CN104987576A - Polyethylene composition, preparing method thereof and high polymer product capable of being painted, high in resistance and resistant to temperature - Google Patents
Polyethylene composition, preparing method thereof and high polymer product capable of being painted, high in resistance and resistant to temperature Download PDFInfo
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- CN104987576A CN104987576A CN201510400275.9A CN201510400275A CN104987576A CN 104987576 A CN104987576 A CN 104987576A CN 201510400275 A CN201510400275 A CN 201510400275A CN 104987576 A CN104987576 A CN 104987576A
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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 invention relates to a polyethylene composition, a preparing method thereof and a high polymer product capable of being painted, high in resistance and resistant to temperature. The polyethylene composition comprises polyethylene, maleic anhydride stem grafting vinyl copolymer, polarity vinyl copolymer, a cross-linking agent and coagent. For 100 parts of polyethylene, 10-30 parts of maleic anhydride stem grafting vinyl copolymer, 3-15 parts of polarity vinyl copolymer, 0.03-10 parts of cross-linking agent and 0.03-8 parts of coagent by weight are included. The painting attaching force and the mechanical impact performance of the high polymer product prepared through the composition are improved, and meanwhile the high-temperature creep resisting performance of the product is well improved.
Description
Technical field
The present invention relates to a kind of polyethylene composition, this polyethylene composition may be used for the superpolymer goods preparing paintable high-impact heatproof, also relate to the preparation method of this polyethylene composition, and the superpolymer goods of the paintable high-impact heatproof using this polyethylene composition to prepare.
Background technology
Thermoplastic olefin material refers to olefin polymer, or the uncrosslinked blend of olefin polymer and polyolefin elastomer, and they can by be polymerized or closed mixing machine physical blending obtains in the reactor.These materials are generally not paintable, and reason is that paint or coating etc. are mainly made up of polyurethanes, acrylic acid or the like, epoxies or melamine class polar materials, and thermoplastic olefin material is generally non-polar material, the non-constant of the adhesivity between them.For overcoming the paintable of this type of material, general use binding agent realizes the connection between thermoplastic olefin material and layer of lacquer, but such a process increases product expense, and and is not durable.
EP0662496A2 discloses a kind of paintable or printable composition, and said composition comprises polyolefine or polyolefine/rubber blend, and at least one additive.Particularly, polyolefine or polyolefine/rubber blend comprise polyethylene, polypropylene, their multipolymer, or they are mixed with ethylene propylene copolymer.Additive can be maleic anhydride grafted polyethylene or polypropylene, or ethylene oxide or propylene oxide polymerization preparation single function or multifunction polyester.
EP063442A1 discloses a kind of compound, the reaction product containing polypropylene and functional poly propylene and polyetheramine.Paintable, shock resistance and molding mobility that above-mentioned blend display improves.
CN1229813A discloses a kind of polymer composition that can directly paint, it comprises (1) thermoplastic olefin polymer, (2) aliphatic α is used, the alfon of β-unsaturated dicarboxylic acid acid anhydride grafting or the propylene copolymer containing ethene or 4-8 carbonatomα-olefin, (3) fusing point is lower than 116 DEG C and the acid number oxidized polyethlene wax that is less than 40, (4) with the functionalized polymeric of the acid anhydride radical reaction of graftomer, aliphatic α is used with optional (5), the polyolerin elastomer of β-unsaturated dicarboxylic acid acid anhydride grafting, (6) aliphatic α is used, the ethene polymers of β-unsaturated dicarboxylic acid acid anhydride grafting.Compared with common thermoplastic's elastomerics, above-mentioned polymkeric substance shows good paint adhesion and wearing quality.
WO9325617A2 discloses a kind of paintable thermoplastic compounds, comprise the grafted polyethylene of (A) at least 50 % by weight, wherein graft is the unsaturated compounds containing at least one double bond and at least one functional acid group based on poly at least 0.01 % by weight; And the thermoplastic polymer of (B) at least one polar functionalities.Unsaturated organic compound is maleic anhydride, and thermoplastic polymer is the polyolefine of urethane, polyester, epoxy resin, polyamine and polar functionalities.
EP0696302B2 discloses a kind of paintable composition of olefin copolymer, be characterised in that, the mixture containing polypropylene and graft modification polypropylene, the linear tetrafluoroethylene polymer of non-grafting or graft modification substantially, ethene and α, the multipolymer of beta-unsaturated carbonyl.
But in the actual use of thermoplastic olefin material, not only require paintability, but also require impact and the heat resistance of material, to meet the actual needs of product.Therefore need to consider to provide and can meet paintability, impact-resistance and durothermic thermoplastic olefin material simultaneously.
Summary of the invention
The object of the invention is to overcome that existing thermoplastic olefin material paintability is poor, erosion-resisting characteristics is poor and temperature tolerance is not enough, the defect of goods needs can not be met, provide the superpolymer goods of polyethylene composition and preparation method thereof and paintable high-impact heatproof.
