US20100210788A1 - Electron deficient olefins - Google Patents

Electron deficient olefins Download PDF

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US20100210788A1
US20100210788A1 US12/766,457 US76645710A US2010210788A1 US 20100210788 A1 US20100210788 A1 US 20100210788A1 US 76645710 A US76645710 A US 76645710A US 2010210788 A1 US2010210788 A1 US 2010210788A1
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alkyl
aryl
cyanoacrylate
cyanoacrylates
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Ciaran B. McArdle
Ligang Zhao
Stefano Gherardi
Kevin Murnaghan
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Henkel IP and Holding GmbH
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Henkel Loctite Ireland Ltd
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Priority to US14/663,722 priority patent/US20150191424A1/en
Priority to US14/945,843 priority patent/US9481640B2/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/15—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound oxygen atoms bound to the same unsaturated acyclic carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/17—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and doubly-bound oxygen atoms bound to the same acyclic carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/19—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and carboxyl groups, other than cyano groups, bound to the same saturated acyclic carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/23—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and carboxyl groups, other than cyano groups, bound to the same unsaturated acyclic carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/593—Dicarboxylic acid esters having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/30—Nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates

Definitions

  • This invention relates to novel electron deficient olefins, such as certain 2-cyanoacrylates or methylidene malonates, prepared using an imine or an iminium salt.
  • Cyanoacrylate adhesives are known for their fast adhesion and ability to bond a wide variety of substrates. They are marketed as “super glue” type adhesives. They are useful as an all-purpose adhesive since they are a single component adhesive, very economical as only a small amount will do, and generally do not require any equipment to effectuate curing.
  • cyanoacrylate monomers have been produced by way of a Knoevenagel condensation reaction between a formaldehyde precursor, such as paraformaldehyde, and an alkyl cyanoacetate with a basic catalyst. During the reaction, cyanoacrylate monomer forms and polymerises in situ to a prepolymer. The prepolymer is subsequently thermally cracked or depolymerised, yielding cyanoacrylate monomer.
  • This approach has remained essentially the same over time, though various improvements and variants have been introduced. See e.g. U.S. Pat. Nos. 6,245,933, 5,624,699, 4,364,876, 2,721,858, 2,763,677 and 2,756,251.
  • U.S. Pat. No. 5,703,267 defines a process for producing a 2-cyanoacrylic acid which comprises subjecting a 2-cyanoacrylate and an organic acid to a transesterification reaction.
  • U.S. Pat. No. 5,455,369 defines an improvement in a process for preparing methyl cyanoacrylate, in which methyl cyanoacetate is reacted with formaldehyde to form a polymer that is then depolymerized to the monomeric product, and in which the purity of yield is 96% or better.
  • the improvement of the '369 patent is reported to be conducting the process in a poly(ethylene glycol)diacetate, dipropionate, or dibutyrate, having a number average molecular weight of 200-400, as the solvent.
  • U.S. Pat. No. 6,096,848 defines a process for the production of a biscyanoacrylate, which comprises the steps of esterifying a 2-cyanoacrylic acid or transesterifying an alkyl ester thereof to obtain a reaction mixture; and fractionally crystallizing the reaction mixture to obtain the biscyanoacrylate.
  • U.S. Pat. No. 4,587,059 defines a process for the preparation of monomeric 2-cyanoacrylates comprising the steps of (a) reacting (i) a 2,4-dicyanoglutarate with (ii) formaldehyde, cyclic or linear polymers of formaldehyde, or a mixture thereof, in the presence of between about 0.5 and about 5 mols of water per mol of 2,4-dicyanoglutarate, at an acid pH of about 3 to slightly less than 7, and at a temperature of about 70 to about 140, to form an oligomeric intermediate product, and (b) removing water that is present from step (a) and thermolyzing the oligomeric intermediate product for a period of time sufficient to effect its conversion to monomeric 2-cyanoacrylates.
  • cyanoacrylate esters bearing moisture, base, acid, thermally sensitive or otherwise reactive moieties may not be conveniently produced and isolated under Knoevenagel reaction conditions.
  • cyanoacrylates with reactive functionality in the ester side chain are known (see e.g. Buck and U.S. Pat. Nos. 3,975,422, 3,903,055, 4,003,942, 4,012,402, and 4,013,703)
  • the cyanoacrylates with reactive functionality in the ester side chain are prepared in a multi-step process involving protective group strategies and functional group transformations to arrive at adducts which must subsequently be deprotected to yield cyanoacrylates with additional functionality.
