CN105419076B - A kind of special construct blow-molded of the automobile plastic fuel tank of resisting environmental stress and cracking - Google Patents
A kind of special construct blow-molded of the automobile plastic fuel tank of resisting environmental stress and cracking Download PDFInfo
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- CN105419076B CN105419076B CN201510979280.XA CN201510979280A CN105419076B CN 105419076 B CN105419076 B CN 105419076B CN 201510979280 A CN201510979280 A CN 201510979280A CN 105419076 B CN105419076 B CN 105419076B
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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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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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
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2400/00—Characteristics for processes of polymerization
- C08F2400/02—Control or adjustment of polymerization parameters
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- Cooling, Air Intake And Gas Exhaust, And Fuel Tank Arrangements In Propulsion Units (AREA)
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Abstract
The invention discloses a kind of special construct blow-molded of the automobile plastic fuel tank of resisting environmental stress and cracking, resisting environmental stress and cracking abilities>8000h is mainly prepared by the raw material of following parts by weight：99.50~99.80 parts of ethylene hervene copolymer polyvinyl resin, 0.05~0.35 part of antioxidant, 0.03~0.15 part of auxiliary antioxidant, 0.02 ~ 0.06 part of releasing agent.The automobile plastic fuel tank construct blow-molded has higher melt strength, excellent environmental stress cracking resistance and creep resistant and good chemical resistance, is suitable for the machine-shaping of single layer and multilayer automobile plastic fuel tank.
Description
Technical field
The invention belongs to blow molded plastic fields, and in particular to a kind of automobile plastic fuel tank of resisting environmental stress and cracking is special
Construct blow-molded.
Background technology
Fuel tank plastic is an important directions of Hyundai Motor plastic, the requirement with automotive light weight technology and height
Density polyethylene materials performance is continually developed, and application of the plastics on automobile is more and more extensive, and the application amount of automobile plastic is more
It is to become one of the mark for weighing Trend of Auto Manufacturing Technologies level and new material R ＆ D Level.Compared with metal fuel tank, automobile modeling
Material fuel tank is light-weight, babinet can be integrally formed, shape flexible design, antiseepage corrosion resistance and good, simple production process, efficiency
Height has longer service life.
Plastic fuel tank generally includes single layer and multilayered structure.Monolayer plastic fuel tank is usually by the direct hollow blow moldings of HDPE
Molding, is generally used for the fuel tank of the macromoleculars fuel oil such as diesel oil.Another security performance more preferably multilayer fuel tank, at present
Common combustion multilayer oil tank is generally six layers, and structure is divided into HDPE layer (addition carbon black color masterbatch), material-returning layer, bonding from outside to inside
Layer, barrier layer, adhesive layer, HDPE internal layers.Since multilayer fuel tank has barrier layer, fire resistant oil penetrating power is stronger, fuel oil
Infiltration capacity is smaller than 0.2g/24h, is fuel tank most environmentally friendly on our times.
Fuel tank of vehicle generally requires higher molecular weight with the special construct blow-moldeds of HDPE, to ensure that product is preferably rigid
Property and creep resistance, while special construct blow-molded should also have impact resistance, corrosion-resistant, resisting environmental stress and cracking, barrier, antistatic
Equal excellent performances and preferable processing performance.Currently, petro-chemical corporation is devoted to the special blowing material of fuel tank of vehicle both at home and abroad
The exploitation of material, the more well-known trade mark have HB111R, Total of the Lupolen4261AG of Basell companies, JPE companies of Japan public
The MS201BN etc. of department.Current country HDPE process units by production technology due to being restricted, it is difficult to produce satisfactory
The special construct blow-molded of automobile plastic fuel tank (abbreviation fuel tank of vehicle PP Pipe Compound) on six layers of fuel tank can be applied, and
Fuel tank of vehicle PP Pipe Compound security performance is more demanding, needs the heavy test by automobile industry security performance certification, automobile
Plastic fuel tank production domesticization becomes an insoluble problem, and fuel tank of vehicle PP Pipe Compound have to largely rely on import, raw material
It is expensive, and it is difficult to ensure supply.
