CN101463154A - Phosphorus-nitrogen expansion type flame-retardant material and production method thereof - Google Patents

Phosphorus-nitrogen expansion type flame-retardant material and production method thereof Download PDF

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CN101463154A
CN101463154A CNA2008102185577A CN200810218557A CN101463154A CN 101463154 A CN101463154 A CN 101463154A CN A2008102185577 A CNA2008102185577 A CN A2008102185577A CN 200810218557 A CN200810218557 A CN 200810218557A CN 101463154 A CN101463154 A CN 101463154A
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China
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retardant
phosphorus
expansion type
many carbon
type flame
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CNA2008102185577A
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Chinese (zh)
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朱建一
张金柱
江国荣
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佛山市顺德区华塑龙塑料实业有限公司
朱建一
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Priority to CNA2008102185577A priority Critical patent/CN101463154A/en
Publication of CN101463154A publication Critical patent/CN101463154A/en

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Abstract

The invention relates to a phosphorus-nitrogen intumescent flame retardant material, which is characterized in that the phosphorus-nitrogen intumescent flame retardant materials comprises polyolefin resin, phosphoric acids compound, carbonaceous polyol compound, azotic carbonaceous compound, toughener, chemical inhibitor, packing and lubricant. The contents of all components are respectively according to the mass percent: 59%-73% of polyolefin resin, 8%-21% of phosphoric acids compound, 3%-14% of carbonaceous polyol compound, 3%-16% of azotic carbonaceous compound, 4%-10% of toughener, 0.1%-0.8% of chemical inhibitor, 0.5%-10% of packing and 0.1%-0.5% of lubricant. The phosphorus-nitrogen intumescent flame retardant material has good flame retardant materials, no precipitation, and no drippag, nontoxic and less smoke.

Description

A kind of phosphorus-nitrogen expansion type flame-retardant material and manufacture method thereof
Technical field
The present invention relates to a kind of expanding flame-proof material and manufacture method thereof, is a kind of phosphorus-nitrogen expansion type flame-retardant material and manufacture method thereof specifically.
Background technology
Along with the development of telling of polymer material science, macromolecular material has been widely used in fields such as national economy, national defense construction.Yet the macromolecular material that great majority are commonly used is inflammable or flammable, and can discharge a large amount of poisonous gases and black smoke in its combustion processes, thereby has restricted the application of macromolecular material in other field.How to improve macromolecular material inflammable phenomenon, reduce the toxic gas and the black smoke that discharge in the macromolecular material combustion processes, be a research focus.In the prior art, people all add fire retardant in macromolecular material in the production process of macromolecule material product, its goods are had do not fire or difficult performance of firing.But, present fire retardant is halogen-containing fire retardant material mostly, because the Halogen fire retardant material can produce toxic gas in the incendiary process, environmental pollution is bigger, also can cause damage, so the Halogen fire retardant material has been the research tendency of a fire retardant material by the replacement of bittern-free flame-proof material to HUMAN HEALTH.In addition, metal hydroxides also can be used as fire retardant material, as magnesium hydroxide, and aluminium hydroxide etc.The fire retardant mechanism of inorganic combustion inhibitor is: resolve into metal oxide and water when burning, absorb a large amount of heats, dehydration reaction produces a large amount of water vapour dilution inflammable gass simultaneously, and metal oxide forms a tectum, thereby stops oxygen to burn away.But because this class inorganic combustion inhibitor addition is generally bigger, therefore the influence to the processing characteristics of macromolecular material is bigger.Existing another kind of fire retardant is an expansion type flame retardant; its principle is to adopt fire retardant composite, and its thermal destruction product promotes polymer surfaces carbonization of dewatering rapidly, forms carburization zone; the combustion by evaporation and the decomposition combustion that utilize the simple substance charcoal not produce flame reach the fire retardant mechanism of the effect of fire-resisting protection.Be that single component or three component expansion type flame retardants all have following shortcoming: first single component salt mainly is synthetic in water, and productive rate is lower; It two is that the relative molecular mass of main component of expansion type flame retardant is low, and is incompatible with matrix in the course of processing, is easy to migration or separates out phenomenon, causes the fire retardant material mechanical property to descend, and does not reach fire-retardant effect.The relative molecular weight of the expanding fire retardant that uses on market simultaneously is low, thereby makes the poor stability of fire retardant material, and anti-transport property is poor, finally causes the physicals of fire retardant material to reduce degraded appearance.And macromolecular material and expansion type flame retardant consistency are poor, thereby cause the mechanical property of polymkeric substance to descend.
Summary of the invention
Goal of the invention of the present invention is to overcome the deficiencies in the prior art, a kind of good flame retardation effect is provided, does not have the phosphorus-nitrogen expansion type flame-retardant material of separating out, do not have drippage and nontoxic few cigarette
Another goal of the invention of the present invention provides a kind of method of making above-mentioned phosphorus-nitrogen expansion type flame-retardant material.
Goal of the invention of the present invention is achieved in that a kind of phosphorus-nitrogen expansion type flame-retardant material, it is characterized in that: described phosphorus-nitrogen expansion type flame-retardant material comprises polyolefin resin, phosphate compound, many carbon polyol, nitrogenous many carbon compounds, coupling coating, toughner, oxidation inhibitor, filler and lubricant, and each components contents is calculated by mass percentage and is respectively polyolefin resin 59%-73%; Phosphate compound 8%-21%; Many carbon polyol 3%-14%; Nitrogenous many carbon compounds 3%-16%; Coupling coating 0.1%-0.6%; Toughner 4%-10%; Oxidation inhibitor 0.1%-0.8%; Filler 0.5%-10%; Lubricant 0.1%-0.5%.
Ratio between described phosphate compound, many carbon polyol and the nitrogenous many carbon compounds three is (1.8-4.7): (0.6-2.5): (0.4-2.8), three's mass fraction sum accounts for the 23%-28% of total mass umber.
Described phosphate compound is an ammonium polyphosphate.
Described many carbon polyol is a tetramethylolmethane.
Described nitrogenous many carbon compounds is that the wherein a kind of or mentioned component of melamine cyanurate, ortho-phosphoric acid two trimeric cyanamides mixes with arbitrary proportion.
Described polyolefin resin is a polypropylene.
Described coupling coating is an aluminium titanium composite coupler.
Described toughner is ethylene-propylene rubber(EPR).
Described oxidation inhibitor is four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] the wherein a kind of or mentioned component of pentaerythritol ester (antioxidant 1010), β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester (antioxidant 1076) mixes with arbitrary proportion.
Described oxidation inhibitor is that the wherein a kind of or mentioned component of tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) esters (oxidation inhibitor 168), tricresyl phosphite (nonyl phenyl) ester (oxidation inhibitor TNP) mixes with arbitrary proportion.
Described filler is that the wherein a kind of or mentioned component of polynite, brucite, zeolite, expanded graphite mixes with arbitrary proportion.
Described lubricant is that the wherein a kind of or mentioned component of methyl-silicone oil, whiteruss mixes with arbitrary proportion.
A kind of method of making above-mentioned phosphorus-nitrogen expansion type flame-retardant material, its step is as follows:
A: with phosphate compound, many carbon polyol and nitrogenous many carbon compounds under 100 ℃ of environment forced air drying 3-6 hour respectively;
B: take by weighing dry good phosphate compound, many carbon polyol and nitrogenous many carbon compounds by weight ratio, in high-speed mixer, stir and add the coupling coating after 3-5 minute, restir 5-8 minute, compound is joined in the hopper of twin screw extruder, through extruding → cooling off → steps such as drying → pelletizing finish the preparation of multifunctional flame-proof master batch.
C: take by weighing polyolefin resin, toughner, oxidation inhibitor, filler and lubricant by weight ratio, add the multifunctional flame-proof master batch in the b step, in high-speed mixer, stirred 3-5 minute;
D: the material that mixes in the c step is joined the hopper of twin screw extruder, under 180-240 ℃ extruder temperature, presses the rate of feeding feeding of 5Hz-15Hz, through extruding → cooling off → drying → pelletizing packaging and other steps finishes.
The present invention has the following advantages:
1, in the phosphorus-nitrogen expansion type flame-retardant material of the present invention owing to adopted the compound system of phosphate compound, many carbon polyol and nitrogenous many carbon compounds, phosphate compound can produce the phosphoric acid or the metaphosphoric acid of many carbon of esterification polyol, generate phosphoric acid ester and derivative thereof, this phosphoric acid ester and derivative thereof can produce inorganics and form the carbon residue excess under decomposition temperature.Nitrogenous many carbon compounds can be used as the catalyzer that generates phosphoric acid ester and derivative thereof, and discharges non-flammable gases, thus its can effectively improve polyolefin resin inflammable, phenomenon such as drippage appears.
2, adopted the compound system of phosphate compound, many carbon polyol and nitrogenous many carbon compounds in the phosphorus-nitrogen expansion type flame-retardant material of the present invention, when combustion decomposition, can not discharge toxic gas, and the smog that the phosphorus nitrogen systems produces when decomposing is few, thereby life security that can critical people when macromolecular material burns.
3, adopt phosphorus nitrogen compound system in the phosphorus-nitrogen expansion type flame-retardant material of the present invention, because the molecular weight of phosphate compound and nitrogenous many carbon compounds molecular chain is less, macromole mainly is a polyolefin resin, and the snappiness of polyolefin resin is better, so this material has good processing properties.In addition, the flame retarding efficiency of phosphorus nitrogen compound system is higher, so its usage quantity is also less, can significantly reduce the production cost of material.
