CN116948288A - Polyolefin in-situ blend and preparation method and application thereof - Google Patents
Polyolefin in-situ blend and preparation method and application thereof Download PDFInfo
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- CN116948288A CN116948288A CN202310948838.2A CN202310948838A CN116948288A CN 116948288 A CN116948288 A CN 116948288A CN 202310948838 A CN202310948838 A CN 202310948838A CN 116948288 A CN116948288 A CN 116948288A
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- polyolefin
- situ blend
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- 229920000098 polyolefin Polymers 0.000 title claims abstract description 163
- 239000000203 mixture Substances 0.000 title claims abstract description 73
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 31
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000005977 Ethylene Substances 0.000 claims abstract description 16
- 239000002135 nanosheet Substances 0.000 claims abstract description 8
- 239000004711 α-olefin Substances 0.000 claims abstract description 7
- 239000000155 melt Substances 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 4
- 229920001577 copolymer Polymers 0.000 claims abstract description 3
- 229920001519 homopolymer Polymers 0.000 claims abstract description 3
- 239000012184 mineral wax Substances 0.000 claims abstract description 3
- 229920001903 high density polyethylene Polymers 0.000 claims description 32
- 239000004700 high-density polyethylene Substances 0.000 claims description 32
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 30
- -1 polyethylene Polymers 0.000 claims description 27
- 238000006116 polymerization reaction Methods 0.000 claims description 27
- 239000001993 wax Substances 0.000 claims description 25
- 239000004698 Polyethylene Substances 0.000 claims description 22
- 229920000573 polyethylene Polymers 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 10
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 10
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 10
- 229920001684 low density polyethylene Polymers 0.000 claims description 10
- 239000004702 low-density polyethylene Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 7
- 239000007791 liquid phase Substances 0.000 claims description 7
- 239000012968 metallocene catalyst Substances 0.000 claims description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 7
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 6
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 6
- 239000002064 nanoplatelet Substances 0.000 claims description 5
- 239000004209 oxidized polyethylene wax Substances 0.000 claims description 5
- 235000013873 oxidized polyethylene wax Nutrition 0.000 claims description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 4
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 4
- JVSWJIKNEAIKJW-UHFFFAOYSA-N 2-Methylheptane Chemical compound CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 4
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Chemical compound CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 claims description 4
- LAIUFBWHERIJIH-UHFFFAOYSA-N 3-Methylheptane Chemical compound CCCCC(C)CC LAIUFBWHERIJIH-UHFFFAOYSA-N 0.000 claims description 4
- VLJXXKKOSFGPHI-UHFFFAOYSA-N 3-methylhexane Chemical compound CCCC(C)CC VLJXXKKOSFGPHI-UHFFFAOYSA-N 0.000 claims description 4
- PFEOZHBOMNWTJB-UHFFFAOYSA-N 3-methylpentane Chemical compound CCC(C)CC PFEOZHBOMNWTJB-UHFFFAOYSA-N 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 4
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 2
- 239000001282 iso-butane Substances 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 2
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 claims description 2
- HPKBFHDRGPIYAG-UHFFFAOYSA-N tris(2,4,6-trifluorophenyl)borane Chemical compound FC1=CC(F)=CC(F)=C1B(C=1C(=CC(F)=CC=1F)F)C1=C(F)C=C(F)C=C1F HPKBFHDRGPIYAG-UHFFFAOYSA-N 0.000 claims description 2
- AGOOAFIKKUZTEB-UHFFFAOYSA-N tris(3,5-difluorophenyl)borane Chemical compound FC1=CC(F)=CC(B(C=2C=C(F)C=C(F)C=2)C=2C=C(F)C=C(F)C=2)=C1 AGOOAFIKKUZTEB-UHFFFAOYSA-N 0.000 claims description 2
- YPVVTWIAXFPZLS-UHFFFAOYSA-N tris(4-fluorophenyl)borane Chemical compound C1=CC(F)=CC=C1B(C=1C=CC(F)=CC=1)C1=CC=C(F)C=C1 YPVVTWIAXFPZLS-UHFFFAOYSA-N 0.000 claims description 2
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000003014 reinforcing effect Effects 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 5
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000006384 oligomerization reaction Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000000051 modifying effect Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
