CN1152892C - Binuclear cyclopentadinyl titanium imide as olefine polymerizing catalyst - Google Patents
Binuclear cyclopentadinyl titanium imide as olefine polymerizing catalyst Download PDFInfo
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- CN1152892C CN1152892C CNB991241916A CN99124191A CN1152892C CN 1152892 C CN1152892 C CN 1152892C CN B991241916 A CNB991241916 A CN B991241916A CN 99124191 A CN99124191 A CN 99124191A CN 1152892 C CN1152892 C CN 1152892C
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Abstract
The present invention discloses a novel binuclear cyclopentadinyl titanium imide catalyst for olefinic polymerization. In the present invention, a substituent with steric hindrance or a substituent containing hetero atoms is connected to a benzene ring or a cyclopentadine ring so as to increase steric hindrance, or the benzene ring or the cyclopentadine ring is coordinated with central metal to change the space environment or electron environment of an active center, and thus, a binuclear cyclopentadiene titanium imide compound is synthesized. The compound is a high efficiency catalyst for olefinic polymerization, catalytic efficiency for ethylene can reach 8*10<5>gPE/molTi. h, and catalytic polymerization efficiency for phenylethylene is greater than 1*10<5>gPS/molTi. mols. h.
Description
Technical field
The present invention relates to a kind of binuclear cyclopentadinyl titanium imide type catalyzer that is applied to olefinic polymerization.
Background technology
At present the annual production of polyethylene, polypropylene, polystyrene three big macromolecule products has reached more than one hundred million tons in the world, and they have become modern humans's indispensable integral part of living.Catalyzer then is an important factor in the olefin polymerization process.Therefore develop various efficient special olefin polymerization catalysis and become the focus in chemical boundary.Especially the eighties, Kaminsky at first found the catalyst system that this efficient promotor of methoxyl group alumina alkane (MAO) and dimethyl zirconocene are formed, and under certain conditions, catalytic efficiency is up to 100,000,000 times.After this synthetic various metallocene catalysts more are subjected to various countries and pay attention to.
Recently, it is main catalyzer that Du Pont and U.S. north Caro woods university (J.A.C.S.1995,117,6419 and 1998,120,888) have developed a kind of novel diimine complex compound cooperatively, and with catalyzed polymerization ethene, propylene, the catalyzed conversion number is up to 2 * 10
6Inferior/h.Since then, metal contains the N heterocyclic compound and has been subjected to favor, and its structural formula is:
European patent EP 416,815 had been reported the titanium nitrogen heterocyclic that contains the Si bridge in 1989:
A luxuriant nitrogen heterocyclic that does not contain silicon bridge has been synthesized in Hughes (Journal of Organometallic Chemistry 1997,528,195) the employing tertiary butyl, the reaction of cyclopentadiene substituted propyl amine and four (dimethylamino) titanium in 1997:
Green in the same year (Journal of Organometallic Chemistry 1997,541,121) has made and has contained the silica-based titanium nitrogen heterocyclic of front three:
Though above-mentioned catalyzer has advantages of high catalytic activity, because its raw material sources are comparatively difficult, preparation technology is comparatively complicated, and production cost is higher relatively, so brought certain obstacle for large-scale industrial production.
1996 P.P.Power (Journal of Organometallic Chemistry 1996,513,173) with (THF Mg NPh)
6Be the nitrogen heterocyclic ring that raw material has synthesized two titaniums, its structural formula is:
But the catalytic result to them does not appear in the newspapers.
In sum, though industrial employed various types of olefins polymerizing catalyst all has advantage separately at present, but also exist some deficiency in actual use, therefore, branch of industry wishes that the parties concerned constantly provide novel, have catalyzer more highly active, that preparation is more simple and production cost is lower, to satisfy the industrial needs of develop rapidly.
Summary of the invention
The objective of the invention is to, provide a kind of olefin polymerization catalysis more highly active, that preparation is more simple and production cost is lower that has, to overcome the existing in prior technology defective;
Design of the present invention is such:
The present invention has connected the sterically hindered substituting group or has connected and contained heteroatomic substituting group on phenyl ring or luxuriant ring, sterically hindered to increase, or change the space environment or the electronic environment in active centre with the central metal coordination, to reach the purpose that is beneficial to alkene coordination and chainpropagation, to improve the catalytic activity and the selectivity of catalyzer.
