CN110016178A - A kind of ternary hybrid inorganic-organic materials composite flame-retardant agent and its application - Google Patents
A kind of ternary hybrid inorganic-organic materials composite flame-retardant agent and its application Download PDFInfo
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- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
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Abstract
The invention discloses a kind of ternary hybrid inorganic-organic materials composite flame-retardant agent and its application, DOPO and benzoquinones are dissolved in ethoxy ethanol, react to obtain ODOPB；Dicyanodiamine, boric acid are completely soluble in water, are stirred at a certain temperature to water evaporating completely, are calcined in tube furnace, obtain boron doped g-C3N4；Ammonium molybdate, thiocarbamide are completely soluble in water, are stirred at a certain temperature to water evaporating completely, are calcined in tube furnace, obtain MoS2；ODOPB,g-C3N4And MoS2It is dissolved in the sulfuric acid solution of suitable concentration, stirs evenly after mixing, centrifuge washing, vacuum drying obtains tri compound fire retardant.It is main flame-retardant composition that composite flame-retardant agent of the present invention, which selects the inorganic fire retardants of clean and effective, is aided with organic fire-retardant, while enhancing flame retardance of polymer effect, keeps the mechanical property of original material.
Description
Technical field
The invention belongs to material processing technical fields, are related to a kind of fire retardant, and in particular to a kind of ternary organic and inorganic is miscellaneous
Change Material cladding fire retardant；The invention further relates to a kind of applications of composite flame-retardant agent.
Background technique
Ethylene-vinyl acetate copolymer (EVA) is thermoplastic indispensable in life, in food packaging, electricity
The fields such as line cable insulation material, hot melt adhesive are widely used.EVA great convenience people live while, there is also
Flammable high disadvantage, affect the security of the lives and property of people.Therefore, probing into synthesis has flame retardant effect EVA material
Method becomes research hotspot.
In order to improve the anti-flammability of EVA material, holds easy-to-blend property using EVA in the prior art, be prepared for one
Series modified palygorskite addition type EVA composite flame-proof material.But palygorskite is added to EVA as a kind of silicate clay
In, compatibility is poor, can reduce the mechanical property of material itself.
Molybdenum disulfide (MoS2) there is two-dimensional network structure similar to graphene, surface area ratio is larger, active height, is moistening
There is application in the fields such as lubrication prescription, catalyst, intercalation chemistry.Currently, Many researchers are by MoS2Nanometer sheet is poly- for enhancing
Close hot property, flame retardant property and the mechanical property of object material.MoS2Nano flake can be with the release of trap heat, in condensed phase side
The fire retardancy of face raising material.
Summary of the invention
The object of the present invention is to provide a kind of ternarys of flame retardant property that can enhance ethylene-vinyl acetate copolymer to have
Machine-inorganic hybrid material composite flame-retardant agent.
It is a further object to provide a kind of applications of above-mentioned composite flame-retardant agent.
To achieve the above object, the technical scheme adopted by the invention is that: a kind of ternary hybrid inorganic-organic materials are compound
The preparation method of fire retardant is made in this way:
1) by the addition miscellaneous -10- phospho hetero phenanthrene -10- oxide (DOPO) 15 of 9,10- dihydro-9-oxy in 20~50mL ethoxy ethanol
The ratio of 15~25g of~20g and benzoquinones takes the miscellaneous -10- phospho hetero phenanthrene -10- oxidation of ethoxy ethanol, 9,10- dihydro-9-oxy respectively
Object and benzoquinones, DOPO and benzoquinones are dissolved in ethoxy ethanol, 110~130 DEG C at a temperature of react 5 hours, obtain phospho hetero phenanthrene
Oxide (ODOPB)；
1 ︰ 2~8 in mass ratio, takes boric acid and dicyanodiamine respectively, completely dissolves in water, 60~80 DEG C at a temperature of stir
Mixing, until water evaporating completely, is placed in the environment that temperature is 500~700 DEG C and calcines 3~7 h, obtain boron doped carbonitride
(g-C3N4)；
1 ︰ 1~4 in mass ratio, takes ammonium molybdate and thiocarbamide respectively, completely dissolves in water, mixed in 60~80 DEG C of at a temperature of stirring
It closes, until water evaporating completely, is placed in the environment that temperature is 500~700 DEG C and calcines 3~7 h, obtain molybdenum disulfide (MoS2)；
2) 1 ︰ in mass ratio, 1 ︰ 1~5, takes ODOPB, g-C respectively3N4And MoS2, it is 3~8 that molal volume concentration is dissolved in after mixing
In the sulfuric acid solution of mol/L, stir evenly, distillation be washed to neutrality, 50~80 DEG C at a temperature of be dried in vacuo, be made ternary
Hybrid inorganic-organic materials composite flame-retardant agent (ODOPB@g-C3N4@MoS2).
Another technical solution of the present invention is: a kind of above-mentioned composite flame-retardant agent is in enhancing ethene-vinyl acetate
Application in ester copolymer flame retardant property.Specifically: it weighs EVA and is placed in plastics processing mill, melted at 110 DEG C, being then added can be swollen
Swollen graphite (EG) and ODOPB@g-C3N4@MoS2, it is subsequently poured into mold (mm × 3.2 of 130 mm × 6.5 mm) hydraulic
Hot pressing 240s on vulcanizing press, moves to the cooling 1min of hydraulic press, and demoulding obtains composite material batten.(EVA, EG and ODOPB@
g-C3N4@MoS2Dosage see below table 1)
Composite flame-retardant agent of the present invention selects the MoS with two-dimensional slice structure2, g-C3N4Splendid thermal stability is shown, can be shown
The flame retardant property of enhancing high molecular material is write, it is then compound with organic phosphorus flame retardant ODOPB, keep or optimize the power of polymer
Learn performance.
