CN105538735B - A kind of controllable containing content and continuous polypropylene material of α scorching layers and preparation method thereof in order - Google Patents
A kind of controllable containing content and continuous polypropylene material of α scorching layers and preparation method thereof in order Download PDFInfo
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- CN105538735B CN105538735B CN201510894284.8A CN201510894284A CN105538735B CN 105538735 B CN105538735 B CN 105538735B CN 201510894284 A CN201510894284 A CN 201510894284A CN 105538735 B CN105538735 B CN 105538735B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0011—Combinations of extrusion moulding with other shaping operations combined with compression moulding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0022—Combinations of extrusion moulding with other shaping operations combined with cutting
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
Abstract
The present invention relates to a kind of controllable containing content and continuous polypropylene material of α scorching layers and preparation method thereof in order, disclose a kind of method that a large amount of α scorchings in order are prepared in polypropylene material, it is characterized in polypropylene and α nucleators according to a certain ratio after mixing granulation, with pure PP GRANULES, by microbedding co-extrusion device melting extrusion, obtain a kind of containing the high-toughness polypropylene of a large amount of α scorchings and α scorching sequential 2 Ds alternating stratified material.The present invention, which solves common preparation technology, can not prepare substantial amounts of, orderly α scorchings, the problems such as can not regulating and controlling the content of α scorchings, and the present invention is simple to operate, can consecutive production, convenient operation and control, steady quality, production efficiency is high, has wide industrialization and market prospects.
Description
Technical field
The present invention relates to a kind of controllable containing content and continuous polypropylene material of α scorching layers and preparation method thereof in order,
More particularly to used a kind of micro-nano stratiform coextrusion technology prepare virgin pp layer and with the addition of the α of α nucleators-
The multilayer material that polypropylene layer is alternately arranged, it is controllable, continuous orderly and height-oriented that this polypropylene multi-layer material contains content
α scorching layers, belong to polymer matrix composite preparation technology field.
Background technology
Polypropylene is because its cheap price and excellent properties are widely used in production and living.As
A kind of semicrystalline polymeric, its performance of polypropylene and purposes also heavily depend on its crystallization behavior and its crystallization is brilliant
Type.Polypropylene mainly has 3 kinds of crystal formations:α crystalline substances, β crystalline substances and γ crystalline substances [Meille S V, et al. Macromolecules 1990,
23, 4114-4121].Wherein, alpha-crystal form polypropylene, which has, increases firm, raising heat distortion temperature, creep resistant, reduces turbidity, improves system
Product surface gloss etc. acts on.It is mainly alpha-crystal form by the homogeneous crystallization of melt natural cooling under common processing conditions, but
In natural cooling, α crystals growth speed is slow, and α spherulite sizes are larger, negligible amounts, and the mechanical property of material is improved not
Greatly, therefore in order to prepare a large amount of α spherocrystals, α spherulite sizes are reduced, the crystalline rate of α spherocrystals are improved, wherein most effective most easy
Method is exactly additional α nucleators.At this stage, α nucleators be widely used in improve polyacrylic mechanical property with
And microporous barrier such as prepares at the field.
In addition, also there is some other a variety of crystal habits, such as spherocrystal, shish-kebab and scorching in polypropylene.Sent out from nineteen fifty-two
Since existing scorching structure, scholars have carried out substantial amounts of research work.When PP melts contact with out-phase surface, out-phase surface can
Formed density it is very high crystallize into epipole, make PP chips growth can only along fall in out-phase surface direction carry out, cause chip
In PP scorchings arranged in parallel.The research to PP scorchings is concentrated mainly on abductive approach, Review On The Nucleation Mechanism, law of development, knot at present
Brilliant dynamics and influence to mechanical property etc. [Ning N, et al. Progress in Polymer
Science, 2012, 37: 1425– 1455.]。
It is to add or be formed in situ fiber in PP matrixes to prepare the most frequently used method of PP scorchings, and its formation mechenism substantially may be used
It is divided into stress mechanism of nucleation and impurity nucleation mechanism.Kinds of fibers, surface treatment, crystallization temperature, shear action and PP molecular weight
It is an important factor for influenceing the formation of PP scorchings.Different types of fiber has different nucleation capabilities, when fiber nucleation capability not
Qiang Shi, can be by being handled fiber surface or coating nucleator in fiber surface to induce scorching to generate.
Numerous studies show that the generation of PP scorchings can improve the bonding of fiber and basal body interface, improve interfacial stress and pass
Pass, so as to improve interface shear strength.Many scholars also study the macro-mechanical property for finding that PP scorchings can improve material, such as draw
Stretch intensity, impact strength, bending strength etc. [Quan H, et al. Compos. Sci. Technol. 2005,65,
999-1021]。
In view of scorching structure and α crystalline substances be to improving the contribution of Properties of Polypropylene, we it may be speculated that with scorching structure and
The α scorchings of alpha-crystal form have potential advantage for improving Properties of Polypropylene.Research work of the people to scorching is concentrated mainly on fibre
Dimension induction polypropylene produce scorching structure, multiple fiber such as glass, carbon fiber, carbon pipe, aramid fiber, natural fiber etc. all by with
To study scorching structure [Quan H, et al. Compos. Sci. Technol. 2005,65,999-1021].Fiber
In the research work for inducing scorching, induction scorching is mainly by stretching fiber [Varga J, et al. J. Polym.
Sci. Part B: Polym. Phys. 1996, 34, 657-670.].Meanwhile part researcher is also by nucleator and fiber
And for induce generation scorching, Nngae et al. [Nagae S, et al. J. Mter. Lett.1995,14,1234-
1236.] AMPP coated with nucleator efficiency allows the glass without induction crystallizing power to be tied in static state on glass
Scorching is produced in brilliant process.
These above-mentioned methods for preparing α scorchings, either stretch fiber, add α nucleators still by fiber and nucleation
Agent is combined, and α scorchings are primarily generated at the contact surface of fiber and matrix in Pp System.In conventional methods where, the arrangement of fiber
It is relatively mixed and disorderly, therefore the scorching of induced synthesis is isotropic on the whole, it is difficult to enhancing is realized in particular directions.Only pass through
The means such as shearing field make fiber-wall-element model, can just obtain anisotropic scorching, but these methods still difficulty makes PP scorchings height-oriented
And scorching is in one-dimensional distribution in fiber surface.In addition, being influenceed by fibre length and processing conditions, fiber is difficult in Impact direction
Upper continuously distributed, nor continuous, its enhancing effect is affected the scorching of formation.Importantly, traditional preparation side
The content of α scorchings prepared by method in the base is uncontrollable, it is difficult to obtains the scorching system of different content, is more difficult to obtain
The product of high α scorchings content.This just seriously hinders improvement of the α scorchings to performances such as matrix pore-forming, barriers, and these need to exist
There are a large amount of multidimensional α scorchings systems in order to be studied, also counteracts that unique crystal habit potential application valency this to α scorchings
The exploration of value.Therefore, preparing continuous, height-oriented and controllable content PP scorchings needs new idea and method.
In PP matrixes, the α scorchings that conventional method obtains are except the tool degree of orientation is not high, discontinuous and content is uncontrollable
Outside problem, also there is following limitation in its research:(1)Resulting phenomenon and rule substantially obtain in PP bodies,
That is PP is not in constrained state;(2)In terms of influence of the PP scorchings to performance is confined to mechanical property, to functionalization
Study less;(3)The formation of scorching be unable to do without fiber, induces the research of PP scorchings seldom using only nucleator, because existing
There is method to be difficult to oriented alignment of the nucleator in PP.
In summary, how to solve the problems, such as that existing PP scorchings research is present, and how to realize PP bases micro-nano material height
Performance and functionalization, construct continuous PP scorchings in order in restricted clearance using nucleator and regulate and control knot of the PP scorchings in restricted clearance
Brilliant behavior is a kind of effective means.Therefore, applicant is creatively determined α nucleators using the spacing effect of micro-nano layer coextrusion
To the specific region for being distributed in PP films, form PP layers and PP/ α are nucleated the layer structure that oxidant layer is alternately arranged, PP is limited in stratiform
Layer constructs continuous orderly α scorchings.α scorchings layer is located at virgin pp layer and consistency of thickness, α scorchings be formed at virgin pp layer and
The interface and edge of α-polypropylene layer grow perpendicular to the direction at interface, and α scorchings are continuously distributed along boundary layer and α-chip is orderly
Arrangement.The thickness of α scorching layers is determined by nucleator species, nucleation agent content, crystallization temperature and pure PP thickness degree.α scorchings contain
Amount is controllable, is together decided on by the number of plies and thickness and crystallization temperature of virgin pp layer.By adjust nucleator species,
Content, continuity and the degree of order of the controllable PP scorchings of content, the number of plies, Thickness ratio, the PP scorchings formed have continuous, height
Orientation, the regulatable feature of content, the Fundamental Aspects research for PP scorchings is provided a powerful means.
