CN115677893A - Gas-liquid mixing feeding method in polyolefin polymerization reaction process - Google Patents
Gas-liquid mixing feeding method in polyolefin polymerization reaction process Download PDFInfo
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- 238000002156 mixing Methods 0.000 title claims abstract description 116
- 238000000034 method Methods 0.000 title claims abstract description 61
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 51
- 239000007788 liquid Substances 0.000 title claims abstract description 50
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 41
- 239000012071 phase Substances 0.000 claims abstract description 68
- 239000000463 material Substances 0.000 claims abstract description 37
- 239000007791 liquid phase Substances 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 238000002360 preparation method Methods 0.000 claims abstract description 27
- 239000011259 mixed solution Substances 0.000 claims abstract description 21
- 238000001816 cooling Methods 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims description 57
- -1 ethylene, propylene, butylene Chemical group 0.000 claims description 36
- 239000003960 organic solvent Substances 0.000 claims description 35
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 34
- 239000004711 α-olefin Substances 0.000 claims description 25
- 239000012968 metallocene catalyst Substances 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 17
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- ZOICEQJZAWJHSI-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl)boron Chemical compound [B]C1=C(F)C(F)=C(F)C(F)=C1F ZOICEQJZAWJHSI-UHFFFAOYSA-N 0.000 claims description 10
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 10
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 10
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims description 10
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 claims description 10
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 10
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 10
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 10
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 claims description 10
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 10
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 10
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 10
- 229940106006 1-eicosene Drugs 0.000 claims description 5
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 claims description 5
- GDBLZKMJBVGZTR-UHFFFAOYSA-K Cl[Ti](OC1=C(C=CC=C1)C1=CC=CC=C1)(C1(C(=C(C(=C1C)C)C)C)C)Cl Chemical compound Cl[Ti](OC1=C(C=CC=C1)C1=CC=CC=C1)(C1(C(=C(C(=C1C)C)C)C)C)Cl GDBLZKMJBVGZTR-UHFFFAOYSA-K 0.000 claims description 5
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 claims description 5
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 5
- 229940069096 dodecene Drugs 0.000 claims description 5
- 239000001282 iso-butane Substances 0.000 claims description 5
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000012005 post-metallocene catalyst Substances 0.000 claims description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 5
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 5
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 5
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 5
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 claims description 5
- OLFPYUPGPBITMH-UHFFFAOYSA-N tritylium Chemical compound C1=CC=CC=C1[C+](C=1C=CC=CC=1)C1=CC=CC=C1 OLFPYUPGPBITMH-UHFFFAOYSA-N 0.000 claims description 5
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 claims description 5
- KGWXYUFIQHXOIL-UHFFFAOYSA-K CC(C)C1=CC=CC(C(C)C)=C1O[Ti](Cl)(Cl)C1(C)C(C)=C(C)C(C)=C1C Chemical compound CC(C)C1=CC=CC(C(C)C)=C1O[Ti](Cl)(Cl)C1(C)C(C)=C(C)C(C)=C1C KGWXYUFIQHXOIL-UHFFFAOYSA-K 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- FJMJPZLXUXRLLD-UHFFFAOYSA-L [Cl-].[Cl-].C1=CC2=CC=CC=C2C1[Zr+2]([SiH](C)C)C1C2=CC=CC=C2C=C1 Chemical compound [Cl-].[Cl-].C1=CC2=CC=CC=C2C1[Zr+2]([SiH](C)C)C1C2=CC=CC=C2C=C1 FJMJPZLXUXRLLD-UHFFFAOYSA-L 0.000 claims description 4
- 239000001273 butane Substances 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- YQRRFEPNTPQQHU-UHFFFAOYSA-L [Cl-].[Cl-].C(C=1C(O)=CC=CC1)=C1C(C=CC=C1)N=[Ti+2]=NC1C(C=CC=C1)=CC=1C(O)=CC=CC1 Chemical compound [Cl-].[Cl-].C(C=1C(O)=CC=CC1)=C1C(C=CC=C1)N=[Ti+2]=NC1C(C=CC=C1)=CC=1C(O)=CC=CC1 YQRRFEPNTPQQHU-UHFFFAOYSA-L 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- XLMHRUKPJFDOAS-UHFFFAOYSA-N CCC(C)(C(C)(C)C)N[Ti](C)(C[SiH](C)C)C1C=CC=C1.Cl.Cl Chemical compound CCC(C)(C(C)(C)C)N[Ti](C)(C[SiH](C)C)C1C=CC=C1.Cl.Cl XLMHRUKPJFDOAS-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 24
- 230000000694 effects Effects 0.000 abstract description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 16
- 238000003756 stirring Methods 0.000 description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 13
- 239000005977 Ethylene Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 229920006124 polyolefin elastomer Polymers 0.000 description 5
- 239000003426 co-catalyst Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000014509 gene expression Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- BHTKQUGPJWEUOJ-UHFFFAOYSA-N C[SiH](C)C[Ti](C)(NC(C(C)(C)C)(CC)C)C1C=CC=C1 Chemical compound C[SiH](C)C[Ti](C)(NC(C(C)(C)C)(CC)C)C1C=CC=C1 BHTKQUGPJWEUOJ-UHFFFAOYSA-N 0.000 description 2
- VMZMXDNPNZSQOM-UHFFFAOYSA-N C[SiH](C)C[Ti](C)(NC(C)(C)C)C1C=C(C2=CC=CC=C12)C=1NC=CC1 Chemical compound C[SiH](C)C[Ti](C)(NC(C)(C)C)C1C=C(C2=CC=CC=C12)C=1NC=CC1 VMZMXDNPNZSQOM-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- AECTWRMNKTVPEM-UHFFFAOYSA-L [Cl-].[Cl-].CC1=C(C(C2=CC=CC=C12)[Zr+2](C1C=CC2=CC=CC=C12)=[SiH2])C Chemical compound [Cl-].[Cl-].CC1=C(C(C2=CC=CC=C12)[Zr+2](C1C=CC2=CC=CC=C12)=[SiH2])C AECTWRMNKTVPEM-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- XMGMFRIEKMMMSU-UHFFFAOYSA-N phenylmethylbenzene Chemical compound C=1C=CC=CC=1[C]C1=CC=CC=C1 XMGMFRIEKMMMSU-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
Classifications
-
- 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
Abstract
The invention provides a gas-liquid mixing feeding method in a polyolefin preparation process, which comprises the following steps of firstly, mixing all gas-phase materials in the polyolefin preparation process to obtain mixed gas; mixing all liquid-phase materials in the polyolefin preparation process under pressure, and cooling to obtain a mixed solution; and finally, mixing the mixed gas and the mixed solution obtained in the step again at the first temperature, and then carrying out polymerization reaction to obtain the polyolefin. The method comprises three steps of gas phase mixing, liquid phase mixing and gas-liquid mixing, wherein the gas phase, the liquid phase and the catalyst are fully and uniformly mixed by controlling parameters such as gas-liquid phase proportion, temperature, pressure, reaction residence time and the like, so that the reaction effect is improved.
Description
Technical Field
The invention belongs to the technical field of feeding processes of polyolefin solution polymerization, relates to a gas-liquid mixing feeding method in a polyolefin preparation process, and particularly relates to a gas-liquid mixing feeding method in a polyolefin polymerization reaction process.
Background
Polyolefin elastomers are one of the development directions of high-end polyolefins, and are important projects for encouraging development in recent countries. Under the large condition of development of green low-carbon clean energy, development of the photovoltaic industry is vigorous, and the demand of polyolefin elastomers is rapidly increased. The main application fields of the high-performance polyolefin elastomer mainly come from high-end pipes, industrial pipelines, automobile parts, medical equipment, prosthetic implants and the like, and related materials modified by the polyolefin elastomer are widely applied to the fields of automobile parts, electric wires and cables, mechanical tools, household articles, toys, entertainment and sports articles, soles, sealing elements, hot melt adhesives and the like. The polyolefin elastomer can replace materials such as rubber, flexible PVC, EPDM, EPR, EMA, EVA, TPV, SBC, LDPE and the like, is applied to different products such as automobile baffles, flexible guide pipes, conveying belts, printing rollers, sports shoes, electric wires and cables, automobile parts, durable goods, extruded parts, compression molding parts, sealing materials, pipe fittings, fabric coatings and the like, can also be used as a low-temperature impact modifier to improve the low-temperature impact resistance of PP, and can be used as a thermoplastic elastomer to be applied to the field of automobiles.
The gas-liquid feeding mode commonly used in the polyolefin polymerization process at present roughly comprises the following steps: the gas phase required by the reaction is mixed firstly, then the liquid phase is mixed, and finally the gas and the liquid are mixed. However, the conventional gas-liquid mixing feeding mode can affect the reaction effect of polyolefin preparation.
Therefore, how to find a more suitable feeding method in the polyolefin preparation process, especially a feeding method for the polyolefin solution polymerization process, to solve the above-mentioned problems of the gas-liquid feeding method in the polyolefin preparation process, and to facilitate the industrial application, and to satisfy the various requirements of the industrial application, has become one of the problems to be solved by many front-line researchers in the industry.
Disclosure of Invention
In order to solve the technical problems, the invention provides a gas-liquid mixing feeding method in the polyolefin preparation process. The improved method for gas-liquid mixed feeding provided by the invention has the advantages that the gas phase, the liquid phase and the catalyst are fully and uniformly mixed by controlling parameters such as gas-liquid phase proportion, temperature, pressure, reaction residence time and the like, so that the reaction effect is improved, and the improved method is also suitable for industrial production and practical application.
The invention provides a gas-liquid mixing feeding method in a polyolefin preparation process, which comprises the following steps:
1) Mixing all gas-phase materials in the polyolefin preparation process to obtain mixed gas;
mixing all liquid-phase materials in the polyolefin preparation process under pressure, and cooling to obtain a mixed solution;
2) And (3) mixing the mixed gas and the mixed solution obtained in the step again at the first temperature, and then carrying out polymerization reaction to obtain the polyolefin.
Preferably, the mixing pressure is 0.3-10 MPa;
the mixing is normal temperature mixing;
preferably, the gas phase material comprises one or more of ethylene, propylene, butylene, hydrogen and nitrogen;
the ratio of the partial pressure of a single gas phase material in the total pressure of all the gas phase materials to the molar ratio of the single gas phase material in all the gas phase materials is (0.5-2): 1.
preferably, the liquid phase material comprises one or more of C3-C20 linear or branched alpha-olefin, organic solvent, main catalyst and cocatalyst;
the procatalyst comprises a single site metallocene catalyst and/or a post metallocene catalyst.
