CN1302025C - Olefin hydrocarbon polymerization catalyst of IVB group with Xifo alkali coordination and its preparation and use - Google Patents
Olefin hydrocarbon polymerization catalyst of IVB group with Xifo alkali coordination and its preparation and use Download PDFInfo
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Abstract
The present invention relates to an olefin hydrocarbon polymerization catalyst of a Schiff base coordination IVB group with a substituting group and a preparation method and use thereof. Aromatic amine containing ethyl and ethenyl is firstly prepared by the present invention, aromatic amine and 3-alkyl salicyl aldehyde react in anhydrous alcohol to make Schiff base ligand, and the ligand and MCl4 react to obtain the IVB group complex compound olefin polymerization catalyst of Schiff base. Copolymerization is triggered to the catalyst and styrene by a free radical initiator, and the high molecular Schiff base IVB group complex compound olefin polymerization catalyst is obtained. The catalyst of the present invention has high catalytic activity to the polymerization of ethylene, and the molecular weight of the obtained polymer is as high as 270 thousand (Mv). The macroscopic shape of the obtained polymer is in different shapes of a filament shape or a powder shape, etc. through controlling polymerization conditions. The present invention has the advantages of mild preparation condition of the catalyst, simple operation and high yield.
Description
Technical field
The invention belongs to catalyst preparation technical field, be specifically related to olefin polymerization catalysis of a kind of western Buddhist alkali coordination IVB group 4 transition metal and its production and application.
Technical background
Since polythene material commercialization before half a century, the polyolefin industry development is swift and violent.World today's scope polyolefine annual production exceeds 7,000 hundred million tons, wherein except that being that major part is by Z-N catalyzer and chromium-based catalysts preparation the new LDPE (film grade) of being produced by radical polymerization process (LDPE) than small part.Organometallic Chemistry and in the catalysis in olefine polymerization Application for Field has been opened up the New Times of polymer science.Since nineteen fifty-three Karl Ziegler and GiulioNatta discovery Ziegler/Natta olefin polymerization catalyst system, with rapid changepl. never-ending changes and improvements as the organometallics catalyzer of olefinic polymerization.What wherein have decisive significance is: the 60-70 age is found the SHOP catalyzer, IVB family metallocene catalyst because of using methylaluminoxane (MAO) to cause finding in 1980, nineteen ninety-five Brookhart study group finds that neutral diimine is that the nickelous of part and palladium complex are the catalyzer of the high branch high-molecular weight polymer of preparation, and the western Buddhist alkali of developing in 1999 is all joined type IVB group 4 transition metal olefin polymerization catalysis.And western Buddhist alkali all to join type IVB group 4 transition metal olefin polymerization catalysis be unique up to now catalyzer that can compare favourably with metallocene catalyst aspect catalytic activity, be named as the FI catalyzer.
Summary of the invention
The purpose of this invention is to provide the olefin polymerization catalysis and its production and application that a kind of contraposition at the aniline ring contains the western Buddhist alkali coordination IVB group 4 transition metal of alkyl.
The olefin polymerization catalysis that the present invention proposes is that wherein two chlorine atoms are in cis position by the octahedral complex of western Buddhist alkali [N-, O] and [Cl-] and the element coordination formation of IVB family; This catalyzer by with the catalyzer of styrene copolymerized formation high molecular, this two classes olefin polymerization catalysis has high reactivity.
Another object of the present invention provides the method for a class with FI Preparation of Catalyst high molecular weight polymers.The alkylene that this method is introduced in by western Buddhist alkali structure and styrene copolymerisation form the high molecular catalyzer, the secure satisfactory grades polymkeric substance of son amount of this catalyst olefinic polymerization.Overcome the low shortcoming of FI catalyzer resulting polymers molecular weight.
The component expression formula of catalyzer provided by the invention is [L
2MCl
2], L represents to contain or pbz polymer segmental west Buddhist alkali ligand not, and M is an IVB family metallic element, and Cl represents the chlorine atom.Concrete structure is as follows:
Wherein, R represents ethyl, vinyl, perhaps vinyl and styrene copolymerized formed polymer segment.M can select Ti or Zr etc. for use.They help catalysis to form the olefin polymerizating activity center by methylaluminoxane (MMAO).
Preparation of catalysts process provided by the invention is as follows:
(1) preparation of 3-alkyl salicylic aldehyde
The structural formula of 3-alkyl salicylic aldehyde is:
The preparation route is as follows:
The preparation of 3-alkyl salicylic aldehyde: under the Grignard reagent effect, heat in toluene solution with Paraformaldehyde 96, triethylamine and to finish reaction by vicinal alkylene phenol; 3-alkyl salicylic aldehyde crude product is used SiO
2Post/sherwood oil or hexane wash-out get pure product.
(2) preparation of aromatic amine
The structural formula of aromatic amine is:
(2-1) to the preparation of ethylaniline: synthetic route is as follows:
Ethylbenzene under-10 ℃-0 ℃ with nitrosonitric acid or the vitriol oil is nitrated must reduce to ethylaniline in acidic medium with iron powder then to nitro ethylbenzene.
(2-2) to the preparation of vinyl aniline: synthetic route is as follows
Bromination must be to the nitro bromobenzyl under heating condition with para-nitrotoluene, and the nitro bromobenzyl is obtained p-nitrophenyl ethene with uncommon (Wittig) reaction of loving and respect one's elder brother Wei of formaldehyde experience, experiences to reduce obtaining vinyl aniline then in alkaline medium with vat powder.
(3) preparation of Schiff base ligand
The structural formula of Schiff base ligand is:
Wherein, R is ethyl or vinyl.
With the dehydrated alcohol is solvent, and aromatic amine and 3-alkyl salicylic aldehyde at room temperature stirring reaction 15-20 hour filter, and wash filter residue with ethyl acetate, evaporation remove desolvate crude product, use SiO
2(10-15: 1) wash-out gets the pure product of Schiff base ligand for post, sherwood oil or hexane/ethyl acetate.The mass ratio that fragrance revolves amine and 3-alkyl salicylic aldehyde is 1-1.5: 1.
(4) western Buddhist alkali is all joined the preparation of type IVB group 4 transition metal olefin polymerization catalysis
The structural formula that west Buddhist alkali is all joined type IVB group 4 transition metal olefin polymerization catalysis is:
Wherein, M is Ti or Zr, and R is ethyl or vinyl.
Preparation of catalysts is carried out under anhydrous and oxygen-free and high purity inert gas (as argon gas) protective condition, is solvent with tetrahydrofuran (THF) or ether, the Schiff base ligand and the MCl that will be made by step (3)
4By 2.0-2.1: 1 (mol) proportioning feeds intake; The solution of Schiff base ligand 1.5-3 hour becomes lithium salts with the hexane solution reaction of n-Butyl Lithium or KH at-72 ℃ to the room temperature earlier, drops to MCl then
4Solution in stirring at room 12-18 hour, carry out aftertreatment again and get final product.For example, vacuum concentration is to doing; Add methylene chloride and stirred 10-20 minute, vacuum concentration is to doing again, and with dichloromethane extraction and the centrifugal lithium salts precipitation of removing, concentrated extract gets catalyzer with the normal hexane chromatography, productive rate 40-80%.Here MCl
4In M be IVB family element.
(5) high molecular Preparation of catalysts
The structural formula of high molecular catalyzer is:
Wherein, M is Ti or Zr, and R is vinyl and styrene copolymerized formed polymer segment.
Under the anaerobic anhydrous condition, to all join type IVB group 4 transition metal olefin polymerization catalysis, vinylbenzene, radical initiator Diisopropyl azodicarboxylate by the substituent western Buddhist alkali of alkene that contains that step (4) make, join successively in the 30-50ml solvent (as toluene) and mix, under 75-85 ℃ of temperature copolyreaction 15-20 hour then, wherein, the mol ratio of catalyzer, vinylbenzene, Diisopropyl azodicarboxylate is 1: 100-1000: 1-5.Carry out aftertreatment after the reaction and get final product, comprise being cooled to room temperature, vacuum concentration is removed most of solvent, add hexane and stir, centrifugal, tell supernatant liquid, solid is with toluene dissolving, normal hexane precipitation, and is centrifugal, remove supernatant liquid, and it is colourless to the upper strata clear liquid to repeat this process; The jelly of gained drying under vacuum sonization catalyst solid powder that secures satisfactory grades.
Above-mentioned catalyzer of the present invention is used for vinyl polymerization, and concrete steps are as follows:
Polyreaction is carried out under the anhydrous and oxygen-free condition, in normal pressure or highly compressed ethene atmosphere downhill reaction system, add 35-90ml solvent, 0.3-5ml promotor methylaluminoxane, the described catalyzer of 0.5-1ml successively, in room temperature to 80 ℃ following reaction 15-60 minute, the input of termination ethene, with the ethanolic soln termination reaction that contains 1% hydrochloric acid, products therefrom is filtered, use washing with alcohol, and got polyethylene in 30-50 ℃ of vacuum-drying 20-30 hour.
Embodiment
The preparation of embodiment 1:3-tertiary butyl salicylic aldehyde
The preparation of Grignard reagent: the MAGNESIUM METAL that takes by weighing 1.848g (0.077mol); join in the 100ml there-necked flask; and in there-necked flask, adding a magnetic stir bar, fit on constant pressure funnel, reflux condensing tube and protection airbag eliminate the moisture content in the device under vacuum.In constant pressure funnel, add the 50ml anhydrous diethyl ether then, in there-necked flask, add wherein about 30ml anhydrous diethyl ether by constant pressure funnel again.(5.2ml, 0.070mol) anhydrous monobromethane shake constant pressure funnel and make the diethyl ether solution of monobromethane evenly mixed to add 7.63g again in constant pressure funnel.Start magnetic agitation, open reflux condensation mode water, the rate of addition of diethyl ether solution of control monobromethane makes reaction keep gentle reflux, keeps 30min after being added dropwise to complete and makes and react completely.
The preparation of 3-tertiary butyl salicylic aldehyde: take by weighing 9.000 (0.060mol) o-tert-butylphenol with the 250ml there-necked flask; add magnetic stir bar; assembling constant pressure funnel, reflux condensing tube and protection airbag; there-necked flask is the oil bath of assembling whiteruss down; open magnetic agitation, under vacuum, eliminate the moisture content in the device and charge into argon gas.Add 40ml anhydrous tetrahydro furan (THF) to there-necked flask, shift prepared Grignard reagent supernatant liquor in constant pressure funnel by steel pipe, and wash with the 20ml anhydrous diethyl ether, supernatant liquor is transferred in the constant pressure funnel equally.Open reflux condensation mode water, at room temperature drip Grignard reagent to there-necked flask by constant pressure funnel, about 45min adds, and keeps reaction 2hr again, will discharge the gas that is produced pitch time in this reinforced process.In reaction system, add the 100ml dry toluene then, under vacuum, remove low-boiling point materials such as tetrahydrofuran (THF), ether.(95%, 0.150mol) (about 8hr that refluxes in the 100-110 ℃ of oil bath finishes reaction for 12.5ml, 0.090mol) triethylamine and 50ml toluene for Paraformaldehyde 96,9.090g to add 4.700g in there-necked flask.Prepare 10% aqueous solution 300ml of 36.5% concentrated hydrochloric acid, under the ice-water bath cooling, slowly add above-mentioned reaction mixture and fully stirring.The upper strata organic layer is collected in the mixed system phase-splitting, again with the organic layer of extracted with diethyl ether to the phase-splitting colourless till.Merge organic layer, eliminate solvent with anhydrous sodium sulfate drying, filtration, evaporation and get crude product, use SiO
