CN107805350A - High-dispersion nano OMMT/Polypropylene Composites and preparation method thereof - Google Patents

High-dispersion nano OMMT/Polypropylene Composites and preparation method thereof Download PDF

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CN107805350A
CN107805350A CN201710980930.1A CN201710980930A CN107805350A CN 107805350 A CN107805350 A CN 107805350A CN 201710980930 A CN201710980930 A CN 201710980930A CN 107805350 A CN107805350 A CN 107805350A
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polypropylene
nano
ommt
master batch
melt
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郑云龙
黄志杰
屈国梁
王海华
杨仓先
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Nakahiro Junl (shanghai) New Material Co Ltd
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Nakahiro Junl (shanghai) New Material Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/20Compounding polymers with additives, e.g. colouring
    • C08J3/22Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10Homopolymers or copolymers of propene
    • C08J2323/14Copolymers of propene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2451/00Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/06Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/005Additives being defined by their particle size in general
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • C08K3/346Clay

Abstract

The invention discloses a kind of high-dispersion nano OMMT/Polypropylene Composites, its raw material is included high flowing low crushing-resistant copolymerization propylene 25% 50% by mass fraction;Low flowing high-impact co-polypropylene 30% 50%;Long metallocene polyolefin tenacity-increased dose of block 5% 15%;Nm-class montmorillonite filled master batch 10% 30%.The invention also discloses a kind of preparation method of high-dispersion nano OMMT/Polypropylene Composites.High-dispersion nano OMMT/Polypropylene Composites of the present invention and preparation method thereof, the processing problem " easily assembled, difficult scattered " when melt blending is extruded for nano-powder material, employ double rank extrusions, the processing mode that secondary combination shearing is kneaded, the dispersion problem of nano-powder material is efficiently solved, especially in high level(≥15%)Under obturator distribution situation, given full play to " small size, Gao Zenggang " nano effect.

Description

High-dispersion nano OMMT/Polypropylene Composites and preparation method thereof
Technical field
The present invention relates to fields such as high polymer materials, specially a kind of class montmorillonite filled polypropylene composite materials material of high-dispersion nano Material and preparation method thereof.
Background technology
Polypropylene is the polyolefine material of the good high comprehensive performance of a kind of lightweight, high-performance, easy processing, chemical resistance, Its general density is all in (0.9g/cm3-0.93g/cm3), far below other type materials such as ABS, PC, PS, PA, therefore it is used for Low-density, the base resin of light material have geneogenous advantage;Polypropylene PP advantage is in the side in its molecular chain structure The presence of chain methyl so that polymer chain is easier rule and piled up, so as to formed compact structure, function admirable microcosmic crystal Structure, this is the basic reason for the polythene PE material that its performance is especially rigidly far above similar density;Meanwhile also remain The good processing fluidity of polyolefine material and preferable cost advantage, thus develop neck in current light weight material in automobile Had a wide range of applications in domain, usually as modified base resin material.
Nano-powder filled polypropylene material is the emerging field being modified in recent years on polypropylene high performance;Nanometer material Material, which possesses high decentralization and extremely low particle diameter (less than 100 nanometers), its excellent dimensional effect, can be obviously improved poly- third The inflexible target of alkene material, and be unlikely to that its toughness is greatly lowered, thus be a kind of polypropylene modification method of rigidity-toughness balanced, But also the processing dispersiveness to nano-powder material proposes high requirement.Due to the self aggregation characteristic of nano-powder material, Nano-powder material content used is than relatively low (≤10%) in conventional blending extrusion, as described in CN106366456 High-performance nano montmorillonite RPP material, due to using single-order blending extrusion, nano-powder content is only 5-8%, and Compatilizer used is conventional maleic anhydride grafts;CN104045909 uses phenolic resin modified nano imvite, although effect Fruit is preferable, but employs chemical-solvent method modification mode, it is difficult to suitable for large-scale industrialization volume production, and easily produces solvent Pollution.
The content of the invention
The purpose of the present invention is:A kind of high-dispersion nano OMMT/Polypropylene Composites are provided, it is existing to solve Technological deficiency in technology.
Realizing the technical scheme of above-mentioned purpose is:A kind of high-dispersion nano OMMT/Polypropylene Composites, it is former Material includes the low crushing-resistant copolymerization propylene 25%-50% of high flowing by mass fraction;Low flowing high-impact co-polypropylene 30%-50%; Long metallocene polyolefin tenacity-increased dose 5% -15% of block;Nm-class montmorillonite filled master batch 10%-30%.
