CN107540712A - A kind of modified phosphazene compound, Preparation method and use - Google Patents
A kind of modified phosphazene compound, Preparation method and use Download PDFInfo
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- CN107540712A CN107540712A CN201610486961.7A CN201610486961A CN107540712A CN 107540712 A CN107540712 A CN 107540712A CN 201610486961 A CN201610486961 A CN 201610486961A CN 107540712 A CN107540712 A CN 107540712A
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- OYRGAMMTFYAZNI-UHFFFAOYSA-N C#[N+][NH+]([O-])O[N+](O)=O Chemical compound C#[N+][NH+]([O-])O[N+](O)=O OYRGAMMTFYAZNI-UHFFFAOYSA-N 0.000 description 1
Abstract
The present invention relates to a kind of modified phosphazene compound, the modified phosphazene compound has the structure shown in formula (I).The present invention accesses the group of coupling agent in phosphazene compound, phosphazene compound can be made while base material raising fire resistance is introduced, play the effect of coupling, increase the compatibility of phosphazene compound and base material, the defects of substrate stability that reduction is brought due to introducing fire retardant in the prior art is poor, and mechanical strength reduces.
Description
Technical field
The invention belongs to the technical field of fire retardant matter, more particularly to modification phosphazene compound containing coupling agent group,
Preparation method and the purposes on composite metal substrate.
Background technology
Using mobile phone, computer, video camera, electronic game machine as the electronic product of representative, with air-conditioning, refrigerator, television image, sound
The various products that articles for use etc. use for the family expenses of representative, office electric equipment products and other field are rung, for safety, significant portion
Product require that it possesses different degrees of fire resistance.
In order that product reaches required fire resistance or grade, traditional technology usually uses to be added into material system
Add the inorganic fire-retarded thing of such as class such as the metal hydroxides of aluminium hydroxide hydrate, magnesium hydroxide hydrate containing the crystallization water
Matter and into system material add such as brominated amount of brominated bisphenol A, brominated bisphenol a type epoxy resin it is higher or containing halogen
The higher organic chemicals of amount, in order to improve the anti-flammability of these organic chemicals for containing halogen, also usually in body
Such as antimony oxide is added in system to the disagreeableness inorganic chemistry fire retardant material of environment.
Due to using halogen-containing fire retardant matter, it can produce the noxious material such as two of no degradability or difficult degradation when burning
Dislike English class organic halogen chemical contamination environment, influence the mankind and animal health.
For the purpose of environmental protection, use is phosphorous, the not halogen-containing compound such as nitrogenous is made instead of halogen contained compound
For fire retardant, particularly on electronics, electric, Electric Industrial, (there was only one in a molecule using the simple function with reactivity
Individual active reactive group) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide hereinafter referred to as DOPO), it is more to use
DOPO derivative compound adds as flame-retardant composition or does not add aluminium hydroxide hydrate, magnesium hydroxide hydrate reaches resistance
The effect of combustion.
In electronic applications, usually used DOPO and novolac type epoxy resin, o-cresol formaldehyde epoxy resin, bisphenol-A
The product (abbreviation DOPO epoxy resin) of the high cost such as phenol aldehyde type epoxy resin, polyfunctional epoxy resin and DOPO reactions is extensive
Using the epoxide resin material as copper-clad plate purposes.
These have a good fire resistance using the copper-clad plate manufactured by DOPO epoxy resin, but cohesiveness, heat-resisting
Property, processability etc. the defects of many be present, be not suitable for high multilayer, high reliability, high cohesiveness that manufacture modern communicationses need, good
The needs of good processing characteristics, and due to high cost, it is unfavorable for spreading to the consumption that such as mobile phone requires low cost
The civil goods such as electronics field.
It is anti-usually using DOPO and such as bisphenol-A, Bisphenol F, phenolic resin, phenol, orthoresol etherate in electronic applications
It should be made and regard epoxy curing agent or anti-flammability thing containing phenolic compounds (general designation phosphorus containing phenolic resin) containing DOPO skeletons
Matter additive, using the fire retardant of the epoxide resin material as copper-clad plate purposes.
