A kind of preparation method of phosphor-containing halogen-free low-smoke and flame retardant epoxy resin composite material
Technical field
The present invention relates to a kind of preparation of halogen-free smoke inhibition fire retardant, more particularly to a kind of phosphor-containing halogen-free low-smoke and flame retardant asphalt mixtures modified by epoxy resin
The preparation of resin composite material, belongs to fire proofing technical field and technical field of polymer materials.
Background technology
Epoxy resin is to refer to the organic compound containing two or more epoxide groups in molecule, it is characterized in that point
Contain active epoxide group in minor structure chain, epoxide group can be located at the end of strand, middle or circlewise structure.By
Contain active epoxide group in molecular structure, them is crosslinked reaction with polytype curing agent and is formed not
The molten high polymer with tridimensional network.Epoxy resin after solidification has good physics, chemical property, to metal and
The surface of nonmetallic materials has excellent adhesive strength, and dielectric properties are good, and deformation retract rate is small, product size stability
Good, hardness is high, and pliability preferably, to alkali and most of solvent-stable, thus is widely used in national defence, each department of national economy.
It is specifically most widely used in the following aspects:
1st, coating.Application of the epoxy resin in coating accounts for larger ratio, it can be made differ from one another, the product that purposes is different
Kind.
2nd, adhesive.Epoxy resin is in addition to bad to the non-polar plastic caking property such as polyolefin, for various metals
Material such as aluminium, steel, iron, copper;Nonmetallic materials such as glass, timber, concrete etc.;And thermosetting plastics such as phenolic aldehyde, amino, no
Saturated polyester etc. has excellent adhesive property, therefore has the title of all-purpose adhesive.Epoxy adhesive is the important product of sqtructural adhesive
Kind.
3rd, electronic apparatus material.Because the insulating properties of epoxy resin are high, structural strength is big and many such as good seal performance
Unique advantage, is used widely in the insulation and encapsulation of high and low voltage electrical equipment, motor and electronic component, and development is very
It hurry up.It is mainly used in:(1)The cast of electrical equipment, motor insulating envelope.Such as electromagnet, contactor coil, transformer, dry type transformation
The hermetically sealed insulating envelope of entirety of the high and low voltage electrical equipments such as device.(2)It is widely used in the device equipped with electronic component and circuit
Embedding is insulated.Turn into the indispensable important insulating materials of electronics industry.(3)Electron level epoxy molding plastic is used for semiconductor element
The plastic packaging of device.Development is exceedingly fast in recent years.Due to its superior performance, big substituted traditional metal, ceramics and glass-encapsulated
Trend.(4)Epoxy laminate plastics are very wide in electronics, appliance field application.The development of wherein epoxy copperplate is especially rapid,
One of basic material as electronics industry.Largely should in addition, epoxy insulation coating, dielectric adhesive and electric adhesive also have
With.
4th, engineering plastics and composite.Epoxy engineering plastics mainly include the epoxy molding plastic and ring for high-pressure molding
Oxygen layer compression molding material, and epoxy foam plastics.Epoxy engineering plastics can also regard a kind of epoxy composite material of broad sense as.Ring
O compoiste material mainly has fiber glass epoxy(Universal composite)With epoxy construction composite, the epoxy of such as pultrusion
Section bar, Wrapping formed hollow revolving body product and high-performance composite materials.Epoxy composite material be chemical industry and Aeronautics and Astronautics,
A kind of important structural material and functional material of the high-tech sectors such as military project.
5th, civil material.Be mainly used as anti-corrosion terrace, epoxy resin mortar and concrete product, high class pavement and airfield runway,
Fast repairing material, the grouting material of foundation, architecture adhesion agent and coating etc..
Although the physical property of epoxy resin is very good, also there is that fatal, common epoxy resin is very easy to
Burning, its oxygen index (OI) only has 19% or so, there is huge disaster hidden-trouble, especially in electronic products field and building materials field.By
The fire incident that epoxy resin triggers is very more, therefore, how to improve the anti-flammability of epoxy resin, can be safer
It is the problem of many scientific research personnel need solution to serve society.
