阅读说明：本技术 超低灰分聚烯烃及制备方法与应用 (Ultra-low ash polyolefin, preparation method and application ) 是由 雷剑兰 黄启谷 于 2021-07-06 设计创作，主要内容包括：超低灰分聚烯烃及制备方法与应用,在洗涤罐中加入通用聚烯烃,采用本专利技术经一次洗涤或多次洗涤,获得灰分含量小于20PPm、分子量分布在3.3-5.6之间、等规度高于97％、熔点高于164℃的超低灰分聚烯烃粉料或超低灰分窄分子量分布聚烯烃粒料；所述的聚烯烃是聚乙烯或聚乙烯共聚物、聚丙烯或聚丙烯共聚物,灰分含量在40-200PPm之间,重均分子量在2000-10000000g/mol；制备的超低灰分聚烯烃适用于电容器薄膜料、电池隔膜料、高压电缆料、超高压电缆料或医卫用材料等。本发明的制备方法工艺简单、成本低,对设备要求低,能耗小,环境污染小,生产过程中无二氧化碳产生,零排放。(The preparation method and application of the ultra-low ash polyolefin, wherein the general polyolefin is added into a washing tank, and the ultra-low ash polyolefin powder or the ultra-low ash polyolefin granules with narrow molecular weight distribution, the ash content of which is less than 20PPm, the molecular weight distribution of which is between 3.3 and 5.6, the isotacticity of which is higher than 97 percent and the melting point of which is higher than 164 ℃ are obtained by adopting the technology of the patent through one-time washing or multiple-time washing; the polyolefin is polyethylene or polyethylene copolymer, polypropylene or polypropylene copolymer, the ash content is between 40 and 200PPm, and the weight average molecular weight is 2000-10000000 g/mol; the prepared ultra-low ash polyolefin is suitable for capacitor film materials, battery diaphragm materials, high-voltage cable materials, ultrahigh-voltage cable materials, medical and sanitary materials and the like. The preparation method has the advantages of simple process, low cost, low requirement on equipment, low energy consumption, low environmental pollution, no carbon dioxide generation in the production process and zero emission.)

1. The preparation method of the ultra-low ash polyolefin is characterized in that 100 parts of polyolefin with ash content of 40-200PPm, 50-250 parts of ethanol, 0.005-20 parts of isooctanol, 50-250 parts of petroleum ether with boiling point of 65-160 ℃ and 0.5-30 parts of urea are added into a washing tank, stirred, washed at 45-130 ℃ for 0.5-8 hours, washed once or for a plurality of times, filtered and dried to obtain ultra-low ash polyolefin powder or ultra-low ash polyolefin granules; wherein the ultra-low ash polyolefin powder or the ultra-low ash polyolefin pellets are polyethylene powder with ash content less than 20PPm or polyethylene pellets with ash content less than 20 PPm; wherein the ultra-low ash polyolefin powder or the ultra-low ash polyolefin pellet is polypropylene powder with ash content less than 20PPm or polypropylene pellet with ash content less than 20 PPm; wherein, the preparation method of the ultra-low ash polyolefin does not generate carbon dioxide in the production process.

2. The ultra-low ash polyolefin and the process for preparing the same as claimed in claim 1, wherein said isooctanol is 2-ethyl-1-hexanol, 2-methyl-1-heptanol, 2-methyl-2-heptanol, 6-methyl-1-heptanol, 6-methyl-3-heptanol, 4-ethyl-1-hexanol or a mixture thereof, and the mass ratio of isooctanol to polyolefin is (0.005-20): 100.

3. the ultra-low ash polyolefin and the preparation method thereof according to claim 1, wherein the petroleum ether with a boiling point of 65-160 ℃ is a mixture of hydrocarbon compounds with a boiling range of 60-90 ℃ or 90-160 ℃, and the mass ratio of the petroleum ether with a boiling point of 65-160 ℃ to the polyolefin is (50-250): 100.

4. the ultra-low ash polyolefin and process for preparation according to claim 1, wherein the urea is urea or urea derivative, wherein the urea derivative is urea, urea-formaldehyde, isobutylidene diurea or butylidene diurea, wherein the mass ratio of ethanol, urea and polyolefin is (50-250): (0.5-30): 100.

5. the ultra-low ash polyolefin and the preparation method thereof as claimed in claim 1, wherein the polyolefin is polyethylene or polyethylene copolymer, polypropylene or polypropylene copolymer, the ash content is between 40-200PPm, and the weight average molecular weight is 2000-.

6. The ultra-low ash polyolefin and the preparation method thereof as claimed in claim 1, wherein the polypropylene has an ash content of 40-200PPm, a weight average molecular weight of 2000-10000000g/mol, and an isotacticity of not less than 93%.

7. Use of the ultra low ash polyolefin according to any of claims 1-6 for capacitor film materials, battery separator materials, high voltage cable materials, ultra high voltage cable materials, medical and hygiene materials or neutron radiation prevention materials.

Technical Field

The invention belongs to the field of polyolefin resin or polyolefin plastic or polyolefin elastomer, and particularly relates to a preparation method and application of polyolefin resin or polyolefin plastic or polyolefin elastomer with high-end ultralow ash content and narrow molecular weight distribution and polyolefin resin or polyolefin plastic or polyolefin elastomer with high-end ultralow ash content and narrow molecular weight distribution.

