CN108570119B - Solid catalyst component containing naphthalenediamine compound, catalyst and application thereof - Google Patents

Solid catalyst component containing naphthalenediamine compound, catalyst and application thereof Download PDF

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CN108570119B
CN108570119B CN201710140629.XA CN201710140629A CN108570119B CN 108570119 B CN108570119 B CN 108570119B CN 201710140629 A CN201710140629 A CN 201710140629A CN 108570119 B CN108570119 B CN 108570119B
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naphthalenediamine
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catalyst component
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CN108570119A (en
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王志武
李树行
李华姝
张军伟
胡乐
代金松
马庆利
高勇
陈颢
焦文杰
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Renqiu Lihe Technology Ltd.
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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
    • 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
    • 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

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Abstract

The invention provides a solid catalyst component containing a naphthalenediamine compound, which comprises Mg, Ti, halogen and at least one electron donor, wherein the electron donor is a1, 8-naphthalenediamine compound selected from a general formula (I). The invention also discloses a catalyst containing the solid catalyst component and application of the catalyst in olefin polymerization reaction, in particular application in propylene polymerization reaction. The catalyst has high activity, the obtained polymer has high isotacticity and wide and adjustable molecular weight distribution, and when the catalyst is compounded with a diether compound to be used as an internal electron donor, the low-ash polymer can be produced.

Description

Solid catalyst component containing naphthalenediamine compound, catalyst and application thereof
Technical Field
The invention relates to a method for CH2The present invention relates to a solid catalyst component for the polymerization of olefins, wherein R is hydrogen or a hydrocarbyl group containing from 1 to 12 carbon atoms, more particularly to a solid catalyst component containing a naphthalenediamine compound, a catalyst containing the solid catalyst component and the use of the catalyst in the polymerization of olefins, in particular propylene.
Background
In the propylene polymerization industry, the most widely studied and used catalyst is the Ziegler-Natta catalyst, which is prepared by adding an internal electron donor during the titanium loading of an active magnesium chloride support. Since the internal electron donor can change the catalyst performance to the greatest extent, research and search of an ideal internal electron donor compound become a focus and hot spot of research on Z-N catalysts. At present, the research on internal electron donors at home and abroad mainly focuses on: 1) traditional fatty acid ester and aromatic acid ester compounds, mainly represented by phthalate ester compounds; 2) diethers (e.g. EP0361493, EP 0728724); 3) succinate compounds (e.g. WO9856834, WO0063261, WO 03022894); 4) glycol ester compounds (e.g., WO9856834, WO0063261, WO 03022894); 5) other functional group compounds (CN1105671, CN1242780, US20060128558) and the like.
However, in practical applications, the above compounds have certain problems as internal electron donors of catalysts for olefin polymerization, such as low activity of catalysts using binary aromatic carboxylic acid ester compounds as internal electron donors, narrow relative molecular mass distribution of the Prepared Polypropylene (PP), and great harm to human reproductive health and environment due to the use of phthalate compounds as common plasticizers; although the catalyst using the 1, 3-diether compound as the internal electron donor has high activity and good hydrogen regulation sensitivity, the prepared PP has narrow relative molecular mass distribution and is not beneficial to developing PP with different brands; the succinate compound is used as an internal electron donor, has the advantages that the synthesized PP has wider relative molecular mass distribution, and has the defects that the stereoregularity of the PP and the hydrogen regulation sensitivity of the catalyst need to be improved; the activity of the glycol ester catalytic system is not as good as that of the diether system.
The 1, 3-diether compound needs to be prepared through two-step reaction, the production flow is longer, the preparation yield of the succinate compound is lower, and the main raw materials of the diol ester compound such as 2, 4-pentanediol are difficult to prepare and have higher price, so the production cost of the electron donor compound is higher, and the market popularization of the product is not facilitated.
Therefore, it is an object of the industry to develop a novel electron donor with excellent activity, good stereospecificity, wide or adjustable molecular weight distribution, good polymer comprehensive properties, and low production cost, and apply the electron donor in the preparation of high-efficiency Ziegler-Natta catalysts. The 1, 8-naphthalenediamine compound provided by the invention can better solve the problems.
In addition, when the catalyst prepared by adopting a single internal electron donor cannot meet the specific requirements of a polypropylene product, for example, the catalyst is required to have the characteristics of high activity, high stereospecificity and high hydrogen response, the compounding use of multiple internal electron donors is also an effective method for solving the problem, namely when the Z-N catalyst is prepared, two or more than two internal electron donors are used simultaneously, and the comprehensive performance of the Z-N catalyst is improved by adjusting the content of different internal electron donors in the Z-N catalyst.
Disclosure of Invention
The invention aims to provide a method for CH2Solid catalyst component for CHR olefin polymerization.
It is another object of the present invention to provide a method for preparing the solid catalyst component.
It is a further object of the present invention to provide the solid catalyst component in CH2Use in the preparation of a CHR olefin polymerisation catalyst.
In order to achieve the object of the present invention, the present invention provides a solid catalyst Component (CH) containing a naphthalenediamine compound2CHR olefins, where R is hydrogen or a hydrocarbyl group containing 1 to 12 carbon atoms), comprising Mg, Ti, halogen and at least one electron donor selected from 1, 8-naphthalenediamines of general formula (i):
Figure BDA0001242705590000021
wherein R is1-R6Identical or different, is H; halogen; c1-C20May contain one or more heteroatoms selected from N, O, S, P, Si and halogen; r1、R2、R3And R4Two or more of which may be bonded to each other to form a ring; rI-RIVIdentical or different, is H; c1-C20May contain one or more hetero atoms selected from N, O, S, P, Si and halogenAn atom which may contain an unsaturated bond; rI-RIVMay be bonded to form a ring or an unsaturated bond.
Preferably, R1-R6Identical or different, is H; halogen; c1-C20Linear or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, alkyl which is halogenated or substituted with the N, O, S, P, Si heteroatom, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl; or is selected from heterocyclic aryl substituents; r1-R6Two or more of which may be bonded to each other to form a cyclic structure, which may be saturated or unsaturated; rI-RIVIdentical or different, is H; c1-C20Linear or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, alkyl which is halogenated or substituted with the N, O, S, P, Si heteroatom, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl; or is selected from heterocyclic aryl substituents; rI—RIVMay be bonded to form a ring or an unsaturated bond.
In one embodiment, R1-R6At least one (or two, or three, or four) R group(s) in (a) is selected from the group consisting of substituted hydrocarbyl groups containing 1 to 20 carbon atoms, unsubstituted hydrocarbyl groups containing 1 to 20 carbon atoms, alkoxy groups containing 1 to 20 carbon atoms, heteroatoms, and combinations thereof.
In one embodiment, R1-R6Any adjacent R groups in (a) may be linked to form an inter-ring structure or an intra-ring structure. The inter/intra ring structures may or may not be aromatic. In one embodiment, the inter/intra ring structure is a C5 membered ring or a C6 membered ring.
Among the compounds represented by the above general formula (I), a compound represented by the following general formula (II) is preferable:
Figure BDA0001242705590000031
wherein the radical R1—R6、RIIAnd RIVHas the same meaning as in the general formula (I); r7Is C1-C20May contain one or more heteroatoms selected from N, O, S, P, Si and halogen as substituents of carbon atoms or hydrogen atoms or both, preferably being C1-C20Linear or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, alkyl which is halogenated or substituted with the N, O, S, P, Si heteroatom, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl.
Specific examples of the compounds included in the general formula (II) are:
1, 8-diethylamide-naphthalenediamine; 1, 8-di-n-propionamide-naphthalene diamine; 1, 8-diisopropylamide-naphthalene diamine; 1, 8-di-n-butylamide-naphthalenediamine; 1, 8-diisobutyramide-naphthalene diamine; 1, 8-di-n-pentanamide-naphthalene diamine; 1, 8-diisovaleramide-naphthalene diamine; 1, 8-dicyclopentanecarboxamide-naphthalenediamine; 1, 8-di-n-hexanamide-naphthalenediamine; 1, 8-dicyclohexylformamide-naphthalene diamine; 1, 8-diheptanoamide-naphthalene diamine; 1, 8-dioctylamide-naphthalenediamine; 1, 8-dinonylamide-naphthalene diamine; 1, 8-didecanamide-naphthalene diamine; 1, 8-bis [ undecamide ] -naphthalenediamine; 1, 8-bis [ dodecanamide ] -naphthalenediamine; 1, 8-bis [ tridecylamide ] -naphthalenediamine; 1, 8-ditetradecanoamide-naphthalenediamine; 1, 8-bis [ pentadecamide ] -naphthalenediamine; 1, 8-bis [ hexadecanamide ] -naphthalenediamine; 1, 8-bis [ heptadecacarboxamide ] -naphthalenediamine; 1, 8-bis [ octadecanamide ] -naphthalenediamine; 1, 8-bis [ nonadecanamide ] -naphthalenediamine; 1, 8-bis [ eicosamide ] -naphthalenediamine; 1, 8-dibenzocarboxamide-naphthalene diamine; 1, 8-di-p-chlorobenzamide-naphthalene diamine; 1, 8-di-o-chlorobenzamide-naphthalene diamine; 1, 8-m-chlorobenzamide-naphthalene diamine; 1, 8-di-p-methylbenzamide-naphthalenediamine; 1, 8-di-p-methoxybenzamide-naphthalenediamine; 1, 8-di-p-nitrobenzamide-naphthalene diamine; 1, 8-di-m-bromobenzamide-naphthalene diamine; 1, 8-diphenoxyformamide-naphthalene diamine; 1, 8-dinaphthamide-naphthalenediamine; 1, 8-di-p-trifluoromethylbenzamide-naphthalenediamine; 1, 8-dipentafluorobenzamide-naphthalenediamine; 1, 8-di-p-propylbenzamide-naphthalenediamine; 1, 8-di-p-tert-butylbenzamide-naphthalenediamine; 1, 8-di-p-isobutylbenzamide-naphthalenediamine; 1, 8-di-m-trimethylbenzamide-naphthalenediamine; 1, 8-bis [ N-benzamide-N-tert-butyl ] -naphthalenediamine; 1, 8-bis [ N-benzamide-N-phenyl ] -naphthalenediamine; 1, 8-bis [ N-benzamide-N-p-methylphenyl ] -naphthalenediamine.
1, 8-di-n-ethoxyamide-naphthylenediamine; 1, 8-di-n-propoxide-naphthalenediamine; 1, 8-di-n-butoxyamide-naphthalenediamine; 1, 8-diisobutylamide-naphthalene diamine; 1, 8-di-n-pentyloxyamide-naphthalenediamine; 1, 8-diisopentyloxyamide-naphthalenediamine; 1, 8-di-n-hexyloxyamide-naphthalenediamine; 1, 8-di-n-heptyloxyamide-naphthylenediamine; 1, 8-di-n-octyloxyamide-naphthalenediamine; 1, 8-di-n-nonanoyloxy-naphthalene diamine 1, 8-di-n-decanoyloxyamide-naphthalene diamine; 1, 8-phenoxyformamide-naphthylenediamine; 1, 8-p-methylphenyloxyformamide-naphthylenediamine; 1, 8-p-methoxyphenoxyformamide-naphthalenediamine; 1, 8-p-chlorophenoxyformamide-naphthalene diamine; 1, 8-p-nitrobenzamide-naphthalene diamine; 1, 8-m-chlorophenoxyformamide-naphthalene diamine; 1, 8-o-chlorophenoxyformamide-naphthalene diamine; 1, 8-p-trifluoromethyl-phenoxy-formamide-naphthalene diamine.
Among the compounds of the general formula (II), one is preferably a compound of the following general formula (III):
Figure BDA0001242705590000041
wherein the radical R1-R6Has the same meaning as in the general formula (I), R7Has the same meaning as in the general formula (II), R8And R8’Identical or different, selected from H; c1-C20May contain one or more heteroatoms selected from N, O, S, P, Si and halogen as substituents of carbon atoms or hydrogen atoms or both, preferably C1-C20Linear or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, alkyl which is halogenated or substituted with the N, O, S, P, Si heteroatom, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl; or is selected from heterocyclic aryl substituents.
