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CN103756124A - Polypropylene foaming material, production and preparation method of product - Google Patents

Polypropylene foaming material, production and preparation method of product Download PDF

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Publication number
CN103756124A
CN103756124A CN201310432735.7A CN201310432735A CN103756124A CN 103756124 A CN103756124 A CN 103756124A CN 201310432735 A CN201310432735 A CN 201310432735A CN 103756124 A CN103756124 A CN 103756124A
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China
Prior art keywords
polypropylene
foaming
acid
component
acrylic acid
Prior art date
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Pending
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CN201310432735.7A
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Chinese (zh)
Inventor
张庆录
王加亮
徐建明
田相松
王世修
杜鹏
杨秀涛
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SHANDONG ZHONGHONG PLASTIC INDUSTRY Co Ltd
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SHANDONG ZHONGHONG PLASTIC INDUSTRY Co Ltd
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Priority to CN201310432735.7A priority Critical patent/CN103756124A/en
Publication of CN103756124A publication Critical patent/CN103756124A/en
Pending legal-status Critical Current

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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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • 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
    • B29C48/397—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 a single screw
    • 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
    • B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
    • B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • 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
    • B29C2948/92552—Frequency
    • 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
    • B29C2948/9258—Velocity
    • 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
    • B29C2948/9258—Velocity
    • B29C2948/9259—Angular velocity
    • 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
    • B29C2948/92923—Calibration, after-treatment or cooling zone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/02—Cellular or porous
    • B32B2305/022—Foam
    • 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
    • C08J2323/10—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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The invention relates to a polypropylene foaming material, which comprises the following raw materials, by weight: 100% of polypropylene (A), 1-30% of an ethylene-acrylic acid copolymer (B), 0.5-5% of an accelerator (C), 0.01-1% of an initiator (D), 0.1-0.5% of an antioxidant (E), 0.1-2% of a lubricant (F), and 0.2-2.0% of a foaming agent (G). According to the present invention, the polypropylene foaming plate produced by using the polypropylene foaming materials is extruded and molded by using a one-step method, wherein the method is simple and convenient, the production efficiency is improved, and the production cost is reduced; and the ethylene-acrylic acid polymer is adopted as the polypropylene grafting monomer, such that the disadvantage of easy cross-linking of the conjugated diene compound is avoided, and the melt has characteristics of high strength and excellent ductility.

Description

The preparation method of a kind of polypropylene foam material, goods and goods
The invention belongs to high molecular foam material production technical field, be specifically related to the preparation method of polypropylene foam material, goods and goods, more specifically, relate to and with single screw extrusion machine, polypropylene and properties-correcting agent reaction modifying are improved to melt strength of polypropylene and complete single stage method extrusion moulding polypropylene foam material of foaming process and preparation method thereof simultaneously.
Background technology
Porous plastics has light weight, heat insulation, sound insulation, buffering, specific tenacity advantages of higher.Therefore in fields such as packing, industry, agricultural, communications and transportation, war industry, space industry and daily necessities, be used widely.The development of China's porous plastics since the 90's of 20th century is also very rapid, and principal item has that urethane (PU) is soft, rigid foam, polystyrene (Ps) and foam polyolefin material.But PU can produce harmful isocyanic ester residue in foaming process, cannot recycle simultaneously; And the without putrefaction of foaming Ps products waste, difficult recovery cause " white pollution ", the European Economic Community in 1991 has formulated enforceable " packing rule ", foaming Ps is listed in to " avoiding use " scope.Foaming PE heatproof is low, and modulus is little, has limited its Application Areas.And expanded polypropylene is except having the advantage of general foam material, also there is good thermostability (maximum operation (service) temperature can reach 120 ℃), higher toughness and tensile strength.Because polypropylene molecule exists a methyl, its chemical structure has determined that the degradation property of polypropylene itself is obviously better than polystyrene and polyethylene, makes it can replace polystyrene foamed to prepare environmentally friendly packing material.Based on above-mentioned advantage, polypropylene foam material especially has competitive power at automobile and packaging field application at many industrial circles, alternative existing polystyrene and polyethylene foam-material, and application prospect is boundless.
