CN107573648A - Reactive phosphorus nitrile compound, curing agent and the sulfur-bearing phosphonitrile epoxy resin of sulfur-bearing - Google Patents
Reactive phosphorus nitrile compound, curing agent and the sulfur-bearing phosphonitrile epoxy resin of sulfur-bearing Download PDFInfo
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- CN107573648A CN107573648A CN201610523588.8A CN201610523588A CN107573648A CN 107573648 A CN107573648 A CN 107573648A CN 201610523588 A CN201610523588 A CN 201610523588A CN 107573648 A CN107573648 A CN 107573648A
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Abstract
The invention discloses the reactive phosphorus nitrile compound of sulfur-bearing, curing agent, sulfur-bearing phosphonitrile epoxy resin.The reactive phosphorus nitrile compound of the sulfur-bearing its there is structure shown in formula (I).The fire-retardant compound has good anti-flammability, and its solidfied material has good heat resistance, water resistance, cohesiveness and mechanical performance, electrical property.In addition, the phosphazene compound, which is applied to composite metal substrate and wiring board, can improve its anti-flammability, while economical and environmentally friendly friendly.
Description
Technical field
The present invention relates to the technical field of fire retardant matter, more particularly to the reactive phosphorus nitrile compound of sulfur-bearing, curing agent, contain
Sulphur phosphonitrile epoxy resin.
Background technology
The family such as the electronic products such as mobile phone, computer, video camera, electronic game machine, air-conditioning, refrigerator, television image, sound equipment articles for use
With, office electric equipment products and the various products that use of other field, for safety, it is required for possessing different degrees of anti-flammability
Energy.
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.
For the purpose of environmental protection, people replace chemical combination containing halogen using the not halogen-containing compound such as phosphorous, nitrogenous
Thing as fire retardant, particularly in electronics, electrically, on Electric Industrial, using the simple function with reactivity (in a molecule only
Have an active reactive group) flame-retardant composition, such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is (hereinafter referred to as
DOPO), it is more derivative compound using DOPO, addition or does not add aluminium hydroxide hydrate, magnesium hydroxide hydrate
To reach flame retardant effect.
In electronic applications, usually used DOPO and novolac type epoxy resin, o-cresol formaldehyde epoxy resin, bisphenol-A
The high cost such as phenol aldehyde type epoxy resin, the product (abbreviation DOPO epoxy resin) of polyfunctional epoxy resin reaction, as covering copper
The epoxide resin material of plate purposes.These use the copper-clad plate manufactured by DOPO epoxy resin, have good fire resistance, but
There is the defects of many in cohesiveness, heat resistance, processability etc., be not suitable for manufacturing high multilayer, the Gao Ke that modern communicationses need
By property, high cohesiveness, excellent machinability product.Simultaneously because cost is higher, it is unfavorable for spreading to the low costs such as mobile phone and disappears
The civil goods such as power-consuming son field.
With the further raising of people's multiple stratification, high reliability request short to electronic product, small, thin, high, civilian consumption
The factor such as the popularization of electronics and increasingly severeer pollution pressure, there is an urgent need to good anti-flammability, resistance in market
The copper-clad plate material of hot, good mechanical performance and dielectric properties.
The content of the invention
In view of this, one aspect of the present invention provides a kind of reactive phosphorus nitrile compound of sulfur-bearing, and the reactive phosphorus nitrilation closes
Thing has good flame-retardance, heat resistance, good mechanical performance.
A kind of reactive phosphorus nitrile compound of sulfur-bearing, it has the molecular structure as shown in formula (I)：
In formula (I), R2Arbitrary organic group is represented, Z is inertia nucleophilic group, and R is reactive nucleophilic group, and M is ring three
Phosphonitrile base M1, the phosphonitrile base M of ring more than four2Or non-annularity polyphosphazene base M3In it is a kind of or at least two combination；A be more than
Null integer, such as 1,2,3,4,5,6,7,8,9,10 or 11, b and c are the integer more than or equal to 1, for example, 1,2,3,
4th, 5,6,7,8,9,10,11,12 or 13, c be preferably greater than 2 integer；A, b and c threes sum is more than or equal to 6.
In the present invention, the arbitrary organic group, condition is that the specified atom is no more than normal valency, and is produced
Raw stable compound.Preferably, R2Represent substituted or unsubstituted straight chained alkyl or branched alkyl, substituted or unsubstituted ring
It is any one in alkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl
Kind or its at least two combination.
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.
It should hand over, in M1And M2In the expression of structural formula, there is symbolOnly to " ring-type "
A kind of signal of structure.M1、M2And M3InThe key connected on middle P atoms only represents substituent in three
Substitution occurs on P atoms, is not to be construed as the expression of methyl.
In the flame-retardant compound of the present invention, it should be understood that the group being connected with M is connected on M phosphorus atoms,
That is M1、M2And M3The side base on phosphorus atoms in structure.Further illustrate, M1、M2And M3Occur in structure on P atoms
Two singly-bounds are not to be construed as two methyl, and two singly-bounds are merely representative of M1、M2And M3Side base is connected by P atoms.M can be with
The phosphorus atoms of same position are connected, the phosphorus atoms of diverse location can also be connected.
