公开(公告)号：WO2014177480A1

公开(公告)日：2014-11-06

申请号：PCT/EP2014/058531

申请日：2014-04-28

Applicant: BOREALIS AG

Inventor： SAEED, Irfan ,  KOKKO, Esa ,  WALDVOGEL, Päivi ,  MUSTONEN, Marja ,  GAROFF, Thomas

IPC: C08F110/06 ,  C08F4/651 ,  C08F4/655 ,  C08F4/02

CPC classification number: C08F210/08 ,  C08F210/16 ,  C08F2500/12 ,  C08F2500/18 ,  C08F4/651 ,  C08F4/6555 ,  C08F4/025

Abstract: Procatalyst comprising an inorganic support, a chlorine compound carried on said support, a magnesium compound carried on said support, a titanium compound carried on said support, and a compound comprising two oxygen containing rings, wherein said two rings are linked via a bridge selected from the group consisting of carbon bridge, silicon bridge, ethane-1.2- diyl bridge, ethene-1,2-diyl bridge, alkylaminomethyl bridge and imine bridge.

Abstract translation: 主催化剂包括无机载体，载于所述载体上的氯化合物，载于所述载体上的镁化合物，载于所述载体上的钛化合物和包含两个含氧环的化合物，其中所述两个环通过选自以下的桥连接： 由碳桥，硅桥，乙烷-1,2-二桥，乙烯-1,2-二桥，烷基氨基甲基桥和亚胺桥组成。

公开(公告)号：WO2010125022A1

公开(公告)日：2010-11-04

申请号：PCT/EP2010/055519

申请日：2010-04-26

Applicant: BOREALIS AG ,  GAROFF, Thomas ,  WALDVOGEL, Päivi ,  KALLIO, Kalle ,  ERIKSSON, Virginie ,  AITTOLA, Aki ,  KOKKO, Esa

Inventor： GAROFF, Thomas ,  WALDVOGEL, Päivi ,  KALLIO, Kalle ,  ERIKSSON, Virginie ,  AITTOLA, Aki ,  KOKKO, Esa

IPC: C08F10/00 ,  C08F210/02 ,  C08L23/08

CPC classification number: C08F210/16 ,  C08L2314/02 ,  C08F210/08 ,  C08F2500/12 ,  C08F2500/18 ,  C08F2500/08 ,  C08F2500/10

Abstract: Ziegler-Natta catalyzed linear low density polyethylene which satisfies the following conditions: a) a density, according to ISO 1183, of from 900 to 925 kg/m 3 , b) a C 4 -C 10 -comonomer content, determined by Fourier transform infrared spectroscopy, of 1 to 16 wt% c) a weight average molecular weight Mw, determined by gel permeation chromatography, of at least 200 000, d) wherein the linear low density polyethylene comprises, by Crystallisation Analysis Fractionation (CRYSTAF) an amorphous fraction soluble at a temperature below 30°C of at most 10 wt% and a fraction crystallising between 60 to 75°C of at least 35 wt% and e) by temperature rising elution fractionation (TREF) analysis, at least 70 wt% of a crystallising polymer component having an elution temperature range from 60°C to 94°C and less than 10 wt% of a crystallising polymer component having an elution temperature range from 30°C to 60° and, f) by Gel Permeation chromatography using an Fourier transform infrared spectroscopy detector (GPC-FTIR), a substantially constant short chain branching profile across the molecular weight distribution (MWD) or g) by Gel Permeation chromatography coupled with Fourier transform infrared spectroscopy instruments (GPC-FTIR), a revers short chain branching profile across the molecular weight distribution (MWD), the linear low density polyethylene being produced in the presence of a special Ziegler- Natta procatalyst and a halogenated aluminium alkyl cocatalyst of the formula (IV) (C 1 -C 4 - alkyl) m -AI-X 3-m1 , wherein X is chlorine, bromine, iodine or fluorine and m is 1 or 2.

