CN106609000A - Polyethylene combination, preparation method thereof and modified crosslinked polyethylene - Google Patents
Polyethylene combination, preparation method thereof and modified crosslinked polyethylene Download PDFInfo
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- CN106609000A CN106609000A CN201510698122.7A CN201510698122A CN106609000A CN 106609000 A CN106609000 A CN 106609000A CN 201510698122 A CN201510698122 A CN 201510698122A CN 106609000 A CN106609000 A CN 106609000A
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- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/247—Heating methods
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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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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- 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
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/16—Ethene-propene or ethene-propene-diene copolymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
Abstract
The invention discloses a polyethylene combination, a preparation method thereof and modified crosslinked polyethylene. Based on the total weight of the polyethylene combination, the polyethylene combination comprises 50-90 wt% of polyethylene, 0-15 wt% of polyolefin elastomer, 1-10 wt% of compatilizer, 5-40 wt% of inorganic filler, 1-2 wt% of cross-linking agents, 0.1-1 wt% of crosslinking agents and 0.1-1 wt% of antioxidants and processing agents, specifically, the compatilizer is at least one of high density polyethylene chlorinating grafting maleic anhydride, maleic anhydride-grafted ethylene-octene copolymer, glycidyl methacrylate grafted ethylene-octene copolymer, glycidyl methacrylate grafted polyethylene, acrylic acid grafted polyethylene and silane grafted polyethylene. Thus, the obtained modified crosslinked polyethylene can integrate high impact resistance, high modulus, high impact strength and excellent high-temperature creeping resistance.
Description
Technical field
The present invention relates to a kind of polyethylene composition and preparation method thereof, and handed over by the polyethylene composition
The modified crosslinking polyethylene that connection reaction is obtained.
Background technology
Polyethylene is one of the most important material for being widely used in every field, can by as extrusion molding,
The forming methods such as blowing, injection, film modeling, rotational moulding are processed into various different shape products.However, simple
Polythene material cannot meet many applications to intensity, modulus, toughness, thermostability high request.Mesh
Before, it is crosslinked and filling is the effective way for improving polythene material performance.
Wherein filling is easy, the effective method of material modification.Realize that effectively filling needs to select to close
To meet different performance requirements, the otherwise addition of filler will affect the performance of end article to suitable filler.
And for the filling of crosslinked polyethylene is with greater need for the suitable filler of selection.
CN102061030A discloses high-abrasion-resistant corrosion-resistant inorganic particle crosslinking polyethylene composite material,
The material is made up of A and the components of B two：Component A constitutes linear Low Density Polyethylene, polyethylene and changes
Property agent, antioxidant；B component composition has high density polyethylene (HDPE), linear low density polyethylene, ultra-fine Al2O3、
Nanometer MoS2, dispersed lubricant, surface conditioning agent, cross-linking agent and assistant crosslinking agent.The composite
Preparing includes that component A is mixed extruding pelletization by (1), then standby with the process of Surface Treatment with Plasma instrument；
(2) B component passes through first by ultra-fine Al2O3, nanometer MoS2With surface conditioning agent process, then with it
He prepares component mixing extruding pelletization；(3) component A and B component are mixed to get into composite.Should
Composite can have excellent rigid, hardness, resistance to chemical attack and barrier.
CN102492213A discloses a kind of rotational molding grade cross-linked polyethylene wear-resistant composite and its preparation side
Method, the composite is consisted of：Linear low density polyethylene 76.7-79%, ultra-high molecular weight polyethylene
4-19%, cross-linking agent 0.15-4%, antioxidant 0.15-1% and surface-treated inorganic filler 4-12%.
Wherein surface-treated inorganic filler be crossed with coupling agent treatment molybdenum bisuphide, chromite powder, graphite,
At least one in fluorite, Vermiculitum, titanium dioxide, tungsten sulfide, vulcanized lead, Kaolin, rare earth.Nothing
The surface treatment method of machine filler is：Coupling agent adds and is added dropwise over being mixed in inorganic filler after ethanol water
Close, be then dried.The composite provides the anti-wear performance of material.
CN102417650A discloses a kind of wear-resisting crosslinking PE multiple tubes, and the composite pipe sections are into including：
100 parts of polyethylene, anti-scratch liniment 1-3 parts, carbon fiber 0-10 parts, elastomer 0-5 parts, antioxidant 0.05-0.2
Part, crosslinking accelerator 0.2-1 parts and lubricant 0.5-1 parts.The preparation of the multiple tube includes：By each component
Mixing extruding pelletization, then mixes with the silane crosslinker mixture being made up of silane and cross-linked evocating agent for PE
Dispensing, the PE mixed ingredients are finally extruded and are crosslinked obtain wear-resisting crosslinking PE multiple tubes.
CN1051370A discloses the polyethylene product of a kind of phosphate ester-containing and Inorganic Fillers Filled, the product
Product using phosphate monoester as coupling agent treatment calcium carbonate powder surface after be filled in polyethylene product, match somebody with somebody
Fang Zufen is：100 parts of polyethylene, Calcium Carbonate 10-500 part, phosphate monoester 0.5-10 part/100 part CaCO3。
CN102558643A is related to a kind of inorganic powder filling-modified PE agglomerate and preparation method thereof, group
Divide and parts by weight are：At 10-30 part PE, 60-85 part inorganic powder material powder body, 0.5-3 parts surface
Reason agent, 0.5-5 parts Tissuemat E and 0.5-1.5 part paraffin.Specifically disclosed preparation method includes：First will
Inorganic particle and surface conditioning agent are mixed into compound, then by PE, Tissuemat E, paraffin and compound
Mixing and extruding pelletization master batch.
But polyethylene products are in actual use, not only need excellent impact strength, high tenacity,
High-moduluss, will also there is excellent high temperature resistant croop property.Therefore need to provide new modified crosslinking polyethylene.
The content of the invention
The invention aims to solve the performance for how improving polyethylene to provide with excellent anti-impact
The problem of the polythene material of hit intensity, high tenacity, high-moduluss and high temperature resistant croop property, there is provided one
Plant polyethylene composition and preparation method thereof and modified crosslinking polyethylene.
Particularly, how the present invention is crosslinked poly- second in order to effectively utilizes flyash is as filler for improving
Alkene has carried out many researchs.
To achieve these goals, the present invention provides a kind of polyethylene composition, with the gross weight of said composition
On the basis of amount, said composition includes polyethylene, the polyolefin elastic of 0-15 weight % of 50-90 weight %
Body, the compatilizer of 1-10 weight %, the inorganic filler of 5-40 weight %, the cross-linking agent of 1-2 weight %, 0.1-1
The crosslinking coagent of weight %, and the antioxidant and processing aid of 0.1-1 weight %；Wherein, compatilizer is
Maleic anhydride grafted polyethylene, maleic anhydride grafted ethene-octene copolymer, Glycidyl methacrylate are sweet
Grease grafted ethene-octene copolymer, glycidyl methacrylate graft polyethylene, acrylic acid connect
At least one in branch polyethylene and silane grafted polyethylene.
Preferably, the impact strength of modified crosslinking polyethylene is more than obtained in the polyethylene composition
23KJ/m2, more than 1000MPa, high temperature creep rate is less than 50% for bending moduluses.
Present invention also offers a kind of method of the polyethylene composition for preparing the present invention, including：By poly- second
Alkene, cross-linking agent, crosslinking coagent, antioxidant, processing aid, inorganic filler, compatilizer and optional poly-
Olefin elastomer is mixed, and the mixture for obtaining is carried out into extruding pelletization.
Present invention also offers a kind of modified crosslinking polyethylene, the modified crosslinking polyethylene is by by the present invention
Polyethylene composition carry out cross-linking reaction and obtain.
