English:
[0007] In another aspect of this invention, the activator comprises a chemically- treated solid oxide, which comprises a solid oxide treated with an electron- withdrawing anion. In yet another aspect of this invention, the activator comprises a chemically-treated solid oxide in combination with an organoaluminum compound.
[0019] Examples of aromatic groups, in each instance, include, but are not limited to, phenyl, naphthyl, anthracenyi, and the like, including substituted derivatives thereof, in each instance having from 6 to about 25 carbons. Substituted derivatives of aromatic compounds include, but are not limited to, to IyI, xylyl, mesityl, and the like, including any heteroatom substituted derivative thereof.
[0020] Examples of cyclic groups, in each instance, include, but are not limited to, cycloparaffms, cycloolefins, cycloacetylenes, arenes such as phenyl, bicyclic groups and the like, including substituted derivatives thereof, in each instance having from about 3 to about 20 carbon atoms.
[0034] Examples of inorganic groups that may be used as substituents, in each instance, include, but are not limited to, -SO2X, -OAlX2, -OSiX3, -OPX2, -SX, - OSO2X5 -AsX2, -As(O)X 2, -PX2, and the like, wherein X can be a monoanionic group such as halide, hydride, amide, alkoxide, alkyl thiolate, and the like, and wherein any alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl group or substituent on these ligands has from 1 to about 20 carbon atoms.
[0057] Similarly, in another aspect of this invention, the chemically treated solid oxide comprises a chlorided solid oxide in the form of a particulate solid, thus a source of chloride ion is added to the oxide by treatment with a chloriding agent. The chloride ion may be added to the oxide by forming a slurry of the oxide in a suitable solvent. In another aspect of the present invention, the solid oxide can be treated with a chloriding agent during the calcining step. Any chloriding agent capable of serving as a source of chloride and thoroughly contacting the oxide during the calcining step can be used. For example, volatile organic chloriding agents may be used. Examples of volatile organic chloriding agents useful in this aspect of the invention include, but are not limited to, certain freons, perchlorobenzene, chloromethane, dichloromethane, chloroform, carbon tetrachloride, and combinations thereof. Gaseous hydrogen chloride or chlorine itself can also be used with the solid oxide during calcining. One convenient method of contacting the oxide with the chloriding agent is to vaporize a chloriding agent into a gas stream used to fluidize the solid oxide during calcination.
[0058] In one aspect, the amount of fluoride or chloride ion present before calcining the solid oxide can be generally from about 2 to about 50% by weight, where the weight percents are based on the weight of the solid oxide, for example silica- alumina, before calcining. In another aspect, the amount of fluoride or chloride ion present before calcining the solid oxide can be from about 3 to about 25% by weight, and in another aspect, from about 4 to about 20% by weight. If the fluoride or chloride ion are added during calcining, such as when calcined in the presence of CCl4, there is typically no fluoride or chloride ion in the solid oxide before calcining. Once impregnated with halide, the halided oxide may be dried by any method known in the art including, but not limited to, suction filtration followed by evaporation, drying under vacuum, spray drying, and the like, although it is also possible to initiate the calcining step immediately without drying the impregnated solid oxide.
[0069] In another aspect, (X6) can be an alkoxide or aryloxide, any one of which having from 1 to about 10 carbon atoms, halide, or hydride. In yet another aspect, (X6) is independently fluoro or chloro.
[0077] Thus, aluminoxanes that may be used as activators in this invention are generally represented generally by formulas such as (R-Al-O)n, R(R-Al-O)nAlR2, and the like, wherein the R group is typically a linear or branched Ci-C6 alkyl such as methyl, ethyl, propyl, butyl, pentyl, or hexyl wherein n typically represents an integer from 1 to about 50. In one embodiment, the aluminoxane compounds of this invention include, but are not limited to, methylaluminoxane, ethylaluminoxane, n- propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane, t-butyl- aluminoxane, sec-butylaluminoxane, iso-butylaluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, iso-pentylaluminoxane, neopentylaluminoxane, or combinations thereof.
[0081] Organoaluminoxanes can be prepared by various procedures which are well known in the art. Examples of organoaluminoxane preparations are disclosed in U.S. Patent Nos. 3,242,099 and 4,808,561, each of which is incorporated herein by reference, in its entirety. One example of how an aluminoxane may be prepared is as follows. Water which is dissolved in an inert organic solvent may be reacted with an aluminum alkyl compound such as AlR3 to form the desired organoaluminoxane compound. While not intending to be bound by this statement, it is believed that this synthetic method can afford a mixture of both linear and cyclic (R-Al-O)n aluminoxane species, both of which are encompassed by this invention. Alternatively, organoaluminoxanes may be prepared by reacting an aluminum alkyl compound such as AlR3 with a hydrated salt, such as hydrated copper sulfate, in an inert organic solvent.
[0085] Although not intending to be bound by the following theory, these examples of fluoroorgano borate and fluoroorgano boron compounds, and related compounds, are thought to form "weakly-coordinating" anions when combined with organometal compounds, as disclosed in U.S. Patent 5,919,983, which is incorporated herein by reference in its entirety.
[0086] Generally, any amount of organoboron compound can be utilized in this invention. In one aspect, the molar ratio of the organoboron compound to the transition metal compound in the composition is from about 0.1:1 to about 10:1. In another aspect, the amount of the fluoroorgano boron or fluoroorgano borate compound used as a cocatalyst or activator for the transition metal compound is in a range of from about 0.5 mole to about 10 moles of boron compound per mole of transition metal compound. In one aspect, the amount of fluoroorgano boron or fluoroorgano borate compound used as a cocatalyst or activator for the transition metal compound is in a range of from about 0.8 mole to about 5 moles of boron compound per mole of transition metal compound.
[0090] Examples of ionizing ionic compounds include, but are not limited to, the following compounds: tri(n-butyl)ammonium tetrakis(p-tolyl)borate, tri(n-butyl)- ammonium tetrakis(m-tolyl)borate, tri(n-butyl)ammonium tetrakis(2,4-dimethyl)- borate, tri(n-butyl) ammonium tetrakis(3,5-dimethylphenyl)borate, tri(n-butyl)- ammonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(p-tolyl)borate, N,N-dimethylanilinium tetrakis(m-tolyl)borate, N,N-dimethylanilinium tetrakis(2,4- dimethylphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-dimethylphenyl)borate, N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, N5N- dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(p- tolyl)borate, triphenylcarbenium tetrakis(m-tolyl)borate, triphenylcarbenium tetrakis(2,4-dimethylphenyl)borate, triphenylcarbenium tetrakis(3,5- dimethylphenyl)borate, triphenylcarbenium tetrakis[3,5-bis(trifluoro- methyl)phenyl]borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, tropylium tetrakis(p-tolyl)borate, tropylium tetrakis(m-tolyl)borate, tropylium tetrakis(2,4-dimethylphenyl)borate, tropylium tetrakis(3 , 5-dimethylphenyl)borate, tropylium tetrakis[3,5-bis(trifluororaethyl)phenyl]borate, tropylium tetrakis(pentafluorophenyl)borate, lithium tetrakis(pentafluorophenyl)borate, lithium tetrakis(phenyl)borate, lithium tetrakis(p-tolyl)borate, lithium tetrakis(m- tolyl)borate, lithium tetrakis(2,4-dimethylphenyl)borate, lithium tetrakis(3,5- dimethylphenyl)borate, lithium tetrafluoroborate, sodium tetrakis(pentafluoro- phenyl)borate, sodium tetrakis(phenyl) borate, sodium tetrakis(p-tolyl)borate, sodium tetrakis(m-tolyl)b orate, sodium tetrakis(2,4-dimethylphenyl)borate, sodium tetrakis(3,5-dimethylphenyl)borate, sodium