CN109370232A - A kind of plastics environmentally friendly composite halogen-free fire retardant and preparation method thereof - Google Patents
A kind of plastics environmentally friendly composite halogen-free fire retardant and preparation method thereof Download PDFInfo
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- CN109370232A CN109370232A CN201811167402.5A CN201811167402A CN109370232A CN 109370232 A CN109370232 A CN 109370232A CN 201811167402 A CN201811167402 A CN 201811167402A CN 109370232 A CN109370232 A CN 109370232A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K2003/026—Phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
Abstract
The present invention relates to technical field of flame retardant, more particularly to a kind of plastics environmentally friendly composite halogen-free fire retardant and preparation method thereof, the raw material including following parts by weight: melamine derivative, coated ammonium polyphosphate, dihydroxyalkyl phosphinates, bisphenol A tetraphenyl diphosphate, hydroquinone bis phosphoric acid phenyl ester oligomer, whiteness encapsulated red phosphorus, resorcinol diphosphate, Vitrified powder, organic sesqui siloxane, nano silica, inorganic fire retardants, smoke suppressant, antioxidant, lubricant.Fire retardant of the invention has excellent flame retardant property, and has the advantages that Halogen, low cigarette, low toxicity, anti-molten drop and non-corrosive gas；And when being used for plastics, fine and close ceramic product can be formed when burning reaches certain temperature, low at porcelain temperature, at porcelain densification, the ceramic product of formation has good elevated temperature strength and heat resistanceheat resistant stream impact capacity.
Description
Technical field
The present invention relates to technical field of flame retardant, and in particular to a kind of plastics environmentally friendly composite halogen-free fire retardant and its preparation
Method.
Background technique
Fire retardant, assigns the functional aid of combustible polymers flame retardancy, and fire-retardant primarily directed to high molecular material sets
Meter.
The extensive use of plastics, synthetic rubber, the big synthetic material of synthetic fibers three in the world today is well-known,
And headed by plastics, as one of present social four big basic material, plastics are at present in building, electric power, telecommunication, electric appliance, energy
The number of applications and application range in the fields such as source, communications and transportation, agricultural, health care, aerospace, information and national defense industry all with
Day all increasings.Plastics have many excellent performances as a kind of important alternative materials, such as light weight, have great plasticity,
But the weakness that most plastics have one fatal, it is exactly that they almost belong to inflammable or combustible material, only
Has basic fire source, they can be ignited in air and sustained combustion, have occurred that very in present society
The fire mostly caused about being ignited for plastic material causes the heavy injures and deaths of personnel and the heavy losses of property, therefore utilizes
Some means or method inflammable or flammable plastics can be become to be not easy to be ignited perhaps light rear very short time self-extinguishment or
It is ignited that after-combustion speed is very slow, so as to greatly reduce the generation of fire, the purpose of this namely plastic flame technology.At present
Although fire-retardant for plastic in the market can play fire-retardant effect, halogen element is typically contained, not environmentally, and also will affect modeling
The mechanical property of material.
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 plastics environmental protection
Composite halogen-free fire retardant, which has excellent flame retardant property, and has Halogen, low cigarette, low toxicity, anti-molten drop and corrosion-free
The advantages of property gas；And when being used for plastics, fine and close ceramic product can be formed when burning reaches certain temperature, at porcelain temperature
Low, at porcelain densification, the ceramic product of formation has good elevated temperature strength and heat resistanceheat resistant stream impact capacity.
Another object of the present invention is to provide a kind of plastics preparation method of environmentally friendly composite halogen-free fire retardant, the preparations
Method and step is simple, convenient operation and control, and quality is 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 environmentally friendly composite halogen-free fire retardant of plastics, including such as
The raw material of lower parts by weight:
30-50 parts of melamine derivative
20-40 parts of coated ammonium polyphosphate
10-30 parts of dihydroxyalkyl phosphinates
10-20 parts of bisphenol A tetraphenyl diphosphate
5-15 parts of phenyl ester oligomer of hydroquinone bis phosphoric acid
4-8 parts of whiteness encapsulated red phosphorus
3-7 parts of resorcinol diphosphate
8-12 parts of Vitrified powder
6-10 parts of organic sesqui siloxane
4-8 parts of nano silica
2-6 parts of inorganic fire retardants
1-5 parts of smoke suppressant
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.
