CN111087705B - Foaming composition, foaming material, preparation method and application thereof - Google Patents

Foaming composition, foaming material, preparation method and application thereof Download PDF

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CN111087705B
CN111087705B CN201911374687.4A CN201911374687A CN111087705B CN 111087705 B CN111087705 B CN 111087705B CN 201911374687 A CN201911374687 A CN 201911374687A CN 111087705 B CN111087705 B CN 111087705B
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foaming
polyethylene
antioxidant
polypropylene
mixed
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CN111087705A (en
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范宇
王炳德
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Shenzhen Hantang Materials Co ltd
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Shenzhen Hantang 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
    • C08J9/06—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 chemical blowing agent
    • C08J9/10—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 chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
    • 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
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • 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
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B29C48/41—Intermeshing counter-rotating 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
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/505—Screws
    • B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
    • 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
    • C08J9/0014—Use of organic additives
    • C08J9/0028—Use of organic additives containing nitrogen
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/10—Polymers of propylene
    • B29K2023/12—PP, i.e. polypropylene
    • 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
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • 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
    • C08J2323/14—Copolymers of propene
    • 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
    • C08J2423/10—Homopolymers or copolymers of propene
    • C08J2423/12—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
    • 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
    • C08J2423/10—Homopolymers or copolymers of propene
    • C08J2423/14—Copolymers of propene
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    • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers

Abstract

The invention provides a foaming composition, a foaming material prepared from the foaming composition, and a product containing the foaming material. The foaming composition comprises the following components in percentage by mass: 21-93.6% of propylene polymer, 5-35% of polyethylene, 0-20% of elastomer, 1-20% of foaming agent, 0.1-1% of nucleating agent, 0.1-5% of crosslinking assistant and 0.2-3% of antioxidant; the crosslinking assistant is at least one selected from aniline and derivatives thereof, triazole and derivatives thereof, a combination of aniline and derivatives thereof and acrylate compounds, and a combination of triazole and derivatives thereof and acrylate compounds. The invention also provides a preparation method of the foaming material. The problems that the foaming agent is easy to decompose, the equipment requirement precision is high, the odor and VOC of the foaming material prepared by the salt bath foaming process exceed the standard and the like in the existing homodromous double-screw side feeding, extruding, radiating, crosslinking and foaming process can be solved.

Description

Foaming composition, foaming material, preparation method and application thereof
Technical Field
The invention relates to the technical field of foaming materials, in particular to a foaming composition, a foaming material prepared from the foaming composition and a product containing the foaming material.
Background
Compared with the currently commonly used polystyrene and polyethylene foam materials, the foamed polypropylene has remarkable advantages, such as more excellent mechanical property, higher temperature resistance, heat insulation and heat preservation, better elastic recovery, and the like, and is a green environment-friendly material which can be degraded in the natural world, and the like.
The conventional polypropylene foam preparation methods mainly comprise the following four methods: supercritical gas extrusion foaming, chemical foaming agent extrusion foaming, intermittent mould pressing foaming, and equidirectional double-screw side feeding extrusion radiation crosslinking foaming.
Extruding and foaming by supercritical gas, mixing polypropylene, a nucleating agent, an elastomer and gas (carbon dioxide, nitrogen, butane and fluorine-containing alkane, combination) at high pressure, and relieving pressure by a mould to prepare a polypropylene foaming material which is often applied to the industries of cups and packages; extruding and foaming the chemical foaming agent, namely extruding the polypropylene, the elastomer, the nucleating agent, the chemical foaming agent and the crosslinking agent by a screw rod, crosslinking, decomposing to form a high-pressure mixture, and releasing the pressure of the paper cup polypropylene foamed sheet by a mould, so that the paper cup polypropylene foamed sheet is applied to the industries of structural parts such as luggage cases, billboards and the like; preparing polypropylene by intermittent die pressing foaming, wherein polypropylene and a blending modification thereof are mainly extruded and molded, cut into pieces or particles, put into a high-temperature high-pressure kettle body, insulated and inflated at high pressure to form a supercritical mixture, and then decompressed to prepare foamed polypropylene sheets or particles; the polypropylene foaming material is prepared by extruding polypropylene, an elastomer, a chemical foaming agent, a cross-linking agent and a nucleating agent through sectional feeding and extruding for preparing a plastic mixed sheet, then performing radiation cross-linking, performing high-temperature foaming through a salt bath, and cleaning the surface of foam cotton.
However, the above preparation methods all have certain defects: the polypropylene foam material prepared by supercritical gas extrusion foaming has the advantages of nonuniform bubble, crisp property and high requirement on the strength of the polypropylene melt, so the polypropylene foam material is rarely applied commercially; chemical foaming agentThe polypropylene foam material prepared by extrusion foaming has thick and large foam holes and high density, and the process limit can only reach 250kg/m 3 The density and the brittleness of the composite material are mainly used as structural materials; the polypropylene foaming material prepared by intermittent mould pressing foaming has fine foam cavity and good impact resistance, but only can be used for preparing very thick sheets, depends on die cutting equipment, has high requirements on high temperature resistance and high pressure of the equipment, has large investment and high cost, and limits the commercial application of the equipment; the irradiation cross-linking foaming preparation polypropylene material is extruded in feeding of syntropy twin-screw side, the process control degree of difficulty is big, syntropy twin-screw internal shear is high, the foamer easily decomposes, liquid, powder side feed is high to feeding equipment precision, the input is big, especially salt bath foaming process, the salt substance washs, it all can lead to environmental pollution all to retrieve etc., simultaneously foaming material invades completely in the salt bath, pyrolysis micromolecule very easily remains in the cotton material of bubble, smell and VOC exceed standard, can not satisfy the environmental protection, the increasingly high auto industry requirement of comfort level.
Therefore, it is necessary to develop a method for preparing polypropylene foam which overcomes the above-mentioned drawbacks.
Disclosure of Invention
The present application was made by the inventors based on the following problems and recognitions:
the existing radiation crosslinking foaming process adopts the co-rotating twin-screw side feeding to extrude and foam, the process control difficulty is large, the co-rotating twin-screw internal shearing is high, the foaming agent is easy to decompose, and the liquid and powder side feeding has high precision and large investment on feeding equipment. If a raw material processing system which is the same as that of the co-rotating twin screws is adopted, the co-rotating twin screws are directly changed into the counter-rotating parallel twin screws, so that the crosslinking is uneven, the foam holes are thick, and the crosslinking degree is low. Accordingly, the present inventors have conducted extensive studies on processing materials and finally have solved the above-mentioned problems by selecting an appropriate crosslinking assistant, thereby completing the present invention.
