WO1996027640A1 - Epoxy-cyanate ester compositions - Google Patents
Epoxy-cyanate ester compositions Download PDFInfo
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- WO1996027640A1 WO1996027640A1 PCT/US1996/000544 US9600544W WO9627640A1 WO 1996027640 A1 WO1996027640 A1 WO 1996027640A1 US 9600544 W US9600544 W US 9600544W WO 9627640 A1 WO9627640 A1 WO 9627640A1
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- cyanate ester
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- 0 *=NC1(c2ccccc2-c2ccccc12)O Chemical compound *=NC1(c2ccccc2-c2ccccc12)O 0.000 description 2
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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
- 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
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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
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/065—Preparatory processes
- C08G73/0655—Preparatory processes from polycyanurates
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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
- C08G59/20—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 epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
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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
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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
-
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/903—Interpenetrating network
Definitions
- This invention relates to mixed epoxy resin and cyanate ester resin compositions that can be cured to interpenetrating polymer networks (TPNs).
- the IPNs provide high temperature stable vibration damping materials, adhesives, binders for abrasives, and protective coatings.
- IPNs have been disclosed.
- Energy-curable compositions comprising interpenetrating polymer networks of epoxy resins and acrylate resins have been described (see, for example, U.S. Patent Nos. 5,262,232 and 5,086,088) in which the compositions are stated to be useful as pressure sensitive adhesives and as vibration damping materials.
- the compositions have limited utility at higher temperatures.
- Cyanate esters which can be prepared by reacting polyhydric phenols with cyanogen bromide, as described in U.S. Patent No. 3,553,244, are thermosetting resins having high heat resistance and, at the same time, considerable brittleness.
- Interpenetrating polymer networks of cyanate ester resins and acrylate resins show considerably increased flexibility as well as resistance to moderately high temperature degradation. See, for example, U.S. Patent No. 5,331,018.
- industrial applications at temperatures exceeding 275°C. are becoming more common, and the need exists for materials that are both flexible and durable at these temperatures.
- Blends of cyanate ester resins and epoxy resins have been described.
- U.S. Patent Nos. 4,604,452, 4,785,075, 4,902,752, 4,983,683, 5,068,309, and 5, 149,863 describe various blends of cyanate ester resins with glycidyl ethers of polyhydric phenols ('452 and O75) or with thermoplastic resins such as polysulfones, polyetherimides, polyarylethers, etc., terminated with epoxy groups ('752 and '683). Compositions of various morphologies and properties were obtained. Single polymer networks or polymer blends were obtained, but no interpenetrating polymer networks are disclosed.
- 4,797,454 describes cyanate-functional oxazolinylpolysiloxanes useful for toughening resin systems such as epoxies and cyanates.
- Oligomeric epoxy-terminated siloxanes e.g., glycidyl ethers
- dicyanates e.g., glycidyl ethers
- cross- reaction of glycidyl ethers with cyanates is faster than self-condensation of the epoxy compounds, so that no interpenetrating polymer network is formed.
- U.S. Patent No. 4,956,393 describes heat curable cyanate adhesive compositions comprising a cyanate ester resin, an epoxy resin, and a catalyst effective to promote the elevated temperature cure of the composition. Both polysiloxyl and cycloaliphatic epoxy resins are disclosed, while tin catalysts, e.g., tin octanoate, are said to be preferred for the polymerizations (col. 7, lines 8-9). In Example 9, a non-Bronsted acid initiator is used in an uncured composition comprising cycloaliphatic epoxy, cyanate ester, and polyimide.
- U.S. Patent No. 5,043,411 describes a thermosetting cyanate ester resin containing an epoxy resin pre-condensed with an aromatic amine or aromatic amide.
- catalyst for the cyanate ester polymerization only a coordination metal compound soluble in nonylphenol is described.
- Catalysts for the epoxy condensation reaction include amine salts, imidazoles, tertiary amines or hindered phenols. Interpenetrating polymer networks are not disclosed.
- U.S. Patent No. 5,330,684 describes Z-axis conductive adhesive compositions comprising cyanate ester resins, film-forming thermoplastic resins, epoxy resins including cycloaliphatic epoxies, an organometallic catalyst, and conductive particles. No Bronsted acids are disclosed as catalysts. Summary of the Invention
- the present invention provides a polymerizable composition of matter comprising a cycloaliphatic epoxy resin, a cyanate ester resin, optionally a polyol, a Bronsted acid as initiator, and optionally a stabilizer for the initiator.
- the present invention can provide an interpenetrating polymer network (IPN) prepared from the above-de-scribed polymerizable composition.
