CN111662498B - Polyolefin composition and preparation method and application thereof - Google Patents
Polyolefin composition and preparation method and application thereof Download PDFInfo
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- 229920000098 polyolefin Polymers 0.000 title claims abstract description 48
- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims description 25
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 122
- 229920001038 ethylene copolymer Polymers 0.000 claims abstract description 113
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims abstract description 82
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims abstract description 60
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 39
- 239000005977 Ethylene Substances 0.000 claims description 38
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 238000009826 distribution Methods 0.000 claims description 23
- 238000002425 crystallisation Methods 0.000 claims description 21
- 230000008025 crystallization Effects 0.000 claims description 21
- 239000000376 reactant Substances 0.000 claims description 18
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 16
- -1 ethylene, butylene Chemical group 0.000 claims description 14
- 239000000155 melt Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 150000001336 alkenes Chemical class 0.000 claims description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 239000002685 polymerization catalyst Substances 0.000 claims description 10
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 8
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000012968 metallocene catalyst Substances 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 9
- ALSOCDGAZNNNME-UHFFFAOYSA-N ethene;hex-1-ene Chemical group C=C.CCCCC=C ALSOCDGAZNNNME-UHFFFAOYSA-N 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 25
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 239000012530 fluid Substances 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000004698 Polyethylene Substances 0.000 description 9
- 229920000573 polyethylene Polymers 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 229920001684 low density polyethylene Polymers 0.000 description 4
- 239000004702 low-density polyethylene Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000005243 fluidization Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- IZWAHXMQCUUOJB-UHFFFAOYSA-N CC(C)(C(C)C)[Si](OC)(OC)OC.C(C)(C)(CCC)[Si](OC)(OC)OC Chemical compound CC(C)(C(C)C)[Si](OC)(OC)OC.C(C)(C)(CCC)[Si](OC)(OC)OC IZWAHXMQCUUOJB-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 159000000032 aromatic acids Chemical class 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 238000002288 cocrystallisation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 229920006284 nylon film Polymers 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical group CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a polyolefin composition comprising: butene/ethylene copolymers; and a hexene/ethylene copolymer, preferably the mass ratio of the butene/ethylene copolymer to the hexene/ethylene copolymer is (0.05 to 0.5): 1, preferably (0.1-0.3): 1, most preferably (0.1-0.2): 1. the butene-ethylene copolymer and the hexene-ethylene copolymer are used in a specific ratio, so that the polyolefin composition has a wide processing temperature range and good tensile property.
Description
Technical Field
The invention relates to the field of polyolefin materials, and in particular relates to a polyolefin composition and a preparation method and application thereof.
Background
Biaxially Oriented Polyethylene (BOPE) is a Polyethylene film prepared by using a biaxial orientation technology of a polymer, namely, between the glass transition temperature and the melting point of Polyethylene, a non-Oriented sheet is sequentially stretched longitudinally and transversely, a molecular chain has bidirectional orientation on a plane, and finally, the sheet is cooled and shaped under the condition of tensioning. BOPE thickness is even, tensile strength is high, anti puncture ability reinforce, heat-seal strength is high, the environmental protection, has excellent separation performance and low temperature resistance, and it mainly is applied to the complex film now, can guarantee under the circumstances that the intensity of film can not reduce, plays the effect of attenuate. For example, the BOPE can be used in combination with biaxially oriented nylon film (BOPA), biaxially oriented polyester film (BOPET), etc. to package various foods or daily necessities.
However, since 2009 biaxial stretching technology was first applied to polyethylene films, BOPE is not widely produced and applied in China today. The main reasons are that the polyethylene has the characteristics of easy crystallization, high crystallization rate, high crystallinity and the like, so that a crystalline region of the polyethylene is easy to rapidly grow and rupture a membrane in the stretching process, the relaxation time of a polyethylene molecular chain is short, the thickness of the prepared film is uneven, and the processing and stretching temperature range is narrower than that of PP, PA and PET.
An innovative polyethylene product suitable for biaxial stretching by a flat film method, which is pioneered by the Japan three-well chemical company, is prepared by combining certain mLDPE (low density polyethylene) and LDPE with bimodal distribution of relative molecular mass as raw material resin of BOPE. This mLDPE is produced using a specific metallocene catalyst and is expensive. The exxon meifu company prepares BOPE by a 5-layer polyethylene and polypropylene coextrusion process using an 80-percent vldpe (ultra low density polyethylene) and 20-percent ldpe blend as the coextruded surface layer, which has the disadvantage of greater operational difficulty.
