CN1167720C - Polymeric catalyst system of norbornaene and its preparing process - Google Patents
Polymeric catalyst system of norbornaene and its preparing process Download PDFInfo
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- CN1167720C CN1167720C CNB021263183A CN02126318A CN1167720C CN 1167720 C CN1167720 C CN 1167720C CN B021263183 A CNB021263183 A CN B021263183A CN 02126318 A CN02126318 A CN 02126318A CN 1167720 C CN1167720 C CN 1167720C
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Abstract
The present invention relates to a catalytic system for polymerizing norbornene as a complex of nitrogen, oxygen and nickel. The catalytic system is composed of <2-(2'-substituent-hydroxyphenyl)-4, 5-diphenyl imidazole>-(1-naphthyl)-(triphenylphosphine) nickel (II) complex as a main catalyst and methyl aluminoxane (MAO) as a cocatalyst. The present invention has the advantages of simple technology, easy raw material obtainment and low cost. Catalytic activity reaches 1.62*10<9>g polynorbornene per molar catalyst per hour per atmospheric pressure (1.62*10<9>g/molNi. h. atm). by changing reaction conditions, the activity of the catalyst (1*10<4>-1.62*10<9>g PNB/(molNi. h. atm)), polynorbornene yield(20 to 100%), molecular weight ((1*10<5>-3.5*10<6>) and molecular weight distribution (1.5 to 20) can be adjusted within a wide range.
Description
Technical field
The present invention relates to a kind of norbornylene and derivative polymeric catalyst system thereof of being used for, relate in particular to a kind of norbornylene and derivative polymeric [2-(2 '-substituted 4-hydroxy phenyl)-4,5-diphenyl-imidazole]-complex-catalyzed system of (1-naphthyl)-(triphenylphosphine) nickel (II) thereof of being used for.
The invention still further relates to the preparation method of above-mentioned catalyst system.
The invention still further relates to the purposes of above-mentioned catalyst system in norbornylene and derivative polymerization thereof.
Background technology
Dicyclo [2.2.1] hept-2-ene" is commonly called as and is norbornylene.Norbornylene and derivative thereof can carry out polymerization by three kinds of modes showing down:
Different polymerization methodses obtain the polymkeric substance of different structure and character.First kind of polymerization methods is called ring-opening metathesis polymerization (ROMP), is the maximum a kind of norbornene polymerization mode of research, and industrial polynorbornene Norsorex technology is exactly the application of ROMP in actual production.Second kind of polymerization methods about norbornylene is positively charged ion or radical polymerization mode (cationic or radical), and it is few that people understand, and products obtained therefrom also only is that 2,7 of norbornylene connects oligopolymer.In the third polymerization methods, still the twin nuclei that has kept norbornylene in the product, only be to have opened the two keys of π-π, be similar to traditional olefinic polymerization mode, therefore be called as vinyl polymerization (Vinylpolymerization), the vinyl polymerization of this cycloolefin is also referred to as " addition polymerization " (additionpolymerization) sometimes.
Different with first kind of ROMP polymerization methods and second kind of positively charged ion or radical polymerization mode (cationicor radical) products obtained therefrom, vinyl polymerization mode resulting polymers no longer contains two keys, and can obtain the polymkeric substance of higher molecular weight.The homogeneous phase vinyl polymerization can obtain the polymer materials of function uniqueness, and many solvents are presented inertia.Resulting polymers not only has excellent machining property, and has high glass transition, has the optical clarity that good thermotolerance is become reconciled, has very strong anti-ultraviolet radiation ability (can be used as protective material), high tension fracture value and low-tension (preparing high transparent film); The low-k of polynorbornene makes it can be used as the interface dielectric medium in the microelectronic device, thereby realizes efficient mutually connection the between the interface; In addition, such polynorbornene material has good viscosity, can be bonded at securely on various films and the substrate.In a word, norbornene polymer is widely used in top coat or the protective layer of making electrical condenser (comdenser) or thermal insulator (insulator) and liquid-crystal display.
Every year is produced a large amount of norbornylene byproducts in petrochemical industry, still, because China does not have catalyzer well to convert it into norbornene polymer, and most norbornylene resource is wasted.Simultaneously, China needs the norbornene polymers such as sealer of high price import liquid-crystal display.
Summary of the invention
The object of the present invention is to provide a kind of [2-(2 '-substituted 4-hydroxy phenyl)-4,5-diphenyl-imidazole]-complex-catalyzed system of (1-naphthyl)-(triphenylphosphine) nickel (II);
Another object of the present invention is to provide a kind of method for preparing above-mentioned catalyst system;
Another purpose of the present invention is to provide the application of a kind of above-mentioned catalyst system in norbornylene and derivative polymerization thereof.
For achieving the above object, catalyst system provided by the invention comprises Primary Catalysts and promotor, and described Primary Catalysts is [2-(2 '-substituted 4-hydroxy phenyl)-4, the 5-diphenyl-imidazole]-(1-naphthyl)-(triphenylphosphine) nickel (II) title complex, be shown below:
Wherein, R
1Be methyl, ethyl, propyl group, sec.-propyl, normal-butyl, the tertiary butyl, isobutyl-, methoxyl group, oxyethyl group, chlorine atom, bromine atoms or iodine atom.
Described promotor is methylaluminoxane (MAO).
