CN107573485A - Phosphazene compound, curing agent, composition epoxy resin, pre-impregnated sheet and composite metal substrate - Google Patents
Phosphazene compound, curing agent, composition epoxy resin, pre-impregnated sheet and composite metal substrate Download PDFInfo
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- CN107573485A CN107573485A CN201610523513.XA CN201610523513A CN107573485A CN 107573485 A CN107573485 A CN 107573485A CN 201610523513 A CN201610523513 A CN 201610523513A CN 107573485 A CN107573485 A CN 107573485A
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- XJOULNBPEXJJOH-UHFFFAOYSA-N CCC(C)(C(C1)C=C2C1=C2C)C1=CCC(C)CC=C1 Chemical compound CCC(C)(C(C1)C=C2C1=C2C)C1=CCC(C)CC=C1 XJOULNBPEXJJOH-UHFFFAOYSA-N 0.000 description 1
- 0 CN(*)C*N(C)* Chemical compound CN(*)C*N(C)* 0.000 description 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N Cc1ccc(C)cc1 Chemical compound Cc1ccc(C)cc1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention provides a kind of phosphazene compound, curing agent, composition epoxy resin, pre-impregnated sheet and composite metal substrate, the phosphazene compound has structure shown in Formulas I, phosphazene compound of the invention by using Formulas I structure, make the phosphazene compound that there is good anti-flammability, its solidfied material has good heat resistance, water resistance, cohesiveness and mechanical performance, electrical property, is a kind of fire retardant matter also with larger economy and environmentally friendly friendly.For the Tg of the copper-clad plate obtained using the phosphazene compound up to 152 165 DEG C, T peel strengths can reach 2.0 2.3kg/mm2, interlaminar strength can reach 1.85 1.90kg/mm2, saturated water absorption can reach less than 0.22%, heat decomposition temperature can reach 410 DEG C and more than, bending strength can reach 12.3 13.3kg/mm2, flammability (UL 94) reaches the ranks of V 0, while economic, environmental protection.
Description
Technical field
The present invention relates to the technical field of fire retardant matter, more particularly to phosphazene compound, curing agent, epoxy composite
Thing, pre-impregnated sheet and composite metal substrate.
Background technology
With developing rapidly for economy, electric wire is widely used in industry-by-industry field, due to electric
The frequent generation of fire incident, the fire-retardant problem of electric wire gradually cause the attention of countries in the world；Discharged during cable fire
A large amount of smog and poisonous, corrosive gas are the hazards in fire, hamper people's safe escape and fire-fighting work,
Make lives and properties by heavy losses.
Traditional technology typically uses addition aluminium hydroxide hydrate, magnesium hydroxide hydrate etc. into material system to contain
The inorganic fire-retarded material such as the metal hydroxides of the crystallization water, and brominated bisphenol A, bmminated bisphenol-A type are added into material system
The method of the higher organic fire-resisting material of the content of halogen such as epoxy resin, product is set to reach required fire resistance or wait
Level.In order to improve the anti-flammability of these organic chemicals for containing halogen, such as antimony oxide is also usually added into system
Deng to the disagreeableness inorganic fire-retarded material of environment.
Halogen-containing fire retardant matter can produce the noxious material of no degradability or difficult degradation in burning, and (such as dioxin has
Machine halogen chemical substance), pollution environment, influence the mankind and animal health.
The non-halogen flame-retardant cable of prior art causes because of addition organophosphorus ester and/or phosphorus nitrogen expansion type flame-retardant system
Mechanical performance declines to a great extent, and flame retardant rating is low, the shortcomings such as temperature resistant grade is low.
The content of the invention
In view of this, first aspect present invention provides a kind of phosphazene compound, the phosphazene compound have good flame-retardance,
Heat resistance, good mechanical performance.
A kind of phosphazene compound, it has the molecular structure as shown in formula I：
In formula I, R1And R2It independently is any inertia nucleophilic group for meeting its chemical environment, R3And R4To meet its change
Learn any organic group of environment, X1And X2It independently is-O-Ar-O- ,-S-R5-S-、-NH-R6-NH-、-NH-R7-O-、-S-R11NH-、-O-R12COO- or-S-R13Any one in COO-, R5、R6、R7、R8、R9、R10、R11、R12
And R13To meet any organic group of its chemical environment, Y1And Y2It independently is any nucleophilic group for meeting its chemical environment
Group；M is the phosphonitrile base M of ring three1, the phosphonitrile base M of ring more than four2Or non-annularity polyphosphazene base M3In any one or at least two
Combination, m, n are the integer more than or equal to zero；A, b, c, d are the integer more than or equal to zero, and a+b+c+d+2 is equal to phosphorus on M groups
2 times of atom number.
In the present invention, it is described to meet that its chemical environment is to refer to atom adjacent thereto to be connected, the change stablized
Learn connecting key.
Preferably, R1And R2It independently is substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, substitution
Or unsubstituted aryloxy group, substituted or unsubstituted alkoxy aryl, substituted or unsubstituted heteroarylalkoxy, substitution or not
Substituted alkyl sulfenyl, substituted or unsubstituted artyl sulfo, substituted or unsubstituted carboxylic acid ester groups, substituted or unsubstituted carbon
Any one in perester radical, substituted or unsubstituted sulfonate group or substituted or unsubstituted phosphonate group；The alkoxy,
Cycloalkyloxy, aryloxy group, alkoxy aryl, heteroarylalkoxy, alkyl sulfenyl, artyl sulfo, carbonate group, sulfonate group or
The substituent of phosphonate group independently is straight or branched alkyl, alkoxy, cycloalkyloxy, aryl, aryloxy group, arylalkoxy
Any one in base, heteroaryl, alkyl sulfenyl, artyl sulfo, carboxylic acid ester groups, carbonate group, sulfonate group or phosphonate group
Or at least two combination, the substituent do not contain reactive end-capping group；For example, the substituent for do not contain OH ,-
CN、-NH2、-SH、-COOH、-CHO、-CONH2Isoreactivity group；Illustrated with instantiation, when substituent is carboxylic acid ester groups,
It can not be the formic acid ester group that one end still carries carboxyl.
Specifically, R1And R2CH can independently be3O-、CH3CH2O-、CH3S-、CH3CH2CH2S-、CH3COO- or PhO- (Ph
Represent phenyl) in any one.
R in the present invention1And R2Can be that identical group can also be different groups.
Preferably, R3And R4It independently is substituted or unsubstituted straight or branched alkylidene, substituted or unsubstituted Asia
Cycloalkyl, substituted or unsubstituted arlydene, substituted or unsubstituted inferior heteroaryl, substituted or unsubstituted arlydene
Alkylidene, substituted or unsubstituted alkylenearylene, substituted or unsubstituted alkylidene inferior heteroaryl or it is substituted or
Any one in unsubstituted inferior heteroaryl alkylidene.
Specifically, R3And R4- CH can independently be2-、-CH2CH2CH2-、 In any one.
Preferably, R5、R6、R7、R8、R11、R12And R13It independently is substituted or unsubstituted straight or branched alkylidene, takes
Generation or unsubstituted cycloalkylidene, substituted or unsubstituted arlydene, substituted or unsubstituted inferior heteroaryl, substitution
Or unsubstituted arylidene alkylene, substituted or unsubstituted alkylenearylene, substituted or unsubstituted alkylidene are sub-
Any one in heteroaryl or substituted or unsubstituted inferior heteroaryl alkylidene.
Specifically, R5、R6、R7、R8、R11、R12And R13- CH can independently be2-、-CH2CH2CH2-、In appoint
Meaning is a kind of.
Preferably, R9And R10It independently is substituted or unsubstituted straight or branched alkyl, substituted or unsubstituted ring
Alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, substituted or unsubstituted aryl, take
Generation or unsubstituted heteroaryl, substituted or unsubstituted substituted or unsubstituted aryloxy group, substituted or unsubstituted aryl
Alkoxy, substituted or unsubstituted alkyl-aryloxy, substituted or unsubstituted heteroarylalkoxy, substituted or unsubstituted alcoxyl
Base heteroaryl, substituted or unsubstituted heteroaryl oxyalkyl, substituted or unsubstituted miscellaneous alkyl aryl, substituted or unsubstituted alkane
Base aryl, substituted or unsubstituted aryl alkyl, substituted or unsubstituted miscellaneous alkyl aryl, substituted or unsubstituted alkyl sulfide
Base, substituted or unsubstituted artyl sulfo, substituted or unsubstituted carboxylic acid ester groups, substituted or unsubstituted carbonate group, substitution
Or any one in unsubstituted sulfonate group or substituted or unsubstituted phosphonate group.