Specifically, the invention provides the following technical scheme:
in one aspect, the present invention provides a foaming composition, which comprises, by mass: 21-93.6% of propylene polymer, 5-35% of polyethylene, 0-20% of elastomer, 1-20% of foaming agent, 0.1-1% of nucleating agent, 0.1-5% of crosslinking assistant and 0.2-3% of antioxidant; the crosslinking assistant is at least one selected from aniline and derivatives thereof, triazole and derivatives thereof, a combination of aniline and derivatives thereof and acrylate compounds, and a combination of triazole and derivatives thereof and acrylate compounds.
Preferably, the propylene polymer has a melt index of 0.2 to 5g/10min and is selected from at least one of isotactic polypropylene, syndiotactic polypropylene, trackless polypropylene, block polypropylene, impact modified polypropylene, polypropylene-ethylene copolymer, polypropylene-butene copolymer, MAH-g-polypropylene-ethylene copolymer, MAH-g-polypropylene-butene copolymer, metallocene polypropylene-ethylene copolymer, metallocene polypropylene-butene copolymer.
Preferably, the polyethylene is selected from at least one of low density polyethylene, linear low density polyethylene, metallocene polyethylene, high density polyethylene;
the elastomer is a polyolefin elastomer or a rubber elastomer.
Preferably, the polyolefin elastomer is at least one selected from the group consisting of a copolymer of ethylene and propylene, a copolymer of ethylene and octene, and a copolymer of ethylene and vinyl acetate.
Preferably, the rubber elastomer is at least one selected from natural rubber, ethylene propylene rubber, styrene butadiene rubber and silicone rubber.
Preferably, the foaming agent is at least one selected from the group consisting of azodicarbonamide, diisopropyl azodicarboxylate, dinitrosopentamethyl tetramine, oxalyl hydrazine, trinitrotrimethylene triamine, p-toluenesulfonyl azide, 4-phenyltetrazole, and biurea.
Preferably, the nucleating agent is selected from at least one of kaolin, montmorillonite, clay, talc, calcium carbonate, mica, magnesium oxide, zinc oxide, alumina, carbon black, silica, glass, quartz, or titanium oxide.
Preferably, the antioxidant includes at least one of 2, 6-di-tert-butyl-4-ethylphenol, 2, 6-di-tert-butyl-4-methylphenol, 2, 6-di-tert-butyl- α -dimethylamino-p-cresol, 2,4, 6-tri-tert-butylphenol, ditetradecylthiodipropionate, antioxidant 1010, antioxidant CA, antioxidant B215, antioxidant B225, antioxidant 168, antioxidant 405, dilaurylthiodipropionate (DLTP), dioctadecylthiodipropionate (DSTP).
Preferably, the aniline and the derivative thereof are selected from at least one of aniline, acetanilide, acetophenone, p-toluidine and diphenylamine; the triazole and the derivative thereof are selected from at least one of 1,2, 4-triazole, methyl benzotriazole, voriconazole and tedizolid; the acrylate is at least one of ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate (TMPTMA), tetramethylolmethane triacrylate, tripropyl isocyanurate and trimethylolpropane triacrylate.
In another aspect, the present invention provides a method for preparing a foamed material using a foaming composition, comprising:
s1, mixing an elastomer, a foaming agent, a crosslinking assistant, a nucleating agent and an antioxidant through an internal mixer, and granulating through a single-screw extruder to obtain a first mixed master batch;
optionally S2, mixing the antioxidant and the crosslinking aid with the propylene polymer and the polyethylene, and granulating by using a double-screw extruder to obtain second mixed master batches;
s3, extruding the first mixed master batch, the optional second mixed master batch, the propylene polymer and the optional polyethylene into a sheet by using a counter-rotating parallel double-screw extruder to obtain a foamed substrate;
s4, carrying out radiation crosslinking on the foaming substrate to obtain a foaming master slice;
and S5, placing the foaming master slice in a foaming furnace for foaming to obtain the foaming material.
Preferably, the length-diameter ratio of the screws of the counter-rotating parallel twin screws is 18-45:1, the diameter of the screw is 30-150mm.
Preferably, in S1, the first mixed master batch is selected from any one of a first mixed master batch a, a first mixed master batch B, and a first mixed master batch C;
wherein, by mass percentage, the first mixed masterbatch A comprises: 0.2-5% of nucleating agent, 0.2-5% of antioxidant, 0.2-6% of crosslinking assistant, 4-10% of foaming agent and 74-95.4% of polyethylene;
the first mixed master batch B comprises the following components in percentage by mass: 0.2-5% of nucleating agent, 0.2-5% of antioxidant, 0.2-6% of crosslinking assistant, 10-20% of foaming agent, 14-69.4% of polyethylene and 20-50% of elastomer;
the first mixed master batch C comprises the following components in percentage by mass: 0.2-5% of nucleating agent, 0.2-5% of antioxidant, 0.2-6% of crosslinking assistant, 20-40% of foaming agent, and polyethylene: 34-79.4 percent of elastomer and 0-10 percent of elastomer.
The composition of the first mixed masterbatch can be selected according to the specific application of the prepared foaming material.
And mixing the first mixed master batch A, the first mixed master batch B and the first mixed master batch C in an internal mixer, and then granulating by using a single-screw extruder.
Preferably, in S2, the second mixed mother particle includes, by mass: 0.3-8% of antioxidant, 0.3-8% of crosslinking assistant, 50-80% of polypropylene and 4-49.4% of polyethylene.
The raw materials of the second mixed masterbatch can be mixed by using a high-speed mixer or a common mixer, and then granulated by using a double-screw extruder.
Preferably, in the S3, by mass, the first mixed mother particle is 5 to 50%, the second mixed mother particle is 0 to 20%, the polyethylene is 0 to 20%, and the polypropylene is 10 to 94.5%.
The selection of each component in each mixed master batch is the same as that of each component in the foaming agent composition.
Preferably, the radiation crosslinking manner in S4 includes: high-speed electron field radiation, X-ray radiation, gamma ray radiation, proton radiation, ion field radiation.
Preferably, the foaming in S5 is performed using an electric heating gas cycle.
In another aspect, the invention provides a foamed material comprising the above-described foamed composition or obtained by the method of one of the above-described methods.
Specifically, the density of the foaming material is 500-28kg/m 3 。
Furthermore, the invention also relates to a foamed product which comprises the foamed material. The foamed articles include, but are not limited to: automobile interior trim, floor mat separators, trunk shells, leather inner mats, air conditioning insulating pipes and the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the formula of the composition is adjusted, the crosslinking auxiliary agent containing aniline or/and triazole is used, and the anisotropic parallel double-screw extruder is matched to perform an extrusion molding process, so that the crosslinking degree of the polypropylene material is improved, the crosslinking is more uniform, the foam holes are more delicate, the extrusion shearing force of the anisotropic parallel double-screw extruder is smaller, and the stability of the product in the preparation process of the polypropylene sheet is ensured.
