CN105563976B - A kind of polypropylene self-reinforced composite material and preparation method thereof - Google Patents
A kind of polypropylene self-reinforced composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of polypropylene self-reinforced composite material and preparation method thereof, wherein, this method comprises the following steps：(1) high-melting-point polypropylene and beta crystal-type nucleater are subjected to mixing as sandwich layer polypropylene；(2) using low melting point polypropylene as outer layer polypropylene；(3) the sandwich layer polypropylene and the outer layer polypropylene co-extrusion modling are obtained into coextrusion polypropylene strap；(4) polypropylene fabric of plain weave, twill, satin weave or three-dimensional will be obtained through braiding after coextrusion polypropylene strap stretching；(5) the first crystalline p p sheet, intermediate sheet and the second crystalline p p sheet are stacked gradually into hot pressing, wherein, the polypropylene fabric is intermediate sheet.The present invention adds beta crystal-type nucleater in preparation process to be more prone to stretching, and not easy to break, stretching ratio is higher, and material mechanical performance is more stable.
Description
Technical field
The present invention relates to a kind of polypropylene self-reinforced composite material and preparation method thereof.
Background technology
For many years, the polypropylene as general-purpose plastics, because its cost is low, source is wider, light, easy to be recycled etc.
Feature and be widely studied and applied.Polypropylene has excellent mechanical performance and optical property, but due to containing in its segment
Have substantial amounts of pending methyl group so that polypropylene material is generally limited by relatively low impact strength and weatherability, this be also researcher all
Wish solve the problems, such as.
Polyacrylic beta crystal is hexagonal crystal system, and research finds to be easier to harden in beta crystal drawing process, so as to gather around
There is higher impact flexibility, and simultaneously, Beta-crystalline polyacrylic also has relatively low heat distortion temperature, therefore β is added in polypropylene
Nucleator, beta crystal ratio is improved increasingly by the welcome and concern of researcher, the preferable polypropylene of toughness is in capacitor film
Middle application is wider.
Polyacrylic modified enhancement method includes chemical method modification and Physical is modified, and wherein Physical is modified is included altogether again
Mixed method, completion method, enhancing method and feature method.And mainly have two kinds of filler enhancing and self-reinforcing to polyacrylic enhancing, wherein
Filler enhancing is comprising using the materials such as mica, carbon fiber, glass fibre to be blended with matrix, so as to realize the raising of performance.But
It is generally between these fillers and matrix and incompatible, even if being dispersed among matrix, answering between filler and basal body interface
Power transmission efficiency is still than relatively low.With the generation of high performance polymer fiber, especially polypropylene fibre so that self-reinforcing
Mode be increasingly becoming focus of concern.1975, Leeds university researchers proposed so that " single polymers are multiple first
The concept of condensation material ", and prepare high density polyethylene (HDPE) self-reinforced composite material.The advantages of self-reinforcing, is reinforcement and matrix
It is fully compatible, hence in so that composite has more excellent impact flexibility, dimensional stability and relatively low thermal expansion
Coefficient.And by changing the structure of reinforcement, then the performance can of composite is greatly improved.So as to further widen
The use range of material.
At present, three kinds of methods are compounded with using what polymer fiber prepared self-reinforced composite material：Pellicular cascade method, melting
Infusion process and pressure sintering.Wherein pellicular cascade method should not complete wetting because matrix melt viscosity is high；The life of melt impregnation
The production cycle is longer, and cost is too high；Pressure sintering is allowed to melt compound due to directly to fiber heat pressurization, is taken to retain fiber
To causing processing temperature window narrow, cause greatly to limit.
Therefore, how to prepare while toughness reinforcing strengthens, processing temperature is wider and the self-reinforcing of reservation fiber-wall-element model is compound
The preparation method of material needs further to study and find.
The content of the invention
It is an object of the invention to overcome in the prior art processing temperature it is narrow, mechanical property is low, and matrix and enhancing
Body infiltrates incomplete defect, and provides a kind of polypropylene self-reinforced composite material and preparation method thereof.