The content of the invention
For above-mentioned the deficiencies in the prior art, controllable containing content it is an object of the invention to provide one kind and continuous orderly α
Polypropylene material of scorching layer and preparation method thereof, the polypropylene prepared using this method contain it is continuous orderly, height-oriented and
The regulatable α scorchings of content.
The present invention technical principle be:The condition of the formation of α scorchings is with fine and close nucleating point matrix or fiber surface
Induced growth so that chip is along the direction cross growth perpendicular to matrix or fiber surface.Therefore, it is coextruded and is filled using microbedding
Put, obtain the layer structure that α-PP layers and pure PP layers are alternately arranged.Come using the α nucleators in α-PP layers, being distributed in interface
Pure PP layers are induced to produce scorching.Because the crystallization temperature of α-PP layers and pure PP layers is present, therefore, in PP layers, the α of interface-
Scorching first grows, and ties up the growing space of α spherocrystals, finally gives polypropylene material of the PP layers based on α scorchings.Meanwhile pass through
The thickness ratio of Melt Pump regulation α-PP layers and pure PP layers is controlled, can make it that α-PP layers are relatively thin, PP layers are relatively thick, entirely
The content of α scorchings is relatively more in system, obtains the polypropylene material of high content of alpha scorching;Pass through the number of regulating course multiplier
To adjust the thickness of PP layers so that a kind of containing a large amount of, sequential 2 D α so as to obtain in PP layers based on α scorching structures
The polypropylene material of scorching.
The present invention is based on above-mentioned principle, and technical scheme is used by realizing foregoing invention purpose:The present invention includes as follows
Step:
The first step, by PP GRANULES and α nucleators by mass fraction proportioning 99.9%-99.0%:0.1%-1.0% is matched somebody with somebody
Material obtains raw material components;
Second step, by raw material components drying, premixing, it is granulated, α-PP GRANULES is obtained after drying;
3rd step, the α-PP GRANULES and neat polypropylene pellets that second step is obtained are put into by extruder respectively(A、B)、
Melt Pump(C、D), distributor(E), multiplier(F), mouth mold(G), tri-roll press machine(H)And hauling machine(I)The micro-nano layer of composition
The two extruderses of shape co-extruder(A、B)In, after fusion plastification, two strands of melts pass through Melt Pump(C、D)Pressurization and metering
Afterwards in distributor(E)Middle overlapping, by n multiplier(F)Cutting and overlapping after, from outlet mold(G)Outflow, then by three rollers
Calender(H)Compacting and hauling machine(I)Traction and obtain 2n+1Layer virgin pp layer and α-polypropylene layer are alternately arranged poly-
Propylene material.
Above-mentioned polypropylene material of α scorching layers and preparation method thereof in order a kind of controllable containing content and continuous, it is special
Sign is to set up following steps between above-mentioned second step and the 3rd step:α-PP GRANULES that second step is obtained(High content
Masterbatch)Double screw extruder melt blending, extrusion, granulation are put into after being mixed with virgin pp proportioning, is accurately contained after drying
α-PP GRANULES of amount;The extrusion that resulting α-PP GRANULES is put into the microbedding co-extruder in the 3rd step again
In machine.
Above-mentioned polypropylene material of α scorching layers and preparation method thereof in order a kind of controllable containing content and continuous, it is special
The α nucleators that sign is to use are aromatic carboxylic acid salt, dibenzyl sorbitol class, substituted aryl heterocycle phosphate(Salt)
Any one in class, dehydroabietic acid and its esters, branched amide-type, high score subclass and inorganic species or wherein several groups
Close.