tetrafluoroborate, potassium tetrakis- (pentafluorophenyl)borate, potassium tetrakis(phenyl)borate, potassium tetrakis(p- tolyl)borate, potassium tetrakis(m-tolyl)borate, potassium tetrakis(2,4-dimethyl- ρhenyl)borate, potassium tetrakis(3,5-dimethylphenyl)borate, potassium tetrafluoroborate, tri(n-butyl)ammonium tetrakis(p-tolyl)aluminate, tri(n-butyl)ammonium tetrakis(m-tolyl)aluminate, tri(n-butyl) ammonium tetrakis(2,4-dimethyl)aluminate, tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)aluminate, tri(n- butyl)ammonium tetrakis(pentafluorophenyl)aluminate, N,N-dimethylanilinium tetrakis(p-tolyl)aiuminate, N,N-dimethylanilinium tetrakis(m-tolyl)aluminate, N5N- dimethylanilinium tetrakis(2,4-dimethylphenyl)aluminate, N,N-dimethylanilinium tetrakis(3,5-dimethylphenyl)aluminate, N,N-dimethylanilinium tetrakis
[0092] Acyclic, cyclic, polycyclic, terminal (α), internal, linear, branched, substituted, unsubstituted, functionalized, and non-functionalized olefins may be employed in this invention. For example, typical unsaturated compounds that may be polymerized with the catalysts of this invention include, but are not limited to, propylene, 1-butene, 2-butene, 3-methyl-l-butene, isobutylene, 1-pentene, 2- pentene, 3-methyl-l-pentene. 4-methyl- 1-pentene, 1-hexene, 2-hexene, 3-hexene, 3- ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, the four normal octenes, the four normal nonenes, the five normal decenes, and mixtures of any two or more thereof. Cyclic and bicyclic olefins, including but not limited to, cyclopentene, cyclohexene, norbornylene, norbornadiene, and the like, may also be polymerized as described above.
[00129] In the following examples, unless otherwise specified, the syntheses and preparations described therein were carried out under an inert atmosphere such as nitrogen and/or argon. Solvents were purchased from commercial sources and were typically dried over activated alumina prior to use, or distilled from potassium metal prior to use. Unless otherwise specified, reagents were obtained from commercial sources.
[00131] Molecular weights and molecular weight distributions were obtained using a PL 220 SEC high temperature chromatography unit (Polymer Laboratories) with trichlorobenzene (TCB) as the solvent, with a flow rate of 1 mL/minute at a temperature of 145°C. BHT (2,6-di-tert-butyI-4-methylphenol) at a concentration of 0.5 g/L was used as a stabilizer in the TCB. An injection volume of 200 μL was used with a nominal polymer concentration of 1.5 mg/mL. Dissolution of the sample in stabilized TCB was carried out by heating at 1500C for 5 hours with occasional, gentle agitation. The columns used were three Mixed A LS columns (7.8x300mm) and were calibrated with a broad linear polyethylene standard (ChevronPhillips Marlex® BHB 5003 resin) for which the molecular weight had been determined.
[00133] Compound E was purchased from Strem Chemical Company and used as received.
[00136] For each run, to a 1 gallon Autoclave Engineers stirred reactor was added 1 mL of a IM solution of triisobutylaluminum (TIBAL) in hexanes as a co- catalyst, 10 mg of the transition metal complex A and 200 mg of the sulfated alumina from Example 3. The autoclave was sealed and 2 L of isobutane was added and stirring started at 700 rpm. The reactor heating was then initiated. As the reactor approached 600C, ethylene (and 1-hexene, if used) was added. The reactor was held at set point for 60 minutes by feeding ethylene on demand. The polymerization was terminated by venting the volatiles to the flare system. This procedure left the polyethylene as a wet solid in the reactor. The polyethylene solid was then air dried. The results are summarized in Table 1.
