-imine 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
    • C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
    • C08G18/025—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing carbodiimide 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
    • C08G18/088—Removal of water or carbon dioxide from the reaction mixture or reaction components
    • C08G18/0885—Removal of water or carbon dioxide from the reaction mixture or reaction components using additives, e.g. absorbing agents
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/71—Monoisocyanates or monoisothiocyanates
    • 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
    • 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
    • C08G18/80—Masked polyisocyanates

Definitions

  • the present technology is generally related to modification of polycarbodiimides. Specifically, the technology is related to storage stable polycarbodiimides and their preparation in the absence of a solvent.
  • a process for preparing a capped polycarbodiimide, the process including combining in a reaction vessel a diisocyanate, a moisture scavenger, a monoisocyanate, and a catalyst to form a reaction mixture; and heating the reaction mixture to a temperature and for a time sufficient to form a capped polycarbodiimide, wherein the capped polycarbodiimide has 0.1 wt % or less of free isocyanate groups; and the combining and heating are conducted in the absence of a solvent.
  • the capped polycarbodiimides are liquid materials that exhibit Newtonian Rheology.
  • the capped polycarbodiimide has 0.075 wt % or less free isocyanate groups.
  • the temperature may be from about 60° C. to about 120° C.
  • the time may be from about 4 hours to about 48 hours.
  • the diisocyanate may be a compound of formula ONC—R 1 —CNO, wherein R 1 is a linking group.
  • the monoisocyanate is a compound of formula ONC—R 2 , wherein R 2 is an alkyl, cycloalkyl, aromatic, heterocyclic, or heteroaryl.
  • the capped polycarbodiimide may be a polycarbodiimide of formula: R 2 —N ⁇ C ⁇ N—[R 1 —N ⁇ C ⁇ N] n —R 2 , wherein R 1 is a linking group, R 2 is a alkyl, cycloalkyl, aromatic, heterocyclic, or heteroaryl, and n is the polymer repeating unit.
  • R 1 is a linking group
  • R 2 is a alkyl, cycloalkyl, aromatic, heterocyclic, or heteroaryl
  • n is the polymer repeating unit.
  • n designates a repeating unit of the polymer.
  • n may be from about 1 to about 30.
  • n may be from about 1 to about 15.
  • the process may also include contacting the capped polycarbodiimide with a monomeric acid.
  • the monomeric acid may be a compound represented as R 3 C(O)OH, wherein R 3 is a polymerizable group.
  • the monomeric acid may be a fatty acid.
  • a polymer in another aspect, is provided, the polymer being the reaction product of any of the above capped polycarbodiimides and a monomeric acid.
  • the monomeric acid may be a compound represented as R 3 C(O)OH, wherein R 3 is a polymerizable group, or the monomeric acid may be a fatty acid.
  • the polymer may be a chemical-cure (i.e. radically cured) and/or photocurable polymer.
  • the monomeric acid may be a group of formula
  • R 4 may be C 1 -C 18 alkyl
  • E is absent or is S
  • X may be C 1 -C 18 alkyl, aryl, nitrile, or halide
  • R 5 may be a R 5 is alkyl, aryl, aralkyl, —OC(O)alkyl, —C(O)Oalkyl, —OC(O)aryl, —C(O)Oaryl, heteroaryl, heterarylalkyl, heterocyclyl, or heterocyclylalkyl group, optionally substituted
  • n is a repeat unit.
  • n′ is from 1 to 30.
  • FIG. 1 is a Fourier transform infrared spectrum of a polycarbodiimide in the top spectrum, partially modified in the middle spectrum, and a fully modified polycarbodiimide in the bottom spectrum, according to Examples 9 and 10.
  • substituted refers to an alkyl, alkenyl, alkynyl, aryl, or ether group, as defined below (e.g., an alkyl group) in which one or more bonds to a hydrogen atom contained therein are replaced by a bond to non-hydrogen or non-carbon atoms.
  • Substituted groups also include groups in which one or more bonds to a carbon(s) or hydrogen(s) atom are replaced by one or more bonds, including double or triple bonds, to a heteroatom.
  • a substituted group will be substituted with one or more substituents, unless otherwise specified.
  • a substituted group is substituted with 1, 2, 3, 4, 5, or 6 substituents.
  • substituent groups include: halogens (i.e., F, Cl, Br, and I); hydroxyls; alkoxy, alkenoxy, alkynoxy, aryloxy, aralkyloxy, heterocyclyloxy, and heterocyclylalkoxy groups; carbonyls (oxo); carboxyls; esters; urethanes; oximes; hydroxylamines; alkoxyamines; aralkoxyamines; thiols; sulfides; sulfoxides; sulfones; sulfonyls; sulfonamides; amines; N-oxides; hydrazines; hydrazides; hydrazones; azides; amides; ureas; amidines; guanidines; enamines; imides; isocyanates; isothiocyanates; cyanates; thiocyanates; imines; nitro groups; nitriles (i.