These use copper-clad plate of the phosphorus-containing phenolic aldehyde obtained by as part or all of flame-retardant composition, can reach fire-retardant
Purpose, but there is the defects of many in resistance to acids and bases, chemical proofing, cohesiveness, heat resistance, processability etc., be not suitable for system
The high multilayers of modern communicationses needs, high reliability, high cohesiveness, the needs of good processing characteristics are made, and due to high cost
The reason for, it is unfavorable for spreading to such as mobile phone and requires the civil goods fields such as the consumer electronics of low cost.
As electronic industry is to short, small, thin, high multiple stratification, the further raising of high reliability request, civilian consumer electronics
Popularization use and the requirement of the factor such as increasingly severeer pressure of environmental pollution, market has good there is an urgent need to material
Anti-flammability, heat resistance, the cheap anti-flammability material of good mechanical performance.
The content of the invention
In view of the shortcomings of the prior art, it is an object of the invention to provide a kind of modified phosphazene compound, the modified phosphorus
Nitrile compound has the structure shown in formula (I)：
In formula I, R is inertia nucleophilic group；
In
Any a kind；R’1、R’2、R’3、R’4、R’5、R’6、R’7、R’8、R’9、R’10、R’11、R’12、R’13、R’14、R’15、R’16、R’17、
R’18、R’19、R’20、R’21Or R '22It is each independently selected from H or arbitrary organic groups；
M is any a kind or at least two kinds of of combination in phosphazene compound；
A is the integer more than or equal to zero, such as 0,1,2,3,4,5,6,7,8,9,10,13,15 etc., b are more than or equal to 1
Integer, such as 2 times that 1,2,3,4,5,6,7,8,9,10,11,1,4,15 etc., b and a sum are number of phosphorus atoms in M；
X is oxygen atom.
The group of coupling agent is accessed in phosphazene compound, such as titanate esters, esters of silicon acis, zirconate or Aluminate, can be made
Phosphazene compound plays the effect of coupling, thus increases phosphazene compound and base while base material raising fire resistance is introduced
The compatibility of material (such as plastics, resin), the substrate stability that reduction is brought due to introducing fire retardant in the prior art is poor, machinery
The defects of intensity decreases.
In the present invention, so-called inertia nucleopilic reagent refers to that necleophilic reaction can be carried out first, secondly anti-in progress nucleophilic
After answering, after being substituted on phosphonitrile parent M (such as phosphonitrile of ring three, the phosphonitrile of ring four or linear phosphonitrile), no longer with reactivity
Group；So-called reactivity refers to carry out any reaction well known in the art, including nucleophilic displacement of fluorine, addition reaction, soda acid are anti-
Answer, esterification, displacement reaction etc..
The Ti of the present invention is element titanium, and Zr is element zirconium, and Si is elemental silicon, and Al is element aluminum.
Preferably, R of the present invention is selected from-OR14、-SR2、-C≡C-R6、-O-NO2、-I
OrIn any one or at least two combination.
Wherein, R14、R13、R2、R3、R4、R5、R6、R15、R11And R12Independently be substituted or unsubstituted straight chained alkyl or
Branched alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted alkoxy, substitution
Or unsubstituted alkyl sulfenyl, substituted or unsubstituted cycloalkyloxy, substituted or unsubstituted aralkoxy, substitution or unsubstituted
Alkyl-aryloxy, substituted or unsubstituted carbonate group, substituted or unsubstituted sulfonate group, substituted or unsubstituted phosphonic acids
Any one in ester group, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl.
Preferably, the M is selected from the cyclic phosphazene with formula (II) structure, or the linear phosphonitrile with formula (III) structure；
In formula (II) or formula (III), n1And n2It is each independently selected from 3~10 integer, n1It is preferred that 3 or 4, n2It is excellent
Select 5,6,7 or 8.
For M, it can select cyclic phosphazene, such as the phosphonitrile of ring three or/and the phosphonitrile of ring four, can also select linear phosphonitrile,
The linear phosphonitrile is using P=N as repeat unit, with hydrogen atom or methyl blocking；On the P atoms of the M, at least grafting-X-
Y, and R is alternatively grafted, realize the purpose of the Grafting-coupling Agent group on M.
It is preferred that the M is the phosphonitrile base M of ring three1, the phosphonitrile base M of ring four2Or non-annularity polyphosphazene base M3In any a kind or extremely
Few 2 kinds combination.
