CN107400495A - A kind of preparation method of silazane hydridization cyanate ester adhesive - Google Patents
A kind of preparation method of silazane hydridization cyanate ester adhesive Download PDFInfo
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- CN107400495A CN107400495A CN201710623039.2A CN201710623039A CN107400495A CN 107400495 A CN107400495 A CN 107400495A CN 201710623039 A CN201710623039 A CN 201710623039A CN 107400495 A CN107400495 A CN 107400495A
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- silazane
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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
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Abstract
The invention discloses a kind of preparation method of silazane hydridization cyanate ester adhesive, including：Step 1,0~200 part of solid packing, 0~20 part of solid pigment, 0~5 part of chopped strand are added in 100 parts of cyanates, be well mixed, obtain the first mixture；Step 2,5~30 parts of silazane are added into the first mixture, be well mixed, obtain the second mixture；Step 3, the second mixture is de-gassed, obtains silazane hydridization cyanate ester adhesive.Beneficial effects of the present invention：By the use of silazane hydridization cyanate as the matrix resin of high-temperature resistance adhesive, the temperature tolerance and inoxidizability of cyanate are improved, corresponding filler is matched and prepares resistant to elevated temperatures adhesive；While cyanate ester adhesive adhesive property is kept, its high-temperature behavior is improved；It disclosure satisfy that demand of the Aeronautics and Astronautics field to high-temperature-resistant structure adhesive.
Description
Technical field
The present invention relates to high-temperature resistance adhesive technical field, more particularly to a kind of system of silazane hydridization cyanate ester adhesive
Preparation Method.
Background technology
With the development of the industry such as high-tech development, particularly Aero-Space, electronics, machinery, weapons, for structure glue
Stick proposes higher requirement, such as temperature tolerance, anti-fatigue performance.
Current organic structure adhesive mainly includes epoxide resin type and polyimide type etc., but based on epoxy resin
Adhesive heatproof be less than 200 DEG C；Polyimide type adhesive has good temperature tolerance, but solidification temperature is high；Cyanate resin
Fat has good heat resistance and manufacturability, the adhesive structure part high available for heat resistant requirements, but its temperature tolerance still is apparent not enough, and
And high-temperature oxidation resistance is poor.
The content of the invention
In view of above-mentioned analysis, the present invention is intended to provide a kind of preparation method of silazane hydridization cyanate ester adhesive, is used
To solve the problems, such as existing cyanate ester adhesive binding agent temperature tolerance deficiency, high-temperature oxidation resistance difference.
The purpose of the present invention is mainly achieved through the following technical solutions：
A kind of preparation method of silazane hydridization cyanate ester adhesive, is mainly included the following steps that：
Step 1, in 100 parts of cyanates add 0~200 part of solid packing, 0~20 part of solid pigment, 0~5 part be chopped
Fiber, it is well mixed, obtains the first mixture；
Step 2,5~30 parts of silazane are added into the first mixture, be well mixed, obtain the second mixture；
Step 3, the second mixture is de-gassed, obtains silazane hydridization cyanate ester adhesive.
The preparation method of silazane hydridization cyanate ester adhesive of the present invention is simple, can reduce solidification temperature, meanwhile, it is capable to
Realize and produce in enormous quantities.
Further, in the step 3, vacuum outgas 5~10 minutes is carried out to second mixture.
Further, the preparation method also includes step 4, and the step 4 is that the high tenacity cyanate that will be obtained is gluing
Agent carries out curing process with base material, and the curing process is that the silazane hydridization cyanate ester adhesive is first pre- at 30~70 DEG C
Solidification 1~5 hour, is then warming up to 130~240 DEG C, 1~4 hour hardening time again.
Cyanate ester adhesive of the present invention can realize the abundant solidification of adhesive, improve the adhesive property under high temperature.This hair
The bright matrix resin by the use of silazane hydridization cyanate as high-temperature resistance adhesive, improve silazane hydridization cyanate ester adhesive
Heat-resisting quantity and inoxidizability, while match corresponding filler and prepare resistant to elevated temperatures adhesive, disclosure satisfy that Aeronautics and Astronautics
Demand Deng field to high-temperature-resistant structure adhesive.
Further, the silazane hydridization cyanate ester adhesive is first in 45~60 DEG C of precuring 1~5 hour, Ran Houzai
150~200 DEG C are warming up to, 1~4 hour hardening time.
Further, the viscosity of second mixture is 0.1~200Pas.
The viscosity of second mixture of the invention is easy to construct in 0.1~200Pas.
Further, the cyanate is at least the cyanate of difunctionality.
The cyanate that present invention selection is at least difunctionality is because degree of functionality is related to the formation of cross-linking system, if official
Energy degree is few, then can not form cross-linking system, can not solidify.
Further, the cyanate is difunctionality or polyfunctional cyanate, cyanic acid ester oligomer, cyanate prepolymer
In one or more of mixtures.
Raw material cyanate can be liquid cyanate or the organic solvent solution of cyanate, the concentration control of cyanic acid ester solution
System is more than 70%.
Further, the cyanate is cyanate ester monomer or cyanate prepolymer, the cyanate ester monomer or cyanogen
Acid esters prepolymer is made individually or as mutual mixture or as the mixture of other simple function cyanates
With.
The prepolymer is the material for referring to further be crosslinked, and can act as difunctionality cyanate or oligomeric cyanate
It is：4,4 '-bis- (phenylcyanate) isopropyl alkanes (B10), 4,4 '-bis- (phenylcyanate) ethane (L10), Novolac Cyanate Eater Resin
Or Cyclopeutadiene type cyanate (P10) (N10).
Further, the silazane is one or more of mixtures of silazane oligomer or silicon nitrogen silane copolymer；
Contain silazine link in the molecular structure of the silazane oligomer or silicon nitrogen silane copolymer；The silazane oligomer is molecule knot
There is the silazane of 2~10 silicon atoms, the silicon nitrogen silane copolymer is at least to contain 11 silicon atoms in molecular structure in structure
Silazane above.
