English:
[0005] One method of making the aforementioned polymer blends is by mixing two different polymers after they have been polymerized to achieve a target set of properties. However, this method is relatively expensive making it much more desirable to make blends by direct polymerization. Blending by direct polymerization is well known in the prior art and typically uses multiple reactors in series, where the product from one reactor is fed to a second reactor having a different polymerizing environment, resulting in a final product that is an intimate mix of two different products. Examples of such processes employing vanadium catalysts in series reactor operation to produce different types of EPDM compositions are disclosed in U.S. Patent Nos. 3,629,212, 4,016,342, and 4,306,041.
[0007] U.S. Patent No. 6,207,756 describes a process for producing a blend of a continuous phase of a semi-crystalline plastic, such as polypropylene, and a discontinuous phase of an amorphous elastomer, such as a terpolymer of ethylene, a C 3 -C 20 alpha olefin and a non-conjugated diene. The blends are produced in series reactors by producing a first polymer component in a first reactor, directing the effluent to a second reactor and producing the second polymer component in solution in the second reactor in the presence of the first polymeric component. U.S Patent No. 6,319,998 also discloses using series solution polymerizations to produce blends of ethylene copolymers. U.S. Patent No. 6,770,714 discloses the use of parallel polymerizations to produce different polymeric components that are then blended through extrusion or using other conventional mixing equipment. One polymeric component is a propylene homopolymer or copolymer and the second polymeric component is an ethylene copolymer.
[0015] Preferably, said dispersed phase comprises particles of said thermoplastic first polymer having an average particle size less than 10 microns, preferably less than 5 microns, more preferably less than 3 micron.
[0017] In one embodiment, no more than about 70 wt%, preferably no more than about 50 wt%, and more preferably no more than 30 wt%, of the second polymer is extractable in cyclohexane at 23°C.
[0018] Conveniently, said dispersed phase comprises less than 50 wt%, such as less than 30 wt%, for example less than 20 wt% of the total heterogeneous polymer blend.
[0020] Preferably, the second polymer is produced from a plurality of comonomers comprising at least one C 3 to C 20 olefin and at least one polyene.
[0021] In a further aspect, the invention resides in a process for producing a heterogeneous polymer blend comprising (a) a dispersed phase comprising a thermoplastic first polymer having at least 30% crystallinity ; and (b) a continuous phase comprising a second polymer different from the first polymer, the second polymer having a crystallinity less than that of the first polymer and being at least partially cross-linked, the process comprising:
[0025] Conveniently, said catalyst selected in (a) is a single site catalyst comprising at least one catalyst component, normally a metallocene, and at least one activator.
[0027] tn one embodiment, the catalyst employed in contacting (c) is the same as the catalyst employed in contacting (b).
[0028] hi another embodiment, the catalyst employed in contacting (c) is the different from the catalyst employed in contacting (b) and catalyst quenching is applied between the contacting (b) and the contacting (c).
[0029] In one embodiment, the product of said contacting (c) is subjected to an additional curing step to further cross-link said second polymer.
[0030] Figures 1 is an atomic force micrograph (AFM) of the polymer blend produced in Example 1.
[0031] Figure 2 is an atomic force micrograph (AFM) of the polymer blend produced in Example 2.
[0032] For purposes of this invention and the claims thereto when a polymer or oligomer is referred to as comprising an olefin, the olefin present in the polymer or oligomer is the polymerized or oligomerized form of the olefin, respectively. Likewise the use of the term polymer is meant to encompass homopolymers and copolymers. In addition the term copolymer includes any polymer having 2 or more monomers. Thus, as used herein, the term "polypropylene" means a polymer made of at least 50% propylene units, preferably at least 70% propylene units, more preferably at least 80% propylene units, even more preferably at least 90% propylene units, even more preferably at least 95% propylene units or 100% propylene units.