PP foaming plate mainly adopts extrusion method to carry out forming process.Extrusion moulding has very high production efficiency, and easily realizes automatization.Early stage PP foaming plate mostly is and adopts two step foam shaping by extrusion methods of crosslinking process prepared.Be about to PP resin and fully mix with whipping agent, linking agent, nucleator etc., then on forcing machine, extrude as sheet material, subsequently the PP sheet material of not foaming is cross-linked, then carries out foaming in foaming furnace.This method is separately carried out batch mixing and foaming, and forcing machine only carries out the mixing of foaming component, and the polypropylene foam material that the method obtains is due to crosslinked not reproducible utilization, and environment is easily polluted.Chinese patent CN201010134664.9 (application on March 26th, 2010) discloses a kind of novel high-rate crosslinking foaming polypropylene board and preparation method thereof.This high-rate crosslinking foaming polypropylene board comprises acrylic resin, linking agent, antiaging agent and whipping agent master batch, utilize irradiation method overcome temperature higher than fusing point after the rapid downward trend of melt strength of polypropylene, prepared the product of excellent property.But the method is a kind of crosslinking prepares polypropylene foam material, obtains expanded polypropylene and does not have returnability, not recyclable as packing and automotive material use, will cause environmental pollution.Similar patent also has Chinese patent CN101081914A, CN1131277C.
Chinese patent CN102115561 B discloses a kind of method of physical foaming polypropylene sheet material, and the method adopts high melt strength, propylene, adds the auxiliary agents such as nucleator and bubble stabilizer.But high melt strength, propylene preparation process complexity, price is high, and domestic market ability to accept is limited.Similarly patent also has CN102295807 A, CN101352945 B and US6251319 (application on April 30th, 1999) etc.
Chinese patent CN 102504325 A disclose the preparation method who adopts plain polypropylene and carbon 5 cut reactive grafting extrusion foamings.Carbon 5 cut smell weights, not environmental protection, and in carbon 5 cuts take alkane as main, olefinic double bonds content rareness, the chance of graft reaction is few, the complete processing requirement meeting of preparing expanded polypropylene is relatively strict, and extrusion foaming is made troubles.
Chinese patent CN99111834.0 (application on July 30th, 1999) discloses a kind of method of producing non-cross-linking PP based resin foam sheet, the extrusion foaming device that is located between forcing machine and die head and is taken over the toothed gear pump being connected by die head is used in this invention, makes likely to produce the foam piece of Aphron and good appearance.But before mouth mould, increase toothed gear pump, improved the process complexity of foaming plate, be unfavorable for the pressure-controlling of melt extrusion process.
  
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of with low cost, the simple single stage method polypropylene of complete processing extruded foaming materials and preparation method thereof.
The object of the invention is to be achieved through the following technical solutions:
Single stage method polypropylene extruded foaming materials, the parts by weight of its raw material composition are:
Polypropylene (A) 100 weight parts
Ethylene acrylic acid co polymer (B) 1-30 weight part, preferably 10-15% weight part
Promotor (C) 0.5-5%
Initiator (D) 0.01～1 weight part
Oxidation inhibitor (E) 0.1-0.5 weight part
Lubricant (F) 0.1-2 weight part.
Whipping agent (G) 0.2-2.0 weight part
Described polypropylene is homo-polypropylene, Co-polypropylene, atactic copolymerized polypropene or its combination, and requiring melt polypropylene flow rate is 1.0-10g/10min, preferably 2-4g/10min.
Described ethylene acrylic acid co polymer is that the polymerization degree is 1000-10000, acrylic acid content 6-15%, the preferably ethylene acrylic acid co polymer of acrylic acid content 9-11%.Ethylene acrylic acid co polymer, under metal-salt or metal oxide effect, forms the star-like grafts of ethylene acrylic, and this grafts with polypropylene grafted, forms polypropylene long-chain branch under peroxidation, thereby produces high melt strength, propylene.
Described promotor is metal oxide, metal hydroxides and stearate composition thereof, is specially zinc oxide, calcium oxide, magnesium oxide, aluminum oxide, calcium hydroxide, magnesium hydroxide, aluminium hydroxide, Zinic stearas, calcium stearate, Magnesium Stearate, aluminum stearate and combination thereof.
