WO2017108946A1 - Compositions de résine thermodurcissable - Google Patents

Compositions de résine thermodurcissable Download PDF

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WO2017108946A1
WO2017108946A1 PCT/EP2016/082172 EP2016082172W WO2017108946A1 WO 2017108946 A1 WO2017108946 A1 WO 2017108946A1 EP 2016082172 W EP2016082172 W EP 2016082172W WO 2017108946 A1 WO2017108946 A1 WO 2017108946A1
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group
groups
carbon atoms
formula
bis
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PCT/EP2016/082172
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Chris Mason
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Hexcel Composites Limited
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08L79/085—Unsaturated polyimide precursors

Definitions

  • the present invention relates to [(2-ethoxy-5-trans-1 -propen-1 -yl)-phenoxy] - terminated compounds and to heat-curable resin compositions based on
  • polymaleimide resin systems comprising such [(2-ethoxy-5-trans-1 -propen-1 -yl)- phenoxy] - terminated compounds as co-monomers.
  • the present invention also relates to crosslinked resins obtainable by curing such compositions.
  • Compounds of the present invention can be used amongst others in the following fields: Structural adhesives, matrix resins for fiber prepregs, moulding compounds, as well as structural and/or electrical composites.
  • the present invention also relates to the production and use of meta and/or para vinyl phenols, particularly meta and of meta and/or para propenylphenols and in particular meta vinyl phenols and especially meta isopropenyl phenol.
  • the invention further relates to the use of meta or para vinyl phenols and of meta or para propenylphenols as end cap molecules and also to the use of certain molecules that have been encapped with a vinyl phenol or propenylphenol as curatives particularly in polymaleamide resin systems and polymaleimide
  • Curable thermosetting compositions based on polymaleimide building blocks and co- monomers are established resins for fiber composites, adhesives, moulding and potting compounds. These resins are known for their high temperature resistance.
  • the co-monomer part of the composition influences several uncured and cured resin properties. Importantly, a suitable choice of this co-monomer part is required for modifying the processing properties of the uncured resin, in particular to adjust rheological properties such as flow and viscosity and to influence the cure kinetic properties.
  • Desired properties of the cured polymaleimide/co-monomer system include high glass transition temperature (Tg), high modulus retention at temperatures around 250 °C, high heat resistance in terms of thermal oxidative stability (TOS) and durability, high toughness and damage tolerance and temperature cycling resistance to microcracking. Further desired properties include low moisture and solvent uptake and low dielectric constant (DC).
  • Tg glass transition temperature
  • TOS thermal oxidative stability
  • DC dielectric constant
  • thermosetting compositions based on polymaleinnides and alkenylphenoxy compounds are known, for example, from US Patent Nos. 4,789,704 (1988),
  • Desirable properties of uncured bismaleimide/co-monomer systems with respect to their use for composites and fiber reinforced composites in particular include low viscosity at processing temperature, low processing temperature, sufficient pot life at processing temperature, good storage stability in the form of resins and intermediate products such as prepregs, glues or compounds as well as fast cure kinetics (fast reaction of co-monomers and polymaleinnides) during manufacture of composites.
  • Tg glass transition temperature
  • alkenylphenols The manufacture of alkenylphenols is described by P. Y. Chen et al at page 655 of Tetrahedron 69 (2013).
  • This document discloses a process described for the production of para vinyl phenol reacted alkyltriphenyl phosphorous bromide with potassium tertiary butoxide in tetrahydro furan (THF) followed by reaction with para hydroxyl benzaldehyde in THF.
  • THF tetrahydro furan
  • the solution is then quenched with a saturated NH4CI solution, concentrated in vacuo to dichloride and then washed with brine and dried over MgSO4.
  • the purified residue includes vinyl propenyl and phenol propenyl.
  • the invention provides a simpler process for the manufacture of alkenyl phenols and propenyl phenols and vinyl phenols in particular.
  • the invention reacts a triphenyl phosphorous bromide with potassium tertiary butoxide to form an intermediate and reacts the intermediate with para hydroxyl benzaldehyde converting the product into a phenolate and extracting the phenolate into an aqueous phase followed by acidification and re-extraction into an organic solvent such as ethyl acetate.
  • an object of the present invention resided in providing co- monomers for use in polymaleimide/co-monomer systems as well as such
  • polymaleimide/co-monomer systems characterized by fast cure kinetics (fast reaction of co-monomers and polymaleimides) and good processing properties of such polymaleimide/co-monomer systems, yielding copolymers with a low tendency to absorb water thus resulting in copolymers with (i) good mechanical properties at elevated temperatures and/or (ii) a low tendency to suffer from microcracks under conditions of thermal cycling and/or (iii) good electrical properties (low dielectric constant).
  • D is an x-functional group
  • x is an integer > 2; with the provisio that
  • the x-functional group D is not a polycarbonate with an average molar mass in the range of 15000 g/mol to 150000 g/mol.
  • vanitrope (2-Ethoxy-5-trans-1 -propen-1 -yl)-phenol is commonly called vanitrope.
  • a vanitrope- terminated polycarbonate of specific molecular mass as such has been disclosed in the prior art (cf. JP3220567B2, paragraph [0047], example 4: Average molar mass of 20800 g/mol and weighted average molar mass of 51200 g/mol), however, no mention was made in the prior art concerning the usefulness of this polycarbonate as a co-monomer for polymaleimides.
  • D is not a polycarbonate.
  • trans (E)-2-Ethoxy-5-(1 - propenyl)phenoxy-substituted compounds of formula (I) is trans (E)-2-Ethoxy-5-(1 - propenyl)phenol, which is commercially available. Due to enantiomeric purity (trans (E) configuration) of the (1 -propenyl) group in this molecule the compounds of the present invention according to formula (I) do not contain any cis (Z)- isomers.
  • D in formula (I) is a difunctional group selected from the following:
  • heterocyclic group with 3 to 5 carbon atoms and at least one nitrogen sulfur or oxygen atom in the heterocyclic ring;
  • (e) bridged multicyclic group consisting of at least two groups selected from the following: monocarbocyclic aromatic groups, dicarbocyclic aromatic groups, cycloalkylene groups; wherein these groups are linked to each other by direct carbon-carbon bonds or by divalent groups; wherein preferably the divalent groups are selected from the following: oxy-group, thio-group, alkylene-group with 1 to 3 carbon atoms, sulfone-group, methanone-group;
  • AR 1 , AR 2 , AR 3 , AR 4 , AR 5 and AR 6 are independently difunctional aliphatic or aromatic residues; and wherein n is an integer selected in the range from 2 to 100 and represents the number of repeating structural units in the polymer backbone; group of the following structure
  • R 26 is a monofunctional group selected from the following: alkyl or alkenyl group with 2 to 12 carbon atoms,
  • D in formula (I) is a difunctional group selected from the following:
  • n is an integer selected in the range from 2 to 100 and represents the number of repeating structural units in the polymer backbone.
  • the present invention further relates to curable compositions comprising: i. at least one [(2-ethoxy-5-trans-1 -propen-1 -yl)-phenoxy]-terminated
  • D is an x-functional group; and x is an integer > 2; and ii. at least one polyimide of formula (II)
  • B is a difunctional group containing a carbon-carbon double bond
  • A is a y-functional group
  • y is an integer > 2.
