CN102502680A - Method for preparing sub-micron zinc borate by using glycerol - Google Patents
Method for preparing sub-micron zinc borate by using glycerol Download PDFInfo
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- CN102502680A CN102502680A CN2011103100313A CN201110310031A CN102502680A CN 102502680 A CN102502680 A CN 102502680A CN 2011103100313 A CN2011103100313 A CN 2011103100313A CN 201110310031 A CN201110310031 A CN 201110310031A CN 102502680 A CN102502680 A CN 102502680A
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Abstract
The invention relates to a method for preparing sub-micron zinc borate by using glycerol and water, comprising the following steps: (1) preparing the mixed solution of glycerol and water; (2) adding boric acid and zinc oxide into the mixed solution of glycerol and water, and mixing uniformly; (3) adding seed crystal, stirring and refluxing; and (4) filtering or centrifugally settling the reaction product obtained in the step (3) while the reaction product is hot, washing by using the solution of glycerol and water, filtering or centrifugally settling, and drying to obtain the sub-micron zinc borate powder. The zinc borate prepared by adopting the method can be the sub-micron zinc borate with the grain size of less than 1 micron along with the difference of reaction temperature and material ratio, and the zinc borate with the grain size of less than 500 microns can be obtained under the optimum condition. A variety of xZnO.yB2O3.zH2O products can be obtained by adopting the glycerol and the water by adjusting the material ratio, the liquid-solid ratio and the optimum reaction temperature. The zinc borate has a wide range of application.
Description
Technical field
The present invention relates to a kind of preparation method of zinc borate, be specifically related to a kind of method of utilizing USP Kosher to prepare the submicron order zinc borate.
Background technology
The earliest from mid-term in 20th century; Zinc borate just begins widespread use in industry; Can be used as nontoxic, free of contamination fire retardant, lubrication oil antiwear antifriction inorganic additives, high-strength ceramic fusing assistant such as it; Also can be applicable in timber, the paper, make said timber, paper mildew-resistant, anticorrosion, mothproof, can also be used for the aspects such as flame-retardant additive of medicine, waterproof fabric, ceramic glaze, coating mould inhibitor, sterilant, rust-inhibiting paint, polymkeric substance.Zinc borate can be fire-retardant; Can suppress cigarette again; Promote the formation of carbon distribution, can eliminate electric arc, also be widely used in aspects such as various fibers, resin, rubber item, electrical apparatus insulation material, electronic products shell, auto parts wall material, electric wire, cable, anti-flaming dope fire-retardant, press down cigarette.
Developed more than 20 kind of zinc borate at present, they are general molecular formula xZnOyB all
2O
3ZH
2O, just zinc/boron is than different.Wherein comparatively commonly below several kinds: (1) Firebrake 415 (also being heat-resisting zinc borate), its dehydration temperature is 413 ℃, thereby can be used for the high engineering plastics of processing temperature, like polyetherketone, polysulfones and polyetherimide; (2) high temperature level zinc borate (ZB-33), the temperature of its dehydration 1% is 250 ℃, thereby can be used for the various engineering plastics, and can in soft, semi-rigid and filler PVC and plastisol, replace Sb
2O
3(3) anhydrous zinc borate, molecular formula are 2ZnO3B
2O
3But, this fire retardant heatproof to 600 ℃, particularly the heat release rate is low, and it can be used as the high superpolymer of a series of processing temperatures (like polyetherketone, polysulfones, nylon, fluorine-containing polymer etc.) excellent fire retardant agent and presses down fumicants; (4) high hydrate zinc borate, its water-content reach 30% (the Firebrake ZB moisture 14% of standard), and it has higher water-content and extremely low dehydration temperature (100 ℃), is specially adapted to the expanded polystyrene veneer coating, in the soft bubble of PU with high hydrate zinc borate instead of part Sb
2O
3, the material smoke density can descend 30%, and can promote the generation of charcoal layer; (5) most popular zinc borate is 2ZnO3B in the industry
2O
33.5H
2O or 2ZnO3B
2O
37H
2O, its feature is except that having flame retardant properties, also has smoke elimination concurrently; Extinguish arcs; Functions such as insect protected are used for rubber item, adhesive tape, sebific duct, coating, canvas, Glass Steel Tile, electric wire, electric elements, rust proof paint etc. at home successively, and market outlet is very wide.
In the prior art; The preparation method that zinc borate is commonly used mainly contains following 3 kinds: with zinc hydroxide and boric acid is the synthetic zinc borate of raw material; With zinc salt, borax or zinc salt, borax and zinc oxide is the synthetic zinc borate of raw material, is the synthetic zinc borate of raw material with zinc oxide and boric acid.
