CN106916416A - A kind of phosphorous nitrogenous Halogenless fire retarded epoxy resin glue, prepreg and high temperature resistant halogen-free flame-retardant insulation fabric part - Google Patents
A kind of phosphorous nitrogenous Halogenless fire retarded epoxy resin glue, prepreg and high temperature resistant halogen-free flame-retardant insulation fabric part Download PDFInfo
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- CN106916416A CN106916416A CN201710242794.6A CN201710242794A CN106916416A CN 106916416 A CN106916416 A CN 106916416A CN 201710242794 A CN201710242794 A CN 201710242794A CN 106916416 A CN106916416 A CN 106916416A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B17/00—Insulators or insulating bodies characterised by their form
- H01B17/56—Insulating bodies
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B19/00—Apparatus or processes specially adapted for manufacturing insulators or insulating bodies
Abstract
The present invention relates to the phosphorous nitrogenous Halogenless fire retarded epoxy resin glue of one kind, prepreg and high temperature resistant halogen-free flame-retardant insulation fabric part, by weight, the composition of raw materials of the epoxide-resin glue includes following components：40~60 parts of phosphor-containing halogen-free epoxy resin；4.5~20 parts of Triallyl isocyanurate；4,4 ' 6~22.5 parts of BMI diphenyl-methanes；5~10.8 parts of curing agent；0.5~1.5 part of curing accelerator；0.5~1 part of colouring agent；10~25 parts of solvent.Prepreg, the insulation fabric part being made of epoxide-resin glue of the invention, with heat-resisting quantity（H grades）, anti-flammability can reach 0 grade of flame-retardant standard of UL94 V, and total halogen content is less than 500PPM, while having excellent electric property, mechanical performance, caking property and heat resistance.The insulation fabric part can further improve the H grades of fire resistance of laminate, its reliability for using be improved, the need for meeting domestic and international market.
Description
Technical field
The present invention relates to phosphorous nitrogenous Halogenless fire retarded epoxy resin glue of one kind and preparation method thereof, using the epoxide-resin glue
The prepreg and high temperature resistant halogen-free flame-retardant insulation fabric part of preparation.
Background technology
As electronic component power increases, whole machine packing density more and more higher, electronic installation fire casualty takes place frequently therewith,
In order to prevent fire from occurring, various electronic components all have to comply with fire safety requirement, in the material of composition insulation fabric part
In, glass fibre will not burn, therefore, to manufacture flame retardant type insulation fabric part must just add anti-flammability material in resin
Material, the element in the VIIth race is in itself or compound is respectively provided with certain fire resistance.Therefore, the resin containing halogen often turns into
Preferable flame resistance insulating materials base material.However, because the electron wastes containing halides are in decomposition and combustion process, can
Poisonous gas (bromine, hydrogen bromide, PBDF and many bromos two harmful and damage the ozone layer can be discharged
Benzoxazine etc.), so being also constantly subjected to the query of people.As a result of which, phosphorous or nitrogen-containing compound is used as fire-retardant
Agent substitution brominated flame-retardant has turned into a kind of new thinking.
A kind of phosphorous nitrogenous halogen-free flame retardant epoxy resin composition is disclosed such as Chinese patent CN1238422C and containing this group
The prepreg and laminate of compound, said composition include containing in a kind of epoxy resin of non-halogenated, a kind of product and molecule
There are the curing agent and curing accelerator of nitrogen, a kind of product is by least containing a P-H or P-C key in molecule
Phosphorus-containing compound with molecule at least containing one be selected from carbon-carbon double bond, epoxy bond, alcoholic hydroxyl, phenolic hydroxyl group, carbonyl, ammonia
The compound reaction of the functional group of base, cyanic acid ester group and NCO and obtain, said composition is phosphorous and nitrogen, does not also add times
What halogen or inorganic combustion inhibitor, said composition has preferable flame retardant type and electric property, but its mechanical performance is short of.
The content of the invention
The technical problems to be solved by the invention are to overcome the deficiencies in the prior art, there is provided a kind of improved phosphorous nitrogenous nothing
Halogen fire retarding epoxide resin glue and preparation method thereof.
The present invention also provides a kind of prepreg and high temperature resistant halogen-free flame-retardant insulation fabric part.