  • compositions of the present invention D in formula (I) is a difunctional group selected from the following:
  • heterocyclic group with 3 to 5 carbon atoms and at least one nitrogen sulfur or oxygen atom in the heterocyclic ring;
  • (e) bridged multicyclic group consisting of at least two groups selected from the following: monocarbocyclic aromatic groups, dicarbocyclic aromatic groups, cycloalkylene groups; wherein these groups are linked to each other by direct carbon-carbon bonds or by divalent groups; wherein preferably the divalent groups are selected from the following: oxy-group, thio-group, alkylene-group with 1 to 3 carbon atoms, sulfone-group, methanone-group; one of the groups of the following structures
  • AR 1 , AR 2 , AR 3 , AR 4 , AR 5 and AR 6 are independently difunctional aliphatic or aromatic residues; and wherein n is an integer selected in the range from 2 to 100 and represents the number of repeating structural units in the polymer backbone; group of the following structure
  • R 26 is a monofunctional group selected from the following: alkyl or alkenyl group with 2 to 12 carbon atoms,
  • compositions of the present invention D in formula (I) is a difunctional group selected from the following:
  • n is an integer selected in the range from 2 to 100 and represents the number of repeating structural units in the polymer backbone.
  • the y-functional group A in the polyimide according to formula (II) is selected from the following difunctional groups: a) alkylene group with 2 to 12 carbon atoms; b) cycloalkylene group with 5 to 6 carbon atoms; c) heterocyclic group with 4 to 5 carbon atoms and at least one nitrogen, oxygen, or sulphur atom in the ring; d) mono- or dicarbocyclic group; e) bridged multicyclic group consisting of at least two groups selected from the following: monocarbocyclic aromatic groups, dicarbocyclic aromatic groups, cycloalkylene groups; wherein these groups are linked to each other by direct carbon-carbon bonds or by divalent groups; wherein preferably the divalent groups are selected from the following: oxy-group, thio-group, alkylene-group with 1 to 3 carbon atoms, sulfone-group, methanone-group, or one of the following groups
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 are independently alkyl groups with 1 to 6 carbon atoms;
  • R 7 and R 8 are independently alkylene groups with 1 to 6 carbon atoms; group defined by formula (III)
  • R 9 is one of the following groups
  • compositions of the present invention B in the polyimide according to formula (II), is selected from the following difunctional groups:
  • polyimide according to formula (II) is selected from the following:
  • 4,4'-bismaleimidodiphenylmethane bis(3-methyl-5-ethyl-4- maleimidophenyl)methane, bis(3,5-dimethyl-4-maleimidophenyl)methane, 4,4'- bismaleimidodiphenylether, 4,4'-bismaleimidodiphenylsulfone, 3,3'- bismaleimidodiphenylsulfone, bismaleimidodiphenylindane, 2,4-bismaleimidotoluene, 2,6-bismaleimidotoluene, 1 ,3-bismaleimidobenzene, 1 ,2-bismaleimidobenzene, 1 ,4- bismaleimidobenzene, 1 ,2-bismaleimidoethane, 1 ,6-bismaleimidohexane, 1 ,6- bismaleimido-(2,2,4-trimethyl)hexane, 1 ,6-bismale
  • compositions of the present invention D in formula (I) is a difunctional group selected from the following:
  • n is an integer selected in the range from 2 to 100 and represents the number of repeating structural units in the polymer backbone.
  • polyimide according to formula (II) is selected from the following:
  • 4,4'-bismaleimidodiphenylmethane bis(3-methyl-5-ethyl-4- maleimidophenyl)methane, bis(3,5-dimethyl-4-maleimidophenyl)methane, 4,4'- bismaleimidodiphenylether, 4,4'-bismaleimidodiphenylsulfone, 3,3'- bismaleimidodiphenylsulfone, bismaleimidodiphenylindane, 2,4- bismaleimidotoluene, 2,6-bismaleimidotoluene, 1 ,3-bismaleinnidobenzene, 1 ,2- bismaleinnidobenzene, 1 ,4-bismaleimidobenzene, 1 ,2-bismaleinnidoethane, 1 ,6- bismaleinnidohexane, 1 ,6-bismaleimido-(2,2,4-trimethyl)hexane
  • the present invention further relates to curable compositions as defined above further comprising one or more cure inhibitors to retard the polymerisation reaction, thus modifying processability and storage stability of the compositions and intermediate products, such as prepregs, moulding compounds and resin solutions.
  • Suitable cure inhibitors are Hydroquinone, 1 ,4-Naphthoquinone, lonole and phenothiazine which are used at concentrations between 0.1 wt% and 2.0 wt%, based on the total weight of the composition. It is advantageous to dissolve the inhibitor in one of the components prior to the preparation of the mixture.
  • the present invention further relates to curable compositions as defined above further comprising one or more cure accelerators in order to accelerate the curing process.
  • cure accelerators are added in an amount of 0.01 wt% to 5 wt%, preferably in an amount of 0.1 wt% to 2 wt% based on the total weight of the curable composition.
  • Suitable cure accelerators include ionic and free radical polymerization catalysts.
  • free radical polymerization catalysts include (a) organic peroxides such as ditertiary butyl peroxide, diamylperoxide and t- butylperbenzoate and (b) azo compounds such as azobisisobutyronitrile.
  • ionic catalysts are alkali metal compounds, tertiary amines such as triethylamine, dimethylbenzylannine, dimethylaniline,azabicyclooctane, heterocyclic amines such as quinoline, N-methylmorpholine, methylimidazole and phenylimidazole and
  • the cure accelerators can be admixed with the components of the curable composition or may be added during the production of the prepolymers either by a powder blending process or by a solvent blending process.
  • Curable Compositions Comprising a Secondary Co-monomer Component
  • the present invention further relates to curable compositions comprising in addition to the at least one [2-ethoxy-5-(trans-1 -propen-1 -yl)phenoxy]- terminated compound according to formula (I) as defined above and the at least one polyimide of formula (II) as defined above, a secondary co-monomer component, which consists of one or a combination of at least two co-monomers selected from the following: alkenylphenol, alkenylphenyl ether, alkenyl phenol ether, polyamine, aminophenol, aminoacid hydrazide, cyanate ester, diallyl phthalate, triallyl isocyanurate, triallyl cyanurate, styrene, divinylbenzene, wherein the secondary co- monomer component represents between 1 wt% and 30 wt% of the total
  • These secondary co-monomers may act as diluents for the compositions of the invention modifying their viscosity and/or processability.
  • the secondary co- monomers may also act as cure accelerators or as cure retardants in the
  • compositions of the invention are provided.
  • the secondary co-monomer component consists of one or a combination of at least two co-monomers selected from the following:
  • R 10 is a difunctional group
  • R 11 and R 12 are independently alkenyl groups with 2 to 6 carbon atoms a compound of formula (V)
  • R 13 is a difunctional group
  • R 14 and R 15 are independently alkenyl groups with 2 to 6 carbon atoms
  • R 16 is a difunctional group
  • R 17 and R 18 are independently alkenyl groups with 2 to 6 carbon atoms; a compound of formula (VII)
  • R 19 is a difunctional group
  • R 20 and R 21 are independently alkenyl groups with 2 to 6 carbon atoms
  • R 22 is a y ' -functional group
  • R 23 is an alkenyl group with 2 to 6 carbon atoms
  • y ' is an integer > 2;
  • R 24 is a y " -functional group
  • R 25 is alkenyl group with 2 to 6 carbon atoms
  • y " is an integer > 2.
  • residues R 10 in formula IV and R 13 in formula V are selected from the following groups:
  • R 22 in formula VIII and R 24 in formula IX are difunctional groups selected from the following groups
  • residues R 23 in formula VIII and R 25 in formula IX are 1 -propen-1 -yl or 2- propen-1 -yl groups.