Preferably, the R '1、R’2、R’3、R’4、R’5、R’6、R’7、R’8、R’9、R’10、R’11、R’12、R’13、R’14、R
’15、R’16、R’17、R’18、R’19、R’20、R’21Or R '22It is each independently selected from H, substituted or unsubstituted C1~C20 hydrocarbon
Base carbonyl, substituted or unsubstituted C1~C20 alkenyl carbonyl, substituted or unsubstituted C1~C20 alkynylcarbonyl groups, substitution or
It is unsubstituted C3~C20 cycloalkane carbonyl, substituted or unsubstituted C6~C20 aromatic hydrocarbon carbonyl, substituted or unsubstituted
C1~C20 miscellaneous aromatic hydrocarbon carbonyl or substituted or unsubstituted C1~C20 hydrocarbyl amino carbonyl, preferably methyl carbonyl, ethyl
Carbonyl, propyl group carbonyl, butyl carbonyl, pentylcarbonyl, hexyl carbonyl, heptyl carbonyl, nonyl carbonyl, decyl carbonyl, carbon hendecyl
Carbonyl, carbon dodecyl carbonyl, carbon tritriacontyl carbonyl, carbon pentadecyl carbonyl, carbon octadecyl carbonyl, vinyl carbonyl, acetenyl carbonyl
Base, acrylic carbonyl, propinyl carbonyl, cyclobutenyl carbonyl, butynyl carbonyl, cyclohexyl-carbonyl, cyclopentylcarbonyl, suberyl carbonyl
Base, phenylcarbonyl group, tolyl carbonyl, ethylbenzene carbonyl, furyl carbonyl, PYRIDYLCARBONYL, methylpyrrole base carbonyl, amino second
Any a kind in base carbonyl, aminobutyl carbonyl, aminodecyl carbonyl and aminoheptyl carbonyl.
Preferably, the modified phosphazene compound be the modification phosphazene compound with following structure in any a kind or
At least two kinds of mixture of person：
In any a kind or at least two kinds of of combination.
The two of the object of the invention are to provide a kind of preparation method of the modification phosphazene compound as described in the first purpose, described
Method comprises the following steps：
By phosphonitrile chlorideNecleophilic reaction occurs with inertia nucleophilic raw material, substitutes the part chlorine atom on M
For R, continue to occur with H-X-Y or Na-X-Y afterwards, remaining chlorine atom on M is substituted by-X-Y；
Wherein, M, R, X and Y have the restriction scope as described in the first purpose.
Art technology is any it will be clearly understood that for phosphonitrile parent M, and it has more than one P atoms, each P atomic energy
2 side-chain radicals are enough grafted, during preparation, each phosphorus atoms substitution chance is almost identical, therefore, is reacting
Cheng Zhong, number and the position of substituent can not be controlled completely, therefore, the product being prepared often through methods described is
One mixture, but these mixtures are without departing from invention which is intended to be protected.
In order to facilitate the course of reaction is understood, it is as follows that spy enumerates nonrestrictive example：
By hexachlorocyclotriph,sphazeneNecleophilic reaction, the phosphorus of substitution chlordene ring three occurs with inertia nucleophilic raw material phenol
NitrileOn part chlorine atom be phenoxy group, Zhi HouyuContinue to occur,
By hexachlorocyclotriph,sphazeneUpper remaining chlorine atom is substituted by
In the above-mentioned methods, not can determine that phenoxy group andIt is substituted in the phosphorus of ring three
Which position of nitrile, it can not determine that any one phosphonitrile ring of ring three all instead of identical group, therefore, methods described obtains
Product be likely to be the mixture being made up of following product：
And the ratio of several each materials does not limit；In addition, it is unreacted to contain other in the mixture
The materials such as raw material, catalyst.
In the chemical constitution, substituent is not connected on some atom of the phosphonitrile of ring three, but has been drawn in ring three
In the ring of phosphonitrile, it is intended that on the premise of valence state demand is met, the substituent can be substituted in the optional position of the phosphonitrile of ring three.
The three of the object of the invention are to provide a kind of resin combination, include the modification phosphazene compound described in the first purpose.
The four of the object of the invention are to provide a kind of pre-impregnated sheet, and its resin combination as described in the third purpose is impregnated with or is coated on
Base material forms.
Preferably, the base material is fiberglass substrate, polyester base material, polyimide base material, ceramic base material or carbon fiber
Base material.
