CN109354764A - A kind of nano-cellulose reinforced polypropylene foamed material and preparation method thereof - Google Patents

A kind of nano-cellulose reinforced polypropylene foamed material and preparation method thereof Download PDF

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CN109354764A
CN109354764A CN201811063989.5A CN201811063989A CN109354764A CN 109354764 A CN109354764 A CN 109354764A CN 201811063989 A CN201811063989 A CN 201811063989A CN 109354764 A CN109354764 A CN 109354764A
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polypropylene
cellulose
nano
extruder
parts
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汪龙
汪彪
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Hefei Huaju Microscience New Materials Co Ltd
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Hefei Huaju Microscience New Materials Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2401/02—Cellulose; Modified cellulose
    • C08J2401/04—Oxycellulose; Hydrocellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

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Abstract

The present invention discloses a kind of nano-cellulose reinforced polypropylene foamed material and preparation method thereof, is made of by weight following components: 88-97.8 parts of polypropylene；2-10 parts of cellulose；0.2-2 parts of compatilizer；Supercritical fluid is the 1-10% of polypropylene weight.The present invention improves the interface of polypropylene and nano-cellulose using maleic anhydride inoculated polypropylene as compatilizer, and composite material is made to have high-intensitive and high-modulus.Meanwhile nano-cellulose one forms filler network, the melt strength of reinforced polypropylene in polypropylene；It is alternatively arranged as polyacrylic crystal nucleating agent, improves polyacrylic foaming capacity.Polypropylene/Nano cellulose composite material is prepared using the method being blended is squeezed out, simple process is suitble to large-scale industrial production.

Description

A kind of nano-cellulose reinforced polypropylene foamed material and preparation method thereof
Technical field
The present invention relates to a kind of polypropylene materials and preparation method thereof, and in particular to a kind of nano-cellulose reinforced polypropylene Foamed material and preparation method thereof belongs to field of high polymer material processing.
Background technique
Foamed plastics is one kind using polymer as matrix, the internal poromerics containing bulk gas, is a kind of special Solid/gas composite material.Compared with unexpanded plastics, foamed plastics have light, sound insulation, heat-insulated, specific strength is high, Gao Chong The features such as hit intensity and strong absorbability, therefore in packing business, automobile industry, transport service, daily necessities, war industry, locomotory apparatus Material and building etc. are used widely.Currently, most widely used foamed plastics mainly has expanded polystyrene (EPS) (PS), foaming poly- Urethane (PU) and expanded polyolefin plastics three categories.Generally use fluorochlorohydrocarbon or butane as foaming during foamed polystyrene Agent influences environment, while product degradation leads to " white pollution " again.Polyurethane foam is related to having human body during the preparation process Harmful isocyanates, furthermore polyurathamc is thermosetting polymer, it is difficult to recycle secondary use.Poly- second in expanded polyolefin Alkene foamed material, intensity is low, and temperature tolerance is poor, it is difficult to for having certain requirements place to mechanical property and temperature.
Polypropylene material have excellent mechanical performance, higher heat resistance, it is resistant to chemical etching, be easy to be recycled etc. spies Point.Thus compared with the poly- PS and PE that foams, expanded polypropylene has the advantages that very much.Firstly, excellent mechanical property: with PE phase Than again PP has higher rigidity and bending modulus, while the shock resistance of PP is better than PS.Secondly, high-fire resistance: foaming PE Heat resisting temperature range is 70-80 DEG C, and foam PS is also usually less than 80 DEG C, and the PP maximum operation (service) temperature that foams is up to 120 DEG C, can be with It is used for a long time at high temperature.In addition, foaming PP also has the ability of excellent absorption energy, significant thermal insulation, good resistance to Stress cracking resistance and excellent chemical corrosion resistance.Thus, PP foamed material has in the industries such as auto industry and food packaging Broad application prospect and huge competitiveness can replace traditional foam PS and PE.
