CN109179445A - The preparation of 2335 type zinc borates and microscopic appearance regulate and control method - Google Patents
The preparation of 2335 type zinc borates and microscopic appearance regulate and control method Download PDFInfo
- Publication number
- CN109179445A CN109179445A CN201811249987.5A CN201811249987A CN109179445A CN 109179445 A CN109179445 A CN 109179445A CN 201811249987 A CN201811249987 A CN 201811249987A CN 109179445 A CN109179445 A CN 109179445A
- Authority
- CN
- China
- Prior art keywords
- zinc
- hydroxide
- solution
- type
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical class [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 69
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims abstract description 46
- 229940007718 zinc hydroxide Drugs 0.000 claims abstract description 44
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 25
- 229960001763 zinc sulfate Drugs 0.000 claims abstract description 25
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 25
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004327 boric acid Substances 0.000 claims abstract description 20
- 230000000694 effects Effects 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 12
- 230000008859 change Effects 0.000 claims abstract description 5
- 239000000047 product Substances 0.000 claims description 21
- 230000033228 biological regulation Effects 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003063 flame retardant Substances 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 238000012544 monitoring process Methods 0.000 claims description 2
- 230000000877 morphologic effect Effects 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 2
- 229910052708 sodium Inorganic materials 0.000 claims 2
- 239000011734 sodium Substances 0.000 claims 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 239000011787 zinc oxide Substances 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000010899 nucleation Methods 0.000 abstract description 6
- 230000006911 nucleation Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 230000001788 irregular Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 230000008676 import Effects 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 23
- 239000007788 liquid Substances 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- -1 acetone Sulfone Chemical class 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/12—Borates
- C01B35/127—Borates of heavy metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention provides a kind of microscopic appearances of 2335 type zinc borates to regulate and control method, using boric acid, zinc hydroxide as Material synthesis zinc borate, the preparation of different activity zinc hydroxides is realized from the haptoreaction mode and reaction temperature of sodium hydroxide solution by change zinc sulfate, the reaction activity demand of zinc hydroxide is matched by adjusting the synthesis temperature of zinc borate, to control the reaction rate of zinc hydroxide and boric acid, the crystal nucleation rate and crystal growth rate for further influencing zinc borate are realized and are regulated and controled to the microscopic appearance of crystalline product.The present invention be able to solve traditional zinc borate production technology product microscopic appearance it is irregular, in terms of defect, produce the controllable differentiated products of series of stable, suitable for different application fields, the situation that the high-end zinc borate products in China need to rely on market import can be effectively reversed, there are boundless market prospects.
Description
Method field
The present invention relates to the preparations of zinc borate, and in particular to the preparation of 2335 type zinc borates of one kind and microscopic appearance regulation side
Method belongs to halogen-free flame retardants field.
Background method
It is sub- to be soluble in hydrochloric acid, sulfuric acid, diformazan for zinc borate, white powder, not soluble in water, ethyl alcohol, n-butanol, benzene, acetone
Sulfone.Thermal stability is good, easily disperses, nontoxic.
Zinc borate have it is fire-retardant, glow at charcoal, suppression cigarette, suppression and prevent from generating molten drop, less toxic, inexpensive, transparency is high and not
The features such as easily precipitating.The multifunctional synergistic additive that can be used as antimony oxide or other halogen flames, can effectively improve fire-retardant
Performance, the generation of smog when reducing burning, and the performance of the chemistry of adjustable Plastic Rubber Products, machinery, electricity etc.；As containing
The partially or completely environment-friend substitution product of the fire retardants such as halogen, are widely directly applied in the processing of plastics and rubber, such as poly-
Vinyl chloride (PVC), polypropylene (PP), reinforced polyamide, polychlorostyrene rouge, polystyrene (PS), epoxy resin, gathers polyethylene (PE)
Resin acid vinyl and natural rubber (NR), butadiene-styrene rubber (SBR), neoprene (CR) etc.；It can be applied to paper, fiber
Fabric, decorative panel, flooring laminate, wallpaper, carpet, ceramic glaze, fungicide, in the production of coating, to improve flame retardant property；It can also
It is enough in anti-corrosion, far infrared absorbs, the fields such as fungi-proofing processing of the insect prevention of timber.And because of zinc borate dehydration temperature with higher
Degree still retains the crystallization water, therefore commercial value with higher, the increasingly concern by market at 250 DEG C or more.