(2) According to the invention, different types of mixed master batches are prepared according to the material characteristics in the process of processing and forming. The foaming agent is easy to decompose in the processing process, so that the foaming agent is mixed with polyethylene or an elastomer for processing, the interval between the melting temperature of the material and the decomposition temperature of the foaming agent is a processing interval, the melting temperature of the polyethylene is lower than that of the polypropylene, and the processing interval is larger.
(3) The invention adopts different granulation processing modes of banburying granulation and twin-screw granulation, considers the easy decomposition physical property of the foaming agent and the difficult dispersion performance of the elastomer, simultaneously makes the processing process cleaner, reduces the instability of feeding extrusion equipment and liquid and dust and improves the consistency of products.
(4) The invention adopts the electric heating circulating hot gas for foaming to prepare the polypropylene foaming material, the process is more environment-friendly, the cleaning process and the recovery process in the salt bath process are reduced, and the TVOC and the smell of the product are lower.
Drawings
FIG. 1: the embodiment of the invention provides a flow chart of a preparation method of a foaming material.
Detailed Description
Hereinafter, the present invention is described in more detail.
(1) Foaming composition
The foaming composition comprises the following components in percentage by mass: 21-93.6% of propylene polymer, 5-35% of polyethylene, 0-20% of elastomer, 1-20% of foaming agent, 0.1-1% of nucleating agent, 0.1-5% of crosslinking assistant and 0.2-3% of antioxidant; the crosslinking assistant is at least one selected from aniline and derivatives thereof, triazole and derivatives thereof, a combination of aniline and derivatives thereof and acrylate compounds, and a combination of triazole and derivatives thereof and acrylate compounds.
In the foaming agent composition, the aniline crosslinking assistant can enable free radicals to be more stable, meanwhile, aniline is high in electron cloud density and good in activity, benzene rings have large pi bonds, the activation energy formed by the free radicals can be greatly reduced, the service life of the free radicals is prolonged, but the aniline crosslinking assistant is too high in activity and is more beneficial to low-rate products. The triazole and the derivative crosslinking assistant thereof can stabilize free radicals, prolong the service life of the free radicals, and are particularly more stable in the decomposition process of the foaming agent, so that the triazole and the derivative crosslinking assistant thereof are more favorable for high-rate products.
The foaming material prepared by the foaming composition has the advantages of good toughness, low smell, low TVOC content, large performance span and wide density range, and can be widely applied to excellent comprehensive performance of various industries and the like. The blowing agent compositions described above are particularly useful in radiation crosslinking processes, especially those made using counter-rotating parallel twin screws.
According to some embodiments of the present invention, there is provided a foaming composition suitable for radiation crosslinking, comprising, in mass percent: 21-93.6% of propylene polymer, 5-35% of polyethylene, 0-20% of elastomer, 1-20% of foaming agent, 0.1-1% of nucleating agent, 0.1-5% of crosslinking assistant and 0.2-3% of antioxidant; the crosslinking assistant is at least one selected from aniline and derivatives thereof, triazole and derivatives thereof, a combination of aniline and derivatives thereof and acrylate compounds, and a combination of triazole and derivatives thereof and acrylate compounds.
According to further embodiments of the present invention, there is provided a radiation crosslinked foamed composition suitable for manufacturing using counter-rotating parallel twin screws, comprising, in mass percent: 21-93.6% of propylene polymer, 5-35% of polyethylene, 0-20% of elastomer, 1-20% of foaming agent, 0.1-1% of nucleating agent, 0.1-5% of crosslinking assistant and 0.2-3% of antioxidant; the crosslinking assistant is at least one selected from aniline and derivatives thereof, triazole and derivatives thereof, a combination of aniline and derivatives thereof and acrylate compounds, and a combination of triazole and derivatives thereof and acrylate compounds.
Specifically, the proper propylene polymer variety is selected according to the extrusion processing conditions, one of the important indexes is the melt index, and the melt index in the invention is preferably 0.2-5g/10min (230 ℃/2.16 kg). The range of the melt index is more beneficial to the thickness uniformity and the stability in the extrusion process. Melt means too high fluidity to make a sheet as water does, no stickiness, and low molecular weight, resulting in poor performance.
The propylene polymer may be a propylene copolymer or a propylene homopolymer, the latter being preferred.
Preferred examples of the propylene polymer include, but are not limited to: the polypropylene is selected from isotactic polypropylene, syndiotactic polypropylene, impact modified polypropylene, polypropylene-ethylene copolymer, polypropylene-butylene copolymer, maleic anhydride grafted polypropylene (MAH-g-polypropylene), MAH-g-polypropylene-ethylene copolymer, MAH-g-polypropylene-butylene copolymer, metallocene polypropylene-ethylene copolymer, metallocene polypropylene-butylene copolymer, and the different types of propylene polymers can be used alone or in combination.
More preferably, the propylene polymer is a trackless co-polypropylene. The trackless co-polypropylene has more irregular molecular weight and higher melt strength, and is beneficial to irradiation crosslinking and foaming processes.
The amount of the propylene polymer is from 21 to 93.6% based on the total mass of the foamed composition.
Preferred ranges for the amount of the propylene polymer include, but are not limited to: 21-40%, 40-65%, 65-90%, 40-60%, 60-70%, 70-80%, 80-95%, 44-55%, 55-65%, 65-75%, 75-85%, 85-95%. The selection may be made according to the type of actual foamed article.
In some embodiments, the propylene polymer is used in amounts such as: 65%, 70%, 75%, 80%, 86%, 90%, etc.
The invention adds polyethylene to improve the melt extrusion flow property of polypropylene, increases the radiation crosslinking activity of single-component polypropylene, improves the melt strength and the foaming property of a foaming main body, can select low-density polyethylene, metallocene polyethylene and high-density polyethylene, and the different types of polyethylene can be used independently or in combination. Preferably low density polyethylene, most preferably linear low density polyethylene. The low density polyethylene is beneficial to a foaming process, but has poor physical properties, and the high density polyethylene has high crystallinity and less branching although having high physical properties, is not beneficial to forming a closed cell structure, and is easy to collapse in foam cavities, so that the compression strength is low, and the support strength is insufficient.
The polyethylene is used in an amount of 5 to 35% based on the total mass of the foamed composition. The polyethylene content is high, the temperature resistance is insufficient, the polyethylene content is too low, the irradiation is easy to degrade, the melt strength is low, and the foaming process is not facilitated.
Preferred ranges for the amount of polyethylene include, but are not limited to: 5-10%, 10-30%, 5-15%, 15-35%, 10-20%, 20-30%, 15-25%, 25-35%, 10-35%.
In some embodiments, the polyethylene is used in an amount of 10 to 35%, for example: 10%, 15%, 20%, 25%, 30%, 35%, etc.
