CN117586441A - Narrow-distribution ultra-high molecular weight polymer based on alpha-olefin, and preparation method and application thereof - Google Patents
Narrow-distribution ultra-high molecular weight polymer based on alpha-olefin, and preparation method and application thereof Download PDFInfo
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- 238000009826 distribution Methods 0.000 title claims abstract description 85
- 239000004711 α-olefin Substances 0.000 title claims abstract description 57
- 229920006158 high molecular weight polymer Polymers 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 100
- 239000003054 catalyst Substances 0.000 claims abstract description 92
- 229920000642 polymer Polymers 0.000 claims abstract description 66
- 239000000178 monomer Substances 0.000 claims abstract description 54
- 230000009467 reduction Effects 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 9
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000011777 magnesium Substances 0.000 claims description 43
- 238000001914 filtration Methods 0.000 claims description 33
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 25
- -1 ethyl-isobutyl Chemical group 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- 238000001291 vacuum drying Methods 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 10
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 claims description 9
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-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 5
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- RTAQCQOZRWKSTQ-UHFFFAOYSA-N CC(C)C[Mg]CC(C)C Chemical compound CC(C)C[Mg]CC(C)C RTAQCQOZRWKSTQ-UHFFFAOYSA-N 0.000 claims description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 3
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 3
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 3
- YHNWUQFTJNJVNU-UHFFFAOYSA-N magnesium;butane;ethane Chemical compound [Mg+2].[CH2-]C.CCC[CH2-] YHNWUQFTJNJVNU-UHFFFAOYSA-N 0.000 claims description 3
- DLPASUVGCQPFFO-UHFFFAOYSA-N magnesium;ethane Chemical compound [Mg+2].[CH2-]C.[CH2-]C DLPASUVGCQPFFO-UHFFFAOYSA-N 0.000 claims description 3
- 230000001603 reducing effect Effects 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000001924 cycloalkanes Chemical class 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000003426 co-catalyst Substances 0.000 claims 1
- 239000003638 chemical reducing agent Substances 0.000 abstract description 26
- 229920001577 copolymer Polymers 0.000 description 99
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 88
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 73
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 62
- 238000012360 testing method Methods 0.000 description 53
- 239000000243 solution Substances 0.000 description 48
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 44
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 32
- 229940069096 dodecene Drugs 0.000 description 29
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
- 238000004062 sedimentation Methods 0.000 description 23
- 238000007334 copolymerization reaction Methods 0.000 description 22
- 230000006399 behavior Effects 0.000 description 16
- 230000009477 glass transition Effects 0.000 description 16
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 15
- 230000009471 action Effects 0.000 description 15
- 150000001336 alkenes Chemical class 0.000 description 15
- 238000012512 characterization method Methods 0.000 description 15
- 238000003780 insertion Methods 0.000 description 15
- 230000037431 insertion Effects 0.000 description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 15
- 230000006641 stabilisation Effects 0.000 description 15
- 238000011105 stabilization Methods 0.000 description 15
- 239000000725 suspension Substances 0.000 description 15
- 238000004458 analytical method Methods 0.000 description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 13
- 230000007935 neutral effect Effects 0.000 description 13
- 229920013639 polyalphaolefin Polymers 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000005311 nuclear magnetism Effects 0.000 description 12
- 238000001179 sorption measurement Methods 0.000 description 12
- 239000003708 ampul Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- 238000005859 coupling reaction Methods 0.000 description 8
- 229920001519 homopolymer Polymers 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000010907 mechanical stirring Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 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 description 2
- ZMZGFLUUZLELNE-UHFFFAOYSA-N 2,3,5-triiodobenzoic acid Chemical compound OC(=O)C1=CC(I)=CC(I)=C1I ZMZGFLUUZLELNE-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical group ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 238000004639 Schlenk technique Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012660 binary copolymerization Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N dodecahydrosqualene Natural products CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 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 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17D—PIPE-LINE SYSTEMS; PIPE-LINES
- F17D1/00—Pipe-line systems
- F17D1/08—Pipe-line systems for liquids or viscous products
- F17D1/16—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/14—Monomers containing five or more carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/14—Monomers containing five or more carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Public Health (AREA)
- Water Supply & Treatment (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention discloses a narrow-distribution ultra-high molecular weight polymer based on alpha-olefin, and a preparation method and application thereof, belonging to the technical field of oil drag reducer, wherein the preparation method comprises the following steps: mixing a hydrocarbon compound solvent with alpha-olefin, sequentially adding a cocatalyst and a Ti-Mg catalyst, carrying out polymerization reaction for 2-168 h at the temperature of minus 30-30 ℃, and adding a terminator to terminate the reaction after the polymerization is completed to obtain a reaction solution; the acidified precipitant is added into the reaction liquid, and the reaction liquid is filtered, washed, dissolved, adsorbed, filtered, settled, washed and vacuum dried to obtain the polymer with narrow distribution and ultra-high molecular weight (drag reduction efficiency can reach more than 60%), the molecular weight and structure of the polymer are controllable, the molecular weight distribution is narrow (< 3), no external electron donor is needed, the solvent consumption is small, and the monomer conversion rate is high.
Description
Technical Field
The invention belongs to the technical field of oil drag reducers, and particularly relates to an alpha-olefin-based narrow-distribution ultrahigh molecular weight polymer, and a preparation method and application thereof.
Background
With the development of industry, petroleum as blood in modern industry and people's production and life become inseparable. The demand for petroleum and petroleum products in modern society is increasing year by year. The pipeline transportation is used as the most important transportation mode of the oil products, and has the advantages of high transportation efficiency, low maintenance cost and the like. However, in the pipeline transportation process, turbulent vortex can be generated for kinetic energy is lost along a non-radial direction, and the phenomenon can accelerate pipeline aging to bring potential safety hazards, and meanwhile, energy loss of a conveying pump can be caused, so that the petroleum transportation efficiency is reduced. In order to cope with the phenomenon, a small amount of drag reducer is often added into oil products in engineering so as to improve the pipeline transportation efficiency and reduce the pressure drop of oil pipelines.
The conventional pipeline transportation drag reducer can be divided into a polymer drag reducer, a surfactant drag reducer and a molecular association drag reducer, wherein the application range is the widest, the cost is the lowest, and the most attractive drag reducer belongs to an ultra-high molecular weight poly alpha-olefin (PAO) drag reducer, and the ppm addition of the drag reducer can obviously reduce the pipeline pressure drop, improve the transportation efficiency, has the advantages of small using amount, good oil solubility, no pollution to samples and the like, and is concerned by academic circles and industry. A number of polymeric materials having drag reducing effects have been developed, including poly (1-hexene), poly (1-octene), poly (ethylene-propylene) (EP type), poly (ethylene-propylene-octene) (EPO type), polyethylene oxide (PEO), polyacrylamide, etc., which are the dominant drag reducer materials. The EP type and the EPO type realize commercialization, the drag reduction efficiency can reach 20%, and the EP type and the EPO type have the advantages of higher thermal decomposition temperature, better solubility and the like, and have wide application in various high-end fields. However, EP-type and EPO-type drag reducers are large in dosage and easy to degrade, which not only limits the service time of the drag reducer, but also increases the cost of the drag reducer. The polymer taking long-chain alpha-olefin as a monomer has a unique fully branched structure, and shows a random coil shape after being dissolved in an oil product, thereby being beneficial to improving the drag reduction efficiency. For example, ma Yangong et al prepared a binary copolymerization drag reducer of 1-pentene and 1-dodecene, and found that the introduction of 1-pentene monomer into the copolymer can reduce crystallinity and enhance solubility, but the prepared polymer has smaller molecular weight and wide molecular weight distribution, and is difficult to realize efficient regulation and control of molecular weight.
