311:
170:. Ziegler–Natta catalysts have been used in the commercial manufacture of various polyolefins since 1956. As of 2010, the total volume of plastics, elastomers, and rubbers produced from alkenes with these and related (especially Phillips) catalysts worldwide exceeds 100 million tonnes. Together, these polymers represent the largest-volume commodity plastics as well as the largest-volume commodity chemicals in the world.
639:
477:
777:
Polymerization reactions of alkenes with solid titanium-based catalysts occur at special titanium centers located on the exterior of the catalyst crystallites. Some titanium atoms in these crystallites react with organoaluminum cocatalysts with the formation of Ti–C bonds. The polymerization reaction
338:
groups in the figure. In the isotactic polymers, all stereogenic centers CHR share the same configuration. The stereogenic centers in syndiotactic polymers alternate their relative configuration. A polymer that lacks any regular arrangement in the position of its alkyl substituents (R) is called
280:) was discovered to greatly enhance the activity of the titanium-based catalysts. These catalysts were so active that the removal of unwanted amorphous polymer and residual titanium from the product (so-called deashing) was no longer necessary, enabling the commercialization of
339:
atactic. Both isotactic and syndiotactic polypropylene are crystalline, whereas atactic polypropylene, which can also be prepared with special
Ziegler–Natta catalysts, is amorphous. The stereoregularity of the polymer is determined by the catalyst used to prepare it.
650:
describes the growth of stereospecific polymers. This mechanism states that the polymer grows through alkene coordination at a vacant site at the titanium atom, which is followed by insertion of the C=C bond into the Ti−C bond at the active center.
814:
The two chain termination reactions occur quite rarely in
Ziegler–Natta catalysis and the formed polymers have a too high molecular weight to be of commercial use. To reduce the molecular weight, hydrogen is added to the polymerization reaction:
461:. The modifiers react both with inorganic ingredients of the solid catalysts as well as with organoaluminum cocatalysts. These catalysts polymerize propylene and other 1-alkenes to highly crystalline isotactic polymers.
569:
Ziegler–Natta catalysts of the third class, non-metallocene catalysts, use a variety of complexes of various metals, ranging from scandium to lanthanoid and actinoid metals, and a large variety of ligands containing
261:. In that process, the particle bed in the reactor was either not fluidized or not fully fluidized. In 1968, the first gas-phase fluidized-bed polymerization process, the Unipol process, was commercialized by
1002:
Nowlin, T. E.; Mink, R. I.; Kissin, Y. V. (2010). "Supported
Magnesium/Titanium-Based Ziegler Catalysts for Production of Polyethylene". In Hoff, Ray; Mathers, Robert T. (eds.).
635:, which is ion-paired to some derivative(s) of MAO. A polymer molecule grows by numerous insertion reactions of C=C bonds of 1-alkene molecules into the Zr–C bond in the ion:
177:
discovered that chromium catalysts are highly effective for the low-temperature polymerization of ethylene, which launched major industrial technologies culminating in the
1171:
Alt, H. G.; Koppl, A. (2000). "Effect of the Nature of
Metallocene Complexes of Group IV Metals on Their Performance in Catalytic Ethylene and Propylene Polymerization".
1534:
303:
and other 1-alkenes. He discovered that these polymers are crystalline materials and ascribed their crystallinity to a special feature of the polymer structure called
609:
The structure of active centers in
Ziegler–Natta catalysts is well established only for metallocene catalysts. An idealized and simplified metallocene complex Cp
646:
Many thousands of alkene insertion reactions occur at each active center resulting in the formation of long polymer chains attached to the center. The
405:. A third component of most catalysts is a carrier, a material that determines the size and the shape of catalyst particles. The preferred carrier is
322:
The concept of stereoregularity in polymer chains is illustrated in the picture on the left with polypropylene. Stereoregular poly(1-alkene) can be
1273:
Britovsek, G. J. P.; Gibson, V. C.; Wass, D. F. (1999). "The Search for New-Generation Olefin
Polymerization Catalysts: Life beyond Metallocenes".
