CN114478888B - Polyolefin elastomer and preparation method thereof - Google Patents
Polyolefin elastomer and preparation method thereof Download PDFInfo
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- CN114478888B CN114478888B CN202210252302.2A CN202210252302A CN114478888B CN 114478888 B CN114478888 B CN 114478888B CN 202210252302 A CN202210252302 A CN 202210252302A CN 114478888 B CN114478888 B CN 114478888B
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- propylene
- titanium
- butene
- monomer
- alkyl aluminum
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- 229920006124 polyolefin elastomer Polymers 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 52
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 52
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000005977 Ethylene Substances 0.000 claims abstract description 21
- 229920000098 polyolefin Polymers 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 12
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 86
- 238000006243 chemical reaction Methods 0.000 claims description 43
- 239000000178 monomer Substances 0.000 claims description 38
- -1 alkyl aluminum compound Chemical class 0.000 claims description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 29
- 239000001257 hydrogen Substances 0.000 claims description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims description 29
- 239000010936 titanium Substances 0.000 claims description 28
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 27
- 229910052719 titanium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 230000009471 action Effects 0.000 claims description 5
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 229920001083 polybutene Polymers 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 229920001971 elastomer Polymers 0.000 abstract description 3
- 229920001577 copolymer Polymers 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 229920000642 polymer Polymers 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 238000007670 refining Methods 0.000 description 12
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 12
- 230000001276 controlling effect Effects 0.000 description 9
- 239000007791 liquid phase Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 150000002148 esters Chemical group 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 230000000379 polymerizing effect Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 239000012968 metallocene catalyst Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- SHSGDXCJYVZFTP-UHFFFAOYSA-N 4-ethoxybenzoic acid Chemical compound CCOC1=CC=C(C(O)=O)C=C1 SHSGDXCJYVZFTP-UHFFFAOYSA-N 0.000 description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- NMVXHZSPDTXJSJ-UHFFFAOYSA-L 2-methylpropylaluminum(2+);dichloride Chemical compound CC(C)C[Al](Cl)Cl NMVXHZSPDTXJSJ-UHFFFAOYSA-L 0.000 description 1
- XCSGHNKDXGYELG-UHFFFAOYSA-N 2-phenoxyethoxybenzene Chemical compound C=1C=CC=CC=1OCCOC1=CC=CC=C1 XCSGHNKDXGYELG-UHFFFAOYSA-N 0.000 description 1
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 description 1
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- AVWGMYDWIAZFGI-UHFFFAOYSA-N [2-ethyl-1-(3,3,3-trifluoropropyl)piperidin-2-yl]-dimethoxysilane Chemical compound FC(CCN1C(CCCC1)(CC)[SiH](OC)OC)(F)F AVWGMYDWIAZFGI-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- MEWFSXFFGFDHGV-UHFFFAOYSA-N cyclohexyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C1CCCCC1 MEWFSXFFGFDHGV-UHFFFAOYSA-N 0.000 description 1
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZVMRWPHIZSSUKP-UHFFFAOYSA-N dicyclohexyl(dimethoxy)silane Chemical compound C1CCCCC1[Si](OC)(OC)C1CCCCC1 ZVMRWPHIZSSUKP-UHFFFAOYSA-N 0.000 description 1
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 1
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003900 succinic acid esters Chemical class 0.000 description 1
- HXLWJGIPGJFBEZ-UHFFFAOYSA-N tert-butyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(C)(C)C HXLWJGIPGJFBEZ-UHFFFAOYSA-N 0.000 description 1
- NETBVGNWMHLXRP-UHFFFAOYSA-N tert-butyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C(C)(C)C NETBVGNWMHLXRP-UHFFFAOYSA-N 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- JAYPHJBLPAEMEX-UHFFFAOYSA-N trimethoxy(2-methylpentan-2-yl)silane Chemical compound CCCC(C)(C)[Si](OC)(OC)OC JAYPHJBLPAEMEX-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/08—Butenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- 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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention provides a preparation method of a polyolefin elastomer, which adopts two-stage polymerization to prepare the polyolefin elastomer. According to the invention, through adjusting the feeding process in the polyolefin elastomer preparation process, the catalytic activity of the catalyst and the molecular chain structure of the prepared polyolefin product are improved, and the toughness of the prepared polyolefin product is further improved. After propylene (or ethylene) is introduced into the main chain of the polybutene in the polymerization section, the regular arrangement of partial polybutene chain segments is destroyed to form an amorphous area with rubber elasticity, but the addition amount of the comonomer in the polymerization section is between 0 and 50 percent (wt), so that the polybutene chain segments which can be partially crystallized are reserved as physical crosslinking points to provide strength for the material, the copolymer has good thermoplasticity, and the special structure endows the material with good elasticity and excellent toughness.
