CN107400235A - Cyanate hybridized polymer and cyanate composite material - Google Patents
Cyanate hybridized polymer and cyanate composite material Download PDFInfo
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- CN107400235A CN107400235A CN201710623579.0A CN201710623579A CN107400235A CN 107400235 A CN107400235 A CN 107400235A CN 201710623579 A CN201710623579 A CN 201710623579A CN 107400235 A CN107400235 A CN 107400235A
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Abstract
The present invention relates to a kind of cyanate hybridized polymer and cyanate composite material, belong to cyanate technical field, while high glass-transition temperature, good dielectric properties and the good mechanical performance of cyanate ester resin is kept, improve the toughness and fire resistance of cyanate ester resin.The raw material of cyanate hybridized polymer includes the diamines of raw material cyanate and the chain link containing silica；The mass ratio of raw material cyanate and the diamines of the chain link containing silica is more 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 polymer and cyanate composite material.
Background technology
Cyanate ester resin is new containing two or more cyanate functional groups (- OCN) in a kind of molecular structure
Type thermosetting resin, it has good resistance to thermooxidation and anti-flammability, glass transition temperature is (250 DEG C -290 DEG C) high, inhales
Moist low, under the wide temperate zone of wideband dielectric constant (2.4-3.5) low advantage, in Aero-Space, machinery, electronics, automobile etc.
Industry is with a wide range of applications.But itself fragility of cyanate is higher, so as to strongly limit application.
In the prior art, the method for toughening modifying being carried out to cyanate ester resin mainly includes rubber toughened method, thermosetting tree
Fat toughness reinforcing method, Toughened With High Performance Thermoplastics method, unsaturates toughness reinforcing method and organosilicon toughness reinforcing method.
Wherein, cyanate ester resin is carried out using rubber toughened method, Toughened With High Performance Thermoplastics method, unsaturates toughness reinforcing method
Toughening modifying, while toughness is improved, the high high-temp stability of cyanate ester resin can be caused substantially reduce.For thermosetting
Resin toughening method, mainly using epoxy resin or phenolic resin as toughening material, but both resins are improving cyanic acid
While the toughness of ester resin, the dielectric properties of cyanate ester resin in itself can be caused to reduce.For organic-silicon-modified cyanate,
Mainly using cage modle polysilsesquioxane (polyhedral oligomeric silsesquioxane, abbreviation POSS) and
Silazane is as toughener, right although both toughener will not cause the reduction of the high high-temp stability of cyanate ester resin
It is less obvious in the toughness effect for improving cyanate.
The content 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 of cyanate ester resin is kept, improve
The toughness and fire resistance of cyanate ester resin.
The purpose of the present invention is mainly achieved through the following technical solutions：
In a first aspect, the invention provides a kind of cyanate hybridized polymer, the raw material of cyanate hybridized polymer includes
The diamines of raw material cyanate and the chain link containing silica；The mass ratio of raw material cyanate and the diamines of the chain link containing silica is more than or equal to
10：7.
Further, cyanate hybridized polymer is cyanate hybrid prepolymer thing or hydridization cyanate ester resin.
Further, cyanate raw material is the organic solvent solution of liquid cyanate or cyanate.
Further, the diamines of the chain link containing silica is the diamine monomer of the chain link containing silica or the diamines of the chain link containing silica
Organic solvent solution.
Further, organic solvent be alkane solvents, aromatic solvent, ketones solvent, one kind in ether solvent or
A variety of arbitrary proportion mixing.
Further, raw material cyanate is at least one of cyanate of aliphatic cyanate, formula (I~III)；
Logical formula (I) is
Logical formula (II) is
Logical formula (III) is
R in formula1~R8For H, C1~C10 straight or branched alkyls, C3~C8 cycloalkyl, C1~C10 alkoxies, halogen,
One kind in phenyl or phenoxy group；
R9For one kind in 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 alkylidenes,
O, N=N, C=N, C=C, COO, C=N-N=C, the alkylene oxide group with C1-C8 alkylidenes, S, Si (CH3)2
Or N-R9
One kind in or.
Further, halogen F, Cl, Br or I.
Further, raw material cyanate is phenylene -1,3- dicyanate, phenylene-Isosorbide-5-Nitrae-dicyanate, 2,4,5-
Trifluoro phenylene -1,3- dicyanates, 4,4 '-bis- (phenylcyanate) methane, dicyclopentadiene type ethylene rhodanate, 4,4 '-it is bis-
(phenylcyanate) isopropyl alkane, 2,2- double (4- cyanic acid ester group-phenyl) HFC-236fa, Cyclopeutadiene type cyanate, phenol aldehyde type cyanogen
At least one of acid esters, 4,4 '-methylenediphenyl dicyanate or logical formula (IV)；
Logical formula (IV) is
R in formula10For C3~C12 aliphatic alkyls.
Further, the formula of the diamines of the chain link containing silica is
M is integer, 0≤m≤100；
R11、R11′、R12And R12′For hydrogen, the substituted or unsubstituted alkyl of straight chain, side chain substituted or unsubstituted alkane
Base, cycloalkyl, the substituted or unsubstituted alkenyl of straight chain, the substituted or unsubstituted alkenyl of side chain, cycloalkenyl group, straight chain take
One kind in generation or unsubstituted alkynyl, the substituted or unsubstituted alkynyl of side chain, cycloalkynyl radical, substituted or unsubstituted aryl；
R13And R14For the substituted or unsubstituted alkyl of straight chain, the substituted or unsubstituted alkyl of side chain, cycloalkyl, straight
The substituted or unsubstituted alkenyl of chain, the substituted or unsubstituted alkenyl of side chain, cycloalkenyl group, straight chain it is substituted or unsubstituted
One kind in alkynyl, the substituted or unsubstituted alkynyl of side chain, cycloalkynyl radical, substituted or unsubstituted aryl；
As 0 ＜ m≤100, R15And R16For hydrogen, the substituted or unsubstituted alkyl of straight chain, side chain substitution or do not take
It is the alkyl in generation, cycloalkyl, the substituted or unsubstituted alkenyl of straight chain, the substituted or unsubstituted alkenyl of side chain, cycloalkenyl group, straight
In the substituted or unsubstituted alkynyl of chain, the substituted or unsubstituted alkynyl of side chain, cycloalkynyl radical, substituted or unsubstituted aryl
One kind.