The invention provides a kind of polypropylene self-reinforced composite material, wherein, the polypropylene self-reinforced composite material includes
The first crystalline p p sheet, intermediate sheet and the second crystalline p p sheet stacked gradually from top to bottom；
Wherein, first crystalline p p sheet and second crystalline p p sheet are low melting point polypropylene；
The intermediate sheet is poly- the third of the woven obtained plain weave of coextrusion polypropylene strap, twill, satin weave or three-dimensional
Alkene fabric, and the coextrusion polypropylene strap includes outer layer and sandwich layer, the outer layer is low melting point polypropylene, and the sandwich layer contains
There are high-melting-point polypropylene and beta crystal-type nucleater.
Present invention also offers a kind of preparation method of polypropylene self-reinforced composite material, this method comprises the following steps：
(1) high-melting-point polypropylene and beta crystal-type nucleater are subjected to mixing as sandwich layer polypropylene；
(2) using low melting point polypropylene as outer layer polypropylene；
(3) the sandwich layer polypropylene and the outer layer polypropylene co-extrusion modling are obtained into coextrusion polypropylene strap；
(4) polypropylene for obtaining plain weave, twill, satin weave or three-dimensional after coextrusion polypropylene strap stretching through braiding is knitted
Thing；
(5) the first crystalline p p sheet, intermediate sheet and the second crystalline p p sheet are stacked gradually into hot pressing, wherein, it is described poly-
Polypropylene fabric is intermediate sheet.
The present inventor is real by substantial amounts of science in order to overcome matrix to infiltrate incomplete defect with reinforcement
Test, it is found that beta crystal-type nucleater is added in the preparation process of polypropylene strap to be more prone to stretching, it is not easy to break, draw
It is higher to stretch multiplying power, material mechanical performance is more stable.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The invention provides a kind of polypropylene self-reinforced composite material, wherein, the polypropylene self-reinforced composite material includes
The first crystalline p p sheet, intermediate sheet and the second crystalline p p sheet stacked gradually from top to bottom；
Wherein, first crystalline p p sheet and second crystalline p p sheet are low melting point polypropylene；
The intermediate sheet is poly- the third of the woven obtained plain weave of coextrusion polypropylene strap, twill, satin weave or three-dimensional
Alkene fabric, and the coextrusion polypropylene strap includes outer layer and sandwich layer, the outer layer is low melting point polypropylene, and the sandwich layer contains
There are high-melting-point polypropylene and beta crystal-type nucleater.
According to the present invention, on the basis of the gross weight of the polypropylene self-reinforced composite material, first polypropylene foil
The total content of material and second crystalline p p sheet can be 50-95wt%, and the content of the intermediate sheet can be 5-
50wt%, it is preferable that the total content of first crystalline p p sheet and second crystalline p p sheet is 75-90wt%, described
The content of intermediate sheet is 10-25wt%.
According to the present invention, the outer layer of the coextrusion polypropylene strap and the percentage by weight of sandwich layer can be 1：9-19；
Preferably, the outer layer of the coextrusion polypropylene strap and the percentage by weight of sandwich layer are 1：11.5-15.7；That is, phase
Accordingly, if on the basis of the gross weight of the coextrusion polypropylene strap, the outer layer of the coextrusion polypropylene strap
Content can be 5-10 parts by weight, and the content of the sandwich layer of the coextrusion polypropylene strap can be 90-95 parts by weight, preferably
Ground, the content of the outer layer of the coextrusion polypropylene strap is 6-8 parts by weight, and the sandwich layer of the coextrusion polypropylene strap contains
Measure as 92-94 parts by weight.
According to the present invention, on the basis of the sandwich layer of the coextrusion polypropylene strap of 100 parts by weight, the high-melting-point gathers
The content of propylene can be 90-95 parts by weight, and the content of the beta crystal-type nucleater can be 5-10 parts by weight, it is preferable that described
The polyacrylic content of high-melting-point is 92-94 parts by weight, and the content of the beta crystal-type nucleater is 6-8 parts by weight.