  • the secondary co-monomer component consists of one or a combination of at least two co-monomers selected from the following:
  • the [2-ethoxy-5-trans-(1 -propen-1 -yl)phenoxy]-substituted compounds according to formula (I) can be synthesized by a variety of well known chemical reactions from trans (E)-2-Ethoxy-5-(1 -propenyl)phenol (Vanitrope) and appropiate polyfunctional, preferably difunctional, starting materials.
  • (e) bridged multicyclic group consisting of at least two groups selected from the following: monocarbocyclic aromatic groups, dicarbocyclic aromatic groups, cycloalkylene groups; wherein these groups are linked to each other by direct carbon-carbon bonds or by divalent groups; wherein preferably the divalent groups are selected from the following: oxy-group, thio-group, alkylene-group with 1 to 3 carbon atoms, sulfone-group, methanone-group; are obtained by the reaction of 2-ethoxy-5-trans (1 -propen-1 -yl)phenol (Vanitrope) in the form of its sodium or potassium salt with the corresponding dihalo compound , Hal-D-Hal, by use of the Williamson ether synthesis route, or by a nucleophilic halodisplacement reaction.
  • monocarbocyclic aromatic groups dicarbocyclic aromatic groups, cycloalkylene groups
  • divalent groups are selected from the following: oxy-group, thio-group,
  • a preferred group of target compounds (I) may be prepared by reaction of Vanitrope, in the form of its sodium or potassium salt, with ⁇ , ⁇ -dihaloalkanes, in a neutral solvent at temperatures around 60 °C - 80 °C, to provide a, -bis(trans-2 ethoxy-5-(1 - propenyl))alkanes.
  • Another group of compounds according to formula (I) may be prepared by reaction of Vanitrope with dihalobenzophenone at a temperature of 170 °C - 190 °C in the presence of N-methyl pyrrol idone as a solvent and a catalyst, for example potassium carbonate.
  • the synthesis may be modified such that dihalobenzophenone is reacted with a bisphenol, resorcinol or hydroquinone or bisphenol-A for example, to form a halo-terminated polyetherketone which is then endcapped with Vanitrope.
  • 4,4'- dichlorodiphenylsulfone may be used instead of dihalobenzophenone in the syntheses to provide the corresponding 4,4'-bis(2-ethoxy-5-trans-(1 -propen-1 - yl)phenoxy)diphenylsulfone or the corresponding Vanitrope-endcapped
  • n is an integer selected in the range from 2 to 100 and represents the number of repeating structural units in the polymer backbone, and wherein AR 1 and AR 2 are independently difunctional aliphatic or aromatic residues, can be synthesized from the corresponding dicarboxylic acids and Vanitrope by an esterification reaction. Vanitrope terminated polyesters can also be obtained from carboxyterminated polyesters and Vanitrope through esterification.
  • AR 3 is a difunctional aliphatic or aromatic residue
  • AR 3 can be prepared by the fusion reaction of epoxy compounds with Vanitrope at temperatures between 80 °C and 150 °C in the presence of a catalyst such as triphenylphosphine or alkylt phenylphosphonium halides.
  • the reaction may be performed in the presence of an organic solvent or in the absence of a diluent.
  • Vanitrope and polyepoxy compound may be such that no residual epoxy groups remain at the end of the reaction or the amount of Vanitrope may be lower than stoichiometric to provide a compound containing free unreacted epoxy groups.
  • the preferred epoxy compounds to be used in this synthesis are 1 ,3-bisglycidylresorcinol, 4,4'-bisglycidylbisphenol-A, 4,4'-bisgycidylbisphenol-F and any other glycidylethers of bisphenols or polyphenols such as phenolnovolaks or bisphenolnovolaks. Also triglycidy-p-aminophenol or tetraglycidymethylene dianiline are suitable starting materials. High molecular weight phenoxy resins synthesized from polyepoxy resin and bisphenols with terminal epoxy groups are suitable epoxy compounds for Vanitrope terminated phenoxy resins.
  • n is an integer selected in the range from 2 to 100 and represents the number of repeating structural units in the polymer backbone, can be synthesized by reaction of Vanitrope with phosgene to provides the Vanitrope carbonate, with bisphenol-A bischloroformiate to provide Vanitrope/Bisphenol-A carbonate, or with a chlorofomiate-terminated polycarbonate to a Vanitrope terminated polycarbonate.
  • D represents one of the following structures
  • n is an integer selected in the range from 2 to 100 and represents the number of repeating structural units in the polymer backbone, and wherein AR 4 and AR 6 are independently difunctional aliphatic or aromatic residues, can be synthesized by reaction of Vanitrope with a bis-isocyanate or an isocyanate terminated
  • organic polyisocyanates may be employed to react with the Vanitrope including aromatic, aliphatic and cycloaliphatic polyisocyanates.
  • Representative compounds include toluene 2,6-diisocyanate, toluene 2,4- diisocyanate, m-phenylene diisocyanate, 4,4'-bisphenylene diisocyanate, 1 ,5- naphthalene diisocyanate, 4,4'bisisocyanatodiphenylmethane, 4,4'- bisisocyanatodiphenylether, 1 ,6-bisisocyanatohexane, 2,2,4-trimethyl hexamethylene diisocyanate, isophorone diisocyanate and any other polyisocyanate.
  • advantageous polyisocyanates to be reacted with Vanitrope are those obtained by the reaction of a bis-isocyanate with polyalkylene ether glycols, providing isocyanate terminated macropolyisocyanates. Products based on polypropylene ether glycols are of particular interest because of their low moisture absorption.
  • the present invention further relates to processes for the manufacture of curable compositions according to the invention, comprising the step of blending the components of the composition using a powder-, melt-, solvent-assisted or other blending process resulting in solid, low-melting, or tacky curable compositions.
  • the present invention relates to processes for the manufacture of curable compositions of the invention, comprising the step of: blending the components of a composition comprising a comonomer component of the invention and a polyimide component as defined above at a temperature ranging from 70 °C to 250 °C to obtain curable compositions as low melting low viscosity masses (resins).
  • the blending temperatures may be varied over a relatively wide range.
  • the method is carried out at temperatures from 90 °C to 170 °C, preferably from 100 °C to 160 °C.
  • the present invention relates to processes for the manufacture of curable compositions of the invention, comprising the step of:
  • curable composition as a solvent-free, low melting, low viscosity mass (resin).
  • the comonomer component of the invention and the polyimide component as defined above are dissolved in the solvent at elevated temperature.
  • Suitable solvents and diluents are all customary inert organic solvents. They include but are not limited to ketones such as acetone, methylethyl ketone, cyclohexanone; glycol ethers such as methyl glycol, methyl glycol acetate, propylene glycol monomethyl ether (methyl proxitol), methyl proxitol acetate, diethylene glycol, and diethylene glycol monomethyl ether; toluene and xylene, preferably in combination with 1 ,3-dioxolane as a co-solvent.
  • ketones such as acetone, methylethyl ketone, cyclohexanone
  • glycol ethers such as methyl glycol, methyl glycol acetate, propylene glycol monomethyl ether (methyl proxitol), methyl proxitol acetate, diethylene glycol, and diethylene glycol monomethyl ether
  • the solvent is 1 ,3-dioxolane or a 1 ,3-dioxolane-containing solvent.