The five of the object of the invention are to provide a kind of composite metal substrate, and it includes more than one preimpregnation as described in the fourth purpose
Plate carries out surface metal-clad successively, 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 that CEM-1 copper-clad plates, CEM-3 copper-clad plates, FR-4 copper-clad plates, FR-5 cover copper
Plate, CEM-1 aluminium bases, CEM-3 aluminium bases, FR-4 aluminium bases or FR-5 aluminium bases.
The six of the object of the invention are to provide a kind of wiring board, in the Surface Machining of the composite metal substrate described in the fifth purpose
Circuit forms.
The seven of the object of the invention are to provide a kind of flexible copper-clad plate, the flexible copper-clad plate include more than one such as purpose it
Four pre-impregnated sheets and the copper foil for the pre-impregnated sheet one or both sides being overlying on after overlapping.
The eight of the object of the invention are to provide a kind of purposes of the modification phosphazene compound as described in the first purpose, the modification
Phosphazene compound is used for IC package version, HDI encapsulation version, Automobile Plate or copper-clad plate.
Compared with prior art, the present invention has the advantages that：
The present invention accesses the group of coupling agent in phosphazene compound, such as titanate esters, esters of silicon acis, zirconate or Aluminate,
Phosphazene compound can be made to play the effect of coupling while base material raising fire resistance is introduced, thus increase phosphonitrile chemical combination
The compatibility of thing and base material (such as plastics, resin), reduce the substrate stability brought in the prior art due to introducing fire retardant
Difference, mechanical strength reduce the defects of.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in understanding the present invention, is not construed as the concrete restriction to the present invention.
In order to facilitate description scheme and method, in the structural formula of compound prepared by embodiment of the present invention, do not mark
Go out particular location of the substituent on phosphonitrile parent, it is intended that any position can substitute the substituent；In addition, for implementing
The number of substituent in the structural formula of compound described in example, it also simply schematically show methods described and be prepared
Product, the quantity of its substituent are the average value of substituent in the product, and the product for being not offered as obtaining is a structure
Compound.
Embodiment 1
A kind of modified phosphazene compound, there is following structure：
Wherein, it is average by 3 phenoxy groups and 3 on the phosphonitrile of ring threeGroup substitutes；
Preparation method is：
Hexachlorocyclotriph,sphazene 1mol, acetone 200mL, benzene are put into three mouthfuls of 2000mL glass reactors with agitating device
Phenol sodium 3mol and3mol, stir, while leading to nitrogen, be warming up to 60 DEG C, use
60min instills 20% sodium hydroxide solution to pH value neutrality, is kept for 60 DEG C of temperature, 15 hours of stirring reaction.After reaction, thing is used
Inorganic constituents and moisture in the method removal system of reason, distill solvent in system, obtain being modified phosphazene compound, ester equivalent is
355g/eq。
Proton nmr spectra sign is carried out to obtained modification phosphazene compound, it is as a result as follows：
1H NMR(CDCl3,500MHz):6.7~6.8,7.0~7.15,6.8~6.9 (benzene ring hydrogens), 2.2~2.3,
1.25~1.35,1.55~1.6,0.95~1.02 (hydrogen on hexyl).
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, carbonyl absorption peak 3400 in ester~
3500cm-1With 1750~1800cm-1, 2800~2900cm of C-H absworption peaks-1。
Orthoresol of the epoxide equivalent as 200g/eq is added using above-mentioned modified phosphazene compound A 177g as coupling curing agent
Formaldehyde epoxy resin 100g, curing accelerator 2-methylimidazole 0.2g, prepares composition epoxy resin.Using the epoxy composite
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 for thing, is named as a and covers copper
Plate, tests the performance of a copper-clad plates, and its result represents in table -1.
Embodiment 2
A kind of modified phosphazene compound, there is following structure：
Wherein, it is average by 2 on the phosphonitrile of ring three
Individual Phenylmethoxy and 4Group substitutes；
Preparation method is：
Hexachlorocyclotriph,sphazene 1mol, acetone 200mL, benzene are put into three mouthfuls of 2000mL glass reactors with agitating device
Base sodium methoxide 2mol and4mol, stir, while leading to nitrogen, be warming up to 60 DEG C,
20% sodium hydroxide solution is instilled to pH value neutrality with 60min, is kept for 60 DEG C of temperature, 15 hours of stirring reaction.After reaction, use
Inorganic constituents and moisture in the method removal system of physics, distill solvent in system, obtain being modified phosphazene compound, ester equivalent
For 572g/eq.
