CN106397837A - Preparation method of superfine ZSM-5 molecular sieve-red phosphorus synergistic flame retardant - Google Patents
Preparation method of superfine ZSM-5 molecular sieve-red phosphorus synergistic flame retardant Download PDFInfo
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- CN106397837A CN106397837A CN201610817146.4A CN201610817146A CN106397837A CN 106397837 A CN106397837 A CN 106397837A CN 201610817146 A CN201610817146 A CN 201610817146A CN 106397837 A CN106397837 A CN 106397837A
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
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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
- C08K3/02—Elements
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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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
- C08K3/02—Elements
- C08K2003/026—Phosphorus
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention relates to a preparation method of a superfine ZSM-5 molecular sieve-red phosphorus synergistic flame retardant. The method comprises the steps of mixing a ZSM-5 molecular sieve and a certain amount of NiCl2 solution at the concentration of 0.1 mol/L, performing ion exchange at 60 DEG C for 30 to 120 minutes, filtering, washing and drying, putting into a quartz tube reactor, introducing hydrogen at 400 to 450 DEG C for 20 to 90 minutes, introducing hydrogen phosphide at 4410 to 440 DEG C for 2 to 10 hours, heating the sample in a reaction container isolated from air at 260 to 290 DEG C and preserving heat for 10 to 60 minutes to obtain the ZSM-5 molecular sieve-red phosphorus synergistic flame retardant with 5 to 37 percent (mass ratio) of red phosphorus loaded in a pore channel. The preparation process is simple, the defect in single use of the red phosphorus flame retardant is solved and the prepared flame retardant has high flame resistance.
Description
Technical field
The invention belongs to technical field of flame retardant is and in particular to a kind of ultra-fine ZSM-5 molecular sieve-red phosphorus synergistic fire retardant
Preparation method.
Background technology
With the enhancing of health of people environmental consciousness, seek environmental protection, low toxicity, efficient, multi-functional fire retardant have become resistance
The inexorable trend of combustion agent industry.The fire-retardant new technique such as super-refinement technology, microencapsulation technology, compounded technology, crosslinking technological is
Constantly develop.
In modern flame-retarded technology, the compounding of fire retardant is extremely important one side.Compounding is exactly to utilize fire retardant
Between interaction, to improve fire resistance, i.e. the cooperative effect of fire retardant.There is the fire-retardant effect of flame-retardant system of cooperative effect
Really good, fire resistance strengthens, not only can be fire-retardant but also can press down cigarette, also has some special functions, applied range, cost
Low, economic benefit can be significantly improved, be to realize one of non-halogen effective way of fire retardant.Red phosphorus is used in combination with other fire retardants
When, there is significant fire-resistant synergistic effect.
Inorganic combustion inhibitor has that good stability, nontoxic or low toxicity, corrosivity are little, lower-price characteristic, but its fire-retardant effect
Rate is low, it usually needs a large amount of interpolations just can have preferable flame retardant effect.Therefore, while improving fire block articles performance, it adds
Work degradation, mechanical property declines to a great extent, and has a strong impact on the quality of product.Research shows：The granularity of fire retardant is less, in base
In material, dispersion is bigger, and flame retardant effect is better.In recent years, Nano-technology Development is rapid, and nano material is used widely, now
Typically in micron order, if being reduced to nanoscale, flame retardant effect will significantly improve the fire retardant particle diameter using, the interpolation of fire retardant
Amount will be greatly lowered, it is possible to resolve the contradiction between Flame Retardancy energy and mechanical property.
