CN105542041B - Poly 1-butene and preparation method thereof - Google Patents
Poly 1-butene and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of poly- 1 butylene and preparation method thereof, this method includes：Olefin polymerization catalyst system and monomer containing 1 butylene are continuously introduced into gas-phase polymerization reactor under olefin polymerization conditions, carry out gas-phase continuous polymerization reaction, and the material discharge gas-phase polymerization reactor after continuous polymerization is reacted；The olefin polymerization conditions include：Temperature is 60 85 DEG C, and pressure is 0.3 1.5MPa；Residence time of the monomer containing 1 butylene in the gas-phase polymerization reactor is 30 120 minutes；1 butylene containing 60 100 moles of % in the monomer containing 1 butylene.Poly- 1 butylene produced by the present invention has higher isotacticity (more than 97%) and relatively low ash content, and the fusing point of poly- 1 butylene is higher than 110 DEG C, suitable for the preparation of tubing.
Description
Technical field
The present invention relates to a kind of preparation method of poly 1-butene, and poly 1-butene obtained by this method.
Background technology
Poly 1-butene (1-PB) has prominent creep resistance, environmental stress crack resistance, wearability, reelability and good
Mechanical performance, compared to other plastics (e.g., PVC, CPVC, HDPE, PP and crosslinking PE etc.), it can be less than 90 DEG C for a long time
Use, and in 105-110 DEG C of short-period used.Based on above characteristic, poly 1-butene is suitable for making tubing, food film and thin plate,
It even can be used for the hot water pipe and direct drinking water project pipe of domestic water, ensure water quality non-secondary pollution.In addition, and metal
Pipeline is compared, the energy consumption only respectively steel and the 1/8 of aluminium and 1/4, and poly 1-butene of the poly 1-butene tubing of production unit volume
Tubing is avoided that the problems such as the getting rusty of metal pipe material, galvano-cautery perforation.
High isotactic polybutene-1 can be produced and be machined using traditional polyolefin polymerization technology (such as：Squeeze
Pressure, injection or blow molding etc.).In current industrial production, the catalysis based on Ziegler-Natta catalyst is mainly used
Agent prepares poly 1-butene.The technique for carrying out 1- butene polymerizations using the catalyst mainly has substance law and solwution method, with continuous or
Batch process produces.
Domestic some producers carry out the production of poly 1-butene, batch of the poly 1-butene of this method production using mass polymerization
Secondary stability is poor and is not suitable for large-scale industrial production；Solwution method is since production process is relatively easy to control, polymerization technique letter
It is single, it is current more common method, this method includes：1- butylene is subjected to polymerisation in the presence of solvent, is then carried out
Washing, separation and dry last handling process.The method of the post processing is similar to rubber, and obtained resin is easily gathered into
Block.And solvent content is higher in block resin, extrusion molding failure of the resin in the follow-up processing such as extrusion can be caused, is such as managed
The block of wall surface is raised, uneven color is even etc..Using olefin gas-phase continuous polymerization method can obtain isotacticity it is higher, batch
The less polyolefin of secondary difference property.But different from common ethene, propylene, 1- butylene is liquid in room temperature, using gas phase into
Reaction system more difficult control during row polymerization, system are easily lumpd, the difficulty for causing product to convey and process, and can force reaction
Terminate.The gas-phase continuous polymerization of 1- butylene is difficult to realize in the prior art.
US4503203 discloses the method for carrying out 1- butylene gas-phase polymerizations using gas phase flowing bed process, and this method includes：
Using Ziegler-Natta catalyst and diethyl aluminum chloride as the catalyst system and catalyzing of co-catalyst, it is less than first in temperature of reactor
26 DEG C, pressure triggers the polymerization of 1- butene monomers under conditions of being 0.03-0.23MPa, when anti-device device material position is in 5-10%, by temperature
Degree rises to more than 30 DEG C, and pressure continues to polymerize under conditions of being 0.38-0.41MPa.In this method, stop of the material in reactor
Time be at least 100 it is small when more than, and high to catalyst requirement, it is co-catalyst to be only capable of using diethyl aluminum chloride, is reacted
The change of strict temperature control is needed in journey, otherwise polymer easily lumps, and forces reaction terminating.
