CN117003921A - Catalyst for ethylene and propylene copolymerization and application thereof - Google Patents
Catalyst for ethylene and propylene copolymerization and application thereof Download PDFInfo
- Publication number
- CN117003921A CN117003921A CN202210450277.9A CN202210450277A CN117003921A CN 117003921 A CN117003921 A CN 117003921A CN 202210450277 A CN202210450277 A CN 202210450277A CN 117003921 A CN117003921 A CN 117003921A
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- Prior art keywords
- catalyst
- ethylene
- propylene
- copolymerization
- borate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 36
- 238000007334 copolymerization reaction Methods 0.000 title claims abstract description 27
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims description 25
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims description 22
- 239000005977 Ethylene Substances 0.000 title claims description 22
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 polypropylene Polymers 0.000 claims abstract description 15
- 229910000085 borane Inorganic materials 0.000 claims abstract description 11
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 3
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical group 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 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000010574 gas phase reaction Methods 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 239000004743 Polypropylene Substances 0.000 abstract description 6
- 229920001155 polypropylene Polymers 0.000 abstract description 6
- 229920001577 copolymer Polymers 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical class C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 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 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 238000007613 slurry method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229920006030 multiblock copolymer Polymers 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
Classifications
-
- 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
- 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
-
- 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 catalyst system consists of a catalyst for preparing isotactic polypropylene and a borane or borate compound, and can catalyze and obtain a copolymerization product with longer propylene sequence of a crystalline fraction or high crystalline fraction content. The catalyst system has the advantages of strong applicability, high catalytic efficiency and easy obtainment.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a catalyst for ethylene and propylene copolymerization and application thereof.
Background
The ethylene-propylene copolymer is a synthetic polymer material with wide application, wherein the ethylene-propylene copolymer (EPR) with the ethylene content of 20-50 percent has the property of an elastomer and is widely applied as a plastic toughening modifier. The isotactic polypropylene (iPP) has poor toughness and transparency, is difficult to be used in the application fields of manufacturing pipes and the like, and can be used for preparing a modified polypropylene material with impact resistance far higher than that of the common iPP by blending proper amount of EPR into the iPP, thereby being applied to various fields of automobile bumpers, impact-resistant injection-molded products and the like. However, EPR with random sequence distribution is incompatible with iPP, and the EPR phase region in the iPP/EPR blend material obtained by blending the EPR and the iPP has larger size, so that the toughening effect of the EPR can not be fully exerted.
One type of catalyst common to EPR industrial production is a heterogeneous catalyst system consisting of a granular main catalyst formed by loading titanium chloride on magnesium chloride and an organic aluminum cocatalyst, and the synthesized EPR contains more crystalline fractions (generally about 20%). Previous studies have shown that the crystalline fraction in EPR prepared by titanium-based catalyst system consists of a series of ethylene-propylene multiblock copolymers with different compositions, wherein the relatively longer propylene-sequence block copolymer chain is compatible with both iPP and ethylene-propylene random copolymer, thus playing a role in compatibilization in the blending material of iPP and EPR, reducing the size of the EPR phase region and improving the toughening effect of random copolymer. It is expected that EPR with longer propylene sequence is prepared and then blended with iPP to prepare high-performance polyolefin material with excellent rigidity and toughness, so that more catalysts for ethylene propylene copolymerization are required to be developed.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art and provides a catalyst for ethylene and propylene copolymerization and application thereof.
The technical scheme of the invention is as follows: a catalyst for ethylene and propylene copolymerization, which consists of the following four components:
(A) The structural formula is TiCl 4 /MgCl 2 ID or TiCl 4 /MgCl 2 ·ID/SiO 2 Wherein ID is an internal electron donor;
(B) An organoaluminum compound;
(C) The structural formula is R 1 R 2 Si(OCH 3 ) 2 Wherein R is 1 、R 2 Each independently is an alkyl group having 1 to 6 carbons, a cycloalkyl group, or a phenyl group;
(D) A borane or borate compound, wherein the borane is tris (pentafluorophenyl) borane; the borate is trityl tetra (pentafluorophenyl) borate; or trityl tetrakis (pentafluorophenyl) borate, wherein the methyl para-position on the benzene ring of the trityl tetrakis (pentafluorophenyl) borate is respectively substituted by R, wherein three R substituents are respectively and independently halogen, alkyl, cycloalkyl or phenyl containing 1-6 carbons.