However, the melt strength due to plain polypropylene is low, foam window narrows, is not suitable for being directly used in foaming, generally exist It needs to carry out enhancing modification to polypropylene before foaming.The method for improving polypropylene expanded ability at present mainly has following three kinds:
First is that changing polypropylene molecule chain structure, branching or crosslinked polypropylene are formed, high melt strength, propylene is obtained (HMSPP).For example BASELL company in 1994 has researched and developed successfully and has synthesized HMSPP with direct polymerization method.But the production technology is multiple Miscellaneous, which only rests in several companies, at the same HMSPP is at high cost and foaming process in use flammable organic foaming Agent, equipment are needed by special technological processing for explosion protection feature, it is difficult to a wide range of to promote.
Second is that polypropylene and other polymers are blended, foamed using the melt characteristic of different polymer.For example, CN101275002A is disclosed polypropylene and ultra-high molecular weight polyethylene blending, is then foamed and is gathered using physical blowing agent Acryl foam plastics.CN104292611B, which is disclosed, a kind of utilizes polypropylene and polyethylene and polyacrylic semicrystalline polymeric The method for being blended to prepare foamed material, the technique commonly use intermittent foaming technique, obtain good foam structure. CN105694233A discloses a kind of method being blended using polypropylene and alpha-olefin low polymers to prepare PP foam material. But due to the poor compatibility between different polymers compositions, the cell uniformity and mechanical property of gained foamed material are generally all It is lower, while the addition of low molecular weight solubilizer can reduce product strength.
Third is that the addition of filler can significantly improve polyacrylic foaming capacity, while the mechanics of expanded polypropylene can also be improved Performance is a kind of method for effectively improving its foaming capacity.Such as CN101538387B disclose it is a kind of using polypropylene and The method that filler blending prepares foamed material, filler used are mainly carbon black, graphite and magnesium hydroxide.CN105623098A is disclosed A kind of preparation method improving polypropylene expanded ability using long glass fibres.
But filler added by reinforced polypropylene foaming capacity is substantially inorganic filler at present.With getting worse Problem of environmental pollution, using the renewable resource in nature as the filler of polymer, in final offal treatment and original Material all has better environmental benefit using upper.As cellulose most important in biological fiber, have natural reproducible, Source is wide, widely distributed, agriculture non-food stuff is leading, low-density, high intensity, high reaction activity, thus cellulose as polymerization The reinforced phase and filler of object have good application prospect.However, since cellulose surface is polar, it is difficult in nonpolar substrates As being evenly distributed in polypropylene, in interface gap easy to form and defect when the two mixes, and between cellulose and polypropylene matrix It is poor that low cohesive force will lead to gained composite materials property.For that purpose it is necessary to which mating surface processing and suitable compatilizer come Excellent polypropylene/the cellulose composite material of processability, it is final to obtain the excellent PP foam material of foam performance.
Summary of the invention
In view of the problems of the existing technology, it is an object of that present invention to provide a kind of foaming of nano-cellulose reinforced polypropylene Material and preparation method thereof, gained polypropylene extruded foaming materials expansion ratio height, meet lightweight requirements at uniform foam cell.
Technical solution of the present invention:
A kind of nano-cellulose reinforced polypropylene foamed material, it is characterised in that: it is made of by weight following components:
88-97.8 parts of polypropylene；
2-10 parts of cellulose；
0.2-2 parts of compatilizer；
Supercritical fluid is the 1-10% of polypropylene weight.
Further scheme, selected polyacrylic number-average molecular weight are 20-50 ten thousand；Selected cellulose is nano-cellulose.
Further scheme, selected compatilizer are maleic anhydride inoculated polypropylene；The supercritical fluid is nitrogen, titanium dioxide The gas of one or more kinds of mixing of carbon, air, argon gas.
Preferably, the nitrogen is the 1-3% of polypropylene weight；Carbon dioxide is the 4-10% of polypropylene weight.
Another goal of the invention of the invention is to provide a kind of system of above-mentioned nano-cellulose reinforced polypropylene foamed material Preparation Method comprising following steps:
(1) it by the pulp dilution containing cellulose, is then added in ball mill and is handled, removed using strong mechanical force To nano-cellulose slurries；
(2) 88-97.8 parts and 0.2-2 parts of compatilizer agent of the polypropylene feed openings by double screw extruder are added, then It will be added containing 2-10 parts of cellulose of nano-cellulose slurries by the auxiliary feed ports of extruder, melt blending passes through simultaneously Exhaust outlet on extruder barrel excludes vapor, then obtains polypropylene/Nano cellulose through extrusion, underwater cooling, pelletizing Composite material；
(3) polypropylene/Nano cellulose composite material is placed in foamed system, after material molten to be composite, is faced super Boundary's fluid is inputted in screw rod by the gas injection port on extruder by metering pump, and single-phase polymer/gas melt is obtained；Then to it It foams, PP foam material is obtained after cooling and shaping.
Further scheme, paper pulp described in step (1) are bleached kraft pulp；Nanofiber in the nanofiber slurries The mass content of element is 5-40%.
Further scheme, pulp dilution described in step (1) are to be diluted with distilled water into the slurry that mass concentration is 2-7% Liquid, the temperature of the ball mill are 30-70 DEG C, and the charging rate of slurries is 700-1000ml/min.
Further scheme, selected compatilizer is maleic anhydride inoculated polypropylene in step (2)；The polypropylene/Nano is fine The mass content for tieing up nano-cellulose in plain composite material is 2-10%；The extruder temperature of double screw extruder is 170-240 DEG C, Screw speed is 100-200rpm.
Further scheme, foamed system is that double screw extruder, single screw extrusion machine or second order series connection squeeze out in step (3) Machine；The supercritical fluid is nitrogen or carbon dioxide, and wherein nitrogen is the 1-3% of polypropylene weight；Carbon dioxide is poly- The 4-10% of propylene weight.
It is furthermore preferred that the second order tandem extruder is by the first rank double screw extruder and second-order single screw extrusion machine It is connected in series, is to be placed in polypropylene/Nano cellulose composite material in the first rank double screw extruder to melt, by shooting flow Body is inputted in screw rod by the gas injection port on extruder by metering pump, and single-phase polymer/gas melt is obtained；It then will be single-phase poly- It closes and foams in object/gas melt importing second-order single screw extrusion machine, PP foam material is obtained after cooling and shaping；
In the first rank double screw extruder melting zone temperature be 170-230 DEG C, screw speed 15-25r/min；Institute State in second-order single screw extrusion machine temperature at head be 115-150 DEG C, at head pressure be 8-24MPa, screw speed 10- 20r/min。
Mouth mold in the present invention in foamed system can be flat mouth mould, circular mouth mold or annular die, be met not with preparation With the PP foam material of demand.
Beneficial effects of the present invention:
(1) present invention has obtained nano-cellulose in such a way that high mechanical force is removed, and can be obtained large batch of containing receiving The paper pulp of rice cellulose.
(2) present invention improves the boundary of polypropylene and nano-cellulose using maleic anhydride inoculated polypropylene as compatilizer Face, the composite material have high-intensitive and high-modulus.Meanwhile polypropylene/Nano cellulose is prepared using the method being blended is squeezed out Composite material, simple process are suitble to large-scale industrial production.
(3) filler network on the one hand can be formed in polypropylene using nano-cellulose, the melt of reinforced polypropylene is strong Degree；On the other hand, cellulose can be used as polyacrylic crystal nucleating agent, promote polyacrylic crystal property.Therefore, Nanowire The addition of dimension element can significantly improve polyacrylic foaming capacity.
(4) present invention prepares polypropylene foam, abscess-size, cell density and expansion ratio using extrusion foaming technology It can be regulated and controled by nanofiber cellulose content, density of foaming agent and blowing temperature, there is height Modulatory character, be able to satisfy difference Application demand.
(5) the resulting nano-cellulose reinforced polypropylene foamed material of the present invention has highly controllable expansion ratio and Even pore structure, expansion ratio 5-45, mean cell diameter are not more than 50 μm, and cell density can reach 108-9/cm3.
(6) present invention is foamed using second order tandem extruder, can be effectively using nano-cellulose as poly- The crystallization nucleating agent and rheology modifier of propylene, so as to improve polyacrylic foam performance.