The active material that phosphorus flame retardant is efficient due to it, low toxicity, low cigarette become fire retardant, especially red phosphorus are a kind of excellent
Fire retardant, its fire retardant mechanism is：Decomposes, form the Metaphosphoric acid with extremely strong dehydration property, so that the polymer of burning
Superficial charring, charring layer one side can reduce the releasing of fuel gas, on the other hand also has heat-absorbing action；In addition, red phosphorus with
After oxygen forms PO free radical entrance gas phase, a large amount of H, HO free radicals can be caught.But when using, there is following asking in red phosphorus
Topic：Inflammable, explosive, hypertoxic PH can be released with air Long Term Contact3Gas；This easily makes color articles as redness；Easily inhale
Water, with polymer poor compatibility.Disadvantages mentioned above seriously limits the direct application of red phosphorus.By red phosphorus through microencapsulation technology at
Reason, can overcome the disadvantages mentioned above in red phosphorus performance, eliminate hidden danger in storing, production, the course of processing for the red phosphorus：Two is can be white
Degreeization, to desalinate the color of red phosphorus, widens the range of application of red phosphorus；Three is the compatibility that can improve with base material, reduces to base material
The impact of physical and mechanical property；Four is can be realized the compounding of multiple ignition-proof elements (fire retardant), improved by the selection to capsule material
Flame-retardant smoke inhibition efficiency.Du Long is superfine to have studied the brucite and red phosphorus microcapsule cooperative flame retardant to ethylene-vinyl acetate copolymer
Effect（Longchao Du, Baojun Qu and Zhenjin Xu. Flammability characteristics and
synergistic effect of hydrotalcite with microencapsulated red phosphorus in
halogen-free flame retardant EVA composite. Polymer Degradation and Stability
91 (2006) 995-1001.）.Although the flame retardant effect of red phosphorus microcapsule is pretty good, its preparation technology is more complicated, fire retardant
Granular size is wayward, limits it and widely uses.
Porous material may apply to improve the performance of fire retardant in fire retardant, especially to macromolecular material heat stability
Raising particularly evident.At present, some researchers existing have carried out the research to such flame retardant performance.Ye Lei etc. studies
The multi-walled carbon nano-tubes and magnesium hydroxide cooperative flame retardant effect to ethylene-vinyl acetate copolymer, works as multi-walled carbon nano-tubes
Addition be 2% when, can substantially reduce the HRR of ethylene-vinyl acetate copolymer, mass loss rate reaches
50%-60%, makes the oxygen index (OI) of fire retardant improve 5%（Lei Ye, Qianghua Wu and Baojun Qu. Synergistic
effects and mechanism of multiwalled carbon nanotubes with magnesium
hydroxide in halogen-free flame retardant EVA/MH/MWNT nanocomposites. Polymer
Degradation and Stability 94 (2009) 751–756.）.
The structure cell composition of ZSM-5 molecular sieve is represented by NanAlnSi96-nO192·16H2O.The crystal of ZSM-5 molecular sieve
Structure is made up of silicon (aluminum) oxygen tetrahedron, silicon (aluminum) oxygen tetrahedron by public summit oxygen bridge formed five yuan of silicon (aluminum) rings, 8
Such five-membered ring forms the basic structural unit of ZSM-5 molecular sieve.The pore passage structure of ZSM-5 molecular sieve is in ellipse by section
The straight tube shape duct (pore size is 0.54 nm × 0.56 nm) of shape and section are approximately circular Z-shaped duct (duct
A size of 0.52 nm × 0.58 nm) to intersect and formed, the size of two kinds of channel intersections is 0.9 nm.Metal in duct
Ion has ion-exchange capacity, also has certain fire resistance as inorganic material.
The purpose of the present invention is exactly that good for the red phosphorus flame-retardant performance, advantage of ultra-fine ZSM-5 molecular sieve and fire retardant is compounding
Synergistic concentrates on one, and the several respects both solving to be used alone red phosphorus combustion inhibitor presence are not enough, can prepare granule big again
The little fire retardant for submicron, uniform particle sizes.This fire retardant remains that red phosphorus combustion inhibitor is efficient, the advantage of low cigarette, low toxicity, sends out again
Wave ZSM-5 molecular sieve to the chemiluminescence of red phosphorus flame-retardant moreover it is possible to effective control fire-retardant particles size, micro-denier flame resistant agent
The compatibility with organic material can also be improved, be favorably improved mechanical property and the heat stability of flame-proof composite material.This
The ZSM-5 molecular sieve load red phosphorus micro-denier flame resistant agent of bright preparation has extensively in organic coating and high molecular film material flame retardant area
Wealthy application prospect.