[0034] hi contrast, a "homogeneous blend" is a composition having substantially one morphological phase in the same state. For example a blend of two polymers where one polymer is miscible with another polymer is said to be homogeneous in the solid state. Such morphology is determined using scanning electron microscopy. By miscible is meant that that the blend of two or more polymers exhibits single-phase behavior for the glass transition temperature, e.g. the Tg would exist as a single, sharp transition temperature on a dynamic mechanical thermal analyzer (DMTA) trace of tan δ (i.e., the ratio of the loss modulus to the storage modulus) versus temperature. By contrast, two separate transition temperatures would be observed for an immiscible blend, typically corresponding to the temperatures for each of the individual components of the blend. Thus a polymer blend is miscible when there is one Tg indicated on the
[0036] By virtue of the fact that the second polymer of the polymer blend of the invention is formed as at least partially cross-linked particles in the polymerization reactor, the need for a subsequent dynamic vulcanization step and hence the need for addition of processing oil can be avoided. It is, however, to be appreciated that in some cases the polymer blend of the invention may be subjected to post-polymerization curing and/or vulcanization to produce additional cross-linking of the second polymer.
[0046] Exemplary thermoplastic polymers include the family of polyolefin resins, polyesters (such as polyethylene terephthalate, polybutylene terephthalate), polyamides (such as nylons), polycarbonates, styrene-acrylonitrile copolymers, polystyrene, polystyrene derivatives, polyphenylene oxide, polyoxymethylene, and fluorine-containing thermoplastics. The preferred thermoplastic resins are crystalline polyolefms that are formed by polymerizing C 2 to C 20 olefins such as, but not limited to, ethylene, propylene and C 4 to C 12 α-olefins, such as 1-butene, 1-hexene, 1-octene, 2-methyl-l-propene, 3-methyl-l-ρentene, 4-methyl-l- pentene, 5-methyl- 1-hexene, and mixtures thereof. Copolymers of ethylene and propylene or ethylene or propylene with another α-olefin, such as butene-1; pentene- 1 ,2-methylpentene- 1 ,3-methylbutene- 1 ; hexene- 1 ,3-methylpentene- 1 ,4- methylpentene-l,3,3-dimethylbutene-l; heρtene-1; hexene-1; methylhexene-1; dimethylpentene-1 trimethylbutene-1; ethylpentene-1; octene-1; methylpentene-1; dimethylhexene-1; trimethylpentene-1; ethylhexene-1; methylethylpentene-1; diethylbutene-1; propylpentane-1; decene-1; methyhionene-1; nonene-1; dimethyloctene-1; trimethylheptene-1; ethyloctene-1; methylethylbutene-1; diethylhexene-1 and dodecene-1, may also be used.
[0049] The dispersed particles of the first polymer typically have an average size of less than 10 microns, preferably less than 5 microns, more preferably less than 3 microns.
[0071] In one embodiment, the catalyst employed to produce the second polymer component is the same as, or is compatible with, the catalyst used to produce the thermoplastic first polymer. In such a case, the first and second polymerization zones can be in a multiple-zone reactor, or separate, series- connected reactors, with the entire effluent from the first polymerization zone, including any active catalyst, being transferred to the second polymerization zone. Additional catalyst can then be added, as necessary, to the second polymerization zone, in which case the elastomeric second polymer is derived from both the catalysts introduced into the first and the second polymerization zones. In a particularly preferred embodiment, the process of the invention is conducted in two or more series-connected, continuous flow, stirred tank or tubular reactors using metallocene catalysts.
[0095] In another embodiment, the polymer blend described herein has an ultimate elongation (as measured by ISO 37) of 20 % or more, preferably 30 % or more, more preferably 40 % or more.
[0096] In another embodiment, the polymer blend described herein has a compression set (as measured by ISO 815A) of 90 % or less, preferably 70 % or less, more preferably 50 % or less, more preferably 30 % or less,.
[0098] In another embodiment, the polymer blend described herein has an oil swell (as measured by ASTM D471) of 500 % or less, preferably 250 % or less, more preferably 100 % or less.
