WO1990009962A1 - Stannates and hydroxystannates - Google Patents

Stannates and hydroxystannates Download PDF

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Publication number
WO1990009962A1
WO1990009962A1 PCT/GB1990/000279 GB9000279W WO9009962A1 WO 1990009962 A1 WO1990009962 A1 WO 1990009962A1 GB 9000279 W GB9000279 W GB 9000279W WO 9009962 A1 WO9009962 A1 WO 9009962A1
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WIPO (PCT)
Prior art keywords
water
hydroxystannate
zinc
soluble
stannate
Prior art date
Application number
PCT/GB1990/000279
Other languages
French (fr)
Inventor
Paul Andrew Cusack
Jeremy Arthur Pearce
Original Assignee
Barry, Beresford, Thomas, Kingcome
Dean, Ronald, Richard
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Barry, Beresford, Thomas, Kingcome, Dean, Ronald, Richard filed Critical Barry, Beresford, Thomas, Kingcome
Publication of WO1990009962A1 publication Critical patent/WO1990009962A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof

Definitions

  • This invention is concerned with improvements in and relating to stannates and, more particularly, is concerned with the preparation of zinc hydroxystannate [ZnSn(0H) g ] and zinc stannate (ZnSnO-.) .
  • Zinc hydroxystannate may conveniently be prepared in particulate form by a double decomposition reaction between a water-soluble hydroxystannate (generally an alkali metal hydroxystannate such as sodium hydroxystannate) and a water-soluble zinc salt (such as zinc nitrate or zinc chloride) in an aqueous medium, i.e. by adding an aqueous solution of the soluble hydroxystannate to an aqueous solution of the soluble zinc salt or vice.versa.
  • a water-soluble hydroxystannate generally an alkali metal hydroxystannate such as sodium hydroxystannate
  • a water-soluble zinc salt such as zinc nitrate or zinc chloride
  • the resultant precipitated zinc hydroxystannate typically has a particle size of 0.5 to 5 microns, with an average of about 2 microns.
  • the precipitated zinc hydroxystannate may be converted to the anhydrous stannate by simple heating, e.g. at temperatures of 200 to 450"c. It has recently been found that the zinc hydroxystannate and zinc stannate, in particulate form, are useful as fire-retardant additives for polymeric materials, typically in amounts of 1 to 5 % by weight.
  • a more finely divided zinc-hydroxystannate having generally improved fire-retardant properties when incorporated in polymeric materials, may be produced by double decomposition by adding, to a body of water, (i) an aqueous solution of a water-soluble hydroxystannate and (ii) an aqueous solution of a water-soluble zinc salt.
  • a process for the production of zinc hydroxystannate which comprises simultaneously and separately adding, to a body of water, (i) an aqueous solution of a water-soluble hydroxystannate and (ii) an aqueous solution of a water-soluble zinc salt.
  • the water soluble hydroxystannate used as starting material is most conveniently an alkali metal hydroxystannate, especially sodium hydroxystannate.
  • the water-soluble zinc salt may conveniently be, for example, zinc nitrate or zinc chloride although, of course, other water-soluble zinc salts may be used.
  • the concentration of water-soluble hydroxystannate in the starting solution thereof is suitably from 25 to 300 g/2, preferably about 135 g/s.
  • the concentration of zinc chloride is suitably from 12.5 to 550 g/2, preferably about 70 q/ z .
  • the relative volumes of the two solutions and their concentrations should, as will be appreciated / be such as to give substantially stoichiometric amounts of the two reactants to avoid wastage and contamination.
  • the process of the invention may be carried out as a batch process, i.e. one in which a predetermined volume of each of the two starting solutions is added to a predetermined volume of water.
  • the process may be carried out as a continuous process, for example one in which the two starting solutions are continuously fed, each at a predetermined rate, to a body of water, generally one to which water is also fed at a predetermined rate and from which excess water and precipitated zinc hydroxystannate are removed at a rate to compensate for the rate of introduction of starting solutions and water.
  • the ratio of the total volume of the starting solutions to the body of water is suitably from 20:1 to 1:1, preferably about 4:1
  • the body of water to which the starting solutions are added is preferably stirred or otherwise agitated. In general fast agitation is preferred since it gives rise to a product of smaller primary particle size. Similarly, a lower rate of addition of the starting solution generally gives rise to a product of smaller primary particle size.
  • a material having improved fire-retardant properties may be obtained by incorporating a surfactant or dispersant in the body of water and/or in the starting solution(s).