Present invention selection silazane oligomer or silicon nitrogen silane copolymer are because silazane oligomer or silicon nitrogen silane copolymer
The solidification temperature of cyanate can be reduced, improves the temperature tolerance of cyanate.
Further, the silazane be silazane, boron aluminium silazane, carbon silazane or silica silazane one kind or
Several mixtures.
Further, the formula of the silazane is
The formula of the boron aluminium silazane is
The formula of the silica silazane is
The formula of the carbon silazane is
R in formula17、R11、R11'、R13、R13'、R15And R15'For H, the alkyl of straight or branched, straight or branched alkenyl, straight
The aryl of chain or side chain, the aryl alkyl of straight or branched, straight or branched alkenyl aryl in one kind；
R17'For in H, the alkyl of straight or branched, the alkenyl of straight or branched, the aryl of straight or branched, logical formula (V)
One kind, logical formula (V) are
R12And R12'For one kind in H, C1~C4 alkyl, phenyl；
R14And R14'For one kind in H, the alkyl of straight or branched, the alkenyl of straight or branched, logical formula (VI), formula
(VI) it is
R16For C1~C10 alkylidene；
M is B or Al；
M, k, p, q, o, s are integer；0≤m≤2000,0≤k≤2000, as m=0, k ≠ 0, as k=0, m ≠ 0；1
≤s≤50；1≤p≤100；0≤q≤2000,1≤o≤1000.
Further, the solid packing is III A, IV A main groups, B races, the oxide of lanthanide series metal, carbide, nitridation
At least one of thing, boride, silicide.
Solid packing is added in the present invention can play enhancing, toughness reinforcing to adhesive and improve durothermic effect.
Further, the solid pigment is inorganic pigment.
Preferably, the solid pigment is iron oxide red, chrome yellow or titanium white.
Further, the chopped strand is carbon fiber, silicon carbide fibre, alumina fibre, quartz fibre, glass fibers
Dimension, silicon nitride fiber, silicon nitride or boron nitride, the chopped strand length are 1~5 millimeter.
The chopped strand of the present invention 1~5 mm length of selection, can play a part of toughness reinforcing, if chopped strand is too short, nothing
Method plays the effect of toughness reinforcing, if chopped strand is oversize, can not be well mixed the various raw materials of cyanate ester adhesive.
The present invention has the beneficial effect that：
(1) present invention improves cyanate by the use of silazane hydridization cyanate as the matrix resin of high-temperature resistance adhesive
Temperature tolerance and inoxidizability, while match corresponding filler and prepare resistant to elevated temperatures adhesive；
(2) adhesive of the invention improves its high-temperature behavior while cyanate ester adhesive adhesive property is kept；
(3) adhesive prepared by the present invention disclosure satisfy that need of the fields such as Aeronautics and Astronautics to high-temperature-resistant structure adhesive
Ask.
Embodiment
The present invention is using cyanate or its difunctionality, oligomer or polyfunctional cyanate or its prepolymer and silicon for being modified
Azane oligomer or polymer, solid packing, chopped strand, solid pigment carry out quantitative mixing, you can high temperature resistant is prepared
Sqtructural adhesive.
The preparation method of high-temperature-resistant structure adhesive of the present invention is：
One is added in 100 parts of cyanates or its difunctionality, oligomer or polyfunctional cyanate for being modified or its prepolymer
After quantitative auxiliary packing is well mixed, corresponding curing agent is added, is deaerated 5~10 minutes after mixing well, you can as resistance to height
Warm sqtructural adhesive uses.
The curing of high-temperature-resistant structure adhesive of the present invention is：
The adhesive first in 30~70 DEG C of preferably 45~60 DEG C of precuring 1~5 hour, is then warming up to 130~240 again
DEG C, preferably 150~200 DEG C, 1~4 hour hardening time.
Wherein, cyanate is one kind in difunctionality or polyfunctional cyanate, cyanic acid ester oligomer, cyanate prepolymer
Or several mixture；Cyanate can be the organic solvent solution of liquid cyanate or cyanate, cyanic acid ester solution it is dense
Degree control is more than 70%.
The structural formula of cyanate is
Or at least one of aliphatic cyanate；
In formula I, R1To R4For hydrogen, C1-C10 alkyl, C3-C8 cycloalkyl, C1-C10 alkoxies, halogen, phenyl or phenoxy group
In one kind, wherein alkyl or aryl can be fluorinated or partially fluorinated；
In formula II, R1To R8For hydrogen, C1-C10 alkyl, C3-C8 cycloalkyl, C1-C10 alkoxies, halogen, phenyl or benzene oxygen
One kind in base, wherein alkyl or aryl can be fluorinated or partially fluorinated；
Z represents chemical bond, SO2、CF2、CH2、CHF、CH(CH3), isopropylidene, hexafluoroisopropyli,ene, C1-C10 alkylenes
Base, O, NR9, N=N, CH=N, CH=CH, COO, CH=N-N=CH, there is the alkylene oxide groups of C1-C8 alkylidenes, S, Si
(CH3)2Or
In formula III, R9For one kind in H or C1-C10 alkyl, 0≤n≤20, n are integer.