Preferably, the alpha-olefins include one or more of propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and 1-eicosene;
the procatalyst comprises one or more of diphenylcarbaryl-cyclopentadienyl-fluorenyl zirconium dichloride, diphenylcarbaryl-cyclopentadienyl- (2-dimethylamino-fluorenyl) zirconium dichloride, bis [2- (3 ',5' -di-tert-butylphenyl) -indenyl ] zirconium dichloride, biscyclopentadienyl-bisphenoxy zirconium, vinyl-bisindenyl-bisphenoxy zirconium, bis (salicylidene-phenylimino) titanium dichloride, [ N- (3,5-di-tert-butylsalicylidene) -2-diphenylphosphinobenzimide ] titanium trichloride, dimethylsilyl bisindenyl zirconium dichloride, dimethylsilyl-tetramethylcyclopentadienyl-tert-butylamino-dimethyltitanium dichloride, dimethylsilyl-3-pyrrolylindenyl-tert-butylamino-dimethyltitanium dichloride, pentamethylcyclopentadienyl- (2-phenylphenoxy) -titanium dichloride and pentamethylcyclopentadienyl- (2,6-diisopropylphenoxy) -titanium dichloride.
Preferably, the cocatalyst comprises one or more of methylalumoxane compound, modified methylalumoxane compound, tris (pentafluorophenyl) boron compound, triphenylcarbenium tetrakis (pentafluorophenyl) boron compound, N-dimethylanilinium tetrakis (pentafluorophenyl) boron compound, triisobutylaluminum, and trimethylaluminum;
the organic solvent comprises one or more of butane, isobutane, cyclobutane, n-pentane, isopentane, toluene and xylene.
Preferably, the pressure of the pressurized mixing is 0.3 to 10MPa;
the specific way of mixing under pressure comprises: firstly, premixing alpha-olefin and an organic solvent, premixing a main catalyst and the organic solvent, premixing an auxiliary catalyst and the organic solvent, and then mixing the alpha-olefin, the main catalyst and the organic solvent under pressure; or premixing the alpha-olefin, part of the cocatalyst and the organic solvent, premixing the main catalyst and the organic solvent, premixing the rest of the cocatalyst and the organic solvent, and mixing the alpha-olefin, the part of the cocatalyst and the organic solvent under pressure.
Preferably, the cooling temperature is-35 ℃ to-10 ℃.
The first temperature is 100-200 ℃.
Preferably, in the remixing process, the gas phase partial pressure is 0.15 to 4MPa;
the pressure of the remixing is 0.3-10 MPa;
the time for mixing again is 10-150 min.
Preferably, the pressure of the polymerization reaction is 1 to 10MPa;
the temperature of the polymerization reaction is 100-200 ℃;
the time of the polymerization reaction is 5-150 min.
The invention provides a gas-liquid mixing feeding method in a polyolefin preparation process, which comprises the following steps of firstly, mixing all gas-phase materials in the polyolefin preparation process to obtain mixed gas; mixing all liquid-phase materials in the polyolefin preparation process under pressure, and cooling to obtain a mixed solution; and finally, mixing the mixed gas and the mixed solution obtained in the step again at the first temperature, and then carrying out polymerization reaction to obtain the polyolefin. Compared with the prior art, the invention aims at the problem that the reaction effect of polyolefin preparation can be influenced by a gas-liquid mixing feeding mode in the existing polyolefin solvent polymerization process.
Based on the method, the invention particularly designs a gas-liquid mixing feeding method in the polyolefin preparation process, which comprises three steps of gas-phase mixing, liquid-phase mixing and gas-liquid mixing, wherein the gas phase, the liquid phase and a catalyst are fully and uniformly mixed by controlling parameters such as gas-liquid phase ratio, temperature, pressure, reaction residence time and the like, so that the reaction effect is improved.
The improved method for gas-liquid mixed feeding provided by the invention prevents the adverse gas-phase contact caused by heat release in the reaction process from influencing the polymerization efficiency by cooling the liquid phase to low temperature; by controlling the total pressure and the gas phase partial pressure, the turbulence formed by stirring in the polymerization kettle is reduced, the gas-liquid phase is in full contact with the catalyst, the solubility of the gas phase is improved, and the reaction efficiency is improved.
The experimental result shows that compared with the traditional method, the gas-liquid mixed feeding method provided by the invention can improve the molecular weight of the polymer by 10000-20000, reduce the molecular weight distribution by 0.7-1.0 and improve the tensile strength by about 1MPa.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
The raw material used in the present invention is not particularly limited in purity, and the present invention is preferably one having a purity which is industrially pure or conventional in the field of polyolefin polymer production.
All noun expressions and abbreviations used in the present invention belong to the conventional noun expressions and abbreviations in the art, and each noun expression and abbreviation is clearly and unambiguously understood in the relevant field of application by a person skilled in the art based on the noun expressions and abbreviations.
The invention provides a gas-liquid mixed feeding method in a polyolefin preparation process, which comprises the following steps:
1) Mixing all gas-phase materials in the polyolefin preparation process to obtain mixed gas;
mixing all liquid-phase materials in the polyolefin preparation process under pressure, and cooling to obtain a mixed solution;
2) And mixing the mixed gas and the mixed solution obtained in the step again at the first temperature, and then carrying out polymerization reaction to obtain the polyolefin.
Firstly, mixing all gas-phase materials in the polyolefin preparation process to obtain mixed gas;
mixing all liquid-phase materials in the polyolefin preparation process under pressure, and cooling to obtain a mixed solution.