Described initiator is selected from peroxide, azo radical initiator or its combination; Be specially BP, dicumyl peroxide, di-t-butyl peroxide, Diisopropyl azodicarboxylate or its combination.
Described oxidation inhibitor is 3,5-di-t-butyl-4-hydroxy phenylpropionic acid octadecyl ester, 2,6-tert-butyl-4-methyl-Phenol, 2, the 6-tertiary butyl-a-dimethylin Pyrogentisinic Acid, three (2,4-tert-butyl-phenyl) one or more compounds in phosphorous acid ester, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and thio-2 acid dilaurate.
Described lubricant is one or more compounds in single stearic acid glycerine lipoprotein, erucicamide, stearic acid, ethylene bis stearamide, ethylene dilaurate acid amides.
Described whipping agent is azo foaming agent, preferably Cellmic C 121 (AC).
A kind of polypropylene foamed plate, comprises three layers, and its center core layer adopts the present composition to make, cortex is the polypropylene of non-foaming, cortex material can adopt virgin pp, also can add the modified master of different performances in cortex material, obtains the foaming plate of different physical characteristics.Add colour batch, can make colored polypropylene expanded plate; Add static inhibitor, can make antistatic polypropylene foamed board; Add high rigidity masterbatch, as increase firm polypropylene, fiber glass reinforced polypropylene, talcum powder Reinforced Polypropylene etc. can make high rigid polypropylene foamed board; POE, EVA, ethylene-propylene rubber(EPR) etc. add elastomerics, as can be made high-toughness polypropylene foamed board; Add toxilic acid grafting PP polar materials, can make surface has the polypropylene expanded plate etc. of certain polarity.
The foaming plate thickness 0.5-5mm making.Described polypropylene foamed plate, gel content is 0, foaming layer cell diameter is not more than 100um; Density≤0.6g/cm 3, transverse tensile strength>=12.5MPa, longitudinal tensile strength>=8MPa, transverse breakage elongation>=150%, longitudinal fracture elongation>=100%.
It is as follows that the present invention walks polypropylene foamed plate preparation method:
1) mix: take in proportion each component, put into homogenizer and fully mix 5-6 minute, guarantee that mixing temperature is not less than 50 degree.
2) cooling and absorbing: by the cooling placement at least 24 hours under the environment of sealing of mixed raw material.
3) extrusion foaming: extrusion equipment adopts ABC tri-machine co-extrusions, and wherein forcing machine B is as foaming layer forcing machine, and A, C are as the cortex forcing machine of non-foaming.Mixture is added in single screw extrusion machine B, and single screw slenderness ratio is greater than 30:1, rotating speed 20-60r/min, and forcing machine design temperature is 170-220 degree, die temperature 160-180 degree; The extruded material process divider of single screw extrusion machine A and C and the foaming layer that forcing machine B extrudes are compound, and through rack-style flat plate mold extrusion foaming, the foaming plate of extruding obtains finished product after three roller cooling and shaping cuttings.
Adopt three machine co-extrusions, be conducive to improve foaming plate surface quality and product performance.
Beneficial effect: the present invention adopts single stage method extrusion moulding polypropylene foam material, and the method is simple, convenient, has improved production efficiency, has reduced production cost.The present invention adopts ethylene, propylene acid polymer as polyacrylic grafted monomer, avoided easily crosslinked shortcoming of conjugated diene compound, and melt strength is high, and ductility is good.Major equipment of the present invention is homogenizer and single screw extrusion machine, and facility investment is few, and technique is simple, easily controls, with low cost.
Accompanying drawing explanation
Fig. 1 is comparative example microphotograph
Fig. 2 is embodiment 3 microphotographs
Fig. 3 is embodiment 5 microphotographs
Fig. 4 is embodiment 7 microphotographs
Embodiment
Embodiment 1
Starting material component: component (A) is 100 parts of homopolymerization PP powders, Shandong Kai Chemical Co., Ltd. produces, and the trade mark is 045, MFR 3.0g/10min; Component (B) is 10 parts of ethylene acrylic acid co polymers, acrylic acid content 11%; Component (C) is 1 part of super fine zinc oxide; Component (D) is 0.08 part of dicumyl peroxide; Component (E) is 0.15 part of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 0.3 part of thio-2 acid dilaurate; Component (F) is 0.5 part of stearic acid Tegin 55G; Component (G) is 0.4 part of blowing agent AC.
