CN1068331C - 含喹啉氧基或吡啶氧基配位体的过渡金属催化剂体系 - Google Patents

含喹啉氧基或吡啶氧基配位体的过渡金属催化剂体系 Download PDF

Info

Publication number
CN1068331C
CN1068331C CN96194004A CN96194004A CN1068331C CN 1068331 C CN1068331 C CN 1068331C CN 96194004 A CN96194004 A CN 96194004A CN 96194004 A CN96194004 A CN 96194004A CN 1068331 C CN1068331 C CN 1068331C
Authority
CN
China
Prior art keywords
catalyzer
catalyst
catalyst system
transition metal
metal catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN96194004A
Other languages
English (en)
Other versions
CN1188481A (zh
Inventor
S·纳吉
R·克里什纳莫蒂
J·A·泰里尔
L·V·克里伯斯
M·克克曼
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lyondell Chemical Co
Original Assignee
Lyondell Petrochemical Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lyondell Petrochemical Co filed Critical Lyondell Petrochemical Co
Publication of CN1188481A publication Critical patent/CN1188481A/zh
Application granted granted Critical
Publication of CN1068331C publication Critical patent/CN1068331C/zh
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/28—Titanium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/46—Titanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/48—Zirconium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/49—Hafnium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
    • B01J2531/56—Vanadium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
    • B01J2531/57—Niobium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/62—Chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/66—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/828—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/226—Sulfur, e.g. thiocarbamates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2420/00—Metallocene catalysts
    • C08F2420/04—Cp or analog not bridged to a non-Cp X ancillary anionic donor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Pyridine Compounds (AREA)

Abstract

公开了一种助催化剂和通式(1)的二齿吡啶过渡金属催化剂的催化剂组合物，式中Y为O、S、NR、(2)或(3)。R各独立地选自氢或C1-6烷基，M为钛、锆或铪；X各独立地选自卤素、C1-6烷基、C1-6烷氧基或(4)；L为X、环戊二烯基、C1-6烷基取代的环戊二烯基、茚基、芴基或(5)；R′各独立地选自R、C1-6烷氧基、C1-16芳基、卤素或CF3；n为1-4。
也公开了制备聚α-烯烃的方法，该方法包括用该催化剂组合物或具有下述通式(6)的催化剂的催化剂组合物聚合α-烯烃单体，式中Y、M、L、X和R′如前所定义。

Description

含喹啉氧基或吡啶氧基配位体的过渡金属催化剂体系
本发明涉及用于聚合α-烯烃的催化剂，特别涉及使用含吡啶或喹啉部分的二齿配位体的过渡金属催化剂进行的乙烯聚合。与US3,900,452中公开的反应产物不同，其中TiCl3 -吡啶盐中的钛形成一与杂环氮连接的非σ键，而本发明化合物含有的钛与氮形成一非σ键，同时又与氧原子形成一σ键，氧原子又与杂环连接。
直到最近，聚烯烃的生产主要还是使用常规的齐格勒催化体系。典型的齐格勒催化剂是由含过渡金属的化合物和一种或多种有机金属化合物组成的。例如聚乙烯是用诸如三氯化钛和氯化二乙基铝，或四氯化钛、三氯氧化钒与三乙基铝的混合物之类的齐格勒催化剂生产的。这些种类的催化剂比较便宜，但是它们的活性低，必须以高浓度使用。残留于聚合物中的催化剂使聚合物产生黄或灰色，而且紫外线稳定性和长期稳定性差；再者，含氯的残留物能腐蚀聚合物加工设备。因此时常需要从聚合物里清除催化剂残留物或在聚合物中加中和剂和稳定剂，以克服残留物的有害作用，这样就增加了生产成本。另外，用齐格勒催化剂产生分子量分布较宽的聚合物，这是在许多应用中(诸如注射模塑)不希望有的。在掺入α-烯烃共聚单体时，它们也是较差的，这使聚合物密度控制产生困难。要达到某一密度可能要求大量过量的共聚单体。许多高级α-烯烃(诸如1-辛烯)，如果需要掺入，则只能掺入极低的量。
自从发现齐格勒催化体系以来，虽然已有了大量的改进，但这些催化剂现在已被近期发现的金属茂催化剂所代替。典型的金属茂催化剂是由具有一个或多个环戊二烯基环状配位体的过渡金属化合物组成的。当金属茂与和传统齐格勒催化剂一起使用的有机金属化合物(诸如烷基铝)一起使用时，其活性很低，但当与作为助催化剂的铝氧烷一起使用时，则有很高的活性。其活性一般很高而无须自聚合物中除去其残留物。再者，用它们生产的聚合物分子量很高并且分子量分布很窄。它们也能很好地掺入α-烯烃共聚单体。
然而，在较高的温度下，金属茂催化剂趋于生产分子量较低的聚合物。因此，它们能用于约在80-90℃下进行的乙烯气相和淤浆聚合，但一般在增加温度时它们不能很好地进行。在较高温度下于溶液中进行的乙烯聚合是理想的，因为它具有较大的灵活性以生产分子量范围和密度较宽同时又可以用各种不同种类的共聚单体的聚合物。溶液聚合可以生产能在许多不同应用中使用的聚合物。例如可生产用作食品包装隔离膜的高分子量和高密度聚乙烯(PE)薄膜，和韧性好和抗中强度大的低密度乙烯共聚物。
现已发现了作为α-烯烃聚合催化剂其活性非常好的新颖二齿吡啶过渡金属化合物；也已发现至今为止无疑是具有任何催化性能的二齿喹啉过渡金属化合物，这些化合物也是优良的α-烯烃聚合催化剂。这些催化剂能生产性质与用金属茂催化剂生产的聚合物非常接近的聚合物，即聚合物有窄的分子量分布并均匀引入共聚单体。
含有二齿吡啶基配位体的本发明过渡金属催化剂的通式如下：
Figure C9619400400041
式中Y为O、S、NR、 R各独立地选自氢或C1-6烷基，R＇各独立地选自R、C1-6烷氧基、C6-16芳基、卤素或CF3,M为钛、锆或铪,X各独立地选自氢、C1-6烷基、C1-6烷氧基或 L为X、环戊二烯基、C1-6烷基取代的环戊二烯基、茚基、芴基或m为0-4,n为1-4。式中，基团Y最好是氧，因为这样的化合物较容易制备。同理，基团R最好是甲基，R＇最好是氢。基团L最好是卤素，更优选氯，因为这样的催化剂有较优越的性能，并且容易制备。同理，基团X最好是卤素，特别是氯；基团M最好是钛。
二齿吡啶配合物的制备在实施例中说明，但一般它们能通过将具有酸式质子的取代吡啶前体与具有式MX3L的化合物在HX清除剂存在下进行反应而制备。反应是化学计量的，优选清除剂的化学计量。适合的清除剂的实例包括比取代吡啶碱性更强的化合物，诸如三乙胺、吡啶、氢化钠和丁基锂。如果清除剂是比取代吡啶更强的碱，就可制取取代吡啶的盐，并以取代吡啶盐为原料。当反应优选在溶剂中进行时，反应物只要求有部分的溶解度。可以使用非质子溶剂，诸如四氢呋喃(THF)、乙醚、甲苯、或二甲苯，浓度可用约0.2-20wt％固体，优选约5-10wt％固体。反应的发生温度约为-78℃至室温左右。反应进行时有沉淀形成，产物可用甲苯、二氯甲烷、乙醚或类似的提取剂进行提取。
本发明的二齿喹啉过渡金属催化剂具有如下的通式：
Figure C9619400400061
式中R、R＇、L、M、X和n如前所定义。
喹啉过渡金属催化剂的制取方法与吡啶过渡金属催化剂类似，只是以取代喹啉(诸如8-羟基喹啉)代替取代吡啶。也可在溶剂中使用丁基锂以制取8-羟基喹啉的锂盐，8-羟基喹啉的锂盐也可用作起始原料。
因为催化剂在正常情况下是与有机金属助催化剂结合使用的，所以最好是将催化剂溶于助催化剂也能溶解的溶剂中。例如，如果甲基铝氧烷(MAO)或聚甲基铝氧烷(PMAO)为助催化剂，那么可以使用甲苯、二甲苯、苯或乙苯作溶剂。优选的助催化剂是MAO，因为用它能得到高的活性和分子量分布较窄的聚合物。在聚合中使用的有机金属助催化剂与催化剂之摩尔比一般在0.01∶1-100,000∶1的范围，优选1∶1-10,000的范围。
可以替代的助催化剂是含非配位的惰性阴离子的酸式盐(见US5,064,802)。酸式盐一般是非亲核化合物，它是由庞大的配位体连接在硼原子或铝原子上组成的，诸如四(五氟苯基)硼酸锂、四(五氟苯基)铝酸锂、四(五氟苯基)硼酸苯胺翁和它们的混合物。当这些化合物与催化剂反应时，所得到的阴离子相信是与含金属的阳离子成弱配位的。酸式盐与催化剂的摩尔比可在约0.01∶1-约1000∶1的范围，但最好是约1∶1-10∶1。从催从剂和酸式盐制备活性催化剂体系的方法没有限制，但优选的方法是在-78℃至约150℃的温度范围将它们在惰性溶剂中混合；需要时也可在单体的存在下进行混合。酸式盐可与上述的有机金属助催化剂结合使用。
催化剂和助催化剂可置于诸如硅胶、矾土、硅石、氧化镁或二氧化钛之类的载体上使用，但因它们对聚合物有污染，所以载体不是优选的。然而根据所使用的方法也可以需要载体。例如在气相聚合法和淤浆聚合法中一般需要有载体，以便控制所生产的聚合物的颗粒大小和阻止反应器壁结垢。使用载体时是将催化剂和助催化剂溶于溶剂，然后例如用蒸发溶剂的方法将其沉淀在载体材料上。助催化剂也可沉积在载体上或与载体化催化剂分别导入反应器。
催化剂是以常规方法用于烯属烃单体的聚合中。不饱和单体(诸如苯乙烯)可用本发明的催化剂来聚合，但它特别适用于聚合诸如丙烯、1-丁烯、1-己烯、1-辛烯、特别是乙烯之类的α-烯烃。
催化剂也可用常规方法用于诸如乙烯、丙烯、1-丁烯、1-己烯、1-辛烯等的不饱和单体混合物的共聚合，乙烯和诸如1,3-丁二烯、1,4-己二烯、1,5-己二烯等的二烯烃的混合物的共聚合；乙烯和诸如降冰片烯、亚乙基降冰片烯、乙烯基降冰片烯、降冰片二烯等的不饱和单体的混合物的共聚合。
本发明的催化剂可在各种不同的聚合方法中使用。它们可用于液相聚合法(淤浆、溶液、悬浮液、本体相聚合或其结合)，高压流体相或气相聚合法。这些方法可在系列或单级中使用。聚合反应区的压力可为约15psia至约50,000psia,温度可为约-78℃至约300℃。
实施例1
双(2-吡啶氧基)二氯化钛的合成
在0.02摩尔2-羟基吡啶和0.02摩尔三乙胺于50ml THF的溶液中在0℃下滴加0.01摩尔四氯化钛溶液，于室温下搅拌过夜。过滤后，蒸发THF溶液，从残留物中提取产物。产物结构如下：
Figure C9619400400081
实施例2
(环戊二烯基)(2-吡啶氧基)二氯化钛的制备
于0℃下将2-羟基吡啶(0.002摩尔)和三乙胺(0.002摩尔)于50ml乙醚中的溶液加入0.002摩尔环戊二烯基三氯化钛于50ml乙醚中的溶液，并搅拌过夜。从乙醚滤液中回收产物。产物结构如下：
实施例3
喹啉氧基过渡金属催化剂制备通法
在-78℃下将各种8-羟基喹啉衍生物的锂盐(用丁基锂制备)甲苯浆液与相应的钛或锆化合物(四氯化钛、四氯化锆、环戊二烯基三氯化钛或环戊二烯基三氯化锆)混合，并在室温下搅拌过夜。用甲苯或二氯甲烷提取，从反应混合物回收配合物。制备8-喹啉氧基三氯化钛(Ⅲ)是在-78℃下将0.01摩尔8-羟基喹啉的锂盐于30ml甲苯中的浆液(用1.45克(0.01摩尔)羟基喹啉和MeLi制备)加入1.9克(0.01摩尔)TiCl4于20ml甲苯中的溶液，并在室温下搅拌过夜。分离出沉淀，用甲苯洗涤，以100ml CH2Cl2提取。除去CH2Cl2后，分离得到棕色微晶状固体0.7克。
用类似方法由用2.28克(0.01摩尔)5,7-二氯-2-甲基-8-羟基喹啉制得的锂盐制备8-(2-甲基-5,7-二氯喹啉)氧基三氯化钛(Ⅳ)2.3克。
Figure C9619400400093
