CN105384853B - Cocatalyst composition and its application - Google Patents

Cocatalyst composition and its application Download PDF

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CN105384853B
CN105384853B CN201410464313.2A CN201410464313A CN105384853B CN 105384853 B CN105384853 B CN 105384853B CN 201410464313 A CN201410464313 A CN 201410464313A CN 105384853 B CN105384853 B CN 105384853B
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alkyl
hydrogen
linear
aluminium
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CN105384853A (en
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郭峰
汪文睿
易玉明
李传峰
任鸿平
汪开秀
魏金花
杨爱武
陈韶辉
柏基业
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China Petroleum and Chemical Corp
Sinopec Yangzi Petrochemical Co Ltd
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China Petroleum and Chemical Corp
Sinopec Yangzi Petrochemical Co Ltd
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Abstract

The present invention relates to a kind of cocatalyst composition and its applications, relate more specifically to a kind of cocatalyst composition, it is characterized in that, reaction product and aikyiaiurnirsoxan beta including alkyl aluminum and water, wherein in terms of Al, the molar ratio of the reaction product of the alkyl aluminum and water and the aikyiaiurnirsoxan beta is 0.5: 1 to less than 4: 1.The invention further relates to the applications comprising the catalyst system of the cocatalyst composition and the cocatalyst composition in the complex-catalyzed olefine-cycloolefin copolymer of Nonmetallocene.Cocatalyst composition of the invention is cheaper compared to aikyiaiurnirsoxan beta cost.

Description

Cocatalyst composition and its application
Technical field
The present invention relates to a kind of cocatalyst compositions, are especially suitable for the complex-catalyzed olefine of Nonmetallocene With the copolyreaction of cycloolefin.The invention further relates to the catalyst systems comprising the cocatalyst composition, the co-catalyst group Close object helping in the complex-catalyzed olefine-cycloolefin copolymer of Nonmetallocene using and using the cocatalyst composition The olefine of catalysis and the copolymerization process of cycloolefin.
Background technique
As society is constantly progressive, development in science and technology is maked rapid progress, and the demand to high performance material is also increasing.Alkene Hydrocarbon-cyclic olefine copolymer, especially ethylene-cycloolefin hydrocarbon copolymer are a kind of excellent amorphous thermoplastic high molecular material, tool There is the features such as high transparency, low water absorbable, high-fire resistance and high refractive index.The high-end product utilized as C5 series comprehensive One of, it is expected to that PC and PMMA is replaced to be applied to optical component.In addition, the material can also be in packaging, electronic component, medical apparatus etc. Field has potential great market.
Known Nonmetallocene complex can be used as the catalyst of manufacture ethylene-cycloolefin hydrocarbon copolymer, and at present in non-cyclopentadienyl gold Generally using aikyiaiurnirsoxan beta such as methylaluminoxane (MAO) or the aluminium methyl of modification in the ethylene-cyclic olefin copolymerization of metal complex catalysis Oxygen alkane (MMAO) is used as co-catalyst.But since the price of aikyiaiurnirsoxan beta is higher, so that Nonmetallocene complex is further R and D become extremely difficult.
A kind of Nonmetallocene complex is disclosed in Chinese patent application 200610028959.1 and its in ethylene and ring-type Application in alpha-olefinic copolymerization.This kind of Nonmetallocene complex is for being catalyzed ethylene-The homogeneous or solution copolymerization of cycloolefin When mainly use MAO or MMAO as co-catalyst, and while the use of alkyl aluminum or halogenated alkyl aluminium being co-catalyst does not have substantially Activity, and formed using boron fluothane and boron alkyl class co-catalyst with halogenated alkyl aluminium composite catalyst when activity it is also opposite It is lower.
Further, since processing performance is poor when molecular weight is larger, therefore olefine-cyclic olefine copolymer molecular weight is usual Not Ying Tai great.However, the molecular weight of gained copolymer is usually larger when aikyiaiurnirsoxan beta is used alone as co-catalyst, such as viscous Average molecular weight is usually 100,000 or more.
In addition, glass transition temperature Tg is one important indicator of olefine-cyclic olefine copolymer thermal level, improve The application field of copolymerized product can be not only extended to the occasion of applied at elevated temperature by glass transition temperature, but also for needing height The application of temperature disinfection also becomes to be particularly suitable for.However, when aikyiaiurnirsoxan beta is used alone as co-catalyst, the glass of gained copolymer It is still unsatisfactory to change transition temperature.
Therefore, the current status of the prior art be still required it is a kind of suitable for the alkene complex-catalyzed in Nonmetallocene Co-catalyst used in hydrocarbon-cycloolefin copolymer, the co-catalyst is compared to aikyiaiurnirsoxan beta cost is cheaper, is more advantageous to copolymer Molecular weight control and/or can be improved the glass transition temperature of copolymer.
Summary of the invention
The present inventor passes through diligent the study found that by using low-cost alkyl aluminum on the basis of existing technology Composite catalyst is formed with specific molar ratio with the reaction product and aikyiaiurnirsoxan beta of water, so that it may it is aforementioned to solve at least one The problem of, and have thus completed the present invention.
Specifically, the present invention relates to the contents of following aspect.
1. cocatalyst composition, which is characterized in that reaction product and aikyiaiurnirsoxan beta including alkyl aluminum and water, wherein with Al The reaction product of meter, the alkyl aluminum and water and the molar ratio of the aikyiaiurnirsoxan beta are 0.5: 1 to less than 4: 1, preferably 0.5-3.9 ∶1。
2. according to cocatalyst composition described in aspect 1, which is characterized in that the reaction product of the alkyl aluminum and water is Alkyl aluminum and water press 1-5: 1, preferably 1-3: 1, the reaction product of more preferable 1.5-2.5: 1 molar ratio.
3. the cocatalyst composition according to aspect 1 or 2, which is characterized in that the alkyl aluminum is shown in following formula (A) Compound:
Al(R)3 (A)
Wherein group R is same or different to each other, and is each independently selected from C1-C8Alkyl is preferably each independently selected from first Base, ethyl and isobutyl group.
4. the cocatalyst composition according to any one of aspect 1-3, which is characterized in that the alkyl aluminum is selected from three Aluminium methyl (Al (CH3)3), triethyl aluminum (Al (CH2CH3)3), tri-n-n-propyl aluminum (Al (C3H7)3), triisobutyl aluminium (Al (i- C4H9)3), three n-butylaluminums (Al (C4H9)3), triisopentyl aluminium (Al (i-C5H11)3), three n-pentyl aluminium (Al (C5H11)3), three just Hexyl aluminium (Al (C6H13)3), three isohesyl aluminium (Al (i-C6H13)3), diethylmethyl aluminium (Al (CH3)(CH3CH2)2), dimethyl Aluminium ethide (Al (CH3CH2)(CH3)2) or their any combination, more preferable trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, three Aluminium isobutyl or their any combination, further preferred trimethyl aluminium, triisobutyl aluminium or their any combination, and most It is preferred that trimethyl aluminium.
5. the cocatalyst composition according to any one of aspect 1-4, which is characterized in that the aikyiaiurnirsoxan beta is selected from first One of base aikyiaiurnirsoxan beta, the methylaluminoxane of modification, ethylaluminoxane, isobutyl aluminium alkoxide and normal-butyl aikyiaiurnirsoxan beta are more Kind, it is preferably selected from one of methylaluminoxane, the methylaluminoxane of modification and isobutyl aluminium alkoxide or a variety of, is most preferably selected from Methylaluminoxane, the methylaluminoxane of modification and their any combination.
6. catalyst system, which is characterized in that urged including being helped described in any one of Nonmetallocene complex and aspect 1-5 Agent composition, the preferably described Nonmetallocene complex are selected from non-cyclopentadienyl shown in lower formula (I), lower formula (II) and following formula (I-1) One of metal complex is a variety of:
It is aforementioned it is various in, group R1To group R4, group R7With group R9It can be the same or different, each independently Selected from hydrogen and C1-4Linear chain or branched chain alkyl, preferably hydrogen；Group Y is O or S, preferably O；Group A is S or O, preferably S；Group R5It is C1-6Linear chain or branched chain alkyl, preferably C1-6Linear or branched alkyl group, more preferable C1-3Linear or branched alkyl group；Group R6With group R8 Can be identical or different, it is each independently selected from C3-6Linear chain or branched chain alkyl, preferably isopropyl or tert-butyl, especially uncle Butyl；Group R10It is hydrogen or C1-6Linear chain or branched chain alkyl, preferably hydrogen；Group M is selected from periodic table of elements III-th family to X I race Metallic element, preferred group ivb metallic element, more preferable Ti；Group X is halogen, preferably chlorine；Symbol --- represent coordinate bond.
7. according to catalyst system described in aspect 6, which is characterized in that the Nonmetallocene complex is following structural formula One of compound or their arbitrary proportion mixture:
8. the catalyst system according to aspect 6 or 7, which is characterized in that the cocatalyst composition in terms of Al Molar ratio with the Nonmetallocene complex in terms of metal M is 300-1500: 1, more preferably 500-1000: 1.
9. olefine-the ring complex-catalyzed in Nonmetallocene of cocatalyst composition described in any one of aspect 1-5 Application in olefin-copolymerization, the preferably described Nonmetallocene complex are selected from shown in lower formula (I), lower formula (II) and following formula (I-1) One of Nonmetallocene complex or a variety of:
It is aforementioned it is various in, group R1To group R4, group R7With group R9It can be the same or different, each independently Selected from hydrogen and C1-4Linear chain or branched chain alkyl, preferably hydrogen；Group Y is O or S, preferably O；Group A is S or O, preferably S；Group R5It is C1-6Linear chain or branched chain alkyl, preferably C1-6Linear or branched alkyl group, more preferable C1-3Linear or branched alkyl group；Group R6With group R8 Can be identical or different, it is each independently selected from C3-6Linear chain or branched chain alkyl, preferably isopropyl or tert-butyl, especially uncle Butyl；Group R10It is hydrogen or C1-6Linear chain or branched chain alkyl, preferably hydrogen；Group M is selected from periodic table of elements III-th family to X I race Metallic element, preferred group ivb metallic element, more preferable Ti；Group X is halogen, preferably chlorine；Symbol --- represent coordinate bond.
10. the combination of the reaction product and aikyiaiurnirsoxan beta of the alkyl aluminum and water olefine-ring complex-catalyzed in Nonmetallocene Application in olefin-copolymerization, wherein the molar ratio of the reaction product of the alkyl aluminum and water and the aikyiaiurnirsoxan beta is 0.5 in terms of Al : 1 to less than 4: 1, preferably 0.5-3.9: 1, the preferably described Nonmetallocene complex be selected from lower formula (I), lower formula (II) and under One of Nonmetallocene complex shown in formula (I-1) is a variety of:
It is aforementioned it is various in, group R1To group R4, group R7With group R9It can be the same or different, each independently Selected from hydrogen and C1-4Linear chain or branched chain alkyl, preferably hydrogen；Group Y is O or S, preferably O；Group A is S or O, preferably S；Group R5It is C1-6Linear chain or branched chain alkyl, preferably C1-6Linear or branched alkyl group, more preferable C1-3Linear or branched alkyl group；Group R6With group R8 Can be identical or different, it is each independently selected from C3-6Linear chain or branched chain alkyl, preferably isopropyl or tert-butyl, especially uncle Butyl；Group R10It is hydrogen or C1-6Linear chain or branched chain alkyl, preferably hydrogen；Group M is selected from periodic table of elements III-th family to X I race Metallic element, preferred group ivb metallic element, more preferable Ti；Group X is halogen, preferably chlorine；Symbol --- represent coordinate bond.
11. the copolymerization process of a kind of olefine and cycloolefin, which is characterized in that including using Nonmetallocene complex as main reminder Agent and with the anti-of alkyl aluminum defined in cocatalyst composition or aspect 10 described in any one of aspect 1-5 and water Answering the group of product and aikyiaiurnirsoxan beta to be combined into co-catalyst is copolymerized olefine with cycloolefin, or to appoint in aspect 6-8 Catalyst system described in one is that catalyst is copolymerized olefine with cycloolefin, and the preferably described Nonmetallocene is matched It closes object and is selected from one of Nonmetallocene complex shown in lower formula (I), lower formula (II) and following formula (I-1) or a variety of:
It is aforementioned it is various in, group R1To group R4, group R7With group R9It can be the same or different, each independently Selected from hydrogen and C1-4Linear chain or branched chain alkyl, preferably hydrogen；Group Y is O or S, preferably O；Group A is S or O, preferably S；Group R5It is C1-6Linear chain or branched chain alkyl, preferably C1-6Linear or branched alkyl group, more preferable C1-3Linear or branched alkyl group；Group R6With group R8 Can be identical or different, it is each independently selected from C3-6Linear chain or branched chain alkyl, preferably isopropyl or tert-butyl, especially uncle Butyl；Group R10It is hydrogen or C1-6Linear chain or branched chain alkyl, preferably hydrogen；Group M is selected from periodic table of elements III-th family to X I race Metallic element, preferred group ivb metallic element, more preferable Ti；Group X is halogen, preferably chlorine；Symbol --- represent coordinate bond.
