CN108948248A - Method and device for producing polyolefin elastomer by gas phase method and application of polyolefin elastomer - Google Patents
Method and device for producing polyolefin elastomer by gas phase method and application of polyolefin elastomer Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 86
- 229920006124 polyolefin elastomer Polymers 0.000 title claims abstract description 56
- 238000004519 manufacturing process Methods 0.000 claims abstract description 53
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000007789 gas Substances 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 150000001336 alkenes Chemical class 0.000 claims abstract description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 21
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 polyethylene Polymers 0.000 claims abstract description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000005977 Ethylene Substances 0.000 claims abstract description 14
- 229920000573 polyethylene Polymers 0.000 claims abstract description 13
- 239000004698 Polyethylene Substances 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract 2
- 239000012808 vapor phase Substances 0.000 claims description 48
- 239000000463 material Substances 0.000 claims description 18
- 238000000889 atomisation Methods 0.000 claims description 12
- 238000002347 injection Methods 0.000 claims description 11
- 239000007924 injection Substances 0.000 claims description 11
- 239000012530 fluid Substances 0.000 claims description 10
- 238000003860 storage Methods 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 239000007921 spray Substances 0.000 claims description 6
- 238000011144 upstream manufacturing Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 2
- 230000003203 everyday effect Effects 0.000 claims description 2
- 238000009434 installation Methods 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 229920001971 elastomer Polymers 0.000 description 10
- 239000000806 elastomer Substances 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000012071 phase Substances 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000003426 co-catalyst Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 239000012968 metallocene catalyst Substances 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910010068 TiCl2 Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000003863 metallic catalyst Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 2
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- MXVFWIHIMKGTFU-UHFFFAOYSA-N C1=CC=CC1[Hf] Chemical compound C1=CC=CC1[Hf] MXVFWIHIMKGTFU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- HEAMQYHBJQWOSS-UHFFFAOYSA-N ethene;oct-1-ene Chemical compound C=C.CCCCCCC=C HEAMQYHBJQWOSS-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/34—Polymerisation in gaseous state
Landscapes
- 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)
- Polymerisation Methods In General (AREA)
Abstract
A method for producing polyolefin elastomer by a gas phase method, a device and an application of the polyolefin elastomer are provided, the method comprises the steps of carrying out reaction in a reactor using polyethylene particles as a seed bed, introducing raw material mixed gas comprising ethylene, hydrogen and nitrogen into the reactor to enable the polyethylene particles in the seed bed to flow and reach a fluidized state, then adding a catalyst into the reactor and introducing atomized liquid-drop-shaped comonomer into the reactor to carry out reaction, wherein the comonomer is long-chain olefin with 6-18 carbon atoms, and the density of the prepared polymerization product is 0.865-0.910g/cm3The long-chain olefin content is 6 to 40 wt%.
Description
Technical field
The present invention relates to a kind of manufacturing technique methods of ethylene octane copolymer, and more specifically, the present invention relates to one kind to adopt
Long-chain olefin is used to carry out the process of vapor phase method synthesis of polyolefins class elastomer as comonomer.
Background technique
Ethylene octane copolymer is a kind of ethylene with higher co-monomer content/advanced a- olefin random copolymer, is belonged to
In novel thermoplastic elastomer, being not required to vulcanization has elasticity, molecular weight and short-chain branch narrowly distributing, and co-monomer content is high
(10%-30%wt) has excellent cold resistance and ageing-resistant performance, good mechanical property and processing performance, can partially replace
For EP rubbers, be also widely used as the impact modifier of the polyolefine materials such as polypropylene, to prepare instrument board, bumper bar,
Connector and plug, pipeline, instrument part, sheet material, garden tool set and construction material, can also be directly prepared into molded product and
Extrusion molding product is the novel elastomer material of a kind of high-performance, high added value.
Currently, ethylene octane copolymer adopts metallocene catalysis technology and solution polymerization technique produces.By changing cyclopentadienyl
Metallic catalyst structure can accurately regulate and control the microstructure of polymer, to obtain the production with different chain structures and purposes
Product.The Insite that Dow Chemical Company is combined using self-control constrained geometry (CGC) metallocene catalyst and solution polymerization process
Technology produces two class POE products, class I goods name are as follows: Engage (0.865~0.895g/cm of density3), including ethylene-octene
16, elastomer, ethylene-butylene elastomer 8, another kind of trade name Affinity (0.895~0.915g/cm of density3),
For such ethylene-octene copolymer product octene-1 mass fraction less than 20%, Dow Chemical Company is called plastic body.Dow chemistry
The Chinese patent CN93105687.X of company's application is anti-with continuously stirring using CGC metallocene catalyst and solution polymerization process
Device is answered, elastomer, molecular weight distribution 1.5-2.5 are obtained.Major catalyst [C5Me4(Me2SiNi-Bu)]TiCl2, co-catalyst
Three (pentafluorophenyl group) boron, operating condition 3.5MPa, 114 DEG C, obtained -1 copolymer density 0.903g/cm of ethylene/octene3, MWD
It is 1.86.In patent WO9314132, major catalyst dialkyl group silicon bridge cyclopentadienyl group tert-butylamine titanocene compound (Me2Si
(C5Me4)(Nt-Bu)TiCl2), MAO, 3.1MPa, 120-160 DEG C of co-catalyst, Isopar (C8-C10 aliphatic hydrocarbon) solvent condition
Under, ethylene/1- octene copolymer is carried out, catalytic activity is greater than 1.2 × 107GPE/molTih, the density 0.8972- of copolymer
0.9233g/cm3。
In the Chinese patent CN99812381.1 of Exxon company, describe in aliphatic solvents with deliquescent enough
Means of special bridged metallocene catalysts (the fluorenes cyclopentadienyl hafnium metallic catalyst on carbon bridging containing triethyl group silicon substrate benzene substituent group), especially suitable for
Solution olefin polymerization process.It is co-catalyst by solvent, tri-n-octylaluminium of hexane under the conditions of nitrogen, 140 DEG C, 1.83MPa,
Ethylene and octene-1 copolymerization catalytic activity are greater than 8.5 × 106The octene-1 content of gPE/molMh, resulting polymers are greater than 6
ω %, molecular weight distribution are greater than 2.2；Under the conditions of 190 DEG C, 8.5MPa, hexane is solvent, (p-Et3Si-Ph)2C(2,7-Di-
tBu-Flu)(Cp)HfMe2For major catalyst, tri-n-octylaluminium is co-catalyst, the octene-1 content 17 of resulting polymers
ω %, molecular weight distribution 2.3.In patent CN99812494.X, the hafnocene catalyst replaced using non-coordinating anion, 140
DEG C, under the conditions of 1.83MPa, with triisobutyl aluminium (TIBA) co-catalyst, catalytic activity is up to 1 × 107GPE/molM, gained are poly-
The octene-1 content for closing object is greater than 20%.
Company of Mitsui elastomer Singapore (MELS) and LG Corp of South Korea are developed in succession using solution polymerization process
Series of polyolefins elastomer product is applied to the fields such as automobile component, footwear material, cable, sheet material and film.
Vapor phase method can produce full density polythene product because not influenced by so-called " liquid solvent ", at the same have both compared with
Low cost of investment and operating cost, is applied widely in industrial production, and this year largely introduces at home.Fluidized bed
Reactor is uniquely made in reactor types and gas-phase polyethylene production technology the most commonly used in industrial production polyethylene
Reactor types.
Currently, domestic ethylene octane copolymer, mainly from external import, the country is still confined to urge mostly to its research
Agent synthesis, product modification etc..
Summary of the invention
The purpose of the present invention is to provide a kind of methods of vapor phase method production polyolefin elastomer, to solve in the prior art
The liquid long-chain alhpa olefin of high comonomer content is unevenly distributed, altogether in gas phase seed bed in polyolefin elastic production procedure
The problem of poly- performance difference.
The object of the invention is also to provide the devices and polyolefin elastomer of a kind of vapor phase method production polyolefin elastomer
Application.
To achieve the above object, the present invention provides a kind of method of vapor phase method production polyolefin elastomer, with polyethylene
Particle is passed through reactor as being reacted in the reactor of seed bed, by the material mixed gas including ethylene, hydrogen and nitrogen
It is interior, make the polyethylene particle in seed bed occur to flow and reach fluidized state, catalyst is then added into reactor and leads to
The comonomer for entering atomized droplet-like is reacted, and the comonomer is that carbon atom number is 6~18 long-chain olefins, system
Standby polymerizate density is 0.865-0.910g/cm3, long-chain olefin content is 6-40wt%.
The method of vapor phase method production polyolefin elastomer of the present invention, wherein Ethylene mass point in material mixed gas
Number is 35~50%, and hydrogen quality score is 2~5%, and nitrogen mass score is 48~60%.
The method of vapor phase method production polyolefin elastomer of the present invention, wherein the volume fraction of seed bed is 0.05
~0.1.
The method of vapor phase method production polyolefin elastomer of the present invention, wherein the mass flow of long-chain olefin is second
The 10~50% of alkene mass flow.
The method of vapor phase method production polyolefin elastomer of the present invention, wherein temperature maintains 70 DEG C in reactor
Between~140 DEG C, pressure is maintained between 1.5MPa~2.5MPa.
To achieve the above object, the present invention also provides a kind of device of vapor phase method production polyolefin elastomer, described devices
For above-mentioned method, comprising:
Reactor, the reactor include narrow diameter section, extension diameter section and wide path, and the wide path diameter is greater than narrow diameter section,
Extension diameter section connects narrow diameter section and wide path and diameter becomes larger from the bottom to top, and the narrow diameter section bottom is equipped with circulating air entrance,
Circulation line entrance is equipped at the top of the wide path, the narrow diameter section lower sidewall is equipped with catalyst inlet and comonomer enters
Mouthful, the narrow diameter section side wall upper part is equipped with discharge port；
Catalyst storage tank, the catalyst storage tank are connected to catalyst inlet；
Unstripped gas hybrid system, the unstripped gas hybrid system are connected to circulating air entrance；
Comonomer atomization system, the comonomer atomization system are connected to comonomer entrance；And
Circulation line, described circulation line one end are connected to circulating air entrance, and the other end is connect with circulation line entrance, institute
Circulation line is stated equipped with gas-liquid separator.
The device of vapor phase method of the present invention production polyolefin elastomer, wherein in the narrow diameter section lower section by down toward
On be successively additionally provided with gas flow guiding ring and gas distribution grid.
The device of vapor phase method production polyolefin elastomer of the present invention, wherein the comonomer atomization system packet
Contain:
One ejection medium inlet valve, arrival end are connect with a high-pressure fluid delivery pump；
One nozzle unit, including a nozzle and straight tube, one end of the straight tube connect nozzle, and the other end and the injection are situated between
The outlet end of matter inlet valve connects, and the nozzle protrudes into the comonomer entrance, the pressure of the high-pressure fluid delivery pump
Greater than the pressure in the reactor, long-chain olefin enters the straight tube by ejection medium inlet valve under the action of pressure difference
And it is sprayed into the reactor along the straight tube through the nozzle；
One online more changing device, including an outer tube, an airtight valve, two limiters and a sealing element, the outer tube
It is set in outside the straight tube, the airtight valve is mounted on the straight tube and controls the straight tube and extraneous on-off, described
Two limiters are respectively provided on the outer tube at the both ends of airtight valve, to fixed jacket pipe and the straight tube to prevent from acting in pressure
Under be extruded, the sealing element is screwed on the outer tube and is located at the upstream of the airtight valve, and passing through rotating seal will
The straight tube and the outer tube are dismantled simultaneously or are fixed；
One nitrogen inlet valve is arranged in the gap on the outer tube and between the straight tube and outer tube and is connected to, nitrogen
Gas is flowed in the gap between the straight tube and outer tube and is purged around nozzle by nitrogen inlet valve.
The device of vapor phase method production polyolefin elastomer of the present invention, wherein the pressure of the high-pressure fluid delivery pump
The difference of pressure in power and reactor is 0.4-1.0MPa.
The device of vapor phase method production polyolefin elastomer of the present invention, wherein the diameter of the nozzle can be according to anti-
Answer diameter, the fluidized state selection plane injection in reactor or the conical jet of device.
The device of vapor phase method production polyolefin elastomer of the present invention, wherein the shape of the nozzle is fan-shaped spray
Mouth or conical nozzle.
The device of vapor phase method production polyolefin elastomer of the present invention, wherein of the injection of the conical nozzle
Angle is 60 degree to 120 degree.
The device of vapor phase method production polyolefin elastomer of the present invention, wherein the plane of the fan nozzle is sprayed
Subtended angle be 45 degree to 90 degree.
The device of vapor phase method of the present invention production polyolefin elastomer, wherein the internal diameter of the straight tube is 1/8 cun~
1/2 cun.
The device of vapor phase method production polyolefin elastomer of the present invention, wherein the wall thickness of the straight tube is according to reaction
It pressure in device and is determined according to the difference of the pressure in the pressure and reactor of the high-pressure fluid delivery pump, the straight tube
The range of wall thickness is 0.014 cun~0.083 cun.
The device of vapor phase method production polyolefin elastomer of the present invention, wherein the comonomer inlet is equipped with
One installs nozzle, and nozzle unit described in the installing pipe confession passes through and supports the nozzle unit.
Polyolefin elastomer production is carried out using the device of vapor phase method production polyolefin elastomer method particularly includes: reaction
Using polyethylene particle as seed bed in device, the material mixed gas including ethylene, hydrogen and nitrogen is entered by circulating air entrance
The narrow diameter section of reactor makes the polyethylene particle in seed bed occur to flow and reaches fluidized state, then passes through catalyst inlet
Catalyst is added, and is reacted by the comonomer that comonomer entrance is passed through atomized droplet-like, in reactor
Each stock material, when passing through the extension diameter section of reactor in uphill process, solid phase and gas phase and liquid phase separation, solid phase return to reaction
The reaction was continued in device, and gas phase and liquid phase enter in circulation line, and gas phase and liquid phase pass through the gas-liquid separator on circulation line point
From being circulated back in reactor that the reaction was continued, polyethylene product obtained after some time, and pass through discharge port and be discharged.
The material mixed gas of gas phase and the catalyst of liquid phase and long-chain olefin enter after circulation line, ethylene, hydrogen, nitrogen
The raw materials such as gas after circulating air compressor, circulating air heat exchanger by circulating air pipeline through circulating air entrance from fluidized bed bottom
Portion enters reactor, and liquid phase enters storage tank after separation, reenters reaction by comonomer entrance after feed pump
Device participates in polymerization reaction.
Preferably, in the charging course of injection of material mixed gas, need by gas flow guiding ring carry out it is pre-dispersed, later
Disperse and distribute again using gas distribution grid.
Except the air-flow by unstripped gas carries out the flowing and fluidisation of seed bed, seed bed can also pass through churned mechanically work
It is flowed and is fluidized with promoting it to realize.
To achieve the above object, the present invention also provides a kind of polyolefin elastomers in medical package material, automobile parts, electricity
Application in line cable, everyday articles and toy.
Beneficial effects of the present invention: the present invention provides the method, apparatus of a kind of vapor phase method production polyolefin elastomer and poly-
The application of olefin elastomer, the comonomer that droplet-like is added in reactor by the design of atomizer are reacted, high
Content higher alpha-long-chain olefin and ethylene copolymer prepare polyolefin elastomer, solve high comonomer content in current technology
Liquid long-chain alhpa olefin is unevenly distributed in gas phase seed bed, the problem of copolymerization performance difference.
Detailed description of the invention
Fig. 1 is the production technological process that vapor phase method of the present invention produces polyolefin elastomer；
Fig. 2 is the schematic diagram of reactor of the present invention；
Fig. 3 is the structural schematic diagram of comonomer atomization system of the present invention；
Fig. 4 is the structural schematic diagram of the nozzle unit of the present invention equipped with conical nozzle；
Fig. 5 is the structural schematic diagram of the nozzle unit of the present invention equipped with fan nozzle.
Wherein, appended drawing reference:
1 reactor
2 seed beds
3 unstripped gas hybrid systems
4 catalyst preparation systems
5 catalyst storage tanks
6 comonomer atomization systems
7 circulation lines
8 gas-liquid separators
9 gas flow guiding rings
10 gas distribution grids
11 catalyst inlets
12 comonomer entrances
13 circulation line entrances
14 circulating air entrances
15 discharge ports
16 pressure monitoring mouths
17 temperature monitoring mouths
18 nozzles
19 conical nozzles
20 fan nozzles
21 outer tubes
22 reactors
23 installation nozzles
24 nitrogen inlet valves
25 airtight valves
26 limiters
27 sealing elements
28 ejection medium inlet valves
29 straight tubes
Specific embodiment
A kind of method of vapor phase method production polyolefin elastomer, in the reactor 1 using polyethylene particle as seed bed 2
It is reacted, the material mixed gas including ethylene, hydrogen and nitrogen is passed through in reactor 1, the polyethylene in seed bed 2 is made
Grain occurs to flow and reaches fluidized state, and catalyst is then added into reactor 1 and is passed through being total to for atomized droplet-like
Polycondensation monomer is reacted, and the comonomer is that carbon atom number is 6~18 long-chain olefins, and the polymerizate density of preparation is
0.865-0.910g/cm3, long-chain olefin content is 6-40wt%.
The method of vapor phase method production polyolefin elastomer of the present invention, wherein Ethylene mass point in material mixed gas
Number is 35~50%, and hydrogen quality score is 2~5%, and nitrogen mass score is 48~60%.
The method of vapor phase method production polyolefin elastomer of the present invention, wherein the volume fraction of seed bed 1 is 0.05
~0.1.
The method of vapor phase method production polyolefin elastomer of the present invention, wherein the mass flow of long-chain olefin is second
The 10~50% of alkene mass flow.
The method of vapor phase method production polyolefin elastomer of the present invention, wherein temperature maintains 70 DEG C in reactor 1
Between~140 DEG C, pressure is maintained between 1.5MPa~2.5MPa.
Fig. 1 is the production technological process that vapor phase method of the present invention produces polyolefin elastomer, and Fig. 2 is institute of the present invention
The schematic diagram for stating reactor, in conjunction with shown in Fig. 1 and Fig. 2, a kind of device of vapor phase method production polyolefin elastomer, comprising:
Reactor 1, the reactor 1 include narrow diameter section, extension diameter section and wide path, and the wide path diameter is greater than narrow diameter
Section, extension diameter section connects narrow diameter section and wide path and diameter becomes larger from the bottom to top, and the narrow diameter section bottom enters equipped with circulating air
Mouthfuls 14, it is equipped with circulation line entrance 13 at the top of the wide path, the narrow diameter section lower sidewall is equipped with catalyst inlet 11 and altogether
Polycondensation monomer entrance 12, the narrow diameter section side wall upper part are equipped with discharge port 15, are additionally provided with 16 He of pressure detecting mouth in the narrow diameter section
Temperature detection mouth 17；
Catalyst storage tank 5, the catalyst storage tank 5 are connected to catalyst inlet 11, and the catalyst storage tank 5 is also
It is connected with catalyst preparation system 4；
Unstripped gas hybrid system 3, the unstripped gas hybrid system 3 are connected to circulating air entrance 14；
Comonomer atomization system 6, the comonomer atomization system 6 are connected to comonomer entrance 12；And
Circulation line 7, described 7 one end of circulation line are connected to circulating air entrance 14, the other end and circulation line entrance 13
Connection, the circulation line 7 are equipped with gas-liquid separator 8.
The device of vapor phase method of the present invention production polyolefin elastomer, wherein in the narrow diameter section lower section by down toward
On be successively additionally provided with gas flow guiding ring 9 and gas distribution grid 10.
Fig. 3 is the structural schematic diagram of comonomer atomization system of the present invention, as shown in figure 3, the comonomer mist
Change system 6 includes:
One ejection medium inlet valve 28, arrival end connect with a high-pressure fluid delivery pump and (are not drawn into figure)；
One end of one nozzle unit, including a nozzle 18 and straight tube 29, the straight tube 29 connects nozzle 18, the other end and institute
The outlet end connection of ejection medium inlet valve 28 is stated, the nozzle 18 protrudes into the comonomer entrance 12, the high-pressure spray
The pressure of body delivery pump is greater than the pressure in the reactor 1, and long-chain olefin is entered under the action of pressure difference by ejection medium
Mouth valve 28 enters the straight tube 29 and sprays into the reactor 1 along the straight tube 29 through the nozzle 18；
One online more changing device, including an outer tube 21, an airtight valve 25, two limiters 26 and a sealing element 27, institute
Outer tube 21 is stated to be set in outside the straight tube 29, the airtight valve 25 be mounted on the straight tube 29 and control the straight tube 29 with
Extraneous on-off, is respectively provided with two limiters 26, to fixed jacket pipe 21 on the outer tube 21 at the both ends of the airtight valve 25
With the straight tube 29 to prevent from being extruded under pressure, the sealing element 27 is screwed on the outer tube 21 and is located at institute
The straight tube 29 is dismantled simultaneously or is fixed with the outer tube 21 by rotating seal 27 by the upstream for stating airtight valve 25；
The gap on the outer tube 21 and between the straight tube 29 and outer tube 21 is arranged in one nitrogen inlet valve 24
Connection, nitrogen are flowed and in the week of nozzle 18 by nitrogen inlet valve 24 in the gap between the straight tube 29 and outer tube 21
Enclose purging.
The structure of nozzle 18 can be selected according to the fluidized state in the diameter of reactor 1, reactor 1, such as nozzle 18 is set
It is set to conical nozzle 19, fan nozzle 20, fan nozzle 20 can carry out plane injection, and conical nozzle 19 can carry out tapered injection
It penetrates, spray angle needs are selected and adjusted according to fluidized state.The subtended angle of conical jet is 60 degree to 120 degree, plane spray
The subtended angle penetrated is 45 degree to 90 degree.
21 internal diameter of outer tube should be greater than the outer diameter of the straight tube 29 of nozzle 18, be free to move axially convenient for nozzle straight tube along it,
And it is conducive to the nitrogen smooth flow of protection.
6 main function of airtight valve in online more changing device is to cut off reactor 1 during nozzle straight tube is replaced online
It is exchanged with extraneous.
Limiter 26 in online more changing device is respectively arranged one in 25 upstream and downstream of airtight valve in the form of cutting ferrule, uses
In preventing casing and nozzle straight tube from being squeezed out by high pressure.In a specific embodiment of the invention, the upstream and downstream are bases
It defines the flow direction of the liquid phase material of nozzle unit conveying.
The upstream of airtight valve 25 should be arranged in sealing element 27 in online more changing device, and in replacement nozzle casing online
When taken out together with nozzle straight tube.It is noted that nitrogen inlet valve 24 is mounted on the downstream of airtight valve 25.
Fig. 4 is the structural schematic diagram of the nozzle unit equipped with conical nozzle；Fig. 5 is the nozzle unit equipped with fan nozzle
Structural schematic diagram.As shown in Figure 4 and 5, the outer profile of nozzle is straight tube, and internal diameter is determined according to the amount of injection of alkene, model
Enclose 1/8 cun~1/2 cun；The wall thickness of nozzle by reactor 3 pressure and pressure difference determine, 0.014 cun~0.083 cun of range.
When nozzle unit pumped (conveying) medium, pressure to be offered needed for high-pressure fluid delivery pump is 0.4~1.0MPa, i.e. nozzle
The pressure difference at system both ends is at least 0.4~1.0MPa, and the conveying of medium and dispersity can be made normal.
The following are the detailed descriptions of specific embodiments of the present invention, but are not limited to the specific embodiment.
By following process conditions, using ethylene as primary raw material, using a kind of single active center's metallocene catalyst, gathered
The production of olefin elastomer POE.
Obtained product performance index such as following table
By comparative example it can be seen that after atomization system is added in polymerization reaction system, under same polymerizing condition,
Polymerization product density is lower, and product glass transition temperature is lower, illustrates that the product degree of branching is high, co-monomer content is higher.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to the protection scope of the claims in the present invention.
Claims (17)
1. a kind of method of vapor phase method production polyolefin elastomer, which is characterized in that using polyethylene particle as seed bed
It is reacted in reactor, the material mixed gas including ethylene, hydrogen and nitrogen is passed through in reactor, made poly- in seed bed
Ethylene particle occurs to flow and reaches fluidized state, and catalyst is then added into reactor and is passed through atomized droplet-like
Comonomer reacted, the comonomer is that carbon atom number is 6~18 long-chain olefins, and the polymerizate density of preparation is
0.865-0.910g/cm3, long-chain olefin content is 6-40wt%.
2. the method for vapor phase method production polyolefin elastomer according to claim 1, which is characterized in that in material mixed gas
Mass fraction of ethylene is 35~50%, and hydrogen quality score is 2~5%, and nitrogen mass score is 48~60%.
3. the method for vapor phase method production polyolefin elastomer according to claim 1, which is characterized in that the volume of seed bed
Score is 0.05~0.1.
4. the method for vapor phase method production polyolefin elastomer according to claim 1, which is characterized in that the matter of long-chain olefin
Measure 10~50% that flow is Ethylene mass flow.
5. the method for vapor phase method production polyolefin elastomer according to claim 1, which is characterized in that temperature in reactor
It maintains between 70 DEG C~140 DEG C, pressure maintains between 1.5MPa~2.5MPa.
6. a kind of device of vapor phase method production polyolefin elastomer, which is characterized in that described device is in Claims 1 to 5
Described in any item methods, comprising:
Reactor, the reactor include narrow diameter section, extension diameter section and wide path, and the wide path diameter is greater than narrow diameter section, expanding
Section connects narrow diameter section and wide path and diameter becomes larger from the bottom to top, and the narrow diameter section bottom is equipped with circulating air entrance, described
Circulation line entrance is equipped at the top of wide path, the narrow diameter section lower sidewall is equipped with catalyst inlet and comonomer entrance, institute
Narrow diameter section side wall upper part is stated equipped with discharge port；
Catalyst storage tank, the catalyst storage tank are connected to catalyst inlet；
Unstripped gas hybrid system, the unstripped gas hybrid system are connected to circulating air entrance；
Comonomer atomization system, the comonomer atomization system are connected to comonomer entrance；And
Circulation line, described circulation line one end are connected to circulating air entrance, and the other end is connect with circulation line entrance, described to follow
Endless tube road is equipped with gas-liquid separator.
7. the device of vapor phase method production polyolefin elastomer according to claim 6, which is characterized in that in the narrow diameter section
Lower section is successively additionally provided with gas flow guiding ring and gas distribution grid from the bottom to top.
8. the device of vapor phase method production polyolefin elastomer according to claim 6, which is characterized in that the comonomer
Atomization system includes:
One ejection medium inlet valve, arrival end are connect with a high-pressure fluid delivery pump；
One end of one nozzle unit, including a nozzle and straight tube, the straight tube connects nozzle, and the other end enters with the ejection medium
The outlet end connection of mouth valve, the nozzle protrude into the comonomer entrance, and the pressure of the high-pressure fluid delivery pump is greater than
Pressure in the reactor, long-chain olefin enter the straight tube and edge by ejection medium inlet valve under the action of pressure difference
The straight tube sprayed into the reactor through the nozzle；
One online more changing device, including an outer tube, an airtight valve, two limiters and a sealing element, the outer tube are arranged
Outside the straight tube, the airtight valve is mounted on the straight tube and controls the straight tube and extraneous on-off, described closed
Two limiters are respectively provided on the outer tube at the both ends of valve, to fixed jacket pipe and the straight tube with prevent under pressure by
It squeezes out, the sealing element is screwed onto the upstream on the outer tube and being located at the airtight valve, will be described by rotating seal
Straight tube and the outer tube are dismantled simultaneously or are fixed；
One nitrogen inlet valve is arranged in the gap on the outer tube and between the straight tube and outer tube and is connected to, and nitrogen is logical
Nitrogen inlet valve is crossed to flow in the gap between the straight tube and outer tube and purge around nozzle.
9. the device of vapor phase method production polyolefin elastomer according to claim 8, which is characterized in that the high-pressure fluid
The difference of pressure in the pressure and reactor of delivery pump is 0.4-1.0MPa.
10. the device of vapor phase method production polyolefin elastomer according to claim 8, which is characterized in that the nozzle
Diameter can according in the diameter of reactor, reactor fluidized state selection plane injection or conical jet.
11. the device of vapor phase method production polyolefin elastomer according to claim 10, which is characterized in that the nozzle
Shape is fan nozzle or conical nozzle.
12. the device of vapor phase method production polyolefin elastomer according to claim 10, which is characterized in that the tapered injection
The subtended angle of the injection of mouth is 60 degree to 120 degree.
13. the device of vapor phase method production polyolefin elastomer according to claim 10, which is characterized in that the fan-shaped spray
The subtended angle of the plane injection of mouth is 45 degree to 90 degree.
14. the device of vapor phase method production polyolefin elastomer according to claim 10, which is characterized in that the straight tube
Internal diameter is 1/8 cun~1/2 cun.
15. the device of vapor phase method production polyolefin elastomer according to claim 10, which is characterized in that the straight tube
Wall thickness is true according to the pressure in reactor and according to the difference of the pressure in the pressure and reactor of the high-pressure fluid delivery pump
Fixed, the range of the wall thickness of the straight tube is 0.014 cun~0.083 cun.
16. the device of vapor phase method production polyolefin elastomer according to claim 8, which is characterized in that the copolymerization is single
Body inlet is equipped with an installation nozzle, and nozzle unit described in the installing pipe confession passes through and supports the nozzle unit.
17. polyolefin elastomer according to any one of claims 1 to 5 is in medical package material, automobile parts, electric wire electricity
Application in cable, everyday articles and toy.
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