CN107502277B - High-toughness cyanate ester adhesive - Google Patents
High-toughness cyanate ester adhesive Download PDFInfo
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- CN107502277B CN107502277B CN201710623196.3A CN201710623196A CN107502277B CN 107502277 B CN107502277 B CN 107502277B CN 201710623196 A CN201710623196 A CN 201710623196A CN 107502277 B CN107502277 B CN 107502277B
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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
- C09J179/00—Adhesives based on 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 C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2272—Ferric oxide (Fe2O3)
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2289—Oxides; Hydroxides of metals of cobalt
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/10—Silicon-containing compounds
Abstract
The invention relates to the technical field of high-temperature-resistant binders, and particularly relates to a high-toughness cyanate ester adhesive which mainly comprises, by mass, 100 parts of cyanate ester, 5-30 parts of diamine containing silica chain links, 0-300 parts of solid fillers, 0-10 parts of chopped fibers and 0-30 parts of solid pigments. The invention has the beneficial effects that: in the high-toughness cyanate ester adhesive, diamine containing silica chain links is introduced as a curing agent, so that a shielding effect is achieved on connected hydrocarbyl groups, and the oxidation resistance stability can be improved; meanwhile, the connecting bond has larger rotation flexibility, so that the silicon-oxygen bond is introduced into the cyanate monomer, and the rigidity of the connecting unit in the monomer can be effectively reduced, thereby achieving the purpose of improving the toughness of the cyanate and meeting the requirements of the fields of aviation, aerospace and the like on the high-temperature resistant structural adhesive.
Description
Technical Field
The invention relates to the technical field of high-temperature-resistant adhesives, in particular to a high-toughness cyanate ester high-temperature-resistant adhesive based on diamine containing silicon-oxygen chain links as a curing agent.
Background
The cyanate resin has high heat resistance (the glass transition temperature is 240-290 ℃), low moisture absorption rate and high bonding performance, so that the cyanate resin is widely applied to bonded structural parts with better heat resistance requirements.
In order to lower the curing temperature and reduce the curing time of the cyanate ester resin, a catalyst is usually added, and the commonly used catalyst is mainly an active hydrogen-containing compound such as nonylphenol, diaminodiphenyl sulfone, catechol, phosphoric acid and the like and a transition metal salt such as zinc octoate, magnesium octoate, naphthenate, acetylacetone compound and the like, but the transition metal salt or complex cannot be dissolved in the molten cyanate ester resin, which not only affects the catalytic effect but also the residual catalyst particles affect the performance of the cured resin, and meanwhile, the small molecular catalyst generates stress and defects in a polymer during cyanate ester polymerization, so that the brittleness of the cured cyanate ester is increased.
Disclosure of Invention
In view of the above analysis, the present invention aims to provide a high-toughness cyanate ester adhesive to solve the problem of high brittleness of the existing cyanate ester adhesive.
The purpose of the invention is mainly realized by the following technical scheme:
the high-toughness cyanate ester adhesive mainly comprises the following raw materials in parts by mass:
100 parts of cyanate ester, namely the ethylene rhodanate,
5 to 30 parts of diamine containing siloxane chain units,
0 to 300 parts of a solid filler,
0 to 10 parts of a short-cut fiber,
0-30 parts of solid pigment.
In the invention, diamine containing silica chain links is used as a curing agent to prepare the high-toughness cyanate ester adhesive, and the silica bond is a covalent bond with longer bond length and higher bond energy, so that the silicon-oxygen bond has a shielding effect on the connected hydrocarbyl groups and can improve the oxidation resistance stability; meanwhile, the connecting bond has larger rotation flexibility, so that the silicon-oxygen bond is introduced into the cyanate monomer, and the rigidity of the connecting unit in the monomer can be effectively reduced, thereby achieving the purpose of improving the toughness of the cyanate and meeting the requirements of the fields of aviation, aerospace and the like on the high-temperature resistant structural adhesive.
Further, 10-20 parts of diamine containing silicon-oxygen chain links.
According to the invention, 10-20 parts of diamine containing silicon-oxygen chain links is selected, so that the curing speed of cyanate can be effectively controlled.
Further, the cyanate ester is one or a mixture of two or more of bifunctional or multifunctional cyanate ester, oligomer cyanate ester, cyanate ester prepolymer or modified cyanate ester.
The cyanate can be liquid cyanate or organic solvent solution of cyanate, and the concentration of the cyanate solution is controlled to be more than 70%; the invention selects at least difunctional cyanate esters in order to form a crosslinking system, which cannot be formed and cured because of the low functionality.