Detailed description of the invention
Fig. 1 is ODOPB, g-C3N4With ODOPB@g-C3N4@MoS2Infrared comparison diagram.
Fig. 2 is the comparison diagram of heat release rate after epoxy resin and graphene oxide composite flame-proof material obtained burning.
Specific embodiment
Preparation method of the present invention is described in detail below by specific embodiment.
Embodiment 1
The 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide of 15g and 15g benzoquinones are dissolved in 20mL ethoxy ethanol,
110 DEG C at a temperature of react 5 hours, obtain phospho hetero phenanthrene oxide；1 ︰ 2 in mass ratio, takes boric acid and dicyanodiamine, completely respectively
Be dissolved in the water, 60 DEG C at a temperature of be stirred, until water evaporating completely, be placed in the environment that temperature is 500 DEG C and calcine
3h obtains boron doped carbonitride；1 ︰ 1 in mass ratio, takes ammonium molybdate and thiocarbamide respectively, completely dissolves in water, in 60 DEG C of temperature
It is stirred under degree, until water evaporating completely, is placed in the environment that temperature is 500 DEG C and calcines 3h, obtain molybdenum disulfide；In mass ratio
1 ︰, 1 ︰ 1, takes phospho hetero phenanthrene oxide, boron doped carbonitride and molybdenum disulfide respectively, and molal volume concentration is dissolved in after mixing and is
In the sulfuric acid solution of 3mol/L, stir evenly, distillation be washed to neutrality, 50 DEG C at a temperature of be dried in vacuo, obtained ternary has
Machine-inorganic hybrid material composite flame-retardant agent (ODOPB@g-C3N4 @MoS2).
It weighs 70g EVA and is placed in plastics processing mill, melted at 110 DEG C, be then mixed in a certain ratio EG and ODOPB@g-
C3N4@MoS2(see Table 1) is subsequently poured into mold (mm × 3.2 of 130 mm × 6.5 mm) on hydraulic flat vulcanizer hot
240 s are pressed, cooling 1 min of hydraulic press is moved to, demoulding obtains composite material batten.
The structure and performance of composite flame-retardant agent made from embodiment 1
1. infrared analysis
Fig. 1 is ODOPB, g-C3N4With ODOPB@C3N4-B@MoS2Infrared comparison diagram.In the spectrum of ODOPB, 1456 cm-1
Locate CH2And CH3Rocking vibration peak, 1195 cm-1Place is the stretching vibration peak of P=O, 756 cm-1Place replaces virtue between indicating
The presence of ring, the presence of phosphorous functional group prove that ODOPB has been synthesized；Boron doped g-C3N4Spectrum in, 1639 cm-1
Place is the stretching vibration peak of C=N, is g-C3N4Typical characteristic peak, and appear in ODOPB@g-C3N4@MoS2Spectrum in, and
937 cm-1With 1100 cm-1, correspond to MoS2S-S and Mo-O key, can prove that tri compound fire retardant has synthesized accordingly.
2. Analysis of Compatibility
Fig. 2 is the plane of disruption scanning electron microscope that composite flame-retardant agent made from embodiment 1 is added to the composite flame-proof material formed in EVA
Figure.It can be seen from the figure that adding the surface the EVA uniform ground after the composite flame-retardant agent, dense non-porous illustrates composite flame-retardant agent
There is good compatibility with basis material, the original mechanical property of EVA material will not be damaged.
3. Analysis on Mechanism
MoS2In combustion, the barrier action similar to graphene, montmorillonite, MoS are played2Fine and close reticular structure packet
The surface of polymer is overlayed on, the burning of polymeric inner matrix can be reduced, acts synergistically and hinders with the bulking effect of expansible graphite
Keep off heat transfer；The heated decomposing shape PO of phospho hetero phenanthrene functional group and phenoxyl radicals in ODOPB, capture H and OH is certainly
By base, quenching effect is played to inhibit combustion reaction；Boron doped g-C3N4During pyrolysis, NO, NO are released2It can consume
Oxygen simultaneously takes away a part of heat, and the compound of boracic can promote to form fine and close layer of charcoal, generates barrier effect, reduces smog
It generates.
The temperature that borate switchs to glassy state can be improved in ODOPB, enhances the compatibility of fire retardant and polymer, reduces addition
Damage of the fire retardant to polymer mechanical performance itself.The synergistic effect of ternary flame retardant is in gas phase and condensed phase to EVA material
Material all has excellent flame retardant effect.
Embodiment 2
By miscellaneous 16 g of -10- phospho hetero phenanthrene -10- oxide (DOPO) of addition 9,10- dihydro-9-oxy and benzene in 30 mL ethoxy ethanols
The ratio of 16 g of quinone takes ethoxy ethanol, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and benzoquinones respectively, will
DOPO and benzoquinones are dissolved in ethoxy ethanol, 110 DEG C at a temperature of react 5 hours, obtain phospho hetero phenanthrene oxide；1 ︰ in mass ratio
3, take boric acid and dicyanodiamine respectively, completely dissolve in water, 60 DEG C at a temperature of be stirred, until water evaporating completely,
It is placed in the environment that temperature is 500 DEG C and calcines 3h, obtain boron doped carbonitride；1 ︰ 2 in mass ratio, takes ammonium molybdate and sulphur respectively
Urea completely dissolves in water, 60 DEG C at a temperature of be stirred, until water evaporating completely, be placed in the environment that temperature is 500 DEG C
Middle calcining 3h, obtains molybdenum disulfide；1 ︰ in mass ratio, 1 ︰ 1, takes phospho hetero phenanthrene oxide, boron doped carbonitride and curing respectively
Molybdenum is dissolved in the sulfuric acid solution that molal volume concentration is 3mol/L after mixing, stirs evenly, and distillation is washed to neutrality, at 50 DEG C
At a temperature of be dried in vacuo, be made ternary hybrid inorganic-organic materials composite flame-retardant agent.