Preferably, when cyanate is Formulas I, cyanate can select phenylene -1,3- dicyanate, phenylene-Isosorbide-5-Nitrae -
Dicyanate or 2,4,5- trifluoro phenylene -1,3- dicyanates；When cyanate is formula II, cyanate can select 4,4 '-
Double (phenylcyanate) methane, dicyclopentadiene type ethylene rhodanate, 4,4 '-bis- (phenylcyanate) isopropyl alkanes, 2,2- double (4- cyanic acid
Ester group-phenyl) HFC-236fa；Aliphatic cyanate is difunctionality aliphatic cyanate or multifunctional aliphatic cyanate,
The structural formula of aliphatic cyanate is
N≡C-O-R10- O-C ≡ N formulas IV
One or more fluorine atoms can be contained in the aliphatic group of difunctionality or polyfunctional aliphatic cyanate；
In formula IV, R10Divalent hydrocarbon/alkyl of the organic non-aromatic containing 3~12 carbon atoms is represented, organic non-aromatic
The hydrogen atom of divalent hydrocarbon/alkyl can partly or entirely be substituted by fluorine atom.
It is noted that cyanate can be cyanate ester monomer or cyanate prepolymer, cyanate ester monomer or cyanic acid
Ester prepolymer is used individually or as mutual mixture or as the mixture of other simple function cyanates；
Prepolymer is the material for referring to further be crosslinked, and can act as difunctionality cyanate or oligomeric cyanate is：4,4 '-bis-
(phenylcyanate) isopropyl alkane (B10), 4,4 '-bis- (phenylcyanate) ethane (L10), Novolac Cyanate Eater Resin (N10) or rings penta
Diene type cyanate (P10).
It is noted that silazane is that silazane oligomer or the one or more of of silicon nitrogen silane copolymer mix in the present invention
Compound；Contain silazine link in the molecular structure of silazane oligomer or silicon nitrogen silane copolymer；Silazane oligomer is molecular structure
In there is the silazane of 2~10 silicon atoms, silicon nitrogen silane copolymer be in molecular structure at least containing 11 silicon atoms more than
Silazane.
It is noted that silazane be silazane, boron aluminium silazane, carbon silazane or one kind in silica silazane or
A variety of mixtures or modified silazane, modified borosilicate azane, carbon modified silazane, modified aluminium silazane or modification
One or more of mixtures in silica silazane.
It is noted that the formula of silazane is
The formula of boron aluminium silazane is
The formula of silica silazane is
The formula of carbon silazane is
R in formula17、R11、R11'、R13、R13'、R15And R15'For H, the alkyl of straight or branched, straight or branched alkenyl, straight
The aryl of chain or side chain, the aryl alkyl of straight or branched, straight or branched alkenyl aryl in one kind；
R17'For in H, the alkyl of straight or branched, the alkenyl of straight or branched, the aryl of straight or branched, logical formula (V)
One kind, logical formula (V) are
R12And R12'For one kind in H, C1~C4 alkyl, phenyl；
R14And R14'For one kind in H, the alkyl of straight or branched, the alkenyl of straight or branched, logical formula (VI), formula
(VI) it is
R16For C1~C10 alkylidene；
M is B or Al；
M, k, p, q, o, s are integer；0≤m≤2000,0≤k≤2000, as m=0, k ≠ 0, as k=0, m ≠ 0；1
≤s≤50；1≤p≤100；0≤q≤2000,1≤o≤1000.
It is noted that in the present invention solid packing be III A, IV A main groups, B races, the oxide of lanthanide series metal, carbide,
At least one of nitride, boride, silicide.
It is noted that solid pigment is inorganic pigment in the present invention, such as iron oxide red, chrome yellow or titanium white.
It is noted that chopped strand is carbon fiber, silicon carbide fibre, alumina fibre, quartz fibre, glass in the present invention
Glass fiber, silicon nitride fiber, silicon nitride or boron nitride, chopped strand length are 1~5 millimeter.
Wherein, the method for respective performances involved in present invention test and standard are according to following standard
GJB444-1988《Adhesive drawing by high temperature shear strength experimental method (metal to metal)》
GB/T7124-2008《Adhesive tensile shear method of testing (metal to metal)》
GB/T14992-2005《The classification of high temperature alloy and intermetallic compound high-temperature material and the trade mark》
Embodiment 1
The present embodiment is in 100 part 4,4 '-bis- middle additions of (phenylcyanate) ethane (L10), 80 parts of SiO2, 40 parts of ZrB2、10
Part SiC, 10 parts of TiC are as solid packing, 3 parts of SiO2As chopped strand, 3 parts of Fe2O3As solid pigment, fully mix, then
20 parts of silazane are added, after vacuum outgas 5 minutes, obtain high temperature resistant silicon azane hydridization cyanate ester adhesive, invention adhesive
For plastics, metal, graphite, ceramic composite materials bonding, wherein, 4,4 '-bis- (phenylcyanate) ethane (L10)
Structural formula is shown in formula 1, and the structural formula of silazane is shown in formula 2.
The curing process of high temperature resistant silicon azane hydridization cyanate ester adhesive is in the present embodiment：It is first pre- solid under the conditions of 45 DEG C
Change 2 hours, be then warming up to 150 DEG C of 2 hours hardening times again, be cooled to room temperature, the high temperature resistant silicon azane after test solidification is miscellaneous
Change the room temperature adhesion strength of cyanate ester adhesive.
The structural formula of 4,4 '-bis- (phenylcyanate) ethane is
The structural formula of silazane is
High temperature resistant silicon azane hydridization cyanate ester adhesive after this implementation is solidified is used for the bonding of different substrate materials, tests it
Room temperature shear strength, as shown in table 1.
Room temperature adhesion strength of the silazane hydridization cyanate ester adhesive of table 1 to different substrate materials
Embodiment 2
The present embodiment is in 100 part 4,4 '-bis- middle additions of (phenylcyanate) ethane (L10), 80 parts of SiO2, 40 parts of ZrB2、10
Part SiC, 10 parts of TiC are as solid packing, 3 parts of SiO2As chopped strand, 3 parts of Fe2O3As solid pigment, fully mix, then
Add silazane, the addition mass fraction of silazane is 5 parts of (a), 10 parts of (b), 15 parts of (c), 20 parts of (d), 25 parts of (e), (f) 30
Part, after vacuum outgas 5 minutes, obtain high temperature resistant silicon azane hydridization cyanate ester adhesive；
The present invention from steel as bonding substrates, wherein, the structural formula of 4,4 '-bis- (phenylcyanate) ethane (L10) is shown in
Formula 1, the structural formula of silazane are shown in formula 2.
