CN107286421A - The automotive oil tank polyethylene composition of gas fluidized-bed process production - Google Patents
The automotive oil tank polyethylene composition of gas fluidized-bed process production Download PDFInfo
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- CN107286421A CN107286421A CN201610228231.7A CN201610228231A CN107286421A CN 107286421 A CN107286421 A CN 107286421A CN 201610228231 A CN201610228231 A CN 201610228231A CN 107286421 A CN107286421 A CN 107286421A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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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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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
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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
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Abstract
The present invention relates to a kind of automotive oil tank polyethylene composition of gas fluidized-bed process production, said composition is made up of high density polyethylene (HDPE) and additive, the additive is that antioxidant, processing aid, lubricant and carbon fiber compounding are formed, the addition of additive can improve product tensile yield strength, product is met automotive oil tank material products requirement.
Description
Technical field
The present invention relates to a kind of polyethylene composition, specifically a kind of automobile oil of gas fluidized-bed process production
Case polyethylene composition.
Background technology
In recent years, China's automobile industry is lasting, quick, develop in a healthy way, and is counted according to National Information Center,
Automobile sales volume in 2011 reaches 19,000,000, and wherein passenger car (car, MPV, SUV) sales volume is
11320000, issued according to Development Research Center of the State Council, Automotive Engineering Society joint《Chinese automobile is produced
Industry blue book》Prediction, Chinese 2010~the year two thousand twenty of passenger car increases close to 10%, the year of the year two thousand twenty
Aggregate demand is up to 23,370,000.The utilization rate of current domestic production automobile plastic fuel tank has reached 70%
Left and right.Calculated by automobile multilayer composite plastic fuel tank weight 6-10Kg, current China's automotive oil tank PP Pipe Compound
About 100,000 tons/year of aggregate demand, consumption market is concentrated mainly on East China, south China, the Northeast, East China
Area has that Yangzhou Asia is general, Wuhu along Rong Deng fuel tanks manufacturing enterprise, year, materials were at 4~60,000 tons；South China has
The fuel tank manufacturing enterprises such as Kao Taisi, 8,000 generations, year materials at 1~20,000 tons, northeast has that Changchun Asia is general, examine Thailand
This etc., ten thousand tons of year materials 1-2,1.4 ten thousand yuan/ton of price, whole dependence on import, imported product is mainly
HB111R of 4261AG, JPE company of Basell companies etc..
Plastic fuel tank has advantages below compared with metallic oil tank：
(1) it is lightweight.Generally, the wall thickness of iron fuel tank is at least 1.2mm, automobile plastic fuel tank it is flat
Equal wall thickness is 4mm.Because the density of iron is 7.8g/cm3, along with iron fuel tank outer surface will do antirust treatment,
So that its density can reach 8.0g/cm3, and the density of HDPE plastic material is 0.945g/cm3Left and right,
Therefore an iron fuel tank with isometric(al) is than 2.5 times of plastic fuel tank weight.
(2) antiseptic power is strong.Because plastics have very strong ability resistant to chemical etching, therefore automobile plastic
Fuel tank will not produce some impurity because of corrosion, start so that impurity will not be caused to enter by oil supply system
Machine and the damage for causing engine, reduce its service life.
(3) moulding is random.It is more and more with configuration of automobiles, in order to make full use of space, modern vapour
The exterior design of car becomes more and more compacter.From unlike metal fuel tank, plastic fuel tank is typically to adopt
With the mode of a blow molding, complex-shaped special-shaped product can be molded, therefore be conducive in automobile
In the case that general layout has determined, suitable fuel tank is molded according to existing chassis remaining space
Shape, and increase the volume of fuel tank as much as possible, this is that metal fuel tank is incomparable.
(4) it is safe, it will not be exploded because of thermal expansion.At present, most plastic fuel tank is all
It is fabricated by using the polythene material of HMW.The heat conductivity of this material is very low, only metal
1%.Meanwhile, High molecular weight polyethylene has well elastic and rigid, in -40 DEG C and 90 DEG C of situation
Under can still keep good mechanical performance, after shock can voluntarily resilience without produce permanent deformation, simultaneously
Electric spark will not be produced in friction or knockout process and is caused an explosion accident, even if automobile catches fire accidentally,
Also it will not be exploded because of plastic fuel tank expanded by heating, therefore plastic fuel tank has very high safety
Property.
(5) production cost is low, and processing technology is simple, and though many complicated product-formings all can one-shot forming,
And material can be recycled the product scrapped after crushed.