Detailed description of the invention:
Fig. 1 is polypropylene/cellulose composite material crystallization curve figure of raw material polypropylene and preparation in example IV,
Fig. 2 is the scanning electron microscope (SEM) photograph of one gained PP foam material of embodiment.
Specific embodiment
Following embodiment is several typical embodiments, can not limit effect of the invention, the technology of this field Personnel are referred to embodiment and are reasonably designed technical solution, can equally obtain result of the invention.
Crystallization curve, expansion ratio, the test method of cell density are as follows in the present invention:
Crystallization curve: polyacrylic crystallization curve can be obtained with differential scanning calorimetry (DSC) instrument, by 5-7mg or so Sample be put into DSC instrument, 250 DEG C, isothermal 5min are heated to from 30 DEG C with the heating rate of 10 DEG C/min first, then with The rate of temperature fall of 10 DEG C/min is reduced to 30 DEG C from 250 DEG C, records cooling procedure curve, and it is bent that polyacrylic crystallization can be obtained Line.
Expansion ratio: testing the density of foamed material and unfoamed material according to GB/T6343-2009 standard respectively, for Foamed sample is measured using drainage, and the expansion ratio of foamed sample is then calculated.Expansion ratio (Φ)=ρpolymer/ ρfoam, wherein ρpolymerFor the density of unfoamed material, ρfoamFor the density of foamed material.
Cell density: microcellular foam material is quenched through liquid nitrogen disconnected, after section metal spraying, using scanning electron microscope (SEM) Observe the foam structure inside foamed material.Abscess-size is measured using Image J software and calculates cell density.Wherein steep Hole density N (unit: a/cm3)=(n/A)3/2× Φ, n are the abscess number on selected stereoscan photograph, and A is scanned photograph Real area (unit: cm2), Φ is expansion ratio.
Embodiment 1
(1) bleached kraft pulp containing cellulose is diluted to the slurries of 2wt% with distilled water, is then existed with ball mill 30 DEG C carry out decentralized processing to slurries under 750ml/min charging rate, obtain nano-cellulose slurries.
(2) 40 parts of the nano-cellulose slurries by nano-cellulose mass content for 5%, maleic anhydride inoculated polypropylene 97.8 parts of melt blendings in double screw extruder of polypropylene that 0.2 part and number-average molecular weight are 250,000, obtain nanofiber Polypropylene/cellulose composite material that cellulose content is 1%.
(3) composite material is placed in the first rank double screw extruder, melting temperature is 170-230 DEG C, and screw speed is 15r/min, while 9.78 parts of nitrogen (the 1% of polypropylene quality) is inputted into screw rod by the gas injection port metering pump on extruder It is interior, it is uniformly mixed, obtains single-phase polymer/gas melt.
(4) single-phase polymer/gas melt is imported in second-order single screw extrusion machine, reduces second-order single screw rod and squeezes out Machine melt temperature, melt temperature is 180-200 DEG C, screw speed 10r/min, while reducing extruder temperature at head, makes machine Melt temperature is 115 DEG C at head, and pressure is 24MPa at head, foams finally by die extrusion and obtains after cooling and shaping PP foam material.
It is illustrated in figure 2 the scanning electron microscope (SEM) photograph of PP foam material prepared by the present embodiment, after tested gained poly- third The expansion ratio of alkene foam is 24 times, and mean cell diameter is 47 μm, and cell density is 2.2 × 108A/cm3。
Embodiment 2
(1) bleached kraft pulp containing cellulose is diluted to the slurries of 2wt% with distilled water, is then existed with ball mill 40 DEG C carry out decentralized processing to slurries under 700ml/min charging rate, obtain nano-cellulose slurries.
(2) 40 parts of the nano-cellulose slurries by nano-cellulose mass content for 5%, maleic anhydride inoculated polypropylene 97.8 parts of melt blendings in double screw extruder of polypropylene that 0.2 part and number-average molecular weight are 350,000, obtain nanofiber Polypropylene/cellulose composite material that cellulose content is 1%.
(3) composite material is placed in the first rank double screw extruder, melting temperature is 170-230 DEG C, screw speed For 20r/min, while by 1.956 parts of nitrogen gas by being uniformly mixed in the gas injection port metering pump input screw rod on extruder, Obtain single-phase polymer/gas melt.
