CN110964143A - Polyethylene base resin for beverage bottle cap and preparation method thereof - Google Patents
Polyethylene base resin for beverage bottle cap and preparation method thereof Download PDFInfo
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Abstract
The polyethylene base resin is prepared by adopting a high-activity Ti/Cr series slurry catalyst to catalyze the copolymerization of ethylene and α -olefin with more than three carbons on the basis of a gas-phase fluidized bed polyethylene process of a single reactor, and taking hydrogen as a molecular weight regulator.
Description
Technical Field
The invention relates to a preparation method of polyethylene, in particular to polyethylene base resin for beverage bottle caps produced by a gas-phase fluidized bed process.
Background
With the widespread use of plastic bottle packaging in many fields, bottle caps are becoming more and more important, and the bottle caps are becoming more and more prominent in beverage, dairy, daily chemical, medical, or other industries. The bottle cap is used as a link in plastic bottle packaging, and is very important for ensuring the product quality.
Since the mid-90 s of the last century, PET bottled beverages produced by coca-cola companies used plastic bottle caps instead of aluminum caps, and thus, the plastic bottle caps were pushed to the front of beverage packages. After that, the powerful packaging enterprises and beverage manufacturers in China introduce foreign equipment, and the large-scale production and application of plastic bottle caps are started. World-known lid-making machines such as belief lid, sago, oka, heuski, etc. have also entered our country. Nowadays, the plastic bottle cap which is light and thin and easy to open is used for beverage packaging, so that convenience is brought to consumers, and the development of the beverage industry is accelerated.
At present, enterprises for producing HDPE bottle cap materials at home and abroad adopt different production processes, and the main production processes are three types: (1) the gas phase method comprises the following steps: the gas phase method process does not need a solvent in the polymerization reaction process, does not have solvent residue, and is more suitable for producing bottle cap materials; (2) slurry polymerization process: by adopting the slurry process, the product has good processing performance and can meet the requirement of food sanitation performance; (3) loop + gas phase process: by taking Borstar process production as a representative in northern Europe chemical industry, and adopting a combined process of a supercritical ring pipe and a gas phase, the solubility of the oligomer in a solvent is improved in a supercritical state, the content of the oligomer in the product is greatly reduced, and meanwhile, the two reactors are connected in series, so that the molecular weight distribution of the product is wider, and the processing performance is good.
CN 201210302019.2 discloses a polyethylene resin composition for manufacturing bottle caps, which is characterized in that the polyethylene resin is added with a composite slipping agent and nano zinc oxide to meet the slipping requirement without generating peculiar smell. The composition mainly comprises the following components: polyethylene resin, a composition of erucamide and oleamide in a certain proportion, polyethylene glycol, nano zinc oxide and an antioxidant.
CN 201010500727.8A high-toughness and high-brightness polyethylene bottle cap and a preparation method thereof, the high-toughness and high-brightness polyethylene bottle cap is prepared by dispersing materials composed of the following components in parts by weight in a high-speed kneading machine, and finally performing injection molding to obtain the bottle cap, wherein the polyethylene 100 parts, the color master batch 0.5-5 parts, the toughening agent 5-10 parts, the brightening agent 1-5 parts, and the auxiliary agent 5-10 parts. The impact strength of the material is more than or equal to 50kJ/m2The yield strength is more than or equal to 10MPa, and the glossiness is more than or equal to 80 percent.
CN 201310492905.0 discloses a nucleating master batch for improving the production speed of a polyethylene bottle cap, which mainly comprises the following components in percentage by weight: 95-99 parts of PE; 0.5-2.5 parts of nucleating agent; 0.1-0.9 part of hydrotalcite and 0.1-0.9 part of antioxidant; 0.1-0.9 part of dispersant. The nucleating agent and the PE are blended, extruded and granulated, and the prepared nucleating master batch can effectively improve the crystallization temperature of the polyethylene, so that the production speed of the polyethylene bottle cap is improved.
CN 201410526592.0 discloses a high impact polypropylene bottle cap material and a preparation method thereof, and discloses the high impact polypropylene bottle cap material, wherein the melt flow rate is 6-8 g/10min, the bonding ethylene content is 10.0-12.0%, the cantilever beam notch impact strength is more than or equal to 120J/m, the flexural modulus is more than or equal to 1100MPa, the thermal deformation temperature is more than or equal to 100 ℃, and the high impact polypropylene bottle cap material is prepared by mixing random copolymerization polypropylene, an antioxidant, an acid absorbent, a stiffening agent and a slipping agent, wherein the melt flow rate of the random copolymerization polypropylene is 6-8 g/10min, the bonding ethylene content is 10.0-12.0%, the weight average molecular weight is 270000-300000, and the molecular weight distribution is 4.10-4.50. The invention also discloses a preparation method of the bottle cap material. The bottle cap material has good rigidity and toughness balance, high heat deformation temperature, high glossiness, low shrinkage rate, good slip property and processability, and can meet the process requirements of different high-speed cap making processing equipment.
CN 201010515978.3A polypropylene composition for use in the production of carbonated beverage bottle caps, the present invention relates to a polypropylene composition for use in the production of carbonated beverage bottle caps, the composition comprising: homo-polypropylene: 30-60 parts, the isotacticity is more than 99%, and the MFR is 1-30g/10 min; 30-60 parts of block copolymer polypropylene MFR1-15g/10 min; polyethylene: 4 to 20 portions of the modified starch with the density of 0.955 to 0.968g/cm3MFR of 1 to 15g/10 min; 5-15 parts of polyolefin elastomer; nucleating agent: 0.05-0.2 part; the content of the slipping agent is as follows: 0.3-1 part of the product has excellent rigidity, better impact resistance and good stress whitening resistance.
Chromium-based catalysts are used primarily to produce High Density Polyethylene (HDPE) having a broad relative molecular mass distribution, and the high relative molecular mass portion of the HDPE often contains a small number of long chain branches, and thus has unique rheological and processing properties. However, since chromium catalysts have poor copolymerization properties and long initiation induction period, they are not favorable for the production of high-performance and high-value-added products, and therefore, it is necessary to modify them. Titanium is the most commonly used material for surface modification of silica gel supports for chromium-based catalysts. The chromium-based catalyst using titanium modified silica gel as a carrier can be used for producing polymers with high Melt Flow Rate (MFR) and wide relative molecular mass distribution, and is particularly suitable for processing large hollow containers, gas pipes and water supply pipes which can resist long-term static pressure, automobile fuel tanks and the like.
