CN107304268A - A kind of anti-flaming polyolefin composition and preparation method thereof - Google Patents
A kind of anti-flaming polyolefin composition and preparation method thereof Download PDFInfo
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- CN107304268A CN107304268A CN201610252554.XA CN201610252554A CN107304268A CN 107304268 A CN107304268 A CN 107304268A CN 201610252554 A CN201610252554 A CN 201610252554A CN 107304268 A CN107304268 A CN 107304268A
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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
- C08K3/32—Phosphorus-containing compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
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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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
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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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
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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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The present invention provides a kind of preparation method of anti-flaming polyolefin composition, and it comprises the following steps：(a) parts by weight of polyolefin 70~120, the parts by weight of expansion type flame retardant 15~100 are weighed；(b) dry-blend is obtained by the polyolefin and expansion type flame retardant are dry-mixed, then add the dry-blend in the first extruder, melting extrusion obtains premix；(c) premix is added in the second extruder, and is passed through at the 1/5~1/3 of the screw rod of the second extruder the carbon dioxide of above-critical state, melting extrusion obtains anti-flaming polyolefin composition.The present invention can promote expansion type flame retardant dispersed in polyolefin using the carbon dioxide of above-critical state, so as to obtain the anti-flaming polyolefin composition of excellent fireproof performance.The present invention also provides a kind of anti-flaming polyolefin composition.
Description
Technical field
The present invention relates to applied to fire-retardant technical field of polymer materials, more particularly to a kind of fire retardant polyolefin
Compound and preparation method thereof.
Background technology
Polyolefine material has abundant raw material, cheap, to be easily worked shaping, combination property superior etc. excellent
Point, is widely used in the fields such as agricultural, machinery, electronics, packaging, automobile, building materials, but itself is easy
Combustion, fire resistance is poor, thus needs in many applications to carry out flame retardant treatment.At present, polyolefin
It is fire-retardant to be realized mainly by the various fire retardants of addition, although traditional halogen containing flame-retardant is with good fire resistance,
But a large amount of smog and toxic gas are also easy to produce in the production and use process, produce secondary pollution, therefore research and development
Non halogen flame retardant polyolefin composite is particularly important.
Expansion type flame retardant using phosphorus nitrogen as ignition-proof element is one of conventional flame-retardant system of polyolefin, and its is main
Including：Catalyst (acid source), carburization agent (carbon source), swelling agent (source of the gas).During burning, expansion type flame-retarding
Agent can form the carbonaceous froth bed of one layer of bulk multi-hole in polymer surfaces, and this separation layer can isolate oxygen,
Heat transfer is prevented, so as to play fire retardation.
However, existing expansion type flame retardant and compatible polyolefin are poor, it is difficult to uniform in matrix polymer
It is scattered.And in order to which the flame retardant effect for reaching good usually requires to add a large amount of fire retardants, have a strong impact on multiple
The mechanical property of condensation material, this limits the use of phosphorus-nitrogen expansion type fire retardant to a certain extent.For example
It is high that publication number CN10134830A Chinese patent applications disclose addition of the expansion type flame retardant in polypropylene
Up to 50%.In order to improve fire resistance, reduce fire retardant addition, it usually needs expansion type flame retardant with
Other additive compounds are used, such as hydrotalcite, montmorillonite, titanium dioxide.But hydrotalcite and montmorillonite etc.
It is equally poor with compatible polyolefin, it is difficult to dispersed, thus usually require to carry out surface modification treatment.But
Be due to hydrotalcite and montmorillonite etc. modification usually require in the organic solvents such as toluene carry out, its have connects
Rate is low for branch, complex operation shortcoming, and organic solvent exist in use volatile, pollution environment and
Harmful the problems such as.
The content of the invention
In view of the above-mentioned problems, it is an object of the invention to provide a kind of dispersion effect is good, flame retarding efficiency is high, raw
Efficiency high, simple to operate, efficient, environmental protection anti-flaming polyolefin composition and preparation method thereof are produced, with
Solve the problems of the prior art.
