CN107400235B - Cyanate hybridized polymer and cyanate composite material - Google Patents
Cyanate hybridized polymer and cyanate composite material Download PDFInfo
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- CN107400235B CN107400235B CN201710623579.0A CN201710623579A CN107400235B CN 107400235 B CN107400235 B CN 107400235B CN 201710623579 A CN201710623579 A CN 201710623579A CN 107400235 B CN107400235 B CN 107400235B
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- 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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- 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
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
Abstract
The present invention relates to a kind of cyanate hybridized polymer and cyanate composite materials, belong to cyanate technical field, while high glass-transition temperature, good dielectric properties and the good mechanical performance for keeping cyanate ester resin, improve the toughness and flame retardant property of cyanate ester resin.The raw material of cyanate hybridized polymer includes the diamines of raw material cyanate and siliceous oxygen chain link；The mass ratio of the diamines of raw material cyanate and siliceous oxygen chain link is greater than or equal to 10:7.Cyanate hybridized polymer provided by the invention can be used for cyanate composite material.
Description
Technical field
The present invention relates to a kind of cyanate more particularly to a kind of cyanate hybridized polymers and cyanate composite material.
Background technique
Cyanate ester resin is novel containing two or more cyanate functional groups (- OCN) in a kind of molecular structure
Thermosetting resin, with good resistance to thermooxidation and (250 DEG C -290 DEG C) anti-flammability, glass transition temperature high, moisture absorptions
Property dielectric constant (2.4-3.5) low advantage low, under the wide temperate zone of wideband, in works such as aerospace, machinery, electronics, automobiles
Industry is with a wide range of applications.But itself brittleness of cyanate is higher, to strongly limit application.
In the prior art, the method for carrying out toughening modifying to cyanate ester resin mainly includes rubber toughened method, thermosetting property tree
Rouge toughening method, Toughened With High Performance Thermoplastics method, unsaturates toughening method and organosilicon toughening method.
Wherein, cyanate ester resin is increased using rubber toughened method, Toughened With High Performance Thermoplastics method, unsaturates toughening method
Tough modification, while improving toughness, the high high-temp stability that will lead to cyanate ester resin are substantially reduced.For thermosetting resin
Toughening method, mainly using epoxy resin or phenolic resin as toughening material, but both resins are improving cyanate resin
While the toughness of rouge, the dielectric properties that will lead to cyanate ester resin itself are reduced.For organic-silicon-modified cyanate, mainly
Made using cage modle polysilsesquioxane (polyhedral oligomeric silsesquioxane, abbreviation POSS) and silazane
For toughener, although both toughener not will cause the reduction of the high high-temp stability of cyanate ester resin, for improving cyanogen
The toughness effect of acid esters is less obvious.
Summary of the invention
In view of above-mentioned analysis, the present invention is intended to provide a kind of cyanate hybridized polymer and cyanate composite material,
While high glass-transition temperature, good dielectric properties and the good mechanical performance for keeping cyanate ester resin, improve
The toughness and flame retardant property of cyanate ester resin.
The purpose of the present invention is mainly achieved through the following technical solutions:
In a first aspect, the present invention provides a kind of cyanate hybridized polymer, the raw material of cyanate hybridized polymer includes
The diamines of raw material cyanate and siliceous oxygen chain link；Raw material cyanate and the mass ratio of the diamines of siliceous oxygen chain link are greater than or equal to
10:7.
Further, cyanate hybridized polymer is cyanate hybrid prepolymer object or hydridization cyanate ester resin.
Further, cyanate raw material is the organic solvent solution of liquid cyanate or cyanate.
Further, the diamines of siliceous oxygen chain link is that the diamine monomer of siliceous oxygen chain link or the diamines of siliceous oxygen chain link have
Solvent solution.
Further, organic solvent be one of alkane solvents, aromatic solvent, ketones solvent, ether solvent or
A variety of arbitrary proportion mixing.
Further, raw material cyanate is at least one of aliphatic cyanate, the cyanate of general formula (I~III)；
Logical formula (I) is
Logical formula (II) is
Logical formula (III) is
R in formula1~R8For H, C1~C10 linear or branched alkyl group, C3~C8 naphthenic base, C1~C10 alkoxy, halogen, benzene
One of base or phenoxy group；
R9For one of H or C1-C10 alkyl, n is integer, 0≤n≤20；
Z is chemical bond, SO2、CF2、CH2、CHF、CH(CH3), isopropylidene, hexafluoroisopropyli,ene, C1-C10 alkylidene,
O, N=N, C=N, C=C, COO, C=N-N=C, the alkylene oxide group with C1-C8 alkylidene, S, Si (CH3)2
Or N-R9
Or
Or
One of or.
Further, halogen F, Cl, Br or I.
Further, raw material cyanate be phenylene -1,3- dicyanate, phenylene-Isosorbide-5-Nitrae-dicyanate, 2,4,5- tri-
Fluorine phenylene -1,3- dicyanate, 4,4 '-bis- (phenylcyanate) methane, dicyclopentadiene type ethylene rhodanate, 4,4 '-bis- (phenyl
Cyanate) isopropyl alkane, bis- (the 4- cyanic acid ester group-phenyl) hexafluoropropane of 2,2-, Cyclopeutadiene type cyanate, Novolac Cyanate Eater Resin,
At least one of 4,4 '-methylenediphenyl dicyanates or logical formula (IV)；
Logical formula (IV) is
N≡C-O-R10-O-C≡N
R in formula10For C3~C12 aliphatic alkyl.
Further, the general formula of the diamines of siliceous oxygen chain link is
M is integer, 0≤m≤100；
R11、R11′、R12And R12′For hydrogen, the substituted or unsubstituted alkyl of straight chain, branch substituted or unsubstituted alkane
Base, naphthenic base, the substituted or unsubstituted alkenyl of straight chain, branch substituted or unsubstituted alkenyl, cycloalkenyl, straight chain substitution
Or one of the substituted or unsubstituted alkynyl of unsubstituted alkynyl, branch, cycloalkynyl radical, substituted or unsubstituted aryl；
R13And R14For the substituted or unsubstituted alkyl of straight chain, the substituted or unsubstituted alkyl of branch, naphthenic base, straight
The substituted or unsubstituted alkenyl of chain, the substituted or unsubstituted alkenyl of branch, cycloalkenyl, straight chain substituted or unsubstituted alkynes
One of base, the substituted or unsubstituted alkynyl of branch, cycloalkynyl radical, substituted or unsubstituted aryl；
As 0 < m≤100, R15And R16For hydrogen, the substituted or unsubstituted alkyl of straight chain, branch it is substituted or unsubstituted
Alkyl, naphthenic base, the substituted or unsubstituted alkenyl of straight chain, the substituted or unsubstituted alkenyl of branch, cycloalkenyl, straight chain
Substituted or unsubstituted alkynyl, the substituted or unsubstituted alkynyl of branch, cycloalkynyl radical, one in substituted or unsubstituted aryl
Kind.