  • the amount of 1 ,3-dioxolane in the solvent mixture ranges from 20 wt% to 80 wt%, e.g. from 30 wt% to 70 wt% or from 40 wt% to 60 wt%.
  • the molar ratio between the unsaturated imide groups and reactive alkenyl groups in the composition ranges from 1 .0 to 0.1 , e.g.
  • Preparation of the curable compositions of this invention can be carried out without any diluent or solvent in that the components as powders, pastes or liquids are intimately mixed, if necessary at elevated temperature, to obtain a homogeneous blend of the monomers or a prepolymer depending on the duration of the
  • An extruder process may be used to control and set the required melting temperature, to provide the necessary temperature for prepolymerization in the reaction zone and to set the time at temperature by the throughput.
  • the extrudate, after cooling, may be a hot melt product or a solidified melt which can be milled to a resin powder.
  • reaction inhibitors are hydroquinone, 1 ,4-naphthoquinone and phenothiazine which are used at
  • concentrations between 0.1 wt% and 2.0 wt%, based on the total weight of the composition. It is advantageous to dissolve the inhibitor in one of the components prior to the preparation of the composition.
  • compositions comprising a secondary co-monomer component
  • the curable compositions of the present invention may be processed from the melt.
  • a secondary co-monomer component may be added, which consists of one or more co-monomers selected from the following: alkenylphenol, alkenylphenyl ether, alkenyl phenol ether, polyamine, aminophenol, aminoacid hydrazide, cyanate ester, diallyl phthalate, triallyl isocyanurate, triallyl cyanurate, styrene, divinylbenzene, wherein the secondary co-monomer component represents between 1 wt% and 30 wt% of the total composition.
  • allyl-type secondary co-monomer components such as diallylbisphenol-A, bisphenol-A diallylether, diallylphthalate, triallylisocyanurate and triallylcyanurate when added to the curable composition slow down polymerisation kinetics and therefore widen the processing window.
  • Secondary co-monomer components like styrene or divinylbenzene are very effective in concentrations between 10 wt% and 20 wt% but accelerate polymersation kinetics, providing faster curing resins and lowering their polymerisation temperature. Therefore, secondary co-monomer components are an additional tool to modify cure velocity of the curable compositions of the invention.
  • compositions comprising thermoplastic toughening modifier
  • Curable compositions of the present invention may further include from 0 wt% to about 30 wt%, based on the total weight of the composition, of a thermoplastic polymer such as, for example, a polyaryl ether, a polyaryl sulfone, a polyarylate, a polyamide, a polyaryl ketone, a polyimide, a polyimide-ether, a polyolefin, an ABS resin, a polydiene or diene copolymer or mixtures thereof.
  • Thermoplastics such as polysulfons and phenoxy resins are particularly miscible with the curable
  • compositions of the present invention may be used to adjust resin viscosity and control flow during cure.
  • Thermoplastic polymers may also be added to improve the fracture toughness.
  • Thermoplastic polymers can be added to the curable
  • compositions as fine powders may be dissoved in either the [2-ethoxy-5-trans-(1 - propen-1 -yl)phenoxy]-substituted compound (I) or a secondary co-monomer component.
  • curable compositions of the invention can be isolated by customary techniques and processes (cf. e.g. examples section). Pre-polymers of Curable Compositions of the Invention and Processes for their
  • the present invention relates to the use of a curable composition as defined above for the preparation of a prepolymer.
  • curable compositions of the invention are useful for the preparation of partially cross-linked products (i.e. prepolymers).
  • Prepolymers are prepared by heating curable compositions as defined above to temperatures of 80 °C to 350 °C, preferably to 100 °C to 250 °C for a time sufficient to obtain a prepolymer which is still formable upon applying heat and/or pressure. Optionally this is performed in the presence of a cure catalyst or cure stabilizer.
  • the invention therefore provides compounds of the general formula
  • aromatic rings may be substituted or unsubstituted.
  • the invention further provides reacting meta propenylphenol with benzophenone.
  • aromatic rings may be substituted or unsubstituted as curatives for polymaleinnide resins.
  • polymaleimides such as bismaleimides as we have found the meta compound to be more reactive with bismaleimides than the ortho and the para version.
  • the invention further provides a polymaleinnide, preferably a bismaleimide, containing a compound of the general formula
  • the aromatic rings may be substituted or unsubstituted as a curative.
  • Bismaleimides are a class of compounds comprising two maleimide groups
  • thermosetting resins which can be used in fibre reinforced composites. Curatives are included with the resin to lower the cure temperature and/or control the rate of cure. Additionally they are included to control the low temperature viscosity of the uncured resin to aid in moulding.
  • the meta and para compounds of this invention are particularly useful in these applications.
  • Para and meta propenylphenol were prepared by reacting para or meta phenoxy benzladehyde with triphenyl phosphobromide and tertiary butyl potassium in tetrahyde furan as follows.
  • the para or meta propenylphenol was converted to the phenolate and then extracted into an aqueous phase where it was acidified and re-extracted into ethylacetate.
  • the structure of the para or meta propenylphenol was verified by NMR showing the presence of both cis and trans isomers.
  • the materials were used as curatives in a bismaleimide.
  • Suitable catalysts include ionic and free radical polymerization catalysts.
  • free radical polymerization catalysts include (a) organic peroxides such as ditertiary butyl peroxide, diamylperoxide and t- butylperbenzoate and (b) azo compounds such as azobisisobutyronitrile.
  • ionic catalysts examples include alkali metal compounds, tertiary amines such as triethylamine, dimethylbenzylannine, dimethylaniline,azabicyclooctane, heterocyclic amines such as quinoline, N-methylmorpholine, methyl imidazole and phenylimidazole and phosphorous compounds such as triphenylphosphine and quaternary phosphonium halides.
  • the catalysts can be admixed with the components of the curable
  • composition or may be added during the production of the prepolymers either by a powder blending process or by a solvent blending process as described above.
  • the present invention further comprises curable pre-polymers obtainable from curable compositions according to the invention, by a process comprising the step of heating the curable composition to a temperature in the range of 50 °C to 250 °C, preferably to 70 °C to 170 °C, for a time sufficient to obtain a pre- polymer, which is still formable upon the application of heat and/or pressure.
  • high boiling point polar solvents such as dimethylformamide, dimethylacetamide, N-methyl pyrrol idone, and butyrolactone can in principle be used.
  • solvents generally yields prepolymers with high contents of residual solvents.
  • low boiling solvent mixtures containing 1 ,3-dioxolane may be used. These preferably include, but are not limited to, solvent mixtures of 1 ,3-dioxolane with ketones such as acetone, methylethylketone, cyclohexanone or glycol ethers such as ethylene glycol ether, propylene glycol ether, butylene glycol ether and their acetates.
  • ketones such as acetone, methylethylketone, cyclohexanone
  • glycol ethers such as ethylene glycol ether, propylene glycol ether, butylene glycol ether and their acetates.
  • solvent mixtures comprising 1 ,3-dioxolane and the above-identified solvents
  • solvent mixtures are useful for the preparation of solvent free prepolymers.
  • the so obtained prepolymers can be processed to void-free fiber-reinforced composites.
  • the solvent mixture comprises up to 50 wt%, preferably up to 40 wt% of ketones such as acetone, methylethylketone, cyclohexanone, or glycol ethers such as ethylene glycol ether, propylene glycol ether, butylene glycol ether, and their acetates based on the total weight of the solvent mixture.
  • ketones such as acetone, methylethylketone, cyclohexanone
  • glycol ethers such as ethylene glycol ether, propylene glycol ether, butylene glycol ether, and their acetates based on the total weight of the solvent mixture.
