CN103589098A - Preparation method of flame retardant master batches in macromolecules - Google Patents
Preparation method of flame retardant master batches in macromolecules Download PDFInfo
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- CN103589098A CN103589098A CN201310552655.5A CN201310552655A CN103589098A CN 103589098 A CN103589098 A CN 103589098A CN 201310552655 A CN201310552655 A CN 201310552655A CN 103589098 A CN103589098 A CN 103589098A
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- bismuth
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- chloride solution
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Abstract
The invention relates to a preparation method of flame retardant master batches in macromolecules, which sequentially comprises the following process schemes: 1, preparing nano bismuth oxide with a particle size D50 of 0.1mum to 1mum by a bismuth metal gasification oxidation method; 2, preparing bismuth oxychloride with a particle size D50 of 0.5mum to 15mum by a bismuth chloride solution hydrolysis method 3, taking 99.5 weight parts of macromolecule mixture, carrying out high temperature softening, adding the nano bismuth oxide and the bismuth oxychloride to carry out mechanical stirring, and extruding on a double-screw extruder to obtain the bismuth system compound uniformly-dispersed master batches. The preparation method solves the problem that bismuth compound particles are difficult to disperse so as not to improve the flame retardant effect of a macromolecule product, does not need to be added with dispersants comprising a wetting agent and has an obvious superior flame retardant efficiency to the prior art. Under the condition of the same flame retardance and smoke suppression performance, since the adding amount of the flame retardant master batches is reduced, additive cost of the macromolecule product is reduced the flame retardant master batches are environmental-friendly flame retardant master batches.
Description
Technical field
The present invention relates to a kind of preparation method for polymer fire-retardant master granule, it provides flame retardant resistance spy and/or cigarette rejection characteristic to macromolecule products such as polyvinyl chloride (PVC).
Background technology
Known in the state of the art have various energy as fire retardant and/or smoke inhibitor, and these fire retardants and/or smoke inhibitor play fire retardation with multiple mechanism, and it comprises:
A) release-salt hydrate of water and/or carbonic acid gas (for example five Magnesium sulfate heptahydrates, aluminum trihydrate, magnesium hydroxide, hydrocarbonate of magnesia etc.), at high temperature decomposes, and in thermo-negative reaction, discharges water and/or carbonic acid gas with knock down the flame;
B) formation of charcoal-when in high temperature, charcoal organizer, comprises organophosphate, zn cpds, and nitrogen compound (for example trimeric cyanamide ester and polymeric amide) and metal borate can form charcoal barrier, and inflammable material and fire screen is exhausted;
C) blocking-up of the capture/oxygen of free radical-independent halogen compounds and the compound of antimonous oxide or antimony all burn prevention.Dominant mechanism it is believed that it is above combustion substance, to have formed dense gas blanket, suppresses or has stoped oxygen to approach easy firing material, also thinks on evidence that antimony halides can remove the free radical in flame, thus stopped reaction;
D) inhibitor of the inhibition-cigarette of cigarette is to work by means of the complete oxidation of the carbonaceous material forming in flame and/or the formation of charcoal or glass.They are the catalyzer of oxidizing reaction and/or charcoal or glass-former normally. and typical smoke inhibitor is molybdenum oxide and ferrocene or other metallocenes;
Above-mentioned all fire retardants and/or smoke inhibitor be ripe used in the prior art all, for the macromolecule products such as polyvinyl chloride (PVC) provide flame retardant resistance or low cigarette.Regrettably in the macromolecule product that, the use of these fire retardants and/or smoke inhibitor usually applies it, produce some undesirable character.Such as antimonous oxide and Halogen organic compound are used in conjunction with, antimony has toxicity, and when it is used as fire retardant, the amount of being fuming is large, and the toxic gases such as the N0 containing in the toxic smoke producing in combustion processes, C0 and HCl are directly threatening the mankind's life security in fire.So limited its application in expensive goods or specific environment.
Published european patent application No273458 narrated the halogenide that uses bismuth or antimony with the mixture of amine or the halogenide of bismuth and antimony with the mixture of amine as flame-retardant additive, these mixtures have such structural formula:
R(MeX
3)Y
Wherein:
-R is a kind of amine; be selected from 2-guanidine-benzoglyoxaline, isophorone diamine, Dyhard RU 100, guanamines, melamine, piperazine; these aminated compoundss are available alkyl, aromatic base or an acyl substituted optionally; and the compound that includes 2 to 9 triazine rings, their ring by least one-NH-base condenses or combination each other:
-Me is bismuth or antimony;
-X is chlorine or bromine;
-Y is the number of 0.3 to 4;
According to described patent application, this flame-retardant additive is not having in solvent situation, reactant to be mixed and is heating and close, or heating is synthesized by reactant being placed in solvent or in suspension.The product that obtains is in small, broken bits, and optionally available stearic acid is coated.But above-mentioned additive can only or be distributed in the non-polymer beads of extruding with solution form with the solid (using suitable wetting agent) that ground.When the powder of resulting grinding, cross when thick, use the solid grinding to have and makes it in single polymer beads, the shortcoming of disperseing inhomogeneously.In fact flame-retardant additive is to be mainly distributed on the surface of this particle.While meanwhile, using above-mentioned additive solution, also can relate to relevant some problem of selecting suitable solvent.Although bismuth and antimony belong to congeners, in physicochemical property, there is similarity, bismuth compound is also with the effect that presses down cigarette, and the proportion of bismuth compound is larger 60% than weisspiessglanz, has high bulk density; At PVC goods, add man-hour, bismuth compound particle is difficult to be uniformly dispersed in goods, and therefore, bismuth compound is difficult to improve the flame retardant effect of high molecular products in the application of flame-retardant smoke inhibition.
Summary of the invention
A kind of preparation method for polymer fire-retardant master granule proposed by the invention, its object is intended to solve that bismuth compound particle is difficult to disperse and the flame retardant effect that cannot improve high molecular products.
Technical scheme of the present invention is: a kind of preparation method for polymer fire-retardant master granule, comprises following process program successively:
1) to prepare its particle diameter of nano bismuth oxide D50 be 0.1 μ m-1 μ m to bismuth metal forms by using gasification and oxidation;
2) to prepare its particle diameter of pearl white D50 be 0.5 μ m-15 μ m to bismuth chloride solution water solution;
3) get 99.5 parts of macromolecule mixture weight parts, under 80 ℃ of-180 ℃ of high-temperatures of temperature, cause it and soften, 0.25 part of nano bismuth oxide of weight part and 0.25 part of pearl white are added; Or add separately 0.5 part of nano bismuth oxide; Or add separately 0.5 part of pearl white; Carry out mechanical type stirring, time 10min-240min; The masterbatch mixing is extruded on twin screw extruder; Obtain the bismuth based compound master batch that is uniformly dispersed;
Above-mentioned bismuth metal forms by using gasification and oxidation is prepared nano bismuth oxide and is:
A adds the smart bismuth of content 99.99% in electric arc furnace, by bismuth ingot heat fused, and at temperature 3000-4000 ℃, under pressure 0.6-0.95 atmospheric condition, makes smart bismuth gasification produce bismuth steam;
B bismuth steam sucks and sends into after reactor along high temperature conduit through negative pressure, with send in reactor that air suction inlet is come in freezing air converge, high temperature bismuth steam is absorbed and generates nano level solid oxide bismuth particle by negative pressure oxidation, simultaneously, reactor sucks after freezing air, flue-gas temperature is reduced to 170 ℃ of left and right, cooling through circulating water cooling device, part compared with coarse particles bismuth oxide micro-powder productive set at reactor bottom, through the discharge of accumulated powder relief outlet, send step a back to and repeat gasification generation bismuth steam, the bismuth oxide micro-powder of productive set does not enter cyclone together with flue gas;
C, in cyclone, is carrying the flue gas of bismuth oxide micro-powder secretly through cyclone dust collection, and particle diameter is collected at the bismuth oxide micro-powder of 2-10 μ m, through discharging, then sends step a back to and repeats gasification generation bismuth steam;
The ash-laden gas that d discharges through c step, then gather dust through pulse bagroom, obtaining particle diameter D50 is the nano bismuth oxide of 0.1 μ m-1 μ m.
