WO2009075743A2 - Curable compositions containing isocyanate-based tougheners - Google Patents
Curable compositions containing isocyanate-based tougheners Download PDFInfo
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- WO2009075743A2 WO2009075743A2 PCT/US2008/013290 US2008013290W WO2009075743A2 WO 2009075743 A2 WO2009075743 A2 WO 2009075743A2 US 2008013290 W US2008013290 W US 2008013290W WO 2009075743 A2 WO2009075743 A2 WO 2009075743A2
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- diisocyanate
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- curable composition
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- 0 *N(C1)COc2c1cccc2 Chemical compound *N(C1)COc2c1cccc2 0.000 description 2
- FMZPVXIKKGVLLV-UHFFFAOYSA-N C(c1ccccc1OC1)N1c1ccccc1 Chemical compound C(c1ccccc1OC1)N1c1ccccc1 FMZPVXIKKGVLLV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
- C08K5/357—Six-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
- C08L2666/20—Macromolecular compounds having nitrogen in the main chain according to C08L75/00 - C08L79/00; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
Definitions
- the present invention relates to curable compositions comprising (a) N- arylated benzoxazines, and (b) a prepolymer produced from a diisocyanate having two isocyanate groups with different reactivity.
- Epoxy resins can also be mixed with copolymers based on butadiene and acrylonitrile to enhance the impact strength and/or the flexibility of the cured product. Ordinarily, however, such copolymers compromise the tensile shear strength and the glass transition temperature of the resulting cured products.
- U.S. Patent No. 5,278,257 refers to and claims a composition containing a copolymer based on at least one 1 ,3-diene and at least one polar, ethylenically unsaturated comonomer, a phenol-terminated polyurethane, polyurea or polyurea-urethane of a certain formula, after the removal of the terminal isocyanate, amino or hydroxyl groups, which is soluble or dispersible in epoxy resins, it being necessary for at least one of these groups to be a tertiary amine and where the ratio by weight of the comonomer to the polyurethane, polyurea or polyurea-urethane is from 5:1 to 1 :5, and an epoxy resin having at least two 1 ,2-epoxide groups per molecule.
- U.S. Patent Application Publication No. 2005/0070634 describes a composition comprising a) one or more epoxy resins; b) one or more rubber modified epoxy resins; c) one or more toughening compositions comprising the reaction product of one or more isocyanate terminated prepolymers and one or more capping compounds having one or more bisphenolic, phenolic, benzyl alcohol, aminophenyl or, benzylamino moieties where the reaction product is terminated with the capping compound; d) one or more curing agents and one or more catalysts for epoxy resins which initiates cure at a temperature of about 100 0 C or greater; and e) optionally, fillers, adhesion promoters, wetting agents and Theological additives useful in epoxy adhesive compositions.
- the resulting adhesive composition is reported to have a viscosity at 45°C of about 20 Pa s to about 400 Pa s.
- Blends of epoxy resins and benzoxazines are also known. See e
- Blends of benzoxazines and curable materials other than epoxy and/or phenolics are also known.
- U.S. Patent No. 6,620,925 (Musa) is directed to and claims a curable composition comprising certain benzoxazine compounds without reactive functionality other than the benzoxazine (apart from allyl and propargyl which are disclosed but not claimed) and a curable compound or resin selected from vinyl ethers, vinyl silanes, compounds or resins containing vinyl or allyl functionality, thiol-enes, compounds or resins containing cinnamyl or styrenic functionality, fumarates, maleates, acrylates, maleimides, cyanate esters, and hybrid resins containing both vinyl silane and cinnamyl, styrenic, acrylate or maleimide functionality.
- U.S. Patent No. 6,743,852 discloses combinations of liquid benzoxazines and a thermosetting resin composition for adhering materials with dissimilar coefficients of thermal expansion comprising a) a benzoxazine compound in liquid form, b) thermoset compounds including epoxy, cyanate ester, maleimide, acrylate, methacrylate, vinyl ether, styrenic, vinyl ester, propargyl ether, diallyl amide, aromatic acetylene, benzocyclobutene, thiolenes, maleate, oxazoline, and itaconate, c) optionally, one or more anti-oxidants, bleed control agents, fillers, diluents, coupling agents, adhesion promoters, flexibilizers, dyes and pigments, and d) a cure initiator.
- Polyurethane Prepolymer and flexible Epoxy A comparative study", Polym. Eng. Sci. (2005) 288-296 the use of isophorone diisocyanate based polyurethane-prepolymers alloyed with polybenzoxazine and flexible epoxy.
- Cured compositions showing improved toughness and compression after impact are disclosed in International Patent Application Publication No. WO 2007/064801 A1 (Li).