Classifications
-
- 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
- C08L23/06—Polyethene
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
-
- 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
-
- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a polyolefin in-situ blend and a preparation method and application thereof. The polyolefin in-situ blend comprises polyolefin A and polyolefin B, wherein the polyolefin A is an ethylene homopolymer or a copolymer of ethylene and alpha-olefin, the weight average molecular weight of the polyolefin A is more than or equal to 800kg/mol, and the mass ratio of the polyolefin A to the polyolefin in-situ blend is 50-99wt%; polyolefin B is a synthetic mineral wax having a weight average molecular weight of 300-30000g/mol. In particular, polyolefin A on the surface of the polyolefin in-situ blend particles presents a nano-sheet structure, the thickness of the nano-sheet is 10-300nm, the distance between adjacent platelets is 200-4000nm, and the thickness and the distance of the nano-sheet can be adjusted by the type and the content of polyolefin B. The melt index of the polyolefin in-situ blend is in the range of 0.1-12g/10min. The polyolefin in-situ blend is added into the general polyolefin material in an amount of 1-50wt%, so that the tensile breaking strength of the general polyolefin material is improved by 40-250%, and the notch impact strength of the cantilever Liang Shan is improved by 200-700%.
Description
Technical Field
The invention relates to a polyolefin material, in particular to a polyolefin in-situ blend and a preparation method and application thereof.
Background
Polyolefin resins (e.g., high density polyethylene HDPE, low density polyethylene LDPE, linear low density polyethylene LLDPE, etc.) are widely used in packaging, construction, automobiles, etc. fields by virtue of excellent chemical stability, easy processing, low cost, etc. Compared with other engineering plastics, the polyolefin material has the defects of low strength, poor heat resistance, easiness in generating static electricity, poor heat conductivity and the like, so that the application of the polyolefin material in various engineering fields is greatly limited. The functional auxiliary agent with a certain proportion can improve various defects, endow one or more functional characteristics to the functional auxiliary agent, develop functional materials with intelligent characteristics, greatly improve the additional value of the polyolefin materials, widen the application field of the polyolefin materials, and have important significance for the practicability of the polyolefin materials.
The improvement of the strength, the rigidity and the toughness of polyolefin resin is an important problem to be solved for a long time, and a common polyolefin reinforcing modification mode is an additive type, namely, inorganic salts or inorganic oxides such as calcium carbonate, titanium dioxide and the like are added into polyolefin materials such as high-density polyethylene HDPE, low-density polyethylene LDPE, linear low-density polyethylene LLDPE and the like according to the proportion of 0.5-5% in a molten state so as to achieve the aim of improving the strength, the rigidity and the toughness of the polyolefin materials. However, there is a problem of compatibility between inorganic salts or inorganic oxides such as calcium carbonate and titanium dioxide and polyolefin materials, and it is difficult to achieve good blending, and the modifying effect is limited. If an excessive amount of inorganic salt or inorganic oxide is added, phase separation easily occurs, and instead the strength, rigidity and toughness of the polyolefin material are lowered. The development of a novel polyolefin-based reinforcing material is an original purpose of the present invention, and it is desirable to be able to design and prepare a polyolefin-based reinforcing material to solve the problems of poor blending compatibility, low addition ratio and limited modification reinforcing and toughening effects in the material modification process.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a polyolefin in-situ blend, a preparation method and application thereof, wherein the polyolefin in-situ blend can be used as a reinforcing auxiliary agent to realize the reinforcing and toughening of a general polyolefin material, and the polyolefin in-situ blend and the general polyolefin material have excellent processability and are easy to process when being blended and molded.
