CN103819935A - Method for preparing magnesium hydrate fire retardant through surface modification treatment by using composite wet method - Google Patents
Method for preparing magnesium hydrate fire retardant through surface modification treatment by using composite wet method Download PDFInfo
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Abstract
The invention discloses a method for preparing magnesium hydrate fire retardant through surface modification treatment by using a composite wet method. The method comprises the following steps: firstly, mixing a water solution of a soluble magnesium salt with an alkali water solution according to a chemical stoichiometric ratio so as to obtain a magnesium hydrate precipitate sizing agent, aging or performing hydro-thermal treatment on the obtained magnesium hydrate precipitate sizing agent, controlling the temperature to be 40-180 DEG C, subsequently performing hyperdispersant and fatty acid (or sodium/or sylvite) compounding wet method surface wrapping modification treatment on magnesium hydrate, and finally dehydrating, drying, crushing and grading the wrapped sizing agent. The powder modified by using the method is good in processing property, excellent and remarkable inflaming retarding and smoke inhibition function, and is applicable to situation of different demands. The method is reasonable in process, low in cost, wide in product application field, large in market potential, high in competitiveness and has remarkable economic and social benefits.
Description
Technical field
The invention belongs to surface modification and process the preparing technical field of flame retardant of magnesium hydroxide, especially relate to a kind of compound wet method surface coating modification of hyper-dispersant and lipid acid (or sodium/or sylvite) that adopts and prepare the method for the flame retardant of magnesium hydroxide of favorable dispersity.
Background technology
Along with the continuous expansion of macromolecular material Application Areas, flame-retarded technology also causes people's attention day by day.The fire retardant of at present practical application is various in style, mainly contains the aluminium system, magnesium system, antimony system, molybdenum system of halogen system, organophosphorus system, phosphorus-nitrogen system, silicon-type and mineral-type etc.Owing to having 80% to be choked to death and to die by cigarette in fire, therefore in contemporary fire retardant technology, " press down cigarette " more even more important than " fire-retardant ".Fire retardant developing direction is in the world: (1) is non-halogenated.Mainly to replace a large amount of halogenated flame retardants that use now with inorganic combustion inhibitor.(2) fire retardant super-refinement.Fire retardant particle is thinner, and the impact of the physicals on added material will be less, even can play the effect of enhancing.(3) fire retardant surface treatment.Process inorganic combustion inhibitor by surface chemistry method, to strengthen the avidity of itself and macromolecular material.(4) synergy of research flame-retardant system.Different fire retardants is carried out composite, strengthening in flame retardant effect, reduce the consumption of fire retardant.Therefore, develop efficient, to press down cigarette, low toxicity inorganic combustion inhibitor and will more and more be subject to user's favor.
Due to inorganic combustion inhibitor in synthetic materials apart from outside flame retardant effect, also have the effect of being fuming and hydrogenchloride generates of suppressing, and give material non-toxic, non-corrosiveness, thereby be used widely.Magnesium hydroxide produce, use and discarded process in all unharmful substance discharges, and can also in and the combustion processes acidity and the corrosive gases that produce, be a kind of environment-friendly fire retardant.Magnesium hydroxide heat decomposition temperature is high, exceed 140 ℃ than current conventional inorganic combustion inhibitor aluminium hydroxide, can make the synthetic materials that adds magnesium hydroxide can bear higher processing temperature, be beneficial to and accelerate extrusion molding speed, shorten molding cycle, also contribute to improve flame retarding efficiency simultaneously.