Above-mentioned bismuth chloride solution water solution is prepared pearl white and is; A, preparation bismuth chloride solution: get density 1.45g/cm
3bismuth chloride stoste, add concentrated hydrochloric acid and the pure water of mass percent concentration 30-32%; The volume ratio of concentrated hydrochloric acid, pure water and bismuth chloride stoste is 1: 8-9: 10-11;
B is synthetic: get and be equivalent to a step and prepare the pure water of bismuth chloride solution body product 5-10 times and add hcl acidifying, obtain hydrochloric 2% acidifying pure water; Be heated to 85-90 ℃, constant temperature; With stirrer, constantly stir acidifying pure water, control stirrer rotating speed 250-450r/min, with the speed of 20-25mL/min, in acidifying pure water, drip the bismuth chloride solution that a step is prepared lentamente; When bismuth to be chlorinated hydrolysis forms chlorine oxygen bismuth nucleus, the rate of addition of controlling bismuth chloride solution is 12mL/min, allows the chlorine oxygen bismuth nucleus slabbing chlorine oxygen bismuth of growing up slowly; Along with sheet chlorine oxygen bismuth quantity is more and more, the rate of addition of bismuth chloride solution also will increase along with adjusting; After prepared bismuth chloride solution all drips, continue to keep the stirrer stirred reaction mixture 0.5-1 hour for constant temperature of 85-90 ℃, then be 2.5-3.5 by the pH value of the analytical pure ammoniacal liquor adjustment reaction mixture of 8-15%, complete synthetic;
C processing granular shape pearl white: by step b, gained reaction mixture filtering separation; In filter, thing is washed 3-5 time with deionized water or pure water rinsing, centrifuge dripping, and sending temperature is that the loft drier of 100-120 ℃ is dried, making D50 is the particulate state pearl white of 0.5 μ m-15 μ m.
Above-mentioned D50 refers to: corresponding particle diameter when the cumulative particle sizes percentile of nano bismuth oxide or pearl white reaches 50%.Its physical significance is that the particle that particle diameter is greater than it accounts for 50%, and the particle that is less than it also accounts for 50%, D50 and is also meso-position radius or median particle diameter.
Fire-retardant master granule of the present invention main component be bismuth, bismuth has asepsis environment-protecting.With bismuth, make fire retardant and can eliminate drawback in Sb system fire retardant.
The production of fire-retardant master granule of the present invention does not need to add dispersion agent and comprises wetting agent, does not need the halogenide preliminary election of bismuth to be dissolved in liquid reaction medium yet.Than published european patent application No273458, having omitted liquid reaction medium will remove gradually in reaction process, make it under normal pressure or decompression under the step of evaporation, but do not affect the realization of flame retardant resistance spy of the present invention and/or cigarette rejection characteristic.Fire-retardant master granule of the present invention is compared with the compound fire-retardant master granule of antimonous oxide or antimony with traditional halogen compounds, through the test of injection moulding in injection moulding machine, using sample size of the present invention is 50mm*6mm*2mm, when addition is 0.5 part, the oxygen index of the macromolecule products such as polyvinyl chloride (PVC) rises to 38.5-42.0 by 29.5, more than rising Liao Jin10Ge unit, the amount of being fuming obviously reduces, flame retarding efficiency increases, and is obviously better than the acquisition polymer oxygen index of european patent application No273458.Under the condition of same flame retarding and smoke suppressing properties, because saving the additive cost that makes macromolecule product that adds of fire-retardant master granule, and bismuth compound fire-retardant master granule has no side effect to human body, is environmentally friendly fire-retardant master granule.Along with people's living standard is improved day by day, also require the more and more Law on Environmental Protection of Gao， developed country and more and more severe to the fire safety rules of high-grade macromolecular material, the restriction application that following fire retardant trend is Sb system fire retardant.This means that bismuth flame retardant has fabulous application prospect, and there is boundless market potential.
Embodiment
Embodiment 1
80 parts of PP, 19.5 parts of chloroprene rubbers, 0.5 part of bismuth oxide, (D
50≈ 300nm), heat is melted under condition at 160 ℃, stirs 2h; The masterbatch mixing is extruded on twin screw extruder;
Then injection moulding test in injection moulding machine, sample size is 50mm*6mm*2mm, obtaining polymer oxygen index is 38.5.
Embodiment 2
79.5 parts of PP, 20 parts of chloroprene rubbers, 0.5 part of pearl white (D
50≈ 1.5 μ m), heat is melted under condition and is stirred 2h at 160 ℃, and the masterbatch mixing is extruded on twin screw extruder;
Then injection moulding test in injection moulding machine, sample size is 50mm*6mm*2mm, obtaining high molecular products oxygen index is 42.0.
Embodiment 3
79 parts of PP, 21 parts of chloroprene rubbers, 0.25 part of bismuth oxide (D
50≈ 500nm), 0.25 part of pearl white (D
50≈ 1 μ m), heat is melted under condition at 160 ℃, stirs 2h; The masterbatch mixing is extruded on twin screw extruder;
Then injection moulding test in injection moulding machine, sample size is 50mm*6mm*2mm, obtaining polymer oxygen index is 41.5.
