CN1067089C - 一种制备聚丙烯组合物的方法 - Google Patents

一种制备聚丙烯组合物的方法 Download PDF

Info

Publication number
CN1067089C
CN1067089C CN90103904A CN90103904A CN1067089C CN 1067089 C CN1067089 C CN 1067089C CN 90103904 A CN90103904 A CN 90103904A CN 90103904 A CN90103904 A CN 90103904A CN 1067089 C CN1067089 C CN 1067089C
Authority
CN
China
Prior art keywords
propylene
weight
ethylene
ethene
gram
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 - Lifetime
Application number
CN90103904A
Other languages
English (en)
Other versions
CN1047514A (zh
Inventor
朱利亚诺·切金
弗洛里亚诺·古列尔米
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.)
Himont Inc
Basell North America Inc
Original Assignee
Himont Inc
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=11165769&utm_source=***_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=CN1067089(C) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Himont Inc filed Critical Himont Inc
Publication of CN1047514A publication Critical patent/CN1047514A/zh
Application granted granted Critical
Publication of CN1067089C publication Critical patent/CN1067089C/zh
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • 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
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
    • C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
    • C08F297/083—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins the monomers being ethylene or propylene
    • 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
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
    • C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
    • C08F297/083—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins the monomers being ethylene or propylene
    • C08F297/086—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins the monomers being ethylene or propylene the block polymer contains at least three blocks
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/02—Heterophasic composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/10—Peculiar tacticity
    • C08L2207/14—Amorphous or atactic polypropylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2308/00—Chemical blending or stepwise polymerisation process with the same catalyst
    • 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
    • Y10S526/909—Polymerization characterized by particle size of product
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
  • Polymerization Catalysts (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

平均直径在500至7000微米之间的球形可流动颗粒的聚丙烯组合物具有宝贵的塑弹特性，该组合物具有下列组分：
A)10至60重量分的等规指数大于90的聚丙烯均聚物或丙烯含量在85%(重量)以上和等规指数大于85的丙烯与乙烯和/或一个α-烯烃(如丁烯-1、戊烯-1或4-甲基-1-戊烯)的结晶丙烯共聚物；
B)10至40重量分的含有在室温下不溶于二甲苯的乙烯的聚合物部分；
C)30至60重量分的含有任意小比例的在室温可溶于二甲苯的二烯烃并含有40至70%(重量)乙烯的非晶态乙烯-丙烯共聚物部分。