用类似的步骤由2.28克(0.01摩尔)5,7-二氯-2-甲基-8-羟基喹啉和1.165克(0.005摩尔)四氯化锆制备1.0克对比配合物双[8-(2-甲基-5,7-二氯喹啉)氧基]二氯化锆(Ⅴ)
Figure C9619400400101
(环戊二烯基)(8-喹啉氧基)二氯化锆(Ⅵ)和(环戊二烯基)[8-(2-甲基-5,7-二氯喹啉)氧基]二氯化锆(Ⅶ)的制备是用由1.45克(0.01摩尔)8-羟基喹啉或1.15克(0.005摩尔)5,7-二氯-2-甲基-8-羟基喹啉制得的锂盐在-78℃下与等摩尔量的环戊二烯基三氯化锆在甲苯中进行反应。在搅拌过夜和过滤后，从甲苯溶液分离到产物(0.62克Ⅵ和1.7克Ⅶ)。
实施例4
聚合反应
在研究中所有的聚合反应均在一个1.7升的反应器中进行。在进行聚合反应前反应器在用氮气吹扫下加热至130℃并保持在该温度30分钟进行“烘烤”。将乙烯、氢、己烯、丁烯和氮通过含13X分子筛的柱进行处理。在一典型的聚合反应中，反应器中加入0.850升己烷或甲苯，并用注射器加入要求体积的稀PMAO(AKZO公司)。监测盛氢的1升高压不锈钢容器的压力降(Δp)将所需的氢加入反应器。用加压氮将催化剂的甲苯溶液加入反应器。在整个实验过程中反应器保持在等温条件下。在反应器中通入乙烯并通过调压器在需要时加入乙烯将压力控制在150psi。在反应器的温度和压力稳定后，将催化剂浆液加入反应器，聚合反应开始。用布洛克斯质流计(Brooks mass flow meter)监测乙烯流量。
使反应器放气终止聚合反应，聚合物经过滤而回收。加入约1000ppm丁基化羟甲苯/己烷(BHT)以稳定聚合物，并在80℃于真空炉中进一步脱挥发物2小时。按ASTM D-1238测定聚合物的熔体流动性。按ASTM D-150585在密度梯度柱中测压塑模制品的聚合物密度。
                         反应条件记录在下表中。
实验号   催化剂   温度(℃)   共聚单体  共聚单体(克)  催化剂(毫摩尔)   摩尔Al/M H2,ΔP 反应时间(分钟)
    1     Ⅰ     80     无     0     9.5E-3     1897     0     15
    2     Ⅰ     80     无     0     4.7E-3     3795     0     15
    3     Ⅰ     80     无     0     4.7E-3     1897     20     15
    4     Ⅰ     80     无     0    4.7E-3     1897     50     10
    5     Ⅰ     80     丁烯     20     4.7E-3     1897     20     15
    6     Ⅱ     80     无     0     9.0E-3     1001     0     60
    7     Ⅲ     80     丁烯     10     8.4E-3     1074     10     30
    8     Ⅲ     80     无     10     8.4E-3     1074     10     30
    9     Ⅳ     80     丁烯     0     6.6E-3     1324     0     30
    10     Ⅳ     80     丁烯     10     6.6E-3     1324     10     30
  11*     Ⅴ     80     丁烯     10     1.14E-2     1175     0     10
  12*     Ⅴ     80     丁烯     10     4.06E-3     1645     0     10
  13*     Ⅴ     80     丁烯     10     8.12E-3     1645     0     10
    14     Ⅵ     80     丁烯     10     6.74E-3     991     0     15
    15     Ⅵ     80     丁烯     10     1.35E-2     991     0     15
    16     Ⅵ     80     丁烯     10     1.35E-2     1288     5     15
    17     Ⅵ     80     丁烯     10     1.89E-2     1132     15     15
    18     Ⅵ     110     丁烯     10     1.89E-2     1132     0     15
    19     Ⅶ     80     丁烯     10     1.10E-2     1212     0     15
    20     Ⅶ     80     丁烯     10     1.10E-2     1212     5     15
    21     Ⅶ     110     丁烯     10     1.54E-2     1126     15     15
    22     Ⅶ     80     丁烯     10     1.54E-2     1126     0     15
    23     Ⅶ     80     丁烯     10     1.54E-2     2078     0     15
表中“Al/M”为催化剂的PMAO中的铝对金属(钛或锆)的摩尔比*对比实施例下表为聚合反应结果
实验号 催化剂产率(kg/gm/h)      MI2     MI20     MFR      密度     Mw/Mn
    1     179.0   ＜0.01   ＜0.01    -
    2     153.2   ＜0.01   ＜0.01    -
    3     165.5   ＜0.01     1.8    -
    4     133.1   ＜0.01     2.47    -
    5     272.9   ＜0.01     0.964    -
    6     62.9   ＜0.01   ＜0.01    -
    7     99.2     0.90     16.9    18.9     0.9513     2.51
    8     167.9     0.41     4.2    10.2     3.67
    9     103.2   ＜0.01     -    -
    10     24.8   ＜0.01     -    -
    11*     低       -     -    -
    12*     无       -     -    -
    13*     无       -     -    -
    14     无       -     -    -
    15     98.1   ＜0.01     1.15    -
    16     177.7     0.93     21.4    23.1
    17     137.6     1.31     34.5    26.3
    18     159.0     0.81     16.1    19.8
    19     119.8   ＜0.01     .83     -
    20     198.7     0.46     11.4    24.7
    21     157.8     0.63     17.8    28.2
    22     160.1     0.06     12.8    -
    23     112.1     0.06     1.84    29.7
*对比实施例表中的Kg/gM/h为每克催化剂每小时生产的聚合物千克数。聚合物的熔体指数根据ASTM D-1238条件E和条件F测定。MI2是用2.16公斤重量(条件E)测定的熔体指数。MI20是用21.6公斤重量(条件F)测定的熔体指数。MFR是MI20/MI2比。聚合物密度根据ASTM D-1505测定。聚合物分子量分布的测定使用Wa-ters 150C凝胶渗透色谱仪，温度为135℃，溶剂为1,2,4-三氯苯。用重均分子量(Mw)和Mw/Mn(数均分子量)比表示分子量分布特征。
用本发明的催化剂可得到好的生产率和高分子量聚合物，由其极低的MI值可证实，甚至在较高温度(110℃)下催化剂Ⅵ和Ⅶ也是如此。