Description
Technical Field
The invention relates to the technical field of high molecular polymers, in particular to a polyolefin elastomer and a preparation method thereof.
Background
Polyolefin elastomers have recently been proposed as novel polymeric materials having properties intermediate between rubber and thermoplastic, both elastomeric and thermoplastic processability. Polyolefin elastomer has wide application in the aspect of toughening modification of polypropylene, and has become the first choice of polypropylene toughening agent.
Most polyolefin elastomer products are prepared by metallocene catalysts at present, but the domestic metallocene catalyst preparation technology is basically in a laboratory stage, cannot realize industrialization, and has high catalyst cost; the metallocene polyolefin elastomer has complex polymerization process, no mature polymerization process exists in China, the raw material cost is high, and the requirement of the metallocene catalyst on the raw material purity is high, so that the cost of the metallocene prepared polyolefin elastomer is greatly increased.
The Z-N catalyst is developed by 6 generations, the preparation technology and the polymerization process thereof are mature, the requirement on the purity of raw materials is low, and the production cost is low, so that the development of the polyolefin elastomer of the Z-N catalyst system becomes a problem to be solved urgently by the technicians in the field.
Disclosure of Invention
In view of the above, the present invention aims to provide a polyolefin elastomer and a method for preparing the same.
The invention provides a preparation method of a polyolefin elastomer, which adopts two-stage polymerization to prepare the polyolefin elastomer.
In the present invention, the method for preparing polyolefin comprises the steps of:
(1) Under the action of a supported titanium catalyst, an alkyl aluminum compound and an external electron donor, carrying out polymerization reaction on a propylene monomer, a 1-butene monomer and hydrogen to obtain a prepolymerized phase;
(2) Under the action of an alkyl aluminum compound and an external electron donor, polymerizing the prepolymerization phase, 1-butene, propylene (or ethylene) monomer and hydrogen to obtain a polyolefin elastomer;
in the present invention, the polyolefin elastomer of the present invention is preferably produced in an apparatus or device having an impurity content of 0 or an impurity content satisfying the polymerization experiment.
In the present invention, the step (1) is preferably to polymerize a liquid propylene monomer, a 1-butene monomer, an alkyl aluminum compound, an external electron donor, a titanium-supported catalyst and hydrogen to obtain a pre-polymerized phase. In the present invention, the polymerization reaction temperature in the step (1) is preferably-10 to 80 ℃, more preferably 10 to 70 ℃, still more preferably 20 to 60 ℃, and most preferably 30 to 50 ℃; the polymerization time is preferably 0.1 to 10 hours, more preferably 0.3 to 5 hours, and most preferably 0.5 to 2 hours. In the present invention, after the polymerization reaction in the step (1) reaches a predetermined time or conversion rate, unreacted propylene monomer and 1-butene monomer are recovered to obtain uniform spherical particles (prepolymerized phase) having catalytic activity.