Description

一种制备聚丙烯组合物的方法
本发明涉及具有弹性性质、球形颗粒、特殊流动性和表观密度特性的热塑性聚丙烯组合物以及它们的制备方法。
在最近几年中，具有弹性而且能保持使用相同的设备和通常热塑性材料所用的方法转变为制品的能力的聚丙烯组合物已经越来越显得重要。
已经发现所述组合物(有时被称作聚烯烃热塑性弹性体)首先在汽车、电缆和体育用品领域中的应用，由于该组合物具有良好性能，有代替更昂贵的以苯乙烯和丁二烯为基础的热塑性橡胶的趋向。
该组合物在动态硫化条件下，将乙烯-丙烯橡胶(EPR)或乙烯-丙烯-二烯橡胶(EPDM)与结晶聚烯烃(特别是聚丙烯)混合而制备。
这种制备方法包括大量消耗能量及组分的机械均匀性不总是给予最终产品所需的最佳平衡性能。
因此，需要通过聚合方法以产生具有所需的弹性-塑性平衡的聚烯烃组合物。
USP4298721描述了在聚合过程中直接制备具有弹性-塑性的聚合物产品的方法。
在这份专利中所述的热塑性弹性体可以通过使用在卤化镁上载有特殊类型的催化剂聚合乙烯-丙烯混合物而制得。用这种方法得到的共聚物具有弹性塑性性质，但不耐热，因为他们具有相对低的熔点(约100-130℃)。
USP4489195描述了使用载在卤化镁上的立体有规催化剂，进行两阶段聚合制备聚烯烃热塑性弹性体；第一阶段生成聚丙烯均聚物，第二阶段中最好在气相下进行制得一种弹性的乙烯/丙烯共聚物。
为了防止颗粒的附聚作用，在第二阶段中应维持相当低的温度(在50℃)，得到粉状聚合物。
从热交换及减少催化剂生产率的观点来说，在橡胶共聚物形成阶段，需要在相对低的温度下进行操作，对该方法极其不利。根据该专利提供的资料，该组合物不包含在室温下不溶于二甲苯中的乙烯聚合物的部分。
USP4491652描述了用二阶段制备聚丙烯热塑性弹性体的方法，在第一阶段使丙烯聚合成聚丙烯均聚物，在第二阶段使乙烯-丙烯的混合物聚合形成橡胶共聚物。第二阶段是在溶剂存在下于60°至80℃温度下进行的。在该温度下进行操作，获得带有生成团块的部分溶解的橡胶状共聚物，然后必须***。按照该专利，这种***是通过磨碎来完成的。事实上，大家都知道，当橡胶状乙烯-丙烯共聚物的百分率超过总聚合物的20％时，不可避免颗粒的附聚作用，甚至操作是在立体有规催化剂存在下进行也是如此(见欧洲公开专利申请0029651和比利时专利876413)。
当乙烯-丙烯共聚合阶段在气相中进行，附聚现象特别关键，在气相中进行该方法，实际上防止了反应器的污垢。
现在，意料不到的是已经找到了使用载在氯化镁上特殊催化剂，即使在气相过程中，可得到具有塑弹特性，流动性及堆积密度特性足够高的球形颗粒聚丙烯组合物，而且允许使用同样的转化成产品的通常的方法，而不需要预先造粒操作。
由于该组合物具有塑弹特性，可适合于所预见到传统的热塑性聚烯烃弹性体的所有应用。
此外，因为该组合物是生成的橡胶相均匀分布在聚丙烯基质中条件下获得的，其性能比通过组分的机械混合而得到的相应组合物好。
最后，由于组合物是用很高的活性催化剂制得的，在所述组合物中催化剂残余物的量是如此的小以致不需要将它除去。
本发明的组合物包括：
A)，10-60重量分，优选20～50重量分的等规指数大于90，优选是在95和98之间的聚丙烯均聚物或丙烯与乙烯和/或一种α-烯烃CH2=CHR(其中R为2-6碳的烷基)的结晶共聚物，它含有大于85％(重量)的丙烯，其等规指数大于85；
B)，10-40重量分含有在室温下不溶于二甲苯的乙烯的聚合物部分；
C)，30～60重量分，优选为30～50重量分的无定形乙烯-丙烯共聚物部分，它们含有任意小比例的二烯烃(在室温下可溶于二甲苯)及40-70％(重量)的乙烯。
被聚合的乙烯总含量为20至60％(重量)之间。
不同部分的分子量(在四氢化萘中于135℃，测定的特性粘度而确定的)随组分的性质和最终产品的熔体指数而变化。包括在下面较佳范围内：
-对于部分A)为0.5至3分升/克；
-对于部分B)加C)为2至8分升/克。
正如已指出的，得到的组合物为球形颗粒，其平均直径在500至7000微米之间，在70℃下的流动性小于30秒；填充堆积密度大于0.4克/厘米3，尤其是在0.4～0.6克/厘米3之间。
组合物呈现至少一个熔化峰(在差示扫描量热法(DSC)中温度高于140℃测定)；挠曲模量低于700MPa，更好的是在200至500MPa之间；维卡(VICAT)软化点大于50℃；肖氏A硬度大于80，肖氏D硬度大于30；75％的永久变形小于60％，特别是在20至50％之间；拉伸应力大于6MPa，特别是在8至20MPa之间。
组合物在电子显微镜下检验表明，分散相是由无定形乙烯-丙烯共聚物构成，具有平均颗粒尺寸小于2μm。
由组合物获得的制成品，特别是在汽车、电缆和体育用品领域中应用。
用聚合方法制备的组合物，至少包括二个阶段，其中在第一阶段中丙烯聚合成组分A)，后一阶段使乙烯-丙烯混合物聚合成组分B)和C)。
操作是在液相或气相或液-气相下进行的。
一个较佳的方法是用液体丙烯作稀释剂的丙烯均聚阶段和除了丙烯部分脱气外没有中间阶段的气相的丙烯和乙烯共聚阶段。
丙烯的聚合可以在乙烯或一个α-烯烃例如丁烯-1、戊烯-1、4-甲基戊烯-1存在下进行，其质量使所得产品的等规指数大于85％。
丙烯和乙烯的共聚也可以在另-α-烯烃或二烯烃(共轭或非共轭)例如丁二烯1,4-己二烯、1,4-己二烯1,5-己二烯、亚乙基-降冰片烯-1存在下进行。
在丙烯聚合阶段和在丙烯及乙烯共聚阶段的反应温度可以相同或不相同，在均聚合情况下一般为40℃至90℃之间，更好的是50至80℃之间，共聚合情况为50至70℃之间。
第一阶段的压力是在工作温度下，与液体丙烯蒸汽压力相竞争，可通过少量用于供给催化剂混合物的惰性稀释剂的蒸汽压力和作为分子量的调节剂的氢的过压得以改进。
关于共聚阶段的压力，如果在气相下进行，可在5至30大气压之间；关于二个阶段的停留时间，依赖于所希望的均聚合部分和双聚合物B和C部分之间的关系而变化，一般在30分至8个小时之时。已知的传统的链转移剂例如氢和二乙基锌可作分子量调节剂使用。
聚合使用的催化剂包括含有载在氯化镁上的钛化合物和电子给体化合物(内给体)的固体化合物与三烷基铝化合物和电子给体化合物(外给体)的反应产物。
为了获得本发明提出的具有高堆积密度流动颗粒的组合物，固体催化剂成分应呈现出下列特性是至关重要的。
-表面积小于100米2/克，特别在50至80米2/克之间；
-孔率：在0.25至0.4厘米3/克之间；
-x射线光谱：卤素存在在33.5°与35°之间的角2处，并在2v=14.95时无反射。
催化剂组分是由下述方法制备。
对一摩尔氯化镁一般含有3摩尔醇的氯化镁与醇的加合物可通过在与加合物不溶混的惰性烃液体中乳化熔融的加合物，然后很快冷却乳状液，以便使加合物固化成球形颗粒而获得球状颗粒。
然后，在温度为50°至130℃之间加热循环中对颗粒进行部分脱醇，使其醇含量对每摩尔氯化镁为3至1-1.5摩尔。
接着将加合物悬浮在浓度为40-50克/升的冷四氯化钛中，然后在80°-135℃中保持1-2小时。
在四氯化钛中还要加一种电子-给体化合物，后者最好选自邻苯二甲酸的烷基、环烷基或芳基酯，例如邻苯二甲酸二异丁基、2-正-丁基和2-正-辛基酯。
通过过滤或沉降起热分离过量的四氯化钛，并用四氯化钛重复处理一次或多次；然后用庚烷或己烷洗涤固体并干燥。
如此得到的催化剂组分具有下列特性：
-表面积：小于100米2/克。特另在50至80米2/克之间；
-孔率：0.25～0.4厘米3/克；
-孔体积分布为孔隙半径大于100A的大于50％。
-X射线光谱：存在的卤素在33.5°至35°的2v角之间具有最大强度，并在14.95°的2v处无反射。
催化剂可以通过催化剂组分与三烷基铝化合物，更好的是三乙基铝、三异丁基铝和电子一给体化合物相混合而获得，电子一给体化合物最好从式为R′R″Si(OR)2的硅烷化合物中选取,其式中的R′和R″可以是相同或不同的1-18个碳原子的烷基、环烷基、或芳基，和R是1-4个碳的烷基。
典型的硅烷是二苯基二甲氧基硅烷、二环己基二甲氧基硅烷、甲基叔丁基二甲氧基硅烷和二异丙基二甲氧基硅烷。
如苯基三乙氧基硅烷之类的硅烷化合物也可应用。
铝/钛之比通常在10至200之间，硅烷/铝的摩尔比在1/5至1/50之间。
催化剂可以用少量的烯烃(预聚合)预接触保持催化剂在烃溶剂中成悬浮液，在室温至60℃之间的温度下聚合，产生聚合物的量为催化剂重量的0.5至3倍。
操作也可在液体单体中进行，在这种情况下产生聚合物的量可高达催化剂重量的1000倍。
在实例和正文中所列出的有关性能数据由使用下述方法测定的：
性能                    方法-流动性指数(M.F.R.L.)    ASTM-D1238-乙烯％(重量)            光谱学I.R.-特性粘度                在四氢化萘中于135℃测定-二甲苯可溶物％(重量)    (看前实例的注)-挠曲模量                 ASTM-D790-切口悬臂梁式弹性         ASTM-D256-维卡(1公斤)软化点        ASTM-D1525-A/D肖氏硬度              ASTM-D2240-75％的永久变形           ASTM-D421-拉伸应力                 ASTM-D638-表面积                   B.E.T.-孔率                     B.E.T.-堆积密度                 DIN-53194-流动性                   取100克聚合物流过一个漏
                      斗所化时间，其漏斗打出的出
                      口的直径为1.27厘米，并且
                      壁与垂直线成20°的倾斜。-粒度              ASTM-D    1921-63-耐泛白            由被试验的聚合物的冲击盘来测定，该冲击
               盘由带有一个直径12.7毫米和重量78
               克的半球形冲头组成的锤头的压力注塑获得，
               测量所得泛白(h)的最小高度和设备容许
               的最大高度(76厘米)下泛白面积的大小。
进行各种物理机械试验用的样品由球形颗粒的聚合物(在模压之前先用0.1％(重量)的IRGANOX1010及0.1％(重量)的BHT(2,6-二叔丁基对甲酚进行预稳定)在下列条件下，并使用GBF V160注压机直接模压成。
-熔化聚合物的温度：190℃；
-模温60℃；
-注射时间20秒；
-冷却时间25秒。
总的双聚合物的重量百分率(％BP=％C+％B)，通过测定在第二阶段装入丙烯-乙烯混合物的重量并将它与最终产品的重量比较来计算
在前面正文所描述的A、B和C三部分重量百分率按下列方法来确定：
％A=100-％BP
％C=Sc-P.SP
其中，Sc和Sp分别是最终产品和聚丙烯部分A的二甲苯可溶部分的重量百分率，p是所述的部分与最终产品之间的重量比。
％B=100-％A=％C
含有在共聚物部分C可溶于二甲苯的乙烯重量酚率用下列公式来计算
在部分C中乙烯的百分率=CF-CP·Q/y其中：CF=最终产品可溶于二甲苯的乙烯％(重量)。
Cp=聚丙烯部分A可溶于二甲苯的乙烯％(重量)。
Q=部分A可溶于二甲苯的重量百分率乘以部分A的重量与最
终产品相比，再被最终产品可溶于二甲苯的重量部分去除。
y=C的重量百分率乘以总的双聚合物的重量百分率再用100
去除注意：溶于二甲苯百分率的测定
将2.5克聚合物于135℃，不断搅拌下，溶于250毫升二甲苯中，仍进行搅拌，20分钟后使溶液冷却至25℃，然后使其静止30分钟。
用过滤纸将沉淀物过滤，溶液在氮气流中蒸发，剩余物在80℃真空干燥，直至恒重。用这方法可计算在室温下聚合物溶于二甲苯中的重量百分率。室温下不溶于二甲苯的聚合物重量百分率可认为为聚合物的等规指数，因此，所得到的值基本上与用汽腾的正-庚烷萃取所测定的等规指数相符合。通过此规定构成聚丙烯的等规指数。
实施例一般的操作方法
试验在带有螺旋磁性搅拌器(大约90转/分)的22升不锈钢高压釜中进行。
除非另有指明，反应过程中的温度和压力保持恒定。
气相用过程气体一色层谱连续地进行分析。
在二个阶段中操作是间歇操作：第一阶段由丙烯在液体单体中的均聚合组成，第二阶段由乙烯和丙烯在气相中的共聚合组成。A)第一阶段
在高压釜内于20℃按下列次序引进物料：
16升液体丙烯及催化剂配合物，该配合物由固体组分(大约0.15克)与75毫升10％的三乙基铝己烷溶液和适量的苯基三乙氧基硅烷(PES)-(AL/PES摩尔比=10)混合物组成。
催化剂***是以丙烯压力输入，在大约10分钟内将温度升为70℃，并在整个聚合期间保持恒定，为了保持所需恒定浓度，不断分析气相中的氢气和加入的氢气。
无论什么时候，乙烯都用作共聚单体，为了保持气相中恒定的百分率，不断加入适量的这种烯烃。
在一确定时间之后，实际上所有剩余单体在大气压于60℃下通过脱气而除去。B)第二阶段
来自第一阶段的均聚物，取出为了各种分析用的样品后，保持在被确定的温度中，为了要获得气相组成及压力按所需比例量按次序加入。
在聚合过程中，通过加入如所需双聚合物相同组成及容纳在90℃的装有恒温器的钢瓶内的乙烯-丙烯混合物来保持压力恒定。
进料的持续时间根据催化剂***的反应及及打算供给相应的均聚物和双聚合物组分所需的双聚合物量而变化。在试验结束时，排出粉末，并进行稳定，再在60℃氮气流下恒温箱干燥，由制得的球形颗粒的MgCl2·3C2H5OH加合物来制备所用催化剂组分，可按照U.S.4399054实例2的方法进行，但操作中用3000转/分代替10000转/分，然后加合物在氮气流中由50℃逐渐加热到100℃进行脱醇，直至醇含量达到每摩尔氯化镁为1.5摩尔为止。
经部分脱醇的加合物，其表面积=9.1米2/克，堆积密度=0.564克/厘米3。
将25克所述加合物在0℃搅拌下加到625毫升的TiCl4中，在1个小时内加热到100℃，当温度达到40℃时，按镁/邻苯二甲酸二异丁酯的摩尔比=8添加邻苯二甲酸二异丁酯，放置沉降，然后趁热虹吸液体，加入550毫升的TiCl4并在120℃加热1小时。放置沉降，然后趁热虹吸液体。使用200毫升的无水己烷，于60℃洗涤固体6次，然后在室温下再洗涤3次。经真空干燥的固体表示出如下特性：
-孔率=0.261厘米3/克；
-表面积=66.5米2/克；
-堆积密度=0.440克/厘米3。进行的全部试验及有关的操作条件列于表1A和1B中。
在实例2和4所用的外给体为二苯基二甲氧基硅烷代替苯基三乙氧基硅烷。
              表1A
                表1B
Figure 9010390400161
             表1B(续)
Figure 9010390400171
N.B.=“不破裂”
对于本领域的普通技术人员来说，在阅读了上述说明后对本发明所公开的其它特征、优点及实施例将会很快明白，尽管本发明的具体实施例已作了很详细描述。在不违背本发明的精神、范围、所描述的内容及保护范围可以对这些实施例作些变化和改变。