According to an object of the present invention, there is provided an in-situ polyolefin blend comprising polyolefin A and polyolefin B, wherein polyolefin A is an ethylene homopolymer or a copolymer of ethylene and an alpha-olefin, having a weight average molecular weight of not less than 800kg/mol, and wherein polyolefin A is present in an amount of 50 to 99% by weight based on the mass of the in-situ polyolefin blend; polyolefin B is synthetic mineral wax with weight average molecular weight of 300-30000g/mol, and the mass ratio of polyolefin B to polyolefin in-situ blend is 1-50wt%; polyolefin A on the surface of the polyolefin in-situ blend particles presents a nano-sheet structure, the thickness of the nano-sheet is 10-300nm, and the distance between adjacent platelets is 200-4000 nm; the melt index of the polyolefin in-situ blend is in the range of 0.1-12g/10min.
According to a preferred embodiment of the invention, the in-situ blend of polyolefin has a molecular weight distribution index of 30 to 500, a branching degree of polyolefin A of 0.1 to 50C/10000C, a melting point of 130 to 145 ℃, a branching degree of polyolefin B of 0.1 to 50C/10000C and a melting point of 50 to 110 ℃.
According to a preferred embodiment of the present invention, the polyolefin B uniformly occupies the space between the polyolefin a nanoplatelets, and the crystallinity of the polyolefin in-situ blend is 60 to 99%.
According to a preferred embodiment of the present invention, the thickness and spacing of the nanoplatelets can be adjusted by the type and content of the polyolefin B.
According to another object of the present invention, there is provided a process for the preparation of the above polyolefin in situ blend: the reaction kettle is subjected to dewatering and deoxidization treatment in advance, the polyolefin B is completely dissolved in the solvent C in advance, the solvent C in which the polyolefin B is dissolved is added into the reaction kettle, then the solvent C, the catalyst promoter, the catalyst and the ethylene or the ethylene and the alpha-olefin are sequentially added, the mass concentration of the polyolefin B in a liquid phase in the reaction kettle is kept to be 0.5-15wt%, the polymerization reaction is carried out for a period of time at a set temperature and pressure, and the polyolefin in-situ blend is obtained after cooling, discharging and drying.
According to a preferred embodiment of the invention, the polyolefin B is selected from polyolefin materials having a molecular weight not higher than 10000g/mol, preferably one or more of polyethylene wax, polypropylene wax, polyamide wax, fischer-tropsch wax, paraffin wax, oxidized polyethylene wax, oxidized polypropylene wax.
According to a preferred embodiment of the present invention, the solvent C is selected from one or more of n-butane, isobutane, n-pentane, isopentane, n-hexane, cyclohexane, 2-methylpentane, 3-methylpentane, n-heptane, 2-methylhexane, 3-methylhexane, n-octane, 2-methylheptane, 3-methylheptane, n-nonane, n-decane.
According to a preferred embodiment of the invention, the cocatalyst is selected from one or more of methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, butylaluminoxane, trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum dichloride, triphenylborane, tris (4-fluorophenyl) borane, tris (pentafluorophenyl) borane, tris (3, 5-difluorophenyl) borane, tris (2, 4, 6-trifluorophenyl) borane; the catalyst is selected from one or more of metallocene catalyst, late transition metal catalyst, ziegler-Natta catalyst, non-metallocene catalyst and FI catalyst. .
According to a preferred embodiment of the present invention, the alpha-olefin selected for polymerization is one or more of 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene or 1-decene.
According to a preferred embodiment of the invention, it is characterized in that the polymerization is carried out at a temperature of 50-110℃and a pressure of 1-50bar and a polymerization time of 0.1-10h.
According to a third object of the present invention, there is provided the use of the above-described polyolefin in situ blend as a general purpose polyolefin material blending modifier. The general purpose polyolefin material may be HDPE, LDPE, LLDPE, POE, EVA or the like.
Preferably, the polyolefin in-situ blend is added into HDPE or LDPE or LLDPE or POE or EVA in an amount of 1-50wt%, so that the tensile breaking strength of the HDPE or LDPE or LLDPE or POE or EVA is improved by 40-250%, and the notch impact strength of the cantilever Liang Shan is improved by 200-700%.