Disclosure of Invention
In view of the problems of the prior art, it is an object of the present invention to provide a polyolefin composition, which is imparted with a wide processing temperature range and good tensile properties by blending a butene-ethylene copolymer and a hexene-ethylene copolymer at a specific ratio, and a method for producing the same and use thereof.
In one aspect, the present invention provides a polyolefin composition comprising:
butene/ethylene copolymers; and
a hexene/ethylene copolymer which is a copolymer of ethylene,
wherein the mass ratio of the butene/ethylene copolymer to the hexene/ethylene copolymer is (0.05-0.5): 1, preferably (0.1-0.3): 1, most preferably (0.1-0.2): 1.
in the research of the present inventors, it was found that when the butene/ethylene copolymer and the hexene/ethylene copolymer are used in combination, particularly when the butene/ethylene copolymer and the hexene/ethylene copolymer are used in combination in the specific ratio, a cocrystallization phenomenon occurs, the melting range of the polyolefin composition is widened, and the biaxial stretching temperature range of the polyolefin composition is increased, so that the prepared film has excellent mechanical properties, such as high tensile yield strength, high tensile rupture strength and high elastic modulus. And the addition of the butene/ethylene copolymer with a specific ratio can better improve the processability of the hexene/ethylene copolymer under the condition of ensuring that the tensile property is not remarkably reduced, so that the polyolefin composition is more suitable for domestic biaxial stretching production lines.
According to the invention, when the mass ratio of butene/ethylene copolymer to hexene/ethylene copolymer is (0.05 to 0.5): 1, the polyolefin composition has the advantages of slow crystallization rate and long molecular chain relaxation time; when the mass ratio of the butene/ethylene copolymer to the hexene/ethylene copolymer is (0.1-0.2): 1, the polyolefin composition also has the advantages of good tensile properties and a wide drawing processing temperature window.
According to the invention, the butene/ethylene copolymer is preferably an α -butene/ethylene copolymer; the hexene/ethylene copolymer is preferably an alpha-hexene/ethylene copolymer.
In some preferred embodiments of the present invention, the butene/ethylene copolymer has a content of structural units derived from butene of 0.1mol% to 10.0mol%, preferably 1.0mol% to 6.0mol%, more preferably 2.0mol% to 4.0mol%, and most preferably 3.0mol% to 3.5mol%.
In some preferred embodiments of the present invention, the hexene/ethylene copolymer contains structural units derived from hexene in an amount of 0.1mol% to 10.0mol%, preferably 1.0mol% to 6.0mol%, more preferably 2.0mol% to 4.0mol%, and most preferably 3.0mol% to 3.5mol%.
According to the present invention, when the content of the structural unit derived from butene and/or the content of the structural unit derived from hexene is within the above-specified range, the degree of entanglement of the heterogeneous molecular chains is maximized, which is advantageous in obtaining a wide processing temperature range and good tensile properties.
In some preferred embodiments of the invention, the butene/ethylene copolymer has a density of 0.715g/cm 3 -1.130g/cm 3 Preferably 0.915g/cm 3 -0.930g/cm 3 Most preferably 0.920g/cm 3 -0.930g/cm 3 。
In some preferred embodiments of the invention, the butene/ethylene copolymer has a melt index MI 2.16 Is 10g/10min-100g/10min, preferably 30g/10min-60g/10min, and most preferably 40g/10min-50g/10min.
In some preferred embodiments of the present invention, the weight average molecular weight of the butene/ethylene copolymer is below 50000, preferably from 10000 to 50000, most preferably from 30000 to 50000.
In some preferred embodiments of the invention, the butene/ethylene copolymer has a molecular weight distribution ranging from 1 to 10, preferably from 3 to 5, most preferably from 3 to 4.
In some preferred embodiments of the present invention, the molecular chain relaxation time of the butene/ethylene copolymer is from 0.1s to 10s, preferably from 1s to 3s, and most preferably from 1s to 2s.
In some preferred embodiments of the present invention, the butene/ethylene copolymers have a crystallization rate function value ranging from 10 to 50, preferably ranging from 30 to 35, and most preferably ranging from 30 to 32.
In some preferred embodiments of the present invention, the hexene/ethylene copolymer has a density of 0.715g/cm 3 -1.130g/cm 3 Preferably 0.915g/cm 3 -0.930g/cm 3 Most preferably 0.920g/cm 3 -0.925g/cm 3 。
In some preferred embodiments of the invention, the hexene/ethylene copolymer has a melt index MI 2.16 Is 0.01g/10min-10g/10min, preferably 0.1g/10min-2g/10min, and most preferably 0.5g/10min-1.5g/10min.