Meanwhile, a certain amount of polyolefin elastomer or rubber elastomer can be added according to the requirements of soft rebound and touch feeling.
The polyolefin elastomers include, but are not limited to: from the group consisting of copolymers of ethylene and propylene, copolymers of ethylene and octene, and copolymers of ethylene and vinyl acetate, these components may be used alone or in combination.
The rubber-like elastomers include, but are not limited to: natural rubber, ethylene propylene rubber, styrene butadiene rubber and silicon rubber, and the components can be used singly or in combination.
The elastomer is used in an amount of 0 to 20% based on the total mass of the foamed composition.
Preferred ranges for the amount of the elastomer include, but are not limited to: 0-5%, 5-10%, 10-15%, 15-20%, 0-10%, 10-20%, 5-15%, 15-20%.
In order to improve the thermal stability and the cross-linkable performance of the polypropylene foaming product, aromatic amine, hindered phenol chemical and derivatives thereof are added as main antioxidants and sulfur and phosphorus compounds are added as auxiliary antioxidants.
The dosage of the antioxidant is 0.2-3%.
Preferred ranges for the amount of the antioxidant include, but are not limited to: 0.2-1%, 1-2%, 2-3% and 1-3%.
The foaming agent is a substance capable of forming pores, and can be divided into a chemical foaming agent, a physical foaming agent and a surfactant. Chemical blowing agents are preferred in the present invention. Blowing agents above the melting point of the material and below the decomposition temperature of the material may be used.
Specifically, examples of the blowing agent include, but are not limited to: azodicarbonamide (AC), diisopropyl azodicarboxylate, dinitrosopentamethyl tetramine (H blowing agent), oxalyl hydrazine, trinitrotrimethylene triamine, p-toluenesulfonyl azide, 4-phenyltetrazole, and biurea, and these blowing agents may be used alone or in combination.
Preferably, the blowing agent is an AC or H blowing agent, more preferably AC.
The amount of the foaming agent is 1 to 20% based on the total mass of the foamed composition.
Preferred ranges for the amount of blowing agent include, but are not limited to: 1-5%, 5-10%, 10-15%, 1-10% and 5-20%.
Meanwhile, a crosslinking assistant can be added to improve the radiation degradation performance of the polypropylene, wherein the monomer comprises bifunctionality, trifunctionality and higher functionality, and aniline and derivatives thereof or triazole and derivatives thereof are preferably used in the radiation crosslinking process prepared by using counter-rotating parallel twin screws.
Examples of crosslinking aids for said anilines and derivatives thereof include, but are not limited to: the aniline compound is selected from aniline, acetanilide, acetophenone, p-toluidine or diphenylamine.
These components may be used alone or in combination.
Examples of the triazole and derivatives thereof crosslinking aids include, but are not limited to: 1,2, 4-triazole, methyl benzotriazole, voriconazole, tedizolid or derivative thereof.
These components may be used alone or in combination.
The acrylate is at least one or derivative of ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, tetramethylolmethane triacrylate, tripropyl isocyanurate and trimethylolpropane triacrylate.
The amount of the crosslinking aid is 0.1 to 5% based on the total mass of the foaming composition.
Preferred ranges for the amount of the crosslinking coagent include, but are not limited to: 0.1-1%, 1-2%, 2-3%, 3-4%, 4-5%, 1-3%, 3-5%, 2-4%, 2-5%.
In order to improve the foaming pore-forming performance of the foaming material, a certain amount of nucleating agent can be selectively added, and the nucleating agent is inorganic particles with fine particles.
Examples of such nucleating agents include, but are not limited to: kaolin, montmorillonite, clay, talc, calcium carbonate, mica, magnesium oxide, zinc oxide, alumina, carbon black, silica, glass, quartz, titanium oxide, and these components may be used alone or in combination.
The nucleating agent is used in an amount of 0.1 to 1% based on the total mass of the foamed composition.
Preferred ranges of the amount of the nucleating agent include, but are not limited to: 0.1-0.5%, 0.5-1%, 0.6-1%, 0.1-0.3%, 0.3-0.5%, 0.3-1%.
(2) Preparation method of foaming material
The preparation method of the foaming material provided by the invention is shown in figure 1, and specifically comprises the following steps:
s1, mixing an elastomer, a foaming agent, a crosslinking assistant, a nucleating agent and an antioxidant through an internal mixer, and granulating through an extruder of a single-screw extruder to obtain first mixed master batches;
optionally S2, mixing the antioxidant and the crosslinking assistant with the propylene polymer and the polyethylene, and granulating by using a double-screw extruder to obtain second mixed master batches;
s3, extruding the first mixed master batch, the optional second mixed master batch, the propylene polymer and the optional polyethylene into a sheet by using a counter-rotating parallel double-screw extruder to obtain a foamed substrate;
s4, carrying out radiation crosslinking on the foaming substrate to obtain a foaming master slice;
and S5, placing the foaming master slice in a foaming furnace for foaming to obtain the foaming material.
I. Granulation process
The invention selects banburying and single/double screw granulation modes according to the characteristics of the material, and selects the banburying granulation method because the foaming agent is sensitive to the temperature, thereby not only uniformly dispersing liquid, powder and solid resin, but also avoiding the decomposition of the foaming agent material due to overhigh local temperature to prepare foaming mixed master batches (namely first mixed master batches), and simultaneously carrying out double screw granulation on part of the crosslinking auxiliary agent, the antioxidant, the nucleating agent, polyethylene and polypropylene, and preparing the auxiliary agent mixed master batches (namely second mixed master batches) by utilizing the excellent dispersing and shearing properties of the auxiliary agent mixed master batches.
Specifically, in S1, the first mixed mother particle is selected from any one of a first mixed mother particle a, a first mixed mother particle B, and a first mixed mother particle C.
The first mixed master batch A comprises the following components in percentage by mass: 0.2-5% of nucleating agent (for example: 0.2%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%), antioxidant 0.2-5% (e.g., 0.2%, 0.5%, 0.1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%), crosslinking aid 0.2-6% (e.g., 0.2%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%), blowing agent 4-10% (e.g., 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%), polyethylene 74-95.4% (e.g., 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 94%, 95%, 4.5%).
In the first mixed masterbatch A, the preferable ranges of the nucleating agent include, but are not limited to: 0.2-1%, 1-3%, 3-5% and 1-5%.
In the first mixed masterbatch A, the preferable ranges of the antioxidant include, but are not limited to: 0.2-1%, 1-3%, 3-5% and 1-5%.
In the first mixed masterbatch A, the preferable range of the crosslinking assistant includes, but is not limited to: 0.2-1%, 1-3%, 3-6%, 1-5%, 1-6%, 2-6%.