Background

The ethylene capacity of China reaches 2600 ten thousand tons per year, the equivalent ethylene self-supporting rate reaches about 70%, the propylene capacity reaches 2200 ten thousand tons per year, and the self-supporting rate is about 75% in 2015 years; the consumption of the polyethylene is increased by 4.2 percent every year, and the consumption reaches 2100 ten thousand tons in 2015; the consumption of polypropylene increases by 5.0% every year, and the consumption reaches 1650 ten thousand tons every 2015. In 2016, the Chinese polyethylene capacity reaches about 1700 ten thousand tons per year, the yield is about 1400 ten thousand tons, the apparent consumption is about 2400 ten thousand tons, and the net import is nearly 1000 ten thousand tons; the capacity of the polypropylene can reach about 2200 ten thousand tons per year, the output is about 1800 ten thousand tons, the apparent consumption is about 2100 ten thousand tons, and the net import amount is about 300 ten thousand tons. However, the high-end polyolefin self-sufficiency rate in China in 2014-2015 was about 38%, and the import foreign exchange was $ 143.3 billion. In 2020, China has demand for high-end polyolefin of 1115 ten thousand tons and yield of 774 ten thousand tons, and the self-supporting rate is close to 70%. However, in 2020, statistics show that the demand of China for high-end polyolefin reaches 1115 ten thousand tons, and the output is 774 ten thousand tons, and the estimated self-sufficiency rate is nearly 70% originally, and actually is about 30%. In particular, high-end polyolefins including high-end polyethylene and polypropylene still need to be imported in large quantities. Ultra-low ash polypropylene, ultra-low ash polyethylene and the like are imported. The polyolefin film industry for the high-end capacitor starts late, but develops abnormally rapidly, the total industrial output value of the capacitor and the matched equipment manufacturing industry in China in 2007 is 163.94 billion yuan, and the sales income is 154.68 billion yuan; in 2012, the number of the cells increased to 366.42 hundred million yuan and 358.42 hundred million yuan respectively. With the further development of digitalization, informatization and networking construction, the increasing investment of the country in the aspects of power grid construction, electrified railway construction, energy-saving illumination, hybrid electric vehicles and the like and the upgrading of consumer electronic products, the market of thin film electronic containers in China will steadily increase at a speed of about 10%. The german electronics association expressed that the global consumer electronics market size increased by 14% from 7830 to 8910 billion euros in 2015. Among them, the most accelerated current market belongs to the middle east and africa, and the expected increase is 27%, the increase rate of the north american market is 22%, and the increase rate is ranked second. The western european market is expected to increase by 4%. The Asian market is still the largest technical consumer goods market in the world, the increasing rate of the Asian emerging market reaches 17%, and the market of the Asian developed countries is expected to increase by 13%.

The accumulated requirements of new energy resources of China on the thin film in 2015 and 2020 will exceed 6000 tons and 33000 tons respectively.

The construction of the extra-high voltage smart grid becomes the development trend of the future power grid. 6200 million yuan of construction of 20 extra-high voltage lines is put into the national power grid in 2013-2017. The preparation of ultra high voltage cables and high voltage cables requires a large amount of ultra low ash polyethylene or ultra low ash polypropylene.

The proportion of high-end products to the total products will increase year by year. With the development of new energy industry, the technology of the film capacitor industry is promoted to be upgraded, and the new development space of the film capacitor industry is expanded. The installed capacity of a new energy power generation market represented by solar energy and wind energy reaches 110GW (ground wire), and the demand of thin film materials reaches 6000 tons. With the acceleration of the railway electrification process, the market of the ultrathin high-temperature-resistant polypropylene film also rapidly grows correspondingly. The density of the ultra-low ash polypropylene material is 0.9g/cm³Is one of the lightest resin varieties and has the excellent performances of high transparency, light specific gravity, easy processing, high strength, acid and alkali resistance, good electrical insulation property and the like. Domestic ultra-low ash polyolefin resins are currently completely imported, and the main suppliers are northern Europe chemical industry, Korean oiling and Singapore. The japan korea has been refusing to export ultra-low ash polyolefin resin materials to our country.

The synthetic polyolefin comprises polyethylene, polypropylene or their copolymer, the adopted catalyst is supported Z-N catalyst, supported metallocene catalyst, supported Cr catalyst, etc., the carrier is magnesium chloride, alkoxy magnesium or silicon oxide, etc., during polymerization, alkyl aluminum or alkoxy aluminum as cocatalyst or external electron donor siloxane compound is also added, and the catalyst active component is transition metal salt or transition metal complex. The carrier, the catalyst active component, the cocatalyst or the external electron donor are all retained in the polyolefin product, and become ash to be remained in the polyolefin product. The level of ash content directly affects the properties and uses of polyolefin materials. The ash content is measured by the method specified in GB/T9345.1-2008. The ash content of 100PPm or more is defined as high ash content, 60 to 100PPm is defined as medium ash content, 35 to 60PPm is defined as low ash content, and the ash content of 20PPm or less is defined as ultra-low ash content. At present, China cannot produce polyolefin with ultralow ash content.

