CN109401224A - A kind of halogen-free expansion fire retardant and preparation method thereof - Google Patents
A kind of halogen-free expansion fire retardant and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to technical field of flame retardant, more particularly to a kind of halogen-free expansion fire retardant and preparation method thereof, the raw material including following parts by weight: melamine derivative, coated ammonium polyphosphate, pyrrolotriazine derivatives, pentaerythritol phosphate, trihydroxyethyl isocyanuric ester, organic sesqui siloxane, nano silica, synergistic flame retardant, smoke suppressant, at charcoal promotor, coupling agent, antioxidant, lubricant.Expansion type flame retardant good flame retardation effect of the invention, and additive amount is few, can farthest reduce the influence to plastics physical and mechanical property, also has the advantages that Halogen, low cigarette, low toxicity, anti-molten drop and non-corrosive gas；And fine and close porous foam layer of charcoal is formed in material surface in burning, the release of the further degradation and combustible of internal layer high polymer to surface can be not only prevented, but also heat source can be prevented to the transmitting of high polymer and isolation oxygen source, to prevent the sprawling and propagation of flame.
Description
Technical field
The present invention relates to technical field of flame retardant, and in particular to a kind of halogen-free expansion fire retardant and preparation method thereof.
Background technique
Expansion type flame retardant is a kind of novel halogen-free flame retardants, because it discharges the gas that smog is few, discharges in burning
The advantages that layer of charcoal that harmless and burning generates can be effectively prevented polymer molten drop, especially suitable for the fire-retardant of polymer, institute
To be increasingly taken seriously in expansion type flame retardant fire-retardant research at home and abroad.
Expansion type flame retardant system mainly contains acid source, charcoal source and foaming source three classes component.In traditional expansion type flame-retarding
In agent system, is generally mostly formed with ammonium polyphosphate, polyalcohol and melamine compounding ingredients, therefore, generally believe intumescent system
Fire retardant mechanism are as follows: ammonium polyphosphate is thermally decomposed, generate have strong dehydration phosphoric acid and pyrophosphoric acid, make pentaerythritol ester
Change, and then dehydration carbonization.Reacting the ammonia that the water vapour formed and melamine decompose expands layer of charcoal, ultimately forms more than one layer
The layer of charcoal of micropore protects polymer body, reaches fire-retardant purpose to completely cut off air and heat transfer.
Existing expansion type flame retardant can express low cigarette, nontoxic, good flame retardation effect and certain resistance to melt-dropping property, but still
It is ideal not enough in the presence of such as flame retardant effect, the problem of the additive amount of fire retardant is larger etc..
Summary of the invention
In order to overcome shortcoming and defect existing in the prior art, the purpose of the present invention is to provide a kind of halogen-free expansibles
Fire retardant, the expansion type flame retardant good flame retardation effect, and additive amount is few, can farthest reduce to plastics physical and mechanical property
Influence, also have the advantages that Halogen, low cigarette, low toxicity, anti-molten drop and non-corrosive gas；And in burning in material surface shape
At fine and close porous foam layer of charcoal, the release of the further degradation and combustible of internal layer high polymer to surface can be not only prevented, but also can
Prevent heat source to the transmitting of high polymer and isolation oxygen source, to prevent the sprawling and propagation of flame.
Another object of the present invention is to provide a kind of preparation method of halogen-free expansion fire retardant, the preparation method steps
Simply, convenient operation and control, quality are stablized, and high production efficiency, production cost is low, can large-scale industrial production.
The purpose of the invention is achieved by the following technical solution: a kind of halogen-free expansion fire retardant, including following parts by weight
Raw material:
20-40 parts of melamine derivative
20-40 parts of coated ammonium polyphosphate
10-30 parts of pyrrolotriazine derivatives
10-20 parts of pentaerythritol phosphate
5-15 parts of trihydroxyethyl isocyanuric ester
6-10 parts of organic sesqui siloxane
4-8 parts of nano silica
3-7 parts of synergistic flame retardant
2-6 parts of smoke suppressant
At 2-4 parts of charcoal promotor
1-3 parts of coupling agent
1-2 parts of antioxidant
0.5-1.5 parts of lubricant.
Preferably, the melamine derivative is by melamine salt of pentaerythritol bis (dihydrogen phosphate), 24,8,10- tetra-
Bis- melamine salt of oxygen -3,9- hosphospiro [5,5] hendecane -3,9- dioxy -3,9- and (2,6,7- tri- oxygen -1- phosphorus-bicyclic
[2,2,2] octane -1- oxygen methyl) mixture that is formed with weight ratio 2-4:1-2:1 of phosphate melamine salt.The present invention passes through
Type, compounding and the proportion of strict control melamine derivative have Halogen, low cigarette, low-corrosiveness, low water absorbable, low water
The advantages that dissolubility, stream drop are less, flame retarding efficiency is high, at low cost.