Specific examples of the compounds included in the general formula (III) are:
1, 8-bis [ N-acetyl-N-propyl ] -naphthalenediamine; 1, 8-bis [ N-acetyl-N-isopropyl ] -naphthalenediamine; 1, 8-bis [ N-propionyl-N-butyl ] -naphthalenediamine; 1, 8-bis [ N-isobutyryl-N-isobutyl ] -naphthalenediamine; 1, 8-bis [ N-isovaleryl-N-pentyl ] -naphthalenediamine; 1, 8-bis [ N-cyclopentoyl-N-isoamyl ] -naphthalenediamine; 1, 8-bis [ N-hexanoyl-N-hexyl ] -naphthalenediamine; 1, 8-bis [ N-cyclohexanecarboxyl-N-heptyl ] -naphthalenediamine; 1, 8-bis [ N-decanoyl-N-decyl ] -naphthalenediamine; 1, 8-bis [ N-hexanoyl-N-cyclohexylmethyl ] -naphthalenediamine; 1, 8-bis [ N-cyclopentoyl-N-cyclopentylmethyl ] -naphthalenediamine; 1, 8-bis [ N-decanoyl-N-undecyl ] -naphthalenediamine; 1, 8-bis [ N-dodecanoyl-N-dodecyl ] -naphthalenediamine; 1, 8-bis [ N-isovaleryl-N-tetradecyl ] -naphthalenediamine; 1, 8-bis [ N-hexanoyl-N-hexadecyl ] -naphthalenediamine; 1, 8-bis [ N-decanoyl-N-octadecyl ] -naphthalenediamine; 1, 8-bis [ N-cyclohexanecarboxyl-N-eicosyl ] -naphthalenediamine;
1, 8-bis [ N-benzoyl-N-benzyl ] -naphthalenediamine; 1, 8-bis [ N-benzoyl-N-benzhydryl ] -naphthalenediamine; 1, 8-bis [ N-phenoxyformyl-N-benzyl ] -naphthalenediamine; 1, 8-bis [ N-p-methoxybenzoyl-N-benzyl ] -naphthalenediamine; 1, 8-bis [ N-p-methylbenzoyl-N-benzyl ] -naphthalenediamine; 1, 8-bis [ N-p-nitrobenzoyl-N-benzyl ] -naphthalenediamine; 1, 8-bis [ N-p-chlorobenzoyl-N-benzyl ] -naphthalenediamine; 1, 8-bis [ N-m-chlorobenzoyl-N-benzyl ] -naphthalenediamine; 1, 8-bis [ N-o-chlorobenzoyl-N-benzyl ] -naphthalenediamine; 1, 8-bis [ N-p-trifluoromethylbenzoyl-N-benzyl ] -naphthalenediamine; 1, 8-bis [ N-m-trimethylbenzoyl-N-benzyl ] -naphthalenediamine; 1, 8-bis [ N-m-bromobenzoyl-N-benzyl ] -naphthalenediamine; 1, 8-bis [ N-naphthoyl-N-benzyl ] -naphthalenediamine; 1, 8-bis [ N-p-tert-butylbenzoyl-N-benzyl ] -naphthalenediamine; 1, 8-bis [ N-benzoyl-N-p-methylbenzyl ] -naphthalenediamine; 1, 8-bis [ N-benzoyl-N-p-methoxybenzyl ] -naphthalenediamine; 1, 8-bis [ N-benzoyl-N-p-nitrophenylmethyl ] -naphthalenediamine; 1, 8-bis [ N-benzoyl-N-p-chlorobenzyl ] -naphthalenediamine; 1, 8-bis [ N-benzoyl-N-m-chlorobenzyl ] -naphthalenediamine; 1, 8-bis [ N-benzoyl-N-o-chlorobenzyl ] -naphthalenediamine; 1, 8-bis [ N-benzoyl-N-m-trimethylbenzyl ] -naphthalenediamine; 1, 8-bis [ N-benzoyl-N-p-tert-butyl benzyl ] -naphthalenediamine; 1, 8-bis [ N-m-chlorobenzoyl-N-m-chlorobenzyl ] -naphthalenediamine; 1, 8-bis [ N-p-tert-butylbenzoyl-N-p-tert-butylbenzyl ] -naphthalenediamine; 1, 8-bis [ N-m-trimethylbenzoyl-N-m-trimethylbenzyl ] -naphthalenediamine;
1, 8-bis [ N-acetyl-N-benzyl ] -naphthalenediamine; 1, 8-bis [ N-acetyl-N-benzhydryl ] -naphthalenediamine; 1, 8-bis [ N-propionyl-N-benzyl ] -naphthalenediamine; 1, 8-bis [ N-butyryl-N-benzyl ] -naphthalenediamine; 1, 8-bis [ N-isobutyryl-N-benzyl ] -naphthalenediamine; 1, 8-bis [ N-valeryl-N-p-methoxybenzyl ] -naphthalenediamine; 1, 8-bis [ N-isovaleryl-N-p-nitrophenylmethyl ] -naphthalenediamine; 1, 8-bis [ N-cyclopentacacyl-N-p-chlorobenzyl ] -naphthalenediamine; 1, 8-bis [ N-hexanoyl-N-m-chlorobenzyl ] -naphthalenediamine; 1, 8-bis [ N-cyclohexanecarboxyl-N-o-chlorobenzyl ] -naphthalenediamine; 1, 8-bis [ N-heptanoyl-N-p-tert-butyl benzyl ] -naphthalenediamine; 1, 8-bis [ N-octanoyl-N-m-trimethylbenzyl ] -naphthalenediamine; 1, 8-bis [ N-nonanoyl-N-benzyl ] -naphthalenediamine; 1, 8-bis [ N-decanoyl-N-benzyl ] -naphthalenediamine; 1, 8-bis [ N-undecanoyl-N-benzyl ] -naphthalenediamine; 1, 8-bis [ N-dodecanoyl-N-benzyl ] -naphthalenediamine; 1, 8-bis [ N-tetradecanoyl-N-benzyl ] -naphthalenediamine; 1, 8-bis [ N-hexadecanoyl-N-benzyl ] -naphthalenediamine; 1, 8-bis [ N-octadecanoyl-N-benzyl ] -naphthalenediamine; 1, 8-bis [ N-eicosyl-N-benzyl ] -naphthalenediamine;
1, 8-bis [ N-benzoyl-N-propyl ] -naphthalenediamine; 1, 8-bis [ N-benzoyl-N-isopropyl ] -naphthalenediamine; 1, 8-bis [ N-benzoyl-N-butyl ] -naphthalenediamine; 1, 8-bis [ N-benzoyl-N-isobutyl ] -naphthalenediamine; 1, 8-bis [ N-m-trimethylbenzoyl-N-pentyl ] -naphthalenediamine; 1, 8-bis [ N-p-tert-butylbenzoyl-N-isoamyl ] -naphthalenediamine; 1, 8-bis [ N-p-methylbenzoyl-N-hexyl ] -naphthalenediamine; 1, 8-bis [ N-p-methoxybenzoyl-N-heptyl ] -naphthalenediamine; 1, 8-bis [ N-p-chlorobenzoyl-N-decyl ] -naphthalenediamine; 1, 8-bis [ N-o-chlorobenzoyl-N-cyclohexylmethyl ] -naphthalenediamine; 1, 8-bis [ N-m-chlorobenzoyl-N-cyclopentylmethyl ] -naphthalenediamine; 1, 8-bis [ N-benzoyl-N-undecyl ] -naphthalenediamine; 1, 8-bis [ N-benzoyl-N-dodecyl ] -naphthalene diamine; 1, 8-bis [ N-benzoyl-N-tetradecyl ] -naphthalenediamine; 1, 8-bis [ N-benzoyl-N-hexadecyl ] -naphthalenediamine; 1, 8-bis [ N-benzoyl-N-octadecyl ] -naphthalenediamine; 1, 8-bis [ N-benzoyl-N-eicosyl ] -naphthalenediamine;
1, 8-bis [ N-phenoxyformyl-N-isopropyl ] -naphthalenediamine; 1, 8-bis [ N-phenoxyformyl-N-benzyl ] -naphthalenediamine; 1, 8-bis [ N-phenoxyformyl-N-benzhydryl ] -naphthalenediamine; 1, 8-bis [ N-phenoxyformyl-N-butyl ] -naphthalenediamine; 1, 8-bis [ N-p-methylphenoxycarbonyl-N-isopropyl ] -naphthalenediamine; 1, 8-bis [ N-p-methoxyphenoxyformyl-N-isopropyl ] -naphthalenediamine; 1, 8-bis [ N-m-chlorophenoxyformyl-N-isopropyl ] -naphthalenediamine; 1, 8-bis [ N-p-trifluoromethylbenzoyl-N-isopropyl ] -naphthalenediamine; 1, 8-bis [ N-hexyloxycarbonyl-N-isopropyl ] -naphthalenediamine; 1, 8-bis [ N-carbethoxy-N-isopropyl ] -naphthalenediamine; 1, 8-bis [ N-butyloxycarbonyl-N-isopropyl ] -naphthalenediamine; 1, 8-bis [ N-hexyloxycarbonyl-N-benzyl ] -naphthalenediamine; 1, 8-bis [ N-hexyloxycarbonyl-N-benzhydryl ] -naphthalenediamine; 1, 8-bis [ N-hexyloxycarbonyl-N-pentyl ] -naphthalenediamine; 1, 8-bis [ N-ethoxycarbonyl-N-benzyl ] -naphthalenediamine; 1, 8-bis [ N-ethoxycarbonyl-N-benzhydryl ] -naphthalenediamine; 1, 8-bis [ N-N-ethoxycarbonyl-N-N-pentyl ] -naphthalenediamine.
Of the compounds represented by the general formula (I), another preferred compound is a compound represented by the following general formula (IV):
Figure BDA0001242705590000061
wherein the radical R1-R6Has the same meaning as in the general formula (I); r8And R8’Has the same meaning as in the general formula (III).
Specific examples of the compounds included in the general formula (III) are:
1, 8-diethyleneimine-naphthalenediamine; 1, 8-di-n-propyleneimine-naphthalenediamine; 1, 8-diisopropylimine-naphthalenediamine; 1, 8-di-n-butylimine-naphthalenediamine; 1, 8-diisobutylimine-naphthalenediamine; 1, 8-di-n-pentylimine-naphthalenediamine; 1, 8-diisoamylimine-naphthalene diamine; 1, 8-dicyclopentylmethylimine-naphthalenediamine; 1, 8-di-n-hexylimine-naphthalenediamine; 1, 8-dicyclohexylmethane-diamine; 1, 8-diheptylimine-naphthalenediamine; 1, 8-dioctanimine-naphthalenediamine; 1, 8-dinonylimine-naphthylenediamine; 1, 8-didecylimine-naphthalenediamine; 1, 8-bis [ undecamine ] -naphthalenediamine; 1, 8-bis [ dodecamine ] -naphthalenediamine; 1, 8-bis [ tridecylimine ] -naphthalenediamine; 1, 8-ditetradecylimine-naphthalenediamine; 1, 8-bis [ pentadecimi ] -naphthalenediamine; 1, 8-bis [ hexadecimal ] -naphthalenediamine; 1, 8-bis [ heptadecaimino ] -naphthalenediamine; 1, 8-bis [ octadecylidene ] -naphthalenediamine; 1, 8-bis [ nonadecamino ] -naphthalenediamine; 1, 8-bis [ eicosanimidoyl ] -naphthalenediamine; 1, 8-diphenylmethanimine-naphthalenediamine; 1, 8-bis [ diphenylmethanimine ] -naphthalenediamine; 1, 8-di-p-chlorobenzeneimine-naphthalenediamine; 1, 8-bis-o-chlorobenzeneimine-naphthalenediamine; 1, 8-di-m-chlorobenzeneimine-naphthalenediamine; 1, 8-di-p-methylbenzylidene imine-naphthalenediamine; 1, 8-di-p-methoxybenzeneimine-naphthalenediamine; 1, 8-di-p-nitrobenzeneimine-naphthalenediamine; 1, 8-bis-bromobenzimide-naphthalene diamine; 1, 8-diphenoxyazomethine-naphthalenediamine; 1, 8-dinaphthaleneimine-naphthalenediamine; 1, 8-di-p-trifluoromethylbenzimide-naphthalene diamine; 1, 8-dipentafluorophenylimine-naphthalenediamine; 1, 8-di-p-propylbenzimide-naphthalene diamine; 1, 8-di-p-tert-butylbenzimide-naphthylenediamine; 1, 8-di-p-isobutylbenzimide-naphthylenediamine; 1, 8-di-trimethylbenzimide-naphthalene diamine.
The 1, 8-naphthalenediamine compounds of the present invention can be synthesized by various reactions, for example, reacting a substituted or unsubstituted 1, 8-naphthalenediamine with an acid chloride or chloroformate to give RIIAnd RIVA compound of formula (II) when H;
Figure BDA0001242705590000062
when R isIIAnd RIVCompounds of the general formula (II) which are different from H and identical are obtainable by a process of the formula which is particularly suitable for the preparation of compounds of the formulaIIA compound of the general formula (II) which is an aryl, substituted aryl, heterocycle, t-butyl, etc. group:
Figure BDA0001242705590000071
the compound of formula (III) as a preferred compound of formula (II) can be obtained by reacting a substituted or unsubstituted 1, 8-naphthalenediamine with an aldehyde or ketone, followed by reduction and then with an acid chloride or chloroformate:
Figure BDA0001242705590000072
reacting a substituted or unsubstituted 1, 8-naphthalenediamine with an aldehyde or ketone to give a compound of the general formula (IV):
Figure BDA0001242705590000073
one aspect of the solid catalyst component of the present invention is a catalyst component comprising only said 1, 8-naphthalenediamine compound of the general formula (I).
In another aspect of the solid catalyst component of the present invention, in addition to the 1, 8-naphthalenediamine compound of the general formula (I), at least one further electron donor compound is included, selected from L ewis bases containing one or more electronegative groups, wherein the electron donor atom is selected from the group consisting of N, O, S, P, As or Sn, preferably from the group consisting of diethers, esters, diketos and diamines, when the 1, 8-naphthalenediamine compound is used together with other internal electron donor compounds as disclosed above, a catalyst with adjustable properties is obtained.
The molar ratio of the 1, 8-naphthalenediamine compound to the other electron-donor compound is 0.01 to 100, preferably 0.02 to 50, more preferably 0.05 to 20.
Another electron-donor compound other than the 1, 8-naphthalenediamine compound of formula (I) is preferably selected from the 1, 3-diethers of formula (V):
Figure BDA0001242705590000081
wherein: r, R1、R2、R3、R4And R5Which may be identical or different, represent H or a linear or branched alkyl, cycloalkyl, aryl, alkylaryl or arylalkyl radical having from 1 to 18 carbon atoms; r6And R7And may be the same or different and represent a straight-chain or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 5 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms and an arylalkyl group; r to R7One or more of the groups may be linked to form a cyclic structure, and may each comprise one or more heteroatoms selected from halogen, N, O, S, P, and Si.
Specific examples of ethers that can be advantageously used include: 2- (2-ethylhexyl) 1, 3-dimethoxypropane, 2-isopropyl-1, 3-dimethoxypropane, 2-butyl-1, 3-dimethoxypropane, 2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-1, 3-dimethoxypropane, 2-phenyl-1, 3-dimethoxypropane, 2-tert-butyl-1, 3-dimethoxypropane, 2-cumyl-1, 3-dimethoxypropane, 2- (2-phenylethyl) -1, 3-dimethoxypropane, 2- (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2- (p-chlorophenyl) -1, 3-dimethoxypropane, 2- (diphenylmethyl) -1, 3-dimethoxypropane, 2 (1-naphthyl) -1, 3-dimethoxypropane, 2 (p-fluorophenyl) -1, 3-dimethoxypropane, 2- (1-decahydronaphthyl) -1, 3-dimethoxypropane, 2 (p-tert-butylphenyl) -1, 3-dimethoxypropane, 2, 2-dicyclohexyl-1, 3-dimethoxypropane, 2, 2-diethyl-1, 3-dimethoxypropane, 2, 2-dipropyl-1, 3-dimethoxypropane, 2, 2-dibutyl-1, 3-dimethoxypropane, 2, 2-diethyl-1, 3-diethoxypropane, 2, 2-dicyclopentyl-1, 3-dimethoxypropane, 2, 2-dipropyl-1, 3-diethoxypropane, 2, 2-dibutyl-1, 3-diethoxypropane, 2-methyl-2-ethyl-1, 3-dimethoxypropane, 2-methyl-2-propyl-1, 3-dimethoxypropane, 2-methyl-2-benzyl-1, 3-dimethoxypropane, 2-methyl-2-phenyl-1, 3-dimethoxypropane, 2-methyl-2-cyclohexyl-1, 3-dimethoxypropane, 2-methyl-2-methylcyclohexyl-1, 3-dimethoxypropane, 2, 2-bis (p-chlorophenyl) -1, 3-dimethoxypropane, 2, 2-bis (2-phenylethyl) -1, 3-dimethoxypropane, 2, 2-bis (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2-methyl-2-isobutyl-1, 3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2, 2-bis (p-methylphenyl) -1, 3-dimethoxypropane, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2, 2-diisobutyl-1, 3-dimethoxypropane, 2, 2-diphenyl-1, 3-dimethoxypropane, 2, 2-dibenzyl-1, 3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1, 3-dimethoxypropane, 2, 2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane, 2, 2-diisobutyl-1, 3-diethoxypropane, 2, 2-diisobutyl-1, 3-dibutoxypropane, 2-isobutyl-2-isopropyl-1, 3-dimethoxypropane, 2, 2-di-sec-butyl-1, 3-dimethoxypropane, 2, 2-di-tert-butyl-1, 3-dimethoxypropane, 2, 2-dineopentyl-1, 3-dimethoxypropane, 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, 2-phenyl-2-benzyl-1, 3-dimethoxy __ -ylpropane, 2-cyclohexyl-2-cyclohexylmethyl-1, 3-dimethoxypropane. 1, 1-bis (methoxymethyl) -cyclopentadiene; 1, 1-bis (methoxymethyl) -2,3,4, 5-tetramethylcyclopentadiene; 1, 1-bis (methoxymethyl) -2,3,4, 5-tetraphenylcyclopentadiene; 1, 1-bis (methoxymethyl) -2,3,4, 5-tetrafluorocyclopentadiene; 1, 1-bis (methoxymethyl) -3, 4-dicyclopentylcyclopentadiene; 1, 1-bis (methoxymethyl) indene; 1, 1-bis (methoxymethyl) -2, 3-dimethylindene; 1, 1-bis (methoxymethyl) -4,5,6, 7-tetrahydroindene; 1, 1-bis (methoxymethyl) -2,3,6, 7-tetrafluoroindene; 1, 1-bis (methoxymethyl) -4, 7-dimethylindene; 1, 1-bis (methoxymethyl) -3, 6-dimethylindene; 1, 1-bis (methoxymethyl) -4-phenylindene; 1, 1-bis (methoxymethyl) -4-phenyl-2-methylindene; 1, 1-bis (methoxymethyl) -4-cyclohexylindene; 1, 1-bis (methoxymethyl) -7- (3,3, 3-trifluoropropyl) indene; 1, 1-bis (methoxymethyl) -7-trimethylsilylindole; 1, 1-bis (methoxymethyl) -7-trifluoromethylindene; 1, 1-bis (methoxymethyl) -4, 7-dimethyl-4, 5,6, 7-tetrahydroindene; 1, 1-bis (methoxymethyl) -7-methylindene; 1, 1-bis (methoxymethyl) -7-cyclopentylindole; 1, 1-bis (methoxymethyl) -7-isopropylindene; 1, 1-bis (methoxymethyl) -7-cyclohexylindene; 1, 1-bis (methoxymethyl) -7-tert-butylindene; 1, 1-bis (methoxymethyl) -7-tert-butyl-2-methylindene; 1, 1-bis (methoxymethyl) -7-phenylindene; 1, 1-bis (methoxymethyl) -2-phenylindene; 1, 1-bis (methoxymethyl) -1H-benzo [ e ] indene; 1, 1-bis (methoxymethyl) -1H-2-methylbenzo [ e ] indene; 9, 9-bis (methoxymethyl) fluorene; 9, 9-bis (methoxymethyl) -2,3,6, 7-tetramethylfluorene; 9, 9-bis (methoxymethyl) -2,3,4,5,6, 7-hexafluorofluorene; 9, 9-bis (methoxymethyl) -2, 3-benzofluorene; 9, 9-bis (methoxymethyl) -2,3,6, 7-dibenzofluorene; 9, 9-bis (methoxymethyl) -2, 7-diisopropylfluorene; 9, 9-bis (methoxymethyl) -1, 8-dichlorofluorene; 9, 9-bis (methoxymethyl) -2, 7-dicyclopentylfluorene; 9, 9-bis (methoxymethyl) -1, 8-difluorofluorene; 9, 9-bis (methoxymethyl) -1,2,3, 4-tetrahydrofluorene; 9, 9-bis (methoxymethyl) -1,2,3,4,5,6,7, 8-octahydrofluorene; 9, 9-bis (methoxymethyl) -4-tert-butylfluorene.
The other electron donor compound than the 1, 8-naphthalenediamine compound of the general formula (I) is preferably a monocarboxylic ester or a polycarboxylic ester compound, and specific examples thereof are an aromatic dicarboxylic acid compound and an aliphatic dicarboxylic acid ester compound:
diesters of aromatic dicarboxylic acids, such as phthalic diesters or terephthalic diesters. The phthalic diesters include: dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, methyl ethyl phthalate, methyl isopropyl phthalate, methyl n-propyl phthalate, ethyl n-butyl phthalate, ethyl isobutyl phthalate, di-n-pentyl phthalate, diisopentyl phthalate, dihexyl phthalate, di-n-heptyl phthalate, di-n-octyl phthalate, diisooctyl phthalate, 2-dimethylhexyl phthalate, 2-ethylhexyl phthalate, di-n-nonyl phthalate, diisodecyl phthalate, 2-dimethylheptyl phthalate, n-hexyl phthalate, n-butyl (2-ethylhexyl) phthalate, n-hexyl phthalate, n-nonyl isononyl phthalate, isopentyl n-decyl phthalate, n-undecyl phthalate, isopentyl isohexyl phthalate, n-hexyl phthalate (2-methylhexyl phthalate), n-hexyl (2-ethylhexyl) phthalate, n-hexyl (isononyl) phthalate, n-hexyl (n-decyl) phthalate, n-heptyl (2-ethylhexyl) phthalate, n-heptyl (isononyl) phthalate, n-heptyl (nonyl) phthalate, and 2-ethylhexyl (isononyl) phthalate. These esters may be used alone or in combination of two or more. The terephthalic acid diester includes: dimethyl terephthalate, diethyl terephthalate, di-n-propyl terephthalate, diisopropyl terephthalate, di-n-butyl terephthalate, diisobutyl terephthalate, ethyl methyl terephthalate, methyl isopropyl terephthalate, ethyl (n-propyl) terephthalate, ethyl (n-butyl) terephthalate, ethyl (isobutyl) terephthalate, di-n-pentyl terephthalate, diisopentyl terephthalate, dihexyl terephthalate, di-n-heptyl terephthalate, di-n-octyl terephthalate, diison-octyl terephthalate, di-2, 2-dimethylhexyl terephthalate, di-2-ethylhexyl terephthalate, di-n-nonyl terephthalate, diisononyl terephthalate, diisodecyl terephthalate, di-n-butyl terephthalate, di-isobutyl terephthalate, di-n-butyl terephthalate, di-hexyl terephthalate, di, Di (2, 2-dimethylethylheptyl) terephthalate, n-butyl isohexyl terephthalate, n-butyl (2-ethylhexyl) terephthalate, n-hexyl n-pentyl terephthalate, n-pentyl isohexyl terephthalate, isopentyl (heptyl) terephthalate, terephthalic acid, n-pentyl (2-ethylhexyl) terephthalate, n-pentyl (isononyl) terephthalate, isopentyl (n-decyl) terephthalate, n-pentyl (undecyl) terephthalate, isopentyl (isohexyl) terephthalate, n-hexyl (2-ethylhexyl) terephthalate, n-hexyl (isononyl) terephthalate, n-hexyl (n-decyl) terephthalate, n-heptyl (2-ethylhexyl) terephthalate, n-heptyl (isononyl) terephthalate, n-heptyl (neodecyl) terephthalate, n-hexyl (iso-hexyl) terephthalate, n-hexyl (iso-nonyl) terephthalate, n-hexyl (n-decyl) terephthalate, n-hexyl (iso-decyl) terephthalate, n-hexyl (neo, And 2-ethylhexyl (isononyl) terephthalate. These esters may be used alone or in combination of two or more.
Among these diesters, it is recommended to use one or a mixture of two or more of diethyl phthalate, dipropyl butyl phthalate, diisopropyl terephthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-octyl phthalate, diisooctyl phthalate, di-n-butyl terephthalate, diisobutyl terephthalate, di-n-octyl terephthalate, diisooctyl terephthalate, di-2-ethylhexyl terephthalate, and diisodecyl phthalate.
Particularly preferably, among the polycarboxylic acid ester compounds, a succinic acid ester compound selected from the group consisting of those of the general formula (VI):
Figure BDA0001242705590000101
wherein the radical R1And R2Equal to or different from each other, is a C1-C20 linear or branched alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkaryl group, optionally comprising heteroatoms; r3-R6Wherein at least two radicals are different from hydrogen and are selected from C1-C20Linear or branched alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkaryl radicals, optionally containing hetero atoms, and, in addition, the radicals R3-R6May be joined together to form a ring. R1And R2Preferred are C1-C8 alkyl, cycloalkyl, aryl, aralkyl and alkaryl groups. Particularly preferred are compounds wherein R is1And R2Selected from primary alkyl groups, in particular branched primary alkyl groups. Suitable R1And R2Examples of (B) are methyl, ethyl, n-propyl, n-butyl, isobutyl, neopentyl, 2-ethylhexyl. Particularly preferred are ethyl, isobutyl and neopentyl.
One of the preferred classes of compounds described by the general formula (VI) is that wherein R is3-R5Is hydrogen and R6Are branched alkyl, cycloalkyl, aryl, aralkyl and alkaryl groups having from 3 to 10 carbon atoms. Particularly preferred are compounds wherein R is6Is a branched primary alkyl group or cycloalkyl group having 3 to 10 carbon atoms. Specific examples of suitable mono-substituted succinate compounds are diethyl sec-butylsuccinate, diethyl hexylsuccinate, diethyl cyclopropylsuccinate, diethyl norbornylsuccinate, totalDiethyl hydrosuccinate, diethyl trimethylsiluccinate, diethyl methoxysuccinate, diethyl p-methoxyphenylsuccinate, diethyl p-chlorophenylsuccinate, diethyl phenylsuccinate, diethyl cyclohexylsuccinate, diethyl benzylsuccinate, diethyl cyclohexylmethylsuccinate, diethyl tert-butylsuccinate, diethyl isobutylsuccinate, diethyl isopropylsuccinate, diethyl neopentylsuccinate, diethyl isopentylsuccinate, diethyl 1-trifluoromethylethyl succinate, diethyl fluorenylsuccinate, 1-ethoxycarbonyldiisobutyl phenylsuccinate, diisobutyl sec-butylsuccinate, diisobutyl hexylsuccinate, diisobutyl cyclopropylsuccinate, diisobutyl norbornylsuccinate, diisobutyl perhydrosuccinate, diisobutyl trimethylsilylsuccinate, Diisobutyl methoxysuccinate, diisobutyl p-methoxyphenylsuccinate, diisobutyl p-chlorophenoxysuccinate, diisobutyl cyclohexylsuccinate, diisobutyl benzylsuccinate, diisobutyl cyclohexylmethylsuccinate, diisobutyl t-butylsuccinate, diisobutyl isobutylsuccinate, diisobutyl isopropylsuccinate, diisobutyl neopentylsuccinate, diisobutyl isopentylsuccinate, diisobutyl 1-trifluoromethylethyl succinate, diisobutyl fluorenylsuccinate, dipentyl sec-butylsuccinate, dipentyl hexylsuccinate, dipentyl cyclopropylsuccinate, dineopentyl norbornylsuccinate, dipentyl perhydrosuccinate, dineopentyl trimethylsilylsuccinate, dineopentyl methoxysuccinate, dipentyl p-methoxyphenylsuccinate, dineopentyl p-chlorophenylsuccinate, Dipentyl phenylsuccinate, dipentyl cyclohexylsuccinate, dipentyl benzylsuccinate, dipentyl cyclohexylmethylsuccinate, dipentyl tert-butylsuccinate, dipentyl isobutylsuccinate, dipentyl isopropylsuccinate, dipentyl neopentylsuccinate, dipentyl isopentylsuccinate, (1-trifluoromethylethyl) succinate, dineopentyl fluorenylsuccinate.
Another preferred class of compounds within formula (VI) areIn which R is3-R6At least two of which are different from hydrogen and are selected from C1-C20 linear or branched alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkaryl groups, optionally containing heteroatoms. Particularly preferred are compounds in which two groups other than hydrogen are attached to the same carbon atom. Specific examples of suitable di-substituted succinates are: diethyl 2, 2-dimethylsuccinate, diethyl 2-ethyl-2-methylsuccinate, diethyl 2-benzyl-2-isopropylsuccinate, diethyl 2-cyclohexylmethyl-2-isobutylsuccinate, diethyl 2-cyclopentyl-2-n-butylsuccinate, diethyl 2, 2-diisobutylsuccinate, diethyl 2-cyclohexyl-2-ethylsuccinate, diethyl 2-isopropyl-2-methylsuccinate, diethyl 2-tetradecyl-2-ethylsuccinate, diethyl 2-isobutyl-2-ethylsuccinate, diethyl 2- (1-trifluoromethylethyl) -2-methylsuccinate, diethyl 2-isopentyl-2-isobutylsuccinate, diethyl 2-ethylsuccinate, diethyl 2-ethyl-2-isobutylsuccinate, diethyl 2-cyclohexylsuccinate, diethyl 2-isopropylsuccinate, diethyl 2-isobutylsuccinate, diethyl 2-ethylsuccinate, diethyl 2-cyclopentylmethyl-2-butylsuccinate, diethyl 2-isobutyl, Diethyl 2-phenyl-2-n-butylsuccinate, diisobutyl 2, 2-dimethylsuccinate, diisobutyl 2-ethyl-2-methylsuccinate, diisobutyl 2-benzyl-2-isopropylsuccinate, diisobutyl 2-cyclohexylmethyl-2-isobutylsuccinate, diisobutyl 2-cyclopentyl-2-n-butylsuccinate, diisobutyl 2, 2-diisobutylsuccinate, diisobutyl 2-cyclohexyl-2-ethylsuccinate, diisobutyl 2-isopropyl-2-methylsuccinate, diisobutyl 2-tetradecyl-2-ethylsuccinate, diisobutyl 2-isobutyl-2-ethylsuccinate, diisobutyl 2- (1-trifluoromethylethyl) -2-methylsuccinate, diisobutyl 2-isobutyl-2-methylsuccinate, Diisobutyl 2-isopentyl-2-isobutylsuccinate, diisobutyl 2-phenyl-2-n-butylsuccinate, dipentyl 2, 2-dimethylsuccinate, dipentyl 2-ethyl-2-methylsuccinate, dipentyl 2-benzyl-2-isopropylsuccinate, dipentyl 2-cyclohexylmethyl-2-isobutylsuccinate, dipentyl 2-cyclopentyl-2-n-butylsuccinate, dipentyl 2, 2-diisobutylsuccinate, dipentyl 2-cyclohexyl-2-ethylsuccinate, dipentyl 2-isopropyl-2-methylsuccinate, dipentyl 2-tetradecyl-2-ethylsuccinate, dipentyl 2-isobutyl-2-ethylsuccinate, 2- (1-trifluoromethylethyl) -2-methylphosphonic acid dipentyl ester, 2-isopentyl-2-isobutylsuccinic acid dipentyl esterEster, 2-phenyl-2-n-butylsuccinate dipentyl ester.
In addition, particular preference is given to compounds in which at least two radicals other than hydrogen are bonded to different carbon atoms, i.e. R3And R5Or R4And R6. Specific examples of suitable compounds are diethyl 2, 3-bis (trimethylsilyl) succinate, diethyl 2-sec-butyl-3-methylsuccinate, diethyl 2- (3,3, 3-trifluoropropyl) -3-methylsuccinate, diethyl 2, 3-bis (2-ethylbutyl) succinate, diethyl 2, 3-diethyl-2-isopropylsuccinate, diethyl 2, 3-diisopropyl-2-methylsuccinate, diethyl 2, 3-dicyclohexyl-2-methylsuccinate, diethyl 2, 3-dibenzylsuccinate, diethyl 2, 3-diisopropylsuccinate, diethyl 2, 3-bis (cyclohexylmethyl) succinate, diethyl 2, 3-di-tert-butylsuccinate, Diethyl 2, 3-diisobutylsuccinate, diethyl 2, 3-dineopentylsuccinate, diethyl 2, 3-diisopentylsuccinate, diethyl 2, 3-bis (1-trifluoromethylethyl) succinate, diethyl 2, 3-ditetradecylsuccinate, diethyl 2, 3-difluorenylsuccinate, diethyl 2-isopropyl-3-isobutylsuccinate, diethyl 2-tert-butyl-3-isopropylsuccinate, diethyl 2-isopropyl-3-cyclohexylsuccinate, diethyl 2-isopentyl-3-cyclohexylsuccinate, diethyl 2-tetradecyl-3-cyclohexylsuccinate, diethyl 2-cyclohexyl-3-cyclopentylsuccinate, diethyl 2-isopentylsuccinate, diethyl 2-tetradecyl-3-cyclohexylsuccinate, diethyl 2-cyclohexyl-3-cyclopentylsuccinate, Diethyl 2,2, 3, 3-tetramethylsuccinate, diethyl 2,2, 3, 3-tetraethylsuccinate, diethyl 2,2, 3, 3-tetrapropylsuccinate, diethyl 2, 3-diethyl-2, 3-diisopropylsuccinate, diethyl 2,2, 3, 3-tetrafluorosuccinate, diisobutyl 2, 3-bis (trimethylsilyl) succinate, diisobutyl 2-sec-butyl-3-methylsuccinate, diisobutyl 2- (3,3, 3-trifluoropropyl) -3-methylsuccinate, diisobutyl 2, 3-bis (2-ethylbutyl) succinate, diisobutyl 2, 3-diethyl-2-isopropylsuccinate, diisobutyl 2, 3-diisopropyl-2-methylsuccinate, Diisobutyl 2, 3-dicyclohexyl-2-methylsuccinate, diisobutyl 2, 3-dibenzylsuccinate, diisobutyl 2, 3-diisopropylsuccinate, diisobutyl 2, 3-bis (cyclohexylmethyl) succinate, and diisobutyl 2, 3-di-tert-butylDiisobutyl sulfosuccinate, diisobutyl 2, 3-diisobutyl succinate, diisobutyl 2, 3-dineopentylsuccinate, diisobutyl 2, 3-diisopentylsuccinate, diisobutyl 2, 3-bis (1-trifluoromethylethyl) succinate, diisobutyl 2, 3-ditetradecylsuccinate, diisobutyl 2, 3-difluorenylsuccinate, diisobutyl 2-isopropyl-3-isobutylsuccinate, diisobutyl 2-tert-butyl-3-isopropylsuccinate, diisobutyl 2-isopropyl-3-cyclohexylsuccinate, diisobutyl 2-isopentyl-3-cyclohexylsuccinate, diisobutyl 2-tetradecyl-3-cyclohexylmethylsuccinate, diisobutyl 2-cyclohexyl-3-cyclopentylsuccinate, Diisobutyl 2,2, 3, 3-tetramethylsuccinate, diisobutyl 2,2, 3, 3-tetraethylsuccinate, diisobutyl 2,2, 3, 3-tetrapropylsuccinate, diisobutyl 2, 3-diethyl-2, 3-dipropylsuccinate, diisobutyl 2,2, 3, 3-tetrafluorosuccinate, dipentyl 2, 3-bis (trimethylsilyl) succinate, dipentyl 2-sec-butyl-3-methylsuccinate, dipentyl 2- (3,3, 3-trifluoropropyl) -3-methylsuccinate, dipentyl 2, 3-bis (2-ethylbutyl) succinate, dipentyl 2, 3-diethyl-2-isopropylsuccinate, dipentyl 2, 3-diisopropyl-2-methylsuccinate, Dipentyl 2, 3-dicyclohexyl-2-methylsuccinate, dipentyl 2, 3-dibenzylsuccinate, dipentyl 2, 3-diisopropylsuccinate, dipentyl 2, 3-bis (cyclohexylmethyl) succinate, dipentyl 2, 3-di-tert-butylsuccinate, dipentyl 2, 3-diisobutylsuccinate, dipentyl 2, 3-dineopentylsuccinate, dipentyl 2, 3-diisopentylsuccinate, dipentyl 2,3- (1-trifluoromethylethyl) succinate, dipentyl 2, 3-ditetradecyl succinate, dipentyl 2, 3-difluorenylsuccinate, dipentyl 2-isopropyl-3-isobutylsuccinate, dipentyl 2-tert-butyl-3-isopropylsuccinate, 2-isopropyl-3-cyclohexylsuccinate dipentyl, 2-isopentyl-3-cyclohexylsuccinate dipentyl, 2-tetradecyl-3-cyclohexylmethylsuccinate dipentyl, 2-cyclohexyl-3-cyclopentylsuccinate dipentyl, 2,3, 3-tetramethylsuccinate dipentyl, 2,3, 3-tetraethylsuccinate dipentyl, 2,3, 3-tetrapropylsuccinate dipentylDipentyl 2, 3-diethyl-2, 3-diisopropylsuccinate and dipentyl 2,2, 3, 3-tetrafluorosuccinate.
As mentioned above, the radicals R being attached to the same carbon atom3-R6Also preferred are compounds of formula (VI) in which two or four are linked together to form a ring. Specific examples of suitable compounds are 1- (ethoxycarbonyl) -1- (ethoxyacetyl) -2, 6-dimethylcyclohexane, 1- (ethoxycarbonyl) -1- (ethoxyacetyl) -2, 5-dimethylcyclopentane, 1- (ethoxycarbonyl) -1- (ethoxyacetylmethyl) -2-methylcyclohexane, 1- (ethoxycarbonyl) -1- (ethoxyacetylcyclohexyl) cyclohexane.
The above-mentioned compounds can be used in the form of pure isomers or in the form of mixtures of enantiomers, or in the form of mixtures of positional isomers and enantiomers. When a pure isomer is to be used, it is generally isolated by conventional techniques well known in the art. In particular, some of the succinates of the invention may be used as pure racemic or meso forms, or alternatively as mixtures of the two forms.
The other electron donor compound other than the 1, 8-naphthalenediamine compound is preferably selected from glycol ester compounds of the general formula (VII):
Figure BDA0001242705590000131
in the formula R1-R6、R1’-R2’Is the same or different hydrogen, halogen or substituted or unsubstituted straight chain or branched C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl, C7-C20 arylalkyl, C2-C10 alkenyl or C10-C20 condensed ring aryl; but R is1’And R2’Not being hydrogen, R1-R6Optionally looped or not looped.
The diol ester compounds may be, for example: 1, 3-propanediol dibenzoate, 2-methyl-1, 3-propanediol dibenzoate, 2-ethyl-1, 3-propanediol dibenzoate, 2-propyl-1, 3-propanediol dibenzoate, 2-butyl-1, 3-propanediol dibenzoate, 2-dimethyl-1, 3-propanediol dibenzoate, 2-ethyl-2-butyl-1, 3-propanediol dibenzoate, 2-diethyl-1, 3-propanediol dibenzoate, 2-methyl-2-propyl-1, 3-propanediol dibenzoate, 2-isopropyl-2-isopentyl-1, 3-propanediol dibenzoate, 2-methyl-1, 3-propanediol, 2, 4-pentanediol dibenzoate, 3-methyl-2, 4-pentanediol dibenzoate, 3-ethyl-2, 4-pentanediol dibenzoate, 3-propyl-2, 4-pentanediol dibenzoate, 3-butyl-2, 4-pentanediol dibenzoate, 3-dimethyl-2, 4-pentanediol dibenzoate, 2-methyl-1, 3-pentanediol dibenzoate, 2-dimethyl-1, 3-pentanediol dibenzoate, 2-ethyl-1, 3-pentanediol dibenzoate, 2-butyl-1, 3-pentanediol dibenzoate, 2-methyl-1, 3-pentanediol dibenzoate, 3-propanediol dibenzoate, 3-, 2-Ethyl-1, 3-pentanediol dibenzoate, 2-propyl-1, 3-pentanediol dibenzoate, 2-butyl-1, 3-pentanediol dibenzoate, 2-dimethyl-1, 3-pentanediol dibenzoate, 2-methyl-1, 3-pentanediol dibenzoate, 2-dimethyl-1, 3-pentanediol dibenzoate, 2-ethyl-1, 3-pentanediol dibenzoate, 2-butyl-1, 3-pentanediol dibenzoate, 2, 4-trimethyl-1, 3-pentanediol dibenzoate, 3-methyl-3-butyl-2, 4-pentanediol dibenzoate, 2-propyl-1, 3-pentanediol dibenzoate, 2-methyl-3-butyl-2, 4-pentanediol dibenzoate, 2-methyl-1, 3-pentanediol dibenzoate, 2-methyl-2, 3-, 2, 2-dimethyl-1, 5-pentanediol dibenzoate, 3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, and the like. Pentanediol esters and heptanediol esters are preferred.
The solid catalyst component for olefin polymerization according to the present invention comprises a titanium compound, a magnesium compound, at least one 1, 8-naphthalenediamine compound selected from the above, and a precursor of the magnesium compound selected from at least one of: xnMg(OR)2-n，MgCl2·mROH，R2-nMgXn，MgCl2/SiO2，MgCl2/Al2O3Or a mixture of a magnesium halide and a titanium alkoxide, where m is a number from 0.1 to 6, 0 < n > 2, X is halogen, R is C1-C20A hydrocarbon group of (a); the general formula of the titanium compound is TiXN(OR)4-NWherein R is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, and N is 1 to 4.
One of the solid catalyst components for olefin polymerization of the present invention preferably comprises a titanium compound, a magnesium compound, (i) at least one 1, 8-naphthalenediamine compound selected from the above, and (ii) at least one monofunctional or polyfunctional electron donor compound of ether, ester, ketone or amine, the precursor of the magnesium compound being selected from at least one of: xnMg(OR)2-n，MgCl2·mROH，R2-nMgXn，MgCl2/SiO2，MgCl2/Al2O3Or a mixture of a magnesium halide and a titanium alkoxide, where m is a number from 0.1 to 6, 0 < n > 2, X is halogen, R is C1-C20A hydrocarbon group of (a); the general formula of the titanium compound is TiXN(OR)4-NWherein R is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, and N is 1 to 4.
The magnesium compound of the present invention is preferably a magnesium hydrocarbyloxy compound.
The magnesium compound of the present invention is further preferably an alcoholate of a magnesium dihalide.
The titanium compound of the present invention includes titanium tetrachloride, titanium tetrabromide, titanium tetraiodide or an alkyltitanium halide such as methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride, dimethoxytitanium dichloride, diethoxytitanium dichloride, dipropoxytitanium dichloride, di-n-butoxytitanium dichloride, trimethoxytitanium chloride, triethoxytitanium chloride, tripropoxytitanium chloride or tri-n-butoxytitanium chloride. One or more of these titanium halides may be used in combination. Among them, titanium tetrachloride is preferably used.
The preparation of the solid catalyst component of the present invention can be carried out according to several methods:
according to one of the processes, with TiCl4Or an aromatic hydrocarbon (e.g., toluene, xylene, etc.) solution of titanium alkoxide may be reacted with a magnesium dihydrocarbyloxide compound such as magnesium dialkoxide or magnesium diaryloxide at-25 to 0 deg.C and halogenated at 80 to 130 deg.C. With TiCl4The treatment with the aromatic hydrocarbon solution of (a) may be repeated one or more times, and the above-mentioned additives may be added in one or more portions in a plurality of such treatmentsOr the 1, 8-naphthalenediamine compound and the second electron donor compound. The preparation can be carried out, for example, with reference to the preparation of the titanium-containing solid catalyst component disclosed in US 5077357: adding magnesium ethoxide, tetraethoxy titanium, o-cresol, ethanol and chlorobenzene in sequence, and stirring; mixing TiCl4Adding chlorobenzene solution into the liquid quickly, heating until the chlorobenzene solution is dissolved completely, and continuing heating to a specific temperature; by using N2Continuously stirring for a certain time after the ethanol reactant is taken away by bubbling, washing once by adopting hot chlorobenzene and twice by adopting isooctane, and then washing by adopting N2Drying to obtain the carrier. Or according to another example: sequentially mixing TiCl4Adding tetraethoxy titanium, ethoxy magnesium and o-cresol into chlorobenzene, and stirring; adding ethanol, and continuously stirring for 3h at high temperature after the magnesium ethoxide is dissolved; filtering while hot, washing with warm chlorobenzene once, washing with isooctane once, and finally N2And (5) drying.
According to another method, an alcoholate or chlorohydrin of magnesium and an excess of TiCl containing in solution the above-mentioned 1, 8-naphthalenediamine compound or the above-mentioned 1, 8-naphthalenediamine compound and a second electron-donor compound4Reacting at 80-135 deg.C. According to a preferred method, the general formula TiXn(OR)4-nWherein R is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, and n is 1 to 4; preference is given to TiCl4And is represented by the formula MgCl2The adduct of mROH, where m is a number from 0.1 to 6, preferably from 2 to 3.5, and R is a hydrocarbon radical having from 1 to 20 carbon atoms, to prepare the solid catalyst component. The adduct can be suitably made spherical by the following method: the alcohol and magnesium chloride are mixed in the presence of an inert hydrocarbon immiscible with the adduct, and the emulsion is rapidly quenched, thereby solidifying the adduct in the form of spherical particles. MgCl in spherical form prepared according to this process2Examples of mROH adducts are described in US4399054 and US 4469648. The adduct thus obtained can be directly reacted with the titanium compound or it can be previously subjected to a thermal controlled dealcoholation (80-130 ℃) to obtain an adduct in which the number of moles of alcohol is generally lower than 3, preferably between 0.1 and 2.5. Can be prepared by mixingThe adduct (dealcoholated or as such) is suspended in cold TiCl4(generally-25-0 ℃) with a titanium compound; the mixture is heated to 80-130 ℃ and held at this temperature for 0.5-2 hours. With TiCl4The treatment may be performed one or more times. In the presence of TiCl4The above-mentioned 1, 8-naphthalenediamine compound, or the above-mentioned 1, 8-naphthalenediamine compound and the second electron-donor compound may be added during the treatment, and the treatment may be repeated one or more times.
Another method for preparing the solid catalyst component of the present invention comprises grinding together anhydrous magnesium chloride and the above-mentioned 1, 8-naphthalenediamine compound, or the above-mentioned 1, 8-naphthalenediamine compound and a second electron donor compound under conditions in which magnesium dichloride is activated. The product thus obtained can be used with an excess of TiCl at a temperature of between 80 and 130 DEG C4One or more treatments. After the treatment, the mixture is washed with a hydrocarbon solvent until free of chloride ions. According to a further process, the product obtained by co-grinding magnesium dichloride in the anhydrous state, the titanium compound and the above-mentioned 1, 8-naphthalenediamine compound is treated with a halogenated hydrocarbon such as 1, 2-dichloroethane, chlorobenzene, dichloromethane. The treatment is carried out at a temperature between 40 ℃ and the boiling point of the halogenated hydrocarbon for 1 to 4 hours. The product is then typically washed with an inert hydrocarbon solvent such as hexane.
According to another method, the magnesium dichloride is preactivated according to well known methods and then used with an excess of TiCl at a temperature of about 80-135 ℃4And (2) treating, wherein the 1, 8-naphthalenediamine compound or the 1, 8-naphthalenediamine compound and a second electron donor compound are contained in the solution. With TiCl4Treated multiple times and the solid washed with hexane to remove any reacted TiCl4。
Further processes include, also, the preparation with reference to the titanium-containing solid catalyst component preparation process disclosed in CN 1208045: firstly, contacting a liquid magnesium compound and a liquid titanium compound at a low temperature in the presence of a compound selected from the group consisting of alcohols, phenols, ketones, aldehydes, ethers, amines, pyridines and esters, precipitating a solid, the temperature at the time of contacting being generally-70 to 200 ℃, preferably-30 to 130 ℃, and the above-mentioned 1, 8-naphthalenediamine compound, or the above-mentioned 1, 8-naphthalenediamine compound and a second electron donor compound being treated during the contacting.
Another process for the preparation of the solid catalyst component of the present invention comprises: dissolving a magnesium compound in a solvent system consisting of an organic epoxy compound, an organic phosphorus compound and an inert diluent (the inert diluent is pentane, hexane, heptane, octane, decane, benzene, toluene, xylene and derivatives thereof or a mixture of any of the compounds in any proportion, preferably toluene, heptane or hexane), forming a uniform solution, mixing the uniform solution with a titanium compound, and precipitating a solid in the presence of a precipitation aid; the solid is treated by the 1, 8-naphthalenediamine compound or the 1, 8-naphthalenediamine compound and a second electron donor compound to be loaded on the solid, and if necessary, treated by titanium tetrahalide and an inert diluent to obtain the product, wherein the precipitation assistant is one of organic acid anhydride, organic acid, ether and ketone. The components are calculated by each mole of magnesium halide, the organic epoxy compound is 0.2-10 moles, the organic phosphine compound is 0.1-3 moles, the precipitation aid is 0-1.0 mole, and the Ti compound is 0.5-150 moles.
The solid catalyst component of the present invention can also be used in SiO2An inorganic oxide such as alumina or a porous resin, activated by a well-known method, and then used with an excess of TiCl at a temperature of about 80 to 135 deg.C4And (3) treating, namely adding the 1, 8-naphthalenediamine compound or the 1, 8-naphthalenediamine compound and a second electron donor compound in the treating process.
The above reaction results in the formation of magnesium halide in active form (generally, crystalline magnesium halide is structured and has little Ti to be supported, thus having low catalytic activity, and to prepare a supported catalyst having high activity, magnesium halide must be subjected to an activation treatment which comprises physically and/or chemically making it into crystallites so that active centers are supported on the surface, edges and defects of magnesium halide, and the treated crystallites of magnesium halide suitable for supporting Ti are referred to as "active magnesium halide"). In addition to these reactions, other methods are known in the literature for forming magnesium halide in active form starting from compounds other than magnesium halide.
In any of the preparation methods, the above electron donor compounds can be added as such or can be prepared in situ by, for example, employing suitable precursors which can be converted in the desired electron donor compound, for example, by means of known chemical reactions such as esterification, transesterification, and the like. Generally, relative to MgCl2The electron donor compound is used in a molar ratio of 0.01 to 5, preferably 0.05 to 2.0.
In any of the preparation methods, the above-mentioned 1, 8-naphthalenediamine compound, or the above-mentioned 1, 8-naphthalenediamine compound and the second electron donor compound may be added simultaneously or separately in any combination in any order in the preparation process, in one batch or in parts.
The solid catalyst component of the present invention is converted into a catalyst for olefin polymerization by reaction with an organoaluminum compound according to a known method. In particular, it is an object of the present invention to provide a process for the preparation of the olefin CH2A catalyst for the polymerization of ═ CHR, where R is hydrogen or a hydrocarbyl group containing 1 to 12 carbon atoms, comprising the product of the reaction of:
(a) the solid catalyst component of the invention contains Mg, Ti and halogen, at least one 1, 8-naphthalene diamine compound selected from the above, optionally, a mono-functional or multi-functional electron donor compound containing or not containing one ether, ester, ketone or amine,
(b) at least one compound of the general formula AlRnX(3-n)Wherein R is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms; x is halogen, n is an integer of more than or equal to 0 and less than or equal to 3; and, optionally,
(c) at least one external electron donor compound.
Preferably, the alkylaluminum compound (b) is selected from the trialkyl such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, trioctylaluminumA base compound. It is also possible to use trialkylaluminums with alkylaluminum halides, alkylaluminum hydrides or compounds such as AlEt2Cl and Al2Et3Cl3Such as alkylaluminum sesquichlorides, alkylaluminoxanes may also be used.
For applications requiring good isotacticity, an external electron donor compound may be used. The external electron donor compound is selected from the compounds with the general formula RnSi(OR1)4-nSiloxane compound of the formula (I), wherein R and R1Is C1-C18Optionally a heteroatom; n is an integer of 0-3.
The siloxane compound may specifically be: trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-n-butylmethoxysilane, triisobutylethoxysilane, tricyclohexylmethylsilane, tricyclohexylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-propyldiethoxysilane, diisopropyldiethoxysilane, di-n-butyldiethoxysilane, diisobutyldiethoxysilane, di-t-butyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-t-butyldiethoxysilane, di-n-butyldiethoxysilane, n-butylmethyldimethoxysilane, di (2-ethylhexyl) dimethoxysilane, di (n-butyldimethoxysilane), di (n, Bis (2-ethylhexyl) diethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylisopropyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldiethoxysilane, cyclopentylisopropyldiethoxysilane, cyclopentylisobutyldimethoxysilane, cyclohexyl-n-propyldimethoxysilane, cyclohexyl-n-propyldiethoxysilane, cyclohexyl-n-butyldiethoxysilane, pentylmethyldimethoxysilane, pentylmethyldiethoxysilane, pentylethyldimethoxysilane, pentylethyldiethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylethoxysilane, 2-ethylhexyltrimethoxysilane, cyclohexyldimethoxysilane, cyclohexyldiethoxysilane, 2-ethylhexyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, tert-butyltrimethoxysilane, n-butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-ethylhexyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclopentyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-ethylhexyltrimethoxysilane, vinyltrimethoxysilane, 2-ethylhexyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3, 5-dimethylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane, bis (3-methylcyclohexyl) dimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, bis (4-methylcyclohexyl) dimethoxysilane, 3, 5-dimethylcyclohexylcyclohexyldimethoxysilane, bis (3, 5-dimethylcyclohexyl) dimethoxysilane, pentakis (, Tetrapropoxysilane and tetrabutoxysilane. Among these organosilicon compounds, the following are preferred: di-n-propyldimethoxysilane, di-isopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-t-butyldimethoxysilane, di-n-butyldiethoxysilane, t-butyltrimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclopentylmethyl-dimethoxysilane, cyclopentylmethyl-diethoxysilane, cyclopentylethyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane and 3, 5-dimethylcyclopentyldimethoxysilane, and the like. These compounds C may be used alone or in admixture thereof.
Examples of preferred silicon compounds are cyclohexylmethyldimethoxysilane; diisopropyl dimethoxysilane; di-n-butyldimethoxysilane; diisobutyldimethoxysilane; diphenyldimethoxysilane; phenyltriethoxysilane; methyl tert-butyl dimethoxysilane; dicyclopentyldimethoxysilane; 2-ethylpiperidinyl-2-tert-butyldimethoxysilane and (1, 1, 1-trifluoro-2-propyl) -2-ethylpiperidinyldimethoxysilane and (1, 1, 1-trifluoro-2-propyl) -methylsulfanyltrimethoxysilane, cyclohexyltrimethoxysilane; t-butyltrimethoxysilane and thexyltrimethoxysilane.
The catalyst of the invention can be used for olefin CH2In the (co) polymerization of ═ CHR, the olefins mentioned are ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene.
For the polymerization of olefins using the catalysts of the present invention, both homopolymerization and copolymerization can be carried out using the catalysts prepared by components a, b or c as described above. The molar ratio of Al in component b to Ti in component a is generally from 1 to 1000, preferably from 50 to 800; when component c is contained, the molar ratio of component c to component b is 0.002 to 10, preferably 0.01 to 2, and most preferably 0.01 to 0.5.
The olefin polymerization catalyst of the present invention preferably comprises the following components or the reaction product of the following components, i.e., does not require the use of an external electron donor:
a) the above solid catalyst component;
b) at least one compound of the general formula AlRnX(3-n)Wherein R is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms; x is halogen, n is an integer of 0-3.
The olefin polymerization, homopolymerization and copolymerization preferably employ only the catalysts prepared by components a and b described above, the molar ratio of Al in component b to Ti in component a being from 1 to 1000mol, preferably from 50 to 800.
The feeding sequence of the components is arbitrary, and the component b is preferably added into the polymerization system first and then the component a is added; when component c is used, it is preferred to add component c after component b and finally component a.
The polymerization process in the present invention may be carried out with or without a solvent. The olefin monomer may be in the gas phase or the liquid phase. Further addition of hydrogen can serve as a molecular weight regulator. The polymerization can of course also be carried out without molecular weight regulators. The polymerization temperature is not higher than 200 ℃, preferably 20 to 100 ℃, more preferably 40 to 80 ℃. The polymerization pressure is not more than 10MPa, preferably 1 to 5 MPa. Either continuous polymerization or batch polymerization processes may be used. And the polymerization reaction may be carried out in one, two or more steps.
The olefins to be homopolymerized or copolymerized using the catalyst of the present invention include linear olefins: ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-nonene, 1-decene; branched olefins such as: 3-methyl-1-butene and 4-methyl-1-pentene; dienes such as: butadiene, vinylcyclopentene, and vinylcyclohexene. The catalyst of the present invention is preferably used in polyethylene and polypropylene. These olefins may be used alone or in combination of two or more.
The polymerization of olefins (referred to herein as bulk polymerization) using the catalyst components a, b, c of the present invention is preferably carried out by prepolymerization to increase the isotacticity, particle properties, etc. of the active polymer of the catalyst. The prepolymerization process can also be used for styrene homopolymerization.
The order of addition of the components and monomers in the prepolymerization process is arbitrary. It is preferred to add component b to the olefin gas which contains the inert or to be polymerized and then to add the olefin or olefins to be polymerized after addition of component a. In the course of the olefin prepolymerization using an organosilane, it is advisable to add component b to the prepolymerization system of an inert gas or an olefin gas to be polymerized, then to add component c, then to add component a, and finally to add the olefin.
The 1, 8-naphthalene diamine compound is used as an internal electron donor, the activity of the obtained catalyst is high, the obtained polypropylene has high isotacticity and adjustable molecular weight distribution, and the polypropylene with wider molecular weight distribution can be obtained. When the 1, 8-naphthalene diamine compound and the diether compound are compounded, the activity of the obtained catalyst is obviously higher than that of the 1, 8-naphthalene diamine compound and the diether compound which are respectively and independently used, the molecular weight distribution of the obtained polyolefin is moderate and wider than that of the polyolefin obtained by the diether catalyst, and the defect that the diether catalyst is high in activity but narrow in polymer molecular weight distribution can be overcome. The polymer obtained by the catalyst component without the external electron donor still has high isotacticity and ultrahigh activity, and still maintains high-level activity along with the prolonging of polymerization time, and the obtained polyolefin has low ash content, so that the catalyst component is suitable for producing low-ash polymer products.
Detailed Description
The present invention will be further described with reference to the following examples, which are provided for the purpose of illustration and are not intended to limit the scope of the present invention.
The compounds listed in the examples are given by way of illustration only and are not intended to limit the invention, other compounds falling within the scope of the invention but not mentioned in the examples.
Determination of the isotacticity of the Polymer
Measured by heptane extraction (6 hours boiling extraction with heptane). Two grams of dried polymer samples were extracted in an extractor with boiling heptane for 6 hours, and the ratio of the weight of the polymer (g) to 2, which was obtained by drying the residue to constant weight, was the isotacticity.
Determination of the molecular weight distribution of the Polymer
The measurement was carried out by gel permeation chromatography type P L-220 using trichlorobenzene as a solvent at 150 ℃ as a standard (polystyrene, flow rate 1.0M L/min, column: 3xPlgel 10um M1 Xed-B300 X7.5nm).
The polymer ash content was determined according to GB/T9345.1-2008.
General formula (II)
TABLE 1
Figure BDA0001242705590000201
Figure BDA0001242705590000202
TABLE 2
Figure BDA0001242705590000211
Figure BDA0001242705590000212
TABLE 3
Figure BDA0001242705590000213
Figure BDA0001242705590000221
Polymerization 1
Polymerization evaluation was carried out with a solid catalyst as a component of an olefin polymerization catalyst:
after a 5L stainless steel reaction kettle is fully replaced by nitrogen, adding a triethylaluminum hexane solution with the concentration of 5m L of 0.5 mol/L, a methylcyclohexyldimethoxysilane (CMMS) hexane solution with the concentration of 1m L of 0.1 mol/L and 10mg of a prepared catalyst, then adding 10m L hexane to flush a feeding line, adding 2L (in a standard state) hydrogen and 2.5L refined propylene, controlling the reaction to carry out prepolymerization for 5 minutes at 20 ℃, heating to 70 ℃, carrying out polymerization reaction for 1 hour at the temperature, cooling the reaction kettle after the reaction is finished, stopping stirring, discharging a reaction product, and drying to obtain a polymer.
Preparation of solid catalyst component
The operations for preparing the catalyst in the examples are all carried out under the protection of high-purity nitrogen. Specific examples are as follows.
Example 1
Adding 10g of diethoxymagnesium and 80m L toluene into 500ml of a 5-neck flask which is fully replaced by nitrogen and is provided with a stirrer to prepare a suspension, then maintaining the temperature at minus 10 ℃, dropwise adding titanium tetrachloride 20m L, slowly heating the system to 10 ℃ after dropwise adding, dropwise adding titanium tetrachloride 60m L, slowly heating to 90 ℃, adding 4g of 1, 8-diisovaleramide-naphthalene diamine (A1), continuously heating to 120 ℃ and keeping the temperature for 2 hours, then carrying out pressure filtration on the liquid, filtering out the liquid, washing the obtained solid for 3 times at 125 ℃ by using 120m L titanium tetrachloride, washing the obtained solid for 2 times at 60 ℃ by using 150m L hexane, washing for 2 times at room temperature, filtering out the liquid and drying to obtain solid powder, namely the solid catalyst component, wherein the titanium content, the internal electron donor content and the polymerization data of the solid catalyst component are shown in a table 4.
Examples 2 to 27
The solid catalyst component was prepared as in example 1 except that 1, 8-diisovaleramide-naphthalenediamine was sequentially replaced with the compounds shown in tables 1 to 3, respectively.
Example 28
In a 500ml 5-neck flask with stirring which was sufficiently purged with nitrogen gas, 10g of MgCl was charged at-15 ℃2·3C2H5Suspension of OH microspheres and 150m of L titanium tetrachloride was prepared, which was then maintained at-15 ℃ for 1 hour, slowly warmed to 80 ℃ and 3g of 1, 8-bis [ N-benzoyl-N-benzyl ] was added]Naphthalene diamine (A20), heating to 110 deg.C, holding the temperature for 1 hr, press filtering, washing the solid with 120m L m titanium tetrachloride at 125 deg.C for 3 times, washing the solid with 150m L hexane at 60 deg.C for 4 times, filtering, and drying to obtain the solid catalyst component.
Example 29
8g of anhydrous magnesium chloride, 38m L decane and 35m L2-ethylhexanol were reacted at 130 ℃ for 2 hours to form a homogeneous solution, 1.7g of phthalic anhydride was added to the solution, and the mixture was stirred at 130 ℃ for 1 hour to completely dissolve the phthalic anhydride in the homogeneous solution, the obtained homogeneous solution was cooled to room temperature and added dropwise to 200m L titanium tetrachloride maintained at-20 ℃ over 1 hour, the mixed solution was heated to 110 ℃ over 4 hours after completion of the dropwise addition, 3g of 1, 8-bis [ N-benzoyl-N-benzyl ] -naphthalenediamine (A20) was added when the temperature reached 110 ℃, the mixture was stirred at the above temperature for 2 hours, after 2 hours of reaction, a solid portion was suspended in 275m L titanium tetrachloride and reacted at 110 ℃ for 2 hours, after the reaction, the solid portion was collected by thermal filtration, washed thoroughly with decane and hexane at 110 ℃ and then dried to obtain a solid catalyst component.
Example 30
In a 500ml 5-neck flask with stirring which is fully replaced by nitrogen, 10g of anhydrous magnesium chloride, 150m L toluene, 17m L epichlorohydrin and 16m L tributyl phosphate are added at room temperature, the temperature is raised to 50 ℃ under stirring and maintained for 2 hours, the solid is completely dissolved, then 2.40g of phthalic anhydride is added and maintained for 1 hour, the solution is cooled to-25 ℃, 110m L is added dropwise in the 1 hour, the temperature is slowly raised to 80 ℃, the solid is gradually washed out in the temperature raising process, 3g of 1, 8-bis [ N-benzoyl-N-benzyl ] -naphthalene diamine (A20) is added, the temperature is maintained for 1 hour at 80 ℃, 200m L toluene is washed twice after filtration, then 120m L toluene and 80m L titanium tetrachloride are added, the temperature is continuously raised to 110 ℃, the liquid is kept for 2 hours at constant temperature, then the liquid is subjected to pressure filtration and repeated treatment once again, the liquid is filtered, the obtained solid is washed 1 time with 100m L dichloroethane, 4 times with hexane, and the solid catalyst component is obtained after drying.
Comparative example 1
The solid catalyst component was prepared as in example 1, except that 4g of 1, 8-diisovaleryl-naphthalenediamine (A1) was replaced with 3g of di-n-butyl phthalate.
Comparative example 2
A solid catalyst component was prepared as in example 26, except that 1, 8-bis [ N-benzoyl-N-benzyl ] -naphthalenediamine (A20) was changed to di-N-butyl phthalate.
Comparative example 3
A solid catalyst component was prepared as in example 27, except that 1, 8-bis [ N-benzoyl-N-benzyl ] -naphthalenediamine (A20) was replaced with di-N-butyl phthalate.
Comparative example 4
The solid catalyst component was prepared as in example 28, except that 1, 8-bis [ N-benzoyl-N-benzyl ] -naphthalenediamine (A20) was replaced with di-N-butyl phthalate.
TABLE 4
Figure BDA0001242705590000231
Figure BDA0001242705590000241
The polymerization results in Table 4 show that the catalysts prepared by using 1, 8-naphthalenediamine compounds as internal electron donors and using four different catalyst preparation processes have excellent activity when used for propylene polymerization. Under the same preparation process, the activity of most of catalysts adopting o-phenylenediamine compounds as internal electron donors is higher than that of catalysts adopting phthalic acid ester, and the highest activity can reach 68.6 Kg/gCat.h-1The molecular weight distribution of the obtained polypropylene is remarkably wider than that of the polypropylene obtained by a phthalate catalyst, and can reach 9.3 at most, and because the molecular weight distributions of different polymers of substituent groups and functional groups in the compound are different, one or more compounds meeting specific molecular weight distribution indexes can be selected according to needs to adjust the molecular weight distribution of a polymer product.
Example 31
In 500ml nitrogen fully replaced 5-neck flask with stirring, adding 10g diethoxy magnesium and 80m L toluene to prepare suspension, then maintaining at-10 ℃, dropwise adding titanium tetrachloride 20m L, slowly heating the system to 10 ℃ after dropwise adding, dropwise adding titanium tetrachloride 60m L, then slowly heating to 90 ℃, adding 3g of 1, 8-bis [ N-benzoyl-N-benzyl ] -naphthalene diamine (A20) and 1g of 9, 9-bis (methoxymethyl) fluorene, then continuously heating to 120 ℃, keeping the temperature constant for 2 hours, then carrying out pressure filtration on the liquid, filtering out the liquid, washing the obtained solid for 3 times at 125 ℃ by using 120m L titanium tetrachloride, washing the obtained solid for 2 times at 60 ℃ by using 150m L hexane, washing for 2 times at room temperature, filtering out the liquid and drying to obtain solid powder, namely the solid catalyst component, wherein the titanium content, the internal electron donor content and the polymerization data of the solid catalyst component are shown in Table 5.
Example 32
A solid catalyst component was prepared as in example 31, except that 1, 8-bis [ N-benzoyl-N-benzyl ] -naphthalenediamine (A20) was replaced with 1, 8-dibenzoyl-naphthalenediamine (A4).
Example 33
A solid catalyst component was prepared as in example 31, except that 1, 8-bis [ N-benzoyl-N-benzyl ] -naphthalenediamine (A20) was replaced with 1, 8-dibenzylimine-naphthalenediamine (A15).
Example 34
A solid catalyst component was prepared as in example 31, except that 1, 8-bis [ N-benzoyl-N-benzyl ] -naphthalenediamine (A20) was replaced with 1, 8-bis [ N-N-hexanoyl-N-hexyl ] -naphthalenediamine (A19).
Example 35
A solid catalyst component was prepared as in example 31, except that 1, 8-bis [ N-benzoyl-N-benzyl ] -naphthalenediamine (A20) was replaced with 1, 8-bis [ N-m-chlorobenzyl-N-m-chlorobenzyl ] -naphthalenediamine (A22).
Example 36
A solid catalyst component was prepared as in example 31, except that 1, 8-bis [ N-benzoyl-N-benzyl ] -naphthalenediamine (A20) was replaced with 1, 8-bis [ N-isovaleryl-N-benzyl ] -naphthalenediamine (A17).
Example 37
A solid catalyst component was prepared as in example 31, except that 3g of 1, 8-bis [ N-benzoyl-N-benzyl ] -naphthalenediamine (A20) and 1g of 9, 9-bismethoxymethylfluorene were replaced with 3g of 1, 8-bis [ N-benzoyl-N-benzyl ] -naphthalenediamine (A20) and 1g of di-N-butyl phthalate.
Example 38
A solid catalyst component was prepared as in example 31, except that 3g of 1, 8-bis [ N-benzoyl-N-benzyl ] -naphthalenediamine (A20) and 1g of 9, 9-bismethoxymethylfluorene were replaced with 3g of 1, 8-bis [ N-benzoyl-N-benzyl ] -naphthalenediamine (A20) and 1g of ethyl 2-isopropyl-2-isopentyl-malonate.
Example 39
A solid catalyst component was prepared as in example 31, except that 3g of 1, 8-bis [ N-benzoyl-N-benzyl ] -naphthalenediamine (A20) and 1g of 9, 9-bismethoxymethylfluorene were replaced with 3g of 1, 8-bis [ N-benzoyl-N-benzyl ] -naphthalenediamine (A20) and 1g of diethyl 2, 3-diisopropylsuccinate.
Example 40
A solid catalyst component was prepared as in example 31, except that 3g of 1, 8-bis [ N-benzoyl-N-benzyl ] -naphthalenediamine (A20) and 1g of 9, 9-bismethoxymethylfluorene were replaced with 3g of 1, 8-bis [ N-benzoyl-N-benzyl ] -naphthalenediamine (A20) and 1g of 2, 4-pentanediol dibenzoate.
EXAMPLE 41
A solid catalyst component was prepared as in example 31, except that 3g of 1, 8-bis [ N-benzoyl-N-benzyl ] -naphthalenediamine (A20) and 1g of 9, 9-bismethoxymethylfluorene were replaced with 2g of 1, 8-bis [ N-benzoyl-N-benzyl ] -naphthalenediamine (A20) and 2g of 9, 9-bismethoxymethylfluorene.
Example 42
A solid catalyst component was prepared as in example 31, except that 3g of 1, 8-bis [ N-benzoyl-N-benzyl ] -naphthalenediamine (A20) and 1g of 9, 9-bismethoxymethylfluorene were replaced with 1g of 1, 8-bis [ N-benzoyl-N-benzyl ] -naphthalenediamine (A20) and 3g of 9, 9-bismethoxymethylfluorene.
Example 43
A solid catalyst component was prepared as in example 31, except that 3g of 1, 8-bis [ N-benzoyl-N-benzyl ] -naphthalenediamine (A20) and 1g of 9, 9-bismethoxymethylfluorene were replaced with 3g of 1, 8-bis [ N-benzoyl-N-benzyl ] -naphthalenediamine (A20) and 1.5g of 9, 9-bismethoxymethylfluorene.
Example 44
A solid catalyst component was prepared as in example 31, except that 3g of 1, 8-bis [ N-benzoyl-N-benzyl ] -naphthalenediamine (A20) and 1g of 9, 9-bismethoxymethylfluorene were replaced with 2g of 1, 8-bis [ N-benzoyl-N-benzyl ] -naphthalenediamine (A20) and 1g of 9, 9-bismethoxymethylfluorene.
Example 45
A solid catalyst component was prepared as in example 31, except that 3g of 1, 8-bis [ N-benzoyl-N-benzyl ] -naphthalenediamine (A20) and 1g of 9, 9-bismethoxymethylfluorene were replaced with 2g of 1, 8-bis [ N-m-chlorobenzoyl-N-m-chlorobenzyl ] -naphthalenediamine (A22) and 2g of 9, 9-bismethoxymethylfluorene.
Example 46
A solid catalyst component was prepared as in example 31, except that 3g of 1, 8-bis [ N-benzoyl-N-benzyl ] -naphthalenediamine (A20) and 1g of 9, 9-bismethoxymethylfluorene were replaced with 1g of 1, 8-bis [ N-m-chlorobenzoyl-N-m-chlorobenzyl ] -naphthalenediamine (A22) and 3g of 9, 9-bismethoxymethylfluorene.
Example 47
A solid catalyst component was prepared as in example 31, except that 3g of 1, 8-bis [ N-benzoyl-N-benzyl ] -naphthalenediamine (A20) and 1g of 9, 9-bismethoxymethylfluorene were replaced with 3g of 1, 8-bis [ N-m-chlorobenzoyl-N-m-chlorobenzyl ] -naphthalenediamine (A22) and 1.5g of 9, 9-bismethoxymethylfluorene.
Example 48
A solid catalyst component was prepared as in example 31, except that 3g of 1, 8-bis [ N-benzoyl-N-benzyl ] -naphthalenediamine (A20) and 1g of 9, 9-bismethoxymethylfluorene were replaced with 2g of 1, 8-bis [ N-m-chlorobenzoyl-N-m-chlorobenzyl ] -naphthalenediamine (A22) and 1g of 9, 9-bismethoxymethylfluorene.
Example 49
A solid catalyst component was prepared as in example 28, except that 3g of 1, 8-bis [ N-benzoyl-N-benzyl ] -naphthalenediamine (A20) was changed to 3g of 1, 8-bis [ N-m-chlorobenzoyl-N-m-chlorobenzyl ] -naphthalenediamine (A22) and 1g of 9, 9-bismethoxymethylfluorene.
Example 50
A solid catalyst component was prepared as in example 29, except that 3g of 1, 8-bis [ N-benzoyl-N-benzyl ] -naphthalenediamine (A20) was changed to 3g of 1, 8-bis [ N-m-chlorobenzoyl-N-m-chlorobenzyl ] -naphthalenediamine (A22) and 1g of 9, 9-bismethoxymethylfluorene.
Example 51
A solid catalyst component was prepared as in example 30, except that 3g of 1, 8-bis [ N-benzoyl-N-benzyl ] -naphthalenediamine (A20) was changed to 3g of 1, 8-bis [ N-m-chlorobenzoyl-N-m-chlorobenzyl ] -naphthalenediamine (A22) and 1g of 9, 9-bismethoxymethylfluorene.
Comparative example 5
The solid catalyst component was prepared as in example 1, except that 1, 8-diisovaleramide-naphthylenediamine (a1) was replaced with 9, 9-methoxymethylfluorene.
Comparative example 6
The solid catalyst component was prepared as in example 1 except that 1, 8-diisovaleramide-naphthalene diamine was replaced with 2-isopropyl-2-isopentyl-malonic acid ethyl ester.
Comparative example 7
The solid catalyst component was prepared as in example 1 except that 1, 8-diisovaleramide-naphthalenediamine was replaced with diethyl 2, 3-diisopropylsuccinate.
Comparative example 8
The solid catalyst component was prepared as in example 1, except that 1, 8-diisovaleramide-naphthalene diamine was replaced with 2, 4-pentanediol dibenzoate.
TABLE 5
Figure BDA0001242705590000271
Figure BDA0001242705590000281
DNBP di-n-butyl phthalate, F L U9, 9-methoxymethyl fluorene
DIE: 2-isopropyl-2-isoamyl-malonic acid ethyl ester, SUC: 2, 3-Diisopropylsuccinic acid diethyl ester
BRD: 2, 4-pentanediol dibenzoate, "-" indicates that the item is absent
As can be seen from the data in Table 5, when different 1, 8-naphthalenediamine and 9, 9-bis (oxymethyl) fluorene are compounded as the internal electron donor of the catalyst component, the activity of the catalyst is significantly higher than that of the catalyst using 1, 8-naphthalenediamine and 9, 9-bis (oxymethyl) fluorene as the internal electron donor, and the molecular weight distribution of the obtained polymer is between that of the 1, 8-naphthalenediamine compound and 9, 9-bis (oxymethyl) fluorene. When other conditions fix that the compounding ratio of only the 1, 8-naphthalene diamine compound and the 9, 9-bis (oxymethylene) fluorene is different, the activity of the catalyst and the molecular weight distribution of the obtained polymer are different, and the highest activity can be improved to 98.3KgPP/gCat, and the molecular weight distribution of the polymer is moderate.
Similarly, when the 1, 8-naphthalenediamine compound is compounded with an internal electron donor such as a phthalic acid ester or a glycol ester, the obtained polymer has a broader molecular weight distribution and a higher activity. The compound of the o-phenylenediamine compound and the compounds can obviously improve the activity of the catalyst and widen the molecular weight distribution range of the polymer.
Polymerization conditions 2
Polymerization evaluation was carried out under the following conditions using a solid catalyst as a component of an olefin polymerization catalyst:
after a 5L stainless steel reaction kettle was sufficiently replaced with nitrogen, a triethylaluminum hexane solution (the amount of triethylaluminum is shown as Al/Ti in Table 4) having a concentration of 0.5 mol/L and 3-5mg of the prepared catalyst were added, 10m L hexane was then added to flush the feed line, 2L (under standard conditions) of hydrogen and 2.5L of purified propylene were added, the reaction was controlled to prepolymerize at 20 ℃ for 5 minutes, the temperature was raised to 70 ℃ and the polymerization was carried out at that temperature for the corresponding time (see Table 6). after the completion of the reaction, the reaction kettle was cooled and stirred to discharge the reaction product, and the polymer was obtained by drying, the results are shown in Table 6.
Example 52 example 57
Polymerization was carried out under the polymerization conditions 2 and those shown in Table 6 using CAT-41 as a catalyst, and the results are shown in Table 6.
Example 58 to example 63
Polymerization was carried out under the polymerization conditions 2 and the conditions shown in Table 6 using the catalyst CAT-45, and the results are shown in Table 6.
Comparative example 9
Polymerization was carried out using the catalyst REF-1 under the conditions described in polymerization conditions 2 and Table 6, and the results are shown in Table 6.
Comparative example 10-comparative example 13
The polymerization was carried out under the conditions described in polymerization conditions 2 and Table 6 using catalysts REF-5 to REF-8, respectively, and the polymerization results are shown in Table 6.
TABLE 6
Figure BDA0001242705590000291
As can be seen from the data in Table 6, when the catalysts CAT-41 and CAT-45 compounded by 1, 8-naphthalene diamine compound and 9, 9-bis (oxymethyl) fluorene are used as an ethoxy magnesium carrier, an external electron donor compound is not used during polymerization, so that the catalyst has ultrahigh activity which is far higher than that of a non-compounded catalyst (comparative examples 9-13) under the same polymerization conditions, and the high isotacticity of more than 98.0 percent is still maintained. When the polymerization time is extended from 60 minutes to 90 minutes and 120 minutes, the catalyst can maintain the ultra-high activity without deterioration. The ash content of the obtained polypropylene is lower when low Al/Ti is adopted, and can be reduced to 31ppm at least.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined generally in dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the specification and relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

Claims (23)

1. A solid catalyst component containing a naphthalenediamine compound, comprising Mg, Ti, halogen and at least one electron donor selected from 1, 8-naphthalenediamine compounds of the general formula (I):
Figure FDA0002539466750000011
wherein R is1-R6Identical or different, is H; halogen; c1-C20May contain one or more heteroatoms selected from N, O, S, P, Si and halogen; r1—R6Two or more of which may be bonded to each other to form a ring; rI-RIVIdentical or different, is H; c1-C20May contain one or more heteroatoms selected from N, O, S, P, Si and halogen, may contain unsaturated bonds; rI—RIVMay be bonded to form a ring or an unsaturated bond.
2. The solid catalyst component according to claim 1, wherein in the general formula (I), R is1-R6Identical or different, is H; halogen; c1-C20Linear or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, halo or substituted with the N, O, S, P, Si heteroatom; or is selected from heterocyclic aryl substituents; r1-R6Two or more of which may be bonded to each other to form a cyclic structure, which may be saturated or unsaturated; rI-RIVIdentical or different, is H; c1-C20Linear or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, halo or substituted with the N, O, S, P, Si heteroatom; or is selected from heterocyclic aryl substituents; rI-RIVMay be bonded to form a ring or an unsaturated bond.
3. The solid catalyst component according to claim 1, characterized in that the electron donor is selected from compounds of general formula (II):
Figure FDA0002539466750000012
wherein the radical R1-R6、RIIAnd RIVHas the same meaning as in the general formula (I); r7Is C1-C20May contain one or more heteroatoms selected from N, O, S, P, Si and halogen as substituents of carbon atoms or hydrogen atoms or both.
4. The solid catalyst component according to claim 3 in which R is7Is C1-C20Linear or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, halo or substituted with the N, O, S, P, Si heteroatom.
5. The solid catalyst component according to claim 3, characterized in that the electron donor is selected from compounds of general formula (III):
Figure FDA0002539466750000021
wherein the radical R1-R6Has the same meaning as in the general formula (I), R7Has the same meaning as in the general formula (II), R8And R8’Identical or different, selected from H; c1-C20May contain one or more heteroatoms selected from N, O, S, P, Si and halogen as substituents of carbon atoms or hydrogen atoms or both.
6. The solid catalyst component according to claim 5 in which R is8Or R8’Is C1-C20Linear or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, alkyl which is halo-or substituted by the heteroatom N, O, S, P, Si, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, or phenylalkyl,An indenyl group; or is selected from heterocyclic aryl substituents.
7. The solid catalyst component according to claim 1, characterized in that the electron donor is selected from compounds of general formula (IV):
Figure FDA0002539466750000022
wherein the radical R1-R6Has the same meaning as in the general formula (I); r8And R8’Has the same meaning as in the general formula (III).
8. The solid catalyst component according to any of claims 1 to 7, characterized in that it comprises only 1, 8-naphthalenediamine compounds selected from said general formula (I) as electron donors.
9. The solid catalyst component according to any of claims 1 to 7 comprising, in addition to the 1, 8-naphthalenediamine compound of general formula (I), another electron donor compound selected from L ewis bases containing one or more electronegative groups, wherein the electron donor atom is selected from the group consisting of N, O, S, P, As or Sn.
10. The solid catalyst component according to claim 9, characterized in that the further electron donor compound is selected from the group of electron donor compounds of diethers, esters, diketones and diamines.
11. The solid catalyst component of claim 9, wherein the molar ratio of the 1, 8-naphthalenediamine compound to the another electron donor compound is 0.01-100.
12. The solid catalyst component of claim 11, wherein the molar ratio of the 1, 8-naphthalenediamine compound to the another electron donor compound is 0.02-50.
13. The solid catalyst component of claim 12, wherein the molar ratio of the 1, 8-naphthalenediamine compound to the another electron donor compound is 0.05-20.
14. The solid catalyst component according to claim 10, characterized in that the diether compound is selected from 1,3 diethers of general formula (V):
Figure FDA0002539466750000031
wherein: r, R1、R2、R3、R4And R5Which may be identical or different, represent H or a linear or branched alkyl, cycloalkyl, aryl, alkylaryl or arylalkyl radical having from 1 to 18 carbon atoms; r6And R7And may be the same or different and represent a straight-chain or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 5 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms and an arylalkyl group; r to R7One or more of the groups may be linked to form a cyclic structure, and may each comprise one or more heteroatoms selected from halogen, N, O, S, P, and Si.
15. The solid catalyst component according to claim 10, wherein the ester compound is a monocarboxylic acid ester or a polycarboxylic acid ester compound.
16. The solid catalyst component according to claim 15 in which the polycarboxylic acid ester compound is a diester of an aromatic dicarboxylic acid.
17. The solid catalyst component according to claim 16 characterized in that the diester of an aromatic dicarboxylic acid is a phthalic diester or a terephthalic diester.
18. The solid catalyst component according to claim 10, characterized in that the ester compound is selected from succinates of general formula (VI):
Figure FDA0002539466750000041
wherein the radical R1And R2Identical or different from each other, is C1-C20A linear or branched alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkaryl group, optionally comprising heteroatoms; r3-R6Wherein at least two radicals are different from hydrogen and are selected from C1-C20Linear or branched alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkaryl radicals, optionally containing hetero atoms, and, in addition, the radicals R3-R6May be joined together to form a ring.
19. The solid catalyst component according to claim 10, characterized in that the ester compound is selected from the group of diol ester compounds of general formula (VII):
Figure FDA0002539466750000042
in the formula R1-R6、R1’-R2’Is the same or different hydrogen, halogen or substituted or unsubstituted straight chain or branched C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl, C7-C20 arylalkyl, C2-C10 alkenyl or C10-C20 condensed ring aryl; but R is1’And R2’Not being hydrogen, R1-R6Optionally looped or not looped.
20. The solid catalyst component according to claim 1 comprising the reaction product of a titanium compound, a magnesium compound and at least one compound selected from the 1, 8-naphthalenediamines, the precursor of the magnesium compound being selected from at least one of: xnMg(OR)2-n，MgCl2·mROH，R2-nMgXn，MgCl2/SiO2，MgCl2/Al2O3Or a mixture of a magnesium halide and a titanium alkoxide, where m is a number from 0.1 to 6, 0 < n > 2, X is halogen, R is hydrogen or C1-C20A hydrocarbon group of (a); the general formula of the titanium compound is TiXN(OR)4-NWherein R is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, and N is 1 to 4.
21. A process for preparing the solid catalyst component for olefin polymerization according to any one of claims 1 to 20, comprising: contacting a magnesium compound and a titanium compound with at least one internal electron donor compound selected from the 1, 8-naphthalenediamine compounds to obtain a solid catalyst component.
22. For olefin CH2A catalyst for the polymerization of ═ CHR, where R is hydrogen or a hydrocarbyl group containing 1 to 12 carbon atoms, characterized in that it comprises the product of the reaction:
(a) the solid catalyst component of any one of claims 1 to 20;
(b) at least one compound of the general formula AlRnX(3-n)Wherein R is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms; x is halogen, n is an integer of more than or equal to 0 and less than or equal to 3; and, optionally,
(c) at least one selected from the group consisting of RnSi(OR1)4-nAs an external electron donor compound, wherein R and R1Is C1-C18Optionally a heteroatom; n is an integer of 0-3.
23. For olefins CH2A process for the polymerization of ═ CHR comprising homopolymerization, prepolymerization and copolymerization, wherein R is hydrogen or a hydrocarbyl group containing 1 to 12 carbon atoms, carried out in the presence of a catalyst as claimed in claim 22.
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