- IPN interpenetrating polymer network
- a method of polymerizing monomers to provide an IPN comprising the step of polymerizing a miscible mixture of cycloaliphatic epoxy resin, a cyanate ester resin, optionally a polyol, and, as cationic initiator, a Bronsted acid, and optionally a stabilizer for the initiator, the energy for polymerization of the cycloaliphatic epoxy and cyanate ester resins being provided at temperatures differing by at least 20°C so as to sequentially polymerize the resins and provide an IPN.
- the initial temperature of cure for the cycloaliphatic epoxy and the higher temperature of cure for the cy.anate ester resin depend on the curable composition and the curatives employed.
- a mixed cycloaliphatic epoxy resin and cyanate ester resin composition comprising a Bronsted acid as initiator when subjected to two different temperatures (at least 20°C apart) can be sequentially polymerized to provide an IPN which is stable at temperatures of at least about 300°C for at least one hour.
- the IPNs are essentially free of epoxy-cyanate interreaction (cross- reaction) product. It has been found that the use of Bronsted acid as initiator provides an interpenetrating polymer network which is responsible for high temperature stability of the cured product.
- the present invention provides the art with useful vibration damping, adhesive, abrasive, and coating compositions which are stable to temperatures of at least 300°C for prolonged periods of time in the absence of oxygen.
- “Bronsted acid” means a compound capable of donating a proton, optionally with heating; the term includes compounds capable of generating a Bronsted acid;
- stabilizer means an additive that controls the activity of a Bronsted acid initiator
- “.sequentially polymerized” means polymerization of cycloaliphatic epoxy at a lower temperature followed by polymerization of cyanate ester at a higher temperature;
- interpenetrating polymer network means a plurality of intermeshed polymers, each highly crosslinked, with essentially no cycloaliphatic epoxy-cyanate ester cross-reactions;
- B-stage means at least partial cure of at least one component in a resin mixture, provided that all components are not fully cured; such a composition comprises monomeric and polymeric materials.
- the compositions of the present invention offer environmentally desirable solventless processing.
- An added advantage is the sequential thermal cure of the components which can provide the cyanate ester-cycloaliphatic epoxies as either two-part liquid precursor or as a "B-staged" two-part composition.
- the starting materials exhibit low vapor pressure because of their relatively high molecular weights.
- the present invention compositions can be processed under the ambient environment, e.g., in the presence of oxygen. Additionally, the present invention IPNs can retain their flexibility at temperatures of at least 300°C for at least one hour. Such materials make particularly useful vibration damping materials.
- FIG. 1 shows DMA (dynamic mechanical analysis) scans from -70 to 280°C for two compositions, A (comparative) and B (present invention).
- FIG. 2 shows DMA scans of a comparative composition comprising glycidyl epoxy resin C (non-annealed) and D (annealed).
- FIG. 3 shows DMA scans E and F from -70 to >250°C of comparative sample/.
- FIG. 4 shows DMA scans G (non-annealed) and H (annealed) from -70 to >250°C of comparative sample II.
- FIG. 5 shows DMA scans I (non-annealed), J (intermediate annealed), and K
- sample I_ (fully annealed) from ⁇ 50 to >250°C for sample I_ a composition within the present invention.
- FIG. 6 shows a DSC scan of the cure exotherm for a comparative composition.
- FIG. 7 shows a DSC scan of cure exotherms for a composition of the present invention.
- FIG. 8 shows a DSC scan of the cure exotherm of a comparative composition.
- FIG. 9 shows a DSC scan of cure exotherms for a composition of the present invention.
- compositions of the present invention provide vibration-damping, adhesive, abrasive binder, and coating materials exhibiting remarkably high temperature stability and utility over a broad range of temperatures.
- vibration damping materials comprising IPNs of the present invention are stable over a temperature range of about 0 to at least 300°C.
- compositions of the present invention comprise resins which are cured in sequential fashion using a single catalyst, a Bronsted acid, which activates the epoxy resin component at a temperature preferably at or near room temperature, then activates cyanate trimerization into poly(triazines) at temperatures at least 20°C higher, preferably 50°C higher, and more preferably 50 to 100°C higher. It appears that Bronstead acids afford a much faster cycloaliphatic epoxy polymerization than cyanate ester polymerization at a specific temperature in the range of 0 to 150°C.
- the distinct separation in cure temperatures provides convenient processing and handling; the two-part system can be mixed and cured on site, or a "B-staged" film comprising at least partially cured cycloaliphatic epoxy resin and uncured cyanate ester can be prepared and easily transported to the work site where it can be cut or formed into a desired shape, applied between workpieces and thermally cured.