Ten thousand tons of the annual requirement 2-3 of China's zinc borate at present, but since the product of domestic autonomous production is in the microcosmic of product
There are patterns on pattern it is irregular, homogeneity is poor the problems such as, product is added into the materials such as macromolecule and causes material mechanical performance
It is poor, with external product there are still a certain distance, cause to produce in the zinc borate flame retardant of electric equal high-end fields application
Product are still completely dependent on import.
Therefore the preparation and microscopic appearance regulation method for developing a kind of zinc borate have very important theory significance and reality
Border meaning, while there is the huge market demand and vast market prospect.
Summary of the invention
The purpose of the present invention is for overcome above-mentioned existing zinc borate synthetic method product microscopic appearance it is irregular, reunite it is tight
The deficiency of weight etc. provides the preparation and microscopic appearance regulation method of a kind of 2335 type zinc borates.
To achieve the above object, the present invention uses following methods scheme:
A kind of preparation method of 2335 type zinc borate, comprising the following steps: (1) solution of zinc sulfate and sodium hydroxide solution,
Homogeneous reaction occurs by specific material adding manner, 40min is reacted at 15-35 DEG C, filters, filter cake is dried
To zinc hydroxide；(2) zinc hydroxide, boric acid are uniformly mixed with three kinds of materials of water, 2.5~8.5h are reacted at 80~105 DEG C,
Centrifugation, dry 2335 type zinc borate flame retardant products.
Preferably, the mass fraction of sodium hydroxide solution is 16-32%.
Preferably, the mass fraction of solution of zinc sulfate is 25%~35%.
Preferably, the molar ratio of zinc sulfate and sodium hydroxide is 1:1.9~2.1.
Preferably, the drying condition of zinc hydroxide is to be dried in vacuo in step (1), 80-100 DEG C of temperature, the time 30~60
Minute.
Preferably, the molar ratio of boric acid and zinc hydroxide is 1~3:1.
Preferably, the solid-to-liquid ratio of mixed material is 1.3:1 in step (2).Wherein, solid refers to the weight of zinc hydroxide and boric acid
Amount, liquid refer to that the quality of water, solid-to-liquid ratio are the weight ratio of the two.
Preferably, the drying condition of zinc borate is 105~150 DEG C of temperature, the time 2~3 hours in step (2).
On the basis of a kind of preparation method of above-mentioned 2335 type zinc borate, the present invention provides right in a kind of preparation process
In the regulation method of product microscopic appearance, specific method is the haptoreaction mode by changing zinc sulfate and sodium hydroxide solution
And the reaction activity that reaction temperature realizes the preparation of different activity zinc hydroxides, adjusts zinc borate synthesis temperature matching zinc hydroxide
The conditions such as demand control the reaction rate of zinc hydroxide and boric acid, further influence nucleation rate and life of the zinc borate in system
Long rate, this is formed by microscopic appearance to zinc borate and plays an important role.
A kind of microscopic appearance regulation method method of 2335 type zinc borate, comprising the following steps: 2335 type zinc borates are by upper
Method preparation is stated, the microcosmic of 2335 type zinc borates is regulated and controled by one of regulation (one), (two) parameter or two kinds of parameters
Pattern；
(1) the haptoreaction mode of zinc sulfate and sodium hydroxide solution；
(2) molar ratio of boric acid and zinc hydroxide, modification scope are 1~3:1.