Claims (6)

1．一种催化剂体系，包括：
(a)一种助催化剂，和
(b)一种催化剂，包括选自锆、钛和铪的过渡金属和配位到金属上的双齿配位体，其中该配位体是8-喹啉氧基或2-吡啶氧基配位体。
2．权利要求1的催化剂体系，其中助催化剂选自甲基铝氧烷(MAO)、聚甲基铝氧烷(PMAO)和非配位惰性阴离子的酸式盐。
3．权利要求1的催化剂体系，其中该配位体是被C1-6烷基、C1-6烷氧基、卤素或CF3取代的2-吡啶氧基和8-喹啉氧基。
4．载体化的权利要求1的催化剂体系。
5．在权利要求1的催化剂体系存在下聚合乙烯的方法。
6．在权利要求1的催化剂体系存在下聚合一种或多种线性或枝化α-烯烃的方法。
CN96194004A 1995-04-17 1996-03-18 含喹啉氧基或吡啶氧基配位体的过渡金属催化剂体系 Expired - Fee Related CN1068331C (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US08/423,232 1995-04-17
US08/423,232 US5637660A (en) 1995-04-17 1995-04-17 Polymerization of α-olefins with transition metal catalysts based on bidentate ligands containing pyridine or quinoline moiety

Publications (2)

Publication Number Publication Date
CN1188481A CN1188481A (zh) 1998-07-22
CN1068331C true CN1068331C (zh) 2001-07-11

Family

ID=23678124

Family Applications (1)

Application Number Title Priority Date Filing Date
CN96194004A Expired - Fee Related CN1068331C (zh) 1995-04-17 1996-03-18 含喹啉氧基或吡啶氧基配位体的过渡金属催化剂体系

Country Status (12)

Country Link
US (3) US5637660A (zh)
EP (2) EP0832089B1 (zh)
JP (1) JPH11503785A (zh)
KR (1) KR19990007920A (zh)
CN (1) CN1068331C (zh)
AU (1) AU5314496A (zh)
BR (1) BR9608224A (zh)
DE (2) DE69615554T2 (zh)
ES (2) ES2255914T3 (zh)
MX (1) MX9707982A (zh)
RU (1) RU2169735C2 (zh)
WO (1) WO1996033202A2 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102781981A (zh) * 2010-02-19 2012-11-14 陶氏环球技术有限责任公司 烯烃单体聚合方法及其催化剂