- the compositions of the invention are environmentally responsible, in that no solvents are used in any step of their formulation or use. Because the individual components are typically odorless, low vapor pressure liquids whose cures are unaffected by ambient oxygen, they can be handled and processed with only nominal precautions.
- Cyanate ester resins comprise cyanate ester compounds (monomers and oligomers) each having one or preferably two or more -OCN functional groups, -and typically having a cyanate equivalent weight of from about 50 to about 500, preferably from about 50 to about 250. Molecular weight of the monomers and oligomers are typically from about 150 to about 2000. If the molecular weight is too low, the cyanate ester may have a crystalline structure which is difficult to dissolve. If the molecular weight is too high, the compatibility of the cyanate ester with other resins may be poor.
- compositions of the invention include one or more cyanate esters according to formulas I, ⁇ , m or IV.
- Formula I is represented by
- Q(OCN) p I where p is an integer from 1 to 7, preferably from 2 to 7, and wherein Q comprises a mono-, di-, tri-, or tetravalent aromatic hydrocarbon containing from 5 to 30 carbon atoms and zero to 5 aliphatic, cyclic aliphatic, or polycyclic aliphatic, mono- or divalent hydrocarbon linking groups containing 7 to 20 carbon atoms.
- Q may comprise 1 to 10 heteroatoms selected from the group consisting of non- peroxidic oxygen, sulfur, non-phosphino phosphorus, non-amino nitrogen, halogen, and silicon.
- each R 1 is independently hydrogen, an alkyl group having from one to three carbon atoms, or a cyanate group (-OC ⁇ N), with the proviso that at least one R 1 group is a cyanate group.
- each of the R 1 groups is either -H, methyl or a cyanate group, with at least two R 1 groups being cyanate groups.
- Formula m is represented by
- each R 3 is independently -H, a lower alkyl group having from about 1 to about 5 carbon atoms, or a cyanate ester group, and preferably is a hydrogen, methyl or a cyanate ester group, with the proviso that the R 3 s together comprise at least one cyanate ester group.
- Useful cyanate ester compounds include, but are not limited to the following: 1,3- and 1,4-dicyanatobenzene; 2-tert-butyl- 1 ,4-dicyanatobenzene; 2,4-dimethyl- 1 ,3-dicyanatobenzene; 2, 5-di-tert-butyl- 1 ,4-dicyanatobenzene; tetramethyl-l,4-dicyanatobenzene;
- cyanic acid esters derived from phenolic resins e.g., as disclosed in U.S. Patent No. 3,962,184, cyanated novolac resins derived from novolac, e.g., as disclosed in U.S. Patent No. 4,022,755, cyanated bis-phenol-type polycarbonate oligomers derived from bisphenol-type polycarbonate oligomers, as disclosed in U.S. Patent No. 4,026,913, cyano-terminated polyarylene ethers as disclosed in U.S. Patent No. 3,595,900, and dicyanate esters free of ortho hydrogen atoms as disclosed in U.S. Patent No.
- Polycyanate compounds obtained by reacting a phenol-formaldehyde precondensate with a halogenated cyanide are also useful.
- Examples of preferred cyanate ester resin compositions include low molecular weight (M_) oligomers, e.g., from about 250 to about 5000, e.g., bisphenol-A dicyanates such as AroCyTM "B-30 Cyanate Ester Semisolid Resin”; low molecular weight oligomers of tetra o-methyl bis-phenol F dicyanates, such as "AroCyTM M-30 Cyanate Ester Semisolid Resin”; low molecular weight oligomers of thiodiphenol dicyanates, such as AroCyTM "T-30", all of which are commercially available from Ciba-Geigy Corp., Hawthorne, NY.
- M_ low molecular weight
- Cycloaliphatic epoxy resins useful in the invention preferably are selected from 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (ERL-4221), 2-(3 ,4-epoxy)cyclohexylmethyl-5 , 5 ' -spiro(3 ,4-epoxy)cyclohexane-m-dioxane (ERL- 4234), and bis((4-methyl-7-oxabicyclo(4.1.0)hept-3-yl)methyl) adipate (ERL-4299), all of which are available from Union Carbide Corp., Tarrytown, NY.
- cycloaliphatic epoxies that are useful in the present invention include vinyl cyclohexene monoxide (Union Carbide Corp.), cyclohexene oxide (Aldrich Chemical Co., Milwaukee, WI), vinyl cyclohexene dioxide (ERL 4206TM, Union Carbide Corp.), and limonene oxide, limonene dioxide, and ⁇ -pinene oxide (these three being available from Elf Atochem, Philadelphia, PA).