[00125] It will be understood by those skilled in the art that the steps outlined above may be varied, depending upon the desired result. For example, an extruded sheet of the compositions of this invention may be directly thermoformed or blow molded without cooling, thus skipping a cooling step. Other parameters may be varied as well in order to achieve a finished composite article having desirable features.
[00127] In another embodiment, this invention relates to:
[00131] Peak melting point (Tm) and peak crystallization temperature (Tc) were determined using the following procedure according to ASTM E 794-85. Crystallinity was calculated using heat of fusion determined using ASTM D 3417- 99. Differential scanning calorimetric (DSC) data were obtained using a TA Instruments model QlOO machine or a Perkin-Elmer DSC-7. Samples weighing approximately 5-10 mg were sealed in aluminum sample pans. The DSC data were recorded by first heating a sample from room temperature to 200°C at a rate of 10°C/minute (1st melt). Then the sample was kept at 200 0 C for 5 minutes before ramping at 10°C/minute to -100°C, followed by isothermal for 5 minutes at -100°C then heating to 200°C at a rate of 10°C/minute (2nd melt). Both the first and second cycle thermal events were recorded. The peak melting temperature and heat of fusion reported in the examples were obtained from the second melt. Areas under the melting curves were measured and used to determine the heat of fusion and the degree of crystallinity. The percent crystallinity is calculated using the formula, [area under the curve (Joules/gram) / B (Joules/gram)] * 100, where B is the heat of fusion for the homopolymer of the major monomer component. These values for B were obtained from the Polymer Handbook, Fourth Edition, published by John Wiley and Sons, New York 1999. A value of 189 J/g (B) was used as the heat of fusion for 100% crystalline polypropylene. A value of 290 J/g is used for the heat of fusion for 100% crystalline polyethylene. For polymers displaying multiple cooling and melting peaks, all the peak crystallization temperatures and peaks melting temperatures were reported. The heat of fusion for each melting peak was calculated individually.
[00139] Loss Modulus (E"), Storage Modulus (E') and β relaxation were measured by dynamic mechanical thermal analysis (DMTA). The instrument used was the RSA II, Rheometrics Solid Analyzer II from TA Instruments, New Castle, DE. The instrument was operated in tension mode and used molded rectangular samples. Sample conditions were: 0.1% strain, 1 Hz frequency, and 2°C per minute heating rate, covering the temperature range from -135°C to the melting point of the sample. Samples were molded at about 200°C. Typical sample dimensions were 23 mm length x 6.4 mm width x thickness between 0.25 mm and 0.7 mm, depending on the sample. Tan δ is the ratio of E 1 VE'. The output of these DMTA experiments is the storage modulus (E') and loss modulus (E"). The storage modulus measures the elastic response or the ability of the material to store energy, and the loss modulus measures the viscous response or the ability of the material to dissipate energy. The ratio of E'VE' (= tan δ) gives a measure of the damping ability of the material. Energy dissipation mechanisms (i.e., relaxation modes) show up as peaks in tan δ, and are associated with a drop in E' as a function of temperature. The uncertainty associated with reported values of E' is expected to be on the order of ±10%, due to variability introduced by the molding process.
[00148] 1,9-decadiene was used as the diene cross-linking agent in the second polymerization stage. The 1,9-decadiene was obtained from Sigma- Aldrich and was purified by first passing through an alumina column activated at high temperature under nitrogen, followed by a molecular sieve activated at high temperature under nitrogen.
[00149] Rac-dimethylsilyl bis(2-methyl-4-phenylindenyl) zirconium dimethyl catalyst (Catalyst A) was used in the first stage to produce polypropylene and [di(p-triethylsilylphenyl) methylene] (cyclopentadienyl) (3,8-di-t- butylfluorenyl)hafhium dimethyl catalyst (Catalyst B) (obtained from Albemarle) was used in the second stage to produce ethylene propylene diene rubber. Both catalysts were preactivated by dimethylanilinum tetrakis(heptafluoro-2-naphthyl) borate at a molar ratio of 1:1 in toluene. Details of the experimental conditions, catalysts employed and the properties of the resultant polymer blends are listed in Table IA below.