US3580898 also discloses that a kind of method of 1- butylene gas-phase polymerization, and it is 40- that this method, which is included in temperature of reactor,
55 DEG C, pressure 0.55-0.69MPa, and ensure that space-time yield carries out 1- butylene under conditions of being 1-8 Pounds Per Hours/cubic feet
Polymerization, but during rate of polymerization it is relatively low, obtained polymer ash content is higher, can influence the performance of poly 1-butene product.
Therefore, there is an urgent need for developing a kind of method of new 1- butene polymerizations, this method can realize that the gas phase of 1- butylene is continuously gathered
Close.
The content of the invention
Poly 1-butene isotacticity it is an object of the invention to solve to synthesize in the prior art is low and ash content is high and is difficult to
The defects of realizing poly 1-butene gas-phase continuous polymerization, so that a kind of preparation method of poly 1-butene is provided, and by party's legal system
The poly 1-butene obtained.
The present invention provides a kind of preparation method of poly 1-butene, wherein, this method includes：Will under olefin polymerization conditions
Olefin polymerization catalyst system and monomer containing 1- butylene are continuously introduced into gas-phase polymerization reactor, carry out gas-phase continuous polymerization
Reaction, and the material discharge gas-phase polymerization reactor after continuous polymerization is reacted；The olefin polymerization conditions include：Temperature is
60-85 DEG C, pressure 0.3-1.5MPa；Residence time of the monomer containing 1- butylene in the gas-phase polymerization reactor
For 30-120 minutes；1- butylene containing 60-100 moles of % in the monomer containing 1- butylene.
Present invention also offers the poly 1-butene as made from the above method.
The preparation method of the present invention is to catalyst without particular/special requirement, and catalyst activity is higher, and resulting polymers are reacting
The defects of material discharge line being blocked in device there is no a large amount of cakings, therefore The inventive method achieves the gas of poly 1-butene
Phase continuous production.In addition, the poly 1-butene as made from the method for the present invention has higher isotacticity (more than 97%), use
Residual catalyst content is few in CPI technology for detection poly 1-butenes, suitable for the preparation of tubing.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides a kind of preparation method of poly 1-butene, wherein, this method includes：Will under olefin polymerization conditions
Olefin polymerization catalyst system and monomer containing 1- butylene are continuously introduced into gas-phase polymerization reactor, carry out gas-phase continuous polymerization
Reaction, and the material discharge gas-phase polymerization reactor after continuous polymerization is reacted；The olefin polymerization conditions include：Temperature is
60-85 DEG C, pressure 0.3-1.5MPa；Residence time of the monomer containing 1- butylene in the gas-phase polymerization reactor
For 30-120 minutes；1- butylene containing 60-100 moles of % in the monomer containing 1- butylene.
The present inventor has found under study for action, when the temperature that the monomer containing 1- butylene carries out polymerisation is
60-85 DEG C, pressure 0.3-1.5MPa, can when residence time of the monomer in gas-phase polymerization reactor is 30-120 minutes
The polymer that avoids is inter-adhesive in the reactor, caking, realizes the material discharge gas-phase polymerization after continuous polymerization reaction
Reactor, ensures that polymerization continuously can be carried out swimmingly, and makes the composition of the poly 1-butene of preparation uniform, and performance is stablized.
From the angle for improving polymerization rate, it is preferable that the olefin polymerization conditions include：Temperature is 65-75
DEG C, pressure 0.7-1.3MPa.
According to the present invention, in the monomer containing 1- butylene, the content of 1- butylene is 60-100 moles of %.That is, this hair
Bright preparation method can be used for the homopolymerization of 1- butylene, can be used for the combined polymerization by 1- butylene and other olefinic monomers.
Other described olefinic monomers can be that ethene, propylene and formula are CH2At least one of alpha-olefin of=CHR, wherein R are C3-
C10Straight or branched alkyl.
In the present invention, the instantiation of the alpha-olefin includes but not limited to amylene (such as 1- amylenes), 4- methyl-1-pentenes
Alkene, hexene (such as 1- hexenes), heptene (such as 1- heptene) or octene (such as 1- octenes).
In order to further improve the isotacticity of obtained poly 1-butene, the preferably described monomer containing 1- butylene is 1- fourths
Alkene.
According to the present invention, the olefin polymerization catalyst system can be catalyzed 1- butylene and its for commonly used in the art
His alkene carries out the various catalyst systems of organic vertical structure polymerization.Preferably, the olefin polymerization catalyst system contains solid
Component, external donor compound and organo-aluminum compound, the solid constituent contain carrier and load on the carrier
Titanium compound and internal electron donor compound.