In a preferred embodiment of the invention, the nm-class montmorillonite filled master batch is by nano imvite powder, methyl Glycidyl acrylate graft polypropylene forms, wherein, the quality of the nano imvite powder accounts for the nano imvite The 50% of filler parent granule quality.
In a preferred embodiment of the invention, the glycidyl methacrylate graft polypropylene is melt blending Grafted polypropylene material prepared by Graft Method, its grafting rate are 0.6% -1.2%.
In a preferred embodiment of the invention, described nano imvite powder is density 1.7g/cm3, scattered yardstick 3.5nm-5nm inorganic particle.
In a preferred embodiment of the invention, long metallocene polyolefin tenacity-increased dose of the block has primary structure special Sign, the key structural feature are the long block polyoctenamer segment catalyzed and synthesized by new metallocene catalyst.
In an of the invention preferred embodiment, described height flows low crushing-resistant copolymerization propylene, in 230 DEG C, 2.16Kg Under test condition, its melt index is 60g/10min-150g/10min, notch impact strength >=10kJ/cm3;Described low stream For dynamic high-impact co-polypropylene under 230 DEG C, 2.16Kg test condition, its melt index be 5g/10min-30g/10min, scarce Mouth impact strength >=30kJ/cm3
The second object of the present invention is:A kind of high-dispersion nano OMMT/Polypropylene Composites preparation side is provided Method, double rank second meltings based on physical blending process are kneaded scattered mode, do not produce any solvent and other Organic Pollutions, And be granulated after disperseing twice when the powder content of material can be made to be promoted to 20% and still possess good dispersion effect, without It is green as causing powder reuniting.
Realizing the technical scheme of above-mentioned purpose is:A kind of high-dispersion nano OMMT/Polypropylene Composites preparation side Method, comprise the following steps:Step S1) obtain the raw materials of described high-dispersion nano OMMT/Polypropylene Composites;Step Rapid S2) height in the mixing raw material flows low crushing-resistant copolymerization propylene, low flowing high-impact co-polypropylene, long block metallocene and gathers Olefinic tougheners obtain the first mixture;Step S3) prepare the melt of the nm-class montmorillonite filled master batch;Step S4) by institute The first mixture is stated to be positioned in the main feeding bin for tightly engaging parallel dual-screw extruding machine, and through feed screw by described first Mixture is added in the main barrel of extruder and melted;Step S5) by the melt of the nm-class montmorillonite filled master batch from described The lateral spout for tightly engaging parallel dual-screw extruding machine is injected into main barrel;Step S6) the first of molten condition is mixed The melt of compound and nm-class montmorillonite filled master batch batch mixing, shearing, scattered, and through tightly engaging parallel dual-screw extruding machine together Extrusion, obtains extrudate;Step S7) extrudate cooling, drying, granulation are handled, obtain PP composite material.
In a preferred embodiment of the invention, the step S3) comprise the following steps:Step S31) obtain described in preparation The dispensing of nm-class montmorillonite filled master batch, the dispensing include nano imvite powder, glycidyl methacrylate graft Polypropylene each 50%;Step S32) dispensing is mixed, obtain the second mixture;Step S33) by second mixture It is positioned in the main feeding bin of taper Strong shear single screw extrusion machine, is obtained through chemical melting graft reaction nm-class montmorillonite filled The melt of master batch, and extruded through taper Strong shear single screw extrusion machine, then by the nm-class montmorillonite filled master batch of the extrusion Melt is injected into described tightly engage inside the main barrel of parallel dual-screw extruding machine.
