CN109809426A - The water-bath of ultra-fine flower-shaped line borate fire retardant-hydro-thermal linkage synthesis - Google Patents
The water-bath of ultra-fine flower-shaped line borate fire retardant-hydro-thermal linkage synthesis Download PDFInfo
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Abstract
The invention discloses a kind of water-bath of ultra-fine flower-shaped line borate-hydro-thermal linkage synthetic methods, are related to technical field of inorganic chemical industry.Specific step is as follows: calcium salt, alkali source, boron source being dissolved in water respectively, first aqueous slkali is added drop-wise in calcium source solution, and adds induction crystallizing agent, B solution is added drop-wise in mixed solution again, it stirs evenly and is transferred in water-bath, reaction time 4-10h, 50-90 DEG C of reaction temperature；Above-mentioned white intermediate product is gone in reaction kettle, 120-180 DEG C of the hydro-thermal reaction time 4-24h, reaction temperature；Ultra-fine flower-shaped line borate is finally obtained after post-treated again.Product of the present invention is ultra-fine flower-shaped line borate, and pattern is uniform, and purity is high has broad application prospects；Flower-shaped line borate is synthesized using water-bath-hydro-thermal method, reaction condition is mild, and reaction mother liquor recoverable, safety is good, and low energy consumption.
Description
Technical field:
The present invention relates to technical field of inorganic chemical industry, and in particular to the water-bath of ultra-fine flower-shaped line borate fire retardant-hydro-thermal connection
Dynamic circuit connector at.
Background technique:
Fire retardant more and more important role of performer in our life, to environment during fire retardant use
The problem of influence, also obtains the concern of people gradually, and the non-halogen of it, Non-toxic, Composite and suppression fuming become fire retardant not
Carry out development trend.And boron flame retardant is exactly the fire retardant for having many advantages, such as that thermal stability is good, toxicity is low, eliminating smoke a kind of in this way,
And it is good with other fire retardant compounding effects, there is extraordinary development prospect.
Line borate price is lower in boron flame retardant, itself will not generate secondary dirt without toxic during fire-retardant
Dye, very environmentally friendly, the fire retardant that can be used in the organic materials such as plastics, rubber.As addition type inorganic fire retardants, to make boric acid
Calcium is preferably evenly dispersed in polymer base material and merges, the synthesis for the line borate crystal of extraordinary pattern, specified particle size,
Demand is increasing.
The Chinese patent of Publication No. CN104817094A discloses a kind of by hydro-thermal-thermal transition preparation hydration and anhydrous
The method of multistage porous line borate microballoon, but the said goods particle morphology homogeneity is poor, is unformed state；Publication No.
The Chinese patent of CN106082252A also discloses a kind of preparation method for being hydrated line borate microballoon and anhydrous boric acid calcium microballoon,
Product granularity is more uniform, but pattern is irregular, and granularity is larger, runs counter to the fine development trend of present fire proofing.
Summary of the invention:
Technical problem to be solved by the present invention lies in a kind of ultra-fine, monodisperse is provided, with the line borate of regular morphology
Crystal powder fire proofing.By water-bath-hydro-thermal linkage synthesis induction crystallizing agent is added, to control line borate in the present invention
Pattern and granularity.
The following technical solution is employed for the technical problems to be solved by the invention to realize:
The water-bath of ultra-fine flower-shaped line borate fire retardant-hydro-thermal linkage synthesis, comprising the following steps:
(1) aqueous slkali is added drop-wise in calcium salt soln, and induction crystallizing agent is added, be uniformly mixed, obtain mixed solution；
(2) boron source is dissolved in water, and be added in mixed solution, mixed slurry is made；
(3) mixed slurry is transferred in water-bath, reaction time 4-10h, 50-90 DEG C of reaction temperature；
(4) above-mentioned white intermediate product is transferred in reaction kettle, the hydro-thermal reaction time 4-24h, reaction temperature 120-180
DEG C, it is cooled to room temperature, obtains hydrothermal product；
(5) by hydrothermal product by washing, filtering, 120 DEG C of dry 8h obtain ultra-fine flower-shaped line borate particle.
The Ca/B molar ratio is 1:2.5-5, and calcium salt is selected from one of calcium nitrate, calcium chloride or calcium acetate, and boron source is
Technical grade boric acid, alkali source are industrial sodium hydroxide.
The induction crystallizing agent is one of hydrolysis substance, nano aluminium oxide, nano silica of aluminium or silicon or several
Kind, induce the additive amount of crystallizing agent for the 0.5%-10% of calcium source content.And the final pH of crystallizing agent is induced to control in 9.5-
11.0.The induction crystallizing agent is other than the pattern of control line borate and granularity, moreover it is possible to accelerate the rate of line borate synthesis, improve boron
The purity of sour calcium.