To achieve these goals, the invention provides a kind of polyethylene composition, this polyethylene composition comprises: polyethylene, maleic anhydride grafted ethene multipolymer, polar ethylene base co-polymer, and linking agent and crosslinking coagent; Wherein, relative to the described polyethylene of 100 weight parts, the content of described maleic anhydride grafted ethene multipolymer is 10-30 weight part, the content of described polar ethylene base co-polymer is 3-15 weight part, the content of described linking agent is 0.03-10 weight part, and the content of described crosslinking coagent is 0.03-8 weight part.
Present invention also offers a kind of preparation method of polyethylene composition, the method comprises: the crosslinking coagent of the polar ethylene copolymer of the maleic anhydride grafted ethene multipolymer of 10-30 weight part, 3-15 weight part, the linking agent of 0.03-10 weight part and 0.03-8 weight part is carried out melt blending by (1); (2) blend step (1) obtained and the polyethylene of 100 weight parts carry out melt blending; Preferably, the temperature of described melt blending is 140-160 DEG C.
Present invention also offers a kind of preparation method of polyethylene composition, the method comprises: the crosslinking coagent of the polar ethylene copolymer of the maleic anhydride grafted ethene multipolymer of the polyethylene of 100 weight parts, 10-30 weight part, 3-15 weight part, the linking agent of 0.03-10 weight part and 0.03-8 weight part is carried out low-temperature mixed by (I); (II) mixture that step (I) obtains is carried out melt blending; Preferably, the temperature of described low-temperature mixed is 20-50 DEG C, and the temperature of described melt blending is 140-160 DEG C.
Present invention also offers a kind of preparation method of polyethylene composition, the method comprises: the linking agent of the polyethylene of 100 weight parts, 0.03-10 weight part and the crosslinking coagent of 0.03-8 weight part are carried out melt blending by (A); (B) blend step (I) obtained and the maleic anhydride grafted ethene multipolymer of 10-30 weight part, the polar ethylene copolymer of 3-15 weight part carry out melt blending; Preferably, the temperature of described melt blending is 140-160 DEG C.
Present invention also offers polyethylene composition prepared by method provided by the invention.
Present invention also offers a kind of superpolymer goods of the paintable high-impact heatproof containing polyethylene composition provided by the invention.
The present invention has better paintability, impact and durothermic superpolymer goods to provide, provide a kind of polyethylene composition, by combined to polyethylene, maleic anhydride grafted ethene multipolymer and polar ethylene base co-polymer in the composition of said composition, and compositely add specific linking agent and crosslinking coagent, said composition being experienced forming process prepares in superpolymer goods process, carry out heat cross-linking, can form the cross-linking system between above-mentioned various polymkeric substance in the goods obtained, the dimethylbenzene insolubles content of goods is more than 60%.Only simple interpolation improves the blended and goods that obtain of component compared to existing technology, and goods provided by the invention obviously have the performance of improvement, and spray paint sticking power and the mechanical shock performance of goods are improved, while goods high temperature resistant creep property be also enhanced admirably.
Goods prepared by polyethylene composition provided by the invention can have following advantage and effect:
A goods that () the present invention obtains have excellent cohesive force of spraying paint, and the adhesion effect that sprays paint reaches more than 1 grade, and common polythene goods spray paint adhesion effect below 4 grades;
B goods that () the present invention obtains have outstanding heat resistance, undeformed in 30 minutes at 200 DEG C, and common polythene goods are out of shape at 200 DEG C of Flashmelts;
C goods that () the present invention obtains have perfect mechanical shock performance, and relative common polythene goods, notched Izod impact strength is greater than 60kJ/m
2.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Fig. 1 is that molded specimens pattern left standstill before and after 25min at 200 DEG C prepared by comparative example 1 and embodiment 1-2 contrasts photo; A (), for before standing 200 DEG C, (b) is for after standing 200 DEG C of 25min.
Fig. 2 is the photo comparison that comparative example 1-2 and embodiment 1 paint film adhesive performance are tested.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of polyethylene composition, this polyethylene composition comprises: polyethylene, maleic anhydride grafted ethene multipolymer, polar ethylene base co-polymer, and linking agent and crosslinking coagent; Wherein, relative to the described polyethylene of 100 weight parts, the content of described maleic anhydride grafted ethene multipolymer is 10-30 weight part, the content of described polar ethylene base co-polymer is 3-15 weight part, the content of described linking agent is 0.03-10 weight part, and the content of described crosslinking coagent is 0.03-8 weight part.
Preferably, the content of described maleic anhydride grafted ethene multipolymer is 10-25 weight part, is more preferably 15-20 weight part.
Preferably, the content of described polar ethylene base co-polymer is 3-10 weight part, is more preferably 5-10 weight part.
Preferably, the content of described linking agent is 0.05-8 weight part, is more preferably 0.1-6 weight part.
Preferably, the content of described crosslinking coagent is 0.05-6 weight part, is more preferably 0.1-4 weight part.
According to the present invention, can performance required for end article, choose the polyethylene as matrix in polyethylene composition of the present invention.Under preferable case, in described polyethylene composition, wherein, described poly density is greater than 0.935g/cm
3, be preferably greater than 0.945g/cm
3, be more preferably 0.955-0.965g/cm
3.
Preferably, described poly melting index is greater than 0.1g/10min, is preferably 5-20g/min.Be more preferably 6-15g/min.