(1) be the synthetic zinc borate of raw material with zinc hydroxide and boric acid, its reaction formula is as follows:
aZn(OH)
2+bH
3BO
3→aZnO·(b/2)B
2O
3·cH
2O+(2a-c)H
2O
CN 101486469A discloses a kind of a kind of preparation of superfine low hydration zinc borate that discloses, and zinc salt is dissolved in the vaal water, and heating is dissolved it fully, the solution of preparation 0.5～2.5mol/L; Mineral alkali is dissolved in the vaal water alkaline solution of preparation 3.0～8.0mol/L; Will before described two kinds of solution mix, under 20 ℃～80 ℃ constant temperatures, stirred 20～60 minutes fast, acquisition contains the turbid liquid of ultra-fine zinc hydroxide; In said zinc hydroxide suspension liquid, add vaal water, the zinc hydroxide solid content is adjusted to 0.1～5mol/L; Extraordinarily go into boric acid by 1～6 of zinc hydroxide molar weight; Add 0.1%～0.5% non-ionics simultaneously; Under 20 ℃～80 ℃ constant temperatures, stirred 20～60 minutes fast, centrifugal results deposition promptly gets superfine low hydration zinc borate with 2～4 after drying of vaal water washing.
This preparing method's advantage is that product is single, the no three wastes, and the utilization ratio of boric acid is very high.But its required zinc hydroxide must be used the zinc salt on-site prepn, and therefore preparation is inconvenient, and inevitably produces by product and waste water.Domestic Dandong chemical industry synthesized the low hydration zinc borate of 3.5 water with this method.But because the limitation of this method, the follow-up study of relevant this method is rare.
(2) be the synthetic zinc borate of raw material with zinc salt, borax or zinc salt, borax and zinc oxide, its reaction formula is as follows:
aZnSO
4+aNa
2B
4O+bZnO+cH
2O→(a+b)ZnO·aB
2O
3·dH
2O+aNa
2SO
4+(c-d)H
2O
With zinc salt, borax is that raw material is the patented process of U.S.'s borax and chemical company.CN 101186308B discloses a kind of preparation method of nano level zinc borate; Said method comprises borax solution, boric acid aqueous solution and the zinc sulfate solution of preparing 0.5～2.0mol/L respectively, and above-mentioned three kinds of solution at 0～60 ℃ of constant temperature, were stirred 5～60 minutes with 500～3000 rev/mins mechanical stirring speed; Separate the zinc borate throw out; More than 3 times clear water washing zinc borate throw out, and, promptly get the nano level zinc borate with its vacuum-drying.
The cost of material of this method is low, but in reaction process, generates two kinds of by products, and postprocessing working procedures is complicated.And this method requires relatively harsher to reaction conditions, only under the condition of strictness control, can obtain qualified product.Borax, zinc salt and zinc oxide method are actually a kind of improvement of borax, zincate process, and the purpose that adds zinc oxide is to improve the utilization ratio of borax, has reduced the separating step of boric acid, has reduced cost.
(3) be the synthetic zinc borate of raw material with zinc oxide and boric acid, its chemical formula is as follows:
aZnO+bH
3BO
3→aZnO·(b/2)B
2O
3·cH
2O+[(3b-2c)/2]H
2O
Appear in the newspapers the end of the seventies in last century abroad with the synthetic zinc borate of this method, domestic then is about the nineties in last century, to begin to research and develop and achieve success.For example, He Qiong etc. disclose a kind of with zinc oxide and boric acid be raw material synthesizing submicron low-hydrate zinc borate method (He Qiong etc., the dissolvent thermal modification legal system is equipped with the submicron order low-hydrate zinc borate; Inorganic chemicals industry; The 38th the 4th phase of volume, in April, 2006), it adds 10g ZnO and 216mL redistilled water in three-necked flask; Fully stir, add 54g H then in batches
3BO
3, 70 ℃ of isothermal reaction 6h cross and to filter filter cake, wash the gained filter cake successively 3 times with redistilled water and absolute ethyl alcohol, 105 ℃ dry head product.Take by weighing this head product of 20g in autoclave, add absolute ethyl alcohol, coefficient 0.80 is tightened post-heating to 120 ℃ constant temperature 10h with kettle cover.Taking-up naturally cools to room temperature, filters, and filter cake washs 3 times with zero(ppm) water and absolute ethyl alcohol successively, after 105 ℃ of following dryings, gets the finished product.
This method has been eliminated employing zinc hydroxide trouble caused, compares with borax one zincate process, and it has advantages such as technology is simple, operation is few, product is single, and mother liquor can directly recycle, three-waste free pollution.
The composition of zinc borate has sizable difference with the difference of synthesis condition, even the 2ZnO3B that generally acknowledges now
2O
33.5H
2Crystal water in the O zinc borate be not yet strict be 3.5, but the different 2ZnO3B of water cut
2O
3NH
2The average moisture content of O.Therefore the research of carrying out both at home and abroad mainly is the research and the applied research thereof of synthesis condition that meets the zinc borate of application requiring about composition.And the preparation of the zinc borate of super-refinement is among the research, and US 3549316A is open: borax or boric acid is soluble in water, and add zinc oxide or comprise the sulphuric acid soln of zinc oxide; Or zinc sulfate or other zinc solutions; Be heated at least 70 ℃, after reaction for some time, obtain zinc borate through filtration or the separation of other means; Through X-ray check, the 2ZnO3B of acquisition
2O
33.5H
2The O zinc borate is at nano level.