The method of the above-mentioned catalyst system of preparation provided by the invention, its key step comprises:
(A) N, the preparation of O bitooth ligand:
In 3 milliliters of Glacial acetic acid, add respectively: substituted salicylic aldehydes 0.8-1.2 mmole, benzil 0.8-1.5 mmole, ammonium acetate 6.4-7.5 mmole, place flask, after stirring and refluxing 4-15 hour, this mixing solutions is cooled to room temperature, stirs then in the following impouring 500-2500 milliliter saturated sodium bicarbonate solution, obtain white solid, filter, this white solid is dissolved in the 20-300 milliliter methylene dichloride, use Skellysolve A to wherein diffusion, separate out white products, productive rate 85-96%;
Substituted salicylic aldehydes of the present invention is a salicylic aldehyde, the 3-tertiary butyl-2-hydroxy benzaldehyde, the 4-tertiary butyl-2-hydroxy benzaldehyde, 3,5-di-t-butyl-2-hydroxy benzaldehyde, 3-isobutyl--2-hydroxy benzaldehyde, 3-naphthyl-2-hydroxy benzaldehyde, 3-anthryl-2-hydroxy benzaldehyde, 3,5-diisobutyl-2-hydroxy benzaldehyde, 3-normal-butyl-2-hydroxy benzaldehyde, 4-normal-butyl-2-hydroxy benzaldehyde, 5-normal-butyl-2-hydroxy benzaldehyde, 4-nitro-2-hydroxy benzaldehyde, 4-nitroso-group-2-hydroxy benzaldehyde, 5-nitro-2-hydroxy benzaldehyde, 5-nitroso-group-2-hydroxy benzaldehyde, 6-nitro-2-hydroxy benzaldehyde, 6-nitroso-group-2-hydroxy benzaldehyde, 3-methoxyl group-2-hydroxy benzaldehyde, 4-methoxyl group-2-hydroxy benzaldehyde, 5-methoxyl group-2-hydroxy benzaldehyde, 6-methoxyl group-2-hydroxy benzaldehyde, 3,5-two iodo-2-hydroxy benzaldehydes, 4-iodo-2-hydroxy benzaldehyde, 5-iodo-2-hydroxy benzaldehyde, 3,5-two chloro-2-hydroxy benzaldehydes, 3-chloro-2-hydroxy benzaldehyde, 5-chloro-2-hydroxy benzaldehyde, 4-chloro-2-hydroxy benzaldehyde, 3,5-two bromo-2-hydroxy benzaldehydes, 4-fluoro-2-hydroxy benzaldehyde, 5-fluoro-2-hydroxy benzaldehyde, 3-fluoro-2-hydroxy benzaldehyde, 6-fluoro-2-hydroxy benzaldehyde, 3,5-two fluoro-2-hydroxy benzaldehydes, 4-bromo-2-hydroxy benzaldehyde, 3-methyl-2-hydroxy benzaldehyde, 4-methyl-2-hydroxy benzaldehyde, 5-methyl-2-hydroxy benzaldehyde, 6-methyl-2-hydroxy benzaldehyde, 3,5-dimethyl-2-hydroxy benzaldehyde, 3-sec.-propyl-2-hydroxy benzaldehyde, 4-sec.-propyl-2-hydroxy benzaldehyde, 3,5-di-isopropyl-2-hydroxy benzaldehyde, 33-ethyl-2-hydroxy benzaldehyde or 3,5-diethyl-2-hydroxy benzaldehyde.Wherein preferred salicylic aldehyde, 4-methoxyl group-2-hydroxy benzaldehyde, 4-nitro-2-hydroxy benzaldehyde, the 3-tertiary butyl-2-hydroxy benzaldehyde, 3-naphthyl-2-hydroxy benzaldehyde, 3,5-di-t-butyl-2-hydroxy benzaldehyde, 3-isobutyl--2-hydroxy benzaldehyde, 3-anthryl-2-hydroxy benzaldehyde, 3,5-diisobutyl-2-hydroxy benzaldehyde, 3-normal-butyl-2-hydroxy benzaldehyde, 3,5-two iodo-2-hydroxy benzaldehydes, 3,5-two bromo-2-hydroxy benzaldehydes, 3,5-two chloro-2-hydroxy benzaldehydes, 3-sec.-propyl-2-hydroxy benzaldehyde, 3,5-di-isopropyl-2-hydroxy benzaldehyde, 3-ethyl-2-hydroxy benzaldehyde or 3,5-diethyl-2-hydroxy benzaldehyde.
(B) preparation of Primary Catalysts:
Trans-[chlorine (1-naphthyl) (two (triphenylphosphine))] nickel (trans-chloro (1-naphthyl) bis (triphenylphosphane) nickel (II)) is dissolved in ratio in the 5-50ml methylene dichloride in every 1mmol, makes solution 1;
A certain amount of step (A) gained white products is dissolved in the 2-50ml anhydrous tetrahydro furan (THF) by 1mmol, stirs the sodium hydride (NaH) of amount of substance such as adding and white products down, reaction was made solution 2 after 30-120 minute under anhydrous condition;
Stir down, press N, the mol ratio 1 of O bitooth ligand and trans-[chlorine (1-naphthyl) (two (triphenylphosphine))] nickel (trans-chloro (1-naphthyl) bis (triphenylphosphane) nickel (II)): 0.8-1 splashes into solution 1 in the solution 2, reacted 5 minutes to 3 days, filter, obtain product.
