CN101117366B - Method for catalyzing copolymerization of ethylene and norbornene - Google Patents
Method for catalyzing copolymerization of ethylene and norbornene Download PDFInfo
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- CN101117366B CN101117366B CN200710056015XA CN200710056015A CN101117366B CN 101117366 B CN101117366 B CN 101117366B CN 200710056015X A CN200710056015X A CN 200710056015XA CN 200710056015 A CN200710056015 A CN 200710056015A CN 101117366 B CN101117366 B CN 101117366B
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Abstract
The invention relates to a method of catalyzing the copolymerization of ethylene and norborene, belonging to the synthetizing method of alkenes copolymer technical field. The metallocene compound is used as the main catalyst, aluminum alkyl oxygen alkane or aluminum alkyl and boracic compound are used as the promoter to constitute with; in the condition of polymerization temperature 60 to 100 DEG C and reacting 5 to 3 minutes, the toluene solution of ethylene and norborene is catalyzed to react with the catalyst system. The catalyst system listed by the invention catalyzes ethylene and norborene for copolymerization, the catalytic activity is high, the maxlmum molecular weight of the multipolymer can achieve 550,000, and the norborene content in the multipolymer can be adjusted, in particular to the norborene content is more than the 50 percent, thereby increasing the application scope of the product of the invention.
Description
Technical field
The invention belongs to the technical field of olefin copolymer synthetic method, for a kind of use contains the method for phenoxy group side chain constrained geometry configuration metallocene catalyst system catalyzed ethylene and norbornylene copolymerization, to obtain the adjustable high molecular weight copolymer of norbornylene content in the product.
Background technology
Since synthetic being in the news of 1990s ethene and norbornene copolymer, ethene and norbornene copolymer have caused the extensive concern of scientific research personnel and modern industry with its exclusive characteristics.Ethene and norbornene copolymer are a kind of thermoplastic polymers that prospects for commercial application is arranged very much, it has high glass transition temp (Tg), outstanding moisture resistance, optical transparence, very strong resistance to chemical attack, can be widely used in fields such as food product pack, health care, simultaneously, can be used as the high-density storing device as a kind of outstanding substrate material.And the high multipolymer of norbornylene content has low-k, as the interface dielectric medium that is used for microelectronic device can be realized the efficient connection between the interface.The annual output that a large amount of norbornylene byproducts is all arranged in the petrochemical complex, but owing to China has good catalyzer to make it be converted into corresponding polymerization product most of resource is wasted, but will spend the polymkeric substance of substantial contribution import norbornylene to be used for products such as liquid-crystal display simultaneously.
At present, the catalyst system that is used for synthesizing ethylene and norbornene copolymer mainly contains: be the early transition metal compound for catalysis system of representative and be the rear transition metal catalyst system of representative with iron, cobalt, nickel with titanium, zirconium, hafnium.Metallocene compound is the typical case in early transition metal compound for catalysis system, is that focus often is the focus that people study at rear transition metal compound for catalysis system Central Asia amine nickel compound.Kaminsky seminar (Macromol.Chem.1989,190,515-526Makromol.Chem., Macromol.Symp.1991,47,83-93; Polym.Bull. (Berlin) 1993,31,175-182; Macromol.Chem.Phs.1996,197,3907-3945),
Seminar (J.appl.Polym.Sci.1997,63,1063-1070; J.appl.Polym.Sci.1997,63,1071-1076), (Macromolecules 1998 in Fink seminar, 31,4669-4673) (Macromolecules 1999,32 with Waymouth seminar, 2816-2825) all use the homogeneous phase metallocene catalyst system to carry out the research of ethene and norbornylene copolymerization, the products therefrom molecular weight distribution from several ten thousand to hundreds of thousands of.
Summary of the invention
The synthetic method that the purpose of this invention is to provide a kind of ethene efficiently and norbornene copolymer.With constrained geometry configuration metallocene catalyst system catalyzed ethylene that contains the phenoxy group side chain and norbornylene copolymerization, catalytic activity height, copolymerization product molecular weight height, monomeric content is adjustable within the specific limits altogether in the products obtained therefrom.This catalysis process uses metallocene catalyst, and polymerization is finished in catalysis under alkylaluminoxane or aluminum alkyls/boron compound activation.
The present invention uses constrained geometry configuration metallocene catalyst system catalyzed ethylene and the norbornylene copolymerization that contains the phenoxy group side chain, and wherein the structure of metallocene catalyst is as follows:
Wherein, luxuriant ring is 2,3,4,5-tetramethyl-ring pentadienyl or 3,4-phenylbenzene cyclopentadienyl; M is transition metals Ti, zirconium or hafnium; Two X are halogen, alkyl etc.; R
1Be the phenoxy group ortho-substituent, R
2Be all the other locational one or more substituting groups of phenoxy group phenyl ring, R
1And R
2Can be alkyl or aryl.
When being Primary Catalysts with the said structure metallocene compound, the optional alkylaluminoxane of promotor or by aluminum alkyls with contain the co-catalyst system that boronation and thing constitute together.When elected alkylaluminoxane was promotor, alkylaluminoxane was methylaluminoxane, modified methylaluminoxane, ethyl aikyiaiurnirsoxan beta or isobutyl aluminium alkoxide, or their mixture.Preferable methyl aikyiaiurnirsoxan beta, more preferably modified methylaluminoxane.Wherein in the promotor in aluminium and the Primary Catalysts mol ratio of transition metal be (500～2000): 1.When elected aluminum alkyls and boron-containing compound were promotor, aluminum alkyls was trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, aluminium diethyl monochloride, or their mixture; Boron-containing compound is Ph
3CB (C
6F
5)
4, B (C
6F
5)
3, PhNMe
2HB (C
6F
5)
4Or Ph
3CB[(CF
3)
2C
6H
3]
4The preferred triisobutyl aluminium of aluminum alkyls wherein, the preferred Ph of boron compound
3CB (C
6F
5)
4Wherein in the promotor in aluminium, boron and the Primary Catalysts mol ratio of transition metal be 50～200: 1～2: 1.
