CN104987576B - The high polymer product of polyethylene composition and preparation method thereof and paintable high-impact heatproof - Google Patents
The high polymer product of polyethylene composition and preparation method thereof and paintable high-impact heatproof Download PDFInfo
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- CN104987576B CN104987576B CN201510400275.9A CN201510400275A CN104987576B CN 104987576 B CN104987576 B CN 104987576B CN 201510400275 A CN201510400275 A CN 201510400275A CN 104987576 B CN104987576 B CN 104987576B
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- 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
- C08L23/04—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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- 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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- C—CHEMISTRY; METALLURGY
- 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
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Abstract
The present invention relates to a kind of polyethylene composition and preparation method thereof and the high polymer product of paintable high-impact heatproof.The polyethylene composition includes：Polyethylene, maleic anhydride grafted ethene copolymer, polar ethylene base co-polymer, and crosslinking agent and crosslinking coagent；Wherein, relative to the polyethylene of 100 parts by weight, the content of the maleic anhydride grafted ethene copolymer is 10 30 parts by weight, the content of the polar ethylene base co-polymer is 3 15 parts by weight, the content of the crosslinking agent is 0.03 10 parts by weight, and the content of the crosslinking coagent is 0.03 8 parts by weight.The spray painting adhesive force and mechanical shock performance of the high polymer product prepared by said composition are improved, while the high temperature resistant croop property of product is also admirably enhanced.
Description
Technical field
The present invention relates to a kind of polyethylene composition, the polyethylene composition can be used for preparing paintable high-impact heatproof
High polymer product, further relate to the preparation method of the polyethylene composition, and use prepared by the polyethylene composition applying
Paint the high polymer product of high-impact heatproof.
Background technology
Thermoplastic olefin material refers to olefin polymer, or olefin polymer and polyolefin elastomer uncrosslinked blending
Thing, they can by polymerize in the reactor or closed mixing machine physical blending be made.These materials are usually to apply
Paint, reason is paint or coating etc. mainly by polyurethanes, acrylic compounds, epoxies or melamine class polar materials group
Into, and thermoplastic olefin material is generally non-polar material, the adhesiveness between them is excessively poor.To overcome such material
Paintable, the general connection realized using binding agent between thermoplastic olefin material and layer of lacquer, but the increase of this method
Product expense, and and be not durable.
EP0662496A2 discloses a kind of paintable or printable composition, and said composition includes polyolefin or poly-
Alkene/rubber blend, and at least one additive.Specifically, polyolefin or polyolefin/rubber blend include poly- second
Alkene, polypropylene, their copolymer, or they are mixed with ethylene propylene copolymer.It can be maleic anhydride that additive, which is,
Grafted polyethylene or polypropylene, or ethylene oxide or the single function or multifunction polyester of propylene oxide polymerization preparation.
EP063442A1 discloses a kind of compound, the reaction production containing polypropylene and functional poly propylene and polyetheramine
Thing.Blends described above shows improved paintable, shock resistance and molding mobility.
CN1229813A discloses a kind of polymer composition that can directly paint, and it includes (1) thermoplastic olefin
Thing, Noblen or contain ethene or 4-8 carbon atom α-alkene that (2) are grafted with aliphatic series α, β-unsaturated dicarboxylic acid acid anhydride
The propylene copolymer of hydrocarbon, (3) fusing point is less than 116 DEG C and acid number is less than 40 OPE, (4) and graft polymers
The functionalized polymeric of anhydride group reaction, and the polyolefin elastomer that optional (5) are grafted with aliphatic series α, β-unsaturated dicarboxylic acid acid anhydride,
(6) ethene polymers being grafted with aliphatic series α, β-unsaturated dicarboxylic acid acid anhydride.With common thermoplastic's elastomer phase ratio, it is above-mentioned poly-
Compound shows preferable paint adhesion and durability.
WO9325617A2 discloses a kind of paintable thermoplastic compounds, poly- comprising (A) at least 50 weight % grafting
Ethene, wherein graft are at least 0.01 weight % based on polyethylene containing at least one double bond and at least one functional acid
The unsaturated compoundses of group；And the thermoplastic polymer of (B) at least one polar functionalities.Unsaturated organic compound is
Maleic anhydride, thermoplastic polymer is the polyolefin of polyurethane, polyester, epoxy resin, polyamine and polar functionalities.
EP0696302B2 discloses a kind of paintable composition of olefin copolymer, is characterised by, containing polypropylene and connecing
The mixture of branch modified polypropene, substantially non-grafted or graft modification linear tetrafluoroethylene polymer, ethene and α, β-insatiable hunger
With the copolymer of carbonyl.
But in the actual use of thermoplastic olefin material, paintability is not required nothing more than, but also require material
Impact and heat resistance, to meet being actually needed for product.Therefore needing to consider offer can be while meeting to apply
Paint property, impact resilience and durothermic thermoplastic olefin material.
The content of the invention
The invention aims to overcome, existing thermoplastic olefin material paintability is poor, erosion-resisting characteristics is poor and resistance to
Warm nature is not enough, it is impossible to which the defect for meeting product needs resists there is provided polyethylene composition and preparation method thereof and paintable height
Rush the high polymer product of heatproof.
