CN106608996A - Polyethylene composition and preparation method thereof, and modified crosslinked polyethylene - Google Patents
Polyethylene composition and preparation method thereof, and modified crosslinked polyethylene Download PDFInfo
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- CN106608996A CN106608996A CN201510696146.9A CN201510696146A CN106608996A CN 106608996 A CN106608996 A CN 106608996A CN 201510696146 A CN201510696146 A CN 201510696146A CN 106608996 A CN106608996 A CN 106608996A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/247—Heating methods
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/16—Ethene-propene or ethene-propene-diene copolymers
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Abstract
The invention discloses a polyethylene composition and a preparation method thereof, and modified crosslinked polyethylene. With the total weight of the composition as a benchmark, the composition comprises 50 to 80 wt% of polyethylene, 1 to 5 wt% of a polyolefin elastomer, 1 to 10 wt% of a compatibilizer, 5 to 40 wt% of a surface treatment chopped glass fiber, 0 to 2 wt% of a nucleating agent, 0.3 to 2 wt% of a crosslinking agent, 0.1 to 1 wt% of a crosslinking agent, and 0.1 to 1 wt% of an antioxidant and a processing aid; the surface treatment chopped glass fiber is obtained by surface treatment of a chopped glass fiber with a coupling agent; the coupling agent is at least one of a silane coupling agent, a titanate coupling agent and a borate coupling agent, and the end group of the silane coupling agent contains at least one of an amino group, an acryloyl group and a ureido group. The modified crosslinked polyethylene is further obtained from the composition, and improved properties can be achieved.
Description
Technical field
The present invention relates to a kind of polyethylene composition and preparation method thereof, and handed over by the polyethylene composition
The modified crosslinking polyethylene that connection reaction is obtained.
Background technology
Polyethylene is one of the most important organic material for being widely used in every field, can be by as squeezed
The forming methods such as modeling, blowing, injection, film modeling, rotational moulding are processed into various different shape products.However,
Simple polythene material cannot meet many applications to intensity, modulus, toughness, heat resistance high request.
Typically can strengthen to improve the performance of polythene material with crosslinked and filling.
CN103627057A discloses a kind of continuous glass fibre strengthens polyethylene prepreg tape, by comprising with
The component of lower weight portion is made：100 parts of base polyethylene, toughener 5-8 parts, compatilizer 3-5 parts,
Antioxidant 0.6-1.2 parts, glass fibre 40-60 parts.This invention is not crosslinked to polyethylene.
CN102691832B discloses a kind of preparation method of fiberglass reinforced HDPE binary wall twisting and pipes, bag
Include a, prepare high density polyethylene (HDPE) compound：100 parts of high density polyethylene (HDPE), peroxide initiator 0.02-2
Part, polyfunctional monomer 0.2-5 parts, high molecular weight compatibilizer 2-10 parts, antioxidant 0.05-0.5 parts；b、
Prepare modified long glass fibres：100 parts of long glass fibres, silane coupler 0.5-5 parts；C, will be highly dense
Degree polyethylene compound presses 60-95 with modified glass fibre:The weight proportion of 5-40 is in double screw extruder
On carry out reaction co-extrusion, Jing moulds extrusion and Vacuum shaping obtain glass fiber reinforcement high density polyethylene (HDPE)
Hollow square tube；D, by glass fiber reinforcement high density polyethylene (HDPE) hollow square tube Jing spiral windings and expect heat
Melten gel welding machine is fabricated to fiberglass reinforced HDPE binary wall twisting and pipes.
But, short glass fiber is different from long glass fibres, how to enable short glass fiber fine
Be filled in polyethylene crosslinking system, improve the performance of polythene material, there is provided more preferable mechanical property,
Need to provide new technology.
The content of the invention
The invention aims to solve the performance for how improving cross-linking polyethylene materials, staple glass is made
Fiber is filled into the problem in crosslinked polyethylene, there is provided a kind of polyethylene composition and preparation method thereof and
Modified crosslinking polyethylene.
To achieve these goals, the present invention provides a kind of polyethylene composition, with the gross weight of said composition
On the basis of amount, the polyethylene of said composition including 50-80 weight %, the polyolefin elastomer of 1-5 weight %,
The compatilizer of 1-10 weight %, the surface treatment short glass fiber of 5-40 weight %, 0-2 weight % into
The crosslinking coagent of core agent, the crosslinking agent of 0.3-2 weight % and 0.1-1 weight %, and 0.1-1 weight %
Antioxidant and processing aid；Wherein, the surface treatment short glass fiber is by the way that staple glass is fine
Tie up to be obtained after coupling agent surface treatment；The coupling agent is silane coupler, titanate coupling agent and boron
At least one in acid esters coupling agent, the end group of the silane coupler contains amino group, acryloyl-oxy
At least one in base group and ureido groups.