Compared with the prior art, the invention has the following outstanding gain effects: (1) In the polyolefin in-situ blend of the present invention, the high molecular weight polyolefin A component and the low molecular weight polyolefin B component have microphase separation structures (see FIG. 1 and FIG. 2), which exhibit interpenetration. The microphase separation structure ensures that when the polyolefin in-situ blend is blended with a general polyolefin material, the lubricating effect of the low molecular weight polyolefin B on the high molecular weight polyolefin A and the general polyolefin molecular chains is quicker and more remarkable, the molecular chains of the high molecular weight polyolefin A can be opened more quickly, and entanglement among the molecular chains and in the molecular chains is less, so that the molecular chain orientation degree of the polyolefin A is higher in the orientation process, a cross-crystal reinforced structure is easier to form, and the strength, the rigidity and the toughness of the general polyolefin material (HDPE, LDPE, LLDPE, POE, EVA and the like) are greatly improved.
(2) When the polyolefin in-situ blend is used for reinforcing the general polyolefin material, the wax molecular chain lubricating efficiency of the low molecular weight polyolefin B is higher, so that the screw processing and molding period is shorter, the torque of the material to the screw is lower, and the processing and molding are more efficient.
Drawings
FIG. 1 is a scanning electron microscope image of the polyolefin in situ blends of examples 1-4.
FIG. 2 is a scanning electron micrograph of the surface of polyolefin A particles of examples 1-4 after elution of polyolefin component B with n-heptane for the polyolefin in situ blend.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The following methods were used to test the structure or properties of the polyolefin produced in the examples:
scanning Electron Microscopy (SEM) was used to test the platelet thickness and platelet spacing of the polyolefin material (see fig. 2).
Differential Scanning Calorimeter (DSC) is used to determine the melting point and crystallinity of polyolefin materials.
High temperature Gel Permeation Chromatography (GPC) is used for the molecular weight and distribution of polyolefin materials.
The universal tester is used for testing the tensile breaking strength of the polyolefin material.
The impact tester was used to test the notched impact strength of the cantilever Liang Shan of the polyolefin material.
Nuclear magnetic resonance spectrometer 13 C-NMR) was used to test the branching degree of polyolefin materials.
Melt index meters are used to test the melt index of polyolefin materials.
And separating out the polyolefin B component in the polyolefin in-situ blend by adopting an n-heptane heating leaching mode, so as to determine the mass ratio of the polyolefin A to the polyolefin B.
Example 1
The polymerization reaction device is purged with high-purity nitrogen to remove moisture and oxygen in the reaction device. Polyethylene wax (weight average molecular weight 800g/mol, melting point 86 ℃, branching degree 2.3C/10000C) is dissolved in normal hexane in advance, normal hexane solution of the polyethylene wax is added into a reaction kettle, then normal hexane, methylaluminoxane and supported metallocene catalyst are added, the polyethylene wax accounts for 5 weight percent of the total mass of liquid phase in the reaction kettle, ethylene is introduced to start polymerization, the polymerization temperature is 80 ℃, the polymerization pressure is 12bar, the polymerization time is 2h, and the polyolefin in-situ blend 1 is obtained after cooling, discharging and drying.
The characterization result of the polyolefin in-situ blend 1 is shown in table 1, and the reinforcing and toughening result of the polyolefin in-situ blend 1 on the high-density polyethylene HDPE is shown in table 2 (the polyolefin in-situ blend 1 accounts for 10wt% of the total mass of the reinforced and toughened product).
Example 2
The polymerization reaction device is purged with high-purity nitrogen to remove moisture and oxygen in the reaction device. Polyethylene wax (weight average molecular weight 1300g/mol, melting point 96 ℃, branching degree 2.1C/10000C) is dissolved in n-heptane in advance, n-heptane solution of the polyethylene wax is added into a reaction kettle, n-heptane, methylaluminoxane, supported metallocene catalyst and comonomer 1-hexene are added, the polyethylene wax accounts for 3 weight percent of the total mass of liquid phase in the reaction kettle, ethylene is introduced to start polymerization, the polymerization temperature is 76 ℃, the polymerization pressure is 8bar, the polymerization time is 3h, and the polyolefin in-situ blend 2 is obtained after cooling, discharging and drying.
