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    • 2. 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。
    • 3. 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。
    • 4. 发明授权
    • Partially crosslinked plastics materials of propylene copolymers
    • 丙烯共聚物的部分交联塑料材料
    • US5371144A
    • 1994-12-06
    • US025861
    • 1993-03-03
    • Sibylle BrosiusHarald SchwagerSusanne HahnBernd L. Marczinke
    • Sibylle BrosiusHarald SchwagerSusanne HahnBernd L. Marczinke
    • C08F8/42C08F255/00C08F8/00
    • C08F8/42C08F255/00
    • Partially crosslinked plastics materials having a melt flow index of from 0.1 to 100 g/10 min at 230.degree. C. and under a weight of 2.16 kg, containinga) a polymer of from 25 to 97% by weight of a propylene copolymer (I) which contains from 0.1 to 15% by weight of polymerized C.sub.2 -C.sub.10 -alk-1-enes and of from 3 to 75% by weight of a further propylene copolymer (II) which contains from 15 to 80% by weight of polymerized C.sub.2 -C.sub.10 -alk-1-enes andb) an organosilane compound of the following formula (I)A.sub.4-n SiR.sub.n (I)where the radicals A are identical or different and are each an acrylate or methacrylate or vinyl, the radicals R are identical or different and are each C.sub.1 -C.sub.8 -alkoxy or C.sub.1 -C.sub.8 -acetoxy and n is 1, 2 or 3,are obtainable by reacting the polymer a) with the organosilane compound b) in the presence of a free radical initiator and a condensation catalyst at from 180 to 280.degree. C. and from 1 to 100 bar and in the course of average residence times of the reaction mixture of from 0.2 to 10 minutes.The novel plastics materials have in particular improved processibility and thermoformability, a lower sealing temperature and better white fracture behavior.
    • 在230℃和2.16kg重量下熔体流动指数为0.1-100g / 10min的部分交联塑料材料,其包含a)25至97重量%的丙烯共聚物(I ),其含有0.1至15重量%的聚合的C 2 -C 10 - 烷-1-烯和3至75重量%的另外的丙烯共聚物(II),其含有15至80重量%的聚合的C 2 -C 10 - 烷-1-烯和b)下式(I)的有机硅烷化合物,其中基团A相同或不同,各自为丙烯酸酯或甲基丙烯酸酯或乙烯基,其中基团R是相同的 或不同的,并且各自为C 1 -C 8 - 烷氧基或C 1 -C 8 - 乙酰氧基且n为1,2或3,可通过使聚合物a)与有机硅烷化合物b)在自由基引发剂和缩合物 催化剂为180-280℃和1-100巴,反应混合物的平均停留时间为0.2-10分钟 ute。 新颖的塑料材料具有特别改进的加工性和热成型性,较低的密封温度和更好的白色断裂性能。
    • 7. 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。
    • 8. 发明授权
    • Zieger-natta-type catalyst systems
    • 齐格纳塔型催化剂体系
    • US5166113A
    • 1992-11-24
    • US759980
    • 1991-09-17
    • Harald SchwagerPeter KoelleJuergen KerthRalf Zolk
    • Harald SchwagerPeter KoelleJuergen KerthRalf Zolk
    • C08F10/00
    • C08F10/00
    • Ziegler-Natta-type catalyst systems containing, as active constituents,a) a titanium-containing solid component which also contains magnesium, halogen and a carboxylic acid ester, and, as cocatalyst,b) an aluminum compound,wherein the carboxylic acid ester in the solid component is a diester of a carboxylic acid of the formula Ia or Ib ##STR1## where R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are identical or different and are hydrogen, C.sub.1 - to C.sub.15 -alkyl, C.sub.7 - to C.sub.15 -alkylaryl, or 5- to 7-membered cycloalkyl, which may itself carry C.sub.1 - to C.sub.10 -alkyl groups, are particularly suitable for the preparation of polypropylene and copolymers of propylene containing minor amounts of other .alpha.,.beta.-unsaturated olefinic compounds having from 2 to 12 carbon atoms.
    • 含有作为活性成分的齐格勒 - 纳塔型催化剂体系a)含镁,卤素和羧酸酯的含钛固体组分,和作为助催化剂的b)铝化合物,其中羧酸酯在 固体组分是式Ia或Ib的羧酸的二酯(Ia)其中R 1,R 2,R 3和R 4相同或不同,为氢,C 1至C 15 - 烷基 可以自身携带C1-至C10烷基的C 7 -C 15烷基芳基或5-至7-元环烷基特别适用于制备聚丙烯和含有少量其它α,β- 具有2至12个碳原子的不饱和烯烃化合物。
    • 9. 发明授权
    • Preparation of propylene-ethylene copolymers
    • 丙烯 - 乙烯共聚物的制备
    • US5147928A
    • 1992-09-15
    • US660252
    • 1991-02-25
    • Juergen KerthHarald SchwagerRalf Zolk
    • Juergen KerthHarald SchwagerRalf Zolk
    • C08F2/34C08F10/00C08F210/06C08F297/08
    • C08F297/083
    • Propylene-ethylene copolymers are prepared in an agitated bed of solids by first polymerizing propylene from the gas phase in a first polymerization zone at 20-40 bar and 60.degree.-90.degree. C. by addition of a Ziegler-Natta catalyst system, and copolymerizing in a second polymerization zone at 7-35 bar and 40.degree.-70.degree. C. the finely divided polymer from the first polymerization zone with a mixture of olefins a process which comprises copolymerizing in the second polymerization zone with a mixture of propylene, ethylene and a further .alpha.-olefin of from 4 to 10 carbon atoms, setting the ratio of the partial pressures between propylene and ethylene within the range from 100:20 to 100:120 and that of the partial pressures between propylene and the further .alpha.-olefin within the range from 100:1 to 100:20, setting the pressure in the second polymerization zone at at least 5 bar below the pressure in the first polymerization zone, and determining the weight ratio between the monomers reacted in the first polymerization zone and those reacted in the second polymerization zone in such a way that said weight ratio is within the range from 100:10 to 100:50.
    • 丙烯 - 乙烯共聚物在搅拌的固体床中通过首先在20-40巴和60-90℃的第一聚合区中通过加入齐格勒 - 纳塔催化剂体系在气相中聚合丙烯来制备,并共聚合 在7-35巴和40-70℃的第二聚合区中,来自第一聚合区的细分聚合物与烯烃混合物的方法,该方法包括在第二聚合区中与丙烯,乙烯和 另外的4-10个碳原子的α-烯烃使丙烯和乙烯之间的分压比在100:20至100:120的范围内,丙烯与其它α-烯烃之间的分压比 范围为100:1至100:20,将第二聚合区中的压力设定在第一聚合区内的压力以下至少5巴,并测定单体之间的重量比 在第一聚合区和第二聚合区中反应的那些,使得所述重量比在100:10至100:50的范围内。