- cycloaliphatic mono- and di-epoxy oligo-siloxanes which include ⁇ , ⁇ -di-(3,4-cyclohexene-2-ethyl) siloxanes, such as ⁇ , ⁇ -di-(3,4- cyclohexene-2-ethyl)-tetramethyl disiloxane, ⁇ , ⁇ -di(3 ,4-cyclohexene-2-ethyl)- hexamethyl trisiloxane, as well as ⁇ -3,4-cyclohexene-2-ethyl siloxanes, such as ⁇ - 3,4-cyclohexene-2-ethyl pentamethyl disiloxane.
- epoxies can be prepared according to the method of Crivello et al., J. Poly. Sci., A: Poly. Chem. 2S, PP 479- 503 (1990).
- compositions of the invention may include acyclic aliphatic, cycloaliphatic and oligomeric polyhydroxy compounds commonly known as polyols.
- Polyols are known in the art for their reaction with polyepoxy resins to form so- called “chain-extended” epoxies, wherein low- to medium-molecular weight copolymers are formed.
- chain-extended epoxy resins can add flexibility and resilience to compositions of the invention without compromising their thermal stability.
- Amine chain-extenders are preferably avoided in the present invention because significant amounts of amines (i.e., 10% weight percent or greater of the total composition) interfere with the action of the initiator.
- Polyols useful in the present invention preferably have two to five, more preferably two to four, hydroxyl groups.
- useful polyols include, but are not limited to, 1,2-ethanediol, 1,2-propanediol, 1,3 -propanediol, 1,4-butanediol, 1,3- butanediol, 2-methyl- 1,3 -propanediol, 2, 2-dimethyl- 1,3 -propanediol, and 2-ethyl- 1,6-hexanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, glycerol, trimethylolpropane, 1,2,6-hexanetriol, trimethylolethane, pentaerythritol, quinitol, mannitol, diethylene glycol, tri
- Useful higher molecular weight polyols include the polyethylene and polypropylene oxide polymers in the molecular weight range of 200 to 20,000 such as the CarbowaxTM polyethyleneoxide materials supplied by Union Carbide, Tarrytown, NY, caprolactone polyols in the molecular weight range of 200 to 5,000, such as the ToneTM polyol materials supplied by Union Carbide, polytetramethylene ether glycol in the molecular weight range of 200 to 4,000, such as the TerathaneTM materials supplied by Dupont (Wilmington, DE), hydroxyl terminated polybutadiene resins such as the Poly bdTM supplied by Elf Atochem, Philadelphia, PA, or equivalent materials supplied by other manufacturers.
- Polytetramethylene ether glycols such as Poly THF 250TM, Poly THF CD 1000TM, and Poly THF CD 2000TM, all available from BASF, Mount Olive, NJ, are particularly useful polyols.
- Polyether polyols and polyester polyols are particularly useful.
- the alcohol functional component can be present as a mixture of materials and comprises poly-hydroxyl containing materials.
- the compositions preferably comprises an amount sufficient to provide an epoxy to hydroxy weight ratio in the composition between about 0.3:1 to 100:1, preferably between about 0.5: 1 to 2: 1.
- the ratio of (epoxy resin plus optional polyol) to cyanate ester resin in the composition of the invention is in the weight percent range (40 to 80) to (60 to 20), preferably (50 to 65) to (50 to 35).
- Bronsted acid initiators useful in the present invention include any of the strong protic acids (i.e., proton donors) whose anions are sufficiently non- nucleophilic, nonbasic and nonreducing so as to prevent initiator deactivation and cationic chain termination.
- the conjugate base of such acids typically has a pK, of zero or less.
- Useful Bronsted acids of the invention include:
- R is fully fluorinated, and contains less than 20 carbon atoms, preferably less than 8 carbon atoms, and, more preferably, contains from 1 to 3 carbon atoms;
- Y is hydrogen or an ammonium cation having at least one hydrogen on the nitrogen atom;
- Q' is a divalent radical of the general formula -NY- or -CR 4 Y-, wherein R 4 is selected from the group consisting of H, Cl, Br, I, alkyl having from 1 to 19 carbon atoms, alkenyl having from 3 to 20 carbon atoms, aryl having up to 20 carbon atoms (preferably up to 10 carbon atoms), alkaryl having from 7 to 20 carbon atoms, or R SO 2 ; and Y is as defined above.
- Preferred salts of fluoroalkanesulfonic acids are those wherein Y is as defined above; preferred bis(fluoroalkylsulfonyl) methanes are those wherein Q' is selected from the group consisting of -NH-, and -CHCR/SO 2 )-;
- acid-generating esters as described, for example, in U. S. Patent No. 3,907,706.
- acid-generating esters which decompose thermally are the esterification product of a tertiary alkyl alcohol and an acid that forms a chelation complex with a metal cation of a metal salt, and preferably comprise:
- any tertiary alcohols that form an ester reaction product with an appropriate acid may be used, including, but not limited to, t-butanol, 1,1- dimethylpropanol, l-methyl-2-ethylpropanol, 1,1-dimethyl-n-butanol, 1,1-dimethyl- n-pentanol, 1,1-diphenylethanol, 1,1-dibenzylethanol, and the like, with
- chelating acids preferably selected from the group consisting of oxalic, phosphoric, phosphorous, malonic, succinic, fumaric, glycolic, lactic, gamma-hydroxybutyric, oxalacetic, tartaric, pyruvic, acetoacetic, mercaptosuccinic, thiophosphoric, chromic, vanadic, and related acids.
- Metal salts which can be useful with the above thermally-decomposable esters are those comprising essentially any metal; all metals inclusive of and to the left of aluminum, germanium, antimony and polonium on the periodic chart of the elements, and the rare earth metals can function in the invention. According to the Periodic Table in Advanced Organic Chemistry, Cotton -and Wilkinson, 2d. Ed., Wiley Interscience Publishers, 1966, more preferred metals would be those of Groups LA, HA, VIA, Vffl, LB, ILB, IIIB, IVB and VB, VIB (CAS version of the Periodic Table) and lanthanum, titanium, zirconium, chromium, molybdenum, manganese, cesium and gadolinium.
- Counterions for the metal cations can be essentially any negatively-charged species commonly associated with a metal, and may include, but are not limited to, chloride, bromide, iodide, fluoride, fluoroalkylsulfonides and bis(fluoroalkylsulfonyl)methides generated from the above- noted fluoroalkylsulfonic acids and bis(fluoroalkylsulfonyl)methanes, those derived from mineral acids such as sulfonic, sulfuric, phosphonic, phosphoric, and the like; (3) aromatic amine salts of antimony hexafluoride, as described, for example, in U. S. Patent No. 3,542,828.
- Such salts preferably comprise compounds of the general formula wherein each R 3 may be independently H or the -same or different alkyl groups having from between 1 and 20 carbon atoms, and aryl, alkaryl, alkoxyaryl or haloaryl having up to 20 carbon atoms, provided that at least one R 5 is not hydrogen.
- Representative amines useful as hexafluoroantimonate salts include, but are not limited to, aniline, diphenylamine, triphenylamine, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, hexylamine, nonylamine, (trichlorophenyl)amine, tritolylamine, and the like.
- Anilinium hexafluoroantimonate is a preferred example of this class of catalysts; (4) hydroxylamine salts of antimony hexafluoride, as described, for example, in U. S. Patent No. 3,879,312, which may be represented by the general formula R 6 R 7 N(OH)H + SbF 6 " , wherein R 6 may be H, alkyl, aryl, aralkyl, alkaryl groups comprising up to 20 carbon atoms, preferably up to 10 carbon atoms, and R 7 may be alkyl, aryl, aralkyl, alkaryl groups comprising up to 20 carbon atoms, preferably up to 10 carbon atoms.
- Preferred groups include tolyl and benzyl, with benzyl being particularly preferred.
- these catalysts include hexafluoroantimonates of mono- and diphenylhydroxylammonium, mono- and dibenzylhydroxylammonium, mono- and bis(m-chlorophenyl)hydroxylammonium, and mono- and bis-(p-tolyl)hydroxylammonium.
- Dibenzylhydroxylammonium hexafluoroantimonate is a most preferred example of this class of catalysts;
- salts of the general formula MF m OR 8 TT which are formed by the general reaction of an alcohol R 8 OH with a functionally complementary compound comprising a perfluoro group MF m , wherein OR 8 is the residue of an aliphatic or aromatic alcohol preferably having a molecular weight (M.) of 32 to at least about 100,000, and a primary or secondary hydroxyl functionality of at least 1, preferably at least 2; M is an atom selected from the group consisting of boron, antimony, arsenic, phosphorous, and the like; and m is the valence of the atom M.
- perfluorometal compounds are BF 3) PF S , AsFj, SbFs, and related compounds, and the like.
- a example of this class of compounds is the complex formed by the reaction of BF 3 with methanol;
- each R 9 is independently hydrogen, primary or secondary alkyl group having from 1 to about 10 carbon atoms, or benzyl;
- R 10 , R n , and R 12 are independently hydrogen, an alkyl group having 1 to 10 carbon atoms, benzyl, or an electron donating group, or at least one of R 10 and R n is joined together with R 12 to form a benzo group; provided that, if no benzo group is present in the hindered amine, at least one of R 9 , R 10 , and R n is an alkyl group or an electron donating group; and if R 10 , R 11 and one R 9 is hydrogen, the other R 9 is an alkyl group having at least two carbon atoms.