In the present invention, the pressure of the mixing is preferably 0.3 to 10MPa, more preferably 1 to 8MPa, and still more preferably 3 to 6MPa.
In the present invention, the mixing is preferably normal temperature mixing.
In the present invention, the gas phase material preferably comprises one or more of ethylene, propylene, butylene, hydrogen and nitrogen, and more preferably ethylene, propylene, butylene, hydrogen or nitrogen.
In the present invention, the ratio of the partial pressure of a single gas phase material in the total pressure of all gas phase materials to the molar ratio of the single gas phase material in all gas phase materials is preferably (0.5-2): 1, more preferably (0.8 to 1.7): 1, more preferably (1.1 to 1.4): 1.
in the present invention, the liquid phase material preferably comprises one or more of C3 to C20 linear or branched alpha-olefin, organic solvent, main catalyst and co-catalyst, more preferably one or more of C3 to C16 linear or branched alpha-olefin, organic solvent, main catalyst and co-catalyst, more preferably one or more of C3 to C12 linear or branched alpha-olefin, organic solvent, main catalyst and co-catalyst, more preferably C3 to C8 linear or branched alpha-olefin, organic solvent, main catalyst or co-catalyst.
In the present invention, the main catalyst preferably comprises a single-site metallocene catalyst and/or a post-metallocene catalyst, more preferably a single-site metallocene catalyst or a post-metallocene catalyst.
In the present invention, the α -olefin preferably includes one or more of propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and 1-eicosene, and more preferably propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene or 1-eicosene.
In the present invention, the main catalyst preferably comprises one or more of diphenylcarbaryl-cyclopentadienyl-fluorenyl zirconium dichloride, diphenylcarbaryl-cyclopentadienyl- (2-dimethylamino-fluorenyl) zirconium dichloride, bis [2- (3 ',5' -di-tert-butylphenyl) -indenyl ] zirconium dichloride, biscyclopentadienyl-bisphenoxy zirconium, vinyl-bisindenyl-bisphenoxy zirconium, bis (salicylidene-benzimidino) titanium dichloride, [ N- (3,5-di-tert-butylsalicylidene) -2-diphenylphosphinimide ] titanium trichloride, dimethylsilyl-bisindenyl zirconium dichloride, dimethylsilyl-tetramethylcyclopentadienyl-tert-butylamino-dimethyltitanium, dimethylsilyl-3-pyrrolylindenyl-tert-butylamino-dimethyltitanium, pentamethylcyclopentadienyl- (2-phenylphenoxy) -titanium dichloride and pentamethylcyclopentadienyl- (3262 zxft-diisopropylphenoxy) -3262-diisopropylphenoxy) -titanium dichloride, more preferably diphenylcarba-bridging-cyclopentadienyl-fluorenyl-zirconium dichloride, diphenylcarba-bridging-cyclopentadienyl- (2-dimethylamino-fluorenyl) zirconium dichloride, bis [2- (3 ',5' -di-tert-butylphenyl) -indenyl ] zirconium dichloride, biscyclopentadienyl-bisphenoxyzirconium, vinyl-bisindenyl-bisphenoxyzirconium, bis (salicylidene-phenylimino) titanium dichloride, [ N- (3,5-di-tert-butylsalicylidene) -2-diphenylphosphinophenylimide ] titanium trichloride, dimethylsilyl bisindenyl zirconium dichloride, dimethylsilyl-tetramethylcyclopentadienyl-tert-butylamino-dimethyl titanium, dimethylsilyl-3-pyrrolylindenyl-tert-butylamino-dimethyl titanium, pentamethylcyclopentadienyl- (2-phenylphenoxy) -titanium dichloride or pentamethylcyclopentadienyl- (2,6-diisopropylphenoxy) -titanium dichloride.
In the present invention, the cocatalyst preferably includes one or more of methylaluminoxane compound, modified methylaluminoxane compound, tris (pentafluorophenyl) boron compound, triphenylcarbenium tetrakis (pentafluorophenyl) boron compound, N-dimethylanilinium tetrakis (pentafluorophenyl) boron compound, triisobutylaluminum and trimethylaluminum, and more preferably methylaluminoxane compound, modified methylaluminoxane compound, tris (pentafluorophenyl) boron compound, triphenylcarbenium tetrakis (pentafluorophenyl) boron compound, N-dimethylanilinium tetrakis (pentafluorophenyl) boron compound, triisobutylaluminum or trimethylaluminum.
In the present invention, the organic solvent preferably includes one or more of butane, isobutane, cyclobutane, n-pentane, isopentane, toluene and xylene, more preferably butane, isobutane, cyclobutane, n-pentane, isopentane, toluene or xylene.
In the present invention, the pressure of the mixing under pressure is preferably 0.3 to 10MPa, more preferably 1 to 8MPa, and still more preferably 3 to 6MPa.
In the present invention, the specific manner of mixing under pressure preferably includes: firstly, premixing alpha-olefin and an organic solvent, premixing a main catalyst and the organic solvent, premixing an auxiliary catalyst and the organic solvent, and then mixing the alpha-olefin, the main catalyst and the organic solvent under pressure; or premixing the alpha-olefin, part of the cocatalyst and the organic solvent, premixing the main catalyst and the organic solvent, premixing the rest of the cocatalyst and the organic solvent, and mixing the alpha-olefin, the part of the cocatalyst and the organic solvent under pressure.