The polyethylene composition that the present invention is provided, Jing is further crosslinked the modified crosslinking polyethylene for obtaining, can
With with excellent impact strength, high tenacity, high-moduluss, and high temperature resistant croop property is good, so as to more preferable
Ground meets the application of polyethylene products.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The present invention provides a kind of polyethylene composition, on the basis of the gross weight of said composition, said composition
Polyethylene, the polyolefin elastomer of 0-15 weight % including 50-90 weight %, the phase of 1-10 weight %
Appearance agent, the inorganic filler of 5-40 weight %, the cross-linking agent of 1-2 weight %, the crosslinking of 0.1-1 weight % are helped
Agent, and the antioxidant and processing aid of 0.1-1 weight %；Wherein, compatilizer is maleic anhydride grafting
High density polyethylene (HDPE), maleic anhydride grafted ethene-octene copolymer, glycidyl methacrylate connect
Branch ethylene-octene copolymer, glycidyl methacrylate graft polyethylene, acrylic acid-grafted poly- second
At least one in alkene and silane grafted polyethylene.
, according to the invention it is preferred in the case of, the impact of modified crosslinking polyethylene is strong obtained in the compositionss
Degree is more than 23KJ/m2, more than 1000MPa, high temperature creep rate is less than 50% for bending moduluses.
Preferably, inorganic filler be flyash, white carbon, Pulvis Talci, Calcium Carbonate and kieselguhr in extremely
Few one kind.
It is preferred that the mean diameter of the inorganic filler is less than 40 microns.
According to the present invention, for above-mentioned specific inorganic filler the compatilizer of specific consumption, preferred feelings are selected
Under condition, the compatilizer is 1 with the weight ratio of the inorganic filler:1 to 1:20.Can provide final
Modified crosslinking polyethylene is with more excellent performance.
, according to the invention it is preferred in the case of, the density of the polyethylene is 0.92-0.97g/cm3, it is described
The melt index of polyethylene is 0.1-20g/10min.It can be specifically commercially available polyethylene
DMDA8007, melt index is 8g/10min (testing standard ASTM D-1238,190 DEG C, 2.16kg),
Density is 0.963g/cm3(testing standard：ASTM D-1505).
According to the present invention it is possible to polyolefin elastomer is added, and the polyolefin elastomer for selecting can be with nothing
Machine filler, polyethylene have preferable synergy, further improve the property of final modified crosslinking polyethylene
Energy.Under preferable case, the polyolefin elastomer is ethylene-C4-8Olefin copolymer, EP rubbers, three
At least one in first EP rubbers and ethylene-vinyl acetate copolymer.Wherein, the ethylene-C4-8Alkene
Copolymer can be by vinyl monomer and C4-8The compound that olefinic monomer Jing copolyreaction is obtained, such as second
Alkene-butadiene copolymer or ethylene-octene copolymer etc..It is preferred that the polyolefin elastomer is ethylene-octene
Copolymer and/or ternary ethylene-propylene copolymer.
Preferably, said composition includes the polyolefin elastomer of 3-5 weight %.Polyolefin elastomer and institute
The weight ratio for stating inorganic filler is 1:1 to 1:20, preferably 1：4 to 1：6.7；Polyolefin elastomer
It is 1 with the weight ratio of polyethylene:50 to 1:5, preferably 1：25 to 1：10.8.
, according to the invention it is preferred in the case of, the cross-linking agent is cumyl peroxide, benzoyl peroxide first
Acyl, di-isopropylbenzene hydroperoxide, tert-butyl hydroperoxide, 2,5- dimethyl -2,5- di-tert-butyl peroxides
Hexane, 2,5- dimethyl -2,5- di-tert-butyl peroxides -3- alkynes, diacyl peroxide, di-t-butyl
Peroxide, alkyl peroxide, dilauroyl peroxide, methyl ethyl ketone peroxide and cyclohexanone peroxide
In at least one；It is preferred that the cross-linking agent is cumyl peroxide, benzoyl peroxide, two tertiary fourths
Base peroxide, 2,5- dimethyl -2,5- di-t-butyl hexane peroxides and 2,5- dimethyl -2,5- di-t-butyls
Peroxidating at least one in -3- alkynes.
The crosslinking coagent is triallylcyanurate, Triallyl isocyanurate, trihydroxy methyl third
At least one in alkane trimethyl acrylic ester and trimethylolpropane trimethacrylate.