The inventor discloses the method that a kind of pure water law prepares the submicron order zinc borate at first to file CN 201110184949.8, said method comprising the steps of: 1) the pure water mixed solution of preparation alcohol and water; 2) in said pure water mixed solution, add boric acid and zinc oxide, mix; The mass ratio of said zinc oxide and boric acid is 1: 5.9-1: 8.3; 3) add crystal seed, under 80-100 ℃ of temperature of reaction stirring and refluxing 1-4 hour; 4) the product filtered while hot of step 3 gained, washing, oven dry, the submicron order zinc borate that promptly gets.The alcohol that said method adopts is low-carbon alcohol, the more preferably alcohol of 1-8 carbon atom, the further preferred alcohol of 2-5 carbon atom.Said alcohol is monohydroxy-alcohol or divalent alcohol or polyvalent alcohol, such as methyl alcohol, ethanol, terepthaloyl moietie, propyl alcohol, USP Kosher, butanols, amylalcohol, hexanol or its mixture.From the consideration of economic benefit and technique effect, said alcohol is methyl alcohol, ethanol, propyl alcohol, terepthaloyl moietie and composition thereof more preferably, said low-carbon alcohol most preferred ethanol.Said method can effectively prepare the submicron order zinc borate, but the 2ZnO3B of its preparation
2O
33.5H
2The O zinc borate, exist like limit: (1) particle is assembled easily, and is dispersed bad, need when adding crystal seed, add some tensio-active agents, could make its dispersiveness produce a desired effect; (2) for the zinc borate of other kinds, such as 4ZnOB
2O
3H
2O (FB415), 2ZnO3B
2O
37H
2O, 2ZnO3B
2O
39H
2O, ZnOB
2O
32H
2O etc., said method waits checking; (3) selection of its crystal seed must be consistent with the target zinc borate.
Therefore, how to optimize reaction conditions,, can utilize pure water law to prepare various submicron order zinc borates, such as 2ZnO3B with a kind of blanket method
2O
33.5H
2O, 4ZnOB
2O
3H
2O, 2ZnO3B
2O
37H
2O, 2ZnO3B
2O
39H
2O, ZnOB
2O
32H
2O etc. are the technical barriers that affiliated technical field faces.
Summary of the invention
To the deficiency of prior art, one of the object of the invention is to provide a kind of method of utilizing USP Kosher to prepare the submicron order zinc borate.
Zinc borate preparation method of the present invention, it remains pure water law, but its specific alcohol that adopts: the alcohol mixture of USP Kosher or USP Kosher and other low-carbon alcohol.
The discovery that the contriver is joyful, the alcohol mixture of USP Kosher and USP Kosher and other low-carbon alcohol is used for pure water law and prepares the submicron order zinc borate, can prepare to be close to all types of xZnOyB
2O
3ZH
2Therefore the O zinc borate adopts the pure water law of the alcohol mixture of USP Kosher and USP Kosher and other low-carbon alcohol, and versatility is very good.
Secondly; The discovery that the contriver is surprised, adopt said USP Kosher or said alcohol mixture after, the preparation method of submicron order zinc borate of the present invention; Need when adding crystal seed, not add tensio-active agent, the zinc borate particle of its acquisition has better dispersiveness compared to prior art.
Once more, the discovery that the contriver is surprised, adopt said USP Kosher or said alcohol mixture after, the preparation method of submicron order zinc borate of the present invention, the crystal seed of interpolation no longer receives the restriction identical with the target crystal seed, the selection face of crystal seed is widened greatly.
Low-carbon alcohol in the alcohol mixture according to the invention; Be preferably the alcohol of 1-8 carbon atom; The alcohol of further preferred 2-5 carbon atom, said alcohol can be monohydroxy-alcohol or divalent alcohol or polyvalent alcohol, such as methyl alcohol, ethanol, terepthaloyl moietie, propyl alcohol, butanols, amylalcohol, hexanol or its mixture.
Submicron order of the present invention, according to the routine definition of affiliated technical field, meaning particle diameter is 100 nanometers (containing 100 nanometers)～1 micron (not containing 1 micron).The submicron order zinc borate that the present invention is prepared, its median size are generally less than 500 nanometers.
The zinc borate of preparing method's preparation according to the invention is not limited only to prepare 2ZnO3B
2O
33.5H
2O can also successfully prepare 4ZnOB
2O
3H
2O (FB415), 2ZnO3B
2O
37H
2O, 2ZnO3B
2O
39H
2O or ZnOB
2O
32H
2Submicron order zinc borates such as O, therefore preparing method's of the present invention applicable surface to be far longer than the contriver at first to file CN 201110184949.8.
The preparation method of submicron order zinc borate of the present invention said method comprising the steps of:
1) prepares the pure water mixed solution of USP Kosher and water, or dispose the pure water mixed solution of USP Kosher, other low-carbon (LC) alcohol and waters;
2) in said pure water mixed solution, add boric acid or borate and zinc oxide or inorganic zinc salt, mix; The mol ratio that the add-on of said boric acid or borate, zinc oxide or inorganic zinc salt should satisfy zinc and boron is 1: 0.4-1: 15 (mass ratio that is converted to zinc oxide and boric acid is 1: 0.3-1: 9);
3) add crystal seed xZnOyB
2O
3ZH
2O, stirring and refluxing 1.5～8 hours or longer time under 35-110 ℃ of temperature of reaction;
4) product of step 3 gained wash while hot, filtration or centrifugal settling, oven dry promptly gets submicron order zinc borate of the present invention.