(4) single-phase polymer/gas melt is imported in second-order single screw extrusion machine, and reduces second-order single screw rod and squeezes Machine melt temperature is 180-200 DEG C, screw speed 15r/min out, while reducing extruder temperature at head, makes to melt at head Temperature is 120 DEG C, pressure is 20MPa at head, foams finally by die extrusion and obtains polypropylene after cooling and shaping Foamed material.
The expansion ratio of gained polypropylene foam is 27 times after tested, and mean cell diameter is 45 μm, cell density 3.5 ×108A/cm3。
Embodiment 3
(1) bleached kraft pulp containing cellulose is diluted to the slurries of 2wt% with distilled water, is then existed with ball mill 40 DEG C carry out decentralized processing to slurries under 700ml/min charging rate, obtain nano-cellulose slurries.
(2) 40 parts of the nano-cellulose slurries by nano-cellulose mass content for 5%, maleic anhydride inoculated polypropylene 97.8 parts of melt blendings in double screw extruder of polypropylene that 0.2 part and number-average molecular weight are 450,000, obtain nanofiber Polypropylene/cellulose composite material that cellulose content is 1%.
(3) composite material is placed in the first rank double screw extruder, melting temperature is 170-230 DEG C, and screw speed is 25r/min, while by 2.934 parts of nitrogen by being uniformly mixed, obtaining list in the gas injection port metering pump input screw rod on extruder The polymer of phase/gas melt.
(4) single-phase polymer/gas melt is imported in second-order single screw extrusion machine, and reduces second-order single screw rod and squeezes Machine melt temperature out, melt temperature is 180-200 DEG C, screw speed 15r/min, while reducing extruder temperature at head, is made Melt temperature is 120 DEG C at head, and pressure is 20MPa at head, foams finally by die extrusion and obtains after cooling and shaping To PP foam material.
The expansion ratio of gained polypropylene foam is 29 times after tested, and mean cell diameter is 42 μm, cell density 4.8 ×108A/cm3。
Embodiment 4
(1) bleached kraft pulp containing cellulose is diluted to the slurries of 5wt% with distilled water, is then existed with ball mill 50 DEG C carry out decentralized processing to slurries under 900ml/min charging rate, obtain nano-cellulose slurries.
(2) 25 parts of the nano-cellulose slurries by nano-cellulose mass content for 20%, maleic anhydride inoculated polypropylene 1 94 parts of melt blendings in double screw extruder of polypropylene that part and number-average molecular weight are 250,000, obtain nanofiber cellulose content For 5% polypropylene/cellulose composite material.
As shown in Figure 1, polypropylene/cellulose composite material knot that raw material polypropylene and nanofiber cellulose content are 5% Brilliant curve graph.It is seen that polyacrylic peak crystallization is 113 DEG C；Due to the increase of nano-cellulose significantly improve it is poly- The peak crystallization of propylene illustrates that nano-cellulose is polypropylene so polypropylene/cellulose composite material peak crystallization is 125 DEG C A kind of effective crystal nucleating agent, so that polyacrylic foaming capacity can be improved.
(3) composite material is placed in the first rank double screw extruder, melting temperature is 170-230 DEG C, and screw speed is 20r/min, while by 3.76 parts of carbon dioxide by being uniformly mixed, obtaining in the gas injection port metering pump input screw rod on extruder To single-phase polymer/gas melt.
(4) single-phase polymer/gas melt is imported in second-order single screw extrusion machine, and reduces second-order single screw rod and squeezes Machine melt temperature out, melt temperature is 180-200 DEG C, screw speed 15r/min, while reducing extruder temperature at head, is made Melt temperature is 140 DEG C at head, and pressure is 12MPa at head, foams finally by die extrusion and obtains after cooling and shaping To PP foam material.
The expansion ratio of gained polypropylene foam is 31 times after tested, and mean cell diameter is 38 μm, cell density 6.7 ×108A/cm3。
Embodiment 5
(1) bleached kraft pulp containing cellulose is diluted to the slurries of 5wt% with distilled water, is then existed with ball mill 60 DEG C carry out decentralized processing to slurries under 850ml/min charging rate, obtain nano-cellulose slurries.
(2) 25 parts of the nano-cellulose slurries by nano-cellulose mass content for 20%, maleic anhydride inoculated polypropylene 1 94 parts of melt blendings in double screw extruder of polypropylene that part and number-average molecular weight are 350,000, obtain nanofiber cellulose content For 5% polypropylene/cellulose composite material.
(3) composite material is placed in the first rank double screw extruder, melting temperature is 170-230 DEG C, and screw speed is 25r/min, while by 6.58 parts of carbon dioxide by being uniformly mixed, obtaining in the gas injection port metering pump input screw rod on extruder To single-phase polymer/gas melt.
(4) single-phase polymer/gas melt is imported in second-order single screw extrusion machine, and reduces second-order single screw rod and squeezes Machine melt temperature out, melt temperature is 180-200 DEG C, screw speed 20r/min, while reducing extruder temperature at head, is made Melt temperature is 135 DEG C at head, and pressure is 15MPa at head, foams finally by die extrusion and obtains after cooling and shaping To PP foam material.
The expansion ratio of gained polypropylene foam is 35 times after tested, and mean cell diameter is 33 μm, cell density 8.7 ×108A/cm3。
Embodiment 6
(1) bleached kraft pulp containing cellulose is diluted to the slurries of 5wt% with distilled water, is then existed with ball mill 60 DEG C carry out decentralized processing to slurries under 850ml/min charging rate, obtain nano-cellulose slurries.
(2) 25 parts of the nano-cellulose slurries by nano-cellulose mass content for 20%, maleic anhydride inoculated polypropylene 1 94 parts of melt blendings in double screw extruder of polypropylene that part and number-average molecular weight are 450,000, obtain nanofiber cellulose content For 5% polypropylene/cellulose composite material.
(3) composite material is placed in the first rank double screw extruder, melting temperature is 170-230 DEG C, and screw speed is 25r/min, while by 9.4 parts of carbon dioxide by being uniformly mixed, obtaining in the gas injection port metering pump input screw rod on extruder Single-phase polymer/gas melt.
(4) single-phase polymer/gas melt is imported in second-order single screw extrusion machine, and reduces second-order single screw rod and squeezes Machine melt temperature out, melt temperature is 180-200 DEG C, screw speed 20r/min, while reducing extruder temperature at head, is made Melt temperature is 130 DEG C at head, and pressure is 16MPa at head, foams finally by die extrusion and obtains after cooling and shaping To PP foam material.
The expansion ratio of gained polypropylene foam is 40 times after tested, and mean cell diameter is 29 μm, cell density 1.5 ×109A/cm3。
Embodiment 7
(1) bleached kraft pulp containing cellulose is diluted to the slurries of 7wt% with distilled water, is then existed with ball mill 70 DEG C carry out decentralized processing to slurries under 1000ml/min charging rate, obtain nano-cellulose slurries.
(2) 25 parts of the nano-cellulose slurries by nano-cellulose mass content for 40%, maleic anhydride inoculated polypropylene 2 88 parts of melt blendings in double screw extruder of polypropylene that part and number-average molecular weight are 450,000, obtain nanofiber cellulose content For 10% polypropylene/cellulose composite material.
(3) composite material is placed in the first rank double screw extruder, melting temperature is 170-230 DEG C, and screw speed is 25r/min, while 7.04 parts of carbon dioxide (the 8% of polypropylene quality) is inputted into spiral shell by the gas injection port metering pump on extruder In bar, it is uniformly mixed, obtains single-phase polymer/gas melt.
(4) single-phase polymer/gas melt is imported in second-order single screw extrusion machine, and reduces second-order single screw rod and squeezes Machine melt temperature out, melt temperature is 180-210 DEG C, screw speed 20r/min, while reducing extruder temperature at head, is made Melt temperature is 150 DEG C at head, and pressure is 14MPa at head, foams finally by die extrusion and obtains after cooling and shaping To PP foam material.
