CN107286421B - Polyethylene composition for automobile fuel tank produced by gas-phase fluidized bed process - Google Patents
Polyethylene composition for automobile fuel tank produced by gas-phase fluidized bed process Download PDFInfo
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Abstract
The invention relates to a polyethylene composition for an automobile oil tank, which is produced by a gas-phase fluidized bed process, and consists of high-density polyethylene and an additive, wherein the additive is formed by compounding an antioxidant, a processing aid, a lubricant and carbon fibers, and the tensile impact strength of the product can be improved by adding the additive, so that the product meets the requirements of automobile oil tank material products.
Description
Technical Field
The invention relates to a polyethylene composition, in particular to a polyethylene composition for an automobile oil tank, which is produced by a gas-phase fluidized bed process.
Background
In recent years, the automobile industry in China is continuously, rapidly and healthily developed, according to statistics of a national information center, the automobile sales volume in 2011 reaches 1900 million vehicles, wherein the sales volume of passenger vehicles (cars, MPVs and SUVs) is 1132 million vehicles, according to the forecast of 'blue book of automobile industry' jointly issued by the development research center of State academy and the society of automotive engineering, the growth of the Chinese passenger vehicles in 2010-2020 is nearly 10%, and the total annual demand in 2020 reaches 2337 million vehicles. The utilization rate of the plastic fuel tanks for producing automobiles in China at present reaches about 70 percent. Calculated according to the weight of the multilayer composite plastic oil tank of the automobile of 6-10Kg, the total demand of the special material of the oil tank of the automobile in China is about 10 ten thousand tons/year at present, the consumption market is mainly concentrated in the areas of east China, south China and northeast China, the areas of east China have oil tank production enterprises such as Yangzhou Asia general, Wuhu Shunlong, etc., the annual material consumption is 4-6 ten thousand tons; oil tank production enterprises such as Coretals and eight thousand generations exist in the south China, annual materials are 1-2 ten thousand tons, vinpocetine, Coretals and the like exist in the northeast, the annual materials are 1-2 ten thousand tons, the selling price is 1.4 ten thousand yuan/ton, the enterprises all depend on import, and imported products mainly include 4261AG of Basell company and HB111R of JPE company.
Compared with a metal fuel tank, the plastic fuel tank has the following advantages:
(1) the weight is light. Typically, the wall thickness of the iron tank is at least 1.2mm, the average wall of an automotive plastic fuel tankThe thickness is 4 mm. Since the density of iron is 7.8g/cm3Then the outer surface of the iron oil tank is subjected to rust prevention treatment, so that the density of the iron oil tank can reach 8.0g/cm3And the density of the HDPE plastic material is 0.945g/cm3And about, therefore, an iron fuel tank with the same volume is 2.5 times heavier than a plastic fuel tank.
(2) The anti-corrosion capability is strong. Because plastics have very strong chemical corrosion resistance ability, consequently car plastic fuel tank can not produce some impurity because of corroding to can not lead to impurity to get into the engine through oil supply system and lead to the damage of engine, reduce its life.
(3) The modeling is free. With increasing vehicle configurations, modern vehicles are becoming more compact in exterior design in order to make full use of space. Different from a metal fuel tank, a plastic fuel tank usually adopts a one-time blow molding mode, and can mold a special-shaped product with a complex shape, so that the plastic fuel tank is beneficial to molding a proper fuel tank shape according to the existing chassis residual space under the condition that the overall arrangement of an automobile is determined, and the volume of the fuel tank is increased as much as possible, which is incomparable to the metal fuel tank.
(4) Has high safety and will not explode due to thermal expansion. At present, most plastic fuel tanks are made of high molecular weight polyethylene materials. The thermal conductivity of this material is very low, being only 1% of that of metal. Meanwhile, the high molecular weight polyethylene has good elasticity and rigidity, can still maintain good mechanical properties at the temperature of minus 40 ℃ and 90 ℃, can rebound automatically after collision without permanent deformation, can not generate electric sparks to cause explosion accidents in the friction or collision process, and can not explode due to thermal expansion of the plastic fuel tank even if an automobile is carelessly ignited, so that the plastic fuel tank has high safety.