, according to the invention it is preferred in the case of, the antioxidant is antioxidant 1010, irgasfos 168, resists
At least one in oxygen agent 1098, antioxidant 264 and bisphenol-A；It is preferred that the antioxidant is antioxidant
1010, irgasfos 168.
, according to the invention it is preferred in the case of, the processing aid is zinc stearate, calcium stearate, Hard Fat
At least one in sour magnesium and stearic acid.It is preferred that the processing aid is stearic acid and/or calcium stearate.
Present invention also offers a kind of method of the polyethylene composition for preparing present invention offer, the method bag
Include：By polyethylene, cross-linking agent, crosslinking coagent, antioxidant, processing aid, inorganic filler, compatilizer
Mixed with optional polyolefin elastomer, and the mixture for obtaining is carried out into extruding pelletization.
, according to the invention it is preferred in the case of, the temperature of extruding pelletization is 135-155 DEG C.Extruding pelletization can
To carry out in double screw extruder, preferred screw slenderness ratio can be 18/1, and the rotating speed of screw rod is
60-100 rev/min.
Present invention also offers a kind of modified crosslinking polyethylene, the modified crosslinking polyethylene is by by the present invention
Polyethylene composition carry out cross-linking reaction and obtain.
In the present invention, the modified crosslinking polyethylene can have more preferable material property.Specifically, it is described
The impact strength of modified crosslinking polyethylene is 23-77KJ/m2, bending moduluses are 1010-1360MPa, resistance to
High creep rate is 28-49%.
, according to the invention it is preferred in the case of, the temperature of the cross-linking reaction is 180-220 DEG C, and crosslinking is anti-
The time answered is 15-25min.
In the present invention, the approach for completing the cross-linking reaction can be so that there is no particular limitation, can be with various
The reaction molding mode of plastic processing is carried out.Such as described cross-linking reaction can be selected by compression molding
During complete, preparation is suitable to the sheet material of material properties test.Can also be prepared by other molding modes
The polyethylene products such as tubing, section bar, sheet material.
Hereinafter will be described the present invention by embodiment.
In following examples and comparative example,
Izod (having otch) impact strengths are measured and determined according to the method for ASTM D-256, test
Carry out at 23 DEG C, instrument is U.S.'s ceast balance weight impact testing machines；
Method measurement and determination that bending moduluses pass through ASTM D-790, test is carried out at 23 DEG C,
Instrument is U.S. Instron5965 type electronic universal material testing machines；
Method measurement and determination that tensile strength passes through ASTM D-638, test is carried out at 23 DEG C,
Instrument is U.S. Instron5965 type electronic universal material testing machines；
High temperature creep property is hung in an oven by the way that tensile bars fixture is clamped into batten upper end, under
End hangs up the counterweight of 0.25kg, and constant temperature 30min, then takes out test specimens by sample in 200 DEG C of baking ovens
The elongation change of product.