Abstract translation: 齐格勒 - 纳塔催化的线性低密度聚乙烯，其满足以下条件：a）根据ISO 1183的密度为900至925kg / m 3，b）通过傅立叶变换红外光谱测定的C 4 -C 10共聚单体含量， c）通过凝胶渗透色谱测定的至少200000重量平均分子量Mw，d）其中线性低密度聚乙烯通过结晶分析分馏（CRYSTAF）包含在 温度低于30℃至多10重量％，并且在60至75℃之间结晶至少35重量％的馏分和e）通过升温洗脱分馏（TREF）分析，至少70重量％的结晶聚合物组分 具有洗脱温度范围为60℃至94℃且小于10重量％的洗脱温度范围为30℃至60℃的结晶聚合物组分，f）通过使用傅里叶变换红外光谱的凝胶渗透色谱法 （GPC-FTIR），通过凝胶渗透色谱与傅立叶变换红外光谱仪（GPC-FTIR）结合，分子量分布（MWD）基本恒定的短链支化谱，或g），反向短链支化谱 分子量分布（MWD），线性低密度聚乙烯是在特殊的齐格勒 - 纳塔前催化剂和式（Ⅳ）的卤化烷基铝助催化剂（C1-C4烷基）m-AI-X3- m1，其中X是氯，溴，碘或氟，m是1或2。

公开(公告)号：WO2010125018A1

公开(公告)日：2010-11-04

申请号：PCT/EP2010/055513

申请日：2010-04-26

Applicant: BOREALIS AG ,  GAROFF, Thomas ,  WALDVOGEL, Päivi ,  KALLIO, Kalle ,  ERIKSSON, Virginie

Inventor： GAROFF, Thomas ,  WALDVOGEL, Päivi ,  KALLIO, Kalle ,  ERIKSSON, Virginie

IPC: C08F4/655 ,  C08F210/16

CPC classification number: C08F210/16 ,  C08F4/6555 ,  C08F210/08 ,  C08F2500/12 ,  C08F2500/18 ,  C08F2500/08

Abstract: Ziegler-Natta catalyst composition capable of producing ethylene/alpha-olefins copolymers, particularly linear low density polyethylene; the composition having an improved stability of its behaviour during polymerization in respect to time. The Ziegler-Natta catalyst composition comprises: 1. Ziegler-Natta catalyst composition for the production of ethylene copolymers comprising A) a procatalyst, which procatalyst comprises a) an Al compound having the formula Al(alkyl) x Cl 3-x (I), where alkyl is an alkyl group with 1 to 12 and 0 ≤ x ≤ 3, b) a magnesium hydrocarbyloxy compound of formula Mg(OR 1 ) 2-n (R 2 ) n (II), wherein each R 1 and R 2 is independently a C 1-20 hydrocarbon residue which may optionally be substituted with halogen and 0 ≤ n y Ti(OR 3 ) 4-y (III), wherein R 3 is a C 2-20 hydrocarbon residue and y is 1, 2, 3 or 4, with compounds a), b) and c) being supported on a particulate inorganic carrier and B) a halogenated aluminium alkyl cocatalyst of the formula (IV) (C 1 -C 4 -alkyl) m -Al-X 3-m , wherein X is chlorine, bromine, iodine or fluorine and m is 1 or 2.

Abstract translation: 能够生产乙烯/α-烯烃共聚物，特别是线性低密度聚乙烯的齐格勒 - 纳塔催化剂组合物; 该组合物在聚合过程中相对于时间具有改进的其行为稳定性。 齐格勒 - 纳塔催化剂组合物包括：1.用于生产乙烯共聚物的齐格勒 - 纳塔催化剂组合物，其包含A）前催化剂，其前体催化剂包含a）具有式Al（烷基）xCl 3-x（I）的Al化合物，其中 烷基是具有1至12且0 = x = 3的烷基，b）式Mg（OR 1）2-n（R 2）n（II）的镁烃氧基化合物，其中每个R 1和R 2独立地为C 1-20 可以任选被卤素取代的烃残基，和0 = n yTi（OR 3）4-y（III），其中R 3是C 2-20烃基，y是1,2,3或4，与化合物a），b ）和c）负载在颗粒状无机载体上，B）式（Ⅳ）的卤化烷基铝助催化剂（C1-C4烷基）m-Al-X3-m，其中X为氯，溴，碘或氟 m为1或2。

