CN103387712B - A graphene-modified flame-retardant polypropylene material and a preparation method thereof - Google Patents

A graphene-modified flame-retardant polypropylene material and a preparation method thereof Download PDF

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CN103387712B
CN103387712B CN201310308938.5A CN201310308938A CN103387712B CN 103387712 B CN103387712 B CN 103387712B CN 201310308938 A CN201310308938 A CN 201310308938A CN 103387712 B CN103387712 B CN 103387712B
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temperature
humidity province
halogen
polypropylene
flame
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CN103387712A (en
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贺芳
孙兆懿
孟征
钱晶
郭新利
黄兴宇
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Beijing Aerospace Chemical and Technology Corporation
Beijing Institute of Aerospace Testing Technology
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BEIJING AEROSPACE CHEMICAL AND TECHNOLOGY Corp
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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
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04—Particle-shaped
    • 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
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • 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
    • B29C48/40—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 using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • 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
    • B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
    • B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
    • 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
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B29C2948/9259—Angular velocity
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92885—Screw or gear
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895—Barrel or housing
    • 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
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0022—Combinations of extrusion moulding with other shaping operations combined with cutting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/10—Polymers of propylene
    • B29K2023/12—PP, i.e. polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0026—Flame proofing or flame retarding agents

Abstract

The invention relates to a polypropylene material, and particularly relates to a graphene-modified flame-retardant polypropylene material. Halogen-free flame-retardant polypropylene comprises 69-77 wt% of polypropylene, 23-25 wt% of a flame retardant and 0.01-2 wt% of a flame retardant synergist, wherein the flame retardant is at least one selected from a melamine polyphosphate, ammonium polyphosphate and pentaerythritol, and the flame retardant synergist is selected from modified graphene. The flame-retardant polypropylene material has effectively improved flame retardant property and improved mechanical properties.

Description

Anti-flaming polypropylene material of a kind of Graphene modification and preparation method thereof
Technical field
The present invention relates to a kind of polypropylene material, specifically, relate to a kind of anti-flaming polypropylene material with Graphene modification.
Background technology
In recent years, halogen-free fire retardant plastic enjoys people's concern, and halogen-free flameproof PP develops rapidly especially, by calendar year 2001, has exceeded 20% halogen-free flameproof product in global fire-retardant PP.In the halogen-free flame retardants that is applicable to PP, mainly containing aluminium hydroxide (ATH), magnesium hydroxide (MH), micro encapsulation red phosphorus, expanded graphite and phosphorus one nitrogen is expanding fire retardant (IFR) etc., wherein especially with IFR user's favor the most.But traditional expanding fire retardant also exists some problems, such as the foamed char compactness generating is poor, thermostability is not good enough, flame retarding efficiency is not ideal enough.Therefore, develop efficient, heat-resisting IFR, be still in current flame retardant area an interested problem for it.
Graphene is current the thinnest known material, and it has unique Two-dimensional Carbon atom laminated structure, and meanwhile, Graphene has very good electroconductibility.In addition, Graphene also has some other excellent physics-chem characteristic, as high absorbability, high chemical stability, up to the theoretical specific surface area of 2630 ㎡/g, ferromegnetism, good thermal conductivity etc.
Document Graphene filled polymer nanocomposites(Journal of Materials Chemistry, 2010) and document Functionalized Graphenes and Thermoplastic Nanocomposites Based upon Expanded Graphite Oxide(Polymer Science & Technology General, 2009) preparation of Graphene/polymkeric substance (nano-complex) is disclosed in, and disclose Graphene has been joined to PP, PU, SAN, PA6, PC, in PMMA, can improve its mechanical property, electric property, thermomechanical property, and some potential application are mentioned, as be used for structural strengthening, function intensified, for sensor, anti-electrostatic and EMI shielding material, electrode strip, inductive material etc.In prior art, only generally introduced the application in polymkeric substance of some Graphenes, the open Graphene of document not can be used as a kind of flame retardant.
For this reason, special proposition the present invention.
Summary of the invention
Primary goal of the invention of the present invention is to have proposed a kind of halogen-free anti-flaming polypropylene material.
The second goal of the invention of the present invention has been to propose the preparation method of this halogen-free anti-flaming polypropylene material.
