CN106065126A - A kind of high concentration high melanism microcapsule coated red phosphorus combustion inhibitor master batch and preparation method thereof - Google Patents
A kind of high concentration high melanism microcapsule coated red phosphorus combustion inhibitor master batch and preparation method thereof Download PDFInfo
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- 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
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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
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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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
- C08K9/10—Encapsulated ingredients
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- 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
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Abstract
The invention discloses a kind of high concentration high melanism microcapsule coated red phosphorus combustion inhibitor master batch and preparation method thereof, it is to be prepared from by encapsulated red phosphorus and improved polyalkene carrier, and the mass ratio of encapsulated red phosphorus and improved polyalkene carrier is 7:3；Described encapsulated red phosphorus is prepared from cladding raw material by red phosphorus powder；Described preparation method includes red phosphorus pretreatment, addition cladding raw material, in-situ polymerization cladding, filters the step such as washing, dry, pelletize.The present invention effectively improve red phosphorus combustion inhibitor in use blackness not, coordinate black dyes still cannot effectively contaminate black problem, flame retarding efficiency can be improved simultaneously, improve the chemical stability of red phosphorus and the compatibility of polymeric substrate.
Description
Technical field
The invention belongs to synthesize the auxiliary agent technical field of macromolecular material, be specifically related to a kind of high concentration micro-glue of high melanism
Capsule Wrapped up Phosphorus Fire Retardant master batch and preparation method thereof.
Background technology
Along with the development of Polymer Technology, the synthetic material of excellent performance starts to enter into the every field of national economy.With
This simultaneously, people also have in the face of new fire threat.Owing to macromolecular material is mostly combustible, and in the process of burning
Middle meeting discharges substantial amounts of toxic and harmful, and therefore, carrying out macromolecular material flame-retardant modified is following macromolecule modified neck
Important research direction, one, territory.Fire retardant, also known as fireproof agent, fire-proofing chemical or incombustible agent, is a kind of for promoting material flame resistance,
Stop the auxiliary agent that material is ignited and suppresses flame to propagate；It is mainly used in fire-retardant synthesis macromolecular material and natural polymer
Material (includes plastics, fiber, rubber, coating etc.).The material being added with fire retardant is difficult to compared with the material of fire retardant
It is ignited, and the diffusion of flame transmission and toxic and harmful can be suppressed in a fire, be substantially reduced the danger of fire, it is ensured that
The goods such as various plastics, rubber can be safer use.
Red phosphorus combustion inhibitor is purplish red or the most browny a kind of amorphous powder, for inorganic no-halogen fire retardant, flame retarding efficiency
Height, with low cost.But, some defect that red phosphorus combustion inhibitor exists seriously limits its application in high molecular fire retardant field,
As: (1) red phosphorus can be generated H by slowly oxidation in atmosphere3PO2、H3PO3、H3PO4Deng material, easily separate out after long-term placement, deteriorate
Material mechanical performance, corrosion processing equipment；(2), during red phosphorus flame-retardant goods life-time service, PH is slowly discharged3Gas, pollutes environment,
Harm people's is healthy；(3) compatibility of inorganic red phosphorus and organic resin is poor, and bad dispersibility in resin, to high polymer
Effect on Mechanical Properties relatively big, also limit the performance of fire resistance to a certain extent；(4) red phosphorus outward appearance is rufous, its resistance
Combustion product can only make redness or black, and is difficult to reach the effect of black.Disadvantage mentioned above significantly limit the direct of red phosphorus
Use, thus red phosphorus need to be processed, such as micro encapsulation etc., increase its stability, the compatibility etc. so that it is can reach
Use standard, the advantage giving full play to its high efficiency low cost.
Summary of the invention
In order to overcome the deficiencies in the prior art, it is an object of the invention to provide a kind of high concentration high melanism microcapsule coated
Red phosphorus combustion inhibitor master batch, by red phosphorus powder is coated with, improve the chemical stability of red phosphorus, polymer base material compatible
Property.
Another object of the present invention is to provide the system of a kind of high concentration high melanism microcapsule coated red phosphorus combustion inhibitor master batch
Preparation Method, the microcapsule coated red phosphorus combustion inhibitor being obtained a kind of essence black by the technique and condition controlling microcapsule coated is female
Grain, improves red phosphorus flame-retardant goods and is difficult to contaminate black, the drawback of " black touched with red ".
