CN109280107A - A kind of catalyst system and its application for olefinic polymerization - Google Patents
A kind of catalyst system and its application for olefinic polymerization Download PDFInfo
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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
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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
- C08F110/02—Ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/647—Catalysts containing a specific non-metal or metal-free compound
- C08F4/649—Catalysts containing a specific non-metal or metal-free compound organic
- C08F4/6493—Catalysts containing a specific non-metal or metal-free compound organic containing halogen
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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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/647—Catalysts containing a specific non-metal or metal-free compound
- C08F4/649—Catalysts containing a specific non-metal or metal-free compound organic
- C08F4/6494—Catalysts containing a specific non-metal or metal-free compound organic containing oxygen
Abstract
The invention belongs to olefin polymerization catalysis field, a kind of catalyst system for olefinic polymerization and its application are disclosed.The catalyst system includes the reaction product of following components: 1) ingredient of solid catalyst includes the reaction product of following components: ultra-fine carrier, magnesium halide, halogenated titanium, internal electron donor b and optional internal electron donor a；2) co-catalyst；3) at least one of three black false hellebore hydrocarbons and their derivates of ring shown in formula (I), M in formula (I) external donor compound: are selected from1、M2、M3、M4、M5And M6It is identical or different, it each is selected from hydrogen, hydroxyl, amino, aldehyde radical, carboxyl, acyl group, halogen atom ,-R1Or-OR2, wherein R1And R2Respectively substituted or unsubstituted C1~C10Alkyl, substituent group are selected from hydroxyl, amino, aldehyde radical, carboxyl, acyl group, halogen atom, alkoxy or hetero atom.
Description
Technical field
The invention belongs to olefin polymerization catalysis fields, and in particular to a kind of catalyst system for olefinic polymerization and its
Using.
Background technique
In the past 60 years, with the continuous development of olefin polymerization catalysis technology, Ziegler-Natta type polyolefin catalyst
Activity, hydrogen tune susceptibility and copolymerization performance and the bulk density of its polymer powder material, melt index, molecular weight distribution, fine powder
The parameters such as content and copolymerization units distribution have obtained significant optimization.But it is to be able to better adapt to industrial need
It asks, produces the superior product of performance, then the above-mentioned parameter of such catalyst and its polymerization powder also needs to further increase.
In the prior art, its hydrogen tune susceptibility can be improved by introducing internal electron donor into catalyst, such as:
CN1958620A introduces type siloxane electron donor；CN1743347A introduces benzoic ether/carboxylic of ortho alkoxy substitution
Acid esters (or diether) compounds electron donor；CN102295717A and CN103772536A introduces benzoate compounds conduct
Electron donor, to improve the hydrogen response of catalyst.Can also by into catalyst introduce inside/outside electron donor,
To improve the copolymerization performance of catalyst, such as: CN1726230A introduces ether, ester, amine, ketone or nitrile electronic donor compound；
CN1798774A is using alcohol, glycol, ester, ketone, amine, amide, nitrile, alkoxy silane and fatty ether as electron donor compound；
CN101050248A introduces alcohol, ketone, amine, amide, nitrile, alkoxy silane, fatty ether and aliphatic carboxylic acid esters' electron donor.
It records according to prior art, in the polymerization process of Ziegler-Natta type polypropylene catalyst, introduces outer give
Electron is the well-known technique in the field with the property for adjusting polymer；However, in Ziegler-Natta type polyethylene catalysts
Polymerization process introduce external electron donor report it is then less.Studies have shown that such as in Ziegler-Natta type polyethylene catalysts
Polymerization process introduce external electron donor, then the parameters such as the activity of catalyst, hydrogen tune susceptibility and copolymerization performance can not all must
To optimization, partial properties reduce instead.Ziegler-Natta type polyethylene catalysts external electron donor skill due to the above reasons,
Art not yet industrializes, and report in the prior art is less.
Therefore, it is urgent to provide a kind of external electron donors, can improve Ziegler-Natta type polyolefin catalyst simultaneously
The parameters such as activity, hydrogen tune susceptibility and copolymerization performance.
Summary of the invention
In order to solve the above-mentioned problems in the prior art, the present invention provides a kind of caltalyst for olefinic polymerization
System and its application, by introducing the external electron donor-ring with special nature in Ziegler-Natta type polyolefin catalyst
Three black false hellebore hydrocarbons and their derivates can improve activity, hydrogen tune susceptibility and the copolymerization performance of catalyst simultaneously.
According to the first aspect of the invention, the present invention provides a kind of catalyst system for olefinic polymerization, the catalysis
Agent system includes the reaction product of following components:
1) ingredient of solid catalyst:
Reaction product comprising following components: ultra-fine carrier, magnesium halide, halogenated titanium, internal electron donor b and optionally interior are given
Electron a；
The internal electron donor b is selected from C2~C10Arrcostab, the C of aliphatic saturated monocarboxylic acid7~C10Aromatic carboxylic acids Arrcostab, C2
~C10Aliphatic ether, C3~C10Cyclic ethers and C3~C10At least one of saturated fat ketone；
The internal electron donor a is selected from least one of three black false hellebore hydrocarbons and their derivates of ring shown in formula (I)；
2) co-catalyst:
Selected from organo-aluminum compound, the general formula of the organo-aluminum compound is AlR1 dX1 3-d, R in formula1For hydrogen or Cl~C20
Alkyl, X1For halogen atom, 0 d≤3 <；
3) external donor compound:
At least one of three black false hellebore hydrocarbons and their derivates of ring shown in formula (I),
M in formula (I)1、M2、M3、M4、M5And M6It is identical or different, it each is selected from hydrogen, hydroxyl, amino, aldehyde radical, carboxyl, acyl
Base, halogen atom ,-R1Or-OR2, wherein R1And R2Respectively substituted or unsubstituted C1~C10Alkyl, substituent group be selected from hydroxyl,
Amino, aldehyde radical, carboxyl, acyl group, halogen atom, alkoxy or hetero atom；
As two group M adjacent on phenyl ring1And M2Or M3And M4Or M5And M6It each is selected from-R1Or-OR2When, two
It is optionally mutually cyclic between a adjacent group.