2Post/sherwood oil wash-out, the solution of the orange band of collection the first layer, it is 3-tertiary butyl salicylic aldehyde 9.078g (0.051mol) that evaporating solvent gets orange red oil, productive rate 85%, molecular formula C
11H
14NO
2 1HNMR(CDCl
3)：δ1.419(s，9H，t-Bu)，6.962(dd，1H，aromatic-H)，7.370(d，1H，aromatic-H)，7.534(d，1H，aromatic-H)，9.887(s，1H，CHO)，11.788(s，1H，OH)。
Embodiment 2: to the preparation of nitro ethylbenzene
At the mixture that in 53.000g (0.500mol) ethylbenzene that stirs, drips 34.650g (0.550mol) nitrosonitric acid and 98% sulfuric acid 52g (0.520mol) under-10 to-5 ℃.Colourless mixture is flavescence gradually.Drip off the afterreaction thing and stir 40min at 40 ℃.Phase-splitting removes sub-cloud acid, and organic layer is distinguished water, saturated sodium bicarbonate solution, water washing, uses anhydrous magnesium sulfate drying, and vacuum fractionation (88 ℃, 11mmHg) must be faint yellow to nitro ethylbenzene liquid 55.120g, productive rate 73%.FT-IR：3110，3079，2972，2937，2877，2451，1927，1798，1682，1600，1518，1496，1458，1346，1317，1240，1180，1110，1054，1015，967，891，856，788，772，746，696，663，632，615，510。
1HNMR(CDCl
3)：δ1.289(t，3H，CH
3)，2.723-2.799(q，2H，CH，)，7.330-7.359(d，2H，aromatic-H)，8.146-8.152(d，2H，aromatic-H)。
Embodiment 3: to the preparation of ethylaniline
To nitro ethylbenzene with excess iron powder in the aqueous ammonium chloride solution medium of 1mol/L under 60-80 ℃, adopt the mode in batches add iron powder reduce red liquid to ethylaniline, productive rate about 50%.FT-IR：3570，3450，2940，1610，1520，1280，1190，1120，820。
1HNMR(CDCl
3)：δ1.1(t，3H，CH
3)，δ2.5(q，2H，CH
2)，δ3.2(m，2H，NH
2)，δ6.4(d，2H，aromatic-H)，δ6.8(d，2H，aromatic-H)。
Embodiment 4: to the preparation of nitro bromobenzyl
Under 145 ℃ in the para-nitrotoluene 68.500g (0.500mol) that stirs dropping simple substance bromine 84.000g (0.525mol, 27ml).The tail gas that reaction produces absorbs with alkaline aqueous solution.After dripping, keeps simple substance bromine reaction 0.5hr.Make reactant be cooled to 100 ℃ of agreements, slowly pour in about 500ml sherwood oil (boiling range 60-90 ℃) at the following reactant of stirring cooling conditions.Filtering and collecting cooled solid is crude product.Getting white needle-like crystals with sherwood oil (boiling range 60-90 ℃) recrystallization is to nitro bromobenzyl 44.280g, productive rate 41%.Molecular formula C
7H
6NO
2Br.FT-IR：3100，3035，2860，2452，1611，1598，1540，1485，1442，1417，1392，1347，1324，1297，1226，1202，1175，1106，1092，1012，857，817，753，694，630，597，525，470。
1HNMR(CDCl
3)：δ4.524(s，2H，CH
2Br)，7.5545-7.5913(d，2H，aromatic-H)，8.201-8.230(d，2H，aromatic-H).
Embodiment 5: bromination is to the preparation of nitrobenzyl triphenyl phosphonium
Under noble gas protection, 85 ℃ to nitro bromobenzyl 10.800g (0.050mol) and triphenylphosphine 13.100g (0.050mol) stirring reaction 3hr in 150ml benzene.Produce a large amount of white precipitates.Cooled and filtered is collected this precipitation, and with the ether washing, vacuum-drying gets white solid powder 23.183g, productive rate 97%.Molecular formula C
25H
21NO
2PBr.FT-IR：3058，2991，2862，2772，1822，1593，1519，1485，1437，1347，1163，1111，996，871，858，750，719，690，635，547，525，506，497。
1HNMR(CDCl
3)：δ1.597(s，2H，CH
2)，5.884-5.935(d，2H，aromatic-H)，7.265-7.438(d，2H，aromatic-H)，7.460-7.913(m，15H，aromatic-H)。
Embodiment 6: the preparation of p-nitrophenyl ethene
In a 250ml reaction flask that contains magnetic stir bar, add bromination to nitrobenzyl triphenyl phosphonium 19.120g (0.040mol) and 37-40% formaldehyde solution 75ml.Under room temperature, stirring, slowly drip the 30ml aqueous solution that is dissolved with 1.600g sodium hydroxide.Drip each time after the solution redness is taken off fully.After finishing, reaction uses extracted with diethyl ether, it is crude product that collected organic layer also uses anhydrous sodium sulfate drying, vacuum-evaporation to get yellow oil, and crude product is through silica gel column chromatography, it is p-nitrophenyl ethene 5.424g that petroleum ether/ethyl ether (10: 1) gets the white needle-like crystals thing as eluent, productive rate 91%.Molecular formula C
8H
7NO
2FT-IR：3078，3013，2939，2843，2638，2449，1927，1855，1795，1686，1628，1596，1514，1452，1427，1403，1344，1319，1290，1204，1182，1110，1030，1012，989，925，858，827，777，765，707，615，536，489，439。
1HNMR(CDCl
3)：δ5.488-5.964(dd，2H，＝CH
2)，6.740-6.799(q，1H，＝CH)，7.528-7.557(d，2H，aromatic-H)，8.183-8.212(d2H，aromatic).
Embodiment 7: bromination 1,1 '-di-n-octyl-4, the preparation of 4 '-dipyridyl
4,4 '-dipyridyl and two times of excessive n-Octyl Bromides stir 3hr at 85-90 ℃ and form a large amount of cured products, use washed with dichloromethane, and solid collected by filtration gets the yellow-green colour chip solid with ethyl alcohol recrystallization, productive rate 65%.Molecular formula C
26H
42N
2Br
2 1HNMR(D
2O)：δ0.729(t，6H，2CH
3)，1.037-1.249(m，24H，12CH
2)，4.608(t，4H，2BrCH
2)，8.415-8.435(d，4H，pyridium-H)，8.986-9.008(d，4H，pyridium-H).
