CN114891140A - Preparation method of polyolefin copolymer with low ash content and high comonomer content - Google Patents
Preparation method of polyolefin copolymer with low ash content and high comonomer content Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/08—Butenes
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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
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
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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
- C08F210/14—Monomers containing five or more carbon atoms
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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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/06—Butadiene
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- 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
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- 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
Abstract
The invention discloses a preparation method of a polyolefin copolymer with low ash content and high comonomer content. The preparation of the polyolefin copolymer with low ash content and high comonomer content is realized by adding a polymerization solution, an olefin monomer, a comonomer, a cocatalyst and a main catalyst in a single reactor in sequence and adding the component A. The component A is added flexibly and canThe catalyst can be premixed with the catalyst or can be sequentially added into a reaction kettle together with the catalyst, wherein the addition of the component A can greatly reduce the using amount of the cocatalyst, improve the activity and strengthen the insertion capacity of the comonomer, namely the polymerization activity is improved by 5-500 percent and the insertion rate of the comonomer is improved by 5-100 percent. The density of the copolymer prepared by the method is 0.86g/cm 3 ～0.93g/cm 3 In between, the ash content is less than 1000 ppm. The method has the advantages of high production efficiency, simple operation, short flow, low equipment investment, low energy consumption and the like, can efficiently prepare the polyolefin copolymer, and has the characteristic of being generally suitable for polyolefin catalysts.
Description
Technical Field
The invention relates to the field of olefin polymerization reaction, in particular to a preparation method of a polyolefin copolymer with low ash content and high comonomer content.
Background
The polymerization reaction in which two or more monomers participate together is called copolymerization, and the resulting polymer contains two or more monomer units, and such polymers are called copolymers. Well-known copolymers include styrene-butadiene-styrene block copolymer (SBS), acrylonitrile-butadiene-styrene terpolymer (ABS), ethylene-vinyl acetate copolymer (EVA), ethylene-octene copolymer (POE), and the like. Copolymers can be classified into random copolymers, alternating copolymers, block copolymers and graft copolymers according to the arrangement of various monomers in the molecular chain of the copolymer. The appearance of the copolymer endows the material with abundant and various performances, and widens the application field of the material.
At present, people can realize the high-efficiency preparation of olefin copolymers through the preparation process and the design of catalysts. Patent CN102558448A realizes the preparation of olefin copolymers by polymerizing monomers in a first stage by means of a slurry process, removing the solvent and oligomers dissolved therein in a second stage by means of a filter press and drying in the same apparatus, and then copolymerizing the resulting polymer and monomers in a third stage. Although the polyolefin copolymer prepared by the method has low oligomer content, the mode of preparing the copolymer by multiple stages and reactors has the obvious problems of large equipment size, more engineering investment, high operation cost, complex operation process and the like. During the copolymerization reaction, with the continuous insertion of the comonomer, the viscosity of the system is rapidly increased, which is not beneficial to the reaction. By increasing the reaction temperature, the viscosity of the reaction system can be reduced, which is beneficial to improving the conversion per pass, but the catalyst can be subjected to sintering deactivation and thermal deactivation at higher temperature, and shows lower polymerization activity. Patent CN103122042A discloses a method for preparing ethylene- α -olefin copolymer by continuous solution polymerization using transition metal catalyst having specific quinoline group. Quinoline group ligand effectively inhibits the decomposition of the active center of the catalyst at high temperature, so that the catalyst has better high-temperature stability, and the prepared copolymer has the characteristics of narrow molecular weight distribution, uniform comonomer distribution and the like. However, the preparation process of the catalytic system is complicated.
Disclosure of Invention
The present invention aims to solve the problems of the prior art in the field of preparing copolymers and it is desirable to provide a process for preparing a low ash, high comonomer content, high quality polyolefin copolymer.