The present invention chooses USP Kosher or USP Kosher and other low-carbon alcohol, and its pure water law is not only applicable to polytype zinc borate submicron particles, also makes particle disperse (referring to the electromicroscopic photograph in the accompanying drawing) more, helps its application.
Preferably, the preparation method of submicron order zinc borate of the present invention said method comprising the steps of:
1) by volume 1: 2-1: 13 process the pure water mixed solution of USP Kosher and water, and reflux;
2) be 1 by boric acid and zinc oxide and said pure water mixed solution mass ratio: 2-1: 13, in said pure water mixed solution, add boric acid or borate and zinc oxide or inorganic zinc salt, mix; The mol ratio that said boric acid or borate, zinc oxide or inorganic zinc salt add-on should satisfy zinc and boron is 1: 0.4-1: 15 (mass ratio of amounting to zinc oxide and boric acid is 1: 0.3-1: 9);
3) add crystal seed xZnOyB
2O
3ZH
2O, stirring and refluxing 1.5-8 hour or longer time under 35-110 ℃ of temperature of reaction;
4) the product filtered while hot or the centrifugal settling of step 3 gained, with alcohol solution washing and the activation of adding tensio-active agent, heated and stirred is filtered or centrifugal settling, and oven dry can get the submicron order zinc borate.
Preparing method of the present invention, it can prepare multiple submicron order zinc borate, but to various dissimilar zinc borates, can further be optimized preparation process condition, then prepares better effects if.Its processing condition can be optimized for:
In the step (1), the ratio of USP Kosher and water or USP Kosher and the alcohol mixture of other low-carbon alcohol and the ratio (all abbreviate pure water ratio as, be volume ratio) of water are 1: 2～1: 13, preferred 1: 4～1: 9;
In the step (2), said solid-to-liquid ratio (weight ratio) can be 1: 2～1: 9, preferred 1: 3～1: 5; Said solid-to-liquid ratio means boric acid or borate and zinc oxide or inorganic zinc salt, with the mass ratio of pure water mixed solution.
In the step (2), said boric acid or borate and zinc oxide or inorganic zinc salt, preferred boric acid and zinc oxide.
In the step (3), the said stirring and refluxing time can be 1.5～8 hours, preferred 2～5 hours, and more preferably 2～3 hours;
For high water nano-zinc borate 2ZnO3B
2O
37H
2O, 2ZnO3B
2O
39H
2O or ZnOB
2O
32H
2O, its processing condition further are preferably:
In the step (2), the mol ratio of Zn and B corresponds to 1: 0.5～and 1: 15, preferred 1: 2～1: 15, further preferred 1: 4～1: 7; Accordingly, being converted to zinc oxide and boric acid mass ratio can be 1: 0.3～1: 9, preferred 1: 2～1: 9, and further preferred 1: 3～1: 5;
In the step (3), said temperature of reaction can be 35～110 ℃, preferred 40～70 ℃, and more preferably 50～60 ℃.
For low water nano-zinc borate 2ZnO3B
2O
33.5H
2O, its processing condition further are preferably:
In the step (2), the mol ratio of Zn and B corresponds to 1: 0.5～and 1: 15, preferred 1: 2～1: 15, further preferred 1: 4～1: 7; Accordingly, being converted to zinc oxide and boric acid mass ratio can be 1: 0.3～1: 9, preferred 1: 2～1: 9, and further preferred 1: 3～1: 5;
In the step (3), said temperature of reaction can be 35～110 ℃, preferred 80～105 ℃, and more preferably 85～95 ℃.
For low water nano-zinc borate 4ZnOB
2O
3H
2O (FB415), its processing condition further are preferably:
In the step (2), the mol ratio of Zn and B corresponds to 1: 0.5～and 1: 15, preferred 1: 0.5～1: 5; Accordingly, be converted to zinc oxide and boric acid mass ratio and can be 1: 0.3～1: 9, preferred 1: 0.4～1: 4;
In the step (3), said temperature of reaction can be 35～110 ℃, preferred 90～110 ℃, and further preferred 100～110 ℃, more preferably 105 ℃.
Crystal seed xZnOyB of the present invention
2O
3ZH
2O, can with the applicant before formerly technological identical, select its target zinc borate kind, for example when needing preparation 2ZnO3B
2O
33.5H
2During O, the crystal seed of interpolation is 2ZnO3B
2O
33.5H
2O; When needs prepare 2ZnO3B
2O
39H
2During O, the crystal seed of interpolation is 2ZnO3B
2O
39H
2O.
