CN105462048B - The preparation method of the dedicated construct blow-molded of the automobile plastic fuel tank of resisting environmental stress and cracking - Google Patents
The preparation method of the dedicated construct blow-molded of the automobile plastic fuel tank of resisting environmental stress and cracking Download PDFInfo
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- CN105462048B CN105462048B CN201510975304.4A CN201510975304A CN105462048B CN 105462048 B CN105462048 B CN 105462048B CN 201510975304 A CN201510975304 A CN 201510975304A CN 105462048 B CN105462048 B CN 105462048B
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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
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- C08K5/52—Phosphorus bound to oxygen only
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Abstract
The invention discloses a kind of preparation methods of the dedicated construct blow-molded of the automobile plastic fuel tank of resisting environmental stress and cracking, include the following steps：(1) in the presence of diluent is in recurrent state and catalyst always, feed ethylene and 1- hexene are placed in reaction vessel and are reacted, reaction temperature is 94 ~ 100 DEG C, is reacted to 0.943 ~ 0.947kg/m of 5.3 ~ 6.5g/10min of melt flow rate (MFR) and density of reaction product3When, stop reaction, obtains ethylene hervene copolymer polyvinyl resin；(2) 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 and 0.02 ~ 0.06 part of zinc stearate are taken, after mixing, kneading machine extruding pelletization is added, particle is cooling in cooling water, the dedicated construct blow-molded of the automobile plastic fuel tank of acquisition melt strength with higher, excellent environmental stress cracking resistance and creep resistant and good chemical corrosion resistance, the machine-shaping suitable for single layer, multilayer automobile plastic fuel tank.
Description
Technical field
The invention belongs to blow molded plastic fields, and in particular to a kind of resisting environmental stress and cracking automobile plastic fuel tank is dedicated to be blown
The preparation method of moulding material.
Background technique
Fuel tank plastic is an important directions of Hyundai Motor plastic, requirement and height with automotive light weight technology
Density polyethylene materials performance is continually developed, plastics on automobile using more and more extensive, the application amount of automobile plastic is more
It is to become to measure one of Trend of Auto Manufacturing Technologies level and mark of new material R & D Level.Compared with metal fuel tank, automobile modeling
Material fuel tank is light-weight, cabinet 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 molding 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 layer.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 dedicated construct blow-molded of HDPE, to guarantee that product is preferably rigid
Property and creep resistance, while dedicated 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 dedicated blow molding 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 company, JPE company of Japan public
The MS201BN etc. of department.Current country HDPE process units is due to the restriction by production technology, it is difficult to produce satisfactory
The dedicated 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 authenticated by automobile industry security performance, 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.
Summary of the invention
The object of the present invention is to provide a kind of systems of the dedicated construct blow-molded of the automobile plastic fuel tank of resisting environmental stress and cracking
Preparation Method, resulting automobile plastic fuel tank construct blow-molded ahexene content with higher, wider molecular weight distribution, performance etc.
Feature, product melt strength with higher, excellent environmental stress cracking resistance (ESCR/FNCT) and creep resistant are good
Good chemical corrosion resistance, the machine-shaping suitable for single layer, multilayer automobile plastic fuel tank.
The object of the invention is achieved through the following technical solutions：A kind of automobile plastic fuel tank of resisting environmental stress and cracking is dedicated
The preparation method of construct blow-molded, includes the following steps：
(1) in the presence of diluent is in recurrent state and catalyst always, feed ethylene and 1- hexene 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) ethylene is taken
99.50~99.80 parts of hervene copolymer polyvinyl resin, 0.05~0.35 part of antioxidant, 0.03~0.15 part of auxiliary antioxidant and
0.02~0.06 part of zinc stearate, after mixing, kneading machine extruding pelletization is added, particle is cooling in cooling water, obtains automobile modeling
Expect the dedicated construct blow-molded of fuel tank.
The amount ratio of ethylene and 1- hexene is 1000 ﹕ 15~30 in step (1) of the present invention；The dosage of 1- hexene is to urge
4~6 times of agent dosage.The dosage of the diluent is 34~39kg/h.