The application of catalyst system provided by the invention in the polymerization of norbornylene or derivatives thereof, under the nitrogen environment, Primary Catalysts is dissolved in the organic solvent, its ratio is 1 μ mol: 2-30ml, add norbornylene again, the mol ratio 2000-100000 of norbornylene and Primary Catalysts,-30-120 ℃ of reaction, preferably-15-100 ℃, add promotor, promotor/Primary Catalysts mol ratio is 50-5000, adds 2-15mL isopropylcarbinol termination reaction after reacting 5 second-500 minute, and 5 ‰ the acidic alcohol that adds 50-500ml again makes polymer precipitation complete.
Norbornylene of the present invention can also be its derivative, be specially: dicyclo [2.2.1] hept-2-ene" (norbomene), capric acid (dicyclo [2.2.1] heptan-5-alkene-2-first) ester (bicyclo[2,2,1] hept-5-ene-2-ylmethyl decanoate), dicyclo [2.2.1] heptan-5-alkene-2-carboxylate methyl ester (bicyclo[2,2,1] hept-5-ene-2-carboxylic acid methyl ester), dicyclo [2.2.1] heptan-5-alkene-2-methyl alcohol (bicyclo[2,2,1] hept-5-ene-2-methanol), dicyclo [2.2.1] heptan-5-alkene-2-carboxylic acid, ethyl ester (bicyclo[2,2,1] hept-5-ene-2-carboxylic acid ethylester), dicyclo [2.2.1] heptan-positive butyl ester (bicyclo[2 of 5-alkene-2-carboxylic acid, 2,1] hept-5-ene-2-carboxylic acid n-butyl ester), dicyclo [2.2.1] heptan-5-alkene-2-carboxylic acid isobutyl ester (bicyclo[2,2,1] hept-5-ene-2-carboxylic acid iso-butyl ester), dicyclo [2.2.1] heptan-5-alkene-2-carboxylic acid (bicyclo[2,2,1] hept-5-ene-2-carboxylic acid), 5-ethylidene-dicyclo [2.2.1] hept-2-ene" (bicyclo[2,2,1] hept-2-ene-5-ethylene), dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxylic anhydride (carbic anhydride), dicyclo [2.2.1] heptan-5-alkene-2,3-dimethyl dicarboxylate (bicyclo[2,2,1] hept-5-ene-2,3-dicarboxylic acid dimethyl ester), dicyclo [2.2.1] heptan-5-alkene-2,3-diethyl dicarboxylate (bicyclo[2,2,1] hept-5-ene-2,3-dicarboxylic acid diethyl ester), dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxylic acid di-n-butyl (bicyclo[2,2,1] hept-5-ene-2,3-dicarboxylic acid di-n-butyl ester) or dicyclo [2.2.1] heptan-5-alkene-2,3-diisobutyl dicarboxylate (bicyclo[2,2,1] hept-5-ene-2,3-dicarboxylic acid di-isobutyl ester).
Described organic solvent is toluene, chlorobenzene, 1,2-dichlorobenzene, normal hexane, 1,2-ethylene dichloride or 1,2,4-trichlorobenzene.
Catalyst system of the present invention has following feature:
1, catalyst system therefor preparation of the present invention is simple, and raw material is easy to get, and stable performance.
2, catalyst system of the present invention has been realized the vinyl polymerization (addition polymerization) to norbornylene and derivative thereof, resulting polymkeric substance can be by adjusting the different ratios of MAO/ catalyzer, or by changing the volume of reaction solvent, or by changing temperature of reaction or solvent to reach molecular weight and the molecular weight distribution of adjusting polymkeric substance, the purpose of telomerized polymer form and performance, thus be met the norbornylene of different demands and purposes and the polymkeric substance of derivative thereof.
3, catalyst system catalytic activity height of the present invention, active in 1 * 10
4-1.62 * 10
9GPNB/ (molNihatm).
Embodiment
Embodiment one:
1.N, the preparation of O bitooth ligand: with 30 milliliters of Glacial acetic acid, 8.8 the ammonium acetate of the 3-tertiary butyl-2-hydroxy benzaldehyde of mmole (mmol) and the benzil of 8.6 mmoles (mmol) and 64 mmoles (mmol) places 250 milliliters of (mL) round-bottomed flasks, after the stirring and refluxing 4 hours, this mixing solutions is cooled to room temperature, in 500 milliliters of saturated sodium bicarbonate solutions of impouring, obtain white solid under stirring then.Filter, this white solid is dissolved in 50 milliliters of methylene dichloride, to wherein diffusion, separate out white crystal, productive rate 85% with Skellysolve A.Ultimate analysis measured value: C, 81.51; H, 6.55; N, 7.56; O, 4.38%; C
25H
24N
2The theoretical value of O: C, 81.49; H, 6.57; N, 7.60; O, 4.34%;
1H NMR (CDCl
3): 1.49 (s, 9H), 5.31 (s, 1H), 6.85-7.83 (m, 13H), 10.02 (s, 1H);
2. Preparation of catalysts:
The above-mentioned gained white products of 2 mmoles is dissolved in the 20ml anhydrous tetrahydro furan (THF), stir the sodium hydride (NaH) that adds 2 mmoles down, reaction is after 60 minutes under anhydrous condition, stir down, be added dropwise to the dichloromethane solution that 40ml is dissolved with trans-[chlorine (1-naphthyl) (two (triphenylphosphine))] nickel (trans-chloro (1-naphthyl) bis (triphenylphosphane) nickel (II)) (2 mmole), react after 8 hours, filter, obtain product.Ultimate analysis measured value: C, 78.03; H, 5.57; N, 3.44; Ni, 7.18; O, 1.97; P, 3.81%; C
53H
45N
2The theoretical value of NiOP: C, 78.05; H, 5.56; N, 3.43; Ni, 7.20; O, 1.96; P, 3.80%.
