CN109111932A - A kind of pre-dispersed composite flame-retardant agent filler of clay and preparation method - Google Patents
A kind of pre-dispersed composite flame-retardant agent filler of clay and preparation method Download PDFInfo
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- CN109111932A CN109111932A CN201810935008.5A CN201810935008A CN109111932A CN 109111932 A CN109111932 A CN 109111932A CN 201810935008 A CN201810935008 A CN 201810935008A CN 109111932 A CN109111932 A CN 109111932A
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- retardant agent
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/08—Organic materials containing halogen
Abstract
The invention discloses a kind of lithium battery fire extinguishing packing material addictive preparation method, mainly includes that bromine fire-retardant agent pretreatment, clay treatment and fire retardant are produced, composite flame-proof material is tested, obtain material requested.Bromine fire-retardant agent molecule is since, to be easier to adsorb and be dispersed in the clay layer stripped down, hydrophobic bromine fire-retardant agent molecule is hence into clay intercalated middle composite nanometer flame retardant of the formation based on clay with the interaction of the silicate surfaces of clay.In this patent, fusion method is because have the characteristics that efficient, flexible and technology maturation, the result have important directive function for industrialized production clay composite flame-retardant agent.
Description
Technical field
The present invention relates to the invention belongs to field of new materials, and in particular to a kind of pre-dispersed composite flame-retardant agent filler of clay and
Preparation method.
Background technique
Bromine fire-retardant agent application effect in thermoplastic resin is best, and maximum application amount is halogen-containing fire retardant,
It is wherein especially most widely used with deca-BDE etc., is developed in recent market and deca-BDE is steady in bromine content and heat
Similar decabromodiphenylethane fire retardant on qualitative and on molecular structure, decabromodiphenylethane burning do not generate carcinogenic substance
Matter " dioxin ", and flame retarding efficiency and the resin used, technique and deca-BDE are almost the same, raw material is easy to get in addition, at
Have advantage not available for other fire retardants in sheet, thus is able to promote rapidly extensively.With regard to the specific cognition of application process
From the point of view of, decabromodiphenylethane is that the bromine fire-retardant agent of representative has flame retarding efficiency height, material obtained in thermoplastic resin
Mechanical property is good, and manufacturing technique requirent is uncomplicated, is easily worked, relatively good with the resin compatibles such as plastics, can be relatively easy
Produce that flame retardant property is fine by adding fire retardant melt blending, and the fire-retardant material changed too much does not occur for material property
Material.In addition, the maximum advantage of bromine fire-retardant agent also resides in its very high cost performance and recoverable and long-acting resistance
Combustion property.
The agent of bromine fire-retardant also has a weakness of its own, for example over-emitting black exhaust when burning, has certain corrosivity, even has
A little products also have toxicity etc., these are to limit its widely applied unfavorable aspect.Therefore, in current process conditions and skill
Under the conditions of art, industrial circle is all in the follow-on efficient flame-retarding agent of active development.
Clay is the alumino-silicate that particle is very small and plasticity is strong, and synusia is by oxygen-octahedron and alumina octahedral group
At, clay or a kind of important raw mineral materials, large specific surface area has elecrtonegativity on particle, therefore has good physics
Adsorptivity and chemical mobility of the surface have the ability exchanged with other cations.It is generally known by people at present and study application
Stratified material, be widely used as polymeric additive because of its intercalation effect and bulking effect.Clay/polymer nanocomposite is compound
Material have the characteristics that it is economical, simple and easy to get, environmental-friendly be widely used in the heat-barrier material that blocks water, resistance oxygen sealing material, medicine
The fields such as fluorescent material of object slow-released carrier, organic-inorganic composition.In general, these excellent performances of clay material
It is related with clay extent of exfoliation in the polymer and dispersion degree.For example, clay removing after specific surface area at hundred times increase because
And cause the raising of Young's modulus.
To sum up, clay material is incorporated fire retardant, in fire-fighting and fire extinguishing Material Field, is all that market needs, while can
To fill the blank of existing fire extinguishing material clay material technology.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of pre-dispersed composite flame-retardant agent filler of clay and preparation methods, answer
For can effectively solve the problems such as liquid state batteries fire fire-fighting efficiency is low in lithium battery fire extinguishing material, lithium electricity can be effectively promoted
The fire safety evaluating guarantee in pond is with a wide range of applications in battery energy storage field.