  • alkyl groups include straight chain and branched alkyl groups having from 1 to about 20 carbon atoms, and typically from 1 to 12 carbons or, in some embodiments, from 1 to 8 carbon atoms.
  • alkyl groups include cycloalkyl groups as defined below. Alkyl groups may be substituted or unsubstituted. Examples of straight chain alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups.
  • branched alkyl groups include, but are not limited to, isopropyl, sec-butyl, t-butyl, neopentyl, and isopentyl groups.
  • Representative substituted alkyl groups may be substituted one or more times with, for example, amino, thio, hydroxy, cyano, alkoxy, and/or halo groups such as F, Cl, Br, and I groups.
  • haloalkyl is an alkyl group having one or more halo groups. In some embodiments, haloalkyl refers to a per-haloalkyl group.
  • Alkylene groups are divalent alkyl groups.
  • Cycloalkyl groups are cyclic alkyl groups such as, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups.
  • the cycloalkyl group has 3 to 8 ring members, whereas in other embodiments the number of ring carbon atoms range from 3 to 5, 6, or 7. Cycloalkyl groups may be substituted or unsubstituted.
  • Cycloalkyl groups further include polycyclic cycloalkyl groups such as, but not limited to, norbornyl, adamantyl, bornyl, camphenyl, isocamphenyl, and carenyl groups, and fused rings such as, but not limited to, decalinyl, and the like. Cycloalkyl groups also include rings that are substituted with straight or branched chain alkyl groups as defined above.
  • Representative substituted cycloalkyl groups may be mono-substituted or substituted more than once, such as, but not limited to: 2,2-; 2,3-; 2,4-; 2,5-; or 2,6-disubstituted cyclohexyl groups or mono-, di-, or tri-substituted norbornyl or cycloheptyl groups, which may be substituted with, for example, alkyl, alkoxy, amino, thio, hydroxy, cyano, and/or halo groups.
  • Alkenyl groups are straight chain, branched or cyclic alkyl groups having 2 to about 28 carbon atoms, and further including at least one double bond. In some embodiments alkenyl groups have from 1 to 12 carbons, or, typically, from 1 to 8 carbon atoms. Alkenyl groups may be substituted or unsubstituted. Alkenyl groups include, for instance, vinyl, propenyl, 2-butenyl, 3-butenyl, isobutenyl, cyclohexenyl, cyclopentenyl, cyclohexadienyl, butadienyl, pentadienyl, and hexadienyl groups among others.
  • Alkenyl groups may be substituted similarly to alkyl groups.
  • Divalent alkenyl groups i.e., alkenyl groups with two points of attachment, include, but are not limited to, CH—CH ⁇ CH 2 , C ⁇ CH 2 , or C ⁇ CHCH 3 .
  • aryl or “aromatic,” groups are cyclic aromatic hydrocarbons that do not contain heteroatoms.
  • Aryl groups include monocyclic, bicyclic and polycyclic ring systems.
  • aryl groups include, but are not limited to, phenyl, azulenyl, heptalenyl, biphenylenyl, indacenyl, fluorenyl, phenanthrenyl, triphenylenyl, pyrenyl, naphthacenyl, chrysenyl, biphenyl, anthracenyl, indenyl, indanyl, pentalenyl, and naphthyl groups.
  • aryl groups contain 6 to 14 carbons, and in others from 6 to 12 or even 6 to 10 carbon atoms in the ring portions of the groups.
  • aryl groups includes groups containing fused rings, such as fused aromatic-aliphatic ring systems (e.g., indanyl, tetrahydronaphthyl, and the like).
  • Aryl groups may be substituted or unsubstituted.
  • Heteroaryl groups are aromatic ring compounds containing 5 or more ring members, of which, one or more is a heteroatom such as, but not limited to, N, P, O, and S. Unless expressly indicated otherwise, heteroaryl groups may be substituted or unsubstituted.
  • Heteroaryl groups include, but are not limited to, groups such as pyrrolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, thiophenyl, benzothiophenyl, furanyl, benzofuranyl, indolyl, azaindolyl (pyrrolopyridyl), indazolyl, benzimidazolyl, imidazopyridyl (azabenzimidazolyl), pyrazolopyridyl, triazolopyridyl, benzotriazolyl, benzoxazolyl, benzothiazolyl, benzothiadiazolyl, imidazopyridyl, isoxazolopyridyl, thianaphthalenyl, purinyl, xanthiny
  • Heterocyclyl groups include non-aromatic ring compounds containing 3 or more ring members, of which one or more is a heteroatom such as, but not limited to, N, O, and S.