Preferably, the coated ammonium polyphosphate is by melamine-formaldehyde coated ammonium polyphosphate, silane coated ammonium polyphosphate and not
The mixture that saturated resin coated ammonium polyphosphate is formed with weight ratio 1-2:0.5-1.5:1.The present invention is coated by strict control
Type, compounding and the proportion of ammonium polyphosphate under high temperature, can resolve into rapidly ammonia and polyphosphoric acid, ammonia can dilute in gas phase
Oxygen concentration, thus play a part of prevent burning.Polyphosphoric acid is strong dehydrating agent, and polymer dehydration carbonization can be made to form layer of charcoal,
Completely cut off contact of the polymer with oxygen, plays a part of to prevent burning in solid phase.
Preferably, the pyrrolotriazine derivatives are poly- 2- ethyl alcohol amido -4,6- ethylenediamine base -1,3,5-triazines.The present invention is logical
Cross using poly- 2- ethyl alcohol amido -4,6- ethylenediamine base -1,3,5-triazines, have colourless, Halogen, low toxicity, low cigarette, low-corrosiveness,
The advantages that uvioresistant irradiation, flame retarding efficiency high, at low cost, it is also used as carbon forming agent use.
The pentaerythritol phosphate is 1- oxo-4- methyl-1-phospha-2,6,7- trioxa-l-phosphabicyclo [2,2,2] octane.
The present invention has flame retardant effect by using 1- oxo-4- methyl-1-phospha-2,6,7- trioxa-l-phosphabicyclo [2,2,2] octane
Good, stability is good, also has extraordinary water resistance, solvent resistance.
For the present invention by using pentaerythritol phosphate, fire retardant obtained has the fire-retardant effect for efficiently, pressing down cigarette, low toxicity
Fruit.
Preferably, the organic sesqui siloxane is random silsesquioxane, trapezoidal half siloxane, bridge shape silsesquioxane
At least one of alkane and cagelike silsesquioxane.The present invention has good increasing by using above-mentioned organic sesqui siloxane
Tough performance can also improve product and obtain mechanical strength, heat resistance and anti-flammability.More preferably, organic silsesquioxane
Alkane is poly- (trimethylsiloxy group) silsesquioxane of cage type eight, epoxy group cagelike silsesquioxane and the trapezoidal silsesquioxane of vinyl
The mixture that alkane is formed with weight ratio 1:0.5-1.5:1.5-2.5.
Preferably, the surface of the nano silica is through silane coupler modified processing, method of modifying are as follows: configuration body
Than the ethanol/water solution for being 3-10:1 the nano silica for accounting for ethanol/water solution quality 1%-10% is added, in 3000- in product
High speed shear under the revolving speed of 4000rpm adds the silane coupling agent for accounting for ethanol/water solution quality 1%-10%, and it is molten that oxalic acid is added
Liquid makes the pH value of reaction system in 3-4, after reacting 1.5-2.5h, filters, washing, the nano-silica modified up to surface after dry
SiClx；Wherein, the silane coupling agent is by γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-methacryloxy
Propyl trimethoxy silicane and three isopropoxy silane of γ-methacryloxypropyl are with weight ratio 0.4-0.8:1:0.5-
The mixture of 1.5 compositions.The present invention is modified processing to the surface of nano silica using silane coupling agent, and strictly controls
Processing parameter processed and the type of silane coupling agent, compounding and proportion, can improve Nano-meter SiO_22It, can be with the compatibility of resin
Improve the intensity and heat resistance of resin.
Preferably, the synergistic flame retardant is by zinc borate, magnesium hydroxide and aluminium hydroxide with weight ratio 1.5-2.5:
The mixture of 0.5-1.5:1 composition.The present invention passes through type, compounding and the proportion of strict control synergistic flame retardant, can be improved
The flame retardant effect of material.
The smoke suppressant is by ferrocene, antimony oxide and ammonium octamolybdate with weight ratio 0.5-1.5:1.5-2.5:1 group
At mixture.The present invention passes through type, compounding and the proportion of strict control smoke suppressant, it is possible to reduce toxic smoke in combustion process
It generates.
Preferably, described at charcoal promotor is by pentaerythrite, poly- p-phenylene ethene diamine and phenolic resin with weight
Than the mixture of 1:0.8-1.2:0.5-1.5 composition.The present invention is by strict control at the type, compounding and weight of charcoal promotor
Proportion, can fast rapid-result charcoal.
The coupling agent is by tetravinyl tetramethyl-ring tetrasiloxane, vinyltriethoxysilane and glycidol ether
The mixture that base propyl trimethoxy silicane is formed with weight ratio 2-4:0.8-1.2:1.The present invention passes through strict control coupling agent
Type, compounding and weight proportion, the viscosity of molten synthetic resin can be reduced, improve the dispersion degree of filler to improve processability
Can, and then product is made to obtain good surface quality and machinery, heat and electrical property.
Preferably, the antioxidant is by β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, three
The mixing that [2.4- di-tert-butyl-phenyl] phosphite ester and the double lauryls of thio-2 acid are formed with weight ratio 1-2:0.8-1.2:1
Object.The present invention passes through type, compounding and the weight proportion of strict control antioxidant, can delay or inhibit material oxidation process
It carries out, to prevent the aging of material and prolong its service life.
The lubricant is by oxidized polyethylene wax, pentaerythritol stearate and N, N- ethylenebis ricinoleic acid acid amide
The mixture formed with weight ratio 0.8-1.2:1.4-2.2:1.The present invention passes through the type of strict control lubricant, compounding and again
Amount proportion, can make material in process improves the mobility of material and the release property of product, can reduce difficulty of processing,
Save energy consumption.
A kind of preparation method of halogen-free expansion fire retardant, includes the following steps:
(1) melamine derivative, coated ammonium polyphosphate, pyrrolotriazine derivatives, pentaerythritol phosphate, three are weighed in parts by weight
Hydroxyethyl isocyanurate ester, organic sesqui siloxane, nano silica, synergistic flame retardant, smoke suppressant, at charcoal promotor, idol
Join agent, antioxidant and lubricant, is respectively dried to moisture content lower than 0.1%, is then crushed to 10-50 μm of partial size respectively；
(2) 10-30min will be mixed in the raw material investment high-speed mixer after above-mentioned dries pulverizing, obtains mixture；And in N, N-
Cladding processing carried out to said mixture with ethylene-vinyl acetate resin in dimethylformamide, ethylene-vinyl acetate resin with
The weight ratio of mixture is 1: 50-100.
The beneficial effects of the present invention are: expansion type flame retardant good flame retardation effect of the invention, and additive amount is few, it can be maximum
The influence to plastics physical and mechanical property is reduced to degree, also there is Halogen, low cigarette, low toxicity, anti-molten drop and non-corrosive gas
The advantages of；And fine and close porous foam layer of charcoal is formed in material surface in burning, it can both prevent the further of internal layer high polymer
The release of degradation and combustible to surface, and heat source can be prevented to the transmitting of high polymer and isolation oxygen source, to prevent flame
Sprawling and propagation.
For expansion type flame retardant of the invention by using smoke suppressant, smoke suppressing effect is good, can reduce thermoplastic polyurethane
The toxic gas and smog generated in burning.
Expansion type flame retardant of the invention can be used for thermoplastic polyester engineering plastics such as PBT, PET etc. or other plastics.
Specific embodiment
For the ease of the understanding of those skilled in the art, below with reference to embodiment, the present invention is further illustrated, real
The content that the mode of applying refers to not is limitation of the invention.
Embodiment 1
A kind of halogen-free expansion fire retardant, the raw material including following parts by weight:
20 parts of melamine derivative
20 parts of coated ammonium polyphosphate
10 parts of pyrrolotriazine derivatives
10 parts of pentaerythritol phosphate
5 parts of trihydroxyethyl isocyanuric ester
6 parts of organic sesqui siloxane
4 parts of nano silica
3 parts of synergistic flame retardant
2 parts of smoke suppressant
At 2 parts of charcoal promotor
1 part of coupling agent
1 part of antioxidant
0.5 part of lubricant.
The melamine derivative is by melamine salt of pentaerythritol bis (dihydrogen phosphate), 2,4,8,10- tetra- oxygen -3,9- bis-
Bis- melamine salt of phosphorus loop coil [5,5] hendecane -3,9- dioxy -3,9- and (2,6,7- tri- oxygen -1- phosphorus-bicyclic [2,2,2] are pungent
Alkane -1- oxygen methyl) mixture that is formed with weight ratio 2:1:1 of phosphate melamine salt.
The coated ammonium polyphosphate is by melamine-formaldehyde coated ammonium polyphosphate, silane coated ammonium polyphosphate and unsaturated tree
The mixture that rouge coated ammonium polyphosphate is formed with weight ratio 1:0.5:1.
The pyrrolotriazine derivatives are poly- 2- ethyl alcohol amido -4,6- ethylenediamine base -1,3,5- triazine.The pentaerythrite phosphoric acid
Ester is 1- oxo-4- methyl-1-phospha-2,6,7- trioxa-l-phosphabicyclo [2,2,2] octane.
The organic sesqui siloxane is poly- (trimethylsiloxy group) silsesquioxane of cage type eight, epoxy group cage type sesquialter silicon
The mixture that oxygen alkane and vinyl trapezoidal half siloxane are formed with weight ratio 1:0.5:1.5.
The surface of the nano silica is through silane coupler modified processing, method of modifying are as follows: configuring volume ratio is
The nano silica for accounting for ethanol/water solution quality 1% is added in the ethanol/water solution of 3:1, the high speed under the revolving speed of 3000rpm
Shearing adds the silane coupling agent for accounting for ethanol/water solution quality 1%, and oxalic acid solution, which is added, makes the pH value of reaction system 3, instead
It after answering 1.5h, filters, washing, the nano silica modified up to surface after dry；Wherein, the silane coupling agent be by
γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane and γ-methyl-prop
The mixture that three isopropoxy silane of alkene acryloxypropylethoxysilane is formed with weight ratio 0.4:1:0.5.
The synergistic flame retardant is made of zinc borate, magnesium hydroxide and aluminium hydroxide with weight ratio 1.5:0.5:1 mixed
Close object；The mixture that the smoke suppressant is made of ferrocene, antimony oxide and ammonium octamolybdate with weight ratio 0.5:1.5:1.
Described at charcoal promotor is by pentaerythrite, poly- p-phenylene ethene diamine and phenolic resin with weight ratio 1:0.8-
1.2:0.5-1.5 the mixture of composition；The coupling agent is by tetravinyl tetramethyl-ring tetrasiloxane, vinyl triethoxyl
The mixture that silane and glycidoxypropyltrimethoxysilane alkane are formed with weight ratio 2:0.8:1.
The antioxidant is by β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, three [bis- uncles of 2.4-
Butyl phenyl] mixture that is formed with weight ratio 1:0.8:1 of the double lauryls of phosphite ester and thio-2 acid；The lubricant is
By oxidized polyethylene wax, pentaerythritol stearate and N, N- ethylenebis ricinoleic acid acid amide is with weight ratio 0.8:1.4:1 group
At mixture
A kind of preparation method of halogen-free expansion fire retardant, includes the following steps:
(1) melamine derivative, coated ammonium polyphosphate, pyrrolotriazine derivatives, pentaerythritol phosphate, three are weighed in parts by weight
Hydroxyethyl isocyanurate ester, organic sesqui siloxane, nano silica, synergistic flame retardant, smoke suppressant, at charcoal promotor, idol
Join agent, antioxidant and lubricant, is respectively dried to moisture content lower than 0.1%, is then crushed to 10 μm of partial size respectively；
(2) 10min will be mixed in the raw material investment high-speed mixer after above-mentioned dries pulverizing, obtains mixture；And in N, N- bis-
Cladding processing carried out to said mixture with ethylene-vinyl acetate resin in methylformamide, ethylene-vinyl acetate resin and mixed
The weight ratio for closing object is 1: 50.
Embodiment 2
A kind of halogen-free expansion fire retardant, the raw material including following parts by weight:
25 parts of melamine derivative
25 parts of coated ammonium polyphosphate
15 parts of pyrrolotriazine derivatives
12 parts of pentaerythritol phosphate
8 parts of trihydroxyethyl isocyanuric ester
7 parts of organic sesqui siloxane
5 parts of nano silica
4 parts of synergistic flame retardant
3 parts of smoke suppressant
At 2.5 parts of charcoal promotor
1.5 parts of coupling agent
1.2 parts of antioxidant
0.8 part of lubricant.
The melamine derivative is by melamine salt of pentaerythritol bis (dihydrogen phosphate), 2,4,8,10- tetra- oxygen -3,9- bis-
Bis- melamine salt of phosphorus loop coil [5,5] hendecane -3,9- dioxy -3,9- and (2,6,7- tri- oxygen -1- phosphorus-bicyclic [2,2,2] are pungent
Alkane -1- oxygen methyl) mixture that is formed with weight ratio 2.5:1-.2:1 of phosphate melamine salt.
The coated ammonium polyphosphate is by melamine-formaldehyde coated ammonium polyphosphate, silane coated ammonium polyphosphate and unsaturated tree
The mixture that rouge coated ammonium polyphosphate is formed with weight ratio 1.2:0.8:1.
The pyrrolotriazine derivatives are poly- 2- ethyl alcohol amido -4,6- ethylenediamine base -1,3,5- triazine.The pentaerythrite phosphoric acid
Ester is 1- oxo-4- methyl-1-phospha-2,6,7- trioxa-l-phosphabicyclo [2,2,2] octane.
The organic sesqui siloxane is poly- (trimethylsiloxy group) silsesquioxane of cage type eight, epoxy group cage type sesquialter silicon
The mixture that oxygen alkane and vinyl trapezoidal half siloxane are formed with weight ratio 1:0.8:1.8.
The surface of the nano silica is through silane coupler modified processing, method of modifying are as follows: configuring volume ratio is
The nano silica for accounting for ethanol/water solution quality 3% is added in the ethanol/water solution of 5:1, the high speed under the revolving speed of 3200rpm
Shearing, adds the silane coupling agent for accounting for ethanol/water solution quality 3%, and oxalic acid solution, which is added, makes the pH value of reaction system 3.5,
It after reacting 1.8h, filters, washing, the nano silica modified up to surface after dry；Wherein, the silane coupling agent be by
γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane and γ-methyl-prop
The mixture that three isopropoxy silane of alkene acryloxypropylethoxysilane is formed with weight ratio 0.5:1:0.8.
The synergistic flame retardant is made of zinc borate, magnesium hydroxide and aluminium hydroxide with weight ratio 1.8:0.8:1 mixed
Close object；The mixture that the smoke suppressant is made of ferrocene, antimony oxide and ammonium octamolybdate with weight ratio 0.8:1.8:1.
Described at charcoal promotor is by pentaerythrite, poly- p-phenylene ethene diamine and phenolic resin with weight ratio 1:0.9:
The mixture of 0.8 composition；The coupling agent is by tetravinyl tetramethyl-ring tetrasiloxane, vinyltriethoxysilane and contracting
The mixture that water glycerol ether propyl trimethoxy silicane is formed with weight ratio 2.5:0.9:1.