The synthetic of Primary Catalysts metallocene compound can reference literature Yuetao Zhang and Ying Mu
*Organometallics 2003,22,3877-3883; Organometallics 2004,23,540-546.Among the present invention, preferred Primary Catalysts metallocene compound is 2-(2,3,4,5-tetramethyl-ring pentadienyl)-4,6-di-tert-butylphenol oxygen base titanium dichloride, 2-(2,3,4,5-tetramethyl-ring pentadienyl)-4,6-di-tert-butylphenol oxygen base zirconium dichloride, 2-(2,3,4,5-tetramethyl-ring pentadienyl)-4,6-di-tert-butylphenol oxygen base hafnium dichloride, 2-(2,3,4,5-tetramethyl-ring pentadienyl)-4,6-di-tert-butylphenol oxygen base dimethyl titanium.Preferred Primary Catalysts metallocene compound is 2-(2,3,4,5-tetramethyl-ring pentadienyl)-4,6-di-tert-butylphenol oxygen base titanium dichloride
Usefulness provided by the invention contains the constrained geometry configuration metallocene catalyst system catalyzed ethylene of phenoxy group side chain and the method for norbornylene copolymerization, is meant the ethene and the toluene system of the norbornylene polymerization reaction take place that contacts with the catalyst system with aforementioned component.
When being promotor formation catalyst system with aluminum alkyls/boron compound, the method for concrete catalyzed ethylene and norbornylene copolymerization is as described below.
The method of a kind of catalyzed ethylene and norbornylene copolymerization, it is characterized in that, use by metallocene compound to be Primary Catalysts and the constrained geometry configuration metallocene catalyst system that contains the phenoxy group side chain that constitutes as promotor with aluminum alkyls/boron compound, the structure of described metallocene compound is as follows:
Wherein, luxuriant ring is single the replacement or polysubstituted cyclopentadienyl, indenyl or fluorenyl, and substituent R is selected from hydrogen, alkyl, aryl respectively; M is transition metals Ti, zirconium or hafnium; Two X are halogen, alkyl, alkoxyl group, amido, aryl; R
1Be the phenoxy group ortho-substituent, R
2Be all the other locational one or more substituting groups of phenoxy group phenyl ring, R
1And R
2Be alkyl or aryl; Described aluminum alkyls is trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, aluminium diethyl monochloride, or their mixture; Described boron compound is Ph
3CB (C
6F
5)
4, B (C
6F
5)
3, PhNMe
2HB (C
6F
5)
4Or Ph
3CB[(CF
3)
2C
6H
3]
4In the promotor in aluminium, boron and the Primary Catalysts mol ratio of transition metal be 50～200: 1～2: 1;
Be aggregated in the autoclave and carry out; Reactor 140～160 ℃ of bakings 2～3 hours under vacuum before the polymerization charge into 30～100 ℃ that reduce to setting behind the atmospheric ethene, inject the toluene solution of boron compound and norbornylene; Again aluminum alkyls is mixed mutually with metallocene compound and change in the reactor, feed ethylene gas and begin reaction to pressure 1～5atm, homo(io)thermism is reacted emptying reactor after 5～30 minutes at 30～100 ℃ in the reaction process, stops polyreaction with the HCl/ methanol solution; Leach polymkeric substance, use methanol wash, 50～70 ℃ of vacuum-dryings to constant weight; Wherein the mol ratio of transition metal is 1 * 10 in the consumption of norbornylene and the Primary Catalysts
5: 1,2 * 10
5: 1,3 * 10
5: 1,4 * 10
5: 1 or 5 * 10
5: 1.
When being promotor formation catalyst system with the alkylaluminoxane, the method for concrete catalyzed ethylene and norbornylene copolymerization is as described below.
The method of a kind of catalyzed ethylene and norbornylene copolymerization, it is characterized in that, use by metallocene compound to be Primary Catalysts and the constrained geometry configuration metallocene catalyst system that contains the phenoxy group side chain that constitutes as promotor with alkylaluminoxane, the structure of described metallocene compound is as follows:
Wherein, luxuriant ring is single the replacement or polysubstituted cyclopentadienyl, indenyl or fluorenyl, and substituent R is selected from hydrogen, alkyl, aryl respectively; M is transition metals Ti, zirconium or hafnium; Two X are halogen, alkyl, alkoxyl group, amido, aryl; R
1Be the phenoxy group ortho-substituent, R
2Be all the other locational one or more substituting groups of phenoxy group phenyl ring, R
1And R
2Be alkyl or aryl; Described alkylaluminoxane is methylaluminoxane, modified methylaluminoxane, ethyl aikyiaiurnirsoxan beta or isobutyl aluminium alkoxide, or their mixture; Wherein in the promotor in aluminium and the Primary Catalysts mol ratio of transition metal be 500～2000: 1;
Be aggregated in the autoclave and carry out; Reactor 140～160 ℃ of bakings 2～3 hours under vacuum before the polymerization charge into 30～100 ℃ that reduce to setting behind the atmospheric ethene, inject the toluene solution of norbornylene; With alkylaluminoxane with change in the reactor after metallocene compound mixes mutually, feed ethylene gas and begin reaction to pressure 1～2atm, constant 60～100 ℃ of temperature of reaction react 5～30 minutes emptying reactors, usefulness HCl/ methanol solution termination polyreaction; Leach polymkeric substance, use methanol wash, 50～70 ℃ of vacuum-dryings to constant weight; Wherein the mol ratio of transition metal is 2 * 10 in the consumption of norbornylene and the Primary Catalysts
5: 1 or 3 * 10
5: 1.
The temperature that the present invention carries out copolymerization is 30～100 degree, and ethylene pressure is less than 6atm, and the concentration of norbornylene is less than 6 moles.Before polymerization, the toluene of the alkene of use and dissolving boron compound purifies; Perhaps must purify and drying, to remove the small amount of impurities that makes catalytic activity reduction even inactivation.
