CN111116779A - Propylene polymer and preparation method thereof - Google Patents

Propylene polymer and preparation method thereof Download PDF

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Publication number
CN111116779A
CN111116779A CN201811289919.1A CN201811289919A CN111116779A CN 111116779 A CN111116779 A CN 111116779A CN 201811289919 A CN201811289919 A CN 201811289919A CN 111116779 A CN111116779 A CN 111116779A
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substituted
unsubstituted
propylene
propylene polymer
molecular weight
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张军辉
高榕
周俊领
郭子芳
林洁
李季禹
张晓帆
赵惠
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D01F6/06—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins from polypropylene
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Engineering & Computer Science (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

The invention discloses a propylene polymer which has no melting point through DSC test, is a random propylene polymer, has the weight-average molecular weight of 30000-400000 and the molecular weight distribution of 1.0-3.0, and is preferably 1.0-1.5. The invention also discloses a preparation method of the propylene polymer, which comprises the steps of contacting propylene with a catalyst under the condition of olefin polymerization reaction; the catalyst comprises a main catalyst and a cocatalyst, wherein the main catalyst is selected from a metal complex shown in a formula I:

Description

Propylene polymer and preparation method thereof
Technical Field
The invention relates to a propylene polymer and a preparation method thereof, in particular to a random propylene polymer without a melting point and a preparation method thereof, belonging to the field of propylene polymers.
Background
China is the country with the fastest increase of the consumption of synthetic resin and the largest import country of the synthetic resin, the polyolefin yield accounts for nearly 60 percent at present, and the olefin resin has excellent environmental harmony compared with other resin materials and is used as a material for key popularization in the automobile industry of developed countries. Polypropylene is one of the synthetic resins which is fastest in development, has the largest yield and extremely wide application, and can reach 7000 ten thousand tons in 2017. The atactic polypropylene has the characteristics of good solubility, moisture resistance, chemical resistance and the like; can be used as coating and adhesive components, main agents of blends, special material blending agents, sealants and the like. The random polypropylene synthesized by the traditional heterogeneous Ziegler-Natta catalyst still contains isotactic chain segments, and is not true random polypropylene.
In 1995, Brookhart et al reported a class of α -diimine nickel and palladium complexes, which have better catalytic effect on olefin polymerization, better tolerance to polar monomers, and capability of catalyzing copolymerization of olefin and polar monomers, so that research on post-transition metal catalysts is emphasized, such a class of α -diimine nickel catalysts can catalyze oligomerization or polymerization of ethylene at normal or low temperature with high activity under the action of methylaluminoxane or alkylaluminum. Bazan et al reported a-ketone- β -diimine nickel catalyst (chem. Commun.2009,6177-6179) to catalyze propylene polymerization at-10 ℃ to obtain an olefin product with a molecular weight distribution of 1.05.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a propylene polymer and a preparation method thereof.
According to one aspect of the present invention there is provided a propylene polymer which is a random propylene polymer having a weight average molecular weight of 30000-400000 and a molecular weight distribution of 1.0 to 3.0.
According to some embodiments of the invention, the propylene polymer has no melting point, is a completely random propylene polymer, and has a molecular weight distribution of 1.0 to 1.5, and may be, for example, 1.1, 1.2, 1.3, 1.4, and any value therebetween.
According to another aspect of the present invention, there is provided a process for producing the above propylene polymer, comprising contacting propylene with a catalyst under olefin polymerization conditions; the catalyst comprises a main catalyst and a cocatalyst, wherein the main catalyst is selected from a metal complex shown in a formula I:
Figure BDA0001849843210000021
in the formula I, R1-R4Same or different, eachIndependently selected from hydrogen, halogen and substituted or unsubstituted C1-C20A hydrocarbon group of R1-R4Can form rings with each other arbitrarily; r5Selected from hydrogen and substituted or unsubstituted C1-C20A hydrocarbon group of (a); r9And R10Same or different, each independently selected from substituted or unsubstituted C1-C30A hydrocarbon group of (a); m is a group VIII metal; x is selected from the group consisting of halogen and substituted or unsubstituted hydrocarbyl; n is an integer satisfying the valence of M.
According to a preferred embodiment of the invention, in formula I, R1-R4Same or different, each independently selected from hydrogen and substituted or unsubstituted C1-C10A hydrocarbon group of R1-R4Can form rings with each other arbitrarily; preferably R1And R4Bonded to form a ring, R2And R3Bonding to form a ring; r5Selected from hydrogen and substituted or unsubstituted C1-C10Is preferably C1-C10More preferably C1-C6Alkyl groups of (a); r9And R10Same or different, each independently selected from substituted or unsubstituted C1-C30Is preferably C1-C20More preferably C1-C20An alkylaryl group of (a); m is a group VIII metal; x is selected from the group consisting of halogen and substituted or unsubstituted hydrocarbyl; n is an integer satisfying the valence of M.