- Suitable electron donating groups include hydroxyl group, branched straight chain or cyclic alkyl or alkoxy groups having up to 18 carbon atoms and amine groups.
- the substituted pentafluoroantimonic acid can have the formula HSbFjX, wherein X is halogen, hydroxy, or -OR 13 , wherein OR 13 is the residue of an aliphatic or aromatic alcohol preferably having a molecular weight (Mn) of 32 to at least about 100,000, and a primary or secondary hydroxyl functionality of at least 1, preferably at least 2.
- the most preferred alcohol is diethylene glycol, i.e., the most preferred -OR 13 group is 2-(2-hydroxyethoxy)ethoxy, -and the most preferred example of this class of catalysts is the equimolar reaction product of antimony pentafluoride, diethylene glycol (DEG) and 2,6-diethylaniline (DEA).
- the initiator can be present in the range of 0.1 to 10 percent by weight of the polymerizable composition, preferably 0.5 to 5 percent.
- an effective amount of an aromatic amine as stabilizer (less than 10 weight percent, preferably 0.1 to 8 weight percent based on the total composition) can be used with the catalyst to inhibit premature curing.
- High temperature .stable resins of the invention are prepared generally by admixture of a cyanate ester resin, cycloaliphatic epoxy resin, preferably a polyether polyol, and a suitable Bronsted acid.
- the mixture can be spread on a suitable heat-resistant release liner, then cured at 90 - 150°C, preferably 100 - 125°C, for 1-15 minutes, preferably 5-8 minutes.
- the resultant film is a flexible, tough sheet that can be cut or shaped, then applied between workpieces that are to be bonded together. Subsequent heating, preferably at temperatures above 200°C, cures the cyanate ester component and produces, in this embodiment, a temperature- resistant vibration-damping bond.
- a curable mixture may be cast into a preferred shape or into a cavity, then heated to cure the composition in place. Heating can be carried out in a single continuous operation or in two distinct steps, separated in time.
- the initiator provides for independent polymerization of the cycloaliphatic epoxy resin and the cyanate ester resin.
- a tough, high-temperature protective coating may be prepared by heating a composition of the invention that has been applied directly on a substrate.
- the present invention LPNs provide ultra high temperature damping materials, high temperature adhesives, binders for use in high temperature abrasives, and high temperature protective coatings.
- IPN In the IPN there are two intermeshed components, each highly crosslinked, and not swellable by solvents.
- the polymerizable composition of the present invention can be provided as a kit comprising a two-part composition, a first part comprising a cycloaliphatic epoxy resin and a cyanate ester resin, and a second part comprising a Bronsted acid initiator and optionally a polyol.
- LAC means a mixture comprising a 1:1:2.93 weight-to-weight ratio of SbFj: diethylene glycol (DEG) and 2,6- diethylaniline (DEA), as stabilizer, the preparation of which is described in U.S. Patent No. 4,503,211, example 1.
- sample A A second aliquot (sample A) was taken and mixed with one part (relative to the weight of the aliquot) of dicyclopentadienyl iron antimony hexafluoride (Cp 2 FeSbF6, a Lewis acid initiator), 40% by weight in 3- methyltetrahydrothiophene- 1,1 -dioxide (3 -methyl sulfolane, available from Aldrich).
- Samples A and B were knife-coated between 0.050 mm silicone-release-coated polyethylene terephthalate sheets and the sandwich construction was heated in a convection oven at 125°C for 7 minutes such that the resin mixture formed a flexible free-standing film.
- the release liners were removed and a sample of the resin film was cut into a 51 x 12.5 mm coupon which was sandwiched between two 0.25 mm thick steel coupons of the same size as the resin film coupon and analyzed by dynamic mechanical analysis (DMA) in a constrained layer geometry using a Seiko Instruments DMS 110 Rheometer using a 20 mm flexure fixture. Samples A and B were annealed for two hours at 260°C. DMA tracings of tan delta values of the two samples are shown in FIG. 1. This trial shows that Lewis acid catalysis afforded a single-phase morphology exhibiting a narrow temperature range where tan delta > 0.06, thus limiting its utility as a vibration damping material.
- DMA dynamic mechanical analysis
- Tan delta indicates the vibration damping efficiency of a material. Tan delta values of 0.06 are accepted in the art as a minimum for adequate damping for such a metal-polymer- metal composite.