Aspect flame retardant of magnesium hydroxide production, the prostatitis in the world is walked by Japan at present.The at present production of flame retardant of magnesium hydroxide of Japan is still take sea water bittern method as main, especially with the tool popularity of the product of consonance (Kyowa) company (9kt/a) and TMG company (12kt/a).The former has 6 kinds at least under trade name Kisuma, and the latter has two kinds under one's name at Finemag.US and European is later than Japan to the research of flame retardant of magnesium hydroxide, but there is the impetus of catching up from behind, output maximum, flame retardant of magnesium hydroxide producing country that kind is maximum are developed at present, and along with U.S. domestic is in the fundamental research in this field and the applied research expansion that deepens continuously, the production of US and European flame retardant of magnesium hydroxide goods has realized seriation substantially, take Huber company of the U.S. and Albemarle Corporation of the U.S. as representative.Magnesium hydroxide Zemgen10,30 two kinds that Huber company produces are not carry out surface treatment, can in PVC and other thermoplastics, apply, and Zemgen15, the 35th, the magnesium hydroxide after surface treatment dispersing property improves, is applied in various polymkeric substance.Under the refined precious trade name Magnifin producing of the U.S., have 10 kinds at least, comprise 3 of unmodified kinds, and 7 of the kinds of lipid acid, silane coupling agent, special composite modified processing.In general, the good mechanical performance of the magnesium hydroxide of silane coupling agent processing, but silane coupling agent facile hydrolysis are so modification is main mainly with dry method greatly, higher to the requirement of modified device.Dead Sea bromine group of Israel is take high density chlorination magnesium as raw material, adopt Pintsch process-hydrating process to prepare flame retardant of magnesium hydroxide, the built factory that produces ten thousand tons per year, this product purity high (>98%), pattern rule, good dispersity, the feature of this technique is can be continuously, scale operation, weak point is that facility investment is large, process energy consumption is high, and a large amount of hydrochloric acid of by-product also need to find new outlets simultaneously.
When magnesium hydroxide is used as fire retardant, must, through special processing and surface modification, possess specific crystalline form.General requirement: (1) crystalline form is fiber shape, can increase unit elongation and the flexural strength of material like this; (2) purity must be high, and purity is higher, and flame retardant effect is better; (3) particle is the smaller the better, and various aspects of performance comprises that flame retardant effect, smoke elimination and mechanical property are all improved; (4) surface polarity is low, and in material, dispersed and consistency increases, and on material mechanical impact minimizing, so carry out surface treatment with suitable tensio-active agent and consumption, improves the consistency with high molecular polymer.The magnesium hydroxide that only possesses above feature could be compatible better with macromolecular material.As U.S. Pat: 4126593 use polyhydric alcohol fatty acid esters carry out surface modification to magnesium hydroxide, add in fluoropolymer resin, and its mobility shock strength is significantly increased, and moldability, apparent property, self-gravitation all improve a lot; U.S. Pat: 6011086 use sorbitan ester modified magnesium hydroxide, add in polymer materials, and its mechanical property, processing characteristics, flame retardant properties are all improved; It is surface-modifying agent that Chinese patent CN1541943A adopts saturated fatty acid sodium-salt, sylvite or amine salt, and the magnesium hydroxide products good dispersity of preparation, has higher processing temperature, and is used as the fire retardant of the products such as plastics, rubber, building materials.
Summary of the invention
In general, selecting all kinds of saturated or unsaturated fatty acidss to carry out modification to magnesium hydroxide is effectively, has soft aliphatic long-chain because cover the organic acid on magnesium hydroxide surface, can be on organic base-material molecule bending winding, strengthen bonding force, play certain effect to improving consistency.But because organic acid only has unit molecule long-chain, its geometry and sterically hindered congenital defect, and the bonding force with carboxyl strong not, always make this type of modified product occur that in application process coating layer easily comes off, base-material dispersion force is not or because increasing consumption, the shortcoming that Mechanical Properties of Products declines, makes it to serve as common fillers and uses to reduce goods cost, and can not carry out as functional filler the overall performance of strongthener.
The object of the invention is: for the existing magnesium hydroxide preparation technology of China problem that particularly process for modifying surface exists, providing a kind of adopts the compound wet-process modified processing of hyper-dispersant and lipid acid (or sodium salt/or sylvite) to prepare the method for high-dispersion magnesium hydroxide combustion inhibitor, give full play to the synergistic effect between the properties-correcting agent of different functional groups, can be coated on more firmly the surface of magnesium hydroxide by the interaction between functional group, the flame retardant of magnesium hydroxide of processing through this method has good dispersing property, add to and in application system, there is good reinforcing function, can effectively improve mechanical property and the heat-resistant stability of material.
Technical scheme of the present invention is: the method for flame retardant of magnesium hydroxide is prepared in a kind of compound surface modification processing, in turn includes the following steps:
(1) by the aqueous solution and the alkaline aqueous solution of stoichiometric ratio mixing solubility magnesium salts, obtain magnesium hydrate precipitate slurry; The inventive method start from the magnesium salts that amount of substance concentration is 0.5-4mol/L, as magnesium chloride, magnesium sulfate, magnesium acetate, magnesium nitrate etc., or their combination, then adding amount of substance concentration by control is the control to pH value with maintenance as sodium hydroxide, potassium hydroxide, calcium hydroxide or ammoniacal liquor of 0.5-4mol/L basic solution, generates thus the precipitation of magnesium hydroxide;
(2) the magnesium hydrate precipitate slurry of slaking or the above-mentioned gained of hydrothermal treatment consists, controls temperature at 40-180 ℃, and this phases-time is 30-120min;
(3) compound surface modification is processed the above-mentioned magnesium hydroxide slurry through overcuring or hydrothermal treatment consists gained; Select a kind of or more than one mixtures in the longer chain fatty acids such as Palmiticacid, stearic acid, oleic acid, palmitinic acid, linolic acid, lauric acid as coating, require the wherein fatty acid content of carbonatoms between 18-20 to be greater than 50%, in sodium hydroxide hydrothermal solution, add above-mentioned lipid acid, sodium hydroxide concentration accounts for the 5-15% of lipid acid, control temperature at 60-80 ℃, reaction times is 10-30min, forms the saponification coating liquid of 1-10%; If use sodium salt or the sylvite of above-mentioned lipid acid, do not need saponification, directly sodium salt or sylvite are dissolved in 60-80 ℃ of hot water and obtain saponification liquor; In above-mentioned saponification liquor, add hyper-dispersant, this type of hyper-dispersant contains the multiple functional group such as hydroxyl, carboxyl, can be anchored at by functional group the surface of magnesium hydroxide;
(4) under strong stirring condition, heat magnesium hydroxide slurry, control temperature at 60-90 ℃, the reaction times is 30-90min.After reaction, slurries filtration is dried, finally forms the magnesium hydrate powder of compound surface processing.
Described magnesium salt solution is soluble magnesium salt compound, is selected from magnesium chloride, magnesium sulfate, magnesium acetate, magnesium nitrate etc., or the combination of above-claimed cpd.
The amount of substance concentration of described magnesium salts is 0.5-4mol/L, and preferred concentration is 1.0-2.0mol/L.
The alkali of described basic solution is selected from sodium hydroxide, potassium hydroxide, calcium hydroxide or ammonia soln.
The amount of substance concentration of described basic solution is 0.5-4mol/L, and preferred concentration is 1.0-2.0mol/L; Basic solution during reaction keeps pH to be not less than 8.5.
Slaking or hydrothermal treatment consists time are 30-120min, and preferably the time is 60min, control temperature at 40-180 ℃.
Selected high-quality, longer chain fatty acid, carbonatoms is at C14 between C22, and wherein C18-C20 content is greater than 50%, or the sodium salt of above-mentioned lipid acid or sylvite.
Selected lipid acid is that a kind of or more than one mixtures in the longer chain fatty acids such as Palmiticacid, stearic acid, oleic acid, palmitinic acid, linolic acid, lauric acid are as coating; The ratio that the lipid acid consumption using accounts for butt magnesium hydroxide quality is 0.1-10%, is preferably 0.5-6%, more preferably 1-4%.
Described hyper-dispersant is mainly made up of anchoring section and solvent chain, and anchoring section mainly contains the polar group of the multiple functional group such as hydroxyl, carboxyl, and solvent chain is mainly nonpolar long-chain fat carbochain, and molecular weight is between 3000-10000.
The ratio that the hyper-dispersant consumption using accounts for butt magnesium hydroxide quality is 0.1-10%, is preferably 0.5-6%, more preferably 1-4%.
Beneficial effect of the present invention: the super fine magnesium hydroxide flaky powder median size of making through scheme of the present invention is 0.8-1.3 μ m, and purity is up to 99.5%, and favorable dispersity.The SEM photo of this product of meaning as shown in Figure 2, super fine magnesium hydroxide particle structure in the form of sheets; The size distribution figure (being recorded by MALVERN MASTERSIZER 2000) of this product of meaning, can find out: the particle diameter of ultrafine magnesium hydroxide powder body concentrates on 0.8-1.3 μ m as shown in Figure 3; Can find out from attached X-ray diffractogram illustrated in Figure 4 (XRD): this spectrogram and magnesium hydroxide standard spectrogram JCPDS7-239 are in full accord, do not occur impurity peaks, main peak is sharp-pointed, illustrates that product purity is very high, crystal formation is hexagonal system structure, and crystallization is complete.
