公开(公告)号：US20170216825A1

公开(公告)日：2017-08-03

申请号：US15500647

申请日：2015-07-30

Applicant: VERSALIS S.P.A.

Inventor： Francesco MASI ,  Anna SOMMAZZI ,  Mario POLESELLO

IPC: B01J27/138 ,  C08F210/16 ,  C08F4/655 ,  B01J27/135

CPC classification number: B01J27/138 ,  B01J27/135 ,  C08F4/655 ,  C08F210/16 ,  C08F2410/03 ,  C08F4/6557 ,  C08F210/14 ,  C08F2500/12 ,  C08F4/6555

Abstract: An improved solid Ziegler-Natta type catalyst for the (co)polymerisation of ethylene and α-olefins, particularly in high-temperature processes, such as for example adiabatic solution processes and high-pressure adiabatic processes with elevated productivity, is provided. Said catalyst is obtained by means of an original process comprising dissolving in hydrocarbons, compounds of titanium, magnesium and optionally a metal selected from hafnium and zirconium, and reprecipitating them in two steps in succession, the first of which is chlorination and the second reduction.

公开(公告)号：US20200207891A1

公开(公告)日：2020-07-02

申请号：US16634122

申请日：2018-07-25

Applicant: Versalis S.P.A.

Inventor： Anna SOMMAZZI ,  Giovanni RICCI ,  Giuliano FISCALETTI ,  Francesco MASI ,  Giuseppe LEONE

IPC: C08F136/06 ,  C07F15/06

Abstract: Process for the preparation of 1,2 syndiotactic polybutadiene comprising polymerizing 1,3-butadiene in the presence of a catalytic system comprising: at least one cobalt complex with a phosphine ligand having general formula (I): wherein: R1, R2 and R3, mutually identical or different, are selected from branched C4-C20 alkyl groups, preferably C4-C15, C6-C30 cycloalkyl groups, preferably Ce-Cis, said cycloalkyl groups being substituted, C6-C30 aryl groups, preferably Ce-Cis, optionally substituted; provided that at least two of R1, R2 and R3 are selected from C6-C30 aryl groups, preferably Ce-Cis, optionally substituted; X1 and X2, mutually identical or different, represent a halogen atom such as, for example, chlorine, bromine, iodine; at least one aluminoxane having general formula (II): (R4)2-AI-0-[-AI(R5)-0-]m-AI-(R6)2 (II) wherein R4, R5 and R6, mutually identical or different, represent a hydrogen atom, or a halogen atom such as, for example, chlorine, bromine, iodine, fluorine; or are selected from linear or branched C1-C20 alkyl groups, cycloalkyl groups, aryl groups, said groups being optionally substituted with one or more silicon or germanium atoms; and m is an integer ranging from 0 to 1000; said process being carried out at a temperature ranging from 0° C. to +60° C., preferably ranging from 0° C. to +30° C.

公开(公告)号：US20190270832A1

公开(公告)日：2019-09-05

申请号：US16343716

申请日：2017-10-20

Applicant: Versalis S.p.A.

Inventor： Giovanni RICCI ,  Guido PAMPALONI ,  Anna SOMMAZZI ,  Massimo GUELFI ,  Francesco MASI

IPC: C08F36/06 ,  C07F15/02 ,  C08F36/08

Abstract: A process for preparing conjugated diene (co)polymers comprising polymerizing at least one conjugated diene in the presence of a catalytic system comprising: (a) at least one pyridyl iron (III) complex having general formula (I) or (II): wherein: —R1, R2, R3 and R4, identical or different, represent a hydrogen atom; or are selected from linear or branched, optionally halogenated C1-C20, preferably C1-C15, alkyl groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups; —R5 represents a hydrogen atom, or is selected from linear or branched, optionally halogenated C1-C20, preferably C1-C15, alkyl groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups; —X, identical or different, represent a halogen atom such as, for example, chlorine, bromine, iodine; or are selected from linear or branched C1-C20, preferably C1-C15, alkyl groups, —OCOR6 groups or —OR6 groups wherein R6 is selected from linear or branched C1-C20, preferably C1-C15, alkyl groups. —n is 3; (b) at least one co-catalyst selected from organo-aluminum derivatives, preferably from: (b1) aluminum compounds having general formula (III): Al(R7)(R8)(R9) (IIl) wherein R7 represents a hydrogen atom, or is selected from linear or branched C1-C20 alkyl groups, cycloalkyl groups, aryl groups, alkylaryl groups, arylalkyl groups, alkoxy groups; R8 and R9, identical or different, are selected from linear or branched C1-C20 alkyl groups, cycloalkyl groups, aryl groups, alkylaryl groups, arylalkyl groups; (b2) aluminoxanes having general formula (IV): (R10)2—Al—O—[-AI(R11)—O-]m-AI-(R12)2 (IV), wherein R10, R11 and R12, identical or different, represent a hydrogen atom, or a halogen atom such as chlorine, bromine, iodine, fluorine; or are selected from linear or branched C1-C20 alkyl groups, cycloalkyl groups, aryl groups, said groups being optionally substituted with one or more silicon or germanium atoms; and m is an integer ranging from 0 to 1000; (b3) partially hydrolyzed organo-aluminum derivatives; (b4) haloaluminum alkyls having general formula (V) or (VI): AI(R13)p(X′)3-p (V) AI2(R13)q(X′)3-q (VI) wherein p is 1 or 2; q is an integer ranging from 1 to 5; R13, identical or different, are selected from linear or branched C1-C20 alkyl groups; X′ represents a chlorine or bromine atom, preferably chlorine; provided that said co-catalyst (b) is not selected from organo-boron derivatives.