To solve above technical problem, the present invention is adopted the following technical scheme that：
A kind of phosphorous nitrogenous Halogenless fire retarded epoxy resin glue, by weight, the composition of raw materials bag of the epoxide-resin glue
Include following components：
According to the present invention, the phosphor-containing halogen-free epoxy resin can be that phosphorus content is a series of phosphorous more than or equal to 1.7wt.%
Halogenless fire retarded epoxy resin.
The phosphor-containing halogen-free fire retarding epoxide resin can be prepared by the following method and obtain, and the preparation method includes following step
Suddenly：
Weigh formula ratio DOPO (9,10-dihydro-oxa-10-phosph-aphenanthrene-10-oxide) and
Novolac epoxy resin F51 is stirred and gradually heated up in container, resin is fully dissolved, and is gradually heating to 160 DEG C of reactions
15min, is then cooled to 60 DEG C or so, adds appropriate solvent lysate, can obtain dark-brown phosphorous epoxy resin glue.
According to the present invention, the curing agent be not halogen-containing curing agent, including amine curing agent, acid anhydride type curing agent,
One or more in high score subclass curing agent of combination.
Preferably, the amine curing agent includes but is not limited to 950 curing agent, 954 curing agent, dimethylformamide, double
One or more in cyanamide, MDA (DDM), 4,4- DADPSs (DDS) etc..
According to the present invention, the curing accelerator is not halogen-containing curing accelerator, including tertiary amines, imidazoles, is had
One or more in machine phosphorus compound class curing accelerator of combination.
Preferably, during the tertiary amines curing accelerator includes but is not limited to benzyl dimethylamine (BDMA), triethanolamine etc.
One or more.
Preferably, the imidazoles curing accelerator includes but is not limited to 2-methylimidazole (2-MZ), 2- phenylimidazoles
One or more in (2PZ) etc..
Preferably, the organic phosphorus compound class curing accelerator includes but is not limited to triphenylphosphine etc..
According to the present invention, the colouring agent is pigment.The pigment is heatproof pigment.
According to the present invention, the solvent is the one kind or several in acetone, DMF, toluene, dimethylbenzene etc.
Kind.
A kind of preparation method of above-mentioned phosphorous nitrogenous Halogenless fire retarded epoxy resin glue, comprises the following steps：By phosphor-containing halogen-free
Epoxy resin, Triallyl isocyanurate and 4,4 '-BMI diphenyl-methane stirred under the conditions of 90~100 DEG C to
It is uniformly dispersed, is subsequently adding curing agent and curing accelerator is well mixed, be cooled to 40~50 DEG C, adds colouring agent and solvent to stir
Mix uniform, obtain final product the phosphorous nitrogenous Halogenless fire retarded epoxy resin glue.
Preferably, it is 1~2 hour to be set forth in the mixing time stirred under the conditions of 90~100 DEG C.
In the present invention, all described in raw material can not have by commercially available and/or take known means to prepare
When being illustrated, the requirement of standard chemical products is satisfied by.
Another technical scheme that the present invention takes is：A kind of prepreg, is impregnated or coating glue by base material, is then dried
Form, the glue includes above-mentioned phosphorous nitrogenous Halogenless fire retarded epoxy resin glue.
Preferably, the base material includes alkali-free glass fiber cloth.If thickness is 0.14mm, nominal weight 160g/m2Nothing
Alkali containing glass fibre cloth.
It is highly preferred that the alkali-free glass fiber cloth is through the alkali-free glass fiber cloth of silane treatment.
Preferably, the phosphorous nitrogenous dried quality of Halogenless fire retarded epoxy resin glue accounts for the prepreg gross mass
40% ± 5%.It is highly preferred that the phosphorous nitrogenous dried quality of Halogenless fire retarded epoxy resin glue accounts for the prepreg
The 40% ± 1% of gross mass.
Preferably, before the phosphorous nitrogenous Halogenless fire retarded epoxy resin glue is used to impregnate or coat, will be described phosphorous nitrogenous
The solid content of Halogenless fire retarded epoxy resin glue is adjusted to 70% ± 5%, 23 DEG C of 1 DEG C of scholars, applies 4 glasss of viscosity in 60~80s.
According to a preferred aspect of the present invention, the prepreg is prepared by the following method and obtains：Base material is impregnated
In phosphorous nitrogenous Halogenless fire retarded epoxy resin glue, the base material after impregnation is dried to described under the conditions of 120~150 DEG C and phosphorous contained
Nitrogen Halogenless fire retarded epoxy resin glue is in semi-cured state, obtains final product the prepreg.