The specification of the ethylene of step (1) of the present invention is preferably：
Ethylene：Purity >=99.20% C2H2≤5×10-6 CO≤1×10-6
O2≤2×10-6 H2O≤1×10-6 COS≤0.02×10-6。
The specification of the 1- hexene of step (1) of the present invention is preferably：
1- hexene：Purity >=98.5% H2O≤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。
The diluent of step (1) of the present invention is preferably iso-butane.Wherein, the iso-butane of preferably following specification：
Iso-butane：Purity >=95.0% acetylene≤2 × 10-6Total sulfur≤1 × 10-6
Total olefin≤100 × 10-6Water≤20 × 10-6 O2≤5×10-6。
The catalyst of step (1) of the present invention is chromium-based catalysts, the chromium-based catalysts produced such as Grace company of the U.S.963。
In step (2) of the present invention, when kneading machine is kneaded, adjusting kneading machine second segment barrel temperature is 230 DEG C, 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 thermally conductive 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 dedicated construct blow-molded of automobile plastic fuel tank prepared by the present invention has sufficiently high molecular weight and reasonable point
Son amount distribution, high antioxygenic property meet the required processing performance of automobile plastic fuel tank blow molding and every physical mechanics
Performance has excellent rigidity-toughness balanced performance, low-temperature impact performance outstanding, excellent resisting environmental stress and cracking and resistance to full notch
Croop property.Resisting environmental stress and cracking (ESCR) of the invention>8000h is much better than import production much larger than the 500h of imported product
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
Product.
(2) the dedicated 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 reasonable molecular weight distribution and excellent rigid-tough balance and excellent resistance to environment to answer
Power cracking performance.
Specific embodiment
The catalyst activation treatment of following embodiment uses conventional method, specially：Catalyst is by opening tank bottom
Portion's valve, falls into activator by gravity, from the hot burning gas and fluidized hot air heat-activated furnace of the burner hearth of activation furnace
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 type, and extruder has 7 sections of cylinders.
Catalyst is chromium-based catalysts, the chromium-based catalysts produced using Grace company963。
Polymer grade ethylene：Purity >=99.20%, C2H2≤5×10-6, CO≤1 × 10-6, O2≤2×10-6, H2O≤1×
10- 6,
COS≤0.02×10-6。
1- hexene：Purity >=98.5%, H2O≤20×10-6, CO≤5 × 1O-6, monoolefine >=98.5%, isomery alhpa olefin
≤ 1%, just
Non- alhpa olefin≤1% of structure, positive structure alhpa olefin >=96%, peroxide≤1 × 10-6, sulphur≤1 × 10-6。
Iso-butane：Purity >=95.0%, acetylene≤2 × 10-6, total sulfur≤1 × 10-6, total olefin≤100 × 10-6, water≤
20×10-6, O2≤5×10-6。
The dedicated construct blow-molded of the 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, additional amount 112kg/h
3) 1- hexene additional amount 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- hexene 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 additional amount 457kg/h, catalyst feeding quantity 112kg/h, ethylene and 1- hexene react to obtain melt
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 phenyl) propionic acid] pentaerythritol esters；Auxiliary antioxidant
It is bis- (2,4- di-tert-butyl-phenyl) 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 are mixed, it is added and is kneaded
Machine squeezes out particle into cooling water, obtains particulate polyethylene product automobile plastic fuel tank construct blow-molded.
When kneading machine is kneaded, adjusting kneading machine second segment barrel temperature is 230 DEG C, 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 thermally conductive oil temperature for heating kneading machine is 260 DEG C, and the temperature for adjusting particle cooling water is 68 DEG C, and particle is 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, additional amount 149kg/h
3) 1- hexene additional amount 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- hexene 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- hexene are reacted and melted
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 phenyl) propionic acid] pentaerythritol esters；Auxiliary antioxidant
It is bis- (2,4- di-tert-butyl-phenyl) 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 are mixed, it is added and is kneaded
Machine squeezes out particle into cooling water, obtains particulate polyethylene product automobile plastic fuel tank construct blow-molded.
When kneading machine is kneaded, adjusting kneading machine second segment barrel temperature is 230 DEG C, 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 thermally conductive 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, additional amount 196.1kg/h
3) 1- hexene additional amount 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- hexene 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 33.8t t/h, 1- hexene inlet amount is 842.8kg/h, catalyst feeding quantity 196.1kg/h, ethylene and the reaction of 1- hexene
Obtaining melt flow rate is 5.5g/10min, density 0.945g/cm3Ethylene hervene copolymer polyvinyl resin, molecular weight
19.3 are distributed as, 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 phenyl) propionic acid] pentaerythritol esters；Auxiliary antioxidant
It is bis- (2,4- di-tert-butyl-phenyl) 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 are mixed, it is added and is kneaded
Machine squeezes out particle into cooling water, obtains particulate polyethylene product automobile plastic fuel tank construct blow-molded.
When kneading machine is kneaded, adjusting kneading machine second segment barrel temperature is 230 DEG C, 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 thermally conductive 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, additional amount 210.7kg/h
3) 1- hexene additional amount 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- hexene 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- hexene 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 phenyl) propionic acid] pentaerythritol esters；Auxiliary antioxidant
It is bis- (2,4- di-tert-butyl-phenyl) 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 are mixed, it is added and is kneaded
Machine squeezes out particle into cooling water, obtains particulate polyethylene product automobile plastic fuel tank construct blow-molded.