- the so disclosed curable compositions comprise (a) a large variety of benzoxazines, in combination with (b) a combination of adducts one of which is prepared from hydroxy- containing compounds, isocyanate-containing compounds and phenolic compounds and the second of which is prepared from the first adduct and epoxy-containing compounds, (c) epoxy resins and (d) optionally tougheners.
- the present invention provides compositions that include N-arylated benzoxazine components in combination with end-capped prepolymers (prepared from diisocyanates containing two isocyanate groups with different reactivity).
- Such curable compositions according to the invention show sufficient flexural modulus and toughness, even without added epoxy resin.
- the curable compositions of the present invention can also be supplemented with epoxy resins without losing their advantages properties in case the use of the epoxy resin is desired for specific applications.
- compositions comprising: (A) an
- N-arylated benzoxazine component N-arylated benzoxazine component
- B a prepolymer of the following general structure:
- P is a z-valent residue of an oligomer or polymer
- X and Y independently are selected from the group consisting of NR', O and S 1 where R' is hydrogen or a residue selected from the group consisting of aliphatic, heteroaliphatic, araliphatic, heteroaraliphatic, aromatic and heteroaromatic residues
- D is a divalent residue of a diisocyanate comprising two isocyanate groups having different reactivity, from which the two isocyanate groups with different reactivity have been removed to form two binding sites (valences);
- E is an end-capping residue, selected from the group consisting of aliphatic, heteroaliphatic, araliphatic, heteroaraliphatic, aromatic and heteroaromatic residues
- z is an integer of 1 to 12.
- the prepolymer can be build by reacting a polymer P-(XH) Z , wherein the z XH groups are independently NHR', OH or SH, are reacted with a diisocyanate D-(NCO) 2 and an end-capping reagent E-YH.
- the reaction is preferably carried out in a way that each of the z XH groups is reacted with one molecule of the diisocyanate to obtain an isocyanate terminated intermediate having the following structure:
- Suitable polymers P-(XH) Z , diisocyanates D-(NCO) 2 and end-cappers E-YH will be described in detail below as well as suitable N-arylated benzoxazines.
- compositions of the present invention are in particular suitable as adhesives, sealants and matrices for the preparation of reinforced material such as prepregs and towpreg.
- the invention also provides a cured product of the composition of the present invention, in particular cured products containing bundles or layers of fibers, and a method of preparing such material.
- N-arylated benzoxazines refers to any benzoxazines carrying an aryl residue directly bound at the benzoxazine nitrogen atom.
- One group of N-arylated benzoxazines of the present invention may be embraced by the following structure:
- X is selected from a direct bond (when m is 2), alkyl (when m is 1), alkylene
- R 1 is aryl
- R 4 is selected from hydrogen, halogen, alkyl, alkenyl, or R 4 is a divalent residue creating a naphthoxazine residue out of the benzoxazine structure.
- R 2 are the same or different aryl residues and R 4 are the same or different and defined as above.
- R 1 , R 2 and R 4 are as defined above.
- N-arylated benzoxazine may be embraced by the following structure:
- Y is selected from biphenyl (when p is 2), diphenyl methane (when p is 2), diphenyl isopropane (when p is 2), diphenyl sulfide (when p is 2), diphenyl sulfoxide (when p is 2), diphenyl sulfone (when p is 2), and diphenyl ketone (when p is 2), and R 4 is selected from hydrogen, halogen, alkyl, alkenyl or R 4 is a divalent residue creating a naphthoxazine residue out of the benzoxazine structure.
- Benzoxazines of general structure VII are preferred.
- N-arylated benzoxazines include:
- the 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 an aryl residue 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 naphthoxazine residue out of the benzoxazine structure.
- R is an aryl residue 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 naphthoxazine 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 last of which offers among others Bisphenol A- aniline, Bisphenol A-methylamin, Bisphenol F-aniline benzoxazine resins. If desired, however, instead of using commercially available sources, the 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 aryl amine.
- a phenolic compound such as a bisphenol A, bisphenol F, bisphenol S or thiodiphenol
- the N-arylated benzoxazine may be present in the inventive composition in an amount in the range of about 50 to about 95 percent by weight, more preferably about 55 to about 85 percent by weight, and most preferably about 60 to about 80 percent by weight, based on the total weight of components A) and B) of the curable composition of the present invention.
- Amount of less than 50 percent by weight will usually negatively affect the flexural modulus of the cured compositions and amounts excluding 95 percent of N-arylated benzoxazines will usually lead to cured composition with only small increase in toughness represented by Ki C and G 1C values.
- Benzoxazine polymerization can be self-initiated under elevated temperature conditions and also by inclusion of anhydrides and/or cationic initiators, such as Lewis acids, and other known cationic initiators, such as metal halides; organometallic derivatives; metallophorphyrin compounds such as aluminum phthalocyanine chloride; methyl tosylate, methyl triflate, and triflic acid; and oxyhalides.