The another technical scheme that the present invention takes is：A kind of high temperature resistant halogen-free flame-retardant insulation fabric part, by above-mentioned semi-solid preparation
Piece compacting is formed.
Preferably, the structural member is formed by a prepreg compacting or folded by prepreg more than one described
Compacting is formed after putting.
A kind of preparation method of above-mentioned high temperature resistant halogen-free flame-retardant insulation fabric part, comprises the following steps：
(1) preparation of phosphorous nitrogenous Halogenless fire retarded epoxy resin glue：By phosphor-containing halogen-free epoxy resin, triallyl isocyanide urea
Acid esters and 4,4 '-BMI diphenyl-methane is stirred under the conditions of 90~100 DEG C to being uniformly dispersed, and is subsequently adding curing agent
It is well mixed with curing accelerator, 40~50 DEG C are cooled to, add colouring agent and stirring solvent uniform, obtain final product described phosphorous nitrogenous
Halogenless fire retarded epoxy resin glue；
(2) preparation of prepreg：During base material impregnated in into phosphorous nitrogenous Halogenless fire retarded epoxy resin glue, the base after impregnation
Material is dried to the phosphorous nitrogenous Halogenless fire retarded epoxy resin glue in semi-cured state under the conditions of 120~150 DEG C, is obtained final product described
Prepreg；
(3) preparation of structural member：Prepreg is cut into the size of needs, a prepreg is then positioned over mould
Suppressed in tool or compacting in mould is positioned over after more than one prepreg is stacked, cool down molding, sizing is then placed into
Dried 4~6 hours under the conditions of 160~l80 DEG C, obtain final product the structural member, wherein 200~230 DEG C of the temperature suppressed in the mould,
Pressure is 10~14MPa, the time is 0.5~1.5 hour.
Due to the implementation of above-mentioned technical proposal, the present invention has the following advantages that compared with prior art：
The phosphorous nitrogenous Halogen of epoxide-resin glue of the invention, Triallyl isocyanurate and 4,4 '-BMI
The addition of diphenyl-methane coordinates other raw material components to improve the performances such as the mechanical performance and electric property of epoxide-resin glue.Using
Prepreg, insulation fabric part that epoxide-resin glue of the invention is made, with heat-resisting quantity (H grades), anti-flammability can reach
UL94V-0 grades of flame-retardant standard, total halogen content is less than 500PPM, while having excellent electric property, mechanical performance, caking property
And heat resistance.The insulation fabric part can further improve the H grades of fire resistance of laminate, improve its reliability for using, and meet
The need for domestic and international market.
Specific embodiment
The present invention is described further below by specific embodiment.
Embodiment 1
The present embodiment provides a kind of phosphorous nitrogenous Halogenless fire retarded epoxy resin glue, and composition of raw materials is referring to table 1, and this is phosphorous nitrogenous
Step is prepared Halogenless fire retarded epoxy resin glue by the following method：The phosphor-containing halogen-free epoxy resin of the mass parts of precise 40
In equipped with motor mechanical agitator, electroheat pair, the reactor of reflux condenser, agitator is opened, open electroheat pair heating
Epoxy resin temperature is maintained at 100 DEG C, the Triallyl isocyanurate (TAIC) and 12 of 20 mass parts is sequentially added afterwards
The 4 of mass parts, 4 '-BMI diphenyl-methane (BMI), persistently stir 1h, until being uniformly dispersed.It is then slowly added to
950 curing agent of 7.2 mass parts, the 2PZ of 1 mass parts, then 2h is persistently stirred, make curing agent and curing accelerator fully dispersed
It is even.After being cooled to 40 DEG C, No. 50 green pigments of 0.8 mass parts and the acetone of 19 mass parts are added, then be sufficiently stirred for 30min.
After cooling, barrelling is filtered, obtain final product phosphorous nitrogenous Halogenless fire retarded epoxy resin glue.
The phosphorous nitrogenous Halogenless fire retarded epoxy resin glue of the present embodiment is used to prepare prepreg, the prepreg passes through
Following methods are prepared：
(1) it contains admittedly to take the sample test of a small amount of phosphorous nitrogenous Halogenless fire retarded epoxy resin glue, fine-tuning according to test result
The solid content of above-mentioned glue is between 70% ± 5%；Its viscosity is further measured, makes it at 23 DEG C of 1 DEG C of scholars, apply 4 glasss viscous
Degree is between 60~80s.