In order to solve the above technical problems, the technical solution adopted by the present invention is that: a kind of pre-dispersed composite flame-retardant agent of clay is filled out
Material and preparation method, include the following steps:
1) agent of bromine fire-retardant pre-processes
10 grams of powder of bromine fire-retardant agent are taken, dissolution is dispersed in chloroform (proportionate relationship as solvent and solute), then
Chlorosulfonic acid (ClSO2OH) solution 15-150mL that mass fraction is 5.0-35.0% is added, the stir process time is 10-60 points
Then clock is freezed or is spray-dried the powdered modified fire retardant of acquisition, that is, isolates the modified flame-retardant in chloroformic solution
Agent.
2) clay treatment and fire retardant are produced
The modified flame-retardant agent obtained in 10 grams of powdered steps 1 is taken, is dispersed into emulsus with 20mL THF tetrahydro furan orchid solution
Liquid；20g clay is dispersed in 20mL THF and is stirred 24 hours；The two mixed liquor is mixed according to volume ratio 1:1 again, stirring 24
Hour, it is centrifugated out sediment, sediment is freeze-dried or is spray dried to compound fire proofing.
3) composite flame-proof material is tested
For composite material Thermal Degradation Experiments by directly heating in Muffle furnace to sample 10-60 minutes, temperature is Celsius from 200
It spends to cooling after 800 degrees Celsius, then XRD test is carried out to sample, all samples all use Philips X ' Pert Pro
(PANalytical, USA) powder sample X ray test instrument Cu K α (at 40kV and 40mA)。
As an improvement bromine fire-retardant agent powder described in the step 1) includes decabromodiphenylethane, ten bromines two
At least one of phenylate.
As an improvement the mass fraction of the step 1) chlorosulfonic acid is 5%.
As an improvement the mass fraction of the step 1) chlorosulfonic acid is 35%.
As an improvement the amount of the solution of the step 1) chlorosulfonic acid is 15ml.
As an improvement the amount of the solution of the step 1) chlorosulfonic acid is 150ml.
As an improvement the heating time in the step 3) is 30 minutes.
As an improvement the centrifugal treating revolving speed in the step 2) is 60 rpms, the processing time is 30 minutes.
As an improvement the solution in the step 2) is dried mode preferably spray drying.
As an improvement heating process in the step 3) is to heat after material package.
The technical solution adopted by the present invention, the beneficial effect is that: in the invention, bromine fire-retardant agent molecule due to
Silicate surfaces interaction with clay is hydrophobic to be easier to adsorb and be dispersed in the clay layer stripped down
Bromine fire-retardant agent molecule is hence into clay intercalated middle composite nanometer flame retardant of the formation based on clay.In this patent, it melts
Melt method because having the characteristics that efficiently, flexibly have with technology maturation, the result for industrialized production clay composite flame-retardant agent
Important directive function.
Detailed description of the invention:
The X-ray map of various difference samples under 300 DEG C for the treatment of temperatures of Fig. 1；
The X-ray map of various difference samples under 800 DEG C for the treatment of temperatures of Fig. 2.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with attached drawing to embodiment party of the present invention
Formula is described in further detail.
Embodiment one: by taking decabromodiphenylethane as an example:
The embodiment of the invention provides a kind of pre-dispersed composite flame-retardant agent filler of clay and preparation methods, this method comprises:
1. bromine fire-retardant agent pre-processes
By 10 grams of powder of bromine fire-retardant agent, dissolution is dispersed in chloroform, adds the chlorosulfonic acid that mass fraction is 5.0%
Solution 15mL, stir process time are 30 minutes, after isolate modified flame-retardant agent in chloroformic solution, freezing or spray drying
Obtain powdered modified fire retardant.
2. clay treatment
The powdered modified fire retardant of 10g is dispersed into emulsion with 20mL THF tetrahydro furan orchid solution；20g clay is dispersed
It is stirred 24 hours in 20mL THF；The two is mixed according to volume ratio 1:1 again, stirs 24 hours, is centrifugated out sediment.
Sediment is freeze-dried or is spray dried to compound fire proofing.