Preferably, M includes at least 50wt% phosphonitrile base M of ring three1, at most 48wt% the phosphonitrile base M of ring more than four2And
At most 48wt% non-annularity polyphosphazene base 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 48wt%, that is, is referred to, M2Content can be 0~48wt%.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%, 17wt%, 20wt%, 23wt%, 26wt%, 29wt%, 32wt%, 35wt%, 38wt%,
42wt%, 45wt% or 48wt%.
In the present invention, M3Content is at most 48wt%, that is, is referred to, M3Content can be 0~48wt%.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%, 11wt%, 14wt%, 17wt%, 20wt%, 23wt%, 26wt%, 29wt%, 32wt%, 35wt%, 38wt%,
42wt%, 45wt% or 48wt%.
In the present invention, if M1Content is less than 50wt%, or M2More than 48wt%, then with the reacted life of epoxy resin
Heat resistance, water resistance and mechanical performance can be damaged in use into thing.If M3Content is more than 48%, then is reacted with epoxy resin
Product afterwards would be possible to cause inconvenient for use because viscosity is excessive in use, and because molecular weight is excessive make its performance
The bad result such as suffer damage.
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, the Z is the inertia nucleophilic group provided by nucleopilic reagent.In the present invention, the inertia parent
Core group refers to that the nucleophilic group does not have reactivity, refers specifically to, a kind of functional group, and it lives without common sense
Property group, it be not easy with the speed of a reality routine organic synthesis under conditions of reacted, be directed to the present invention
Phosphazene compound refers to, and reacts remaining by nucleopilic reagent and chloro phosphazene compound dehalogenation compound (such as NaCl, KCl, HCl)
, without common sense reactivity functional group.Nucleophilic is carried out for example with hydroquinones, obtains O-Ar-OH, Ar is benzene
Base, because remaining group O-Ar-OH has reactivity, therefore, it is not belonging to the inertia nucleophilic group of the present invention.
In the present invention, the nucleopilic reagent refers to, and the nucleopilic reagent of nucleophilic substitution can occur with halo phosphonitrile.
During nucleophilic substitution, nucleopilic reagent sloughs leaving group, the halogen atom in nucleophilic group attack halo phosphonitrile, parent
Core group is connected with M.Methanol CH is used for example, working as3When as nucleopilic reagent and halo phosphonitrile nucleophilic substitution occurs for OH,
CH3OH sloughs H+, methoxyl group CH3Halogen atom in O- substitution halo phosphonitriles, is connected, now Z is with-the P in phosphonitrile
CH3O-。
Preferably, R is selected from-OR14、-SR15、-C≡C-R6、-O-NO2,-I orIn any one or at least two combination；
R14、R15、R3、R4、R5、R6、R13、R16、R11And R12It independently is substituted or unsubstituted straight chained alkyl or side chain
Alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted alkoxy, substitution or not
Substituted alkyl sulfenyl, substituted or unsubstituted cycloalkyloxy, substituted or unsubstituted aralkoxy, substituted or unsubstituted alkane
Base aryloxy group, substituted or unsubstituted carbonate group, substituted or unsubstituted sulfonate group, substituted or unsubstituted phosphonate ester
Any one in base, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl.
In the present invention, the R is reactive nucleophilic group, and it refers to, a kind of functional group, and it carries active group, and it holds
Change places or reacted with the speed of a reality under conditions of the organic synthesis of routine, it is nucleopilic reagent and chloro phosphonitrile
The functional group of the remaining reaction containing common sense after compound nucleophilic substitution.
Preferably, the R is selected from-O-R20-OH、-O-R21-SH、-O-R22-NH-R23、-S-R24-OH、-S-R26-SH、-S-R28-NH-R29OrIn any one or at least two combination；
R20、R21、R22、R24、R25、R26、R27、R28And R30It independently is substituted or unsubstituted straight chained alkyl or side chain
Alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted alkoxy, substitution or not
Substituted alkyl sulfenyl, substituted or unsubstituted cycloalkyloxy, substituted or unsubstituted aralkoxy, substituted or unsubstituted alkane
Base aryloxy group, substituted or unsubstituted carbonate group, substituted or unsubstituted sulfonate group, substituted or unsubstituted phosphonate ester
Any one in base, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl, R23、R29And R31It independently is
Hydrogen atom, substituted or unsubstituted straight chained alkyl or branched alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted virtue
Alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkyl sulfenyl, substituted or unsubstituted cycloalkyloxy, substitution
Or unsubstituted aralkoxy, substituted or unsubstituted alkyl-aryloxy, substituted or unsubstituted carbonate group, substitution or do not take
The sulfonate group in generation, substituted or unsubstituted phosphonate group, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl
In any one.