Content of the invention
The technical solution used in the present invention is：A kind of preparation method of ZSM-5 molecular sieve-red phosphorus synergistic fire retardant, this
Bright with submicron ZSM-5 molecular sieve, hydrogen phosphide as primary raw material, first in ZSM-5 molecular sieve duct, load Ni, then make phosphatization
Hydrogen is generated yellow phosphorus by Ni catalytic decomposition in ZSM-5 molecular sieve duct, and yellow phosphorus is then converted to red phosphorus, you can ultra-fine ZSM-5 is obtained
Molecular sieve-red phosphorus synergistic fire retardant.Comprise the following steps：
（1）NiCl by ZSM-5 molecular sieve and a certain amount of 0.1mol/L2Solution mixes, ion exchange certain time at 60 DEG C
Afterwards, filter, wash, be dried, obtain loading Ni in duct2+ZSM-5 molecular sieve；
（2）Will（1）The sample of preparation is placed in quartz tube reactor, is passed through hydrogen reducing certain time at a certain temperature, obtains
The ZSM-5 molecular sieve of Ni is loaded in duct；
（3）Will（2）The ZSM-5 molecular sieve of the load Ni of preparation, in quartz tube reactor, is passed through hydrogen phosphide at a certain temperature
Certain time, hydrogen phosphide is made to be decomposed into yellow phosphorus in ZSM-5 molecular sieve duct；
（4）Will（3）The sample of preparation is heated to uniform temperature in the reaction vessel of isolation air, and held for some time, by Huang
Phosphorus is converted to red phosphorus, obtains loading the ZSM-5 molecular sieve-red phosphorus synergistic fire retardant of red phosphorus in duct.
In a preferred embodiment, described ZSM-5 molecular sieve particle diameter is 100-500nm.
In a preferred embodiment, the NiCl of described ZSM-5 molecular sieve and 0.1mol/L2Solution mix, at 60 DEG C from
The time that son exchanges is 30-120min.
In a preferred embodiment, the Ni loading in described ZSM-5 molecular sieve duct2+In hydrogen, the temperature of reduction is
400-450 DEG C, the time is 20-90min.
In a preferred embodiment, the temperature that described hydrogen phosphide decomposes in ZSM-5 molecular sieve duct is 410-440 DEG C,
Time is 2-10h.
In a preferred embodiment, described yellow phosphorus be converted to red phosphorus heating-up temperature be 260-290 DEG C, the time be 10-
60min.
Product red phosphorus content prepared by the present invention is 5-37%（Mass ratio）.
The advantage of fire retardant prepared by the present invention is to solve the deficiency being used alone red phosphorus combustion inhibitor presence, can prepare
Submicron-scale, the fire retardant of uniform particle sizes.This fire retardant remains that red phosphorus combustion inhibitor is efficient, the advantage of low cigarette, low toxicity, sends out again
Wave ZSM-5 molecular sieve to the chemiluminescence of red phosphorus flame-retardant moreover it is possible to effective control fire-retardant particles size, micro-denier flame resistant agent
The compatibility with organic material can also be improved, be favorably improved mechanical property and the heat stability of flame-proof composite material.This
Bright technology of preparing can be decomposed effective control phosphine gas in ZSM-5 molecular sieve duct, and highly effective flame-retardant can be controlled to become to share out bonus
Phosphorus only enters inside ZSM-5 molecular sieve duct, and without depositing in molecular sieve surface, preparation technology is simpler.The present invention is also
The recycling of sodium hypophosphite industry byproduct phosphine gas provides new way.