The present invention is by using dihydroxyalkyl phosphinates, bisphenol A tetraphenyl diphosphate, hydroquinone bis phosphoric acid benzene
Ester, whiteness encapsulated red phosphorus oligomer and resorcinol diphosphate, fire retardant obtained have the resistance for efficiently, pressing down cigarette, low toxicity
Fuel efficiency fruit.
Preferably, the Vitrified powder is by ammonium borate, bismuth oxide glass powder, glass fibre and wollastonite in powder with weight ratio
The mixture of 0.8-1.2:1:0.4-0.8:0.5-1.5 composition.The present invention passes through the type of strict control Vitrified powder, compounds and match
Than that can make product ceramic at high temperature, improve flame retardant effect.
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 inorganic fire retardants 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, 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.
It preferably, further include 4- ((N- phenethyl -4- (o-tolyl oxygroup) benzamido) methyl) benzoic acid 1-5
Part, Ca2[(O3PCH2)2NCH2CONHC3N3(NH2)2] 1-5 parts.The present invention is by using 4- ((N- phenethyl -4- (o-tolyl
Oxygroup) benzamido) methyl) benzoic acid, there is excellent flame retardant property；The present invention is by using Ca2[(O3PCH2)2NCH2CONHC3N3(NH2)2], excellent fireproof performance, environmental protection.
A kind of plastics preparation method of environmentally friendly composite halogen-free fire retardant, includes the following steps:
(1) above-mentioned raw materials are weighed in parts by weight, are put into high-speed mixer and are mixed 10-30min, obtain mixture；
(2) compound powder is broken to partial size is 10-50 μm, and plastics are made with environmentally friendly composite halogen-free fire retardant.
The beneficial effects of the present invention are: fire retardants of the invention to have excellent flame retardant property, and has Halogen, low
The advantages of cigarette, low toxicity, anti-molten drop and non-corrosive gas；And when being used for plastics, densification can be formed when burning reaches certain temperature
Ceramic product, low at porcelain temperature, at porcelain densification, there is good elevated temperature strength and heat resistanceheat resistant stream to rush for the ceramic product of formation
Hit ability.
For fire retardant of the invention by using smoke suppressant, smoke suppressing effect is good, can reduce thermoplastic polyurethane and burn
When the toxic gas and smog that generate.
Fire 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 environmentally friendly composite halogen-free fire retardant of plastics, the raw material including following parts by weight:
30 parts of melamine derivative
20 parts of coated ammonium polyphosphate
10 parts of dihydroxyalkyl phosphinates
10 parts of bisphenol A tetraphenyl diphosphate
5 parts of oligomer of hydroquinone bis phosphoric acid phenyl ester
4 parts of whiteness encapsulated red phosphorus
3 parts of resorcinol diphosphate
8 parts of Vitrified powder
6 parts of organic sesqui siloxane
4 parts of nano silica
2 parts of inorganic fire retardants
1 part of smoke suppressant
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 Vitrified powder is by ammonium borate, bismuth oxide glass powder, glass fibre and wollastonite in powder with weight ratio 0.8:1:
The mixture of 0.4:0.5 composition.
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 inorganic fire retardants 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.
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.
It further include 4- ((N- phenethyl -4- (o-tolyl oxygroup) benzamido) methyl) 1 part of benzoic acid, Ca2
[(O3PCH2)2NCH2CONHC3N3(NH2)2] 1 part.