Preferably, the polyolefin elastomer is ethene-C4-8Olefin copolymer, EP rubbers, ternary second
At least one in third rubber and ethylene-vinyl acetate copolymer；The compatilizer is that maleic anhydride is grafted second
Alkene-octene copolymer and/or glycidyl methacrylate graft ethylene-octene copolymer.
Preferably, the impact strength of modified crosslinking polyethylene is more than obtained in the polyethylene composition
16KJ/m2, more than 1600MPa, heat distortion temperature is more than 80 DEG C, and high temperature resistant creep rate is little for bending modulus
In 3%.
Present invention also offers a kind of method of the polyethylene composition for preparing the present invention, including：(1) will
Coupling agent is surface-treated to short glass fiber and is dried, and obtains being surface-treated short glass fiber；
(2) by polyethylene, polyolefin elastomer, compatilizer, nucleator, crosslinking agent, crosslinking coagent, anti-
Oxygen agent, processing aid and surface treatment short glass fiber are mixed, and the mixture for obtaining is carried out
Extruding pelletization.
Present invention also offers a kind of modified crosslinking polyethylene, the modified crosslinking polyethylene is by by the present invention
Polyethylene composition carry out cross-linking reaction and obtain.
Material property in order to improve crosslinked polyethylene of the invention, by selecting to add staple glass fine
Dimension is filled, while containing in the polyethylene composition for providing at the surface of specific coupling agent treatment
Reason short glass fiber, and with the polyolefin elastomer of specific consumption, polyethylene, compatilizer and filling
Short glass fiber is mutually cooperateed with, it is possible to achieve short glass fiber is more preferable, be more effectively carried out filling, changes
Enter the material property of crosslinked polyethylene.Correspondingly, in the preparation process of the said composition that the present invention is provided,
Take and carry out in advance short glass fiber surface to be modified, then with preferred polyethylene, polyolefin elastomer,
Crosslinking agent, crosslinking coagent and other auxiliary agents are mixed with special ratios, there is provided the final modified friendship for obtaining
Connection polyethylene with better performance improvement, with high-modulus, high impact, high temperature resistant croop property and
Heat resistance.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The present invention provides a kind of polyethylene composition, on the basis of the gross weight of said composition, said composition
Polyethylene, the polyolefin elastomer of 1-5 weight %, 1-10 weight % including 50-80 weight % it is compatible
Agent, the surface treatment short glass fiber of 5-40 weight %, the nucleator of 0-2 weight %, 0.3-2 weight
The crosslinking agent of % and the crosslinking coagent of 0.1-1 weight %, and 0.1-1 weight % antioxidant and processing help
Agent；Wherein, it is described surface treatment short glass fiber be by by short glass fiber with coupling agent surface
Obtain after process；The coupling agent is in silane coupler, titanate coupling agent and boric acid ester coupler
At least one, the end group of the silane coupler contains amino group, acryloxy group and urea groups base
At least one in group.
, according to the invention it is preferred in the case of, the impact of modified crosslinking polyethylene is strong obtained in the composition
Degree is more than 16KJ/m2, more than 1600MPa, heat distortion temperature is more than 80 DEG C, and high temperature resistant is compacted for bending modulus
Variability is less than 3%.
According to the present invention, the coupling agent of specific consumption is selected for short glass fiber, under preferable case,
The surface treatment short glass fiber is 100 with the weight ratio of the coupling agent：0.5 to 100：3,
Preferably 100:0.8 to 100：2.Final modified crosslinking polyethylene can be provided with more excellent performance.
In the present invention, the fibre diameter of the short glass fiber is 8-15 μm, preferably 9-13 μm；
Length is 3-8mm, preferably 3-5mm.Short glass fiber with above-mentioned diameter and length is being used for
More preferable material property can be provided when preparing modified crosslinking polyethylene.
According to the present invention, can aid in short glass fiber and be filled into be crosslinked from specific coupling agent and gather
In ethene.Preferably, the coupling agent is 3- aminopropyl triethoxysilanes, 3- methyl (acryloxy)
Propyl trimethoxy silicane, VTES, 3- ureido-propyl trimethoxy silanes and metatitanic acid
At least one in ester coupling agent.
According to the present invention it is possible to polyolefin elastomer is added, and the polyolefin elastomer for selecting can be with institute
Stating polyethylene has preferable synergy, can further improve short glass fiber in crosslinked polyethylene
Fillibility, improve the performance of final modified crosslinking polyethylene.Under preferable case, the polyethylene with
The weight ratio of the polyolefin elastomer is 5:1 to 80:1, preferably 10:1 to 77:1.
In accordance with the present invention it is preferred that, the polyolefin elastomer is ethene-C4-8Olefin copolymer, second third
At least one in rubber, ethylene propylene diene rubber and ethylene-vinyl acetate copolymer.Wherein, the ethene
-C4-8Olefin copolymer can be by vinyl monomer and C4-8The chemical combination that olefinic monomer Jing copolyreaction is obtained
Thing.Such as ethylene-butadiene copolymer or ethylene-octene copolymer etc..