In the present invention, the cooling temperature is preferably-35 ℃ to-10 ℃, more preferably-30 ℃ to-15 ℃, and still more preferably-25 ℃ to-20 ℃.
Finally, at the first temperature, the mixed gas and the mixed liquid obtained in the step are mixed again, and then the polymerization reaction is carried out, so that the polyolefin is obtained.
In the present invention, the first temperature is preferably 100 to 200 ℃, more preferably 120 to 180 ℃, and more preferably 140 to 160 ℃.
In the present invention, the partial pressure of the gas phase in the remixing step is preferably 0.15 to 4MPa, more preferably 0.5 to 3MPa, and still more preferably 1 to 2MPa.
In the present invention, the pressure of the remixing is preferably 0.3 to 10MPa, more preferably 1 to 8MPa,
in the present invention, the time for the remixing is preferably 10 to 150min, more preferably 40 to 120min, and still more preferably 70 to 90min.
In the present invention, the pressure of the polymerization reaction is preferably 1 to 10MPa, more preferably 3 to 8MPa, and still more preferably 5 to 6MPa.
In the present invention, the temperature of the polymerization reaction is preferably 100 to 200 ℃, more preferably 120 to 180 ℃, and still more preferably 140 to 160 ℃.
In the present invention, the time for the polymerization reaction is preferably 5 to 150min, more preferably 30 to 120min, and still more preferably 60 to 90min.
The invention is an integral and refined integral technical scheme, better improves the mixing effect of gas-liquid mixed feeding, and improves the reaction effect and the performance of a polymer product, and the feeding method of liquid-liquid mixing in the polyolefin preparation process can specifically comprise the following steps:
the gas-liquid mixing feeding method in the polymerization reaction process mainly comprises three steps of gas-phase mixing, liquid-phase mixing and gas-liquid mixing.
(1) Gas-phase mixing: mixing all gas-phase materials in the polymerization process at normal temperature, and controlling the pressure to be 0.3-10 MPa;
(2) Liquid phase mixing: all liquid phase materials are mixed under the pressure of 0.3-10MPa and then cooled to minus 10 ℃ to minus 35 ℃;
(3) Gas-liquid mixing: controlling the temperature at 100-200 ℃, mixing the mixed gas phase and liquid phase under the pressure of 0.3-10MPa, and carrying out polymerization reaction.
Further, the gas phase material in the (1) process can be one or more of ethylene, propylene, butylene, hydrogen and nitrogen; the total pressure during the mixing is preferably 0.3-5MPa, wherein the proportion of the partial pressure of the individual gas-phase materials in the total pressure is equal to 0.5-2 times, preferably 1 time, the molar proportion of the gas-phase materials;
further, the liquid phase material in the process (2) can be one or more of linear chain or branched chain alpha-olefin with 3-20 carbon atoms, organic solvent, main catalyst and cocatalyst. Wherein the alpha-olefin is preferably propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene, 1-eicosene; the organic solvent is preferably n-butane, isobutane, cyclobutane, n-pentane or isopentane; the main catalyst is a single-site metallocene catalyst or a post-metallocene catalyst, preferably diphenylcarbanion-cyclopentadienyl-fluorenyl-zirconiumdichloride, diphenylcarbanion-cyclopentadienyl- (2-dimethylamino-fluorenyl) zirconiumdichloride, bis [2- (3 ',5' -di-tert-butylphenyl) -indenyl ] zirconiumdichloride, biscyclopentadienyl-bisphenoxyzirconium, vinyl-bisindenyl-bisphenoxyzirconium, bis (salicylidene-benzimidyl) titaniumdichloride, [ N- (3,5-di-tert-butylsalicylidene) -2-diphenylphosphinophenylimine ] titaniumtrichloride, dimethylsilanediyl bisindenyl zirconium dichloride, dimethylsilane-tetramethylcyclopentadienyl-tert-butylamino-dimethyltitanium, dimethylsilane-3-pyrrolylindenyl-tert-butylamino-dimethyltitanium, pentamethylcyclopentadienyl- (2-phenylphenoxy) -titaniumdichloride, pentamethylcyclopentadienyl- (2,6-diisopropylphenoxy) -titaniumdichloride; the cocatalyst is preferably methylaluminoxane compound, modified methylaluminoxane compound, tris (pentafluorophenyl) boron compound, triphenylcarbenium tetrakis (pentafluorophenyl) boron compound, N-dimethylanilinium tetrakis (pentafluorophenyl) boron compound, triisobutylaluminum, trimethylaluminum. The mixing pressure is preferably 1-3MPa, and the cooling temperature is preferably-30 ℃. The mixing modes of the liquid-phase materials can be combined and mixed randomly, and the following mixing modes are preferred: mixing alpha-olefin with a solvent, mixing a main catalyst with the solvent, mixing a cocatalyst with the solvent, and mixing the three; alpha-olefin, part of cocatalyst and solvent are mixed, main catalyst and solvent are mixed, the rest cocatalyst and solvent are mixed, and then the three are mixed.
Further, in the gas-liquid mixing process described in the (3), the total reaction pressure may be 0.3 to 10MPa, preferably 0.3 to 5MPa. The partial pressure of the gas phase may be suitably increased in order to sufficiently contact the gas phase with the liquid phase at a constant temperature and total pressure. Optimum gas phase partial pressure P g Can be calculated from the solubility of the gas in the liquid and Henry's law g ＝C A /H，C A The molar concentration of the gas, and H the solubility coefficient of the gas, can be obtained by looking up a table. The gas phase partial pressure is usually preferably from 0.15 to 4MPa, more preferably from 0.25 to 3MPa. In the gas-liquid mixing process, the residence time of the reaction is 10min-150min, more preferably 10min-100min, and further preferably 15min-80min; more preferably 20min to 40min. The temperature during the gas-liquid mixing process is preferably 130-180 ℃.