[00137] To a 1 gallon Autoclave Engineers stirred reactor was added 15 mg of the transition metal complex B, 200 mg of the sulfated alumina from Example 3, and 1 mL of a IM solution of triisobutylaluminum (TIBAL) in hexanes as a co- catalyst. The autoclave was sealed and 2 L of isobutane were added and stirring started at 700 rpm. The reactor heating was then initiated. As the reactor approached 600C, ethylene addition was begun. The set point of 900C and 550 psig was then rapidly attained. The reactor was held at set point for 60 minutes by feeding ethylene on demand. The polymerization was terminated by venting the volatiles to the flare system. This procedure left the polyethylene as a wet solid in the reactor. The polyethylene solid was then air dried. The results are summarized in Table 2.
[00140] To a 1 gallon Autoclave Engineers stirred reactor was added transition metal complex E5 sulfated alumina from Example 3, and 0.5 mL of a IM solution of triisobutylaluminum in hexanes. The autoclave was sealed and 2 L of isobutane was added and stirring started at 700 rpm. The reactor heating was then initiated. As the reactor approached 60°C, ethylene addition was begun. The set point of 900C and 550 psig was then rapidly attained. The reactor was held at set point for 60 minutes by feeding ethylene on demand. The polymerization was terminated by venting the volatiles to the flare system. This procedure left the polyethylene as a wet solid in the reactor. The polyethylene solid was air dried. The results are summarized in Table 5.

中文:
[0007]在本发明的另一个方面,活化剂包括化学处理的固体氧化物,其包括用吸电子阴离子处理的固体氧化物。仍在本发明的另一个方面,活化剂包括与有机铝化合物结合的化学处理的固体氧化物。
[0019]芳基的实例,在每一种情况下,包括但不限于,苯基、萘基、蒽基和类似基团,包括其取代的衍生物,在每一种情况下,所述衍生物具有6至大约25个碳。芳族化合物的取代衍生物包括但不限于,甲苯基、二甲苯基、2,4,6-三甲苯基(mesityl)和类似基团,包括其任何杂原子取代的衍生物。
[0020]环状基团的实例,在每一种情况下,包括但不限于,环烷、环烯、环炔(cycloacetylene)、芳烃如苯基、双环基团及类似物,包括其取代的衍生物,在每一种情况下,所述衍生物具有大约3到大约20个碳原子。
[0034]可以被用作取代基的无机基团的实例,在每一种情况下,包括但不限于-SO2X、-OAlX2、-OSiX3、-OPX2、-SX、-OSO2X、-AsX2、-As(O)X2、-PX2及类似基团,其中X可以是单阴离子基团,如卤化物、氢化物、酰胺、醇盐、烷基硫醇酯及类似物,并且其中在这些配体上的任何烷基、环烷基、芳基、芳烷基、取代的烷基、取代的芳基或取代的芳烷基具有1到大约20个碳原子。
[0057]同样地,在本发明的另一方面,化学处理的固体氧化物包括颗粒固体形式的氯化固体氧化物,因此,通过用氯化剂处理,氯化物离子源被加入到氧化物中。通过在合适的溶剂中形成氧化物的浆液,氯化物离子可以被加入到氧化物中。在本发明的另一个方面,固体氧化物可以在煅烧步骤期间用氯化剂处理。可以使用任何能够作为氯化物源使用并且在煅烧步骤期间充分接触氧化物的氯化剂。例如,可以使用挥发性的有机氯化剂。在本发明的该方面有用的挥发性有机氯化剂的实例包括,但不限于,某些氟利昂、全氯苯、氯代甲烷、二氯甲烷、氯仿、四氯化碳及其组合。气态氯化氢或氯本身也可以在煅烧过程中与固体氧化物一起使用。使氧化物与氯化剂接触的一种便利的方法是在煅烧过程中将氯化剂蒸发到用于流化固体氧化物的气流中。
[0058]一方面,在煅烧固体氧化物之前存在的氟化物或氯化物离子的量通常可为按重量计大约2%至大约50%,其中重量百分比是基于煅烧之前的固体氧化物,如二氧化硅-氧化铝的重量。另一方面,在煅烧固体氧化物之前存在的氟化物或氯化物离子的量可以是按重量计大约3至大约25%,并且在另一方面,为按重量计的大约4至大约20%。如果在煅烧过程中加入氟化物或氯化物离子,如在CCl4存在下煅烧时,则在煅烧之前在固体氧化物中典型地没有氟化物或氯化物离子。一旦用卤化物浸渍,卤化氧化物可以通过本领域已知的任何方法干燥,这些方法包括,但不限于,吸滤随后蒸发、真空下干燥、喷雾干燥及类似方法,尽管也可能立即开始煅烧步骤,而不需干燥被浸渍的固体氧化物。
[0069]在另一方面,(X6)可以是醇盐或芳族氧化物——其任何一个具有1至大约10个碳原子、卤化物或氢化物。仍在另一方面,(X6)独立地是氟基或氯基。
[0077]因此,可以在本发明中作为活化剂使用的铝氧烷通常由通式如(R-Al-O)n、R(R-Al-O)nAlR2及类似分子式表示,其中R基团典型地是直链或支链C1-C6烷基,如甲基、乙基、丙基、丁基、戊基或己基,其中n典型地代表1到大约50的整数。在一个实施方式中,本发明的铝氧烷化合物包括,但不限于,甲基铝氧烷、乙基铝氧烷、正丙基铝氧烷、异丙基铝氧烷、正丁基铝氧烷、叔丁基铝氧烷、仲丁基铝氧烷、异丁基铝氧烷、1-戊基铝氧烷、2-戊基铝氧烷、3-戊基铝氧烷、异戊基铝氧烷、新戊基铝氧烷或其组合。
[0081]可以通过本技术领域熟知的多种方法制备有机铝氧烷。有机铝氧烷制备的例子被公开在美国专利3,242,099和4,808,561中,其每一个在此以其全部引入作为参考。铝氧烷如何制备的一个例子如下。溶于惰性有机溶剂中的水可与烷基铝化合物如AlR3反应,形成期望的有机铝氧烷化合物。虽然不意图被该陈述所限制,但是据认为,这种合成方法可以提供直链和环状(R-Al-O)n铝氧烷种类的混合物,这两个种类都包括在本发明中。可选地,通过使烷基铝化合物如AlR3与水合盐如水合硫酸铜在惰性有机溶剂中反应,可以制备有机铝氧烷。