Specific embodiment
Embodiment 1
NiCl by the ZSM-5 molecular sieve for 100nm for the 15g median and 500mL 0.1mol/L2Solution mixes, at 60 DEG C
Lower stirring 120min, filter, washing, be dried after, be placed in quartz tube reactor, after being passed through hydrogen 90min at 450 DEG C, 440 DEG C
Under be passed through hydrogen phosphide, react 10h, after cooling, sample be heated to 290 DEG C in the reaction vessel of isolation air, insulation
60min, obtains loading the fire retardant of red phosphorus in the ZSM-5 molecular sieve duct that red phosphorus content is 37%, this fire retardant is mixed with polyethylene
The oxygen index (OI) closing the fire proofing of preparation is 33.6.
Embodiment 2
NiCl by the ZSM-5 molecular sieve for 500nm for the 15g median and 500mL 0.1mol/L2Solution mixes, at 60 DEG C
Lower stirring 30min, filter, washing, be dried after, be placed in quartz tube reactor, after being passed through hydrogen 20min at 400 DEG C, 410 DEG C
Under be passed through hydrogen phosphide, react 2h, after cooling, sample be heated to 260 DEG C in the reaction vessel of isolation air, be incubated 10min,
Obtain in the ZSM-5 molecular sieve duct that red phosphorus content is 5%, loading the fire retardant of red phosphorus, this fire retardant and polyethylene are mixed with
Fire proofing oxygen index (OI) be 28.7.
Embodiment 3
NiCl by the ZSM-5 molecular sieve for 300nm for the 15g median and 500mL 0.1mol/L2Solution mixes, at 60 DEG C
Lower stirring 75min, filter, washing, be dried after, be placed in quartz tube reactor, after being passed through hydrogen 55min at 425 DEG C, 425 DEG C
Under be passed through hydrogen phosphide, react 6h, after cooling, sample be heated to 275 DEG C in the reaction vessel of isolation air, be incubated 35min,
Obtain in the ZSM-5 molecular sieve duct that red phosphorus content is 16%, loading the fire retardant of red phosphorus, this fire retardant and polyethylene are mixed with
Fire proofing oxygen index (OI) be 31.3.
Embodiment 4
NiCl by the ZSM-5 molecular sieve for 100nm for the 15g median and 500mL 0.1mol/L2Solution mixes, at 60 DEG C
Lower stirring 120min, filter, washing, be dried after, be placed in quartz tube reactor, after being passed through hydrogen 20min at 450 DEG C, 440 DEG C
Under be passed through hydrogen phosphide, react 10h, after cooling, sample be heated to 290 DEG C in the reaction vessel of isolation air, insulation
60min, obtains loading the fire retardant of red phosphorus in the ZSM-5 molecular sieve duct that red phosphorus content is 11%, this fire retardant is mixed with polyethylene
The oxygen index (OI) closing the fire proofing of preparation is 29.9.
Embodiment 5
NiCl by the ZSM-5 molecular sieve for 100nm for the 15g median and 500mL 0.1mol/L2Solution mixes, at 60 DEG C
Lower stirring 120min, filter, washing, be dried after, be placed in quartz tube reactor, after being passed through hydrogen 90min at 450 DEG C, 440 DEG C
Under be passed through hydrogen phosphide, react 6h, after cooling, sample be heated to 290 DEG C in the reaction vessel of isolation air, be incubated 60min,
Obtain in the ZSM-5 molecular sieve duct that red phosphorus content is 30%, loading the fire retardant of red phosphorus, this fire retardant and polyethylene are mixed with
Fire proofing oxygen index (OI) be 33.0.
Oxygen index (OI)（Fire resistance）Test experiments：
By the fire retardant of above-described embodiment 1,2,3,4 and 5 preparation and polyethylene mixing（Wherein fire retardant accounts for 30%）, at 120 DEG C
Twin-roll mixing 10min, makes the laminar sample that thickness is 1mm.Oxygen index (OI) test is carried out according to GB/T2406 1993.