- anhydrides and/or cationic initiators such as Lewis acids, and other known cationic initiators, such as metal halides; organometallic derivatives; metallophorphyrin compounds such as aluminum phthalocyanine chloride; methyl tosylate, methyl triflate, and triflic acid; and oxyhalides.
- basic materials such as imidizaoles, may be used to initiate polymerization.
- the PP as noted are prepared reacting one or more hydroxyl, amino and/or thiol containing polymers, in particular such polymers introducing thermoplastic properties into the prepolymer, with one or more diisocyanates having two isocyanate groups with different reactivity and one or more end-capping agents (“end-cappers”) comprising at least one hydroxyl, thiol or amino group being reactive towards isocyanate.
- one or more hydroxyl, amino and/or thiol containing polymers in particular such polymers introducing thermoplastic properties into the prepolymer, with one or more diisocyanates having two isocyanate groups with different reactivity and one or more end-capping agents (“end-cappers”) comprising at least one hydroxyl, thiol or amino group being reactive towards isocyanate.
- the hydroxyl, amino and/or thiol containing polymer is reacted with one or more diisocyanates having two isocyanate groups with different reactivity for a time and amount sufficient to ensure isocyanate capping of the hydroxyl, amino and/or thiol containing polymer or oligomer.
- the polymer or oligomer may be mixed with one or more diisocyanates having two isocyanate groups with different reactivity and reacted at a temperature in the range of about 50 0 C to about 80 0 C for a period of about 0.5 to 2.5 hours, desirably under an inert atmosphere, such as a nitrogen blanket, to form an isocyanate- terminated prepolymer intermediate, with which the end-capper is reacted resulting in the formation of prepolymer to be used in the compositions of the present invention.
- Alternative routes can be used to prepare the prepolymer, as well.
- Illustrative of such alternative routes is where the reaction is performed in the presence of a condensation catalyst.
- a condensation catalyst examples include the stannous salts of carboxylic acids, such as stannous octoate, stannous oleate, stannous acetate, and stannous laureate; dialkyltin dicarboxylates, such as dibutyltin dilaureate and dibutyltin diacetate; tertiary amines and tin mercaptides.
- the amount of catalyst employed is generally between about 0.00025 and about 5 percent by weight of the catalyzed reactants, depending on the nature of the reactants.
- the PP (i.e. component B) may be used in an amount of 5 to 50, such as 10 to 30, most preferably 15 to 25 percent by weight, based on the total weight of components A) and B) of the curable composition of the invention.
- the polymeric or oligomeric part P of the P-(XH) Z polymer may be of such nature to introduce thermoplastic properties to the pre-polymer. Therefore the chemical nature is variable in a wide range embracing polyethers, polyesters, polyamides, polyacrylates, polymethacrylates, polybutadienes, and polysiloxanes, of which the polyethers are desirable.
- P can be linear or branched.
- P itself can already include urethane, urea or thiourethane groups originating from the reaction of low-molecular weight polyol, polyamines or polythiols.
- a triol such as glycerol or trimethylolpropane
- a polyisocyanate such as a diisocyanate
- an isocyanate terminated low-molecular weight monomer to which for example polyetherpolyols such as polyether diols can be attached.
- diisocyanates it is most preferred to use diisocyanates wherein the two isocyanate groups exhibit different reactivity.
- the hydroxyl, amino and/or thiol containing polymer (P-(XH) 2 , definitions as above) used to make the prepolymer should preferably have a number average molecular weight ("M n ”) of 500 to 4,000 g/mol more preferably 700 to 2,000 g/mol and most preferably 800 to 1 ,600 g/mol, as measured by gel permeation chromatography ("GPC”) using polyethylene glycol standards for calibration purposes.
- M n number average molecular weight
- the PP thus should have a number average molecular weight in the range of 1 ,000 to 100,000 g/mol, such as 2,000 to 40,000 g/mol, measured as before with GPC.
- the most preferred residue P is a polyalkylene oxide residue.
- the polyalkylene oxide include a series of hydrocarbon groups separated by oxygen atoms and terminated with hydroxyl, amino or thiol.
- the hydrocarbon groups should preferably be alkylene groups - straight or branched chain - and should preferably have from 2 to about 6 carbons, such as about 2 to about 4 carbon atoms, desirably about 3 to about 4 carbon atoms.
- the alkylene groups may be thus derived from ethylene oxide, propylene oxides, butylene oxides or tetrahydrofuran.
- the hydroxyl, amino and/or thiol terminated polyalkylene oxide should preferably have a number average molecular weight of about 500 to about 4,000 g/mol, such as about 700 to about 2,000 g/mol and most preferably 800 to
- a preferred hydroxy-containing polymer to be used as P-(XH) 2 can be described by structure XX:
- R v and R w independently are H, methyl or ethyl
- z is 1-6, preferably 2-3 and x is 12-45, such as 20-35.
- R v and R w are H and z is 2 to 3 and the number-average molecular weight determined by the value of x is between 500 and 4000 g/mol more preferably 700 to 2000 g/mol and most preferably 800 to 1600 g/mol.
- a preferred amino-containing polymer to be used as P-(XH) 2 can be described by structure XXI:
- R v , R w , z and x are defined as in structure XXIII, and R u is H or alkyl. Those compounds lead to polyurea containing prepolymers.
- hydroxy, amino and/or thiol containing polyalkylene ethers should be used in a molar ratio of OH, amino and/or SH groups to isocyanate groups of the one or more diisocyanates having two isocyanate groups with different reactivity in a range of 1 :0.9 to
- 1 :4.0 such as 1 :1.0 to 1 :2.5, for instance 1 :1.85.
- the integer z in P-(XH) 2 ranges from 1 to 12, preferable 1 to 6, more preferable 2 to 4 and most preferable z is 2 or 3.
- Diisocyanates having two isocyanate groups with different reactivity D-(NCO)?
- Crucial for the present invention is to use a diisocyanate for reaction with the hydroxy, amino and/or thiol containing polymers P-(XH) 2 , which has two isocyanate groups having different reactivity.
- the different reactivity is influenced especially by the spatial requirements, steric hindrances and/or electron density in the vicinity of an isocyanate group at given reaction conditions.
- a 13 C-NMR spectrum taken from the diisocyanate candidate and compared with the reaction product between P- (XH) Z and die diisocyanate candidate will easily reveal a preference of the more reactive isocyanate group of the diisocyanate towards the XH groups of P-(XH) 2 , in that the NMR signal for the carbon atom of the more reactive isocyanate group will disappear more than the carbon atom signal of the lower reactive isocyanate group. Since the NMR signal intensity is quantifiable the ratio of both reaction products - the one between P-(XH) 2 and the more reactive isocyanate group and the one with the less reactive isocyanate group of the diisocyanate - can be determined.
- At least 70 % by weight of the product should be attributed to the reaction with the more reactive isocyanate group of the diisocyanate. Even more preferably at least 80 % by weight and most preferably at least 90 % by weight of the reaction product between P-(XH) 2 and the diisocyanate having two isocyanate groups with different reactivity should be attributable to the reaction with the more reactive isocyanate group.
- Another approach to determine different reactivities of isocyanate groups in a diisocyanate is to react 1 mol of diisocyanate with 1 mol of n-hexanol and to determine the ratio of the products, i.e. monourethane, diurethane and unreacted diisocyanate.
- Asymmetric diisocyanates for the purposes of this invention are aromatic, aliphatic or cycloaliphatic diisocyanates, preferably having a molecular weight of about 160 g/mol to 500 g/mol which possess NCO groups having a different reactivity.
- aromatic asymmetric diisocyanates examples include 2,4-toluene diisocyanate (2,4-TDI), naphthalene 1 ,8-diisocyanate (1 ,8-NDI) and 2,4'-methylenediphenyl diisocyanate (2,4'-MDI).
- Suitable cycloaliphatic asymmetric diisocyanates are 1- isocyanatomethyl-3-isocyanato-1 ,5,5-trimethylcyclohexane (isophorone diisocyanate, IPDI),
- 2-isocyanatopropylcyclohexyl isocyanate 1-methyl-2,4-diisocyanatocyclohexane or hydrogenation products of the aforementioned aromatic diisocyanates, especially hydrogenated 2,4'-MDI or 4-methylcyclohexane-1 ,3-diisocyanate (H-TDI).
- Examples of aliphatic asymmetric diisocyanates are 1 ,6-diisocyanato-2,2,4- trimethylhexane, 1 ,6-diisocyanato-2,4,4-trimethylhexane, 2-butyl-2-ethylpentamethylene diisocyanate and lysine diisocyanate.
- Preferred asymmetric diisocyanates are 2,4-toluene diisocyanate (2,4-TDI) and 2,4'-methylenediphenyl diisocyanate (2,4'-MDI).
- 2,4'-methylenediphenyl diisocyanate (2,4'-MDI) comprehends a polyisocyanate having a 2,4'-MDI content of more than 95% by weight, more preferably of more than 97.5% by weight. Additionally the 2,2'-MDI content is below 0.5% by weight, more preferably below 0.25% by weight.