The remarkable advantages such as compared with current some surface treatment methods, the present invention has raw material and is easy to get, and processing requirement is simple, and production process is easy to control, and product good dispersion property, manufacturing cost are low.Through this method powder that modification obtains good dispersity in resin, processing characteristics is good, show significantly fire-retardant, press down the function of cigarette, the occasion needing applicable to difference, such as PVC, EVA isoelectric line cable, the polyolefin resines such as PP, PE, rubber, the fields such as engineering plastics.Technique of the present invention is reasonable, with low cost, and product applications is extensive, and market potential is large, and competitive power is strong, has significant economic and social benefit, and advanced technology has significant progress.
Accompanying drawing explanation
Fig. 1 is the process flow diagram that the present invention obtains magnesium hydrate powder method.
Fig. 2 is the microscopic appearance SEM photo of the magnesium hydroxide of present method gained.
Fig. 3 is the size distribution figure of the magnesium hydroxide of present method gained.
Fig. 4 is the X-ray powder diffraction pattern of the magnesium hydroxide that obtains of the present invention.
Embodiment
As shown in Figure 1, the method for favorable dispersity flame retardant of magnesium hydroxide is prepared in a kind of compound surface modification processing, in turn includes the following steps in reference:
(1) by the aqueous solution and the alkaline aqueous solution of stoichiometric ratio mixing solubility magnesium salts, obtain magnesium hydrate precipitate slurry; The inventive method start from the magnesium salts that amount of substance concentration is 0.5-4mol/L, as magnesium chloride, magnesium sulfate, magnesium acetate, magnesium nitrate etc., or their combination, then adding amount of substance concentration by control is the control to pH value with maintenance as sodium hydroxide, potassium hydroxide, calcium hydroxide or ammoniacal liquor of 0.5-4mol/L basic solution, generates thus the precipitation of magnesium hydroxide;
(2) the magnesium hydrate precipitate slurry of slaking or the above-mentioned gained of hydrothermal treatment consists, controls temperature at 40-180 ℃, and this phases-time is 30-120min;
(3) compound surface modification is processed the above-mentioned magnesium hydroxide slurry through overcuring or hydrothermal treatment consists gained; Select a kind of or more than one mixtures in the longer chain fatty acids such as Palmiticacid, stearic acid, oleic acid, palmitinic acid, linolic acid, lauric acid as coating, require the wherein fatty acid content of carbonatoms between 18-20 to be greater than 50%, in sodium hydroxide hydrothermal solution, add above-mentioned lipid acid, sodium hydroxide concentration accounts for the 5-15% of lipid acid, control temperature at 60-80 ℃, reaction times is 10-30min, forms the saponification coating liquid of 1-10%; If use sodium salt or the sylvite of above-mentioned lipid acid, do not need saponification, directly sodium salt or sylvite are dissolved in 60-80 ℃ of hot water and obtain saponification liquor; In above-mentioned saponification liquor, add hyper-dispersant, this type of hyper-dispersant contains the multiple functional group such as hydroxyl, carboxyl, can be anchored at by functional group the surface of magnesium hydroxide;
(4) under strong stirring condition, heat magnesium hydroxide slurry, control temperature at 60-90 ℃, the reaction times is 30-90min.After reaction, slurries filtration is dried, finally forms the magnesium hydrate powder of compound surface processing.
Described magnesium salt solution is soluble magnesium salt compound, is selected from magnesium chloride, magnesium sulfate, magnesium acetate, magnesium nitrate etc., or the combination of above-claimed cpd.
The amount of substance concentration of described magnesium salts is 0.5-4mol/L, and preferred concentration is 1.0-2.0mol/L.
The alkali of described basic solution is selected from sodium hydroxide, potassium hydroxide, calcium hydroxide or ammonia soln.
The amount of substance concentration of described basic solution is 0.5-4mol/L, and preferred concentration is 1.0-2.0mol/L; It is 8.5 or larger pH value that basic solution during reaction keeps pH value.
Slaking or hydrothermal treatment consists time are 30-120min, and preferably the time is 60min, control temperature at 40-180 ℃.
Selected high-quality, longer chain fatty acid, carbonatoms is at C14 between C22, and wherein C18-C20 content is greater than 50%, or the sodium salt of above-mentioned lipid acid or sylvite.