Proton nmr spectra sign is carried out to obtained modification phosphazene compound, it is as a result as follows：
1H NMR(CDCl3,500MHz):7.15~7.23 (the benzene ring hydrogens of phenyl methyl oxygen), 4.75~4.83 (benzene
The hydrogen of the methylene of ylmethyl oxygen), 7.05~7.15 (hydrogen on the phenyl of benzoic ether), the 3.49 (methylene of benzoic ether
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, P-O-C key absworption peaks 1035cm-1, 1500~1600cm of phenyl ring skeleton vibrations-1, carbonyl absorption peak 3400 in ester~
3500cm-1With 1750~1800cm-1, 2800~2900cm of C-H absworption peaks-1。
Orthoresol of the epoxide equivalent as 200g/eq is added using above-mentioned modified phosphazene compound A 286g as coupling curing agent
Formaldehyde epoxy resin 100g, curing accelerator 2-methylimidazole 0.5g, prepares composition epoxy resin.Using the epoxy composite
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 for thing, is named as b and covers copper
Plate, tests the performance of b copper-clad plates, and its result represents in table -1.
Embodiment 3
A kind of modified phosphazene compound, there is following structure：
Wherein, it is average by 1 tert-butyl group on the phosphonitrile of ring three
Epoxide and 4Group substitutes；
Preparation method is：
Hexachlorocyclotriph,sphazene 1mol, acetone 200mL, uncle are put into three mouthfuls of 2000mL glass reactors with agitating device
Butyl sodium alkoxide 1mol and5mol, stir, while leading to nitrogen, be warming up to 60 DEG C, use 60min
It is neutral to pH value to instill 20% sodium hydroxide solution, is kept for 60 DEG C of temperature, 15 hours of stirring reaction.After reaction, with physics
Inorganic constituents and moisture in method removal system, distill solvent in system, obtain being modified phosphazene compound, ester equivalent is
305g/eq。
Proton nmr spectra sign is carried out to obtained modification phosphazene compound, it is as a result as follows：
1H NMR(CDCl3,500MHz):7.0~7.2 (the benzene ring hydrogens of benzoic ether), the 1.21 (methyl of the tert-butyl group
On hydrogen), 3.49 (hydrogen of the methylene of benzoic ether).
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, carbonyl absorption peak 3400 in ester~
3500cm-1With 1750~1800cm-1, 2800~2900cm of C-H absworption peaks-1。
Adjacent first of the epoxide equivalent as 200g/eq is added using above-mentioned modified phosphazene compound A 152.5g as coupling curing agent
Novolac epoxy resin 100g, curing accelerator 2-methylimidazole 0.2g, prepares composition epoxy resin.Using the epoxy resin group
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 for compound, is named as c and covers copper
Plate, tests the performance of c copper-clad plates, and its result represents in table -1.
Embodiment 4
A kind of modified phosphazene compound, there is following structure：
Wherein, it is average by 2 tolyls on the phosphonitrile of ring three
Epoxide and 6Group substitutes；
Preparation method is：
The phosphonitrile 1mol of eight chlorine ring four, acetone 300mL, first are put into three mouthfuls of 2000mL glass reactors with agitating device
Base sodium phenate 2mol and6mol, stir, while leading to nitrogen, be warming up to 60 DEG C, use 60min
It is neutral to pH value to instill 20% sodium hydroxide solution, is kept for 60 DEG C of temperature, 15 hours of stirring reaction.After reaction, with physics
Inorganic constituents and moisture in method removal system, distill solvent in system, obtain being modified phosphazene compound, ester equivalent is
335g/eq。
Proton nmr spectra sign is carried out to obtained modification phosphazene compound, it is as a result as follows：
1H NMR(CDCl3,500MHz):7.0~7.2 (the benzene ring hydrogens of benzoic ether), the 3.49 (Asias of benzoic ether
The hydrogen of methyl), 2.35 (hydrogen on the methyl of aminomethyl phenyl epoxide), 6.61,6.89 (hydrogen on the phenyl of aminomethyl phenyl epoxide).