Specifically, R9And R10- CH can independently be3、-OCH3、-CN、-COOH、-CHO、-CONH2It is or any one in Ph-
Kind.
Preferably, Y1And Y2It independently is substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, substitution
Or unsubstituted aryloxy group, substituted or unsubstituted alkoxy aryl, substituted or unsubstituted heteroarylalkoxy, substitution or not
Substituted alkyl sulfenyl, substituted or unsubstituted artyl sulfo, substituted or unsubstituted carboxylic acid ester groups, substituted or unsubstituted carbon
Any one in perester radical, substituted or unsubstituted sulfonate group or substituted or unsubstituted phosphonate group.
Specifically, Y1And Y2- OCH can independently be3、PhO-、CH3S-, PhS- or CH3Any one in COO-.
In the present invention, substituted or unsubstituted straight chained alkyl or branched alkyl be preferably substituted or unsubstituted C1~
C12 (such as C1, C2, C3, C4, C5, C6, C7, C8, C9, C10 or C11) straight chained alkyls or branched alkyl, further preferred C1~
C8 straight chained alkyls or branched alkyl, it is methyl when carbon number is 1, when carbon number is 2, as ethyl.
Substituted or unsubstituted cycloalkyl be preferably substituted or unsubstituted C3~C12 (such as C4, C5, C6, C7, C8,
C9, C10 or C11) cycloalkyl.
Substituted or unsubstituted alkoxy be preferably substituted or unsubstituted C1~C12 (such as C2, C3, C4, C5, C6,
C7, C8, C9, C10 or C11) alkoxy.
Substituted or unsubstituted cycloalkyloxy be preferably substituted or unsubstituted C3~C12 (such as C4, C5, C6, C7,
C8, C9, C10 or C11) cycloalkyloxy.
Substituted or unsubstituted aryl be preferably phenyl, benzyl, naphthyl, Deng.
Substituted or unsubstituted heteroaryl is five yuan or six membered heteroaryl, more preferably substituted or unsubstituted furan
Mutter base or pyridine radicals.
Substituted or unsubstituted aryl alkyl is preferably C7-C13 (such as C8, C9, C10, C11 or C12) aryl alkyl.
Substituted or unsubstituted alkylaryl is preferably C7-C13 (such as C8, C9, C10, C11 or C12) alkylaryl.
Substituted or unsubstituted alkoxy aryl is preferably C7-C13 (such as C8, C9, C10, C11 or C12) alkoxy aromatic
Base.
Substituted or unsubstituted heteroaryl alkyl is preferably C7-C13 (such as C8, C9, C10, C11 or C12) heteroaryl alkane
Base.
Substituted or unsubstituted miscellaneous alkyl aryl is preferably C7-C13 (such as C8, C9, C10, C11 or C12) alkyl heteroaryl
Base.
Substituted or unsubstituted straight-chain alkyl-sub be preferably C1-C12 (such as C2, C3, C4, C5, C6, C7, C8, C9,
C10 or C11) straight-chain alkyl-sub.
Substituted or unsubstituted branched alkylidene be preferably C1-C12 (such as C2, C3, C4, C5, C6, C7, C8, C9,
C10 or C11) branched alkylidene.
Substituted or unsubstituted arlydene is preferably C6-C13 (such as C7, C8, C9, C10, C11 or C12) arlydene.
Substituted or unsubstituted inferior heteroaryl is preferably C5-C13 (such as C6, C7, C8, C9, C10, C11 or C12)
Inferior heteroaryl.
Substituted or unsubstituted alkylenearylene is preferably C7-C13 (such as C8, C9, C10, C11 or C12) alkylene
Base arlydene.
Substituted or unsubstituted arylidene alkylene is preferably C7-C13 (such as C8, C9, C10, C11 or C12) alkylene
Base arlydene.
Substituted or unsubstituted alkylidene inferior heteroaryl is preferably C6-C13 (such as C7, C8, C9, C10, C11 or C12)
Alkylidene inferior heteroaryl.
Substituted or unsubstituted inferior heteroaryl alkylidene is preferably C6-C13 (such as C7, C8, C9, C10, C11 or C12)
Inferior heteroaryl alkylidene.
Substituted or unsubstituted alkoxy heteroaryl is preferably C7-C13 (such as C8, C9, C10, C11 or C12) alkoxy
Heteroaryl.
Substituted or unsubstituted heteroarylalkoxy is preferably C7-C13 (such as C8, C9, C10, C11 or C12) heteroaryl
Alkoxy.
Substituted or unsubstituted heteroaryl oxyalkyl is preferably C7-C13 (such as C8, C9, C10, C11 or C12) heteroaryl
Oxyalkyl.
Substituted or unsubstituted alkoxy aryl is C7-C12 (such as C8, C9, C10 or C11) aralkoxy.
Substituted or unsubstituted alkyl-aryloxy is preferably C7-C12 (such as C8, C9, C10 or C11) alkyl-aryloxy.
Substituted or unsubstituted alkyl sulfenyl is preferably C1-C8 (such as C1, C2, C3, C4, C5, C6, C7 or C8) alkyl sulfide
Base.
Substituted or unsubstituted artyl sulfo is preferably C7-C12 (such as C8, C9, C10 or C11) artyl sulfo.
Term " substituted " used in the present invention refer to any one or more hydrogen atoms on specified atom by selected from
The substituent substitution of designated groups, condition is that the specified atom is no more than normal valency, and the result substituted is to produce stabilization
Compound.When substituent is oxo group or ketone group (i.e.=O), then 2 hydrogen atoms on atom are substituted.Ketone substitutes
Base is not present on aromatic rings." stable compound " be refer to it is sufficiently strong strongly from reactant mixture separation to effective
Purity is simultaneously configured to compounds effective.
In the present invention, M is the phosphonitrile base M of ring three1, the phosphonitrile base M of ring more than four2, non-annularity polyphosphazene base M3In one kind or
At least two combination.
Preferably, M includes at least 50wt%M1, at most 30wt%M2And at most 45wt%M3。
In the present invention, M1Content is at least 50wt%, i.e. M1Content can be 50wt~100wt%, M1For main body into
Point.Work as M1When content is 100wt%, then M is not contained2And M3.The typical but non-limiting M of the present invention1Content can be
50wt%, 51wt%, 55wt%, 58wt%, 60wt%, 65wt%, 70wt%, 74wt%, 75wt%, 80wt%, 85wt%,
90wt%, 92wt%, 95wt%, 98wt% or 100wt%.
In the present invention, M2Content is at most 30wt%, that is, is referred to, M2Content can be 0~30wt%.Work as M2Content is
During 0wt%, that is, refer to, do not contain M2.The typical but non-limiting M of the present invention2Content can be 0wt%, 2wt%, 5wt%,
8wt%, 11wt%, 14wt%, 16wt%, 17wt%, 19wt%, 20wt%, 22wt%, 25wt%, 27wt%, 28wt% or
29wt%.
In the present invention, M3Content is at most 45wt%, that is, is referred to, M3Content can be 0~45wt%.Work as M3Content is
During 0wt%, that is, refer to, do not contain M3.The typical but non-limiting M of the present invention3Content can be 0wt%, 2wt%, 5wt%,
8wt%, 10wt%, 12wt%, 14wt%, 16wt%, 18wt%, 20wt%, 23wt%, 25wt%, 27wt%, 28wt%,
30wt%, 32wt%, 35wt%, 38wt%, 40wt%, 43wt% or 45wt%.
In the present invention, M1、M2And M3Mass percent sum is 100%.
If M1Content is less than 50wt%, or M2It is more than 30wt%, then in use with the reacted product of epoxy resin
Heat resistance, water resistance and mechanical performance etc. will be damaged must performance；M3Content comprise up to the 45% of phosphazenium groups gross mass.
If exceeding the content, would be possible in use with the reacted product of epoxy resin because viscosity is excessive, inconvenient for use, with
And its performance is set the bad result such as to suffer damage because molecular weight is excessive.
Preferably, M1Structure is：
M2Structure is：
Wherein, x is more than or equal to 4；
M3Structure is：
Wherein, y is more than or equal to 3.
Pay attention to, M1、M2In the expression of structural formula, there is symbolOnly to one kind of " ring-type " structure
Signal.