When kneading machine is kneaded, adjusting kneading machine second segment barrel temperature is 230 DEG C, 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 thermally conductive 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, additional amount 187.3kg/h
3) 1- hexene additional amount 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- hexene 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- hexene react to obtain
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 phenyl) propionic acid] pentaerythritol esters；Auxiliary antioxidant
It is bis- (2,4- di-tert-butyl-phenyl) 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 are mixed, it is added and is kneaded
Machine squeezes out particle into cooling water, obtains particulate polyethylene product automobile plastic fuel tank construct blow-molded.
When kneading machine is kneaded, adjusting kneading machine second segment barrel temperature is 230 DEG C, 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 thermally conductive 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, additional amount 172kg/h
3) 1- hexene additional amount 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- hexene 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- hexene react to obtain
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 phenyl) propionic acid] pentaerythritol esters；Auxiliary antioxidant
It is bis- (2,4- di-tert-butyl-phenyl) 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 are mixed, it is added and is kneaded
Machine squeezes out particle into cooling water, obtains particulate polyethylene product automobile plastic fuel tank construct blow-molded.
When kneading machine is kneaded, adjusting kneading machine second segment barrel temperature is 230 DEG C, 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 thermally conductive 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 content of the automobile plastic fuel tank construct blow-molded of above-described embodiment 1~6 see the table below：
| 1- hexene co-monomer content | 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：
Note the full notch tensile creep FNCT of * test condition be：With having a size of 100mm*10mm*10mm sample, (notch is deep
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 is as it can be seen that fuel tank of vehicle construct blow-molded mechanical performance provided by the invention and existing imported oil
Case material is suitable, has excellent processing performance and physical and mechanical property, and rigidity-toughness balanced performance is good, and low-temperature impact performance is prominent, full
Sufficient fuel tank blow molding requires.Environmental stress cracking resistance of the invention and full notch tensile croop property are 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 spirit or essential characteristics of the invention, of the invention
Above-described embodiment can only all be considered the description of the invention rather than limit that all substantial technologicals according to the present invention are to above
Any subtle modifications, equivalent variations and modifications, belong in the range of technical solution of the present invention made by embodiment.
Claims (6)
1. a kind of preparation method of the dedicated construct blow-molded of the automobile plastic fuel tank of resisting environmental stress and cracking, characterized in that including
Following steps：
(1) in the presence of diluent is in recurrent state and catalyst always, feed ethylene and 1- hexene is placed in reaction and held
Reacted in device, reaction temperature be 94 ~ 100 DEG C, react to reaction product 5.3 ~ 6.5g/10min of melt flow rate (MFR) and
0.943 ~ 0.947g/cm of density3When, stop reaction, obtains ethylene hervene copolymer polyvinyl resin；
(2) 99.50~99.80 parts of ethylene hervene copolymer polyvinyl resin, 0.05~0.35 part of antioxidant, auxiliary antioxidant are taken
0.03~0.15 part and 0.02 ~ 0.06 part of zinc stearate, after mixing, kneading machine extruding pelletization is added, particle is cold in cooling water
But, the dedicated construct blow-molded of automobile plastic fuel tank is obtained；
The molecular weight distribution of the ethylene hervene copolymer polyvinyl resin be 15.3~21.8, weight average molecular weight be 27.3 ten thousand~
37.2 ten thousand.
2. the preparation side of the dedicated construct blow-molded of the automobile plastic fuel tank of resisting environmental stress and cracking according to claim 1
Method, characterized in that the amount ratio of ethylene and 1- hexene is 1000 ﹕ 15 ~ 30 in the step (1)；The dosage of 1- hexene is catalysis
4 ~ 6 times of agent dosage.
3. the preparation side of the dedicated construct blow-molded of the automobile plastic fuel tank of resisting environmental stress and cracking according to claim 1
Method, characterized in that the dosage of the diluent is 34 ~ 39kg/h.
4. the preparation side of the dedicated construct blow-molded of the automobile plastic fuel tank of resisting environmental stress and cracking according to claim 3
Method, characterized in that the diluent of the step (1) is iso-butane.
5. the preparation side of the dedicated construct blow-molded of the automobile plastic fuel tank of resisting environmental stress and cracking according to claim 1
Method, characterized in that the catalyst of the step (1) is chromium-based catalysts.
6. the preparation side of the dedicated construct blow-molded of the automobile plastic fuel tank of resisting environmental stress and cracking according to claim 1
Method, characterized in that in the step (2), when kneading machine is kneaded, adjusting kneading machine second segment barrel temperature is 230 DEG C, 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 thermally conductive oil temperature for heating kneading machine is 260 DEG C, and is adjusted cold
But the temperature of water is 50~70 DEG C, and cooling water flow is 600~700m3/h。
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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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| 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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