Families Citing this family (178)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5637660A (en) * 1995-04-17 1997-06-10 Lyondell Petrochemical Company Polymerization of α-olefins with transition metal catalysts based on bidentate ligands containing pyridine or quinoline moiety
EP0852230B1 (en) * 1995-08-31 2001-12-05 Sumitomo Chemical Company Limited Transition metal complexes, catalyst for olefin polymerization, and process for producing olefin polymers
US5852146A (en) * 1996-06-27 1998-12-22 Union Carbide Chemicals & Plastics Technology Corporation Catalyst for the production of olefin polymers
US5856258A (en) * 1996-10-15 1999-01-05 Northwestern University Phenolate constrained geometry polymerization catalyst and method for preparing
US6432862B1 (en) * 1996-12-17 2002-08-13 E. I. Du Pont De Nemours And Company Cobalt catalysts for the polymerization of olefins
US6214761B1 (en) * 1996-12-17 2001-04-10 E. I. Du Pont De Nemours And Company Iron catalyst for the polymerization of olefins
US6417305B2 (en) * 1996-12-17 2002-07-09 E. I. Du Pont De Nemours And Company Oligomerization of ethylene
US6451938B1 (en) 1997-02-25 2002-09-17 Exxon Mobil Chemical Patents Inc. Polymerization catalyst system comprising heterocyclic fused cyclopentadienide ligands
TW420693B (en) * 1997-04-25 2001-02-01 Mitsui Chemicals Inc Olefin polymerization catalysts, transition metal compounds, and <alpha>-olefin/conjugated diene copolymers
US6136748A (en) * 1997-07-02 2000-10-24 Union Carbide Chemicals & Plastics Technology Corporation Catalyst composition for the polymerization of olefins
US6268447B1 (en) * 1998-12-18 2001-07-31 Univation Technologies, L.L.C. Olefin polymerization catalyst
US6103657A (en) * 1997-07-02 2000-08-15 Union Carbide Chemicals & Plastics Technology Corporation Catalyst for the production of olefin polymers
US6096676A (en) * 1997-07-02 2000-08-01 Union Carbide Chemicals & Plastics Technology Corporation Catalyst for the production of olefin polymers
US6642316B1 (en) 1998-07-01 2003-11-04 Exxonmobil Chemical Patents Inc. Elastic blends comprising crystalline polymer and crystallizable polym
CN1067690C (zh) * 1998-03-04 2001-06-27 中国科学院化学研究所 一种间规聚合的催化剂体系及其制备方法和用途
GB9809207D0 (en) * 1998-04-29 1998-07-01 Bp Chem Int Ltd Novel catalysts for olefin polymerisation
US6333389B2 (en) * 1998-12-18 2001-12-25 Univation Technologies, Llc Olefin polymerization catalysts, their production and use
US6303719B1 (en) 1998-12-18 2001-10-16 Univation Technologies Olefin polymerization catalyst system
US6180552B1 (en) 1999-04-07 2001-01-30 Equistar Chemicals, L.P. Transition metal complexes containing neutral, multidentate azacyclic ligands
US6204216B1 (en) 1999-04-15 2001-03-20 Equistar Chemicals, L.P. Olefin polymerization catalysts containing amine derivatives
US6201076B1 (en) 1999-04-29 2001-03-13 Equistar Chemicals, L.P. Olefin polymerization process with fatty amine additives for improved activity and reduced fouling
US6020493A (en) * 1999-05-06 2000-02-01 Equistar Chemicals, Lp Single-site catalyst preparation
US6271325B1 (en) 1999-05-17 2001-08-07 Univation Technologies, Llc Method of polymerization
US6211311B1 (en) 1999-05-25 2001-04-03 Equistar Chemicals, L.P. Supported olefin polymerization catalysts
US6291386B1 (en) 1999-05-25 2001-09-18 Equistar Chemicals, Lp Process for the in-situ preparation of single-site transition metal catalysts and polymerization process
US6239062B1 (en) 1999-09-02 2001-05-29 Equistar Chemicals, L.P. Olefin polymerization catalysts containing indolyl-amido ligands
US6194527B1 (en) 1999-09-22 2001-02-27 Equistar Chemicals, L.P. Process for making polyolefins
US6265504B1 (en) 1999-09-22 2001-07-24 Equistar Chemicals, Lp Preparation of ultra-high-molecular-weight polyethylene
US6232260B1 (en) 1999-10-14 2001-05-15 Equistar Chemicals, L.P. Single-site catalysts for olefin polymerization
US6228959B1 (en) 1999-10-15 2001-05-08 Equistar Chemicals, L.P. Single-site catalysts containing homoaromatic ligands
US6274684B1 (en) 1999-10-22 2001-08-14 Univation Technologies, Llc Catalyst composition, method of polymerization, and polymer therefrom
US6624107B2 (en) 1999-10-22 2003-09-23 Univation Technologies, Llc Transition metal catalyst compounds having deuterium substituted ligand and catalyst systems thereof
US6417304B1 (en) 1999-11-18 2002-07-09 Univation Technologies, Llc Method of polymerization and polymer produced therefrom
US6271323B1 (en) 1999-10-28 2001-08-07 Univation Technologies, Llc Mixed catalyst compounds, catalyst systems and their use in a polymerization process
US6265505B1 (en) 1999-11-18 2001-07-24 Univation Technologies, Llc Catalyst system and its use in a polymerization process
US6300439B1 (en) 1999-11-08 2001-10-09 Univation Technologies, Llc Group 15 containing transition metal catalyst compounds, catalyst systems and their use in a polymerization process
US6300438B1 (en) 1999-10-22 2001-10-09 Univation Technolgies, Llc Hafnium transition metal catalyst compounds, catalyst systems and their use in a polymerization process
US6380328B1 (en) 1999-12-10 2002-04-30 Univation Technologies, Llc Catalyst systems and their use in a polymerization process
KR100710963B1 (ko) * 1999-11-01 2007-04-24 더블유.알. 그레이스 앤드 컴파니 -씨오엔엔. 활성의 불균일 지지된 비덴테이트 또는 트리덴테이트계의올레핀 중합 촉매
US6294626B1 (en) 1999-11-15 2001-09-25 Equistar Chemicals, Lp Olefin polymerization catalysts containing modified boraaryl ligands
US6281155B1 (en) 1999-11-19 2001-08-28 Equistar Chemicals, L.P. Supported olefin polymerization catalysts
US6281306B1 (en) 1999-12-16 2001-08-28 Univation Technologies, Llc Method of polymerization
US6239239B1 (en) * 2000-02-17 2001-05-29 Equistar Chemicals, L.P. Quinolinoxy and pyridinoxy single-site catalysts containing benzyl ligands
US6255415B1 (en) * 2000-02-29 2001-07-03 Equistar Chemicals, L.P. Ethylene polymerization process
US6476165B1 (en) 2000-03-08 2002-11-05 Equistar Chemicals, Lp Olefin polymerization process using fatty amine additives and boron-modified supported catalyst
US6498221B1 (en) * 2000-03-30 2002-12-24 Equistar Chemicals, Lp Single-site catalysts containing chelating N-oxide ligands
US6812304B2 (en) 2000-06-14 2004-11-02 Equistar Chemicals, Lp Process for producing improved premixed supported boraaryl catalysts
EP1303543A1 (en) * 2000-07-17 2003-04-23 Univation Technologies LLC A catalyst system and its use in a polymerization process
US6433088B1 (en) 2000-08-04 2002-08-13 Equistar Chemicals, Lp Clear and printable polypropylene films
US6486270B1 (en) 2000-08-25 2002-11-26 Equistar Chemicals, Lp High molecular weight, medium density polyethylene
US6355733B1 (en) 2000-10-13 2002-03-12 Equistar Chemicals, Lp Polyethylene blends and films
US6414099B1 (en) 2000-10-18 2002-07-02 Equistar Chemicals, Lp Single-site catalysts based on caged diimide ligands
WO2002046249A2 (en) 2000-11-07 2002-06-13 Symyx Technologies, Inc. Methods of copolymerizing ethylene and isobutylene and polymers made thereby
US6660678B1 (en) 2000-11-21 2003-12-09 Equistar Chemicals, Lp Single-site catalysts for olefin polymerization
EP1700870B9 (en) 2000-12-06 2009-09-02 Eidgenössische Technische Hochschule Zürich Melt-processible, wear resistant polyethylene
CA2430852A1 (en) * 2000-12-06 2002-06-13 Omlidon Technologies Llc Melt-processible, wear resistant polyethylene
US6878662B2 (en) 2000-12-28 2005-04-12 Univation Technologies, Llc Polymerization catalyst system, polymerization process and polymer therefrom