3. norbornene polymerization: will have the 250 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add the prepared catalyzer of 5 μ mol steps 2,20 milliliters of toluene, add 1.00 gram norbornylenes (norbornene monomer and catalyst molar ratio are 2100) again, stir after 5 minutes in the time of 25 ℃, add 3.6 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 1000), reaction is after 60 minutes in the time of 25 ℃, add the 5ml isopropylcarbinol and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 40 hours, get polymkeric substance 0.5607 gram, transformation efficiency 56.07%, catalyst activity are 1.1 * 10
5GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 8.3 * 10
5, number-average molecular weight (Mn) is 1.9 * 10
5, Mw/Mn is 4.4.
Embodiment two:
1, Preparation of catalysts: the preparation method is with embodiment one.
2, norbornene polymerization: will have the 250 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add the prepared catalyzer of 5 μ mol steps 1,20 milliliters of toluene, add 1.00 gram norbornylenes (norbornene monomer and catalyst molar ratio are 2100) again, stir after 5 minutes in the time of 25 ℃, add 5.4 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 1500), reaction is after 60 minutes in the time of 25 ℃, add the 5ml isopropylcarbinol and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 40 hours, get polymkeric substance 0.3480 gram, transformation efficiency 34.8%, catalyst activity are 7.0 * 10
4GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 2.6 * 10
5, number-average molecular weight (Mn) is 1.5 * 10
5, molecular weight distribution is 1.7.
Embodiment three:
1, Preparation of catalysts: the preparation method is with embodiment one.
2, norbornene polymerization: will have the 250 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add the prepared catalyzer of 5 micromoles (μ mol) step 1,20 milliliters of toluene, add 1.00 gram norbornylenes (norbornene monomer and catalyst molar ratio are 2100) again, stir after 5 minutes in the time of 25 ℃, add 7.2 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 60 minutes in the time of 25 ℃, add the 5ml isopropylcarbinol and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 40 hours, get polymkeric substance 0.5602 gram, transformation efficiency 56.02%, catalyst activity are 1.1 * 10
5GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 1.2 * 10
6, number-average molecular weight (Mn) is 3.5 * 10
5, molecular weight distribution is 3.4.
Embodiment four:
1, Preparation of catalysts: the preparation method is with embodiment one.
2, norbornene polymerization: will have the 250 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add the prepared catalyzer of 5 micromoles (μ mol) step 1,30 milliliters of toluene, add 4.708 gram norbornylenes (norbornene monomer and catalyst molar ratio are 10000) again, stir after 5 minutes in the time of 25 ℃, add 3.6 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 1000), reaction is after 30 minutes in the time of 25 ℃, add the 5ml isopropylcarbinol and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 40 hours, get polymkeric substance 1.8619 grams, transformation efficiency 39.55%, catalyst activity are 7.45 * 10
5GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 5.8 * 10
5, number-average molecular weight (Mn) is 3.2 * 10
5, molecular weight distribution is 1.8.
Embodiment five:
1, Preparation of catalysts: the preparation method is with embodiment one.
2, norbornene polymerization: will have the 250 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add the prepared catalyzer of 5 micromoles (μ mol) step 1,30 milliliters of toluene, add 9.415 gram norbornylenes (norbornene monomer and catalyst molar ratio are 20000) again, stir after 5 minutes in the time of 25 ℃, add 7.2 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 minute in the time of 25 ℃, add the 5ml isopropylcarbinol and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 40 hours, get polymkeric substance 4.3430 grams, transformation efficiency 46.13%, catalyst activity are 5.21 * 10
7GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 3.9 * 10
5, number-average molecular weight (Mn) is 1.4 * 10
5, molecular weight distribution is 2.8.
Embodiment six:
1, Preparation of catalysts: the preparation method is with embodiment one.
2, norbornene polymerization: will have the 250 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add the prepared catalyzer of 5 micromoles (μ mol) step 1,30 milliliters of toluene, add 18.83 gram norbornylenes (norbornene monomer and catalyst molar ratio are 40000) again, in the time of 25 ℃, stir after 5 minutes, add 7.2 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), in the time of 25 ℃, reacted for 20 seconds after, add the 5ml isopropylcarbinol and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 40 hours, get polymkeric substance 5.8178 grams, transformation efficiency 30.90%, catalyst activity are 2.09 * 10
8GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 3.2 * 10
5, number-average molecular weight (Mn) is 2.1 * 10
5, molecular weight distribution is 1.5.
Embodiment seven:
1, Preparation of catalysts: the preparation method is with embodiment one.
2, norbornene polymerization: will have the 250 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add the prepared catalyzer of 5 micromoles (μ mol) step 1,30 milliliters of toluene, add 4.708 gram norbornylenes (norbornene monomer and catalyst molar ratio are 10000) again, stir after 5 minutes in the time of 50 ℃, add 7.2 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 30 minutes in the time of 50 ℃, add the 5ml isopropylcarbinol and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 40 hours, get polymkeric substance 2.6355 grams, transformation efficiency 55.95%, catalyst activity are 1.05 * 10
6GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 8.9 * 10
5, number-average molecular weight (Mn) is 2.5 * 10
5, molecular weight distribution is 3.56.