The ash content of the required ultra-low ash polyolefin resin material is less than or equal to 20PPM, the molecular weight distribution is narrow, and the molecular weight distribution is required to be between 3.8 and 5.5. Due to the harsh conditions required, it is necessary to treat the polyolefin powder that has not been deactivated or has been deactivated during the polyolefin production process. The processing technology is a key core technology for preparing the ultralow-ash polyolefin resin material. The polyolefin includes polyethylene, polypropylene or copolymers thereof.

The invention unexpectedly discovers that in the process of treating the polyolefin powder which is not inactivated or is inactivated, ethanol, isooctanol, petroleum ether with the boiling point of 65-160 ℃, urea or urea derivative are added into a washing tank, and the washing is carried out for one time or multiple times, so as to obtain the ultra-low ash content polyolefin resin material, wherein the ash content is less than or equal to 20PPm, and the molecular weight is distributed between 3.8 and 5.5. If the polypropylene powder which is not inactivated or inactivated is treated, the polypropylene powder is washed once or for a plurality of times to obtain the polypropylene resin material with ultralow ash content, high melting point and high isotacticity, the isotacticity is equal to or higher than 98 percent, the melting point is higher than 164 ℃, the ash content is less than 20PPm, and the molecular weight is distributed between 4.0 and 5.5.

Disclosure of Invention

It is an object of the present invention to provide an ultra low ash polyolefin which is an ultra low ash content polyethylene powder or ultra low ash content polyethylene pellets; ultra-low ash content, narrow molecular weight distribution polyethylene powder or ultra-low ash content, narrow molecular weight distribution polyethylene pellets; polypropylene powder with ultra-low ash content or polypropylene granules with ultra-low ash content; polypropylene powder with ultralow ash content and narrow molecular weight distribution or polypropylene granules with ultralow ash content and narrow molecular weight distribution; ultra-low ash content, narrow molecular weight distribution, high isotactic polypropylene powder or ultra-low ash content, narrow molecular weight distribution, high isotactic polypropylene granules; the polypropylene powder with ultra-low ash content, narrow molecular weight distribution, high melting point and high isotacticity or the polypropylene granules with ultra-low ash content, narrow molecular weight distribution, high melting point and high isotacticity; the ultra-low ash content polyolefin with narrow molecular weight distribution prepared by the invention is particularly suitable for capacitor film materials, lithium battery diaphragm materials, high-voltage cable materials or ultrahigh-voltage cable materials or medical and sanitary materials and the like.

The second purpose of the invention is to provide a preparation method and application of the ultra-low ash polyolefin; the invention discloses a process for treating polyolefin powder which is not inactivated or inactivated, wherein ethanol, isooctanol and petroleum ether with the boiling point of 65-160 ℃, urea or urea derivatives are added into a washing tank (tank), stirred, washed for 0.5-8 hours at the temperature of 45-130 ℃, and washed once or for multiple times to obtain the ultra-low ash polyolefin resin material, wherein the ash content is less than 20PPm, and the molecular weight is distributed between 3.8-5.3. If the polypropylene powder which is not inactivated or inactivated is treated, the polypropylene powder is washed once or for a plurality of times to obtain the polypropylene resin material with ultralow ash content, high melting point and high isotacticity, the isotacticity is higher than 98 percent, the melting point is higher than 164 ℃, the ash content is less than 20PPM, and the molecular weight distribution is between 4.0 and 5.5

The ultra-low ash polyolefin and the preparation method and the application thereof are characterized in that: the ash content of the required ultra-low ash polyolefin resin material is less than or equal to 20PPM, the molecular weight distribution is narrow, and the molecular weight distribution is required to be between 3.8 and 5.3; because of the harsh conditions required, polyolefin powder which is not inactivated or is inactivated needs to be treated in the polyolefin production process; the treatment technology is a key core technology for preparing the ultra-low ash content polyolefin resin material, is monopolized by foreign petrochemical companies at present, and still belongs to the technology of 'neck clamping' at home; the polyolefin comprises polyethylene, polypropylene or copolymers thereof.

The ultra-low ash polyolefin and the preparation method and the application thereof are characterized in that: the ultralow-ash narrow molecular weight distribution polyolefin prepared by the preparation method of the main-sheet ultralow-ash polyolefin obtains an ultralow-ash polyolefin resin material, the ash content is less than 20PPm, and the molecular weight is distributed between 3.8 and 5.3; if the polypropylene powder which is not inactivated or inactivated is treated, the polypropylene powder is washed once or for a plurality of times to obtain the polypropylene resin material with ultralow ash content, high melting point and high isotacticity, the isotacticity is higher than 98 percent, the melting point is higher than 164 ℃, the ash content is less than 20PPM, and the molecular weight is distributed between 4.0 and 5.3.

The ultra-low ash polyolefin and the preparation method and the application thereof are characterized in that: the isotacticity and melting point of the polypropylene with ultra-low ash content and narrow molecular weight distribution prepared by the preparation method of the main-grade ultra-low ash content polyolefin are obviously improved; generally, the isotacticity of polypropylene is improved by 1%, and the mechanical property of the polypropylene material is obviously improved; the melting point of the ultra-low ash content narrow molecular weight distribution polypropylene is higher than 165 ℃ and the polypropylene can be used as a high temperature resistant capacitor film material, and the market price is 2000 yuan/ton higher.