(2) from the thickness after silane treatment for the alkali-free glass fiber cloth of 0.14mm impregnated in phosphorous nitrogenous halogen-free flameproof
In epoxide-resin glue, the fiber cloth after impregnation toasts 15min at 130 DEG C, most solvent is volatilized, and controls the resin glue of fabric
Content is obtained prepreg in 40% ± l% or so.
Obtained prepreg is used to prepare insulation fabric part, the structural member is prepared by the following method and obtains：By mould
Tool is preheated in advance, and prepreg obtained above size as required is carried, then thickness overlapping on demand, is positioned over
Preheat and be covered with the mould of heatproof barrier film, one layer of barrier film is repaved on the prepreg for stacking, then matched moulds compacting,
Progressively temperature-pressure, until temperature is raised to 220 DEG C, applying pressure is 12MPa, is persistently incubated l h.Power supply is then turned off, is led to cold
But by mould fast cooling, molding when mold temperature is cooled to below 100 DEG C is then charged into being shaped in special product box water,
Its cooling strain is prevented, 5h in 170 DEG C of baking ovens is then put in.
Embodiment 2
The present embodiment provides a kind of phosphorous nitrogenous Halogenless fire retarded epoxy resin glue, and composition of raw materials is referring to table 1, and this is phosphorous nitrogenous
Step is prepared Halogenless fire retarded epoxy resin glue by the following method：The phosphor-containing halogen-free epoxy resin of the mass parts of precise 50
In equipped with motor mechanical agitator, electroheat pair, the reactor of reflux condenser, agitator is opened, open electroheat pair heating
Epoxy resin temperature is maintained at 90 DEG C, the TAIC of the 15 mass parts and BMI of 7 mass parts sequentially added afterwards, persistently stir 2h,
Until being uniformly dispersed.950 curing agent of 7.2 mass parts, the 2PZ of 1 mass parts are then slowly added to, then persistently stir 1h, made solid
Agent and curing accelerator are fully dispersed uniform.After being cooled to 50 DEG C, No. 50 green pigments and 19 mass of 0.8 mass parts are added
The acetone of part, then it is sufficiently stirred for 30min.After cooling, barrelling is filtered, obtain final product phosphorous nitrogenous Halogenless fire retarded epoxy resin glue.
The phosphorous nitrogenous Halogenless fire retarded epoxy resin glue that the present embodiment is prepared is used to prepare prepreg and insulation
The preparation method of structural member, prepreg and insulation fabric part is referring to embodiment 1.
Embodiment 3
The present embodiment provides a kind of phosphorous nitrogenous Halogenless fire retarded epoxy resin glue, and composition of raw materials is referring to table 1, and this is phosphorous nitrogenous
Step is prepared Halogenless fire retarded epoxy resin glue by the following method：The phosphor-containing halogen-free epoxy resin of the mass parts of precise 60
In equipped with motor mechanical agitator, electroheat pair, the reactor of reflux condenser, agitator is opened, open electroheat pair heating
Epoxy resin temperature is maintained at 90 DEG C, the TAIC of the 6 mass parts and BMI of 6 mass parts is sequentially added afterwards, lasting stirring
1.5h, until being uniformly dispersed.950 curing agent of 7.2 mass parts, the 2PZ of 1 mass parts are then slowly added to, then are persistently stirred
1.5h, makes curing agent and curing accelerator fully dispersed uniform.After being cooled to 45 DEG C, No. 50 green face of 0.8 mass parts are added
The acetone of material and 19 mass parts, then it is sufficiently stirred for 30min.After cooling, barrelling is filtered, obtain final product phosphorous nitrogenous halogen-free flameproof asphalt mixtures modified by epoxy resin
Fat glue.
The phosphorous nitrogenous Halogenless fire retarded epoxy resin glue that the present embodiment is prepared is used to prepare prepreg and insulation
The preparation method of structural member, prepreg and insulation fabric part is referring to embodiment 1.