The present invention provides a kind of preparation method of anti-flaming polyolefin composition, and it comprises the following steps：
(a) parts by weight of polyolefin 70~120, the parts by weight of expansion type flame retardant 15~100 are weighed；
(b) dry-blend is obtained by the polyolefin and expansion type flame retardant are dry-mixed, the dry-blend is then added the
In one extruder, melting extrusion obtains premix；
(c) premix is added in the second extruder, and 1/5~1/3 of the screw rod in the second extruder
Place is passed through the carbon dioxide of above-critical state, and melting extrusion obtains anti-flaming polyolefin composition.
It is preferred that, polyolefin described in step (a) is polyethylene, polypropylene, EP rubbers, ethyl vinyl acetate second
At least one of alkene copolymer, ethylene-octene copolymer.
It is preferred that, expansion type flame retardant described in step (a) presses (2~4) by acid source, carbon source, source of the gas：(0~
1)：The mass ratio of (0~1) is mixed, wherein the acid source be APP, melamine polyphosphate,
In ammonium dihydrogen phosphate, hypophosphites, cyanuric acid, tricresyl phosphate, alkyl phosphate, phosphonate ester at least
One kind, the carbon source is starch, pentaerythrite, bipentaerythrite, tripentaerythritol, sorbierite, phenolic aldehyde
At least one of resin, cyclodextrin, the source of the gas are dicyandiamide, melamine, urea, Lauxite
At least one of.
It is preferred that, the mass ratio of the expansion type flame retardant described in step (a) accounts for the gross mass of the dry-blend
15%~45%.
It is preferred that, the quality of the carbon dioxide of above-critical state described in step (c) accounts for the premix gross mass
1%~20%.
It is preferred that, the carbon dioxide of above-critical state is passed through in step (c) at the 1/4 of the screw rod of the second extruder.
It is preferred that, the temperature in the first half area of the screw rod of the second extruder described in step (c) for 170 DEG C~
210 DEG C, the temperature in the later half area of screw rod is 160 DEG C~220 DEG C.
It is preferred that, the injection pressure of the carbon dioxide of above-critical state described in step (c) is 7MPa~30MPa.
The present invention also provides a kind of anti-flaming polyolefin composition obtained using above-mentioned preparation method, described fire-retardant
Polyolefin complex includes expansion type flame retardant and polyolefin, and the expansion type flame retardant is dispersed in polyene
Hydrocarbon.
Relative in traditional expansion type flame retardant adding technology, having that fire retardant is scattered uneven, addition is big,
Flame retarding efficiency is low, destruction mechanical property the problems such as, the polyolefin in anti-flaming polyolefin composition of the present invention
In high-temperature heating, carbon source in the expansion type flame retardant is dehydrated into charcoal under acid source effect, and
The acid source is decomposed under the gas effect of generation, forms the carbonaceous layer of bulk multi-hole.The carbonaceous layer of the formation
The heat transfer between polyolefin and thermal source can be weakened, and prevent gas diffusion.In addition, the intumescent hinders
Combustion agent is thermally decomposed the non-combustible gas such as formed ammonia and also acts as acting on for dilution fuel gas, so as to hinder
Only flame transmission, makes polyolefin from further degraded, burning, to obtain good flame retardant effect.