In the structural formula I of the present invention, m, n are the integer more than or equal to zero, and m, n can be zero simultaneously, can also be different
When be zero, such as m can be but be not limited to 0,1,2,3,4,5,6,7,8,9 or 10, n can be but be not limited to 0,1,2,3,4,5,
6th, 7,8,9 or 10.
A, b, c, d are the integer more than or equal to zero, and both c, d can not be zero simultaneously, that is, ensure that M institutes band group at least contains
There is a group (such as-SH or-OH) with reactivity.
In the structural formula of the present invention, the group being connected with M is connected with the phosphorus atoms in M.And in formula I
Middle a+b+c+d+2 is equal to 2 times of number of phosphorus atoms on M groups, that is, ensures that phosphorus atoms reach the saturation shape that chemical valence is pentavalent on M
State.
Phosphazene compound provided by the invention is a kind of Halogen phosphazene compound, all groups or base in its chemical formula
Halogen is not contained in the substituent of group.Therefore, halogen is not contained in the substituent of group and group of the present invention.
Preferably, the halogen-free flameproof thing is a kind of in the compound with following structure or at least two combinations：
Wherein M is the phosphonitrile base of ring three.
Second aspect, the present invention provide a kind of preparation method of the phosphazene compound.
The phosphazene compound of the formula I of the present invention is that nucleophilic substitution occurs with nucleopilic reagent by phosphonitrile chloride to be prepared into
Arrive.
Phosphonitrile chloride refers to M-Cla+b+c+d+2, nucleopilic reagent refers to R1、R2、-S-R3-SH、-O-R4-OH、X1、X2、Y1And Y2
Corresponding affinity reagent, for example, working as R1For methoxyl group when, it is possible to achieve nucleophilic displacement of fluorine occurs by methoxyl group with phosphonitrile chloride
The affinity reagent being connected on M phosphorus atoms can be methanol or sodium methoxide；Work as R2For methylsulfany (CH3When S-), it is possible to achieve
The affinity reagent that methylsulfany is connected on M phosphorus atoms with phosphonitrile chloride generation nucleophilic substitution can be methyl mercaptan
Or sodium methyl mercaptide；As-S-R3- SH is-S-CH2CH2During-SH, it is possible to achieve with phosphonitrile chloride occur nucleophilic substitution will-
S-CH2CH2The affinity reagent that-SH is connected on M phosphorus atoms can be HS-CH2CH2-SH；As-O-R4- OH isWhen, it is possible to achieve nucleophilic substitution occurs with phosphonitrile chloride willIt is connected to M phosphorus
Affinity reagent on atom can beSame method can realize X1、X2、Y1And Y2Connection, X1And X2
Corresponding nucleopilic reagent be at least with M nucleophilic substitution can occur containing two and by X1And X2It is connected on M phosphorus atoms
The nucleopilic reagent of active reactive group.
At least containing a group-SH or-OH with reactivity in the phosphazene compound of formula I.C, which person is in d
Zero, then show that the reactant for participating in necleophilic reaction does not contain the reactant corresponding to it.
In the nucleophilic substitution, the chlorine in phosphonitrile chloride is substituted.Necleophilic reaction can use known in this field
Method complete, such as refer to " progress of polyphosphazene, Zhang Hongwei etc., material Leader 2010 year the 7th phase of volume 24 ".
The instantiation of the catalyst used in necleophilic reaction have the metal chlorides such as zinc chloride, magnesium chloride, aluminium chloride, boron trifluoride and
The lewis bases such as its complex compound, sodium hydroxide.These catalyst can one or more be used in mixed way, the present invention in have no especially
Regulation.Here " phosphorus cyanogen chloride " refers to the compound that M groups are connected with Cl in formula (I).Can as phosphonitrile chloride
Synthesized with solvent, catalyst known to use in known reaction scheme, can also use phosphorus pentachloride with ammonium chloride according to public affairs
The method known is synthesized after phosphorus chloride cyanogen compound, handles purification by physical method or does not purify direct manufacture, its PCl5+
NH4Cl→1/n(NPCl2) n+4HCl, it is mainly tripolymer (PNCl in the reaction product2)3(that is, hexachlorocyclotriph,sphazene) and
The tetramer (PNCl2)4, reaction product is again by by the way that slowly distillation can obtain pure hexachlorocyclotriph,sphazene in 60 DEG C of vacuum.Chlorine
More than Dai Huansi phosphonitriles and chloro non-annularity polyphosphazene can also be prepared by prior art.
In above-mentioned preparation method, nucleopilic reagent necessarily includes the nucleopilic reagent containing at least two active reactive groups
(i.e.-S-R3-SH、-O-R4-OH、X1、X2Corresponding affinity reagent, R3、R4、X1、X2Restriction is same as above), to obtain tying shown in formula (I)
The attachment structure of group and ensure at least to contain a reactivity END CAPPED GROUP in structure shown in formula I in the phosphazene compound of structure
Group.The example of the nucleopilic reagent of at least two active reactive groups can include but is not limited to hydroquinones, resorcinol, naphthalene two
Phenol, mixing benzenediol, 1,4- naphthols, bisphenol-A, bisphenol S, Bisphenol F, the mercaptan of 1,4- phenyl two, 1,2- dithioglycols, 1,3- the third two
Mercaptan, terephthalic acid (TPA) etc..
Except it is above-mentioned containing the nucleopilic reagent of at least two active reactive groups in addition to, can also use contain an active reaction base
Other nucleopilic reagents of group, if monohydric alcohol (for example, methanol, ethanol) or its sodium salt, phenol, unary carboxylation are (for example, acetic acid
Sodium), monoamine (for example, methylamine, ethamine), unitary mercaptan (for example, methyl mercaptan, ethyl mercaptan) etc..
In the reaction of nucleopilic reagent and phosphonitrile chloride, the nucleophilic examination containing an active reactive group can be first used
Agent and phosphonitrile chloride react, and part substitutes the chlorine in phosphonitrile chloride, then use again and described contain at least two active reactions
The nucleopilic reagent of group reacts with phosphonitrile chloride, to obtain the phosphazene compound of formula (I) structure.
The third aspect, the present invention provide a kind of curing agent of epoxy resin, and the epoxy resin obtained using the curing agent is consolidated
Compound has good flame-retardance, heat resistance, good mechanical performance.
A kind of curing agent of epoxy resin, its part or fully be structure shown in above-mentioned Formulas I phosphonitrile chemical combination
Thing.
Preferably, for the reactive group equivalents reacted using same epoxy resin to count, the phosphazene compound accounts for curing agent 30%
More than, for example, 33%, 35%, 38%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%,
90%th, 95% or 100%, particularly preferably 55%~100%.
" the reactive group equivalents reacted using same epoxy resin as count " is referred to reactive phosphorus nitrilation and closed it is understood that term
The relative usage of both thing, curing agent is using both reactive group equivalents that each contained same epoxy resin reacts for calculating
Benchmark.For the phosphazene compound of sulfur-bearing, reactive group is sulfydryl, rather than sulphur atom.
Certainly in the case of forming curing agent in sulfydryl phosphazene compound part, its other curing agent formed can use normal
With the curing agent (being named as curing agent B) used with epoxy resin.Curing agent B instantiation is free of the more phenolic group of nitrogen to be not phosphorous
Compound, nitrogenous more phenol-based compounds, phosphorous more phenol-based compounds, nitrogenous phosphorous more phenol-based compounds, amine compound, benzo
One kind or at least two combination in oxazine resin, acid anhydrides, polyacid and boron trifluoride and its complex compound.
Preferably, the amine compound is fatty amine or aromatic amine, such as dicyandiamide, diethyl triamine, diaminourea two
One kind or at least two combination in phenylmethane or diaminodiphenylsulfone.
Preferably, more phenol-based compounds are bisphenol-A, Bisphenol F, bisphenol S, linear phenolic resin, o-cresol aldehyde tree
One kind or at least two combination in fat, bisphenol A phenolic resin.
Fourth aspect, the present invention provide a kind of with good flame-retardance, heat resistance, the epoxy resin of good mechanical performance
Composition.
A kind of composition epoxy resin, comprising epoxy resin, and the curing agent described in third aspect present invention.