According to a preferred embodiment of the invention, in formula I, R1-R4Same or different, each independently selected from hydrogen, halogen and substituted or unsubstituted C1～C10Linear alkyl, substituted or unsubstituted C of3～C10Branched alkyl or cycloalkyl, substituted or unsubstituted C2～C10Linear alkenyl of (A), substituted or unsubstituted C3～C10Substituted or unsubstituted C6～C10Aryl, substituted or unsubstituted C7～C10Alkylaryl or arylalkyl of, substituted or unsubstituted C2～C10A substituted or unsubstituted C4～C10And substituted or unsubstituted C1～C10Alkoxy of R1-R4Can form rings with each other arbitrarily; preferably R1And R4Bonded to form a ring, R2And R3Bonding to form a ring; r5Selected from hydrogen and substituted or unsubstituted C1～C10Linear alkyl, substituted or unsubstituted C of3～C10Branched alkyl or cycloalkyl of, preferably C1-C10Straight and branched alkyl of (2), more preferably C1-C6Linear and branched alkyl groups of (a); r9And R10Same or different, each independently selected from substituted or unsubstituted C1～C30Linear alkyl, substituted or unsubstituted C of3～C30Branched alkyl or cycloalkyl, substituted or unsubstituted C2～C30Linear alkenyl of (A), substituted or unsubstituted C3～C30Substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted C7～C30Alkylaryl or arylalkyl of, substituted or unsubstituted C2～C30A substituted or unsubstituted C4～C30And substituted or unsubstituted C1～C30Alkoxy of (3), preferably C1-C20More preferably C1-C20An alkylaryl group of (a); m is a group VIII metal; x is selected from the group consisting of halogen, substituted or unsubstituted alkyl, and substituted or unsubstituted alkoxy; n is an integer satisfying the valence of M.
According to some embodiments of the invention, the procatalyst is selected from the group consisting of metal complexes represented by formula II:
Figure BDA0001849843210000031
in the formula II, R1-R10Same or different, each independently selected from hydrogen, halogen and substituted or unsubstituted C1-C20Is preferably C1-C10Alkyl of R1-R10Can form rings with each other arbitrarily; r21And R22Identical or different, are each independently selected from hydrogen, halogen and substituted or unsubstituted hydrocarbon radicals, preferably C1-C10The hydrocarbon group of (A), R being on the same benzene ring21And R22Can form a ring with each other; r5Selected from hydrogen and substituted or unsubstituted C1-C10Is preferably C1-C10More preferably C1-C6Alkyl groups of (a); m is a group VIII metal; x is selected from the group consisting of halogen and substituted or unsubstituted hydrocarbyl.
According to a preferred embodiment of the invention, in formula II, R1-R10Same or different, each independently selected from hydrogen, halogen and substituted or unsubstituted C1～C10Linear alkyl, substituted or unsubstituted C of3～C10Branched alkyl or cycloalkyl, substituted or unsubstituted C2～C10Linear alkenyl of (A), substituted or unsubstituted C3～C10Substituted or unsubstituted C6～C10Aryl, substituted or unsubstituted C7～C10Alkylaryl or arylalkyl of, substituted or unsubstituted C2～C10A substituted or unsubstituted C4～C10And substituted or unsubstituted C1～C10Alkoxy of (3), preferably C1-C6Linear alkyl and linear alkyl of R1-R10Can form rings with each other arbitrarily; r21And R22Same or different, each independently selected from hydrogen, halogen and substituted or unsubstituted C1～C10Linear alkyl, substituted or unsubstituted C of3～C10Branched alkyl or cycloalkyl, substituted or unsubstituted C2～C10Linear alkenyl of (A), substituted or unsubstituted C3～C10Substituted or unsubstituted C6～C10Aryl, substituted or unsubstituted C7～C10Alkylaryl or arylalkyl of, substituted or unsubstituted C2～C10Lipoheterocyclic radical of, substituted orUnsubstituted C4～C10And substituted or unsubstituted C1～C10Alkoxy of (2), R on the same phenyl ring21And R22Can form a ring with each other; r5Selected from hydrogen and substituted or unsubstituted C1～C10Linear alkyl, substituted or unsubstituted C of3～C10Branched alkyl or cycloalkyl of, preferably C1-C6Alkyl group of (1).
According to a preferred embodiment of the invention, M is nickel and X is halogen.
According to the invention, said substitution means R1-R4、R5、R9-R10、R1-R10、R21Or R22The hydrocarbon group in (1), preferably alkyl, cycloalkyl, aryl, alkylaryl or arylalkyl group, may be optionally substituted with a heteroatom at a carbon atom in the main chain, and the hydrogen atom bonded to the carbon atom may be optionally substituted with a heteroatom, alkyl or alkoxy group; the hetero atom includes an oxygen atom, a nitrogen atom, a boron atom, a sulfur atom, a phosphorus atom, a silicon atom, a germanium atom, a tin atom, a halogen atom and the like.