The invention provides a gas-liquid mixing feeding method in a polyolefin polymerization reaction process. The feeding method for gas-liquid mixing in the polyolefin preparation process comprises three steps of gas-phase mixing, liquid-phase mixing and gas-liquid mixing again, wherein the gas phase, the liquid phase and the catalyst are fully and uniformly mixed by controlling parameters such as gas-liquid phase proportion, temperature, pressure, reaction residence time and the like, so that the reaction effect is improved.
The improved method for gas-liquid mixed feeding provided by the invention prevents the adverse gas-phase contact caused by heat release in the reaction process from influencing the polymerization efficiency by cooling the liquid phase to low temperature; by controlling the total pressure and the gas phase partial pressure, the turbulence formed by stirring in the polymerization kettle is reduced, the gas-liquid phase is in full contact with the catalyst, the solubility of the gas phase is improved, and the reaction efficiency is improved.
The experimental result shows that compared with the traditional method, the gas-liquid mixed feeding method provided by the invention can improve the molecular weight of the polymer by 10000-20000, reduce the molecular weight distribution by 0.7-1.0 and improve the tensile strength by about 1MPa.
For further illustration of the present invention, the following will describe in detail a feeding method of gas-liquid mixing in polyolefin production process provided by the present invention with reference to the following examples, but it should be understood that these examples are carried out on the premise of the technical solution of the present invention, and the detailed embodiments and specific operation procedures are given only for further illustration of the features and advantages of the present invention, not for limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
The present invention is not particularly limited with respect to the sources of the raw materials in the following examples, and they may be prepared by a preparation method known to those skilled in the art or commercially available.
Example 1
The method of gas-liquid feeding mode in polyolefin polymerization process includes the following steps:
(1) Feeding gas-phase ethylene at the speed of 18kg/h, feeding hydrogen at the speed of 1g/h, and fully and uniformly mixing the gas-phase ethylene and the hydrogen in a reactor A under the pressure of 1 MPa;
(2) Mixing 10g of diphenylcarbon bridge-cyclopentadienyl-fluorenyl zirconium dichloride of a metallocene catalyst with 5000g of normal hexane, stirring for 2 hours, mixing 40g of methylaluminoxane compound modified by a cocatalyst with 300g of normal hexane, stirring for 2 hours, controlling the feeding speed of 70kg/h of 1-octene, the feeding speed of 70kg/h of normal hexane, the feeding speed of 300g/h of mixed cocatalyst mixed liquor, the feeding speed of 100g/h of mixed metallocene catalyst mixed liquor, mixing the metallocene catalyst mixed liquor, the cocatalyst mixed liquor, 1-octene and normal hexane for 30 minutes at 3MPa, and cooling to-25 ℃ through a cooler;
(3) And (3) mixing the mixed liquid obtained in the step (1) and the mixed liquid obtained in the step (2) together in a reaction kettle, and calculating to obtain the optimal gas phase partial pressure Pg =1.5MPa. Controlling the gas phase partial pressure to be 1.5MPa, and reacting at 170 ℃ for 20min to carry out polymerization.
Example 2
The method of gas-liquid feeding mode in polyolefin polymerization process includes the following steps:
(1) Feeding gas-phase ethylene at the speed of 18kg/h, feeding hydrogen at the speed of 1g/h, and fully and uniformly mixing the gas-phase ethylene and the hydrogen in a reactor A under the pressure of 1 MPa;
(2) Mixing 10g of diphenylcarbon bridge-cyclopentadienyl-fluorenyl zirconium dichloride of a metallocene catalyst with 5000g of normal hexane, stirring for 2 hours, mixing 40g of methylaluminoxane compound modified by a cocatalyst with 300g of normal hexane, stirring for 2 hours, controlling the feeding speed of 70kg/h of 1-octene, the feeding speed of 70kg/h of normal hexane, the feeding speed of 300g/h of mixed cocatalyst mixed liquor, the feeding speed of 100g/h of mixed metallocene catalyst mixed liquor, mixing the metallocene catalyst mixed liquor, the cocatalyst mixed liquor, 1-octene and normal hexane for 30 minutes at 3MPa, and cooling to-25 ℃ through a cooler;
(3) Mixing the mixed solution obtained in the step (1) and the mixed solution obtained in the step (2) in a reaction kettle, calculating to obtain the optimal gas phase partial pressure Pg =1.5MPa and controlling the gas phase partial pressure to be 1.5MPa on the premise of controlling the total pressure to be 3MPa, and reacting at 150 ℃ for 20min to carry out polymerization.