Cortex material: Co-polypropylene, Qilu Petrochemical Company produces, trade mark EPS30R, MFR 2.0g/10min.
Single screw extrusion machine structure and function: the single screw extrusion machine B screw diameter 90mm adopting, length-to-diameter ratio is 33:1, speed control by frequency variation adopts 5 sections and adds control temp.Single screw rod A, C screw diameter 45mm, length-to-diameter ratio 33:1,4 sections of temperature controls.
Mould adopts rack-style flat mould, 7 sections of temperature controls, die lip gap 1.5mm, products thickness 2mm.
Single stage method extrusion moulding polypropylene foamed plate and preparation method thereof: in high-speed mixer, by above-mentioned all components mixing 5-6 minute, guarantee that temperature is not less than 50 degree, in the HDPE film bag of sealing, place 24 hours, then process reactive extrusion-foaming process in single screw extrusion machine, obtains product of the present invention.Control 40 revs/min of forcing machine rotating speeds.
Each section of temperature of single screw extrusion machine A, C is: 180 ℃, 220 ℃, 230 ℃, 220 ℃
Each section of temperature control of single forcing machine B is: 170 ℃, 190 ℃, 200 ℃, 210 ℃, 200 ℃
Die temperature, 182 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃, 182 ℃
Divider: 185 ℃, runner temperature: 190 ℃.
Comparative example
Starting material component: component (A) is 100 parts of homopolymerization PP powders, Shandong Kai Chemical Co., Ltd. produces, and the trade mark is 045, MFR 3.0g/10min; Component (B) is 0 part of ethylene acrylic acid co polymer; Component (C) is 0 part of super fine zinc oxide; Component (D) is 0 part of dicumyl peroxide; Component (E) is 0.15 part of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 0.3 part of thio-2 acid dilaurate; Component (F) is 0.5 part of stearic acid Tegin 55G; Component (G) is 0.4 part of blowing agent AC.
All the other operating method are identical with embodiment 1.
Embodiment 2
Starting material component: component (A) is 100 parts of homopolymerization PP powders, Shandong Kai Chemical Co., Ltd. produces, and the trade mark is 045, MFR 3.0g/10min; Component (B) is 10 parts of ethylene acrylic acid co polymers, acrylic acid content 11%; Component (C) is 1 part of super fine zinc oxide; Component (D) is 0.12 part of dicumyl peroxide; Component (E) is 0.15 part of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 0.3 part of thio-2 acid dilaurate; Component (F) is 0.5 part of stearic acid Tegin 55G; Component (G) is 0.4 part of blowing agent AC.
Forcing machine B Temperature Setting: 170 ℃, 192 ℃, 197 ℃, 205 ℃, 195 ℃
Die temperature, 180 ℃, 178 ℃, 178 ℃, 178 ℃, 178 ℃, 178 ℃, 180 ℃
Operating method is identical with embodiment 1.
Embodiment 3
Starting material component: component (A) is 100 parts of homopolymerization PP powders, Shandong Kai Chemical Co., Ltd. produces, and the trade mark is 045, MFR 3.0g/10min; Component (B) is 15 parts of ethylene acrylic acid co polymers, acrylic acid content 11%; Component (C) is 1 part of super fine zinc oxide; Component (D) is 0.15 part of dicumyl peroxide; Component (E) is 0.15 part of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 0.3 part of thio-2 acid dilaurate; Component (F) is 0.5 part of stearic acid Tegin 55G; Component (G) is 0.4 part of blowing agent AC.
Forcing machine B Temperature Setting: 170 ℃, 188 ℃, 195 ℃, 198 ℃, 190 ℃
Die temperature, 177 ℃, 175 ℃, 175 ℃, 175 ℃, 175 ℃, 175 ℃, 177 ℃
All the other operating method are identical with embodiment 1.
Embodiment 4
Starting material component: component (A) is 100 parts of homopolymerization PP powders, Shandong Kai Chemical Co., Ltd. produces, and the trade mark is 045, MFR 3.0g/10min; Component (B) is 15 parts of ethylene acrylic acid co polymers, acrylic acid content 11%; Component (C) is 1 part of super fine zinc oxide; Component (D) is 0.15 part of dicumyl peroxide; Component (E) is 0.15 part of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 0.3 part of thio-2 acid dilaurate; Component (F) is 0.5 part of stearic acid Tegin 55G; Component (G) is 0.5 part of blowing agent AC.