At present, the fire-retardant research of epoxy resin is concentrated mainly on additive flame retardant, although currently solve epoxy resin
The problem of burning, but the mechanical performance of epoxy resin is sacrificed, limit its application field.In recent years, it is intrinsic fire-retardant to grind
It is a very popular problem to study carefully, and is also most to be hopeful to solve that high polymer material is fire-retardant and mechanical performance is conflicting arranges
Apply.But intrinsic fire-retardant shortcoming is to prepare cost height, and the suppression cigarette capability improving to material is not enough.Therefore, using it is intrinsic it is fire-retardant and
The advantage of additive flame retardant, the two is combined, and prepares a kind of LSOH anti-flaming epoxy resin composite material, can be effective
The combustion problem of epoxy resin is solved, can also retain the mechanical performance of epoxy resin, make it have wider purposes.
The content of the invention
The purpose of the present invention be for fire retarding epoxide resin is present in the prior art the problem of there is provided a kind of novel phosphorus-containing without
Halogen low-smoke and flame retardant epoxy resin composite material and preparation method thereof.
First, the preparation of phosphor-containing halogen-free low-smoke and flame retardant epoxy resin composite material
(1)The synthesis of the phosphorus phosphonitrile (PN-OH) of precursor 6 (4- hydroxyphenoxies) ring three:Using tetrahydrofuran as solvent, anhydrous K2CO3
For catalyst, parahydroxyben-zaldehyde is with hexachlorocyclotriph,sphazene in 45 ~ 65 DEG C of h of back flow reaction 20 ~ 24;Filtering, washing, merge filter
Liquid is simultaneously concentrated into the 1/2 ~ 1/5 of original volume, is settled, washed with distilled water, and with re-crystallizing in ethyl acetate, vacuum drying obtains yellowish
The phosphonitrile (PN-CHO) of color solid 6 (4- aldehyde radicals phenoxy group) ring three;Again in THF- methanol mixed solvents, make sodium borohydride solids with
The phosphonitrile of 6 (4- aldehyde radicals phenoxy group) ring three h of reduction reaction 8 ~ 12 at room temperature, vacuum distillation goes out after solvent with distillation water sedimentation, takes out
Filter, is recrystallized after washing with absolute ethyl alcohol, is dried in vacuo, it is the phosphorus phosphonitrile of 6 (4- hydroxyphenoxies) ring three to obtain white product
(PN-OH)。
The mass ratio of hexachlorocyclotriph,sphazene and parahydroxyben-zaldehyde is 1:3~1:6;Catalyst K2CO3Consumption be hydroxy benzenes
0.5 ~ 1 times of formaldehyde and hexachlorocyclotriph,sphazene gross mass.
In THF- methanol mixed solvents, the volume ratio of THF and methanol is 2:1~5:1;Sodium borohydride solids and 6 (4- aldehyde radicals
Phenoxy group) ring three phosphonitrile mass ratio be 0.5:1~1:1.
(2)The synthesis of phosphor-containing flame-proof resin:By the phosphorus phosphonitrile of 6 (4- hydroxyphenoxies) ring three, cetyl trimethyl bromination
After ammonium, epoxychloropropane mixing, in being stirred vigorously 1 ~ 3 h at 80 ~ 120 DEG C;Then mixture is cooled to 40 ~ 55 DEG C, and
The NaOH aqueous solution is added, 8 ~ 12 h are reacted in 40 ~ 55 DEG C;Filtering separates out product after the completion of reaction, and is washed product with hot water
To neutrality, with anhydrous sodium sulfate drying, vacuum distillation removes unreacted epoxychloropropane, obtains water white transparency low-viscosity phosphorous
Epoxy resin;
The mass ratio of cetyl trimethylammonium bromide and the phosphorus phosphonitrile of 6 (4- hydroxyphenoxies) ring three is 1:35~1:45;Six alkyl
Trimethylammonium bromide is 1 with epoxychloropropane mass ratio:2000~1:2500;NaOH effect is the byproduct salt of neutralization reaction
Acid, its addition is the 2% ~ 5% of three's gross mass.