The synthesis of drag reducers previously reported has relied primarily on conventional ziegler-natta type catalysts, which are heterogeneous and have multiple active sites, resulting in a broad molecular weight distribution index of the resulting polymer, typically between 8 and 20. Although the apparent molecular weight of the product is relatively high, which may exceed three million or more, the product composition is heterogeneous, in which a large number of high, low molecular weight, unequal mixtures are present. Since low molecular components reduce drag reduction efficiency, this directly affects the stability of product composition and performance, and makes it difficult to achieve a substantial increase in drag reduction efficiency by effectively increasing the content of components having high drag reduction efficiency. Therefore, obtaining a polyalphaolefin drag reducer with narrow molecular weight distribution and uniform high molecular weight component distribution by reasonably designing the composition of the catalyst system is a highly desirable problem
Disclosure of Invention
The invention provides a narrow-distribution and ultra-high molecular weight polymer based on alpha-olefin, a preparation method and application thereof, wherein the polymer obtained by the invention is a copolymer or a homopolymer, the catalyst composition is optimized, the catalyst for preparing the narrow-distribution and ultra-high molecular weight copolymer based on the alpha-olefin comprises a Ti-Mg catalyst which is a main catalyst and triethylaluminum which is a cocatalyst, and the catalyst efficiently catalyzes homo-polymerization and copolymerization of long-chain alpha-olefin, so that a series of high-performance poly alpha-olefin (PAO) drag reducing agents with ultra-high molecular weight and narrow molecular weight distribution (the molecular weight distribution index can be as low as 1.5) are prepared. Aiming at the state of the art, the polymerization conditions are optimized, the synthesis of copolymer materials with high comprehensive performance (high temperature resistance, high drag reduction performance, ultra-high molecular weight, high shear resistance and the like) is realized, and the wide application of ultra-high molecular weight copolymers in the oil product pipeline transportation field is further widened.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a narrow distribution, ultra-high molecular weight polymer based on alpha-olefins having the structural formula:
wherein x=5000 to 50000, y=5000 to 50000, z 1 =0 or 250 to 10000; z 2 =0 or 250 to 10000, a=2 to 18, b=2 to 18, the above letters (a, b, x, y, z 1 And z 2 ) The numbers are represented, in the actual sense, by the number of repetitions of the structural unit in brackets. z 1 And z 2 The actual values in the same polymer are not necessarily the same (e.g. z in a certain polymer 1 ＝z 2 =5000, but z in another polymer 1 ＝0，z 2 ＝6000)。
Further, the narrow distribution, ultra-high molecular weight polymer based on alpha-olefins has the formula x=25000, y=25000; a=4, b=6.
Further, the narrow distribution, ultra-high molecular weight alpha-olefin-based polymer exhibits a white or transparent amorphous solid, has tackiness and elasticity; absence of T g The method comprises the steps of carrying out a first treatment on the surface of the A weight average molecular weight of greater than 300X 10 4 g/mol, and the molecular weight distribution is between 1.5 and 3.0; the conversion rate of the monomer is between 60 and 100 percent; the drag reduction efficiency of the polymer is between 20% and 60%.
The invention has the advantages of narrow distribution based on alpha-olefin, high drag reduction efficiency of ultra-high molecular weight polymer reaching more than 60%, controllable molecular weight and structure of the polymer, narrow molecular weight distribution (3), no need of adding external electron donor, low solvent consumption and high monomer conversion rate.
The invention also provides a preparation method of the narrow-distribution ultrahigh molecular weight polymer based on the alpha-olefin, which comprises the following steps:
mixing a hydrocarbon compound solvent with a polymerization monomer, sequentially adding a cocatalyst and a heterogeneous multi-active center Ti-Mg catalyst, carrying out polymerization reaction for 2-168 h at the temperature of minus 30-30 ℃, adding a terminator to terminate the reaction after the polymerization is completed, and obtaining a reaction solution, and preferably carrying out polymerization for 2-12 h at the temperature of minus 5-0 ℃;
adding an acidified precipitant into the reaction liquid, and obtaining the narrow-distribution and ultra-high molecular weight polymer based on alpha-olefin through filtering, washing, dissolving, adsorbing, filtering, settling, washing and vacuum drying.
Further, the hydrocarbon solvent includes at least one of benzene and its homologs (toluene and xylene), naphthalene and its homologs, alkane and its homologs, and cycloalkane and its homologs.
Further, the total volume of the polymerization is 50-200 mL.
Further, the molar concentration of the polymerized monomer in the hydrocarbon solvent is 0.1 to 4mol/L.
Further, the polymerized monomer is an alpha-olefin comprising a C-number 4 ～C 20 One or more of the alpha-olefins.
Further, the method for preparing the narrow-distribution ultra-high molecular weight polymer based on the alpha-olefin further comprises a process of adding 4-methyl 1-pentene or 3-methyl 1-butene, wherein the 4-methyl 1-pentene or 3-methyl 1-butene accounts for 0.5 to 10 percent of the total mole of the polymerized monomers. The addition or non-addition of the 4-methyl-1-pentene and the 3-methyl-1-butene has different effects, and the addition of a small amount of one of the two monomers during copolymerization can increase the drag reduction effect of the polymer at low temperature; but when the modified polypropylene is used under normal temperature, the modified polypropylene has better drag reduction effect without adding the modified polypropylene during copolymerization.
Further, when 4-methyl 1-pentene or 3-methyl 1-butene is added, hydrocarbon compound solvent, polymerization monomer and 4-methyl 1-pentene or 3-methyl 1-butene are mixed, then cocatalyst and Ti-Mg catalyst are sequentially added, polymerization is carried out for 2-168 hours at the temperature of minus 30-30 ℃, and a terminator is added after polymerization is completed, so as to obtain reaction liquid;
adding an acidified precipitant into the reaction liquid, and obtaining the narrow-distribution and ultra-high molecular weight polymer based on alpha-olefin through filtering, washing, dissolving, adsorbing, filtering, settling, washing and vacuum drying.
Further, the polymerized monomer is 1-hexene, 1-octene, 1-decene or 1-dodecene, and the molar concentration of the polymerized monomer in the hydrocarbon compound solvent is 1-4 mol/L.
Further, the cocatalyst is at least one of Methylaluminoxane (MAO), dry methylaluminoxane (dMAO), ethylaluminoxane (EAO), ethyl-isobutyl aluminoxane (EBAO), trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, ethylaluminum dichloride, diethylaluminum chloride, diethyl zinc, diethyl magnesium, diisobutylmagnesium or n-butylethylmagnesium.
Further, the cocatalyst is Methylaluminoxane (MAO), dry methylaluminoxane (dMAO), ethylaluminoxane (EAO), ethyl-isobutylaluminoxane (EBAO), trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, ethylaluminum dichloride, diethylaluminum chloride, diethylzinc, diethylmagnesium, diisobutylmagnesium or a mixture of n-butylethylmagnesium with tripentylphenylborane, triperfluorobiphenylborane, triphenylmethyl tetrakis (pentafluorophenyl) borate and tert-butyltriphenylmethyl tetrakis (pentafluorophenyl) borate. The cocatalyst is preferably triethylaluminium (Et) 3 Al)。
Further, the molar ratio of the cocatalyst to the multi-active-center Ti-Mg catalyst is 1:1-500:1.
Further, the multi-active center Ti-Mg catalyst is a type of catalyst supported on MgCl 2 TiCl on the upper part 4 Multiple active site catalysts.
Further, the molar ratio of the cocatalyst to the Ti-Mg catalyst is from 25:1 to 100:1, preferably 25:1.
Further, an adsorbent is added during adsorption, and the adsorbent comprises one of 100-500 mesh silica gel powder, 100-800 mesh neutral alumina and 100-200 mesh molecular sieve, preferably 200-300 mesh neutral alumina.