But the wonderful discovery of contriver, the present invention is through adopting the alcohol mixture of USP Kosher and USP Kosher, described crystal seed xZnOyB
2O
3ZH
2The selection of O can not receive the restriction of target zinc borate kind.For example as preparation 2ZnO3B
2O
33.5H
2During O, the crystal seed of interpolation can be for the zinc borate of other kinds, such as 4ZnOB
2O
3H
2O or ZnOB
2O
32H
2O etc.
Preferably; In the method for preparing the submicron order zinc borate of the present invention; When prepared submicron order zinc borate had reunion to a certain degree, for alleviating the reaction of reuniting, the present invention was preferably when reaction begins to add crystal seed; Add tensio-active agent simultaneously, and crystal seed, tensio-active agent and reactant are mixed.
Said tensio-active agent can be this area tensio-active agent that plays dissemination commonly used; The preferred sodium laurylsulfonate of the present invention, sodium lauryl sulphate, FM, Vinylpyrrolidone polymer or its mixture, further preferred sodium laurylsulfonate is or/and sodium lauryl sulphate.
Described dosage of surfactant is the 0.4-2% of material total mass, preferred 0.6-0.9%.
Owing to adopted technique scheme, compared with prior art, the present invention has following advantage and effect:
(1), adopt pure water law can make submicron-grade superfine zinc borate xZnOyB through thermogravimetric and electronic microscope photos
2O
3ZH
2The O molecular diameter reaches submicron order, and product cut size can be less than 500 nanometers.The zinc borate that said method makes according to the difference of temperature of reaction and material ratio, shows that through the thermogravimetric analysis result product can be particle diameter submicron zinc borate xZnOyB
2O
3ZH
2O is like 2ZnO3B
2O
37H
2O, 2ZnO3B
2O
39H
2O, 2ZnO3B
2O
33.5H
2O etc.; Use USP Kosher or USP Kosher to mix use with other alcohol; Or select suitable properties-correcting agent (tensio-active agent) can make product be easy to disperse, powder through super-refinement, not only helps the dispersion of particle in the macromolecule matrix material as fire retardant; Reduce consumption, and can improve the interface binding power between fire retardant and macromolecular material.
(2) versatility; These article are particularly suitable to the PVC material; And being widely used in industry such as not halogen-containing plastics, rubber, coating, weaving again, spendable material has: SE, unsaturated polyester, urethane, epoxy resin, ABS resin, polycarbonate, Vilaterm, Vestolen PP 7052 etc.
(3) nontoxic antimycotic antiseptic property, constant zine ion and the borate ion that produces trace of these article, thereby can be at the mould bactericidal property of material surface natural birth biological and ecological methods to prevent plant disease, pests, and erosion, these article are used for the home decoration material in a large number and are particularly suitable for wet environment the America and Europe.
(4) transparency, approaching because of these article refractive index with plastics, can be used for the fire-retardant of transparent plastics.
The submicron order zinc borate of the present invention's preparation is a kind of novel inorganic materials, has purposes very widely.
Description of drawings
Fig. 1-1～Fig. 4-2 is the thermal multigraph and the sem photograph of the submicron order zinc borate of employing USP Kosher and water preparation, and product is 2ZnO3B
2O
33.5H
2O;
Fig. 5-1～Fig. 7-2 mixes the thermal multigraph and the sem photograph of the submicron order zinc borate of alcohol and water preparation for adopting USP Kosher with methyl alcohol, primary isoamyl alcohol, pinakon etc.; Particle diameter is less than 500 nanometers, and dispersion, and product is 2ZnO3B
2O
33.5H
2O;
Fig. 8-1 and Fig. 8-2 is main pure water solvent for adopting USP Kosher, second alcohol and water, and temperature of reaction is 105 ℃, the thermal multigraph and the sem photograph of the submicron order zinc borate of preparation.Product is 4ZnOB
2O
3H
2O;
Fig. 9-1 and Fig. 9-2 is main pure water solvent for adopting USP Kosher, second alcohol and water, and temperature of reaction is 60 ℃, the thermal multigraph and the sem photograph of the submicron order zinc borate of preparation; Product is 2ZnO3B
2O
37H
2O;
Figure 10-1 and Figure 10-2 adopts the pure aqueous fusion agent of USP Kosher instead of ethanol, and temperature of reaction is 40 ℃, the submicron order zinc borate sem photograph of preparation, and the products obtained therefrom particle obviously changes, particle diameter＜500nm; There is certain agglomeration in product; Product is ZnOB
2O
32H
2O.
Embodiment
For ease of understanding the present invention, it is following that the present invention enumerates embodiment.Those skilled in the art should understand, and said embodiment only is used for helping to understand the present invention, should not be regarded as concrete restriction of the present invention.