Further, the structural formula of the cyanate is shown as
Or an aliphatic cyanate ester;
in the formula I, R1To R4Is one of hydrogen, C1-C10 alkyl, C3-C8 cycloalkyl, C1-C10 alkoxy, halogen, phenyl or phenoxy;
in the formula II, R1To R8Is one of hydrogen, C1-C10 alkyl, C3-C8 cycloalkyl, C1-C10 alkoxy, halogen, phenyl or phenoxy;
z is a chemical bond, SO2、CF2、CH2、CHF、CH(CH3) Isopropylidene, hexafluoroisopropylidene, C1-C10 alkylene, O, NR9N-N, CH-N, CH-CH, COO, CH-N-CH, alkyleneoxy with C1-C8 alkylene, S, Si (CH)3)2Or
In the formula III, R9Is H or one of C1-C10 alkyl, n is more than or equal to 0 and less than or equal to 20, and n is an integer.
Preferably, when the cyanate ester is of formula I, the cyanate ester is phenylene-1, 3-dicyanate, phenylene-1, 4-dicyanate or 2,4, 5-trifluorophenylene-1, 3-dicyanate; when the cyanate ester is of formula ii, the cyanate ester is 4,4 '-bis (phenyl cyanate) methane, dicyclopentadiene type cyanate ester, 4' -bis (phenyl cyanate) isopropane or 2, 2-bis (4-cyanate-phenyl) hexafluoropropane; the aliphatic cyanate ester is difunctional aliphatic cyanate ester or multifunctional aliphatic cyanate ester,
the structural formula of the aliphatic cyanate is shown in the specification
In the formula IV, R10Is an organic non-aromatic divalent hydrocarbon/hydrocarbon radical whose hydrogen atoms can be partially or fully substituted by fluorine atoms.
Preferably, the number of carbon atoms of the organic non-aromatic divalent hydrocarbon/hydrocarbon group is 3 to 12.
Further, the cyanate esters can be used as cyanate ester monomers or cyanate ester prepolymers, either alone or as a mixture with each other or as a mixture with other monofunctional cyanate esters.
The prepolymer is a substance capable of further crosslinking and can be used as difunctional cyanate or oligocyanate as: 4,4 '-bis (phenylcyanate) isopropane (B10), 4' -bis (phenylcyanate) ethane (L10), phenolic cyanate (N10) or cyclopentadiene cyanate (P10).
Further, the diamine containing siloxane chain segment has the general formula
In formula V, R11、R12Is one of hydrogen, linear substituted or unsubstituted alkyl, branched substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, linear substituted or unsubstituted alkenyl, branched substituted or unsubstituted alkenyl, substituted or unsubstituted cycloalkenyl, linear substituted or unsubstituted alkynyl, branched substituted or unsubstituted alkynyl, substituted or unsubstituted cycloalkynyl, and substituted or unsubstituted aryl;
R11′、R12' is hydrogen, straightOne of a substituted or unsubstituted alkyl, branched substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, linear substituted or unsubstituted alkenyl, branched substituted or unsubstituted alkenyl, substituted or unsubstituted cycloalkenyl, linear substituted or unsubstituted alkynyl, branched substituted or unsubstituted alkynyl, substituted or unsubstituted cycloalkynyl, and substituted or unsubstituted aryl;
R13、R14is one of hydrogen, linear substituted or unsubstituted alkyl, branched substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, linear substituted or unsubstituted alkenyl, branched substituted or unsubstituted alkenyl, substituted or unsubstituted cycloalkenyl, linear substituted or unsubstituted alkynyl, branched substituted or unsubstituted alkynyl, substituted or unsubstituted cycloalkynyl, and substituted or unsubstituted aryl;
R15、R16is one of hydrogen or linear substituted or unsubstituted alkyl, branched substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, linear substituted or unsubstituted alkenyl, branched substituted or unsubstituted alkenyl, substituted or unsubstituted cycloalkenyl, linear substituted or unsubstituted alkynyl, branched substituted or unsubstituted alkynyl, substituted or unsubstituted cycloalkynyl, substituted or unsubstituted aryl,
m is an integer, and m is more than or equal to 0 and less than or equal to 100;
when m is>At 0, R is preferred11And R11' same, preferably R12And R12' same.
Furthermore, the diamines containing siloxane segments are monomers, used individually or as a mixture with one another or as further monofunctional amine compounds containing siloxane segments.
Further, the solid filler is one or a mixture of more of oxides, carbides, nitrides, borides and silicides of IIIA, IVA main groups, B groups and lanthanide series metals.
The solid filler can play a role in reinforcing, toughening and improving the temperature resistance of the cyanate adhesive.
Further, the solid pigment is an inorganic pigment.
Preferably, the solid pigment is iron red, chrome yellow or titanium white.
Further, the chopped fiber is carbon fiber, silicon carbide fiber, alumina fiber, quartz fiber, glass fiber, silicon nitride fiber, aluminum nitride or boron nitride.
Further, the length of the chopped fiber is 1-5 mm.
The method selects the chopped fibers with the length of 1-5 mm, and can play a toughening role, if the chopped fibers are too short, the toughening effect cannot be achieved, and if the chopped fibers are too long, various raw materials of the cyanate ester adhesive cannot be uniformly mixed.
The cyanate ester adhesive can realize the full curing of the adhesive and improve the bonding property at high temperature.
The invention has the following beneficial effects:
(1) the invention provides a cyanate ester adhesive based on diamine containing silica chain links as a curing agent, wherein the silica bonds are covalent bonds with longer bond length and higher bond energy, play a role in shielding connected hydrocarbyl groups and can improve the oxidation resistance stability; meanwhile, the connecting bond has larger rotation flexibility, so that the silicon-oxygen bond is introduced into the cyanate monomer, and the rigidity of the connecting unit in the monomer can be effectively reduced, thereby achieving the purpose of improving the toughness of the cyanate and effectively meeting the requirements of the fields of aviation, aerospace and the like on the high-temperature resistant structural adhesive;
(2) the preparation method of the high-toughness cyanate ester adhesive is simple and easy to implement, can reduce the curing temperature, and simultaneously meets the requirement of mass production of the cyanate ester adhesive;
(3) the curing method of the high-toughness cyanate ester adhesive can realize the full curing of the adhesive and improve the bonding performance at high temperature.
Detailed Description
The high-temperature-resistant adhesive can be prepared by quantitatively mixing cyanate ester, silazane oligomer or polymer, solid filler, chopped fiber and solid pigment; the cyanate ester adopted by the invention is one or a mixture of more of difunctional or multifunctional cyanate ester, cyanate ester oligomer or cyanate ester prepolymer.
According to the invention, the diamine containing silica chain links is used as the curing agent to prepare the cyanate adhesive, and the silica bonds are covalent bonds with longer bond length and higher bond energy, so that the siloxane bonds can shield the connected hydrocarbyl groups, and the oxidation resistance stability can be improved; meanwhile, the connecting bond has larger rotation flexibility, so that the silicon-oxygen bond is introduced into the cyanate monomer, and the rigidity of the connecting unit in the monomer can be effectively reduced, thereby achieving the purpose of improving the toughness of the cyanate and meeting the requirements of the fields of aviation, aerospace and the like on the high-temperature resistant structural adhesive.
The preparation method of the cyanate ester adhesive comprises the following steps:
adding a certain amount of auxiliary filler into 100 parts of bifunctional, low-polymer or polyfunctional cyanate ester or prepolymer or modified substance thereof, uniformly mixing, adding a corresponding diamine curing agent containing silicon-oxygen chain joints, uniformly mixing, and degassing for 5-10 minutes to obtain the high-temperature-resistant structural adhesive.
The curing method of the cyanate ester adhesive comprises the following steps:
the adhesive is cured for 1-4 hours at 130-240 ℃, preferably 150-200 ℃.
Wherein, the method and the standard of the corresponding performance test involved in the invention are all according to the following standards
GB/T2568 + 1995 method for testing tensile property of resin casting body
GJB444-1988 Experimental method for high-temperature tensile shear strength of adhesive (Metal-to-Metal)
GB/T7124-2008 "adhesive tensile shear test method (Metal to Metal)
GB/T14992-2005 Classification and trade mark of high temperature alloy and intermetallic compound high temperature material
The cyanate ester in the invention is one or a mixture of more of difunctional or multifunctional cyanate ester monomer, cyanate ester oligomer, cyanate ester hybrid prepolymer or modified cyanate ester; the cyanate in the invention can be liquid cyanate or organic solvent solution of cyanate, and the concentration of the cyanate solution is controlled to be more than 70%; the organic solvent may be one or more of an alkane solvent, an aromatic solvent, a ketone solvent and an ether solvent mixed at any ratio, and for example, the organic solvent may be one or more of n-hexane, toluene, xylene, acetone, diethyl ether or dibutyl ether mixed at any ratio.
The structural formula of the cyanate ester is preferably
Or an aliphatic cyanate ester;
in the formula I, formula II, formula III, R1To R8Is one of hydrogen, C1-C10 alkyl, C3-C8 cycloalkyl, C1-C10 alkoxy, halogen (e.g., F, Cl, Br or I), phenyl or phenoxy, wherein C1-C10 alkyl, C3-C8 cycloalkyl, C1-C10 alkoxy, phenyl or phenoxy can be fully or partially fluorinated;
R9is H or one of C1-C10 alkyl, n is more than or equal to 0 and less than or equal to 20, and n is an integer;
z is a chemical bond, SO2、CF2、CH2、CHF、CH(CH3) Isopropylidene, hexafluoroisopropylidene, C1-C10 alkylene, O, NR9N-N, CH-N, CH-CH, COO, CH-N-CH, alkyleneoxy with C1-C8 alkylene, S, Si (CH)3)2Or
When the cyanate ester is of formula I, the cyanate ester may be phenylene-1, 3-dicyanate, phenylene-1, 4-dicyanate or 2,4, 5-trifluorophenylene-1, 3-dicyanate;
when the cyanate ester is of formula ii, the cyanate ester may be 4,4 '-bis (phenyl cyanate) methane, dicyclopentadiene type cyanate ester, 4' -bis (phenyl cyanate) isopropane or 2, 2-bis (4-cyanate-phenyl) hexafluoropropane;
when the aliphatic cyanate ester is a difunctional or polyfunctional aliphatic cyanate ester, the aliphatic cyanate ester may contain one or more fluorine atoms in the aliphatic group.