In order to solve the above technical problems, the present invention provides a method for preparing a low ash, high comonomer content polyolefin copolymer having a density in the range of 0.86g/cm 3 ～0.93g/cm 3 (ii) a The preparation method comprises the following steps:
adding a solvent A, an olefin monomer, a comonomer, a main catalyst, a cocatalyst and a component A into a reactor, and carrying out polymerization reaction for a certain time at preset temperature and pressure to obtain a polyolefin copolymer with low ash content and high comonomer content, wherein the ash content of the polyolefin copolymer is 1 ppm-1000 ppm, and the molar insertion rate of the comonomer is 5% -100%; wherein the molar ratio range of the main catalyst metal to the component A is 3000: 1-1: 1, the molar ratio of main metal elements of the cocatalyst and the main catalyst is in a range of 1: 1-1000: 1, the component A can be premixed with a main catalyst or can be added into a reaction kettle with the main catalyst respectively;
the component A is a non-metal polar group molecule containing O, F, Cl, S, N or P elements. According to some embodiments of the present invention, the component a is one or more of siloxanes, silazanes, silicophospholanes, ethers and esters. According to some embodiments of the present invention, component a is one or more of triethylenesilylphosphane, divinylcarboxoxane, tetravinylether, hexavinylester, siloxane, fluorocarbon, fluorochloroalkane, wherein the molar ratio of the procatalyst metal to component a is in the range of 1000: 1-5: 1. The addition of the component A can improve the polymerization activity by 5-500 percent and improve the insertion rate of the comonomer by 5-100 percent.
According to some embodiments of the invention, the solvent A is toluene, ethylbenzene, benzene, n-hexane, cyclohexane, n-heptane, cyclopentane, C 4 ～C 18 The normal paraffin, the isoparaffin and the cycloparaffin in the (C) are one or more.
According to some embodiments of the invention, the olefin monomer is one or more of ethylene, propylene, butene, butadiene, pentene; the comonomer is one or more of alpha-olefin of C4-C20.
According to some embodiments of the invention, the comonomer is one or more of 1-octene, 1-hexene, 1-butene, 1-decene.
According to some embodiments of the present invention, the main catalyst is selected from one or more of a Ziegler Natta catalyst, a FI catalyst, a rare earth amine based complex, a late transition metal catalyst, and a metallocene catalyst; the cocatalyst is selected from one or more of methylaluminoxane, modified methylaluminoxane, triethylaluminum, n-butyllithium, triisobutylaluminum, trimethylaluminum, trifluorophenylboron, tributylammonium tetrakis (pentafluorophenyl) aluminum, trifluoroborane and tetrapentafluorophenylborate, and the molar ratio range of the main metal elements of the cocatalyst to the main catalyst is 50: 1-800: 1.
according to some embodiments of the invention, the predetermined temperature range is-50 ℃ to 230 ℃; the preset pressure range is 1 bar-200 bar; the polymerization reaction time ranges from 1min to 1000 min.
According to some embodiments of the invention, the predetermined temperature range is-20 ℃ to 200 ℃; the preset pressure range is 3 bar-100 bar; the polymerization reaction time ranges from 5min to 360 min.
According to some embodiments of the present invention, the polyolefin copolymer preferably has an ash content in the range of 5ppm to 600ppm, more preferably 5 to 300 ppm; the comonomer molar insertion rate is preferably in the range of 5-30%; more preferably 8% to 27%;copolymer M w <5000 is 3 to 9 percent by mass.
Compared with the prior art, the method has the advantages that the third component (component A) is introduced, the interaction between the third component and the active component (the main metal element of the main catalyst and the coordination and composite structure of the main metal element) is strengthened through physical adsorption and adhesion effects, the interaction between the active components is avoided, the active center is stabilized, meanwhile, the main catalyst still keeps a stable structure at high temperature due to the introduction of the third component, and the reduction of the activity of the main catalyst caused by the mutual adsorption between the active components is avoided. The improvement of the stability of the active center can obviously improve the tolerance temperature of the main catalyst, and the high activity is still shown even if the polymerization temperature reaches 200 ℃, the invention can improve the polymerization activity by 5-15 percent, can improve the insertion rate of the comonomer by 5-30 percent, and prepare the copolymer with low ash content and high comonomer content.
Detailed description of the invention
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which the specific conditions are not specified, were conducted under the conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available on the market.
The characterization method of the structure and the performance of the polyolefin copolymer comprises the following steps:
(1) density: determined according to the method of GB/1033-.
(2) Ash content: measured according to GB/T9345.1-2008 and inductively coupled plasma ICP.
(3) Comonomer insertion rate: according to 13 C-NMR measurement and calculation.
(4) Weight average molecular weight: measured by high temperature permeation gel chromatography HT-GPC.
(5) Melt index: the melt flow rate was determined according to GB/T-3682-2000 conditions (190 ℃ C., load of 2.16 kg), and is generally designated MI 2.16.