Second aspect, the present invention provides a kind of cyanate composite materials, including above-mentioned cyanate hybridized polymer.
Compared with prior art, the present invention has the beneficial effect that:
Cyanate composite material provided by the invention passes through the diamine reactant of raw material cyanate and siliceous oxygen chain link, by silicon oxygen
Chain link is introduced into the strand of cyanate, in the high glass-transition temperature for keeping cyanate ester resin, good dielectric properties
While with good mechanical performance, the toughness and flame retardant property of cyanate ester resin are improved, allows to be widely used in
The fields such as wave material, structural material, adhesive, coating.
Other features and advantages of the present invention will illustrate in the following description, also, partial become from specification
It obtains it is clear that understand through the implementation of the invention.The objectives and other advantages of the invention can be by written explanation
Specifically noted structure is achieved and obtained in book, claims.
Specific embodiment
The preferred embodiment of the present invention is detailed below.
In a first aspect, the present invention provides a kind of cyanate hybridized polymer, raw material includes raw material cyanate and siliceous
The mass ratio of the diamines of oxygen chain link, the two is greater than or equal to 10:7.
Compared with prior art, cyanate hybridized polymer provided by the invention passes through raw material cyanate and siliceous oxygen chain
Silicon oxygen chain link is introduced into the strand of cyanate by the diamine reactant of section, in the high glass transition for keeping cyanate ester resin
While temperature, good dielectric properties and good mechanical performance, the toughness and flame retardant property of cyanate ester resin are improved, is made
It can be widely applied to the fields such as electromagnetic wave transparent material, structural material, adhesive, coating.
Illustratively, the mass ratio of the diamines of raw material cyanate and siliceous oxygen chain link is 10:4~10:1, by the matter of the two
For amount than limiting within the above range, obtained cyanate hybridized polymer can have high tenacity and high glass transition temperature with general formula
Degree.
It should be noted that above-mentioned cyanate hybridized polymer can refer to hydridization cyanate ester resin, it can also also refer to system
The dissolvable and/or fusible intermediate product of standby hydridization cyanate ester resin process, i.e. cyanate hybrid prepolymer object.
In order to improve the performance of above-mentioned cyanate hybridized polymer some aspects, the raw material of cyanate hybridized polymer may be used also
To include filler (for example, titanium dioxide, iron powder and tinfoil paper etc.), the mass ratio of raw material cyanate and filler is 10:1~10:3.
The structure of the diamines to raw material cyanate and siliceous oxygen chain link is described in detail below.
Wherein, raw material cyanate can be difunctionality or polyfunctional cyanate ester monomer, the oligomer of cyanate, cyanate
One of polymer, modified cyanic acid ester or a variety of mixtures, for example, aliphatic cyanate, general formula (I~III)
At least one of cyanate.
Logical formula (I) is
R in formula1~R4For H, C1~C10 linear or branched alkyl group, C3~C8 naphthenic base, C1~C10 alkoxy, halogen (example
Such as, F, Cl, Br or I), one of phenyl or phenoxy group, wherein C1~C10 linear or branched alkyl group, C3~C8 naphthenic base,
C1~C10 alkoxy, phenyl and phenoxy group can be fully fluorinated or partially fluorinated.It should be noted that R1~R4It can be identical
Or it is different, it does not limit one by one herein.
Illustratively, the raw material cyanate for leading to formula (I) can be phenylene -1,3- dicyanate, phenylene-Isosorbide-5-Nitrae-dicyan
Acid esters, 2,4,5- trifluoro phenylene -1,3- dicyanate.
Logical formula (II) is
R in formula1~R8For H, C1~C10 linear or branched alkyl group, C3~C8 naphthenic base, C1~C10 alkoxy, halogen (example
Such as, F, Cl, Br or I), one of phenyl or phenoxy group, wherein C1~C10 linear or branched alkyl group, C3~C8 naphthenic base,
C1~C10 alkoxy, phenyl and phenoxy group can be fully fluorinated or partially fluorinated.It should be noted that R1~R8It can be identical
Or it is different, it does not limit one by one herein.
Z is chemical bond, SO2、CF2、CH2、CHF、CH(CH3), isopropylidene, hexafluoroisopropyli,ene, C1-C10 alkylidene,
O, N=N, C=N, C=C, COO, C=N-N=C, the alkylene oxide group with C1-C8 alkylidene, S, Si (CH3)2
Or N-R9
Or
Or
OrOne of.
Illustratively, the raw material cyanate for leading to formula (II) can be 4,4 '-bis- (phenylcyanate) methane, dicyclopentadiene
Type cyanate, 4,4 '-bis- (phenylcyanate) isopropyl alkanes (B10), 2,2- bis- (4- cyanic acid ester group-phenyl) hexafluoropropane, 4,4 '-
Bis- (phenylcyanate) ethane (L10) or Cyclopeutadiene type cyanate (P10).
Logical formula (III) is
R in formula9For one of H or C1-C10 alkyl, n is integer, 0≤n≤20.
Illustratively, the raw material cyanate for leading to formula (III) can be Novolac Cyanate Eater Resin (N10) or 4,4 '-methylene two
Phenyl dicyanate.
Aliphatic cyanate can be the cyanate of general formula (IV), and logical formula (IV) is
N≡C-O-R10-O-C≡N
R in formula10For aliphatic alkyl, wherein aliphatic alkyl can be fully fluorinated or partially fluorinated.Illustratively,
Aliphatic alkyl can be C3~C12 aliphatic alkyl.
For the diamines of siliceous oxygen chain link, general formula is
M is integer, 0≤m≤100, illustratively, 0≤m≤10；
R11、R12、R11′And R12′Can for hydrogen, the substituted or unsubstituted alkyl of straight chain, branch it is substituted or unsubstituted
Alkyl, naphthenic base, the substituted or unsubstituted alkenyl of straight chain, the substituted or unsubstituted alkenyl of branch, cycloalkenyl, straight chain take
One of generation or unsubstituted alkynyl, the substituted or unsubstituted alkynyl of branch, cycloalkynyl radical, substituted or unsubstituted aryl.