Selected lipid acid is that a kind of or more than one mixtures in the longer chain fatty acids such as Palmiticacid, stearic acid, oleic acid, palmitinic acid, linolic acid, lauric acid are as coating; The ratio that the lipid acid consumption using accounts for butt magnesium hydroxide quality is 0.1-10%, is preferably 0.5-6%, more preferably 1-4%.
Described hyper-dispersant is mainly made up of anchoring section and solvent chain, and anchoring section mainly contains the polar group of the multiple functional group such as hydroxyl, carboxyl, and solvent chain is mainly nonpolar long-chain fat carbochain, and molecular weight is between 3000-10000.
The ratio that the hyper-dispersant consumption using accounts for butt magnesium hydroxide quality is 0.1-10%, is preferably 0.5-6%, more preferably 1-4%.
The super fine magnesium hydroxide flaky powder median size of making through scheme of the present invention is 0.8-1.3 μ m, and purity is up to 99.5%, and favorable dispersity.The SEM photo of this product of meaning as shown in Figure 2, super fine magnesium hydroxide particle structure in the form of sheets; The size distribution figure (being recorded by MALVERN MASTERSIZER 2000) of this product of meaning, can find out: the particle diameter of ultrafine magnesium hydroxide powder body concentrates on 0.8-1.3 μ m as shown in Figure 3; Can find out from attached X-ray diffractogram illustrated in Figure 4 (XRD): this spectrogram and magnesium hydroxide standard spectrogram JCPDS7-239 are in full accord, do not occur impurity peaks, main peak is sharp-pointed, illustrates that product purity is very high, crystal formation is hexagonal system structure, and crystallization is complete.
Can further illustrate content of the present invention with example below, only illustrate and embody processing method of the present invention for being used for, rather than limiting the scope of the invention and application places.To those skilled in the art, obviously when using distinct device and common available raw material to implement time of the present invention, can introduce new modification, still such modification can not be thought and exceeded by the determined scope of the present invention of claims.
Embodiment 1:
Taking a certain amount of hydrated magnesium chloride is dissolved in distilled water, amount of substance concentration is controlled at 1.0mol/L, takes a certain amount of sodium hydroxide and is dissolved in distilled water, and amount of substance concentration is controlled at 1.0mol/L, under the effect of strong stirring, alkaline solution is joined in magnesium chloride solution, and pH value is controlled at 10.0, obtains magnesium hydrate precipitate, heating slurry to 60 ℃, keep 60min, obtain the slurry that slaking is good, continue heating slurry to 75 ℃ modification to be covered.Meanwhile take the relative butt magnesium hydroxide of 3.5%(, lower with) lipid acid and 10% sodium hydroxide (with respect to the amount of lipid acid, lower with), saponification 10min at 80 ℃, form 5% saponification liquor, add 1.5% hyper-dispersant (based on butt magnesium hydroxide, lower same) simultaneously.The saponification liquor preparing is added in slurry to whip modified 60min.Then filter, wash, be dried, crushing and classification, obtain surface-treated magnesium hydrate powder.
Embodiment 2:
Taking a certain amount of hydrated magnesium chloride is dissolved in distilled water, amount of substance concentration is controlled at 1.0mol/L, takes a certain amount of sodium hydroxide and is dissolved in distilled water, and amount of substance concentration is controlled at 1.0mol/L, under the effect of strong stirring, alkaline solution is joined in magnesium chloride solution, and pH value is controlled at 10.0, obtains magnesium hydrate precipitate, heating slurry to 60 ℃, keep 60min, obtain the slurry that slaking is good, continue heating slurry to 75 ℃ modification to be covered.Meanwhile take 3.5% lipid acid and 10% sodium hydroxide, saponification 10min at 80 ℃, forms 5% saponification liquor, adds 2.5% hyper-dispersant simultaneously.The saponification liquor preparing is added in slurry to whip modified 60min.Then filter, wash, be dried, crushing and classification, obtain surface-treated magnesium hydrate powder.