In foregoing description, 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, preferably C1~C8 straight chains
Alkyl or branched alkyl, it is methyl when carbon number is C1, when carbon number is C2, as ethyl.
The substituted or unsubstituted cycloalkyl be preferably carbon number for C3~C12 (such as C4, C5, C6, C7, C8,
C9, C10 or C11) substituted or unsubstituted cycloalkyl.
Substituted or unsubstituted aryl is preferably phenyl, benzyl, 1,2,3,4- tetralyls,Deng.The example of phenyl includes
Xenyl, terphenyl, benzyl, phenethyl or phenylpropyl etc..
Substituted or unsubstituted heteroaryl is five yuan or six membered heteroaryl.
Substituted or unsubstituted alkoxy is C1-C12 (such as C1, C2, C3, C4, C5, C6, C7, C8, C9, C10 or C11)
Alkoxy.
Substituted or unsubstituted aralkyl is C7-C12 (such as C8, C9, C10 or C11) aralkyl.
Substituted or unsubstituted alkyl sulfenyl is C1-C8 (such as C1, C2, C3, C4, C5, C6, C7 or C8) alkyl sulfenyl.
Substituted or unsubstituted cycloalkyloxy is C3-C8 (such as C4, C5, C6, C7 or C8) cycloalkyloxy,
Substituted or unsubstituted aralkoxy is C7-C12 (such as C8, C9, C10 or C11) aralkoxy.
Substituted or unsubstituted alkyl-aryloxy is C7-C12 (such as C8, C9, C10 or C11) alkyl-aryloxy.
Preferably, the substituted or unsubstituted alkoxies of the R or aryloxy.
The example of alkoxy includes, but are not limited to methoxyl group, ethyoxyl, isopropoxy, propoxyl group, butoxy and penta oxygen
Base.Alkoxy grp can be substituted by substituents, as alkenyl, alkynyl, halogen, hydroxyl, alkyl carbonyl oxy, aryl-carbonyl oxygen,
Alkoxy carbonyloxy group, aryloxy group carbonyloxy group, carboxylate, alkyl-carbonyl, aryl carbonyl, alkoxy carbonyl, amino carbonyl, alkyl ammonia
Base carbonyl, dialkyl amino carbonyl, alkylthiocarbonyl, alkoxy, phosphate, phosphonate radical close, phosphinic acids root close, amino (including
Alkyl amino, dialkyl amido, arylamino, ammonia diaryl base and alkyl aryl amino), acylamino- (including alkyl-carbonyl ammonia
Base, aryl-amino-carbonyl, carbamoyl and urea groups), amidino groups, imino group, sulfydryl, alkylthio group, arylthio, carbothioic acid ester,
It is sulfuric ester, alkyl sulphinyl, sulfonic group, sulfamoyl, sulfonamido, nitromethyla, trifluoromethyl, cyano group, azido, miscellaneous
Ring group, alkylaryl or aromatics or heteroaromatic group.The example of the alkoxy grp of halogen substitution includes, but are not limited to a fluorine methoxy
Base, difluoro-methoxy, trifluoromethoxy, a chloromethane epoxide, dichloro methoxyl group, trichloromethoxy.
The example of the aryl oxide includes phenoxy group, benzyloxy, naphthoxy or biphenylyloxy, and the aryl oxide can be by alkane
Base etc. substitutes.
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, exemplary phosphazene compound be the phosphazene compound with following structure in any one or
The mixture of person at least two：
(OH-Ph-O)5-M-S-Ph、(OH-Ph-O)4-M-(S-CH3)2、(OH-Ph-O)4-M-(S-Ph)2、(OH-Ph-O
)3-M-(S-Ph)3、(OH-Ph-O)2-M-(S-Ph)4、
The reactive phosphorus nitrile compound of the present invention is by phosphonitrile chloride is entered with sulfhydryl compound with the nucleopilic reagent containing R
Obtained by row nucleophilic substitution.
Phosphonitrile chloride refers toSulfhydryl compound refers to：R2- SH, containing R
Nucleopilic reagent be the nucleopilic reagent containing reactive nucleophilic group, such as HO-Ar-OH.Pay attention to, above-mentioned R, Z, R2、M、a、b、c
As in the structural formula of reactive phosphorus nitrile compound.
In the nucleophilic substitution, chlorine is substituted by sulfhydryl compound, produces hydrogen chloride.Nucleophilic can use known in this field
Method prepare, 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 of necleophilic reaction has the metal chlorides such as zinc chloride, magnesium chloride, aluminium chloride, boron trifluoride and its complexing
The lewis bases such as thing, sodium hydroxide.These catalyst can one or more be used in mixed way, the present invention in have no special rule
It is fixed.Phosphonitrile chloride can use the most commonly used hexachlorocyclotriph,sphazene in source.The nucleopilic reagent containing Z group can first be used
Nucleophilic displacement of fluorine is carried out, nucleophilic displacement of fluorine is then carried out using sulfhydryl compound, parent is finally carried out using the nucleopilic reagent containing R group
Core substitutes, and nucleopilic reagent is commercially available or is obtained according to prior art.