Above-mentioned polypropylene material of α scorching layers and preparation method thereof in order a kind of controllable containing content and continuous, it is special
Sign is any value of the extruder A and extruder B of micro-nano stratiform the co-extruder rotating ratio between 0.1-10(Including 0.1
With 10), Melt Pump C and Melt Pump D flow ratio is identical with extruder A and extruder B rotating speed ratio;The quantity of multiplier
N=0,1,2,3,4,5,6,7,8,9,10,11,12,13,14;The thickness of outlet mold is 0.1-4mm, width 20-1500mm;Lead
The hauling speed for drawing machine is 0.1-10m/min;The roller temperature of tri-roll press machine is 100-140 DEG C.
Above-mentioned polypropylene material of α scorching layers and preparation method thereof in order a kind of controllable containing content and continuous, it is special
The gross thickness for the polypropylene material that sign is to prepare is 0.05-4mm;Width is 18-1500mm;Total number of plies is 2n+1(N=0,1,
2,3,4,5,6,7,8,9,10,11,12,13,14);Interface layer number is 2n+1-1(N=0,1,2,3,4,5,6,7,8,9,10,
11,12,13,14);Any value of the Thickness ratio of virgin pp layer and α-polypropylene layer between 0.1-10(Including 0.1 and 10).
Above-mentioned polypropylene material of α scorching layers and preparation method thereof in order a kind of controllable containing content and continuous, it is special
Sign is extruder(A、B)Charge door, transportation section, melt zone, homogenizing zone, distributor(E), layer multiplier(F)Temperature point
Wei not be 100~180 °C, 160~240 °C, 160~240 °C, 160~240 °C, 160~240 °C, 160~240 °C.
Multi-layer polypropylene material prepared by the present invention has following distinguishing feature:
(1)The structure of the material by virgin pp layer with the α-polypropylene layer that with the addition of α nucleators as shown in Fig. 2 replaced
Arrangement forms, and total number of plies is 2n+1(N is for integer and more than or equal to 0), gross thickness T, overall width D.Virgin pp layer and α-poly-
Continuous interfacial layer between propylene layer be present, the quantity of boundary layer is 2n+1-1.The thickness ratio of virgin pp layer and α-polypropylene layer is
r。
(2)α scorchings layer is located at virgin pp layer and consistency of thickness, and α scorchings are formed at virgin pp layer and α-polypropylene layer
Interface and grown along perpendicular to the direction at interface, α scorchings are continuously distributed along boundary layer and α-chip ordered arrangement.α scorchings
The thickness of layer is determined by nucleator species, nucleation agent content, crystallization temperature and pure PP thickness degree.The content of α scorchings be it is controllable,
Together decided on by the number of plies and thickness and crystallization temperature of virgin pp layer.According to preparation condition, α-polypropylene layer can be horizontal by α
Crystalline substance is full of, and can not be also full of by α scorchings.
(3)Total number of plies 2 of materialn+1With interface layer number 2n+1- 1 is determined by multiplier quantity n in micro-nano stratiform co-extruder
Fixed, the thickness ratio of virgin pp layer and α-polypropylene layer is by corresponding extruder rotating speed coarse adjustment and melt pump discharge accuracy controlling.
The gross thickness and width of material are determined by outlet mold size and hauling speed.The crystallization temperature of material by tri-roll press machine roller temperature
Determine.
(4) polypropylene α scorchings are obviously improved to the toughness of material, pass through the content of β scorchings in adjustment and control system
Obtain the high-toughness polypropylene material with high content β scorchings.
The present invention has advantages below:
(1)The method provided by the present invention that a large amount of α scorchings in order are prepared in polypropylene material, can obtain one layer of α
The multilayer material, toughness, mechanical property to polypropylene material etc. that spherocrystal, one layer of α scorching are alternately arranged has clear improvement.
(2)In the methods provided by the present invention that a large amount of orderly α scorchings are prepared in polypropylene material, PP thickness degree can
Adjust(Melt Pump accuracy controlling can be passed through), PP scorchings can be studied in different scale stratiform restricted clearance(Micron order is to nanoscale)
Nucleation and growth mechanism.
(3)α scorching contents prepared by the present invention are adjustable, can be by adjusting nucleator species, nucleation agent content, stratiform material
The number of plies, the content of interlayer Thickness ratio regulation and control PP scorchings of material.
