CN115028764A - In-situ synthesis method of polyolefin elastomer - Google Patents
In-situ synthesis method of polyolefin elastomer Download PDFInfo
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- 229920006124 polyolefin elastomer Polymers 0.000 title claims abstract description 38
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 29
- 238000001308 synthesis method Methods 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 90
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 60
- 238000006384 oligomerization reaction Methods 0.000 claims abstract description 59
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000005977 Ethylene Substances 0.000 claims abstract description 44
- 239000004711 α-olefin Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 230000009471 action Effects 0.000 claims abstract description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 239000011651 chromium Substances 0.000 claims abstract description 4
- OIDRXSLJYDFQAZ-UHFFFAOYSA-N N[Hf].N1=CC=CC=C1 Chemical compound N[Hf].N1=CC=CC=C1 OIDRXSLJYDFQAZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000001412 amines Chemical class 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 35
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 17
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 14
- 229910052796 boron Inorganic materials 0.000 claims description 14
- 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 9
- 230000035484 reaction time Effects 0.000 claims description 8
- 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 6
- 239000012442 inert solvent Substances 0.000 claims description 5
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 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 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 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 3
- 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 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-O dimethyl(phenyl)azanium Chemical compound C[NH+](C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-O 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 63
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
- 238000010438 heat treatment Methods 0.000 description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 23
- 239000000243 solution Substances 0.000 description 21
- 238000006116 polymerization reaction Methods 0.000 description 20
- 239000000047 product Substances 0.000 description 20
- 238000001035 drying Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 238000010907 mechanical stirring Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- -1 polyethylene Polymers 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- 208000005156 Dehydration Diseases 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- CQXDWZIITWYXEJ-UHFFFAOYSA-N [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CN(C)C1=CC=CC=C1 Chemical compound [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CN(C)C1=CC=CC=C1 CQXDWZIITWYXEJ-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GGSUCNLOZRCGPQ-UHFFFAOYSA-O diethyl(phenyl)azanium Chemical compound CC[NH+](CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-O 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- 238000005829 trimerization reaction Methods 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
-
- 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 discloses an in-situ synthesis method of a polyolefin elastomer, which takes ethylene as the only raw material and prepares the polyolefin elastomer in situ under the action of a diphosphonic amine chromium oligomerization catalyst and a pyridine amino hafnium copolymerization catalyst. The invention avoids adding expensive alpha-olefin as raw material, and uses single reactor to prepare in situ, which greatly simplifies the preparation process flow and equipment cost of polyolefin elastomer. Compared with the prior art, the polyolefin elastomer product prepared based on the method has lower density and crystallinity, higher molecular weight, narrower molecular weight distribution and excellent comprehensive performance.
Description
Technical Field
The invention belongs to the field of polymers, and particularly relates to a synthetic method for preparing a polyolefin elastomer by ethylene in-situ copolymerization.
Background
Polyolefin elastomers (POE) are a class of polyolefin materials obtained by random copolymerization of ethylene and high-carbon α -olefins (1-butene, 1-hexene, 1-octene, etc.). Owing to the continuous development of olefin coordination polymerization catalysts and their cocatalysts, the introduction of a large amount of alpha-olefin monomers into polyethylene segments has been achieved. As an elastomer material prepared by using a special catalysis technology, POE has a unique molecular chain structure, wherein a polyethylene chain segment plays a role of a physical cross-linking point, and the crystallinity of the polyethylene chain segment is weakened by the introduction of a large amount of alpha-olefin comonomers in a main chain, so that the material integrally presents rubber elasticity, and simultaneously has excellent physical and mechanical properties and good processing performance, and has the dual characteristics of plastics and rubber.