  • heterocyclyl groups include 3 to 20 ring members, whereas other such groups have 3 to 6, 3 to 10, 3 to 12, or 3 to 15 ring members.
  • Heterocyclyl groups encompass unsaturated, partially saturated and saturated ring systems, such as, for example, imidazolyl, imidazolinyl and imidazolidinyl groups. Unless expressly indicated otherwise, heterocyclyl groups may be substituted or unsubstituted.
  • Heterocyclyl groups include, but are not limited to, aziridinyl, azetidinyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, thiazolidinyl, tetrahydrothiophenyl, tetrahydrofuranyl, dioxolyl, furanyl, thiophenyl, pyrrolyl, pyrrolinyl, imidazolyl, imidazolinyl, pyrazolyl, pyrazolinyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, thiazolinyl, isothiazolyl, thiadiazolyl, oxadiazolyl, piperidyl, piperazinyl, morpholinyl, thiomorpholinyl, tetrahydropyranyl, tetrahydrothiopyranyl,
  • substituted heterocyclyl groups may be mono-substituted or substituted more than once, such as, but not limited to, pyridyl or morpholinyl groups, which are 2-, 3-, 4-, 5-, or 6-substituted, or disubstituted with various substituents such as those listed above.
  • a polycarbodiimide may be post-polymerization modified (i.e. “post-modified” or “post-modification”) by reaction with a monomeric acid.
  • post-modified polycarbodiimides There are two types of post-modified polycarbodiimides described herein.
  • the polycarbodiimides have long pot-lives. For example, the pot-life may be greater than 1 year.
  • pot-life indicates that the composition maintains a molecular weight, flowability, and reactivity over the described time period at room temperature. In the above example of the pot-life of greater than 1 year, this includes, but is not limited to, pot-lives of at least 16 months, 18 months, 2 years, 30 months, 3 years, 42 months, or 4 years.
  • the first type is a photo-curable, or chemically-curable polycarbodiimide.
  • the photo-curable polycarbodiimides are formed by reaction of a polycarbodiimide with a photo-curable monomeric acid, such that the post-modification product retains the photo-curable character of the monomeric acid.
  • Such materials may be used in a wide variety of applications where photo-curing is desirable.
  • the post-modified polycarbodiimides may be used in sealants, elastomers, coatings, or adhesives. Coatings may include inks.
  • Chemically-curable materials are those that may be cured via free radical mechanisms, or catalyzed mechanisms.
  • the second type of post-modified polycarbodiimide is a fatty acid-modified polycarbodiimide.
  • the fatty acid-modified polycarbodiimides are formed by reaction of a polycarbodiimide with a fatty acid, to incorporate the greasy, longer chain fatty acid residues into the polycarbodiimide.
  • the fatty acids may be saturated, monounsaturated, or polyunsaturated.
  • Such fatty acid post-modified polycarbodiimides may be used in a wide variety of applications where radical curing is desirable, such as in alkyd resins.
  • the fatty acid post-modified polycarbodiimides may be used as wood coatings, pigment dispersants, oil field applications.
  • the reactions used to prepare the materials are conducted in the absence of solvent, or other solvent-type monomers.
  • the reactions avoid the use of solvents such as, but not limited to, methylene chloride, chloroform, trichloroethylene, hexachloroethylene, carbon tetrachloride, benzene, toluene, xylene, ethyl acetate, butyl acetate, or the like.
  • the reaction also avoids the use of “solvent” monomers beyond the monomeric acid.
  • Such solvent monomers include, but are not limited to, styrene, ⁇ -methylstyrene, vinyl alcohol, vinyl esters, glycols, glycol esters, amides, and vinyl amides. All of the materials in the reaction pot are either the polycarbodiimide (or mixture of any two or more polycarbodiimides) or monomeric acid (or mixture of any two or more monomeric acids), along with any processing aid such as, but not limited to, moisture scavengers and/or catalysts. Catalyst residue from the catalyst used to prepare the polycarbodiimide may be present.
  • the moisture scavenger may be triphenylphosphite.
  • the catalyst may be phospholene oxide, or any of the catalysts described in U.S. Pat. No. 6,489,503, incorporated herein by reference.
  • the post-modified polycarbodiimides are also liquid materials at room temperature that exhibit Newtonian behavior. That is, the liquids have a constant viscosity at different shear rates.
  • the post-modified polycarbodiimides may have, for example, a number average molecular weight range from about 400 to about 6000 for an acrylic modified polycarbodiimide, from about 600 to about 13000 for an oleic acid modified polycarbodiimide, from about 400 to about 1200 for a hybrid polycarbodiimide (as defined below). The molecular weight will vary depending on the specific monomeric acid used to modify the capped polycarbodiimide.