The expansion ratio of gained polypropylene foam is 12 times after tested, and mean cell diameter is 48 μm, cell density 1.2 ×108A/cm3。
Comparative example 1
(1) polypropylene that number-average molecular weight is 250,000 is placed in the first rank double screw extruder, melting temperature 170- 230 DEG C, screw speed 15r/min, it is in terms of 100 parts by polymers compositions, while group is divided into 7 carbon dioxide by extruder On gas injection port metering pump input screw rod in, be uniformly mixed, obtain single-phase polymer/gas melt.
(2) second-order Single Screw Extruder and Melt temperature is reduced, melt temperature is 180-200 DEG C, screw speed 10r/ Min, while extruder temperature at head is reduced, making 140 DEG C of melt temperature at head, pressure is 10MPa at head, finally by Die extrusion foams and obtains PP foam material after cooling and shaping.
The expansion ratio of gained polypropylene foam is 4 times after tested, and mean cell diameter is 200 μm, cell density 2.1 ×105A/cm3。
Comparative example 2
(1) polypropylene that number-average molecular weight is 450,000 is placed in the first rank double screw extruder, melting temperature 170- 230 DEG C, screw speed 15r/min, it is in terms of 100 parts by polymers compositions, while group is divided into 1 nitrogen by extruder Gas injection port metering pump inputs in screw rod, is uniformly mixed, obtains single-phase polymer/gas melt.
(2) second-order Single Screw Extruder and Melt temperature is reduced, melt temperature is 180-200 DEG C, screw speed 10r/ Min, while extruder temperature at head is reduced, making 135 DEG C of melt temperature at head, pressure is 8MPa at head, finally by Die extrusion foams and obtains PP foam material after cooling and shaping.
The expansion ratio of gained polypropylene foam is 9 times after tested, and mean cell diameter is 180 μm, cell density 4.5 ×105A/cm3。
It should be understood that for those of ordinary skills, it can be modified or changed according to the above description, And all these modifications and variations all should belong to protection scope of the present invention.

Claims (10)

1. a kind of nano-cellulose reinforced polypropylene foamed material, it is characterised in that: it is made of by weight following components:
88-97.8 parts of polypropylene；
2-10 parts of cellulose；
0.2-2 parts of compatilizer；
Supercritical fluid is the 1-10% of polypropylene weight.
2. a kind of nano-cellulose reinforced polypropylene foamed material according to claim 1, it is characterised in that: selected poly- third The number-average molecular weight of alkene is 20-50 ten thousand；Selected cellulose is nano-cellulose.
3. a kind of nano-cellulose reinforced polypropylene foamed material according to claim 1, it is characterised in that: selected compatible Agent is maleic anhydride inoculated polypropylene；The supercritical fluid be nitrogen, carbon dioxide, air, argon gas one kind or it is a kind of with Upper mixed gas.
4. a kind of nano-cellulose reinforced polypropylene foamed material according to claim 3, it is characterised in that: the nitrogen For the 1-3% of polypropylene weight；Carbon dioxide is the 4-10% of polypropylene weight.
5. a kind of preparation method of nano-cellulose reinforced polypropylene foamed material, it is characterised in that: the following steps are included:
(1) it by the pulp dilution containing cellulose, is then added in ball mill and is handled, removed and received using strong mechanical force Rice cellulose slurries；
(2) 88-97.8 parts and 0.2-2 parts of compatilizer agent of the polypropylene feed openings by double screw extruder are added, then will contained There are 2-10 parts of cellulose of nano-cellulose slurries to be added by the auxiliary feed ports of extruder, melt blending, while passing through extrusion Exhaust outlet on machine barrel excludes vapor, then through extrusion, underwater cooling, that pelletizing obtains polypropylene/Nano cellulose is compound Material；
(3) polypropylene/Nano cellulose composite material is placed in foamed system, after material molten to be composite, by shooting flow Body is inputted in screw rod by the gas injection port on extruder by metering pump, and single-phase polymer/gas melt is obtained；Then it is carried out Foaming, obtains PP foam material after cooling and shaping.
6. preparation method according to claim 1, it is characterised in that: paper pulp described in step (1) is bleached kraft pulp； The mass content of nano-cellulose is 5-40% in the nanofiber slurries.