Preferably, the aliphatic cyanate has the structural formula
In the formula IV, R10Is an organic non-aromatic divalent hydrocarbon/hydrocarbon group, wherein hydrogen atoms of the organic non-aromatic divalent hydrocarbon/hydrocarbon group may be partially or fully substituted by fluorine atoms.
Preferably, the number of carbon atoms of the organic non-aromatic divalent hydrocarbon/hydrocarbon group is 3 to 12.
At the same time, cyanate esters can be used as cyanate ester monomers, cyanate ester prepolymers, either alone or as a mixture with one another or as a mixture of other monofunctional cyanate esters.
Prepolymers are those which are capable of further crosslinking and which can be used as difunctional cyanates or oligocyanates are: 4,4 '-bis (phenylcyanate) isopropane (B10), 4' -bis (phenylcyanate) ethane (L10), phenolic cyanate (N10) or cyclopentadiene cyanate (P10).
Diamines containing siloxane units of the formula
In formula V, R11、R12Is hydrogen, linear substituted or unsubstituted alkyl, branched substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, linear substituted or unsubstituted alkenyl, branched substituted or unsubstituted alkenyl, substituted or unsubstituted cycloalkenyl, linear substituted or unsubstituted alkynyl, branched substituted or unsubstituted alkynyl, substitutedOr one of unsubstituted cycloalkynyl, substituted or unsubstituted aryl;
preferably, R11And R12And may be hydrogen, methyl, vinyl or phenyl.
R11′、R12' is one of hydrogen, linear substituted or unsubstituted alkyl, branched substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, linear substituted or unsubstituted alkenyl, branched substituted or unsubstituted alkenyl, substituted or unsubstituted cycloalkenyl, linear substituted or unsubstituted alkynyl, branched substituted or unsubstituted alkynyl, substituted or unsubstituted cycloalkynyl, substituted or unsubstituted aryl;
preferably, R11′R12′Can be hydrogen, methyl, vinyl or phenyl;
R13、R14is one of hydrogen, linear substituted or unsubstituted alkyl, branched substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, linear substituted or unsubstituted alkenyl, branched substituted or unsubstituted alkenyl, substituted or unsubstituted cycloalkenyl, linear substituted or unsubstituted alkynyl, branched substituted or unsubstituted alkynyl, substituted or unsubstituted cycloalkynyl, and substituted or unsubstituted aryl;
preferably, R13And R14May be methyl, vinyl or phenyl;
R15、R16is one of hydrogen or linear substituted or unsubstituted alkyl, branched substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, linear substituted or unsubstituted alkenyl, branched substituted or unsubstituted alkenyl, substituted or unsubstituted cycloalkenyl, linear substituted or unsubstituted alkynyl, branched substituted or unsubstituted alkynyl, substituted or unsubstituted cycloalkynyl, substituted or unsubstituted aryl,
m is an integer, and m is more than or equal to 0 and less than or equal to 100;
when m is>At 0, R is preferred11And R11' same, preferably R12And R12' same;
notably, R11、R11′、R12、R12′、R13、R14、R15And R16May be the same or different.
Notably, the siloxane segment-containing diamines are siloxane segment-containing diamine monomers, used alone or as a mixture with each other or as other monofunctional siloxane segment-containing amine compounds.
It is noted that the solid filler used in the present invention is one or a mixture of oxides, carbides, nitrides, borides or silicides of IIIA, IVA main groups, B groups and lanthanides.
It is to be noted that the solid pigment used in the present invention is an inorganic pigment, preferably iron red, chrome yellow or titanium white.
Notably, the chopped fibers used in the present invention are carbon fibers, silicon carbide fibers, alumina fibers, quartz fibers, glass fibers, silicon nitride fibers, aluminum nitride, or boron nitride. The length of the chopped fiber is 1-5 mm.
Example 1
Adding 5 parts of siloxane diamine (a) shown in a structural formula 2, 5 parts of (b), 10 parts of (c), 15 parts of (d), 20 parts of (e), 25 parts of (f) and 30 parts of (f) into 100 parts of 4, 4' -bis (phenyl cyanate) ethane (L10) with a structural formula 1, uniformly mixing, vacuum degassing for 5 minutes, pouring into a mold, heating to 180 ℃, curing for 2 hours, cooling to room temperature, and testing the tensile strength and elongation of the cast body. For comparison, the tensile strength and elongation of the test after L10 was fully cured are listed in table 1.