Have many advantages, such as just because of plastic fuel tank different from metal fuel tank so that plastic fuel tank
Alternative metals fuel tank, multilayer fuel tank replacing single-layer fuel tank turn into the main flow side of current automobile industry development
To.
First automobile plastic fuel tank is public by German Volkswagen motor corporations, BASF in the world
What department and Kautex companies developed in 1960s joint study, and in Porsche (during guarantor
It is prompt) it is successfully applied on sport car.Automobile plastic fuel tank has been obtained in economically developed US and European
To developing rapidly and extensive use, European manufacturer INERGY and KAUTEX TEXTRON is public
Department is always the leader status in world's plastic fuel tank, but as automobile plastic fuel tank is in North America
With flourishing for Japanese car market, the ratio of external plastic fuel tank has reached more than 90%.
Country's HDPE fuel tank PP Pipe Compounds used in fuel tank manufacturing enterprise are import at present, according to production work
HDPE fuel tank PP Pipe Compounds can be divided into two classes by skill and used catalyst again：
(1) gas-phase process：Basell companies are urged using Lupotech G bubble agitations bed process, chromium system
The 4261AG products of agent exploitation.
(2) aq slurry process：JPE companies are developed using Innovene S techniques, chromium-based catalysts
HB111R products；Phillip companies are using the monocyclic pipe slurry process of Phillips, chromium-based catalysts exploitation C579
Product.
Both the above technique produces the melt flow rate (MFR) of product at 5.0~7.0g/10min (21.6kg),
Density is 0.945~0.950g/cm3, used in fuel tank processing enterprise at home, after enterprise's use
Feedback information from the point of view of, the processing characteristics for the fuel tank PP Pipe Compound that two kinds of techniques are produced, mechanical property, impact
There is no significant difference on the key performances such as performance.At present, worldwide also not using gas-phase fluidized-bed
The technology of technique productions automotive oil tank PP Pipe Compound.
CN 1753729A disclose a kind of chromium-based catalysts that can control molecular weight and molecualr weight distribution and gathered
The system and method for ethene are closed, is additionally provided by using the catalyst system life containing two kinds of chrome catalysts
Bimodal polyethylene is produced, but the performance of product is not obviously improved, it is impossible to automotive oil tank PP Pipe Compound is produced.
In Japan Patent 200202412, Monoi discloses what is prepared by being sintered under non reducing conditions
What inorganic epoxide compound was loaded contains Cr6+Solid constituent (A), the alkoxide containing dialkylaluminum functional group
The purposes of thing (B) and trialkylaluminium (C).Resulting ethene polymers has good resistance to environment should
Power cracking behavior and good resistance to blowing creep properties.U.S. application 2002042428 discloses a kind of in hydrogen
The method that the chrome catalysts (A) of lower use trialkyl aluminium compound load carry out vinyl polymerization coexists, wherein
Chrome catalysts are lived by calcining the Cr compounds loaded on an inorganic in non-reducing atmosphere
Change makes Cr atoms be converted into hexavalent state, and A is then handled in unreactive hydrocarbons solvent using trialkyl aluminium compound
And solvent is removed in a short time and obtained.
Hasebe etc., Japan Patent 2001294612 is disclosed comprising inorganic oxide supported Cr chemical combination
Thing (being calcined at 300 DEG C~1100 DEG C in non-reducing atmosphere), R3-nAlLn(R=C1-12 alkyl；L=C1-8
Alkoxy, phenoxy group；0<n<1) with the catalyst of Lewis base organic compounds.The Catalyst Production has
There are HMW and the polyethylene of Narrow Molecular Weight Distribution.
In Japan Patent 2001198811, Hasebe etc. discloses on probation comprising the (load of Cr oxides
In fire resistant compound and by the heat-activated under non reducing conditions) and R3-nAlLn(R=C1-6 alkane
Base；L=C1-8 alkoxies, phenoxy group；0.5<n<1) polymerizing olefins with catalyst.In SiO2Load
CrO3With 0.9:1MeOH-Et3Make vinyl polymerization in the presence of the reaction product of Al mixtures, producing melting means is
The polymer that 0.18g/10min (under 190 DEG C, 2.16kg load) and 1- ahexene contents are 1.6mg/g.
In Chinese patent 1214344, a kind of chromium base catalysis of load for ethene gas-phase polymerization relate to
Agent, the catalyst is by using the inorganic oxygen containing hydroxyl on inorganic chromium open air and anhydrous solution impregnation surface
Compound carrier；Dry in atmosphere；Make particle activation in oxygen；Lived with being reduced using organo-aluminum compound
It is prepared by the catalyst intermediate of change.10g silica gel is mixed with the 0.05mol/LCrO3 aqueous solution, in 80-120
12h is dried at DEG C, 2h is bakeed at 200 DEG C and 4h is bakeed at 600 DEG C, using 25% ethoxyquin two
The hexane solution reduction of aluminium ethide, produces the fine catalyst that Cr contents are 0.25% and Al/Cr ratios are 3.