Example 1
150L of a toluene/ethylbenzene solution (1: 2: 4 mix), 50L of comonomer 1-hexene, 100mL of 1mol/L triethylaluminum cocatalyst, 0.5g of triethylsilylphosphane and 1g of procatalyst, i.e., Ziegler-Natta catalyst, were added sequentially in a single 300L reactor, wherein the molar ratio of procatalyst metal to component A was 30: 1, the molar ratio of main metal elements of the cocatalyst to the main catalyst is 50: 1, adding trivinyl-based phosphane (component A) and a catalyst into a reactor in sequence; introducing an olefin monomer ethylene, adjusting the preset temperature to 60 ℃ and the preset pressure to 10bar, and carrying out polymerization reaction for 30min to obtain a copolymerization product. The copolymerization activity and the related physical properties of the product are detailed in Table 1.
Example 2
150L of n-hexane/cyclohexane solution (2: 1 mixed), 50L of comonomer 1-octene, 100mL of 1mol/L n-butyllithium cocatalyst, 2g of fluorochloroalkane and 1.5g of main catalyst, namely Fi catalyst, are sequentially added into a single 300L reactor, wherein the molar ratio of the main catalyst metal to the component A is 5: 1, the molar ratio of main metal elements of the cocatalyst to the main catalyst is 100: 1, adding the fluorochloroalkane (component A) and a catalyst into a reactor in sequence; introducing olefin monomer ethylene, adjusting the preset temperature to 20 ℃ below zero and the preset pressure to 25bar, and carrying out polymerization reaction for 20min to obtain a copolymerization product. The copolymerization activity and the related physical properties of the product are detailed in Table 1.
Example 3
120L of n-heptane solution, 80L of comonomer 1-butene, 80mL of 1mol/L methylaluminoxane cocatalyst, 0.3g of siloxane and 1.6g of main catalyst, namely a post-transition metal catalyst are sequentially added into a single 300L reactor, wherein the molar ratio of the main catalyst metal to the component A is 80: 1, the molar ratio of main metal elements of the cocatalyst to the main catalyst is 120: 1, adding siloxane (component A) and a catalyst into a reaction kettle in sequence; introducing olefin monomer ethylene, adjusting the preset temperature to 100 ℃ and the preset pressure to 8bar, and carrying out polymerization reaction for 40min to obtain a copolymerization product. The copolymerization activity and the related physical properties of the product are detailed in Table 1.
Example 4
170L of cyclopentane solution, 30L of comonomer 1-decene, 110mL of 1mol/L triisobutylaluminum cocatalyst, 0.1g of tetravinyl ether and 1.2g of main catalyst, namely metallocene catalyst, are sequentially added into a single 300L reactor, wherein the molar ratio of the main catalyst metal to the component A is 1000: 1, the molar ratio of the main metal elements of the cocatalyst to the main catalyst is 200: 1, mixing tetravinyl ether (component A) and a catalyst in advance, and adding the mixture into a reactor; introducing olefin monomer propylene to adjust the preset temperature to 160 ℃ and the preset pressure to 3bar, and carrying out polymerization reaction for 5min to obtain a copolymerization product. The copolymerization activity and the related physical properties of the product are detailed in Table 1.
Example 5
100L of n-hexane/n-heptane solution (4: 1 mixed), 100L of comonomer 1-octene, 50mL of 1mol/L trimethylaluminum/1 g of trifluoroborane cocatalyst, 0.4g of fluorocarbon and 1.1g of main catalyst, i.e. metallocene catalyst, were added in sequence in a single 300L reactor, wherein the molar ratio of main catalyst metal to component A was 90: 1, the molar ratio of main metal elements of the cocatalyst to the main catalyst is 150: 1, mixing fluorocarbon (component A) and a catalyst, and adding the mixture into a reactor; introducing olefin monomer ethylene, adjusting the preset temperature to 200 ℃ and the preset pressure to 100bar, and carrying out polymerization reaction for 15min to obtain a copolymerization product. The copolymerization activity and the correlation of the products are detailed in Table 1.
