CN107226876A - A kind of polyvinyl preparation method - Google Patents
A kind of polyvinyl preparation method Download PDFInfo
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- CN107226876A CN107226876A CN201610168279.3A CN201610168279A CN107226876A CN 107226876 A CN107226876 A CN 107226876A CN 201610168279 A CN201610168279 A CN 201610168279A CN 107226876 A CN107226876 A CN 107226876A
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- mixing liquid
- olefin
- ethene
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- 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
- C08F210/02—Ethene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to a kind of polyvinyl preparation method, including：It is that the major catalyst in catalyst system is transported in reactor by carrier logistics with mixing liquid I, the mixing liquid I includes alkane, alkene and co-catalyst；Stream I II is obtained after supplement olefin feedstocks are added into the stream I I flowed out from reactor, stream I II is divided into stream I IIa and IIIb, stream I IIa and IIIb are back to sidepiece and the bottom of reactor respectively；In the reactor, it is aggregated to obtain ethene polymers and discharged from reactor；Wherein, the alkene includes alhpa olefin and ethene；And the molar concentration rate of alhpa olefin and ethene is at least 1 in the mixing liquid.Polymer prepared in accordance with the present invention, its mist degree is low and tack is high.The invention further relates to application of the ethene polymers of heretofore described method preparation in film article.
Description
Technical field
The present invention relates to a kind of preparation method of polymer, specifically, the present invention relates to the polyvinyl system of one kind
The application of Preparation Method and ethylene copolymer and its film article.
Background technology
At present, polypropylene double-way stretched film (BOPP) is the major product of high-grade packaging field, because it has quality
Gently, the advantages of transparent, nontoxic, moistureproof and high mechanical strength.And novel polyethylene biaxially oriented film (BOPE) shows than BOPP
More excellent performance is gone out, its quality lighter, transparency, glossiness and printing effect is more preferable.BOPE is mainly 3-5 tunic knots
Structure, most commonly 3 layers, be respectively outside basic unit, sandwich layer basic unit and functional layer.The main component of sandwich layer is polyethylene (PE), PE
Addition account for 99% or so of sandwich layer weight.The main linear low density polyethylene (LDPE)s of PE used in traditional polyethylene film
(LLDPE), low density polyethylene (LDPE) (LDPE) and metallocene linear-low density polyethylene (mLLDPE).LLDPE blown films it is transparent
Property it is not good, mist degree is big, and this is primarily due to comprise only short-chain branch in common LLDPE, and short-chain branch is more to cause LLDPE crystallinity
Higher, so that film clarity is reduced, mist degree is higher.Meanwhile, the more difficult control of LLDPE film surfaces viscosity is directly affected
The use of film and the Transport Safety of Bale Cargo.
Although there is document to disclose a kind of method for adjusting addO-on therapy raising polyethylene film tack at present.By adding
Plus the collocation of the adjacent octanoic acid of two phthalic acid two of plasticizer and dioctyl adipate, and inorganic filler calcium carbonate and aluminum oxide match somebody with somebody
Close so that the extensibility and obdurability of preservative film are improved, and then tack is strengthened.But the certain applications field of film, such as
Food fresh keeping etc., its tack relies primarily on the realization of plastics self-characteristic.And additive the problem of be related to spilling unavoidably, Jin Erke
The application of film can be influenceed.
For this reason, the present inventor is studied, it is therefore an objective to solve association area prior art institute sudden and violent
The problem of exposing, expect to provide and a kind of the high-performance ethene that mist degree is low, tack is high is prepared using fluidized-bed reactor gather
The method of composition powder.
The content of the invention
In view of above the deficiencies in the prior art, an object of the present invention is that providing one kind prepares polyvinyl side
Method, the method achieve using single reactor to prepare that mist degree is low, the good high-performance ethene polymers product of transparency；And/or
The good high-performance ethene polymers product of bond properties.
Another object of the present invention is to provide a kind of ethene polymers prepared according to methods described in film system
Application in product.The film article such as packaging material or Commercial goods labelses etc..
According to an aspect of the invention, there is provided a kind of polyvinyl preparation method, including：Use mixing liquid I
The major catalyst in catalyst system is transported in reactor for carrier logistics, the mixing liquid comprising alkane, alkene and
Co-catalyst；Supplement olefin feedstocks are added into the stream I I flowed out from reactor, stream I II is obtained, stream I II is divided into
Stream I IIa and IIIb, stream I IIa and IIIb are back to sidepiece and the bottom of reactor respectively；In the reactor, it is aggregated to obtain
Discharged to ethene polymers and from reactor；Wherein, the alkene includes alpha-olefin and ethene, and α in the mixing liquid I-
The mol ratio of alkene and ethene is at least 1.
In the method for the invention, Matter Transfer is carried out in whole reaction system, so that recycling raw materials.Wherein,
The stream I I flowed out from reactor mass flow is larger, is big flow Matter Transfer, after a small amount of charging of supplement, obtains logistics
III.In the method for the invention, mixing liquid I and stream I IIa and IIIb are added in reactor, wherein the alkane contained
Hydrocarbon, the latent heat of vaporization of alkane is high, and the shifting heat of alkane is big so that the different conversion zone of temperature is presented in reactor；And it is mixed
Closing has high alpha-olefin content in liquid I；Therefore, the different temperatures bar of olefinic monomer different zones in fluidized-bed reactor
High side chain, the olefin polymer of the HMW of low-density and low side chain, highdensity low molecule can be respectively obtained under part
The olefin polymer of amount, it is hereby achieved that the olefin polymer of height molecular weight constantly mixes the product of fluidisation, and is improved
The molecule segment or the content of strand of highly -branched degree, and because alkane can be with removing in larger raising fluidized-bed reactor
Heat energy power, therefore the method for the present invention can improve the mist degree and tack of ethylene copolymer, and the space-time yield of production is obtained
Significantly improve.
In the method for the invention, the olefinic monomer in stream I II and mixing liquid I is as raw material, in fluidized-bed reaction
It is polymerize respectively in the different reaction zone of multiple temperature in device.Different polymerization temperature and different olefin monomer concentrations can be with
Obtain structure and performance different olefin polymer.According to the present invention, made of a kind of mixing solution comprising alkane and alkene
Carrier can further form cryogenic reaction zone by catalyst transport to reactor in reactor, further improve high branch
The strand content of change degree.The mist degree and tack of the polyethylene according to said method made are improved；And then, improve what is obtained
The combination property of film article, such as puncture resistance, tangent modulus, tearing toughness, tack and light transmittance are improved, and
Reduce mist degree.
