CN103154050B - Olefine polymerizing process - Google Patents
Olefine polymerizing process Download PDFInfo
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- CN103154050B CN103154050B CN201180050746.8A CN201180050746A CN103154050B CN 103154050 B CN103154050 B CN 103154050B CN 201180050746 A CN201180050746 A CN 201180050746A CN 103154050 B CN103154050 B CN 103154050B
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- dibenzoate
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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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/06—Propene
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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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
Abstract
The method of the propylene (co) polymerization that a kind of temperature at 77 to 95 DEG C in the presence of a catalyst is carried out, described catalyst includes reacting, by organo-aluminum compound and ingredient of solid catalyst, the product obtained, and described ingredient of solid catalyst comprises Mg, Ti and the electronic donor compound capable selected from concrete diol ester.
Description
The preparation that the present invention relates to carry out at comparative high temperature in the presence of concrete ziegler-natta polymerization catalysts gathers
The method of alkene.
The polymerization of alkene is exothermic reaction, therefore, it is necessary to provide the device making bed cool down, to remove heat of polymerization.
Under not having this cooling, bed tempertaure increases, until such as catalyst becomes inertia, or bed starts to melt.At alkene
Fluidised bed polymerisation in, remove heat of polymerization method for optimizing be by by a kind of gas in the temperature less than required polymerization temperature
(fluidizing gas) provides polymer reactor；Pass the gas through fluid bed, to take away heat of polymerization；Gas is removed from reactor, and
Cooled down by by external heat exchanger；And make it be recycled to bed.
The temperature of recyclegas in scalable heat exchanger, so that fluid bed is maintained at required polymerization temperature.Make α alkene
In this method of polymerized hydrocarbon, recyclegas generally comprises monomeric olefin, optionally with such as inert dilution gas (such as nitrogen) and/
Or gaseous chain transfer agent (such as, hydrogen) is together.Therefore, recyclegas, for providing bed by monomer, makes bed fluidize, and makes bed protect
Hold temperature required.
(that is, space-time yield, with the polymerization produced to know the productivity ratio in the above-mentioned type industrial gases fluidized-bed reactor
Thing weight/unit volume space reactor/unit interval represents) by being limited from the maximum rate of reactor heat extraction.Heat extraction speed
Rate can increase with several means, and this also depends on type of polymerization technique.Such as, in gas fluidised bed polymerisation, followed by raising
The speed of ring gas, reduces the temperature of recyclegas, changes the thermal capacity of recyclegas, can increase heat extraction.
In liquid phase polymerization, by reducing the temperature of the refrigerant liquid of circulation in jacketed reactor, or by improving
Circulation rate, can increase the degree of heat extraction.
But, the speed of the recyclegas that can use in industry reality and circulating liquid there is is physical constraints.Specifically
Saying, in fluidized bed gas-phase polymerization, exceed this limit, bed may become unstable, or carries away reactor the most in the gas flow,
Cause circular route to block, and damage circulating air compressor or aerator.
The most restricted to recyclegas in practice and the coolable degree of circulating cooling liquid.This is mainly by economic consideration
Determine, in practice, generally determined by the temperature of on-the-spot available industrial colling.If it is required, available refrigeration, but this
Increase production cost.
Known heat extraction efficiency is the function of temperature difference between polymer reactor and cooling fluid.Under these conditions, if
Added to cool down the temperature of fluid by weather conditions, then can be by improving heat extraction at higher polymerization temperature operation reactor.
But, along with temperature raises, the antigravity system of industrial use has notable polymerization activity to decay, these actual feelings
Condition hinders the practice of this probability.Obviously, when higher temperature operation, the reduction of polymerization activity hinders and obtains heat extraction effect
Rate.
USP 7,388,061 is open belongs to formula R1-CO-O-CR3R4-A-CR5R6-O-CO-R2Diol ester, wherein R1And R2
Group may be the same or different, and can be to have being substituted or unsubstituting hydrocarbyl of 1 to 20 carbon atom, R3-R6Group can identical or
Difference, is selected from hydrogen, halogen or has being substituted or unsubstituting hydrocarbyl of 1 to 20 carbon atom, R1-R6Group optionally comprises one
Individual or multiple replacement carbon, hydrogen atom or both hetero atoms, described hetero atom selected from nitrogen, oxygen, sulfur, silicon, phosphorus and halogen atom,
R3-R6Two or more groups of group can connect into saturated or unsaturated monocycle or multi-ring；A is singly-bound or divalent linker
Group, and a length of 1-10 the atom of chain between two free radicals, wherein said divalent linker be selected from aliphatic, alicyclic and
Aromatic divalent radical group, and portability C1-C20 is linear or branched substituent；One or more on above-mentioned divalent linker
Carbon atom and/or hydrogen atom and substituent group can be replaced by the hetero atom selected from nitrogen, oxygen, sulfur, silicon, phosphorus and halogen atom, and even
Meet two or more the described substituent groups on group and above-mentioned R3-R6Group can connect into saturated or unsaturated monocycle or multi-ring.
The embodiment reported in the literature typically shows the ability manufacturing the polymer with wide molecular weight distribution.Just polymerization
For activity and stereospecificity, the performance of catalyst is that very poor (see embodiment 68 and 86) is to good.All propylene polymerizations try
Test and carry out at 70 DEG C.Not in the data of higher temperature propylene polymerization.But, in embodiment 105 and 106, use about
In the same catalyst of the embodiment 95 and 96 described in 70 DEG C of propylene polymerizations, carry out vinyl polymerization at 85 DEG C.Gather at 85 DEG C of ethylene
Close display in terms of polymerization activity far below the result 70 DEG C of propylene polymerization activity.
It addition, reduce active self-extinguishment carbon monoxide-olefin polymeric to prepare to have in the temperature higher than 70 DEG C, special in the world
Profit application WO2009/085649 advises preparing with the diol ester of type described in USP 7,388,061 and alkyl aluminum co-catalysis
Agent, selective control agent and some optional activity limit the catalytic component that agent is applied in combination.Carry out in hydrocarbon slurry is poly-
Conjunction embodiment shows, forwards the polymerization temperature of 100 DEG C to from the polymerization temperatures of 67 DEG C, and activity drops to the 46% of initial value, thereby indicate that
Substantial attenuation.
It has been surprisingly discovered that when certain temperature range is for propylene polymerization, the concrete subclass of diol ester does not show decay,
On the contrary, display polymerization activity increases.Accordingly, because more effectively heat extraction and more high polymerization activity, these catalyst make to be polymerized
Journey is more efficient at high temperature.
Therefore, it is an object of the invention to the propylene (being total to) that temperature at 77 to 95 DEG C in the presence of a catalyst carries out gather
The method closed, described catalyst includes by organo-aluminum compound and ingredient of solid catalyst and optional external electronic donor chemical combination
The product that thing reaction obtains, described ingredient of solid catalyst comprises Mg, Ti and the electronic donor compound capable with following formula (A)
(A)
-wherein R1-R4Group is the most identical or different, for hydrogen or optionally comprise selected from halogen, the hetero atom of P, S, N and Si
C1-C15Alkyl, its condition is R1And R4Being asynchronously hydrogen, R group is the most identical or different, looped selected from can optionally connect
C1-C15Alkyl, and n is the integer of 0 to 5.
Method is preferably carried out the temperature of 80 to 95 DEG C, more preferably higher than 80 to 95 DEG C, is especially more than 80 to 90 DEG C, the most especially
It is higher than 80 to 88 DEG C.
Preferably in the electron donor of formula (A), R1And R4It is independently selected from C1-C15Alkyl, C6-C14Aryl, C3-C15Cycloalkyl
And C7-C15Aryl alkyl or alkylaryl.More preferably R1And R4Selected from C1-C10Alkyl, even more preferably selected from C1-C5Alkyl, tool
Body is methyl.
Preferably in the electron donor of formula (A), R2-R3Group is independently selected from hydrogen, C1-C15Alkyl, C6-C14Aryl, C3-C15
Cycloalkyl and C7-C15Aryl alkyl or alkylaryl.More preferably R2And R3Selected from hydrogen or C1-C10Alkyl, even more preferably selected from hydrogen
Or C1-C5Alkyl, specifically, methyl.In a preferred embodiment, hydrogen and methyl are preferably used.A concrete reality
Execute in scheme, R2And R3Both are hydrogen.
Preferably in the electron donor of formula (A), R group is selected from C1-C15Alkyl, C6-C14Aryl, C3-C15Cycloalkyl and C7-
C15Aryl alkyl or alkylaryl.More preferably R is selected from C1-C10Alkyl, even more preferably selected from C1-C5Alkyl.The most excellent
Choosing is methyl, ethyl, n-pro-pyl and normal-butyl.Index n can be that 0 to 5(includes end points), preferably 1 to 3, more preferably 1.Work as n
When being 1, substituent R is preferably at 4 of benzoate ring.
It addition, in the electron donor of formula (A), preferred structure is wherein R1And R4It is methyl simultaneously, R2And R3For hydrogen, n
It is 1, on 4 of phenyl ring those structures that R group is methyl, ethyl, n-pro-pyl or normal-butyl.