Embodiment eight:
1, Preparation of catalysts: the preparation method is with embodiment one.
2, norbornene polymerization: will have the 250 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add the prepared catalyzer of 5 micromoles (μ mol) step 1,30 milliliters of toluene, add 4.708 gram norbornylenes (norbornene monomer and catalyst molar ratio are 10000) again, stir after 5 minutes in the time of 0 ℃, add 7.2 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 30 minutes in the time of 0 ℃, add the 5ml isopropylcarbinol and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 40 hours, get polymkeric substance 2.7135 grams, transformation efficiency 57.64%, catalyst activity are 1.09 * 10
6GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 7.3 * 10
5, number-average molecular weight (Mn) is 3.4 * 10
5, molecular weight distribution is 2.15.
Embodiment nine:
1, Preparation of catalysts: the preparation method is with embodiment one.
2, norbornene polymerization: will have the 250 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add the prepared catalyzer of 5 micromoles (μ mol) step 1,30 milliliters of toluene, add 4.708 gram norbornylenes (norbornene monomer and catalyst molar ratio are 10000) again, stir after 5 minutes in the time of 100 ℃, add 7.2 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 30 minutes in the time of 100 ℃, add the 5ml isopropylcarbinol and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 40 hours, get polymkeric substance 1.7685 grams, transformation efficiency 37.56%, catalyst activity are 7.07 * 10
5GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 1.5 * 10
6, number-average molecular weight (Mn) is 1.6 * 10
5, molecular weight distribution is 9.8.
Embodiment ten:
1, Preparation of catalysts: the preparation method is with embodiment one.
2, norbornene polymerization: will have the 250 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add the prepared catalyzer of 5 μ mol steps 1,20 milliliter 1, the 2-dichlorobenzene adds 18.832 gram norbornylenes (norbornene monomer and catalyst molar ratio are 40000) again, stirs after 5 minutes in the time of 25 ℃, add 4.3 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 1200), after in the time of 25 ℃, reacting for 6 seconds, add the 5ml isopropylcarbinol and stop polymerization, add 200 milliliter 5 ‰ acidic alcohol (volume ratio) again, under room temperature, stirred 10 hours, leave standstill 2 hours after-filtration then, resulting polymers gets polymkeric substance 13.4521 grams in 80 ℃ of vacuum-dryings 40 hours, transformation efficiency 71.43%, catalyst activity are 1.62 * 10
9GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 1.7 * 10
6, number-average molecular weight (Mn) is 6.1 * 10
5, molecular weight distribution is 2.8.
Embodiment 11:
1, N, the preparation of O bitooth ligand: with 30 milliliters of Glacial acetic acid, 8.8 3 of mmole (mmol), the benzil of 5-two iodo-2-hydroxy benzaldehydes and 8.6 mmoles (mmol) and the ammonium acetate of 64 mmoles (mmol) place 250 milliliters of (mL) round-bottomed flasks, after the stirring and refluxing 6 hours, this mixing solutions is cooled to room temperature, in 500 milliliters of saturated sodium bicarbonate solutions of impouring, obtains white solid under stirring then.Filter, in the molten 80 milliliters of methylene dichloride of this white solid, to wherein diffusion, separate out white crystal, productive rate 95% with Skellysolve A.
2, Preparation of catalysts:
The above-mentioned gained white products of 2 mmoles is dissolved in the 20ml anhydrous tetrahydro furan (THF), stir the sodium hydride (NaH) that adds 2 mmoles down, reaction is after 60 minutes under anhydrous condition, stir down, be added dropwise to the dichloromethane solution that 40ml is dissolved with trans-[chlorine (1-naphthyl) (two (triphenylphosphine))] nickel (trans-chloro (1-naphthyl) bis (triphenylphosphane) nickel (II)) (2 mmole), react after 8 hours, filter, obtain product, productive rate 54.62%.
3, norbornene polymerization: will have the 250 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add the prepared catalyzer of 5 micromoles (μ mol) step 1,20 milliliter 1, the 2-ethylene dichloride, add again 6.209 the gram dicyclos [2.2.1] heptan-5-alkene-2-methyl alcohol (bicyclo[2,2,1] hept-5-ene-2-methanol) (dicyclo [2.2.1] heptan-5-alkene-2-methyl alcohol monomer and catalyst molar ratio are 10000) stirs after 5 minutes in the time of 25 ℃, add 7.2 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction added the 5ml isopropylcarbinol and stops polymerization after 30 minutes in the time of 25 ℃, added 100 milliliter 5 ‰ acidic alcohol (volume ratio) again, under room temperature, stirred 10 hours, leave standstill 2 hours after-filtration then, resulting polymers gets polymkeric substance 3.7643 in 80 ℃ of vacuum-dryings 40 hours, transformation efficiency 60.63%, catalyst activity are 1.5 * 10
6GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 2.2 * 10
6, number-average molecular weight (Mn) is 3.2 * 10
5, molecular weight distribution is 6.88.
Embodiment 12:
1, Preparation of catalysts: the preparation method is with embodiment 11.