Embodiment 8: to the preparation of vinyl aniline
The stirring of reaction flask make-up machinery, reflux condensing tube and the dropping funnel of 500ml, add p-nitrophenyl ethene 4.470g (0.030mol), bromination 1 in the reaction flask, 1 '-di-n-octyl-4,4 '-dipyridyl 0.813g (1.5mmol), 20ml water and 160ml methylene dichloride are added with the aqueous solution of the 110ml that contains salt of wormwood 20.700g (0.150mol) and sodium hyposulfate 23.490g (0.135mol) in the dropping funnel.Reaction system is protected with noble gas, drips stirring reaction 8hr down at 35 ℃.Lower floor's organic layer is collected in the cooling back.The water dichloromethane extraction, the organic phase of merging is used anhydrous sodium sulfate drying, and vacuum-evaporation gets adopting dark liquid, uses silica gel column chromatography, and petroleum ether/ethyl ether (10: 1) wash-out gets white plates crystal 1.264g, productive rate 35.4%.Molecular formula C
8H
9N.FT-IR：3361，3220，3083，3055，3005，2976，2868，2711，2613，2355，1969，1888，1779，1706，1660，1609，1516，1483，1437，1413，1366，1317，1284，1208，1178，1120，1092，1071，1027，992，894，831，748，722，695，641，541，493。
1HNMR(CDCl
3)：δ3.650(s，2H，NH
2)，4.981-5.569(dd，2H，＝CH
2)，6.563-6.657(q，1H，＝CH)，6.619-6.646(d，2H，aromatic-H)，7.211-7.238(d，2H，aromatic-H).
Embodiment 9: the preparation of western Buddhist alkali N-(4 '-ethenylphenyl)-3-tertiary butyl salicylic alidehyde imine part
Take by weighing 3.560g (0.020mol) 3-tertiary butyl salicylic aldehyde with the 100ml there-necked flask, add magnetic stir bar, assembling constant pressure funnel and protection airbag are opened magnetic agitation, fill exhaust three times with the vacuum argon system.Add exsiccant 4
Molecular sieve 3.077g, 30ml warp
The dehydrated alcohol that molecular sieve was handled.In constant pressure funnel, add 20ml through 4
Dehydrated alcohol that molecular sieve is handled and 2.380g (0.020mol) at room temperature drop in the there-necked flask vinyl aniline, and about 30min adds.Stirring reaction 15hr at room temperature filters then, washs filter residue with ethyl acetate, collects filtrate and washing lotion, evaporation remove desolvate crude product, use SiO
2Post, petrol ether/ethyl acetate (15: 1) wash-out are collected the solution of the orange colour band of the first layer, evaporation remove desolvate orange red oily west Buddhist alkali 3-tertiary butyl salicylidene to the pure product 5.022g of vinyl benzene amine ligand (0.018mol), productive rate 90%.FT-IR：3084，2999，2957，2910，2873，1615，1593，1575，1506，1483，1456，1434，1406，1391，1361，1310，1274，1235，1192，1171，1145，1114，1088，1025，1012，988，971，930，908，868，842，798，750，668，641，612，560，524，502，408。
1HNMR(CDCl
3)：δ1.471(s，9H，t-Bu)，5.249-5.793(dd，2H，ethenyl＝CH
2)，6.607-6.689(q，1H，ethenyl＝CH)，6.879-7.480(m，7H，aromatic-H)，8.646(s，1H，CH＝N)，13.899(s，1H，OH).
Embodiment 10: the preparation of western Buddhist alkali N-(4 '-ethylphenyl)-3-tertiary butyl salicylic alidehyde imine part
Take by weighing 3.560g (0.020mol) 3-tertiary butyl salicylic aldehyde with the 100ml there-necked flask, add magnetic stir bar, assembling constant pressure funnel and protection airbag are opened magnetic agitation, fill exhaust three times with the vacuum argon system.Add exsiccant 4
Molecular sieve 3.077g, 30ml are through 4
The dehydrated alcohol that molecular sieve is handled.In constant pressure funnel, add 20ml through 4
The dehydrated alcohol that molecular sieve is handled reaches ethylaniline 2.420g (0.020mol), at room temperature drops in the there-necked flask, and about 30min adds.Stirring reaction 15hr at room temperature filters then, washs filter residue with ethyl acetate, collects filtrate and washing lotion, evaporation remove desolvate crude product, use SiO
2Post, petrol ether/ethyl acetate (15: 1) wash-out are collected the solution of the orange colour band of the first layer, evaporation remove desolvate red western Buddhist alkali 3-tertiary butyl salicylidene to the pure product 5.339g of ethylaniline part (0.019mol), productive rate 95%.Molecular formula C
19H
23NO.FT-IR：3382，3055，2962，2872，1617，1596，1574，1508，1483，1458，1434，1390，1361，1310，1273，1237，1191，1174，1145，1115，1088，1061，1017，971，931，867，847，836，798，750，697，668，612，562，538，494，408.
1HNMR(CDCl
3)：δ1.258(t，3H，CH
3)，1.471(s，9H，t-Bu)，2.637-2.713(q，2H，CH
2)，6.838-7.406(m，7H，aromatic-H)，8.621(s，1H，CH＝N)，13.986(s，1H，
OH).
