CN110128693B - Polyolefin foam material and preparation method thereof - Google Patents

Polyolefin foam material and preparation method thereof Download PDF

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CN110128693B
CN110128693B CN201810135220.3A CN201810135220A CN110128693B CN 110128693 B CN110128693 B CN 110128693B CN 201810135220 A CN201810135220 A CN 201810135220A CN 110128693 B CN110128693 B CN 110128693B
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stage screw
screw
parts
weight
temperature
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CN110128693A (en
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庞永艳
郑文革
黄朋科
刘伟
吴明辉
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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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
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/505—Screws
    • 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
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • 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
    • C08J9/0066—Use of inorganic compounding ingredients
    • 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
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92885—Screw or gear
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92904—Die; Nozzle zone
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/06—CO2, N2 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/08—Supercritical fluid
    • 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
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • 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
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • 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
    • 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
    • C08J2323/16—Ethene-propene or ethene-propene-diene copolymers
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—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
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—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
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—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
    • C08J2423/16—Ethene-propene or ethene-propene-diene copolymers

Abstract

The invention relates to a polyolefin foam material and a preparation method thereof, wherein the preparation method comprises the following steps: (a) weighing 80-120 parts by weight of polyolefin, 40-220 parts by weight of inorganic flame retardant and 0-20 parts by weight of synergist, mixing, adding into an extruder, and performing melt extrusion to obtain a premix; (b) adding the premix into a single-screw extruder, and extruding and foaming to obtain a polyolefin foam material; the single-screw extruder comprises an upper-stage screw and a lower-stage screw which are connected in series, the temperature of the upper-stage screw is 140-230 ℃, the temperature of the lower-stage screw is 90-180 ℃, the temperature of an extrusion die is 90-175 ℃, and supercritical carbon dioxide is injected at 1/5-1/3 of the upper-stage screw. The resulting polyolefin foam had a cell density of 104cell/cm3～1012cell/cm3The expansion ratio is 1.05-25. The preparation method improves the dispersion effect of the flame retardant, and the obtained polyolefin foam material has the advantages of uniform cell structure, high foaming rate, controllable orientation degree, excellent flame retardant property and excellent mechanical property.

Description

Polyolefin foam material and preparation method thereof
Technical Field
The invention relates to the technical field of preparation of high polymer materials, in particular to a polyolefin foam material and a preparation method thereof.
Background
Polyolefin foam materials are composed only of carbon and hydrogen elements, are extremely combustible, and are more combustible than unfoamed polyolefin materials, so that flame retardant treatment of the foamed polyolefin materials is particularly important.
Compared with flame-retardant foaming materials such as polyurethane, polystyrene, melamine and the like, the flame-retardant treatment of the polyolefin foaming material is relatively late to start, and the defects of low foaming ratio, poor flame retardant dispersion effect, uneven cellular structure of the foaming material, poor mechanical property, low production phase ratio and the like exist, the technical difficulty is high, and related core technologies are rarely reported at home and abroad at present.
Disclosure of Invention
Therefore, it is necessary to provide a polyolefin foam material and a preparation method thereof, wherein the preparation method is simple to operate and high in production efficiency, and the prepared polyolefin foam material is uniform in cell structure, high in foaming rate, good in flame retardant effect and excellent in mechanical property.
A preparation method of a polyolefin foam material comprises the following steps:
(a) weighing 80-120 parts by weight of polyolefin, 40-220 parts by weight of inorganic flame retardant and 0-20 parts by weight of synergist, mixing, adding into an extruder, and performing melt extrusion to obtain a premix;
(b) Adding the premix into a single-screw extruder, and extruding and foaming to obtain a polyolefin foam material; the single-screw extruder comprises an upper-stage screw and a lower-stage screw which are connected in series, the temperature of the upper-stage screw is 140-230 ℃, the temperature of the lower-stage screw is 90-180 ℃, the temperature of an extrusion die is 90-175 ℃, and supercritical carbon dioxide is injected at 1/5-1/3 parts of the upper-stage screw.
The preparation method of the polyolefin foam material has the following advantages:
firstly, the preparation method integrates processing and foaming, can continuously and efficiently prepare the foaming material and meet the increasing requirements of the polyolefin foaming material. And the single-screw extruder comprises an upper-stage screw and a lower-stage screw which are connected in series, the upper-stage screw mainly plays a role in plasticizing and melting the polymer and primarily mixing the polymer melt and the supercritical carbon dioxide, and the lower-stage screw mainly plays a role in fully mixing the polymer melt and the supercritical carbon dioxide and facilitating the foaming of the polymer in an extrusion die through temperature control. And thirdly, the supercritical carbon dioxide is used as a foaming agent, so that the foaming agent is green and environment-friendly, has low price, and has strong plasticizing capacity and diffusion capacity. The plasticizing and mass transfer effects of the supercritical carbon dioxide can improve the dispersion of the flame retardant, and further improve the cellular structure of the foaming material. Therefore, the preparation method effectively solves the problems that the inorganic flame retardant is easy to agglomerate and is difficult to process when the addition amount is large, improves the dispersion effect of the flame retardant, and improves the flame retardant efficiency of the flame retardant.
The invention also provides a polyolefin foam material prepared by the preparation method, and the polyolefin foam material has the cell density of 104cell/cm3～1012cell/cm3The expansion ratio is 1.05-25.
The polyolefin foam material prepared by the preparation method has controllable density, uniform cell structure and high foaming multiplying power, and finally can obtain excellent flame retardant property and mechanical property.
Drawings
FIG. 1 is a scanning electron micrograph of a cell structure of a polyolefin foam prepared in example 1 of the present invention;
FIG. 2 is a photograph showing mechanical properties of the polyolefin foam prepared in example 1 of the present invention.
Detailed Description
The polyolefin foam material and the preparation method thereof provided by the present invention will be further explained below.
The invention provides a preparation method of a polyolefin foam material, which comprises the following steps:
(a) weighing 80-120 parts by weight of polyolefin, 40-220 parts by weight of inorganic flame retardant and 0-20 parts by weight of synergist, mixing, adding into an extruder, and performing melt extrusion to obtain a premix;
(b) adding the premix into a single-screw extruder, and extruding and foaming to obtain a polyolefin foam material; the single-screw extruder comprises an upper-stage screw and a lower-stage screw which are connected in series, the temperature of the upper-stage screw is 140-230 ℃, the temperature of the lower-stage screw is 90-180 ℃, the temperature of an extrusion die is 90-175 ℃, and supercritical carbon dioxide is injected at 1/5-1/3 parts of the upper-stage screw.
In the step (a), the polyolefin is at least one of polyethylene, polypropylene, ethylene-propylene rubber and ethylene-octene copolymer. The inorganic flame retardant is at least one of magnesium hydroxide, aluminum hydroxide, expanded graphite, red phosphorus, zinc oxide, titanium oxide, aluminum oxide, silicon dioxide, zinc borate, zinc stannate, silicate, ammonium salt, phosphate and hypophosphite. The synergist is at least one of antimony trioxide, montmorillonite, calcium carbonate, potassium carbonate, magnesium carbonate, dolomite, magnesite, hydrotalcite, tremolite and kaolin. The total mass of the inorganic flame retardant and the synergist accounts for 40-70% of the mass of the premix.
In the step (a), the extruder is a single-screw extruder or a double-screw extruder, and the temperature of the single-screw extruder or the double-screw extruder is 140-230 ℃. Preferably, the polyolefin, the inorganic flame retardant and the synergist are uniformly mixed by a high-speed mixer, and then added into a single-screw extruder or a double-screw extruder to be melt-extruded to obtain a premix.