The structural formula of the 4, 4' -bis (phenyl cyanate) ethane is shown in the specification
The structural formula of the silicon-oxygen diamine is
TABLE 1 test results for tensile strength and elongation of siloxanediamine cured cyanate ester resins
It can be seen from table 1 that the toughness of cyanate ester is significantly improved by adding siloxane diamine to cyanate ester.
Example 2
In this example, 60 parts by mass of SiO was added to 100 parts by mass of 4, 4' -bis (phenylcyanate) ethane (L10)230 parts of B4C. 10 parts of SiC, 10 parts of B as solid filler and 3 parts of Fe2O3And (2) fully and uniformly mixing the solid pigment, adding 20 parts of silicon-oxygen diamine with the structural formula shown in the specification 2, vacuum degassing for 10 minutes to prepare the high-toughness cyanate ester adhesive, wherein the adhesive is used for bonding metal, curing a bonded part at 150 ℃ for 2 hours, cooling to room temperature, and testing the bonding strength at 25 ℃, 200 ℃, 250 ℃, 300 ℃ and 400 ℃, wherein the test results are shown in table 2.
TABLE 2 adhesive bond strength at different temperatures
As can be seen from Table 2, the adhesive still has a high strength at 400 ℃.
Example 3
In this example, a solid filler is added to 100 parts by mass of 4, 4' -bis (phenyl cyanate) ethane (L10): 40 parts of Al2O340 parts of Si3N415 parts of B4C and 5 parts of Y2O33 parts of Cr2O33 parts of quartz fiber with the thickness of 1-2 mm as solid pigment is used as chopped fiber, curing agent silicon-oxygen diamine with the structural formula shown as the formula 2 is added, the adding amount of the silicon-oxygen diamine is 20 parts, after vacuum degassing is carried out for 10 minutes, high-toughness cyanate ester adhesive is prepared, the adhesive is used for bonding metal, a bonding piece is cured for 2 hours at the temperature of 150 ℃, the temperature is cooled to room temperature, and a test room is used for testing the metalThe adhesive strength was mild at 250 ℃ and the test results are shown in Table 3.
TABLE 3 adhesive bond strength at different temperatures
| Test temperature (. degree. C.) | 25 | 250 |
| Adhesive Strength (MPa) | 17.4 | 16.1 |
As can be seen from Table 3, the adhesive still has a high strength at 250 ℃.
Example 4
In this example, a solid filler is added to 100 parts by mass of 4, 4' -bis (phenyl cyanate) ethane (L10): 40 parts of Al2O340 parts of Si3N415 parts of B4C and 5 parts of Y2O33 parts of Cr2O35 parts of quartz fiber with the thickness of 1-2 mm serving as solid pigment is added as chopped fiber, curing agent silicon-oxygen diamine with the structural formula shown in the specification 2 is added, the adding amount of the silicon-oxygen diamine is 20 parts, vacuum degassing is carried out for 10 minutes, high-toughness cyanate ester adhesive is prepared, the adhesive is used for bonding metal, a bonding piece is cured for 2 hours at the temperature of 150 ℃, the temperature is cooled to room temperature, the bonding strength at the room temperature and the temperature of 250 ℃ is tested, and the test results are shown in table 4.
TABLE 4 adhesive bond strength at different temperatures
| Test temperature (. degree. C.) | 25 | 250 |
| Adhesive Strength (MPa) | 17.6 | 16.5 |
As can be seen from Table 4, the adhesive still has a high strength at 250 ℃.
Example 5
In this example, a solid filler is added to 100 parts by mass of 4, 4' -bis (phenyl cyanate) ethane (L10): 40 parts of Al2O340 parts of Si3N415 parts of B4C and 5 parts of Y2O33 parts of Cr2O33 parts of 1-2 mm carbon fibers are used as solid pigments, a curing agent silicon-oxygen diamine with the structural formula shown in the specification 2 is added, the adding amount of the silicon-oxygen diamine is 20 parts, vacuum degassing is carried out for 10 minutes, a high-toughness cyanate ester adhesive is prepared, the adhesive is used for bonding metal, a bonding piece is cured for 2 hours at the temperature of 150 ℃, the temperature is cooled to room temperature, the bonding strength at the room temperature and the temperature of 250 ℃ is tested, and the test results are shown in table 5.
TABLE 5 adhesive bond strength at different temperatures
| Test temperature (. degree. C.) | 25 | 250 |
| Strong adhesionDegree (MPa) | 18.1 | 16.3 |
As can be seen from Table 5, the adhesive still has a high strength at 250 ℃.
Example 6
In this example, 60 parts by mass of SiO was added to 100 parts by mass of 4, 4' -bis (phenylcyanate) ethane (L10)230 parts of B4C. 10 parts of SiC, 10 parts of B as solid filler and 3 parts of Fe2O3The high-toughness cyanate ester adhesive is used for bonding metal, a bonding piece is solidified for 2 hours at 150 ℃, cooled to room temperature, and tested at room temperature and 250 ℃ for bonding strength, and test results are shown in table 6.