Second aspect, the invention provides a kind of cyanate composite material, 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 is by raw material cyanate and the diamine reactant of the chain link containing silica, by silicon
Oxygen chain link is incorporated into the strand of cyanate, is keeping high glass-transition temperature, the good dielectricity of cyanate ester resin
While can be with good mechanical performance, the toughness and fire resistance of cyanate ester resin be improved, can be widely applied to it
The fields such as electromagnetic wave transparent material, structural material, adhesive, coating.
Other features and advantages of the present invention will illustrate in the following description, also, partial become from specification
Obtain it is clear that or being understood by implementing the present invention.The purpose of the present invention and other advantages can be by the explanations write
Specifically noted structure is realized and obtained in book, claims.
Embodiment
The preferred embodiments of the present invention are detailed below.
In a first aspect, the invention provides a kind of cyanate hybridized polymer, its raw material includes raw material cyanate and siliceous
The diamines of oxygen chain link, both mass ratioes are more than or equal to 10：7.
Compared with prior art, cyanate hybridized polymer provided by the invention, passes through raw material cyanate and chain containing silica
The diamine reactant of section, silica chain link is incorporated into the strand of cyanate, is keeping the high glass transition of cyanate ester resin
While temperature, good dielectric properties and good mechanical performance, the toughness and fire resistance of cyanate ester resin are improved,
It is set to can be widely applied to the fields such as electromagnetic wave transparent material, structural material, adhesive, coating.
Exemplarily, the mass ratio of the diamines of raw material cyanate and the chain link containing silica is 10：4~10：1, by both matter
For amount than limiting within the above range, obtained cyanate hybridized polymer can possess high tenacity and high glass transition with formula
Temperature.
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 thing.
In order to improve the performance of the above-mentioned some aspects of cyanate hybridized polymer, the raw material of cyanate hybridized polymer is also
Filler (for example, titanium dioxide, iron powder and tinfoil paper etc.) can be included, the mass ratio of raw material cyanate and filler is 10：1~10：
3。
The structure of raw material cyanate and the diamines of the chain link containing silica will be described in detail below.
Wherein, raw material cyanate can be difunctionality or polyfunctional cyanate ester monomer, the oligomer of cyanate, cyanic acid
One or more mixtures in ester polymer, modified cyanic acid ester, for example, aliphatic cyanate, formula (I~III)
At least one of cyanate.
Logical formula (I) is
R in formula1~R4For H, C1~C10 straight or branched alkyls, C3~C8 cycloalkyl, C1~C10 alkoxies, halogen
One kind in (for example, F, Cl, Br or I), phenyl or phenoxy group, wherein, C1~C10 straight or branched alkyls, C3~C8 cycloalkanes
Base, C1~C10 alkoxies, phenyl and phenoxy group can be with fully fluorinated or partially fluorinated.It should be noted that R1~R4Can be with
It is identical or different, do not limit one by one herein.
Exemplarily, the raw material cyanate for leading to formula (I) can be phenylene -1,3- dicyanate, phenylene-Isosorbide-5-Nitrae-two
Cyanate, 2,4,5- trifluoro phenylene -1,3- dicyanates.
Logical formula (II) is
R in formula1~R8For H, C1~C10 straight or branched alkyls, C3~C8 cycloalkyl, C1~C10 alkoxies, halogen
One kind in (for example, F, Cl, Br or I), phenyl or phenoxy group, wherein, C1~C10 straight or branched alkyls, C3~C8 cycloalkanes
Base, C1~C10 alkoxies, phenyl and phenoxy group can be with fully fluorinated or partially fluorinated.It should be noted that R1~R8Can be with
It is identical or different, do not limit one by one herein.
Z is chemical bond, SO2、CF2、CH2、CHF、CH(CH3), isopropylidene, hexafluoroisopropyli,ene, C1-C10 alkylidenes,
O, N=N, C=N, C=C, COO, C=N-N=C, the alkylene oxide group with C1-C8 alkylidenes, S, Si (CH3)2
In one kind.
Exemplarily, the raw material cyanate for leading to formula (II) can be 4,4 '-bis- (phenylcyanate) methane, bicyclic penta 2
Ene-type cyanate, 4,4 '-bis- (phenylcyanate) isopropyl alkanes (B10), 2,2- double (4- cyanic acid ester group-phenyl) HFC-236fa, 4,
4 '-bis- (phenylcyanate) ethane (L10) or Cyclopeutadiene type cyanate (P10).
Logical formula (III) is
R in formula9For one kind in H or C1-C10 alkyl, n is integer, 0≤n≤20.
Exemplarily, 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 formula (IV), and logical formula (IV) is
R in formula10For aliphatic alkyl, wherein, aliphatic alkyl can be with fully fluorinated or partially fluorinated.Exemplarily,
Aliphatic alkyl can be C3~C12 aliphatic alkyls.