12. copolymerization process described in application or aspect 11 described in any one of aspect 9-10, wherein the olefine selects From C2-6One of olefine is a variety of, optimal ethylene.
13. copolymerization process described in application or aspect 11 described in any one of aspect 9-10, wherein the cycloolefin is Optionally by one or more C1-10Linear chain or branched chain alkyl (preferably C1-10Linear or branched alkyl group or C2-10Linear chain or branched chain alkene Base) replace C3-20Cycloolefin is preferably selected from optionally by one or more C1-10Linear chain or branched chain alkyl (preferably C1-10Straight chain or Branched alkyl or C2-10Linear chain or branched chain alkenyl) replace cyclopentene, optionally by one or more C1-10Linear chain or branched chain alkyl (preferably C1-10Linear or branched alkyl group or C2-10Linear chain or branched chain alkenyl) cyclopentadiene, optionally one or more that replaces C1-10Linear chain or branched chain alkyl (preferably C1-10Linear or branched alkyl group or C2-10Linear chain or branched chain alkenyl) replace bicyclic penta 2 One of alkene and following formula (Y) compound represented are a variety of, are more preferably selected from norbornene, ethylidene norbornene, ethylene Base norbornene, norbornadiene, 5- methyinorbornene, tetracyclododecen, three cyclododecenes, tricyclic hendecene, five rings ten One of pentaene, five ring hexadecenes and 8- ethyltetracyclo laurylene are a variety of,
In formula (Y), group Ra to group Rh can be the same or different, and be each independently selected from hydrogen and C1-10Straight chain or Branched hydrocarbyl (preferably C1-10Linear or branched alkyl group or C2-10Linear chain or branched chain alkenyl), be preferably each independently selected from hydrogen, C1-3Linear or branched alkyl group or C2-3Linear chain or branched chain alkenyl；The integer that n is 0 to 6, preferably 0 or 1；SymbolIt represents single Key or double bond.
Technical effect
The cost of Invention cocata lysts composition is far below aikyiaiurnirsoxan beta, especially MAO and MMAO, but in Nonmetallocene In use, when can realize and use the aikyiaiurnirsoxan beta of same amount quite even in complex-catalyzed olefine-cycloolefin copolymer Slightly higher Copolymerization activity, although in some cases activity it is slightly lower but still within the acceptable range.
In addition, when using cocatalyst composition of the invention, it can be neatly by adjusting co-catalyst combination The component of object and component proportion regulate and control the molecular weight of copolymerization product, thus obtain viscosity average molecular weigh below 100,000, Even in 50,000 copolymers below.
In addition, olefine-cyclenes can be greatly improved when using certain preferred cocatalyst compositions of the invention The glass transition temperature of hydrocarbon copolymerization product.
Specific embodiment
Detailed description of the preferred embodiments below, it should be noted however that protection of the invention Range is not limited to these specific embodiments, and but is determined by the appended claims.
In the context of the present invention, unless otherwise defined explicitly or the meaning has exceeded those skilled in the art's Understand range, more than 3 carbon atoms hydrocarbon or hydrocarbon derivative group (such as propyl, propoxyl group, butyl, butane, butylene, butylene Base, hexane etc.) identical meaning when all having when not titled with prefix " just " with titled with prefix " just ".For example, propyl is generally managed Solution is n-propyl, and butyl is generally understood as normal-butyl, unless otherwise clear.
All publications, patent application, patent and the other bibliography that this specification is mentioned all are incorporated by reference into Herein.Unless otherwise defined, all technical and scientific terms used herein all there are those skilled in the art routinely to manage The meaning of solution.In case of conflict, it is subject to the definition of this specification.
When this specification with prefix " well known to those skilled in the art ", " prior art " or its export material similar to term Whens material, substance, method, step, device or component etc., object derived from the prefix is covered this field when the application proposes and is routinely made Those of with, but also include also being of little use at present, it will but become art-recognized for suitable for those of similar purpose.
In the context of the present specification, other than the content clearly stated, any matters or item that do not mention are equal It is directly applicable in those of known in the art without carrying out any change.Moreover, any embodiment described herein can be with It is freely combined with one or more other embodiments described herein, the technical solution or technical idea formed therefrom regards For the original disclosure of the present invention or a part of original description, and be not considered as not disclosing or be expected herein it is new in Hold, unless those skilled in the art think that the combination is obvious unreasonable.
In the context of the present invention, term " linear chain or branched chain alkyl " includes linear or branched alkyl group, linear chain or branched chain Alkenyl and linear chain or branched chain alkynyl.As the linear chain or branched chain alkyl, preferably linear or branched alkyl group.For example, C1-4Straight chain or Branched hydrocarbyl includes C1-4Linear or branched alkyl group, C2-4Linear chain or branched chain alkenyl and C2-4Linear chain or branched chain alkynyl, wherein it is preferred that C1-4Linear or branched alkyl group.
In the context of the present invention, term " halogen " includes fluorine, chlorine, bromine and iodine, wherein it is preferred that chlorine.
In the case where not clearly indicating, all percentages, number, the ratio etc. being previously mentioned in this specification be all with On the basis of weight, unless not meeting the conventional understanding of those skilled in the art when using weight as benchmark.
According to the present invention, first aspect is related to a kind of cocatalyst composition, which is characterized in that including alkyl aluminum and water Reaction product and aikyiaiurnirsoxan beta, wherein the molar ratio of the reaction product of the alkyl aluminum and water and the aikyiaiurnirsoxan beta is 0.5 in terms of Al : 1 to less than 4: 1, preferably 0.5-3.9: 1, more preferably 0.8-3.5: 1, more preferably 1-3: 1.
According to the present invention, it as the alkyl aluminum, for example can enumerate such as following formula (A) compound represented:
Al(R)3 (A)
In the formula (A), group R is same or different to each other, and is each independently selected from C1-C8Alkyl, wherein it is preferred that methyl, Ethyl and isobutyl group.
According to the present invention, as the alkyl aluminum, preferably trimethyl aluminium (Al (CH3)3), triethyl aluminum (Al (CH2CH3)3)、 Tri-n-n-propyl aluminum (Al (C3H7)3), triisobutyl aluminium (Al (i-C4H9)3), three n-butylaluminums (Al (C4H9)3), triisopentyl aluminium (Al(i-C5H11)3), three n-pentyl aluminium (Al (C5H11)3), tri-n-hexyl aluminum (Al (C6H13)3), three isohesyl aluminium (Al (i- C6H13)3), diethylmethyl aluminium (Al (CH3)(CH3CH2)2) and dimethyl ethyl aluminium (Al (CH3CH2)(CH3)2) etc., more preferably Trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum and triisobutyl aluminium, further preferred trimethyl aluminium, triethyl aluminum and three isobutyls Base aluminium.In this respect, for the purpose for realizing high catalytic activity (i.e. high co-catalysis performance), most preferably trimethyl aluminium and three isobutyls Base aluminium；For the purpose for realizing better molecular weight control, most preferably triethyl aluminum.
According to the present invention, the alkyl aluminum and the reaction product of water refer to obtaining after alkyl aluminum above-mentioned is reacted with water Hydrolysate, hereafter also abbreviation alkyl aluminum hydrolysis product or hydrolysate sometimes.In the reaction, the alkyl aluminum and water rub You are than generally 1-5: 1, preferably 1-3: 1, more preferably 1.5-2.5: 1.
According to a preferred embodiment, the hydrolysate in inert atmosphere (such as nitrogen) and solvent (such as toluene) by depositing Alkyl aluminum is set to react to obtain with water under, reaction temperature can be -150 DEG C to room temperature, preferably -100 DEG C to -40 DEG C.
According to the present invention, the reaction product of these alkyl aluminums and water can be used alone, or with arbitrary ratio It is applied in combination a variety of.
According to the present invention, as the aikyiaiurnirsoxan beta, for example linear alumoxanes shown in following formula (B): (R) (R) can be enumerated Al-(Al(R)-O)nCyclic aluminoxane shown in-O-Al (R) (R) and following formula (C) :-(Al (R)-O-)n+2,
In formula above-mentioned (B) and formula (C), group R is same or different to each other, and is each independently selected from C1-C8Alkyl, In preferably methyl, ethyl, normal-butyl and isobutyl group, more preferable methyl.N is the arbitrary integer within the scope of 1-50, preferably 10-30 model Enclose interior arbitrary integer.
According to the present invention, the aikyiaiurnirsoxan beta can by further by it is known in the art it is any in a manner of modified it is (existing There is technology to be also referred to as the aikyiaiurnirsoxan beta modified).As the aikyiaiurnirsoxan beta of the modification, for example the methylaluminoxane of modification can be enumerated (MMAO).As the MMAO, commercially available product can be directly used, it can also be such as public according to United States Patent (USP) US5041584 The method opened is manufactured.The aikyiaiurnirsoxan beta of the modification is also easily known as aikyiaiurnirsoxan beta herein.
According to the present invention, as the aikyiaiurnirsoxan beta, preferably methylaluminoxane, the methylaluminoxane of modification, ethylaluminoxane, Isobutyl aluminium alkoxide and normal-butyl aikyiaiurnirsoxan beta, more preferable methylaluminoxane, the methylaluminoxane of modification and isobutyl aluminium alkoxide, most It is preferred that the methylaluminoxane of methylaluminoxane and modification.
According to the present invention, these aikyiaiurnirsoxan betas can be used alone, or is applied in combination with arbitrary ratio a variety of.
In the present invention, as needed, the cocatalyst composition can also be comprising without the auxiliary of promoting catalysis Co-ingredients, such as solvent and diluent are preferably substantially free of the other co-catalysts additionally added, such as alkyl aluminum, halogenated alkyl Aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt etc..Herein, the substance of so-called " additional addition " refers in situ in the reaction Other than the substance of generation, the substance that separately adds.
According to some embodiments of the present invention, the cocatalyst composition substantially reacts production by alkyl aluminum and water Object and aikyiaiurnirsoxan beta composition, or be made of the reaction product and aikyiaiurnirsoxan beta of alkyl aluminum and water.It is so-called " substantially by alkyl aluminum and water Reaction product and aikyiaiurnirsoxan beta composition ", refer to the cocatalyst composition in addition to comprising the hydrolysate and aikyiaiurnirsoxan beta Except, solvent used as needed can also be further included, so that the cocatalyst composition is presented for convenience The solution state of user's operation.
According to the present invention, second aspect is related to a kind of catalyst system, which is characterized in that including Nonmetallocene complex and Cocatalyst composition of the invention.
According to the present invention, in the catalyst system, the cocatalyst composition preferably in terms of Al and with metal M The molar ratio of the Nonmetallocene complex of meter is 300-1500: 1, more preferably 500-1000: 1.
According to the present invention, the third aspect is related to the cocatalyst composition of the invention chain complex-catalyzed in Nonmetallocene Application in alkene-cycloolefin copolymer.
According to the present invention, fourth aspect is related to the copolymerization process of a kind of olefine and cycloolefin, which is characterized in that including with Nonmetallocene complex is major catalyst and makes olefine and cycloolefin as co-catalyst using cocatalyst composition of the invention It is copolymerized, or is copolymerized olefine with cycloolefin as catalyst using catalyst system of the invention.
According to the present invention, the copolymerization process preferably includes to contact olefin feedstock first again with the Nonmetallocene complex The step of being contacted with the cocatalyst composition, or including make olefin feedstock simultaneously with the Nonmetallocene complex and institute The step of stating cocatalyst composition contact.
According to the present invention, in invention catalyst system above-mentioned, the application of Invention cocata lysts composition and this hair In bright copolymerization process, the Nonmetallocene complex is preferably selected from change shown in lower formula (I) compound represented, lower formula (II) Close object and following formula (I-1) compound represented.These Nonmetallocene complexs can be used alone, or arbitrarily to compare Example is applied in combination a variety of.
According to the present invention, it is aforementioned it is various in, group R1To group R4, group R7With group R9It can be identical or not Together, hydrogen and C are each independently selected from1-4Linear chain or branched chain alkyl, is preferably each independently selected from hydrogen and C1-4Linear chain or branched chain alkane Base is more preferably each independently selected from hydrogen and methyl, more preferable hydrogen.
According to the present invention, it is aforementioned it is various in, group Y is O or S, preferably O.
According to the present invention, it is aforementioned it is various in, group A is S or O, preferably S.
According to the present invention, it is aforementioned it is various in, group R5It is C1-6Linear chain or branched chain alkyl, preferably C1-6Linear chain or branched chain alkane Base, more preferable C1-3Linear or branched alkyl group, most preferable, ethyl, n-propyl or isopropyl.
According to the present invention, it is aforementioned it is various in, group R6With group R8Can be identical or different, it is each independently selected from C3-6 Linear chain or branched chain alkyl such as C3-6Linear or branched alkyl group is preferably each independently selected from C3-6Branched alkyl, more preferable isopropyl Base or tert-butyl, especially tert-butyl.
According to the present invention, it is aforementioned it is various in, group R10It is hydrogen or C1-6Linear chain or branched chain alkyl, preferably hydrogen or C1-4Straight chain Or branched alkyl, more preferable hydrogen, methyl and ethyl, most preferably hydrogen.
According to the present invention, it is aforementioned it is various in, group M be selected from periodic table of elements III-th family to X I race metallic element, It is preferred that group ivb metallic element such as titanium, zirconium and hafnium, more preferable Ti.
According to the present invention, it is aforementioned it is various in, group X is halogen, including fluorine, chlorine, bromine and iodine, wherein it is preferred that chlorine.
According to the present invention, it is aforementioned it is various in, symbol --- represent coordinate bond.
According to the present invention, as the Nonmetallocene complex, one of compound of more preferably following structural formula or its The mixture of meaning ratio, but not limited to this:
According to the present invention, formula (I) compound represented can such as be manufactured by following manufacturing method.
According to the present invention, which such as includes making to change shown in following formula (I-A) compound represented and lower formula (X) Close the step of object occurs complexation reaction, obtains the formula (I) compound represented (hereinafter referred to as coordination step A).
MX4 (X)
According to the present invention, in formula (X), metallic element of the group M selected from periodic table of elements III-th family to X I race is excellent Group ivb metallic element such as titanium, zirconium and hafnium are selected, wherein more preferable titanium.
According to the present invention, in formula (X), group X is halogen, including fluorine, chlorine, bromine and iodine, wherein it is preferred that chlorine.
According to the present invention, when carrying out the coordination step A, formula (X) compound represented and the formula (I-A) institute The molar ratio of the compound shown is generally 0.7-1.5, preferably 0.9-1.3, more preferable 1-1.2.
According to the present invention, the coordination step A can be in the presence of a solvent.The present invention is to the solvent without spy Other restriction, as long as it can dissolve the formula (X) compound represented and the formula (I-A) compound represented but not interfere The complexation reaction.Specifically, as the solvent, for example C can be enumerated1-20Alkane, C6-20Aromatic hydrocarbon and C4-20Rouge Cyclic hydrocarbon etc., wherein it is preferred that C6-12Aromatic hydrocarbon, most preferably toluene, dimethylbenzene, trimethylbenzene.These solvents can be used alone, Or it is applied in combination with arbitrary ratio a variety of.
According to the present invention, to the dosage of the solvent, there is no particular limitation, as long as being conducive to complexation reaction progress Any dosage can use, for example can enumerate the molar ratio of the solvent and the formula (I-A) compound represented is 5- 200, preferably 10-100, but it is not limited to this.
According to the present invention, generally -80-100 DEG C of the reaction temperature of the coordination step A, it is preferably -50-70 DEG C, more excellent - 30-50 DEG C of choosing.
According to the present invention, the reaction pressure of the coordination step A can be any pressure for being suitble to the complexation reaction to carry out, But for the sake of implementing for convenience, generally normal pressure to 0.2MPa.
According to the present invention, the reaction time of the coordination step A is generally 0.1-72 hours, and preferably 0.2-48 hours, more It is preferred that 1-24 hours.
According to the present invention, as needed, in order to promote the progress of reaction, the complexation reaction of the coordination step A can be It is carried out under stirring (for example speed of agitator is 100-1000rpm).
According to the present invention, as needed, the complexation reaction of the coordination step A can under the atmosphere of protective gas into Row.As the protective gas, for example inert gas such as nitrogen can be enumerated etc..
It according to the present invention, can be from this by conventional separate mode after the complexation reaction of the coordination step A It reacts in the mixture obtained and isolates the formula (I) compound represented as reaction product.As the separate mode, For example it can enumerate to filter perhaps first to filter and wash or be optionally further dried again.Alternatively, as needed, can also lead to Recrystallization, column chromatography method or preparation chromatography etc. is crossed to purify the reaction product of the acquisition.
According to the present invention, the method being filtered, washed and dried is not particularly limited, is can according to need Using those of commonly used in the art.As needed, the washing is general carries out 1-6 times, preferably 2-3 times.Wherein, washing is used Solvent is preferably identical as solvent used in complexation reaction, and however, you can also not same.As the drying, for example inertia can be enumerated Gas dry method, boulton process or heating under vacuum seasoning etc., wherein it is preferred that adding under inert gas seasoning or vacuum Heated drying method, most preferably heating under vacuum seasoning.At this point, the temperature range of the drying is generally room temperature to 140 DEG C, dry Time is generally 2-20 hours, and but it is not limited to this.
According to the present invention, in the formula (I-A), group R1To group R4, group R7With group R9It can be identical or not Together, hydrogen and C are each independently selected from1-4Linear chain or branched chain alkyl, is preferably each independently selected from hydrogen and C1-4Linear chain or branched chain alkane Base is more preferably each independently selected from hydrogen and methyl, more preferable hydrogen.
According to the present invention, in the formula (I-A), group Y is O or S, preferably O.
According to the present invention, in the formula (I-A), group A is S or O, preferably S.
According to the present invention, in the formula (I-A), group R5It is C1-6Linear chain or branched chain alkyl, preferably C1-6Linear chain or branched chain Alkyl, more preferable C1-3Linear or branched alkyl group, most preferable, ethyl, n-propyl or isopropyl.
According to the present invention, in the formula (I-A), group R6With group R8Can be identical or different, it is each independently selected from C3-6Linear chain or branched chain alkyl such as C3-6Linear or branched alkyl group is preferably each independently selected from C3-6Branched alkyl, it is more preferably different Propyl or tert-butyl, especially tert-butyl.
According to the present invention, in the formula (I-A), group R10It is hydrogen or C1-6Linear chain or branched chain alkyl, preferably hydrogen or C1-4Directly Chain or branched alkyl, more preferable hydrogen, methyl and ethyl, most preferably hydrogen.
According to the present invention, as formula (I-A) compound represented, more preferably following structural formula compound represented,
According to the present invention, formula (I-A) compound represented, for example following manufacturing method system can be passed through It makes.
According to the present invention, the manufacturing method such as may include following step (1) and step (2).
Step (1): make lower formula (III) compound represented and lower formula (IV) compound represented that condensation reaction occur, obtain Formula (V) compound represented must be descended.
According to the present invention, in the formula (III), group R1To group R4It can be the same or different, select each independently From hydrogen and C1-4Linear chain or branched chain alkyl, is preferably each independently selected from hydrogen and C1-4Linear or branched alkyl group, more preferably respectively solely On the spot it is selected from hydrogen and methyl, more preferable hydrogen.
According to the present invention, in the formula (III), group A is S or O, preferably S.
According to the present invention, in the formula (III), group R5It is C1-6Linear chain or branched chain alkyl, preferably C1-6Linear chain or branched chain Alkyl, more preferable C1-3Linear or branched alkyl group, most preferable, ethyl, n-propyl or isopropyl.
According to the present invention, as formula (III) compound represented, preferably 2- aminophenyl Dimethyl sulfide.
According to the present invention, in the formula (IV), group R7With group R9It can be the same or different, select each independently From hydrogen and C1-4Linear chain or branched chain alkyl, is preferably each independently selected from hydrogen and C1-4Linear or branched alkyl group, more preferably respectively solely On the spot it is selected from hydrogen and methyl, more preferable hydrogen.
According to the present invention, in the formula (IV), group Y is O or S, preferably O.
According to the present invention, in the formula (IV), group R6With group R8Can be identical or different, it is each independently selected from C3-6 Linear chain or branched chain alkyl such as C3-6Linear or branched alkyl group is preferably each independently selected from C3-6Branched alkyl, more preferable isopropyl Base or tert-butyl, especially tert-butyl.
According to the present invention, in the formula (IV), group R10It is hydrogen or C1-6Linear chain or branched chain alkyl, preferably hydrogen or C1-4Straight chain Or branched alkyl, more preferable hydrogen, methyl and ethyl, most preferably hydrogen.
According to the present invention, as formula (IV) compound represented, preferably 3,5- di-tert-butyl salicylaldehyde.
According to the present invention, in the formula (V), group R1To group R4, group R7With group R9It can be identical or not Together, hydrogen and C are each independently selected from1-4Linear chain or branched chain alkyl, is preferably each independently selected from hydrogen and C1-4Linear chain or branched chain alkane Base is more preferably each independently selected from hydrogen and methyl, more preferable hydrogen.
According to the present invention, in the formula (V), group Y is O or S, preferably O.
According to the present invention, in the formula (V), group A is S or O, preferably S.
According to the present invention, in the formula (V), group R5It is C1-6Linear chain or branched chain alkyl, preferably C1-6Linear chain or branched chain alkane Base, more preferable C1-3Linear or branched alkyl group, most preferable, ethyl, n-propyl or isopropyl.
According to the present invention, in the formula (V), group R6With group R8Can be identical or different, it is each independently selected from C3-6 Linear chain or branched chain alkyl such as C3-6Linear or branched alkyl group is preferably each independently selected from C3-6Branched alkyl, more preferable isopropyl Base or tert-butyl, especially tert-butyl.
According to the present invention, in the formula (V), group R10It is hydrogen or C1-6Linear chain or branched chain alkyl, preferably hydrogen or C1-4Straight chain Or branched alkyl, more preferable hydrogen, methyl and ethyl, most preferably hydrogen.
According to the present invention, the reaction of the step (1) can carry out in the presence of solvent (hereinafter referred to as the first solvent). As first solvent, for example C can be enumerated1-15Fatty alcohol, C6-20Aromatic alcohol, C4-20Alicyclic ring alcohol, C1-20Alkane, C6-20Fragrance Hydrocarbon or C4-20Alicyclic, wherein it is preferred that C1-4Fatty alcohol, most preferably methanol or ethyl alcohol.These first solvents can be used alone, It can also be used with combination of two or more, or as needed, the form as aqueous solution uses.
According to the present invention, to the dosage of first solvent, there is no particular limitation, as long as being conducive to the step (1) Any dosage that condensation reaction carries out can use, for example can enumerate rubbing for the first solvent and formula (IV) compound represented Your ratio is 5-200: 1, preferably 15-50: 1, but it is not limited to this.
According to the present invention, when carrying out the condensation reaction of the step (1), formula (IV) compound represented and formula (III) The molar ratio of compound represented is usually 0.5-2: 1, and preferably 0.8-1.2: 1.
According to the present invention, the reaction of the step (1) can carry out in the presence of a catalyst.As the catalyst, For example organic carboxyl acid can be enumerated, it further can such as enumerate C1-10Aliphatic carboxylic acid, C6-20Aromatic carboxylic acid or C4-20Rouge Cycloaliphatic carboxylic, wherein it is preferred that C1-4Aliphatic carboxylic acid, most preferably acetic acid.These catalyst can be used alone, can also two kinds or Multiple combinations use.To the dosage of the catalyst, there is no particular limitation, as long as can promote the reaction of the step (1) into Capable any dosage can use, for example can enumerate the catalyst and the molar ratio of formula (IV) compound represented is 0.002-0.5: 1, preferably 0.01-0.1: 1, but it is not limited to this.
According to the present invention, generally -20-150 DEG C of the reaction temperature of the step (1), preferably 20-120, more preferable 50- 90℃。
According to the present invention, the reaction pressure of the step (1) can be suitble to the reaction carry out any pressure, but in order to For the sake of facilitating implementation, generally normal pressure to 0.5MPa.
According to the present invention, the reaction time of the step (1) is generally 0.1-20 hours, preferably 1-12 hours, more preferably 2-6 hours.
According to the present invention, as needed, in order to promote the progress reacted, the condensation reaction of the step (1) can stirred It mixes and is carried out under (for example speed of agitator is 100-1000rpm).
According to the present invention, the step (1) after reaction, can be anti-from the condensation by conventional separate mode The formula (V) compound represented is isolated in the mixture that should be obtained.As the separate mode, for example can enumerate Filter, which is perhaps first filtered, to be washed again or is optionally further dried.Alternatively, as needed, can also by column chromatography method or Preparation chromatography etc. purifies formula (V) compound represented of the acquisition.
According to the present invention, the method being filtered, washed and dried is not particularly limited, is can according to need Using those of commonly used in the art.As needed, the washing is general carries out 1-6 times, preferably 2-3 times.Wherein, washing is used Solvent is preferably identical as first solvent, and however, you can also not same.As the drying, for example inert gas drying can be enumerated Method, boulton process or heating under vacuum seasoning etc., wherein it is preferred that inert gas seasoning or heating under vacuum seasoning, Most preferably heating under vacuum seasoning.At this point, the temperature range of the drying is generally room temperature to 140 DEG C, drying time is general It is 2-20 hours, but it is not limited to this.
Step (2): the formula (V) compound represented is restored, for example uses reducing agent, is obtained shown in the formula (I-A) Compound.
According to the present invention, to reducing agent used in step (2), there is no particular limitation, as long as can be only by the formula (V)-the CR in compound represented molecular structure center10=N- is reduced to-CHR10- NH- (without change the compound other Molecular structure does not cause especially the group A especially S in its molecular structure to remove) any reducing agent can be used.Make For the reducing agent, for example the combination of metal hydride or metal and acid can be enumerated.These reducing agents can be used alone, It can also be used with combination of two or more.
According to the present invention, as the metal hydride, for example can to enumerate organic synthesis field conventional for this purpose Any metal hydride used specifically can such as enumerate alkali metal hydride (such as NaH) or alkali metal and Al or B shape At complex hydride (such as LiAlH4、NaBH4Deng), wherein it is preferred that LiAlH4.As the use of the metal hydride at this time The molar ratio of amount, the metal hydride and formula (V) compound represented such as can be 0.25-4: 1, preferably 0.5-2: 1.
According to the present invention, the metal and acid combination in, as the metal, for example, can enumerate Li, Fe, Mg and The active metal of the chemical property such as Zn, wherein for cheap and angle that is being easy to get, preferably Fe or Zn.As described Acid, for example the inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid or middle strong acid or C can be enumerated1-10Fatty acid, C6-20Aromatic acid and C4-20The organic carboxyl acids such as alicyclic acid.These metals or acid can be used alone, and can also be used with combination of two or more.
According to the present invention, in the combination of the metal and acid, the molar ratio of the metal and the acid such as can be 5-200: 1, preferably 20-100: 1.When being used as reducing agent, as the combined dosage of the metal and acid, for example can enumerate So that the molar ratio of the metal and formula (V) compound represented is 1-30: 1, preferably 2-10: 1.
According to the present invention, the reduction reaction of the step (2) can be in the presence of solvent (hereinafter referred to as the second solvent) It carries out.As second solvent, for example water, ether (such as ether), C can be enumerated1-15Fatty alcohol, C6-20Aromatic alcohol, C4-20Rouge Cyclic alcohol, C1-20Aliphatic hydrocarbon, C6-20Aromatic hydrocarbon and C4-20Alicyclic, wherein it is preferred that water, ether, toluene, methanol, ethyl alcohol or propyl alcohol. These second solvents can be used alone, and can also be used with combination of two or more.
According to the present invention, to the dosage of second solvent, there is no particular limitation, as long as being conducive to the step (2) Any dosage that reduction reaction carries out can use, for example can enumerate rubbing for the second solvent and formula (V) compound represented Your ratio is 2-500: 1, preferably 5-200: 1, but it is not limited to this.
According to the present invention, the reaction temperature of the step (2) is generally 10-150 DEG C, preferably 50-110 DEG C, more preferable 70- 100℃。
According to the present invention, the reaction pressure of the step (2) can be suitble to the reaction carry out any pressure, but in order to For the sake of facilitating implementation, generally normal pressure to 0.2MPa.
According to the present invention, the reaction time of the step (2) is generally 0.1-20 hours, preferably 0.2-10 hours, more excellent It selects 0.3-5 hours.
According to the present invention, as needed, in order to promote the progress reacted, the reduction reaction of the step (2) can stirred It mixes and is carried out under (for example speed of agitator is 100-1000rpm).
According to the present invention, as needed, the reduction reaction of the step (2) can under the atmosphere of protective gas into Row.As the protective gas, for example inert gas such as nitrogen can be enumerated etc..
According to the present invention, the step (2) after reaction, can be obtained from the reaction by conventional separate mode The formula (I-A) compound represented is isolated in the mixture obtained.As the separate mode that can be used at this time, such as can be with Enumerate the methods of filtering-filtrate decompression concentration-cooling precipitation, standing-clear liquid concentration-precipitating.
According to the present invention, as needed, the formula (I-A) compound represented so obtained can also be by routine The purification process known such as recrystallization method (for example using methylene chloride, toluene etc. as recrystallization solvent) is purified, and It is not particularly limited.Alternatively, as needed, it can also be by column chromatography method or preparation chromatography etc. to the formula of the acquisition (I-A) compound represented is purified.
According to the present invention, formula (II) compound represented can such as be manufactured by following manufacturing method.
According to the present invention, which such as includes making shown in aforementioned formula (V) compound represented and aforementioned formula (X) The step of complexation reaction occurs for compound, obtains the formula (II) compound represented (hereinafter referred to as coordination step B).
According to the present invention, when carrying out the coordination step B, formula (X) compound represented and the formula (V) are shown The molar ratio of compound be generally 0.7-1.5, preferably 0.9-1.3, more preferable 1-1.2.
According to the present invention, the coordination step B can be carried out in the presence of solvent (also referred to as third solvent).The present invention To the third solvent, there is no particular limitation, as long as it can dissolve the formula (X) compound represented and the formula (V) institute The compound that shows but do not interfere the complexation reaction.Specifically, as the third solvent, for example C can be enumerated1-20 Alkane, C6-20Aromatic hydrocarbon and C4-20Alicyclic etc., wherein it is preferred that C6-12Aromatic hydrocarbon, most preferably toluene, dimethylbenzene, trimethylbenzene.These Third solvent can be used alone, or is applied in combination with arbitrary ratio a variety of.
According to the present invention, to the dosage of the third solvent, there is no particular limitation, as long as being conducive to the complexation reaction Any dosage carried out can use, for example can enumerate the molar ratio of third solvent and the formula (V) compound represented For 5-200, preferably 10-100, but it is not limited to this.
According to the present invention, generally -80-100 DEG C of the reaction temperature of the coordination step B, it is preferably -50-70 DEG C, more excellent - 30-50 DEG C of choosing.
According to the present invention, the reaction pressure of the coordination step B can be any pressure for being suitble to the complexation reaction to carry out, But for the sake of implementing for convenience, generally normal pressure to 0.2MPa.
According to the present invention, the reaction time of the coordination step B is generally 0.1-72 hours, preferably 0.2-484, when, more It is preferred that 1-24 hours.
According to the present invention, as needed, in order to promote the progress of reaction, the complexation reaction of the coordination step B can be It is carried out under stirring (for example speed of agitator is 100-1000rpm).
According to the present invention, as needed, the complexation reaction of the coordination step B can under the atmosphere of protective gas into Row.As the protective gas, for example inert gas such as nitrogen can be enumerated etc..
It according to the present invention, can be from this by conventional separate mode after the complexation reaction of the coordination step B It reacts in the mixture obtained and isolates the formula (II) compound represented as reaction product.As the separation side Formula, for example can enumerate to filter perhaps first to filter and wash or be optionally further dried again.Alternatively, as needed, it can be with The reaction product of the acquisition is purified by recrystallization, column chromatography method or preparation chromatography etc..
According to the present invention, the method being filtered, washed and dried is not particularly limited, is can according to need Using those of commonly used in the art.As needed, the washing is general carries out 1-6 times, preferably 2-3 times.Wherein, washing is used Solvent is preferably identical as the third solvent, and however, you can also not same.As the drying, for example inert gas drying can be enumerated Method, boulton process or heating under vacuum seasoning etc., wherein it is preferred that inert gas seasoning or heating under vacuum seasoning, Most preferably heating under vacuum seasoning.At this point, the temperature range of the drying is generally room temperature to 140 DEG C, drying time is general It is 2-20 hours, but it is not limited to this.
According to the present invention, formula (I-1) compound represented can such as be manufactured by following manufacturing method, Wherein the manufacturing method such as may include following step (1) and step (2).
Step (1): the step of making previously described formula (I-A) compound represented dehydrogenation (hereinafter referred to as dehydrogenation step).
According to the present invention, according to the step (1), make group NH and group contained by previously described formula (I-A) compound represented H removing on YH, thus to obtain anion structural compounds shown in formula (I-B).
According to the present invention, do not have to the method for making previously described formula (I-A) compound represented dehydrogenation and generating the anion structure There is special restriction, any method that can be used for this purpose and routinely using this field.For example, by making the formula (I-A) Compound represented is reacted with metal hydride, and the dehydrogenation can be realized.
According to the present invention, as the hydride, for example alkali metal hydride (such as NaH or KH) can be enumerated, In preferred KH.As the dosage of the metal hydride at this time, the metal hydride and the formula (I-A) compound represented Molar ratio such as can be 2-6: 1, preferably 2-4: 1.
According to the present invention, the dehydrogenation step can be in the presence of a solvent.As the solvent, for example can lift C out6-12Aromatic hydrocarbon, halogenated C1-10Alkane and ether solvent etc..It specifically can such as enumerate toluene, dimethylbenzene, tetrahydrofuran, stone Oily ether, ether, 2,4- dioxane, methylene chloride, 1,2- dichloroethanes and carbon tetrachloride etc., most preferably tetrahydrofuran.These Solvent can be used alone, or is applied in combination with arbitrary ratio a variety of.
According to the present invention, to the dosage of the solvent, there is no particular limitation, as long as being conducive to dehydrogenation reaction progress Any dosage can use, for example the solvent can be enumerated and the molar ratio of the formula (I-A) compound represented is 100-2000: 1, preferably 200-1000: 1, but it is not limited to this.
According to the present invention, the reaction temperature of the dehydrogenation step is generally -80-100 DEG C, preferably-50-70 DEG C, more preferably- 30-50℃。
According to the present invention, the reaction pressure of the dehydrogenation step can be any pressure for being suitble to the complexation reaction to carry out, But for the sake of implementing for convenience, generally normal pressure to 0.2MPa.
According to the present invention, the reaction time of the dehydrogenation step is generally 0.1-72 hours, preferably 0.2-48 hours, more excellent It selects 1-24 hours.
According to the present invention, as needed, in order to promote the progress of reaction, the dehydrogenation step (for example can be stirred in stirring Revolving speed is mixed to carry out under 100-1000rpm).
According to the present invention, as needed, the dehydrogenation step can carry out under the atmosphere of protective gas.As described Protective gas, for example inert gas such as nitrogen can be enumerated etc..
According to the present invention, after the dehydrogenation reaction of the dehydrogenation step, by removing any solvent that may be used, Obtaining anion shown in the formula (I-B), (its counter ion counterionsl gegenions such as can be the alkali derived from the alkali metal hydride Metal cation) reaction product of the structural compounds as the dehydrogenation step.As the mode for removing solvent, such as can be with Rotary evaporation is enumerated except solvent method, vacuum are except solvent method etc., but it is not limited to this.
Step (2): shown in the reaction product (i.e. formula (I-B) compound represented) and aforementioned formula (X) for obtaining step (1) Compound complexation reaction, the step of obtaining the formula (I-1) compound represented (hereinafter referred to as coordination step C) occurs.
According to the present invention, when carrying out the coordination step C, so that the formula (X) compound represented and the formula (I- B) molar ratio of compound represented commonly reaches 0.7-1.5, preferably 0.9-1.3, more preferable 1-1.2.
According to the present invention, the coordination step C can be carried out in the presence of solvent (also referred to as the 4th solvent).The present invention To the 4th solvent, there is no particular limitation, as long as it can dissolve the formula (X) compound represented and the formula (I-B) Compound represented but do not interfere the complexation reaction.Specifically, as the 4th solvent, for example can enumerate C1-20Alkane, C6-20Aromatic hydrocarbon and C4-20Alicyclic etc., wherein it is preferred that C6-12Aromatic hydrocarbon, most preferably toluene, dimethylbenzene, trimethylbenzene. These the 4th solvents can be used alone, or is applied in combination with arbitrary ratio a variety of.
According to the present invention, to the dosage of the 4th solvent, there is no particular limitation, as long as being conducive to the complexation reaction Any dosage carried out can use, for example can enumerate mole of the 4th solvent and the formula (I-B) compound represented Than for 5-200, preferably 10-100, but it is not limited to this.
According to the present invention, the reaction temperature of the coordination step C is generally -80-100 DEG C, preferably-50-70 DEG C, more preferably- 30-50℃。
According to the present invention, the reaction pressure of the coordination step C can be any pressure for being suitble to the complexation reaction to carry out, But for the sake of implementing for convenience, generally normal pressure to 0.2MPa.
According to the present invention, the reaction time of the coordination step C is generally 0.1-72 hours, preferably 0.2-48 hours, more It is preferred that 1-24 hours.
According to the present invention, as needed, in order to promote the progress of reaction, the complexation reaction of the coordination step C can be It is carried out under stirring (for example speed of agitator is 100-1000rpm).
According to the present invention, the complexation reaction needs of the coordination step C carry out under the atmosphere of protective gas.As institute State protective gas, for example inert gas such as nitrogen can be enumerated etc..
It according to the present invention, can be from this by conventional separate mode after the complexation reaction of the coordination step C It reacts in the mixture obtained and isolates the formula (I-1) compound represented as reaction product.As the separation side Formula, for example can enumerate to filter perhaps first to filter and wash or be optionally further dried again.Alternatively, as needed, it can be with The reaction product of the acquisition is purified by recrystallization, column chromatography method or preparation chromatography etc..
According to the present invention, the method being filtered, washed and dried is not particularly limited, is can according to need Using those of commonly used in the art.As needed, the washing is general carries out 1-6 times, preferably 2-3 times.Wherein, washing is used Solvent is preferably identical as the 4th solvent, and however, you can also not same.As the drying, for example inert gas drying can be enumerated Method, boulton process or heating under vacuum seasoning etc., wherein it is preferred that inert gas seasoning or heating under vacuum seasoning, Most preferably heating under vacuum seasoning.At this point, the temperature range of the drying is generally room temperature to 140 DEG C, drying time is general It is 2-20 hours, but it is not limited to this.
Known to those skilled in the art to be, aforementioned all method and steps are preferably in the item of substantially anhydrous and oxygen-free It is carried out under part.Substantially anhydrous and oxygen-free mentioned here refers to content of the content continuously less than 50ppm and oxygen of water in system Continuously less than 300ppm.
For copolymerization process according to the present invention, other than the following content particularly pointed out, what other were not explained It is conventional that content (such as feeding manner etc. of polymerization reactor, reaction raw materials or catalyst etc.) can directly be applicable in this field Those of know, it is not particularly limited, the description thereof will be omitted herein.
According to the present invention, the olefine refers to the alkene with straight or branched structure, specifically can such as lift C out2-10Straight or branched alkene, wherein it is preferred that C2-6Straight or branched alkene or C2-3Olefine, more preferable ethylene.
According to the present invention, these olefines can be used alone, and can also be used with combination of two or more.
According to the present invention, the cycloolefin refers to the alkene with double bond on ring, specifically can such as enumerate C3-20Ring Alkene.As the C3-20Cycloolefin specifically can such as enumerate cyclobutane, cyclopentene, cyclopentadiene, cyclohexene, hexamethylene two The monocyclic cycloalkenyls such as alkene, cycloheptene, cycloheptadiene, cyclo-octatetraene hydrocarbon and dicyclopentadiene, norbornene, norbornadiene, Equal loop coils, bridged ring or condensed ring formula is bicyclic or polycyclic ring Alkene.As the C3-20Cycloolefin, cyclopentene, cyclopentadiene, dicyclopentadiene, norbornene or Fourth Ring 12 Alkene.
According to the present invention, the C3-20Cycloolefin optionally further by it is one or more (such as 1 to 5,1 to 4,1 to 3,1 to 2 or 1) C1-10Linear chain or branched chain alkyl is located to replace in place.As the C1-10Linear chain or branched chain Alkyl, preferably C1-10Linear or branched alkyl group or C2-10Linear chain or branched chain alkenyl, more preferable C1-4Linear or branched alkyl group or C2-4Linear chain or branched chain alkenyl, wherein more preferable methyl, ethyl, vinyl or ethidine.
According to embodiment of the present invention, as the C3-20Cycloolefin, for example can further enumerate following formula (Y) Compound represented.
According to the present invention, in formula (Y), group Ra to group Rh can be the same or different, and be each independently selected from Hydrogen and C1-10Linear chain or branched chain alkyl.As the C1-10Linear chain or branched chain alkyl, preferably C1-10Linear or branched alkyl group or C2-10Linear chain or branched chain alkenyl.
According to embodiment of the present invention, in formula (Y), group Ra to group Rh can be the same or different, It is each independently selected from hydrogen, C1-4Linear or branched alkyl group and C2-4Linear chain or branched chain alkenyl such as C2-3Linear chain or branched chain alkenyl, In more preferably methyl, ethyl, vinyl or ethidine.
According to the present invention, in formula (Y), the integer that n is 0 to 6, preferably 0 or 1.
According to the present invention, in formula (Y), symbolRepresent singly-bound or double bond.
Embodiment according to the present invention, as the formula (Y) compound represented, preferably norbornene, ethylidene drop Bornylene, vinyl norbornene, norbornadiene, 5- methyinorbornene, tetracyclododecen, three cyclododecenes, tricyclic ten One alkene, five cyclopentadecylenes, five ring hexadecenes and 8- ethyltetracyclo laurylene.
According to the present invention, cycloolefin above-mentioned can be used alone, and can also be used with combination of two or more.
According to the present invention, when carrying out the copolyreaction, the amount ratio of the cycloolefin and the olefine (mole Than) it is generally 0.1-50: 1, preferably 0.2-40: 1, more preferably 1-25: 1.
According to the present invention, to the reactive mode of the copolymerization process, there is no particular limitation, can use known in this field Those of, for example solwution method, substance law can be enumerated etc., wherein it is preferred that solwution method.
According to the present invention, the copolymerization process as needed can be in the presence of a solvent.It is used as the copolymerization Solvent can enumerate this field and those of routinely use when carrying out the copolymerization of olefine and cycloolefin, and dosage can also refer to The conventional amount used of the prior art, is not particularly limited.For concrete example, as the copolymerization solvent, such as can be with Enumerate C4-20Alkane, C6-30Aromatic hydrocarbon, C3-30Alicyclic, C1-20Halogenated alkane, C3-20Halogenated alicyclic and C6-30Halogenated aromatic Deng wherein it is preferred that C4-12Linear chain or branched chain alkane, C3-12Cycloalkane, C6-12Aromatic hydrocarbons, C1-12Linear chain or branched chain halogenated alkane, C3-12Halogen For cycloalkane and C6-12Halogenated aryl hydrocarbon, more preferable C4-9Linear chain or branched chain alkane, C4-9Cycloalkane, C6-9Aromatic hydrocarbons, C1-8Straight chain or branch Chain halogenated alkane, C3-8Halogenated cycloalkane and C6-9Halogenated aryl hydrocarbon, most preferably pentane, hexane, hexamethylene or toluene.These copolymerization It can be used alone, or be applied in combination with arbitrary ratio a variety of with solvent.
According to the present invention, the reaction pressure (stagnation pressure) of the copolyreaction is generally 0.1-5.0MPa, preferably 0.1- 2.5MPa, more preferable 0.1-2.0MPa, but is not limited thereto.
According to the present invention, the temperature of the copolyreaction is generally 0-120 DEG C, preferably 0-100 DEG C, and more preferable 30-90 DEG C, But is not limited thereto.
According to the present invention, the copolyreaction can carry out under the conditions of having existing for hydrogen, can also be in no hydrogen It is carried out under the conditions of existing.In the presence of hydrogen, the partial pressure of hydrogen can be the 0.01-99% of previous reaction pressure, It is preferred that 0.01-50%, but is not limited thereto.
According to the present invention, the copolyreaction can carry out under the conditions of having existing for inert gas, can also not have It is carried out under the conditions of inert gas is existing.In the presence of an inert gas, the partial pressure of inert gas can be previous reaction The 0.01-99% of pressure, preferably 0.01-50%, but is not limited thereto.As the inert gas, for example can enumerate Nitrogen, helium or argon gas etc..These inert gases can be used alone, and also can according to need with arbitrary ratio group It closes using a variety of.
Embodiment
The present invention is illustrated using embodiment in further detail below, however, the present invention is not limited to these examples.
Each performance parameter involved in following embodiment and comparative example measures as follows.
(1) polymerization activity
(unit is g (P) (mol (M) h) to the polymerization activity of catalyst-1, wherein P refers to copolymer, and M refers to metal member Plain M such as Ti) it is calculated according to following formula:
Polymerization activity=m1×4×Mw/m2
Wherein,
m1For the amount (g) for the copolymer that 15 minutes polymerization times obtain；
Mw is the molecular weight of catalyst；
m2For the additional amount (g) of catalyst.
(2) the molecular weight M η of polymer
The viscosity average molecular weigh M η of polymer is calculated in accordance with the following methods:
According to standard ASTM D4020-00, high temperature dilution type Ubbelohde viscometer method (capillary inner diameter 0.44- is used 0.60mm, constant temperature bath medium are No. 300 silicone oil, and dilution is decahydronaphthalene with solvent, and measuring temperature is 135 DEG C) the measurement copolymerization Then the inherent viscosity η of object calculates the viscosity average molecular weigh M η of the copolymer according to following formula.
η=5.37 × 10 M4×[η]1.37
Wherein, η is inherent viscosity.
(3) glass transition temperature (Tg)
The Tg of copolymer uses dsc measurement.Specifically, weighing 9mg copolymer to be tested as sample.The sample is first 200 DEG C are heated to by 30 DEG C with the rate of 10 DEG C/min, 3min is stopped, then be down to 30 DEG C with the rate of 10 DEG C/min, stops Then 3min rises to 200 DEG C with the rate of 10 DEG C/min.It is analyzed using second of heating curve.
The manufacture embodiment of Nonmetallocene complex
Manufacture embodiment 1
2- aminobenzoic thioether (0.2mol), dehydrated alcohol are sequentially added in a dry 500ml three-necked flask (160ml), 3,5- di-tert-butyl salicylaldehyde (0.2mol), acetic acid (0.3ml), react 2hr after being warming up to reflux temperature, are cooled to Room temperature, filtering are washed three times with dehydrated alcohol, vacuum drying, obtain 2- aminobenzoic thioether contracting 3,5- di-tert-butyl salicylaldehyde 49.7g, referred to as ligand L 1,
L1。
Elemental analysis: C 74.57% (theoretical value 74.32%)；H 8.35% (theoretical value 8.22%)；(the reason of N 4.07% By value 3.94%).1H nuclear-magnetism δ=13.4 (OH), 8.6 (CHN), 7.5-7.1 (Ar-H), 3.25 (SCH3), 1.45 (C (CH3)3), 1.35(C(CH3)3)。
Manufacture embodiment 2
2- aminobenzene dipropyl sulfide (0.2mol), dehydrated alcohol are sequentially added in a dry 500ml three-necked flask (160ml), 3,5- di-tert-butyl salicylaldehyde (0.2mol), acetic acid (0.3ml), react 2hr after being warming up to reflux temperature, are cooled to Room temperature, filtering are washed three times with dehydrated alcohol, vacuum drying, obtain 2- aminobenzene dipropyl sulfide contracting 3,5- di-tert-butyl salicylaldehyde 49.7g, referred to as ligand L 2,
L2。
Elemental analysis: C 74.57% (theoretical value 75.15%)；H 8.35% (theoretical value 8.67%)；(the reason of N 3.95% By value 3.65%).1H nuclear-magnetism δ=13.4 (OH), 8.55 (CHN), 7.5-7.1 (Ar-H), 2.10 (CH2CH3), 1.47 (C (CH3)3), 1.35 (C (CH3)3), 1.17 (CH2CH3)。
Manufacture embodiment 3
2- aminobenzoic thioether (0.2mol), dehydrated alcohol are sequentially added in a dry 500ml three-necked flask (160ml), 3,5- di-tert-butyl salicylaldehyde (0.2mol), acetic acid (0.3ml), react 2hr after being warming up to reflux temperature, are cooled to Room temperature, filtering are washed three times with dehydrated alcohol, vacuum drying, obtain 2- aminobenzoic thioether contracting 3,5- di-tert-butyl salicylaldehyde 49.7g。
It is slowly added to hydrogenate into the toluene solution of 2- aminobenzoic thioether contracting 3,5- di-tert-butyl salicylaldehyde (0.1mol) The diethyl ether solution of aluminium lithium (0.2mol) continues to be stirred to react 30 minutes after the completion of being added, whole by the way that ice water is added into reaction solution Only react.Column Chromatographic purification obtains compound shown in following formula, referred to as ligand L 3,
L3。
Elemental analysis: C 73.67% (theoretical value 73.90%)；H 8.71% (theoretical value 8.74%)；(the reason of N 4.08% By value 3.92%).1H nuclear-magnetism δ=13.3 (OH), 8.6 (CHN), 7.5-7.1 (Ar-H), 5.0 (NH), 3.3 (SCH3), 1.45 (C (CH3)3), 1.3 (C (CH3)3)。
Manufacture embodiment 4
At 20 °C, by the 54ml toluene solution containing 0.025mol ligand L 1 in a 250ml three-necked flask It is added dropwise to containing 0.031mol TiCl46ml toluene in, continue to be stirred at room temperature reaction 12 hours, mistake after being added dropwise Filter, filtrate vacuum drying obtains crude product, is recrystallized to give compound shown in following formula with dichloromethane/hexane, referred to as non- Metallocene complex C1,
C1。
Elemental analysis: C 52.11% (theoretical value 51.84%)；H 5.63% (theoretical value 5.54%)；(the reason of N 2.98% By value 2.75%).1H nuclear-magnetism δ=8.79 (CHN), 7.83-7.40 (Ar-H), 3.08 (SCH3), 1.57 (C (CH3)3), 1.35 (C (CH3)3)。
Manufacture embodiment 5
At 20 °C, by the 54ml toluene solution containing 0.025mol ligand L 2 in a 250ml three-necked flask It is added dropwise to containing 0.031mol TiCl46ml toluene in, continue to be stirred at room temperature reaction 12 hours, mistake after being added dropwise Filter, filtrate vacuum drying obtains crude product, is recrystallized to give compound shown in following formula with dichloromethane/hexane, referred to as non- Metallocene complex C2,
C2。
Elemental analysis: C 54.10% (theoretical value 53.60%)；H 5.73% (theoretical value 6.0%)；N 2.45% is (theoretical Value 2.60%).1H nuclear-magnetism δ=8.7 (CHN), 7.8-7.4 (Ar-H), 3.45 (SCH2), 2.05 (CH2CH3), 1.55 (C (CH3)3), 1.35 (C (CH3)3), 1.15 (CH2CH3)。
Manufacture embodiment 6
At 20 °C, by the 54ml toluene solution containing 0.025mol ligand L 3 in a 250ml three-necked flask It is added dropwise to containing 0.031mol TiCl46ml toluene in, continue to be stirred at room temperature reaction 12 hours, mistake after being added dropwise Filter, filtrate vacuum drying obtains crude product, is recrystallized to give compound shown in following formula with dichloromethane/hexane, referred to as non- Metallocene complex C3,
C3。
Elemental analysis: C 52.02% (theoretical value 51.63%)；H 8.71% (theoretical value 8.59%)；(the reason of N 2.68% By value 2.74%).1H nuclear-magnetism δ=8.85 (CH2N), 7.82-7.40 (Ar-H), 4.95 (NH), 3.09 (SCH3), 1.55 (C (CH3)3), 1.30 (C (CH3)3)。
Manufacture embodiment 7
Under the conditions of -20 DEG C, by the 150ml THF solution containing 0.01mol ligand L 3 in a 250ml three-necked flask It is added dropwise in the mixed liquor of 0.02mmol KH and 30ml THF, is stirred to react to recovery to room temperature, continues to stir 2hr, vacuum is removed Solvent is removed, 40ml toluene is added, this liquid is added dropwise to containing 0.011mol TiCl at room temperature440ml toluene in, drip Continue that reaction 12 hours, filtering is stirred at room temperature after finishing, filtrate vacuum drying obtains crude product, with dichloromethane/hexane It is recrystallized to give compound shown in following formula, referred to as Nonmetallocene complex C4,
C4。
Elemental analysis: C55.58% (theoretical value 55.59%)；H 6.31% (theoretical value 6.15%)；N 2.87% is (theoretical Value 2.95%).1H nuclear-magnetism δ=8.93 (CH2N), 7.82-7.40 (Ar-H), 3.13 (SCH3), 1.50 (C (CH3)3), 1.30 (C (CH3)3)。
The preparation embodiment of alkyl aluminum hydrolysis product
Triisobutyl aluminium hydrolysate (BAO) prepares embodiment:
Under the nitrogen atmosphere of 0.1MPa, taken out at one sequentially added in roasting 250ml flask toluene (17.7ml) and Triisobutyl aluminium (0.0177mmol), immigration is maintained in -40 DEG C of liquid nitrogen below/methyl acetate bath, 60 points after being fully cooled Deionized water (0.0885mol) is added dropwise in clock, is warmed to room temperature naturally after completion of dropwise addition, the reaction was continued 12 hours obtains BAO solution.
Triethyl aluminum hydrolysate (EAO) prepares embodiment:
Under the nitrogen atmosphere of 0.1MPa, taken out at one sequentially added in roasting 250ml flask toluene (17.7ml) and Triethyl aluminum (0.0177mmol), immigration is maintained in -40 DEG C of liquid nitrogen below/methyl acetate bath, 60 minutes after being fully cooled Interior dropwise addition deionized water (0.0885mol), is warmed to room temperature naturally after completion of dropwise addition, and the reaction was continued 12 hours obtains EAO solution.
Trimethyl aluminium hydrolysate (SMAO) prepares embodiment:
Under the nitrogen atmosphere of 0.1MPa, toluene (17.7ml), three are sequentially added through taking out in roasting 250ml flask at one Aluminium methyl (0.0177mmol), immigration is maintained in -40 DEG C of liquid nitrogen below/methyl acetate bath, after being fully cooled in 60 minutes It is added dropwise deionized water (0.0885mol), is warmed to room temperature naturally after completion of dropwise addition, the reaction was continued 12 hours obtains SMAO solution.
Hydrolysate obtained in the above alkyl aluminum hydrolysis product preparation embodiment is directly used in the form of acquired solution In Application Example below.
Olefin-copolymerization Application Example
Application Example 1
Under the ethylene atmosphere of 0.1MPa, in 70 DEG C of oil baths, first is sequentially added through taking out in roasting 250ml flask at one Benzene (44.3ml), triisobutyl aluminium hydrolysate (BAO, 1mmol) produced above, methylaluminoxane (MAO, 1mmol) and drop Bornylene (0.018mol) is eventually adding the toluene solution for the Nonmetallocene complex C1 that 1ml is manufactured in manufacture embodiment 4 (containing 2 μm of ol complexs), copolyreaction is carried out under stiring.After reaction carries out 15 minutes reaction was completed, with containing 5% hydrochloric acid Ethyl alcohol stopped reaction, product are dried under vacuum to constant weight at 50 DEG C and obtain ethylene-norbornene copolymer after being filtered, washed.It surveys Viscosity average molecular weigh the M η and Tg of copolymer are measured, and calculates the polymerization activity of catalyst, the results are shown in Table 1.
Application Example 2
Under the ethylene atmosphere of 0.1MPa, in 70 DEG C of oil baths, first is sequentially added through taking out in roasting 250ml flask at one Benzene (43.7ml), triisobutyl aluminium hydrolysate (BAO, 1.5mmol) produced above, methylaluminoxane (MAO, 0.5mmol) With norbornene (0.018mol), the toluene for being eventually adding the Nonmetallocene complex C1 that 1ml is manufactured in manufacture embodiment 4 is molten Liquid (contains 2 μm of ol complexs), carries out copolyreaction under stiring.Reaction was completed after reaction carries out 15 minutes, with containing 5% hydrochloric acid Ethyl alcohol stopped reaction, product is dried under vacuum to constant weight at 50 DEG C and obtains ethylene-norbornene copolymer after being filtered, washed. Viscosity average molecular weigh the M η and Tg of copolymer are measured, and calculates the polymerization activity of catalyst, the results are shown in Table 1.
Application Example 3
Under the ethylene atmosphere of 0.1MPa, in 70 DEG C of oil baths, first is sequentially added through taking out in roasting 250ml flask at one Benzene (44.3ml), triethyl aluminum hydrolysate (EAO, 1mmol) produced above, methylaluminoxane (MAO, 1mmol) He Jiangbing Piece alkene (0.018mol) is eventually adding the toluene solution for the Nonmetallocene complex C1 that 1ml is manufactured in manufacture embodiment 4 (containing 2 μm ol complex), copolyreaction is carried out under stiring.Reaction was completed after reaction carries out 15 minutes, with the ethyl alcohol for containing 5% hydrochloric acid Stopped reaction, product are dried under vacuum to constant weight at 50 DEG C and obtain ethylene-norbornene copolymer after being filtered, washed.Measurement is altogether Viscosity average molecular weigh the M η and Tg of polymers, and the polymerization activity of catalyst is calculated, it the results are shown in Table 1.
Application Example 4
Under the ethylene atmosphere of 0.1MPa, in 70 DEG C of oil baths, first is sequentially added through taking out in roasting 250ml flask at one Benzene (41.3ml), trimethyl aluminium hydrolysate (SMAO, 1mmol) produced above, methylaluminoxane (MAO, 1mmol) He Jiangbing Piece alkene (0.018mol) is eventually adding the toluene solution for the Nonmetallocene complex C1 that 1ml is manufactured in manufacture embodiment 4 (containing 2 μm ol complex), copolyreaction is carried out under stiring.Reaction was completed after reaction carries out 15 minutes, with the ethyl alcohol for containing 5% hydrochloric acid Stopped reaction, product are dried under vacuum to constant weight at 50 DEG C and obtain ethylene-norbornene copolymer after being filtered, washed.Measurement is altogether Viscosity average molecular weigh the M η and Tg of polymers, and the polymerization activity of catalyst is calculated, it the results are shown in Table 1.
Application Example 5
Under the ethylene atmosphere of 0.1MPa, in 70 DEG C of oil baths, first is sequentially added through taking out in roasting 250ml flask at one Benzene (44.3ml), trimethyl aluminium hydrolysate (SMAO, 1.5mmol) produced above, methylaluminoxane (MAO, 0.5mmol) and Norbornene (0.018mol) is eventually adding the toluene solution for the Nonmetallocene complex C1 that 1ml is manufactured in manufacture embodiment 4 (containing 2 μm of ol complexs), copolyreaction is carried out under stiring.After reaction carries out 15 minutes reaction was completed, with containing 5% hydrochloric acid Ethyl alcohol stopped reaction, product are dried under vacuum to constant weight at 50 DEG C and obtain ethylene-norbornene copolymer after being filtered, washed.It surveys Viscosity average molecular weigh the M η and Tg of copolymer are measured, and calculates the polymerization activity of catalyst, the results are shown in Table 1.
Application Example 6
Under the ethylene atmosphere of 0.1MPa, in 70 DEG C of oil baths, first is sequentially added through taking out in roasting 250ml flask at one Benzene (44.3ml), triisobutyl aluminium hydrolysate (BAO, 1mmol) produced above, methylaluminoxane (MAO, 1mmol) and drop Bornylene (0.018mol) is eventually adding the toluene solution for the Nonmetallocene complex C2 that 1ml is manufactured in manufacture embodiment 5 (containing 2 μm of ol complexs), copolyreaction is carried out under stiring.After reaction carries out 15 minutes reaction was completed, with containing 5% hydrochloric acid Ethyl alcohol stopped reaction, product are dried under vacuum to constant weight at 50 DEG C and obtain ethylene-norbornene copolymer after being filtered, washed.It surveys Viscosity average molecular weigh the M η and Tg of copolymer are measured, and calculates the polymerization activity of catalyst, the results are shown in Table 1.