2, norbornene polymerization: will have the 250 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add the prepared catalyzer of 5 micromoles (μ mol) step 1,20 milliliters of chlorobenzenes, add 9.416 gram norbornylenes (norbornene monomer and catalyst molar ratio are 20000) again, in the time of 25 ℃, stir after 5 minutes, add 7.2 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), in the time of 25 ℃, reacted for 20 seconds after, add the 5ml isopropylcarbinol and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 40 hours, get polymkeric substance 6.124 grams, transformation efficiency 65.04%, catalyst activity are 2.2 * 10
8GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 3.1 * 10
6, number-average molecular weight (Mn) is 2.2 * 10
5, molecular weight distribution is 14.1.
Embodiment 13:
1.N, the preparation of O bitooth ligand: with 30 milliliters of Glacial acetic acid, 8.8 the ammonium acetate of the 3-methoxyl group-2-hydroxy benzaldehyde of mmole (mmol) and the benzil of 8.6 mmoles (mmol) and 64 mmoles (mmol) places 250 milliliters of (mL) round-bottomed flasks, after the stirring and refluxing 4 hours, this mixing solutions is cooled to room temperature, in 500 milliliters of saturated sodium bicarbonate solutions of impouring, obtain white solid under stirring then.Filter, this white solid is dissolved in 50 milliliters of methylene dichloride, to wherein diffusion, separate out white crystal, productive rate 85% with Skellysolve A.
2. Preparation of catalysts:
The above-mentioned gained white products of 2 mmoles is dissolved in the 20ml anhydrous tetrahydro furan (THF), stir the sodium hydride (NaH) that adds 2 mmoles down, reaction is after 60 minutes under anhydrous condition, stir down, be added dropwise to the dichloromethane solution that 40ml is dissolved with trans-[chlorine (1-naphthyl) (two (triphenylphosphine))] nickel (trans-chloro (1-naphthyl) bis (triphenylphosphane) nickel (II)) (2 mmole), react after 8 hours, filter, obtain product, productive rate 93%.
3, norbornene polymerization: will have the 250 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add the prepared catalyzer of 5 micromoles (μ mol) step 1,20 milliliters of toluene, add again 15.219 the gram dicyclos [2.2.1] heptan-5-alkene-2-carboxylate methyl ester (bicyclo[2,2,1] hept-5-ene-2-carboxylic acidmethyl ester) (dicyclo [2.2.1] heptan-5-alkene-2-carboxylate methyl ester monomer and catalyst molar ratio are 20000), stir after 5 minutes in the time of 25 ℃, add 7.2 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 30 minutes in the time of 25 ℃, add the 5ml isopropylcarbinol and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 40 hours, get polymkeric substance 3.326 grams, transformation efficiency 21.85%, catalyst activity are 1.3 * 10
6GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 3.4 * 10
5, number-average molecular weight (Mn) is 2.1 * 10
5, molecular weight distribution is 1.6.
Embodiment 14:
1, Preparation of catalysts: the preparation method is with embodiment 13.
2, norbornene polymerization: will have the 250 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add the prepared catalyzer of 5 micromoles (μ mol) step 1,20 milliliters of toluene, add 1.00 gram norbornylenes (norbornene monomer and catalyst molar ratio are 2100) again, stir after 5 minutes in the time of 25 ℃, add 1.8 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 500), reaction is after 30 minutes in the time of 25 ℃, add the 5ml isopropylcarbinol and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 40 hours, get polymkeric substance 0.5653 gram, transformation efficiency 56.53%, catalyst activity are 1.13 * 10
5GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 7.5 * 10
5, number-average molecular weight (Mn) is 3.2 * 10
5, molecular weight distribution is 2.3.
Embodiment 15:
1, Preparation of catalysts: the preparation method is with embodiment 13.
2, norbornene polymerization: will have the 250 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add the prepared catalyzer of 5 micromoles (μ mol) step 1,30 milliliters of toluene, add 4.708 gram norbornylenes (norbornene monomer and catalyst molar ratio are 10000) again, stir after 5 minutes in the time of 25 ℃, add 1.8 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 500), reaction is after 30 minutes in the time of 25 ℃, add the 5ml isopropylcarbinol and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 40 hours, get polymkeric substance 1.3580 grams, transformation efficiency 28.84%, catalyst activity are 5.43 * 10
5GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 9.80 * 10
5, number-average molecular weight (Mn) is 2.94 * 10
5, molecular weight distribution is 3.33.
Embodiment 16:
1, N, the preparation of O bitooth ligand: with 30 milliliters of Glacial acetic acid, 8.8 the ammonium acetate of the 3-naphthyl-2-hydroxy benzaldehyde of mmole (mmol) and the benzil of 8.6 mmoles (mmol) and 64 mmoles (mmol) places 250 milliliters of (mL) round-bottomed flasks, after the stirring and refluxing 4 hours, this mixing solutions is cooled to room temperature, in 500 milliliters of saturated sodium bicarbonate solutions of impouring, obtain white solid under stirring then.Filter, this white solid is dissolved in 50 milliliters of methylene dichloride, to wherein diffusion, separate out white crystal, productive rate 85% with Skellysolve A.
2, Preparation of catalysts:
The above-mentioned gained white products of 2 mmoles is dissolved in the 20ml anhydrous tetrahydro furan (THF), stir the sodium hydride (NaH) that adds 2 mmoles down, reaction is after 60 minutes under anhydrous condition, stir down, be added dropwise to the dichloromethane solution that 40ml is dissolved with trans-[chlorine (1-naphthyl) (two (triphenylphosphine))] nickel (trans-chloro (1-naphthyl) bis (triphenylphosphane) nickel (II)) (2 mmole), react after 8 hours, filter, obtain product, productive rate 54%.