(3)It is prepared by LSOH anti-flaming epoxy resin composite material:By step(2)Gained phosphorous epoxy resin is heated to
100 ~ 120 DEG C, curing agent, curing accelerator, anti-flaming smoke-inhibiting agent, zinc hydroxide and magnesium gluconate are separately added with agitation,
Mould is poured into after the h of constant temperature stirring and dissolving 1 ~ 3, prior to the 120 DEG C h of isothermal curing 1 ~ 4 solidify 0.5 ~ 3 h, i.e., then at 160 DEG C
Obtain LSOH anti-flaming epoxy resin composite material;
Curing agent is 4,4- MDAs(DDM)Or 4,4- diaminodiphenylsulfones(DDS), the addition of curing agent be containing
0.01 ~ 0.1 times of phosphorus epoxy resin quality.
Curing accelerator is boron trifluoride ethylamine complex compound, and its addition is the 0.01 ~ 0.05 of phosphorous epoxy resin quality
Times.
Anti-flaming smoke-inhibiting agent is palygorskite, and its addition is 0.01 ~ 0.1 times of phosphorous epoxy resin quality.
The effect of zinc hydroxide is to provide zinc source, favourable into carbon during to burning, and its addition is phosphorous epoxy resin quality
0.05 ~ 0.1 times.
The effect of magnesium gluconate is to provide fire-retardant gas carbon dioxide and carbon forming agent magnesium elements, and its addition is phosphorous ring
0.005 ~ 0.05 times of oxygen resin quality.
The synthetic route of LSOH anti-flaming epoxy resin is as follows:
Epoxy resin prepared by the present invention1H NMR spectras are shown in Fig. 1.6.79 ~ 7.24ppm is mainly it can be seen from collection of illustrative plates
The formant of phenyl ring Hydrogen Proton in compound, the CH that 2.47 ~ 2.77ppm is belonged on epoxide ring2, 3.26ppm and 3.70ppm
Belong to the CH being joined directly together with epoxide ring2, 3.41ppm belongs to CH on epoxide ring, the compound structure with it is expected consistent.
Epoxy resin infrared spectrogram prepared by the present invention is shown in Fig. 2.Figure it is seen that 1208cm-1 For phosphonitrile structure
Middle P=N stretching vibration absworption peak, 609cm-1With 526cm-1For the P-Cl stretching vibration absworption peaks in phosphazene compound;
3390cm-1For PN-OH compound O-H stretching vibration peaks;In PN-CHO, 609cm-1With 526cm-1The P-Cl stretching vibration peaks at place
Disappear, it was demonstrated that Cl is fully substituted in HCCP;955cm-1And 833cm-1For C-O-C stretching vibration absworption peak, above analytical table
Bright, PNEP is the epoxy resin containing phosphonitrile, and structure is consistent with the expected structure of synthetic route.
Carbon-coating surface after Epoxy burns prepared by the present invention(a)And it is internal(b)Stereoscan photograph is shown in Fig. 3.From Fig. 3
As can be seen that a large amount of nanoscale little particles are accumulated on carbon-coating surface, it is fine and close, continuous, it may be possible to which that phosphorus-containing groups are fired in resin material
Burn after decomposing, is combined with carbon and be attached to material surface and form fine and close effectively carbon-coating.Carbon-coating inner surface is smooth, hard, continuous, interior
There are many depressions on surface, and this is mainly generation steam and other gases in combustion process and does not break through carbon-coating barrier, stays in material
Inside, forms a large amount of pits region.This shows that carbon-coating can give full play to heat-insulated, oxygen barrier, press down the effect of cigarette, has effectively carried height
The fire resistance of resin material.
2nd, phosphor-containing halogen-free low-smoke and flame retardant epoxy resin composite material performance test
1st, fire resistance
Method of testing:Using GB/T2460-93 standard testings.
Test result:Oxygen index (OI) reaches more than 32, and horizontal vertical is burnt V-0 grades, and smoke density is less than 75.
