CN112876595B - Preparation process of ultrapure PE resin and ultrapure PE resin prepared by preparation process - Google Patents

Preparation process of ultrapure PE resin and ultrapure PE resin prepared by preparation process Download PDF

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CN112876595B
CN112876595B CN202110080788.1A CN202110080788A CN112876595B CN 112876595 B CN112876595 B CN 112876595B CN 202110080788 A CN202110080788 A CN 202110080788A CN 112876595 B CN112876595 B CN 112876595B
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solution
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ethylene
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CN112876595A (en
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刘晓霞
徐波
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Suzhou Hanpu Evan Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention relates to the field of PE (polyethylene) resin, in particular to a preparation process of ultrapure PE resin and the ultrapure PE resin prepared by the preparation process, wherein the preparation process of the ultrapure PE resin comprises the following steps: (1) Mixing ethylene, olefin with 3-7 carbon atoms and a solvent, feeding the mixture by adopting a cold material and a hot material, and reacting the mixture in the presence of a catalyst; (2) adding a deactivating agent to terminate the reaction; and (3) removing impurities and purifying to obtain the product. The preparation process of the ultra-pure PE resin has the advantages of simple operation, concise flow, high reaction speed, wide ranges of density, melt index and stress index of the obtained ultra-pure PE resin, convenient product grade switching, few byproducts, 95.0 percent of conversion per pass of ethylene and 98.5 percent of utilization rate.

Description

Preparation process of ultrapure PE resin and ultrapure PE resin prepared by preparation process
Technical Field
The invention relates to the field of PE (polyethylene) resin, in particular to a preparation process of ultrapure PE resin and the ultrapure PE resin prepared by the preparation process.
Background
Solution polymerization is one of the important polymerization methods in the field of polymer manufacturing, and has the advantages of small volume of a polymerization reactor, short polymerization reaction time, less transition materials when product grades are switched, high production flexibility, high single-pass conversion rate of monomers, low gel content, uniform monomer distribution, stable product quality, production of products with special properties and the like, so that solution polymerization always has one of the directions of close attention of people. However, in the industrial production process of producing PE resin from ethylene, the polymer wall adhesion phenomenon is serious, which brings inconvenience to the subsequent cleaning work, and simultaneously, other olefin materials in the feeding material bring difficulty to the subsequent purification process, especially the content of solvent impurities is high.
Disclosure of Invention
In view of the problems of the prior art, a first aspect of the present invention provides a process for preparing an ultrapure PE resin, comprising the steps of:
(1) Mixing ethylene, olefin with 3-7 carbon atoms and a solvent, feeding the mixture by adopting a cold material and a hot material, and reacting the mixture in the presence of a catalyst;
(2) Adding a deactivating agent to terminate the reaction;
(3) Removing impurities and purifying to obtain the product.
In a preferred embodiment of the present invention, when the olefin having 3 to 7 carbon atoms includes butene, the weight ratio of ethylene to butene is 1: (0.1-0.3).
As a preferred technical scheme of the invention, the butene is 1-butene and/or 2-butene.
As a preferable technical scheme of the invention, the butene is 1-butene and 2-butene, and the weight ratio of the butene to the 2-butene is 1: (0.5-1.3).
As a preferred technical scheme of the invention, the temperature of the cold material is 30-60 ℃.
As a preferred technical scheme of the invention, the temperature of the hot material is 100-200 ℃.
As a preferred embodiment of the present invention, the step (1) includes: mixing ethylene, olefin with 3-7 carbon atoms and a solvent, feeding by adopting two materials of cold and hot materials within 3min, wherein the weight ratio of the cold material to the hot material is 1: (5-10), after feeding for 3-5min, adjusting the feeding content of the cold material and the hot material to ensure that the weight ratio of the cold material to the hot material is 1: (0.3-0.6), and then reacting in the presence of a catalyst.
In a preferred embodiment of the present invention, the deactivating agent is one or more selected from acetylacetone, isopropanolamine, modified or unmodified fatty acids.
As a preferred embodiment of the present invention, the step (3) includes: heating the material obtained in the step (2) to 286-305 ℃, performing flash evaporation treatment under the pressure of 2500-3500KPa, performing treatment on the material by using a filler modified by dicarboxylic acid with 4-6 carbon atoms, extruding, granulating, and performing gas stripping and drying to obtain the product.