Six layers of fuel tank of vehicle extrusion-blown modling machine-shaping are extremely complex, it is desirable that fuel tank of vehicle PP Pipe Compound has good add
Work performance and forming stability.Since fuel tank of vehicle is the critical component in the gadget of automobile engine periphery, when automobilism
Engine circumferential component temperature is higher, therefore it is required that fuel tank of vehicle PP Pipe Compound should have the performance of rigidity-toughness balanced.In addition, automobile
Fuel tank is chronically under the conditions of the concussion caused by road conditions are jolted, and needs long-term loading temperature is higher to contain various heterogeneities
Vehicle fuel have to the environmental stress cracking resistance of material higher in the use environment for being chronically at such complexity
It is required that.Resisting environmental stress and cracking ability is an important indicator of high density polyethylene (HDPE) fuel tank of vehicle PP Pipe Compound, if can improve
The resisting environmental stress and cracking ability of material can extend service life of the automotive oil tank material in severe complex environment.
Invention content
The object of the present invention is to provide a kind of special construct blow-molded of the automobile plastic fuel tank of resisting environmental stress and cracking, the vapour
There is vehicle plastic fuel tank construct blow-molded the features such as higher ahexene content, wider molecular weight distribution, performance, product to have excellent
Different environmental stress cracking resistance (ESCR/FNCT) and creep resistant, good chemical resistance are suitable for single layer, more
The machine-shaping of layer automobile plastic fuel tank.
The object of the invention is achieved through the following technical solutions：A kind of automobile plastic fuel tank blowing of resisting environmental stress and cracking
Material, resisting environmental stress and cracking ability>8000h is mainly prepared by the raw material of following parts by weight：
The melt flow rate (MFR) of ethylene hervene copolymer polyvinyl resin of the present invention is 5.3~6.5g/10min and density
For 0.943~0.947g/cm3, molecular weight distribution is 15~25, and weight average molecular weight is 250,000~400,000, by the following method
It prepares：In the presence of diluent is in recurrent state and catalyst always, feed ethylene and 1- hexenes are placed in reaction
Container is reacted, and reaction temperature is 94~100 DEG C, is reacted to 5.3~6.5g/10min of melt flow rate (MFR) of reaction product
With 0.943~0.947g/cm of density3When, stop reaction, obtains ethylene hervene copolymer polyvinyl resin.The ethylene hervene copolymer
Polyvinyl resin has excellent rigid-tough balance and excellent environmental stress cracking resistance.
1- hexenes molar percentage >=0.45Mol%, quality hundred in ethylene hervene copolymer polyvinyl resin of the present invention
Divide than being >=1.40Wt%.
The amount ratio of ethylene of the present invention and 1- hexenes is 1000 ﹕ 15~25；The dosage of 1- hexenes is catalyst amount
4~6 times.The dosage of the diluent is 34~39kg/h.
The specification of ethylene of the present invention is preferably：
Ethylene：Purity >=99.20%C2H2≤5×10-6CO≤1×10-6
O2≤2×10-6H2O≤1×10-6COS≤0.02×10-6。
The specification of 1- hexenes of the present invention is preferably：
1- hexenes：Purity >=98.5%H2O≤20×10-6CO≤5×1O-6
Monoolefine >=non-alhpa olefin≤1% of the positive structure of 98.5% isomery alhpa olefin≤1%
Peroxide≤1 × 10 of positive structure alhpa olefin >=96%-6Sulphur≤1 × 10-6。
Diluent of the present invention is preferably iso-butane.Wherein, the iso-butane of preferably following specification：
Iso-butane：Acetylene≤2 × 10 of purity >=95.0%-6Total sulfur≤1 × 10-6
Total olefin≤100 × 10-6Water≤20 × 10-6O2≤5×10-6。
Catalyst of the present invention is chromium-based catalysts, the chromium-based catalysts produced such as Grace companies of the U.S.963。
Antioxidant of the present invention is for improving the processing stability of material and long-acting thermal oxidative aging, wherein antioxygen
Agent uses phenolic antioxidant, auxiliary antioxidant to use phosphite ester kind antioxidant.
Phenolic antioxidant of the present invention is preferably four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythrites
Ester；The phosphite ester kind antioxidant is bis- (2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites.
Removal when material processing can be improved in releasing agent of the present invention, in the present invention preferably zinc stearate.