Another aspect of the invention provides a kind of curing agent of epoxy resin, the epoxy resin cure obtained using the curing agent
Thing has good flame-retardance, heat resistance, the curing agent of good mechanical performance.
A kind of curing agent of epoxy resin, its part or be fully above-mentioned flame-retardant compound.
The curing agent of the present invention is limited without special flame-retardant compound content.Such as flame-retardant compound part composition solidification
Agent.In such cases, for the reactive group equivalents reacted using same epoxy resin to count, single aromatic ring phenolic group phosphorus-nitrogen compound accounts for curing agent
More than 30%, particularly preferably 55%~100%.It is understood that term " the reactive group equivalent reacted with same epoxy resin
Number is meter " refer to the relative usage of both reactive phosphorus nitrile compound, curing agent with both each contained by same epoxy resin it is anti-
The reactive group equivalents answered is the benchmark calculated.For the phosphazene compound containing mercapto, reactive group is phenolic hydroxyl group, rather than sulphur is former
Son.
Certainly in the case of forming curing agent in flame-retardant compound part, its other curing agent formed can use it is conventional with
The curing agent (being named as curing agent B) that epoxy resin uses.Curing agent B instantiation is free of the more phenolic group chemical combination of nitrogen to be not phosphorous
Thing, nitrogenous more phenol-based compounds, phosphorous more phenol-based compounds, nitrogenous phosphorous more phenol-based compounds, amine compound, benzoxazine
One kind in resin, acid anhydrides, polyacid and boron trifluoride and its complex compound or at least two.Here, amine compound is fat
Amine or aromatic amine, such as dicyandiamide, diethyl triamine, MDA, diaminodiphenylsulfone；More phenol-based compounds are double
Phenol A, Bisphenol F, bisphenol S, linear phenolic resin, o-cresol urea formaldehyde, one kind in bisphenol A phenolic resin or at least two.
Another aspect of the invention provides a kind of with good flame-retardance, heat resistance, the epoxy resin of good mechanical performance
Composition.
A kind of composition epoxy resin, include epoxy resin, and above-mentioned curing agent.
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 generally 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.Herein, it will be readily appreciated by those skilled in the art that when being necessary certainly, can also use alicyclic epoxy resin,
The relatively low epoxy resin of the ratio of viscosities such as chain type aliphatic type epoxy resin or ester formula epoxy resin, these epoxy resin can be independent
Using can also two or more be used together, the present invention has no special regulation to this, and the present invention is to these asphalt mixtures modified by epoxy resin
Fat proportioning amount it is also not specially provided, with reach ensure safe and environment-friendly and required performance on the premise of obtain purpose 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, sulfur-bearing 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 any two or more combinations.
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.
Auxiliary agent can be added into system according to being actually needed.Auxiliary agent can be it is general or special, as defoamer,
The materials such as coupling agent, toughener, levelling agent, releasing agent, toughener, the present invention are not spy to the species and addition of adding auxiliary agent
Other regulation, can be as needed, is defined by the safe and environment-friendly purpose thing that obtains.
In order to improve the fire resistance of composition epoxy resin, sulfur-bearing phosphonitrile ring can be increased in composition epoxy resin
Oxygen tree fat and fire-retarded epoxy resin.Fire-retarded epoxy resin content of halogen is preferred but is not limited to the epoxy not higher than 0.2%
Resin.The instantiation of fire-retarded epoxy resin be 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 contain
One kind in sulfur type epoxy resin or at least two.Sulfur-bearing phosphonitrile epoxy resin by the sulfur-bearing reactive phosphorus nitrile compound and ring
Oxygen tree fat is generated by condensation reaction, in view of the concrete technology of condensation reaction will be described below.
Further aspect of the present invention provides a kind of with good flame-retardance, heat resistance, the sulfur-bearing phosphonitrile of good mechanical performance
Epoxy resin.
A kind of sulfur-bearing phosphonitrile epoxy resin, it is by non-halogen epoxy resin and if above-mentioned reactive phosphorus nitrile compound is in ring
Under conditions of the epoxy radicals surplus of oxygen tree fat, 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 sulfur-bearing phosphonitrile epoxy resin solid content is 5~100% can be made, particularly preferred is that sulfur-bearing 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.
Another aspect of the invention provides 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 more phenolic group phosphorus azo-cycle oxygen epoxy resins described above.
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
The fatty amines such as base diphenyl-methane, diaminodiphenylsulfone or aromatic amine；Can also be two or more phenol-based compounds or
Contain in mixture, such as a molecule such as bisphenol-A, Bisphenol F, bisphenol S, linear phenolic resin, bisphenol A phenolic resin, benzo
Oxazine resin, acid anhydrides, polyacid, boron trifluoride and its complex compound etc., these epoxy curing agents can be used alone, also may be used
With two kinds or it is several be used in mixed way, usage amount generally contrast epoxy resin equivalent proportion 0.4~1.5 (eq) between.
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.