Claims (7)

1．一种制备聚丙烯组合物的方法，所述组合物包括：A)10-60重量份的等规指数大于90的聚丙烯均聚物或丙烯与乙烯和/或一个CH2=CHR烯烃的结晶共聚物，其中R为2-6个碳的烷基，该共聚物含有85％(重量)以上的丙烯，其等规指数大于85；B)10-40重量份的含有在室温下不溶于二甲苯的乙烯的结晶聚合物部分；C)30-60重量份无定形乙烯-丙烯共聚物部分，并含有任意小比例的在室温下溶于二甲苯的二烯烃及含有40至70％(重量)的乙烯，所述组合物的挠曲模量小于700 MPa，75％的永久变形小于60％，拉伸应力为8-20 MPa，
所述方法包括丙烯或丙烯与乙烯和/或α-烯烃以形成聚合物相A)的聚合阶段和乙烯-丙烯混合物聚合成聚合物相B)和C)的阶段，所用催化剂为由三烷基铝化合物和包括载在氯化镁上的钛的卤化物或钛的卤素-醇化物和电子-给体化合物的固体组分获得的；所述的固体组分的表面积小于100米2/克，孔率为0.25至0.4厘米3/克，孔体积分布为孔的半径大于100的为50％以上，显示了X射线光谱在33.5°至35°的角2Q之间含有卤素最大强度，并表明在14.95°的2Q处无反射，所述聚合反应在40～90℃的温度气相压力为0.5-3 Mpa和停留时间为30分钟～8小时的条件下进行。
2.根据权利要求1的方法，其中聚合的乙烯的总含量为20-60％(重量)。
3．根据权利要求1或2的方法，其中所得聚丙烯组合物的挠曲模量为200-500MPa，永久变形为20-50％，拉伸应力为8-20MPa。
4．根据权利要求1或2的方法，其中所得聚丙烯组合物呈球形，其颗粒的平均直径为500-7000微米，流动性小于30秒，填充堆积密度大于0.4克/厘米3。
5．根据权利要求1的方法，其中丙烯的聚合阶段是在液体单体中进行的，并且乙烯-丙烯共聚的阶段是在气相中进行的。
6．根据权利要求1的方法，该方法在气相中进行。
7．根据权利要求1的方法，其中所述的乙烯-丙烯混合物的共聚在一个二烯烃的存在下进行。
CN90103904A 1989-04-28 1990-04-28 一种制备聚丙烯组合物的方法 Expired - Lifetime CN1067089C (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
IT20328A/1989 1989-04-28
IT20328A/89 1989-04-28
IT8920328A IT1230133B (it) 1989-04-28 1989-04-28 Composizioni polipropileniche plasto-elastiche

Publications (2)

Publication Number Publication Date
CN1047514A CN1047514A (zh) 1990-12-05
CN1067089C true CN1067089C (zh) 2001-06-13

Family

ID=11165769

Family Applications (1)

Application Number Title Priority Date Filing Date
CN90103904A Expired - Lifetime CN1067089C (zh) 1989-04-28 1990-04-28 一种制备聚丙烯组合物的方法

Country Status (27)

Country Link
US (1) US5302454A (zh)
EP (1) EP0400333B1 (zh)
JP (1) JP2950908B2 (zh)
KR (1) KR0160511B1 (zh)
CN (1) CN1067089C (zh)
AR (1) AR244740A1 (zh)
AT (1) ATE130014T1 (zh)
AU (1) AU634229B2 (zh)
BR (1) BR9001989A (zh)
CA (1) CA2015683C (zh)
CZ (1) CZ283097B6 (zh)
DD (1) DD294031A5 (zh)
DE (1) DE69023392T2 (zh)
ES (1) ES2081870T3 (zh)
FI (1) FI99016C (zh)
HU (1) HU218855B (zh)
IL (1) IL94153A (zh)
IT (1) IT1230133B (zh)
MX (1) MX20476A (zh)
MY (1) MY112377A (zh)
NO (1) NO176442C (zh)
PL (1) PL164127B1 (zh)
PT (1) PT93922B (zh)
RU (1) RU2092502C1 (zh)
SK (1) SK280805B6 (zh)
YU (1) YU82690A (zh)
ZA (1) ZA902972B (zh)