Claims (1)
1. a kind of preparation method of ultra-fine ZSM-5 molecular sieve-red phosphorus synergistic fire retardant is it is characterised in that comprise the following steps：With
Submicron ZSM-5 molecular sieve, hydrogen phosphide are primary raw material, by the NiCl of ZSM-5 molecular sieve and a certain amount of 0.1mol/L2Solution mixes
Close, after ion exchange certain time at 60 DEG C, filter, wash, be dried, obtain loading Ni in duct2+ZSM-5 molecular sieve,
Then it is placed in quartz tube reactor, is passed through hydrogen at a certain temperature, obtain in duct, loading the ZSM-5 molecular sieve of Ni, it
It is passed through hydrogen phosphide at a certain temperature afterwards, makes hydrogen phosphide be decomposed into yellow phosphorus in ZSM-5 molecular sieve duct, by it in isolation air
Reaction vessel in be heated to uniform temperature, yellow phosphorus is converted to red phosphorus, obtain in duct load red phosphorus ZSM-5 molecular sieve-
Red phosphorus synergistic fire retardant；The particle diameter of ZSM-5 molecular sieve is 100-500nm；ZSM-5 molecular sieve and NiCl2Solion exchanges
Time is 30-120min；The Ni of load in ZSM-5 molecular sieve duct2+In hydrogen, the temperature of reduction is 400-450 DEG C, the time
For 20-90min；Hydrogen phosphide decomposition temperature in ZSM-5 molecular sieve duct is 410-440 DEG C, and the time is 2-10h；Yellow phosphorus is changed
Heating-up temperature for red phosphorus is 260-290 DEG C, and the time is 10-60min；The fire retardant red phosphorus content of preparation is 5-37%（Quality
Than）.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116178947A (en) * | 2023-03-31 | 2023-05-30 | 南京京锦元科技实业有限公司 | Low-corrosiveness glass fiber reinforced flame-retardant nylon 66 material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6033206A (en) * | 1983-07-29 | 1985-02-20 | Nippon Chem Ind Co Ltd:The | Phosphorus-zeolite composite, its manufacture, and flame retardant |
| JPH06157013A (en) * | 1992-11-19 | 1994-06-03 | Nippon Chem Ind Co Ltd | Stabilized red phosphorus composition and flame retardant polymeric material |
| CN102935371A (en) * | 2012-11-16 | 2013-02-20 | 南开大学 | Catalyst for preparing yellow phosphorus through catalytic decomposition of phosphine gas and preparation method thereof |
| CN103906825A (en) * | 2011-12-06 | 2014-07-02 | 英派尔科技开发有限公司 | Phosphorus loaded particles and methods for their preparation and use |
-
2016
- 2016-09-12 CN CN201610817146.4A patent/CN106397837B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6033206A (en) * | 1983-07-29 | 1985-02-20 | Nippon Chem Ind Co Ltd:The | Phosphorus-zeolite composite, its manufacture, and flame retardant |
| JPH06157013A (en) * | 1992-11-19 | 1994-06-03 | Nippon Chem Ind Co Ltd | Stabilized red phosphorus composition and flame retardant polymeric material |
| CN103906825A (en) * | 2011-12-06 | 2014-07-02 | 英派尔科技开发有限公司 | Phosphorus loaded particles and methods for their preparation and use |
| CN102935371A (en) * | 2012-11-16 | 2013-02-20 | 南开大学 | Catalyst for preparing yellow phosphorus through catalytic decomposition of phosphine gas and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116178947A (en) * | 2023-03-31 | 2023-05-30 | 南京京锦元科技实业有限公司 | Low-corrosiveness glass fiber reinforced flame-retardant nylon 66 material and preparation method thereof |
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