In the first mixed mother particle a, preferable ranges of the foaming agent include, but are not limited to: 4-6%, 4-8%, 5-10% and 6-10%.
In the first mixed mother particle a, the preferable ranges of polyethylene include, but are not limited to: 74-80%, 80-96%, 74-85% and 85-96%.
The first mixed master batch B comprises the following components in percentage by mass: 0.2-5% (e.g., 0.2%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%), 0.2-6% (e.g., 0.2%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%), 10-20% (e.g., 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%), 14-69.4% (e.g., 14%, 20%, 25%, 0%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 69.4%), 20-50% (e.g., 20%, 23%, 25%, 35%, 28%, 30%, 43%, 40%, 48%).
In the first mixed masterbatch B, the preferable ranges of the nucleating agent include, but are not limited to: 0.2-1%, 1-3%, 3-5% and 1-5%.
In the first mixed masterbatch B, the preferable ranges of the antioxidant include, but are not limited to: 0.2-1%, 1-3%, 3-5% and 1-5%.
In the first mixed mother particle B, preferable ranges of the crosslinking assistant include, but are not limited to: 0.2-1%, 1-3%, 3-6%, 1-5%, 1-6%, 2-6%.
In the first mixed mother particle B, preferable ranges of the foaming agent include, but are not limited to: 10-15% and 15-20%.
In the first mixed mother particle a, the preferable ranges of polyethylene include, but are not limited to: 14-20%, 20-50%, 30-70%, 40-70% and 50-70%.
The first mixed master batch C comprises the following components in percentage by mass: 0.2-5% (e.g., 0.2%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%), 0.2-6% (e.g., 0.2%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%), 20-40% (e.g., 20%, 23%, 25%, 28%, 30%, 33%, 35%, 38%, 40%, 43%, 45%, 48%, 50%) of a nucleating agent, 0.2-5% (e.g., 0.2%, 0.5%, 3%, 4%, 4.5%, 5%, 6%), a blowing agent, and polyethylene: 34-79.4% (e.g., 34%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 79.4%), elastomer 0-10% (e.g., 0%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%).
In the first mixed mother particle C, preferred ranges of the nucleating agent include, but are not limited to: 0.2-1%, 1-3%, 3-5% and 1-5%.
In the first mixed masterbatch C, preferred ranges of the antioxidant include, but are not limited to: 0.2-1%, 1-3%, 3-5% and 1-5%.
In the first mixed masterbatch C, preferable ranges of the crosslinking assistant include, but are not limited to: 0.2-1%, 1-3%, 3-6%, 1-5%, 1-6%, 2-6%.
In the first mixed mother particle C, preferred ranges of the foaming agent include, but are not limited to: 20-30% and 30-40%.
In the first mixed masterbatch C, the preferable ranges of the polyethylene include, but are not limited to: 34-45%, 45-60%, 60-80%, 34-50%, 50-70%, 70-80% and 50-80%.
The composition of the first mixed masterbatch can be selected according to the specific application of the prepared foaming material.
And mixing the first mixed master batch A, the first mixed master batch B and the first mixed master batch C in an internal mixer, and then granulating by using a single-screw extruder.
Preferably, in S2, the second mixed mother particle includes, by mass: 0.3-8% (e.g., 0.2%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%) of an antioxidant, 0.3-8% (e.g., 0.2%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%) of a crosslinking aid, 50-80% (e.g., 50%, 55%, 60%, 65%, 70%, 75%, 80%) of polypropylene, 4-49.4% (e.g., 4%, 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 49.4%) of polyethylene.
In the second mixed masterbatch, the preferable ranges of the antioxidant include, but are not limited to: 0.3-1%, 1-3%, 3-5% and 5-8%.
Preferred ranges of cross-linking aids in the second mixed masterbatch pellet include, but are not limited to: 0.2-1%, 1-3%, 3-5%, 5-8%, 1-5%, 3-8%.
In the second mixed mother particle, the preferable ranges of polypropylene include, but are not limited to: 50-60%, 60-70%, 50-70% and 70-80%.
In the second mixed mother particle, the preferable ranges of polyethylene include, but are not limited to: 4-10%, 10-30%, 30-50%, 4-15%, 15-35%, 35-50%.
The raw materials of the second mixed masterbatch can be mixed by using a high-speed mixer or a common mixer, and then granulated by using a double-screw extruder.
In the various mixed master batches, the selection of the components is as follows:
preferably, the propylene polymer has a melt index of 0.2 to 5g/10min (230 ℃/2.16 kg) and is selected from at least one of isotactic polypropylene, syndiotactic polypropylene, trackless polypropylene, block polypropylene, impact modified polypropylene, polypropylene-ethylene copolymer, polypropylene-butene copolymer, MAH-g-polypropylene-ethylene copolymer, MAH-g-polypropylene-butene copolymer, metallocene polypropylene-ethylene copolymer, metallocene polypropylene-butene copolymer.
Preferably, the polyethylene is selected from at least one of low density polyethylene, linear low density polyethylene, metallocene polyethylene, high density polyethylene.
The elastomer is a polyolefin elastomer or a rubber elastomer.
Preferably, the polyolefin elastomer is at least one selected from the group consisting of a copolymer of ethylene and propylene, a copolymer of ethylene and octene, and a copolymer of ethylene and vinyl acetate.
Preferably, the rubber elastomer is at least one selected from natural rubber, ethylene propylene rubber, styrene butadiene rubber and silicone rubber.
Preferably, the foaming agent is at least one selected from the group consisting of azodicarbonamide, diisopropyl azodicarboxylate, dinitrosopentamethyl tetramine, oxalyl hydrazine, trinitrotrimethylene triamine, p-toluenesulfonyl azide, 4-phenyltetrazole, and biurea.
Preferably, the nucleating agent is selected from at least one of kaolin, montmorillonite, clay, talc, calcium carbonate, mica, magnesium oxide, zinc oxide, alumina, carbon black, silica, glass, quartz or titanium oxide.
Preferably, the antioxidant comprises at least one of 2, 6-di-tert-butyl-4-ethylphenol, 2, 6-di-tert-butyl-4-methylphenol, 2, 6-di-tert-butyl-alpha-dimethylamino-p-cresol, 2,4, 6-tri-tert-butylphenol, ditetradecylthiodipropionate, antioxidant 1010, antioxidant CA, antioxidant B215, antioxidant B225, antioxidant 168, antioxidant 405, DLTP and DSTP.
The crosslinking assistant is at least one selected from aniline and derivatives thereof, triazole and derivatives thereof, a combination of aniline and derivatives thereof and acrylate compounds, and a combination of triazole and derivatives thereof and acrylate compounds.