Embodiment 3
By miscellaneous -10- phospho hetero phenanthrene -10- oxide (DOPO) 16g of addition 9,10- dihydro-9-oxy and benzoquinones in 35mL ethoxy ethanol
The ratio of 16g takes ethoxy ethanol, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and benzoquinones respectively, by DOPO
Be dissolved in ethoxy ethanol with benzoquinones, 110 DEG C at a temperature of react 5 hours, obtain phospho hetero phenanthrene oxide；1 ︰ 4 in mass ratio, point
Do not take boric acid and dicyanodiamine, completely dissolve in water, 60 DEG C at a temperature of be stirred, until water evaporating completely, be placed in
3h is calcined in the environment that temperature is 550 DEG C, obtains boron doped carbonitride；1 ︰ 3 in mass ratio, takes ammonium molybdate and thiocarbamide respectively, complete
Fully dissolved Yu Shuizhong, 60 DEG C at a temperature of be stirred, until water evaporating completely, be placed in the environment that temperature is 550 DEG C and forge
3h is burnt, molybdenum disulfide is obtained；1 ︰ in mass ratio, 1 ︰ 1, takes ODOPB, g-C respectively3N4And MoS2, molal volume concentration is dissolved in after mixing
To stir evenly in the sulfuric acid solution of 3mol/L, distillation is washed to neutrality, 50 DEG C at a temperature of be dried in vacuo, ternary is made
Hybrid inorganic-organic materials composite flame-retardant agent.
Embodiment 4
By miscellaneous -10- phospho hetero phenanthrene -10- oxide (DOPO) 16g of addition 9,10- dihydro-9-oxy and benzoquinones in 40mL ethoxy ethanol
The ratio of 16g takes ethoxy ethanol, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and benzoquinones respectively, by DOPO
Be dissolved in ethoxy ethanol with benzoquinones, 115 DEG C at a temperature of react 5 hours, obtain ODOPB；1 ︰ 5 in mass ratio, takes boron respectively
Acid and dicyanodiamine, completely dissolve in water, 60 DEG C at a temperature of be stirred, until water evaporating completely, being placed in temperature is
4h is calcined in 550 DEG C of environment, obtains boron doped carbonitride g-C3N4；1 ︰ 4 in mass ratio, takes ammonium molybdate and thiocarbamide, completely respectively
Be dissolved in the water, 60 DEG C at a temperature of be stirred, until water evaporating completely, be placed in the environment that temperature is 550 DEG C and calcine
3h obtains MoS2；1 ︰ in mass ratio, 1 ︰ 1, takes ODOPB, g-C respectively3N4And MoS2, it is 3mol/ that molal volume concentration is dissolved in after mixing
In the sulfuric acid solution of L, stir evenly, distillation be washed to neutrality, 50 DEG C at a temperature of be dried in vacuo, be made ternary it is organic-nothing
Machine hybrid material composite flame-retardant agent.
Embodiment 5
By miscellaneous -10- phospho hetero phenanthrene -10- oxide (DOPO) 16g of addition 9,10- dihydro-9-oxy and benzoquinones in 40mL ethoxy ethanol
The ratio of 16g takes ethoxy ethanol, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and benzoquinones respectively, by DOPO
Be dissolved in ethoxy ethanol with benzoquinones, 115 DEG C at a temperature of react 5 hours, obtain ODOPB；1 ︰ 6 in mass ratio, takes boron respectively
Acid and dicyanodiamine, completely dissolve in water, 60 DEG C at a temperature of be stirred, until water evaporating completely, being placed in temperature is
4h is calcined in 550 DEG C of environment, obtains g-C3N4；1 ︰ 4 in mass ratio, takes ammonium molybdate and thiocarbamide respectively, completely dissolves in water,
It is stirred at a temperature of 60 DEG C, until water evaporating completely, is placed in the environment that temperature is 550 DEG C and calcines 3h, obtain MoS2；By matter
Ratio 1 ︰, 1 ︰ 1 is measured, takes ODOPB, g-C respectively3N4And MoS2, it is dissolved in after mixing in the sulfuric acid solution that molal volume concentration is 3mol/L,
Stir evenly, distillation be washed to neutrality, 50 DEG C at a temperature of be dried in vacuo, obtain the compound resistance of ternary hybrid inorganic-organic materials
Fire agent.