The curing process of high temperature resistant silicon azane hydridization cyanate ester adhesive is in the present embodiment：It is first pre- solid under the conditions of 45 DEG C
Change 2 hours, be then warming up to 150 DEG C of 2 hours hardening times again, be cooled to room temperature, test its room temperature and 250 DEG C of adhesive properties；
Meanwhile the present embodiment prepares comparative example 1, comparative example 1 is to mix L10 with filler, and specific test result is shown in Table 2.
The adhesive property of silazane hydridization cyanate ester adhesive prepared by the different silazane dosages of table 2
| Sample | Room temperature adhesion strength (MPa) | 250 DEG C of adhesion strengths (MPa) |
| 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 |
By table 2, it can be seen that silazane hydridization cyanate ester adhesive prepared by addition silazane is glued at room temperature with 250 DEG C
Connect functional.
Embodiment 3
The present embodiment is in 100 part 4,4 '-bis- middle additions of (phenylcyanate) ethane (L10), 80 parts of SiO2, 40 parts of ZrB2、10
Part SiC, 10 parts of TiC are as solid packing, 5 parts of SiO2As chopped strand, 3 parts of Fe2O3As solid pigment, fully mix, then
20 parts of silazane are added, after vacuum outgas 10 minutes, obtain high temperature resistant silicon azane hydridization cyanate ester adhesive, the present invention selects steel
For bonding substrates, wherein, the structural formula of 4,4 '-bis- (phenylcyanate) ethane (L10) is shown in formula 1, and the structural formula of silazane is shown in formula
2。
The curing process of high temperature resistant silicon azane hydridization cyanate ester adhesive is in the present embodiment：It is first pre- solid under the conditions of 45 DEG C
Change 2 hours, be then warming up to 150 DEG C of 2 hours hardening times again, be cooled to room temperature, test its room temperature and 250 DEG C of adhesive properties,
Specifically it is shown in Table 3.
The adhesive property of the high temperature resistant silicon azane hydridization cyanate ester adhesive of table 3
| Room temperature adhesion strength (MPa) | 250 DEG C of adhesion strengths (MPa) | |
| Adhesion strength (MPa) | 16.1 | 10.4 |
By table 3, it can be seen that silazane hydridization cyanate ester adhesive manufactured in the present embodiment is be bonded with 250 DEG C in room temperature
It is functional.
Embodiment 4
The present embodiment is in 100 part 4,4 '-bis- middle additions of (phenylcyanate) ethane (L10), 80 parts of SiO2, 40 parts of ZrB2、10
Part SiC, 10 parts of TiC are as solid packing, 5 parts of SiO2As chopped strand, 3 parts of Fe2O3As solid pigment, fully mix, then
20 parts of silazane are added, after vacuum outgas 10 minutes, obtain high temperature resistant silicon azane hydridization cyanate ester adhesive, the present invention selects steel
For bonding substrates, wherein, the structural formula of 4,4 '-bis- (phenylcyanate) ethane (L10) is shown in formula 1, and the structural formula of silazane is shown in formula
3。
The curing process of high temperature resistant silicon azane hydridization cyanate ester adhesive is in the present embodiment：It is first pre- solid under the conditions of 45 DEG C
Change 2 hours, be then warming up to 150 DEG C of 2 hours hardening times again, be cooled to room temperature, test its room temperature and 250 DEG C of adhesive properties,
Specifically it is shown in Table 4.
The adhesive property of the high temperature resistant silicon azane hydridization cyanate ester adhesive of table 4
| Room temperature adhesion strength (MPa) | 250 DEG C of adhesion strengths (MPa) | |
| Adhesion strength (MPa) | 18.6 | 11.9 |
By table 4, it can be seen that silazane hydridization cyanate ester adhesive manufactured in the present embodiment is be bonded with 250 DEG C in room temperature
It is functional.
Embodiment 5
The present embodiment is in 100 part 4,4 '-bis- middle additions of (phenylcyanate) ethane (L10), 80 parts of SiO2, 40 parts of ZrB2、10
Part SiC, 10 parts of TiC are as solid packing, 5 parts of SiO2As chopped strand, 3 parts of Fe2O3As solid pigment, fully mix, then
20 parts of silazane are added, after vacuum outgas 10 minutes, obtain high temperature resistant silicon azane hydridization cyanate ester adhesive, the present invention selects steel
For bonding substrates, wherein, the structural formula of 4,4 '-bis- (phenylcyanate) ethane (L10) is shown in formula 1, and the structural formula of silazane is shown in formula
4。
The curing process of high temperature resistant silicon azane hydridization cyanate ester adhesive is in the present embodiment：It is first pre- solid under the conditions of 45 DEG C
Change 2 hours, be then warming up to 150 DEG C of 2 hours hardening times again, be cooled to room temperature, test its room temperature and 250 DEG C of adhesive properties,
Specifically it is shown in Table 5.
The adhesive property of the high temperature resistant silicon azane hydridization cyanate ester adhesive of table 5
| Room temperature adhesion strength (MPa) | 250 DEG C of adhesion strengths (MPa) | |
| Adhesion strength (MPa) | 18.2 | 10.6 |
By table 5, it can be seen that silazane hydridization cyanate ester adhesive manufactured in the present embodiment is be bonded with 250 DEG C in room temperature
It is functional.