(4)α scorchings prepared by the present invention are different from the column scorching of one dimension fibre induction, two-dimentional interface it is continuous, have
Sequence is arranged, in height-oriented.
(5)Due to being the preparation for realizing polypropylene material in an extruder, method provided by the invention, which has, simply easily to be grasped
Make, the features such as production cost is low, efficiency high, and plant maintenance facilitates.
(6)Method provided by the invention is without using solvent, it is not necessary to subsequent treatment, has nontoxic, free of contamination feature.
Specific good effect caused by the present invention, it can be illustrated by latter embodiments.
Brief description of the drawings
The present invention is further illustrated below in conjunction with the accompanying drawings.
Fig. 1 is the structural representation of micro-nano stratiform co-extruder involved in the present invention.In figure, A, B:Extruder, C,
D:Melt Pump, E:Distributor, F:Layer multiplier, G:Outlet mold, H:Tri-roll press machine, I:Hauling machine.
Fig. 2 is the formation of alternately stratiform PP membrane structures schematic diagram and scorching.In figure, gross thickness T, overall width D.
Fig. 3 is the petrographic microscope photo of alternately stratiform PP films.
Embodiment
The present invention is further described specifically by the following examples.In following embodiment, each component
Dosage is weight consumption.It is necessarily pointed out that following examples are served only for, the present invention is described further, no
It is understood that and the present invention is done according to the invention described above content for limiting the scope of the invention, art skilled person
Go out some nonessential modifications and adaptations, still fall within protection scope of the present invention.
Embodiment 1
The raw material of a kind of controllable containing the content and continuous polypropylene material of α scorching layers in order includes following components and quality
Fractional content:
Constituent mass fraction
Polypropylene(PP) 50
α polypropylene(α-PP) 50
Wherein, α-polypropylene granules are by virgin pp and the basic salt of the substituted aryl heterocycle aluminum phosphate of 0.5% mass fraction
Class α nucleators(Trade name NA-21)Extruded after overmulling by double screw extruder and be granulated to obtain.
Virgin pp and α-polypropylene granules are put into by extruder, Melt Pump, distributor, multiplier, mouth mold, three respectively
Roll calendar and haulage gear into micro-nano stratiform co-extruder two extruderses(A、B)In, after fusion plastification, two strands of melts
Pass through Melt Pump(C、D)Pressurization and metering after in distributor(E)Middle overlapping, by n multiplier(F)Cutting and overlapping
Afterwards, from outlet mold(G)Outflow, then by tri-roll press machine(H)Compacting and hauling machine(I)Traction be made virgin pp layer and
The polypropylene material that α-polypropylene layer is alternately arranged.Extruder A and extruder B rotating ratio are 1, Melt Pump C and Melt Pump D's
Flow ratio is identical with extruder A and extruder B rotating speed ratio, quantity n=5 of multiplier, and the thickness of outlet mold is 2mm, wide
Spend for 40mm, the hauling speed of hauling machine is 1m/min;The roller temperature of tri-roll press machine is 110 DEG C.Extruder(A、B)Charging
Mouth, transportation section, melt zone, homogenizing zone, distributor(E), layer multiplier(F)Temperature be respectively 180 °C, 190 °C, 200 °C,
200°C、200°C、195°C。
The gross thickness of prepared alternate multiple material is 2mm;Width is 40mm;Total number of plies is 64(n= 5);Boundary layer
Quantity is 63(n= 5);The Thickness ratio of virgin pp layer and α-polypropylene layer is 1.
POM tests are carried out to prepared sample, test result difference is as shown in Figure 3.The result of items test is real,
Substantial amounts of α scorchings are obtained in pure PP layers, and α scorchings are along the direction symmetric growth perpendicular to bed boundary, in highly taking
To.Experimental results are shown, in alternate multiple material, the content of alpha-crystal reaches 34.9%, after calculating, α scorchings
Content is up to 89.4%.