US 4454242 and US 4451573 use silanols together with chromium oxide catalysts treated with zirconium or titanium and magnesium alkyl compounds to produce improved Environmental Stress Cracking Resistance (ESCR) products. US3887494, CN1031945C and CN1088620C adopt a method of coprecipitation or cogel of silicon oxide, titanium and chromium components to modify the catalyst, the existence of titanium has little influence on the activity of the catalyst, and the relative molecular mass of the prepared polymer is reduced and the MFR is increased along with the increase of the content of titanium. The preparation of chromium-containing catalyst with titanium-containing or titanium-and chromium-containing silica gel requires spray drying or azeotropic drying of the coprecipitate or cogel to obtain the carrier, and the carrier also requires long-term aging under neutral pH condition. After aging, washing with ammonium salt or dilute acid, and aging in alkaline aqueous suspension for a long time, even adding hole-protecting agent. The preparation process is complex, the time consumption is long, the aging process has decisive influence on the pore structure of the catalyst, and the preparation repeatability is poor. Titanium is present in the catalyst in the form of anatase titanium dioxide, which has a poor effect on the MFR when producing high density polyethylene. The patents US4294724 and CN1443203A also relate to loading titanium tetraisopropoxide and other compounds in an organic acid environment, but the method has the disadvantages of long preparation process route of the catalyst, complex preparation means, easy damage to the pore structure of the carrier, high cost and the like.
The preparation process of the titanium modified chromium catalyst is simple, the initiation induction time of ethylene polymerization is shortened, the molecular weight distribution of the product is widened, the performance of the obtained polyethylene is improved, the active center of the chromium catalyst is redistributed due to the introduction of titanium, a new chromium active center is generated, and new polymerization characteristics and purposes of the chromium catalyst are endowed. Titanium can be added to the supported chromium-based catalyst by various methods, and the modified titanium can be divided into surface titanium and structural titanium, and the final active component is titanium oxide. However, in essence, the introduction of titanium is added to the support and surface of the catalyst before the chromium active site, and the activity of titanium during the polymerization process is negligible.
In addition, the titanium modified chromium catalyst is fed by solid catalyst dry powder, has poor fluidity, is easy to bond and agglomerate in a catalyst storage tank or form a bridge, and cannot be added into a gas-phase fluidized bed reactor through an automatic valve, so that the catalyst cannot be continuously fed, and the reaction is forced to stop. The slurry or liquid catalyst is a catalyst for gas phase ethylene polymerization process, and is a suspension or solution catalyst dispersed in viscous liquid, and has solid content of about 20% and solid particle diameter less than 50 microns. Compared with silica gel supported solid catalyst, the slurry catalyst has the advantages of high activity, low cost, good quality of polymerization products and the like, and has a tendency of replacing the traditional solid catalyst. The existing slurry catalysts are all titanium catalysts. The prior art lacks a cheap and simple method for producing polyethylene by using a high-activity Ti/Cr series slurry catalyst.
The invention is innovative that in a gas-phase fluidized bed reactor, a high-activity catalyst is adopted to catalyze ethylene and α -olefin copolymerization with more than three carbons, and hydrogen is taken as a molecular weight regulator to prepare the polyethylene base resin for the beverage bottle cap.
Disclosure of Invention
The polyethylene base resin has the characteristics of good melt flowability, excellent processing performance, high mechanical strength, good sanitary performance and the like, and can meet various performances of a polyethylene special material for a non-gassy beverage bottle cap. The preparation method of the polyethylene base resin for the beverage bottle cap provided by the invention is easy to implement and stable in product performance.
The invention provides a beverage bottle capThe polyethylene base resin is used, wherein the weight average molecular weight of the polyethylene base resin is 8-15 ten thousand, the molecular weight distribution index is 7-15, the α -olefin mass content is 2-8 per thousand, the melt flow rate is 1.8-3.0 g/10min (2.16kg), 50.0-80.0 g/10min (21.6kg), and the density is 0.948-0.955 g/cm3The tensile yield strength is more than 20MPa, the bending strength is more than 10MPa, the bending modulus is more than 500MPa, and the impact strength at minus 30 ℃ is more than 3kJ/m2The full-notch creep strength is more than 50h, and the melt strength at 210 ℃ is more than 10 cN.
The polyethylene base resin for the beverage bottle cap is prepared by catalyzing ethylene and α -olefin copolymerization with more than three carbons by adopting a high-activity Ti/Cr series slurry catalyst on a gas-phase fluidized bed polyethylene process of a single reactor, and taking hydrogen as a molecular weight regulator.
The polyethylene base resin for the beverage bottle cap is characterized in that the active center of the high-activity Ti/Cr slurry catalyst is preferably a titanium and chromium composite double-active center, and the catalyst activity is more than 2.0 kgPE/gcat.
The polyethylene base resin for the beverage bottle cap disclosed by the invention is characterized in that the high-activity Ti/Cr slurry catalyst preferably comprises the following components in percentage by weight: 60-80% of mineral oil and 20-40.0% of solid catalyst;
wherein, the content of titanium accounts for 0.1-10.0 wt% of the solid catalyst, and the content of chromium accounts for 0.1-10.0 wt% of the solid catalyst.
The invention also provides a preparation method of the polyethylene base resin for the beverage bottle cap, which is the preparation method of the polyethylene base resin for the beverage bottle cap and comprises the following steps:
s1 preprocessing stage:
adding polyethylene powder resin into a gas-phase fluidized bed reactor as a seed bed, and replacing the reactor with inert components for more than three times;
and S2 passivation stage:
starting a compressor to perform flow replacement on the polyethylene powder resin for more than 72 hours, and adding a cocatalyst into the fluidized bed reactor to perform passivation treatment;
and S3 component adjustment stage:
sequentially adding ethylene, α -olefin, inert components, refrigerant and molecular weight regulator into a reactor;
s4 polymerization stage:
when the concentration of each component in the reactor reaches a set value, adjusting the reaction temperature and the reaction pressure, controlling the reaction time, and adding a high-activity Ti/Cr series slurry catalyst to initiate polymerization.