The present invention provides to the specific species of composition epoxy resin epoxy resin without special, as long as containing epoxy radicals
Compound be epoxy resin.Can use epoxy resin commonly used in the art, for example, with liquid bisphenol A types epoxy resin,
Liquid bisphenol F types epoxy resin, solid-state bisphenol A type epoxy resin fat, solid-state bisphenol f type epoxy resin fat, bisphenol-s epoxy resin,
Biphenyl type epoxy resin is two functional epoxy resins of representative, with solid-state, liquid or semisolid novolac type epoxy resin, neighbour
Cresol novolak epoxy resins, bisphenol-A phenolic epoxy resin, the trifunctional above epoxy that acyclic isoprenoid type epoxy resin is representative
Resin.
Preferably, the epoxy resin also includes passes through contracting as the phosphazene compound shown in formula I and epoxy resin
Close the phosphonitrile epoxy resin of reaction generation, and other fire-retarded epoxy resins.
In order to improve the fire resistance of composition epoxy resin, formula I can be increased in composition epoxy resin
The phosphonitrile epoxy resin that shown phosphazene compound is generated with epoxy resin by condensation reaction, and other flame retardant epoxy trees
Fat.
Preferably, other described fire-retarded epoxy resin content of halogen are preferred but are not limited to the epoxy not higher than 0.2%
Resin.
The instantiation of other fire-retarded epoxy resins is DOPO types epoxy resin, phosphorous type epoxy resin, nitrogenous
Type epoxy resin, nitrogenous phosphorous type epoxy resin, phosphorus-containing phenolic aldehyde epoxy resin, nitrogenous novolac epoxy resin containing phosphorous, silicon-contained type
Epoxy resin and one kind in sulfur-type epoxy resin or at least two combination.
Phosphonitrile epoxy resin is generated by phosphazene compound as described above with epoxy resin by condensation reaction.
Herein, it will be readily appreciated by those skilled in the art that when being necessary certainly, ester ring type asphalt mixtures modified by epoxy resin can also be used
The relatively low epoxy resin of ratio of viscosities such as fat, chain type aliphatic type epoxy resin or ester formula epoxy resin, these epoxy resin can be with
Be used alone can also two or more be used together, the present invention has no special regulation to this, and the present invention is to these rings
Oxygen tree fat proportioning amount it is also not specially provided, with reach ensure safe and environment-friendly and required performance on the premise of obtain mesh
Thing.
In composition epoxy resin, can also according to being actually needed, comprising curing accelerator, solvent, supporting material and filler,
Auxiliary agent, fire-retarded epoxy resin, sulfydryl phosphonitrile epoxy resin.
The addition of curing accelerator is for rapid curing.The present invention is to used curing accelerator without special rule
It is fixed, use common epoxy resin curing accelerator, such as imidazoles, triphenylphosphine and its derivative species, tertiary amines, season
The General Catalyst of the epoxy curing agent curing reaction such as amine salt, boron trifluoride and its derivative species, these promotions
Agent both can be used alone, can also two or more be used in mixed way, the number of usage amount can be as needed, with safety, ring
Guarantor obtains purpose thing and is defined, of the invention and not specially provided, usually, contrasts the epoxy resin ingredient in curing system, with
0.001%~2.5% is proper, and more suitably scope is between 0.03%~1.2%.
Primarily to by the curing agent and epoxy resin in composition epoxy resin, it may be such that using epoxy group solvent
Compound obtains the pre-impregnated sheet of high quality, bonding sheet.For the type and quantity using solvent, the present invention has no special regulation,
Such as acetone, butanone, DMF, DMAC, ethanol, methanol, cyclohexanone, 1,4- dioxane, petroleum solvent, toluene, dimethylbenzene, two
The organic solvents such as chloromethanes, dimethyl carbonate, with reach ensure safe and environment-friendly and required performance on the premise of obtain
Purpose thing.Preferably, from as each composition such as butanone has, good dissolubility, toxicity is not strong, boiling point is more moderate
Organic solvent；If the material not readily dissolved in epoxy resin ingredient containing crystallinity such as dicyandiamides, can use a part or
All organic solvents such as nitrogenous class such as DMF, DMAC.It is understood that in solidification process solvent be can by heat come
Improve the speed of volatilization.
Purpose of the supporting material based on the mechanical property for improving final solidfied material, such as glass fibre, carbon fiber and polyester
One kind of fiber or at least two combination.
Filler be in order to increase its some function, property or reduce cost, can be added into curing system as silica,
The inorganic fillers such as diatomite, kaolin, calcium carbonate, mica, titanium dioxide, magnesium hydroxide, aluminium hydroxide, these inorganic fillers can be with
Be used alone, can also two kinds or it is several be used in mixed way, usage amount is typically advisable with the 500phr no more than epoxy resin ingredient.
According to being actually needed, the composition epoxy resin can also include auxiliary agent.Auxiliary agent can be it is general or special,
Such as one kind in defoamer, coupling agent, toughener, levelling agent or releasing agent or at least two combination, the present invention is helped addition
The species and addition of agent do not do special regulation, can be as needed, are defined by the safe and environment-friendly purpose thing that obtains.
5th aspect, the present invention provide a kind of with good flame-retardance, heat resistance, the phosphonitrile epoxy of good mechanical performance
Resin.
A kind of phosphonitrile epoxy resin, be as shown in non-halogen epoxy resin and formula I phosphazene compound in epoxy
Under conditions of the epoxy radicals surplus of resin, by reacting obtained epoxy resin product.
" epoxy resin functional group is superfluous " is defined by the epoxide equivalent of epoxy resin product in below 3585g/eq, more excellent
Selection of land is in below 1520g/eq.
In above-mentioned polycondensation reaction, the temperature of reaction is typically in 40~250 DEG C of scope, more preferably in 60~180 DEG C of model
Enclose, the present invention does not do special regulation, on the premise of ensuring safety and environmental protection, obtains purpose thing selection and is defined.As for the contracting
Poly- reaction, can be carried out under catalyst or without catalysts conditions.Catalyst is added in generally requiring to reaction system, the present invention
Species and addition to catalyst number have no special regulation, usually such as imidazoles, triphenylphosphine and its derivative
The General Catalyst that the epoxy resin such as class, tertiary amines, quaternary ammonium salts react with aldehydes matter can use, and these catalyst were both
Can be used alone, can also two or more be used in mixed way, usage amount reactive material typically in contrast system all exists
Between 100~20000ppm, it is more typically between 200~5000ppm.As for the medium of reaction, it can be solvent-free or have a solvent.
Special regulation, such as the ketones solvent such as acetone, butanone, cyclohexanone, benzene,toluene,xylene, mixing two are had no to reaction dissolvent
The aromatic solvents such as toluene, dichloromethane, chloroform, chlorobenzene etc. contain chlorinated solvents, ether, butyl ether, glycol monoethyl ether
Deng ethers or ether alcohols solvent, petroleum solvent naphtha, alcohols solvent such as butanol, isobutanol etc. can use, and these solvents can
Be used alone, can also two kinds or it is several be used in mixed way, usage amount number, can be determined according to actual conditions, generally
The dosage that sulfydryl phosphonitrile epoxy resin solid content is 5~100% can be made, particularly preferred is that sulfydryl phosphonitrile epoxy resin can be made to contain admittedly
Measure the dosage for 20~100%.In view of the general principle of polycondensation reaction has been known technology, will not be repeated here.
Special regulation is had no to non-halogen epoxy resin in the present invention, " non-halogen epoxy resin ", which refers to, here is free of
There are the epoxy resin of halogen atom, or the epoxy resin that content of halogen is very low.Such as with liquid bisphenol A types epoxy resin, liquid
Bisphenol f type epoxy resin, solid-state bisphenol A type epoxy resin fat, solid-state bisphenol f type epoxy resin fat, bisphenol-s epoxy resin, biphenyl
Type epoxy resin is two functional epoxy resins of representative, with solid-state, liquid or semisolid novolac type epoxy resin, adjacent methyl
Novolac epoxy resin, bisphenol-A phenolic epoxy resin, the trifunctional above asphalt mixtures modified by epoxy resin that acyclic isoprenoid type epoxy resin is representative
Fat.Herein, it will be readily appreciated by those skilled in the art that when being necessary certainly, alicyclic epoxy resin, chain can also be used
The relatively low epoxy resin of the ratio of viscosities such as formula aliphatic type epoxy resin or ester formula epoxy resin, these epoxy resin can individually make
With can also two or more be used together, the present invention special regulation is had no to this.Above-mentioned epoxy resin both can be with one
Reaction is partially or mostly first participated in, question response adds the epoxy resin ginseng of other compositions again to a certain extent or completely after reaction
With reaction, can also all required epoxy resin segmentation input reactions or disposable input reaction, the present invention does not do special
Regulation, with ensure it is safe and environment-friendly on the premise of obtain purpose thing.