  • the same approach has been described to arrive at a cyanoacrylate-capped polyisobutylene by Kennedy et al., J. Macromol Sci. Chem., A28, 209 (1991).
  • U.S. Pat. No. 5,142,098 describes a copper catalysed reaction of malonates and formaldehyde to form methylidenemalonate monomers that are trapped in situ by a “diene” anthracene in a Diels-Alder reaction.
  • the '098 patent describes a diester adduct of anthracene, that is a precursor for a methylidenemalonate monomer with one ethyl ester and one glycidyl ester.
  • the '098 patent indicates that reaction—a retro Diels-Alder thermolysis step—was not successful for the preparation of the particular methylidene malonate bearing the glycidyl functionality in the ester side chain.
  • the retro Diels-Alder reaction has been reported as useful in the syntheses of other methylidene malonates (see e.g. J-L. De Keyser et al., J. Org. Chem., 53, 4859 (1988)).
  • the present invention provides novel electron deficient olefins, such as 2-cyanoacrylates or methylidene malonates, with a reactive functional group in the ester side chain, prepared using an imine or an iminium salt.
  • novel compounds are electron deficient olefins within structure I:
  • X is (a) an electron withdrawing group
  • n 0 or 1.
  • g is 1. However, if g>1, D is should be H.
  • D is selected from H, alkyl or aryl
  • n is 0 or 1
  • A, B, 1, 2, 3, 4, 5, and 6 are each references to bond designations.
  • Z is a reactive functionality
  • n is 0 or 1 and g is 1.
  • the reactive functionality of Z in structure III may be selected from epoxides, episulfides, oxetanes, thioxetanes, dioxolanes, dioxanes, isocyanates, maleimides, oxazolines, succinimides, 2-cyanoacrylates, methyiidene malonates, acrylonitrile, (meth)acrylates, carboxylic acids and derivatives thereof, cyanoacetates, methylene malonates, hydroxyls, silanes, siloxanes, titanates, or zirconates.
  • the present invention also provides compositions of the compounds of structures I, together with a stabilizer package comprising at least one of a free radical stabilizer and an anionic stabilizer; and optionally, one or more additives selected from cure accelerators, thickeners, thixotropes, tougheners, thermal resistance-conferring agents, or plasticizers.
  • the present invention further provides compositions of the compounds of structures I, II or III, together with a cyanoacrylate or a methylidene malonate.
  • the present invention further provides compositions of certain of the compounds of structures I, II or III, together with a coreactant, such as one selected from epoxides, episulfides, oxetanes, thioxetanes, dioxolanes, dioxanes, isocyanates, maleimides, oxazolines, (meth)acrylates, cyanoacrylates, methylidene malonates or vinyl ethers.
  • a coreactant such as one selected from epoxides, episulfides, oxetanes, thioxetanes, dioxolanes, dioxanes, isocyanates, maleimides, oxazolines, (meth)acrylates, cyanoacrylates, methylidene malonates or vinyl ether
  • FIG. 1 depicts a synthetic scheme by which iminium salts may be prepared.
  • FIG. 2 depicts a synthetic scheme by which a precursor to an inventive electron deficient olefin may be prepared.
  • FIG. 3 depicts a synthetic scheme by which the precursor to an inventive electron deficient olefin (from FIG. 2 ) is used with the iminium salt (from FIG. 1 ) to form the inventive electron deficient olefin.
  • the present invention provides electron deficient olefins within structure I:
  • X is (a) an electron withdrawing group, or (b) Y;
  • n 0 or 1.
  • g is 1. However, if g>1, D is should be H.
  • X is an electron withdrawing group (such as CN, CO 2 R, CO 2 H, COCl, COR, COPO(OR) 2 , COPOR 2 , SO 2 R, SO 3 R or NO 2 , where R is C 1-4 ) or E, E is as shown,
  • D is selected from H, alkyl or aryl
  • n is 0 or 1
  • A, B, 1, 2, 3, 4, 5, and 6 are each references to bond designations.
  • Q may be an amide or thioamide embraced by
  • T is O or S and U or V are each independently selected from H or R, where R is C 1-4 .
  • the vinyl group labeled ‘6’ is disposed 6 bond lengths distance from the vinyl group labeled ‘1’, ignoring side branches and where Q is not H.