The preparation method of the polyethylene base resin for the beverage bottle cap, disclosed by the invention, is characterized in that the active center of the high-activity Ti/Cr slurry catalyst is preferably a titanium and chromium composite double-active center, and the activity of the catalyst is more than 2.0 kgPE/gcat.
The preparation method of the polyethylene base resin for the beverage bottle cap, disclosed by the invention, comprises the following steps of preferably, the high-activity Ti/Cr slurry catalyst comprises the following components in percentage by weight: 60-80% of mineral oil and 20-40.0% of solid catalyst;
wherein, the content of titanium accounts for 0.1-10.0 wt% of the solid catalyst, and the content of chromium accounts for 0.1-10.0 wt% of the solid catalyst.
The preparation method of the polyethylene base resin for the beverage bottle cap, disclosed by the invention, has the advantage that in the S4 polymerization reaction stage, the reaction pressure is preferably 1.4-2.8 MPa.
The preparation method of the polyethylene base resin for the beverage bottle cap, disclosed by the invention, comprises the step of S4 polymerization reaction, wherein the reaction temperature is preferably 70-110 ℃.
The preparation method of the polyethylene base resin for the beverage bottle cap, disclosed by the invention, has the advantage that in the S4 polymerization reaction stage, the reaction time is preferably 0.5-8 hours.
The preparation method of the polyethylene base resin for the beverage bottle cap, disclosed by the invention, is characterized in that the mole percentage content of water and oxygen in the gas-phase fluidized bed reactor is preferably less than 10 ppm.
The preparation method of the polyethylene base resin for the beverage bottle cap comprises the step of adjusting the component S3, wherein the inert component is nitrogen, and the molar percentage of the inert component is 0-50%.
The preparation method of the polyethylene base resin for the beverage bottle cap, disclosed by the invention, is characterized in that the refrigerant is preferably 1-pentane, 1-hexane or a mixture of the 1-pentane and the 1-hexane, and the molar percentage of the refrigerant is 0-50%.
The preparation method of the polyethylene base resin for the beverage bottle cap, disclosed by the invention, is characterized in that the mole percentage of ethylene in the gas-phase fluidized bed reactor is preferably 50-70%.
The preparation method of the polyethylene base resin for the beverage bottle caps, disclosed by the invention, comprises the step of preferably selecting α -olefin from 1-butene, 1-hexene and a mixture of the 1-butene and the 1-hexene in the gas-phase fluidized bed reactor, wherein the molar ratio of α -olefin to ethylene in the reactor is 0.01-0.1.
The preparation method of the polyethylene base resin for the beverage bottle cap, disclosed by the invention, is characterized in that the molecular weight regulator in the gas-phase fluidized bed reactor is preferably hydrogen, and the molar ratio of the hydrogen to ethylene in the reactor is 0.05-0.15.
In the preparation method of the polyethylene base resin for the beverage bottle cap, the cocatalyst is preferably an alkyl aluminum compound in the S2 passivation treatment stage.
The method for preparing the polyethylene base resin for the beverage bottle cap is characterized in that the alkyl aluminum compound is preferably methylaluminoxane, ethoxydiethylaluminum, trimethylaluminum, triethylaluminum, triisobutylaluminum or monochlorodiethylaluminum.
The preparation method of the polyethylene base resin for the beverage bottle cap, disclosed by the invention, is characterized in that the adding amount of the alkyl aluminum compound is preferably 2-5% of the weight of the seed bed.
The invention can also be detailed as follows:
the polyethylene base resin is prepared by using high-activity Ti/Cr series slurry catalyst to catalyze the copolymerization of ethylene and α -olefin with more than three carbons in a single-reactor gas-phase fluidized bed polyethylene process, and using hydrogen as a molecular weight regulator, wherein the weight of the polyethylene base resin isThe average molecular weight is 8-15 ten thousand, the molecular weight distribution index is 7-15, the α -olefin content is 2-8 per thousand, the melt flow rate is 1.8-3.0 g/10min (2.16kg), 50.0-80.0 g/10min (21.6kg), the density is 0.948-0.955 g/cm3The tensile yield strength is more than 20MPa, the bending strength is more than 10MPa, the bending modulus is more than 500MPa, and the impact strength at minus 30 ℃ is more than 3kJ/m2The full-notch creep strength is more than 50h, and the melt strength at 210 ℃ is more than 10 cN.
The invention also provides a preparation method of the polyethylene base resin for the beverage bottle cap, which comprises the following steps of S1 pretreatment stage, wherein a certain amount of polyethylene powder resin is added into a gas-phase fluidized bed reactor as a seed bed, an inert component is adopted to replace the reactor for more than three times, S2 passivation stage is to start a compressor to replace the powder resin for more than 72 hours in a flowing manner, and a certain amount of cocatalyst is added into the fluidized bed reactor for passivation, S3 component adjustment stage is to add ethylene, α -olefin, the inert component, a refrigerant and a molecular weight regulator into the reactor in sequence according to a certain proportion, and S4 polymerization stage is to add a high-activity Ti/Cr series slurry catalyst to initiate polymerization reaction under the conditions that the reaction temperature is 70-110 ℃ and the reaction pressure is 1.4-2.8 MPa after the concentration of each component in the reactor reaches a set value.
The polyethylene base resin for the beverage bottle cap has the advantages that the active center of the high-activity Ti/Cr slurry catalyst is a titanium and chromium composite double-active center, and the activity of the catalyst is more than 2.0 kgPE/gcat.
The high-activity Ti/Cr series slurry catalyst comprises the following components in percentage by weight: 60-80% of mineral oil and 20-40.0% of solid catalyst; the titanium content accounts for 0.1-10.0 wt% of the solid catalyst, and the chromium content accounts for 0.1-10.0 wt% of the solid catalyst.