In some preferred embodiments of the present invention, the hexene/ethylene copolymer has a weight average molecular weight of 100000 or more, preferably 100000-500000, most preferably 100000-150000.
In some preferred embodiments of the present invention, the hexene/ethylene copolymer has a molecular weight distribution of 1 to 10, preferably 3 to 6, most preferably 4 to 6.
In some preferred embodiments of the present invention, the hexene/ethylene copolymer has a molecular chain relaxation time of 0.1s to 30s, preferably 5s to 10s, and most preferably 5s to 7s.
In some preferred embodiments of the present invention, the hexene/ethylene copolymer has a crystallization rate function value in the range of 10 to 50, preferably 30 to 35, most preferably 31 to 33.
In some preferred embodiments of the present invention, the polyolefin composition has a density of 0.715g/cm 3 -1.130g/cm 3 Preferably 0.915g/cm 3 -0.930g/cm 3 Most preferably 0.920g/cm 3 -0.925g/cm 3 。
In some preferred embodiments of the invention, the polyolefin composition has a melt index MI 2.16 Is 0.01g/10min-10g/10min, preferably 0.1g/10min-3g/10min, and most preferably 1.0g/10min-3.0g/10min.
In some preferred embodiments of the present invention, the polyolefin composition has a weight average molecular weight above 100000, preferably ranging from 100000 to 500000, most preferably ranging from 100000 to 120000.
In some preferred embodiments of the invention, the polyolefin composition has a molecular weight distribution of from 1 to 10, preferably from 3 to 6, most preferably from 4 to 5.
In some preferred embodiments of the present invention, the polyolefin composition has a molecular chain relaxation time of more than 2.5s, preferably more than 3s.
In some preferred embodiments of the present invention, the polyolefin composition has a crystallization rate function value of less than 31, preferably less than 30.
According to the present invention, when the values of the parameters of the butene/ethylene copolymer and of the hexene/ethylene copolymer are within the above specified ranges, it is advantageous to obtain a polyolefin composition having a density and a melt index MI 2.16 The values of parameters such as the weight average molecular weight, the molecular weight distribution, the molecular chain relaxation time, and the crystallization rate function are within the above-specified ranges, thereby obtaining a desired processing temperature range and tensile properties.
In still another aspect, the present invention provides a method for preparing a polyolefin composition, comprising:
melt blending the butene/ethylene copolymer and the hexene/ethylene copolymer to produce the polyolefin composition.
In some preferred embodiments of the invention, the melt blending conditions include a pressure of from 1MPa to 50MPa, preferably from 10MPa to 40MPa, and most preferably from 15MPa to 30MPa.
In some preferred embodiments of the invention, the melt blending conditions include a temperature of from 100 ℃ to 300 ℃, preferably from 150 ℃ to 200 ℃, and most preferably from 160 ℃ to 195 ℃.
According to the present invention, the melt blending mode is not limited, and it is preferable to perform melt blending in a torque rheometer and set different temperatures in 10 zones of the torque rheometer, for example, the temperature of the torque rheometer is set to 160 to 170 ℃ in the first zone, 175 to 185 ℃ in the second zone, 175 to 185 ℃ in the third zone, 185 to 190 ℃ in the fourth zone, 185 to 190 ℃ in the fifth zone, 185 to 190 ℃ in the sixth zone, 190 to 195 ℃ in the seventh zone, 190 to 195 ℃ in the eighth zone, 190 to 195 ℃ in the ninth zone, and 190 to 195 ℃ in the tenth zone.
In some preferred embodiments of the present invention, the method for preparing the butene/ethylene copolymer comprises:
contacting a reactant stream comprising ethylene, butene and a condensing agent with an olefin polymerization catalyst to polymerize the ethylene and butene and produce the butene/ethylene copolymer.
In some preferred embodiments of the present invention, the reactant stream comprising ethylene, butene, and condensing agent comprises ethylene in an amount of from 20.0mol% to 23.0mol%.
In some preferred embodiments of the present invention, the reactant stream comprising ethylene, butene, and a condensing agent comprises butene in an amount of from 3.0mol% to 3.5mol%.
In some preferred embodiments of the present invention, the reactant stream comprising ethylene, butene, and a condensing agent comprises from 15.0mol% to 17.5mol% of the condensing agent.