In an of the invention preferred embodiment, the taper Strong shear single screw extrusion machine is from the taper Strong shear list spiral shell The charge door of the main barrel of bar extruder is sequentially provided with humidity province to head outlet, and the temperature of each humidity province is followed successively by:60℃、 190℃、210℃、225℃、230℃、 230℃、230℃。
In a preferred embodiment of the invention, the parallel dual-screw extruding machine that tightly engages tightly engages in the same direction from this The charge door of the main barrel of double screw extruder is sequentially provided with humidity province to head outlet, and the temperature of each humidity province is followed successively by:60 ℃、160℃、190℃、195℃、 200℃、210℃、210℃。
It is an advantage of the invention that:The high-dispersion nano OMMT/Polypropylene Composites of the present invention and its preparation side Method, for nano-powder material when melt blending is extruded " easily aggregation, difficult scattered " processing problem, employ double ranks extrusions, The processing mode that secondary combination shearing is kneaded, efficiently solves the dispersion problem of nano-powder material, especially contains higher The obturator distribution situation under (>=15%) is measured, has given full play to " small size, Gao Zenggang " nano effect.It is molten by difference Refer to, the polypropylene matrix of different anti-impact characteristics compounding, and the use of long block POE toughener, make obtained modified polypropene The performance indications of composite are obviously improved, especially the impact property in low temperature (- 30 DEG C).Pass through the technology of the present invention The high-dispersion nano OMMT/Polypropylene Composites that scheme is prepared, on the premise of low-density, low filling (0.95g/cm3-1.00g/cm3), the year-on-year current material modified lifting 60-80% of conventional talc of its bending modulus, reach 1700MPa or so, level similar in notch impact strength holding are arrived, and -30 DEG C of low temperature notched impact strengths lift 20%- 30%, it is 11 kJ/m2-12kJ/m2, this will be attributed to the fact that the nano-filled body of high dispersive and gathering with long block polyoctenamer segment The cooperative effect of olefinic tougheners, it is that one kind takes into account rigidity, toughness both sides high performance modified polypropene technical scheme.
Embodiment
The present invention illustrated below can be used to the specific embodiment implemented.
A kind of high-dispersion nano OMMT/Polypropylene Composites, its raw material include height by mass fraction and flow low resist Rush co-polypropylene 25%-50%;Low flowing high-impact co-polypropylene 30% -50%;Long metallocene polyolefin tenacity-increased dose of block 5%-15%;Nm-class montmorillonite filled master batch 10%-30%.The nm-class montmorillonite filled master batch by nano imvite powder, Glycidyl methacrylate graft polypropylene forms, wherein, the quality of the nano imvite powder accounts for the nanometer and covered Take off the 50% of native filler parent granule quality.The glycidyl methacrylate graft polypropylene is prepared for melt blending Graft Method Grafted polypropylene material, its grafting rate is 0.6%-1.2%.In a preferred embodiment of the invention, described nanometer is covered It is density 1.7g/cm to take off native powder3, scattered yardstick 3.5nm-5nm inorganic particle.The long block is metallocene polyolefin tenacity-increased Agent has key structural feature, and the key structural feature includes the long block polyoctenamer catalyzed and synthesized by new metallocene catalyst Segment.
The present invention is further explained with reference to specific embodiment and comparative example.Wherein, embodiment and comparative example Raw material and quality it is as shown in table 1 below.
Table 1:Embodiment 1-5 and comparative example 1 feed components and quality proportioning table.
(unit:g)
The embodiment of the present invention is raw materials used to be described as follows:
PP-1:Height flows low crushing-resistant copolymerization propylene, and melt index MFR is 60g/10min (230 DEG C, 2.16Kg), breach Impact strength 6.7kJ/m2
PP-2:Height flows low crushing-resistant copolymerization propylene, and melt index MFR is 70g/10min (230 DEG C, 2.16Kg), breach Impact strength 5.9kJ/m2
PP-3:Low flowing high-impact co-polypropylene, melt index MFR are 8g/10min (230 DEG C, 2.16Kg), and breach rushes Hit intensity 48kJ/m2
PP-4:Low flowing high-impact co-polypropylene, melt index MFR is 10g/10min (230 DEG C, 2.16Kg), breach Impact strength 54kJ/m2
Long metallocene polyolefin tenacity-increased dose of block:Melt index MFR is 2.0g/10min (190 DEG C, 2.16Kg).
Nano imvite -1:Nano imvite powder, it is 3.5-5.5nm to disperse yardstick (XRD d001).
Nano imvite -2:Nano imvite powder, it is 3.5-5nm to disperse yardstick (XRD d001).
Glycidyl methacrylate graft polypropylene:PP-g-MAH, co-polypropylene matrix, chemical determination grafting rate For 1.0%.
Talcum powder:Dioxide-containing silica 60%, 3000 mesh.