Embodiment 6
By miscellaneous -10- phospho hetero phenanthrene -10- oxide (DOPO) 16g of addition 9,10- dihydro-9-oxy and benzene in 45 mL ethoxy ethanols
The ratio of quinone 16g takes ethoxy ethanol, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and benzoquinones respectively, will
DOPO and benzoquinones are dissolved in ethoxy ethanol, 115 DEG C at a temperature of react 5 hours, obtain ODOPB；1 ︰ 7 in mass ratio, respectively
Take boric acid and dicyanodiamine, completely dissolve in water, 60 DEG C at a temperature of be stirred, until water evaporating completely, be placed in temperature
Degree obtains g-C to calcine 4h in 550 DEG C of environment3N4；1 ︰ 2 in mass ratio, takes ammonium molybdate and thiocarbamide respectively, is dissolved completely in water
In, 65 DEG C at a temperature of be stirred, until water evaporating completely, be placed in the environment that temperature is 500 DEG C and calcine 4h, obtain
MoS2；1 ︰ in mass ratio, 1 ︰ 2, takes ODOPB, g-C respectively3N4And MoS2, the sulphur that molal volume concentration is 4mol/L is dissolved in after mixing
In acid solution, stir evenly, be washed till neutrality through distilled water, 55 DEG C at a temperature of be dried in vacuo, obtain ternary hybrid inorganic-organic material
Expect composite flame-retardant agent.
Embodiment 7
By miscellaneous -10- phospho hetero phenanthrene -10- oxide (DOPO) 16g of addition 9,10- dihydro-9-oxy and benzoquinones in 50mL ethoxy ethanol
The ratio of 16g takes ethoxy ethanol, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and benzoquinones respectively, by DOPO
Be dissolved in ethoxy ethanol with benzoquinones, 115 DEG C at a temperature of react 5 hours, obtain ODOPB；1 ︰ 8 in mass ratio, takes boron respectively
Acid and dicyanodiamine, completely dissolve in water, 60 DEG C at a temperature of be stirred, until water evaporating completely, being placed in temperature is
4h is calcined in 550 DEG C of environment, obtains g-C3N4；1 ︰ 3 in mass ratio, takes ammonium molybdate and thiocarbamide respectively, completely dissolves in water,
It is stirred at a temperature of 65 DEG C, until water evaporating completely, is placed in the environment that temperature is 550 DEG C and calcines 4h, obtain MoS2；By matter
Ratio 1 ︰, 1 ︰ 2 is measured, takes ODOPB, g-C respectively3N4And MoS2, it is dissolved in after mixing in the sulfuric acid solution that molal volume concentration is 4mol/L,
Stir evenly, through distillation be washed to neutrality, 55 DEG C at a temperature of be dried in vacuo, it is compound to obtain ternary hybrid inorganic-organic materials
Fire retardant.
Embodiment 8
In the ratio that 15 g of DOPO and 15 g of benzoquinones are added in 25mL ethoxy ethanol, ethoxy ethanol, DOPO and benzene are taken respectively
DOPO and benzoquinones are dissolved in ethoxy ethanol by quinone, 115 DEG C at a temperature of react 5 hours, obtain ODOPB；1 ︰ 2 in mass ratio,
Take boric acid and dicyanodiamine respectively, completely dissolve in water, 65 DEG C at a temperature of be stirred, until water evaporating completely, set
4h is calcined in the environment that temperature is 550 DEG C, obtains g-C3N4；1 ︰ 4 in mass ratio, takes ammonium molybdate and thiocarbamide respectively, is dissolved completely in
In water, 65 DEG C at a temperature of be stirred, until water evaporating completely, be placed in the environment that temperature is 550 DEG C and calcine 4h, obtain
MoS2；1 ︰ in mass ratio, 1 ︰ 2, takes ODOPB, g-C respectively3N4And MoS2, it is 4 mol/L's that molal volume concentration is dissolved in after mixing
In sulfuric acid solution, stir evenly, distillation be washed to neutrality, 55 DEG C at a temperature of be dried in vacuo, obtain ternary hybrid inorganic-organic
Material cladding fire retardant.
Embodiment 9
In the ratio that 16 g of DOPO and 17 g of benzoquinones are added in 30mL ethoxy ethanol, ethoxy ethanol, DOPO and benzene are taken respectively
DOPO and benzoquinones are dissolved in ethoxy ethanol by quinone, 120 DEG C at a temperature of react 5 hours, obtain ODOPB；1 ︰ 3 in mass ratio,
Take boric acid and dicyanodiamine respectively, completely dissolve in water, 65 DEG C at a temperature of be stirred, until water evaporating completely, set
4h is calcined in the environment that temperature is 600 DEG C, obtains g-C3N4；1 ︰ 2 in mass ratio, takes ammonium molybdate and thiocarbamide respectively, is dissolved completely in
In water, 70 DEG C at a temperature of be stirred, until water evaporating completely, be placed in the environment that temperature is 550 DEG C and calcine 4h, obtain
MoS2；1 ︰ in mass ratio, 1 ︰ 2, takes ODOPB, g-C respectively3N4And MoS2, it is 4 mol/L's that molal volume concentration is dissolved in after mixing
In sulfuric acid solution, stir evenly, distillation be washed to neutrality, 60 DEG C at a temperature of be dried in vacuo, obtain ternary hybrid inorganic-organic
Material cladding fire retardant.
Embodiment 10
In the ratio that 17 g of DOPO and 17 g of benzoquinones are added in 30mL ethoxy ethanol, ethoxy ethanol, DOPO and benzene are taken respectively
DOPO and benzoquinones are dissolved in ethoxy ethanol by quinone, 120 DEG C at a temperature of react 5 hours, obtain ODOPB；1 ︰ 4 in mass ratio,
Take boric acid and dicyanodiamine respectively, completely dissolve in water, 70 DEG C at a temperature of be stirred, until water evaporating completely, set
4h is calcined in the environment that temperature is 600 DEG C, obtains g-C3N4；1 ︰ 2 in mass ratio, takes ammonium molybdate and thiocarbamide respectively, is dissolved completely in
In water, 75 DEG C at a temperature of be stirred, until water evaporating completely, be placed in the environment that temperature is 600 DEG C and calcine 4h, obtain
MoS2；1 ︰ in mass ratio, 1 ︰ 2, takes ODOPB, g-C respectively3N4And MoS2, the sulphur that molal volume concentration is 5mol/L is dissolved in after mixing
In acid solution, stir evenly, distillation be washed to neutrality, 60 DEG C at a temperature of be dried in vacuo, obtain ternary hybrid inorganic-organic material
Expect composite flame-retardant agent.