In order to realize object of the present invention, the technical scheme of employing is:
The present invention relates to a kind of halogen-free anti-flaming polypropylene material, in this halogen-free polypropylene flame redardant, contain polypropylene 69～77wt%, fire retardant 23～25wt%, fire retarding synergist 0.01～2wt%; Wherein, fire retardant is selected from least one in melamine polyphosphate (MPP), ammonium polyphosphate, tetramethylolmethane (PER); Fire retarding synergist is selected from Graphene, preferably modified graphene.
The first optimal technical scheme of the present invention is: in halogen-free polypropylene flame redardant, also contain toughner, described toughner is selected from the graft copolymer of polyhutadiene, and its mass percentage content is 0.1～4% of halogen-free polypropylene flame redardant quality, preferably 1～4%.
The second optimal technical scheme of the present invention is: the graft copolymer 1～4wt% that contains polypropylene 69～77wt%, fire retardant 23～25wt%, Graphene 1～2wt%, polyhutadiene in halogen-free polypropylene flame redardant.
The 3rd optimal technical scheme of the present invention is: in described halogen-free polypropylene flame redardant, also contain compatilizer, described compatilizer is selected from maleic anhydride inoculated polypropylene or ST-4, its mass percentage content is 0.001～4% of halogen-free polypropylene flame redardant quality, preferably 0.01～2%.
The 4th optimal technical scheme of the present invention is: described fire retardant is the mixture of melamine polyphosphate and tetramethylolmethane, and the weight ratio of melamine polyphosphate and tetramethylolmethane is 1～5:1, preferably 2～4:1, more preferably 3:1.
The 5th optimal technical scheme of the present invention is: described modified graphene is selected from phosphoric doped graphene, and wherein the doping of phosphoric is 1～8wt%, preferably 3～6wt%.
The preparation method who the invention still further relates to this anti-flaming polypropylene material, comprises the following steps: first, by the blending extrusion granulation in proportion of fire retardant, fire retarding synergist and/or toughner, prepare flame-retardant master batch; And then by flame-retardant master batch and polypropylene after dispersing and mixing, by forcing machine melting, mixing, extrude, cooling, dry, pelletizing, be packaged to be finished product.
Wherein, the extruding pelletization temperature of preparing flame-retardant master batch is: the first humidity province temperature is 170～180 ℃; The second humidity province temperature is 185～195 ℃; The 3rd humidity province temperature is 200～210 ℃; The 4th humidity province temperature is 215～225 ℃; Head temperature is 205～215 ℃; Engine speed: 30～40 revs/min.Be preferably: the first humidity province temperature is 175～180 ℃; The second humidity province temperature is 190～195 ℃; The 3rd humidity province temperature is 205～210 ℃; The 4th humidity province temperature is 210～215 ℃; Head temperature is 210～215 ℃; Engine speed: 35～40 revs/min.
Wherein, by after flame-retardant master batch and polypropylene dispersing and mixing, while extruding by forcing machine, the each subregion temperature of barrel is: the first humidity province temperature is 175～185 ℃; The second humidity province temperature is 180～190 ℃; The 3rd humidity province temperature is 190～200 ℃; The 4th humidity province temperature is 205～215 ℃; Head temperature is 200～210 ℃; Engine speed: 30～40 revs/min.Be preferably, the first humidity province temperature is 185～190 ℃; The second humidity province temperature is 190～195 ℃; The 3rd humidity province temperature is 195～200 ℃; The 4th humidity province temperature is 210～215 ℃; Head temperature is 205～210 ℃; Engine speed: 35～40 revs/min.
Wherein, in extrusion, forcing machine is twin screw extruder, single screw extrusion machine.
Below technical scheme of the present invention is made further explanation.