(5) The production cost is low, the processing technology is simple, no matter how complex product shapes are, the product can be formed in one step, and the material of the scrapped product after being crushed can be recycled.
The plastic fuel tank has many advantages different from the metal fuel tank, so that the plastic fuel tank instead of the metal fuel tank and the multilayer fuel tank instead of the single-layer fuel tank become the mainstream direction of the development of the automobile industry at present.
The first plastic fuel tank of the automobile in the world was developed by Volkswagen automobile company, BASF company and Kautex company in the united research of the 20 th century and 60 th generation, and was successfully used in Porsche sports cars. Automobile plastic fuel tanks have been rapidly developed and widely used in economically developed U.S. and europe, and manufacturers of INERGY and KAUTEX TEXTRON in europe have been in the leaders of plastic fuel tanks in the world, but with the explosive development of automobile plastic fuel tanks in north america and japan automobile markets, the proportion of foreign plastic fuel tanks has reached more than 90%.
The HDPE oil tank special material that domestic oil tank manufacturing enterprise used at present is imported, can divide into two types according to production technology and the catalyst that uses the HDPE oil tank special material again:
(1) the gas phase method comprises the following steps: the product 4261AG developed by Basell company by using Lupotech G gas phase stirred bed process and chromium-based catalyst.
(2) The slurry method comprises the following processes: JPE company, HB111R developed by Innovene S process and chromium catalyst; the Phillip company developed the C579 product using a Phillips single loop slurry process, a chromium-based catalyst.
The melt flow rate of the products produced by the two processes is 5.0-7.0 g/10min (21.6kg), and the density is 0.945-0.950 g/cm3The special material for the oil tank is used in domestic oil tank processing enterprises, and the key properties such as the processing property, the mechanical property, the impact property and the like of the special material for the oil tank produced by the two processes are not obviously different according to feedback information after the enterprise uses the special material. At present, no technology for producing the special material for the automobile oil tank by adopting a gas-phase fluidized bed process exists in the world.
CN 1753729A discloses a system and a method for polymerizing ethylene by using a chromium-based catalyst with controllable molecular weight and molecular weight distribution, and also provides a method for producing bimodal polyethylene by using a catalyst system containing two chromium catalysts, but the performance of the product is not obviously improved, and the system cannot be used for producing special materials for automobile fuel tanks.
In Japanese patent 200202412, Monoi discloses inorganic oxide-supported Cr-containing materials prepared by sintering under non-reducing conditions6+The use of a solid component (A), an alkoxide (B) containing a dialkylaluminium functionality and an aluminium trialkyl (C). The resulting ethylene polymers have good environmental stress crack resistance and good blow creep resistance. U.S. application 2002042428 discloses a process for the polymerization of ethylene in the co-presence of hydrogen using a trialkylaluminum compound-supported chromium catalyst (a) obtained by calcining and activating a Cr compound supported on an inorganic oxide support in a non-reducing atmosphere to convert the Cr atom to the hexavalent state, then treating a with a trialkylaluminum compound in an inert hydrocarbon solvent and removing the solvent in a short time.
Hasebe et al, Japanese patent 2001294612, disclose a catalyst comprising an inorganic oxide supported Cr compound (calcined at 300 ℃ C. to 1100 ℃ C. in a non-reducing atmosphere), R3-nAlLn(R-C1-12 alkyl; L-C1-8 alkoxy, phenoxy; 0<n<1) And a lewis basic organic compound. The catalyst produces polyethylene having a high molecular weight and a narrow molecular weight distribution.
In Japanese patent 2001198811, Hasebe et al disclose that compounds containing Cr oxide (supported on a refractory compound and activated by heating under non-reducing conditions) and R are tried3-nAlLn(R-C1-6 alkyl; L-C1-8 alkoxy, phenoxy; 0.5<n<1) The catalyst of (3) polymerizes olefins. In SiO2Loaded CrO3And 0.9:1MeOH-Et3Ethylene was polymerized in the presence of the reaction product of the Al mixture, giving a polymer having a melt index of 0.18g/10min (at 190 ℃ under a load of 2.16 kg) and a 1-hexene content of 1.6 mg/g.