According to the present invention, the low melting point polypropylene can be atactic copolymerized polypropene, and the low melting point is polyacrylic
Fusing point is 130-140 DEG C, and molecular weight Mw is 3.4 × 105To 1 × 106, molecular weight distribution PD is 3-30, melt index 3-
15g/10min；Specifically, in the present invention, the atactic copolymerized polypropene is not particularly limited, and can be the routine of this area
Selection, it is preferable that the atactic copolymerized polypropene is F560EPS or F800E.
According to the present invention, the high-melting-point polypropylene can be isotactic polypropylene, and the polyacrylic fusing point of the high-melting-point
For 160-170 DEG C, molecular size range and molecular weight distribution do not limit specifically, in the present invention, it is preferred to molecular weight Mw be
3.8×105To 4 × 105, molecular weight distribution PD is 5.06-7.35, melt index 2-3.5g/10min；Specifically, in this hair
In bright, the isotactic polypropylene is not particularly limited, and can be the conventional selection of this area, it is preferable that the isotactic polypropylene
For F300C and T30S.
According to the present invention, the sandwich layer fusing point of the coextrusion polypropylene strap can be 160-170 DEG C.
According to the present invention, the beta crystal-type nucleater can be aromatic amine nucleator, rare earth compounding class nucleator, quinoline
One or more in quinoline acridine ketone nucleator, fused ring compound class nucleator and compounding nucleator.
According to the present invention, the beta crystal-type nucleater can be 2,6- cyclohexanedimethanols acid amides, N'N- dicyclohexyl -2,
One or more in 6- naphthalenes diamides and composite nucleating agent VP101B, it is preferable that the beta crystal-type nucleater is composite nucleating agent
VP101B；Wherein, the composite nucleating agent VP101B contains ultra-fine rubber particles and organic phosphate C29H42O2PNa。
Present invention also offers a kind of preparation method of polypropylene self-reinforced composite material, this method comprises the following steps：
(1) high-melting-point polypropylene and beta crystal-type nucleater are subjected to mixing as sandwich layer polypropylene；
(2) using low melting point polypropylene as outer layer polypropylene；
(3) the sandwich layer polypropylene and the outer layer polypropylene co-extrusion modling are obtained into coextrusion polypropylene strap；
(4) polypropylene for obtaining plain weave, twill, satin weave or three-dimensional after coextrusion polypropylene strap stretching through braiding is knitted
Thing；
(5) the first crystalline p p sheet, intermediate sheet and the second crystalline p p sheet are stacked gradually into hot pressing, wherein, it is described poly-
Polypropylene fabric is intermediate sheet.
According to the present invention, in step (3), using it is three-layer co-extruded go out casting machine, add core in two extruders respectively
Layer polypropylene and outer layer polypropylene, extrusion flow casting molding obtain coextrusion polypropylene strap；Wherein, carry out extruding flow casting molding
Condition is not particularly limited, and can be the conventional selection of this area, in the present invention, it is preferred to, carry out the condition of extrusion molding
Including：Temperature can be 150-200 DEG C, and screw speed can be 10rpm-70rpm during extrusion.
According to the present invention, in step (4), coextrusion polypropylene strap is cut out as 10mm-20mm bands first, so
After redraw (at low temperature at a slow speed), wherein, the condition of the stretching includes：Temperature can be 80-130 DEG C, and rate of extension can
Think 0.1m/min-100m/min, stretching ratio can be 1-16 times；Preferably, the temperature of the stretching is 100 DEG C -120
DEG C, rate of extension 1m/min-10m/min, stretching ratio is 3-15 times.