Families Citing this family (151)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2600829B2 (ja) * 1988-08-04 1997-04-16 三井石油化学工業株式会社 ポリプロピレン樹脂組成物
IL95097A0 (en) * 1989-08-23 1991-06-10 Himont Inc Thermoplastic olefin polymer and its preparation
IT1240613B (it) * 1990-03-26 1993-12-17 Enichem Anic Spa Catalizzatore supportato per la polimerizzazione e la copolimerizzazione di composti olefinicamente insaturi, e procedimento di (co) polimerizzazione impiegante lo stesso
IT1241094B (it) * 1990-03-30 1993-12-29 Himont Inc Polimeri del propilene iperpuri (capacitor grade)
IT1243188B (it) * 1990-08-01 1994-05-24 Himont Inc Composizioni poliolefiniche elastoplastiche
US5212246A (en) * 1990-09-28 1993-05-18 Himont Incorporated Olefin polymer films
TW259804B (zh) * 1992-01-18 1995-10-11 Hoechst Ag
IT1254202B (it) * 1992-02-06 1995-09-14 Himont Inc Manufatti accoppiati comprendenti un tessuto-non-tessuto e un film in materiali poliolefinici e procedimento per la loro preparazione
AU662202B2 (en) * 1992-02-24 1995-08-24 Montell North America Inc. Polyolefin compositions having good transparency and impact resistance
FI112233B (fi) * 1992-04-01 2003-11-14 Basell Polyolefine Gmbh Katalyytti olefiinipolymerointia varten, menetelmä sen valmistamiseksi ja sen käyttö
EP0574821B1 (en) * 1992-06-18 1998-03-11 Montell Technology Company bv Process and apparatus for the gas-phase polymerization of olefins
IT1256157B (it) † 1992-10-09 1995-11-29 Composizione polimerica per fibre polipropileniche soffici, fibre ottenute da tale composizione e manufatti derivati da dette fibre
US5331047A (en) * 1993-02-17 1994-07-19 Himont Incorporated Olefin polymer films
IT1264781B1 (it) * 1993-04-06 1996-10-10 Himont Inc Procedimento per il rivestimento di tubi metallici con materiali poliolefinici
US5432009A (en) * 1993-06-17 1995-07-11 Sekisui Kagaku Kogyo Kabushiki Kaisha Film for first-aid sticking plaster
US5414027A (en) * 1993-07-15 1995-05-09 Himont Incorporated High melt strength, propylene polymer, process for making it, and use thereof
IT1264555B1 (it) * 1993-08-03 1996-10-02 Himont Inc Processo di slush moulding di polveri di composizioni poliolefiniche
US5360868A (en) * 1993-08-30 1994-11-01 Himont Incorporated Polyolefin compositions having a high balance of stiffness and impact strength
US5338801A (en) * 1993-10-20 1994-08-16 Himont Incorporated Compositions of propylene polymer materials and olefin polymer materials with reduced gloss
IT1265452B1 (it) * 1993-12-27 1996-11-22 Himont Inc Film poliolefinici compositi adatti per imballaggio
US5409992A (en) * 1994-02-28 1995-04-25 Himont Incorporated Calenderable blends containing broad molecular weight distribution propylene polymer material
JP2839840B2 (ja) * 1994-08-19 1998-12-16 昭和電工株式会社 プロピレン樹脂組成物
US5460884A (en) * 1994-08-25 1995-10-24 Kimberly-Clark Corporation Soft and strong thermoplastic polymer fibers and nonwoven fabric made therefrom
CA2162946C (en) * 1994-11-21 2004-01-06 Kazuyuki Watanabe Propylene block copolymer and process for producing the same
CA2217123A1 (en) * 1995-05-02 1996-11-07 Steven Ray Stopper Nonwoven-film laminates
IT1274503B (it) * 1995-05-15 1997-07-17 Montell North America Inc Fibre poliolefiniche ad elevata tenacita'
US5662978A (en) * 1995-09-01 1997-09-02 Kimberly-Clark Worldwide, Inc. Protective cover fabric including nonwovens
IT1276121B1 (it) * 1995-11-14 1997-10-24 Montell Technology Company Bv Film multistrato estensibili
IT1276120B1 (it) * 1995-11-14 1997-10-24 Montell Technology Company Bv Film multistrato estensibili basati su lldpe
ATE215571T1 (de) 1995-11-24 2002-04-15 Chisso Corp Propylenzusammensetzung, verfahren zu deren herstellung, polypropylenzusammensetzung und geformte gegenstände
IT1282683B1 (it) * 1996-02-23 1998-03-31 Montell North America Inc Mescole di bitume e di polimeri olefinici atti alla modifica dei bitumi
US6103647A (en) * 1996-03-14 2000-08-15 Kimberly-Clark Worldwide, Inc. Nonwoven fabric laminate with good conformability
MX9800203A (es) 1996-05-06 1998-04-30 Montell Technology Company Bv Composiciones de poliolefina para peliculas sellables con calor que tienen resistencia controlada a la peladura.
JP3719715B2 (ja) 1996-06-24 2005-11-24 モンテル ノース アメリカ インコーポレーテッド 高透明性で高柔軟性の弾性プラスチックポリオレフィン組成物
KR19980017267A (ko) * 1996-08-30 1998-06-05 백영배 폴리프로필렌 탄성체의 제조방법
US5861463A (en) * 1996-10-31 1999-01-19 The Dow Chemical Company Impact-modified thermoplastic polyolefins and articles fabricated therefrom
AT408229B (de) * 1997-02-11 2001-09-25 Borealis Ag Verwendung von thermoplastischen elastomeren zur verbesserung der stabilität von polyolefinen gegenüber ionisierender strahlung
US5964743A (en) * 1997-02-27 1999-10-12 Kimberly-Clark Worldwide, Inc. Elastic absorbent material for personal care products
US6407028B1 (en) 1997-03-29 2002-06-18 Basell Technology Company Bv Magnesium dichloride-alcohol adducts, process for their preparation and catalyst components obtained therefrom
HUP0001557A3 (en) * 1997-03-29 2010-01-28 Montell Technology Company Bv Magnesium dichloride-alcohol adducts, process for their preparation and catalyst components obtained therefrom
AU773932B2 (en) * 1997-03-29 2004-06-10 Montell Technology Company B.V. Magnesium dichloride-alcohol adducts, process for their preparation and catalyst components obtained therefrom
US6323152B1 (en) 1998-03-30 2001-11-27 Basell Technology Company Bv Magnesium dichloride-alcohol adducts process for their preparation and catalyst components obtained therefrom
US6218023B1 (en) 1997-04-21 2001-04-17 Montell North America, Inc. Co-extruded laminate comprising at least one propylene graft copolymer layer
US6013734A (en) * 1997-04-29 2000-01-11 Montell North America Inc. Thermoplastic olefin composition containing an ethylene polymer for making molded parts having a good paint adhesion/durability balance
TW400341B (en) 1997-05-22 2000-08-01 Chisso Corp Propyene polymer blends, processes of producing the same, and polypropylene resin compositions
IT1292138B1 (it) * 1997-06-12 1999-01-25 Montell Technology Company Bv Film multistrato estensibili
GB9712663D0 (en) 1997-06-16 1997-08-20 Borealis As Process
JP4037468B2 (ja) 1997-06-24 2008-01-23 ボレアリス エー／エス プロピレンを含む異相ポリマーの製造方法