The material for using in the following Examples and Comparative Examples is as follows：
Polyethylene DMDA8007 (english abbreviation is HDPE) is purchased from Shenhua packet header, and melt index is
8g/10min (testing standard ASTM D-1238,190 DEG C, 2.16kg), density is 0.963g/cm3(survey
Test-object is accurate：ASTM D-1505)；
Flyash, former ash is isolated to the flyash of different-grain diameter, average grain from Beijing Thermal Power Plant
Footpath is 2.6 microns；
Kieselguhr：CD04, purchased from Shengzhou Hua Li diatomite products company limited, mean diameter is 21.3
Micron；
Pulvis Talci：BHS-503, purchased from Xu Feng powder body company limited of Quanzhou City, mean diameter is 5.6 micro-
Rice；
Ethylene-octene copolymer (POE 8200), is purchased from DOW Chemical, and melt flow rate (MFR) is 5g/10min
(testing standard ASTM D-1238,190 DEG C, 2.16kg), density is 0.873g/cm3(testing standard：
ASTM D-1505)；
Ternary ethylene-propylene copolymer (EPDM NORDELIP 4570), purchased from Dow Chemical, ethylene
The content of construction unit is 50 weight portions；
Maleic anhydride grafted high density polyethylene (MAH-g-HDPE, GR204), melt flow rate (MFR)
For 12g/10min (testing standard ASTM D-1238,190 DEG C, 2.16kg), density is 0.954g/cm3
(testing standard：ASTM D-1505)；
Maleic anhydride grafted ethene-octene copolymer (MAH-g-POE, GR216), melt flow rate (MFR)
For 1.25g/10min (testing standard ASTM D-1238,190 DEG C, 2.16kg), density is 0.875g/cm3
(testing standard：ASTM D-1505)；
Glycidyl methacrylate graft ethylene-octene copolymer (POE-g-GMA, SOG-02),
Purchased from the liter macromolecule new material Science and Technology Ltd. of Nantong day；
Peroxide cross-linking agent：2,5- dimethyl -2,5- bis- (tert-butyl peroxy base) hexane, crosslinking coagent：Triolefin
Propyl group isocyanuric acid ester, is purchased from Akzo Nobel N.V.；
Antioxidant：Antioxidant 1010, irgasfos 168, are purchased from Chemical Reagent Co., Ltd., Sinopharm Group；
Processing aid：Stearic acid, calcium stearate, are purchased from Chemical Reagent Co., Ltd., Sinopharm Group.
In following examples, each component content is calculated by inventory when preparing in polyethylene composition.
Embodiment 1
This example demonstrates that the preparation method and modified crosslinking polyethylene of the polyethylene composition of the present invention.
(1) polyethylene composition processed：By the mistake of high density polyethylene (HDPE) DMDA8007,10g of 540g
Oxide cross linking agent 2,5- dimethyl -2,5- two (tert-butyl peroxy base) hexane, the crosslinking coagent triallyl of 2g
The ethylene-octene copolymer of isocyanuric acid ester, 50g, the glycidyl methacrylate graft second of 10g
Alkene-octene copolymer (POE-g-GMA), the antioxidant 1010 of 4g, the irgasfos 168 of 4g and 200g
Flyash, 5min is stirred to mix homogeneously by homogenizer, then squeezed by twin screw
Go out machine melt blending, pelletize, the screw slenderness ratio of double screw extruder is 18/1, the rotating speed of screw rod is 100
Rev/min, blending temperature during Screw Extrusion is 150 DEG C, is prepared into polyethylene composition SPE-1；
(2) it is crosslinked：SPE-1 is carried out into compression molding 20min at 200 DEG C, modified crosslinking is obtained and is gathered
Ethylene.
Modified crosslinking polyethylene is carried out into performance test, 1 is the results are shown in Table.
Embodiment 2
This example demonstrates that the preparation method and modified crosslinking polyethylene of the polyethylene composition of the present invention.
(1) polyethylene composition processed：By the mistake of high density polyethylene (HDPE) DMDA8007,7g of 500g
Oxide cross linking agent 2,5- dimethyl -2,5- two (tert-butyl peroxy base) hexane, the crosslinking coagent triallyl of 4g
Isocyanuric acid ester, the maleic anhydride grafted ethene-octene copolymer (POE-g-MAH) of 100g, 3g
The flyash of antioxidant 1010, the irgasfos 168 of 3g and 400g, is stirred by homogenizer
5min to mix homogeneously, then by double screw extruder melt blending, pelletize, double screw extruder
Screw slenderness ratio be 18/1, the rotating speed of screw rod is 60 revs/min, and blending temperature during Screw Extrusion is 155
DEG C, it is prepared into polyethylene composition SPE-2；
(2) it is crosslinked：SPE-2 is carried out into compression molding 20min at 200 DEG C, modified crosslinking is obtained and is gathered
Ethylene.
Modified crosslinking polyethylene is carried out into performance test, 1 is the results are shown in Table.
Embodiment 3
This example demonstrates that the preparation method and modified crosslinking polyethylene of the polyethylene composition of the present invention.