The traditional method for synthesizing POE is a high-temperature solution polymerization process, i.e. the ethylene and alpha-olefin are randomly copolymerized in a specific solvent under the action of a catalyst, and the process temperature is above the melting point of a polymerization product. The current worldwide POE production technology is represented by the instite technology of the combination of constrained geometry metallocene catalyst (CGC) and solution polymerization process by the dow chemical company in usa, which has completed the industrial production of POE in 1993. However, industrial production of POE still cannot be realized at home at present, and research aiming at POE is mostly focused on modification and application of POE products. In addition, the production process of polymer-grade linear alpha-olefin for preparing POE is also an important factor for restricting the industrialization of POE. Ethylene oligomerization catalysis is a main method for preparing linear alpha-olefin, is different from traditional methods such as alkane catalytic cracking and fatty alcohol dehydrogenation, and the ethylene oligomerization method for preparing the alpha-olefin has advantages in product quality and industrial flow, and is one of the main industrial production methods of the alpha-olefin at present. Traditional ethylene oligomerization catalysis often obtains multi-component linear alpha-olefin in a wide range, the proportion of the alpha-olefin with specific carbon number is low, and high-purity alpha-olefin is obtained by rectification separation with high energy consumption. Therefore, the high-selectivity oligomerization catalysis of the ethylene provides an important path for producing single alpha-olefin with a specific carbon number. The british petroleum company Carter et al (chem. commu.2002, 858.) found that a chromium catalytic system using a bis-phosphonimine (PNP) ligand can catalyze ethylene trimerization with high selectivity under milder conditions to yield nearly 90% of 1-hexene. The Saxol publication EP1581342A1 improves the ligand structure and catalyzes the tetramerization of ethylene at 45 ℃ and 4.5MPa to obtain 1-octene as the main product.
The POE in the prior art is prepared by copolymerization, and the problem of high preparation cost caused by the need of adding expensive alpha-olefin as a raw material generally exists; partially uses ethylene as raw material to prepare POE, but has the problems of complex preparation process flow and higher separation energy consumption.
Disclosure of Invention
The invention provides an in-situ synthesis method of polyolefin elastomer, aiming at the defects of the prior art, the method can prepare the polyolefin elastomer with excellent performance by taking ethylene as the only raw material under the action of an oligomerization catalyst and a copolymerization catalyst without additionally using alpha-olefin with high price, avoids the separation process of the alpha-olefin prepared in situ, greatly simplifies the process flow of the polyolefin elastomer and reduces the equipment cost.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides an in-situ synthesis method of a polyolefin elastomer, which comprises the following steps: in an inert solvent and in the presence of an oligomerization catalyst and a cocatalyst, carrying out oligomerization reaction by taking ethylene as a raw material to obtain alpha-olefin, then adding a copolymerization catalyst and the cocatalyst, and carrying out in-situ copolymerization reaction under the action of the catalyst to prepare a polyolefin elastomer;
the oligomerization catalyst is a diphosphonic amine chromium catalyst with a structural formula A; the copolymerization catalyst is a pyridine amino hafnium catalyst with a structural formula B; the molar ratio of the oligomerization catalyst to the copolymerization catalyst is 0.2: 1-20: 1;
the catalyst promoter for oligomerization reaction is the same as or different from the catalyst promoter for copolymerization reaction; the cocatalyst for oligomerization reaction is an aluminum-containing cocatalyst and/or a boron-containing cocatalyst; the cocatalyst of the copolymerization reaction is an aluminum-containing cocatalyst and/or a boron-containing cocatalyst;
in the in-situ synthesis method of the present invention, preferably, the inert solvent is one or more of normal alkane, isoparaffin, cycloparaffin and branched-chain aromatic hydrocarbon.
Further preferably, the reaction temperature of the oligomerization reaction is 10-100 ℃, the ethylene pressure is 1-10 MPa, and the oligomerization reaction time is 0.1-2 h; the temperature of the copolymerization reaction is 30-150 ℃, the ethylene pressure is 1-10 MPa, and the copolymerization reaction time is 0.1-1 h.
Further, in order to control the selectivity and reaction efficiency of the ethylene oligomer, preferably, the oligomerization reaction conditions include: the reaction temperature is 30-70 ℃, the ethylene pressure is 1-5 MPa, and the reaction time is 0.4-1 h.
Further, in order to control the composition of the copolymerization product and the copolymerization efficiency, preferably, the copolymerization reaction conditions include: the reaction temperature is 80-140 ℃, the ethylene pressure is 1-4 MPa, and the reaction time is 0.1-0.5 h.
In the in-situ synthesis method, the aluminum-containing cocatalyst is preferably one or more of methylaluminoxane, modified methylaluminoxane, triethylaluminum and triisobutylaluminum; the boron-containing cocatalyst is preferably one or more of tris (pentafluorophenyl) boron, triphenylcarbenium tetrakis (pentafluorophenyl) boron, N-dimethylanilinium tetrakis (pentafluorophenyl) boron.
In the in-situ synthesis method, if the cocatalyst of the oligomerization reaction is an aluminum-containing cocatalyst, the molar ratio of the oligomerization catalyst to the aluminum-containing cocatalyst is 1 (50-1000);
if the cocatalyst for the oligomerization reaction is an aluminum-containing cocatalyst and a boron-containing cocatalyst, the molar ratio of the oligomerization catalyst to the aluminum-containing cocatalyst to the boron-containing cocatalyst is 1 (50-1000) to 1-5;
if the cocatalyst of the copolymerization reaction is an aluminum-containing cocatalyst, the molar ratio of the copolymerization catalyst to the aluminum-containing cocatalyst is 1 (50-1000);
if the cocatalyst of the copolymerization reaction is a boron-containing cocatalyst, the molar ratio of the copolymerization catalyst to the boron-containing cocatalyst is 1 (1-5).
Furthermore, the concentration of the oligomerization catalyst in the catalytic system in the oligomerization reaction is 1-20 mu mol/L; the concentration of the copolymerization catalyst in the catalytic system in the copolymerization reaction is 1-20 mu mol/L;
in the present invention, the addition mode of the oligomerization or copolymerization catalyst system is not required, and the catalyst and the cocatalyst may be prepared in advance and then added to the reactor, or the cocatalyst and the catalyst may be added to the reactor separately.
The method of the invention also comprises the following steps: adding chain terminator such as methanol and ethanol after copolymerization reaction.
Compared with the prior art, the in-situ synthesis method of the polyolefin elastomer has the following beneficial effects:
the in-situ synthesis method of the invention takes ethylene as the only raw material, firstly alpha-olefin is obtained under the action of an oligomerization catalyst, and then the high-performance polyolefin elastomer is prepared in situ under the action of a copolymerization catalyst, the method does not need to additionally add expensive alpha-olefin as the raw material, and the prepared polyolefin elastomer has a small amount of 4-carbon branched chains under the condition of taking 6-carbon branched chains as the main raw material, thereby effectively reducing the cost of the raw material, simultaneously avoiding complex process flow and higher separation energy consumption, and simplifying the production device; the density of the polyolefin elastomer product prepared by the method can be reduced by 5-10%, the molecular weight is increased by 50-120%, the molecular weight distribution is reduced by 10-50%, and the product comprehensive performance is excellent.
Detailed Description
The technical scheme and the technical effect of the invention are further explained by combining the specific embodiments.
The invention provides an in-situ synthesis method of a polyolefin elastomer, which comprises the following steps: in inert solvent and in the presence of oligomerization catalyst and cocatalyst, ethylene is oligomerized to obtain alpha-olefin, and then copolymerization catalyst and cocatalyst are added to prepare polyolefin elastomer in situ under the action of the alpha-olefin.
In the preparation process of the polyolefin elastomer, the combined catalytic system of the oligomerization catalyst and the copolymerization catalyst with a specific structure is used, so that the polyolefin elastomer can be prepared by only using ethylene as a raw material under the condition of not additionally and independently adding alpha-olefin as a comonomer. Therefore, the problem of the source of alpha-olefin in the conventional preparation process of the polyolefin elastomer can be solved, a single reaction device is used, the equipment cost is reduced, and the complex process flow and higher separation energy consumption are avoided.
The present invention will be described in detail below by way of examples.