Durand etc., U.S. patent 5,075,395 is described by under the conditions of fluidised bed polymerisation and/or mechanical
Make ethene under stirring in the chromium oxide compound comprising being combined with particulate vector and by being heat-treated activation
In the presence of contacted with charge powder eliminate vinyl polymerization in induction period method, tell catalyst with pre-
The form of polymers is used.Durand methods are characterised by, by making the charge powder and organic calorize
Compound contact is handled the charge powder of oil in advance, causes ethene in prepolymer in this way
In the presence of contacted with charge powder after immediately begin to polymerization.
In U.S. patents 4,559,394, McDaniel, which is described, uses chrome catalysts and tertiary alcohol olefin polymerization.
The patent, which describes the addition alcohol into chromated oxide, improves chromium distribution.McDaniel is in activation of catalyst
The tertiary alcohol is added before.Interestingly, McDaniel is described can not reach above-mentioned mesh using silanol
's.
Ikegaim etc., U.S. patent 4,454,242 and 4,451,573 using silanol together with using zirconium or titanium and
The chromium oxide catalyst of alkyl magnesium compound processing is to prepare improved environmental stress crack resistance (ESCR)
Product.
It has been prepared for the chrome catalysts of the silanol based on chromium cyclopentadienyl and silanol and has been deposited onto on silica
To improve catalyst activity, such as Karol U.S. patents 4, described in 153,576.License to Mitsubishi
Chemical Industries, Ltd. U.S. patents 3,767,635；3,629,216；Introduced with 3,759,918
Five alkyl siloxy aluminium alkane are added in the chromium oxide catalyst of load useful poly- to prepare
Ethene.
Catalyst based on chromated oxide (CrOx) has high activity, moderate induction time and production
The polymer being distributed with HMW and intermediate molecular weight.Based on Silylchromate catalysts have compared with
Weak activity, but polymer of the production with wider powder Mass Distribution.Silylchromate catalysts are usual
Catalyst price than chromated oxide is high.It is required that obtaining a kind of method, this method causes regulation based on chromium oxidation
The catalyst of thing uses the catalysis based on silyl chromate so that the polymer produced by them reaches
The performance of the polymer of agent production.For the background information about silylchromate catalysis, see, for example,
Carrick etc. U.S. patents 3,324,095 and 3,324,101.Prior art lacks a kind of for being modified chromium oxygen
Compound catalyst by its polymer produced will erratically to be adjusted to reaching based on silicyl chromic acid
Cheap, the simple method of the polymer of salt catalyst system production.
The present invention is a kind of automotive oil tank polyethylene composition of gas fluidized-bed process production, using the party
Method has production cost low, the characteristics of product mechanical property is good, and there is presently no produce automobile using this method
The relevant report of fuel tank PP Pipe Compound.
The present invention is the automotive oil tank polyethylene composition and system of a kind of gas fluidized-bed process production of exploitation
Preparation Method, the automotive oil tank of individual layer or six layers of co-extrusion can be produced using the polyethylene composition of the present invention.
The content of the invention
It is an object of the invention to provide a kind of automotive oil tank polyethylene group of gas fluidized-bed process production
Compound, said composition is made up of high density polyethylene (HDPE) and additive, the additive be antioxidant, processing aid,
Lubricant and carbon fiber compounding are formed, and said composition addition, the tension impact that can significantly improve polyethylene is strong
Degree.
The automotive oil tank polyethylene composition of gas fluidized-bed process production of the present invention, including such as the following group
Point：High density polyethylene (HDPE) and additive；
In the polyethylene composition, count by weight, high density polyethylene (HDPE) is 100 parts；Additive is
0.04-0.8 parts；
The additive is that antioxidant, processing aid, lubricant and carbon fiber compounding are formed, highly dense with every gram
Spend on the basis of polyethylene, its addition is respectively：
Antioxidant：100-3000ppm；
Processing aid：100-1000ppm；
Lubricant：100-2000ppm；
Carbon fiber：100-2000ppm.
The automotive oil tank polyethylene composition of gas fluidized-bed process production of the present invention, wherein, institute
It is preferably chopped silk to state carbon fiber, and diameter is preferably 1-10mm.
The automotive oil tank polyethylene composition of gas fluidized-bed process production of the present invention, wherein, institute
It is preferably 2,6- di-tert-butyl-4-methy phenols, β-(3,5 di-t-butyl -4- hydroxy benzenes) to state antioxidant
Propionic acid octadecanol ester, three (Isosorbide-5-Nitrae-di-tert-butyl-phenyl) phosphite esters and 1,3,5- tri- (3,5- bis-
Tertiary butyl-4-hydroxy benzyl) one or more in isocyanuric acid.
The automotive oil tank polyethylene composition of gas fluidized-bed process production of the present invention, wherein, institute
It is preferably calcium stearate or zinc stearate to state processing aid.
The automotive oil tank polyethylene composition of gas fluidized-bed process production of the present invention, wherein, institute
It is preferably the one or more in erucyl amide, oleamide and fluoroelastomer to state lubricant.
The automotive oil tank polyethylene composition of gas fluidized-bed process production of the present invention, wherein, it is excellent
Choosing, the carbon fiber is added in fluid bed in ethylene polymerisation process, and the antioxidant, processing are helped
Agent and lubricant are added in kneading machine in polyethylene sends granulation process.
The automotive oil tank polyethylene composition of gas fluidized-bed process production of the present invention, wherein, it is excellent
Choosing, the polyethylene composition is 4.0~10.0g/10min in 21.6kg counterweights melt flow rate (MFR),
Density is 0.942~0.950g/cm3。
The automotive oil tank polyethylene composition of gas fluidized-bed process production of the present invention, wherein, it is excellent
Choosing, described -50 DEG C of tensile yield strengths of polyethylene composition are more than or equal to 140KJ/m2, -30 DEG C of stretchings
Impact strength is more than or equal to 170KJ/m2, 0 DEG C of tensile yield strength is more than or equal to 220KJ/m2, 25 DEG C of stretchings
Impact strength is more than or equal to 280KJ/m2, 50 DEG C of tensile yield strengths are more than or equal to 260KJ/m2, 70 DEG C of drawings
Impact strength is stretched more than or equal to 240KJ/m2。
Automotive oil tank of the present invention is with polyethylene composition using chromium titanium complex catalyst in gas phase fluidization
Produced in bed polyethylene process.
The present invention relates to a kind of automotive oil tank polyethylene composition of gas fluidized-bed process production, the combination
Thing is made up of high density polyethylene (HDPE) and additive, and the additive is antioxidant, processing aid, lubricant and carbon
Fiber compounding is formed, and the addition of additive can improve product tensile yield strength, product is met automobile oil
The requirement of case material products.
Embodiment
Embodiments of the invention are elaborated below：The present embodiment is premised on technical solution of the present invention
It is lower to be implemented, give detailed embodiment and process, but protection scope of the present invention be not limited to it is following
Embodiment, the experimental method of unreceipted actual conditions in the following example, generally according to normal condition.
The addition of antioxidant：
In the present invention, the addition to antioxidant is not particularly limited, and leads to production with every gram of high density polyethylene (HDPE)
On the basis of, add antioxidant 100-3000ppm；If the addition of antioxidant is less than 100ppm, due to
The addition of antioxidant is too small, causes product to ftracture aging, and the addition of antioxidant is more than 3000ppm,
Because antioxidant consumption is excessive, cause to waste, and be not easy to product machine-shaping, have no other beneficial effects.
The addition of processing aid：
In the present invention, the addition to adsorbent is not particularly limited, and leads to production with every gram of high density polyethylene (HDPE)
On the basis of, add adsorbent 100-1000ppm；If the addition of processing aid is less than 100ppm, by
It is too small in the addition of processing aid, it is impossible to which that playing improves surface, the effect of stable processing, and processing aid
Addition more than 1000ppm, cause waste, have no other beneficial effects.
The addition of lubricant：
In the present invention, the addition to lubricant is not particularly limited, and leads to production with every gram of high density polyethylene (HDPE)
On the basis of, add lubricant 100-2000ppm；If the addition of lubricant is less than 100ppm, due to
The addition of lubricant is too small, it is impossible to work, and the addition of lubricant is more than 2000ppm, due to lubrication
Agent consumption is excessive, causes to waste, and is not easy to product machine-shaping, has no other beneficial effects.
The addition of carbon fiber：
In the present invention, the addition to carbon fiber is not particularly limited, and leads to production with every gram of high density polyethylene (HDPE)
On the basis of, add carbon fiber 100-2000ppm；If the addition of carbon fiber is less than 100ppm, due to
The addition of carbon fiber is too small, and the tensile yield impact strength of product is not improved, and the addition of carbon fiber
Amount is more than 2000ppm, and consumption is excessive, and carbon fiber can condense, and be not easy to product machine-shaping, have no
Other beneficial effects.