In chinese patent 1214344, a supported chromium-based catalyst for the gas phase polymerization of ethylene by impregnating an inorganic oxide support having hydroxyl groups on the surface with inorganic chromium outdoor and anhydrous solution; drying in air; activating the particles in oxygen; and reduction of the activated catalyst intermediate with an organoaluminum compound. 10g of silica gel was mixed with 0.05mol/LCrO3 aqueous solution, dried at 80-120 ℃ for 12h, baked at 200 ℃ for 2h and at 600 ℃ for 4h, reduced with 25% diethyl aluminum ethoxide in hexane to yield a powder catalyst with a Cr content of 0.25% and an Al/Cr ratio of 3.
Durand et al, U.S. patent 5,075,395, describe a process for eliminating the induction period in the polymerization of ethylene by contacting ethylene under fluid bed polymerization conditions and/or with mechanical agitation with a charged powder in the presence of a chromium oxide compound bound to a particulate support and activated by heat treatment, said catalyst being used in the form of a prepolymer. The Durand process is characterized in that the charged powder of petroleum is treated beforehand by contacting it with an organoaluminium compound in such a way that the polymerization of ethylene starts immediately after the contact with the charged powder in the presence of the prepolymer.
In U.S. patent 4,559,394, McDaniel describes the polymerization of olefins using a chromium catalyst and a tertiary alcohol. The patent teaches that the addition of an alcohol to the chromium oxide improves the chromium distribution. McDaniel added the tertiary alcohol prior to catalyst activation. Interestingly, McDaniel teaches that the use of silanols does not achieve the above objectives.
Ikegaim et al, u.s. patents 4,454,242 and 4,451,573 use silanol in conjunction with a chromium oxide catalyst treated with zirconium or titanium and an alkyl magnesium compound to produce an improved Environmental Stress Cracking Resistance (ESCR) product.
Chromium catalysts based on chromocene and silanol have been prepared and deposited on silica to increase catalyst activity as described in U.S. patent 4,153,576 to Karol et al. U.S. patent 3,767,635 to mitsubishi chemical Industries, ltd; 3,629,216, respectively; and 3,759,918 describe the addition of pentaalkylsiloxy alane to supported chromium oxide catalysts to make useful polyethylene.
Chromium oxide (CrOx) based catalysts have high activity, moderate induction times and produce polymers with high and intermediate molecular weight distributions. The silylchromate based catalysts have a weaker activity but produce polymers with a broader powder mass distribution. Silyl chromate catalysts are generally more expensive than chromium oxide catalysts. It is required to obtain a process which allows the adjustment of the chromium oxide-based catalysts so that the polymers produced by them reach the properties of the polymers produced using the silylchromate-based catalysts. For background information on silylchromate catalysis, see, e.g., U.S. Pat. nos. 3,324,095 and 3,324,101 to Carrick et al. The prior art lacks an inexpensive, simple method for modifying chromium oxide catalysts to variably adjust the polymers produced thereby to polymers produced based on silylchromate catalyst systems.
The invention relates to a polyethylene composition for an automobile oil tank, which is produced by a gas-phase fluidized bed process, and the polyethylene composition has the characteristics of low production cost and good mechanical property of a product, and no relevant report about the production of a special material for the automobile oil tank by the method exists at present.
The invention discloses a polyethylene composition for an automobile oil tank produced by a gas-phase fluidized bed process and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a polyethylene composition for an automobile oil tank, which is produced by a gas-phase fluidized bed process, and consists of high-density polyethylene and an additive, wherein the additive is formed by compounding an antioxidant, a processing aid, a lubricant and carbon fibers, and the tensile impact strength of the polyethylene can be obviously improved by adding the composition.
The polyethylene composition for the automobile oil tank produced by the gas-phase fluidized bed process comprises the following components: high density polyethylene and additives;
in the polyethylene composition, the high-density polyethylene accounts for 100 parts by weight; 0.04-0.8 part of additive;
the additive is prepared by compounding an antioxidant, a processing aid, a lubricant and carbon fibers, and the addition amounts of the high-density polyethylene per gram are as follows:
antioxidant: 100-3000 ppm;
processing aid: 100-1000 ppm;
lubricant: 100-;
carbon fiber: 100-2000 ppm.