The second aspect of the invention provides an ultrapure PE resin prepared by the preparation process of the ultrapure PE resin, wherein the density of the ultrapure PE resin is 918-964Kg/m 3 The melt index at 190 ℃/2.16kg is 0.25-120g/10min, and the stress index is 1.2-2.
Compared with the prior art, the invention has the following beneficial effects:
(1) The preparation process of the ultrapure PE resin has the advantages of simple operation, concise flow, high reaction speed, wide ranges of density, melt index and stress index of the obtained ultrapure PE resin, convenient product grade switching, few byproducts, 95.0 percent of ethylene single-pass conversion rate and 98.5 percent of utilization rate;
(2) The invention controls the types and weight ratio of the materials, and has no wall sticking phenomenon in the preparation process of the PE resin, thereby saving the operation of cleaning a reactor and reducing the working flow;
(3) Treating by using a dicarboxylic acid modified filler with 4-6 carbon atoms, so that the catalyst wrapped by the PE resin branched chain is exposed on the surface, and removing the catalyst, a solvent, water, methanol, ketones and the like in time in a purification stage, thereby improving the purity of the PE resin;
(4) Simultaneously feeding cold and hot materials, and regulating the feeding temperature of the reactor by controlling the proportion of the cold and hot materials to ensure that the polymerization reaction is carried out within a certain temperature range;
(5) When the weight ratio of the acetylacetone to the isopropanolamine is (2.2-3.4): 1, the efficiency is high during deactivation treatment, and the method is not influenced by the steric hindrance of olefin in the reaction raw material.
Detailed Description
The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
The invention provides a preparation process of an ultrapure PE resin, which comprises the following steps:
(1) Mixing ethylene, olefin with 3-7 carbon atoms and a solvent, feeding the mixture by adopting a cold material and a hot material, and reacting the mixture in the presence of a catalyst;
(2) Adding a deactivating agent to terminate the reaction;
(3) Removing impurities and purifying to obtain the product.
Step (1)
In one embodiment, when the olefin having 3 to 7 carbon atoms includes butene, the weight ratio of ethylene to butene is 1: (0.1-0.3).
Preferably, the weight ratio of ethylene to butene is 1:0.2.
preferably, the butene comprises 1-butene and 2-butene, and the weight ratio of the 1: (0.5-1.3); more preferably, the weight ratio of 1-butene to 2-butene is 1:0.8.
the applicant has surprisingly found that, in the production of PE resins, when the weight ratio between ethylene and butene is 1: (0.1-0.3) there is some adhesion of material to the walls of the reactor, which, if not cleaned in time, affects the overall processing of the polyethylene and affects the discharge, the applicant has found unexpectedly that when the butenes comprise 1-butene and 2-butene in a weight ratio of 1: (0.5-1.3), the reactor wall is cleaner in the polyethylene production process, the clean operation is reduced, and the production process is smoothly carried out. The applicant believes that the possible reason is when the butenes include 1-butene and 2-butene and their weight ratio is 1: (0.5-1.3), it hinders the efficiency of coordination of ethylene on the vacancy of titanium atom or vanadium atom, and at the same time, under the condition, the ethylene molecule is not easy to displace, so that the probability of producing small molecule polymer is reduced, and the wall sticking phenomenon is reduced.
The solvent used in the present invention is not particularly limited, and may be selected conventionally by those skilled in the art.
In one embodiment, the solvent is cyclohexane.
Preferably, the weight ratio of cyclohexane to ethylene is (8-15): 1; more preferably, the weight ratio of cyclohexane to ethylene is 12:1.
in one embodiment, the temperature of the cold mass is 30-60 ℃.
Preferably, the temperature of the cold mass is 50 ℃.
In one embodiment, the temperature of the hot mass is from 100 to 200 ℃.
Preferably, the temperature of the hot mass is 160 ℃.
Adopt cold and hot material simultaneous feed in this application, through the proportion of control cold and hot material, adjust the feeding temperature of reactor, make polymerization go on at certain temperature range.
In one embodiment, the step (1) comprises: mixing ethylene, olefin with 3-7 carbon atoms and a solvent, feeding by adopting two materials of cold and hot materials within 3min, wherein the weight ratio of the cold material to the hot material is 1: (5-10), after feeding for 3-5min, adjusting the feeding content of the cold material and the hot material to ensure that the weight ratio of the cold material to the hot material is 1: (0.3-0.6) and then reacting in the presence of a catalyst.
In a preferred embodiment, the step (1) comprises: mixing ethylene, olefin with 3-7 carbon atoms and a solvent, feeding by adopting two materials of cold and hot materials within 3min, wherein the weight ratio of the cold material to the hot material is 1: and 8, after feeding for 5min, adjusting the feeding content of the cold material and the hot material to ensure that the weight ratio of the cold material to the hot material is 1:0.4, followed by reaction in the presence of a catalyst.
In one embodiment, the reaction temperature is from 200 to 300 ℃.
In one embodiment, the reaction pressure is 11277-16671KPa.
In the production of full density polyethylene, the skilled person can routinely select the reaction temperature and reaction pressure according to the density of the polyethylene produced, according to the application.
The preparation process of the PE resin can produce the PE resin with the density of 918-964Kg/m 3 126 products with different brands and melt index of 0.25-120g/10min and stress index of 1.2-2.0.
In one embodiment, the catalyst comprises a main catalyst and a cocatalyst.
Preferably, the main catalyst is one or more of a titanium catalyst and/or a vanadium catalyst; more preferably, the main catalyst is a titanium-based catalyst or a vanadium-based catalyst.
Preferably, the weight ratio of the titanium catalyst to the vanadium catalyst is (1-4): 1; more preferably, the weight ratio of the titanium-based catalyst to the vanadium-based catalyst is 1:1.
preferably, the cocatalyst is an aluminum alkyl.
Preferably, the alkyl aluminum is selected from one or more of triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, tri-n-octyl aluminum, tri (2-ethyl) hexyl aluminum, diethyl aluminum monochloride and diethyl aluminum ethoxide; further preferably, the aluminum alkyls are diethylaluminum monochloride and diethylaluminum ethoxide.
The titanium-based catalyst, the vanadium-based catalyst, the ratio of the main catalyst to the cocatalyst and the ratio between the two cocatalysts are not particularly limited, and those skilled in the art can make routine selections according to the density of the polyethylene to be produced by combining the descriptions in the present application.
The proportion of catalyst in the feed is not particularly limited in this application and can be routinely selected by those skilled in the art.
In one embodiment, the catalyst comprises from 0.0005 to 5wt% of the total of ethylene and olefins having from 3 to 7 carbon atoms.
Preferably, the catalyst accounts for 3.4wt% of the total amount of the olefins having 3 to 7 carbon atoms.
Step (2)
In one embodiment, the deactivating agent is selected from one or more of acetylacetone, isopropanolamine, modified or unmodified fatty acids.
Preferably, the modified fatty acid is a fatty acid modified with a basic group and/or a porphyrin group.
The alkaline group and porphyrin group modified fatty acid deactivation treatment method is high in efficiency and is not affected by steric hindrance of olefin in reaction raw materials.
The basic group and the modification method described herein are not particularly limited, and those skilled in the art can select them conventionally.
In one embodiment, the deactivating agents are acetylacetone and isopropanolamine.
Preferably, the weight ratio of the acetylacetone to the isopropanolamine is (2.2-3.4): 1; more preferably, the weight ratio of acetylacetone to isopropanolamine is 2.8:1.
when the weight ratio of the acetylacetone to the isopropanolamine is (2.2-3.4): 1, the efficiency is high during deactivation treatment, and the method is not influenced by the steric hindrance of olefin in the reaction raw material.
The amount of the deactivator to be added is not particularly limited and may be selected by those skilled in the art in a conventional manner.
Step (3)
In one embodiment, the step (3) comprises: heating the material obtained in the step (2) to 286-305 ℃, performing flash evaporation treatment under the pressure of 2500-3500KPa, performing treatment on the material by using a filler modified by dicarboxylic acid with 4-6 carbon atoms, extruding, granulating, and performing gas stripping and drying to obtain the product.
In a preferred embodiment, the step (3) comprises: heating the material obtained in the step (2) to 292 ℃, performing flash evaporation treatment under 3000KPa pressure, performing treatment on the filler modified by dicarboxylic acid with 4-6 carbon atoms, extruding, granulating, and performing gas stripping drying to obtain the product.