Preferably, the aniline and the derivative thereof are selected from at least one of aniline, acetanilide, acetophenone, p-toluidine and diphenylamine; the triazole and the derivative thereof are selected from at least one of 1,2, 4-triazole, methyl benzotriazole, voriconazole and tedizolid; the acrylate is at least one of ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, tetramethylolmethane triacrylate, tripropyl isocyanurate and trimethylolpropane triacrylate.
II. Master slice extrusion molding process
The foaming mixed master batch (namely the first mixed master batch), the auxiliary agent mixed master batch (namely the second mixed master batch), the polypropylene and the polyethylene are mixed and extruded by the incongruous parallel double screws, so that the cleanness of the workshop environment is ensured, dust is avoided, the influence on the material performance caused by nonuniform liquid feeding is avoided, compared with liquid, dust measuring and feeding equipment, the equipment investment is small, the safety and the environmental protection are realized, meanwhile, the material shearing is small and the temperature is more uniform under the condition that the extrusion pressure is ensured by the incongruous parallel double screws, and the problems of high internal shearing of the equidirectional double screws, easy decomposition of a foaming agent and unstable process are solved.
Preferably, the first mother mixture particle is 5 to 50% (e.g., 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 50%), the second mother mixture particle is 0 to 20% (e.g., 0%, 0.5%, 1%, 3%, 5%, 8%, 10%, 13%, 15%, 18%, 20%), the polyethylene is 0 to 20% (e.g., 0%, 1%, 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20%), and the polypropylene is 10 to 95% (e.g., 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%) by mass.
Preferred ranges of the first mixed masterbatch include, but are not limited to: 5-10%, 10-30%, 30-50%, 4-15%, 15-35%, 35-50% and 10-50%.
Preferred ranges of the second mixed masterbatch include, but are not limited to: 0.5-3%, 3-5%, 5-10%, 10-20%, 3-10%, 5-20%, 3-20%, 0.5-20%.
Preferred ranges for the polyethylene include, but are not limited to: 0-5%, 5-10%, 10-20%, 3-10%, 5-20%.
Preferred ranges for the polypropylene include, but are not limited to: 10-20%, 10-30%, 30-50%, 50-75%, 75-95%, 15-50%, 50-80%, 80-95%, 20-60%, 30-70%, 30-80%.
Preferably, the length-diameter ratio of the screws of the counter-rotating parallel twin screws is 18-45:1, the diameter of the screw is 30-150mm. The length-diameter ratio is too small, the material is not uniformly dispersed, the plasticization is poor, the length-diameter ratio is too large, the material is aged and decomposed, and the selection of the length-diameter ratio of the screw is particularly critical for foaming agent heat-sensitive materials. The screw has too small diameter, low productivity, overlarge diameter, uneven temperature distribution, high technical difficulty and high manufacturing cost, and is only suitable for experimental equipment.
Preferred ranges for the screw length to diameter ratio include, but are not limited to: 18-25: 1. 25-35: 1. 35-45: 1. 25-45:1.
in some embodiments, the screw length to diameter ratio is 25: 1. 33: 1. 40: 1. 42:1;
preferred ranges for the screw diameter include, but are not limited to: 30-50mm, 50-80mm, 80-100mm, 100-120mm, 120-150mm, 30-100mm, 100-150mm, 30-80mm, 80-150mm, 40-110mm.
In some embodiments, the screw has a diameter of 40mm, 65mm, 92mm, or 110mm.
The geometrical size and the apparent condition of the foaming master slice basically determine the width, the thickness and the apparent quality of a final foaming product, the main process conditions are temperature, rotating speed, head pressure and die gap, and various process parameters are selected to ensure that the master slice has uniform plasticization, uniform thickness, smooth surface and uniform internal stress on the premise of no decomposition or micro-decomposition of a material foaming agent. Theoretically speaking, the corresponding relationship between the thickness d0 of the master slice and the thickness d1 of the product is
Figure BDA0002340609720000101
d 0 (n is the expansion ratio), the width relationship is similar. However, in actual production, because the master slice has internal stress, the width and the thickness of the master slice need to be properly corrected
Figure BDA0002340609720000102
d 0 D, correction; after the master slice is heated in a foaming furnace in the foaming process, the width and the thickness of the master slice are increased and the length is shortened under the action of internal stress, so that the specification and the size of a product are influenced after foaming; the existence of internal stress greatly affects the change rule of the product size in the foaming process; in addition, the existence of internal stress can cause the product to curl and block in the foaming process, so the internal stress in the master piece must be eliminated as much as possible. In order to eliminate internal stress, a die temperature machine is arranged at three rollers of the extruder in the extrusion process, so that the cooling water temperature at the three rollers is constant at a certain temperature, and thus, the master slice is discharged at the die opening of the extruder and then is guided to the three rollers in the cooling process without rapid cooling to generate the internal stress; meanwhile, in the continuous operation process of the screw, the temperature in the screw is gradually increased due to friction heat generation, and the preparation of temperature sensitive materials is not facilitated, so that the inner diameter of the screw is cooled by high-temperature oil, and the production consistency of equipment is ensured.
III, radiation crosslinking process
Radiation crosslinking is a technical means for initiating a crosslinking reaction between polymer long chains by using various kinds of radiation. The term "radiation" in the present invention refers to various nuclear radiations such as high-speed electron field, X-ray, gamma ray, proton, ion field, etc., and the application of light radiation such as ultraviolet light, etc. belongs to the field of photochemistry, and can also use ultraviolet light to initiate crosslinking reaction, which is called photocrosslinking. The irradiation penetrates through the resin sheet to be changed into a radiation cross-linked polypropylene sheet, the molecular chain structure of the irradiation cross-linked polypropylene sheet is changed from a linear structure to a net structure, the melt strength of the resin sheet is improved, and the resin sheet can be foamed and formed through a foaming furnace.
Specifically, the radiation crosslinking manner in S4 includes, but is not limited to: high-speed electron field radiation, X-ray radiation, gamma ray radiation, proton radiation, ion field radiation.
IV, foaming process
The foaming is to examine the diamond testing of all the processes, and the foaming process is crucial to the performance of the foaming material, and the TVOC content and the odor grade of the prepared foaming material are superior to those of the foaming polypropylene foam prepared by the traditional process because the foaming is carried out by adopting the electric heating gas circulation. Although the traditional salt bath foaming is beneficial to heat conduction, the defects of difficult gas exchange, complex subsequent salt cleaning process, easy residue of small molecules and the like exist, so the smell and TVOC are high.
Specifically, the foaming manner in S4 is foaming using an electric heating gas cycle.
The invention selects the electric heating circulating hot gas for foaming to replace the traditional salt bath foaming, and has supplementary effect.