Example 6
140L of C were added sequentially in a single 300L reactor 6 -C 10 The catalyst comprises an isoalkane solution, 60L of comonomer 1-butene, 90mL of 1mol/L modified methylaluminoxane cocatalyst, 0.7g of hexavinyl ester and 1.3g of a main catalyst, namely a rare earth amino complex catalyst, wherein the molar ratio of the main catalyst metal to the component A is 10: 1, the molar ratio of main metal elements of the cocatalyst to the main catalyst is 200: 1, sequentially adding hexavinyl ester (component A) and a catalyst into a reaction kettle; and introducing an olefin monomer butene, adjusting the preset temperature to 90 ℃ and the preset pressure to 30bar, and carrying out polymerization reaction for 10min to obtain a copolymerization product. The copolymerization activity and the properties of the product are shown in Table 1.
Example 7
150L of C were added sequentially in a single 300L reactor 10 -C 18 N-alkane solution, 50L of comonomer 1-octene, 4g of trifluorophenylboron catalyst,0.5g of divinyl carboxane and 0.9g of a main catalyst, namely a late transition metal catalyst, wherein the molar ratio of the main catalyst metal to the component A is 30: 1, the molar ratio of main metal elements of the cocatalyst to the main catalyst is 800: 1, adding divinyl carboxane (component A) and a catalyst into a reaction kettle in sequence; introducing olefin monomer pentene to adjust the preset temperature to be 30 ℃ and the preset pressure to be 6bar, and carrying out polymerization reaction for 360min to obtain a copolymerization product. The copolymerization activity and the related physical properties of the product are detailed in Table 1.
Example 8
160L of C were added sequentially in a single 300L reactor 4 -C 6 Cycloparaffin solution, 40L comonomer 1-hexene, 2g tributylammonium tetrakis (pentafluorophenyl) aluminum cocatalyst, 0.3g fluorocarbon and 1g procatalyst, i.e. Ziegler-Natta catalyst, wherein the molar ratio of procatalyst metal to component A is 40: 1, the molar ratio of main metal elements of the cocatalyst to the main catalyst is 60: 1, adding fluorocarbon (component A) and a catalyst into a reaction kettle in sequence; introducing an olefin monomer butadiene to adjust the preset temperature to 110 ℃ and the preset pressure to 16bar, and carrying out polymerization reaction for 60min to obtain a copolymerization product. The copolymerization activity and the related physical properties of the product are detailed in Table 1.
Example 9
170L of cyclohexane solution, 30L of comonomer 1-decene, 2.6g of tetrakispentafluorophenylborate cocatalyst, 0.5g of triethylsilylphospholane and 1.2g of a main catalyst, i.e., a Fi catalyst, were sequentially added to a single 300L reactor, wherein the molar ratio of the main catalyst metal to component A was 15: 1, the molar ratio of main metal elements of the cocatalyst to the main catalyst is 120: 1, adding trivinyl-based phosphane (component A) and a catalyst into a reaction kettle in sequence; introducing olefin monomer propylene to adjust the preset temperature to 80 ℃ and the preset pressure to 40bar, and carrying out polymerization reaction for 120min to obtain a copolymerization product. The copolymerization activity and the related physical properties of the product are detailed in Table 1.
Comparative example 1
100L of n-hexane/n-heptane solution (4: 1 mixed), 100L of comonomer 1-octene, 50mL of 1mol/L trimethylaluminum/1 g of trifluoroborane cocatalyst and 1.1g of main catalyst, namely metallocene catalyst, are sequentially added into a single 300L reactor, wherein the molar ratio of the cocatalyst to the main metal elements of the main catalyst is 150: 1, introducing an olefin monomer ethylene, adjusting the preset temperature to 200 ℃ and the preset pressure to 100bar, and carrying out polymerization reaction for 15min to obtain a copolymerization product. The copolymerization activity and the related physical properties of the product are detailed in Table 1.
Comparative example 2
160L of C were added sequentially in a single 300L reactor 4 -C 6 Cycloparaffin solution, 40L of comonomer 1-hexene, 2g of tributylammonium tetrakis (pentafluorophenyl) aluminum cocatalyst and 1g of main catalyst, namely a Ziegler-Natta catalyst, wherein the molar ratio of the main metal elements of the cocatalyst to the main catalyst is 60: 1; introducing an olefin monomer butadiene to adjust the preset temperature to 110 ℃ and the preset pressure to 16bar, and carrying out polymerization reaction for 60min to obtain a copolymerization product. The copolymerization activity and the related physical properties of the product are detailed in Table 1.