Listed catalyst system catalyzed ethylene and norbornylene copolymerization among the present invention, the catalytic activity height, the copolymerization product molecular weight is up to 550,000, and norbornylene content is adjustable in the copolymerization product, especially adjustable in greater than 50% scope at norbornylene content, increased the range of application of product of the present invention.
Embodiment
Below by detailed example the present invention is described, but the present invention is not limited to this.
Embodiment 1
Be aggregated in the 250mL autoclave and carry out, reactor 150 ℃ of bakings 2-3 hour under vacuum before the polymerization charge into to reduce to behind the atmospheric ethene and set 30 ℃.With triisobutyl aluminium (200 μ mol) and catalyst A
1: change over to after 2-(2,3,4,5-tetramethyl-ring pentadienyl)-4,6-di-tert-butylphenol oxygen base titanium dichloride (1 μ mol) mix mutually and contain 100ml Ph
3CB (C
6F
5)
4In the reactor of the toluene solution of (1.0 μ mol) and norbornylene (0.1mol), the ethylene gas that feeds constant pressure 5atm begins reaction, and homo(io)thermism is 30 ℃ in the reaction process.The 30min afterreaction finishes, and the emptying reactor stops polyreaction with the 5%HCl/ methanol solution.Leach polymkeric substance, water and methyl alcohol thorough washing, 60 ℃ of vacuum-dryings are to constant weight.Obtain product 14.2g, reactive behavior is 4.7 * 10
5Gmol
-1Min
-1, contain norbornylene 5.7% in the product, molecular weight 55 * 10
4
Embodiment 2
Be aggregated in the 250mL autoclave and carry out, reactor 150 ℃ of bakings 2-3 hour under vacuum before the polymerization charge into to reduce to behind the atmospheric ethene and set 75 ℃.With triisobutyl aluminium (75 μ mol) and catalyst A
1Change over to after (1 μ mol) mixes mutually and contain 100ml Ph
3CB (C
6F
5)
4In the reactor of the toluene solution of (1.2 μ mol) and norbornylene (0.1mol), the ethylene gas that feeds constant pressure 5atm begins reaction, homo(io)thermism is 75 ℃ in the reaction process.The 20min afterreaction finishes, and the emptying reactor stops polyreaction with the 5%HCl/ methanol solution.Leach polymkeric substance, water and methyl alcohol thorough washing, 60 ℃ of vacuum-dryings are to constant weight.Obtain product 12.8g, reactive behavior is 6.4 * 10
5Gmol
-1Min
-1, contain norbornylene 7.6% in the product, molecular weight 54 * 10
4
Embodiment 3
Be aggregated in the 250mL autoclave and carry out, reactor 150 ℃ of bakings 2-3 hour under vacuum before the polymerization charge into to reduce to behind the atmospheric ethene and set 100 ℃.With triisobutyl aluminium (100 μ mol) and catalyst A
2: change over to after 2-(2,3,4,5-tetramethyl-ring pentadienyl)-4,6-di-tert-butylphenol oxygen base zirconium dichloride (1 μ mol) mix mutually and contain 100ml Ph
3CB (C
6F
5)
4In the reactor of the toluene solution of (1.5 μ mol) and norbornylene (0.2mol), the ethylene gas that feeds constant pressure 5atm begins reaction, and homo(io)thermism is 100 ℃ in the reaction process.The 20min afterreaction finishes, and the emptying reactor stops polyreaction with the 5%HCl/ methanol solution.Leach polymkeric substance, water and methyl alcohol thorough washing, 60 ℃ of vacuum-dryings are to constant weight.Obtain product 15.1g, reactive behavior is 7.6 * 10
5Gmol
-1Min
-1, contain norbornylene 17% in the product, molecular weight 52 * 10
4
Embodiment 4
Be aggregated in the 250mL autoclave and carry out, reactor 150 ℃ of bakings 2-3 hour under vacuum before the polymerization charge into to reduce to behind the atmospheric ethene and set 75 ℃.With triisobutyl aluminium (75 μ mol) and catalyst A
1Change over to after (1 μ mol) mixes mutually and contain 100ml Ph
3CB (C
6F
5)
4In the reactor of the toluene solution of (1.6 μ mol) and norbornylene (0.2mol), the ethylene gas that feeds constant pressure 4atm begins reaction, and homo(io)thermism is 75 ℃ in the reaction process.The 20min afterreaction finishes, and the emptying reactor stops polyreaction with the 5%HCl/ methanol solution.Leach polymkeric substance, water and methyl alcohol thorough washing, 60 ℃ of vacuum-dryings are to constant weight.Obtain product 15.4g, reactive behavior is 7.7 * 10
5Gmol
-1Min
-1, contain norbornylene 24% in the product, molecular weight 51 * 10
4
Embodiment 5
Be aggregated in the 250mL autoclave and carry out, reactor 150 ℃ of bakings 2-3 hour under vacuum before the polymerization charge into to reduce to behind the atmospheric ethene and set 75 ℃.With triisobutyl aluminium (75 μ mol) and catalyst A
1Change over to after (1 μ mol) mixes mutually and contain 100ml Ph
3CB (C
6F
5)
4In the reactor of the toluene solution of (1.5 μ mol) and norbornylene (0.3mol), the ethylene gas that feeds constant pressure 3atm begins reaction, and homo(io)thermism is 75 ℃ in the reaction process.The 20min afterreaction finishes, and the emptying reactor stops polyreaction with the 5%HCl/ methanol solution.Leach polymkeric substance, water and methyl alcohol thorough washing, 60 ℃ of vacuum-dryings are to constant weight.Obtain product 15.6g, reactive behavior is 7.8 * 10
5Gmol
-1Min
-1, contain norbornylene 32% in the product, molecular weight 48 * 10
4
Embodiment 6
Be aggregated in the 250mL autoclave and carry out, reactor 150 ℃ of bakings 2-3 hour under vacuum before the polymerization charge into to reduce to behind the atmospheric ethene and set 75 ℃.With triisobutyl aluminium (75 μ mol) and catalyst A
1Change over to after (1 μ mol) mixes mutually and contain 100ml Ph
3CB (C
6F
5)
4In the reactor of the toluene solution of (1.5 μ mol) and norbornylene (0.4mol), the ethylene gas that feeds constant pressure 2atm begins reaction, and homo(io)thermism is 75 ℃ in the reaction process.The 20min afterreaction finishes, and the emptying reactor stops polyreaction with the 5%HCl/ methanol solution.Leach polymkeric substance, water and methyl alcohol thorough washing, 60 ℃ of vacuum-dryings are to constant weight.Obtain product 15.4g, reactive behavior is 7.7 * 10
5Gmol
-1Min
-1, contain norbornylene 46% in the product, molecular weight 46 * 10
4
Embodiment 7
Be aggregated in the 250mL autoclave and carry out, reactor 150 ℃ of bakings 2-3 hour under vacuum before the polymerization charge into to reduce to behind the atmospheric ethene and set 75 ℃.With triisobutyl aluminium (75 μ mol) and catalyst A
1Change over to after (1 μ mol) mixes mutually and contain 100ml Ph
3CB (C
6F
5)
4In the reactor of the toluene solution of (1.7 μ mol) and norbornylene (0.5mol), the ethylene gas that feeds constant pressure 1atm begins reaction, and homo(io)thermism is 75 ℃ in the reaction process.The 20min afterreaction finishes, and the emptying reactor stops polyreaction with the 5%HCl/ methanol solution.Leach polymkeric substance, water and methyl alcohol thorough washing, 60 ℃ of vacuum-dryings are to constant weight.Obtain product 14.8g, reactive behavior is 7.4 * 10
5Gmol
-1Min
-1, contain norbornylene 74% in the product, molecular weight 44 * 10
4
Embodiment 8
Be aggregated in the 250mL autoclave and carry out, reactor 150 ℃ of bakings 2-3 hour under vacuum before the polymerization charge into to reduce to behind the atmospheric ethene and set 70 ℃.With triisobutyl aluminium (75 μ mol) and catalyst A
1Change over to after (1 μ mol) mixes mutually and contain 100ml Ph
3CB (C
6F
5)
4In the reactor of the toluene solution of (1.4 μ mol) and norbornylene (0.4mol), the ethylene gas that feeds constant pressure 2atm begins reaction, and homo(io)thermism is 70 ℃ in the reaction process.The 5min afterreaction finishes, and the emptying reactor stops polyreaction with the 5%HCl/ methanol solution.Leach polymkeric substance, water and methyl alcohol thorough washing, 60 ℃ of vacuum-dryings are to constant weight.Obtain product 10.4g, reactive behavior is 2.08 * 10
6Gmol
-1Min
-1, contain norbornylene 68% in the product, molecular weight 44 * 10
4
Embodiment 9
Be aggregated in the 250mL autoclave and carry out, reactor 150 ℃ of bakings 2-3 hour under vacuum before the polymerization charge into to reduce to behind the atmospheric ethene and set 80 ℃.With triethyl aluminum (50 μ mol) and catalyst A
4: 2-(2,3,4,5-tetramethyl-ring pentadienyl)-4 changes over to after 6-di-tert-butylphenol oxygen base dimethyl titanium (1 μ mol) mixes mutually and contains 100ml Ph
3CB (C
6F
5)
4In the reactor of the toluene solution of (1.6 μ mol) and norbornylene (0.4mol), the ethylene gas that feeds constant pressure 2atm begins reaction, and homo(io)thermism is 80 ℃ in the reaction process.The 10min afterreaction finishes, and the emptying reactor stops polyreaction with the 5%HCl/ methanol solution.Leach polymkeric substance, water and methyl alcohol thorough washing, 60 ℃ of vacuum-dryings are to constant weight.Obtain product 12.0g, reactive behavior is 1.2 * 10
6Gmol
-1Min
-1, contain norbornylene 57% in the product, molecular weight 46 * 10
4
Embodiment 10
Be aggregated in the 250mL autoclave and carry out, reactor 150 ℃ of bakings 2-3 hour under vacuum before the polymerization charge into to reduce to behind the atmospheric ethene and set 50 ℃.With trimethyl aluminium (60 μ mol) and catalyst A
2Change over to after (1 μ mol) mixes mutually and contain 100ml PhNMe
2HB (C
6F
5)
4In the reactor of the toluene solution of (1.2 μ mol) and norbornylene (0.3mol), the ethylene gas that feeds constant pressure 1atm begins reaction, and homo(io)thermism is 50 ℃ in the reaction process.The 15min afterreaction finishes, and the emptying reactor stops polyreaction with the 5%HCl/ methanol solution.Leach polymkeric substance, water and methyl alcohol thorough washing, 60 ℃ of vacuum-dryings are to constant weight.Obtain product 7.9g, reactive behavior is 5.3 * 10
5Gmol
-1Min
-1, contain norbornylene 34% in the product, molecular weight 16 * 10
4
Embodiment 11
Be aggregated in the 250mL autoclave and carry out, reactor 150 ℃ of bakings 2-3 hour under vacuum before the polymerization charge into to reduce to behind the atmospheric ethene and set 80 ℃.With triisobutyl aluminium (200 μ mol) and catalyst A
2Change over to after (1 μ mol) mixes mutually and contain 100ml PhNMe
2HB (C
6F
5)
4In the reactor of the toluene solution of (1.8 μ mol) and norbornylene (0.2mol), the ethylene gas that feeds constant pressure 1atm begins reaction, and homo(io)thermism is 80 ℃ in the reaction process.The 10min afterreaction finishes, and the emptying reactor stops polyreaction with the 5%HCl/ methanol solution.Leach polymkeric substance, water and methyl alcohol thorough washing, 60 ℃ of vacuum-dryings are to constant weight.Obtain product 10.6g, reactive behavior is 1.06 * 10
6Gmol
-1Min
-1, contain norbornylene 68% in the product, molecular weight 36 * 10
4
Embodiment 12