For solving the problems referred to above, the technical solution adopted in the present invention is as follows:
A kind of high concentration high melanism microcapsule coated red phosphorus combustion inhibitor master batch, it is to be carried by encapsulated red phosphorus and improved polyalkene
Body is prepared from, and the mass ratio of encapsulated red phosphorus and improved polyalkene carrier is 7:3；Described encapsulated red phosphorus is by red phosphorus powder and cladding
Raw material is prepared from, and wherein cladding raw material includes water, aniline hydrochloride, Ammonium persulfate., Polyethylene Glycol；Wherein red phosphorus and cladding raw material
In the consumption of each component be respectively as follows: in parts by weight
Red phosphorus 60-80 part,
Water 120-400 part,
Polyethylene Glycol 0.5-3 part,
Aniline hydrochloride 3-8 part,
Ammonium persulfate. 2.4-9.6 part.
As further scheme, the consumption of each component in red phosphorus of the present invention and cladding raw material is in parts by weight
It is respectively as follows:
Red phosphorus 65-75 part,
Water 200-280 part,
Polyethylene Glycol 1-2 part,
Aniline hydrochloride 5-8 part,
Ammonium persulfate. 4-8 part.
A kind of preparation method of high concentration high melanism microcapsule coated red phosphorus combustion inhibitor master batch, it comprises the following steps:
1) red phosphorus dispersion processes: the red phosphorus emulsion after grinding remove impurity adds Polyethylene Glycol stirring and emulsifying 30-60 minute；
2) add aniline hydrochloride: under stirring at normal temperature state, in above-mentioned steps 1) system in be slowly added to aniline hydrochloride；
3) polyaniline-coated red phosphorus: be dissolved in the water by Ammonium persulfate., obtains ammonium persulfate solution, the most at normal temperatures will
Ammonium persulfate solution is slowly added into above-mentioned steps 2) system in, after having added continue stirring；
4) filter washing: step 3) reacted product filter after wash, obtain microcapsule coated red phosphorus；
5) be dried, pelletize: by step 4) the microcapsule coated red phosphorus that obtains is dried, mix with improved polyalkene carrier,
Use double screw extruder pelletize, i.e. obtain high concentration high melanism microcapsule coated red phosphorus combustion inhibitor master batch.
As further scheme, in preparation method of the present invention, step 1) time of stirring is 30-60 minute.
As further scheme, in preparation method of the present invention, step 2) aniline hydrochloride control to divide at 15-30
Clock adds completely.
As further scheme, in preparation method of the present invention, step 3) ammonium sulfate controls to divide at 30-60
Clock has added, and ammonium sulfate continues stirring reaction 3-5 hour after having added.
As further scheme, in preparation method of the present invention, the consumption of described Ammonium persulfate. is 0.8-1.2 times
The aniline hydrochloride of equivalent.
As further scheme, in preparation method of the present invention, step 5) using 60-80 DEG C of degree vacuum to do
Dry.
As further scheme, preparation method of the present invention is additionally included in step 1) front red phosphorus is carried out pretreatment
Step, concrete steps include:
Grind: former for red phosphorus powder is mixed in proportion with water, circular grinding 5 to 8 hours in sand mill；
Remove impurity: the red phosphorus serosity after grinding is heated to 80 DEG C with the sulfuric acid solution of 5% and reacts 0.5 to 1 hour, washes after filtration
Wash to neutrality；Then it is heated to 80 DEG C with the Cyanogran. of 5% and the sodium hydroxide solution of 1.5%, stirs 0.5 to 1 hour, filter
Rear washing is to neutrality, the lower vacuum drying of 65-75 DEG C 18-22 hour.