The ultra-low ash polyolefin and the preparation method and the application thereof are characterized in that: the preparation method of the ultralow-ash polyolefin disclosed by the invention is simple in process, low in cost, low in equipment requirement, low in energy consumption and low in environmental pollution.

The ultra-low ash polyolefin and the preparation method and the application thereof are characterized in that: according to the preparation method of the ultra-low ash polyolefin, no carbon dioxide is generated in the production process, and zero emission of the carbon dioxide is realized.

The ultra-low ash polyolefin and the preparation method and application thereof are characterized in that the ultra-low ash polyolefin prepared by the invention is suitable for capacitor film materials, battery diaphragm materials, high-voltage cable materials, ultrahigh-voltage cable materials, medical and health materials or neutron radiation prevention materials and the like.

The ultra-low ash polyolefin and the preparation method and the application thereof are characterized in that: the embodiment of the invention claims that the mass ratio of the raw materials is as follows:

adding 100 parts of polyolefin into a washing tank, wherein the ash content is between 40 and 200 PPm;

adding 50-250 parts of ethanol;

adding 0.005-20 parts of isooctyl alcohol;

adding 50-250 parts of petroleum ether with the boiling point of 65-160 ℃;

adding 0.5-30 parts of urea;

stirring; washing temperature: 45-130 ℃; washing time: 0.5-8 hours; washing one or more times; filtering; drying; powder material; or granulation.

The ultra-low ash polyolefin and the preparation method and the application thereof are characterized in that: the polyolefin is polyethylene or polyethylene copolymer, polypropylene or polypropylene copolymer, the ash content is between 40 and 200PPm, and the weight average molecular weight is 2000-10000000 g/mol.

The ultra-low ash polyolefin and the preparation method and the application thereof are characterized in that: the polypropylene has ash content of 40-200PPm, weight average molecular weight of 2000-10000000g/mol and isotacticity of not less than 93%.

The ultra-low ash polyolefin and the preparation method and the application thereof are characterized in that: the isooctyl alcohol is 2-ethyl-1-hexanol, 2-methyl-1-heptanol, 2-methyl-2-heptanol, 6-methyl-1-heptanol, 6-methyl-3-heptanol, 4-ethyl-1-hexanol, etc. or a mixture thereof, and the mass ratio of isooctyl alcohol to polyolefin is (0.005-20): 100, in particular, acts to eliminate magnesium ions, the effect being to reduce the ash content of the polyolefin.

The ultra-low ash polyolefin and the preparation method and the application thereof are characterized in that: the ethanol is a dispersant and a cosolvent which plays a role of isooctanol, the isooctanol plays a role in eliminating magnesium ions, titanium ions, aluminum ions, silicon ions and the like, and the effect is to reduce the ash content of polyolefin, wherein the mass ratio of the ethanol to the isooctanol to the polyolefin is (50-250): (0.005-20): 100.

the ultra-low ash polyolefin and the preparation method and the application thereof are characterized in that: the petroleum ether with the boiling point of 65-160 ℃ is a mixture of hydrocarbon compounds with the boiling range of 60-90 ℃ or 90-160 ℃, has the functions of a dispersing agent and dissolving low-molecular-weight polyolefin, and has the effects of improving the molecular weight of the polyolefin and narrowing the molecular weight distribution of the polyolefin; wherein the mass ratio of petroleum ether with a boiling point of 65-160 ℃ to polyolefin is (50-250): 100.

the ultra-low ash polyolefin and the preparation method and the application thereof are characterized in that: the petroleum ether with the boiling point of 65-160 ℃ is a mixture of hydrocarbon compounds with the boiling range of 60-90 ℃ or 90-160 ℃, has the functions of a dispersing agent and dissolving atactic polypropylene or low-isotacticity polypropylene, and has the effect of improving the isotacticity of polypropylene.

The ultra-low ash polyolefin and the preparation method and the application thereof are characterized in that: the petroleum ether with the boiling point of 65-160 ℃ is a mixture of hydrocarbon compounds with the boiling range of 60-90 ℃ or 90-160 ℃, has the functions of a dispersing agent and dissolving silicon compounds in polyolefin, and has the effect of reducing the ash content of the polyolefin.

The ultra-low ash polyolefin and the preparation method and the application thereof are characterized in that: the urea is urea or urea derivatives, wherein the urea derivatives are urea, urea formaldehyde, isobutylidene diurea, butylidene diurea or the like or a mixture of the urea derivatives and the urea derivatives, are dissolved in ethanol, play a role in partially eliminating magnesium ions, partially eliminating titanium ions and partially eliminating aluminum ions, and have the effect of reducing the ash content of polyolefin; wherein, the mass ratio of the ethanol to the urea to the polyolefin is (50-250): (0.5-30): 100, respectively; wherein, the combination of urea and magnesium ion, titanium ion or aluminum ion can be used as fertilizer for various crops or plants.

The ultra-low ash polyolefin and the preparation method and the application thereof are characterized in that: the stirring is closed stirring, and the closed stirring is used for preventing ethanol, isooctanol, petroleum ether and the like from leaking or preventing other impurities from entering a washing tank.