Embodiment 4
The present embodiment provides a kind of phosphorous nitrogenous Halogenless fire retarded epoxy resin glue, and composition of raw materials is referring to table 1, and this is phosphorous nitrogenous
Step is prepared Halogenless fire retarded epoxy resin glue by the following method：The phosphor-containing halogen-free epoxy resin of the mass parts of precise 45
In equipped with motor mechanical agitator, electroheat pair, the reactor of reflux condenser, agitator is opened, open electroheat pair heating
Epoxy resin temperature is maintained between 95 DEG C, the TAIC of the 13.5 mass parts and BMI of 13.5 mass parts is sequentially added afterwards, hold
Continuous stirring 1h, until being uniformly dispersed.950 curing agent of 7.2 mass parts, the 2PZ of 1 mass parts are then slowly added to, then are persistently stirred
2h is mixed, makes curing agent and curing accelerator fully dispersed uniform.After being cooled to 50 DEG C, No. 50 green face of 0.8 mass parts are added
The acetone of material and 19 mass parts, then it is sufficiently stirred for 30min.After cooling, barrelling is filtered, obtain final product phosphorous nitrogenous halogen-free flameproof asphalt mixtures modified by epoxy resin
Fat glue.
The phosphorous nitrogenous Halogenless fire retarded epoxy resin glue that the present embodiment is prepared is used to prepare prepreg and insulation
The preparation method of structural member, prepreg and insulation fabric part is referring to embodiment 1.
Embodiment 5
The present embodiment provides a kind of phosphorous nitrogenous Halogenless fire retarded epoxy resin glue, and composition of raw materials is referring to table 1, and this is phosphorous nitrogenous
Step is prepared Halogenless fire retarded epoxy resin glue by the following method：The phosphor-containing halogen-free epoxy resin of the mass parts of precise 45
In equipped with motor mechanical agitator, electroheat pair, the reactor of reflux condenser, agitator is opened, open electroheat pair heating
Epoxy resin temperature is maintained at 90 DEG C, the TAIC of the 4.5 mass parts and BMI of 22.5 mass parts is sequentially added afterwards, persistently stir
2h is mixed, until being uniformly dispersed.950 curing agent of 7.2 mass parts, the 2PZ of 1 mass parts are then slowly added to, then persistently stir 1h,
Make curing agent and curing accelerator fully dispersed uniform.After being cooled to 50 DEG C, No. 50 green pigments and 19 of 0.8 mass parts are added
The acetone of mass parts, then it is sufficiently stirred for 30min.After cooling, barrelling is filtered, obtain final product phosphorous nitrogenous Halogenless fire retarded epoxy resin glue.
The phosphorous nitrogenous Halogenless fire retarded epoxy resin glue that the present embodiment is prepared is used to prepare prepreg and insulation
The preparation method of structural member, prepreg and insulation fabric part is referring to embodiment 1.
Embodiment 6
The present embodiment provides a kind of phosphorous nitrogenous Halogenless fire retarded epoxy resin glue, composition of raw materials referring to table 1, the epoxy resin
Step is prepared glue by the following method：The phosphor-containing halogen-free epoxy resin of the mass parts of precise 45 is in equipped with motor machinery
In agitator, electroheat pair, the reactor of reflux condenser, agitator is opened, be set to certain rotating speed stirring, opened electroheat pair and add
Heat makes epoxy resin temperature be maintained between 95 DEG C, and the TAIC of the 4.5 mass parts and BMI of 22.5 mass parts is sequentially added afterwards,
1.5h is persistently stirred, until being uniformly dispersed.The DDM of 7.2 mass parts, the 2PZ of 1 mass parts are then slowly added to, then are persistently stirred
1.5h, makes curing agent and curing accelerator fully dispersed uniform.After being cooled to 50 DEG C, No. 50 green face of 0.8 mass parts are added
The acetone of material and 19 mass parts, then it is sufficiently stirred for 30min.After cooling, barrelling is filtered, obtain final product phosphorous nitrogenous halogen-free flameproof asphalt mixtures modified by epoxy resin
Fat glue.
The phosphorous nitrogenous Halogenless fire retarded epoxy resin glue that the present embodiment is prepared is used to prepare prepreg and structure
The preparation method of part, prepreg and structural member is referring to embodiment 1.
Embodiment 7
The present embodiment provides a kind of phosphorous nitrogenous Halogenless fire retarded epoxy resin glue, composition of raw materials referring to table 1, the epoxy resin
Step is prepared glue by the following method：The phosphor-containing halogen-free epoxy resin of the mass parts of precise 45 is in equipped with motor machinery
In agitator, electroheat pair, the reactor of reflux condenser, agitator is opened, be set to certain rotating speed stirring, opened electroheat pair and add
Heat makes epoxy resin temperature be maintained at 100 DEG C, and the TAIC of the 4.5 mass parts and BMI of 22.5 mass parts is sequentially added afterwards, continues
Stirring 1h, until being uniformly dispersed.The dicyandiamide of 7.2 mass parts, the 2PZ of 1 mass parts are then slowly added to, then persistently stir 1h,
Make curing agent and curing accelerator fully dispersed uniform.After being cooled to 40 DEG C, No. 50 green pigments and 19 of 0.8 mass parts are added
The acetone of mass parts, then it is sufficiently stirred for 30min.After cooling, barrelling is filtered, obtain final product phosphorous nitrogenous Halogenless fire retarded epoxy resin glue.