Can use the polyethylene be obtained commercially in the present invention, such as polyethylene DMDA8007, melting index is 8g/10min (testing standard ASTM D-1238,190 DEG C, 2.16kg), and density is 0.963g/cm
3(testing standard: ASTM D-1505).
According to the present invention, operable maleic anhydride grafted ethene multipolymer can bring required performance for end article.Under preferable case, the density of described maleic anhydride grafted ethene multipolymer is 0.850-0.960g/cm
3; Be preferably 0.880-0.940g/cm
3.
Preferably, the melting index of described maleic anhydride grafted ethene multipolymer is 2-10g/min; Be preferably 3-8g/min.
More preferably, in described maleic anhydride grafted ethene multipolymer, the grafted maleic anhydride amount of titration measuring is 0.3-1.2 % by weight; Be preferably 0.5-1.0 % by weight.
The maleic anhydride grafted ethene multipolymer be obtained commercially can be used in the present invention, such as maleic anhydride graft high density polyethylene(HDPE) (MAH-g-HDPE GR204), melt flow rate (MFR) is 12g/10min (testing standard ASTM D-1238,190 DEG C, 2.16kg), density is 0.954g/cm
3(testing standard: ASTM D-1505), grafted maleic anhydride amount is 0.6-0.8 % by weight (volumetry); 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), and density is 0.875g/cm
3(testing standard: ASTMD-1505), grafted maleic anhydride amount is 0.5-1.0 % by weight (volumetry).
According to the present invention, under preferable case, the density of described polar ethylene base co-polymer is greater than 0.875g/cm
3, be preferably 0.935-0.965g/cm
3.
According to the present invention, under preferable case, described polar ethylene base co-polymer can be ethylene-vinyl acetate copolymer (EVA) and/or ethylene-vinyl alcohol copolymer (EVOH).Be preferably ethylene-vinyl acetate copolymer; More preferably, in ethylene-vinyl acetate copolymer, the content of vinyl acetate between to for plastic is greater than 20 % by weight.
The ethylene-vinyl acetate copolymer (EVA) be obtained commercially can be used in the present invention, such as ethylene vinyl acetate (EVA UE654-04), melt flow rate (MFR) is 30g/10min (testing standard ASTM D-1238,190 DEG C, 2.16kg), density is 0.955g/cm
3(testing standard: ASTMD-1505).Ethylene-vinyl alcohol copolymer (EVOH), such as ethylene-vinyl alcohol copolymer (EVOHOH3003), melt flow rate (MFR) is 3g/10min (testing standard ASTM D-1238,190 DEG C, 2.16kg), and density is 1.2g/cm
3(testing standard: ASTM D-1505).
According to the present invention, described linking agent and crosslinking coagent are used for providing crosslinking structure, to improve the performance of goods for the goods finally obtained.Described linking agent and crosslinking coagent can provide polyethylene, being cross-linked with each other between maleic anhydride grafted ethene multipolymer and polar ethylene base co-polymer.Under preferable case, described linking agent is selected from 2,5-dimethyl-2,5-di-t-butyl peroxy-3-hexin, dicumyl peroxide, t-butylcumylperoxide, 2,5-2，5-dimethyl-2，5-di(t-butyl peroxy)2，5-hexane, 3,3,5,7,7-pentamethyl--1,2, one or more in 4-tri-oxygen ring in heptan and Isosorbide-5-Nitrae-dual-tert-butyl cumene hydroperoxide.
According to the present invention, under preferable case, described crosslinking coagent is one or more in triallylcyanurate, cyanacrylate, trimethylolpropane trimethacrylate and Viscoat 295.
In the present invention, described polyethylene composition can also contain one package stabilizer.More preferably, relative to the polyethylene of 100 weight parts, the content of described one package stabilizer is 0.1-2 weight part, is preferably 0.2-1.2 weight part.Described one package stabilizer can be the one package stabilizer of this area routine, for improving stability and the resisting ageing for long time performance of the goods prepared by described polyethylene composition.Described one package stabilizer can be commercially available prod, particularly, such as, can be Irganox 1010, Irganox 168 etc.
In the present invention, other additives that described polyethylene composition can also use containing this area routine, to improve the performance of the goods prepared by described polyethylene composition further.Other additives described can be UV additive, pigment and processing aid etc.Described UV additive is for improving the ageing-resistant performance of the goods prepared by described polyethylene composition.Described pigment may be used for the outward appearance improving the goods prepared by described polyethylene composition, and being applicable to pigment of the present invention can for commercially available fire-resistant oxidation resistant pigment product.Described processing aid may be used for improving processing characteristics when described polyethylene composition carries out forming process, such as, can be conventional releasing agent, lubricant, slipping agent etc.In described polyethylene composition, relative to the polyethylene of 100 weight parts, the content of other additives described can be 0-10 weight part, is preferably 0.01-5 weight part.
Present invention also offers a kind of preparation method of polyethylene composition, the method comprises: the crosslinking coagent of the polar ethylene copolymer of the maleic anhydride grafted ethene multipolymer of 10-30 weight part, 3-15 weight part, the linking agent of 0.03-10 weight part and 0.03-8 weight part is carried out melt blending by (1); (2) blend step (1) obtained and the polyethylene of 100 weight parts carry out melt blending.
Preferably, the temperature of described melt blending is 140-160 DEG C.
In the preparation method of polyethylene composition provided by the invention, described melt blending is all implemented in twin screw extruder.
Each component in this preparation method: polyethylene, maleic anhydride grafted ethene multipolymer, polar ethylene base co-polymer, linking agent and crosslinking coagent are described above, repeat no more.In addition, one package stabilizer and other additives can also be added in this preparation method in step (1), as detailed above, repeat no more.
Present invention also offers a kind of preparation method of polyethylene composition, the method comprises: the crosslinking coagent of the polar ethylene copolymer of the maleic anhydride grafted ethene multipolymer of the polyethylene of 100 weight parts, 10-30 weight part, 3-15 weight part, the linking agent of 0.03-10 weight part and 0.03-8 weight part is carried out low-temperature mixed by (I); (II) mixture that step (I) obtains is carried out melt blending.
Preferably, the temperature of described low-temperature mixed is 20-50 DEG C, and the temperature of described melt blending is 140-160 DEG C.
In the preparation method of polyethylene composition provided by the invention, described low-temperature mixed can be implemented in high speed mixer; Described melt blending is all implemented in twin screw extruder.
Each component in this preparation method: polyethylene, maleic anhydride grafted ethene multipolymer, polar ethylene base co-polymer, linking agent and crosslinking coagent are described above, repeat no more.In addition, one package stabilizer and other additives can also be added in this preparation method in step (I), as detailed above, repeat no more.
Present invention also offers a kind of preparation method of polyethylene composition, the method comprises: the linking agent of the polyethylene of 100 weight parts, 0.03-10 weight part and the crosslinking coagent of 0.03-8 weight part are carried out melt blending by (A); (B) blend step (A) obtained and the maleic anhydride grafted ethene multipolymer of 10-30 weight part, the polar ethylene copolymer of 3-15 weight part carry out melt blending.
Preferably, the temperature of described melt blending is 140-160 DEG C.
In the preparation method of polyethylene composition provided by the invention, described melt blending is all implemented in twin screw extruder.
Each component in this preparation method: polyethylene, maleic anhydride grafted ethene multipolymer, polar ethylene base co-polymer, linking agent and crosslinking coagent are described above, repeat no more.In addition, one package stabilizer and other additives can also be added in this preparation method in step (B), as detailed above, repeat no more.
Present invention also offers polyethylene composition prepared by method provided by the invention.
Present invention also offers a kind of superpolymer goods of the paintable high-impact heatproof containing polyethylene composition provided by the invention.
Preferably, these goods obtain by described polyethylene composition is carried out heat cross-linking, and the temperature of described heat cross-linking is 180-230 DEG C.
Preferably, the dimethylbenzene insolubles content of these goods is more than 60 % by weight, and the remaining ratio of paint film is greater than 90%, and the adhesion effect that sprays paint reaches more than 1 grade, and notched Izod impact strength is greater than 60kJ/m
2.
Can find out to obtain in goods to there is crosslinking structure by the dimethylbenzene insolubles content of goods, goods have the performance of above-mentioned improvement thus.
In the present invention, described forming process can be preferably one or more in rotational moulding, mold pressing, curtain coating, injection moulding.The goods being particularly suitable for producing can be armoured case, automobile fuel tank, chemical drum etc.
Below will be described the present invention by embodiment.
The testing method of correlation performance parameters involved in following examples and comparative example is as follows:
(1) impact property testing method
Get load weighted composition pellet 100mm × 120mm × 4mm mould compressing tablet sample preparation, and intercept 10mm × 80mm × 4mm sample, a 2mm dark ▽ type breach is made a call in portion in the sample to which, then after test room places 24 hours, uses CEAST impact experiment machine to test according to ISO-180 method.
(2) modulus in flexure testing method
Get load weighted composition pellet 100mm × 120mm × 4mm mould compressing tablet, and intercept 10mm × 80mm × 4mm sample, then after test room places 24 hours, use Instron5965 type trier to test according to ASTM-D 790 method, the elastic mould value of program fetch section 0.005-0.0025mm/mm is the modulus in flexure of composition material.
(3) paint film adhesion test
Paint film adhesion adopts cross-hatching to test.Adopt single-edge blade first on the test plate (panel) of drying, to cut 11 lines in the same direction, spacing is 1mm, and then vertically same spacing cuts 11 lines, requires that the edge of a knife just in time can penetrate coating and touch ground in cutting, otherwise invalid.Obtain 100 little squares that the length of side is 1mm like this, then pasted with scotch tape on the grid pulled, and uncovered adhesive tape, then observed paint film evaluation, be divided into 6 grades such as 0,1,2,3,4,5.0 grade is best, and cut edge is completely level and smooth, and none lattice comes off; 5 grades is the poorest, and along cut edge, large fragment peels off or coming off partly or entirely appears in some grids coating, and area of infection is obviously greater than state when 65%.
(4) high temperature deformation testing method
Get load weighted composition pellet 100mm × 120mm × 4mm mould compressing tablet and intercept 10mm × 40mm × 4mm sample, by the sample topography A before the sample cameras record pyroprocessing that makes, then be seated in 200 DEG C of constant temperature ovens and heat 25 minutes, with the sample topography B after cameras record pyroprocessing after taking out, the sample variation before and after contrast treatment.
(5) goods dimethylbenzene insolubles content measures
Mensuration dimethylbenzene insolubles content is adopted to obtain according to ASTM-D2765.Get a certain amount of polyvinyl resin chip, being wrapped in 120 object copper mesh, putting into the Erlenmeyer flask with reflux, take dimethylbenzene as solvent, and boiling reflux, after at least 24 hours, is dried to constant weight, calculates the content of insolubles, i.e. gel content.
All carry out sample preparation 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 melting index is 8g/10min (testing standard ASTM D-1238,190 DEG C, 2.16kg), and density is 0.963g/cm
3(testing standard: ASTM D-1505);
Ethylene vinyl acetate (EVA UE654-04) is purchased from Taiwan polymers company limited, and melt flow rate (MFR) is 30g/10min (testing standard ASTM D-1238,190 DEG C, 2.16kg), and density is 0.955g/cm
3(testing standard: ASTM D-1505); Ethylene-vinyl alcohol copolymer (EVOHOH3003) is purchased from du pont company, and melt flow rate (MFR) is 3g/10min (testing standard ASTMD-1238,190 DEG C, 2.16kg), and density is 1.2g/cm
3(testing standard: ASTM D-1505);
Maleic anhydride graft high density polyethylene(HDPE) (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), and density is 0.954g/cm
3(testing standard: ASTM D-1505), grafted maleic anhydride amount is 0.6-0.8 % by weight (volumetry); Maleic anhydride grafted ethene based elastomeric (MAH-g-POE GR216) is purchased from DOW Chemical, and melt flow rate (MFR) is 1.25g/10min (testing standard ASTM D-1238,190 DEG C, 2.16kg), and density is 0.875g/cm
3(testing standard: ASTM D-1505), grafted maleic anhydride amount is 0.5-1.0 % by weight (volumetry);
Peroxide cross-linking agent 2,5-dimethyl-2,5-bis-(tert-butyl peroxy base) hexane, crosslinking coagent cyanacrylate is purchased from Akzo Nobel N.V.;
Other chemical reagent is all purchased from Chemical Reagent Co., Ltd., Sinopharm Group.
Comparative example 1
By 1000g high density polyethylene(HDPE) DMDA8007, carrying out stirring 5 minutes to mixing with 50g ethylene vinyl acetate EVAUE654-04 by homogenizer, being then prepared into polyethylene composition C1 (HDPE-5EVA) by the twin screw extruder melt blending of low sheraing, granulating working procedure.
Wherein, the screw slenderness ratio of described twin screw extruder is 18/1, and the rotating speed of screw rod is 100 revs/min, and blending temperature during Screw Extrusion is 150 DEG C.
The impact property of obtained polyethylene composition, resistance to elevated temperatures, paint film clinging power test result and dimethylbenzene insolubles content are 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) DMDA8007,6.5g peroxide cross-linking agent 2,5-dimethyl-2,5-bis-(tert-butyl peroxy base) hexane, 10g crosslinking coagent cyanacrylate, 50g ethylene-vinyl acetate copolymer EVA UE654-04, carries out stirring 5 minutes to mixing by homogenizer, is then prepared into polyethylene composition C2 (XLPE-5EVA) by the twin screw extruder melt blending of low sheraing, granulating working procedure.
Wherein, the screw slenderness ratio of described twin screw extruder is 18/1, and the rotating speed of screw rod is 100 revs/min, and blending temperature during Screw Extrusion is 150 DEG C.
The impact property of obtained polyethylene composition, resistance to elevated temperatures, paint film clinging power test result and dimethylbenzene insolubles content are in table 1.Paint film adhesive performance test result is shown in Fig. 2.
Comparative example 3
By 1000g high density polyethylene(HDPE) DMDA8007, with 50g ethylene-vinyl acetate copolymer EVAUE654-04, and 150g maleic anhydride graft high density polyethylene(HDPE) MAH-g-HDPE GR204 carries out stirring 5 minutes to mixing by homogenizer, be then prepared into polyethylene composition C3 (HDPE-5EVA-15MAH-g-HDPE) by the twin screw extruder melt blending of low sheraing, granulating working procedure.
Wherein, the screw slenderness ratio of described twin screw extruder is 18/1, and the rotating speed of screw rod is 100 revs/min, and blending temperature during Screw Extrusion is 150 DEG C.
The impact property of obtained polyethylene composition, modulus in flexure, paint film clinging power test result and dimethylbenzene insolubles content are in table 1.
Embodiment 1
By 1000g high density polyethylene(HDPE) DMDA8007,6.5g peroxide cross-linking agent 2,5-dimethyl-2,5-bis-(tert-butyl peroxy base) hexane, 10g crosslinking coagent cyanacrylate, 100g ethylene-vinyl acetate copolymer EVA UE654-04, carrying out stirring 5 minutes to mixing with 100g maleic anhydride graft high density polyethylene(HDPE) MAH-g-HDPE GR204 by homogenizer, being then prepared into polyethylene composition E1 (XLPE-10EVA-10MAH-g-HDPE) by the twin screw extruder melt blending of low sheraing, granulating working procedure.
Wherein, the screw slenderness ratio of described twin screw extruder is 18/1, and the rotating speed of screw rod is 100 revs/min, and blending temperature during Screw Extrusion is 150 DEG C.
The impact property of obtained polyethylene composition, resistance to elevated temperatures, paint film clinging power test result and dimethylbenzene insolubles content are 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 | |
| Shock strength (kJ/m 2) | 5 | 72 | 4 | 69 |
| The remaining ratio (%) of paint film | 0 | 40 | 40 | 97 |
| Paint film clinging power grade | 5 | 4 | 4 | 0 |
| Resistance to elevated temperatures | Extreme difference | Fabulous | Extreme difference | Fabulous |
| Dimethylbenzene insolubles content (% by weight) | 0 | 64 | 0 | 66 |
By in above-mentioned table 1, comparative example 1 is visible with the result of embodiment 1, does not form crosslinking structure, its shock strength, paint film adhesion and resistance to elevated temperatures all extreme differences in comparative example 1.
For comparative example 1, the shock strength of embodiment 1 improves 1300% respectively, and the remaining ratio of paint film brings up to 97% by 0, and resistance to elevated temperatures is improved as fabulous (see Fig. 1) by extreme difference.
Comparative example 2 is compared with embodiment 1 result, maleic anhydride grafted ethene multipolymer is not added in composition due to comparative example 2, the shock strength of comparative example 2 is suitable with embodiment 1 with resistance to elevated temperatures, but the paint film adhesion of embodiment 1 is significantly improved (see table 1 and Fig. 2) than comparative example 2.
Comparative example 3, compared with embodiment 1 result, does not add cross linker system in the composition due to comparative example 3, does not form crosslinking structure in comparative example 3, and its shock strength, resistance to elevated temperatures, paint film adhesion be extreme difference (see table 1) all.Embodiment 1 composition experience forming process is prepared in superpolymer goods process, and can form the cross-linking system between above-mentioned various polymkeric substance in the goods obtained, the dimethylbenzene insolubles content of goods is more than 60%.Compared with comparative example, obviously there is the performance of improvement, not only make spray paint sticking power and the mechanical shock performance of goods be improved, be enhanced the high temperature resistant creep property of goods simultaneously admirably.
Comparative example 4
By 13g peroxide cross-linking agent 2,5-dimethyl-2,5-bis-(tert-butyl peroxy base) hexane, 20g crosslinking coagent cyanacrylate, carrying out stirring 5 minutes to mixing with 400g maleic anhydride graft high density polyethylene(HDPE) MAH-g-HDPEGR204 by homogenizer, being then prepared into composition C4A by the twin screw extruder melt blending of low sheraing, granulating working procedure.
By 1000g high density polyethylene(HDPE) DMDA8007, carrying out stirring 5 minutes to mixing with 216.5 mixed composition C3A by homogenizer, being then prepared into polyethylene composition C4 (XLPE-20MAH-g-HDPE) by the twin screw extruder melt blending of low sheraing, granulating working procedure.
Wherein, the screw slenderness ratio of described twin screw extruder is 18/1, and the rotating speed of screw rod is 100 revs/min, and blending temperature during Screw Extrusion is 150 DEG C.
The impact property of obtained polyethylene composition, modulus in flexure, paint film clinging power test result and dimethylbenzene insolubles content are in table 2.
Comparative example 5
By 13g peroxide cross-linking agent 2,5-dimethyl-2,5-bis-(tert-butyl peroxy base) hexane, 20g crosslinking coagent cyanacrylate, carrying out stirring 5 minutes to mixing with 100g ethylene vinyl acetate EVA UE654-04 and 100g maleic anhydride graft high density polyethylene(HDPE) MAH-g-HDPE GR204 by homogenizer, being then prepared into composition C5A by the twin screw extruder melt blending of low sheraing, granulating working procedure.
By 1000g high density polyethylene(HDPE) DMDA8007, carrying out stirring 5 minutes to mixing with the mixed composition C4A of 116.5g by homogenizer, being then prepared into polyethylene composition C5 (XLPE-5EVA-5MAH-g-HDPE) by the operation such as twin screw extruder melt blending, granulation of low sheraing.
Wherein, the screw slenderness ratio of described twin screw extruder is 18/1, and the rotating speed of screw rod is 100 revs/min, and blending temperature during Screw Extrusion is 150 DEG C.
The impact property of obtained polyethylene composition, modulus in flexure, paint film clinging power test result and dimethylbenzene insolubles content are in table 2.
Comparative example 6
By 13g peroxide cross-linking agent 2,5-dimethyl-2,5-bis-(tert-butyl peroxy base) hexane, 20g crosslinking coagent cyanacrylate, carrying out stirring 5 minutes to mixing with 400g ethylene-vinyl acetate copolymer EVA UE654-04 and 800g maleic anhydride graft high density polyethylene(HDPE) MAH-g-HDPE GR204 by homogenizer, being then prepared into composition C6A by the twin screw extruder melt blending of low sheraing, granulating working procedure.
By 1000g high density polyethylene(HDPE) DMDA8007, carrying out stirring 5 minutes to mixing with the mixed composition C6A of 616.5g by homogenizer, being then prepared into polyethylene composition C6 (XLPE-20EVA-40MAH-g-HDPE) by the twin screw extruder melt blending of low sheraing, granulating working procedure.
Wherein, the screw slenderness ratio of described twin screw extruder is 18/1, and the rotating speed of screw rod is 100 revs/min, and blending temperature during Screw Extrusion is 150 DEG C.
The impact property of obtained polyethylene composition, modulus in flexure, paint film clinging power test result and dimethylbenzene insolubles content are in table 2.
Comparative example 7
By 13g peroxide cross-linking agent 2,5-dimethyl-2,5-bis-(tert-butyl peroxy base) hexane, 20g crosslinking coagent cyanacrylate, carrying out stirring 5 minutes to mixing with 600g ethylene-vinyl acetate copolymer EVA UE654-04 and 400g maleic anhydride graft high density polyethylene(HDPE) MAH-g-HDPE GR204 by homogenizer, being then prepared into composition C7A by the twin screw extruder melt blending of low sheraing, granulating working procedure.
By 1000g high density polyethylene(HDPE) DMDA8007, carrying out stirring 5 minutes to mixing with the mixed composition C7A of 516.5g by homogenizer, being then prepared into polyethylene composition C7 (XLPE-30EVA-20MAH-g-HDPE) by the twin screw extruder melt blending of low sheraing, granulating working procedure.
Wherein, the screw slenderness ratio of described twin screw extruder is 18/1, and the rotating speed of screw rod is 100 revs/min, and blending temperature during Screw Extrusion is 150 DEG C.
The impact property of obtained polyethylene composition, modulus in flexure, paint film clinging power test result and dimethylbenzene insolubles content are in table 2.
Embodiment 2
By 13g peroxide cross-linking agent 2,5-dimethyl-2,5-bis-(tert-butyl peroxy base) hexane, 20g crosslinking coagent cyanacrylate, carrying out stirring 5 minutes to mixing with 100g ethylene-vinyl acetate copolymer EVA UE654-04 and 300g maleic anhydride graft high density polyethylene(HDPE) MAH-g-HDPE GR204 by homogenizer, being then prepared into composition E2A by the twin screw extruder melt blending of low sheraing, granulating working procedure.
By 1000g high density polyethylene(HDPE) DMDA8007, carrying out stirring 5 minutes to mixing with the mixed composition E2A of 216.5g by homogenizer, being then prepared into polyethylene composition E2 (XLPE-5EVA-15MAH-g-HDPE) by the twin screw extruder melt blending of low sheraing, granulating working procedure.
Wherein, the screw slenderness ratio of described twin screw extruder is 18/1, and the rotating speed of screw rod is 100 revs/min, and blending temperature during Screw Extrusion is 150 DEG C.
The impact property of obtained polyethylene composition, modulus in flexure, paint film clinging power test result and dimethylbenzene insolubles content are in table 2.
Embodiment 3
By 2000g high density polyethylene(HDPE) DMDA8007,13g peroxide cross-linking agent 2,5-dimethyl-2,5-bis-(tert-butyl peroxy base) hexane, 20g crosslinking coagent cyanacrylate carries out stirring 5 minutes to mixing by homogenizer, is then prepared into composition E3B by the twin screw extruder melt blending of low sheraing, granulating working procedure.
By 50g ethylene vinyl acetate EVA UE654-04,150g maleic anhydride grafted ethene based elastomeric MAH-g-POE GR216, carrying out stirring 5 minutes to mixing with 1016.5g composition E3B by homogenizer, being then prepared into polyethylene composition E3 (XLPE-5EVA-15MAH-g-POE) by the twin screw extruder melt blending of low sheraing, granulating working procedure.
Wherein, the screw slenderness ratio of described twin screw extruder is 18/1, and the rotating speed of screw rod is 100 revs/min, and blending temperature during Screw Extrusion is 150 DEG C.
The impact property of obtained polyethylene composition, modulus in flexure, paint film clinging power test result and dimethylbenzene insolubles content are in table 2.
Embodiment 4
By 2000g high density polyethylene(HDPE) DMDA8007,13g peroxide cross-linking agent 2,5-dimethyl-2,5-bis-(tert-butyl peroxy base) hexane, 20g crosslinking coagent cyanacrylate carries out stirring 5 minutes to mixing by homogenizer, is then prepared into composition E4B by the twin screw extruder melt blending of low sheraing, granulating working procedure.
By 50g ethylene-vinyl alcohol copolymer EVOH OH3003,150g maleic anhydride grafted ethene based elastomeric MAH-g-POE GR216, carrying out stirring 5 minutes to mixing with 1016.5g composition E4B by homogenizer, being then prepared into polyethylene composition E4 (XLPE-5EVOH-15MAH-g-POE) by the twin screw extruder melt blending of low sheraing, granulating working procedure.