A kind of plastics preparation method of environmentally friendly composite halogen-free fire retardant, includes the following steps:
(1) above-mentioned raw materials are weighed in parts by weight, are put into high-speed mixer and are mixed 10min, obtain mixture；
(2) compound powder is broken to partial size is 10 μm, and plastics are made with environmentally friendly composite halogen-free fire retardant.
Embodiment 2
A kind of environmentally friendly composite halogen-free fire retardant of plastics, the raw material including following parts by weight:
35 parts of melamine derivative
25 parts of coated ammonium polyphosphate
15 parts of dihydroxyalkyl phosphinates
12 parts of bisphenol A tetraphenyl diphosphate
8 parts of oligomer of hydroquinone bis phosphoric acid phenyl ester
5 parts of whiteness encapsulated red phosphorus
4 parts of resorcinol diphosphate
9 parts of Vitrified powder
7 parts of organic sesqui siloxane
5 parts of nano silica
3 parts of inorganic fire retardants
2 parts of smoke suppressant
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 Vitrified powder is by ammonium borate, bismuth oxide glass powder, glass fibre and wollastonite in powder with weight ratio 0.9:1:
The mixture of 0.5:0.8 composition.
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 inorganic fire retardants 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.
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 0.9:1.5:1
The mixture of composition.
It further include 4- ((N- phenethyl -4- (o-tolyl oxygroup) benzamido) methyl) 2 parts of benzoic acid, Ca2
[(O3PCH2)2NCH2CONHC3N3(NH2)2] 2 parts.
A kind of plastics preparation method of environmentally friendly composite halogen-free fire retardant, includes the following steps:
(1) above-mentioned raw materials are weighed in parts by weight, are put into high-speed mixer and are mixed 15min, obtain mixture；
(2) compound powder is broken to partial size is 20 μm, and plastics are made with environmentally friendly composite halogen-free fire retardant.
Embodiment 3
A kind of environmentally friendly composite halogen-free fire retardant of plastics, the raw material including following parts by weight:
40 parts of melamine derivative
30 parts of coated ammonium polyphosphate
20 parts of dihydroxyalkyl phosphinates
15 parts of bisphenol A tetraphenyl diphosphate
10 parts of oligomer of hydroquinone bis phosphoric acid phenyl ester
6 parts of whiteness encapsulated red phosphorus
5 parts of resorcinol diphosphate
10 parts of Vitrified powder
8 parts of organic sesqui siloxane
6 parts of nano silica
4 parts of inorganic fire retardants
3 parts of smoke suppressant
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 Vitrified powder is by ammonium borate, bismuth oxide glass powder, glass fibre and wollastonite in powder with weight ratio 1:1:0.6:1
The mixture of composition.
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 inorganic fire retardants 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.
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.
It further include 4- ((N- phenethyl -4- (o-tolyl oxygroup) benzamido) methyl) 3 parts of benzoic acid, Ca2
[(O3PCH2)2NCH2CONHC3N3(NH2)2] 3 parts.
A kind of plastics preparation method of environmentally friendly composite halogen-free fire retardant, includes the following steps:
(1) above-mentioned raw materials are weighed in parts by weight, are put into high-speed mixer and are mixed 20min, obtain mixture；
(2) compound powder is broken to partial size is 30 μm, and plastics are made with environmentally friendly composite halogen-free fire retardant.
Embodiment 4
A kind of environmentally friendly composite halogen-free fire retardant of plastics, the raw material including following parts by weight:
45 parts of melamine derivative
35 parts of coated ammonium polyphosphate
25 parts of dihydroxyalkyl phosphinates
18 parts of bisphenol A tetraphenyl diphosphate
12 parts of oligomer of hydroquinone bis phosphoric acid phenyl ester
7 parts of whiteness encapsulated red phosphorus
6 parts of resorcinol diphosphate
11 parts of Vitrified powder
9 parts of organic sesqui siloxane
7 parts of nano silica
5 parts of inorganic fire retardants
4 parts of smoke suppressant
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 Vitrified powder is by ammonium borate, bismuth oxide glass powder, glass fibre and wollastonite in powder with weight ratio 1.1:1:
The mixture of 0.7:1.2 composition.