The polyethylene composition for the automobile fuel tank produced by the gas-phase fluidized bed process is characterized in that the carbon fibers are preferably short cut filaments, and the diameter of the carbon fibers is preferably 1-10 mm.
The polyethylene composition for the automobile oil tank produced by the gas-phase fluidized bed process is characterized in that the antioxidant is preferably one or more of 2, 6-di-tert-butyl-4-methylphenol, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester, tris (1, 4-di-tert-butylphenyl) phosphite and 1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid.
The polyethylene composition for the automobile fuel tank produced by the gas-phase fluidized bed process is characterized in that the processing aid is preferably calcium stearate or zinc stearate.
The polyethylene composition for the automobile oil tank produced by the gas-phase fluidized bed process is characterized in that the lubricant is one or more of erucamide, oleamide and fluoroelastomer.
The polyethylene composition for the automobile fuel tank produced by the gas-phase fluidized bed process of the invention is characterized in that the carbon fibers are preferably added into the fluidized bed in the ethylene polymerization process, and the antioxidant, the processing aid and the lubricant are preferably added into the mixing roll in the polyethylene consignment granulation process.
The polyethylene composition for the automobile fuel tank produced by the gas-phase fluidized bed process is preferably one having a melt flow rate of 4.0-10.0 g/10min and a density of 0.942-0.950 g/cm under a weight of 21.6kg3。
The polyethylene composition for the automobile fuel tank produced by the gas-phase fluidized bed process, provided by the invention, preferably has a tensile impact strength of 140KJ/m or more at-50 DEG C2And a tensile impact strength at-30 ℃ of 170KJ/m or more20 ℃ tensile impact strength of 220KJ/m or more2Stretching at 25 DEG CThe impact strength is more than or equal to 280KJ/m2Tensile impact strength at 50 ℃ of 260KJ/m or more2Tensile impact strength at 70 ℃ of 240KJ/m or more2。
The polyethylene composition for the automobile oil tank is produced by adopting a chromium-titanium composite catalyst in a gas-phase fluidized bed polyethylene process.
The invention relates to a polyethylene composition for an automobile oil tank, which is produced by a gas-phase fluidized bed process, and consists of high-density polyethylene and an additive, wherein the additive is formed by compounding an antioxidant, a processing aid, a lubricant and carbon fibers, and the tensile impact strength of the product can be improved by adding the additive, so that the product meets the requirements of automobile oil tank material products.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
The addition amount of the antioxidant is as follows:
in the present invention, the amount of the antioxidant to be added is not particularly limited, and is usually 3000ppm based on each gram of high density polyethylene, with the addition of 100-; if the addition amount of the antioxidant is less than 100ppm, the product is cracked and aged due to the excessively small addition amount of the antioxidant, and the addition amount of the antioxidant exceeds 3000ppm, so that the waste is caused due to the excessively large use amount of the antioxidant, the product is not easy to machine and mold, and no other beneficial effects are realized.
The addition amount of the processing aid is as follows:
in the present invention, the amount of the adsorbent is not particularly limited, but 100ppm of the adsorbent is added per gram of the high density polyethylene; if the amount of the processing aid added is less than 100ppm, the effect of improving the surface and stabilizing the processing cannot be achieved due to the excessively small amount of the processing aid added, and the amount of the processing aid added exceeds 1000ppm, which causes waste and has no other beneficial effects.
Addition amount of lubricant:
in the present invention, the amount of the lubricant added is not particularly limited, but 100-2000ppm of the lubricant is added per gram of the high density polyethylene; if the amount of the lubricant added is less than 100ppm, the effect cannot be obtained because the amount of the lubricant added is too small, while the amount of the lubricant added exceeds 2000ppm, waste is caused because the amount of the lubricant used is too large, and the product is not easy to be formed and has no other beneficial effects.
The addition amount of the carbon fiber:
in the present invention, the amount of the carbon fiber added is not particularly limited, and the carbon fiber is added in an amount of 100-2000ppm based on each gram of the high density polyethylene; if the addition amount of the carbon fiber is less than 100ppm, the tensile yield impact strength of the product is not obviously improved due to the fact that the addition amount of the carbon fiber is too small, the addition amount of the carbon fiber exceeds 2000ppm, the carbon fiber is condensed due to too much use amount, the product is not easy to machine and form, and other beneficial effects are not achieved.
