WO2009115488A1 - Procédé de copolymérisation - Google Patents

Procédé de copolymérisation Download PDF

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Publication number
WO2009115488A1
WO2009115488A1 PCT/EP2009/053072 EP2009053072W WO2009115488A1 WO 2009115488 A1 WO2009115488 A1 WO 2009115488A1 EP 2009053072 W EP2009053072 W EP 2009053072W WO 2009115488 A1 WO2009115488 A1 WO 2009115488A1
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WIPO (PCT)
Prior art keywords
polymerizable composition
component
benzoxazine
formula
catalyst
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PCT/EP2009/053072
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English (en)
Inventor
Takeshi Endo
Atsushi Sudo
Hiroshi Yamashita
Jin Nishida
Thomas Huver
Rainer SCHÖNFELD
Andreas Taden
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Henkel Ag & Co. Kgaa
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Publication of WO2009115488A1 publication Critical patent/WO2009115488A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule

Definitions

  • the present invention relates to methods of selectively copolymerizing at least one benzoxazine component and at least one epoxy component.
  • Properties of polymers are often adapted to meet certain technical requirements by the use of a mixture of monomers in the polymerization process.
  • the polymerization of a mixture of two or more monomers is often referred to as copolymerization and leads, for example, to copolymers containing two different types of monomers.
  • Copolymers of epoxy and benzoxazine components are known. See e.g. U.S. Patent Nos. 4,607,091 (Schreiber), 5,021 ,484 (Schreiber), and 5,200,452 (Schreiber). These copolymers appear to be potentially useful commercially, as the epoxy resins can reduce the melt viscosity of benzoxazines allowing for the use of higher filler loading while maintaining a processable viscosity. However, epoxy resins oftentimes undesirably increase the temperature at which benzoxazines polymerize.
  • the present invention provides a method for selectively copolymerizing at least one benzoxazine component and at least one epoxy component.
  • the method includes the steps of providing a polymerizable composition comprising at least one benzoxazine component, and at least one epoxy component, providing at least one catalyst and subjecting the polymerizable composition and the at least one catalyst to conditions appropriate to selectively polymerize the polymerizable composition.
  • said at least one catalyst is selected from a) at least one nitrogen containing heterocycle and/or derivatives thereof, and/or b) at least one catalyst according to formula (I),
  • the polymerizable compositions used in said method are in particular suitable as coatings, adhesives, sealants and matrices for the preparation of reinforced material such as prepregs and towpregs and/or can be used in injection molding or extrusion.
  • the invention also provides a cured product obtained by the inventive method, in particular a cured product containing bundles or layers of fibers, and a method of preparing such material.
  • the at least one benzoxazine component can be any curable monomer, oligomer or polymer comprising at least one benzoxazine moiety.
  • X is selected from a direct bond (when o is 2), alkyl (when o is 1 ), alkylene (when o is 2-4), carbonyl (when o is 2), sulfur (when o is 1 ), thioether (when o is 2), sulfoxide (when o is 2), sulfone (when o is 2) and oxygen (when o is 2)
  • R 1 is selected from hydrogen, alkyl, alkenyl and aryl
  • R 4 is selected from hydrogen, halogen, alkyl and alkenyl, or R 4 is a divalent residue creating a naphthoxazine residue out of the benzoxazine structure.
  • R 1 and R 2 are the same or different and are selected from hydrogen, alkyl, such as methyl, ethyl, propyls and butyls, alkenyl, such as allyl, and aryl, and R 4 are the same or different and defined as above.
  • Representative benzoxazines within structure (B-Il) include:
  • the at least one benzoxazine may be embraced by the following structure (B-VII):
  • B-VII where p is 2, Y is selected from biphenyl, diphenyl methane, diphenyl isopropane, diphenyl sulfide, diphenyl sulfoxide, diphenyl sulfone, and diphenyl ketone, and R 4 is selected from hydrogen, halogen, alkyl and alkenyl, or R 4 is a divalent residue creating a naphthoxazine residue out of the benzoxazine structure.
  • additional benzoxazines are within the following structures:
  • the at least one benzoxazine component may include the combination of multifunctional benzoxazines and monofunctional benzoxazines, or may be the combination of one or more multifunctional benzoxazines or one or more monofunctional benzoxazines.