The filler is not particularly limited, and silica, alumina and the like can be cited, and those skilled in the art can select them conventionally.
In one embodiment, the filler is silica.
In one embodiment, the dicarboxylic acid is glutaric acid.
The applicant unexpectedly finds that the glutaric acid modified filler is used for treating the PE resin polymer, so that the catalyst wrapped by the PE resin branched chain is exposed on the surface, the catalyst, the solvent, the water, the methanol, the ketone and the like are cleaned in time, and the purity of the PE resin is improved.
In one embodiment, the method of making the dicarboxylic acid modified filler comprises the steps of:
1. firstly, mixing 15mL of ethyl orthosilicate and 100mL of absolute ethyl alcohol to obtain solution A, dissolving 30mL of concentrated ammonia water (25 wt%) in 150mL of absolute ethyl alcohol, mixing to obtain solution B, dripping the solution A into the solution B in a 40% constant-temperature water bath, reacting for 20 hours, centrifuging, washing and drying;
2. adding 1g of the substance obtained in the step 1 into a beaker filled with 50mL of acetonitrile, performing ultrasonic treatment, adding 7g of dicarboxylic acid, continuously stirring, heating to 60 ℃ under reflux until the dicarboxylic acid is completely dissolved, then pouring the solution in the beaker into a three-neck flask, heating to 75 ℃ under reflux, continuously stirring, keeping the temperature for 24 hours, cooling the product to 65 ℃, performing hot suction filtration, performing centrifugal washing for 4 times by using a mixed solution of absolute ethyl alcohol and deionized water, and performing vacuum drying at 120 ℃ to obtain the product.
In the preparation process of the ultra-pure PE resin, the total content of metal impurities in the production environment needs to be strictly controlled to be below 3ppm, the control method is not particularly limited, and the technical personnel in the field can make routine selection.
Production environments include, but are not limited to, raw material preparation, pipelines, manual operating environments, and the like.
The metal impurities are B, mg, na, al, P, K, ca, mn, fe, ni, cu, zn, as, pb and Cr. The second aspect of the invention provides an ultrapure PE resin prepared by the preparation process of the PE resin, wherein the density of the ultrapure PE resin is 918-964Kg/m 3 The melt index of 190 ℃/2.16kg is 0.25-120g/10min, and the stress index is 1.2-2.
Examples
Hereinafter, the present invention will be described in more detail by way of examples, but it should be understood that these examples are merely illustrative and not restrictive. The starting materials used in the examples which follow are all commercially available unless otherwise stated.
Example 1
Embodiment 1 of the present application provides a preparation process of an ultrapure PE resin, specifically as follows:
(1) Mixing ethylene, butylene and cyclohexane, feeding by adopting two materials of cold and hot materials within 3min, wherein the weight ratio of the cold material to the hot material is 1: and 5, after feeding for 3min, adjusting the feeding content of the cold material and the hot material to ensure that the weight ratio of the cold material to the hot material is 1:0.3, then carrying out a reaction at the temperature of 200 ℃ and 11277KPa in the presence of a catalyst;
(2) Adding a deactivating agent to terminate the reaction;
(3) Heating the material obtained in the step (2) to 286 ℃, performing flash evaporation treatment under the pressure of 2500KPa, performing filler treatment modified by glutaric acid, extruding, granulating, and performing gas stripping and drying to obtain the modified filler.
The weight ratio of the ethylene to the butylene is 1:0.1; the butene is 1-butene and 2-butene, and the weight ratio is 1:0.5; the weight ratio of cyclohexane to ethylene is 8:1.
the temperature of the cold material is 30 ℃ and the temperature of the hot material is 100 ℃.
The catalyst is a main catalyst and a cocatalyst, the main catalyst is titanium chloride and vanadium trichloride, and the weight ratio is 1:1; the cocatalyst is diethyl aluminum monochloride and diethyl ethoxy aluminum, and the weight ratio is 1:1; the catalyst accounts for 3.4wt% of the total amount of ethylene and butylene, and the weight ratio of the main catalyst to the cocatalyst is 1:100.
the deactivating agent is acetylacetone and isopropanolamine in a weight ratio of 2.2:1.