Embodiment
Phosphorus-nitrogen expansion type flame-retardant material of the present invention comprises polyolefin resin, phosphate compound, many carbon polyol, nitrogenous many carbon compounds, coupling coating, toughner, oxidation inhibitor, filler, lubricant and fire retardant, and wherein each components contents is calculated by mass percentage and is respectively polyolefin resin 59%-73%; Phosphate compound 8%-21%; Many carbon polyol 3%-14%; Nitrogenous many carbon compounds 3%-16%; Coupling coating 0.1%-0.6%; Toughner 4%-10%; Oxidation inhibitor 0.1%-0.8%; Filler 0.5%-10%; Lubricant 0.1%-0.5%.Polyolefin resin adopts polypropylene, and phosphate compound, many carbon polyol and nitrogenous many carbon compounds form compound system, phosphate compound can produce the phosphoric acid or the metaphosphoric acid of many carbon of esterification polyol, generates phosphoric acid ester and derivative thereof.Reaction can generate three (1-oxos-2 between phosphate compound, many carbon polyol and the nitrogenous many carbon compounds three, 6,7-trioxa-1-phospha dicyclo [2.2.2] octane methylene radical-4) phosphoric acid ester or 2,2-dimethyl-1, phosphate derivatives such as ammediol-two (neopentyl glycol) biphosphonate improve flame retardant effect.This phosphoric acid ester and derivative thereof can produce inorganics and form the carbon residue excess under decomposition temperature.Nitrogenous many carbon compounds can be used as the catalyzer that generates phosphoric acid ester and derivative thereof, and discharges non-flammable gases.For this system can be played one's part to the full, ratio between phosphate compound, many carbon polyol and the nitrogenous many carbon compounds three is (1.8-4.7): (0.6-2.5): (0.4-2.8), three's mass fraction sum accounts for the 23%-28% of total mass umber.Phosphate compound adopts ammonium polyphosphate, also can adopt the wherein a kind of or mentioned component of ammonium polyphosphate, melamine pyrophosphate, positive two triphosphoric acid trimeric cyanamides, polyphosphoric acid melamine, ortho-phosphoric acid trimeric cyanamide to mix with arbitrary proportion; Many carbon polyol adopts tetramethylolmethane, also can adopt the wherein a kind of or mentioned component of dipentaerythritol, tripentaerythritol, starch, resol to mix with arbitrary proportion; Nitrogenous many carbon compounds then adopts melamine cyanurate or ortho-phosphoric acid two trimeric cyanamides or above composition to mix with arbitrary proportion, also can adopt the wherein a kind of or mentioned component of melamine cyanurate, trimeric cyanamide, ortho-phosphoric acid trimeric cyanamide, positive two triphosphoric acid trimeric cyanamides, melamine pyrophosphate, melamino-formaldehyde, boric acid trimeric cyanamide to mix with arbitrary proportion.The molecular chain of above-mentioned three base polymers all has the small molecular weight group, thereby its molecular chain flexibility is stronger, and material is easy to processing, and the reactive group of above-mentioned three base polymers is all more, so the consistency between the three is stronger.Coupling coating aluminium titanium composite coupler, it plays coating, link coupled effect.Toughner is selected ethylene-propylene rubber(EPR) for use, has good consistency between ethylene-propylene rubber(EPR) and polypropylene, ammonium polyphosphate, tetramethylolmethane, melamine cyanurate and ortho-phosphoric acid two trimeric cyanamides, and its toughening effect is good.Oxidation inhibitor can be selected four [β-(3 for use, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010) or β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester (antioxidant 1076), or tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) esters (oxidation inhibitor 168) or tricresyl phosphite (nonyl phenyl) ester (oxidation inhibitor TNP).The consistency of above-mentioned four kinds of oxidation inhibitor and phosphorus nitrogen carbon compound system is stronger, and its antioxidant effect is good.In addition, contain alcohol radical or phosphorous acid base in the above-mentioned oxidation inhibitor, in the material polymerization process, can play the effect that replenishes group.Filler selects for use the wherein a kind of or mentioned component of polynite, brucite, zeolite, expanded graphite to mix with arbitrary proportion, and the consistency between above-mentioned filler and the polyolefin resin is good, and can strengthen the mechanical property of polyolefin resin.Lubricant selects for use the wherein a kind of or mentioned component of methyl-silicone oil, whiteruss to mix with arbitrary proportion.Because the molecular chain of polyolefin resin is regular type molecular structure, and after adding the small molecular weight group, strengthen the regularity of its molecular chain easily, can improve the flowability of polyolefin resin melt behind the adding lubricant, make polyolefin resin be easy to processing.The method steps of making this phosphorus-nitrogen expansion type flame-retardant material comprises:
A: with phosphate compound, many carbon polyol and nitrogenous many carbon compounds under 100 ℃ of environment forced air drying 3-6 hour respectively;
B: take by weighing dry good phosphate compound, many carbon polyol and nitrogenous many carbon compounds by weight ratio, in high-speed mixer, stir and add the coupling coating after 3-5 minute, restir 5-8 minute, compound is joined in the hopper of twin screw extruder, through extruding → cooling off → steps such as drying → pelletizing finish the preparation of multifunctional flame-proof master batch.
C: take by weighing polyolefin resin, toughner, oxidation inhibitor, filler and lubricant by weight ratio, add the multifunctional flame-proof master batch in the b step, in high-speed mixer, stirred 3-5 minute;
D: the material that mixes in the c step is joined the hopper of twin screw extruder, under 180-240 ℃ extruder temperature, presses the rate of feeding feeding of 5Hz-15Hz, through extruding → cooling off → drying → pelletizing packaging and other steps finishes.
Below by table 1 each embodiment is further specified the present invention, but therefore do not limit the invention in the described scope of embodiments.