Embodiment 1:A kind of high-dispersion nano OMMT/Polypropylene Composites preparation method, comprises the following steps. Step S1) raw materials of described high-dispersion nano OMMT/Polypropylene Composites is obtained according to table 1:Polypropylene (PP-2) (nanometer is covered de- for 50g, polypropylene (PP-3) 30g, metallocene polyolefin tenacity-increased dose of 10g of long block, nm-class montmorillonite filled master batch Soil -1) 5g, PP-g-GMA 5g.Step S2) polypropylene (PP-2) in the mixing raw material, polypropylene (PP-3), long block cyclopentadienyl Metal polyolefine toughener obtains the first mixture.Step S3) prepare the melt of the nm-class montmorillonite filled master batch;It is described Step S3) comprise the following steps.Step S31) dispensing for preparing the nm-class montmorillonite filled master batch is obtained, the dispensing includes Nano imvite powder, glycidyl methacrylate graft polypropylene each 50%.Step S32) dispensing is mixed, obtain To the second mixture.Step S33) second mixture is positioned over to the main feeding bin of taper Strong shear single screw extrusion machine In, the melt of nm-class montmorillonite filled master batch is obtained through chemical melting graft reaction, and through taper Strong shear single screw extrusion machine Extrusion, then the melt of the nm-class montmorillonite filled master batch of the extrusion is injected into and described tightly engages parallel dual-screw extruding machine Main barrel inside.The taper Strong shear single screw extrusion machine adds from the main barrel of the taper Strong shear single screw extrusion machine Material mouth is sequentially provided with humidity province to head outlet, and the temperature of each humidity province is followed successively by:60℃、190℃、210℃、225℃、230 ℃、230℃、230℃.Step S4) first mixture is positioned over to the main feeding for tightly engaging parallel dual-screw extruding machine In storehouse, and first mixture is added in the main barrel of extruder through feed screw and melted.Step S5) by the nanometer The melt of class montmorillonite filled master batch is injected into main barrel from the lateral spout for tightly engaging parallel dual-screw extruding machine. Step S6) by the melt of the first mixture of molten condition and nm-class montmorillonite filled master batch together batch mixing, shearing, scattered, and Through tightly engaging parallel dual-screw extruding machine extrusion, extrudate is obtained.It is described that to tightly engage parallel dual-screw extruding machine tight from this The charge door of the main barrel of close meshing co rotating twin screw extrusion is sequentially provided with humidity province, the temperature of each humidity province to head outlet It is followed successively by:60℃、160℃、190℃、195℃、200℃、210℃、210℃.Extruder screw a diameter of 35mm, draw ratio L/ D is 40, and engine speed is 250 revs/min.Step S7) extrudate cooling, drying, granulation are handled, obtain polypropylene composite materials material Material.
Embodiment 2:A kind of high-dispersion nano OMMT/Polypropylene Composites preparation method, comprises the following steps. Step S1) raw materials of described high-dispersion nano OMMT/Polypropylene Composites is obtained according to table 1:Polypropylene (PP-1) 40g, polypropylene (PP-3) 42g, metallocene polyolefin tenacity-increased dose of 8g of long block, nm-class montmorillonite filled master batch (nano imvite -2)5g、PP-g-GMA 5g.Step S2) polypropylene (PP-1), polypropylene (PP-3), long block cyclopentadienyl gold in the mixing raw material Category polyolefine toughener obtains the first mixture.Step S3) prepare the melt of the nm-class montmorillonite filled master batch;The step Rapid S3) comprise the following steps.Step S31) dispensing for preparing the nm-class montmorillonite filled master batch is obtained, the dispensing includes receiving Rice montmorillonite powder, glycidyl methacrylate graft polypropylene each 50%.Step S32) dispensing is mixed, obtain Second mixture.Step S33) second mixture is positioned in the main feeding bin of taper Strong shear single screw extrusion machine, The melt of nm-class montmorillonite filled master batch is obtained through chemical melting graft reaction, and is squeezed through taper Strong shear single screw extrusion machine Go out, then the melt of the nm-class montmorillonite filled master batch of the extrusion is injected into and described tightly engages parallel dual-screw extruding machine Inside main barrel.Charging of the taper Strong shear single screw extrusion machine from the main barrel of the taper Strong shear single screw extrusion machine Mouth is sequentially provided with humidity province to head outlet, and the temperature of each humidity province is followed successively by:60℃、190℃、210℃、225℃、 230 ℃、230℃、230℃.Step S4) first mixture is positioned over to the main feeding for tightly engaging parallel dual-screw extruding machine In storehouse, and first mixture is added in the main barrel of extruder through feed screw and melted.Step S5) by the nanometer The melt of class montmorillonite filled master batch is injected into main barrel from the lateral spout for tightly engaging parallel dual-screw extruding machine. Step S6) by the melt of the first mixture of molten condition and nm-class montmorillonite filled master batch together batch mixing, shearing, scattered, and Through tightly engaging parallel dual-screw extruding machine extrusion, extrudate is obtained.It is described that to tightly engage parallel dual-screw extruding machine tight from this The charge door of the main barrel of close meshing co rotating twin screw extrusion is sequentially provided with humidity province, the temperature of each humidity province to head outlet It is followed successively by:60℃、160℃、190℃、195℃、200℃、210℃、210℃.Extruder screw a diameter of 35mm, draw ratio L/ D is 40, and engine speed is 250 revs/min.Step S7) extrudate cooling, drying, granulation are handled, obtain polypropylene composite materials material Material.
Embodiment 3:A kind of high-dispersion nano OMMT/Polypropylene Composites preparation method, comprises the following steps. Step S1) raw materials of described high-dispersion nano OMMT/Polypropylene Composites is obtained according to table 1:Polypropylene (PP-1) 44g, polypropylene (PP-4) 30g, metallocene polyolefin tenacity-increased dose of 10g of long block, nm-class montmorillonite filled master batch (nano imvite -1)8g、PP-g-GMA 8g.Step S2) polypropylene (PP-1), polypropylene (PP-4), long block cyclopentadienyl gold in the mixing raw material Category polyolefine toughener obtains the first mixture.Step S3) prepare the melt of the nm-class montmorillonite filled master batch;The step S3) comprise the following steps.Step S31) dispensing for preparing the nm-class montmorillonite filled master batch is obtained, the dispensing includes nanometer Montmorillonite powder, glycidyl methacrylate graft polypropylene each 50%.Step S32) dispensing is mixed, obtain Two mixtures.Step S33) second mixture is positioned in the main feeding bin of taper Strong shear single screw extrusion machine, pass through Chemical melting graft reaction obtains the melt of nm-class montmorillonite filled master batch, and is extruded through taper Strong shear single screw extrusion machine, Then the melt of the nm-class montmorillonite filled master batch of the extrusion is injected into the master for tightly engaging parallel dual-screw extruding machine Inside machine barrel.Charge door of the taper Strong shear single screw extrusion machine from the main barrel of the taper Strong shear single screw extrusion machine Humidity province is sequentially provided with to head outlet, the temperature of each humidity province is followed successively by:60℃、190℃、210℃、225℃、 230℃、 230℃、230℃.Step S4) first mixture is positioned over to the main feeding bin for tightly engaging parallel dual-screw extruding machine In, and first mixture is added in the main barrel of extruder through feed screw and melted.Step S5) nanometer is covered The melt for taking off native filler parent granule is injected into main barrel from the lateral spout for tightly engaging parallel dual-screw extruding machine.Step Rapid S6) by the melt of the first mixture of molten condition and nm-class montmorillonite filled master batch together batch mixing, shearing, scattered, and pass through Parallel dual-screw extruding machine extrusion is tightly engaged, obtains extrudate.It is described that to tightly engage parallel dual-screw extruding machine close from this The charge door of the main barrel of meshing co rotating twin screw extrusion is sequentially provided with humidity province to head outlet, the temperature of each humidity province according to It is secondary to be:60℃、160℃、190℃、195℃、200℃、210℃、210℃.Extruder screw a diameter of 35mm, draw ratio L/D For 40, engine speed is 250 revs/min.Step S7) extrudate cooling, drying, granulation are handled, obtain polypropylene composite materials material Material.
Embodiment 4:A kind of high-dispersion nano OMMT/Polypropylene Composites preparation method, comprises the following steps. Step S1) raw materials of described high-dispersion nano OMMT/Polypropylene Composites is obtained according to table 1:Polypropylene (PP-2) 30g, polypropylene (PP-4) 38g, metallocene polyolefin tenacity-increased dose of 8g of long block, nm-class montmorillonite filled master batch (nano imvite -1)12g、PP-g-GMA 12g.Step S2) polypropylene (PP-2) in the mixing raw material, polypropylene (PP-4), long block cyclopentadienyl Metal polyolefine toughener obtains the first mixture.Step S3) prepare the melt of the nm-class montmorillonite filled master batch;It is described Step S3) comprise the following steps.Step S31) dispensing for preparing the nm-class montmorillonite filled master batch is obtained, the dispensing includes Nano imvite powder, glycidyl methacrylate graft polypropylene each 50%.Step S32) dispensing is mixed, obtain To the second mixture.Step S33) second mixture is positioned over to the main feeding bin of taper Strong shear single screw extrusion machine In, the melt of nm-class montmorillonite filled master batch is obtained through chemical melting graft reaction, and through taper Strong shear single screw extrusion machine Extrusion, then the melt of the nm-class montmorillonite filled master batch of the extrusion is injected into and described tightly engages parallel dual-screw extruding machine Main barrel inside.The taper Strong shear single screw extrusion machine adds from the main barrel of the taper Strong shear single screw extrusion machine Material mouth is sequentially provided with humidity province to head outlet, and the temperature of each humidity province is followed successively by:60℃、190℃、210℃、225℃、 230 ℃、230℃、230℃.Step S4) first mixture is positioned over to the main feeding for tightly engaging parallel dual-screw extruding machine In storehouse, and first mixture is added in the main barrel of extruder through feed screw and melted.Step S5) by the nanometer The melt of class montmorillonite filled master batch is injected into main barrel from the lateral spout for tightly engaging parallel dual-screw extruding machine. Step S6) by the melt of the first mixture of molten condition and nm-class montmorillonite filled master batch together batch mixing, shearing, scattered, and Through tightly engaging parallel dual-screw extruding machine extrusion, extrudate is obtained.It is described that to tightly engage parallel dual-screw extruding machine tight from this The charge door of the main barrel of close meshing co rotating twin screw extrusion is sequentially provided with humidity province, the temperature of each humidity province to head outlet It is followed successively by:60℃、160℃、190℃、195℃、200℃、210℃、210℃.Extruder screw a diameter of 35mm, draw ratio L/ D is 40, and engine speed is 250 revs/min.Step S7) extrudate cooling, drying, granulation are handled, obtain polypropylene composite materials material Material.
Embodiment 5:A kind of high-dispersion nano OMMT/Polypropylene Composites preparation method, comprises the following steps. Step S1) raw materials of described high-dispersion nano OMMT/Polypropylene Composites is obtained according to table 1:Polypropylene (PP-1) 30g, polypropylene (PP-4) 35g, metallocene polyolefin tenacity-increased dose of 5g of long block, nm-class montmorillonite filled master batch (nano imvite -2)15g、PP-g-GMA 15g.Step S2) polypropylene (PP-1) in the mixing raw material, polypropylene (PP-4), long block cyclopentadienyl Metal polyolefine toughener obtains the first mixture.Step S3) prepare the melt of the nm-class montmorillonite filled master batch;It is described Step S3) comprise the following steps.Step S31) dispensing for preparing the nm-class montmorillonite filled master batch is obtained, the dispensing includes Nano imvite powder, glycidyl methacrylate graft polypropylene each 50%.Step S32) dispensing is mixed, obtain To the second mixture.Step S33) second mixture is positioned over to the main feeding bin of taper Strong shear single screw extrusion machine In, the melt of nm-class montmorillonite filled master batch is obtained through chemical melting graft reaction, and through taper Strong shear single screw extrusion machine Extrusion, then the melt of the nm-class montmorillonite filled master batch of the extrusion is injected into and described tightly engages parallel dual-screw extruding machine Main barrel inside.The taper Strong shear single screw extrusion machine adds from the main barrel of the taper Strong shear single screw extrusion machine Material mouth is sequentially provided with humidity province to head outlet, and the temperature of each humidity province is followed successively by:60℃、190℃、210℃、225℃、 230 ℃、230℃、230℃.Step S4) first mixture is positioned over to the main feeding for tightly engaging parallel dual-screw extruding machine In storehouse, and first mixture is added in the main barrel of extruder through feed screw and melted.Step S5) by the nanometer The melt of class montmorillonite filled master batch is injected into main barrel from the lateral spout for tightly engaging parallel dual-screw extruding machine. Step S6) by the melt of the first mixture of molten condition and nm-class montmorillonite filled master batch together batch mixing, shearing, scattered, and Through tightly engaging parallel dual-screw extruding machine extrusion, extrudate is obtained.It is described that to tightly engage parallel dual-screw extruding machine tight from this The charge door of the main barrel of close meshing co rotating twin screw extrusion is sequentially provided with humidity province, the temperature of each humidity province to head outlet It is followed successively by:60℃、160℃、190℃、195℃、200℃、210℃、210℃.Extruder screw a diameter of 35mm, draw ratio L/ D is 40, and engine speed is 250 revs/min.Step S7) extrudate cooling, drying, granulation are handled, obtain polypropylene composite materials material Material.