Embodiment 6
The present embodiment is in 100 part 4,4 '-bis- middle additions of (phenylcyanate) ethane (L10), 80 parts of SiO2, 40 parts of ZrB2、10
Part SiC, 10 parts of TiC are as solid packing, 5 parts of SiO2As chopped strand, 3 parts of Fe2O3As solid pigment, fully mix, then
20 parts of silazane are added, after vacuum outgas 10 minutes, obtain high temperature resistant silicon azane hydridization cyanate ester adhesive, the present invention selects steel
For bonding substrates, wherein, the structural formula of 4,4 '-bis- (phenylcyanate) ethane (L10) is shown in formula 1, and the structural formula of silazane is shown in formula
5。
The curing process of high temperature resistant silicon azane hydridization cyanate ester adhesive is in the present embodiment：It is first pre- solid under the conditions of 45 DEG C
Change 2 hours, be then warming up to 150 DEG C of 2 hours hardening times again, be cooled to room temperature, test its room temperature and 250 DEG C of adhesive properties,
Specifically it is shown in Table 6.
The adhesive property of the high temperature resistant silicon azane hydridization cyanate ester adhesive of table 6
| Room temperature adhesion strength (MPa) | 250 DEG C of adhesion strengths (MPa) | |
| Adhesion strength (MPa) | 18.3 | 10.5 |
By table 6, it can be seen that silazane hydridization cyanate ester adhesive manufactured in the present embodiment is be bonded with 250 DEG C in room temperature
It is functional.
Embodiment 7
The present embodiment is in 100 part 4,4 '-bis- middle additions of (phenylcyanate) ethane (L10), 80 parts of SiO2, 40 parts of ZrB2、10
Part SiC, 10 parts of TiC are as solid packing, 5 parts of SiO2As chopped strand, 3 parts of Fe2O3As solid pigment, fully mix, then
Add 20 parts of silazane, it is 1 that silazane, which is formula 5 and formula 4 according to mass ratio,:1 is mixed to get, after vacuum outgas 10 minutes,
Obtaining high temperature resistant silicon azane hydridization cyanate ester adhesive, the present invention is bonding substrates from steel, wherein, 4,4 '-bis- (phenyl cyanic acid
Ester) structural formula of ethane (L10) is shown in formula 1, the structural formula of silazane is shown in formula 4 and formula 5.
The curing process of high temperature resistant silicon azane hydridization cyanate ester adhesive is in the present embodiment：It is first pre- solid under the conditions of 45 DEG C
Change 2 hours, be then warming up to 150 DEG C of 2 hours hardening times again, be cooled to room temperature, test its room temperature and 250 DEG C of adhesive properties,
Specifically it is shown in Table 7.
The adhesive property of the high temperature resistant silicon azane hydridization cyanate ester adhesive of table 7
| Room temperature adhesion strength (MPa) | 250 DEG C of adhesion strengths (MPa) | |
| Adhesion strength (MPa) | 18.5 | 10.5 |
By table 7, it can be seen that silazane hydridization cyanate ester adhesive manufactured in the present embodiment is be bonded with 250 DEG C in room temperature
It is functional.
Embodiment 8
The present embodiment is in 100 part 4,4 '-bis- middle additions of (phenylcyanate) ethane (L10), 80 parts of SiO2, 40 parts of ZrB2、10
Part SiC, 10 parts of TiC are as solid packing, 5 parts of SiO2As chopped strand, 3 parts of Fe2O3As solid pigment, fully mix, then
20 parts of silazane are added, after vacuum outgas 10 minutes, obtain high temperature resistant silicon azane hydridization cyanate ester adhesive, the present invention selects steel
For bonding substrates, wherein, the structural formula of 4,4 '-bis- (phenylcyanate) ethane (L10) is shown in formula 1, and the structural formula of silazane is shown in formula
4。
The curing process of high temperature resistant silicon azane hydridization cyanate ester adhesive is in the present embodiment：It is first small in 30 DEG C of precuring 5
When, 130 DEG C are then warming up to again, 4 hours hardening times, is cooled to room temperature, test its room temperature and 250 DEG C of adhesive properties, specifically
It is shown in Table 8.
The adhesive property of the high temperature resistant silicon azane hydridization cyanate ester adhesive of table 8
| Room temperature adhesion strength (MPa) | 250 DEG C of adhesion strengths (MPa) | |
| Adhesion strength (MPa) | 18.0 | 9.7 |
By table 8, it can be seen that silazane hydridization cyanate ester adhesive manufactured in the present embodiment is be bonded with 250 DEG C in room temperature
It is functional.
Embodiment 9
The present embodiment is in 100 part 4,4 '-bis- middle additions of (phenylcyanate) ethane (L10), 80 parts of SiO2, 40 parts of ZrB2、10
Part SiC, 10 parts of TiC are as solid packing, 5 parts of SiO2As chopped strand, 3 parts of Fe2O3As solid pigment, fully mix, then
20 parts of silazane are added, after vacuum outgas 10 minutes, obtain high temperature resistant silicon azane hydridization cyanate ester adhesive, the present invention selects steel
For bonding substrates, wherein, the structural formula of 4,4 '-bis- (phenylcyanate) ethane (L10) is shown in formula 1, and the structural formula of silazane is shown in formula
4。
The curing process of high temperature resistant silicon azane hydridization cyanate ester adhesive is in the present embodiment：It is first small in 55 DEG C of precuring 2
When, 170 DEG C are then warming up to again, 2 hours hardening times, is cooled to room temperature, test its room temperature and 250 DEG C of adhesive properties, specifically
It is shown in Table 9.
The adhesive property of the high temperature resistant silicon azane hydridization cyanate ester adhesive of table 9
| Room temperature adhesion strength (MPa) | 250 DEG C of adhesion strengths (MPa) | |
| Adhesion strength (MPa) | 19.1 | 11.3 |
By table 9, it can be seen that silazane hydridization cyanate ester adhesive manufactured in the present embodiment is be bonded with 250 DEG C in room temperature
It is functional.