Embodiment 11: the preparation of dichloride [N-(4 '-ethenylphenyl)-3-tertiary butyl salicylic alidehyde imine] network zirconium (IV)
Under the anhydrous and high-purity argon gas protective condition, take by weighing 3-tertiary butyl salicylidene in anaerobic, add 20ml tetrahydrofuran (THF) (THF), be cooled to-72 ℃ with ethanol/the dry ice bath with the magnetic agitation dissolving to vinyl benzene amine ligand 1.674g (6.00mmol).Measure the hexane solution 3.83ml (6.12mmol, 1.02 times) of 1.6M n-Butyl Lithium then with syringe, slowly be injected under-72 ℃ in the THF solution of 3-tertiary butyl salicylidene allyl amine part, have gas to emit this moment.Remove dry ice/ethanol bath after adding, at room temperature the about 2.5hr of reaction becomes lithium salts, and this process produces the gas of expanded by heating.Have to an exsiccant and to add the anhydrous and oxygen-free THF20ml that handles through sodium Metal 99.5 in the reaction flask of magnetic stir bar, take by weighing zirconium tetrachloride (ZrCl
4) white powder 0.713g (98%, 3mmol), under agitation slowly be added among the THF, at this moment ZrCl by the glass Y-tube
4Dissolve colourless solution, be cooled to-72 ℃ with ethanol/the dry ice bath, above-mentioned lithium salt solution is dropped to ZrCl
4In the solution, remove dry ice/ethanol bath after being added dropwise to complete, stirring at room 15hr hour.Under vacuum, be concentrated into driedly then, add the 20ml methylene dichloride, restir 15min, vacuum concentration is to doing then.With 20ml * 3 dichloromethane extractions and centrifugation lithium salts, migrate out supernatant liquor with steel pipe, concentrate this extraction liquid, get catalyst solid thing 1.077g-1.292g, productive rate 50-60% with the normal hexane chromatography.Molecular formula C
38H
40N
2O
2Cl
2Zr.EI-MS：718，667，622，578，552，538，524，279，264，237.FT-IR：3078，2957，2908，2871，1605，1589，1552，1504，1481，1460，1427，1388，1362，1318，1288，1266，1243，1189，1172，1149，1111，1089，1015，988，909，879，864，843，798，755，685，651，628，589，547，496，449，434.Analysisfound(C
38H
40N
2O
2Cl
2Zr)：C63.76(63.51)，H5.74(5.57)，N4.45(3.90)。This catalyst structure is as follows:
Embodiment 12: the preparation of dichloride [N-(4 '-ethylphenyl)-3-tertiary butyl salicylic alidehyde imine] network zirconium (IV)
Under the anhydrous and high-purity argon gas protective condition, take by weighing 3-tertiary butyl salicylidene in anaerobic, add 20ml tetrahydrofuran (THF) (THF), be cooled to-72 ℃ with ethanol/the dry ice bath with the magnetic agitation dissolving to ethylaniline ligand 1 .686g (6.00mmol).Measure the hexane solution 3.83ml (6.12mmol, 1.02 times) of 1.6M n-Butyl Lithium with syringe then and slowly be injected under-72 ℃ in the THF solution of part, have gas to emit this moment.Remove dry ice/ethanol bath after adding, at room temperature the about 2.5hr of reaction becomes lithium salts, and this process produces the gas of expanded by heating.Have to an exsiccant and to add the anhydrous and oxygen-free THF20ml that handles through sodium Metal 99.5 in the reaction flask of magnetic stir bar, take by weighing zirconium tetrachloride (ZrCl
4) white powder 0.713g (98%, 3mmol), under agitation slowly be added among the THF, at this moment ZrCl by the glass Y-tube
4Dissolve colourless solution, be cooled to-72 ℃ with ethanol/the dry ice bath, above-mentioned lithium salt solution is dropped to ZrCl
4In the solution, remove dry ice/ethanol bath after being added dropwise to complete, stirring at room 15hr hour.Under vacuum, be concentrated into driedly then, add the 20ml methylene dichloride, restir 15min, vacuum concentration is to doing then.With 20ml * 3 dichloromethane extractions and centrifugation lithium salts, migrate out supernatant liquor with steel pipe, concentrate this extraction liquid, get catalyst solid thing 1.083g-1.230g, productive rate 50-60% with the normal hexane chromatography.Molecular formula C
38H
44N
2O
2Cl
2Zr.EI-MS：722，684，669，634，598，440，424，282，264，237，217，203.FT-IR：3078，2960，2869，1610，1589，1554，1502，1483，1462，1428，1390，1360，1319，1283，1266，1242，1189，1149，1119，1091，1062，1049，1018，983，963，943，878，862，839，798，755，730，684，631，605，584，562，542，514，502，480，463，445，436.Analysis?found(C
38H
44N
2O
2Cl
2Zr)：C63.24(63.16)，H6.51(6.09)，N4.25(3.88)。This catalyst structure is as follows:
Embodiment 13: the preparation of dichloride [N-(4 '-ethenylphenyl)-3-tertiary butyl salicylic alidehyde imine] network titanium (IV):
In anaerobic under the anhydrous and high-purity argon gas protective condition; take by weighing 3-tertiary butyl salicylidene to vinyl benzene amine ligand 1.674g (6.00mmol); add the 20ml anhydrous diethyl ether and dissolve, at-72 ℃ of hexane solution 3.83ml (6.12mmol, 1.02 times) that add the 1.6M n-Butyl Lithium down with magnetic agitation.Remove dry ice/ethanol bath after adding, at room temperature the about 2.5hr of reaction becomes lithium salts, and this process produces the gas of expanded by heating.Have to an exsiccant and to add the anhydrous diethyl ether 20ml that handles through sodium Metal 99.5 in the reaction flask of magnetic stir bar, take by weighing titanium tetrachloride (TiCl
4) 0.57g (3mmol), under agitation slowly mix with ether by the glass Y-tube, get yellow suspension liquid.Be cooled to-72 ℃ then, add the lithium salt solution of prepared part, remove dry ice/ethanol bath after being added dropwise to complete, stirring at room 15hr hour.Under vacuum, be concentrated into dried then.With 20ml * 3 dichloromethane extractions and centrifugation lithium salts, migrate out supernatant liquor with steel pipe, concentrate this extraction liquid, get catalyst solid thing 1.588g, productive rate 78.4% with the normal hexane chromatography.EI-MS：639(M-Cl)，604。FT-IR：3082，2958，2906，2870，1605，1589，1553，1503，1481，1462，1423，1384，1363，1315，1284，1264，1242，1190，1171，1148，1112，1087，1015，987，906，882，865，844，814，753，691，653，631，589，552，494，470，441。Ultimate analysis (C
38H
40N
2O
2Cl
2Ti calculated value %): C67.05 (67.56), H6.37 (5.92), N4.75 (4.15).
Embodiment 14: high molecular west Buddhist alkali is all joined the preparation of type IVB group 4 transition metal olefin polymerization catalysis
Under the anaerobic anhydrous condition, the western Buddhist alkali that contains vinyl of embodiment 13 gained is all joined type IVB group 4 transition metal olefin polymerization catalysis 0.222g (0.3mmol), vinylbenzene 6ml, Diisopropyl azodicarboxylate (AIBN) 0.216g, 30ml toluene adds in the 50ml ampere bottle of being with magnetic stir bar successively, stirring reaction 18hr in 80 ℃ oil bath.Be cooled to room temperature, vacuum concentration is removed most of solvent, gets the opaque mixture of yellow gluey thickness, add 20ml hexane stirring, centrifugal, tell supernatant liquid, solid with toluene dissolving, normal hexane precipitation, centrifugal, remove supernatant liquid, it is colourless to the upper strata clear liquid to repeat this process.The solid of gained drying under vacuum is light yellow solid powder 1.292g.ICP-AES：Zr8.49mg/g。GPC：PDI＝1.4483，Mn＝14948。This catalyst structure is as follows:
Embodiment 15: the preparation of olefin polymerization catalysis solution and promotor
(1) take by weighing the catalyst fines 0.0154g of embodiment 11 gained, add 25ml toluene, vibration dissolve the homogeneous phase pale yellow solution, numbering: CVN, concentration is 0.86umolZr/ml;
(2) take by weighing the catalyst fines 0.0100g of embodiment 12 gained, add 20ml toluene, vibration dissolve the homogeneous phase pale yellow solution, numbering: CET, concentration is 0.69umolZr/ml;
(3) take by weighing the catalyst fines 0.0107g of embodiment 13 gained, add 10ml toluene, vibration dissolve the homogeneous phase pale yellow solution, numbering: CVNT, concentration is 1.58umolTi/ml;
(4) the catalyst fines 0.1190g that takes by weighing embodiment 14 gained adds 15ml toluene, vibration dissolve the homogeneous phase pale yellow solution, numbering: CPSC10, concentration is 0.74umolZr/ml;
Promotor is the toluene solution of methylaluminoxane (MMAO), and concentration is 2.20M.
Polymerization termination and polyethylene precipitation agent are acidic ethanol, are that the concentration that contains 36.5% hydrochloric acid is 1% industrial alcohol solution.
Embodiment 16: vinyl polymerization
200ml glass reaction bottle toasts under the vacuum in advance, feeds the normal pressure ethylene gas, and ethene air pressure is normal pressure.Add 40ml toluene then, under agitation add 0.5mlMMAO, 1mlCVNT and 10ml toluene successively.Stirring reaction 30min under room temperature stops the input of ethylene gas then, stops stirring, in the impouring 200ml acidic ethanol, filter, with resulting polymers washing with alcohol, filtration, and, getting the 0.445g polymkeric substance in 40 ℃ of vacuum-dryings 24 hours, catalytic activity is 0.562 * 10
6G PE/molTi.hr.Polyethylene viscosity-average molecular weight 344686, PDI=4.455.DSC: unimodal, fusing point Tm=135.539 ℃, melting enthalpy Δ Hm=157.479J/g.
Embodiment 17: vinyl polymerization
200ml glass reaction bottle toasts under the vacuum in advance, feeds the normal pressure ethylene gas, and ethene air pressure is normal pressure.Add 40ml toluene then, under agitation add 0.5mlMMAO, 1mlCVN and 10ml toluene successively.Stirring reaction 30min under room temperature stops the input of ethylene gas then, stops stirring, and in the impouring 200ml acidic ethanol, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 0.550g, and catalytic activity is 1.282 * 10
6G PE/molZr.hr.Polyethylene viscosity-average molecular weight 10351, DSC: unimodal, fusing point Tm=127.742 ℃, melting enthalpy Δ Hm=229.644J/g.
Embodiment 18: vinyl polymerization
200ml glass reaction bottle toasts under the vacuum in advance, feeds the normal pressure ethylene gas, and ethene air pressure is normal pressure.Add people 40ml toluene then, under agitation add 1.0mlMMAO, 1mlCVN and 10ml toluene successively.Stirring reaction 30min under room temperature stops the input of ethylene gas then, stops stirring, and in the impouring 200ml acidic ethanol, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 1.124g, and catalytic activity is 2.620 * 10
6G PE/molZr.hr.Polyethylene viscosity-average molecular weight 10118, DSC: unimodal, fusing point Tm=124.267 ℃, melting enthalpy Δ Hm=213.309J/g.
Embodiment 19: vinyl polymerization
200ml glass reaction bottle toasts under the vacuum in advance, feeds the normal pressure ethylene gas, and ethene air pressure is normal pressure.Add people 40ml toluene then, under agitation add 1.5mlMMAO, 1mlCVN and 10ml toluene successively.Stirring reaction 30min under room temperature stops the input of ethylene gas then, stops stirring, and in the impouring 200ml acidic ethanol, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 1.360g, and catalytic activity is 3.170 * 10
6G PE/molZr.hr.Polyethylene viscosity-average molecular weight 7609, DSC: bimodal, fusing point Tm=117.33 ℃, melting enthalpy Δ Hm=201.17J/g; Tm=123.95 ℃, melting enthalpy Δ Hm=232.39J/g.
Embodiment 20: vinyl polymerization
200ml glass reaction bottle toasts under the vacuum in advance, feeds the normal pressure ethylene gas, and ethene air pressure is normal pressure.Add people 40ml toluene then, under agitation add 2.0mlMMAO, 1mlCVN and 10ml toluene successively.Stirring reaction 30min under room temperature stops the input of ethylene gas then, stops stirring, and in the impouring 200ml acidic ethanol, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 2.437g, and catalytic activity is 5.681 * 10
6G PE/molZr.hr.Polyethylene viscosity-average molecular weight 6596, DSC: bimodal, fusing point Tm=110.33 ℃; Fusing point Tm=125.347 ℃, melting enthalpy Δ Hm=229.698J/g.
Embodiment 21: vinyl polymerization
200ml glass reaction bottle toasts under the vacuum in advance, feeds the normal pressure ethylene gas, and ethene air pressure is normal pressure.Add people 40ml toluene then, under agitation add 3.0mlMMAO, 1mlCVN and 10ml toluene successively.Stirring reaction 30min under room temperature stops the input of ethylene gas then, stops stirring, and in the impouring 200ml acidic ethanol, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 3.091g, and catalytic activity is 7.206 * 10
6G PE/molZr.hr.Polyethylene viscosity-average molecular weight 4708, DSC: broad peak, fusing point Tm=99.67 ℃; Fusing point Tm=116.67 ℃; Fusing point Tm=122.054 ℃, melting enthalpy Δ Hm=221.659J/g.
Embodiment 22: vinyl polymerization
200ml glass reaction bottle toasts under the vacuum in advance, feeds the normal pressure ethylene gas, and ethene air pressure is normal pressure.Add people 40ml toluene then, under agitation add 0.5mlMMAO, 1.5mlCET and 10ml toluene successively.Stirring reaction 30min under room temperature stops the input of ethylene gas then, stops stirring, and in the impouring 200ml acidic ethanol, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 0.739g, and catalytic activity is 1.423 * 10
6G PE/molZr.hr.Polyethylene viscosity-average molecular weight 7720.