Preferably, the haptoreaction mode of solution of zinc sulfate and sodium hydroxide solution includes the following three types in the present invention:
(1) first solution of zinc sulfate is added in reaction flask, opens stirring, sodium hydroxide solution is then added dropwise thereto；
It is reacted 40 minutes at 15 DEG C, filtering, drying obtain the zinc hydroxide of model ZnO-1；The characteristics of model zinc hydroxide is
Partial size is small, reaction activity is high；
(2) first sodium hydroxide solution is added in reaction flask, opens stirring, solution of zinc sulfate is then added dropwise thereto；
It is reacted 40 minutes at 25 DEG C, filtering, drying obtain the zinc hydroxide of model ZnO-2；The characteristics of model zinc hydroxide is
Partial size is big, reaction activity is low；
(3) solution of zinc sulfate is added into reaction flask simultaneously with sodium hydroxide solution, opens and stirs, in monitoring system
PH value realizes system pH between 8-10 by adjusting zinc sulfate and sodium hydroxide addition rate, obtains model ZnO-3
Zinc hydroxide；The characteristics of model zinc hydroxide be partial size between above two model, reaction activity it is moderate.
Preferably, according to above-mentioned regulation method, the size control range of 2335 type zinc borates is 2~10 μm, Morphological control
Range is graininess, sheet and bulk morphologies.
Preferably, it is prepared as described above method, it can also be by changing one of following parameter or two or more parameters
Adjusting the microscopic appearance of 2335 type zinc borates: the reaction time of (one) zinc hydroxide and boric acid, modification scope is 2.5~
8.5h；(2) reaction temperature of zinc hydroxide and boric acid, modification scope are 80~105 DEG C；(3) drying temperature of zinc borate is adjusted
Controlling range is 105~150 DEG C；(4) drying time of zinc borate, adjustable range are 2~3 hours.
Beneficial effects of the present invention:
The preparation of zinc hydroxide of the present invention is created different by the synthesis that change material Adding Way is zinc hydroxide
It is a kind of mistake of response type crystallization that condition, zinc solution and sodium hydroxide solution homogeneous reaction, which prepare zinc hydroxide precipitation substantially,
Journey can realize the different crystal morphology of generation by changing crystallization condition.Solution of zinc sulfate is added dropwise to strong basicity liquid alkaline
In solution, as the increase zinc hydroxide of dripping quantity is slowly precipitated, this is because the polyhydroxy hydrogen-oxygen generated under the synthesis condition
Change zinc ligand has biggish solubility under strong basicity, and zinc hydroxide degree of supersaturation is low, and crystallization rate is slower, crystal growth rate
Greater than nucleation rate, material grains are big.Otherwise liquid alkaline is added dropwise in faintly acid solution of zinc sulfate, the quick crystallization precipitating of meeting is brilliant
Body nucleation rate is greater than growth rate, and material grains are small.It, can be by regulating and controlling material to realize further median diameter regulation
Contact ratio makes system pH in alkalescent (pH=8-10) range, realizes the matching of crystal nucleation rate and growth rate,
Obtain median particle size product.For most solid matters, reaction activity is proportional to its specific surface area, is inversely proportional to partial size,
The present invention is three kinds of model zinc hydroxides by partial size different demarcation, and the smaller reaction activity of partial size is higher.It is higher to react activity
Zinc hydroxide is very fast with the reaction speed of boric acid in the synthesis process of zinc borate, and matching suitable reaction temperature can be thus achieved
To the stability contorting of zinc borate crystalline rate.Different zinc borates can be regulated and controled out from the reaction rate of boric acid by changing zinc hydroxide
Crystal nucleation rate and crystal growth rate, the rate-matched of the two and the microscopic appearance of zinc borate are directly related.Pass through this
The regulation and control scheme of invention, realize the uniform rule of zinc borate products, and fine particle, sheet, bulk can be prepared etc.
The zinc borate products of pattern.
Implementation of the invention is able to solve traditional zinc borate production technology product microscopic appearance is irregular, the side such as inhomogenous
The defect in face produces the controllable differentiated products of series of stable, suitable for different application fields, can effectively reverse me
The high-end zinc borate products of state need to rely on the situation of market import, have boundless market prospects.
Detailed description of the invention
Fig. 1 is the SEM picture of 1 product of embodiment；
Fig. 2 is the SEM picture of 2 product of embodiment；
Fig. 3 is the SEM picture of 3 product of embodiment；
Fig. 4 is the SEM picture of 4 product of embodiment；
Specific embodiment
The present invention will be further elaborated combined with specific embodiments below, it should which explanation, following the description are only
In order to explain the present invention, its content is not defined.