  • X is an electron withdrawing group (such as CN, CO 2 R, CO 2 H, COCl, COR, COPO(OR) 2 , COPOR 2 , SO 2 R, SO 3 R or NO 2 , where R is C 1-4 ) or F, D is selected from H, alkyl or aryl, Z is a reactive functionality, n is 0 or 1 and g is 1.
  • the reactive functionality of Z in structure III may be selected from epoxides, episulfides, oxetanes, thioxetanes, dioxolanes, dioxanes, isocyanates, maleimides, oxazolines, succinimides, 2-cyanoacrylates, methylidene malonates, acrylonitrile, (meth)acrylates, carboxylic acids and derivatives thereof, cyanoacetates, methylene malonates, hydroxyls, silanes, siloxanes, titanates, or zirconates.
  • novel electron deficient olefins within the scope of the invention include
  • R 1 -R 2 , A-B, E, R 3 , w, y and z are as defined above.
  • the iminium salt embraced within structure VII is as follows:
  • the iminium salt is embraced more specifically by structure VIIA as follows:
  • R 1 -R 2 , A-B, E, R 3 , w, y and z, and X are as defined above.
  • the imine in some cases may be an imine having an onium salt, such as an ammonium or amine salt functionality.
  • the imines may be termed an “ionic liquid” (or “IL”) or a task specific ionic liquid (or, “TSIL”), as will be discussed in more detail below.
  • the iminium salts may be termed an “ionic liquid” (or “IL”) or a task specific ionic liquid (or, “TSIL”), as will be discussed in more detail below.
  • the imine of structure VI or the iminium salt of structure VII is particularly stable at room temperature conditions when in the presence of the precursor to the electron deficient olefin, a modest amount of heat may be useful to allow the reaction to generate electron deficient olefins. Exposure to elevated temperature conditions is particularly desirable with iminium salts of structure VII.
  • an aldehyde compound having the structure R 3 R 4 C ⁇ O, where R 3 is hydrogen and R 4 is a hydrogen, vinyl or propargyl.
  • the aldehyde compound may be an aldehyde itself or a source of an aldehyde, such as one that yields an aldehyde like formaldehyde under appropriate reaction conditions.
  • the aldehyde compound in a desirable embodiment includes formaldehyde or a source thereof, such as paraformaldehyde (see FIG. 1 ), formalin, or 1,3,5-trioxane, or vinyl aldehydes, such as acrolein.
  • a reactant with such an aldehyde is a primary amine.
  • Primary amines attached to a carbon bearing no alpha protons are particularly desirable, such as t-alkyl primary amines.
  • Rohm and Haas Co., Philadelphia, Pa. has sold commercially for a number of years a series of t-alkyl primary amines, which are designated as PRIMENE-brand amines.
  • t-alkyl primary amines available from Rohm and Haas include PRIMENE 81-R and PRIMENE JM-T. These PRIMENE-brand t-alkyl primary amines have highly branched alkyl chains (represented schematically by circle symbols in the Figures for simplicity) in which the amino nitrogen atom is attached directly to a tertiary carbon. These t-alkyl primary amines consist of mixtures of isomeric amines, with PRIMENE 81-R consisting of an isomeric mixture with C 12 -C 14 carbon branches and having an average molecular weight of 185 and PRIMENE JM-T consisting of an isomeric mixture with C 16 -C 22 carbon branches and having average molecular weight of 269.
  • PRIMENE MD also known as menthanediamine (1,8-diamino-p-menthane) or (4-amino- ⁇ , ⁇ -4-trimethyl-cyclohexanemethanamine, CAS No. 80-52-4
  • menthanediamine is a primary alicyclic diamine, in which both amino groups are attached to tertiary carbon atoms.
  • menthanediamine is somewhat less reactive than similar straight chain diamines.
  • PRIMENE TOA has tertiary octyl chains and a molecular weight of 129.
  • PRIMENE 81-R MSA iminium salt formed in reaction (2) of FIG. 1 , is used.
  • the imines whether or not bearing ammonium salt functionality or whether or not they are tethered to a support, are then reacted with compounds containing a methylene linkage having at least one, desirably two, electron withdrawing substituent(s) attached thereto.
  • a methylene compound useful as a precursor to an electron deficient olefin is depicted in FIG. 2 , which illustrates the esterification of cyanoacetic acid with alpha hydroxymethyl acrylate.
  • the electron withdrawing substituent is selected from nitrile, carboxylic acids, carboxylic esters, sulphonic or suphinic acids or their esters, ketones, phosphocarbonyl, or nitro.