6th aspect, the present invention provide a kind of with good flame-retardance, heat resistance, the flame retardant combination of good mechanical performance
Thing.
A kind of fire-retardant combination, include the phosphonitrile epoxy resin as described in terms of the 5th.
Polyphenol base epoxy can be comprised only in above-mentioned fire-retardant combination, can also add others has flame retardant resin,
Such as DOPO types epoxy resin, phosphorous type epoxy resin, nitrogenous type epoxy resin, nitrogenous phosphorous type epoxy resin, phosphorus-containing phenolic aldehyde
Resin, nitrogenous phenolic resin containing phosphorous, silicon-contained type epoxy resin and sulfur-type epoxy resin.Certainly can also be as needed, add
Curing agent, auxiliary agent, the filler of curing accelerator and halogen-free flame-retardance.
Curing agent has no special regulation in the present invention, and the material for being typically used as epoxy curing agent can be employed as this hair
The curing agent of bright epoxy resin composition.Instantiation can be amino-compound, such as dicyandiamide, diethyl triamine, diamino
One kind or at least two combination in the fatty amines such as base diphenyl-methane, diaminodiphenylsulfone or aromatic amine；It can also be two
Or more than two phenol-based compounds or mixture, such as bisphenol-A, Bisphenol F, bisphenol S, linear phenolic resin, bisphenol-A phenolic tree
Contain in one molecule such as fat, benzoxazine colophony, acid anhydrides, polyacid, boron trifluoride and its complex compound etc., these epoxy resin
Curing agent can be used alone, can also two kinds or it is several be used in mixed way, usage amount generally contrast epoxy resin equivalent proportion
Between 0.4~1.5 (eq).
For rapid curing, it is often necessary to add curing accelerator.The present invention is to used curing accelerator without special
Regulation, using the usually used curing accelerator of epoxy resin, for example, imidazoles, triphenylphosphine and its derivative species,
The General Catalyst of the epoxy curing agent curing reaction such as tertiary amines, quaternary ammonium salts, boron trifluoride and its derivative species,
These accelerator both can be used alone, can also two or more be used in mixed way, the number of usage amount can be as needed,
It is defined by the safe and environment-friendly purpose thing that obtains, it is of the invention and not specially provided, usually, contrast the epoxy resin in curing system
Composition, proper with 0.001%~2.5%, more suitably scope is between 0.03%~1.2%.
Filler be in order to increase its some function, property or reduce cost, can be added into curing system as silica,
The inorganic fillers such as diatomite, kaolin, calcium carbonate, mica, titanium dioxide, magnesium hydroxide, aluminium hydroxide, these inorganic fillers can be with
Be used alone, can also two kinds or it is several be used in mixed way, usage amount is typically with the 500phr (phr no more than epoxy resin ingredient
Represent the number contained by per hectogram) it is advisable.
In above-mentioned fire-retardant combination, it is general or special as disappeared that some can be added into system according to being actually needed
The materials such as infusion, coupling agent, toughener, levelling agent, the present invention do not do special regulation to the species and addition of adding auxiliary agent,
Can be as needed, it is defined by the safe and environment-friendly purpose thing that obtains.
7th aspect, the present invention provide a kind of pre-impregnated sheet, and it is impregnated with or be coated on base material by fire-retardant combination described above
Form.
Base material can be fiberglass substrate, polyester base material, polyimide base material, ceramic base material or carbon fiber base material etc..
Here, the concrete technology condition of its impregnation or coating is not particularly limited." pre-impregnated sheet " is also well known to those skilled in the art
" bonding sheet ".
Eighth aspect, the present invention provide a kind of composite metal substrate, and it includes more than one such as above-mentioned pre-impregnated sheet and entered successively
Row surface metal-clad is overlapping, pressing forms.
Here, the material of surface metal-clad is the alloy of aluminium, copper, iron and its any combination.The tool of composite metal substrate
Body example has CEM-1 copper-clad plates, CEM-3 copper-clad plates, FR-4 copper-clad plates, FR-5 copper-clad plates, CEM-1 aluminium bases, CEM-3 aluminium bases
Plate, FR-4 aluminium bases or FR-5 aluminium bases.
9th aspect, the present invention provide a kind of wiring board, formed in the Surface Machining circuit of above-mentioned composite metal substrate.
The raw material of flame-retardant composition or composition epoxy resin is formed with good by being solidificated on composite metal substrate
The coating of good fire resistance, wiring board, such as electronic industry, electric, Electric Industrial, communications and transportation, Aero-Space, object for appreciation can be improved
Tool industry etc. needs the extensive use of the industries such as the machine of wiring board, equipment, instrument, instrument.
Tenth aspect, the present invention provide a kind of plastic packaging material, and it includes the epoxy composite described in fourth aspect present invention
Thing or the fire-retardant combination as described in sixth aspect present invention.Can according to being actually needed, select conventional functional stuffing according to
Conventional dosage is added into above-mentioned composition epoxy resin or above-mentioned fire-retardant combination to be configured to plastic packaging material.
Above-mentioned term " ××× base or group ", which refers to, sloughs one or more hydrogen atoms in ××× molecular structure of compounds
Or remaining part after other atoms or atomic group.
Relative to prior art, the invention has the advantages that：
The present invention makes the phosphazene compound have good anti-flammability, it is solid by using the phosphazene compound of Formulas I structure
Compound has good heat resistance, water resistance, cohesiveness and mechanical performance, electrical property, is a kind of also to have larger economy
And the fire retardant matter of environmentally friendly friendly.The Tg of the copper-clad plate obtained using the fire-retardant compound can reach 152-165 DEG C, T- strippings
2.0-2.3kg/mm is can reach from intensity2, interlaminar strength can reach 1.85-1.90kg/mm2, saturated water absorption can reach
Less than 0.22%, heat decomposition temperature can reach 410 DEG C and more than, bending strength can reach 12.3-13.3kg/mm2, flammability
(UL-94) V-0 ranks are reached.Therefore, using Formulas I structure phosphazene compound prepare copper-clad plate have good heat resistance,
Water resistance, cohesiveness and mechanically and electrically performance, its anti-flammability, while economic, environmental protection can be improved.
Embodiment
Technical scheme is further illustrated with reference to embodiment.
In the examples below, raw materials used phosphonitrile chloride (such as phosphorus cyanogen of chlordene ring three) can be according to conjunction of the present invention
Synthesize to obtain into method or synthetic method known in the art, remaining raw material can be by being commercially available.
Embodiment 1
In the present embodiment, phosphazene compound has following structure：
Hexachlorocyclotriph,sphazene 1mol, acetone 250ml, double is put into three mouthfuls of 2000ml glass reactors with agitating device
Phenol A 3mol, sodium methyl mercaptide 3mol, stir, while leading to nitrogen, be warming up to 60 DEG C, 20% sodium hydroxide is instilled with 60min
Solution 620g, kept for 60 DEG C of temperature, 15 hours of stirring reaction.After reaction, with the moisture in physical method removal system, after
The insoluble matter in the system of removing is filtered off, distills solvent in system, obtains the phosphazene compound A that phenolic hydroxyl equivalent is 320g/eq
1mol。
Proton nmr spectra sign is carried out to obtained phosphazene compound A, it is as a result as follows：
1H NMR(CDCl3,500MHz):6.6-7.0 (m, 24H, phenyl ring on hydrogen), 5.0 (s, 3H, phenolic hydroxyl group hydrogen), 2.0 (m,
9H,SCH 3) 1.6 (m, 18H, bisphenol-A group on methyl hydrogen).
The position of infrared spectrum characteristic peak：The characteristic absorption peak 1217cm of P=N keys in phosphazene backbone-1, P- in phosphazene backbone
N 874cm-1, the absworption peak 2995cm of methyl ether-1, P-O-C key absworption peaks 1035cm-1, the skeleton of phenyl ring shakes in bisphenol-A group
Dynamic absworption peak 1611cm-1、1509cm-1、1446cm-1, phenolic hydroxyl group absworption peak 3610cm-1、1260cm-1。
Using above-mentioned phosphazene compound A 160g as curing agent, the o-cresol formaldehyde epoxy that epoxide equivalent is 200g/eq is added
Resin 100g, curing accelerator 2-methylimidazole 0.2g, prepares composition epoxy resin.Then the composition epoxy resin is used
The standard copper-clad plate sample for meeting the standards such as national standard, UL is made according to general copper-clad plate production process, is named as a copper-clad plates,
The performance of a copper-clad plates is tested, its result represents in table -1.