2nd, mechanical performance
Method of testing:Using GB/T9341-88 and GB/T1843-80 standards.
Test result:Bending strength:28 ~ 31 MPa, impact strength:3.80~3.99 KJ/m2。
As can be seen here, the LSOH anti-flaming epoxy resin composite material that prepared by the present invention has good fire retardancy,
Also there is the property of low cigarette, and satisfactory mechanical property simultaneously, can be widely used in electronic device, engineering building materials field.
Brief description of the drawings
The epoxy resin that Fig. 1 is prepared for the present invention1H NMR spectras;
The infrared spectrogram for the epoxy resin that Fig. 2 is prepared for the present invention;
Carbon-coating surface and inner scanning electromicroscopic photograph after the Epoxy burns that Fig. 3 is prepared for the present invention.
Embodiment
Below by preparation method of the specific embodiment to phosphor-containing halogen-free low-smoke and flame retardant epoxy resin composite material of the present invention
And performance is described further.
Embodiment 1
(1)The synthesis of the phosphorus phosphonitrile (PN-OH) of precursor 6 (4- hydroxyphenoxies) ring three
30 g parahydroxyben-zaldehydes and 250 mL THF are placed in 500 mL flasks, magnetic agitation makes it fully molten under normal temperature
Solution;20 g anhydrous Ks are added afterwards2CO3And stir.10 g hexachlorocyclotriph,sphazenes are dissolved in 50 mLTHF, then slow drop
Enter(Time for adding is about 1 h)In the tetrahydrofuran solution of parahydroxyben-zaldehyde;65 DEG C are warming up to after 0.5 h, magnetic agitation is returned
24 h of stream reaction;Filtering, and with THF cyclic washings several times;Merging filtrate is simultaneously concentrated into after original volume about 1/5, anti-to instill greatly
Measure in distilled water and settle, filtering is precipitated and with distillation water washing 3 times, finally with re-crystallizing in ethyl acetate 2 times, 50 DEG C of vacuum are dry
Dry 12 h, obtains the phosphonitrile (PN-CHO) of faint yellow solid -6 (4- aldehyde radicals phenoxy group) ring three, yield is 56%;
The phosphonitrile of 10 g6 (4- aldehyde radicals phenoxy group) ring three is added in 1000mL three-necked flasks, 100 ml THF/ methanol solutions are added
(THF/ methanol=2/1v/v), 5 g sodium borohydride solids are added portionwise after dissolving is stirred at room temperature.12 h are reacted at room temperature, are depressurized
Distill out it is counter after a large amount of solvents instill in a large amount of distilled water, obtain white precipitate, suction filtration, a small amount of THF washed products for several times, with nothing
Water-ethanol is recrystallized 2 times, and 80 DEG C of 12 h of vacuum drying obtain the phosphorus phosphonitrile (PN-OH) of product 6 (4- hydroxyphenoxies) ring three, yield
91%。
(2)The synthesis of phosphorus-containing flame-retardant epoxy resin
By the phosphorus phosphonitrile of 35g 6 (4- hydroxyphenoxies) ring three, 1 g cetyl trimethylammonium bromides and 2000 g epoxy chloropropionates
Alkane is added in 250mL three-necked flasks, and 3 h are stirred vigorously at 120 DEG C, mixture then is cooled into 55 DEG C, and add 90 g
The 50% NaOH aqueous solution, 12 h are reacted at 55 DEG C.After the completion of reaction by precipitate be filtered to remove and with hot water by product wash to
Neutrality, with anhydrous sodium sulfate drying, and vacuum distillation removes unreacted epoxychloropropane, finally obtains water white transparency low-viscosity
Phosphorous epoxy resin, yield is about 84%.
(3)It is prepared by LSOH anti-flaming epoxy resin composite material
1000 g phosphorous epoxy resins are heated to 120 DEG C of stirrings, 10g 4,4- MDAs is added(DDM)Or 4,
4- diaminodiphenylsulfones(DDS)With 10 g boron trifluoride ethylamine complex compounds, 10 g palygorskites, 50 g zinc hydroxides and 5 g
After magnesium gluconate, the min of constant temperature stirring and dissolving 30, mould is poured into.First in 120 DEG C of h of isothermal curing 4, then 160 DEG C of solidifications 3
h.Prepare the mm of the mm of the mm and 80 mm of the mm of 120 mm × 6.5 × 3 × 10 × 4 strip LSOH anti-flaming asphalt mixtures modified by epoxy resin
Resin composite material sample.
(4)The performance of LSOH anti-flaming epoxy resin composite material
Flame Retardancy energy:Oxygen index (OI) reaches 32, and horizontal vertical is burnt V-0 grades, smoke density 73.
Mechanical performance:Bending strength:31 MPa, impact strength:3.99 KJ/m2。
Embodiment 2
(1)The synthesis of the phosphorus phosphonitrile (PN-OH) of precursor 6 (4- hydroxyphenoxies) ring three
60 g parahydroxyben-zaldehydes and 500 mL THF are placed in 1000 mL flasks, magnetic agitation makes it fully molten under normal temperature
Solution;70 g anhydrous Ks are added afterwards2CO3And stir.10 g hexachlorocyclotriph,sphazenes are dissolved in 50 mLTHF, then slow drop
Enter(Time for adding is about 1 h)In the tetrahydrofuran solution of parahydroxyben-zaldehyde;45 DEG C are warming up to after 0.5 h, magnetic agitation is returned
20 h of stream reaction;Filtering, and with THF cyclic washings several times;Merging filtrate is simultaneously concentrated into after original volume about 1/2, anti-to instill greatly
Measure in distilled water and settle, filtering is precipitated and with distillation water washing 3 times, finally with re-crystallizing in ethyl acetate 2 times, 50 DEG C of vacuum are dry
Dry 12 h, obtains the phosphonitrile (PN-CHO) of faint yellow solid -6 (4- aldehyde radicals phenoxy group) ring three, yield is 56%;
The phosphonitrile of 10g 6 (4- aldehyde radicals phenoxy group) ring three is added in 1000mL three-necked flasks, 100ml THF/ methanol solutions are added
(THF/ methanol=5/1 v/v), 10 g sodium borohydride solids are added portionwise after dissolving is stirred at room temperature.8h is reacted at room temperature, is depressurized
Distill out it is counter after a large amount of solvents instill in a large amount of distilled water, obtain white precipitate, suction filtration, a small amount of THF washed products for several times, with nothing
Water-ethanol is recrystallized 2 times, and 80 DEG C of 12 h of vacuum drying obtain the phosphorus phosphonitrile (PN-OH) of product 6 (4- hydroxyphenoxies) ring three, produced
Rate 91%.
(2)The synthesis of phosphorus-containing flame-retardant epoxy resin
By the phosphorus phosphonitrile of 45g 6 (4- hydroxyphenoxies) ring three, 1 g cetyl trimethylammonium bromides and 2500 g epoxy chloropropionates
Alkane is added in 2500 mL three-necked flasks, and 1 h is stirred vigorously at 80 DEG C, mixture then is cooled into 40 DEG C, and add
The 101.8 g 50% NaOH aqueous solution, 8 h are reacted at 40 DEG C.Precipitate is filtered to remove after the completion of reaction and will be produced with hot water
Thing is washed to neutrality, with anhydrous sodium sulfate drying, and vacuum distillation removes unreacted epoxychloropropane, finally obtains colourless
Bright low-viscosity phosphorous epoxy resin, yield is about 84%.
(3)It is prepared by LSOH anti-flaming epoxy resin composite material
1000 g phosphorous epoxy resins are heated to 120 DEG C of stirrings, 100 g4,4- MDAs are added(DDM)Or 4,
4- diaminodiphenylsulfones(DDS)With 50 g boron trifluoride ethylamine complex compounds, 100 g palygorskites, 100 g zinc hydroxides and
After 100 g magnesium gluconates, the min of constant temperature stirring and dissolving 50, mould is poured into.First in 120 DEG C of h of isothermal curing 4, then 160 DEG C
Solidify 3 h.Prepare the mm of the mm of the mm and 80 mm of the mm of 120 mm × 6.5 × 3 × 10 × 4 strip LSOH anti-flaming
Epoxy resin composite material sample.
(4)The performance of LSOH anti-flaming epoxy resin composite material
Flame Retardancy energy:Oxygen index (OI) reaches 36, and horizontal vertical is burnt V-0 grades, smoke density 58.
Mechanical performance:Bending strength:28 MPa, impact strength: 3.80 KJ/m2。
Embodiment 3
(1)The synthesis of the phosphorus phosphonitrile (PN-OH) of precursor 6 (4- hydroxyphenoxies) ring three
40 g parahydroxyben-zaldehydes and 500 mL THF are placed in 1000 mL flasks, magnetic agitation makes it fully molten under normal temperature
Solution;35 g anhydrous Ks are added afterwards2CO3And stir.10 g hexachlorocyclotriph,sphazenes are dissolved in 50 mLTHF, then slow drop
Enter(Time for adding is about 1 h)In the tetrahydrofuran solution of parahydroxyben-zaldehyde;55 DEG C are warming up to after 0.5 h, magnetic agitation is returned
22 h of stream reaction;Filtering, and with THF cyclic washings several times;Merging filtrate is simultaneously concentrated into after original volume about 1/4, anti-to instill greatly
Measure in distilled water and settle, filtering is precipitated and with distillation water washing 3 times, finally with re-crystallizing in ethyl acetate 2 times, 50 DEG C of vacuum are dry
Dry 12 h, obtains the phosphonitrile (PN-CHO) of faint yellow solid -6 (4- aldehyde radicals phenoxy group) ring three, yield is 56%;
The phosphonitrile of 10 g6 (4- aldehyde radicals phenoxy group) ring three is added in 1000mL three-necked flasks, 100 ml THF/ methanol solutions are added
(THF/ methanol=4/1 v/v), 6 g sodium borohydride solids are added portionwise after dissolving is stirred at room temperature.10h is reacted at room temperature, and decompression is steamed
Distillate it is counter after a large amount of solvents instill in a large amount of distilled water, obtain white precipitate, suction filtration, a small amount of THF washed products for several times, with anhydrous
Ethyl alcohol recrystallization 2 times, 80 DEG C of 12 h of vacuum drying, obtains the phosphorus phosphonitrile (PN-OH) of product 6 (4- hydroxyphenoxies) ring three, yield
91%。
(2)The synthesis of phosphorus-containing flame-retardant epoxy resin
By the phosphorus phosphonitrile of 40g 6 (4- hydroxyphenoxies) ring three, 1 g cetyl trimethylammonium bromides and 2200 g epoxy chloropropionates
Alkane is added in 2500 mL three-necked flasks, and 2 h are stirred vigorously at 100 DEG C, mixture then are cooled into 50 DEG C, and add
The 40.72 g 50% NaOH aqueous solution, 10 h are reacted at 50 DEG C.Precipitate is filtered to remove after the completion of reaction and will be produced with hot water
Thing is washed to neutrality, with anhydrous sodium sulfate drying, and vacuum distillation removes unreacted epoxychloropropane, finally obtains colourless
Bright low-viscosity phosphorous epoxy resin, yield is about 84%.
(3)It is prepared by LSOH anti-flaming epoxy resin composite material
1000 g phosphorous epoxy resins are heated to 120 DEG C of stirrings, 80 g4,4- MDAs are added(DDM)Or 4,
4- diaminodiphenylsulfones(DDS)With 40 g boron trifluoride ethylamine complex compounds, 60 g palygorskites, 60 g zinc hydroxides and 10 g
After magnesium gluconate, the min of constant temperature stirring and dissolving 30, mould is poured into.First in 120 DEG C of h of isothermal curing 4, then 160 DEG C of solidifications 3
h.Prepare the mm of the mm of the mm and 80 mm of the mm of 120 mm × 6.5 × 3 × 10 × 4 strip LSOH anti-flaming asphalt mixtures modified by epoxy resin
Resin composite material sample.