Antioxidant species：
In the present invention, the species to antioxidant is not particularly limited, and usual antioxidant can be enumerated as 2,
6- di-tert-butyl-4-methy phenols, β-(3,5 di-t-butyl -4- hydroxy benzenes) propionic acid octadecanol ester,
Three (Isosorbide-5-Nitrae-di-tert-butyl-phenyl) phosphite esters, 1,3,5- tri- (3,5- di-t-butyl -4- hydroxyl benzyls
Base) one or more in isocyanuric acid.
Processing aid species：
In the present invention, processing aid species is not particularly limited, usual processing aid can be enumerated as firmly
Resin acid calcium or zinc stearate.
Lubricant species：
In the present invention, lubricant species is not particularly limited, usual lubricant can be with erucyl amide, oil
One or more in sour acid amides or fluoroelastomer.
Carbon fiber species：
In the present invention, carbon fiber species is not particularly limited, usual carbon fiber is the silk that is chopped, a diameter of
1-10mm。
High density polyethylene (HDPE)：
In the present invention, produced using special chromium-based catalysts in Unipol polyethylene process, it is special
Levy and be 21.6kg counterweight 4.0~10.0g/10min of melt flow rate (MFR), density is 0.942~0.950g/cm3。
If high density polyethylene (HDPE) melt flow rate (MFR) is less than 4.0g/10min, due to high density polyethylene (HDPE) melt
Flow rate is too small, causes unsuitable machine-shaping, and high density polyethylene (HDPE) melt flow rate (MFR) is more than
10.0g/10min, because high density polyethylene (HDPE) melt flow rate (MFR) is excessive, causes difficult processing to be molded, has no it
Its beneficial effect；
If high density polyethylene (HDPE) density is less than 0.942g/cm3, because high density polyethylene (HDPE) density is too small, make
Partially soft into fuel tank, mechanical property is not enough, is easily deformed；And high density polyethylene (HDPE) Density Density is more than 0.950
g/cm3, because high density polyethylene (HDPE) density is excessive, cause product partially hard, partially crisp, impact property is bad,
Especially under cryogenic using easily cracking.
Embodiment 1：
Carbon fiber is in the automotive oil tank polyethylene composition produced using gas fluidized-bed process, composition
Be chopped silk, a diameter of 7mm, and content is 100ppm (on the basis of every gram of high density polyethylene (HDPE))；Antioxygen
Agent is 2,6- di-tert-butyl-4-methy phenols, and content is 100ppm (using every gram of high density polyethylene (HDPE) as base
It is accurate)；Processing aid is calcium stearate, and content is 800ppm (on the basis of every gram of high density polyethylene (HDPE))；
Lubricant is erucyl amide and oleamide, and content is 500ppm and 100ppm is (poly- with every gram of high density
On the basis of ethene).
Melt flow rate (MFR) 5.5g/10min is determined using 21.6kg counterweights, density is 0.942g/cm3.The group
- 50 DEG C of tensile yield strength 145KJ/m of compound2, -30 DEG C of tensile yield strength 178KJ/m2, 0 DEG C of stretching punching
Hit intensity 229KJ/m2, 25 DEG C of tensile yield strength 286KJ/m2, 50 DEG C of tensile yield strength 270KJ/m2,
70 DEG C of tensile yield strength 248KJ/m2。
Embodiment 2：
Carbon fiber is in the automotive oil tank polyethylene composition produced using gas fluidized-bed process, composition
Be chopped silk, a diameter of 3mm, and content is 1000ppm (on the basis of every gram of high density polyethylene (HDPE))；It is anti-
Oxygen agent is β-(3,5 di-t-butyl -4- hydroxy benzenes) propionic acid octadecanol ester and 2,6- di-t-butyl -4-
Methylphenol, content is respectively 300ppm (on the basis of every gram of high density polyethylene (HDPE))；Processing aid is hard
Resin acid zinc, content is 400ppm (on the basis of every gram of high density polyethylene (HDPE))；Lubricant is oleamide,
Content is 1600ppm (on the basis of every gram of high density polyethylene (HDPE)).
Melt flow rate (MFR) 9.0g/10min is determined using 21.6kg counterweights, density is 0.946g/cm3.The group
- 50 DEG C of tensile yield strength 156KJ/m of compound2, -30 DEG C of tensile yield strength 185KJ/m2, 0 DEG C of stretching punching
Hit intensity 237KJ/m2, 25 DEG C of tensile yield strength 297KJ/m2, 50 DEG C of tensile yield strength 275KJ/m2,
70 DEG C of tensile yield strength 255KJ/m2。
Embodiment 3：
Carbon fiber is in the automotive oil tank polyethylene composition produced using gas fluidized-bed process, composition
Be chopped silk, a diameter of 5mm, and content is 1400ppm (on the basis of every gram of high density polyethylene (HDPE))；It is anti-
Oxygen agent is three (Isosorbide-5-Nitrae-di-tert-butyl-phenyl) phosphite esters and 1,3,5- tri- (3,5- di-t-butyl -4-
Hydroxybenzyl) isocyanuric acid, content is respectively 900ppm and 500ppm (with every gram of high density polyethylene (HDPE)
On the basis of)；Processing aid is calcium stearate, and content is 100ppm (using every gram of high density polyethylene (HDPE) as base
It is accurate)；Lubricant is fluoroelastomer and erucyl amide, and content is that 900ppm and 300ppm is (high with every gram
On the basis of density polyethylene).
Melt flow rate (MFR) 4.5g/10min is determined using 21.6kg counterweights, density is 0.950g/cm3.The group
- 50 DEG C of tensile yield strength 152KJ/m of compound2, -30 DEG C of tensile yield strength 174KJ/m2, 0 DEG C of stretching punching
Hit intensity 223KJ/m2, 25 DEG C of tensile yield strength 284KJ/m2, 50 DEG C of tensile yield strength 265KJ/m2,
70 DEG C of tensile yield strength 244KJ/m2。
Embodiment 4：
Carbon fiber is in the automotive oil tank polyethylene composition produced using gas fluidized-bed process, composition
Be chopped silk, a diameter of 2mm, and content is 1800ppm (on the basis of every gram of high density polyethylene (HDPE))；It is anti-
Oxygen agent is 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) isocyanuric acids and β-(3,5 two
Tertiary butyl-4-hydroxy benzene) propionic acid octadecanol ester, content is respectively 900ppm (with every gram of high density polyethylene (HDPE)
On the basis of)；Processing aid is calcium stearate, and content is 700ppm (using every gram of high density polyethylene (HDPE) as base
It is accurate)；Lubricant is erucyl amide, and content is 300ppm (on the basis of every gram of high density polyethylene (HDPE)).
Melt flow rate (MFR) 8.0g/10min is determined using 21.6kg counterweights, density is 0.944g/cm3.The group
- 50 DEG C of tensile yield strength 143KJ/m of compound2, -30 DEG C of tensile yield strength 183KJ/m2, 0 DEG C of stretching punching
Hit intensity 238KJ/m2, 25 DEG C of tensile yield strength 302KJ/m2, 50 DEG C of tensile yield strength 280KJ/m2,
70 DEG C of tensile yield strength 240KJ/m2。
Embodiment 5：
Carbon fiber is in the automotive oil tank polyethylene composition produced using gas fluidized-bed process, composition
Be chopped silk, a diameter of 1mm, and content is 900ppm (on the basis of every gram of high density polyethylene (HDPE))；Antioxygen
Agent is β-(3,5 di-t-butyl -4- hydroxy benzenes) propionic acid octadecanol ester and three (Isosorbide-5-Nitraes-di-tert-butyl
Base) phosphite ester, content is respectively 1000ppm and 500ppm (on the basis of every gram of high density polyethylene (HDPE))；
Processing aid is zinc stearate, and content is 300ppm (on the basis of every gram of high density polyethylene (HDPE))；Lubrication
Agent is oleamide and fluoroelastomer, and content is 1000ppm and 500ppm (with every gram of high density polyethylene (HDPE)
On the basis of).
Melt flow rate (MFR) 7.0g/10min is determined using 21.6kg counterweights, density is 0.943g/cm3.The group
- 50 DEG C of tensile yield strength 158KJ/m of compound2, -30 DEG C of tensile yield strength 187KJ/m2, 0 DEG C of stretching punching
Hit intensity 226KJ/m2, 25 DEG C of tensile yield strength 288KJ/m2, 50 DEG C of tensile yield strength 285KJ/m2,
70 DEG C of tensile yield strength 247KJ/m2。
Embodiment 6：
Carbon fiber is in the automotive oil tank polyethylene composition produced using gas fluidized-bed process, composition
Be chopped silk, a diameter of 10mm, and content is 1600ppm (on the basis of every gram of high density polyethylene (HDPE))；It is anti-
Oxygen agent is 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) isocyanuric acids, the tertiary fourths of 2,6- bis-
Base -4- methylphenols and β-(3,5 di-t-butyl -4- hydroxy benzenes) propionic acid octadecanol ester, content is respectively
800ppm, 500ppm and 600ppm (on the basis of every gram of high density polyethylene (HDPE))；Processing aid is hard
Resin acid zinc, content is 1000ppm (on the basis of every gram of high density polyethylene (HDPE))；Lubricant is fluoroelastomer,
Content is 1000ppm (on the basis of every gram of high density polyethylene (HDPE)).
