CN107400496B - Silazane hybrid cyanate adhesive - Google Patents
Silazane hybrid cyanate adhesive Download PDFInfo
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- CN107400496B CN107400496B CN201710623592.6A CN201710623592A CN107400496B CN 107400496 B CN107400496 B CN 107400496B CN 201710623592 A CN201710623592 A CN 201710623592A CN 107400496 B CN107400496 B CN 107400496B
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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
- 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
- C08G73/0644—Poly(1,3,5)triazines
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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
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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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention relates to the technical field of high-temperature-resistant adhesives, and particularly relates to a silazane hybrid cyanate adhesive which mainly comprises, by mass, 100 parts of cyanate, 5-30 parts of silazane, 0-200 parts of solid filler, 0-20 parts of solid pigment and 0-5 parts of chopped fibers. The invention has the beneficial effects that: according to the invention, silazane hybridized cyanate is used as matrix resin for the high-temperature-resistant adhesive, so that the temperature resistance and the oxidation resistance of the cyanate are improved, and the high-temperature-resistant adhesive is prepared by matching corresponding fillers; the high-temperature performance of the cyanate ester adhesive is improved while the adhesive property of the cyanate ester adhesive is maintained; the adhesive prepared by the invention can meet the requirements of the fields of aviation, aerospace and the like on high-temperature-resistant structural adhesives.
Description
Technical Field
The invention relates to the technical field of high-temperature-resistant adhesives, in particular to a silazane hybrid cyanate adhesive.
Background
With the development of high technology, especially the development of the industries of aerospace, electronics, machinery, weaponry and the like, higher requirements are put forward on structural adhesives, such as temperature resistance, fatigue resistance and the like.
The existing organic structure adhesive mainly comprises epoxy resin type, polyimide type and the like, but the temperature resistance of the adhesive mainly taking epoxy resin is lower than 200 ℃; the polyimide type adhesive has good temperature resistance, but high curing temperature; the cyanate ester resin has good heat resistance and manufacturability, can be used for bonding structural parts with high heat resistance requirements, but has poor temperature resistance and poor high-temperature oxidation resistance.
Disclosure of Invention
In view of the above analysis, the present invention aims to provide a high temperature resistant silazane hybrid cyanate adhesive, which is used to solve the problems of insufficient temperature resistance and poor high temperature oxidation resistance of the existing cyanate adhesive.
The purpose of the invention is mainly realized by the following technical scheme:
the silazane hybridized cyanate 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 a silazane,
0 to 200 parts of a solid filler,
0 to 20 parts of a solid pigment,
0-5 parts of chopped fibers.
According to the invention, the silazane hybridized cyanate is used as matrix resin for the high-temperature-resistant adhesive, so that the high temperature resistance and the oxidation resistance of the silazane hybridized cyanate adhesive are improved, and the high-temperature-resistant adhesive is prepared by matching with corresponding fillers, so that the requirements of the fields of aviation, aerospace and the like on the high-temperature-resistant structural adhesive can be met.
Further, the cyanate ester is at least a difunctional cyanate ester.
The cyanate ester which is at least difunctional is selected in the present invention because the functionality is related to the formation of a crosslinking system, and if the functionality is low, the crosslinking system cannot be formed and cannot be cured.
Further, the cyanate ester is one or a mixture of two or more of difunctional or multifunctional cyanate ester, cyanate ester oligomer and cyanate ester prepolymer.
The cyanate can be liquid cyanate or organic solvent solution of cyanate, and the concentration of cyanate solution is controlled to be above 70%.
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, wherein the alkyl or aryl group can be fluorinated or partially fluorinated;
in the formula II, R1To R8Is one of hydrogen, C1-C10 alkyl, C3-C8 cycloalkyl, C1-C10 alkoxy, halogen, phenyl or phenoxy, wherein the alkyl or aryl group may be fluorinated or partially fluorinated;
z represents a bond, SO2、CF2、CH2、CHF、CH(CH3) Isopropylidene, hexafluoroisopropylidene, C1-C10 alkylene, O, NR9N-N, CH-N, CH-CH, COO, CH-N-CH, alkyleneoxy having C1-C8 alkylene group, 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 represented by formula ii, the cyanate ester is 4,4 '-bis (phenyl cyanate) methane, dicyclopentadiene type cyanate ester, 4, 4' -bis (phenyl cyanate) isopropane, 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
The aliphatic group of the difunctional aliphatic cyanate ester or the multifunctional aliphatic cyanate ester can contain one or more fluorine atoms;
in the formula IV, R10Represents an organic non-aromatic divalent hydrocarbon/hydrocarbon group containing 3 to 12 carbon atoms, the hydrogen atoms of which can be partially or fully substituted by fluorine atoms.
Further, the cyanate ester is a cyanate ester monomer or a cyanate ester prepolymer, which are used alone or as a mixture with each other or as a mixture of other monofunctional cyanate esters.
The prepolymer is a substance capable of further crosslinking, and what can be used as a bifunctional cyanate or an oligocyanate is: 4,4 '-bis (phenylcyanate) isopropane (B10), 4' -bis (phenylcyanate) ethane (L10), phenolic cyanate (N10) or cyclopentadiene cyanate (P10).