公开(公告)号：WO2011039152A1

公开(公告)日：2011-04-07

申请号：PCT/EP2010/064299

申请日：2010-09-28

Applicant: BOREALIS AG ,  JOHANSSON, Solveig ,  GAROFF, Thomas ,  WALDVOGEL, Päivi

Inventor： JOHANSSON, Solveig ,  GAROFF, Thomas ,  WALDVOGEL, Päivi

IPC: C08F4/655 ,  C08F4/651 ,  C08F4/02 ,  C08F210/16

CPC classification number: C08F210/16 ,  B01J27/135 ,  B01J31/0212 ,  B01J31/128 ,  B01J31/143 ,  B01J31/38 ,  B01J37/14 ,  C08F110/02 ,  Y02P20/52 ,  C08F4/6555 ,  C08F4/025 ,  C08F4/651 ,  C08F2500/12 ,  C08F2500/03 ,  C08F2500/18 ,  C08F2500/20 ,  C08F210/14

Abstract: Process for preparing an improved solid procatalyst of a Ziegler-Natta catalyst system comprising the following steps: a) reacting an metal alkyl with the formula (I) Al(R 1 ) 3 , wherein each R 1 independently represents an alkyl group of 1 to 6 carbon atoms with an alkyl metal halide compound of the formula (II) Al(R 2 ) m X 3-m , wherein each R 2 independently represents an alkyl group of 1 to 6 carbon atoms; each X is independently a halogen; 0 ≤ m 2 ) or a gas containing oxygen (O 2 ) to give a second reaction product, c) either the first reaction product or the second reaction product is reacted with a magnesium compound of the formula (III) R 3 n (OR 4 ) 2-n Mg, wherein R 3 and R 4 independently represent a C 1 -C 20 alkyl group and 0≤ n ≤ 2 and n may or may not be an integer, yielding a procatalyst precursor d) optionally contacting the procatalyst precursor with an alkyl metal halide compound of the formula (II) and/or with a magnesium compound of the formula (III), and e) contacting either the procatalyst precursor or the reaction product of step d) with a titanium halide compound having the formula (IV) (OR 5 ) p TiX 2 4-p , wherein each R 5 independently represents a C 1 -C 20 alkyl group, each X 2 is independently a halogen; 0 ≤ p ≤ 3 and p may or may not be an integer, in order to yield the solid procatalyst and its use for the production of polyethylene homo- or copolymers with a PDI below 4 down to 3.

Abstract translation: 制备齐格勒 - 纳塔催化剂体系的改进的固体前催化剂的方法，包括以下步骤：a）使烷基金属与式（I）Al（R 1）3反应，其中每个R 1独立地表示1至6个碳原子的烷基 原子与式（II）的烷基金属卤化物化合物Al（R2）mX3-m，其中每个R2独立地表示1至6个碳原子的烷基; 每个X独立地是卤素; 0 = m <3，并且m可以是或不是整数，由此式（I）的金属烷基或式（II）的烷基金属卤化物已经首先与惰性载体接触，以产生第一反应 产物b）用氧气（O 2）或含氧气（O 2）的气体处理第一反应产物以产生第二反应产物，c）将第一反应产物或第二反应产物与下式的镁化合物 III）R3 n（OR4）2-nMg，其中R3和R4独立地表示C1-C20烷基且0 = n = 2，n可以是或不是整数，得到前催化剂前体d）任选地使前催化剂前体 与式（II）的烷基金属卤化物和/或与式（III）的镁化合物反应，和e）使前催化剂前体或步骤d）的反应产物与具有式 （IV）（OR5）pTiX2 4-p，其中每个R 5独立地表示C 1 -C 20烷基 每个X 2独立地是卤素; 0 = p = 3，p可以为整数，以产生固体前催化剂及其用于生产低于4的PDI的聚乙烯均聚物或共聚物的用途。