  • R is alkyl, such as methyl, ethyl, propyls and butyls, or aryl with or without substitution on one, some or all of the available substitutable sites, and R 4 is selected from hydrogen, halogen, alkyl and alkenyl, or R 4 is a divalent residue creating a maphthoxazine residue out of the benzoxazine structure.
  • Benzoxazines are presently available commercially from several sources, including Huntsman Advanced Materials; Georgia-Pacific Resins, Inc.; and Shikoku Chemicals Corporation, Chiba, Japan.
  • the at least one benzoxazine may typically be prepared by reacting a phenolic compound, such as a bisphenol A, bisphenol F, bisphenol S or thiodiphenol, with an aldehyde and an alkyl or aryl amine.
  • a phenolic compound such as a bisphenol A, bisphenol F, bisphenol S or thiodiphenol
  • U.S. Patent No. 5,543,516, hereby expressly incorporated herein by reference describes a method of forming benzoxazines, where the reaction time can vary from a few minutes to a few hours, depending on reactant concentration, reactivity and temperature. See also Burke et al., J. Org. Chem. , 30(10), 3423 (1965); see generally U.S. Patent Nos. 4,607,091 (Schreiber), 5,021 ,484 (Schreiber), 5,200,452 (Schreiber) and 5,443,91 1 (Schreiber).
  • the at least one epoxy component can be any curable monomer, oligomer or polymer comprising at least one, preferably at least two epoxy group.
  • the at least one epoxy component used may include multifunctional epoxy- containing components, such as C 1 -C 2S alkyl-, poly-phenol glycidyl ethers; polyglycidyl ethers of pyrocatechol, resorcinol, hydroquinone, 4,4'-dihydroxydiphenyl methane (or bisphenol F, such as RE-303-S or RE-404-S available commercially from Nippon Kayuku, Japan), 4,4'-dihydroxy-3,3'- dimethyldiphenyl methane, 4,4'-dihydroxydiphenyl dimethyl methane (or bisphenol A), 4,4'- dihydroxydiphenyl methyl methane, 4,4'-dihydroxydiphenyl cyclohexane, 4,4'-dihydroxy-3,3'- dimethyldiphenyl propane, 4,4'-dihydroxydiphenyl sulfone, and tris(4-hydroxyphenyl) methane; polyglycidy
  • epoxy components suitable for use in the present invention are polyglycidyl derivatives of phenolic compounds, such as those available under the tradenames EPON 825, EPON 826, EPON 828, EPON 1001 , EPON 1007 and EPON 1009, cycloaliphatic epoxy-containing compounds such as Araldite CY179 from Huntsman or waterborne dispersions under the tradenames EPI-REZ 3510, EPI-REZ 3515, EPI-REZ 3520, EPI-REZ 3522, EPI-REZ 3540 or EPI-REZ 3546 from Hexion; DER 331 , DER 332, DER 383, DER 354, and DER 542 from Dow Chemical Co.; GY285 from Huntsman, Inc.; and BREN-S from Nippon Kayaku, Japan.
  • polyglycidyl derivatives of phenolic compounds such as those available under the tradenames EPON 825, EPON 826, EPON 828, EPON 1001 , EPON 1007
  • epoxy-components include polyepoxides prepared from polyols and the like and polyglycidyl derivatives of phenol-formaldehyde novolacs, the latter of which are available commercially under the tradenames DEN 431 , DEN 438, and DEN 439 from Dow Chemical Company and a waterborne dispersion ARALDITE PZ 323 from Huntsman.
  • Cresol analogs are also available commercially such as ECN 1273, ECN 1280, ECN 1285, and ECN 1299 or waterborne dispersions ARALDITE ECN 1400 from Huntsman, Inc. SU-8 and EPI- REZ 5003 are bisphenol A-type epoxy novolacs available from Hexion.
  • Epoxy or phenoxy functional modifiers to improve adhesion, flexibility and toughness such as the HELOXY brand epoxy modifiers 67, 71 , 84, and 505.
  • the epoxy or phenoxy functional modifiers may be used in an amount of about 1 :1 to about 5:1 with regard to the heat curable resin.
  • epoxy resins epoxy components
  • the polymerizable composition may comprise further polymerizable components preferably selected from lactones, lactams, oxetanes, tetrahydrofuranes, aziridines, oxazolines, acid anhydrides, and/or phenolic resins and/or mixtures thereof.