公开(公告)号：US20180201702A1

公开(公告)日：2018-07-19

申请号：US15741896

申请日：2016-07-28

Applicant: Versalis S.P.A.

Inventor： Anna SOMMAZZI ,  Guido PAMPALONI ,  Giovanni RICCI ,  Francesco MASI ,  Giuseppe LEONE

IPC: C08F36/08 ,  C08F36/06 ,  C07F7/28

CPC classification number: C08F36/08 ,  C07F7/003 ,  C07F7/28 ,  C08F4/64044 ,  C08F4/64048 ,  C08F36/06

Abstract: Nitrogen titanium complex having general formula (I) or (II), wherein: —R1 represents a hydrogen atom; or is selected from linear or branched C1-C20 alkyl groups, preferably C1-C15, optionally halogenated, cycloalkyl groups optionally substituted, aryl groups optionally substituted; —R2, R3, R4 and R5, identical or different, represent a hydrogen atom; or are selected from linear or branched C1-C20 alkyl groups, preferably C1-C15, optionally halogenated, cycloalkyl groups optionally substituted, aryl groups optionally substituted, nitro groups, hydroxyl groups, amino groups; —Y represents a NH—R6 group wherein R6 represents a hydrogen atom, or is selected from linear or branched C1-C20 alkyl groups, preferably C1-C15, optionally halogenated, cycloalkyl groups optionally substituted, aryl groups optionally substituted; or a N—R7 group wherein R7 is selected from linear or branched C1-C20 alkyl groups, preferably C1-C15, optionally halogenated, cycloalkyl groups optionally substituted, aryl groups optionally substituted; —X1, X2, X3 and X4, identical or different, represent a halogen atom, such as, for example, chlorine, bromine, iodine, preferably chlorine; or are selected from linear or branched C1-C20 alkyl groups, preferably C1-C15, —OCOR8 or —OR8 groups wherein R8 is selected from linear or branched C1-C20 alkyl groups, preferably C1-C15; or one of X1, X2 and X3 is selected from ethers, such as, for example, diethylether, tetrahydrofuran (THF), dimethoxyethane, preferably tetrahydrofuran (THF); —n is 1 in the case wherein Y represents a NH—R6 group wherein R6 has the same meanings reported above; or is 0 in the case wherein Y represents a N—R7 group wherein R7 has the same meanings reported above, or in the case wherein one of X1, X2 and X3 is selected from ethers; —R′1, R′2, R′3, R′4, R′5, R′6 and R′7, identical or different, represent a hydrogen atom; or are selected from linear or branched C1-C20 alkyl groups, preferably C1-C15, optionally halogenated, cycloalkyl groups optionally substituted, aryl groups optionally substituted; —X′1 and X′2, identical or different, represent a halogen atom such as, for example, chlorine, bromine, iodine, preferably chlorine; or are selected from linear or branched C1-C20 alkyl groups, preferably C1-C15, —OCOR′8 groups or —OR′8 groups wherein R′ 8 is selected from linear or branched C1-C20 alkyl groups, preferably C1-C15; —Y′ is selected from ethers such as, for example, diethylether, tetrahydrofuran (THF), dimethoxyethane, preferably is tetrahydrofuran (THF); or Y′ represents a group having general formula (III), wherein R′1, R′2, R′3, R′4, R′5, R′6 and R′7, have the same meanings as reported above; —m is 0 or 1. Said nitrogen titanium complex having general formula (I) or (II) can be advantageously used in a catalytic system for the (co)polymerization of conjugated dienes.