The dosage of the supercritical carbon dioxide in the step (b) is 0.5-12% of the mass of the premix. The injection pressure of the supercritical carbon dioxide is 7 MPa-25 MPa.
The pressure of the single-screw extruder in the step (b) is 7MPa to 30 MPa.
The temperature of the lower-stage screw in the step (b) is lower than that of the upper-stage screw, the difference is T, and T is more than or equal to 20 ℃ and less than or equal to 80 ℃.
Because the melt strength is too high to be beneficial to the growth of the foam holes, and the melt strength is too low to be beneficial to the fixation of the foam holes, the single-screw extruder adopted by the invention comprises an upper-stage screw and a lower-stage screw which are connected in series. The upper-stage screw mainly plays a role in plasticizing and melting a polymer and primarily mixing a polymer melt and supercritical carbon dioxide, and the lower-stage screw mainly plays a role in fully mixing the polymer melt and the supercritical carbon dioxide and facilitating foaming of the polymer in an extrusion die through temperature control. The temperature of the lower-stage screw is lower than that of the upper-stage screw, the difference is T, and T is more than or equal to 20 ℃ and less than or equal to 80 ℃. Thus ensuring that the supercritical carbon dioxide can be dissolved in the polymer melt to form a uniform system, thereby forming a uniform cell structure; meanwhile, the strength of the polymer melt is ensured to be more suitable for foaming, and a better cell structure and a larger expansion ratio are formed.
In order to obtain the polyolefin foaming material with more uniform foam cells, preferably, supercritical carbon dioxide is injected at 1/4 of the upper-stage screw, the dosage of the supercritical carbon dioxide is 1-10% of the mass of the premix, the injection pressure of the supercritical carbon dioxide is 10 MPa-20 MPa, the temperature of the upper-stage screw is 140-200 ℃, the temperature of the lower-stage screw is 100-175 ℃, the difference between the temperature of the lower-stage screw and the temperature of the upper-stage screw is T, T is more than or equal to 20 ℃ and less than or equal to 50 ℃, and the pressure of the single-screw extruder is 8 MPa-18 MPa.
After the step (b) of extrusion foaming to obtain the polyolefin foam material, the method also comprises a step (c): and (3) drawing and collecting the polyolefin foaming material by using a drawing device, wherein the drawing ratio of the drawing device is 0-80, and the drawing speed is 0.1-3.0 m/s. The traction device is equipment with a traction function, and comprises but is not limited to casting equipment, calendaring equipment, a granulator and spinning equipment. By adjusting the stretching speed of the traction device, the orientation of the polymer molecular chain can be adjusted, so that the orientation degree of the polyolefin foam material can be adjusted, and the mechanical property of the polyolefin foam material can be improved.
Considering that the strength of the polyolefin foam material is low when the draft ratio is 0, the draft ratio is preferably 1 to 30.
The preparation method of the polyolefin foam material integrates processing and foaming, can continuously and efficiently prepare the foam material, has the advantages of environmental protection, low energy consumption, high production efficiency and the like, and meets the increasing requirements of the polyolefin foam material.
In the processing process of the preparation method, the single-screw extruder comprises an upper-stage screw and a lower-stage screw which are connected in series, the upper-stage screw mainly plays roles in plasticizing and melting the polymer and primarily mixing the polymer melt and the supercritical carbon dioxide, and the lower-stage screw mainly plays roles in fully mixing the polymer melt and the supercritical carbon dioxide and facilitating the foaming of the polymer in an extrusion die through temperature control.
The preparation method adopts supercritical carbon dioxide as a foaming agent, and the foaming agent is green and environment-friendly, has low price, and has strong plasticizing capacity and diffusion capacity. The plasticizing and mass transfer effects of the supercritical carbon dioxide can improve the dispersion of the flame retardant, and further improve the cellular structure of the foaming material.