According to the present invention, the mode of used hot pressing is not particularly limited, and can be the conventional selection of this area, preferably
For double roller hot pressing；In step (5), the condition of the laminating hot pressing includes：Temperature can be 135-200 DEG C, and hot pressing pressure can
Think 3-7MPa, preheating time can be the 180-300 seconds, and pressing time can be the 10-60 seconds.
The present invention is described in detail with reference to embodiments.
In following examples, atactic copolymerized polypropene be Sinopec oil of SPC Co., Ltd production F560EPS or
F800E, there is no the special raw material emphasized directly can be obtained from market purchasing in following examples；
Extrusion casting machine is purchased from Labtech Engineering companies, model LMCR-300；
Differential scanning calorimeter is purchased from PerkinEimer companies, model Diamond DSC；
MTS companies of the U.S., the mechanical property of model CMT6104 test articles are purchased from omnipotent test machine；Wherein, according to
The method measurement provided in ISO179.
Embodiment 1
The present embodiment is used for the preparation method for illustrating polypropylene self-reinforced composite material provided by the invention.
Sandwich layer polypropylene：Beta crystal-type nucleater VP101B by fusing point for 165 DEG C of high-melting-point polypropylene F300C and 6wt%
It is well mixed, wherein, on the basis of the sandwich layer of the coextrusion polypropylene strap of 100 parts by weight, the high-melting-point polypropylene
Content be 94 parts by weight, the content of the beta crystal-type nucleater is 6 parts by weight；Wherein, the polyacrylic molecular weight Mw of the high-melting-point
For 3.8 × 105, PD 5.06, melt index 3.0g/10min；
Outer layer polypropylene：Fusing point is 135 DEG C of low melting point polypropylene F560EPS, and the polyacrylic fusing point of the low melting point originates
Temperature is 130.5 DEG C, and molecular weight Mw is 3.6 × 105, PD 6.4, melt index 3.0g/10min；
Prepare it is three-layer co-extruded go out polypropylene strap：Using it is three-layer co-extruded go out casting machine, added respectively in two extruders
Sandwich layer polypropylene and outer layer polypropylene, it is 180 DEG C in temperature, screw speed is under 35rpm, extrudes flow casting molding；Wherein, it is described
The percentage by weight of the outer layer and sandwich layer that are coextruded polypropylene strap is 1：19；
Prepare polypropylene fabric：Again by it is three-layer co-extruded go out polypropylene strap temperature be 115 DEG C at, rate of extension 1m/
Min simple tensions to 10 times, and by this it is three-layer co-extruded go out crystalline p p sheet cut out as band wide 10mm, by square crossing
Together, the number of plies is 2 layers to mode plain weave；
Laminating hot pressing：Using the polypropylene fabric as intermediate layer, using the outer layer identical poly- third with the polypropylene fabric
Alkene sheet material is used as two layers up and down, and 5min is preheated at 135 DEG C, and pressurize 60s under 7MPa pressure, recycles cold pressing, is in pressure
7MPa pressurizations 30s；
As a result polypropylene self-reinforced composite material F1 provided by the invention is obtained；Wherein, answered with the polypropylene self-reinforcing
On the basis of the gross weight of condensation material, first crystalline p p sheet and the second crystalline p p sheet total content are 90wt%, institute
The content for stating intermediate sheet is 10wt%.
Tested according to tensile property testing standard GB-T1040, polypropylene self-reinforced composite material F1 tensile strength
47.8MPa is brought up to, 111.5% is improved relative to matrix material.
Tested according to the method provided in GB-T9341, polypropylene self-reinforced composite material F1 bending strength is brought up to
1.9MPa, 11.8% is improved relative to matrix material.
Embodiment 2
The present embodiment is used for the preparation method for illustrating polypropylene self-reinforced composite material provided by the invention.