According to the second aspect of the invention, the present invention provides a kind of above-mentioned caltalysts to tie up in olefin polymerization
Using.
Catalyst system for olefinic polymerization of the invention is used as by using three black false hellebore hydrocarbons and their derivates of ring and gives outside
Electron, can improve activity, hydrogen response and the copolymerization performance of catalyst simultaneously, in addition, using catalyst of the invention
The bulk density and copolymerization units content for the polymerization powder that system is prepared increase.
Specific embodiment
To keep the present invention easier to understand, below in conjunction with specific embodiment, the present invention will be described in detail, these realities
It applies mode and only serves illustrative, be not intended to restrict the invention.
According to the first aspect of the invention, the present invention provides a kind of catalyst system for olefinic polymerization, the catalysis
Agent system includes the reaction product of following components:
1) ingredient of solid catalyst:
Reaction product comprising following components: ultra-fine carrier, magnesium halide, halogenated titanium, internal electron donor b and optionally interior are given
Electron a；
The internal electron donor b is selected from C2~C10Arrcostab, the C of aliphatic saturated monocarboxylic acid7~C10Aromatic carboxylic acids Arrcostab, C2
~C10Aliphatic ether, C3~C10Cyclic ethers and C3~C10At least one of saturated fat ketone；
The internal electron donor a is selected from least one of three black false hellebore hydrocarbons and their derivates of ring shown in formula (I)；
2) co-catalyst:
Selected from organo-aluminum compound, the general formula of the organo-aluminum compound is AlR1 dX1 3-d, R in formula1For hydrogen or Cl~C20
Alkyl, X1For halogen atom, 0 d≤3 <；
3) external donor compound:
At least one of three black false hellebore hydrocarbons and their derivates of ring shown in formula (I),
M in formula (I)1、M2、M3、M4、M5And M6It is identical or different, it each is selected from hydrogen, hydroxyl, amino, aldehyde radical, carboxyl, acyl
Base, halogen atom ,-R1Or-OR2, wherein R1And R2Respectively substituted or unsubstituted C1~C10Alkyl, substituent group be selected from hydroxyl,
Amino, aldehyde radical, carboxyl, acyl group, halogen atom, alkoxy or hetero atom；
As two group M adjacent on phenyl ring1And M2Or M3And M4Or M5And M6It each is selected from-R1Or-OR2When, two
It is optionally mutually cyclic between a adjacent group.
In the present invention, alkyl can be alkyl, naphthenic base, alkenyl, alkynyl, aryl or aralkyl etc..Wherein, C1~C10Alkane
Base refers to C1~C10Straight chained alkyl or C3~C10Branched alkyl, non-limiting example include: methyl, ethyl, n-propyl,
Isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl, tertiary pentyl, neopentyl, n-hexyl, n-heptyl,
N-octyl, dimethylhexanyl and positive decyl.
C3~C10The example of naphthenic base can include but is not limited to: cyclopropyl, cyclopenta, cyclohexyl, 4- methylcyclohexyl,
4- ethylcyclohexyl, 4- n-propyl cyclohexyl and 4- normal-butyl cyclohexyl.
C6~C10The example of aryl can include but is not limited to: phenyl, 4- aminomethyl phenyl and 4- ethylphenyl.
C2~C10The example of alkenyl can include but is not limited to: vinyl and allyl.
C2~C10The example of alkynyl can include but is not limited to: acetenyl and propargyl.
C7~C10The example of aralkyl can include but is not limited to: phenyl methyl, phenylethyl, phenyl n-propyl, phenyl
Normal-butyl, phenyl t-butyl and propyloxy phenyl base.
In the present invention, " substituted C1~C10Alkyl " refer to " C1~C10Alkyl " on a hydrogen atom (preferably hydrogen
Atom) or carbon atom replaced by the substituent group.
The hetero atom refers to the three black false hellebore hydrocarbons and their derivates of other rings other than halogen atom, carbon atom and hydrogen atom
Molecular structure on the atom that generally comprises, such as O, N, S, P, Si and B etc..
Preferably, in formula (I), M1、M2、M3、M4、M5And M6It is identical or different, it is former each to be selected from hydroxyl, amino, aldehyde radical, halogen
Son ,-R1Or-OR2, and R1And R2It each is selected from by the substituted or unsubstituted C of halogen atom1~C10Alkyl.
It is highly preferred that the three black false hellebore hydrocarbons and their derivates of ring are selected from least one of following compound:
Compound A:M1=M2=M3=M4=M5=M6=OCH3；
Compound B:M1=M2=M3=M4=M5=M6=OCH2CH3；
Compound C:M1=M2=M3=M4=M5=M6=OCH2CH2CH3；
Compound D:M1=M2=M3=M4=M5=M6=OCH (CH3)2；
Compound E:M1=M2=M3=M4=M5=M6=OCH2CH2CH2CH3；
Compound F:M1=M3=M5=OCH3；M2=M4=M6=OCH2CH3；
Compound G:M1=M3=M5=OCH3；M2=M4=M6=OCH2CH2CH3；
Compound H:M1=M3=M5=OCH3；M2=M4=M6=OCH2CH2CH2CH3；
Compound I:M1=M2=M3=M4=M5=M6=OH；
Compound J:M1=M3=M5=OCH3；M2=M4=M6=OH；
Compound K: M1=M3=M5=OCH3；M2=M4=M6=NH2；
Compound L: M1=M3=M5=OCH3；M2=M4=M6=Cl；
Compound M:M1=M3=M5=OCH3；M2=M4=M6=Br；
Compound N: M1=M3=M5=OCH3；M2=M4=M6=I；
Compound O:M1=M3=M5=OCH3；M2=M4=M6=CHO；
Compound P:M1=M3=M5=OCH3；M2=M4=M6=OCH2CH2CH2Br；
Compound Q: M1=M2=M3=M4=M5=M6=OCH2CH2Cl。
In addition, working as M1=M3=M5=X, M2=M4=M6(X, Y respectively indicate the above-mentioned M of the present invention to=Y1、M3、M5And M2、M4、
M6Selectable group, and X is different from Y) when, there may be following isomers: M for the three black false hellebore hydrocarbons and their derivates of ring1=M4
=M5=X, M2=M3=M6=Y.However the isomers is also within the scope of the present invention.
