CN112745440B - Impact-resistant polypropylene and preparation method thereof - Google Patents
Impact-resistant polypropylene and preparation method thereof Download PDFInfo
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- CN112745440B CN112745440B CN201911039533.XA CN201911039533A CN112745440B CN 112745440 B CN112745440 B CN 112745440B CN 201911039533 A CN201911039533 A CN 201911039533A CN 112745440 B CN112745440 B CN 112745440B
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- 229920001155 polypropylene Polymers 0.000 title claims abstract description 48
- -1 polypropylene Polymers 0.000 title claims abstract description 47
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 95
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 95
- 239000007787 solid Substances 0.000 claims abstract description 69
- 229920000642 polymer Polymers 0.000 claims abstract description 66
- 239000000843 powder Substances 0.000 claims abstract description 65
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 48
- 239000007791 liquid phase Substances 0.000 claims abstract description 43
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000012071 phase Substances 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 22
- 239000004711 α-olefin Substances 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 21
- 239000005977 Ethylene Substances 0.000 claims description 21
- 230000014759 maintenance of location Effects 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000011144 upstream manufacturing Methods 0.000 abstract description 6
- 229920001971 elastomer Polymers 0.000 description 12
- 239000007789 gas Substances 0.000 description 10
- 230000000536 complexating effect Effects 0.000 description 9
- 239000008188 pellet Substances 0.000 description 6
- 238000010668 complexation reaction Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- 229920002943 EPDM rubber Polymers 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 4
- 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 3
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920005629 polypropylene homopolymer Polymers 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920006124 polyolefin elastomer Polymers 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 238000009835 boiling Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- XZFXULUXIPPWEW-UHFFFAOYSA-N dimethoxy-methyl-propan-2-ylsilane Chemical compound CO[Si](C)(OC)C(C)C XZFXULUXIPPWEW-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- MGDOJPNDRJNJBK-UHFFFAOYSA-N ethylaluminum Chemical compound [Al].C[CH2] MGDOJPNDRJNJBK-UHFFFAOYSA-N 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 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
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 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
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-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
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- OJAJJFGMKAZGRZ-UHFFFAOYSA-N trimethyl(phenoxy)silane Chemical compound C[Si](C)(C)OC1=CC=CC=C1 OJAJJFGMKAZGRZ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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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)
Abstract
The invention relates to the field of propylene polymerization, and discloses impact-resistant polypropylene and a preparation method thereof. The process for preparing impact polypropylene comprises: (1) Prepolymerizing propylene in the presence of a catalyst system; (2) Then, the material after the prepolymerization reaction, hydrogen and propylene are contacted for homopolymerization reaction to obtain polymer powder; (3) Introducing polymer powder and liquid-phase propylene into a gas-solid separator provided with a gas-phase outlet, wherein the liquid-phase propylene is vaporized in the gas-solid separator so as to carry and discharge light components from the gas-phase outlet of the gas-solid separator; (4) And (4) carrying out copolymerization reaction of propylene and alpha-olefin on the basis of removing the polymer powder carrying the light components in the step (3) to obtain the impact-resistant polypropylene powder. The invention also discloses impact polypropylene prepared by the method. The method can obtain the polymer product with high impact strength by effectively reducing the light components carried by the polymer powder at the upstream to enter the downstream reaction.
Description
Technical Field
The invention relates to the field of propylene polymerization, in particular to impact-resistant polypropylene and a preparation method thereof.
Background
The polypropylene is mainly classified into homo-polypropylene, random polypropylene and impact polypropylene, and the homo-polypropylene has poor impact resistance due to the characteristics of molecular structures. The impact-resistant polypropylene has good rigidity-toughness balance due to the rigidity of the homopolymerized polypropylene and the impact resistance of the ethylene propylene rubber component, and is widely applied to the fields of automobiles, household appliances, injection molding containers and the like.
The current polypropylene industry has two major categories of methods for improving the impact resistance of polypropylene. The first type is a blending modification method, in which polypropylene and an elastomer are physically blended to obtain a polypropylene product with good impact resistance, and common elastomers include ethylene propylene diene monomer (EPR), ethylene Propylene Diene Monomer (EPDM), polyolefin elastomer (POE), powdered rubber and the like. The second way is a multistage reactor preparation method, generally, propylene homopolymerization is carried out in a first-stage reactor(s) to obtain a propylene polymer, then polymer powder is conveyed to a second-stage reactor to carry out copolymerization of propylene and alpha-olefin, and a propylene-alpha-olefin rubber phase is generated in pores of particles of the homopolymerized propylene polymer, thereby realizing the respective formation of a polypropylene matrix phase and a rubber phase. The second way is also the currently mainstream way of making impact polypropylene.
