CN104448546B - A kind of catalytic flame retardancy mineral macromolecular material and preparation method thereof - Google Patents

A kind of catalytic flame retardancy mineral macromolecular material and preparation method thereof Download PDF

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CN104448546B
CN104448546B CN201410312392.5A CN201410312392A CN104448546B CN 104448546 B CN104448546 B CN 104448546B CN 201410312392 A CN201410312392 A CN 201410312392A CN 104448546 B CN104448546 B CN 104448546B
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mineral
macromolecular material
flame retardancy
dolomite
catalytic
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CN104448546A (en
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张以河
尹玉霞
吕凤柱
甄志超
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China University of Geosciences Beijing
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China University of Geosciences Beijing
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
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    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
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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
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract

A kind of catalytic flame retardancy mineral macromolecular material of invention and preparation method thereof, belongs to technical field of function materials.Catalytic flame retardancy mineral macromolecular material of the invention with macromolecule pellet, catalyst and flame retardation catalyst as raw material, wherein, flame retardation catalyst is prepared by the following method：During water-soluble metal salt and dolomite press certain mass than input water, metal salt solution and dolomite stirring reaction are obtained into mineral slurry, calcining in Muffle furnace is put into after then mineral slurry is dried.The preparation method of catalytic flame retardancy mineral macromolecular material of the invention is：Macromolecule pellet, fire retardant and flame retardation catalyst are mixed in proportion, melting mixing extrusion obtains a kind of catalytic flame retardancy mineral macromolecular material.The invention provides a kind of catalytic flame retardancy mineral macromolecular material and preparation method thereof, raw material easily obtain, can be mass-produced and low cost.