Embodiment 1
The aqueous solution 644g (1mol) of 25% zinc sulfate is added into reaction flask, opens stirring, controlled at 15 DEG C, to
32% sodium hydroxide solution 237.5g (1.9mol) is added dropwise in reaction flask, 40min is reacted at 15 DEG C, filters, 90 DEG C of vacuum
Dry 45min obtains model ZnO-1 zinc hydroxide.99g zinc hydroxide (1mol) and 185.5g boric acid (3mol), 218.8g water are existed
4.5h is reacted at 80 DEG C, is centrifugated, and dry 2h obtains ZB-1 model zinc borate at 125 DEG C, and microscopic appearance is uniform particle diameter
Graininess, about 2 μm of partial size D50.
Embodiment 2
The sodium hydroxide solution of the aqueous solution 644g (1mol) and 32% of 25% zinc sulfate is added dropwise simultaneously into reaction flask
262.5g (2.1mol) opens stirring, and maintaining reaction temperature is 25 DEG C, and adjusting the two rate of addition maintains reacting liquid pH value
Between 8-10,40min, filtering are reacted, 90 DEG C of vacuum drying 45min obtain model ZnO-2 zinc hydroxide.By 99g zinc hydroxide
(1mol) reacts 4.5h at 90 DEG C with 123.6g boric acid (2mol), 171.2g water, centrifuge separation, and dry 2h obtains ZB- at 125 DEG C
3 model zinc borates, microscopic appearance be uniform particle diameter sheet, about 4 μm of partial size D50.
Embodiment 3
32% sodium hydroxide solution 237.5g (1.9mol) is added into reaction flask, stirring is opened, controlled at 35
DEG C, the aqueous solution 460g (1mol) of 35% zinc sulfate is added dropwise, 40min is reacted at 25 DEG C, filters, 90 DEG C of vacuum drying 45min
Obtain model ZnO-3 zinc hydroxide.99g zinc hydroxide (1mol) and 61.83g boric acid (1mol), 123.7g water is anti-at 95 DEG C
4.5h is answered, is centrifugated, dry 2h obtains ZB-3 model zinc borate at 125 DEG C, and microscopic appearance is the bulk of uniform particle diameter, partial size
About 8 μm of D50.
Embodiment 4
32% sodium hydroxide solution 237.5g (1.9mol) is added into reaction flask, stirring is opened, controlled at 35
DEG C, the aqueous solution 460g (1mol) of 35% zinc sulfate is added dropwise, 40min is reacted at 35 DEG C, filters, 90 DEG C of vacuum drying 45min
Obtain model ZnO-4 zinc hydroxide.99g zinc hydroxide (1mol) and 61.83g boric acid (1mol), 123.7g water is anti-at 105 DEG C
4.5h is answered, is centrifugated, dry 2h obtains ZB-3 model zinc borate at 125 DEG C, and microscopic appearance is the bulk of uniform particle diameter, partial size
About 10 μm of D50.
Above-mentioned, although specific embodiments of the present invention have been described, not to the limit of the scope of the present invention
System, on the basis of method of the invention, art processes personnel do not need to make the creative labor can make various and repair
Change or deforms still within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of 2335 type zinc borates, which comprises the following steps: (1) solution of zinc sulfate and hydrogen-oxygen
Change sodium solution, homogeneous reaction is occurred by specific material adding manner, 40min is reacted at 15-35 DEG C, is filtered, to filter cake
It is dried to obtain zinc hydroxide；(2) zinc hydroxide, boric acid are uniformly mixed with three kinds of materials of water, are reacted at 80~105 DEG C
2.5~8.5h, centrifugation, dry 2335 type zinc borate flame retardant products.
2. a kind of preparation method of 2335 type zinc borate according to claim 1, which is characterized in that sodium hydroxide solution
Mass fraction is 16-32%.
3. a kind of preparation method of 2335 type zinc borate according to claim 1, which is characterized in that the matter of solution of zinc sulfate
Measuring score is 25%~35%.