US5952423A (en) * 1997-07-18 1999-09-14 Baxter International Inc. Plastic compositions for medical containers and methods for providing such containers and for storing red blood cells
US6468258B1 (en) 1997-07-18 2002-10-22 Baxter International Inc. Plastic compositions including vitamin E for medical containers and methods for providing such compositions and containers
IT1295925B1 (it) 1997-10-28 1999-05-28 Montell North America Inc Composizioni polipropileniche ad elevato contenuto di cariche minerali pesanti, adatte al rivestimento di tubi metallici
JPH11181179A (ja) * 1997-12-22 1999-07-06 Sumitomo Chem Co Ltd 粉末成形用オレフィン系熱可塑性エラストマー組成物、粉末成形用粉末及び成形体
US6486246B1 (en) * 1998-02-03 2002-11-26 Montell Technology Company Bv Polyolefin based hot melt adhesive composition
US5962573A (en) * 1998-02-13 1999-10-05 Montell North America Inc. Directly paintable thermoplastic olefin composition containing oxidized polyethylene waxes
US6046273A (en) * 1998-02-27 2000-04-04 Montell North America Inc. Thermal stability of alpha-substituted acrylate graft copolymers
DE19815046A1 (de) 1998-04-03 1999-10-14 Borealis Ag Polyolefinfolien und Polyolefinbeschichtungen von Substraten
IT1302029B1 (it) * 1998-08-19 2000-07-20 Montech Usa Inc Processo per produrre composizioni polimeriche eterofasiche ecomposizioni cosi' ottenute
US6649548B1 (en) 1998-10-02 2003-11-18 Kimberly-Clark Worldwide, Inc. Nonwoven web and film laminate with improved strength and method of making the same
JP2000230089A (ja) 1998-10-16 2000-08-22 Mitsubishi Chemicals Corp オレフィン系熱可塑性エラストマー組成物及びその製造方法
US6454989B1 (en) 1998-11-12 2002-09-24 Kimberly-Clark Worldwide, Inc. Process of making a crimped multicomponent fiber web
DE69937204T2 (de) 1998-12-30 2008-06-19 Prysmian Cavi E Sistemi Energia S.R.L. Kabel mit einer wiederverwertbaren beschichtung
ES2235850T3 (es) 1999-04-02 2005-07-16 Basell Poliolefine Italia S.P.A. Acoplamiento de partes metalicas con un material plastico.
US6495760B1 (en) 1999-04-03 2002-12-17 Pirelli Cevi E Sistemi S.P.A, Self-extinguishing cable with low-level production of fumes, and flame-retardant composition used therein
US6143825A (en) * 1999-05-14 2000-11-07 Montell Technology Company Bv Adhesive propylene polymer compositions suitable for coating substrates
US6489019B1 (en) 1999-05-19 2002-12-03 Basell Poliolefine Italia S.P.A. High surface gloss, co-extruded sheets from olefin polymer materials
US6306518B1 (en) 1999-05-19 2001-10-23 Montell Technology Company Bv High surface gloss, co-extruded sheets from propylene polymer materials
JP2001072815A (ja) * 1999-09-07 2001-03-21 Chisso Corp プロピレン系樹脂組成物
US6613704B1 (en) * 1999-10-13 2003-09-02 Kimberly-Clark Worldwide, Inc. Continuous filament composite nonwoven webs
US6777056B1 (en) 1999-10-13 2004-08-17 Kimberly-Clark Worldwide, Inc. Regionally distinct nonwoven webs
EP1106647B1 (en) * 1999-12-07 2004-03-17 Mitsubishi Chemical Corporation Propylene-based copolymer composition
US6624099B1 (en) 1999-12-17 2003-09-23 Basell Poliolefine Italia S.P.A. Glass-reinforced multi-layer sheets from olefin polymer materials
CA2359817A1 (en) 1999-12-23 2001-07-05 Basell Technology Company B.V. Flame-proof polyolefin compositions
US6326434B1 (en) 2000-02-16 2001-12-04 Equistar Chemicals, Lp Extrusion compositions with improved melt flow
JP5312716B2 (ja) * 2000-03-09 2013-10-09 旭化成ケミカルズ株式会社 ウレタン系エラストマー
JP5086509B2 (ja) 2000-03-22 2012-11-28 バセル テクノロジー カンパニー ビー．ブイ． 熱収縮性のシール可能な多層フィルム
US6451897B1 (en) 2000-06-16 2002-09-17 Basell Technology Company Bv Nanocomposites made from polypropylene graft copolymers
US6433063B1 (en) 2000-06-30 2002-08-13 Basell Technology Company Bv Directly paintable thermoplastic olefin composition with improved conductivity
JP2002018887A (ja) 2000-07-12 2002-01-22 Chisso Corp ポリプロピレン樹脂発泡成形体
US6723792B2 (en) * 2000-09-15 2004-04-20 Basell Poliolefine Italia S.P.A. Nonextruded dispersions and concentrates of additives on olefin polymers
DE10047772A1 (de) 2000-09-27 2002-04-18 Kalle Nalo Gmbh & Co Kg Polyamidhaltige Kunststoff-Zusammensetzungen und daraus hergestellte Folien
US6667367B1 (en) 2000-10-10 2003-12-23 Basell Poliolefine Italia S.P.A. Directly paintable polypropylene graft copolymers
WO2002100738A1 (en) * 2001-06-07 2002-12-19 Mitsubishi Chemical Corporation Duplex container
ATE307847T1 (de) 2001-06-15 2005-11-15 Basell Poliolefine Srl Verfahren zum vernetzen von thermoplastischem olefin und elastomer enthaltenden zusammensetzungen
EP1279699A1 (en) * 2001-07-27 2003-01-29 Baselltech USA Inc. Soft polyolefin compositions
US6806319B2 (en) * 2001-08-08 2004-10-19 Basell Polioelfine Italia S.P.A. Retarding the thermal degradation of polymers using unsaturated aliphatic compounds
US6777484B2 (en) 2001-08-08 2004-08-17 Basell Poliolefine Italia S.P.A. Polypropylene graft copolymer/fluorinated polyolefin blends
US6506847B1 (en) 2001-08-08 2003-01-14 Basell Poliolefine Italia S.P.A. Controlling the molecular weight of graft copolymers using polymerizable chain transfer agents
EP1448705B1 (en) 2001-11-28 2010-04-28 Prysmian S.p.A. Easy tearable cable component and telecommunication cable comprising said component
ATE405594T1 (de) * 2002-01-15 2008-09-15 Advanced Elastomer Systems Thermoplastische elastomere
EP1483325B1 (en) 2002-03-12 2006-05-31 Basell Poliolefine Italia S.r.l. Polyolefin compositions having high fluidity
US6743864B2 (en) * 2002-03-12 2004-06-01 Basell Poliolefine Italia S.P.A. Polyolefin compositions having high tenacity
KR100973457B1 (ko) * 2002-03-29 2010-08-02 바셀 폴리올레핀 이탈리아 에스.알.엘 마그네슘 디클로라이드-에탄올 첨가생성물 및 그로부터수득된 촉매 성분
US7998579B2 (en) 2002-08-12 2011-08-16 Exxonmobil Chemical Patents Inc. Polypropylene based fibers and nonwovens
US8003725B2 (en) 2002-08-12 2011-08-23 Exxonmobil Chemical Patents Inc. Plasticized hetero-phase polyolefin blends
US7531594B2 (en) 2002-08-12 2009-05-12 Exxonmobil Chemical Patents Inc. Articles from plasticized polyolefin compositions
EP1530611B1 (en) 2002-08-12 2013-12-04 ExxonMobil Chemical Patents Inc. Plasticized polyolefin compositions
US7271209B2 (en) 2002-08-12 2007-09-18 Exxonmobil Chemical Patents Inc. Fibers and nonwovens from plasticized polyolefin compositions
CA2520220A1 (en) 2003-03-31 2004-10-14 Pirelli & C. S.P.A. Thermoplastic material comprising a vulcanized rubber in a subdivided form