In the present invention, the mass ratio of the propylene monomer to the 1-butene monomer in the step (1) is preferably 0.1 to 100:1, more preferably 0.5 to 30:1, most preferably 1 to 20:1; the total mass ratio of the hydrogen to the propylene monomer to the 1-butene monomer is preferably 0.001-20:100, more preferably 0.01-15:100, and most preferably 0.1-10: 100; the molar ratio of titanium element to propylene monomer and 1-butene monomer in the titanium-supported catalyst is preferably 1 to 1000 multiplied by 10 -7 1, more preferably 10 to 800X 10 -7 1, more preferably 100 to 600X 10 -7 1, most preferably 200 to 400X 10 -7 1, a step of; the molar ratio of the aluminum element in the alkyl aluminum compound to the titanium element in the titanium-supported catalyst is preferably 10-500:1, more preferably 20-300:1, more preferably 50-150:1, and most preferably 80-120:1; the molar ratio of the external electron donor to the titanium element in the titanium-supported catalyst is preferably 0.1-50:1, more preferably 1-35:1, more preferably 5-25:1, and most preferably 10-20:1.
In the present invention, the step (A2) is preferably to add an alkyl aluminum compound, liquid phase 1-butene, propylene (or ethylene) monomer and hydrogen to the prepolymerization phase for polymerization to obtain a polyolefin elastomer. In the present invention, the polymerization reaction temperature in the step (A2) is preferably-10 to 80 ℃, more preferably 0 to 70 ℃, more preferably 10 to 60 ℃, more preferably 20 to 50 ℃, and most preferably 30 to 40 ℃; the polymerization time is preferably 0.1 to 48 hours, more preferably 0.5 to 40 hours, still more preferably 1 to 30 hours, still more preferably 1.5 to 20 hours, and most preferably 2 to 15 hours.
In the present invention, the total mass ratio of the hydrogen to the 1-butene and propylene (or ethylene) monomers in the step (A2) is preferably 0.001 to 20:100, more preferably 0.01 to 15:100, and most preferably 0.1 to 10:100; the molar ratio of the aluminum element in the alkyl aluminum compound to the titanium element in the titanium-supported catalyst is preferably 10-500:1, more preferably 50-150:1, and most preferably 80-120:1; the molar ratio of aluminum element to external electron donor in the alkyl aluminum compound is preferably 5-200:1, more preferably 10-150:1, more preferably 50-120:1, and most preferably 80-100:1.
In the present invention, the mass ratio of the propylene (or ethylene) monomer to the 1-butene monomer in the step (A2) is preferably 0 to 99:100, more preferably 1 to 80:100, more preferably 2 to 60:100, and most preferably 3 to 50:100.
In the present invention, the step (B2) is preferably to add an alkyl aluminum compound, an external electron donor, a 1-butene monomer, a propylene (or ethylene) monomer and hydrogen to the prepolymerization phase for polymerization to obtain a polyolefin elastomer. In the present invention, the polymerization reaction temperature in the step (B2) is preferably-10 to 80 ℃, more preferably 0 to 70 ℃, more preferably 10 to 60 ℃, more preferably 20 to 50 ℃, and most preferably 30 to 40 ℃; the polymerization time is preferably 0.1 to 48 hours, more preferably 0.5 to 40 hours, still more preferably 1 to 30 hours, still more preferably 1.5 to 20 hours, and most preferably 2 to 15 hours.
In the present invention, the total mass ratio of the hydrogen to the 1-butene and propylene (or ethylene) monomers in the step (B2) is preferably 0.001 to 20:100, more preferably 0.01 to 15:100, and most preferably 0.1 to 10:100; the molar ratio of the aluminum element in the alkyl aluminum compound to the titanium element in the titanium-supported catalyst is preferably 10-500:1, more preferably 50-150:1, and most preferably 80-120:1; the molar ratio of aluminum element to external electron donor in the alkyl aluminum compound is preferably 5-200:1, more preferably 10-150:1, more preferably 50-120:1, and most preferably 70-100:1.
In the present invention, the mass ratio of the propylene (or ethylene) monomer to the 1-butene monomer in the step (B2) is preferably 0 to 99:100, more preferably 1 to 80:100, still more preferably 2 to 60:100, and most preferably 3 to 50:100.