3. composite fire retardant product is subjected to fire resistant flame retardant test at different temperatures, it is as a result shown, when heat treatment temperature
When degree is within the scope of 300 DEG C to 500 DEG C, composite fire retardant is within 2 minutes processing time without generating significantly at discoloration
Change；But under 800 DEG C for the treatment of temperature since 500 DEG C, quality is obviously deepened, and illustrates composite fire retardant in this temperature
Occurs degradation under processing.
Embodiment two: for deca-BDE:
The embodiment of the invention provides a kind of pre-dispersed composite flame-retardant agent filler of clay and preparation methods, this method comprises:
1. bromine fire-retardant agent pre-processes
By 10 grams of powder of bromine fire-retardant agent, dissolution is dispersed in chloroform, adds the chlorine sulphur that mass fraction is 35.0%
Acid solution 150mL, stir process time are 60 minutes, after isolate modified flame-retardant agent in chloroformic solution, freezing or spraying
It is dry to obtain powdered modified fire retardant.
2. clay treatment
The powdered modified fire retardant of 10g is dispersed into emulsion with 20mL THF tetrahydro furan orchid solution；20g clay is dispersed
It is stirred 24 hours in 20mL THF；The two is mixed according to volume ratio 1:1 again, stirs 24 hours, is centrifugated out sediment.
Sediment is freeze-dried or is spray dried to composite fire retardant material.3. composite flame-proof material is tested
For composite material Thermal Degradation Experiments by directly heating in Muffle furnace to sample 10-60 minutes, temperature is Celsius from 200
It spends to cooling after 800 degrees Celsius, then XRD test is carried out to sample, all samples all use Philips X ' Pert Pro
(PANalytical, USA) powder sample X ray test instrument Cu K α (at 40kV and 40mA).
The X-ray profiling results of various different composite type samples of flame retardant are as shown in Figure 1.It can be seen from the chart, it is original
The peak position XRD of [001] of clay is the result shows that at 3.75 numerical value of abscissa.These results explanation, in excessively high processing temperature
Under degree, the bromine fire-retardant agent in clay has Partial digestion, causes the Layered-space structure of clay to be changed, to influence
Removing of the clay in polymeric system.
And as control, under 800 DEG C for the treatment of temperatures, the X-ray profiling results of various difference bromine fire-retardant agent samples
As shown in Figure 2.It can be seen from the chart, modified bromine fire-retardant agent can be removed completely in clay systems, to disperse
In lamellar clay system.Thus, these results explanation, suitable modification be compound bromine fire-retardant agent it is important because
Element.
In addition to above preferred embodiment, there are other embodiments of the invention, and those skilled in the art can be according to this
Various changes and variants are made in invention, and as long as it does not depart from the spirit of the invention, should belong to appended claims of the present invention and determines
The range of justice.
Claims (10)
1. a kind of pre-dispersed composite flame-retardant agent filler of clay and preparation method, include the following steps: 1), bromine fire-retardant agent locates in advance
Reason: taking 10 grams of powder of bromine fire-retardant agent, and dissolution is dispersed in chloroform (proportionate relationship as solvent and solute), adds matter
Chlorosulfonic acid (ClSO2OH) solution 15-150mL that score is 5.0-35.0% is measured, the stir process time is 10-60 minutes, then
It is freezed or is spray-dried and obtain powdered modified fire retardant, that is, isolate the modified flame-retardant agent in chloroformic solution；2) it, glues
Soil processing and fire retardant are produced: the modified flame-retardant agent obtained in 10 grams of powdered steps 1 are taken, with 20mL THF tetrahydro furan orchid solution
It is dispersed into emulsion；20g clay is dispersed in 20mL THF and is stirred 24 hours；Again by the two mixed liquor according to volume ratio 1:1
Mixing stirs 24 hours, is centrifugated out sediment, is freeze-dried or is spray dried to compound fire proofing for sediment；
3), composite flame-proof material test: composite material Thermal Degradation Experiments by being directly heated in Muffle furnace to sample 10-60 minutes,
Temperature from 200 degrees Celsius to 800 degree Celsius after it is cooling, then XRD test is carried out to sample, all samples all use Philips X '
Pert Pro (PANalytical, USA) powder sample X ray test instrument Cu K α (at 40kV and
40mA)。
2. a kind of pre-dispersed composite flame-retardant agent filler of clay according to claim 1 and preparation method, it is characterised in that: institute
Stating the agent powder of bromine fire-retardant described in step 1) includes at least one of decabromodiphenylethane, deca-BDE.