A kind of pre-impregnated sheet, it is impregnated with or is coated on base material by fire-retardant combination described above and forms.Base material can be glass
Fiber base material, polyester base material, polyimide base material, ceramic base material or carbon fiber base material etc..Here, it is impregnated with or is coated with specific
Process conditions are not particularly limited." bonding sheet " that " pre-impregnated sheet " is also well known to those skilled in the art.
A kind of composite metal substrate, it include more than one as above-mentioned pre-impregnated sheet carry out successively surface metal-clad it 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.
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.
A kind of plastic packaging material, it is by above-mentioned composition epoxy resin or such as above-mentioned fire-retardant combination.Can according to being actually needed,
Conventional functional stuffing is selected to be added according to the dosage of routine 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.
In the present invention, Ph is phenyl.
The reactive phosphorus nitrile compound of sulfur-bearing of the present invention has good anti-flammability, and its solidfied material has well heat-resisting
Property, water resistance, cohesiveness and mechanical performance, electrical property, be a kind of also fire-retardant with larger economy and environmentally friendly friendly
Material.The Tg of the copper-clad plate obtained using the fire-retardant compound can reach 152 DEG C and more than, T- peel strengths can reach
1.92kg/mm2More than and, interlaminar strength can reach 1.85kg/mm2More than and, saturated water absorption can reach 0.28% with
Under, heat decomposition temperature can reach 409 DEG C and more than, bending strength can reach 12.2kg/mm2More than and, flammability (UL-94) reaches
To V-0 ranks, dielectric constant is.
Embodiment
Technical scheme is further illustrated with reference to embodiment.
Embodiment 1
Phosphonitrile structural formula is as follows：
Wherein, M is ring
Three phosphonitriles, it is average on the phosphonitrile of ring three to be substituted by 5 bisphenol-A groups and 1 phenylsulfartyl group；
The phosphorus cyanogen 1mol of chlordene ring three, acetone 200ml, benzene are put into three mouthfuls of 2000ml glass reactors with agitating device
Mercaptan 1mol and bisphenol-A 5mol, stir, lead to nitrogen, while being warming up to 60 DEG C, 30% hydrogen-oxygen is instilled with 60min
Change sodium solution 414g, kept for 60 DEG C of temperature, 15 hours of stirring reaction.After reaction, with the moisture in physical method removal system,
The insoluble matter in removal system is refiltered, solvent in system is distilled, obtains flame-retardant compound.This purpose product is named
For A.
The low dielectric phosphazene compound of modification to obtaining carries out proton nmr spectra sign, as a result as follows：
1H NMR(CDCl3,500MHz):6.6~6.7,6.8~7.0,7.1~7.2 (benzene ring hydrogens), 1.60~1.70
(hydrogen on methyl), 5.0 (hydrogen on hydroxyl).
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, P-O-C key absworption peaks 1035cm-1, 1500~1600cm of phenyl ring skeleton vibrations-1, methyl stretching vibration peak
2850cm-1。
Using above-mentioned 300g A materials and 100g epoxide equivalents, the linear phenolic resin as 105g/eq is curing agent, with 150g
The linear phenolic epoxy resin that the liquid bisphenol A epoxy resin and 100g epoxide equivalents that epoxide equivalent is 187g/eq are 120g/eq
For epoxy resin, 0.06g 2-methylimidazole and the homogeneous wiring solution-forming of appropriate butanone stirring are being added, is being named as combination
The equivalent proportion of thing -1, epoxy resin and curing agent is 1.Then it is made using composition -1 according to general copper-clad plate production process
Meet the standard copper-clad plate sample of the standards such as national standard, UL, be named as a copper-clad plates, test the performance of a copper-clad plates, its result table-
Represented in 1.
Embodiment 2
Phosphazene compound structural formula is as follows：
Wherein, M is the phosphonitrile of ring four,
It is average on the phosphonitrile of ring four to be substituted by 5 bisphenol-A groups and 3 phenylsulfartyl groups；
The phosphorus cyanogen 1mol of chlordene ring four, acetone 200ml, benzene are put into three mouthfuls of 2000ml glass reactors with agitating device
Mercaptan 3mol and bisphenol-A 5mol, stir, lead to nitrogen, while being warming up to 60 DEG C, 30% hydrogen-oxygen is instilled with 60min
Change sodium solution 500g, kept for 60 DEG C of temperature, 15 hours of stirring reaction.After reaction, with the moisture in physical method removal system,
The insoluble matter in removal system is refiltered, solvent in system is distilled, obtains flame-retardant compound.This purpose product is named
For B.
The low dielectric phosphazene compound of modification to obtaining carries out proton nmr spectra sign, as a result as follows：
1H NMR(CDCl3,500MHz):6.6~6.7,6.8~7.0,7.1~7.2 (benzene ring hydrogens), 1.60~1.70
(hydrogen on methyl), 5.0 (hydrogen on hydroxyl).