- 2,4-toluene diisocyanate (2,4-TDI) comprehends a polyisocyanate having a 2,4-TDI content of more than 95% by weight, preferably of more than 97.5% by weight, and very preferably of more than 99% by weight.
- the one or more end-capping used to react with the isocyanate-terminated group of the isocyanate-terminated PP have the general formular E-YH, wherein E is an end- capping residue, selected from the group consisting of aliphatic, heteroaliphatic, araliphatic, heteroaliphatic, aromatic and heteroaromatic residues and YH is selected from NHR', OH and SH with R' being defined as above for the XH group(s) of P-(XH) 2 .
- E can be further substituted for example by reactive functional groups such as
- E is a phenolic group. More preferable E-YH is a bisphenol such as bisphenol A, bisphenol P, bisphenol M, bisphenol F 1 bisphenol S, bisphenol AP, bisphenol E or bisphenol TMC, or a hydroxyphenyl ether such as p-hydroxyphenyl ether and p- hydroxyphenyl thioether, or 4,4'-dihydroxy benzophenone, 4,4'-Dihydroxydiphenyl, 2,2'- dihydroxydiphenyl, or 4,4'-cyclohexyliden diphenol, resorcinol or hydrochinon.
- a bisphenol such as bisphenol A, bisphenol P, bisphenol M, bisphenol F 1 bisphenol S, bisphenol AP, bisphenol E or bisphenol TMC, or a hydroxyphenyl ether such as p-hydroxyphenyl ether and p- hydroxyphenyl thioether, or 4,4'-dihydroxy benzophenone, 4,4'-Dihydroxydipheny
- E does not necessarily has to contain a reactive functional group or an aromatic residue.
- the end-capping agent and the isocyanate-terminated PP may be reacted at an appropriate temperature for a sufficient time to cause reaction between the isocyanate groups and the YH groups on the capping agent. Preferably, this reaction continues for a period of about 30 minutes to 4 hours, at a temperature in the range of about 60 to about 100 0 C, preferably about 70 to about 90 0 C, most preferably about 80 to about 90 0 C.
- a catalyst such as any of the condensation catalysts discussed above (e.g. dibutyltin dilaurate), may be used to enhance reaction times in preparing the PP. Of course combinations of such compounds may be used herein.
- an appropriate amount of end-capper is to be used to facilitate such reaction.
- the precise amount of course will depend on the nature, identity and amount of the remaining reactants that are used to form the adduct and as such will be left to the discretion of those persons of ordinary skill in the art.
- the inventive compositions may further comprise as component C) one or more epoxy resins, i.e. epoxy-containing compounds even though the addition of epoxy resins is not necessary.
- the amount of epoxy resins employed does not exceed 60 wt.-%, more preferably 40 wt.-% and most preferably 30 wt.-%.
- Particularly preferable are curable compositions of the present invention that are essentially free of epoxy resins. Commercially available epoxy-containing compounds for use in the curable compositions of the present invention are illustrated below.
- the epoxy-containing compounds used may include multifunctional epoxy- containing compounds, such as Ci-C 2 ⁇ 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;
- epoxy-containing compounds 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
- Suitable epoxy-containing compounds 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. [0072 ] Cresol analogs are also available commercially such as ECN 1273, ECN
- ARALDITE ECN 1400 from Huntsman, Inc. SU-8 and EPI-REZ 5003 are bisphenol A-type epoxy novolacs available from Hexion.
- 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-containing compounds
- the epoxy-containing compounds can be used in the composition of the present invention in an amount of preferably 0 to 60, more preferably 5 to 50 and most preferably 10 to 30 percent by weight based on the total weight of the curable composition.
- Optional additives preferably 0 to 60, more preferably 5 to 50 and most preferably 10 to 30 percent by weight based on the total weight of the curable composition.
- inventive compositions may also contain curing catalysts, which are known to those skilled in the art.
- Examples of curing agents generally include phenolic compounds such as phenol, bisphenol A, bisphenol F or phenol-formaldehyde resins, amines such as imidazole and imidazole derivatives, sulfonic acids such as para-toluene sulfonic acid, Lewis acids such as boron or aluminum halides and aliphatic and aromatic carboxylic acids.
- the curing agent is present in an amount sufficient to cure the composition, such as about 1 to about 15 parts per hundred parts of curable composition, for instance about 3 to about 10 parts per hundred parts of curable composition.
- the curing temperatures of the inventive compositions are between
- the inventive compositions can be used at relatively moderate temperatures to achieve very good productivity.
- the curing can if desired be conducted in two stages, for example, by interrupting the curing process or, if a curing agent is employed for elevated temperatures, by allowing the curable composition to cure partially at lower temperatures.
- 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 curable compositions to reduce their viscosity.
- 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 compositions, may be used in the inventive compositions.