Example 1
Heating and drying a 500mL polymerization reaction kettle, vacuumizing for three times, vacuumizing again, introducing 200mL n-hexane subjected to water removal treatment into the reaction kettle, heating to 50 ℃ under mechanical stirring, introducing ethylene gas with the pressure of 2MPa, introducing 2mL (oligomerization catalyst: 1 mu mol/mL; methylaluminoxane: 1mmol/mL) of toluene solution of an oligomerization catalyst, reacting for 0.5h under the conditions, raising the temperature to 110 ℃, keeping the ethylene pressure at 2MPa, introducing 1mL (copolymerization catalyst: 1 mu mol/mL; methylaluminoxane: 1mmol/mL) of toluene solution of a copolymerization catalyst, continuing to react for 0.2h, adding 10mL of ethanol, and stopping the reaction to obtain 4.88g of a polymerization product.
Example 2
Heating and drying a 500mL polymerization reaction kettle, vacuumizing for three times, vacuumizing again, introducing 200mL n-hexane subjected to water removal treatment into the reaction kettle, heating to 40 ℃ under mechanical stirring, introducing ethylene gas with the pressure of 1.5MPa, introducing 2mL (1 mu mol/mL of oligomerization catalyst and 1mmol/mL of methylaluminoxane) of toluene solution of the oligomerization catalyst, reacting for 0.5h under the conditions, raising the temperature to 130 ℃, introducing 1mL (1 mu mol/mL of copolymerization catalyst and 1.5 mu mol/mL of triphenylcarbenium (pentafluorophenyl) boron) of the ethylene pressure of 2MPa of the copolymerization catalyst, continuing to react for 0.2h, and adding 10mL of ethanol to terminate the reaction to obtain 4.02g of a polymerization product.
Example 3
Heating and drying a 500mL polymerization reaction kettle, vacuumizing for three times, vacuumizing again, introducing 200mL n-hexane subjected to water removal treatment into the reaction kettle, heating to 60 ℃ under mechanical stirring, introducing ethylene gas with the pressure of 2.5MPa, introducing 1mL (oligomerization catalyst: 1 mu mol/mL; methylaluminoxane: 1mmol/mL) of toluene solution of the oligomerization catalyst, reacting for 0.8h under the conditions, raising the temperature to 120 ℃, introducing 1.5MPa of ethylene pressure, introducing 1mL (copolymerization catalyst: 1 mu mol/mL; triphenylcarbenium (pentafluorophenyl) boron: 1.5 mu mol/mL) of toluene solution of the copolymerization catalyst, continuing to react for 0.2h, and adding 10mL of ethanol to terminate the reaction to obtain 2.49g of a polymerization product.
Example 4
Heating and drying a 500mL polymerization reaction kettle, vacuumizing for three times, vacuumizing again, introducing 200mL N-hexane subjected to water removal treatment into the reaction kettle, heating to 70 ℃ under mechanical stirring, introducing ethylene gas with the pressure of 3.5MPa, introducing 2mL (oligomerization catalyst: 1 mu mol/mL; triethylaluminum: 0.1 mmol/mL; methylaluminoxane: 0.5mmol/mL) of toluene solution of the oligomerization catalyst, reacting for 0.6h under the conditions, raising the temperature to 140 ℃, introducing 2mL (copolymerization catalyst: 1 mu mol/mL) of toluene solution of the copolymerization catalyst and N, N-dimethylanilinium (pentafluorophenyl) boron: 1.5 mu mol/mL, continuing to react for 0.3h, adding 10mL of ethanol, and terminating the reaction to obtain 4.37g of a polymerization product.