Further, the precipitant includes at least one of ethanol, methanol, petroleum ether, diethyl ether, n-hexane, acetone, n-pentane, tetrahydrofuran, and dichloromethane. Preferably, the precipitating agent is a mixed solution of ethanol and hydrochloric acid with the mass fraction of 0.5wt% (volume ratio of 50:1).
The invention directly designs a high-efficiency catalytic system, optimizes the catalyst composition, and can ensure narrow distribution (molecules) by efficiently catalyzing polymerization of two or more long-chain alpha-olefinsThe weight distribution is between 1.5 and 3), the crystallization performance is greatly reduced while the ultra-high molecular weight is realized, the distribution is narrower, so that the long chain of a high molecular weight section with a drag reduction effect is more, and the method for preparing the narrow-distribution ultra-high molecular weight drag reducer is not reported up to the present. The invention uses the load to load on MgCl 2 TiCl on the upper part 4 As a main catalyst, triethylaluminum (Et) 3 Al) is used as a cocatalyst to catalyze the copolymerization of alpha-olefin, a series of high-performance poly alpha-olefin (PAO) drag reducing agents with ultra-high molecular weight and narrow molecular weight distribution (the molecular weight distribution index can be as low as 1.5) are synthesized, and the method has wide development prospect in the field of drag reduction in oil pipeline transportation.
The invention also provides application of the narrow-distribution ultra-high molecular weight polymer based on the alpha-olefin in drag reduction materials.
The invention explores the rule of influence of different concentrations, different monomer feed ratios and different molecular weights on the drag reduction performance of the polymer. In addition, the synthesized series of copolymers are characterized, and the microscopic chemical structure of the polymer is characterized by adopting a high Wen Heci carbon spectrum, the molecular weight and the distribution of the polymer are tested by adopting high-temperature GPC, the thermal behaviors of the polymer are researched by DSC and XRD, the thermal decomposition temperature of the polymer is characterized by TGA, the drag reduction performance of the polymer is tested by adopting a loop pipeline circulation experiment, and the like.
The invention mainly uses MgCl 2 TiCl on the upper part 4 As a main catalyst and alkyl aluminum as a cocatalyst, different catalytic systems are formed, and the ratio of the main catalyst to the cocatalyst, the reaction temperature, the reaction time and the initial monomer molar ratio are optimized to synthesize a series of narrow-distribution ultrahigh molecular weight high molecular polymers with excellent drag reduction performance. First, according to the excellent copolymerization ability of Ti-Mg catalyst to various alpha-olefins, the influence of the polymerization molecular weight of the alpha-olefins under different conditions is systematically studied to realize the control of the molecular weight of the polymer. In addition, the rule of influence on the drag reduction performance of the polymer is explored by changing the monomer proportion and different reaction conditions.
GPC results show that the total concentration of the monomers is kept fixed in a Ti-Mg catalyst polymerization system, the reaction time is prolonged, the molecular weight of the copolymer is increased, and the drag reduction performance is improved; the molar ratio of the monomer to the catalyst is increased, the molecular weight of the polymer is increased, and the drag reduction performance is improved and then reduced. In general, drag reduction rates can be up to 60% or more.
In conclusion, the invention can efficiently synthesize the ultra-high molecular weight poly alpha-olefin with narrow molecular weight distribution, and the obtained polymer with high drag reduction performance is expected to be widely applied to the field of oil pipeline transportation.
Compared with the prior art, the invention has the following advantages and technical effects:
the invention synthesizes a series of narrow-distribution ultra-high molecular weight poly alpha-olefins by utilizing Ti-Mg catalyst in combination with cocatalyst (alkyl aluminum) and external electron donor, according to the characteristics of the catalyst having copolymerization capability to different alpha-olefins, the invention can realize the high efficiency and the controllability of the monomer content, the molecular weight, the distribution and the chain segment microstructure in the polymer according to the different monomer feeding ratio, the reaction time and the mole ratio of the monomer to the catalyst, and can prepare the narrow-distribution ultra-high molecular weight poly alpha-olefins with high drag reduction performance, and the molecular weight of the copolymer prepared by the invention is 3 to 10 multiplied by 10 6 The g/mol ratio is adjustable. By adjusting the feed ratio of different alpha-olefins, the drag reduction efficiency of the copolymer can be changed. Drag reduction efficiencies can be as high as 60% when the ratio of 1-octene to 1-decene in the polymer is near 1:1. It is notable that the low-cost alkyl metal is used as a cocatalyst in the invention, and the catalyst can be matched with Ti-Mg catalyst to catalyze the copolymerization of the two catalysts with high efficiency, so that the catalyst has potential of commercial value. In addition, the narrow-distribution ultra-high molecular weight poly-alpha-olefin synthesized by the method can also maintain better heat resistance, and strategies for synthesizing the narrow-distribution ultra-high molecular weight poly-alpha-olefin are not reported in various technical fields, so that the wide application of the narrow-distribution ultra-high molecular weight poly-alpha-olefin material in the field of oil product pipeline transportation is expected to be widened.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application, illustrate and explain the application and are not to be construed as limiting the application. In the drawings:
FIG. 1 is a high temperature GPC chart of 1-octene/1-decene copolymers of some examples;
FIG. 2 is a graph of the primary cooling curve (a) and the secondary heating curve (b) of DSC of 1-octene/1-decene copolymer in some examples;
FIG. 3 is an XRD plot of the 1-octene/1-decene copolymer of some of the examples;
FIG. 4 is a molecular weight-drag reduction histogram of the 1-octene/1-decene copolymer of some examples;
FIG. 5 is a plot of polymerization time versus molecular weight (a) and polymerization time versus drag reduction ratio for a 1-octene/1-decene copolymer of some of the examples.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The solvents involved in the present invention are all post-treated anhydrous and oxygen-free solvents, and in addition, all moisture and oxygen sensitive operations in the preparation of narrow-distribution, ultra-high molecular weight alpha-olefin based polymers are performed by those skilled in the art in an MBraun glove box or under nitrogen protection using standard Schlenk techniques.
The narrow distribution, ultra-high molecular weight polymers based on alpha-olefins obtained were tested for their chemical structure by nuclear magnetic resonance spectroscopy (NMR), their thermal properties by Differential Scanning Calorimeter (DSC), their molecular weight and molecular weight distribution by high temperature gel chromatography (GPC). Wherein the copolymer 1 H and 13 CNMR is measured by Bruker-400 nuclear magnetic resonance at 120deg.C, TMS is an internal standard, and the solvent is deuterated o-dichlorobenzene or deuterated 1, 2-tetrachloroethane. Copolymer glass transition temperature (T) g ) Determined by differential scanning calorimeter (Q2000 DSC), test procedure is: heating to 100 ℃ at 20 ℃/min, preserving heat for 3min to eliminate the heat history of the material, then cooling to-70 ℃ at the speed of 10 ℃/min, and preserving heat for 3min to obtain a cooling curve; and finally, heating to 100 ℃ at a speed of 10 ℃/min, and preserving heat for 3min to obtain a secondary heating curve. The crystallization performance of the polymer was measured by X-ray diffractometry (XRD), and the polymer was prepared into a 0.5mm thick film for testing, with a test angle range of 2θ=10° to 90 °, and a scan speed of 10 °/min. Gel chromatography was measured using a Gel Permeation Chromatograph (GPC) PL GPC-220 type gel permeation chromatograph. The tester is RI-Laser, the PL EasiCal PS-1 is used as standard sample, the packed column is Plgel 10 μm MIXED-BLS,1,2, 4-Trichlorobenzene (TCB) is used as solvent (0.05wt% of 2, 6-di-tert-butyl-4-methylphenol (BHT) is added as antioxidant, the test temperature is 150deg.C, the flow rate is 1.0mL/min. According to industry standard SY%T6578-2016 (technical Specification for conveying additive drag reducer for oil pipeline), taking a drag reducing polymer to be tested and No. 0 diesel oil to prepare a solution of 1g/L, and measuring by using an indoor loop drag reduction testing device after the polymer is completely dissolved and uniformly distributed. Through testing, under the same conditions, the friction pressure drop of the test pipe section of the indoor loop is measured before and after the drag reducer is added into the liquid, the drag reduction rate is calculated according to the formula (1), and the drag reduction effect of the drag reducer is evaluated according to the drag reduction rate.
Wherein DR is drag reduction effect (%), ΔP 0 For the solvent without the drag reducer, the pressure drop (KPa) and delta P generated by friction of the test instrument pipeline under a certain temperature condition DRA To prepare a solution of drag reducer at a certain concentration, the solution is passed through the same pipeline to obtain the pressure drop (KPa) of the oil after the drag reducer is added.
The Ti-Mg catalyst of the invention has the brand of LP-21-S01, and other cocatalysts, polymerization monomers, solvents and the like are purchased from Annaiji chemical company in China.
The technical scheme of the invention is further described by the following examples.
Example 1
Preparation method of narrow-distribution ultrahigh molecular weight polymer based on alpha-olefin by adopting Ti-Mg catalyst/Et 3 The coordination copolymerization of olefin by using Al as catalyst is carried out under anhydrous and anaerobic condition, all polymerization reactions are carried out, and the weighing of polymerization bottles, syringes, ampoule bottles and other glass vessels for transferring catalyst, cocatalyst, solution and the like are subjected to anhydrous and anaerobic treatment. The specific reaction steps are as follows: 100mmol of 1-octene (concentration: 2 mol/L) was added under nitrogen atmosphere using a Schlenk's experimental apparatus; after stabilization, triethylaluminum solution (0.6 mmol) as a cocatalyst and a cyclohexane suspension of a Ti-Mg catalyst (16 mu mol) are sequentially added, the total capacity of a polymerization bottle is maintained at 50mL, and the polymerization bottle is stirred and reacted for 120min under the action of 400rpm at 0 ℃; after the polymerization was completed, the reacted solution was poured dropwise into a container containing 300m Settling in a beaker with L-ethanol/hydrochloric acid (volume ratio of 50:1), filtering, washing, redissolving the polymer with 50mL of dimethylbenzene, adsorbing with neutral alumina, settling again, filtering again, and vacuum drying to obtain 1-octene homopolymer with a structural formula ofx≈3.5×10 5 And (5) carrying out subsequent characterization.
The 1-octene homopolymer obtained above was subjected to nuclear magnetism and DSC tests, and the results of the tests show that the homopolymer has no glass transition temperature, and the polymerization shows amorphous behavior, and the monomer conversion rate is 87.16%. Analysis of the high temperature GPC result showed that the weight average molecular weight was 3.89×10 6 g/mol, narrow molecular weight distribution (pdi=2.21). The loop pipeline circulation test result shows that the drag reduction efficiency of the copolymer is 43.01%. The data for the specific copolymers are shown in table 1.
Example 2
Preparation method of narrow-distribution ultrahigh molecular weight polymer based on alpha-olefin by adopting Ti-Mg catalyst/Et 3 The coordination copolymerization of olefin by using Al as catalyst is carried out under anhydrous and anaerobic condition, all polymerization reactions are carried out, and the weighing of polymerization bottles, syringes, ampoule bottles and other glass vessels for transferring catalyst, cocatalyst, solution and the like are subjected to anhydrous and anaerobic treatment. The specific reaction steps are as follows: 83mmol of 1-octene (concentration: 1.67 mol/L) was added under nitrogen atmosphere using a Schlenk's experimental apparatus; then 17mmol of 1-decene (concentration 0.33 mol/L) was added; after stabilization, triethylaluminum solution (0.6 mmol) as a cocatalyst and a cyclohexane suspension of a Ti-Mg catalyst (16 mu mol) are sequentially added, the total capacity of a polymerization bottle is maintained at 50mL, and the polymerization bottle is stirred and reacted for 120min under the action of 400rpm at 0 ℃; after the polymerization is finished, the reacted solution is poured into a beaker containing 300mL of ethanol/hydrochloric acid (volume ratio of 50:1) dropwise for sedimentation, then the polymer is dissolved again by 50mL of dimethylbenzene after filtration and washing, and the 1-octene/1-decene copolymer is obtained by neutral alumina adsorption, sedimentation, filtration and vacuum drying, wherein the structural formula is that x≈2.9×10 5 ，y≈0.6×10 5 And (5) carrying out subsequent characterization.
The 1-octene/1-decene copolymer obtained in the above was subjected to nuclear magnetism and DSC test, and the results of the test showed that the 1-decene insertion rate in the 1-octene/1-decene copolymer obtained by polymerization in this example was 16.7mol% and substantially identical to the monomer feed ratio. The copolymer had no glass transition temperature and the polymerization exhibited amorphous behavior with a monomer conversion of 84.51%. Analysis of the high temperature GPC results showed a weight average molecular weight of 3.99X10 6 g/mol, narrow molecular weight distribution (pdi=3.01). The loop pipeline circulation test result shows that the drag reduction efficiency of the copolymer is 48.10%. The data for the specific copolymers are shown in table 1.
Example 3
Preparation method of narrow-distribution ultrahigh molecular weight polymer based on alpha-olefin by adopting Ti-Mg catalyst/Et 3 The coordination copolymerization of olefin by using Al as catalyst is carried out under anhydrous and anaerobic condition, all polymerization reactions are carried out, and the weighing of polymerization bottles, syringes, ampoule bottles and other glass vessels for transferring catalyst, cocatalyst, solution and the like are subjected to anhydrous and anaerobic treatment. The specific reaction steps are as follows: 75mmol of 1-octene (concentration: 1.5 mol/L) was added under nitrogen atmosphere using a Schlenk's experimental apparatus; then 25mmol of 1-decene (concentration 0.5 mol/L) was added; after stabilization, triethylaluminum solution (0.6 mmol) as a cocatalyst and a cyclohexane suspension of a Ti-Mg catalyst (16 mu mol) are sequentially added, the total capacity of a polymerization bottle is maintained at 50mL, and the polymerization bottle is stirred and reacted for 120min under the action of 400rpm at 0 ℃; after the polymerization is finished, the reacted solution is poured into a beaker containing 300mL of ethanol/hydrochloric acid (volume ratio of 50:1) dropwise for sedimentation, then the polymer is dissolved again by 50mL of dimethylbenzene after filtration and washing, and the 1-octene/1-decene copolymer is obtained by neutral alumina adsorption, sedimentation, filtration and vacuum drying, wherein the structural formula is that x≈2.5×10 5 ，y≈0.8×10 5 And (5) carrying out subsequent characterization.
For the above-mentioned obtainedThe 1-octene/1-decene copolymer obtained by polymerization in this example showed a 1-decene insertion rate of 24.8mol% and a monomer feed ratio substantially consistent with the results of nuclear magnetic resonance and DSC tests. The copolymer had no glass transition temperature and the polymerization exhibited amorphous behavior with a monomer conversion of 85.87%. Analysis of the high temperature GPC results showed that the weight average molecular weight was 3.65X10 6 g/mol, narrow molecular weight distribution (pdi=2.70). The loop pipeline circulation test result shows that the drag reduction efficiency of the copolymer is 49.12%. The data for the specific copolymers are shown in table 1.
Example 4
Preparation method of narrow-distribution ultrahigh molecular weight polymer based on alpha-olefin by adopting Ti-Mg catalyst/Et 3 The coordination copolymerization of olefin by using Al as catalyst is carried out under anhydrous and anaerobic condition, all polymerization reactions are carried out, and the weighing of polymerization bottles, syringes, ampoule bottles and other glass vessels for transferring catalyst, cocatalyst, solution and the like are subjected to anhydrous and anaerobic treatment. The specific reaction steps are as follows: 50mmol of 1-octene (concentration: 1.0 mol/L) was added under nitrogen atmosphere using a Schlenk's experimental apparatus; then, 50mmol of 1-decene (1.0 mol/L) was added; after stabilization, triethylaluminum solution (0.6 mmol) as a cocatalyst and a cyclohexane suspension of a Ti-Mg catalyst (16 mu mol) are sequentially added, the total capacity of a polymerization bottle is maintained at 50mL, and the polymerization bottle is stirred and reacted for 120min under the action of 400rpm at 0 ℃; after the polymerization is finished, the reacted solution is poured into a beaker containing 300mL of ethanol/hydrochloric acid (volume ratio of 50:1) dropwise for sedimentation, then the polymer is dissolved again by 50mL of dimethylbenzene after filtration and washing, and the 1-octene/1-decene copolymer is obtained by neutral alumina adsorption, sedimentation, filtration and vacuum drying, wherein the structural formula is that x≈1.7×10 5 ，y≈1.8×10 5 And (5) carrying out subsequent characterization.
The 1-octene/1-decene copolymer obtained in the above-mentioned manner was subjected to nuclear magnetic resonance and DSC tests, and the results of the tests showed that the 1-decene insertion rate in the 1-octene/1-decene copolymer obtained by polymerization in this example was 496mol% and the monomer feeding ratio is basically consistent. The copolymer had no glass transition temperature and the polymerization exhibited amorphous behavior with a monomer conversion of 82.84%. Analysis of the high temperature GPC results showed a weight average molecular weight of 4.50X10 6 g/mol, narrow molecular weight distribution (pdi=2.87). The loop pipeline circulation test result shows that the drag reduction efficiency of the copolymer is 56.37%. The data for the specific copolymers are shown in table 1.
Example 5
Preparation method of narrow-distribution ultrahigh molecular weight polymer based on alpha-olefin by adopting Ti-Mg catalyst/Et 3 The coordination copolymerization of olefin by using Al as catalyst is carried out under anhydrous and anaerobic condition, all polymerization reactions are carried out, and the weighing of polymerization bottles, syringes, ampoule bottles and other glass vessels for transferring catalyst, cocatalyst, solution and the like are subjected to anhydrous and anaerobic treatment. The specific reaction steps are as follows: 25mmol of 1-octene (concentration: 0.5 mol/L) was added under nitrogen atmosphere using a Schlenk's experimental apparatus; then, 75mmol of 1-decene (1.5 mol/L) was added; after stabilization, triethylaluminum solution (0.6 mmol) as a cocatalyst and a cyclohexane suspension of a Ti-Mg catalyst (16 mu mol) are sequentially added, the total capacity of a polymerization bottle is maintained at 50mL, and the polymerization bottle is stirred and reacted for 120min under the action of 400rpm at 0 ℃; after the polymerization is finished, the reacted solution is poured into a beaker containing 300mL of ethanol/hydrochloric acid (volume ratio of 50:1) dropwise for sedimentation, then the polymer is dissolved again by 50mL of dimethylbenzene after filtration and washing, and the 1-octene/1-decene copolymer is obtained by neutral alumina adsorption, sedimentation, filtration and vacuum drying, wherein the structural formula is that x≈0.9×10 5 ，y≈2.6×10 5 And (5) carrying out subsequent characterization.
The 1-octene/1-decene copolymer obtained in the above was subjected to nuclear magnetism and DSC test, and the results of the test showed that the 1-octene insertion rate in the 1-octene/1-decene copolymer obtained by polymerization in this example was 24.2mol% and was substantially consistent with the monomer feed ratio. The copolymer had no glass transition temperature and the polymerization exhibited amorphous behavior with a monomer conversion of 82.74%. High temperature GPC resultsAnalysis showed that the weight average molecular weight was 4.44×10 6 g/mol, narrow molecular weight distribution (pdi=2.64). The loop pipeline circulation test result shows that the drag reduction efficiency of the copolymer is 42.61%. The data for the specific copolymers are shown in table 1.
Example 6
Preparation method of narrow-distribution ultrahigh molecular weight polymer based on alpha-olefin by adopting Ti-Mg catalyst/Et 3 The coordination copolymerization of olefin by using Al as catalyst is carried out under anhydrous and anaerobic condition, all polymerization reactions are carried out, and the weighing of polymerization bottles, syringes, ampoule bottles and other glass vessels for transferring catalyst, cocatalyst, solution and the like are subjected to anhydrous and anaerobic treatment. The specific reaction steps are as follows: 17mmol of 1-octene (concentration: 0.33 mol/L) was added under nitrogen atmosphere using a Schlenk's experimental apparatus; then 83mmol of 1-decene (1.67 mol/L) was added; after stabilization, triethylaluminum solution (0.6 mmol) as a cocatalyst and a cyclohexane suspension of a Ti-Mg catalyst (16 mu mol) are sequentially added, the total capacity of a polymerization bottle is maintained at 50mL, and the polymerization bottle is stirred and reacted for 120min under the action of 400rpm at 0 ℃; after the polymerization is finished, the reacted solution is poured into a beaker containing 300mL of ethanol/hydrochloric acid (volume ratio of 50:1) dropwise for sedimentation, then the polymer is dissolved again by 50mL of dimethylbenzene after filtration and washing, and the 1-octene/1-decene copolymer is obtained by neutral alumina adsorption, sedimentation, filtration and vacuum drying, wherein the structural formula is that x≈0.6×10 5 ，y≈2.8×10 5 And (5) carrying out subsequent characterization.
The 1-octene/1-decene copolymer obtained in the above was subjected to nuclear magnetism and DSC test, and the results of the test showed that the 1-octene insertion rate in the 1-octene/1-decene copolymer obtained by polymerization in this example was 17.2mol% and was substantially consistent with the monomer feed ratio. The copolymer has no glass transition temperature, and the polymerization shows amorphous behavior, and the monomer conversion rate is 88.20%. Analysis of the high temperature GPC results showed a weight average molecular weight of 3.88X10 6 g/mol, narrow molecular weight distribution (pdi=2.80). The loop pipeline circulation test result shows that the drag reduction efficiency of the copolymer is39.79%. The data for the specific copolymers are shown in table 1.
Example 7
Preparation method of narrow-distribution ultrahigh molecular weight polymer based on alpha-olefin by adopting Ti-Mg catalyst/Et 3 The coordination copolymerization of olefin by using Al as catalyst is carried out under anhydrous and anaerobic condition, all polymerization reactions are carried out, and the weighing of polymerization bottles, syringes, ampoule bottles and other glass vessels for transferring catalyst, cocatalyst, solution and the like are subjected to anhydrous and anaerobic treatment. The specific reaction steps are as follows: 100mmol of 1-decene (concentration: 2 mol/L) was added under nitrogen atmosphere using a Schlenk's experimental apparatus; after stabilization, triethylaluminum solution (0.6 mmol) as a cocatalyst and a cyclohexane suspension of a Ti-Mg catalyst (16 mu mol) are sequentially added, the total capacity of a polymerization bottle is maintained at 50mL, and the polymerization bottle is stirred and reacted for 120min under the action of 400rpm at 0 ℃; after the polymerization is finished, the reacted solution is poured into a beaker containing 300mL of ethanol/hydrochloric acid (volume ratio of 50:1) dropwise for sedimentation, then the polymer is dissolved again by 50mL of dimethylbenzene after filtration and washing, and the 1-decene homopolymer is obtained by neutral alumina adsorption, sedimentation, filtration and vacuum drying, wherein the structural formula is as follows x≈3.0×10 5 And (5) carrying out subsequent characterization.