  • polycarbodiimides are made by a process such that they lack residual isocyanate (NCO) groups, or at least have a very high percentage of —N ⁇ C ⁇ N— linkages in comparison to residual NCO groups.
  • NCO isocyanate
  • any remaining NCO groups are so few as to be undetectable by infrared spectroscopy methods.
  • polycarbodiimides may have 0.3 wt % or fewer free NCO groups. In some embodiments, there are 0.1 wt % or fewer free NCO groups. In other embodiments, there are 0.075 wt % or fewer free NCO groups. In yet further embodiments, there are no free NCO groups.
  • a post-modified polycarbodiimide is formed in a process generally described in Scheme 1.
  • a polycarbodiimide is reacted with a monomeric acid (R 3 C(O)OH), which may be a polymerizable acid, to form a post-modified polycarbodiimide.
  • the polycarbodiimide is a capped polycarbodiimide at the “*” positions in the illustrated compounds.
  • a “capped polycarbodiimide” is a polycarbodiimide that is free of isocyanate groups.
  • the caps on the polycarbodiimide may be aliphatic or aromatic caps derived from monoisocyanates.
  • groups such as, but not limited to, butyl, (trialkoxysilyl)propyl, 3-isopropenyl- ⁇ , ⁇ -dimethylbenzyl, phenyl, naphthyl, p-toluene sulfonyl, and tolyl may be used.
  • the capped groups remain in the post-modified material as an O- or N-acyl urea group.
  • the polycarbodiimide may be prepared according to the reaction described in Scheme 2.
  • the capped polycarbodiimide is prepared in process that includes combining in a reaction vessel a diisocyanate, a moisture scavenger, a monoisocyanate, and a catalyst to form a reaction mixture. The reaction mixture is then heated to a temperature and for a time sufficient to form the capped polycarbodiimide.
  • the capped polycarbodiimide has 0.25 wt % or less of free isocyanate groups; and the combining and heating steps of the process are conducted in the absence of a solvent.
  • the capped polycarbodiimide has 0.1 wt % or less of free isocyanate groups.
  • the diisocyanate, monoisocyanate, moisture scavenger, and catalyst may be added to a reactor all together or in any order.
  • the diisocyanate, monoisocyanate, and moisture scavenger are added together and heated prior to addition of the catalyst.
  • the temperature during heating may be from about 30° C. to about 200° C., according to some embodiments. In other embodiments, the temperature is from about 60° C. to about 120° C. In yet other embodiments, the temperature is from about 100° C. to about 110° C.
  • the time may be from about 2 hours to 48 hours. In some embodiments, the time is from about 4 hours to 20 hours. In other embodiments, the time is from about 4 hours to 14 hours.
  • R 1 is a linking group, which in the diisocyanate is the group on which the isocyanates are located. Also included in the reaction medium is a monoisocyanate (R 2 NCO) that results in the end groups capping the polycarbodiimide R 1 and R 2 may individually be alkyl, cycloalkyl, aromatic, heterocyclic, or heteroaryl.
  • R 1 and R 2 may individually be a C 1 -C 12 alkyl, C 1 -C 12 cycloalkyl, a C 6 -C 12 aromatic, a C 6 -C 12 heterocyclyl, or a C 6 -C 12 heteroaryl group.
  • R 1 and R 2 may individually be a methylene, ethylene, propylene, isopropylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decalinylene, dodecylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, tolyl, or xylyl.
  • R 1 is an aryl group.
  • R 1 may preferably be phenyl, tolyl, or xylyl.
  • R 2 is an aryl group.
  • R 2 may preferably be phenyl, tolyl, or xylyl.
  • R 2 is methyl, ethyl, propyl isopropyl, butyl, pentyl hexyl, heptyl, octyl, nonyl, decalinyl, dodecyl, tetradecyl, hexadecyl, octadecyl, cyclohexyl, phenyl, tolyl, tolyl isomers, 2,2-diphenyl, 2,2-diphenylethyl, phenylsulfonyl, toluenesulfonyl phenyl isomers, 3-isopropenyl- ⁇ , ⁇ -dimethylbenzyl, 3-(triethoxysilyl)propyl, 4-(chlorosulfonyl)phenyl, chlorosulfonyl, 1-naphthalene, 2-naphthalene, 1-(1-naphthyl)ethyl
  • Illustrative diisocyantes include, but are not limited to, m-phenylene diisocyanate; 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; hexamethylene diisocyanate; 1,4-phenylene diisocyanate; tetramethylene diisocyanate; cyclohexane-1,4-diisocyanate; hexahydrotoluene diisocyanate; methylenediisocyanate; 2,6-diisopropylphenyl isocyanate; m-xylylene diisocyanate; dodecyl isocyanate; 3,3′-dichloro-4,4′-diisocyanato-1,1′-biphenyl; 1,6-diisocyanato-2,2,4-trimethylhexane; 3,3′-dimethoxy-4,4′-biphenylene diisocyanate;
  • the diisocyanate is 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, or a mixture of 2,4- and 2,6-toluene diisocyanate.