The method provided according to the present invention, carrier is done by catalyst transport with a kind of mixing solution comprising alkane and alkene
Into reactor, and in mixing liquid the molar content of alpha-olefin is not less than ethene, and the alpha-olefin at initial stage of catalyst action contains
Amount is high so that the degree of branching rise of polyethylene, density reduction (LDPE low density polyethylene (LDPE)s).The polymerization obtained according to the present invention
Thing, in the case of close molecular weight so that the mist degree and tack of polymer are improved.
According to a preferred embodiment of the present invention, the mixing liquid I be able to will can be sponsored as carrier logistics
Agent powder is delivered in reaction system.Wherein, preferably first major catalyst is transported to and polymerisation with a rotating machinery
In the pipeline or pipe fitting of device connection, then major catalyst powder is delivered in reaction system with mixing liquid I again.According to this hair
A bright specific embodiment, the rotating machinery is selected from pump, compressor, blower fan and reductor.
According to a preferred embodiment of the present invention, the catalyst system includes Ziegler-Natta catalyst, cyclopentadienyl gold
Metal catalyst, transition-metal catalyst, inorganic chrome catalysts and organic chrome catalysts.The catalyst system includes co-catalyst
And major catalyst.In a specific example, the amount of major catalyst and co-catalyst is conventional amount used in the art, such as main
The mol ratio of catalyst and co-catalyst is with the active metal metal in the active metallic element and co-catalyst in major catalyst
The mol ratio of element is 1:1-6:1.In a specific embodiment, the co-catalyst included in the mixing liquid I is three
Aluminium ethide.In another specific example, amount of the co-catalyst in mixing liquid is that (weight contains at least 150ppm
Amount).
According to a preferred embodiment of the present invention, the mol ratio of alpha-olefin and ethene is (1- in the mixing liquid I
5)：1, preferably (1.3-5)：1.In a more preferred case, the mol ratio of alpha-olefin and ethene is in the mixing liquid I
(1.5-5)：1.Now, the content of alpha-olefin is higher so that the degree of branching rise of polyethylene, density reduction, meanwhile, at close point
In the case of son amount so that the mist degree and tack of polyethylene (or ethene polymers, copolymerization of ethylene is referred both to herein) are obtained
Further improve.
According to another preferred embodiment of the present invention, in the mixing liquid I, the content of alkane is 5-
80wt%.In situations where it is preferred, the content of the alkane in mixing liquid I is 10-65wt%.Control the alkane in mixing liquid
Content, is conducive to controlling reaction temperature, forms cryogenic reaction zone.
According to another preferred embodiment of the present invention, the mass flow of the mixing liquid I accounts for stream I I quality
The 0.05%-5% of flow, preferably in 0.1%-3%.
In a specific embodiment, the present invention in alkane comprising butane, iso-butane, pentane, isopentane, just oneself
At least one of alkane, hexamethylene and heptane.The alkane of the restriction, its latent heat of vaporization is high, moves heat big；Be conducive in reaction
The reaction zone of differential responses temperature is formed in device.
According to a preferred embodiment of the present invention, the reaction pressure in the reactor is 0.5-10MPa, reaction temperature
Spend for 40-150 DEG C.In a specific example, the reaction pressure in reactor is 1.5-5MPa.It is specific real at another
Apply in example, the reaction temperature in the reactor is 60-100 DEG C.
According to the present invention, the alkane in the alkane in the alkane, such as mixing liquid I, such as stream I IIa or IIIb, its
The latent heat of vaporization is high, moves heat greatly, can be used as condensing agent.Therefore, there is the polymerization zone that alkane is inputted in reactor
Reaction temperature it is different from the reaction temperature of other polymerization zones.It is described anti-according to the specific embodiment of the present invention
It is fluidized-bed reactor to answer device.Logistics is whole including fluidized-bed reactor, pipeline, heat-exchange apparatus, separation equipment etc.
Matter Transfer is carried out in individual reaction system.
According in the specific preferred embodiment of the present invention, the reaction zone that temperature is different is included in the reactor.
There is the polymerization zone that condensing agent (alkane) is inputted in the reactor, temperature is relatively low, is cryogenic reaction zone, defeated without condensing agent
The polymerization zone entered, it is of a relatively high, it is high temperature reaction zone.According to the specific embodiment of the present invention, the low-temp reaction
The reaction temperature in area is controlled at 60-75 DEG C, preferably 65-75 DEG C；The reaction temperature of high temperature reaction zone is controlled at 75-100 DEG C, preferably
80-90℃。
According to a preferred embodiment of the present invention, the apparent fluidizing gas velocity of the fluidized-bed reactor is 0.1-10m/
s.The method of the present invention strictly controls the purpose of the apparent fluidizing gas velocity of fluidized-bed reactor to be to ensure reactor fluidized state
It is good to avoid powder from largely being taken out of simultaneously.When apparent fluidizing gas velocity is 0.3-0.8m/s, method of the invention can enter one
Step ensures fluidized-bed reactor quiet run, while ensureing being stabilized for cryogenic reaction zone and high temperature reaction zone.Reason may
It is apparent fluidizing gas velocity higher than the starting fluidization rate speed of body series powder while less than the band of most powder particles
Go out speed.
According to a preferred embodiment of the present invention, in the stream I I flowed out from reactor, alkane is included, it is also possible to include
Unreacted olefinic monomer (may relate to ethene and alpha-olefin).Stream I I and stream I II, component therein is more or less the same, matter
Amount flow is also more or less the same.In a specific example, stream I I mass flow account for the 90% of stream I II mass flows with
On, preferably 95% with up to 100%.
As the progress of reaction and the discharging of polymer are, it is necessary to supplement olefin feedstocks.(it is related to supplement through supplementing olefin feedstocks
Ethylene feed and the charging of supplement alpha-olefin) after charging, in the obtained stream I II, the content of alkene is 1.0-
60.0mol%, such as preferred 5.0-55.0mol%.Wherein, in a specific example, in the stream I II, alpha-olefin
Molar concentration accounts for the molar concentration of ethene in 20%-60%.
According to a preferred embodiment of the present invention, conditioning agent and/or inert component are included in the stream I II.Adopt
With conditioning agent, the polyvinyl molecular weight of gained and molecular weight distribution can be polymerize according to the different adjustment of regulation agent content.
Wherein, the conditioning agent is preferably hydrogen.Using inert component, the partial heat produced by can removing in polymerization process, also
Logistics III composition can be adjusted.Wherein, the inert component is preferably nitrogen.Now, the stream I I flowed out from reactor
In, conditioning agent and/or inert component may be included.In an instantiation, in the stream I II, the conditioning agent contains
Amount control is 0.3-14.5mol%.In another instantiation, in the stream I II, the amount control of the inert component
For 25.0-75.0mol%.In an instantiation, in stream I II described in the logistics, the content control of alkane is 0.5-
50.0mol%, such as 1.0-35.0mol%.According to technique needs, the charging of supplement alkane, inert component can be also included in stream I II
At least one of charging and supplement conditioning agent charging, to better control over the composition in stream I II.