According to some embodiments of the invention, the procatalyst is selected from at least one of the metal complexes represented by formula II below:
the complex 1: r1＝R3＝R4＝R6＝Me，R2＝R5＝R7＝R8＝R9＝R10＝R21＝R22＝H，R5＝Me，X＝Br；
And (2) the complex: r1＝R3＝R4＝R6＝Et，R2＝R5＝R7＝R8＝R9＝R10＝R21＝R22＝H，R5＝Me，X＝Br；
And (3) complex: r1＝R3＝R4＝R6＝iPr，R2＝R5＝R7＝R8＝R9＝R10＝R21＝R22＝H，R5＝Me，X＝Br；
The complex 4: r1＝R3＝R4＝R6＝Me，R2＝R5＝R7＝R8＝R9＝R10＝R21＝R22＝H，R5＝Et，X＝Br；
And (3) a complex 5: r1＝R3＝R4＝R6＝Et，R2＝R5＝R7＝R8＝R9＝R10＝R21＝R22＝H，R5＝Et，X＝Br；
The complex 6: r1＝R3＝R4＝R6＝iPr，R2＝R5＝R7＝R8＝R9＝R10＝R21＝R22＝H，R5＝Et，X＝Br；
The complex 7: r1＝R3＝R4＝R6＝Me，R2＝R5＝R7＝R8＝R9＝R10＝R21＝R22＝H，R5＝Me，X＝Cl；
The complex 8: r1＝R3＝R4＝R6＝Et，R2＝R5＝R7＝R8＝R9＝R10＝R21＝R22＝H，R5＝Me，X＝Cl；
The complex 9: r1＝R3＝R4＝R6＝iPr，R2＝R5＝R7＝R8＝R9＝R10＝R21＝R22＝H，R5＝Me，X＝Cl；
The complex 10: r1＝R3＝R4＝R6＝Me，R2＝R5＝R7＝R8＝R9＝R10＝R21＝R22＝H，R5＝Et，X＝Cl；
The complex 11: r1＝R3＝R4＝R6＝Et，R2＝R5＝R7＝R8＝R9＝R10＝R21＝R22＝H，R5＝Et，X＝Cl；
The complex 12: r1＝R3＝R4＝R6＝iPr，R2＝R5＝R7＝R8＝R9＝R10＝R21＝R22＝H，R5＝Et，X＝Cl；
The complex 13:
Figure BDA0001849843210000051
the complex 14:
Figure BDA0001849843210000052
the complex 15:
Figure BDA0001849843210000053
the compound 16:
Figure BDA0001849843210000054
the complex 17:
Figure BDA0001849843210000055
the complex 18:
Figure BDA0001849843210000061
according to some embodiments of the present invention, the concentration of the main catalyst in the reaction system is 0.0001 to 1000mmol/L, for example, 0.0001mmol/L, 0.0005mmol/L, 0.001mmol/L, 0.005mmol/L, 0.01mmol/L, 0.05mmol/L, 0.1mmol/L, 0.3mmol/L, 0.5mmol/L, 0.8mmol/L, 1mmol/L, 5mmol/L, 8mmol/L, 10mmol/L, 20mmol/L, 30mmol/L, 50mmol/L, 70mmol/L, 80mmol/L, 100mmol/L, 200mmol/L, 300mmol/L, 500mmol/L, 700mmol/L, 800mmol/L, 1000mmol/L and any value therebetween, preferably 0.001 to 50mmol/L, more preferably 0.01 to 10 mmol/L.
According to some embodiments of the invention, the cocatalyst is selected from an organoaluminium compound and/or an organoboron compound.
According to a preferred embodiment of the invention, the organoaluminium compound is chosen from alkylaluminoxanes or compounds of general formula AlR "n' X13-n 'organoaluminum compound (aluminum alkyl or aluminum alkyl halide) of the general formula AlR "n' X1In 3-n ', R' is selected from hydrogen and C1-C20Or C is a hydrocarbon group1-C20Hydrocarbyloxy, preferably C1-C20Alkyl radical, C1-C20Alkoxy radical, C7-C20Aralkyl or C6-C20An aryl group; x1Is halogen, preferably chlorine or bromine; 0<n' is less than or equal to 3. Specific examples of the organoaluminum compound include, but are not limited to: trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, trioctylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride, Methylaluminoxane (MAO) and Modified Methylaluminoxane (MMAO). Preferably, the organoaluminum compounds are Methylaluminoxane (MAO) and diethylaluminum monochloride.
According to a preferred embodiment of the invention, the organoboron compound is selected from an aryl boron and/or a borate. The arylborole is preferably a substituted or unsubstituted phenylborone, more preferably tris (pentafluorophenyl) boron. The borate is preferably N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and/or triphenylmethyl tetrakis (pentafluorophenyl) borate.
According to a preferred embodiment of the present invention, when the cocatalyst is an organoaluminum compound, the molar ratio of aluminum in the cocatalyst to M in the procatalyst is (1-10000000):1, e.g. 1:1, 5:1, 10:1, 20:1, 50:1, 100:1, 200:1, 300:1, 500:1, 700:1, 800:1, 1000:1, 2000:1, 3000:1, 5000:1, 10000:1, 100000:1, 1000000:1, 10000000:1 and any value in between, preferably (1-100000):1, more preferably (10-10000): 1; when the cocatalyst is an organoboron compound, the molar ratio of boron in the cocatalyst to M in the procatalyst is (0.1-1000):1, for example, 0.1:1, 0.2:1, 0.5:1, 0.7:1, 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 6:1, 7:1, 8:1, 10:1, 20:1, 50:1, 100:1, 200:1, 300:1, 500:1, 700:1, 800:1, 1000:1, and any value therebetween, preferably (0.1-500): 1.
According to some embodiments of the invention, the conditions of the polymerization reaction comprise: the reaction temperature is-78 ℃ to 200 ℃, preferably-20 ℃ to 150 ℃, more preferably 0 to 100 ℃; the reaction time is 10-200min, preferably 20-60 min.
In the present invention, the "reaction system" is meant to include the totality of the solvent, propylene and the catalyst.
According to another aspect of the present invention, there is also provided a method for preparing the above metal complex as a procatalyst, comprising the steps of:
(1) reacting α -diimine compound with organic metal compound under anhydrous and oxygen-free conditions, and hydrolyzing to obtain amino imine ligand, wherein the α -diimine compound has a structure shown in formula III, and the amino imine ligand has a structure shown in formula IV:
Figure BDA0001849843210000071
(2) carrying out coordination reaction on the amino imine ligand prepared in the step (1) and MXn or derivatives thereof under anhydrous and oxygen-free conditions to obtain the metal complex; wherein M is a group VIII metal, preferably nickel; x is selected from halogen and substituted or unsubstituted hydrocarbyl, preferably halogen.
According to some embodiments of the invention, in formula III, R1-R4、R9And R10Is as defined in formula I; in the formula IV, R1-R4、R5、R9And R10Is as defined in formula I.