Forcing machine B Temperature Setting: 170 ℃, 185 ℃, 190 ℃, 195 ℃, 188 ℃
Die temperature, 173 ℃, 172 ℃, 172 ℃, 172 ℃, 172 ℃, 172 ℃, 173 ℃
All the other operating method are identical with embodiment 1.
Embodiment 5
Starting material component: component (A) is 100 parts of trackless copolymerization homopolymerization PP powders, Nanjing, Nanjing Chemical Co., Ltd. produces, and the trade mark is 045, MFR 4.5g/10min; Component (B) is 15 parts of ethylene acrylic acid co polymers, acrylic acid content 11%; Component (C) is 1 part of super fine zinc oxide; Component (D) is 0.18 part of dicumyl peroxide; Component (E) is 0.15 part of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 0.3 part of thio-2 acid dilaurate; Component (F) is 0.5 part of stearic acid Tegin 55G; Component (G) is 0.5 part of blowing agent AC.
Forcing machine B Temperature Setting: 170 ℃, 182 ℃, 185 ℃, 188 ℃, 182 ℃
Die temperature, 177 ℃, 175 ℃, 175 ℃, 175 ℃, 175 ℃, 175 ℃, 177 ℃
All the other operating method are identical with embodiment 1.
Embodiment 6
Starting material component: component (A) is 50 parts of Co-polypropylene, Qilu Petrochemical Company produces, trade mark EPS30R, MFR 2.0g/10min; 50 parts of homopolymerization PP powders, Shandong Kai Chemical Co., Ltd. produces, and the trade mark is 045, MFR 3.0g/10min; Component (B) is 15 parts of ethylene acrylic acid co polymers, acrylic acid content 11%; Component (C) is 1 part of super fine zinc oxide; Component (D) is 0.15 part of dicumyl peroxide; Component (E) is 0.15 part of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 0.3 part of thio-2 acid dilaurate; Component (F) is 0.5 part of stearic acid Tegin 55G; Component (G) is 0.5 part of blowing agent AC.
Forcing machine B Temperature Setting: 170 ℃, 185 ℃, 190 ℃, 195 ℃, 188 ℃
Die temperature, 177 ℃, 175 ℃, 175 ℃, 175 ℃, 175 ℃, 175 ℃, 177 ℃
All the other operating method are identical with embodiment 1.
Embodiment 7
Starting material component: component (A) is 100 parts of copolymerization PP, Qilu Petrochemical Company produces, and the trade mark is EPS30R, MFR 2.0g/10min; Component (B) is 10 parts of ethylene acrylic acid co polymers, acrylic acid content 11%; Component (C) is 1 part of super fine zinc oxide; Component (D) is 0.12 part of dicumyl peroxide; Component (E) is 0.15 part of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 0.3 part of thio-2 acid dilaurate; Component (F) is 0.5 part of stearic acid Tegin 55G; Component (G) is 0.5 part of blowing agent AC.
Forcing machine B Temperature Setting: 170 ℃, 185 ℃, 190 ℃, 195 ℃, 188 ℃
Die temperature, 177 ℃, 175 ℃, 175 ℃, 175 ℃, 175 ℃, 175 ℃, 177 ℃
All the other operating method are identical with embodiment 1.
 
Tensile strength: according to GB1040-92 test, adopt III type sample, draw speed is 50mm/min.
Foaming product average cell size is measured take electromicroscopic photograph as foundation
The three-layer co-extruded polypropylene foamed plate material property of each embodiment gained can be in Table 1.