Compared to existing technology, the beneficial effects of the present invention is:
High concentration high melanism microcapsule coated red phosphorus combustion inhibitor master batch the most of the present invention uses aniline hydrochloride conduct
Raw material, owing to polyaniline is originally as black, after being coated on red phosphorus surface, concentrates the red phosphorus of dye dark red, contaminates black efficiency high, can be big
The big addition reducing black dyes, improves simultaneously and contaminates black effect, solve black touched with red drawback；
In high concentration high melanism microcapsule coated red phosphorus combustion inhibitor master batch the most of the present invention, the polyaniline-coated of formation
It is strong that layer self has char forming ability, and has fire-retardant synergistic effect between red phosphorus, can be effectively improved flame retarding efficiency；
High concentration high melanism microcapsule coated red phosphorus combustion inhibitor master batch the most of the present invention is by red phosphorus Surface coating
One strata aniline organic resin, (such as high density polyolefins etc. change with polymer base material as fire retardant effectively to mention red phosphorus
Property polyolefin) between there is the good compatibility, reduce the impact on Polymer Mechanical performance；
High concentration high melanism microcapsule coated red phosphorus combustion inhibitor master batch the most of the present invention in preparation process, formation
Polyaniline resin forms nucleocapsid structure after being coated with by red phosphorus, by red phosphorus and the oxygen in air and water isolation, improves the change of red phosphorus
Learn stability.
Below in conjunction with detailed description of the invention, the present invention is described in further detail.
Detailed description of the invention
High concentration high melanism microcapsule coated red phosphorus combustion inhibitor master batch of the present invention, is to be gathered by encapsulated red phosphorus and modification
Olefin carrier is prepared from, and the mass ratio of encapsulated red phosphorus and improved polyalkene carrier is 7:3；Described encapsulated red phosphorus is by red phosphorus powder
Being prepared from cladding raw material, wherein cladding raw material includes water, aniline hydrochloride, Ammonium persulfate., Polyethylene Glycol；Wherein red phosphorus and bag
The consumption covering each component in raw material is respectively as follows: in parts by weight
Red phosphorus 60-80 part,
Water 120-400 part,
Polyethylene Glycol 0.5-3 part,
Aniline hydrochloride 3-8 part,
Ammonium persulfate. 2.4-9.6 part.
As further scheme, the consumption of each component in red phosphorus of the present invention and cladding raw material is in parts by weight
It is respectively as follows:
Red phosphorus 65-75 part,
Water 200-280 part,
Polyethylene Glycol 1-2 part,
Aniline hydrochloride 5-8 part,
Ammonium persulfate. 4-8 part.
During finding the micro encapsulation cladding of red phosphorus in the research of the present invention, whether the interpolation of dispersant is to cladding effect
Fruit impact is relatively big, and wherein the hydrogen bond in Polyethylene Glycol and the affinity interaction of itself make Polyethylene Glycol be adsorbed in glue relatively easily
Grain surface forms one layer of polymer protective film, encloses colloidal particle, and its molecular link serpentine-like stretching to makes tool in aqueous solution
There is certain thickness, therefore when the colloid particle of band same sex electric charge is close to each other, electrostatic repulsion is plus high molecular sterically hindered
Effect, plays peptizaiton.
A kind of preparation method of high concentration high melanism microcapsule coated red phosphorus combustion inhibitor master batch, it comprises the following steps:
1) red phosphorus dispersion processes: joins in reactor by formula ratio by part water and red phosphorus, is stirring evenly and then adding into poly-
Ethylene glycol stirs to emulsifying；
2) add aniline hydrochloride: under stirring at normal temperature state, in above-mentioned steps 1) system in be slowly added to aniline hydrochloride；
3) polyaniline-coated red phosphorus: be dissolved in remaining water by Ammonium persulfate., obtain ammonium persulfate solution, then often
Under temperature, ammonium persulfate solution is added to above-mentioned steps 2) system in, continue stirring after having added to reaction completely；
4) filter washing: step 3) reacted product filter after wash, obtain microcapsule coated red phosphorus；
5) be dried, pelletize: by step 4) the microcapsule coated red phosphorus that obtains uses double screw extruder pelletize after drying, to obtain final product
To high concentration high melanism microcapsule coated red phosphorus combustion inhibitor master batch.
As further scheme, in preparation method of the present invention, step 1) time of stirring is 30-60 minute.
As further scheme, in preparation method of the present invention, step 2) aniline hydrochloride control to divide at 15-30
Clock adds completely.