The molecular structural formula of the benzyl tetra (pentafluorophenyl) borate is shown in the formula 1), and the trityl tetra (pentafluorophenyl) borate is shown in the formula 2).
The method comprises the steps of (1),
formula 2.
The catalyst composition provided by the invention consists of a catalyst system for preparing isotactic polypropylene and a borane or borate compound, and can be used for catalyzing the copolymerization of ethylene and propylene to obtain a copolymerization product with a crystalline fraction of which the propylene sequence is longer or a copolymerization product with a crystalline fraction of which the content is higher. In the catalyst system of isotactic polypropylene, a small amount of organic compound with electron donating group (called external electron donor) is added in addition to the granular main catalyst (supported titanium catalyst) and alkyl aluminum cocatalyst which are formed by loading titanium chloride on magnesium chloride, so as to improve the stereospecificity of the catalyst and prepare the polypropylene with high isotacticity.
As a further improvement of the technical scheme, in order to improve the catalytic efficiency, the ID is a carboxylate or an ether.
As a further improvement of the technical scheme, in order to improve the catalytic efficiency, the ID is phthalate, succinate, 1, 3-diether compound or 1, 2-diether compound.
As a further improvement of the technical scheme, in order to improve the catalytic efficiency, the organosilicon compound comprises Ph 2 Si(OCH 3 ) 2 、(cy-C 5 H 9 ) 2 Si(OCH 3 ) 2 Or (cy-C) 6 H 11 )(CH 3 )Si(OCH 3 ) 2 。
As a further improvement of the technical scheme, the organic aluminum compound is triethylaluminum or triisobutylaluminum in order to improve the catalytic efficiency and the availability.
As a further improvement of the technical scheme, in order to improve the catalytic efficiency, the molar ratio of aluminum to titanium in the catalyst is 10-500: 1.
as a further improvement of the technical scheme, in order to improve the catalytic efficiency, the molar ratio of aluminum to silicon in the catalyst is 2-50: 1.
as a further improvement of the technical scheme, in order to improve the catalytic efficiency, the molar ratio of boron to silicon in the catalyst is 0.1-5: 1.
the use of said catalyst for the copolymerization of ethylene and propylene, the copolymerization of ethylene and propylene being carried out in a batch or continuous manner by slurry or gas phase reaction under the action of said catalyst. The slurry method is that ethylene and propylene carry out slurry copolymerization reaction in hydrocarbon solvent containing catalyst system and a small amount of hydrogen, viscous solution of copolymerization product is obtained after a certain time of reaction, and solid ethylene-propylene copolymer is obtained after hydrocarbon solvent in the solution is removed; gaseous ethylene and propylene are subjected to gas phase copolymerization reaction in the presence of a catalyst system and a small amount of hydrogen to directly synthesize the granular ethylene-propylene copolymer.
The four components used in the catalyst system of the invention can be purchased through public market, when ethylene propylene is copolymerized by a batch slurry polymerization process, a certain amount of purified dry hydrocarbon solvent can be added into a kettle reactor, and after the reaction kettle is raised to a preset temperature, a cocatalyst, an external electron donor and borane or borate compound are sequentially added into the reaction kettle. And (3) pressing ethylene/propylene mixed gas with set pressure into the reactor under stirring until the gas-liquid balance is achieved, and finally adding main catalyst powder or slurry thereof into the reactor to start the polymerization reaction. After a certain period of reaction, the monomer pressure is removed, and residual monomers and solvent are removed under reduced pressure, so that the copolymer particles can be obtained.