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 inorganic fire retardants 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.
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.
It further include 4- ((N- phenethyl -4- (o-tolyl oxygroup) benzamido) methyl) 4 parts of benzoic acid, Ca2
[(O3PCH2)2NCH2CONHC3N3(NH2)2] 4 parts.
A kind of plastics preparation method of environmentally friendly composite halogen-free fire retardant, includes the following steps:
(1) above-mentioned raw materials are weighed in parts by weight, are put into high-speed mixer and are mixed 25min, obtain mixture；
(2) compound powder is broken to partial size is 40 μm, and plastics are made with environmentally friendly composite halogen-free fire retardant.
Embodiment 5
A kind of environmentally friendly composite halogen-free fire retardant of plastics, the raw material including following parts by weight:
50 parts of melamine derivative
40 parts of coated ammonium polyphosphate
30 parts of dihydroxyalkyl phosphinates
20 parts of bisphenol A tetraphenyl diphosphate
15 parts of oligomer of hydroquinone bis phosphoric acid phenyl ester
8 parts of whiteness encapsulated red phosphorus
7 parts of resorcinol diphosphate
12 parts of Vitrified powder
10 parts of organic sesqui siloxane
8 parts of nano silica
6 parts of inorganic fire retardants
5 parts of smoke suppressant
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 Vitrified powder is by ammonium borate, bismuth oxide glass powder, glass fibre and wollastonite in powder with weight ratio 1.2:1:
The mixture of 0.8:1.5 composition.
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 inorganic fire retardants 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.
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.
It further include 4- ((N- phenethyl -4- (o-tolyl oxygroup) benzamido) methyl) 5 parts of benzoic acid, Ca2
[(O3PCH2)2NCH2CONHC3N3(NH2)2] 5 parts.
A kind of plastics preparation method of environmentally friendly composite halogen-free fire retardant, includes the following steps:
(1) above-mentioned raw materials are weighed in parts by weight, are put into high-speed mixer and are mixed 30min, obtain mixture；
(2) compound powder is broken to partial size is 50 μm, and plastics are made with environmentally friendly composite halogen-free fire retardant.
After tested, when fire retardant of the invention is applied to plastic products, flame retardant property can achieve 1.6mm UL94 V-0
Grade, there is excellent flame retardant property, and light transmittance can achieve 80% or more after burning, and there is Halogen, low cigarette, low toxicity, prevent melting
The advantages of drop and non-corrosive gas；And when being used for plastics, fine and close ceramic product can be formed when burning reaches certain temperature,
Low at porcelain temperature, at porcelain densification, the ceramic product of formation has good elevated temperature strength and heat resistanceheat resistant stream impact capacity.
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 environmentally friendly composite halogen-free fire retardant of plastics, it is characterised in that: the raw material including following parts by weight:
30-50 parts of melamine derivative
20-40 parts of coated ammonium polyphosphate
10-30 parts of dihydroxyalkyl phosphinates
10-20 parts of bisphenol A tetraphenyl diphosphate
5-15 parts of phenyl ester oligomer of hydroquinone bis phosphoric acid
4-8 parts of whiteness encapsulated red phosphorus
3-7 parts of resorcinol diphosphate
8-12 parts of Vitrified powder
6-10 parts of organic sesqui siloxane
4-8 parts of nano silica
2-6 parts of inorganic fire retardants
1-5 parts of smoke suppressant
1-2 parts of antioxidant
0.5-1.5 parts of lubricant.