The above-mentioned special construct blow-molded of automobile plastic fuel tank is prepared by the following method：
(1) in the presence of diluent is in recurrent state and catalyst always, feed ethylene and 1- hexenes are placed in instead
It answers in container and is reacted, reaction temperature is 94~100 DEG C, is reacted to 5.3~6.5g/ of melt flow rate (MFR) of reaction product
0.943~0.947g/cm of 10min and density3When, stop reaction, obtains ethylene hervene copolymer polyvinyl resin；
(2) add after ethylene hervene copolymer polyvinyl resin, antioxidant and auxiliary antioxidant mixing by above-mentioned metering ratio
Enter kneading machine extruding pelletization, particle is cooling in cooling water, obtains automobile plastic fuel tank construct blow-molded.
In step (2) of the present invention, when kneading machine is kneaded, it is 230 DEG C to adjust kneading machine second segment barrel temperature, third
Section barrel temperature is 235 DEG C, and the 4th section of barrel temperature is 240 DEG C, and the 5th section of barrel temperature of kneading machine is 245 DEG C, the 6th section of cylinder
Temperature is 250 DEG C, and the 7th section of barrel temperature is 260~270 DEG C；The heat conduction oil temperature for heating kneading machine is 260 DEG C, and is adjusted
The temperature of cooling water is 50~70 DEG C, and cooling water flow is 600~700m3/h。
Compared with the prior art, the present invention has the following advantages：
(1) the special construct blow-molded of automobile plastic fuel tank of the invention has sufficiently high molecular weight and rational molecular weight
Distribution, high antioxygenic property meet the required processing performance of automobile plastic fuel tank blowing and every physical and mechanical property,
With excellent rigidity-toughness balanced performance, low-temperature impact performance outstanding, excellent resisting environmental stress and cracking and resistance to full notch creep
Performance.The resisting environmental stress and cracking (ESCR) of the present invention>8000h is much larger than the 500h of imported product, is much better than imported product.
Resistance to full notch creep performance>40h, also much larger than the 3h or 15h of imported product, resistance to full notch creep performance is much better than import production
Product.
(2) the special construct blow-molded mechanical property of automobile plastic fuel tank provided by the invention is better than Entry plastic vehicle fuel
Case product can replace imported product to be applied to industrialized production single layer to multilayer automobile plastic fuel tank and produce.
(3) in the preparation of ethylene hervene copolymer polyvinyl resin of the invention, by using chromium-based catalysts and adjustment
The conditions such as ratio, reaction temperature and ethylene feed amount between comonomer ethylene and hexene make ethylene hervene copolymer polyethylene
There is resin sufficiently high molecular weight and rational molecular weight distribution and excellent rigid-tough balance and excellent resistance to environment to answer
Power cracking performance.
Specific implementation mode
The catalyst activation treatment of following embodiment uses conventional method, specially：Catalyst is by opening tank bottom
Portion's valve, falls by gravity in activator, comes from the hot burning gas of the burner hearth of activation furnace and fluidized hot air heat-activated stove
And catalyst, after fluidizing gas is upwardly through distribution grid, is come into full contact with catalyst and make activation of catalyst.
Kneading machine uses the extruder of Coperion ZSK-350 types, extruder to have 7 sections of cylinders.
Catalyst is chromium-based catalysts, the chromium-based catalysts produced using Grace companies963。
Polymer grade ethylene：The C of purity >=99.20%2H2≤5×10-6 CO≤1×10-6
O2≤2×10-6 H2O≤1×10-6 COS≤0.02×10-6。
1- hexenes：The H of purity >=98.5%2O≤20×10-6 CO≤5×1O-6
Monoolefine >=non-alhpa olefin≤1% of the positive structure of 98.5% isomery alhpa olefin≤1%
Positive structure alhpa olefin >=96%
Peroxide≤1 × 10-6Sulphur≤1 × 10-6。
Iso-butane：Acetylene≤2 × 10 of purity >=95.0%-6Total sulfur≤1 × 10-6
Total olefin≤100 × 10-6Water≤20 × 10-6 O2≤5×10-6。
The special construct blow-molded of automobile plastic fuel tank of following embodiment is referred to as automobile plastic fuel tank construct blow-molded.