The phosphorous nitrogenous Halogenless fire retarded epoxy resin glue that the present embodiment is prepared is used to prepare prepreg and structure
The preparation method of part, prepreg and structural member is referring to embodiment 1.
Embodiment 8
The present embodiment provides a kind of phosphorous nitrogenous Halogenless fire retarded epoxy resin glue, composition of raw materials referring to table 1, the epoxy resin
Step is prepared glue by the following method：The phosphor-containing halogen-free epoxy resin of the mass parts of precise 45 is in equipped with motor machinery
In agitator, electroheat pair, the reactor of reflux condenser, agitator is opened, be set to certain rotating speed stirring, opened electroheat pair and add
Heat makes epoxy resin temperature be maintained at 100 DEG C, and the TAIC of the 4.5 mass parts and BMI of 22.5 mass parts is sequentially added afterwards, continues
Stirring 2h, until being uniformly dispersed.It is then slowly added to 950 curing agent and 3.6DDM of 7.2 mass parts, the 2PZ of 1 mass parts, then
1h is persistently stirred, makes curing agent and curing accelerator fully dispersed uniform.After being cooled to 50 DEG C, the 50 of 0.8 mass parts are added
The acetone of number green pigment and 19 mass parts, then it is sufficiently stirred for 30min.After cooling, barrelling is filtered, obtain final product phosphorous nitrogenous halogen-free flameproof
Epoxide-resin glue.
The phosphorous nitrogenous Halogenless fire retarded epoxy resin glue that the present embodiment is prepared is used to prepare prepreg and structure
The preparation method of part, prepreg and structural member is referring to embodiment 1.
Embodiment 9
The present embodiment provides a kind of phosphorous nitrogenous Halogenless fire retarded epoxy resin glue, composition of raw materials referring to table 1, the epoxy resin
Step is prepared glue by the following method：The phosphor-containing halogen-free epoxy resin of the mass parts of precise 45 is in equipped with motor machinery
In agitator, electroheat pair, the reactor of reflux condenser, agitator is opened, be set to certain rotating speed stirring, opened electroheat pair and add
Heat makes epoxy resin temperature be maintained at 90 DEG C, and the TAIC of the 4.5 mass parts and BMI of 22.5 mass parts is sequentially added afterwards, continues
Stirring 1.2h, until being uniformly dispersed.950 curing agent and 3.6 dicyandiamides of 7.2 mass parts are then slowly added to, 1 mass parts
2PZ, then 1.8h is persistently stirred, make curing agent and curing accelerator fully dispersed uniform.After being cooled to 42 DEG C, 0.8 matter is added
No. 50 green pigments of part and the acetone of 19 mass parts are measured, then is sufficiently stirred for 30min.After cooling, barrelling is filtered, obtained final product phosphorous nitrogenous
Halogenless fire retarded epoxy resin glue.
The phosphorous nitrogenous Halogenless fire retarded epoxy resin glue that the present embodiment is prepared is used to prepare prepreg and structure
The preparation method of part, prepreg and structural member is referring to embodiment 1.
Comparative example 1
This comparative example provides a kind of phosphorous nitrogenous Halogenless fire retarded epoxy resin glue, and composition of raw materials does not add referring to table 1 in formula
Plus 4,4 '-BMI diphenyl-methane, other are with embodiment 1.
The phosphorous nitrogenous Halogenless fire retarded epoxy resin glue that this comparative example is prepared is used to prepare prepreg and structure
The preparation method of part, prepreg and structural member is referring to embodiment 1.
Comparative example 2
This comparative example provides a kind of phosphorous nitrogenous Halogenless fire retarded epoxy resin glue, and composition of raw materials does not add referring to table 1 in formula
Plus 4,4 '-BMI diphenyl-methane and Triallyl isocyanurate, other are with embodiment 1.
The phosphorous nitrogenous Halogenless fire retarded epoxy resin glue that this comparative example is prepared is used to prepare prepreg and structure
The preparation method of part, prepreg and structural member is referring to embodiment 1.