The type of antioxidant:
in the present invention, the kind of the antioxidant is not particularly limited, and the antioxidant is usually one or more selected from 2, 6-di-tert-butyl-4-methylphenol, octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tris (1, 4-di-tert-butylphenyl) phosphite, and 1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid.
The types of processing aids:
in the present invention, the kind of the processing aid is not particularly limited, and examples of the processing aid include calcium stearate and zinc stearate.
Lubricant type:
in the present invention, the type of lubricant is not particularly limited, and generally, the lubricant may be one or more of erucamide, oleamide, and fluoroelastomer.
The type of carbon fiber:
in the present invention, the kind of the carbon fiber is not particularly limited, and the carbon fiber is usually a chopped strand having a diameter of 1 to 10 mm.
High density polyethylene:
in the invention, a special chromium catalyst is adopted to produce the polyethylene by the Unipol polyethylene process, and the polyethylene is characterized in that the melt flow rate of a 21.6kg weight is 4.0-10.0 g/10min, and the density is 0.942-0.950 g/cm3。
If the flow rate of the high-density polyethylene melt is less than 4.0g/10min, the high-density polyethylene melt is not suitable for processing and molding due to too low flow rate, and the flow rate of the high-density polyethylene melt is more than 10.0g/10min, the high-density polyethylene melt is difficult to process and mold due to too high flow rate, and no other beneficial effects exist;
if the high density polyethylene has a density of less than 0.942g/cm3The density of the high-density polyethylene is too low, so that the oil tank is soft, insufficient in mechanical property and easy to deform; while the density of the high-density polyethylene is more than 0.950g/cm3The high density polyethylene has too high density, so that the product is hard and brittle, has poor impact performance, and is easy to crack particularly under low temperature conditions.
Example 1:
the polyethylene composition for the automobile oil tank is produced by adopting a gas-phase fluidized bed process, wherein carbon fibers in the composition are chopped fibers, the diameter of the chopped fibers is 7mm, and the content of the chopped fibers is 100ppm (based on per gram of high-density polyethylene); the antioxidant is 2, 6-di-tert-butyl-4-methylphenol, and the content is 100ppm (based on per gram of high-density polyethylene); the processing aid is calcium stearate with the content of 800ppm (based on each gram of high-density polyethylene); the lubricants were erucamide and oleamide at levels of 500ppm and 100ppm (per gram of high density polyethylene).
The melt flow rate was measured with a 21.6kg weight for 5.5g/10min and the density was 0.942g/cm3. The composition has a tensile impact strength of 145KJ/m at-50 DEG C2And a tensile impact strength of 178KJ/m at-30 DEG C2229KJ/m tensile impact strength at 0 DEG C2Tensile impact strength at 25 ℃ of 286KJ/m2Tensile impact strength at 50 ℃ of 270KJ/m2Tensile impact strength at 70 ℃ of 248KJ/m2。
Example 2:
the polyethylene composition for the automobile oil tank is produced by adopting a gas-phase fluidized bed process, wherein carbon fibers in the composition are chopped fibers, the diameter of the chopped fibers is 3mm, and the content of the chopped fibers is 1000ppm (based on per gram of high-density polyethylene); the antioxidant is beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester and 2, 6-di-tert-butyl-4-methylphenol, the content is 300ppm (based on each gram of high density polyethylene); the processing aid is zinc stearate with the content of 400ppm (based on per gram of high-density polyethylene); the lubricant was oleamide at a level of 1600ppm (per gram of high density polyethylene).
The melt flow rate was measured with a 21.6kg weight at 9.0g/10min and the density at 0.946g/cm3. The composition has a tensile impact strength of 156KJ/m at-50 DEG C2And a tensile impact strength at-30 ℃ of 185KJ/m2Tensile impact strength at 0 ℃ of 237KJ/m225 ℃ tensile impact strength 297KJ/m2Tensile impact strength at 50 ℃ of 275KJ/m2Tensile impact strength at 70 ℃ of 255KJ/m2。
Example 3:
the polyethylene composition for the automobile oil tank is produced by adopting a gas-phase fluidized bed process, wherein carbon fibers in the composition are chopped fibers, the diameter of the chopped fibers is 5mm, and the content of the chopped fibers is 1400ppm (based on per gram of high-density polyethylene); the antioxidant is tris (1, 4-di-tert-butylphenyl) phosphite and 1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, the contents of which are 900ppm and 500ppm (based on per gram of high-density polyethylene); the processing aid is calcium stearate with the content of 100ppm (based on per gram of high-density polyethylene); the lubricants were fluoroelastomer and erucamide at levels of 900ppm and 300ppm (per gram of high density polyethylene).
The melt flow rate was 4.5g/10min with a 21.6kg weight and a density of 0.950g/cm3. The composition has a tensile impact strength of 152KJ/m at-50 DEG C2And a tensile impact strength at-30 ℃ of 174KJ/m20 ℃ tensile impact strength of 223KJ/m2Tensile impact strength at 25 ℃ of 284KJ/m2Tensile impact strength at 50 ℃ of 265KJ/m270 ℃ tensile impact strength of 244KJ/m2。
Example 4:
the polyethylene composition for the automobile oil tank is produced by adopting a gas-phase fluidized bed process, wherein carbon fibers in the composition are chopped fibers, the diameter of the chopped fibers is 2mm, and the content of the chopped fibers is 1800ppm (based on per gram of high-density polyethylene); the antioxidant is 1, 3, 5-tri (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid and beta- (3, 5-di-tert-butyl-4-hydroxybenzyl) propionic acid octadecyl ester, the content of each is 900ppm (based on per gram of high density polyethylene); the processing aid is calcium stearate with the content of 700ppm (based on each gram of high-density polyethylene); the lubricant was erucamide at a level of 300ppm (per gram of high density polyethylene).
The melt flow rate was measured with a 21.6kg weight at 8.0g/10min and the density at 0.944g/cm3. The composition has tensile impact strength of 143KJ/m at-50 DEG C2And-30 ℃ tensile impact strength 183KJ/m2Tensile impact strength at 0 ℃ of 238KJ/m2Tensile impact strength at 25 ℃ of 302KJ/m250 ℃ tensile impact strength of 280KJ/m2Tensile impact strength at 70 ℃ of 240KJ/m2。
Example 5:
the polyethylene composition for the automobile oil tank is produced by adopting a gas-phase fluidized bed process, wherein carbon fibers in the composition are chopped fibers, the diameter of the chopped fibers is 1mm, and the content of the chopped fibers is 900ppm (based on per gram of high-density polyethylene); the antioxidant is beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester and tris (1, 4-di-tert-butylphenyl) phosphite, and the contents are 1000ppm and 500ppm (based on each gram of high-density polyethylene); the processing aid is zinc stearate with the content of 300ppm (based on per gram of high-density polyethylene); the lubricants were oleamide and fluoroelastomer at levels of 1000ppm and 500ppm (per gram of high density polyethylene).
The melt flow rate was measured with a 21.6kg weight at 7.0g/10min and the density at 0.943g/cm3. The composition has a tensile impact strength of 158KJ/m at-50 DEG C2And a tensile impact strength at-30 ℃ of 187KJ/m20 ℃ tensile impact strength 226KJ/m2Tensile impact strength at 25 ℃ of 288KJ/m2Tensile impact strength at 50 ℃ of 285KJ/m2Tensile impact strength at 70 ℃ of 247KJ/m2。
Example 6:
the polyethylene composition for the automobile oil tank is produced by adopting a gas-phase fluidized bed process, wherein carbon fibers in the composition are chopped fibers with the diameter of 10mm, and the content of the carbon fibers is 1600ppm (based on per gram of high-density polyethylene); the antioxidant is 1, 3, 5-tri (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, 2, 6-di-tert-butyl-4-methylphenol and beta- (3, 5-di-tert-butyl-4-hydroxybenzene) propionic acid octadecyl ester, and the contents are respectively 800ppm, 500ppm and 600ppm (based on per gram of high-density polyethylene); the processing aid is zinc stearate with the content of 1000ppm (based on per gram of high-density polyethylene); the lubricant was a fluoroelastomer and was present in an amount of 1000ppm (per gram of high density polyethylene).