Embodiment 10
The present embodiment adds Si in 100 part 4,4 '-bis- (phenylcyanate) ethane (L10)3N4150 parts, B430 parts of C,
SiO210 parts, Al2O35 parts are used as solid packing, 5 parts of SiO2As chopped strand, 3 parts of Fe2O3It is fully mixed as solid pigment
It is even, add 20 parts of silazane, after vacuum outgas 10 minutes, obtain high temperature resistant silicon azane hydridization cyanate ester adhesive, the present invention
It is bonding substrates from steel, wherein, the structural formula of 4,4 '-bis- (phenylcyanate) ethane (L10) is shown in formula 1, the structure of silazane
Formula is shown in formula 4.
The curing process of high temperature resistant silicon azane hydridization cyanate ester adhesive is in the present embodiment：It is first pre- solid under the conditions of 45 DEG C
Change 2 hours, be then warming up to 150 DEG C of 2 hours hardening times again, be cooled to room temperature, test its room temperature and 250 DEG C of adhesive properties,
Specifically it is shown in Table 10.
The adhesive property of the high temperature resistant silicon azane hydridization cyanate ester adhesive of table 10
| Room temperature adhesion strength (MPa) | 250 DEG C of adhesion strengths (MPa) | |
| Adhesion strength (MPa) | 18.5 | 10.4 |
By table 10, it can be seen that silazane hydridization cyanate ester adhesive manufactured in the present embodiment is glued at room temperature with 250 DEG C
Connect functional.
Embodiment 11
The present embodiment is in 100 part 4,4 '-bis- (phenylcyanate) ethane (L10) and the cyanic acid of 4,4 '-methylenediphenyl two
80 parts of SiO are added in the mixture of ester2, 40 parts of ZrB2, 10 parts of SiC, 10 parts of TiC are as solid packing, 5 parts of SiO2As chopped
Fiber, 3 parts of Fe2O3As solid pigment, fully mix, add 20 parts of silazane, after vacuum outgas 10 minutes, obtain resistance to height
Warm silazane hydridization cyanate ester adhesive, 4,4 '-bis- (phenylcyanate) ethane (L10) and 4,4 '-methylenediphenyl dicyan
The quality parts ratio of acid esters is 2:10, the present invention from steel is bonding substrates, wherein, 4,4 '-bis- (phenylcyanate) ethane
(L10) structural formula is shown in formula 1, and the structural formula of silazane is shown in formula 4.
The curing process of high temperature resistant silicon azane hydridization cyanate ester adhesive is in the present embodiment：It is first pre- solid under the conditions of 45 DEG C
Change 2 hours, be then warming up to 150 DEG C of 2 hours hardening times again, be cooled to room temperature, test its room temperature and 250 DEG C of adhesive properties,
Specifically it is shown in Table 11.
The adhesive property of the high temperature resistant silicon azane hydridization cyanate ester adhesive of table 11
| Room temperature adhesion strength (MPa) | 250 DEG C of adhesion strengths (MPa) | |
| Adhesion strength (MPa) | 18.9 | 10.8 |
By table 11, it can be seen that silazane hydridization cyanate ester adhesive manufactured in the present embodiment is glued at room temperature with 250 DEG C
Connect functional.
Embodiment 12
The present embodiment is in 100 part 4,4 '-bis- middle additions of (phenylcyanate) ethane (L10), 80 parts of SiO2, 40 parts of ZrB2、10
Part SiC, 10 parts of TiC are as solid packing, 5 parts of SiO2As chopped strand, 3 parts of Fe2O3As solid pigment, fully mix, then
20 parts of borosilicate azane are added, after vacuum outgas 10 minutes, obtain high temperature resistant silicon azane hydridization cyanate ester adhesive, the present invention selects
Steel is bonding substrates, wherein, the structural formula of 4,4 '-bis- (phenylcyanate) ethane (L10) is shown in formula 1, the structural formula of borosilicate azane
See formula 6.
The curing process of high temperature resistant silicon azane hydridization cyanate ester adhesive is in the present embodiment：It is first pre- solid under the conditions of 45 DEG C
Change 2 hours, be then warming up to 150 DEG C of 2 hours hardening times again, be cooled to room temperature, test its room temperature and 250 DEG C of adhesive properties,
Specifically it is shown in Table 12.
The adhesive property of the high temperature resistant silicon azane hydridization cyanate ester adhesive of table 12
| Room temperature adhesion strength (MPa) | 250 DEG C of adhesion strengths (MPa) | |
| Adhesion strength (MPa) | 19.8 | 12.2 |
By table 12, it can be seen that silazane hydridization cyanate ester adhesive manufactured in the present embodiment is glued at room temperature with 250 DEG C
Connect functional.
Embodiment 13
The present embodiment is in 100 part 4,4 '-bis- middle additions of (phenylcyanate) ethane (L10), 80 parts of SiO2, 40 parts of ZrB2、10
Part SiC, 10 parts of TiC are as solid packing, 5 parts of SiO2As chopped strand, 3 parts of Fe2O3As solid pigment, fully mix, then
20 parts of silica azane are added, after vacuum outgas 10 minutes, obtain high temperature resistant silicon azane hydridization cyanate ester adhesive, the present invention selects
Steel is bonding substrates, wherein, the structural formula of 4,4 '-bis- (phenylcyanate) ethane (L10) is shown in formula 1, the structural formula of silica azane
See formula 7.
The curing process of high temperature resistant silicon azane hydridization cyanate ester adhesive is in the present embodiment：It is first pre- solid under the conditions of 45 DEG C
Change 2 hours, be then warming up to 150 DEG C of 2 hours hardening times again, be cooled to room temperature, test its room temperature and 250 DEG C of adhesive properties,
Specifically it is shown in Table 13.