Description

A kind of catalytic flame retardancy mineral macromolecular material and preparation method thereof
Technical field
The present invention relates to a kind of catalytic flame retardancy mineral macromolecular material and preparation method thereof, belong to functional material technology neck Domain.
Background technology
Fire is a kind of common disaster, and at present, the people in the whole world all suffer from the fire hazard situation of very severe.According to system Meter, in China, 1950~2010 years there is fire 545.9 ten thousand times in the whole nation altogether, cause about 190,000 people death, about 320,000 people injured, Direct economic loss is up to 345.8 hundred million yuan.Quick economic development makes our have a varicolored life, but ultra-large building and people Member's gathering place is on the increase, and the use of new material, especially novel high polymer material considerably increases fire risk.Since The thirties in last century, macromolecular material enters the every field and aspect of national economy and people's lives, and the mankind begin to face Against new fire threat, because the macromolecular material overwhelming majority is all flammable or inflammable.
In order to ensure the security of the lives and property of the people, the generation of fire, the flame-retardant high-molecular of green low toxicity are prevented and reduced Material obtains the favor of countries in the world, and is widelyd popularize and applied.At present, in the family of environmental protection fire retarding agent, inorganic ore deposit Thing is the novel inorganic fire retardant of green, can be used for macromolecule and fills fire-retardant, nontoxic pollution-free.But it is in actual applications, inorganic Mineral flame retardants have the shortcomings that flame retarding efficiency is low, addition is big, it usually needs add more than 50wt%, can have base material There is fire resistance.Therefore, in order to overcome this shortcoming, the treatment such as surface modified, fine, compounding are often carried out to its fire retardant and is come The addition of inorganic mineral fire retardant is reduced, the flame retarding efficiency of flame-retardant system is improved.
Predict that catalytic flame retardancy is a kind of new and effective flame-retardant system, is had in flame retarded polymeric material field according to brainstrust Wide application prospect.Research for catalytic flame retardancy shows that flame retardation catalyst can be obvious in expansion type flame-retarding macromolecular material Improve fire resistance.Bourbigot S etc. have found that a small amount of 4A molecular sieves of addition are to be greatly improved APP/PER/ polyolefin bodies Fire resistance (Bourbigot S, Lebrasm, Delobelr, the et al.4A zeolite synergistic agent of system in new flame retardant intumescen formulations of polyethylenic polymers- Study of the effect of the constituentmonomers.Polym.Degrad.Stab., 1996,54 (23)：275-287).Feng Caimin is to the Cr that 2% is added in MPP/PEPA/PP composites2O3It is flame retardation catalyst, fire-retardant PP's Being greatly improved by limited oxygen index is high, (Feng Caimin, Liu Hongbo, Mai Qianzhi wait .Cr2O3The preparation of the fire-retardant PP of synergy and The research plastics of its thermal degradation performance, 2009,38 (3)：42-44).
At present, research of the catalytic flame retardancy in expansion type flame-retarding macromolecular material is more, and the mineral in environmental protection hinder Combustion macromolecular material is rarely reported.Therefore, the method for catalytic flame retardancy is introduced into mineral fire proofing, prepares catalytic flame retardancy mineral Macromolecular material, can further improve the fire resistance of fire-retardant mineral macromolecular material.Catalytic flame retardancy mineral macromolecular material Raw material sources extensively, cheap, process is simple, and environment-protecting asepsis are pollution-free, beneficial to large-scale production, is anticipated with reality Justice.
The content of the invention
It is an object of the invention to provide a kind of catalytic flame retardancy mineral macromolecular material and preparation method thereof, raw material are easily obtained Obtain, can be mass-produced and low cost.
Catalytic flame retardancy mineral macromolecular material of the invention with macromolecule pellet, fire retardant and flame retardation catalyst as raw material, The mass parts ratio of each constitutive material is respectively：Macromolecule pellet 20~80, fire retardant 20~80, flame retardation catalyst 1~10.Its In, flame retardation catalyst is prepared by the following method：During water-soluble metal salt presses certain mass than input water with dolomite, by gold Category salting liquid obtains mineral slurry with 3~7h of dolomite stirring reaction, then starches in being dried at 90~120 DEG C mineral, is finally putting into In 2~4h of calcining at 300~400 DEG C in Muffle furnace.
Described metal oxide is the mixture of one or more in iron oxide, cobalt oxide, nickel oxide.
Described water-soluble metal salt is (1~70): (19~30) with the mass ratio of dolomite.
Described fire retardant is the mixing of one or more in shepardite, montmorillonite, hydrotalcite, vermiculite, gibbsite Thing.
Described macromolecule pellet is the mixture of one or more in PP, PE, PVC, PS, ABS, PA, PC, PU.
A kind of preparation method of catalytic flame retardancy mineral macromolecular material of the invention is：By macromolecule pellet, fire retardant and Flame retardation catalyst mixes in proportion, melting mixing extrusion, obtains catalytic flame retardancy mineral macromolecular material.
Dolomite is natural minerals present in nature, and for flame retardation catalyst carrier, wide material sources are cheap, Prepared flame retardation catalyst can further improve the fire resistance of macromolecular material.Therefore, dolomite is processed into fire-retardant urging Agent is added in macromolecular material, not only has important application prospect in flame retarded polymeric material field, and with very Big potential age deduction.
The present invention has the advantages that compared with prior art.
The fire-retardant mineral macromolecular material of the catalytic flame retardancy mineral macromolecular material prepared by the present invention, less catalyst It is a kind of new method for improving Flame Retardancy energy with preferable anti-flammability, meanwhile, the present invention requires to set in preparation process Standby simple, easy to operate, economic worth is high, easily realizes large-scale production, therefore, the present invention is in the neck such as high molecular fire retardant material There is very big application prospect in domain.
Specific embodiment
Embodiment one
A kind of catalytic flame retardancy mineral macromolecular material loads nickel oxide with polypropylene (PP) pellet, shepardite and dolomite Flame retardation catalyst is raw material, and the quality of each constitutive material is respectively：PP pellets：6.5kg, shepardite：3kg, dolomite nickel-loaded Oxide fire retardant catalyst：0.5kg.Wherein, dolomite nickel-loaded oxide fire retardant catalyst is prepared by the following method：Nitre Sour nickel puts into water with dolomite in mass ratio 35: 65, and then nickel nitrate solution and dolomite stirring reaction 3h starch mineral In being dried at 100 DEG C, it is finally putting into Muffle furnace in calcining 3h at 400 DEG C.
A kind of preparation method of catalytic flame retardancy mineral macromolecular material is by the load of above-mentioned PP pellets, shepardite and dolomite Nickel oxide flame retardation catalyst, the melting mixing extrusion at 215 DEG C obtains being catalyzed brucite flame-retardant PP materials.
The linear burning rate of the catalysis brucite flame-retardant PP materials obtained by this example is 20.7mm/min, compared with without catalysis Brucite flame-retardant PP materials reduction by 35.9%.
Embodiment two
A kind of catalytic flame retardancy mineral macromolecular material is with polypropylene (PP) pellet, shepardite and dolomite supported ferriferous oxide Flame retardation catalyst is raw material, and the quality of each constitutive material is respectively：PP pellets：6.5kg, shepardite：3kg, dolomite load iron Oxide fire retardant catalyst：0.5kg.Wherein, dolomite supported ferriferous oxide flame retardation catalyst is prepared by the following method：Nitre In sour iron and dolomite in mass ratio 1: 1 input water, by iron nitrate solution and dolomite stirring reaction 4h, then by mineral starch in Dried at 120 DEG C, be finally putting into Muffle furnace in calcining 3h at 400 DEG C.
A kind of preparation method of catalytic flame retardancy mineral macromolecular material is by the load of above-mentioned PP pellets, shepardite and dolomite Ferriferous oxide flame retardation catalyst, the melting mixing extrusion at 215 DEG C obtains being catalyzed brucite flame-retardant PP materials.
The linear burning rate of the catalysis brucite flame-retardant PP materials obtained by this example is 22.9mm/min, compared with without catalysis Brucite flame-retardant PP materials reduction by 29.1%.

Claims (1)

1. a kind of catalytic flame retardancy mineral macromolecular material, its constitutive material and mass parts ratio are as follows：
Polypropylene (PP) pellet 65
Shepardite 30
Dolomite loads nickel oxide 5,
Described dolomite loads nickel oxide, and its preparation method is：Nickel nitrate puts into water with dolomite in mass ratio 35: 65 In, then nickel nitrate solution and dolomite stirring reaction 3h is starched in being dried at 100 DEG C mineral, it is finally putting into Muffle furnace In calcining 3h at 400 DEG C,
Mix above-mentioned in proportion, melting mixing extrusion obtains catalytic flame retardancy macromolecular material.
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CN103102593A (en) * 2013-02-20 2013-05-15 四川大学 Supported metal oxide catalytic synergistic inorganic flame retardant polypropylene composite material and preparation method thereof

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CN103102593A (en) * 2013-02-20 2013-05-15 四川大学 Supported metal oxide catalytic synergistic inorganic flame retardant polypropylene composite material and preparation method thereof

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