  • the polymerizable composition comprise at least one epoxy component in an amount from about 10 to about 90 percent by weight, preferably from about 20 to about 80 percent by weight and more preferably from about 40 to 60 percent by weight based on the total amount of the polymerizable composition.
  • the polymerizable composition comprise at least one benzoxazine component in an amount from about 10 to about 90 percent by weight, preferably from about 20 to about 80 percent by weight and more preferably from about 40 to 60 percent by weight based on the total amount of the polymerizable composition.
  • the polymerizable composition comprises at least one epoxy component in an amount from about 30 to about 70 percent by weight and at least one benzoxazine component in an amount from about 30 to about 70 percent by weight based on the total amount of the polymerizable composition.
  • the polymerizable composition comprises epoxy group(s) and benzoxazine group(s) in a molar ratio (epoxy to benzoxazine groups) from 95:5 to 5:95, preferable from 80:20 to 20:80.
  • the molar ratio of epoxy group(s) to benzoxazine group(s) in said composition is 50:50.
  • the at least one catalyst used in the inventive method may exclusively be selected from at least one nitrogen containing heterocycle and/or derivatives thereof or may exclusively be selected from catalysts according to formula (I),
  • the at least one catalyst of the present invention may exclusively be selected from metal complexes of organic sulfur containing acids and/or derivatives thereof.
  • the catalyst used in the inventive method is a combination of at least one nitrogen containing heterocycle and/or derivatives thereof, and at least one catalyst according to formula (I),
  • the at least one catalyst used in the inventive method may also be a combination of at least one nitrogen containing heterocycle and/or derivatives thereof, and at least one metal complex of an organic sulfur containing acid and/or derivatives thereof.
  • the at least one catalyst used in the inventive method may also be combination of at least one catalyst according to formula (I),
  • the catalyst used in the inventive method is a combination of at least one nitrogen containing heterocycle and/or derivatives thereof, and at least one catalyst according to formula (I)
  • the at least one nitrogen containing heterocycle according to the present invention can preferably be saturated, unsaturated, or aromatic. It may also be preferred that the at least one nitrogen containing heterocycle is a thiazole, an oxazole, an imidazole, a pyridine, a piperidine, or a pyrimidine, a piperazine, a pyrrole, an indole or a benzthiazolyl. It is further on preferred that there is no acidic functional group present at the at least one nitrogen containing heterocycle. Most preferably, the nitrogen containing heterocyclic moiety is a thiazole and/or an imidazole.
  • the at least one nitrogen containing heterocycle and/or its derivatives according to the present invention are selected from the group of imidazoles and/or imidazole derivatives with formula (II),
  • R 1 , R 2 , R 3 and R 4 being independently selected from hydrogen or aliphatic or aromatic hydrocarbons, whereas it is especially preferred that said imidazole is selected from the group of imidazole, 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2- phenylimidazole, 1 ,2-dimethyl imidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4- methylimidazole, 1-benzyl-2-phenylimidazole, i-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole or 1- aminoethyl-2-methylimidazole.
  • said imidazole is selected from the group of imidazole, 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimid
  • the term "derivative of a nitrogen containing heterocycle” includes catalytically active salts of the nitrogen containing heterocycle, such as salts derived from sulfonic acid, like trifluormethane sulfonic acid.
  • a further catalyst used in the method of the present invention is selected from at least one compound according to formula (I),
  • n 1 , 2, 3 or 4, preferably 2 or 3 and E1 as well as E2 are electron withdrawing substituents
  • E the present invention understands all kind of electron-withdrawing substituents, whereas E 1 and E 2 may be identical or different.
  • the term "electron withdrawing substituent” relates to all substituents having a (-I) and/or (-M) effect. Examples without restricting the scope to those groups are all types of nitrate, sulphate, sulphonic, halogenic, carbonate, carboxylate, formate, aldehyde, keto, acetal, and further groups.
  • the substituent E has a (-I) and a (+M) effect. It is also preferred according to the present invention to have at least one electron-withdrawing substituent, which is a monovalent substituent. It is most preferred according to the present invention if E is selected from the group of halogenic elements, in particular if E is F. It is also preferred if E 1 and E 2 are identical.