Technical scheme:
The said binuclear cyclopentadinyl titanium imide type of the present invention catalyzer is the compound with one of following general structure:
Or
In the formula: X is Cl or Br; R
1Be H, C
2H
5Br or CH
2CH
2OCH
3R
2Be H, CH
3, OCH
3Or N (CH
3)
2, wherein: work as R
1, R
2When being all H, X is Br.
Preferred group is: R
2Be OCH
3Or N (CH
3)
2
Above-mentioned compound is the effective catalyst of olefinic polymerization, and ethylene catalyst efficient can be up to 8 * 10
5GPE/mol Tih, vinylbenzene catalyzed polymerization efficient＞1 * 10
5GPS/molTimolsh.
Above-mentioned binuclear cyclopentadinyl titanium imide type catalyzer is preparation like this:
To replace or unsubstituted luxuriant titanium halide and aryl amine lithium, aryl amine magnesium or pyridine Lithamide and solvent place the stirring heating reactor to react, reacted product adopts conventional method such as recrystallization etc. to carry out purifying, can obtain said compound.
The general structure of said replacement or unsubstituted luxuriant titanium halide is:
Or
R
1, X is the same said;
This compound be prepared as a kind of prior art, at document TransitionMet.Chem., 15, existing report among the 483-485 (1990), the present invention repeats no more.
The general structure of said aryl amine lithium or aryl amine magnesium is:
R
2The same said;
This compound be prepared as a kind of prior art, at document Organometallics, 1994,13,2792 and J.Organomet.Chem. in existing report, the present invention repeats no more;
Said pyridine Lithamide is performed such preparation:
The n-Butyl Lithium of commercially available 2-aminopyridine and equivalent was stirred 2 hours in-20 ℃ and solvent THF (tetrahydrofuran (THF)), after reaction finishes,, can obtain said pyridine Lithamide except that desolvating;
Reaction formula is:
Said solvent is organic solvents such as THF, toluene or benzene.
Reaction can be carried out under the protection of rare gas element;
The triethylamine that also can add equivalent during reaction is to help removing of chlorine.
Reaction expression is as follows:
Or (2)
The processing condition of reaction are such:
Temperature of reaction is-50 a ℃～solvent refluxing temperature, and the reaction times is 4 hours～20 hours, and the proportioning of each material is during reaction:
Luxuriant titanium halide: aryl amine lithium, aryl amine magnesium or pyridine Lithamide=1: (1～1.5) (mol ratio);
Preferred temperature of reaction is-20 a ℃～solvent refluxing temperature, and preferred material proportion is during reaction:
Luxuriant titanium halide: aryl amine lithium, aryl amine magnesium or pyridine Lithamide=1: (1～1.2);
By above-mentioned preparation process as seen, the preparation process of the said compound of the present invention is very simple, and is easy to operate, is easy to suitability for industrialized production.
The said compound of the present invention can be used as olefin polymerization catalysis, especially can be used as ethylene rolymerization catalyst, in polymerization process, Primary Catalysts is the said compound of the present invention, promotor can adopt methylaluminoxane, and the processing condition of polyreaction are identical with conventional olefinic polyreaction.Be solvent with toluene during reaction, the mol ratio of aluminium and titanium is 500～1500, and polymerization time is 10min～2 hour, and polymerization temperature is 35 ℃～70 ℃, and polymerization pressure is 0.1Mpa, and its catalyst activity can reach 8 * 10
5More than the PE/molTih.
Specific implementation method
Below will be further elaborated related content of the present invention by embodiment.
Embodiment 1
[(η
5-C
5H
5) TiCl (μ-NC
6H
3(CH
3)
2-2,6]
2Synthetic:
Structural formula is:
One 100ml there-necked flask is mixed magnetic stirring apparatus, reflux condensing tube, add a luxuriant trichlorine titanium 0.3g, toluene 30-50ml is with 2 of equivalent, 6-dimethyl benzene amido magnesium tetrahydrofuran (THF) title complex adds wherein, reflux and stirred 8 hours, filter, with methylene dichloride/normal hexane recrystallization, get product 0.25g, productive rate 65%.
