CN110229412A - A kind of PP nanocomposite and preparation method thereof - Google Patents

Abstract

The present invention relates to field of nanocomposite materials, specifically, it is related to a kind of PP nanocomposite and preparation method thereof, the nanocomposite is as premix through made from melt blending, the premix is formed by being combined with full be adhered between PP GRANULES of the nano material of liquid medium；When the nanocomposite is in some strength and/or range in stiffness, toughness is promoted with the promotion of intensity and/or rigidity.The preparation method includes that liquid medium and nano material are mixed to get paste, and the paste is adhered to PP GRANULES surface progress melt blending and obtains nanocomposite.Nanocomposite provided by the invention has excellent toughness, and process flow is short, at low cost, is suitble to promote the use of.

Description

A kind of PP nanocomposite and preparation method thereof

Technical field

The present invention relates to field of nanocomposite materials, specifically, being related to a kind of PP nanocomposite and its preparation side Method.

Background technique

It is squeezed out in existing technology frequently with nano material and mixed with polymers, composite material is formed, although such is compound The tensile strength of material is promoted, but the problems such as due to nano material and the poor compatibility of polymer, leads to such material Impact resistance it is generally not high.

To solve the above problems, enabling polymer send out between the gap of nano material frequently with modes such as intercalation in-situ polymerizations It is raw to react to improve the impact resistance of composite material, but the process is time-consuming longer, polymeric reaction condition is harsh, and molten Agent is not easily recycled, and can bring the variations such as environmental pollution.

Patent No. CN101081928A proposes a kind of preparation method of polyamide/nano montmorillonite masterbatch, using water Auxiliary law prepares polyamide/nano montmorillonite masterbatch, and it is intercalator that preparation method, which is with deionized water, and the illiteracy of purifying is taken off Mud is added step-wise to the polyamides that prescription amount melts completely by soil and deionized water mixing, fully dispersed obtained montmorillonite mud Amine, then polyamide/nano montmorillonite masterbatch is obtained through extruding pelletization.Preparation method is simple, and production cost is low, but this method It is to add montmorillonite mud after molten polyamide, will lead to montmorillonite mud and have not enough time to be thoroughly mixed with copolymer, The water of interlayer just because of high-temperature gasification, causes polyamide to fail to timely enter interlayer, meanwhile, only by water generation Energy, which is not enough to be completely exfoliated between cheating engaging layer, thus cannot obtain the composite material that type is completely exfoliated, properties of product Receive strong influence.

In view of this, the present invention is specifically proposed.

Summary of the invention

The present invention is intended to provide a kind of nanocomposite, including nano material and polypropylene, the sky of the nano material The stretched processing of gap does not need to carry out intercalation in-situ polymerization, can further increase polypropylene while promoting intensity and receive The toughness of nano composite material material.

In order to achieve the above objectives, the present invention specifically adopts the following technical scheme that

A kind of PP nanocomposite, which is characterized in that the nanocomposite is by premix through melt blending system , the premix is formed by being combined with full be adhered between PP GRANULES of the nano material of liquid medium；It is described The toughness of nanocomposite is promoted with the promotion of intensity and/or rigidity.

In above scheme, using macromolecule as the nanocomposite of base-material, in the mechanical property lifting process for representing intensity In, it can be lost in terms of toughness, can even be lower than the toughness of base-material itself sometimes, reduce the scope of application of material；Study carefully Its reason is due to poor compatibility between the part nano material component in composite material and part macromolecule, in addition, nanometer material Material itself produce reunion in process, can not it is evenly dispersed in the composite, also result in certain mechanical properties Missing.Nanocomposite provided by the invention is combined with liquid medium in nano material, and is combined with liquid for described The nano material adherency of medium is wrapped in PP GRANULES surface and forms mixture, by said mixture through melt blending, utilizes Processing temperature-rise period enables liquid medium undergo phase transition, so that nano material is dispersed in polypropylene, greatly improves multiple The toughness of condensation material.

In above scheme, the liquid medium include at least water, can also include isopentane, pentane, petroleum ether, oneself Alkane, hexamethylene, isooctane, trifluoroacetic acid, trimethylpentane, pentamethylene, heptane, butyl chloride, trichloro ethylene, carbon tetrachloride, three Trichlorotrifluoroethane, propyl ether, toluene, paraxylene, chlorobenzene, o-dichlorohenzene, diethyl ether, benzene, isobutanol, ethylene dichloride, just Butanol, butyl acetate, propyl alcohol, methylisobutylketone, tetrahydrofuran, ethyl acetate, isopropanol, ethyl alcohol, chloroform, methyl ethyl ketone, Dioxane, pyridine, acetone, nitromethane, acetic acid, acetonitrile, dimethylformamide, methanol, methylamine, dimethylamine, second Ether, pentane, methylene chloride, carbon disulfide, 1,1- dichloroethanes, trifluoroacetic acid, 1,1,1- trichloroethanes, ethyl alcohol, butanone, 1,2- dichloroethanes, glycol dimethyl ether, triethylamine, propionitrile, 4-methyl-2 pentanone, ethylenediamine, butanol, acetic acid, ethylene glycol Monomethyl ether, octane, morpholine, ethylene glycol monoethyl ether, dimethylbenzene, meta-xylene, acetic anhydride, ortho-xylene, N, N- dimethyl formyl One or more of amine, cyclohexanone, cyclohexanol, furfural, N-METHYLFORMAMIDE；Preferably water.

Further scheme of the invention are as follows: the nano material includes the one of zero dimensional nanometer materials or monodimension nanometer material Kind is a variety of, and the liquid medium injects and fill the gap of nano material, forms the paste with tack.