Embodiment 1
In flask, add 30g boric acid and 140mL water and 16.9mL USP Kosher, the stirring heating reaction keeps 95 ℃ to add the 1g crystal seed, sneaks into 18.6g boric acid; And in 1 hour, add a 8.2g zinc oxide by part; (the solid-liquid mass ratio of boric acid and zinc oxide and pure water is 1: 2.7, and the mass ratio of zinc oxide and boric acid is 1: 5.9), stirring reaction is at 95 ℃ of following 2h; Filtration washing is also dry, obtains product.(accompanying drawing 1-1 and Fig. 1-2)
In flask, add 40g boric acid and 187mL water and 20mL USP Kosher; The stirring heating reaction keeps 95 ℃ to add the 1g crystal seed, sneaks into 33.6g boric acid, and (the solid-liquid mass ratio of boric acid and zinc oxide and pure water is 1: 2.6 in 1 hour, to add 8.2g zinc oxide by part; The mass ratio of zinc oxide and boric acid is 1: 9); Stirring reaction is at 95 ℃ of following 2h, and filtration washing is also dry, obtains product.(accompanying drawing 2-1 and accompanying drawing 2-2)
In flask, add 160mL water and 13mL USP Kosher solution and 25g boric acid, be heated with stirring to 90 ℃ and make its dissolving, add following material subsequently: 7.8g boric acid, 0.5g crystal seed.And in 1 hour, add a 8.2g zinc oxide by part.(the solid-liquid mass ratio of boric acid and zinc oxide and pure water is 1: 4.3, and the mass ratio of zinc oxide and boric acid is 1: 4) reacted lasting 2h down at 90 ℃, and filtration washing is also dry, obtains product.(accompanying drawing 3-1 and Fig. 3-2)
Embodiment 4
The BORAX PENTAHYDRATE-99.9MIN that in flask, adds 25.2g; 54.1g boric acid add 220mL water and 28mL USP Kosher, again sulfuric acid and the 52mL water of 7.1g zinc oxide 8.7g 96% are processed solution, two kinds of solution are slowly mixed; Solution begins crystallization; Add the 0.5g crystal seed again, mix, continue to stir 3h down at 105 ℃.(the solid-liquid mass ratio of borax, boric acid and zinc oxide and pure water is 1: 3.7, and the mol ratio of zinc chloride and boric acid, the contained zinc of borax and boron is 1: 13.9) filtered product, and pure water washing, and 110 ℃ of dryings 12 hours obtain product 2ZnO3B
2O
33.5H
2O (accompanying drawing 4-1 and Fig. 4-2).
25.2g borax, 54.1g boric acid are joined 280mL deionized water and 60mL primary isoamyl alcohol 15mL USP Kosher, dissolve down at 95 ℃ and process solution; The 12.6g zinc chloride is dissolved in 50mL water; Two kinds of solution are mixed and add crystal seed 0.5g, (the solid-liquid mass ratio of borax, boric acid and zinc chloride and pure water is 1: 4.3, and the mol ratio of zinc chloride and boric acid, the contained zinc of borax and boron is 1: 12.3); React 3h down at 100 ℃, the product decant is separated, the solution of the second alcohol and water of the FM of adding 0.8g; 90 ℃ were heated 3-5 minute down, and surface active and pure water washing separate through centrifugal settling; 110 ℃ of dryings 12 hours obtain product 2ZnO3B
2O
33.5.(accompanying drawing 5-1 and Fig. 5-2).
Embodiment 6
The BORAX PENTAHYDRATE-99.9MIN that in flask, adds 25.2g; 54.1g boric acid add methyl alcohol and the 7mL USP Kosher of 220mL water and 53mL, again sulfuric acid and the 52mL water of 7.1g zinc oxide and 8.7g 96% are processed solution, two kinds of solution are slowly mixed; Solution begins crystallization; Add the 0.5g crystal seed again, mix, continue to stir 5h down at 95 ℃.(the solid-liquid mass ratio of borax, boric acid and zinc oxide and pure water is 1: 3.8, and the mol ratio of zinc chloride and boric acid, the contained zinc of borax and boron is 1: 13.1) separated the product decant; 90 ℃ of addings contain the solution of second alcohol and water of the dodecyloxy sodium sulfonate of 0.6g; Surface active and washing separate through centrifugal settling, and the product decant is separated; 110 ℃ of dryings 12 hours obtain product 2ZnO3B
2O
33.5.(accompanying drawing 6-1 and Fig. 6-2)
Embodiment 7
In flask, add 30g boric acid and 140mL water and 16.9mL terepthaloyl moietie and 7mL USP Kosher, the stirring heating reaction keeps 95 ℃ to add the 1g crystal seed, sneaks into 18.6g boric acid; And in 1 hour, add a 8.2g zinc oxide, (the solid-liquid mass ratio of boric acid and zinc oxide and pure water is 1: 2.9, and the mass ratio of zinc oxide and boric acid is 1: 5.9) by part; Stirring reaction separates the product decant at 95 ℃ of following 2h, adds and contains the solution that the Vilaterm that adds 0.7g adjoins the second alcohol and water of pyrrolidone; Heating is also stirred, and 90 ℃ were heated 3-5 minute surface active and pure water washing down; Separate through centrifugal settling, 110 ℃ of dryings 12 hours obtain product 2ZnO3B
2O
33.5.(accompanying drawing 7-1 and Fig. 7-2)
Embodiment 8
In flask, in solution, add the ZnSO4.7H of 4.3g (0.015mol) with the five water sodium tetraborates of the deionized water of 75mL and 25mL dissolve with ethanol 4.6g (0.0158mol)
2O and 25mL water generate white precipitate immediately.The crystal seed that under boiling state, adds 8.55g (0.105mol) ZnO and the previous preparation of 0.5g.105 ℃ of ebuillition of heated back flow reaction 5 hours.(the solid-liquid mass ratio of borax and zinc oxide, zinc sulfate and pure water is 1: 6.9, and the mol ratio of contained zinc of zinc oxide and zinc sulfate and borax and boron is 1: 0.53) filtered product, and pure water washing, and 110 ℃ of dryings 12 hours obtain product 4ZnOB
2O
3H
2O, (accompanying drawing 8-1 and accompanying drawing 8-2).
Embodiment 9
With the 25.2g borax, 54.1g boric acid joins 280mL deionized water and 70mL ethanol, 1mL USP Kosher, 95 ℃ down dissolving process solution.The 12.6g zinc chloride is dissolved in 50mL water.Two kinds of solution are mixed and add crystal seed 0.5g; (the solid-liquid mass ratio of borax, boric acid and zinc chloride and pure water is 1: 4.2, and the mol ratio of zinc chloride and boric acid, the contained zinc of borax and boron is 1: 12.3) reacted 5h down at 60 ℃; Product is filtered; And pure water washing, 110 ℃ of dryings 12 hours obtain product 2ZnO3B
2O
37H
2O (accompanying drawing 9-1 and accompanying drawing 9-2).
With the 25.2g borax, 54.1g boric acid joins 280mL deionized water and 15mL USP Kosher, dissolves down at 95 ℃ and processes solution; The 12.6g zinc chloride is dissolved in 50mL water, two kinds of solution are mixed and add crystal seed 0.5g, (the solid-liquid mass ratio of borax, boric acid and zinc chloride and pure water is 1: 3.7; The mol ratio of zinc chloride and boric acid, the contained zinc of borax and boron is 1: 12.3); React 5h down at 40 ℃, filtration washing is also dry, obtains product.Resulting product molecular formula is ZnOB
2O
32H
2O.(accompanying drawing 10-1 and Figure 10-2).
Shown in said embodiment 1-10 and accompanying drawing 1-10, after adopting USP Kosher alcohol water law and optimizing processing condition, the present invention has successfully prepared the zinc borate of submicron order.Through material ratio, the liquid-solid ratio of selecting to suit, when temperature of reaction is the 40-70 ℃ of zinc borate 2ZnO3B that can prepare Gao Shui
2O
37H
2O, temperature of reaction are 80-105 ℃ can get 2ZnO3B
2O
33.5, product can be 4ZnOB when temperature of reaction was higher than 100 ℃
2O
3H
2O (FB411).Use USP Kosher or USP Kosher to mix and use pure water law, or use tensio-active agent, can get said zinc borate uniform particles and dispersion with other ground low-carbon alcohol.
Applicant's statement; The present invention explains detailed process condition of the present invention and technical process through the foregoing description; But the present invention is not limited to above-mentioned detailed process condition and technical process, does not mean that promptly the present invention must rely on above-mentioned detailed process condition and technical process could be implemented.The person of ordinary skill in the field should understand, and to any improvement of the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. the preparation method of a submicron order zinc borate is characterized in that, said method comprising the steps of:
1) prepares the pure water mixed solution of USP Kosher and water, or dispose the pure water mixed solution of USP Kosher, other low-carbon (LC) alcohol and waters;
2) in said pure water mixed solution, add boric acid or borate and zinc oxide or inorganic zinc salt, mix; The mol ratio that the add-on of said boric acid or borate, zinc oxide or inorganic zinc salt should satisfy zinc and boron is 1: 0.4-1: 15 (mass ratio that is converted to zinc oxide and boric acid is 1: 0.3-1: 9);
3) add crystal seed xZnOyB
2O
3ZH
2O, stirring and refluxing 1.5～8 hours or longer time under 35-110 ℃ of temperature of reaction;
4) product of step 3 gained wash while hot, filtration or centrifugal settling, oven dry promptly gets said submicron order zinc borate.
2. preparation method as claimed in claim 1 is characterized in that, said method comprising the steps of:
1) by volume 1: 2-1: 13 process the pure water mixed solution of USP Kosher and water, and reflux;
2) be 1 by boric acid and zinc oxide and said pure water mixed solution mass ratio: 2-1: 13, in said pure water mixed solution, add boric acid or borate and zinc oxide or inorganic zinc salt, mix; The mol ratio that said boric acid or borate, zinc oxide or inorganic zinc salt add-on should satisfy zinc and boron is 1: 0.4-1: 15 (mass ratio of amounting to zinc oxide and boric acid is 1: 0.3-1: 9);
3) add crystal seed xZnOyB
2O
3ZH
2O, stirring and refluxing 1.5-8 hour or longer time under 35-110 ℃ of temperature of reaction;
4) the product filtered while hot or the centrifugal settling of step 3 gained, with alcohol solution washing and the activation of adding tensio-active agent, heated and stirred is filtered or centrifugal settling, and oven dry can get the submicron order zinc borate.