The ultra-low ash polyolefin and the preparation method and the application thereof are characterized in that: the washing temperature is 45-130 ℃.

The ultra-low ash polyolefin and the preparation method and the application thereof are characterized in that: the washing time is 0.5-8 hours.

The polyolefin with ultralow ash content and narrow molecular weight distribution, the preparation method and the application are characterized in that: the washing is one washing or multiple washing, wherein the multiple washing is two or more washing.

The polyolefin with ultralow ash content and narrow molecular weight distribution, the preparation method and the application are characterized in that: the product is polyolefin powder or polyolefin pellets.

The ultra-low ash polyolefin and the preparation method and the application thereof are characterized in that: the ultra-low ash content polyolefin prepared by the method disclosed by the patent has the advantages that the ash content of the polyolefin is obviously reduced, and the ash content of the polyolefin is lower than 20 PPm.

The ultra-low ash polyolefin and the preparation method and the application thereof are characterized in that: the ultra-low ash polyolefin prepared by the method disclosed by the patent has narrow molecular weight distribution.

The ultra-low ash polyolefin and the preparation method and the application thereof are characterized in that: the method disclosed by the patent is adopted to prepare the polyolefin with ultra-low ash content, so that the isotacticity of the polyolefin is improved.

The ultra-low ash polyolefin and the preparation method and the application thereof are characterized in that: the melting point of the ultra-low ash polyolefin prepared by the method disclosed by the patent is increased.

The ultra-low ash polyolefin and the preparation method and the application thereof are characterized in that: the molecular weight of the ultra-low ash polyolefin prepared by the method disclosed by the patent is increased.

The invention discloses an ultralow-ash narrow molecular weight distribution polyolefin, and a combustion method GB/T9345.1-2008 is adopted in an ash content determination method.

The melting point of the polyolefin was determined by DSC.

The molecular weight and molecular weight distribution of the polyolefin were determined by high temperature GPC.

The isotacticity of polypropylene was determined by solvent extraction.

XPS is used to determine the content of magnesium, titanium, aluminium, silicon or chlorine in the ash.

The present invention will be further described with reference to the following specific embodiments, but the scope of the present invention is not limited to the following examples.

The specific implementation mode is as follows:

example 1

According to the formulation of the invention, at 40m³The washing tank of (2) is charged with an ash content of 200PPm and a molecular weight of 21X 10⁴10 tons of polypropylene, 10 tons of ethanol, 10 tons of petroleum ether with the boiling point of 60-90 ℃, 0.1 ton of 2-ethyl-1-hexanol and 0.1 ton of urea in g/mol are stirred for 2.5 hours at 50 ℃ and filtered; adding 10 tons of ethanol, 10 tons of petroleum ether with the boiling point of 90-120 ℃, 0.1 ton of isooctanol,0.1 ton of urea, stirring for 3.5 hours at 70 ℃, and filtering; adding 10 tons of ethanol, 10 tons of petroleum ether with the boiling point of 60-90 ℃, 0.1 ton of isooctanol and 0.1 ton of urea again, stirring for 1.5 hours at 50 ℃, filtering and drying to obtain 9.91 tons of polypropylene powder.

Example 2

According to the formulation of the invention, at 20m³The ash content of the washing tank is 150PPm and the molecular weight is 32 x 10⁴5 tons of polypropylene in g/mol, 5 tons of ethanol, 0.03 ton of 2-ethyl-1-hexanol, 0.02 ton of 2-methyl-1-heptanol, 5 tons of petroleum ether with a boiling point of 90-120 ℃ and 0.05 ton of urea are added, stirred for 3.5 hours at 80 ℃ and filtered; adding 5 tons of ethanol, 5 tons of petroleum ether, 0.05 ton of isooctanol and 0.05 ton of urea again, stirring for 3 hours at 70 ℃, and filtering; and adding 5 tons of ethanol, 5 tons of petroleum ether, 0.05 ton of isooctanol and 0.05 ton of urea again, stirring for 2.5 hours at the temperature of 60 ℃, filtering, drying and granulating to obtain 4.95 tons of polypropylene granules.

Example 3

According to the formulation of the invention, at 10m³The ash content of the washing tank is 120PPm and the molecular weight is 45 x 10⁴2.5 tons of polypropylene in g/mol, 2.5 tons of ethanol, 2.5 tons of petroleum ether with the boiling point of 90-120 ℃, 0.02 ton of 2-methyl-2-heptanol and 0.05 ton of urea are added, stirred for 3.5 hours at 75 ℃ and filtered; adding 2 tons of ethanol, 3 tons of petroleum ether with the boiling point of 80-90 ℃, 0.05 ton of isooctanol and 0.05 ton of urea again, stirring for 3 hours at 70 ℃, and filtering; adding 1 ton of ethanol, 3 tons of petroleum ether, 0.05 ton of isooctanol and 0.02 ton of urea again, stirring for 2 hours at 60 ℃, filtering and drying to obtain 2.48 tons of polypropylene powder.

Example 4

According to the formulation of the invention, at 20m³The ash content of the washing tank is 80PPm and the molecular weight is 12 multiplied by 10⁴5 tons of ethanol, 0.05 ton of 6-methyl-1-heptanol, 5 tons of petroleum ether with the boiling point of 120-; adding 3 tons of ethanol, 8 tons of petroleum ether, 0.05 ton of isooctanol and 0.05 ton of urea again, stirring for 3 hours at 70 ℃, and filtering; adding 5 tons of ethanol, 5 tons of petroleum ether and isooctyl alcohol again0.05 ton of urea and 0.05 ton of urea, stirring for 2.5 hours at 60 ℃, filtering, drying and granulating to obtain 4.97 tons of polypropylene granules.

Example 5

According to the formulation of the invention, at 20m³The ash content of the washing tank is 50PPm and the molecular weight is 86X 10⁴5 tons of ethanol, 0.06 ton of 2-ethyl-1-hexanol, 5 tons of petroleum ether with the boiling point of 90-130 ℃ and 0.05 ton of isobutylidene diurea are added into 5 tons of polypropylene of g/mol, stirred for 3.5 hours at 80 ℃ and filtered; adding 3 tons of ethanol, 8 tons of petroleum ether, 0.008 ton of isooctanol and 0.05 ton of urea again, stirring for 3 hours at 70 ℃, and filtering; and adding 5 tons of ethanol, 5 tons of petroleum ether, 0.008 tons of isooctanol and 0.05 tons of urea again, stirring for 2.5 hours at 50 ℃, filtering, drying and granulating to obtain 4.98 tons of polypropylene granules.

Example 6

According to the formulation of the invention, at 20m³The ash content of the washing tank is 40PPm and the molecular weight is 21X 10⁴5 tons of polypropylene in g/mol, 5 tons of ethanol, 0.06 ton of isooctanol, 9 tons of petroleum ether with the boiling point of 90-120 ℃ and 0.05 ton of urea are added, stirred for 3.5 hours at 75 ℃ and filtered; adding 3 tons of ethanol, 8 tons of petroleum ether, 0.008 ton of isooctanol and 0.05 ton of crotonobiurea again, stirring for 3 hours at 70 ℃, and filtering; and adding 4 tons of ethanol, 0.06 ton of isooctanol, 6 tons of petroleum ether and 0.05 ton of urea again, stirring for 3 hours at 70 ℃, filtering and drying to obtain 4.97 tons of polypropylene powder.

Example 7

According to the formulation of the invention, at 20m³The ash content of the washing tank is 40PPm and the molecular weight is 28 multiplied by 10⁴5 tons of ethanol, 0.06 ton of isooctanol, 9 tons of petroleum ether with the boiling point of 110-130 ℃ and 0.05 ton of urea are added into 5 tons of polypropylene of g/mol, stirred for 4.5 hours at 75 ℃, filtered and dried to obtain 4.97 tons of polypropylene powder.

Example 8

According to the formulation of the invention, at 20m³The ash content of the washing tank is 120PPm and the molecular weight is 33X 10⁴5 tons of polyethylene in g/mol, 5 tons of ethanol, 0.06 ton of isooctanol, 9 tons of petroleum ether and urea are added0.05 ton, stirred for 3.5 hours at 75 ℃ and filtered; adding 3 tons of ethanol, 8 tons of petroleum ether, 0.008 ton of isooctanol and 0.05 ton of urea again, stirring for 3 hours at 70 ℃, and filtering; adding 3 tons of ethanol, 8 tons of petroleum ether, 0.008 tons of isooctanol and 0.05 tons of urea again, stirring for 3 hours at 70 ℃, filtering and drying to obtain 4.98 tons of polyethylene powder.

Example 9

According to the formulation of the invention, at 20m³The ash content of the washing tank is 65PPm and the molecular weight is 21X 10⁵5 tons of polyethylene in g/mol, 5 tons of ethanol, 0.06 ton of isooctanol, 9 tons of petroleum ether and 0.05 ton of urea are added, stirred for 3.5 hours at 75 ℃, and filtered; adding 3 tons of ethanol, 8 tons of petroleum ether, 0.008 tons of isooctanol and 0.05 tons of urea again, stirring for 3 hours at 70 ℃, filtering and drying to obtain 4.985 tons of polyethylene powder.

Example 10

According to the formulation of the invention, at 20m³The ash content of the washing tank is 120PPm and the molecular weight is 73 multiplied by 10⁴5 tons of polyethylene in g/mol, 5 tons of ethanol, 0.06 ton of isooctanol, 9 tons of petroleum ether and 0.05 ton of urea are added, stirred for 3.5 hours at 75 ℃, and filtered; adding 3 tons of ethanol, 8 tons of petroleum ether, 0.008 ton of isooctanol and 0.05 ton of urea again, stirring for 3 hours at 70 ℃, and filtering; adding 3 tons of ethanol, 8 tons of petroleum ether, 0.008 tons of isooctanol and 0.05 tons of urea again, stirring for 3 hours at 70 ℃, filtering and drying to obtain 4.982 tons of polyethylene powder.