The object of the invention is to study that a kind of flame retardant properties is good, the halogen-free polypropylene flame redardant of environmental protection, the present invention adopts Graphene to improve the properties of polypropylene flame redardant.Graphene is current the thinnest known material, and it has unique Two-dimensional Carbon atom laminated structure, and meanwhile, Graphene has very good electroconductibility.In addition, Graphene also has some other excellent physics-chem characteristic, as high absorbability, high chemical stability, up to the theoretical specific surface area of 2630 ㎡/g, ferromegnetism, good thermal conductivity etc.The grapheme material that the Graphene adopting in the present invention can adopt ultrathin sectioning, oxidation reduction process, chemical Vapor deposition process to prepare.For example can select graphene oxide JCGO-1, JCGO-2(Nanjing Ji Cang nanosecond science and technology company limited), its performance is as shown in table 1,2:
Table 1: sheet graphene oxide JCGO-1 performance perameter:
Figure BDA00003548236600031
Table 2: graphene oxide powder JCGO-2
Dianmeter 1～5μm
Thickness 0.8～1.2nm
Single?layer?ratio >99%
Purity >99%
The modified graphene of selecting in the present invention is P element doping Graphene more preferably, and wherein the doping of P element is 1～8wt%, preferably 3～6wt%.Concrete preparation method is: adopt improved Hummers oxidation style to be oxidized graphite: get Graphite Powder 99 and join 3ml and contain 1g K 2s 2o 8with 1g P 2o 5dense H 2sO 4in solution, be cooled to room temperature after heating 6h at 80 ℃, distilled water diluting, suction filtration, be washed to filtrate for neutral, air drying; Under condition of ice bath, get preoxidation graphite 2g obtained above and join the dense H of 46ml ice 2sO 4in solution, carefully slowly add 6gKMnO 4, stir 2h at 35 ℃, add subsequently 92mL distilled water, then in 15min, continue to add 280mL distilled water and 5mL30%H2O2, filtered while hot, it is neutral using successively 500ml HCl and a large amount of distilled water (volume ratio is 1:10) to wash to filtrate, air drying is stand-by.Under being stirred, above-mentioned dry graphite oxide 0.5g joins in 1L distilled water ultrasonic 3h, 4000rmin -1lower centrifugal 30min, supernatant liquid is concentration and is about 0.5mgml -1gO dispersion liquid.Get the GO dispersion liquid 30ml of above-mentioned preparation, add phosphoric acid by the consumption of 1:20, after magnetic agitation 30min, gained solution is proceeded in teflon-lined hydrothermal reaction kettle, naturally cooling after 160 ℃ of reaction 3h, obtain black solid, 10 postlyophilizations of centrifuge washing, had both obtained product P element doping Graphene.The Graphene that adopts scanning electron microscopic observation to prepare is individual layer sheet structure, by XPS analysis, determines that the content of P element in the P doped graphene of preparing is 5wt%.Use P doped graphene to can further improve the flame retarding efficiency of resin.
Confirm by the test to Graphene content, in polypropylene flame redardant, add weight percent content and be 1～2% Graphene, effectively raise the flame retardant properties of fire-retardant PP, and promoted the mechanical property of fire retardant material, it is best that the performance of the mechanics parameters such as its tensile strength, modulus in flexure, socle girder notched Izod impact strength reaches.
The present invention is simultaneously the selection to the fire retardant in polypropylene flame redardant and consumption improvement also, confirms by experiment, adopts the mixture of the 3:1 of melamine polyphosphate and tetramethylolmethane to prepare polypropylene flame redardant, and it is best that polyacrylic flame retardant effect and mechanical property reach.
In polypropylene flame redardant of the present invention, can also further add various auxiliary materials to increase polyacrylic performance of the present invention, in the present invention, add toughner, further to increase the toughness of polypropylene flame redardant, improve shock strength; Can also further add compatilizer, increase the consistency of polymkeric substance, thereby further improve the mechanical property of polypropylene flame redardant.
The specific embodiment of the present invention only limits to further explain and explanation the present invention, not to Composition of contents restriction of the present invention.
