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    • 1. 发明授权
    • Process for the production of high-flow propylene/ethylene copolymers
    • 生产高流动性丙烯/乙烯共聚物的方法
    • US5639822A
    • 1997-06-17
    • US355307
    • 1994-12-12
    • Klaus-Dieter HungenbergHarald SchwagerKlaus Dieter RuemplerPatrik Mueller
    • Klaus-Dieter HungenbergHarald SchwagerKlaus Dieter RuemplerPatrik Mueller
    • C08F2/34C08F2/38C08F4/642C08F4/646C08F210/06C08F297/08
    • C08F297/083C08F210/06
    • High-flow propylene/ethylene copolymers which have a melt flow index of from 2 to 200 g/min under a load of 2.16 kg at 230.degree. C. and which may be produced from the gas phase by polymerization in two stages in an agitated fixed bed in the presence of hydrogen acting as chain stoppage regulator and using a Ziegler-Natta catalyst system comprising a titaniferous solid component which contains a magnesium compound on finely divided silicon oxide or on finely divided aluminum oxide or on a finely divided aluminum silicate having the empirical formula SiO.sub.2.aAl.sub.2 O.sub.3, where a stands for a value between 0.001 and 2, and an aluminum component, by means of a procedure comprisinga) a first polymerization stage in which propylene is polymerized under a pressure of from 20 to 40 bar and at a temperature of from 60.degree. to 90.degree. C., the ratio of the partial pressure of the hydrogen to that of the propylene being adjusted to from 1:100 to 10:100, followed byb) a second polymerization stage, which consists in the polymerization, at a temperature of from 40.degree. to 100.degree. C., of a mixture of propylene and ethylene and the addition thereof, in the form of polymerized units, to the polypropylene produced in the first polymerization stage, the pressure in this second polymerization stage being from 10 to 30 bar and at least 7 bar lower than that used in the first polymerization stage, while the ratio of the partial pressure of the hydrogen to that of the propylene is adjusted to from 2:100 to 12:100 and the ratio of the weight of monomer converted in the first stage to that of monomer converted in the second stage is kept within the range of 1:1 to 20:1.
    • 高流动性丙烯/乙烯共聚物,其在230℃负载2.16kg时的熔体流动指数为2〜200g / min,可以通过在搅拌固定 在作为链停止调节剂的氢气存在下,使用齐格勒 - 纳塔催化剂体系,其包含含钛固体组分,其在细碎的氧化硅上或在细碎的氧化铝上或在具有经验的细碎的硅酸铝上含有镁化合物 其中a表示0.001和2之间的值,以及铝组分,通过包括以下步骤的方法:a)第一聚合阶段,其中丙烯在20至40巴的压力下聚合, 温度为60℃至90℃,氢气与丙烯的分压比为1:100至10:100,接着是b)第二聚合阶段,其中con 在40至100℃的温度下聚合丙烯和乙烯的混合物,并将其以聚合单元的形式加入到在第一聚合阶段中生产的聚丙烯中, 该第二聚合阶段为10至30巴,比第一聚合阶段中使用的低至少7巴,而氢与丙烯分压的比例调节至2:100至12: 100,第一阶段中转化的单体重量与在第二级转化的单体的重量比保持在1:1至20:1的范围内。
    • 5. 发明授权
    • Olefin polymers partially crosslinked with bismaleimido compounds
    • 烯烃聚合物与双马来酰亚胺化合物部分交联
    • US5461119A
    • 1995-10-24
    • US342027
    • 1994-11-16
    • Bernd L. MarczinkeHarald SchwagerJuergen Kerth
    • Bernd L. MarczinkeHarald SchwagerJuergen Kerth
    • C08F8/00C08F8/30C08F8/34C08F8/32
    • C08F8/30C08F8/34