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, carbonyl absorption peak 3400 in ester~
3500cm-1With 1750~1800cm-1, 2800~2900cm of C-H absworption peaks-1。
Orthoresol of the epoxide equivalent as 200g/eq is added using above-mentioned modified phosphazene compound A 167g as coupling curing agent
Formaldehyde epoxy resin 100g, curing accelerator 2-methylimidazole 0.2g, prepares composition epoxy resin.Using the epoxy composite
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 for thing, is named as d and covers copper
Plate, tests the performance of d copper-clad plates, and 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, use
Appropriate butanone is dissolved into solution, and with normal glass cloth, according to the preparation method of routine, it is 50% to cover copper to obtain resinous amount
Plate e, 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 used
Appropriate butanone is dissolved into solution, and with normal glass cloth, according to the preparation method of routine, it is 50% to cover copper to obtain resinous amount
Plate f.The properties for covering copper f represent in table -1.
Formula (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；
(6) dielectric constant and dielectric loss are tested according to standard ASTM D150 dielectric constants.
Embodiment 5
A kind of modified phosphazene compound, there is following structure：
Wherein, it is average by 3 tert-butyl groups on the phosphonitrile of ring three
Epoxide and 5Group substitutes；
Preparation method is：
The phosphonitrile 1mol of eight chlorine ring four, acetone 300mL, uncle are put into three mouthfuls of 2000mL glass reactors with agitating device
Butyl sodium alkoxide 2mol and6mol, stir, while leading to nitrogen, be warming up to 60 DEG C, use
60min instills 20% sodium hydroxide solution to pH value neutrality, is kept for 60 DEG C of temperature, 15 hours of stirring reaction.After reaction, thing is used
Inorganic constituents and moisture in the method removal system of reason, distill solvent in system, obtain being modified phosphazene compound, ester equivalent is
330g/eq。
Proton nmr spectra sign is carried out to obtained modification phosphazene compound, it is as a result as follows：
1H NMR(CDCl3,500MHz):1.21 (hydrogen in tert-butyl group epoxide), 1.06 (on the tert-butyl group of tertbutyl methyl
Hydrogen), 2.15 (hydrogen on the methyl of tertbutyl methyl).
The position of infrared spectrum characteristic peak：The characteristic absorption peak 1217cm- of P=N keys in phosphazene backbone1, in phosphazene backbone
P-N 874cm-1, P-O-C key absworption peaks 1035cm-1, 3400~3500cm- of carbonyl absorption peak in ester1With 1750~1800cm
-1, 2800~2900cm- of C-H absworption peaks1。
Using：A kind of engineering plastics, raw materials by weight portion include following component：
Preparation method is：Extruder blending extrusion is used after raw material is mixed according to formula rate, you can obtain engineering plastics；
The Tg (DSC) for the engineering plastics being prepared is 156 DEG C, saturated water absorption 0.3%, and 396 DEG C of heat decomposition temperature is curved
Qu Qiangdu 12.5kg/mm2, flammability (UL-94) is V-0.
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 (10)
1. a kind of modified phosphazene compound, it is characterised in that the modified phosphazene compound has the structure shown in formula (I)：
In formula I, R is inertia nucleophilic group；
In
Any a kind；R’1、R’2、R’3、R’4、R’5、R’6、R’7、R’8、R’9、R’10、R’11、R’12、R’13、R’14、R’15、R’16、R’17、
R’18、R’19、R’20、R’21Or R '22It is each independently selected from H or arbitrary organic groups；
M is any a kind or at least two kinds of of combination in phosphazene compound；
A is the integer more than or equal to zero, and b is the integer more than or equal to 1, b and a sums are 2 times of number of phosphorus atoms in M；
X is oxygen atom.
2. modified phosphazene compound as claimed in claim 1, it is characterised in that R is selected from-OR14、-SR2、-C
≡C-R6、-O-NO2,-I orIn any one or at least two combination；
R14、R13、R2、R3、R4、R5、R6、R15、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 M is selected from the cyclic phosphazene with formula (II) structure, or the linear phosphonitrile with formula (III) structure；
In formula (II) or formula (III), n1And n2It is each independently selected from 3~10 integer, n1It is preferred that 3 or 4, n2It is preferred that 5,6,
7 or 8；
It is preferred that the phosphonitrile base M of ring three1, the phosphonitrile base M of ring four2Or non-annularity polyphosphazene base M3In any a kind or at least two kinds of of combination；
Preferably, the R '1、R’2、R’3、R’4、R’5、R’6、R’7、R’8、R’9、R’10、R’11、R’12、R’13、R’14、R’15、R
’16、R’17、R’18、R’19、R’20、R’21Or R '22It is each independently selected from H, substituted or unsubstituted C1~C20 hydrocarbyl oxycarbonyl
Base, substituted or unsubstituted C1~C20 alkenyl carbonyl, substituted or unsubstituted C1~C20 alkynylcarbonyl groups, substitution do not take
C3~the C20 in generation cycloalkane carbonyl, substituted or unsubstituted C6~C20 aromatic hydrocarbon carbonyl, substituted or unsubstituted C1~
C20 miscellaneous aromatic hydrocarbon carbonyl or substituted or unsubstituted C1~C20 hydrocarbyl amino carbonyl, preferably methyl carbonyl, ethylcarbonyl group,
Propyl group carbonyl, butyl carbonyl, pentylcarbonyl, hexyl carbonyl, heptyl carbonyl, nonyl carbonyl, decyl carbonyl, carbon hendecyl carbonyl,
Carbon dodecyl carbonyl, carbon tritriacontyl carbonyl, carbon pentadecyl carbonyl, carbon octadecyl carbonyl, vinyl carbonyl, acetenyl carbonyl, third
Alkenyl carbonyl, propinyl carbonyl, cyclobutenyl carbonyl, butynyl carbonyl, cyclohexyl-carbonyl, cyclopentylcarbonyl, cycloheptylcarbonyl, benzene
Base carbonyl, tolyl carbonyl, ethylbenzene carbonyl, furyl carbonyl, PYRIDYLCARBONYL, methylpyrrole base carbonyl, amino-ethyl carbonyl
Any a kind in base, aminobutyl carbonyl, aminodecyl carbonyl and aminoheptyl carbonyl.
3. modified phosphazene compound as claimed in claim 1, it is characterised in that the modified phosphazene compound is with as follows
Any a kind in the modification phosphazene compound of structure or at least two kinds of mixtures：
In any a kind or at least two kinds of of combination.
A kind of 4. preparation method of modification phosphazene compound as described in one of claims 1 to 3, it is characterised in that the side
Method comprises the following steps：
By phosphonitrile chlorideNecleophilic reaction occurs with inertia nucleophilic raw material, it is R to substitute the part chlorine atom on M, it
Continue that nucleophilic displacement of fluorine occurs with H-X-Y or Na-X-Y afterwards, remaining chlorine atom on M is substituted by-X-Y；
Wherein, M, R, X and Y have the restriction scope as described in one of claims 1 to 3.
5. a kind of resin combination, it is characterised in that include the modification phosphazene compound described in one of claim 1-3.
A kind of 6. pre-impregnated sheet, it is characterised in that its be impregnated with or be coated on base material by resin combination as claimed in claim 5 and
Into；
Preferably, the base material is fiberglass substrate, polyester base material, polyimide base material, ceramic base material or carbon fiber base material.
7. a kind of composite metal substrate, it is characterised in that it includes more than one pre-impregnated sheet as claimed in claim 6 and carried out successively
Surface metal-clad, overlapping, pressing form；
Preferably, the material of the surface metal-clad is the alloy of aluminium, copper, iron and its any combination；
Preferably, the composite metal substrate be 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, FR-4 aluminium bases or FR-5 aluminium bases.
8. a kind of wiring board, it is characterised in that formed in the Surface Machining circuit of the composite metal substrate described in claim 7.
9. a kind of flexible copper-clad plate, it is characterised in that the flexible copper-clad plate includes more than one preimpregnation as claimed in claim 6
Plate and the copper foil for the pre-impregnated sheet one or both sides being overlying on after overlapping.
A kind of 10. purposes of modification phosphazene compound as described in one of claim 1-3, it is characterised in that the modified phosphorus
Nitrile compound is used for IC package version, HDI encapsulation version, Automobile Plate or copper-clad plate.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250147A (en) * | 2011-05-17 | 2011-11-23 | 北京理工大学 | Preparation method and application of cyclotriphosphazene containing silicon functional groups |
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2016
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250147A (en) * | 2011-05-17 | 2011-11-23 | 北京理工大学 | Preparation method and application of cyclotriphosphazene containing silicon functional groups |
Non-Patent Citations (1)
| Title |
|---|
| HARRY R. ALLCOCK ET AL.: "The Synthesis and Structure of Triphenylsiloxycyclotriphosphazenes", 《HETEROATOM CHEMISTRY》 * |
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