It is preferred that the polyolefin elastomer is ternary ethylene-propylene copolymer and/or ethylene-octene copolymer.
In the present invention, the material property of crosslinked polyethylene is improved for the short glass fiber that collaboration is filled
Purpose, preferably the present invention polyethylene composition in by polyethylene, surface treatment short glass fiber and
The consumption weight ratio with above-mentioned restriction, can provide synergy and be more beneficial between polyolefin elastomer
Improve the material property of final crosslinked polyethylene.
, according to the invention it is preferred in the case of, the density of the polyethylene is 0.92-0.97g/cm3；It is described
The melt index of polyethylene is 0.1-20g/10min.
, according to the invention it is preferred in the case of, the compatilizer is maleic anhydride grafted ethene-octene copolymer
Thing and/or glycidyl methacrylate graft ethylene-octene copolymer.
, according to the invention it is preferred in the case of, the crosslinking agent is cumyl peroxide, benzoyl peroxide first
Acyl, di-isopropylbenzene hydroperoxide, TBHP, 2,5- dimethyl -2,5- di-tert-butyl peroxides
Hexane, -3- alkynes, peroxidating two acyl substratess, the peroxidating two of 2,5- dimethyl -2,5- di-tert-butyl peroxides
At least one in the tert-butyl group, dilauroyl peroxide, methyl ethyl ketone peroxide and cyclohexanone peroxide.
, according to the invention it is preferred in the case of, the crosslinking coagent is triallylcyanurate, three allyls
In base isocyanuric acid ester, trimethylol-propane trimethacrylate and trimethylolpropane trimethacrylate
At least one.
, according to the invention it is preferred in the case of, the nucleator be potassium sorbate, sodium citrate, benzoic acid,
At least one in benzoate, oxalate, organic phosphate and talcum powder.
, according to the invention it is preferred in the case of, the antioxidant is antioxidant 1010, irgasfos 168, resists
At least one in oxygen agent 1098, antioxidant 264 and bisphenol-A.
, according to the invention it is preferred in the case of, the processing aid is zinc stearate, and calcium stearate is stearic
At least one in sour magnesium and stearic acid.
Present invention also offers a kind of method of the polyethylene composition for preparing the present invention, including：(1) will
Coupling agent is surface-treated to short glass fiber and is dried, and obtains being surface-treated short glass fiber；
(2) by polyethylene, polyolefin elastomer, compatilizer, nucleator, crosslinking agent, crosslinking coagent, anti-
Oxygen agent, processing aid and surface treatment short glass fiber are mixed, and the mixture for obtaining is carried out
Extruding pelletization.
Wherein, the method that coupling agent is surface-treated to short glass fiber can configure second for (I)
Determining alcohol is the ethanol solution of 95 weight %, and coupling agent added into the ethanol solution, and stirring 5min is to equal
It is even；(II) short glass fiber is added in the ethanol solution added with coupling agent, 30min is stirred, then
Filtered and collected short glass fiber.The short glass fiber of collection is put in 110 DEG C of baking ovens,
It is dried 2 hours, obtains being surface-treated short glass fiber.
In accordance with the present invention it is preferred that, in step (2), a) polyethylene, crosslinking agent, crosslinking are helped
Agent, polyolefin elastomer are mixed makes masterbatch；B) by masterbatch, compatilizer, nucleator, antioxidant,
Processing aid and surface treatment short glass fiber carry out being mixed into polyethylene composition.
In the present invention, carry out being mixed in step (2) and step by step enter each component of polyethylene composition
Row mixing.First polyethylene, crosslinking agent, crosslinking coagent, polyolefin elastomer can be added in step a)
To enter stirred in homogenizer 3-10min to being well mixed, be subsequently adding double screw extruder and melted
Blending and extruding pelletization, make masterbatch.Each component is mixed in homogenizer in step b), then
Add double screw extruder to carry out melt blending and extruding pelletization, obtain after the particle for obtaining is dried
Polyethylene composition.The screw slenderness ratio of the double screw extruder can be 18/1, and the rotating speed of screw rod is
60-100 rev/min.
, according to the invention it is preferred in the case of, in step (2), the masterbatch and described of being mixed
It is melt blending to be mixed into polyethylene composition, and the temperature of the melt blending is 135-155 DEG C.
Present invention also offers a kind of modified crosslinking polyethylene, the modified crosslinking polyethylene is by by the present invention
Polyethylene composition carry out cross-linking reaction and obtain.
In the present invention, on the basis of the gross weight of the modified crosslinking polyethylene, the modified crosslinking polyethylene
Short glass fiber containing 5-40 weight %；Preferably comprise the short glass fiber of 20-30 weight %.
In the present invention, the modified crosslinking polyethylene can have more preferable material property.Specifically, it is described
The impact strength of modified crosslinking polyethylene is 19-31KJ/m2, bending modulus is 1680-2012MPa, heat
Deformation temperature is 86-115 DEG C, and resistance to high creep rate is 0-1.1%.