- the LAC initiator can be replaced by an equivalent number of moles of HC(SO 2 CF 3 ) 3 or HN(SO 2 CF 3 ) 2 to provide compositions having desirable properties within the present invention.
- Cyanate ester resin QUARTEX 7187 can be used instead of B-30 to provide a composition having desirable properties within the present invention.
- the mixture was coated via a Meyer bar apparatus (#28) onto a 0.20 mm (8 mil) thick steel sheet and immediately covered with a second steel sheet to form a sandwich.
- the sandwich construction was heated at 150°C in a convection oven for 10 minutes, and then a coupon of 51 x 12 mm was cut from the sandwich, then annealed in a convection oven at 260°C for two hours and cooled.
- the sample was processed in a DMA rheometer (as in Example 1) four times by ramping from ambient temperature to 250°C at 5°C per minute, cooling rapidly with liquid nitrogen, then cycling twice from -40°C to 250°C at the same heating rate and holding at that temperature for 20 minutes, then cycling over the same range and holding for 50 minutes, then recording the tan delta from ambient at 275°C.
- the results are shown in FIG. 2. It is clear that the resin had lost essentially all of its vibration damping ability by the time the fourth scan is taken.
- scan C of FIG. 2 represents data before annealing and scan D data was after annealing at 250°C for the combined total of 90 minutes. The data show poor thermal stability as indicated by scan D. In scan D there were no thermal ranges having tan delta values of 0.06 or above.
- a stock solution of two parts B-30 cyanate ester resin available from Ciba- Geigy, Ardsley, NY
- one part bis((4-methyl-7-oxabicyclo[4.1.0]hept-3-yl)methyl) adipate available as ERL-4299 from Union Carbide Corp., Tarrytwon, NY
- polytetrahydrofuran polyol PolyTHF CD 1000TM polyol chain extender, BASF, Mount Olive, NY
- Cure times and temperatures were varied according to the relative effectiveness of the catalyst in order to obtain approximately the same degree of cure for each sample.
- the "B-staged” films were removed from the liners and a piece approximately 5 cm x 1.3 cm was cut from each and laminated by hand between two 0.20 mm thick steel shims of similar dimensions.
- Each of the sandwich constructions was subjected to dynamic mechanical analysis (DMA) using a Seiko DMS-100 instrument equipped with a 20 mm flexure fixture, using the temperature cycling regimen shown in Table 2.
- DMA dynamic mechanical analysis
- the "B-staged” samples continued to cure and were deemed to be largely cured by the end of the 30-minute (scan 2) hold at 260°C. Tangent delta vs. temperature data are shown in FIGS.
- Scan E (sample I from TABLE 1, scan procedure 4) represents non-annealed material and scan F (sample I from TABLE 1, scan procedure 8) represents the same sample which was annealed through eight scan cycles as shown in Table 2.
- the data show that comparative annealed sample / exhibited poor thermal stability.
- Scan G (sample II, from Table 1, scan procedure 4) represents non-annealed material and scan H (sample II, from Table 1, scan procedure 8) represents the same sample which was annealed through eight scan cycles as shown in Table 2. Both scans of sample II show narrow ranges for damping utility. Scans J (sample III, from Table 1, scan procedure 6) and K (sample III, from
- Table 1, scan procedure 8) show excellent thermal stability. Both scans show broadened damping utility of sample III.
- Scan I (sample III, from Table 1, scan procedure 4) represents a non-annealed sample. Scans I, J, and K relate to the same sample (III). Results presented in FIGS. 3, 4, -and 5 clearly show the superior high temperature damping characteristics of the LPN system obtained when a Bronsted acid catalyst system, LAC, was used (FIG. 5). In order to be considered a good damping material, the tan ⁇ should be above 0.06 over an extended temperature range. Only the IPN prepared according to the present invention exhibited the desired damping characteristics.
- the Figures also show superior high-temperature stability of the IPN system of the present invention , since damping ability was retained after repeated exposure to temperatures in excess of 300°C.
- the area under the curve having tan ⁇ values equal to or greater than 0.06 remained essentially constant in FIG. 5 but decreased significantly for FIGS. 3 and 4.
- a stock solution containing 30 g of 2 parts of bisphenol-A dicyanate (B-30 cyanate ester resin), 2 parts bis((4-methyl-7-oxabicyclo[4.1.0]hept-3-yl)methyl) adipate (ERL-4299), polytetramethylene ether glycol (PolyTHF CD 1000) polyol chain extender was prepared and stirred with 1.5 g LAC catalyst system until a uniform color was attained. The mixture was divided, with one portion coated onto steel stock (see below) and one portion coated between two KaptonTM polyimide films (see below).