Embodiment 11
In in 30 mL ethoxy ethanols be added 18 g of DOPO and 18 g of benzoquinones ratio, take respectively ethoxy ethanol, DOPO and
DOPO and benzoquinones are dissolved in ethoxy ethanol by benzoquinones, 120 DEG C at a temperature of react 5 hours, obtain ODOPB；1 ︰ in mass ratio
4, take boric acid and dicyanodiamine respectively, completely dissolve in water, 75 DEG C at a temperature of be stirred, until water evaporating completely,
It is placed in the environment that temperature is 600 DEG C and calcines 5 h, obtain g-C3N4；1 ︰ 2 in mass ratio, takes ammonium molybdate and thiocarbamide respectively, completely molten
In Xie Yushui, 80 DEG C at a temperature of be stirred, until water evaporating completely, be placed in the environment that temperature is 600 DEG C and calcine 5
H obtains MoS2；1 ︰ in mass ratio, 1 ︰ 2, takes ODOPB, g-C respectively3N4And MoS2, it is 5 mol/ that molal volume concentration is dissolved in after mixing
In the sulfuric acid solution of L, stir evenly, distillation be washed to neutrality, 60 DEG C at a temperature of be dried in vacuo, obtain ternary organic and inorganic
Hybrid material composite flame-retardant agent.
Embodiment 12
In the ratio that DOPO 17g and benzoquinones 18g are added in 30mL ethoxy ethanol, ethoxy ethanol, DOPO and benzene are taken respectively
DOPO and benzoquinones are dissolved in ethoxy ethanol by quinone, 120 DEG C at a temperature of react 5 hours, obtain ODOPB；1 ︰ 4 in mass ratio,
Take boric acid and dicyanodiamine respectively, completely dissolve in water, 80 DEG C at a temperature of be stirred, until water evaporating completely, set
5 h are calcined in the environment that temperature is 600 DEG C, obtain g-C3N4；1 ︰ 3 in mass ratio, takes ammonium molybdate and thiocarbamide respectively, is completely dissolved
Yu Shuizhong, 65 DEG C at a temperature of be stirred, until water evaporating completely, be placed in the environment that temperature is 600 DEG C and calcine 5 h,
Obtain MoS2；1 ︰ in mass ratio, 1 ︰ 3, takes ODOPB, g-C respectively3N4And MoS2, it is 5mol/L's that molal volume concentration is dissolved in after mixing
In sulfuric acid solution, stir evenly, distillation be washed to neutrality, 65 DEG C at a temperature of be dried in vacuo, obtain ternary hybrid inorganic-organic
Material cladding fire retardant.
Embodiment 13
In in 30 mL ethoxy ethanols be added 19 g of DOPO and 19 g of benzoquinones ratio, take respectively ethoxy ethanol, DOPO and
DOPO and benzoquinones are dissolved in ethoxy ethanol by benzoquinones, 120 DEG C at a temperature of react 5 hours, obtain ODOPB；1 ︰ in mass ratio
5, take boric acid and dicyanodiamine respectively, completely dissolve in water, 65 DEG C at a temperature of be stirred, until water evaporating completely,
It is placed in the environment that temperature is 600 DEG C and calcines 6 h, obtain g-C3N4；1 ︰ 3 in mass ratio, takes ammonium molybdate and thiocarbamide respectively, completely molten
In Xie Yushui, 65 DEG C at a temperature of be stirred, until water evaporating completely, be placed in the environment that temperature is 600 DEG C and calcine 6
H obtains MoS2；1 ︰ in mass ratio, 1 ︰ 3, takes ODOPB, g-C respectively3N4And MoS2, it is 5mol/L that molal volume concentration is dissolved in after mixing
Sulfuric acid solution in, stir evenly, distillation be washed to neutrality, 65 DEG C at a temperature of be dried in vacuo, it is miscellaneous to obtain ternary organic and inorganic
Change Material cladding fire retardant.
Embodiment 14
In the ratio that DOPO 20g and benzoquinones 20g are added in 30mL ethoxy ethanol, ethoxy ethanol, DOPO and benzene are taken respectively
DOPO and benzoquinones are dissolved in ethoxy ethanol by quinone, 120 DEG C at a temperature of react 5 hours, obtain ODOPB；1 ︰ 5 in mass ratio,
Take boric acid and dicyanodiamine respectively, completely dissolve in water, 70 DEG C at a temperature of be stirred, until water evaporating completely, set
4 h are calcined in the environment that temperature is 650 DEG C, obtain g-C3N4；1 ︰ 3 in mass ratio, takes ammonium molybdate and thiocarbamide respectively, is completely dissolved
Yu Shuizhong, 70 DEG C at a temperature of be stirred, until water evaporating completely, be placed in the environment that temperature is 650 DEG C and calcine 4h, obtain
MoS2；1 ︰: 1 ︰ 3 in mass ratio, takes ODOPB, g-C respectively3N4And MoS2, it is 5mol/L's that molal volume concentration is dissolved in after mixing
In sulfuric acid solution, stir evenly, distillation be washed to neutrality, 70 DEG C at a temperature of be dried in vacuo, be made ternary organic and inorganic it is miscellaneous
Change Material cladding fire retardant.