  • a solution of the curable composition of the invention comprises from 30 wt% to 70 wt%, preferably from 40 wt% to 60 wt% of solvent, e.g. of 1 ,3- dioxolane, or solvent mixtures comprising 1 ,3-dioloxane, and the above-identified solvents.
  • solvent e.g. of 1 ,3- dioxolane, or solvent mixtures comprising 1 ,3-dioloxane, and the above-identified solvents.
  • concentrations are typically used in industrial dip coating processes.
  • the prepolymers of the curable composition of the invention can be isolated by generally customary processes, e.g. by evaporation of the solvent if the subsequent use is solvent free.
  • the prepolymers which are obtained according to the method of the invention are still soluble in selected organic solvents. Further, the prepolymers of the invention are still fusible and formable upon the application of heat and/or pressure.
  • the present invention relates to a curable prepolymer obtainable according to a method as described above.
  • the invention relates to the use of a curable composition as defined above or of a prepolymer as defined above for the preparation of a crosslinked polymer.
  • curable compositions and curable prepolymers of the invention are useful for the preparation of crosslinked polymers.
  • the invention relates to a method for the preparation of a crosslinked polymer comprising the step of:
  • reaction temperatures may be varied over a relatively wide range.
  • the method is carried out at temperatures from 80 °C to 270 °C, more preferably from 90 °C to 260 °C, most preferably from 100 °C to 250 °C.
  • the present invention further comprises crosslinked polymers obtainable from the curable compositions according to the invention by a process comprising the step of heating the curable composition to a temperature in the range of 70 °C to 280 °C for a time sufficient to obtain a polymer.
  • the conversion may take place with simultaneous shaping under pressure to obtain mouldings, laminates, adhesive bonds, and foams.
  • the curable composition it is possible to admix the curable composition with additives such as fillers, pigments, colorants, and flame retardants.
  • Suitable fillers are glass- or carbon fibers, graphite, quartz, metal powders, and metal oxides.
  • Mould release agents such as silicone oil, waxes, Zn and K-stearates may also be added.
  • the present invention relates to mouldings, laminates, adhesive bonds, and foams obtainable by processing of the curable composition and curable prepolymers of the invention.
  • curable compositions and prepolymers of the invention are useful for the preparation of composite materials.
  • the curable compositions of the present invention can be processed by known methods of the powder moulding industry for producing mouldings, with curing taking place with simultaneous shaping under pressure.
  • the curable compositions are admixed with additives such as fillers, colorants and flame retardants.
  • additives such as fillers, colorants and flame retardants.
  • Ideal fillers for example are short glass fibers, short carbon fibers or aramid fibers, paticulate fillers such as quartz, silica, ceramics, metal powders and carbon powder.
  • two or more different fillers may be used at the same time.
  • One of the preferred uses of the curable compositions of the present invention is as binders for fiber composites.
  • fibers such as glass, carbon or aramid in the form of ravings, fabrics, short fiber mats, or felts are impregnated with the curable composition, employing a solution of the said curable composition to impregnate said reinforcements.
  • a prepreg is left, which in the second phase may be cured at a temperature between 180 °C and 350 °C, optionally under pressure.
  • a preferred application of the curable compositions of the present invention is as hot-melt resins for fiber-reinforced composites.
  • the curable compositions are processed as hot melts to a resin film on a carrier foil, subsequently fibers, in the form of rovings or fabrics, are pressed into the molten resin film to form a prepreg.
  • curable compositions which have a low viscosity at low temperature are advantageous in order to provide adequate impregnation of fiber rovings or fabric.
  • One of the preferred applications of the curable compositions of the present invention is as resins for fiber laminates.
  • Prepregs manufactured by either the solvent/sol ution- or the hot-melt process from glass-, carbon- or aramid fibers, in the form ofises or rovings, are stacked to provide a prepreg laminate, which subsequently is cured under pressure or in a vacuum bag at a temperature between 150 °C and 280 °C preferably between 170 °C and 260 °C.
  • the invention relates to a method for the preparation of a composite material comprising the steps of:
  • the curable composition or the prepolymer as defined above is applied onto or blended with a fibrous or particulate reinforcement (filler) with the use of standard processing techniques, e.g with the use of the hot melt or solution-based prepregging, resin transfer moulding (RTM), resin infusion moulding (RIM), filament winding (FW) or compounding techniques.
  • a fibrous or particulate reinforcement filler
  • standard processing techniques e.g with the use of the hot melt or solution-based prepregging, resin transfer moulding (RTM), resin infusion moulding (RIM), filament winding (FW) or compounding techniques.
  • Curing may be carried out at temperatures ranging from 70 °C to 280 °C, preferably at temperatures ranging from 80 °C to 270 °C, more preferably at temperatures ranging from 90 °C to 260 °C, most preferably at temperatures ranging from 100 °C to 250 °C for a time sufficient to complete cure.
  • the present invention further comprises processes for the manufacture of composite materials comprising the steps of combining a curable composition according to the invention or a curable pre-polymer according to the invention, with a fibrous or particulate reinforcement, and curing the resultant product.
  • the composite material is a fiber-reinforced composite.
  • the composite material is a particulate-filled composite.
  • the present invention relates to a method for the preparation of a composite material comprising the steps of:
  • Process step c) may be carried out at temperatures ranging from 70 °C to 280 °C, preferably at temperatures ranging from 80 °C to 270 °C, more preferably at temperatures ranging from 90 °C to 260 °C, most preferably at temperatures ranging from 100 °C to 250 °C for a time sufficient to complete cure.
  • the conversion of the curable compositions or prepolymers of the invention into the crosslinked (cured) polymer may be carried out, in the presence of a curing catalyst as defined above.
  • a preferred application of the curable compositions of the invention is resins for fiber- reinforced composites.
  • the curable compositions of the invention are processed as hot melts to resin film on a carrier foil, which is subsequently used to prepare prepolymers by pressing fibers in the form of rovings or fabrics into the resin film.
  • curable compositions which have a low viscosity at low temperature are advantageous in order to provide adequate impregnation of fiber rowings or fabric.
  • the present invention comprises composite materials obtainable by a process according to the invention.
  • curable means that an original compound(s) or mixture material(s) can be transformed into a solid, substantially non-flowing material by means of chemical reaction, crosslinking, radiation crosslinking or the like.
  • mixture means a physical or mechanical aggregation or a combination of two or more individual, chemically distinct compounds that are not chemically united.
  • polyimide component means one polyimide or a mixture of two or more polyimides, preferably one polyimide or a mixture of two to four polyimides.
  • the term "comonomer” means a compound that can undergo polymerization or copolymerization, thereby contributing constitutional units to the essential structure of a polymer.
  • the term "comonomer component” means one comonomer or a mixture of two or more comonomers, preferably one comonomer or a mixture of two to four comonomers.
  • alkenylphenol means organic compounds comprising at least one alkenyl-substituted phenol group.
  • alkenylphenol comprises alkenylphenols, wherein two phenol groups are bridged via a difunctional group, e.g. alkenylbisphenols. Examples include 3,3'-diallyl-bisphenol A.
  • alkenylphenyl ether means organic compounds
  • alkenylphenyl ether comprises alkenylphenyl ethers, wherein two phenyl groups are bridged by a difunctional group, e.g. alkenylbisphenol ether. Examples include diallyl ether of bisphenol A.