For the diamines of the chain link containing silica, its formula is
M is integer, 0≤m≤100, exemplarily, 0≤m≤10；
R11、R12、R11′And R12′It can be the substitution or unsubstituted of hydrogen, the substituted or unsubstituted alkyl of straight chain, side chain
Alkyl, cycloalkyl, the substituted or unsubstituted alkenyl of straight chain, substituted or unsubstituted alkenyl, cycloalkenyl group, the straight chain of side chain
Substituted or unsubstituted alkynyl, the substituted or unsubstituted alkynyl of side chain, cycloalkynyl radical, in substituted or unsubstituted aryl
It is a kind of.
Exemplarily, R11、R11′、R12And R12′Can be hydrogen, methyl, vinyl or phenyl.
R13And R14Can be substituted or unsubstituted alkyl, substituted or unsubstituted alkyl, the cycloalkanes of side chain of straight chain
Base, the substituted or unsubstituted alkenyl of straight chain, the substituted or unsubstituted alkenyl of side chain, cycloalkenyl group, straight chain substitution or do not take
One kind in the alkynyl in generation, the substituted or unsubstituted alkynyl of side chain, cycloalkynyl radical, substituted or unsubstituted aryl.
Exemplarily, R13And R14Can be methyl, vinyl or phenyl.
As 0 ＜ m≤100, R15And R16For hydrogen, the substituted or unsubstituted alkyl of straight chain, side chain substitution or do not take
It is the alkyl in generation, cycloalkyl, the substituted or unsubstituted alkenyl of straight chain, the substituted or unsubstituted alkenyl of side chain, cycloalkenyl group, straight
In the substituted or unsubstituted alkynyl of chain, the substituted or unsubstituted alkynyl of side chain, cycloalkynyl radical, substituted or unsubstituted aryl
One kind.
It should be noted that R11、R11′、R12、R12′、R13、R14、R15And R16Can be with identical or different, herein not one by one
Limit.
Under normal circumstances, the vitrifying of the cyanate hybridized polymer prepared using the aliphatic diamine of chain link containing silica is turned
Temperature is less than the glass transition temperature of the cyanate hybridized polymer prepared using the aromatic diamine of same content.
It should be noted that diamine monomer of the diamines of the above-mentioned chain link containing silica for the chain link containing silica or chain link containing silica
Diamines organic solvent solution；Similarly, cyanate raw material is the organic solvent solution of liquid cyanate or cyanate.
Wherein, organic solvent can be alkane solvents, aromatic solvent, ketones solvent, one kind in ether solvent or
A variety of arbitrary proportion mixing, exemplarily, organic solvent can be in n-hexane, toluene, dimethylbenzene, acetone, ether or butyl ether
One or more arbitrary proportions mixing.
Second aspect, the invention provides a kind of cyanate composite material, and it includes 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
The beneficial effect of polymer is identical, will not be repeated here.
The third aspect, the invention provides a kind of preparation method of cyanate hybridized polymer, comprise the following steps：
Step S1：The diamines of the chain link containing silica is mixed with raw material cyanate (can be added drop-wise to raw material cyanate siliceous
In the diamines of oxygen chain link), stir, reacted, obtain cyanate hybrid prepolymer body；
Step S2：The temperature of ascending step S1 reaction system so that cyanate performed polymer crosslinks curing reaction,
Obtain 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 upper
It is identical to state the beneficial effect of cyanate hybridized polymer, will not be repeated here.
Specifically, the preparation method of above-mentioned cyanate hybridized polymer, comprises the following steps：
Step S11：The diamines of the chain link containing silica is mixed with raw material cyanate, stirred, it is anti-at 0 DEG C~70 DEG C
5min~600min is answered, obtains cyanate performed polymer, the mass ratio of raw material cyanate and the diamines of the chain link containing silica is more than or waited
In 10：7, the mol ratio of cyanic acid ester group and amido is more than or equal to 10：4；
Step S12：The temperature of step S11 reaction system is increased to 100 DEG C~230 DEG C, 0.5h~3h is incubated, makes
Obtain cyanate performed polymer and crosslink curing reaction, obtain hydridization cyanate ester resin.
Wherein, step S11 heating processing procedure for diamines and the raw material cyanate of the chain link containing silica mixture 0 DEG C~
35 DEG C of insulation 3min~360min, then heat to 40 DEG C~70 DEG C insulation 2min~240min.
Step S12 heating processing procedure is that the temperature of step S11 reaction system is increased into 100 DEG C~130 DEG C insulations
10min~2h, then heat to 200 DEG C~230 DEG C insulation 20min~1h.
Embodiment 1
By 4,4 '-bis- (phenylcyanate) ethane (L10) and 4,4 '-(silica of 1,1,3,3- tetravinyls -1,3- two) two
Aniline mixes, and both mass ratioes are 10：3, stir, react 2h at 0 DEG C, then heat to 40 DEG C, react 2h, obtain
Cyanate hybrid prepolymer thing；Cyanate hybrid prepolymer thing is incubated 2h at 130 DEG C, then heats to 200 DEG C of insulation 1h, then delay
Slowly room temperature is dropped to, obtains the translucent hydridization cyanate ester resin of yellowish-brown.
The structural formula of 4,4 '-bis- (phenylcyanate) ethane is
The structural formula of 4,4 '-(silica of 1,1,3,3- tetravinyls -1,3- two) diphenylamines is
By test, 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 '-(silica of 1,1,3,3- tetramethyls -1,3- two) hexichol
Amine mixes, and both mass ratioes are 10：4, stir, react 2h at 0 DEG C, then heat to 40 DEG C, react 2h, obtain cyanogen
Acid esters hybrid prepolymer thing；Cyanate hybrid prepolymer thing is incubated 2h at 130 DEG C, then heats to 200 DEG C of insulation 1h, then slowly
Room temperature is dropped to, obtains the translucent hydridization cyanate ester resin of yellowish-brown.
The structural formula of 4,4 '-(silica of 1,1,3,3- tetramethyls -1,3- two) diphenylamines is
By test, 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 '-(silica of 1,1,3,3- tetramethyls -1,3- two) hexichol
Amine mixes, and both mass ratioes are 10：3.5, stir, react 2h at 0 DEG C, then heat to 40 DEG C, react 2h, obtain
Cyanate hybrid prepolymer thing；Cyanate hybrid prepolymer thing is incubated 2h at 130 DEG C, then heats to 200 DEG C of insulation 1h, then delay
Slowly room temperature is dropped to, obtains the translucent hydridization cyanate ester resin of yellowish-brown.
By test, 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 '-(silica of 1,1,3,3- tetramethyls -1,3- two) hexichol
Amine mixes, and both mass ratioes are 10：3, stir, react 2h at 0 DEG C, then heat to 40 DEG C, react 2h, obtain cyanogen
Acid esters hybrid prepolymer thing；Cyanate hybrid prepolymer thing is incubated 2h at 130 DEG C, then heats to 200 DEG C of insulation 1h, then slowly
Room temperature is dropped to, obtains the translucent hydridization cyanate ester resin of yellowish-brown.
By test, 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 '-(silica of 1,1,3,3- tetramethyls -1,3- two) hexichol
Amine mixes, and both mass ratioes are 10：2.5, stir, react 2h at 0 DEG C, then heat to 40 DEG C, react 2h, obtain
Cyanate hybrid prepolymer thing；Cyanate hybrid prepolymer thing is incubated 2h at 130 DEG C, then heats to 200 DEG C of insulation 1h, then delay
Slowly room temperature is dropped to, obtains the translucent hydridization cyanate ester resin of yellowish-brown.
By test, 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 '-(silica of 1,1,3,3- tetramethyls -1,3- two) hexichol
Amine mixes, and both mass ratioes are 10：2, stir, react 2h at 0 DEG C, then heat to 40 DEG C, react 2h, obtain cyanogen
Acid esters hybrid prepolymer thing；Cyanate hybrid prepolymer thing is incubated 2h at 130 DEG C, then heats to 200 DEG C of insulation 1h, then slowly
Room temperature is dropped to, obtains the translucent hydridization cyanate ester resin of yellowish-brown.
By test, 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 '-(silica of 1,1,3,3- tetramethyls -1,3- two) hexichol
Amine mixes, and both mass ratioes are 10：1, stir, react 2h at 0 DEG C, then heat to 40 DEG C, react 2h, obtain cyanogen
Acid esters hybrid prepolymer thing；Cyanate hybrid prepolymer thing is incubated 2h at 130 DEG C, then heats to 200 DEG C of insulation 1h, then slowly
Room temperature is dropped to, obtains the translucent hydridization cyanate ester resin of yellowish-brown.
By test, 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) react 2h at 0 DEG C, 40 DEG C are then heated to, 2h is reacted, obtains
Cyanate prepolymer；Cyanate prepolymer is incubated 2h at 130 DEG C, then heats to 200 DEG C of insulation 1h, then be slowly decreased to room
Temperature, obtain cyanate ester resin.
By test, the glass transition temperature of the cyanate ester resin of comparative example 1 is 250 DEG C, and fracture toughness is
0.53MPa.m1/2, bending strength 165MPa.
1~embodiment of comparative example 7 and comparative example 1 understand that being incorporated into silica chain link can in cyanate strand
The fracture toughness of hydridization cyanate ester resin is obviously improved, and its glass transition temperature is basically unchanged.
Embodiment 8
By raw material cyanate (4,4 '-bis- (phenylcyanate) isopropyl alkanes and 4,4 '-bis- (phenylcyanate) ethane it is mixed
Compound, both mass ratioes are 1：10) mixed with 4,4 '-(silica of 1,1,3,3- tetramethyl -1,3- bis-) diphenylamines, both
Mass ratio is 10：2, stir, react 2h at 0 DEG C, then heat to 40 DEG C, react 2h, obtain cyanate hybrid prepolymer
Thing；Cyanate hybrid prepolymer thing is incubated 2h at 130 DEG C, then heats to 200 DEG C of insulation 1h, then is slowly decreased to room temperature, is obtained
The translucent hydridization cyanate ester resin of yellowish-brown.
The structural formula of 4,4 '-bis- (phenylcyanate) isopropyl alkanes is
By test, 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 raw material cyanate (4,4 '-bis- (phenylcyanate) isopropyl alkanes and 4,4 '-bis- (phenylcyanate) ethane it is mixed
Compound, both mass ratioes are 1.5：10) mixed with 4,4 '-(silica of 1,1,3,3- tetramethyl -1,3- bis-) diphenylamines, both
Mass ratio be 10：2, stir, react 2h at 0 DEG C, then heat to 40 DEG C, react 2h, obtain cyanate hybrid prepolymer
Thing；Cyanate hybrid prepolymer thing is incubated 2h at 130 DEG C, then heats to 200 DEG C of insulation 1h, then is slowly decreased to room temperature, is obtained
The translucent hydridization cyanate ester resin of yellowish-brown.
By test, 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 raw material cyanate (4,4 '-bis- (phenylcyanate) isopropyl alkanes and 4,4 '-bis- (phenylcyanate) ethane it is mixed
Compound, both mass ratioes are 2：10) mixed with 4,4 '-(silica of 1,1,3,3- tetramethyl -1,3- bis-) diphenylamines, both
Mass ratio is 10：2, stir, react 2h at 0 DEG C, then heat to 40 DEG C, react 2h, obtain cyanate hybrid prepolymer
Thing；Cyanate hybrid prepolymer thing is incubated 2h at 130 DEG C, then heats to 200 DEG C of insulation 1h, then is slowly decreased to room temperature, is obtained
The translucent hydridization cyanate ester resin of yellowish-brown.
By test, the glass transition temperature of the hydridization cyanate ester resin of embodiment 10 is 257 DEG C, and fracture is tough
Property is 1.44MPa.m1/2, bending strength 133MPa.
Embodiment 11
By raw material cyanate (4,4 '-bis- (phenylcyanate) isopropyl alkanes and 4,4 '-bis- (phenylcyanate) ethane it is mixed
Compound, both mass ratioes are 2.5：10) mixed with 4,4 '-(silica of 1,1,3,3- tetramethyl -1,3- bis-) diphenylamines, both
Mass ratio be 10：2, stir, react 2h at 0 DEG C, then heat to 40 DEG C, react 2h, obtain cyanate hybrid prepolymer
Thing；Cyanate hybrid prepolymer thing is incubated 2h at 130 DEG C, then heats to 200 DEG C of insulation 1h, then is slowly decreased to room temperature, is obtained
The translucent hydridization cyanate ester resin of yellowish-brown.
By test, the glass transition temperature of the hydridization cyanate ester resin of embodiment 11 is 258 DEG C, and fracture is tough
Property is 1.38MPa.m1/2, bending strength 142MPa.
Embodiment 12
By raw material cyanate (4,4 '-bis- (phenylcyanate) isopropyl alkanes and 4,4 '-bis- (phenylcyanate) ethane it is mixed
Compound, both mass ratioes are 3：10) mixed with 4,4 '-(silica of 1,1,3,3- tetramethyl -1,3- bis-) diphenylamines, both
Mass ratio is 10：2, stir, react 2h at 0 DEG C, then heat to 40 DEG C, react 2h, obtain cyanate hybrid prepolymer
Thing；Cyanate hybrid prepolymer thing is incubated 2h at 130 DEG C, then heats to 200 DEG C of insulation 1h, then is slowly decreased to room temperature, is obtained
The translucent hydridization cyanate ester resin of yellowish-brown.
By test, the glass transition temperature of the hydridization cyanate ester resin of embodiment 12 is 263 DEG C, and fracture is tough
Property is 1.35MPa.m1/2, bending strength 146MPa.
Embodiment 13
By raw material cyanate (4,4 '-bis- (phenylcyanate) isopropyl alkanes and 4,4 '-bis- (phenylcyanate) ethane it is mixed
Compound, both mass ratioes are 4：10) mixed with 4,4 '-(silica of 1,1,3,3- tetramethyl -1,3- bis-) diphenylamines, both
Mass ratio is 10：2, stir, react 2h at 0 DEG C, then heat to 40 DEG C, react 2h, obtain cyanate hybrid prepolymer
Thing；Cyanate hybrid prepolymer thing is incubated 2h at 130 DEG C, then heats to 200 DEG C of insulation 1h, then is slowly decreased to room temperature, is obtained
The translucent hydridization cyanate ester resin of yellowish-brown.
By test, the glass transition temperature of the hydridization cyanate ester resin of embodiment 113 is 265 DEG C, and fracture is tough
Property is 1.37MPa.m1/2, bending strength 151MPa.
Embodiment 14
By raw material cyanate (4,4 '-bis- (phenylcyanate) isopropyl alkanes and 4,4 '-bis- (phenylcyanate) ethane it is mixed
Compound, both mass ratioes are 5：10) mixed with 4,4 '-(silica of 1,1,3,3- tetramethyl -1,3- bis-) diphenylamines, both
Mass ratio is 10：2, stir, react 2h at 0 DEG C, then heat to 40 DEG C, react 2h, obtain cyanate hybrid prepolymer
Thing；Cyanate hybrid prepolymer thing is incubated 2h at 130 DEG C, then heats to 200 DEG C of insulation 1h, then is slowly decreased to room temperature, is obtained
The translucent hydridization cyanate ester resin of yellowish-brown.
By test, the glass transition temperature of the hydridization cyanate ester resin of embodiment 14 is 268 DEG C, and fracture is tough
Property is 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
Silica) diphenylamines mixing, both mass ratioes are 10：3, stir, react 2h at 0 DEG C, then heat to 40 DEG C, reaction
2h, obtain cyanate hybrid prepolymer thing；Cyanate hybrid prepolymer thing is incubated 2h at 130 DEG C, then heats to 200 DEG C of insulations
1h, then room temperature is slowly decreased to, obtain the translucent hydridization cyanate ester resin of yellowish-brown.
The structural formula of 4,4 '-(silica of 1,3- dimethyl -1,3- divinyl -1,3- two) diphenylamines is
By test, 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 the 4,4 '-(silicon of 1,3- dimethyl -1,3- diphenyl -1,3- two
Oxygen) diphenylamines mixing, both mass ratioes are 10：3, stir, react 2h at 0 DEG C, then heat to 40 DEG C, react 2h,
Obtain cyanate hybrid prepolymer thing；Cyanate hybrid prepolymer thing is incubated 2h at 130 DEG C, then heats to 200 DEG C of insulation 1h,
Room temperature is slowly decreased to again, obtains the translucent hydridization cyanate ester resin of yellowish-brown.
The structural formula of 4,4 '-(silica of 1,3- dimethyl -1,3- diphenyl -1,3- two) diphenylamines is
By test, 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 1,3- pairs of (amine ethyl) tetramethyl disiloxanes are mixed, two
The mass ratio of person is 10：3, stir, react 2h at 0 DEG C, then heat to 40 DEG C, react 2h, it is pre- to obtain cyanate hydridization
Polymers；Cyanate hybrid prepolymer thing is incubated 2h at 130 DEG C, then heats to 200 DEG C of insulation 1h, then is slowly decreased to room temperature, is obtained
To the translucent hydridization cyanate ester resin of yellowish-brown.