[00150] The in-reactor produced polymer blend produced in Example 1 was subjected to solvent extraction. The amount of each fraction is listed in Table IA. The amount of each fraction is listed as the weight percent of total in-reactor produced polymer blend. Degree of cross-linking is defined as:
[00154] A sample of the polymer blend produced in Example 1 was melt mixed in a Brabender mixer and molded under compression into plaques, and tested for thermoplastic elastomer applications. Further samples of the polymer blend produced in Example 1 were further cured by dynamic vulcanization. The vulcanization was effected by conventional techniques within a Brabender mixer along with the other added ingredients listed in Table IB. Silicon hydride DC 25804 (1.97 %) was obtained from Dow Corning. The silicon hydride was a polysiloxane with silicon hydride functionality. Platinum catalyst mixture (PC085) (2.63%) was obtained from United Chemical Technologies Inc. The catalyst mixture included 0.0055 parts by weight platinum catalyst and 2.49 parts by weight mineral oil. Zinc oxide was obtained from Zinc Corporation of America and paraffinic oil Paralux 600 IR was obtained from Chevron Oil Corporation. The performance data obtained according to the procedures described above are listed in Table IB.
[00155] This sample was produced in a 2-liter autoclave reactor following the same procedure as that used in Example 1, except that no air injection was used in between Stage 1 and Stage 2 polymerization. The same catalyst was used in both stages of polymerization, and the catalyst was preactivated with N 5 N- dimethylanilinium tetrakis (pentafluorophenyl) borate (obtained from Albemarle) at a molar ratio of about 1:1 in toluene. Triisobutyl aluminum (TEBAL) (25 wt% in toluene, purchased from Sigma- Aldrich) was used as a scavenger. The detailed reaction conditions and polymer properties are listed in Table 2A.