Embodiment 1
Phosphorus-nitrogen expansion type flame-retardant material of the present invention comprises polyolefin resin, phosphate compound, many carbon polyol, nitrogenous many carbon compounds, coupling coating, toughner, oxidation inhibitor, filler, lubricant and fire retardant.Polyolefin resin is a polypropylene; Phosphate compound is an ammonium polyphosphate; Many carbon polyol is a tetramethylolmethane; Nitrogenous many carbon compounds is a melamine cyanurate; The coupling coating is an aluminium titanium composite coupler; Toughner is ethylene-propylene rubber(EPR); Oxidation inhibitor is antioxidant 1010 and oxidation inhibitor 168 mixtures; Filler is a brucite; Lubricant is methyl-silicone oil and whiteruss mixture.Each components contents is calculated by mass percentage and is respectively polypropylene: 73%; Ammonium polyphosphate: 8%; Tetramethylolmethane: 11%; Melamine cyanurate: 3%; Aluminium titanium composite coupler: 0.1%; Ethylene-propylene rubber(EPR): 4%; Antioxidant 1010: 0.1%; Oxidation inhibitor 168:0.1%; Brucite: 0.5%; Methyl-silicone oil: 0.1%; Whiteruss: 0.1%.
The method steps of making this phosphorus-nitrogen expansion type flame-retardant material is:
A: earlier with ammonium polyphosphate, tetramethylolmethane and melamine cyanurate under 100 ℃ of environment dry 3 hours respectively;
B: take by weighing dry good ammonium polyphosphate, tetramethylolmethane and melamine cyanurate by weight ratio, in high-speed mixer, stir after 3-5 minute and add aluminium titanium composite coupler, restir 5-8 minute, compound is joined in the hopper of twin screw extruder, through extruding → cooling off → steps such as drying → pelletizing finish the preparation of multifunctional flame-proof master batch.
C: take by weighing polypropylene, ethylene-propylene rubber(EPR), antioxidant 1010, oxidation inhibitor 168, brucite, methyl-silicone oil and whiteruss by weight ratio, add the multifunctional flame-proof master batch in the b step, in high-speed mixer, stirred 5 minutes;
D: the material that mixes in the c step is joined the hopper of twin screw extruder, under 200 ℃ temperature, finish through fusion → mixing → shear → extrude → cool off → drying → pelletizing packaging and other steps according to the rate of feeding of 10Hz.
The sample of this embodiment is through GB/T 2406-1993 and GB/T 2408-1996 test, and its burns oxygen index is 30, and fire-retardant rank is V0, and combustion processes does not have drippage.
Embodiment 2
Phosphorus-nitrogen expansion type flame-retardant material of the present invention comprises polyolefin resin, phosphate compound, many carbon polyol, nitrogenous many carbon compounds, coupling coating, toughner, oxidation inhibitor, filler, lubricant and fire retardant.Polyolefin resin is a polypropylene; Phosphate compound is an ammonium polyphosphate; Many carbon polyol is a tetramethylolmethane; Nitrogenous many carbon compounds is melamine cyanurate and ortho-phosphoric acid two trimeric cyanamide mixtures; The coupling coating is an aluminium titanium composite coupler; Toughner is ethylene-propylene rubber(EPR); Oxidation inhibitor is antioxidant 1076 and oxidation inhibitor 168 mixtures; Filler is an expanded graphite; Lubricant is a whiteruss.Each components contents is calculated by mass percentage and is respectively polypropylene: 59%; Ammonium polyphosphate: 21%; Tetramethylolmethane: 3%; Melamine cyanurate: 2%; Ortho-phosphoric acid two trimeric cyanamides: 2%; Aluminium titanium composite coupler: 0.6%; Ethylene-propylene rubber(EPR): 9%; Antioxidant 1076: 0.4%; Oxidation inhibitor 168:0.4%; Expanded graphite: 2.5%; Whiteruss: 0.1%.
The method steps of making this phosphorus-nitrogen expansion type flame-retardant material is:
A: earlier with ammonium polyphosphate, tetramethylolmethane, melamine cyanurate and ortho-phosphoric acid two trimeric cyanamides under 100 ℃ of environment dry 4 hours respectively;
B: take by weighing dry good ammonium polyphosphate, tetramethylolmethane, melamine cyanurate and ortho-phosphoric acid two trimeric cyanamides by weight ratio, in high-speed mixer, stir after 3-5 minute and add aluminium titanium composite coupler, restir 5-8 minute, compound is joined in the hopper of twin screw extruder, through extruding → cooling off → steps such as drying → pelletizing finish the preparation of multifunctional flame-proof master batch.
C: take by weighing the multifunctional flame-proof master batch in polypropylene, ethylene-propylene rubber(EPR), antioxidant 1076, oxidation inhibitor 168, expanded graphite and the whiteruss adding b step by weight ratio, in high-speed mixer, stirred 3 minutes;
D: the material that mixes in the c step is joined the hopper of twin screw extruder, under 240 ℃ temperature, finish through fusion → mixing → shear → extrude → cool off → drying → pelletizing packaging and other steps according to the rate of feeding of 15Hz.
The sample of this embodiment is through GB/T 2406-1993 and GB/T 2408-1996 test, and its burns oxygen index is 32, and fire-retardant rank is V0, and combustion processes does not have drippage.