Embodiment 2
In the present embodiment, phosphazene compound has following structure：
Hexachlorocyclotriph,sphazene 1mol, acetone 250ml, second are put into three mouthfuls of 2000ml glass reactors with agitating device
Two mercaptan 6mol, stir, lead to nitrogen, while being warming up to 60 DEG C, 20% sodium hydroxide solution is instilled with 60min
620g, kept for 60 DEG C of temperature, 15 hours of stirring reaction, after reaction, with the moisture in physical method removal system, after elimination
Except the insoluble matter in system, solvent in system is distilled, it is 110g/eq phosphazene compound B 1mol to obtain mercapto equivalents..
Proton nmr spectra sign is carried out to obtained phosphazene compound B, it is as a result as follows：
1H NMR(CDCl3,500MHz):δ2.8(m,24H,HS-CH 2CH 2S-),1.5(s,6H,HS-CH2CH2S-)。
The position of infrared spectrum characteristic peak：The characteristic absorption peak 1217cm of P=N keys in phosphazene backbone-1, P- in phosphazene backbone
N 874cm-1, the absworption peak 2995cm of methyl ether-1, P-O-C key absworption peaks 1035cm-1, CH2- S absworption peak 2980cm-1,-SH
Absworption peak 2560cm-1。
Using above-mentioned phosphazene compound B 55g as curing agent, the o-cresol formaldehyde asphalt mixtures modified by epoxy resin that epoxide equivalent is 200g/eq is added
Fat 100g, curing accelerator 2-methylimidazole 0.2g, prepares composition epoxy resin.Then pressed using the composition epoxy resin
The standard copper-clad plate sample for meeting the standards such as national standard, UL is made according to general copper-clad plate production process, is named as b copper-clad plates, surveys
The performance of b copper-clad plates is tried, its result represents in table -1.
Embodiment 3
In the present embodiment, phosphazene compound has following structure：
Hexachlorocyclotriph,sphazene 1mol, acetone 250ml, benzene are put into three mouthfuls of 2000ml glass reactors with agitating device
Thiophenol 3mol, sodium methoxide 2mol, ethylene glycol 1mol, stir, while leading to nitrogen, be warming up to 60 DEG C, 20% is instilled with 60min
Sodium hydroxide solution 620g, 60 DEG C of temperature are kept, 15 hours of stirring reaction, then add hexachlorocyclotriph,sphazene 1mol, are continued
Reaction 2 hours, hydroquinones 2mol, sodium methoxide 3mol are added afterwards, continue reaction 6 hours.After reaction, removed with physical method
Moisture in system, the insoluble matter in removal system is refiltered, distill solvent in system, it is 500g/ to obtain hydroxyl equivalent
Eq phosphazene compounds C1mol.
Proton nmr spectra sign is carried out to obtained phosphazene compound C, it is as a result as follows：
1H NMR(CDCl3,500MHz):δ7.0-7.2(m,15H,Hydrogen on phenyl ring in group), 6.6 (m,
8H,Hydrogen on phenyl ring in group), 5.0 (m, 2H,Hydrogen on hydroxyl in group), 3.7 (d,
4H,O-CH 2CH 2O-),3.4(t,15H,O-CH 3)。
The position of infrared spectrum characteristic peak：The characteristic absorption peak 1217cm of P=N keys in phosphazene backbone-1, P- in phosphazene backbone
N 874cm-1, the absworption peak 2995cm of methyl ether-1, P-O-C key absworption peaks 1035cm-1, CH2- O absworption peak 2983cm-1, phenol
Hydroxyl absorption peak 3610cm-1、1260cm-1。
Using above-mentioned phosphazene compound C250g as curing agent, the o-cresol formaldehyde asphalt mixtures modified by epoxy resin that epoxide equivalent is 200g/eq is added
Fat 100g, curing accelerator 2-methylimidazole 0.2g, prepares composition epoxy resin.Then pressed using the composition epoxy resin
The standard copper-clad plate sample for meeting the standards such as national standard, UL is made according to general copper-clad plate production process, is named as c copper-clad plates, surveys
The performance of c copper-clad plates is tried, its result represents in table -1.
Embodiment 4
In the present embodiment, phosphazene compound has following structure：
Hexachlorocyclotriph,sphazene 1mol, acetone 250ml, second are put into three mouthfuls of 2000ml glass reactors with agitating device
Two mercaptan 5mol and hydroquinones 1mol, stir, while leading to nitrogen, be warming up to 60 DEG C, 20% hydrogen-oxygen is instilled with 60min
Change sodium solution 620g, keep 60 DEG C of temperature, 15 hours of stirring reaction, then add hexachlorocyclotriph,sphazene 1mol, continue reaction 5
Hour, bisphenol-A 1mol, sodium methoxide 4mol are added afterwards, continue reaction 10 hours.After reaction, with physical method removal system
Moisture, refilter the insoluble matter in removal system, distill solvent in system, obtain phenolic hydroxyl equivalent for 1200g/eq,
Mercapto equivalents are 240g/eq phosphazene compound D 1mol.
Proton nmr spectra sign is carried out to obtained flame-retardant compound, it is as a result as follows：
1H NMR(CDCl3,500MHz):δ 6.5-7.0 (m, 44H, phenyl ring on hydrogen), 5.0 (s, 5H, phenolic hydroxyl group hydrogen), 2.8
(m,20H,HS-CH 2CH 21.7 (s, 30H, methyl on hydrogen)), S- 1.5 (s, 5H, methyl on hydrogen).
The position of infrared spectrum characteristic peak：The characteristic absorption peak 1217cm of P=N keys in phosphazene backbone-1, P- in phosphazene backbone
N 874cm-1, the absworption peak 2995cm of methyl ether-1, P-O-C key absworption peaks 1035cm-1, CH2- O absworption peak 2983cm-1, it is double
The skeletal vibration absworption peak 1611cm of phenyl ring in phenol A groups-1、1509cm-1、1446cm-1, phenolic hydroxyl group absworption peak 3610cm-1、
1260cm-1。
Using above-mentioned phosphazene compound D 120g as curing agent, the o-cresol formaldehyde epoxy that epoxide equivalent is 200g/eq is added
Resin 100g, curing accelerator 2-methylimidazole 0.2g, prepares composition epoxy resin.Then the composition epoxy resin is used
The standard copper-clad plate sample for meeting the standards such as national standard, UL is made according to general copper-clad plate production process, is named as d copper-clad plates,
The performance of d copper-clad plates is tested, its result represents in table -1.
Comparative example 1
Epoxide equivalent is 200g/eq o-cresol formaldehyde epoxy resin 200g, adds the line that phenolic hydroxyl equivalent is 105g/eq
Type phenolic resin curative 105g and hexaphenoxycyclotriphosphazene 70g and 0.2g as fire retardant 2-methylimidazole, system
Standby composition epoxy resin.Then it is made using the composition epoxy resin according to general copper-clad plate production process and meets state
The standard copper-clad plate sample e of the standards such as mark, UL, copper-clad plate e properties represent in table -1.
Comparative example 2
Epoxide equivalent is 200g/eq o-cresol formaldehyde epoxy resin 200g, and adding has such as the resinification of formula (1) structure
Compound 220g, ester equivalent are 220g/eq and hexaphenoxycyclotriphosphazene 70g and 0.2g as fire retardant pyridine azoles, are made
Standby composition epoxy resin.Then it is made using the composition epoxy resin according to general copper-clad plate production process and meets state
The standard copper-clad plate sample f of the standards such as mark, UL.Copper-clad plate f properties represent in table -1.
Embodiment and the test result of comparative example are as shown in following table -1 (in view of specific method of testing has been people in the art
Known to member, method is no longer described in detail at this).
Table -1
The test data of above table, show fire-retardant compound and its derivative of the present invention when use is consolidated in epoxy resin
When in change system and other systems, there is good anti-flammability, its solidfied material has good heat resistance, water resistance, cohesiveness
With mechanical performance, electrical property.The fire-retardant compound of the present invention belongs to that low cost, raw material sources are abundant, properties are good
The environment-friendly type flame-retardant material of the novel environmental friendly of energy-saving and emission-reducing.