Be aggregated in the 250mL autoclave and carry out, reactor 150 ℃ of bakings 2-3 hour under vacuum before the polymerization charge into to reduce to behind the atmospheric ethene and set 80 ℃.With triisobutyl aluminium (150 μ mol) and catalyst A
3: 2-(2,3,4,5-tetramethyl-ring pentadienyl)-4 changes over to after 6-di-tert-butylphenol oxygen base hafnium dichloride (1 μ mol) is mixed mutually and contains 100ml Ph
3CB[(CF
3)
2C
6H
3]
4In the reactor of the toluene solution of (2.0 μ mol) and norbornylene (0.2mol), the ethylene gas of feeding 2atm is closed the ethene air-supplying valve and is begun reaction, and homo(io)thermism is 80 ℃ in the reaction process.The 10min afterreaction finishes, and the emptying reactor stops polyreaction with the 5%HCl/ methanol solution.Leach polymkeric substance, water and methyl alcohol thorough washing, 60 ℃ of vacuum-dryings are to constant weight.Obtain product 7.0g, reactive behavior is 7 * 10
5Gmol
-1Min
-1, contain norbornylene 80% in the product, molecular weight 24 * 10
4
Embodiment 13
Be aggregated in the 250mL autoclave and carry out, reactor 150 ℃ of bakings 2-3 hour under vacuum before the polymerization charge into to reduce to behind the atmospheric ethene and set 70 ℃.With trimethyl aluminium (35 μ mol), triethyl aluminum (25 μ mol), triisobutyl aluminium (40 μ mol) and catalyst A
1Change over to after (1 μ mol) mixes mutually and contain 100mlPh
3CB (C
6F
5)
4In the reactor of the toluene solution of (2.0 μ mol) and norbornylene (0.4mol), the ethylene gas that feeds constant pressure 2atm begins reaction, and homo(io)thermism is 70 ℃ in the reaction process.The 5min afterreaction finishes, and the emptying reactor stops polyreaction with the 5%HCl/ methanol solution.Leach polymkeric substance, water and methyl alcohol thorough washing, 60 ℃ of vacuum-dryings are to constant weight.Obtain product 11.6g, reactive behavior is 2.32 * 10
6Gmol
-1Min
-1, contain norbornylene 76% in the product, molecular weight 32 * 10
4
Embodiment 14
Be aggregated in the 250mL autoclave and carry out, reactor 150 ℃ of bakings 2-3 hour under vacuum before the polymerization charge into to reduce to behind the atmospheric ethene and set 60 ℃.With methylaluminoxane (500 μ mol) and catalyst A
4(1 μ mol) changes in the reactor of the toluene solution that contains 100ml norbornylene (0.2mol) after mixing mutually, and the ethylene gas that feeds constant pressure 1atm begins reaction, and homo(io)thermism is 60 ℃ in the reaction process.The 10min afterreaction finishes, and the emptying reactor stops polyreaction with the 5%HCl/ methanol solution.Leach polymkeric substance, water and methyl alcohol thorough washing, 60 ℃ of vacuum-dryings are to constant weight.Obtain product 6.4g, reactive behavior is 6.4 * 10
5Gmol
-1Min
-1, contain norborneol 49% in the product, molecular weight 30 * 10
4
Embodiment 15
Be aggregated in the 250mL autoclave and carry out, reactor 150 ℃ of bakings 2-3 hour under vacuum before the polymerization charge into to reduce to behind the atmospheric ethene and set 75 ℃.With methylaluminoxane (1000 μ mol) and catalyst A
4(1 μ mol) changes in the reactor of the toluene solution that contains 100ml norbornylene (0.3mol) after mixing mutually, and the ethylene gas that feeds constant pressure 2atm begins reaction, and homo(io)thermism is 75 ℃ in the reaction process.The 5min afterreaction finishes, and the emptying reactor stops polyreaction with the 5%HCl/ methanol solution.Leach polymkeric substance, water and methyl alcohol thorough washing, 60 ℃ of vacuum-dryings are to constant weight.Obtain product 7.9g, reactive behavior is 1.58 * 10
6Gmol
-1Min
-1, contain norbornylene 65% in the product, molecular weight 29 * 10
4
Embodiment 16
Be aggregated in the 250mL autoclave and carry out, reactor 150 ℃ of bakings 2-3 hour under vacuum before the polymerization charge into to reduce to behind the atmospheric ethene and set 100 ℃.With ethyl aikyiaiurnirsoxan beta (1500 μ mol) and catalyst A
3(1 μ mol) changes in the reactor of the toluene solution that contains 100ml norbornylene (0.2mol) after mixing mutually, and the ethylene gas that feeds constant pressure 2atm begins reaction, and homo(io)thermism is 100 ℃ in the reaction process.The 10min afterreaction finishes, and the emptying reactor stops polyreaction with the 5%HCl/ methanol solution.Leach polymkeric substance, water and methyl alcohol thorough washing, 60 ℃ of vacuum-dryings are to constant weight.Obtain product 4.4g, reactive behavior is 4.4 * 10
5Gmol
-1Min
-1, contain norbornylene 36% in the product, molecular weight 36 * 10
4
Embodiment 17
Be aggregated in the 250mL autoclave and carry out, reactor 150 ℃ of bakings 2-3 hour under vacuum before the polymerization charge into to reduce to behind the atmospheric ethene and set 75 ℃.With modified methylaluminoxane (1500 μ mol) and catalyst A
4(1 μ mol) changes in the reactor of the toluene solution that contains 100ml norbornylene (0.3mol) after mixing mutually, closes the ethene air-supplying valve behind the ethylene gas of feeding 2atm and begins reaction, and homo(io)thermism is 75 ℃ in the reaction process.The 5min afterreaction finishes, and the emptying reactor stops polyreaction with the 5%HCl/ methanol solution.Leach polymkeric substance, water and methyl alcohol thorough washing, 60 ℃ of vacuum-dryings are to constant weight.Obtain product 8.1g, reactive behavior is 1.62 * 10
6Gmol
-1Min
-1, contain norbornylene 74% in the product, molecular weight 33 * 10
4
Embodiment 18
Be aggregated in the 250mL autoclave and carry out, reactor 150 ℃ of bakings 2-3 hour under vacuum before the polymerization charge into to reduce to behind the atmospheric ethene and set 80 ℃.With isobutyl aluminium alkoxide (1500 μ mol) and catalyst A
2(1 μ mol) changes in the reactor of the toluene solution that contains 100ml norbornylene (0.2mol) after mixing mutually, and the ethylene gas that feeds constant pressure 2atm begins reaction, and homo(io)thermism is 80 ℃ in the reaction process.The 10min afterreaction finishes, and the emptying reactor stops polyreaction with the 5%HCl/ methanol solution.Leach polymkeric substance, water and methyl alcohol thorough washing, 60 ℃ of vacuum-dryings are to constant weight.Obtain product 5.5g, reactive behavior is 5.5 * 10
5Gmol
-1Min
-1, contain norbornylene 37% in the product, molecular weight 29 * 10
4
Embodiment 19
Be aggregated in the 250mL autoclave and carry out, reactor 150 ℃ of bakings 2-3 hour under vacuum before the polymerization charge into to reduce to behind the atmospheric ethene and set 90 ℃.With isobutyl aluminium alkoxide (2000 μ mol) and catalyst A
2(1 μ mol) changes in the reactor of the toluene solution that contains 100ml norbornylene (0.3mol) after mixing mutually, closes the ethene air-supplying valve behind the ethylene gas of feeding 2atm and begins reaction, and homo(io)thermism is 90 ℃ in the reaction process.The 10min afterreaction finishes, and the emptying reactor stops polyreaction with the 5%HCl/ methanol solution.Leach polymkeric substance, water and methyl alcohol thorough washing, 60 ℃ of vacuum-dryings are to constant weight.Obtain product 5.0g, reactive behavior is 5 * 10
5Gmol
-1Min
-1, contain norbornylene 39% in the product, molecular weight 27 * 10
4
Embodiment 20
Be aggregated in the 250mL autoclave and carry out, reactor 150 ℃ of bakings 2-3 hour under vacuum before the polymerization charge into to reduce to behind the atmospheric ethene and set 60 ℃.With isobutyl aluminium alkoxide (1500 μ mol) and catalyst A
1(1 μ mol) changes in the reactor of the toluene solution that contains 100ml norbornylene (0.3mol) after mixing mutually, closes the ethene air-supplying valve behind the ethylene gas of feeding 2atm and begins reaction, and homo(io)thermism is 60 ℃ in the reaction process.The 30min afterreaction finishes, and the emptying reactor stops polyreaction with the 5%HCl/ methanol solution.Leach polymkeric substance, water and methyl alcohol thorough washing, 60 ℃ of vacuum-dryings are to constant weight.Obtain product 5.2g, reactive behavior is 1.7 * 10
5Gmol
-1Min
-1, contain norbornylene 34% in the product, molecular weight 28 * 10
4
Embodiment 21
Be aggregated in the 250mL autoclave and carry out, reactor 150 ℃ of bakings 2-3 hour under vacuum before the polymerization charge into to reduce to behind the atmospheric ethene and set 90 ℃.With isobutyl aluminium alkoxide (1500 μ mol) and catalyst A
4(1 μ mol) changes in the reactor of the toluene solution that contains 100ml norbornylene (0.3mol) after mixing mutually, closes the ethene air-supplying valve behind the ethylene gas of feeding 2atm and begins reaction, and homo(io)thermism is 90 ℃ in the reaction process.The 30min afterreaction finishes, and the emptying reactor stops polyreaction with the 5%HCl/ methanol solution.Leach polymkeric substance, water and methyl alcohol thorough washing, 60 ℃ of vacuum-dryings are to constant weight.Obtain product 5.1g, reactive behavior is 1.7 * 10
5Gmol
-1Min
-1, contain norbornylene 33% in the product, molecular weight (28 * 10
4
Embodiment 22
Be aggregated in the 250mL autoclave and carry out, reactor 150 ℃ of bakings 2-3 hour under vacuum before the polymerization charge into to reduce to behind the atmospheric ethene and set 75 ℃.With methylaluminoxane (700 μ mol), ethyl aikyiaiurnirsoxan beta (500 μ mol), isobutyl aluminium alkoxide (300 μ mol) and catalyst A
1(1 μ mol) changes in the reactor of the toluene solution that contains 100ml norbornylene (0.2mol) after mixing mutually, and the ethylene gas that feeds constant pressure 1atm begins reaction, and homo(io)thermism is 75 ℃ in the reaction process.The 5min afterreaction finishes, and the emptying reactor stops polyreaction with the 5%HCl/ methanol solution.Leach polymkeric substance, water and methyl alcohol thorough washing, 60 ℃ of vacuum-dryings are to constant weight.Obtain product 9g, reactive behavior is 1.8 * 10
6Gmol
-1Min
-1, contain norbornylene 57% in the product, molecular weight 30 * 10
4
Embodiment 23
The Primary Catalysts metallocene compound is divided into A by structure
1, A
2, A
3, A
4Deng 4 classes, have:
A
1: 2-(2,3,4,5-tetramethyl-ring pentadienyl)-4,6-di-tert-butylphenol oxygen base titanium dichloride.
Simultaneously: A
1Also can be 2-(2,3,4,5-tetramethyl-ring pentadienyl)-and 6-tert-butyl phenol oxygen base titanium dichloride, 2-(2,3,4,5-tetramethyl-ring pentadienyl)-4-tert-butyl phenol oxygen base titanium dichloride, 2-(2,3,4,5-tetramethyl-ring pentadienyl)-6-phenyl phenol oxygen base titanium dichloride, 2-(2,3,4,5-tetramethyl-ring pentadienyl)-6-sylvan oxygen base titanium dichloride, 2-(2,3,4,5-tetramethyl-ring pentadienyl)-4 sylvan oxygen base titanium dichloride, 2-(3,4-phenylbenzene cyclopentadienyl)-4,6-di-tert-butylphenol oxygen base titanium dichloride.