the preparation method of the glutaric acid modified filler comprises the following specific steps:
1. firstly, mixing 15mL of ethyl orthosilicate and 100mL of absolute ethyl alcohol to obtain solution A, dissolving 30mL of concentrated ammonia water (25 wt%) in 150mL of absolute ethyl alcohol, mixing to obtain solution B, dripping the solution A into the solution B in a 40% constant-temperature water bath, reacting for 20 hours, centrifuging, washing and drying;
2. adding 1g of the substance obtained in the step 1 into a beaker containing 50mL of acetonitrile, performing ultrasonic treatment, adding 7g of glutaric acid, continuously stirring, heating to 60 ℃ under reflux until the dicarboxylic acid is completely dissolved, then pouring the solution in the beaker into a three-neck flask, heating to 75 ℃ under reflux, continuously stirring, keeping the temperature for 24h, cooling the product to 65 ℃, performing hot pumping filtration, performing centrifugal washing for 4 times by using a mixed solution of absolute ethyl alcohol and deionized water, and performing vacuum drying at 120 ℃ to obtain the product.
Example 2
Embodiment 2 of the present application provides a preparation process of an ultrapure PE resin, specifically as follows:
(1) Mixing ethylene, butylene and cyclohexane, feeding by adopting two materials of cold and hot materials within 3min after feeding, wherein the weight ratio of the cold material to the hot material is 1: and 10, after feeding for 3min, adjusting the feeding content of the cold material and the hot material to ensure that the weight ratio of the cold material to the hot material is 1:0.6, then reacting at 300 ℃ and 16671KPa in the presence of a catalyst;
(2) Adding a deactivating agent to terminate the reaction;
(3) And (3) heating the material obtained in the step (2) to 305 ℃, performing flash evaporation treatment under 3500KPa pressure, performing glutaric acid modified filler treatment, extruding, granulating, and performing gas stripping and drying to obtain the modified filler.
The weight ratio of the ethylene to the butylene is 1:0.3; the butene is 1-butene and 2-butene, and the weight ratio of the butene to the 2-butene is 1:1.3; the weight ratio of cyclohexane to ethylene is 15:1.
the temperature of the cold material is 60 ℃ and the temperature of the hot material is 200 ℃.
The catalyst is a main catalyst and a cocatalyst, the main catalyst is titanium chloride and vanadium trichloride, and the weight ratio is 4:1; the cocatalyst is diethyl aluminum monochloride and diethyl ethoxy aluminum, and the weight ratio is 1:1; the catalyst accounts for 3.4wt% of the total amount of ethylene and butylene, and the weight ratio of the main catalyst to the cocatalyst is 1:100.
the deactivating agent is acetylacetone and isopropanolamine in a weight ratio of 3.4:1.
the preparation method of the glutaric acid modified filler comprises the following specific steps:
1. firstly, mixing 15mL of ethyl orthosilicate and 100mL of absolute ethyl alcohol to obtain solution A, dissolving 30mL of concentrated ammonia water (25 wt%) in 150mL of absolute ethyl alcohol, mixing to obtain solution B, dripping the solution A into the solution B in a 40% constant-temperature water bath, reacting for 20 hours, centrifuging, washing and drying;
2. adding 1g of the substance obtained in the step 1 into a beaker containing 50mL of acetonitrile, performing ultrasonic treatment, adding 7g of glutaric acid, continuously stirring, heating to 60 ℃ under reflux until the dicarboxylic acid is completely dissolved, then pouring the solution in the beaker into a three-neck flask, heating to 75 ℃ under reflux, continuously stirring, keeping the temperature for 24h, cooling the product to 65 ℃, performing hot pumping filtration, performing centrifugal washing for 4 times by using a mixed solution of absolute ethyl alcohol and deionized water, and performing vacuum drying at 120 ℃ to obtain the product.
Example 3
Embodiment 3 of the present application provides a preparation process of an ultrapure PE resin, specifically as follows:
(1) Mixing ethylene, butylene and cyclohexane, feeding by adopting two materials of cold and hot materials within 3min, wherein the weight ratio of the cold material to the hot material is 1: and 8, after feeding for 3min, adjusting the feeding content of the cold material and the hot material to ensure that the weight ratio of the cold material to the hot material is 1:0.4, then reacting at 300 ℃ and 16671KPa in the presence of a catalyst;
(2) Adding a deactivating agent to terminate the reaction;
(3) And (3) heating the material obtained in the step (2) to 292 ℃, performing flash evaporation treatment under 3000KPa pressure, performing glutaric acid modified filler treatment, extruding, granulating, and performing gas stripping and drying to obtain the modified filler.