(4)The performance of LSOH anti-flaming epoxy resin composite material
Flame Retardancy energy:Oxygen index (OI) reaches 35, and horizontal vertical is burnt V-0 grades, smoke density 65.
Mechanical performance:Bending strength:30 MPa, impact strength: 3.90 KJ/m2。
Embodiment 4
(1)The synthesis of the phosphorus phosphonitrile (PN-OH) of precursor 6 (4- hydroxyphenoxies) ring three
50 g parahydroxyben-zaldehydes and 500 mL THF are placed in 1000 mL flasks, magnetic agitation makes it fully molten under normal temperature
Solution;60 g anhydrous Ks are added afterwards2CO3And stir.10 g hexachlorocyclotriph,sphazenes are dissolved in 50 mLTHF, then slow drop
Enter(Time for adding is about 1 h)In the tetrahydrofuran solution of parahydroxyben-zaldehyde;65 DEG C are warming up to after 0.5 h, magnetic agitation is returned
24 h of stream reaction;Filtering, and with THF cyclic washings several times;Merging filtrate is simultaneously concentrated into after original volume about 1/4, anti-to instill greatly
Measure in distilled water and settle, filtering is precipitated and with distillation water washing 3 times, finally with re-crystallizing in ethyl acetate 2 times, 50 DEG C of vacuum are dry
Dry 12 h, obtains the phosphonitrile (PN-CHO) of faint yellow solid -6 (4- aldehyde radicals phenoxy group) ring three, yield is 56%;
The phosphonitrile of 10 g6 (4- aldehyde radicals phenoxy group) ring three is added in 1000mL three-necked flasks, 200 ml THF/ methanol solutions are added
(THF/ methanol=3/1 v/v), 9 g sodium borohydride solids are added portionwise after dissolving is stirred at room temperature.12 h are reacted at room temperature, are depressurized
Distill out it is counter after a large amount of solvents instill in a large amount of distilled water, obtain white precipitate, suction filtration, a small amount of THF washed products for several times, with nothing
Water-ethanol is recrystallized 2 times, and 80 DEG C of 12 h of vacuum drying obtain the phosphorus phosphonitrile (PN-OH) of product 6 (4- hydroxyphenoxies) ring three, produced
Rate 91%.
(2)The synthesis of phosphorus-containing flame-retardant epoxy resin
By the phosphorus phosphonitrile of 40g 6 (4- hydroxyphenoxies) ring three, 1 g cetyl trimethylammonium bromides and 2300 g epoxy chloropropionates
Alkane is added in 2500 mL three-necked flasks, and 3 h are stirred vigorously at 120 DEG C, mixture then is cooled into 55 DEG C, and add 80
The g 50% NaOH aqueous solution, 12 h are reacted at 55 DEG C.Precipitate is filtered to remove after the completion of reaction and product is washed with hot water
To neutral, with anhydrous sodium sulfate drying, and vacuum distillation removes unreacted epoxychloropropane, finally obtains water white transparency low glutinous
Phosphorous epoxy resin is spent, yield is about 84%.
(3)It is prepared by LSOH anti-flaming epoxy resin composite material
1000 g phosphorous epoxy resins are heated to 120 DEG C of stirrings, 30 g4,4- MDAs are added(DDM)Or 4,
4- diaminodiphenylsulfones(DDS)With 20 g boron trifluoride ethylamine complex compounds, 50 g palygorskites, 40 g zinc hydroxides and 30 g
After magnesium gluconate, the min of constant temperature stirring and dissolving 30, mould is poured into.First in 120 DEG C of h of isothermal curing 4, then 160 DEG C of solidifications 3
h.Prepare the mm of the mm of the mm and 80 mm of the mm of 120 mm × 6.5 × 3 × 10 × 4 strip LSOH anti-flaming asphalt mixtures modified by epoxy resin
Resin composite material sample.
(4)The performance of LSOH anti-flaming epoxy resin composite material
Flame Retardancy energy:Oxygen index (OI) reaches 34, and horizontal vertical is burnt V-0 grades, smoke density 70.
Mechanical performance:Bending strength:28.6 MPa, impact strength: 3.93 KJ/m2。
Embodiment 5
(1)The synthesis of the phosphorus phosphonitrile (PN-OH) of precursor 6 (4- hydroxyphenoxies) ring three
50 g parahydroxyben-zaldehydes and 500 mL THF are placed in 1000 mL flasks, magnetic agitation makes it fully molten under normal temperature
Solution;30 g anhydrous Ks are added afterwards2CO3And stir.10 g hexachlorocyclotriph,sphazenes are dissolved in 50 mLTHF, then slow drop
Enter(Time for adding is about 1 h)In the tetrahydrofuran solution of parahydroxyben-zaldehyde;65 DEG C are warming up to after 0.5 h, magnetic agitation is returned
24 h of stream reaction;Filtering, and with THF cyclic washings several times;Merging filtrate is simultaneously concentrated into after original volume about 1/4, anti-to instill greatly
Measure in distilled water and settle, filtering is precipitated and with distillation water washing 3 times, finally with re-crystallizing in ethyl acetate 2 times, 50 DEG C of vacuum are dry
Dry 12 h, obtains the phosphonitrile (PN-CHO) of faint yellow solid -6 (4- aldehyde radicals phenoxy group) ring three, yield is 56%;
The phosphonitrile of 10 g6 (4- aldehyde radicals phenoxy group) ring three is added in 1000mL three-necked flasks, 100ml THF/ methanol solutions are added
(THF/ methanol=2/1 v/v), 7g sodium borohydride solids are added portionwise after dissolving is stirred at room temperature.12 h are reacted at room temperature, are depressurized
Distill out it is counter after a large amount of solvents instill in a large amount of distilled water, obtain white precipitate, suction filtration, a small amount of THF washed products for several times, with nothing
Water-ethanol is recrystallized 2 times, and 80 DEG C of 12 h of vacuum drying obtain the phosphorus phosphonitrile (PN-OH) of product 6 (4- hydroxyphenoxies) ring three, produced
Rate 91%.
(2)The synthesis of phosphorus-containing flame-retardant epoxy resin
By the phosphorus phosphonitrile of 35g 6 (4- hydroxyphenoxies) ring three, 1 g cetyl trimethylammonium bromides and 2400 g epoxy chloropropionates
Alkane is added in 2500 mL three-necked flasks, and 3 h are stirred vigorously at 120 DEG C, mixture then is cooled into 55 DEG C, and add 70
The g 50% NaOH aqueous solution, 12 h are reacted at 55 DEG C.Precipitate is filtered to remove after the completion of reaction and product is washed with hot water
To neutral, with anhydrous sodium sulfate drying, and vacuum distillation removes unreacted epoxychloropropane, finally obtains water white transparency low glutinous
Phosphorous epoxy resin is spent, yield is about 84%.
(3)It is prepared by LSOH anti-flaming epoxy resin composite material
1000 g phosphorous epoxy resins are heated to 120 DEG C of stirrings, 30 g4,4- MDAs are added(DDM)Or 4,
4- diaminodiphenylsulfones(DDS)With 45 g boron trifluoride ethylamine complex compounds, 70 g palygorskites, 45 g zinc hydroxides and 50 g
After magnesium gluconate, the min of constant temperature stirring and dissolving 50, mould is poured into.First in 120 DEG C of h of isothermal curing 4, then 160 DEG C of solidifications 3
h.Prepare the mm of the mm of the mm and 80 mm of the mm of 120 mm × 6.5 × 3 × 10 × 4 strip LSOH anti-flaming asphalt mixtures modified by epoxy resin
Resin composite material sample.
(4)The performance of LSOH anti-flaming epoxy resin composite material
Flame Retardancy energy:Oxygen index (OI) reaches 35, and horizontal vertical is burnt V-0 grades, smoke density 72.
Mechanical performance:Bending strength:30 MPa, impact strength: 3.85 KJ/m2。