    • Partially crosslinked olefin polymers are obtainable by reactinga) an ethylene polymer having a density of from 0.90 to 0.98 g/cm.sup.3 orb) a polymer of from 25 to 95% by weight of a propylene homopolymer and from 5 to 75% by weight of a propylene copolymer with polymerized C.sub.2 -C.sub.10 -alk-1-enes, the comonomer content being from 1 to 45% by weight, based on the total polymer,in the absence of free radical initiators, with from 0.001 to 5% by weight, based on the olefin polymer, of a bismaleimido compound of the general formula (I) ##STR1## where R is C.sub.1 -C.sub.20 -alkyl which may be interrupted by one or more oxygen atoms, or is C.sub.5 -C.sub.7 -cycloalkyl or C.sub.6 -C.sub.15 -aryl, each of which in turn may be substituted by one or more C.sub.1 -C.sub.10 -alkyl and/or C.sub.1 -C.sub.6 -alkoxy and/or C.sub.1 -C.sub.4 -dialkylamino groups, or is a radical of the following formula (II)R.sup.1 -Z-R.sup.2 (II)where R.sup.1 and R.sup.2 independently of one another are each C.sub.1 -C.sub.10 -alkyl, C.sub.5 -C.sub.7 -cycloalkyl or C.sub.6 -C.sub.10 -aryl, each of which in turn may be substituted by one or more C.sub.1 -C.sub.10 -alkyl and/or C.sub.1 -C.sub.6 -alkoxy and/or C.sub.1 -C.sub.4 -dialkylamino groups, and Z is C.sub.1 -C.sub.10 -alkyl, C.sub.1 -C.sub.4 -dialkylamino, oxygen or sulfonyl.
    • 部分交联的烯烃聚合物可通过使a)密度为0.90至0.98g / cm 3的乙烯聚合物或b)25至95重量%的丙烯均聚物和5至75重量%的丙烯均聚物的聚合物 具有聚合的C 2 -C 10 - 烷-1-烯的丙烯共聚物,在不存在自由基引发剂的情况下,基于总聚合物,共聚单体含量为1至45重量%,含有0.001至5重量% 基于烯烃聚合物,通式(I)的双马来酰亚胺化合物其中R是可被一个或多个氧原子间隔的C 1 -C 20烷基,或者是C 5 -C 7 - 环烷基或 C 6 -C 15 - 芳基,其各自依次可被一个或多个C 1 -C 10 - 烷基和/或C 1 -C 6 - 烷氧基和/或C 1 -C 4二烷基氨基取代,或者是下式的基团 II)其中R 1和R 2彼此独立的R 1 -Z-R 2(II)各自为C 1 -C 10 - 烷基,C 5 -C 7 - 环烷基或C 6 -C 10 - 芳基,它们各自可以被一个或多个 C 1 -C 10 - 烷基和/或C 1 -C 6 - 烷氧基和/或C 1 -C 4 - 二烷基氨基,Z为C 1 -C 10 - 烷基,C 1 -C 4 - 二烷基氨基,氧或磺酰基。
    • 8. 发明授权
    • Propylene-ethylene copolymers made from three different constituents
    • 由三种不同成分制成的丙烯 - 乙烯共聚物
    • US06300434B1
    • 2001-10-09
    • US08524024
    • 1995-09-06
    • Harald SchwagerJuergen Kerth
    • Harald SchwagerJuergen Kerth
    • C08F402
    • C08F297/086
    • Propylene-ethylene copolymers obtainable by three-step polymerization from the gas phase in an agitated fixed bed by means of a Ziegler-Natta catalyst system which, in addition to a titanium-containing solid component, also contains, as cocatalyst, an aluminum compound, where, in a first polymerization step, propylene is polymerized at from 60 to 90° C. and at from 20 to 40 bar and at a mean residence time of the reaction mixture of from 0.5 to 5 hours, then, in a second polymerization step, a mixture of propylene and ethylene is polymerized onto the polymer obtained from the first polymerization step at from 40 to 110° C. and from 5 to 30 bar, this pressure being at least 7 bar below the pressure in the first polymerization step, and at a mean residence time of the reaction mixture of from 0.2 to 4 hours, and then, in a third polymerization step, ethylene or a mixture of ethylene and propylene is polymerized onto the polymer obtained from the second polymerization step at from 40 to 110° C. and from 5 to 30 bar and at a mean residence time of the reaction mixture of from 0.1 to 5 hours, the weight ratio between the monomers reacted in the first and second polymerization steps being adjusted to from 1:1 to 20:1 and the weight ratio between the monomers reacted in the first two polymerization steps and those reacted in the third polymerization step being adjusted to from 1:2 to 20:1.