  • the diisocyanate includes 100% 2,4-toluene diisocyanate; 80% 2,4-toluene diisocyanate, 20% 2,6-toluene diisocyanate; or 65% 2,4-toluene diisocyanate, 35% 2,6-toluene diisocyanate.
  • Illustrative monoisocyanates, R 2 NCO, that may be used in forming the polycarbodiimide include, but are not limited to, chlorosulfonyl isocyanate; trichloromethyl isocyanate; trichloroacetyl isocyanate; trichloroacetyl isocyanate; chloroacetyl isocyanate; vinyl isocyanate; methyl isocyanatoformate; 2-bromoethyl isocyanate; 2-chloroethyl isocyanate; 2-chloroethyl isocyanate; ethyl isocyanate; isocyanato(methoxy)methane; allyl isocyanate; ethyl isocyanatoformate; 3-chloropropyl isocyanate; isopropyl isocyanate; propyl isocyanate; (trimethylsilyl)isocyanate; isocyanatocyclobutane;
  • R 3 is alkyl, alkenyl, or a group of formula —CH 2 C(X)(CH 3 )(CH 2 CHR 5 ) x SC(S)ER 4 , wherein E is absent or S, R 4 is alkyl or alkenyl, R 5 is alkyl, aryl, aralkyl, —OC(O)alkyl, —C(O)Oalkyl, —OC(O)aryl, —C(O)Oaryl, heteroaryl, heterarylalkyl, heterocyclyl, or heterocyclylalkyl, and x is from 0 to 20.
  • R 3 is an alkyl. In some embodiments, R 3 is an alkenyl. In some embodiments, R 3 is a group of formula —CH 2 C(X)(CH 3 )(CH 2 CHR 5 ) n SC(S)ER 4 . Mixtures of any two or more such monomeric acids may be used as the monomeric acid.
  • the monomeric acid comprises a compound represented as R 3 C(O)OH, wherein R 3 is a C 8 -C 24 alkyl, a C 8 -C 24 alkylene, or a group of formula —CH 2 C(X)(CH 3 )(CH 2 CHR 5 ) n SC(S)SR 4 , wherein E is absent or s, R 4 is a C 1 -C 12 alkyl, a C 2 -C 12 alkenyl, R 5 is phenyl or tolyl, and x is from 0 to 30.
  • the acid may be a monomeric acid, where the carboxyl group of the acid in conjunction with R 3 forms a photo-curable group, or alternatively, the acid is a fatty acid.
  • the polymerizable group, R 3 provides photo-curable properties to the polymer.
  • R 3 may be preserved and is not involved in the reaction to form the post-modified polycarbodiimide.
  • the photo-curable R 3 may react to form higher molecular weight polymers, or cross-links between polymers.
  • R 3 alone, or in conjunction with the carboxyl group of the acid may be a photo-curable group.
  • Illustrative examples of photo-curable groups include, but are not limited to, vinyl groups and allylic groups.
  • the monomeric acid used in the process may be a fatty acid.
  • some fatty acids may be represented as R 3 C(O)OH, where R 3 is a C 8 -C 24 alkyl or a C 8 -C 24 alkylene.
  • fatty acids include, but are not limited to, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolaidic acid, ⁇ -linolenic acid, arachidonic acid, eicosapentaenoic acid, euricic acid, or docosahexaenoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, or cerotic acid. A mixture of any two or more such acids may also be used.
  • the monomeric acid used in the process may be a mixture of a vinyl acid (i.e. where R 3 is an alkylene as described herein) and a fatty acid.
  • the ratio of vinyl acid to fatty acid may range from 0.01:9.99 to 9.90:0.01 by weight.
  • the monomeric acid may be a thiocarbonate acid of formula:
  • thiocarbonate acid may be using in combination with any of the monomeric acids, including vinyl acids and fatty acids, described herein.
  • E is absent or is S
  • R 4 may be C 1 -C 18 alkyl
  • X is alkyl, aryl, nitrile, or halide
  • x is the repeat group associate with the addition of a vinyl monomer
  • R 5 may be an R 5 is alkyl, aryl, aralkyl, —OC(O)alkyl, —C(O)Oalkyl, —OC(O)aryl, —C(O)Oaryl, heteroaryl, heterarylalkyl, heterocyclyl, or heterocyclylalkyl group, or a substituted group.