Further scheme of the invention are as follows: the consistency of the paste is 0~100mm, but is not 0mm；The paste It include: 1 parts by weight of nano material, 0.02~100 parts by weight of liquid medium；Preferably, it is also preferable to include help the paste 0~50 parts by weight of agent, but be not 0.

In above scheme, compared to the prior art to nano-material modified filtering and dry process, nanometer of the invention After material is between liquid medium is injected gap, paste continuous, and that there is certain tack, the paste are formd Object has certain consistency, but consistency is not 0mm, represents the paste to be combined with liquid medium and having a constant current The semisolid of dynamic property, therefore can be by the nano material paste uniform adhesion for being combined with liquid medium in polypropylene Grain surface improves processability with the common feeding of PP GRANULES to the equipment of melt blending.Preferably, in order to improve The amount of the combined liquid medium of nano material, can also be added auxiliary agent.

Further scheme of the invention are as follows: the zero dimensional nanometer materials and monodimension nanometer material include nano silicon oxide, are received Rice titanium oxide, nano zircite, nano zine oxide, nano aluminium oxide, nanogold, nano silver, nano-silicon, are received nano-nickel oxide Rice carbon, carbon nano-fiber, carbon nanotube, nano-graphite, nano boron powder, nano-sulfur, nano lanthanum oxide, Nanometer-sized Neodymium Oxide, nanometer Erbium oxide, nano oxidized praseodymium, nano yttrium oxide, nano europium oxide, nanometer tungsten oxide, nanometer silicon carbide, is received nano-cerium oxide One of rice tellurium oxide, nano oxidized niobium, nano-hafnium oxide or nanoscale molybdenum oxide are a variety of.

In above scheme, the ion exchange capacity between nano material and liquid medium is lower, and ion exchange does not almost occur, So that liquid medium enters the paste that nano material forms high viscosity containing large amount of liquid amount, convenient for further processing.

Further scheme of the invention are as follows: the characterization parameter of the nanocomposite intensity includes tensile strength, rigidity Characterization parameter include bending strength, the characterization parameter of toughness includes impact strength, the tensile strength of the nanocomposite In 10~40MPa range and/or bending strength in 15~55MPa range, impact strength is strong with tensile strength and/or bending The promotion of degree and improve 10~80%.

Further scheme of the invention are as follows: the nano material is 0.1~20:100 with polyacrylic mass ratio, preferably For 1~10:100, more preferably 3~8:100；The polyacrylic isotactic index be 90~99.5%, preferably 95~ 99%；The polyacrylic melt flow rate (MFR) be 0.1~2000g/10min, preferably 0.2~100g/10min, more preferably For 0.3~80g/10min.

In above scheme, due to frequently with polyacrylic isotactic index it is higher, generally greater than 95%, therefore corresponding Its crystallinity is higher, and plasticization temperature and heat resistance improve, but the problem of will appear toughness decline, and the application is by polypropylene It is packed into the nano material interlayer through interlayer divergence process, so that performance boost of the composite material in terms of toughness is larger.

The present invention also provides a kind of preparation methods of nanometer composite polypropylene material, which is characterized in that the preparation side Method includes the following steps:

(1) liquid medium and nano material are mixed, obtain paste；

(2) paste will be obtained in step (1) to mix with PP GRANULES, enables paste is full to be adhered to polypropylene Intergranular obtains premix；

(3) premix in step (2) is subjected to melt blending, obtains nanocomposite；

Preferably, the step (1) further includes that liquid medium, nano material and auxiliary agent are mixed, and obtains paste Object.

In the above method, there is certain consistency semisolid paste since liquid medium and nano material to be mixed to get Object, therefore slipping phenomenon will not occur for while being added to extrusion equipment after paste and PP GRANULES mixing, it can direct feeding Nanocomposite, processing easy to produce are prepared, and it is multiple to avoid nanometer caused by liquid medium in the prior art gasifies too early The poor problem of condensation material performance, through experiments, it was found that, compared with the prior art, nano combined material made from mixing of the invention Expect that performance is more superior.

According to above-mentioned preparation method, in step (3), when melt blending, moulded in temperature greater than or equal to thermoplastic polymer When changing temperature, liquid medium gasification in nanometer mixing material, the gasification separates the nano material of reunion, while the gas Change uniformly transfers heat in thermoplastic polymer and nano material；Preferably, the gasification is soft by thermoplastic polymer Change, and reduces the plasticization temperature of thermoplastic polymer.

According to above-mentioned preparation method, in step (3), it is higher than the boiling point of liquid medium in the temperature of melt blending and reaches During polypropylene plasticization temperature, liquid medium gasification separates the nano material of reunion；The boiling point of the liquid medium Lower than polyacrylic plasticization temperature, the boiling point is preferably not higher than 180 DEG C, and the liquid medium is preferably water；The liquid The weight ratio of medium and nano material is 0.02~100:1, preferably 5~50:1, more preferably 5~20:1.

In the above method, the application use will be added simultaneously in conjunction with the higher nano material of liquid medium amount with polypropylene Process equipment, due to the lyophile media processes (forming paste) previously to nano material, so that nano material contains liquid Amount improves, therefore when entering polypropylene melt tabetisol, although system temperature is already higher than the boiling point of liquid medium, nanometer material Contained liquid medium is more so that phase transformation evaporation process can carry out simultaneously with polyacrylic melting process between expecting gap, just makes Molten state polypropylene can smoothly enter into the gap of nano material, and improve the impact property of final products.And the prior art In, the technical solution of the nano material containing liquid is added frequently with first melting is carried out to polymer, and due to nano material parent The undertreatment of liquid medium reduces nano material and polyacrylic compatibility so that wherein liquid medium evaporation is too fast, So that the toughness of final products declines；On the other hand, in the prior art, nano material first is added undoubtedly to polymer melting The time for extending product preparation, waste time cost.