According to a preferred embodiment of the present invention, the stream I II is compressed with after gas-liquid separation, is divided into logistics
IIIa and IIIb.Wherein, stream I IIa flows into reactor by the sidepiece of reactor.And the bottom that stream I IIb passes through reactor
Flow into reactor.According to the specific embodiment of the present invention, the alkane total amount that the alkane in stream I IIa is accounted in stream I II
60-90wt%.Namely most of the alkane in stream I II flows into reactor by stream I IIa from the sidepiece of reactor.According to
The 10-50wt% for the alkene total amount that alkene in the specific embodiment of the present invention, stream I IIa is accounted in stream I II.
According to another specific embodiment of the present invention, in IIIa and IIIb, there are conditioning agent and inert component.Wherein
The amount of conditioning agent is the amount 50-100%wt of conditioning agent in III in IIIb.The amount of inert component is inert component in III in IIIa
Amount 10-100%wt.Wherein, the 10-100wt% for the alpha-olefin total amount that the alpha-olefin in stream I IIa is accounted in stream I II.
In the method for the invention, the temperature of the polymerization zone refers to the maximum temperature in the polymerization zone.
According to the specific embodiment of the present invention, alkane and olefinic monomer in stream I IIa are passed through fluidized-bed reactor from side,
And the remaining alkane and olefinic monomer in stream I II in the form of stream I IIb from bottom input fluidized-bed reactor.By
This can further improve the removal efficiency of heat and the space-time yield of reaction in reactor.
In the method for the invention, olefin polymer is after fluidized-bed reactor outflow, into storage tank and scavenging tank
The olefinic monomer in removing olefin polymer is purged with inert component, further removing olefinic polymerization in degassing cabin is then entered back into
Olefinic monomer inside thing, from degassing cabin bottom, discharge is granulated last ethene polymers.
According to the present invention, the alpha-olefin is in propylene, 1- butylene, 1- amylenes, 1- hexenes, 1- octenes and 1- decene
It is at least one.
According to a preferred embodiment of the present invention, prepared ethene polymers, the 'alpha '-olefin monomers unit institute
The molar content accounted for is 1-30%.The content of the 'alpha '-olefin monomers unit of the polymer is higher than prepared by other method, branch
Change degree is high；And wherein 'alpha '-olefin monomers unit head be connected the content of (refer to be connected with two carbon atoms of side base be joined directly together) (can
Pass through C13Nuclear-magnetism is determined) it is higher than prepared by other method；And then, be conducive to improving mist degree and tack.
According to a preferred embodiment of the present invention, prepared polyvinyl density is in 0.890g/cm3Extremely
0.922g/cm3, preferably 0.895 to 0.917g/cm3.It is molten under conditions of 230 DEG C and 2.16kg in the ethene polymers
Body flow rate is 0.1-10g/10min, preferably 0.5-5.0g/10min.The polyvinyl weight average molecular weight is
20000-250000, molecular weight distributing index is 2-15.
According to a preferred embodiment of the present invention, according to ISO11357-3 by differential scanning calorimetry with 20 DEG C/minute
The rate of heat addition of clock is determined, and polyvinyl fusing point is 110-130 DEG C, preferably 115-125 DEG C.It is described polyvinyl
Mist degree is less than 12.0%, preferably shorter than 10.3%, more preferably less than 9.6%.The value of the polyvinyl tack exists
0.2N/cm2-1N/cm2, preferably 0.3N/cm2-1N/cm2。
In the method for the invention, the space-time yield refers to the production of the olefin polymer of unit bed volume unit interval
Amount.
According to a further aspect of the invention, the ethene polymers of above method preparation is additionally provided in film article
Using.It includes, and ethene polymers is prepared first with the above method, is subsequently used for film article.The film article is preferably wrapped
Include packaging material and/or Commercial goods labelses.Ethene polymers provided by the present invention can be widely applied to boiling film, high transparency
The membrane materials such as film, barrier protection film, heat-sealing film, label film.
Compared with prior art, the present invention prepares ethene polymers, and profit using fluidized-bed reactor band liquid condensing technique
Major catalyst is sent into reactor, the side that stream I IIa passes through reactor with the mixing liquid containing high alpha-olefin/ethylene molar ratio
Portion flows into reactor, and stream I IIb flows into reactor by the bottom of reactor；Further it can be formed more in reactor
The different reaction zone of many temperature, obtains high and low molecular weight and the high and low degree of branching is microcosmic well mixed, further increases and contains
The content of the strand of highly -branched degree, reduces density.The method according to the invention, technical process is simple；It is easy to operate；Facility
That invests is with low cost；Continuous-stable is good；Diversified ethene polymers (copolymer) product can be produced；Obtained polymerization
The mist degree of produce product is low, and tack is high.
Brief description of the drawings
Technical scheme in order to illustrate the embodiments of the present invention more clearly, makes required in being described below to embodiment
Accompanying drawing, which is done, simply to be introduced, it is therefore apparent that the accompanying drawing in brief description is only some embodiments of the present invention, for this
For the those of ordinary skill of field, on the premise of not paying creative work, it can also obtain other according to these accompanying drawings
Accompanying drawing.
Fig. 1 represents a kind of schematic diagram for the reaction unit for realizing the inventive method.
Fig. 2 represents to form the schematic diagram in the different olefinic polyreaction area of multiple temperature in fluidized-bed reactor.
In figure, identical component is indicated by identical reference.Accompanying drawing is not drawn according to actual ratio.
Reference is described as follows：
1 distribution grid
2 fluidized-bed reactors；
3 compression devices；
4 heat-exchange apparatus；
5 separation equipments；
6 feed pumps；
7 gas circulation lines；
8 discharge tanks；
9 scavenging tanks；
10 degassing cabins；
11 fluid line for mixed solution I to be introduced major catalyst as carrier logistics to reactor；
12 and 19 are used for the fluid line of stream I IIa introducing reactors；
13 are used for the fluid line of the taking-up solid ethylene polymer from reactor；
14 are used for H2、N2The fluid line of circulation line is introduced with ethene；
15 are used for the fluid line of alpha-olefin comonomer introducing circulation line；
16 are used for the fluid line of condensing agent introducing circulation line；
17 for the fluid line for the stream I IIb introducing reactors for isolating separation equipment；
18 pump for mixing liquid I to be delivered to pipeline 11；
19 device for major catalyst powder to be added to pipeline 11.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.It is unreceipted specific in embodiment
Condition person, the condition advised according to normal condition or manufacturer is carried out.Agents useful for same or the unreceipted production firm person of instrument, be
Can be by the conventional products of acquisition purchased in market.