[0085]虽然不意欲为下述理论所束缚,但当与有机金属化合物结合时,氟有机硼酸盐和氟有机硼化合物及其相关化合物的这些例子被认为是形成“弱配位”阴离子,如在美国专利5,919,983中所公开的,在此引入其全部作为参考。
[0086]通常,可以在本发明中使用任何量的有机硼化合物。在一个方面,组合物中的有机硼化合物与过渡金属化合物的摩尔比为大约0.1∶1至大约10∶1。在另一方面,作为过渡金属化合物的助催化剂或活化剂使用的氟有机硼或氟有机硼酸盐化合物的量,在每摩尔过渡金属化合物为大约0.5摩尔至大约10摩尔硼化合物的范围内。在一方面,作为过渡金属化合物的助催化剂或活化剂使用的氟有机硼或氟有机硼酸盐化合物的量,在每摩尔过渡金属化合物为大约0.8摩尔至大约5摩尔硼化合物的范围内。
[0090]电离化离子化合物的例子包括,但不限于下列化合物:三(正丁基)铵四(对甲苯基)硼酸盐、三(正丁基)铵四(间甲苯基)硼酸盐、三(正丁基)铵四(2,4-二甲基)硼酸盐、三(正丁基)铵四(3,5-二甲基苯基)硼酸盐、三(正丁基)铵四[3,5-双(三氟甲基)苯基]硼酸盐、三(正丁基)铵四(五氟苯基)硼酸盐、N,N-二甲基苯铵四(对甲苯基)硼酸盐、N,N-二甲基苯铵四(间甲苯基)硼酸盐、N,N-二甲基苯铵四(2,4-二甲基苯基)硼酸盐、N,N-二甲基苯铵四(3,5-二甲基苯基)硼酸盐、N,N-二甲基苯铵四[3,5-双(三氟甲基)苯基]硼酸盐、N,N-二甲基苯铵四(五氟苯基)硼酸盐、三苯基碳鎓四(对甲苯基)硼酸盐、三苯基碳鎓四(间甲苯基)硼酸盐、三苯基碳鎓四(2,4-二甲基苯基)硼酸盐、三苯基碳鎓四(3,5-二甲基苯基)硼酸盐、三苯基碳鎓四[3,5-双(三氟甲基)苯基]硼酸盐、三苯基碳鎓四(五氟苯基)硼酸盐、鎓四(对甲苯基)硼酸盐、鎓四(间甲苯基)硼酸盐、鎓四(2,4-二甲基苯基)硼酸盐、鎓四(3,5-二甲基苯基)硼酸盐、鎓四[3,5-双(三氟甲基)苯基]硼酸盐、鎓四(五氟苯基)硼酸盐、四(五氟苯基)硼酸锂、四(苯基)硼酸锂、四(对甲苯基)硼酸锂、四(间甲苯基)硼酸锂、四(2,4-二甲基苯基)硼酸锂、四(3,5-二甲基苯基)硼酸锂、四氟硼酸锂、四(五氟苯基)硼酸钠、四(苯基)硼酸钠、四(对甲苯基)硼酸钠、四(间甲苯基)硼酸钠、四(2,4-二甲基苯基)硼酸钠、四(3,5-二甲基苯基)硼酸钠、四氟硼酸钠、四(五氟苯基)硼酸钾、四(苯基)硼酸钾、四(对甲苯基)硼酸钾、四(间甲苯基)硼酸钾、四(2,4-二甲基苯基)硼酸钾、四(3,5-二甲基苯基)硼酸钾、四氟硼酸钾、三(正丁基)铵四(对甲苯基)铝酸盐、三(正丁基)铵四(间甲苯基)铝酸盐、三(正丁基)铵四(2,4-二甲基)铝酸盐、三(正丁基)铵四(3,5-二甲基苯基)铝酸盐、三(正丁基)铵四(五氟苯基)铝酸盐、N,N-二甲基苯铵四(对甲苯基)铝酸盐、N,N-二甲基苯铵四(间甲苯基)铝酸盐、N,N-二甲基苯铵四(2,4-二甲基苯基)铝酸盐、N,N-二甲基苯铵四(3,5-二甲基苯基)铝酸盐、N,N-二甲基苯铵四(五氟苯基)铝酸盐、三苯基碳鎓四(对甲苯基)铝酸盐、三苯基碳鎓四(间甲苯基)铝酸盐、三苯基碳鎓四(2,4-二甲基苯基)铝酸盐、三苯基碳鎓四(3,5-二甲基苯基)铝酸盐、三苯基碳鎓四(五氟苯基)铝酸盐、鎓四(对甲苯基)铝酸盐、鎓四(间甲苯基)铝酸盐、鎓四(2,4-二甲基苯基)铝酸盐、鎓四(3,5-二甲基苯基)铝酸盐、鎓四(五氟苯基)铝酸盐、四(五氟苯基)铝酸锂、四(苯基)铝酸锂、四(对甲苯基)铝酸锂、四(间甲苯基)铝酸锂、四(2,4-二甲基苯基)铝酸锂、四(3,5-二甲基苯基)铝酸锂、四氟铝酸锂、四(五氟苯基)铝酸钠、四(苯基)铝酸钠、四(对甲苯基)铝酸钠、四(间甲苯基)铝酸钠、四(2,4-二甲基苯基)铝酸钠、四(3,5-二甲基苯基)铝酸钠、四氟铝酸钠、四(五氟苯基)铝酸钾、四(苯基)铝酸钾、四(对甲苯基)铝酸钾、四(间甲苯基)铝酸钾、四(2,4-二甲基苯基)铝酸钾、四(3,5-二甲基苯基)铝酸钾、四氟铝酸钾,然而,在本发明中,电离化离子化合物不限于这些。