Embodiment 2
The raw material of a kind of controllable containing the content and continuous polypropylene material of α scorching layers in order includes following components and quality
Fractional content:
Constituent mass fraction
Polypropylene(PP) 50
α polypropylene(α-PP) 50
Wherein, α-polypropylene granules are nucleated by the substituted aryl heterocycle sodium phosphate class α of virgin pp and 0.5% mass fraction
Agent class(Trade name NA-11)Extruded after overmulling by double screw extruder and be granulated to obtain.
Virgin pp and α-polypropylene granules are put into by extruder, Melt Pump, distributor, multiplier, mouth mold, three respectively
Roll calendar and haulage gear into micro-nano stratiform co-extruder two extruderses(A、B)In, after fusion plastification, two strands of melts
Pass through Melt Pump(C、D)Pressurization and metering after in distributor(E)Middle overlapping, by n multiplier(F)Cutting and overlapping
Afterwards, from outlet mold(G)Outflow, then by tri-roll press machine(H)Compacting and hauling machine(I)Traction and virgin pp layer and α-
The polypropylene material that polypropylene layer is alternately arranged.Extruder A and extruder B rotating ratio are 1, Melt Pump C and Melt Pump D stream
Amount ratio is identical with extruder A and extruder B rotating speed ratio, quantity n=1 of multiplier, 3,5, and the thickness of outlet mold is
1mm, width 80mm, the hauling speed of hauling machine is 2m/min;The roller temperature of tri-roll press machine is 110 DEG C.Extruder(A、B)'s
Charge door, transportation section, melt zone, homogenizing zone, distributor(E), layer multiplier(F)Temperature be respectively 180 °C, 190 °C, 200 °
C、200°C、200°C、195°C。
The gross thickness of prepared alternate multiple material is 1mm;Width is 80mm;Total number of plies is 4,16,64(n= 5);Boundary
Surface layer quantity 3,15,63(n= 5);The Thickness ratio of virgin pp layer and α-polypropylene layer is 1.
Prepared sample is tested, DSC and XRD result show the increase with the number of plies, the increase of α crystalline substances content.
With reference to the result of polarisation and Electronic Speculum it has been confirmed that increased α crystalline substances are the α scorchings in interface growth.After calculating, 4
Layer, the content of 16 layers and the α scorchings in 64 layers of sample are 19.1%, 26.4% and 39.5% respectively.
In summary, we, which have prepared scorching content, to regulate and control, and scorching show it is continuous, orderly, height-oriented
Crystal structure alternate multiple material.
Embodiment 3
The raw material of a kind of controllable containing the content and continuous polypropylene material of α scorching layers in order includes following components and quality
Fractional content:
Constituent mass fraction
Polypropylene(PP) 75
α polypropylene(α-PP) 25
Wherein, α-polypropylene granules are by virgin pp and the dibenzyl sorbitol class α nucleators of 0.5% mass fraction(Business
Name of an article T5688)Extruded after overmulling by double screw extruder and be granulated to obtain.
Virgin pp and α-polypropylene granules are put into by extruder, Melt Pump, distributor, multiplier, mouth mold, three respectively
Roll calendar and haulage gear into micro-nano stratiform co-extruder two extruderses(A、B)In, after fusion plastification, two strands of melts
Pass through Melt Pump(C、D)Pressurization and metering after in distributor(E)Middle overlapping, by n multiplier(F)Cutting and overlapping
Afterwards, from outlet mold(G)Outflow, then by tri-roll press machine(H)Compacting and hauling machine(I)Traction and virgin pp layer and α-
The polypropylene material that polypropylene layer is alternately arranged.Extruder A and extruder B rotating ratio are 3:1, Melt Pump C and Melt Pump D's
Flow ratio is identical with extruder A and extruder B rotating speed ratio, quantity n=6 of multiplier, and the thickness of outlet mold is 1.5mm,
Width is 200mm, and the hauling speed of hauling machine is 2m/min;The roller temperature of tri-roll press machine is 120 DEG C.Extruder(A、B)Plus
Material mouth, transportation section, melt zone, homogenizing zone, distributor(E), layer multiplier(F)Temperature be respectively 180 °C, 190 °C, 200 °C,
200°C、200°C、195°C。
The gross thickness of prepared alternate multiple material is 1.5mm;Width is 200mm;Total number of plies is 128(n= 6);Boundary
Surface layer quantity 127(n= 6);The Thickness ratio of virgin pp layer and α-polypropylene layer is 3:1.