According to above-mentioned preparation method, in step (3), the premix that the paste and PP GRANULES are mixed to get exists Feeding to hot melt process equipment carries out melt blending under the conditions of no pressure.

In the above method, hot melt process equipment includes but is not limited to mixer, open mill or screw extruder (parallel/cone Shape/mono-/bis -/tri- screw rods), when using screw extruder, premix that the shape object and PP GRANULES are mixed to get from Without pressure feed zone charging, the charging under the conditions of no pressure is realized.In the present invention, can by nano material directly with polypropylene Grain directly mixes and carries out feeding, has benefited from nano material and forms the paste with certain consistency in conjunction with liquid medium, Slipping phenomenon is prevented, on the other hand the content of the liquid medium as contained by nano material is higher, passes through the in premix When one melting zone, liquid medium therein will not the gasification of phase transformation too early, allow the polypropylene of melting preferably to infiltrate into and receive The nanocomposite of good mechanical properties is formed between the gap of rice material.

According to above-mentioned preparation method, the step (1) further includes auxiliary agent being added in nano material to improve nano material Liquid content, the liquid medium for enabling the nano material be combined accounts for the 50~98% of paste gross mass, preferably 60~ 98%, more preferably 80~98%；The auxiliary agent and the mass ratio of nano material are 0.01~50:1, preferably 0.1~5:1, More preferably 0.2~1:1, the auxiliary agent include carboxylate surface active agent, sulfate salt surfactant, sulphonate surface Activating agent, phosphate ester salt surfactant, amine salt surfactant, quaternary surfactant, heterocyclic type surfactant, Nonionic surfactant, natural water soluble high molecular, one or more of synthetic water soluble high molecular and its prepolymer.

In the above method, the premix in the present invention taken polypropylene as the base material, contains during the preparation process using lower The auxiliary agent of amount, its purpose is to form the environment of lyophile medium between the gap of nano material, to improve paste Liquid content；High-content intercalator used in intercalation polymeric compared to the prior art, significantly reduces auxiliary agent to nano combined The influence of material overall performance.

In above scheme, the ability that liquid medium enters nano material is can be improved in the addition of auxiliary agent, to increase nanometer The consistency of material blends；In addition, the addition of auxiliary agent can also improve the boiling point of liquid medium, liquid medium gas in advance is prevented Change evolution.Due to generating the reaction temperature of gel nano material in the present invention at room temperature, requirement to auxiliary agent It is not high, therefore it is wider to be suitable for the invention the alternative range of auxiliary agent.

The auxiliary agent includes but is not limited to one or more of following component:

A. surfactant:

1, anionic surfactant: it is divided into carboxylate, sulfuric acid, sulfonate and phosphate ester salt.

(1) soap kind is higher fatty acid salt, and general formula of molecular structure is (RCOO)-nMn+.With stearic acid, oleic acid, laurel Acid etc. is more common.According to the difference of its metal ion (Mn+), there are alkali metal soap, alkaling earth metal base and organic amine soap etc..

(2) hydrosulphate is mainly the sulfuric acid ester of sulfated oil and higher aliphatic, general formula of molecular structure ROSO3- M+, there are commonly lauryl sodium sulfate (also known as " sldium lauryl sulfate "), sodium hexadecyl sulfate (also known as " cetanol sulfuric acid Sodium "), sodium stearyl sulfate (also known as " stearyl alcohol sodium sulphate ") etc..

(3) sulphonic acid compound mainly has aliphatic sulfonic compound, sulfo group aryl sulfonic acid compound, sulfo group naphthalene sulfonic acids compound etc.

2, cationic surfactant: containing nitrogen-atoms in the hydrophilic group ion of cationic surfactant, according to nitrogen original The position difference of son in the molecule is divided into amine salt, quaternary ammonium salt and heterocyclic type three classes.As benzalkonium chloride (trade name " geramine "), Benzalkonium bromide (trade name " bromogeramine "), chlorination (bromination) cetyl pyridinium (trade name " Xi Bailin ") etc.

3, zwitterionic surfactant: lecithin, amino acid pattern, betaine type

4, nonionic surfactant: fatty glyceride, fatty acid sorbitan (sapn), polysorbate (tween), alkane Base phenol polyethenoxy ether, fatty alcohol polyoxyethylene ether, fatty acid methyl ester APEO, detergent series.

B. water soluble polymer includes:

1, natural class macromolecule

Starch

Seaweeds: sodium alginate, agar-agar.

Natural plant gum class: Arabic gum, tragacanth gum, locust bean gum, tamarind seed polysaccharide glue, sesbania gum, carrageenan, guar gum, fruit Glue.

Animal glue class: gelatin, casein, chitosan.

Microbiological gum: xanthan gum, gellan gum, hyaluronic acid.

2, class macromolecule and its prepolymer are synthesized

(1) polymeric type water soluble polymer and its prepolymer

Polyacrylamide, polyacrylic acid, polymethylacrylic acid and its copolymer, polyvinyl alcohol, polyethylene glycol, polyoxygenated Ethylene, polyvinylpyrrolidone, polymaleic anhydride, polydimethyl diallyl ammonium chloride, polyvinylamine, poly- divinyl miaow Oxazoline, sulfonate styrene maleic anhydride copolymer, opens Pu Shi resin at kayexalate.

(2) polycondensation class water soluble polymer and its prepolymer

Water soluble amino resin, water soluble phenol resin, water soluble alkyd resin, water-soluble epoxy resin, water-soluble poly Urethane resin, polyethylene imine, poly-aspartate, poly-epoxy succinic acid, polyamine epichlorohydrin resin, polyamide second Two urea formaldehydes, ammonia-epichlorohydrin resin, heavy polyamine epichlorohydrin resin, ammonia-dimethylamine-epichlorohydrin resin, N, N- dimethyl 1,3- propane diamine and epichlorohydrin resin.