Embodiment 23: vinyl polymerization
200ml glass reaction bottle toasts under the vacuum in advance, feeds the normal pressure ethylene gas, and ethene air pressure is normal pressure.Add people 40ml toluene then, under agitation add 1.0mlMMAO, 1.5mlCET and 10ml toluene successively.Stirring reaction 30min under room temperature stops the input of ethylene gas then, stops stirring, and in the impouring 200ml acidic ethanol, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 1.573g, and catalytic activity is 3.028 * 10
6G PE/molZr.hr.Polyethylene viscosity-average molecular weight 7782, DSC: unimodal, fusing point Tm=127.649 ℃, melting enthalpy Δ Hm=219.289J/g (heating up for the first time).
Embodiment 24: vinyl polymerization
200ml glass reaction bottle toasts under the vacuum in advance, feeds the normal pressure ethylene gas, and ethene air pressure is normal pressure.Add people 40ml toluene then, under agitation add 1.5mlMMAO, 1.0mlCET and 10ml toluene successively.Stirring reaction 30min under room temperature stops the input of ethylene gas then, stops stirring, and in the impouring 200ml acidic ethanol, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 1.512g, and catalytic activity is 4.367 * 10
6G PE/molZr.hr.Polyethylene viscosity-average molecular weight 7782.
Embodiment 25: vinyl polymerization
200ml glass reaction bottle toasts under the vacuum in advance, feeds the normal pressure ethylene gas, and ethene air pressure is normal pressure.Add people 40ml toluene then, under agitation add 0.5mlMMAO, 1.0mlCET and 10ml toluene successively.Stirring reaction 30min under room temperature stops the input of ethylene gas then, stops stirring, and in the impouring 200ml acidic ethanol, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 1.851g, and catalytic activity is 5.346 * 10
6G PE/molZr.hr.Polyethylene viscosity-average molecular weight 7873.
Embodiment 26: vinyl polymerization
200ml glass reaction bottle toasts under the vacuum in advance, feeds the normal pressure ethylene gas, and ethene air pressure is normal pressure.Add people 40ml toluene then, under agitation add 0.5mlMMAO, 1.0mlCET and 10ml toluene successively.Stirring reaction 30min under room temperature stops the input of ethylene gas then, stops stirring, and in the impouring 200ml acidic ethanol, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 2.701g, and catalytic activity is 7.800 * 10
6G PE/molZr.hr.Polyethylene viscosity-average molecular weight 5448.
Embodiment 27: vinyl polymerization
200ml glass reaction bottle toasts under the vacuum in advance, feeds the normal pressure ethylene gas, and ethene air pressure is normal pressure.Add people 40ml toluene then, under agitation add 0.5mlMMAO, 1mlCPSC10 and 10ml toluene successively.Stirring reaction 30min under room temperature stops the input of ethylene gas then, stops stirring, and in the impouring 200ml acidic ethanol, filters, and gets traces of polymer.
Embodiment 28: vinyl polymerization
200ml glass reaction bottle toasts under the vacuum in advance, feeds the normal pressure ethylene gas, and ethene air pressure is normal pressure.Add people 40ml toluene then, under agitation add 2.0mlMMAO, 1.0mlCPSC10 and 10ml toluene successively.Stirring reaction 30min under room temperature stops the input of ethylene gas then, stops stirring, and in the impouring 200ml acidic ethanol, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 0.564g, and catalytic activity is 1.524 * 10
6G PE/molZr.hr.Polyethylene viscosity-average molecular weight 42612.
Embodiment 29: vinyl polymerization
200ml glass reaction bottle toasts under the vacuum in advance, feeds the normal pressure ethylene gas, and ethene air pressure is normal pressure.Add people 40ml toluene then, under agitation add 3.5mlMMAO, 1.0mlCPSC10 and 10ml toluene successively.Stirring reaction 30min under room temperature stops the input of ethylene gas then, stops stirring, and in the impouring 200ml acidic ethanol, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 1.412g, and catalytic activity is 3.816 * 10
6G PE/molZr.hr.Polyethylene glues equal molecule 13479.
Embodiment 30: vinyl polymerization
200ml glass reaction bottle toasts under the vacuum in advance, feeds the normal pressure ethylene gas, and ethene air pressure is normal pressure.Add people 40ml toluene then, under agitation add 5.0mlMMAO, 1.0mlCPSC10 and 10ml toluene successively.Stirring reaction 30min under room temperature stops the input of ethylene gas then, stops stirring, and in the impouring 200ml acidic ethanol, filters, and with resulting polymers washing with alcohol, filtration, and in 40 ℃ of vacuum-dryings 24 hours, gets 0.968g, and catalytic activity is 2.616 * 10
6G PE/molZr.hr.Polyethylene viscosity-average molecular weight 18976.
Embodiment 31: vinyl polymerization
The 400ml polymermaking autoclave toasts 1.5hr in advance under 90 ℃ of vacuum, adjusting and constant in 70 ℃ then feeds ethylene gas, and this moment, ethene air pressure was normal pressure.Under agitation add 80ml toluene, 1.0mlMMAO, 1mlCPSC10 and 10ml toluene successively.Regulating the ethene input air pressure is 4.5atm, and stirring reaction 1hr stops the input of ethylene gas then, stops stirring, in the impouring 200ml acidic ethanol, filter, with resulting polymers washing with alcohol, filtration, and, getting 5.969g in 40 ℃ of vacuum-dryings 24 hours, catalytic activity is 1.792 * 10
6G PE/molZr.hr.Polyethylene viscosity-average molecular weight 80965.The resulting polymers mode of appearance is thread.