4. a kind of preparation method of 2335 type zinc borate according to claim 1, which is characterized in that zinc sulfate and hydroxide
The molar ratio of sodium is 1:1.9~2.1.
5. a kind of preparation method of 2335 type zinc borate according to claim 1, which is characterized in that hydrogen-oxygen in step (1)
The drying condition for changing zinc is to be dried in vacuo, 80-100 DEG C of temperature, the time 30~60 minutes.
6. a kind of preparation method of 2335 type zinc borate according to claim 1, which is characterized in that boric acid and zinc hydroxide
Molar ratio be 1~3:1.
7. a kind of preparation method of 2335 type zinc borate according to claim 1, which is characterized in that boric acid in step (2)
The drying condition of zinc is 105~150 DEG C of temperature, the time 2~3 hours.
8. a kind of microscopic appearance of 2335 type zinc borates regulates and controls method method, which comprises the following steps: 2335 type boron
Sour zinc is prepared according to the above method, regulates and controls 2335 type boric acid by one of regulation (one), (two) parameter or two kinds of parameters
The microscopic appearance of zinc；
(1) the haptoreaction mode of zinc sulfate and sodium hydroxide solution；
(2) molar ratio of boric acid and zinc hydroxide, modification scope are 1~3:1.
9. a kind of microscopic appearance of 2335 type zinc borate according to claim 8 regulates and controls method method, which is characterized in that sulphur
The haptoreaction mode of sour zinc solution and sodium hydroxide solution includes the following three types:
(1) first solution of zinc sulfate is added in reaction flask, opens stirring, sodium hydroxide solution is then added dropwise thereto；15
It is reacted 40 minutes at DEG C, filtering, drying obtain the zinc hydroxide of model ZnO-1；The characteristics of model zinc hydroxide is partial size
Small, reaction activity height；
(2) first sodium hydroxide solution is added in reaction flask, opens stirring, solution of zinc sulfate is then added dropwise thereto；25
It is reacted 40 minutes at DEG C, filtering, drying obtain the zinc hydroxide of model ZnO-2；The characteristics of model zinc hydroxide is partial size
Greatly, reaction activity is low；
(3) solution of zinc sulfate is added into reaction flask simultaneously with sodium hydroxide solution, opens and stirs, pH value in monitoring system,
System pH is realized between 8-10 by adjusting zinc sulfate and sodium hydroxide addition rate, obtains the hydrogen of model ZnO-3
Zinc oxide；The characteristics of model zinc hydroxide be partial size between above two model, reaction activity it is moderate.
10. a kind of microscopic appearance of 2335 type zinc borate according to claim 8 regulates and controls method method, which is characterized in that
The size control range of 2335 type zinc borates is 2~10 μm, and Morphological control range is graininess, sheet and bulk.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811249987.5A CN109179445B (en) | 2018-10-25 | 2018-10-25 | 2335 type zinc borate preparation and microstructure regulation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811249987.5A CN109179445B (en) | 2018-10-25 | 2018-10-25 | 2335 type zinc borate preparation and microstructure regulation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109179445A true CN109179445A (en) | 2019-01-11 |
| CN109179445B CN109179445B (en) | 2022-02-18 |
Family
ID=64943488
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811249987.5A Active CN109179445B (en) | 2018-10-25 | 2018-10-25 | 2335 type zinc borate preparation and microstructure regulation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109179445B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06256013A (en) * | 1993-02-26 | 1994-09-13 | Hakusui Chem Ind Ltd | Production of zinc borate |
| CN1296916A (en) * | 2000-12-29 | 2001-05-30 | 山东大学 | Process for preparing nm powder of zinc oxide |
| CN101298333A (en) * | 2008-07-02 | 2008-11-05 | 武汉大学 | Preparation of 2ZnO.2B2O3.3.5H2O zinc borate |
| CN101486469A (en) * | 2009-02-27 | 2009-07-22 | 甄曰菊 | Preparation of superfine low hydration zinc borate |