Further, the silazane is one or a mixture of silazane oligomer or silazane polymer; the molecular structure of the silazane oligomer or the silazane polymer contains a silicon-nitrogen bond; the silazane oligomer is a silazane with 2-10 silicon atoms in a molecular structure, and the silazane polymer is a silazane with at least 11 silicon atoms in the molecular structure.
The silazane oligomer or silazane polymer is selected for the present invention because the silazane oligomer or silazane polymer can lower the curing temperature of cyanate ester and increase the temperature resistance of cyanate ester.
Further, the silazane is one or a mixture of silazane, boron/aluminum silazane, carbosilazane or siloxysilazane.
Further, the silazane has the general formula
The general formula of the boron/aluminum-silicon-nitrogen alkane is shown in the specification
The silasiloxane has the general formula
The carbosilazane has the general formula
In the formula R17、R11、R11'、R13、R13'、R15And R15'Is one of H, linear or branched alkyl, linear or branched alkenyl, linear or branched aryl, linear or branched arylalkyl and linear or branched alkenylaryl;
R17'is one of H, linear or branched alkyl, linear or branched alkenyl, linear or branched aryl and a general formula (V)
R12And R12'Is one of alkyl and phenyl of H, C1-C4;
R14and R14'Is one of H, linear or branched alkyl, linear or branched alkenyl and general formula (VI)
R16Is an alkylene group of C1 to C10;
m is B or Al;
m, k, p, q, o and s are integers; m is more than or equal to 0 and less than or equal to 2000, k is more than or equal to 0 and less than or equal to 2000, when m is equal to 0, k is not equal to 0, and when k is equal to 0, m is not equal to 0; s is more than or equal to 1 and less than or equal to 50; p is more than or equal to 1 and less than or equal to 100; q is more than or equal to 0 and less than or equal to 2000, and o is more than or equal to 1 and less than or equal to 1000.
Further, the solid filler is at least one of oxides, carbides, nitrides, borides and silicides of IIIA, IVA main groups, B groups and lanthanide series metals.
The solid filler added in the invention can play a role in reinforcing, toughening and improving the temperature resistance of the adhesive.
Further, the solid pigment is an inorganic pigment.
Preferably, the solid pigment is iron red, chrome yellow or titanium white.
Further, the chopped fibers are carbon fibers, silicon carbide fibers, alumina fibers, quartz fibers, glass fibers, silicon nitride or boron nitride, and the length of the chopped fibers 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 invention has the following beneficial effects:
(1) according to the invention, silazane hybridized cyanate is used as matrix resin for the high-temperature-resistant adhesive, so that the temperature resistance and the oxidation resistance of the cyanate are improved, and the high-temperature-resistant adhesive is prepared by matching corresponding fillers;
(2) the adhesive of the invention improves the high temperature performance while maintaining the bonding performance of the cyanate adhesive;
(3) the adhesive prepared by the invention can meet the requirements of the fields of aviation, aerospace and the like on high-temperature-resistant structural adhesives.
Detailed Description
The invention adopts cyanate ester or modified bifunctional, oligomeric or multifunctional cyanate ester or prepolymer thereof to quantitatively mix with silazane oligomer or polymer, solid filler, chopped fiber and solid pigment, thus obtaining the high temperature resistant structural adhesive.
The preparation method of the high-temperature resistant structural adhesive comprises the following steps:
100 parts of cyanate ester or the modified bifunctional, oligomeric or multifunctional cyanate ester or the prepolymer thereof is added with a certain amount of auxiliary filler to be uniformly mixed, then the corresponding curing agent is added, and the mixture is uniformly mixed and degassed for 5-10 minutes, so that the high-temperature-resistant structural adhesive can be used.
The curing method of the high-temperature resistant structural adhesive comprises the following steps:
the adhesive is pre-cured for 1-5 hours at 30-70 ℃, preferably 45-60 ℃, and then heated to 130-240 ℃, preferably 150-200 ℃, and cured for 1-4 hours.
Wherein, the cyanate is one or a mixture of more of difunctional or polyfunctional cyanate, cyanate oligomer and cyanate prepolymer; 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 structural formula of the cyanate is
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, wherein the alkyl or aryl group can be fluorinated or partially fluorinated;
in the formula II, R1To R8Is one of hydrogen, C1-C10 alkyl, C3-C8 cycloalkyl, C1-C10 alkoxy, halogen, phenyl or phenoxy, wherein the alkyl or aryl group may be fluorinated or partially fluorinated;
z represents a bond, SO2、CF2、CH2、CHF、CH(CH3) Isopropylidene, hexafluoroisopropylidene, C1-C10 alkylene, O, NR9N-N, CH-N, CH-CH, COO, CH-N-CH, alkyleneoxy having C1-C8 alkylene group, 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 may be selected from phenylene-1, 3-dicyanate, phenylene-1, 4-dicyanate or 2,4, 5-trifluorophenylene-1, 3-dicyanate; when the cyanate ester is represented by formula II, 4,4 '-bis (phenyl cyanate ester) methane, dicyclopentadiene cyanate ester, 4, 4' -bis (phenyl cyanate ester) isopropane, 2, 2-bis (4-cyanate ester-phenyl) hexafluoropropane may be selected as the cyanate ester; 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
The aliphatic group of the difunctional or polyfunctional aliphatic cyanate ester can contain one or more fluorine atoms;
in the formula IV, R10Represents an organic non-aromatic divalent hydrocarbon/hydrocarbon group having 3 to 12 carbon atoms, the hydrogen atoms of which can be partially or fully substituted by fluorine atoms.