1234:
Corradini, P.; Guerra, G.; Cavallo, L. (2004). "Do New
Century Catalysts Unravel the Mechanism of Stereocontrol of Old Ziegler–Natta Catalysts?".
659:
On occasion, the polymer chain is disengaged from the active centers in the chain termination reaction. Several pathways exist for termination:
617:
represents a typical precatalyst. It is unreactive toward alkenes. The dihalide reacts with MAO and is transformed into a metallocenium ion Cp
1287:
469:
A second class of
Ziegler–Natta catalysts are soluble in the reaction medium. Traditionally such homogeneous catalysts were derived from
1324:
1367:
381:
The overlap between these two subclasses is relatively small because the requirements to the respective catalysts differ widely.
847:
Another termination process involves the action of protic (acidic) reagents, which can be intentionally added or adventitious.
17:
597:
Most
Ziegler–Natta catalysts and all the alkylaluminium cocatalysts are unstable in air, and the alkylaluminium compounds are
1045:
435:
All modern supported
Ziegler–Natta catalysts designed for polymerization of propylene and higher 1-alkenes are prepared with
1382:
1474:
1155:
1019:
968:
1509:
1504:
1469:
1630:
1519:
1514:
1499:
281:
555:, metallocene catalysts can produce either isotactic or syndiotactic polymers of propylene and other 1-alkenes.
1524:
1402:
1107:"Development of Group Iv Molecular Catalysts for High Temperature Ethylene-Α-Olefin Copolymerization Reactions"
935:
725:
Another type of chain termination reaction called a β-hydride elimination reaction also occurs periodically:
473:, but the structures of active catalysts have been significantly broadened to include nitrogen-based ligands.
1645:
1317:
417:
are packed into the silica pores. All these catalysts are activated with organoaluminum compounds such as
1575:
647:
1640:
1392:
564:
413:
with a diameter of 30–40 mm. During the catalyst synthesis, both the titanium compounds and MgCl
190:
1655:
1650:
1464:
1428:
1333:
1310:
155:
62:
based on titanium compounds are used in polymerization reactions in combination with cocatalysts,
353:
54:). Two broad classes of Ziegler–Natta catalysts are employed, distinguished by their solubility:
314:
Short segments of polypropylene, showing examples of isotactic (above) and syndiotactic (below)
1609:
1494:
436:
385:
182:
265:
to produce polyethylene. In the mid-1980s, the Unipol process was further extended to produce
1529:
525:
927:
384:
Commercial catalysts are supported by being bound to a solid with a high surface area. Both
1484:
1347:
918:
Giuliano Cecchin; Giampiero Morini; Fabrizio Piemontesi (2003). "Ziegler–Natta Catalysts".
392:
362:-based catalysts) for alkene polymerization can be roughly subdivided into two subclasses:
206:
287:
The fluidized-bed process remains one of the two most widely used processes for producing
205:
Cl) gave comparable activities for the production of polyethylene. Natta used crystalline
8:
1604:
1423:
1397:
1352:
449:
as a support. Another component of all such catalysts is an organic modifier, usually an
1635:
1418:
1372:
601:. The catalysts, therefore, are always prepared and handled under an inert atmosphere.
443:
399:
273:
174:
1599:
1570:
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1489:
1291:
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1252:
1189:
1151:
1128:
1041:
1015:
964:
931:
874:
494:
418:
213:
178:
101:
67:
299:
Natta first used polymerization catalysts based on titanium chlorides to polymerize
1565:
1459:
1362:
1357:
1283:
1244:
1181:
1118:
1007:
956:
923:
917:
549:
548:. Depending on the type of their cyclopentadienyl ligands, for example by using an
529:
506:
410:
304:
100:. They are usually used in combination with a different organoaluminum cocatalyst,
86:
59:
594:(S). The complexes are activated using MAO, as is done for metallocene catalysts.