  • alkenylphenol ether means organic compounds comprising at least one alkenylphenoxy group, e.g. an ether group wherein the ether oxygen atom is connected on one hand to an alkenylphenyl group and on the other hand to a an alkyl or an aryl group.
  • alkenylphenol ether comprises organic compounds, wherein two alkenylphenoxy groups are bridged by a difunctional group, e.g. by an aromatic group such as a benzophenone group. Examples include bis-(o- propenylphenoxy)benzophenone.
  • polyamine means an organic compound having two or more primary amino groups -IMH2. Examples include, but are not limited to 4,4'- diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, diaminodiphenylindane, m-phenylenediamine, p-phenylenediamine, 2,4- diaminotoluene, 2,6-diaminotoluene, m-xylylenediamine and aliphatic diamines such as ethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, 1 ,12- diaminododecane.
  • aminophenol means amino-substituted phenols. Examples include m-aminophenol and p-aminophenol.
  • amino acid hydrazides means any hydrazides of amino acids. Examples include m-aminobenzhydrazide and p-aminobenzhydrazide.
  • cyanate ester means a bisphenol or polyphenol, e.g.
  • novolac derivative, in which the hydrogen atom of the phenolic OH group is substituted by a cyano-group, resulting in an -OCN group.
  • examples include bisphenol A dicyanate ester, commercially available as, e.g. Primaset BADCy from Lonza or AroCy B-10 from Huntsman, as well as other Primaset or AroCy types, e.g.
  • Any bond intersected by a bracket indicates a bond that connects the moiety within the bracket to other moieties of the same compound.
  • the two bonds of the ethenyl group intersected by the bracket on the right side connect this moiety to other moieties of the compound containing this ethenyl group.
  • halogen means a fluorine, chlorine, bromine or iodine atom, preferably a fluorine or chlorine atom, more preferably a fluorine atom.
  • alkyi means a straight-chain or branched alkyi group.
  • alkyi with n to m carbon atoms means an alkyi group with n to m carbon atoms. If not denoted otherwise, "alkyi” means an alkyi with 1 to 6 carbon atoms.
  • preferred alkyi groups are straight-chain or branched alkyi groups with 1 to 4 carbon atoms. Examples of straight-chain and branched alkyl groups include, but are not limited to methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert. -butyl, the isomeric pentyls, the isomeric hexyls, preferably methyl and ethyl and most preferred methyl .
  • alkylene means a difunctional alkyl group.
  • alkylene with n to m carbon atoms means an alkylene group with n to m carbon atoms. If not denoted otherwise, "alkylene” means an alkylene with 1 to 12 carbon atoms.
  • preferred alkylene groups are alkylene groups with 1 to 9 carbon atoms, more preferably from 1 to 6 carbon atoms. Examples include, but are not limited to methylene, ethylene, propylene, butylene, hexamethylene and 2,2,4-trimethylhexamethylene. Particularly preferred is 2,2,4-trimethylhexamethylene.
  • alkenylene means a difunctional alkenyl group.
  • alkenylene with n to m carbon atoms means an alkenylene group with n to m carbon atoms. If not denoted otherwise, "alkenylene” means an alkenylene with 2 to 12 carbon atoms.
  • preferred alkenylene groups are alkenylene groups with 2 to 10 carbon atoms, more preferably from 2 to 6 carbon atoms. Examples include, but are not limited to ethenylene, propenylene, and butenylene. Particularly preferred is ethenylene.
  • alkoxy means a straight-chain or branched alkyl group, which is bonded to the compound via an oxygen atom (-O-).
  • alkoxy with n to m carbon atoms means an alkoxy with n to m carbon atoms. If not denoted otherwise, "alkoxy” means a straight-chain or branched alkyl group with 1 to 6 carbon atoms. In the context of the present invention, preferred alkoxy groups are straight-chain or branched alkoxy groups with 1 to 4 carbon atoms.
  • alkenyl means a straight-chain or branched hydrocarbon group comprising a carbon-carbon double bond.
  • alkenyl with n to m carbon atoms means an alkenyl with n to m carbon atoms. If not denoted otherwise,
  • alkenyl means a straight-chain or branched hydrocarbon group comprising a carbon-carbon double bond in any desired position and 2 to 10 carbon atoms.
  • preferred alkenyl groups comprise a carbon-carbon double bond in any desired position and 2 to 6, more preferably 2 to 4 carbon atoms.
  • alkenyl groups include, but are not limited to ethenyl, 1 -propenyl, 2- propenyl, isopropenyl, 1 -butenyl, 2-butenyl, 3-butenyl and isobutenyl. Preferred examples are 1 -propenyl and 2-propenyl.
  • monocarbocyclic group means a “monocarbocyclic aliphatic group” or a “monocarbocyclic aromatic group”.
  • dicarbocyclic group means a a "dicarbocyclic aliphatic group” or a “dicarbocyclic aromatic group” group.
  • monocarbocyclic aliphatic group means a cycloalkylene group.
  • cycloalkyi means a monofunctional carbocyclic saturated ring system.
  • cycloalkyi with n to m carbon atoms means a cycloalkyi with n to m carbon atoms. If not denoted otherwise, "cycloalkyi” means a cycloalkyi group with 5 to 6 carbon atoms. Examples of cycloalkyi groups include, but are not limited to cyclopropanyl, cyclobutanyl, cyclopentanyl, cyclohexanyl, cycloheptanyl or cyclooctanyl, preferably cyclopentanyl and cyclohexanyl.
  • cycloalkylene means a difunctional carbocyclic saturated ring system.
  • cycloalkylene with n to m carbon atoms means a cycloalkylene with n to m carbon atoms. If not denoted otherwise, "cycloalkylene” means a cycloalkylene group with 3 to 8 carbon atoms. In the context of the present invention preferred cycloalkylene groups are cycloalkylene groups with 5 to 7, more preferably 5 or 6 carbon atoms.
  • Examples include, but are not limited to cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene or cyclooctylene, preferably cyclopentylene and cyclohexylene.
  • dicarbocyclic aliphatic group means a difunctional bicyclic condensed, bridged or fused saturated ring system. If not denoted otherwise, “dicarbocyclic aliphatic group” means a difunctional bicyclic condensed, bridged or fused saturated ring system with 9 to 20 carbon atoms. Examples include, but are not limited to decalinyl, hydrindanyl and norbornyl.
  • difunctional mono- or dicyclic aromatic system preferably with 6 to 12 carbon atoms, preferably a monocyclic aromatic system.
  • examples include, but are not limited to, toluene, phenylene, naphthylene, tetrahydronaphthylene, indenylene, indanylene, pentalenylene, fluorenylene and the like, preferably toluene, phenylene or
  • aryl means a monofunctional mono- or dicyclic aromatic system, preferably with 6 to 12 carbon atoms, preferably a monocyclic aromatic system. Examples include, but are not limited to, toluyl, phenyl, naphthyl,
  • heterocyclic group means a “heterocyclic aliphatic group” or a “heterocyclic aromatic group”
  • heterocyclic aliphatic group means a difunctional saturated ring system which, in addition to carbon atoms, comprises one, two or three atoms selected from nitrogen, oxygen and/or sulfur.
  • Preferred heterocyclic aliphatic groups are those containing 3 to 5 carbon atoms and one nitrogen, oxygen or sulfur atom.
  • heterocyclic aromatic group means a monocyclic aromatic 5- or 6- membered ring, which comprises one, two or three atoms selected from nitrogen, oxygen and/or sulfur, or a bicyclic aromatic group comprising two 5- or 6- membered rings, in which one or both rings can contain one, two or three atoms selected from nitrogen, oxygen or sulfur.