In some embodiments, the method of preparing the foamed material comprises:
s1, mixing an elastomer or/and polyethylene, a foaming agent, a crosslinking assistant, a nucleating agent and an antioxidant through an internal mixer, and granulating through an extruder of a single-screw extruder to obtain first mixed master batches;
s2, mixing the antioxidant and the crosslinking assistant with the propylene polymer and the polyethylene, and granulating by using a double-screw extruder to obtain second mixed master batches;
s3, extruding the first mixed master batch, the second mixed master batch, the propylene polymer and the optional polyethylene into a sheet by using a counter-rotating parallel double-screw extruder to obtain a foamed substrate;
s4, carrying out radiation crosslinking on the foaming substrate to obtain a foaming master slice;
and S5, placing the foaming master slice in a foaming furnace for foaming to obtain the foaming material.
In other embodiments, the method of preparing the foamed material comprises:
s1, mixing an elastomer or/and polyethylene, a foaming agent, a crosslinking assistant, a nucleating agent and an antioxidant through an internal mixer, and granulating through an extruder of a single-screw extruder to obtain first mixed master batches;
s3, extruding the first mixed master batch, the propylene polymer and the optional polyethylene into a sheet by using a counter-rotating parallel double-screw extruder to obtain a foamed substrate;
s4, carrying out radiation crosslinking on the foaming substrate to obtain a foaming master slice;
and S5, placing the foaming master slice in a foaming furnace for foaming to obtain the foaming material.
(3) Foaming material and foaming product
The density of the foaming material provided by the invention is 500-28kg/m 3 。
Preferred ranges for the density of the foamed material include, but are not limited to: 500-255kg/m 3 、500-260kg/m 3 、500-270kg/m 3 、500-280kg/m 3 、500-290kg/m 3 、500-300kg/m 3 、500-320kg/m 3 、500-350kg/m 3 、500-400kg/m 3 、400-300kg/m 3 、300-200kg/m 3 、200-100kg/m 3 、100-80kg/m 3 、80-60kg/m 3 、60-40kg/m 3 、40-28kg/m 3 。
The foaming material can be applied to the manufacture of similar products such as automobile products, furniture products, automobile interiors, floor mat clapboards, trunk shells, leather inner mats, air-conditioning heat-insulating pipes and the like.
The term "optionally" in the present invention means that it may or may not be optionally contained according to actual needs. For example, "optional S2" means either including step S2 or not including step S2; "optional second mixed masterbatch" means that the second mixed masterbatch is contained or not contained; by "optional polyethylene" is meant either polyethylene-containing or polyethylene-free.
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
Example 1
The foaming material comprises the following components: the high-density polyethylene composition comprises, by mass, 10% of linear low-density polyethylene, 85% of trackless co-polypropylene, 0.5% of TMPTMA,1.0% of aniline, 0.5% of antioxidant 1010,1% of DSTP,1.5% of azodicarbonamide and 0.5% of calcium carbonate nucleating agent.
The first mixed master batch A comprises the following components in percentage by mass: 4.17 percent of calcium carbonate, 3.33 percent of antioxidant 1010, 6.66 percent of DSTP, 8.33 percent of aniline, 12.5 percent of azodicarbonamide and 65 percent of polyethylene.
The second mixed master batch comprises the following components in percentage by mass: antioxidant 1010% by weight, DSTP 2% by weight, TMPTMA5% by weight, polypropylene 70% by weight and polyethylene 22% by weight.
Mixing the first mixed master batch A12%, the second mixed master batch 10% and the trackless polypropylene 78% in percentage by mass, and then performing extrusion molding on the mixture in a manner that the diameter is 110 screw rods, and the length-diameter ratio is 28:1, extruding and molding the counter-rotating twin screws, and foaming at high temperature to prepare 300kg/m 3 The IXPP foam of (1) has the properties specified in Table 1. The density IXPP foam can be mainly applied to draw-bar boxes and structural members, replaces the traditional extrusion cross-linked foaming polypropylene foam, and has better toughness and finer foam holes.
TABLE 1
Figure BDA0002340609720000121
Example 2
The foaming material comprises the following components: 32 percent of linear low-density polyethylene, 30 percent of elastomer, 28.3 percent of trackless polypropylene, 1.2 percent of TMPTMA,0.6 percent of aniline, 0.3 percent of antioxidant 1010,0.6 percent of DSTP,0.5 percent of silicon dioxide nucleating agent and 6.5 percent of azodicarbonamide foaming agent.
The first mixed master batch B comprises the following components in percentage by mass: 0.83% of silicon dioxide, 0.3% of antioxidant 1010,0.6% of antioxidant aid, 1.2% of TMPTMA, 10.83% of azodicarbonamide, 50% of elastomer and 36.24% of polyethylene.
The second mixed master batch comprises the following components in percentage by mass: main antioxidant 1010.2%, DSTP 2.4%, aniline 6%, 4.8% of TMPTMA, polypropylene 53% and polyethylene 32.6%.
Mixing 60% of first mixed master batch B, 10% of second mixed master batch, 7% of polyethylene and 23% of polypropylene in percentage by mass, and then mixing the mixture in a proportion that the diameter is 92mm, the length-diameter ratio is 40:1, extruding and molding by using counter-rotating parallel twin screws, and foaming at high temperature to prepare the high-density polyurethane foam with the density of 66kg/m 3 The IXPP foam of (1) has the properties specified in Table 2. The IXPP foam can be compounded with TPO, PVC and TPU, and then vacuum forming is carried out, so that the IXPP foam can be widely applied to industries such as automobile interior decoration, furniture leather and the like.
TABLE 2
Figure BDA0002340609720000131
Example 3
The foaming material comprises the following components: by mass percentage, 35% of linear low density polyethylene, 47% of trackless copolymerized polypropylene, 1% of 1,2, 4-triazole, 0.5% of antioxidant 1010,1% of DLTP,0.5% of calcium carbonate nucleating agent and 15% of azodicarbonamide.
The first mixed master batch C comprises the following components in percentage by mass: 1.11 percent of calcium carbonate, 1.11 percent of antioxidant 1010, 2.22 percent of DLTP, 2.22 percent of 1,2, 4-triazole, 33.33 percent of azodicarbonamide and 60 percent of polyethylene.
Mixing the first mixed master batch C45%, linear low-density polyethylene 8% and trackless polypropylene 47% in percentage by mass, and then mixing the mixture in a ratio of the diameter to the length-diameter ratio of 92mm to 36:1, performing extrusion molding on the counter-rotating parallel twin screws, and performing high-temperature foaming to prepare the polyurethane foam with the density of 29kg/m 3 The IXPP foam material can be applied to air conditioner heat preservation, floor heat insulation, and under the same density condition, the strength and toughness are higher than other foam materials, and the IXPP foam material can be applied to the packaging field with high requirements on temperature resistance.