  • R 5 may be functionalized with an acid or ester groups.
  • the thiocarbonate acid include, but are not limited to, 2-(4-methoxyphenylcarbonothioylthio)-ethanoic acid; 2-(phenylcarbonothioylthio)-propanoic acid; 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid; 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid; 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid; and 3,5-bis(2-dodecylthiocarbonothioylthio-1-oxopropoxy)benzoic acid, a trithiocarbonate acid terminated-polystyrene, -polyacrylate, -polymethacrylate, -polyvinyl
  • R 5 may be derived from a vinylic monomer such as, but not limited to, styrene, ⁇ -methylstyrene, isobutyl acrylate, hydroxyethyl caprolactone acrylate, hexyl acrylate, isodecyl acrylate, lauryl acrylate, behenyl acrylate, allyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, tert.-butylaminoethyl methacrylate, lauryl methacrylate, stearyl methacrylate, behenyl methacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, PEG 200 dimethacrylate, trimethylolpropane trim
  • the post-modified polycarbodiimide of Scheme 1 is provided.
  • Such a polymer may be of the formula:
  • R 1 , R 2 , and R 3 are as defined above.
  • R is an arylene
  • R 2 is a vinyl group
  • R 3 is a C 8 -C 24 alkyl or C 8 -C 24 alkylene.
  • the bracketing indicates the repeat unit of the polymer.
  • the polymer is:
  • x, y, and z indicate the repeat units in the polymer. Individually, x, y, and z may range from 0 to 30. In some embodiments, the sum of x, y, and z may be from 5 to 50. In some embodiments, the sum of x, y, and z may be from 10 to 35. In some embodiments, the sum of x, y, and z may be about 29.
  • the post-modified polycarbodiimides may have a weight average molecular weight of from about 300 to about 30,000 g/mol. In some embodiments, the weight average molecular weight is from about 300 to about 20,000 g/mol. In some embodiments, the weight average molecular weight is from about 300 to about 10,000 g/mol. In some embodiments, the weight average molecular weight is from about 300 to about 2,500 g/mol.
  • a process of preparing a post-modified polycarbodiimide includes contacting a capped polycarbodiimide with a monomeric acid to form a mixture which is solvent-free. Furthermore, the process of contacting the monomeric acid with the post-modified polycarbodiimide may be catalyst free. In other words, the mixture may contain only the capped polycarbodiimide, or mixture of capped polycarbodiimides, and the monomer acid, or mixture of monomeric acids. The mixture may also include any catalyst residue from the catalyst that may have been employed in the preparation of the capped polycarbodiimide.
  • the process conditions are quite mild.
  • the contacting may be conducted at, or about, room temperature.
  • the temperature of the process may be from about 25° C. to about 40° C.
  • the process is conducted at a temperature of about 25° C. to about 30° C.
  • There may be an exothermic response as the acid and polycarbodiimide proceeds that may be managed through cooling and controlled addition of the acid.
  • the process uses a capped polycarbodiimide that may be a polymer of formula:
  • R 1 is a linking group
  • R 2 is an end cap derived from a monoisocyanate.
  • the linking group is alkyl, cycloalkyl, aromatic, heterocyclic, or heteroaryl.
  • R 1 and R 2 may individually be a C 1 -C 12 alkyl, C 1 -C 12 cycloalkyl, a C 6 -C 12 aromatic, a C 6 -C 12 heterocyclyl, or a C 6 -C 12 heteroaryl.
  • R 1 and R 2 include, but are not limited to, methylene, ethylene, propylene, isopropylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decalinylene, dodecylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, a tolyl, or a xylyl.
  • R 1 is an arylene group.
  • R 1 in some embodiments, is 1,3-phenylene, 1,4-phenylene, a tolyl, or a xylyl.
  • R 2 in some embodiments, is 1,3-phenylene, 1,4-phenylene, a tolyl, or a xylyl.
  • the monomeric acid used in the process may be a compound represented as R 3 C(O)OH, wherein R 3 is a polymerizable group.
  • the polymerizable group may be an alkylene group, such as a vinyl group.
  • Illustrative monomeric acids include, but are not limited to, acrylic acid, methacrylic acid, vinylphosphoric acid, or 4-vinylphenylboronic acid.
  • the post-modified polycarbodiimide may be a photo and/or chemical-curable polymer. That is, illustrative monomeric acids such as acrylic acid and methacrylic acid are photo and/or chemical-curable materials. Because the vinyl group, which imparts photo and/or chemical-curable character, does not take part in the reaction with the polycarbodiimide, the photo- and/or chemical curable character of the moiety containing the vinyl group is maintained in the post-modified polycarbodiimide. Such a group may be exploited in further uses of the post-modified polycarbodiimide when used in photo and/or chemical-cure applications.