3. a kind of pre-dispersed composite flame-retardant agent filler of clay according to claim 1 and preparation method, it is characterised in that: institute
The mass fraction for stating step 1) chlorosulfonic acid is 5%.
4. a kind of pre-dispersed composite flame-retardant agent filler of clay according to claim 1 and preparation method, it is characterised in that: institute
The mass fraction for stating step 1) chlorosulfonic acid is 35%.
5. a kind of pre-dispersed composite flame-retardant agent filler of clay according to claim 1 and preparation method, it is characterised in that: institute
The amount for stating the solution of step 1) chlorosulfonic acid is 15ml.
6. a kind of pre-dispersed composite flame-retardant agent filler of clay according to claim 1 and preparation method, it is characterised in that: institute
The amount for stating the solution of step 1) chlorosulfonic acid is 150ml.
7. a kind of pre-dispersed composite flame-retardant agent filler of clay according to claim 1 and preparation method, it is characterised in that: institute
Stating the heating time in step 3) is 30 minutes.
8. a kind of pre-dispersed composite flame-retardant agent filler of clay according to claim 1 and preparation method, it is characterised in that: institute
Stating the centrifugal treating revolving speed in step 2) is 60 rpms, and the processing time is 30 minutes.
9. a kind of pre-dispersed composite flame-retardant agent filler of clay according to claim 1 and preparation method, it is characterised in that: institute
The solution stated in step 2) is dried mode preferably spray drying.
10. a kind of pre-dispersed composite flame-retardant agent filler of clay according to claim 1 and preparation method, it is characterised in that:
Heating process in the step 3) is to heat after material package.
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| CN201810935008.5A CN109111932A (en) | 2018-08-16 | 2018-08-16 | A kind of pre-dispersed composite flame-retardant agent filler of clay and preparation method |
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| CN201810935008.5A CN109111932A (en) | 2018-08-16 | 2018-08-16 | A kind of pre-dispersed composite flame-retardant agent filler of clay and preparation method |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1958720A (en) * | 2006-11-24 | 2007-05-09 | 北京理工大学 | Composite flame retardant in bromine series, preparation method and application |
| CN102575100A (en) * | 2009-09-14 | 2012-07-11 | 三菱瓦斯化学株式会社 | Flame-retardant polyamide resin composition |
| US20140024734A1 (en) * | 2012-07-20 | 2014-01-23 | Lanxess Deutschland Gmbh | Halogen-free poly(alkylene phosphates) |
| CN103642125A (en) * | 2013-11-21 | 2014-03-19 | 浙江大学宁波理工学院 | Nano-clay and nitrogen phosphorus flame retardant synergistic flame retardant polypropylene material and preparation method thereof |
| CN103788408A (en) * | 2014-01-22 | 2014-05-14 | 广州辰东化工科技有限公司 | DOPO modified inorganic fire retardant and preparation method thereof |
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2018
- 2018-08-16 CN CN201810935008.5A patent/CN109111932A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1958720A (en) * | 2006-11-24 | 2007-05-09 | 北京理工大学 | Composite flame retardant in bromine series, preparation method and application |
| CN102575100A (en) * | 2009-09-14 | 2012-07-11 | 三菱瓦斯化学株式会社 | Flame-retardant polyamide resin composition |
| US20140024734A1 (en) * | 2012-07-20 | 2014-01-23 | Lanxess Deutschland Gmbh | Halogen-free poly(alkylene phosphates) |
| CN103642125A (en) * | 2013-11-21 | 2014-03-19 | 浙江大学宁波理工学院 | Nano-clay and nitrogen phosphorus flame retardant synergistic flame retardant polypropylene material and preparation method thereof |
| CN103788408A (en) * | 2014-01-22 | 2014-05-14 | 广州辰东化工科技有限公司 | DOPO modified inorganic fire retardant and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| 胡源等: "阻燃聚合物/无机物纳米复合材料的若干前沿问题探讨", 《中国科学技术大学学报》 * |
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Application publication date: 20190101 |