Example 5
Heating and drying a 500mL polymerization reaction kettle, vacuumizing for three times, vacuumizing again, introducing 200mL n-hexane subjected to water removal treatment into the reaction kettle, heating to 70 ℃ under mechanical stirring, introducing ethylene gas with the pressure of 4.5MPa, introducing 2mL of toluene solution of an oligomerization catalyst (the oligomerization catalyst is 1 mu mol/mL; triisobutylaluminum is 0.1 mmol/mL; triphenylcarbetetrakis (pentafluorophenyl) boron is 1 mu mol/mL), reacting for 0.4h under the conditions, raising the temperature to 150 ℃, introducing 2mL of toluene solution of a copolymerization catalyst (the copolymerization catalyst is 1 mu mol/mL; tris (pentafluorophenyl) boron is 1.5 mu mol/mL), continuing to react for 0.3h, adding 10mL of ethanol, and terminating the reaction to obtain 5.12g of a polymerization product.
Example 6
Heating and drying a 500mL polymerization reaction kettle, vacuumizing and introducing nitrogen for three times, vacuumizing again, introducing 200mL n-hexane subjected to dehydration treatment into the reaction kettle, after heating to 40 ℃ under mechanical stirring, ethylene gas with the pressure of 1.5MPa is introduced, 2mL of toluene solution of an oligomerization catalyst (oligomerization catalyst: 1. mu. mol/mL; tributylaluminum: 0.1 mmol/mL; N, N-diethylanilinium tetrakis (pentafluorophenyl) boron: 1. mu. mol/mL) is introduced, then reacting for 1h under the conditions, raising the temperature to 120 ℃, leading the ethylene pressure to be 3MPa, 2mL of a toluene solution of a copolymerization catalyst (copolymerization catalyst: 1. mu. mol/mL; 1.5. mu. mol/mL of N, N-diethylaniliniumtetrakis (pentafluorophenyl) boron) was introduced, the reaction was continued for 0.4 hour, and 10mL of ethanol was added to terminate the reaction, whereby 3.64g of a polymer product was obtained.
Example 7
Heating and drying a 500mL polymerization reaction kettle, vacuumizing for three times, vacuumizing again, introducing 200mL n-hexane subjected to water removal treatment into the reaction kettle, heating to 55 ℃ under mechanical stirring, introducing ethylene gas with the pressure of 3MPa, introducing 2mL (1 mu mol/mL of oligomerization catalyst; 0.5mmol/mL of triethylaluminum; 0.5mmol/mL of methylaluminoxane) of toluene solution of the oligomerization catalyst, reacting for 0.5h under the conditions, raising the temperature to 110 ℃, introducing 2mL (1 mu mol/mL of copolymerization catalyst; 0.5mmol/mL of methylaluminoxane) of toluene solution of the copolymerization catalyst, continuing to react for 0.3h, and adding 10mL of ethanol to terminate the reaction to obtain 4.58g of a polymerization product.
Example 8
Heating and drying a 500mL polymerization reaction kettle, vacuumizing for three times, vacuumizing again, introducing 200mL n-hexane subjected to water removal treatment into the reaction kettle, heating to 65 ℃ under mechanical stirring, introducing ethylene gas with the pressure of 4MPa, introducing 1.5mL (1 mu mol/mL; methylaluminoxane: 0.5mmol/mL) of toluene solution of an oligomerization catalyst, reacting for 0.5h under the conditions, raising the temperature to 130 ℃, introducing 1mL (1 mu mol/mL; methylaluminoxane: 1mmol/mL) of toluene solution of a copolymerization catalyst, continuing to react for 0.2h, and adding 10mL of ethanol to terminate the reaction, thereby obtaining 2.62g of a polymerization product.
Comparative example 1
Heating and drying a 500mL polymerization reaction kettle, vacuumizing for three times, introducing nitrogen, vacuumizing again, introducing 200mL n-hexane and 20mL 1-octene subjected to water removal treatment into the reaction kettle, heating to 130 ℃ under mechanical stirring, and introducingEthylene gas at a pressure of 3MPa and the CGC catalyst Cp SiMe was introduced 2 NBu t TiCl 2 Then reacted for 0.2h under the conditions of 1mL of toluene solution (CGC catalyst: 1. mu. mol/mL; methylaluminoxane: 1mmol/mL), and 10mL of ethanol was added to terminate the reaction, to obtain 4.17g of a polymer product.