  • Such compounds are reacted with iminium salts for example as depicted in FIG. 3 to form novel electron deficient olefins.
  • these compounds have two or more electron withdrawing substituents, which may be the same or different, such as nitrile and carboxylic acid ester—in this case, a cyanoacrylate.
  • the reactivity of these compounds in large part depends on the degree of electron withdrawing capability of the particular substituent, and the number of substituents on the active methylene carbon.
  • the reaction to form the novel electron deficient olefins may proceed with or without heating or cooling, depending of course on the specific reactants and the scale of the reaction.
  • Decomposition of the source of formaldehyde e.g., paraformaldehyde
  • the temperature may be reached through an external heating element or internally by means of the exotherm that may be generated, depending of course on the identity of the reactants.
  • the temperature of the reaction should be controlled however to accommodate any such exothermic processes.
  • the time of reaction may be monitored by reference to the formation of the desired novel electron deficient olefin product.
  • a 1 H NMR spectrometer is a particularly useful tool in this regard.
  • the time of reaction may be as little as 1 minute, for instance, or longer or shorter for that matter depending again on the identity of the specific, reactants, the scale of the reaction and whether heat is introduced to or removed from the reaction conditions.
  • the novel electron deficient olefin may be isolated by direct distillation under vacuum out of the reaction mixture or by freezing it in a solid form and separating off the liquid phase.
  • novel electron deficient olefin may be stabilized during the synthesis and/or isolation procedure, and also in the isolated product to improve its shelf life.
  • Suitable stabilizers include stabilizer packages that may contain one or more of free radical stabilizers and acidic stabilizers.
  • free radical stabilizers include hydroquinone, pyrocatechol, resorcinol or derivatives thereof, such as hydroquinone monoethyl ether, or phenols, such as di-t-butylphenol or 2,6-di-t-butyl-p-cresol, 2,2′-methylene-bis-(4-methyl-6-t-butylphenol), bisphenol A, dihydroxydiphenylmethane, and styrenized phenols.
  • hydroquinone pyrocatechol
  • resorcinol or derivatives thereof such as hydroquinone monoethyl ether
  • phenols such as di-t-butylphenol or 2,6-di-t-butyl-p-cresol, 2,2′-methylene-bis-(4-methyl-6-t-butylphenol), bisphenol A, dihydroxydiphenylmethane, and styrenized phenols.
  • acidic stabilizers include sulfuric acid, hydrochloric acid, sulfonic acids, such as methane, ethane or higher sulfonic acids, p-toluene sulfonic acid, phosphoric acid or polyphosphoric acids, silyl esters of strong acids, such as trialkyl chlorosilanes, dialkyl dichlorosilanes, alkyl trichlorosilanes, tetrachlorosilane, trialkyl silylsulfonic acids, trialkyl silyl-p-toluene sulfonates, bis-trialkyl silylsulfate and trialkyl silylphosphoric acid esters.
  • sulfonic acids such as methane, ethane or higher sulfonic acids, p-toluene sulfonic acid, phosphoric acid or polyphosphoric acids
  • silyl esters of strong acids such as trialkyl chlorosilanes
  • the amount of either stabilizer used to stabilize the electron deficient olefin prepared by the inventive processes is well known to those of ordinary skill in the art, and may be varied depending on the properties of the resulting composition made from the so formed electron deficient olefin.
  • the present invention also provides compositions of the compounds of structures I, II or III, together with a stabilizer package comprising at least one of a free radical stabilizer and an anionic stabilizer; and optionally, one or more additives selected from cure accelerators, thickeners, thixotropes, tougheners, thermal resistance-conferring agents, or plasticizers.
  • the cure accelerators that may be included with the inventive electron deficient olefins to form inventive compositions include calixarenes and oxacalixarenes, silacrowns, crown ethers, cyclodextrins, poly(ethyleneglycol) di(meth)acrylates, ethoxylated hydric compounds and combinations thereof.
  • calixarenes those within the following structure are useful herein:
  • R 1 is alkyl, alkoxy, substituted alkyl or substituted alkoxy
  • R 2 is H or alkyl
  • n is 4, 6 or 8.
  • calixarene is tetrabutyl tetra[2-ethoxy-2-oxoethoxy]calix-4-arene.
  • crown ethers A host of crown ethers are known.