(3) other

Water Soluble Maleic Anhydride oil, dicyandiamide formaldehyde resin, rosin amine-ethylene oxide condensate, poly N-ethylene yl acetamide, Water-soluble poly-sucrose.

3, semi-synthetic class macromolecule

Modified cellulose and converted starch.

Preferably synthetic class macromolecule and its prepolymer.

According to above-mentioned preparation method, nano material and the adding manner of auxiliary agent include being added at one time in the step (1) It is added in batches；It is respectively 0.01-100g/min that speed, which is added, preferably 5-10g/min, more preferable 7g/min.

According to above-mentioned preparation method, the step (1) further includes implementing physical dispersion, the physics point to nano material Dissipate includes but is not limited to colloid mill, ball milling, ultrasound, vortex, etching auxiliary, gas shock etc.；Preferably, the physical dispersion For ultrasound, the frequency of the ultrasonic field is 800~1000Hz, and power is 200~1000W.

According to above-mentioned preparation method, the preparation method further includes addition latex shape in the paste made from step (1) Resulting mixture, the mixture is blended with polypropylene fusion later, and the mass ratio of the latex and paste is 0.1~10:1, The latex includes styrene-acrylic emulsion, acrylic acid ester emulsion, acrylic emulsion, silicone acrylic emulsion, aqueous polyurethane emulsion, fluorine carbon cream Liquid, rosin resin lotion, terpinol, acrylate and vinyl acetate emulsion, aqueous epoxy resin emulsion, styrene-butadiene latex, Heveatex, white glue cream, chlorine One of fourth latex, pure C latex, carboxylic styrene butadiene latex, styrene-acrylic latex are a variety of.

In the above method, after the completion of prepared by the nano material paste for being combined with liquid medium, latex can also be utilized Mixed processing is carried out to paste precast body, and the paste after latex mixed processing is melted altogether simultaneously with polypropylene Row following process is infiltrated, above-mentioned mixed processing has greatly delayed the release rate of liquid medium between gap, effectively prevent liquid Phase transformation occurs to early in medium, on the other hand, when the mixed processing of latex and paste further improves liquid medium phase transformation The scale of nano material gap expansion is conducive to the gap realization filling that polymer travels further into nano material.

According to above-mentioned preparation method, the preparation method further includes before or during melt blending to paste and poly- The age resister being added in the premix that particulate propylene is formed, the age resister and polyacrylic weight ratio are 0.1~1: 100, preferably 0.3:100；The age resister is selected from amine antioxidants, phenolic antioxidant, thio-2 acid vinegar kind antioxidant One or more of with phosphorous vinegar kind antioxidant.

In the above method, the age resister includes:

Amine antioxidants: there are ketoamine condensation product, secondary diarylamine, substituted p-phenylenediamine, hindered amine；

Phenolic antioxidant: alkylation monophenols, alkylation polyphenol, thiobisphenol and polyphenol can be divided into.Alkylation monophenols and Polyphenol antioxidant principal item has antioxidant 264,1076,2246,1035,1010,3114 and 1790；Thiobisphenol it is main Kind has antioxidant 2246 and 300；Polyatomic phenol antioxidant principal item has 2,5 1 di-t-butyl hydroquinones and 2,5 12 uncles penta Base quinhydrones；

Thio-2 acid vinegar and phosphorous vinegar kind antioxidant；Its principal item has anti-aging agent TNP, Ultranox624 and Asia Tricresyl phosphate (2,4 1 di-tert-butyl) ester.

Other type antioxidants: 2 one coloured glaze base benzo miaow trade name antioxidant MBs, dibutyl dithiocaarbamate Nickel trade name antioxidant NBC, there are also zinc dialkyl dithiophosphates.

The age resister specifically includes: anti-aging agent RD, antioxidant A W, antioxidant BLE, antioxidant A, anti-aging agent OD, 4,4 '-bis- (α-methylbenzyl) diphenylamines, 4,4 '-bis- (α, α-methylbenzyl) diphenylamines, N, N ,-di-sec-butyl-p-phenyl enediamine, Anti-aging agent 4030, antioxidant 4010, antioxidant 4010NA, antioxidant 4020, antioxidant 264, antioxidant 1076, antioxidant 2216, antioxidant 1035, antioxidant 1010, antioxidant 3114, antioxidant 1790, antioxidant 2246,2,5- di-t-butyl hydrogen Quinone, antioxidant TNP, Ultranox624, phosphorous acid three (2,4- di-tert-butyl-phenyl) ester, antioxidant MB, is prevented anti-oxidant DLTP Old agent NBC, zinc dialkyl dithiophosphate.

The present invention also provides a kind of premix, the premix includes paste and polypropylene；The paste packet It includes: 1 parts by weight of nano material, liquid medium 5-100 parts by weight, auxiliary agent 0-50 parts by weight, but be not 0；The paste covers Premix is formed on PP GRANULES surface；Preferably, during preparing paste, successively by nano material and auxiliary agent It is added into liquid medium and is dispersed；It is furthermore preferred that it is described dispersion include ultrasound, shearing, stirring, ball milling, colloid mill, Vortex, etching auxiliary or gas shock；It is further preferred that nano material and the adding manner of auxiliary agent include being added at one time It is added in batches.