As a further improvement of the technical scheme, the mol ratio of ethylene to propylene in the catalytic reaction is 0.1-10: 1.
compared with the prior art, the catalyst has outstanding substantive characteristics and remarkable progress, and particularly, compared with a polymerization system only added with an organic silicon external electron donor, the average length of propylene sequences of crystalline fractions in ethylene-propylene copolymer products is increased by more than 30 percent. In some products of the copolymerization system containing a borane or borate compound, the average length of the propylene sequence of the crystalline fraction is not increased, but the content of the crystalline fraction is increased by 30% or more. Furthermore, the catalyst system has strong applicability, can be used for a gas phase method and a slurry method, and can be used for continuous and batch reactions. In a further aspect, the catalyst system of the present invention has high catalytic efficiency and a polymerization time (or average residence time of a continuous process) of from 0.5 to 4 hours. The catalyst system of the invention has the advantages of high catalytic efficiency, strong applicability and easy availability.
Detailed Description
The technical scheme of the invention is further described in detail through the following specific embodiments.
In the examples, the catalytic efficiency of the polymerization reaction is expressed in grams of copolymer produced per gram of catalyst per hour (g EPR/g catalyst.hr). The crystalline fraction content of the ethylene propylene copolymer was determined by dissolution separation, namely: the copolymer is first dissolved in boiling n-octane, and the solution is cooled to room temperature to separate out solid crystalline fraction, which is then filtered to separate out crystalline fraction, dried and weighed. The propylene unit content and the average length of propylene sequences (nP) of the crystalline fraction in the copolymer were determined by nmr carbon spectrometry.
Example 1
500 ml of n-heptane and a cocatalyst Al (C) were added in sequence to a 1 liter reaction kettle with a mechanical stirring device under the protection of high purity nitrogen 2 H 5 ) 3 External electron donor Ph 2 Si(OCH 3 ) 2 And tris (pentafluorophenyl) borane C 18 BF 15 Wherein, the cocatalyst is 5.64mmol, the external electron donor is 0.141mmol, and the borane compound is 0.282mmol. The kettle is heated to 70 ℃ under stirring, the nitrogen in the kettle is removed by vacuumizing, the ethylene/propylene mixed gas with the mol ratio of 1:1.5 is pressed into the kettle to the gauge pressure of 0.2MPa, and after the solvent absorbs the monomer to be saturated, 0.050g of main catalyst is added to start the polymerization reaction. (the main catalyst has TiCl as the main component 4 、MgCl 2 And diisobutyl phthalate, the titanium content of which is 2.7. 2.7 wt percent, and the addition amount of the main catalyst is 0.0282mmol calculated by Ti. ) The gas pressure in the reactor was maintained at 0.2MPa gauge during the polymerization by continuously supplementing an ethylene/propylene mixture at a sufficient pressure ratio of 1:1.5. After 30 minutes of reaction under stirring at a rate of 400 rpm, the reaction was terminated and the ethylene-propylene copolymer was recovered. The catalyst efficiency, calculated on the weight of the product, was 1250g EPR/g catalyst. The crystalline fraction of the copolymer had a content of 20%, the propylene content in the crystalline fraction was 19% (mol), and the average length of the propylene sequence was 6.2.
Example 2
In comparison with example 1, except that the borane compound C18BF15 is changed to trityltetra (pentafluorophenyl) borate C 43 H 15 BF 20 The rest of the operations and conditions were the same except for the above. The catalyst efficiency of the copolymerization reaction was 1200g EPR/g catalyst.h. The crystalline fraction content of the copolymer was 25%. The propylene content of the crystalline fraction was 23% (mol) and the average length of the propylene sequences was 4.8.
Example 3
In comparison with example 2, the trityl tetrakis (pentafluorophenyl) borate C was removed 43 H 15 BF 20 The molar ratio to titanium is increased to 20: except 1, the rest of the operation and conditions are the same. The catalyst efficiency of the copolymerization reaction was 1270g EPR/g catalyst.h. The crystalline fraction content of the copolymer was 32%. Propylene of crystalline fractionThe alkene content was 26 mol% and the average length of the propylene sequence was 4.2.
Comparative example
In comparison with example 1, no borane compound C was added 18 BF 15 The rest of the operations and conditions were the same. The catalyst efficiency of the copolymerization reaction was 1350g EPR/g catalyst.h. The crystalline fraction content of the copolymer was 22%. The propylene content of the crystalline fraction was 17% (mol) and the average length of the propylene sequences was 3.5.
Finally, it should be noted that the above-mentioned embodiments are only for illustrating the technical scheme of the present invention and are not limiting; while the invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that the present invention may be modified and equivalents substituted for elements thereof; without departing from the spirit of the invention, it is intended to cover the scope of the invention as claimed.
Claims (10)
1. A catalyst for ethylene and propylene copolymerization, which is characterized by comprising the following four components:
(A) The structural formula is TiCl 4 /MgCl 2 ID or TiCl 4 /MgCl 2 ·ID/SiO 2 Wherein ID is an internal electron donor;
(B) An organoaluminum compound;
(C) The structural formula is R 1 R 2 Si(OCH 3 ) 2 Wherein R is 1 、R 2 Each independently is an alkyl group having 1 to 6 carbons, a cycloalkyl group, or a phenyl group;
(D) A borane or borate compound, wherein the borane is tris (pentafluorophenyl) borane; the borate is trityl tetra (pentafluorophenyl) borate; or trityl tetra (pentafluorophenyl) borate, wherein the para-position of the methyl group on the benzene ring is respectively substituted by R substituents, and three R substituents are respectively and independently halogen, alkyl containing 1-6 carbons, cycloalkyl or phenyl.
2. The catalyst for the copolymerization of ethylene and propylene according to claim 1, wherein the ID is a carboxylate or an ether.
3. The catalyst for copolymerization of ethylene and propylene according to claim 2, wherein: the ID is phthalate, succinate, 1, 3-diether compound and 1, 2-diether compound.
4. The catalyst for the copolymerization of ethylene and propylene according to claim 1, wherein the organosilicon compound comprises Ph 2 Si(OCH 3 ) 2 、(cy-C 5 H 9 ) 2 Si(OCH 3 ) 2 Or (cy-C) 6 H 11 )(CH 3 )Si(OCH 3 ) 2 。
5. The catalyst for the copolymerization of ethylene and propylene according to claim 1, wherein the organoaluminum compound is triethylaluminum or triisobutylaluminum.
6. The catalyst for the copolymerization of ethylene and propylene according to claim 1, wherein the molar ratio of aluminum to titanium in the catalyst is 10 to 500:1.
7. the catalyst for the copolymerization of ethylene and propylene according to claim 1, wherein the molar ratio of aluminum to silicon in the catalyst is 2 to 50:1.
8. the catalyst for the copolymerization of ethylene and propylene according to claim 1, wherein the molar ratio of boron to silicon in the catalyst is 0.1 to 5:1.
9. use of a catalyst according to any of claims 1-8, characterized in that ethylene and propylene are copolymerized in a batch or continuous manner by slurry or gas phase reaction under the action of the catalyst.
10. The use of the catalyst according to claim 9, wherein the molar ratio of ethylene to propylene in the catalytic reaction is between 0.1 and 10:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210450277.9A CN117003921A (en) | 2022-04-27 | 2022-04-27 | Catalyst for ethylene and propylene copolymerization and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210450277.9A CN117003921A (en) | 2022-04-27 | 2022-04-27 | Catalyst for ethylene and propylene copolymerization and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117003921A true CN117003921A (en) | 2023-11-07 |
Family
ID=88564067
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210450277.9A Pending CN117003921A (en) | 2022-04-27 | 2022-04-27 | Catalyst for ethylene and propylene copolymerization and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117003921A (en) |
-
2022
- 2022-04-27 CN CN202210450277.9A patent/CN117003921A/en active Pending
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