The characterizing method of ethene polymers structure and performance
(1) sign of melting temperature and crystallization temperature：Differential scanning calorimetry (DSC).
Testing sample 6mg or so is weighed, 220 DEG C or so are heated to 20 DEG C/min speed, and kept in nitrogen stream
2min, is then cooled to 40 DEG C or so by it with 20 DEG C/min speed, and 2min is kept at this temperature with crystallized sample.Then
The sample is warming up into 220 DEG C with 20 DEG C/min heating rate to melt again.Record melting scanning, obtains thermal analysis curue, and
Thus melting temperature and crystallization temperature are read.
(2) sign of weight average molecular weight (Mw)：Gel permeation chromatography (GPC).
By testing sample with 70mg/50ml stabilisation 1,2,4- trichloro-benzenes (250 μ g/ml BHT (CAS REGISTRY
NUMBER 128-37-0) concentration prepare；Then sample is heated to 170 DEG C and is kept for 2.5 hours to be dissolved；Measurement is
Stabilize solvent to enter on Waters GPCV2000, under the conditions of 145 DEG C, with 1.0ml/min. flow rate, with identical
Capable；Three Polymer Lab posts are used in series (Plgel, 20 μm of mixing ALS, 300X 7.5mm).
(3) measure of molecular weight distributing index (PDI)：The RMS-800 type plate rheometers of Rheometrics companies.
Operated under the conditions of vibration frequency increases to 100rad/s from 0.1rad/s.Intersect modulus (crossover
Modulus) PI can be derived by below equation：PI=105/Gc, wherein, Gc is intersects modulus, and it is true as G '=G "
Fixed value (being represented with Pa), wherein G ' is storage modulus, and G " is loss modulus.
(4) sign of melt flow index (MFR)：Determined under the conditions of 230 DEG C/2.16kg according to ISO method 1133.
(5) measure of ethylene contents：IR spectroscopic methodologies.
(6) measure of alpha-olefin content：IR spectroscopic methodologies.
(7) measure of density：Determined according to ISO 1183.
(8) thickness：Determined according to GB/T 6672-2001.
(9) tearing strength：According to ASTM D1922.
(10) puncture resistance：Determined according to BB/T 0024-2004.
(11) transparency：Determined according to BB/T 0024-2004；
(12) mist degree：Determined according to GB/T 2410-2008,.
(13) tack：Determined according to GB/T 10457-2009.
In a specific example, as shown in figure 1, internally having in the fluidized-bed reactor 2 that nitrogen is fluidized, lead to first
Cross device 19 as the major catalyst powder in Ziegler-Natta catalyst is added to by feeding device be connected with reactor 2
In pipeline 11, the mixing liquid I containing alkane and alkene is transported in pipeline 11 using pumping unit 18, done using mixing liquid I
Major catalyst powder is transported in reactor 2 by carrier, and cocatalyst is also contained in mixing liquid I, wherein, pipeline 11 and reaction
The connector of device 2 can have one or more.Pipeline 7 is connected with the top expanded section of fluidized-bed reactor 2, is come from for receiving
Stream I I in fluidized-bed reactor 2.Material in stream I I may include unreacted olefinic monomer and alkane etc..Through mending
Stream I II is obtained after filling olefin feedstocks (can be by 14 and pipeline 15).According to experiment needs, also alkane can be supplemented into stream I I
Hydrocarbon charging (by pipeline 16) and supplement conditioning agent (can pass through pipeline 14, such as H2) and inert component charging (pipe can be passed through
Line 14, such as N2) etc., to obtain stream I II.Stream I II is given into the bottom that stream I IIa and IIIb distribution are passed through reactor
And top.In an instantiation, from heat exchanger 4 come out stream I II pass through gas-liquid separator 5, be divided into stream I IIa and
IIIb.Condensing agent total content is predominantly located in stream I IIa in stream I II, and stream I IIa passes through fluid line 12 and 19
(can increase feed rate by pump 6) sprays into fluidized-bed reactor 2, and remaining condensing agent is located in stream I IIb, and with fluid hose
Road 17 enters fluidized-bed reactor 2 in the lower section of distribution grid 1.Wherein, the connector of pipeline 19 and reactor 2 can have one or
It is multiple.Method in the present invention, forms high temperature reaction zone and cryogenic reaction zone, as shown in Figure 2 in fluidized-bed reactor.
A represents high temperature reaction zone, and B represents cryogenic reaction zone.
The solid polymer generated in polymerisation is intermittently from the discharging of fluid line 13, successively by discharge tank 8, purging
After tank 9 and the devolatilization of degassing cabin 10 processing, it is transported to downstream section and is processed further.Obtain ethene polymers.
Embodiment 1
The present embodiment uses the TiCl3 of magnesium chloride load for major catalyst (major catalyst inlet amount 2.18kg/h), with three
Aluminium ethide as co-catalyst Ziegler-Natta catalyst.Wherein, the molar ratio of major catalyst and co-catalyst is with Ti/
Al is calculated as 3.11.Reaction process is shown in Fig. 1.
Mixing liquid I mass flow is 1.8t/h, accounts for the 0.42% of stream I I mass flow.In mixing liquid I,
Alkane isopentane content accounts for the 50 weight % (molar content is 49%) of mixing liquid, and olefin(e) centent accounts for 50 weights of mixing liquid
% (molar content is 51%) is measured, wherein, ethylene contents account for the 4.9 weight % (molar content is 12.5%) of mixing liquid, 1-
Ahexene content accounts for the 45.1 weight % of mixing liquid (molar content is 38.5%).In mixing liquid I also containing 200ppm three
Ethyl aluminum cocatalyst.
Apparent fluidizing gas velocity in reactor is 0.75m/s.The pressure of reactor is 2.1MPa, and temperature is 89 DEG C.
In stream I I after supplement charging, stream I II is obtained.Stream I I mass flow accounts for stream I II mass flow
97.8%.Isopentane in stream I II, 80wt% is located in stream I IIa, and remaining is located in stream I IIb.
Polymerization time is 2h, finally obtains the own binary polymer A of the bipolymer of ethene/1- hexenes, i.e. second.
Stream I II each component content is see table 1 below in the present embodiment.
Table 1
The performance of the own binary polymer A of second prepared by the present embodiment and the characterization result of structure are see table 4 below.
Embodiment 2
The present embodiment uses the TiCl of magnesium chloride load3For major catalyst (major catalyst inlet amount 1.75kg/h), with three
Aluminium ethide as co-catalyst Ziegler-Natta catalyst.Wherein, the molar ratio of major catalyst and co-catalyst is with Ti/
Al is calculated as 3.11.Reaction process is shown in Fig. 1.
