CN102060306A - Method for preparing superfine zinc borate - Google Patents

Method for preparing superfine zinc borate Download PDF

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Publication number
CN102060306A
CN102060306A CN 201110000900 CN201110000900A CN102060306A CN 102060306 A CN102060306 A CN 102060306A CN 201110000900 CN201110000900 CN 201110000900 CN 201110000900 A CN201110000900 A CN 201110000900A CN 102060306 A CN102060306 A CN 102060306A
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zinc borate
solution
borax
zinc
kinds
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CN102060306B (en
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殷恒波
廖喜慧
于洋
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Jiangsu University
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Jiangsu University
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Abstract

The invention discloses a method for preparing superfine zinc borate. The method for preparing the superfine zinc borate comprises the following steps of: preparing aqueous solution from borax and zinc sulfate which serve as raw materials; placing the two kinds of solution into a three-neck flask according to the ratio of the two kinds of solution of 1:1; adding an organic modifier, namely polyethylene glycol (PEG-400, the average molecular weight is 380 to 420) or polyvinyl alcohol (the average molecular weight is 120,000 to 150,000), in an amount which is 0.5 to 0.8 percent of the total mass of the liquid; stirring uniformly. heating the mixture to be 60 to 95 DEG C, and continuously stirring for 1.5 hours at the mechanically stirring speed of 500 revolutions per minute; and after the reaction is finished, filtering, washing with water and performing vacuum drying at the temperature of 80 DEG C. In the zinc borate prepared by the method, the structural formula is 2ZnO.3B2O3.3.5H2O and the grain size is between 40 and 950 nm. The zinc borate product has small grain size and uniformly-distributed dimension; the reaction condition is easy to control; the cost is low; the preparation process is simple and the flow is simple and convenient; and requirements of industrialized production are met.

Description

A kind of method for preparing superfine zinc borate
Technical field
The objective of the invention is to disclose a kind of is raw material with borax, zinc sulfate, and prepares the method for superfine zinc borate by adding organic modifier, belongs to field of inorganic materials.
Background technology
Zinc borate is a kind of non-halogen flame retardant of environment-friendly type, according to forming different (XZnO YB 2O 3ZH 2O), fire retardant has tens kinds.The most frequently used kind is this product-3.5 hydrate zinc borate, claims the ZB-2335 fire retardant again.Characteristics such as this product is nontoxic, low water solubility, high thermal stability, granularity is little, proportion is little, good dispersity are widely used in fields such as plastics, rubber, coating as a kind of efficient flame-retarding agent.The manufacturing process of zinc borate generally is to adopt boric acid and zinc oxide reaction, or adopts borax and zinc salt reaction at present, makes zinc borate.For example Chinese patent 200910010594.3, and name is called: a kind of organic acid modified zinc borate.Adopt zinc oxide and boric acid to prepare zinc borate in this invention, this method is introduced organic acid zinc borate is modified, and has increased reaction cost, simultaneously, long reaction time, energy consumption is big.Chinese patent 200610028724.2, name is called a kind of method for preparing nano-zinc borate, and the method complicated operation of this Invention Announce has by product to produce in the reaction process, need subsequent disposal, has increased reaction cost.
Hydration zinc borate is a kind of mineral compound of surperficial possess hydrophilic property, and dispersion that it is relatively more weak in organic medium and performance such as compatible have limited the Application Areas of hydration zinc borate.Therefore, to the zinc borate surface carry out organic molecule modification, improve the performance of zinc borate in organic medium, improve the consistency of inorganic zinc borate compound and polymkeric substance macromolecular material, have crucial meaning.
The present invention proposes the contriver has done the basis of conscientious research to existing zinc borate preparation technology on.
Summary of the invention
Of the present invention in order to overcome above-mentioned deficiency of the prior art, disclosing a kind of is raw material with borax, zinc sulfate, and prepares the method for superfine zinc borate by interpolation organic modifier polyoxyethylene glycol or polyvinyl alcohol.
The method for preparing superfine zinc borate of the present invention is carried out according to following steps:
With borax, zinc sulfate is the borax solution of preparation of raw material 0.30-1.60mol/L, the zinc sulfate solution of 0.30-1.60mol/L, pressing the mol ratio of 1:1 mixes above-mentioned two kinds of solution, add after the organic modifier polyoxyethylene glycol of the 0.5-0.8% account for the liquid total mass or polyvinyl alcohol stir, be warming up to 60-95 ℃, continue to stir 1.5h with 500 rev/mins mechanical stirring speed; After reaction finishes, filter, wash 80 ℃ of vacuum dryings; The particle diameter of gained zinc borate is between 40-950nm;
Wherein said polyoxyethylene glycol is PEG-400, and its molecular-weight average is 380-420; Wherein said polyvinyl alcohol phase molecular-weight average 12-15 ten thousand, alcoholysis degree 88%.
The present invention compares with existing zinc borate technology of preparing and has the following advantages:
Borax, zinc sulfate are easy as the stable reaction of feedstock production zinc borate, are easy to carry out in various reactors.The present invention shortens by beginning to add organic modifier polyoxyethylene glycol (PEG-400, molecular-weight average are 380-420) or polyvinyl alcohol (molecular-weight average 12-15 ten thousand) in reaction, make the reaction times that obtains product, has reduced the energy consumption of reaction; Simultaneously, the product surface performance improves, and is difficult for suction, is easy to store.Products obtained therefrom detects through X-ray crystalline diffraction instrument, and the structural formula of the zinc borate that is generated is all: 2ZnO 3B 2O 33.5H 2O, particle diameter is between 40-950nm; The grain diameter of product is little, even size distribution, and reaction conditions is easy to control, cost is low, and preparation technology is simple, and simple flow meets industrial production requirement.
Embodiment
Comparative Examples 1:
With borax, zinc sulfate is the borax solution of preparation of raw material 0.30mol/L, the zinc sulfate solution of 0.30mol/L, mol ratio by 1:1 places there-necked flask with above-mentioned two kinds of solution, be warming up to 60 ℃, continue to stir 2.5h with 500 rev/mins mechanical stirring speed; After reaction finishes, filter, wash 80 ℃ of vacuum dryings.The gained zinc borate detects through X-ray crystalline diffraction instrument, and structural formula is: 2ZnO 3B 2O 33.5H 2O, particle diameter are 87 μ m.
Comparative Examples 2:
With borax, zinc sulfate is the borax solution of preparation of raw material 0.30mol/L, the zinc sulfate solution of 0.30mol/L, mol ratio by 1:1 places there-necked flask with above-mentioned two kinds of solution, be warming up to 95 ℃, continue to stir 2.5h with 500 rev/mins mechanical stirring speed; After reaction finishes, filter, wash 80 ℃ of vacuum dryings.The gained zinc borate detects through X-ray crystalline diffraction instrument, and structural formula is: 2ZnO 3B 2O 33.5H 2O, particle diameter are 44 μ m.
Embodiment 1:
With borax, zinc sulfate is the borax solution of preparation of raw material 0.30mol/L, the zinc sulfate solution of 0.30mol/L, mol ratio by 1:1 places there-necked flask with above-mentioned two kinds of solution, add 0.5% the organic modifier polyoxyethylene glycol (PEG-400 account for the liquid total mass, molecular-weight average is 380-420) stir after, be warming up to 60 ℃, continue to stir 1.5h with 500 rev/mins mechanical stirring speed; After reaction finishes, filter, wash 80 ℃ of vacuum dryings.The gained zinc borate detects through X-ray crystalline diffraction instrument, and structural formula is: 2ZnO 3B 2O 33.5H 2O, particle diameter are 43nm.
Embodiment 2:
With borax, zinc sulfate is the borax solution of preparation of raw material 0.30mol/L, the zinc sulfate solution of 0.30mol/L, mol ratio by 1:1 places there-necked flask with above-mentioned two kinds of solution, add after 0.5% the organic modifier polyvinyl alcohol (molecular-weight average 12-15 ten thousand) account for the liquid total mass stirs, be warming up to 60 ℃, continue to stir 1.5h with 500 rev/mins mechanical stirring speed; After reaction finishes, filter, wash 80 ℃ of vacuum dryings.The gained zinc borate detects through X-ray crystalline diffraction instrument, and structural formula is: 2ZnO 3B 2O 33.5H 2O, particle diameter are 117nm.
Embodiment 3:
With borax, zinc sulfate is the borax solution of preparation of raw material 1.60mol/L, the zinc sulfate solution of 1.60mol/L, mol ratio by 1:1 places there-necked flask with above-mentioned two kinds of solution, add after 0.5% the organic modifier polyvinyl alcohol (molecular-weight average 12-15 ten thousand) account for the liquid total mass stirs, be warming up to 95 ℃, continue to stir 1.5h with 500 rev/mins mechanical stirring speed; After reaction finishes, filter, wash 80 ℃ of vacuum dryings.The gained zinc borate detects through X-ray crystalline diffraction instrument, and structural formula is: 2ZnO 3B 2O 33.5H 2O, particle diameter are 196nm.
Embodiment 4:
With borax, zinc sulfate is the borax solution of preparation of raw material 1.60mol/L, the zinc sulfate solution of 1.60mol/L, mol ratio by 1:1 places there-necked flask with above-mentioned two kinds of solution, add 0.5% the organic modifier polyoxyethylene glycol (PEG-400 account for the liquid total mass, molecular-weight average is 380-420) stir after, be warming up to 95 ℃, continue to stir 1.5h with 500 rev/mins mechanical stirring speed; After reaction finishes, filter, wash 80 ℃ of vacuum dryings.The gained zinc borate detects through X-ray crystalline diffraction instrument, and structural formula is: 2ZnO 3B 2O 33.5H 2O, particle diameter are 313nm.
Embodiment 5:
With borax, zinc sulfate is the borax solution of preparation of raw material 1.60mol/L, the zinc sulfate solution of 1.60mol/L, mol ratio by 1:1 places there-necked flask with above-mentioned two kinds of solution, add 0.8% the organic modifier polyoxyethylene glycol (PEG-400 account for the liquid total mass, molecular-weight average is 380-420) stir after, be warming up to 95 ℃, continue to stir 1.5h with 500 rev/mins mechanical stirring speed; After reaction finishes, filter, wash 80 ℃ of vacuum dryings.The gained zinc borate detects through X-ray crystalline diffraction instrument, and structural formula is: 2ZnO 3B 2O 33.5H 2O, particle diameter are 488nm.
Embodiment 6:
With borax, zinc sulfate is the borax solution of preparation of raw material 1.60mol/L, the zinc sulfate solution of 1.60mol/L, mol ratio by 1:1 places there-necked flask with above-mentioned two kinds of solution, add after 0.8% the organic modifier polyvinyl alcohol (molecular-weight average 12-15 ten thousand) account for the liquid total mass stirs, be warming up to 95 ℃, continue to stir 1.5h with 500 rev/mins mechanical stirring speed; After reaction finishes, filter, wash 80 ℃ of vacuum dryings.The gained zinc borate detects through X-ray crystalline diffraction instrument, and structural formula is: 2ZnO 3B 2O 33.5H 2O, particle diameter are 602nm.
Embodiment 7:
With borax, zinc sulfate is the borax solution of preparation of raw material 0.30mol/L, the zinc sulfate solution of 0.30mol/L, mol ratio by 1:1 places there-necked flask with above-mentioned two kinds of solution, add after 0.8% the organic modifier polyvinyl alcohol (molecular-weight average 12-15 ten thousand) account for the liquid total mass stirs, be warming up to 60 ℃, continue to stir 1.5h with 500 rev/mins mechanical stirring speed; After reaction finishes, filter, wash 80 ℃ of vacuum dryings.The gained zinc borate detects through X-ray crystalline diffraction instrument, and structural formula is: 2ZnO 3B 2O 33.5H 2O, particle diameter are 761nm.
Embodiment 8:
With borax, zinc sulfate is the borax solution of preparation of raw material 0.30mol/L, the zinc sulfate solution of 0.30mol/L, mol ratio by 1:1 places there-necked flask with above-mentioned two kinds of solution, add 0.8% the organic modifier polyoxyethylene glycol (PEG-400 account for the liquid total mass, molecular-weight average is 380-420) stir after, be warming up to 60 ℃, continue to stir 1.5h with 500 rev/mins mechanical stirring speed; After reaction finishes, filter, wash 80 ℃ of vacuum dryings.The gained zinc borate detects through X-ray crystalline diffraction instrument, and structural formula is: 2ZnO 3B 2O 33.5H 2O, particle diameter are 943nm.

Claims (3)

1. method for preparing superfine zinc borate, it is characterized in that carrying out according to following steps: with borax, zinc sulfate is the borax solution of preparation of raw material 0.30-1.60mol/L, the zinc sulfate solution of 0.30-1.60mol/L, pressing the mol ratio of 1:1 mixes above-mentioned two kinds of solution, after the organic modifier that adds the 0.5-0.8% account for the liquid total mass stirs, be warming up to 60-95 ℃, continue to stir 1.5h with 500 rev/mins mechanical stirring speed; After reaction finishes, filter, wash 80 ℃ of vacuum dryings; The particle diameter of gained zinc borate is between 40-950nm; Wherein said organic modifier is polyoxyethylene glycol or polyvinyl alcohol.
2. a kind of method for preparing superfine zinc borate according to claim 1 is characterized in that wherein said polyoxyethylene glycol is PEG-400, and its molecular-weight average is 380-420.
3. a kind of method for preparing superfine zinc borate according to claim 1 is characterized in that wherein said polyvinyl alcohol phase molecular-weight average 12-15 ten thousand.
CN2011100009002A 2011-01-05 2011-01-05 Method for preparing superfine zinc borate Expired - Fee Related CN102060306B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103964455A (en) * 2014-05-30 2014-08-06 山东川君化工股份有限公司 Preparation method of zinc borate 3.5-hydrate
CN109438976A (en) * 2018-09-29 2019-03-08 东莞市意普万尼龙科技股份有限公司 Copolymer nylon product and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101254927A (en) * 2008-03-28 2008-09-03 江南大学 Method for preparing active zinc borate by one-step proccess
CN101780962A (en) * 2010-04-01 2010-07-21 山东川君化工股份有限公司 Method for preparing decahydrate zinc borate

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101254927A (en) * 2008-03-28 2008-09-03 江南大学 Method for preparing active zinc borate by one-step proccess
CN101780962A (en) * 2010-04-01 2010-07-21 山东川君化工股份有限公司 Method for preparing decahydrate zinc borate

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
《Materials Research Bulletin》 20071231 Shi Xixi,et.al PEG-300 assisted hydrothermal synthesis of 4ZnO.B2O3.H2O nanorods 1649-1656 1-3 第42卷, 2 *
《化工新型材料》 20080930 张小苗等 超空心纳米非晶态硼酸锌阻燃剂的制备 60-62 1-3 第36卷, 第9期 2 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103964455A (en) * 2014-05-30 2014-08-06 山东川君化工股份有限公司 Preparation method of zinc borate 3.5-hydrate
CN103964455B (en) * 2014-05-30 2016-01-20 山东川君化工股份有限公司 The preparation method of 3.5 hydrate zinc borates
CN109438976A (en) * 2018-09-29 2019-03-08 东莞市意普万尼龙科技股份有限公司 Copolymer nylon product and preparation method thereof
CN109438976B (en) * 2018-09-29 2021-06-08 辰东意普万新材料(广东)有限公司 Copolymerized nylon product and preparation method thereof

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