Embodiment 32: vinyl polymerization
The 400ml polymermaking autoclave toasts 1.5hr in advance under 90 ℃ of vacuum, adjusting and constant in 50 ℃ then feeds ethylene gas, and this moment, ethene air pressure was normal pressure.Under agitation add 80ml toluene, 1.0mlMMAO, 1mlCPSC10 and 10ml toluene successively.Regulating the ethene input air pressure is 4.5atm, and stirring reaction 1hr stops the input of ethylene gas then, stops stirring, in the impouring 200ml acidic ethanol, filter, with resulting polymers washing with alcohol, filtration, and, getting 9.724g in 40 ℃ of vacuum-dryings 24 hours, catalytic activity is 13.140 * 10
6G PE/molZr.hr.Polyethylene viscosity-average molecular weight 259414.
Embodiment 33: vinyl polymerization
The 400ml polymermaking autoclave toasts 1.5hr in advance under 90 ℃ of vacuum, adjusting and constant in 30 ℃ then feeds ethylene gas, and this moment, ethene air pressure was normal pressure.Under agitation add 80ml toluene, 1.0mlMMAO, 1mlCPSC10 and 10ml toluene successively.Regulating the ethene input air pressure is 4.5atm, and stirring reaction 1hr stops the input of ethylene gas then, stops stirring, in the impouring 200ml acidic ethanol, filter, with resulting polymers washing with alcohol, filtration, and, getting 11.017g in 40 ℃ of vacuum-dryings 24 hours, catalytic activity is 14.888 * 10
6G PE/molZr.hr.Polyethylene viscosity-average molecular weight 278484.DSC: unimodal, fusing point Tm=133.561 ℃, melting enthalpy Δ Hm=222.227J/g.
Claims (7)
1, a kind of olefin polymerization catalysis that contains substituting group west Buddhist alkali coordination IVB family is characterized in that the component expression formula is [L
2MCl
2], L represents to contain or pbz polymer segmental west Buddhist alkali ligand not, and M is an IVB family metallic element, and Cl represents the chlorine atom; Concrete structure is as follows:
Wherein, R represents ethyl, vinyl, perhaps vinyl and styrene copolymerized formed polymer segment, and M is Ti or Zr.
2,, it is characterized in that being dichloride (nitrogen-to ethylphenyl)-3-tertiary butyl salicylic alidehyde imine network zirconium (IV) catalyzer that its structural formula is as follows according to the described catalyzer of claim 1:
3,, it is characterized in that being dichloride (nitrogen-to ethenylphenyl)-3-tertiary butyl salicylic alidehyde imine network zirconium (IV) catalyzer that its structural formula is as follows according to the described catalyzer of claim 1:
4,, it is characterized in that being the IVB family west Buddhist alkali olefin polymerization catalysis of the high molecular of loaded by polystyreneization that its structural formula is as follows according to the described catalyzer of claim 1:
M=Ti or Zr
Expression vinyl and styrene copolymerized formed polymer segment
5, a kind of preparation method who contains the olefin polymerization catalysis of substituting group west Buddhist alkali coordination IVB family as claimed in claim 1 is characterized in that:
(1) preparation 3-alkyl salicylic aldehyde: under the Grignard reagent effect, heat in toluene solution with Paraformaldehyde 96, triethylamine and to finish reaction by vicinal alkylene phenol; 3-alkyl salicylic aldehyde crude product is used SiO
2Post/sherwood oil or hexane wash-out get pure product;
(2) preparation aromatic amine:
1. prepare ethylaniline: ethylbenzene at-10 ℃-0 ℃ down with nitrosonitric acid with the vitriol oil is nitrated must reduce to ethylaniline in acidic medium with iron powder then to nitro ethylbenzene;
2. prepare vinyl aniline: must obtain p-nitrophenyl ethene to the nitro bromobenzyl with formaldehyde experience wittig reaction to the nitro bromobenzyl with para-nitrotoluene bromination under heating condition, in alkaline medium, experience reduction with vat powder then and obtain vinyl aniline;
(3) preparation Schiff base ligand: with the dehydrated alcohol is solvent, and aromatic amine and 3-alkyl salicylic aldehyde at room temperature stirring reaction 15-20 hour filter, and wash filter residue with ethyl acetate, evaporation except that desolvate crude product, use SiO
2Post, sherwood oil or hexane/ethyl acetate wash-out get the pure product of Schiff base ligand, and the mass ratio that fragrance revolves amine and 3-alkyl salicylic aldehyde is 1-1.5: 1;
(4) the western Buddhist alkali of preparation is all joined type IVB group 4 transition metal olefin polymerization catalysis: carrying out under anhydrous and oxygen-free and high purity inert gas protective condition, is solvent with tetrahydrofuran (THF) or ether, the Schiff base ligand and the MCl that will be made by step (3)
4Proportioning by 2.0-2.1: 1mol feeds intake; The solution of Schiff base ligand 1.5-3 hour becomes lithium salts with the hexane solution reaction of n-Butyl Lithium or KH at-72 ℃ to the room temperature earlier, drops to MCl then
4Solution in, stirring at room 12-18 hour, carry out aftertreatment again and get final product, wherein, MCl
4In M be IVB group 4 transition metal element.
6, Preparation of catalysts method according to claim 5, it is characterized in that the resulting substituent western Buddhist alkali olefin polymerization catalysis of alkene, vinylbenzene and the Diisopropyl azodicarboxylate of containing mixed copolyreaction in solvent, temperature of reaction 75-85 ℃, time 15-20 hour; The molar ratio of west Buddhist alkali olefin polymerization catalysis, vinylbenzene, Diisopropyl azodicarboxylate is 1: 100-1000: 1-5.
7, a kind of as the described application of olefin polymerization catalysis in ethylene high pressure or polymerization under atmospheric pressure that contains substituting group west Buddhist alkali coordination IVB family of claim 1-4, it is characterized in that: polyreaction is carried out under the anhydrous and oxygen-free condition, in normal pressure or highly compressed ethene atmosphere downhill reaction system, add the 35-90ml solvent successively, 0.3-5ml promotor methylaluminoxane, 0.5-1ml described catalyzer, in room temperature to 80 ℃ following reaction 15-60 minute, the input of termination ethene, with the ethanolic soln termination reaction that contains 1% hydrochloric acid, products therefrom is filtered, use washing with alcohol, and got polyethylene in 30-50 ℃ of vacuum-drying 20-30 hour.
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| US6410664B1 (en) * | 1997-03-24 | 2002-06-25 | Cryovac, Inc. | Catalyst compositions and processes for olefin polymers and copolymers |
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