Embodiment 1
The raw material of ethylene hervene copolymer vinyl：
1) polymer grade ethylene inlet amount 30t/h
2) catalyst：Chromium-based catalysts963 addition 112kg/h
3) 1- hexenes addition 457kg/h
4) diluent iso-butane 36kg/h
The preparation method of ethylene hervene copolymer ethylene：
Diluent iso-butane is in recurrent state always, ethylene and 1- hexenes is injected separately into annular-pipe reactor, strictly
Ethylene hexene feed ratio is controlled, and the catalyst of activated processing is added, controls 94.8 DEG C of reaction temperature in reactor, ethylene
Inlet amount 30t/h, 1- hexene addition 475kg/h, catalyst feeding quantity 112kg/h, melt is obtained by the reaction in ethylene and 1- hexenes
Flowing velocity is 6.2g/10min, density 0.945g/cm3Ethylene hervene copolymer polyvinyl resin, molecular weight distribution is
15.3, weight average molecular weight is 27.3 ten thousand.
The raw material (parts by weight) of automobile plastic fuel tank construct blow-molded：
Wherein antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters；Auxiliary antioxidant
It is bis- (2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites.
The preparation method of automobile plastic fuel tank construct blow-molded：
By above-mentioned dosage, after ethylene hervene copolymer polyvinyl resin, antioxidant and auxiliary antioxidant mixing, it is added and is kneaded
Machine squeezes out in particle to cooling water, obtains particulate polyethylene product automobile plastic fuel tank construct blow-molded.
When kneading machine is kneaded, it is 230 DEG C to adjust kneading machine second segment barrel temperature, and third section barrel temperature is 235 DEG C, the
Four sections of barrel temperatures are 240 DEG C, and the 5th section of barrel temperature is 245 DEG C, and the 6th section of barrel temperature is 250 DEG C, the 7th section of cylinder temperature
Degree is 260 DEG C；The heat conduction oil temperature for heating kneading machine is 260 DEG C, and the temperature for adjusting particle cooling water is 68 DEG C, particle cooling
Water flow is 680m3/h。
Embodiment 2
The raw material of ethylene hervene copolymer vinyl：
1) polymer grade ethylene inlet amount 38t/h
2) catalyst：Chromium-based catalysts963 addition 149kg/h
3) 1- hexenes addition 795kg/h
4) diluent iso-butane 36.8kg/h
The preparation method of ethylene hervene copolymer vinyl：
Diluent iso-butane is in recurrent state always, ethylene and 1- hexenes is injected separately into annular-pipe reactor, strictly
Ethylene hexene feed ratio is controlled, and activated catalyst in advance is added, controls 98.2 DEG C of reaction temperature in reactor, ethylene
Inlet amount 38t/h, 1- hexene inlet amount is 795kg/h, catalyst feeding quantity 149kg/h, and ethylene and 1- hexenes are obtained by the reaction molten
Body flowing velocity is 5.4g/10min, density 0.945g/cm3Ethylene hervene copolymer polyvinyl resin, molecular weight distribution is
16.8, weight average molecular weight is 36.7 ten thousand.
The raw material (parts by weight) of automobile plastic fuel tank construct blow-molded：
Wherein antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters；Auxiliary antioxidant
It is bis- (2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites.
The preparation method of automobile plastic fuel tank construct blow-molded：
By above-mentioned dosage, after ethylene hervene copolymer polyvinyl resin, antioxidant and auxiliary antioxidant mixing, it is added and is kneaded
Machine squeezes out in particle to cooling water, obtains particulate polyethylene product automobile plastic fuel tank construct blow-molded.
When kneading machine is kneaded, it is 230 DEG C to adjust kneading machine second segment barrel temperature, and third section barrel temperature is 235 DEG C, the
Four sections of barrel temperatures are 240 DEG C, and five sections of barrel temperatures are 245 DEG C, and the 6th section of barrel temperature is 250 DEG C, the 7th section of barrel temperature
It is 260 DEG C；The heat conduction oil temperature for heating kneading machine is 260 DEG C, and the temperature for adjusting particle cooling water is 68 DEG C, particle cooling water
Flow is 680m3/h。
Embodiment 3
The raw material of ethylene hervene copolymer vinyl：
1) polymer grade ethylene inlet amount 33.8t/h
2) catalyst：Chromium-based catalysts963 addition 196.1kg/h
3) 1- hexenes addition 842.8kg/h
4) diluent iso-butane 35.8kg/h
The preparation method of ethylene hervene copolymer vinyl：
Diluent iso-butane is in recurrent state always, ethylene and 1- hexenes is injected separately into annular-pipe reactor, strictly
Control ethylene hexene feed ratio, and be added in advance activated catalyst, control reactor in 95 DEG C of reaction temperature, ethylene into
Doses 33.8tt/h, 1- hexene inlet amount is 842.8kg/h, catalyst feeding quantity 196.1kg/h, and ethylene and 1- hexenes react
It is 5.5g/10min, density 0.945g/cm to melt flow rate3Ethylene hervene copolymer polyvinyl resin, molecular weight point
Cloth is 19.3, and weight average molecular weight is 35.6 ten thousand.
The raw material (parts by weight) of automobile plastic fuel tank construct blow-molded：
Wherein antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters；Auxiliary antioxidant
It is bis- (2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites.
The preparation method of automobile plastic fuel tank construct blow-molded：
By above-mentioned dosage, after ethylene hervene copolymer polyvinyl resin, antioxidant and auxiliary antioxidant mixing, it is added and is kneaded
Machine squeezes out in particle to cooling water, obtains particulate polyethylene product automobile plastic fuel tank construct blow-molded.
When kneading machine is kneaded, it is 230 DEG C to adjust kneading machine second segment barrel temperature, and third section barrel temperature is 235 DEG C, the
Four sections of barrel temperatures are 240 DEG C, and five sections of barrel temperatures are 245 DEG C, and the 6th section of barrel temperature is 250 DEG C, the 7th section of barrel temperature
It is 260 DEG C；The heat conduction oil temperature for heating kneading machine is 260 DEG C, and the temperature for adjusting particle cooling water is 68 DEG C, particle cooling water
Flow is 680m3/h。
Embodiment 4
The raw material of ethylene hervene copolymer vinyl：
1) polymer grade ethylene inlet amount 35.1t/h
2) catalyst：Chromium-based catalysts963 addition 210.7kg/h
3) 1- hexenes addition 872kg/h
4) diluent iso-butane 37.6g/h
The preparation method of ethylene hervene copolymer vinyl：
Diluent iso-butane is in recurrent state always, ethylene and 1- hexenes is injected separately into annular-pipe reactor, strictly
Ethylene hexene feed ratio is controlled, and activated catalyst in advance is added, controls 99.0 DEG C of reaction temperature in reactor, ethylene
Inlet amount 35.1t/h, 1- hexene inlet amount is 872kg/h, catalyst feeding quantity 210.7kg/h, and ethylene and 1- hexenes react
It is 6.0g/10min, density 0.944g/cm to melt flow rate3Ethylene hervene copolymer polyvinyl resin, molecular weight point
Cloth is 21.8, and weight average molecular weight is 28.3 ten thousand.
The raw material (parts by weight) of automobile plastic fuel tank construct blow-molded：
Wherein antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters；Auxiliary antioxidant
It is bis- (2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites.
The preparation method of automobile plastic fuel tank construct blow-molded：
By above-mentioned dosage, after ethylene hervene copolymer polyvinyl resin, antioxidant and auxiliary antioxidant mixing, it is added and is kneaded
Machine squeezes out in particle to cooling water, obtains particulate polyethylene product automobile plastic fuel tank construct blow-molded.
When kneading machine is kneaded, it is 230 DEG C to adjust kneading machine second segment barrel temperature, and third section barrel temperature is 235 DEG C, the
Four sections of barrel temperatures are 240 DEG C, and five sections of barrel temperatures are 245 DEG C, and the 6th section of barrel temperature is 250 DEG C, the 7th section of barrel temperature
It is 260 DEG C；The heat conduction oil temperature for heating kneading machine is 260 DEG C, and the temperature for adjusting particle cooling water is 68 DEG C, particle cooling water
Flow is 680m3/h。
Embodiment 5
The raw material of ethylene hervene copolymer vinyl：
1) polymer grade ethylene inlet amount 37t/h
2) catalyst：Chromium-based catalysts963 addition 187.3kg/h
3) 1- hexenes addition 877kg/h
4) diluent iso-butane 37.8kg/h
The preparation method of ethylene hervene copolymer vinyl：
Diluent iso-butane is in recurrent state always, ethylene and 1- hexenes is injected separately into annular-pipe reactor, strictly
Ethylene hexene feed ratio is controlled, and activated catalyst in advance is added, controls 94.3 DEG C of reaction temperature in reactor, ethylene
Inlet amount 37t/h, 1- hexene inlet amount is 877kg/h, catalyst feeding quantity 187.3kg/h, and ethylene and 1- hexenes are obtained by the reaction
Melt flow rate is 5.7g/10min, density 0.945g/cm3Ethylene hervene copolymer polyvinyl resin, molecular weight distribution
It is 16.1, weight average molecular weight is 37.2 ten thousand.