The characterization result of the polyolefin in-situ blend 2 is shown in table 1, and the reinforcing and toughening result of the polyolefin in-situ blend 2 on the high-density polyethylene HDPE is shown in table 2 (the polyolefin in-situ blend 2 accounts for 20wt% of the total mass of the reinforced and toughened product).
Example 3
The polymerization reaction device is purged with high-purity nitrogen to remove moisture and oxygen in the reaction device. Oxidized polyethylene wax (weight average molecular weight 3700g/mol, melting point 104 ℃, branching degree 2.7C/10000C) is dissolved in n-heptane in advance, n-heptane solution of the oxidized polyethylene wax is added into a reaction kettle, n-heptane, triethylaluminum, supported Ziegler Natta catalyst and comonomer 1-octene are added, the oxidized polyethylene wax accounts for 6 weight percent of the total mass of liquid phase in the reaction kettle, ethylene is introduced to start polymerization, polymerization temperature is 86 ℃, polymerization pressure is 17bar, polymerization time is 4h, and polyolefin in-situ blend 3 is obtained after cooling, discharging and drying.
The characterization result of the polyolefin in-situ blend 3 is shown in table 1, and the reinforcing and toughening result of the polyolefin in-situ blend 3 on the high-density polyethylene HDPE is shown in table 2 (the polyolefin in-situ blend 3 accounts for 8wt% of the total mass of the reinforced and toughened product).
Example 4
The polymerization reaction device is purged with high-purity nitrogen to remove moisture and oxygen in the reaction device. The preparation method comprises the steps of pre-dissolving Fischer-Tropsch wax (weight average molecular weight 700g/mol, melting point 76 ℃ and branching degree 1.0C/10000C) in n-pentane, adding n-pentane solution of the Fischer-Tropsch wax into a reaction kettle, adding n-pentane, triethylaluminum and a supported Ziegler Natta catalyst, wherein the Fischer-Tropsch wax accounts for 8wt% of the total mass of liquid phase in the reaction kettle, introducing ethylene to start polymerization, polymerizing at the temperature of 76 ℃, polymerizing at the pressure of 6bar for 7h, cooling, discharging and drying to obtain the polyolefin in-situ blend 4.
The characterization result of the polyolefin in-situ blend 4 is shown in table 1, and the reinforcing and toughening result of the polyolefin in-situ blend 4 on the high-density polyethylene HDPE is shown in table 2 (the polyolefin in-situ blend 4 accounts for 25wt% of the total mass of the reinforced and toughened product).
Comparative example 1
After the commercial ultra-high molecular weight polyethylene powder and polyethylene wax are physically blended (wherein the weight average molecular weight of the ultra-high molecular weight polyethylene is 2260kg/mol, the branching degree is 0.12C/10000C, the mass ratio is 86wt%, the weight average molecular weight of the polyethylene wax is 0.8kg/mol, the branching degree is 2.1C/10000C, the mass ratio is 14 wt%) and then the blend is melt blended with the high-density polyethylene HDPE for injection molding, and the mechanical property characterization result is shown in Table 2 (the high-density polyethylene HDPE accounts for 90wt% of the total mass of the blend injection molded product).
Comparative example 2
A Hostalen series process is adopted to prepare a high-density polyethylene product composed of a high-molecular-weight polyethylene component and a low-molecular-weight polyethylene component, and the high-density polyethylene product belongs to a PE 100-grade pipe material. The mass ratio of the high molecular weight polyethylene component to the low molecular weight polyethylene component in the high density polyethylene product was 48:52. The weight average molecular weight of the high density polyethylene product was 246kg/mol and the molecular weight distribution was 28.9, wherein the weight average molecular weight of the high molecular weight polyethylene component was 402kg/mol and the weight average molecular weight of the low molecular weight polyethylene component was 102kg/mol. The results of the mechanical property characterization of the high-density polyethylene injection molding sample are shown in table 2.