公开(公告)号：WO2010125020A1

公开(公告)日：2010-11-04

申请号：PCT/EP2010/055517

申请日：2010-04-26

Applicant: BOREALIS AG ,  GAROFF, Thomas ,  WALDVOGEL, Päivi ,  KALLIO, Kalle ,  ERIKSSON, Virginie ,  AITTOLA, Aki ,  KOKKO, Esa

Inventor： GAROFF, Thomas ,  WALDVOGEL, Päivi ,  KALLIO, Kalle ,  ERIKSSON, Virginie ,  AITTOLA, Aki ,  KOKKO, Esa

IPC: C08F210/16 ,  C08F2/00 ,  C08F4/655

CPC classification number: C08F210/16 ,  C08F2/14 ,  C08F4/6555 ,  C08F2/001 ,  C08F2/34 ,  C08F210/08 ,  C08F2500/18 ,  C08F2500/12 ,  C08F2500/05 ,  C08F2500/07 ,  C08F2500/02 ,  C08F2500/08 ,  C08F2500/01 ,  C08F210/14

Abstract: Multi-stage polymerization process for the production of a multi-modal linear low density polyethylene in at least two staged reactors connected in series comprising at least (i) polymerizing in a first slurry phase stage ethylene monomers and optionally one or more alpha- olefine comonomers, in the presence of a Ziegler-Natta polymerization catalyst system to obtain a first polyethylene fraction component (A) (ii) polymerizing in a second gas or slurry phase stage ethylene monomers and one or more alpha- olefine comonomers, in the presence of a Ziegler-Natta polymerization catalyst system to obtain a second polyethylene fraction component (B), whereby the Ziegler-Natta polymerisation catalyst system comprises C) a procatalyst, which procatalyst comprises a) an Al compound having the formula AI(alkyl) x CI 3-x (l), where alkyl is an alkyl group with 1 to 12 and 0 1 ) 2-n (R 2 ) n (II), wherein each R 1 and R 2 is independently a C 1-20 hydrocarbon residue which may optionally be substituted with halogen and O y Ti(OR 3 ) 4-y (III), wherein R 3 is a C 2-20 hydrocarbon residue and y is 1, 2, 3 or 4 and compounds a), b) and c) being deposited on a particulate inorganic support and D) a halogenated aluminium alkyl cocatalyst of the formula (IV) (C 1 -C 4 -alkyl) m -AI-X 3-m , wherein X is chlorine, bromine, iodine or fluorine and m is 1 or 2, and yielding a multimodal linear low density polyethylene with a narrow molecular weight distribution, whereby the process shows a higher comonomer conversion compared to multi-stage processes using non-halogenated cocatalysts.

Abstract translation: 用于在串联连接的至少两个阶段反应器中生产多模式线性低密度聚乙烯的多级聚合方法，包括至少（i）在第一浆料相阶段聚合乙烯单体和任选的一种或多种α-烯烃共聚单体 在齐格勒 - 纳塔聚合催化剂体系的存在下，获得第一聚乙烯级分组分（A）（ⅱ）在第二气体或浆料相阶段聚合乙烯单体和一种或多种α-烯烃共聚单体，在 齐格勒 - 纳塔聚合催化剂体系，以获得第二聚乙烯级分组分（B），其中齐格勒 - 纳塔聚合催化剂体系包含C）前催化剂，其主催化剂包含a）具有式AI（烷基）xCI3-x（ 其中烷基是具有1至12和0 1）2-n（R2）n（II）的烷基，其中每个R 1和R 2独立地为可任选被 卤素和O yTi（OR 3）4-y（III），其中R 3是C 2-20烃残基，y是1,2,3或4，并且化合物a），b）和c）沉积在颗粒状无机载体上 和D）式（Ⅳ）（C1-C4烷基）m-Al-X3-m的卤化烷基铝助催化剂，其中X是氯，溴，碘或氟，m是1或2，并产生多峰 具有窄分子量分布的线性低密度聚乙烯，由此与使用非卤化助催化剂的多阶段方法相比，该方法显示出更高的共聚单体转化率。

公开(公告)号：WO2010097352A1

公开(公告)日：2010-09-02

申请号：PCT/EP2010/052173

申请日：2010-02-22

Applicant: BOREALIS AG ,  GAROFF, Thomas ,  WALDVOGEL, Päivi ,  KALLIO, Kalle ,  ERIKSSON, Virginie ,  AITTOLA, Aki ,  KOKKO, Esa

Inventor： GAROFF, Thomas ,  WALDVOGEL, Päivi ,  KALLIO, Kalle ,  ERIKSSON, Virginie ,  AITTOLA, Aki ,  KOKKO, Esa

IPC: C08F10/00 ,  C08F4/685

CPC classification number: C08F10/00 ,  C08F110/02 ,  C08F210/16 ,  Y02P20/52 ,  C08F4/6357 ,  C08F4/685 ,  C08F2/001 ,  C08F2500/07 ,  C08F2500/12 ,  C08F2500/05 ,  C08F2500/18 ,  C08F210/14 ,  C08F2500/08

Abstract: Multi-stage polymerization process for the production of a multi-modal linear low density polyethylene in at least two staged reactors connected in series comprising at least (i) polymerizing in a first slurry phase stage ethylene monomers and optionally one or more alpha-olefine comonomers, in the presence of a Ziegler-Natta polymerization catalyst system to obtain a first polyethylene fraction component (A) (ii) polymerizing in a second gas or slurry phase stage ethylene monomers and one or more alpha-olefine comonomers, in the presence of a Ziegler-Natta polymerization catalyst system to obtain a second polyethylene fraction component (B), whereby the Ziegler-Natta polymerization catalyst system comprises 1) a solid procatalyst formed by contacting at least: a) a Mg-alcoholate complex of the formula (I): Mg(OR 1 ) 2-n (R 1 ) n , wherein each R 1 independently represents a C 1 -C 20 hydrocarbyl group and 0 ≤ n 2 ) m X 3-m , wherein each R 2 independently represents an alkyl of up to 6 carbon atoms; each X is independently a halogen; 0 ≤ m 1 -C 20 -alkyl group, 0 ≤ x ≤ 2; 1 ≤ y ≤ 3; 0 ≤ z ≤ 2 and x + y + z = 3; x, y and z may or may not be an integer, yielding a multi-modal polyethylene, whereby the process shows a reduced change of comonomer response with polymerization time and a more stable comonomer conversion with polymerization time compared to multistage processes using Ziegler-Natta catalysts with 100% Ti.

Abstract translation: 用于在至少两个串联反应器中连续串联生产多模式线性低密度聚乙烯的多级聚合方法，包括至少（i）在第一浆料相阶段聚合乙烯单体和任选的一种或多种α-烯烃共聚单体 在齐格勒 - 纳塔聚合催化剂体系存在下，得到第一聚乙烯级分组分（A）（ⅱ）在第二种气相或淤浆相阶段中聚合乙烯单体和一种或多种α-烯烃共聚单体，在 齐格勒 - 纳塔聚合催化剂体系，得到第二聚乙烯组分（B），其中齐格勒 - 纳塔聚合催化剂体系包括：1）通过使至少与下列物质接触而形成的固体前催化剂：a）式（I）的Mg-醇化物络合物， ：Mg（OR1）2-n（R1）n，其中每个R1独立地表示C1-C20烃基，0 = n2）mX3-m，其中每个R2独立地表示至多6个碳原子的烷基; 每个X独立地是卤素; 0 = m <3和m，并且可以是或不是整数，c）钒化合物和钛化合物，以提供V:Ti的摩尔比为10:90至90:10，以产生 固体前催化剂和2）式（III）的一种或多种有机金属助催化剂，其中每个R独立地为C 1 -C 20 - 烷基，0 = x = 2; 1 = y = 3; 0 = z = 2，x + y + z = 3; x，y和z可以是或不是整数，产生多峰聚乙烯，由此与使用齐格勒 - 纳塔（Ziegler-Natta）的多阶段方法相比，该方法显示了聚合时间下共聚单体响应的变化减小和聚合时间的更稳定的共聚单体转化 具有100％Ti的催化剂。

公开(公告)号：WO2010097351A1

公开(公告)日：2010-09-02

申请号：PCT/EP2010/052172

申请日：2010-02-22

Applicant: BOREALIS AG ,  GAROFF, Thomas ,  WALDVOGEL, Päivi ,  KALLIO, Kalle ,  ERIKSSON, Virginie ,  AITTOLA, Aki ,  KOKKO, Esa

Inventor： GAROFF, Thomas ,  WALDVOGEL, Päivi ,  KALLIO, Kalle ,  ERIKSSON, Virginie ,  AITTOLA, Aki ,  KOKKO, Esa

IPC: C08F10/00 ,  C08F4/685 ,  C08F2/00

CPC classification number: C08F10/00 ,  C08F110/02 ,  C08F210/16 ,  C08F2410/03 ,  Y10T428/139 ,  C08F4/6357 ,  C08F4/685 ,  C08F2/001 ,  C08F2500/07 ,  C08F2500/12 ,  C08F2500/05 ,  C08F2500/18 ,  C08F210/14 ,  C08F2500/08

Abstract: Multi-stage polymerization process for the production of a multi-modal linear low density polyethylene in at least two staged reactors connected in series comprising at least (i) polymerizing in a first slurry phase stage ethylene monomers and optionally one or more alpha-olefine comonomers, in the presence of a Ziegler-Natta polymerization catalyst system to obtain a first polyethylene fraction component (A) (ii) polymerizing in a second gas or slurry phase stage ethylene monomers and one or more alpha-olefine comonomers, in the presence of a Ziegler-Natta polymerization catalyst system to obtain a second polyethylene fraction component (B), whereby the Ziegler-Natta polymerization catalyst system comprises: 1) a solid procatalyst formed by contacting at least: a) a Mg-alcoholate complex of the formula (I): Mg(OR 1 ) 2-n (R 1 ) n , wherein each R 1 independently represents a C 1 -C 20 hydrocarbyl group and 0 2 ) m X 3-m , wherein each R 2 independently represents an alkyl of up to 6 carbon atoms; each X is independently a halogen; 0 1 -C 20 -alkyl group, 0

Abstract translation: 用于在至少两个串联反应器中连续串联生产多模式线性低密度聚乙烯的多级聚合方法，包括至少（i）在第一浆料相阶段聚合乙烯单体和任选的一种或多种α-烯烃共聚单体 在齐格勒 - 纳塔聚合催化剂体系存在下，得到第一聚乙烯级分组分（A）（ⅱ）在第二种气相或淤浆相阶段中聚合乙烯单体和一种或多种α-烯烃共聚单体，在 齐格勒 - 纳塔聚合催化剂体系，以获得第二聚乙烯部分组分（B），由此齐格勒 - 纳塔聚合催化剂体系包括：1）通过使至少与下式接触形成的固体前催化剂：a）式 ）：Mg（OR 1）2-n（R 1）n，其中每个R 1独立地表示C 1 -C 20烃基和O 2）m X 3-m，其中每个R 2独立地表示至多6个碳原子的烷基; 每个X独立地是卤素; 0