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, P-O-C key absworption peaks 1035cm-1, 1500~1600cm of phenyl ring skeleton vibrations-1, methyl stretching vibration peak
2850cm-1。
Using above-mentioned 500g B substances and 100g epoxide equivalents, the linear phenolic resin as 105g/eq is curing agent, with 150g
The linear phenolic epoxy resin that the liquid bisphenol A epoxy resin and 100g epoxide equivalents that epoxide equivalent is 187g/eq are 120g/eq
For epoxy resin, 0.06g 2-methylimidazole and the homogeneous wiring solution-forming of appropriate butanone stirring are being added, is being named as combination
The equivalent proportion of thing -2, epoxy resin and curing agent is 1.Then it is made using composition -2 according to general copper-clad plate production process
Meet the standard copper-clad plate sample of the standards such as national standard, UL, be named as b copper-clad plates, test the performance of b copper-clad plates, its result table-
Represented in 1.
Embodiment 3
Phosphazene compound structural formula is as follows：
Wherein, M is the phosphonitrile of ring three, ring
It is average on three phosphonitriles to be substituted by 5 bisphenol-A groups and 1 phenylsulfartyl group；
The phosphorus cyanogen 1mol of chlordene ring three, acetone 200ml, uncle are put into three mouthfuls of 2000ml glass reactors with agitating device
Butanethiol 3mol and dimethyl bisphenol A 3mol, stir, lead to nitrogen, while 60 DEG C are warming up to, with 60min drops
Enter 30% sodium hydroxide solution 414g, kept for 60 DEG C of temperature, 15 hours of stirring reaction.After reaction, with physical method removing body
Moisture in system, the insoluble matter in removal system is refiltered, distill solvent in system, obtain flame-retardant compound 328g.Survey
The phenolic group equivalent for obtaining flame-retardant compound is 267g/eq.This purpose product is named as C.
The low dielectric phosphazene compound of modification to obtaining carries out proton nmr spectra sign, as a result as follows：
1H NMR(CDCl3,500MHz):6.6~6.7,6.8~7.0,7.1~7.2 (benzene ring hydrogens), 1.60~1.70
(hydrogen on methyl), 5.0 (hydrogen on hydroxyl).
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, P-O-C key absworption peaks 1035cm-1, 1500~1600cm of phenyl ring skeleton vibrations-1, methyl stretching vibration peak
2850cm-1。
Using above-mentioned 200g C materials and 100g epoxide equivalents, the linear phenolic resin as 105g/eq is curing agent, with 150g
The linear phenolic epoxy resin that the liquid bisphenol A epoxy resin and 100g epoxide equivalents that epoxide equivalent is 187g/eq are 120g/eq
For epoxy resin, 0.06g 2-methylimidazole and the homogeneous wiring solution-forming of appropriate butanone stirring are being added, is being named as combination
The equivalent proportion of thing -3, epoxy resin and curing agent is 1.Then it is made using composition -3 according to general copper-clad plate production process
Meet the standard copper-clad plate sample of the standards such as national standard, UL, be named as c copper-clad plates, test the performance of c copper-clad plates, its result table-
Represented in 1.
Embodiment 4
Phosphazene compound structural formula is as follows：
(OH-Ph-O)4-M-(S-CH2-CH3)2Wherein, M is the phosphonitrile of ring three, is averaged on the phosphonitrile of ring three by 4 hydroxy phenyls
Epoxide group and 1 methyl mercapto group group substitution；
The phosphorus cyanogen 1mol of chlordene ring three, acetone 200ml, second are put into three mouthfuls of 2000ml glass reactors with agitating device
Mercaptan 2mol and hydroquinones A 4mol, stir, lead to nitrogen, while being warming up to 60 DEG C, 30% is instilled with 60min
Sodium hydroxide solution 414g, kept for 60 DEG C of temperature, 15 hours of stirring reaction.After reaction, with physical method removal system
Moisture, the insoluble matter in removal system is refiltered, distill solvent in system.This purpose product is named as D.
Using above-mentioned 200g D materials and 100g epoxide equivalents, the linear phenolic resin as 105g/eq is curing agent, with 150g
The linear phenolic epoxy resin that the liquid bisphenol A epoxy resin and 100g epoxide equivalents that epoxide equivalent is 187g/eq are 120g/eq
For epoxy resin, 0.06g 2-methylimidazole and the homogeneous wiring solution-forming of appropriate butanone stirring are being added, is being named as combination
The equivalent proportion of thing -4, epoxy resin and curing agent is 1.Then it is made using composition -5 according to general copper-clad plate production process
Meet the standard copper-clad plate sample of the standards such as national standard, UL, be named as d copper-clad plates, test the performance of d copper-clad plates, its result table-
Represented in 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, the properties for covering copper e 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.The properties for covering copper f represent in table -1.
Embodiment and the test result of comparative example are as shown in following table -1：
The performance comparision of the various copper-clad plates of table -1
Table -1
Method of testing：
(1) water absorption rate
100mm × 100mm × 1.6mm sheet materials are placed in 105 DEG C of baking oven and dry 1h, weighs and is placed on after cooling
Boiling 120min under 105kPa vapour pressure, finally dries and weighs and calculate water absorption rate.
(2) glass transition temperature Tg
The width for preparing test sample is about 8-12mm, length 60mm, and measurement is set on the resistance to DMA Q800 that speed of Germany
Pattern is beam mode, scanning temperature be room temperature to 200 DEG C, read loss tangent maximum when corresponding temperature be the sample
Glass transition temperature Tg.
(3) bending strength
25.4mm × 63.5m sample is prepared, using its thickness of vernier caliper measurement, by the test of material universal testing machine
Pattern is adjusted to crooked test pattern, and setting spacing is 15.9mm, test speed 0.51mm/min, takes the flat of 3 parallel testings
Average, test temperature are respectively room temperature and 180 DEG C.
(4) peel strength determines
Copper-clad laminated board is cut into 100mm × 3mm test film, using anti-stripping instrument experimental rig, with speed 50.8mm/
Min carries out stripping layering to copper foil, tests the peel strength of copper foil and resin, the bonding between the bigger explanation resin of numerical value and copper foil
Power is better.
(5) flammability is tested according to standard ANSL UL94-1985.
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 detailed process equipment of the present invention and technological process by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, it is above-mentioned detailed not mean that the present invention has to rely on
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, selection of concrete mode etc., all fall within the present invention's
Within the scope of protection domain and disclosure.
Claims (11)
1. the reactive phosphorus nitrile compound of a kind of sulfur-bearing, it is characterised in that it has the molecular structure as shown in formula (I)：
In formula (I), R2Arbitrary organic group is represented, Z is inertia nucleophilic group, and R is reactive nucleophilic group, and M is the phosphonitrile base of ring three
M1, the phosphonitrile base M of ring more than four2Or non-annularity polyphosphazene base M3In one kind and its any combination；
A is the integer more than or equal to zero, and b and c are the integer more than or equal to 1, and a, b and c three sum are number of phosphorus atoms in M
2 times.
2. phosphazene compound as claimed in claim 1, it is characterised in that R2Represent substituted or unsubstituted straight chained alkyl or branch
Alkyl group, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted aryl or substitution or not
Any one in substituted heteroaryl or its at least two combination；
Preferably, Z is selected from-OR14、-SR15、-O-NO2,-I orIn any one or at least two combination；
R14、R15、R3、R4、R5、R6、R13、R16、R11And R12Independently be substituted or unsubstituted straight chained alkyl or branched alkyl,
It is substituted or unsubstituted cycloalkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted
Alkyl sulfenyl, substituted or unsubstituted cycloalkyloxy, substituted or unsubstituted aralkoxy, substituted or unsubstituted alkyl virtue oxygen
Base, substituted or unsubstituted carbonate group, substituted or unsubstituted sulfonate group, substituted or unsubstituted phosphonate group, substitution
Or any one in unsubstituted aryl or substituted or unsubstituted heteroaryl；
Preferably, the R is selected from-O-R20-OH、-O-R21-SH、-O-R22-NH-R23、-S-R24-OH、
-S-R26-SH、-S-R28-NH-R29OrIn
Any one or at least two combination；
R20、R21、R22、R24、R25、R26、R27、R28And R30Independently be substituted or unsubstituted straight chained alkyl or branched alkyl,
It is substituted or unsubstituted cycloalkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted
Alkyl sulfenyl, substituted or unsubstituted cycloalkyloxy, substituted or unsubstituted aralkoxy, substituted or unsubstituted alkyl virtue oxygen
Base, substituted or unsubstituted carbonate group, substituted or unsubstituted sulfonate group, substituted or unsubstituted phosphonate group, substitution
Or any one in unsubstituted aryl or substituted or unsubstituted heteroaryl, R23、R29And R31Independently be hydrogen atom,
Substituted or unsubstituted straight chained alkyl or branched alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aralkyl, take
Generation or unsubstituted alkoxy, substituted or unsubstituted alkyl sulfenyl, substituted or unsubstituted cycloalkyloxy, substitution or unsubstituted
Aralkoxy, substituted or unsubstituted alkyl-aryloxy, substituted or unsubstituted carbonate group, substituted or unsubstituted sulfonic acid
It is any in ester group, substituted or unsubstituted phosphonate group, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl
It is a kind of；
Preferably, the phosphazene compound is any one in the phosphazene compound with following structure or at least two
Mixture：
(OH-Ph-O)5-M-S-Ph、(OH-Ph-O)4-M-(S-CH3)2、(OH-Ph-O)4-M-(S-Ph)2、(OH-Ph-O)3-M-
(S-Ph)3、(OH-Ph-O)2-M-(S-Ph)4、
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.