3, norbornene polymerization: will have the 250 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add the prepared catalyzer of 5 micromoles (μ mol) step 1,30 milliliters of toluene, add 4.708 gram norbornylenes (norbornene monomer and catalyst molar ratio are 10000) again, stir after 5 minutes in the time of 25 ℃, add 10.7 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 3000), reaction is after 30 minutes in the time of 25 ℃, add the 5ml isopropylcarbinol and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 40 hours, get polymkeric substance 1.8645 grams, transformation efficiency 39.60%, catalyst activity are 7.46 * 10
5GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 2.5 * 10
6, number-average molecular weight (Mn) is 3.4 * 10
5, molecular weight distribution is 7.4.
Embodiment 17:
1, Preparation of catalysts: the preparation method is with embodiment 16.
2, norbornene polymerization: will have the 250 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add the prepared catalyzer of 5 micromoles (μ mol) step 1,30 milliliters of toluene, add 4.708 gram norbornylenes (norbornene monomer and catalyst molar ratio are 10000) again, stir after 5 minutes in the time of 75 ℃, add 7.2 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 30 minutes in the time of 75 ℃, add the 5ml isopropylcarbinol and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 40 hours, get polymkeric substance 2.1510 grams, transformation efficiency 45.69%, catalyst activity are 8.61 * 10
5GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 1.3 * 10
6, number-average molecular weight (Mn) is 5.1 * 10
5, molecular weight distribution is 2.55.
Embodiment 18:
1, Preparation of catalysts: the preparation method is with embodiment 16.
2, norbornene polymerization: will have the 250 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add the prepared catalyzer of 5 micromoles (μ mol) step 1,30 milliliters of toluene, add again 8.31 the gram dicyclos [2.2.1] heptan-5-alkene-2-carboxylic acid, ethyl ester (bicyclo[2,2,1] hept-5-ene-2-carboxylic acidethyl ester) (dicyclo [2.2.1] heptan-5-alkene-2-carboxylic acid, ethyl ester monomer and catalyst molar ratio are 10000), stir after 5 minutes in the time of 75 ℃, add 7.2 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 30 minutes in the time of 75 ℃, add the 5ml isopropylcarbinol and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 40 hours, get polymkeric substance 2.8971 grams, transformation efficiency 34.86%, catalyst activity are 1.16 * 10
6GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 2.3 * 10
6, number-average molecular weight (Mn) is 7.5 * 10
5, molecular weight distribution is 3.07.
Embodiment 19:
1, Preparation of catalysts: the preparation method is with embodiment 16.
2, norbornene polymerization: will have the 250 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add the prepared catalyzer of 5 micromoles (μ mol) step 1,30 milliliters of toluene, add again 5.2558 the gram dicyclos [2.2.1] heptan-5-alkene-2,3-dimethyl dicarboxylate (bicyclo[2,2,1] hept-5-ene-2,3-dicarboxylic acid dimethyl ester) (dicyclo [2.2.1] heptan-5-alkene-2,3-dimethyl dicarboxylate monomer and catalyst molar ratio are 5000), in the time of 75 ℃, stir after 5 minutes, add 7.2 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 30 minutes in the time of 75 ℃, add the 5ml isopropylcarbinol and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again, under room temperature, stirred 10 hours, leave standstill 2 hours after-filtration then, resulting polymers gets polymkeric substance 1.354 grams in 80 ℃ of vacuum-dryings 40 hours, transformation efficiency 25.76%, catalyst activity are 5.4 * 10
5GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 3.4 * 10
5, number-average molecular weight (Mn) is 1.6 * 10
5, molecular weight distribution is 2.2.
Embodiment 20:
1, Preparation of catalysts: the preparation method is with embodiment 16.
2, norbornene polymerization: will have the 250 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add the prepared catalyzer of 5 micromoles (μ mol) step 1,30 milliliters of chlorobenzenes, add 5.3085 gram 5-ethylidene-dicyclo [2.2.1] hept-2-ene" (bicyclo[2 again, 2,1] alkene (norbornene monomer and catalyst molar ratio are 10000) hept-2-ene-5-ethylene), stir after 5 minutes in the time of 75 ℃, add 7.2 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 30 minutes in the time of 75 ℃, add the 5ml isopropylcarbinol and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 40 hours, get polymkeric substance 3.214 grams, transformation efficiency 60.54%, catalyst activity are 1.29 * 10
6GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 3.1 * 10
6, number-average molecular weight (Mn) is 7.6 * 10
5, molecular weight distribution is 4.08.
Claims (5)
1, a kind of nitrogen-oxygen nickel complex norbornene polymerization catalyst system, comprise Primary Catalysts and promotor, it is characterized in that, described Primary Catalysts is [2-(2 '-substituted 4-hydroxy phenyl)-4, the 5-diphenyl-imidazole]-(1-naphthyl)-(triphenylphosphine) nickel (II) title complex, its structure is shown below:
Wherein, R
1Be methyl, ethyl, propyl group, sec.-propyl, normal-butyl, the tertiary butyl, isobutyl-, methoxyl group, oxyethyl group, chlorine atom, bromine atoms or iodine atom.
Described promotor is a methylaluminoxane.