  • the monomeric acid using the process may be a fatty acid.
  • some fatty acids may be represented as R 3 C(O)OH, where R 3 is a C 8 -C 24 alkyl or a C 8 -C 24 alkylene.
  • fatty acids include, but are not limited to, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, ⁇ -linolenic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, euricic acid, or docosahexaenoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, or cerotic acid.
  • Higher unsaturation in the fatty acid e.g. linoleic (2 double bonds) or linolenic (3 double bonds)
  • the monomeric acid may be an thiocarbonate acid of formula:
  • E is absent or is S
  • R 4 may be C 1 -C 18 alkyl
  • X is alkyl, aryl, nitrile, or halide.
  • Illustrative examples of the thiocarbonate acid include, but are not limited to, 2-(4-methoxyphenylcarbonothioylthio)-ethanoic acid; 2-(phenylcarbonothioylthio)-propanoic acid; 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid; 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid; 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid; and 3,5-bis(2-dodecylthiocarbonothioylthio-1-oxopropoxy)benzoic acid, a thiocarbonate acid, or a trithi
  • the capped polycarbodiimide may be reacted with any of the above monomeric acids to form the post-modified polycarbodiimide.
  • the post-modified polycarbodiimide may then be further modified with a vinylic monomer to provide a hybrid polymer.
  • Such an embodiment may be illustrated by the following scheme, using a thiocarbonate acid as an illustrative monomeric acid, but where any of the monomeric acids may be used.
  • the vinylic monomer is represented as H 2 C ⁇ CHR 5 , where R 5 is an alkyl, aryl, aralkyl, —OC(O)alkyl, —C(O)Oalkyl, —OC(O)aryl, —C(O)Oaryl, heteroaryl, heterarylalkyl, heterocyclyl, or heterocyclylalkyl group, an x is the repeat unit in the polymer.
  • the value of x may be 0 (where the vinylic monomer is not present), or x may be from 1 to 50. In some embodiments, x is from 1 to 15.
  • Vinylic monomers may include, but are not limited to, styrene and ⁇ -methylstyrene, isobutyl acrylate, hydroxyethyl caprolactone acrylate, hexyl acrylate, isodecyl acrylate, lauryl acrylate, behenyl acrylate, allyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, tert.-butylaminoethyl methacrylate, lauryl methacrylate, stearyl methacrylate, behenyl methacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, PEG 200 dimethacrylate, trimethylolpropane trimethacrylate, 2-ethylhexyl acrylate, N-viny
  • a thiocarbonate acid is the monomeric acid
  • it may initially be modified with the vinylic monomer (to form a thiocarbonate-polyvinylic-acid as a monomeric acid) prior to reaction with the post-modified polycarbodiimide.
  • the polycarbodiimide used in the processes may be prepared or commercially obtained.
  • the polycarbodiimide may be a polymer derived from a monomer of formula ONC—R 1 —CNO, in the absence of a solvent, where R 1 is as defined above in any of the embodiments.
  • R is an arylene group such as, but not limited to, phenylene, tolylene, or xylylene.
  • the capped polycarbodiimide may be prepared by combining in a reaction vessel a diisocyanate, a moisture scavenger, a monoisocyanate, and a catalyst to form a reaction mixture; and heating the reaction reaction mixture to a temperature and for a time sufficient to form a capped polycarbodiimide.
  • the diisocyanate, moisture scavenger, and a monoisocyanate are as described above and below.
  • the capped polycarbodiimide prepared has 0.25 wt % or less of free isocyanate groups, and, in the process, the combining and heating are conducted in the absence of a solvent.
  • illustrative temperatures are from about 30° C. to about 200° C. In some embodiments, the temperature is from about 60° C. to about 120° C. In yet other embodiments, the temperature is from about 100° C. to about 110° C.
  • Example 3 may be followed with ratios of 2,4-toluene diisocyanate:2,6-toluene diisocyanate ranging from 100:0 to 65:35.
  • Example 1 Complete conversion of a toluene diisocyanate-based polycarbodiimide (carbodiimide-acrylic acid) (Example 1) to a UV and/or chemical curable resin.
  • a toluene diisocyanate-based polycarbodiimide from Example 1 (5 g) was reacted with acrylic acid (2 g) by mechanical mixing at ambient temperature. The reaction was instantaneous and exothermic. The disappearance of the carbodiimide was monitored by infrared spectroscopy. Upon completion a post-modified polycarbodiimide was obtained.
  • Example 1 Partial conversion of a toluene diisocyanate-based polycarbodiimide (carbodiimide-acrylic acid) (Example 1) to a UV and/or chemical curable resin.