Therefore, the preparation method effectively solves the problems that the inorganic flame retardant is easy to agglomerate and is difficult to process when the addition amount is large, improves the dispersion effect of the flame retardant, and improves the flame retardant efficiency of the flame retardant.
The invention also provides a polyolefin foam material prepared by the preparation method, and the polyolefin foam material has the cell density of 104cell/cm3～1012cell/cm3The expansion ratio is 1.05-25.
The polyolefin foam material obtained by the preparation method comprises at least two of polyolefin, inorganic flame retardant and synergist, and the inorganic flame retardant and the synergist are uniformly dispersed in the polyolefin foam material. The obtained polyolefin foam material has controllable density, uniform cell structure, high foaming multiplying power and controllable orientation degree, and can finally obtain excellent flame retardant property and mechanical property. Therefore, the polyolefin foam material can be widely applied to the fields of automobiles, packaging, electronic products, building materials and the like.
Hereinafter, the polyolefin and the preparation method thereof will be further described by the following specific examples.
Example 1:
80 parts by weight of polypropylene, 100 parts by weight of magnesium hydroxide and 10 parts by weight of calcium carbonate are weighed.
The raw materials are mixed by a high-speed mixer and then added into a double-screw extruder, and the mixture is melted and extruded at 200 ℃ to obtain the premix.
The premix is added to a single screw extruder comprising an upper stage screw and a lower stage screw in series. Wherein the temperature of the upper-stage screw of the single-screw extruder is set to be 200 ℃, the temperature of the lower-stage screw is set to be 167 ℃, and the temperature of the extrusion die is set to be 165 ℃. At 1/4 of the upper stage screw, 6 parts by weight of supercritical carbon dioxide was injected under a pressure of 17 MPa. And (3) maintaining the pressure in the single-screw extruder at 10MPa, extruding and foaming, and stretching by adopting a casting device to obtain the polypropylene foam material, wherein the stretching speed of the casting device is 1.4m/s, and the draft ratio is 3.1.
Example 2:
80 parts by weight of polypropylene, 20 parts by weight of polyethylene and 160 parts by weight of aluminum hydroxide were weighed.
The raw materials are mixed by a high-speed mixer and then added into a single-screw extruder, and the mixture is melted and extruded at 200 ℃ to obtain a premix.
The premix is added to a single screw extruder comprising an upper stage screw and a lower stage screw in series. Wherein the temperature of the upper-stage screw of the single-screw extruder is set to be 200 ℃, the temperature of the lower-stage screw is set to be 172 ℃, and the temperature of the extrusion die is 172 ℃. 8 parts by weight of supercritical carbon dioxide was injected into 1/4 of the upper-stage screw at an injection pressure of 20 MPa. The pressure in the single screw extruder is maintained at 8.0MPa, and the polypropylene/polyethylene composite foaming material can be obtained by extrusion foaming and stretching by adopting a calendering device. Wherein the drawing speed of the calendering equipment is 0.5m/s and the draw ratio is 10.
Example 3:
100 parts by weight of polyethylene, 120 parts by weight of magnesium hydroxide and 20 parts by weight of aluminum hydroxide were weighed.
The raw materials are mixed by a high-speed mixer and then added into a double-screw extruder, and the mixture is melted and extruded at 190 ℃ to obtain the premix.
The premix is added to a single screw extruder comprising an upper stage screw and a lower stage screw in series. Wherein the temperature of the upper-stage screw of the single-screw extruder is set to be 180 ℃, the temperature of the lower-stage screw is set to be 120 ℃, and the temperature of the extrusion die is set to be 115 ℃. At 1/4 of the upper stage screw, 5 parts by weight of supercritical carbon dioxide was injected under an injection pressure of 18 MPa. And (3) maintaining the pressure in the single-screw extruder at 11MPa, extruding and foaming, and stretching by adopting spinning equipment to obtain the polyethylene foam material. Wherein the drawing speed of the spinning equipment is 3.0m/s and the draw ratio is 30.