Sandwich layer polypropylene：Beta crystal-type nucleater 2,6- benzene by fusing point for 165 DEG C of high-melting-point polypropylene T30S and 8wt%
Dioctyl phthalate Cyclohexamide be blended, wherein, by 100 parts by weight it is described it is three-layer co-extruded go out polypropylene strap sandwich layer on the basis of, institute
It is 92 parts by weight to state the polyacrylic content of high-melting-point, and the content of the beta crystal-type nucleater is 8 parts by weight；Wherein, the high-melting-point gathers
The molecular weight Mw of propylene is 4.0 × 105, PD 7.35, melt index 3.5g/10min；
Outer layer polypropylene：Fusing point is 135 DEG C of low melting point polypropylene F560EPS, and the polyacrylic fusing point of the low melting point originates
Temperature is 130.5 DEG C, and molecular weight Mw is 3.6 × 105, PD 6.4, melt index 3.0g/10min；
Prepare it is three-layer co-extruded go out polypropylene strap：Using it is three-layer co-extruded go out casting machine, added respectively in two extruders
Sandwich layer polypropylene and outer layer polypropylene, it is 180 DEG C in temperature, screw speed is under 35rpm, extrudes flow casting molding；Wherein, it is described
The percentage by weight of the outer layer and sandwich layer that are coextruded polypropylene strap is 1：9；
Prepare polypropylene fabric：Again by it is three-layer co-extruded go out polypropylene strap temperature be 115 DEG C at, rate of extension 1m/
Min simple tensions to 10 times, and by the simple tension polypropylene strap cut out for 10mm it is wide, the plain weave in the way of square crossing
Together, the number of plies is 5 layers；
Laminating hot pressing：Using the polypropylene fabric as intermediate layer, using the outer layer identical poly- third with the polypropylene fabric
Alkene sheet material is used as two layers up and down, and 210s is preheated at 150 DEG C, and pressurize 60s under 7MPa pressure, recycles cold pressing, is in pressure
7MPa pressurizations 30s；
As a result polypropylene self-reinforced composite material F2 provided by the invention is obtained；Wherein, answered with the polypropylene self-reinforcing
On the basis of the gross weight of condensation material, the total content of first crystalline p p sheet and second crystalline p p sheet is 75wt%,
The content of the intermediate sheet is 25wt%.
Tested according to tensile property testing standard GB-T1040, polypropylene self-reinforced composite material F2 tensile strength
52.3MPa is brought up to, 131.4% is improved relative to matrix material.
Tested according to the method provided in GB-T9341, polypropylene self-reinforced composite material F2 bending strength is brought up to
2.1MPa, 23.5% is improved relative to matrix material.
Embodiment 3
The present embodiment is used for the preparation method for illustrating polypropylene self-reinforced composite material provided by the invention.
Sandwich layer polypropylene：Beta crystal-type nucleater N'N- bis- by fusing point for 165 DEG C of high-melting-point polypropylene F300C and 6wt%
Cyclohexyl -2,6- naphthalene diamides is blended, wherein, on the basis of the sandwich layer of the coextrusion polypropylene strap of 100 parts by weight, institute
It is 94 parts by weight to state the polyacrylic content of high-melting-point, and the content of the beta crystal-type nucleater is 6 parts by weight；Wherein, the high-melting-point gathers
The molecular weight Mw of propylene is 3.8 × 105, PD 5.06, melt index 3.0g/10min；
Outer layer polypropylene：Fusing point is 135 DEG C of low melting point polypropylene F800E, and the polyacrylic fusing point starting of the low melting point is warm
Spend for 128.4 DEG C, molecular weight Mw is 3.4 × 105, PD 4.0, melt index 7.5g/10min；
Prepare polypropylene fabric：Using it is three-layer co-extruded go out casting machine, respectively in two extruders add sandwich layer polypropylene
It it is 180 DEG C in temperature, screw speed is under 35rpm, extrudes flow casting molding with outer layer polypropylene；Wherein, the coextrusion poly- third
The outer layer of alkene band and the percentage by weight of sandwich layer are 1：19；
Prepare polypropylene fabric：Again by it is three-layer co-extruded go out polypropylene strap temperature be 110 DEG C at, rate of extension 3m/
Min simple tensions to 8 times, and by this it is three-layer co-extruded go out crystalline p p sheet cut out as band wide 10mm, by the side of square crossing
Together, the number of plies is 3 layers to formula plain weave；
Laminating hot pressing：Using the polypropylene fabric as intermediate layer, using the outer layer identical poly- third with the polypropylene fabric
Alkene sheet material is used as two layers up and down, and 180s is preheated at 180 DEG C, and pressurize 60s under 5MPa pressure, recycles cold pressing, is in pressure
7MPa pressurizations 30s；
As a result polypropylene self-reinforced composite material F3 provided by the invention is obtained；Wherein, answered with the polypropylene self-reinforcing
On the basis of the gross weight of condensation material, the total content of first crystalline p p sheet and second crystalline p p sheet is 85wt%,
The content of the intermediate sheet is 15wt%.