1438:
1433:
1236:
1123:
1106:
533:
366:
catalysts suitable for homopolymerization of ethylene and for ethylene/1-alkene
1555:
1454:
1377:
254:
63:
1035:
1011:
1624:
1550:
1288:
10.1002/(SICI)1521-3773(19990215)38:4<428::AID-ANIE428>3.0.CO;2-3
899:
882:
861:
499:
These catalysts are metallocenes together with a cocatalyst, typically MAO, −
454:
288:
266:
262:
258:
231:
1037:
Polypropylene Production via Gas Phase Process, Technology Economics Program
850:
370:
reactions leading to copolymers with a low 1-alkene content, 2–4 mol% (
1302:
1295:
1256:
1193:
1132:
887:
869:
856:
481:
327:
163:
159:
109:
51:
39:
35:
960:
310:
284:(LLDPE) resins and allowed the development of fully amorphous copolymers.
1479:
470:
406:
125:
105:
1173:
778:
of alkenes occurs similarly to the reactions in metallocene catalysts:
598:
587:
398:
give active catalysts. The support in the majority of the catalysts is
1248:
1185:
1591:
1387:
1104:
517:
367:
323:
315:
300:
243:
228:
167:
93:
579:
359:
358:
The first and dominant class of titanium-based catalysts (and some
239:
235:
162:, for his discovery of first titanium-based catalysts, and Italian
89:
47:
43:
1148:
Organometallics 1, Complexes with Transition Metal-Carbon σ-Bonds
638:
521:
113:
104:(or methylalumoxane, MAO). These catalysts traditionally contain
97:
1264:
Takahashi, T. (2001). "Titanium(IV) Chloride-Triethylaluminum".
242:
and Ziegler–Natta catalysts refer to systems for conversions of
1227:
Alkene Polymerization Reactions with Transition Metal Catalysts
1092:
Alkene Polymerization Reactions with Transition Metal Catalysts
591:
571:
121:
642:
Simplified mechanism for Zr-catalyzed ethylene polymerization.
476:
181:. A few years later, Ziegler discovered that a combination of
458:
450:
371:
331:
1006:(Online ed.). John Wiley & Sons. pp. 131–155.
604:
505:−. The idealized metallocene catalysts have the composition
377:
catalysts suitable for the synthesis of isotactic 1-alkenes.
334:
groups in polymer chains consisting of units −−, like the CH
1028:
893:
250:
1535:
Arene complexes of univalent gallium, indium, and thallium
989:
Stereoregular Polymers and Stereospecific Polymerizations
851:
Commercial polymers prepared with Ziegler–Natta catalysts
166:, for using them to prepare stereoregular polymers from
120:
Ziegler–Natta catalysts are used to polymerize terminal
85:
Homogeneous catalysts usually based on complexes of the
1233:
1150:. New York: Oxford University Press. pp. 69–71.
1004:
Handbook of Transition Metal Polymerization Catalysts
953:
Handbook of Transition Metal Polymerization Catalysts
528:. Typically, the organic ligands are derivatives of
294:
1272:
1206:
1105:Klosin, J.; Fontaine, P. P.; Figueroa, R. (2015).
1070:. New York: Wiley-InterScience. pp. 136–139.
1622:
1001:
82:. This class of catalyst dominates the industry.
920:Kirk-Othmer Encyclopedia of Chemical Technology
27:Catalyst for synthesis of polymers of 1-alkenes
1266:Encyclopedia of Reagents for Organic Synthesis
982:
980:
1318:
330:depending on the relative orientation of the
1332:
986:
951:Hoff, Ray; Mathers, Robert T., eds. (2010).
558:
536:(Cp) rings are linked with bridges, like −CH
253:developed a gas-phase, mechanically-stirred
977:
950:
1419:Oxidative addition / reductive elimination
1325:
1311:
955:(Online ed.). John Wiley & Sons.
347:
1263:
1211:. New York: VCH Verlag. pp. 423–425.
1122:
605:Mechanism of Ziegler–Natta polymerization
480:A post-metallocene catalyst developed at
1368:Polyhedral skeletal electron pair theory
1170:
1145:
654:
637:
488:
475:
464:
309:
1209:Organometallics: a Concise Introduction
944:
928:10.1002/0471238961.2609050703050303.a01
14:
1623:
1224:
1207:Elschenbroich, C.; Salzer, A. (1992).
1089:
1085:
1083:
1081:
1079:
1077:
1061:
1059:
1057:
1306:
1098:
987:Natta, G.; Danusso, F., eds. (1967).
234:. Usually Ziegler catalysts refer to
1475:Transition metal fullerene complexes
1065:
866:Copolymers of ethylene and 1-alkenes
1090:Kissin, Y. V. (2008). "Chapter 4".
1074:
1054:
24:
1510:Transition metal carbyne complexes
1505:Transition metal carbene complexes
1470:Transition metal indenyl complexes
1218:
238:-based systems for conversions of
25:
1667:
1520:Transition metal alkyne complexes
1515:Transition metal alkene complexes
295:Stereochemistry of poly-1-alkenes
1525:Transition-metal allyl complexes
1068:Organotransition Metal Chemistry
1500:Transition metal acyl complexes
1200:
1164:
282:linear low-density polyethylene
124:(ethylene and alkenes with the
1139:
995:
911:
892:Amorphous poly-alpha-olefins (
173:In the early 1950s workers at
13:
1:
1111:Accounts of Chemical Research
905:
532:. In some complexes, the two
442:as the active ingredient and
1124:10.1021/acs.accounts.5b00065
7:
1576:Shell higher olefin process
1383:Dewar–Chatt–Duncanson model
112:oxygen- and nitrogen-based
10:
1672:
1465:Cyclopentadienyl complexes
1429:β-hydride elimination
1403:Metal–ligand multiple bond
562:
492:
351:
342:
149:
1589:
1543:
1530:Transition metal carbides
1447:
1411:
1340:
1012:10.1002/9780470504437.ch6
565:Post-metallocene catalyst
559:Non-metallocene catalysts
191:diethylaluminium chloride
46:used in the synthesis of
1334:Organometallic chemistry
1268:. John Wiley & Sons.
156:Nobel Prize in Chemistry
1495:Half sandwich compounds
648:Cossee–Arlman mechanism
354:Heterogeneous catalysis
348:Heterogeneous catalysts
1631:Coordination complexes
1610:Bioinorganic chemistry
1229:. Amsterdam: Elsevier.
1225:Kissin, Y. V. (2008).
1094:. Amsterdam: Elsevier.
643:
485:
319:
183:titanium tetrachloride
158:was awarded to German
32:Ziegler–Natta catalyst
18:Ziegler-Natta catalyst
1581:Ziegler–Natta process
1485:Metal tetranorbornyls
1276:Angew. Chem. Int. Ed.
1146:Bochmann, M. (1994).
961:10.1002/9780470504437
655:Termination processes
641:
526:titanocene dichloride
489:Metallocene catalysts
479:
465:Homogeneous catalysts
313:
1646:Industrial processes
1590:Related branches of
1348:Crystal field theory
1066:Hill, A. F. (2002).
249:Also, in the 1960s,
212:in combination with
1605:Inorganic chemistry
1424:Migratory insertion
1398:Agostic interaction
1353:Ligand field theory
257:process for making
60:supported catalysts
1490:Sandwich compounds
1448:Types of compounds
1373:Isolobal principle
1040:. Intratec. 2012.
644:
486:
320:
274:magnesium chloride
175:Phillips Petroleum
66:compounds such as
1641:Polymer chemistry
1618:
1617:
1600:Organic chemistry
1571:Olefin metathesis
1561:Grignard reaction
1460:Grignard reagents
1249:10.1021/ar030165n
1186:10.1021/cr9804700
1047:978-0-615-66694-5
991:. Pergamon Press.
875:Polymethylpentene
792:−CHR–polymer + CH
495:Kaminsky catalyst
227:to produce first
179:Phillips catalyst
108:but also feature
102:methylaluminoxane
68:triethylaluminium
16:(Redirected from
1663:
1566:Monsanto process
1363:d electron count
1358:18-electron rule
1327:
1320:
1313:
1304:
1303:
1299:
1269:
1260:
1230:
1213:
1212:
1204:
1198:
1197:
1180:(4): 1205–1222.
1168:
1162:
1161:
1143:
1137:
1136:
1126:
1117:(7): 2004–2016.
1102:
1096:
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1051:
1032:
1026:
1025:
999:
993:
992:
984:
975:
974:
948:
942:
941:
915:
879:Polycycloolefins
829:−CHR–polymer + H
768:
767:
766:
763:
742:
741:
740:
737:
708:
707:
706:
703:
676:
675:
674:
671:
630:
629:
628:
625:
530:cyclopentadienyl
411:amorphous silica
368:copolymerization
305:stereoregularity
21:
1671:
1670:
1666:
1665:
1664:
1662:
1661:
1660:
1656:1953 in Germany
1651:1953 in science
1621:
1620:
1619:
1614:
1585:
1539:
1455:Gilman reagents
1443:
1439:Carbometalation
1434:Transmetalation
1407:
1336:
1331:
1237:Acc. Chem. Res.
1221:
1219:Further reading
1216:
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534:cyclopentadiene
515:
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497:
491:
467:
455:aromatic diacid
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1556:Cativa process
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1300:
1282:(4): 428–447.
1270:
1261:
1243:(4): 231–241.
1231:
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1199:
1163:
1156:
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563:Main article:
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493:Main article:
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352:Main article:
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296:
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277:
272:In the 1970s,
255:polymerization
223:
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208:
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198:
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151:
148:
147:
146:
140:
136:
128:double bond):
118:
117:
87:group 4 metals
83:
79:
75:
71:
64:organoaluminum
58:Heterogeneous
50:of 1-alkenes (
34:, named after
26:
9:
6:
4:
3:
2:
1668:
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1552:
1551:Carbonylation
1549:
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1378:π backbonding
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1157:9780198558132
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1134:
1130:
1125:
1120:
1116:
1112:
1108:
1101:
1093:
1086:
1084:
1082:
1080:
1078:
1069:
1062:
1060:
1058:
1049:
1043:
1039:
1038:
1031:
1023:
1021:9780470504437
1017:
1013:
1009:
1005:
998:
990:
983:
981:
972:
970:9780470504437
966:
962:
958:
954:
947:
939:
933:
929:
925:
922:. Wiley-VCH.
921:
914:
910:
901:
900:Polyacetylene
898:
895:
891:
889:
886:
884:
883:Polybutadiene
881:
878:
876:
873:
871:
868:
865:
863:
862:Polypropylene
860:
858:
855:
854:
848:
837:
823:
818:
817:
816:
800:
786:
781:
780:
779:
728:
727:
726:
685:
662:
661:
660:
652:
649:
640:
636:
602:
600:
595:
593:
589:
581:
573:
566:
556:
554:
552:
544:− or >SiPh
535:
531:
527:
523:
519:
508:
503:
496:
483:
478:
474:
472:
462:
460:
456:
452:
448:
441:
433:
431:
412:
408:
404:
397:
390:
382:
376:
373:
369:
365:
364:
363:
361:
355:
340:
333:
329:
325:
317:
312:
308:
306:
302:
292:
290:
289:polypropylene
285:
283:
275:
270:
268:
267:polypropylene
264:
263:Union Carbide
260:
259:polypropylene
256:
252:
247:
245:
241:
237:
233:
232:polypropylene
230:
226:
211:
192:
184:
180:
176:
171:
169:
165:
161:
157:
143:
134:
131:
130:
129:
127:
123:
115:
111:
107:
103:
99:
95:
91:
88:
84:
69:
65:
61:
57:
56:
55:
53:
52:alpha-olefins
49:
45:
41:
37:
33:
19:
1580:
1544:Applications
1480:Metallocenes
1279:
1274:
1265:
1240:
1235:
1226:
1208:
1202:
1177:
1172:
1166:
1147:
1141:
1114:
1110:
1100:
1091:
1067:
1036:
1030:
1003:
997:
988:
952:
946:
919:
913:
888:Polyisoprene
870:Polybutene-1
857:Polyethylene
846:
843:−CHR–polymer
835:
821:
813:
810:−CHR–polymer
798:
784:
776:
724:
683:
658:
645:
608:
596:
568:
550:
501:
498:
482:Dow Chemical
471:metallocenes
468:
434:
383:
380:
374:resins), and
357:
328:syndiotactic
321:
298:
286:
271:
248:
172:
164:Giulio Natta
160:Karl Ziegler
153:
141:
132:
119:
110:multidentate
106:metallocenes
40:Giulio Natta
36:Karl Ziegler
31:
29:
1393:spin states
773:=CR–polymer
721:=CR–polymer
409:spheres of
407:microporous
1625:Categories
1341:Principles
1174:Chem. Rev.
937:0471238961
906:References
599:pyrophoric
588:phosphorus
524:) such as
1636:Catalysts
1592:chemistry
1412:Reactions
1388:Hapticity
839:Ti−H + CH
695:=CHR → Cp
590:(P), and
516:(M = Ti,
324:isotactic
316:tacticity
301:propylene
244:propylene
229:isotactic
168:propylene
154:The 1963
94:zirconium
1296:29711786
1257:15096060
1194:11749264
1133:26151395
796:=CHR → L
580:nitrogen
360:vanadium
240:ethylene
236:titanium
139:=CHR → −
135: CH
90:titanium
48:polymers
44:catalyst
806:-CHR–CH
769:−H + CH
553:-bridge
459:diether
343:Classes
150:History
122:alkenes
114:ligands
98:hafnium
42:, is a
1294:
1255:
1192:
1154:
1131:
1044:
1018:
967:
934:
717:R + CH
592:sulfur
572:oxygen
453:of an
207:α-TiCl
189:) and
70:, Al(C
825:Ti–CH
802:Ti–CH
788:Ti–CH
747:−CHR)
681:−CHR)
457:or a
451:ester
372:LLDPE
332:alkyl
276:(MgCl
193:(Al(C
185:(TiCl
126:vinyl
1292:PMID
1253:PMID
1190:PMID
1152:ISBN
1129:PMID
1042:ISBN
1016:ISBN
965:ISBN
932:ISBN
894:APAO
755:→ Cp
743:−(CH
691:+ CH
677:−(CH
613:ZrCl
551:ansa
444:MgCl
437:TiCl
419:Al(C
400:MgCl
393:TiCl
391:and
386:TiCl
251:BASF
214:Al(C
38:and
1284:doi
1245:doi
1182:doi
1178:100
1119:doi
1008:doi
957:doi
924:doi
833:→ L
751:−CH
713:−CH
709:−CH
687:−CH
586:),
578:),
540:−CH
512:MCl
326:or
307:.
246:.
96:or
1627::
1290:.
1280:38
1251:.
1241:37
1188:.
1127:.
1115:48
1113:.
1109:.
1076:^
1056:^
1014:.
979:^
963:.
930:.
765:Zr
739:Zr
729:Cp
705:Zr
673:Zr
663:Cp
631:CH
627:Zr
582:(N
574:(O
522:Hf
520:,
518:Zr
507:Cp
432:.
291:.
269:.
145:−;
92:,
30:A
1326:e
1319:t
1312:v
1298:.
1286::
1259:.
1247::
1196:.
1184::
1160:.
1135:.
1121::
1050:.
1024:.
1010::
973:.
959::
940:.
926::
896:)
841:3
836:n
831:2
827:2
822:n
819:L
808:2
804:2
799:n
794:2
790:2
785:n
782:L
771:2
762:+
757:2
753:3
749:n
745:2
736:+
731:2
719:2
715:2
711:2
702:+
697:2
693:2
689:3
684:n
679:2
670:+
665:2
633:3
624:+
619:2
615:2
611:2
584:2
576:2
546:2
542:2
538:2
514:2
510:2
502:n
484:.
446:2
439:4
429:3
427:)
425:5
423:H
421:2
415:2
402:2
395:3
388:4
336:3
318:.
278:2
224:3
222:)
220:5
218:H
216:2
209:3
203:2
201:)
199:5
197:H
195:2
187:4
142:n
137:2
133:n
116:.
80:3
78:)
76:5
74:H
72:2
20:)
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