3. according to claim 1 or claim 2 preparation method is characterized in that, in the step (1), the ratio of USP Kosher and water or USP Kosher and the alcohol mixture of other low-carbon alcohol and the volume ratio of water are 1: 2～1: 13, preferred 1: 4～1: 9;
Preferably, in the step (2), said solid-to-liquid ratio weight ratio is 1: 2～1: 9, preferred 1: 3～1: 5;
Preferably, in the step (3), preferred 2～5 hours of said stirring and refluxing time, more preferably 2～3 hours.
4. like each preparation method of claim 1-3, it is characterized in that said zinc borate is 4ZnOB
2O
3H
2O, 2ZnO3B
2O
33.5H
2O, 2ZnO3B
2O
37H
2O, 2ZnO3B
2O
39H
2O or ZnOB
2O
32H
2O.
5. like each preparation method of claim 1-4, it is characterized in that, for high water nano-zinc borate 2ZnO3B
2O
37H
2O, 2ZnO3B
2O
39H
2O or ZnOB
2O
32H
2O, its processing condition are preferably:
In the step (2), the mol ratio of Zn and B corresponds to 1: 0.5～and 1: 15, preferred 1: 2～1: 15, further preferred 1: 4～1: 7;
Preferably, in the step (3), preferred 40～70 ℃ of said temperature of reaction, more preferably 50～60 ℃.
6. like each preparation method of claim 1-4, it is characterized in that, for low water nano-zinc borate 2ZnO3B
2O
33.5H
2O, its processing condition further are preferably:
In the step (2), the mol ratio of Zn and B corresponds to 1: 0.5～and 1: 15, preferred 1: 2～1: 15, further preferred 1: 3～1: 5;
Preferably, in the step (3), preferred 80～105 ℃ of said temperature of reaction, more preferably 85～95 ℃.
7. like each preparation method of claim 1-4, it is characterized in that, for low water nano-zinc borate 4ZnOB
2O
3H
2O, its processing condition further are preferably:
In the step (2), the mol ratio of Zn and B corresponds to 1: 0.5～and 1: 5;
Preferably, in the step (3), said temperature of reaction is 90～110 ℃, preferred 100～110 ℃, and more preferably 105 ℃.
8. like each preparation method of claim 1-7, it is characterized in that, when step 3 adds crystal seed, add tensio-active agent simultaneously, and crystal seed, tensio-active agent and reactant are mixed;
Preferably, said tensio-active agent is sodium laurylsulfonate, sodium lauryl sulphate, FM, Vinylpyrrolidone polymer or its mixture; Preferred sodium laurylsulfonate is or/and sodium lauryl sulphate;
Preferably; Described dosage of surfactant is the 0.4-2% of material total mass, preferred 0.6-0.9%.
9. like each preparation method of claim 1-8; It is characterized in that; Said low-carbon alcohol is the alcohol of 1-8 carbon atom; The alcohol of further preferred 2-5 carbon atom, said alcohol can be monohydroxy-alcohol or divalent alcohol or polyvalent alcohol, such as methyl alcohol, ethanol, terepthaloyl moietie, propyl alcohol, butanols, amylalcohol, hexanol or its mixture.
10. like each preparation method of claim 1-9, it is characterized in that, described submicron order zinc borate, its median size is less than 500 nanometers.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107235496A (en) * | 2017-07-07 | 2017-10-10 | 辽宁大学 | A kind of Firebrake ZB ZnB2O4The low temperature preparation method of luminescent material |
| CN109279618A (en) * | 2018-10-25 | 2019-01-29 | 青岛科技大学 | It is a kind of for repairing the reparation liquid and restorative procedure of 2335 type zinc borate defects |
| CN110240173A (en) * | 2019-07-24 | 2019-09-17 | 山东泰星新材料股份有限公司 | 112 zinc borate flame retardants of one kind and its preparation method and application |
| WO2020106250A1 (en) * | 2018-09-25 | 2020-05-28 | Akdeniz Kimya Sanayi Ve Ticaret A.S. | A process for synthesis of zinc borate |
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| CN101254927A (en) * | 2008-03-28 | 2008-09-03 | 江南大学 | Method for preparing active zinc borate by one-step proccess |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107235496A (en) * | 2017-07-07 | 2017-10-10 | 辽宁大学 | A kind of Firebrake ZB ZnB2O4The low temperature preparation method of luminescent material |
| WO2020106250A1 (en) * | 2018-09-25 | 2020-05-28 | Akdeniz Kimya Sanayi Ve Ticaret A.S. | A process for synthesis of zinc borate |
| CN109279618A (en) * | 2018-10-25 | 2019-01-29 | 青岛科技大学 | It is a kind of for repairing the reparation liquid and restorative procedure of 2335 type zinc borate defects |
| CN109279618B (en) * | 2018-10-25 | 2022-01-28 | 青岛科技大学 | Repair liquid and repair method for repairing 2335 type zinc borate defects |
| CN110240173A (en) * | 2019-07-24 | 2019-09-17 | 山东泰星新材料股份有限公司 | 112 zinc borate flame retardants of one kind and its preparation method and application |
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