The present invention is illustrated by the above examples, but the present invention is not limited to the above examples, that is, the present invention is not limited to the above examples. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of the raw materials of the product of the present invention, and the addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (16)

1. A foam material, characterized by comprising a foaming composition consisting of: the composite material comprises the following components in percentage by mass: 21-93.6% of propylene polymer, 5-35% of polyethylene, 0-20% of elastomer, 1-20% of foaming agent, 0.1-1% of nucleating agent, 0.1-5% of crosslinking assistant and 0.2-3% of antioxidant; the crosslinking assistant is at least one selected from aniline and derivatives thereof, and a combination of aniline and derivatives thereof and acrylate compounds, and the aniline and derivatives thereof are at least one selected from aniline, acetanilide, p-toluidine and diphenylamine; the acrylate is at least one of ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, tetramethylolmethane triacrylate and trimethylolpropane triacrylate;
the preparation method of the foaming material comprises the following steps:
s1, mixing an elastomer or/and polyethylene, a foaming agent, a crosslinking assistant, a nucleating agent and an antioxidant through an internal mixer, and granulating through an extruder of a single-screw extruder to obtain first mixed master batches;
optionally S2, mixing the antioxidant and the crosslinking assistant with the propylene polymer and the polyethylene, and granulating by using a double-screw extruder to obtain second mixed master batches;
s3, extruding the first mixed master batch, the optional second mixed master batch, the propylene polymer and the optional polyethylene into sheets by using a counter-rotating parallel double-screw extruder to obtain a foamed substrate;
s4, carrying out radiation crosslinking on the foaming substrate to obtain a foaming master slice;
and S5, placing the foaming master slice in a foaming furnace for foaming to obtain the foaming material.
2. The foamed material of claim 1, wherein the propylene polymer has a melt index of 0.2-5g/10min and is selected from at least one of isotactic polypropylene, syndiotactic polypropylene, atactic polypropylene, block polypropylene, impact modified polypropylene, polypropylene-ethylene copolymer, polypropylene-butene copolymer, MAH-g-polypropylene-ethylene copolymer, MAH-g-polypropylene-butene copolymer, metallocene polypropylene.
3. The foamed material according to claim 1, wherein the polyethylene is at least one selected from the group consisting of low density polyethylene, linear low density polyethylene, metallocene polyethylene, and high density polyethylene.
4. The foam material of claim 1, wherein the elastomer is a polyolefin elastomer or a rubber elastomer, and the polyolefin elastomer is at least one selected from the group consisting of a copolymer of ethylene and propylene, a copolymer of ethylene and octene, and a copolymer of ethylene and vinyl acetate; the rubber elastomer is at least one selected from natural rubber, ethylene propylene rubber, styrene butadiene rubber and silicon rubber.
5. The foam of claim 1, wherein the blowing agent is at least one selected from the group consisting of azodicarbonamide, diisopropyl azodicarboxylate, dinitrosopentamethyl tetramine, oxalyl hydrazine, trinitrotrimethylene triamine, p-toluenesulfonyl azide, 4-phenyltetrazole, and biurea.
6. The foam of claim 1, wherein the nucleating agent is selected from at least one of kaolin, montmorillonite, clay, talc, calcium carbonate, mica, magnesium oxide, zinc oxide, alumina, carbon black, silica, glass, quartz, or titanium oxide.
7. The foam of claim 1, wherein the antioxidant is at least one selected from the group consisting of 2, 6-di-tert-butyl-4-ethylphenol, 2, 6-di-tert-butyl-4-methylphenol, 2, 6-di-tert-butyl- α -dimethylamino-p-cresol, 2,4, 6-tri-tert-butylphenol, ditetradecylthiodipropionate, antioxidant 1010, antioxidant CA, antioxidant B215, antioxidant B225, antioxidant 168, antioxidant 405, DLTP, and DSTP.
8. A process for the preparation of a foamed material according to any of claims 1 to 7, comprising:
s1, mixing an elastomer or/and polyethylene, a foaming agent, a crosslinking assistant, a nucleating agent and an antioxidant through an internal mixer, and granulating through an extruder of a single-screw extruder to obtain first mixed master batches;
optionally S2, mixing the antioxidant and the crosslinking aid with the propylene polymer and the polyethylene, and granulating by using a double-screw extruder to obtain second mixed master batches;
s3, extruding the first mixed master batch, the optional second mixed master batch, the propylene polymer and the optional polyethylene into a sheet by using a counter-rotating parallel double-screw extruder to obtain a foamed substrate;
s4, carrying out radiation crosslinking on the foaming substrate to obtain a foaming master slice;
and S5, placing the foaming master slice in a foaming furnace for foaming to obtain the foaming material.
9. The process for producing a foamed material according to claim 8, wherein the length-to-diameter ratio of the screws of the counter-rotating parallel twin screws is from 18 to 45:1, the diameter of the screw is 30-150mm.
10. The method according to claim 8, wherein in S1, the first mixed mother particle is selected from any one of a first mixed mother particle a, a first mixed mother particle B, and a first mixed mother particle C;
wherein, by mass percentage, the first mixed masterbatch A comprises: 0.2-5% of nucleating agent, 0.2-5% of antioxidant, 0.2-6% of crosslinking assistant, 4-10% of foaming agent, and polyethylene: 74 to 95.4 percent;
the first mixed master batch B comprises the following components in percentage by mass: 0.2-5% of nucleating agent, 0.2-5% of antioxidant, 0.2-6% of crosslinking assistant, 10-20% of foaming agent, 14-69.4% of polyethylene and 20-50% of elastomer;
the first mixed master batch C comprises the following components in percentage by mass: 0.2-5% of nucleating agent, 0.2-5% of antioxidant, 0.2-6% of crosslinking assistant, 20-40% of foaming agent, 34-79.4% of polyethylene and 0-10% of elastomer.
11. The method for preparing the foam material according to claim 8, wherein in S2, the second mixed mother particle comprises, in mass percent: 0.3-8% of antioxidant, 0.3-8% of crosslinking assistant, 50-80% of polypropylene and 4-49.4% of polyethylene.
12. The method for preparing the foaming material according to claim 8, wherein in the step S3, the first mixed master batch is 5-50%, the second mixed master batch is 0-20%, the polyethylene is 0-20%, and the polypropylene is 10-94.5% by mass.
13. The method of claim 8, wherein the radiation crosslinking in S4 comprises: high-speed electron field radiation, X-ray radiation, gamma ray radiation, proton radiation, ion field radiation; the foaming mode in S5 is foaming using an electric heating gas cycle.
14. The foaming of any of claims 1-7The material is characterized in that the density of the foaming material is 500-28kg/m 3 。
15. Foamed article, characterized in that it comprises the foamed material according to any one of claims 1 to 7, 14.
16. The foamed article of claim 15, wherein the foamed article comprises an automotive interior, a floor mat partition, a trunk shell, a leather inner mat, or an air conditioning insulating tube.
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