Example 11

According to the formulation of the invention, at 20m³The ash content of the washing tank is 90PPm and the molecular weight is 33X 10⁵5 tons of polyethylene in g/mol, 5 tons of ethanol, 0.06 ton of isooctanol, 9 tons of petroleum ether and 0.05 ton of urea are added, stirred for 3.5 hours at 75 ℃, and filtered; adding 3 tons of ethanol, 8 tons of petroleum ether, 0.008 ton of isooctanol and 0.05 ton of urea again, stirring for 3 hours at 70 ℃, and filtering; adding 3 tons of ethanol, 8 tons of petroleum ether, 0.008 tons of isooctanol and 0.05 ton of urea again, stirring for 3 hours at 70 ℃, filtering and drying to obtain 4.981 tons of polyethylene powder.

Example 12

According to the formulation of the invention, a 500mL wash tank was charged with an ash content of 80PPm and a molecular weight of 61X 10⁵150g of polyethylene per mol, 200g of ethanol, 16g of isooctanol, 250g of petroleum ether and 5g of urea are added, stirred for 3.5 hours at 75 ℃, and filtered; adding 300g of ethanol, 180g of petroleum ether, 4g of isooctanol and 2g of urea again, stirring for 3 hours at 70 ℃, and filtering; 160g of ethanol, 180g of petroleum ether, 8g of isooctanol and 5g of urea are added again, stirred for 3 hours at 70 ℃, filtered and dried to obtain 149g of polyethylene powder.

Example 13

According to the formulation of the invention, a 500mL wash tank was charged with an ash content of 80PPm and a molecular weight of 91X 10⁵150g of polyethylene per mol, 220g of ethanol, 12g of isooctanol, 200g of petroleum ether and 5g of urea are added, stirred for 3.5 hours at 75 ℃, and filtered; adding 300g of ethanol, 180g of petroleum ether, 5g of isooctanol and 2g of urea again, stirring for 3 hours at 70 ℃, and filtering; and adding 180g of ethanol, 180g of petroleum ether, 5g of isooctanol and 5g of urea again, stirring for 3 hours at 70 ℃, filtering and drying to obtain 148g of polyethylene powder.

Comparative example 1

At 10m³The ash content of the washing tank is 120PPm and the molecular weight is 32 x 10⁴2.5 tons of polypropylene in g/mol, 2.5 tons of ethanol, 2.5 tons of petroleum ether, 0.02 ton of n-octanol and 0.05 ton of urea are added, stirred for 3.5 hours at 75 ℃ and filtered; adding 2 tons of ethanol, 3 tons of petroleum ether, 0.05 ton of n-octanol and 0.05 ton of urea again, stirring for 3 hours at 70 ℃, and filtering; and adding 1 ton of ethanol, 3 tons of petroleum ether, 0.05 ton of n-octanol and 0.02 ton of urea again, stirring for 2 hours at 60 ℃, filtering and drying to obtain 2.49 tons of polypropylene powder.

Comparative example 2

At 10m³The ash content of the washing tank is 120PPm and the molecular weight is 32 x 10⁴2.5 tons of polypropylene in g/mol, 2.5 tons of ethanol, 2.5 tons of petroleum ether, 0.02 ton of heptanol and 0.05 ton of urea are added, stirred for 3.5 hours at 75 ℃, and filtered; adding 2 tons of ethanol, 3 tons of petroleum ether, 0.05 ton of heptanol and 0.05 ton of urea again, stirring for 3 hours at 70 ℃, and filtering; adding 1 ton of ethanol and 3 tons of petroleum ether again0.05 ton of heptanol and 0.02 ton of urea, stirring for 2 hours at 60 ℃, filtering and drying to obtain 2.491 tons of polypropylene powder.

Comparative example 3

At 10m³The ash content of the washing tank is 120PPm and the molecular weight is 32 x 10⁴2.5 tons of polypropylene in g/mol, 2.5 tons of ethanol, 2.5 tons of petroleum ether, 0.02 ton of amyl alcohol and 0.05 ton of urea are added, stirred for 3.5 hours at 75 ℃ and filtered; adding 2 tons of ethanol, 3 tons of petroleum ether, 0.05 ton of amyl alcohol and 0.05 ton of urea again, stirring for 3 hours at 70 ℃, and filtering; and adding 1 ton of ethanol, 3 tons of petroleum ether, 0.05 ton of amyl alcohol and 0.02 ton of urea again, stirring for 2 hours at the temperature of 60 ℃, filtering and drying to obtain 2.492 tons of polypropylene powder.

Comparative example 4

At 10m³The ash content of the washing tank is 120PPm and the molecular weight is 32 x 10⁴2.5 tons of polypropylene in g/mol, 2.5 tons of ethanol, 2.5 tons of petroleum ether, 0.02 ton of n-nonanol and 0.05 ton of urea are added, stirred for 3.5 hours at 75 ℃, and filtered; adding 2 tons of ethanol, 3 tons of petroleum ether, 0.05 ton of n-nonanol and 0.05 ton of urea again, stirring for 3 hours at 70 ℃, and filtering; adding 1 ton of ethanol, 3 tons of petroleum ether, 0.05 ton of n-nonanol and 0.02 ton of urea again, stirring for 2 hours at 60 ℃, filtering and drying to obtain 2.488 tons of polypropylene powder.