According to the present invention, the carrier can be the conventional selection of this area, such as can be magnesium compound or silica gel.
When the carrier is silica gel, titanium compound and internal electron donor compound can be supported on silica gel, so as to prepare described
Solid constituent.The silica gel can be various silica gel commonly used in the art, be not particularly limited.
, can be by by titanium compound and internal electron donor compound and magnesium compound when the carrier is magnesium compound
Reaction is carried out so as to prepare the solid constituent, i.e. the solid constituent is titanium compound and internal electron donor compound and magnesium
The reaction product of compound.The magnesium compound can be the conventional selection of this area.For example, the magnesium compound can be formula
Magnesium compound shown in I,
R2-MgR1 (I)
In Formulas I, R1And R2Can be each chlorine, bromine, iodine, C1-C5Straight or branched alkoxyl and C1-C5Straight chain
Or one kind in branched alkyl.
In the present invention, C1-C5Straight or branched alkoxyl include but not limited to：It is methoxyl group, ethyoxyl, positive propoxy, different
Propoxyl group, n-butoxy, isobutoxy, tert-butoxy, n-pentyloxy, isoamoxy, tertiary amoxy and neopentyl oxygen.
In the present invention, C1-C5The example of straight or branched alkyl can be but be not limited to：It is methyl, ethyl, n-propyl, different
Propyl group, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl and neopentyl.
According to the present invention, the titanium compound can be common various titanium compounds in olefin polymerization catalysis.It is described
The example of titanium compound can be but be not limited to：Titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxides, tetraethoxy
One or more in titanium, a chlorine triethoxy titanium, one ethanolato-titanium of dichlorodiethyl epoxide titanium and trichlorine.Preferably, the titanium
Compound is titanium tetrachloride.
According to the present invention, the internal electron donor compound can be the common various internal electron donors of field of olefin polymerisation
Compound, such as：The internal electron donor compound can be the one or more in ditridecyl phthalate based compound.It is excellent
Selection of land, the internal electron donor compound is diisobutyl phthalate, n-butyl phthalate, phthalic acid two
One or more in n-propyl, diisopropyl phthalate, diethyl phthalate and repefral.
According to the present invention, the content of each component can be the conventional selection of this area in the solid constituent.For example, institute
When to state carrier be magnesium compound, in the solid constituent, the titanium compound, internal electron donor compound and magnesium compound
Molar ratio can be 0.01-50：0.01-50：1.The solid constituent is for example referred to the side described in CN102453150A
Method is made, and can also be commercially available, details are not described herein.
According to the present invention, the olefin polymerization catalyst system is in addition to containing solid constituent, also containing organo-aluminium chemical combination
Thing and external donor compound.
According to the present invention, the organo-aluminum compound can be various organo-aluminum compounds commonly used in the art.Usually,
The organo-aluminum compound can be one kind or more in trimethyl aluminium, triethyl aluminum, triisobutyl aluminium and diethyl aluminum chloride
Kind.Preferably, the organo-aluminum compound is triethyl aluminum.
According to the present invention, the external donor compound can be the conventional selection of this area.It is for example, described outer to electricity
Donor compound can be can as the carboxylic acid of the external donor compound of olefin polymer catalyst system, acid anhydrides, ester,
One or more in ketone, ether, alcohol, organic phosphorus compound and organo-silicon compound.Preferably, the external donor compound
For one or more compounds in organo-silicon compound.It is further preferred that the external donor compound is double
One or more in cyclopenta dimethoxysilane, diisopropyl dimethoxy silane and diisobutyl dimethoxy silicon.
According to the present invention, in the olefin polymerization catalyst system, the solid constituent, organo-aluminum compound and give outside
Molar ratio between electron compound is not particularly limited, and can be the conventional selection of this area.
In the present invention, the molar ratio of aluminium and the titanium in the solid constituent in the usual organo-aluminum compound can be
1-300：1, the molar ratio of the organo-aluminum compound and the external donor compound can be 1-40：1.
A preferred embodiment of the invention, aluminium in the organo-aluminum compound with the solid constituent
The molar ratio of titanium is 10-80：1, the molar ratio of the organo-aluminum compound and the external donor compound is 5-30：1, this
Sample can further improve waiting for poly 1-butene and provide.
The present invention is not particularly limited the dosage of the alkene catalyst system, can be that field of olefin polymerisation is conventional
Content.Usually, the molecular weight of polymerization rate and resulting polymers in order to balance, under preferable case, with described solid
The mass ratio of body component meter, the alkene catalyst system and the dosage of the monomer containing 1- butylene is 1：103-106。
According to the present invention, the quantity of the gas-phase polymerization reactor can carry out appropriate choosing according to practical application
Select.Such as：Gas-phase polymerization reactor can be one, or multiple (such as：2).The method according to the invention, in institute
State gas-phase polymerization reactor for it is multiple when, the multiple gas-phase polymerization reactor can be to be connected in parallel between each other, can also
To be connected in series.When the multiple gas-phase polymerization reactor is to be connected in series, the thing of previous gas-phase polymerization reactor output
The monomer for expecting to contain 1- butylene with another part in next gas-phase polymerization reactor contacts.
According to the present invention, the gas-phase polymerization reactor can be various gas-phase polymerization reactors commonly used in the art, example
Such as：Fluidized-bed reactor and horizontal type agitated bed gas-phase polymerization reactor.Poly 1-butene preparation method according to the present invention is especially suitable
Implement in horizontal type agitated bed gas-phase polymerization reactor.
In a kind of preferred embodiment of the present invention, the gas-phase polymerization reactor is horizontal type agitated bed gas-phase polymerization
Reactor, and the horizontal type agitated bed Gas-phase reactor is a horizontal type agitated bed gas-phase polymerization reactor.
, according to the invention it is preferred to which the polymerisation carries out in presence of hydrogen, in the case, hydrogen can be with growth
Poly 1-butene strand occur chain transfer reaction so that polymerisation terminate, obtain the less polymer of relative molecular weight,
So as to play the role of adjusting poly 1-butene relative molecular weight.The molar ratio ratio of hydrogen and the monomer containing 1- butylene can be with
For 0.001-0.1：1, it is preferably 0.008-0.1:1.
According to the present invention, in the gas-phase continuous polymerization reaction process, the material position of the gas-phase polymerization reactor can be
30-70%, is preferably 40-60%.
In the present invention, the material position refers to that the volume of solid and liquid in reactor accounts for the percentage of reactor volume.
In the present invention, the conversion per pass typically 15-30% of monomer after the continuous polymerization reaction.It is it is preferred that described
Method further includes, and the material for discharging gas-phase polymerization reactor is carried out flash separation, by the list of the unreacted butylene containing 1-
Weight is newly passed through progress gas-phase continuous polymerization reaction in the gas-phase polymerization reactor.The detailed process of the flash separation is this
The selection of field routine, details are not described herein.
Present invention also offers poly 1-butene made from the above method.The poly 1-butene as made from the method for the present invention has
Higher isotacticity (more than 97%), residual catalyst content is few in poly 1-butene, suitable for the preparation of tubing.
The present invention will be described in detail with reference to embodiments.
In following embodiments and comparative example, the solid constituent of catalyst uses the description of embodiment 1 in CN102453150A
Method obtains, and internal electron donor compound therein is n-butyl phthalate.
The activity of catalyst is measured using gas phase polymerization process.
The measure of isotacticity：Poly 1-butene is extracted to the percentage measured shared by insoluble matter after 48h in the ether of boiling to contain
Amount.
Titanium and aluminium element content (are purchased from Shenzhen moral spectrometer using the X fluorescence spectrometer of model DX320L in poly 1-butene
Device Co., Ltd) measure, content analysis scope is 1ppm.
The test of poly 1-butene fusing point carries out on Q2000 type differential scanning calorimeter instruments, and test method is：Heating speed
Rate is 10 DEG C/min, and temperature range is 30-180 DEG C, as a result takes cooling data and second of heating data.
Embodiment 1
The present embodiment is used for illustrating poly 1-butene according to the present invention and preparation method.
Catalyst solid constituent is continuously added to 50m with 0.61g/h3Continuous horizontal type agitated bed Gas-phase reactor in, use
Pump is continuously added to triethyl aluminum, its addition causes the molar ratio of the titanium in aluminium and catalyst solid constituent in triethyl aluminum
Al/Ti=50, is continuously added to diisopropyl dimethoxy silane external electron donor (wherein, external electron donor and catalyst solid
The molar ratio of titanium in component is Si/Ti=10).Then, 1- butylene is passed through into the reactor and hydrogen is polymerize
Reaction, wherein, the pressure in reactor be 1.1MPa, and the temperature in reactor is 65 DEG C, and hydrogen/1- butylene in reactor rubs
You are than (H2/C4) it is that the mean residence time of 0.008,1- butylene and hydrogen in the reactor is 60min, reactor material position is
40%.
Do not occur the phenomenon that polymer beads block the material discharge line of reactor in polymerization process.Catalyst activity
And the property of the poly 1-butene prepared is shown in table 1.
Embodiment 2
The present embodiment is used for illustrating poly 1-butene according to the present invention and preparation method.
Catalyst solid constituent is continuously added to 50m with 0.61g/h3Continuous horizontal type agitated bed Gas-phase reactor in, use
Pump is continuously added to triethyl aluminum, its addition causes the molar ratio of the titanium in aluminium and catalyst solid constituent in triethyl aluminum
Al/Ti=50, is continuously added to diisopropyl dimethoxy silane external electron donor (wherein, external electron donor and catalyst solid
The molar ratio of titanium in component is Si/Ti=20).Then, 1- butylene is passed through into the reactor and hydrogen is polymerize
Reaction, wherein, the pressure in reactor be 1.3MPa, and the temperature in reactor is 75 DEG C, and hydrogen/1- butylene in reactor rubs
You are than (H2/C4) it is that the mean residence time of 0.008,1- butylene and hydrogen in the reactor is 60min, reactor material position is
40%.
Do not occur the phenomenon that polymer beads block the material discharge line of reactor in polymerization process.Catalyst activity
And the property of the poly 1-butene prepared is shown in table 1.
Embodiment 3
The present embodiment is used for illustrating poly 1-butene according to the present invention and preparation method.
Catalyst solid constituent is continuously added to 50m with 0.61g/h3Continuous horizontal type agitated bed Gas-phase reactor in, use
Pump is continuously added to triethyl aluminum, its addition causes the molar ratio of the titanium in aluminium and catalyst solid constituent in triethyl aluminum
Al/Ti=50, is continuously added to diisopropyl dimethoxy silane external electron donor (wherein, external electron donor and catalyst solid
The molar ratio of titanium in component is Si/Ti=30).Then, 1- butylene is passed through into the reactor and hydrogen is polymerize
Reaction, wherein, the pressure in reactor be 1.2MPa, and the temperature in reactor is 70 DEG C, and hydrogen/1- butylene in reactor rubs
You are than (H2/C4) it is that the mean residence time of 0.008,1- butylene and hydrogen in the reactor is 60min, reactor material position is
40%.
Do not occur the phenomenon that polymer beads block the material discharge line of reactor in polymerization process.Catalyst activity
And the property of the poly 1-butene prepared is shown in table 1.
Embodiment 4
The present embodiment is used for illustrating poly 1-butene according to the present invention and preparation method.
Poly 1-butene is prepared using method same as Example 1, unlike, the pressure in reactor is 1.1MPa,
Temperature in reactor is 80 DEG C, does not occur showing for the material discharge line of polymer beads blocking reactor in polymerization process
As.The property of catalyst activity and the poly 1-butene of preparation is shown in table 1.
Embodiment 5
The present embodiment is used for illustrating poly 1-butene according to the present invention and preparation method.
Poly 1-butene is prepared using method same as Example 1, unlike, the addition of triethyl aluminum causes three second
, there are not polymer particles in polymerization process in the molar ratio Al/Ti=100 of the titanium in aluminium and catalyst solid constituent in base aluminium
Grain blocks the phenomenon of the material discharge line of reactor.The property of catalyst activity and the poly 1-butene of preparation is shown in table 1
Go out.
Embodiment 6
The present embodiment is used for illustrating poly 1-butene according to the present invention and preparation method.
Poly 1-butene is prepared using method same as Example 1, unlike, with the 1- butylene and ethene of identical partial pressure
Monomer mixture (content of 1- butylene is 95 moles of %) replace 1- butylene in embodiment 1, the temperature in reactor is 65
DEG C, do not occur the phenomenon that polymer beads block the material discharge line of reactor in polymerization process.Catalyst activity and
The property of the poly 1-butene of preparation is shown in table 1.