  • examples which may be used herein include 15-crown-5,18-crown-6, dibenzo-18-crown-6, benzo-15-crown-5-dibenzo-24-crown-8, dibenzo-30-crown-10, tribenzo-18-crown-6, asym-dibenzo-22-crown-6, dibenzo-14-crown-4, dicyclohexyl-18-crown-6, dicyclohexyl-24-crown-8, cyclohexyl-12-crown-4, 1,2-decalyl-15-crown-5,1,2-naphtho-15-crown-5,3,4,5-naphtyl-16-crown-5,1,2-methyl-benzo-18-crown-6,1,2-methylbenzo-5,6-methylbenzo-18-crown-6,1,2-t-butyl-18-crown-6,1,2-vinylbenzo-15-
  • silacrowns again many are known, and are reported in the literature.
  • a typical silacrown may be represented within the following structure:
  • R 3 and R 4 are organo groups which do not themselves cause polymerization of the cyanoacrylate monomer
  • R 5 is H or CH 3 and n is an integer of between 1 and 4.
  • suitable R 3 and R 4 groups are R groups, alkoxy groups, such as methoxy, and aryloxy groups, such as phenoxy.
  • the R 3 and R 4 groups may contain halogen or other substituents, an example being trifluoropropyl.
  • groups not suitable as R 4 and R 5 groups are basic groups, such as amino, substituted amino and alkylamino.
  • cyclodextrins may be used in connection with the present invention.
  • those described and claimed in U.S. Pat. No. 5,312,864 (Wenz), the disclosure of which is hereby expressly incorporated herein by reference, as hydroxyl group derivatives of an ⁇ -, ⁇ - or ⁇ -cyclodextrin which is at least partly soluble in the cyanoacrylate would be appropriate choices for use herein as the first accelerator component.
  • poly(ethylene glycol) di(meth)acrylates suitable for use herein include those within the following structure:
  • n is greater than 3, such as within the range of 3 to 12, with n being 9 as particularly desirable. More specific examples include PEG 200 DMA (where n is about 4), PEG 400 DMA (where n is about 9), PEG 600 DMA (where n is about 14), and PEG 800 DMA (where n is about 19), where the number (e.g., 400) represents the average molecular weight of the glycol portion of the molecule, excluding the two methacrylate groups, expressed as grams/mole (i.e., 400 g/mol).
  • a particularly desirable PEG DMA is PEG 400 DMA.
  • ethoxylated hydric compounds or ethoxylated fatty alcohols that may be employed
  • appropriate ones may be chosen from those within the following structure:
  • C m can be a linear or branched alkyl or alkenyl chain
  • m is an integer between 1 to 30, such as from 5 to 20
  • n is an integer between 2 to 30, such as from 5 to 15, and R in this connection may be H or alkyl, such as C 1-6 alkyl.
  • DEHYDOL 100 Commercially available examples of materials within the above structure include those offered under the DEHYDOL tradename from Henkel KGaA, Dusseldorf, Germany, such as DEHYDOL 100.
  • the cure accelerator should be included in the compositions in an amount within the range of from about 0.01% to about 10% by weight, with the range of about 0.1 to about 0.5% by weight being desirable, and about 0.4% by weight of the total composition being particularly desirable.
  • inventive electron deficient olefins may be included with inventive electron deficient olefins to form inventive compositions to confer additional physical properties, such as improved shock resistance, thickness (for instance, polymethyl methacrylate), thixotropy (for instance fumed silica), color, and enhanced resistance to thermal degradation
  • maleimide compounds such as N,N′-meta-phenylene bismaleimide (see U.S. Pat. No. 3,988,299 (Malofsky)
  • certain mono, poly or hetero aromatic compounds characterized by at least three substitutions on an aromatic ring thereof, two or more of which being electron withdrawing groups see U.S. Pat. No. 5,288,794 (Attarwala)
  • certain quinoid compounds see U.S. Pat. No.
  • alkylating agents such as polyvinyl benzyl chloride, 4-nitrobenzyl chloride, and combinations thereof, silylating agents, and combinations thereof (see U.S. Pat. No. 6,093,780 (Attarwala)), the disclosures of each of which are hereby incorporated herein by reference.
  • Such additives therefore may be selected from certain acidic materials (like citric acid), thixotropy or gelling agents, thickeners, dyes, thermal degradation resistance enhancers, and combinations thereof. See e.g. U.S. patent application Ser. No. 11/119,703 and U.S. Pat. Nos. 5,306,752, 5,424,344 and 6,835,789, the disclosures of each of which are hereby incorporated herein by reference.
  • additives may be used in the inventive compositions individually in an amount from about 0.05% to about 20%, such as about 1% to 15%, desirably 5% to 10% by weight, depending of course on the identity of the additive.
  • citric acid may be used in the inventive compositions in an amount of 5 to 500 ppm, desirably 10 to 100 ppm.
  • inventive electron deficient olefins may render it less desirable to include one or more these additives with the inventive electron deficient olefins to form inventive compositions.
  • the present invention further provides compositions of the inventive compounds, together with a cyanoacrylate, a methylidene malonate or combinations thereof.
  • cyanoacrylate used in combination with the inventive compounds is one within structure IV:
  • R 1 is selected from C 1-16 alkyl, alkoxyalkyl, cycloalkyl, alkenyl (such as allyl), alkynyl, arylalkyl, aryl, or haloalkyl groups.
  • the cyanoacrylate with structure IV is selected from methyl cyanoacrylate, ethyl-2-cyanoacrylate, propyl cyanoacrylates, butyl cyanoacrylates, octyl cyanoacrylates, allyl cyanoacrylate, ⁇ -methoxyethyl cyanoacrylate and combinations thereof.
  • methylidene malonate used in combination with the inventive compounds is one within structure V:
  • R 2 and R 3 are each independently selected from C 1-16 alkyl, alkoxyalkyl, cycloalkyl, alkenyl, aralkyl, aryl, allyl or haloalkyl groups.
  • the present invention further provides compositions of certain of the compounds of structure I, together with a coreactant, such as one selected from epoxides (such as cycloaliphatic epoxies), episulfides, oxetanes, thioxetanes, dioxolanes, dioxanes, isocyanates, maleimides, oxazolines, (meth)acrylates, acrylamides, cyanoacrylates, methylidene malonates or vinyl ethers.
  • a coreactant such as one selected from epoxides (such as cycloaliphatic epoxies), episulfides, oxetanes, thioxetanes, dioxolanes, dioxanes, isocyanates, maleimides, oxazolines, (meth)acrylates, acrylamides, cyanoacrylates, methylidene malonates or vinyl ethers.
  • PRIMENE 81-R imine was prepared by reaction of PRIMENE 81-R amine with a stoichiometric equivalent of paraformaldehyde and removal of water of condensation. All imines formed were distillable liquids and existed in stable monomeric imine forms as confirmed by 1 H NMR 60 MHz (CDCl 3 ) 2H s (br) 7.45 ppm and FTIR (1650 cm ⁇ 1 ).
  • PRIMENE 81-R iminium-MSA was prepared from PRIMENE 81-R imine by adding dropwise with stirring methane sulfonic acid at ice water bath temperature, yielding a pale yellow iminium salt.
  • reaction product was washed consecutively with 30% brine and water.
  • organic layer was dried over anhydrous sodium sulfate, filtered and the solvent removed by rotary evaporator.
  • the crude reaction product was purified by vacuum distillation (120-126° C./0.2 mbar), with the ester of structure A (102 g, 0.52 mol) isolated in a 52% yield.
  • reaction product was washed consecutively with 30% brine and water, and the organic layer was dried over anhydrous sodium sulfate, filtered and the solvent removed by rotary evaporator.
  • the crude reaction product was purified by vacuum distillation (98-100° C./0.1 mbar) and the ester, C was isolated in 80% yield.
  • reaction product was washed consecutively with 30% brine and water, and the organic layer was dried over anhydrous sodium sulfate, filtered and the solvent removed by rotary evaporator.
  • the crude reaction product was purified by vacuum distillation (86-88° C./0.05 mbar) and 7.5 g, 38 mmol of the ester, D was isolated in 49% yield.
  • the table below shows the starting intermediate, the resulting electron deficient olefin, the purity of the resulting electron deficient olefin and the yield in which some of the electron deficient olefins described above were obtained.

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US9481640B2 (en) 2016-11-01
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US20160075641A1 (en) 2016-03-17
US20150191424A1 (en) 2015-07-09
WO2009053484A2 (en) 2009-04-30
WO2009053484A3 (en) 2009-06-25
EP2217559B1 (en) 2017-06-28
ES2634631T3 (es) 2017-09-28
EP2217559A2 (en) 2010-08-18
JP2011500769A (ja) 2011-01-06
KR101571913B1 (ko) 2015-11-25
KR20100097116A (ko) 2010-09-02
JP5639892B2 (ja) 2014-12-10

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