Embodiment
Embodiment 1～7
Table 3 is component and the mass percent of the anti-flaming polypropylene material of embodiment 1-7, and wherein fire retardant employing melamine polyphosphate (MPP) is 3:1 with tetramethylolmethane (PER) compound proportion, and synergist adopts P element doping Graphene;
Table 3:
? PP（wt%） Fire retardant (wt%) Graphene (wt%)
Embodiment 1 100 0 0
Embodiment 2 75 25 0
Embodiment 3 75 24.9 0.1
Embodiment 4 75 24.5 0.5
Embodiment 5 75 24 1
Embodiment 6 75 23 2
Embodiment 7 75 22.5 2.5
Preparation method is:
Adopt improved Hummers oxidation style to be oxidized graphite: to get Graphite Powder 99 and join 3ml and contain 1g K 2s 2o 8with 1g P 2o 5dense H 2sO 4in solution, be cooled to room temperature after heating 6h at 80 ℃, distilled water diluting, suction filtration, be washed to filtrate for neutral, air drying; Under condition of ice bath, get preoxidation graphite 2g obtained above and join the dense H of 46ml ice 2sO 4in solution, carefully slowly add 6gKMnO 4, stir 2h at 35 ℃, add subsequently 92mL distilled water, then in 15min, continue to add 280mL distilled water and 5mL30%H2O2, filtered while hot, it is neutral using successively 500ml HCl and a large amount of distilled water (volume ratio is 1:10) to wash to filtrate, air drying is stand-by.Under being stirred, above-mentioned dry graphite oxide 0.5g joins in 1L distilled water ultrasonic 3h, 4000rmin -1lower centrifugal 30min, supernatant liquid is concentration and is about 0.5mgml -1gO dispersion liquid.Get the GO dispersion liquid 30ml of above-mentioned preparation, add phosphoric acid by the consumption of 1:20, after magnetic agitation 30min, gained solution is proceeded in teflon-lined hydrothermal reaction kettle to naturally cooling after 160 ℃ of reaction 3h, obtain black solid, 10 postlyophilizations of centrifuge washing, had both obtained product P element doping Graphene, and the Graphene that adopts scanning electron microscopic observation to prepare is individual layer sheet structure, by XPS analysis, the content of determining P element in P doped graphene is 5wt%.
After fire retardant, fire retarding synergist are fully mixed under high-speed stirring, carry out granulation with twin screw extruder, make flame-retardant master batch, prilling temperature is: the first humidity province temperature is 175～180 ℃; The second humidity province temperature is 190～195 ℃; The 3rd humidity province temperature is 205～210 ℃; The 4th humidity province temperature is 210～215 ℃; Head temperature is 210～215 ℃; Engine speed: 35～40 revs/min.By flame-retardant master batch and PP after dispersing and mixing, by twin screw extruder melting, mixing, extrude, cooling, dry, pelletizing and packing.The each subregion temperature of barrel should remain on: the first humidity province temperature is 185～190 ℃; The second humidity province temperature is 190～195 ℃; The 3rd humidity province temperature is 195～200 ℃; The 4th humidity province temperature is 210～215 ℃; Head temperature is 205～210 ℃; Engine speed: 35～40 revs/min.
Performance to embodiment 1～7 product detects, and detected result is as shown in table 4:
Table 4:
Figure BDA00003548236600051
Interpretation of result: can find out by embodiment 1 and embodiment 2, added fire retardant and can effectively improve the flame retardant properties of PP material, but mechanical property can decline to some extent.And can find out by embodiment 2～7, the flame retardant properties of having added the PP material of Graphene further improves, and illustrates that Graphene and fire retardant systems have produced synergy, and along with the increase of Graphene addition, flame retardant properties is become better and better, and the tensile strength of material also increases gradually.
Embodiment 8～14
Table 5 is component and the mass percent of the anti-flaming polypropylene material of embodiment 8～14, and fire retardant is the mixture of melamine polyphosphate and tetramethylolmethane (PER), and synergist adopts P element doping Graphene;
Table 5:
? PP（wt%） MPP（wt%） PER（wt%） Graphene (wt%)
Embodiment 8 75 0 23 2
Embodiment 9 75 19.2 3.8 2
Embodiment 10 75 17.25 5.75 2
Embodiment 11 75 15.3 7.7 2
Embodiment 12 75 11.5 11.5 2
Embodiment 13 75 7.7 15.3 2
Embodiment 14 75 5.75 17.25 2
Preparation method is:
After fire retardant, fire retarding synergist are fully mixed under high-speed stirring, carry out granulation with twin screw extruder, make flame-retardant master batch, prilling temperature is: the first humidity province temperature is 170～180 ℃; The second humidity province temperature is 185～195 ℃; The 3rd humidity province temperature is 200～210 ℃; The 4th humidity province temperature is 215～225 ℃; Head temperature is 205～215 ℃; Engine speed: 30～40 revs/min; By flame-retardant master batch and PP after dispersing and mixing, by twin screw extruder melting, mixing, extrude, cooling, dry, pelletizing and packing.The each subregion temperature of barrel should remain on: the first humidity province temperature is 175～185 ℃; The second humidity province temperature is 180～190 ℃; The 3rd humidity province temperature is 190～200 ℃; The 4th humidity province temperature is 205～215 ℃; Head temperature is 200～210 ℃; Engine speed: 30～40 revs/min.
Performance to embodiment 8～14 products detects, and detected result is as shown in table 6:
Table 6:
Figure BDA00003548236600061
As can be seen from the above embodiments, adopt fire retardant of the present invention, can reach each performance perameter optimum.
Embodiment 15～17
Table 7 is component and the mass percent of the anti-flaming polypropylene material of embodiment 15～17, and toughner adopts the graft copolymer of polyhutadiene, and synergist adopts P element doping Graphene;
Table 7:
Figure BDA00003548236600062
Figure BDA00003548236600071
Preparation method is:
After fire retardant, fire retarding synergist, toughner are fully mixed under high-speed stirring, carry out granulation with twin screw extruder, make flame-retardant master batch, prilling temperature is: the first humidity province temperature is 175～180 ℃; The second humidity province temperature is 190～195 ℃; The 3rd humidity province temperature is 205～210 ℃; The 4th humidity province temperature is 210～215 ℃; Head temperature is 210～215 ℃; Engine speed: 35～40 revs/min.By flame-retardant master batch and PP after dispersing and mixing, by twin screw extruder melting, mixing, extrude, cooling, dry, pelletizing and packing.The each subregion temperature of barrel should remain on: the first humidity province temperature is 185～190 ℃; The second humidity province temperature is 190～195 ℃; The 3rd humidity province temperature is 195～200 ℃; The 4th humidity province temperature is 210～215 ℃; Head temperature is 205～210 ℃; Engine speed: 35～40 revs/min.
Performance to embodiment 15～17 products detects, and detected result is as shown in table 8:
Table 8:
Figure BDA00003548236600072
As can be seen from the above embodiments, interpolation toughner can improve the shock strength of halogen-free flameproof PP, but when addition is too large, the flame retardant resistance to material has a certain impact.
Embodiment 18～20:
Table 9 is component and the mass percent of the anti-flaming polypropylene material of embodiment 18～20, and compatilizer adopts maleic anhydride inoculated polypropylene, and synergist adopts P element doping Graphene;
Table 9:
Figure BDA00003548236600073
Preparation method: by fire retardant, fire retarding synergist and compatilizer mixing granulation, all the other techniques are with embodiment 15.
Performance to embodiment 18～20 products detects, and detected result is as shown in table 10:
Table 10:
Sample Tensile strength Modulus in flexure The punching of socle girder breach Limiting oxygen index(LOI) UL-94 Whether there is molten
? /MPa /MPa Hit intensity/kJm -2 % ? ?
Embodiment 18 27.2 986 4.2 31.6 V0 No
Embodiment 19 27.8 994 4.6 31.4 V0 No
Embodiment 20 27.6 963 4.6 31.3 V0 No
As can be seen from the above embodiments, add a certain amount of compatilizer and can improve the mechanical property of halogen-free flameproof PP, but too large addition is little to the Effect on Mechanical Properties of material.
Comparative example 1～3:
Table 11 is each group of component of comparative example 1～3, and shared heavy mass percent is with embodiment 6, and wherein fire retardant employing melamine polyphosphate (MPP) is 3:1 with tetramethylolmethane (PER) compound proportion;
Table 11:
Sample PP Fire retardant Graphene
Comparative example 1 PP MPP and PER mass ratio 3:1 JCGO-1
Comparative example 2 PP MPP and PER mass ratio 3:1 JCGO-2
Comparative example 3 PP MPP and PER mass ratio 3:1 P doped graphene
The preparation method of P doped graphene is with embodiment 1; Table 12 is the performance test results of each embodiment flame-proof ABS resin:
Table 12:
Comparative example 4～7:
Adopt ammonium polyphosphate (APP) and tetramethylolmethane (PER) to make fire retardant, method according to embodiment 1 is prepared anti-flaming polypropylene material, synergist is P doped graphene (preparation method of P element doping Graphene is with embodiment 1), and each weight percentages of components is as shown in table 13:
Table 13:
? PP（wt%） APP（wt%） PER（wt%） Graphene (wt%)
Comparative example 4 100 0 0 0
Comparative example 5 75 18.75 6.25 0
Comparative example 6 75 18.675 6.225 0.1
Comparative example 7 75 18.375 6.125 0.5
Comparative example 8 75 18 6 1
Comparative example 9 75 17.25 5.75 2
The performance of comparative example 4～9 products is detected, and detected result is as shown in table 14:
Table 14:
Figure BDA00003548236600091
From above comparative example, its performance of anti-flaming polypropylene material that adopts ammonium polyphosphate and tetramethylolmethane to prepare as fire retardant adopt melamine polyphosphate and tetramethylolmethane poor as the effect of fire retardant, proves that employing melamine polyphosphate and tetramethylolmethane can reach optimal effectiveness as fire retardant.

Claims (9)

1. a halogen-free anti-flaming polypropylene material, is characterized in that, contains the graft copolymer 2% of polypropylene 69～77wt%, fire retardant 23～25wt%, Graphene 1～2wt%, polyhutadiene in described halogen-free polypropylene flame redardant, and total amount is 100%; Described fire retardant is that weight ratio is melamine polyphosphate and the tetramethylolmethane of 3:1;
Described halogen-free anti-flaming polypropylene material preparation method is: first, by the blending extrusion granulation in proportion of the graft copolymer of fire retardant, Graphene and polyhutadiene, prepare flame-retardant master batch; And then by flame-retardant master batch and polypropylene after dispersing and mixing, by forcing machine melting, mixing, extrude, cooling, dry, pelletizing, be packaged to be finished product.
2. halogen-free anti-flaming polypropylene material according to claim 1, is characterized in that, contains the graft copolymer 2% of polypropylene 72wt%, fire retardant 24wt%, Graphene 2wt%, polyhutadiene in halogen-free polypropylene flame redardant; Described fire retardant is that weight ratio is melamine polyphosphate and the tetramethylolmethane of 3:1.
3. halogen-free anti-flaming polypropylene material according to claim 1, it is characterized in that, in described halogen-free polypropylene flame redardant, also contain compatilizer, described compatilizer is selected from maleic anhydride inoculated polypropylene or ST-4, and the mass percentage content of described compatilizer is 0.001～4% of halogen-free polypropylene flame redardant quality.
4. halogen-free anti-flaming polypropylene material according to claim 3, is characterized in that, the mass percentage content of described compatilizer is 0.01～2% of halogen-free polypropylene flame redardant quality.
5. halogen-free anti-flaming polypropylene material according to claim 1, is characterized in that, the extruding pelletization temperature of preparing flame-retardant master batch is: the first humidity province temperature is 170～180 ℃; The second humidity province temperature is 185～195 ℃; The 3rd humidity province temperature is 200～210 ℃; The 4th humidity province temperature is 215～225 ℃; Head temperature is 205～215 ℃; Engine speed: 30～40 revs/min.
6. halogen-free anti-flaming polypropylene material according to claim 5, is characterized in that, the first humidity province temperature is 175～180 ℃; The second humidity province temperature is 190～195 ℃; The 3rd humidity province temperature is 205～210 ℃; The 4th humidity province temperature is 210～215 ℃; Head temperature is 210～215 ℃; Engine speed: 35～40 revs/min.
7. halogen-free anti-flaming polypropylene material according to claim 1, is characterized in that, by after flame-retardant master batch and polypropylene dispersing and mixing, while extruding by forcing machine, the each subregion temperature of barrel is: the first humidity province temperature is 175～185 ℃; The second humidity province temperature is 180～190 ℃; The 3rd humidity province temperature is 190～200 ℃; The 4th humidity province temperature is 205～215 ℃; Head temperature is 200～210 ℃; Engine speed: 30～40 revs/min.
8. halogen-free anti-flaming polypropylene material according to claim 7, is characterized in that, the first humidity province temperature is 185～190 ℃; The second humidity province temperature is 190～195 ℃; The 3rd humidity province temperature is 195～200 ℃; The 4th humidity province temperature is 210～215 ℃; Head temperature is 205～210 ℃; Engine speed: 35～40 revs/min.
9. according to the anti-flaming polypropylene material described in the arbitrary claim of claim 5～8, it is characterized in that, in extrusion, forcing machine is twin screw extruder, single screw extrusion machine.
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