- 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 silica nanoparticle can be pre-dispersed in epoxy resins, and may be selected from those commercially available under the tradename NANOPOX, such as NANOPOX XP 0314, XP 0516, XP 0525, and XP F360 from Nano Resins, Germany.
- NANOPOX products are silica nanoparticle dispersions in epoxy resins, at a level of up to about 50% by weight. These NANOPOX products are believed to have a particle size of about 5 nm to about 80 nm.
- NANOPOX XP 0314 is reported by the manufacturer to contain 40 weight percent of silica particles having a particle size of less than 50 nm diameter in a cycloaliphatic epoxy resin.
- Other kinds of fillers may also include core-shell-particles as for example disclosed in International Patent Application Publication No. WO 2007/064801 A1 (Li) the disclosure of which is incorporated herein by reference.
- the curable compositions of the present invention may be cured to obtain cured products having a flexural modulus and flexural strength being the same or higher than the values for a composition not containing component B), i. e. PP, in particular in formulations that do not need to contain epoxy resins.
- a composition not containing component B i. e. PP
- K 1C and G 1C values should be increased compared to compositions not containing component B).
- One aim of the present invention is to provide curable composition, which comprise after curing a flexural modulus of 2800 MPa or more, more preferably 3000 MPa or more and most preferably 3500 MPa or more and exhibit G 1C values above 200 J/m 2 , more preferably above 250 J/m 2 and most preferably above 350 J/m 2 or even as high as at least about 400 J/m 2 or at least about 450 J/m 2 .
- the invention relates also to the use of the curable compositions in the formation of prepregs or towpregs formed from a layer or bundle of fibers infused with the inventive heat curable composition.
- 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 the inventive heat curable composition; and (c) joining the heat curable 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 heat curable 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 the inventive heat curable composition in liquid form; (c) passing the layer or bundle of fibers through the liquid heat curable composition to infuse the layer or bundle of fibers with the heat curable composition; and (d) removing excess heat curable 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 compositions 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 inventive composition 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.
- an adhesion promoter such as the inorganic filler noted above, or a different one
- a filler such as the inorganic filler noted above, or a different one
- a thermoplastic additive such as the inorganic filler noted above, or a different one
- a reactive or non-reactive diluent such as the inorganic filler noted above, or a different one
- a thixotrope such as the inorganic filler noted above, or a different one
- the inventive compositions in adhesive form may be placed in film form, in which case a support e.g.
- curable compositions including MDA-phenyl benzoxazine and N-phenyl benzoxazine as a N-arylated benzoxazine matrix resin are used.
- Cycloaliphatic diepoxide (CY) Sample 1 (as a control sample) consists of MDA-phenyl benzoxazine alone.
- Samples 2 and 3 are control samples comprising 80 % by weight of MDA- phenyl benzoxazine and 20 % by weight of pre-polymers prepared by use of symmetric diisocyanates, i.e. having two isocyanate groups of identical reactivity.
- the pre-polymer used in Sample 2 is R-PU I and the pre-polymer used in Sample 3 is R-PU II.
- Samples according to the invention are Samples 4 to 18. Sample 4 is an 80/20
- Samples 5, 6 and 7 are 90/10 (w/w), 80/20 (w/w) and 70/30 (w/w) mixtures of MDA-phenyl benzoxazine and PU II.
- Samples 8 to 18 contain 80 % by weight of MDA-phenyl benzoxazine and 20 % by weight of a pre-polymer toughener.
- the pre-polymer toughener of Sample 8 is PU III, of Sample 9 is PU IV, of Sample 10 is PU V, of Sample 11 is PU VII, of Sample 12 is PU VIII, of Sample 13 is PU IX, of Sample 14 is PU X, of Sample 15 is PU Xl, of Sample 16 is PU XII, of Sample 17 is PU XIII and of Sample 18 is PU XIV.
- Samples 19 to 21 contain 80 % by weight of MDA-phenyl benzoxazine and 20
- the pre-polymer toughener of Sample 19 is PU XV
- of Sample 20 is PU XVI
- of Sample 21 is PU XVII.
- Samples 22 and 23 contain 80 % by weight of MDA-phenyl benzoxazine and
- the pre-polymer toughener of Sample 22 is R-PU III and of Sample 23 is R-PU IV.
- Samples 24 describes an 80/20 (w/w) mixtures of a benzoxazine resin mixture and pre-polymer toughener PU II.
- the benzoxazine resin mixture is 60/40 (w/w) of MDA- phenyl benzoxazine and N-phenyl benzoxazine.
- Samples 25 describes an 80/20 (w/w) mixture of a benzoxazine resin mixture and pre-polymer toughener PU IV.