Compared to prior art, preparation method of the present invention is super by being passed through at the 1/5~1/3 of the screw rod
The carbon dioxide of critical state, has stronger plasticizing capacity and diffusion using the carbon dioxide of the above-critical state
Ability, can significantly reduce the viscosity of polyolefin melt.On the one hand, actual processing temperature can be greatly reduced in this,
So as to effectively suppress the decomposition of the material such as acid source APP etc., carbon source pentaerythrite in process, have
The problem of decomposition temperature that effect solves fire retardant in the prior art is less than the processing temperature of polymer.On the other hand,
The carbon dioxide of above-critical state can reduce the viscosity of polymer melt as machining medium, be conducive to fire-retardant
Agent disperses；Meanwhile, it can significantly reduce the interfacial tension of expansion type flame retardant and polyolefin, so as to increase
The contact probability of expansion type flame retardant and polyolefin, therefore significantly enhance expansion type flame retardant in polyolefin
In dispersibility, efficiently solve expansion type flame retardant agglomeration traits and it is scattered uneven the problems such as so that
Improve the flame retarding efficiency and mechanical property of anti-flaming polyolefin composition.The preparation method also has green ring
Guarantor, the advantage that energy consumption is low, production efficiency is high, obtained anti-flaming polyolefin composition is in color and luster, mechanical property
In terms of also improved.
Brief description of the drawings
Fig. 1 is the stereoscan photograph of anti-flaming polypropylene composite prepared by the embodiment of the present invention 1.
Fig. 2 is the stereoscan photograph of anti-flaming polypropylene composite prepared by comparative example 1.
Embodiment
The technical scheme in embodiment of the present invention will be clearly and completely described below, it is clear that institute
The embodiment of description is only a part of embodiment of the invention, rather than whole embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art are obtained under the premise of creative work is not made
The all other embodiment obtained, belongs to the scope of protection of the invention.
The invention provides a kind of preparation method of anti-flaming polyolefin composition, it comprises the following steps：
(a) parts by weight of polyolefin 70~120, the parts by weight of expansion type flame retardant 15~100 are weighed；
(b) polyolefin and expansion type flame retardant are mixed to get dry-blend, the dry-blend is then added the
In one extruder, melting extrusion obtains premix；
(c) premix is added in the second extruder, and 1/5~1/3 of the screw rod in the second extruder
Place is passed through the carbon dioxide of above-critical state, and extrusion obtains the composite polyolefine material of efficient halogen-free anti-inflaming.
In step (a), the polyolefin is that polyethylene, polypropylene, EP rubbers, ethene-vinyl acetate are common
At least one of polymers, ethylene-octene copolymer.The expansion type flame retardant is by acid source, carbon source, source of the gas
By (2~4)：(0~1)：The mass ratio of (0~1) is mixed.It is preferred that, the acid source of the addition,
The mass ratio of carbon source and source of the gas is 3:1:1, the mass ratio of the polyolefin and expansion type flame retardant for (70~
120)：(20~150).
Acid source in the expansion type flame retardant can be APP, melamine polyphosphate, biphosphate
At least one of ammonium, hypophosphites, cyanuric acid, tricresyl phosphate, alkyl phosphate, phosphonate ester.It is excellent
Choosing, the acid source is APP or melamine polyphosphate.Carbon source in the expansion type flame retardant
Can be starch, pentaerythrite, bipentaerythrite, tripentaerythritol, sorbierite, phenolic resin, cyclodextrin
At least one of.It is preferred that, the carbon source is starch or pentaerythrite.In the expansion type flame retardant
Source of the gas is at least one of dicyandiamide, melamine, urea, Lauxite.It is preferred that, the source of the gas
For melamine.
In step (b), a high-speed mixer can be first passed through and mix the polyolefin and expansion type flame retardant
To dry-blend, then the dry-blend is added in the first extruder by the charging aperture of the first extruder and carried out
Melt blending, extrusion obtains premix.First extruder concretely double screw extruder.It is described
The temperature of first extruder is 180 DEG C~220 DEG C.
In step (c), the premix is added to the second extruder by the charging aperture of the second extruder
It is interior, and it is passed through at the 1/5~1/3 of the screw rod of the second extruder the carbon dioxide of above-critical state, melting extrusion
Obtain anti-flaming polyolefin composition.The quality of the carbon dioxide of the above-critical state accounts for mixture gross mass
1%~20%.The injection pressure of the carbon dioxide of the above-critical state is 7MPa~30MPa.Described second squeezes
It is the single screw extrusion machine independently built to go out machine.The temperature in the first half area of the screw rod of second extruder is
170 DEG C~210 DEG C, the temperature in the later half area of screw rod is 160 DEG C~220 DEG C.Pressure in second extruder
Power is 7MPa~30MPa.