Applicant states that the present invention illustrates the phosphazene compound of the present invention, curing agent, asphalt mixtures modified by epoxy resin by above-described embodiment
Oil/fat composition, pre-impregnated sheet and composite metal substrate, but the invention is not limited in above-described embodiment, that is, do not mean that the present invention must
Above-described embodiment, which must be relied on, to be implemented.Person of ordinary skill in the field is right it will be clearly understood that any improvement in the present invention
The equivalence replacement of each raw material of product of the present invention and the addition of auxiliary element, the selection of concrete mode etc., all fall within the guarantor of the present invention
Protect within the scope of scope and disclosure.
Claims (10)
1. a kind of phosphazene compound, it is characterised in that it has the molecular structure as shown in formula I：
In formula I, R1And R2It independently is any inertia nucleophilic group for meeting its chemical environment, R3And R4To meet its chemical environment
Any organic group, X1And X2It independently is-O-Ar-O- ,-S-R5-S-、-NH-R6-NH-、-NH-R7-O-、-S-R11NH-、-O-R12COO- or-S-R13Any one in COO-, R5、R6、R7、R8、R9、R10、R11、R12
And R13To meet any organic group of its chemical environment, Y1And Y2It independently is any nucleophilic group for meeting its chemical environment
Group；M is the phosphonitrile base M of ring three1, the phosphonitrile base M of ring more than four2Or non-annularity polyphosphazene base M3In any one or at least two
Combination, m, n are the integer more than or equal to zero；A, b, c, d are that both integers, c, d more than or equal to zero can not be zero simultaneously, and a+
B+c+d+2 is equal to 2 times of number of phosphorus atoms on M groups.
2. phosphazene compound according to claim 1, it is characterised in that R1And R2It independently is substituted or unsubstituted alkane
Epoxide, substituted or unsubstituted cycloalkyloxy, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkoxy aryl, take
Generation or unsubstituted heteroarylalkoxy, substituted or unsubstituted alkyl sulfenyl, substituted or unsubstituted artyl sulfo, substitution or
Unsubstituted carboxylic acid ester groups, substituted or unsubstituted carbonate group, substituted or unsubstituted sulfonate group or substitution or unsubstituted
Phosphonate group in any one；The alkoxy, cycloalkyloxy, aryloxy group, alkoxy aryl, heteroarylalkoxy, alkane
Base sulfenyl, artyl sulfo, carbonate group, the substituent of sulfonate group or phosphonate group independently are straight or branched alkyl, alkane
Epoxide, cycloalkyloxy, aryl, aryloxy group, alkoxy aryl, heteroaryl, alkyl sulfenyl, artyl sulfo, carboxylic acid ester groups, carbonic ester
In base, sulfonate group or phosphonate group any one or at least two combination, the substituent do not contain reactive end-blocking
Group；
Preferably, R3And R4It independently is substituted or unsubstituted straight or branched alkylidene, substituted or unsubstituted sub- cycloalkanes
Base, substituted or unsubstituted arlydene, substituted or unsubstituted inferior heteroaryl, substituted or unsubstituted arlydene alkylene
Base, substituted or unsubstituted alkylenearylene, substituted or unsubstituted alkylidene inferior heteroaryl or substituted or do not take
Any one in the inferior heteroaryl alkylidene in generation；
Preferably, R5、R6、R7、R8、R11、R12And R13Independently be substituted or unsubstituted straight or branched alkylidene, substitution
Or unsubstituted cycloalkylidene, substituted or unsubstituted arlydene, substituted or unsubstituted inferior heteroaryl, substitution or not
Substituted arylidene alkylene, substituted or unsubstituted alkylenearylene, substituted or unsubstituted alkylidene Asia heteroaryl
Any one in base or substituted or unsubstituted inferior heteroaryl alkylidene；
Preferably, R9And R10Independently be substituted or unsubstituted straight or branched alkyl, substituted or unsubstituted cycloalkyl,
Substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, substituted or unsubstituted aryl, substitution or
Unsubstituted heteroaryl, substituted or unsubstituted substituted or unsubstituted aryloxy group, substituted or unsubstituted alkoxy aryl,
Substituted or unsubstituted alkyl-aryloxy, substituted or unsubstituted heteroarylalkoxy, substituted or unsubstituted alkoxy heteroaryl
Base, substituted or unsubstituted heteroaryl oxyalkyl, substituted or unsubstituted miscellaneous alkyl aryl, substituted or unsubstituted alkyl virtue
Base, substituted or unsubstituted aryl alkyl, substituted or unsubstituted miscellaneous alkyl aryl, substituted or unsubstituted alkyl sulfenyl, take
Generation or unsubstituted artyl sulfo, substituted or unsubstituted carboxylic acid ester groups, substituted or unsubstituted carbonate group, substitution or do not take
Any one in the sulfonate group in generation or substituted or unsubstituted phosphonate group；
Preferably, Y1And Y2It independently is substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, substitution or not
Substituted aryloxy group, substituted or unsubstituted alkoxy aryl, substituted or unsubstituted heteroarylalkoxy, substitution or unsubstituted
Alkyl sulfenyl, substituted or unsubstituted artyl sulfo, substituted or unsubstituted carboxylic acid ester groups, substituted or unsubstituted carbonic ester
Any one in base, substituted or unsubstituted sulfonate group or substituted or unsubstituted phosphonate group；
Preferably, M1Structure is：
M2Structure is：
Wherein, x is more than or equal to 4；
M3Structure is：
Wherein, y is more than or equal to 3；
Preferably, M includes at least 50wt%M1, at most 30wt%M2And at most 45wt%M3；
Preferably, the halogen-free flameproof thing is a kind of in the compound with following structure or at least two combinations：
Wherein M is the phosphonitrile base of ring three.
A kind of 3. curing agent of epoxy resin, it is characterised in that what it was formed be partially or fully such as claim 1 or
2 phosphazene compounds.
Preferably, for the reactive group equivalents reacted using same epoxy resin to count, the phosphazene compound accounts for curing agent more than 30%；
It is further preferred that the reactive group equivalents reacted using same epoxy resin is counts, the sulfydryl phosphazene compound accounts for solidification
The 55%~100% of agent；
Preferably, the curing agent is also comprising curing agent B, the curing agent B for it is not phosphorous without the more phenol-based compounds of nitrogen, it is nitrogenous
More phenol-based compounds, phosphorous more phenol-based compounds, nitrogenous phosphorous more phenol-based compounds, amine compound, benzoxazine colophony, acid
One kind or at least two combination in acid anhydride, polyacid and boron trifluoride and its complex compound；
Preferably, the amine compound is in dicyandiamide, diethyl triamine, MDA or diaminodiphenylsulfone
It is a kind of or at least two combination；
Preferably, more phenol-based compounds be bisphenol-A, it is Bisphenol F, bisphenol S, linear phenolic resin, o-cresol urea formaldehyde, double
One kind or at least two combination in phenol A phenolic resin.
4. a kind of composition epoxy resin, it is characterised in that include epoxy resin, and curing agent as claimed in claim 3；
Preferably, the epoxy resin is two functions or two function above epoxy resin；
Preferably, two functional epoxy resins are liquid bisphenol A types epoxy resin, liquid bisphenol F types epoxy resin, solid-state bisphenol-A
Type epoxy resin, solid-state bisphenol f type epoxy resin fat and one kind in bisphenol-s epoxy resin, biphenyl type epoxy resin or at least
Two kinds of combination；
Preferably, epoxy resin more than two functions is phenol aldehyde type epoxy resin, o-cresol formaldehyde epoxy resin, bisphenol-A phenolic
One kind or at least two combination of epoxy resin and acyclic isoprenoid type epoxy resin；
Preferably, the epoxy resin also includes passes through condensation as the phosphazene compound described in claim 1 or 2 and epoxy resin
React the phosphonitrile epoxy resin of generation, and other fire-retarded epoxy resins；
Preferably, other described fire-retarded epoxy resin content of halogen are not higher than 0.2%；
Preferably, other described fire-retarded epoxy resins are DOPO types epoxy resin, phosphorous type epoxy resin, nitrogenous type ring oxygen tree
Fat, nitrogenous phosphorous type epoxy resin, phosphorus-containing phenolic aldehyde epoxy resin, nitrogenous novolac epoxy resin containing phosphorous, silicon-contained type epoxy resin
With one kind in sulfur-type epoxy resin or at least two combination；
Preferably, the composition epoxy resin also includes curing accelerator；
Preferably, the curing accelerator is imidazoles, triphenylphosphine and its derivative species, tertiary amines, quaternary ammonium salts and trifluoro
Change boron and its one kind in derivative species or at least two combination；
Preferably, the dosage of the curing accelerator is account for epoxy resin gross mass 0.001~2.5%, more preferably
0.03~1.2%；
Preferably, the composition epoxy resin also includes supporting material and filler；
Preferably, the supporting material is one kind in glass fibre, carbon fiber and polyester fiber or at least two combination；
Preferably, the filler is silica, diatomite, kaolin, calcium carbonate, mica, titanium dioxide, magnesium hydroxide, hydrogen-oxygen
Change one kind in aluminium or at least two combination；
Preferably, the dosage of the filler is no more than 500phr for epoxy resin gross mass；
Preferably, the composition epoxy resin also includes auxiliary agent, and the auxiliary agent is defoamer, coupling agent, toughener, levelling agent
Or one kind in releasing agent or at least two combination.
