One of purpose of the present invention is to provide a kind of binuclear cyclopentadinyl titanium imide as olefine polymerizing catalyst more highly active, that preparation is more simple and production cost is lower that has, to overcome the existing in prior technology defective;
Two of purpose of the present invention is to disclose said Preparation of catalysts method.
Three of purpose of the present invention is to provide a kind of application of said catalyzer.
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.
Said catalyzer is the binuclear cyclopentadinyl titanium imide type compound that a class has one of following general structure:
Wherein: X is Cl or Br; R
1Be H, C
2H
5Br or CH
2CH
2OCH
3In one;
R
2Be H, CH
3, OCH
3Or N (CH
3)
2In one.
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/molTih, vinylbenzene catalyzed polymerization efficient>1 * 10
5GPS/molTimolsh.
Above-mentioned binuclear cyclopentadinyl titanium imide type compound also 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 Transition Met.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:
Or
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: (1)
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.
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:
General-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 ,-30 ℃ 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, 2H), 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),3.31?3.30(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%.N4.24%.
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 30ml. 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 triethylamine of the 2-of equivalent than pyridine Lithamide and 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%.H 4.54%.N 4.83%.
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%.H 4.77%.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.