According to the preparation method of the polyethylene base resin for the beverage bottle cap, the pressure of a fluidized bed reactor is 1.4-2.8 MPa;
according to the preparation method of the polyethylene base resin for the beverage bottle cap, the reaction temperature of a fluidized bed is 70-110 ℃;
according to the preparation method of the polyethylene base resin for the beverage bottle cap, the reaction time of the fluidized bed is 0.5-8 hours;
according to the preparation method of the polyethylene base resin for the beverage bottle cap, the requirement of the mole percentage content of water and oxygen in a fluidized bed reactor is less than 10 ppm;
according to the preparation method of the polyethylene base resin for the beverage bottle cap, the inert component in the fluidized bed reactor is nitrogen, and the molar percentage content is 0-50%;
according to the preparation method of the polyethylene base resin for the beverage bottle cap, a refrigerant in a fluidized bed reactor can be 1-pentane, 1-hexane or a mixture of the 1-pentane and the 1-hexane, and the molar percentage content is 0-50%.
According to the preparation method of the polyethylene base resin for the beverage bottle cap, the mol percentage content of ethylene in a fluidized bed reactor is 50-70%;
according to the preparation method of the polyethylene base resin for the beverage bottle cap, α -olefin with more than three carbons in a fluidized bed reactor is 1-butene, 1-hexene and a mixture of the 1-butene and the 1-hexene, and the molar ratio of α -olefin to ethylene in the reactor is 0.01-0.1;
according to the preparation method of the polyethylene base resin for the beverage bottle cap, the molecular weight regulator in the fluidized bed reactor is hydrogen, and the molar ratio of the hydrogen to the ethylene in the reactor is 0.05-0.15;
the invention relates to a preparation method of polyethylene base resin for beverage bottle caps, wherein a cocatalyst in a fluidized bed reactor is an alkyl aluminum compound;
the invention relates to a preparation method of polyethylene base resin for beverage bottle caps, wherein an alkyl aluminum compound in a fluidized bed reactor is one of methylaluminoxane, ethoxy diethyl aluminum, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum or chloro diethyl aluminum;
according to the preparation method of the polyethylene base resin for the beverage bottle cap, disclosed by the invention, the alkyl aluminum compound in the fluidized bed reactor is only used at the stage of passivating the seed bed, and the addition amount is 2-5% of the weight of the seed bed.
The invention has the beneficial effects that:
the invention controls the polyethylene base resin used for the beverage bottle cap to have proper melt flow rate, density and proper molecular weight distribution through the process conditions of polymerization temperature, pressure, reaction gas composition, catalyst and the like, thereby meeting the requirements of good processing performance, various physical and mechanical properties, sanitation and the like of the pressed bottle cap. The polyethylene base resin for beverage bottle caps prepared by the method does not use a solvent, and is beneficial to controlling the odor of products. The invention has mild reaction, not only ensures that the catalyst has higher activity, but also can ensure that the generation of low molecular weight parts influencing the smell is reduced, and simultaneously avoids the occurrence of unfavorable phenomena such as implosion and the like caused by the excessively fast release of the activity of the catalyst.
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.
A50 kg/h gas-phase full-density polyethylene pilot plant is adopted, 200kg of powder resin is added into a gas-phase fluidized bed reactor to serve as a seed bed, nitrogen is adopted to replace the reactor for more than three times, a compressor is started to replace the powder resin for more than 72h in a flowing mode, a certain amount of triethyl aluminum is added into the fluidized bed reactor to perform passivation treatment, ethylene, a comonomer, nitrogen, isopentane and hydrogen are introduced into the reactor to serve as raw material gases in the reaction, component adjustment is performed through the nitrogen, when the concentration of each component, the reaction temperature and the reaction pressure in the reactor reach set values, a catalyst is added to initiate polymerization reaction, 1000kg of resin is produced in an accumulated mode, the powder resin is taken out to perform performance evaluation, and the result is shown in.
Example 1:
the polyethylene base resin for beverage bottle caps is produced on a gas-phase fluidized bed polyethylene device, a high-activity Ti/Cr series slurry catalyst is adopted, and the weight percentage of each component is as follows: 72.0% of mineral oil and 28.0% of solid catalyst; the titanium content in the solid catalyst was 0.25 wt%, the chromium content in the solid catalyst was 0.25 wt%, and the catalyst activity was 2.5 kgPE/gcat. The specific production process comprises the following steps:
the reactor pressure is 1.4MPa, the reaction temperature is 70 ℃, the mole percentage content of water and oxygen in the reactor is required to be less than 10ppm, the mole percentage content of nitrogen is 29%, the mole percentage content of ethylene is 57.2%, the mole percentage content of isopentane is 7%, the mole ratio of α -olefin to ethylene is 0.04, the mole ratio of hydrogen to ethylene is 0.08, and the α -olefin of the comonomer is 1-butene.
The performance test result of the polyethylene special material prepared by the process is as follows:
the melt flow rate was 55.4g/10min with a 21.6kg weight, 1.8g/10min with a 2.16kg weight and a density of 0.9483g/cm3Tensile yield strength of 23.0MPa, bending strength of 15.7MPa, bending modulus of 574MPa, impact strength of 3.9kJ/m at-30 DEG C2Full notch creep strength 59h, melt strength at 210 ℃ 10.8 cN.
Example 2:
the polyethylene base resin for beverage bottle caps is produced on a gas-phase fluidized bed polyethylene device, a high-activity Ti/Cr series slurry catalyst is adopted, and the weight percentage of each component is as follows: 72.0% of mineral oil and 28.0% of solid catalyst; the titanium content in the solid catalyst was 0.25 wt%, the chromium content in the solid catalyst was 0.25 wt%, and the catalyst activity was 5.5 kgPE/gcat. The specific production process comprises the following steps:
the reactor pressure is 1.4MPa, the reaction temperature is 110 ℃, the mole percentage content of water and oxygen in the reactor is required to be less than 10ppm, the mole percentage content of nitrogen is 18 percent, the mole percentage content of ethylene is 57.9 percent, the mole percentage content of isopentane is 16 percent, the mole ratio of α -olefin to ethylene is 0.03, the mole ratio of hydrogen to ethylene is 0.11, and α -olefin of comonomer is 1-butene.