Embodiment 3
Phosphorus-nitrogen expansion type flame-retardant material of the present invention comprises polyolefin resin, phosphate compound, many carbon polyol, nitrogenous many carbon compounds, coupling coating, toughner, oxidation inhibitor, filler, lubricant and fire retardant.Polyolefin resin is a polypropylene; Phosphate compound is an ammonium polyphosphate; Many carbon polyol is a tetramethylolmethane; Nitrogenous many carbon compounds is ortho-phosphoric acid two trimeric cyanamides; The coupling coating is an aluminium titanium composite coupler; Toughner is ethylene-propylene rubber(EPR); Oxidation inhibitor is antioxidant 1010 and oxidation inhibitor TNP mixture; Filler is the mixture of polynite, brucite, zeolite and expanded graphite; Lubricant is methyl-silicone oil and whiteruss mixture.Each components contents is calculated by mass percentage and is respectively polypropylene: 60%; Ammonium polyphosphate: 8%; Tetramethylolmethane: 14%; Ortho-phosphoric acid two trimeric cyanamides: 3%; Aluminium titanium composite coupler: 0.3%; Ethylene-propylene rubber(EPR): 4%; Antioxidant 1010: 0.1%; Oxidation inhibitor TNP:0.1%; Polynite: 3%; Brucite: 3%; Zeolite: 2%; Expanded graphite: 2%; Methyl-silicone oil: 0.3%; Whiteruss: 0.2%.
The method steps of making this phosphorus-nitrogen expansion type flame-retardant material is:
A: earlier with ammonium polyphosphate, tetramethylolmethane and ortho-phosphoric acid two trimeric cyanamides under 100 ℃ of environment dry 5 hours respectively;
B: take by weighing dry good ammonium polyphosphate, tetramethylolmethane and ortho-phosphoric acid two trimeric cyanamides by weight ratio, in high-speed mixer, stir after 3-5 minute and add aluminium titanium composite coupler, restir 5-8 minute, compound is joined in the hopper of twin screw extruder, through extruding → cooling off → steps such as drying → pelletizing finish the preparation of multifunctional flame-proof master batch.
C: take by weighing the multifunctional flame-proof master batch in polypropylene, ethylene-propylene rubber(EPR), antioxidant 1010, oxidation inhibitor TNP, polynite, brucite, zeolite, expanded graphite, methyl-silicone oil and the whiteruss adding b step by weight ratio, in high-speed mixer, stirred 5 minutes;
D: the material that mixes in the c step is joined the hopper of twin screw extruder, under 180 ℃ temperature, finish through fusion → mixing → shear → extrude → cool off → drying → pelletizing packaging and other steps according to the rate of feeding of 5Hz.
The sample of this embodiment is through GB/T 2406-1993 and GB/T 2408-1996 test, and its burns oxygen index is 32, and fire-retardant rank is V0, and combustion processes does not have drippage.
Embodiment 4
Phosphorus-nitrogen expansion type flame-retardant material of the present invention comprises polyolefin resin, phosphate compound, many carbon polyol, nitrogenous many carbon compounds, coupling coating, toughner, oxidation inhibitor, filler, lubricant and fire retardant.Polyolefin resin is a polypropylene; Phosphate compound is an ammonium polyphosphate; Many carbon polyol is a tetramethylolmethane; Nitrogenous many carbon compounds is a melamine cyanurate; The coupling coating is an aluminium titanium composite coupler; Toughner is ethylene-propylene rubber(EPR); Oxidation inhibitor is antioxidant 1076 and oxidation inhibitor 168 mixtures; Filler is polynite; Lubricant is a methyl-silicone oil.Each components contents is calculated by mass percentage and is respectively polypropylene: 61%; Ammonium polyphosphate: 9%; Tetramethylolmethane: 3%; Melamine cyanurate: 16%; Aluminium titanium composite coupler: 0.2%; Ethylene-propylene rubber(EPR): 10%; Antioxidant 1076: 0.05%; Oxidation inhibitor 168:0.05%; Polynite: 0.5%; Methyl-silicone oil: 0.2%.
The method steps of making this phosphorus-nitrogen expansion type flame-retardant material is:
A: earlier with ammonium polyphosphate, tetramethylolmethane and melamine cyanurate under 100 ℃ of environment dry 3 hours respectively;
B: take by weighing dry good ammonium polyphosphate, tetramethylolmethane and melamine cyanurate by weight ratio, in high-speed mixer, stir after 3-5 minute and add aluminium titanium composite coupler, restir 5-8 minute, compound is joined in the hopper of twin screw extruder, through extruding → cooling off → steps such as drying → pelletizing finish the preparation of multifunctional flame-proof master batch.
C: take by weighing the multifunctional flame-proof master batch in polypropylene, ethylene-propylene rubber(EPR), antioxidant 1076, oxidation inhibitor 168, polynite and the methyl-silicone oil adding b step by weight ratio, in high-speed mixer, stirred 4 minutes;
D: the material that mixes in the c step is joined the hopper of twin screw extruder, under 210 ℃ temperature, finish through fusion → mixing → shear → extrude → cool off → drying → pelletizing packaging and other steps according to the rate of feeding of 11Hz.
The sample of this embodiment is through GB/T 2406-1993 and GB/T 2408-1996 test, and its burns oxygen index is 31, and fire-retardant rank is V0, and combustion processes does not have drippage.
