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    • 3. 发明申请
    • PREPARATION OF SINGLE-SITE CATALYSTS
    • 单壁催化剂的制备
    • WO2011076618A1
    • 2011-06-30
    • PCT/EP2010/069634
    • 2010-12-14
    • BOREALIS AGKALLIO, KalleMUSTONEN, MarjaCASTRO, PascalDENIFL, Peter
    • KALLIO, KalleMUSTONEN, MarjaCASTRO, PascalDENIFL, Peter
    • C08F10/00C08F4/6592
    • C08F10/00C08F4/65927C08F110/06C08F2410/01C08F4/65912
    • Process for the preparation of a catalyst system comprising the steps of (a) preparing a solution (A) comprising (i) a transition metal compound of formula (I) L m R n M q wherein "M" is a transition metal of anyone of the groups 3 to 10 of the periodic table (IUPAC), each "X" is independently a monovalent σ-ligand, each "L" is independently an organic ligand which coordinates to the transition metal (M), "R" is a bridging group linking said organic ligands (L), "m" is 2 or 3, preferably 2, "n" is 0, 1 or 2, preferably 1, "q" is 1, 2 or 3, preferably 2, m+q is equal to the valency of the transition metal (M), (ii) a cocatalyst (Co) comprising an element (E) of group 13 of the periodic table (IUPAC), preferably a cocatalyst (Co) comprising a compound of A1, (iii) a solvent (A'), (b) generating an emulsion by dispersing the solution (A) in a solvent (B) and in the presence of a surfactant (S) wherein (i) the solvent (B) constitutes the continuous phase of the emulsion and (ii) the solution (A) constitutes in form of droplets the dispersed phase of the emulsion, (iii) the transition metal compound of formula (I) and the cocatalyst (Co) are present in the droplets, and (iv) the surfactant (S) is a reaction product (RP) of at least one compound of formula (II) and a compound (C) comprising an element (E) of group 13 of the periodic table (IUPAC), preferably a compound comprising A1, the formula (II) is wherein R 1 is a semi-, highly- or perfluorinated hydrocarbon residue, and R 2 is a residue selected from the group consisting of -C(R 3 )=C(R 3' )-R 4 , wherein R 3 , R 4 , R 3' , are independently from each other selected from the group consisting of H, C 1 to C 20 alkyl, C 2 to C 20 alkenyl, C 2 to C 20 alkinyl, (c) solidifying said dispersed phase to convert said droplets to solid particles and (d) optionally recovering said particles to obtain said catalyst system.
    • 制备催化剂体系的方法,包括以下步骤:(a)制备溶液(A),其包含(i)式(I)的过渡金属化合物LmRnMq,其中“M”是3至 10的周期表(IUPAC)中,每个“X”独立地是一价s配体,“L”分别是与过渡金属(M)配位的有机配体,“R”是连接所述有机物 配体(L),“m”为2或3,优选2,“n”为0,1或2,优选1,“q”为1,2或3,优选2,m + q等于 的过渡金属(M),(ii)包含周期表第13族元素(E)的助催化剂(Co)(IUPAC),优选包含A1化合物的助催化剂(Co),(iii)溶剂 (A'),(b)通过将溶液(A)分散在溶剂(B)中并在表面活性剂(S)的存在下产生乳液,其中(i)溶剂(B)构成乳液的连续相 和(ii)溶液(A )构成液滴的形式,乳液的分散相,(iii)式(I)的过渡金属化合物和助催化剂(Co)存在于液滴中,和(iv)表面活性剂(S)是反应产物 (II)的至少一种化合物和包含元素周期表第13族元素(E)的化合物(I)的(RP),优选包含A1,式(II)的化合物,其中R1 是一个半,高度或全氟化的烃残基,R2是选自-C(R 3)= C(R 3')-R 4的残基,其中R 3,R 4,R 3'彼此独立地是 选自H,C1至C20烷基,C2至C20烯基,C2至C20炔基,(c)固化所述分散相以将所述液滴转化为固体颗粒,和(d)任选地回收所述颗粒以获得所述催化剂体系 。
    • 4. 发明申请
    • LINEAR LOW DENSITY POLYETHYLENE WITH UNIFORM OR REVERSED COMONOMER COMPOSITION DISTRIBUTION
    • 线性低密度聚乙烯具有均匀或反转的人气组合物分布
    • WO2010125022A1
    • 2010-11-04
    • PCT/EP2010/055519
    • 2010-04-26
    • BOREALIS AGGAROFF, ThomasWALDVOGEL, PäiviKALLIO, KalleERIKSSON, VirginieAITTOLA, AkiKOKKO, Esa
    • GAROFF, ThomasWALDVOGEL, PäiviKALLIO, KalleERIKSSON, VirginieAITTOLA, AkiKOKKO, Esa
    • C08F10/00C08F210/02C08L23/08
    • C08F210/16C08L2314/02C08F210/08C08F2500/12C08F2500/18C08F2500/08C08F2500/10
    • 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.