Example 4:
100 parts by weight of polypropylene, 20 parts by weight of ethylene propylene rubber and 180 parts by weight of magnesium hydroxide are weighed.
The raw materials are mixed by a high-speed mixer and then added into a single-screw extruder, and the mixture is melted and extruded at 200 ℃ to obtain a premix.
The premix is added to a single screw extruder comprising an upper stage screw and a lower stage screw in series. Wherein the temperature of the upper-stage screw of the single-screw extruder is set to be 200 ℃, the temperature of the lower-stage screw is set to be 165 ℃, and the temperature of the extrusion die is 162 ℃. At 1/4 of the upper stage screw, 3 parts by weight of supercritical carbon dioxide was injected, and the injection pressure was set to 20 MPa. And (3) maintaining the pressure in the single-screw extruder at 16MPa, extruding and foaming, and stretching by adopting a casting device to obtain the polypropylene/ethylene propylene rubber composite flame-retardant foaming material. Wherein the drawing speed of the casting apparatus was 0.1m/s and the draft ratio was 0.5.
Example 5:
100 parts by weight of polypropylene, 120 parts by weight of magnesium hydroxide and 5 parts by weight of kaolin are weighed.
The raw materials are mixed by a high-speed mixer and then added into a double-screw extruder, and the mixture is melted and extruded at 200 ℃ to obtain the premix.
The premix is added to a single screw extruder comprising an upper stage screw and a lower stage screw in series. Wherein the temperature of the upper-stage screw of the single-screw extruder is set to be 200 ℃, the temperature of the lower-stage screw is set to be 172 ℃, and the temperature of the extrusion die is 170 ℃. At 1/4 of the upper stage screw, 4 parts by weight of supercritical carbon dioxide was injected, and the injection pressure was set to 15 MPa. And (3) maintaining the pressure in the single-screw extruder at 10MPa, extruding and foaming, and stretching by adopting a calendering device to obtain the polypropylene foam material. Wherein the drawing speed of the calendering equipment is 1.8m/s and the draft ratio is 15.
Example 6:
weighing 90 parts by weight of polypropylene, 30 parts by weight of polyethylene and 190 parts by weight of magnesium hydroxide.
The raw materials are mixed by a high-speed mixer and then added into a single-screw extruder, and the mixture is melted and extruded at 200 ℃ to obtain a premix.
The premix is added to a single screw extruder comprising an upper stage screw and a lower stage screw in series. Wherein the temperature of the upper-stage screw of the single-screw extruder is set to be 200 ℃, the temperature of the lower-stage screw is set to be 175 ℃, and the temperature of the extrusion die is set to be 175 ℃. 2 parts by weight of supercritical carbon dioxide was injected into 1/4 of the upper-stage screw at an injection pressure of 20 MPa. The pressure in the single-screw extruder is maintained at 16MPa, the polypropylene/polyethylene composite flame-retardant foam material is extruded and foamed, and the polypropylene/polyethylene composite flame-retardant foam material is obtained by adopting tape casting equipment for stretching. Wherein the drawing speed of the casting apparatus is 0.6m/s and the draft ratio is 1.
Example 7:
100 parts by weight of ethylene propylene rubber and 200 parts by weight of magnesium hydroxide are weighed.
The raw materials are mixed by a high-speed mixer and then added into a double-screw extruder, and the mixture is melted and extruded at 160 ℃ to obtain the premix.
The premix is added to a single screw extruder comprising an upper stage screw and a lower stage screw in series. Wherein the temperature of the upper-stage screw of the single-screw extruder is 150 ℃, the temperature of the lower-stage screw is 90 ℃, and the temperature of the extrusion die is 90 ℃. 2 parts by weight of supercritical carbon dioxide was injected into 1/4 of the upper-stage screw at an injection pressure of 18 MPa. And (3) maintaining the pressure in the single-screw extruder at 11MPa, extruding and foaming, and stretching by adopting a casting device to obtain the ethylene propylene rubber flame-retardant foaming material. Wherein the casting apparatus has a drawing speed of 1.8m/s and a draft ratio of 20.