The antioxidant is by β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, three [bis- uncles of 2.4-
Butyl phenyl] mixture that is formed with weight ratio 1.2:0.9:1 of the double lauryls of phosphite ester and thio-2 acid；The lubricant
It is by oxidized polyethylene wax, pentaerythritol stearate and N, N- ethylenebis ricinoleic acid acid amide is with weight ratio 0.9:1.6:1
The mixture of composition
A kind of preparation method of halogen-free expansion fire retardant, includes the following steps:
(1) melamine derivative, coated ammonium polyphosphate, pyrrolotriazine derivatives, pentaerythritol phosphate, three are weighed in parts by weight
Hydroxyethyl isocyanurate ester, organic sesqui siloxane, nano silica, synergistic flame retardant, smoke suppressant, at charcoal promotor, idol
Join agent, antioxidant and lubricant, is respectively dried to moisture content lower than 0.1%, is then crushed to 20 μm of partial size respectively；
(2) 15min will be mixed in the raw material investment high-speed mixer after above-mentioned dries pulverizing, obtains mixture；And in N, N- bis-
Cladding processing carried out to said mixture with ethylene-vinyl acetate resin in methylformamide, ethylene-vinyl acetate resin and mixed
The weight ratio for closing object is 1: 60.
Embodiment 3
A kind of halogen-free expansion fire retardant, the raw material including following parts by weight:
30 parts of melamine derivative
230 parts of coated ammonium polyphosphate
20 parts of pyrrolotriazine derivatives
15 parts of pentaerythritol phosphate
10 parts of trihydroxyethyl isocyanuric ester
8 parts of organic sesqui siloxane
6 parts of nano silica
5 parts of synergistic flame retardant
4 parts of smoke suppressant
At 3 parts of charcoal promotor
2 parts of coupling agent
1.5 parts of antioxidant
1 part of lubricant.
The melamine derivative is by melamine salt of pentaerythritol bis (dihydrogen phosphate), 2,4,8,10- tetra- oxygen -3,9- bis-
Bis- melamine salt of phosphorus loop coil [5,5] hendecane -3,9- dioxy -3,9- and (2,6,7- tri- oxygen -1- phosphorus-bicyclic [2,2,2] are pungent
Alkane -1- oxygen methyl) mixture that is formed with weight ratio 3:1.5:1 of phosphate melamine salt.
The coated ammonium polyphosphate is by melamine-formaldehyde coated ammonium polyphosphate, silane coated ammonium polyphosphate and unsaturated tree
The mixture that rouge coated ammonium polyphosphate is formed with weight ratio 1.5:1:1.
The pyrrolotriazine derivatives are poly- 2- ethyl alcohol amido -4,6- ethylenediamine base -1,3,5- triazine.The pentaerythrite phosphoric acid
Ester is 1- oxo-4- methyl-1-phospha-2,6,7- trioxa-l-phosphabicyclo [2,2,2] octane.
The organic sesqui siloxane is poly- (trimethylsiloxy group) silsesquioxane of cage type eight, epoxy group cage type sesquialter silicon
The mixture that oxygen alkane and vinyl trapezoidal half siloxane are formed with weight ratio 1:1:2.
The surface of the nano silica is through silane coupler modified processing, method of modifying are as follows: configuring volume ratio is
The nano silica for accounting for ethanol/water solution quality 5% is added in the ethanol/water solution of 6:1, the high speed under the revolving speed of 3500rpm
Shearing, adds the silane coupling agent for accounting for ethanol/water solution quality 5%, and oxalic acid solution, which is added, makes the pH value of reaction system 3.5,
It after reacting 2h, filters, washing, the nano silica modified up to surface after dry；Wherein, the silane coupling agent be by
γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane and γ-methyl-prop
The mixture that three isopropoxy silane of alkene acryloxypropylethoxysilane is formed with weight ratio 0.6:1:1.
The mixture that the synergistic flame retardant is made of zinc borate, magnesium hydroxide and aluminium hydroxide with weight ratio 2:1:1；
The mixture that the smoke suppressant is made of ferrocene, antimony oxide and ammonium octamolybdate with weight ratio 1:2:1.
Described at charcoal promotor is by pentaerythrite, poly- p-phenylene ethene diamine and phenolic resin with weight ratio 1:1:1
The mixture of composition；The coupling agent is by tetravinyl tetramethyl-ring tetrasiloxane, vinyltriethoxysilane and shrink
The mixture that glycerol ether propyl trimethoxy silicane is formed with weight ratio 3:1:1.
The antioxidant is by β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, three [bis- uncles of 2.4-
Butyl phenyl] mixture that is formed with weight ratio 1.5:1:1 of the double lauryls of phosphite ester and thio-2 acid；The lubricant is
By oxidized polyethylene wax, pentaerythritol stearate and N, N- ethylenebis ricinoleic acid acid amide is formed with weight ratio 1:1.8:1
Mixture
A kind of preparation method of halogen-free expansion fire retardant, includes the following steps:
(1) melamine derivative, coated ammonium polyphosphate, pyrrolotriazine derivatives, pentaerythritol phosphate, three are weighed in parts by weight
Hydroxyethyl isocyanurate ester, organic sesqui siloxane, nano silica, synergistic flame retardant, smoke suppressant, at charcoal promotor, idol
Join agent, antioxidant and lubricant, is respectively dried to moisture content lower than 0.1%, is then crushed to 30 μm of partial size respectively；
(2) 20min will be mixed in the raw material investment high-speed mixer after above-mentioned dries pulverizing, obtains mixture；And in N, N- bis-
Cladding processing carried out to said mixture with ethylene-vinyl acetate resin in methylformamide, ethylene-vinyl acetate resin and mixed
The weight ratio for closing object is 1: 80.