Mixing liquid I mass flow is 1.3t/h, accounts for the 0.30% of stream I I mass flow.In mixing liquid I, alkane
Hydrocarbon isopentane content accounts for the 45 weight % (molar content is 35%) of mixing liquid, and olefin(e) centent accounts for 55 weight % of mixing liquid
(molar content is 65%), wherein, ethylene contents account for the 8.8 weight % (molar content is 17.8%) of mixing liquid, 1- butylene
Content accounts for 46.2 weight % of mixing liquid) (molar content is 47.2%), the also triethyl group containing 180ppm in mixing liquid
Aluminum cocatalyst.
Apparent fluidizing gas velocity in reactor is 0.70m/s.The pressure of fluidized-bed reactor is 2.0MPa, and temperature is 88
℃。
In stream I I after supplement charging, stream I II is obtained.Stream I I mass flow accounts for stream I II mass flow
96.8%.Isopentane in stream I II, 80wt% is located in stream I IIa, and remaining is located in stream I IIb.
Polymerization time is 2h, finally obtains the bipolymer of Ethylene/1-butene, i.e. second fourth binary polymer B.
Stream I II each component content is see table 2 below in the present embodiment.
Table 2
The performance of second fourth binary polymer B prepared by the present embodiment and the characterization result of structure are see table 4 below.
Embodiment 3
The present embodiment uses the TiCl of magnesium chloride load3For Ziegler-Natta catalyst (major catalyst inlet amount
2.03kg/h), co-catalyst is used as using triethyl aluminum.Wherein, the molar ratio of major catalyst and co-catalyst is calculated as with Ti/Al
3.11.Reaction process is shown in Fig. 1.
Mixing liquid I mass flow is 1.7t/h, accounts for the 0.37% of stream I I mass flow.In mixing liquid I, alkane
Hydrocarbon n-hexane content accounts for the 25 weight % (molar content is 25%) of mixing liquid, and olefin(e) centent accounts for 75 weight % of mixing liquid
(molar content is 75%), wherein, ethylene contents account for 7.8 weight % (molar content 23.8%) of mixing liquid, and 1- octenes contain
Amount accounts for the also triethyl aluminum containing 180ppm in the 67.2 weight % (molar content is 51.2%) of mixing liquid, mixing liquid and helped
Catalyst.
Apparent fluidizing gas velocity in reactor is 0.68m/s.The pressure of fluidized-bed reactor is 2.1MPa, and temperature is 87
℃。
In stream I I after supplement charging, stream I II is obtained.Stream I I mass flow accounts for stream I II mass flow
97.2%.Isopentane in stream I II, 80wt% be located at stream I IIa in, its be located at stream I IIb in.
Stream I II each component content is see table 3 below in the present embodiment.
Table 3
The performance of the pungent binary polymer C of second prepared by the present embodiment and the characterization result of structure are see table 4 below.
Comparative example 1
This comparative example uses the method disclosed in embodiment 35 in WO00/02929A1, and raw material is used as using ethene and 1- hexenes
To prepare the own binary polymer D of second.
The own binary polymer D of second performance and the characterization result of structure prepared by this comparative example please participate in table 4 below.
Comparative example 2
Be the same as Example 1, difference is, no mixing liquid I, and co-catalyst and major catalyst are added directly into reactor
In, prepare the own binary polymer E of second using ethene and 1- hexenes as raw material.Namely the method in this comparative example is similar to
CN104628904CN, but inlet amount is different.The performance of the own binary polymer E of second prepared by this comparative example and structure
Characterization result please participate in table 4 below.
Comparative example 3
Be the same as Example 2, difference is, does not have mixing liquid I, and co-catalyst and major catalyst are added directly into reaction
In device, second fourth binary polymer F is prepared using ethene and 1- butylene as raw material.Namely the method in this comparative example is similar to
CN104628904CN, but inlet amount is different.The performance of the own binary polymer F of second prepared by this comparative example and structure
Characterization result please participate in table 4 below.
Table 4
From above example 1-3 and the preparation-obtained polyvinyl characterization result of comparative example, embodiment 1-3
In the own polymer A of second, the polymer D-F of second fourth polymer B and the pungent polymer C of second compared to comparative example 1-3 that prepare
There is smaller molecular weight distribution index PI, the ethene polymers that this explanation is obtained using the inventive method has narrower molecule
Amount distribution.
In addition, in same monomer, and polymer weight average molecular weight relatively in the case of, utilize the inventive method system
Standby obtained copolymer, its melt index MFR is relatively low, and density, mist degree are significantly lower than the polymer of comparative example, and tack will height
Copolymer in comparative example (see embodiment 1 and comparative example 1 and 2, embodiment 2 and comparative example 3).This is related to production method
's.Production method in the present invention, the strand content of highly -branched degree is more, and chain entanglement degree rises, and bond properties is improved,
And then density reduction, mist degree are reduced and tack raising.
In embodiment 1-3, octene is most long as the branch lengths of the copolymer of comonomer；Butylene is used as comonomer
The branch lengths of copolymer are most short, therefore mist degree is C ＜ A ＜ B, and tack C ＞ A ＞ B.
From above example 1-3 and the preparation-obtained polyvinyl characterization results of comparative example 1-3, further
Carrier is done using a kind of mixing solution containing alkane and alkene major catalyst is transported in reactor, and control wherein alpha-olefin
With the mol ratio of ethene, be more beneficial for improving the content of the strand of the degree containing highly -branched, be conducive to making density polymer reduction,
Mist degree is reduced and tack is improved.
It is the embodiment of BOPE film preparations below
Embodiment 4
(1) preparation of BOPE films
The BOPE films of the present embodiment include totally three layers of exterior layer 1, sandwich layer and exterior layer 2, exterior layer 1 and exterior layer 2 successively
It is connected respectively with the two sides of sandwich layer, exterior layer 1 and 2 is the outermost layer that film is directly contacted with external environment.
Exterior layer 1 and exterior layer 2 it is raw materials used and proportioning be：The 70wt% Mitsui chemical company trade mark is SP1520
LLDPE (LLDPE), 10wt% LG chemical companies of the South Korea trade mark is H5200 COPP (MFR=
2g/10min), the 16wt% Exxon Mobil chemical company trade mark is Exceed1327KD metallocene PE (MPE),
4wt% bonding-prevention master batch (ABPP 905DCPP).
Sandwich layer is raw materials used and proportioning is：The ethene obtained in 94wt% embodiment 1/1- hexene copolymers (second oneself two
First polymer A), 3wt% smooth functional master batch (603PP), the 3wt% material of the carbon eight (ethene of metallocene catalyst synthesis-pungent
Alkene copolymer, Tao Shi 488-4A).