| CN104609437A (en) * | 2015-02-03 | 2015-05-13 | 中国科学院过程工程研究所 | Preparation method of superfine 2335 zinc borate fire retardant |
-
2018
- 2018-10-25 CN CN201811249987.5A patent/CN109179445B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06256013A (en) * | 1993-02-26 | 1994-09-13 | Hakusui Chem Ind Ltd | Production of zinc borate |
| CN1296916A (en) * | 2000-12-29 | 2001-05-30 | 山东大学 | Process for preparing nm powder of zinc oxide |
| CN101298333A (en) * | 2008-07-02 | 2008-11-05 | 武汉大学 | Preparation of 2ZnO.2B2O3.3.5H2O zinc borate |
| CN101486469A (en) * | 2009-02-27 | 2009-07-22 | 甄曰菊 | Preparation of superfine low hydration zinc borate |
| CN104609437A (en) * | 2015-02-03 | 2015-05-13 | 中国科学院过程工程研究所 | Preparation method of superfine 2335 zinc borate fire retardant |
Non-Patent Citations (1)
| Title |
|---|
| 陈志玲 等: ""纳米级低水硼酸锌的微波合成、表征及应用"", 《北京石油化工学院学报》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109179445B (en) | 2022-02-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104497435B (en) | Preparation method of ultravioresistant PVC composite material suitable for plateau environment | |
| CA1254717A (en) | Magnesium hydroxide and process for its production | |
| CN110028702B (en) | Nano-silica-doped nano-cellulose material and preparation method and application thereof | |
| CN103937032A (en) | Cellulose nanocrystal/graphene composite colored film and fast preparation method thereof | |
| CN106673027A (en) | Preparation and synthesis method of hexagonal flaky magnesium hydroxide fire retardant | |
| CN111943246B (en) | Preparation method and application of calcium carbonate special for waterproof breathable film | |
| KR100906009B1 (en) | Electroconductive zinc oxide powder and method for production thereof, and electroconductive composition | |
| CN108570257A (en) | A kind of method of modifying of ammonium polyphosphate for aqueous fire-proof coating | |
| CN113045762A (en) | Modified MOFs flame retardant and preparation method and application thereof | |
| CN104448948B (en) | The preparation method of modified hypo-aluminum orthophosphate | |
| CN106589656B (en) | A kind of fire-retardant master granule and its flame retardant type PVC wood plastic wall board being prepared | |
| CN108047500B (en) | Aluminum silicate coated hydrotalcite flame retardant | |
| CN109179445A (en) | The preparation of 2335 type zinc borates and microscopic appearance regulate and control method | |
| CN110698772A (en) | Modified ammonium polyphosphate/modified graphene oxide flame-retardant runway particle material | |
| CN102827495A (en) | Preparation method of high transparent precipitated silica for plastic anti-block agent | |
| CN108864971A (en) | A kind of preparation method of automobile-used rupture pressure disc | |
| CN112898811B (en) | Antibacterial self-repairing microcapsule, preparation method thereof and application thereof in coating | |
| CN110357134B (en) | Particle size control method in aluminum hydroxide synthesis process | |
| CN105948105A (en) | SnO2/ZnO nano composite material and preparation method thereof | |
| CN100398441C (en) | Method of preparing nano-zinc borate | |
| CN112408440A (en) | Process for preparing superfine coral velvet-shaped environment-friendly magnesium hydroxide by batch hydrothermal method | |
| CN109575469A (en) | The preparation method of the dedicated calcium acetylacetonate of PVC heat stabilizer | |
| CN113698821B (en) | Ultraviolet barrier coating and preparation method and application thereof | |
| CN108706606A (en) | A kind of process preparing zinc borate | |
| CN109319793A (en) | A kind of preparation method of Gao Bibiao, high oil absorption white carbon black |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Liu Qikui Inventor after: Yue Tao Inventor after: Feng Weichun Inventor after: Di Yunge Inventor after: Gao Weidan Inventor after: Li Peipei Inventor after: Wang Hao Inventor before: Xing Wenguo Inventor before: Yue Tao Inventor before: Feng Weichun Inventor before: Wang Ruifei Inventor before: Gao Weidan Inventor before: Tang Xiaochan |
|
| CB03 | Change of inventor or designer information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |