CN107022110B - The preparation of compound antimony oxide and its application in high flame retardant EVA expanded materials - Google Patents
The preparation of compound antimony oxide and its application in high flame retardant EVA expanded materials Download PDFInfo
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- CN107022110B CN107022110B CN201710354806.4A CN201710354806A CN107022110B CN 107022110 B CN107022110 B CN 107022110B CN 201710354806 A CN201710354806 A CN 201710354806A CN 107022110 B CN107022110 B CN 107022110B
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- antimony oxide
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- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K3/2279—Oxides; Hydroxides of metals of antimony
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G30/00—Compounds of antimony
- C01G30/004—Oxides; Hydroxides; Oxyacids
- C01G30/005—Oxides
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- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
Abstract
The invention discloses a kind of preparation of compound antimony oxide and its applications in high flame retardant EVA expanded materials, it is prepared into antimony oxide crude product under the auxiliary reacted under alkaline condition by CO 2 supercritical using antimony pentoxide and carbon monoxide, and it is mixed with aluminium hydroxide, compound antimony oxide is prepared by ultrasound precipitation method, without using halogenated flame retardant, under the use premise for reducing aluminium hydroxide fire retardant, effectively enhance the flame retardant property of antimony oxide, it is applied in the preparation of EVA expanded materials, the expanded material of preparation not only has the prerequisite every excellent properties of common expanded material, and also possess excellent flame retardant property, its application range in various inflammable building packaging materials is widened.
Description
Technical field
The present invention relates to the preparation of expanded material auxiliary agent field more particularly to a kind of compound antimony oxide and its in high resistant
Application in combustion property EVA expanded materials.
Background technology
Expanded material refers to generating the substance that bubble makes the foaming of porous mass in substance internal gasifier, has weight
Light, specific strength height, excellent insulation performance, the advantage that buffer capacity is notable and adsorption capacity is strong are measured, has been widely used
In fields such as auto industry, building industry, packaging industry, agricultural, water process and air filtrations；Such as manufacture foamed plastics, bubble
Foam rubber, foamed resin etc..
It is by ethylene (E) and second that EVA, which is by ethylene-vinyl acetate copolymer (also referred to as ethene-vinyl acetate copolymer),
Sour ethylene (VA) is copolymerized and is made, and EVA expanded materials are as other expanded materials, when applied to building packaging industry,
The requirement of flame retardant property seems particularly significant, and current way is all that addition fire retardant appropriate reaches effect in formula, often
Fire retardant magnesium hydroxide, aluminium hydroxide have the effect of EVA foamed products certain, but usage amount is larger, and right
In the high product of flame-retardancy requirements, flame retardant effect is also not highly desirable, also has a kind of flame retardant products of Japan in addition, but do not meet
ROHS is instructed.
Antimony oxide is a kind of preferable additive flame retardant, is all being generally to hinder with other halogen systems as fire retardant
Combustion agent synergistic effect could generate preferable effect, but wherein halogen, and when burning can discharge a large amount of smog and toxic have corrosion
The pernicious gas of property, and the death by accident occurred in fire, 80 percent is all since the asphyxia of smog and pernicious gas is made
At, therefore a kind of halogen-free flame retardants suitable for EVA expanded materials is worth research.
Invention content
Goal of the invention：In order to solve the problems of in the prior art, the present invention proposes compound antimony oxide
Preparation method and its application in high flame retardant EVA expanded materials have preferable flame retardant effect and avoid big when burning
The release of smog and pernicious gas is measured, environmental protection is practical.
Technical solution：To achieve these objectives, the present invention takes following technical scheme：The preparation of compound antimony oxide, packet
Include following steps：
(1) by antimony pentoxide, strong base solution merging supercritical reaction kettle, it is passed through reducing agent carbon monoxide, is opened super
Acoustic device opens carbon dioxide steel cylinder, dioxy controlled at 300-350 DEG C, pressure 10-15MPa after reacting 20-30min
Change carbon gas after cold is cooled to liquid, enters in reaction kettle after being pressurizeed by high-pressure pump, the reaction was continued 20-40min；
(2) it opens pressure relief opening and the pressure in supercritical reaction kettle is dropped into normal pressure, obtain powder；
(3) powder of collection is obtained into antimony oxide head product in 800-900 DEG C of temperature lower calcination；
(4) by antimony oxide head product and aluminium hydroxide with 5:1 mass ratio is prepared into compound using ultrasound precipitation method
Antimony oxide.
More preferably, the strong base solution is sodium hydroxide or potassium hydroxide.
The invention also discloses the applications of above-mentioned compound antimony oxide, are used for the preparation of high flame retardant EVA expanded materials.
More preferably, the preparation method for being applied to high flame retardant EVA expanded materials is by EVA, regenerated polythene, foaming
Agent, zinc oxide, stearic acid, crosslinking agent, compound antimony oxide, calcium carbonate are placed in mixer and carry out mixing treatment, through mill, go out
Piece, sulfur foam, cooling and shaping, cutting, punching, printing obtain required high flame retardant EVA expanded materials.