Comparative example 3
The polyethylene in-situ blend prepared by adopting a double-kettle serial process, wherein the first kettle is ethylene monomer oligomerization reaction to obtain an oligomerization component with the molecular weight of 58-1000g/mol, wherein an olefin component with the carbon number of less than 20 is a liquid phase component (main component), an olefin component with the carbon number of more than 20 is a solid phase component (secondary component), and the mass concentration of the secondary component in a reaction system is less than 0.2wt%. The second reaction kettle is a copolymerization reaction of ethylene and a product in the first kettle, a supported metallocene catalyst is used as a main catalyst, a cocatalyst is aluminum alkyl, the polymerization temperature is 60 ℃, a polyethylene in-situ blend with a weight average molecular weight of 320kg/mol and a molecular weight distribution of 2.8 is obtained, the main component in the in-situ blend is a polyethylene component obtained by polymerization in the second kettle, and the few components are olefin minor components which do not participate in the copolymerization reaction in the first kettle. The results of the mechanical property characterization of the polyethylene in-situ blend injection molding sample are shown in Table 2.
Table 1 characterization of polyolefin in situ blends of examples 1-4 results
| Example 1 | Example 2 | Example 3 | Example 4 | |
| Polyolefin A weight average molecular weight (kg/mol) | 2300 | 1670 | 1290 | 3120 |
| Polyolefin A is the mass ratio (wt%) of the blend | 86 | 92 | 76 | 88 |
| Polyolefin A melting point (. Degree. C.) | 143.2 | 142.8 | 141.6 | 143.6 |
| Degree of branching of polyolefin A (C/10000C) | 0.8 | 11.3 | 5.6 | 0.6 |
| Average thickness (nm) of polyolefin A nanosheets | 23.6 | 20.7 | 26.1 | 31.5 |
| Polyolefin A average spacing (nm) | 530 | 660 | 290 | 1200 |
| Polyolefin B weight average molecular weight (kg/mol) | 0.8 | 1.3 | 3.7 | 0.7 |
| Polyolefin B is the mass ratio (wt%) | 14 | 8 | 4 | 12 |
| Polyolefin B melting point (. Degree. C.) | 86 | 96 | 104 | 76 |
| Degree of branching of polyolefin B (C/10000C) | 2.3 | 2.1 | 2.7 | 1.0 |
| Polyolefin in situ blend melt index (g/10 min) a | 3.6 | 5.7 | 4.3 | 1.2 |
| Polyolefin in situ blend molecular weight distribution | 128 | 182 | 105 | 312 |
| Polyolefin in situ blend crystallinity (%) | 68.3 | 62.4 | 65.9 | 67.3 |
a Melt temperature of 190℃and load of 10kg.
TABLE 2 in situ polyolefin blend results for reinforcing and toughening general purpose polyolefin
As shown in tables 1 and 2, the reinforcing and toughening results of the polyolefin in-situ blends of examples 1-4 on the general polyolefin high density polyethylene HDPE show that the reinforcing and toughening effects on the HDPE are remarkable and are obviously better than those of the physical blend of the ultra-high molecular weight polyethylene and the polyethylene wax of comparative example 1. This is mainly because the polyethylene wax in the polyolefin in-situ blend has a remarkable lubricating effect on the high molecular weight polyethylene component, can better open the high molecular weight polyethylene molecular chain, and can form more oriented structures and cross-crystal structures in the injection molding orientation process, so that the reinforcing effect on the strength, the rigidity and the toughness is better. In the melt blending process of the physically blended ultra-high molecular weight polyethylene and polyethylene wax powder and HDPE, the opening degree of the ultra-high molecular weight polyethylene molecular chain is insufficient, and the physical entanglement in and among the molecular chain is excessive, so that the formation of an orientation structure is insufficient in the injection molding orientation process, and the reinforcing and toughening effects on the HDPE are limited. In contrast, the polyethylene samples of comparative examples 2 and 3, the high molecular weight component thereof did not contain the nano-platelet structure shown in fig. 2, and the molecular weight of the high molecular weight component was low, resulting in slower opening of the molecular chain during the thermoforming process, and the formation of the oriented structure with low content, resulting in poor mechanical properties of the injection molded bars.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The polyolefin in-situ blend is characterized by comprising polyolefin A and polyolefin B, wherein the polyolefin A is an ethylene homopolymer or a copolymer of ethylene and alpha-olefin, the weight average molecular weight of the polyolefin A is more than or equal to 800kg/mol, and the polyolefin A accounts for 50-99wt% of the polyolefin in-situ blend; polyolefin B is synthetic mineral wax with weight average molecular weight of 300-30000g/mol, and the mass ratio of polyolefin B to polyolefin in-situ blend is 1-50wt%; the polyolefin A on the surface of the polyolefin in-situ blend particles presents a nano-sheet structure, the thickness of the nano-sheet is 10-300nm, the distance between adjacent platelets is 200-4000nm, and the melt index of the polyolefin in-situ blend is 0.1-12g/10min.
2. The in situ polyolefin blend according to claim 1, wherein the in situ polyolefin blend has a molecular weight distribution index of 30 to 500, a branching degree of polyolefin a of 0.1 to 50C/10000C, a melting point of 130 to 145 ℃, a branching degree of polyolefin B of 0.1 to 50C/10000C, and a melting point of 50 to 110 ℃.
3. The polyolefin in-situ blend according to claim 1, wherein the polyolefin B uniformly occupies the space between the polyolefin a nanoplatelets and the crystallinity of the polyolefin in-situ blend is between 60 and 99%; the thickness and spacing of the nanoplatelets can be adjusted by the type and content of polyolefin B.
4. A process for preparing the polyolefin in-situ blend according to any of claims 1 to 3, characterized in that: the reaction kettle is subjected to dewatering and deoxidization treatment in advance, the polyolefin B is completely dissolved in the solvent C in advance, the solvent C in which the polyolefin B is dissolved is added into the reaction kettle, then the solvent C, the catalyst promoter, the catalyst and the ethylene or the ethylene and the alpha-olefin are sequentially added, the mass concentration of the polyolefin B in a liquid phase in the reaction kettle is kept to be 0.5-15wt%, the polymerization reaction is carried out for a period of time at a set temperature and pressure, and the polyolefin in-situ blend is obtained after cooling, discharging and drying.
5. The method according to claim 4, wherein the polyolefin B is selected from polyolefin materials having a molecular weight not higher than 10000g/mol, preferably one or more of polyethylene wax, polypropylene wax, polyamide wax, fischer-tropsch wax, paraffin wax, oxidized polyethylene wax, oxidized polypropylene wax.
6. The process according to claim 4, wherein the solvent C is selected from one or more of n-butane, isobutane, n-pentane, isopentane, n-hexane, cyclohexane, 2-methylpentane, 3-methylpentane, n-heptane, 2-methylhexane, 3-methylhexane, n-octane, 2-methylheptane, 3-methylheptane, n-nonane, n-decane.
7. The process of claim 4 wherein the cocatalyst is selected from one or more of methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, butylaluminoxane, trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum dichloride, triphenylborane, tris (4-fluorophenyl) borane, tris (pentafluorophenyl) borane, tris (3, 5-difluorophenyl) borane, tris (2, 4, 6-trifluorophenyl) borane; the catalyst is selected from one or more of metallocene catalyst, late transition metal catalyst, ziegler-Natta catalyst, non-metallocene catalyst and FI catalyst. .
8. The process of claim 4 wherein the alpha-olefin selected for polymerization is one or more of 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, or 1-decene.
9. The process according to claim 4, wherein the polymerization is carried out at a temperature of 50 to 110℃and a pressure of 1 to 50bar for a polymerization time of 0.1 to 10 hours.
10. Use of a polyolefin in-situ blend according to any of claims 1 to 3, wherein the polyolefin in-situ blend is added to HDPE or LDPE or LLDPE or POE or EVA in an amount of 1 to 50wt% to increase the tensile break strength of HDPE or LDPE or LLDPE or POE or EVA by 40 to 250% and the notched impact strength of cantilever Liang Shan by 200 to 700%.
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