Tested according to tensile property testing standard GB-T1040, polypropylene self-reinforced composite material F3 tensile strength
49.3MPa is brought up to, 111.5% is improved relative to matrix material.
Tested according to the method provided in GB-T9341, polypropylene self-reinforced composite material F3 bending strength is brought up to
2.0MPa, 18.1% is improved relative to matrix material.
Embodiment 4
The present embodiment is used for the preparation method for illustrating polypropylene self-reinforced composite material provided by the invention.
Polypropylene self-reinforced composite material is prepared according to method same as Example 1, described in embodiment 3
Polypropylene fabric, its difference from Example 1 is：Preheating temperature in hot pressing is brought up to 200 DEG C, during preheating
Between be 150s, moulding pressure 5MPa, pressing time 45s.
As a result polypropylene self-reinforced composite material F4 provided by the invention is obtained；Wherein, answered with the polypropylene self-reinforcing
On the basis of the gross weight of condensation material, the total content of first crystalline p p sheet and second crystalline p p sheet is 70wt%,
The content of the intermediate sheet is 30%.
Tested according to tensile property testing standard GB-T1040, polypropylene self-reinforced composite material F4 tensile strength
51.9MPa is brought up to, 129.6% is improved relative to matrix material.
Tested according to the method provided in GB-T9341, polypropylene self-reinforced composite material F4 bending strength is brought up to
2.2MPa, 29.4% is improved relative to matrix material.
Embodiment 5
The present embodiment is used for the preparation method for illustrating polypropylene self-reinforced composite material provided by the invention.
Polypropylene self-reinforced composite material is prepared according to method same as Example 1, described in embodiment 3
Polypropylene strap is coextruded, its difference from Example 3 is：The coextrusion polypropylene strap is stretched to 15 times；And
The polypropylene fabric is preheated into 180s at 150 DEG C, pressurize 60s under 5MPa pressure；
As a result polypropylene self-reinforced composite material F5 provided by the invention is obtained；Wherein, answered with the polypropylene self-reinforcing
On the basis of the gross weight of condensation material, the total content of first crystalline p p sheet and second crystalline p p sheet is 50wt%,
The content of the intermediate sheet is 50wt%.
Tested according to tensile property testing standard GB-T1040, polypropylene self-reinforced composite material F5 tensile strength
48.9MPa is brought up to, 116.4% is improved relative to matrix material.
Tested according to the method provided in GB-T9341, polypropylene self-reinforced composite material F5 bending strength is brought up to
2.0MPa, 17.6% is improved relative to matrix material.
Comparative example 1
Polypropylene self-reinforced composite material is prepared according to method same as Example 1, institute's difference is, is preparing
During sandwich layer is polyacrylic, beta crystal-type nucleater is not added；
As a result polypropylene self-reinforced composite material DF1 is made；Wherein, with the gross weight of the polypropylene self-reinforced composite material
On the basis of amount, the total content of first crystalline p p sheet and second crystalline p p sheet is 90wt%, the intermediate sheet
Content be 10wt%.
Tested according to tensile property testing standard GB-T1040, polypropylene self-reinforced composite material DF1 tensile strength
39.6MPa is brought up to, 75.2% is improved relative to matrix material.