Embodiment 15
In the ratio that DOPO 15g and benzoquinones 16g are added in 35 mL ethoxy ethanols, ethoxy ethanol, DOPO and benzene are taken respectively
DOPO and benzoquinones are dissolved in ethoxy ethanol by quinone, 125 DEG C at a temperature of react 5 hours, obtain ODOPB；1 ︰ 6 in mass ratio,
Take boric acid and dicyanodiamine respectively, completely dissolve in water, 70 DEG C at a temperature of be stirred, until water evaporating completely, set
5h is calcined in the environment that temperature is 650 DEG C, obtains g-C3N4；1 ︰ 3 in mass ratio, takes ammonium molybdate and thiocarbamide respectively, is dissolved completely in
In water, 75 DEG C at a temperature of be stirred, until water evaporating completely, be placed in the environment that temperature is 650 DEG C and calcine 5h, obtain
MoS2；1 ︰ in mass ratio, 1 ︰ 4, takes ODOPB, g-C respectively3N4And MoS2, the sulphur that molal volume concentration is 5mol/L is dissolved in after mixing
In acid solution, stir evenly, distillation be washed to neutrality, 70 DEG C at a temperature of be dried in vacuo, obtain ternary hybrid inorganic-organic material
Expect composite flame-retardant agent.
Embodiment 16
In the ratio that DOPO 16g and benzoquinones 16g are added in 35 mL ethoxy ethanols, ethoxy ethanol, DOPO and benzene are taken respectively
DOPO and benzoquinones are dissolved in ethoxy ethanol by quinone, 125 DEG C at a temperature of react 5 hours, obtain ODOPB；1 ︰ 6 in mass ratio,
Take boric acid and dicyanodiamine respectively, completely dissolve in water, 75 DEG C at a temperature of be stirred, until water evaporating completely, set
6h is calcined in the environment that temperature is 650 DEG C, obtains g-C3N4；1 ︰ 3 in mass ratio, takes ammonium molybdate and thiocarbamide respectively, is dissolved completely in
In water, 80 DEG C at a temperature of be stirred, until water evaporating completely, be placed in the environment that temperature is 650 DEG C and calcine 6h, obtain
(MoS2；1 ︰ in mass ratio, 1 ︰ 3, takes ODOPB, g-C respectively3N4And MoS2, it is 5mol/L's that molal volume concentration is dissolved in after mixing
In sulfuric acid solution, stir evenly, distillation be washed to neutrality, 70 DEG C at a temperature of be dried in vacuo, obtain ternary hybrid inorganic-organic
Material cladding fire retardant.
Embodiment 17
In the ratio that DOPO 17g and benzoquinones 17g are added in 35 mL ethoxy ethanols, ethoxy ethanol, DOPO and benzene are taken respectively
DOPO and benzoquinones are dissolved in ethoxy ethanol by quinone, 125 DEG C at a temperature of react 5 hours, obtain ODOPB；1 ︰ 6 in mass ratio,
Take boric acid and dicyanodiamine respectively, completely dissolve in water, 75 DEG C at a temperature of be stirred, until water evaporating completely, set
7h is calcined in the environment that temperature is 650 DEG C, obtains g-C3N4；1 ︰ 4 in mass ratio, takes ammonium molybdate and thiocarbamide respectively, is dissolved completely in
In water, 65 DEG C at a temperature of be stirred, until water evaporating completely, be placed in the environment that temperature is 650 DEG C and calcine 7h, obtain
MoS2；1 ︰ in mass ratio, 1 ︰ 4, takes ODOPB, g-C respectively3N4And MoS2, the sulphur that molal volume concentration is 6mol/L is dissolved in after mixing
In acid solution, stir evenly, through distillation be washed to neutrality, 75 DEG C at a temperature of be dried in vacuo, obtain ternary hybrid inorganic-organic
Material cladding fire retardant.
Embodiment 18
In the ratio that DOPO 18g and benzoquinones 18g are added in 35mL ethoxy ethanol, ethoxy ethanol, DOPO and benzene are taken respectively
DOPO and benzoquinones are dissolved in ethoxy ethanol by quinone, 125 DEG C at a temperature of react 5 hours, obtain ODOPB；1 ︰ 6 in mass ratio,
Take boric acid and dicyanodiamine respectively, completely dissolve in water, 80 DEG C at a temperature of be stirred, until water evaporating completely, set
4h is calcined in the environment that temperature is 700 DEG C, obtains g-C3N4；1 ︰ 4 in mass ratio, takes ammonium molybdate and thiocarbamide respectively, is dissolved completely in
In water, 70 DEG C at a temperature of be stirred, until water evaporating completely, being placed in temperature is 700℃Environment in calcine 4 h, obtain two
Molybdenum sulfide (MoS2)；1 ︰ in mass ratio, 1 ︰ 4, takes ODOPB, g-C respectively3N4And MoS2, molal volume concentration is dissolved in after mixing is
In the sulfuric acid solution of 6mol/L, stir evenly, distillation be washed to neutrality, 75 DEG C at a temperature of be dried in vacuo, obtain ternary it is organic-
Inorganic hybrid material composite flame-retardant agent.
Embodiment 19
In the ratio that DOPO 19g and benzoquinones 19g are added in 35mL ethoxy ethanol, ethoxy ethanol, DOPO and benzene are taken respectively
DOPO and benzoquinones are dissolved in ethoxy ethanol by quinone, 125 DEG C at a temperature of react 5 hours, obtain ODOPB；1 ︰ 7 in mass ratio,
Take boric acid and dicyanodiamine respectively, completely dissolve in water, 65 DEG C at a temperature of be stirred, until water evaporating completely, set
5 h are calcined in the environment that temperature is 700 DEG C, obtain g-C3N4；1 ︰ 4 in mass ratio, takes ammonium molybdate and thiocarbamide respectively, is completely dissolved
Yu Shuizhong, 75 DEG C at a temperature of be stirred, until water evaporating completely, be placed in the environment that temperature is 700 DEG C and calcine 5h, obtain
MoS2；1 ︰ in mass ratio, 1 ︰ 4, takes ODOPB, g-C respectively3N4And MoS2, the sulphur that molal volume concentration is 6mol/L is dissolved in after mixing
In acid solution, stir evenly, distillation be washed to neutrality, 75 DEG C at a temperature of be dried in vacuo, obtain ternary hybrid inorganic-organic material
Expect composite flame-retardant agent.
Embodiment 20
In the ratio that DOPO 18g and benzoquinones 18g are added in 40mL ethoxy ethanol, ethoxy ethanol, DOPO and benzene are taken respectively
DOPO and benzoquinones are dissolved in ethoxy ethanol by quinone, 125 DEG C at a temperature of react 5 hours, obtain ODOPB；1 ︰ 7 in mass ratio,
Take boric acid and dicyanodiamine respectively, completely dissolve in water, 70 DEG C at a temperature of be stirred, until water evaporating completely, set
5 h are calcined in the environment that temperature is 700 DEG C, obtain g-C3N4；1 ︰ 4 in mass ratio, takes ammonium molybdate and thiocarbamide respectively, is completely dissolved
Yu Shuizhong, 75 DEG C at a temperature of be stirred, until water evaporating completely, be placed in the environment that temperature is 700 DEG C and calcine 5h, obtain
MoS2；1 ︰ in mass ratio, 1 ︰ 4, takes ODOPB, g-C respectively3N4And MoS2, the sulphur that molal volume concentration is 6mol/L is dissolved in after mixing
In acid solution, stir evenly, distillation be washed to neutrality, 75 DEG C at a temperature of be dried in vacuo, obtain ternary hybrid inorganic-organic material
Expect composite flame-retardant agent.
Embodiment 21
In the ratio that DOPO 19g and benzoquinones 19g are added in 40mL ethoxy ethanol, ethoxy ethanol, DOPO and benzene are taken respectively
DOPO and benzoquinones are dissolved in ethoxy ethanol by quinone, 125 DEG C at a temperature of react 5 hours, obtain ODOPB；1 ︰ 7 in mass ratio,
Take boric acid and dicyanodiamine respectively, completely dissolve in water, 75 DEG C at a temperature of be stirred, until water evaporating completely, set
6h is calcined in the environment that temperature is 700 DEG C, obtains g-C3N4；1 ︰ 4 in mass ratio, takes ammonium molybdate and thiocarbamide respectively, is dissolved completely in
In water, 80 DEG C at a temperature of be stirred, until water evaporating completely, be placed in the environment that temperature is 700 DEG C and calcine 6h, obtain
MoS2；1 ︰ in mass ratio, 1 ︰ 5, takes ODOPB, g-C respectively3N4And MoS2, the sulphur that molal volume concentration is 6mol/L is dissolved in after mixing
In acid solution, stir evenly, distillation be washed to neutrality, 80 DEG C at a temperature of be dried in vacuo, obtain ternary hybrid inorganic-organic material
Expect composite flame-retardant agent.
Embodiment 22
In the ratio that DOPO 18g and benzoquinones 18g are added in 45mL ethoxy ethanol, ethoxy ethanol, DOPO and benzene are taken respectively
DOPO and benzoquinones are dissolved in ethoxy ethanol by quinone, 130 DEG C at a temperature of react 5 hours, obtain ODOPB；1 ︰ 8 in mass ratio,
Take boric acid and dicyanodiamine respectively, completely dissolve in water, 70 DEG C at a temperature of be stirred, until water evaporating completely, set
7h is calcined in the environment that temperature is 700 DEG C, obtains g-C3N4；1 ︰ 4 in mass ratio, takes ammonium molybdate and thiocarbamide respectively, is dissolved completely in
In water, 80 DEG C at a temperature of be stirred, until water evaporating completely, be placed in the environment that temperature is 700 DEG C and calcine 6h, obtain
MoS2；1 ︰ in mass ratio, 1 ︰ 5, takes ODOPB, g-C respectively3N4And MoS2, the sulphur that molal volume concentration is 7mol/L is dissolved in after mixing
In acid solution, stir evenly, distillation be washed to neutrality, 80 DEG C at a temperature of be dried in vacuo, obtain ternary hybrid inorganic-organic material
Expect composite flame-retardant agent.
Embodiment 23
In the ratio that DOPO 19g and benzoquinones 19g are added in 45mL ethoxy ethanol, ethoxy ethanol, DOPO and benzene are taken respectively
DOPO and benzoquinones are dissolved in ethoxy ethanol by quinone, 130 DEG C at a temperature of react 5 hours, obtain ODOPB；1 ︰ 8 in mass ratio,
Take boric acid and dicyanodiamine respectively, completely dissolve in water, 70 DEG C at a temperature of be stirred, until water evaporating completely, set
7h is calcined in the environment that temperature is 700 DEG C, obtains g-C3N4；1 ︰ 4 in mass ratio, takes ammonium molybdate and thiocarbamide respectively, is dissolved completely in
In water, 80 DEG C at a temperature of be stirred, until water evaporating completely, be placed in the environment that temperature is 700 DEG C and calcine 7h, obtain
MoS2；1 ︰ in mass ratio, 1 ︰ 5, takes ODOPB, g-C respectively3N4And MoS2, the sulphur that molal volume concentration is 8mol/L is dissolved in after mixing
In acid solution, stir evenly, distillation be washed to neutrality, 80 DEG C at a temperature of be dried in vacuo, obtain ternary hybrid inorganic-organic material
Expect composite flame-retardant agent.