Exterior layer 1, exterior layer 2 and sandwich layer material are well mixed in above ratio, storage tank is then sent to, through pipeline
Three single screw extrusion machine extrusions are delivered to respectively, then are extruded into pipe through triple extrusion die head, and pipe layering part by weight is outer
Portion's layer 1：Sandwich layer：Exterior layer 2=20:60:20, the screw diameter of the single screw extrusion machine of exterior layer is 50mm, and draw ratio is 30:
1, extrusion temperature is 220 DEG C, and the screw diameter of the single screw extrusion machine of sandwich layer is 100mm, and draw ratio is 30：1, extrusion temperature is
220 DEG C, extruded material converges to form pipe in triple extrusion die head, and the temperature of extrusion die is 223 DEG C, and the pipe of extrusion is through cold
But rear haulage enters drawing oven.Pipe is filled with compressed air in drawing oven and stretched, and draft temperature is 116 DEG C, horizontal
It is 2.2-2.7 to draw ratio, longitudinal stretching multiple is 2.2-2.7, you can the film that thickness is 25 μm is obtained, after biaxial tension
Film force to cool down through vane, to point splitting after wind, cutting obtains final products, i.e. BOPE films G.
(2) performance characterization of BOPE films
The performance characterization of BOPE films G prepared by the present embodiment is the results detailed in table 5 below.
Embodiment 5
(1) preparation of BOPE films
The BOPE films of the present embodiment include totally three layers of exterior layer 1, sandwich layer and exterior layer 2, exterior layer 1 and exterior layer 2 successively
It is connected respectively with the two sides of sandwich layer, exterior layer 1 and 2 is the outermost layer that film is directly contacted with external environment.
Exterior layer 1 and exterior layer 2 it is raw materials used and proportioning be：The 70wt% Mitsui chemical company trade mark is SP1520
LLDPE (LLDPE), 10wt% LG chemical companies of the South Korea trade mark is H5200 COPP (MFR=
2g/10min), the 16wt% Exxon Mobil chemical company trade mark is Exceed1327KD metallocene PE (MPE),
4wt% bonding-prevention master batch.
Sandwich layer is raw materials used and proportioning is：Ethylene/1-butene copolymer (the second fourth two obtained in 94wt% embodiment 2
First polymer B), 3wt% smooth functional master batch (be the same as Example 4), the 3wt% material of carbon eight (be the same as Example 4).
Exterior layer 1, exterior layer 2 and sandwich layer material are well mixed in above ratio, storage tank is then sent to, through pipeline
Three single screw extrusion machine extrusions are delivered to respectively, then are extruded into pipe through triple extrusion die head, and pipe layering part by weight is outer
Portion's layer 1：Sandwich layer：Exterior layer 2=20:60:20, the screw diameter of the single screw extrusion machine of exterior layer is 50mm, and draw ratio is 30:
1, extrusion temperature is 220 DEG C, and the screw diameter of the single screw extrusion machine of sandwich layer is 100mm, and draw ratio is 30：1, extrusion temperature is
220 DEG C, extruded material converges to form pipe in triple extrusion die head, and the temperature of extrusion die is 223 DEG C, and the pipe of extrusion is through cold
But rear haulage enters drawing oven.Pipe is filled with compressed air in drawing oven and stretched, and draft temperature is 116 DEG C, horizontal
It is 2.2-2.7 to draw ratio, longitudinal stretching multiple is 2.2-2.7, you can the film that thickness is 25 μm is obtained, after biaxial tension
Film force to cool down through vane, to point splitting after wind, cutting obtains final products, i.e. BOPE films H.
(2) performance characterization of BOPE films
The performance characterization of BOPE films H prepared by the present embodiment is the results detailed in table 5 below.
Embodiment 6
(1) preparation of BOPE films
The BOPE films of the present embodiment include totally three layers of exterior layer 1, sandwich layer and exterior layer 2, exterior layer 1 and exterior layer 2 successively
It is connected respectively with the two sides of sandwich layer, exterior layer 1 and 2 is the outermost layer that film is directly contacted with external environment.
Exterior layer 1 and exterior layer 2 it is raw materials used and proportioning be：The 70wt% Mitsui chemical company trade mark is SP1520
LLDPE (LLDPE), 10wt% LG chemical companies of the South Korea trade mark is H5200 COPP (MFR=
2g/10min), the 16wt% Exxon Mobil chemical company trade mark is Exceed1327KD metallocene PE (MPE),
4wt% bonding-prevention master batch (be the same as Example 4).
Sandwich layer is raw materials used and proportioning is：The ethene obtained in 94wt% embodiment 3/1- octene copolymers (second pungent two
First polymer C), 3wt% smooth functional master batch (be the same as Example 4), the 3wt% material of carbon eight (be the same as Example 4).
Exterior layer 1, exterior layer 2 and sandwich layer material are well mixed in above ratio, storage tank is then sent to, through pipeline
Three single screw extrusion machine extrusions are delivered to respectively, then are extruded into pipe through triple extrusion die head, and pipe layering part by weight is outer
Portion's layer 1：Sandwich layer：Exterior layer 2=20:60:20, the screw diameter of the single screw extrusion machine of exterior layer is 50mm, and draw ratio is 30:
1, extrusion temperature is 220 DEG C, and the screw diameter of the single screw extrusion machine of sandwich layer is 100mm, and draw ratio is 30：1, extrusion temperature is
220 DEG C, extruded material converges to form pipe in triple extrusion die head, and the temperature of extrusion die is 223 DEG C, and the pipe of extrusion is through cold
But rear haulage enters drawing oven.Pipe is filled with compressed air in drawing oven and stretched, and draft temperature is 116 DEG C, horizontal
It is 2.2-2.7 to draw ratio, longitudinal stretching multiple is 2.2-2.7, you can the film that thickness is 25 μm is obtained, after biaxial tension
Film force to cool down through vane, to point splitting after wind, cutting obtains final products, i.e. BOPE films I.
(2) performance characterization of BOPE films
The performance characterization of BOPE films I prepared by the present embodiment is the results detailed in table 5 below.
Comparative example 4
(1) preparation of BOPE films
The BOPE films of the present embodiment include totally three layers of exterior layer 1, sandwich layer and exterior layer 2, exterior layer 1 and exterior layer 2 successively
It is connected respectively with the two sides of sandwich layer, exterior layer 1 and 2 is the outermost layer that film is directly contacted with external environment.
Exterior layer 1 and exterior layer 2 it is raw materials used and proportioning be：The 70wt% Mitsui chemical company trade mark is SP1520
LLDPE (LLDPE), 10wt% LG chemical companies of the South Korea trade mark is H5200 COPP (MFR=
2g/10min), the 16wt% Exxon Mobil chemical company trade mark is Exceed1327KD metallocene PE (MPE),
4wt% bonding-prevention master batch (be the same as Example 4).