In the present invention, the pulse feeding time of propylene (or ethylene) in the step (B2) is preferably 1 to 100 times, more preferably 2 to 50 times, most preferably 4 to 20 times, and the relevant technicians of the initial pulse propylene feeding time and pulse time interval can operate according to practical situations.
In the present invention, the polymerization reaction in the step (1), the step (A2) and the step (B2) may be carried out in a batch process, a semi-continuous process or a continuous process.
In the invention, the equipment adopted for preparing the polyolefin can be a single reaction kettle or two reaction kettles connected in series, and if the equipment is a single reaction kettle, the step (1) is finished, and then the step (A2) or the step (B2) is continuously carried out in the reaction kettle; if two reaction kettles are connected in series, the step (1) is carried out in a first reaction kettle, and after the step (1) is finished, the obtained polypropylene phase is transferred to a second reaction kettle to carry out the step (A2) or the step (B2). The method for preparing polyolefin provided by the invention can be used in the working section of small-scale test, pilot-scale test or industrial production.
In the invention, after the step (A2) or the step (B2) is reacted for a preset polymerization time, unreacted raw materials are recycled, and the obtained reaction product is subjected to gas-solid separation to obtain the polyolefin product.
In the present invention, it is preferable to granulate the polyolefin product after mixing the polyolefin product with an auxiliary agent after obtaining the polyolefin. In the present invention, the auxiliary agent preferably includes one or more of an antioxidant, a stabilizer, a lubricant and a dispersant. In the present invention, the method of granulation is preferably twin-screw or single-screw extrusion granulation.
In the present invention, the titanium-supported catalyst preferably contains an internal electron donor; the titanium-supported catalyst preferably comprises a titanium compound and an internal electron donor. In the present invention, the titanium-supported catalystThe titanium compound of (C) is preferably a titanium halide, more preferably TiCl 4 、TiI 4 And TiBr 4 One or more of the following; the internal electron donor in the titanium-supported catalyst is preferably one or more of an ester compound, an ether compound, a ketone compound and an acid anhydride compound, and more preferably one of benzoic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid, phenylacetic acid, diisobutyl phthalate, dibutyl phthalate, benzoquinone, methyl benzoate, succinic acid ester and ethyl benzoate. In the present invention, the titanium-supported catalyst is preferably a Ziegler-Natta catalyst, more preferably a spherical or spheroidal Ziegler-Natta catalyst. The source of the titanium-supported catalyst is not particularly limited and is commercially available.
In the present invention, the titanium element content in the titanium-supported catalyst is preferably 1 to 5%, more preferably 2 to 4%, most preferably 3%; the mass content of the internal electron donor in the titanium-supported catalyst is preferably 0.005 to 20%, more preferably 0.01 to 18%, more preferably 0.1 to 15%, more preferably 1 to 12%, more preferably 3 to 10%, and most preferably 5 to 8%.
In the present invention, the alkylaluminum compound is preferably one or more of alkylaluminum, alkylaluminum halide and alkylaluminum hydride, more preferably one or more of triethylaluminum, triisobutylaluminum, dimethylaluminum monochloride, methylaluminum dichloride, diethylaluminum monochloride, diisobutylaluminum monochloride, monoisobutylaluminum dichloride, diethylaluminum hydride and diisobutylaluminum hydride.
In the present invention, the external electron donor is preferably one or more of an organosiloxane compound and a diether compound, more preferably one or more of dicyclohexyl dimethoxy silane, cyclohexyl trimethoxy silane, diisopropyl dimethoxy silane, tert-butyl trimethoxy silane, tert-hexyl trimethoxy silane, methylcyclohexyl dimethoxy silane, diphenyl dimethoxy silane, methyl tert-butyl dimethoxy silane, dicyclopentyl dimethoxy silane, 2-ethylpiperidyl-2-tert-butyl dimethoxy silane, 1-trifluoropropyl-2-ethylpiperidyl-dimethoxy silane, ethyltrimethoxy silane, propyltrimethoxy silane, phenyl trimethoxy silane, phenyl triethoxy silane, 1, 3-diether, 1, 4-diether and ethylene glycol diphenyl ether.