Embodiment 24
In the ratio that DOPO 20g and benzoquinones 20g are added in 45mL ethoxy ethanol, ethoxy ethanol, DOPO and benzene are taken respectively
DOPO and benzoquinones are dissolved in ethoxy ethanol by quinone, 130 DEG C at a temperature of react 5 hours, obtain ODOPB；1 ︰ 8 in mass ratio,
Take boric acid and dicyanodiamine respectively, completely dissolve in water, 80 DEG C at a temperature of be stirred, until water evaporating completely, set
7h is calcined in the environment that temperature is 700 DEG C, obtains g-C3N4；1 ︰ 4 in mass ratio, takes ammonium molybdate and thiocarbamide respectively, is dissolved completely in
In water, 80 DEG C at a temperature of be stirred, until water evaporating completely, be placed in the environment that temperature is 700 DEG C and calcine 7h, obtain
MoS2；1 ︰ in mass ratio, 1 ︰ 5, takes ODOPB, g-C respectively3N4And MoS2, the sulphur that molal volume concentration is 8mol/L is dissolved in after mixing
In acid solution, stir evenly, distillation be washed to neutrality, 80 DEG C at a temperature of be dried in vacuo, obtain ternary hybrid inorganic-organic material
Expect composite flame-retardant agent.
Embodiment 25
In the ratio that DOPO 20g and benzoquinones 20g are added in 50mL ethoxy ethanol, ethoxy ethanol, DOPO and benzene are taken respectively
DOPO and benzoquinones are dissolved in ethoxy ethanol by quinone, 130 DEG C at a temperature of react 5 hours, obtain ODOPB；1 ︰ 8 in mass ratio,
Take boric acid and dicyanodiamine respectively, completely dissolve in water, 80 DEG C at a temperature of be stirred, until water evaporating completely, set
7h is calcined in the environment that temperature is 700 DEG C, obtains g-C3N4；1 ︰ 4 in mass ratio, takes ammonium molybdate and thiocarbamide respectively, is dissolved completely in
In water, 80 DEG C at a temperature of be stirred, until water evaporating completely, being placed in temperature is 700℃Environment in calcine 7h, obtain
MoS2；1 ︰ in mass ratio, 1 ︰ 5, takes ODOPB, g-C respectively3N4And MoS2, the sulphur that molal volume concentration is 8mol/L is dissolved in after mixing
In acid solution, stir evenly, distillation be washed to neutrality, 80 DEG C at a temperature of be dried in vacuo, obtain ternary hybrid inorganic-organic material
Expect composite flame-retardant agent.
Ternary hybrid inorganic-organic materials composite flame-retardant agent made from the various embodiments described above is compounded with expansible graphite (EG)
After apply in EVA basis material, oxygen index (OI) (LOI) is as shown in table 1.
The oxygen index (OI) of 1 composite material of table
The composite flame-retardant agent obtained it can be seen from the data in table is applied after compounding with expansible graphite (EG) in EVA material
In, when the mass ratio of composite flame-retardant agent and EG are 1:9, flame retardant effect is best, oxygen index (OI) 32.5%.
Claims (3)
1. a kind of ternary hybrid inorganic-organic materials composite flame-retardant agent, which is characterized in that the composite flame-retardant agent is made in this way:
1) by addition 15~20g of the miscellaneous -10- phospho hetero phenanthrene -10- oxide of 9,10- dihydro-9-oxy in 20~50 mL ethoxy ethanols
With the ratio of 15~25g of benzoquinones, ethoxy ethanol, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and benzene are taken respectively
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and benzoquinones are dissolved in ethoxy ethanol by quinone, at 110~130 DEG C
At a temperature of react 5 hours, obtain phospho hetero phenanthrene oxide；
1 ︰ 2~8 in mass ratio, takes boric acid and dicyanodiamine respectively, completely dissolves in water, 60~80 DEG C at a temperature of stir
Mixing, until water evaporating completely, is placed in the environment that temperature is 500~700 DEG C and calcines 3~7h, obtain boron doped carbonitride；
1 ︰ 1~4 in mass ratio, takes ammonium molybdate and thiocarbamide respectively, completely dissolves in water, mixed in 60~80 DEG C of at a temperature of stirring
It closes, until water evaporating completely, is placed in the environment that temperature is 500~700 DEG C and calcines 3~7h, obtain molybdenum disulfide；
2) 1 ︰ in mass ratio, 1 ︰ 1~5 takes phospho hetero phenanthrene oxide, boron doped carbonitride and molybdenum disulfide respectively, is dissolved in after mixing
It in sulfuric acid solution, stirs evenly, is washed till neutrality, be dried in vacuo, obtain ternary hybrid inorganic-organic materials composite flame-retardant agent.
2. ternary hybrid inorganic-organic materials composite flame-retardant agent as described in claim 1, which is characterized in that the step 2
In, the molal volume concentration of sulfuric acid solution used is 3~8 mol/L.
3. ternary hybrid inorganic-organic materials composite flame-retardant agent described in a kind of claim 1 is to prepare ethylene-vinyl acetate total
Application in polymers fire proofing.
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