Prepared sample is tested, the content of α scorchings reaches 68.5%, and shows continuous orderly crystal knot
Structure.Compared with α-polypropylene prepared by common blending, tension fracture elongation rate is promoted to 723.1% by 235.6%, the toughness of material
Significantly improve.
Embodiment 4
A kind of raw material of controllable containing the content and continuous polypropylene material of α scorching layers in order include following components and
Mass fraction content:
Constituent mass fraction
Polypropylene(PP) 75
α polypropylene(α-PP) 25
Wherein, α-polypropylene granules are by virgin pp and the dibenzyl sorbitol class α nucleators of 0.5% mass fraction(Business
Name of an article T5688)Extruded after overmulling by double screw extruder and be granulated to obtain.
Virgin pp and α-polypropylene granules are put into by extruder, Melt Pump, distributor, multiplier, mouth mold, three respectively
Roll calendar and haulage gear into micro-nano stratiform co-extruder two extruderses(A、B)In, after fusion plastification, two strands of melts
Pass through Melt Pump(C、D)Pressurization and metering after in distributor(E)Middle overlapping, by n multiplier(F)Cutting and overlapping
Afterwards, from outlet mold(G)Outflow, then by tri-roll press machine(H)Compacting and hauling machine(I)Traction and virgin pp layer and α-
The polypropylene material that polypropylene layer is alternately arranged.Extruder A and extruder B rotating ratio are 3:1, Melt Pump C and Melt Pump D's
Flow ratio is identical with extruder A and extruder B rotating speed ratio, quantity n=6 of multiplier, and the thickness of outlet mold is 1.5mm,
Width is 200mm, and the hauling speed of hauling machine is 2m/min;The roller temperature of tri-roll press machine is 130 DEG C.Extruder(A、B)Plus
Material mouth, transportation section, melt zone, homogenizing zone, distributor(E), layer multiplier(F)Temperature be respectively 180 °C, 190 °C, 200 °C,
200°C、200°C、195°C。
The gross thickness of prepared alternate multiple material is 1.5mm;Width is 200mm;Total number of plies is 128(n= 6);Boundary
Surface layer quantity 127(n= 6);The Thickness ratio of virgin pp layer and α-polypropylene layer is 3:1.
The roller temperature of tri-roll press machine is adjusted to 130 DEG C, prepared sample is tested, α scorchings still show
Continuous orderly crystal structure, but the content of α scorchings is reduced to 51.7%.
Embodiment 5
The raw material of a kind of controllable containing the content and continuous polypropylene material of α scorching layers in order includes following components and quality
Fractional content:
Constituent mass fraction
Polypropylene(PP) 25
α polypropylene(α-PP) 75
Wherein, α-polypropylene granules are by virgin pp and the bicyclic carboxylic acid salt α nucleators of 1% mass fraction(HPN-68L)
Extruded after overmulling by double screw extruder and be granulated to obtain.
Virgin pp and α-polypropylene granules are put into by extruder, Melt Pump, distributor, multiplier, mouth mold, three respectively
Roll calendar and haulage gear into micro-nano stratiform co-extruder two extruderses(A、B)In, after fusion plastification, two strands of melts
Pass through Melt Pump(C、D)Pressurization and metering after in distributor(E)Middle overlapping, by n multiplier(F)Cutting and overlapping
Afterwards, from outlet mold(G)Outflow, then by tri-roll press machine(H)Compacting and hauling machine(I)Traction and virgin pp layer and α-
The polypropylene material that polypropylene layer is alternately arranged.Extruder A and extruder B rotating ratio are 1:3, Melt Pump C and Melt Pump D's
Flow ratio is identical with extruder A and extruder B rotating speed ratio, quantity n=3 of multiplier, and the thickness of outlet mold is 1mm, wide
Spend for 20mm, the hauling speed of hauling machine is 3m/min;The roller temperature of tri-roll press machine is 140 DEG C.Extruder(A、B)Charging
Mouth, transportation section, melt zone, homogenizing zone, distributor(E), layer multiplier(F)Temperature be respectively 180 °C, 190 °C, 200 °C,
200°C、200°C、195°C。
The gross thickness of prepared alternate multiple material is 1mm;Width is 20mm;Total number of plies is 16(n= 3);Boundary layer
Quantity 15(n= 3);The Thickness ratio of virgin pp layer and α-polypropylene layer is 1:3.