The performance test result of the polyethylene special material prepared by the process is as follows:
the melt flow rate was measured with a 21.6kg weight at 72.3g/10min and with a 2.16kg weight at meltThe bulk flow rate was 2.8g/10min and the density was 0.9492g/cm3Tensile yield strength of 24.6MPa, bending strength of 14.8MPa, bending modulus of 524MPa, and impact strength of 3.6kJ/m at-30 DEG C2Full notch creep strength 61h, melt strength 10.5cN at 210 ℃.
Example 3:
the polyethylene base resin for beverage bottle caps is produced on a gas-phase fluidized bed polyethylene device, a high-activity Ti/Cr series slurry catalyst is adopted, and the weight percentage of each component is as follows: 72.0% of mineral oil and 28.0% of solid catalyst; the titanium content in the solid catalyst was 0.5 wt%, the chromium content in the solid catalyst was 0.5 wt%, and the catalyst activity was 4.5 kgPE/gcat. The specific production process comprises the following steps:
the reactor pressure is 2.8MPa, the reaction temperature is 70 ℃, the mole percentage content of water and oxygen in the reactor is required to be less than 10ppm, the mole percentage content of nitrogen is 21%, the mole percentage content of ethylene is 57.9%, the mole percentage content of isopentane is 13%, the mole ratio of α -olefin to ethylene is 0.03, the mole ratio of hydrogen to ethylene is 0.11, and the α -olefin of the comonomer is 1-butene.
The performance test result of the polyethylene special material prepared by the process is as follows:
the melt flow rate was determined to be 59.7g/10min with a 21.6kg weight, 0.9524g/cm with a density of 2.2g/10min with a 2.16kg weight3Tensile yield strength of 22.7MPa, bending strength of 13.8MPa, bending modulus of 567MPa, impact strength at-30 ℃ of 3.8kJ/m2Full notch creep strength 54h, melt strength at 210 ℃ 11.3 cN.
Example 4:
the polyethylene base resin for beverage bottle caps is produced on a gas-phase fluidized bed polyethylene device, a high-activity Ti/Cr series slurry catalyst is adopted, and the weight percentage of each component is as follows: 80.0% of mineral oil and 20.0% of solid catalyst; the titanium content in the solid catalyst was 1.0 wt%, the chromium content in the solid catalyst was 1.0 wt%, and the catalyst activity was 9.6 kgPE/gcat. The specific production process comprises the following steps:
the reactor pressure is 2.8MPa, the reaction temperature is 110 ℃, the mole percentage content of water and oxygen in the reactor is required to be less than 10ppm, the mole percentage content of nitrogen is 16%, the mole percentage content of ethylene is 57.4%, the mole percentage content of isopentane is 21%, the mole ratio of α -olefin to ethylene is 0.05, the mole ratio of hydrogen to ethylene is 0.1, and the α -olefin of the comonomer is 1-butene.
The performance test result of the polyethylene special material prepared by the process is as follows:
the melt flow rate was measured to be 73.4g/10min with a 21.6kg weight, the melt flow rate was measured to be 2.6g/10min with a 2.16kg weight, and the density was 0.9488g/cm3Tensile yield strength of 22.7MPa, bending strength of 16.2MPa, bending modulus of 538MPa, and impact strength of 3.8kJ/m at-30 DEG C2Full notch creep strength 53h, melt strength at 210 ℃ 10.6 cN.
Example 5:
the polyethylene base resin for beverage bottle caps is produced on a gas-phase fluidized bed polyethylene device, a high-activity Ti/Cr series slurry catalyst is adopted, and the weight percentage of each component is as follows: 80% of mineral oil and 20% of solid catalyst; the titanium content in the solid catalyst was 1.5 wt%, the chromium content in the solid catalyst was 2.0 wt%, and the catalyst activity was 8.1 kgPE/gcat. The specific production process comprises the following steps:
the reactor pressure is 2.0MPa, the reaction temperature is 100 ℃, the mole percentage content of water and oxygen in the reactor is required to be less than 10ppm, the mole percentage content of nitrogen is 26%, the mole percentage content of ethylene is 59.9%, the mole percentage content of isopentane is 7%, the mole ratio of α -olefin to ethylene is 0.02, the mole ratio of hydrogen to ethylene is 0.10, and the α -olefin of the comonomer is 1-butene.
The performance test result of the polyethylene special material prepared by the process is as follows:
the melt flow rate was 58.3g/10min with a 21.6kg weight, 2.2g/10min with a 2.16kg weight and a density of 0.9507g/cm3Tensile yield strength of 24.5MPa, bending strength of 13.7MPa, bending modulus of 545MPa, and impact strength of 3.4kJ/m at-30 DEG C2Full notch creep strength 55h, melt strength 10.7cN at 210 ℃.
Example 6:
the polyethylene base resin for beverage bottle caps is produced on a gas-phase fluidized bed polyethylene device, a high-activity Ti/Cr series slurry catalyst is adopted, and the weight percentage of each component is as follows: 60.0% of mineral oil and 40.0% of solid catalyst; the titanium content in the solid catalyst was 2.5 wt%, the chromium content in the solid catalyst was 0.2 wt%, and the catalyst activity was 2.3 kgPE/gcat. The specific production process comprises the following steps:
the reactor pressure is 1.6MPa, the reaction temperature is 70 ℃, the mole percentage content of water and oxygen in the reactor is required to be less than 10ppm, the mole percentage content of nitrogen is 24%, the mole percentage content of ethylene is 62%, the mole percentage content of isopentane is 9%, the mole ratio of α -olefin to ethylene is 0.01, the mole ratio of hydrogen to ethylene is 0.07, and the mole ratio of α -olefin of comonomer is 1-hexene.
The performance test result of the polyethylene special material prepared by the process is as follows:
the melt flow rate was measured with a 21.6kg weight at 52.7g/10min, the melt flow rate was measured with a 2.16kg weight at 1.8g/10min and the density was 0.9526g/cm3Tensile yield strength of 26.6MPa, bending strength of 15.8MPa, bending modulus of 536MPa, and impact strength of 3.7kJ/m at-30 DEG C2Full notch creep strength 63h, melt strength at 210 ℃ 11.0 cN.