  • the preferred metal centers are selected from manganese (Mn), iron (Fe), and cobalt (Co). Nevertheless also further metal centers which show metal:ligand complexing properties like those specific metals fall under the scope of this invention.
  • metals in the transition group of the periodic system metals which are capable of forming metal:ligand complexes are preferred for the purpose of the present invention. Examples are metals like Fe, Co, Ni, Cr, Mo, W, V, Nb, Ta, Ti, Zr, Hf, In, Mn, Cu, Zn, Cd.
  • the most preferred metals in the view of the present invention are selected from manganese (Mn), iron (Fe), and cobalt (Co).
  • organic sulfur containing acid and/or the derivative of an organic sulfur containing acid according to the present invention are selected from the group of sulfonic acids according to formula (IV)
  • R 5 is selected from optionally substituted aryl and alkyl groups.
  • R 5 is selected from fluorinated alkyl goups, such as CF 3 , C 2 F 5 , C 3 F 7 and C 4 F 9 .
  • organic sulfonic acid of the present invention is selected from the group of sulfonic acids according to formula (V), (Vl), (VII) and (VIII).
  • the preferred metal (M) in formula (III) is selected from alkali metals, such as lithium (Li), sodium (Na), potassium (K), alkali earth metals, such as magnesium (Mg), calcium (Ca), barium (Ba), scandium (Sc), yttrium (Y), lanthanoid metals, such as lanthanum (La), cerium (Ce), europium (Eu), ytterbium (Yb), copper (Cu), zinc (Zn), and boron (B). Particularly preferable are Sc, Y, and lanthanoid as metal (M).
  • alkali metals such as lithium (Li), sodium (Na), potassium (K)
  • alkali earth metals such as magnesium (Mg), calcium (Ca), barium (Ba), scandium (Sc), yttrium (Y), lanthanoid metals, such as lanthanum (La), cerium (Ce), europium (Eu), ytterbium (Yb
  • the at least one epoxy component and the at least one benzoxazine component can be copolymerized selectively.
  • selective copolymerization preferably refers to a copolymerization process, where the polymerization kinetics of the at least one benzoxazine and the at least one epoxy component can be controlled at the same time by using at least one catalyst of the present invention. Therefore the chemical nature of the cured product can be controlled by the inventive method and a copolymer selected from the group consisting of hybrid copolymers consisting of two homopolymers, materials having an interpenetrate network-structure, block copolymers, graft copolymers, and/or statistical copolymers, and/or mixtures thereof can be obtained.
  • the method of the present invention allows to cure one component in preference to the other component or allows to cure both components at substantially the same time.
  • the at least one catalyst begins to cure at least one epoxy component first in preference to the first curing benzoxazine component.
  • the at least one catalyst begins to cure all epoxy components present in the polymerizable composition first in preference to the first curing benzoxazine component.
  • the at least one catalyst begins to cure the first curing epoxy component and the first curing benzoxazine component at substantially the same time.
  • the at least one catalyst begins to cure at least one benzoxazine component first in preference to the first curing epoxy component.
  • the at least one catalyst begins to cure all benzoxazine components present in the polymerizable composition first in preference to the first curing epoxy component.
  • gins to cure first preferably refers to the polymerization kinetics of the at least one benzoxazine component and the at least one epoxy component in the polymerizable composition.
  • a component is cured first in preference to the other component if after 50% conversion of the faster curing component the slower curing component shows a conversion of less than 30%, preferably less than 20% and more preferably less than 10%, 5% or 2%.
  • gins to cure at substantially the same time preferably refers to the polymerization kinetics of the at least one benzoxazine component and the at least one epoxy component in the polymerizable composition. According to the present invention, two components are cured substantially at the same time if after 50% conversion of one component the other component shows a conversion of 40 to 60%, preferably of 45 to 55%.
  • each component can easily be determined by a man skilled in the art using known techniques, such as GC-analysis, NMR- or IR spectroscopy.
  • the at least one catalyst selected from at least one nitrogen containing heterocycle and/or derivatives thereof begins to cure at least one benzoxazine component first in preference to the first curing epoxy component, such as 3,4-epoxycyclohexyl-1- carboxylic-acid methyl ester, or begins to cure at least one epoxy component, such as glycidyl phenyl ether first in preference to the first curing benzoxazine component.
  • the at least one catalyst selected from a catalyst according to formula (I) begins to cure the first curing epoxy component, such as 3,4- epoxycyclohexyl-1 -carboxylic-acid methyl ester, and the first curing benzoxazine component at substantially the same time or begins to cure at least one epoxy component, such glycidyl phenyl ether, first in preference to the first curing benzoxazine component.
  • first curing epoxy component such as 3,4- epoxycyclohexyl-1 -carboxylic-acid methyl ester
  • the first curing benzoxazine component at substantially the same time or begins to cure at least one epoxy component, such glycidyl phenyl ether, first in preference to the first curing benzoxazine component.
  • the at least one catalyst selected from at least one metal complex of an organic sulfur containing acid and/or at least one metal complex of a derivative of an sulfur containing acid begins to cure at least one epoxy component, such as 3,4- epoxycyclohexyl-1 -carboxylic-acid methyl ester, or glycidyl phenyl ether, first in preference to the first curing benzoxazine component.
  • at least one epoxy component such as 3,4- epoxycyclohexyl-1 -carboxylic-acid methyl ester, or glycidyl phenyl ether
  • the at least one catalyst is present in an amount sufficient to cure the polymerizable composition.
  • the molar ratio between said components (epoxy component and benzoxazine component) and said at least one catalyst is 90:10 to 99.9 to 0.1 , preferably 95:5 to 99.5:0.5.
  • the polymerizable composition is polymerized at conditions appropriate to selectively polymerize the polymerizable composition.
  • the polymerizable composition is polymerized at temperatures from 5O 0 C to 300 0 C, preferably from 7O 0 C to 25O 0 C, more preferably from 100 0 C to 15O 0 C and/or pressures between 1 to 10 atm, preferably under atmospheric pressure.
  • reactive diluents for example styrene oxide, butyl glycidyl ether, 2,2,4-trimethylpentyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether or glycidyl esters of synthetic, highly branched, mainly tertiary, aliphatic monocarboxylic acids, oxazoline group containing compounds may be added to the polymerizable composition to reduce its viscosity.
  • reactive diluents for example styrene oxide, butyl glycidyl ether, 2,2,4-trimethylpentyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether or glycidyl esters of synthetic, highly branched, mainly tertiary, aliphatic monocarboxylic acids, oxazoline group
  • additives which the inventive polymerizable composition can include are tougheners, plasticizers, extenders, microspheres, fillers and reinforcing agents, for example coal tar, bitumen, textile fibres, glass fibres, asbestos fibres, boron fibres, carbon fibres, mineral silicates, mica, powdered quartz, hydrated aluminum oxide, bentonite, wollastonite, kaolin, silica, aerogel or metal powders, for example aluminium powder or iron powder, and also pigments and dyes, such as carbon black, oxide colors and titanium dioxide, fire-retarding agents, thixotropic agents, flow control agents, such as silicones, waxes and stearates, which can, in part, also be used as mold release agents, adhesion promoters, antioxidants and light stabilizers, the particle size and distribution of many of which may be controlled to vary the physical properties and performance of the inventive polymerizable composition.
  • tougheners for example coal tar, bitumen, textile fibres, glass fibres,
  • fillers When used, fillers are used in an amount sufficient to provide the desired rheological properties.
  • Fillers may be used in an amount up to about 50 percent by weight, such as about 5 to about 32 percent by weight, for instance about 10 to about 25 percent by weight.
  • the fillers may be inorganic ones, such as silicas.
  • the silica filler may be a silica nanoparticle.
  • the polymerizable compositions used in the inventive method are in particular suitable as coatings, adhesives, sealants and matrices for the preparation of reinforced material such as prepregs and towpregs and/or can be used in injection molding or extrusion or in the formation of prepregs or towpregs formed from a layer or bundle of fibers infused with the polymerizable composition.
  • the invention also provides a cured product obtained by the inventive method, in particular cured products containing bundles or layers of fibers, and a method of preparing such material.
  • the invention relates to processes for producing a prepreg or a towpreg.
  • One such process includes the steps of (a) providing a layer or bundle of fibers; (b) providing a polymerizable composition used in the inventive method; and (c) joining said polymerizable composition and the layer or bundle of fibers to form a prepreg or a towpreg assembly, respectively, and exposing the resulting prepreg or towpreg assembly to elevated temperature and pressure conditions sufficient to infuse the layer or bundle of fibers with the polymerizable composition to form a prepreg or towpreg, respectively.