Melt flow rate (MFR) 10.0g/10min is determined using 21.6kg counterweights, density is 0.945g/cm3.Should
- 50 DEG C of tensile yield strength 140KJ/m of composition2, -30 DEG C of tensile yield strength 176KJ/m2, 0 DEG C of stretching
Impact strength 220KJ/m2, 25 DEG C of tensile yield strength 280KJ/m2, 50 DEG C of tensile yield strengths
275KJ/m2, 70 DEG C of tensile yield strength 252KJ/m2。
Embodiment 7：
Carbon fiber is in the automotive oil tank polyethylene composition produced using gas fluidized-bed process, composition
Be chopped silk, a diameter of 8mm, and content is 1200ppm (on the basis of every gram of high density polyethylene (HDPE))；It is anti-
Oxygen agent is three (Isosorbide-5-Nitrae-di-tert-butyl-phenyl) phosphite esters, and content is 2000ppm (with every gram of high density
On the basis of polyethylene)；Processing aid is calcium stearate, and content is 900ppm (with every gram of high-density polyethylene
On the basis of alkene)；Lubricant is fluoroelastomer, and content is 100ppm (using every gram of high density polyethylene (HDPE) as base
It is accurate).
Melt flow rate (MFR) 4.0g/10min is determined using 21.6kg counterweights, density is 0.947g/cm3.The group
- 50 DEG C of tensile yield strength 154KJ/m of compound2, -30 DEG C of tensile yield strength 170KJ/m2, 0 DEG C of stretching punching
Hit intensity 235KJ/m2, 25 DEG C of tensile yield strength 294KJ/m2, 50 DEG C of tensile yield strength 260KJ/m2,
70 DEG C of tensile yield strength 250KJ/m2。
Embodiment 8：
Carbon fiber is in the automotive oil tank polyethylene composition produced using gas fluidized-bed process, composition
Be chopped silk, a diameter of 4mm, and content is 2000ppm (on the basis of every gram of high density polyethylene (HDPE))；It is anti-
Oxygen agent is β-(3,5 di-t-butyl -4- hydroxy benzenes) propionic acid octadecanol ester, three (Isosorbide-5-Nitraes-di-t-butyl
Phenyl) phosphite ester and 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) isocyanuric acids contain
Measure as 1500ppm, 500ppm and 300ppm (on the basis of every gram of high density polyethylene (HDPE))；Processing aid
For zinc stearate, content is 200ppm (on the basis of every gram of high density polyethylene (HDPE))；Lubricant is oleic acid
Acid amides, content is 2000ppm (on the basis of every gram of high density polyethylene (HDPE)).
Melt flow rate (MFR) 5.0g/10min is determined using 21.6kg counterweights, density is 0.949g/cm3.The group
- 50 DEG C of tensile yield strength 160KJ/m of compound2, -30 DEG C of tensile yield strength 180KJ/m2, 0 DEG C of stretching punching
Hit intensity 244KJ/m2, 25 DEG C of tensile yield strength 305KJ/m2, 50 DEG C of tensile yield strength 271KJ/m2,
70 DEG C of tensile yield strength 243KJ/m2。
Embodiment 9：
Carbon fiber is in the automotive oil tank polyethylene composition produced using gas fluidized-bed process, composition
Be chopped silk, a diameter of 9mm, and content is 300ppm (on the basis of every gram of high density polyethylene (HDPE))；Antioxygen
Agent is 2,6- di-tert-butyl-4-methy phenols, content be 3000ppm (using every gram of high density polyethylene (HDPE) as
Benchmark)；Processing aid is zinc stearate, and content is 500ppm (on the basis of every gram of high density polyethylene (HDPE))；
Lubricant is erucyl amide, oleamide and fluoroelastomer, and content is respectively 600ppm (with every gram of high density
On the basis of polyethylene).