2. a kind of environmentally friendly composite halogen-free fire retardant of plastics according to claim 1, it is characterised in that: the melamine
Derivative be by melamine salt of pentaerythritol bis (dihydrogen phosphate), 2,4,8,10- tetra- oxygen -3,9- hosphospiro [5,5] hendecanes -3,
Bis- melamine salt of 9- dioxy -3,9- and (2,6,7- tri- oxygen -1- phosphorus-bicyclic [2,2,2] octane -1- oxygen methyl) phosphate trimerization
The mixture that cyanamide salt is formed with weight ratio 2-4:1-2:1.
3. a kind of environmentally friendly composite halogen-free fire retardant of plastics according to claim 1, it is characterised in that: the poly- phosphorus of cladding
Sour ammonium is by melamine-formaldehyde coated ammonium polyphosphate, silane coated ammonium polyphosphate and unsaturated-resin coated ammonium polyphosphate with weight
Than the mixture of 1-2:0.5-1.5:1 composition.
4. a kind of environmentally friendly composite halogen-free fire retardant of plastics according to claim 1, it is characterised in that: the Vitrified powder is
It is made of ammonium borate, bismuth oxide glass powder, glass fibre and wollastonite in powder with weight ratio 0.8-1.2:1:0.4-0.8:0.5-1.5
Mixture.
5. a kind of environmentally friendly composite halogen-free fire retardant of plastics according to claim 1, it is characterised in that: organic sesquialter
Siloxanes be random silsesquioxane, trapezoidal half siloxane, bridge shape silsesquioxane and cagelike silsesquioxane at least
It is a kind of.
6. a kind of environmentally friendly composite halogen-free fire retardant of plastics according to claim 1, it is characterised in that: the nano-silica
The surface of SiClx is through silane coupler modified processing, method of modifying are as follows: the ethanol/water solution that configuration volume ratio is 3-10:1,
It is added and accounts for the nano silica of ethanol/water solution quality 1%-10%, the high speed shear under the revolving speed of 3000-4000rpm, then plus
Enter to account for the silane coupling agent of ethanol/water solution quality 1%-10%, oxalic acid solution, which is added, makes the pH value of reaction system in 3-4, reaction
It after 1.5-2.5h, 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 0.4-0.8:1:0.5-1.5.
7. a kind of environmentally friendly composite halogen-free fire retardant of plastics according to claim 1, it is characterised in that: described inorganic fire-retarded
The mixture that agent is made of zinc borate, magnesium hydroxide and aluminium hydroxide with weight ratio 1.5-2.5:0.5-1.5:1；The suppression cigarette
The mixture that agent is made of ferrocene, antimony oxide and ammonium octamolybdate with weight ratio 0.5-1.5:1.5-2.5:1.
8. a kind of environmentally friendly composite halogen-free fire retardant of plastics according to claim 1, it is characterised in that: the antioxidant is
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
The mixture that the double lauryls of thio-2 acid are formed with weight ratio 1-2:0.8-1.2:1；The lubricant is by oxidic polyethylene
Wax, pentaerythritol stearate and N, N- ethylenebis ricinoleic acid acid amide are formed with weight ratio 0.8-1.2:1.4-2.2:1
Mixture.
9. a kind of environmentally friendly composite halogen-free fire retardant of plastics according to claim 1, it is characterised in that: further include 4- ((N-
Phenethyl -4- (o-tolyl oxygroup) benzamido) methyl) 1-5 parts of benzoic acid, Ca2[(O3PCH2)2NCH2CONHC3N3
(NH2)2] 1-5 parts.
10. such as a kind of described in any item preparation methods of the environmentally friendly composite halogen-free fire retardant of plastics use of claim 1-9, feature
It is: includes the following steps:
(1) above-mentioned raw materials are weighed in parts by weight, are put into high-speed mixer and are mixed 10-30min, obtain mixture；
(2) compound powder is broken to partial size is 10-50 μm, and plastics are made with environmentally friendly composite halogen-free fire retardant.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112409391A (en) * | 2020-11-20 | 2021-02-26 | 云南江磷集团股份有限公司 | Melamine borate salt thermal polycondensate anti-dropping agent and application thereof in PA6 |
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