KR100777354B1 (ko) * 2003-05-28 2007-11-28 미쓰이 가가쿠 가부시키가이샤 프로필렌계 중합체 조성물 및 그 용도
US8192813B2 (en) 2003-08-12 2012-06-05 Exxonmobil Chemical Patents, Inc. Crosslinked polyethylene articles and processes to produce same
US8568382B2 (en) 2004-03-29 2013-10-29 The Procter & Gamble Company Disposable absorbent articles having co-elongation
US7820875B2 (en) 2004-03-29 2010-10-26 The Procter & Gamble Company Disposable absorbent articles being adaptable to wearer's anatomy
US20050215972A1 (en) * 2004-03-29 2005-09-29 Roe Donald C Disposable absorbent articles with zones comprising elastomeric components
US8198200B2 (en) * 2004-03-29 2012-06-12 The Procter & Gamble Company Web materials having both plastic and elastic properties
ES2341977T3 (es) * 2004-06-28 2010-06-30 Dow Global Technologies Inc. Promotores de adhesion para materiales estratificados multiestructurales.
JP2008524391A (ja) 2004-12-17 2008-07-10 エクソンモービル・ケミカル・パテンツ・インク ポリマーブレンドから生成されるフィルム
WO2006065649A1 (en) 2004-12-17 2006-06-22 Exxonmobil Chemical Patents Inc. Heterogeneous polymer blends and molded articles therefrom
US7319077B2 (en) 2004-12-17 2008-01-15 Exxonmobil Chemical Patents Inc. Polymer blends and nonwoven articles therefrom
ATE467658T1 (de) 2004-12-17 2010-05-15 Exxonmobil Chem Patents Inc Homogenes polymerblend und artikel daraus
US8389615B2 (en) 2004-12-17 2013-03-05 Exxonmobil Chemical Patents Inc. Elastomeric compositions comprising vinylaromatic block copolymer, polypropylene, plastomer, and low molecular weight polyolefin
EP1827825A1 (en) 2004-12-21 2007-09-05 Basell Poliolefine Italia S.r.l. Heat-sealable polyolefin films
CA2592143A1 (en) * 2004-12-23 2006-06-29 Basell Poliolefine Italia S.R.L. Polyolefinic compositions having good whitening resistance
US20060251858A1 (en) * 2005-05-06 2006-11-09 Kimberly-Clark Worldwide, Inc. Elastic, breathable barrier films and laminates
US9644092B2 (en) 2005-06-22 2017-05-09 Exxonmobil Chemical Patents Inc. Heterogeneous in-situ polymer blend
US7951872B2 (en) 2005-06-22 2011-05-31 Exxonmobil Chemical Patents Inc. Heterogeneous polymer blend with continuous elastomeric phase and process of making the same
US9745461B2 (en) 2005-06-22 2017-08-29 Exxonmobil Chemical Patents Inc. Vulcanized polymer blends
US7928164B2 (en) 2005-06-22 2011-04-19 Exxonmobil Chemical Patents Inc. Homogeneous polymer blend and process of making the same
WO2007011541A1 (en) 2005-07-15 2007-01-25 Exxonmobil Chemical Patents Inc. Elastomeric compositions
EP1762577A1 (en) * 2005-09-02 2007-03-14 Total Petrochemicals Research Feluy Impact copolymer of propylene prepared in single reactor
BRPI0520599A2 (pt) 2005-10-07 2009-10-06 Pirelli & C Spa poste de serviço, material compósito termoplástico, e, processo para a produção de um poste de serviço
JP5300482B2 (ja) 2005-10-14 2013-09-25 バーゼル・ポリオレフィン・イタリア・ソチエタ・ア・レスポンサビリタ・リミタータ 低光沢性の弾塑性プラスチックポリオレフィン組成物
RU2008120239A (ru) 2005-11-22 2009-11-27 Базелль Полиолефин Италия С.Р.Л. (It) Полиолефиновые композиции со слабым блеском
WO2007071494A1 (en) 2005-12-21 2007-06-28 Basell Poliolefine Italia S.R.L. Compositions obtained from recycled polyolefins
EP2089469B1 (en) 2006-12-07 2011-08-10 Basell Poliolefine Italia S.r.l. Polyolefin compositions having low hardness and low gloss
JP5237961B2 (ja) 2006-12-07 2013-07-17 バーゼル・ポリオレフィン・イタリア・ソチエタ・ア・レスポンサビリタ・リミタータ 低い硬度及び低い光沢を有するポリオレフィン組成物
US8227550B2 (en) 2006-12-20 2012-07-24 Basell Poliolefine Italia S.R.L. Filled polyolefin compositions
EP2121829B1 (en) 2006-12-20 2012-02-01 Basell Poliolefine Italia S.r.l. Polypropylene compositions containing fillers and/or pigments
US8309659B2 (en) 2006-12-20 2012-11-13 Basell Poliolefine Italia S.R.L. Filled polyolefin compositions
ATE500293T1 (de) * 2007-10-17 2011-03-15 Basell Poliolefine Srl Heterophasige polyolefinzusammensetzungen mit verbesserten zugeigenschaften
JP2009221323A (ja) * 2008-03-14 2009-10-01 Sumitomo Chemical Co Ltd プロピレン系ブロック共重合体粒子群
US20100247824A1 (en) * 2009-03-24 2010-09-30 Baxter International Inc. Non-pvc films having peel seal layer
US20100247935A1 (en) * 2009-03-24 2010-09-30 Baxter International Inc. Non-pvc films having barrier layer
PL2414438T3 (pl) * 2009-03-31 2013-05-31 Basell Poliolefine Italia Srl Koncentrat poliolefinowy i kompozycja nadająca się do formowania wtryskowego
US8722803B2 (en) 2009-07-31 2014-05-13 Basell Poliolefine Italia S.R.L. Polyolefinic compositions
EP2480707B1 (en) 2009-09-21 2014-03-05 Basell Poliolefine Italia S.r.l. Polymer filament
PL2563957T3 (pl) 2010-04-30 2018-09-28 Basell Polyolefine Gmbh Polimerowy filament lub włókno
WO2011156215A2 (en) 2010-06-09 2011-12-15 Mannington Mills, Inc. Floor covering composition containing renewable polymer
FR2961517B1 (fr) * 2010-06-18 2014-04-11 Thermoplastiques Cousin Tessier Composition elastomerique reticulee, et produit comprenant une telle composition
US8389632B2 (en) 2011-02-09 2013-03-05 Equistar Chemicals, Lp Co-continuous heterophase polymer compositions containing high melt strength polypropylene for extrusion coating
ITMI20111572A1 (it) 2011-09-01 2013-03-02 R & D Innovaction S R L Composizioni antifiamma e relativo processo di produzione
WO2013156996A1 (en) * 2012-04-16 2013-10-24 Enrad Ltd Elastomer precursor comprising thermoplastic vulcanizate or rubber particles incorporated into a thermoplastic polymer in a rubber matrix
NL2013566B1 (en) 2014-10-02 2016-09-27 2Ndair B V Laminate and use thereof.
WO2017089124A1 (en) * 2015-11-24 2017-06-01 Basell Polyolefine Gmbh Blown polyolefin films
KR101957049B1 (ko) * 2017-10-11 2019-03-11 한화토탈 주식회사 전력 케이블 절연체용 폴리프로필렌 수지
KR102103087B1 (ko) * 2018-07-03 2020-04-21 엘에스전선 주식회사 전력 케이블
EP3819918A4 (en) * 2018-07-03 2022-03-23 LS Cable & System Ltd. POWER CABLE
JP7106241B2 (ja) * 2019-01-09 2022-07-26 バーゼル・ポリオレフィン・イタリア・ソチエタ・ア・レスポンサビリタ・リミタータ オレフィンの重合用触媒成分
CN113195621B (zh) 2019-01-14 2023-06-09 巴塞尔聚烯烃意大利有限公司 聚烯烃组合物
WO2021233875A1 (en) 2020-05-22 2021-11-25 Basell Poliolefine Italia S.R.L. Highly filled and flexible polyolefin composition
WO2022128794A1 (en) 2020-12-15 2022-06-23 Basell Poliolefine Italia S.R.L. Polyolefin composition with high transparency
WO2024099691A1 (en) 2022-11-07 2024-05-16 Basell Poliolefine Italia S.R.L. Polyolefin composition containing a recycled material