(1) polyethylene composition processed：By the mistake of high density polyethylene (HDPE) DMDA8007,5g of 750g
Oxide cross linking agent cumyl peroxide, the crosslinking coagent Triallyl isocyanurate of 5g, 50g
Maleic anhydride grafted ethene-octene copolymer (POE-g-MAH), the antioxidant 1010 of 2g, 2g it is anti-
The kieselguhr of oxygen agent 168 and 200g, is stirred 5min to mix homogeneously, so by homogenizer
Afterwards by double screw extruder melt blending, pelletize, the screw slenderness ratio of double screw extruder is 18/1,
The rotating speed of screw rod is 80 revs/min, and blending temperature during Screw Extrusion is 135 DEG C, is prepared into polyethylene group
Compound SPE-3；
(2) it is crosslinked：SPE-3 is carried out into compression molding 20min at 200 DEG C, modified crosslinking is obtained and is gathered
Ethylene.
Modified crosslinking polyethylene is carried out into performance test, 1 is the results are shown in Table.
Embodiment 4
This example demonstrates that the preparation method and modified crosslinking polyethylene of the polyethylene composition of the present invention.
(1) polyethylene composition processed：By the mistake of high density polyethylene (HDPE) DMDA8007,7g of 750g
Oxide cross linking agent cumyl peroxide, the crosslinking coagent Triallyl isocyanurate of 3g, 30g
Ternary ethylene-propylene copolymer, the maleic anhydride grafted ethene-octene copolymer (POE-g-MAH) of 30g, 3g
Antioxidant 1010, the irgasfos 168 of 3g and 200g kieselguhr, stirred by homogenizer
5min is mixed to mix homogeneously, then by double screw extruder melt blending, pelletize, twin-screw extrusion
The screw slenderness ratio of machine is 18/1, and the rotating speed of screw rod is 100 revs/min, blending temperature during Screw Extrusion
For 150 DEG C, polyethylene composition SPE-4 is prepared into；
(2) it is crosslinked：SPE-4 is carried out into compression molding 25min at 180 DEG C, modified crosslinking is obtained and is gathered
Ethylene.
Modified crosslinking polyethylene is carried out into performance test, 1 is the results are shown in Table.
Embodiment 5
This example demonstrates that the preparation method and modified crosslinking polyethylene of the polyethylene composition of the present invention.
(1) polyethylene composition processed：By the mistake of high density polyethylene (HDPE) DMDA8007,7g of 680g
Oxide cross linking agent cumyl peroxide, the crosslinking coagent Triallyl isocyanurate of 4g, 80g
Maleic anhydride grafted ethene-octene copolymer (POE-g-MAH), the antioxidant 1010 of 2g, 2g it is anti-
The Pulvis Talci of oxygen agent 168 and 250g, is stirred 5min to mix homogeneously, so by homogenizer
Afterwards by double screw extruder melt blending, pelletize, the screw slenderness ratio of double screw extruder is 18/1,
The rotating speed of screw rod is 100 revs/min, and blending temperature during Screw Extrusion is 150 DEG C, is prepared into polyethylene group
Compound SPE-5；
(3) it is crosslinked：SPE-5 is carried out into compression molding 15min at 220 DEG C, modified crosslinking is obtained and is gathered
Ethylene.
Modified crosslinking polyethylene is carried out into performance test, 1 is the results are shown in Table.
Embodiment 6
This example demonstrates that the preparation method and modified crosslinking polyethylene of the polyethylene composition of the present invention.
(1) polyethylene composition processed：By the mistake of high density polyethylene (HDPE) DMDA8007,7g of 750g
Oxide cross linking agent 2,5- dimethyl -2,5- two (tert-butyl peroxy base) hexane, the crosslinking coagent triallyl of 4g
Isocyanuric acid ester, the maleic anhydride grafted ethene-octene copolymer (POE-g-MAH) of 50g, 2g it is anti-
The irgasfos 168 of oxygen agent 1010,2g and the flyash of 200g, by homogenizer 5min is stirred
To mix homogeneously, then by double screw extruder melt blending, pelletize, the screw rod of double screw extruder
Draw ratio is 18/1, and the rotating speed of screw rod is 100 revs/min, and blending temperature during Screw Extrusion is 150 DEG C,
It is prepared into polyethylene composition SPE-6；
(3) it is crosslinked：SPE-6 is carried out into compression molding 20min at 180 DEG C, modified crosslinking is obtained and is gathered
Ethylene.