Comparative example 2
Heating and drying 500mL of polymerization reaction kettle, vacuumizing for three times, introducing 200mL of n-hexane and 20mL of 1-octene which are subjected to water removal treatment into the reaction kettle after vacuumizing again, heating to 110 ℃ under mechanical stirring, introducing ethylene gas with the pressure of 2MPa, and introducing CGC catalyst Cp SiMe 2 NBu t TiCl 2 1mL of toluene solution (CGC catalyst: 1. mu. mol/mL; triisobutylaluminum: 0.2 mmol/mL; triphenylcarbetetrakis (pentafluorophenyl) boron: 1.5. mu. mol/mL), and reacted under these conditions for 0.2h, 10mL of ethanol was added to terminate the reaction, whereby 2.83g of a polymer product was obtained.
Comparative example 3
Heating and drying a 500mL polymerization reaction kettle, vacuumizing for three times, vacuumizing again, introducing 200mL n-hexane subjected to water removal treatment into the reaction kettle, heating to 45 ℃ under mechanical stirring, introducing ethylene gas with the pressure of 2MPa, introducing 1.5mL (oligomerization catalyst: 1 mu mol/mL; methylaluminoxane: 1mmol/mL) of toluene solution of an oligomerization catalyst, reacting for 0.5h under the conditions, raising the temperature to 120 ℃, introducing the ethylene pressure to 3MPa, and introducing a CGC catalyst CpSiMe 2 NBu t TiCl 2 1mL of the resulting toluene solution (CGC catalyst: 1. mu. mol/mL; methylaluminoxane: 1mmol/mL) was reacted for 0.2 hour, and 10mL of ethanol was added to terminate the reaction, whereby 3.46g of a polymer product was obtained.
Comparative example 4
Heating and drying a 500mL polymerization reaction kettle, vacuumizing for three times, vacuumizing again, introducing 200mL n-hexane subjected to water removal treatment into the reaction kettle, heating to 60 ℃ under mechanical stirring, introducing ethylene gas with the pressure of 3MPa, introducing 1mL (oligomerization catalyst: 1 mu mol/mL; methylaluminoxane: 1mmol/mL) of toluene solution of an oligomerization catalyst, reacting for 0.5h under the conditions, raising the temperature to 140 ℃, and introducing ethylenePressure 3MPa, and introduction of CGC catalyst Cp SiMe 2 NBu t TiCl 2 1mL of the toluene solution (CGC catalyst: 1. mu. mol/mL; triethylaluminum: 0.2 mmol/mL; triphenylcarbenium tetrakis (pentafluorophenyl) boron: 1. mu. mol/mL) was reacted for 0.2 hour, and 10mL of ethanol was added to terminate the reaction, whereby 4.29g of a polymer was obtained.
The reaction products of examples 1-8 of the present invention and the comparative reaction products were analyzed and the results are shown in the following table:
it can be seen from the results of product analysis that the reaction products of examples 1-8 of the present invention have the characteristics of narrow molecular weight distribution, low melting point, low crystallinity, and low glass transition temperature, and the density range is 0.857g/cm 3 ～0.906g/cm 3 The melting point range is 63.6-128.3 deg.C, the crystallinity range is 5.4-19.3%, and the molecular weight (Mw) range is 14.1 × 10 4 g/mol～26.4×10 4 g/mol, the molecular weight distribution (PDI) range is 1.29-2.43, the glass transition temperature range is-68.3 ℃ to-48.7 ℃, and the melt index range is 0.5g/10min to 14.5g/10 min.
Compared with the comparative examples 1-4 which use the metallocene catalyst as the ethylene/alpha-olefin copolymerization catalyst to prepare the polyolefin elastomer through direct copolymerization or ethylene in-situ copolymerization, the polyolefin elastomer product with more excellent performance can be obtained by controlling the process conditions by using the in-situ synthesis method described in the invention.