The raw material (parts by weight) of automobile plastic fuel tank construct blow-molded：
Wherein antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters；Auxiliary antioxidant
It is bis- (2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites.
The preparation method of automobile plastic fuel tank construct blow-molded：
By above-mentioned dosage, after ethylene hervene copolymer polyvinyl resin, antioxidant and auxiliary antioxidant mixing, it is added and is kneaded
Machine squeezes out in particle to cooling water, obtains particulate polyethylene product automobile plastic fuel tank construct blow-molded.
When kneading machine is kneaded, it is 230 DEG C to adjust kneading machine second segment barrel temperature, and third section barrel temperature is 235 DEG C, the
Four sections of barrel temperatures are 240 DEG C, and five sections of barrel temperatures are 245 DEG C, and the 6th section of barrel temperature is 250 DEG C, the 7th section of barrel temperature
It is 260 DEG C；The heat conduction oil temperature for heating kneading machine is 260 DEG C, and the temperature for adjusting particle cooling water is 68 DEG C, particle cooling water
Flow is 680m3/h。
Embodiment 6
The raw material of ethylene hervene copolymer vinyl：
1) polymer grade ethylene inlet amount 35.6t/h
2) catalyst：Chromium-based catalysts963 addition 172kg/h
3) 1- hexenes addition 818.8kg/h
4) diluent iso-butane 36.1kg/h
The preparation method of ethylene hervene copolymer vinyl：
Diluent iso-butane is in recurrent state always, ethylene and 1- hexenes is injected separately into annular-pipe reactor, strictly
Control ethylene hexene feed ratio, and be added in advance activated catalyst, control reactor in 96 DEG C of reaction temperature, ethylene into
Doses 35.6t/h, 1- hexene inlet amount is 818.8kg/h, catalyst feeding quantity 172kg/h, and ethylene and 1- hexenes are obtained by the reaction
Melt flow rate is 5.8g/10min, density 0.946g/cm3Ethylene hervene copolymer polyvinyl resin, molecular weight distribution
It is 19.2, weight average molecular weight is 31.2 ten thousand.
The raw material (parts by weight) of automobile plastic fuel tank construct blow-molded：
Wherein antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters；Auxiliary antioxidant
It is bis- (2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites.
The preparation method of automobile plastic fuel tank construct blow-molded：
By above-mentioned dosage, after ethylene hervene copolymer polyvinyl resin, antioxidant and auxiliary antioxidant mixing, it is added and is kneaded
Machine squeezes out in particle to cooling water, obtains particulate polyethylene product automobile plastic fuel tank construct blow-molded.
When kneading machine is kneaded, it is 230 DEG C to adjust kneading machine second segment barrel temperature, and third section barrel temperature is 235 DEG C, the
Four sections of barrel temperatures are 240 DEG C, and five sections of barrel temperatures are 245 DEG C, and the 6th section of barrel temperature is 250 DEG C, the 7th section of barrel temperature
It is 260 DEG C；The heat conduction oil temperature for heating kneading machine is 260 DEG C, and the temperature for adjusting particle cooling water is 68 DEG C, particle cooling water
Flow is 680m3/h。
The 1- hexene co-monomer contents of the automobile plastic fuel tank construct blow-molded of above-described embodiment 1~6 see the table below：
| 1- hexene co-monomer contents | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Mol% | 0.59 | 0.56 | 0.55 | 0.61 | 0.52 | 0.48 |
| Wt% | 1.74 | 1.65 | 1.62 | 1.80 | 1.53 | 1.42 |
The performance of the automobile plastic fuel tank construct blow-molded of above-described embodiment 1~6 see the table below：
Noting the test condition of the full notch tensile creep FNCT of * is：It is that (notch is deep for 100mm*10mm*10mm samples with size
Spend 1.6mm),
It is impregnated using 2% ArkopalN-100 solution, is tested under conditions of 80 DEG C of temperature, stress 4MPa.