A
1Also can be 2-(3,4-phenylbenzene cyclopentadienyl)-6-tert-butyl phenol oxygen base titanium dichloride, 2-(3,4-phenylbenzene cyclopentadienyl)-4-tert-butyl phenol oxygen base titanium dichloride, 2-(3,4-phenylbenzene cyclopentadienyl)-6-phenyl phenol oxygen base titanium dichloride, 2-(3,4-phenylbenzene cyclopentadienyl)-6-sylvan oxygen base titanium dichloride, 2-(3,4-phenylbenzene cyclopentadienyl)-4 sylvan oxygen base titanium dichloride, 2-(3,4-phenylbenzene cyclopentadienyl)-4,6-di-tert-butylphenol oxygen base titanium dichloride.
Use A
12-(2 in arbitrary compound alternate embodiment in the class, 3,4,5-tetramethyl-ring pentadienyl)-4,6-di-tert-butylphenol oxygen base titanium dichloride, all can realize catalyzed ethylene and norbornylene copolymerization, but polymerization gained result 2-of no use (2,3,4,5-tetramethyl-ring pentadienyl)-4,6-di-tert-butylphenol oxygen base titanium dichloride is good like that as the result of Primary Catalysts gained.
A
2: 2-(2,3,4,5-tetramethyl-ring pentadienyl)-4,6-di-tert-butylphenol oxygen base zirconium dichloride.
A
2: also can be: 2-(2,3,4,5-tetramethyl-ring pentadienyl)-4-tert-butyl phenol oxygen base zirconium dichloride, 2-(2,3,4,5-tetramethyl-ring pentadienyl)-and 6-phenyl phenol oxygen base zirconium dichloride, 2-(2,3,4,5-tetramethyl-ring pentadienyl)-6-sylvan oxygen base zirconium dichloride, 2-(2,3,4,5-tetramethyl-ring pentadienyl)-4 sylvan oxygen base zirconium dichlorides, 2-(3,4-phenylbenzene cyclopentadienyl)-4,6-di-tert-butylphenol oxygen base zirconium dichloride.
A
2Also can be 2-(3,4-phenylbenzene cyclopentadienyl)-6-tert-butyl phenol oxygen base zirconium dichloride, 2-(3,4-phenylbenzene cyclopentadienyl)-4-tert-butyl phenol oxygen base zirconium dichloride, 2-(3,4-phenylbenzene cyclopentadienyl)-6-phenyl phenol oxygen base zirconium dichloride, 2-(3,4-phenylbenzene cyclopentadienyl)-6-sylvan oxygen base zirconium dichloride, 2-(3,4-phenylbenzene cyclopentadienyl)-4 sylvan oxygen base zirconium dichlorides, 2-(3,4-phenylbenzene cyclopentadienyl)-4,6-di-tert-butylphenol oxygen base zirconium dichloride.
Use A
22-(2 in arbitrary compound alternate embodiment in the class, 3,4,5-tetramethyl-ring pentadienyl)-4,6-di-tert-butylphenol oxygen base zirconium dichloride,, all can realize catalyzed ethylene and norbornylene copolymerization, but polymerization gained result is 2-(2 of no use, 3,4,5-tetramethyl-ring pentadienyl)-4,6-di-tert-butylphenol oxygen base zirconium dichloride is good like that as the result of Primary Catalysts gained.
A
3: 2-(2,3,4,5-tetramethyl-ring pentadienyl)-4,6-di-tert-butylphenol oxygen base hafnium dichloride.
A
3: also can be: 2-(2,3,4,5-tetramethyl-ring pentadienyl)-4-tert-butyl phenol oxygen base hafnium dichloride, 2-(2,3,4,5-tetramethyl-ring pentadienyl)-and 6-phenyl phenol oxygen base hafnium dichloride, 2-(2,3,4,5-tetramethyl-ring pentadienyl)-6-sylvan oxygen base hafnium dichloride, 2-(2,3,4,5-tetramethyl-ring pentadienyl)-4 sylvan oxygen base hafnium dichloride, 2-(3,4-phenylbenzene cyclopentadienyl)-4,6-di-tert-butylphenol oxygen base hafnium dichloride.
A
3Also can be 2-(3,4-phenylbenzene cyclopentadienyl)-6-tert-butyl phenol oxygen base hafnium dichloride, 2-(3,4-phenylbenzene cyclopentadienyl)-4-tert-butyl phenol oxygen base hafnium dichloride, 2-(3,4-phenylbenzene cyclopentadienyl)-6-phenyl phenol oxygen base hafnium dichloride, 2-(3,4-phenylbenzene cyclopentadienyl)-6-sylvan oxygen base hafnium dichloride, 2-(3,4-phenylbenzene cyclopentadienyl)-4 sylvan oxygen base hafnium dichloride, 2-(3,4-phenylbenzene cyclopentadienyl)-4,6-di-tert-butylphenol oxygen base hafnium dichloride.
Use A
32-(2 in a kind of alternate embodiment of class metallocene compound, 3,4,5-tetramethyl-ring pentadienyl)-4,6-di-tert-butylphenol oxygen base hafnium dichloride is made Primary Catalysts, polymerization result 2-(2 of no use, 3,4,5-tetramethyl-ring pentadienyl)-4,6-di-tert-butylphenol oxygen base hafnium dichloride is good as the result of Primary Catalysts gained.
A
4Be 2-(2,3,4,5-tetramethyl-ring pentadienyl)-4,6-di-tert-butylphenol oxygen base dimethyl titanium.
A
4Also can be: 2-(2,3,4,5-tetramethyl-ring pentadienyl)-4-tert-butyl phenol oxygen base dialkyl group titanium, 2-(2,3,4,5-tetramethyl-ring pentadienyl)-and 6-phenyl phenol oxygen base dialkyl group titanium, 2-(2,3,4,5-tetramethyl-ring pentadienyl)-6-sylvan oxygen base dialkyl group titanium, 2-(2,3,4,5-tetramethyl-ring pentadienyl)-4 sylvan oxygen base dialkyl group titaniums, 2-(3,4-phenylbenzene cyclopentadienyl)-4,6-di-tert-butylphenol oxygen base dialkyl group titanium.