The three-layer co-extruded polypropylene foamed plate performance of table 1 table

Claims (9)

1. a polypropylene foam material, consists of following raw material in weight fraction:
Polypropylene (A) 100
Ethylene acrylic acid co polymer (B) 1-30
Promotor (C) 0.5-5%
Initiator (D) 0.01-1
Oxidation inhibitor (E) 0.1-0.5
Lubricant (F) 0.1-2
Whipping agent (G) 0.2-2.0
Described polypropylene is homo-polypropylene, Co-polypropylene, atactic copolymerized polypropene or its combination, and melt flow rate (MFR) is 1.0-10g/10min;
The described ethylene acrylic acid co polymer polymerization degree is 1000-10000, and vinylformic acid weight percentage is 6-15%;
Described promotor is metal oxide, metal hydroxides and stearate composition thereof and combination thereof;
Described initiator is selected from peroxide, azo radical initiator or its combination; Be specially BP, dicumyl peroxide, di-t-butyl peroxide, Diisopropyl azodicarboxylate or its combination;
Described oxidation inhibitor is 3,5-di-t-butyl-4-hydroxy phenylpropionic acid octadecyl ester, 2,6-tert-butyl-4-methyl-Phenol, 2, the 6-tertiary butyl-a-dimethylin Pyrogentisinic Acid, three (2,4-tert-butyl-phenyl) one or more compounds in phosphorous acid ester, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and thio-2 acid dilaurate;
Described lubricant is one or more compounds in single stearic acid glycerine lipoprotein, erucicamide, stearic acid, ethylene bis stearamide, ethylene dilaurate acid amides;
Described whipping agent is azo foaming agent.
2. polypropylene foam material according to claim 1, the acrylic acid content that it is characterized in that ethylene acrylic acid co polymer is 9-11%.
3. polypropylene foam material according to claim 2, the content that it is characterized in that ethylene acrylic acid co polymer is 10-15 weight part.
4. polypropylene foam material according to claim 2, is characterized in that promotor is zinc oxide, calcium oxide, magnesium oxide, aluminum oxide, calcium hydroxide, magnesium hydroxide, aluminium hydroxide, Zinic stearas, calcium stearate, Magnesium Stearate, aluminum stearate and combination thereof.
5. polypropylene foam material according to claim 1, is characterized in that melt polypropylene flow rate is 2-4g/10min.
6. polypropylene foam material according to claim 1, is characterized in that whipping agent is Cellmic C 121.
7. a polypropylene foamed plate, comprises three layers, and its center core layer adopts foam material of the present invention, two polypropylene that cortex is non-foaming.
8. polypropylene foamed plate according to claim 7, wherein the gel content of core layer foaming material is 0.
9. described in claim 7, the preparation method of polypropylene foamed plate is as follows:
1) mix: take in proportion each component, put into homogenizer and fully mix 5-6 minute, guarantee that mixing temperature is not less than 50 degree;
2) cooling and absorbing: by the cooling placement at least 24 hours under the environment of sealing of mixed raw material;
3) extrusion foaming: extrusion equipment adopts ABC tri-machine co-extrusions, wherein forcing machine B is as foaming layer forcing machine, A, C are as the cortex forcing machine of non-foaming, mixture is added in single screw extrusion machine B, single screw slenderness ratio is greater than 30:1, rotating speed 20-60r/min, forcing machine design temperature is 170-220 degree, die temperature 160-180 degree; The extruded material process divider of single screw extrusion machine A and C and the foaming layer that forcing machine B extrudes are compound, and through rack-style flat plate mold extrusion foaming, the foaming plate of extruding obtains finished product after three roller cooling and shaping cuttings.
CN201310432735.7A 2013-09-22 2013-09-22 Polypropylene foaming material, production and preparation method of product Pending CN103756124A (en)

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US11628657B2 (en) 2017-03-31 2023-04-18 Toray Plastics (America), Inc. Method of making coextruded, cross-linked polyolefin foam with TPU cap layers
CN107118490A (en) * 2017-05-26 2017-09-01 合肥会通新材料有限公司 A kind of chemical micro foaming composite material of polypropylene injection and preparation method thereof
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US11590677B2 (en) 2019-03-29 2023-02-28 Toray Plastics (America), Inc. Method of making coextruded, crosslinked polyolefin foam with KEE cap layers
US11590730B2 (en) 2019-03-29 2023-02-28 Toray Plastics (America), Inc. Coextruded, crosslinked polyolefin foam with KEE cap layers
CN110239180A (en) * 2019-07-09 2019-09-17 太仓富宇塑胶科技有限公司 A kind of EPP buffer protection clad plate
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