More preferably, the crosslinking agent is the mixture of di-tert-butyl peroxide and peroxidating lauryl.
Further, the crosslinking agent is di-tert-butyl peroxide and peroxidating lauryl mass ratio is 3:1 it is mixed
Close object.
More preferably, the foaming agent is vegetalitas foaming agent.
More preferably, the additive amount of the antimony oxide is the 5%-10% of total amount by weight.
Advantageous effect：The preparation of a kind of compound antimony oxide provided by the invention and its in high flame retardant EVA foaming materials
Application in material, using antimony pentoxide and carbon monoxide under alkaline condition by under the auxiliary of CO 2 supercritical reaction
It is prepared into antimony oxide crude product, and it is mixed with aluminium hydroxide, compound three oxidation two is prepared by ultrasound precipitation method
Antimony effectively enhances the resistance of antimony oxide under the use premise without using halogenated flame retardant, reduction aluminium hydroxide fire retardant
Performance is fired, is applied in the preparation of EVA expanded materials, the expanded material of preparation not only there is common expanded material must have
Every excellent properties, and also possess excellent flame retardant property, widened its answering in various inflammable building packaging materials
Use range.
Specific implementation mode
Embodiment 1：
The preparation of compound antimony oxide, includes the following steps：
(1) by antimony pentoxide, sodium hydroxide solution merging supercritical reaction kettle, it is passed through reducing agent carbon monoxide, is beaten
Vltrasonic device is opened, controlled at 300 DEG C, pressure 10MPa, carbon dioxide steel cylinder, carbon dioxide gas are opened after reacting 20min
Body enters after being pressurizeed by high-pressure pump in reaction kettle, the reaction was continued 20min after cold is cooled to liquid；
(2) it opens pressure relief opening and the pressure in supercritical reaction kettle is dropped into normal pressure, obtain powder；
(3) powder of collection is obtained into antimony oxide head product in 800 DEG C of temperature lower calcinations；
(4) by antimony oxide head product and aluminium hydroxide with 5:1 mass ratio is prepared into compound using ultrasound precipitation method
Antimony oxide.
Embodiment 2：
The preparation of compound antimony oxide, includes the following steps：
(1) by antimony pentoxide, potassium hydroxide solution merging supercritical reaction kettle, it is passed through reducing agent carbon monoxide, is beaten
Vltrasonic device is opened, controlled at 350 DEG C, pressure 15MPa, carbon dioxide steel cylinder, carbon dioxide gas are opened after reacting 30min
Body enters after being pressurizeed by high-pressure pump in reaction kettle, the reaction was continued 40min after cold is cooled to liquid；
(2) it opens pressure relief opening and the pressure in supercritical reaction kettle is dropped into normal pressure, obtain powder；
(3) powder of collection is obtained into antimony oxide head product in 900 DEG C of temperature lower calcinations；
(4) by antimony oxide head product and aluminium hydroxide with 5:1 mass ratio is prepared into compound using ultrasound precipitation method
Antimony oxide.
Embodiment 3：
The preparation of compound antimony oxide, includes the following steps：
(1) by antimony pentoxide, sodium hydroxide solution merging supercritical reaction kettle, it is passed through reducing agent carbon monoxide, is beaten
Vltrasonic device is opened, controlled at 330 DEG C, pressure 13MPa, carbon dioxide steel cylinder, carbon dioxide gas are opened after reacting 25min
Body enters after being pressurizeed by high-pressure pump in reaction kettle, the reaction was continued 30min after cold is cooled to liquid；
(2) it opens pressure relief opening and the pressure in supercritical reaction kettle is dropped into normal pressure, obtain powder；
(3) powder of collection is obtained into antimony oxide head product in 850 DEG C of temperature lower calcinations；
(4) by antimony oxide head product and aluminium hydroxide with 5:1 mass ratio is prepared into compound using ultrasound precipitation method
Antimony oxide.
Embodiment 4：
A kind of application of compound antimony oxide prepared by above-described embodiment 3 is used for the system of high flame retardant EVA expanded materials
Standby, specific preparation method is EVA, regenerated polythene, vegetalitas foaming agent, zinc oxide, stearic acid, crosslinking agent, compound three oxidation
Two antimony, calcium carbonate are placed in mixer and carry out mixing treatment, through mill, slice, sulfur foam, cooling and shaping, cutting, punching, print
Brush, obtains required high flame retardant EVA expanded materials；The crosslinking agent is di-tert-butyl peroxide and peroxidating lauryl quality
Than being 2:1 mixture；And the additive amount of compound antimony oxide is the 8% of total amount by weight.