The weight ratio of the ethylene to the butylene is 1:0.2; the butene is 1-butene and 2-butene, and the weight ratio is 1:0.8; the weight ratio of the cyclohexane to the ethylene is 12:1.
the temperature of the cold material is 50 ℃ and the temperature of the hot material is 160 ℃.
The catalyst is a main catalyst and a cocatalyst, the main catalyst is titanium chloride and vanadium trichloride, and the weight ratio is 4:1; the cocatalyst is diethyl aluminum monochloride and diethyl ethoxy aluminum, and the weight ratio is 1:1; the catalyst accounts for 3.4wt% of the total amount of ethylene and butylene, and the weight ratio of the main catalyst to the cocatalyst is 1:100.
the deactivator is acetylacetone and isopropanolamine, and the weight ratio is 2.8:1;
the preparation method of the glutaric acid modified filler comprises the following specific steps:
1. firstly, mixing 15mL of ethyl orthosilicate and 100mL of absolute ethyl alcohol to obtain solution A, dissolving 30mL of concentrated ammonia water (25 wt%) in 150mL of absolute ethyl alcohol, mixing to obtain solution B, dripping the solution A into the solution B in a 40% constant-temperature water bath, reacting for 20 hours, centrifuging, washing and drying;
2. adding 1g of the substance obtained in the step 1 into a beaker containing 50mL of acetonitrile, performing ultrasonic treatment, adding 7g of dicarboxylic acid, continuously stirring, heating to 60 ℃ under reflux until glutaric acid is completely dissolved, then pouring the solution in the beaker into a three-neck flask, heating to 75 ℃ under reflux, continuously stirring, keeping the temperature for 24h, cooling the product to 65 ℃, performing hot pumping filtration, performing centrifugal washing for 4 times by using a mixed solution of absolute ethyl alcohol and deionized water, and performing vacuum drying at 120 ℃ to obtain the product.
Example 4
Embodiment 4 of the present invention provides a process for preparing an ultrapure PE resin, which is substantially the same as embodiment 3 except that the butene is 1-butene.
Example 5
Embodiment 5 of the present invention provides a process for preparing an ultrapure PE resin, which is substantially the same as embodiment 3 except that the butene is 2-butene.
Example 6
Example 5 of the present invention provides a process for preparing an ultrapure PE resin, as set forth in example 3, wherein the butene is replaced with propylene.
Example 7
Embodiment 7 of the present invention provides a preparation process of an ultrapure PE resin, which is the same as embodiment 3 in specific embodiment, except that in step (3), the material obtained in step (2) is heated to 292 ℃, subjected to flash evaporation at 3000KPa, subjected to filler treatment, extruded, granulated, stripped, and dried to obtain the ultrapure PE resin.
The preparation method of the filler comprises the following specific steps:
firstly, mixing 15mL of tetraethoxysilane and 100mL of absolute ethyl alcohol to obtain a solution A, dissolving 30mL of concentrated ammonia water (25 wt%) in 150mL of absolute ethyl alcohol to obtain a solution B, dripping the solution A into the solution B in a 40% constant-temperature water bath, reacting for 20 hours, centrifuging, washing and drying.
Example 8
Embodiment 8 of the present invention provides a preparation process of an ultrapure PE resin, which is the same as embodiment 3 in specific embodiment, except that the material obtained in step (2) in step (3) is heated to 292 ℃, subjected to flash evaporation under 3000KPa, treated with a filler modified with valeric acid, extruded, granulated, and air-stripped to dry, thereby obtaining the ultrapure PE resin.
The preparation method of the valeric acid modified filler specifically comprises the following steps:
1. firstly, mixing 15mL of ethyl orthosilicate and 100mL of absolute ethyl alcohol to obtain solution A, dissolving 30mL of concentrated ammonia water (25 wt%) in 150mL of absolute ethyl alcohol, mixing to obtain solution B, dripping the solution A into the solution B in a 40% constant-temperature water bath, reacting for 20 hours, centrifuging, washing and drying;
2. adding 1g of the substance obtained in the step 1 into a beaker containing 50mL of acetonitrile, performing ultrasonic treatment, adding 7g of valeric acid, continuously stirring, heating to 60 ℃ under reflux until the dicarboxylic acid is completely dissolved, then pouring the solution in the beaker into a three-neck flask, heating to 75 ℃ under reflux, continuously stirring, keeping the temperature for 24h, cooling the product to 65 ℃, performing hot suction filtration, centrifugally washing for 4 times by using a mixed solution of absolute ethyl alcohol and deionized water, and performing vacuum drying at 120 ℃ to obtain the compound.