Example 7:
the polyethylene base resin for beverage bottle caps is produced on a gas-phase fluidized bed polyethylene device, a high-activity Ti/Cr series slurry catalyst is adopted, and the weight percentage of each component is as follows: 72.0% of mineral oil and 28.0% of solid catalyst; the titanium content in the solid catalyst was 5.5 wt%, the chromium content in the solid catalyst was 2.0 wt%, and the catalyst activity was 5.1 kgPE/gcat. The specific production process comprises the following steps:
the reactor pressure is 1.5MPa, the reaction temperature is 110 ℃, the mole percentage content of water and oxygen in the reactor is required to be less than 10ppm, the mole percentage content of nitrogen is 13%, the mole percentage content of ethylene is 57.1%, the mole percentage content of isopentane is 22%, the mole ratio of α -olefin to ethylene is 0.01, the mole ratio of hydrogen to ethylene is 0.13, and the α -olefin of the comonomer is 1-hexene.
The performance test result of the polyethylene special material prepared by the process is as follows:
the melt flow rate was 66.4g/10min with a 21.6kg weight, 2.7g/10min with a 2.16kg weight and a density of 0.9537g/cm3Tensile yield strength of 24.8MPa, bending strength of 14.3MPa, bending modulus of 539MPa, impact strength of 3.9kJ/m at-30 DEG C2Full notch creep strength 54h, melt strength at 210 ℃ 11.7 cN.
Example 8:
the polyethylene base resin for beverage bottle caps is produced on a gas-phase fluidized bed polyethylene device, a high-activity Ti/Cr series slurry catalyst is adopted, and the weight percentage of each component is as follows: 72.0% of mineral oil and 28.0% of solid catalyst; the titanium content in the solid catalyst was 0.5 wt%, the chromium content in the solid catalyst was 5.0 wt%, and the catalyst activity was 4.7 kgPE/gcat. The specific production process comprises the following steps:
the reactor pressure is 2.8MPa, the reaction temperature is 80 ℃, the mole percentage content of water and oxygen in the reactor is required to be less than 10ppm, the mole percentage content of nitrogen is 25%, the mole percentage content of ethylene is 55.4%, the mole percentage content of isopentane is 13%, the mole ratio of α -olefin to ethylene is 0.02, the mole ratio of hydrogen to ethylene is 0.10, and the mole ratio of α -olefin of comonomer is 1-hexene.
The performance test result of the polyethylene special material prepared by the process is as follows:
the melt flow rate was 57.60g/10min with a 21.6kg weight, 0.9528g/cm density at 2.0g/10min with a 2.16kg weight3Tensile yield strength of 27.2MPa, bending strength of 16.3MPa, bending modulus of 612MPa, and impact strength of 3.2kJ/m at-30 DEG C2Full notch creep strength 54h, melt strength 10.9cN at 210 ℃.
Example 9:
the polyethylene base resin for beverage bottle caps is produced on a gas-phase fluidized bed polyethylene device, a high-activity Ti/Cr series slurry catalyst is adopted, and the weight percentage of each component is as follows: 72.0% of mineral oil and 28.0% of solid catalyst; the titanium content in the solid catalyst was 10.0 wt%, the chromium content in the solid catalyst was 10.0 wt%, and the catalyst activity was 9.1 kgPE/gcat. The specific production process comprises the following steps:
the reactor pressure is 2.8MPa, the reaction temperature is 110 ℃, the mole percentage content of water and oxygen in the reactor is required to be less than 10ppm, the mole percentage content of nitrogen is 19%, the mole percentage content of ethylene is 53.1%, the mole percentage content of isopentane is 20%, the mole ratio of α -olefin to ethylene is 0.01, the mole ratio of hydrogen to ethylene is 0.14, and the α -olefin of the comonomer is 1-hexene.
The performance test result of the polyethylene special material prepared by the process is as follows:
the melt flow rate was 75.4g/10min with a 21.6kg weight, 2.8g/10min with a 2.16kg weight and a density of 0.9541g/cm3Tensile yield strength of 25.8MPa, bending strength of 13.4MPa, bending modulus of 528MPa, and impact strength of 4.1kJ/m at-30 DEG C2Full notch creep strength 57h, melt strength at 210 ℃ 11.1 cN.
Example 10:
the polyethylene base resin for beverage bottle caps is produced on a gas-phase fluidized bed polyethylene device, a high-activity Ti/Cr series slurry catalyst is adopted, and the weight percentage of each component is as follows: 72.0% of mineral oil and 28.0% of solid catalyst; the titanium content in the solid catalyst was 7.5 wt%, the chromium content in the solid catalyst was 7.5 wt%, and the catalyst activity was 7.5 kgPE/gcat. The specific production process comprises the following steps:
the reactor pressure is 2.0MPa, the reaction temperature is 100 ℃, the mole percentage content of water and oxygen in the reactor is required to be less than 10ppm, the mole percentage content of nitrogen is 8%, the mole percentage content of ethylene is 59.9%, the mole percentage content of isopentane is 25%, the mole ratio of α -olefin to ethylene is 0.01, the mole ratio of hydrogen to ethylene is 0.11, and the mole ratio of α -olefin of comonomer is 1-hexene.
The performance test result of the polyethylene special material prepared by the process is as follows:
the melt flow rate was measured with a 21.6kg weight at 61.2g/10min, using 2.1A melt flow rate of 2.2g/10min measured with a 6kg weight of 0.9546g/cm density3Tensile yield strength of 26.0MPa, bending strength of 14.5MPa, bending modulus of 556MPa, and impact strength of 3.4kJ/m at-30 DEG C2Full notch creep strength 57h, melt strength at 210 ℃ 10.8 cN.