Embodiment 3:
Taking a certain amount of hydrated magnesium chloride is dissolved in distilled water, amount of substance concentration is controlled at 2.0mol/L, takes a certain amount of sodium hydroxide and is dissolved in distilled water, and amount of substance concentration is controlled at 2.0mol/L, under the effect of strong stirring, alkaline solution is joined in magnesium chloride solution, and pH value is controlled at 10.5, obtains magnesium hydrate precipitate, heating slurry to 60 ℃, keep 60min, obtain the slurry that slaking is good, continue heating slurry to 80 ℃ modification to be covered.Meanwhile take 4.0% lipid acid and 15% sodium hydroxide, saponification 10min at 80 ℃, forms 10% saponification liquor, adds 2.0% hyper-dispersant simultaneously.The saponification liquor preparing is added in slurry to whip modified 60min.Then filter, wash, be dried, crushing and classification, obtain surface-treated magnesium hydrate powder.
Embodiment 4:
Taking a certain amount of hydrated magnesium chloride is dissolved in distilled water, amount of substance concentration is controlled at 2.0mol/L, takes a certain amount of sodium hydroxide and is dissolved in distilled water, and amount of substance concentration is controlled at 2.0mol/L, under the effect of strong stirring, alkaline solution is joined in magnesium chloride solution, and pH value is controlled at 10.5, obtains magnesium hydrate precipitate, heating slurry to 60 ℃, keep 60min, obtain the slurry that slaking is good, continue heating slurry to 80 ℃ modification to be covered.Meanwhile take 3.0% lipid acid and 15% sodium hydroxide, saponification 10min at 80 ℃, forms 10% saponification liquor, adds 3.0% hyper-dispersant simultaneously.The saponification liquor preparing is added in slurry to whip modified 60min.Then filter, wash, be dried, crushing and classification, obtain surface-treated magnesium hydrate powder.
Embodiment 5:
Taking a certain amount of hydrated magnesium chloride is dissolved in distilled water, amount of substance concentration is controlled at 2.0mol/L, takes a certain amount of sodium hydroxide and is dissolved in distilled water, and amount of substance concentration is controlled at 2.0mol/L, under the effect of strong stirring, alkaline solution is joined in magnesium chloride solution, and pH value is controlled at 10.5, obtains magnesium hydrate precipitate, heating slurry to 60 ℃, keep 60min, obtain the slurry that slaking is good, continue heating slurry to 80 ℃ modification to be covered.Meanwhile take 2.0% lipid acid and 15% sodium hydroxide, saponification 10min at 80 ℃, forms 10% saponification liquor, adds 4.0% hyper-dispersant simultaneously.The saponification liquor preparing is added in slurry to whip modified 60min.Then filter, wash, be dried, crushing and classification, obtain surface-treated magnesium hydrate powder.
Embodiment 6:
Taking a certain amount of hydrated magnesium chloride is dissolved in distilled water, amount of substance concentration is controlled at 1.0mol/L, taking a certain amount of sodium hydroxide is dissolved in distilled water, amount of substance concentration is controlled at 1.0mol/L, under the effect of strong stirring, alkaline solution is joined in magnesium chloride solution, pH value is controlled at 10.0, obtain magnesium hydrate precipitate, slurry is transferred in autoclave, be airtightly heated to 150 ℃, keep 120min, obtain the slurry that hydrothermal treatment consists is crossed, cooling pressure release slurry to 80 ℃ modification to be covered.Meanwhile take 1.5% lipid acid and 10% sodium hydroxide, saponification 10min at 80 ℃, forms 5% saponification liquor, adds 1.5% hyper-dispersant simultaneously.The saponification liquor preparing is added in slurry to whip modified 60min.Then filter, wash, be dried, crushing and classification, obtain surface-treated magnesium hydrate powder.
Embodiment 7:
Taking a certain amount of hydrated magnesium chloride is dissolved in distilled water, amount of substance concentration is controlled at 1.0mol/L, taking a certain amount of sodium hydroxide is dissolved in distilled water, amount of substance concentration is controlled at 1.0mol/L, under the effect of strong stirring, alkaline solution is joined in magnesium chloride solution, pH value is controlled at 10.0, obtain magnesium hydrate precipitate, slurry is transferred in autoclave, be airtightly heated to 180 ℃, keep 60min, obtain the slurry that hydrothermal treatment consists is crossed, cooling pressure release slurry to 80 ℃ modification to be covered.Meanwhile take 2.0% lipid acid and 10% sodium hydroxide, saponification 10min at 80 ℃, forms 5% saponification liquor, adds 1.0% hyper-dispersant simultaneously.The saponification liquor preparing is added in slurry to whip modified 60min.Then filter, wash, be dried, crushing and classification, obtain surface-treated magnesium hydrate powder.