Claims (1)
1. for a preparation method for polymer fire-retardant master granule, it is characterized in that: comprise successively following technique:
1) to prepare its particle diameter of nano bismuth oxide D50 be 0.1 μ m-1 μ m to bismuth metal forms by using gasification and oxidation;
2) to prepare its particle diameter of pearl white D50 be 0.5 μ m-15 μ m to bismuth chloride solution water solution;
3) get 99.5 parts of macromolecule mixture weight parts, under 80 ℃ of-180 ℃ of high-temperatures of temperature, cause it and soften, 0.25 part of nano bismuth oxide of weight part and 0.25 part of pearl white are added; Or add separately 0.5 part of nano bismuth oxide; Or add separately 0.5 part of pearl white; Carry out mechanical type stirring, time 10min-240min; The masterbatch mixing is extruded on twin screw extruder; Obtain the bismuth based compound master batch that is uniformly dispersed;
Above-mentioned bismuth metal forms by using gasification and oxidation is prepared nano bismuth oxide and is:
A adds the smart bismuth of content 99.99% in electric arc furnace, by bismuth ingot heat fused, and at temperature 3000-4000 ℃, under pressure 0.6-0.95 atmospheric condition, makes smart bismuth gasification produce bismuth steam;
B bismuth steam sucks and sends into after reactor along high temperature conduit through negative pressure, with send in reactor that air suction inlet is come in freezing air converge, high temperature bismuth steam is absorbed and generates nano level solid oxide bismuth particle by negative pressure oxidation, simultaneously, reactor sucks after freezing air, flue-gas temperature is reduced to 170 ℃ of left and right, cooling through circulating water cooling device, part compared with coarse particles bismuth oxide micro-powder productive set at reactor bottom, through the discharge of accumulated powder relief outlet, send step a back to and repeat gasification generation bismuth steam, the bismuth oxide micro-powder of productive set does not enter cyclone together with flue gas;
C, in cyclone, is carrying the flue gas of bismuth oxide micro-powder secretly through cyclone dust collection, and particle diameter is collected at the bismuth oxide micro-powder of 2-10 μ m, through discharging, then sends step a back to and repeats gasification generation bismuth steam;
The ash-laden gas that d discharges through c step, then gather dust through pulse bagroom, obtaining particle diameter D50 is the nano bismuth oxide of 0.1 μ m-1 μ m;
Above-mentioned bismuth chloride solution water solution is prepared pearl white and is; A, preparation bismuth chloride solution: get density 1.45g/cm
3bismuth chloride stoste, add concentrated hydrochloric acid and the pure water of mass percent concentration 30-32%; The volume ratio of concentrated hydrochloric acid, pure water and bismuth chloride stoste is 1: 8-9: 10-11;
B is synthetic: get and be equivalent to a step and prepare the pure water of bismuth chloride solution body product 5-10 times and add hcl acidifying, obtain hydrochloric 2% acidifying pure water; Be heated to 85-90 ℃, constant temperature; With stirrer, constantly stir acidifying pure water, control stirrer rotating speed 250-450r/min, with the speed of 20-25mL/min, in acidifying pure water, drip the bismuth chloride solution that a step is prepared lentamente; When bismuth to be chlorinated hydrolysis forms chlorine oxygen bismuth nucleus, the rate of addition of controlling bismuth chloride solution is 12mL/min, allows the chlorine oxygen bismuth nucleus slabbing chlorine oxygen bismuth of growing up slowly; Along with sheet chlorine oxygen bismuth quantity is more and more, the rate of addition of bismuth chloride solution also will increase along with adjusting; After prepared bismuth chloride solution all drips, continue to keep the stirrer stirred reaction mixture 0.5-1 hour for constant temperature of 85-90 ℃, then be 2.5-3.5 by the pH value of the analytical pure ammoniacal liquor adjustment reaction mixture of 8-15%, complete synthetic;
C processing granular shape pearl white: by step b, gained reaction mixture filtering separation; In filter, thing is washed 3-5 time with deionized water or pure water rinsing, centrifuge dripping, and sending temperature is that the loft drier of 100-120 ℃ is dried, making D50 is the particulate state pearl white of 0.5 μ m-15 μ m.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104310471A (en) * | 2014-11-14 | 2015-01-28 | 山东大学 | Method for compositing bismuth oxychloride pearlescent pigment |
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| CN104310471A (en) * | 2014-11-14 | 2015-01-28 | 山东大学 | Method for compositing bismuth oxychloride pearlescent pigment |
| CN104310471B (en) * | 2014-11-14 | 2016-01-13 | 山东大学 | A kind of method of synthesizing bismuth oxychloride pearlescent pigment |
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Application publication date: 20140219 |