Further, during red phosphorus microcapsule, while the formation of polyaniline resin, realize the cladding to red phosphorus,
During this is coated with, if the response time is the shortest, being coated with uneven, rough, polyaniline resin is divided with red phosphorus
From phenomenon；Time is oversize, and the operation phase is long, and the stable degree of microcapsule coated red phosphorus combustion inhibitor reduces；Control ammonium sulfate molten
The ground acceleration of liquid can effectively control the formation speed of polyaniline, in order to make the formation of polyaniline and red phosphorus cladding speed and
Form balance in effect, improve efficiency and the revenge quality of revenge, as further scheme, preparation method of the present invention
In, step 3) ammonium sulfate controls to have added at 30-60 minute, and ammonium sulfate continues stirring reaction 3-5 after having added
Hour.Additionally, find in the research of the present invention, mixing speed is also one of factor affecting covered effect, mixing speed mistake
Little, it is coated with uneven, surface of microcapsule is coarse, and covered effect is poor；Mixing speed is excessive, occurs coacervation between granule,
Affect covered effect equally.As further scheme, in above-mentioned preparation method, described step 3) mixing speed be 350-
450 turns/min.Preferably 400 turns/min.
As further scheme, in preparation method of the present invention, the consumption of described Ammonium persulfate. is 0.8-1.2 times
The aniline hydrochloride of equivalent.
As further scheme, in preparation method of the present invention, step 5) using 60-80 DEG C of degree vacuum to do
Dry.
Find core must be had during cladding to condense, and for big particle, small particles is more easy in the present invention
For condensation nucleus.Therefore, for the red phosphorus being wrapped by, particle diameter is the least more easily improves scattered effect after red phosphorus, the easiest
Cladding, the uniformity of cladding and effect are the best, can obtain the microcapsule coated red phosphorus powder of ultra-fine grain.Accordingly, as entering one
The scheme of step, above-mentioned preparation method is additionally included in step 1) the front step that red phosphorus is carried out pretreatment, concrete steps include:
Grind: after former for red phosphorus powder is mixed with a certain proportion of water, add sand mill and grind 5-10 hour, after being ground
Red phosphorus serosity
Remove impurity: the red phosphorus powder after grinding is heated to 80 DEG C with 5% sulfuric acid solution, stirs 1 hour, after filtration in washing extremely
Property；Then being heated to 80 DEG C with 5% Cyanogran. and 1.5% sodium hydroxide solution, stir 1 hour, after filtration, washing is to neutral, in
It is vacuum dried 18-22 hour at 65-75 DEG C.
The following is specific embodiment of the present invention, in the following embodiments, raw material, reagent and the equipment etc. that are used remove
All can be obtained by commercially available mode outside particular determination.
Embodiment 1
A kind of high concentration high melanism microcapsule coated red phosphorus combustion inhibitor master batch, is by encapsulated red phosphorus and improved polyalkene carrier
Being prepared from, the mass ratio of encapsulated red phosphorus and improved polyalkene carrier is 7:3；Described encapsulated red phosphorus is former with cladding by red phosphorus powder
Material is prepared from, and wherein cladding raw material includes water, aniline hydrochloride, Ammonium persulfate., Polyethylene Glycol；Wherein red phosphorus and cladding raw material in
The consumption of each component be respectively as follows: in parts by weight
60 parts of red phosphorus,
120 parts of water,
Polyethylene Glycol 0.5 part,
Aniline hydrochloride 3 parts,
Ammonium persulfate. 2.4 parts；
The preparation method of described high concentration high melanism microcapsule coated red phosphorus combustion inhibitor master batch comprises the following steps:
1) grind: after former for red phosphorus powder is mixed with a certain proportion of water, add sand mill and grind 5 hours, after being ground
Red phosphorus serosity；
2) remove impurity: the red phosphorus serosity after grinding is heated to 80 DEG C with 5% sulfuric acid solution, stirs 1 hour, wash after filtration to
Neutral；Then being heated to 80 DEG C with 5% Cyanogran. and 1.5% sodium hydroxide solution, stir 1 hour, after filtration, washing is to neutral,
It is vacuum dried 22 hours at 65 DEG C；
3) red phosphorus dispersion processes: the red phosphorus emulsion after grinding remove impurity adds Polyethylene Glycol stirring and emulsifying 30 minutes；
4) add aniline hydrochloride: under stirring at normal temperature state, in above-mentioned steps 3) system in be slowly added to aniline hydrochloride；
5) polyaniline-coated red phosphorus: be dissolved in the water by Ammonium persulfate., obtains ammonium persulfate solution, the most at normal temperatures will
Ammonium persulfate solution is slowly added into above-mentioned steps 2) system in, continue stirring after having added to abundant reaction 3 hours, stir
Mixing speed is 350 turns/min；
7) filter washing: step 3) reacted product filter after wash, obtain microcapsule coated red phosphorus；
8) be dried, pelletize: by step 4) the microcapsule coated red phosphorus that obtains uses 60 DEG C of degree vacuum drying tanks to use after drying
Double screw extruder pelletize, i.e. obtains high concentration high melanism microcapsule coated red phosphorus combustion inhibitor master batch.