TABLE 1 polyolefin copolymer respective physical property indexes
From the physical indexes of polyolefin blends in Table 1, it can be found that the polymerization activity is obviously improved and the molar content of the comonomer is greatly improved after the component A is added in the examples 1 to 9, and the ash content of the product obtained by an ash determination method is lower. The main reason is that the interaction between the third component and the active component of the main catalyst is strengthened by physical adsorption and adhesion effect in the preparation process of the catalyst, the interaction between the active components is avoided, the active center is stabilized, and the main catalyst shows better polymerization behavior in the polymerization process.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
Claims (10)
1. Low ash, high comonomer content polyA process for the preparation of an olefin copolymer, characterized in that the polyolefin copolymer has a density in the range of 0.86g/cm 3 ～0.93g/cm 3 (ii) a The preparation method comprises the following steps:
adding a solvent A, an olefin monomer, a comonomer, a main catalyst, a cocatalyst and a component A into a reactor, and carrying out polymerization reaction for a certain time at preset temperature and pressure to obtain a polyolefin copolymer with low ash content and high comonomer content, wherein the ash content of the polyolefin copolymer is 1 ppm-1000 ppm, and the molar insertion rate of the comonomer is 5% -100%; wherein the molar ratio range of the main catalyst metal to the component A is 3000: 1-1: 1, the molar ratio of main metal elements of the cocatalyst and the main catalyst is 1: 1-1000: 1, the component A can be premixed with a main catalyst or can be added into a reaction kettle with the main catalyst respectively;
the component A is a non-metal polar group molecule containing O, F, Cl, S, N or P elements.
2. The method for preparing polyolefin copolymer with low ash content and high comonomer content as claimed in claim 1, wherein the solvent A is toluene, ethylbenzene, benzene, n-hexane, cyclohexane, n-heptane, cyclopentane, C 4 ～C 18 The normal paraffin, the isoparaffin and the cycloparaffin in the (C) are one or more.
3. The method of claim 1, wherein the olefin monomer is one or more of ethylene, propylene, butylene, butadiene, and pentene; the comonomer is C 4 ～C 20 One or more of (a) alpha-olefins.
4. The method of claim 3, wherein the comonomer is one or more of 1-octene, 1-hexene, 1-butene, and 1-decene.
5. The method of claim 1, wherein the main catalyst is selected from one or more of a Ziegler Natta catalyst, a FI catalyst, a rare earth amine based complex, a late transition metal catalyst, and a metallocene catalyst; the cocatalyst is selected from one or more of methylaluminoxane, modified methylaluminoxane, triethylaluminum, n-butyllithium, triisobutylaluminum, trimethylaluminum, trifluorophenylboron, tributylammonium tetrakis (pentafluorophenyl) aluminum, trifluoroborane and tetrapentafluorophenylborate, and the molar ratio of the main metal elements of the cocatalyst to the main catalyst is 50: 1-800: 1.
6. the method for preparing polyolefin copolymer with low ash content and high comonomer content as claimed in claim 1, wherein the predetermined temperature range is-50 ℃ to 230 ℃; the preset pressure range is 1 bar-200 bar; the polymerization reaction time ranges from 1min to 1000 min.
7. The method for preparing polyolefin copolymer with low ash content and high comonomer content as claimed in claim 1, wherein the predetermined temperature range is-20 ℃ to 200 ℃; the preset pressure range is 3 bar-100 bar; the polymerization reaction time ranges from 5min to 360 min.
8. The method of claim 1, wherein the component A is one or more selected from the group consisting of siloxanes, silazanes, phosphosiloxanes, ethers and esters.
9. The method of claim 1, wherein the component A is one or more selected from the group consisting of trivinyl phosphino alkane, divinyl carbosiloxane, tetravinyl ether, hexavinyl ester, siloxane, fluorocarbon, and fluorochloroalkane, and the molar ratio of the main catalyst metal to the component A is in the range of 1000: 1-5: 1.
10. the method of claim 1, wherein the polyolefin copolymer has an ash content preferably ranging from 5ppm to 600ppm, and a comonomer molar insertion rate preferably ranging from 8% to 27%; copolymer M w <5000 is 3 to 9 percent by mass.
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| CN111087501A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | 1-butene polymer and 1-butene continuous slurry polymerization process |
| CN109438604A (en) * | 2018-11-08 | 2019-03-08 | 宁波工程学院 | The low density polyethylene (LDPE) preparation method of anti-stick kettle |
| CN109796546A (en) * | 2018-12-19 | 2019-05-24 | 宁波大学 | A kind of preparation method and application of olefin polymerization heterogeneous catalysis |
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