Wherein, the screw slenderness ratio of described twin screw extruder is 18/1, and the rotating speed of screw rod is 100 revs/min, and blending temperature during Screw Extrusion is 150 DEG C.
The impact property of obtained polyethylene composition, modulus in flexure, paint film clinging power test result and dimethylbenzene insolubles content are in table 2.
Table 2
By in above-mentioned table 2, comparative example 4 is visible with the result of embodiment 2-3, and comparative example 4 paint film adhesion is fabulous, but shock strength is poor, and embodiment 2-3 has the raising of 81% and 94% respectively relative to the shock strength of comparative example 4.
Embodiment 2-3 improves significantly relative to the paint film adhesion of comparative example 5, and the remaining ratio of its paint film is increased to 90% by 50%, and paint film clinging power grade also has 4 to bring up to 1 grade.
The impact property of comparative example 5 and paint film adhesion are all poor, mainly because resin matrix is non-cross-linked polyvinyl; And the paint film cohesiveness of comparative example 6 and comparative example 7 is better, but impact property is slightly poor, and mainly maleic anhydride grafted polyethylene consumption is too much, can cause mechanical shock degradation.
Ethylene-vinyl acetate copolymer component, for embodiment 3, is replaced with ethylene-vinyl alkoxide component by embodiment 4, the impact property of final blend, modulus in flexure, and paint film tackyness all has outstanding representation.
Claims (13)
1. a polyethylene composition, this polyethylene composition comprises: polyethylene, maleic anhydride grafted ethene multipolymer, polar ethylene base co-polymer, and linking agent and crosslinking coagent; Wherein, relative to the described polyethylene of 100 weight parts, the content of described maleic anhydride grafted ethene multipolymer is 10-30 weight part, the content of described polar ethylene base co-polymer is 3-15 weight part, the content of described linking agent is 0.03-10 weight part, and the content of described crosslinking coagent is 0.03-8 weight part.
2. polyethylene composition according to claim 1, wherein, described poly density is greater than 0.935g/cm
3, melting index is greater than 0.1g/10min.
3. polyethylene composition according to claim 1, wherein, the density of described maleic anhydride grafted ethene multipolymer is 0.850-0.960g/cm
3, melting index is 2-10g/min.
4. polyethylene composition according to claim 1, wherein, the density of described polar ethylene base co-polymer is greater than 0.875g/cm
3; Preferably, described polar ethylene base co-polymer is ethylene-vinyl acetate copolymer and/or ethylene-vinyl alcohol copolymer.
5. polyethylene composition according to claim 1, wherein, described linking agent is selected from 2,5-dimethyl-2,5-di-t-butyl peroxy-3-hexin, dicumyl peroxide, t-butylcumylperoxide, 2,5-dimethyl-2,5-bis-(t-butylperoxy) hexane, 3,3,5,7,7-pentamethyl--1, one or more in 2,4-tri-oxygen ring in heptan and Isosorbide-5-Nitrae-dual-tert-butyl cumene hydroperoxide.
6. polyethylene composition according to claim 1, wherein, described crosslinking coagent is one or more in triallylcyanurate, cyanacrylate, trimethylolpropane trimethacrylate and Viscoat 295.
7. prepare a method for polyethylene composition according to any one of claim 1-6, the method comprises:
(1) crosslinking coagent of the polar ethylene copolymer of the maleic anhydride grafted ethene multipolymer of 10-30 weight part, 3-15 weight part, the linking agent of 0.03-10 weight part and 0.03-8 weight part is carried out melt blending;
(2) blend step (1) obtained and the polyethylene of 100 weight parts carry out melt blending.
8. prepare a method for polyethylene composition according to any one of claim 1-6, the method comprises:
(I) crosslinking coagent of the polar ethylene copolymer of the maleic anhydride grafted ethene multipolymer of the polyethylene of 100 weight parts, 10-30 weight part, 3-15 weight part, the linking agent of 0.03-10 weight part and 0.03-8 weight part is carried out low-temperature mixed;
(II) mixture that step (I) obtains is carried out melt blending.
9. prepare a method for polyethylene composition according to any one of claim 1-6, the method comprises:
(A) linking agent of the polyethylene of 100 weight parts, 0.03-10 weight part and the crosslinking coagent of 0.03-8 weight part are carried out melt blending;
(B) blend step (A) obtained and the maleic anhydride grafted ethene multipolymer of 10-30 weight part, the polar ethylene copolymer of 3-15 weight part carry out melt blending.
10. polyethylene composition prepared by the method according to any one of claim 7-9.
The superpolymer goods of 11. 1 kinds of paintable high-impact heatproofs containing the polyethylene composition according to any one of claim 1-6 and 10.
12. superpolymer goods according to claim 11, wherein, these goods obtain by the polyethylene composition according to any one of claim 1-6 and 10 is carried out heat cross-linking, and the temperature of described heat cross-linking is 180-230 DEG C.
13. superpolymer goods according to claim 11 or 12, wherein, the dimethylbenzene insolubles content of these goods is more than 60 % by weight, and the remaining ratio of paint film is greater than 90%, and the adhesion effect that sprays paint reaches more than 1 grade, and notched Izod impact strength is greater than 60kJ/m
2.
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