Illustratively, R11、R11′、R12And R12′It can be hydrogen, methyl, vinyl or phenyl.
R13And R14It can be the substituted or unsubstituted alkyl of straight chain, substituted or unsubstituted alkyl, the cycloalkanes of branch
Base, the substituted or unsubstituted alkenyl of straight chain, the substituted or unsubstituted alkenyl of branch, cycloalkenyl, the substitution of straight chain do not take
One of the alkynyl in generation, the substituted or unsubstituted alkynyl of branch, cycloalkynyl radical, substituted or unsubstituted aryl.
Illustratively, R13And R14It can be methyl, vinyl or phenyl.
As 0 < m≤100, R15And R16For hydrogen, the substituted or unsubstituted alkyl of straight chain, branch it is substituted or unsubstituted
Alkyl, naphthenic base, the substituted or unsubstituted alkenyl of straight chain, the substituted or unsubstituted alkenyl of branch, cycloalkenyl, straight chain
Substituted or unsubstituted alkynyl, the substituted or unsubstituted alkynyl of branch, cycloalkynyl radical, one in substituted or unsubstituted aryl
Kind.
It should be noted that R11、R11′、R12、R12′、R13、R14、R15And R16Can be same or different, herein not one by one
It limits.
Under normal conditions, using the glass transition of the cyanate hybridized polymer of siliceous oxygen chain link aliphatic diamine preparation
Temperature is lower than the glass transition temperature of the cyanate hybridized polymer prepared using the aromatic diamine of same content.
It should be noted that the diamines of above-mentioned siliceous oxygen chain link is the diamine monomer or siliceous oxygen chain link of siliceous oxygen chain link
The organic solvent solution of diamines；Similarly, cyanate raw material is the organic solvent solution of liquid cyanate or cyanate.
Wherein, organic solvent can for one of alkane solvents, aromatic solvent, ketones solvent, ether solvent or
A variety of arbitrary proportion mixing, illustratively, organic solvent can be in n-hexane, toluene, dimethylbenzene, acetone, ether or butyl ether
One or more arbitrary proportions mixing.
Second aspect, the present invention provides a kind of cyanate composite materials comprising above-mentioned cyanate hybridized polymer.
Compared with prior art, the beneficial effect of cyanate composite material provided by the invention and above-mentioned cyanate hydridization are poly-
The beneficial effect for closing object is identical, and details are not described herein.
The third aspect, the present invention provides a kind of preparation methods of cyanate hybridized polymer, include the following steps:
Step S1: the diamines of siliceous oxygen chain link is mixed with raw material cyanate (can be added drop-wise to raw material cyanate siliceous
In the diamines of oxygen chain link), it stirs evenly, is reacted, obtain cyanate hybrid prepolymer body；
Step S2: the temperature of the reaction system of ascending step S1 obtains so that cyanate performed polymer crosslinks curing reaction
To hydridization cyanate ester resin.
Compared with prior art, the beneficial effect of the preparation method of cyanate hybridized polymer provided by the invention with it is above-mentioned
The beneficial effect of cyanate hybridized polymer is identical, and details are not described herein.
Specifically, the preparation method of above-mentioned cyanate hybridized polymer, includes the following steps:
Step S11: the diamines of siliceous oxygen chain link being mixed with raw material cyanate, is stirred evenly, and is reacted at 0 DEG C~70 DEG C
5min~600min, obtains cyanate performed polymer, and raw material cyanate and the mass ratio of the diamines of siliceous oxygen chain link are greater than or equal to
The molar ratio of 10:7, cyanic acid ester group and amido is greater than or equal to 10:4；
Step S12: being increased to 100 DEG C~230 DEG C for the temperature of the reaction system of step S11, keep the temperature 0.5h~3h, so that
Cyanate performed polymer crosslinks curing reaction, obtains hydridization cyanate ester resin.
Wherein, the heating processing procedure of step S11 is the diamines of siliceous oxygen chain link and the mixture of raw material cyanate 0 DEG C~35
DEG C heat preservation 3min~360min, then heat to 40 DEG C~70 DEG C heat preservation 2min~240min.
The heating processing procedure of step S12 is that the temperature of the reaction system of step S11 is increased to 100 DEG C~130 DEG C heat preservations
10min~2h then heats to 200 DEG C~230 DEG C heat preservation 20min~1h.
Embodiment 1
By 4,4 '-bis- (phenylcyanate) ethane (L10) and 4,4 '-(two silicon oxygen of 1,1,3,3- tetravinyl -1,3-) two
The mass ratio of aniline mixing, the two is 10:3, is stirred evenly, and in 0 DEG C of reaction 2h, then heats to 40 DEG C, reacts 2h, obtain cyanogen
Acid esters hybrid prepolymer object；By cyanate hybrid prepolymer object in 130 DEG C of heat preservation 2h, 200 DEG C of heat preservation 1h are then heated to, then slowly drop
To room temperature, the translucent hydridization cyanate ester resin of yellowish-brown is obtained.
The structural formula of 4,4 '-bis- (phenylcyanate) ethane is
The structural formula of 4,4 '-(two silicon oxygen of 1,1,3,3- tetravinyl -1,3-) diphenylamines is
By test it is found that the glass transition temperature of the hydridization cyanate ester resin of embodiment 1 is 235 DEG C.
Embodiment 2
By 4,4 '-bis- (phenylcyanate) ethane (L10) and 4,4 '-(two silicon oxygen of 1,1,3,3- tetramethyl -1,3-) hexichol
The mass ratio of amine mixing, the two is 10:4, is stirred evenly, and in 0 DEG C of reaction 2h, then heats to 40 DEG C, reacts 2h, obtain cyanic acid
Ester hybrid prepolymer object；By cyanate hybrid prepolymer object in 130 DEG C of heat preservation 2h, 200 DEG C of heat preservation 1h are then heated to, then are slowly decreased to
Room temperature obtains the translucent hydridization cyanate ester resin of yellowish-brown.
The structural formula of 4,4 '-(two silicon oxygen of 1,1,3,3- tetramethyl -1,3-) diphenylamines is
By test it is found that the glass transition temperature of the hydridization cyanate ester resin of embodiment 2 is 180 DEG C, fracture toughness
For 2.13MPa.m1/2, bending strength 85MPa.