1HNMR：2.70(s，12H)，6.34(s，10H)，6.97((m，6H).IR：3424(s)，2985(s)，2851(s)，2734(s)，2556(s)，2237(m)，1976(w)，1623(m)，1585(m)，1525
(s)，1474(s)，1441(m)，1263(w)，1179(w)，1093(w)，1017(s)，856(s)，620(s)，535(s)；
Ultimate analysis:
Calculated value: C 58.35%.H 5.27%.N 5.23%
Actual measurement: C 58.40%.H 5.30%.N 5.44%.
Embodiment 2
[(η
5-C
5H
4CH
2CH
2Br) TiBr (μ-NC
6H
4OCH
3-O]
2Synthetic:
The 100ml there-necked flask is mixed magnetic stirring apparatus, dropping funnel, adds the luxuriant titanium tribromide 0.5g of bromotrifluoromethane, THF80ml ,-300 ℃ of tetrahydrofuran solutions that drip the ORTHO ANISIDINE base lithium of equivalent down.Dropwise stirring at room 5.5 hours.Drip the triethylamine of equivalent then, restir.Remove and desolvate, the methylbenzene extraction recrystallization gets product 0.15g, productive rate 69%.
1HNMR：2.87(m，4H)，3.30(m，4H)，4.29(s，6H)，5.89(m，2H)，6.18(m，2H)，6.24(m，2
H)，6.35(m，2H)，7.01(m，8H)；IR：3418(vs)，2939(s)，2679(s)，2491(m)，1603(m)，1489(vs)，804(vs)，753(vs)，
622(s)，591(s)，467(m)；
Ultimate analysis:
Calculated value: C 39.94%.H 3.59%.N 3.33%
Actual measurement: C 39.95%.H 3.82%.N 3.28%.
Embodiment 3
[(η
5-C
5H
4CH
2CH
2OCH
3) TiCl (μ-NC
6H
4OCH
3-O]
2Synthetic:
Add the luxuriant titanous chloride 0.45g of methoxyethyl under the 100ml there-necked flask nitrogen gas stream, THF 25ml drips the THF solution that is equivalent to 1.2 normal ORTHO ANISIDINE base lithiums, stirring at room down at 30 ℃.Drip the triethylamine of equivalent, stir and remove unnecessary solvent after 4 hours.Methylbenzene extraction, the low temperature recrystallization gets the dark red crystal, productive rate 75%.
1HNMR：2.67(m，4H)，3.15(s，6H)，3.313.30(m，4H)，4.22(s，6H)，5.79(m，2H)，6.00(m，2H)，6
.13(m，6H)，6.23(m，2H)，6.85(m，2H)。IR：3430(m)，3091(w)，2929(m)，2868(s)，1626(w)，1478(vs)，1383(w)，
1281(m)，1256(vs)，1219(s)，1180(m)，1112(vs)，1038(m)，1007(s)，820(s)，74
3(s)660(vs)，561(w)；
Ultimate analysis:
Calculated value: C 54.99%.H 5.54%.N 4.27%
Actual measurement: C 54.90%.H 5.53%.N 4.24%.
Embodiment 4
[(η
5-C
5H
4) TiCl (μ-NC
6H
4N (CH
3)
2-O)]
2Synthetic:
In the 100ml there-necked flask, add a luxuriant titanous chloride 0.60g9 under the nitrogen gas stream, use benzene 40ml, and the N of equivalent, the title complex of N-dimethyl O-Phenylene Diamine base magnesium tetrahydrofuran (THF) refluxed 20 hours, filtered, and concentrated in CH
2CL
2Recrystallization gets the dark red product in the/sherwood oil, productive rate 56%.
1HNMR：2.89(s，12H)，6.26(s，10H)，6.81(m，4H)，7.16(m，4H).IR：3406(w)，3055(w)，2903(w)，1579(m)，1469(s)，1446(s)，1308(m)，1281(s)，1261(m)，124
0(m)，1149(m)，1097(m)，1029(m)，914(s)，830(m)，806(s)，
750(s)，644(s)，614(m)，495(m)，420(m)。
Ultimate analysis:
Calculated value: C, 55.25%.H, 5.35%.N, 9.91%
Actual measurement: C, 54.45%.H, 5.12%.N, 9.96%.
