CN108570119A - A kind of ingredient of solid catalyst containing naphthylenediamine class compound, catalyst and its application - Google Patents

A kind of ingredient of solid catalyst containing naphthylenediamine class compound, catalyst and its application Download PDF

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CN108570119A
CN108570119A CN201710140629.XA CN201710140629A CN108570119A CN 108570119 A CN108570119 A CN 108570119A CN 201710140629 A CN201710140629 A CN 201710140629A CN 108570119 A CN108570119 A CN 108570119A
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naphthylenediamine
bis
compound
alkyl
ingredient
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CN108570119B (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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Beijing Li Hezhixin Science And 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 present invention provides a kind of ingredient of solid catalyst containing naphthylenediamine class compound, and it includes Mg, Ti, halogen and at least one electron donor, which is 1, the 8 naphthylenediamine class compounds in general formula (I).The invention also discloses the applications containing the catalyst of the ingredient of solid catalyst and the catalyst in olefinic polyreaction, the application especially in propylene polymerization.Catalyst activity of the present invention is high, and resulting polymers isotacticity is high, molecular weight distribution is wide and adjustable, when with diether compound compounding as internal electron donor, can produce low ash content polymer.

Description

A kind of ingredient of solid catalyst containing naphthylenediamine class compound, catalyst and its Using
Technical field
The present invention relates to one kind being used for CH2The ingredient of solid catalyst of=CHR olefinic polymerizations, wherein R is hydrogen or contains 1-12 The hydrocarbyl group of a carbon atom, it is more particularly related to which the ingredient of solid catalyst containing naphthylenediamine class compound, contains The application of the catalyst of the ingredient of solid catalyst and the catalyst in olefinic polyreaction, especially in propylene polymerization In application.
Background technology
In propylene polymerization industry, the catalyst studied and be most widely used is Ziegler-Natta catalyst, this is urged Agent is prepared by internal electron donor is added during carrying out load titanium to active magnesium chloride support.Due to internal electron donor Catalyst performance can farthest be changed, therefore study and find ideal internal electron donor compound to become Z-N catalyst The focus and hot spot of research.Currently, being focused primarily upon both at home and abroad for the research of internal electron donor：1) traditional aliphatic ester and Aromatic esters compound, main representative are phthalate compounds；2) diether compound (such as EP0361493, EP0728724)；3) succinate compound compound (such as WO9856834, WO0063261, WO03022894)；4) diol-lipid Compound (such as WO9856834, WO0063261, WO03022894)；5) other functional groups compound (CN1105671, CN1242780, US20060128558) etc..
But in practical applications, above compound all exists as the internal electron donor of catalyst for olefines polymerizing and centainly asks Topic, the catalyst activity for such as making internal electron donor using binary aromatic carboxylic acid's ester type compound is not high, made polypropylene (PP) Relative molecular mass distribution is also relatively narrow, and phthalate compound is as common plasticizer, to the healthy reproduction of people There is very big harm with environment；Using 1, although the catalyst activity that 3- diether compounds make internal electron donor is higher, and urge Agent hydrogen response, but the relative molecular mass distribution of made PP is narrow, is unfavorable for developing the PP of the different trades mark；Succinic acid Ester type compound makees internal electron donor, and advantage is that the PP relative molecular mass distributions of synthesis are wider, is disadvantageous in that PP's is vertical The hydrogen response of structure regularity and catalyst is to be improved；And the activity of diol-lipid catalyst system and catalyzing is whole not as good as two ethers System is ideal.
1,3- diether compound needs, succinate compound compound preparation longer by two-step reaction preparation production procedure Yield is relatively low, and the more difficult preparation of primary raw material such as 2, the 4- pentanediols of diol-lipid compound leads to higher price, therefore above-mentioned gives The production cost of electron compound is higher, is unfavorable for the marketing of product.
Therefore, develop that good activity, stereoselectivity are good, molecular weight distribution is wider or adjustable, polymer comprehensive performance It is good, while the novel electron donor of low production cost and be to make great efforts in the industry applied to efficient Ziegler-Natta catalyst is prepared Target.A kind of 1,8- naphthylenediamines class compound provided by the invention can preferably solve the above problems.
In addition, when the catalyst prepared using single internal electron donor cannot be satisfied the particular requirement of polypropylene product, Such as the characteristics of requiring catalyst to be provided simultaneously with high activity, high stereoselectivity and high hydrogen response, a variety of internal electron donors Be used in compounding be also solves the problems, such as this effective ways, i.e., when preparing Z-N catalyst, at the same use two kinds or two kinds with On internal electron donor, and improve the comprehensive of Z-N catalyst by adjusting content of the different internal electron donors in Z-N catalyst Close performance.
Invention content
The purpose of the present invention is to provide one kind being used for CH2The ingredient of solid catalyst of=CHR olefinic polyreactions.
Another object of the present invention is to provide the preparation methods of the ingredient of solid catalyst.
It is still another object of the present invention to provide the ingredients of solid catalyst in CH2It is prepared by=CHR olefin polymerization catalysis In application.
In order to achieve the object of the present invention, the present invention provides the ingredients of solid catalyst containing naphthylenediamine class compound (CH2=CHR alkene, wherein R are hydrogen or the hydrocarbyl group containing 1-12 carbon atom), it includes Mg, Ti, halogens and and at least one Kind electron donor, the electron donor are 1, the 8- naphthylenediamine class compounds in general formula (I)：
Wherein, R1-R6It is identical or different, it is H；Halogen；C1-C20Alkyl, containing selected from N, O, S, P, Si and halogen One or more hetero atoms；R1、R2、R3And R4It is therein two or more to be mutually bonded cyclization；RI-RIVIt is identical or different, be H；C1-C20Alkyl, containing selected from N, O, S, P, Si and halogen one or more hetero atoms, unsaturated bond can be contained；RI- RIVBonding cyclization or unsaturated bond.
Preferably, R1-R6It is identical or different, it is H；Halogen；C1-C20Linear chain or branched chain alkyl, naphthenic base, alkenyl, ester Base, phenyl, alkyl phenyl, phenylalkyl, indenyl, benzyl, halogenated or the alkyl, the cycloalkanes that are replaced by N, O, S, P, Si hetero atom Base, phenyl, alkyl phenyl, phenylalkyl, indenyl, benzyl；Or it is selected from heterocyclic aryl substituent group；R1-R6Two therein or more It is a to be mutually bonded circlewise structure, it is saturation or undersaturated；RI-RIVIt is identical or different, it is H；C1-C20Straight chain Or the alkyl of branch, naphthenic base, alkenyl, ester group, phenyl, alkyl phenyl, phenylalkyl, indenyl, benzyl, it is halogenated or by N, O, S, P, alkyl, naphthenic base, phenyl, alkyl phenyl, phenylalkyl, indenyl, the benzyl of Si hetero atoms substitution；Or it is selected from heterocyclic aryl Substituent group；RI—RIVBonding cyclization or unsaturated bond.
In one embodiment, R1-R6At least one of (or two or three or four) R group be selected from substitution The hydrocarbyl group comprising 1 to 20 carbon atom, it is unsubstituted include 1 to 20 carbon atom hydrocarbyl group, include 1 to 20 The alkoxy base of carbon atom, hetero atom, and combinations thereof.
In one embodiment, R1-R6In any adjacent R group can connect to form knot in interannular structure or ring Structure.Structure can be or can not be aromatics in interannular/ring.In one embodiment, structure is C5 membered rings in interannular/ring Or C6 membered rings.
In compound described in above-mentioned general formula (I), one is preferably the compound of the following general formula (II)：
Wherein, group R1—R6、RIIAnd RIVThere is meaning identical with formula (I) is led to；R7For C1-C20Alkyl, can contain One or more hetero atoms selected from N, O, S, P, Si and halogen, as carbon atom either hydrogen atom or the substituent group of the two, Preferably it is C1-C20The alkyl of linear chain or branched chain, naphthenic base, alkenyl, ester group, phenyl, alkyl phenyl, phenylalkyl, indenyl, Benzyl, halogenated or the alkyl, naphthenic base, phenyl, alkyl phenyl, phenylalkyl, indenyl, the benzyl that are replaced by N, O, S, P, Si hetero atom Base.
Being included in the specific example of the compound in general formula (II) is：
1,8- diacetayl amide-naphthylenediamine；1,8- bis- positive propionamide-naphthylenediamine；1,8- diisopropyl amide-naphthylenediamine；1,8- Di-n-butyramide-naphthylenediamine；1,8- bis- isobutyramides-naphthylenediamine；1,8- bis- n-valeramides-naphthylenediamine；1,8- diisoamyl amide- Naphthylenediamine；1,8- bis- penta formamide of ring-naphthylenediamine；1,8- bis- n-caproamides-naphthylenediamine；1,8- bis- hexamethylene formamide-naphthylenediamine； 1,8- bis- heptamides-naphthylenediamine；1,8- bis- caprylamides-naphthylenediamine；1,8- bis- pelargonamides-naphthylenediamine；1,8- bis- decyl amide-naphthalene two Amine；1,8- bis- [undecanoic amide]-naphthylenediamine；1,8- bis- [lauramide]-naphthylenediamine；1,8- bis- [tridecanoyl amine]-naphthylenediamine；1, 8- bis- [myristamide]-naphthylenediamine；1,8- bis- [pentadecanoyl amine]-naphthylenediamine；1,8- bis- [palmitamide]-naphthylenediamine；1,8- bis- [heptadecanoyl amine]-naphthylenediamine；1,8- bis- [stearamide]-naphthylenediamine；1,8- bis- [19 amide]-naphthylenediamine；1,8- bis- [20 Amide]-naphthylenediamine；1,8- dibenzamide-naphthylenediamine；1,8- bis- to chlorobenzamide-naphthylenediamine；1,8- bis- adjacent chlorobenzoyl Amine-naphthylenediamine；1,8- bis- chlorobenzamide-naphthylenediamine；1,8- bis- to methyl benzamide-naphthylenediamine；1,8- bis- to methoxy Yl-benzamide-naphthylenediamine；1,8- bis- p-nitrophenyl formamide-naphthylenediamine；1,8- bis- brombenzamide-naphthylenediamine；1,8- Hexichol oxygen formamide-naphthylenediamine；1,8- bis- naphthalenecarboxamides-naphthylenediamine；1,8- bis- to trifluoromethyl benzamide-naphthylenediamine；1, Bis- phenyl-pentafluoride formamides of 8--naphthylenediamine；1,8- bis- to propyl benzamide-naphthylenediamine；1,8- bis- to t-butylbenzamide-naphthalene Diamines；1,8- bis- to isobutyl-benzene formamide-naphthylenediamine；1,8- bis- trimethylbenzoyl amine-naphthylenediamine；1,8- bis- [N- benzene Formyl amine-n-tertiary butyl]-naphthylenediamine；1,8- bis- [N- benzoyl amine-n -s phenyl]-naphthylenediamine；1,8- bis- [N- benzoyl amine-n -s P-methylphenyl]-naphthylenediamine.
1,8- bis- positive ethoxylate amids-naphthylenediamine；1,8- bis- positive third oxanamide-naphthylenediamine；1,8- bis- positive fourth oxanamide-naphthalene two Amine；1,8- bis- isobutyl oxanamide-naphthylenediamine；1,8- bis- positive penta oxanamide-naphthylenediamine；1,8- diisoamyl oxanamide-naphthylenediamine；1, The just own oxanamide-naphthylenediamines of 8- bis-；1,8- bis- positive oxanamide in heptan-naphthylenediamine；1,8- bis- just pungent oxanamide-naphthylenediamine；1,8- bis- Positive nonyl oxanamide-naphthylenediamine 1, bis- positive decimemide-naphthylenediamines of 8-；1,8- benzene oxygen formamide-naphthylenediamine；1,8- to methylenedioxy phenoxy Formamide-naphthylenediamine；1,8- to methoxybenzene oxygen formamide-naphthylenediamine；1,8- to chlorobenzene oxygen formamide-naphthylenediamine；1,8- pair Nitrobenzene oxygen formamide-naphthylenediamine；Chlorobenzene oxygen formamide-naphthylenediamine between 1,8-；1,8- neighbour's chlorobenzene oxygen formamide-naphthylenediamine；1, 8- is to trifluoromethylbenzene oxygen formamide-naphthylenediamine.
In compound described in logical formula (II), one kind is preferably the compound of the following general formula (III)：
Wherein, group R1-R6There is meaning identical with formula (I) is led to, R7There is meaning identical with formula (II) is led to, R8With R8’It is identical or different, it is selected from H；C1-C20Alkyl, containing selected from N, O, S, P, Si and halogen one or more hetero atoms, As carbon atom either hydrogen atom or the substituent group of the two, preferably C1-C20Linear chain or branched chain alkyl, naphthenic base, alkene Base, ester group, phenyl, alkyl phenyl, phenylalkyl, indenyl, benzyl, it is halogenated or replaced by N, O, S, P, Si hetero atom alkyl, Naphthenic base, phenyl, alkyl phenyl, phenylalkyl, indenyl, benzyl；Or it is selected from heterocyclic aryl substituent group.