The structural formula of the siloxane diamine in the embodiment is
TABLE 6 adhesive bond strength at different temperatures
| Test temperature (. degree. C.) | 25 | 250 |
| Adhesive Strength (MPa) | 15.3 | 11.9 |
As can be seen from Table 6, the adhesive still has a high strength at 250 ℃.
Example 7
In this example, 60 parts by mass of SiO was added to 100 parts by mass of 4, 4' -bis (phenylcyanate) ethane (L10)230 parts of B4C. 10 parts of SiC, 10 parts of B as solid filler and 3 parts of Fe2O3The high-toughness cyanate ester adhesive is used for bonding metal, a bonding piece is solidified for 2 hours at 150 ℃, cooled to room temperature, and tested at room temperature and 250 ℃ for bonding strength, and test results are shown in table 7.
TABLE 7 adhesive bond strength at different temperatures
| Test temperature (. degree. C.) | 25 | 250 |
| Adhesive Strength (MPa) | 14.8 | 10.5 |
As can be seen from Table 7, the adhesive still has a high strength at 250 ℃.
Example 8
This example is carried out using 100 parts by mass of 4, 4' -bis (phenylcyanate) isopropane (B10) and L10 cyanogenA mixture of acid esters, wherein 4,4 '-bis (phenylcyanate) isopropane (B10) and L10 cyanate are mixed in a mass ratio (g) of 1:10(h)2:10(I)3:10(J)4:10(k)5:10, and 60 parts of SiO 2 is added to the mixture of 4, 4' -bis (phenylcyanate) isopropane (B10) and L10 cyanate230 parts of B4C. 10 parts of SiC, 10 parts of B as solid filler and 3 parts of Fe2O3The high-toughness cyanate ester adhesive is used for bonding metal, a bonding piece is solidified for 2 hours at 150 ℃, cooled to room temperature, and tested at room temperature and 250 ℃ for bonding strength, and test results are shown in table 8.
TABLE 8 adhesive bond strength at different temperatures
As can be seen from Table 8, the adhesive still has a high strength at 250 ℃.
Example 9
This example is a method of adding 60 parts of SiO to 100 parts by mass of 4, 4' -methylenediphenyldicyanate230 parts of B4C. 10 parts of SiC, 10 parts of B as solid filler and 3 parts of Fe2O3The solid pigment is fully and uniformly mixed, silicon-oxygen diamine with the structural formula shown in the time 2 is added, the adding amount of the silicon-oxygen diamine is 20 parts, after vacuum degassing is carried out for 10 minutes, the high-toughness cyanate ester adhesive is prepared, the adhesive is used for bonding metal, a bonding piece is solidified for 2 hours at the temperature of 150 ℃, the bonding strength is measured at the room temperature and the temperature of 250 ℃, and the measurement result is shown in table 9.
TABLE 9 adhesive bond strength at different temperatures
| Test temperature (. degree. C.) | 25 | 250 |
| Adhesive Strength (MPa) | 18.2 | 16.3 |
As can be seen from Table 9, the adhesive still has a high strength at 250 ℃.
Example 10
In this example, 60 parts of SiO was added to 100 parts by mass of a phenolic cyanate ester230 parts of B4C. 10 parts of SiC, 10 parts of B as solid filler and 3 parts of Fe2O3The solid pigment is fully and uniformly mixed, silicon-oxygen diamine with the structural formula shown in the time 2 is added, the adding amount of the silicon-oxygen diamine is 20 parts, after vacuum degassing is carried out for 10 minutes, the high-toughness cyanate ester adhesive is prepared, the adhesive is used for bonding metal, a bonding piece is solidified for 2 hours at the temperature of 150 ℃, the bonding strength is measured at the room temperature and the temperature of 250 ℃, and the measurement result is shown in the table 10.
TABLE 10 adhesive bond strength at different temperatures
| Test temperature (. degree. C.) | 25 | 250 |
| Adhesive Strength (MPa) | 19.4 | 18.7 |
As can be seen from Table 10, the adhesive still has a high strength at 250 ℃.
Example 11
In the embodiment, 100 parts by mass of p-phenyl dicyanate is added, wherein the structural formula of the p-phenyl dicyanate is shown in formula 5, the phenyl dicyanate is prepared into 75% solution, and 60 parts of SiO is added230 parts of B4C. 10 parts of SiC, 10 parts of B as solid filler and 3 parts of Fe2O3The solid pigment is fully and uniformly mixed, then siloxane diamine with the structural formula shown in the time 2 is added, the adding amount of the siloxane diamine is 20 parts, after vacuum degassing is carried out for 10 minutes, the high-toughness cyanate ester adhesive is prepared, a steel plate is used as a base material of the adhesive, the adhesive is solidified for 2 hours at the temperature of 150 ℃, the temperature is cooled to room temperature, the bonding strength is tested at the room temperature and the temperature of 250 ℃, and the test results are shown in table 11.