Example 11:
the polyethylene base resin for beverage bottle caps is produced on a gas-phase fluidized bed polyethylene device, a high-activity Ti/Cr series slurry catalyst is adopted, and the weight percentage of each component is as follows: 72.0% of mineral oil and 28.0% of solid catalyst; the titanium content in the solid catalyst was 1.0 wt%, the chromium content in the solid catalyst was 1.0 wt%, and the catalyst activity was 6.3 kgPE/gcat. The specific production process comprises the following steps:
the reactor pressure is 2.0MPa, the reaction temperature is 90 ℃, the mole percentage content of water and oxygen in the reactor is required to be less than 10ppm, the mole percentage content of nitrogen is 22%, the mole percentage content of ethylene is 59.5%, the mole percentage content of isopentane is 12%, the mole ratio of α -olefin to ethylene is 0.02, the mole ratio of hydrogen to ethylene is 0.09, and the mole ratio of α -olefin of comonomer is 1-hexene.
The performance test result of the polyethylene special material prepared by the process is as follows:
the melt flow rate was measured with a 21.6kg weight at 56.6g/10min, the melt flow rate was measured with a 2.16kg weight at 2.1g/10min and the density was 0.9518g/cm3Tensile yield strength of 22.8MPa, bending strength of 16.7MPa, bending modulus of 547MPa, impact strength of 3.5kJ/m at-30 DEG C2Full notch creep strength 59h, melt strength at 210 ℃ 10.4 cN.
Example 12:
the polyethylene base resin for beverage bottle caps is produced on a gas-phase fluidized bed polyethylene device, a high-activity Ti/Cr series slurry catalyst is adopted, and the weight percentage of each component is as follows: 72.0% of mineral oil and 28.0% of solid catalyst; the titanium content in the solid catalyst was 1.0 wt%, the chromium content in the solid catalyst was 1.0 wt%, and the catalyst activity was 3.6 kgPE/gcat. The specific production process comprises the following steps:
the reactor pressure is 1.8MPa, the reaction temperature is 80 ℃, the mole percentage content of water and oxygen in the reactor is required to be less than 10ppm, the mole percentage content of nitrogen is 16%, the mole percentage content of ethylene is 55.2%, the mole percentage content of isopentane is 22%, the mole ratio of α -olefin to ethylene is 0.04, the mole ratio of hydrogen to ethylene is 0.12, and the α -olefin of the comonomer is 1-hexene.
The performance test result of the polyethylene special material prepared by the process is as follows:
the melt flow rate was 71.3g/10min with a 21.6kg weight, 2.6g/10min with a 2.16kg weight and a density of 0.9492g/cm3Tensile yield strength 23.7MPa, bending strength 14.6MPa, bending modulus 582MPa, impact strength 4.3kJ/m at-30 DEG C2Full notch creep strength 56h, melt strength at 210 ℃ 10.6 cN.
Example 13:
the polyethylene base resin for beverage bottle caps is produced on a gas-phase fluidized bed polyethylene device, a high-activity Ti/Cr series slurry catalyst is adopted, and the weight percentage of each component is as follows: 72.0% of mineral oil and 28.0% of solid catalyst; the titanium content in the solid catalyst was 1.0 wt%, the chromium content in the solid catalyst was 1.0 wt%, and the catalyst activity was 5.7 kgPE/gcat. The specific production process comprises the following steps:
the reactor pressure is 1.9MPa, the reaction temperature is 100 ℃, the mole percentage content of water and oxygen in the reactor is required to be less than 10ppm, the mole percentage content of nitrogen is 19%, the mole percentage content of ethylene is 57.3%, the mole percentage content of isopentane is 18%, the mole ratio of α -olefin to ethylene is 0.02, the mole ratio of hydrogen to ethylene is 0.08, and the α -olefin of the comonomer is 1-hexene.
The performance test result of the polyethylene special material prepared by the process is as follows:
the melt flow rate was 55.8g/10min with a 21.6kg weight, 0.9508g/cm density at 1.9g/10min with a 2.16kg weight3Tensile yield strength of 26.1MPa, bending strength of 15.0MPa, bending modulus of 577MPa, impact strength of 3.8kJ/m at-30 DEG C2Full notch creep strength of 55h, melt strength at 210 ℃11.4cN。
Example 14:
the polyethylene base resin for beverage bottle caps is produced on a gas-phase fluidized bed polyethylene device, a high-activity Ti/Cr series slurry catalyst is adopted, and the weight percentage of each component is as follows: 72.0% of mineral oil and 28.0% of solid catalyst; the titanium content in the solid catalyst was 1.0 wt%, the chromium content in the solid catalyst was 1.0 wt%, and the catalyst activity was 7.3 kgPE/gcat. The specific production process comprises the following steps:
the reactor pressure is 2.2MPa, the reaction temperature is 110 ℃, the mole percentage content of water and oxygen in the reactor is required to be less than 10ppm, the mole percentage content of nitrogen is 20%, the mole percentage content of ethylene is 59%, the mole percentage content of isopentane is 14%, the mole ratio of α -olefin to ethylene is 0.02, the mole ratio of hydrogen to ethylene is 0.10, and the α -olefin of the comonomer is 1-hexene.
The performance test result of the polyethylene special material prepared by the process is as follows:
the melt flow rate was measured with a 21.6kg weight at 62.3g/10min, the melt flow rate was measured with a 2.16kg weight at 2.2g/10min and the density was measured at 0.9503g/cm3Tensile yield strength of 25.6MPa, bending strength of 14.4MPa, bending modulus of 540MPa, and impact strength of 3.4kJ/m at-30 DEG C2Full notch creep strength 59h, melt strength 10.5cN at 210 ℃.
Example 15:
the polyethylene base resin for beverage bottle caps is produced on a gas-phase fluidized bed polyethylene device, a high-activity Ti/Cr series slurry catalyst is adopted, and the weight percentage of each component is as follows: 72.0% of mineral oil and 28.0% of solid catalyst; the titanium content in the solid catalyst was 1.0 wt%, the chromium content in the solid catalyst was 1.0 wt%, and the catalyst activity was 6.6 kgPE/gcat. The specific production process comprises the following steps:
the reactor pressure is 2.4MPa, the reaction temperature is 90 ℃, the mole percentage content of water and oxygen in the reactor is required to be less than 10ppm, the mole percentage content of nitrogen is 18%, the mole percentage content of ethylene is 56.3%, the mole percentage content of isopentane is 19%, the mole ratio of α -olefin to ethylene is 0.04, the mole ratio of hydrogen to ethylene is 0.08, and the α -olefin of the comonomer is 1-hexene.