Embodiment 4
A kind of halogen-free expansion fire retardant, the raw material including following parts by weight:
35 parts of melamine derivative
5 parts of coated ammonium polyphosphate
25 parts of pyrrolotriazine derivatives
18 parts of pentaerythritol phosphate
12 parts of trihydroxyethyl isocyanuric ester
9 parts of organic sesqui siloxane
7 parts of nano silica
36 parts of synergistic flame retardant
25 parts of smoke suppressant
At 3.5 parts of charcoal promotor
2.5 parts of coupling agent
1.8 parts of antioxidant
1.2 parts of lubricant.
The melamine derivative is by melamine salt of pentaerythritol bis (dihydrogen phosphate), 2,4,8,10- tetra- oxygen -3,9- bis-
Bis- melamine salt of phosphorus loop coil [5,5] hendecane -3,9- dioxy -3,9- and (2,6,7- tri- oxygen -1- phosphorus-bicyclic [2,2,2] are pungent
Alkane -1- oxygen methyl) mixture that is formed with weight ratio 3.5:1.8:1 of phosphate melamine salt.
The coated ammonium polyphosphate is by melamine-formaldehyde coated ammonium polyphosphate, silane coated ammonium polyphosphate and unsaturated tree
The mixture that rouge coated ammonium polyphosphate is formed with weight ratio 1.8:1.2:1.
The pyrrolotriazine derivatives are poly- 2- ethyl alcohol amido -4,6- ethylenediamine base -1,3,5- triazine.The pentaerythrite phosphoric acid
Ester is 1- oxo-4- methyl-1-phospha-2,6,7- trioxa-l-phosphabicyclo [2,2,2] octane.
The organic sesqui siloxane is poly- (trimethylsiloxy group) silsesquioxane of cage type eight, epoxy group cage type sesquialter silicon
The mixture that oxygen alkane and vinyl trapezoidal half siloxane are formed with weight ratio 1:1.2:2.2.
The surface of the nano silica is through silane coupler modified processing, method of modifying are as follows: configuring volume ratio is
The nano silica for accounting for ethanol/water solution quality 8% is added in the ethanol/water solution of 8:1, the high speed under the revolving speed of 3800rpm
Shearing, adds the silane coupling agent for accounting for ethanol/water solution quality 8%, and oxalic acid solution, which is added, makes the pH value of reaction system 3.5,
It after reacting 2.2h, filters, washing, the nano silica modified up to surface after dry；Wherein, the silane coupling agent be by
γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane and γ-methyl-prop
The mixture that three isopropoxy silane of alkene acryloxypropylethoxysilane is formed with weight ratio 0.7:1:1.2.
The synergistic flame retardant is made of zinc borate, magnesium hydroxide and aluminium hydroxide with weight ratio 2.2:1.2:1 mixed
Close object；The mixture that the smoke suppressant is made of ferrocene, antimony oxide and ammonium octamolybdate with weight ratio 1.2:2.2:1.
Described at charcoal promotor is by pentaerythrite, poly- p-phenylene ethene diamine and phenolic resin with weight ratio 1:1.1:
The mixture of 1.2 compositions；The coupling agent is by tetravinyl tetramethyl-ring tetrasiloxane, vinyltriethoxysilane and contracting
The mixture that water glycerol ether propyl trimethoxy silicane is formed with weight ratio 3.5:1.1:1.
The antioxidant is by β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, three [bis- uncles of 2.4-
Butyl phenyl] mixture that is formed with weight ratio 1.8:1.1:1 of the double lauryls of phosphite ester and thio-2 acid；The lubricant
It is by oxidized polyethylene wax, pentaerythritol stearate and N, N- ethylenebis ricinoleic acid acid amide is with weight ratio 1.1:2:1 group
At mixture
A kind of preparation method of halogen-free expansion fire retardant, includes the following steps:
(1) melamine derivative, coated ammonium polyphosphate, pyrrolotriazine derivatives, pentaerythritol phosphate, three are weighed in parts by weight
Hydroxyethyl isocyanurate ester, organic sesqui siloxane, nano silica, synergistic flame retardant, smoke suppressant, at charcoal promotor, idol
Join agent, antioxidant and lubricant, is respectively dried to moisture content lower than 0.1%, is then crushed to 40 μm of partial size respectively；
(2) 25min will be mixed in the raw material investment high-speed mixer after above-mentioned dries pulverizing, obtains mixture；And in N, N- bis-
Cladding processing carried out to said mixture with ethylene-vinyl acetate resin in methylformamide, ethylene-vinyl acetate resin and mixed
The weight ratio for closing object is 1: 90.
Embodiment 5
A kind of halogen-free expansion fire retardant, the raw material including following parts by weight:
40 parts of melamine derivative
40 parts of coated ammonium polyphosphate
30 parts of pyrrolotriazine derivatives
20 parts of pentaerythritol phosphate
15 parts of trihydroxyethyl isocyanuric ester
10 parts of organic sesqui siloxane
8 parts of nano silica
7 parts of synergistic flame retardant
6 parts of smoke suppressant
At 4 parts of charcoal promotor
3 parts of coupling agent
2 parts of antioxidant
1.5 parts of lubricant.