In the present invention, the three black false hellebore hydrocarbons and their derivates of ring can be prepared one of as follows:
Method 1: in the presence of acidic materials and optional halogenated hydrocarbons, by phenyl ring analog derivative A shown in formula (II) with
Formaldehyde or derivatives thereof is reacted, to obtain the three black false hellebore hydrocarbons and their derivates of ring；
Method 2: in the presence of acidic materials, phenyl ring analog derivative B shown in catalysis type (III) carries out condensation reaction, thus
To the three black false hellebore hydrocarbons and their derivates of ring；
Method 3: in the presence of a lewis acid, in halogenated hydrocarbons, phenyl ring analog derivative A and formaldehyde shown in catalysis type (II)
Or derivatives thereof reacted, to obtain the three black false hellebore hydrocarbons and their derivates of ring；
Wherein, to M7、M8、M9、M10Definition and M1~M6It is identical, details are not described herein.
The acidic materials can be selected from hydrochloric acid, perchloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, pyrosulfuric acid, sulfurous acid, phosphorus
Acid, pyrophosphoric acid, at least one of phosphorous acid, boric acid, formic acid, acetic acid, benzoic acid, trifluoroacetic acid, sulfonic acid and benzene sulfonic acid.
The halogenated hydrocarbons can be selected from carbon tetrachloride, chloroform, methylene chloride, bromomethane, monochlorethane, a chlorine third
Alkane, a chlorobutane, a chloropentane, a chlorohexane, bromic ether, 1,2- dichloroethanes, 1,3- dichloropropane, bis- neoprene of 1,4-
In alkane, 1,5- dichloropentane, 1,6- dichloro hexane, chlorocyclopentane, chlorocyclohexane, monochloro-benzene, dichloro-benzenes and bromobenzene
It is at least one.
The lewis acid can be selected from least one in boron trifluoride ether, ferric trichloride, alchlor and titanium tetrachloride
Kind.
The derivative of formaldehyde can be selected from paraformaldehyde, for example, metaformaldehyde.
In the above each method, the dosage of various raw materials is referred to routine techniques selection, repeats no more herein.
According to the present invention, the ultra-fine carrier can be common organic or inorganic in spray drying type polyolefin catalyst
Carrier, it is preferable that the ultra-fine carrier is selected from aluminium oxide, active carbon, clay, silica (silica gel), titanium dioxide, polyphenyl second
At least one of alkene and calcium carbonate, more preferably silica.
The partial size of the ultra-fine carrier can be 0.01~10 μm, preferably 0.01~5 μm, more preferably 0.01~2 μm,
Most preferably 0.01~1 μm.
Most preferably, the ultra-fine carrier is 0.01~1 μm of silica, the catalyst particle shape which generates is good,
Intensity is high, non-breakable.
In the present invention, the ultra-fine carrier can be bought with market, be also referred to preparation method in the prior art and obtained,
The present invention is not particularly limited this.
According to the present invention, the magnesium halide is generally selected from MgCl2、MgBr2And MgI2At least one of, preferably
MgCl2。
According to the present invention, the halogenated titanium can be selected from TiCl3、TiCl4、TiBr4And TiI4At least one of, preferably
For TiCl3And/or TiCl4。
According to the present invention, the specific example of the internal electron donor b includes but is not limited to: methyl formate, methyl acetate, second
Acetoacetic ester, propyl acetate, butyl acetate, acetic acid n-octyl, methyl benzoate, ethyl benzoate, ethyl p-methyl benzoate, second
Ether, hexyl ether, propylene oxide, 2,2- dimethyl -1,3- di ethyl propyl ether, 1,2- 1,2-dimethoxy benzene, tetrahydrofuran, acetone, fourth
Ketone and methyl iso-butyl ketone (MIBK) etc..
Preferably, the internal electron donor b is selected from methyl formate, ethyl acetate, butyl acetate, ether, hexyl ether, tetrahydro furan
It mutters, at least one of acetone and methyl iso-butyl ketone (MIBK).
In addition, the ingredient of solid catalyst can also include internal electron donor c, the internal electron donor c can be selected from
Different from other Organic Alcohols of the internal electron donor a and b, organic acid, organic acid esters, organic acid halides, organic acid anhydride, ether,
Ketone, amine, phosphate, amide, carbonic ester, phenol, pyridine and high-molecular compound with polar group etc., such as: acrylic acid second
Ester, butyl acrylate, methanol, ethyl alcohol, propyl alcohol, isopropanol, butanol, isooctanol, octylame, triethylamine, phenol, hydroquinone, ring
Oxidative ethane, epoxychloropropane, trimethyl phosphate, triethyl phosphate, tricresyl phosphate propyl ester, tributyl phosphate, triphenyl phosphate, phosphoric acid
Three own esters, polymethyl methacrylate, polystyrene, Hydrin, polyethylene oxide etc..
In the present invention, the internal electron donor a and the external donor compound can be identical or different.
According to the present invention, the ingredient of solid catalyst can be prepared using following methods:
1) magnesium halide, halogenated titanium, internal electron donor b and optional internal electron donor a are subjected to dissolution reaction, mother is made
Liquid；
2) ultra-fine carrier and the mother liquor are blended, slurry liquid is made；
3) the slurry liquid is spray-dried, obtains the ingredient of solid catalyst.
Specifically, the method may include following steps:
S1: magnesium halide, halogenated titanium, internal electron donor b and optional internal electron donor a are mixed and anti-at 0~90 DEG C
0.5~5h is answered, mother liquor is made；
S2: at 0~90 DEG C, ultra-fine carrier and mother liquor is blended into 0.5~3h, slurry liquid is made；
S3: slurry liquid made from S2 is spray-dried, and obtains the ingredient of solid catalyst.
Wherein, the spray drying carries out on spray dryer, and the condition of spray drying generally includes: inlet temperature is
80~240 DEG C, preferably 120~200 DEG C；Outlet temperature is 60~130 DEG C, preferably 90~120 DEG C.
The ultra-fine carrier for preparing slurry liquid should be the drying carrier for not adsorbing water, and the ultra-fine carrier is in slurry liquid
In content need to meet to be formed and be suitable for subject to the slurry liquid that is spray-dried, the content of ultra-fine carrier in the slurry liquid
Usually 3~50wt%, preferably 5~30wt%.
Under preferable case, in the ingredient of solid catalyst, the molar ratio of the halogenated titanium and the magnesium halide is 1 ︰ 20
The molar ratio of~1 ︰ 2, the halogenated titanium and the internal electron donor b are 1 ︰, 1~1 ︰ 600, the internal electron donor a and the halogen
The molar ratio for changing titanium is 0~0.2 ︰ 1.
Preferably, the organo-aluminum compound be selected from triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium,
At least one of one aluminium ethide of aluminium diethyl monochloride and dichloro；Wherein, the ingredient of solid catalyst and organic calorize
The molar ratio Yi Tai ︰ aluminium for closing object is calculated as 1 ︰, 1~1 ︰ 1000,10~1 ︰ 200 of preferably 1 ︰.
In the present invention, the organo-aluminum compound is also used as the activator component of the ingredient of solid catalyst, will
Titanium atom in the ingredient of solid catalyst is reduced into the state that the alkene such as ethylene can be made effectively to polymerize, and obtains consolidating for prereduction
Body catalyst component.
It, can be in the presence of atent solvent, by the ingredient of solid catalyst and organo-aluminium when as activator component
Compound is reacted, and the ingredient of solid catalyst of prereduction is obtained.
The atent solvent refers to inert hydrocarbon solvent, preferably iso-butane, hexane, heptane, hexamethylene, naphtha, pumping
The atent solvents such as the aliphatic saturated hydrocarbons such as excess oil, hydrogasoline, kerosene, benzene, toluene and dimethylbenzene or aromatic hydrocarbon；More preferably first
Benzene, n-hexane or hexamethylene.
In addition, as activator component and as co-catalyst in use, the type of organo-aluminum compound selection can
With identical or different.
According to the present invention, the molar ratio of the external donor compound and titanium in the ingredient of solid catalyst is 0.5 ︰
1~50 ︰ 1.
According to the second aspect of the invention, the present invention provides a kind of above-mentioned caltalyst and ties up to answering in olefin polymerization
With.
In the present invention, the olefin polymerization includes homopolymerization reaction and the copolymerization of alkene.
Specifically, catalyst system of the invention can be used for the homopolymerization of ethylene；It is ethylene and butylene, amylene, hexene, pungent
The combined polymerization of the combined polymerization of alkene or 4-methyl-1-pentene, preferably ethylene and butylene.
In addition, the catalyst system be suitable for it is various under the conditions of polymerization reaction, for example, the olefin polymerization can
To be carried out in liquid phase or gas phase, or can also be carried out under the operation that liquid phase is combined with gas phase polymerization stage.The temperature of polymerization
Degree can be 0~150 DEG C, preferably 60~90 DEG C.
Medium used by liquid phase polymerization can be selected from iso-butane, hexane, heptane, hexamethylene, naphtha, raffinate oil, add
The atent solvents such as the aliphatic saturated hydrocarbons such as hydrogen gasoline, kerosene, benzene,toluene,xylene or aromatic hydrocarbon, preferably toluene, n-hexane or
Hexamethylene.
In addition, making molecular weight regulator using hydrogen to adjust the molecular weight of final polymer.
The present invention will be described in detail by way of examples below.
In the following Examples and Comparative Examples:
1, in ingredient of solid catalyst titanium elements relative weight percents: use spectrophotometry.
2, the composition of ingredient of solid catalyst: liquid nuclear-magnetism is used1H-NMR。
3, it melt index (MI): according to ASTM D1238-99, load 2.16kg, measures at 190 DEG C.
4, copolymerization units content in polymer powders: liquid nuclear-magnetism is used13C-NMR is determined.
5, in polymer powders hexane extractable content weight percent: resulting whole powder slurries nitrogen will be polymerize
It is transferred in standard cylindrical container, is thoroughly dried in ventilation condition, obtain blocky powder, vertically cut the blocky powder of gained
20g is placed it in container after crushing, is extracted 2h with 300mL hexane at 50 DEG C, is then extracted 20mL extracting solution, place it in
In the surface plate being precisely weighed, the surface plate being completely dried is weighed, the mass weight gain of surface plate is m1(g), and thus
The weight percent for calculating hexane extractable content is 75m1%.
6, in polymerization reaction, the pressure in kettle is absolute pressure.
Preparation example 1~3 is used to illustrate the preparation method of the three black false hellebore hydrocarbons and their derivates of ring.
Preparation example 1
Under condition of ice bath, 1,2- 1,2-dimethoxy benzene (1.0g) is added drop-wise to formalin (4mL/38%)/0.1mL tri-
It in the mixture of chloromethanes/concentrated hydrochloric acid (6mL), is reacted, after 30 minutes, solution becomes starchiness, continues to stir at room temperature
4h.Solid is collected by filtration, ice water washing thoroughly obtains 0.5g formula (IV) compound represented A after drying.
Preparation example 2
Under condition of ice bath, 3- methoxyl group -4- ethyoxyl-benzyl alcohol (3g) is dissolved in 30mL methanol, in ice bath and stirring
The perchloric acid 15mL of lower dropwise addition 65%.Under nitrogen protection, ice bath stirring 18h.30mL water is slowly added into reaction product, with
After make that organic phase is extracted with dichloromethane.After organic phase is carefully washed with sodium hydrate aqueous solution, then it is washed with deionized,
It is dry.It is purified after organic phase is thoroughly drained using column chromatography, obtains 1g such as formula (V) compound represented F.
Preparation example 3
Under condition of ice bath, the bromo- benzyl alcohol of 3- methoxyl group -4- (3.6g) is dissolved in 30mL methanol, under ice bath and stirring
65% perchloric acid 15mL is added dropwise.Under nitrogen protection, ice bath stirring 18h.30mL water is slowly added into reaction product, then
Make that organic phase is extracted with dichloromethane.It after organic phase is carefully washed with sodium hydrate aqueous solution, then is washed with deionized, does
It is dry.It is purified after thoroughly draining using column chromatography, obtains 0.8g formula (VI) compound represented M.
Examples 1 to 3 is for illustrating that catalyst system and caltalyst of the invention tie up in olefin polymerization
Using.
Embodiment 1
(1) preparation of ingredient of solid catalyst
It is blown to one by nitrogen and 1.5g TiCl is successively added in the 250mL there-necked flask of row4, the anhydrous MgCl of 4.4g2With
100mL tetrahydrofuran is warming up to 65 DEG C, at this temperature isothermal reaction 3h under stirring, be cooled to 35 DEG C, obtain mother liquor.
Blow to one by nitrogen be added in the 250mL there-necked flask of row 6g silica gel (Cabot Corporation TS-610,
Partial size is 0.02~0.1 μm), the mother liquor after cooling is added, is kept for 35 DEG C of temperature, after stirring 1h, the mother after silica gel is blended
Liquid is spray-dried with spray dryer, spray condition: 180 DEG C of inlet temperature, 110 DEG C of outlet temperature, obtaining solid catalysis
Agent component a, composition are shown in Table 1.
(2) pre-reduction treatment
Blow 100mL hexane be successively added in the 250mL there-necked flask of row by nitrogen to one, 5g ingredient of solid catalyst and
4mL tri-n-hexyl aluminum (1M), is warming up to 50 DEG C, at this temperature constant temperature 1h under stirring, add 9mL aluminium diethyl monochloride
(1M) continues constant temperature 1h, filters off mother liquor, dry after hexane repeatedly washs, and the solid for obtaining the prereduction of good fluidity is urged
Agent component a.
(3) homopolymerization is reacted
1. low hydrogen gas/ethylene ratio polymerization reaction
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is sufficiently displaced from, 1L hexane is added, 1.0mL concentration is 1M
The triethyl aluminum and 0.01mmol compound A as made from preparation example 1, add and consolidated by prereduction prepared by the above method
Body catalyst component a (titanium containing 0.6mg), is warming up to 75 DEG C, and being passed through hydrogen makes pressure in kettle reach 0.28MPa, then is passed through ethylene
So that stagnation pressure in kettle is reached 1.03MPa, polymerize 2h under the conditions of 85 DEG C, polymerization result is shown in Table 2.
2. the polymerization reaction of high hydrogen/ethylene ratio
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is sufficiently displaced from, 1L hexane is added, 1.0mL concentration is 1M
The triethyl aluminum and 0.01mmol compound A as made from preparation example 1, add and consolidated by prereduction prepared by the above method
Body catalyst component a (titanium containing 0.6mg), is warming up to 75 DEG C, and being passed through hydrogen makes pressure in kettle reach 0.68MPa, then is passed through ethylene
So that stagnation pressure in kettle is reached 1.03MPa, polymerize 2h under the conditions of 85 DEG C, polymerization result is shown in Table 2.
(4) copolymerization
Configure the gaseous mixture of ethylene/butylene first in distribution tank, the molar ratio of gaseous mixture be ethylene/butylene=
0.85/0.15。
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is sufficiently displaced from, 1L hexane is added, 1.0mL concentration is 1M
The triethyl aluminum and 0.01mmol compound A as made from preparation example 1, add and consolidated by prereduction prepared by the above method
Body catalyst component a (titanium containing 0.6mg), is warming up to 70 DEG C, and being passed through hydrogen makes pressure in kettle reach 0.28MPa, then be passed through ethylene/
Butylene gaseous mixture makes stagnation pressure in kettle reach 0.73MPa, polymerize 2h under the conditions of 80 DEG C, polymerization result is shown in Table 3.
Embodiment 2
(1) preparation of ingredient of solid catalyst and pre-reduction treatment
With embodiment 1.
(2) homopolymerization is reacted
1. low hydrogen gas/ethylene ratio polymerization reaction
With embodiment 1, but the type of external electron donor and additional amount are changed into 0.01mmol as made from preparation example 2
Compound F, polymerization result are shown in Table 2.
2. the polymerization reaction of high hydrogen/ethylene ratio
With embodiment 1, but the type of external electron donor and additional amount are changed into 0.01mmol as made from preparation example 2
Compound F, polymerization result are shown in Table 2.
(3) copolymerization
With embodiment 1, but the type of external electron donor and additional amount are changed into 0.01mmol as made from preparation example 2
Compound F, polymerization result are shown in Table 3.
Embodiment 3
(1) preparation of ingredient of solid catalyst
It is blown to one by nitrogen and 1.5g TiCl is successively added in the 250mL there-necked flask of row4, the anhydrous MgCl of 4.4g2, 0.1g
Compound M and the 100mL tetrahydrofuran as made from preparation example 3, is warming up to 65 DEG C, at this temperature isothermal reaction 3h under stirring,
35 DEG C are cooled to, mother liquor is obtained.
Blow to one by nitrogen be added in the 250mL there-necked flask of row 6g silica gel (Cabot Corporation TS-610,
Partial size is 0.02~0.1 μm), the mother liquor after cooling is added, is kept for 35 DEG C of temperature, after stirring 1h, the mother after silica gel is blended
Liquid is spray-dried with spray dryer, spray condition: 180 DEG C of inlet temperature, 110 DEG C of outlet temperature, obtaining solid catalysis
Agent component b, composition are shown in Table 1.
(2) pre-reduction treatment
Blow 100mL hexane be successively added in the 250mL there-necked flask of row by nitrogen to one, 5g ingredient of solid catalyst and
4mL tri-n-hexyl aluminum (1M), is warming up to 50 DEG C, at this temperature constant temperature 1h under stirring, add 9mL aluminium diethyl monochloride
(1M) continues constant temperature 1h, filters off mother liquor, dry after hexane repeatedly washs, and the solid for obtaining the prereduction of good fluidity is urged
Agent component b.
(3) homopolymerization is reacted
1. low hydrogen gas/ethylene ratio polymerization reaction
With embodiment 1, but the type of external electron donor and additional amount are changed into 0.02mmol as made from preparation example 3
Compound M, and add be prereduction ingredient of solid catalyst b, polymerization result is shown in Table 2.
2. the polymerization reaction of high hydrogen/ethylene ratio
With embodiment 1, but the type of external electron donor and additional amount are changed into 0.02mmol as made from preparation example 3
Compound M, and add be prereduction ingredient of solid catalyst b, polymerization result is shown in Table 2.
(4) copolymerization
With embodiment 1, but the type of external electron donor and additional amount are changed into 0.02mmol as made from preparation example 3
Compound M, and add be prereduction ingredient of solid catalyst b, polymerization result is shown in Table 3.
Comparative example 1
(1) preparation of ingredient of solid catalyst and pre-reduction treatment
As described in Example 1.
(2) homopolymerization is reacted
1. low hydrogen gas/ethylene ratio polymerization reaction
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is sufficiently displaced from, 1L hexane is added and 1.0mL concentration is 1M
Triethyl aluminum, add by the above method prepare prereduction ingredient of solid catalyst a (titanium containing 0.6mg), be warming up to
75 DEG C, being passed through hydrogen makes pressure in kettle reach 0.28MPa, then being passed through ethylene makes stagnation pressure in kettle reach 1.03MPa, in 85 DEG C of conditions
Lower polymerization 2h, polymerization result are shown in Table 2.
2. the polymerization reaction of high hydrogen/ethylene ratio
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is sufficiently displaced from, 1L hexane is added and 1.0mL concentration is 1M
Triethyl aluminum, add by the above method prepare prereduction ingredient of solid catalyst a (titanium containing 0.6mg), be warming up to
75 DEG C, being passed through hydrogen makes pressure in kettle reach 0.68MPa, then being passed through ethylene makes stagnation pressure in kettle reach 1.03MPa, in 85 DEG C of conditions
Lower polymerization 2h, polymerization result are shown in Table 2.
(3) copolymerization
Configure the gaseous mixture of ethylene/butylene first in distribution tank, the molar ratio of gaseous mixture be ethylene/butylene=
0.85/0.15。
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is sufficiently displaced from, 1L hexane is added and 1.0mL concentration is 1M
Triethyl aluminum, add by the above method prepare prereduction ingredient of solid catalyst a (titanium containing 0.6mg), be warming up to
70 DEG C, being passed through hydrogen makes pressure in kettle reach 0.28MPa, then being passed through ethylene/butylene gaseous mixture reaches stagnation pressure in kettle
0.73MPa polymerize 2h under the conditions of 80 DEG C, and polymerization result is shown in Table 3.
Comparative example 2
(1) preparation of ingredient of solid catalyst and pre-reduction treatment
As described in Example 1.
(2) homopolymerization is reacted
1. low hydrogen gas/ethylene ratio polymerization reaction
With embodiment 1, but the type of external electron donor and additional amount are changed into the ethyl benzoate of 0.01mmol, gathers
Conjunction the results are shown in Table 2.
2. the polymerization reaction of high hydrogen/ethylene ratio
With embodiment 1, but the type of external electron donor and additional amount are changed into the ethyl benzoate of 0.01mmol, gathers
Conjunction the results are shown in Table 2.
(3) copolymerization
With embodiment 1, but the type of external electron donor and additional amount are changed into the ethyl benzoate of 0.01mmol, gathers
Conjunction the results are shown in Table 3.
Comparative example 3
(1) preparation of ingredient of solid catalyst and pre-reduction treatment
As described in Example 1.
(2) homopolymerization is reacted
1. low hydrogen gas/ethylene ratio polymerization reaction
With embodiment 1, but the type of external electron donor and additional amount are changed into 1, the 2- O-phthalic of 0.01mmol
Ether, polymerization result are shown in Table 2.
2. the polymerization reaction of high hydrogen/ethylene ratio
With embodiment 1, but the type of external electron donor and additional amount are changed into 1, the 2- O-phthalic of 0.01mmol
Ether, polymerization result are shown in Table 2.
(3) copolymerization
With embodiment 1, but the type of external electron donor and additional amount are changed into 1, the 2- O-phthalic of 0.01mmol
Ether, polymerization result are shown in Table 3.
Comparative example 4
(1) preparation of ingredient of solid catalyst and pre-reduction treatment
As described in Example 3.
(2) homopolymerization is reacted
1. low hydrogen gas/ethylene ratio polymerization reaction
With comparative example 1, but add be prereduction ingredient of solid catalyst b, polymerization result is shown in Table 2.
2. the polymerization reaction of high hydrogen/ethylene ratio
With comparative example 1, but add be prereduction ingredient of solid catalyst b, polymerization result is shown in Table 2.
(3) copolymerization
With comparative example 1, but add be prereduction ingredient of solid catalyst b, polymerization result is shown in Table 3.
Comparative example 5
(1) preparation of ingredient of solid catalyst and pre-reduction treatment
As described in Example 3.
(2) homopolymerization is reacted
1. low hydrogen gas/ethylene ratio polymerization reaction
With embodiment 1, but the type of external electron donor and additional amount are changed into dimethyl -1 2,2- of 0.02mmol,
3- di ethyl propyl ether, and add be prereduction ingredient of solid catalyst b, polymerization result is shown in Table 2.
2. the polymerization reaction of high hydrogen/ethylene ratio
With embodiment 1, but the type of external electron donor and additional amount are changed into dimethyl -1 2,2- of 0.02mmol,
3- di ethyl propyl ether, and add be prereduction ingredient of solid catalyst b, polymerization result is shown in Table 2.
(3) copolymerization
With embodiment 1, but the type of external electron donor and additional amount are changed into dimethyl -1 2,2- of 0.02mmol,
3- di ethyl propyl ether, and add be prereduction ingredient of solid catalyst b, polymerization result is shown in Table 3.
Table 1
Table 2
From the data of table 2:
1, invention catalyst system and is not added by addition three black false hellebore hydrocarbons and their derivates of ring as external electron donor
The catalyst system of external electron donor is compared, in low hydrogen second than can improve simultaneously poly- in the polymerization reaction with high hydrogen second ratio
The activity of catalyst for ethylene system, hydrogen tune susceptibility, and the bulk density of polymerization powder；
2, by other compounds (listed compound only serve it is illustrative, such as ethyl benzoate, 1,2- 1,2-dimethoxy benzene
With 2,2- dimethyl -1,3- di ethyl propyl ether) as external electron donor be added catalyst system after, the work of catalyst system
Property, hydrogen tune susceptibility, and polymerization powder bulk density but decrease.
Table 3
From the data of table 3:
1, after the present invention is by introducing catalyst system as external electron donor for three black false hellebore hydrocarbons and their derivates of ring, polymerization
The copolymerization units content of powder improves, and hexane extractable content is reduced.This explanation is with copolymerization units content in polymerization powder
It improves, the copolymerization units content in lower-molecular-weight component is reduced, and the copolymerization units content in medium/high molecular weight component improves.
It follows that three black false hellebore hydrocarbons and their derivates of ring improve the copolymerization performance of catalyst system, so that it is comprehensive to be conducive to product
The raising of energy.
2, by other compounds (listed compound only serve it is illustrative, such as ethyl benzoate, 1,2- 1,2-dimethoxy benzene
With 2,2- dimethyl -1,3- di ethyl propyl ether) as external electron donor introduce catalyst system after, polymerize the copolymerization list of powder
First content and hexane extractable content reduce.This illustrates that above-mentioned external electron donor reduces the addition probability of comonomer, although
Hexane extractable content also decreases, but this is not the raising of catalyst system copolymerization performance.
The embodiment of the present invention is described above, above description is exemplary, and non-exclusive, and also not
It is limited to disclosed embodiment.Without departing from the scope and spirit of illustrated embodiment, for the art
Many modifications and changes are obvious for those of ordinary skill.
Claims (10)
1. a kind of catalyst system for olefinic polymerization, which is characterized in that the catalyst system includes the reaction of following components
Product:
1) ingredient of solid catalyst:
Reaction product comprising following components: ultra-fine carrier, magnesium halide, halogenated titanium, internal electron donor b and optional interior electron
Body a；
The internal electron donor b is selected from C2~C10Arrcostab, the C of aliphatic saturated monocarboxylic acid7~C10Aromatic carboxylic acids Arrcostab, C2~C10
Aliphatic ether, C3~C10Cyclic ethers and C3~C10At least one of saturated fat ketone；
The internal electron donor a is selected from least one of three black false hellebore hydrocarbons and their derivates of ring shown in formula (I)；
2) co-catalyst:
Selected from organo-aluminum compound, the general formula of the organo-aluminum compound is AlR1 dX1 3-d, R in formula1For hydrogen or Cl~C20Alkyl,
X1For halogen atom, 0 d≤3 <；
3) external donor compound:
At least one of three black false hellebore hydrocarbons and their derivates of ring shown in formula (I),
M in formula (I)1、M2、M3、M4、M5And M6It is identical or different, it each is selected from hydrogen, hydroxyl, amino, aldehyde radical, carboxyl, acyl group, halogen
Atom ,-R1Or-OR2, wherein R1And R2Respectively substituted or unsubstituted C1~C10Alkyl, substituent group be selected from hydroxyl, amino,
Aldehyde radical, carboxyl, acyl group, halogen atom, alkoxy or hetero atom；
As two group M adjacent on phenyl ring1And M2Or M3And M4Or M5And M6It each is selected from-R1Or-OR2When, two phases
It is optionally mutually cyclic between adjacent group.
2. catalyst system according to claim 1, wherein in formula (I), M1、M2、M3、M4、M5And M6It is identical or different,
It each is selected from hydroxyl, amino, aldehyde radical, halogen atom ,-R1Or-OR2, and R1And R2It each is selected from substituted or unsubstituted by halogen atom
C1~C10Alkyl.
3. catalyst system according to claim 1 or 2, wherein the three black false hellebore hydrocarbons and their derivates of ring are selected from following
At least one of compound:
Compound A:M1=M2=M3=M4=M5=M6=OCH3；
Compound B:M1=M2=M3=M4=M5=M6=OCH2CH3；
Compound C:M1=M2=M3=M4=M5=M6=OCH2CH2CH3；
Compound D:M1=M2=M3=M4=M5=M6=OCH (CH3)2；
Compound E:M1=M2=M3=M4=M5=M6=OCH2CH2CH2CH3；
Compound F:M1=M3=M5=OCH3；M2=M4=M6=OCH2CH3；
Compound G:M1=M3=M5=OCH3；M2=M4=M6=OCH2CH2CH3；
Compound H:M1=M3=M5=OCH3；M2=M4=M6=OCH2CH2CH2CH3；
Compound I:M1=M2=M3=M4=M5=M6=OH；
Compound J:M1=M3=M5=OCH3；M2=M4=M6=OH；
Compound K: M1=M3=M5=OCH3；M2=M4=M6=NH2；
Compound L: M1=M3=M5=OCH3；M2=M4=M6=Cl；
Compound M:M1=M3=M5=OCH3；M2=M4=M6=Br；
Compound N: M1=M3=M5=OCH3；M2=M4=M6=I；
Compound O:M1=M3=M5=OCH3；M2=M4=M6=CHO；
Compound P:M1=M3=M5=OCH3；M2=M4=M6=OCH2CH2CH2Br；
Compound Q: M1=M2=M3=M4=M5=M6=OCH2CH2Cl。
4. catalyst system according to claim 1, wherein the ultra-fine carrier be selected from aluminium oxide, active carbon, clay,
At least one of silica, titanium dioxide, polystyrene and calcium carbonate；The partial size of the ultra-fine carrier is 0.01~10 μ
m。
5. catalyst system according to claim 1, wherein the magnesium halide is selected from MgCl2、MgBr2And MgI2In extremely
Few one kind；The halogenated titanium is TiCl3And/or TiCl4。
6. catalyst system according to claim 1, wherein the ingredient of solid catalyst is prepared using following methods:
1) magnesium halide, halogenated titanium, internal electron donor b and optional internal electron donor a are subjected to dissolution reaction, mother liquor is made；
2) ultra-fine carrier and the mother liquor are blended, slurry liquid is made；
3) the slurry liquid is spray-dried, obtains the ingredient of solid catalyst.
7. catalyst system according to claim 6, wherein in the slurry liquid content of ultra-fine carrier be 3~
50wt%, preferably 5~30wt%.
8. catalyst system according to claim 1 or 6, wherein the molar ratio of the halogenated titanium and the magnesium halide is
The molar ratio of 1 ︰, 20~1 ︰ 2, the halogenated titanium and the internal electron donor b are 1 ︰, 1~1 ︰ 600.
9. catalyst system according to claim 1, wherein the external donor compound and the solid catalyst
The molar ratio of titanium is 0.5 ︰, 1~50 ︰ 1 in component.
10. caltalyst described in any one of claim 1~9 ties up to the application in olefin polymerization.
Priority Applications (9)
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| CN201710592383.XA CN109280107B (en) | 2017-07-19 | 2017-07-19 | Catalyst system for olefin polymerization and application thereof |
| JP2020502696A JP7038797B2 (en) | 2017-07-19 | 2018-07-19 | Olefin polymerization catalyst containing cyclotribellatrilen and its derivatives |
| CN201880002860.5A CN109526217B (en) | 2017-07-19 | 2018-07-19 | Olefin polymerization catalyst containing cyclotri veratrum hydrocarbon and derivatives thereof |
| US16/631,482 US11401356B2 (en) | 2017-07-19 | 2018-07-19 | Olefin polymerization catalyst comprising cyclotriveratrylene and derivatives thereof |
| KR1020207002897A KR102336976B1 (en) | 2017-07-19 | 2018-07-19 | Olefin polymerization catalyst comprising cyclotiberatrylene and derivatives thereof |
| RU2020103744A RU2740916C1 (en) | 2017-07-19 | 2018-07-19 | Olefin polymerisation catalyst comprising cyclotriveratrilene and derivatives thereof |
| BR112020001201-7A BR112020001201B1 (en) | 2017-07-19 | 2018-07-19 | ZIEGLER-NATTA CATALYST SYSTEM FOR OLEFIN POLYMERIZATION, SOLID CATALYST COMPONENT FOR OLEFIN POLYMERIZATION AND OLEFIN POLYMERIZATION PROCESS |
| EP18835679.4A EP3656754A4 (en) | 2017-07-19 | 2018-07-19 | Olefin polymerization catalyst comprising cyclotriveratrylene and derivatives thereof |
| PCT/CN2018/096248 WO2019015638A1 (en) | 2017-07-19 | 2018-07-19 | Olefin polymerization catalyst comprising cyclotriveratrylene and derivatives thereof |
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| CN110734510A (en) * | 2018-07-19 | 2020-01-31 | 中国石油化工股份有限公司 | Olefin polymerization catalyst containing cyclotri veratrum hydrocarbon and its derivatives |
| CN113004452A (en) * | 2021-04-27 | 2021-06-22 | 辛集市旭远新材料科技有限公司 | Impact-resistant polypropylene and preparation method thereof |
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