7. preparation method according to claim 1, it is characterised in that: pulp dilution described in step (1) is to use distilled water The slurries that mass concentration is 2-7% are diluted to, the temperature of the ball mill is 30-70 DEG C, and the charging rate of slurries is 700- 1000ml/min。
8. preparation method according to claim 1, it is characterised in that: selected compatilizer connects in step (2) for maleic anhydride Branch polypropylene；The mass content of nano-cellulose is 2-10% in the polypropylene/Nano cellulose composite material；Twin-screw squeezes The extruder temperature of machine is 170-240 DEG C out, screw speed 100-200rpm.
9. preparation method according to claim 1, it is characterised in that: in step (3) foamed system be double screw extruder, Single screw extrusion machine or second order tandem extruder；The supercritical fluid is nitrogen or carbon dioxide, and wherein nitrogen is poly- third The 1-3% of alkene weight；Carbon dioxide is the 4-10% of polypropylene weight.
10. preparation method according to claim 9, it is characterised in that: the second order tandem extruder is double by the first rank Screw extruder and second-order single screw extrusion machine are connected in series, and are that polypropylene/Nano cellulose composite material is placed in first It is melted in rank double screw extruder, supercritical fluid is inputted in screw rod by the gas injection port on extruder by metering pump, is obtained Single-phase polymer/gas melt；Then single-phase polymer/gas melt is imported in second-order single screw extrusion machine and is sent out Bubble, obtains PP foam material after cooling and shaping；
In the first rank double screw extruder melting zone temperature be 170-230 DEG C, screw speed 15-25r/min；Described In second order single screw extrusion machine at head temperature be 115-150 DEG C, at head pressure be 8-24MPa, screw speed 10-20r/ min。
CN201811063989.5A 2018-09-12 2018-09-12 A kind of nano-cellulose reinforced polypropylene foamed material and preparation method thereof Pending CN109354764A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110305358A (en) * 2019-07-19 2019-10-08 南京法宁格节能科技股份有限公司 A kind of preparation method of the modification XPS material for rail traffic
CN110343287A (en) * 2019-07-19 2019-10-18 南京法宁格节能科技股份有限公司 A kind of modified foaming polypropylene material and preparation method thereof for automobile instrument panel
CN111548563A (en) * 2020-06-18 2020-08-18 黑龙江省科学院技术物理研究所 Lignin reinforced polypropylene composite material and preparation method thereof
CN111548552A (en) * 2019-02-08 2020-08-18 松下知识产权经营株式会社 Foamed molded article
CN115536938A (en) * 2022-10-19 2022-12-30 上汽通用五菱汽车股份有限公司 Microporous plant fiber composite material and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1861368A (en) * 2006-06-09 2006-11-15 北京化工大学 Method for producing non-cross-linking PP foam material

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1861368A (en) * 2006-06-09 2006-11-15 北京化工大学 Method for producing non-cross-linking PP foam material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LONG WANG ET AL: "Effects of hydrophobic-modified cellulo...tion polypropylene nanocomposite foams", 《COMPOSITES：PART A》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111548552A (en) * 2019-02-08 2020-08-18 松下知识产权经营株式会社 Foamed molded article
CN110305358A (en) * 2019-07-19 2019-10-08 南京法宁格节能科技股份有限公司 A kind of preparation method of the modification XPS material for rail traffic
CN110343287A (en) * 2019-07-19 2019-10-18 南京法宁格节能科技股份有限公司 A kind of modified foaming polypropylene material and preparation method thereof for automobile instrument panel
CN111548563A (en) * 2020-06-18 2020-08-18 黑龙江省科学院技术物理研究所 Lignin reinforced polypropylene composite material and preparation method thereof
CN115536938A (en) * 2022-10-19 2022-12-30 上汽通用五菱汽车股份有限公司 Microporous plant fiber composite material and preparation method thereof
CN115536938B (en) * 2022-10-19 2023-11-21 上汽通用五菱汽车股份有限公司 Microporous plant fiber composite material and preparation method thereof

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Application publication date: 20190219