The non-limiting example of structure (A) is following material: 2,4-PD dibenzoate, 3-methyl-2,4-PD
Dibenzoate, 3-ethyl-2,4-PD dibenzoate, 3-n-pro-pyl-2,4-PD dibenzoate, 3-isopropyl
Base-2,4-PD dibenzoate, 3-normal-butyl-2,4-PD dibenzoate, 3-isobutyl group-2,4-PD hexichol
Formic acid esters, the 3-tert-butyl group-2,4-PD dibenzoate, 3-n-pentyl-2,4-PD dibenzoate, 3-isopentyl-
2,4-PD dibenzoate, 3-cyclopenta-2,4-PD dibenzoate, 3-cyclohexyl-2,4-PD hexichol first
Acid esters, 3-phenyl-2,4-PD dibenzoate, 3-(2-naphthyl)-2,4-PD dibenzoate, 3-pi-allyl-2,
4-glycol dibenzoate, 3,3-dimethyl-2,4-PD dibenzoate, 3-ethyl-3-methyl-2,4-PD two
Benzoate, 3-methyl-3-isopropyl-2,4-PD dibenzoate, 3,3-diisopropyl-2,4-PD dibenzoic acid
Ester, 3-isopentyl-2-isopropyl-2,4-PD dibenzoate, 3,5-heptandiol dibenzoate, 4,6-nonanediol hexichol
Formic acid esters, 2,6-dimethyl-3,5-heptandiol dibenzoate, 5,7-undecane dibenzoate, 2,8-dimethyl-4,
6-nonanediol dibenzoate, 2,2,6,6-tetramethyl-3,5-heptandiol dibenzoate, 6,8-tridecane diols dibenzoic acid
Ester, 2,10-dimethyl-5,7-undecane dibenzoate, 1,3-bicyclopentyl-1,3-propylene glycol dibenzoate, 1,
Double (the 2-naphthalene of 3-dicyclohexyl-1,3-propylene glycol dibenzoate, 1,3-diphenyl-1,3-propylene glycol dibenzoate, 1,3-
Base)-1,3-propylene glycol dibenzoate, 2,4-hexanediol dibenzoate, 2,4-heptandiol dibenzoate, 2-methyl-3,
5-hexanediol dibenzoate, 2,4-ethohexadiol dibenzoate, 2-methyl-4,6-heptandiol dibenzoate, 2,2-diformazan
Base-3,5-hexanediol dibenzoate, 2-methyl-5,7-ethohexadiol dibenzoate, 2,4-nonanediol dibenzoate, 1-ring
Amyl group-1,3 butylene glycol dibenzoate, 1-cyclohexyl-1,3 butylene glycol dibenzoate, 1-phenyl-1,3 butylene glycol hexichol
Formic acid esters, 1-(2-naphthyl)-1,3 butylene glycol dibenzoate, 2,4-PD-bis-(4-methyl benzoic acid ester), 2,4-penta 2
Alcohol-bis-(3-methyl benzoic acid ester), 2,4-PD-bis-(4-ethylamino benzonitrile acid esters), 2,4-PD-bis-(4-n-propylbenzene
Formic acid esters), 2,4-PD-bis-(4-n-butylbenzoic acid ester), 2,4-PD-bis-(4-isopropyl acid ester), 2,4-
Pentanediol-bis-(4-isobutyl-benzene formic acid esters), 2,4-PD-bis-(4-p t butylbenzoic acid ester), 2,4-PD-bis-(4-
Phenylbenzoate), 2,4-PD-bis-(3,4-mesitylenic acid ester), 2,4-PD-bis-(2,4,6-trimethylbenzene
Formic acid esters), 2,4-PD-bis-(2,6-mesitylenic acid ester), 2,4-PD-two-(2-naphthoate), 3-methyl-
2,4-PD-bis-(4-n-propylbenzene formic acid esters), 3-isopentyl-2,4-PD-bis-(4-n-propylbenzene formic acid esters), 1,1,
1,5,5,5-hexafluoro-2,4-PD-bis-(4-ethylamino benzonitrile acid esters), the fluoro-2,4-PD of 1,1,1-tri--bis-(4-ethylo benzenes
Formic acid esters), 1,3-double (4-chlorphenyl)-1,3-propylene glycol-bis-(4-ethylamino benzonitrile acid esters), 1-(2,3,4,5,6-phenyl-pentafluoride
Base)-1,3 butylene glycol-bis-(4-ethylamino benzonitrile acid esters), 1,1-bis-fluoro-4-phenyl-2,4-butanediol-bis-(4-n-propylbenzene first
Acid esters), 1,1,1-tri-fluoro-5,5-dimethyl-2,4-hexanediol-bis-(4-n-propylbenzene formic acid esters), 1,1,1-tri-fluoro-4-(2-
Furyl)-2,4-butanediol-bis-(4-n-propylbenzene formic acid esters), fluoro-4-phenyl-2,4-butanediol-bis-(4-is just for 1,1,1-tri-
Propylbenzoic acid ester), the fluoro-4-of 1,1,1-tri-(2-thienyl)-2,4-butanediol-bis-(4-n-propylbenzene formic acid esters), 1,1,1-
Three fluoro-4-(4-chlorphenyl)-2,4-butanediol-bis-(4-n-propylbenzene formic acid esters), the fluoro-4-of 1,1,1-tri-(2-naphthyl)-2,4-
Butanediol-bis-(4-n-propylbenzene formic acid esters), the chloro-2,4-PD of 3--bis-(4-n-propylbenzene formic acid esters).