In some preferred embodiments of the present invention, the polymerization reaction has a reaction temperature of 20 ℃ to 120 ℃ and a polymerization pressure of 2.0MPa to 3.0MPa.
According to the present invention, the reactant stream containing ethylene, butene and condensing agent also includes hydrogen and nitrogen.
According to the present invention, hydrogen can be used to adjust the molecular weight of the polymerization product; the nitrogen gas can play a role of fluidization in the reactor, so that the reaction materials flow.
According to the invention, the hydrogen content in the reactant stream containing ethylene, butene and condensing agent is between 3.0mol% and 3.5mol%.
According to the invention, the nitrogen content in the reactant stream containing ethylene, butene and condensing agent is between 55.0mol% and 60.0mol%.
In some preferred embodiments of the present invention, the hexene/ethylene copolymer is prepared by a method comprising:
contacting a reactant stream comprising ethylene, butene and a condensing agent with an olefin polymerization catalyst to polymerize ethylene and hexene to produce the hexene/ethylene copolymer;
in some preferred embodiments of the present invention, the reactant stream comprising ethylene, butene, and condensing agent comprises ethylene in an amount from 25.0mol% to 28.0mol%.
In some preferred embodiments of the present invention, the hexene content in the reactant stream containing ethylene, butene and condensing agent is from 3.0mol% to 4.0mol%.
In some preferred embodiments of the present invention, the reactant stream comprising ethylene, butene, and a condensing agent comprises from 15.0mol% to 17.5mol% of the condensing agent.
In some preferred embodiments of the present invention, the polymerization reaction has a reaction temperature of 20 ℃ to 120 ℃ and a polymerization pressure of 2.0MPa to 3.0MPa.
According to the present invention, the reactant stream containing ethylene, butene and condensing agent also includes hydrogen and nitrogen.
According to the invention, the hydrogen content in the reactant stream containing ethylene, butene and condensing agent is between 4.0mol% and 4.5mol%.
According to the invention, the nitrogen content in the reactant stream containing ethylene, butene and condensing agent is between 50.0mol% and 55.0mol%.
In a particular embodiment, according to the present invention, the preparation of butene/ethylene copolymers or hexene/ethylene copolymers can be carried out in a fluidized bed reactor, with particular operating steps comprising: replacing air in the fluidized bed reactor by nitrogen, and fluidizing the seed bed under the condition of nitrogen; then adding a small amount of olefin polymerization catalyst into the fluidized bed reactor, and gradually reducing the introduction amount of nitrogen; then adding an olefin polymerization catalyst to a preset dosage, adding ethylene, butene (or hexene), hydrogen and a condensing agent in gradually increasing input quantities to form a circulating medium, and finally enabling the composition of the circulating medium to be in a specific range of the application. The condensate is recovered and recycled to the fluidized bed reactor.
In some preferred embodiments of the present invention, the olefin polymerization catalyst is selected from at least one of a ziegler-natta catalyst, a metallocene catalyst, and a late transition metal catalyst.
In some preferred embodiments of the present invention, the condensing agent is selected from at least one of isopentane, cyclohexane, n-hexane, and n-heptane.
According to the present invention, olefin polymerization catalysts (e.g., ziegler-Natta, metallocene, and late transition metal catalysts) prepared by methods known in the art can be applied to the present invention and achieve the desired technical effects.
The present invention is preferably a Ziegler-Natta catalyst or a composite catalyst composed of a Ziegler-Natta catalyst and a metallocene catalyst and/or a late transition metal catalyst.
The Ziegler-Natta catalyst system comprises: 1) A solid component containing a titanium compound and an electron-donor compound (internal donor) supported on a magnesium dihalide, preferably magnesium chloride; 2) An alkylaluminum compound (cocatalyst); optionally 3) an electron-donor compound (external donor); wherein the electron-donor compound (internal donor) is selected from ethers, ketones, lactones, compounds containing N, P and or S atoms, and compounds of mono-and dicarboxylic acid esters; the alkylaluminum compounds are trialkylaluminum compounds, such as Al-triethyl, al-triisobutyl and Al-tri-n-butyl; the electron-donor compound (external donor) is selected from aromatic acid esters (e.g. alkyl benzoates, heterocyclic compounds), particularly preferably a silicon compound containing at least one Si-OR bond (wherein R is a hydrocarbon group), further preferably tert-hexyltrimethoxysilane (2, 3-dimethyl-2-trimethoxysilyl-butane).
In a further aspect, the present invention provides a use of the above polyolefin composition or the polyolefin composition produced according to the above production method as a raw material for biaxially oriented polyolefin.
According to the invention, the term "butene/ethylene copolymer" refers to the copolymerization product of butene and ethylene; the term "hexene/ethylene copolymer" refers to the copolymerization product of hexene and ethylene.
The polyolefin composition or the polyolefin composition prepared by the preparation method provided by the invention has the advantages of large molecular weight, wide molecular weight distribution, low crystallization rate and long molecular chain relaxation time, and finally leads to the widening of the processing temperature interval of the resin and the enhancement of the stretchability of the film, thereby meeting the application requirements of BOPE.
Drawings
FIG. 1 is a schematic view showing the reaction apparatus in production examples 1 and 2.
DrawingsDescription of the labeling: 1-a distribution plate; 2-a fluidized bed reactor; 3-a compression device; 4-a heat exchange device; 5-separation equipment; 6-a feed pump; 7-a gas circulation line; 8-discharging tank; 9-purging the tank; 10-degassing a bin; 11-a fluid conduit for introducing a hydrocarbon polymerization catalyst into the fluidized bed reactor; 12-a fluid conduit for introducing a condensate, olefin monomer, etc. into the fluidized bed reactor; 13-a fluid conduit for withdrawing a polymerization product from the fluidized bed reactor; 14-for the supply of H 2 、N 2 And a fluid conduit for introducing ethylene into the recycle line; 15-a fluid conduit for introducing olefin monomer into the recycle line; 16-a fluid conduit for introducing a condensing agent into the circulation line; 17-a fluid conduit for introducing the stream separated by the separation device into the reactor.
Detailed Description
The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to the following description.
The properties of the products obtained were tested according to the following criteria:
the product was tested for Melt Index (MI) according to GB/T3682-2000 2.16 190 ℃ under a load of 2.16 kg);
testing the density of the product according to GB/T1033.2-2010;
testing the thickness of the film product according to GB/T6672-2001;
tensile properties of the product were measured using ASTM D882.
The properties of the product obtained were tested using the following instruments:
measuring the weight average molecular weight and the molecular weight distribution of the product by a Polymer Laboratories PL-220 type gel permeation chromatograph;
measuring and calculating a function of the crystallization rate of the product by using a TA Q200 differential scanning calorimeter;
measuring the molecular chain relaxation time of the product by using a HAAKE RS6000 type rotational rheometer;
measuring the content of alpha-olefin by a Nicolet5700 type infrared spectrometer;
the tensile properties of the products were measured using an SRI800 laboratory synchronous biaxial stretcher.
The melt blending operation was carried out using a HAAKE Polylab OS type torque rheometer.
Preparation example 1
Preparation of 1-butene/ethylene copolymers
In the fluidized-bed reactor 2 with internal nitrogen fluidization as shown in FIG. 1, a small amount of Ziegler-Natta catalyst (solid component TiCl-loaded) was first continuously fed through a line 11 at a rate of 0.1kg/h 3 The cocatalyst of the magnesium chloride is triethyl aluminum, al: ti = 60) and fed with ethylene via line 14, 1-butene via line 15 and a small amount of isopentane condensate via line 16. Then, the flow rate of the Ziegler-Natta catalyst was gradually increased to 5kg/h, and the flow rate of isopentane was gradually increased while keeping the fluidizing gas velocity constant. As the reaction proceeds, ethylene continues to be fed through line 14 and 1-butene feed gas continues to be fed through line 15, thereby forming a circulating medium in the fluidized bed reactor. Wherein, the components and contents in the circulating medium are as follows: 20.6mol% of ethylene, 3.2mol% of 1-butene, 3.3mol% of hydrogen, 56.1mol% of nitrogen and 16.8mol% of isopentane.
The circulating medium from the fluidized bed reactor 2 was received through a pipe 7 connected to the top expanded section of the fluidized bed reactor 2 (the circulating medium was received at a pressure of 2.2MPa and a temperature of 89 ℃). The circulating medium is treated by a heat exchanger 4 and then subjected to gas-liquid separation by a gas-liquid separator 5. Thus, 80wt% of the total content of the condensing agent in the circulating medium is separately injected into the fluidized bed reactor 2 through the fluid pipe 12 at a position 2m above the distribution plate 1, and the rest of the condensing agent and the olefin monomer enter the fluidized bed reactor 2 along with the fluid pipe 17 below the distribution plate 1, thereby forming an upper high-temperature reaction zone (the highest temperature is 91 ℃) and a lower low-temperature reaction zone (the lowest temperature is 74 ℃) in the fluidized bed reactor, and the apparent fluidizing gas velocity is 0.41m/s.