The melt flow rate was measured with a 21.6kg weight at 10.0g/10min and the density at 0.945g/cm3. The composition has a tensile impact strength of 140KJ/m at-50 DEG C2And a tensile impact strength at-30 ℃ of 176KJ/m20 ℃ tensile impact strength of 220KJ/m225 ℃ tensile impact strength of 280KJ/m2Tensile impact strength at 50 ℃ of 275KJ/m2Tensile impact strength at 70 ℃ of 252KJ/m2。
Example 7:
the polyethylene composition for the automobile oil tank is produced by adopting a gas-phase fluidized bed process, wherein carbon fibers in the composition are chopped fibers, the diameter of the chopped fibers is 8mm, and the content of the chopped fibers is 1200ppm (based on per gram of high-density polyethylene); the antioxidant is tris (1, 4-di-tert-butylphenyl) phosphite in an amount of 2000ppm (per gram of high-density polyethylene); the processing aid is calcium stearate with the content of 900ppm (based on per gram of high-density polyethylene); the lubricant was a fluoroelastomer and was present in an amount of 100ppm (per gram of high density polyethylene).
The melt flow rate was measured with a 21.6kg weight at 4.0g/10min and the density at 0.947g/cm3. The composition has a tensile impact strength of 154KJ/m at-50 DEG C2And a tensile impact strength at-30 ℃ of 170KJ/m2Tensile impact strength at 0 ℃ of 235KJ/m2Tensile impact strength at 25 ℃ of 294KJ/m2Tensile impact strength at 50 ℃ of 260KJ/m2Tensile impact strength at 70 ℃ of 250KJ/m2。
Example 8:
the polyethylene composition for the automobile oil tank is produced by adopting a gas-phase fluidized bed process, wherein carbon fibers in the composition are short shreds, the diameter of the short shreds is 4mm, and the content of the short shreds is 2000ppm (based on per gram of high-density polyethylene); the antioxidant is beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester, tris (1, 4-di-tert-butylphenyl) phosphite and 1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, and the contents are 1500ppm, 500ppm and 300ppm (based on per gram of high-density polyethylene); the processing aid is zinc stearate with the content of 200ppm (based on per gram of high-density polyethylene); the lubricant was oleamide at a level of 2000ppm (per gram of high density polyethylene).
The melt flow rate was measured with a 21.6kg weight at 5.0g/10min and the density at 0.949g/cm3. The composition has a tensile impact strength of 160KJ/m at-50 DEG C2And a tensile impact strength of 180KJ/m at-30 DEG C20 ℃ tensile impact strength of 244KJ/m2Tensile impact strength at 25 ℃ of 305KJ/m250 ℃ tensile impact strength 271KJ/m2Tensile impact strength at 70 ℃ of 243KJ/m2。
Example 9:
the polyethylene composition for the automobile oil tank is produced by adopting a gas-phase fluidized bed process, wherein carbon fibers in the composition are chopped fibers, the diameter of the chopped fibers is 9mm, and the content of the chopped fibers is 300ppm (based on per gram of high-density polyethylene); the antioxidant is 2, 6-di-tert-butyl-4-methylphenol, and the content is 3000ppm (based on per gram of high-density polyethylene); the processing aid is zinc stearate with the content of 500ppm (based on per gram of high-density polyethylene); the lubricants were erucamide, oleamide, and fluoroelastomer, each at a level of 600ppm (per gram of high density polyethylene).
The melt flow rate was measured with a 21.6kg weight at 6.5g/10min and the density at 0.948g/cm3. The composition has a tensile impact strength of 147KJ/m at-50 DEG C2And a tensile impact strength at-30 ℃ of 172KJ/m2Tensile impact strength at 0 ℃ of 232KJ/m2Tensile impact strength at 25 ℃ of 300KJ/m250 ℃ tensile impact strength of 280KJ/m2Tensile impact strength at 70 ℃ of 251KJ/m2。
Example 10:
the polyethylene composition for the automobile oil tank is produced by adopting a gas-phase fluidized bed process, wherein carbon fibers in the composition are chopped fibers with the diameter of 6mm and the content of 1000ppm (based on per gram of high-density polyethylene); the antioxidant is 1, 3, 5-tri (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, and the content is 2600ppm (based on per gram of high-density polyethylene); the processing aid is zinc stearate with the content of 700ppm (based on each gram of high-density polyethylene); the lubricant was a fluoroelastomer and was present in an amount of 900ppm (per gram of high density polyethylene).