[0092]可以在本发明中使用无环、环状、多环、末端(α)、中间、直链、支化的、取代的、未取代的、官能化的和非官能化的烯烃。例如,典型的可以用本发明的催化剂聚合的不饱和化合物包括,但不限于,丙烯、1-丁烯、2-丁烯、3-甲基-1-丁烯、异丁烯、1-戊烯、2-戊烯、3-甲基-1-戊烯、4-甲基-1-戊烯、1-己烯、2-己烯、3-己烯、3-乙基-1-己烯、1-庚烯、2-庚烯、3-庚烯、四种正辛烯(the four normaloctenes)、四种正壬烯(the four normal nonenes)、五种正癸烯(the five normaldecenes)及其任意两种或多种的混合物。环烯烃和双环烯烃,包括但不限于,环戊烯、环己烯、降冰片烯、降冰片二烯及其类似物,也可以如上面所述被聚合。
[00129]在下列实施例中,除非另外指明,此处描述的合成和制备在惰性气氛如氮和/或氩下进行。从商业来源购买溶剂并且典型地在使用之前在活化氧化铝上干燥,或者在使用之前从钾金属中蒸馏。除非另外指明,试剂从商业来源获得。
[00131]使用PL 220 SEC高温色谱单元(high temperature chromatography unit)(Polymer Laboratories),以三氯苯(TCB)作为溶剂,在145°C的温度下,以1毫升/分钟的流速,获得分子量和分子量分布。浓度为0.5克/升的BHT(2,6-二-叔丁基-4-甲基苯酚)被用做TCB中的稳定剂。使用200微升的注射体积,公称(nominal)聚合物浓度为1.5毫克/毫升。通过在150°C加热5小时,偶而伴有温和的搅拌,在稳定的TCB中溶解样品。所使用的柱是三根Mixed A LS柱(7.8×300mm),并且用分子量已经确定的宽线性聚乙烯标准(broad linear polyethylene standard)(ChevronPhillipsBHB 5003树脂)进行校准。
[00133]化合物E购买自Strem Chemical公司并且如收到时使用。
[00136]对于每一试验,向1加仑高压釜工程搅拌反应器中加入1mL作为助催化剂的己烷中的1M三异丁基铝(TIBAL)溶液、10mg过渡金属络合物A和200mg来自实施例3的硫酸化氧化铝。密封高压釜并且加入2L异丁烷,在700转/分下开始搅拌。随后开始反应器加热。当反应器达到60°C时,加入乙烯(和1-己烯,如果使用的话)。通过按需要送入乙烯,使反应器在设置点保持60分钟。通过将挥发物排放到废气处理系统终止聚合。该过程在反应器中留下聚乙烯,为湿润固体。随后风干该聚乙烯固体。结果总结在表1中。
[00137]向1加仑高压釜工程搅拌反应器中加入15mg过渡金属络合物B、200mg来自实施例3的硫酸化氧化铝以及1mL作为助催化剂的己烷中的1M三异丁基铝(TIBAL)溶液。密封高压釜并且加入2L异丁烷,以700转/分开始搅拌。随后开始反应器加热。当反应器达到60°C时,开始加入乙烯。然后迅速达到90°C和550psig的设置点。通过按需要供给乙烯,使反应器在设置点保持60分钟。通过将挥发物排放到废气处理系统,终止聚合。该过程在反应器中留下聚乙烯,为湿润固体。随后风干该聚乙烯固体。结果总结在表2中。
[00140]向1加仑高压釜工程搅拌反应器中加入过渡金属络合物E、来自实施例3的硫酸化氧化铝以及0.5mL己烷中的1M三异丁基铝溶液。密封高压釜并且加入2L异丁烷,以700转/分开始搅拌。随后开始反应器加热。当反应器达到60°C时,开始加入乙烯。然后迅速达到90°C和550psig的设置点。通过按需要供给乙烯,使反应器在设置点保持60分钟。通过将挥发物排放到废气处理系统,终止聚合。该过程将聚乙烯留在反应器中,为湿润固体。风干该聚乙烯固体。结果总结在表5中。