In order to ensure that the carbon dioxide of above-critical state has preferable mixed effect with the premix, it is preferred that
The carbon dioxide of above-critical state, the dioxy of the above-critical state are passed through at the 1/4 of the screw rod of the second extruder
The quality for changing carbon accounts for the 2%~10% of the mixture gross mass, the injection of the carbon dioxide of the above-critical state
Pressure is 10MPa~20Mpa, the temperature in the second extruder first half area for 180 DEG C~200 DEG C, screw rod
The temperature in later half area be 180 DEG C~210 DEG C, the pressure in second extruder is 8MPa~18MPa.
Compared to prior art, preparation method of the present invention is super by being passed through at the 1/5~1/3 of the screw rod
The carbon dioxide of critical state, has stronger plasticizing capacity and diffusion using the carbon dioxide of the above-critical state
Ability, can significantly reduce the viscosity of polyolefin melt.On the one hand, actual processing temperature can be greatly reduced in this,
So as to effectively suppress the decomposition of the material such as acid source APP etc., carbon source pentaerythrite in process, have
The problem of decomposition temperature that effect solves fire retardant in the prior art is less than the processing temperature of polymer.On the other hand,
The carbon dioxide of above-critical state can reduce the viscosity of polymer melt as machining medium, be conducive to fire-retardant
Agent disperses；Meanwhile, it can significantly reduce the interfacial tension of expansion type flame retardant and polyolefin, so as to increase
The contact probability of expansion type flame retardant and polyolefin, therefore significantly enhance expansion type flame retardant in polyolefin
In dispersibility, efficiently solve expansion type flame retardant agglomeration traits and it is scattered uneven the problems such as so that
Improve the flame retarding efficiency and mechanical property of anti-flaming polyolefin composition.The preparation method also has green ring
Guarantor, the advantage that energy consumption is low, production efficiency is high, obtained anti-flaming polyolefin composition is in color and luster, mechanical property
In terms of also improved.
The present invention also provides a kind of anti-flaming polyolefin composition obtained using above-mentioned preparation method.It is described fire-retardant
Polyolefin complex includes expansion type flame retardant and polyolefin, and the expansion type flame retardant is dispersed in polyene
Hydrocarbon.
Relative in traditional expansion type flame retardant adding technology, having that fire retardant is scattered uneven, addition is big,
Flame retarding efficiency is low, destruction mechanical property the problems such as, the polyolefin in anti-flaming polyolefin composition of the present invention
In high-temperature heating, carbon source in the expansion type flame retardant is dehydrated into charcoal under acid source effect, and
The acid source is decomposed under the gas effect of generation, forms the carbonaceous layer of bulk multi-hole.The carbonaceous layer of the formation
The heat transfer between polyolefin and thermal source can be weakened, and prevent gas diffusion.In addition, the intumescent hinders
Combustion agent is thermally decomposed the non-combustible gas such as formed ammonia and also acts as acting on for dilution fuel gas, so as to hinder
Only flame transmission, makes polyolefin from further degraded, burning, to obtain good flame retardant effect.
Fire retardant polyolefin composite material of the present invention and preparation method thereof is said with reference to specific embodiment
It is bright：
Embodiment 1：
Weigh about 80 parts by weight of polypropylene, 23 parts by weight APPs and 6 parts by weight pentaerythrites.
Added after above-mentioned each raw material is mixed through high-speed mixer in the first extruder, melting extrusion is pre-mixed
Thing.
Premix is added in the second extruder；Wherein, the first half area temperature of screw rod is set to 200 DEG C, screw rod
Later half area's temperature be set to 185 DEG C；The titanium dioxide of about 5 parts by weight above-critical states is injected at the 1/4 of screw rod
Carbon, injection pressure is set to 18MPa；Pressure in second extruder maintains 10MPa, and extruding pelletization is obtained
Anti-flaming polypropylene composite.
Embodiment 2：
Weigh about 90 parts by weight of polypropylene, 30 parts by weight of ethylene-octene copolymer, 30 parts by weight melamines
Quadrafos and 6 weight starch.
Added after above-mentioned each raw material is mixed through high-speed mixer in the first extruder, melting extrusion is pre-mixed
Thing.
Premix is added in the second extruder；Wherein, the first half area temperature of screw rod is set to 195 DEG C, screw rod
Later half area's temperature be set to 190 DEG C；The carbon dioxide of about 6 parts by weight above-critical states is injected at the 1/4 of screw rod,
Injection pressure is set to 16MPa；Pressure in second extruder maintains 12MPa, and extruding pelletization obtains fire-retardant
The compound of polypropylene/ethylene-octene copolymer.
Embodiment 3：
Weigh about 110 weight account polyethylenes, 25 parts by weight APPs, 6 parts by weight pentaerythrites, 6 weight
Part melamine.
Added after above-mentioned each raw material is mixed through high-speed mixer in the first extruder, melting extrusion is pre-mixed
Thing.
Premix is added in the second extruder；Wherein, the first half area temperature of screw rod is set to 200 DEG C, screw rod
Later half area's temperature be set to 180 DEG C；The titanium dioxide of about 10 parts by weight above-critical states is injected at the 1/4 of screw rod
Carbon, injection pressure is set to 15MPa；Pressure in second extruder maintains 9MPa, and extruding pelletization is hindered
Fire polyethylene composite.
Embodiment 4：
Weigh about 100 parts by weight of ethylene-vinyl acetate copolymer eva, 26 parts by weight melamine phosphates and
12 parts by weight pentaerythrites.
Added after above-mentioned each raw material is mixed through high-speed mixer in the first extruder, melting extrusion is pre-mixed
Thing.
Premix is added in the second extruder；Wherein, the first half area temperature of screw rod is set to 210 DEG C, screw rod
Later half area's temperature be set to 200 DEG C；The titanium dioxide of about 7 parts by weight above-critical states is injected at the 1/4 of screw rod
Carbon, injection pressure is set to 20MPa；Pressure in second extruder maintains 8MPa, and extruding pelletization is hindered
Fire ethylene-vinyl acetate copolymer compound.
Embodiment 5：
Weigh about 80 parts by weight of polypropylene, 25 parts by weight EP rubbers, 30 parts by weight of phosphoric acid front three phenyl esters and
10 parts by weight bipentaerythrites.
Added after above-mentioned each raw material is mixed through high-speed mixer in the first extruder, melting extrusion is pre-mixed
Thing.
Premix is added in the second extruder；Wherein, the first half area temperature of screw rod is set to 190 DEG C, screw rod
Later half area's temperature be set to 205 DEG C；The carbon dioxide of about 5 parts by weight above-critical states is injected at the 1/4 of screw rod,
Injection pressure is set to 18MPa；Pressure in second extruder maintains 8MPa, and extruding pelletization obtains fire-retardant poly-
Propylene/EP rubbers compound.
Comparative example 1：
Weigh about 80 parts by weight of polypropylene, 23 parts by weight APPs and 6 parts by weight pentaerythrites.
Added after above-mentioned each raw material is mixed through high-speed mixer in the first extruder, melting extrusion is pre-mixed
Thing.
Premix is added in the second extruder；Wherein, the first half area temperature of screw rod is set to 200 DEG C, screw rod
Later half area's temperature be set to 185 DEG C；The carbon dioxide entrance of above-critical state at the 1/4 of screw rod is closed, is directly led to
Cross the second extruder extruding pelletization and obtain anti-flaming polypropylene composite.
Comparative example 2：
Weigh about 90 parts by weight of polypropylene, 30 parts by weight of ethylene-octene copolymer, 30 parts by weight melamines
Phosphate and 6 weight starch.
Added after above-mentioned each raw material is mixed through high-speed mixer in the first extruder, melting extrusion is pre-mixed
Thing.
Premix is added in the second extruder；Wherein, the first half area temperature of screw rod is set to 195 DEG C, screw rod
Later half area's temperature be set to 190 DEG C；The carbon dioxide entrance of above-critical state at the 1/4 of screw rod is closed, is directly led to
Cross the second extruder extruding pelletization and obtain flame-retardant polypropylene/ethylene-octene copolymer compound.
Micro Distribution, fire resistance and power are carried out to the product obtained by embodiment 1 to 5, comparative example 1 and 2
Performance characterization is learned, 1 is the results are shown in Table.Wherein, micro Distribution is characterized：Using ZEISS SEM；
Fire resistance is characterized：Using VOUCH 5801A oxygen index (OI)s testers and the vertical-horizontals of VOUCH 5402
UL-94 burning testers；Mechanical property is characterized：Using INSTRON universal testing machines and Chalpy impact
Strength-testing machine.
Table 1
From table 1, relative to comparative example 1 and 2, the anti-flaming polyolefin composition that embodiment 1 to 5 is obtained
Superior flame retardant property, its oxygen index (OI) is high, and can by UL-94 V-0 grades, its tensile strength and
Notch impact strength increases.It is excellent that this illustrates that the anti-flaming polyolefin composition that this preparation method is obtained has
Good fire resistance and mechanical property, beneficial to commercial application.
From Fig. 1 and Fig. 2, the expansion type flame retardant that the present embodiment 1 obtains anti-flaming polyolefin composition is equal
It is even to be distributed in polyolefin, and expansion type flame retardant agglomeration is more serious in comparative example 1.
The explanation of above example is only intended to the method and its core concept for helping to understand the present invention.It should refer to
Go out, for those skilled in the art, under the premise without departing from the principles of the invention, also
Some improvement and modification can be carried out to the present invention, these are improved and modification also falls into the claims in the present invention
In protection domain.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or uses this
Invention.A variety of modifications to these embodiments will be apparent for those skilled in the art,
Generic principles defined herein can without departing from the spirit or scope of the present invention, other
Realized in embodiment.Therefore, the present invention is not intended to be limited to the embodiments shown herein, but will
Meet the most wide scope consistent with features of novelty with principles disclosed herein.
Claims (9)
1. a kind of preparation method of anti-flaming polyolefin composition, it comprises the following steps：
(a) parts by weight of polyolefin 70~120, the parts by weight of expansion type flame retardant 15~100 are weighed；
(b) dry-blend is obtained by the polyolefin and expansion type flame retardant are dry-mixed, the dry-blend is then added the
In one extruder, melting extrusion obtains premix；
(c) premix is added in the second extruder, and 1/5~1/3 of the screw rod in the second extruder
Place is passed through the carbon dioxide of above-critical state, and melting extrusion obtains anti-flaming polyolefin composition.
2. a kind of preparation method of anti-flaming polyolefin composition as claimed in claim 1, it is characterised in that
Polyolefin described in step (a) is polyethylene, polypropylene, EP rubbers, ethylene-vinyl acetate copolymer, second
At least one of alkene-octene copolymer.
3. a kind of preparation method of anti-flaming polyolefin composition as claimed in claim 1, it is characterised in that
Expansion type flame retardant described in step (a) presses (2~4) by acid source, carbon source, source of the gas：(0~1)：(0~1)
Mass ratio mix, wherein the acid source be APP, melamine polyphosphate, biphosphate
At least one of ammonium, hypophosphites, cyanuric acid, tricresyl phosphate, alkyl phosphate, phosphonate ester, institute
Carbon source is stated for starch, pentaerythrite, bipentaerythrite, tripentaerythritol, sorbierite, phenolic resin, ring
At least one of dextrin, the source of the gas be dicyandiamide, melamine, urea, Lauxite at least
It is a kind of.
4. a kind of preparation method of anti-flaming polyolefin composition as claimed in claim 1, it is characterised in that
The mass ratio of expansion type flame retardant described in step (a) accounts for the 15%~45% of the gross mass of the dry-blend.
5. a kind of preparation method of anti-flaming polyolefin composition as claimed in claim 1, it is characterised in that
The quality of the carbon dioxide of above-critical state described in step (c) accounts for the 1%~20% of the premix gross mass.
6. a kind of preparation method of anti-flaming polyolefin composition as claimed in claim 1, it is characterised in that
The carbon dioxide of above-critical state is passed through in step (c) at the 1/4 of the screw rod of the second extruder.
7. a kind of preparation method of fire retardant polyolefin composite material as claimed in claim 1, it is characterised in that
The temperature in the first half area of the screw rod of the second extruder described in step (c) be 170 DEG C~210 DEG C, screw rod it is later half
The temperature in area is 160 DEG C~220 DEG C.
8. a kind of preparation method of anti-flaming polyolefin composition as claimed in claim 1, it is characterised in that
The injection pressure of the carbon dioxide of above-critical state described in step (c) is 7MPa~30MPa.
9. a kind of anti-flaming polyolefin composition obtained using such as any one of claim 1 to 8 preparation method,
Characterized in that, the anti-flaming polyolefin composition includes expansion type flame retardant and polyolefin, the intumescent
Fire retardant is dispersed in polyolefin.
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| CN107840996A (en) * | 2017-11-29 | 2018-03-27 | 西华大学 | A kind of expanding fire retardant and preparation method thereof |
| CN107857938A (en) * | 2017-11-29 | 2018-03-30 | 宁波海雨新材料科技有限公司 | A kind of halogen-free anti-flaming polypropylene material and its preparation method and application |
| CN110054809A (en) * | 2019-04-18 | 2019-07-26 | 宁波一舟塑胶有限公司 | Composite flame retardant, preparation method thereof and application thereof in polypropylene |
| CN110128741A (en) * | 2018-02-09 | 2019-08-16 | 中国科学院宁波材料技术与工程研究所 | Foam polyolefin material and preparation method thereof |
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| CN113583366A (en) * | 2021-07-14 | 2021-11-02 | 会通新材料(上海)有限公司 | High-temperature-resistant low-compression-deformation flame-retardant thermoplastic elastomer and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107840996A (en) * | 2017-11-29 | 2018-03-27 | 西华大学 | A kind of expanding fire retardant and preparation method thereof |
| CN107857938A (en) * | 2017-11-29 | 2018-03-30 | 宁波海雨新材料科技有限公司 | A kind of halogen-free anti-flaming polypropylene material and its preparation method and application |
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| CN110054809A (en) * | 2019-04-18 | 2019-07-26 | 宁波一舟塑胶有限公司 | Composite flame retardant, preparation method thereof and application thereof in polypropylene |
| CN110054809B (en) * | 2019-04-18 | 2021-04-06 | 宁波一舟塑胶有限公司 | Composite flame retardant, preparation method thereof and application thereof in polypropylene |
| CN110437553A (en) * | 2019-07-11 | 2019-11-12 | 佛山市德联邦盛光电科技股份有限公司 | A kind of fire retardant polystyrene plate and its processing method |
| CN112440545A (en) * | 2020-11-25 | 2021-03-05 | 浙江金科复合材料科技有限公司 | Manufacturing process of halogen-free flame-retardant polyethylene plastic-wood-steel composite board |
| CN113583366A (en) * | 2021-07-14 | 2021-11-02 | 会通新材料(上海)有限公司 | High-temperature-resistant low-compression-deformation flame-retardant thermoplastic elastomer and preparation method thereof |
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