- the same number of moles of any of anilinium C(SO 2 CF 3 ) 3 , lithium tris(trifluoromethylsulfonyl) methide -and di(tert-butyl)oxalate, or dibenzylhydroxylammonium hexafluoroantimonate can be used as initiator to provide compositions having desirable properties within the present invention.
- Example s Comparison of Cure Profiles of glycidyl epoxy/cyanate ester (comparative) and cycloaliphatic epoxy/cyanate ester compositions.
- Example 2 An aliquot of the mixture of Example 2 (comparative) was separated (prior to coating) for DSC (differential scanning calorimetry) analysis, shown in FIG. 6 (comparative).
- the instrument used was a Seiko DSC .Analyzer, Model. No. DSC220C. The sample was heated at 10°C per minute.
- the scan of FIG. 6 shows that the cure exotherms of the glycidyl epoxy resin and cyanate ester resin almost completely coincide. The scan indicates that a substantial amount of the product is a copolymer of cyanate ester and glycidyl epoxy.
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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)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP52683996A JP3749940B2 (en) | 1995-03-03 | 1996-01-16 | Epoxy cyanate ester composition |
DE69607328T DE69607328T2 (en) | 1995-03-03 | 1996-01-16 | EPOXY CYANATE ESTER COMPOSITIONS |
AU46999/96A AU4699996A (en) | 1995-03-03 | 1996-01-16 | Epoxy-cyanate ester compositions |
BR9607691A BR9607691A (en) | 1995-03-03 | 1996-01-16 | Composition of polymerizable material Process for polymerizing monomers to provide an interpenetrating polymeric network and kit |
EP96902686A EP0813576B1 (en) | 1995-03-03 | 1996-01-16 | Epoxy-cyanate ester compositions |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/398,230 US5494981A (en) | 1995-03-03 | 1995-03-03 | Epoxy-cyanate ester compositions that form interpenetrating networks via a Bronsted acid |
US08/398,230 | 1995-03-03 |
Publications (1)
Publication Number | Publication Date |
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WO1996027640A1 true WO1996027640A1 (en) | 1996-09-12 |
Family
ID=23574540
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1996/000544 WO1996027640A1 (en) | 1995-03-03 | 1996-01-16 | Epoxy-cyanate ester compositions |
Country Status (9)
Country | Link |
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US (1) | US5494981A (en) |
EP (1) | EP0813576B1 (en) |
JP (1) | JP3749940B2 (en) |
KR (1) | KR100416574B1 (en) |
AU (1) | AU4699996A (en) |
BR (1) | BR9607691A (en) |
CA (1) | CA2213333A1 (en) |
DE (1) | DE69607328T2 (en) |
WO (1) | WO1996027640A1 (en) |
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WO2020219885A1 (en) | 2019-04-26 | 2020-10-29 | Stepan Company | Polyol-epoxide polymers for nvh damping applications |
CN110437569B (en) * | 2019-08-09 | 2021-03-02 | 株洲飞鹿高新材料技术股份有限公司 | Damping emulsion with interpenetrating network structure and preparation method thereof |
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- 1996-01-16 DE DE69607328T patent/DE69607328T2/en not_active Expired - Fee Related
- 1996-01-16 KR KR1019970706107A patent/KR100416574B1/en not_active IP Right Cessation
- 1996-01-16 WO PCT/US1996/000544 patent/WO1996027640A1/en active IP Right Grant
- 1996-01-16 CA CA002213333A patent/CA2213333A1/en not_active Abandoned
- 1996-01-16 BR BR9607691A patent/BR9607691A/en not_active Application Discontinuation
- 1996-01-16 EP EP96902686A patent/EP0813576B1/en not_active Expired - Lifetime
- 1996-01-16 JP JP52683996A patent/JP3749940B2/en not_active Expired - Fee Related
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Also Published As
Publication number | Publication date |
---|---|
EP0813576A1 (en) | 1997-12-29 |
CA2213333A1 (en) | 1996-09-12 |
BR9607691A (en) | 1998-07-07 |
EP0813576B1 (en) | 2000-03-22 |
US5494981A (en) | 1996-02-27 |
KR19980702700A (en) | 1998-08-05 |
JP3749940B2 (en) | 2006-03-01 |
DE69607328T2 (en) | 2000-07-27 |
JPH11501075A (en) | 1999-01-26 |
AU4699996A (en) | 1996-09-23 |
DE69607328D1 (en) | 2000-04-27 |
KR100416574B1 (en) | 2004-06-23 |
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