US6673882B2 (en) * 2001-02-12 2004-01-06 Equistar Chemicals, Lp Supported single-site catalysts useful for olefin polymerization
US6664349B2 (en) 2001-03-29 2003-12-16 Equistar Chemicals, Lp Ethylene polymerization process
US6579957B2 (en) 2001-04-11 2003-06-17 Equistar Chemicals, Lp Single-site catalysts based on anionic thiopyran dioxide ligands
ATE485319T1 (de) 2001-04-12 2010-11-15 Exxonmobil Chem Patents Inc Verfahren zur polymerisation von propylen und ethylen in lösung
US6391988B1 (en) 2001-04-18 2002-05-21 Equistar Chemicals L.P. Tris(pyrazoyl) based anions
US6583240B2 (en) 2001-05-23 2003-06-24 Equistar Chemicals, Lp Ethylene polymerization process
US6759361B2 (en) * 2001-06-04 2004-07-06 Equistar Chemicals, Lp Aluminoboronate activators for single-site olefin polymerization catalysts
US6489414B1 (en) * 2001-06-06 2002-12-03 Equistar Chemicals, Lp Chelating pyrimidines as ligands for single-site olefin polymerization catalysts
US6544918B1 (en) 2001-07-17 2003-04-08 Equistar Chemicals, Lp Olefin polymerization catalysts containing chelating dianionic ligands
US6583242B2 (en) 2001-08-02 2003-06-24 Equistar Chemicals, Lp Supported olefin polymerization catalysts
US7439379B2 (en) 2001-09-14 2008-10-21 Sumitomo Chemical Co., Ltd. Transition metal complex, catalyst for olefin polymerization, and process for producing olefin polymer with the same
US7834112B2 (en) * 2001-09-14 2010-11-16 Basell Polyolefine Gmbh Method of polymerization of olefins
DE10145453A1 (de) * 2001-09-14 2003-06-05 Basell Polyolefine Gmbh Monocyclopentadienylkomplexe mit einem kondensierten Heterocyclus
CN1160381C (zh) * 2001-09-27 2004-08-04 中国石油化工股份有限公司 含双席夫碱配体的烯烃聚合催化剂及制备方法与应用
US6927256B2 (en) 2001-11-06 2005-08-09 Dow Global Technologies Inc. Crystallization of polypropylene using a semi-crystalline, branched or coupled nucleating agent
US7122689B2 (en) * 2001-11-06 2006-10-17 Symyx Technologies, Inc. Titanium substituted pyridyl amine complexes, catalysts and processes for polymerizing ethylene and stryene
SG147306A1 (en) 2001-11-06 2008-11-28 Dow Global Technologies Inc Isotactic propylene copolymers, their preparation and use
US6960635B2 (en) * 2001-11-06 2005-11-01 Dow Global Technologies Inc. Isotactic propylene copolymers, their preparation and use
US6906160B2 (en) * 2001-11-06 2005-06-14 Dow Global Technologies Inc. Isotactic propylene copolymer fibers, their preparation and use
US6919467B2 (en) 2001-12-18 2005-07-19 Univation Technologies, Llc Imino-amide catalyst compositions for the polymerization of olefins
US6831187B2 (en) 2001-12-18 2004-12-14 Univation Technologies, Llc Multimetallic catalyst compositions for the polymerization of olefins
US7001863B2 (en) 2001-12-18 2006-02-21 Univation Technologies, Llc Monoamide based catalyst compositions for the polymerization of olefins
US6864205B2 (en) 2001-12-18 2005-03-08 Univation Technologies, Llc Heterocyclic-amide catalyst compositions for the polymerization of olefins
US7199255B2 (en) 2001-12-18 2007-04-03 Univation Technologies, Llc Imino-amide catalysts for olefin polymerization
US6586545B1 (en) 2001-12-20 2003-07-01 Equistar Chemicals, Lp Complexes based on four-membered cyclic anionic six-electron-donor ligands
US6596826B1 (en) 2001-12-20 2003-07-22 Equistar Chemicals, Lp Olefin polymerization catalysts containing 1,3-diboretanyl ligands
US6635728B2 (en) * 2002-01-10 2003-10-21 Equistar Chemicals, Lp Preparation of ultra-high-molecular-weight polyethylene
US6613841B2 (en) 2002-01-28 2003-09-02 Equistar Chemicals, Lp Preparation of machine direction oriented polyethylene films
US6780807B2 (en) 2002-02-04 2004-08-24 Equistar Chemicals L.P. Acyclic anionic six-electron-donor ancillary ligands
US6825296B2 (en) * 2002-03-29 2004-11-30 The University Of Hong Kong Catalyst component for olefin polymerization
US6693157B2 (en) * 2002-04-08 2004-02-17 Equistar Chemicals, Lp Olefin polymerization catalysts containing triquinane ligands
US6908972B2 (en) 2002-04-16 2005-06-21 Equistar Chemicals, Lp Method for making polyolefins
US7094723B2 (en) * 2002-04-18 2006-08-22 Equistar Chemicals Lp Catalysts containing at least one heterocyclic ligand for improving the catalysts' performance of olefin polymerization
US6642326B1 (en) 2002-05-03 2003-11-04 Equistar Chemicals, Lp Use of silanes to enhance activity in single-site polymerizations
US6649698B1 (en) 2002-05-17 2003-11-18 Equistar Chemicals, Lp Polyethylene blends
US6762255B2 (en) 2002-06-06 2004-07-13 Equistar Chemicals L.P. Prealkylated olefin polymerization catalysts and olefin polymerization employing such catalysts
US6630547B1 (en) 2002-06-11 2003-10-07 Equistar Chemicals, Lp Use of silanes to control molecular weight in olefin polymerizations
US7105672B2 (en) * 2002-08-19 2006-09-12 The University Of Hong Kong Cyclometallated catalysts
US6765074B2 (en) 2002-09-27 2004-07-20 Equistar Chemicals, Lp Olefin polymerization process
KR101113341B1 (ko) 2002-10-15 2012-09-27 엑손모빌 케미칼 패턴츠 인코포레이티드 올레핀 중합용 다중 촉매 시스템 및 이로부터 제조된중합체
US7223822B2 (en) 2002-10-15 2007-05-29 Exxonmobil Chemical Patents Inc. Multiple catalyst and reactor system for olefin polymerization and polymers produced therefrom
US6884749B2 (en) 2002-10-17 2005-04-26 Equistar Chemicals L.P. Supported catalysts which reduce sheeting in olefin polymerization, process for the preparation and the use thereof
US6630548B1 (en) 2002-11-01 2003-10-07 Equistar Chemicals, Lp Static reduction
US7579407B2 (en) * 2002-11-05 2009-08-25 Dow Global Technologies Inc. Thermoplastic elastomer compositions
US7459500B2 (en) * 2002-11-05 2008-12-02 Dow Global Technologies Inc. Thermoplastic elastomer compositions
US6716936B1 (en) 2002-12-16 2004-04-06 Equistar Chemicals L.P. Cascaded boiling pool slurry reactors for producing bimodal low to medium density polyethylene polymers
US6713576B1 (en) 2003-02-25 2004-03-30 Equistar Chemicals, Lp Olefin polymerization catalysts based on convex, polcyclic ligands
ATE469927T1 (de) 2003-03-21 2010-06-15 Dow Global Technologies Inc Verfahren zur herstellung von polyolefinen mit kontrollierter morphologie
WO2004089963A1 (en) * 2003-04-04 2004-10-21 San Diego State University Foundation Compositions and methods for facilitating reaction at room temperature
US6710005B1 (en) * 2003-04-10 2004-03-23 Equistar Chemicals, Lp Aluminoxane modification
US6984599B2 (en) * 2003-04-23 2006-01-10 Equistar Chemicals, Lp Olefin polymerization catalysts based on hydroxyl-depleted calixarene ligands
US6774078B1 (en) 2003-04-23 2004-08-10 Equistar Chemicals, Lp Olefin polymerization catalysts based on annulated cyclopentadienyl ligands
US6953764B2 (en) 2003-05-02 2005-10-11 Dow Global Technologies Inc. High activity olefin polymerization catalyst and process
US6995216B2 (en) * 2003-06-16 2006-02-07 Equistar Chemicals, Lp Process for manufacturing single-site polyolefins
US6767975B1 (en) 2003-07-14 2004-07-27 Equistar Chemicals, Lp Olefin polymerization with pyridine moiety-containing singe-site catalysts
US6930156B2 (en) * 2003-10-22 2005-08-16 Equistar Chemicals, Lp Polymer bound single-site catalysts
US20050148742A1 (en) * 2004-01-02 2005-07-07 Hagerty Robert O. Method for controlling sheeting in gas phase reactors
US20070073012A1 (en) * 2005-09-28 2007-03-29 Pannell Richard B Method for seed bed treatment before a polymerization reaction
US7985811B2 (en) * 2004-01-02 2011-07-26 Univation Technologies, Llc Method for controlling sheeting in gas phase reactors
US7011892B2 (en) * 2004-01-29 2006-03-14 Equistar Chemicals, Lp Preparation of polyethylene films
US20050200046A1 (en) * 2004-03-10 2005-09-15 Breese D. R. Machine-direction oriented multilayer films
US7037987B2 (en) * 2004-03-26 2006-05-02 Rohn And Haas Company Olefin polymerization catalyst and polymerization process
PL1732756T3 (pl) * 2004-04-05 2011-04-29 Leucadia Inc Degradowalna siatka
US7598328B2 (en) * 2004-04-07 2009-10-06 Dow Global Technologies, Inc. Supported catalysts for manufacture of polymers
US7175918B2 (en) * 2004-04-27 2007-02-13 Equistar Chemicals, Lp Polyolefin compositions
WO2006009980A2 (en) * 2004-06-21 2006-01-26 Exxonmobil Chemical Patents Inc. Olefin polymerisation process
US8440125B2 (en) 2004-06-28 2013-05-14 Equistar Chemicals, Lp Polyethylene films having high resistance to deformation or elongation
CA2473378A1 (en) * 2004-07-08 2006-01-08 Nova Chemicals Corporation Novel borate activator
US7125939B2 (en) * 2004-08-30 2006-10-24 Equistar Chemicals, Lp Olefin polymerization with polymer bound single-site catalysts
US7402546B2 (en) * 2004-09-23 2008-07-22 Equistar Chemicals, Lp Magnesium chloride support
EP1805226A1 (en) 2004-10-29 2007-07-11 Exxonmobil Chemical Patents Inc. Catalyst compound containing divalent tridentate ligand
WO2006066126A2 (en) * 2004-12-16 2006-06-22 Symyx Technologies, Inc. Phenol-heterocyclic ligands, metal complexes, and their uses as catalysts
US8034461B2 (en) * 2005-02-09 2011-10-11 Equistar Chemicals, Lp Preparation of multilayer polyethylene thin films
US20060177641A1 (en) * 2005-02-09 2006-08-10 Breese D R Multilayer polyethylene thin films
US7414006B2 (en) * 2005-03-09 2008-08-19 Exxonmobil Chemical Patents Inc. Methods for oligomerizing olefins
US7425661B2 (en) * 2005-03-09 2008-09-16 Exxonmobil Chemicals Patents Inc. Methods for oligomerizing olefins
US8461223B2 (en) 2005-04-07 2013-06-11 Aspen Aerogels, Inc. Microporous polycyclopentadiene-based aerogels
US9469739B2 (en) 2005-04-07 2016-10-18 Aspen Aerogels, Inc. Microporous polyolefin-based aerogels
DE112006001733T5 (de) 2005-07-01 2008-07-31 Albemarle Corporation Aluminoxanatsalzzusammensetzungen mit verbesserter Stabilität in aromatischen und aliphatischen Lösungsmitteln
US7232604B2 (en) * 2005-07-28 2007-06-19 Equistar Chemicals, Lp Flame retardant crosslinkable compositions and articles
US7273914B2 (en) * 2005-08-03 2007-09-25 Equistar Chemicals, Lp Olefin polymerization methods
US7091291B1 (en) 2005-11-23 2006-08-15 Equistar Chemicals, Lp Olefin polymerization process
US7608327B2 (en) * 2005-12-20 2009-10-27 Equistar Chemicals, Lp High tear strength film
EP1803747A1 (en) 2005-12-30 2007-07-04 Borealis Technology Oy Surface-modified polymerization catalysts for the preparation of low-gel polyolefin films
US7982085B2 (en) * 2006-02-03 2011-07-19 Exxonmobil Chemical Patents Inc. In-line process for generating comonomer
US8003839B2 (en) * 2006-02-03 2011-08-23 Exxonmobil Chemical Patents Inc. Process for generating linear apha olefin comonomers
US8076524B2 (en) * 2006-02-03 2011-12-13 Exxonmobil Chemical Patents Inc. Process for generating alpha olefin comonomers
US8404915B2 (en) * 2006-08-30 2013-03-26 Exxonmobil Chemical Patents Inc. Phosphine ligand-metal compositions, complexes, and catalysts for ethylene trimerizations
US8629280B2 (en) * 2007-01-08 2014-01-14 Exxonmobil Chemical Patents Inc. Methods for oligomerizing olefins with chromium pyridine ether catalysts
WO2008085658A1 (en) * 2007-01-08 2008-07-17 Exxonmobil Chemical Patents Inc. Methods for oligomerizing olefins with chromium pyridine thioether catalysts
US8138348B2 (en) * 2007-01-08 2012-03-20 Exxonmobil Chemical Patents Inc. Methods for oligomerizing olefins with chromium pyridine mono-oxazoline catalysts
EP2121183A1 (en) * 2007-01-08 2009-11-25 ExxonMobil Chemical Patents Inc. Chromium complexes of pyridine bis (oxazoline)-ligands for ethylene dimerization
US20080163978A1 (en) * 2007-01-09 2008-07-10 Botros Maged G Process for producing multi-layer structures having improved metal adhesion
US7794848B2 (en) * 2007-01-25 2010-09-14 Equistar Chemicals, Lp MDO multilayer polyethylene film
BRPI0703586B1 (pt) 2007-10-19 2018-02-06 Braskem S.A Catalisador metaloceno suportado, e, copolímeros de etileno com alfa-olefinas de alto e ultra alto peso molecular
US20090286944A1 (en) * 2008-05-15 2009-11-19 Symyx Technologies, Inc. Select phenol-heterocycle ligands, metal complexes formed therefrom, and their uses as catalysts
KR101142117B1 (ko) * 2008-09-25 2012-05-09 에스케이이노베이션 주식회사 전이금속 촉매계 및 이를 이용한 에틸렌 단독중합체 또는 에틸렌과 α-올레핀의 공중합체 제조방법
KR101142122B1 (ko) * 2008-09-30 2012-05-09 에스케이이노베이션 주식회사 새로운 전이금속 촉매계 및 이를 이용한 에틸렌 단독중합체또는 에틸렌과 α-올레핀의 공중합체 제조방법
US20100120308A1 (en) * 2008-11-13 2010-05-13 Conwed Plastics Llc Oxo-biodegradable netting
EP2408684B1 (de) * 2009-03-20 2013-08-21 Basf Se Biologisch abbaubares material aus einem polymer enthaltenden porösen metallorganischen gerüstmaterial
US8227653B2 (en) 2009-03-27 2012-07-24 Exxonmobil Chemical Patents Inc. Olefin oligomerization reaction processes exhibiting reduced fouling
US7858718B1 (en) * 2009-07-22 2010-12-28 Equistar Chemicals, Lp Catalysts based on 2-aryl-8-anilinoquinoline ligands
US8153544B2 (en) * 2009-07-22 2012-04-10 Equistar Chemicals, Lp Method for preparing non-metallocene catalysts
US8158733B2 (en) 2009-07-22 2012-04-17 Equistar Chemicals, Lp Catalysts based on 2-(2-aryloxy)quinoline or 2-(2-aryloxy)dihydroquinoline ligands
CA2688217C (en) * 2009-12-11 2016-07-12 Nova Chemicals Corporation Multi reactor process
PL2526129T3 (pl) * 2010-01-21 2018-05-30 Saudi Basic Industries Corporation (Sabic) Sposób polimeryzacji etylenu
CN101857651B (zh) * 2010-06-12 2012-06-20 上海化工研究院 具有单活性中心的超高分子量聚乙烯催化剂的制备方法
US20120016092A1 (en) 2010-07-14 2012-01-19 Sandor Nagy Catalysts based on quinoline precursors
WO2012024472A1 (en) 2010-08-18 2012-02-23 Sun Chemical Corporation Chlorine-free ink and coating compositions & a method for printing on untreated polyolefin films with improved adhesion
ES2540117T3 (es) 2010-11-22 2015-07-08 Albemarle Corporation Composiciones de activador, su preparación, y su uso en catálisis
BR112014026674B1 (pt) 2012-04-27 2021-10-05 W.R.Grace & Co.-Conn Composição de precursor de ativador e processo de formação
BR112017005470B8 (pt) * 2014-09-17 2023-09-26 Versalis Spa Complexo de piridina de zircônio, sistema catalítico, processo para a (co)polimerização de dienos conjugados e processo para polimerização de 1,3-butadieno
CA2864573C (en) 2014-09-22 2021-07-06 Nova Chemicals Corporation Shrink film from single site catalyzed polyethylene
SG11201703851UA (en) 2014-11-25 2017-06-29 Univation Tech Llc Methods of controlling polyolefin melt index
CA2874895C (en) 2014-12-16 2022-02-15 Nova Chemicals Corporation High modulus single-site lldpe
KR101931234B1 (ko) 2016-02-12 2018-12-21 주식회사 엘지화학 신규한 리간드 화합물 및 전이금속 화합물
WO2017138783A1 (ko) * 2016-02-12 2017-08-17 주식회사 엘지화학 신규한 리간드 화합물 및 전이금속 화합물
CN112646065B (zh) * 2019-10-11 2022-11-18 中国石油化工股份有限公司 一种新型单茂过渡金属化合物、包含其的催化剂组合物与应用
CN111747995B (zh) * 2020-07-30 2023-02-21 上海化工研究院有限公司 一种含氮芳氧基茂钛化合物及其制备方法和应用
US20240209124A1 (en) 2021-04-30 2024-06-27 Exxonmobil Chemical Patents Inc. Processes for transitioning between different polymerization catalysts in a polymerization reactor
CN116410224B (zh) * 2023-06-05 2023-11-10 研峰科技(北京)有限公司 一种环戊二烯三氯化钛的合成工艺

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3900452A (en) * 1963-06-07 1975-08-19 Montedison Spa Olefinic copolymers and process for the preparation thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5149880A (en) * 1990-01-16 1992-09-22 The Texas A & M University System Nitrogen-containing aromatic heterocyclic ligand-metal complexes and their use for the activation of hydrogen peroxide and dioxygen in the reaction of organic compounds
US5637660A (en) * 1995-04-17 1997-06-10 Lyondell Petrochemical Company Polymerization of α-olefins with transition metal catalysts based on bidentate ligands containing pyridine or quinoline moiety
US5852146A (en) * 1996-06-27 1998-12-22 Union Carbide Chemicals & Plastics Technology Corporation Catalyst for the production of olefin polymers

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3900452A (en) * 1963-06-07 1975-08-19 Montedison Spa Olefinic copolymers and process for the preparation thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102781981A (zh) * 2010-02-19 2012-11-14 陶氏环球技术有限责任公司 烯烃单体聚合方法及其催化剂

Also Published As

Publication number Publication date
ES2255914T3 (es) 2006-07-16
DE69635719D1 (de) 2006-04-06
CN1188481A (zh) 1998-07-22
ES2164878T3 (es) 2002-03-01
WO1996033202A3 (en) 1996-11-28
RU2169735C2 (ru) 2001-06-27
DE69615554D1 (de) 2001-10-31
WO1996033202A2 (en) 1996-10-24
EP1059310A2 (en) 2000-12-13
JPH11503785A (ja) 1999-03-30
US20040097670A1 (en) 2004-05-20
US6759493B1 (en) 2004-07-06
AU5314496A (en) 1996-11-07
BR9608224A (pt) 1999-11-30
DE69615554T2 (de) 2002-05-08
EP1059310A3 (en) 2004-08-04
KR19990007920A (ko) 1999-01-25
MX9707982A (es) 1998-02-28
EP0832089B1 (en) 2001-09-26
US5637660A (en) 1997-06-10
US6790918B2 (en) 2004-09-14
DE69635719T2 (de) 2006-09-28
EP0832089A2 (en) 1998-04-01
EP1059310B1 (en) 2006-01-11

Similar Documents

Publication Publication Date Title
CN1068331C (zh) 含喹啉氧基或吡啶氧基配位体的过渡金属催化剂体系
US6528670B1 (en) Bridged metallocenes for olefin copolymerization
EP0491842B1 (en) Monocyclopentadienyl transition metal olefin polymerization catalysts
US20010018505A1 (en) Polymerization catalyst systems and their use
CN1185787A (zh) 作为烯烃聚合催化剂的氮杂硼啉基金属配合物
WO1998034964A1 (en) Group 5 transition metal compounds
WO1998041530A1 (en) Transition metal metallacyclopentadienyl compounds
EP1417213A1 (en) Method for making late transition metal catalysts for olefin polymerization
US6100414A (en) Cyclopentadienyl transition metal compounds useful as polymerization catalysts
CN115667325A (zh) 杂化催化剂组合物、包含其的催化剂及它们的制备方法
KR20130027316A (ko) 담지 메탈로센 촉매의 제조방법 및 이를 이용하여 제조된 담지 메탈로센 촉매
CN105308059A (zh) 催化剂组合物、其制备方法及使用其制备聚烯烃的方法
US5990033A (en) Syndiotactic prochiral olefin polymerization using non-aromatic, anionic, dienyl group containing complexes
CN107459592A (zh) 改性硅胶载体和负载化茂金属催化剂及制备方法和茂金属催化剂体系
US6228959B1 (en) Single-site catalysts containing homoaromatic ligands
CA2218638C (en) Polymerization of alpha-olefins with transition metal catalysts based on bidentate ligands containing pyridine or quinoline moiety
US6228958B1 (en) Azaborolinyl metal complexes as olefin polymerization catalysts
US6294626B1 (en) Olefin polymerization catalysts containing modified boraaryl ligands
CA2219816C (en) Azaborolinyl metal complexes as olefin polymerization catalysts
MXPA00009362A (en) Cyclopentadienyl transition metal compounds, as polymerization catalysts
MXPA00002637A (en) Cyclopentaphenanthreneyl metal complexes and polymerization process

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20010711

Termination date: 20110318