Embodiment 5
Phosphorus-nitrogen expansion type flame-retardant material of the present invention comprises polyolefin resin, phosphate compound, many carbon polyol, nitrogenous many carbon compounds, coupling coating, toughner, oxidation inhibitor, filler, lubricant and fire retardant.Polyolefin resin is a polypropylene; Phosphate compound is an ammonium polyphosphate; Many carbon polyol is a tetramethylolmethane; Nitrogenous many carbon compounds is melamine cyanurate and ortho-phosphoric acid two trimeric cyanamide mixtures; The coupling coating is an aluminium titanium composite coupler; Toughner is ethylene-propylene rubber(EPR); Oxidation inhibitor is antioxidant 1010, antioxidant 1076, oxidation inhibitor 168 and oxidation inhibitor TNP mixture; Filler is polynite and zeolite mixture; Lubricant is methyl-silicone oil and whiteruss mixture.Each components contents is calculated by mass percentage and is respectively polypropylene: 68%; Ammonium polyphosphate: 10%; Tetramethylolmethane: 5%; Melamine cyanurate: 4%; Ortho-phosphoric acid two trimeric cyanamides: 3%; Aluminium titanium composite coupler: 0.2%; Ethylene-propylene rubber(EPR): 5%; Antioxidant 1010: 0.1%; Antioxidant 1076: 0.1%; Oxidation inhibitor 168:0.1%; Oxidation inhibitor TNP:0.1%; Polynite: 2%; Zeolite: 2%; Methyl-silicone oil: 0.1%; Whiteruss: 0.1%.
The method steps of making this phosphorus-nitrogen expansion type flame-retardant material is:
A: earlier with ammonium polyphosphate, tetramethylolmethane, melamine cyanurate and ortho-phosphoric acid two trimeric cyanamides under 100 ℃ of environment dry 5 hours respectively;
B: take by weighing dry good ammonium polyphosphate, tetramethylolmethane, melamine cyanurate and ortho-phosphoric acid two trimeric cyanamides by weight ratio, in high-speed mixer, stir after 3-5 minute and add aluminium titanium composite coupler, restir 5-8 minute, compound is joined in the hopper of twin screw extruder, through extruding → cooling off → steps such as drying → pelletizing finish the preparation of multifunctional flame-proof master batch.
C: take by weighing the aluminium titanium composite coupler in polypropylene, ethylene-propylene rubber(EPR), antioxidant 1010, antioxidant 1076, oxidation inhibitor 168, oxidation inhibitor TNP, polynite, zeolite, methyl-silicone oil and the whiteruss adding b step by weight ratio, in high-speed mixer, stirred 5 minutes;
D: the material that mixes in the c step is joined the hopper of twin screw extruder, under 200 ℃ temperature, finish through fusion → mixing → shear → extrude → cool off → drying → pelletizing packaging and other steps according to the rate of feeding of 11Hz.
The sample of this embodiment is through GB/T 2406-1993 and GB/T 2408-1996 test, and its burns oxygen index is 31, and fire-retardant rank is V0, and combustion processes does not have drippage.
Embodiment 6
Phosphorus-nitrogen expansion type flame-retardant material of the present invention comprises polyolefin resin, phosphate compound, many carbon polyol, nitrogenous many carbon compounds, coupling coating, toughner, oxidation inhibitor, filler, lubricant and fire retardant.Polyolefin resin is a polypropylene; Phosphate compound is an ammonium polyphosphate; Many carbon polyol is a tetramethylolmethane; Nitrogenous many carbon compounds is melamine cyanurate and ortho-phosphoric acid two trimeric cyanamide mixtures; The coupling coating is an aluminium titanium composite coupler; Toughner is ethylene-propylene rubber(EPR); Oxidation inhibitor is antioxidant 1010 and oxidation inhibitor 168 mixtures; Filler is brucite and expanded graphite mixture; Lubricant is a whiteruss.Each components contents is calculated by mass percentage and is respectively polypropylene: 66%; Ammonium polyphosphate: 13%; Tetramethylolmethane: 4%; Melamine cyanurate: 5%; Ortho-phosphoric acid two trimeric cyanamides: 1%; Aluminium titanium composite coupler: 0.1%; Ethylene-propylene rubber(EPR): 6%; Antioxidant 1010: 0.2; Oxidation inhibitor 168:0.3%; Brucite: 2.1%; Expanded graphite: 2.1%; Whiteruss: 0.2%.
The method steps of making this phosphorus-nitrogen expansion type flame-retardant material is:
A: earlier with ammonium polyphosphate, tetramethylolmethane, melamine cyanurate and ortho-phosphoric acid two trimeric cyanamides under 100 ℃ of environment dry 5 hours respectively;
B: take by weighing dry good ammonium polyphosphate, tetramethylolmethane, melamine cyanurate and ortho-phosphoric acid two trimeric cyanamides by weight ratio, in high-speed mixer, stir after 3-5 minute and add aluminium titanium composite coupler, restir 5-8 minute, compound is joined in the hopper of twin screw extruder, through extruding → cooling off → steps such as drying → pelletizing finish the preparation of multifunctional flame-proof master batch.
C: take by weighing the multifunctional flame-proof master batch in polypropylene, ethylene-propylene rubber(EPR), antioxidant 1010, oxidation inhibitor 168, brucite, expanded graphite and the whiteruss adding b step by weight ratio, in high-speed mixer, stirred 4 minutes;
D: the material that mixes in the c step is joined the hopper of twin screw extruder, under 210 ℃ temperature, finish through fusion → mixing → shear → extrude → cool off → drying → pelletizing packaging and other steps according to the rate of feeding of 12Hz.
The sample of this embodiment is through GB/T 2406-1993 and GB/T 2408-1996 test, and its burns oxygen index is 32, and fire-retardant rank is V0, and combustion processes does not have drippage.
Embodiment 7
Phosphorus-nitrogen expansion type flame-retardant material of the present invention comprises polyolefin resin, phosphate compound, many carbon polyol, nitrogenous many carbon compounds, coupling coating, toughner, oxidation inhibitor, filler, lubricant and fire retardant.Polyolefin resin is a polypropylene; Phosphate compound is an ammonium polyphosphate; Many carbon polyol is a tetramethylolmethane; Nitrogenous many carbon compounds is melamine cyanurate and ortho-phosphoric acid two trimeric cyanamide mixtures; The coupling coating is an aluminium titanium composite coupler; Toughner is ethylene-propylene rubber(EPR); Oxidation inhibitor is antioxidant 1010 and oxidation inhibitor 168 mixtures; Filler is a zeolite; Lubricant is a methyl-silicone oil.Each components contents is calculated by mass percentage and is respectively polypropylene: 63%; Ammonium polyphosphate: 17%; Tetramethylolmethane: 6%; Melamine cyanurate: 1%; Ortho-phosphoric acid two trimeric cyanamides: 3%; Aluminium titanium composite coupler: 0.2%; Ethylene-propylene rubber(EPR): 7%; Antioxidant 1010: 0.3; Oxidation inhibitor 168:0.3%; Zeolite: 2%; Methyl-silicone oil: 0.2%.
The method steps of making this phosphorus-nitrogen expansion type flame-retardant material is:
A: earlier with ammonium polyphosphate, tetramethylolmethane, melamine cyanurate and ortho-phosphoric acid two trimeric cyanamides under 100 ℃ of environment dry 5 hours respectively;
B: take by weighing dry good ammonium polyphosphate, tetramethylolmethane, melamine cyanurate and ortho-phosphoric acid two trimeric cyanamides by weight ratio, in high-speed mixer, stir after 3-5 minute and add aluminium titanium composite coupler, restir 5-8 minute, compound is joined in the hopper of twin screw extruder, through extruding → cooling off → steps such as drying → pelletizing finish the preparation of multifunctional flame-proof master batch.
C: take by weighing the multifunctional flame-proof master batch in polypropylene, ethylene-propylene rubber(EPR), antioxidant 1010, oxidation inhibitor 168, zeolite and the methyl-silicone oil adding b step by weight ratio, in high-speed mixer, stirred 4 minutes;
D: the material that mixes in the c step is joined the hopper of twin screw extruder, under 220 ℃ temperature, finish through fusion → mixing → shear → extrude → cool off → drying → pelletizing packaging and other steps according to the rate of feeding of 12Hz.
The sample of this embodiment is through GB/T 2406-1993 and GB/T 2408-1996 test, and its burns oxygen index is 30, and fire-retardant rank is V0, and combustion processes does not have drippage.
Table 1 (wherein content is all calculated by mass percentage)

Claims (13)

1, a kind of phosphorus-nitrogen expansion type flame-retardant material, it is characterized in that: described phosphorus-nitrogen expansion type flame-retardant material comprises polyolefin resin, phosphate compound, many carbon polyol, nitrogenous many carbon compounds, toughner, oxidation inhibitor, filler and lubricant, and each components contents is calculated by mass percentage and is respectively polyolefin resin 59%-73%; Phosphate compound 8%-21%; Many carbon polyol 3%-14%; Nitrogenous many carbon compounds 3%-16%; Coupling coating 0.1%-0.6%; Toughner 4%-10%; Oxidation inhibitor 0.1%-0.8%; Filler 0.5%-10%; Lubricant 0.1%-0.5%.
2, according to the described phosphorus-nitrogen expansion type flame-retardant material of claim 1, it is characterized in that: the ratio between described phosphate compound, many carbon polyol and the nitrogenous many carbon compounds three is (1.8-4.7): (0.6-2.5): (0.4-2.8), three's mass fraction sum accounts for the 23%-28% of total mass umber.
3, according to the described phosphorus-nitrogen expansion type flame-retardant material of claim 1, it is characterized in that: described phosphate compound is an ammonium polyphosphate.
4, according to the described phosphorus-nitrogen expansion type flame-retardant material of claim 1, it is characterized in that: described many carbon polyol is a tetramethylolmethane.
5, according to the described phosphorus-nitrogen expansion type flame-retardant material of claim 1, it is characterized in that: described nitrogenous many carbon compounds is that melamine cyanurate or ortho-phosphoric acid two trimeric cyanamides or above composition mix with arbitrary proportion.
6, according to the described phosphorus-nitrogen expansion type flame-retardant material of claim 1, it is characterized in that: described polyolefin resin is a polypropylene.
7 according to the described phosphorus-nitrogen expansion type flame-retardant material of claim 1, it is characterized in that: described coupling coating is an aluminium titanium composite coupler.
8, according to the described phosphorus-nitrogen expansion type flame-retardant material of claim 1, it is characterized in that: described toughner is ethylene-propylene rubber(EPR).