Example 8:
100 parts by weight of polyethylene, 190 parts by weight of magnesium hydroxide and 5 parts by weight of kaolin are weighed.
The raw materials are mixed by a high-speed mixer and then added into a single-screw extruder, and the mixture is melted and extruded at 170 ℃ to obtain a premix.
The premix is added to a single screw extruder comprising an upper stage screw and a lower stage screw in series. Wherein the temperature of the upper-stage screw of the single-screw extruder is 170 ℃, the temperature of the lower-stage screw is 140 ℃, and the temperature of the extrusion die is 140 ℃. At 1/4 of the upper stage screw, 7 parts by weight of supercritical carbon dioxide was injected under a pressure of 17 MPa. And (3) maintaining the pressure in the single-screw extruder at 10MPa, extruding and foaming, and stretching by adopting a casting device to obtain the polyethylene flame-retardant foaming material. Wherein the casting apparatus has a drawing speed of 2.0m/s and a draft ratio of 50.
Example 9:
weighing 90 parts by weight of ethylene-octene copolymer, 40 parts by weight of zinc borate and 20 parts by weight of antimony trioxide.
The raw materials are mixed by a high-speed mixer and then added into a double-screw extruder, and the mixture is melted and extruded at 140 ℃ to obtain the premix.
The premix is added to a single screw extruder comprising an upper stage screw and a lower stage screw in series. Wherein the temperature of the upper-stage screw of the single-screw extruder is set as 140 ℃, the temperature of the lower-stage screw is set as 100 ℃, and the temperature of the extrusion die is set as 100 ℃. At 1/3 of the upper stage screw, 0.5 part by weight of supercritical carbon dioxide was injected at an injection pressure of 7 MPa. And (3) maintaining the pressure in the single-screw extruder at 7MPa, extruding and foaming, and stretching by adopting a casting device to obtain the polypropylene foam material. Wherein the casting apparatus has a drawing speed of 2.5m/s and a draft ratio of 80.
Example 10:
100 parts of polypropylene, 110 parts of aluminum hydroxide, 110 parts of expanded graphite and 10 parts of montmorillonite are weighed.
The raw materials are mixed by a high-speed mixer and then added into a double-screw extruder, and the mixture is melted and extruded at 230 ℃ to obtain the premix.
The premix is added to a single screw extruder comprising an upper stage screw and a lower stage screw in series. Wherein the temperature of the upper-stage screw of the single-screw extruder is 230 ℃, the temperature of the lower-stage screw is 175 ℃, and the temperature of the extrusion die is 175 ℃.2 parts by weight of supercritical carbon dioxide was injected into 1/5 of the upper-stage screw at an injection pressure of 10 MPa. And (3) maintaining the pressure in the single-screw extruder at 18MPa, extruding and foaming, and stretching by adopting a casting device to obtain the polypropylene foam material. Wherein the drawing speed of the casting apparatus was 0.2m/s and the draft ratio was 2.1.
Example 11:
weighing 80 parts by weight of polypropylene, 30 parts by weight of ethylene propylene rubber, 50 parts by weight of magnesium hydroxide, 50 parts by weight of zinc stannate, 5 parts by weight of hydrotalcite and 5 parts by weight of dolomite.
The raw materials are mixed by a high-speed mixer and then added into a double-screw extruder, and the mixture is melted and extruded at 220 ℃ to obtain a premix.