Beneficial effects of the present invention:
(1) present invention synthesizes granularity between 0.5-5 um by addition induction crystallizing agent and water-bath-hydro-thermal two-step method
Flower-shaped line borate, uniform product appearance, purity is high, have broad application prospects, and raw materials used is all technical grade, is easy to
Produce in enormous quantities；
(2) flower-shaped line borate is synthesized using water-bath-hydro-thermal method, reaction condition is mild, reaction mother liquor recoverable, safety
Property is good, and low energy consumption.
Detailed description of the invention:
Fig. 1 is the XRD spectrum of flower-shaped line borate obtained in embodiment 1；
Fig. 2 is the SEM spectrum of flower-shaped line borate obtained in embodiment 1；
Fig. 3 is the SEM spectrum of lamella line borate obtained in embodiment 2；
Fig. 4 is the SEM spectrum of line borate obtained in embodiment 3.
Specific embodiment:
In order to be easy to understand the technical means, the creative features, the aims and the efficiencies achieved by the present invention, tie below
Specific embodiment is closed, the present invention is further explained.
Embodiment 1
(1) 15ml second level water is added to and is filled in 0.0268mol calcium nitrate solid beaker, 5 min of magnetic agitation；
(2) 15ml second level water is added to and is filled in 0.0536mol NaOH solid beaker, 5 min of magnetic agitation；
(3) NaOH solution is slowly dropped in calcium salt soln, and adds the nano aluminium oxide that calcium content is 5%；
(4) 60ml second level water is added to and is filled in 0.0911mol boric acid solid beaker, heating is stirred to boric acid and dissolved；
(5) boric acid solution is added drop-wise to mixed solution obtained by (3), rate of addition 5ml/min continues to stir 10min；
(6) by (5) mixed slurry be transferred in water-bath, 85 DEG C of water-bath 6h；
(7) by (6) mixed slurry be transferred in water heating kettle, cooled to room temperature after 150 DEG C of hydro-thermal 14h obtains water
Hot；
(8) by hydrothermal product successively by washing, filtering, 120 DEG C of dry 8h obtain ultra-fine flower-shaped line borate particle.
Flower-shaped line borate (the 4CaO5B that the present embodiment is prepared2O3·7H2O XRD spectrum) is as shown in Figure 1.From
As can be seen that flower-shaped 4CaO5B in figure2O3·7H2The XRD diagram of O matched with XRD standard card JCPDS No.09-0147 compared with
It is good, illustrate that product group becomes pure phase substance.
Flower-shaped line borate (the 4CaO5B that the present embodiment is prepared2O3·7H2O SEM image) is as shown in Figure 2.From
As can be seen that line borate crystal is assembled into biggish laminated structure by two-dimensional nano piece in figure, lamella assembles again, is formed similar
In the flower-like structure of lantern, for partial size at 3-5 μm, particle diameter distribution is uniform.
Embodiment 2
(1) 15ml second level water is added to and is filled in 0.0268mol calcium nitrate solid beaker, 5 min of magnetic agitation；
(2) 15ml second level water is added to and is filled in 0.0536mol NaOH solid beaker, 5 min of magnetic agitation；
(3) NaOH solution is slowly dropped in calcium salt soln, and adds the silicon hydrolysate that content is 8%；
(4) 60ml second level water is added to and is filled in 0.0911mol boric acid solid beaker, heating is stirred to boric acid and dissolved；
(5) boric acid solution is added drop-wise to mixed solution obtained by (3), rate of addition 5ml/min continues to stir 10min；
(6) by (5) mixed slurry be transferred in water-bath, 85 DEG C of water-bath 6h；
(7) by (6) mixed slurry be transferred in water heating kettle, cooled to room temperature after 150 DEG C of hydro-thermal 14h obtains water
Hot；
(8) by hydrothermal product successively by washing, filtering, 120 DEG C of dry 8h obtain ultra-fine flower-shaped line borate particle.
Line borate (the 4CaO5B that the present embodiment is prepared2O3·7H2O SEM image) is as shown in Figure 3.It can from figure
To find out, the line borate nanometer sheet of hydrothermal synthesis is stacked with, and forms multilayer chip structure, for partial size at 3-5 μm, particle diameter distribution is equal
It is even.
Embodiment 3
(1) 15ml second level water is added to and is filled in 0.0268mol calcium nitrate solid beaker, 5 min of magnetic agitation；
(2) 15ml second level water is added to and is filled in 0.0536mol NaOH solid beaker, 5 min of magnetic agitation；
(3) NaOH solution is slowly dropped in calcium salt soln, does not add line borate induction crystallizing agent；
(4) 60ml second level water is added to and is filled in 0.0911mol boric acid solid beaker, heating is stirred to boric acid and dissolved；
(5) boric acid solution is added drop-wise to mixed solution obtained by (3), rate of addition 5ml/min continues to stir 10min；
(6) by (5) mixed slurry be transferred in water-bath, 6h is stirred at room temperature；
(7) by (6) mixed slurry be transferred in water heating kettle, cooled to room temperature after 150 DEG C of hydro-thermal 14h obtains water
Hot；
(8) by hydrothermal product successively by washing, filtering, 120 DEG C of dry 8h obtain ultra-fine flower-shaped line borate particle.
Line borate (the 4CaO5B that the present embodiment is prepared2O3·7H2O SEM image) is as shown in Figure 4.It can from figure
To find out, the line borate of hydrothermal synthesis is that two-dimensional nano piece stacks the microballoon to be formed, and for partial size at 10 μm, particle diameter distribution is uneven.
The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (3)
1. the water-bath of ultra-fine flower-shaped line borate fire retardant-hydro-thermal linkage synthesis, it is characterised in that: the following steps are included:
(1) aqueous slkali is added drop-wise in calcium salt soln, and induction crystallizing agent is added, be uniformly mixed, obtain mixed solution；
(2) boron source is dissolved in water, and be added in mixed solution, mixed slurry is made；
(3) mixed slurry is transferred in water-bath, reaction time 4-10h, 50-90 DEG C of reaction temperature；
(4) above-mentioned white intermediate product is transferred in reaction kettle, 120-180 DEG C of the hydro-thermal reaction time 4-24h, reaction temperature,
It is cooled to room temperature, obtains hydrothermal product；
(5) by hydrothermal product by washing, filtering, 120 DEG C of dry 8h obtain ultra-fine flower-shaped line borate particle.
2. the water-bath of ultra-fine flower-shaped line borate fire retardant according to claim 1-hydro-thermal linkage synthesis, it is characterised in that:
The Ca/B molar ratio is 1:2.5-5, and calcium salt is selected from one of calcium nitrate, calcium chloride or calcium acetate, and boron source is technical grade boron
Acid, alkali source are industrial sodium hydroxide.
3. the water-bath of ultra-fine flower-shaped line borate fire retardant according to claim 1-hydro-thermal linkage synthesis, it is characterised in that:
The induction crystallizing agent is one or more of hydrolysis substance, nano aluminium oxide, nano silica of aluminium or silicon, induction knot
The additive amount of brilliant agent is the 0.5%-10% of calcium source content., and the final pH of crystallizing agent is induced to control in 9.5-11.0.
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| CN201910156648.0A CN109809426B (en) | 2019-03-01 | 2019-03-01 | Water bath-hydrothermal linkage synthesis of superfine flower-like calcium borate flame retardant |
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| CN201910156648.0A CN109809426B (en) | 2019-03-01 | 2019-03-01 | Water bath-hydrothermal linkage synthesis of superfine flower-like calcium borate flame retardant |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120072547A (en) * | 2010-12-24 | 2012-07-04 | 한국화학연구원 | Green emitting calcium borate silicate based phosphor |
| CN103819182A (en) * | 2013-12-31 | 2014-05-28 | 苏州大学 | Calcium borate silicate biological material as well as preparation and application thereof |
| CN105821476A (en) * | 2016-05-09 | 2016-08-03 | 曲阜师范大学 | Mild hydrothermal-thermal transition synthetic method for high-draw-ratio hydrated and anhydrous calcium borate nanowhisker |
| CN106082252A (en) * | 2016-05-28 | 2016-11-09 | 曲阜师范大学 | A kind of hydration Calcium pyroborate microsphere, anhydrous boric acid calcium microsphere and preparation method thereof |
-
2019
- 2019-03-01 CN CN201910156648.0A patent/CN109809426B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120072547A (en) * | 2010-12-24 | 2012-07-04 | 한국화학연구원 | Green emitting calcium borate silicate based phosphor |
| CN103819182A (en) * | 2013-12-31 | 2014-05-28 | 苏州大学 | Calcium borate silicate biological material as well as preparation and application thereof |
| CN105821476A (en) * | 2016-05-09 | 2016-08-03 | 曲阜师范大学 | Mild hydrothermal-thermal transition synthetic method for high-draw-ratio hydrated and anhydrous calcium borate nanowhisker |
| CN106082252A (en) * | 2016-05-28 | 2016-11-09 | 曲阜师范大学 | A kind of hydration Calcium pyroborate microsphere, anhydrous boric acid calcium microsphere and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| WANCHENG ZHU ET AL.，: "Hierarchical Laminar Superstructures of Rhombic Priceite (Ca4B10O19•7H2O): Facile Hydrothermal Synthesis, Shape Evolution, Optical, and Thermal Decomposition Properties", 《CRYSTAL GROWTH DESIGN》 * |
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