At the above temperature, pressure and superficial fluidization gas velocity, ethylene and 1-butene are subjected to polymerization reaction for 2 hours to generate 1-butene/ethylene copolymer. Intermittently discharging the generated solid-phase 1-butene/ethylene copolymer from a fluid pipeline 13, carrying out devolatilization treatment on the solid-phase 1-butene/ethylene copolymer sequentially through a discharge tank 8, a purge tank 9 and a degassing bin 10, and then conveying the solid-phase 1-butene/ethylene copolymer to a downstream working section for further processing to obtain the 1-butene/ethylene copolymer.
The 1-butene/ethylene copolymer obtained was measured to contain 3.0mol% of 1-butene, and had a weight average molecular weight of 37092, a molecular weight distribution index of 3.9, and a melt index MI at 190 ℃ and 2.16kg 2.16 50g/10min, density 0.926g/cm 3 The molecular chain relaxation time was 1.566s, and the crystallization rate function value was 31.188.
Preparation example 2
Preparation of 1-hexene/ethylene copolymers
A1-hexene/ethylene copolymer was prepared in the same manner as in preparation example 1, except that:
the components and contents in the circulating medium are as follows: 25.4mol% ethylene, 3.5mol% 1-hexene, 4.2mol% hydrogen, 50.8mol% nitrogen and 16.1mol% isopentane;
the pressure of the circulating medium received by the pipeline 7 is 2.3MPa; and
the maximum temperature of the high-temperature reaction zone in the upper part of the fluidized bed reactor was 90 ℃ and the minimum temperature of the low-temperature reaction zone in the lower part was 73 ℃ and the superficial fluidizing gas velocity was 0.42m/s.
The 1-hexene/ethylene copolymer obtained was measured to contain 3.4mol% of 1-butene, had a weight average molecular weight of 123622, a molecular weight distribution index of 5.1, and a melt index MI at 190 ℃ and 2.16kg 2.16 1.0g/10min, density 0.921g/cm 3 The molecular chain relaxation time was 6.088s, and the crystallization rate function value was 32.569.
Preparation example 3
1-butene/ethylene copolymer was prepared in the manner as in preparation example 1, except that the components and contents in the circulating medium were as follows: 22.1mol% of ethylene, 7.5mol% of 1-butene, 2.9mol% of hydrogen, 47.0mol% of nitrogen and 20.5mol% of isopentane.
The 1-butene/ethylene copolymer produced was measured to contain 5.2mol% of 1-butene.
Preparation example 4
1-hexene/ethylene copolymer was prepared in the manner described in preparation 1, with the only difference that the components and contents in the circulating medium were as follows: 18.7mol% of ethylene, 8.3mol% of 1-hexene, 3.1mol% of hydrogen, 37.9mol% of nitrogen and 32.0mol% of isopentane.
The 1-butene/ethylene copolymer produced was measured to contain 4.9mol% of 1-hexene.
Example 1
The 1-butene/ethylene copolymer obtained in production example 1 and the 1-hexene/ethylene copolymer obtained in production example 2 were vacuum-dried for 3 days, and then the 1-butene/ethylene copolymer and the 1-hexene/ethylene copolymer were melt-blended under twin-screw action in a torque rheometer in a mass ratio of the 1-butene/ethylene copolymer to the 1-hexene/ethylene copolymer of 0.1. Wherein,
the rotation speed of the twin screw was set at 300rpm and the pressure was 20MPa. The temperature of the torque rheometer is set to be 160-170 ℃ in the first zone, 175-185 ℃ in the second zone, 175-185 ℃ in the third zone, 185-190 ℃ in the fourth zone, 185-190 ℃ in the fifth zone, 185-190 ℃ in the sixth zone, 190-195 ℃ in the seventh zone, 190-195 ℃ in the eighth zone, 190-195 ℃ in the ninth zone and 190-195 ℃ in the tenth zone.
The extruded polyolefin composition J1 was cut into pellets by a pelletizer and tested for properties, and the results are shown in tables 1 and 2.
Example 2
A polyolefin composition J2 was prepared in the same manner as in example 1, except that the mass ratio of the 1-butene/ethylene copolymer to the 1-hexene/ethylene copolymer was 0.18.
The performance of J2 was tested and the results are shown in tables 1 and 2.
Example 3
A polyolefin composition J3 was produced in the same manner as in example 1 except that the mass ratio of the 1-butene/ethylene copolymer to the 1-hexene/ethylene copolymer was 0.25.
The performance of J3 was tested and the results are shown in tables 1 and 2.
Example 4
A polyolefin composition J4 was prepared in the same manner as in example 1 except that the mass ratio of the 1-butene/ethylene copolymer to the 1-hexene/ethylene copolymer was 0.33.
The performance of J4 was tested and the results are shown in tables 1 and 2.
Example 5
A polyolefin composition J5 was prepared in the same manner as in example 1 except that the mass ratio of the 1-butene/ethylene copolymer to the 1-hexene/ethylene copolymer was 0.43.
The performance of J5 was tested and the results are shown in tables 1 and 2.
Example 6
Polyolefin composition J6 was prepared as in example 1, except that the 1-butene/ethylene copolymer obtained in preparation 3 was used in place of the 1-butene/ethylene copolymer obtained in preparation 1.
The performance of J6 was tested and the results are shown in tables 1 and 2.
Example 7
Polyolefin composition J7 was prepared as in example 1, except that the 1-hexene/ethylene copolymer prepared in preparation 4 was used instead of the 1-hexene/ethylene copolymer prepared in preparation 2.
The performance of J7 was tested and the results are shown in tables 1 and 2.
Example 8
Polyolefin composition J8 was prepared in the same manner as in example 1 except that the 1-butene/ethylene copolymer obtained in preparation example 3 and the 1-hexene/ethylene copolymer obtained in preparation example 4 were used in place of the 1-butene/ethylene copolymer obtained in preparation example 1 and the 1-hexene/ethylene copolymer obtained in preparation example 2, respectively.
The performance of J8 was tested and the results are shown in tables 1 and 2.
Comparative example 1
Provided is a 1-octene/ethylene copolymer containing 1.8mol% of 1-octene, having a weight average molecular weight of 86005, a molecular weight distribution index of 3.7, a melt index MI at 190 ℃ and 2.16kg 2.16 2.0g/10min, density 0.918g/cm3, molecular chain relaxation time 1.921s, and crystallization rate function value 30.922.
The resulting copolymer was melt-blended with the 1-butene/ethylene copolymer obtained in preparation example 1 in the blending ratio and blending manner described in example 1 to obtain a polyolefin composition J11.
The performance of J11 was tested and the results are shown in tables 1 and 2.
TABLE 1
TABLE 2
According to the data in tables 1 and 2, the polyolefin composition prepared by the examples of the present application has a large molecular weight, a wide molecular weight distribution, a small crystallization rate, and a long molecular chain relaxation time, which finally results in a widened processing temperature range of the resin and an enhanced stretchability of the film, and meets the application requirements of the BOPE, and is significantly better than other comparative examples and synthetic examples.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined within the scope of the claims and modifications may be made without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A polyolefin composition comprising:
butene/ethylene copolymers; and
a hexene/ethylene copolymer which is a copolymer of ethylene,
the mass ratio of the butene/ethylene copolymer to the hexene/ethylene copolymer is (0.05-0.5): 1;
the butene isThe content of structural units derived from butene in the ethylene copolymer is 1.0mol% to 6.0mol%, and the density of the butene/ethylene copolymer is 0.915g/cm 3 -0.930g/cm 3 Melt index MI 2.16 30g/10min-60g/10min, weight average molecular weight below 50000, molecular weight distribution of 1-10, molecular chain relaxation time of 0.1s-10s, and crystallization rate function value of 10-50;
the hexene/ethylene copolymer has a content of structural units derived from hexene of 1.0mol% to 6.0mol%, and a density of 0.915g/cm 3 -0.930g/cm 3 Melt index MI 2.16 0.1g/10min-2g/10min, weight average molecular weight above 100000, molecular weight distribution of 1-10, molecular chain relaxation time of 0.1s-30s, and crystallization rate function value of 10-50;
the polyolefin composition has a density of 0.915g/cm 3 -0.930g/cm 3 Melt index MI 2.16 0.1g/10min-3g/10min, weight average molecular weight over 100000, molecular weight distribution of 1-10, molecular chain relaxation time greater than 2.5s, and crystallization rate function value less than 31.