Embodiment 2
A kind of high concentration high melanism microcapsule coated red phosphorus combustion inhibitor master batch, is by encapsulated red phosphorus and improved polyalkene carrier
Being prepared from, the mass ratio of encapsulated red phosphorus and improved polyalkene carrier is 7:3；Described encapsulated red phosphorus is former with cladding by red phosphorus powder
Material is prepared from, and wherein cladding raw material includes water, aniline hydrochloride, Ammonium persulfate., Polyethylene Glycol；Wherein red phosphorus and cladding raw material in
The consumption of each component be respectively as follows: in parts by weight
70 parts of red phosphorus,
250 parts of water,
Polyethylene Glycol 2 parts,
Aniline hydrochloride 5 parts,
Ammonium persulfate. 5 parts；
The preparation method of described high concentration high melanism microcapsule coated red phosphorus combustion inhibitor master batch comprises the following steps:
1) red phosphorus dispersion processes: the red phosphorus emulsion after grinding remove impurity adds Polyethylene Glycol stirring and emulsifying 45 minutes；
2) add aniline hydrochloride: under stirring at normal temperature state, in above-mentioned steps 1) system in be slowly added to aniline hydrochloride；
3) polyaniline-coated red phosphorus: be dissolved in the water by Ammonium persulfate., obtains ammonium persulfate solution, the most at normal temperatures will
Ammonium persulfate solution is slowly added into above-mentioned steps 2) system in, continue stirring after having added to abundant reaction 4 hours, stir
Mixing speed is 400 turns/min；
4) filter washing: step 3) reacted product filter after wash, obtain microcapsule coated red phosphorus；
5) be dried, pelletize: by step 4) the microcapsule coated red phosphorus that obtains uses 70 DEG C of degree vacuum drying tanks to use after drying
Double screw extruder pelletize, i.e. obtains high concentration high melanism microcapsule coated red phosphorus combustion inhibitor master batch.
Embodiment 3
A kind of high concentration high melanism microcapsule coated red phosphorus combustion inhibitor master batch, is by encapsulated red phosphorus and improved polyalkene carrier
Being prepared from, the mass ratio of encapsulated red phosphorus and improved polyalkene carrier is 7:3；Described encapsulated red phosphorus is former with cladding by red phosphorus powder
Material is prepared from, and wherein cladding raw material includes water, aniline hydrochloride, Ammonium persulfate., Polyethylene Glycol；Wherein red phosphorus and cladding raw material in
The consumption of each component be respectively as follows: in parts by weight
Red phosphorus 60-80 part,
Water 120-400 part,
Polyethylene Glycol 0.5-3 part,
Aniline hydrochloride 3-8 part,
Ammonium persulfate. 2.4-9.6 part；
The preparation method of described high concentration high melanism microcapsule coated red phosphorus combustion inhibitor master batch comprises the following steps:
1) grind: after former for red phosphorus powder is mixed with a certain proportion of water, add sand mill and grind 5 hours, after being ground
Red phosphorus serosity；
2) remove impurity: the red phosphorus serosity after grinding is heated to 80 DEG C with 5% sulfuric acid solution, stirs 1 hour, wash after filtration to
Neutral；Then being heated to 80 DEG C with 5% Cyanogran. and 1.5% sodium hydroxide solution, stir 1 hour, after filtration, washing is to neutral,
It is vacuum dried 18 hours at 75 DEG C；
3) red phosphorus dispersion processes: the red phosphorus emulsion after grinding remove impurity adds Polyethylene Glycol stirring and emulsifying 60 minutes；
4) add aniline hydrochloride: under stirring at normal temperature state, in above-mentioned steps 3) system in be slowly added to aniline hydrochloride；
5) polyaniline-coated red phosphorus: be dissolved in the water by Ammonium persulfate., obtains ammonium persulfate solution, the most at normal temperatures will
Ammonium persulfate solution is slowly added into above-mentioned steps 2) system in, continue stirring after having added to abundant reaction 5 hours, stir
Mixing speed is 450 turns/min；
6) filter washing: step 3) reacted product filter after wash, obtain microcapsule coated red phosphorus；
7) be dried, pelletize: by step 4) the microcapsule coated red phosphorus that obtains uses 80 DEG C of degree vacuum drying tanks to use after drying
Double screw extruder pelletize, i.e. obtains high concentration high melanism microcapsule coated red phosphorus combustion inhibitor master batch.