Embodiment 8:
Taking a certain amount of hydrated magnesium chloride is dissolved in distilled water, amount of substance concentration is controlled at 1.0mol/L, taking a certain amount of sodium hydroxide is dissolved in distilled water, amount of substance concentration is controlled at 1.0mol/L, under the effect of strong stirring, alkaline solution is joined in magnesium chloride solution, pH value is controlled at 10.0, obtain magnesium hydrate precipitate, slurry is transferred in autoclave, be airtightly heated to 180 ℃, keep 120min, obtain the slurry that hydrothermal treatment consists is crossed, cooling pressure release slurry to 80 ℃ modification to be covered.Meanwhile take 1.0% lipid acid and 10% sodium hydroxide, saponification 10min at 80 ℃, forms 5% saponification liquor, adds 2.0% hyper-dispersant simultaneously.The saponification liquor preparing is added in slurry to whip modified 60min.Then filter, wash, be dried, crushing and classification, obtain surface-treated magnesium hydrate powder.
Compared with more current surface treatment methods, the present invention has raw material and is easy to get, and processing requirement is simple, production process is easy to control, and the remarkable advantage such as product good dispersion property, manufacturing cost are low can be used for PVC, EVA isoelectric line cable, the polyolefin resin such as PP, PE, rubber, the fields such as engineering plastics.
Claims (10)
1. a method for flame retardant of magnesium hydroxide is prepared in compound surface modification processing, it is characterized in that: in turn include the following steps:
(1) by the aqueous solution and the alkaline aqueous solution of stoichiometric ratio mixing solubility magnesium salts, obtain magnesium hydrate precipitate slurry; The inventive method start from the magnesium salts that amount of substance concentration is 0.5-4mol/L, as magnesium chloride, magnesium sulfate, magnesium acetate, magnesium nitrate etc., or their combination, then adding amount of substance concentration by control is the control to pH value with maintenance as sodium hydroxide, potassium hydroxide, calcium hydroxide or ammoniacal liquor of 0.5-4mol/L basic solution, generates thus the precipitation of magnesium hydroxide;
(2) the magnesium hydrate precipitate slurry of slaking or the above-mentioned gained of hydrothermal treatment consists, controls temperature at 40-180 ℃, and this phases-time is 30-120min;
(3) compound surface modification is processed the above-mentioned magnesium hydroxide slurry through overcuring or hydrothermal treatment consists gained; Select a kind of or more than one mixtures in the longer chain fatty acids such as Palmiticacid, stearic acid, oleic acid, palmitinic acid, linolic acid, lauric acid as coating, require the wherein fatty acid content of carbonatoms between 18-20 to be greater than 50%, in sodium hydroxide hydrothermal solution, add above-mentioned lipid acid, sodium hydroxide concentration accounts for the 5-15% of lipid acid, control temperature at 60-80 ℃, reaction times is 10-30min, forms the saponification coating liquid of 1-10%; If use sodium salt or the sylvite of above-mentioned lipid acid, do not need saponification, directly sodium salt or sylvite are dissolved in 60-80 ℃ of hot water and obtain saponification liquor; In above-mentioned saponification liquor, add hyper-dispersant, this type of hyper-dispersant contains the multiple functional group such as hydroxyl, carboxyl, is anchored at the surface of magnesium hydroxide by functional group;
(4) under strong stirring condition, heat magnesium hydroxide slurry, control temperature at 60-90 ℃, the reaction times is 30-90min;
After reaction, slurries filtration is dried, finally forms the magnesium hydrate powder of compound surface processing.
2. the method for flame retardant of magnesium hydroxide is prepared in compound surface modification processing according to claim 1, it is characterized in that: described magnesium salt solution is soluble magnesium salt compound, be selected from magnesium chloride, magnesium sulfate, magnesium acetate, magnesium nitrate etc., or the combination of above-claimed cpd.
3. the method for flame retardant of magnesium hydroxide is prepared in compound surface modification processing according to claim 2, it is characterized in that: the amount of substance concentration of described magnesium salts is 0.5-4mol/L, and preferred concentration is 1.0-2.0mol/L.
4. the method for flame retardant of magnesium hydroxide is prepared in compound surface modification processing according to claim 1, it is characterized in that: the alkali of described basic solution is selected from sodium hydroxide, potassium hydroxide, calcium hydroxide or ammonia soln.