Comparative example 1:The raw material of PP composite material is obtained according to table 1:Polypropylene (PP-2) 45g, polypropylene (PP-3) 30g, metallocene polyolefin tenacity-increased dose of 10g of long block, talcum powder 15g.In the present embodiment, not including nm-class montmorillonite filled mother Grain, and replaced using talcum powder.Mix the height in the raw material and flow low crushing-resistant copolymerization propylene, low flowing high-impact copolymerization third Alkene, metallocene polyolefin tenacity-increased dose of long block, talcum powder obtain mixture.The mixture is positioned over and tightly engages in the same direction pair In the main feeding bin of screw extruder, and the mixture is added in the main barrel of extruder through feed screw and melted.Will It is the mixture batch mixing of molten condition, shearing, scattered, and through tightly engaging parallel dual-screw extruding machine extrusion, obtain extrudate.Institute State tightly engage parallel dual-screw extruding machine from this tightly engage parallel dual-screw extruding machine main barrel charge door to head Outlet is sequentially provided with humidity province, and the temperature of each humidity province is followed successively by: 60℃、160℃、190℃、195℃、200℃、210℃、 210℃.Extruder screw a diameter of 35mm, draw ratio L/D are 40, and engine speed is 250 revs/min.To extrudate cooling, dry Dry, granulation processing, obtains PP composite material.
The Properties of Polypropylene Composite obtained by above-described embodiment 1-5 and comparative example 1 is tested and contrasted below, is surveyed The performance parameter obtained after examination is as shown in table 2, and wherein test parameter standard is as follows, properties of product test:
Density measurement:By ISO1183-1 standard testings;
Melt flow rate (MFR) is tested;By ISO1133-1 standard testings, test condition is 230 DEG C, 2.26Kg;
Tensile property:Carried out by ISO527-2 standards, test rate 5mm/min;
Bending property:Carried out by IS178 standards, span 64mm, test rate 2mm/min;
Impact property:Carried out by ISO179-1 standards on impact tester for simple supported beam, batten breach is A types, is existed respectively Tested under normal temperature (23 DEG C), low temperature (- 30 DEG C);
Shrinkage factor is tested:Tested by ISO 294-4 standards, standard jig is 210 × 140 × 3.2mm;
Nano-powder dispersion size characterizes:Carried out on KYKY-TEM8290 transmission electron microscopes, enlargement ratio difference For 3000 times, nano-powder dispersion particle diameter in test material.
Table 2:Embodiment 1-5 and the PP composite material of comparative example 1 the performance test results.
From table 2 from the point of view of each embodiment 1-5 material properties test data, nano imvite powder used is in dosage In the range of 5%-15%, extruded by double ranks, the processing mode of compound mixing granulator, the dispersion size of its powder can be controlled Make and in below 200nm, meet nano-filled dispersion size requirement;Further contrast each embodiment data to understand, with nanometer The lifting of montmorillonite dosage, its dispersion size are that particle diameter still has the trend lifted successively, show the tendency of its self aggregation not There is radical change, therefore, the dispersion effect of filling powder is more preferable in the case of middle low content (5%-8%), and further lifting is used Measure (15%), the performance indications lifting amplitude and unobvious of material.
With in comparative example 1 by adding the Contrast on effect of the PP composite material obtained by common talcum powder:Equal In the case of content (15%), by adding the PP composite material (embodiment 5) obtained by nm-class montmorillonite filled master batch Properties data all will substantially get well, and bending modulus is promoted to 2090MPa from 1780MPa, and the notch shock under normal temperature, low temperature is strong Degree is also obvious more preferable;And powder content can then be down to 5% or so by embodiment 1, density reduces 8-10%, its bending modulus 1700MPa or so is still maintained at, and toughness index such as normal temperature, low temperature notched impact strength has also carried compared with comparative example 1 Rise.Above-mentioned test data fully shows, modified poly- third is filled in by the nm-class montmorillonite filled master batch of multiple melting mixing Alkene composite, it can be realized really on the premise of relatively lower dosage similar with the modification of the common talcum powder of higher dosage Effect, be a kind of rigidity of General Promotion material, the preferable lightweight solution of toughness index, especially suitable for current vapour The in-car exterior trim such as larger decorative such as bumper, wheel arch, door sill protector, door trim, instrument board product is to high-performance, lightweight lightweight The active demand of modified polypropylene material.
These are only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and All any modification, equivalent and improvement made within principle etc., should be included in the scope of the protection.

Claims (10)

1. a kind of high-dispersion nano OMMT/Polypropylene Composites, it is characterised in that its raw material is included by mass fraction
Height flows low crushing-resistant copolymerization propylene 25%-50%;
Low flowing high-impact co-polypropylene 30%-50%;
Long metallocene polyolefin tenacity-increased dose of 5%-15% of block;
Nm-class montmorillonite filled master batch 10%-30%.