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5810415B2 (ja) * 1974-02-27 1983-02-25 三菱油化株式会社 ヘンセイポリプロピレン ノ セイゾウホウ
US3957919A (en) * 1974-09-24 1976-05-18 Copolymer Rubber & Chemical Corporation Thermoplastic elastomer composition and method for preparation
JPS5710611A (en) * 1980-06-20 1982-01-20 Sumitomo Chem Co Ltd Preparation of thermoplastic elastomer
JPS5761012A (en) * 1980-09-30 1982-04-13 Showa Denko Kk Production of thermoplastic elastic elastomer
JPS5765740A (en) * 1980-10-13 1982-04-21 Mitsui Petrochem Ind Ltd Molding polymer composition
FR2493856B1 (fr) * 1980-11-13 1986-03-21 Naphtachimie Sa Compositions de polypropylene a haute resistance au choc
US4368280A (en) * 1980-12-31 1983-01-11 Mitsubishi Petrochemical Company, Ltd. Partially cross-linkable compositions and process for preparing partially cross-linked thermoplastic elastomers
IT1140221B (it) * 1981-10-14 1986-09-24 Montedison Spa Composizioni polipropileniche aventi migliorate caratteristiche di resistenza all'urto alle basse temperature e procedimento di preparazione
JPS5883016A (ja) * 1981-11-13 1983-05-18 Mitsui Petrochem Ind Ltd プロピレンブロツク共重合体の製法
JPS60115610A (ja) * 1983-11-29 1985-06-22 Toa Nenryo Kogyo Kk プロピレンブロツク共重合体の製造法
IT1206128B (it) * 1984-07-30 1989-04-14 Himont Inc Composizioni polipropileniche resistenti all'urto aventi migliorata resistenza allo sbiancamento.
JPS6195017A (ja) * 1984-10-15 1986-05-13 Mitsubishi Petrochem Co Ltd オレフイン系ブロツク共重合体
JPS61120834A (ja) * 1984-11-15 1986-06-07 Mitsubishi Petrochem Co Ltd 防水シ−ト
JPS6339942A (ja) * 1986-08-05 1988-02-20 Nippon Oil Co Ltd 熱可塑性エラストマ−組成物