Example 3
The method of gas-liquid feeding mode in polyolefin polymerization process includes the following steps:
(1) Feeding gas-phase ethylene at the speed of 18kg/h, feeding hydrogen at the speed of 1g/h, and fully and uniformly mixing the gas-phase ethylene and the hydrogen in a reactor A under the pressure of 1 MPa;
(2) Mixing 10g of diphenylcarbon bridge-cyclopentadienyl-fluorenyl zirconium dichloride of a metallocene catalyst with 5000g of normal hexane, stirring for 2 hours, mixing 40g of methylaluminoxane compound modified by a cocatalyst with 300g of normal hexane, stirring for 2 hours, controlling the feeding speed of 70kg/h of 1-octene, the feeding speed of 70kg/h of normal hexane, the feeding speed of 300g/h of mixed cocatalyst mixed liquor, the feeding speed of 100g/h of mixed metallocene catalyst mixed liquor, mixing the metallocene catalyst mixed liquor, the cocatalyst mixed liquor, 1-octene and normal hexane for 30 minutes at 3MPa, and cooling to-25 ℃ through a cooler;
(3) Mixing the mixed solution obtained in the step (1) and the mixed solution obtained in the step (2) in a reaction kettle, calculating to obtain the optimal gas phase partial pressure Pg =1.18MPa on the premise of controlling the total pressure to be 2.5MPa, controlling the gas phase partial pressure to be 1.18MPa, and reacting at 150 ℃ for 20min to carry out polymerization.
Comparative example 1
The traditional method for feeding gas and liquid in the polyolefin polymerization process mainly comprises the following steps:
(1) Feeding gas-phase ethylene at the speed of 18kg/h, feeding hydrogen at the speed of 1g/h, and fully and uniformly mixing the gas-phase ethylene and the hydrogen in a reactor A under the pressure of 1 MPa;
(2) Mixing 10g of diphenylcarbon bridged-cyclopentadienyl-fluorenyl zirconium dichloride and 5000g of normal hexane serving as a metallocene catalyst, stirring for 2 hours, mixing 40g of methylaluminoxane compound modified by a cocatalyst and 300g of normal hexane, stirring for 2 hours, controlling the feeding speed of 70kg/h of 1-octene, the feeding speed of 70kg/h of normal hexane, the feeding speed of 300g/h of mixed cocatalyst mixed liquid, the feeding speed of 100g/h of mixed metallocene catalyst mixed liquid, mixing the metallocene catalyst mixed liquid, the cocatalyst mixed liquid, 1-octene and normal hexane for 30 minutes at 3MPa, and cooling to-25 ℃ by a cooler;
(3) And (3) mixing the mixed solution obtained in the step (1) and the mixed solution obtained in the step (2) in a reaction kettle, controlling the total pressure to be 3MPa, and reacting at 170 ℃ for 20min to carry out polymerization.
Comparative example 2
The traditional method for feeding gas and liquid in the polyolefin polymerization process mainly comprises the following steps:
(1) Feeding gas-phase ethylene at the speed of 18kg/h, feeding hydrogen at the speed of 1g/h, and fully and uniformly mixing the gas-phase ethylene and the hydrogen in a reactor A under the pressure of 1 MPa;
(2) Mixing 10g of diphenylcarbon bridge-cyclopentadienyl-fluorenyl zirconium dichloride of a metallocene catalyst with 5000g of normal hexane, stirring for 2 hours, mixing 40g of methylaluminoxane compound modified by a cocatalyst with 300g of normal hexane, stirring for 2 hours, controlling the feeding speed of 70kg/h of 1-octene, the feeding speed of 70kg/h of normal hexane, the feeding speed of 300g/h of mixed cocatalyst mixed liquor, the feeding speed of 100g/h of mixed metallocene catalyst mixed liquor, mixing the metallocene catalyst mixed liquor, the cocatalyst mixed liquor, 1-octene and normal hexane for 30 minutes at 3MPa, and cooling to-25 ℃ through a cooler;
(3) And (3) mixing the mixed solution obtained in the step (1) and the mixed solution obtained in the step (2) in a reaction kettle, controlling the total pressure to be 3MPa, and reacting at 150 ℃ for 20min to carry out polymerization.
Comparative example 3
The traditional method for feeding gas and liquid in the polyolefin polymerization process mainly comprises the following steps:
(1) Feeding gas-phase ethylene at the speed of 18kg/h, feeding hydrogen at the speed of 1g/h, and fully and uniformly mixing the gas-phase ethylene and the hydrogen in a reactor A under the pressure of 1 MPa;
(2) Mixing 10g of diphenylcarbon bridge-cyclopentadienyl-fluorenyl zirconium dichloride of a metallocene catalyst with 5000g of normal hexane, stirring for 2 hours, mixing 40g of methylaluminoxane compound modified by a cocatalyst with 300g of normal hexane, stirring for 2 hours, controlling the feeding speed of 70kg/h of 1-octene, the feeding speed of 70kg/h of normal hexane, the feeding speed of 300g/h of mixed cocatalyst mixed liquor, the feeding speed of 100g/h of mixed metallocene catalyst mixed liquor, mixing the metallocene catalyst mixed liquor, the cocatalyst mixed liquor, 1-octene and normal hexane for 30 minutes at 3MPa, and cooling to-25 ℃ through a cooler;
(3) And (3) mixing the mixed solution obtained in the step (1) and the mixed solution obtained in the step (2) together in a reaction kettle, controlling the total pressure to be 2.5MPa, and reacting at 150 ℃ for 20min to carry out polymerization.
Referring to table 1, table 1 shows the performance data of the polyolefin polymers prepared in the examples of the present invention and the comparative examples.