  • Another such process for producing a prepreg or towpreg includes the steps of (a) providing a layer or bundle of fibers; (b) providing a polymerizable composition used in the inventive method in liquid form; (c) passing the layer or bundle of fibers through said polymerizable composition to infuse the layer or bundle of fibers with said polymerizable composition; and (d) removing excess of said polymerizable composition from the prepreg or towpreg assembly.
  • the fiber layer or bundle may be constructed from unidirectional fibers, woven fibers, chopped fibers, non-woven fibers or long, discontinuous fibers.
  • the fiber chosen may be selected from carbon, glass, aramid, boron, polyalkylene, quartz, polybenzimidazole, polyetheretherketone, polyphenylene sulfide, poly p-phenylene benzobisoaxazole, silicon carbide, phenolformaldehyde, phthalate and napthenoate.
  • the carbon is selected from polyacrylonitrile, pitch and acrylic
  • the glass is selected from S glass, S2 glass, E glass, R glass, A glass, AR glass, C glass, D glass, ECR glass, glass filament, staple glass, T glass and zirconium oxide glass.
  • inventive polymerizable composition and the prepregs or towpregs are particularly useful in the manufacture and assembly of composite parts for aerospace and industrial end uses, bonding of composite and metal parts, core and core-fill for sandwich structures and composite surfacing.
  • the polymerizable composition used in the inventive method may be in the form of an adhesive, sealant or coating, in which case one or more of an adhesion promoter, a flame retardant, a filler (such as the inorganic filler noted above, or a different one), a thermoplastic additive, a reactive or non-reactive diluent, and a thixotrope may be included.
  • the polymerizable compositions in adhesive form may be placed in film form, in which case a support e.g.
  • Example 2 Copolymerization by 2-ethyl-4-methylimidazole (EMI) at 150 0 C Benzoxazine 1 (1.47 g; 6.51 mmol), epoxide 2 (1.048 g; 6.71 mmol), and EMI (14.7 mg; 0.134 mmol) were mixed to obtain a homogeneous mixture. The mixture was divided into ten portions (253 mg each) and each of them was placed in a test tube. Argon inlets were attached to the resulting 10 test tubes an then they were heated in an oil bath at 150 0 C. From time to time, these test tubes were taken away from the oil bath one-by-one, and each of the mixture was analyzed by GC to determine conversions of the monomers. The resulting time-conversion relationships are shown in Table 2 and visualized in Figure 2.
  • EMI 2-ethyl-4-methylimidazole
  • Benzoxazine 1 (1.463 g; 6.50 mmol), epoxide 2 (1.041 g; 6.66 mmol), and Mn(F-acac) 2 (62.4 mg;
  • the formed material can once again be a hybrid material/copolymer comprising two homopolymers or a graft copolymer, which can be formed by graft polymerization of epoxide 2 from the phenolic side chain of the benzoxazine homopolymer formed in the early stages.
  • Example 5 Copolymerization by 2-ethyl-4-methylimidazole (EMI) at 150 0 C Benzoxazine 1 (1.35 g; 6.00 mmol), epoxide 3 (0.902 g; 6.01 mmol), and EMI (13.2 mg; 0.120 mmol) were mixed to obtain a homogeneous mixture. The mixture was divided into ten portions (200 mg each) and each of them was placed in a test tube. Nitrogen inlets were attached to the resulting 10 test tubes and then they were heated in an oil bath at 150 0 C. From time to time, these test tubes were taken away from the oil bath one-by-one, and each of the mixture was analyzed by GC to determine conversions of the monomers. The resulting time-conversion relationships are shown in Table 5.
  • EMI 2-ethyl-4-methylimidazole
  • Benzoxazine 1 (1.35 g; 6.00 mmol), epoxide 3 (0.903 g; 0.601 mmol), and Mn(F-acac) 2 (56.2 mg;
  • Example 7 Copolymerization by manganese (II) bis(hexafluoroacetoacetonato) (Mn(F-acac) 2 ) at 12O 0 C

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)

Abstract

La présente invention concerne des procédés de copolymérisation sélective d’un composant benzoxazine et d’un composant époxy.