To achieve these goals, the present invention provides a kind of polyethylene composition, and the polyethylene composition includes：Poly- second
Alkene, maleic anhydride grafted ethene copolymer, polar ethylene base co-polymer, and crosslinking agent and crosslinking coagent；Wherein, relative to
The polyethylene of 100 parts by weight, the content of the maleic anhydride grafted ethene copolymer is 10-30 parts by weight, the polarity
The content of ethylenic copolymer is 3-15 parts by weight, and the content of the crosslinking agent is 0.03-10 parts by weight, the crosslinking coagent
Content is 0.03-8 parts by weight.
Present invention also offers a kind of preparation method of polyethylene composition, this method includes：(1) by 10-30 parts by weight
Maleic anhydride grafted ethene copolymer, the polar ethylene copolymer of 3-15 parts by weight, the crosslinking agent of 0.03-10 parts by weight and
The crosslinking coagent of 0.03-8 parts by weight carries out melt blending；(2) blend and the poly- second of 100 parts by weight obtained step (1)
Alkene carries out melt blending；Preferably, the temperature of the melt blending is 140-160 DEG C.
Present invention also offers a kind of preparation method of polyethylene composition, this method includes：(I) by 100 parts by weight
Polyethylene, the maleic anhydride grafted ethene copolymer of 10-30 parts by weight, the polar ethylene copolymer of 3-15 parts by weight, 0.03-10
The crosslinking agent of parts by weight and the crosslinking coagent of 0.03-8 parts by weight carry out low-temperature mixed；(II) mixture for obtaining step (I)
Carry out melt blending；Preferably, the temperature of the low-temperature mixed is 20-50 DEG C, and the temperature of the melt blending is 140-160
℃。
Present invention also offers a kind of preparation method of polyethylene composition, this method includes：(A) by 100 parts by weight
The crosslinking coagent of polyethylene, the crosslinking agent of 0.03-10 parts by weight and 0.03-8 parts by weight carries out melt blending；(B) by step (I)
Obtained blend and maleic anhydride grafted ethene copolymer, the polar ethylene copolymer of 3-15 parts by weight of 10-30 parts by weight
Carry out melt blending；Preferably, the temperature of the melt blending is 140-160 DEG C.
Present invention also offers polyethylene composition prepared by the method that the present invention is provided.
Present invention also offers a kind of height of the paintable high-impact heatproof of the polyethylene composition provided containing the present invention
Polymers product.
There is provided one in order to provide with more preferable paintability, impact and durothermic high polymer product by the present invention
Plant and be total to polyethylene, maleic anhydride grafted ethene copolymer and polar vinyl in polyethylene composition, the composition of said composition
Polymers is combined, and compounds the specific crosslinking agent of addition and crosslinking coagent, and prepared by said composition experience processing and forming into high polymer
During product, heat cross-linking, the cross-linking system that can be formed in the product of acquisition between above-mentioned various polymer, system are carried out
The dimethylbenzene insolubles content of product is more than 60%.Only simple addition improves product obtained by component blending compared with prior art,
The product that the present invention is provided substantially has improved performance, and the spray painting adhesive force and mechanical shock performance of product are improved, together
When product high temperature resistant croop property be also admirably enhanced.
Product prepared by the polyethylene composition that the present invention is provided can have the advantage that and effect：
(a) product that the present invention is obtained has excellent spray painting cohesive force, and spray painting adhesion effect reaches more than 1 grade, and general
The spray painting adhesion effect of logical polyethylene products is below 4 grades；
(b) product that the present invention is obtained has outstanding heat resistance, undeformed in 30 minutes at 200 DEG C, and common
Polyethylene products are deformed in 200 DEG C of Flashmelts；
(c) product that the present invention is obtained has perfect mechanical shock performance, relatively common polyethylene products, notch shock
Intensity is more than 60kJ/m2。
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Brief description of the drawings
Fig. 1 is that the molded specimens of comparative example 1 and embodiment 1-2 preparations stand the pattern contrast before and after 25min at 200 DEG C
Photo；(a) to be subjected to before 200 DEG C, (b) is to be subjected to after 200 DEG C of 25min.
Fig. 2 is the photo comparison that comparative example 1-2 is tested with the paint film adhesive performance of embodiment 1.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides a kind of polyethylene composition, and the polyethylene composition includes：Polyethylene, maleic anhydride grafted ethene
Copolymer, polar ethylene base co-polymer, and crosslinking agent and crosslinking coagent；Wherein, relative to the poly- second of 100 parts by weight
Alkene, the content of the maleic anhydride grafted ethene copolymer is 10-30 parts by weight, and the content of the polar ethylene base co-polymer is
3-15 parts by weight, the content of the crosslinking agent is 0.03-10 parts by weight, and the content of the crosslinking coagent is 0.03-8 parts by weight.
Preferably, the content of the maleic anhydride grafted ethene copolymer is 10-25 parts by weight, more preferably 15-20 weights
Measure part.
Preferably, the content of the polar ethylene base co-polymer is 3-10 parts by weight, more preferably 5-10 parts by weight.
Preferably, the content of the crosslinking agent is 0.05-8 parts by weight, more preferably 0.1-6 parts by weight.
Preferably, the content of the crosslinking coagent is 0.05-6 parts by weight, more preferably 0.1-4 parts by weight.