Comparative example 1
Poly 1-butene is prepared using method same as Example 1, unlike, the temperature in reactor is 90 DEG C, pressure
Power is 1.0MPa, and in reaction process, the inter-adhesive caking of polymer, forces production to stop.Catalyst activity and preparation it is poly-
The property of 1- butylene is shown in table 1.
Comparative example 2
Poly 1-butene is prepared using method same as Example 1, unlike, the temperature of polymerisation is reduced to 50
DEG C, pressure 0.6MPa, in reaction process, the inter-adhesive caking of polymer, forces production to stop.Catalyst activity and preparation
The property of poly 1-butene be shown in table 1.
Comparative example 3
Poly 1-butene is prepared using method same as Example 1, unlike, 1- butylene and hydrogen are in the reactor
Mean residence time is 25min.In reaction process, the inter-adhesive caking of polymer, forces production to stop.Catalyst activity and system
The property of standby poly 1-butene is shown in table 1.
Table 1
Table 1 the results show that compared with comparative example 1-3, the preparation method of embodiment 1-6 can be realized based on 1- butylene
Monomer gas-phase continuous polymerization, while obtained poly 1-butene is with higher isotacticity (more than 97%) also with compared with
Low ash content, the fusing point of poly 1-butene is above 110 DEG C, suitable for the preparation of tubing.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (7)
1. a kind of preparation method of poly 1-butene, it is characterised in that this method includes：By olefinic polymerization under olefin polymerization conditions
Catalyst system and monomer containing 1- butylene are continuously introduced into gas-phase polymerization reactor, carry out gas-phase continuous polymerization reaction, and
Material discharge gas-phase polymerization reactor after continuous polymerization is reacted；The olefin polymerization conditions include：Temperature is 67-75 DEG C,
Pressure is 0.7-1.3MPa；Residence time of the monomer containing 1- butylene in the gas-phase polymerization reactor is 30-120
Minute；1- butylene containing 60-100 moles of % in the monomer containing 1- butylene, the olefin polymerization catalyst system contain
There are solid constituent, external donor compound and organo-aluminum compound, the solid constituent contains carrier and is supported on described
Titanium compound and internal electron donor compound on carrier, the aluminium in the organo-aluminum compound and the titanium in the solid constituent
Molar ratio be 10-80：1, the molar ratio of the organo-aluminum compound and the external donor compound is 5-30：1.
2. according to the method described in claim 1, wherein, the monomer containing 1- butylene is 1- butylene.
3. according to the method described in claim 1, wherein, the gas-phase polymerization reactor is horizontal type agitated bed gas phase polymerization
Device.
4. according to the method described in claim 1, wherein, the polymerisation carries out in presence of hydrogen, hydrogen contains with described
The molar ratio for having the monomer dosage of 1- butylene is 0.008-0.1:1.
5. the method according to claim 1 or 3, wherein, in the gas-phase continuous polymerization reaction process, the gas-phase polymerization
The material position of reactor is 30-70%.
6. according to the method described in claim 5, wherein, in the gas-phase continuous polymerization reaction process, the gas-phase polymerization is anti-
The material position for answering device is 40-60%.
7. according to the method described in any one in claim 1-4 and 6, wherein, the method further includes, and discharge gas phase is gathered
The material for closing reactor carries out flash separation, and it is anti-that the monomer of the unreacted butylene containing 1- is passed through the gas-phase polymerization again
Answer progress gas-phase continuous polymerization reaction in device.
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| CA1309553C (en) * | 1987-03-14 | 1992-10-27 | Takashi Yamawaki | Butene-1 copolymer |
| EP0352362A1 (en) * | 1987-03-19 | 1990-01-31 | Idemitsu Petrochemical Co. Ltd. | Butene-1 copolymer |
| EP0294767A1 (en) * | 1987-06-10 | 1988-12-14 | Idemitsu Petrochemical Co. Ltd. | Process for producing polybutene-1 |
| CN1140545C (en) * | 1998-03-05 | 2004-03-03 | 蒙特尔技术有限公司 | Polybutene-1(CO) polymers and process for their preparation |
| CN102040693A (en) * | 2009-10-23 | 2011-05-04 | 中国石油化工股份有限公司 | Gas-phase polymerization method and polymer of polybutene-1 |
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