Performance evaluation
1. Cleanliness of reactor wall: PE resins were produced by the production processes of examples 1 to 8, respectively, and after one month of continuous production, whether or not substances were adhered to the inner side of the reactor wall was recorded.
2. Cyclohexane content: the contents of cyclohexane in the polyethylene resins prepared in examples 1 to 8 were measured by high performance liquid chromatography, respectively, and it was noted that the contents were excellent if the content of cyclohexane was less than 0.03wt%, good if the content was 0.03 to 0.05wt%, and poor if the content was more than 0.05 wt%.
TABLE 1
Cleanliness of reactor wall Cyclohexane content
Example 1 No matter adhesion Youyou (an instant noodle)
Example 2 No matter adhesion Youyou (an instant noodle)
Example 3 With adhesion of matter Superior food
Example 4 With adhesion of matter Superior food
Example 5 With adhesion of matter Superior food
Example 6 With adhesion of matter Superior food
Example 7 No matter adhesion Good wine
Example 8 No adhesion of matter Good wine
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as can be conceived and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.

Claims (2)

1. A preparation process of ultra-pure PE resin is characterized by comprising the following steps:
(1) Mixing ethylene, butylene and cyclohexane, feeding by adopting two materials of cold and hot materials within 3min, wherein the weight ratio of the cold material to the hot material is 1: and 5, after feeding for 3min, adjusting the feeding content of the cold material and the hot material to ensure that the weight ratio of the cold material to the hot material is 1:0.3, then carrying out 11277KPa reaction at 200 ℃ in the presence of a catalyst;
(2) Adding a deactivating agent to terminate the reaction;
(3) Heating the material obtained in the step (2) to 286 ℃, performing flash evaporation treatment under the pressure of 2500KPa, performing filler treatment modified by glutaric acid, extruding, granulating, and performing gas stripping and drying to obtain the modified filler; the weight ratio of the ethylene to the butylene is 1:0.1; the butene is 1-butene and 2-butene, and the weight ratio is 1:0.5; the weight ratio of the cyclohexane to the ethylene is 8:1;
the catalyst is a main catalyst and a cocatalyst, the main catalyst is titanium chloride and vanadium trichloride, and the weight ratio is 1:1; the cocatalyst is diethyl aluminum monochloride and diethyl aluminum ethoxide, and the weight ratio of the cocatalyst to the diethyl aluminum monochloride is 1:1; the catalyst accounts for 3.4wt% of the total amount of ethylene and butylene, and the weight ratio of the main catalyst to the cocatalyst is 1:100, respectively;
the temperature of the cold material is 30 ℃, and the temperature of the hot material is 100 ℃; the deactivator is acetylacetone and isopropanolamine, and the weight ratio is 2.2:1;
the preparation method of the glutaric acid modified filler comprises the following specific steps:
1) Firstly, mixing 15mL of ethyl orthosilicate and 100mL of absolute ethyl alcohol to obtain solution A, dissolving 30mL of 25wt% concentrated ammonia water in 150mL of absolute ethyl alcohol, mixing to obtain solution B, dripping the solution A into the solution B in a 40% constant-temperature water bath, reacting for 20 hours, centrifuging, washing and drying;
2) Adding 1g of the substance obtained in the step 1 into a beaker filled with 50mL of acetonitrile, performing ultrasonic treatment, adding 7g of glutaric acid, continuously stirring, heating to 60 ℃ under reflux until the dicarboxylic acid is completely dissolved, then pouring the solution in the beaker into a three-neck flask, heating to 75 ℃ under reflux, continuously stirring, keeping the temperature for 24 hours, cooling the product to 65 ℃, performing hot suction filtration, centrifugally washing for 4 times by using a mixed solution of absolute ethyl alcohol and deionized water, and performing vacuum drying at 120 ℃ to obtain the compound.