  • a toluene diisocyanate-based polycarbodiimide from Example 1 (2.0 g) was reacted with acrylic acid (0.5 g) by mechanical mixing at ambient temperature. The reaction was instantaneous and exothermic. A decrease in the vibration of the carbodiimide was monitored by infrared spectroscopy to determine extent of the reaction.
  • N-acylurea of acrylic acid was obtained.
  • Example 1 Partial conversion of a toluene diisocyanate-based polycarbodiimide (carbodiimide-acrylic acid-tripropyneglycol diacrylate) (Example 1) to a UV and/or chemical curable resin.
  • a toluene diisocyanate-based polycarbodiimide from Example 1 (1.0 g) was reacted with acrylic acid (0.24 g), tripropylene glycol diacrylate (0.25 g) by mechanical mixing at ambient temperature. The reaction was instantaneous and exothermic. A decrease in the vibration of the carbodiimide was monitored by infrared spectroscopy to determine extent of the reaction.
  • N-acylurea and tripropylene glycol diacrylate was obtained.
  • Example 1 Partial conversion of a toluene diisocyanate-based polycarbodiimide (carbodiimide-acrylic acid-trimethylolpropane triacrylate) (Example 1) to a UV and/or chemical curable resin.
  • N-acylurea and TMPTA was obtained.
  • ZOLIDINE® XL-29SE Conversion of a commercial polycarbodiimide ZOLIDINE® XL-29SE to a UV curable resin.
  • ZOLIDINE® XL-29SE (10 g) was reacted with acrylic acid (0.89 g) in an orbital shaker at ambient temperature. The reaction was slow and it took 24 hours for the disappearance of the carbodiimide (as monitored by infrared spectroscopy) indicating the completion of the reaction. Upon completion a post-modified polycarbodiimide was obtained.
  • Oleic acid modified toluene diisocyanate-based polycarbodiimide (carbodiimide-Oleic acid 1:1 wt ratio).
  • Oleic acid modified toluene diisocyanate-based polycarbodiimide (carbodiimide-oleic acid 1:2.5 wt ratio).
  • a toluene diisocyanate-based polycarbodiimide from Example 1 was reacted with oleic acid in a 1:2.5 wt ratio in a Parr Pressure reactor at 600 rpm at ambient temperature.
  • the reaction was instantaneous ( ⁇ 10 min) and exothermic. Formation of N-acyl was monitored by infrared spectroscopy to determine the extent of the reaction.
  • the top spectrum is the polycarbodiimide
  • middle is of partially reacted
  • the bottom spectrum is the fully modified spectrum.
  • Post-modified toluene diisocyanate-based polycarbodiimide (carbodiimide-fatty acid-acrylic acid-tripropylene glycol diacrylate).
  • a toluene diisocyanate-based polycarbodiimide from Example 1 (1.0 g) was reacted with acrylic acid (0.24 g) tripropylene glycol diacrylate (0.25 g) and oleic acid (1.0 g) by vigorous mechanical mixing at ambient temperature. The reaction was instantaneous ( ⁇ 10 min) and exothermic. Formation of N-acyl was monitored by infrared spectroscopy to determine the extent of the reaction.
  • N-acylurea (acrylic acid and oleic acid) and tripropylene glycol diacrylate was obtained.
  • Post-modified toluene diisocyanate-based polycarbodiimide (carbodiimide-Fatty acid based resin Pamolyn 380).
  • a toluene diisocyanate-based polycarbodiimide from Example 1 (4.0 g) was reacted with commercially available fatty acid based resin Pamolyn 380 (4.0 g) by vigorous mechanical mixing at ambient temperature. The reaction was instantaneous ( ⁇ 10 min) and exothermic. Formation of N-acyl was monitored by infrared spectroscopy to determine the extent of the reaction. Upon completion a post-modified polycarbodiimide was obtained.
  • Post-modified toluene diisocyanate-based polycarbodiimide (carbodiimide-fatty acid-tung oil).
  • a toluene diisocyanate-based polycarbodiimide from Example 1 (2.0 g) was reacted with oleic acid (2.0 g) and tung oil (0.5 g) by vigorous mechanical mixing at ambient temperature. The reaction was instantaneous ( ⁇ 10 min) and exothermic. Formation of N-acyl was monitored by infrared spectroscopy to determine the extent of the reaction. Upon completion a post-modified polycarbodiimide was obtained.

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KR102411828B1 (ko) 2022-06-22
WO2015127041A1 (en) 2015-08-27
EP3107945A1 (en) 2016-12-28
JP2017507213A (ja) 2017-03-16
TW201602235A (zh) 2016-01-16
EP3107946A1 (en) 2016-12-28
PT3107946T (pt) 2018-11-22

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