Embodiment 5
[(η
5-C
5H
5) TiCl (μ-NC
6H
4N-O)]
2Synthetic:
Add a luxuriant trichlorine titanium 0.38g under the nitrogen gas stream in three-necked bottle, THF 30m1. drips the 2-pyridine Lithamide of equivalent and excessive triethylamine down at-10 ℃, slowly rises to stirring at room 4 hours, remove and desolvate, methylbenzene extraction, recrystallization obtain product 0.45g, productive rate 60%.
1HNMR：6.57(m，4H)，6.66(m，6H)，6.90(m，2H)，7.48(m，2H)，7.70(m，2H)，8.05(m，2H)；
IR(KBr)：3326(s)，3147(s)，2970(s)，1665(s)，1621(s)，1546(w)，1477(m)，1381(m)，1325(w)，1017(m)，997(m)，862(s)，796(s)，768(s)，622(s)，528(s)。
Ultimate analysis:
Calculated value: C 49.94%.H 3.77%.N 11.65%
Actual measurement: C 49.87%.H 3.67%.N 11.54%.
Embodiment 6
[(η
5-C
5H
4CH
2CH
2OCH
3) TiCl (μ-NC
5H
4N-O)]
2Preparation:
Add methoxyethyl under the nitrogen gas stream and replace luxuriant titanous chloride 0.38g in the reaction flask of a 100ml, THF30ml. adds the 2-pyridine Lithamide of equivalent and the triethylamine of equivalent, stirring at room 4 hours down at-20 ℃.Remove and desolvate, methylbenzene extraction and recrystallization obtain product, productive rate 49%
1HNMR：2.59(t，4H)，3.21(s，6H)，3.40(t，4H)，6.11(t，4H)，6.27(t，4H)，6.62(d，2H)，6.87(m，2H)，7.66(m，2H)，8.05(m，2H).
IR(KBr)：3300(s)，3147(s)，2921(m)，1665(s)，1621(s)，1547(w)，1476(w)，1381(w)，1325(w)，1165(w)，1117(w)，998(w)，838(m)，770(m)，511(s)；
Ultimate analysis:
Calculated value: C, 52.29%.H, 5.06%.N, 9.38%
Actual measurement: C, 51.97%.H, 5.37%.N, 9.06%.
Embodiment 7
[(η
5-C
5H
5) TiCl (μ-NC
6H
4OCH
3-O)]
2Preparation:
Method (1):
Add a luxuriant trichlorine titanium 0.4g and a THF 20ml in the nitrogen gas stream downhill reaction bottle,, stirred 4 hours at-10 ℃ of THF solution that add 0.28 gram ORTHO ANISIDINE base lithium down, the triethylamine that adds equivalent stirs, and removes and desolvates, methylbenzene extraction and recrystallization obtain product, productive rate 61%;
Method (2):
Add two luxuriant dichloro titanium 0.8g and toluene 50ml in the nitrogen gas stream downhill reaction bottle, the THF solution that under reflux temperature, adds 0.45 gram ORTHO ANISIDINE base lithium, reacted 4 hours, the triethylamine that adds equivalent, 90 ℃ were stirred 5 hours down, remove and desolvate methylbenzene extraction and recrystallization, obtain product, productive rate 52%.
1HNMR：4.25(s，6H)，6.21(s，10H)，6.85(m，2H)，6.94(m，4H)，7.05(m，2H)；
IR：3421(w)，3099(w)，2941(w)，1587(w)，1475(s)，1488(m)，1319(w)，1279(m)，1254(s)，1217(w)，1171(w)，1111(m)，1008(s)，899(w)，813(vs)，745(s)，644(s)，500(m)，425(m)；
Ultimate analysis:
Calculated value: C 53.47%.H 4.49%.N 5.20%
Actual measurement: C 53.41%.H4.54%.N4.83%.
Embodiment 8
((η
5-C
5H
5) TiCl (μ-NC
6H
3CH
3-2))
2Preparation:
Add a luxuriant trichlorine titanium 0.63g and a THF 50ml in the nitrogen gas stream downhill reaction bottle,, stirred 4 hours at-30 ℃ of THF solution that drip 0.32 gram 2-aminotoluene base lithium down, the triethylamine that adds equivalent stirs, and removes and desolvates, methylbenzene extraction and recrystallization obtain product 0.57 gram, productive rate 78%.