Notably, the cyanate ester can be a cyanate ester monomer or a cyanate ester prepolymer, used alone or as a mixture with each other or as a mixture of other monofunctional cyanate esters; prepolymer means a substance capable of further crosslinking and usable as difunctional cyanate or oligocyanate are: 4,4 '-bis (phenylcyanate) isopropane (B10), 4' -bis (phenylcyanate) ethane (L10), phenolic cyanate (N10) or cyclopentadiene cyanate (P10).
In the invention, the silazane is one or a mixture of silazane oligomer or silazane polymer; the molecular structure of the silazane oligomer or the silazane polymer contains a silicon-nitrogen bond; the silazane oligomer is a silazane having 2-10 silicon atoms in a molecular structure, and the silazane polymer is a silazane having at least 11 silicon atoms in a molecular structure.
It is noted that the silazane is a mixture of one or more of silazane, boron/aluminum silazane, carbosilazane or siloxysilazane, and may also be a mixture of one or more of modified silazane, modified borosilazane, modified carbosilazane, modified aluminum silazane or modified siloxysilazane.
Notably, the silazanes have the formula
The general formula of the boron/aluminum-silicon-nitrogen alkane is
The silasiloxane has the general formula
Carbosilazanes of the general formula
In the formula R17、R11、R11'、R13、R13'、R15And R15'Is one of H, linear or branched alkyl, linear or branched alkenyl, linear or branched aryl, linear or branched arylalkyl and linear or branched alkenylaryl;
R17'is one of H, linear or branched alkyl, linear or branched alkenyl, linear or branched aryl and a general formula (V)
R12And R12'Is one of alkyl and phenyl of H, C1-C4;
R14and R14'Is one of H, linear or branched alkyl, linear or branched alkenyl and general formula (VI)
R16Is an alkylene group of C1 to C10;
m is B or Al;
m, k, p, q, o and s are integers; m is more than or equal to 0 and less than or equal to 2000, k is more than or equal to 0 and less than or equal to 2000, when m is equal to 0, k is not equal to 0, and when k is equal to 0, m is not equal to 0; s is more than or equal to 1 and less than or equal to 50; p is more than or equal to 1 and less than or equal to 100; q is more than or equal to 0 and less than or equal to 2000, and o is more than or equal to 1 and less than or equal to 1000.
It is noted that the solid filler in the invention is at least one of oxides, carbides, nitrides, borides and silicides of IIIA, IVA main group, B group and lanthanide series metals.
It is noted that the solid pigment in the present invention is an inorganic pigment such as iron red, chrome yellow or titanium white.
It is worth noting that the chopped fiber in the invention is carbon fiber, silicon carbide fiber, alumina fiber, quartz fiber, glass fiber, silicon nitride or boron nitride, and the length of the chopped fiber is 1-5 mm.
Wherein, the method and the standard of the corresponding performance test involved in the invention are all according to the following standards
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
Example 1
This example adds 80 parts of SiO to 100 parts of 4, 4' -bis (phenyl cyanate) ethane (L10)240 parts of ZrB210 portions of SiC and 10 portions of TiC as solid fillers, and 3 portions of SiO2As chopped fibers, 3 parts of Fe2O3The high-temperature-resistant silazane hybrid cyanate adhesive is used for bonding plastics, metals, graphite, ceramics and composite materials thereof, wherein 4, 4' -bis (phenyl cyanate) is used as the solid pigment, the solid pigment is fully and uniformly mixed, 20 parts of silazane is added, and the high-temperature-resistant silazane hybrid cyanate adhesive is obtained after vacuum degassing is carried out for 5 minutes) The structural formula of ethane (L10) is shown in formula 1, and the structural formula of silazane is shown in formula 2.
The curing process of the high temperature resistant silazane hybrid cyanate adhesive in the embodiment comprises the following steps: precuring for 2 hours at 45 ℃, then heating to 150 ℃ for curing for 2 hours, cooling to room temperature, and testing the room-temperature bonding strength of the cured high-temperature-resistant silazane hybrid cyanate adhesive.
The structural formula of the 4, 4' -bis (phenyl cyanate) ethane is shown in the specification
The silazane has the structural formula
The cured high-temperature-resistant silazane hybrid cyanate adhesive is used for bonding different base materials, and the room-temperature shear strength of the adhesive is tested, as shown in table 1.