Performance detects
To the high concentration high melanism microcapsule coated red phosphor masterbatch obtained by embodiment 2 and tradition melamine resin
Microcapsule coated red phosphor masterbatch and traditional uncoated red phosphor masterbatch respectively with PA6 and black masterbatch mixing sample preparation, carry out performance survey
Examination；Test concrete formula and be shown in Table 1.
Table 1
Sample preparation testing process:
Mixing extruder extrusion cooling and dicing makes master batch dries sample preparation detection
Examination criteria is shown in Table 2:
Table 2
Testing result sees table 3:
Table 3
Test result analysis:
1) blackening effect: the high concentration high melanism microcapsule coated red phosphorus combustion inhibitor master batch described in embodiment 2, it contaminates black effect
Fruit promotes substantially, coordinates black masterbatch to reach complete blackening effect；The sample that traditional microcapsule coated red phosphor masterbatch prepares, dye
Black effect is general, black touched with red, even if coordinating black masterbatch still cannot hide reddish tint.The sample that uncoated red phosphor masterbatch prepares
Product, not only melanism is incomplete, also has a large amount of red point being distributed in starry sky shape；
2) vertical combustion test: three groups of samples all reach UL94-V0 level flame-retardant standard, wherein, use the embodiment of the present invention 1
The fire-retardant sample that product prepares, in the case of phosphorus content is equal, effect also leads over two groups of matched groups, and reason may have three:
First the fire-retardant synergistic effect between clad and red phosphorus is obvious, and flame retarding efficiency is greatly improved；Secondly clad and polymer phase
Capacitive is good, and red phosphorus is distributed more evenly across in base material, and flame retardant effect gives full play to；Last high concentration height described in embodiment 2 is black
Microcapsules encapsulated red phosphorus master batch red phosphorus content is higher than master batch prepared by traditional handicraft, therefore extremely low master batch addition i.e. can reach
Well (red phosphor masterbatch that the present invention prepares, flame-retardant composition content is 70% to flame retardant effect, and conventional commercial red phosphor masterbatch content is
40%)；
3) Mechanics Performance Testing: the sample that the present invention prepares all is much better than tradition red phosphor masterbatch system at tensile and impact properties
The flame retardant test sample obtained, its reason may have: the covering material that the present invention provides is good with PA6 substrate compatibility, granule and base
Without obvious boundary between material, decrease stress concentration point, improve mechanical property；The red phosphor masterbatch preparation side that the present invention provides
Method, its use improved polyalkene is carrier, and compared to the red phosphor masterbatch of traditional nylon carrier, improved polyalkene is ensureing with high
In the case of those compatible, there is good toughening effect, embodied from hot strength and notch impact strength.
Above-mentioned embodiment is only the preferred embodiment of the present invention, it is impossible to limit the scope of protection of the invention with this,
The change of any unsubstantiality that those skilled in the art is done on the basis of the present invention and replacement belong to institute of the present invention
Claimed scope.