5. a kind of phosphonitrile epoxy resin, it is characterised in that be by non-halogen epoxy resin and phosphorus as claimed in claim 1 or 2
Nitrile compound is under conditions of the epoxy radicals surplus of epoxy resin, by reacting obtained epoxy resin product；
Preferably, the epoxide equivalent of the epoxy resin product is in below 3585g/eq；More preferably in below 1520g/eq；
Preferably, the reaction is carried out under conditions of under catalyst or without catalysts conditions；
Preferably, the catalyst is in imidazoles, triphenylphosphine and its derivative species, tertiary amines and quaternary ammonium salts catalyst
One kind is used alone or at least two are used in mixed way；
Preferably, the dosage of the catalyst be relative to the 0.01~2.5% of phosphazene compound, more preferably 0.02%~
0.5%；
Preferably, the temperature of the reaction is 40~250 DEG C, more preferably 60~180 DEG C.
Preferably, the reaction is solvent-free or have and carry out under conditions of solvent, and the solvent is that ketones solvent, aromatics are molten
Agent, chlorinated solvents, ether solvent, ether alcohols solvent, alcohols solvent and one kind in petroleum solvent naphtha or at least two；
Preferably, the dosage of the solvent is can make the dosage that sulfydryl phosphonitrile epoxy resin solid content is 5~100%, further
Preferably sulfydryl phosphonitrile epoxy resin solid content is 20~100% dosage；
Preferably, the non-halogen epoxy resin is epoxy resin more than two functions or two functions；
Preferably, the epoxy resin of two functions is liquid bisphenol A types epoxy resin, liquid bisphenol F types epoxy resin, solid-state bis-phenol
A types epoxy resin, solid-state bisphenol f type epoxy resin fat and one kind in bisphenol-s epoxy resin, biphenyl type epoxy resin or at least
Two kinds of combination；
Preferably, epoxy resin more than two functions is phenol aldehyde type epoxy resin, o-cresol formaldehyde epoxy resin, bisphenol-A phenolic
One kind or at least two combination of epoxy resin and acyclic isoprenoid type epoxy resin.
6. a kind of fire-retardant combination, it is characterised in that include phosphonitrile epoxy resin as claimed in claim 5；
Preferably, filling out for the epoxy resin with anti-flammability, curing agent, auxiliary agent, curing accelerator and halogen-free flame-retardance is also included
Material；
Preferably, the epoxy resin with anti-flammability is DOPO types epoxy resin, phosphorous type epoxy resin, nitrogenous type ring oxygen
Resin, nitrogenous phosphorous type epoxy resin, phosphorus-containing phenolic aldehyde epoxy resin, nitrogenous novolac epoxy resin containing phosphorous, silicon-contained type asphalt mixtures modified by epoxy resin
Fat and one kind in sulfur-type epoxy resin or at least two combination；
Preferably, the curing agent is more phenol-based compounds, amine compound, benzoxazine colophony, acid anhydrides, polyacid and trifluoro
Change boron and its one kind in complex compound or at least two combination；
Preferably, the amine compound is the fat such as dicyandiamide, diethyl triamine, MDA, diaminodiphenylsulfone
One kind or at least two combination in fat amine or aromatic amine；
Preferably, more phenol-based compounds be bisphenol-A, it is Bisphenol F, bisphenol S, linear phenolic resin, o-cresol urea formaldehyde, double
One kind or at least two combination in phenol A phenolic resin；
Preferably, the dosage of the curing agent and the equivalent proportion of epoxy resin 0.4~1.5；
Preferably, the curing accelerator is imidazoles, triphenylphosphine and its derivative species, tertiary amines, quaternary ammonium salts and trifluoro
Change boron and its one kind in derivative species or at least two combination；
Preferably, the dosage of the curing accelerator is account for epoxy resin gross mass 0.001~2.5%, more preferably
0.03~1.2%；
Preferably, the filler is in silica, kaolin, calcium carbonate, mica, titanium dioxide, magnesium hydroxide, aluminium hydroxide
It is a kind of or at least two combination；
Preferably, the dosage of the filler is below the 500phr of epoxy resin gross mass；
Preferably, the auxiliary agent is one kind in defoamer, coupling agent, toughener and levelling agent or at least two combination.
7. a kind of pre-impregnated sheet, it is characterised in that it is by composition epoxy resin as claimed in claim 4 or such as claim 6
The fire-retardant combination is impregnated with or is coated on base material and forms；
Preferably, the base material is fiberglass substrate, polyester base material, polyimide base material, ceramic base material or carbon fiber base material.
8. a kind of composite metal substrate, it is characterised in that it includes more than more than one pre-impregnated sheet as claimed in claim 7 successively
Carry out surface metal-clad, overlapping, pressing forms；
Preferably, the material of the surface metal-clad is the alloy of aluminium, copper, iron and its any combination；
Preferably, the composite metal substrate is but is not limited to CEM-1 copper-clad plates, CEM-3 copper-clad plates, FR-4 copper-clad plates, FR-5
Copper-clad plate, CEM-1 aluminium bases, CEM-3 aluminium bases, FR-4 aluminium bases or FR-5 aluminium bases.
9. a kind of wiring board, it is characterised in that formed in the Surface Machining circuit of the composite metal substrate described in claim 8.
10. a kind of plastic packaging material, it is characterised in that comprising composition epoxy resin as claimed in claim 4 or such as claim 6
The fire-retardant combination.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610523513.XA CN107573485A (en) | 2016-07-05 | 2016-07-05 | Phosphazene compound, curing agent, composition epoxy resin, pre-impregnated sheet and composite metal substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610523513.XA CN107573485A (en) | 2016-07-05 | 2016-07-05 | Phosphazene compound, curing agent, composition epoxy resin, pre-impregnated sheet and composite metal substrate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107573485A true CN107573485A (en) | 2018-01-12 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610523513.XA Pending CN107573485A (en) | 2016-07-05 | 2016-07-05 | Phosphazene compound, curing agent, composition epoxy resin, pre-impregnated sheet and composite metal substrate |
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| Country | Link |
|---|---|
| CN (1) | CN107573485A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1063252A1 (en) * | 1998-03-13 | 2000-12-27 | Otsuka Kagaku Kabushiki Kaisha | Flame-retardant resin, composition thereof, and process for producing the same |
| CN104403128A (en) * | 2014-10-30 | 2015-03-11 | 东北林业大学 | Phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant, preparation method of phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant, and flame-retardant epoxy resin prepared from phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant |
| CN105348563A (en) * | 2014-12-09 | 2016-02-24 | 广东广山新材料有限公司 | Flame-retardant compound, flame-retardant epoxy resin and flame-retardant composition |
-
2016
- 2016-07-05 CN CN201610523513.XA patent/CN107573485A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1063252A1 (en) * | 1998-03-13 | 2000-12-27 | Otsuka Kagaku Kabushiki Kaisha | Flame-retardant resin, composition thereof, and process for producing the same |
| CN104403128A (en) * | 2014-10-30 | 2015-03-11 | 东北林业大学 | Phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant, preparation method of phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant, and flame-retardant epoxy resin prepared from phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant |
| CN105348563A (en) * | 2014-12-09 | 2016-02-24 | 广东广山新材料有限公司 | Flame-retardant compound, flame-retardant epoxy resin and flame-retardant composition |
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| 卢林刚等: "单组份磷-氮膨胀阻燃剂的合成及成炭性能", 《高分子材料科学与工程》 * |
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