1HNMR：2.22(s，6H)，6.32(s，5H)，6.62(s，5H)，6.80(m，2H)，6.95(m，2H)，7.06(m，2H)，7.16(m，2H)；
IR：3419(m)，2854(s)，2063(s)，1978(m)，1801(w)，1589(m)，1498(s)，1460(m)，1307(w)，1144(w)，1067(w)，1017(s)，858(s)，792(s)，752(s)，620(s)，530(s)；
Ultimate analysis:
Calculated value: C 56.84%.H 4.77%.N 5.52%
Actual measurement: C 57.02%.H4.77%.N 5.29%.
Embodiment 9
With embodiment 7 described compounds is Primary Catalysts, and titanium concentration is [Ti]=7 * 10
-5Mol.dm
-3, be promotor with the methylaluminoxane, control Al/Ti=500, polymerization pressure is P
Ethene=0.1MPa, 50 ℃ were reacted 0.5 hour down, and polymerization activity is 3.2 * 10
5GPE (mol.Ti.h)
-1
Embodiment 10
With embodiment 8 described compounds is Primary Catalysts, and titanium concentration is [Ti]=7 * 10
-5Mol.dm
-3, be promotor with the methylaluminoxane,, control Al/Ti=1000, polymerization pressure is P
Ethene=0.1MPa, 50 ℃ were reacted 0.5 hour down, and polymerization activity is 3.4 * 10
5GPE (mol.Tih)
-1
Embodiment 11
With embodiment 7 described compounds is Primary Catalysts, and titanium concentration is [Ti]=7 * 10
-5Mol.dm
-3, be promotor with the methylaluminoxane, control Al/Ti=1500, polymerization pressure is P
Ethene=0.1MPa, 50 ℃ were reacted 0.5 hour down, and polymerization activity is 3.5 * 10
5GPE (mol.Tih)
-1
Embodiment 12
With embodiment 7 described compounds is Primary Catalysts, and titanium concentration is [Ti]=7 * 10
-5Mol.dm
-3, be promotor with the methylaluminoxane, control Al/Ti=1000, polymerization pressure is P
Ethene=0.1MPa, 35 ℃ were reacted 0.5 hour down, and polymerization activity is 8.07 * 10
5GPE (mol.Tih)
-1
Embodiment 13
With embodiment 7 described compounds is Primary Catalysts, and titanium concentration is [Ti]=7 * 10
-5Mol.dm
-3, be promotor with the methylaluminoxane, control Al/Ti=1000, polymerization pressure is P
Ethene=0.1MPa, 70 ℃ were reacted 0.5 hour down, and polymerization activity is 2.8 * 10
5GPE (mol.Ti.h)
-1
Embodiment 14
Reactor is vacuumized, feed vinylbenzene, add toluene and make solvent, vinylbenzene is dissolved in the toluene, adds the 3.4ml methylaluminoxane, 0.005mmol embodiment 7 described compounds, control Al/Ti=2000,50 ℃ of reactions down are when white appears in polymkeric substance, with 100ml 10%HCl termination reaction, filter, obtain white polymer, washing with alcohol, drying is 12 hours under 50 ℃, can obtain polystyrene, and polymerization activity is 1 * 10
5GPS (mol.Ti.h)
-1, use the butanone recrystallization then, 50 ℃ of following vacuum-dryings, normality is 65% (S-PS) between the polymkeric substance of gained.
Claims (2)
1. binuclear cyclopentadinyl titanium imide as olefine polymerizing catalyst, it is characterized in that: described catalyzer is the compound that a class has one of following general structure:
Or
In the formula: X is Cl or Br; R
1Be H, C
2H
5Br or CH
2CH
2OCH
3R
2Be H, CH
3, OCH
3Or N (CH
3)
2, wherein work as R
1, R
2When being all H, X is Br.
2. catalyzer as claimed in claim 1 is characterized in that, wherein R
2Be OCH
3Or N (CH
3)
2
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|---|---|---|---|
| CNB991241916A CN1152892C (en) | 1999-12-02 | 1999-12-02 | Binuclear cyclopentadinyl titanium imide as olefine polymerizing catalyst |
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|---|---|---|---|
| CNB991241916A CN1152892C (en) | 1999-12-02 | 1999-12-02 | Binuclear cyclopentadinyl titanium imide as olefine polymerizing catalyst |
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| CN1152892C true CN1152892C (en) | 2004-06-09 |
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|---|---|---|---|
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