Claims (8)
1. a high concentration high melanism microcapsule coated red phosphorus combustion inhibitor master batch master batch, it is characterised in that it is by encapsulated red phosphorus
Being prepared from improved polyalkene carrier, the mass ratio of encapsulated red phosphorus and improved polyalkene carrier is 7:3；Described encapsulated red phosphorus by
Red phosphorus powder is prepared from cladding raw material, and wherein cladding raw material includes water, aniline hydrochloride, Ammonium persulfate., Polyethylene Glycol；Wherein
The consumption of each component in red phosphorus and cladding raw material is respectively as follows: in parts by weight
Red phosphorus 60-80 part,
Water 120-400 part,
Polyethylene Glycol 0.5-3 part,
Aniline hydrochloride 3-8 part,
Ammonium persulfate. 2.4-9.6 part.
High concentration high melanism microcapsule coated red phosphorus combustion inhibitor master batch master batch the most according to claim 1, it is characterised in that
The consumption of each component in described red phosphorus and cladding raw material is respectively as follows: in parts by weight
Red phosphorus 65-75 part,
Water 200-280 part,
Polyethylene Glycol 1-2 part,
Aniline hydrochloride 5-8 part,
Ammonium persulfate. 4-8 part.
3. the preparation side of a high concentration high melanism microcapsule coated red phosphorus combustion inhibitor master batch master batch as claimed in claim 1
Method, it is characterised in that it comprises the following steps:
1) red phosphorus dispersion processes: the red phosphorus emulsion after grinding remove impurity adds Polyethylene Glycol stirring and emulsifying 30-60 minute；
2) add aniline hydrochloride: under stirring at normal temperature state, in above-mentioned steps 1) system in be slowly added to aniline hydrochloride；
3) polyaniline-coated red phosphorus: be dissolved in the water by Ammonium persulfate., obtains ammonium persulfate solution, the most at normal temperatures by over cure
Acid ammonium solution is slowly added into above-mentioned steps 2) system in, continue stirring after having added to fully reaction；
4) washing is filtered: the reacted product of step 3) is washed after filtering, and obtains microcapsule coated red phosphorus；
5) dry, pelletize: use double screw extruder pelletize after microcapsule coated red phosphorus vacuum drying step 4) obtained, to obtain final product
To high concentration high melanism microcapsule coated red phosphorus combustion inhibitor master batch.
Preparation method the most according to claim 3, it is characterised in that step 2) aniline hydrochloride control at 15-30 minute
Add completely.
Preparation method the most according to claim 3, it is characterised in that step 3) ammonium sulfate controlled at 30-60 minute
Having added, ammonium sulfate continues stirring reaction 3-5 hour after having added.
Preparation method the most according to claim 3, it is characterised in that the consumption of described Ammonium persulfate. is 0.8-1.2 times and works as
The aniline hydrochloride of amount.
Preparation method the most according to claim 3, it is characterised in that step 5) is using 60-80 DEG C of degree vacuum drying.
8. according to the preparation method described in any one of claim 3-7, it is characterised in that this preparation method is additionally included in step 1)
The front step that red phosphorus is carried out pretreatment, concrete steps include:
Grind: after former for red phosphorus powder mix with a certain proportion of water, addition sand mill grinding 5-10 hour, red after being ground
Phosphorus serosity；
Remove impurity: the red phosphorus serosity after grinding is heated to 80 DEG C with 5% sulfuric acid solution, stirs 1 hour, and after filtration, washing is to neutral；So
Being heated to 80 DEG C with 5% Cyanogran. and 1.5% sodium hydroxide solution afterwards, stir 1 hour, after filtration, washing is to neutral, in 65-75 DEG C
Lower vacuum drying 18-22 hour.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610695620.0A CN106065126B (en) | 2016-08-19 | 2016-08-19 | A kind of high melanism microcapsule coated red phosphorus combustion inhibitor master batch of high concentration and preparation method thereof |
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| CN201610695620.0A CN106065126B (en) | 2016-08-19 | 2016-08-19 | A kind of high melanism microcapsule coated red phosphorus combustion inhibitor master batch of high concentration and preparation method thereof |
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| CN106065126A true CN106065126A (en) | 2016-11-02 |
| CN106065126B CN106065126B (en) | 2019-04-26 |
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| CN106933019A (en) * | 2017-03-17 | 2017-07-07 | 赵征桥 | A kind of photochromic projection screen |
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