2, a kind of method for preparing the described catalyst system of claim 1, its key step comprises:
(A) N, the preparation of O bitooth ligand:
In 3 milliliters of Glacial acetic acid, add respectively: substituted salicylic aldehydes 0.8-1.2 mmole, benzil 0.8-1.5 mmole, ammonium acetate 6.4-7.5 mmole, place flask, after stirring and refluxing 4-15 hour, this mixing solutions is cooled to room temperature, in the impouring 500-2500 milliliter saturated sodium bicarbonate solution, obtains white solid under stirring then, filter, this white solid is dissolved in the 20-300 milliliter methylene dichloride, to wherein diffusion, separates out white products with Skellysolve A;
(B) preparation of Primary Catalysts:
Trans-[chlorine (1-naphthyl) (two (triphenylphosphine))] nickel (II) is dissolved in ratio in the 5-50ml methylene dichloride in every 1mmol, makes solution 1;
Step (A) gained white products is dissolved in the 2-50ml anhydrous tetrahydro furan by 1mmol, stirs the sodium hydride that adds down with white products equivalent, reaction was made solution 2 after 30-120 minute under anhydrous condition;
Stir down, press N, the mol ratio 1 of O bitooth ligand and trans-[chlorine (1-naphthyl) (two (triphenylphosphine))] nickel (II): 0.8-1 splashes into solution 1 in the solution 2, reacts 5 minutes-3 days, filters, and obtains product.
3, method as claimed in claim 2, it is characterized in that, substituted salicylic aldehydes described in the steps A is a salicylic aldehyde, the 3-tertiary butyl-2-hydroxy benzaldehyde, the 4-tertiary butyl-2-hydroxy benzaldehyde, 3,5-di-t-butyl-2-hydroxy benzaldehyde, 3-isobutyl--2-hydroxy benzaldehyde, 3-naphthyl-2-hydroxy benzaldehyde, 3-anthryl-2-hydroxy benzaldehyde, 3,5-diisobutyl-2-hydroxy benzaldehyde, 3-normal-butyl-2-hydroxy benzaldehyde, 4-normal-butyl-2-hydroxy benzaldehyde, 5-normal-butyl-2-hydroxy benzaldehyde, 4-nitro-2-hydroxy benzaldehyde, 4-nitroso-group-2-hydroxy benzaldehyde, 5-nitro-2-hydroxy benzaldehyde, 5-nitroso-group-2-hydroxy benzaldehyde, 6-nitro-2-hydroxy benzaldehyde, 6-nitroso-group-2-hydroxy benzaldehyde, 3-methoxyl group-2-hydroxy benzaldehyde, 4-methoxyl group-2-hydroxy benzaldehyde, 5-methoxyl group-2-hydroxy benzaldehyde, 6-methoxyl group-2-hydroxy benzaldehyde, 3,5-two iodo-2-hydroxy benzaldehydes, 4-iodo-2-hydroxy benzaldehyde, 5-iodo-2-hydroxy benzaldehyde, 3,5-two chloro-2-hydroxy benzaldehydes, 3-chloro-2-hydroxy benzaldehyde, 5-chloro-2-hydroxy benzaldehyde, 4-chloro-2-hydroxy benzaldehyde, 3,5-two bromo-2-hydroxy benzaldehydes, 4-fluoro-2-hydroxy benzaldehyde, 5-fluoro-2-hydroxy benzaldehyde, 3-fluoro-2-hydroxy benzaldehyde, 6-fluoro-2-hydroxy benzaldehyde, 3,5-two fluoro-2-hydroxy benzaldehydes, 4-bromo-2-hydroxy benzaldehyde, 3-methyl-2-hydroxy benzaldehyde, 4-methyl-2-hydroxy benzaldehyde, 5-methyl-2-hydroxy benzaldehyde, 6-methyl-2-hydroxy benzaldehyde, 3,5-dimethyl-2-hydroxy benzaldehyde, 3-sec.-propyl-2-hydroxy benzaldehyde, 4-sec.-propyl-2-hydroxy benzaldehyde, 3,5-di-isopropyl-2-hydroxy benzaldehyde, 3-ethyl-2-hydroxy benzaldehyde or 3,5-diethyl-2-hydroxy benzaldehyde.
4, claim 2 or 3 described methods, it is characterized in that, substituted salicylic aldehydes described in the steps A is a salicylic aldehyde, 4-methoxyl group-2-hydroxy benzaldehyde, 4-nitro-2-hydroxy benzaldehyde, the 3-tertiary butyl-2-hydroxy benzaldehyde, 3-naphthyl-2-hydroxy benzaldehyde, 3,5-di-t-butyl-2-hydroxy benzaldehyde, 3-isobutyl--2-hydroxy benzaldehyde, 3-anthryl-2-hydroxy benzaldehyde, 3,5-diisobutyl-2-hydroxy benzaldehyde, 3-normal-butyl-2-hydroxy benzaldehyde, 3,5-two iodo-2-hydroxy benzaldehydes, 3,5-two bromo-2-hydroxy benzaldehydes, 3,5-two chloro-2-hydroxy benzaldehydes, 3-sec.-propyl-2-hydroxy benzaldehyde, 3,5-di-isopropyl-2-hydroxy benzaldehyde, 3-ethyl-2-hydroxy benzaldehyde or 3,5-diethyl-2-hydroxy benzaldehyde.
5, a kind of as the application of catalyst system in norbornylene and derivative polymerization thereof as described in above-mentioned each claim.
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