The preparation method of above-mentioned PP composite material specifically comprises the following steps:

(1) liquid medium is stirred, while nano material is added with the speed of 0.01~100g/min and is persistently stirred It is uniformly dispersed, the weight ratio of liquid medium and nano material is 0.02~100:1；

(2) it is once added in batches or into the lasting agitating solution of step (1) and helps with the speed of 0.01~100g/min Agent, obtains paste, and the consistency of the paste is 0~100mm, and the weight ratio of the auxiliary agent and nano material is 0.001~ 50:1；

(3) paste and PP GRANULES that step (2) obtains are mixed to get premix；

(4) by the premix of step (3), feeding hot melting equipment, melt blending simultaneously carry out subsequent add under the conditions of no pressure Work obtains nanocomposite.

According to the above method, when the hot melting equipment is screw extruder, engine speed is 30~80Hz, main feeding hopper Revolving speed is 10~30Hz, and extrusion temperature is 150~200 DEG C of an area, two 230~280 DEG C of areas, three 230~280 DEG C of areas, 4th area 230~280 DEG C, five 230~280 DEG C of areas；It is preferred that engine speed is 60Hz, main feeding hopper revolving speed is 20Hz, extrusion temperature one 150~180 DEG C of area, two 245~260 DEG C of areas, three 245~255 DEG C of areas, four 240~250 DEG C of areas, five 240~260 DEG C of areas.Spiral shell The linear velocity of bar revolving speed is 0.6~1m/s.

It further include carrying out mixed processing using latex and paste afterwards in step (2), then walked according to the above method Suddenly the technique of (3).

The invention has the benefit that

1. nanometer composite polypropylene material provided by the invention is in terms of mechanical property, tool especially in terms of impact property There is biggish promotion, and simple process is easy to operate, the used time is short, is suitable for promoting；

2. the present invention melts the higher nano material of liquid content with polypropylene simultaneously, composite processing process is utilized In heat improve the molecular energy of liquid medium combined between nano material gap, promote liquid medium between gap that phase occurs Become, expanded the gap of nano material, realizes filling so that the polypropylene of molten state enters gap；

3. nano material provided by the invention forms the paste having compared with containing large amount of liquid amount through auxiliary agent processing, with poly- third During alkene while melt-processed, time and polypropylene fusion time phase that the liquid medium combined between gap is undergone phase transition Cooperation enters the gap of nano material and is filled conducive to the polypropylene of molten state；

4. nano material provided by the invention is while using liquid medium phase transformation expansion gap, also playing is prevented The effect that nano material is reunited.

Specific embodiment

It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be to the technology in embodiment Scheme is clearly and completely described, and the following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..

Embodiment 1

In the present embodiment, nano material and polyacrylic mass ratio are 12:100, and the liquid medium used uses for water Auxiliary agent be cetylpyridinium chloride, the nano material used is prepared as follows nano combined for nano aluminium oxide Material:

(1) liquid medium is stirred, while nano material is added with the speed of 4.5g/min and carries out continuing stirring point It dissipates uniformly, the weight ratio of liquid medium and nano material is 20:1；

(2) auxiliary agent is added into the lasting agitating solution of step (1) in batches or once with the speed of 0.1g/min, obtained Paste, the consistency of the paste are 34mm, and the weight ratio of the auxiliary agent and nano material is 10:1；

(3) paste and polypropylene that step (2) obtains are mixed to get premix；

(4) by the premix of step (3) from without pressure feed zone feed screw extruder, melt blending simultaneously carries out subsequent add Work obtains nanocomposite.

The engine speed of the extrusion equipment is 30Hz, and main feeding hopper revolving speed is 10Hz, and extrusion temperature is 150 DEG C of an area, Two 230 DEG C of areas, three 240 DEG C of areas, four 280 DEG C of areas, five 260 DEG C of areas, the linear velocity of screw speed are 0.8m/s.

The tensile strength for the nanometer composite polypropylene material that final extruding pelletization obtains is 29MPa, and bending strength is 43MPa, impact strength 81kgcm/cm.

Embodiment 2

In the present embodiment, nano material and polyacrylic mass ratio are 10:100, used liquid medium be acetone and The mass ratio of water, acetone and water is 7:93, and used auxiliary agent is polyacrylic acid and polymaleic anhydride, and weight ratio 1:1 is adopted Nano material is nano-silicon, is prepared as follows nanocomposite:

(1) liquid is stirred, while nano material is added with the speed of 10g/min and is persistently dispersed with stirring Even, the weight ratio of liquid medium and nano material is 100:1；

(2) auxiliary agent is added into the lasting agitating solution of step (1) with the speed of 0.5g/min, obtains paste, it is described The consistency of paste is 25mm, and the weight ratio of the auxiliary agent and nano material is 50:1；

(3) paste and polypropylene that step (2) obtains are mixed to get premix；

(4) by the premix of step (3) from without pressure feed zone feed screw extruder, melt blending simultaneously carries out subsequent add Work obtains nanocomposite.

The engine speed of the extrusion equipment is 80Hz, and main feeding hopper revolving speed is 30Hz, and one area of extrusion temperature is 190 DEG C, Two 280 DEG C of areas, three 260 DEG C of areas, four 260 DEG C of areas, five 250 DEG C of areas；The linear velocity of screw speed is 1m/s.

The tensile strength for the nanometer composite polypropylene material that final extruding pelletization obtains is 30MPa, and bending strength is 41MPa, impact strength 83kgcm/cm.