TABLE 1
| Item | Example 1 | Example 2 | Example 3 |
| Hardness, shore A | 64 | 65 | 65 |
| Tensile strength, MPa | 8.6 | 8.8 | 8.5 |
| Elongation at break,% | 800 | 790 | 810 |
| MFR，(190℃) | 5.2 | 5.3 | 4.9 |
| M W ，x10 4 | 21.4 | 21.6 | 21.8 |
| PDI | 2.0 | 2.1 | 1.9 |
| Item | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Hardness, shore A | 60 | 61 | 61 |
| Tensile strength, MPa | 7.5 | 7.7 | 7.1 |
| Elongation at break,% | 750 | 730 | 780 |
| MFR，(190℃) | 6.7 | 6.9 | 6.5 |
| M W ，x10 4 | 18.9 | 19.2 | 19.5 |
| PDI | 2.7 | 3.0 | 2.6 |
From examples 1 to 3, compared with comparative examples 1 to 3, it can be found that:
by optimizing and controlling the gas phase partial pressure, the tensile strength and the elongation at break of the polymer are obviously improved, the melt index is reduced, the molecular weight is increased, and the molecular weight distribution is smaller. The improvement of the above properties is beneficial to the overall performance of the polymer.
The foregoing detailed description of the present invention provides a method for feeding a mixture of gas and liquid during a polyolefin polymerization process, and the principles and embodiments of the present invention are described herein using specific examples, which are presented only to facilitate an understanding of the method and its core concepts, including the best mode, and to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, it is possible to make various improvements and modifications to the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. A gas-liquid mixing feeding method in a polyolefin preparation process is characterized by comprising the following steps:
1) Mixing all gas-phase materials in the polyolefin preparation process to obtain mixed gas;
mixing all liquid-phase materials in the polyolefin preparation process under pressure, and cooling to obtain a mixed solution;
2) And mixing the mixed gas and the mixed solution obtained in the step again at the first temperature, and then carrying out polymerization reaction to obtain the polyolefin.
2. The feeding method according to claim 1, wherein the pressure of the mixing is 0.3 to 10MPa;
the mixing is normal temperature mixing.
3. The feed process of claim 1, wherein the gas phase feed comprises one or more of ethylene, propylene, butylene, hydrogen, and nitrogen;
the ratio of the partial pressure of a single gas phase material in the total pressure of all the gas phase materials to the molar ratio of the single gas phase material in all the gas phase materials is (0.5-2): 1.
4. the feed method of claim 1, wherein the liquid phase feed comprises one or more of C3 to C20 linear or branched alpha-olefins, organic solvents, procatalysts, and cocatalysts;
the procatalyst comprises a single site metallocene catalyst and/or a post metallocene catalyst.
5. The feed process of claim 4, wherein the alpha-olefins comprise one or more of propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene, and 1-eicosene;
the procatalyst comprises one or more of diphenylcarbaryl-cyclopentadienyl-fluorenyl zirconium dichloride, diphenylcarbaryl-cyclopentadienyl- (2-dimethylamino-fluorenyl) zirconium dichloride, bis [2- (3 ',5' -di-tert-butylphenyl) -indenyl ] zirconium dichloride, biscyclopentadienyl-bisphenoxy zirconium, vinyl-bisindenyl-bisphenoxy zirconium, bis (salicylidene-phenylimino) titanium dichloride, [ N- (3,5-di-tert-butylsalicylidene) -2-diphenylphosphinobenzimide ] titanium trichloride, dimethylsilyl bisindenyl zirconium dichloride, dimethylsilyl-tetramethylcyclopentadienyl-tert-butylamino-dimethyltitanium dichloride, dimethylsilyl-3-pyrrolylindenyl-tert-butylamino-dimethyltitanium dichloride, pentamethylcyclopentadienyl- (2-phenylphenoxy) -titanium dichloride and pentamethylcyclopentadienyl- (2,6-diisopropylphenoxy) -titanium dichloride.
6. The feed process of claim 4, wherein the cocatalyst comprises one or more of methylalumoxane compound, modified methylalumoxane compound, tris (pentafluorophenyl) boron compound, triphenylcarbenium tetrakis (pentafluorophenyl) boron compound, N-dimethylanilinium tetrakis (pentafluorophenyl) boron compound, triisobutylaluminum, and trimethylaluminum;
the organic solvent comprises one or more of butane, isobutane, cyclobutane, n-pentane, isopentane, toluene, and xylene.
7. The feeding method according to claim 4, wherein the pressure of the pressurized mixing is 0.3 to 10MPa;
the specific way of mixing under pressure comprises: firstly, premixing alpha-olefin and an organic solvent, premixing a main catalyst and the organic solvent, premixing an auxiliary catalyst and the organic solvent, and then mixing the alpha-olefin, the main catalyst and the organic solvent under pressure; or premixing the alpha-olefin, part of the cocatalyst and the organic solvent, premixing the main catalyst and the organic solvent, premixing the rest of the cocatalyst and the organic solvent, and mixing the alpha-olefin, the part of the cocatalyst and the organic solvent under pressure.
8. The feeding method according to claim 1, characterized in that the temperature of the cooling is between-35 ℃ and-10 ℃.
The first temperature is 100-200 ℃.
9. The feeding method according to claim 1, wherein the partial pressure of the gas phase during the remixing is 0.15 to 4MPa;
the pressure of the remixing is 0.3-10 MPa;
the time for mixing again is 10-150 min.
10. The feeding method according to claim 1, wherein the pressure of the polymerization reaction is 1 to 10MPa;
the temperature of the polymerization reaction is 100-200 ℃;
the time of the polymerization reaction is 5-150 min.
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