  • Particularly preferred surfactants are polymers of ethylenically unsaturated carboxylic acids and their salts, especially polyacrylic acid and its sodium salt, e.g. the dispersants sold under the trade name "Dispex" .
  • Such dispersants may also be used in the preparation of finely divided zinc hydroxystannate by grinding or mixing preformed zinc hydroxystannate in the presence of the surfactant.
  • the precipitated hydroxystannate may be recovered from the body of water by any convenient liquid/solid separation technique, such as, for example, filtration, centrifugation or decantation.
  • the resulting product may be dried and, if desired, further heated (e.g. to a temperature of 200"cto 450 * C) in order to convert it to the anhydrous zinc stannate.
  • Powders with very fine particle size may be subject to agglomeration, resulting in a large secondary particle size and a consequent low LOI value.
  • the agglomeration may be reversed by grinding/shearing in an organic medium e.g. di-iso-octyl phthalate. This additional process can result in a stabilisation of the ultrafine particles and an increase in the overall LOI value.
  • the zinc hydroxystannate or zinc stannate produced in accordance with the invention is finely divided and thus typically has a primary particle size of less than 0.2 microns.
  • the hydroxystannate or stannate obtained in accordance with the invention finds particular use as a fire-retardant additive for polymeric materials.
  • zinc hydroxystannate and zinc stannate have been found to give good flame- and smoke-retardant performances and do not themselves give rise to undesirable by-products under the action of heat.
  • the zinc hydroxystannate or zinc stannate may act synergistically when combined with halogenated materials in retarding flame propagation and suppressing formation of smoke and toxic gases.
  • halogenated polyester resins are particularly effective in halogenated polyester resins and in rigid and plasticized PVC
  • amounts of the order of about 2% of the hydroxystannate or stannate produce slightly better flame retardancy than a conventional antimony trioxide additive under the same conditions and approximately twice the reduction in smoke and carbon monoxide evolution.
  • the tin compounds not only suppress the total amount of smoke and carbon monoxide but also retard their rate of evolution.
  • zinc hydroxystannate and zinc stannate also exhibit flame and smoke-retardant properties in halogen-free plastics or elastomeric formulations, particularly where the polymer contains a relatively high level of inorganic filler such as alumina trihydrate.
  • the materials of the invention are suitably incorporated in polymeric materials in amounts of 1 to 5%, preferably about 2 % by weight; those obtained in the presence of a surfactant being used at the lower end of this range.
  • a surfactant being used at the lower end of this range.
  • the resultant mixture was separated by centrifuging at 1500 rpm for 5 minutes and the supernatent liquor was decanted off.
  • the precipitate was washed in about 4 litres of distilled water three times, separating each time by centrifuging at 3000 rpm for 30 minutes and decanting. It was then dried at 110"C in an oven overnight. The dried cake was crushed in a mortar and pestle to give 130.99 g (92% yield) of a fine white powder (UF ZHS1).
  • the resultant mixture was separated by centrifuging at 1500 rpm for 5 minutes and the supernatant liquor decanted off.
  • the precipitate was washed in about 4 litres of distilled water three times, separating each time by centrifuging at 3000 rpm for 5 minutes and decanting. It was then dried at 110"C in an oven overnight. The cake was crushed in a mortar and pestle to give 270.3 g (95% yield) of a fine white powder (UF ZHS2).
  • Example 3 A quantity of a powder prepared as in Example 2 was heated at 400"C for 4 hrsa- A 19% weight loss was observed and anhydrous ZnSnO-. was produced, which was also a fine white powder. (UF ZS*).
  • the powder samples were incorporated into a commercial 28% brominated polyester resin (Stypol R126/6 supplied by Freeman Chemicals, Ellesmere Port), using a Silverson shear mixer. Flammability measurements (LOI) are shown below.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Fireproofing Substances (AREA)

Abstract

Zinc hydroxystannate, suitable for use as a fire-retardant additive in plastics material, is obtained by simultaneously adding to a body of water, (i) an aqueous solution of a water-soluble hydroxystannate and (ii) an aqueous solution of a water-soluble zinc salt. The body of water and/or the starting solution(s) may contain a surfactant. The resultant finely-divided hydroxystannate may be heated to convert it to anhydrous zinc stannate which latter may also be used as fire-retardant additive for polymeric materials.