Embodiment 3

In the present embodiment, nano material and polyacrylic mass ratio are 0.1:100, and the liquid medium used uses for water Auxiliary agent be sodium alginate, the nano material used is nano zircite and nanometer silicon carbide, mass ratio 8:2, according to as follows Method prepares nanocomposite:

(1) liquid medium is stirred, while nano material is added with the speed of 0.01g/min and carries out continuing stirring It is uniformly dispersed, the weight ratio of liquid medium and nano material is 50:1；

(2) auxiliary agent is added into the lasting agitating solution of step (1) with the speed of 10g/min, obtains paste, it is described The consistency of paste is 38mm, and the weight ratio of the auxiliary agent and nano material is 0.1:1；

(3) paste and polypropylene that step (2) obtains are mixed to get premix；

(4) by the premix mixer of step (3), melt blending simultaneously carries out following process, obtains nanocomposite.

The tensile strength of finally obtained nanometer composite polypropylene material is 28MPa, bending strength 40MPa, and impact is strong Degree is 85kgcm/cm.

Embodiment 4

In the present embodiment, nano material and polyacrylic mass ratio are 7:100, and the liquid medium used is N, N- diformazan Base formamide, the auxiliary agent used for polyethylene imine and its oligomer, the nano material used for carbon nanotube, use Age resister is antioxidant BLE, is prepared as follows nanocomposite:

(1) liquid medium is stirred, while nano material is added with the speed of 15g/min and carries out continuing stirring point Dissipate that uniformly to apply frequency simultaneously be 800~1000Hz, power is the ultrasound of 200~1000W, liquid medium and nano material Weight ratio is 5:1；

(2) auxiliary agent is added into the lasting agitating solution of step (1) with the speed of 100g/min, obtains paste, it is described The consistency of paste is 59mm, and the weight ratio of the auxiliary agent and nano material is 5:1；

(3) paste and polypropylene that step (2) obtains are mixed to get premix；

(4) by the premix of step (3) from without pressure feed zone feed screw extruder, melt blending simultaneously carries out subsequent add Work obtains nanocomposite.

The engine speed of the extrusion equipment is 60Hz, and main feeding hopper revolving speed is 20Hz, and one area of extrusion temperature is 180 DEG C, Two 245 DEG C of areas, three 255 DEG C of areas, four 250 DEG C of areas, five 240 DEG C of areas；The linear velocity of screw speed is 0.9m/s.

The tensile strength for the nanometer composite polypropylene material that final extruding pelletization obtains is 29MPa, and bending strength is 42MPa, impact strength 84kgcm/cm.

Embodiment 5

In the present embodiment, nano material and polyacrylic mass ratio are 4:100, the liquid medium used be hexamethylene with Water, mass ratio 1:8, the auxiliary agent used for polyamide glyoxal resin, the nano material used for carbon nano-fiber, according to Following method prepares nanocomposite:

(1) liquid medium is stirred, while nano material is added with the speed of 20g/min and carries out continuing stirring point It dissipates uniformly, the weight ratio of liquid medium and nano material is 0.8:1；

(2) auxiliary agent is added into the lasting agitating solution of step (1) with the speed of 1g/min, obtains paste, the cream The consistency of shape object is 49mm, and the weight ratio of the auxiliary agent and nano material is 0.8:1；

(3) paste and polypropylene that step (2) obtains are mixed to get premix；

(4) by the premix feeding open mill of step (3), melt blending simultaneously carries out following process, obtains nano combined material Material.

The tensile strength of finally obtained nanometer composite polypropylene material is 30MPa, bending strength 41MPa, and impact is strong Degree is 86kgcm/cm.

Embodiment 6

In the present embodiment, nano material and polyacrylic mass ratio are 4:100, the liquid medium used for water, use Auxiliary agent is tamarind seed polysaccharide glue, and the nano material used is nano oxidized niobium, and the age resister used is phosphorous acid three (2,4- Di-tert-butyl-phenyl) ester, it is prepared as follows nanocomposite:

(1) liquid medium is stirred, while nano material is added with the speed of 0.02g/min and carries out continuing stirring It is uniformly dispersed, the weight ratio of liquid medium and nano material is 10:1；

(2) auxiliary agent is added into the lasting agitating solution of step (1) with the speed of 0.1g/min, obtains paste, it is described The consistency of paste is 39mm, and the weight ratio of the auxiliary agent and nano material is 2:1, further, by paste and pure C glue Newborn mixed processing；

(3) paste mixed with pure C latex and polypropylene that step (2) obtains are mixed to get premix；

(4) by the premix of step (3) from without pressure feed zone feed screw extruder, melt blending simultaneously carries out subsequent add Work obtains nanocomposite.

The engine speed of the extrusion equipment is 60Hz, and main feeding hopper revolving speed is 30Hz, and one area of extrusion temperature is 160 DEG C, Two 245 DEG C of areas, three 280 DEG C of areas, four 260 DEG C of areas, five 260 DEG C of areas；The linear velocity of screw speed is 0.7m/s.

The tensile strength for the nanometer composite polypropylene material that final extruding pelletization obtains is 37MPa, and bending strength is 50MPa, impact strength 99kgcm/cm.

Embodiment 7

In the present embodiment, nano material and polyacrylic mass ratio are 2:100, and the liquid medium used is water and positive penta The mass ratio 1:10 of alkane, water and pentane, used auxiliary agent are lauryl sodium sulfate, and the nano material used is nanometer Nickel oxide is prepared as follows nanocomposite:

(1) liquid medium is stirred, while nano material is added with the speed of 20g/min and carries out continuing stirring point It dissipates uniformly, the weight ratio of liquid medium and nano material is 40:1；

(2) auxiliary agent is added into the lasting agitating solution of step (1) with the speed of 35g/min, obtains paste, it is described The consistency of paste is 81mm, and the weight ratio of the auxiliary agent and nano material is 7:1；

(3) paste and polypropylene that step (2) obtains are mixed to get premix；

(4) by the premix of step (3) from without pressure feed zone feeding open mill, melt blending simultaneously carries out following process, obtains To nanocomposite.