3. reactive phosphorus nitrile compound according to claim 1, it is characterised in that M includes at least 50wt%M1, at most
30wt%M2And at most 45wt%M3；
Preferably, c is more than or equal to 2；
Preferably, R20For substituted or non-substituted phenyl ring, thick aromatic ring or more aromatic rings, more preferably di- phenyl ring, further
Preferably
A kind of 4. curing agent of epoxy resin, it is characterised in that what it was formed be partially or fully as claim 1~
One of 3 reactive phosphorus nitrile compounds；
Preferably, for the reactive group equivalents reacted using same epoxy resin to count, the reactive phosphorus nitrile compound accounts for curing agent
More than 30%, preferably 55%~100%；
Preferably, the curing agent also includes other curing agent, selected from not phosphorous without the more phenol-based compounds of nitrogen, nitrogenous more phenolic group
It is compound, phosphorous more phenol-based compounds, nitrogenous phosphorous more phenol-based compounds, amine compound, benzoxazine colophony, acid anhydrides, more
First acid and boron trifluoride and its one kind in complex compound or at least two combination；
Preferably, the amine compound is in dicyandiamide, diethyl triamine, MDA or diaminodiphenylsulfone
Any one or at least two combination；
Preferably, more phenol-based compounds are bisphenol-A, Bisphenol F, bisphenol S, linear phenolic resin, o-cresol aldehyde tree or double
One kind or at least two combination in phenol A phenolic resin.
5. a kind of composition epoxy resin, it is characterised in that include epoxy resin, and curing agent as claimed in claim 4；
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, also include and given birth to as the flame-retardant compound as described in one of claim 1-3 with epoxy resin by condensation reaction
Into more phenolic group phosphorus nitrogen epoxy resin, and other kinds of fire-retarded epoxy resin；
Preferably, the other kinds of fire-retarded epoxy resin content of halogen is not higher than 0.2%；
Preferably, the other kinds of fire-retarded epoxy resin 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, siliceous type ring
Oxygen tree fat and one kind in sulfur-type epoxy resin or at least two combination；
Preferably, also comprising 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；
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 500 times of epoxy resin gross mass；
Preferably, the composition epoxy resin also includes auxiliary agent, and the auxiliary agent is defoamer, coupling agent, toughener and levelling
One kind in agent or at least two.
A kind of 6. sulfur-bearing phosphonitrile epoxy resin, it is characterised in that be by non-halogen epoxy resin and as claims 1 to 3 it
The one reactive phosphorus nitrile compound is given birth under conditions of the epoxy radicals surplus of epoxy resin by reacting obtained epoxy resin
Into thing；
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 catalyst without catalyst or have；
Preferably, the catalyst is in imidazoles, triphenylphosphine and its derivative species, tertiary amines and quaternary ammonium salts catalyst
One kind is used alone or a variety of is used in mixed way；
Preferably, the dosage of the catalyst be reactive phosphorus nitrile compound quality 0.01~2.5%, 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 sulfur-bearing phosphonitrile epoxy resin solid content is 5~100%, further
Preferably sulfur-bearing 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；
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 of epoxy resin and acyclic isoprenoid type epoxy resin.
7. a kind of fire-retardant combination, it is characterised in that include sulfur-bearing phosphonitrile epoxy resin as claimed in claim 6；
Preferably, the epoxy fat resin with anti-flammability, curing agent, auxiliary agent, curing accelerator and halogen-free flame-retardance are also included
Filler；
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；
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；
Preferably, the amine compound is the fat such as dicyandiamide, diethyl triamine, MDA, diaminodiphenylsulfone
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 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；
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
One kind or at least two；
Preferably, the dosage of the filler is below the 500phr of epoxy resin gross mass；
Preferably, the auxiliary agent is the one or more in defoamer, coupling agent, toughener and levelling agent.
8. a kind of pre-impregnated sheet, it is characterised in that it is by composition epoxy resin as claimed in claim 5 or such as claim 7
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.
9. 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 8 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.
10. a kind of wiring board, it is characterised in that formed in the Surface Machining circuit of the composite metal substrate described in claim 9.
11. a kind of plastic packaging material, it is characterised in that comprising composition epoxy resin as claimed in claim 5 or such as claim 7
The fire-retardant combination.
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| CN201610523588.8A CN107573648A (en) | 2016-07-05 | 2016-07-05 | Reactive phosphorus nitrile compound, curing agent and the sulfur-bearing phosphonitrile epoxy resin of sulfur-bearing |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109467688A (en) * | 2018-09-17 | 2019-03-15 | 天津慧瑞科技有限公司 | A kind of phosphorus-nitrogen-flexible curing agent of boron synergistic high fire-retardance and its synthetic method |
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- 2016-07-05 CN CN201610523588.8A patent/CN107573648A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467688A (en) * | 2018-09-17 | 2019-03-15 | 天津慧瑞科技有限公司 | A kind of phosphorus-nitrogen-flexible curing agent of boron synergistic high fire-retardance and its synthetic method |
| CN109467688B (en) * | 2018-09-17 | 2021-01-15 | 天津慧瑞科技有限公司 | Phosphorus-nitrogen-boron synergistic high-flame-retardant flexible curing agent and synthesis method thereof |
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Application publication date: 20180112 |