2. Polyolefin composition according to claim 1, characterized in that the mass ratio between the butene/ethylene copolymer and the hexene/ethylene copolymer is (0.1-0.3): 1;
the content of structural units derived from butene in the butene/ethylene copolymer is 2.0mol% to 4.0mol%, and the density of the butene/ethylene copolymer is 0.920g/cm 3 -0.930g/cm 3 Melt index MI 2.16 40g/10min-50g/10min, weight average molecular weight of 10000-50000, molecular weight distribution of 3-5, molecular chain relaxation time of 1s-3s, and crystallization rate function value of 30-35; and/or the presence of a gas in the atmosphere,
the hexene/ethylene copolymer has a content of structural units derived from hexene of 2.0mol% to 4.0mol%, and a density of 0.920g/cm 3 -0.925g/cm 3 Melt index MI 2.16 0.5g/10min-1.5g/10min, weight average molecular weight of 100000-500000, molecular weight distribution of 3-6, molecular chain relaxation time of 5s-10s,the crystallization rate function value is 30-35;
the polyolefin composition has a density of 0.920g/cm 3 -0.925g/cm 3 Melt index MI 2.16 1.0g/10min-3.0g/10min, weight average molecular weight of 100000-500000, molecular weight distribution of 3-6, molecular chain relaxation time greater than 3s and crystallization rate function value less than 30.
3. Polyolefin composition according to claim 2, characterized in that,
the mass ratio of the butene/ethylene copolymer to the hexene/ethylene copolymer is (0.1-0.2): 1;
in the butene/ethylene copolymer, the content of a structural unit derived from butene is 3.0mol% -3.5mol%, the weight average molecular weight of the butene/ethylene copolymer is 30000-50000, the molecular weight distribution is 3-4, the molecular chain relaxation time is 1s-2s, and the crystallization rate function value is 30-32; and/or
In the hexene/ethylene copolymer, the content of a structural unit derived from hexene is 3.0mol% to 3.5mol%, the weight average molecular weight of the hexene/ethylene copolymer is 100000 to 150000, the molecular weight distribution is 4 to 6, the molecular chain relaxation time is 5s to 7s, and the crystallization rate function value is 31 to 33; and/or
The polyolefin composition has a density of 0.920g/cm 3 -0.925g/cm 3 Melt index MI 2.16 1.0g/10min-3.0g/10min, weight average molecular weight of 100000-120000, and molecular weight distribution of 4-5.
4. A process for the preparation of a polyolefin composition according to any of claims 1-3 comprising:
melt blending the butene/ethylene copolymer and the hexene/ethylene copolymer to produce the polyolefin composition,
the conditions of the melt blending include a pressure of 1MPa to 50MPa and a temperature of 100 ℃ to 300 ℃.
5. The method of claim 4, wherein the melt blending conditions include a pressure of 10MPa to 40MPa and a temperature of 150 ℃ to 200 ℃.
6. The method of claim 5, wherein the melt blending conditions include a pressure of 15MPa to 30MPa and a temperature of 160 ℃ to 195 ℃.
7. The process according to claim 4, characterized in that it comprises:
contacting a reactant stream comprising ethylene, butene and a condensing agent with an olefin polymerization catalyst to polymerize the ethylene and butene and produce the butene/ethylene copolymer;
in the reactant flow containing ethylene, butylene and condensing agent, the content of ethylene is 20.0mol% -23.0mol%, the content of butylene is 3.0mol% -3.5mol%, and the content of condensing agent is 15.0mol% -17.5mol%; the reaction temperature of the polymerization reaction is 20-120 ℃, and the polymerization pressure is 2.0-3.0 MPa.
8. The method according to claim 4, wherein the hexene/ethylene copolymer is produced by a method comprising:
contacting a reactant stream comprising ethylene, hexene and a condensing agent with an olefin polymerization catalyst to polymerize the ethylene and hexene to produce the hexene/ethylene copolymer;
in the reactant flow containing ethylene, hexene and a condensing agent, the content of the ethylene is 25.0mol% to 28.0mol%, the content of the hexene is 3.0mol% to 4.0mol%, and the content of the condensing agent is 15.0mol% to 17.5mol%; the reaction temperature of the polymerization reaction is 20-120 ℃, and the polymerization pressure is 2.0-3.0 MPa.
9. The production method according to claim 7, wherein the olefin polymerization catalyst is at least one selected from the group consisting of a Ziegler-Natta catalyst, a metallocene catalyst and a late transition metal catalyst; the condensing agent is at least one selected from isopentane, cyclohexane, n-hexane and n-heptane.
10. Use of a polyolefin composition according to any of claims 1 to 3 or a polyolefin composition prepared by the preparation process according to any of claims 4 to 9 as a biaxially oriented polyolefin feedstock.
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