Comparative example 5

At 10m³The ash content of the washing tank is 120PPm and the molecular weight is 32 x 10⁴2.5 tons of polypropylene in g/mol, 2.5 tons of ethanol, 2.5 tons of petroleum ether, 0.02 ton of 2-nonanol and 0.05 ton of urea are added, stirred for 3.5 hours at 75 ℃, and filtered; adding 2 tons of ethanol, 3 tons of petroleum ether, 0.05 ton of 2-nonanol and 0.05 ton of urea again, stirring for 3 hours at 70 ℃, and filtering; adding 1 ton of ethanol, 3 tons of petroleum ether, 0.05 ton of 2-nonanol and 0.02 ton of urea again, stirring for 2 hours at 60 ℃, filtering and drying to obtain 2.487 tons of polypropylene powder.

Comparative example 6

At 10m³The ash content of the washing tank is 120PPm and the molecular weight is 32 x 10⁴2.5 tons of polypropylene per mol, 2.5 tons of methanol, 2.5 tons of petroleum ether,N-octanol (0.02 ton) and urea (0.05 ton) at 65 deg.C for 3.5 hr, and filtering; adding 2 tons of methanol, 3 tons of petroleum ether, 0.05 ton of n-octanol and 0.05 ton of urea again, stirring for 3 hours at 60 ℃, and filtering; and adding 1 ton of methanol, 3 tons of petroleum ether, 0.05 ton of n-octanol and 0.02 ton of urea again, stirring for 2 hours at 60 ℃, filtering and drying to obtain 2.491 tons of polypropylene powder.

Comparative example 7

At 20m³The ash content of the washing tank is 120PPm and the molecular weight is 33X 10⁴5 tons of polyethylene in g/mol, 5 tons of ethanol, 0.06 ton of n-octanol, 9 tons of petroleum ether and 0.05 ton of urea are added, stirred for 3.5 hours at 75 ℃, and filtered; adding 3 tons of ethanol, 8 tons of petroleum ether, 0.008 ton of n-octanol and 0.05 ton of urea again, stirring for 3 hours at 70 ℃, and filtering; adding 3 tons of ethanol, 8 tons of petroleum ether, 0.008 ton of n-octanol and 0.05 ton of urea again, stirring for 3 hours at 70 ℃, filtering and drying to obtain 4.99 tons of polyethylene powder.

Comparative example 8

At 20m³The ash content of the washing tank is 120PPm and the molecular weight is 33X 10⁴5 tons of polyethylene in g/mol, 5 tons of methanol, 0.06 ton of n-octanol, 9 tons of petroleum ether and 0.05 ton of urea are added, stirred for 3.5 hours at 75 ℃, and filtered; adding 3 tons of methanol, 8 tons of petroleum ether, 0.008 ton of n-octanol and 0.05 ton of urea again, stirring for 3 hours at 70 ℃, and filtering; and adding 3 tons of methanol, 8 tons of petroleum ether, 0.008 ton of n-octanol and 0.05 ton of urea again, stirring for 3 hours at 70 ℃, filtering and drying to obtain 4.991 tons of polyethylene powder.

Comparative example 9

At 20m³The ash content of the washing tank is 40PPm and the molecular weight is 32 multiplied by 10⁴5 tons of polyethylene in g/mol, 5 tons of methanol, 0.06 ton of n-octanol, 9 tons of petroleum ether and 0.05 ton of urea are added, stirred for 3.5 hours at 75 ℃, and filtered; adding 3 tons of methanol, 8 tons of petroleum ether, 0.008 ton of n-octanol and 0.05 ton of urea again, stirring for 3 hours at 70 ℃, and filtering; and adding 3 tons of methanol, 8 tons of petroleum ether, 0.008 ton of n-octanol and 0.05 ton of urea again, stirring for 3 hours at 70 ℃, filtering and drying to obtain 4.992 tons of polyethylene powder.

The results of the ash content of the polyolefin before and after washing are shown in Table 1.

The results of the polyolefin molecular weight and molecular weight distribution before and after washing are shown in Table 2.

The results of polypropylene isotacticity, melting point and polyethylene melting point before and after washing are shown in Table 3.

TABLE 1

TABLE 2

TABLE 3

The technical effects after the implementation of the method disclosed by the patent are as follows:

the ultra-low ash polyolefin and the preparation method and the application thereof are characterized in that: the ultra-low ash content polyolefin prepared by the method disclosed by the patent has the advantages that the ash content of the polyolefin is obviously reduced, and the ash content of the polyolefin is lower than 20 PPm.

The ultra-low ash polyolefin and the preparation method and the application thereof are characterized in that: the ultra-low ash polyolefin prepared by the method disclosed by the patent has narrow molecular weight distribution.

The ultra-low ash polyolefin and the preparation method and the application thereof are characterized in that: the method disclosed by the patent is adopted to prepare the polyolefin with ultra-low ash content, so that the isotacticity of the polyolefin is improved.

The ultra-low ash polyolefin and the preparation method and the application thereof are characterized in that: the melting point of the ultra-low ash polyolefin prepared by the method disclosed by the patent is increased.

The ultra-low ash polyolefin and the preparation method and the application thereof are characterized in that: the molecular weight of the ultra-low ash polyolefin prepared by the method disclosed by the patent is increased.