Being included in the specific example of the compound in logical formula (III) is：
1,8- bis- [N- acetyl-N- n-propyls]-naphthylenediamine；1,8- bis- [N- acetyl-N- isopropyls]-naphthylenediamine；1,8- bis- [N- propionyl-N- normal-butyls]-naphthylenediamine；1,8- bis- [N- isobutyryl-N- isobutyl groups]-naphthylenediamine；1,8- bis- [N- isovaleryls-N- N-pentyl]-naphthylenediamine；1,8- bis- [penta formyl-N- isopentyl of N- rings]-naphthylenediamine；1,8- bis- [the positive hexanoyl-N- n-hexyls of N-]- Naphthylenediamine；1,8- bis- [N- hexamethylene formyl-N- n-heptyls]-naphthylenediamine；1,8- bis- [N- caprinoyl-N- positive decyls]-naphthylenediamine；1,8- Two [N- hexanoyl-N- cyclohexyl methyls]-naphthylenediamines；1,8- bis- [penta formyl-N- methyl cyclopentanes of N- rings]-naphthylenediamine；1,8- bis- [the N- last of the ten Heavenly stems Acyl-N- undecyls]-naphthylenediamine；1,8- bis- [N- lauroyl-N- dodecyls]-naphthylenediamine；1,8- bis- [N- isovaleryls-N- ten Tetraalkyl]-naphthylenediamine；1,8- bis- [the positive hexanoyl-N- cetyls of N-]-naphthylenediamine；1,8- bis- [N- caprinoyl-N- octadecyls]- Naphthylenediamine；1,8- bis- [N- hexamethylene formyl-N- eicosyls]-naphthylenediamine；
1,8- bis- [N- benzoyl-N- benzyls]-naphthylenediamine；1,8- bis- [N- benzoyl-N- benzhydryls]-naphthylenediamine；1, 8- bis- [N- benzene oxygen formyl-N- benzyls]-naphthylenediamine；1,8- bis- [N- is to methoxybenzoyl-N- benzyls]-naphthylenediamine；1,8- bis- [N- is to toluyl-N- benzyls]-naphthylenediamine；1,8- bis- [N- p-nitrophenyl formyl-N- benzyls]-naphthylenediamine；1,8- bis- [N- To chlorobenzoyl-N- benzyls]-naphthylenediamine；1,8- bis- [chlorobenzoyl-N- benzyls between N-]-naphthylenediamine；1,8- bis- [N- neighbour's chlorobenzene Formyl-N- benzyls]-naphthylenediamine；1,8- bis- [N- is to trifluoromethylbenzoyl-N- benzyls]-naphthylenediamine；1,8- bis- [front three between N- Base benzoyl-N- benzyls]-naphthylenediamine；1,8- bis- [Bromophenacyl-N- benzyls between N-]-naphthylenediamine；1,8- bis- [N- naphthalene formyls-N- Benzyl]-naphthylenediamine；1,8- bis- [N- is to tert-butyl benzoyl-N- benzyls]-naphthylenediamine；1,8- bis- [N- benzoyl-N- are to methyl Benzyl]-naphthylenediamine；1,8- bis- [N- benzoyl-N- are to mehtoxybenzyl]-naphthylenediamine；1,8- bis- [- N- pairs of N- benzoyls Nitrobenzene methyl]-naphthylenediamine；1,8- bis- [N- benzoyl-N- are to chlorophenylmethyl]-naphthylenediamine；1,8- bis- [between N- benzoyls-N- Chlorophenylmethyl]-naphthylenediamine；1,8- bis- [N- benzoyl-N- neighbours chlorophenylmethyl]-naphthylenediamine；1,8- bis- [three between N- benzoyls-N- Methylbenzyl]-naphthylenediamine；1,8- bis- [N- benzoyl-N- are to ter .- butylbenzyl]-naphthylenediamine；1,8- bis- [chlorobenzene first between N- Chlorophenylmethyl between acyl-N-]-naphthylenediamine；1,8- bis- [N- is to tert-butyl benzoyl-N- to ter .- butylbenzyl]-naphthylenediamine；1,8- Two [trimethylbenzene methyl between trimethylbenzoyl-N- between N-]-naphthylenediamines；
1,8- bis- [N- acetyl-N- benzyls]-naphthylenediamine；1,8- bis- [N- acetyl-N- benzhydryls]-naphthylenediamine；1,8- bis- [N- propionyl-N- benzyls]-naphthylenediamine；1,8- bis- [the positive butyryl-N- benzyls of N-]-naphthylenediamine；1,8- bis- [N- isobutyryl-N- benzyls Base]-naphthylenediamine；1,8- bis- [the positive valeryl-N- of N- are to mehtoxybenzyl]-naphthylenediamine；1,8- bis- [N- isovaleryl-N- are to nitro Benzyl]-naphthylenediamine；1,8- bis- [penta formyl-N- of N- rings is to chlorophenylmethyl]-naphthylenediamine；1, the 8- bis- [positive hexanoyl-N- m-chloros of N- Benzyl]-naphthylenediamine；1,8- bis- [N- hexamethylene formyl-N- neighbours chlorophenylmethyl]-naphthylenediamine；1,8- bis- [N- oenanthyl-N- are to tertiary fourth Base benzyl]-naphthylenediamine；1,8- bis- [trimethylbenzene methyl between N- decoyls-N-]-naphthylenediamine；1,8- bis- [N- nonanoyl-N- benzyls Base]-naphthylenediamine；1,8- bis- [N- caprinoyl-N- benzyls]-naphthylenediamine；1,8- bis- [N- undecanoyl-N- benzyls]-naphthylenediamine；1,8- bis- [N- lauroyl-N- benzyls]-naphthylenediamine；1,8- bis- [N- myristoyl-N- benzyls]-naphthylenediamine；1,8- bis- [N- palmityl-N- benzyls Base]-naphthylenediamine；1,8- bis- [18 acyl-N- benzyls of N-]-naphthylenediamine；1,8- bis- [20 acyl-N- benzyls of N-]-naphthylenediamine；
1,8- bis- [N- benzoyl-N- n-propyls]-naphthylenediamine；1,8- bis- [N- benzoyl-N- isopropyls]-naphthylenediamine；1, 8- bis- [N- benzoyl-N- normal-butyls]-naphthylenediamine；1,8- bis- [N- benzoyl-N- isobutyl groups]-naphthylenediamine；1,8- bis- [three between N- Toluyl-N- n-pentyls]-naphthylenediamine；1,8- bis- [N- is to tert-butyl benzoyl-N- isopentyl]-naphthylenediamine；1,8- bis- [N- is to toluyl-N- n-hexyls]-naphthylenediamine；1,8- bis- [N- is to methoxybenzoyl-N- n-heptyls]-naphthylenediamine；1, 8- bis- [N- is to chlorobenzoyl-N- positive decyls]-naphthylenediamine；1,8- bis- [N- neighbour chlorobenzoyl-N- cyclohexyl methyls]-naphthylenediamine；1, 8- bis- [chlorobenzoyl-N- methyl cyclopentanes between N-]-naphthylenediamine；1,8- bis- [N- benzoyl-N- undecyls]-naphthylenediamine；1,8- Two [N- benzoyl-N- dodecyls]-naphthylenediamines；1,8- bis- [N- benzoyl-N- myristyls]-naphthylenediamine；1,8- bis- [N- benzene Formyl-N- cetyls]-naphthylenediamine；1,8- bis- [N- benzoyl-N- octadecyls]-naphthylenediamine；1,8- bis- [N- benzoyls-N- Eicosyl]-naphthylenediamine；
1,8- bis- [N- benzene oxygen formyl-N- isopropyls]-naphthylenediamine；1,8- bis- [N- benzene oxygen formyl-N- benzyls]-naphthylenediamine； 1,8- bis- [N- benzene oxygen formyl-N- benzhydryls]-naphthylenediamine；1,8- bis- [N- benzene oxygen formyl-N- normal-butyls]-naphthylenediamine；1,8- Two [N- is to methylenedioxy phenoxy formyl-N- isopropyls]-naphthylenediamines；1,8- bis- [N- is to methoxybenzene oxygen formyl-N- isopropyls]-naphthalene two Amine；1,8- bis- [chlorobenzene oxygen formyl-N- isopropyls between N-]-naphthylenediamine；1,8- bis- [N- is to trifluoromethylbenzene oxygen formyl-N- isopropyls Base]-naphthylenediamine；1,8- bis- [the just own oxygen formyl-N- isopropyls of N-]-naphthylenediamine；1,8- bis- [N- ethoxycarbonyl-N- isopropyls]- Naphthylenediamine；1,8- bis- [the positive fourth oxygen formyl-N- isopropyls of N-]-naphthylenediamine；1,8- bis- [the just own oxygen formyl-N- benzyls of N-]-naphthalene two Amine；1,8- bis- [the just own oxygen formyl-N- benzhydryls of N-]-naphthylenediamine；1,8- bis- [the just own oxygen formyl-N- n-pentyls of N-]-naphthalene two Amine；1,8- bis- [the positive ethoxycarbonyl-N- benzyls of N-]-naphthylenediamine；1,8- bis- [the positive ethoxycarbonyl-N- benzhydryls of N-]-naphthylenediamine； 1,8- bis- [the positive ethoxycarbonyl-N- n-pentyls of N-]-naphthylenediamine.
In compound described in general formula (I), the compound of another preferably the following general formula (IV)：
Wherein, group R1-R6There is meaning identical with formula (I) is led to；R8And R8’There is meaning identical with formula (III) is led to.
Being included in the specific example of the compound in logical formula (III) is：
1,8- bis- ethyleneimines-naphthylenediamine；1,8- bis- positive tetrahydroform-naphthylenediamine；1,8- diisopropyl imines-naphthylenediamine；1,8- Two positive fourth imines-naphthylenediamines；1,8- bis- isobutyl imines-naphthylenediamine；1,8- bis- positive penta imines-naphthylenediamine；1,8- diisoamyl imines- Naphthylenediamine；1,8- bis- penta azomethine of ring-naphthylenediamine；1,8- bis- just own imines-naphthylenediamine；1,8- bis- hexamethylene azomethine-naphthylenediamine； 1,8- bis- heptan imines-naphthylenediamine；1,8- bis- pungent imines-naphthylenediamine；1,8- bis- nonyl imines-naphthylenediamine；1,8- didecyl imines-naphthalene two Amine；1,8- bis- [11 imines]-naphthylenediamine；1,8- bis- [ten diimines]-naphthylenediamine；1,8- bis- [13 imines]-naphthylenediamine；1, 8- bis- [14 imines]-naphthylenediamine；1,8- bis- [15 imines]-naphthylenediamine；1,8- bis- [16 imines]-naphthylenediamine；1,8- bis- [17 imines]-naphthylenediamine；1,8- bis- [18 imines]-naphthylenediamine；1,8- bis- [19 imines]-naphthylenediamine；1,8- bis- [20 Imines]-naphthylenediamine；1,8- NSC 334072-naphthylenediamine；1,8- bis- [NSC 334072]-naphthylenediamine；1,8- bis- is sub- to chlorobenzene first Amine-naphthylenediamine；1,8- bis- adjacent chlorobenzene azomethine-naphthylenediamine；1,8- bis- m-chloro benzimide-naphthylenediamine；1,8- bis- to methylbenzene Azomethine-naphthylenediamine；1,8- di-p-methoxy benzimide-naphthylenediamine；1,8- bis- p-nitrophenyl azomethine-naphthylenediamine；1,8- Two bromobenzene azomethine-naphthylenediamines；1,8- hexichol oxygen azomethine-naphthylenediamine；1,8- dinaphthyl azomethine-naphthylenediamine；1,8- bis- is right Trifluoromethyl benzimide-naphthylenediamine；1,8- bis- phenyl-pentafluoride azomethine-naphthylenediamine；1,8- bis- to propyl benzimide-naphthalene two Amine；1,8- bis- to tert-butyl benzene azomethine-naphthylenediamine；1,8- bis- to isobutyl-benzene azomethine-naphthylenediamine；1,8- bis- trimethyl Benzimide-naphthylenediamine.
1, the 8- naphthylenediamine classes compound of the present invention can be synthesized by various reactions, such as will be substituted or unsubstituted 1,8- naphthylenediamine is reacted with acyl chlorides or chloro-formate, can obtain working as RIIAnd RIVFor H when logical formula (II) compound；
Work as RIIAnd RIVBe not H and it is identical when the compound of logical formula (II) can be obtained by method shown in following formula, this method It is especially suitable for preparing and works as RIIFor the compound of the logical formula (II) of the groups such as aryl, substituted aryl, heterocycle, tertiary butyl：
Logical formula (III) compound is preferred as lead to formula (II) compound one, can be by will be substituted or unsubstituted 1,8- naphthylenediamine is first reacted with aldehydes or ketones, is obtained by the reaction again with acyl chlorides or chloro-formate after reduction reaction：
Substituted or unsubstituted 1,8- naphthylenediamines are reacted with aldehydes or ketones can obtain the compound of logical formula (IV)：
A kind of situation of the ingredient of solid catalyst of the present invention is to contain only 1, the 8- naphthylenediamine classes of the general formula (I) Close object.
Another situation of the ingredient of solid catalyst of the present invention is, except 1, the 8- naphthylenediamines containing the general formula (I) Also include at least another electron donor compound except class compound, which is selected from containing one or more electronegativity The Lewis alkali of group, electron donor atom therein be selected from N, O, S, P, As or Sn composition group, preferably be selected from two ethers, esters, The electron donor compound of diones and Diamines.When 1,8- naphthylenediamine class compounds and other above-mentioned published interior electrons When body compound is used together, the catalyst that performance can be adjusted can be obtained.
The molar ratio of 1,8- naphthylenediamine class compound and another electron donor compound is 0.01-100, preferably 0.02-50, more preferable 0.05-20.
Another electron donor compound except 1, the 8- naphthylenediamine class compounds of general formula (I) preferably, is selected from general formula (V) 1,3-, bis- ethers：
Wherein：R、R1、R2、R3、R4And R5It may be the same or different, represent H or have the straight chain of 1-18 carbon atom or branched alkane Base, naphthenic base, aryl, alkaryl or aralkyl；R6And R7It may be the same or different, represent the straight chain or branch for having 1-20 carbon atom Change the alkaryl and aralkyl of alkyl, the naphthenic base of 3-20 carbon atom, the aryl of 5-20 carbon atom, 7-20 carbon atom；R To R7One or more of group can link to form cyclic structure, may include selected from halogen, one of N, O, S, P and Si or Multiple hetero atoms.
The specific example for the ethers that can be advantageously used includes：2- (2- ethylhexyls) 1,3- dimethoxy propanes, 2- isopropyl -1,3- dimethoxy propanes, 2- butyl -1,3- dimethoxy propanes, 2- sec-butyl -1,3- dimethoxy propanes, 2- cyclohexyl -1,3- dimethoxy propanes, 2- phenyl -1,3- dimethoxy propanes, 2- tertiary butyl -1,3- dimethoxy propanes, 2- cumyl -1,3- dimethoxy propanes, 2- (2- phenylethyls) -1,3- dimethoxy propanes, 2- (2- cyclohexyl-ethyls) -1,3- Dimethoxy propane, 2- (rubigan) -1,3- dimethoxy propanes, 2- (diphenyl methyl) -1,3- dimethoxy propanes, 2 (1- naphthalenes) -1,3- dimethoxy propanes, 2 (p-fluorophenyl) -1,3- dimethoxy propanes, 2- (1- decahydros naphthalene) -1,3- bis- Methoxy propane, 2 (to tert-butyl-phenyl) -1,3- dimethoxy propanes, 2,2- dicyclohexyl -1,3- dimethoxy propanes, 2, 2- diethyl -1,3- dimethoxy propanes, 2,2- dipropyl -1,3- dimethoxy propanes, 2,2- dibutyl -1,3- dimethoxys Propane, 2,2- diethyl -1,3- di ethyl propyl ethers, 2,2- bicyclopentyl -1,3- dimethoxy propanes, 2,2- dipropyl -1, 3- di ethyl propyl ethers, 2,2- dibutyl -1,3- di ethyl propyl ethers, 2- methyl -2- ethyl -1,3- dimethoxy propanes, 2- Methyl-2-propyl -1,3- dimethoxy propane, 2- methyl -2- benzyl -1,3- dimethoxy propanes, phenyl -1 2- methyl -2-, 3- dimethoxy propanes, 2- methyl -2- cyclohexyl -1,3- dimethoxy propanes, 2- methyl -2- methylcyclohexyl -1,3- diformazans Oxygroup propane, 2,2- bis- (rubigan) -1,3- dimethoxy propanes, 2,2- bis- (2- phenylethyls) -1,3- dimethoxys third Alkane, 2,2- bis- (2- cyclohexyl-ethyls) -1,3- dimethoxy propanes, 2- methyl -2- isobutyl group -1,3- dimethoxy propanes, 2- Methyl -2- (2- ethylhexyls) -1,3- dimethoxy propanes, 2,2- bis- (2- ethylhexyls) -1,3- dimethoxy propanes, 2,2- Bis- (p-methylphenyl) -1,3- dimethoxy propanes, 2- methyl -2- isopropyl -1,3- dimethoxy propanes, 2,2- bis- isobutyls Base -1,3- dimethoxy propane, 2,2- diphenyl -1,3- dimethoxy propanes, 2,2- dibenzyl -1,3- dimethoxy propanes, 2- isopropyl -2- cyclopenta -1,3- dimethoxy propanes, 2,2- bis- (cyclohexyl methyl) -1,3- dimethoxy propanes, 2,2- bis- Isobutyl group -1,3- di ethyl propyl ether, 2,2- diisobutyl -1,3- dibutoxy propane, 2- isobutyl group -2- isopropyls -1,3- Dimethoxy propane, 2,2- di-sec-butyl -1,3- dimethoxy propanes, 2,2- di-t-butyl -s 1,3- dimethoxy propanes, 2, 2- di neo-pentyl -1,3- dimethoxy propanes, 2- i-propyl -2- isopentyl -1,3- dimethoxy propanes, 2- phenyl -2- benzyls Base -1,3- dimethoxy _ _ base propane, 2- cyclohexyl -2- cyclohexyl methyl -1,3- dimethoxy propanes.Bis- (the methoxy methyls of 1,1- Base)-cyclopentadiene；Bis- (the methoxy) -2,3,4,5- tetramethyl-ring pentadienes of 1,1-；Bis- (methoxy) -2 1,1-, 3,4,5- tetraphenyl cyclopentadiene；Bis- (the methoxy) -2,3,4,5- tetrafluoro cyclopentadiene of 1,1-；Bis- (the methoxy methyls of 1,1- Base) -3,4- bicyclopentyl cyclopentadiene；Bis- (methoxy) indenes of 1,1-；Bis- (the methoxy) -2,3- dimethyl of 1,1- Indenes；Bis- (the methoxy) -4,5,6,7- tetrahydroindenes of 1,1-；Bis- (the methoxy) -2,3,6,7- tetrafluoro indenes of 1,1-；1,1- is bis- (methoxy) -4,7- dimethyl indenes；Bis- (the methoxy) -3,6- dimethyl indenes of 1,1-；1,1- bis- (methoxies)- 4- phenylindans；Bis- (the methoxy) -4- phenyl -2- methyl indenes of 1,1-；Bis- (the methoxy) -4- cyclohexyl indenes of 1,1-；1, Bis- (methoxy) -7- (3,3,3- trifluoro propyls) indenes of 1-；Bis- (the methoxy) -7- trimethyl silyl indenes of 1,1-； Bis- (the methoxy) -7- trifluoromethyl indenes of 1,1-；Bis- (the methoxy) -4,7- dimethyl -4,5,6,7- tetrahydroindenes of 1,1-； Bis- (the methoxy) -7- methyl indenes of 1,1-；Bis- (the methoxy) -7- cyclopenta indenes of 1,1-；1,1- bis- (methoxies)- 7- isopropyl indenes；Bis- (the methoxy) -7- cyclohexyl indenes of 1,1-；Bis- (the methoxy) -7- tertiary butyl indenes of 1,1-；1,1- is bis- (methoxy) -7- tertiary butyl -2- methyl indenes；Bis- (the methoxy) -7- phenylindans of 1,1-；Bis- (the methoxy methyls of 1,1- Base) -2- phenylindans；Bis- (methoxy) -1H- benzos [e] indenes of 1,1-；Bis- (the methoxy) -1H-2- methyl benzos of 1,1- [e] indenes；Bis- (methoxy) fluorenes of 9,9-；Bis- (the methoxy) -2,3,6,7- tetramethyl fluorenes of 9,9-；Bis- (the methoxyl groups of 9,9- Methyl) -2,3,4,5,6,7- hexafluoro fluorenes；Bis- (the methoxy) -2,3- benzfluorenes of 9,9-；Bis- (methoxy) -2 9,9-, 3,6,7- dibenzo fluorenes；Bis- (the methoxy) -2,7- diisopropyl fluorenes of 9,9-；Bis- (the methoxy) -1,8- dichloros of 9,9- Fluorenes；Bis- (the methoxy) -2,7- bicyclopentyl fluorenes of 9,9-；Bis- (the methoxy) -1,8- difluoro fluorenes of 9,9-；Bis- (the first of 9,9- Oxygroup methyl) -1,2,3,4- tetrahydrochysene fluorenes；Bis- (the methoxy) -1,2,3,4,5,6,7,8- octahydro fluorenes of 9,9-；Bis- (the first of 9,9- Oxygroup methyl) -4- tertiary butyl fluorenes.
Another electron donor compound except 1, the 8- naphthylenediamine class compounds of general formula (I) is preferably monocarboxylic esters Or polybasic carboxylic acid esters compound, specific example are aromatic binary carboxylic acid compound and aliphatic chain dicarboxylic acids esters chemical combination Object：
The diester of aromatic binary carboxylic acid, such as ditridecyl phthalate or bis- terephthalate.Ditridecyl phthalate Including：Repefral, diethyl phthalate, n-propyl phthalate, diisopropyl phthalate, N-butyl phthalate, diisobutyl phthalate, Methyl Benzene-o-dicarboxylate ethyl ester, Methyl Benzene-o-dicarboxylate isopropyl Ester, Methyl Benzene-o-dicarboxylate n-propyl, ethyl phthalate N-butyl, ethyl phthalate isobutyl ester, phthalic acid Two n-pentyl esters, di-iso-amyl phthalate, dihexyl phthalate, heptyl phthalate ester, phthalic acid two N-octyl, diisooctyl phthalate, phthalic acid (2,2- dimethylhexanyl) diester, phthalic acid (2- ethyl hexyls Base) diester, 2-nonyl-phthalate ester, diisooctyl phthalate, phthalic acid (2,2- dimethyl heptyl) diester, N-butyl phthalate dissident's base ester, n-butyl phthalate (2- ethylhexyls) ester, phthalic acid n-pentyl ester just oneself The different nonyl ester of ester, phthalic acid n-pentyl ester, the positive last of the ten Heavenly stems ester of isoamyl phthalate, phthalic acid n-pentyl ester hendecane ester, neighbour The just own ester (2- methylhexyl esters) of phthalic acid isopentyl dissident base ester, phthalic acid, phthalic acid n-hexyl (2- ethyls Hexyl ester), the just own ester (different nonyl ester) of phthalic acid, phthalic acid n-hexyl (positive last of the ten Heavenly stems ester), the positive heptyl ester (2- of phthalic acid Ethylhexyl), the positive heptyl ester of phthalic acid (different nonyl ester), the new nonyl ester of the positive heptyl ester of phthalic acid and phthalic acid 2- ethyls Own ester (different nonyl ester).These esters can be independent or a variety of be used in mixed way.Bis- terephthalate includes：Terephthalic acid (TPA) diformazan Ester, diethyl terephthalate, terephthalic acid (TPA) di-n-propyl ester, terephthalic acid (TPA) diisopropyl ester, di-n-butyl terephthalate, Di-n-butyl terephthalate, isobutyl terephthalate, terephthalic acid (TPA) ethyl ester methyl ester, terephthalic acid (TPA) methyl esters isopropyl Ester, terephthaldehyde's acetoacetic ester (n-propyl), terephthaldehyde's acetoacetic ester (N-butyl), terephthaldehyde's acetoacetic ester (isobutyl ester), to benzene Two n-pentyl ester of dioctyl phthalate, terephthalic acid (TPA) diisoamyl ester, terephthalic acid (TPA) dihexyl, two positive heptyl ester of terephthalic acid (TPA), to benzene two Formic acid di-n-octyl, two different n-octyl of terephthalic acid (TPA), terephthalic acid (TPA) two (2,2- dimethylhexanyl) ester, terephthalic acid (TPA) two (2- ethylhexyls) ester, two positive nonyl ester of terephthalic acid (TPA), terephthalic acid (TPA) dinonyl, terephthalic acid (TPA) diisodecyl ester, to benzene Dioctyl phthalate two (2,2- dimethyl ethyl heptyl) ester, terephthalic acid (TPA) N-butyl dissident ester, terephthalic acid (TPA) N-butyl (2 ethyls Hexyl) ester, the just own ester of terephthalic acid (TPA) n-pentyl ester, terephthalic acid (TPA) n-pentyl ester dissident ester, terephthaldehyde's isoamyl valerate (heptyl ester), Terephthalic acid (TPA), terephthalic acid (TPA) n-pentyl ester (2- ethylhexyls) ester, terephthalic acid (TPA) n-pentyl ester (different nonyl ester), terephthalic acid (TPA) Isopentyl ester (positive last of the ten Heavenly stems ester), terephthalic acid (TPA) n-pentyl ester hendecane ester, terephthaldehyde isoamyl valerate dissident ester, terephthalic acid (TPA) just oneself The just own ester (positive last of the ten Heavenly stems ester) of base (2- ethylhexyls), terephthalic acid (TPA) n-hexyl (isononyl ester), terephthalic acid (TPA), terephthaldehyde Sour n-heptyl (2- ethylhexyls), terephthalic acid (TPA) n-heptyl (isononyl ester), terephthalic acid (TPA) n-heptyl (new last of the ten Heavenly stems ester) and Terephthalic acid (TPA) 2- ethylhexyls (isononyl ester).These esters can be independent or a variety of be used in mixed way.
Diethyl phthalate, dipropyl phthalic butyl ester, terephthalic acid (TPA) two are recommended in these diester Isopropyl ester, n-butyl phthalate, diisobutyl phthalate, di-n-octyl phthalate, phthalic acid two Different monooctyl ester, di-n-butyl terephthalate, isobutyl terephthalate, terephthalic acid (TPA) di-n-octyl, terephthalic acid (TPA) two One or more of different monooctyl ester, (2- ethylhexyls) ester of terephthalic acid (TPA) two or diisooctyl phthalate mix It closes.
It is particularly preferred that the succinate compound compound selected from logical formula (VI) in polybasic carboxylic acid esters compound：
Wherein, group R1And R2, it is same or different to each other, is C1-C20 line styles or branched-alkyl, alkenyl, naphthenic base, virtue Base, aralkyl or alkylaryl group optionally include hetero atom；R3-R6In at least two groups be different from hydrogen and be selected from C1- C20Line style or branched-alkyl, alkenyl, naphthenic base, aryl, aralkyl or alkylaryl group, optionally contain hetero atom, in addition, Group R3-R6It can be connected together and constitute a ring.R1And R2Preferably C1-C8 alkyl, naphthenic base, aryl, aralkyl and alkane virtue Base group.Particularly preferably such compound, wherein R1And R2Selected from primary alkyl, especially branched primary alkyl.Suitable R1 And R2Example be methyl, ethyl, n-propyl, normal-butyl, isobutyl group, neopentyl, 2- ethylhexyls.Particularly preferably second Base, isobutyl group and neopentyl.
One of the preferred compounds category of logical formula (VI) description is such, wherein R3-R5It is hydrogen and R6It is with 3-10 Branched-alkyl, naphthenic base, aryl, aralkyl and the alkylaryl group of a carbon atom.Particularly preferably such compound, Middle R6It is the branched primary alkyl group or group of naphthene base with 3-10 carbon atom.Suitable monosubstituted succinate compound Specific example be sec-butyl diethyl succinate, hexyl diethyl succinate, cyclopropyl diethyl succinate, norborny amber Amber diethyl phthalate, perhydrogenating diethyl succinate, trimethyl-succinic acid diethylester, methoxyl group diethyl succinate, to methoxyl group Phenylsuccinic acid diethylester, rubigan diethyl succinate, phenylsuccinic acid diethylester, cyclohexyl diethyl succinate, benzyl Base diethyl succinate, cyclohexyl methyl diethyl succinate, tertiary butyl diethyl succinate, isobutyl group diethyl succinate, Isopropyl diethyl succinate, neopentyl diethyl succinate, isopentyl diethyl succinate, (1- trifluoromethyls ethyl) amber Diethyl phthalate, fluorenyl diethyl succinate, phenylsuccinic acid (1- ethyoxyl carbonyls diisobutyl ester) (1- (ethoxycarbo Diisobutyl phenylsuccinate), sec-butyl di-iso-octyl succinate, hexyl di-iso-octyl succinate, cyclopropyl amber Amber acid diisobutyl ester, norborny di-iso-octyl succinate, perhydrogenating di-iso-octyl succinate, trimethyl silyl succinic acid Diisobutyl ester, methoxyl group di-iso-octyl succinate, p-methoxyphenyl di-iso-octyl succinate, p-chlorophenyl succinic acid two are different Butyl ester, cyclohexyl di-iso-octyl succinate, benzyl di-iso-octyl succinate, cyclohexyl methyl di-iso-octyl succinate, tertiary butyl Di-iso-octyl succinate, isobutyl group di-iso-octyl succinate, isopropyl di-iso-octyl succinate, two isobutyl of neopentyl succinic acid It is ester, isopentyl di-iso-octyl succinate, (1- trifluoromethyls ethyl) di-iso-octyl succinate, fluorenyl di-iso-octyl succinate, secondary Two peopentyl ester of butyl succinic acid, two peopentyl ester of hexyl succinic acid, two peopentyl ester of cyclopropyl succinic acid, norborny succinic acid two are new Pentyl ester, two peopentyl ester of perhydrogenating succinic acid, two peopentyl ester of trimethyl silyl succinic acid, two peopentyl ester of methoxyl group succinic acid, Two peopentyl ester of p-methoxyphenyl succinic acid, two peopentyl ester of rubigan succinic acid, two peopentyl ester of phenylsuccinic acid, cyclohexyl amber Two peopentyl esters of amber acid, two peopentyl ester of benzyl succinic acid, two peopentyl ester of cyclohexyl methyl succinic acid, tertiary butyl succinic acid two new penta Ester, two peopentyl ester of isobutyl group succinic acid, two peopentyl ester of isopropyl succinic acid, two peopentyl ester of neopentyl succinic acid, isopentyl amber Sour two peopentyl esters, two peopentyl ester of (1- trifluoromethyls ethyl) succinic acid, two peopentyl ester of fluorenyl succinic acid.
Another kind of preferred compound is such, wherein R in compound in logical formula (VI)3-R6In at least two Group is different from hydrogen and is selected from C1-C20 line styles or branched-alkyl, alkenyl, naphthenic base, aryl, aralkyl or alkaryl base Group, optionally contains hetero atom.The group of particularly preferably such compound, two of which non-hydrogen is connected to the same carbon On atom.Suitable two replace the specific example of succinate to be：2,2- dimethylsuccinic diethyl phthalates, 2- Ethyl-2-Methyls Diethyl succinate, 2- benzyl -2- isopropyls diethyl succinate, 2- cyclohexyl methyl -2- isobutyl groups diethyl succinate, 2- Cyclopenta -2- normal-butyls diethyl succinate, 2,2- diisobutyls diethyl succinate, 2- cyclohexyl -2- ethylsuccinic acids two Ethyl ester, 2- isopropyl -2- methyl succinics diethyl phthalate, 2- myristyl -2- ethylsuccinic acids diethylester, 2- isobutyl group -2- second Base diethyl succinate, 2- (1- trifluoromethyls ethyl) -2- methyl succinics diethyl phthalate, 2- isopentyl -2- isobutyl group succinic acids Diethylester, 2- phenyl -2- normal-butyls diethyl succinate, 2,2- dimethyl succinates diisobutyl ester, 2- Ethyl-2-Methyl ambers Sour diisobutyl ester, 2- benzyl -2- isopropyls di-iso-octyl succinate, 2- cyclohexyl methyl -2- isobutyl groups di-iso-octyl succinate, 2- cyclopenta -2- normal-butyls di-iso-octyl succinate, 2,2- diisobutyls di-iso-octyl succinate, 2- cyclohexyl -2- ethyl ambers Amber acid diisobutyl ester, 2- isopropyl -2- methylsuccinic acids diisobutyl ester, 2- myristyl -2- ethylsuccinic acids diisobutyl ester, 2- Isobutyl group -2- ethylsuccinic acids diisobutyl ester, 2- (1- trifluoromethyls ethyl) -2- methylsuccinic acids diisobutyl ester, 2- isopentyl - 2- isobutyl groups di-iso-octyl succinate, 2- phenyl -2- normal-butyls di-iso-octyl succinate, 2,2- dimethyl succinates two new penta Ester, two peopentyl ester of 2- Ethyl-2-Methyls succinic acid, two peopentyl ester of 2- benzyl -2- isopropyls succinic acid, 2- cyclohexyl methyls -2- Two peopentyl ester of isobutyl group succinic acid, two peopentyl ester of 2- cyclopenta -2- normal-butyls succinic acid, 2,2- diisobutyls succinic acid two new penta Ester, two peopentyl ester of 2- cyclohexyl -2- ethylsuccinic acids, two peopentyl ester of 2- isopropyl -2- methylsuccinic acids, 2- myristyls -2- Two peopentyl ester of ethylsuccinic acid, two peopentyl ester of 2- isobutyl group -2- ethylsuccinic acids, 2- (1- trifluoromethyls ethyl) -2- methyl ambers Two peopentyl esters of amber acid, two peopentyl ester of 2- isopentyl -2- isobutyl groups succinic acid, two peopentyl ester of 2- phenyl -2- normal-butyls succinic acid.
In addition, also particularly preferably such compound, the group of wherein at least two non-hydrogen are connected to different carbon atoms, i.e., R3And R5Or R4And R6.The specific example of suitable compound is 2,3- bis- (trimethyl silyl) diethyl succinate, 2- Sec-butyl -3- methyl succinics diethyl phthalate, 2- (3,3,3- trifluoro propyl) -3- methyl succinics diethyl phthalate, (the 2- ethyls of 2,3- bis- Butyl) diethyl succinate, 2,3- diethyl -2- isopropyls diethyl succinate, 2,3- diisopropyl -2- methylsuccinic acids two Ethyl ester, 2,3- dicyclohexyl -2- methyl succinics diethyl phthalate, 2,3- dibenzyl diethyl succinate, 2,3- diisopropyl ambers Diethyl phthalate, 2,3- bis- (cyclohexyl methyl) diethyl succinate, 2,3- di-t-butyls diethyl succinate, 2,3- diisobutyls Diethyl succinate, 2,3- di neo-pentyls diethyl succinate, 2,3- diisoamyl diethyl succinate, (the 1- trifluoros of 2,3- bis- Methylethyl) diethyl succinate, 2,3- bis- (myristyl) diethyl succinate, 2,3-, bis- fluorenyl diethyl succinates, 2- Isopropyl -3- isobutyl groups diethyl succinate, 2- tertiary butyl -3- isopropyls diethyl succinate, 2- isopropyl -3- cyclohexyl ambers Amber diethyl phthalate, 2- isopentyl -3- cyclohexyl diethyl succinate, 2- myristyl -3- cyclohexyl diethyl succinate, 2- rings Hexyl -3- cyclopenta diethyl succinate, 2,2,3,3- tetramethyl diethyl succinates, 2,2,3,3- tetraethyl succinic acid diethyls Ester, 2,2,3,3- tetrapropyl diethyl succinates, 2,3- diethyl -2,3- diisopropyls diethyl succinate, 2,2,3,3- tetra- Fluorine diethyl succinate, 2,3- bis- (trimethyl silyl) di-iso-octyl succinate, 2- sec-butyl -3- methylsuccinic acids two are different Butyl ester, 2- (3,3,3- trifluoro propyl) -3- methylsuccinic acids diisobutyl ester, 2,3- bis- (2- ethyl-butyls) succinic acid, two isobutyl Ester, 2,3- diethyl -2- isopropyls di-iso-octyl succinate, 2,3- diisopropyl -2- methylsuccinic acids diisobutyl ester, 2,3- bis- Cyclohexyl -2- methylsuccinic acids diisobutyl ester, 2,3- dibenzyl di-iso-octyl succinate, 2,3- diisopropyls succinic acid, two isobutyl Ester, 2,3- bis- (cyclohexyl methyl) di-iso-octyl succinate, 2,3- di-t-butyls di-iso-octyl succinate, 2,3- diisobutyl ambers Amber acid diisobutyl ester, 2,3- di neo-pentyls di-iso-octyl succinate, 2,3- diisoamyl di-iso-octyl succinate, 2,3-, bis- (1- Trifluoromethyl ethyl) di-iso-octyl succinate, 2,3- bis- (myristyl) di-iso-octyl succinate, 2,3-, bis- fluorenyl succinic acids two Isobutyl ester, 2- isopropyl -3- isobutyl groups di-iso-octyl succinate, 2- tertiary butyl -3- isopropyls di-iso-octyl succinate, 2- isopropyls Base -3- cyclohexyl di-iso-octyl succinate, 2- isopentyl -3- cyclohexyl di-iso-octyl succinate, 2- myristyl -3- cyclohexyl Methylsuccinic acid diisobutyl ester, 2- cyclohexyl -3- cyclopenta di-iso-octyl succinate, 2,2,3,3- tetramethyl succinic acid, two isobutyl Ester, 2,2,3,3- tetraethyl di-iso-octyl succinates, 2,2,3,3- tetrapropyl di-iso-octyl succinates, 2,3- diethyl -2,3- Dipropyl di-iso-octyl succinate, 2,2,3,3- tetrafluoro di-iso-octyl succinates, 2,3- bis- (trimethyl silyl) succinic acid Two peopentyl esters, two peopentyl ester of 2- sec-butyl -3- methylsuccinic acids, 2- (3,3,3- trifluoro propyl) -3- methylsuccinic acids two new penta Ester, 2,3- bis- (2- ethyl-butyls) succinic acid, two peopentyl ester, 2,3- diethyl -2- isopropyls succinic acid, two peopentyl ester, 2,3- bis- Two peopentyl ester of isopropyl -2- methylsuccinic acids, 2,3- dicyclohexyl -2- methylsuccinic acids, two peopentyl ester, 2,3- dibenzyl ambers Sour two peopentyl esters, 2,3- diisopropyls succinic acid, two peopentyl ester, 2,3- bis- (cyclohexyl methyl) succinic acid, two peopentyl ester, 2,3- bis- Two peopentyl ester of tertiary butyl succinic acid, 2,3- diisobutyls succinic acid, two peopentyl ester, 2,3- di neo-pentyls succinic acid, two peopentyl ester, 2, Two peopentyl ester of 3- diisoamyl succinic acid, 2,3- (1- trifluoromethyls ethyl) succinic acid, two peopentyl ester, 2,3- bis- (myristyl) Two peopentyl ester of succinic acid, 2,3-, bis- fluorenyl succinic acids, two peopentyl ester, two peopentyl ester of 2- isopropyl -3- isobutyl groups succinic acid, uncle 2- Two peopentyl ester of butyl -3- isopropyls succinic acid, two peopentyl ester of 2- isopropyl -3- cyclohexyl succinic acid, 2- isopentyl -3- cyclohexyl Two peopentyl ester of succinic acid, two peopentyl ester of 2- myristyl -3- cyclohexyl methyls succinic acid, 2- cyclohexyl -3- cyclopenta succinic acids Two peopentyl esters, 2,2,3,3- tetramethyl succinic acid, two peopentyl ester, 2,2,3,3- tetraethyl succinic acid, two peopentyl ester 2,2,3,3- tetra- Two peopentyl ester of propyl succinic acid, 2,3- diethyl -2,3- diisopropyls succinic acid, two peopentyl ester, 2,2,3,3- tetrafluoro succinic acids two Peopentyl ester.
Such as group R mentioned above, being connected on same carbon atom3-R6In two or four compositions that link together The compound of the logical formula (VI) of one ring is also preferred.The specific example of suitable compound is 1- (carbethoxyl group) -1- (second Oxygroup acetyl) -2,6- dimethyl cyclohexanes, 1- (carbethoxyl group) -1- (Ethoxyacetyl) -2,5- dimethylcyclopentanes, 1- (second Oxygen carbonyl) -1- (Ethoxyacetylmethyl) -2- hexahydrotoluenes, 1- (carbethoxyl group) -1- (Ethoxyacetylcyclohexyl) Hexamethylene.
Compound above-mentioned can be or different with position in the form of pure isomer or with the form of mixtures of enantiomer The form of mixtures of structure body and enantiomer uses.When pure isomer to be used, common technology well known in the art is generally used It is separated.In particular, certain in succinate of the present invention can be used as pure racemic or meso-form, or alternatively Mixture in the form of both uses.
Another electron donor compound except 1, the 8- naphthylenediamine class compounds is further preferably selected from general formula (VII) glycol ester compounds：
R in formula1-R6、R1’-R2’For identical or different hydrogen, the C1- of halogen or substituted or unsubstituted linear chain or branched chain C20 alkyl, C3-C20 naphthenic base, C6-C20 aryl, C7-C20 alkaryls, C7-C20 aralkyl, C2-C10 alkylenes or C10- C20 fused ring aryls；But R1’And R2’It is not hydrogen, R1-R6One or more of it is optionally cyclic or not cyclic.
The diol-lipid compound specifically can be used：1,3-PD dibenzoate, 2- methyl-1s, 3-propanediol Dibenzoate, 2- ethyls -1,3-PD dibenzoate, 2- propyl -1,3-PD dibenzoate, butyl -1 2-, 3-propanediol dibenzoate, 2,2-dimethyl-1,3-propanediol dibenzoate, 2- ethyls -2- butyl -1,3-PD two Benzoic ether, 2,2- diethyl -1,3-PD dibenzoate, 2- methyl-2-propyls -1,3-PD dibenzoate, 2- isopropyls -2- isopentyl -1,3-PD dibenzoate, 2,4- glycol dibenzoates, 3- methyl -2,4- pentanediols Dibenzoate, 3- ethyls -2,4- glycol dibenzoate, 3- propyl -2,4- glycol dibenzoate, butyl -2 3-, 4- glycol dibenzoates, 3,3- dimethyl -2,4- glycol dibenzoate, 2- methyl-1s, 3- pentanediol dibenzoic acids Ester, 2,2- dimethyl -1,3- glycol dibenzoate, 2- ethyls -1,3- glycol dibenzoate, 2- butyl -1,3- penta Bisbenzoate, 2- methyl-1s, 3- glycol dibenzoates, 2- ethyls -1,3- glycol dibenzoate, 2- third Base -1,3- glycol dibenzoate, 2- butyl -1,3- glycol dibenzoate, 2,2- dimethyl -1,3- pentanediol hexichol Formic acid esters, 2- methyl-1s, 3- glycol dibenzoates, 2,2- dimethyl -1,3- glycol dibenzoate, ethyl -1 2-, 3- glycol dibenzoates, 2- butyl -1,3- glycol dibenzoate, 2,2,4- trimethyl -1,3- pentanediol hexichol first Acid esters, 3- methyl -3- butyl -2,4- glycol dibenzoate, 2,2- dimethyl -1,5-PD dibenzoate, 3,5- Heptandiol dibenzoate, 4- ethyl -3,5- heptandiol dibenzoates etc..It is preferred that pentadiol ester and heptandiol ester.
The present invention the ingredient of solid catalyst for olefinic polymerization, including titanium compound, magnesium compound, selected from above-mentioned The precursor of at least one 1,8- naphthylenediamine class compounds, the magnesium compound is selected from least one：XnMg(OR)2-n, MgCl2· MROH, R2-nMgXn, MgCl2/SiO2, MgCl2/Al2O3Or the mixture of magnesium halide and alcohol titanium, m is the number of 0.1-6 in formula, 0≤ N≤2, X are halogen, and R is C1-C20Alkyl；The general formula of the titanium compound is TiXN(OR)4-N, R is that carbon atom number is in formula The alkyl of 1-20, X are halogen, N=1-4.
One kind of the ingredient of solid catalyst for olefinic polymerization of the present invention is preferably, including titanium compound, magnesium chemical combination Object, (i) are selected from least one of above-mentioned 1,8- naphthylenediamine class compounds, and single official of (ii) at least one ether, ester, ketone or amine It can roll into a ball or polyfunctional group electron donor compound, the precursor of the magnesium compound are selected from least one：XnMg(OR)2-n, MgCl2· MROH, R2-nMgXn, MgCl2/SiO2, MgCl2/Al2O3Or the mixture of magnesium halide and alcohol titanium, m is the number of 0.1-6 in formula, 0≤ N≤2, X are halogen, and R is C1-C20Alkyl；The general formula of the titanium compound is TiXN(OR)4-N, R is that carbon atom number is in formula The alkyl of 1-20, X are halogen, N=1-4.
The magnesium compound of the present invention preferably uses magnesium hydrocarbyloxy compound.
Another alcohol adduct for preferably using magnesium dihalide of magnesium compound of the present invention.
The titanium compound of the present invention includes titanium tetrachloride, titanium tetrabromide, titanium tetra iodide or alkyl halide titanium, alkyl halide titanium Such as methoxytitanium trichloride, ethyoxyl titanium trichloride, propoxyl group titanium trichloride, nbutoxytitanium trichloride, dimethoxy dichloro Change titanium, diethoxy titanium chloride, dipropoxy titanium chloride, two n-butoxy titanium chloride, trimethoxy titanium chloride, three second Oxygroup titanium chloride, tripropoxy titanium chloride or three n-Butoxyl titanium-chlorides.It can be applied in these halogenated titaniums one or more mixed It closes and uses.Wherein preferably use titanium tetrachloride.
The preparation of the ingredient of solid catalyst of the present invention can be carried out according to several method：
According to one of which method, TiCl is used4Or aromatic hydrocarbons (such as toluene, dimethylbenzene etc.) solution of titanium alkoxides can be with It is reacted with two magnesium hydrocarbyloxy compounds of such as dialkoxy magnesium or two aryloxy group magnesium etc at -25-0 DEG C, and at 80-130 DEG C Carry out halogenation.Use TiCl4The processing that carries out of arene solution can be repeated one or more times, and one in repeatedly such processing It is secondary or above-mentioned 1,8- naphthylenediamine class compounds or above-mentioned 1,8- naphthylenediamine class compounds and second of electron is added portionwise Body compound.Such as it can refer to the preparation method of the solids containing titanium catalytic component disclosed in US5077357 and prepared：According to Secondary addition magnesium ethylate, purity titanium tetraethoxide, o-cresol, ethyl alcohol and chlorobenzene, stirring；By TiCl4/ chlorobenzene solution rapidly joins above-mentioned In liquid, heating until completely dissolved, is continuously heating to specific temperature；Utilize N2Bubbling continues to stir after taking away ethanol synthesis object Certain time, then washed once using hot chlorobenzene, isooctane washes twice, then N2Drying can obtain carrier.Or according to another Example：Successively by TiCl4, purity titanium tetraethoxide, magnesium ethylate and o-cresol be added in chlorobenzene, stirring；Ethyl alcohol is added, is waited under high temperature Continue to stir 3h after magnesium ethylate dissolving；Then filtering while hot washed once using warm chlorobenzene, isooctane washed once, last N2 It is dry.
According to another method, the alcoholates or chlorohydrin of magnesium and in the solution contain above-mentioned 1,8- naphthylenediamine classes The excessive TiCl of compound or above-mentioned 1,8- naphthylenediamine class compounds and second of electron donor compound4In 80-135 It is reacted at a temperature of DEG C.Can be TiX by general formula according to preferred methodn(OR)4-nTitanium compound, R is carbon atom number in formula For the alkyl of 1-20, X is halogen, n=1-4；It is preferred that TiCl4, with from general formula be MgCl2The adduct of mROH is reacted and is prepared Ingredient of solid catalyst, m is the number of 0.1-6 in formula, preferably 2-3.5, and R is the alkyl for having 1-20 carbon atom.Adduct It can be conveniently made by the following method spherical：In the presence of the not unreactive hydrocarbons miscible with adduct, alcohol and magnesium chloride are mixed It closes, makes the rapid chilling of the lotion, to make adduct cure in the form of spheric granules.The spherical shape prepared according to the process MgCl2The example description of mROH adducts is found in US4399054 and US4469648.The obtained adduct can be with It is directly reacted with titanium compound or it can first pass through the dealcoholization (80-130 DEG C) of thermal control to obtain a kind of adduction in advance The molal quantity of object, wherein alcohol is generally below 3, preferably between 0.1 and 2.5.It can be by by adduct (dealcoholysis or itself) It is suspended in cold TiCl4It carries out in (general -25-0 DEG C) reacting with titanium compound；Heat the mixture to 80-130 DEG C simultaneously It is kept for 0.5-2 hours at this temperature.Use TiCl4The processing of progress can carry out primary or multiple.With TiCl4Process phase Between above-mentioned 1,8- naphthylenediamine class compounds or above-mentioned 1,8- naphthylenediamine class compounds and second of electron donor can be added Compound is handled, and this processing can be repeated once or repeatedly.
Another method for preparing ingredient of solid catalyst of the present invention includes, by anhydrous magnesium chloride and above-mentioned 1,8- naphthalenes two Aminated compounds or above-mentioned 1,8- naphthylenediamine class compounds and second of electron donor compound are activated in magnesium dichloride Under conditions of grind together.The obtained product can be at a temperature of 80-130 DEG C with excessive TiCl4Processing it is primary or Repeatedly.It is washed until not chloride ion-containing with hydrocarbon solvent after processing.According to further method, two to anhydrous state will be passed through Product obtained from magnesium chloride, titanium compound and above-mentioned 1,8- naphthylenediamine class compounds are co-mulled and made into, using such as 1,2- The halogenated hydrocarbons of dichloroethanes, chlorobenzene, dichloromethane etc is handled.The processing is at 40 DEG C to the temperature between halogenated hydrocarbons boiling point 1-4 hour of lower progress.Then it usually washs to obtain product with the inert hydrocarbon solvent of hexane etc.
According to another method, magnesium dichloride is subjected to pre-activate according to known methods, then at about 80-135 DEG C At a temperature of with excessive TiCl4Processing, wherein containing above-mentioned 1,8- naphthylenediamine class compounds or above-mentioned 1,8- in the solution Naphthylenediamine class compound and second of electron donor compound.Use TiCl4Processing repeatedly and with hexane to solid cleaned with Remove any TiCl for reaction4。
Further method includes that may further reference the preparation of the solids containing titanium catalytic component disclosed in CN1208045 It is prepared by method：First make liquid in the presence of a kind of compound being selected from alcohol, phenol, ketone, aldehyde, ether, amine, pyridine and ester at low temperature Body magnesium compound and liquid titanium compound contact, are settled out solid, and temperature when contact is generally -70-200 DEG C, preferably - 30-130 DEG C, with above-mentioned 1,8- naphthylenediamine class compounds or above-mentioned 1,8- naphthylenediamine class compounds and in contact process Two kinds of electron donor compound processing.
Another method of ingredient of solid catalyst of the present invention includes：Magnesium compound is dissolved in by organic epoxy compound Object, organic phosphorus compound and inert diluent (inert diluent be pentane, hexane, heptane, octane, decane, benzene, toluene, The mixture of diformazan benzene and its derivative or any of the above kind compound arbitrary proportion, preferably toluene, heptane or hexane) composition It in dicyandiamide solution, is mixed with titanium compound after forming homogeneous solution, in the presence of precipitation additive, solids is precipitated；This solid Above-mentioned 1, the 8- naphthylenediamine class compounds of object or above-mentioned 1,8- naphthylenediamine class compounds and second of electron donor compound Processing, makes it be carried on solids, when necessary, then is handled and is obtained with titanium tetrahalide and inert diluent, wherein helping precipitation Agent is one kind in organic acid anhydride, organic acid, ether, ketone.In terms of every mole of magnesium halide, organic epoxy compound object is each component 0.2-10 moles, organic phosphine compound is 0.1-3 moles, and precipitation additive is 0-1.0 moles, and Ti compounds are 0.5-150 moles.
The ingredient of solid catalyst of the present invention can also be used in SiO2, inorganic oxides or the porous resin such as aluminium oxide The magnesium compound of upper load is prepared as carrier, then is activated by well known method, then in about 80-135 DEG C of temperature Lower excessive TiCl4Processing, being added in processing procedure has above-mentioned 1,8- naphthylenediamine class compounds or above-mentioned 1,8- naphthalenes Diamine compounds and second of electron donor compound.
Above-mentioned reaction results in the magnesium halide in activity morphology, and (general crystal magnesium halide compound with regular structure can load Ti it is seldom, thus catalytic activity is low, to prepare the supported catalyst of high activity, and magnesium halide has to pass through activation process.Activation Processing method includes being made into crystallite with method physically and/or chemically, so that activated centre is carried on halogenation magnesium surface, side Edge and fault location, which is " magnesium halide in active ").In addition to these reactions, Also there is known other methods to make by forming the halogenation in activity morphology different from the compound initial substance of magnesium halide in document Magnesium.
In any preparation method, above-mentioned electron donor compound can be directly added into itself or by optional Mode carries out, such as is made in situ by using appropriate precursor, before this is appropriate in the resonable electron donor compound thought of physical efficiency Such as it completes to convert by chemical reaction known to such as esterification, transesterification etc..In general, relative to MgCl2For, with 0.01-5, the preferably molar ratio of 0.05-2.0 use above-mentioned electron donor compound.
In any preparation method, above-mentioned 1,8- naphthylenediamine class compounds or above-mentioned 1,8- naphthylenediamine class chemical combination Object and second electron donor compound can a batch or arbitrarily combine in batches, with random order in preparation process simultaneously or It adds respectively.
The ingredient of solid catalyst of the present invention with reacting for organo-aluminum compound by known method to be converted to by being used for The catalyst of olefinic polymerization.Particularly, it is an object of the present invention to provide one kind being used for alkene CH2=CHR polymerizations are urged Agent, wherein R are hydrogen or the hydrocarbyl group containing 1-12 carbon atom, which includes the product of following substance reaction：
(a) ingredient of solid catalyst of the present invention, containing Mg, Ti and halogen, selected from least one of above-mentioned 1,8- naphthylenediamine class compound, optionally, contain or not contain a kind of ether, ester, ketone or amine simple function group or polyfunctional group to Electron compound,
(b) at least one general formula is AlRnX(3-n)Organo-aluminum compound, R is the alkyl of hydrogen, carbon atom number 1-20 in formula； X is halogen, and n is the integer of 0≤n≤3；With, optionally,
(c) at least one external donor compound.
Preferably, alkyl aluminum compound (b) is selected from such as trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three normal-butyls The trialkyl compound of aluminium, tri-n-hexyl aluminum, trioctylaluminum etc.It is also possible to using trialkylaluminium and aluminum alkyl halide, Alkyl aluminum hydride or such as AlEt2Cl and Al2Et3Cl3Etc alkylaluminium sesquichloride mixture, can also use Alkylaluminoxane.
For needing the application of good isotacticity, external donor compound can be used.External donor compound selects Self-drifting is RnSi(OR1)4-nSilicone compounds, R and R in formula1For C1-C18Alkyl, optional also hetero atom；N be 0≤ The integer of n≤3.
The silicone compounds are concretely：Trimethylmethoxysilane, trimethylethoxysilane, three n-propyl first Oxysilane, three n-propyl Ethoxysilanes, three normal-butyl methoxy silanes, triisobutyl Ethoxysilane, thricyclohexyl first Base silane, thricyclohexyl Ethoxysilane, dimethyldimethoxysil,ne, dimethyl diethoxysilane, diη-propyl diformazan Oxysilane, diisopropyl dimethoxy silane, diη-propyl diethoxy silane, diisopropyldiethoxysilane, two are just Butyl diethoxy silane, diisobutyl diethoxy silane, di-t-butyl dimethoxysilane, di-t-butyl dimethoxy silicon Alkane, di-n-butyl dimethoxysilane, second, isobutyl dimethoxy silane, di-t-butyl diethoxy silane, di-n-butyl two Ethoxysilane, n-butylmethyldimethoxyforane, two (2- ethylhexyls) dimethoxysilanes, two (2- ethylhexyls) two Ethoxysilane, Dicyclohexyldimethoxysilane, dicyclohexyl diethoxy silane, dicyclopentyl dimethoxyl silane, two Cyclopenta diethoxy silane, Cyclohexyl Methyl Dimethoxysilane, cyclohexyl methyl diethoxy silane, cyclohexyl-ethyl two Methoxy silane, cyclohexyl isopropyl dimethoxysilane, cyclohexyl-ethyl diethoxy silane, cyclopentyl-methyl dimethoxy Silane, cyclopentyl ethyl diethoxy silane, cyclopenta isopropyl diethoxy silane, cyclopenta isobutyl group dimethoxy silicon Alkane, cyclohexyl n-propyl dimethoxysilane, cyclohexyl n-propyl diethoxy silane, cyclohexyl normal-butyl diethoxy silicon Alkane, phenyl-methyl dimethoxysilane, phenyl-methyl diethoxy silane, amyl ethyldimethoxysilane, amyl ethyl two Ethoxysilane, cyclohexyldimethyl methoxy silane, cyclohexyl diethylmethoxysilane, cyclohexyl diethyl ylmethoxy silicon Alkane, cyclohexyl diethylethoxysilane, 2- ethylhexyls trimethoxy silane, cyclohexyl dimethoxysilane, cyclohexyl two Ethoxysilane, 2- ethylhexyls triethoxysilane, ethyl trimethoxy silane, ethyl triethoxysilane, n-propyl three Methoxy silane, n-propyl triethoxysilane, isopropyltri-methoxysilane, isopro-pyltriethoxysilane, normal-butyl three Methoxy silane, trimethoxysilane, tert-butyl trimethoxy silane, ne-butyltriethoxysilaneand, cyclohexyl three Methoxy silane, cyclohexyltriethyloxysilane, cyclopentyl-trimethoxy-silane, cyclopenta triethoxysilane, vinyl three Methoxy silane, vinyltriethoxysilane, 2- ethylhexyls trimethoxy silane, 2- ethylhexyls triethoxysilane, Amyltrimethoxysilane, amyl triethoxysilane, tetramethoxy-silicane, tetraethoxysilane, cyclohexyl ring amyl diformazan Oxysilane, cyclohexyl ring amyl diethoxy silane, cyclohexyl ring amyl dipropoxy silane, 3- methyl cyclohexane cyclopentyls Dimethoxysilane, 4- methyl cyclohexane cyclopentyls dimethoxysilane, 3,5- dimethyleyelohexane cyclopentyl dimethoxy silicon Alkane, 3- methyl cyclohexane butylcyclohexyls dimethoxysilane, two (3- methylcyclohexyls) dimethoxysilanes, 4- methyl cyclohexane basic rings Hexyl dimethoxysilane, two (4- methylcyclohexyls) dimethoxysilanes, 3,5- dimethyleyelohexane butylcyclohexyl dimethoxys Silane, two (3,5- Dimethylcyclohexyl) dimethoxysilanes, tetrapropoxysilane, four butoxy silanes.In these organosilicons It is preferred in compound：Diη-propyl dimethoxysilane, diisopropyl dimethoxy silane, di-n-butyl dimethoxysilane, Second, isobutyl dimethoxy silane, di-t-butyl dimethoxysilane, di-n-butyl diethoxy silane, tertiary butyl trimethoxy Silane, Dicyclohexyldimethoxysilane, dicyclohexyl diethoxy silane, Cyclohexyl Methyl Dimethoxysilane, cyclohexyl Ethyl diethoxy silane, cyclohexyl-ethyl dimethoxysilane, cyclohexyl-ethyl diethoxy silane, cyclopentyl-methyl diformazan Oxysilane, cyclopentyl-methyl diethoxy silane, cyclopentyl ethyl dimethoxysilane, cyclohexyl ring dicyclopentyldimetoxy silicon Alkane, cyclohexyl ring amyl diethoxy silane, 3- methyl cyclohexane cyclopentyls dimethoxysilane, 4- methyl cyclohexane cyclopentyls Dimethoxysilane and 3,5- dimethylcyclopentyl dimethoxysilanes etc..These compounds C, which can be used alone or mix, to be made With.
The example of preferred silicon compound has Cyclohexyl Methyl Dimethoxysilane；Diisopropyl dimethoxy silane；Two Normal-butyl dimethoxysilane；Second, isobutyl dimethoxy silane；Dimethoxydiphenylsilane；Phenyl triethoxysilane； Methyl-t-butyldimethoxysilane；Dicyclopentyl dimethoxyl silane；2- ethyl piperidine base -2- t-butyldimethoxysilanes (1,1,1- tri- fluoro- 2- propyl) -2- ethyl piperidine base dimethoxysilanes and (1,1,1- tri- fluoro- 2- propyl)-methyl and first Oxysilane, cyclohexyl trimethoxy silane；Tert-butyl trimethoxy silane and tertiary hexyl trimethoxysilane.
The catalyst of the present invention can be used for alkene CH2In=CHR (co) polymerizations, the alkene is ethylene, propylene, 1- fourths Alkene, 4-methyl-1-pentene, 1- hexenes and 1- octenes.
In order to which the catalyst in the application present invention carries out olefinic polymerization, homopolymerization and copolymerization can be applied above by component A, the catalyst prepared by b or c.The molar ratio of the Ti in Al and component a in usual component b is 1-1000, preferably 50- 800；When containing component c, the molar ratio of component c and component b is 0.002-10, preferably 0.01-2, preferably 0.01-0.5.
Olefin polymerization catalysis of the present invention preferably includes the reaction product of following component or following component, that is, does not need Use external electron donor：
A) above-mentioned ingredient of solid catalyst；
B) at least one general formula is AlRnX(3-n)Organo-aluminum compound, R is the alkyl of hydrogen, carbon atom number 1-20 in formula；X For halogen, n is the integer of 0≤n≤3.
Olefinic polymerization, homopolymerization and copolymerization are preferably only applied above by the catalyst prepared by component a and b, in component b The molar ratio of Ti in Al and component a is 1-1000mol, preferably 50-800.
The charging sequence of each component is arbitrary, and is added in paradigmatic system at first with component b, and the rear component a that is added is preferred； When using component c, component c is added after component b, is eventually adding component a and is preferred.
Polymerization technique in the present invention can be carried out in the case where having solvent or without solvent.Olefinic monomer can be gas Phase or liquid phase.Hydrogen is further added and can be used as molecular weight regulator.Certainly polymerization can also be in not molecular weight regulator In the case of carry out.Polymerization temperature is not higher than 200 DEG C, preferably 20-100 DEG C, more preferable 40-80 DEG C of temperature.Polymerization pressure is not To be more than 10MPa, preferably 1-5MPa.Continuous polymerization or batch polymerization process can be applied.And polymerisation can divide one Step, two steps or multistep carry out.
The alkene that homopolymerization or copolymerization are carried out using catalyst of the present invention includes linear alkene：Ethylene, propylene, 1- fourths Alkene, 1- amylenes, 1- hexenes, 1- heptene, 1- nonenes, 1- decene；Branched-chain alkene is such as：3-methyl-1-butene and 4- methyl-1-pentenes Alkene；Alkadienes is such as：Butadiene, vinylcyclopentene and vinylcyclohexene.Catalyst of the present invention is preferably applied to gather In ethylene and polypropylene.These alkene can be independent or a variety of be used in mixed way.
Using the polymerization (herein referring to mass polymerization) of catalytic component a, b, c of the present invention alkene carried out, recommend to carry out Prepolymerization is come isotacticity, the particle properties etc. that increase the living polymer of catalyst.The prepolymerization technology can be equally used for benzene Ethylene homo.
The charging sequence of each component and monomer is arbitrary in prepolymerization technology.Preferably first component b is added to and is contained In having inertia or the alkene gas that will be polymerize, the one or more alkene to be polymerize then are added after component a is added. Using the alkene of organosilan it is prepolymerized during, it is proposed that the alkene that component b is added to inert gas or polymerize In the prepolymerization system of gas, component c is then added, component a is then added, finally adds alkene.
For the present invention using 1, the 8- naphthylenediamines class compound as internal electron donor, the activity of the catalyst of gained is high, Gained polypropylene has high isotacticity and adjustable molecular weight distribution, and poly- the third of wider molecular weight distribution can be obtained Alkene.When the compounds such as 1,8- naphthylenediamine class compounds and two ethers compound, the activity of the catalyst of gained is significantly higher than difference It is used alone 1,8- naphthylenediamines class class compound and diether compound, and the moderate molecular weight distribution of gained polyolefin and is wider than Polyolefin obtained by diether catalyst, though two ethers catalyst activities high polymer molecular weight narrowly distributings can be overcome.It should Class catalytic component resulting polymers when without using external electron donor still have high isotactic, have super-active, and As polymerization time extension still keeps high-level activity, gained polyolefin ash content is relatively low, is suitble to the low ash content polymeric articles of production.
Specific implementation mode
The present invention is further described with embodiment below, is conducive to be better understood by the present invention and its advantage, effect, but The embodiment is merely to illustrate the present invention rather than the limitation present invention.
The compound enumerated in embodiment is only used as example to illustrate the present invention, does not limit the present invention, other belong to this Invention scope but the compound not referred in embodiment.
The measurement of polymer isotacticity
It is measured (heptane boiling extracting 6 hours) using heptane extraction process.Two grams of dry polymer samples, are placed on extractor It is middle with boiling heptane extract 6 hours after, by residue dry to obtained by constant weight polymer weight (g) with 2 ratio be etc. Normality.
The measurement of polymer molecular weight distribution
Using PL-220 type gel permeation chromatographies, (standard specimen is measured at 150 DEG C by solvent of trichloro-benzenes：Polystyrene, stream Fast 1.0mL/min, pillar：3xPlgel 10um M1Xed-B 300x7.5nm).
The measurement of polymer ash content is measured according to GB/T 9345.1-2008.
Logical formula (II)
Table 1
Table 2
Table 3
Polymerization 1
Component using solid catalyst as olefin polymerization catalysis carries out polymerization evaluation：
In 5L stainless steel cauldrons after nitrogen is sufficiently displaced from, the triethyl aluminum hexane of a concentration of 0.5mol/L of 5mL is added Solution and Cyclohexylmethyldimethoxysilane (CMMS) hexane solution of a concentration of 0.1mol/L of 1mL and the catalyst of preparation Then 10mg is added 10mL hexanes and rinses charge line, add 2L (under standard state) hydrogen and 2.5L refines propylene, control System reaction was warming up to 70 DEG C, at this temperature polymerisation 1 hour in 20 DEG C of pre-polymerizations 5 minutes.After reaction, by reaction kettle Cool down and stop stirring discharge reaction product, through being dried to obtain polymer.
The preparation of ingredient of solid catalyst
The operation that catalyst is prepared in embodiment carries out under high pure nitrogen protection.Specific embodiment is as follows.
Embodiment 1
In 5 mouthfuls of flasks with stirring that 500ml is sufficiently displaced from through nitrogen, 10g diethoxies magnesium and 80mL first is added Benzene prepares suspension, -10 DEG C of dropwise addition titanium tetrachloride 20mL is maintained at, after system is to slowly warm up to 10 DEG C after being added dropwise Titanium tetrachloride 60mL is added dropwise, is to slowly warm up to 90 DEG C again later, is added 4g 1,8- diisoamyls amide-naphthylenediamine (A1), then after It is continuous to be warming up to 120 DEG C of constant temperature 2 hours, then liquid pressure is filtered dry only, elimination liquid, the solid 120mL titanium tetrachlorides of gained It is washed 3 times at 125 DEG C.The solid of gained is washed 2 times with 150mL hexanes at 60 DEG C, room temperature washing 2 times, filters off liquid and drying, It is ingredient of solid catalyst to obtain solid powder.Ti content, internal electron donor content and the aggregate number of ingredient of solid catalyst According to being shown in Table 4.
Embodiment 2-27
Ingredient of solid catalyst preparation method such as embodiment 1, difference are to distinguish 1,8- diisoamyls amide-naphthylenediamine The compound in 1-table of table 3 is replaced in order.
Embodiment 28
In 5 mouthfuls of flasks with stirring that 500ml is sufficiently displaced from through nitrogen, 10gMgCl is added at -15 DEG C2· 3C2H5OH microballoons and 150mL titanium tetrachlorides prepare suspension, are maintained at -15 DEG C 1 hour, are slowly warming up to 80 DEG C, are added 3g 1,8- bis- [N- benzoyl-N- benzyls]-naphthylenediamine (A20), then proceedes to be warming up to 110 DEG C of constant temperature 1 hour, then by liquid Body press filtration is clean, filters off liquid, and the solid of gained is washed 3 times with 120mL titanium tetrachlorides at 125 DEG C.The solid 150mL of gained Hexane washs 4 times at 60 DEG C, filters off liquid and dry to get to ingredient of solid catalyst.
Embodiment 29
The 2-Ethylhexyl Alcohol of anhydrous magnesium chloride 8g, 38mL decane and 35mL reacted at 130 DEG C 2 hours with formed uniformly it is molten Liquid.1.7g phthalic anhydrides are added in solution, mixture stirs 1 hour at 130 DEG C, so that phthalic anhydride is completely molten Solution is in homogeneous solution.Obtained homogeneous solution is cooled to room temperature, and is added drop-wise in 1 hour and is maintained at -20 DEG C of 200mL tetra- In titanium chloride；It drips rear mixed solution and is heated to 110 DEG C in 4 hours, 3g 1,8- bis- are added when temperature reaches 110 DEG C [N- benzoyl-N- benzyls]-naphthylenediamine (A20), mixture stir 2 hours at the temperature disclosed above.After reaction 2 hours, pass through heat Solid portion is collected by filtration.Solid portion is suspended in 275mL titanium tetrachlorides, is reacted 2 hours under the conditions of 110 DEG C.After reaction, Solids portion is collected by heat filtering, is fully washed with decane and hexane at 110 DEG C, solid catalyst is obtained after draining Component.
Embodiment 30
In 5 mouthfuls of flasks with stirring that 500ml is sufficiently displaced from through nitrogen, room temperature addition 10g anhydrous magnesium chlorides, 150mL toluene, 17mL epoxychloropropane and 16mL tributyl phosphates are warming up to 50 DEG C, and maintain 2 hours under stirring, solid is complete Then fully dissolved is added 2.40g phthalic anhydrides, then maintains 1 hour.Solution is cooled to -25 DEG C, is added dropwise in 1 hour Titanium tetrachloride 110mL is to slowly warm up to 80 DEG C, in temperature-rise period, gradually washes out solids.3g 1, [the N- benzene first of 8- bis- is added Acyl-N- benzyls]-naphthylenediamine (A20), it is maintained 1 hour at 80 DEG C.200mL toluene washes twice after filtering, is then added 120mL toluene and 80mL titanium tetrachlorides continue to be warming up to 110 DEG C, then liquid pressure is filtered dry only, repeats place by constant temperature 2 hours Reason is primary.Liquid is filtered off, the solid of gained is washed 1 time with 100mL dichloroethanes, and hexane washs 4 times, and obtaining solid after dry urges Agent component.
Comparative example 1
Ingredient of solid catalyst preparation method such as embodiment 1, difference are by 4g 1,8- diisoamyls acyl-naphthylenediamine (A1) 3g n-butyl phthalates are replaced with.
Comparative example 2
Ingredient of solid catalyst preparation method such as embodiment 26, difference are by 1,8- bis- [N- benzoyl-N- benzyls]- Naphthylenediamine (A20) is changed to n-butyl phthalate.
Comparative example 3
Ingredient of solid catalyst preparation method such as embodiment 27, difference are by 1,8- bis- [N- benzoyl-N- benzyls]- Naphthylenediamine (A20) replaces with n-butyl phthalate.
Comparative example 4
Ingredient of solid catalyst preparation method such as embodiment 28, difference are by 1,8- bis- [N- benzoyl-N- benzyls]- Naphthylenediamine (A20) replaces with n-butyl phthalate.
Table 4
4 polymerization result of table shows, using selected from 1,8- naphthylenediamine class compounds as internal electron donor, using four kinds of differences Catalyst preparation process obtained by catalyst, be used for propylene polymerization when, have excellent activity.Identical preparation process Under, it is most of to use o-phenylenediamine class compound higher than using the activity of phthalic acid ester for the catalyst of internal electron donor, Most highly active is up to 68.6Kg/gCath-1, the polyacrylic molecular weight distribution of gained is integrally than phthalate catalyst institute The polypropylene obtained is significantly wider, most wide to reach 9.3, and due to the different polymer molecular weights of substituent group in compound and functional group It is distributed difference, some for meeting specified molecular weight distribution index can be chosen as needed or certain compounds are poly- to adjust The molecular weight distribution of composition powder.
Embodiment 31
In 5 mouthfuls of flasks with stirring that 500ml is sufficiently displaced from through nitrogen, 10g diethoxies magnesium and 80mL first is added Benzene prepares suspension, -10 DEG C of dropwise addition titanium tetrachloride 20mL is maintained at, after system is to slowly warm up to 10 DEG C after being added dropwise Titanium tetrachloride 60mL is added dropwise, is to slowly warm up to 90 DEG C again later, 3g 1,8- bis- [N- benzoyl-N- benzyls]-naphthylenediamine is added (A20) and the bis- methoxyl methyl fluorenes of 1g 9,9- it, then proceedes to be warming up to 120 DEG C of constant temperature 2 hours, is then filtered dry liquid pressure only, filter Liquid, the solid of gained is gone to be washed 3 times at 125 DEG C with 120mL titanium tetrachlorides.The solid of gained is washed with 150mL hexanes at 60 DEG C It washs 2 times, room temperature washing 2 times, filters off liquid and drying, it is ingredient of solid catalyst to obtain solid powder.Solid catalyst group Ti content, internal electron donor content and the aggregated data divided is shown in Table 5.
Embodiment 32
Ingredient of solid catalyst preparation method such as embodiment 31, difference are by 1,8- bis- [N- benzoyl-N- benzyls]- Naphthylenediamine (A20) replaces with 1,8- dibenzamides-naphthylenediamine (A4).
Embodiment 33
Ingredient of solid catalyst preparation method such as embodiment 31, difference are by 1,8- bis- [N- benzoyl-N- benzyls]- Naphthylenediamine (A20) replaces with 1,8- NSC 334072s-naphthylenediamine (A15).
Embodiment 34
Ingredient of solid catalyst preparation method such as embodiment 31, difference are by 1,8- bis- [N- benzoyl-N- benzyls]- Naphthylenediamine (A20) replaces with 1,8- bis- [the positive hexanoyl-N- n-hexyls of N-]-naphthylenediamine (A19).
Embodiment 35
Ingredient of solid catalyst preparation method such as embodiment 31, difference are by 1,8- bis- [N- benzoyl-N- benzyls]- Naphthylenediamine (A20) replaces with 1,8- bis- [chlorobenzyl between chlorobenzoyl-N- between N-]-naphthylenediamine (A22).
Embodiment 36
Ingredient of solid catalyst preparation method such as embodiment 31, difference are by 1,8- bis- [N- benzoyl-N- benzyls]- Naphthylenediamine (A20) replaces with 1,8- bis- [N- isovaleryl-N- benzyls]-naphthylenediamine (A17).
Embodiment 37
Ingredient of solid catalyst preparation method such as embodiment 31, difference are by the 3g 1, [N- benzoyl-N- benzyls of 8- bis- Base]-naphthylenediamine (A20) and the bis- methoxyl methyl fluorenes of 1g 9,9- replace with 3g 1,8- bis- [N- benzoyl-N- benzyls]-naphthylenediamine (A20) and 1g n-butyl phthalates.
Embodiment 38
Ingredient of solid catalyst preparation method such as embodiment 31, difference are by the 3g 1, [N- benzoyl-N- benzyls of 8- bis- Base]-naphthylenediamine (A20) and the bis- methoxyl methyl fluorenes of 1g 9,9- replace with 3g 1,8- bis- [N- benzoyl-N- benzyls]-naphthylenediamine (A20) and 1g 2- isopropyls -2- isopentyl-malonic ester.
Embodiment 39
Ingredient of solid catalyst preparation method such as embodiment 31, difference are by the 3g 1, [N- benzoyl-N- benzyls of 8- bis- Base]-naphthylenediamine (A20) and the bis- methoxyl methyl fluorenes of 1g 9,9- replace with 3g 1,8- bis- [N- benzoyl-N- benzyls]-naphthylenediamine (A20) and 1g 2,3- diisopropyl diethyl succinates.
Embodiment 40
Ingredient of solid catalyst preparation method such as embodiment 31, difference are by the 3g 1, [N- benzoyl-N- benzyls of 8- bis- Base]-naphthylenediamine (A20) and the bis- methoxyl methyl fluorenes of 1g 9,9- replace with 3g 1,8- bis- [N- benzoyl-N- benzyls]-naphthylenediamine (A20) and 1g 2,4-PD dibenzoates.
Embodiment 41
Ingredient of solid catalyst preparation method such as embodiment 31, difference are by the 3g 1, [N- benzoyl-N- benzyls of 8- bis- Base]-naphthylenediamine (A20) and the bis- methoxyl methyl fluorenes of 1g 9,9- replace with 2g 1,8- bis- [N- benzoyl-N- benzyls]-naphthylenediamine (A20) and the bis- methoxyl methyl fluorenes of 2g 9,9-.
Embodiment 42
Ingredient of solid catalyst preparation method such as embodiment 31, difference are by the 3g 1, [N- benzoyl-N- benzyls of 8- bis- Base]-naphthylenediamine (A20) and the bis- methoxyl methyl fluorenes of 1g 9,9- replace with 1g 1,8- bis- [N- benzoyl-N- benzyls]-naphthylenediamine (A20) and the bis- methoxyl methyl fluorenes of 3g 9,9-.
Embodiment 43
Ingredient of solid catalyst preparation method such as embodiment 31, difference are by the 3g 1, [N- benzoyl-N- benzyls of 8- bis- Base]-naphthylenediamine (A20) and the bis- methoxyl methyl fluorenes of 1g 9,9- replace with 3g 1,8- bis- [N- benzoyl-N- benzyls]-naphthylenediamine (A20) and the bis- methoxyl methyl fluorenes of 1.5g 9,9-.
Embodiment 44
Ingredient of solid catalyst preparation method such as embodiment 31, difference are by the 3g 1, [N- benzoyl-N- benzyls of 8- bis- Base]-naphthylenediamine (A20) and the bis- methoxyl methyl fluorenes of 1g 9,9- replace with 2g 1,8- bis- [N- benzoyl-N- benzyls]-naphthylenediamine (A20) and the bis- methoxyl methyl fluorenes of 1g 9,9-.
Embodiment 45
Ingredient of solid catalyst preparation method such as embodiment 31, difference are by the 3g 1, [N- benzoyl-N- benzyls of 8- bis- Base]-naphthylenediamine (A20) and the bis- methoxyl methyl fluorenes of 1g 9,9- replace with 2g 1,8- bis- [chlorobenzyl between chlorobenzoyl-N- between N-]- Naphthylenediamine (A22) and the bis- methoxyl methyl fluorenes of 2g 9,9-.
Embodiment 46
Ingredient of solid catalyst preparation method such as embodiment 31, difference are by the 3g 1, [N- benzoyl-N- benzyls of 8- bis- Base]-naphthylenediamine (A20) and the bis- methoxyl methyl fluorenes of 1g 9,9- replace with 1g 1,8- bis- [chlorobenzyl between chlorobenzoyl-N- between N-]- Naphthylenediamine (A22) and the bis- methoxyl methyl fluorenes of 3g 9,9-.
Embodiment 47
Ingredient of solid catalyst preparation method such as embodiment 31, difference are by the 3g 1, [N- benzoyl-N- benzyls of 8- bis- Base]-naphthylenediamine (A20) and the bis- methoxyl methyl fluorenes of 1g 9,9- replace with 3g 1,8- bis- [chlorobenzyl between chlorobenzoyl-N- between N-]- Naphthylenediamine (A22) and the bis- methoxyl methyl fluorenes of 1.5g 9,9-.
Embodiment 48
Ingredient of solid catalyst preparation method such as embodiment 31, difference are by the 3g 1, [N- benzoyl-N- benzyls of 8- bis- Base]-naphthylenediamine (A20) and the bis- methoxyl methyl fluorenes of 1g 9,9- replace with 2g 1,8- bis- [chlorobenzyl between chlorobenzoyl-N- between N-]- Naphthylenediamine (A22) and the bis- methoxyl methyl fluorenes of 1g 9,9-.
Embodiment 49
Ingredient of solid catalyst preparation method such as embodiment 28, difference are by the 3g 1, [N- benzoyl-N- benzyls of 8- bis- Base]-naphthylenediamine (A20) is changed to 3g 1, [chlorobenzyl between chlorobenzoyl-N- between the N-]-naphthylenediamines (A22) of 8- bis- and 1g 9, and 9- is bis- Methoxyl methyl fluorenes.
Embodiment 50
Ingredient of solid catalyst preparation method such as embodiment 29, difference are by the 3g 1, [N- benzoyl-N- benzyls of 8- bis- Base]-naphthylenediamine (A20) is changed to 3g 1, [chlorobenzyl between chlorobenzoyl-N- between the N-]-naphthylenediamines (A22) of 8- bis- and 1g 9, and 9- is bis- Methoxyl methyl fluorenes.
Embodiment 51
Ingredient of solid catalyst preparation method such as embodiment 30, difference are by the 3g 1, [N- benzoyl-N- benzyls of 8- bis- Base]-naphthylenediamine (A20) is changed to 3g 1, [chlorobenzyl between chlorobenzoyl-N- between the N-]-naphthylenediamines (A22) of 8- bis- and 1g 9, and 9- is bis- Methoxyl methyl fluorenes.
Comparative example 5
Ingredient of solid catalyst preparation method such as embodiment 1, difference are by 1,8- diisoamyls amide-naphthylenediamine (A1) Replace with 9,9- methoxyl methyl fluorenes.
Comparative example 6
Ingredient of solid catalyst preparation method such as embodiment 1, difference are to replace 1,8- diisoamyls amide-naphthylenediamine For 2- isopropyls -2- isopentyl-malonic ester.
Comparative example 7
Ingredient of solid catalyst preparation method such as embodiment 1, difference are to replace 1,8- diisoamyls amide-naphthylenediamine For 2,3- diisopropyl diethyl succinates.
Comparative example 8
Ingredient of solid catalyst preparation method such as embodiment 1, difference are to replace 1,8- diisoamyls amide-naphthylenediamine For 2,4-PD dibenzoate.
Table 5
DNBP：N-butyl phthalate, FLU：9,9- methoxyl methyl fluorenes
DIE：2- isopropyls -2- isopentyl-malonic ester, SUC：2,3- diisopropyl diethyl succinates
BRD：2,4- glycol dibenzoates, "-" indicate that this does not have
Different 1,8- naphthylenediamines and 9 are respectively adopted it can be seen from 5 data of table, the bis- methoxyl methyl fluorenes of 9- compound conduct When the internal electron donor of catalytic component, the activity of catalyst is all remarkably higher than exclusive use 1,8- naphthylenediamines and exclusive use 9, The bis- methoxyl methyl fluorenes of 9- are the activity of the catalyst of internal electron donor, and the molecular weight distribution of resulting polymers is between 1,8- naphthylenediamines Compound and 9, between the bis- methoxyl methyl fluorenes of 9-.When other conditions fix only 1,8- naphthylenediamines compound and 9, the bis- methoxyl methyls of 9- Fluorenes compounding ratio difference when, catalyst activity it is different with the molecular weight distribution of resulting polymers, highest can be improved to 98.3KgPP/gCat, and polymer molecular weight distribution is moderate.
Equally, when the internal electron donors such as 1,8- naphthylenediamines compound and phthalate, diol-lipid compound, gained Polymer molecular weight distribution it is wider, and active higher.It, can after illustrating that phenylenediamine compound is compounded with above-mentioned a few class compounds The activity of catalyst is significantly improved, and the range of molecular weight distributions of polymer can be widened.
Polymerizing condition 2
Component using solid catalyst as olefin polymerization catalysis carries out polymerization evaluation according to following condition：
In 5L stainless steel cauldrons after nitrogen is sufficiently displaced from, the triethyl aluminum hexane solution of a concentration of 0.5mol/L is added Then (amount of triethyl aluminum is shown in Table the Al/Ti in 4) and the 3-5mg catalyst prepared is added 10mL hexanes and rinses charge line, It adding 2L (under standard state) hydrogen and 2.5L and refines propylene, control reaction was warming up to 70 DEG C in 20 DEG C of pre-polymerizations 5 minutes, The polymerisation corresponding time (being shown in Table 6) at a temperature of this.After reaction, reaction kettle is cooled down and stops stirring and reaction product is discharged, Through being dried to obtain polymer.Acquired results are shown in Table 6.
Embodiment 52- embodiments 57
It is polymerize according to condition described in polymerizing condition 2 and table 6 using catalyst CAT-41, the results are shown in Table 6.
Embodiment 58- embodiments 63
It is polymerize according to condition described in polymerizing condition 2 and table 6 using catalyst CAT-45, the results are shown in Table 6.
Comparing embodiment 9
It is polymerize according to condition described in polymerizing condition 2 and table 6 using catalyst REF-1, the results are shown in Table 6.
Comparing embodiment 10- comparing embodiments 13
Catalyst REF-5~REF-8 is respectively adopted according to condition described in polymerizing condition 2 and table 6 to be polymerize, polymerization knot Fruit is shown in Table 6.
Table 6
It can be seen from 6 data of table 1,8- naphthylenediamines compound and 9, the bis- methoxy first of 9- are used using magnesium ethylate carrier The catalyst CAT-41 and CAT-45 of base fluorenes compounding, without using external donor compound, can obtain superelevation work in polymerization Property, far above the catalyst (comparative example 9- comparative examples 13) of non-compounding under same polymerizing condition, and still maintain 98.0% with On high isotactic.90 minutes and 120 minutes were extended between upon polymerization from 60 minutes, catalyst can keep super-active not wane Subtract.It is relatively low using gained polypropylene ash content when low Al/Ti, it is minimum to be down to 31ppm.
Although above the present invention is described in detail with a general description of the specific embodiments, On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause This, these modifications or improvements, belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Term used herein is only to be illustrated to specific embodiment, is not intended to and limits the invention. Unless otherwise defined, all terms (including technical terms and scientific terms) used herein with it is of the art The understanding of those skilled in the art is identical.Must also it is clear that, it is usually fixed in such as dictionary in addition to having specific definition herein The term of justice should be construed in the context of this specification and the relevant technologies can have the consistent meaning, without what should be explained Idealization or excessively formalization.

Claims (16)

1. a kind of ingredient of solid catalyst containing naphthylenediamine class compound, it includes Mg, Ti, halogen and at least one electrons Body, the electron donor are 1, the 8- naphthylenediamine class compounds in general formula (I)：
Wherein, R1-R6It is identical or different, it is H；Halogen；C1-C20Alkyl, contain one selected from N, O, S, P, Si and halogen Or multiple hetero atoms；R1—R6In two or more be mutually bonded cyclization；RI-RIVIt is identical or different, it is H；C1-C20Hydrocarbon Base can contain unsaturated bond containing one or more hetero atoms selected from N, O, S, P, Si and halogen；RI—RIVIt is bonding at Ring or unsaturated bond.
2. ingredient of solid catalyst according to claim 1, which is characterized in that in general formula (I), R1-R6It is identical or different, For H；Halogen；C1-C20Linear chain or branched chain alkyl, naphthenic base, alkenyl, ester group, phenyl, alkyl phenyl, phenylalkyl, indenes Base, benzyl, halogenated or the alkyl, naphthenic base, phenyl, alkyl phenyl, phenylalkyl, the indenes that are replaced by N, O, S, P, Si hetero atom Base, benzyl；Or it is selected from heterocyclic aryl substituent group；R1-R6It is therein it is two or more be mutually bonded circlewise structure, be It is saturation or undersaturated；RI=RIVIt is identical or different, it is H；C1-C20The alkyl of linear chain or branched chain, naphthenic base, alkenyl, Ester group, phenyl, alkyl phenyl, phenylalkyl, indenyl, benzyl, halogenated or the alkyl, the cycloalkanes that are replaced by N, O, S, P, Si hetero atom Base, phenyl, alkyl phenyl, phenylalkyl, indenyl, benzyl；Or it is selected from heterocyclic aryl substituent group；RI-RIVIt is bonding cyclization or Unsaturated bond.
3. ingredient of solid catalyst according to claim 1, which is characterized in that the electron donor is selected from logical formula (II) Compound：
Wherein, group R1-R6、RIIAnd RIVThere is meaning identical with formula (I) is led to；R7For C1-C20Alkyl, can contain selected from N, O, one or more hetero atoms of S, P, Si and halogen, as carbon atom either hydrogen atom or the substituent group of the two, preferably C1-C20Linear chain or branched chain alkyl, naphthenic base, alkenyl, ester group, phenyl, alkyl phenyl, phenylalkyl, indenyl, benzyl, halogen Generation or alkyl, naphthenic base, phenyl, alkyl phenyl, phenylalkyl, indenyl, the benzyl replaced by N, O, S, P, Si hetero atom.
4. ingredient of solid catalyst according to claim 3, which is characterized in that the electron donor is selected from logical formula (III) Compound：
Wherein, group R1-R6There is meaning identical with formula (I) is led to, R7There is meaning identical with formula (II) is led to, R8And R8’Phase It is same or different, it is selected from H；C1-C20Alkyl, containing selected from N, O, S, P, Si and halogen one or more hetero atoms, as Carbon atom either hydrogen atom or the substituent group of the two, preferably C1-C20Linear chain or branched chain alkyl, naphthenic base, alkenyl, ester Base, phenyl, alkyl phenyl, phenylalkyl, indenyl, benzyl, halogenated or the alkyl, the cycloalkanes that are replaced by N, O, S, P, Si hetero atom Base, phenyl, alkyl phenyl, phenylalkyl, indenyl, benzyl；Or it is selected from heterocyclic aryl substituent group.
5. ingredient of solid catalyst according to claim 1, which is characterized in that the electron donor is selected from logical formula (IV) Compound：
Wherein, group R1-R6There is meaning identical with formula (I) is led to；R8And R8’There is meaning identical with formula (III) is led to.
6. ingredient of solid catalyst according to any one of claims 1-5, which is characterized in that contain only selected from described 1, the 8- naphthylenediamine class compounds of general formula (I) are as electron donor.
7. ingredient of solid catalyst according to any one of claims 1-5, which is characterized in that remove and contain the general formula (I) also include another electron donor compound except 1,8- naphthylenediamine class compounds, the compound be selected from containing there are one or The Lewis alkali of multiple electronegativity groups, group of the electron donor atom therein selected from N, O, S, P, As or Sn composition, such as selected from The electron donor compound of two ethers, esters, diones and Diamines.
8. ingredient of solid catalyst according to claim 7, which is characterized in that 1,8- naphthylenediamine class compound and other one The molar ratio of kind electron donor compound is 0.01-100, preferred 0.02-50, more preferable 0.05-20.
9. ingredient of solid catalyst according to claim 7, which is characterized in that the diether compound is selected from general formula (V) 1,3-, bis- ethers：
Wherein：R、R1、R2、R3、R4And R5It may be the same or different, represent H or have the straight chain or branched-alkyl, ring of 1-18 carbon atom Alkyl, aryl, alkaryl or aralkyl；R6And R7It may be the same or different, represent the straight chain for having 1-20 carbon atom or branched alkane The alkaryl and aralkyl of base, the naphthenic base of 3-20 carbon atom, the aryl of 5-20 carbon atom, 7-20 carbon atom；R to R7 One or more of group can link to form cyclic structure, may include selected from halogen, N, O, S, P and Si one or more Hetero atom.
10. ingredient of solid catalyst according to claim 7, which is characterized in that the ester type compound is monocarboxylic acid Ester or polybasic carboxylic acid esters compound, the diester of optimization aromatic dicarboxylic acids, such as ditridecyl phthalate or terephthalic acid (TPA) Diester.
11. ingredient of solid catalyst according to claim 10, which is characterized in that the ester type compound is selected from general formula (VI) succinate compound compound：
Wherein, group R1And R2, it is same or different to each other, is C1-C20Line style or branched-alkyl, alkenyl, naphthenic base, aryl, virtue Alkyl or alkylaryl group optionally include hetero atom；R3-R6In at least two groups be different from hydrogen and be selected from C1-C20Line style Or branched-alkyl, alkenyl, naphthenic base, aryl, aralkyl or alkylaryl group, optionally contain hetero atom, in addition, group R3-R6It can be connected together and constitute a ring.
12. ingredient of solid catalyst according to claim 7, which is characterized in that the ester type compound is selected from general formula (VII) glycol ester compounds:
R in formula1-R6、R1’-R2’For the C1-C20 alkane of identical or different hydrogen, halogen or substituted or unsubstituted linear chain or branched chain Base, C3-C20 naphthenic base, C6-C20 aryl, C7-C20 alkaryls, C7-C20 aralkyl, C2-C10 alkylenes or C10-C20 are thick Cyclophane base；But R1’And R2’It is not hydrogen, R1-R6One or more of it is optionally cyclic or not cyclic.
13. according to the ingredient of solid catalyst described in any one of claim 1-12, including titanium compound, magnesium compound and extremely The precursor of a kind of few reaction product selected from 1, the 8- naphthylenediamine class compounds, the magnesium compound is selected from least one： XnMg(OR)2-n, MgCl2MROH, R2-nMgXn, MgCl2/SiO2, MgCl2/Al2O3Or the mixture of magnesium halide and alcohol titanium, formula Middle m is the number of 0.1-6, and 0≤n≤2, X are halogen, and R is hydrogen or C1-C20Alkyl；The general formula of the titanium compound is TiXN (OR)4-N, R is the alkyl that carbon atom number is 1-20 in formula, and X is halogen, N=1-4.
14. a kind of method preparing the ingredient of solid catalyst described in any one of claim 1-13 for olefinic polymerization, It is characterized in that, including：Magnesium compound and titanium compound is set to be selected from 1, the 8- naphthylenediamine class internal electron donors at least one Compound contacts, to obtain ingredient of solid catalyst.
15. one kind being used for alkene CH2=CHR polymerization catalyst, wherein R be hydrogen or the hydrocarbyl group containing 1-12 carbon atom, It is characterized in that, includes the product of following substance reaction：
(a) ingredient of solid catalyst described in any one of claim 1-13；
(b) at least one general formula is AlRnX(3-n)Organo-aluminum compound, R is the alkyl of hydrogen, carbon atom number 1-20 in formula；X is Halogen, n are the integer of 0≤n≤3；With, optionally,
(c) at least one general formula that is selected from is RnSi(OR1)4-nSilicone compounds as external donor compound, in formula R and R1For C1-C18Alkyl, optional also hetero atom；N is the integer of 0≤n≤3.
16. being used for alkene CH2The method of=CHR polymerizations, including homopolymerization, pre-polymerization and copolymerization, wherein R are former for hydrogen or containing 1-12 carbon The hydrocarbyl group of son, catalyst described in claim 15 in the presence of, carry out.
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CN1433339A (en) * 1999-12-23 2003-07-30 巴塞尔聚烯烃有限公司 New catalyst system and application thereof
CN101891651A (en) * 2009-05-19 2010-11-24 拜耳材料科技(中国)有限公司 Catalyst used in preparation of N-substituted carbamate and preparation method and application thereof
US20120264664A1 (en) * 2011-03-24 2012-10-18 Dibiase Stephen A Malienated derivatives
CN103923238A (en) * 2013-10-31 2014-07-16 北京利和知信科技有限公司 Catalyst component for olefin polymerization and catalyst
CN104045748A (en) * 2014-06-13 2014-09-17 北京利和知信科技有限公司 Solid catalyst component for olefin polymerization and catalyst

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1433339A (en) * 1999-12-23 2003-07-30 巴塞尔聚烯烃有限公司 New catalyst system and application thereof
CN101891651A (en) * 2009-05-19 2010-11-24 拜耳材料科技(中国)有限公司 Catalyst used in preparation of N-substituted carbamate and preparation method and application thereof
US20120264664A1 (en) * 2011-03-24 2012-10-18 Dibiase Stephen A Malienated derivatives
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