In the present invention, the propylene monomer and the 1-butene monomer are preferably purified before the polymerization reaction is performed. In the invention, the hydrogen is used as a molecular weight regulator, and the molecular weight and the distribution of each polymer are regulated by the hydrogen in two-stage polymerization, so that the molecular weight and the distribution of the polyolefin elastomer synthesized product are regulated.
In the invention, the structure and the performance of the prepared polyolefin can be adjusted in a large range through the implementation of the liquid phase bulk polymerization process. The content of each component in the polyolefin elastomer can be regulated in a larger range by controlling the time of two-stage polymerization reaction, the reaction temperature, the feeding proportion of the monomer, the propylene pulse number and the like, so that the polyolefin elastomer with adjustable structure and performance is obtained.
The invention adopts a two-stage polymerization method to prepare the polyolefin elastomer, wherein the one-stage polymerization is used as the activation and preliminary catalytic polymerization of a catalyst system, and the catalytic activity is fully dispersed and loaded in or on the polymer by controlling the form of the polymer, so that a foundation is laid for the two-stage polymerization.
According to the invention, after propylene (or ethylene) chain segments are introduced into a polybutene main chain, the regular arrangement of part of polybutene chain segments is destroyed, and an amorphous region with rubber elasticity is formed. The 1-butene, propylene (or ethylene) random copolymer and the 1-butene and propylene (or ethylene) block copolymer account for 0.05-80% of the total polymer, so that a part of the crystallized polybutene chain segments are reserved as physical crosslinking points to provide strength for the material, the copolymer has good thermoplasticity, and the method provided by the invention can prepare a high-performance polyolefin elastomer product.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other examples of modifications and alterations will be apparent to those skilled in the art based on the examples herein, and are intended to be within the scope of the invention.
The raw materials used in the following examples of the present invention are all commercially available.
Example 1
Refining 0.7kg of liquid-phase propylene and 1.3kg of 1-butene respectively through a refining system;
after a 10L polymerization kettle is subjected to nitrogen replacement and vacuumizing treatment, triethylaluminum, external electron donor diphenyl dimethoxy silane and MgCl are sequentially added into the reaction kettle 2 TiCl-loaded 4 0.20g of catalyst (titanium carrying amount is 2.3wt%, internal electron donor is esters), 0.5kg of propylene, 0.1kg of 1-butene and 0.8L of hydrogen are put in, wherein Al/Ti=50 (molar ratio), si/Ti=15 (molar ratio). And (3) polymerizing for 30min at the constant temperature of 60 ℃ by a DCS control system, and then evacuating and cooling.
When the temperature of the reaction vessel was lowered to 20 ℃, 1.2kg of 1-butene, 0.2kg of propylene, 3.0l of triethylaluminum and 3.0l of hydrogen were charged into the reaction vessel, and al/ti=50 (molar ratio). And (3) controlling the polymerization at the constant temperature of 35 ℃ for 50min through a DCS control system, then emptying, stopping the reaction, replacing the reaction kettle with nitrogen until the combustible gas content is qualified, and opening the kettle to obtain 1.6kg of polymer.
Example 2
Refining 0.7kg of liquid-phase propylene and 1.3kg of 1-butene respectively through a refining system;
after a 10L polymerization kettle is subjected to nitrogen replacement and vacuumizing treatment, triethylaluminum, external electron donor diphenyl dimethoxy silane and MgCl are sequentially added into the reaction kettle 2 TiCl-loaded 4 0.22g of catalyst (titanium carrying amount is 2.3wt%, internal electron donor is esters), 0.5kg of propylene, 0.2kg of 1-butene and 1.2L of hydrogen are put in, wherein Al/Ti=50 (molar ratio), si/Ti=15 (molar ratio). And (3) polymerizing for 30min at the constant temperature of 60 ℃ by a DCS control system, and then evacuating and cooling.