The premix is added to a single screw extruder comprising an upper stage screw and a lower stage screw in series. Wherein the temperature of the upper-stage screw of the single-screw extruder is set to be 200 ℃, the temperature of the lower-stage screw is set to be 180 ℃, and the temperature of the extrusion die is 175 ℃. 8 parts by weight of supercritical carbon dioxide was injected into 1/3 of the upper-stage screw, and the injection pressure was set to 25 MPa. And (3) maintaining the pressure in the single-screw extruder at 30MPa, extruding and foaming, and stretching by adopting a casting device to obtain the polypropylene foam material. Wherein the drawing speed of the casting apparatus was 1.2m/s and the draft ratio was 28.
Example 12:
80 parts by weight of polypropylene, 20 parts by weight of an ethylene-octene copolymer, 100 parts by weight of titanium oxide, 40 parts by weight of phosphate and 10 parts by weight of potassium carbonate were weighed.
The raw materials are mixed by a high-speed mixer and then added into a double-screw extruder, and the mixture is melted and extruded at 200 ℃ to obtain the premix.
The premix is added to a single screw extruder comprising an upper stage screw and a lower stage screw in series. Wherein the temperature of the upper-stage screw of the single-screw extruder is set to be 200 ℃, the temperature of the lower-stage screw is set to be 160 ℃, and the temperature of the extrusion die is 160 ℃. At 1/4 of the upper stage screw, 12 parts by weight of supercritical carbon dioxide was injected, and the injection pressure was set to 15 MPa. And (3) maintaining the pressure in the single-screw extruder at 15MPa, and extruding and foaming to obtain the polypropylene foaming material.
Example 13:
about 80 parts by weight of polypropylene, 100 parts by weight of magnesium hydroxide and 10 parts by weight of calcium carbonate were weighed.
The raw materials are mixed by a high-speed mixer and then added into a double-screw extruder, and the mixture is melted and extruded at 200 ℃ to obtain the premix.
The premix is added to a single screw extruder comprising an upper stage screw and a lower stage screw in series. Wherein the temperature of the upper-stage screw of the single-screw extruder is set to be 200 ℃, the temperature of the lower-stage screw is set to be 167 ℃, and the temperature of the extrusion die is set to be 165 ℃. At 1/4 of the upper stage screw, 6 parts by weight of supercritical carbon dioxide was injected under a pressure of 17 MPa. The pressure in the single-screw extruder is maintained at 10MPa, and the polypropylene foaming material is obtained by extrusion foaming.
Comparative example 1:
95 parts by weight of polypropylene and 5 parts by weight of calcium carbonate are weighed.
The raw materials are mixed by a high-speed mixer and then added into a double-screw extruder, and the mixture is melted and extruded at 200 ℃ to obtain the premix.
The premix is added to a single screw extruder comprising an upper stage screw and a lower stage screw in series. Wherein the temperature of the upper stage screw of the single screw extruder is set to 200 ℃ and the temperature of the lower stage screw is set to 170 ℃. At 1/4 of the upper stage screw, 4 parts by weight of supercritical carbon dioxide was injected, and the injection pressure was set to 15 MPa. The pressure in the single-screw extruder is maintained at 10MPa, and the polypropylene foaming material is obtained by extrusion foaming.
Comparative example 2:
100 parts by weight of polypropylene are weighed.
The raw materials are mixed by a high-speed mixer and then added into a double-screw extruder, and the mixture is melted and extruded at 200 ℃ to obtain the premix.
The premix is added to a single screw extruder comprising an upper stage screw and a lower stage screw in series. Wherein the temperature of the upper stage screw of the single screw extruder is set to 200 ℃ and the temperature of the lower stage screw is set to 170 ℃. At 1/4 of the upper stage screw, 4 parts by weight of supercritical carbon dioxide was injected, and the injection pressure was set to 15 MPa. And (3) maintaining the pressure in the single-screw extruder at 10MPa, extruding and foaming, and stretching by adopting a casting device to obtain the polypropylene foam material. Wherein the casting apparatus has a drawing speed of 3.6m/s and a draft ratio of 5.
The polyolefin foams obtained in examples 1 to 13 and comparative examples 1 to 2 were characterized in flame retardancy and mechanical properties, and the results are shown in Table 1. Wherein, the flame retardant property characterization adopts a VOUCH 5801A oxygen index tester and a VOUCH 5410 foam horizontal combustion tester.
TABLE 1
Figure BDA0001576067100000111
Figure BDA0001576067100000121
As can be seen from Table 1, the polyolefin foams which are not flame-retardant and modified in comparative example 1 and comparative example 2 belong to flammable samples, and the polyolefin foams which do not pass through the traction device in comparative example 1, example 12 and example 13 have poor mechanical properties.
The flame-retardant polyolefin foam materials obtained in the above examples 1 to 11 have controllable density, uniform cell structure, high foaming ratio, higher oxygen index, foam level combustion grade and specific tensile strength, and excellent flame retardant property and mechanical property.
The polypropylene foaming material obtained in the example 1 is subjected to microstructure and mechanical property characterization, wherein the microstructure distribution characterization adopts ZEISS scanningThe electron microscope and the mechanical property characterization adopt an INSTRON universal tester, and the results are shown in figures 1 and 2. As can be seen from fig. 1, the polypropylene foam has a uniform cell structure. As can be seen from FIG. 2, the density was only 0.22g/cm3The polypropylene foaming material can lift objects which are thousands of times heavier than the polypropylene foaming material, and shows that the polypropylene foaming material has excellent mechanical properties.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (6)

1. The preparation method of the polyolefin foam material is characterized by comprising the following steps:
(a) weighing 80-120 parts by weight of polyolefin, 40-220 parts by weight of inorganic flame retardant and 0-20 parts by weight of synergist, mixing, adding into an extruder, and performing melt extrusion to obtain a premix;
(b) adding the premix into a single-screw extruder, and extruding and foaming to obtain a polyolefin foam material; the single-screw extruder comprises an upper-stage screw and a lower-stage screw which are connected in series, the temperature of the upper-stage screw is 140-230 ℃, the temperature of the lower-stage screw is 90-180 ℃, the temperature of the lower-stage screw is lower than that of the upper-stage screw, the difference is T, T is more than or equal to 20 ℃ and less than or equal to 80 ℃, the temperature of an extrusion die is 90-175 ℃, supercritical carbon dioxide is injected at 1/5-1/3 of the upper-stage screw, the injection pressure of the supercritical carbon dioxide is 7-25 MPa, and the using amount of the supercritical carbon dioxide is 0.5-12% of the mass of the premix;
(c) and (3) drawing and collecting the polyolefin foaming material by using a drawing device, wherein the drawing ratio of the drawing device is 0-80, and the drawing speed is 0.1-3.0 m/s.
2. The method for preparing polyolefin foam according to claim 1, wherein the polyolefin in step (a) is at least one of polyethylene, polypropylene, ethylene-propylene rubber, and ethylene-octene copolymer.
3. The method for preparing polyolefin foam according to claim 1, wherein the inorganic flame retardant in step (a) is at least one of magnesium hydroxide, aluminum hydroxide, expanded graphite, red phosphorus, zinc oxide, titanium oxide, aluminum oxide, silica, zinc borate, zinc stannate, silicate, ammonium salt, phosphate, hypophosphite.
4. The method for preparing polyolefin foam material according to claim 1, wherein the synergist in step (a) is at least one of antimony trioxide, montmorillonite, calcium carbonate, potassium carbonate, magnesium carbonate, dolomite, magnesite, hydrotalcite, tremolite and kaolin.
5. The method for preparing polyolefin foam material according to claim 1, wherein the total mass of the inorganic flame retardant and the synergist in step (a) is 40-70% of the mass of the premix.
6. The polyolefin foam material prepared by the preparation method of any one of claims 1 to 5, wherein the cell density of the polyolefin foam material is 104cell/cm3~1012cell/cm3The expansion ratio is 1.05-25.
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