The melamine derivative is by melamine salt of pentaerythritol bis (dihydrogen phosphate), 2,4,8,10- tetra- oxygen -3,9- bis-
Bis- melamine salt of phosphorus loop coil [5,5] hendecane -3,9- dioxy -3,9- and (2,6,7- tri- oxygen -1- phosphorus-bicyclic [2,2,2] are pungent
Alkane -1- oxygen methyl) mixture that is formed with weight ratio 4:2:1 of phosphate melamine salt.
The coated ammonium polyphosphate is by melamine-formaldehyde coated ammonium polyphosphate, silane coated ammonium polyphosphate and unsaturated tree
The mixture that rouge coated ammonium polyphosphate is formed with weight ratio 2:1.5:1.
The pyrrolotriazine derivatives are poly- 2- ethyl alcohol amido -4,6- ethylenediamine base -1,3,5- triazine.The pentaerythrite phosphoric acid
Ester is 1- oxo-4- methyl-1-phospha-2,6,7- trioxa-l-phosphabicyclo [2,2,2] octane.
The organic sesqui siloxane is poly- (trimethylsiloxy group) silsesquioxane of cage type eight, epoxy group cage type sesquialter silicon
The mixture that oxygen alkane and vinyl trapezoidal half siloxane are formed with weight ratio 1:1.5:2.5.
The surface of the nano silica is through silane coupler modified processing, method of modifying are as follows: configuring volume ratio is
The nano silica for accounting for ethanol/water solution quality 10% is added in the ethanol/water solution of 10:1, high under the revolving speed of 4000rpm
Speed shearing, adds the silane coupling agent for accounting for ethanol/water solution quality 10%, and oxalic acid solution, which is added, makes the pH value of reaction system exist
4, it after reacting 2.5h, filters, washing, the nano silica modified up to surface after dry；Wherein, the silane coupling agent is
By γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane and γ-methyl
The mixture that acryloxypropyl triisopropoxide silane is formed with weight ratio 0.8:1:1.5.
The synergistic flame retardant is made of zinc borate, magnesium hydroxide and aluminium hydroxide with weight ratio 2.5:1.5:1 mixed
Close object；The mixture that the smoke suppressant is made of ferrocene, antimony oxide and ammonium octamolybdate with weight ratio 1.5:2.5:1.
Described at charcoal promotor is by pentaerythrite, poly- p-phenylene ethene diamine and phenolic resin with weight ratio 1:1.2:
The mixture of 1.5 compositions；The coupling agent is by tetravinyl tetramethyl-ring tetrasiloxane, vinyltriethoxysilane and contracting
The mixture that water glycerol ether propyl trimethoxy silicane is formed with weight ratio 4:1.2:1.
The antioxidant is by β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, three [bis- uncles of 2.4-
Butyl phenyl] mixture that is formed with weight ratio 2:1.2:1 of the double lauryls of phosphite ester and thio-2 acid；The lubricant is
By oxidized polyethylene wax, pentaerythritol stearate and N, N- ethylenebis ricinoleic acid acid amide is with weight ratio 1.2:2.2:1 group
At mixture
A kind of preparation method of halogen-free expansion fire retardant, includes the following steps:
(1) melamine derivative, coated ammonium polyphosphate, pyrrolotriazine derivatives, pentaerythritol phosphate, three are weighed in parts by weight
Hydroxyethyl isocyanurate ester, organic sesqui siloxane, nano silica, synergistic flame retardant, smoke suppressant, at charcoal promotor, idol
Join agent, antioxidant and lubricant, is respectively dried to moisture content lower than 0.1%, is then crushed to 50 μm of partial size respectively；
(2) 30min will be mixed in the raw material investment high-speed mixer after above-mentioned dries pulverizing, obtains mixture；And in N, N- bis-
Cladding processing carried out to said mixture with ethylene-vinyl acetate resin in methylformamide, ethylene-vinyl acetate resin and mixed
The weight ratio for closing object is 1: 100.
After tested, when expansion type flame retardant of the invention is applied to plastic products, flame retardant property can achieve 1.4mm
V-0 grades of UL94, good flame retardation effect, and additive amount is few, can farthest reduce the influence to plastics physical and mechanical property, combustion
Light transmittance can achieve 85% or more after burning, also have the advantages that Halogen, low cigarette, low toxicity, anti-molten drop and non-corrosive gas；And
Fine and close porous foam layer of charcoal is formed in material surface in burning, and the further of internal layer high polymer can both have been prevented to degrade and flammable
Release of the object to surface, and heat source can be prevented to the transmitting of high polymer and isolation oxygen source, to prevent the sprawling and biography of flame
It broadcasts.
Above-described embodiment is the preferable implementation of the present invention, and in addition to this, the present invention can be realized with other way,
Do not depart under the premise of present inventive concept it is any obviously replace it is within the scope of the present invention.
