CN104609437A - Preparation method of superfine 2335 zinc borate fire retardant - Google Patents
Preparation method of superfine 2335 zinc borate fire retardant Download PDFInfo
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- CN104609437A CN104609437A CN201510055763.0A CN201510055763A CN104609437A CN 104609437 A CN104609437 A CN 104609437A CN 201510055763 A CN201510055763 A CN 201510055763A CN 104609437 A CN104609437 A CN 104609437A
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- zinc
- zinc borate
- borax
- superfine
- boric acid
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- 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
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- 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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Abstract
The invention provides a preparation method of superfine 2335 zinc borate fire retardant. The fire retardant is prepared from boric acid, sodium borate, zinc sulfate and zinc oxide and the like in the presence of inert microspheres serving as both abradant and a dispersing agent according to a certain proportion and process. The superfine 2335 zinc borate fire retardant prepared by the method has small particle diameter, the median particle diameter d (50) is in the range of 0.5-1.2mu m. The preparation method is simple and the cost is low; the process is clean and environmentally friendly, and pollutant emission is avoided; the superfine 2335 zinc borate fire retardant prepared by the invention has stable and excellent fire retarding and smoke inhibiting performances, so the superfine 2335 zinc borate fire retardant is widely used in products such as plastic, rubber, wire cable, coating and painting.
Description
Technical field
The present invention relates to a kind of ultra-fine 2335 zinc borate flame retardant preparation methods, belong to technical field of inorganic material synthesis.
Technical background
Zinc borate have fire-retardant, press down hood, be environmental protection non-halogen fire retardant, both can be used alone, also can compositely use, being widely used in the aspects such as plastics, rubber, electric wire, electronic products shell, coating, paint, is the special-purpose anti-flaming raw material of rubber conveyer belt and radial.Zinc borate is of a great variety, and wherein molecular composition is 2ZnO3B
2o
33.5H
2o is that most is representative, flame retardant effect is better, widely used fire retardant also referred to as 2335 zinc borates.The size of zinc borate directly affects its dispersiveness in other material, and then affects flame retardant effect and addition, finally affects production cost.The particle diameter of current domestic production zinc borate is mostly more than 3 μm, and submicron-grade superfine 2335 zinc borate is the important directions of its development.
Zinc borate preparation method mainly contains three kinds, i.e. boric acid zinc oxide method, boric acid zinc hydroxide method and borax zincate process, zinc oxide method Problems existing is that zinc oxide is somewhat expensive, zinc hydroxide method Problems existing is that zinc hydroxide needs in situ preparation, borax method cost is lower, need Matter Transfer, treatment process relative complex.
CN 1167730A discloses a kind of preparation method of superfine zinc borate flame retardant.The method for main raw material, adds tensio-active agent with boric acid and zinc oxide at 70 ~ 95 DEG C, reaction 5.5 ~ 8h, at drying temperature 95 DEG C, and obtained 2235 superfine zinc borates.The method adopts zinc oxide method, and need tensio-active agent, cost is higher simultaneously; The method reaction times is also longer, and the zinc borate particle diameter that the method is produced is at 2 ~ 3 μm, and particle diameter comparatively conference affects its dispersiveness, and then affects flame retardant effect.
CN 1321060C discloses a kind of preparation method of zinc borate.The method adopts zinc oxide method, adds water again in stream metamorphosis, in closed reactor, react 6 ~ 12h at 60 ~ 100 DEG C after boric acid and zinc oxide being mixed in advance, under 120 ~ 140 DEG C of dryings, and obtained zinc borate.It is high equally to there is zinc oxide cost in the method, long reaction time, and the wayward zinc borate particle diameter of stream transformation reactions, be difficult to obtain superfine product, the not good problem of flame retardant effect.
CN 101774602A discloses the preparation method of a kind of coarse grain footpath 2335 zinc borate.The method, is reacted more than 6 hours at 60 ~ 100 DEG C for raw material with borax, Zinc Sulphate Heptahydrate and zinc oxide, 2335 zinc borates of obtained median 8 ~ 10 μm.The method subject matter is that the reaction times is long, and temperature of reaction is also higher, and embodiment is all more than 90 DEG C, and owing to can only prepare coarse grain footpath zinc borate, its application is restricted, and can only be used for anticorrosion, can not be used as fire-retardant.
Wu Zhi equality is in " preparation of superfine zinc borate flame retardant and performance study thereof " paper, Liu Xianglei etc. are all studied 2335 zinc borate preparations in " superfine low hydration zinc borate study on the synthesis " paper, the former with borax and zinc chloride for raw material, can synthesis nano zinc borate, but adopt organic dispersing agent, there is recovery problem, high speed shear, severe reaction conditions.The latter with borax, zinc sulfate and boric acid for main raw material, replace zinc oxide with boric acid, significantly reduce the reaction times, the method Problems existing is that temperature of reaction must more than 90 DEG C, and the granularity of the zinc borate obtained can only, below 6 μm, still be difficult to reach good flame retardant effect.
In sum, development or exploitation one effectively can reduce the reaction times, significantly reduce zinc borate grain diameter, and the zinc borate flame retardant preparation method of excellent flame retardancy very has realistic meaning.
The present invention is devoted to solve the technical problem existed in above-mentioned prior art, adopt specific inert microspheres as dispersion grinding medium, to react and size controlling organic coupling, reaction times is significantly reduced, zinc oxide dosage significantly reduces, obtained 2335 zinc borate flame retardant particle diameters are tiny, and median d (50) is 0.5 ~ 1.5 μm, and the flame retarding and smoke suppressing properties of fire retardant is stable, excellent.
Summary of the invention
The invention provides a kind of ultra-fine 2335 zinc borate flame retardant preparation methods, the raw material that this preparation method adopts and composed as follows:
(1) raw materials used is borax, boric acid, zinc sulfate, zinc oxide, water, and dispersion used and grinding medium are inert microspheres;
(2) in above-mentioned raw materials, borax is borax decahydrate, and zinc sulfate is Zinc Sulphate Heptahydrate, and inert microspheres material is zirconium white;
(3) quality group of above-mentioned each raw material becomes: borax 10 ~ 18%, boric acid 10 ~ 16%, zinc sulfate 7 ~ 15%, zinc oxide 0.1 ~ 1%, water 55 ~ 75%;
(4) preferred above-mentioned raw materials quality group becomes: borax 13 ~ 15%, boric acid 12 ~ 14%, zinc sulfate 10 ~ 12%, zinc oxide 0.4 ~ 0.6%, water 60 ~ 70%;
(5) zirconium oxide microballoons is single particle size or multiple mechanical fraction, and microspherulite diameter scope is 0 ~ 5mm, preferably 0 ~ 3mm;
2335 zinc borate flame retardant preparation methods comprise following operation steps:
A. in reactor, a certain amount of water is added;
B. in a, add certain particle size, a certain amount of inert microspheres stir, heat up;
C. in b, add borax and boric acid when temperature is raised to 50 ~ 70 DEG C, make it dissolve completely;
D. in c, add zinc sulfate and zinc oxide, control temperature of reaction about 80 DEG C, reaction 3 ~ 4h, stopped reaction;
E. reaction terminate after by d inert microspheres be separated, reaction mass after filtration, washing, filtrate reclaim, filter cake drying obtains ultra-fine 2335 zinc borates.
According to raw material of the present invention, composition, operating parameters and step, can obtain superfine zinc borate flame retardant, its molecular composition is 2ZnO3B
2o
33.5H
2o, i.e. 2335 zinc borates; Its particle diameter is tiny, and median d (50) is 0.5 ~ 1.5 μm, and the flame retarding and smoke suppressing properties of fire retardant is stable, excellent.
Below in conjunction with drawings and Examples, the present invention is further illustrated.
Accompanying drawing explanation
Fig. 1 is ultra-fine 2335 zinc borate flame retardant preparation technology schematic flow sheets of the present invention.
Embodiment
One exemplary embodiment further describes of the present invention, but these embodiments do not form any limitation of the invention.
Embodiment 1
First in reactor, add 1500ml water, 1000g particle diameter 2.3 ~ 3.0mm zirconium oxide microballoons, open and stir, be warmed up to 70 DEG C, add 300g boric acid and 350g borax decahydrate, until completely dissolved, add 250g Zinc Sulphate Heptahydrate and 10g zinc oxide, controlling temperature of reaction is 80 DEG C, reaction 3.5h, reaction terminates rear filter screen and isolates inert microspheres and filtered while hot, with hot wash filter cake 2 times, filtrate is reclaimed, and filter cake is dry 2.5h at 80 DEG C, obtain zinc borate flame retardant, it consists of 2ZnO3B
2o
33.5H
2o, median d (50) are 0.918 μm.
Embodiment 2
First in reactor, 2000ml water is added, 500g 1.0 ~ 1.8mm particle diameter and 500g 2.3 ~ 3.0mm particle diameter zirconium oxide microballoons, open and stir, be warmed up to 70 DEG C, add 380g boric acid and 420g borax decahydrate, until completely dissolved, add 350g Zinc Sulphate Heptahydrate and 15g zinc oxide, controlling temperature of reaction is 80 DEG C, reaction 4h, reaction terminates rear filter screen and separates inert microspheres and filtered while hot, with hot wash filter cake 2 times, filtrate is reclaimed, and filter cake is dry 3h at 80 DEG C, obtain zinc borate flame retardant, it consists of 2ZnO3B
2o
33.5H
2o, median d (50) are 0.992 μm.
Embodiment 3
First in reactor, 1800ml water is added, 300g particle diameter 1.0 ~ 1.8mm, 300g particle diameter 1.8 ~ 2.3mm and 400g particle diameter 2.3 ~ 3.0mm zirconium oxide microballoons, open and stir, be warmed up to 70 DEG C, add 360g boric acid and 400g borax decahydrate, until completely dissolved, add 335g Zinc Sulphate Heptahydrate and 13g zinc oxide, controlling temperature of reaction is 80 DEG C, reaction 3.5h, reaction terminates rear filter screen and separates inert microspheres and filtered while hot, with hot wash filter cake 2 times, filtrate is reclaimed, filter cake is dry 3.5h at 80 DEG C, obtain zinc borate flame retardant, it consists of 2ZnO3B
2o
33.5H
2o, median d (50) are 0.935 μm.
Although show and described several embodiment of the present invention, the present invention has not been restricted to described embodiment.On the contrary; those skilled in the art should recognize when not departing from principle of the present invention and spirit; can carry out any accommodation and improvement to these embodiments, protection scope of the present invention determined by appended claim and equivalent thereof.
Claims (6)
1. ultra-fine 2335 zinc borate flame retardant preparation methods, is characterized in that:
(1) with borax, boric acid, zinc sulfate, zinc oxide and water for raw material, with inert microspheres be dispersion and grinding medium, react under certain temperature and alr mode, generation molecular formula is 2ZnO3B
2o
33.5H
2the superfine zinc borate flame retardant of O, also claims 2335 zinc borate flame retardants, and the quality group of each raw material becomes: borax 10 ~ 18%, boric acid 10 ~ 16%, zinc sulfate 7 ~ 15%, zinc oxide 0.1 ~ 1%, water 55 ~ 75%;
(2) each raw material adds in reactor according to certain form and order, certain particle size, a certain amount of inert microspheres add in a certain way, stir and control temperature of reaction, through solid-liquid separation, washing after reaction terminates, filtrate is reclaimed, and filter cake drying obtains ultra-fine 2335 zinc borate flame retardants.
2. method according to claim 1, described borax is borax decahydrate, and described zinc sulfate is Zinc Sulphate Heptahydrate; The quality group of each raw material becomes: borax 13 ~ 15%, boric acid 12 ~ 14%, zinc sulfate 10 ~ 12%, zinc oxide 0.4 ~ 0.6%, water 60 ~ 70%.
3. method according to claim 1, described inert microspheres is zirconium oxide microballoons, and be single particle size or many mechanical fractions, microspherulite diameter scope is 0 ~ 5mm.
4. method according to claim 3, described microspherulite diameter scope is 0 ~ 3mm.
5. the method according to right 1 or 2, adds water and inert microspheres first in the reactor, and stirring is warmed up to 50 ~ 70 DEG C and adds borax and boric acid, adds zinc sulfate and zinc oxide after stirring and dissolving is complete.
6. method according to claim 1 and 2, the ultra-fine 2335 zinc borate flame retardant molecular compositions of the present invention are 2ZnO3B
2o
33.5H
2o; Median d (50) is 0.5 ~ 1.5 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510055763.0A CN104609437A (en) | 2015-02-03 | 2015-02-03 | Preparation method of superfine 2335 zinc borate fire retardant |
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| CN201510055763.0A CN104609437A (en) | 2015-02-03 | 2015-02-03 | Preparation method of superfine 2335 zinc borate fire retardant |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109095475A (en) * | 2018-10-25 | 2018-12-28 | 青岛科技大学 | A kind of preparation and size control method of 2335 type zinc borate |
| CN109179445A (en) * | 2018-10-25 | 2019-01-11 | 青岛科技大学 | The preparation of 2335 type zinc borates and microscopic appearance regulate and control method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06256013A (en) * | 1993-02-26 | 1994-09-13 | Hakusui Chem Ind Ltd | Production of zinc borate |
| CN1903722A (en) * | 2006-07-07 | 2007-01-31 | 上海安亿纳米材料有限公司 | Method of preparing nano-zinc borate |
-
2015
- 2015-02-03 CN CN201510055763.0A patent/CN104609437A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06256013A (en) * | 1993-02-26 | 1994-09-13 | Hakusui Chem Ind Ltd | Production of zinc borate |
| CN1903722A (en) * | 2006-07-07 | 2007-01-31 | 上海安亿纳米材料有限公司 | Method of preparing nano-zinc borate |
Non-Patent Citations (1)
| Title |
|---|
| 刘向磊: "超细低水合硼酸锌的制备及母液处理方法的新工艺研究", 《中国学位论文全文数据库》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109095475A (en) * | 2018-10-25 | 2018-12-28 | 青岛科技大学 | A kind of preparation and size control method of 2335 type zinc borate |
| CN109179445A (en) * | 2018-10-25 | 2019-01-11 | 青岛科技大学 | The preparation of 2335 type zinc borates and microscopic appearance regulate and control method |
| CN109179445B (en) * | 2018-10-25 | 2022-02-18 | 青岛科技大学 | 2335 type zinc borate preparation and microstructure regulation method |
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Application publication date: 20150513 |