Description

Stannates and hydroxystannates
This invention is concerned with improvements in and relating to stannates and, more particularly, is concerned with the preparation of zinc hydroxystannate [ZnSn(0H)g] and zinc stannate (ZnSnO-.) .
Zinc hydroxystannate may conveniently be prepared in particulate form by a double decomposition reaction between a water-soluble hydroxystannate (generally an alkali metal hydroxystannate such as sodium hydroxystannate) and a water-soluble zinc salt (such as zinc nitrate or zinc chloride) in an aqueous medium, i.e. by adding an aqueous solution of the soluble hydroxystannate to an aqueous solution of the soluble zinc salt or vice.versa.
The resultant precipitated zinc hydroxystannate typically has a particle size of 0.5 to 5 microns, with an average of about 2 microns. The precipitated zinc hydroxystannate may be converted to the anhydrous stannate by simple heating, e.g. at temperatures of 200 to 450"c. It has recently been found that the zinc hydroxystannate and zinc stannate, in particulate form, are useful as fire-retardant additives for polymeric materials, typically in amounts of 1 to 5 % by weight. It has now been found, in accordance with the present invention, that a more finely divided zinc-hydroxystannate, having generally improved fire-retardant properties when incorporated in polymeric materials, may be produced by double decomposition by adding, to a body of water, (i) an aqueous solution of a water-soluble hydroxystannate and (ii) an aqueous solution of a water-soluble zinc salt.
According to one embodiment of the invention, therefore, there is provided a process for the production of zinc hydroxystannate which comprises simultaneously and separately adding, to a body of water, (i) an aqueous solution of a water-soluble hydroxystannate and (ii) an aqueous solution of a water-soluble zinc salt.
The water soluble hydroxystannate used as starting material is most conveniently an alkali metal hydroxystannate, especially sodium hydroxystannate. The water-soluble zinc salt may conveniently be, for example, zinc nitrate or zinc chloride although, of course, other water-soluble zinc salts may be used.
The concentration of water-soluble hydroxystannate in the starting solution thereof is suitably from 25 to 300 g/2, preferably about 135 g/s. The concentration of zinc chloride is suitably from 12.5 to 550 g/2, preferably about 70 q/ z . The relative volumes of the two solutions and their concentrations should, as will be appreciated/ be such as to give substantially stoichiometric amounts of the two reactants to avoid wastage and contamination.
The process of the invention may be carried out as a batch process, i.e. one in which a predetermined volume of each of the two starting solutions is added to a predetermined volume of water. Alternatively, the process may be carried out as a continuous process, for example one in which the two starting solutions are continuously fed, each at a predetermined rate, to a body of water, generally one to which water is also fed at a predetermined rate and from which excess water and precipitated zinc hydroxystannate are removed at a rate to compensate for the rate of introduction of starting solutions and water. In any case, the ratio of the total volume of the starting solutions to the body of water is suitably from 20:1 to 1:1, preferably about 4:1
The body of water to which the starting solutions are added is preferably stirred or otherwise agitated. In general fast agitation is preferred since it gives rise to a product of smaller primary particle size. Similarly, a lower rate of addition of the starting solution generally gives rise to a product of smaller primary particle size.
However, it has also been found, in accordance with a further feature of the invention, that conditions which encourage aggregation of the primary particles, e.g. a decrease in addition rate, can produce a material which has the advantage that when incorporated in transparent or translucent polymeric materials, it does not markedly affect transparency. This can also be achieved by spray drying a suspension of preformed zinc hydroxystannate.
It has been found, in accordance with a further feature of the invention, that a material having improved fire-retardant properties may be obtained by incorporating a surfactant or dispersant in the body of water and/or in the starting solution(s). Particularly preferred surfactants are polymers of ethylenically unsaturated carboxylic acids and their salts, especially polyacrylic acid and its sodium salt, e.g. the dispersants sold under the trade name "Dispex" . The total amount of surfactant used, calculated as a weight percentage based on the dry yield of suitably from 0.1 to 5%, preferably 0.5 to 1%. Such dispersants may also be used in the preparation of finely divided zinc hydroxystannate by grinding or mixing preformed zinc hydroxystannate in the presence of the surfactant. In the process of the invention, the precipitated hydroxystannate may be recovered from the body of water by any convenient liquid/solid separation technique, such as, for example, filtration, centrifugation or decantation. The resulting product may be dried and, if desired, further heated (e.g. to a temperature of 200"cto 450 *C) in order to convert it to the anhydrous zinc stannate.
Powders with very fine particle size may be subject to agglomeration, resulting in a large secondary particle size and a consequent low LOI value. The agglomeration may be reversed by grinding/shearing in an organic medium e.g. di-iso-octyl phthalate. This additional process can result in a stabilisation of the ultrafine particles and an increase in the overall LOI value.
The zinc hydroxystannate or zinc stannate produced in accordance with the invention is finely divided and thus typically has a primary particle size of less than 0.2 microns.
The hydroxystannate or stannate obtained in accordance with the invention finds particular use as a fire-retardant additive for polymeric materials. Thus, zinc hydroxystannate and zinc stannate have been found to give good flame- and smoke-retardant performances and do not themselves give rise to undesirable by-products under the action of heat. Thus, the zinc hydroxystannate or zinc stannate may act synergistically when combined with halogenated materials in retarding flame propagation and suppressing formation of smoke and toxic gases. They are particularly effective in halogenated polyester resins and in rigid and plasticized PVC Thus, for example, in tests using brominated polyesters, amounts of the order of about 2% of the hydroxystannate or stannate, produce slightly better flame retardancy than a conventional antimony trioxide additive under the same conditions and approximately twice the reduction in smoke and carbon monoxide evolution. The tin compounds not only suppress the total amount of smoke and carbon monoxide but also retard their rate of evolution. Further, zinc hydroxystannate and zinc stannate also exhibit flame and smoke-retardant properties in halogen-free plastics or elastomeric formulations, particularly where the polymer contains a relatively high level of inorganic filler such as alumina trihydrate.
The materials of the invention are suitably incorporated in polymeric materials in amounts of 1 to 5%, preferably about 2 % by weight; those obtained in the presence of a surfactant being used at the lower end of this range. In order that the invention may be well understood the following examples are given by way of illustration only.
Example 1
1 Litre of 0.5 M Na2Sn(0H). solution (133 g/_) and 1 litre of 0.5 M ZnCl2 solution (68 g/fi) were added simultaneously to 500 ml of stirred water. A white precipitate was formed.
The resultant mixture was separated by centrifuging at 1500 rpm for 5 minutes and the supernatent liquor was decanted off. The precipitate was washed in about 4 litres of distilled water three times, separating each time by centrifuging at 3000 rpm for 30 minutes and decanting. It was then dried at 110"C in an oven overnight. The dried cake was crushed in a mortar and pestle to give 130.99 g (92% yield) of a fine white powder (UF ZHS1).
Example 2
1 Litre of 1M Na2Sn(OH)6 solution (267 g/_) and 1 litre of 1M ZnCl2 solution (136 g/_) were added simultaneously to 500 mis of stirred water, to which has been added 14.3 mis of a 10% by weight Dispex N40 solution. This amount of surfactant was that calculated to be 0.5% by weight on expected dry yield of ZnSn(0H)g. A white precipitate was formed.
The resultant mixture was separated by centrifuging at 1500 rpm for 5 minutes and the supernatant liquor decanted off. The precipitate was washed in about 4 litres of distilled water three times, separating each time by centrifuging at 3000 rpm for 5 minutes and decanting. It was then dried at 110"C in an oven overnight. The cake was crushed in a mortar and pestle to give 270.3 g (95% yield) of a fine white powder (UF ZHS2).
Example 3 A quantity of a powder prepared as in Example 2 was heated at 400"C for 4 hrsa- A 19% weight loss was observed and anhydrous ZnSnO-. was produced, which was also a fine white powder. (UF ZS*).
Example 4
1 litre of 1M Na2Sn(OH)6 solution (167 g/_) and 1 litre of 1M ZnCl2 solution (136 g/fi) were added simultaneously to 500 ml of stirred water. A white precipitate was formed. The resultant mixture was separated by centrifuging at 1500 rpm for 5 minutes and the supernatant liquor was decanted off. The precipitate was washed in about 4 litres of distilled water three times, separating each time by centrifuging at 3000 rpm for 15 minutes and decanting. It was then dried at 110°C in an oven overnight. The cake was micronised to give 272.6g (95% yield) of a fine white powder, (UF ZHS3).
Test Results
The powder samples were incorporated into a commercial 28% brominated polyester resin (Stypol R126/6 supplied by Freeman Chemicals, Ellesmere Port), using a Silverson shear mixer. Flammability measurements (LOI) are shown below.
Limiting Oxygen Index (LOI)
1% loading 2% loading
ZHS (commercial grade) 45.5 53.5
UF ZHS1 50.5 53.1
UF ZHS2 54.0 59.5
ZS (commercial grade) 54.6
UF ZS2 64.7
UFZHS3 50.5
UFZH53 (paste dispersion) 57.0

Claims

CLAIMS :
1. A process for the production of zinc hydroxy¬ stannate which comprises simultaneously and separately adding, to a body of water, (i) an aqueous solution of a water-soluble hydroxystannate and (ii) an aqueous solution of a water-soluble zinc salt.
2. A process as claimed in claim 1 in which the body of water and/or the solution of water-soluble hydroxystannate and/or water-soluble zinc salt also contain a surfactant.
3. A process as claimed in claim 2 in which the surfactant is polyacrylic acid or a salt thereof.
4. A process as claimed in any one of the preceding claims in which the zinc hydroxystannate obtained is subsequently heated to convert it to zinc stannate.
5. A polymeric material containing, as a fire-retardant additive, zinc hydroxystannate or zinc stannate when obtained by a process as claimed in any one of the preceding claims.
PCT/GB1990/000279 1989-02-22 1990-02-22 Stannates and hydroxystannates WO1990009962A1 (en)

Applications Claiming Priority (2)

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GB8904031.5 1989-02-22
GB8904031A GB2230255A (en) 1989-02-22 1989-02-22 Zinc stannate and hydroxystannate

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2670214A1 (en) * 1990-12-10 1992-06-12 Rhone Poulenc Chimie STABILIZED COMPOSITIONS OF CHLORINE POLYMER.
EP0537479A1 (en) * 1991-09-18 1993-04-21 Mitsubishi Materials Corporation Zinc stannate powder for molding materials and process for preparation thereof
US5278218A (en) * 1990-12-10 1994-01-11 Rhone-Poulenc Chimie Zinc stannate/zinc hydroxystannate heat-stabilized chloropolymers
EP0748768A1 (en) * 1995-06-13 1996-12-18 Nissan Chemical Industries Ltd. Hydrated zinc stannate sols, coating compositions and optical elements
US6001164A (en) * 1995-06-13 1999-12-14 Nissan Chemical Industries, Ltd. Hydrated zinc stannate sols, coating compositions and optical elements
CN102515185A (en) * 2011-12-08 2012-06-27 西北师范大学 Zinc hydroxystannate-palygorskite clay compound, its preparation and application as fire retardant
CN110294862A (en) * 2019-07-08 2019-10-01 云南锡业集团（控股）有限责任公司研发中心 A kind of preparation method of nano hybridization tinbase smoke suppressant
CN116947086A (en) * 2023-08-01 2023-10-27 东北师范大学 Pomegranate type Zn 2 SnO 4 Preparation method and application of nano flame retardant

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JP3626323B2 (en) * 1997-04-24 2005-03-09 水澤化学工業株式会社 Process for producing hydroxystannate and flame retardant
DE19752481A1 (en) * 1997-11-27 1999-06-02 Cit Alcatel Insulating material based on polyvinyl chloride
WO2014187496A1 (en) 2013-05-23 2014-11-27 Convention Européenne De La Construction Métallique (Cecm) Fire protecting coatings
DE102013111421A1 (en) 2013-05-24 2014-12-11 Contitech Elastomer-Beschichtungen Gmbh Multilayer fabric, especially bellows, with flame-retardant properties
DE202013012526U1 (en) 2013-05-24 2017-05-23 Contitech Elastomer-Beschichtungen Gmbh Multilayer fabric, in particular bellows, with flame-retardant properties
CN103466691B (en) * 2013-09-12 2015-02-25 哈尔滨工程大学 Preparation method of ZnSnO3 nano material with high gas sensitivity
DE102014212046A1 (en) 2014-06-24 2015-12-24 Contitech Transportbandsysteme Gmbh Conveyor with a conveyor belt
DE102015217885A1 (en) * 2015-09-17 2017-03-23 Contitech Elastomer-Beschichtungen Gmbh Flexible article based on at least one elastomer blend

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Title
Chemical Abstracts, volume 95, no. 18, 2 November 1981, (Columbus, Ohio, US), M. Inagaki et al : "Synthesis of calcium, magnesium, cobalt, cadmium, and zinc tin hydroxides (MSn(OH)6) by coprecipitation from aqueous solutions and their thermal decomposition ", see pages 711-711, abstract 161137, & Nippon Kagaku Kaishi 1981, 9(), 1517-151 *
Z. anorg. allg. Chem., Vol. 527, 1985 (Leipzig) M. Inagaki et al: "Syntheses of MSn(OH)6 by Coprecipitation and of MSnO3 by Thermal Decomposition ", *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2670214A1 (en) * 1990-12-10 1992-06-12 Rhone Poulenc Chimie STABILIZED COMPOSITIONS OF CHLORINE POLYMER.
EP0490780A1 (en) * 1990-12-10 1992-06-17 Rhone-Poulenc Chimie Stabilized compositions of a chlorinated polymer
US5278218A (en) * 1990-12-10 1994-01-11 Rhone-Poulenc Chimie Zinc stannate/zinc hydroxystannate heat-stabilized chloropolymers
EP0537479A1 (en) * 1991-09-18 1993-04-21 Mitsubishi Materials Corporation Zinc stannate powder for molding materials and process for preparation thereof
US6001164A (en) * 1995-06-13 1999-12-14 Nissan Chemical Industries, Ltd. Hydrated zinc stannate sols, coating compositions and optical elements
US5891362A (en) * 1995-06-13 1999-04-06 Nissan Chemical Industries, Ltd. Hydrated zinc stannate sols, coating compositions and optical elements
EP0748768A1 (en) * 1995-06-13 1996-12-18 Nissan Chemical Industries Ltd. Hydrated zinc stannate sols, coating compositions and optical elements
US6040372A (en) * 1995-06-13 2000-03-21 Nissan Chemical Industries, Ltd. Hydrated zinc stannate sols, coating compositions and optical elements
CN102515185A (en) * 2011-12-08 2012-06-27 西北师范大学 Zinc hydroxystannate-palygorskite clay compound, its preparation and application as fire retardant
CN110294862A (en) * 2019-07-08 2019-10-01 云南锡业集团（控股）有限责任公司研发中心 A kind of preparation method of nano hybridization tinbase smoke suppressant
CN110294862B (en) * 2019-07-08 2021-07-20 云南锡业集团（控股）有限责任公司研发中心 Preparation method of nano-hybrid tin-based smoke suppressant
CN116947086A (en) * 2023-08-01 2023-10-27 东北师范大学 Pomegranate type Zn 2 SnO 4 Preparation method and application of nano flame retardant
CN116947086B (en) * 2023-08-01 2024-03-05 东北师范大学 Pomegranate type Zn 2 SnO 4 Preparation method and application of nano flame retardant

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GB2230255A (en) 1990-10-17

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