Double (amine ethyl) tetramethyl disiloxanes of 1,3-
By test, 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 '-(silica of 1,1,3,3- tetramethyls -1,3- two) dipropyls
Amine mixes, and both mass ratioes are 10：3, stir, react 2h at 0 DEG C, then heat to 40 DEG C, react 2h, obtain cyanogen
Acid esters hybrid prepolymer thing；Cyanate hybrid prepolymer thing is incubated 2h at 130 DEG C, then heats to 200 DEG C of insulation 1h, then slowly
Room temperature is dropped to, obtains the translucent hydridization cyanate ester resin of yellowish-brown.
The structural formula of double (amine propyl group) tetramethyl disiloxanes of 1,3- is
By test, 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 1,3- pairs of (amine methyl) tetramethyl disiloxanes are mixed, two
The mass ratio of person is 10：3, stir, react 2h at 0 DEG C, then heat to 40 DEG C, react 2h, it is pre- to obtain cyanate hydridization
Polymers；Cyanate hybrid prepolymer thing is incubated 2h at 130 DEG C, then heats to 200 DEG C of insulation 1h, then is slowly decreased to room temperature, is obtained
To the translucent hydridization cyanate ester resin of yellowish-brown.
The structural formula of double (amine methyl) tetramethyl disiloxanes of 1,3- is
By test, the glass transition temperature of the hydridization cyanate ester resin of embodiment 19 is 227 DEG C.
Embodiment 20
By 4,4 '-methylenediphenyl dicyanate and 4,4 '-(silica of 1,1,3,3- tetravinyls -1,3- two) hexichol
Amine mixes, and both mass ratioes are 10：3, stir, react 2h at 0 DEG C, then heat to 40 DEG C, react 2h, obtain cyanogen
Acid esters hybrid prepolymer thing；Cyanate hybrid prepolymer thing is incubated 2h at 130 DEG C, then heats to 200 DEG C of insulation 1h, then slowly
Room temperature is dropped to, obtains the translucent hydridization cyanate ester resin of yellowish-brown.
The structural formula of 4,4 '-methylenediphenyl dicyanate is
By test, 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 4,4 '-(silica of 1,1,3,3- tetravinyl -1,3- bis-) diphenylamines mix, both
Mass ratio is 10：3, stir, react 2h at 0 DEG C, then heat to 40 DEG C, react 2h, obtain cyanate hybrid prepolymer
Thing；Cyanate hybrid prepolymer thing is incubated 2h at 130 DEG C, then heats to 200 DEG C of insulation 1h, then is slowly decreased to room temperature, is obtained
The translucent hydridization cyanate ester resin of yellowish-brown.
The structural formula of Novolac Cyanate Eater Resin is
By test, 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 '-(silica of 1,1,3,3- tetravinyl -1,3- bis-) diphenylamines mix,
Both mass ratioes are 10：3, stir, react 2h at 0 DEG C, then heat to 40 DEG C, react 2h, obtain cyanate hydridization
Prepolymer；Cyanate hybrid prepolymer thing is incubated 2h at 130 DEG C, then heats to 200 DEG C of insulation 1h, then is slowly decreased to room temperature,
Obtain the translucent hydridization cyanate ester resin of yellowish-brown.
The structural formula of dicyclopentadiene type ethylene rhodanate is
By test, the glass transition temperature of the hydridization cyanate ester resin of embodiment 22 is 267 DEG C.
Embodiment 23
By 4,4 '-bis- (phenylcyanate) ethane (L10) and double (amine ethyl) tetramethyls of diamines 1,3- of the chain link containing silica
Disiloxane and 4, the mixture of 4 '-(silica of 1,1,3,3- tetramethyl -1,3- bis-) diphenylamines, both mass ratioes are 1：1)
Mixing, both mass ratioes are 10：3, stir, react 2h at 0 DEG C, then heat to 40 DEG C, react 2h, obtain cyanic acid
Ester hybrid prepolymer thing；Cyanate hybrid prepolymer thing is incubated 2h at 130 DEG C, then heats to 200 DEG C of insulation 1h, then slowly drop
To room temperature, the translucent hydridization cyanate ester resin of yellowish-brown is obtained.
By test, 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) with 4,4 '-(1,1,3,3,5,5- vegolysens, the silicon of 3,5- tri-
Oxygen) diphenylamines mixing, both mass ratioes are 10：3, stir, react 2h at 0 DEG C, then heat to 40 DEG C, react 2h,
Obtain cyanate hybrid prepolymer thing；Cyanate hybrid prepolymer thing is incubated 2h at 130 DEG C, then heats to 200 DEG C of insulation 1h,
Room temperature is slowly decreased to again, obtains the translucent hydridization cyanate ester resin of yellowish-brown.
The structural formula of 4,4 '-(1,1,3,3,5,5- vegolysens, the silica of 3,5- tri-) diphenylamines is
By test, 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 '-(silica of 1,1,3,3- tetravinyls -1,3- two) two
Aniline mixes, and both mass ratioes are 10：3, stir, react 6h at 0 DEG C, then heat to 70 DEG C, react 4h, obtain
Cyanate hybrid prepolymer thing；Cyanate hybrid prepolymer thing is incubated 10min at 100 DEG C, then heats to 230 DEG C of insulation 1h, then
Room temperature is slowly decreased to, obtains the translucent hydridization cyanate ester resin of yellowish-brown.
By test, 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 '-(silica of 1,1,3,3- tetravinyls -1,3- two) two
Aniline mixes, and both mass ratioes are 10：7, stir, react 3min at 35 DEG C, then heat to 70 DEG C, react 2min,
Obtain cyanate hybrid prepolymer thing；Cyanate hybrid prepolymer thing is incubated 2h at 100 DEG C, then heats to 230 DEG C of insulations
20min, then room temperature is slowly decreased to, obtain the translucent hydridization cyanate ester resin of yellowish-brown.