  • examples include, but are not limited to pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, oxazolyl, oxydiazolyl, isoxazolyl,
  • bridged multicydic group means a group consisting of at least two groups selected from the following: monocarbocyclic aromatic groups, dicarbocydic aromatic groups, cydoalkylene groups; wherein these groups are linked to each other by direct carbon-carbon bonds or by divalent groups.
  • Preferred divalent groups are oxy-group, thio-group, alkylene-group with 1 to 3 carbon atoms, sulfone-group, methanone-group, and the following groups:
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 are independently alkyl groups with 1 to 6 carbon atoms;
  • R 7 and R 8 are independently alkylene groups with 1 to 6 carbon atoms.
  • bridged multicydic group means a group consisting of two monocarbocyclic aliphatic groups, which are linked to each other by a direct carbon-carbon bond or by a divalent group such as oxy-group, thio-group, alkylene- group with 1 to 3 carbon atoms, sulfone-group, methanone-group, or one of the following groups:
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 are independently alkyl groups with 1 to 6 carbon atoms;
  • R 7 and R 8 are independently alkylene groups with 1 to 6 carbon atoms.
  • bridged multicyclic group means a group consisting of two cyclohexylene groups, which are linked to each other by a direct carbon-carbon bond or by a divalent group such as oxy-group, thio-group, alkylene-group with 1 to 3 carbon atoms, sulfone-group, methanone-group.
  • bridged multicyclic group means a group consisting of two monocarbocyclic aromatic groups, which are linked to each other by a direct carbon-carbon bond or by a divalent group such as oxy-group, thio-group, alkylene- group with 1 to 3 carbon atoms, sulfone-group, methanone-group, or one of the following groups:
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 are independently alkyl groups with 1 to 6 carbon atoms;
  • R 7 and R 8 are independently alkylene groups with 1 to 6 carbon atoms.
  • bridged multicyclic group means a group consisting of two phenylene groups, which are linked to each other by a direct carbon-carbon bond or by a divalent group such as oxy-group, thio-group, alkylene-group with 1 to 3 carbon atoms, sulfone-group, methanone-group.
  • unsubstituted or “substituted” means that the respective groups are unsubstituted or carry from 1 to 4 substituents selected from the following: alkyl, alkoxy, halogen. Preferred substituents are methyl or ethyl.
  • x-functional group As used herein, the terms "x-functional group”, “y-functional group”, “y ' -functional group” and “y “ -functional group” respectively, denote a group, which is bonded to the remainder of the compound via x, y, y ' , or y " bond(s), respectively.
  • the "x-functional group”, “y-functional group”, “y ' -functional group” and “y “ -functional group” is a difunctional group, i.e. x, y, y ' and y " are preferably 2.
  • difunctional group means a group, which is bonded to the remainder of the compoundsvia two bonds.
  • Difunctional groups include but are not limited to, difunctional aliphatic groups and difunctional aromatic groups.
  • Difunctional aliphatic groups include but are not limited to the following groups:
  • Difunctional aromatic groups include but are not limited to the following groups:
  • difunctional groups include, but are not limited to the following groups:
  • Glass transition temperature or “Tg” means the
  • amorphous solid e.g. polymer
  • amorphous solid e.g. polymer
  • vitreous (glassy) state when the polymer becomes brittle on cooling, or soft on heating.
  • a pseudo second order phase transition in which a supercooled melt yields, on cooling, a glassy structure and properties similar to those of crystalline materials, e.g. of an isotropic solid material.
  • thermometer were added 20 g (0,145 mol) of potassium carbonate, and the mixture was heated to 90 °C, at which temperature 36,8 g (0,21 mol) of vanitrope were added within a few minutes. The mixture was then heated at 150 °C for 4 hours and subsequently cooled down to 120 °C. 150 ml of 1 -methoxy-2-propanol were added to the stirred batch, and after cooling to 80 °C 150ml of iso-propanol were added followed by 200 ml of water. At room temperature the precipitate was separated, filtered off, and crystallized from 400 ml of a 3:5 (vol/vol) MTBE/methanol-mixture. Filtration and drying at 70 °C yielded 47g (82,5%) of an off-white crystalline product. Purity: 98,4% (area % by HPLC). Melting point: 106-107 °C.
  • the wet product was stirred in a mixture of 300 ml of 1 - methoxy-2-propanol and 100 ml of methanol at a temperature of 50-70 °C, then cooled down to 10 °C and 300 ml of water were added to the stirred slurry. After stirring for an additional hour the product was filtered off and washed with methanol. The product was dried at 50 °C in a vacuum oven to yield 35,9 g (83%) of an off- white powder. Purity: 99,5% (HPLC area-%). Melting point: 154-155 °C.
  • the curable compositions of the invention can be obtained according to the following general processes: a. Melt process
  • the polymaleinnide of formula (II), or a mixture of two or more polymaleimides, and at least one 2-ethoxy-5-(trans-1 -propen-1 -yl)phenoxy-substituted compound of formula (I) were melt-blended in a temperature range of 120-140 °C until a clear melt was obtained. Subsequently, the melt thus obtained was further heated in the same temperature range for a time sufficient to obtain a stable melt. Finally, the melt was degassed under reduced pressure of 20 hPa [15 mm Hg] for 2-10 minutes to obtain a curable composition. b.
  • Solvent-assisted process The polymaleinnide of formula (II), or a mixture of two or more polymaleimides, and at least one 2-ethoxy-5-(trans-1 -propenyl)phenoxy-substituted compound of formula (I), and optionally one additional co-monomer and toluene in a solids-to-solvent weight ratio of 1 :1 were heated at 90-100 °C until a clear solution was obtained.
  • the resin/solvent ratio may vary, depending on the solubility of components.
  • Reactivity measurements c.1 . Differential scanning calorimetry (DSC)
  • DSC Differential scanning calorimetric traces, obtained at a defined heating rate (10°C/min) in the temperature range from 20 to 380°C, were used to characterize the cure kinetics of the curable compositions of 2-ethoxy-5-(trans-1 -propen-1 -yl)phenoxy- substituted compound (I) and BMI (II).
  • the cure exothermic maximum, TMAX represents the temperature of maximum heat release at the specified heating rate. The higher is TMAX the slower is the cure of a resin.
  • the gel time was measured by placing 1 g of the resin on an electrically heated metal block with a polished surface, which is capable of being maintained at temperatures between 130°C and 230°C, and continuous stirring and probing the molten sample with a wooden rod, as described in the ISO 8987 and ASTM D4217 norms.
  • compositions of BMI (II) and 2-ethoxy-5-(trans-1 -propen-1 -yl)phenoxy-substituted compounds (I), prepared in examples 7 through 16, are compiled in Table 1 .
  • MDAB 4,4'-bismaleimidodiphenylmethane
  • BAC-BMI 1 ,3-bis(maleimidomethy)cyclohexane
  • C353A eutectic mixture of 4,4'-bismaleimidodiphenylmethane, 2,4- bismaleimidotoluene, and 1 ,6-bismaleimido-2,2,4(4,4,2)-trimethylhexane stabilized with hydroquinone, commercial bismaleimide mixture available from Evonik
  • ME-MDAB bis-(3-ethyl-5-methyl-4-maleimidophenyl)methane.
  • TM124 o,o'-diallylbisphenol-A (commercial product available from Evonik
  • TM123 4,4'-bis(o-propenylphenoxy)benzophenone (commercial product available from Evonik Industries);
  • MDAB 4,4'-bismaleimidodiphenylmethane
  • ME-MDAB bis-(3-ethyl-5-methyl-4-maleimidophenyl)methane;
  • C353A eutectic mixture of 4,4'-bismaleimidodiphenylmethane, 2,4- bismaleimidotoluene, and 1 ,6- bismaleimido-2, 2,4(4,4, 2)-trimethylhexane stabilized with hydroquinone,
  • Tmax were found at lower temperatures, for the faster curing mixtures comprising the vanitrope type co-monomers of this invention.
  • D is an x-functional group
  • x is an integer > 2; with the provisio that
  • the x-functional group D is not a polycarbonate with an average molar mass in the range of 15000 g/mol to 150000 g/mol.
  • cycloalkylene group with 5 or 6 carbon atoms; heterocyclic group with 3 to 5 carbon atoms and at least one nitrogen sulfur or oxygen atom in the heterocyclic ring; mono- or dicarbocyclic group bridged multicyclic group consisting of at least two groups selected from the following: monocarbocyclic aromatic groups, dicarbocyclic aromatic groups, cycloalkylene groups; wherein these groups are linked to each other by direct carbon-carbon bonds or by divalent groups; wherein preferably the divalent groups are selected from the following: oxy-group, thio-group, alkylene-group with 1 to 3 carbon atoms, sulfone-group, methanone-group; one of the groups of the following structures
  • AR 1 , AR 2 , AR 3 , AR 4 , AR 5 and AR 6 are independently difunctional aliphatic or aromatic residues; and wherein n is an integer selected in the range from 2 to 100 and represents the number of repeating structural units in the polymer backbone;
  • Curable composition comprising: i. at least one [(2-ethoxy-5-trans-1 -propen-1 -yl)-phenoxy]-terminated
  • D is an x-functional group
  • x is an integer > 2; and at least one polyimide of formula (II)
  • B is a difunctional group containing a carbon-carbon double bond, and A is a y-functional group;
  • cycloalkylene group with 5 or 6 carbon atoms; heterocyclic group with 3 to 5 carbon atoms and at least one nitrogen sulfur or oxygen atom in the heterocyclic ring; mono- or dicarbocyclic group; bridged multicyclic group consisting of at least two groups selected from the following: monocarbocyclic aromatic groups, dicarbocyclic aromatic groups, cycloalkylene groups; wherein these groups are linked to each other by direct carbon-carbon bonds or by divalent groups; wherein preferably the divalent groups are selected from the following: oxy-group, thio-group, alkylene-group with 1 to 3 carbon atoms, sulfone-group, methanone-group; one of the groups of the following structures
  • AR 1 , AR 2 , AR 3 , AR 4 , AR 5 and AR 6 are independently difunctional aliphatic or aromatic residues; and wherein n is an integer selected in the range from 2 to 100 and represents the number of repeating structural units in the polymer backbone; group of the following structure
  • R 26 is a monofunctional group selected from the following: alkyl or alkenyl group with 2 to 12 carbon atoms,
  • the y-functional group A in the polyimide according to formula (II) is selected from the following difunctional groups: alkylene group with 2 to 12 carbon atoms cycloalkylene group with 5 to 6 carbon atoms c) heterocyclic group with 4 to 5 carbon atoms and at least one nitrogen, oxygen, or sulphur atom in the ring; mono- or dicarbocyclic group e) bridged multicyclic group consisting of at least two groups selected from the following: monocarbocyclic aromatic groups, dicarbocyclic aromatic groups, cycloalkylene groups; wherein these groups are linked to each other by direct carbon-carbon bonds or by divalent groups; wherein preferably the divalent groups are selected from the following: oxy-group, thio-group, alkylene-group with 1 to 3 carbon atoms, sulfone-group, methanone-group, or one of the following groups
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 are independently alkyl groups with 1 to 6 carbon atoms;
  • R 7 and R 8 are independently alkylene groups with 1 to 6 carbon atoms; f) a group defined by fornnula (III)
  • R 9 is one of the following groups
  • polyimide according to formula (II) is selected from the following:
  • 4,4'-bismaleimidodiphenylmethane bis(3-methyl-5-ethyl-4- maleimidophenyl)methane, bis(3,5-dimethyl-4-maleimidophenyl)methane, 4,4'- bismaleimidodiphenylether, 4,4'-bismaleimidodiphenylsulfone, 3,3'- bismaleimidodiphenylsulfone, bismaleimidodiphenylindane, 2,4- bismaleimidotoluene, 2,6-bismaleimidotoluene, 1 ,3-bismaleimidobenzene, 1 ,2- bismaleimidobenzene, 1 ,4-bismaleimidobenzene, 1 ,2-bismaleimidoethane, 1 ,6- bismaleimidohexane, 1 ,6-bismaleimido-(2,2,4-trimethyl)hexane, 1 ,6- bismale
  • n is an integer selected in the range from 2 to 100 and represents the number of repeating structural units in the polymer backbone. and wherein the polyimide according to formula (II) is selected from the following:
  • 4,4'-bismaleimidodiphenylmethane bis(3-methyl-5-ethyl-4- maleimidophenyl)methane, bis(3,5-dimethyl-4-maleimidophenyl)methane, 4,4'- bismaleimidodiphenylether, 4,4'-bismaleimidodiphenylsulfone, 3,3'- bismaleimidodiphenylsulfone, bismaleimidodiphenylindane, 2,4- bismaleimidotoluene, 2,6-bismaleimidotoluene, 1 ,3-bismaleimidobenzene, 1 ,2- bismaleimidobenzene, 1 ,4-bismaleimidobenzene, 1 ,2-bismaleimidoethane, 1 ,6- bismaleimidohexane, 1 ,6-bismaleimido-(2,2,4-trimethyl)hexane, 1 ,6- bismale
  • Curable pre-polymer obtainable from a curable composition according to any one of variants 4 to 10, by a process comprising the step of heating the curable composition to a temperature in the range of 50 °C to 250 °C, preferably to 70
  • Crosslinked polymer obtainable from the curable composition according to any one of variants 4 to 10 by a process comprising the step of heating the curable composition to a temperature in the range of 70 °C to 280 °C for a time sufficient to obtain a polymer.
  • Process for the manufacture of a composite material comprising the steps of combining a curable composition according to any one of variants 4 to 10 or a curable pre-polymer according to variant 12, with a fibrous or particulate reinforcement, and curing the resultant product.
  • Composite material obtainable by a process according to variant 14.

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Des phénols méta-substitués et para-substitués avec alcényle sont amenés en réaction avec de l'hydroxylbenzophénone pour obtenir des composés de la formule générale ou qui sont utilisés en tant qu'agents de vulcanisation de résines polymaléimide.
PCT/EP2016/082172 2015-12-21 2016-12-21 Compositions de résine thermodurcissable WO2017108946A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0230741A2 (fr) * 1986-01-18 1987-08-05 Technochemie GmbH - Verfahrenstechnik Résines durcissables
WO1997018254A1 (fr) * 1995-11-13 1997-05-22 Cytec Technology Corp. Polymeres thermodurcissables pour applications composites et adhesives

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0230741A2 (fr) * 1986-01-18 1987-08-05 Technochemie GmbH - Verfahrenstechnik Résines durcissables
WO1997018254A1 (fr) * 1995-11-13 1997-05-22 Cytec Technology Corp. Polymeres thermodurcissables pour applications composites et adhesives

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