    • 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。
    • 5. 发明申请
    • IMPROVED ETHYLENE POLYMERIZATION CATALYST COMPOSITION
    • 改进的乙烯聚合催化剂组合物
    • WO2010125018A1
    • 2010-11-04
    • PCT/EP2010/055513
    • 2010-04-26
    • BOREALIS AGGAROFF, ThomasWALDVOGEL, PäiviKALLIO, KalleERIKSSON, Virginie
    • GAROFF, ThomasWALDVOGEL, PäiviKALLIO, KalleERIKSSON, Virginie
    • C08F4/655C08F210/16
    • C08F210/16C08F4/6555C08F210/08C08F2500/12C08F2500/18C08F2500/08
    • 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.
    • 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。
    • 6. 发明申请
    • PREPARATION OF POLYPROPYLENE IN THE PRESENCE OF A SINGLE-SITE CATALYST
    • 单壁催化剂存在下聚丙烯的制备
    • WO2011076443A1
    • 2011-06-30
    • PCT/EP2010/058433
    • 2010-06-16
    • BOREALIS AGHUHTANEN, LauriKALLIO, KalleCASTRO, Pascal
    • HUHTANEN, LauriKALLIO, KalleCASTRO, Pascal
    • C08F10/00C08F4/6592
    • C08F10/00C08F4/65927C08F110/06C08F4/65912
    • Process for the preparation of a polypropylene, wherein propylene is polymerised optionally with a comonomer selected from the group consisting of ethylene, a C 4 -C 20 α-olefin and mixtures thereof, in the presence of a catalyst system comprising solid catalyst particles, wherein the solid catalyst particles (a) comprise a transition metal compound of formula (I) L m R n MX q (I) wherein "M" is a transition metal of anyone of the groups 3 to 10 of the periodic table (IUPAC), each "X" is independently a monovalent anionic σ-ligand, each "L" is independently an organic ligand which coordinates to the transition metal (M), each "R" is a bridging group linking two organic ligands (L), "m" is 2 or 3, preferably 2, "n" is 0, 1 or 2, preferably 1, "q" is 1, 2 or 3, preferably 2, m+q is equal to the valency of the transition metal (M), (c) comprise a cocatalyst (Co) comprising an element (E) of group 13 of the periodic table (IUPAC), preferably a cocatalyst (Co) comprising a compound of Al, wherein further the loss of activity of the solid catalyst particles during polymerization is at most 20 %.
    • 制备聚丙烯的方法,其中在包含固体催化剂颗粒的催化剂体系的存在下,丙烯任选地与选自乙烯,C 4 -C 20α-烯烃及其混合物的共聚单体聚合,其中固体 催化剂颗粒(a)包含式(I)的过渡金属化合物LmRnMXq(I)其中“M”是周期表(IUPAC)的第3至10族中的任何一个的过渡金属,每个“X”独立地为 每个“L”独立地是与过渡金属(M)配位的有机配体,每个“R”是连接两个有机配体(L)的桥连基团,“m”是2或3,优选 2,“n”为0,1或2,优选为1,“q”为1,2或3,优选2,m + q等于过渡金属(M)的化合价,(c)包含助催化剂 (Co),其包含元素周期表第13族元素(IUPAC),优选包含Al的化合物的助催化剂(Co),其中f 聚合过程中固体催化剂颗粒的活性降低至多20%。
    • 7. 发明申请
    • IMPROVED MULTI-STAGE PROCESS FOR PRODUCING MULTI-MODAL LINEAR LOW DENSITY POLYETHYLENE
    • 用于生产多模式线性低密度聚乙烯的改进的多级方法
    • WO2010125020A1
    • 2010-11-04
    • PCT/EP2010/055517
    • 2010-04-26
    • BOREALIS AGGAROFF, ThomasWALDVOGEL, PäiviKALLIO, KalleERIKSSON, VirginieAITTOLA, AkiKOKKO, Esa
    • GAROFF, ThomasWALDVOGEL, PäiviKALLIO, KalleERIKSSON, VirginieAITTOLA, AkiKOKKO, Esa
    • C08F210/16C08F2/00C08F4/655
    • C08F210/16C08F2/14C08F4/6555C08F2/001C08F2/34C08F210/08C08F2500/18C08F2500/12C08F2500/05C08F2500/07C08F2500/02C08F2500/08C08F2500/01C08F210/14
    • 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.
    • 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。
    • 8. 发明申请
    • IMPROVED MULTI-STAGE PROCESS FOR PRODUCING MULTI-MODAL ETHYLENE POLYMER COMPOSITION
    • 用于生产多模式乙烯聚合物组合物的改进的多阶段方法
    • WO2010097352A1
    • 2010-09-02
    • PCT/EP2010/052173
    • 2010-02-22
    • BOREALIS AGGAROFF, ThomasWALDVOGEL, PäiviKALLIO, KalleERIKSSON, VirginieAITTOLA, AkiKOKKO, Esa
    • GAROFF, ThomasWALDVOGEL, PäiviKALLIO, KalleERIKSSON, VirginieAITTOLA, AkiKOKKO, Esa
    • C08F10/00C08F4/685
    • C08F10/00C08F110/02C08F210/16Y02P20/52C08F4/6357C08F4/685C08F2/001C08F2500/07C08F2500/12C08F2500/05C08F2500/18C08F210/14C08F2500/08
    • 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.
    • 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。