As explained above, in addition to above electron donor, the catalytic component of the present invention also comprises Ti, Mg and halogen.Specifically
Say, catalytic component includes the titanium compound with at least Ti-halogen bond that is carried on magnesium halide and above-mentioned electricity
Sub-donor compound.Magnesium halide is preferably the MgCl of the activity form being used for Ziegler-Natta catalyst as carrier2, can be from
Patent documentation is extensively understood.Patent USP 4,298,718 and USP 4,495,338 is first to be described in ziegler-natta catalyzed
Middle these compounds of use.Understand from these patents, as carrier or help carrier in olefinic polymerization used catalyst component
The feature of the magnesium dihalide of the activity form used is X-ray spectrum, the strongest diffraction wherein occurred in non-active halide is composed
Line strength reduces, and is replaced towards the halogeno-group shifted relative to the relatively low angle of higher line by its maximum intensity.
The preferred titanium compound used in the catalytic component of the present invention is TiCl4And TiCl3；It addition, be used as formula
Ti(OR)m-yXyTi-halogenohydrin compound, wherein m is the quantivalence of titanium, and y is the number between 1 and m-1, and X is halogen, and R is for having 1
Alkyl to 10 carbon atoms.
Prepare ingredient of solid catalyst to carry out according to several method.A kind of method is included in electronic donor compound capable and exists
Under the temperature of about 80 to 135 DEG C in magnesium alkoxide or chloropharin magnesium (specifically, according to USP 4, the chloropharin compounds of 220,554 preparations)
With excess TiCl4Between reaction.
According to a kind of method for optimizing, by making formula Ti (OR)m-yXy(wherein m is the quantivalence of titanium, and y is between 1 and m
Number, preferably TiCl4) titanium compound with derived from formula MgCl2(wherein p is the number between 0.1 and 6 to pROH, preferably 2 to 3.5, R
For having the alkyl of 1-18 carbon atom) the magnesium chloride of adduct, ingredient of solid catalyst can be prepared.At adduct
Melt temperature (100-130 DEG C) operates under agitation, passes through mixed alcohol in the presence of unreactive hydrocarbons immiscible with adduct
And magnesium chloride, suitably can prepare adduct with spherical.Then, emulsion rapid quenching, thus cause adduct with form of spherical particles
Solidification.The example of the spherical adduct prepared according to the method is described in USP 4,399,054 and USP 4,469,648.Can make
So obtained adduct directly reacts with Ti compound, or can first pass through thermal control dealcoholysis (80-130 DEG C) in advance, to obtain
Wherein the molal quantity of alcohol is generally below the adduct of 3 (preferably between 0.1 and 2.5).By at cold TiCl4In (general 0 DEG C)
Suspension adduct (dealcoholysis or former state), can be carried out and the reaction of Ti compound；Heat the mixture to 80-135 DEG C, and temperature at this
Degree keeps 0.5 to 2 hour.Use TiCl4Process can carry out one or many.Preferably with TiCl4Electron donor is added during process
Compound.The preparation of spherical catalyst components is described in such as european patent application EP-A-395083, EP-A-553805, EP-
A-553806, EPA601525 and WO98/44001.
The ingredient of solid catalyst obtained according to above method shows general 20 and 500m2(preferably 50 Hes between/g
400m2Between/g) surface area (B.E.T. method) and higher than 0.2cm3/ g is (preferably 0.2 and 0.6cm3Between/g) total hole
Gap rate (B.E.T. method).Due to the radius with maximum 10.000 hole porosity (Hg method) generally 0.3 to
1.5cm3/ g, preferably 0.45 to 1cm3/g。
Ingredient of solid catalyst has the mean diameter of 5 to 120 m, more preferably 10 to 100 m.
In these preparation methoies any, required electronic donor compound capable can former state add, or can be a kind of for choosing
Mode with can be by such as known chemical reaction (such as, etherificate, alkylation, esterification etc.) at required electron donor chemical combination
The applicable precursor converted in thing obtains in situ.
Not considering preparation method, the final quantity of electronic donor compound capable should make relative to MgCl2 Mol ratio be 0.01
To 1, preferably 0.05 to 0.5.
In catalytic component, the amount of Ti atom is preferably gross weight 1 to 10% weight relative to described catalytic component, more
Preferably 1.5 to 8% weight, especially 2 to 5% weight.
Organo-aluminum compound is preferably alkyl aluminum compound.Alkyl aluminum compound is preferably selected from trialkyl aluminium compound, example
Such as triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, tri-n-octylaluminium.It is used as trialkylaluminium and halogenation
The mixture of alkyl aluminum, alkyl aluminium hydride or alkyl aluminium sesquichloride is (such as AlEt2Cl and Al2Et3Cl3)。
Be suitable for External Electron Donor Compound include silicon compound, ether, ester, amine, heterocyclic compound (specifically, 2,2,
6,6-tetramethyl piperidine) and ketone.Another kind of preferred External Electron Donor Compound is formula (R7)a(R8)bSi(OR9)cSilication close
Thing, wherein a and b is the integer of 0 to 2, and c is the integer of 1 to 4, and (a+b+c) sum is 4, R7、R8And R9For optionally comprising hetero atom
There is the alkyl of 1-18 carbon atom, cycloalkyl or aryl.Particularly preferably in silicon compound, a is 1, and b is 1, and c is 2, R7
And R8At least one heteroatomic there is the branched-alkyl of 3-10 carbon atom, cycloalkyl or aryl, R selected from optionally comprising9For
C1-C10Alkyl, specifically, for methyl.The example of these preferred silicon compounds is Cyclohexylmethyldimethoxysilane (C
Donor), dimethoxydiphenylsilane, methyl-t-butyl dimethoxysilane, dicyclopentyl dimethoxyl silane (D donor),
(2-ethyl piperidine base)-t-butyldimethoxysilane, (2-ethyl piperidine base) tertiary hexyl dimethoxysilane, (3,3,3-tri-
Fluorine n-pro-pyl) (2-ethyl piperidine base) dimethoxysilane, methyl (3,3,3-trifluoro n-pro-pyl) dimethoxysilane.It addition,
It is also preferred that in silicon compound, a is 0, c is 3, R8For optionally comprising heteroatomic branched-alkyl or cycloalkyl, R9For methyl.This
The example of a little preferably silicon compounds is cyclohexyl trimethoxy silane, tert-butyl trimethoxy silane and tertiary hexyl trimethoxy
Silane.
External Electron Donor Compound is to obtain the organo-aluminum compound of 0.1 to 500 and described External Electron Donor Compound
The amount of mol ratio uses, and preferably 1 to 300, more preferably 3 to 100.
As previously explained, carry out polymerization process with described catalyst at relatively-high temperature liquid phase polymerization and gas-phase polymerization are all had
Benefit.
Liquid phase polymerization can such as be carried out as diluent with liquid inert hydrocarbon in the slurry, or with liquid monomer (propylene)
Carry out as reaction medium body, or for nascent polymer, carry out in the solution as solvent with monomer or unreactive hydrocarbons.Liquid
Phase-polymerization can be carried out in all kinds reactor, such as continuous stirred tank reactor, loop reactor or plug flow reactor.
Can operate at one or more fluid beds or mechanical stirring reactor and carry out gas-phase polymerization.Also two can comprised
The Gas-phase reactor of interconnected polymerization zones is carried out, and one of two regions work under fast fluidization conditions, and another is in action of gravity
Lower polymer flow.
When being aggregated in gas phase and carrying out, operation pressure is typically between 0.5 and 10MPa, preferably between 1 and 5MPa.?
In polymerisation in bulk, operation pressure is typically between 1 and 6MPa, preferably between 1.5 and 4MPa.
In liquid monomer, polymerisation in bulk and gas-phase polymerization are highly preferred.
By being introduced directly into reactor, the catalyst of the present invention former state can be used for polymerization process.In this alternatives, can
Catalyst prepolymerization was made before introducing the first polymer reactor.As used by prior art, term pre-polymerization refers to that catalyst is
With low conversion degree through polymerization procedure.According to the present invention, the amount about 0.1 at the polymer produced is urged to about 1000g/ gram solid
During agent component, it is believed that catalyst is through pre-polymerization.
Pre-polymerization can be carried out with propylene or other alkene.Specifically, particularly preferably make ethylene or its with the highest 20% mole
Measure the mixture pre-polymerization of one or more alpha-olefins.The preferably conversion of prepolymerization catalyst component is about 0.2g to about 500g/ gram admittedly
Body catalyst component.
Prepolymerization step can be carried out 0 to 60 DEG C of temperature in liquid phase or gas phase, preferably 5 to 50 DEG C.Prepolymerization step can
As the part of continuous polymerization process or individually carry out in batch processes online.In order to prepare 0.5 to 20g/ gram of catalyst group
The amount of polymers divided, when using pre-polymerization in batches, preferably makes catalyst and the ethylene pre-polymerization of the present invention.
As explained above, method for optionally with the (co) polymerization of propylene in the mixture of other alkene.It can be used for making
Make crystalline propylene homopolymer or the copolymer containing up to 10% comonomer (such as, ethylene, 1-butane or 1-hexane), or
It is included in 25 DEG C of relatively high crystalline propene polymer parts insoluble in dimethylbenzene for manufacturing and dissolves in dimethylbenzene at 25 DEG C
The shock resistance prolylene polymer composition of relatively low degree of crystallinity copolymer portion.
Following example are given in order to the present invention is better described, but are not intended to the present invention.
Characterize
Measure X.I.
2.5g polymer and 250ml o-Dimethylbenzene are put into the round-bottomed flask being provided with cooler and reflux condenser, and
Keep under nitrogen.The mixture obtained is heated to 135 DEG C, and under agitation keeps about 60 minutes.Make with continuous stirring
Whole solution is cooled to 25 DEG C, then filters insoluble polymer.Then make filtrate flow down at nitrogen and reach constant weight 140 DEG C of evaporations.
The content of described xylene soluble fraction is expressed as the percent of initial 2.5 grams, and difference is X.I.%.
Melt flow (MFR)
Melt flow MIL of polymer is measured according to ISO 1133 (230 DEG C, 2.16Kg).
Embodiment
The step of preparation spherical adduct
The method described in embodiment 2 according to WO98/44009 prepares primary quantity microspheroidal MgCl2·2.8C2H5OH, but
With fairly large operation.So obtained solid adduct is referred to as adduct A.Then, make the part of this solid 30 to 130
DEG C cumulative temperature is through hot dealcoholysis, and flows down operation at nitrogen, until it reaches 50% weight alcohol content.It is referred to as adding by the solid obtained
Compound B.The part making this solid flows down dealcoholysis at nitrogen further, until it reaches 46% w ethanol.This solid is referred to as adduct
C。
Prepare ingredient of solid catalyst 1 (ID=2,4-glycol dibenzoate)
Add to the 500ml round-bottomed flask being equipped with mechanical agitator, cooler and thermometer under nitrogen atmosphere in room temperature
250ml TiCl4.After being cooled to 0 DEG C, in stirring simultaneously, it is sequentially added into 12.5g adduct B and 2,4-pentanediol two to flask
Benzoate (Mg/ID=8 mole).Raise the temperature to 120 DEG C and keep 2 hours.Subsequently, stop stirring, make solid product sink
Fall, and it is siphoned off supernatant, temperature is maintained at 120 DEG C.After removing supernatant, add other fresh TiCl4, again to reach
To original liquid volume.Again heat the mixture to 120 DEG C, and keep 1 hour in this temperature.Again stop stirring, make solid
Body settles, and is siphoned off supernatant.Titanation step 1 time was repeated through 1 hour at 120 DEG C.
Be siphoned off third time titanizing liquid phase after, by solid anhydrous hexane as little as 60 DEG C thermograde wash six
Secondary (6 × 100ml), and at room temperature washing once (100ml).Then, gained solid is dried under vacuum, analyzes, and be used for
Propylene polymerization.Solid comprises 3.6% weight Ti and 9.4% weight ID.
Prepare ingredient of solid catalyst 2 (ID=2,4-pentanediol is double (4-n-propylbenzene formic acid esters))
Repeat above with respect to the preparation described in ingredient of solid catalyst 1, but now in Mg/ID mol ratio equal to 9.5, with 2,
4-pentanediol double (4-n-propylbenzene formic acid esters) is as interior electron donor.The solid obtained comprises 3.7% weight Ti and 10.4% weight
Amount ID.
Prepare ingredient of solid catalyst 3 (ID=3-methyl-2,4-PD dibenzoate)
Repeat above with respect to the preparation described in ingredient of solid catalyst 1, but now by 3-methyl-2,4-pentanediol hexichol first
Acid esters is as interior electron donor.The solid obtained comprises 4.1% weight Ti and 4.7% weight ID.
Prepare ingredient of solid catalyst 4 (ID=2,2,4-trimethyl-1,3-glycol dibenzoate)
Repeat above with respect to the preparation described in ingredient of solid catalyst 1, there is following difference.The internal donor currently used is
2,2,4-trimethyl-1,3-glycol dibenzoate, Mg/ID=6.With adduct A as magnesium precursor.Only use two titanizings
Step, first is carried out 2 hours at 100 DEG C, and second carries out 1 hour at 120 DEG C.The solid obtained comprises 4.7% weight Ti.
Prepare ingredient of solid catalyst 5 (comparative, ID=2-isopentyl-2-isopropyl-1,3-PD hexichol first
Acid esters)
Repeat above with respect to the preparation described in ingredient of solid catalyst 4, there is following difference.The internal donor currently used is
2-isopentyl-2-isopropyl-1,3-glycol dibenzoate, Mg/ID=8.With adduct B as magnesium precursor.The solid obtained
Comprise 4.6% weight Ti.
Prepare ingredient of solid catalyst 6 (comparative, ID=diisobutyl phthalate)
According to the description of catalytic component 1, following difference is utilized to prepare ingredient of solid catalyst.Different with phthalic acid two
Butyl ester (DIBP) as internal donor, Mg/ID=6 mole.By 4 titanation step respectively 100 DEG C, 110 DEG C, 120 DEG C and 120 DEG C
It is prepared.The solid obtained comprises 2.6% weight Ti and 9.7% weight DIBP.
Prepare ingredient of solid catalyst 7 (comparative, ID=1,3-diether)
According to the description of catalytic component 1, following difference is utilized to prepare ingredient of solid catalyst.With the double (methoxyl group of 9,9-
Methyl)-9H-fluorenes as internal donor, Mg/ID=5 mole.3 titanation step are carried out 100 DEG C, 110 DEG C and 110 DEG C respectively.?
To solid comprise 4.4% weight Ti and 13.2% weight internal donor.
Prepare ingredient of solid catalyst 8 (comparative, ID=succinate)
According to the description of catalytic component 1, following difference is utilized to prepare ingredient of solid catalyst.With 2,3-diisopropyl amber
Amber diethyl phthalate as internal donor, Mg/ID=7 mole.Magnesium precursor used is adduct C.Respectively at 110 DEG C, 120 DEG C and 120
DEG C carry out three titanation step.The solid obtained comprises 2.7% weight Ti and 10.5% weight internal donor.
The general step of bulk propylene polymerization
Will be equipped with 4 liters of agitator, Pressure gauge, thermometer, catalyst feed systems, monomer feed line and constant temperature jacket
Steel autoclave nitrogen stream purges 1 hour at 70 DEG C.Then, flow down at propylene at 30 DEG C, be sequentially added into 75ml anhydrous hexane, 50mg
AlEt3, a certain amount of Cyclohexyl Methyl Dimethoxysilane (C donor) (such as, Al/ED mol ratio 20) and about 5mg solid catalysis
Agent component.Close autoclave, be subsequently added 2.0 Nl hydrogen.Then, 1.2kg liquid propene is under agitation sent into.Make temperature at 5 points
It is increased to temperature required in clock, and carries out being polymerized 2 hours in this temperature.Terminate in polymerization, remove unreacted propylene, reclaim poly-
Compound, and be dried 3 hours at 70 DEG C under vacuo.Then, polymer is weighed, and separate with o-Dimethylbenzene, to measure diformazan
The amount of benzene insoluble (X.I.) part.
The general step that propylene is polymerized in the gas phase
With the bench-scale fluid bed being equipped with circulating air compressor, recycle heat exchanger and automatic temperature controller
Reactor makes propylene be polymerized in the gas phase.Prepare fluidized-bed reactor at temperature required, pressure and composition, so make pre-polymerization
Catalyst just reaches desired value after entering it.Polymerization desired value be 20barg pressure, by 93.8% mol propylene, 5% mole third
Alkane and 1.2% moles of hydrogen composition.
In glass flask, 100mL hexane adds the desired amount of triethyl aluminum, dicyclopentyl dimethoxyl silane (D
Donor) and ingredient of solid catalyst.Catalyst pre-contact is made 10 minutes in room temperature.Then it is high that the content making flask enters 1.5L
Pressure still.Close autoclave, add 100 grams of petrogas and 40 grams of propylene.Make catalyst 30 DEG C of pre-polymerizations 15 minutes.Subsequently, make
The content of autoclave enters fluidized-bed reactor prepared as described above.Polymerization is made to carry out 2 hours, simultaneously by being continuously introduced into
The propylene steam that be enough to supplement reaction monomers keeps reactor pressure constant.After 2 hours, discharge the polymer bed generated, de-
Hydrogen, and characterize.
Embodiment 1-4 and comparing embodiment C1 to C6
Use above-mentioned conventional method, the polymerisation in bulk of propylene uses above-mentioned ingredient of solid catalyst.Two differences
Polymerization temperature (70 DEG C and 85 DEG C) test catalyst.Polymerisation in bulk result for different ingredients of solid catalyst and temperature is described
In table 1.
Embodiment 5-10 and comparing embodiment C7 to C20
Use above-mentioned conventional method, the gas-phase polymerization of propylene uses above-mentioned ingredient of solid catalyst.It is polymerized in difference
Temperature test catalyst.The result being polymerized in a fluidized bed reactor for different ingredients of solid catalyst and temperature is depicted in table
In 2.
The embodiment of the polymerisation in bulk of table 1. propylene
The embodiment of the gas-phase polymerization of table 2. propylene
。
Claims (7)
1. a method for the propylene (co) polymerization carried out in the temperature higher than 80 to 95 DEG C in the presence of a catalyst, described catalysis
Agent includes reacting, by organo-aluminum compound and ingredient of solid catalyst and optional External Electron Donor Compound, the product obtained,
Described ingredient of solid catalyst comprises Mg, Ti and selected from the electronic donor compound capable with following formula (A)
(A)
Wherein R1And R4Group is the most identical or different, for hydrogen or optionally comprise selected from halogen, the heteroatomic C of P, S, N and Si1-
C15Alkyl, its condition is R1And R4It is asynchronously hydrogen, R2And R3Both groups are hydrogen, and R group is the most identical or different, and being selected from can
Optionally connect looped C1-C15Alkyl, and n is 1, substituent R at 4 of benzoate ring, and
Described method is carried out in one or more Gas-phase reactor.
2. the process of claim 1 wherein in the donor of formula (A), R1And R4It is independently selected from C1-C15Alkyl, C6-C14Aryl,
C3-C15Cycloalkyl and C7-C15Aryl alkyl or alkylaryl.
3. the method for claim 1 or 2, wherein R1And R4Selected from C1-C10Alkyl.
4. the method for claim 1 or 2, wherein R group is selected from C1-C15Alkyl, C6-C14Aryl, C3-C15Cycloalkyl and C7-C15
Aryl alkyl or alkylaryl.
5. the method for claim 1 or 2, wherein R group is selected from C1-C5Alkyl.
6. the method for claim 1 or 2, wherein organo-aluminum compound is alkyl aluminum compound.
7. the method for claim 1 or 2, wherein external electronic donor is selected from formula (R7)a(R8)bSi(OR9)cSilicon compound, wherein a
Being the integer of 0 to 2 with b, c is the integer of 1 to 4, and (a+b+c) sum is 4, R7、R8And R9Heteroatomic there is 1-for optionally comprising
The alkyl of 18 carbon atoms, cycloalkyl or aryl.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP10187985 | 2010-10-19 | ||
| EP10187985.6 | 2010-10-19 | ||
| PCT/EP2011/068077 WO2012052386A1 (en) | 2010-10-19 | 2011-10-17 | Process for the polymerization of olefins |
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| Publication Number | Publication Date |
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| CN103154050A CN103154050A (en) | 2013-06-12 |
| CN103154050B true CN103154050B (en) | 2016-11-16 |
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| CN201180050746.8A Expired - Fee Related CN103154050B (en) | 2010-10-19 | 2011-10-17 | Olefine polymerizing process |
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| Country | Link |
|---|---|
| EP (1) | EP2630169A1 (en) |
| CN (1) | CN103154050B (en) |
| BR (1) | BR112013008507A2 (en) |
| WO (1) | WO2012052386A1 (en) |
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| CN104761664A (en) * | 2015-03-13 | 2015-07-08 | 北京肯佰恩科技发展有限公司 | Catalyst composition used in olefin polymerization and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1436766A (en) * | 2002-02-07 | 2003-08-20 | 中国石油化工股份有限公司 | Polyester compound for preparing olefine polymerizing catalyst |
| CN1453298A (en) * | 2003-04-21 | 2003-11-05 | 中国石油化工股份有限公司 | Catalyst for olefine polymerizing reaction and its components |
Family Cites Families (14)
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|---|---|---|---|---|
| SE363977B (en) | 1968-11-21 | 1974-02-11 | Montedison Spa | |
| YU35844B (en) | 1968-11-25 | 1981-08-31 | Montedison Spa | Process for obtaining catalysts for the polymerization of olefines |
| GB1603724A (en) | 1977-05-25 | 1981-11-25 | Montedison Spa | Components and catalysts for the polymerisation of alpha-olefins |
| IT1096661B (en) | 1978-06-13 | 1985-08-26 | Montedison Spa | PROCEDURE FOR THE PREPARATION OF SOLID SPHEROIDAL PRODUCTS AT AMBIENT TEMPERATURE |
| IT1098272B (en) | 1978-08-22 | 1985-09-07 | Montedison Spa | COMPONENTS, CATALYSTS AND CATALYSTS FOR THE POLYMERIZATION OF ALPHA-OLEFINS |
| IT1230134B (en) | 1989-04-28 | 1991-10-14 | Himont Inc | COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINE. |
| IT1262935B (en) | 1992-01-31 | 1996-07-22 | Montecatini Tecnologie Srl | COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINE |
| IT1262934B (en) | 1992-01-31 | 1996-07-22 | Montecatini Tecnologie Srl | COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINE |
| IT1256648B (en) | 1992-12-11 | 1995-12-12 | Montecatini Tecnologie Srl | COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINS |
| AUPO591797A0 (en) | 1997-03-27 | 1997-04-24 | Commonwealth Scientific And Industrial Research Organisation | High avidity polyvalent and polyspecific reagents |
| HUP0001557A3 (en) | 1997-03-29 | 2010-01-28 | Montell Technology Company Bv | Magnesium dichloride-alcohol adducts, process for their preparation and catalyst components obtained therefrom |
| CN1169845C (en) | 2002-02-07 | 2004-10-06 | 中国石油化工股份有限公司 | Solid catalyst component for olefine polymerization, catalyst with the component and its application |
| CN1229400C (en) * | 2003-09-18 | 2005-11-30 | 中国石油化工股份有限公司 | Catalyst compoment used for olefinic polymerization and its catalyst |
| JP5740159B2 (en) | 2007-12-21 | 2015-06-24 | ダブリュー・アール・グレイス・アンド・カンパニー−コネチカット | Self-limiting catalyst composition having a bidentate internal donor |
-
2011
- 2011-10-17 BR BR112013008507A patent/BR112013008507A2/en not_active Application Discontinuation
- 2011-10-17 CN CN201180050746.8A patent/CN103154050B/en not_active Expired - Fee Related
- 2011-10-17 WO PCT/EP2011/068077 patent/WO2012052386A1/en active Application Filing
- 2011-10-17 EP EP11770437.9A patent/EP2630169A1/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1436766A (en) * | 2002-02-07 | 2003-08-20 | 中国石油化工股份有限公司 | Polyester compound for preparing olefine polymerizing catalyst |
| CN1453298A (en) * | 2003-04-21 | 2003-11-05 | 中国石油化工股份有限公司 | Catalyst for olefine polymerizing reaction and its components |
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| Publication number | Publication date |
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| BR112013008507A2 (en) | 2017-10-31 |
| WO2012052386A1 (en) | 2012-04-26 |
| EP2630169A1 (en) | 2013-08-28 |
| CN103154050A (en) | 2013-06-12 |
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