Tested according to the method provided in GB-T9341, polypropylene self-reinforced composite material DF1 bending strength improves
To 1.8MPa, 5.9% is improved relative to matrix material.
Comparative example 2
Polypropylene self-reinforced composite material is prepared according to method same as Example 1, institute's difference is, is preparing
During polypropylene fabric, temperature be 100 DEG C at, rate of extension be 0.5m/min simple tensions to 8 times,
As a result polypropylene self-reinforced composite material DF2 is made；Wherein, with the gross weight of the polypropylene self-reinforced composite material
On the basis of amount, the total content of first crystalline p p sheet and second crystalline p p sheet is 75wt%, the intermediate sheet
Content be 25wt%.
Tested according to tensile property testing standard GB-T1040, polypropylene self-reinforced composite material DF2 tensile strength
41.2MPa is brought up to, 82.3% is improved relative to matrix material.
Tested according to the method provided in GB-T9341, polypropylene self-reinforced composite material DF2 bending strength improves
To 1.7MPa, 10.8% is improved relative to matrix material.
Comparative example 3
Polypropylene self-reinforced composite material is prepared according to method same as Example 1, institute's difference is, is being laminated
In hot pressing, the crystalline p p sheet differed using the outer layer with the polypropylene fabric is used as two layers up and down；
As a result polypropylene self-reinforced composite material DF3 provided by the invention is obtained；Wherein, answered with the polypropylene self-reinforcing
On the basis of the gross weight of condensation material, the total content of first crystalline p p sheet and second crystalline p p sheet is 80wt%,
The content of the intermediate sheet is 20wt%.
Tested according to tensile property testing standard GB-T1040, polypropylene self-reinforced composite material DF3 tensile strength
42.3MPa is brought up to, 87.2% is improved relative to matrix material.
Tested according to the method provided in GB-T9341, polypropylene self-reinforced composite material DF3 bending strength improves
To 1.8MPa, 5.9% is improved relative to matrix material.
It can be seen that from above example 1-5 and comparative example 1-3 result：Increased certainly using polypropylene provided by the invention
The preparation method of strong composite, adds beta crystal-type nucleater so that the polypropylene self-reinforcing composite wood of preparation in preparation process
Expect that F1-F5 tests according to tensile property testing standard GB-T1040, tensile strength brings up to 47.8-52.3MPa, relative to matrix
Material improves 111.5%-131.4%；And the polypropylene self-reinforced composite material DF1-DF3 prepared in comparative example 1-3 drawing
Stretch intensity and bring up to 39.6-42.3MPa, 75.2%-87.2% is improved relative to matrix material；
Tested according to the method provided in GB-T9341, polypropylene self-reinforced composite material F1-F5 prepared by embodiment 1-5
Bending strength be 1.9-2.2MPa, improve 11.8%-29.4% relative to matrix material；And prepared in comparative example 1-3
Polypropylene self-reinforced composite material DF1-DF3 bending strength is 1.7-1.9MPa, and 5.9%- is improved relative to matrix material
10.8%；
Therefore, using the preparation method of polypropylene self-reinforced composite material provided by the invention stretching can be made more to hold
Easily, not easy to break, stretching ratio is higher, and material mechanical performance is more stable.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (12)
1. a kind of polypropylene self-reinforced composite material, it is characterised in that the polypropylene self-reinforced composite material is included from top to bottom
The first crystalline p p sheet, intermediate sheet and the second crystalline p p sheet stacked gradually；
Wherein, first crystalline p p sheet and second crystalline p p sheet are low melting point polypropylene；
The intermediate sheet is knitted for the polypropylene of the woven obtained plain weave of coextrusion polypropylene strap, twill, satin weave or three-dimensional
Thing, and the coextrusion polypropylene strap includes outer layer and sandwich layer, the outer layer is low melting point polypropylene, and the sandwich layer contains height
Melt polypropylene and beta crystal-type nucleater, on the basis of the sandwich layer of the coextrusion polypropylene strap of 100 parts by weight, the height
The content of melt polypropylene is 90-95 parts by weight, and the content of the beta crystal-type nucleater is 5-10 parts by weight.