The adhesive property of the high temperature resistant silicon azane hydridization cyanate ester adhesive of table 13
| Room temperature adhesion strength (MPa) | 250 DEG C of adhesion strengths (MPa) | |
| Adhesion strength (MPa) | 18.5 | 10.1 |
By table 13, it can be seen that silazane hydridization cyanate ester adhesive manufactured in the present embodiment is glued at room temperature with 250 DEG C
Connect functional.
Embodiment 14
The present embodiment is in 100 part 4,4 '-bis- middle additions of (phenylcyanate) ethane (L10), 80 parts of SiO2, 40 parts of ZrB2、10
Part SiC, 10 parts of TiC are as solid packing, 5 parts of SiO2As chopped strand, 3 parts of Fe2O3As solid pigment, fully mix, then
20 parts of carbon silazane are added, after vacuum outgas 10 minutes, obtain high temperature resistant silicon azane hydridization cyanate ester adhesive, the present invention selects
Steel is bonding substrates, wherein, the structural formula of 4,4 '-bis- (phenylcyanate) ethane (L10) is shown in formula 1, the structural formula of carbon silazane
See formula 8.
The curing process of high temperature resistant silicon azane hydridization cyanate ester adhesive is in the present embodiment：It is first pre- solid under the conditions of 45 DEG C
Change 2 hours, be then warming up to 150 DEG C of 2 hours hardening times again, be cooled to room temperature, test its room temperature and 250 DEG C of adhesive properties,
Specifically it is shown in Table 14.
The adhesive property of the high temperature resistant silicon azane hydridization cyanate ester adhesive of table 14
| Room temperature adhesion strength (MPa) | 250 DEG C of adhesion strengths (MPa) | |
| Adhesion strength (MPa) | 18.8 | 11.2 |
By table 14, it can be seen that silazane hydridization cyanate ester adhesive manufactured in the present embodiment is glued at room temperature with 250 DEG C
Connect functional.
Embodiment 15
The present embodiment 100 parts to phenyl dicyanate in add 80 parts of SiO2, 40 parts of ZrB2, 10 parts of SiC, 10 parts of TiC make
For solid packing, 3 parts of SiO2As chopped strand, 3 parts of Fe2O3As solid pigment, fully mix, add silazane, silicon nitrogen
The addition mass fraction of alkane is 5 parts of (a), and 10 parts of (b), 15 parts of (c), 20 parts of (d), 25 parts of (e), 30 parts of (f), vacuum outgas 5 divides
Zhong Hou, obtain high temperature resistant silicon azane hydridization cyanate ester adhesive；Phenylcyanate is made into 75% solution,
The present invention selects steel as bonding substrates, wherein, formula 9, the knot of silazane are shown in the structural formula of phenyl dicyanate
Structure formula is shown in formula 2.
The curing process of high temperature resistant silicon azane hydridization cyanate ester adhesive is in the present embodiment：It is first pre- solid under the conditions of 45 DEG C
Change 2 hours, be then warming up to 150 DEG C of 2 hours hardening times again, be cooled to room temperature, test its room temperature and 250 DEG C of adhesive properties,
Specific test result is shown in Table 15.
The adhesive property of the high temperature resistant silicon azane hydridization cyanate ester adhesive of table 15
| Room temperature adhesion strength (MPa) | 250 DEG C of adhesion strengths (MPa) | |
| Adhesion strength (MPa) | 14.4 | 10.1 |
By table 15, it can be seen that silazane hydridization cyanate ester adhesive manufactured in the present embodiment is glued at room temperature with 250 DEG C
Connect functional.
Embodiment 16
The present embodiment adds 80 parts of SiO in 100 parts of Bisphenol F dicyanates2, 40 parts of ZrB2, 10 parts of SiC, 10 parts of TiC make
For solid packing, 3 parts of SiO2As chopped strand, 3 parts of Fe2O3As solid pigment, fully mix, add silazane, silicon nitrogen
The addition mass fraction of alkane is 5 parts of (a), and 10 parts of (b), 15 parts of (c), 20 parts of (d), 25 parts of (e), 30 parts of (f), vacuum outgas 5 divides
Zhong Hou, obtain high temperature resistant silicon azane hydridization cyanate ester adhesive；Bisphenol F dicyanate is made into 85% solution,
The present invention selects steel as bonding substrates, wherein, formula 10, the knot of silazane are shown in the structural formula of phenyl dicyanate
Structure formula is shown in formula 2.
The curing process of high temperature resistant silicon azane hydridization cyanate ester adhesive is in the present embodiment：It is first pre- solid under the conditions of 45 DEG C
Change 2 hours, be then warming up to 150 DEG C of 2 hours hardening times again, be cooled to room temperature, test its room temperature and 250 DEG C of adhesive properties,
Specific test result is shown in Table 16.
The adhesive property of the high temperature resistant silicon azane hydridization cyanate ester adhesive of table 16
| Room temperature adhesion strength (MPa) | 250 DEG C of adhesion strengths (MPa) | |
| Adhesion strength (MPa) | 15.2 | 12.7 |
By table 16, it can be seen that silazane hydridization cyanate ester adhesive manufactured in the present embodiment is glued at room temperature with 250 DEG C
Connect functional.
Embodiment 17
The present embodiment adds 80 parts of SiO in 100 parts of dicyanates2, 40 parts of ZrB2, 10 parts of SiC, 10 parts of TiC are as solid
Filler, 3 parts of SiO2As chopped strand, 3 parts of Fe2O3As solid pigment, fully mix, add silazane, silazane adds
It is 5 parts of (a) to enter mass fraction, 10 parts of (b), 15 parts of (c), 20 parts of (d), 25 parts of (e), 30 parts of (f), after vacuum outgas 5 minutes, is obtained
To high temperature resistant silicon azane hydridization cyanate ester adhesive；Dicyanate is made into 85% solution,
The present invention selects steel as bonding substrates, wherein, formula 11, the knot of silazane are shown in the structural formula of phenyl dicyanate
Structure formula is shown in formula 2.