The performance test result of the polyethylene special material prepared by the process is as follows:
the melt flow rate was 52.9g/10min with a 21.6kg weight, 0.9486g/cm density at 1.9g/10min with a 2.16kg weight3Tensile yield strength of 24.1MPa, bending strength of 16.2MPa, bending modulus of 539MPa, impact strength of 4.2kJ/m at-30 DEG C2Full notch creep strength 62h, melt strength 10.3cN at 210 ℃.
Claims (19)
1. The polyethylene base resin for the beverage bottle cap is characterized in that the weight average molecular weight of the polyethylene base resin is 8-15 ten thousand, the molecular weight distribution index is 7-15, the α -olefin mass content is 2-8 per thousand, the melt flow rate is 1.8-3.0 g/10min (2.16kg), 50.0-80.0 g/10min (21.6kg), and the density is 0.948-0.955 g/cm3The tensile yield strength is more than 20MPa, the bending strength is more than 10MPa, the bending modulus is more than 500MPa, and the impact strength at minus 30 ℃ is more than 3kJ/m2The full-notch creep strength is more than 50h, and the melt strength at 210 ℃ is more than 10 cN.
2. The polyethylene base resin for beverage bottle caps according to claim 1, wherein the polyethylene base resin is prepared by using a high activity Ti/Cr slurry catalyst to catalyze the copolymerization of ethylene and α -olefin with more than three carbons in a single-reactor gas-phase fluidized bed polyethylene process, and using hydrogen as a molecular weight regulator.
3. The polyethylene base resin for beverage bottle caps according to claim 2, wherein the active center of the high activity Ti/Cr slurry catalyst is a titanium/chromium composite dual active center, and the catalyst activity is 2.0kgPE/gcat or above.
4. The polyethylene base resin for beverage bottle caps as claimed in claim 2, wherein the high activity Ti/Cr slurry catalyst comprises the following components in percentage by weight: 60-80% of mineral oil and 20-40.0% of solid catalyst;
wherein, the content of titanium accounts for 0.1-10.0 wt% of the solid catalyst, and the content of chromium accounts for 0.1-10.0 wt% of the solid catalyst.
5. A method for preparing a polyethylene base resin for beverage bottle caps according to any one of claims 1 to 4, comprising the steps of:
s1 preprocessing stage:
adding polyethylene powder resin into a gas-phase fluidized bed reactor as a seed bed, and replacing the reactor with inert components for more than three times;
and S2 passivation stage:
starting a compressor to perform flow replacement on the polyethylene powder resin for more than 72 hours, and adding a cocatalyst into the fluidized bed reactor to perform passivation treatment;
and S3 component adjustment stage:
sequentially adding ethylene, α -olefin, inert components, refrigerant and molecular weight regulator into a reactor;
s4 polymerization stage:
when the concentration of each component in the reactor reaches a set value, adjusting the reaction temperature and the reaction pressure, controlling the reaction time, and adding a high-activity Ti/Cr series slurry catalyst to initiate polymerization.
6. The method for preparing polyethylene base resin for beverage bottle caps according to claim 5, wherein the active center of the high activity Ti/Cr slurry catalyst is a titanium and chromium composite dual active center, and the catalyst activity is more than 2.0 kgPE/gcat.
7. The method for preparing polyethylene base resin for beverage bottle caps according to claim 5, wherein the high activity Ti/Cr slurry catalyst comprises the following components in percentage by weight: 60-80% of mineral oil and 20-40.0% of solid catalyst;
wherein, the content of titanium accounts for 0.1-10.0 wt% of the solid catalyst, and the content of chromium accounts for 0.1-10.0 wt% of the solid catalyst.
8. The method for preparing the polyethylene base resin for the beverage bottle cap according to claim 5, wherein the reaction pressure in the polymerization reaction stage of S4 is 1.4-2.8 MPa.
9. The method for preparing polyethylene base resin for beverage bottle caps according to claim 5, wherein the reaction temperature in the polymerization reaction stage of S4 is 70-110 ℃.
10. The method for preparing polyethylene base resin for beverage bottle caps according to claim 5, wherein the reaction time in the S4 polymerization reaction stage is 0.5-8 hours.
11. The method for preparing polyethylene base resin for beverage bottle caps according to claim 5, wherein the molar percentage content of water and oxygen in the gas-phase fluidized bed reactor is less than 10 ppm.
12. The method for preparing polyethylene base resin for beverage bottle cap according to claim 5, wherein in the adjusting step of the S3 component, the inert component is nitrogen gas, and the molar percentage content is 0-50%.
13. The preparation method of the polyethylene base resin for the beverage bottle cap as claimed in claim 5, wherein the refrigerant is 1-pentane, 1-hexane or a mixture of the two, and the molar percentage of the refrigerant is 0-50%.
14. The preparation method of the polyethylene base resin for the beverage bottle caps as claimed in claim 5, wherein the ethylene is contained in the gas-phase fluidized-bed reactor in a molar percentage of 50-70%.
15. The method of claim 5, wherein the α -olefin is 1-butene, 1-hexene or a mixture thereof in the gas-phase fluidized-bed reactor, and the molar ratio of α -olefin to ethylene in the reactor is 0.01-0.1.
16. The method for preparing polyethylene base resin for beverage bottle caps as claimed in claim 5, wherein the molecular weight regulator in the gas phase fluidized bed reactor is hydrogen, and the molar ratio of hydrogen to ethylene in the reactor is 0.05-0.15.
17. The method of preparing polyethylene base resin for beverage bottle cap according to claim 5, wherein the cocatalyst is alkyl aluminum compound in S2 passivation stage.
18. The method of preparing polyethylene base resin for beverage bottle caps according to claim 17, wherein the alkyl aluminum compound is methylaluminoxane, diethylaluminum ethoxide, trimethylaluminum, triethylaluminum, triisobutylaluminum, or diethylaluminum monochloride.
19. The method for preparing polyethylene base resin for beverage bottle cap according to claim 17, wherein the amount of alkyl aluminum compound added is 2-5% of the weight of the seed bed.
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