2. high-dispersion nano OMMT/Polypropylene Composites according to claim 2, it is characterised in that described to receive The class montmorillonite filled master batch of rice is made up of nano imvite powder, glycidyl methacrylate graft polypropylene, wherein, it is described The quality of nano imvite powder accounts for the 50% of the nm-class montmorillonite filled master batch quality.
3. high-dispersion nano OMMT/Polypropylene Composites according to claim 2, it is characterised in that the first Base glycidyl acrylate graft polypropylene is grafted polypropylene material prepared by melt blending Graft Method, and its grafting rate is 0.6%-1.2%.
4. high-dispersion nano OMMT/Polypropylene Composites according to claim 2, it is characterised in that described Nano imvite powder is density 1.7g/cm3, scattered yardstick 3.5nm-5nm inorganic particle.
5. high-dispersion nano OMMT/Polypropylene Composites according to claim 1, it is characterised in that the length Metallocene polyolefin tenacity-increased dose of block has key structural feature, and the key structural feature includes being urged by new metallocene catalyst The long block polyoctenamer segment being combined to.
6. high-dispersion nano OMMT/Polypropylene Composites according to claim 1, it is characterised in that described Height flows low crushing-resistant copolymerization propylene, and under 230 DEG C, 2.16Kg test condition, its melt index is 60g/10min-150g/ 10min, the kJ/m of notch impact strength >=102;Described low flowing high-impact co-polypropylene is in 230 DEG C, 2.16Kg test-strips Under part, its melt index is 5 g/10min -30 g/10min, the kJ/m of notch impact strength >=302
7. a kind of high-dispersion nano OMMT/Polypropylene Composites preparation method, it is characterised in that comprise the following steps:
Step S1)Obtain the high-dispersion nano OMMT/Polypropylene Composites any one of claim 1-6 Raw material;
Step S2)Mix the height in the raw material and flow low crushing-resistant copolymerization propylene, low flowing high-impact co-polypropylene, long block cyclopentadienyl Metal polyolefine toughener obtains the first mixture;
Step S3)Prepare the melt of the nm-class montmorillonite filled master batch;
Step S4)First mixture is positioned in the main feeding bin for tightly engaging parallel dual-screw extruding machine, and through feeding First mixture is added in the main barrel of extruder by material screw rod to be melted;
Step S5)The melt of the nm-class montmorillonite filled master batch is tightly engaged into the lateral of parallel dual-screw extruding machine from described Spout is injected into main barrel;
Step S6)By the melt of the first mixture of molten condition and nm-class montmorillonite filled master batch together batch mixing, shearing, divide Dissipate, and through tightly engaging parallel dual-screw extruding machine extrusion, obtain extrudate;
Step S7)To extrudate cooling, drying, granulation processing, PP composite material is obtained.
8. high-dispersion nano OMMT/Polypropylene Composites preparation method according to claim 7, its feature exist In the step S3)Comprise the following steps:
Step S31)Obtain and prepare the dispensing of the nm-class montmorillonite filled master batch, the dispensing including nano imvite powder, Glycidyl methacrylate graft polypropylene each 50%;
Step S32)The dispensing is mixed, obtains the second mixture;
Step S33)Second mixture is positioned over to the main feeding bin of taper Strong shear single screw extrusion machine
In, the melt of nm-class montmorillonite filled master batch is obtained through chemical melting graft reaction, and through taper Strong shear list spiral shell
Bar extruder is extruded, and the melt of the nm-class montmorillonite filled master batch of the extrusion then is injected into described tightly engage
Inside the main barrel of parallel dual-screw extruding machine.
9. high-dispersion nano OMMT/Polypropylene Composites preparation method according to claim 8, its feature exist In the taper Strong shear single screw extrusion machine is from the charge door of the main barrel of the taper Strong shear single screw extrusion machine to head Outlet is sequentially provided with humidity province, and the temperature of each humidity province is followed successively by:60℃、190℃、210℃、225℃、230℃、230℃、 230℃。
10. high-dispersion nano OMMT/Polypropylene Composites preparation method according to claim 7, its feature exist In, it is described tightly engage parallel dual-screw extruding machine from this tightly engage parallel dual-screw extruding machine main barrel charge door to Head outlet is sequentially provided with humidity province, and the temperature of each humidity province is followed successively by:60℃、160℃、190℃、195℃、200℃、210 ℃、210℃。
CN201710980930.1A 2017-10-19 2017-10-19 High-dispersion nano OMMT/Polypropylene Composites and preparation method thereof Pending CN107805350A (en)

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Application publication date: 20180316