5. the method for flame retardant of magnesium hydroxide is prepared in compound surface modification processing according to claim 4, it is characterized in that: the amount of substance concentration of described basic solution is 0.5-4mol/L, and preferred concentration is 1.0-2.0mol/L; Basic solution during reaction keeps pH to be not less than 8.5.
6. the method for flame retardant of magnesium hydroxide is prepared in compound surface modification processing according to claim 1, it is characterized in that: slaking or hydrothermal treatment consists time are 30-120min, and preferably the time is 60min, controls temperature at 40-180 ℃.
7. the method for flame retardant of magnesium hydroxide is prepared in compound surface modification processing according to claim 1, it is characterized in that: selected high-quality, longer chain fatty acid, carbonatoms is at C14 between C22, and wherein C18-C20 content is greater than 50%, or the sodium salt of above-mentioned lipid acid or sylvite.
8. the method for flame retardant of magnesium hydroxide is prepared in compound surface modification processing according to claim 1, it is characterized in that: selected lipid acid is that a kind of or more than one mixtures in the longer chain fatty acids such as Palmiticacid, stearic acid, oleic acid, palmitinic acid, linolic acid, lauric acid are as coating; The ratio that the lipid acid consumption using accounts for butt magnesium hydroxide quality is 0.1-10%, is preferably 0.5-6%, more preferably 1-4%.
9. the method for flame retardant of magnesium hydroxide is prepared in compound surface modification processing according to claim 1, it is characterized in that: described hyper-dispersant is mainly made up of anchoring section and solvent chain, anchoring section mainly contains the polar group of the multiple functional group such as hydroxyl, carboxyl, solvent chain is mainly nonpolar long-chain fat carbochain, and molecular weight is between 3000-10000.
10. prepare the method for flame retardant of magnesium hydroxide according to the compound surface modification processing described in claim 1 or 9, it is characterized in that: the ratio that the hyper-dispersant consumption using accounts for butt magnesium hydroxide quality is 0.1-10%, be preferably 0.5-6%, more preferably 1-4%.
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Cited By (8)
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| CN105017793A (en) * | 2015-07-11 | 2015-11-04 | 新疆大学 | Synthesis and preparation method for hydrophobic flame retardant material |
| CN108440995A (en) * | 2018-01-15 | 2018-08-24 | 大连亚泰科技新材料股份有限公司 | A kind of method that wet method prepares modified micro-nano flame retardant of magnesium hydroxide |
| CN108587239A (en) * | 2018-04-10 | 2018-09-28 | 青海民族大学 | A kind of preparation method of modified magnesium hydroxide |
| CN109054450A (en) * | 2018-06-11 | 2018-12-21 | 洛阳中超新材料股份有限公司 | Surface modified magnesium hydroxide and its preparation method and application |
| CN111793248A (en) * | 2020-07-22 | 2020-10-20 | 江西广源化工有限责任公司 | Talcum powder-magnesium hydroxide composite inorganic flame-retardant filler and preparation method thereof |
| CN112724465A (en) * | 2020-12-29 | 2021-04-30 | 宁波艾克姆新材料有限公司 | Flame-retardant silane crosslinked nano modified polyolefin pre-dispersed master batch auxiliary |
| CN113402775A (en) * | 2021-06-21 | 2021-09-17 | 湖南娄底华星锑业有限公司 | Antimony-based composite flame retardant and preparation method thereof |
| CN113789185A (en) * | 2021-10-14 | 2021-12-14 | 华北理工大学 | Preparation method of coal spontaneous combustion inhibitor based on magnesium ion compound |
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| CN112724465A (en) * | 2020-12-29 | 2021-04-30 | 宁波艾克姆新材料有限公司 | Flame-retardant silane crosslinked nano modified polyolefin pre-dispersed master batch auxiliary |
| CN113402775A (en) * | 2021-06-21 | 2021-09-17 | 湖南娄底华星锑业有限公司 | Antimony-based composite flame retardant and preparation method thereof |
| CN113402775B (en) * | 2021-06-21 | 2022-05-20 | 湖南娄底华星锑业有限公司 | Antimony-based composite flame retardant and preparation method thereof |
| CN113789185A (en) * | 2021-10-14 | 2021-12-14 | 华北理工大学 | Preparation method of coal spontaneous combustion inhibitor based on magnesium ion compound |
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