TABLE 1 Room temperature bond Strength of silazane hybrid cyanate ester Adhesives to different substrates
Example 2
This example adds 80 parts of SiO to 100 parts of 4, 4' -bis (phenyl cyanate) ethane (L10)240 parts of ZrB210 portions of SiC and 10 portions of TiC as solid fillers, and 3 portions of SiO2As chopped fibers, 3 parts of Fe2O3Fully and uniformly mixing the solid pigment, and then adding silazane, wherein the silazane is added in parts by mass of (a)5 parts, (b)10 parts, (c)15 parts, (d)20 parts, (e)25 parts and (f)30 parts, and after vacuum degassing is carried out for 5 minutes, the high-temperature-resistant silazane hybrid cyanate adhesive is obtained;
the invention selects steel as a bonding base material, wherein the structural formula of 4, 4' -bis (phenyl cyanate) ethane (L10) is shown as formula 1, and the structural formula of silazane is shown as formula 2.
The curing process of the high temperature resistant silazane hybrid cyanate adhesive in the embodiment comprises the following steps: precuring for 2 hours at 45 ℃, then heating to 150 ℃ for curing for 2 hours, cooling to room temperature, and testing the bonding properties of the materials at room temperature and 250 ℃; meanwhile, in this example, comparative example 1 was prepared, and in comparative example 1, L10 was mixed with a filler, and the specific test results are shown in table 2.
TABLE 2 bonding Properties of silazane hybrid cyanate adhesive prepared with different silazane amounts
| Test specimen | Adhesive Strength at Room temperature (MPa) | Bond Strength (MPa) at 250 ℃ |
| a | 16.9 | 8.5 |
| b | 17.6 | 10.8 |
| c | 18.3 | 11.0 |
| d | 19.2 | 12.2 |
| e | 16.1 | 8.6 |
| f | 15.4 | 7.8 |
| Comparative example 1 | 16.2 | 8.4 |
As can be seen from Table 2, the silazane hybrid cyanate adhesive prepared by adding silazane has good bonding performance at room temperature and 250 ℃.
Example 3
This example adds 80 parts of SiO to 100 parts of 4, 4' -bis (phenyl cyanate) ethane (L10)240 parts of ZrB210 portions of SiC and 10 portions of TiC as solid fillers, and 5 portions of SiO2As chopped fibers, 3 parts of Fe2O3The high-temperature-resistant silazane hybrid cyanate adhesive is prepared by fully and uniformly mixing the solid pigment serving as the pigment, adding 20 parts of silazane and degassing for 10 minutes in vacuum, wherein steel is selected as a bonding base material, and the structural formula of 4, 4' -bis (phenyl cyanate) ethane (L10) is shown as formula 1, and the structural formula of silazane is shown as formula 2.
The curing process of the high temperature resistant silazane hybrid cyanate adhesive in the embodiment comprises the following steps: precuring for 2 hours at 45 ℃, then heating to 150 ℃ for curing for 2 hours, cooling to room temperature, and testing the room temperature and 250 ℃ adhesive property, which is shown in table 3.
TABLE 3 adhesion Properties of high temperature resistant silazane hybrid cyanate ester adhesives
| Adhesive Strength at Room temperature (MPa) | Bond Strength (MPa) at 250 ℃ | |
| Adhesive Strength (MPa) | 16.1 | 10.4 |
As can be seen from Table 3, the silazane hybrid cyanate adhesive prepared in this example has good adhesion performance at room temperature and 250 ℃.
Example 4
This example adds 80 parts of SiO to 100 parts of 4, 4' -bis (phenyl cyanate) ethane (L10)240 parts of ZrB210 portions of SiC and 10 portions of TiC as solid fillers, and 5 portions of SiO2As chopped fibers, 3 parts of Fe2O3The high-temperature-resistant silazane hybrid cyanate adhesive is prepared by fully and uniformly mixing the solid pigment serving as the pigment, adding 20 parts of silazane and degassing for 10 minutes in vacuum, wherein steel is selected as a bonding base material, and the structural formula of 4, 4' -bis (phenyl cyanate) ethane (L10) is shown as formula 1, and the structural formula of silazane is shown as formula 3.
The curing process of the high temperature resistant silazane hybrid cyanate adhesive in the embodiment comprises the following steps: precuring for 2 hours at 45 ℃, then heating to 150 ℃ for curing for 2 hours, cooling to room temperature, and testing the room temperature and 250 ℃ adhesive property, which is shown in table 4.
TABLE 4 adhesion Properties of high temperature resistant silazane hybrid cyanate ester adhesive
| Adhesive Strength at Room temperature (MPa) | Bond Strength (MPa) at 250 ℃ | |
| Adhesive Strength (MPa) | 18.6 | 11.9 |
As can be seen from Table 4, the silazane hybrid cyanate adhesive prepared in this example has good adhesion performance at room temperature and 250 ℃.
Example 5
This example adds 80 parts of SiO to 100 parts of 4, 4' -bis (phenyl cyanate) ethane (L10)240 parts of ZrB210 portions of SiC and 10 portions of TiC as solid fillers, and 5 portions of SiO2As chopped fibers, 3 parts of Fe2O3The high-temperature-resistant silazane hybrid cyanate adhesive is prepared by fully and uniformly mixing the solid pigment serving as the pigment, adding 20 parts of silazane and degassing for 10 minutes in vacuum, wherein steel is selected as a bonding base material, and the structural formula of 4, 4' -bis (phenyl cyanate) ethane (L10) is shown as formula 1, and the structural formula of silazane is shown as formula 4.
The curing process of the high temperature resistant silazane hybrid cyanate adhesive in the embodiment comprises the following steps: precuring for 2 hours at 45 ℃, then heating to 150 ℃ for curing for 2 hours, cooling to room temperature, and testing the room temperature and 250 ℃ adhesive property, which is shown in table 5.
TABLE 5 adhesion Properties of high temperature resistant silazane hybrid cyanate ester Adhesives
| Adhesive Strength at Room temperature (MPa) | Bond Strength (MPa) at 250 ℃ | |
| Adhesive Strength (MPa) | 18.2 | 10.6 |
As can be seen from Table 5, the silazane hybrid cyanate adhesive prepared in this example has good adhesion performance at room temperature and 250 ℃.
Example 6
This example adds 80 parts of SiO to 100 parts of 4, 4' -bis (phenyl cyanate) ethane (L10)240 parts of ZrB210 portions of SiC and 10 portions of TiC as solid fillers, and 5 portions of SiO2As chopped fibers, 3 parts of Fe2O3The high-temperature-resistant silazane hybrid cyanate adhesive is prepared by fully and uniformly mixing the solid pigment, adding 20 parts of silazane, and vacuum degassing for 10 minutes.
The curing process of the high temperature resistant silazane hybrid cyanate adhesive in the embodiment comprises the following steps: precuring for 2 hours at 45 ℃, then heating to 150 ℃ for curing for 2 hours, cooling to room temperature, and testing the room temperature and 250 ℃ adhesive property, which is shown in table 6.
TABLE 6 adhesion Properties of high temperature silazane hybrid cyanate ester Adhesives
| Adhesive Strength at Room temperature (MPa) | Bond Strength (MPa) at 250 ℃ | |
| Adhesive Strength (MPa) | 18.3 | 10.5 |
As can be seen from Table 6, the silazane hybrid cyanate adhesive prepared in this example has good adhesion performance at room temperature and 250 ℃.
Example 7
This example adds 80 parts of SiO to 100 parts of 4, 4' -bis (phenyl cyanate) ethane (L10)240 parts of ZrB210 portions of SiC and 10 portions of TiC as solid fillers, and 5 portions of SiO2As chopped fibers, 3 parts of Fe2O3And (2) fully and uniformly mixing the solid pigment, adding 20 parts of silazane, wherein the silazane is obtained by mixing a formula 5 and a formula 4 according to a mass ratio of 1:1, and vacuum degassing for 10 minutes to obtain the high-temperature-resistant silazane hybrid cyanate adhesive.
The curing process of the high temperature resistant silazane hybrid cyanate adhesive in the embodiment comprises the following steps: precuring for 2 hours at 45 ℃, then heating to 150 ℃ for curing for 2 hours, cooling to room temperature, and testing the room temperature and 250 ℃ adhesive property, which is shown in table 7.
TABLE 7 adhesion Properties of high temperature resistant silazane hybrid cyanate ester adhesives
| Adhesive Strength at Room temperature (MPa) | Bond Strength (MPa) at 250 ℃ | |
| Adhesive Strength (MPa) | 18.5 | 10.5 |
As can be seen from Table 7, the silazane hybrid cyanate adhesive prepared in this example has good adhesion performance at room temperature and 250 ℃.
Example 8
This example adds 80 parts of SiO to 100 parts of 4, 4' -bis (phenyl cyanate) ethane (L10)240 parts of ZrB210 portions of SiC and 10 portions of TiC as solid fillers, and 5 portions of SiO2As chopped fibers, 3 parts of Fe2O3The high-temperature-resistant silazane hybrid cyanate adhesive is prepared by fully and uniformly mixing the solid pigment serving as the pigment, adding 20 parts of silazane and degassing for 10 minutes in vacuum, wherein steel is selected as a bonding base material, and the structural formula of 4, 4' -bis (phenyl cyanate) ethane (L10) is shown as formula 1, and the structural formula of silazane is shown as formula 4.
The curing process of the high temperature resistant silazane hybrid cyanate adhesive in the embodiment comprises the following steps: precuring at 30 ℃ for 5 hours, then heating to 130 ℃, curing for 4 hours, cooling to room temperature, and testing the room temperature and 250 ℃ adhesive property, which is shown in table 8.
TABLE 8 adhesion Properties of high temperature silazane hybrid cyanate ester Adhesives
| Adhesive Strength at Room temperature (MPa) | Bond Strength (MPa) at 250 ℃ | |
| Adhesive Strength (MPa) | 18.0 | 9.7 |
As can be seen from Table 8, the silazane hybrid cyanate adhesive prepared in this example has good adhesion properties at room temperature and 250 ℃.
Example 9
This example adds 80 parts of SiO to 100 parts of 4, 4' -bis (phenyl cyanate) ethane (L10)240 parts of ZrB210 portions of SiC and 10 portions of TiC as solid fillers, and 5 portions of SiO2As chopped fibers, 3 parts of Fe2O3The high-temperature-resistant silazane hybrid cyanate adhesive is prepared by fully and uniformly mixing the solid pigment serving as the pigment, adding 20 parts of silazane and degassing for 10 minutes in vacuum, wherein steel is selected as a bonding base material, and the structural formula of 4, 4' -bis (phenyl cyanate) ethane (L10) is shown as formula 1, and the structural formula of silazane is shown as formula 4.
The curing process of the high temperature resistant silazane hybrid cyanate adhesive in the embodiment comprises the following steps: precuring at 55 ℃ for 2 hours, then heating to 170 ℃, curing for 2 hours, cooling to room temperature, and testing the room temperature and 250 ℃ adhesive property, which is shown in table 9.
TABLE 9 adhesion Properties of high temperature silazane hybrid cyanate ester Adhesives
| Adhesive Strength at Room temperature (MPa) | Bond Strength (MPa) at 250 ℃ | |
| Adhesive Strength (MPa) | 19.1 | 11.3 |
As can be seen from Table 9, the silazane hybrid cyanate adhesive prepared in this example has good adhesion properties at room temperature and 250 ℃.
Example 10
This example is carried out by adding Si to 100 parts of 4, 4' -bis (phenylcyanate) ethane (L10)3N4150 parts of, B4C30 parts, SiO210 parts of Al2O35 parts of SiO as solid filler2As chopped fibers, 3 parts of Fe2O3The high-temperature-resistant silazane hybrid cyanate adhesive is prepared by fully and uniformly mixing the solid pigment serving as the pigment, adding 20 parts of silazane and degassing for 10 minutes in vacuum, wherein steel is selected as a bonding base material, and the structural formula of 4, 4' -bis (phenyl cyanate) ethane (L10) is shown as formula 1, and the structural formula of silazane is shown as formula 4.
The curing process of the high temperature resistant silazane hybrid cyanate adhesive in the embodiment comprises the following steps: precuring for 2 hours at 45 ℃, then heating to 150 ℃ for curing for 2 hours, cooling to room temperature, and testing the room temperature and 250 ℃ adhesive property, which is shown in table 10.
TABLE 10 adhesion Properties of high temperature silazane hybrid cyanate ester Adhesives
| Adhesive Strength at Room temperature (MPa) | Bond Strength (MPa) at 250 ℃ | |
| Adhesive Strength (MPa) | 18.5 | 10.4 |
As can be seen from Table 10, the silazane hybrid cyanate adhesive prepared in this example has good adhesion properties at room temperature and 250 ℃.
Example 11
This example is carried out by adding 80 parts of SiO to 100 parts of a mixture of 4,4 '-bis (phenylcyanate) ethane (L10) and 4, 4' -methylenediphenyldicyanate240 parts of ZrB210 portions of SiC and 10 portions of TiC as solid fillers, and 5 portions of SiO2As chopped fibers, 3 parts of Fe2O3The high-temperature-resistant silazane-hybrid cyanate ester adhesive is obtained by fully and uniformly mixing the solid pigment, adding 20 parts of silazane, and vacuum degassing for 10 minutes, wherein the mass part ratio of 4,4 '-bis (phenyl cyanate) ethane (L10) to 4, 4' -methylene diphenyl dicyanate is 2: 10.
The curing process of the high temperature resistant silazane hybrid cyanate adhesive in the embodiment comprises the following steps: precuring for 2 hours at 45 ℃, then heating to 150 ℃ for curing for 2 hours, cooling to room temperature, and testing the room temperature and 250 ℃ adhesive property, which is shown in table 11.
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) | 18.9 | 10.8 |
As can be seen from Table 11, the silazane hybrid cyanate adhesive prepared in this example has good adhesion properties at room temperature and 250 ℃.
Example 12
This example adds 80 parts of SiO to 100 parts of 4, 4' -bis (phenyl cyanate) ethane (L10)240 parts of ZrB210 portions of SiC and 10 portions of TiC as solid fillers, and 5 portions of SiO2As chopped fibers, 3 parts of Fe2O3The high-temperature-resistant silazane hybrid cyanate adhesive is prepared by taking steel as a bonding base material, wherein the structural formula of 4, 4' -bis (phenyl cyanate) ethane (L10) is shown as formula 1, and the structural formula of the borosilazane is shown as formula 6.
The curing process of the high temperature resistant silazane hybrid cyanate adhesive in the embodiment comprises the following steps: precuring for 2 hours at 45 ℃, then heating to 150 ℃ for curing for 2 hours, cooling to room temperature, and testing the room temperature and 250 ℃ adhesive property, which is shown in table 12.
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) | 19.8 | 12.2 |
As can be seen from Table 12, the silazane hybrid cyanate adhesive prepared in this example has good adhesion properties at room temperature and 250 ℃.
Example 13
This example adds 80 parts of SiO to 100 parts of 4, 4' -bis (phenyl cyanate) ethane (L10)240 parts of ZrB210 portions of SiC and 10 portions of TiC as solid fillers, and 5 portions of SiO2As chopped fibers, 3 parts of Fe2O3The high-temperature-resistant silazane hybrid cyanate adhesive is prepared by fully and uniformly mixing the solid pigment, adding 20 parts of siloxazane, and degassing for 10 minutes in vacuum, wherein steel is used as a bonding base material, wherein the structural formula of 4, 4' -bis (phenyl cyanate) ethane (L10) is shown as formula 1, and the structural formula of siloxazane is shown as formula 7.
The curing process of the high temperature resistant silazane hybrid cyanate adhesive in the embodiment comprises the following steps: precuring for 2 hours at 45 ℃, then heating to 150 ℃ for curing for 2 hours, cooling to room temperature, and testing the room temperature and 250 ℃ adhesive property, which is shown in table 13.
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) | 18.5 | 10.1 |
As can be seen from Table 13, the silazane hybrid cyanate adhesive prepared in this example has good adhesion properties at room temperature and 250 ℃.
Example 14
This example adds 80 parts of SiO to 100 parts of 4, 4' -bis (phenyl cyanate) ethane (L10)240 parts of ZrB210 portions of SiC and 10 portions of TiC as solid fillers, and 5 portions of SiO2As chopped fibers, 3 parts of Fe2O3The high-temperature-resistant silazane hybrid cyanate adhesive is prepared by fully and uniformly mixing the solid pigment, adding 20 parts of carbosilazane, and degassing for 10 minutes in vacuum, wherein steel is used as a bonding base material, and the structural formula of 4, 4' -bis (phenyl cyanate) ethane (L10) is shown as formula 1, and the structural formula of carbosilazane is shown as formula 8.
The curing process of the high temperature resistant silazane hybrid cyanate adhesive in the embodiment comprises the following steps: precuring for 2 hours at 45 ℃, then heating to 150 ℃ for curing for 2 hours, cooling to room temperature, and testing the room temperature and 250 ℃ adhesive property, which is shown in table 14.
TABLE 14 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 | 11.2 |
As can be seen from Table 14, the silazane hybrid cyanate adhesive prepared in this example has good adhesion properties at room temperature and 250 ℃.
Example 15
In this example, 80 parts of SiO were added to 100 parts of p-phenylene dicyanate240 parts of ZrB210 portions of SiC and 10 portions of TiC as solid fillers, and 3 portions of SiO2As chopped fibers, 3 parts of Fe2O3Fully and uniformly mixing the solid pigment, and then adding silazane, wherein the silazane is added in parts by mass of (a)5 parts, (b)10 parts, (c)15 parts, (d)20 parts, (e)25 parts and (f)30 parts, and after vacuum degassing is carried out for 5 minutes, the high-temperature-resistant silazane hybrid cyanate adhesive is obtained; the phenyl cyanate is prepared into 75 percent solution,
the invention selects steel as a bonding base material, wherein the structural formula of p-phenyl dicyanate is shown as formula 9, and the structural formula of silazane is shown as formula 2.
The curing process of the high temperature resistant silazane hybrid cyanate adhesive in the embodiment comprises the following steps: precuring for 2 hours at 45 ℃, then heating to 150 ℃ for curing for 2 hours, cooling to room temperature, and testing the room temperature and 250 ℃ adhesive property, wherein the specific test results are shown in table 15.
TABLE 15 adhesion Properties of high temperature silazane hybrid cyanate ester Adhesives
| Adhesive Strength at Room temperature (MPa) | Bond Strength (MPa) at 250 ℃ | |
| Adhesive Strength (MPa) | 14.4 | 10.1 |
As can be seen from Table 15, the silazane hybrid cyanate adhesive prepared in this example has good adhesion properties at room temperature and 250 ℃.
Example 16
This example is carried out by adding 80 parts of SiO to 100 parts of bisphenol F dicyanate240 parts of ZrB210 portions of SiC and 10 portions of TiC as solid fillers, and 3 portions of SiO2As chopped fibers, 3 parts of Fe2O3Fully and uniformly mixing the solid pigment, and then adding silazane, wherein the silazane is added in parts by mass of (a)5 parts, (b)10 parts, (c)15 parts, (d)20 parts, (e)25 parts and (f)30 parts, and after vacuum degassing is carried out for 5 minutes, the high-temperature-resistant silazane hybrid cyanate adhesive is obtained; bisphenol F dicyanate is prepared into 85 percent solution,
the invention selects steel as a bonding base material, wherein the structural formula of p-phenyl dicyanate is shown as formula 10, and the structural formula of silazane is shown as formula 2.
The curing process of the high temperature resistant silazane hybrid cyanate adhesive in the embodiment comprises the following steps: precuring for 2 hours at 45 ℃, then heating to 150 ℃ for curing for 2 hours, cooling to room temperature, and testing the room temperature and 250 ℃ adhesive property, wherein the specific test results are shown in table 16.
TABLE 16 adhesion Properties of high temperature silazane hybrid cyanate ester Adhesives
| Adhesive Strength at Room temperature (MPa) | Bond Strength (MPa) at 250 ℃ | |
| Adhesive Strength (MPa) | 15.2 | 12.7 |
As can be seen from Table 16, the silazane hybrid cyanate adhesive prepared in this example has good adhesion properties at room temperature and 250 ℃.
Example 17
This example is carried out by adding 80 parts of SiO to 100 parts of dicyanate240 parts of ZrB210 portions of SiC and 10 portions of TiC as solid fillers, and 3 portions of SiO2As chopped fibers, 3 parts of Fe2O3Fully and uniformly mixing the solid pigment, and then adding silazane, wherein the silazane is added in parts by mass of (a)5 parts, (b)10 parts, (c)15 parts, (d)20 parts, (e)25 parts and (f)30 parts, and after vacuum degassing is carried out for 5 minutes, the high-temperature-resistant silazane hybrid cyanate adhesive is obtained; the dicyanate is prepared into 85 percent solution,
the invention selects steel as a bonding base material, wherein the structural formula of p-phenyl dicyanate is shown as formula 11, and the structural formula of silazane is shown as formula 2.
The curing process of the high temperature resistant silazane hybrid cyanate adhesive in the embodiment comprises the following steps: precuring for 2 hours at 45 ℃, then heating to 150 ℃ for curing for 2 hours, cooling to room temperature, and testing the room temperature and 250 ℃ adhesive property, wherein the specific test results are shown in table 17.
TABLE 17 adhesion Properties of high temperature silazane hybrid cyanate ester Adhesives
| Adhesive Strength at Room temperature (MPa) | Bond Strength (MPa) at 250 ℃ | |
| Adhesive Strength (MPa) | 13.1 | 10.5 |
As can be seen from Table 17, the silazane hybrid cyanate adhesive prepared in this example has good adhesion properties at room temperature and 250 ℃.
In conclusion, the invention provides a high temperature resistant silazane hybridized cyanate adhesive and preparation and curing methods thereof, silazane hybridized cyanate is used as matrix resin for the high temperature resistant adhesive, the temperature resistance and the oxidation resistance of the cyanate are improved, and the high temperature resistant adhesive is prepared by matching corresponding fillers; meanwhile, the adhesive prepared by the invention can meet the requirements of the fields of aviation, aerospace and the like on high-temperature-resistant structural adhesives.
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 (6)
1. The silazane hybridized cyanate 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 a silazane,
140 to 200 parts of a solid filler,
3 to 20 parts of a solid pigment,
3-5 parts of chopped fibers;
the solid filler is at least one 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 or boron nitride fibers, and the length of the chopped fibers is 1-5 mm;
the silazane is one or a mixture of silazane, boron/aluminum silazane, carbon silazane or silicon oxygen silazane;
the silazane has the formula
The general formula of the boron/aluminum-silicon-nitrogen alkane is shown in the specification
The silasiloxane has the general formula
The carbosilazane has the general formula
In the formula R17、R11、R11'、R13、R13'、R15And R15' is one of H, linear or branched alkyl, linear or branched alkenyl, linear or branched aryl, linear or branched arylalkyl, linear or branched alkenylaryl;
R17' is one of H, linear or branched alkyl, linear or branched alkenyl, linear or branched aryl, general formula (V) is
R12And R12' is one of alkyl and phenyl of H, C1-C4;
R14and R14' is one of H, linear or branched alkyl, linear or branched alkenyl, general formula (VI) and
R16is an alkylene group of C1 to C10;
m is B or Al;
m, k, p, q, o and s are integers; m is more than or equal to 0 and less than or equal to 2000, k is more than or equal to 0 and less than or equal to 2000, when m is equal to 0, k is not equal to 0, and when k is equal to 0, m is not equal to 0; s is more than or equal to 1 and less than or equal to 50; p is more than or equal to 1 and less than or equal to 100; q is more than or equal to 0 and less than or equal to 2000, and o is more than or equal to 1 and less than or equal to 1000;
the adhesive is used in the fields of aviation and aerospace.
2. A silazane hybrid cyanate ester adhesive according to claim 1, characterized in that said cyanate ester is one or a mixture of two or more of difunctional or multifunctional cyanate ester, cyanate ester oligomer, cyanate ester prepolymer.
3. A silazane hybrid cyanate ester adhesive according to claim 1 or 2, characterized in that the structural formula of the cyanate ester is
Or
Or
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 represents a bond, SO2、CF2、CH2、CHF、CH(CH3) Isopropylidene, hexafluoroisopropylidene, C1-C10 alkylene, O, NR9N-N, CH-N, CH-CH, COO, CH-N-CH, alkyleneoxy having C1-C8 alkylene group, S, Si (CH)3)2Or
Or
Or
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.
4. A silazane hybrid cyanate ester adhesive according to claim 3, characterized in that when said cyanate ester is of 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 represented by formula ii, the cyanate ester is 4,4 '-bis (phenyl cyanate) methane, dicyclopentadiene type cyanate ester, 4, 4' -bis (phenyl cyanate) isopropane, 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, R10Represents an organic non-aromatic divalent hydrocarbon/hydrocarbon group containing 3 to 12 carbon atoms, the hydrogen atoms of which can be partially or fully substituted by fluorine atoms.
5. A silazane hybrid cyanate ester adhesive according to claim 1, wherein said silazane is one or a mixture of silazane oligomer or silazane polymer; the molecular structure of the silazane oligomer or the silazane polymer contains a silicon-nitrogen bond; the silazane oligomer is a silazane with 2-10 silicon atoms in a molecular structure, and the silazane polymer is a silazane with at least 11 silicon atoms in the molecular structure.
6. A silazane hybrid cyanate ester adhesive according to claim 1, characterized in that said solid pigment is an inorganic pigment.
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| 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 |
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| CN101724226A (en) * | 2009-11-20 | 2010-06-09 | 苏州大学 | Modified hot setting resin and preparation method thereof |
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