2. composite according to claim 1, wherein, using the gross weight of the polypropylene self-reinforced composite material as base
The total content of standard, first crystalline p p sheet and second crystalline p p sheet is 50-95 weight %, the intermediate sheet
Content is 5-50 weight %.
3. composite according to claim 1, wherein, the outer layer of the coextrusion polypropylene strap and the weight of sandwich layer
Percentage is 1：9-19.
4. composite according to claim 1, wherein, the low melting point polypropylene is atactic copolymerized polypropene；It is described
High-melting-point polypropylene is isotactic polypropylene.
5. the composite according to claim 1 or 4, wherein, the polyacrylic fusing point of high-melting-point is 160-170 DEG C,
The polyacrylic fusing point of low melting point is 130-140 DEG C.
6. composite according to claim 1, wherein, the beta crystal-type nucleater is aromatic amine nucleator, rare earth is matched somebody with somebody
One or more in compound class nucleator, quinoline acridine ketone nucleator, fused ring compound class nucleator and compounding nucleator.
7. composite according to claim 6, wherein, the beta crystal-type nucleater be 2,6- cyclohexanedimethanols acid amides,
One or more in N'N- dicyclohexyls -2,6- naphthalenes diamides and composite nucleating agent VP101B.
8. a kind of preparation method of the polypropylene self-reinforced composite material in claim 1-7 described in any one, this method bag
Include following steps：
(1) high-melting-point polypropylene and beta crystal-type nucleater are subjected to mixing as sandwich layer polypropylene；
(2) using low melting point polypropylene as outer layer polypropylene；
(3) the sandwich layer polypropylene and the outer layer polypropylene co-extrusion modling are obtained into coextrusion polypropylene strap；
(4) polypropylene fabric of plain weave, twill, satin weave or three-dimensional will be obtained through braiding after coextrusion polypropylene strap stretching；
(5) the first crystalline p p sheet, intermediate sheet and the second crystalline p p sheet are stacked gradually into hot pressing, wherein, the polypropylene
Fabric is intermediate sheet.
9. according to the method for claim 8, wherein, in step (3), the condition of the extrusion molding includes：Temperature is
150-200 DEG C, screw speed is 10rpm-70rpm during extrusion.
10. according to the method for claim 8, wherein, in step (4), the condition of the stretching includes：Temperature is 80-
130 DEG C, rate of extension 0.1m/min-100m/min, stretching ratio is 1-16 times.
11. according to the method for claim 8, wherein, in step (4), the condition of the stretching includes：Temperature is 100-
120 DEG C, rate of extension 1m/min-10m/min, stretching ratio is 3-15 times.
12. according to the method for claim 8, wherein, in step (5), the condition of the laminating hot pressing includes：Temperature is
135-200 DEG C, hot pressing pressure 3-7MPa, preheating time is the 180-300 seconds, and pressing time is the 10-60 seconds.
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| CN107972343B (en) * | 2016-10-21 | 2020-07-24 | 中国石油化工股份有限公司 | Polypropylene composite material, polypropylene self-reinforced composite material and preparation method thereof |
| CN107216584B (en) * | 2017-07-26 | 2019-03-05 | 立昌科技（赣州）有限公司 | A kind of fluororesin alloy and preparation method thereof |
| WO2023078441A1 (en) * | 2021-11-08 | 2023-05-11 | 中国石油化工股份有限公司 | Polypropylene composite material having melting point gradient structure, preparation method therefor and system and use thereof |
| CN115771320B (en) * | 2022-11-21 | 2023-08-22 | 佛山市顺德区南凯新材料实业有限公司 | Polypropylene self-reinforced composite material and preparation method thereof |
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