When the temperature of the reaction vessel was lowered to 20 ℃, 1.1kg of 1-butene, 0.2kg of propylene, 6.0l of triethylaluminum and 6.0l of hydrogen were charged into the reaction vessel, and al/ti=50 (molar ratio). And (3) controlling the polymerization at the constant temperature of 35 ℃ for 50min through a DCS control system, then emptying, stopping the reaction, replacing the reaction kettle with nitrogen until the combustible gas content is qualified, and opening the kettle to obtain 1.7kg of polymer.
Example 3
2.0kg of liquid-phase propylene and 3.0kg of 1-butene are respectively refined by a refining system;
after a 20L polymerization kettle is subjected to nitrogen replacement and vacuumizing treatment, triethylaluminum, external electron donor diphenyl dimethoxy silane and MgCl are sequentially added into the reaction kettle 2 TiCl-loaded 4 0.40g of catalyst (titanium carrying amount is 2.3wt%, internal electron donor is esters), 1.2kg of propylene, 0.4kg of 1-butene and 2.0L of hydrogen are put in, wherein Al/Ti=50 (molar ratio), si/Ti=15 (molar ratio). And (3) polymerizing for 40min at the constant temperature of 60 ℃ by a DCS control system, and then evacuating and cooling.
After the reaction vessel temperature was lowered to 20 ℃, 2.6kg of 1-butene, 0.2kg of propylene, 10.0l of triethylaluminum and 10.0l of hydrogen were charged into the reaction vessel, and al/ti=50 (molar ratio). And (3) controlling the polymerization for 80min at the constant temperature of 35 ℃ by a DCS control system, starting timing after the hydrogen is added in the reaction process, adding 0.2kg of propylene every 15min, adding propylene for 3 times in total, emptying after the polymerization time is reached, stopping the reaction, replacing the reaction kettle with nitrogen until the combustible gas content is qualified, and opening the kettle to obtain 4.1kg of polymer.
Example 4
Refining 1.2kg of liquid-phase propylene and 3.0kg of 1-butene respectively through a refining system, and refining 0.8 of ethylene;
after a 20L polymerization kettle is subjected to nitrogen replacement and vacuumizing treatment, triethylaluminum, external electron donor diphenyl dimethoxy silane and MgCl are sequentially added into the reaction kettle 2 TiCl-loaded 4 0.40g of catalyst (titanium carrying amount is 2.3wt%, internal electron donor is esters), 1.2kg of propylene, 0.4kg of 1-butene and 2.0L of hydrogen are put in, wherein Al/Ti=50 (molar ratio), si/Ti=15 (molar ratio). And (3) polymerizing for 40min at the constant temperature of 60 ℃ by a DCS control system, and then evacuating and cooling.
After the reaction vessel temperature was lowered to 20 ℃, 2.6kg of 1-butene, 0.2kg of ethylene, 10.0l of triethylaluminum and 10.0l of hydrogen were charged into the reaction vessel, and al/ti=50 (molar ratio). And (3) controlling the polymerization for 70min at the constant temperature of 37 ℃ through a DCS control system, starting timing after the hydrogen is added in the reaction process, adding 0.1kg of ethylene every 10min, adding 6 times in total, emptying after the polymerization time is reached, stopping the reaction, replacing the reaction kettle with nitrogen until the combustible gas content is qualified, and opening the kettle to obtain 4.1kg of polymer.
Example 5
Refining 1.3t of liquid-phase propylene and 2.0t of 1-butene respectively by a refining system;
after nitrogen replacement and vacuumizing treatment are adopted in a polymerization kettle of a polypropylene device with the capacity of 10000t/a, triethylaluminum, external electron donor diphenyl dimethoxy silane and MgCl are sequentially added into the reaction kettle 2 TiCl-loaded 4 30g of catalyst (titanium-carrying amount is 2.3wt%, the internal electron donor is esters), 0.6t of propylene, 0.2t of 1-butene and 200g of hydrogen are added, wherein Al/Ti=30 (molar ratio), si/Ti=15 (molar ratio). And (3) controlling the polymerization for 2 hours at the constant temperature of 60 ℃ through a DCS control system, and then evacuating and cooling.
When the temperature of the reaction vessel was lowered to 20 ℃, 1.8t of 1-butene, 0.2t of propylene, triethylaluminum, 500g of hydrogen gas, and al/ti=20 (molar ratio) were charged into the reaction vessel. And (3) controlling the polymerization for 7h at the constant temperature of 35 ℃ through a DCS control system, starting timing after the end of hydrogen input in the reaction process, adding 0.1t of propylene every 1h, adding propylene 5 times in total, emptying after reaching the polymerization time, stopping the reaction, and replacing the reaction kettle with nitrogen until the content of combustible gas is qualified to obtain 2.1t of powdery polymer.
Comparative example 1
The comparative example of Weidame 3588FL was used.
Comparative example 2
Refining 0.7kg of liquid-phase propylene and 1.3kg of 1-butene respectively through a refining system;
after a 10L polymerization kettle is subjected to nitrogen replacement and vacuumizing treatment, triethylaluminum, external electron donor diphenyl dimethoxy silane and MgCl are sequentially added into the reaction kettle 2 TiCl-loaded 4 0.20g of catalyst (titanium carrying amount is 2.3wt%, internal electron donor is esters), 0.7kg of propylene, 1.3kg of 1-butene and 2.0L of hydrogen are put in, wherein Al/Ti=50 (molar ratio), si/Ti=15(molar ratio). And (3) controlling the polymerization at the constant temperature of 40 ℃ for 80min through a DCS control system, then emptying, stopping the reaction, replacing the reaction kettle with nitrogen until the combustible gas content is qualified, and opening the kettle to obtain 1.5kg of polymer.
Example 6
The powdery polymers prepared in examples 1 to 4 and comparative example 1 were subjected to performance test.
The test standard for MFR (melt mass flow rate) is GB/T3682-2018 determination of thermoplastic melt mass flow rate and melt volume flow rate.
The tensile strength is tested in GB/T1040.1-2018 determination of Plastic tensile Property.
The test standard of the tensile strain at break is GB/T1040.1-2018, determination of tensile Property of plastics.
The test standard of the bending strength is GB/T9341-2008 "determination of Plastic bending Property".
The test standard of the impact strength of the cantilever beam is GB/T1843-2008 "determination of impact strength of Plastic cantilever beam".
The test results are shown in Table 1, and Table 1 shows the results of performance tests on the polyolefins prepared in examples 1 to 4 of the present invention and comparative example 1.
TABLE 1 polyolefin elastomer Performance test results for inventive examples 1-4 and comparative example 1
As can be seen from Table 1, the polyolefin prepared by the present invention has good impact resistance.
From the above examples, the present invention provides a method for preparing a polyolefin elastomer, which comprises two-stage polymerization to obtain a polyolefin elastomer; according to the invention, the material feeding process in the polyolefin preparation process is optimized, so that the stereoregularity of the polyolefin product is changed, and the toughness and impact resistance of the prepared polyolefin product are improved. The polyolefin prepared by the feeding process ensures that the polymer has good thermoplasticity and excellent toughness.
While the invention has been described with respect to the preferred embodiments, it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention and are intended to be within the scope of the present invention.
Claims (1)
1. A preparation method of a polyolefin elastomer is characterized in that a polyolefin product is prepared by two-stage polymerization; the method specifically comprises the following steps:
(1) Under the action of a supported titanium catalyst, an alkyl aluminum compound and an external electron donor, carrying out a prepolymerization reaction on a propylene monomer, a 1-butene monomer and hydrogen to obtain a prepolymerized phase;
(A2) Under the action of an alkyl aluminum compound, carrying out polymerization reaction on the prepolymerization phase, the mixed monomer of 1-butene and propylene or ethylene and hydrogen to obtain a polyolefin elastomer; or (b)
(B2) Under the action of an alkyl aluminum compound, carrying out polymerization reaction on the prepolymerization phase, a 1-butene monomer and hydrogen, and adding propylene or ethylene monomer in a pulse manner in the reaction process to carry out reaction to obtain a polyolefin elastomer;
in the step (1), the mass ratio of propylene to 1-butene is 1-20:1,
the mass ratio of the hydrogen to the propylene to the 1-butene is 0.001-20:100,
the total molar ratio of titanium element in the supported titanium catalyst to propylene and 1-butene is 1-1000 multiplied by 10 -7 ：1，
The molar ratio of the aluminum element in the alkyl aluminum compound to the titanium element in the supported titanium catalyst is 10-500:1,
the molar ratio of the external electron donor to the titanium element in the supported titanium catalyst is 0.1-50:1;
in the step (A2), the total mass ratio of the hydrogen to the 1-butene monomer to the propylene or ethylene monomer is 0.001-20:100,
the molar ratio of the aluminum element in the alkyl aluminum compound to the titanium element in the titanium-loaded catalyst in the step (1) is 10-500:1,
the mass ratio of the propylene or ethylene monomer to the 1-butene monomer is 3-50:100;
in the step (B2), the total mass ratio of the hydrogen to the 1-butene monomer to the propylene or ethylene monomer is 0.001-20:100,
the molar ratio of the aluminum element in the alkyl aluminum compound to the titanium element in the titanium-loaded catalyst in the step (1) is 10-500:1,
the molar ratio of the aluminum element in the alkyl aluminum compound to the external electron donor is 0.5-500:1,
the mass ratio of the propylene or ethylene monomer to the 1-butene monomer is 3-50:100;
the propylene pulse frequency is 1-100;
the temperature of the polymerization reaction in the step (1) is-10-80 ℃; the polymerization reaction time is 0.1-10 hours; the temperature of the polymerization reaction in the step (A2) or the step (B2) is-10-80 ℃; the polymerization reaction time is 0.1-48 hours;
the titanium-loaded catalyst contains an internal electron donor, wherein the mass content of titanium element in the titanium-loaded catalyst is 1-4%, and the mass content of the internal electron donor in the titanium-loaded catalyst is 0.1-20%;
the alkyl aluminum compound is one or more of alkyl aluminum, alkyl aluminum halide and alkyl aluminum hydride.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4284738A (en) * | 1980-08-11 | 1981-08-18 | El Paso Polyolefins Company | Ethylene-propylene block copolymerization process and product |
| CN101627058A (en) * | 2007-03-06 | 2010-01-13 | 伊内奥斯美国公司 | Gas-phase propylene polymerization process using staged addition of aluminum alkyl |
| CN104761834A (en) * | 2015-03-30 | 2015-07-08 | 青岛科技大学 | High isotactic polypropylene alloy material and preparation method thereof |
| CN108192005A (en) * | 2017-12-29 | 2018-06-22 | 黄河三角洲京博化工研究院有限公司 | A kind of polyolefin and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4284738A (en) * | 1980-08-11 | 1981-08-18 | El Paso Polyolefins Company | Ethylene-propylene block copolymerization process and product |
| CN101627058A (en) * | 2007-03-06 | 2010-01-13 | 伊内奥斯美国公司 | Gas-phase propylene polymerization process using staged addition of aluminum alkyl |
| CN104761834A (en) * | 2015-03-30 | 2015-07-08 | 青岛科技大学 | High isotactic polypropylene alloy material and preparation method thereof |
| CN108192005A (en) * | 2017-12-29 | 2018-06-22 | 黄河三角洲京博化工研究院有限公司 | A kind of polyolefin and preparation method thereof |
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