Prepared sample is tested, it is found that α scorchings can still cover with pure PP layers, and is showed continuous
Orderly crystal structure.Because the thickness of α-polypropylene layer is thicker, content of the α scorchings in whole system only has 21.7%.
Claims (6)
1. the preparation method of a kind of controllable containing the content and continuous polypropylene material of α scorching layers in order, it is characterised in that the party
Method comprises the following steps:
The first step, PP GRANULES and α nucleators are matched into 99.9%-99.0% according to mass fraction:0.1%-1.0% is carried out
Dispensing obtains raw material components;
Second step, by raw material components drying, premixing, it is granulated, α-PP GRANULES is obtained after drying;
3rd step, the α-PP GRANULES and neat polypropylene pellets that second step is obtained are put into by extruder (A, B), melt respectively
The micro-nano stratiform that pump (C, D), distributor (E), multiplier (F), mouth mold (G), tri-roll press machine (H) and hauling machine (I) are formed is total to
Squeeze device two extruderses (A, B) in, after fusion plastification, after pressurization and metering that two strands of melts pass through Melt Pump (C, D)
Overlap in distributor (E), after the cutting of n multiplier (F) and overlapping, flowed out from outlet mold (G), then by three-roller calendaring
The compacting of machine (H) and the traction of hauling machine (I) and obtain 2n+1Layer is controllable containing content and the virgin pp of continuous α scorchings in order
The high-toughness polypropylene material that layer and α-polypropylene layer are alternately arranged.
2. the preparation of according to claim 1 a kind of controllable containing the content and continuous polypropylene material of α scorching layers in order
Method, it is characterised in that set up following steps between above-mentioned second step and the 3rd step:α-polypropylene that second step is obtained
Input double screw extruder melt blending after grain mixes with virgin pp proportioning, extrusion, granulation and accurately contained after drying
α-PP GRANULES of amount;Resulting α-PP GRANULES is put into the micro-nano stratiform co-extruder in the 3rd step again
In extruder.
3. the preparation of according to claim 1 a kind of controllable containing the content and continuous polypropylene material of α scorching layers in order
Method, it is characterised in that α nucleators can be aromatic carboxylic acid salt, dibenzyl sorbitol class, substituted aryl heterocycle phosphoric acid
In esters, substituted aromatic heterocyclic phosphate class, dehydroabietic acid and its esters, branched amide-type, high score subclass and inorganic species
Any one either wherein several combination.
4. the preparation of according to claim 1 a kind of controllable containing the content and continuous polypropylene material of α scorching layers in order
Method, it is characterised in that the rotating ratio scope of the extruder (A, B) of micro-nano stratiform co-extruder is 0.1≤rotating ratio≤10, is melted
The flow ratio of body pump (C, D) is identical with the rotating speed ratio of extruder (A, B);The quantity n=0,1,2,3,4,5,6 of multiplier,
7,8,9,10,11,12,13,14;The thickness of outlet mold is 0.1-4mm, width 20-1500mm;The hauling speed of hauling machine is
0.1-10m/min;The roller temperature of tri-roll press machine is 100-140 DEG C.
5. the preparation of according to claim 1 a kind of controllable containing the content and continuous polypropylene material of α scorching layers in order
Method, it is characterised in that the gross thickness of the polypropylene material of preparation is 0.05-4mm;Width is 18-1500mm;Total number of plies is 2n +1, interface layer number is 2n+1- 1, wherein n=0,1,2,3,4,5,6,7,8,9,10,11,12,13,14;Virgin pp layer and α-
The Thickness ratio scope of polypropylene layer is 0.1≤thickness ratio≤10.
6. the preparation of according to claim 1 a kind of controllable containing the content and continuous polypropylene material of α scorching layers in order
Method, it is characterised in that charge door, transportation section, melt zone, homogenizing zone, distributor (E), the layer multiplier (F) of extruder (A, B)
Temperature be respectively 100~180 DEG C, 160~240 DEG C, 160~240 DEG C, 160~240 DEG C, 160~240 DEG C, 160~240
℃。
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