Comparative example 3
This comparative example provides a kind of phosphorous nitrogenous Halogenless fire retarded epoxy resin glue, and composition of raw materials does not add referring to table 1 in formula
Plus Triallyl isocyanurate, other are with embodiment 1.
The phosphorous nitrogenous Halogenless fire retarded epoxy resin glue that this comparative example is prepared is used to prepare prepreg and structure
The preparation method of part, prepreg and structural member is referring to embodiment 1.
Table 1 is the composition of raw materials of the phosphorous nitrogenous Halogenless fire retarded epoxy resin glue of embodiment 1~9 and comparative example 1~3
The structural member that embodiment 1~9 and comparative example 1~3 are prepared is carried out into measuring mechanical property, electric property to survey
Examination, physicochemical property test, as a result as shown in table 2~7.
Table 2 is the measuring mechanical property result of the structural member that embodiment 1~9 is prepared
Table 3 is the measuring mechanical property result of the structural member that comparative example 1~3 is prepared
Table 4 is the electric performance test result of the structural member that embodiment 1~9 is prepared
Table 5 is the electric performance test result of the structural member that comparative example 1~3 is prepared
Table 6 is the hot property and physicochemical property test result of the structural member that embodiment 1~9 is prepared
Table 7 is the hot property and physicochemical property test result of the structural member that comparative example 1~3 is prepared
Applicant states that the present invention illustrates method detailed of the invention by above-described embodiment, but the present invention not office
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.
Claims (10)
1. a kind of phosphorous nitrogenous Halogenless fire retarded epoxy resin glue, it is characterised in that by weight, the original of the epoxide-resin glue
Material formula includes following components：
40~60 parts of phosphor-containing halogen-free epoxy resin；
4.5~20 parts of Triallyl isocyanurate；
6~22.5 parts of 4,4 '-BMI diphenyl-methane；
5~10.8 parts of curing agent；
0.5~1.5 part of curing accelerator；
0.5~1 part of colouring agent；
10~25 parts of solvent.
2. phosphorous nitrogenous Halogenless fire retarded epoxy resin glue according to claim 1, it is characterised in that：The phosphor-containing halogen-free ring
Oxygen tree fat can be a series of phosphor-containing halogen-free fire retarding epoxide resins of the phosphorus content more than or equal to 1.7wt. %.
3. phosphorous nitrogenous Halogenless fire retarded epoxy resin glue according to claim 1, it is characterised in that：The curing agent is not for
One or more in halogen-containing curing agent, including amine curing agent, acid anhydride type curing agent, high score subclass curing agent of group
Close.
4. phosphorous nitrogenous Halogenless fire retarded epoxy resin glue according to claim 1, it is characterised in that：The curing accelerator
It is the one kind or many in not halogen-containing curing accelerator, including tertiary amines, imidazoles, organic phosphorus compound class curing accelerator
The combination planted.
5. the preparation of a kind of phosphorous nitrogenous Halogenless fire retarded epoxy resin glue as described in any one of claim 1 ~ 4 claim
Method, it is characterised in that comprise the following steps：By phosphor-containing halogen-free epoxy resin, Triallyl isocyanurate and 4,4 '-span
Carry out acid imide diphenyl-methane to be stirred under the conditions of 90 ~ 100 DEG C to being uniformly dispersed, be subsequently adding curing agent and curing accelerator mixing
Uniformly, 40 ~ 50 DEG C are cooled to, add colouring agent and stirring solvent uniform, obtain final product the phosphorous nitrogenous Halogenless fire retarded epoxy resin
Glue.
6. a kind of prepreg, is impregnated or coating glue by base material, and then drying is formed, it is characterised in that：The glue includes
Phosphorous nitrogenous Halogenless fire retarded epoxy resin glue described in any one of claim 1 ~ 4 claim.
7. prepreg according to claim 6, it is characterised in that：The base material includes alkali-free glass fiber cloth.
8. a kind of high temperature resistant halogen-free flame-retardant insulation fabric part, is formed as the prepreg compacting described in claim 6.
9. high temperature resistant halogen-free flame-retardant insulation fabric part according to claim 8, it is characterised in that：The structural member is by one
The prepreg compacting is formed or suppressed after being stacked by prepreg more than one described and forms.
10. a kind of preparation method of high temperature resistant halogen-free flame-retardant insulation fabric part as claimed in claim 8, it is characterised in that bag
Include following steps：
（1）The preparation of phosphorous nitrogenous Halogenless fire retarded epoxy resin glue：By phosphor-containing halogen-free epoxy resin, Triallyl isocyanurate
With 4,4 '-BMI diphenyl-methane is stirred under the conditions of 90 ~ 100 DEG C to being uniformly dispersed, and is subsequently adding curing agent and solid
Change accelerator to be well mixed, be cooled to 40 ~ 50 DEG C, add colouring agent and stirring solvent uniform, obtain final product the phosphorous nitrogenous Halogen
Fire retarding epoxide resin glue；
（2）The preparation of prepreg：During base material impregnated in into phosphorous nitrogenous Halogenless fire retarded epoxy resin glue, base material after impregnation in
Dried under the conditions of 120 ~ 150 DEG C to the phosphorous nitrogenous Halogenless fire retarded epoxy resin glue in semi-cured state, obtain final product described half solid
Change piece；
（3）The preparation of structural member：Prepreg is cut into the size of needs, then a prepreg is positioned in mould
Suppress or compacting in mould is positioned over after more than one prepreg is stacked, cool down molding, sizing is then placed into 160
Dried 4 ~ 6 hours under the conditions of~l80 DEG C, obtain final product the structural member, wherein 200 ~ 230 DEG C of temperature, the pressure suppressed in the mould
For 10 ~ 14MPa, time are 0.5 ~ 1.5 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710242794.6A CN106916416A (en) | 2017-04-14 | 2017-04-14 | A kind of phosphorous nitrogenous Halogenless fire retarded epoxy resin glue, prepreg and high temperature resistant halogen-free flame-retardant insulation fabric part |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710242794.6A CN106916416A (en) | 2017-04-14 | 2017-04-14 | A kind of phosphorous nitrogenous Halogenless fire retarded epoxy resin glue, prepreg and high temperature resistant halogen-free flame-retardant insulation fabric part |
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|---|---|
| CN106916416A true CN106916416A (en) | 2017-07-04 |
Family
ID=59567186
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| CN201710242794.6A Pending CN106916416A (en) | 2017-04-14 | 2017-04-14 | A kind of phosphorous nitrogenous Halogenless fire retarded epoxy resin glue, prepreg and high temperature resistant halogen-free flame-retardant insulation fabric part |
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| CN100999145A (en) * | 2005-12-31 | 2007-07-18 | 四川东材企业集团有限公司 | Preparation method of glass transition temperature halogenless fire retardant glass cloth laminated board |
| JP2009112159A (en) * | 2007-10-31 | 2009-05-21 | Kyocera Chemical Corp | Coil for sealed type drive motor and its manufacturing method |
| CN102134376A (en) * | 2010-12-29 | 2011-07-27 | 四川东材科技集团股份有限公司 | Halogen-free flame-retardant resin composition and preparation method of prepreg and laminated plate |
| CN105504797A (en) * | 2016-01-06 | 2016-04-20 | 中广核俊尔新材料有限公司 | Multicolor red phosphorus flame-retardant nylon composition and preparation method thereof |
| CN106519569A (en) * | 2016-10-26 | 2017-03-22 | 建滔(佛冈)积层板有限公司 | High-CTI-value halogen-free flame retardant glue solution and prepreg and copper-clad laminate prepared therefrom |
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2017
- 2017-04-14 CN CN201710242794.6A patent/CN106916416A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100999145A (en) * | 2005-12-31 | 2007-07-18 | 四川东材企业集团有限公司 | Preparation method of glass transition temperature halogenless fire retardant glass cloth laminated board |
| JP2009112159A (en) * | 2007-10-31 | 2009-05-21 | Kyocera Chemical Corp | Coil for sealed type drive motor and its manufacturing method |
| CN102134376A (en) * | 2010-12-29 | 2011-07-27 | 四川东材科技集团股份有限公司 | Halogen-free flame-retardant resin composition and preparation method of prepreg and laminated plate |
| CN105504797A (en) * | 2016-01-06 | 2016-04-20 | 中广核俊尔新材料有限公司 | Multicolor red phosphorus flame-retardant nylon composition and preparation method thereof |
| CN106519569A (en) * | 2016-10-26 | 2017-03-22 | 建滔(佛冈)积层板有限公司 | High-CTI-value halogen-free flame retardant glue solution and prepreg and copper-clad laminate prepared therefrom |
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Application publication date: 20170704 |