Sandwich layer is raw materials used and proportioning is：The ethene obtained in 94wt% comparative example 1/1- hexene copolymers (second oneself two
First polymer D), 3wt% smooth functional master batch, the 3wt% material of carbon eight.
Exterior layer 1, exterior layer 2 and sandwich layer material are well mixed in above ratio, storage tank is then sent to, through pipeline
Three single screw extrusion machine extrusions are delivered to respectively, then are extruded into pipe through triple extrusion die head, and pipe layering part by weight is outer
Portion's layer 1：Sandwich layer：Exterior layer 2=20:60:20, the screw diameter of the single screw extrusion machine of exterior layer is 50mm, and draw ratio is 30:
1, extrusion temperature is 220 DEG C, and the screw diameter of the single screw extrusion machine of sandwich layer is 100mm, and draw ratio is 30：1, extrusion temperature is
220 DEG C, extruded material converges to form pipe in triple extrusion die head, and the temperature of extrusion die is 223 DEG C, and the pipe of extrusion is through cold
But rear haulage enters drawing oven.Pipe is filled with compressed air in drawing oven and stretched, and draft temperature is 116 DEG C, horizontal
It is 2.2-2.7 to draw ratio, longitudinal stretching multiple is 2.2-2.7, you can the film that thickness is 25 μm is obtained, after biaxial tension
Film force to cool down through vane, to point splitting after wind, cutting obtains final products, i.e. BOPE films J.
(2) performance characterization of BOPE films
The performance characterization of BOPE films J prepared by the present embodiment is the results detailed in table 5 below.
Comparative example 5
(1) preparation of BOPE films
The BOPE films of the present embodiment include totally three layers of exterior layer 1, sandwich layer and exterior layer 2, exterior layer 1 and exterior layer 2 successively
It is connected respectively with the two sides of sandwich layer, exterior layer 1 and 2 is the outermost layer that film is directly contacted with external environment.
Exterior layer 1 and exterior layer 2 it is raw materials used and proportioning be：The 70wt% Mitsui chemical company trade mark is SP1520
LLDPE (LLDPE), 10wt% LG chemical companies of the South Korea trade mark is H5200 COPP (MFR=
2g/10min), the 16wt% Exxon Mobil chemical company trade mark is Exceed1327KD metallocene PE (MPE),
4wt% bonding-prevention master batch (be the same as Example 4).
Sandwich layer is raw materials used and proportioning is：The ethene obtained in 94wt% comparative example 2/1- hexene copolymers (second oneself two
First polymer E), 3wt% smooth functional master batch (be the same as Example 4), the 3wt% material of carbon eight (be the same as Example 4).
Exterior layer 1, exterior layer 2 and sandwich layer material are well mixed in above ratio, storage tank is then sent to, through pipeline
Three single screw extrusion machine extrusions are delivered to respectively, then are extruded into pipe through triple extrusion die head, and pipe layering part by weight is outer
Portion's layer 1：Sandwich layer：Exterior layer 2=20:60:20, the screw diameter of the single screw extrusion machine of exterior layer is 50mm, and draw ratio is 30:
1, extrusion temperature is 220 DEG C, and the screw diameter of the single screw extrusion machine of sandwich layer is 100mm, and draw ratio is 30：1, extrusion temperature is
220 DEG C, extruded material converges to form pipe in triple extrusion die head, and the temperature of extrusion die is 223 DEG C, and the pipe of extrusion is through cold
But rear haulage enters drawing oven.Pipe is filled with compressed air in drawing oven and stretched, and draft temperature is 116 DEG C, horizontal
It is 2.2-2.7 to draw ratio, longitudinal stretching multiple is 2.2-2.7, you can the film that thickness is 25 μm is obtained, after biaxial tension
Film force to cool down through vane, to point splitting after wind, cutting obtains final products, i.e. BOPE films K.
(2) performance characterization of BOPE films
The performance characterization of BOPE films K prepared by the present embodiment is the results detailed in table 5 below.
Comparative example 6
(1) preparation of BOPE films
The BOPE films of the present embodiment include totally three layers of exterior layer 1, sandwich layer and exterior layer 2, exterior layer 1 and exterior layer 2 successively
It is connected respectively with the two sides of sandwich layer, exterior layer 1 and 2 is the outermost layer that film is directly contacted with external environment.
Exterior layer 1 and exterior layer 2 it is raw materials used and proportioning be：The 70wt% Mitsui chemical company trade mark is SP1520
LLDPE (LLDPE), 10wt% LG chemical companies of the South Korea trade mark is H5200 COPP (MFR=
2g/10min), the 16wt% Exxon Mobil chemical company trade mark is Exceed1327KD metallocene PE (MPE),
4wt% bonding-prevention master batch (be the same as Example 4).
Sandwich layer is raw materials used and proportioning is：Ethylene/1-butene copolymer (the second fourth two obtained in 94wt% comparative example 3
First polymer F), 3wt% smooth functional master batch (be the same as Example 4), the 3wt% material of carbon eight (be the same as Example 4).
Exterior layer 1, exterior layer 2 and sandwich layer material are well mixed in above ratio, storage tank is then sent to, through pipeline
Three single screw extrusion machine extrusions are delivered to respectively, then are extruded into pipe through triple extrusion die head, and pipe layering part by weight is outer
Portion's layer 1：Sandwich layer：Exterior layer 2=20:60:20, the screw diameter of the single screw extrusion machine of exterior layer is 50mm, and draw ratio is 30:
1, extrusion temperature is 220 DEG C, and the screw diameter of the single screw extrusion machine of sandwich layer is 100mm, and draw ratio is 30：1, extrusion temperature is
220 DEG C, extruded material converges to form pipe in triple extrusion die head, and the temperature of extrusion die is 223 DEG C, and the pipe of extrusion is through cold
But rear haulage enters drawing oven.Pipe is filled with compressed air in drawing oven and stretched, and draft temperature is 116 DEG C, horizontal
It is 2.2-2.7 to draw ratio, longitudinal stretching multiple is 2.2-2.7, you can the film that thickness is 25 μm is obtained, after biaxial tension
Film force to cool down through vane, to point splitting after wind, cutting obtains final products, i.e. BOPE films L.
(2) performance characterization of BOPE films
The performance characterization of BOPE films L prepared by the present embodiment is the results detailed in table 5 below.
Table 5
Above example 4,5 and 6 and comparative example 4-6 are compared and understood, it is BOPE films G, H and I tensile strength, anti-tear
Resistance to spalling and puncture resistance and tangent modulus are all substantially better than BOPE films J, K, L.Utilize being total to that the inventive method is prepared
BOPE films G, H, I its tack, mist degree and the translucency that polymers A, B, C are formed are superior to comparative example BOPE films J, K, L.
It is contour that polymeric articles in the present invention can be used for making high transmittance film, label film, suction pipe packaging film and antibacterial film
Hold product.