- the benzoxazine resin mixture is 60/40 (w/w) of MDA- phenyl benzoxazine and N-phenyl benzoxazine.
- Sample 26 describes a 70/20/10 (w/w/w) mixture of a benzoxazine resin mixture, cycloaliphatic diepoxide CY and pre-polymer toughener PU II.
- the benzoxazine resin mixture is 60/40 (w/w) of MDA-phenyl benzoxazine and N-phenyl benzoxazine.
- the curable compositions were cured in sealed containers in a circulating air drying oven at 180 °C for 3 hours. Subsequently the Samples were taken out of the drying oven, removed from the container and cooled to room temperature.
- Samples 2 and 3 are not compatible with the N-arylated benzoxazine, as noted by a lack of homogeneity. Curing of those samples leads to products having sticky surfaces.
- Samples based on pre-polymers as tougheners, where the pre- polymers were synthesized using diisocyanates having two isocyanate groups with different reactivity are homogeneous and do not exhibit tacky surfaces.
- those Samples 4 to 18 show a significant increase of G1c values indicating an increased impact strength. Surprisingly there is no or almost no effect on the glass transition temperature. Furthermore the decrease in flexural strength and flexural modulus is very low.
- Samples 6, 14 and 15 show the influence of the end-capping molecule used to end-cap free isocyanate groups in the synthesis of the pre-polymers.
- Sample 6 makes use of bisphenol A as sole end-capper in the pre-polymer synthesis
- a 50/50 mixture (molar ratio 1 :1 ) of bisphenol A and n-butylamine was used for the preparation of the pre-polymer of Sample 14 .
- the pre-polymer used was only end-capped with n-butylamine. The biggest influence is seen on the flexural modulus, which is decreased when bisphenol A is replaced by n-butylamine.
- n-butylamine capped pre-polymers are still suitable, albeit not being preferred. Therefore phenolic end- cappers are preferred in the present invention. This is even more true for Sample 16, where a pre-polymer is used, which is end-capped with a 3-aminopropanol, still exhibiting a very good G1c value, but a relatively poor flexural modulus.
- Samples 22 and 23 are not compatible with the N-arylated benzoxazine, as noted by a lack of homogeneity.
- Samples 24 to 26 show that the cured products of N-arylated benzoxazine resin mixtures and mixtures of N-arylated benzoxazine resins and an epoxy resin, each mixture comprising a pre-polymer toughener of the present invention exhibit very high G1 c values.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Sealing Material Composition (AREA)
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP08860737.9A EP2217651B1 (en) | 2007-12-06 | 2008-12-02 | Curable compositions containing isocyanate-based tougheners |
BRPI0820687 BRPI0820687B1 (en) | 2007-12-06 | 2008-12-02 | curable, adhesive, sealant or coating compositions containing isocyanate-based stiffeners |
ES08860737T ES2435547T3 (en) | 2007-12-06 | 2008-12-02 | Curable compositions containing isocyanate-based hardeners |
CN2008801186570A CN101939370A (en) | 2007-12-06 | 2008-12-02 | Contain curable compositions based on isocyanic ester toughner |
CA2708261A CA2708261C (en) | 2007-12-06 | 2008-12-02 | Curable compositions containing isocyanate-based tougheners |
US12/765,973 US20100204400A1 (en) | 2007-12-06 | 2010-04-23 | Curable compositions containing isocyanate-based tougheners |
US17/075,162 US20210102035A1 (en) | 2007-12-06 | 2020-10-20 | Curable compositions containing isocyanate-based tougheners |
US18/149,269 US20230159693A1 (en) | 2007-12-06 | 2023-01-03 | Curable compositions containing isocyanate-based tougheners |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US99291607P | 2007-12-06 | 2007-12-06 | |
US60/992,916 | 2007-12-06 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US12/765,973 Continuation US20100204400A1 (en) | 2007-12-06 | 2010-04-23 | Curable compositions containing isocyanate-based tougheners |
Publications (2)
Publication Number | Publication Date |
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WO2009075743A2 true WO2009075743A2 (en) | 2009-06-18 |
WO2009075743A3 WO2009075743A3 (en) | 2009-08-20 |
Family
ID=40756022
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Application Number | Title | Priority Date | Filing Date |
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PCT/US2008/013290 WO2009075743A2 (en) | 2007-12-06 | 2008-12-02 | Curable compositions containing isocyanate-based tougheners |
Country Status (7)
Country | Link |
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US (3) | US20100204400A1 (en) |
EP (1) | EP2217651B1 (en) |
CN (1) | CN101939370A (en) |
BR (1) | BRPI0820687B1 (en) |
CA (1) | CA2708261C (en) |
ES (1) | ES2435547T3 (en) |
WO (1) | WO2009075743A2 (en) |
Cited By (5)
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WO2010031826A1 (en) * | 2008-09-19 | 2010-03-25 | Henkel Ag & Co. Kgaa | Benzoxazine-based compositions containing isocyanate-based tougheners |
WO2011050834A1 (en) * | 2009-10-27 | 2011-05-05 | Henkel Ag & Co. Kgaa | Benzoxazine-containing compositions |
WO2013028281A1 (en) * | 2011-08-22 | 2013-02-28 | Dow Global Technologies Llc | Toughener and toughened epoxy adhesive |
US20150051315A1 (en) * | 2012-02-17 | 2015-02-19 | Huntsman Advanced Materials Americas Llc | Mixture of Benzoxazine, Epoxy and Anhydride |
CN108504290A (en) * | 2018-05-10 | 2018-09-07 | 江苏地基工程有限公司 | A kind of water resistant resin anchor fixing agent and preparation method thereof |
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GB201205574D0 (en) * | 2012-03-29 | 2012-05-16 | Cytec Tech Corp | Benzoxazines and compositions containing the same |
US9777155B2 (en) | 2012-06-27 | 2017-10-03 | Toray Industries, Inc. | Benzoxazine resin composition, prepreg, and fiber-reinforced composite material |
BR112017013941B1 (en) * | 2014-12-29 | 2021-08-24 | Cytec Industries Inc | CURABLE COMPOSITION, COMPOSITE MATERIAL, AND METHODS FOR FORMING A PRE-IMPREGNATE AND FOR MANUFACTURING A COMPOSITE PART, PRE-IMPREGNED |
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2008
- 2008-12-02 BR BRPI0820687 patent/BRPI0820687B1/en active IP Right Grant
- 2008-12-02 CA CA2708261A patent/CA2708261C/en active Active
- 2008-12-02 CN CN2008801186570A patent/CN101939370A/en active Pending
- 2008-12-02 WO PCT/US2008/013290 patent/WO2009075743A2/en active Application Filing
- 2008-12-02 ES ES08860737T patent/ES2435547T3/en active Active
- 2008-12-02 EP EP08860737.9A patent/EP2217651B1/en active Active
-
2010
- 2010-04-23 US US12/765,973 patent/US20100204400A1/en not_active Abandoned
-
2020
- 2020-10-20 US US17/075,162 patent/US20210102035A1/en not_active Abandoned
-
2023
- 2023-01-03 US US18/149,269 patent/US20230159693A1/en not_active Abandoned
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010031826A1 (en) * | 2008-09-19 | 2010-03-25 | Henkel Ag & Co. Kgaa | Benzoxazine-based compositions containing isocyanate-based tougheners |
CN102159636A (en) * | 2008-09-19 | 2011-08-17 | 汉高股份有限及两合公司 | Benzoxazine-based compositions containing isocyanate-based tougheners |
WO2011050834A1 (en) * | 2009-10-27 | 2011-05-05 | Henkel Ag & Co. Kgaa | Benzoxazine-containing compositions |
WO2013028281A1 (en) * | 2011-08-22 | 2013-02-28 | Dow Global Technologies Llc | Toughener and toughened epoxy adhesive |
CN103732647A (en) * | 2011-08-22 | 2014-04-16 | 陶氏环球技术有限责任公司 | Toughener and toughened epoxy adhesive |
JP2014529654A (en) * | 2011-08-22 | 2014-11-13 | ダウ グローバル テクノロジーズ エルエルシー | Tougheners and reinforced epoxy adhesives |
US20150051315A1 (en) * | 2012-02-17 | 2015-02-19 | Huntsman Advanced Materials Americas Llc | Mixture of Benzoxazine, Epoxy and Anhydride |
TWI641648B (en) * | 2012-02-17 | 2018-11-21 | 美商漢士門先進材料美國責任有限公司 | Mixture of benzoxazine, epoxy and anhydride |
CN108504290A (en) * | 2018-05-10 | 2018-09-07 | 江苏地基工程有限公司 | A kind of water resistant resin anchor fixing agent and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
EP2217651A4 (en) | 2012-05-02 |
CA2708261C (en) | 2016-02-02 |
EP2217651A2 (en) | 2010-08-18 |
CN101939370A (en) | 2011-01-05 |
BRPI0820687B1 (en) | 2019-11-26 |
CA2708261A1 (en) | 2009-06-18 |
ES2435547T3 (en) | 2013-12-20 |
US20100204400A1 (en) | 2010-08-12 |
BRPI0820687A2 (en) | 2017-05-09 |
EP2217651B1 (en) | 2013-08-28 |
WO2009075743A3 (en) | 2009-08-20 |
US20230159693A1 (en) | 2023-05-25 |
US20210102035A1 (en) | 2021-04-08 |
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