The structural formula of the p-phenyl dicyanate is shown in the specification
TABLE 11 adhesion Properties of high temperature silazane hybrid cyanate ester Adhesives
| Adhesive Strength at Room temperature (MPa) | Bond Strength (MPa) at 250 ℃ | |
| Adhesive Strength (MPa) | 17.6 | 13.8 |
As can be seen from Table 11, the adhesive still has a high strength at 250 ℃.
Example 12
In the embodiment, 100 parts by mass of bisphenol F dicyanate is added with 60 parts of SiO230 parts of B4C. 10 parts of SiC, 10 parts of B as solid filler and 3 parts of Fe2O3The solid pigment is fully and uniformly mixed, the siloxane diamine with the structural formula shown in the time 2 is added, the adding amount of the siloxane diamine is 20 parts, the high-toughness cyanate ester adhesive is prepared after vacuum degassing is carried out for 10 minutes, the adhesive takes a steel plate as a base material, an adhesive piece is solidified for 2 hours at the temperature of 150 ℃, the temperature is cooled to room temperature, the bonding strength at the room temperature and the temperature of 250 ℃ is tested, and the test results are shown in table 12.
The structural formula of bisphenol F dicyanate is shown in the specification
TABLE 12 adhesion Properties of high temperature silazane hybrid cyanate ester Adhesives
| Adhesive Strength at Room temperature (MPa) | Bond Strength (MPa) at 250 ℃ | |
| Adhesive Strength (MPa) | 18.9 | 16.1 |
As can be seen from Table 12, the adhesive still has a high strength at 250 ℃.
Example 13
In this example, 100 parts by mass of dicyanate, the structural formula of which is shown in formula 7, was added to a 85% solution of dicyanate, and 60 parts of SiO was added230 parts of B4C. 10 parts of SiC, 10 parts of B as solid filler and 3 parts of Fe2O3The high-toughness cyanate ester adhesive is prepared by taking a steel plate as a base material, curing an adhesive piece at 150 ℃ for 2 hours, cooling to room temperature, and testing the room temperature and 250 ℃ bonding strength of the cured high-temperature-resistant silazane hybrid cyanate ester adhesive, wherein the test results are shown in Table 13.
The structural formula of the dicyanate is shown in the specification
TABLE 13 adhesion Properties of high temperature silazane hybrid cyanate ester Adhesives
| Adhesive Strength at Room temperature (MPa) | Bond Strength (MPa) at 250 ℃ | |
| Adhesive Strength (MPa) | 18.8 | 12.3 |
As can be seen from Table 13, the adhesive still has a high strength at 250 ℃.
In conclusion, the invention provides a high-toughness cyanate ester high-temperature-resistant adhesive and preparation and curing methods thereof, the invention takes diamine containing silica chain links as a curing agent, and the silica bonds are covalent bonds with longer bond length and higher bond energy, which play a role in shielding connected hydrocarbyl groups and can improve the oxidation resistance stability; meanwhile, the connecting bond has larger rotation flexibility, so that the silicon-oxygen bond is introduced into the cyanate monomer, and the rigidity of the connecting unit in the monomer can be effectively reduced, thereby achieving the purpose of improving the toughness of the cyanate and meeting the requirements of the fields of aviation, aerospace and the like on the high-temperature resistant structural adhesive.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (4)
1. The high-toughness cyanate ester adhesive is characterized by mainly comprising the following raw materials in parts by mass:
100 parts of cyanate ester, namely the ethylene rhodanate,
10 to 20 parts of diamine containing siloxane chain units,
110 to 300 parts of a solid filler,
3 to 10 parts of short-cut fibers,
3-30 parts of a solid pigment;
the solid filler is one or a mixture of more of oxides, carbides, nitrides, borides and silicides of IIIA, IVA main groups, B groups and lanthanide series metals;
the chopped fibers are carbon fibers, silicon carbide fibers, alumina fibers, quartz fibers, glass fibers, silicon nitride fibers, aluminum nitride fibers or boron nitride fibers, and the length of the chopped fibers is 1-5 mm;
the solid pigment is inorganic pigment, and any one or mixture of iron oxide red, chrome yellow or titanium dioxide;
the diamine containing silicon oxygen chain link has the general formula
In formula V, R11、R12Is one of hydrogen, linear substituted or unsubstituted alkyl, branched substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, linear substituted or unsubstituted alkenyl, branched substituted or unsubstituted alkenyl, substituted or unsubstituted cycloalkenyl, linear substituted or unsubstituted alkynyl, branched substituted or unsubstituted alkynyl, substituted or unsubstituted cycloalkynyl, and substituted or unsubstituted aryl;