The 1-octene homopolymer obtained as described above was subjected to nuclear magnetism and DSC testing, and the results of the tests showed that the homopolymer had no glass transition temperature and the polymerization exhibited amorphous behavior with a monomer conversion of 86.19%. Analysis of the high temperature GPC results showed a weight average molecular weight of 3.80×10 6 g/mol, narrow molecular weight distribution (pdi=2.25). Loop pipe circulation test results show that the drag reduction efficiency of the copolymer is 34.71%. The data for the specific copolymers are shown in table 1.
Example 8
Preparation method of narrow-distribution ultrahigh molecular weight polymer based on alpha-olefin by adopting Ti-Mg catalyst/Et 3 Olefin coordination copolymerization with Al as catalyst, all polymerization reactions are carried out under anhydrous and anaerobic conditions, and magnetic coupling machinery for the reactions is involvedAnd weighing and transferring the catalyst, the cocatalyst, the solution and other glassware through anhydrous and anaerobic treatment by stirring the stainless steel polymerization reaction kettle, the injector, the ampoule bottle and the like. The specific reaction steps are as follows: 50mmol of 1-hexene (concentration: 1.0 mol/L) was added under nitrogen atmosphere using a Schlenk's experimental apparatus; then, 50mmol of 1-dodecene (concentration: 1.0 mol/L) was added; after stabilization, adding a catalyst promoter triethylaluminum solution (0.6 mmol) and a 16 mu mol Ti-Mg catalyst cyclohexane suspension in sequence, maintaining the total capacity of the reaction kettle at 50mL, and stirring and reacting for 2h under the action of 400rpm at-5 ℃; after the polymerization is finished, the reacted solution is poured into a beaker containing 300mL of ethanol/hydrochloric acid (volume ratio of 50:1) dropwise for sedimentation, then the polymer is dissolved again by 50mL of dimethylbenzene after filtration and washing, and the 1-hexene/1-dodecene copolymer is obtained by neutral alumina adsorption, sedimentation, filtration and vacuum drying, wherein the structural formula is that x≈1.6×10 5 ，y≈1.7×10 5 And (5) carrying out subsequent characterization.
The 1-hexene/1-dodecene copolymer obtained in the above was subjected to nuclear magnetism and DSC test, and the results of the test showed that the 1-hexene insertion rate in the 1-hexene/1-dodecene copolymer obtained by polymerization in this example was 50.5mol% and was substantially consistent with the monomer feed ratio. The copolymer has no glass transition temperature, the polymerization shows amorphous behavior, and the monomer conversion rate is 17.50%. Analysis of the high temperature GPC results showed a weight average molecular weight of 4.18X10 6 g/mol, narrow molecular weight distribution (pdi=1.57). The loop pipeline circulation test result shows that the drag reduction efficiency of the copolymer is 35.88%. The data for the specific copolymers are shown in table 1.
Example 9
Preparation method of narrow-distribution ultrahigh molecular weight polymer based on alpha-olefin by adopting Ti-Mg catalyst/Et 3 The coordination copolymerization of olefin by using Al as catalyst is carried out under anhydrous and anaerobic condition, all polymerization reactions are carried out under anhydrous and anaerobic condition, and the magnetic coupling mechanical stirring stainless steel polymerization reaction kettle, injector, ampoule bottle and the like involved in the reaction weigh and transfer catalyst, cocatalyst, solution and the likeThe glassware is subjected to anhydrous and anaerobic treatment. The specific reaction steps are as follows: 50mmol of 1-hexene (concentration: 1.0 mol/L) was added under nitrogen atmosphere using a Schlenk's experimental apparatus; then, 50mmol of 1-dodecene (concentration: 1.0 mol/L) was added; after stabilization, adding a catalyst promoter triethylaluminum solution (0.6 mmol) and a 16 mu mol Ti-Mg catalyst cyclohexane suspension in sequence, maintaining the total capacity of the reaction kettle at 50mL, and stirring and reacting for 4h under the action of 400rpm at-5 ℃; after the polymerization is finished, the reacted solution is poured into a beaker containing 300mL of ethanol/hydrochloric acid (volume ratio of 50:1) dropwise for sedimentation, then the polymer is dissolved again by 50mL of dimethylbenzene after filtration and washing, and the 1-hexene/1-dodecene copolymer is obtained by neutral alumina adsorption, sedimentation, filtration and vacuum drying, wherein the structural formula is that x≈1.7×10 5 ，y≈1.8×10 5 And (5) carrying out subsequent characterization.
The 1-hexene/1-dodecene copolymer obtained in the above was subjected to nuclear magnetism and DSC test, and the results of the test showed that the 1-hexene insertion rate in the 1-hexene/1-dodecene copolymer obtained by polymerization in this example was 50.8mol% and was substantially consistent with the monomer feed ratio. The copolymer had no glass transition temperature and the polymerization exhibited amorphous behavior with a monomer conversion of 41.41%. Analysis of the high temperature GPC results showed a weight average molecular weight of 4.50X10 6 g/mol, narrow molecular weight distribution (pdi=1.65). Loop pipe circulation test results show that the drag reduction efficiency of the copolymer is 44.25%. The data for the specific copolymers are shown in table 1.
Example 10
Preparation method of narrow-distribution ultrahigh molecular weight polymer based on alpha-olefin by adopting Ti-Mg catalyst/Et 3 The coordination copolymerization of olefin by using Al as catalyst is carried out under anhydrous and anaerobic condition, all polymerization reactions are carried out under anhydrous and anaerobic condition, and the magnetic coupling mechanical stirring stainless steel polymerization reaction kettle, injector, ampoule bottle and other weighing and glass vessels for transferring catalyst, cocatalyst, solution and the like are subjected to anhydrous and anaerobic treatment. The specific reaction steps are as follows: using a Schlenk experimental apparatus, and introducing nitrogen Under the conditions, 50mmol of 1-hexene (concentration: 1.0 mol/L) was added; then, 50mmol of 1-dodecene (concentration: 1.0 mol/L) was added; after stabilization, adding a catalyst promoter triethylaluminum solution (0.6 mmol) and a 16 mu mol Ti-Mg catalyst cyclohexane suspension in sequence, maintaining the total capacity of the reaction kettle at 50mL, and stirring and reacting for 12h under the action of 400rpm at-5 ℃; after the polymerization is finished, the reacted solution is poured into a beaker containing 300mL of ethanol/hydrochloric acid (volume ratio of 50:1) dropwise for sedimentation, then the polymer is dissolved again by 50mL of dimethylbenzene after filtration and washing, and the 1-hexene/1-dodecene copolymer is obtained by neutral alumina adsorption, sedimentation, filtration and vacuum drying, wherein the structural formula is thatx≈2.3×10 5 ，y≈2.2×10 5 And (5) carrying out subsequent characterization.
The 1-hexene/1-dodecene copolymer obtained in the above was subjected to nuclear magnetism and DSC test, and the results of the test showed that the 1-hexene insertion rate in the 1-hexene/1-dodecene copolymer obtained by polymerization in this example was 50.5mol% and was substantially consistent with the monomer feed ratio. The copolymer had no glass transition temperature and the polymerization exhibited amorphous behavior with a monomer conversion of 77.38%. Analysis of the high temperature GPC result showed a weight average molecular weight of 5.69×10 6 g/mol, narrow molecular weight distribution (pdi=1.68). The loop pipeline circulation test result shows that the drag reduction efficiency of the copolymer is 53.10%. The data for the specific copolymers are shown in table 1.