Modified crosslinking polyethylene is carried out into performance test, 1 is the results are shown in Table.
Comparative example 1
Polyethylene composition processed：By the peroxide of high density polyethylene (HDPE) DMDA8007,7g of 800g
The crosslinking coagent triallyl isocyanide urea of cross-linking agent 2,5- dimethyl -2,5- two (tert-butyl peroxy base) hexane, 4g
The flyash of acid esters, the antioxidant 1010 of 2g, the irgasfos 168 of 2g and 200g, by high-speed stirred
Machine is stirred 5min to mix homogeneously, double then by double screw extruder melt blending, pelletize
The screw slenderness ratio of screw extruder is 18/1, and the rotating speed of screw rod is 100 revs/min, during Screw Extrusion
Blending temperature is 150 DEG C, is prepared into polyethylene composition DSPE-1；
Crosslinking：DSPE-1 is carried out into compression molding 20min at 200 DEG C, the poly- second of modified crosslinking is obtained
Alkene.
Modified crosslinking polyethylene is carried out into performance test, 1 is the results are shown in Table.
Comparative example 2
Polyethylene composition processed：By the antioxidant of high density polyethylene (HDPE) DMDA8007,2g of 800g
1010th, the flyash of the irgasfos 168 of 2g and 200g, by homogenizer 5min is stirred
To mix homogeneously, then by double screw extruder melt blending, pelletize, the screw rod of double screw extruder
Draw ratio is 18/1, and the rotating speed of screw rod is 100 revs/min, and blending temperature during Screw Extrusion is 150 DEG C,
It is prepared into polyethylene composition DSPE-2；
Crosslinking：DSPE-2 is carried out into compression molding 20min at 200 DEG C, modified poly ethylene is obtained.
Modified crosslinking polyethylene is carried out into performance test, 1 is the results are shown in Table.
Comparative example 3
Polyethylene composition processed：By the peroxide of high density polyethylene (HDPE) DMDA8007,7g of 800g
The crosslinking coagent triallyl isocyanide urea of cross-linking agent 2,5- dimethyl -2,5- two (tert-butyl peroxy base) hexane, 4g
The irgasfos 168 of acid esters, the antioxidant 1010 of 2g and 2g, by homogenizer 5min is stirred
To mix homogeneously, then by double screw extruder melt blending, pelletize, the screw rod of double screw extruder
Draw ratio is 18/1, and the rotating speed of screw rod is 100 revs/min, and blending temperature during Screw Extrusion is 150 DEG C,
It is prepared into polyethylene composition DSPE-3；
Crosslinking：DSPE-3 is carried out into compression molding 20min at 200 DEG C, the poly- second of modified crosslinking is obtained
Alkene.
Modified crosslinking polyethylene is carried out into performance test, 1 is the results are shown in Table.
Comparative example 4
Polyethylene composition processed：By the peroxide of high density polyethylene (HDPE) DMDA8007,7g of 800g
The crosslinking coagent triallyl isocyanide urea of cross-linking agent 2,5- dimethyl -2,5- two (tert-butyl peroxy base) hexane, 4g
The kieselguhr of acid esters, the antioxidant 1010 of 2g, the irgasfos 168 of 2g and 200g, by high-speed stirred
Machine is stirred 5min to mix homogeneously, double then by double screw extruder melt blending, pelletize
The screw slenderness ratio of screw extruder is 18/1, and the rotating speed of screw rod is 100 revs/min, during Screw Extrusion
Blending temperature is 150 DEG C, is prepared into polyethylene composition DSPE-4；
Crosslinking：DSPE-4 is carried out into compression molding 20min at 200 DEG C, the poly- second of modified crosslinking is obtained
Alkene.
Modified crosslinking polyethylene is carried out into performance test, 1 is the results are shown in Table.
Table 1
The poly- second of present invention offer is can be seen that by the data of above-described embodiment and comparative example, and table 1
The modified crosslinking polyethylene that ene compositions are further obtained, can be provided with high impact properties and excellent
High temperature resistant croop property.In concrete such as embodiment 1-4, impact strength has reached 30kJ/m2More than,
Wherein embodiment 1-2, impact strength reaches 60kJ/m2More than, and the high temperature resistant croop property of material
It is better than comparative example 1-2 and embodiment 4.Embodiment 5-6 is compared compared with embodiment 3, with higher mould
Amount.
Claims (10)
1. a kind of polyethylene composition, on the basis of the gross weight of said composition, said composition includes 50-90
The polyethylene of weight %, the polyolefin elastomer of 0-15 weight %, the compatilizer of 1-10 weight %, 5-40
The inorganic filler of weight %, the cross-linking agent of 1-2 weight %, the crosslinking coagent of 0.1-1 weight %, and 0.1-1
The antioxidant and processing aid of weight %；
Wherein, compatilizer is maleic anhydride grafted high density polyethylene, maleic anhydride grafted ethene-octene
Copolymer, glycidyl methacrylate graft ethylene-octene copolymer, Glycidyl methacrylate are sweet
At least one in grease grafted polyethylene, acrylic acid-grafted polyethylene and silane grafted polyethylene.
2. polyethylene composition according to claim 1, wherein, change obtained in the compositionss
Property crosslinked polyethylene impact strength be more than 23KJ/m2, bending moduluses are more than 1000MPa, high-temerature creep
Rate is less than 50%.
3. polyethylene composition according to claim 1, wherein, the compatilizer and the nothing
The weight ratio of machine filler is 1:1 to 1:20.
4. the polyethylene composition according to any one of claim 1-3, wherein, the polyene
Olefin elastomer is ethylene-C4-8Olefin copolymer, EP rubbers, ethylene propylene diene rubber and ethylene-vinyl acetate
At least one in copolymer；The inorganic filler be flyash, white carbon, Pulvis Talci, Calcium Carbonate and
At least one in kieselguhr.
5. the polyethylene composition according to any one of claim 1-3, wherein, the crosslinking
Agent be cumyl peroxide, benzoyl peroxide, di-isopropylbenzene hydroperoxide, tert-butyl hydroperoxide,
2,5- dimethyl -2,5- di-t-butyl hexane peroxides, 2,5- dimethyl -2,5- di-tert-butyl peroxides -3-
Alkynes, diacyl peroxide, di-tert-butyl peroxide, alkyl peroxide, dilauroyl peroxide,
At least one in methyl ethyl ketone peroxide and cyclohexanone peroxide；The crosslinking coagent is triallyl cyanogen urea
Acid esters, Triallyl isocyanurate, trimethylol-propane trimethacrylate and trimethylolpropane
At least one in triacrylate.
6. the polyethylene composition according to any one of claim 1-3, wherein, the antioxygen
Agent be antioxidant 1010, irgasfos 168, antioxidant 1098, antioxidant 264 and bisphenol-A in extremely
Few one kind；The processing aid be zinc stearate, calcium stearate, magnesium stearate and stearic acid at least
It is a kind of.
7. a kind of method of the polyethylene composition prepared any one of claim 1-6, including：
By polyethylene, cross-linking agent, crosslinking coagent, antioxidant, processing aid, inorganic filler, compatilizer and appoint
The polyolefin elastomer of choosing is mixed, and the mixture for obtaining is carried out into extruding pelletization.
8. method according to claim 7, wherein, the temperature of extruding pelletization is 135-155 DEG C.
9. a kind of modified crosslinking polyethylene, the modified crosslinking polyethylene in claim 1-6 by appointing
Polyethylene composition described in one carries out cross-linking reaction and obtains.
10. modified crosslinking polyethylene according to claim 9, wherein, the temperature of the cross-linking reaction
Spend for 180-220 DEG C, the time of cross-linking reaction is 15-25min.
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