Claims (8)
1. A method for in situ synthesis of a polyolefin elastomer, comprising:
in an inert solvent and in the presence of an oligomerization catalyst and a cocatalyst, carrying out oligomerization reaction by taking ethylene as a raw material to obtain alpha-olefin, then adding a copolymerization catalyst and the cocatalyst, and carrying out in-situ copolymerization reaction under the action of the catalyst to prepare a polyolefin elastomer;
the oligomerization catalyst is a diphosphonic amine chromium catalyst with a structural formula A; the copolymerization catalyst is a pyridine amino hafnium catalyst with a structural formula B; the molar ratio of the oligomerization catalyst to the copolymerization catalyst is 0.2: 1-20: 1;
the catalyst promoters of the oligomerization reaction and the copolymerization reaction are the same or different;
the cocatalyst for oligomerization reaction is an aluminum-containing cocatalyst and/or a boron-containing cocatalyst; the cocatalyst of the copolymerization reaction is an aluminum-containing cocatalyst and/or a boron-containing cocatalyst;
2. the in situ synthesis method according to claim 1, wherein the inert solvent is one or more of normal alkane, isoparaffin, cycloparaffin and branched aromatic hydrocarbon.
3. The in-situ synthesis method according to claim 1, wherein the reaction temperature of the oligomerization reaction is 10-100 ℃, the ethylene pressure is 1-10 MPa, and the oligomerization reaction time is 0.1-2 h; the temperature of the copolymerization reaction is 30-150 ℃, the ethylene pressure is 1-10 MPa, and the copolymerization reaction time is 0.1-1 h.
4. The in situ synthesis method of claim 3, wherein the oligomerization conditions comprise: the reaction temperature is 30-70 ℃, the ethylene pressure is 1-5 MPa, and the reaction time is 0.4-1 h.
5. The in situ synthesis method of claim 3, wherein the copolymerization reaction conditions comprise: the reaction temperature is 80-140 ℃, the ethylene pressure is 1-4 MPa, and the reaction time is 0.1-0.5 h.
6. The in-situ synthesis method of claim 1, wherein the aluminum-containing cocatalyst is one or more of methylaluminoxane, modified methylaluminoxane, triethylaluminum and triisobutylaluminum; the boron-containing cocatalyst is one or more of tri (pentafluorophenyl) boron, triphenyl carbenium tetrakis (pentafluorophenyl) boron and N, N-dimethylanilinium tetrakis (pentafluorophenyl) boron.
7. The in situ synthesis method according to claim 4,
if the cocatalyst for the oligomerization reaction is an aluminum-containing cocatalyst, the molar ratio of the oligomerization catalyst to the aluminum-containing cocatalyst is 1 (50-1000);
if the cocatalyst for the oligomerization reaction is an aluminum-containing cocatalyst and a boron-containing cocatalyst, the molar ratio of the oligomerization catalyst to the aluminum-containing cocatalyst to the boron-containing cocatalyst is 1 (50-1000) to 1-5;
if the cocatalyst of the copolymerization reaction is an aluminum-containing cocatalyst, the molar ratio of the copolymerization catalyst to the aluminum-containing cocatalyst is 1 (50-1000);
if the cocatalyst of the copolymerization reaction is a boron-containing cocatalyst, the molar ratio of the copolymerization catalyst to the boron-containing cocatalyst is 1 (1-5).
8. The in-situ synthesis method according to claim 1, wherein in the oligomerization reaction, the concentration of the oligomerization catalyst in the reaction system is 1 to 20 μmol/L; in the copolymerization reaction, the concentration of the copolymerization catalyst in a reaction system is 1-20 mu mol/L.
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| CN1727367A (en) * | 2005-07-27 | 2006-02-01 | 大庆石油学院 | Catalyst system of ethane copolymerization in situ for producing linear polyethylene in low density |
| US20070232481A1 (en) * | 2006-03-10 | 2007-10-04 | Petrochina Company Limited | Catalyst composition for ethylene oligomerization and the use thereof |
| CN113527352A (en) * | 2020-04-17 | 2021-10-22 | 中国石油天然气股份有限公司 | Pyridine amino hafnium compound and preparation method and application thereof |
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