Embodiment 3
By 4,4 '-bis- (phenylcyanate) ethane (L10) and 4,4 '-(two silicon oxygen of 1,1,3,3- tetramethyl -1,3-) hexichol
The mass ratio of amine mixing, the two is 10:3.5, is stirred evenly, and in 0 DEG C of reaction 2h, then heats to 40 DEG C, reacts 2h, obtain cyanogen
Acid esters hybrid prepolymer object；By cyanate hybrid prepolymer object in 130 DEG C of heat preservation 2h, 200 DEG C of heat preservation 1h are then heated to, then slowly drop
To room temperature, the translucent hydridization cyanate ester resin of yellowish-brown is obtained.
By test it is found that the glass transition temperature of the hydridization cyanate ester resin of embodiment 3 is 192 DEG C, fracture toughness
For 1.98MPa.m1/2, bending strength 108MPa.
Embodiment 4
By 4,4 '-bis- (phenylcyanate) ethane (L10) and 4,4 '-(two silicon oxygen of 1,1,3,3- tetramethyl -1,3-) hexichol
The mass ratio of amine mixing, the two is 10:3, is stirred evenly, and in 0 DEG C of reaction 2h, then heats to 40 DEG C, reacts 2h, obtain cyanic acid
Ester hybrid prepolymer object；By cyanate hybrid prepolymer object in 130 DEG C of heat preservation 2h, 200 DEG C of heat preservation 1h are then heated to, then are slowly decreased to
Room temperature obtains the translucent hydridization cyanate ester resin of yellowish-brown.
By test it is found that the glass transition temperature of the hydridization cyanate ester resin of embodiment 4 is 231 DEG C, fracture toughness
For 1.72MPa.m1/2, bending strength 110MPa.
Embodiment 5
By 4,4 '-bis- (phenylcyanate) ethane (L10) and 4,4 '-(two silicon oxygen of 1,1,3,3- tetramethyl -1,3-) hexichol
The mass ratio of amine mixing, the two is 10:2.5, is stirred evenly, and in 0 DEG C of reaction 2h, then heats to 40 DEG C, reacts 2h, obtain cyanogen
Acid esters hybrid prepolymer object；By cyanate hybrid prepolymer object in 130 DEG C of heat preservation 2h, 200 DEG C of heat preservation 1h are then heated to, then slowly drop
To room temperature, the translucent hydridization cyanate ester resin of yellowish-brown is obtained.
By test it is found that the glass transition temperature of the hydridization cyanate ester resin of embodiment 5 is 244 DEG C, fracture toughness
For 1.56MPa.m1/2, bending strength 124MPa.
Embodiment 6
By 4,4 '-bis- (phenylcyanate) ethane (L10) and 4,4 '-(two silicon oxygen of 1,1,3,3- tetramethyl -1,3-) hexichol
The mass ratio of amine mixing, the two is 10:2, is stirred evenly, and in 0 DEG C of reaction 2h, then heats to 40 DEG C, reacts 2h, obtain cyanic acid
Ester hybrid prepolymer object；By cyanate hybrid prepolymer object in 130 DEG C of heat preservation 2h, 200 DEG C of heat preservation 1h are then heated to, then are slowly decreased to
Room temperature obtains the translucent hydridization cyanate ester resin of yellowish-brown.
By test it is found that the glass transition temperature of the hydridization cyanate ester resin of embodiment 6 is 248 DEG C, fracture toughness
For 1.47MPa.m1/2, bending strength 132MPa.
Embodiment 7
By 4,4 '-bis- (phenylcyanate) ethane (L10) and 4,4 '-(two silicon oxygen of 1,1,3,3- tetramethyl -1,3-) hexichol
The mass ratio of amine mixing, the two is 10:1, is stirred evenly, and in 0 DEG C of reaction 2h, then heats to 40 DEG C, reacts 2h, obtain cyanic acid
Ester hybrid prepolymer object；By cyanate hybrid prepolymer object in 130 DEG C of heat preservation 2h, 200 DEG C of heat preservation 1h are then heated to, then are slowly decreased to
Room temperature obtains the translucent hydridization cyanate ester resin of yellowish-brown.
By test it is found that the glass transition temperature of the hydridization cyanate ester resin of embodiment 7 is 252 DEG C, fracture toughness
For 1.34MPa.m1/2, bending strength 163MPa.
Comparative example 1
By 4,4 '-bis- (phenylcyanate) ethane (L10) in 0 DEG C of reaction 2h, 40 DEG C are then heated to, 2h is reacted, obtains
Cyanate prepolymer；By cyanate prepolymer in 130 DEG C of heat preservation 2h, 200 DEG C of heat preservation 1h are then heated to, then are slowly decreased to room
Temperature obtains cyanate ester resin.
By test it is found that the glass transition temperature of the cyanate ester resin of comparative example 1 is 250 DEG C, fracture toughness is
0.53MPa.m1/2, bending strength 165MPa.
1~embodiment of comparative example 7 and comparative example 1 are it is found that silicon oxygen chain link is introduced into can in cyanate strand
It is obviously improved the fracture toughness of hydridization cyanate ester resin, and its glass transition temperature is basically unchanged.
Embodiment 8
By (the mixing of 4,4 '-bis- (phenylcyanate) isopropyl alkanes and 4,4 '-bis- (phenylcyanate) ethane of raw material cyanate
Object, the mass ratio of the two are 1:10) it is mixed with 4,4 '-(1,1,3,3- tetramethyl -1,3-, bis- silicon oxygen) diphenylamines, the quality of the two
Than stirring evenly for 10:2, in 0 DEG C of reaction 2h, 40 DEG C are then heated to, 2h is reacted, obtains cyanate hybrid prepolymer object；By cyanogen
Acid esters hybrid prepolymer object then heats to 200 DEG C of heat preservation 1h in 130 DEG C of heat preservation 2h, then is slowly decreased to room temperature, obtains yellowish-brown half
Transparent hydridization cyanate ester resin.
The structural formula of 4,4 '-bis- (phenylcyanate) isopropyl alkanes is
By test it is found that the glass transition temperature of the hydridization cyanate ester resin of embodiment 8 is 252 DEG C, fracture toughness
For 1.45MPa.m1/2, bending strength 136MPa.
Embodiment 9
By (the mixing of 4,4 '-bis- (phenylcyanate) isopropyl alkanes and 4,4 '-bis- (phenylcyanate) ethane of raw material cyanate
Object, the mass ratio of the two are 1.5:10) it is mixed with 4,4 '-(1,1,3,3- tetramethyl -1,3-, bis- silicon oxygen) diphenylamines, the matter of the two
Amount stirs evenly than being 10:2, in 0 DEG C of reaction 2h, then heats to 40 DEG C, react 2h, obtain cyanate hybrid prepolymer object；It will
Cyanate hybrid prepolymer object then heats to 200 DEG C of heat preservation 1h in 130 DEG C of heat preservation 2h, then is slowly decreased to room temperature, obtains yellowish-brown
Translucent hydridization cyanate ester resin.
By test it is found that the glass transition temperature of the hydridization cyanate ester resin of embodiment 9 is 255 DEG C, fracture toughness
For 1.42MPa.m1/2, bending strength 138MPa.
Embodiment 10
By (the mixing of 4,4 '-bis- (phenylcyanate) isopropyl alkanes and 4,4 '-bis- (phenylcyanate) ethane of raw material cyanate
Object, the mass ratio of the two are 2:10) it is mixed with 4,4 '-(1,1,3,3- tetramethyl -1,3-, bis- silicon oxygen) diphenylamines, the quality of the two
Than stirring evenly for 10:2, in 0 DEG C of reaction 2h, 40 DEG C are then heated to, 2h is reacted, obtains cyanate hybrid prepolymer object；By cyanogen
Acid esters hybrid prepolymer object then heats to 200 DEG C of heat preservation 1h in 130 DEG C of heat preservation 2h, then is slowly decreased to room temperature, obtains yellowish-brown half
Transparent hydridization cyanate ester resin.
By test it is found that the glass transition temperature of the hydridization cyanate ester resin of embodiment 10 is 257 DEG C, fracture toughness
For 1.44MPa.m1/2, bending strength 133MPa.
Embodiment 11
By (the mixing of 4,4 '-bis- (phenylcyanate) isopropyl alkanes and 4,4 '-bis- (phenylcyanate) ethane of raw material cyanate
Object, the mass ratio of the two are 2.5:10) it is mixed with 4,4 '-(1,1,3,3- tetramethyl -1,3-, bis- silicon oxygen) diphenylamines, the matter of the two
Amount stirs evenly than being 10:2, in 0 DEG C of reaction 2h, then heats to 40 DEG C, react 2h, obtain cyanate hybrid prepolymer object；It will
Cyanate hybrid prepolymer object then heats to 200 DEG C of heat preservation 1h in 130 DEG C of heat preservation 2h, then is slowly decreased to room temperature, obtains yellowish-brown
Translucent hydridization cyanate ester resin.
By test it is found that the glass transition temperature of the hydridization cyanate ester resin of embodiment 11 is 258 DEG C, fracture toughness
For 1.38MPa.m1/2, bending strength 142MPa.
Embodiment 12
By (the mixing of 4,4 '-bis- (phenylcyanate) isopropyl alkanes and 4,4 '-bis- (phenylcyanate) ethane of raw material cyanate
Object, the mass ratio of the two are 3:10) it is mixed with 4,4 '-(1,1,3,3- tetramethyl -1,3-, bis- silicon oxygen) diphenylamines, the quality of the two
Than stirring evenly for 10:2, in 0 DEG C of reaction 2h, 40 DEG C are then heated to, 2h is reacted, obtains cyanate hybrid prepolymer object；By cyanogen
Acid esters hybrid prepolymer object then heats to 200 DEG C of heat preservation 1h in 130 DEG C of heat preservation 2h, then is slowly decreased to room temperature, obtains yellowish-brown half
Transparent hydridization cyanate ester resin.
By test it is found that the glass transition temperature of the hydridization cyanate ester resin of embodiment 12 is 263 DEG C, fracture toughness
For 1.35MPa.m1/2, bending strength 146MPa.
Embodiment 13
By (the mixing of 4,4 '-bis- (phenylcyanate) isopropyl alkanes and 4,4 '-bis- (phenylcyanate) ethane of raw material cyanate
Object, the mass ratio of the two are 4:10) it is mixed with 4,4 '-(1,1,3,3- tetramethyl -1,3-, bis- silicon oxygen) diphenylamines, the quality of the two
Than stirring evenly for 10:2, in 0 DEG C of reaction 2h, 40 DEG C are then heated to, 2h is reacted, obtains cyanate hybrid prepolymer object；By cyanogen
Acid esters hybrid prepolymer object then heats to 200 DEG C of heat preservation 1h in 130 DEG C of heat preservation 2h, then is slowly decreased to room temperature, obtains yellowish-brown half
Transparent hydridization cyanate ester resin.
By test it is found that the glass transition temperature of the hydridization cyanate ester resin of embodiment 113 is 265 DEG C, it is broken tough
Property is 1.37MPa.m1/2, bending strength 151MPa.
Embodiment 14
By (the mixing of 4,4 '-bis- (phenylcyanate) isopropyl alkanes and 4,4 '-bis- (phenylcyanate) ethane of raw material cyanate
Object, the mass ratio of the two are 5:10) it is mixed with 4,4 '-(1,1,3,3- tetramethyl -1,3-, bis- silicon oxygen) diphenylamines, the quality of the two
Than stirring evenly for 10:2, in 0 DEG C of reaction 2h, 40 DEG C are then heated to, 2h is reacted, obtains cyanate hybrid prepolymer object；By cyanogen
Acid esters hybrid prepolymer object then heats to 200 DEG C of heat preservation 1h in 130 DEG C of heat preservation 2h, then is slowly decreased to room temperature, obtains yellowish-brown half
Transparent hydridization cyanate ester resin.
By test it is found that the glass transition temperature of the hydridization cyanate ester resin of embodiment 14 is 268 DEG C, fracture toughness
For 1.38MPa.m1/2, bending strength 147MPa.
Embodiment 15
By 4,4 '-bis- (phenylcyanate) ethane (L10) and 4,4 '-(1,3- dimethyl -1,3- divinyl -1,3- two
Silicon oxygen) diphenylamines mixing, the mass ratio of the two is 10:3, is stirred evenly, and in 0 DEG C of reaction 2h, then heats to 40 DEG C, reaction
2h obtains cyanate hybrid prepolymer object；By cyanate hybrid prepolymer object in 130 DEG C of heat preservation 2h, 200 DEG C of heat preservations are then heated to
1h, then it is slowly decreased to room temperature, obtain the translucent hydridization cyanate ester resin of yellowish-brown.
The structural formula of 4,4 '-(two silicon oxygen of 1,3- dimethyl -1,3- divinyl -1,3-) diphenylamines is
By test it is found that the glass transition temperature of the hydridization cyanate ester resin of embodiment 15 is 230 DEG C.
Embodiment 16
By 4,4 '-bis- (phenylcyanate) ethane (L10) and 4,4 '-(two silicon of 1,3- dimethyl -1,3- diphenyl -1,3-
Oxygen) diphenylamines mixing, the mass ratio of the two is 10:3, is stirred evenly, in 0 DEG C of reaction 2h, 40 DEG C are then heated to, reacts 2h,
Obtain cyanate hybrid prepolymer object；By cyanate hybrid prepolymer object in 130 DEG C of heat preservation 2h, 200 DEG C of heat preservation 1h are then heated to, then
It is slowly decreased to room temperature, obtains the translucent hydridization cyanate ester resin of yellowish-brown.
The structural formula of 4,4 '-(two silicon oxygen of 1,3- dimethyl -1,3- diphenyl -1,3-) diphenylamines is
By test it is found that the glass transition temperature of the hydridization cyanate ester resin of embodiment 16 is 242 DEG C.
Embodiment 17
4,4 '-bis- (phenylcyanate) ethane (L10) and bis- (amine ethyl) tetramethyl disiloxanes of 1,3- are mixed, the two
Mass ratio be 10:3, stir evenly, in 0 DEG C of reaction 2h, then heat to 40 DEG C, reaction 2h obtains cyanate hybrid prepolymer
Object；By cyanate hybrid prepolymer object in 130 DEG C of heat preservation 2h, 200 DEG C of heat preservation 1h are then heated to, then are slowly decreased to room temperature, are obtained
The translucent hydridization cyanate ester resin of yellowish-brown.
Bis- (amine ethyl) tetramethyl disiloxanes of 1,3-
By test it is found that the glass transition temperature of the hydridization cyanate ester resin of embodiment 17 is 216 DEG C.
Embodiment 18
By 4,4 '-bis- (phenylcyanate) ethane (L10) and 4,4 '-(two silicon oxygen of 1,1,3,3- tetramethyl -1,3-) dipropyls
The mass ratio of amine mixing, the two is 10:3, is stirred evenly, and in 0 DEG C of reaction 2h, then heats to 40 DEG C, reacts 2h, obtain cyanic acid
Ester hybrid prepolymer object；By cyanate hybrid prepolymer object in 130 DEG C of heat preservation 2h, 200 DEG C of heat preservation 1h are then heated to, then are slowly decreased to
Room temperature obtains the translucent hydridization cyanate ester resin of yellowish-brown.
The structural formula of bis- (amine propyl) tetramethyl disiloxanes of 1,3- is
By test it is found that the glass transition temperature of the hydridization cyanate ester resin of embodiment 18 is 205 DEG C.
Embodiment 19
4,4 '-bis- (phenylcyanate) ethane (L10) and bis- (amine methyl) tetramethyl disiloxanes of 1,3- are mixed, the two
Mass ratio be 10:3, stir evenly, in 0 DEG C of reaction 2h, then heat to 40 DEG C, reaction 2h obtains cyanate hybrid prepolymer
Object；By cyanate hybrid prepolymer object in 130 DEG C of heat preservation 2h, 200 DEG C of heat preservation 1h are then heated to, then are slowly decreased to room temperature, are obtained
The translucent hydridization cyanate ester resin of yellowish-brown.
The structural formula of bis- (amine methyl) tetramethyl disiloxanes of 1,3- is
By test it is found that the glass transition temperature of the hydridization cyanate ester resin of embodiment 19 is 227 DEG C.
Embodiment 20
By 4,4 '-methylenediphenyl dicyanates and 4,4 '-(two silicon oxygen of 1,1,3,3- tetravinyl -1,3-) diphenylamines
The mass ratio of mixing, the two is 10:3, is stirred evenly, and in 0 DEG C of reaction 2h, then heats to 40 DEG C, reacts 2h, obtain cyanate
Hybrid prepolymer object；By cyanate hybrid prepolymer object in 130 DEG C of heat preservation 2h, 200 DEG C of heat preservation 1h are then heated to, then are slowly decreased to room
Temperature obtains the translucent hydridization cyanate ester resin of yellowish-brown.
The structural formula of 4,4 '-methylenediphenyl dicyanates is
By test it is found that the glass transition temperature of the hydridization cyanate ester resin of embodiment 20 is 245 DEG C.
Embodiment 21
By Novolac Cyanate Eater Resin and 4, the mixing of 4 '-(1,1,3,3- tetravinyl -1,3-, bis- silicon oxygen) diphenylamines, the matter of the two
Amount stirs evenly than being 10:3, in 0 DEG C of reaction 2h, then heats to 40 DEG C, react 2h, obtain cyanate hybrid prepolymer object；It will
Cyanate hybrid prepolymer object then heats to 200 DEG C of heat preservation 1h in 130 DEG C of heat preservation 2h, then is slowly decreased to room temperature, obtains yellowish-brown
Translucent hydridization cyanate ester resin.
The structural formula of Novolac Cyanate Eater Resin is
By test it is found that the glass transition temperature of the hydridization cyanate ester resin of embodiment 21 is 267 DEG C.
Embodiment 22
By dicyclopentadiene type ethylene rhodanate and 4,4 '-(1,1,3,3- tetravinyl -1,3-, bis- silicon oxygen) diphenylamines are mixed, and two
The mass ratio of person is 10:3, is stirred evenly, and in 0 DEG C of reaction 2h, then heats to 40 DEG C, reacts 2h, it is pre- to obtain cyanate hydridization
Polymers；By cyanate hybrid prepolymer object in 130 DEG C of heat preservation 2h, 200 DEG C of heat preservation 1h are then heated to, then are slowly decreased to room temperature, are obtained
To the translucent hydridization cyanate ester resin of yellowish-brown.
The structural formula of dicyclopentadiene type ethylene rhodanate is
By test it is found that the glass transition temperature of the hydridization cyanate ester resin of embodiment 22 is 267 DEG C.
Embodiment 23
By bis- (amine ethyl) tetramethyls of diamines 1,3- of 4,4 '-bis- (phenylcyanate) ethane (L10) and siliceous oxygen chain link
Disiloxane and 4, the mixture of 4 '-(1,1,3,3- tetramethyl -1,3-, bis- silicon oxygen) diphenylamines, the mass ratio of the two are 1:1) it is mixed
It closes, the mass ratio of the two is 10:3, is stirred evenly, and in 0 DEG C of reaction 2h, then heats to 40 DEG C, reacts 2h, it is miscellaneous to obtain cyanate
Change prepolymer；By cyanate hybrid prepolymer object in 130 DEG C of heat preservation 2h, 200 DEG C of heat preservation 1h are then heated to, then are slowly decreased to room
Temperature obtains the translucent hydridization cyanate ester resin of yellowish-brown.
By test it is found that the glass transition temperature of the hydridization cyanate ester resin of embodiment 23 is 226 DEG C.
Embodiment 24
By 4,4 '-bis- (phenylcyanate) ethane (L10) and 4,4 '-(1,1,3,3,5,5- vegolysen, tri- silicon of 3,5-
Oxygen) diphenylamines mixing, the mass ratio of the two is 10:3, is stirred evenly, in 0 DEG C of reaction 2h, 40 DEG C are then heated to, reacts 2h,
Obtain cyanate hybrid prepolymer object；By cyanate hybrid prepolymer object in 130 DEG C of heat preservation 2h, 200 DEG C of heat preservation 1h are then heated to, then
It is slowly decreased to room temperature, obtains the translucent hydridization cyanate ester resin of yellowish-brown.
The structural formula of 4,4 '-(1,1,3,3,5,5- vegolysen, tri- silicon oxygen of 3,5-) diphenylamines is
By test it is found that the glass transition temperature of the hydridization cyanate ester resin of embodiment 24 is 203 DEG C.
Embodiment 25
By 4,4 '-bis- (phenylcyanate) ethane (L10) and 4,4 '-(two silicon oxygen of 1,1,3,3- tetravinyl -1,3-) two
The mass ratio of aniline mixing, the two is 10:3, is stirred evenly, and in 0 DEG C of reaction 6h, then heats to 70 DEG C, reacts 4h, obtain cyanogen
Acid esters hybrid prepolymer object；By cyanate hybrid prepolymer object in 100 DEG C of heat preservation 10min, 230 DEG C of heat preservation 1h are then heated to, then are delayed
Slowly room temperature is dropped to, obtains the translucent hydridization cyanate ester resin of yellowish-brown.
By test it is found that the glass transition temperature of the hydridization cyanate ester resin of embodiment 25 is 236 DEG C.
Embodiment 26
By 4,4 '-bis- (phenylcyanate) ethane (L10) and 4,4 '-(two silicon oxygen of 1,1,3,3- tetravinyl -1,3-) two
The mass ratio of aniline mixing, the two is 10:7, is stirred evenly, and in 35 DEG C of reaction 3min, then heats to 70 DEG C, reacts 2min,
Obtain cyanate hybrid prepolymer object；By cyanate hybrid prepolymer object in 100 DEG C of heat preservation 2h, 230 DEG C of heat preservations are then heated to
20min, then it is slowly decreased to room temperature, obtain the translucent hydridization cyanate ester resin of yellowish-brown.
By test it is found that the glass transition temperature of the hydridization cyanate ester resin of embodiment 26 is 168 DEG C.
Embodiment 27
By 4,4 '-bis- (phenylcyanate) ethane (L10) and 4,4 '-(1,1,3,3,5,5- vegolysen, tri- silicon of 3,5-
Oxygen) diphenylamines mixing, the mass ratio of the two is 10:2, stirs evenly, is made into 30~50% toluene solution；By quartz fiber cloth
Dipping in the above solution, obtains prepreg cloth；By above-mentioned prepreg cloth in 60 DEG C of reaction 2h, 2h then is kept the temperature in 200 DEG C of compactings, is obtained
The hydridization cyanate ester resin composite material enhanced to quartz fibre.
By test it is found that the bending strength for the hydridization cyanate ester resin composite material that the quartz fibre of embodiment 27 enhances
For 430MPa, bending modulus 1.34GPa, dielectric constant 2.35, dielectric loss 0.0035.
Embodiment 28
By Novolac Cyanate Eater Resin and 4, the mixing of 4 '-(1,1,3,3,5,5- vegolysen, 3,5- tri- silicon oxygen) diphenylamines, the two
Mass ratio be 10:2, stir evenly, be made into 30~50% toluene solution；In the above solution by quartz fiber cloth dipping,
Obtain prepreg cloth；By above-mentioned prepreg cloth in 60 DEG C of reaction 2h, 2h then is kept the temperature in 200 DEG C of compactings, obtains quartz fibre enhancing
Hydridization cyanate ester resin composite material.
By test it is found that the bending strength for the hydridization cyanate ester resin composite material that the quartz fibre of embodiment 28 enhances
For 480MPa, bending modulus 1.56GPa, dielectric constant 2.41, dielectric loss 0.0038.
Embodiment 29
By 4,4 '-bis- (phenylcyanate) ethane (L10) and 4,4 '-(1,1,3,3,5,5- vegolysen, tri- silicon of 3,5-
Oxygen) diphenylamines mixing, the mass ratio of the two is 10:2, stirs evenly, is made into 30~50% toluene solution；Carbon cloth is soaked
Stain in the above solution, obtains prepreg cloth；By above-mentioned prepreg cloth in 60 DEG C of reaction 2h, 2h then is kept the temperature in 200 DEG C of compactings, is obtained
The hydridization cyanate ester resin composite material of fibre reinforced.
By test it is found that the bending strength of the hydridization cyanate ester resin composite material of the fibre reinforced of embodiment 29 is
620MPa, bending modulus 1.64GPa.
Embodiment 30
By Novolac Cyanate Eater Resin and 4, the mixing of 4 '-(1,1,3,3,5,5- vegolysen, 3,5- tri- silicon oxygen) diphenylamines, the two
Mass ratio be 10:2, stir evenly, be made into 30~50% toluene solution；In the above solution by carbon cloth dipping, it obtains
To prepreg cloth；By above-mentioned prepreg cloth in 60 DEG C of reaction 2h, 2h then is kept the temperature in 200 DEG C of compactings, obtains the hydridization of fibre reinforced
Cyanate ester resin composite material.
By test it is found that the bending strength of the hydridization cyanate ester resin composite material of the fibre reinforced of embodiment 30 is
730MPa, bending modulus 1.72GPa.
Embodiment 31
Phenyl dicyanate and 4,4 '-(1,1,3,3- tetravinyl -1,3-, bis- silicon oxygen) diphenylamines will be mixed, the two
Mass ratio is 10:4, is stirred evenly, and in 10 DEG C of reaction 2h, then heats to 40 DEG C, reacts 2h, obtain cyanate hybrid prepolymer
Object；By cyanate hybrid prepolymer object in 140 DEG C of heat preservation 2h, 220 DEG C of heat preservation 1h are then heated to, then are slowly decreased to room temperature, are obtained
The translucent hydridization cyanate ester resin of yellowish-brown.
To the structural formula of phenyl dicyanate
By test it is found that the glass transition temperature of the hydridization cyanate ester resin of embodiment 31 is 245 DEG C.
Embodiment 32
By 1,3- propane dicyanate and 4, the mixing of 4 '-(1,1,3,3- tetravinyl -1,3-, bis- silicon oxygen) diphenylamines, the two
Mass ratio be 10:4, stir evenly, in 10 DEG C of reaction 2h, then heat to 40 DEG C, reaction 2h obtains cyanate hybrid prepolymer
Object；By cyanate hybrid prepolymer object in 140 DEG C of heat preservation 2h, 220 DEG C of heat preservation 1h are then heated to, then are slowly decreased to room temperature, are obtained
The translucent hydridization cyanate ester resin of yellowish-brown.
The structural formula of 1,3- propane dicyanate is
By test it is found that the glass transition temperature of the hydridization cyanate ester resin of embodiment 32 is 186 DEG C.
It should be noted that test method involved in above-described embodiment is as follows: the test of fracture toughness according to
ASTME399 standard is tested；The test of glass transition temperature is according to the frequency with 1HZ with the heating rate of 2 DEG C/min
Method is tested；The test of bending strength is tested according to GB/T 9341-2000 standard；Dielectric properties use resonant cavity
Method is tested.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
In the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of by anyone skilled in the art,
It should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of cyanate hybridized polymer, which is characterized in that the raw material of the cyanate hybridized polymer includes raw material cyanic acid
The diamines of ester and siliceous oxygen chain link；
The mass ratio of the diamines of the raw material cyanate and the siliceous oxygen chain link is greater than or equal to 10:7.
2. cyanate hybridized polymer according to claim 1, which is characterized in that the cyanate hybridized polymer is cyanogen
Acid esters hybrid prepolymer object or hydridization cyanate ester resin.
3. cyanate hybridized polymer according to claim 1, which is characterized in that the cyanate raw material is liquid cyanic acid
The organic solvent solution of ester or cyanate.
4. cyanate hybridized polymer according to claim 1, which is characterized in that the diamines of the siliceous oxygen chain link be containing
The organic solvent solution of the diamines of the diamine monomer of silicon oxygen chain link or siliceous oxygen chain link.
5. cyanate hybridized polymer according to claim 3 or 4, which is characterized in that the organic solvent is alkanes
One of solvent, aromatic solvent, ketones solvent, ether solvent or the mixing of a variety of arbitrary proportions.
6. cyanate hybridized polymer according to claim 1, which is characterized in that the raw material cyanate is aliphatic cyanogen
At least one of acid esters, cyanate of general formula (I~III)；
Logical formula (I) is
Logical formula (II) is
Logical formula (III) is
R in formula1~R8For H, C1~C10 linear or branched alkyl group, C3~C8 naphthenic base, C1~C10 alkoxy, halogen, phenyl or
One of phenoxy group；
R9For one of H or C1-C10 alkyl, n is integer, 0≤n≤20；
Z is chemical bond, SO2、CF2、CH2、CHF、CH(CH3), isopropylidene, hexafluoroisopropyli,ene, C1-C10 alkylidene, O, N=
N, C=N, C=C, COO, C=N-N=C, the alkylene oxide group with C1-C8 alkylidene, S, Si (CH3)2
Or N-R9
Or
One of.
7. cyanate hybridized polymer according to claim 6, which is characterized in that the halogen is F, Cl, Br or I.
8. cyanate hybridized polymer according to claim 6, which is characterized in that the raw material cyanate is phenylene-
1,3- dicyanate, phenylene -1,4- dicyanate, 2,4,5- trifluoro phenylene -1,3- dicyanate, 4,4 '-bis- (phenylcyanides
Acid esters) methane, dicyclopentadiene type ethylene rhodanate, 4,4 '-bis- (phenylcyanate) isopropyl alkanes, bis- (the 4- cyanic acid ester groups-benzene of 2,2-
Base) hexafluoropropane, Cyclopeutadiene type cyanate, Novolac Cyanate Eater Resin, 4,4 '-methylenediphenyl dicyanates or logical formula (IV)
At least one of；
Logical formula (IV) is
R in formula10For C3~C12 aliphatic alkyl.
9. cyanate hybridized polymer according to claim 1, which is characterized in that the diamines of the siliceous oxygen chain link leads to
Formula is
M is integer, 0≤m≤100；
R11、R11′、R12And R12′For hydrogen, the substituted or unsubstituted alkyl of straight chain, branch substituted or unsubstituted alkyl, cycloalkanes
Base, the substituted or unsubstituted alkenyl of straight chain, the substituted or unsubstituted alkenyl of branch, cycloalkenyl, the substitution of straight chain do not take
One of the alkynyl in generation, the substituted or unsubstituted alkynyl of branch, cycloalkynyl radical, substituted or unsubstituted aryl；
R13And R14It is taken for the substituted or unsubstituted alkyl of straight chain, the substituted or unsubstituted alkyl of branch, naphthenic base, straight chain
Generation or unsubstituted alkenyl, the substituted or unsubstituted alkenyl of branch, cycloalkenyl, the substituted or unsubstituted alkynyl of straight chain, branch
One of the substituted or unsubstituted alkynyl of chain, cycloalkynyl radical, substituted or unsubstituted aryl；
As 0 < m≤100, R15And R16For hydrogen, the substituted or unsubstituted alkyl of straight chain, branch substituted or unsubstituted alkane
Base, naphthenic base, the substituted or unsubstituted alkenyl of straight chain, branch substituted or unsubstituted alkenyl, cycloalkenyl, straight chain substitution
Or one of the substituted or unsubstituted alkynyl of unsubstituted alkynyl, branch, cycloalkynyl radical, substituted or unsubstituted aryl.
10. a kind of cyanate composite material, which is characterized in that including cyanate hydridization as described in any one of claims 1 to 9
Polymer.
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