R11′、R12' is one of hydrogen, linear substituted or unsubstituted alkyl, branched substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, linear substituted or unsubstituted alkenyl, branched substituted or unsubstituted alkenyl, substituted or unsubstituted cycloalkenyl, linear substituted or unsubstituted alkynyl, branched substituted or unsubstituted alkynyl, substituted or unsubstituted cycloalkynyl, substituted or unsubstituted aryl;
R13、R14is one of hydrogen, linear substituted or unsubstituted alkyl, branched substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, linear substituted or unsubstituted alkenyl, branched substituted or unsubstituted alkenyl, substituted or unsubstituted cycloalkenyl, linear substituted or unsubstituted alkynyl, branched substituted or unsubstituted alkynyl, substituted or unsubstituted cycloalkynyl, and substituted or unsubstituted aryl;
R15、R16is one of hydrogen or a linear substituted or unsubstituted alkyl group, a branched substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a linear substituted or unsubstituted alkenyl group, a branched substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkenyl group, a linear substituted or unsubstituted alkynyl group, a branched substituted or unsubstituted alkynyl group, a substituted or unsubstituted cycloalkynyl group, a substituted or unsubstituted aryl group;
m is an integer, and m is more than or equal to 0 and less than or equal to 100;
the high-toughness cyanate ester adhesive is prepared by the following steps:
adding auxiliary filler into 100 parts of cyanate ester, uniformly mixing, adding a diamine curing agent containing silica chain links, and uniformly mixing to obtain an adhesive;
curing the obtained adhesive at 150-200 ℃ for 1-4 hours.
2. The high-toughness cyanate ester adhesive according to claim 1, wherein said cyanate ester is one or a mixture of two or more of difunctional or multifunctional cyanate ester, oligomer cyanate ester, cyanate ester prepolymer or modified cyanate ester.
3. The high-toughness cyanate ester adhesive according to claim 1, wherein said cyanate ester has a structural formula of
Or an aliphatic cyanate ester;
in the formula I, R1To R4Is one of hydrogen, C1-C10 alkyl, C3-C8 cycloalkyl, C1-C10 alkoxy, halogen, phenyl or phenoxy;
in the formula II, R1To R8Is one of hydrogen, C1-C10 alkyl, C3-C8 cycloalkyl, C1-C10 alkoxy, halogen, phenyl or phenoxy;
z is a chemical bond, SO2、CF2、CH2、CHF、CH(CH3) Isopropylidene, hexafluoroisopropylidene, C1-C10 alkylene, O, NR9N-N, CH-N, CH-CH, COO, CH-N-CH, alkyleneoxy with C1-C8 alkylene, S, Si (CH)3)2Or
In the formula III, R9Is one of H or C1-C10 alkyl, n is more than or equal to 0 and less than or equal to n20 and n is an integer.
4. The high-toughness cyanate ester adhesive according to claim 3, wherein when said cyanate ester is represented by formula I, said cyanate ester is phenylene-1, 3-dicyanate, phenylene-1, 4-dicyanate or 2,4, 5-trifluorophenylene-1, 3-dicyanate; when the cyanate ester is of formula ii, the cyanate ester is 4,4 '-bis (phenyl cyanate) methane, dicyclopentadiene type cyanate ester, 4' -bis (phenyl cyanate) isopropane or 2, 2-bis (4-cyanate-phenyl) hexafluoropropane; the aliphatic cyanate ester is difunctional aliphatic cyanate ester or multifunctional aliphatic cyanate ester,
the structural formula of the aliphatic cyanate is shown in the specification
N≡C-O-R10-O-C ≡ N formula IV
In the formula IV, R10Is an organic non-aromatic divalent hydrocarbon/hydrocarbon radical whose hydrogen atoms can be partially or fully substituted by fluorine atoms.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102417808A (en) * | 2011-09-29 | 2012-04-18 | 西北工业大学 | High-temperature-resistant adhesive and preparation method thereof |
| CN102449035A (en) * | 2009-03-16 | 2012-05-09 | 弗劳恩霍弗应用技术研究院 | Hybrid polymers made of cyanates and silazanes, method for the production and use thereof |
| CN103748140A (en) * | 2011-07-11 | 2014-04-23 | 三菱瓦斯化学株式会社 | Curable resin composition and process for producing cured products using same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102449035A (en) * | 2009-03-16 | 2012-05-09 | 弗劳恩霍弗应用技术研究院 | Hybrid polymers made of cyanates and silazanes, method for the production and use thereof |
| CN103748140A (en) * | 2011-07-11 | 2014-04-23 | 三菱瓦斯化学株式会社 | Curable resin composition and process for producing cured products using same |
| CN102417808A (en) * | 2011-09-29 | 2012-04-18 | 西北工业大学 | High-temperature-resistant adhesive and preparation method thereof |
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| Title |
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| 《含硅二胺单体合成及应用研究》;刘达;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20100315(第3期);第1.1.3节、第1.3节、第1.4.3节 * |
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