, according to the invention it is preferred in the case of, the temperature of the cross-linking reaction is 180-220 DEG C, and crosslinking is anti-
The time answered is 15-25min.
In the present invention, the approach for completing the cross-linking reaction can be so that there is no particular limitation, can be with various
The reaction molding mode of plastic processing is carried out.Such as described cross-linking reaction can be selected by compression molding
During complete, preparation is suitable to the sheet material of material properties test.Can also be prepared by other molding modes
The polyethylene products such as tubing, section bar, sheet material.
Hereinafter will be described the present invention by embodiment.
In following examples,
Izod (jagged) impact strengths are measured and determined according to the method for GB/T1843-2008, are surveyed
Examination temperature is 23 DEG C；
Bending modulus is measured and determined according to the method for GBT9341-2008, and test temperature is 23 DEG C；
Tension test is stretched according to GB/T1040-2006 plastic tensile method for testing performances in Instron
Yield strength, maximum tension fracture strength, elongation at break are measured on test instrument：Thickness of sample is 4mm,
Measurement length is 115mm, and width is 10mm, and test rate is 50mm/min, and test temperature is 23
℃；
Heat distortion temperature according to GB/T 1634.2-2004 plastics load deformation temperatures measure；
High temperature creep property is hung in an oven by the way that tensile bars fixture is clamped into batten upper end, lower end
0.25 kilogram of counterweight is hung up, constant temperature 30min, then takes out test specimens by sample in 200 DEG C of baking ovens
The elongation change of product.
The material for using in the following Examples and Comparative Examples is as follows：
Polyethylene DMDA8007 (english abbreviation is HDPE) is purchased from Shenhua packet header, and melt index is
8g/10min (testing standard ASTM D-1238,190 DEG C, 2.16kg), density is 0.963g/cm3(survey
Test-object is accurate：ASTM D-1505)；
Short glass fiber (ECS305K), (a diameter of 8-15 μm, length is 3-8mm), Chongqing state
Border composite Co., Ltd；
Coupling agent：3- aminopropyl triethoxysilanes (KH550), 3- methyl (acryloxy) propyl group three
Methoxy silane (KH570), VTES (GX-150), 3- ureido-propyl trimethoxies
Base silane, titanate coupling agent, are purchased from Chemical Reagent Co., Ltd., Sinopharm Group；
Ethylene-octene copolymer (POE 8200), is purchased from DOW Chemical, and melt flow rate (MFR) is 5g/10min
(testing standard ASTM D-1238,190 DEG C, 2.16kg), density is 0.873g/cm3(testing standard：
ASTM D-1505)；
Ternary ethylene-propylene copolymer (EPDM NORDELIP 4570), purchased from Dow Chemical, ethene
The content of construction unit is 50 weight portions；
Maleic anhydride grafted ethene-octene copolymer (MAH-g-POE, GR216), melt flow rate (MFR)
For 1.25g/10min (testing standard ASTM D-1238,190 DEG C, 2.16kg), density is 0.875g/cm3
(testing standard：ASTM D-1505)；
Glycidyl methacrylate graft ethylene-octene copolymer (POE-g-GMA, SOG-02),
Purchased from the liter macromolecule new material Science and Technology Ltd. of Nantong day；
Peroxide cross-linking agent：2,5- dimethyl -2,5- bis- (tert-butyl peroxy base) hexane, cumyl peroxide,
Crosslinking coagent：Triallyl isocyanurate, is purchased from Akzo Nobel N.V.；
Nucleator：Milliken HPN-20E, are purchased from Shanghai Rongtian Chemical Co., Ltd.；
Antioxidant：Antioxidant 1010, irgasfos 168, are purchased from Chemical Reagent Co., Ltd., Sinopharm Group；
Processing aid：Stearic acid, calcium stearate, are purchased from Chemical Reagent Co., Ltd., Sinopharm Group.
In following examples, each component content is calculated by inventory when preparing in polyethylene composition,
The content of short glass fiber is calculated according to inventory when preparing in the modified crosslinking polyethylene for obtaining.
Embodiment 1
This example demonstrates that the preparation method of the polyethylene composition of the present invention and modified crosslinking polyethylene.
(1) short glass fiber is modified：The coupling agent 3- aminopropyl triethoxysilanes of 1.6g are added
Then stirring 5min will to being well mixed in the ethanol solution (concentration of alcohol is 95 weight %) of 1L
The short glass fiber of 200g adds stirring 30min fully to infiltrate.Remove chopped glass after ethanol solution
Glass fiber dries 2h at 110 DEG C, then washes and dry, and obtains the modified short glass fiber in surface
SGF-1；
(2) polyethylene composition processed：A) by high density polyethylene (HDPE) DMDA8007,7g of 770g
2,5- dimethyl -2,5- two (tert-butyl peroxy base) hexane, the Triallyl isocyanurate of 4g, the ethene of 10g
- octene copolymer is added in homogenizer and stirs 5min, then blend is passed through into double screw extruder
(screw slenderness ratio 18/1,60 revs/min of rotating speed) melt blending, extruding pelletization operation system at 135 DEG C
For into polyethylene master batch；B) by polyethylene master batch, the maleic anhydride grafted ethene-octene copolymer of 20g,
The antioxidant 1010 of polyethylene nucleator HPN-20E, 2g of 10g, the irgasfos 168 of 2g, 5g
The surface treatment short glass fiber SGF-1 of stearic acid and 200g adds homogenizer to be mixed
3min, by the mixture for obtaining double screw extruder melt blending, extruding pelletization work at 145 DEG C are passed through
Sequence, and the prepared polyethylene composition GPE-1 of 2h are dried at 80 DEG C；
(3) it is crosslinked：GPE-1 is carried out into compression molding 20min at 200 DEG C, modified crosslinking is obtained
Polyethylene.
Modified crosslinking polyethylene is carried out into performance test, 1 is the results are shown in Table.
Embodiment 2
This example demonstrates that the preparation method of the polyethylene composition of the present invention and modified crosslinking polyethylene.
(1) short glass fiber is modified：By coupling agent 3- methyl (acryloxy) the propyl group front three of 5g
TMOS adds the middle stirring 5min of ethanol solution (concentration of alcohol is 95 weight %) of 1L extremely to mix
Uniformly, then the short glass fiber addition of 250g is stirred into 30min fully to infiltrate.Remove ethanol molten
Short glass fiber is dried into 2h at 110 DEG C after liquid, then is washed and is dried, obtained surface treatment and be chopped
Glass fibre SGF-2；
(2) polyethylene composition processed：A) by high density polyethylene (HDPE) DMDA8007,5g of 690g
2,5- dimethyl -2,5- two (tert-butyl peroxy base) hexane, the Triallyl isocyanurate of 4g, the ethene of 50g
- octene copolymer is added in homogenizer and stirs 5min, then blend is passed through into double screw extruder
(screw slenderness ratio 18/1,100 revs/min of rotating speed) melt blending, extruding pelletization operation system at 145 DEG C
For into polyethylene master batch.B) by polyethylene master batch, the maleic anhydride grafted ethene-octene copolymer of 10g,
The antioxidant 1010 of polyethylene nucleator HPN-20E, 2g of 10g, the irgasfos 168 of 2g, 5g
The surface treatment short glass fiber SGF-2 of stearic acid and 250g adds homogenizer to be mixed
3min, and the mixture for obtaining is passed through into double screw extruder melt blending, extruding pelletization at 155 DEG C
Operation, and the prepared polyethylene composition GPE-2 of 2h are dried at 80 DEG C；
(3) it is crosslinked：GPE-2 is carried out into compression molding 25min at 180 DEG C, modified crosslinking is obtained
Polyethylene.
Modified crosslinking polyethylene is carried out into performance test, 1 is the results are shown in Table.
Embodiment 3
This example demonstrates that the preparation method of the polyethylene composition of the present invention and modified crosslinking polyethylene.
(1) short glass fiber is modified：The coupling agent 3- ureido-propyl trimethoxy silanes of 4.5g are added
5min is stirred to being well mixed, then in the ethanol solution (concentration of alcohol is 95 weight %) for entering 1L
Stirring 30min is added fully to infiltrate the short glass fiber of 300g.Remove and will be chopped after ethanol solution
Glass fibre dries 2h at 110 DEG C, then washes and dry, and obtains being surface-treated short glass fiber
SGF-3；
(2) polyethylene composition processed：A) by high density polyethylene (HDPE) DMDA8007,7g of 660g
Cumyl peroxide, the Triallyl isocyanurate of 2g, the ethylene-octene copolymer of 20g are added
5min is stirred in homogenizer, then by blend by double screw extruder (screw slenderness ratio 18/1,
80 revs/min of rotating speed) melt blending, extruding pelletization operation are prepared into polyethylene master batch at 155 DEG C.b)
By polyethylene master batch, the maleic anhydride grafted ethene-octene copolymer of 20g, 5g polyethylene nucleator
The table of the antioxidant 1010 of HPN-20E, 4g, the irgasfos 168 of 4g, the calcium stearate of 8g and 300g
Face processes short glass fiber SGF-3 and adds homogenizer to carry out mixing 3min, and mixed by what is obtained
Compound is done by double screw extruder melt blending, extruding pelletization operation at 145 DEG C at 80 DEG C
Dry 2h is obtained polyethylene composition GPE-3；
(3) it is crosslinked：GPE-3 is carried out into compression molding 15min at 220 DEG C, modified crosslinking is obtained
Polyethylene.
Modified crosslinking polyethylene is carried out into performance test, 1 is the results are shown in Table.
Embodiment 4
(1) short glass fiber is modified：By coupling agent 3- methyl (acryloxy) the propyl group front three of 3g
TMOS adds the middle stirring 5min of ethanol solution (concentration of alcohol is 95 weight %) of 1L extremely to mix
Uniformly, then the short glass fiber addition of 300g is stirred into 30min fully to infiltrate.Remove ethanol molten
Short glass fiber is dried into 2h at 110 DEG C after liquid, then is washed and is dried, obtained surface treatment and be chopped
Glass fibre SGF-4；
(2) polyethylene composition processed：A) by high density polyethylene (HDPE) DMDA8007,7g of 600g
Cumyl peroxide, the Triallyl isocyanurate of 4g, the ternary ethylene-propylene copolymer of 50g add high
5min is stirred in fast mixer, then by blend by double screw extruder (screw slenderness ratio 18/1,
80 revs/min of rotating speed) melt blending, extruding pelletization operation are prepared into polyethylene master batch at 145 DEG C.b)
By polyethylene master batch, the glycidyl methacrylate graft ethylene-octene copolymer of 50g, 4g
The surface treatment staple glass of antioxidant 1010, the irgasfos 168 of 4g, the calcium stearate of 4g and 300g
Fiber SGF-4 adds homogenizer to carry out mixing 3min, and the mixture for obtaining is passed through into twin-screw
Extruder melt blending, extruding pelletization operation at 145 DEG C, and 2h is dried at 80 DEG C poly- second is obtained
Ene compositions GPE-4；
(3) it is crosslinked：GPE-4 is carried out into compression molding 20min at 200 DEG C, modified crosslinking is obtained
Polyethylene.
Performance test is carried out, 1 is the results are shown in Table.
Embodiment 5
According to the method for embodiment 1, except for the difference that,
(1) short glass fiber is modified：The coupling agent 3- aminopropyl triethoxysilanes of 1.6g are added
Then stirring 5min will to being well mixed in the ethanol solution (concentration of alcohol is 95 weight %) of 1L
The short glass fiber of 200g adds stirring 30min fully to infiltrate.Remove chopped glass after ethanol solution
Glass fiber dries 2h at 110 DEG C, then washes and dry, and obtains being surface-treated short glass fiber
SGF-5；
(2) polyethylene composition processed：By the 2,5- of high density polyethylene (HDPE) DMDA8007,7g of 770g
Dimethyl -2,5- two (tert-butyl peroxy base) hexane, the Triallyl isocyanurate of 4g, the ethene-pungent of 10g
Alkene copolymer, the maleic anhydride grafted ethene-octene copolymer of 20g, the polyethylene nucleator of 10g
The surface of the antioxidant 1010 of HPN-20E, 2g, the irgasfos 168 of 2g, the stearic acid of 5g and 200g
Processing short glass fiber SGF-5 adds homogenizer to carry out mixing 3min, and by the mixing for obtaining
Thing is dried by double screw extruder melt blending, extruding pelletization operation at 145 DEG C at 80 DEG C
2h is obtained polyethylene composition GPE-5；
(3) it is crosslinked：GPE-5 is carried out into compression molding 20min at 200 DEG C, modified crosslinking is obtained
Polyethylene.
Performance test is carried out, 1 is the results are shown in Table.
Comparative example 1
(1) polyethylene composition processed：By the 2,5- of high density polyethylene (HDPE) DMDA8007,7g of 750g
Dimethyl -2,5- two (tert-butyl peroxy base) hexane, the Triallyl isocyanurate of 4g, the maleic acid of 50g
Acid anhydride grafted polyethylene, the vinyltrimethoxy silane of 4g, the short glass fiber of 200g are added at a high speed
Mixer carries out mixing 3min, and the mixture for obtaining is melted by double screw extruder at 145 DEG C
Blending, extruding pelletization operation, and the prepared polyethylene composition DGPE-1 of 2h are dried at 80 DEG C；
(2) it is crosslinked：DGPE-1 is carried out into compression molding 20min at 200 DEG C, modified crosslinking is obtained
Polyethylene.
Performance test is carried out, 2 are the results are shown in Table.
Comparative example 2
Prepare polyethylene composition：By the antioxygen of high density polyethylene (HDPE) DMDA8007,2g of 1000g
The irgasfos 168 of agent 1010,2g, the calcium stearate of 4g add homogenizer mixing 3min, and will
The mixture for obtaining by double screw extruder melt blending, extruding pelletization operation at 145 DEG C, and
2h is dried at 80 DEG C polyethylene composition DGPE-2 is obtained；
(3) DGPE-2 is carried out into compression molding 20min at 200 DEG C, obtains modified poly ethylene, entered
Row performance test, the results are shown in Table 2.
Comparative example 3
(1) polyethylene composition is prepared：By the high density polyethylene (HDPE) DMDA8007 of 800g, 7g's
Peroxide cross-linking agent 2,5- dimethyl -2,5- bis- (tert-butyl peroxy base) hexane, the allyl of crosslinking coagent three of 4g
Base isocyanuric acid ester, the antioxidant 1010 of 2g, the irgasfos 168 of 2g is appointed with the surface free of 200g
The chopped glass fiber of where reason is stirred 3min to being well mixed by homogenizer, and will obtain
Mixture passes through double screw extruder melt blending, extruding pelletization operation at 145 DEG C, and at 80 DEG C
It is dried 2h and polyethylene composition DGPE-3 is obtained；
(2) it is crosslinked：DGPE-3 is carried out into compression molding 20min at 200 DEG C, modified crosslinking is obtained
Polyethylene.
Performance test is carried out, 2 are the results are shown in Table.
Comparative example 4
(1) polyethylene composition is prepared：By the high density polyethylene (HDPE) DMDA8007 of 1000g, 7g's
Peroxide cross-linking agent 2,5- dimethyl -2,5- bis- (tert-butyl peroxy base) hexane, the allyl of crosslinking coagent three of 4g
Base isocyanuric acid ester, the antioxidant 1010 of 2g, the irgasfos 168 of 2g is stirred by homogenizer
3min is mixed to being well mixed, and the mixture for obtaining is melted by double screw extruder at 145 DEG C
Blending, extruding pelletization operation, and the prepared polyethylene composition DGPE-4 of 2h are dried at 80 DEG C；
(2) it is crosslinked：DGPE-4 is carried out into compression molding 20min at 200 DEG C, modified crosslinking is obtained
Polyethylene.
Performance test is carried out, 2 are the results are shown in Table.
Comparative example 5
(1) polyethylene composition is prepared：By the high density polyethylene (HDPE) DMDA8007 of 800g, 2g's
Antioxidant 1010, the irgasfos 168 of 2g leads to the chopped glass fiber of any process of the surface free of 200g
Cross homogenizer and be stirred 3min to being well mixed, and the mixture for obtaining is squeezed by twin-screw
Go out machine melt blending, extruding pelletization operation at 145 DEG C, and 2h is dried at 80 DEG C and polyethylene is obtained
Composition DGPE-3；
(2) DGPE-3 is carried out into compression molding 20min at 200 DEG C, obtains modified poly ethylene, entered
Row performance test, the results are shown in Table 2.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Impact strength, KJ/m2 | 22.5 | 26.3 | 24.2 | 30.1 | 19.2 |
| Bending strength, MPa | 47.5 | 43.4 | 45.9 | 40.9 | 45.1 |
| Bending modulus, MPa | 2012 | 1876 | 1918 | 1686 | 1923 |
| Tensile strength, MPa | 44.3 | 41.1 | 40 | 35.1 | 40.8 |
| Elongation at break, % | 10.2 | 14.3 | 12.4 | 19.2 | 9.2 |
| Heat distortion temperature, DEG C | 114.6 | 108.3 | 111.2. | 86.8 | 108.5 |
| Creep rate, % | 0 | 0.2 | 0.3 | 1.1 | 0.8 |
Table 2
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |
| Impact strength, KJ/m2 | 15 | 4.3 | 11.3 | 33.9 | 2.9 |
| Bending strength, MPa | 42.0 | 34 | 42.1 | 26.5 | 43.1 |
| Bending modulus, MPa | 1812 | 1320 | 1789 | 1236 | 1849 |
| Tensile strength, MPa | 38.3 | 31.2 | 36 | 27.8 | 39.5 |
| Elongation at break, % | 6.2 | 93 | 6.6 | 168 | 5 |
| Heat distortion temperature, DEG C | 96.1 | 64.5 | 94.5 | 56.7 | 98.8 |
| Creep rate, % | 3.1 | Fracture | 4.5 | 19.3 | Fracture |
By embodiment as can be seen that passing through the inventive method, using surface-treated short glass fiber
Modified crosslinking polyethylene can be prepared.The result data of table 1 can be seen that the poly- second of obtained modified crosslinking
Alkene can effectively improve the modulus of product, keep higher impact strength, reach high-modulus HI high impact
Balance.
Table 2 is the test result of obtained product in comparative example, it can be seen that obtained in comparative example 1-5
Product can not reach the balance of high-modulus and HI high impact, and high temperature resistant croop property is poor.For example, right
In ratio 2 and comparative example 5, polyethylene is uncrosslinked, and the impact strength of product only has 4.3kJ/m2With
2.9kJ/m2.As comparative example 4, only crosslinking do not strengthen, the bending modulus of product only has 1236MPa.Such as
Comparative example 3, i.e. crosslinking strengthen and do not process short glass fiber again, then impact and modulus can not reach
High value.Comparative example 1 is using method disclosed in CN102691832B, wherein long glass fibres is replaced
Short glass fiber is changed to, the results of property as a result tested is not so good as embodiment, illustrates the present invention from specific
Polyethylene composition can just be effectively realized short glass fiber and be filled in crosslinked polyethylene.
Contrast comparative example, embodiments of the invention explanation surface treatment short glass fiber strengthens the poly- second of crosslinking
Alkene has high-modulus, high impact, high temperature resistant croop property and heat resistance concurrently.
Claims (12)
1. a kind of polyethylene composition, on the basis of the gross weight of said composition, said composition includes 50-80
The polyethylene of weight %, the polyolefin elastomer of 1-5 weight %, the compatilizer of 1-10 weight %, 5-40
The surface treatment short glass fiber of weight %, the nucleator of 0-2 weight %, the crosslinking of 0.3-2 weight %
Agent and the crosslinking coagent of 0.1-1 weight %, and the antioxidant and processing aid of 0.1-1 weight %；
Wherein, it is described surface treatment short glass fiber be by by short glass fiber with coupling agent surface
Obtain after process；The coupling agent is in silane coupler, titanate coupling agent and boric acid ester coupler
At least one, the end group of the silane coupler contains amino group, acryloxy group and urea groups base
At least one in group.
2. polyethylene composition according to claim 1, wherein, change obtained in the composition
Property crosslinked polyethylene impact strength be more than 16KJ/m2, bending modulus is more than 1600MPa, thermal deformation temperature
Degree is more than 80 DEG C, and high temperature resistant creep rate is less than 3%.
3. polyethylene composition according to claim 1, wherein, the surface treatment is chopped glass
Glass fiber is 100 with the weight ratio of the coupling agent：0.5 to 100：3；The coupling agent is 3- ammonia third
Ethyl triethoxy silicane alkane, 3- methyl (acryloxy) propyl trimethoxy silicane, vinyl triethoxyl
At least one in silane, 3- ureido-propyl trimethoxy silanes and titanate coupling agent.
4. polyethylene composition according to claim 1, wherein, the polyethylene is poly- with described
The weight ratio of olefin elastomer is 5:1 to 80:1.
5. the polyethylene composition according to any one of claim 1-4, wherein, the polyene
Olefin elastomer is ethene-C4-8Olefin copolymer, EP rubbers, ethylene propylene diene rubber and ethylene-vinyl acetate
At least one in copolymer, the preferably polyolefin elastomer be ternary ethylene-propylene copolymer and/or ethene-
Octene copolymer；The compatilizer is maleic anhydride grafted ethene-octene copolymer and/or methacrylic acid
Ethylene oxidic ester grafted ethene-octene copolymer.
6. the polyethylene composition according to any one of claim 1-4, wherein, the crosslinking
Agent be cumyl peroxide, benzoyl peroxide, di-isopropylbenzene hydroperoxide, TBHP,
2,5- dimethyl -2,5- di-t-butyl hexane peroxides, 2,5- dimethyl -2,5- di-tert-butyl peroxides -3-
Alkynes, peroxidating two acyl substratess, di-t-butyl peroxide, dilauroyl peroxide, methyl ethyl ketone peroxide and
At least one in cyclohexanone peroxide, the crosslinking coagent is triallylcyanurate, triallyl
In isocyanuric acid ester, trimethylol-propane trimethacrylate and trimethylolpropane trimethacrylate
It is at least one.
7. polyethylene composition according to claim 1, wherein, the nucleator is sorbic acid
In potassium, sodium citrate, benzoic acid, benzoate, oxalate, organic phosphate and talcum powder extremely
Few one kind；The antioxidant is antioxidant 1010, irgasfos 168, antioxidant 1098, antioxidant 264
With at least one in bisphenol-A；The processing aid be zinc stearate, calcium stearate, magnesium stearate and
At least one in stearic acid.
8. a kind of method of the polyethylene composition prepared any one of claim 1-7, including：
(1) coupling agent is surface-treated to short glass fiber and is dried, obtained surface treatment short
Cut glass fibre；
(2) by polyethylene, polyolefin elastomer, compatilizer, nucleator, crosslinking agent, crosslinking coagent,
Antioxidant, processing aid and surface treatment short glass fiber carry out being mixed into polyethylene composition.
9. method according to claim 8, wherein, in step (2), a) by polyethylene,
Crosslinking agent, crosslinking coagent, polyolefin elastomer are mixed makes masterbatch；B) by masterbatch, compatilizer,
Nucleator, antioxidant, processing aid and surface treatment short glass fiber carry out being mixed into polyethylene composition
Thing.
10. method according to claim 8 or claim 9, wherein, it is described mixed in step (2)
It is melt blending that masterbatch and the polyethylene composition that is mixed into are made in conjunction, and the temperature of the melt blending is
135-155℃。
A kind of 11. modified crosslinking polyethylenes, the modified crosslinking polyethylene in claim 1-7 by will appoint
Polyethylene composition described in one carries out cross-linking reaction and obtains.
12. modified crosslinking polyethylenes according to claim 11, wherein, the cross-linking reaction
Temperature is 180-220 DEG C, and the time of cross-linking reaction is 15-25min.
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