Melt flow rate (MFR) 6.5g/10min is determined using 21.6kg counterweights, density is 0.948g/cm3.The group
- 50 DEG C of tensile yield strength 147KJ/m of compound2, -30 DEG C of tensile yield strength 172KJ/m2, 0 DEG C of stretching punching
Hit intensity 232KJ/m2, 25 DEG C of tensile yield strength 300KJ/m2, 50 DEG C of tensile yield strength 280KJ/m2,
70 DEG C of tensile yield strength 251KJ/m2。
Embodiment 10：
Carbon fiber is in the automotive oil tank polyethylene composition produced using gas fluidized-bed process, composition
Be chopped silk, a diameter of 6mm, and content is 1000ppm (on the basis of every gram of high density polyethylene (HDPE))；It is anti-
Oxygen agent is 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) isocyanuric acids, and content is 2600ppm
(on the basis of every gram of high density polyethylene (HDPE))；Processing aid is zinc stearate, content be 700ppm (with
On the basis of every gram of high density polyethylene (HDPE))；Lubricant is fluoroelastomer, and content is that 900ppm is (high with every gram
On the basis of density polyethylene).
Melt flow rate (MFR) 6.0g/10min is determined using 21.6kg counterweights, density is 0.946g/cm3.The group
- 50 DEG C of tensile yield strength 149KJ/m of compound2, -30 DEG C of tensile yield strength 171KJ/m2, 0 DEG C of stretching punching
Hit intensity 241KJ/m2, 25 DEG C of tensile yield strength 291KJ/m2, 50 DEG C of tensile yield strength 290KJ/m2,
70 DEG C of tensile yield strength 256KJ/m2。
Claims (8)
1. a kind of automotive oil tank polyethylene composition of gas fluidized-bed process production, including following component：
High density polyethylene (HDPE) and additive；
In the polyethylene composition, count by weight, high density polyethylene (HDPE) is 100 parts；Additive is
0.04-0.8 parts；
The additive is that antioxidant, processing aid, lubricant and carbon fiber compounding are formed, highly dense with every gram
Spend on the basis of polyethylene, its addition is respectively：
Antioxidant：100-3000ppm；
Processing aid：100-1000ppm；
Lubricant：100-2000ppm；
Carbon fiber：100-2000ppm.
2. the automotive oil tank polyethylene composition of gas fluidized-bed process production according to claim 1
Thing, it is characterised in that the carbon fiber is be chopped silk, a diameter of 1-10mm.
3. the automotive oil tank polyethylene composition of gas fluidized-bed process production according to claim 1
Thing, it is characterised in that the antioxidant is 2,6- di-tert-butyl-4-methy phenols, β-(3,5 two uncles
Butyl -4- hydroxy benzenes) propionic acid octadecanol ester, three (Isosorbide-5-Nitrae-di-tert-butyl-phenyl) phosphite esters and 1,
One or more in 3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) isocyanuric acids.
4. the automotive oil tank polyethylene composition of gas fluidized-bed process production according to claim 1
Thing, it is characterised in that the processing aid is calcium stearate or zinc stearate.
5. the automotive oil tank polyethylene composition of gas fluidized-bed process production according to claim 1
Thing, it is characterised in that the lubricant is one kind or several in erucyl amide, oleamide and fluoroelastomer
Kind.
6. the automotive oil tank polyethylene composition of gas fluidized-bed process production according to claim 1
Thing, it is characterised in that the carbon fiber is added in fluid bed in ethylene polymerisation process, the antioxidant,
Processing aid and lubricant are added in kneading machine in polyethylene sends granulation process.
7. the poly- second of automotive oil tank of the gas fluidized-bed process production according to any one of claim 1~6
Ene compositions, it is characterised in that the polyethylene composition is in 21.6kg counterweight melt flow rate (MFR)s
4.0~10.0g/10min, density is 0.942~0.950g/cm3。
8. the poly- second of automotive oil tank of the gas fluidized-bed process production according to any one of claim 1~6
Ene compositions, it is characterised in that described -50 DEG C of tensile yield strengths of polyethylene composition are more than or equal to
140KJ/m2, -30 DEG C of tensile yield strengths are more than or equal to 170KJ/m2, 0 DEG C of tensile yield strength is more than or equal to
220KJ/m2, 25 DEG C of tensile yield strengths are more than or equal to 280KJ/m2, 50 DEG C of tensile yield strengths are more than etc.
In 260KJ/m2, 70 DEG C of tensile yield strengths are more than or equal to 240KJ/m2。
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| CN1388202A (en) * | 2002-07-09 | 2003-01-01 | 杭州华电华源环境工程有限公司 | Heat-conducting polymer material and its prepn |
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