2. A preparation process of ultra-pure PE resin is characterized by comprising the following steps:
(1) Mixing ethylene, butylene and cyclohexane, feeding by adopting two materials of cold and hot materials within 3min, wherein the weight ratio of the cold material to the hot material is 1: and 10, after feeding for 3min, adjusting the feeding content of the cold material and the hot material to ensure that the weight ratio of the cold material to the hot material is 1:0.6, then reacting at 300 ℃ and 16671KPa in the presence of a catalyst;
(2) Adding a deactivating agent to terminate the reaction;
(3) Heating the material obtained in the step (2) to 305 ℃, performing flash evaporation treatment under 3500KPa pressure, performing glutaric acid modified filler treatment, extruding, granulating, and performing gas stripping drying to obtain the product;
the weight ratio of the ethylene to the butylene is 1:0.3; the butene is 1-butene and 2-butene, and the weight ratio is 1:1.3; the weight ratio of the cyclohexane to the ethylene is 15:1;
the temperature of the cold material is 60 ℃, and the temperature of the hot material is 200 ℃;
the catalyst is a main catalyst and a cocatalyst, the main catalyst is titanium chloride and vanadium trichloride, and the weight ratio is 4:1; the cocatalyst is diethyl aluminum monochloride and diethyl ethoxy aluminum, and the weight ratio is 1:1; the catalyst accounts for 3.4wt% of the total amount of ethylene and butylene, and the weight ratio of the main catalyst to the cocatalyst is 1:100;
the deactivating agent is acetylacetone and isopropanolamine in a weight ratio of 3.4:1;
the preparation method of the glutaric acid modified filler comprises the following specific steps:
1) Firstly, mixing 15mL of ethyl orthosilicate and 100mL of absolute ethyl alcohol to obtain solution A, dissolving 30mL of 25wt% concentrated ammonia water in 150mL of absolute ethyl alcohol, mixing to obtain solution B, dripping the solution A into the solution B in a 40% constant-temperature water bath, reacting for 20 hours, centrifuging, washing and drying;
2) Adding 1g of the substance obtained in the step 1 into a beaker containing 50mL of acetonitrile, performing ultrasonic treatment, adding 7g of glutaric acid, continuously stirring, heating to 60 ℃ under reflux until the dicarboxylic acid is completely dissolved, then pouring the solution in the beaker into a three-neck flask, heating to 75 ℃ under reflux, continuously stirring, keeping the temperature for 24h, cooling the product to 65 ℃, performing hot pumping filtration, performing centrifugal washing for 4 times by using a mixed solution of absolute ethyl alcohol and deionized water, and performing vacuum drying at 120 ℃ to obtain the product.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1125954A (en) * 1993-06-21 1996-07-03 Dsm有限公司 Process for the preparation of low molecular weight copolymers of ethylene with at least one other 1-alkene
CN1751072A (en) * 2003-02-17 2006-03-22 三井化学株式会社 Ethylenic polymer and application thereof to molded product
JP2018002759A (en) * 2016-06-27 2018-01-11 旭化成株式会社 Polyethylene-based powder, method for producing polyethylene-based powder, polyethylene-based resin composition, and method for producing crosslinked polyethylene pipe
CN107880197A (en) * 2016-09-30 2018-04-06 中国石化扬子石油化工有限公司 Ultra-high molecular weight polyethylene polyvinyl resin and its preparation method and application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1125954A (en) * 1993-06-21 1996-07-03 Dsm有限公司 Process for the preparation of low molecular weight copolymers of ethylene with at least one other 1-alkene
CN1751072A (en) * 2003-02-17 2006-03-22 三井化学株式会社 Ethylenic polymer and application thereof to molded product
JP2018002759A (en) * 2016-06-27 2018-01-11 旭化成株式会社 Polyethylene-based powder, method for producing polyethylene-based powder, polyethylene-based resin composition, and method for producing crosslinked polyethylene pipe
CN107880197A (en) * 2016-09-30 2018-04-06 中国石化扬子石油化工有限公司 Ultra-high molecular weight polyethylene polyvinyl resin and its preparation method and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
溶液法聚乙烯反应的优化控制与影响因素研究;侯向俊 等;《当代化工》;20141130;第43卷(第11期);第2335-2338页 *

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