PCT/EP2009/053072 2008-03-19 2009-03-16 Procédé de copolymérisation WO2009115488A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2336221A1 (fr) 2010-12-10 2011-06-22 Henkel AG & Co. KGaA Compositions durcissables
CN104781308A (zh) * 2012-09-28 2015-07-15 3M创新有限公司 聚苯并*嗪组合物
US9484123B2 (en) 2011-09-16 2016-11-01 Prc-Desoto International, Inc. Conductive sealant compositions
US20210024748A1 (en) * 2018-03-30 2021-01-28 Toray Industries, Inc. Benzoxazine resin composition, prepreg, and fiber-reinforced composite material

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4628077A (en) * 1983-12-16 1986-12-09 The Standard Oil Company Preparation of polyamide with catalyst comprising transition metal attached to a ligand which contains electron withdrawing groups
US20050181215A1 (en) * 2004-02-02 2005-08-18 Tamura Kaken Corporation Thermosetting resin compositions and film articles
WO2006103185A1 (fr) * 2005-04-01 2006-10-05 Huntsman Advanced Materials (Switzerland) Gmbh Composition contenant de la resine de benzoxazine et d'epoxy
WO2007064801A1 (fr) * 2005-12-02 2007-06-07 Henkel Corporation Compositions durcissables
JP2007231041A (ja) * 2006-02-27 2007-09-13 Sumitomo Bakelite Co Ltd 硬化性樹脂組成物
WO2008034814A2 (fr) * 2006-09-21 2008-03-27 Henkel Ag & Co. Kgaa Formulations contenant de la benzoxazine polymérisable/durcissable à basse température
WO2008034753A1 (fr) * 2006-09-21 2008-03-27 Henkel Ag & Co. Kgaa Polymérisation catalytique à basse température
WO2008051373A2 (fr) * 2006-10-19 2008-05-02 Dow Global Technologies Inc. Compositions de résine époxy durcissables ayant une meilleure adhérence sur les substrats métalliques et leurs procédés de fabrication et d'utilisation

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4628077A (en) * 1983-12-16 1986-12-09 The Standard Oil Company Preparation of polyamide with catalyst comprising transition metal attached to a ligand which contains electron withdrawing groups
US20050181215A1 (en) * 2004-02-02 2005-08-18 Tamura Kaken Corporation Thermosetting resin compositions and film articles
WO2006103185A1 (fr) * 2005-04-01 2006-10-05 Huntsman Advanced Materials (Switzerland) Gmbh Composition contenant de la resine de benzoxazine et d'epoxy
WO2007064801A1 (fr) * 2005-12-02 2007-06-07 Henkel Corporation Compositions durcissables
JP2007231041A (ja) * 2006-02-27 2007-09-13 Sumitomo Bakelite Co Ltd 硬化性樹脂組成物
WO2008034814A2 (fr) * 2006-09-21 2008-03-27 Henkel Ag & Co. Kgaa Formulations contenant de la benzoxazine polymérisable/durcissable à basse température
WO2008034753A1 (fr) * 2006-09-21 2008-03-27 Henkel Ag & Co. Kgaa Polymérisation catalytique à basse température
WO2008051373A2 (fr) * 2006-10-19 2008-05-02 Dow Global Technologies Inc. Compositions de résine époxy durcissables ayant une meilleure adhérence sur les substrats métalliques et leurs procédés de fabrication et d'utilisation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WANG F ET AL: "Photopolymerization of Epoxides with Platinum (II) Bis(acetylacetonato)/Silane Catalysts", MACROMOLECULES, ACS, WASHINGTON, DC, US, vol. 34, 1 January 2001 (2001-01-01), pages 6202 - 6205, XP002477987, ISSN: 0024-9297, [retrieved on 20010803] *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2336221A1 (fr) 2010-12-10 2011-06-22 Henkel AG & Co. KGaA Compositions durcissables
US9484123B2 (en) 2011-09-16 2016-11-01 Prc-Desoto International, Inc. Conductive sealant compositions
CN104781308A (zh) * 2012-09-28 2015-07-15 3M创新有限公司 聚苯并*嗪组合物
US20210024748A1 (en) * 2018-03-30 2021-01-28 Toray Industries, Inc. Benzoxazine resin composition, prepreg, and fiber-reinforced composite material

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