Example 11
Preparation method of narrow-distribution ultrahigh molecular weight polymer based on alpha-olefin by adopting Ti-Mg catalyst/Et 3 The coordination copolymerization of olefin by using Al as catalyst is carried out under anhydrous and anaerobic condition, all polymerization reactions are carried out under anhydrous and anaerobic condition, and the magnetic coupling mechanical stirring stainless steel polymerization reaction kettle, injector, ampoule bottle and other weighing and glass vessels for transferring catalyst, cocatalyst, solution and the like are subjected to anhydrous and anaerobic treatment. The specific reaction steps are as follows: 50mmol of 1-hexene (concentration: 1.0 mol/L) was added under nitrogen atmosphere using a Schlenk's experimental apparatus; then, 50mmol of 1-dodecene (concentration: 1.0 mol) was addedL); after stabilization, adding a catalyst promoter triethylaluminum solution (0.6 mmol) and 16 mu mol of Ti-Mg catalyst cyclohexane suspension in sequence, maintaining the total capacity of the reaction kettle at 50mL, and stirring and reacting for 36h under the action of 400rpm at-5 ℃; after the polymerization is finished, the reacted solution is poured into a beaker containing 300mL of ethanol/hydrochloric acid (volume ratio of 50:1) dropwise for sedimentation, then the polymer is dissolved again by 50mL of dimethylbenzene after filtration and washing, and the 1-hexene/1-dodecene copolymer is obtained by neutral alumina adsorption, sedimentation, filtration and vacuum drying, wherein the structural formula is that x≈2.5×10 5 ，y≈2.4×10 5 And (5) carrying out subsequent characterization.
The 1-hexene/1-dodecene copolymer obtained in the above was subjected to nuclear magnetism and DSC test, and the results of the test showed that the 1-hexene insertion rate in the 1-hexene/1-dodecene copolymer obtained by polymerization in this example was 50.6mol% and was substantially consistent with the monomer feed ratio. The copolymer has no glass transition temperature, the polymerization shows amorphous behavior, and the monomer conversion rate is 98.88%. Analysis of the high temperature GPC results showed that the weight average molecular weight was 6.16X10 6 g/mol, narrow molecular weight distribution (pdi=1.90). The loop pipeline circulation test result shows that the drag reduction efficiency of the copolymer is 60.04%. The data for the specific copolymers are shown in table 1.
Example 12
A process for preparing the narrow-distribution ultrahigh-molecular polymer based on alpha-olefin includes such steps as coordination copolymerization of olefin by Ti-Mg catalyst/TIBA as catalyst, and magnetically coupling reaction while mechanically stirring, and anhydrous and anaerobic treatment. The specific reaction steps are as follows: using a Schlenk experimental apparatus, 50mmol of 1-hexene was added under nitrogen, followed by 50mmol of 1-dodecene; after stabilization, triisobutylaluminum solution (0.6 mmol) as a cocatalyst and a cyclohexane suspension as a Ti-Mg catalyst (16. Mu. Mol) were sequentially added thereto, and the total capacity of the reactor was maintained at 50mL, at Stirring and reacting for 12h at-5 ℃ under the action of 400 rpm; after polymerization, the reacted solution is poured into a beaker containing 300mL of methanol/hydrochloric acid (volume ratio of 50:1) dropwise for sedimentation, then filtered and washed, the polymer is redissolved by 50mL of dimethylbenzene, and the 1-hexene/1-dodecene copolymer is obtained through 100-mesh silica gel powder adsorption, sedimentation, filtration and vacuum drying, wherein the structural formula is thatx≈2.1×10 5 ，y≈2.1×10 5 And (5) carrying out subsequent characterization.
The 1-hexene/1-dodecene copolymer obtained above was subjected to nuclear magnetism and DSC test, and the results of the test showed that the 1-hexene insertion rate of the 1-hexene/1-dodecene copolymer obtained by polymerization in this example was 49.7mol% and was substantially consistent with the monomer feed ratio. The copolymer had no glass transition temperature and the polymerization exhibited amorphous behavior with a monomer conversion of 77.36%. Analysis of the high temperature GPC result showed a weight average molecular weight of 5.34×10 6 g/mol, narrow molecular weight distribution (pdi=1.61). Loop pipeline cycle test results at 0 ℃ show that the drag reduction efficiency of the copolymer is 38.73%. The data for the specific copolymers are shown in table 1.
Example 13
A process for preparing the narrow-distribution ultrahigh-molecular polymer based on alpha-olefin includes such steps as coordination copolymerization of olefin by Ti-Mg catalyst/TIBA as catalyst, and magnetically coupling reaction while mechanically stirring, and anhydrous and anaerobic treatment. The specific reaction steps are as follows: 49mmol of 1-hexene, then 49mmol of 1-dodecene and finally 2mmol of 4-methyl-1-pentene were added using a Schlenk laboratory apparatus with nitrogen; after stabilization, adding triisobutyl aluminum solution (0.6 mmol) as a cocatalyst and cyclohexane suspension as a Ti-Mg catalyst of 16 mu mol in sequence, maintaining the total capacity of the reaction kettle at 50mL, and stirring and reacting for 12h under the action of 400rpm at-5 ℃; after the polymerization was completed, the reacted solution was poured dropwise into a solution containing 300mL of methyl Settling in an alcohol/hydrochloric acid (volume ratio of 50:1) beaker, filtering, washing, redissolving the polymer with 50mL of dimethylbenzene, adsorbing by 100-mesh silica gel powder, settling again, filtering again, and vacuum drying to obtain 1-hexene/1-dodecene/4-methyl 1-pentene copolymer with a structural formula ofx≈1.9×10 5 ，y≈1.9×10 5 ，z≈0.8×10 4 And (5) carrying out subsequent characterization.
The 1-hexene/1-dodecene/4-methyl 1-pentene copolymer obtained in the above manner was subjected to nuclear magnetism and DSC test, and the results of the test showed that the 1-hexene insertion rate in the 1-hexene/1-dodecene/4-methyl 1-pentene copolymer obtained by polymerization in this example was 48.6mol% and the 4-methyl 1-pentene insertion rate was 1.9mol% and was substantially consistent with the monomer feed ratio. The copolymer had no glass transition temperature and the polymerization exhibited amorphous behavior with a monomer conversion of 76.19%. Analysis of the high temperature GPC result showed that the weight average molecular weight was 4.98X10 6 g/mol, narrow molecular weight distribution (pdi=1.72). The results of loop pipeline cycle testing at 0deg.C showed that the drag reduction efficiency of the copolymer was 44.07%. The data for the specific copolymers are shown in table 1.
Example 14
A process for preparing the narrow-distribution ultrahigh-molecular polymer based on alpha-olefin includes such steps as coordination copolymerization of olefin by Ti-Mg catalyst/TMA as catalyst, and magnetically coupling reaction, mechanical stirring, and anhydrous and anaerobic treatment. The specific reaction steps are as follows: using a Schlenk laboratory apparatus, 50mmol of 1-octene was added under nitrogen, followed by 50mmol of 1-decene; after stabilization, adding a trimethylaluminum cocatalyst solution (0.6 mmol) and a 16 mu mol Ti-Mg catalyst cyclohexane suspension in sequence, maintaining the total capacity of the reaction kettle at 50mL, and stirring and reacting for 12h under the action of 400rpm at-5 ℃; after the polymerization was completed, the reacted solution was poured dropwise into a beaker containing 300mL of acetone/hydrochloric acid (volume ratio 50:1) Settling, filtering, washing, dissolving again with 50mL toluene, adsorbing with 100 mesh silica gel powder, settling again, filtering again, and vacuum drying to obtain 1-octene/1-decene copolymer with structural formula ofx≈1.9×10 5 ，y≈1.9×10 5 And (5) carrying out subsequent characterization.