The melt flow rate was measured with a 21.6kg weight at 6.0g/10min and the density at 0.946g/cm3. The composition has a tensile impact strength of 149KJ/m at-50 DEG C2Tensile impact strength at-30 ℃ of 171KJ/m2Tensile impact strength at 0 ℃ of 241KJ/m2Tensile impact strength at 25 ℃ of 291KJ/m250 ℃ tensile impact strength of 290KJ/m2Tensile impact strength at 70 ℃ of 256KJ/m2。
Claims (6)
1. A polyethylene composition for an automobile oil tank produced by a gas-phase fluidized bed process comprises the following components: high density polyethylene and additives;
in the polyethylene composition, the high-density polyethylene accounts for 100 parts by weight; 0.04-0.8 part of additive;
the additive is prepared by compounding an antioxidant, a processing aid, a lubricant and carbon fibers, and the addition amounts of the high-density polyethylene per gram are as follows:
antioxidant: 100-3000 ppm;
processing aid: 100-1000 ppm;
lubricant: 100-;
carbon fiber: 100-;
the polyethylene composition has a melt flow rate of 4.0-10.0 g/10min and a density of 0.942-0.950 g/cm under a weight of 21.6kg3；
The carbon fibers are chopped strands with the diameter of 1-10mm, and are added into the fluidized bed in the ethylene polymerization process.
2. The polyethylene composition for the fuel tank of the automobile produced by the gas-phase fluidized-bed process according to claim 1, wherein the antioxidant is one or more of 2, 6-di-tert-butyl-4-methylphenol, octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tris (1, 4-di-tert-butylphenyl) phosphite and 1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate.
3. The gas phase fluidized bed process-produced polyethylene composition for fuel tanks of automobiles according to claim 1, wherein the processing aid is calcium stearate or zinc stearate.
4. The polyethylene composition for automobile fuel tanks produced by the gas phase fluidized bed process according to claim 1, wherein the lubricant is one or more of erucamide, oleamide and fluoroelastomer.
5. The polyethylene composition for automobile fuel tanks produced by the gas-phase fluidized-bed process according to claim 1, wherein the antioxidant, the processing aid and the lubricant are added to a mixer during the extrusion granulation of polyethylene.
6. The polyethylene composition for the fuel tank of the automobile produced by the gas-phase fluidized bed process according to any one of claims 1 to 5, wherein the polyethylene composition has a tensile impact strength at-50 ℃ of 140KJ/m or more2And a tensile impact strength at-30 ℃ of 170KJ/m or more20 ℃ tensile impact strength of 220KJ/m or more2And the tensile impact strength at 25 ℃ is more than or equal to 280KJ/m2Tensile impact strength at 50 ℃ of 260KJ/m or more2Tensile impact strength at 70 ℃ of 240KJ/m or more2。
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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 |
| CN102417650A (en) * | 2011-11-28 | 2012-04-18 | 浙江伟星新型建材股份有限公司 | Wear-resistant crosslinked PE (Polyethylene) composite pipe and manufacturing method thereof |
| WO2013085788A1 (en) * | 2011-12-09 | 2013-06-13 | Icl-Ip America Inc. | Synergized flame retarded polyolefin polymer composition, article thereof, and method of making the same |
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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 |
| CN102417650A (en) * | 2011-11-28 | 2012-04-18 | 浙江伟星新型建材股份有限公司 | Wear-resistant crosslinked PE (Polyethylene) composite pipe and manufacturing method thereof |
| WO2013085788A1 (en) * | 2011-12-09 | 2013-06-13 | Icl-Ip America Inc. | Synergized flame retarded polyolefin polymer composition, article thereof, and method of making the same |
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