Application Example 7
Under the ethylene atmosphere of 0.1MPa, in 70 DEG C of oil baths, first is sequentially added through taking out in roasting 250ml flask at one Benzene (43.7ml), triisobutyl aluminium hydrolysate (BAO, 1.5mmol) produced above, methylaluminoxane (MAO, 0.5mmol) With norbornene (0.018mol), the toluene for being eventually adding the Nonmetallocene complex C2 that 1ml is manufactured in manufacture embodiment 5 is molten Liquid (contains 2 μm of ol complexs), carries out copolyreaction under stiring.Reaction was completed after reaction carries out 15 minutes, with containing 5% hydrochloric acid Ethyl alcohol stopped reaction, product is dried under vacuum to constant weight at 50 DEG C and obtains ethylene-norbornene copolymer after being filtered, washed. Viscosity average molecular weigh the M η and Tg of copolymer are measured, and calculates the polymerization activity of catalyst, the results are shown in Table 1.
Application Example 8
Under the ethylene atmosphere of 0.1MPa, in 70 DEG C of oil baths, first is sequentially added through taking out in roasting 250ml flask at one Benzene (44.3ml), triisobutyl aluminium hydrolysate (BAO, 1mmol) produced above, methylaluminoxane (MAO, 1mmol) and drop Bornylene (0.018mol) is eventually adding the toluene solution for the Nonmetallocene complex C3 that 1ml is manufactured in manufacture embodiment 6 (containing 2 μm of ol complexs), copolyreaction is carried out under stiring.After reaction carries out 15 minutes reaction was completed, with containing 5% hydrochloric acid Ethyl alcohol stopped reaction, product are dried under vacuum to constant weight at 50 DEG C and obtain ethylene-norbornene copolymer after being filtered, washed.It surveys Viscosity average molecular weigh the M η and Tg of copolymer are measured, and calculates the polymerization activity of catalyst, the results are shown in Table 1.
Application Example 9
Under the ethylene atmosphere of 0.1MPa, in 70 DEG C of oil baths, first is sequentially added through taking out in roasting 250ml flask at one Benzene (44.3ml), triisobutyl aluminium hydrolysate (BAO, 1mmol) produced above, methylaluminoxane (MAO, 1mmol) and drop Bornylene (0.018mol) is eventually adding the toluene solution for the Nonmetallocene complex C4 that 1ml is manufactured in manufacture embodiment 7 (containing 2 μm of ol complexs), copolyreaction is carried out under stiring.After reaction carries out 15 minutes reaction was completed, with containing 5% hydrochloric acid Ethyl alcohol stopped reaction, product are dried under vacuum to constant weight at 50 DEG C and obtain ethylene-norbornene copolymer after being filtered, washed.It surveys Viscosity average molecular weigh the M η and Tg of copolymer are measured, and calculates the polymerization activity of catalyst, the results are shown in Table 1.
Comparative example 1
Under the ethylene atmosphere of 0.1MPa, in 70 DEG C of oil baths, first is sequentially added through taking out in roasting 250ml flask at one Benzene (44.8ml), methylaluminoxane (MAO, 2mmol) and norbornene (0.018mol) are eventually adding 1ml in manufacture embodiment 4 The toluene solution (containing 2 μm of ol complexs) of the Nonmetallocene complex C1 of middle manufacture, carries out copolyreaction under stiring.It is reacting Reaction was completed after carrying out 15 minutes, and with the ethyl alcohol stopped reaction for containing 5% hydrochloric acid, product is dry in 50 DEG C of vacuum after being filtered, washed It is dry to obtain ethylene-norbornene copolymer to constant weight.Viscosity average molecular weigh the M η and Tg of copolymer are measured, and calculates the poly- of catalyst Activity is closed, the results are shown in Table 1.
Comparative example 2
Under the ethylene atmosphere of 0.1MPa, in 70 DEG C of oil baths, first is sequentially added through taking out in roasting 250ml flask at one Benzene (44.5ml), triisobutyl aluminium hydrolysate (BAO, 2mmol) produced above and norbornene (0.018mol), finally plus Enter the toluene solution (containing 2 μm of ol complexs) for the Nonmetallocene complex C1 that 1ml is manufactured in manufacture embodiment 4, under stiring Carry out copolyreaction.Reaction carry out 15 minutes after reaction was completed, with contain 5% hydrochloric acid ethyl alcohol stopped reaction, product through filtering, After washing, constant weight is dried under vacuum at 50 DEG C and obtains ethylene-norbornene copolymer.Measure copolymer viscosity average molecular weigh M η and Tg, and the polymerization activity of catalyst is calculated, it the results are shown in Table 1.
Comparative example 3
Under the ethylene atmosphere of 0.1MPa, in 70 DEG C of oil baths, first is sequentially added through taking out in roasting 250ml flask at one Benzene (44.5ml), triethyl aluminum hydrolysate (EAO, 2mmol) produced above and norbornene (0.018mol), are eventually adding The toluene solution (containing 2 μm of ol complexs) for the Nonmetallocene complex C1 that 1ml is manufactured in manufacture embodiment 4, under stiring into Row copolyreaction.Reaction was completed after reaction carries out 15 minutes, and with the ethyl alcohol stopped reaction for containing 5% hydrochloric acid, product is filtered, washed After washing, constant weight is dried under vacuum at 50 DEG C and obtains ethylene-norbornene copolymer.Measure copolymer viscosity average molecular weigh M η and Tg, and the polymerization activity of catalyst is calculated, it the results are shown in Table 1.
Comparative example 4
Under the ethylene atmosphere of 0.1MPa, in 70 DEG C of oil baths, first is sequentially added through taking out in roasting 250ml flask at one Benzene (44.8ml), methylaluminoxane (MAO, 2mmol) and norbornene (0.018mol) are eventually adding 1ml in manufacture embodiment 5 The toluene solution (containing 2 μm of ol complexs) of the Nonmetallocene complex C2 of middle manufacture, carries out copolyreaction under stiring.It is reacting Reaction was completed after carrying out 15 minutes, and with the ethyl alcohol stopped reaction for containing 5% hydrochloric acid, product is dry in 50 DEG C of vacuum after being filtered, washed It is dry to obtain ethylene-norbornene copolymer to constant weight.Viscosity average molecular weigh the M η and Tg of copolymer are measured, and calculates the poly- of catalyst Activity is closed, the results are shown in Table 1.
Comparative example 5
Under the ethylene atmosphere of 0.1MPa, in 70 DEG C of oil baths, first is sequentially added through taking out in roasting 250ml flask at one Benzene (44.5ml), triisobutyl aluminium hydrolysate (BAO, 2mmol) produced above and norbornene (0.018mol), finally plus Enter the toluene solution (containing 2 μm of ol complexs) for the Nonmetallocene complex C2 that 1ml is manufactured in manufacture embodiment 5, under stiring Carry out copolyreaction.Reaction carry out 15 minutes after reaction was completed, with contain 5% hydrochloric acid ethyl alcohol stopped reaction, product through filtering, After washing, constant weight is dried under vacuum at 50 DEG C and obtains ethylene-norbornene copolymer.Measure copolymer viscosity average molecular weigh M η and Tg, and the polymerization activity of catalyst is calculated, it the results are shown in Table 1.
Comparative example 6
Under the ethylene atmosphere of 0.1MPa, in 70 DEG C of oil baths, first is sequentially added through taking out in roasting 250ml flask at one Benzene (44.8ml), methylaluminoxane (MAO, 2mmol) and norbornene (0.018mol) are eventually adding 1ml in manufacture embodiment 6 The toluene solution (containing 2 μm of ol complexs) of the Nonmetallocene complex C3 of middle manufacture, carries out copolyreaction under stiring.It is reacting Reaction was completed after carrying out 15 minutes, and with the ethyl alcohol stopped reaction for containing 5% hydrochloric acid, product is dry in 50 DEG C of vacuum after being filtered, washed It is dry to obtain ethylene-norbornene copolymer to constant weight.Viscosity average molecular weigh the M η and Tg of copolymer are measured, and calculates the poly- of catalyst Activity is closed, the results are shown in Table 1.
Comparative example 7
Under the ethylene atmosphere of 0.1MPa, in 70 DEG C of oil baths, first is sequentially added through taking out in roasting 250ml flask at one Benzene (44.5ml), triisobutyl aluminium hydrolysate (BAO, 2mmol) produced above and norbornene (0.018mol), finally plus Enter the toluene solution (containing 2 μm of ol complexs) for the Nonmetallocene complex C3 that 1ml is manufactured in manufacture embodiment 6, under stiring Carry out copolyreaction.Reaction carry out 15 minutes after reaction was completed, with contain 5% hydrochloric acid ethyl alcohol stopped reaction, product through filtering, After washing, constant weight is dried under vacuum at 50 DEG C and obtains ethylene-norbornene copolymer.Measure copolymer viscosity average molecular weigh M η and Tg, and the polymerization activity of catalyst is calculated, it the results are shown in Table 1.
Comparative example 8
Under the ethylene atmosphere of 0.1MPa, in 70 DEG C of oil baths, first is sequentially added through taking out in roasting 250ml flask at one Benzene (44.8ml), methylaluminoxane (MAO, 2mmol) and norbornene (0.018mol) are eventually adding 1ml in manufacture embodiment 7 The toluene solution (containing 2 μm of ol complexs) of the Nonmetallocene complex C4 of middle manufacture, carries out copolyreaction under stiring.It is reacting Reaction was completed after carrying out 15 minutes, and with the ethyl alcohol stopped reaction for containing 5% hydrochloric acid, product is dry in 50 DEG C of vacuum after being filtered, washed It is dry to obtain ethylene-norbornene copolymer to constant weight.Viscosity average molecular weigh the M η and Tg of copolymer are measured, and calculates the poly- of catalyst Activity is closed, the results are shown in Table 1.
Comparative example 9
Under the ethylene atmosphere of 0.1MPa, in 70 DEG C of oil baths, first is sequentially added through taking out in roasting 250ml flask at one Benzene (44.5ml), triisobutyl aluminium hydrolysate (BAO, 2mmol) produced above and norbornene (0.018mol), finally plus Enter the toluene solution (containing 2 μm of ol complexs) for the Nonmetallocene complex C4 that 1ml is manufactured in manufacture embodiment 7, under stiring Carry out copolyreaction.Reaction carry out 15 minutes after reaction was completed, with contain 5% hydrochloric acid ethyl alcohol stopped reaction, product through filtering, After washing, constant weight is dried under vacuum at 50 DEG C and obtains ethylene-norbornene copolymer.Measure copolymer viscosity average molecular weigh M η and Tg, and the polymerization activity of catalyst is calculated, it the results are shown in Table 1.
Comparative example 10
Under the ethylene atmosphere of 0.1MPa, in 70 DEG C of oil baths, first is sequentially added through taking out in roasting 250ml flask at one Benzene (44.5ml), triisobutyl aluminium hydrolysate (BAO, 1mmol) and triisobutyl aluminium (1mmol) produced above, He Jiangbing Piece alkene (0.018mol) is eventually adding the toluene solution for the Nonmetallocene complex C4 that 1ml is manufactured in manufacture embodiment 7 (containing 2 μm ol complex), copolyreaction is carried out under stiring.Reaction was completed after reaction carries out 15 minutes, with the ethyl alcohol for containing 5% hydrochloric acid Stopped reaction, product are dried under vacuum to constant weight at 50 DEG C and obtain ethylene-norbornene copolymer after being filtered, washed.Measurement is altogether Viscosity average molecular weigh the M η and Tg of polymers, and the polymerization activity of catalyst is calculated, it the results are shown in Table 1.
The experimental result of 1. olefin-copolymerization Application Example of table
Note:1The molar ratio of co-catalyst each component and the Nonmetallocene complex in terms of Ti in terms of Al, wherein before "/" Numerical value afterwards respectively represents the molar ratio of cocatalyst component and Nonmetallocene complex in the 3rd column before and after "/"；
2The molar ratio of norbornene and ethylene.