The 1-octene/1-decene obtained in the above was subjected to nuclear magnetic resonance and DSC test, and the results of the test showed that the 1-hexene insertion rate in the 1-octene/1-decene copolymer obtained by polymerization in this example was 49.6mol% and was substantially consistent with the monomer feed ratio. The copolymer had no glass transition temperature and the polymerization exhibited amorphous behavior with a monomer conversion of 80.67%. Analysis of the high temperature GPC result showed that the weight average molecular weight was 4.81×10 6 g/mol, narrow molecular weight distribution (pdi=1.64). Loop pipeline cycle test results at 0 ℃ show that the drag reduction efficiency of the copolymer is 37.82%. The data for the specific copolymers are shown in table 1.
Example 15
A process for preparing the narrow-distribution ultrahigh-molecular polymer based on alpha-olefin includes such steps as coordination copolymerization of olefin by Ti-Mg catalyst/TMA as catalyst, and magnetically coupling reaction, mechanical stirring, and anhydrous and anaerobic treatment. The specific reaction steps are as follows: 49mmol of 1-octene, then 49mmol of 1-decene and finally 2mmol of 3-methyl 1-butene were added using a Schlenk laboratory apparatus with nitrogen; after stabilization, adding a trimethylaluminum cocatalyst solution (0.6 mmol) and a 16 mu mol Ti-Mg catalyst cyclohexane suspension in sequence, maintaining the total capacity of the reaction kettle at 50mL, and stirring and reacting for 12h under the action of 400rpm at-5 ℃; after the polymerization is finished, the reacted solution is poured into a beaker containing 300mL of acetone/hydrochloric acid (volume ratio of 50:1) dropwise for sedimentation, then filtered and washed, the polymer is redissolved by 50mL of toluene, and is absorbed by 100-mesh silica gel powder and then sedimented, filtered again and true Air drying to obtain 1-octene/1-decene/3-methyl 1-butene copolymer with structural formula ofx≈1.6×10 5 ，y≈1.6×10 5 ，z≈0.6×10 4 And (5) carrying out subsequent characterization.
The 1-octene/1-decene/3-methyl 1-butene copolymer obtained in the above-mentioned manner was subjected to nuclear magnetism and DSC test, and the results of the test showed that the 1-hexene insertion rate in the 1-octene/1-decene/3-methyl 1-butene copolymer obtained by polymerization in this example was 49.1mol%, and the 4-methyl 1-pentene insertion rate was 1.7mol%, which were substantially the same as the monomer feed ratio. The copolymer had no glass transition temperature and the polymerization exhibited amorphous behavior with a monomer conversion of 79.26%. Analysis of the high temperature GPC result showed that the weight average molecular weight was 4.09×10 6 g/mol, narrow molecular weight distribution (pdi=1.59). Loop pipeline cycle test results at 0 ℃ show that the drag reduction efficiency of the copolymer is 43.79%. The data for the specific copolymers are shown in table 1.
TABLE 1 copolymer property data for the examples a
Note that: a reaction conditions examples 1 to 7 and 14 were 1-octene/1-decene, examples 8 to 11 and 12 were 1-hexene/1-dodecene, example 13 was 1-hexene/1-dodecene/4-methyl 1-pentene, example 15 was 1-octene/1-decene/3-methyl 1-butene, cat.=16. Mu. Mol, al 3 R=0.6 mL (1.0M toluene solution), temperature= -5-0 ℃; b high temperature GPC test; c drag reduction efficiency was calculated from the loop experiments and equation (1), with examples 1-11 at 25℃and examples 12-15 at 0 ℃.
From the data in Table 1, examples 1-7 demonstrate that the 1-octene/1-decene copolymer has better drag reduction efficiency than a homopolymer and an optimal feed ratio of 1:1; examples 8-11 illustrate that the drag reduction efficiency of 1-hexene/1-dodecene copolymers increases with increasing molecular weight. Examples 12-15 demonstrate that the addition of 4-methyl-1-pentene and 3-methyl-1-butene is effective in enhancing drag reduction at low temperatures. Overall, the drag reduction efficiency of the polymer is high, highlighting the performance advantages of the alpha-olefin copolymer.
The foregoing is merely a preferred embodiment of the present application, but the scope of the present application is not limited thereto, and any changes or substitutions easily conceivable by those skilled in the art within the technical scope of the present application should be covered in the scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims (10)
1. A narrow distribution, ultra-high molecular weight polymer based on alpha-olefins, characterized by the following structural formula:
Wherein x=5000 to 50000, y=5000 to 50000, z 1 =0 or 250 to 10000; z 2 =0 or 250 to 10000; a=2 to 18, b=2 to 18.
2. The narrow alpha-olefin based, ultra-high molecular weight polymer of claim 1, wherein the narrow alpha-olefin based, ultra-high molecular weight polymer exhibits a white or transparent amorphous solid, has tackiness and elasticity; absence of T g The method comprises the steps of carrying out a first treatment on the surface of the A weight average molecular weight of greater than 300X 10 4 g/mol, and the molecular weight distribution is between 1.5 and 3.0; the conversion rate of the monomer is between 60 and 100 percent; the drag reduction efficiency of the polymer is between 20% and 60%.
3. A process for the preparation of a narrow distribution, ultra-high molecular weight polymer based on α -olefins according to any of claims 1 to 2, characterized in that it comprises the following steps:
mixing a hydrocarbon compound solvent with a polymerization monomer, sequentially adding a cocatalyst and a Ti-Mg catalyst, carrying out polymerization reaction for 2-168 hours at the temperature of minus 30-30 ℃, and adding a terminator after polymerization to obtain a reaction solution;
adding an acidified precipitant into the reaction liquid, and obtaining the narrow-distribution and ultra-high molecular weight polymer based on alpha-olefin through filtering, washing, dissolving, adsorbing, filtering, settling, washing and vacuum drying.
4. The method for preparing a narrow distribution, ultra high molecular weight polymer based on alpha-olefins according to claim 3, wherein the hydrocarbon solvent comprises at least one of benzene and its homologs, naphthalene and its homologs, alkanes and their homologs, and cycloalkanes and their homologs.
5. The method for preparing a narrow-distribution, ultra-high molecular weight polymer based on alpha-olefin according to claim 3, wherein the molar concentration of the polymerized monomer in the hydrocarbon solvent is 0.1 to 4mol/L.
6. The method for preparing a narrow-distribution ultra-high molecular weight polymer based on alpha-olefin according to claim 5, wherein the polymerized monomers include C 4 ～C 20 One or more of the alpha-olefins.
7. The method for preparing a narrow distribution, ultra-high molecular weight polymer based on alpha-olefin according to claim 3, wherein the method for preparing a narrow distribution, ultra-high molecular weight polymer based on alpha-olefin further comprises a process of adding 4-methyl 1-pentene or 3-methyl 1-butene.
8. The method for preparing a narrow-distribution ultra-high molecular weight polymer based on alpha-olefin according to claim 3, wherein the cocatalyst is at least one of methylaluminoxane, dried methylaluminoxane, ethylaluminoxane, ethyl-isobutyl luminoxane, trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, ethylaluminum dichloride, diethylaluminum chloride, diethyl zinc, diethyl magnesium, diisobutylmagnesium or n-butylethylmagnesium.
9. The method for preparing a narrow distribution, ultra-high molecular weight polymer based on alpha-olefins according to claim 3, wherein the molar ratio of co-catalyst to multi-active-center Ti-Mg catalyst is 1:1 to 500:1.
10. Use of the narrow distribution, ultra-high molecular weight alpha-olefin-based polymer of any one of claims 1-2 in a drag reducing material.
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