Any numerical value mentioned in the present invention, if simply having two between any minimum and any of the highest value
The interval of unit, then include all values of one unit of each increase from minimum to peak.If for example, life is a kind of
The amount of component, or the value of the state-variable such as temperature, pressure, time is 50-90, in this manual it means that specific
List 51-89,52-88 ... and the numerical value such as 69-71 and 70-71.For the value of non-integer, can with due regard to
0.1st, 0.01,0.001 or 0.0001 is a unit.This is only some special examples indicated.In this application, with similar side
Formula, the combination that is possible to of the numerical value between cited minimum and peak is considered to disclose.
When explanation is of the invention it is noted that embodiment described above is only used for, any limit to the present invention is not constituted
System.By referring to exemplary embodiments, invention has been described, it should be appreciated that wherein word used to be descriptive and
Explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation and repaiied
Change, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it is related to
Specific method, material and embodiment, it is not intended that the present invention is limited to wherein disclosed particular case, on the contrary, of the invention
It can be extended to other all methods and applications with identical function.
Claims (13)
1. a kind of polyvinyl preparation method, including：With mixing liquid I it is carrier logistics by sponsoring in catalyst system
Agent is transported in reactor, and the mixing liquid I includes alkane, alkene and co-catalyst；To the thing flowed out from reactor
Flow and supplement olefin feedstocks are added in II, obtain stream I II, stream I II is divided into stream I IIa and IIIb, stream I IIa and IIIb
Sidepiece and the bottom of reactor are back to respectively；In the reactor, it is aggregated to obtain ethene polymers and discharged from reactor；
Wherein, the alkene includes alpha-olefin and ethene, and the mol ratio of alpha-olefin and ethene is at least 1 in the mixing liquid I.
2. according to the method described in claim 1, it is characterised in that the mol ratio of alpha-olefin and ethene in the mixing liquid I
For (1-5)：1, preferably (1.3-5)：1, more preferably (1.5-5)：1；And/or in the mixing liquid I, the content of alkane is 5-
80wt%, preferably 10-65wt%；And/or, the mass flow of the mixing liquid I accounts for stream I I mass flow
0.05%-5%, preferably in 0.1%-3%.
3. method according to claim 1 or 2, it is characterised in that the reaction pressure in the reactor is 0.5-
10MPa, preferably 1.5-5MPa；Reaction temperature is 40-150 DEG C, preferably 60-100 DEG C；And/or, the apparent stream in the reactor
Change gas velocity is 0.1-10m/s, preferably 0.3-0.8m/s.
4. the method according to any one in claim 1-3, it is characterised in that different comprising temperature in the reactor
Reaction zone；And/or the reactor is fluidized-bed reactor.
5. the method according to any one in claim 1-4, it is characterised in that in the stream I II, the content of alkene
For 1.0-60.0mol%, preferably 5.0-55.0mol%；Or the content of alkane is 0.5-50.0mol%, preferably 1.0-
35.0mol%；Or in the stream I II, the molar concentration of alpha-olefin accounts for the 20%-60% of the molar concentration of ethene.
6. the method according to any one in claim 1-5, it is characterised in that the alkane in stream I IIa accounts for logistics
The 60-90wt% of alkane total amount in III；And/or the 10- of alkene total amount that the alkene in stream I IIa is accounted in stream I II
50wt%；And/or, stream I I mass flow accounts for more than the 90% of stream I II mass flow, preferably more than 95%.
7. the method according to any one in claim 1-6, it is characterised in that conditioning agent is included in the stream I II
And/or inert component；Wherein, the conditioning agent is preferably hydrogen；The inert component is preferably nitrogen；It is highly preferred that described
In stream I II, the content of the conditioning agent is 0.3-14.5mol%；And/or in the stream I II, the inert component
Measure as 25.0-75.0mol%.
8. the method according to any one in claim 5-7, it is characterised in that supplement alkane is included in the stream I II
At least one of hydrocarbon charging, the charging of supplement conditioning agent and supplement inert component charging.
9. the method according to any one in claim 1-8, it is characterised in that the alkane comprising butane, iso-butane,
At least one of pentane, isopentane, n-hexane, hexamethylene and heptane；And/or the alpha-olefin be selected from propylene, 1- butylene,
At least one of 1- amylenes, 1- hexenes, 1- octenes and 1- decene.
10. the method according to any one in claim 1-9, it is characterised in that the catalyst system includes neat lattice
Le-Natta catalyst, metallocene catalyst, transition-metal catalyst, inorganic chrome catalysts and organic chrome catalysts.
11. the method according to any one in claim 1-10, it is characterised in that in prepared ethene polymers,
Molar content shared by 'alpha '-olefin monomers unit is 1-30%, preferably 1-10%；
Or prepared ethene polymers has following characteristic：Density is in 0.890g/cm3To 0.922g/cm3Between, preferably
0.895 to 0.917g/cm3；Melt flow rate (MFR) under conditions of 230 DEG C and 2.16kg is 0.1-10g/10min, preferably
0.5-5.0g/10min；Weight average molecular weight is 20000-250000, and molecular weight distributing index is 2-15.
12. the method according to any one in claim 1-11, it is characterised in that the polyvinyl mist degree is low
In 12.0%, preferably shorter than 10.3%, more preferably less than 9.6%；And/or in the ethene polymers, the value of tack is
0.2N/cm2-1N/cm2, preferably 0.3N/cm2-1N/cm2。
13. application of the ethene polymers that in claim 1-12 prepared by any one methods described in film article；It is described
Film article preferably includes packaging material and/or Commercial goods labelses, more preferably boiling film, high transparency film, barrier protection film, heat-sealing film
Or label film.
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| WO2020192402A1 (en) * | 2019-03-27 | 2020-10-01 | 中国石油化工股份有限公司 | Olefin polymerization method and system |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1518867A1 (en) * | 2003-08-11 | 2005-03-30 | Exxonmobil Chemical Patents Inc. | Polymers of ethylene and optionally, copolymerizable esters, films using such polymers and stretch hood packaging processesusing such films |
| CN105802033A (en) * | 2016-03-14 | 2016-07-27 | 浙江大学 | Preparation method and application of polyethylene film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1518867A1 (en) * | 2003-08-11 | 2005-03-30 | Exxonmobil Chemical Patents Inc. | Polymers of ethylene and optionally, copolymerizable esters, films using such polymers and stretch hood packaging processesusing such films |
| CN105802033A (en) * | 2016-03-14 | 2016-07-27 | 浙江大学 | Preparation method and application of polyethylene film |
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|---|---|---|---|---|
| WO2020192402A1 (en) * | 2019-03-27 | 2020-10-01 | 中国石油化工股份有限公司 | Olefin polymerization method and system |
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