Also Published As

Publication number Publication date
CN1047514A (zh) 1990-12-05
EP0400333A2 (en) 1990-12-05
NO901911D0 (no) 1990-04-27
FI99016C (fi) 1997-09-25
NO176442B (no) 1994-12-27
IT8920328A0 (it) 1989-04-28
PT93922A (pt) 1990-11-20
NO176442C (no) 1995-04-05
FI902106A0 (fi) 1990-04-26
NO901911L (no) 1990-10-29
DE69023392T2 (de) 1996-05-15
PL284966A1 (en) 1991-05-20
IL94153A (en) 1994-10-21
FI99016B (fi) 1997-06-13
ZA902972B (en) 1991-01-30
SK211090A3 (en) 2000-08-14
KR900016350A (ko) 1990-11-13
MX20476A (es) 1993-12-01
DE69023392D1 (de) 1995-12-14
SK280805B6 (sk) 2000-08-14
US5302454A (en) 1994-04-12
AR244740A1 (es) 1993-11-30
AU634229B2 (en) 1993-02-18
CA2015683A1 (en) 1990-10-28
HU902617D0 (en) 1990-09-28
IL94153A0 (en) 1991-01-31
JP2950908B2 (ja) 1999-09-20
ATE130014T1 (de) 1995-11-15
HUT55814A (en) 1991-06-28
CZ283097B6 (cs) 1998-01-14
PT93922B (pt) 1996-10-31
MY112377A (en) 2001-06-30
CA2015683C (en) 2002-01-08
AU5457090A (en) 1990-11-01
JPH03205439A (ja) 1991-09-06
ES2081870T3 (es) 1996-03-16
EP0400333A3 (en) 1991-09-25
DD294031A5 (de) 1991-09-19
IT1230133B (it) 1991-10-14
RU2092502C1 (ru) 1997-10-10
YU82690A (en) 1991-10-31
CZ211090A3 (en) 1997-08-13
BR9001989A (pt) 1991-08-13
EP0400333B1 (en) 1995-11-08
PL164127B1 (pl) 1994-06-30
KR0160511B1 (ko) 1999-01-15
HU218855B (hu) 2000-12-28

Similar Documents

Publication Publication Date Title
CN1067089C (zh) 一种制备聚丙烯组合物的方法
CN1057777C (zh) 热塑性烯烃聚合物的制备方法
CN1023807C (zh) 注射成型用聚烯烃组合物制法
CN1144823C (zh) 弹性体丙烯聚合物
CN1125123C (zh) 高劲度丙烯聚合物及其制备方法
RU2444547C2 (ru) Газофазный способ получения гетерофазных сополимеров пропилена
CN1140545C (zh) 聚丁烯-1(共)聚合物及其制备方法
CN1106409C (zh) 制备聚丙烯的方法
KR101171128B1 (ko) 마그네슘 화합물, 올레핀 중합용 촉매 및 올레핀 중합체의제조 방법
CN1092687C (zh) 可动态硫化的聚烯烃组合物
CN1079968A (zh) 在熔融状态下具有改进加工性能的丙烯结晶聚合物及其制备方法
CN1276020C (zh) 高模量、高延性聚烯烃
CN1043507A (zh) 能制备分子量分布很窄的线性聚乙烯的气相乙烯的聚合法
CN1047302A (zh) 用于烯烃聚合的催化组分及催化剂
CN1533412A (zh) 软聚烯烃组合物
CN1832999A (zh) 具有高平衡的刚度和冲击强度的聚烯烃组合物
KR20190083376A (ko) 마스터배치 조성물
CN1176259A (zh) 聚丙烯系树脂及聚丙烯系树脂组合物
JPH09157492A (ja) 熱可塑性樹脂組成物
WO2001018110A1 (fr) Composition de resine propylenique
CN1018926B (zh) 丁烯-1共聚物组合物
JP3024082B2 (ja) プロピレン系ポリマーブレンドおよびその製造方法
KR20220084367A (ko) 폴리프로필렌 조성물 및 성형 물품
JP2006028312A (ja) 環状アミノシラン、α−オレフィンの重合又は共重合用触媒、及びα−オレフィンの重合方法

Legal Events

Date Code Title Description
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C06 Publication
PB01 Publication
C14 Grant of patent or utility model
GR01 Patent grant