    • 丙烯 - 乙烯共聚物可通过齐格勒 - 纳塔催化剂体系在搅拌的固定床中从气相中三步聚合获得,除了含钛固体组分外,还含有作为助催化剂的铝化合物, 其中,在第一聚合步骤中,丙烯在60至90℃和20至40巴之间和反应混合物的平均停留时间为0.5至5小时时聚合,然后在第二聚合步骤 丙烯和乙烯的混合物在从第一聚合步骤获得的聚合物上聚合到40至110℃和5至30巴,该压力比第一聚合步骤中的压力低至少7巴, 在反应混合物的平均停留时间为0.2至4小时,然后在第三聚合步骤中,将乙烯或乙烯和丙烯的混合物聚合到由第二聚合步骤获得的聚合物上,从40至 110℃和5至30巴,反应混合物的平均停留时间为0.1至5小时,在第一和第二聚合步骤中反应的单体之间的重量比被调节至1:1至20 :1,在前两个聚合步骤中反应的单体和在第三聚合步骤中反应的单体之间的重量比被调节至1:2至20:1。
    • 9. 发明授权
    • Bismaleimide-crosslinked, flexible polyolefin blends
    • 双马来酰亚胺交联的柔性聚烯烃共混物
    • US5362808A
    • 1994-11-08
    • US21424
    • 1993-06-07
    • Sibylle BrosiusBernd L. MarczinkeHarald Schwager
    • Sibylle BrosiusBernd L. MarczinkeHarald Schwager
    • C08K5/34C08K5/3415C08L21/00C08L23/06C08L23/08C08L23/10C08L23/12C08L23/14C08L23/16C08L23/22C08L53/02C08K3/24C08L9/02C08L23/26C08L33/08C08L53/00
    • C08L23/14C08K5/3415C08L23/12C08L23/142C08L2205/02C08L2205/03C08L2205/035C08L23/06C08L23/0815C08L23/16C08L23/22C08L2312/00C08L53/02
    • Partially crosslinked polyolefin blends containa) a polymer of from 25 to 97% by weight of a propylene polymer (I), which contains from 0 to 15% by weight of polymerized C.sub.2 -C.sub.10 -alka-1-enes, and of from 3 to 75% by weight of a further propylene polymer (II) which contains from 15 to 80% by weight of polymerized C.sub.2 -C.sub.10 -alka-1-enes,b) a random ethylene copolymer containing from 5 to 20% by weight of polymerized C.sub.3 -C.sub.10 -alk-1-enes and having a density of from 0.89 to 0.925 g/cm.sup.3 at room temperature,c) a rubber-like material having a Shore A hardness of from 30 to 90 andd) a bismaleimido compound of the following formula (I) ##STR1## where R is C.sub.1 -C.sub.20 -alkyl which may be interrupted by one or more oxygen atoms,C.sub.5 -C.sub.7 -cycloalkyl or C.sub.6 -C.sub.15 -aryl, each of which in turn may be substituted by one or more C.sub.1 -C.sub.10 -alkyl and/or C.sub.1 -C.sub.6 -alkoxy and/or C.sub.1 -C.sub.4 -dialkylamino groups, or a radical of the following formula (II)R.sup.1 --Z--R.sup.2 (II)where R.sup.1 and R.sup.2 independently of one another are each C.sub.1 -C.sub.10 -alkyl, C.sub.5 -C.sub.7 -cycloalkyl or C.sub.6 -C.sub.10 -aryl, each of which in turn may be substituted by one or more C.sub.1 -C.sub.10 -alkyl and/or C.sub.1 -C.sub.6 -alkoxy and/or C.sub.1 -C.sub.4 -dialkylamino groups, and Z is C.sub.1 -C.sub.10 -alkyl, C.sub.1 -C.sub.4 -dialkylamino, oxgen or sulfonyl.
    • 部分交联的聚烯烃共混物包含a)25至97重量%的丙烯聚合物(I)的聚合物,其含有0至15重量%的聚合的C 2 -C 10 - 烷-1-烯和3 至75重量%的另外的丙烯聚合物(II),其含有15至80重量%的聚合的C 2 -C 10 - 烷-1-烯,b)无规乙烯共聚物,其含有5至20重量%的聚合的 C3-C10-烷-1-烯并且在室温下的密度为0.89至0.925g / cm3,c)肖氏A硬度为30至90的橡胶状材料,以及d)二 下式(I)其中R是可被一个或多个氧原子间隔的C 1 -C 20烷基,C 5 -C 7 - 环烷基或C 6 -C 15 - 芳基,其中每个可以被取代 通过一个或多个C 1 -C 10 - 烷基和/或C 1 -C 6 - 烷氧基和/或C 1 -C 4 - 二烷基氨基或下式(II)的基团R 1 -Z-R 2(II)其中R 1和R 2独立地 彼此各自为C 1 -C 10 - 烷基, C 5 -C 7 - 环烷基或C 6 -C 10 - 芳基,它们各自可以被一个或多个C 1 -C 10 - 烷基和/或C 1 -C 6 - 烷氧基和/或C 1 -C 4二烷基氨基取代,Z是 C 1 -C 10 - 烷基,C 1 -C 4 - 二烷基氨基,氧基或磺酰基。
    • 10. 发明授权
    • Partially crosslinked composition comprising polymers of propylene and
of ethylene
    • 部分交联的组合物包含丙烯和乙烯的聚合物
    • US5384369A
    • 1995-01-24
    • US238791
    • 1994-05-06
    • Sibylle BrosiusErhard SeilerHarald SchwagerGerhard KressLothar Schlemmer
    • Sibylle BrosiusErhard SeilerHarald SchwagerGerhard KressLothar Schlemmer
    • C08F255/02C08L23/26
    • C08F255/02
    • A partially crosslinked polymer composition comprisinga) a polymer comprising from 25 to 95% by weight of polypropylene and from 5 to 75% by weight of a propylene copolymer with copolymerized C.sub.2 -C.sub.10 -alk-1-enes, the comonomer content being from 1 to 45% by weight, based on the total polymer,b) a random ethylene copolymer containing from 5 to 20% by weight of copolymerized C.sub.3 -C.sub.10 -alk-1-enes and having a density at room temperature of from 0.89 to 0.925 g/cm.sup.3, andc) an organosilane compound of the formula (I)A.sub.4-n SiR.sub.n (I) where A are identical or different acrylates or methacrylates or vinyl groups, R are identical or different C.sub.1 -C.sub.8 -alkoxy or C.sub.1 -C.sub.8 -acetoxy groups, and n is 1, 2 or 3,can be obtained by reacting a polymer mixture of the polymer a) and the random ethylene copolymer b) with the organosilane compound c) in the presence of a free-radical initiator and in the presence of a condensation catalyst at from 180.degree. to 280.degree. C., at from 1 to 100 bar and at a mean residence time of the reaction mixture of from 0.2 to 10 minutes.
    • 一种部分交联的聚合物组合物,其包含a)包含25至95重量%的聚丙烯和5至75重量%的具有共聚的C 2 -C 10 - 烷-1-烯的丙烯共聚物的聚合物,共聚单体含量为1 至45重量%,b)含有5至20重量%的共聚的C 3 -C 10 - 烷-1-烯并且在室温下的密度为0.89至0.925g的无规乙烯共聚物 cm 3,和c)式(I)的有机硅烷化合物A4-nSiRn(I)其中A是相同或不同的丙烯酸酯或甲基丙烯酸酯或乙烯基,R是相同或不同的C 1 -C 8 - 烷氧基或C 1 -C 8 - 乙酰氧基 基团,n为1,2或3,可以通过在自由基引发剂存在下使聚合物a)和无规乙烯共聚物b)的聚合物混合物与有机硅烷化合物c) 的缩合催化剂在180-280℃,1-100巴和平均停留时间下进行 的反应混合物为0.2至10分钟。