Result shown in upper table as it can be seen that fuel tank of vehicle construct blow-molded provided by the invention mechanical performance and existing import
Fuel tank material is suitable, has excellent processing performance and physical and mechanical property, and rigidity-toughness balanced performance is good, and low-temperature impact performance protrudes,
Meet fuel tank blowing to require.The environmental stress cracking resistance and full notch tensile croop property of the present invention is much better than import fuel tank
Material, molding fuel tank product are not easy craze and transfiguration, have longer service life.
The present invention can be summarized with others without prejudice to the concrete form of the spirit or essential characteristics of the present invention, of the invention
Above-described embodiment can only all be considered the description of the invention rather than limit that every substantial technological according to the present invention is to above
Any subtle modifications, equivalent variations and modifications, belong in the range of technical solution of the present invention made by embodiment.
Claims (8)
1. a kind of special construct blow-molded of the automobile plastic fuel tank of resisting environmental stress and cracking, characterized in that its environmental stress resistance is opened
Split ability>8000h is mainly prepared by the raw material of following parts by weight：
99.50~99.70 parts of ethylene hervene copolymer polyvinyl resin
0.12~0.35 part of antioxidant
0.03~0.15 part of auxiliary antioxidant
0.02~0.06 part of releasing agent
5.3~the 6.5g/10min of melt flow rate (MFR) and density 0.943 of the ethylene hervene copolymer polyvinyl resin~
0.947kg/m3, molecular weight distribution is 15~25, and weight average molecular weight is 250,000~400,000, is prepared by the following method acquisition：
In the presence of diluent is in recurrent state and catalyst always, feed ethylene and 1- hexenes are placed in reaction vessel and carried out
Reaction, reaction temperature are 94~100 DEG C, and it is 5.3~6.5g/10min and density to react to the melt flow rate (MFR) of reaction product
For 0.943~0.947kg/m3When, stop reaction, obtains ethylene hervene copolymer polyvinyl resin.
2. the special construct blow-molded of the automobile plastic fuel tank of resisting environmental stress and cracking according to claim 1, characterized in that
The amount ratio of the ethylene and 1- hexenes is 1000 ﹕ 15~25；The dosage of 1- hexenes is 4~6 times of catalyst amount.
3. the special construct blow-molded of the automobile plastic fuel tank of resisting environmental stress and cracking according to claim 1 or claim 2, feature
It is that the dosage of the diluent is 34~39kg/h.
4. the special construct blow-molded of the automobile plastic fuel tank of resisting environmental stress and cracking according to claim 3, characterized in that institute
It is iso-butane to state diluent.
5. the special construct blow-molded of the automobile plastic fuel tank of resisting environmental stress and cracking according to claim 3, characterized in that institute
It is chromium-based catalysts to state catalyst.
6. the special construct blow-molded of the automobile plastic fuel tank of resisting environmental stress and cracking according to claim 3, characterized in that institute
Stating antioxidant uses phenolic antioxidant, auxiliary antioxidant to use phosphite ester kind antioxidant.
7. the special construct blow-molded of the automobile plastic fuel tank of resisting environmental stress and cracking according to claim 6, characterized in that institute
It is four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters to state phenolic antioxidant；The phosphorous acid esters are anti-
Oxygen agent is bis- (2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites.
8. the special construct blow-molded of the automobile plastic fuel tank of resisting environmental stress and cracking according to claim 1, characterized in that institute
It is zinc stearate to state releasing agent.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942733A (en) * | 2012-10-24 | 2013-02-27 | 中国石油化工股份有限公司 | Large hollow container blow molding material and preparation method thereof |
| CN104744796A (en) * | 2015-01-19 | 2015-07-01 | 中国石油化工股份有限公司 | High-hexene grafted high-density polyethylene geomembrane blow-molding material |
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| CN102942733A (en) * | 2012-10-24 | 2013-02-27 | 中国石油化工股份有限公司 | Large hollow container blow molding material and preparation method thereof |
| CN104744796A (en) * | 2015-01-19 | 2015-07-01 | 中国石油化工股份有限公司 | High-hexene grafted high-density polyethylene geomembrane blow-molding material |
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