The tensile strength of finally obtained nanometer composite polypropylene material is 30MPa, bending strength 42MPa, and impact is strong Degree is 86kgcm/cm.

Embodiment 8

In the present embodiment, nano material and polyacrylic mass ratio are 4.5:100, and the liquid medium used uses for water Auxiliary agent be hyaluronic acid, the nano material used is prepared as follows nanocomposite for nano oxidized tellurium:

(1) liquid medium is stirred, while nano material is added with the speed of 0.5g/min and carries out continuing stirring point Dissipate that uniformly to apply frequency simultaneously be 800~1000Hz, power is the ultrasound of 200~1000W, liquid medium and nano material Weight ratio is 3.5:1；

(2) auxiliary agent is added into the lasting agitating solution of step (1) with the speed of 56g/min, obtains paste, it is described The consistency of paste is 47mm, and the weight ratio of the auxiliary agent and nano material is 28:1；

(3) paste and polypropylene that step (2) obtains are mixed to get premix；

(4) by the premix of step (3) from without pressure feed zone feed screw extruder, melt blending simultaneously carries out subsequent add Work obtains nanocomposite.

The engine speed of the extrusion equipment is 70Hz, and main feeding hopper revolving speed is 20Hz, and one area of extrusion temperature is 200 DEG C, Two 230 DEG C of areas, three 280 DEG C of areas, four 230 DEG C of areas, five 280 DEG C of areas；The linear velocity of screw speed is 0.6m/s.

The tensile strength for the nanometer composite polypropylene material that final extruding pelletization obtains is 28MPa, and bending strength is 41MPa, impact strength 84kgcm/cm.

Embodiment 9

In the present embodiment, nano material and polyacrylic mass ratio are 18:100, and the liquid medium used uses for water Auxiliary agent be chitosan and ammonia-dimethylamine-epichlorohydrin resin, chitosan and ammonia-dimethylamine-epichlorohydrin resin Mass ratio is 10:1, and used nano material is nano yttrium oxide, is prepared as follows nanocomposite:

(1) liquid medium is stirred, while nano material is added with the speed of 8g/min and is persistently dispersed with stirring Uniformly applying frequency simultaneously is 800~1000Hz, and power is the ultrasound of 200~1000W, the weight of liquid medium and nano material Amount is than being 40:1；

(2) auxiliary agent is added into the lasting agitating solution of step (1) with the speed of 15g/min, obtains paste, it is described The consistency of paste is 84mm, and the weight ratio of the auxiliary agent and nano material is 9:1, further, by paste and fluorine carbon cream Liquid mixed processing；

(3) paste mixed with fluorine carbon emulsion and polypropylene that step (2) obtains are mixed to get premix；

(4) by the premix of step (3) from without pressure feed zone feed screw extruder, melt blending simultaneously carries out subsequent add Work obtains nanocomposite.

The engine speed of the extrusion equipment is 70Hz, and main feeding hopper revolving speed is 30Hz, and one area of extrusion temperature is 155 DEG C, Two 275 DEG C of areas, three 270 DEG C of areas, four 260 DEG C of areas, five 230 DEG C of areas；The linear velocity of screw speed is 1m/s.

The tensile strength for the nanometer composite polypropylene material that final extruding pelletization obtains is 36MPa, and bending strength is 51MPa, impact strength 103kgcm/cm.

Comparative example 1

In this comparative example, on the basis of embodiment 1, the position of extruder is added in adjustment nano material containing liquid, in no pressure Feeding polypropylene under the conditions of power, in polypropylene after melting zone, the nano material between gap containing liquid medium is fed in pressurization Material is mixed with the polypropylene of molten state.

The difference of comparative example 1 and embodiment is: nano material between polypropylene and gap containing liquid medium is simultaneously non-concurrent Feeding, but first feeding polypropylene and after polypropylene fusion, are combined with the nanometer material of liquid medium between feeding gap of pressurizeing Material is processed.

The tensile strength for the nanometer composite polypropylene material that final extruding pelletization obtains is 24MPa, and bending strength is 31MPa, impact strength 52kgcm/cm.

Mechanics Performance Testing is carried out to Examples 1 to 9 and comparative example 1, respectively obtains tensile strength, bending strength and punching The performance parameter of hit intensity is as shown in the table:

As seen from the above table, the mechanical property of nanocomposite obtained by Examples 1 to 9 is above the performance ginseng of comparative example 1 Number, especially there is promotion by a relatively large margin in bending strength, to find out its cause, being the phase transformation pair that the present invention utilizes liquid medium Nano material has carried out divergence process, is filled so that entering between gap with the polypropylene that nano material melts simultaneously, above-mentioned The heat that processing generates when polymer melting is utilized in divergence process between gap enables liquid medium evaporation generate implosion and struts sky Gap, while using the shearing force for squeezing out processing, gap is further peeled off, so that molten state polypropylene realizes filling, to improve The bending strength and impact strength of product.

Further, it is higher to compare Examples 1 to 8 for the intensity of embodiment 6 and embodiment 9, to find out its cause, being to melt The processing of mixing latex is carried out before processing to nano material paste, so that liquid medium evaporation generates in melting process Implosive force it is stronger, the expansion effect in nano material gap is more preferable, so that polyacrylic filling is more abundant, improves final The mechanical strength of product.

The above is only a better embodiment of the present invention and the applied technical principle.It will be appreciated by those skilled in the art that this hair It is bright to be not limited to specific embodiment described here, be able to carry out for a person skilled in the art it is various it is apparent variation, again Adjustment and substitution are without departing from protection scope of the present invention.Therefore, although by above embodiments to the present invention carried out compared with To be described in detail, but the present invention is not limited to the above embodiments only, without departing from the inventive concept, may be used also To include more other equivalent embodiments, and the scope of the invention is determined by the scope of the appended claims.

Claims (10)

1. a kind of PP nanocomposite, which is characterized in that

The nanocomposite is as premix through made from melt blending, the premix is by being combined with liquid medium Nano material is full to be adhered to and is formed between PP GRANULES；

The toughness of the nanocomposite is promoted with the promotion of intensity and/or rigidity.

2. nanocomposite according to claim 1, which is characterized in that the nano material includes zero dimensional nanometer materials Or monodimension nanometer material is one or more, the liquid medium injects and fills the gap of nano material, and being formed has self-adhesion The paste of property；Preferably, the zero dimensional nanometer materials and monodimension nanometer material include nano silicon oxide, and nano-titanium oxide is received Rice zirconium oxide, nano zine oxide, nano aluminium oxide, nano-nickel oxide, nanogold, nano silver, nano-silicon, nano-sized carbon, carbon nanometer Fiber, carbon nanotube, nano-graphite, nano boron powder, nano-sulfur, nano lanthanum oxide, Nanometer-sized Neodymium Oxide, nano oxidized erbium, nanometer Cerium oxide, nano oxidized praseodymium, nano yttrium oxide, nano europium oxide, nanometer tungsten oxide, nanometer silicon carbide, nano oxidized tellurium, nanometer One of niobium oxide, nano-hafnium oxide or nanoscale molybdenum oxide are a variety of.

3. composite material according to claim 1 or 2, which is characterized in that the consistency of the paste is 0~100mm, but It is not 0mm；

The paste includes:

1 parts by weight of nano material

0.02~100 parts by weight of liquid medium；

The paste it is also preferable to include,

0~50 parts by weight of auxiliary agent, but be not 0.

4. composite material according to any one of claims 1 to 3, which is characterized in that the nanocomposite intensity Characterization parameter include tensile strength, the characterization parameter of rigidity includes bending strength, and the characterization parameter of toughness includes impact strength, The tensile strength of the nanocomposite, in 15~55MPa range, is impacted in 10~40MPa range and/or bending strength Intensity improves 10~80% with the promotion of tensile strength and/or bending strength.

5. composite material described in any one according to claim 1~4, which is characterized in that the nano material and polypropylene Mass ratio be 0.1~20:100, preferably 1~10:100, more preferably 3~8:100；The polyacrylic isotactic index is 90~99.5%, preferably 95~99%；The polyacrylic melt flow rate (MFR) is 0.1~2000g/10min, preferably 0.2~100g/10min, more preferably 0.3~80g/10min.

6. a kind of preparation method of nanometer composite polypropylene material, which is characterized in that the preparation method includes the following steps:

(1) liquid medium and nano material are mixed, obtain paste；

(2) paste will be obtained in step (1) to mix with PP GRANULES, enables paste is full to be adhered between PP GRANULES To premix；

(3) premix in step (2) is subjected to melt blending, obtains nanocomposite；

Preferably, the step (1) further includes that liquid medium, nano material and auxiliary agent are mixed, and obtains paste.

7. preparation method according to claim 6, which is characterized in that high in the temperature of melt blending in the step (3) In liquid medium boiling point and during reaching polypropylene plasticization temperature, liquid medium gasification, by the nano material of reunion point From；The boiling point of the liquid medium is lower than polyacrylic plasticization temperature, and the boiling point is preferably not higher than 180 DEG C, the liquid Medium is preferably water；The weight ratio of the liquid medium and nano material be 0.02~100:1, preferably 5~50:1, more preferably For 5~20:1.

8. preparation method according to claim 6 or 7, which is characterized in that the step (1) further includes in nano material Auxiliary agent is added to improve the liquid content of nano material, the liquid medium for enabling the nano material be combined accounts for paste gross mass 50~98%, preferably 60~98%, more preferably 80~98%；The auxiliary agent and the mass ratio of nano material be 0.01~ 50:1, preferably 0.1~5:1, more preferably 0.2~1:1, the auxiliary agent include carboxylate surface active agent, sulfuric acid table Face activating agent, sulfosalt surfactant, phosphate ester salt surfactant, amine salt surfactant, quaternary surfactant, Heterocyclic type surfactant, nonionic surfactant, natural water soluble high molecular, in synthetic water soluble high molecular and its prepolymer It is one or more of.

9. preparation method according to any one of claims 6 to 8, which is characterized in that the preparation method further include Latex is added in paste made from step (1) and forms mixture, the mixture is blended with polypropylene fusion later, the glue The mass ratio of cream and paste is 0.1~10:1, and the latex includes styrene-acrylic emulsion, acrylic acid ester emulsion, acrylic emulsion, silicon Acrylic emulsion, aqueous polyurethane emulsion, fluorine carbon emulsion, rosin resin lotion, terpinol, acrylate and vinyl acetate emulsion, aqueous epoxy resin emulsion, One of styrene-butadiene latex, Heveatex, white glue cream, polychloroprene latex, pure C latex, carboxylic styrene butadiene latex, styrene-acrylic latex are more Kind.

10. a kind of premix characterized by comprising

The premix includes paste and polypropylene；

The paste includes: 1 parts by weight of nano material, liquid medium 5-100 parts by weight, auxiliary agent 0-50 parts by weight, but is not 0；

The paste, which covers, forms premix on PP GRANULES surface；

Preferably, during preparing paste, successively nano material and auxiliary agent are added into liquid medium and are divided It dissipates；

It is furthermore preferred that the dispersion includes ultrasound, shearing, stirring, ball milling, colloid mill, vortex, etching auxiliary or gas shock；

It is further preferred that nano material and the adding manner of auxiliary agent include being added at one time and being added in batches.