Claims (10)
1. a kind of halogen-free expansion fire retardant, it is characterised in that: the raw material including following parts by weight:
20-40 parts of melamine derivative
20-40 parts of coated ammonium polyphosphate
10-30 parts of pyrrolotriazine derivatives
10-20 parts of pentaerythritol phosphate
5-15 parts of trihydroxyethyl isocyanuric ester
6-10 parts of organic sesqui siloxane
4-8 parts of nano silica
3-7 parts of synergistic flame retardant
2-6 parts of smoke suppressant
At 2-4 parts of charcoal promotor
1-3 parts of coupling agent
1-2 parts of antioxidant
0.5-1.5 parts of lubricant.
2. a kind of halogen-free expansion fire retardant according to claim 1, it is characterised in that: the melamine derivative is
By melamine salt of pentaerythritol bis (dihydrogen phosphate), 2,4,8,10- tetra- oxygen -3,9- hosphospiro [5,5] hendecane -3,9- dioxies -
3,9- bis- melamine salts and (2,6,7- tri- oxygen -1- phosphorus-bicyclic [2,2,2] octane -1- oxygen methyl) phosphate melamine salt
The mixture formed with weight ratio 2-4:1-2:1.
3. a kind of halogen-free expansion fire retardant according to claim 1, it is characterised in that: the coated ammonium polyphosphate be by
Melamine-formaldehyde coated ammonium polyphosphate, silane coated ammonium polyphosphate and unsaturated-resin coated ammonium polyphosphate are with weight ratio 1-2:
The mixture of 0.5-1.5:1 composition.
4. a kind of halogen-free expansion fire retardant according to claim 1, it is characterised in that: the pyrrolotriazine derivatives are poly- 2-
Ethyl alcohol amido -4,6- ethylenediamine base -1,3,5- triazine.The pentaerythritol phosphate is 1- oxo-4- methyl-1-phospha-2,
6,7- trioxa-l-phosphabicyclo [2,2,2] octane.
5. a kind of halogen-free expansion fire retardant according to claim 1, it is characterised in that: the organic sesqui siloxane is
At least one of random silsesquioxane, trapezoidal half siloxane, bridge shape silsesquioxane and cagelike silsesquioxane.
6. a kind of halogen-free expansion fire retardant according to claim 1, it is characterised in that: the table of the nano silica
Face is through silane coupler modified processing, method of modifying are as follows: the ethanol/water solution that configuration volume ratio is 3-10:1, addition account for second
Alcohol/aqueous solution quality 1%-10% nano silica, the high speed shear under the revolving speed of 3000-4000rpm add Zhan Yi
Alcohol/aqueous solution quality 1%-10% silane coupling agent, oxalic acid solution, which is added, makes the pH value of reaction system in 3-4, reacts 1.5-
It after 2.5h, filters, washing, the nano silica modified up to surface after dry；Wherein, the silane coupling agent is by γ-
Glycidyl ether oxygen propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane and γ-methacryl
The mixture that three isopropoxy silane of oxygroup propyl is formed with weight ratio 0.4-0.8:1:0.5-1.5.
7. a kind of halogen-free expansion fire retardant according to claim 1, it is characterised in that: the synergistic flame retardant is by boron
The mixture that sour zinc, magnesium hydroxide and aluminium hydroxide are formed with weight ratio 1.5-2.5:0.5-1.5:1；The smoke suppressant is by two
The mixture that luxuriant iron, antimony oxide and ammonium octamolybdate are formed with weight ratio 0.5-1.5:1.5-2.5:1.
8. a kind of halogen-free expansion fire retardant according to claim 1, it is characterised in that: described at charcoal promotor is by season
The mixture that penta tetrol, poly- p-phenylene ethene diamine and phenolic resin are formed with weight ratio 1:0.8-1.2:0.5-1.5；It is described
Coupling agent is by tetravinyl tetramethyl-ring tetrasiloxane, vinyltriethoxysilane and glycidyl ether propyl trimethoxy
The mixture that base silane is formed with weight ratio 2-4:0.8-1.2:1.
9. a kind of halogen-free expansion fire retardant according to claim 1, it is characterised in that: the antioxidant be by β-(3,
5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, three [2.4- di-tert-butyl-phenyl] phosphite esters and thio dipropyl
The mixture that sour double lauryls are formed with weight ratio 1-2:0.8-1.2:1；The lubricant is by oxidized polyethylene wax, Ji Wusi
Alcohol stearate and N, the mixture that N- ethylenebis ricinoleic acid acid amide is formed with weight ratio 0.8-1.2:1.4-2.2:1.
10. such as a kind of described in any item preparation methods of halogen-free expansion fire retardant of claim 1-9, it is characterised in that: packet
Include following steps:
(1) melamine derivative, coated ammonium polyphosphate, pyrrolotriazine derivatives, pentaerythritol phosphate, three are weighed in parts by weight
Hydroxyethyl isocyanurate ester, organic sesqui siloxane, nano silica, synergistic flame retardant, smoke suppressant, at charcoal promotor, idol
Join agent, antioxidant and lubricant, is respectively dried to moisture content lower than 0.1%, is then crushed to 10-50 μm of partial size respectively；
(2) 10-30min will be mixed in the raw material investment high-speed mixer after above-mentioned dries pulverizing, obtains mixture；And in N, N-
Cladding processing carried out to said mixture with ethylene-vinyl acetate resin in dimethylformamide, ethylene-vinyl acetate resin with
The weight ratio of mixture is 1: 50-100.
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