When as shown in table 1, using composite catalyst, for Nonmetallocene complex C1,500/500 SMAO/MAO institute The polymerization activity of realization against expectation than be used alone MAO Shi Genggao, and in other situations SMAO/MAO, BAO/MAO and The polymerization activity that EAO/MAO is realized then be used alone MAO when it is substantially suitable, although it is slightly lower but still in acceptable model In enclosing.On the contrary, being realized when BAO or EAO is used alone or uses the combination of BAO/ triisobutyl aluminium as co-catalyst Polymerization activity is then far below MAO, or even substantially without polymerization activity.
In addition, the viscosity average molecular weigh of gained copolymer is above 100,000, and makes when individually using MAO as co-catalyst With can be obtained when composite catalyst viscosity average molecular weigh below 100,000,50,000 or less even 20,000 copolymers below.
In addition, using when SMAO/MAO composite catalyst it is even possible that the glass transition temperature Tg of gained copolymer Improve 20 DEG C or more.
Although a specific embodiment of the invention is described in detail above in conjunction with the embodiments, need to refer to Out, the scope of protection of the present invention is not limited by these specific embodiments, but by claims of annex Lai It determines.Those skilled in the art can carry out these embodiments in the range of not departing from technical idea and purport of the invention Change appropriate, and the embodiment after these changes is obviously also included within protection scope of the present invention.

Claims (36)

1. cocatalyst composition, which is characterized in that reaction product and aikyiaiurnirsoxan beta including alkyl aluminum and water, wherein in terms of Al, The molar ratio of the reaction product of the alkyl aluminum and water and the aikyiaiurnirsoxan beta is 0.5: 1 to less than 4: 1, wherein the alkyl aluminum with The reaction product of water by making alkyl aluminum react to obtain with water in the presence of inert atmosphere and solvent, reaction temperature be -150 DEG C extremely Room temperature.
2. cocatalyst composition according to claim 1, which is characterized in that in terms of Al, the alkyl aluminum and water it is anti- Answering the molar ratio of product and the aikyiaiurnirsoxan beta is 0.5-3.9: 1.
3. cocatalyst composition according to claim 1 or 2, which is characterized in that the alkyl aluminum and water react- It is carried out under 100 DEG C to -40 DEG C of reaction temperature.
4. cocatalyst composition according to claim 1 or 2, which is characterized in that the inert atmosphere is nitrogen.
5. cocatalyst composition according to claim 1 or 2, which is characterized in that the solvent is toluene.
6. cocatalyst composition according to claim 1 or 2, which is characterized in that the alkyl aluminum reacts production with water Object is the reaction product that alkyl aluminum and water press 1-5: 1.
7. cocatalyst composition according to claim 1 or 2, which is characterized in that the alkyl aluminum reacts production with water Object is the reaction product for the molar ratio that alkyl aluminum presses 1-3: 1 with water.
8. cocatalyst composition according to claim 1 or 2, which is characterized in that the alkyl aluminum reacts production with water Object is the reaction product for the molar ratio that alkyl aluminum presses 1.5-2.5: 1 with water.
9. cocatalyst composition according to claim 1 or 2, which is characterized in that the alkyl aluminum is shown in following formula (A) Compound:
Al(R)3 (A)
Wherein group R is same or different to each other, and is each independently selected from C1-C8Alkyl.
10. cocatalyst composition according to claim 9, which is characterized in that group R is same or different to each other, respectively Independently selected from methyl, ethyl and isobutyl group.
11. cocatalyst composition according to claim 9, which is characterized in that the alkyl aluminum is selected from trimethyl aluminium (Al (CH3)3), triethyl aluminum (Al (CH2CH3)3), tri-n-n-propyl aluminum (Al (C3H7)3), triisobutyl aluminium (Al (i-C4H9)3), three just Butyl aluminium (Al (C4H9)3), triisopentyl aluminium (Al (i-C5H11)3), three n-pentyl aluminium (Al (C5H11)3), tri-n-hexyl aluminum (Al (C6H13)3), three isohesyl aluminium (Al (i-C6H13)3), diethylmethyl aluminium (Al (CH3)(CH3CH2)2), dimethyl ethyl aluminium (Al (CH3CH2)(CH3)2) or their any combination.
12. cocatalyst composition according to claim 9, which is characterized in that the alkyl aluminum is selected from trimethyl aluminium, three Aluminium ethide, tri-n-n-propyl aluminum, triisobutyl aluminium or their any combination.
13. cocatalyst composition according to claim 9, which is characterized in that the alkyl aluminum is selected from trimethyl aluminium, three Aluminium isobutyl or their any combination.
14. cocatalyst composition according to claim 9, which is characterized in that the alkyl aluminum is trimethyl aluminium.
15. cocatalyst composition according to claim 1 or 2, which is characterized in that the aikyiaiurnirsoxan beta is selected from methyl alumina One of alkane, the methylaluminoxane of modification, ethylaluminoxane, isobutyl aluminium alkoxide and normal-butyl aikyiaiurnirsoxan beta are a variety of.
16. cocatalyst composition according to claim 1 or 2, which is characterized in that the aikyiaiurnirsoxan beta is selected from methyl alumina One of alkane, the methylaluminoxane of modification and isobutyl aluminium alkoxide are a variety of.
17. cocatalyst composition according to claim 1 or 2, which is characterized in that the aikyiaiurnirsoxan beta is selected from methyl alumina Alkane, modification methylaluminoxane and their any combination.
18. catalyst system, which is characterized in that including being helped described in any one of Nonmetallocene complex and claim 1-17 Carbon monoxide-olefin polymeric.
19. catalyst system according to claim 18, which is characterized in that the Nonmetallocene complex is selected from following formula (I), one of Nonmetallocene complex shown in lower formula (II) and following formula (I-1) or a variety of:
It is aforementioned it is various in, group R1To group R4, group R7With group R9It can be the same or different, be each independently selected from hydrogen And C1-4Linear chain or branched chain alkyl；Group Y is O or S；Group A is S or O；Group R5It is C1-6Linear chain or branched chain alkyl；Group R6With Group R8Can be identical or different, it is each independently selected from C3-6Linear chain or branched chain alkyl；Group R10It is hydrogen or C1-6Straight chain or branch Chain alkylene；Group M is selected from periodic table of elements III-th family to the metallic element of X I race；Group X is halogen；Symbol --- representative is matched Position key.
20. catalyst system according to claim 19, which is characterized in that group R1To group R4, group R7With group R9 For hydrogen；Group Y is O；Group A is S；Group R5For C1-6Linear or branched alkyl group；Group R6With group R8Can be identical or different, It is each independently isopropyl or tert-butyl；Group R10For hydrogen；Group M is selected from group ivb metallic element；Group X is chlorine.
21. catalyst system according to claim 20, which is characterized in that group R5For C1-3Linear or branched alkyl group；Base Group R6With group R8For tert-butyl；And group M is Ti.
22. catalyst system described in any one of 8-21 according to claim 1, which is characterized in that help and urge described in terms of Al The molar ratio of agent composition and the Nonmetallocene complex in terms of metal M is 300-1500: 1.
23. catalyst system described in any one of 8-21 according to claim 1, which is characterized in that help and urge described in terms of Al The molar ratio of agent composition and the Nonmetallocene complex in terms of metal M is 500-1000: 1.
24. the olefine-complex-catalyzed in Nonmetallocene of cocatalyst composition described in any one of claim 1-17 Application in cycloolefin copolymer.
25. application according to claim 24, which is characterized in that the Nonmetallocene complex is selected from lower formula (I), following formula (II) and one of Nonmetallocene complex shown in following formula (I-1) or a variety of:
It is aforementioned it is various in, group R1To group R4, group R7With group R9It can be the same or different, be each independently selected from hydrogen And C1-4Linear chain or branched chain alkyl；Group Y is O or S；Group A is S or O；Group R5It is C1-6Linear chain or branched chain alkyl；Group R6With Group R8Can be identical or different, it is each independently selected from C3-6Linear chain or branched chain alkyl；Group R10It is hydrogen or C1-6Straight chain or branch Chain alkylene；Group M is selected from periodic table of elements III-th family to the metallic element of X I race；Group X is halogen；Symbol --- representative is matched Position key.
26. application according to claim 25, which is characterized in that group R1To group R4, group R7With group R9For hydrogen；Base Group Y is O；Group A is S；Group R5For C1-6Linear or branched alkyl group；Group R6With group R8Can be identical or different, respectively solely It is on the spot isopropyl or tert-butyl；Group R10For hydrogen；Group M is selected from group ivb metallic element；Group X is chlorine.
27. application according to claim 26, which is characterized in that group R5For C1-3Linear or branched alkyl group；Group R6With Group R8For tert-butyl；And group M is Ti.
28. the combination of the reaction product and aikyiaiurnirsoxan beta of the alkyl aluminum and water olefine-cycloolefin complex-catalyzed in Nonmetallocene Application in copolymerization, wherein in terms of Al, the molar ratio of the reaction product of the alkyl aluminum and water and the aikyiaiurnirsoxan beta be 0.5: 1 to Less than 4: 1, wherein the reaction product of the alkyl aluminum and water in the presence of inert atmosphere and solvent by keeping alkyl aluminum anti-with water It should obtain, reaction temperature is -150 DEG C to room temperature.
29. application according to claim 28, which is characterized in that in terms of Al, the reaction product of the alkyl aluminum and water with The molar ratio of the aikyiaiurnirsoxan beta is 0.5-3.9: 1.
30. the application according to claim 28 or 29, which is characterized in that the Nonmetallocene complex be selected from lower formula (I), One of Nonmetallocene complex shown in lower formula (II) and following formula (I-1) is a variety of:
It is aforementioned it is various in, group R1To group R4, group R7With group R9It can be the same or different, be each independently selected from hydrogen And C1-4Linear chain or branched chain alkyl；Group Y is O or S；Group A is S or O；Group R5It is C1-6Linear chain or branched chain alkyl；Group R6With Group R8Can be identical or different, it is each independently selected from C3-6Linear chain or branched chain alkyl；Group R10It is hydrogen or C1-6Straight chain or branch Chain alkylene；Group M is selected from periodic table of elements III-th family to the metallic element of X I race；Group X is halogen；Symbol --- representative is matched Position key.
31. application according to claim 30, which is characterized in that group R1To group R4, group R7With group R9For hydrogen；Base Group Y is O；Group A is S；Group R5For C1-6Linear or branched alkyl group；Group R6With group R8Can be identical or different, respectively solely It is on the spot isopropyl or tert-butyl；Group R10For hydrogen；Group M is selected from group ivb metallic element；Group X is chlorine.
32. application according to claim 31, which is characterized in that group R5For C1-3Linear or branched alkyl group；Group R6With Group R8For tert-butyl；And group M is Ti.
33. the copolymerization process of a kind of olefine and cycloolefin, which is characterized in that including using Nonmetallocene complex as major catalyst And with alkyl defined in cocatalyst composition or claim 28 or 29 described in any one of claim 1-17 The group of the reaction product and aikyiaiurnirsoxan beta of aluminium and water, which is combined into co-catalyst, is copolymerized olefine with cycloolefin, or with power It is that catalyst is copolymerized olefine with cycloolefin that benefit, which requires catalyst system described in any one of 18-23,.
34. according to the method for claim 33, which is characterized in that the Nonmetallocene complex is selected from lower formula (I), following formula (II) and one of Nonmetallocene complex shown in following formula (I-1) or a variety of:
It is aforementioned it is various in, group R1To group R4, group R7With group R9It can be the same or different, be each independently selected from hydrogen And C1-4Linear chain or branched chain alkyl；Group Y is O or S；Group A is S or O；Group R5It is C1-6Linear chain or branched chain alkyl；Group R6With Group R8Can be identical or different, it is each independently selected from C3-6Linear chain or branched chain alkyl；Group R10It is hydrogen or C1-6Straight chain or branch Chain alkylene；Group M is selected from periodic table of elements III-th family to the metallic element of X I race；Group X is halogen；Symbol --- representative is matched Position key.
35. according to the method for claim 34, which is characterized in that group R1To group R4, group R7With group R9For hydrogen；Base Group Y is O；Group A is S；Group R5For C1-6Linear or branched alkyl group；Group R6With group R8Can be identical or different, respectively solely It is on the spot isopropyl or tert-butyl；Group R10For hydrogen；Group M is selected from group ivb metallic element；Group X is chlorine.
36. according to the method for claim 35, which is characterized in that group R5For C1-3Linear or branched alkyl group；Group R6With Group R8For tert-butyl；And group M is Ti.
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