The commercially available common EVA with flame retardant property of high flame retardant EVA expanded materials and comparative example prepared to embodiment 4 is sent out
Foam material is measured it according to according to 5455 vertical burn tests of GB/T, and oxygen index (OI) (OI) measurement result is as shown in the table：
Anti-flammability test is carried out, it is as a result as follows：
1 embodiment 4 of table is compared with comparative example oxygen index (OI)
Wherein, the oxygen index (OI) of regulation expanded material should be more than 30 or more just to meet flame-retardant standard in GB8624-2012.Such as
Data are shown in upper table, and high flame retardant EVA expanded material oxygen index (OI)s prepared by the embodiment of the present invention 4 meet flame-retardant materials mark
Standard is better than comparative example.
As it can be seen from table 1 a kind of preparation of compound antimony oxide prepared by the present invention, is applied to high flame retardant EVA
In the preparation of expanded material, the expanded material of preparation not only has the prerequisite every excellent properties of common expanded material,
And also possess excellent flame retardant property, hence it is evident that be better than other similar expanded materials, widened it and packed in various inflammable buildings
Application range in material, and be halogen-free, it is environmentally friendly.
It should be pointed out that for those skilled in the art, without departing from the principle of the present invention,
It can also make several improvements, these improvement also should be regarded as protection scope of the present invention.
Claims (8)
1. the preparation method of compound antimony oxide, it is characterised in that include the following steps：
（1）By in antimony pentoxide, strong base solution merging supercritical reaction kettle, it is passed through reducing agent carbon monoxide, opens ultrasound dress
It sets, controlled at 300-350 DEG C, pressure 10-15MPa, carbon dioxide steel cylinder, carbon dioxide is opened after reacting 20-30min
Gas enters after being pressurizeed by high-pressure pump in reaction kettle, the reaction was continued 20-40min after cold is cooled to liquid；
（2）It opens pressure relief opening and the pressure in supercritical reaction kettle is dropped into normal pressure, obtain powder；
（3）By the powder of collection in 800-900 DEG C of temperature lower calcination, antimony oxide head product is obtained；
（4）By antimony oxide head product and aluminium hydroxide with 5:1 mass ratio is prepared into compound three oxygen using ultrasound precipitation method
Change two antimony.
2. the preparation method of compound antimony oxide according to claim 1, it is characterised in that：The strong base solution is hydrogen
Sodium oxide molybdena or potassium hydroxide.
3. the application of compound antimony oxide prepared by preparation method as described in claim 1, it is characterised in that be used for high resistant
The preparation of combustion property EVA expanded materials.
4. the application of compound antimony oxide according to claim 3, it is characterised in that by EVA, regenerated polythene, foaming
Agent, zinc oxide, stearic acid, crosslinking agent, compound antimony oxide, calcium carbonate are placed in mixer and carry out mixing treatment, through mill, go out
Piece, sulfur foam, cooling and shaping, cutting, punching, printing obtain required high flame retardant EVA expanded materials.
5. the application of compound antimony oxide according to claim 4, it is characterised in that：The crosslinking agent is di-t-butyl
The mixture of peroxide and peroxidating lauryl.
6. the application of compound antimony oxide according to claim 5, it is characterised in that：The crosslinking agent is di-t-butyl
Peroxide and peroxidating lauryl mass ratio are 3:1 mixture.
7. the application of compound antimony oxide according to claim 4, it is characterised in that：The foaming agent is sent out for vegetalitas
Infusion.
8. the application of compound antimony oxide according to claim 4, it is characterised in that：The compound antimony oxide
Additive amount is the 5%-10% of total amount by weight.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710354806.4A CN107022110B (en) | 2017-05-18 | 2017-05-18 | The preparation of compound antimony oxide and its application in high flame retardant EVA expanded materials |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710354806.4A CN107022110B (en) | 2017-05-18 | 2017-05-18 | The preparation of compound antimony oxide and its application in high flame retardant EVA expanded materials |
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| CN107022110B true CN107022110B (en) | 2018-07-31 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103342845B (en) * | 2013-06-25 | 2016-07-06 | 江苏科悦新材料有限公司 | Fire proofing material and preparation method thereof, light fire-proof aluminium-plastic panel |
| CN103554649B (en) * | 2013-11-22 | 2016-01-13 | 广东国立科技股份有限公司 | A kind of EVA foam shoe material of tasteless flame-proof environmental protection |
| CN103943837B (en) * | 2014-04-11 | 2016-05-18 | 浙江大学 | The preparation method of antimony oxide and composite and the application in sodium-ion battery |
| CN104828866B (en) * | 2015-06-09 | 2016-06-01 | 锡矿山闪星锑业有限责任公司 | A kind of high temperature bends down colloidal antimony dry powder and its preparation method of volatilization |
| CN106497124A (en) * | 2016-10-28 | 2017-03-15 | 乐山凯亚达光电科技有限公司 | A kind of antimony oxide flame-retardant master batch and preparation method thereof |
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