The curing process of high temperature resistant silicon azane hydridization cyanate ester adhesive is in the present embodiment：It is first pre- solid under the conditions of 45 DEG C
Change 2 hours, be then warming up to 150 DEG C of 2 hours hardening times again, be cooled to room temperature, test its room temperature and 250 DEG C of adhesive properties,
Specific test result is shown in Table 17.
The adhesive property of the high temperature resistant silicon azane hydridization cyanate ester adhesive of table 17
| Room temperature adhesion strength (MPa) | 250 DEG C of adhesion strengths (MPa) | |
| Adhesion strength (MPa) | 13.1 | 10.5 |
By table 17, it can be seen that silazane hydridization cyanate ester adhesive manufactured in the present embodiment is glued at room temperature with 250 DEG C
Connect functional.
In summary, the invention provides a kind of high temperature resistant silicon azane hydridization cyanate ester adhesive and its preparation, solidification side
Method, the present invention improve the temperature tolerance of cyanate by the use of silazane hydridization cyanate as the matrix resin of high-temperature resistance adhesive
And inoxidizability, while match corresponding filler and prepare resistant to elevated temperatures adhesive；Meanwhile the adhesive energy prepared by the present invention
Enough meets the needs of fields such as Aeronautics and Astronautics are to high-temperature-resistant structure adhesive.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, the change or replacement that can readily occur in,
It should all be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of silazane hydridization cyanate ester adhesive, it is characterised in that mainly include the following steps that：
Step 1,0~200 part of solid packing, 0~20 part of solid pigment, 0~5 part of chopped strand are added in 100 parts of cyanates,
It is well mixed, obtain the first mixture；
Step 2,5~30 parts of silazane are added into the first mixture, be well mixed, obtain the second mixture；
Step 3, the second mixture is de-gassed, obtains silazane hydridization cyanate ester adhesive.
2. the preparation method of a kind of silazane hydridization cyanate ester adhesive according to claim 1, it is characterised in that described
In step 3, vacuum outgas 5~10 minutes is carried out to second mixture.
3. the preparation method of a kind of silazane hydridization cyanate ester adhesive according to claim 1, it is characterised in that described
Preparation method also includes step 4, and the step 4 is that the high tenacity cyanate ester adhesive that will be obtained carries out curing process with base material,
The curing process is then to rise the silazane hydridization cyanate ester adhesive again first in 30~70 DEG C of precuring 1~5 hour
Warm to 130~240 DEG C, 1~4 hour hardening time.
4. the preparation method of a kind of silazane hydridization cyanate ester adhesive according to claim 3, it is characterised in that described
Silazane hydridization cyanate ester adhesive first in 45~60 DEG C of precuring 1~5 hour, is then warming up to 150~200 DEG C, solidification again
1~4 hour time.
5. the preparation method of a kind of silazane hydridization cyanate ester adhesive according to claim 1, it is characterised in that described
The viscosity of second mixture is 0.1~200Pas.
6. the preparation method of a kind of silazane hydridization cyanate ester adhesive according to claim 1, it is characterised in that described
Cyanate is one or more of mixing in difunctionality or polyfunctional cyanate, cyanic acid ester oligomer, cyanate prepolymer
Thing.
7. the preparation method of a kind of silazane hydridization cyanate ester adhesive according to claim 1, it is characterised in that described
Silazane is one or more of mixtures of silazane oligomer or silicon nitrogen silane copolymer；The silazane oligomer or silicon nitrogen
Contain silazine link in the molecular structure of alkane polymer；The silazane is silazane, boron aluminium silazane, carbon silazane or silica
One or more of mixtures of silazane.
8. the preparation method of a kind of silazane hydridization cyanate ester adhesive according to claim 2, it is characterised in that described
The formula of silazane is
The formula of the boron aluminium silazane is
The formula of the silica silazane is
The formula of the carbon silazane is
R in formula17、R11、R11'、R13、R13'、R15And R15'For H, the alkyl of straight or branched, the alkenyl of straight or branched, straight chain or
The aryl of side chain, the aryl alkyl of straight or branched, straight or branched alkenyl aryl in one kind；
R17'For one in H, the alkyl of straight or branched, the alkenyl of straight or branched, the aryl of straight or branched, logical formula (V)
Kind, logical formula (V) is
R12And R12'For one kind in H, C1~C4 alkyl, phenyl；
R14And R14'For one kind in H, the alkyl of straight or branched, the alkenyl of straight or branched, logical formula (VI), logical formula (VI) is
R16For C1~C10 alkylidene；
M is B or Al；
M, k, p, q, o, s are integer；0≤m≤2000,0≤k≤2000, as m=0, k ≠ 0, as k=0, m ≠ 0；1≤s
≤50；1≤p≤100；0≤q≤2000,1≤o≤1000.
9. the preparation method of a kind of silazane hydridization cyanate ester adhesive according to claim 1, it is characterised in that described
Solid packing is III A, IV A main groups, B races, the oxide of lanthanide series metal, carbide, nitride, boride, in silicide extremely
Few one kind；The solid pigment is inorganic pigment.
A kind of 10. preparation method of silazane hydridization cyanate ester adhesive according to claim 1, it is characterised in that institute
Chopped strand is stated as carbon fiber, silicon carbide fibre, alumina fibre, quartz fibre, glass fibre, silicon nitride fiber, silicon nitride
Or boron nitride, the chopped strand length are 1~5 millimeter.
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| CN101724226A (en) * | 2009-11-20 | 2010-06-09 | 苏州大学 | Modified hot setting resin 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 |
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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 |
| CN101724226A (en) * | 2009-11-20 | 2010-06-09 | 苏州大学 | Modified hot setting resin and preparation method thereof |
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