[00156] The in-reactor produced polymer blend of Example 2 was subjected solvent extraction using the procedure described above. The amount of each extracted fraction is expressed as weight percent of total polymer blend, and is listed in Table 2A. The morphology of the blend produced in Example 2 was examined using AFM according to the procedure described above and the results are shown in Figure 2.

中文:
[0005]上述聚合物共混物的一种制备方法是通过在两种不同的聚合物已经聚合后将它们混合以获得一组目标性能。然而,这种方法较昂贵,使得通过直接聚合制造共混物更加合乎需要。通过直接聚合的共混在现有技术中公知的并且通常使用串联的多个反应器,其中将得自一个反应器的产物供给具有不同聚合环境的第二反应器,获得为两种不同产物的均匀混合物的最终产物。在串联反应器操作中采用钒催化剂制备不同类型的EPDM组合物的此类方法的实例在美国专利号3,629,212、4,016,342和4,306,041中进行了公开。
[0007]美国专利号6,207,756描述了具有连续相和不连续相的共混物的制备方法,该连续相为半结晶塑料如聚丙烯,该不连续相为无定形弹性体如乙烯、C3-C20α-烯烃和非共轭二烯的三元共聚物。该共混物在串联反应器中如下制备:在第一反应器中制备第一聚合物组分,将该排出物导向第二反应器并在第二反应器中在第一聚合物组分存在下在溶液中制备第二聚合物组分。美国专利号6,319,998也公开了使用串联溶液聚合制备乙烯共聚物的共混物。美国专利号6,770,714公开了使用并联聚合制备不同的聚合物组分,然后经由挤出或使用其它常规混合设备将所述不同聚合物组分共混。一种聚合物组分是丙烯均聚物或共聚物,而第二聚合物组分是乙烯共聚物。
[0015]优选地,所述分散相包含所述热塑性第一聚合物的颗粒,这些颗粒具有小于10微米,优选小于5微米,更优选小于3微米的平均颗粒尺寸。
[0017]在一个实施方案中,在23°C下第二聚合物的不大于大约70wt%,优选不大于大约50wt%,和更优选不大于30wt%在环己烷中是可萃取的。
[0018]适宜地,所述分散相占全部多相聚合物共混物的小于50wt%,如小于30wt%,例如小于20wt%。
[0020]优选地,所述第二聚合物由包括至少一种C3-C20烯烃和至少一种多烯的许多共聚单体制备。适宜地,该多烯具有至少两个可聚合的不饱和基团并且优选是二烯。
[0021]在另一个方面中,本发明涉及多相聚合物共混物的制备方法,该多相聚合物共混物包括:(a)包含结晶度为至少30%的热塑性第一聚合物的分散相;和(b)包含不同于该第一聚合物的第二聚合物的连续相,该第二聚合物具有比该第一聚合物小的结晶度并且是至少部分交联的;该方法包括:
[0025]适宜地,(a)中选择的所述催化剂是包含至少一种催化剂组分(通常是金属茂)和至少一种活化剂的单位点催化剂。
[0027]在一个实施方案中,接触(c)中采用的催化剂与用于接触(b)中的催化剂相同。
[0028]在另一个实施方案中,用于接触(c)中的催化剂不同于用于接触(b)中的催化剂并且在接触(b)和接触(c)之间实施催化剂猝灭。
[0029]在一个实施方案中,对所述接触(c)的产物实施附加的固化步骤以使所述第二聚合物进一步交联。
[0030]图1是实施例1制备的聚合物共混物的原子力显微照片(AFM)。
[0031]图2是实施例2制备的聚合物共混物的原子力显微照片(AFM)。
[0032]对于本发明和所附权利要求书来说,当提到聚合物或低聚物包含烯烃时,存在于该聚合物或低聚物中的烯烃分别是烯烃的聚合或低聚形式。同样,术语聚合物的使用意欲包括均聚物和共聚物。另外,术语共聚物包括具有2种或更多种单体的任何聚合物。因此,这里使用的术语“聚丙烯”是指由至少50%的丙烯单元,优选至少70%的丙烯单元,更优选至少80%的丙烯单元,甚至更优选至少90%的丙烯单元,甚至更优选至少95%的丙烯单元或100%的丙烯单元组成的聚合物。
[0034]相反,“均相共混物”是指基本上具有一个处于相同状态下的形态相的组合物。例如,其中一种聚合物与另一种聚合物混容的两种聚合物的共混物在固态下被认为是均相的。此种形态使用扫描电子显微术进行测定。所谓的混容是指两种或更多种聚合物的共混物显示玻璃化转变温度的单相行为,例如Tg将作为一个突变的温度存在于tanδ(即,损耗模量对储能模量的比率)对温度的动力学机械热分析仪(DMTA)迹线上。相反,对于不混容的共混物来说,将观察到两个独立的转变温度,其通常对应于共混物单独组分中的每一种的温度。因此,当在DMTA迹线上显示一个Tg时,聚合物共混物是混容的。混容的共混物是均相的,而不混容的共混物是多相的。
[0036]由于本发明的聚合物共混物的第二聚合物形成为在聚合反应器中的至少部分交联的颗粒的事实,所以对后续动态硫化步骤的需要和因此对添加加工油的需要可以得到避免。然而,应领会到,有时本发明的聚合物共混物可以经历聚合后固化和/或硫化处理以产生第二聚合物的附加交联。
[0046]示例性的热塑性聚合物包括以下系列的聚合物:聚烯烃树脂、聚酯(例如聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯)、聚酰胺(例如尼龙)、聚碳酸酯、苯乙烯-丙烯腈共聚物、聚苯乙烯、聚苯乙烯衍生物、聚苯醚、聚甲醛和含氟热塑性塑料。优选的热塑性树脂是结晶聚烯烃,它们是通过将C2-C20烯烃,例如但不限于乙烯、丙烯和C4-C12α-烯烃聚合形成的;该C4-C12α-烯烃例如1-丁烯、1-己烯、1-辛烯、2-甲基-1-丙烯、3-甲基-1-戊烯、4-甲基-1-戊烯、5-甲基-1-己烯以及它们的混合物。还可以使用乙烯和丙烯或乙烯或丙烯与另一种α-烯烃的共聚物,该α-烯烃例如丁烯-1;戊烯-1;2-甲基戊烯-1;3-甲基丁烯-1;己烯-1;3-甲基戊烯-1;4-甲基戊烯-1;3,3-二甲基丁烯-1;庚烯-1;己烯-1;甲基己烯-1;二甲基戊烯-1;三甲基丁烯-1;乙基戊烯-1;辛烯-1;甲基戊烯-1;二甲基己烯-1;三甲基戊烯-1;乙基己烯-1;甲基乙基戊烯-1;二乙基丁烯-1;丙基戊烷-1;癸烯-1;甲基壬烯-1;壬烯-1;二甲基辛烯-1;三甲基庚烯-1;乙基辛烯-1;甲基乙基丁烯-1;二乙基己烯-1和十二碳烯-1。
[0049]第一聚合物的分散颗粒通常具有小于10微米,优选小于5微米,更优选小于3微米的平均尺寸。
[0071]在一个实施方案中,用来制备第二聚合物组分的催化剂与用来制备所述热塑性第一聚合物的催化剂相同或相容。在这种情况下,第一和第二聚合区段可以在一个多区段反应器中,或是独立、串联连接的反应器,其中来自第一聚合区段的全部排出物(包括任何活性催化剂)被转移至第二聚合区段。根据需要,然后可以将附加的催化剂添加到第二聚合区段中,在这种情况下,弹性体第二聚合物衍生自引入到第一和第二聚合区段中的两种催化剂。在一个尤其优选的实施方案中,在两个或更多个串联连接的连续流动搅拌釜式或管式反应器中使用金属茂催化剂进行本发明的方法。
[0095]在另一个实施方案中,本文描述的聚合物共混物具有20%或更高,优选30%或更高,更优选40%或更高的极限伸长率(通过ISO37测量)。
[0096]在另一个实施方案中,本文描述的聚合物共混物具有90%或更低,优选70%或更低,更优选50%或更低,更优选30%或更低的压缩形变(通过ISO815A测量)。
[0098]在另一个实施方案中,本文描述的聚合物共混物具有500%或更低,优选250%或更低,更优选100%或更低的油溶胀(通过ASTMD471测量)。
[00125]本领域技术人员应理解,取决于所需的结果,以上列举的步骤可以改变。例如,本发明的组合物的挤出片材可以直接热成型或吹塑而不用冷却,因此省去了冷却步骤。其它参数也可以改变,以便获得具有所需特征的最终复合制品。
[00127]在另一个实施方案中,本发明涉及:
[00131]使用以下程序根据ASTME794-85测定峰熔点(Tm)和峰结晶温度(Tc)。使用熔化热计算结晶度,该熔化热使用ASTMD3417-99测定。使用TAInstrumentsQ100型设备或Perkin-ElmerDSC-7获得差示扫描量热(DSC)数据。将重量为大约5-10mg的样品封入铝样品盘中。首先以10°C/分钟的速率将样品从室温加热到200°C(第一次熔融)来记录DSC数据。然后在200°C下保持样品5分钟,然后以10°C/分钟等变(ramping)到-100°C,接着在-100°C下等温保持5分钟,然后以10°C/分钟的速率加热到200°C(第二次熔融)。记录第一和第二次循环热结果。实施例中报道的峰熔化温度和熔化热从第二次熔融获得。测量熔化曲线下面的面积并将该面积用来测定熔化热和结晶度。百分率结晶度使用以下公式计算,[曲线下面的面积(焦耳/克)/B(焦耳/克)]×100,其中B是主单体组分的均聚物的熔化热。B的这些值从由JohnWiley和Sons出版的“PolymerHandbook”,第四版(NewYork1999)中获得。189J/g的值(B)用作100%结晶聚丙烯的熔化热。290J/g的值用于100%结晶聚乙烯的熔化热。对于显示了多个冷却和熔融峰的聚合物,报道所有峰结晶温度和峰熔化温度。对每个熔融峰的熔化热进行单独的计算。
[00139]损耗模量(E′′)、储能模量(E′)和β松弛通过动态力学热分析(DMTA)测量。使用的仪器是得自TAInstruments,NewCastle,DE的RSAII,RheometricsSolidAnalyzerII。在张力模式下操作该仪器并使用经模塑的矩形样品。样品条件是:0.1%应变,1Hz频率,和2°C/分钟加热速率,覆盖-135°C至样品熔点的温度范围。在大约200°C下模塑样品。典型的样品尺寸是23mm的长度×6.4mm的宽度×0.25mm-0.7mm的厚度,这取决于样品。tanδ是E′′/E′的比率。这些DMTA实验的输出是储能模量(E′)和损耗模量(E′′)。储能模量量度弹性响应或材料储存能量的能力,而损耗模量量度粘性响应或材料耗散能量的能力。E′′/E′(=tanδ)的比率提供了材料的阻尼能力的衡量标准。能量耗散机理(即松弛模式)显示为tanδ中的峰,并且与作为温度的函数的E′的降低有关。与E′的报道值有关的误差预计约为±10%,这归因于模塑方法引入的差异度。
[00148]在第二聚合阶段中使用1,9-癸二烯作为二烯交联剂。从Sigma-Aldrich获得该1,9-癸二烯并通过让其首先在氮气下穿过在高温下活化的氧化铝柱,接着在氮气下穿过在高温下活化的分子筛而加以纯化。
[00149]在第一阶段中使用外消旋-二甲基·二甲基甲硅烷基双(2-甲基-4-苯基茚基)合锆催化剂(催化剂A)以制备聚丙烯,在第二阶段中使用二甲基·[二(对-三乙基甲硅烷基苯基)亚甲基](环戊二烯基)(3,8-二叔丁基芴基)合铪催化剂(催化剂B)(从Albemarle获得)以制备乙烯丙烯二烯橡胶。通过在甲苯中以1∶1的摩尔比用四(七氟-2-萘基)硼酸二甲基苯铵预活化这两种催化剂。实验条件、采用的催化剂和所得聚合物共混物的性能的详细数据列于下表1A中。
[00150]对实施例1中制备的反应器内制备的聚合物共混物实施溶剂萃取。每种级分的量列于表1A中。每个级分的量作为总反应器内制备的聚合物共混物的重量百分率列出。交联度定义为:
[00154]将实施例1中制备的聚合物共混物的样品在Brabender混合器中熔融混合并在压缩条件下模塑成板材,以及进行热塑性弹性体应用测试。还通过动态硫化进一步固化实施例1制备的聚合物共混物的其它样品。在Brabender混合器内连同表1B中列出的其它添加成分一起通过常规技术进行硫化。氢化硅DC25804(1.97%)从DowCorning获得。该氢化硅是具有氢化硅官能团的聚硅氧烷。铂催化剂混合物(PC085)(2.63%)从UnitedChemicalTechnologiesInc.获得。该混合催化剂包括0.0055重量份铂催化剂和2.49重量份矿物油。氧化锌从ZincCorporationofAmerica获得,链烷油Paralux6001R从ChevronOilCorporation获得。根据上述程序获得的性能数据列于表1B中。
[00155]遵循与实施例1中使用的相同程序在2升高压釜反应器中制备这一样品,不同之处在于在阶段1和阶段2聚合之间不使用空气注入。在两个聚合阶段中使用相同的催化剂,并通过在甲苯中以大约1∶1的摩尔比用四(五氟苯基)硼酸N,N-二甲基苯铵(得自Albemarle)预活化该催化剂。使用三异丁基铝(TIBAL)(25wt%,在甲苯中,购自Sigma-Aldrich)作为清除剂。详细的反应条件和聚合物性能列于表2A中。
[00156]使用上述程序对实施例2的反应器内制备的聚合物共混物实施溶剂萃取。每个萃取级分的量表示为总聚合物共混物的重量百分率并列于表2A中。使用AFM根据上述程序检测实施例2中制备的共混物的形态并在图2中示出结果。