According to the present invention it is possible to which the performance according to required for end article, chooses in the polyethylene composition of the present invention and makees
For the polyethylene of matrix.Under preferable case, in the polyethylene composition, wherein, the density of the polyethylene is more than
0.935g/cm3, preferably greater than 0.945g/cm3, more preferably 0.955-0.965g/cm3。
Preferably, the melt index of the polyethylene is more than 0.1g/10min, preferably 5-20g/min.More preferably 6-
15g/min。
The polyethylene being obtained commercially, such as polyethylene DMDA8007 can be used in the present invention, 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 invention, it is possible to use maleic anhydride grafted ethene copolymer can be the property needed for end article is brought
Energy.Under preferable case, the density of the maleic anhydride grafted ethene copolymer is 0.850-0.960g/cm3；Preferably
0.880-0.940g/cm3。
Preferably, the melt index of the maleic anhydride grafted ethene copolymer is 2-10g/min；Preferably 3-8g/
min。
It is highly preferred that the grafted maleic anhydride amount of titration measuring is 0.3- in the maleic anhydride grafted ethene copolymer
1.2 weight %；Preferably 0.5-1.0 weight %.
The maleic anhydride grafted ethene copolymer being obtained commercially can be used in the present invention, such as maleic anhydride grafting is highly dense
Spend polyethylene (MAH-g-HDPE GR204), melt flow rate (MFR) be 12g/10min (testing standard ASTM D-1238,190 DEG C,
2.16kg), density is 0.954g/cm3(testing standard：ASTM D-1505), grafted maleic anhydride amount is 0.6-0.8 weight %
(titration)；Maleic anhydride grafted ethene based elastomeric (MAH-g-POE GR216), melt flow rate (MFR) is 1.25g/10min
(testing standard ASTM D-1238,190 DEG C, 2.16kg), density is 0.875g/cm3(testing standard：ASTM D-1505), connect
Branch maleic anhydride amount is 0.5-1.0 weight % (titration).
, according to the invention it is preferred in the case of, the density of the polar ethylene base co-polymer is more than 0.875g/cm3, it is preferably
0.935-0.965g/cm3。
, according to the invention it is preferred in the case of, the polar ethylene base co-polymer can be ethylene-vinyl acetate copolymer
And/or ethylene-vinyl alcohol copolymer (EVOH) (EVA).Preferably ethylene-vinyl acetate copolymer；More preferably ethyl vinyl acetate second
In alkene copolymer, the content of vinyl acetate is more than 20 weight %.
The ethylene-vinyl acetate copolymer (EVA) being obtained commercially can be used in the present invention, such as ethylene-vinyl acetate is total to
Polymers (EVA UE654-04), melt flow rate (MFR) is 30g/10min (testing standard ASTM D-1238,190 DEG C, 2.16kg),
Density is 0.955g/cm3(testing standard：ASTM D-1505).Ethylene-vinyl alcohol copolymer (EVOH), such as ethylene-vinyl
Alcohol copolymer (EVOH OH3003), melt flow rate (MFR) be 3g/10min (testing standard ASTM D-1238,190 DEG C,
2.16kg), density is 1.2g/cm3(testing standard：ASTM D-1505).
According to the present invention, the product that the crosslinking agent and crosslinking coagent are used to finally give provides cross-linked structure, to change
The performance of kind product.The crosslinking agent and crosslinking coagent can provide polyethylene, maleic anhydride grafted ethene copolymer and polarity
Being cross-linked with each other between ethylenic copolymer.Under preferable case, the crosslinking agent is selected from 2,5- dimethyl -2,5- di-t-butyl mistakes
Epoxide -3- hexins, cumyl peroxide, t-butylcumylperoxide, 2,5- dimethyl -2,5- two (t-butylperoxy)
One kind or many in hexane, the oxygen rings in heptan of 3,3,5,7,7- pentamethyls -1,2,4- three and 1,4- dual-tert-butyl cumene hydroperoxides
Kind.
, according to the invention it is preferred in the case of, the crosslinking coagent is triallylcyanurate, triallyl isocyanuric acid
One or more in ester, trimethylol-propane trimethacrylate and trimethylolpropane trimethacrylate.
In the present invention, the polyethylene composition can also contain compound stabilizer.It is highly preferred that relative to 100 weights
The polyethylene of part is measured, the content of the compound stabilizer is 0.1-2 parts by weight, preferably 0.2-1.2 parts by weight.It is described compound steady
Determining agent can be for the conventional compound stabilizer in this area, the stability for improving the product prepared by the polyethylene composition
And long-term anti-ageing performance.The compound stabilizer can be commercially available prod, specifically, for example can for Irganox 1010,
Irganox 168 etc..
In the present invention, the polyethylene composition can also contain other additives commonly used in the art, to enter
One step improves the performance of the product prepared by the polyethylene composition.Other described additives can be UV additives, pigment
With processing aid etc..The UV additives are used for the ageing-resistant performance for improving the product prepared by the polyethylene composition.Institute
State pigment to can be used for improving the outward appearance of product prepared by the polyethylene composition, it is adaptable to which pigment of the invention can be
Commercially available fire-resistant oxidation resistant pigment product.The processing aid can be used for improving the polyethylene composition carry out shaping plus
The processing characteristics in man-hour, such as can be conventional releasing agent, lubricant, slipping agent.In the polyethylene composition, phase
For the polyethylene of 100 parts by weight, the content of other additives can be 0-10 parts by weight, preferably 0.01-5 weight
Part.
Present invention also offers a kind of preparation method of polyethylene composition, this method includes：(1) by 10-30 parts by weight
Maleic anhydride grafted ethene copolymer, the polar ethylene copolymer of 3-15 parts by weight, the crosslinking agent of 0.03-10 parts by weight and
The crosslinking coagent of 0.03-8 parts by weight carries out melt blending；(2) blend and the poly- second of 100 parts by weight obtained step (1)
Alkene carries out melt blending.
Preferably, the temperature of the melt blending is 140-160 DEG C.
In the preparation method for the polyethylene composition that the present invention is provided, the melt blending is real in double screw extruder
Apply.
Each component in the preparation method：Polyethylene, maleic anhydride grafted ethene copolymer, polar ethylene base co-polymer,
Crosslinking agent and crosslinking coagent are as described above, repeat no more.In addition, can also be added in the preparation method in step (1) compound
Stabilizer and other additives, as detailed above, are repeated no more.
Present invention also offers a kind of preparation method of polyethylene composition, this method includes：(I) by 100 parts by weight
Polyethylene, the maleic anhydride grafted ethene copolymer of 10-30 parts by weight, the polar ethylene copolymer of 3-15 parts by weight, 0.03-10
The crosslinking agent of parts by weight and the crosslinking coagent of 0.03-8 parts by weight carry out low-temperature mixed；(II) mixture for obtaining step (I)
Carry out melt blending.
Preferably, the temperature of the low-temperature mixed is 20-50 DEG C, and the temperature of the melt blending is 140-160 DEG C.
In the preparation method for the polyethylene composition that the present invention is provided, the low-temperature mixed can be real in high speed mixer
Apply；The melt blending is implemented in double screw extruder.
Each component in the preparation method：Polyethylene, maleic anhydride grafted ethene copolymer, polar ethylene base co-polymer, friendship
Join agent and crosslinking coagent as described above, repeating no more.In addition, can also be added in the preparation method in step (I) compound steady
Determine agent and other additives, as detailed above, repeat no more.
Present invention also offers a kind of preparation method of polyethylene composition, this method includes：(A) by 100 parts by weight
The crosslinking coagent of polyethylene, the crosslinking agent of 0.03-10 parts by weight and 0.03-8 parts by weight carries out melt blending；(B) by step (A)
Obtained blend and maleic anhydride grafted ethene copolymer, the polar ethylene copolymer of 3-15 parts by weight of 10-30 parts by weight
Carry out melt blending.
Preferably, the temperature of the melt blending is 140-160 DEG C.
In the preparation method for the polyethylene composition that the present invention is provided, the melt blending is real in double screw extruder
Apply.
Each component in the preparation method：Polyethylene, maleic anhydride grafted ethene copolymer, polar ethylene base co-polymer, friendship
Join agent and crosslinking coagent as described above, repeating no more.In addition, can also be added in the preparation method in step (B) compound steady
Determine agent and other additives, as detailed above, repeat no more.
Present invention also offers polyethylene composition prepared by the method that the present invention is provided.
Present invention also offers a kind of height of the paintable high-impact heatproof of the polyethylene composition provided containing the present invention
Polymers product.
Preferably, the product can be obtained, the heat cross-linking by the way that described polyethylene composition is carried out into heat cross-linking
Temperature be 180-230 DEG C.
Preferably, the dimethylbenzene insolubles content of the product is more than 60 weight %, and paint film remnants ratios are more than 90%, spray
Paint adhesion effect reaches more than 1 grade, and notch impact strength is more than 60kJ/m2。
It can be seen that in acquisition product there is cross-linked structure by the dimethylbenzene insolubles content of product, thus product has upper
State improved performance.
In the present invention, the processing and forming preferably can be the one or more in rotational moulding, molding, curtain coating, injection.Especially
The product for being adapted to production can be armoured case, automobile fuel tank, chemical drum etc..
The present invention will be described in detail by way of examples below.
The method of testing of involved correlation performance parameters is as follows in following examples and comparative example：
(1) impact property method of testing
Load weighted composition pellet 100mm × 120mm × 4mm mould tabletting sample preparations are taken, and intercept 10mm × 80mm
× 4mm samples, in the sample portion make a call to 2mm depth ▽ type breach, then after test room is placed 24 hours, according to ISO-180
Method is tested using CEAST impact experiment machines.
(2) bending modulus method of testing
Load weighted composition pellet 100mm × 120mm × 4mm mould tablettings are taken, and intercept 10mm × 80mm × 4mm
Sample, then after test room is placed 24 hours, is carried out using Instron5965 types testing machine according to the methods of ASTM-D 790
Test, program fetch section 0.005-0.0025mm/mm elastic mould value is the bending modulus of composition material.
(3) paint film adhesion is tested
Paint film adhesion is tested using cross-hatching.Using single-edge blade first on dry test plate (panel) in the same direction
11 lines are cut, spacing is 1mm, then vertically same spacing cuts 11 lines, it is desirable to which the edge of a knife just can in cutting
Penetrate coating and touch ground, it is otherwise invalid.100 small squares that the length of side is 1mm have so been made, then in the grid pulled
On pasted with adhesive tape, and uncover adhesive tape, then observe paint film and evaluated, be divided into 0,1,2,3,4,5 etc. 6 etc.
Level.0 grade is best, and cut edge is completely smooth, and none lattice comes off；5 grades to be worst, coating peeled off along the big fragment in cut edge or
Some grids partly or entirely come off, and area of infection is significantly greater than state when 65%.
(4) high temperature deformation method of testing
Take load weighted composition pellet 100mm × 120mm × 4mm moulds tabletting and intercept 10mm × 40mm × 4mm
Sample, by sample topography A of the sample made before cameras record high-temperature process, is then seated in 200 DEG C of constant temperature ovens and adds
Heat 25 minutes, uses the sample topography B after cameras record high-temperature process, the sample variation of contrast before and after the processing after taking-up.
(5) product dimethylbenzene insolubles content is determined
Obtained according to ASTM-D2765 using dimethylbenzene insolubles content is determined.A certain amount of polyvinyl resin chip is taken,
In the copper mesh for being wrapped in 120 mesh, it is put into the conical flask with reflux, using dimethylbenzene as solvent, boiling reflux at least 24 is small
Shi Hou, dries the content that insoluble matter is calculated to constant weight, i.e. gel content.
All it is that sample preparation is carried out at 200 DEG C with mold tableting step.
The material used 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 (test marks
Quasi- ASTM D-1238,190 DEG C, 2.16kg), density is 0.963g/cm3(testing standard：ASTM D-1505)；
Ethylene-vinyl acetate copolymer (EVA UE654-04) is purchased from Taiwan polymers Co., Ltd, melt flows speed
Rate is 30g/10min (testing standard ASTM D-1238,190 DEG C, 2.16kg), and density is 0.955g/cm3(testing standard：
ASTM D-1505)；Ethylene-vinyl alcohol copolymer (EVOH OH3003) is purchased from du pont company, and melt flow rate (MFR) is 3g/
10min (testing standard ASTM D-1238,190 DEG C, 2.16kg), density is 1.2g/cm3(testing standard：ASTM D-1505)；
Maleic anhydride grafted high density polyethylene (MAH-g-HDPE GR204) is purchased from DOW Chemical, and melt flow rate (MFR) is
12g/10min (testing standard ASTM D-1238,190 DEG C, 2.16kg), density is 0.954g/cm3(testing standard：ASTM D-
1505), grafted maleic anhydride amount is 0.6-0.8 weight % (titration)；Maleic anhydride grafted ethene based elastomeric (MAH-g-
POE GR216) be purchased from DOW Chemical, melt flow rate (MFR) be 1.25g/10min (testing standard ASTM D-1238,190 DEG C,
2.16kg), density is 0.875g/cm3(testing standard：ASTM D-1505), grafted maleic anhydride amount is 0.5-1.0 weight %
(titration)；
Peroxide cross-linking agent 2,5- dimethyl -2,5- bis- (tert-butyl peroxy base) hexane, crosslinking coagent triallyl isocyanide
Urea acid esters is purchased from Akzo Nobel N.V.；
Other chemical reagent are purchased from Chemical Reagent Co., Ltd., Sinopharm Group.
Comparative example 1
By 1000g high density polyethylene (HDPE) DMDA8007, height is passed through with 50g ethylene-vinyl acetate copolymer EVA UE654-04
Fast mixer is stirred 5 minutes to well mixed, then passes through the double screw extruder melt blending of low sheraing, granulating working procedure
It is prepared into polyethylene composition C1 (HDPE-5EVA).
Wherein, the screw slenderness ratio of the double screw extruder is 18/1, and the rotating speed of screw rod is 100 revs/min, Screw Extrusion
When blending temperature be 150 DEG C.
Impact property, resistance to elevated temperatures, paint film adhesion strength test result and the dimethylbenzene of obtained polyethylene composition are not
Molten thing content is shown in Table 1.High temperature deformation test result is shown in Fig. 1, and paint film adhesive performance test result is shown in Fig. 2.
Comparative example 2
By 1000g high density polyethylene (HDPE)s DMDA8007,6.5g peroxide cross-linking agent 2, (the tertiary fourth of 5- dimethyl -2,5- bis-
Peroxy) hexane, 10g crosslinking coagent Triallyl isocyanurates, 50g ethylene-vinyl acetate copolymer EVA UE654-04,
Be stirred 5 minutes to well mixed by homogenizer, then by the double screw extruder melt blending of low sheraing, make
Grain process is prepared into polyethylene composition C2 (XLPE-5EVA).
Wherein, the screw slenderness ratio of the double screw extruder is 18/1, and the rotating speed of screw rod is 100 revs/min, Screw Extrusion
When blending temperature be 150 DEG C.
Impact property, resistance to elevated temperatures, paint film adhesion strength test result and the dimethylbenzene of obtained polyethylene composition are not
Molten thing content is shown in Table 1.Paint film adhesive performance test result is shown in Fig. 2.
Comparative example 3
By 1000g high density polyethylene (HDPE) DMDA8007, and 50g ethylene-vinyl acetate copolymer EVA UE654-04, and
150g maleic anhydrides grafted high density polyethylene MAH-g-HDPE GR204 are stirred 5 minutes to mixing by homogenizer
Uniformly, polyethylene composition C3 (HDPE- are then prepared into by the double screw extruder melt blending of low sheraing, granulating working procedure
5EVA-15MAH-g-HDPE)。
Wherein, the screw slenderness ratio of the double screw extruder is 18/1, and the rotating speed of screw rod is 100 revs/min, Screw Extrusion
When blending temperature be 150 DEG C.
The impact property of obtained polyethylene composition, bending modulus, paint film adhesion strength test result and dimethylbenzene are insoluble
Thing content is shown in Table 1.
Embodiment 1
By 1000g high density polyethylene (HDPE)s DMDA8007,6.5g peroxide cross-linking agent 2, (the tertiary fourth of 5- dimethyl -2,5- bis-
Peroxy) hexane, 10g crosslinking coagent Triallyl isocyanurates, 100g ethylene-vinyl acetate copolymer EVA UE654-
04, it is stirred 5 minutes by homogenizer with 100g maleic anhydrides grafted high density polyethylene MAH-g-HDPE GR204
To well mixed, polyethylene composition E1 is then prepared into by the double screw extruder melt blending of low sheraing, granulating working procedure
(XLPE-10EVA-10MAH-g-HDPE)。
Wherein, the screw slenderness ratio of the double screw extruder is 18/1, and the rotating speed of screw rod is 100 revs/min, Screw Extrusion
When blending temperature be 150 DEG C.
Impact property, resistance to elevated temperatures, paint film adhesion strength test result and the dimethylbenzene of obtained polyethylene composition are not
Molten thing content is shown in Table 1.High temperature deformation test result is shown in Fig. 1, and paint film adhesive performance test result is shown in Fig. 2.
Table 1
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Embodiment 1 | |
| Impact strength (kJ/m2) | 5 | 72 | 4 | 69 |
| Paint film remnants ratios (%) | 0 | 40 | 40 | 97 |
| Paint film adhesion strength grade | 5 | 4 | 4 | 0 |
| Resistance to elevated temperatures | Extreme difference | It is fabulous | Extreme difference | It is fabulous |
| Dimethylbenzene insolubles content (weight %) | 0 | 64 | 0 | 66 |
In above-mentioned table 1, the result of comparative example 1 and embodiment 1 is visible, and cross-linked structure is not formed in comparative example 1, and it is rushed
Hit intensity, paint film adhesion and resistance to elevated temperatures all extreme differences.
For comparative example 1, the impact strength of embodiment 1 is respectively increased 1300%, and paint film remnants ratios are improved by 0
To 97%, resistance to elevated temperatures is improved as fabulous (see Fig. 1) by extreme difference.
Comparative example 2 is total to compared with the result of embodiment 1 due to not adding maleic anhydride grafted ethene in the composition of comparative example 2
Polymers, the impact strength and resistance to elevated temperatures of comparative example 2 is suitable with embodiment 1, but the paint film adhesion of embodiment 1 compares comparative example
2 are significantly improved and (are shown in Table 1 and Fig. 2).
Comparative example 3 is compared with the result of embodiment 1, due to not adding cross linker system, comparative example 3 in the composition of comparative example 3
In do not form cross-linked structure, its impact strength, resistance to elevated temperatures, paint film adhesion all extreme differences (being shown in Table 1).Embodiment 1 is combined
Thing experience processing and forming is prepared during high polymer product, can be formed in the product of acquisition between above-mentioned various polymer
Cross-linking system, the dimethylbenzene insolubles content of product is more than 60%.Compared with comparative example, hence it is evident that with improved performance, no
Only it is improved the spray painting adhesive force and mechanical shock performance of product, while being admirably enhanced the high temperature resistant creep properties of product
Energy.
Comparative example 4
By 13g peroxide cross-linking agents 2,5- dimethyl -2,5- bis- (tert-butyl peroxy base) hexane, 20g crosslinking coagent triolefins
Propyl group isocyanuric acid ester, is entered with 400g maleic anhydride grafted high density polyethylene MAH-g-HDPE GR204 by homogenizer
Then row stirring is prepared into combination in 5 minutes to well mixed by the double screw extruder melt blending of low sheraing, granulating working procedure
Thing C4A.
By 1000g high density polyethylene (HDPE) DMDA8007, carried out with 216.5 mixed composition C3A by homogenizer
Then stirring is prepared into polyethylene in 5 minutes to well mixed by the double screw extruder melt blending of low sheraing, granulating working procedure
Composition C4 (XLPE-20MAH-g-HDPE).
Wherein, the screw slenderness ratio of the double screw extruder is 18/1, and the rotating speed of screw rod is 100 revs/min, Screw Extrusion
When blending temperature be 150 DEG C.
The impact property of obtained polyethylene composition, bending modulus, paint film adhesion strength test result and dimethylbenzene are insoluble
Thing content is shown in Table 2.
Comparative example 5
By 13g peroxide cross-linking agents 2,5- dimethyl -2,5- bis- (tert-butyl peroxy base) hexane, 20g crosslinking coagent triolefins
Propyl group isocyanuric acid ester, it is poly- with 100g ethylene-vinyl acetate copolymer EVA UE654-04 and 100g maleic anhydrides grafted high density
Ethene MAH-g-HDPE GR204 are stirred 5 minutes to well mixed by homogenizer, then pass through the double of low sheraing
Screw extruder melt blending, granulating working procedure are prepared into composition C5A.
1000g high density polyethylene (HDPE) DMDA8007, the composition C4A mixed with 116.5g are carried out by homogenizer
Then stirring is prepared into poly- second in 5 minutes to well mixed by processes such as double screw extruder melt blending, the granulations of low sheraing
Ene compositions C5 (XLPE-5EVA-5MAH-g-HDPE).
Wherein, the screw slenderness ratio of the double screw extruder is 18/1, and the rotating speed of screw rod is 100 revs/min, Screw Extrusion
When blending temperature be 150 DEG C.
The impact property of obtained polyethylene composition, bending modulus, paint film adhesion strength test result and dimethylbenzene are insoluble
Thing content is shown in Table 2.
Comparative example 6
By 13g peroxide cross-linking agents 2,5- dimethyl -2,5- bis- (tert-butyl peroxy base) hexane, 20g crosslinking coagent triolefins
Propyl group isocyanuric acid ester, with 400g ethylene-vinyl acetate copolymer EVA UE654-04 and 800g maleic anhydride grafted high densities
Polyethylene MAH-g-HDPE GR204 are stirred 5 minutes to well mixed by homogenizer, then pass through low sheraing
Double screw extruder melt blending, granulating working procedure are prepared into composition C6A.
1000g high density polyethylene (HDPE) DMDA8007, the composition C6A mixed with 616.5g are carried out by homogenizer
Then stirring is prepared into polyethylene in 5 minutes to well mixed by the double screw extruder melt blending of low sheraing, granulating working procedure
Composition C6 (XLPE-20EVA-40MAH-g-HDPE).
Wherein, the screw slenderness ratio of the double screw extruder is 18/1, and the rotating speed of screw rod is 100 revs/min, Screw Extrusion
When blending temperature be 150 DEG C.
The impact property of obtained polyethylene composition, bending modulus, paint film adhesion strength test result and dimethylbenzene are insoluble
Thing content is shown in Table 2.
Comparative example 7
By 13g peroxide cross-linking agents 2,5- dimethyl -2,5- bis- (tert-butyl peroxy base) hexane, 20g crosslinking coagent triolefins
Propyl group isocyanuric acid ester, with 600g ethylene-vinyl acetate copolymer EVA UE654-04 and 400g maleic anhydride grafted high densities
Polyethylene MAH-g-HDPE GR204 are stirred 5 minutes to well mixed by homogenizer, then pass through low sheraing
Double screw extruder melt blending, granulating working procedure are prepared into composition C7A.
1000g high density polyethylene (HDPE) DMDA8007, the composition C7A mixed with 516.5g are carried out by homogenizer
Then stirring is prepared into polyethylene in 5 minutes to well mixed by the double screw extruder melt blending of low sheraing, granulating working procedure
Composition C7 (XLPE-30EVA-20MAH-g-HDPE).
Wherein, the screw slenderness ratio of the double screw extruder is 18/1, and the rotating speed of screw rod is 100 revs/min, Screw Extrusion
When blending temperature be 150 DEG C.
The impact property of obtained polyethylene composition, bending modulus, paint film adhesion strength test result and dimethylbenzene are insoluble
Thing content is shown in Table 2.
Embodiment 2
By 13g peroxide cross-linking agents 2,5- dimethyl -2,5- bis- (tert-butyl peroxy base) hexane, 20g crosslinking coagent triolefins
Propyl group isocyanuric acid ester, with 100g ethylene-vinyl acetate copolymer EVA UE654-04 and 300g maleic anhydride grafted high densities
Polyethylene MAH-g-HDPE GR204 are stirred 5 minutes to well mixed by homogenizer, then pass through low sheraing
Double screw extruder melt blending, granulating working procedure are prepared into composition E2A.
1000g high density polyethylene (HDPE) DMDA8007, the composition E2A mixed with 216.5g are carried out by homogenizer
Then stirring is prepared into polyethylene in 5 minutes to well mixed by the double screw extruder melt blending of low sheraing, granulating working procedure
Composition E2 (XLPE-5EVA-15MAH-g-HDPE).
Wherein, the screw slenderness ratio of the double screw extruder is 18/1, and the rotating speed of screw rod is 100 revs/min, Screw Extrusion
When blending temperature be 150 DEG C.
The impact property of obtained polyethylene composition, bending modulus, paint film adhesion strength test result and dimethylbenzene are insoluble
Thing content is shown in Table 2.
Embodiment 3
By 2000g high density polyethylene (HDPE)s DMDA8007,13g peroxide cross-linking agent 2, (the tertiary fourth mistake of 5- dimethyl -2,5- bis-
Epoxide) hexane, 20g crosslinking coagents Triallyl isocyanurate is stirred 5 minutes to well mixed by homogenizer,
Then composition E3B is prepared into by the double screw extruder melt blending of low sheraing, granulating working procedure.
By 50g ethylene-vinyl acetate copolymer EVA UE654-04,150g maleic anhydride grafted ethene based elastomerics MAH-
G-POE GR216, and 1016.5g compositions E3B are stirred 5 minutes to well mixed by homogenizer, then pass through
The double screw extruder melt blending of low sheraing, granulating working procedure are prepared into polyethylene composition E3 (XLPE-5EVA-15MAH-g-
POE)。
Wherein, the screw slenderness ratio of the double screw extruder is 18/1, and the rotating speed of screw rod is 100 revs/min, Screw Extrusion
When blending temperature be 150 DEG C.
The impact property of obtained polyethylene composition, bending modulus, paint film adhesion strength test result and dimethylbenzene are insoluble
Thing content is shown in Table 2.
Embodiment 4
By 2000g high density polyethylene (HDPE)s DMDA8007,13g peroxide cross-linking agent 2, (the tertiary fourth mistake of 5- dimethyl -2,5- bis-
Epoxide) hexane, 20g crosslinking coagents Triallyl isocyanurate is stirred 5 minutes to well mixed by homogenizer,
Then composition E4B is prepared into by the double screw extruder melt blending of low sheraing, granulating working procedure.
By 50g ethylene-vinyl alcohol copolymer EVOH OH3003,150g maleic anhydride grafted ethene based elastomerics MAH-g-
POE GR216, and 1016.5g compositions E4B are stirred 5 minutes to well mixed by homogenizer, then by low
The double screw extruder melt blending of shearing, granulating working procedure are prepared into polyethylene composition E4 (XLPE-5EVOH-15MAH-g-
POE)。
Wherein, the screw slenderness ratio of the double screw extruder is 18/1, and the rotating speed of screw rod is 100 revs/min, Screw Extrusion
When blending temperature be 150 DEG C.
The impact property of obtained polyethylene composition, bending modulus, paint film adhesion strength test result and dimethylbenzene are insoluble
Thing content is shown in Table 2.
Table 2
In above-mentioned table 2, comparative example 4 and embodiment 2-3 result are visible, and the paint film adhesion of comparative example 4 is fabulous, but impact
Intensity is poor, and embodiment 2-3 has 81% and 94% raising relative to the impact strength of comparative example 4 respectively.
Embodiment 2-3 is improved significantly relative to the paint film adhesion of comparative example 5, and its paint film remnants ratios are carried by 50%
Up to 90%, paint film adhesion strength grade also has 4 to bring up to 1 grade.
The impact property and paint film adhesion of comparative example 5 are poor, are non-crosslinked poly- mainly due to resin matrix
Ethene；And the paint film caking property of comparative example 6 and comparative example 7 is preferably, but impact property is slightly poor, mainly maleic anhydride
Grafted polyethylene consumption is excessive, can cause mechanical shock degradation.
Ethylene-vinyl acetate copolymer component is replaced with ethylene-vinyl alcohol group by embodiment 4 for embodiment 3
Point, the impact property of final blend, bending modulus, and paint film tackness are respectively provided with outstanding representation.
Claims (13)
1. a kind of polyethylene composition, the polyethylene composition includes：Polyethylene, maleic anhydride grafted ethene copolymer, polarity
Ethylenic copolymer, and crosslinking agent and crosslinking coagent；Wherein, relative to the polyethylene of 100 parts by weight, the maleic acid
The content of acid anhydride grafted ethylene copolymer is 10-30 parts by weight, and the content of the polar ethylene base co-polymer is 3-15 parts by weight, institute
The content for stating crosslinking agent is 0.03-10 parts by weight, and the content of the crosslinking coagent is 0.03-8 parts by weight；
The density of the maleic anhydride grafted ethene copolymer is 0.850-0.960g/cm3, melt index is 2-10g/10min；
The density of the polar ethylene base co-polymer is more than 0.875g/cm3, the polar ethylene base co-polymer is ethyl vinyl acetate second
In alkene copolymer and/or ethylene-vinyl alcohol copolymer, ethylene-vinyl acetate copolymer, the content of vinyl acetate is more than 20 weights
Measure %.
2. polyethylene composition according to claim 1, wherein, the density of the polyethylene is more than 0.935g/cm3, melting
Index is more than 0.1g/10min.
3. polyethylene composition according to claim 1, wherein, the density of the maleic anhydride grafted ethene copolymer is
0.880-0.940g/cm3, melt index is 3-8g/10min.
4. polyethylene composition according to claim 1, wherein, the density of the polar ethylene base co-polymer is 0.935-
0.965g/cm3。
5. polyethylene composition according to claim 1, wherein, the crosslinking agent is selected from the uncle of 2,5- dimethyl -2,5- bis-
Butyl peroxy -3- hexins, cumyl peroxide, the t-butylcumylperoxide, (tert-butyl groups of 2,5- dimethyl -2,5- two
Peroxy) in hexane, the oxygen rings in heptan of 3,3,5,7,7- pentamethyls -1,2,4- three and 1,4- dual-tert-butyl cumene hydroperoxides one
Plant or a variety of.
6. polyethylene composition according to claim 1, wherein, the crosslinking coagent is triallylcyanurate, three
One kind in allyl iso cyanurate, trimethylol-propane trimethacrylate and trimethylolpropane trimethacrylate or
It is a variety of.
7. a kind of method for preparing polyethylene composition any one of claim 1-6, this method includes：
(1) by the maleic anhydride grafted ethene copolymer, the polar ethylene copolymer of 3-15 parts by weight, 0.03- of 10-30 parts by weight
The crosslinking agent of 10 parts by weight and the crosslinking coagent of 0.03-8 parts by weight carry out melt blending；
(2) blend and the polyethylene of 100 parts by weight obtained step (1) carries out melt blending.
8. a kind of method for preparing polyethylene composition any one of claim 1-6, this method includes：
(I) by the polyethylene of 100 parts by weight, the maleic anhydride grafted ethene copolymer of 10-30 parts by weight, 3-15 parts by weight pole
The crosslinking coagent of sex ethylene copolymer, the crosslinking agent of 0.03-10 parts by weight and 0.03-8 parts by weight carries out low-temperature mixed；
(II) mixture for obtaining step (I) carries out melt blending.
9. a kind of method for preparing polyethylene composition any one of claim 1-6, this method includes：
(A) crosslinking coagent of the polyethylene of 100 parts by weight, the crosslinking agent of 0.03-10 parts by weight and 0.03-8 parts by weight is carried out
Melt blending；
(B) blend for obtaining step (A) and the maleic anhydride grafted ethene copolymer of 10-30 parts by weight, 3-15 parts by weight
Polar ethylene copolymer carry out melt blending.
10. polyethylene composition prepared by the method any one of claim 7-9.
11. a kind of paintable high-impact heatproof of polyethylene composition containing any one of claim 1-6 and 10
High polymer product.
12. high polymer product according to claim 11, wherein, the product is by will be any in claim 1-6 and 10
Polyethylene composition described in carries out heat cross-linking and obtained, and the temperature of the heat cross-linking is 180-230 DEG C.
13. the high polymer product according to claim 11 or 12, wherein, the dimethylbenzene insolubles content of the product is 60 weights
More than % is measured, paint film remnants ratios are more than 90%, and spray painting adhesion effect reaches more than 1 grade, and notch impact strength is more than 60kJ/
m2。
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