The preparation of impact-resistant polypropylene by adopting a multistage reactor usually enters a subsequent reactor along with the entrained gas of polymer powder obtained by a previous stage reactor, and the entrained gas (light component, mainly hydrogen) of the polypropylene powder participates in the subsequent polymerization reaction, so that the molecular weight of the polymer obtained in a gas-phase copolymerization stage is smaller, and the final impact resistance of the polymer is influenced. Therefore, the research on the method for removing the entrained gas in the polymer powder is of great significance.
Disclosure of Invention
The object of the present invention is to overcome the problems of the prior art and to provide a new impact polypropylene and a process for its preparation.
In order to achieve the above object, the present invention provides, in one aspect, a method for preparing impact polypropylene, the method comprising:
(1) Subjecting propylene to a prepolymerization reaction in the presence of a catalyst system comprising a catalyst, a cocatalyst and optionally an external electron donor;
(2) Then the material after the prepolymerization reaction, hydrogen and propylene are contacted to carry out homopolymerization reaction to obtain polymer powder;
(3) Introducing polymer powder and liquid-phase propylene into a gas-solid separator provided with a gas-phase outlet, wherein the liquid-phase propylene is vaporized in the gas-solid separator so as to carry and discharge light components from the gas-phase outlet of the gas-solid separator;
(4) And (4) carrying out copolymerization reaction of propylene and alpha-olefin on the basis of removing the polymer powder carrying light components in the step (3) to obtain impact-resistant polypropylene powder, wherein the alpha-olefin is ethylene and/or alpha-olefin with 4-10 carbon atoms.
In a second aspect, the present invention provides an impact polypropylene produced by the process as described above.
Through the technical scheme, the method provided by the invention effectively reduces the influence of light components (including hydrogen and ethylene) carried by upstream polymer powder on the control of downstream reaction composition by effectively reducing the light components carried by the upstream polymer powder to enter the downstream reaction, thereby being beneficial to improving the performance of a polymer product and being capable of obtaining the polymer product with high impact strength. The invention has low requirement on equipment, and particularly can realize the removal of the entrained light components without additionally introducing equipment in the loop polypropylene production process of liquid-phase bulk polymerization and gas-phase polymerization.
Drawings
For the purpose of illustrating the invention more clearly, the drawings are illustrative of particular embodiments of the invention and are not to be construed as limiting the invention.
FIG. 1 is a schematic flow diagram according to one embodiment of the present invention.
Description of the reference numerals
1. Pre-complexing reactor
2. Prepolymerization reactor
3. First stage polymerization reactor
4. Gas-solid separator
5. Second stage polymerization reactor
100. Feed inlet for first stage polymerization reactor
101. Discharge port of first stage polymerization reactor
102. Liquid phase propylene inlet
103. Gas phase outlet of gas-solid separator
104. Material outlet of gas-solid separator
105. Discharge port of second stage polymerization reactor
106. Gas phase outlet of second stage polymerization reactor
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, the term "removal" is used, without going to the contrary, to mean a reduction of the content of entrained light components by at least 80%; the unit "ppmV" refers to parts per million by volume.
The invention provides a method for preparing impact polypropylene, which is characterized by comprising the following steps:
(1) Subjecting propylene to a prepolymerization reaction in the presence of a catalyst system comprising a (main) catalyst, a cocatalyst and optionally an external electron donor;
(2) Then, the material after the prepolymerization reaction, hydrogen and propylene are contacted for homopolymerization reaction to obtain polymer powder;
(3) Introducing polymer powder and liquid-phase propylene into a gas-solid separator provided with a gas-phase outlet, wherein the liquid-phase propylene is vaporized in the gas-solid separator so as to carry entrained light components to be discharged from the gas-solid outlet of the gas-solid separator;
(4) And (3) carrying out copolymerization reaction of propylene and alpha-olefin on the basis of removing the polymer powder carrying light components in the step (3) to obtain the impact-resistant polypropylene powder, wherein the alpha-olefin is ethylene and/or alpha-olefin with 4-10 carbon atoms.
According to the present invention, in the step (1), there is no particular requirement for the prepolymerization, and the conditions for the prepolymerization may include: the temperature is from-10 ℃ to 50 ℃, preferably from 0 ℃ to 40 ℃, more preferably from 5 ℃ to 20 ℃. The prepolymerization conditions may further comprise: the pressure is 1 to 8MPa, preferably 1.2 to 5.5MPa, more preferably 3 to 4.5MPa. The prepolymerization conditions may further include: the prepolymerization ratio is 0.5 to 1000 times, preferably 5 to 500 times, more preferably 20 to 300 times, particularly 100 to 150 times. "multiple prepolymerization" means the weight ratio of the polymer produced to the catalyst in the prepolymerization stage.
According to the invention, in step (1), the weight ratio of catalyst to propylene is 1 (500-150000), preferably 1 (800-80000), more preferably 1 (15000-20000).
According to the present invention, in the step (1), the catalyst is not particularly limited, and may be any of various existing catalysts suitable for preparing propylene polymers, including single site catalysts such as Ziegler-Natta catalysts or metallocenes.
According to the present invention, in step (1), the prepolymerization reaction can be carried out in the presence of a cocatalyst such as organoaluminum and optionally an external electron donor. According to the method of the present invention, the catalyst, the cocatalyst and the optional external electron donor may or may not be subjected to a pre-complexation reaction before the prepolymerization reaction. The selection of the conditions for the pre-complexation reaction is within the ability of one skilled in the art and will not be described further herein.
Wherein the cocatalyst is generally an organoaluminum, which is not limited to any organoaluminum commonly used in the polyolefin industry at present, but is preferably at least one member selected from the group consisting of trialkylaluminums (e.g., trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, trihexylaluminum, trioctylaluminum, etc.), diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum dichloride and ethylaluminum dichlorideAnd (4) seed selection. The external electron donor is a substance to be selectively used, and generally, when a Ziegler-Natta catalyst is used, the external electron donor is used, but when a single-site catalyst such as a metallocene is used, the external electron donor may not be used. The external electron donor is preferably an organosilicon compound with a general formula of R n Si(OR') 4-n Wherein n is more than 0 and less than or equal to 3, R is selected from hydrogen atom, halogen, alkyl, cycloalkyl, aryl and halogenated alkyl, and R' is selected from alkyl, cycloalkyl, aryl and halogenated alkyl. Specific examples include, but are not limited to: diisopropyldimethoxysilane, cyclohexylmethyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyl-t-butyldimethoxysilane, methylisopropyldimethoxysilane, diphenoxydimethoxysilane, diphenyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, (1, 1-trifluoro-2-propyl) -2-ethylpiperidinyldimethoxysilane, and (1, 1-trifluoro-2-propyl) -methyldimethoxysilane, and the like. The amount of the catalyst, the cocatalyst and the external electron donor can be determined according to the needs, and preferably, the weight ratio of the cocatalyst to the catalyst is 1. The weight ratio of the cocatalyst to the external electron donor can be from 0.1 to 150, preferably from 2 to 1 to 150.
According to the present invention, in the step (2), there is no particular requirement for the conditions of the homopolymerization, and the conditions of the homopolymerization may include: the temperature is 30 to 150 ℃, preferably 50 to 100 ℃. The conditions of the homopolymerization reaction may further include: the pressure is 1-8MPa, preferably 1.2-5.5MPa. The conditions for the homopolymerization reaction may further include: the time is 10-180min, preferably 20-120min.
According to the invention, in step (2), the weight ratio of the material after the prepolymerization, hydrogen and propylene may be (0.02-1): 9.5X 10 -6 -1.4×10 -3 ) 1, preferably (0.05-0.6): (9.5X 10) -6 -5×10 -4 ):1. The amount of propylene used here is only the amount of propylene additionally introduced in step (2), and is not excluded from the list of propylene not being able to be usedThe amount of propylene brought in by the preceding step is avoided.
According to the present invention, step (2) is preferably carried out in a loop reactor.
In the present invention, the polymer powder in the step (3) inevitably carries entrained light components. The entrained lights are typically materials having a boiling point lower than that of propylene, and may be hydrogen, and may also be nitrogen, methane, ethane, ethylene, etc., if present. The inventor of the invention also finds that with the increase of the amount of the propylene in the external liquid phase, the method also has certain removal effect on heavy components such as 1-butene and the like carried in the polymer powder. In the step (3), the liquid-phase propylene is additionally introduced (added) with the liquid-phase propylene, rather than the liquid-phase propylene entrained in the polymer powder or the liquid-phase propylene from the upstream process.
In the present invention, the polymer powder fed into the gas-solid separator usually contains entrained volatile components in an amount of from 500 to 50000ppm by weight, and the light components (i.e., entrained light components, mainly hydrogen) in the volatile components in an amount of from 1000 to 50000ppmV, preferably from 2000 to 10000ppmV. The method of the invention is suitable for removing the light components carried in the polymer powder with various shapes, including particle shape, spherical shape or sphere-like shape.
According to a preferred embodiment of the present invention, in order to more effectively achieve the removal of the entrained light components in the polymer powder, the residence time of the polymer powder in the gas-solid separator is 0.5-20min, more preferably 2-10min, even more preferably 5-10min, such as 5min, 8min, 9min, 10min or any value in between.
In order to more effectively achieve separation of entrained volatile components and propylene from solids after vaporization, the gas-solid separator is preferably a device (e.g., a fluidized bed device) provided with an expansion section at the upper part, which can be designed by calculation methods known in the art, wherein the expansion section is a region free of solid materials, and the ratio of the maximum cross-sectional diameter of the expansion section to the holding section (i.e., the stripping section mentioned below) is generally 1.5-3 (e.g., 1.5, 1.8, 1.9, 2, 2.1, 2.2, 2.5, 3 or any value therebetween), and the height is also set to meet the requirements of solid settlement and avoiding stacking along the wall. Furthermore, the gas-solid separator may be a cyclone separator. The lower part of the gas-solid separator is a stripping section, namely a region where solid materials exist. Maintaining a certain material level of the polypropylene powder in the stripping section, adding the added liquid-phase propylene into a polypropylene powder bed layer below the bubble point temperature, vaporizing under the action of polymerization reaction heat, and stripping out light components carried in the polymer powder. The residence time of the polymer powder in the stripping section is from 0.5 to 20min, preferably from 2 to 10min.
According to the invention, the liquid phase propylene is preferably added in a proportion to the polymer powder, the weight ratio of liquid phase propylene to polymer powder being 0.05-1, more preferably 0.1-0.5, even more preferably 0.2-0.5, such as 0.2, 0.3, 0.4, 0.5 or any value between the above values.
According to the invention, in order to realize the uniform distribution of the liquid-phase propylene in the solid-phase polymer powder, the structures of a spray head, a dispersion pipe, a distribution disc and the like which are common in the field can be adopted. When the scheme of the gas-solid separator with the expansion section arranged at the upper part is adopted, the upper part can be also configured into a power separator, a filter and the like which are increased for realizing good gas-solid separation effect.
According to a preferred embodiment of the invention, the temperature in the gas-solid separator is 50-100 ℃, more preferably 60-80 ℃ (such as 60 ℃, 62 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ or any value in between). The temperature is the temperature in the zone in which the polymer powder is located, for example the stripping section.
According to a preferred embodiment of the present invention, the pressure in the gas-solid separator can be controlled between the pressure of the reactor upstream of the gas-solid separator and the pressure of the equipment downstream of the gas-solid separator, so that the material can be transported and transferred by means of a pressure difference, which may be in the range of 0.1-3MPa, preferably the pressure in the gas-solid separator is in the range of 1-2.5MPa, more preferably 1.5-2MPa (such as 1.5MPa, 1.6MPa, 1.7MPa, 1.8MPa, 1.9MPa, 2MPa or any value in between the above values).
According to the present invention, in the step (4), there is no particular requirement for the conditions of the copolymerization reaction, which may include: the temperature is 50 to 150 ℃ and preferably 60 to 95 ℃. The copolymerization conditions may further include: the pressure is 0.5-4MPa, preferably 1.2-3.5MPa. The copolymerization conditions may further include: the time is 10-180min, preferably 20-90min.
According to a preferred embodiment of the present invention, in the step (4), the α -olefin is used in an amount such that the volume of the α -olefin is 5 to 70% based on the total volume of the α -olefin and propylene in the copolymerization reaction system.
According to the present invention, in the step (4), the α -olefin may be any conventional olefin capable of being polymerized with propylene, for example, the α -olefin is ethylene and/or an α -olefin having 4 to 10 carbon atoms, and is preferably at least one of ethylene, 1-butene, 1-pentene, 1-hexene, 4-methylisoalene, 1-octene and 1-decene.
According to the present invention, step (4) is preferably carried out in a gas phase reactor.
The invention also provides impact polypropylene prepared by the method. The present invention achieves an impact polypropylene product with improved properties by reducing the amount of light components (including hydrogen) entrained with the upstream polymer powder entering downstream reactions during the manufacturing process.
The present invention will be described in detail below by way of examples. In the following examples:
the double-screw extruder is a GLS-30B plastic granulator of Suzhou Congrale rubber and plastic machinery Limited company;
the method for detecting hydrogen is online chromatography, and TGC-2000 type online chromatograph of ABB company is adopted;
ethylene content in the impact polypropylene product: measuring the ethylene content by using a ThermoNicolet200 type infrared analyzer;
rubber phase content
= 1-homopolymeric polymer
Wherein,
= weight of homopolypropylene/weight of total polypropylene product × 100%;
izod impact strength: measured according to the method described in GB/T1843-2008;
melt mass flow rate (melt index, MFR): measured at 230 ℃ under a load of 2.16kg using a melt index apparatus of type 7026 from CEAST, according to the method described in GB/T3682-2000; melt Flow Rate (MFR) of rubber phase Polymer 2 By
Is calculated to obtain wherein
MFR 1 、
MFR 2 MFR is the homopolymeric specific gravity, the homopolymeric melt index, the rubber phase polymeric specific gravity, the rubber phase polymeric melt index, the final polymeric melt index, respectively.
The following examples were carried out on a 25kg/h loop polypropylene pilot plant comprising, as shown in FIG. 1:
the pre-complexing reactor 1 is used for pre-complexing,
the pre-polymerization reactor (2) is provided with a pre-polymerization reactor,
a first-stage polymerization reactor 3 (loop reactor) provided with a first-stage polymerization reactor inlet 100 and a first-stage polymerization reactor outlet 101;
the gas-solid separator 4 comprises an expansion section arranged at the upper part and a stripping section arranged at the lower part, the ratio of the maximum cross section diameter of the expansion section to the maximum cross section diameter of the stripping section is 2, the expansion section is provided with a feed inlet of the gas-solid separator and a gas phase outlet 103 of the gas-solid separator, and the stripping section is provided with a liquid phase propylene inlet 102 and a material outlet 104 of the gas-solid separator;
a second-stage polymerization reactor 5 (gas-phase reactor) provided with a feed port of the second-stage polymerization reactor, a discharge port 105 of the second-stage polymerization reactor, and a gas-phase outlet 106 of the second-stage polymerization reactor;
wherein the discharge port 101 of the first stage polymerization reactor is connected to the feed port of a gas-solid separator, the feed outlet 104 of the gas-solid separator is connected to the feed port of the second stage polymerization reactor, and the second stage polymerization reactor 5 is further provided with a circulation line for circulating the gas discharged from the gas-phase outlet 106 of the second stage polymerization reactor in the second stage polymerization reactor.
Example 1
(1) Pre-complexation and pre-polymerization
The flow rate of the main catalyst (DQC 401 catalyst, beijing Ondah company of China petrochemical catalyst division) is 0.8g/h, the flow rate of the cocatalyst (triethylaluminum, TEA) is 6.33g/h, the flow rate of the external electron donor (diisopropyldimethoxysilane, DIPDMS) is 0.8g/h, and the pre-complexing reaction is carried out in a pre-complexing reactor 1 at 6 ℃ for 8min.
Continuously adding the catalyst system after pre-complexing into a continuous stirred tank type prepolymerization reactor 2, carrying out prepolymerization reaction in a propylene liquid-phase bulk environment, wherein the dosage of propylene is such that the weight ratio of a main catalyst (DQC 401 catalyst) to propylene is 5.33X 10 -5 :1, at a temperature of 12 ℃, a pressure of 4MPa and a reaction residence time of about 10min, under which the prepolymerization multiple of the catalyst is about 120 times.
(2) Homopolymerization of propylene
Continuously introducing the prepolymerized material (15 kg/H) into the first-stage polymerization reactor 3 from the feed inlet 100 of the first-stage polymerization reactor for homopolymerization, wherein the temperature of the loop polymerization reaction is 70 ℃, the reaction pressure is 4MPa, the reaction residence time is about 1H, hydrogen (5.5 g/H) is added into propylene (25 kg/H), the obtained polymer powder is discharged from the discharge outlet 101 of the first-stage polymerization reactor, and the concentration of the hydrogen (marked as H) in the discharged material is detected 2 (101) ) and sampling to determine the MFR of the product 1 。
(3) Gas-solid separation stage
The polymer powder is continuously fed into a stripping section in a gas-solid separator 4 from a feed inlet of the gas-solid separator, and the operating temperature and the operating pressure of the gas-solid separator 4 are respectively 70 ℃ and 1.8MPa. From gas-solid separationContinuously introducing liquid propylene into a liquid-phase propylene inlet 102 of the device, wherein the feeding amounts of polymer powder and the liquid-phase propylene are respectively 15kg/H and 7.5kg/H, the liquid-phase propylene is vaporized in a gas-solid separator so as to carry light components carried by the liquid-phase propylene to be discharged from a gas-phase outlet 103 of the gas-solid separator for recycling, the retention time of the polymer powder in the gas-solid separator is 10min, the polymer powder without the light components carried by the liquid-phase propylene is discharged from a material outlet 104 of the gas-solid separator, and the concentration (marked as H) of hydrogen in the discharged material is detected 2 (104))。
(4) Ethylene/propylene copolymerization
The polymer powder without the entrained light components enters a second-stage polymerization reactor 5 from a feed port of the second-stage polymerization reactor, copolymerization reaction of propylene and ethylene (ethylene/(ethylene + propylene) =0.4 (v/v)) is carried out on the basis of the polymer powder without the entrained light components, the temperature of the copolymerization reaction is 70 ℃, the pressure is 1.4MPa, the retention time is 30min, and the impact polypropylene product is continuously discharged from a discharge port 105 of the second-stage polymerization reactor. The resulting impact polypropylene product was tested for parameters such as MFR, ethylene content and impact strength.
Some experimental parameters and the results of the performance tests of the pellets obtained are shown in Table 1.
Example 2
(1) Pre-complexing and pre-polymerizing
The flow rate of the main catalyst (DQC 401 catalyst, beijing Ondah company of China petrochemical catalyst division) is 0.8g/h, the flow rate of the cocatalyst (triethylaluminum, TEA) is 6.33g/h, the flow rate of the external electron donor (cyclohexylmethyldimethoxysilane, CHMMS) is 0.8g/h, and the pre-complexing reaction is carried out in a pre-complexing reactor 1 at 6 ℃ for 8min.
Continuously adding the catalyst system after pre-complexing into a continuous stirred tank type prepolymerization reactor 2, and carrying out prepolymerization reaction in a propylene liquid-phase body environment, wherein the dosage of propylene is such that the weight ratio of a main catalyst (DQC 401 catalyst) to propylene is 6.15 multiplied by 10 -5 :1, the temperature is 8 ℃, the pressure is 3.5MPa, the reaction time is about 12min, and the prepolymerization multiple of the catalyst under the condition is about 100 times.
(2) Homopolymerization of propylene
Continuously (13 kg/H) introducing the prepolymerized material into a first-stage polymerization reactor 3 from a feed inlet 100 of the first-stage polymerization reactor for homopolymerization, wherein the temperature of loop polymerization is 65 ℃, the reaction pressure is 3.5MPa, the reaction residence time is about 1.1H, hydrogen (5.5 g/H) is added into propylene (23 kg/H), the obtained polymer powder is discharged from a discharge outlet 101 of the first-stage polymerization reactor, and the concentration of the hydrogen (marked as H) in the discharged material is detected 2 (101) ) and sampling to determine the MFR of the product 1 。
(3) Gas-solid separation stage
The polymer powder is continuously fed into a stripping section in a gas-solid separator 4 from a feed inlet of the gas-solid separator, and the operating temperature and the operating pressure of the gas-solid separator 4 are respectively 75 ℃ and 1.9MPa. Continuously introducing liquid propylene from a liquid-phase propylene inlet 102 of a gas-solid separator, wherein the feeding amounts of polymer powder and the liquid-phase propylene are respectively 15kg/H and 6kg/H, the liquid-phase propylene is vaporized in the gas-solid separator so as to carry light components carried by the liquid-phase propylene to be discharged from a gas-phase outlet 103 of the gas-solid separator for recycling, the retention time of the polymer powder in the gas-solid separator is 8min, the polymer powder without the light components carried by the liquid-phase propylene is discharged from a material outlet 104 of the gas-solid separator, and the concentration (marked as H) of hydrogen in the discharged material is detected 2 (104))。
(4) Ethylene/propylene copolymerization
The polymer powder without the entrained light components enters a second-stage polymerization reactor 5 from a feed inlet of the second-stage polymerization reactor, copolymerization reaction of propylene and ethylene (ethylene/(ethylene + propylene) =0.4 (v/v)) is carried out on the basis of the polymer powder without the entrained light components, the temperature of the copolymerization reaction is 70 ℃, the pressure is 1.4MPa, the retention time is 30min, and the impact polypropylene product is continuously discharged from a discharge outlet 105 of the second-stage polymerization reactor. The resulting impact polypropylene product was tested for parameters such as MFR, ethylene content and impact strength.
Some experimental parameters and the results of the property tests of the pellets obtained are shown in Table 1.
Example 3
(1) Pre-complexing and pre-polymerizing
The flow rate of the main catalyst (DQC 401 catalyst, luoyang division of China petrochemical Co., ltd.) was 0.8g/h, the flow rate of the cocatalyst (triethylaluminum, TEA) was 5g/h, the flow rate of the external electron donor (diisopropyldimethoxysilane, DIPDMS) was 0.6g/h, and the pre-complexation reaction was carried out in the pre-complexation reactor 1 at 6 ℃ for 8min.
Continuously adding the catalyst system after pre-complexing into a continuous stirred tank type prepolymerization reactor 2, and carrying out prepolymerization reaction in a propylene liquid-phase body environment, wherein the dosage of propylene is such that the weight ratio of a main catalyst (DQC 401 catalyst) to propylene is 6.15 multiplied by 10 -5 :1, the temperature is 20 ℃, the pressure is 4.5MPa, the reaction residence time is about 12min, and the prepolymerization multiple of the catalyst under the condition is about 150 times.
(2) Homopolymerization of propylene
Continuously (13 kg/H) introducing the prepolymerized material into the first-stage polymerization reactor 3 from the feed inlet 100 of the first-stage polymerization reactor for homopolymerization, wherein the temperature of the loop polymerization reaction is 70 ℃, the reaction pressure is 4.5MPa, the reaction residence time is about 1H, hydrogen (5.5 g/H) is added into the propylene (27 kg/H), the obtained polymer powder is discharged from the discharge outlet 101 of the first-stage polymerization reactor, and the concentration (marked as H) of the hydrogen in the discharged material is detected 2 (101) ) and sampling to determine the MFR of the product 1 。
(3) Gas-solid separation stage
The polymer powder is continuously fed into a stripping section in the gas-solid separator 4 from a feed inlet of the gas-solid separator, and the operating temperature and the pressure of the gas-solid separator 4 are 65 ℃ and 1.7MPa respectively. Continuously introducing liquid propylene from a liquid-phase propylene inlet 102 of a gas-solid separator, wherein the feeding amounts of polymer powder and the liquid-phase propylene are respectively 15kg/H and 5kg/H, the liquid-phase propylene is vaporized in the gas-solid separator so as to carry light components carried by the liquid-phase propylene to be discharged from a gas-phase outlet 103 of the gas-solid separator for recycling, the retention time of the polymer powder in the gas-solid separator is 5min, the polymer powder without the light components carried by the liquid-phase propylene is discharged from a material outlet 104 of the gas-solid separator, and the concentration (marked as H) of hydrogen in the discharged material is detected 2 (104))。
(4) Ethylene/propylene copolymerization
The polymer powder without the entrained light components enters a second-stage polymerization reactor 5 from a feed inlet of the second-stage polymerization reactor, copolymerization reaction of propylene and ethylene (ethylene/(ethylene + propylene) =0.4 (v/v)) is carried out on the basis of the polymer powder without the entrained light components, the temperature of the copolymerization reaction is 70 ℃, the pressure is 1.4MPa, the retention time is 30min, and the impact polypropylene product is continuously discharged from a discharge outlet 105 of the second-stage polymerization reactor. The resulting impact polypropylene product was tested for parameters such as MFR, ethylene content, and impact strength.
Some experimental parameters and the results of the property tests of the pellets obtained are shown in Table 1.
Example 4
(1) The same as example 1;
(2) The same as example 1, except that the amount of hydrogen fed was 10g/h;
(3) The same as example 1;
(4) Same as example 1
Some experimental parameters and the results of the performance tests of the pellets obtained are shown in Table 1.
Comparative example 1
Impact polypropylene was prepared according to the method of example 1 except that in step (3), no liquid phase propylene was introduced. Some experimental parameters and the results of the performance tests of the pellets obtained are shown in Table 1.
Comparative example 2
An impact polypropylene was prepared as in example 1, except that in step (3), the liquid phase propylene was replaced with vapor phase propylene. Some experimental parameters and the results of the performance tests of the pellets obtained are shown in Table 1.
TABLE 1
As can be seen from Table 1, the continuous feeding of liquid phase propylene to the stripping section of the gas-solid separator significantly reduced the concentration of hydrogen entrained to the gas phase reactor with the polymer powder, and thus the MFR of the rubber phase formed in the gas phase reactor 2 Is significantly reduced, i.e. rubber phase aggregationThe molecular weight of the compound increases. The impact strength of the polymer obtained by the method is obviously improved.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. A process for preparing an impact polypropylene, characterized in that the process comprises:
(1) Subjecting propylene to a prepolymerization reaction in the presence of a catalyst system comprising a catalyst, a cocatalyst and optionally an external electron donor;
(2) Then the material after the prepolymerization reaction, hydrogen and propylene are contacted to carry out homopolymerization reaction to obtain polymer powder;
(3) Introducing polymer powder and liquid-phase propylene into a gas-solid separator provided with a gas-phase outlet, wherein the liquid-phase propylene is vaporized in the gas-solid separator so as to carry and entrain light components to be discharged from the gas-phase outlet of the gas-solid separator, the upper part of the gas-solid separator is provided with an expanding section, the lower part of the gas-solid separator is provided with a stripping section, the ratio of the maximum cross-sectional diameter of the expanding section to the maximum cross-sectional diameter of the stripping section is 1.5-3, the weight ratio of the liquid-phase propylene to the polymer powder is 0.05-1, the temperature in the gas-solid separator is 50-100 ℃, the pressure is 0.1-3MPa, and the retention time of the polymer powder in the gas-solid separator is 0.5-20min;
(4) And (4) carrying out copolymerization reaction of propylene and alpha-olefin on the basis of the polymer powder with the light components removed in the step (3) to obtain impact-resistant polypropylene powder, wherein the alpha-olefin is ethylene and/or alpha-olefin with 4-10 carbon atoms.
2. The process according to claim 1, wherein in step (1), the conditions of the prepolymerization comprise: the temperature is-10 ℃ to 50 ℃; the pressure is 1-8MPa; the pre-polymerization multiple is 0.5-1000 times; the weight ratio of catalyst to propylene is 1:500-150000.
3. The process of claim 2, wherein in step (1), the prepolymerization conditions comprise: the temperature is 0-40 ℃; the pressure is 1.2-5.5MPa; the pre-polymerization multiple is 5 to 500 times; the weight ratio of catalyst to propylene is 1:800-80000.
4. The process according to claim 2 or 3, wherein in the step (1), the prepolymerization ratio is 20-300.
5. The method according to claim 1, wherein in step (2), the conditions of the homopolymerization reaction include: the temperature is 30-150 ℃; the pressure is 1-8MPa; the time is 10-180min; the weight ratio of the materials after the prepolymerization reaction, hydrogen to propylene is 0.02-1: 9.5X 10 -6 -1.4×10 -3 ：1。
6. The method according to claim 5, wherein in the step (2), the conditions of the homopolymerization reaction include: the temperature is 50-100 ℃; the pressure is 1.2-5.5MPa; the time is 20-120min; the weight ratio of the materials after the prepolymerization reaction, hydrogen to propylene is 0.05-0.6: 9.5X 10 -6 -5×10 -4 ：1。
7. The process according to claim 1, wherein in step (3), the residence time of the polymer powder in the gas-solid separator is 2 to 10min.
8. The process according to claim 1, wherein in step (3), the weight ratio of the liquid phase propylene to the polymer powder is from 0.1 to 0.5.
9. The method according to claim 1, wherein in step (4), the copolymerization reaction conditions comprise: the temperature is 50-150 ℃; the pressure is 0.5-4MPa; the time is 10-180min.
10. The method of claim 9, wherein in step (4), the copolymerization reaction conditions comprise: the temperature is 60-95 ℃; the pressure is 1.2-3.5MPa; the time is 20-90min.
11. The process according to claim 1, 9 or 10, wherein in the step (4), the α -olefin is used in an amount such that the volume of the α -olefin is 5 to 70% based on the total volume of the α -olefin and propylene in the copolymerization reaction system.
12. An impact polypropylene produced by the process of any one of claims 1 to 11.
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| CN107540772A (en) * | 2016-06-24 | 2018-01-05 | 中国石化扬子石油化工有限公司 | A kind of preparation method of transparent anti-impact acrylic polymers |
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