9, according to the described phosphorus-nitrogen expansion type flame-retardant material of claim 1, it is characterized in that: described oxidation inhibitor is four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] the wherein a kind of or mentioned component of pentaerythritol ester (antioxidant 1010), β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester (antioxidant 1076) mixes with arbitrary proportion.
10, according to the described phosphorus-nitrogen expansion type flame-retardant material of claim 1, it is characterized in that: described oxidation inhibitor is that the wherein a kind of or mentioned component of tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) esters (oxidation inhibitor 168), tricresyl phosphite (nonyl phenyl) ester (oxidation inhibitor TNP) mixes with arbitrary proportion.
11, according to the described phosphorus-nitrogen expansion type flame-retardant material of claim 1, it is characterized in that: described filler is that the wherein a kind of or mentioned component of polynite, brucite, zeolite, expanded graphite mixes with arbitrary proportion.
12, according to the described phosphorus-nitrogen expansion type flame-retardant material of claim 1, it is characterized in that: described lubricant is that the wherein a kind of or mentioned component of methyl-silicone oil, whiteruss mixes with arbitrary proportion.
13, a kind of method of making the described phosphorus-nitrogen expansion type flame-retardant material of claim 1, its step comprises:
A: with phosphate compound, many carbon polyol and nitrogenous many carbon compounds under 100 ℃ of environment forced air drying 3-6 hour respectively;
B: take by weighing dry good phosphate compound, many carbon polyol and nitrogenous many carbon compounds by weight ratio, in high-speed mixer, stir and add the coupling coating after 3-5 minute, restir 5-8 minute, compound is joined in the hopper of twin screw extruder, through extruding → cooling off → steps such as drying → pelletizing finish the preparation of multifunctional flame-proof master batch.
C: take by weighing polyolefin resin, toughner, oxidation inhibitor, filler and lubricant by weight ratio, add the multifunctional flame-proof master batch in the b step, in high-speed mixer, stirred 3-5 minute;
D: the material that mixes in the c step is joined the hopper of twin screw extruder, under 180-240 ℃ extruder temperature, presses the rate of feeding feeding of 5Hz-15Hz, through extruding → cooling off → drying → pelletizing packaging and other steps finishes.
CNA2008102185577A 2008-10-23 2008-10-23 Phosphorus-nitrogen expansion type flame-retardant material and production method thereof CN101463154A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101831134A (en) * 2010-05-10 2010-09-15 宁波市青湖弹性体科技有限公司 Thermoplastic halogen-free flame retarding elastomer composition for electric wire and cable covering materials
CN102796319A (en) * 2012-08-11 2012-11-28 中山赛特工程塑料有限公司 Expansion type flame-retardant polypropylene composite
CN102863691A (en) * 2012-09-17 2013-01-09 深圳市科聚新材料有限公司 Polypropylene composite material and preparation method thereof
CN103627084A (en) * 2013-11-12 2014-03-12 青岛广联达精密机械有限公司 High-hardness PP (polypropylene) alloy
CN104404770A (en) * 2014-12-16 2015-03-11 山东圣泉新材料股份有限公司 Amino resin composition for flame-retardant wet curtain and preparation method and application thereof
CN105001510A (en) * 2015-07-02 2015-10-28 广州科苑新型材料有限公司 Low temperature resistant halogen-free flame-retardant light scattering polypropylene composition and preparation method thereof
CN105802013A (en) * 2016-04-22 2016-07-27 东源顺亨塑胶阻燃材料厂 Flame-retardant masterbatch, flame-retardant masterbatch based phosphorus-nitrogen intumescent flame-retardant material and preparation method thereof
US10280369B2 (en) 2012-04-20 2019-05-07 Board Of Regents Of The University Of Texas System Thermal barrier mixtures and uses thereof

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101831134A (en) * 2010-05-10 2010-09-15 宁波市青湖弹性体科技有限公司 Thermoplastic halogen-free flame retarding elastomer composition for electric wire and cable covering materials
US10280369B2 (en) 2012-04-20 2019-05-07 Board Of Regents Of The University Of Texas System Thermal barrier mixtures and uses thereof
CN102796319A (en) * 2012-08-11 2012-11-28 中山赛特工程塑料有限公司 Expansion type flame-retardant polypropylene composite
CN102863691A (en) * 2012-09-17 2013-01-09 深圳市科聚新材料有限公司 Polypropylene composite material and preparation method thereof
CN103627084A (en) * 2013-11-12 2014-03-12 青岛广联达精密机械有限公司 High-hardness PP (polypropylene) alloy
CN104404770A (en) * 2014-12-16 2015-03-11 山东圣泉新材料股份有限公司 Amino resin composition for flame-retardant wet curtain and preparation method and application thereof
CN105001510A (en) * 2015-07-02 2015-10-28 广州科苑新型材料有限公司 Low temperature resistant halogen-free flame-retardant light scattering polypropylene composition and preparation method thereof
CN105001510B (en) * 2015-07-02 2018-06-12 广州科苑新型材料有限公司 A kind of low temperature resistant halogen-free flameproof light diffusion polypropene composition and preparation method thereof
CN105802013A (en) * 2016-04-22 2016-07-27 东源顺亨塑胶阻燃材料厂 Flame-retardant masterbatch, flame-retardant masterbatch based phosphorus-nitrogen intumescent flame-retardant material and preparation method thereof

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