A
4Also can be 2-(3,4-phenylbenzene cyclopentadienyl)-6-tert-butyl phenol oxygen base dialkyl group titanium, 2-(3,4-phenylbenzene cyclopentadienyl)-4-tert-butyl phenol oxygen base dialkyl group titanium, 2-(3,4-phenylbenzene cyclopentadienyl)-6-phenyl phenol oxygen base dialkyl group titanium, 2-(3,4-phenylbenzene cyclopentadienyl)-6-sylvan oxygen base dialkyl group titanium, 2-(3,4-phenylbenzene cyclopentadienyl)-4 sylvan oxygen base dialkyl group titaniums, 2-(3,4-phenylbenzene cyclopentadienyl)-4,6-di-tert-butylphenol oxygen base dialkyl group titanium.
Use A
42-(2 in a kind of alternate embodiment of class metallocene compound, 3,4,5-tetramethyl-ring pentadienyl)-4,6-di-tert-butylphenol oxygen base dimethyl titanium is made Primary Catalysts, polymerization gained result 2-(2 of no use, 3,4,5-tetramethyl-ring pentadienyl)-4,6-di-tert-butylphenol oxygen base dimethyl titanium is good as the result of Primary Catalysts gained.
In addition, all Primary Catalysts A in the listed embodiment of the present invention
1All available A
2Or A
3Or A
4Replace; A
2All available A
1Or A
3Or A
4Replace; A
3All available A
1Or A
2Or A
4Replace; A
4All available A
1Or A
2Or A
3Replace.Only the gained result is with replacement is preceding not different.
Claims (3)
1. the method for catalyzed ethylene and norbornylene copolymerization, use by metallocene compound to be Primary Catalysts and the constrained geometry configuration metallocene catalyst system that contains the phenoxy group side chain that constitutes as promotor with aluminum alkyls/boron compound, the structure of described metallocene compound is as follows:
Wherein luxuriant ring is single the replacement or polysubstituted cyclopentadienyl, indenyl or fluorenyl, and substituent R is selected from hydrogen, alkyl, aryl respectively; M is transition metals Ti, zirconium or hafnium; Two X are halogen, alkyl, alkoxyl group, amino, aryl; R
1Be the phenoxy group ortho-substituent, R
2Be all the other locational one or more substituting groups of phenoxy group phenyl ring, R
1And R
2Be alkyl or aryl; Described aluminum alkyls is trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, aluminium diethyl monochloride, or their mixture; Described boron compound is Ph
3CB (C
6F
5)
4, B (C
6F
5)
3, PhNMe
2HB (C
6F
5)
4Or Ph
3CB[(CF
3)
2C
6H
3]
4It is characterized in that, in the promotor in aluminium, boron and the Primary Catalysts mol ratio of transition metal be 50～200: 1～2: 1;
Be aggregated in the autoclave and carry out; Reactor 140～160 ℃ of bakings 2～3 hours under vacuum before the polymerization charge into 30～100 ℃ that reduce to setting behind the atmospheric ethene, inject the toluene solution of boron compound and norbornylene; Again aluminum alkyls is mixed mutually with metallocene compound and change in the reactor, feed ethylene gas and begin reaction to pressure 1～5atm, homo(io)thermism is reacted emptying reactor after 5～30 minutes at 30～100 ℃ in the reaction process, stops polyreaction with the HCl/ methanol solution; Leach polymkeric substance, use methanol wash, 50～70 ℃ of vacuum-dryings to constant weight; Wherein the mol ratio of transition metal is 1 * 10 in the consumption of norbornylene and the Primary Catalysts
5: 1,2 * 10
5: 1,3 * 10
5: 1,4 * 10
5: 1 or 5 * 10
5: 1.
2. the method for catalyzed ethylene and norbornylene copolymerization, use by metallocene compound to be Primary Catalysts and the constrained geometry configuration metallocene catalyst system that contains the phenoxy group side chain that constitutes as promotor with alkylaluminoxane, the structure of described metallocene compound is as follows:
Wherein luxuriant ring is single the replacement or polysubstituted cyclopentadienyl, indenyl or fluorenyl, and substituent R is selected from hydrogen, alkyl, aryl respectively; M is transition metals Ti, zirconium or hafnium; Two X are halogen, alkyl, alkoxyl group, amino, aryl; R
1Be the phenoxy group ortho-substituent, R
2Be all the other locational one or more substituting groups of phenoxy group phenyl ring, R
1And R
2Be alkyl or aryl; Described alkylaluminoxane is methylaluminoxane, modified methylaluminoxane, ethyl aikyiaiurnirsoxan beta or isobutyl aluminium alkoxide, or their mixture; It is characterized in that, wherein in the promotor in aluminium and the Primary Catalysts mol ratio of transition metal be 500～2000: 1;
Be aggregated in the autoclave and carry out; Reactor 140～160 ℃ of bakings 2～3 hours under vacuum before the polymerization charge into 30～100 ℃ that reduce to setting behind the atmospheric ethene, inject the toluene solution of norbornylene; With alkylaluminoxane with change in the reactor after metallocene compound mixes mutually, feed ethylene gas and begin reaction to pressure 1～2atm, constant 60～100 ℃ of temperature of reaction react 5～30 minutes emptying reactors, usefulness HCl/ methanol solution termination polyreaction; Leach polymkeric substance, use methanol wash, 50～70 ℃ of vacuum-dryings to constant weight; Wherein the mol ratio of transition metal is 2 * 10 in the consumption of norbornylene and the Primary Catalysts
5: 1 or 3 * 10
5: 1.
3. according to the method for described a kind of catalyzed ethylene of claim 2 and norbornylene copolymerization, it is characterized in that described alkylaluminoxane is methylaluminoxane or modified methylaluminoxane.
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