CN117861584A - Device and method for continuously producing polyolefin elastomer - Google Patents
Device and method for continuously producing polyolefin elastomer Download PDFInfo
- Publication number
- CN117861584A CN117861584A CN202311805697.5A CN202311805697A CN117861584A CN 117861584 A CN117861584 A CN 117861584A CN 202311805697 A CN202311805697 A CN 202311805697A CN 117861584 A CN117861584 A CN 117861584A
- Authority
- CN
- China
- Prior art keywords
- oligomerization
- copolymerization
- catalyst
- kettle
- ethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920006124 polyolefin elastomer Polymers 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000006384 oligomerization reaction Methods 0.000 claims abstract description 141
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 115
- 239000005977 Ethylene Substances 0.000 claims abstract description 51
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000002156 mixing Methods 0.000 claims abstract description 50
- 239000002904 solvent Substances 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims description 72
- 239000000203 mixture Substances 0.000 claims description 30
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 claims description 21
- 239000012752 auxiliary agent Substances 0.000 claims description 18
- 239000007795 chemical reaction product Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 9
- ZOICEQJZAWJHSI-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl)boron Chemical compound [B]C1=C(F)C(F)=C(F)C(F)=C1F ZOICEQJZAWJHSI-UHFFFAOYSA-N 0.000 claims description 7
- 238000006471 dimerization reaction Methods 0.000 claims description 7
- IEVJIMWHPIWBIS-UHFFFAOYSA-N n,n-dihexadecylaniline Chemical compound CCCCCCCCCCCCCCCCN(CCCCCCCCCCCCCCCC)C1=CC=CC=C1 IEVJIMWHPIWBIS-UHFFFAOYSA-N 0.000 claims description 7
- 238000005829 trimerization reaction Methods 0.000 claims description 7
- OHSJPLSEQNCRLW-UHFFFAOYSA-N triphenylmethyl radical Chemical compound C1=CC=CC=C1[C](C=1C=CC=CC=1)C1=CC=CC=C1 OHSJPLSEQNCRLW-UHFFFAOYSA-N 0.000 claims description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 6
- LQZDXSATRKTKIF-UHFFFAOYSA-L CCC(C)(C(C)(C)C)N[Ti+2](C1C=CC=C1)[SiH](C)C.[Cl-].[Cl-] Chemical compound CCC(C)(C(C)(C)C)N[Ti+2](C1C=CC=C1)[SiH](C)C.[Cl-].[Cl-] LQZDXSATRKTKIF-UHFFFAOYSA-L 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 6
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 6
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 5
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 4
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 4
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 4
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 3
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- FRBFQWMZETVGKX-UHFFFAOYSA-K chromium(3+);6-methylheptanoate Chemical compound [Cr+3].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O FRBFQWMZETVGKX-UHFFFAOYSA-K 0.000 claims description 3
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical group [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 claims description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 3
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 3
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000001282 iso-butane Substances 0.000 claims description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 3
- JYLPOJPHFDVWCY-UHFFFAOYSA-K oxolane;trichlorochromium Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3].C1CCOC1 JYLPOJPHFDVWCY-UHFFFAOYSA-K 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000000047 product Substances 0.000 description 11
- 238000005070 sampling Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 238000010924 continuous production Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 5
- -1 polyethylene Polymers 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 229920001038 ethylene copolymer Polymers 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BHTKQUGPJWEUOJ-UHFFFAOYSA-N C[SiH](C)C[Ti](C)(NC(C(C)(C)C)(CC)C)C1C=CC=C1 Chemical compound C[SiH](C)C[Ti](C)(NC(C(C)(C)C)(CC)C)C1C=CC=C1 BHTKQUGPJWEUOJ-UHFFFAOYSA-N 0.000 description 2
- 239000010724 circulating oil Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- 239000004831 Hot glue Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a device and a method for continuously producing polyolefin elastomer, wherein the device comprises an oligomerization mixing kettle, an oligomerization reaction kettle, a copolymerization mixing kettle and a copolymerization reaction kettle which are communicated in sequence. The invention controls the average residence time of ethylene and solvent in the copolymerization reaction kettle and the oligomerization reaction kettle by adding the oligomerization mixing kettle and the copolymerization mixing kettle, so that oligomerization reaction and copolymerization reaction can be continuously carried out, and the stability of products is improved.
Description
Technical Field
The invention belongs to the technical field of polyolefin elastomers, and particularly relates to a device and a method for continuously producing a polyolefin elastomer.
Background
Polyolefin elastomer (POE) is an ethylene/linear alpha-olefin random copolymer with high comonomer content developed by the dow company and the exkesen mobil company in the beginning of the 90 th century, with higher comonomer content and lower density in the POE molecular chain; the polymer molecular chains are all saturated bonds and are nonpolar groups, so that the polyolefin elastomer has the characteristics of excellent ageing resistance, corrosion resistance, thermal stability, water vapor permeation resistance and the like, and is widely applied to the fields of automobile parts, wires and cables, mechanical tools, household articles, toys, entertainment and sports articles, soles, sealing elements, hot melt adhesives and the like.
CN113248643a discloses a polyolefin elastomer, which is obtained by using ethylene as a raw material, and directly carrying out a copolymerization reaction on the obtained product after oligomerization reaction to obtain the polyolefin elastomer; the ethylene oligomerization product is directly pressed into a copolymerization kettle for copolymerization, the whole reaction process is intermittent, continuous production can not be realized, and the product stability is poor.
Disclosure of Invention
In view of the above, the present invention aims to provide an apparatus and a method for continuously producing a polyolefin elastomer, which can realize continuous production of a polyolefin elastomer with good product stability.
The invention provides a device for continuously producing polyolefin elastomer, which comprises an oligomerization mixing kettle, an oligomerization reaction kettle, a copolymerization mixing kettle and a copolymerization reaction kettle which are communicated in sequence:
the top of the oligomerization mixing kettle is provided with an oligomerization mixture discharge port, and the bottom of the oligomerization mixing kettle is provided with an oligomerization additive feed port, an ethylene feed port and a solvent feed port;
the bottom of the oligomerization reaction kettle is provided with an oligomerization mixture material feed inlet and an oligomerization catalyst feed inlet, and the top of the oligomerization reaction kettle is provided with an oligomerization reaction product discharge outlet;
the bottom of the copolymerization mixing kettle is provided with an oligomerization reaction product feed inlet, an ethylene feed inlet and a solvent feed inlet, and the top of the copolymerization mixing kettle is provided with a copolymerization mixture discharge outlet;
the bottom of the copolymerization reactor is provided with a copolymerization mixture feed inlet and a copolymerization catalyst feed inlet, and the top of the copolymerization reactor is provided with a copolymerization reaction product discharge outlet.
The invention provides a method for continuously producing polyolefin elastomer by adopting the device in the technical scheme, which comprises the following steps:
mixing solvent, ethylene and oligomerization auxiliary agent to obtain oligomerization mixed material;
oligomerization reaction is carried out on the oligomerization mixture under the action of an oligomerization catalyst, and an oligomerization reaction product is obtained;
mixing the oligomerization reaction product with a copolymerization auxiliary agent, supplementary ethylene and a solvent to obtain a copolymerization mixture;
and (3) carrying out copolymerization reaction on the copolymerization mixture under the action of a copolymerization catalyst to obtain the polyolefin elastomer.
Preferably, the oligomerization aid is selected from one or more of alkylaluminoxane, alkylaluminum, and organoboron compound;
the oligomerization catalyst is selected from one or more of an ethylene dimerization catalyst, an ethylene trimerization catalyst and an ethylene tetramerization catalyst;
the ethylene dimerization catalyst is selected from Ti (OC) 4 H 9 ) 4 、Ti(OiC 3 H 7 ) 4 And Ti (OC) 6 H 4 CH 3 ) 4 One or more of the following;
the ethylene trimerization catalyst is selected from chromium acetylacetonate, chromium tetrahydrofuran chloride, chromium isooctanoate or a P, N-containing ligand;
the ethylene tetramerization catalyst is selected from a silamine carbon bridged biphosphine chromium complex.
Preferably, the copolymerization catalyst is selected from dimethylsilyl-tetramethyl cyclopentadienyl-t-butylamino-titanium dichloride;
or a molar ratio of 1:1.2 to 5.0 of a mixture of dimethylsilyl-tetramethyl cyclopentadienyl-t-butylamino-dimethyl titanium and a boron agent; the boron agent is selected from one or more of perfluorophenyl boron, triphenylcarbon tetra (pentafluorophenyl) borate, N-dimethylanilinium tetra (pentafluorophenyl) borate and N, N-di (hexadecyl) anilinium tetra (pentafluorophenyl) borate;
the copolymerization auxiliary agent is selected from one or more of triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum dichloride, methylaluminoxane, modified methylaluminoxane, perfluorophenyl boron, triphenylcarbon tetra (pentafluorophenyl) borate, N-dimethylanilinium tetra (pentafluorophenyl) borate and N, N-di (hexadecyl) anilinium tetra (pentafluorophenyl) borate.
Preferably, the oligomerization temperature is 30-100 ℃, and the oligomerization pressure is 0.4-2 MPa;
the temperature of the copolymerization reaction is 60-250 ℃, and the pressure of the copolymerization reaction is 1.0-15.0 MPa.
Preferably, the solvent is selected from one or more of isobutane, n-pentane, isopentane, n-hexane, methylcyclopentane, n-heptane, methylcyclohexane, isooctane and toluene.
Preferably, the residence time of the oligomerization reaction is from 5 to 30 minutes;
the residence time of the copolymerization reaction is 5-30 min.
The invention provides a device for continuously producing polyolefin elastomer, which comprises an oligomerization mixing kettle, an oligomerization reaction kettle, a copolymerization mixing kettle and a copolymerization reaction kettle which are communicated in sequence. The invention controls the average residence time of ethylene and solvent in the copolymerization reaction kettle and the oligomerization reaction kettle by adding the oligomerization mixing kettle and the copolymerization mixing kettle, so that oligomerization reaction and copolymerization reaction can be continuously carried out, and the stability of products is improved.
Drawings
FIG. 1 is a schematic structural view of an apparatus for continuously producing polyolefin elastomer according to the present invention.
Detailed Description
The invention provides a device for continuously producing polyolefin elastomer, which comprises an oligomerization mixing kettle, an oligomerization reaction kettle, a copolymerization mixing kettle and a copolymerization reaction kettle which are communicated in sequence:
the top of the oligomerization mixing kettle is provided with an oligomerization mixture discharge port, and the bottom of the oligomerization mixing kettle is provided with an oligomerization additive feed port, an ethylene feed port and a solvent feed port;
the bottom of the oligomerization reaction kettle is provided with an oligomerization mixture material feed inlet and an oligomerization catalyst feed inlet, and the top of the oligomerization reaction kettle is provided with an oligomerization reaction product discharge outlet;
the bottom of the copolymerization mixing kettle is provided with an oligomerization reaction product feed inlet, an ethylene feed inlet and a solvent feed inlet, and the top of the copolymerization mixing kettle is provided with a copolymerization mixture discharge outlet;
the bottom of the copolymerization reactor is provided with a copolymerization mixture feed inlet and a copolymerization catalyst feed inlet, and the top of the copolymerization reactor is provided with a copolymerization reaction product discharge outlet.
The oligomerization additive feed inlet, the ethylene feed inlet and the solvent feed inlet in the invention can be the same feed inlet, namely, the solvent, the ethylene and the oligomerization additive enter the oligomerization mixing kettle from the same feed inlet. After the oligomerization mixing kettle is filled with the materials, the materials overflow from a kettle ejection valve of the oligomerization mixing kettle and enter the oligomerization reaction kettle from the bottom of the kettle.
The material after oligomerization enters the copolymerization mixing kettle from the kettle top of the oligomerization mixing kettle, the supplemented ethylene, solvent and copolymerization auxiliary agent enter the copolymerization mixing kettle through the other path, the material overflows from a kettle ejection valve after filling the copolymerization mixing kettle, and then enters the copolymerization reaction kettle from the kettle bottom of the copolymerization reaction kettle. The internal pressure of the copolymerization reaction kettle is controlled by a proportional valve; the reaction temperature in the reactor is reached by adjusting the oil bath of the copolymerization reactor. The invention starts the reaction after adding the copolymerization catalyst into the copolymerization reactor, and the residence time of the materials in the copolymerization reactor can be adjusted by changing the flow of the solvent.
According to the invention, the average residence time of ethylene and solvent in the oligomerization reaction kettle and the copolymerization reaction kettle is controlled by adding the mixing kettle and adjusting the flow of the solvent, so that oligomerization and copolymerization reactions can be continuously carried out, and the experimental stability is improved.
The invention provides a method for continuously producing polyolefin elastomer by adopting the device of the technical scheme, which comprises the following steps:
mixing solvent, ethylene and oligomerization auxiliary agent to obtain oligomerization mixed material;
oligomerization reaction is carried out on the oligomerization mixture under the action of an oligomerization catalyst, and an oligomerization reaction product is obtained;
mixing the oligomerization reaction product with a copolymerization auxiliary agent, supplementary ethylene and a solvent to obtain a copolymerization mixture;
and (3) carrying out copolymerization reaction on the copolymerization mixture under the action of a copolymerization catalyst to obtain the polyolefin elastomer.
Before the experiment, under the protection of nitrogen, the oligomerization auxiliary agent, the oligomerization catalyst, the copolymerization auxiliary agent and the copolymerization catalyst are respectively prepared with a solvent into solutions and stored in respective charging tanks; the solvent and ethylene are refined to remove impurities, so as to meet the polymerization requirement. Before the experiment, the reaction kettle, the mixing kettle and the pipeline are cleaned by solution prepared by triisobutylaluminum and a solvent to remove water and oxygen.
The invention mixes solvent, ethylene and oligomerization auxiliary agent to obtain oligomerization mixture. In the invention, the solvent, ethylene and oligomerization auxiliary agent are mixed in an oligomerization mixing kettle; mixing is carried out under the stirring condition, and the stirring speed is 450-550 rpm; the mixing time is 5-30 min; the mixing temperature is 30-100 ℃.
The oligomerization auxiliary agent is one or more selected from alkyl aluminoxane, alkyl aluminum and organic boron compounds; preferably selected from one or more of triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum dichloride, methylaluminoxane (MAO), modified Methylaluminoxane (MMAO), perfluorophenyl boron, triphenylcarbon tetrakis (pentafluorophenyl) borate, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and N, N-di (hexadecyl) anilinium tetrakis (pentafluorophenyl) borate.
The solvent used in the oligomerization mixing kettle is selected from one or more of isobutane, n-pentane, isopentane, n-hexane, methylcyclopentane, n-heptane, methylcyclohexane, isooctane and toluene.
The flow rate of the solvent is 0.5-5 kg/h; the feeding flow of ethylene in the oligomerization mixture kettle is 0.1-1 kg/h; the feeding amount of the oligomerization catalyst is 0.1-100 mu mol/h, and the mol ratio of the oligomerization auxiliary agent to the catalyst is 1.5-10000.
The oligomerization mixture is subjected to oligomerization reaction under the action of an oligomerization catalyst to obtain an oligomerization reaction product. The oligomerization catalyst is selectedOne or more of a self-ethylene dimerization catalyst, an ethylene trimerization catalyst and an ethylene tetramerization catalyst; the ethylene dimerization catalyst is selected from Ti (OC) 4 H 9 ) 4 、Ti(OiC 3 H 7 ) 4 And Ti (OC) 6 H 4 CH 3 ) 4 One or more of the following; the ethylene trimerization catalyst is selected from chromium acetylacetonate, chromium tetrahydrofuran chloride, chromium isooctanoate or a P, N-containing ligand; the ethylene tetramerization catalyst is selected from a silamine carbon bridged biphosphine chromium complex.
In a specific embodiment, the P, N-containing ligand is specifically
The ethylene tetramerization catalyst is
The feeding flow of the oligomerization catalyst is 0.1-100 mu mol/h. The oligomerization reaction temperature is 30-100 ℃, the residence time of the oligomerization reaction kettle is 5-30 min, and the oligomerization reaction pressure is 0.4-2 MPa. The residence time of the materials in the oligomerization reactor can be adjusted by changing the flow of each material. In a specific embodiment, in an oligomerization polymerization kettle, the feeding flow of normal hexane is 1.44kg/h, the feeding flow of oligomerization polyethylene is 0.80kg/h, the flow of oligomerization catalyst promoter is 20 mu mol/h, the feeding flow of oligomerization catalyst is 10mmol/h, the pressure in the oligomerization kettle is controlled at 1MPa, and the oligomerization reaction temperature is 80 ℃.
After the oligomerization reaction product is obtained, the oligomerization reaction product is mixed with a copolymerization auxiliary agent, supplementary ethylene and a supplementary solvent to obtain a copolymerization mixture. The copolymerization auxiliary agent is selected from one or more of triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, dichloroethylaluminum, methylaluminoxane, modified methylaluminoxane, perfluorophenyl boron, triphenylcarbon tetra (pentafluorophenyl) borate, N-dimethylanilinium tetra (pentafluorophenyl) borate and N, N-di (hexadecyl) anilinium tetra (pentafluorophenyl) borate; the flow rate of the copolymerization auxiliary agent is 0.15-1500 mu mol/h. The flow rate of the supplementary ethylene is 0.1-1 kg/h; the flow rate of the supplementary solvent is 0.1-1 kg/h.
After the copolymerization mixture is obtained, the copolymerization mixture is subjected to copolymerization reaction under the action of a copolymerization catalyst to obtain the polyolefin elastomer. The copolymerization catalyst is selected from dimethylsilyl bridging group-tetramethyl cyclopentadienyl-tertiary butylamino-titanium dichloride; or a molar ratio of 1:1.2 to 5.0 of a mixture of dimethylsilyl-tetramethyl cyclopentadienyl-t-butylamino-dimethyl titanium and a boron agent; the boron agent is selected from one or more of perfluorophenyl boron, triphenylcarbon tetra (pentafluorophenyl) borate, N-dimethylanilinium tetra (pentafluorophenyl) borate, and N, N-di (hexadecyl) anilinium tetra (pentafluorophenyl) borate. The feeding flow of the copolymerization catalyst is 0.1-100 mu mol/h. In a specific embodiment, the copolymerization catalyst is dimethylsilyl-tetramethyl cyclopentadienyl-t-butylamino-titanium dichloride.
The temperature of the copolymerization reaction in the invention is 60-250 ℃, preferably 100-200 ℃; the pressure of the copolymerization reaction is 1.0-15.0 MPa; the residence time in the copolymerization reaction kettle is 5-30 min.
The residence time of the materials in the copolymerization reaction kettle can be adjusted by changing the flow rate of the solvent. In a specific embodiment, the temperature of the copolymerization reaction is 140 ℃, the feeding flow rate of the ethylene copolymer is 0.40kg/h, the feeding flow rate of the catalyst copolymer is 20 mu mol/h, the flow rate of the catalyst copolymer promoter is 10mmol/h, and the pressure in the copolymerization kettle is controlled at 4.0MPa.
The invention collects the materials continuously flowing out of the copolymerization reaction kettle, filters and pumps the materials, and carries out vacuum drying for more than 5 hours at the temperature of 100 ℃. In a specific embodiment, after continuous operation for 5 hours, sampling is carried out for 15 minutes each time, sampling is carried out for 3 times continuously, and after the sample is washed by a large amount of acidified ethanol for several times, the sample is dried in vacuum at 100 ℃ for more than 8 hours.
The method provided by the invention directly produces POE products by using ethylene as a raw material, and reduces the cost of purchasing alpha-olefin. The invention adopts a continuous production process, ensures the stability of the product and further reduces the cost; and a continuous production process is adopted, so that the product performance is convenient to adjust.
The invention adopts a continuous production process, the product performance can be directly adjusted by adjusting the material consumption and the reaction condition, and the possibility of industrial continuous production is verified; because the feeding flow and the reaction conditions are more stable in continuous production, the interference factors in intermittent production are reduced, and the performance of the produced POE product is more stable.
The reaction kettle adopted in the invention is heated by the heat conduction oil in the jacket, the heat conduction oil is circularly heated by the circulating oil bath operation, and the cooling water pipe with the electromagnetic valve is arranged in the circulating oil bath. The pressure in the kettle is controlled by a pneumatic proportional valve arranged on a discharging pipe, and the control mode is as follows: the pressure in the kettle is converted into an analog signal through a pressure sensor conversion process, the analog signal is received by an AI module in the PLC and then converted into a digital signal, the digital signal is transmitted to a CPU module for calculation, then the CPU module outputs a new digital signal and converts the output analog signal through an AO module, the analog signal is transmitted to an electric conversion joint on the pneumatic proportional valve and converted into air pressure of 0.2-0.4MPa, and an actuating mechanism of the proportional valve is driven to move up and down: when the pressure in the kettle is greater than the pressure set value, the proportional valve is opened for pressure relief, and when the pressure in the kettle is less than the pressure set value, the proportional valve is closed for pressure holding, so that the dynamic balance of the pressure in the kettle is realized, and the pressure in the kettle is stabilized at +/-1.5 bar of the set value.
The method is carried out in an experimental platform of olefin high-temperature high-pressure double-kettle continuous solution polymerization engineering. The platform is highly automated, the main body is provided with an automatic temperature control system, an automatic pressure control system and an automatic feeding control system, all temperature, pressure and flow data in the system can be monitored and stored on line in real time, and all liquid and gas materials are automatically and continuously fed and discharged. The platform auxiliary system also comprises a gas purification system, a solvent purification system and an inert gas protection system.
In order to further illustrate the present invention, an apparatus and method for continuously producing polyolefin elastomer according to the present invention will be described in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The oligomerization catalyst used in this example: ethylene dimerization catalyst Ti (OC) 4 H 9 ) 4 The method comprises the steps of carrying out a first treatment on the surface of the Copolymerization catalyst: dimethylsilyl-tetramethyl cyclopentadienyl-t-butylamino-titanium dichloride; and (3) a cocatalyst: MMAO; solvent: n-hexane.
The volume of the oligomerization polymerization kettle is 1L, the temperature is set to 80 ℃, the stirring rotation speed is set to 500r/min, the feeding flow of normal hexane is 1.44kg/h, the feeding flow of oligomerization polyethylene is 0.80kg/h, the flow of oligomerization catalyst promoter is 20 mu mol/h, the feeding flow of oligomerization catalyst is 10mmol/h, and the pressure in the oligomerization kettle is 1MPa; the temperature of the copolymerization reaction is 140 ℃, the feeding flow rate of the ethylene copolymer is 0.40kg/h, the feeding flow rate of the catalyst copolymer is 20 mu mol/h, the flow rate of the catalyst copolymer promoter is 10mmol/h, and the pressure in the copolymerization kettle is controlled at 4.0MPa; after the experiment operation is stable for 5 hours, sampling is carried out, each time of sampling is carried out for 15 minutes, sampling is carried out for 3 times continuously, the sample is washed by a large amount of acidified ethanol for several times, and vacuum drying is carried out for more than 8 hours at 100 ℃, and the test results of the sample are shown in table 1:
TABLE 1
Example 2
The oligomerization catalyst used in this example: ethylene trimerization catalyst isCopolymerization catalyst: dimethylsilyl-tetramethyl cyclopentadienyl-t-butylamino-titanium dichloride; and (3) a cocatalyst: MMAO; solvent: n-hexane.
The volume of the oligomerization polymerization kettle is 1L, the temperature is set to 80 ℃, the stirring rotation speed is set to 500r/min, the feeding flow of normal hexane is 1.44kg/h, the feeding flow of oligomerization polyethylene is 0.80kg/h, the flow of oligomerization catalyst promoter is 20 mu mol/h, the feeding flow of oligomerization catalyst is 10mmol/h, and the pressure in the oligomerization kettle is 1MPa; the temperature of the copolymerization reaction is 140 ℃, the feeding flow rate of the ethylene copolymer is 0.40kg/h, the feeding flow rate of the catalyst copolymer is 20 mu mol/h, the flow rate of the catalyst copolymer promoter is 10mmol/h, and the pressure in the copolymerization kettle is controlled at 4.0MPa; after the experiment operation is stable for 5 hours, sampling is carried out, each time of sampling is carried out for 15 minutes, sampling is carried out for 3 times continuously, the sample is washed by a large amount of acidified ethanol for several times, and vacuum drying is carried out for more than 8 hours at 100 ℃, and the test results of the sample are shown in table 2:
TABLE 2
Example 3
The oligomerization catalyst used in this example: ethylene tetramerization catalyst:copolymerization catalyst: dimethylsilyl-tetramethyl cyclopentadienyl-t-butylamino-titanium dichloride; and (3) a cocatalyst: MMAO; solvent: n-hexane.
The volume of the oligomerization polymerization kettle is 1L, the temperature is set to 80 ℃, the stirring rotation speed is set to 500r/min, the feeding flow of normal hexane is 1.44kg/h, the feeding flow of oligomerization polyethylene is 0.80kg/h, the flow of oligomerization catalyst promoter is 20 mu mol/h, the feeding flow of oligomerization catalyst is 10mmol/h, and the pressure in the oligomerization kettle is 1MPa; the temperature of the copolymerization reaction is 140 ℃, the feeding flow rate of the ethylene copolymer is 0.40kg/h, the feeding flow rate of the catalyst copolymer is 20 mu mol/h, the flow rate of the catalyst copolymer promoter is 10mmol/h, and the pressure in the copolymerization kettle is controlled at 4.0MPa; after the experiment operation is stable for 5 hours, sampling is carried out, each time of sampling is carried out for 15 minutes, sampling is carried out for 3 times continuously, the sample is washed by a large amount of acidified ethanol for several times, and vacuum drying is carried out for more than 8 hours at 100 ℃, and the test results of the sample are shown in table 3:
TABLE 3 Table 3
From the above embodiments, the present invention provides an apparatus for continuously producing a polyolefin elastomer, which comprises an oligomerization mixing kettle, an oligomerization reaction kettle, a copolymerization mixing kettle and a copolymerization reaction kettle which are sequentially communicated. The invention controls the average residence time of ethylene and solvent in the copolymerization reaction kettle and the oligomerization reaction kettle by adding the oligomerization mixing kettle and the copolymerization mixing kettle, so that oligomerization reaction and copolymerization reaction can be continuously carried out, and the stability of products is improved.
The foregoing is merely a preferred embodiment of the present invention and 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, which are intended to be comprehended within the scope of the present invention.
Claims (7)
1. The device for continuously producing the polyolefin elastomer comprises an oligomerization mixing kettle, an oligomerization reaction kettle, a copolymerization mixing kettle and a copolymerization reaction kettle which are communicated in sequence:
the top of the oligomerization mixing kettle is provided with an oligomerization mixture discharge port, and the bottom of the oligomerization mixing kettle is provided with an oligomerization additive feed port, an ethylene feed port and a solvent feed port;
the bottom of the oligomerization reaction kettle is provided with an oligomerization mixture material feed inlet and an oligomerization catalyst feed inlet, and the top of the oligomerization reaction kettle is provided with an oligomerization reaction product discharge outlet;
the bottom of the copolymerization mixing kettle is provided with an oligomerization reaction product feed inlet, an ethylene feed inlet and a solvent feed inlet, and the top of the copolymerization mixing kettle is provided with a copolymerization mixture discharge outlet;
the bottom of the copolymerization reactor is provided with a copolymerization mixture feed inlet and a copolymerization catalyst feed inlet, and the top of the copolymerization reactor is provided with a copolymerization reaction product discharge outlet.
2. A process for continuously producing a polyolefin elastomer using the apparatus of claim 1, comprising the steps of:
mixing solvent, ethylene and oligomerization auxiliary agent to obtain oligomerization mixed material;
oligomerization reaction is carried out on the oligomerization mixture under the action of an oligomerization catalyst, and an oligomerization reaction product is obtained;
mixing the oligomerization reaction product with a copolymerization auxiliary agent, supplementary ethylene and a solvent to obtain a copolymerization mixture;
and (3) carrying out copolymerization reaction on the copolymerization mixture under the action of a copolymerization catalyst to obtain the polyolefin elastomer.
3. The method of claim 2, wherein the oligomerization aid is selected from one or more of alkylaluminoxane, alkylaluminum, and organoboron compound;
the oligomerization catalyst is selected from one or more of an ethylene dimerization catalyst, an ethylene trimerization catalyst and an ethylene tetramerization catalyst;
the ethylene dimerization catalyst is selected from Ti (OC) 4 H 9 ) 4 、Ti(OiC 3 H 7 ) 4 And Ti (OC) 6 H 4 CH 3 ) 4 One or more of the following;
the ethylene trimerization catalyst is selected from chromium acetylacetonate, chromium tetrahydrofuran chloride, chromium isooctanoate or a P, N-containing ligand;
the ethylene tetramerization catalyst is selected from a silamine carbon bridged biphosphine chromium complex.
4. A process according to claim 3, wherein the copolymerization catalyst is selected from the group consisting of dimethylsilyl-tetramethylcyclopentadienyl-t-butylamino-titanium dichloride;
or a mixture of dimethylsilyl bridge group-tetramethyl cyclopentadienyl-tertiary butylamino-dimethyl titanium and boron agent in a molar ratio of 1:1.2-5.0; the boron agent is selected from one or more of perfluorophenyl boron, triphenylcarbon tetra (pentafluorophenyl) borate, N-dimethylanilinium tetra (pentafluorophenyl) borate and N, N-di (hexadecyl) anilinium tetra (pentafluorophenyl) borate;
the copolymerization auxiliary agent is selected from one or more of triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum dichloride, methylaluminoxane, modified methylaluminoxane, perfluorophenyl boron, triphenylcarbon tetra (pentafluorophenyl) borate, N-dimethylanilinium tetra (pentafluorophenyl) borate and N, N-di (hexadecyl) anilinium tetra (pentafluorophenyl) borate.
5. The method according to claim 2, wherein the oligomerization temperature is 30-100 ℃, and the oligomerization pressure is 0.4-2 MPa;
the temperature of the copolymerization reaction is 60-250 ℃, and the pressure of the copolymerization reaction is 1.0-15.0 MPa.
6. A process according to claim 3, wherein the solvent is selected from one or more of isobutane, n-pentane, isopentane, n-hexane, methylcyclopentane, n-heptane, methylcyclohexane, isooctane and toluene.
7. A process according to claim 3, characterized in that the oligomerization residence time is 5 to 30min;
the residence time of the copolymerization reaction is 5-30 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311805697.5A CN117861584A (en) | 2023-12-25 | 2023-12-25 | Device and method for continuously producing polyolefin elastomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311805697.5A CN117861584A (en) | 2023-12-25 | 2023-12-25 | Device and method for continuously producing polyolefin elastomer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117861584A true CN117861584A (en) | 2024-04-12 |
Family
ID=90594105
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311805697.5A Pending CN117861584A (en) | 2023-12-25 | 2023-12-25 | Device and method for continuously producing polyolefin elastomer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117861584A (en) |
-
2023
- 2023-12-25 CN CN202311805697.5A patent/CN117861584A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3274686B2 (en) | Polymerization process for producing polyolefin elastomers, cation-forming cocatalyst for activating metallocene procatalysts, polyolefin elastomers having unique properties and products made therefrom | |
| CN109535323B (en) | Preparation method of comb-shaped propenyl polyolefin thermoplastic elastomer | |
| CN109384885B (en) | Preparation method of comb-shaped vinyl polyolefin thermoplastic elastomer | |
| JPH01501633A (en) | Copolymer of ethylene and 1,3-butadiene | |
| NO173242B (en) | PROCEDURE FOR IN-SITU-MIXING POLYMERS | |
| CN111732682B (en) | Preparation method of cross-linked polyolefin for packaging high-light-transmittance solar cell | |
| JP7238135B2 (en) | Olefin polymerization catalyst and olefin polymer prepared using the same | |
| CN115010840A (en) | Preparation method of polyolefin elastomer | |
| CN115028765A (en) | Production method of polyolefin elastomer | |
| CN114539478A (en) | Preparation method of comb-shaped polyolefin thermoplastic elastomer based on feeding strategy regulation and control | |
| CN109535298B (en) | Early transition metal compound and preparation method thereof, catalyst composition for olefin polymerization and application thereof, and method for preparing olefin polymer | |
| CN111635494A (en) | Preparation method of comb-shaped propenyl olefin polymer | |
| CN113248643A (en) | Polyolefin elastomer and preparation method thereof | |
| CN109456445B (en) | Preparation method of comb-shaped propenyl polyolefin thermoplastic elastomer | |
| CN117861584A (en) | Device and method for continuously producing polyolefin elastomer | |
| CN110092856B (en) | Liquid copolymerized olefin, preparation method and application | |
| CN115073634B (en) | Process for producing poly-1-butene and poly-1-butene | |
| CN111662417A (en) | Preparation method of novel crosslinkable comb-shaped propenyl olefin polymer | |
| CN116023572A (en) | High-temperature solution polymerization process for copolymerization of ethylene and alpha-olefin | |
| CN111704703A (en) | Preparation method of crosslinkable comb-shaped vinyl olefin polymer | |
| CN113164946A (en) | Method for stabilizing hydrogenation catalyst | |
| CN111690086B (en) | Preparation method of rapid crosslinking type propenyl polyolefin for packaging solar cell | |
| CN114539477A (en) | Preparation method of ethylene propylene diene monomer | |
| CN114478889B (en) | Ethylene polymer and preparation method and application thereof | |
| CN115558048B (en) | Trimodal polyethylene and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |