CN104558336A - Propylene copolymer and preparation method thereof - Google Patents
Propylene copolymer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a propylene copolymer with low energy consumption and high ethylene content. The method disclosed by the invention adopts a gas phase multi-temperature range technology, a second external electron donor is selectively added under the presence of a highly active ziegler-natta catalyst, so that propylene, or propylene and ethylene can perform propylene homopolymerization and copolymerization in at least three continuous polymerization areas of one or more polymerization reactors. The method disclosed by the invention adopts the gas phase multi-temperature range technology, at a low temperature area, most of polymerization activity of the catalyst is ensured, and at a high-temperature area, the heat exchanger efficiency of a heat exchanger is improved; in addition, the second external electron donor is selectively added, and the second external electron donor is matched with a solid catalyst component, containing titanium, of the ziegler-natta catalyst, so that the reactivity ratio of ethylene in the polyreaction can be effectively increased, the high ethylene content of products is ensured, and besides, the concentration of the ethylene in gas phase composition is reduced; therefore, the energy consumption during production is reduced, and the production capacity of the conventional device is reached.
Description
Technical field
The invention belongs to polypropylene production technical field, particularly a kind of less energy-consumption height ethylene content propylene multipolymer and preparation method thereof.
Background technology
There is the impact polypropylene product of high ethylene content, have the rigidity of alfon and the shock resistance of ethylene-propylene rubber(EPR) component concurrently, there is good rigidity-toughness balanced, be widely used in the fields such as automobile, household electrical appliance and injection moulded containers.
The polypropylene of high ethylene content adopts multistep polymerization method to prepare usually, propylene homo is carried out or random copolymerization obtains propene polymer in the first reactor, then be transported to the copolymerization that next reactor carries out propylene and ethene, in the hole of propylene polymerization composition granule, generate the polymkeric substance based on ethylene-propylene random copolymer.
At present, the impact polypropylene trade mark of the overwhelming majority all uses ethene as comonomer, and propylene-ethylene copolyreaction is carried out in Gas-phase reactor, and Gas-phase reactor removes system response heat by the cooling/condensation of circulation gas.When producing high impact resistance polypropylene product, for improving the ethylene content in product, the corresponding raising ethene of meeting is concentration in gas phase composition, but ethene is a kind of non-condensable gas, the membership that adds of a large amount of vinyl monomer makes the dew point of circulation gas significantly reduce, and is difficult to cooling/condensation, causes that efficiency of heat exchanger is low, load raises, and then cause device output to reduce, affect economic benefit.
Address this problem and usually adopt two kinds of methods: first method improves the thermal load of circulation gas interchanger, such as, change the interchanger that has more high heat load, or an interchanger of connecting after existing interchanger.But increase expense is invested by this scheme, and does not reduce the energy consumption level of device.Another kind method is improved the exchange capability of heat of circulation gas interchanger, method disclosed in Chinese patent CN1421468A, CN1288175C, CN1887917A, CN1887918A and CN100457790A, by strengthening the temperature difference between the cold and hot medium of circulation gas interchanger, and then effectively improve the heat exchange efficiency of interchanger.But the drawback of this method is, the active decay rapidly at higher than the temperature of 80 DEG C of conventional Zigler-Natta catalyzer, causes catalyst consumption cost greatly to improve.Therefore, need to find a kind of method, the exchange capability of heat of copolymerization stage circulation gas interchanger can be improved, reduce energy consumption, do not increase the improvement cost of device and the raw materials cost of production simultaneously.
Summary of the invention
The object of the invention is in order to overcome in prior art prepare high ethylene content propylene multipolymer time, the defect that copolymerization stage circulation gas efficiency of heat exchanger is low, device yields poorly down, the consuming cost of raw materials for production is high, a kind of exchange capability of heat that can improve copolymerization stage circulation gas interchanger is provided, reduce energy consumption, do not increase again the improvement cost of device and the raw materials cost of production and the preparation method of the high propylene copolymer of ethylene content simultaneously.
Another object of the present invention is to provide the high ethylene content propylene multipolymer that above-mentioned preparation method prepares.
The invention provides a kind of preparation method of propylene copolymer, said method comprising the steps of:
(1) under the first alkene gas-phase polymerization reaction conditioned disjunction the liquid-phase polymerization of olefins reaction conditions, under the existence of ziegler natta catalyst, the first olefin feedstock is carried out polyreaction, obtain the first polymerization reaction mixture, wherein, described first olefin feedstock is propylene or propylene and ethene;
(2) under the second alkene gas-phase polymerization reaction condition, under the existence of described first polymerization reaction mixture, selectivity adds the second external electron donor, second olefin feedstock is carried out polyreaction, obtain the second polymerization reaction mixture, wherein, described second olefin feedstock is propylene and ethene;
(3) under alkatrienes gas phase polymerization condition, under the existence of described second polymerization reaction mixture, alkatrienes raw material is carried out polyreaction, obtains propylene copolymer, wherein, described alkatrienes raw material is propylene and ethene;
Wherein, the temperature in described second alkene gas-phase polymerization reaction condition is lower than the temperature in described alkatrienes gas phase polymerization condition, and the temperature in described alkatrienes gas phase polymerization condition is 90-150 DEG C.
Present invention also offers the propylene copolymer prepared according to aforesaid method, in described propylene copolymer, ethylene content is 8-30wt%.
The method of the invention adopts gas phase many warm areas technology, ensures most of polymerization activity of catalyzer in cold zone, improves the heat exchange efficiency of interchanger in high-temperature zone.In addition, in step (2) and step (3), selectivity adds the second external electron donor, described second external electron donor coordinates with the ingredient of solid catalyst of the titaniferous in ziegler natta catalyst, effectively can improve the ethene reactivity ratio in the polyreaction of step (2) and step (3), while ensureing product height ethylene content, reduce the ethylene concentration in gas phase composition, thus reduce production energy consumption, meet the throughput of existing apparatus.
Regulate and control the method for comonomer reactivity ratio according to gas phase many warm areas technology of the present invention and external electron donor, adopt the process of the high ethylene content propylene multipolymer of three steps polymerization preparations, effectively can improve ethene reactivity ratio, reduce exchanger heat load.In the preferred embodiment of the present invention, take alkoxyl magnesium as the solids containing titanium catalyst component of carrier and tetraethoxysilane be external electron donor owing to adopting, after (1) step propylene homo or propylene-ethylene random copolymerization, the propylene-ethylene copolyreaction of (2) step and (3) step is under the effect of the first external electron donor (or second external electron donor), ethene reactivity ratio significantly improves, the ethylene content in gas phase composition can be reduced, thus reduce production energy consumption.In addition, the typical polymerization temperature condition of (2) step can ensure most of polymerization activity of catalyzer, and the high temperature polymerization condition of (3) step can improve the heat exchange efficiency of interchanger further, reduce production energy consumption, the throughput of expansion instrument.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of preparation method of less energy-consumption height ethylene content propylene multipolymer, the method adopts gas phase many warm areas technology, under highly active ziegler natta catalyst (Ziegler-Natta catalyst) exists, with propylene or propylene and ethene for olefin feedstock carries out polyreaction, described polyreaction is carried out at least three continuous print zones of convergency of one or more polymerization reactor.Particularly, said method comprising the steps of:
(1) under the first alkene gas-phase polymerization reaction conditioned disjunction the liquid-phase polymerization of olefins reaction conditions, under the existence of ziegler natta catalyst, the first olefin feedstock is carried out polyreaction, obtain the first polymerization reaction mixture, wherein, described first olefin feedstock is propylene or propylene and ethene;
(2) under the second alkene gas-phase polymerization reaction condition, under the existence of described first polymerization reaction mixture, selectivity adds the second external electron donor, second olefin feedstock is carried out polyreaction, obtain the second polymerization reaction mixture, wherein, described second olefin feedstock is propylene and ethene;
(3) under alkatrienes gas phase polymerization condition, under the existence of described second polymerization reaction mixture, alkatrienes raw material is carried out polyreaction, obtains propylene copolymer, wherein, described alkatrienes raw material is propylene and ethene;
Wherein, the temperature in described second alkene gas-phase polymerization reaction condition is lower than the temperature in described alkatrienes gas phase polymerization condition, and the temperature in described alkatrienes gas phase polymerization condition is 90-150 DEG C.
In the present invention, preferably, the polyreaction in step (1)-(3) is carried out at least three continuous print zones of convergency of one or more polymerization reactor.
According to the present invention, polyreaction in step (1)-(3) is carried out in the polymerization reactor of at least two series connection, wherein, first polymerization reactor is first zone of convergency, second polymerization reactor is divided into the zone of convergency of at least two series connection, is at least respectively second zone of convergency and trimerization region; The polyreaction of step (1) is carried out in first zone of convergency, and does not have particular requirement to the form of polymerization reactor; The polyreaction of step (2) and (3) is carried out respectively in second zone of convergency and trimerization region.Described second polymerization reactor is Gas-phase reactor, preferably carries out in horizontal retort Gas-phase reactor, and the different zones of convergency of the second polymerization reactor have different temperature of reaction, identical or different gas phase composition.
In step (1), described in described first alkene gas-phase polymerization reaction conditioned disjunction, the liquid-phase polymerization of olefins reaction conditions comprises: temperature is 50-89 DEG C, is preferably 60-80 DEG C; Pressure is 1-6MPa, is preferably 2-5MPa; Time is 20-120 minute, is preferably 30-90 minute.
In step (2), described second alkene gas-phase polymerization reaction condition comprises: temperature is 50-89 DEG C, is preferably 60-80 DEG C; Pressure is 1-5MPa, is preferably 2-4MPa; Time is 20-60 minute, is preferably 30-50 minute.
In step (3), described alkatrienes gas phase polymerization condition comprises: temperature is 90-150 DEG C, and temperature is higher, and that gets over energy lifting gear condensing equipment removes heat energy power, reduces equipment operation load, reduces energy consumption; But higher temperature can affect the polymerization activity of polyreaction, along with the rising of temperature, the ethylene content of the finished product and RCC2 can decline to some extent, therefore, in order to take into account condensing equipment energy consumption and product ethylene content, are preferably 90-130 DEG C; Pressure is 1-5MPa, is preferably 2-4MPa; Time is 20-60 minute, is preferably 30-50 minute.
According to the present invention, in step (1)-(3), described pressure is gauge pressure.
In step (1), the additional proportion of propylene and ethene in the additional proportion of described ziegler natta catalyst and the first olefin feedstock, the first olefin feedstock, the mol ratio of hydrogen/propylene in reaction gas phase, as being not particularly limited, be this area routine to select, all have no special requirements.Wherein, in liquid-phase system, in the first olefin feedstock, the mol ratio of ethene and propylene is 0-0.08; In gas phase system, the mol ratio of ethene and propylene is 0-0.05, and in reaction gas phase, the mol ratio of hydrogen/propylene is 0-0.03.
In step (2), the additional proportion of propylene and ethene in the add-on of described second external electron donor and the add-on of the second olefin feedstock, the second olefin feedstock, the mol ratio of hydrogen/propylene in reaction gas phase, as being not particularly limited, be this area routine to select, all have no special requirements.Wherein, the add-on of described second external electron donor meets: (mole number of the ingredient of solid catalyst of titaniferous): (mole number of alkylaluminium cpd): the ratio of the mole number of the first external electron donor and second external electron donor (and) is 1:5-500:0-500, is preferably 1:25-100:25-100.In second olefin feedstock, the mol ratio of ethylene/propene is 0.2-0.5, and in reaction gas phase, the mol ratio of hydrogen/propylene is 0-0.03.
In step (3), the additional proportion of propylene and ethene in the add-on of described alkatrienes raw material and alkatrienes raw material, the mol ratio of hydrogen/propylene in reaction gas phase, as being not particularly limited, being this area routine and selecting, all having no special requirements.Wherein, alkatrienes raw material is the mol ratio of ethylene/propene is 0.2-0.5, and in reaction gas phase, the mol ratio of hydrogen/propylene is 0-0.03.
In the method for the invention, described Ziegler-Natta catalyst can select published Ziegler-Natta catalyst in prior art.Preferably, described Ziegler-Natta catalyst contains:
(1) ingredient of solid catalyst of titaniferous, the ingredient of solid catalyst of described titaniferous is the catalytic product of alkoxyl magnesium compound, titanium compound and internal electron donor compound;
(2) alkylaluminium cpd; And
(3) the first optional external electron donor;
Wherein, the mol ratio of the ingredient of solid catalyst of described titaniferous, described alkylaluminium cpd and described first external electron donor is 1:5-500:0-500, is preferably 1:25-100:25-100.
In the ingredient of solid catalyst of Ziegler-Natta catalyst component (1) titaniferous of the present invention,
Described titanium compound can be selected from logical formula I Ti (OR)
4-nx
ncompound at least one, the R in formula is selected from aliphatic radical that carbonatoms is 1-14 or carbonatoms is the aryl of 7-14, and X is halogen atom, and n is selected from the integer of 0 to 4; When n is for being less than or equal to 2, multiple R of existence can be identical or different.Described halogen atom can be chlorine, bromine or iodine.Concrete, described titanium compound is selected from least one in four titan-alkoxides, titanium tetrahalide, three halogen titan-alkoxides, dihalo-dialkoxy titanium and single halogen tri-alkoxy titanium.More specifically, described four titan-alkoxides are selected from least one in tetramethoxy titanium, purity titanium tetraethoxide, four positive propoxy titaniums, tetraisopropoxy titanium, four titanium n-butoxide, four isobutoxy titaniums, four cyclohexyloxy titaniums, four phenoxide titaniums; Described titanium tetrahalide is selected from least one in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide; Three described halogen titan-alkoxides are selected from least one in trichloromethoxy titanium, tri-chloroethoxy titanium, trichlorine titanium propanolate, trichlorine titanium n-butoxide, tribromo ethanolato-titanium; Described dihalo-dialkoxy titanium is selected from least one in dichloro dimethoxy titanium, dichlorodiethyl oxygen base titanium, dichloro two positive propoxy titanium, dichloro diisopropoxy titanium, dibromo diethoxy titanium; Described single halogen tri-alkoxy titanium is selected from least one in a chlorine trimethoxy titanium, a chlorine triethoxy titanium, a chlorine three positive propoxy titanium, chlorine three titanium isopropoxide; Preferably, described titanium compound is titanium tetrahalide compound, is particularly preferably titanium tetrachloride.
Described alkoxyl magnesium compound can be selected from logical formula II Mg (OR
1)
2-m(OR
2)
mcompound at least one, wherein, R
1and R
2identical or different, being selected from carbonatoms is respectively one in the straight or branched alkyl of 1-8, is preferably methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, n-hexyl, (2-ethyl) hexyl respectively, further preferably, and R
1for ethyl, R
2for (2-ethyl) hexyl; 0≤m≤2, preferably, 0.001≤m≤0.5, further preferably, 0.001≤m≤0.25, most preferably, 0.001≤m≤0.1.It is emphasized that alkoxyl magnesium represented by general formula, illustrate only the composition content of each alkoxyl group, i.e. mol ratio, and the concrete structure of incomplete representation alkoxy magnesium.
Described alkoxyl magnesium compound outward appearance is that class is spherical, and median size (D50) is 10-150um, is preferably 15-100um, is more preferably 18-80um; Its size distribution index SPAN<1.1, preferable particle size dispersion index SPAN<1.05, wherein, the calculation formula following (V) of SPAN:
SPAN=（D90-D10）/D50 (V)
In formula (V), D90 represents that corresponding to accumulating weight point rate be the particle diameter of 90%, and D10 represents that corresponding to accumulating weight point rate be the particle diameter of 10%, and D50 represents that corresponding accumulating weight point rate is the particle diameter of 50%.
According to alkoxyl magnesium compound of the present invention, preferably, adopt by alcohol corresponding to MAGNESIUM METAL, alkoxyl group and Mixed bittern agent under an inert atmosphere back flow reaction prepare.The mol ratio of the halogen atom wherein in MAGNESIUM METAL and Mixed bittern agent is 1:0.0002-1:0.2, preferred 1:0.001-1:0.08; The weight ratio of alcohol and magnesium is 4:1-50:1, preferred 6:1-25:1.Described reaction is carried out between 0 DEG C of reflux temperature to reaction system.Preferably, described temperature of reaction is the reflux temperature of reaction system.The time of described reaction is 2-30 hour.
Described Mixed bittern agent is the combination of halogen and halogen compounds, and described halogen and halogen compounds are that indefiniteness is selected: iodine, bromine, chlorine, magnesium chloride, magnesium bromide, magnesium iodide, Repone K, Potassium Bromide, potassiumiodide, calcium chloride, Calcium Bromide, calcium iodide, mercury chloride, mercuric bromide, red mercury iodide, oxyethyl group magnesium iodide, methoxyl group magnesium iodide, sec.-propyl magnesium iodide, hydrogenchloride, chloroacetyl chloride etc.The combination of preferred iodine and magnesium chloride.The weight ratio of iodine and magnesium chloride is preferably 1:0.02-1:20, is more preferably 1:0.1-1:10.
Described inert atmosphere, comprises nitrogen atmosphere, argon atmospher etc., preferred nitrogen atmosphere.
Described internal electron donor compound comprise in the alkyl ester of aliphatic series and the alkyl ester of aromatic monocarboxylate, aliphatic series and aromatic polycarboxylic acid, aliphatic ether, cyclic aliphatic ether and aliphatic ketone one or more; At least one preferably in the alkyl ester of the alkyl ester of C1-C4 aliphatic saturated monocarboxylic acid, C7-C8 aromatic carboxylic acid, C2-C6 aliphatic ether, C3-C4 cyclic ethers, C3-C6 saturated fatty ketone, 1,3-diether compounds.
Preferably, above-mentioned interior electron donor compound can be phthalate compound shown in formula III,
In formula (III), R
4and R
5identical or different, be separately one that carbonatoms is in the alkaryl of the straight or branched alkyl of 1-12, the cycloalkyl of carbonatoms 3-10 and carbonatoms 6-20, replacement or non-substituted arene base.R
6, R
7, R
8and R
9be all hydrogen; Or wherein three is hydrogen, the straight or branched alkyl that another one is halogen, carbonatoms is 1-4 and carbonatoms are the one in the straight or branched alkoxyl group of 1-4.Described internal electron donor compound is preferably diethyl phthalate, n-butyl phthalate, diisobutyl phthalate, dihexyl phthalate, diheptyl phthalate, O-phthalic di-isooctyl etc.
Described internal electron donor compound is also selected such as formula 1,3-diether compounds shown in (IV),
R in formula (IV)
10and R
11identical or different, be selected from the one in alkaryl that carbonatoms is the straight or branched alkyl of 1-12, the cycloalkyl of carbonatoms 3-10 and carbonatoms 6-20, replacement or non-substituted arene base independently of one another; R
13and R
14identical or different, be selected from the straight or branched alkyl that carbonatoms is 1-10 independently of one another; R
12and R
15identical or different, be selected from the one in the straight or branched alkyl of hydrogen and carbonatoms 1-10 independently of one another, optionally, R
12, R
13, R
14and R
15one or more in group at random link up into ring.Concrete compound is: 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, 9,9-bis-(methoxymethyl) fluorenes, 2-isobutyl--2-sec.-propyl-1,3-Propanal dimethyl acetal, 2,2-dicyclopentyl dimethoxyl propane, 2,2-phenylbenzene-1,3-Propanal dimethyl acetal, 2-isobutyl--2-sec.-propyl-1,3-Propanal dimethyl acetal, 2,2-bicyclopentyl-1,3-Propanal dimethyl acetal, 2,2-diisobutyl-1,3-Propanal dimethyl acetals etc.
According to the ingredient of solid catalyst of titaniferous of the present invention, can be obtained by the method for following steps: by alkoxyl magnesium compound, react with internal electron donor compound and titanium compound under inert diluent exists; The above-mentioned solids inert solvent washing be obtained by reacting is obtained the ingredient of solid catalyst of described titaniferous.
In the preparation method of the ingredient of solid catalyst of described titaniferous, the consumption of described titanium compound is (0.5 ~ 100) relative to the mol ratio of the magnesium in alkoxyl magnesium compound: 1, is preferably (1 ~ 50): 1.The consumption of described internal electron donor compound is (0.005 ~ 10) relative to the mol ratio of magnesium in alkoxyl magnesium compound: 1, is preferably (0.01 ~ 1): 1.The consumption of described inert diluent is relative to the mol ratio (0.5 ~ 100) of the magnesium in alkoxyl magnesium compound: 1, is preferably (1 ~ 50): 1.Preferred inert diluent is toluene.Temperature of reaction is-40 ~ 200 DEG C, is preferably-20 ~ 150 DEG C; Reaction times is 1 minute ~ 20 hours, is preferably 5 minutes ~ 8 hours.
Described inert solvent can be selected from least one in the alkane of C6 ~ C10 or aromatic hydrocarbons, at least one in preferred hexane, heptane, octane, decane, benzene,toluene,xylene or derivatives thereof etc.
According to the preparation of the ingredient of solid catalyst of titaniferous of the present invention, there is no particular limitation for the addition sequence of alkoxyl magnesium compound, internal electron donor compound, inert solvent and titanium compound, such as can under the existence of inert solvent, make each composition mix, each composition can also be diluted with inert solvent in advance and make them mix.For the number of times mixed, also there is no particular limitation, can mix once, also can mix repeatedly.
According to the preparation of the ingredient of solid catalyst of titaniferous of the present invention, preferred washing inert solvent is hexane.For the method for washing, there is no particular limitation, the modes such as preferred decant, filtration.The usage quantity of inert solvent, washing time, washing times are not particularly limited, and usually use 1-1000 mole for the magnesium in the alkoxyl magnesium compound of 1 mole, are preferably the solvent of 10-500 mole, usually washing 1-24 hour, preferred 6-10 hour.In addition from the homogeneity of washing and the aspect of detersive efficiency, preferably stir in washing operation.
Component (2) in catalyzer of the present invention is general formula is (VI) AlR
nx
3-nalkylaluminium cpd, R is hydrogen or carbonatoms in formula (VI) is the alkyl of 1-20, and X is halogen, and n is the number of 1<n≤3; Specifically can be selected from least one in triethyl aluminum, tri-propyl aluminum, three n-butylaluminum, triisobutyl aluminium, tri-n-octylaluminium, triisobutyl aluminium, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride aluminium, ethyl aluminum dichloride, preferred triethyl aluminum or triisobutyl aluminium.
First external electron donor of the component (3) in catalyzer of the present invention can be various external electron donors known in the industry, is not particularly limited.Silicoorganic compound shown in preferred formula (VII),
R
1''
m''R
2''
n''Si(OR
3'')
4-m''-n''（VII）
In formula (VII), R
1' ' and R
2' ' identical or different, be respectively halogen, aryl that cycloalkyl that alkyl that hydrogen atom, carbonatoms are 1-20, carbonatoms are 3-20, carbonatoms are 6-20 and carbonatoms are one in the haloalkyl of 1-20; R
3' ' for carbonatoms is the alkyl of 1-20, carbonatoms is the cycloalkyl of 3-20, carbonatoms is 6-20 aryl and carbonatoms be the one in the haloalkyl of 1-20; M'' and n'' is respectively the integer of 0-3, and m''+n''<4.Described silicoorganic compound can be trimethylmethoxysilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, isopropyl butyldimethoxysilane, di-t-butyl dimethoxysilane, tertbutyl methyl dimethoxysilane, t-butylethyl dimethoxysilane, tertiary butyl propyldimethoxy-silane, ter /-butylisopropyl dimethoxysilane, Cyclohexyl Methyl Dimethoxysilane, Dicyclohexyldimethoxysilane, cyclohexyl-t-butyldimethoxysilane, cyclopentyl-methyl dimethoxysilane, cyclopentyl ethyl dimethoxysilane, dicyclopentyl dimethoxyl silane, cyclopentyl cyclohexyl dimethoxysilane, two (2-methylcyclopentyl) dimethoxysilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, phenyl triethoxysilane, methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, propyl trimethoxy silicane, isopropyltri-methoxysilane, butyl trimethoxy silane, butyl triethoxyl silane, trimethoxysilane, amyltrimethoxysilane, isopentyl Trimethoxy silane, cyclopentyl-trimethoxy-silane, cyclohexyl trimethoxy silane, dimethoxydiphenylsilane, diphenyl diethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, n-propyl Trimethoxy silane, vinyltrimethoxy silane, tetramethoxy-silicane, tetraethoxysilane, one or more in four butoxy silanes.These silicoorganic compound can individually use, and also two or more can be combinationally used.Preferred, described first external electron donor contains at least one in dicyclopentyl dimethoxyl silane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, Cyclohexyl Methyl Dimethoxysilane, dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane, tetraethoxysilane, wherein with diisopropyl dimethoxy silane, tetraethoxysilane best results.
If the first external electron donor of the ziegler natta catalyst selected is not suitable for polyreaction (propylene homo or the propylene-ethylene random copolymerization reaction) requirement in step (1), the first external electron donor being conducive to step (1) can be used, as: as described in the first external electron donor be the external electron donor that vertical structure directional properties is good, simultaneously, in step (2) and (3), selectivity adds the second external electron donor, the add-on of described second external electron donor meets: (mole number of the ingredient of solid catalyst of titaniferous): (mole number of alkylaluminium cpd): the ratio of the mole number of the first external electron donor and second external electron donor (and) is 1:5-500:0-500, be preferably 1:25-100:25-100.The first external electron donor changed or the second external electron donor coordinate with Primary Catalysts (i.e. the ingredient of solid catalyst of titaniferous), to improve the ethene reactivity ratio in gas phase copolymerization.Second external electron donor, except the first above-mentioned external electron donor kind, can also be other material ethene reactivity ratio being had to obvious effect, as at least one in chloroform, zinc ethyl.
Ziegler-Natta catalyst of the present invention adopts special alkoxyl magnesium component, makes this catalyzer have the polymerization of unique applicable high temperature polymerization condition, as: the advantages such as reactive behavior is high and release is steady, segmentation minimizing.
Present invention also offers the high ethylene content propylene multipolymer prepared according to aforesaid method, in described propylene copolymer, ethylene content is 8-30wt%.
Below will be described the present invention by embodiment.
In embodiment, polymkeric substance relevant data obtains by following testing method:
1. ethene and RCC2 content: Thermo Nicolet200 type infrared spectrum analyser, 720-730cm
-1the corresponding total ethylene content of peak area at place; 730-740cm
-1the corresponding free state ethylene content of peak area at place, 720cm
-1, 727cm
-1, 729cm
-1the peak area corresponding copolymerization state ethylene content at place, the two ratio is RCC2.
2. modulus in flexure: measure according to ASTM D790-97.
3. tensile strength: measure according to ASTM D638-00.
4. Izod shock strength: measure according to ASTM D256-00.
5. 721 spectrophotometers of the titanium content in catalyzer are tested.
6. the grain size of dialkoxy magnesium and catalyzer, size-grade distribution Malvern Mastersizer TM2000 laser diffractometry are measured, and normal hexane is dispersion agent (wherein, SPAN=(D90-D10)/D50).
The mensuration of the m value 7. in carrier: get 0.1 gram of carrier, add 10mL1.2mol/L aqueous hydrochloric acid, shakes and makes it decompose in 24 hours, uses gas-chromatography quantitative, be then calculated as follows m value to ethanol wherein and 2-Ethylhexyl Alcohol:
In formula, w1 is 2-Ethylhexyl Alcohol quality, and w2 is ethanol quality.
8. in olefin polymerization catalyst components, internal electron donor content uses Waters600E liquid chromatography to carry out measuring or gas Chromatographic Determination.
9. quench liquid spray flux is the data that quench liquid nozzle flow meter reads from poly-unit.
10. dew point is the temperature of circulation gas heat exchanger exit, can directly read in the controls.
Preparation example:
This preparation example be used for prepare the present invention use high reactivity Ziegler-Natta catalyst in solids containing titanium catalyst component.
After fully replacing the 16L voltage-resistant reactor with agitator with nitrogen, in reactor, add 10L ethanol, 300mL2-ethylhexanol, 11.2g iodine, 8g magnesium chloride and 640g magnesium powder.Stir and make system back flow reaction simultaneously, till no longer including hydrogen discharge.Stopped reaction, uses 3L washing with alcohol, filtration, drying.The dialkoxy-magnesium support obtained.Gained dialkoxy-magnesium support D50=30.2um, Span value 0.81, m value 0.015.Get above-mentioned dialkoxy-magnesium support 650g and toluene 3250mL and be mixed with suspension.Repeating in the withstand voltage reactor of 16L of replacing through high pure nitrogen, add toluene 2600mL and titanium tetrachloride 3900mL, be warming up to 80 DEG C, then the suspension prepared is added in still, constant temperature 1 hour, adds diethyl phthalate 130mL, is slowly warming up to 110 DEG C, constant temperature 2 hours, press filtration obtains solid substance.The mixed solution that gained solid substance adds toluene 5070mL and titanium tetrachloride 3380mL 110 DEG C of stir process 1 hour, so process 3 times.Press filtration, the solid of gained hexanes wash 4 times, each 6000mL, press filtration, drying, obtain the ingredient of solid catalyst of titaniferous.Titanium atom content 2.4wt% in the ingredient of solid catalyst of gained titaniferous, diethyl phthalate content 10.5wt%.
Embodiment 1:
The present embodiment is used for illustrating the preparation method of less energy-consumption height ethylene content propylene multipolymer of the present invention.
1) raw material
The ingredient of solid catalyst of the titaniferous obtained in preparation example is Primary Catalysts; Triethyl aluminum is used as promotor; Tetraethoxysilane (T-Doner) is as the first external electron donor; Propylene, ethene and hydrogen are polymerization-grade, use after removing water, oxygen, and hexane uses after dehydration.
2) testing apparatus
Adopt the polymerization technique of two horizontal retort Gas-phase reactor series connection.Horizontal retort Gas-phase reactor volume 0.2 cubic metre, stirring rake is T-shaped oblique blade, and angle of inclination is 10 degree, and stirring velocity is 100 revs/min.
3) test conditions
(1) step gas-phase propene homopolymerization: (referred to as a district) adds Primary Catalysts, triethyl aluminum, the first external electron donor and propylene in horizontal retort first Gas-phase reactor, carry out polyreaction, wherein, the inlet amount of Primary Catalysts, triethyl aluminum, the first external electron donor is respectively 0.9g/hr, 0.072mol/hr, 0.012mol/hr, Al/Si (mol/mol)=6.0; Propylene feed amount is 15kg/hr; In reaction gas phase, hydrogen/propylene molar ratio is 0.0297; The temperature of polyreaction is 66 DEG C, and pressure is 2.3MPa, and the time is 60 minutes, obtains the first polymerization reaction mixture;
The normal temperature gas-phase copolymerization of (2) step propylene and ethene: in second zone of convergency in horizontal retort second Gas-phase reactor (referred to as 2nd district), under the existence of described first polymerization reaction mixture, add ethene and propylene, carry out polyreaction, ethene and propylene feed amount are respectively 3.6kg/hr, 15kg/hr, and ethylene/propene mol ratio is 0.36; In reaction gas phase, hydrogen/propylene molar ratio is 0.0094; The temperature of polyreaction is 66 DEG C, and pressure is 2.3MPa, and the time is 40 minutes, obtains the second polymerization reaction mixture;
The high temperature gas-phase copolymerization of (3) step propylene and ethene: in the trimerization region in horizontal retort second Gas-phase reactor (referred to as 3rd district), under the existence of described second polymerization reaction mixture, add ethene and propylene, carry out polyreaction, ethene and propylene feed amount are respectively 3.6kg/hr, 15kg/hr, and ethylene/propene mol ratio is 0.36; In reaction gas phase, hydrogen/propylene molar ratio is 0.0094, and the temperature of polyreaction is 95 DEG C, and pressure is 2.3MPa, and the time is 40 minutes, obtains high ethylene content propylene multipolymer.
Concrete technology condition is in table 1.
4) test-results
Carry out the long run test of 48 hours according to above-mentioned condition, device stable operation, the polymkeric substance be obtained by reacting has been carried out analytical test, the results are shown in table 1.
Embodiment 2:
The present embodiment is used for illustrating the preparation method of less energy-consumption height ethylene content propylene multipolymer of the present invention.
1) raw material
Diisopropyl dimethoxy silane (P-Doner) as the first external electron donor, the other the same as in Example 1.
2) testing apparatus, with embodiment 1.
3) test conditions, with embodiment 1.
4) test-results
Carry out the long run test of 48 hours according to above-mentioned condition, device stable operation, the polymkeric substance be obtained by reacting has been carried out analytical test, the results are shown in table 1.
Embodiment 3:
The present embodiment is used for illustrating the preparation method of less energy-consumption height ethylene content propylene multipolymer of the present invention.
1) raw material, with embodiment 1.
2) testing apparatus, with embodiment 1.
3) test conditions
(1) step gas-phase propene homopolymerization is with embodiment 1;
The normal temperature gas-phase copolymerization of (2) step propylene and ethene is with embodiment 1;
The high temperature gas-phase copolymerization of (3) step propylene and ethene: temperature of reaction is 110 DEG C, pressure is 2.3MPa, and the time is 40 minutes; Other conditions are with embodiment 1;
4) test-results
Carry out the long run test of 48 hours according to above-mentioned condition, device stable operation, the polymkeric substance be obtained by reacting has been carried out analytical test, the results are shown in table 1.
Embodiment 4:
The present embodiment is used for illustrating the preparation method of less energy-consumption height ethylene content propylene multipolymer of the present invention.
1) raw material, with embodiment 1.
2) testing apparatus, with embodiment 1.
3) test conditions
(1) step gas-phase propene homopolymerization is with embodiment 1;
The normal temperature gas-phase copolymerization of (2) step propylene and ethene is with embodiment 1;
The high temperature gas-phase copolymerization of (3) step propylene and ethene: temperature of reaction is 125 DEG C, pressure is 2.3MPa, and the time is 40 minutes; Other conditions are with embodiment 1;
4) test-results
Carry out the long run test of 48 hours according to above-mentioned condition, device stable operation, the polymkeric substance be obtained by reacting has been carried out analytical test, the results are shown in table 1.
Embodiment 5:
The present embodiment is used for illustrating the preparation method of less energy-consumption height ethylene content propylene multipolymer of the present invention.
1) raw material, with embodiment 1.
2) testing apparatus, with embodiment 1.
3) test conditions
(1) step gas-phase propene-ethylene random copolymerization: ethene and propylene feed amount are respectively 0.2kg/hr, 15kg/hr, ethylene/propene mol ratio is 0.02; Other conditions are with embodiment 1;
The normal temperature gas-phase copolymerization of (2) step propylene and ethene: with embodiment 1;
The high temperature gas-phase copolymerization of (3) step propylene and ethene: with embodiment 1.
4) test-results
Carry out the long run test of 48 hours according to above-mentioned condition, device stable operation, the polymkeric substance be obtained by reacting has been carried out analytical test, the results are shown in table 1.
Embodiment 6:
The present embodiment is used for illustrating the preparation method of less energy-consumption height ethylene content propylene multipolymer of the present invention.
1) raw material, with embodiment 1.
2) testing apparatus, with embodiment 1.
3) test conditions
(1) step gas-phase propene homopolymerization: the inlet amount of Primary Catalysts, triethyl aluminum, the first external electron donor B-Doner is respectively 0.9g/hr, 0.072mol/hr, 0.006mol/hr, Al/Si (mol/mol)=12.0; Other conditions are with embodiment 1;
The normal temperature gas-phase copolymerization of (2) step propylene and ethene: the inlet amount of the second external electron donor T-Doner is 0.006mol/hr; Other conditions are with embodiment 1;
The high temperature gas-phase copolymerization of (3) step propylene and ethene: condition is with embodiment 1.
4) test-results
Carry out the long run test of 48 hours according to above-mentioned condition, device stable operation, the polymkeric substance be obtained by reacting has been carried out analytical test, the results are shown in table 1.
Comparative example 1:
1) raw material
Second, isobutyl dimethoxy silane (B-Doner) as the first external electron donor, the other the same as in Example 1.
2) testing apparatus, with embodiment 1.
3) test conditions, with embodiment 1.
4) test-results
Carry out the long run test of 48 hours according to above-mentioned condition, device stable operation, the polymkeric substance be obtained by reacting has been carried out analytical test, the results are shown in table 1.
Comparative example 2:
1) raw material, with embodiment 1.
2) testing apparatus, with embodiment 1.
3) test conditions
Second Gas-phase reactor no longer divides the zone of convergency, many warm areas polymerization methods of (2) step and (3) step is changed 66 DEG C of conventional homogeneous temperature distribution, the other the same as in Example 1.
4) test-results
Carry out the long run test of 48 hours according to above-mentioned condition, device stable operation, the polymkeric substance be obtained by reacting has been carried out analytical test, the results are shown in table 1.
As can be seen from Table 1, the testing data of embodiment 1, embodiment 2 and comparative example 1 mainly reflects the impact of different first external electron donor on ethene reactivity ratio and plant energy consumption.In second Gas-phase reactor, the second of copolymerization stage is rare with under third rare mol ratio same case, ethylene content in product in ethylene content and rubber phase changes with the modulation of the first external electron donor, wherein, the ethylene content of P-Doner and T-Doner, apparently higher than B-Doner, illustrates that the reactivity ratio of ethene under P-Doner and T-Doner exists is higher.If when in product, ethylene content is identical, during the gas phase required than B-Doner forms by P-Doner and T-Doner, second is rare low with third rare mol ratio, and the reduction of noncondensable gas content will reduce the energy consumption of the condensing equipment of device.
The testing data of embodiment 1 and comparative example 2 mainly reflects the energy consumption of many warm areas technology in the gas-phase copolymerization stage to device condensing equipment.When the first external electron donor added is identical, in embodiment 1, second Gas-phase reactor is divided into second zone of convergency and trimerization region, have employed many warm areas technology, few obviously than comparative example 2 of the quench liquid spray flux of copolymerization stage, illustrate that many warm areas technology effectively can reduce the operating load of device condensing equipment, thus reduce energy consumption.
The testing data of embodiment 1,3,4 mainly reflects the different polymerization temperatures of many warm areas technology to the energy consumption of device condensing equipment.Along with the lifting of two district's temperature, the quench liquid spray flux of copolymerization stage significantly reduces, illustrate higher polymerization temperature can lifting gear condensing equipment remove heat energy power, reduce equipment operation load, thus reduce energy consumption.But meanwhile, higher copolymerization temperature can affect the polymerization activity in this stage, from data presentation, along with the rising of temperature, ethylene content and RCC2 can slightly decline.Therefore, three district's polymerization temperatures according to needs of production, should choose optimized scheme between condensing equipment energy consumption and product ethylene content.
Embodiment 1 illustrates with the testing data of embodiment 5, and when the first step is polymerized to ethylene-propylene random copolymerization, the ethylene content of product is significantly higher, but its rigidity can decline to some extent, and modulus in flexure reduces.
The testing data explanation of embodiment 1 and embodiment 6, when the first external electron donor add be conducive to raising one district product degree of isotacticity, the second external electron donor add be conducive to improving the ethene reactivity ratio of copolymerization stage time, the finished product can take into account rigidity and the shock resistance of material.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (15)
1. a preparation method for propylene copolymer, is characterized in that, said method comprising the steps of:
(1) under the first alkene gas-phase polymerization reaction conditioned disjunction the liquid-phase polymerization of olefins reaction conditions, under the existence of ziegler natta catalyst, the first olefin feedstock is carried out polyreaction, obtain the first polymerization reaction mixture, wherein, described first olefin feedstock is propylene or propylene and ethene;
(2) under the second alkene gas-phase polymerization reaction condition, under the existence of described first polymerization reaction mixture, selectivity adds the second external electron donor, second olefin feedstock is carried out polyreaction, obtain the second polymerization reaction mixture, wherein, described second olefin feedstock is propylene and ethene;
(3) under alkatrienes gas phase polymerization condition, under the existence of described second polymerization reaction mixture, alkatrienes raw material is carried out polyreaction, obtains propylene copolymer, wherein, described alkatrienes raw material is propylene and ethene;
Wherein, the temperature in described second alkene gas-phase polymerization reaction condition is lower than the temperature in described alkatrienes gas phase polymerization condition, and the temperature in described alkatrienes gas phase polymerization condition is 90-150 DEG C.
2. method according to claim 1, wherein, the polyreaction in step (1)-(3) is carried out at least three continuous print zones of convergency of one or more polymerization reactor.
3. method according to claim 2, wherein, polyreaction in step (1)-(3) is carried out in the polymerization reactor of at least two series connection, wherein, first polymerization reactor is first zone of convergency, second polymerization reactor is divided into the zone of convergency of at least two series connection, is at least respectively second zone of convergency and trimerization region; The polyreaction of step (1) is carried out in first zone of convergency, and the polyreaction of step (2) and (3) is carried out respectively in second zone of convergency and trimerization region.
4. method according to claim 1, wherein, in step (1), described in described first alkene gas-phase polymerization reaction conditioned disjunction, the liquid-phase polymerization of olefins reaction conditions comprises: temperature is 50-89 DEG C, is preferably 60-80 DEG C; Pressure is 1-6MPa, is preferably 2-5MPa; Time is 20-120 minute, is preferably 30-90 minute.
5. method according to claim 1, wherein, in step (2), described second alkene gas-phase polymerization reaction condition comprises: temperature is 50-89 DEG C, is preferably 60-80 DEG C; Pressure is 1-5MPa, is preferably 2-4MPa; Time is 20-60 minute, is preferably 30-50 minute.
6. method according to claim 1, wherein, in step (3), described alkatrienes gas phase polymerization condition comprises: temperature is 90-150 DEG C, is preferably 90-130 DEG C; Pressure is 1-5MPa, is preferably 2-4MPa; Time is 20-60 minute, is preferably 30-50 minute.
7. the method according to claim 1-6 any one, wherein, described ziegler natta catalyst contains:
(1) ingredient of solid catalyst of titaniferous, the ingredient of solid catalyst of described titaniferous is the catalytic product of alkoxyl magnesium compound, titanium compound and internal electron donor compound;
(2) alkylaluminium cpd; And
(3) the first optional external electron donor;
Wherein, the mol ratio of the ingredient of solid catalyst of described titaniferous, described alkylaluminium cpd and described first external electron donor is 1:5-500:0-500, is preferably 1:25-100:25-100.
8. method according to claim 7, wherein, described alkoxyl magnesium compound is selected from formula M g (OR
1)
2-m(OR
2)
mcompound at least one, wherein, R
1and R
2identical or different, being selected from carbonatoms is respectively one in the straight or branched alkyl of 1-8, is preferably methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, n-hexyl, (2-ethyl) hexyl respectively, further preferably, and R
1for ethyl, R
2for (2-ethyl) hexyl; 0≤m≤2, preferably, 0.001≤m≤0.5, further preferably, 0.001≤m≤0.25, most preferably, 0.001≤m≤0.1.
9. method according to claim 7, wherein, described titanium compound is selected from general formula Ti (OR)
4-nx
ncompound at least one, wherein, R is selected from aliphatic radical that carbonatoms is 1-14 or carbonatoms is the aryl of 7-14, and X is halogen atom, and n is selected from the integer of 0 to 4; When n is for being less than or equal to 2, multiple R of existence are identical or different;
Preferably, described titanium compound is selected from least one in four titan-alkoxides, titanium tetrahalide, three halogen titan-alkoxides, dihalo-dialkoxy titanium and single halogen tri-alkoxy titanium.
10. method according to claim 7, wherein, described internal electron donor compound comprise in the alkyl ester of aliphatic series and the alkyl ester of aromatic monocarboxylate, aliphatic series and aromatic polycarboxylic acid, aliphatic ether, cyclic aliphatic ether and aliphatic ketone one or more; Preferably, described internal electron donor compound is selected from least one in the alkyl ester of C1-C4 aliphatic saturated monocarboxylic acid, the alkyl ester of C7-C8 aromatic carboxylic acid, C2-C6 aliphatic ether, C3-C4 cyclic ethers, C3-C6 saturated fatty ketone and 1,3-diether compounds.
11. methods according to claim 7, wherein, described alkylaluminium cpd is general formula is AlR
nx
3-nalkylaluminium cpd, wherein, R is hydrogen or carbonatoms is the alkyl of 1-20, and X is halogen, and n is the number of 1<n≤3; Preferably, described alkylaluminium cpd is selected from least one in triethyl aluminum, tri-propyl aluminum, three n-butylaluminum, triisobutyl aluminium, tri-n-octylaluminium, triisobutyl aluminium, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride aluminium, ethyl aluminum dichloride; Further preferably, described alkylaluminium cpd is triethyl aluminum or triisobutyl aluminium.
12. methods according to claim 7, is characterized in that, described first external electron donor is general formula R
1' '
m''r
2' '
n''si (OR
3' ')
4-m''-n''shown silicoorganic compound, wherein, R
1' ' and R
2' ' identical or different, be respectively halogen, aryl that cycloalkyl that alkyl that hydrogen atom, carbonatoms are 1-20, carbonatoms are 3-20, carbonatoms are 6-20 and carbonatoms are one in the haloalkyl of 1-20; R
3' ' for carbonatoms is the alkyl of 1-20, carbonatoms is the cycloalkyl of 3-20, carbonatoms is 6-20 aryl and carbonatoms be the one in the haloalkyl of 1-20; M'' and n'' is respectively the integer of 0-3, and m''+n''<4.
13. methods according to claim 12, is characterized in that, described first external electron donor is trimethylmethoxysilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, isopropyl butyldimethoxysilane, di-t-butyl dimethoxysilane, tertbutyl methyl dimethoxysilane, t-butylethyl dimethoxysilane, tertiary butyl propyldimethoxy-silane, ter /-butylisopropyl dimethoxysilane, Cyclohexyl Methyl Dimethoxysilane, Dicyclohexyldimethoxysilane, cyclohexyl-t-butyldimethoxysilane, cyclopentyl-methyl dimethoxysilane, cyclopentyl ethyl dimethoxysilane, dicyclopentyl dimethoxyl silane, cyclopentyl cyclohexyl dimethoxysilane, two (2-methylcyclopentyl) dimethoxysilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, phenyl triethoxysilane, methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, propyl trimethoxy silicane, isopropyltri-methoxysilane, butyl trimethoxy silane, butyl triethoxyl silane, trimethoxysilane, amyltrimethoxysilane, isopentyl Trimethoxy silane, cyclopentyl-trimethoxy-silane, cyclohexyl trimethoxy silane, dimethoxydiphenylsilane, diphenyl diethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, n-propyl Trimethoxy silane, vinyltrimethoxy silane, tetramethoxy-silicane, tetraethoxysilane, one or more in four butoxy silanes,
Preferably, described first external electron donor is at least one in dicyclopentyl dimethoxyl silane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, Cyclohexyl Methyl Dimethoxysilane, dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane, tetraethoxysilane; Further preferably, described first external electron donor is diisopropyl dimethoxy silane or tetraethoxysilane.
14. methods according to claim 12 or 13, wherein, the second external electron donor described in step (2) is for the first external electron donor in method described in claim 12 or 13 or be at least one in chloroform, zinc ethyl.
The propylene copolymer that described in 15. claim 1-14 any one, method prepares, is characterized in that, in described propylene copolymer, ethylene content is 8-30wt%.
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| CN110294813A (en) * | 2019-06-25 | 2019-10-01 | 陕西延长中煤榆林能源化工有限公司 | A kind of gas-phase polymerization polypropylene production technology using Mixed electron donor |
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