By test, 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) with 4,4 '-(1,1,3,3,5,5- vegolysens, the silicon of 3,5- tri-
Oxygen) diphenylamines mixing, both mass ratioes are 10：2, stir, be made into 30~50% toluene solution；By quartz fibre
Cloth is immersed in above-mentioned solution, obtains prepreg cloth；Above-mentioned prepreg cloth is reacted into 2h at 60 DEG C, then in 200 DEG C of compacting insulations
2h, obtain the hydridization cyanate ester resin composite material of quartz fibre enhancing.
By test, the bending of the hydridization cyanate ester resin composite material of the quartz fibre enhancing of embodiment 27 is strong
Spend for 430MPa, bending modulus 1.34GPa, dielectric constant 2.35, dielectric loss 0.0035.
Embodiment 28
By Novolac Cyanate Eater Resin and 4,4 '-(1,1,3,3,5,5- vegolysen, 3,5- tri- silica) diphenylamines mix, and two
The mass ratio of person is 10：2, stir, be made into 30~50% toluene solution；Quartz fiber cloth is immersed in above-mentioned solution
In, obtain prepreg cloth；Above-mentioned prepreg cloth is reacted into 2h at 60 DEG C, then in 200 DEG C of compacting insulation 2h, obtains quartz fibre increasing
Strong hydridization cyanate ester resin composite material.
By test, the bending of the hydridization cyanate ester resin composite material of the quartz fibre enhancing of embodiment 28 is strong
Spend for 480MPa, bending modulus 1.56GPa, dielectric constant 2.41, dielectric loss 0.0038.
Embodiment 29
By 4,4 '-bis- (phenylcyanate) ethane (L10) with 4,4 '-(1,1,3,3,5,5- vegolysens, the silicon of 3,5- tri-
Oxygen) diphenylamines mixing, both mass ratioes are 10：2, stir, be made into 30~50% toluene solution；By carbon cloth
It is immersed in above-mentioned solution, obtains prepreg cloth；Above-mentioned prepreg cloth is reacted into 2h at 60 DEG C, is then incubated 2h in 200 DEG C of compactings,
Obtain the hydridization cyanate ester resin composite material of fibre reinforced.
Pass through test, the bending strength of the hydridization cyanate ester resin composite material of the fibre reinforced of embodiment 29
For 620MPa, bending modulus 1.64GPa.
Embodiment 30
By Novolac Cyanate Eater Resin and 4,4 '-(1,1,3,3,5,5- vegolysen, 3,5- tri- silica) diphenylamines mix, and two
The mass ratio of person is 10：2, stir, be made into 30~50% toluene solution；Carbon cloth is immersed in above-mentioned solution,
Obtain prepreg cloth；Above-mentioned prepreg cloth is reacted into 2h at 60 DEG C, then in 200 DEG C of compacting insulation 2h, obtains the miscellaneous of fibre reinforced
Change cyanate ester resin composite material.
Pass through test, the bending strength of the hydridization cyanate ester resin composite material of the fibre reinforced of embodiment 30
For 730MPa, bending modulus 1.72GPa.
Embodiment 31
Will be to phenyl dicyanate and 4, the mixing of 4 '-(silica of 1,1,3,3- tetravinyl -1,3- bis-) diphenylamines, both
Mass ratio be 10：4, stir, react 2h at 10 DEG C, then heat to 40 DEG C, react 2h, it is pre- to obtain cyanate hydridization
Polymers；Cyanate hybrid prepolymer thing is incubated 2h at 140 DEG C, then heats to 220 DEG C of insulation 1h, then is slowly decreased to room temperature, is obtained
To the translucent hydridization cyanate ester resin of yellowish-brown.
To the structural formula of phenyl dicyanate
By test, 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 4,4 '-(silica of 1,1,3,3- tetravinyl -1,3- bis-) diphenylamines mix, and two
The mass ratio of person is 10：4, stir, react 2h at 10 DEG C, then heat to 40 DEG C, react 2h, obtain cyanate hydridization
Prepolymer；Cyanate hybrid prepolymer thing is incubated 2h at 140 DEG C, then heats to 220 DEG C of insulation 1h, then is slowly decreased to room temperature,
Obtain the translucent hydridization cyanate ester resin of yellowish-brown.
The structural formula of 1,3- propane dicyanates is
By test, the glass transition temperature of the hydridization cyanate ester resin of embodiment 32 is 186 DEG C.
It should be noted that method of testing involved in above-described embodiment is as follows：The test of fracture toughness according to
ASTME399 standards are tested；The test of glass transition temperature is according to the frequency with 1HZ with 2 DEG C/min heating rate
Method tested；The test of bending strength is tested according to GB/T 9341-2000 standards；Dielectric properties use resonance
Cell method is tested.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited to
This, any one skilled in the art the invention discloses technical scope in, the change that can readily occur in or replace
Change, should all be included within the scope of the present invention.
Claims (10)
1. a kind of cyanate hybridized polymer, it is characterised in that the raw material of the cyanate hybridized polymer includes raw material cyanic acid
The diamines of ester and the chain link containing silica；
The mass ratio of the raw material cyanate and the diamines of the chain link containing silica is more than or equal to 10：7.
2. cyanate hybridized polymer according to claim 1, it is characterised in that the cyanate hybridized polymer is cyanogen
Acid esters hybrid prepolymer thing or hydridization cyanate ester resin.
3. cyanate hybridized polymer according to claim 1, it is characterised 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, it is characterised in that the diamines of the chain link containing silica be containing
The organic solvent solution of the diamine monomer of silica chain link or the diamines of the chain link containing silica.
5. the cyanate hybridized polymer according to claim 3 or 4, it is characterised in that the organic solvent is alkanes
One or more arbitrary proportions mixing in solvent, aromatic solvent, ketones solvent, ether solvent.
6. cyanate hybridized polymer according to claim 1, it is characterised in that the raw material cyanate is aliphatic cyanogen
At least one of the cyanate of acid esters, formula (I~III)；
Logical formula (I) is
Logical formula (II) is
Logical formula (III) is
R in formula1~R8For H, C1~C10 straight or branched alkyls, C3~C8 cycloalkyl, C1~C10 alkoxies, halogen, phenyl or
One kind in phenoxy group；
R9For one kind in 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 alkylidenes, O, N=
N, C=N, C=C, COO, C=N-N=C, the alkylene oxide group with C1-C8 alkylidenes, S, Si (CH3)2Or N-R9
One kind in or.
7. cyanate hybridized polymer according to claim 6, it is characterised in that the halogen is F, Cl, Br or I.
8. cyanate hybridized polymer according to claim 6, it is characterised in that the raw material cyanate be phenylene-
1,3- dicyanates, phenylene -1,4- dicyanates, 2,4,5- trifluoro phenylene -1,3- dicyanates, 4,4 '-bis- (phenylcyanides
Acid esters) methane, dicyclopentadiene type ethylene rhodanate, 4,4 '-bis- (phenylcyanate) isopropyl alkanes, double (the 4- cyanic acid ester groups-benzene of 2,2-
Base) HFC-236fa, Cyclopeutadiene type cyanate, Novolac Cyanate Eater Resin, 4,4 '-methylenediphenyl dicyanate or logical formula (IV)
At least one of；
Logical formula (IV) is
N≡C-O-R10-O-C≡N
R in formula10For C3~C12 aliphatic alkyls.
9. cyanate hybridized polymer according to claim 1, it is characterised in that the diamines of the chain link containing silica leads to
Formula is
M is integer, 0≤m≤100；
R11、R11′、R12And R12′For hydrogen, the substituted or unsubstituted alkyl of straight chain, side chain substituted or unsubstituted alkyl, cycloalkanes
Base, the substituted or unsubstituted alkenyl of straight chain, the substituted or unsubstituted alkenyl of side chain, cycloalkenyl group, straight chain substitution or do not take
One kind in the alkynyl in generation, the substituted or unsubstituted alkynyl of side chain, cycloalkynyl radical, substituted or unsubstituted aryl；
R13And R14Taken for the substituted or unsubstituted alkyl of straight chain, the substituted or unsubstituted alkyl of side chain, cycloalkyl, straight chain
Generation or unsubstituted alkenyl, the substituted or unsubstituted alkenyl of side chain, cycloalkenyl group, the substituted or unsubstituted alkynyl of straight chain, branch
One kind in 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, side chain substituted or unsubstituted alkane
Base, cycloalkyl, the substituted or unsubstituted alkenyl of straight chain, side chain substituted or unsubstituted alkenyl, cycloalkenyl group, straight chain substitution
Or one kind in the substituted or unsubstituted alkynyl of unsubstituted alkynyl, side chain, cycloalkynyl radical, substituted or unsubstituted aryl.
10. a kind of cyanate composite material, it is characterised in that including the cyanate hydridization as described in any one of claim 1~9
Polymer.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110183654A (en) * | 2019-06-04 | 2019-08-30 | 扬州天启新材料股份有限公司 | A kind of preparation method of fluorine-containing cyanate ester resin |
| CN110372861A (en) * | 2019-06-27 | 2019-10-25 | 扬州天启新材料股份有限公司 | The preparation method of modification dicyclopentadiene type ethylene rhodanate resin with agent of low hygroscopicity |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4839505B2 (en) * | 2000-10-16 | 2011-12-21 | 日立化成工業株式会社 | Adhesive film, manufacturing method thereof, and semiconductor device with adhesive film |
| CN102712755A (en) * | 2010-01-25 | 2012-10-03 | 三井化学株式会社 | Polyimide resin composition, adhesive agent and laminate each comprising same, and device |
| CN103328543A (en) * | 2011-01-18 | 2013-09-25 | 日立化成株式会社 | Modified silicone compound, and thermosetting resin composition, prepreg, laminate plate and printed wiring board using same |
| CN104884533A (en) * | 2012-10-18 | 2015-09-02 | 日产化学工业株式会社 | Composition, liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
| CN105331104A (en) * | 2015-12-12 | 2016-02-17 | 苏州大学 | Modified thermosetting resin and preparation method thereof |
| CN105440283A (en) * | 2016-01-07 | 2016-03-30 | 中国科学院长春应用化学研究所 | Modified cyanate ester resin and preparation method of modified cyanate ester resin |
| CN106947251A (en) * | 2017-04-13 | 2017-07-14 | 江苏先诺新材料科技有限公司 | A kind of low dielectric polymer base wave-penetrating composite material and its preparation method and application |
-
2017
- 2017-07-27 CN CN201710623579.0A patent/CN107400235B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4839505B2 (en) * | 2000-10-16 | 2011-12-21 | 日立化成工業株式会社 | Adhesive film, manufacturing method thereof, and semiconductor device with adhesive film |
| CN102712755A (en) * | 2010-01-25 | 2012-10-03 | 三井化学株式会社 | Polyimide resin composition, adhesive agent and laminate each comprising same, and device |
| CN103328543A (en) * | 2011-01-18 | 2013-09-25 | 日立化成株式会社 | Modified silicone compound, and thermosetting resin composition, prepreg, laminate plate and printed wiring board using same |
| CN104884533A (en) * | 2012-10-18 | 2015-09-02 | 日产化学工业株式会社 | Composition, liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
| CN105331104A (en) * | 2015-12-12 | 2016-02-17 | 苏州大学 | Modified thermosetting resin and preparation method thereof |
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