According to a preferred embodiment of the present invention, the α -diimine compound has a structure as shown in formula V, and the aminoimine ligand has a structure as shown in formula VI:
Figure BDA0001849843210000081
in the formula V, R1-R10、R21And R22Is as defined in formula II; in the formula VI, R1-R10、R5、R21And R22Is as defined in formula II.
According to a preferred embodiment of the present invention, the α -diimine compound is selected from at least one of the compounds represented by the following formula V:
compound 1: r1＝R3＝R4＝R6＝Me，R2＝R5＝R7＝R8＝R9＝R10＝R21＝R22＝H；
Compound 2: r1＝R3＝R4＝R6＝Et，R2＝R5＝R7＝R8＝R9＝R10＝R21＝R22＝H；
Compound 3: r1＝R3＝R4＝R6＝iPr，R2＝R5＝R7＝R8＝R9＝R10＝R21＝R22＝H；
Compound 4:
Figure BDA0001849843210000082
compound 5:
Figure BDA0001849843210000083
compound 6:
Figure BDA0001849843210000084
according to a preferred embodiment of the present invention, the aminoimine ligand is selected from at least one of the compounds represented by the following formula VI:
ligand 1: r1＝R3＝R4＝R6＝Me，R2＝R5＝R7＝R8＝R9＝R10＝R21＝R22＝H，R5＝Me；
Ligand 2: r1＝R3＝R4＝R6＝Et，R2＝R5＝R7＝R8＝R9＝R10＝R21＝R22＝H，R5＝Me；
Ligand 3: r1＝R3＝R4＝R6＝iPr，R2＝R5＝R7＝R8＝R9＝R10＝R21＝R22＝H，R5＝Me；
Ligand 4: r1＝R3＝R4＝R6＝Me，R2＝R5＝R7＝R8＝R9＝R10＝R21＝R22＝H，R5＝Et；
Ligand 5: r1＝R3＝R4＝R6＝Et，R2＝R5＝R7＝R8＝R9＝R10＝R21＝R22＝H，R5＝Et；
Ligand 6: r1＝R3＝R4＝R6＝iPr，R2＝R5＝R7＝R8＝R9＝R10＝R21＝R22＝H，R5＝Et；
Ligand 7:
Figure BDA0001849843210000091
ligand 8:
Figure BDA0001849843210000092
ligand 9:
Figure BDA0001849843210000093
according to some embodiments of the invention, the organometallic compound in step (1) comprises organometallic compounds of the formulae M 'Ra (VII) and M' RaX 'y-a (VIII), formula VII wherein M' is a metal selected from the group consisting of chlorine, zinc, lithium and magnesium; r is selected from C1-10Preferably methyl, ethyl, propyl or butyl; a is an integer satisfying a metal valence state; in formula VIII, M' is a metal selected from chlorine, zinc, lithium and magnesium; r is selected from C1-10Preferably methyl, ethyl, propyl or butyl; x' is halogen, a is an integer of 1 to 3, and y is an integer satisfying a metal valence.
According to a preferred embodiment of the invention, the organometallic compound is chosen from Grignard reagents (MgRX', wherein R is chosen from C)1-10X' is halogen), an alkylaluminum compound, an alkylzinc compound, and an alkyllithium compound.
According to some embodiments of the invention, the MXn or derivative thereof in said step (2) is selected from nickel halides and derivatives thereof, preferably from NiBr2、NiCl2、(DME)NiBr2And (DME) NiCl2。
According to a preferred embodiment of the present invention, the reaction temperature of step (1) is 10 to 120 ℃, preferably 20 to 110 ℃; the reaction time is 2-12h, preferably 3-10 h.
According to a preferred embodiment of the present invention, the reaction temperature of step (2) is 0 to 60 ℃, preferably 20 to 40 ℃; the reaction time is 0.5 to 12 hours, preferably 3 to 8 hours.
According to a further aspect of the present invention there is provided the use of said propylene polymer for the preparation of a fibre, film, medical device or packaging material. The propylene polymer is an elastomer material without double bonds in a molecular chain structure, has excellent tensile and impact resistance, optical property, oxidation resistance and anti-aging property, and has wide application prospect in the aspects of preparing fibers, films, medical instruments or packaging materials and the like.
Compared with the prior art, the invention has the following advantages: the invention can catalyze propylene to polymerize with higher activity at higher temperature to prepare completely random polypropylene, the molecular weight distribution of the polymer is narrower, the molecular weight of the obtained polymer can be regulated and controlled within a certain range by regulating the structure of the complex serving as a main catalyst, and the invention has wide application prospect in the aspects of fibers, films, medical devices, packages and the like.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention in any way.
In the following examples, the evaluation and testing methods involved are as follows:
molecular weight and molecular weight distribution PDI (PDI ═ Mw/Mn) of the polymer: measured at 150 ℃ using PL-GPC220 and 1,2, 4-trichlorobenzene as a solvent (standard: PS, flow rate: 1.0mL/min, column: 3 XPlgel 10um M1 XED-B300X 7.5 nm).
The melting point of the polymer was measured using Differential Scanning Calorimetry (DSC): 10mg of the sample was placed in a crucible and measured on a Pekinelmer DSC 8500 differential scanning calorimeter. Raising the temperature from 0 ℃ to 200 ℃ at a heating rate of 10 ℃/min under the nitrogen atmosphere, preserving the heat for l min, lowering the temperature to 0 ℃ at 10 ℃/min, preserving the heat for 3min, then raising the temperature to 200 ℃ at 10 ℃/min, and recording the second heating scanning data.
The nuclear magnetism of the product is measured by a Bruker DMX 300(300MHz) nuclear magnetic resonance instrument, and Tetramethylsilicon (TMS) is taken as an internal standard.
Example 1
(1) Preparation of ligand 1: 3.52g (8mmol) of alpha-diimine compound 1, sequentially adding 30ml of toluene and 1M of trimethylaluminum (8ml and 8mmol), refluxing for 8 hours, stopping the reaction with sodium hydroxide/ice water, extracting with ethyl acetate, combining organic phases, drying with anhydrous magnesium sulfate, and separating the product by petroleum ether/ethyl acetate column chromatography to obtain colorless crystal ligand 1 with the yield of 85.2%;
1HNMRδ(ppm)7.23-6.88(m,14H),4.84(s,1H),4.73(s,1H),3.85(s,1H,NH),2.02(s,3H,CH3),1.87(s,6H,CH3),1.75(s,6H,CH3)；
(2) preparation of Complex 1: 10ml of (DME) NiBr2(277mg,0.9mmol) of a dichloromethane solution was added dropwise to a 10ml dichloromethane solution of ligand 1(411mg,0.9mmol), stirred at room temperature for 6 hours, precipitated, filtered, washed with ether and dried to obtain a red powdery solid with a yield of 84%; elemental analysis (C)33H32Br2N2Ni): c, 58.71; h, 4.78; n, 4.15; experimental values (%): c, 58.57; h, 4.93; n, 4.08;
(3) polymerization of propylene: adding 13.4mg (20 mu mol) of complex 1 into a 48-channel parallel pressure reactor (PPR, reaction volume 20ml), replacing the reactor with propylene, adding 5ml of Methylaluminoxane (MAO), filling propylene gas, controlling pressure to be 1Mpa, and reacting at 20 ℃ for 1 hour; discharging, neutralizing with 5% hydrochloric acid acidified ethanol solution, drying to obtain polypropylene, and calculating to obtain catalyst activity; the weight average molecular weight Mw and the molecular weight distribution Mw/Mn of the polymer were measured at the same time, and the results are shown in Table 1.
Example 2
The steps (1) and (2) are the same as those in example 1;
(3) polymerization of propylene: adding 13.4mg (20 mu mol) of complex 1 into a 48-channel parallel pressure reactor (PPR, reaction volume 20ml), replacing the reactor with propylene, adding 5ml of Methylaluminoxane (MAO), filling propylene gas, controlling pressure to be 1Mpa, and reacting at 40 ℃ for 1 hour; discharging, neutralizing with 5% hydrochloric acid acidified ethanol solution, drying to obtain polypropylene, and calculating to obtain catalyst activity; the weight average molecular weight Mw and the molecular weight distribution Mw/Mn of the polymer were measured at the same time, and the results are shown in Table 1.
Example 3
The steps (1) and (2) are the same as those in example 1;
(3) polymerization of propylene: adding 13.4mg (20 mu mol) of complex 1 into a 48-channel parallel pressure reactor (PPR, reaction volume 20ml), replacing the reactor with propylene, adding 5ml of Methylaluminoxane (MAO), filling propylene gas, controlling pressure to be 1Mpa, and reacting at 60 ℃ for 1 hour; discharging, neutralizing with 5% hydrochloric acid acidified ethanol solution, drying to obtain polypropylene, and calculating to obtain catalyst activity; the weight average molecular weight Mw and the molecular weight distribution Mw/Mn of the polymer were measured at the same time, and the results are shown in Table 1.
Example 4
The steps (1) and (2) are the same as those in example 1;
(3) polymerization of propylene: adding 13.4mg (20 mu mol) of complex 1 into a 48-channel parallel pressure reactor (PPR, reaction volume 20ml), replacing the reactor with propylene, adding 5ml of Methylaluminoxane (MAO), filling propylene gas, controlling pressure to be 1Mpa, and reacting at 80 ℃ for 1 hour; discharging, neutralizing with 5% hydrochloric acid acidified ethanol solution, drying to obtain polypropylene, and calculating to obtain catalyst activity; the weight average molecular weight Mw and the molecular weight distribution Mw/Mn of the polymer were measured at the same time, and the results are shown in Table 1.
Example 5
The steps (1) and (2) are the same as those in example 1;
(3) polymerization of propylene: 13.4mg (20. mu. mol) of complex 1 was charged into a 48-channel parallel pressure reactor (PPR, reaction volume 20ml), the reactor was purged with propylene, 2ml of diethylaluminum monochloride (2.0mol/L in toluene) was charged, the pressure was controlled at 1MPa, and the reaction was carried out at 80 ℃ for 1 hour; discharging, neutralizing with 5% hydrochloric acid acidified ethanol solution, drying to obtain polypropylene, and calculating to obtain catalyst activity; the weight average molecular weight Mw and the molecular weight distribution Mw/Mn of the polymer were measured at the same time, and the results are shown in Table 1.
Example 6
(1) Preparation of ligand 3: 3.52g (8mmol) of alpha-diimine compound 3, sequentially adding 30ml of toluene and 1M of trimethylaluminum (8ml and 8mmol), refluxing for 8 hours, stopping the reaction with sodium hydroxide/ice water, extracting with ethyl acetate, combining organic phases, drying with anhydrous magnesium sulfate, and separating the product by petroleum ether/ethyl acetate column chromatography to obtain colorless crystal ligand 3 with the yield of 76.2%;
1HNMRδ(ppm)7.21-6.95(m,14H),4.96(s,1H),4.87(s,1H),3.85(s,1H,NH),2.51(m,4H,CH(CH3)2),2.02(s,3H,CH3),1.18(d,3H,CH3),1.11(d,3H,CH3),1.05(d,6H,CH3),0.98(d,6H,CH3),0.60(d,6H,CH3)；
(2) preparation of Complex 3: 10ml of (DME) NiBr2(277mg,0.9mmol) of a dichloromethane solution was added dropwise to a 10ml dichloromethane solution of ligand 3(512mg,0.9mmol), stirred at room temperature for 6 hours, precipitated, filtered, washed with ether and dried to obtain a red powdery solid with a yield of 86%; elemental analysis (C)41H48Br2N2Ni): c, 62.55; h, 6.15; n, 3.56; experimental values (%): c, 62.21; h, 6.43; n, 3.44;
(3) polymerization of propylene: in a 48-channel parallel pressure reactor (PPR, reaction volume 20ml), 15.8mg (20. mu. mol) of complex 3 was added, the reactor was replaced with propylene, 5ml of Methylaluminoxane (MAO) was added, propylene gas was charged, pressure was controlled at 1MPa, and the reaction was carried out at 20 ℃ for 1 hour; discharging, neutralizing with 5% hydrochloric acid acidified ethanol solution, drying to obtain polypropylene, and calculating to obtain catalyst activity; the weight average molecular weight Mw and the molecular weight distribution Mw/Mn of the polymer were measured at the same time, and the results are shown in Table 1.
Example 7
The steps (1) and (2) are the same as in example 6;
(3) polymerization of propylene: in a 48-channel parallel pressure reactor (PPR, reaction volume 20ml), 15.8mg (20. mu. mol) of complex 3 was added, the reactor was replaced with propylene, 5ml of Methylaluminoxane (MAO) was added, propylene gas was charged, pressure was controlled at 1MPa, and the reaction was carried out at 40 ℃ for 1 hour; discharging, neutralizing with 5% hydrochloric acid acidified ethanol solution, drying to obtain polypropylene, and calculating to obtain catalyst activity; the weight average molecular weight Mw and the molecular weight distribution Mw/Mn of the polymer were measured at the same time, and the results are shown in Table 1.
Example 8
The steps (1) and (2) are the same as in example 6;
(3) polymerization of propylene: in a 48-channel parallel pressure reactor (PPR, reaction volume 20ml), 15.8mg (20. mu. mol) of complex 3 was added, the reactor was replaced with propylene, 5ml of Methylaluminoxane (MAO) was added, propylene gas was charged, pressure was controlled at 1MPa, and the reaction was carried out at 60 ℃ for 1 hour; discharging, neutralizing with 5% hydrochloric acid acidified ethanol solution, drying to obtain polypropylene, and calculating to obtain catalyst activity; the weight average molecular weight Mw and the molecular weight distribution Mw/Mn of the polymer were measured at the same time, and the results are shown in Table 1.
Example 9
The steps (1) and (2) are the same as in example 6;
(3) polymerization of propylene: in a 48-channel parallel pressure reactor (PPR, reaction volume 20ml), 15.8mg (20. mu. mol) of complex 3 was added, the reactor was replaced with propylene, 5ml of Methylaluminoxane (MAO) was added, propylene gas was charged, pressure was controlled at 1MPa, and the reaction was carried out at 80 ℃ for 1 hour; discharging, neutralizing with 5% hydrochloric acid acidified ethanol solution, drying to obtain polypropylene, and calculating to obtain catalyst activity; the weight average molecular weight Mw and the molecular weight distribution Mw/Mn of the polymer were measured at the same time, and the results are shown in Table 1.
Example 10
The steps (1) and (2) are the same as in example 6;
(3) polymerization of propylene: in a 48-channel parallel pressure reactor (PPR, reaction volume 20ml), 15.8mg (20. mu. mol) of complex 3 was added, the reactor was replaced with propylene, 2ml of diethylaluminum monochloride (2.0mol/L in toluene) was added, propylene gas was charged, pressure was controlled at 1MPa, and the reaction was carried out at 40 ℃ for 1 hour; discharging, neutralizing with 5% hydrochloric acid acidified ethanol solution, drying to obtain polypropylene, and calculating to obtain catalyst activity; the weight average molecular weight Mw and the molecular weight distribution Mw/Mn of the polymer were measured at the same time, and the results are shown in Table 1.
Example 11
(1) Preparation of ligand 4: 3.52g (8mmol) of alpha-diimine compound 1, adding 30ml of diethyl ether and 2M diethyl zinc (4ml, 8mmol) in sequence, stirring at normal temperature for 3 hours, stopping the reaction with ice water, extracting with ethyl acetate, combining organic phases, drying with anhydrous magnesium sulfate, and separating the product by petroleum ether/ethyl acetate column chromatography to obtain colorless crystal ligand 4 with the yield of 50.1%;
1HNMRδ(ppm)7.22-6.86(m,14H),4.82(s,1H),4.73(s,1H),3.85(s,1H,NH),2.04(m,2H,CH2CH3),1.89(s,6H,CH3),1.74(s,6H,CH3),0.89(t,3H,CH3)；
(2) fitting togetherPreparation of substance 4: 10ml of (DME) NiBr2(277mg,0.9mmol) of a dichloromethane solution was added dropwise to a 10ml dichloromethane solution of ligand 4(424mg,0.9mmol), stirred at room temperature for 6 hours, precipitated, filtered, washed with ether and dried to give a red powdery solid with a yield of 83%; elemental analysis (C)34H34Br2N2Ni): c, 59.26; h, 4.97; n, 4.06; experimental values (%): c, 59.39; h, 5.13; n, 4.24;
(3) polymerization of propylene: adding 13.8mg (20 mu mol) of complex 4 into a 48-channel parallel pressure reactor (PPR, reaction volume 20ml), replacing the reactor with propylene, adding 5ml of Methylaluminoxane (MAO), filling propylene gas, controlling pressure to be 1Mpa, and reacting at 60 ℃ for 1 hour; discharging, neutralizing with 5% hydrochloric acid acidified ethanol solution, drying to obtain polypropylene, and calculating to obtain catalyst activity; the weight average molecular weight Mw and the molecular weight distribution Mw/Mn of the polymer were measured at the same time, and the results are shown in Table 1.
Example 12
The steps (1) and (2) are the same as in example 11;
(3) polymerization of propylene: adding 13.8mg (20 mu mol) of complex 4 into a 48-channel parallel pressure reactor (PPR, reaction volume 20ml), replacing the reactor with propylene, adding 5ml of Methylaluminoxane (MAO), filling propylene gas, controlling pressure to be 1Mpa, and reacting at 80 ℃ for 1 hour; discharging, neutralizing with 5% hydrochloric acid acidified ethanol solution, drying to obtain polypropylene, and calculating to obtain catalyst activity; the weight average molecular weight Mw and the molecular weight distribution Mw/Mn of the polymer were measured at the same time, and the results are shown in Table 1.
Example 13
(1) Preparation of ligand 7: 4.32g (8mmol) of alpha-diimine compound 4, adding 30ml of diethyl ether and 1M of trimethylaluminum (8ml and 8mmol) in sequence, stirring at normal temperature for 3 hours, stopping the reaction with ice water, extracting with ethyl acetate, combining organic phases, drying with anhydrous magnesium sulfate, and separating the product by petroleum ether/ethyl acetate column chromatography to obtain colorless crystal ligand 7 with the yield of 72.1%;
1HNMRδ(ppm)7.68-7.54(m,8H),7.37(m,4H),7.11-7.04(m,6H),5.16(s,1H),5.08(s,1H),4.05(s,1H,NH),1.94(s,3H,CH3),1.89(s,6H,CH3),1.73(s,6H,CH3)；
(2) preparation of Complex 13: 10ml of (DME) NiBr2(277mg,0.9mmol) of a dichloromethane solution was added dropwise to a 10ml dichloromethane solution of ligand 7(501mg,0.9mmol), stirred at room temperature for 6 hours, precipitated, filtered, washed with ether and dried to obtain a red powdery solid with a yield of 82%; elemental analysis (C)41H36Br2N2Ni): c, 63.52; h, 4.68; n, 3.61; experimental values (%): c, 63.74; h, 4.93; n, 3.44;
(3) polymerization of propylene: in a 48-channel parallel pressure reactor (PPR, reaction volume 20ml), 15.4mg (20. mu. mol) of complex 13 was added, the reactor was replaced with propylene, 5ml of Methylaluminoxane (MAO) was added, propylene gas was charged, pressure was controlled at 1MPa, and the reaction was carried out at 60 ℃ for 1 hour; discharging, neutralizing with 5% hydrochloric acid acidified ethanol solution, drying to obtain polypropylene, and calculating to obtain catalyst activity; the weight average molecular weight Mw and the molecular weight distribution Mw/Mn of the polymer were measured at the same time, and the results are shown in Table 1.
Example 14
The steps (1) and (2) are the same as in example 13;
(3) polymerization of propylene: in a 48-channel parallel pressure reactor (PPR, reaction volume 20ml), 15.4mg (20. mu. mol) of complex 13 was added, the reactor was replaced with propylene, 5ml of Methylaluminoxane (MAO) was added, propylene gas was charged, pressure was controlled at 1MPa, and the reaction was carried out at 80 ℃ for 1 hour; discharging, neutralizing with 5% hydrochloric acid acidified ethanol solution, drying to obtain polypropylene, and calculating to obtain catalyst activity; the weight average molecular weight Mw and the molecular weight distribution Mw/Mn of the polymer were measured at the same time, and the results are shown in Table 1.
Comparative example 1
Polymerization of propylene: in a 48-channel parallel pressure reactor (PPR, reaction volume 20ml), 14.6mg (20. mu. mol) of comparative catalyst A (whose structure is shown in formula i below) was charged, the reactor was replaced with propylene, 5ml of Methylaluminoxane (MAO) was charged, and the reaction was carried out at 80 ℃ for 1 hour under a controlled pressure of 1MPa with propylene gas; discharging, neutralizing with 5% hydrochloric acid acidified ethanol solution, and drying. The activity of the catalyst in propylene polymerization is too low and substantially no polymer is formed.
Figure BDA0001849843210000161
Comparative example 2
In a 48-channel parallel pressure reactor (PPR, reaction volume 20ml), 12.8mg (20. mu. mol) of comparative catalyst B (having the structure shown in the following formula ii) was charged, the reactor was replaced with propylene, 5ml of Methylaluminoxane (MAO) was charged, and the reaction was carried out at 80 ℃ for 1 hour under a controlled pressure of 1MPa with a propylene gas. Discharging, neutralizing with 5% hydrochloric acid acidified ethanol solution, and drying. The activity of the catalyst in propylene polymerization is too low and substantially no polymer is formed.
Figure BDA0001849843210000162
TABLE 1
Examples Activity/(10)3g/molcat.h) Mw×10-4 Mw/Mn
Example 1 2.2 3.7 1.3
Example 2 4.3 5.4 1.3
Example 3 6.6 11.2 1.3
Example 4 7.3 9.8 1.4
Example 5 7.0 9.1 1.4
Example 6 0.8 24.0 1.5
Example 7 1.3 28.6 1.5
Example 8 2.6 34.8 1.5
Example 9 3.3 32.1 1.5
Example 10 3.1 21.4 1.5
Example 11 1.3 9.2 1.5
Example 12 2.4 8.0 1.5
Example 13 7.3 13.1 1.4
Example 14 7.9 11.8 1.4
The invention can catalyze propylene to polymerize with higher activity at higher temperature to prepare completely random polypropylene, and the molecular weight of the obtained polymer is regulated and controlled within a certain range by regulating the structure of the complex.
Any numerical value mentioned in this specification, if there is only a two unit interval between any lowest value and any highest value, includes all values from the lowest value to the highest value incremented by one unit at a time. For example, if it is stated that the amount of a component, or a value of a process variable such as temperature, pressure, time, etc., is 50 to 90, it is meant in this specification that values of 51 to 89, 52 to 88 … …, and 69 to 71, and 70 to 71, etc., are specifically enumerated. For non-integer values, units of 0.1, 0.01, 0.001, or 0.0001 may be considered as appropriate. These are only some specifically named examples. In a similar manner, all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be disclosed in this application.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.

Claims (10)

1. A propylene polymer, said propylene polymer being a random propylene polymer having a weight average molecular weight of 30000-400000 and a molecular weight distribution of 1.0-3.0.
2. The propylene polymer according to claim 1, wherein the propylene polymer is a random propylene polymer having no melting point and a molecular weight distribution of 1.0 to 1.5.
3. A process for the preparation of a propylene polymer as claimed in claim 1 or 2, comprising contacting propylene with a catalyst under olefin polymerization conditions; the catalyst comprises a main catalyst and a cocatalyst, wherein the main catalyst is selected from a metal complex shown in a formula I:
Figure FDA0001849843200000011
in the formula I, R1-R4Same or different, each independently selected from hydrogen, halogen and substituted or unsubstituted C1-C20A hydrocarbon group of R1-R4Can form rings with each other arbitrarily; r5Selected from hydrogen and substituted or unsubstitutedSubstituted C1-C20A hydrocarbon group of (a); r9And R10Same or different, each independently selected from substituted or unsubstituted C1-C30A hydrocarbon group of (a); m is a group VIII metal; x is selected from the group consisting of halogen and substituted or unsubstituted hydrocarbyl; n is an integer satisfying the valence of M.
4. The process according to claim 3, wherein R in the formula I1-R4Same or different, each independently selected from hydrogen and substituted or unsubstituted C1-C10A hydrocarbon group of R1-R4Can form rings with each other arbitrarily; preferably R1And R4Bonded to form a ring, R2And R3Bonding to form a ring; r5Selected from hydrogen and substituted or unsubstituted C1-C10Is preferably C1-C10More preferably C1-C6Alkyl groups of (a); r9And R10Same or different, each independently selected from substituted or unsubstituted C1-C30Is preferably C1-C20More preferably C1-C20An alkylaryl group of (a); m is a group VIII metal; x is selected from the group consisting of halogen and substituted or unsubstituted hydrocarbyl; n is an integer satisfying the valence of M.
5. The method according to claim 3 or 4, wherein the procatalyst is selected from the group consisting of metal complexes represented by formula II:
Figure FDA0001849843200000021
in the formula II, R1-R10Same or different, each independently selected from hydrogen, halogen and substituted or unsubstituted C1-C20Is preferably C1-C10More preferably C1-C6Alkyl of R1-R10Can form rings with each other arbitrarily; r21And R22Identical or different, each independently selected from hydrogen, halogen and substituted or unsubstitutedHydrocarbyl, preferably C1-C10The hydrocarbon group of (A), R being on the same benzene ring21And R22R which may form a ring with each other, more preferably on the same benzene ring21And R22Are mutually bonded to form a benzene ring; r5Selected from hydrogen and substituted or unsubstituted C1-C10Is preferably C1-C10More preferably C1-C6Alkyl groups of (a); m is a group VIII metal, preferably nickel; x is selected from halogen and substituted or unsubstituted hydrocarbyl, preferably halogen.
6. The preparation method according to claim 5, wherein the concentration of the main catalyst in the reaction system is 0.0001 to 1000mmol/L, preferably 0.001 to 50 mmol/L.
7. The production method according to any one of claims 3 to 6, wherein the co-catalyst is selected from an organoaluminum compound and/or an organoboron compound;
the organic aluminum compound is selected from one or more of alkyl aluminoxane, alkyl aluminum and alkyl aluminum halide;
and/or the organoboron compound is selected from an aryl boron and/or a borate.
8. The process according to any one of claims 3 to 7, wherein when the cocatalyst is an organoaluminum compound, the molar ratio of aluminum in the cocatalyst to M in the procatalyst is (1-10000000):1, preferably (1-100000):1, more preferably (10-10000): 1; when the cocatalyst is an organic boron compound, the molar ratio of boron in the cocatalyst to M in the main catalyst is (0.1-1000):1, preferably (0.1-500): 1.
9. The production method according to any one of claims 3 to 8, wherein the polymerization reaction conditions include: the reaction temperature is-78 ℃ to 200 ℃, preferably-20 ℃ to 150 ℃; and/or the reaction time is 10-200min, preferably 20-60 min.
10. Use of the propylene polymer according to claim 1 or 2 or the propylene polymer produced by the production process according to any one of claims 3 to 9 for the production of fibers, films, medical devices or packaging materials.
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Citations (2)

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Publication number Priority date Publication date Assignee Title
US5596052A (en) * 1992-12-30 1997-01-21 Montell Technology Company Bv Atactic polypropylene
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Publication number Priority date Publication date Assignee Title
US5596052A (en) * 1992-12-30 1997-01-21 Montell Technology Company Bv Atactic polypropylene
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Title
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赖菁菁等: "《α-二亚胺镍催化剂催化乙烯溶液聚合的性能》", 《合成树脂及塑料》 *

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