公开(公告)号：US20200024379A1

公开(公告)日：2020-01-23

申请号：US16341142

申请日：2017-10-20

Applicant: VERSALIS S.P.A.

Inventor： Anna SOMMAZZI ,  Guido PAMPALONI ,  Giovanni RICCI ,  Francesco MASI ,  Giuseppe LEONE

IPC: C08F136/06 ,  C08F4/70 ,  C08F4/52 ,  A43B13/04

Abstract: Process for the preparation of syndiotactic 1,2-polybutadiene comprising polymerising 1,3-butadiene in the presence of a catalytic system comprising: —at least one pyridyl iron complex having the general formula (I), in which: —R1 represents a hydrogen atom; or a methyl group; —R2 represents a hydrogen atom; or is selected from linear or branched C1-C10, preferably C1-C3, alkyl groups; —X, identical or different to one another, represent a halogen atom such as, for example, chlorine, bromine, iodine; or are selected from linear or branched, C1-C20, preferably C1-C15, alkyl groups, —OCOR3 groups or —OR3 groups in which R3 is selected from linear or branched C1-C20, preferably C1-C15, alkyl groups; —n is 2 or 3; —at least one aluminoxane having the general formula (II), (R4)2-AI-O-[-AI(R5)—O-]m-AI-(R6)2 (ll) in which R4, R5 and R6, identical or different to one another, represent a hydrogen atom, or a halogen atom such as, for example, chlorine, bromine, iodine, fluorine; or are selected from linear or branched C1-C20 alkyl groups, cycloalkyi groups, aryl groups, said groups being optionally substituted with one or more silicon atoms or germanium; and m is an integer ranging from 0 to 1000; in which the molar ratio between the aluminium present in the aluminoxane having the general formula (II) and the iron present in the pyridyl iron complex having the general formula (I) is ranging from 5 to 20, preferably ranging from 8 to 12.

公开(公告)号：US20180291126A1

公开(公告)日：2018-10-11

申请号：US15765811

申请日：2016-12-23

Applicant: versalis S.p.A.

Inventor： Giovanni RICCI ,  Giuseppe LEONE ,  Anna SOMMAZZI ,  Francesco MASI

IPC: C08F36/06 ,  C08F36/08 ,  C08F36/04 ,  C08F4/68 ,  C08F2/06

Abstract: Process for the preparation of (co) polymers of conjugated dienes comprising polymerizing at least one conjugated diene in the presence of a catalytic system comprising at least one vanadium bis-imine complex having the general formula (I): wherein: m is 0 or 1; Z represents a —CR5R6 group wherein R5 and R6, equal to or different from each other, represent a hydrogen atom; or a C1-C20 alkyl group, preferably C1-C15, linear or branched; or a bivalent aromatic group optionally substituted; R1 and R2 equal to or different from each other, represent a hydrogen atom; or they are selected from C1-C20 alkyl groups, preferably C1-C15, linear or branched, optionally halogenated, cycloalkyl groups optionally substituted; or R1 and R2, may be optionally bound each other so as to form, together with the other atoms which they are bound to, a cycle containing from 4 to 6 carbon atoms, saturated, unsaturated, or aromatic, optionally substituted by C1-C20 alkyl groups, preferably C1-C15, linear or branched, said cycle optionally containing heteroatoms such as, for example, oxygen, sulfur, nitrogen, silicon, phosphorus, selenium; R3 and R4, equal to or different from each other, represent a hydrogen atom; or they are selected from C1-C20 alkyl groups, preferably C1-C15, linear or branched, optionally halogenated, cycloalkyl groups optionally substituted, aryl groups optionally substituted; or R2 and R4, may be optionally bound each other so as to form, together with the other atoms which they are bound to, a cycle containing from 3 to 6 carbon atoms, saturated, unsaturated, or aromatic, optionally substituted by C1-C20 alkyl groups, preferably C1-C15, linear or branched, said cycle optionally containing other heteroatoms such as, for example, oxygen, sulfur, nitrogen, silicon, phosphorus, selenium; or R1 and R3, may be optionally bound each other so as to form, together with other atoms which they are bound to, a cycle containing from 3 to 6 carbon atoms, saturated, unsaturated, or aromatic, optionally substituted by C1-C20 alkyl groups, preferably C1-C1, linear or branched, said cycle optionally containing other heteroatoms such as oxygen, sulfur, nitrogen, silicon, phosphorus, selenium; X1, X2 and X3, equal to or different from each other, represent a halogen atom such as, for example, chlorine, bromine, iodine, preferably chlorine; or they are selected from C1-C20 alkyl groups, preferably C1-C15, linear or branched, —OCOR7 groups or —OR7 groups wherein R7 is selected from C1-C20 alkyl groups, preferably C1-C15, linear or branched; Y is selected from ethers such as, for example, diethylether, tetrahydrofuran (THF), dimethoxyethane, preferably is tetrahydrofuran (THF); n is 0 or 1.

公开(公告)号：US20170247397A1

公开(公告)日：2017-08-31

申请号：US15512332

申请日：2015-09-16

Applicant: VERSALIS S.P.A.

Inventor： Guido PAMPALONI ,  Giovanni RCCI ,  Anna SOMMAZZI ,  Francesco MASI ,  Giuseppe LEONE

IPC: C07F7/00 ,  C08F136/06

CPC classification number: C07F7/003 ,  C08F4/60013 ,  C08F4/64013 ,  C08F136/06 ,  C08F4/64044

Abstract: Pyridine complex of zirconium having general formula (I): Said pyridine complex of zirconium having general formula (I) may advantageously be used in a catalytic system for the (co)polymerization of conjugated dienes.

公开(公告)号：US20160264706A1

公开(公告)日：2016-09-15

申请号：US15032207

申请日：2014-11-03

Applicant: VERSALIS S.P.A.

Inventor： Francesco MASI ,  Anna SOMMAZZI ,  Giovanni RICCI ,  Giuseppe LEONE ,  Salvatore COPPOLA

IPC: C08F295/00

CPC classification number: C08F295/00 ,  C08F4/7006 ,  C08F4/7008 ,  C08F4/7042 ,  C08F4/7044

Abstract: Stereoregular diblock polybutadiene composed of a polybutadiene block having a 1,4-cis structure and a polybutadiene block having a syndiotactic 1,2 structure. Said stereoregular diblock polybutadiene can be advantageously used in both the footwear industry (for example, in the production of soles for shoes) and in the production of tires for motor vehicles and/or trucks.

公开(公告)号：US20210245145A1

公开(公告)日：2021-08-12

申请号：US17204570

申请日：2021-03-17

Applicant: Versalis S.p.A.

Inventor： Guido PAMPALONI ,  Anna SOMMAZZI ,  Giovanni RICCI ,  Francesco MASI ,  Giuseppe LEONE

IPC: B01J31/20 ,  C08F36/08 ,  C08F36/06 ,  C08F4/70 ,  C08F4/52

Abstract: An oxo-nitrogenated iron complex having general formula (I) or (II) wherein: R1 and R2 identical or different, represent a hydrogen atom; or are selected from linear or branched, optionally halogenated C1-C20, preferably C1-C15, alkyl groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups; R3, identical or different, represent a hydrogen atom; or are selected from linear or branched, optionally halogenated C1-C20, preferably C1-C15, alkyl groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups; X1 and X2, identical or different, represent a halogen atom such as, for example, chlorine, bromine, iodine; or are selected from linear or branched C1-C20, preferably C1-C15, alkyl groups, —OCOR4 groups or —OR4 groups wherein R4 is selected from linear or branched C1-C20, preferably C1-C15, alkyl groups. Said oxo-nitrogenated iron complex having general formula (I) or (II) can be advantageously used in a catalytic system for the (co)polymerization of conjugated dienes.

公开(公告)号：US20200247832A1

公开(公告)日：2020-08-06

申请号：US16649131

申请日：2018-09-28

Applicant: Versalis S.P.A.

Inventor： Guido PAMPALONI ,  Giovanni RICCI ,  Anna SOMMAZZI ,  Massimo GUELFI ,  Giuseppe LEONE ,  Francesco MASI

IPC: C07F7/28 ,  C08F4/64 ,  C08F4/642 ,  C08F36/06

Abstract: Bis-imine titanium complex having general formula (I): wherein: R1 and R2, mutually identical or different, represent a hydrogen atom; or are selected from linear or branched, optionally halogenated, C1-C20 alkyl groups, preferably C1-C15, optionally substituted cycloalkyl groups; R3 and R4, mutually identical or different, represent a hydrogen atom; or are selected from linear or branched, optionally halogenated, C1-C20 alkyl groups, preferably C1-C15, optionally substituted cycloalkyl groups, optionally substituted aryl groups; X1, X2, X3 and X4, mutually identical or different, represent a halogen atom such as chlorine, bromine, iodine; or are selected from linear or branched C1-C20 alkyl groups, preferably C1-C15, —OCOR5 groups or —OR5 groups wherein R5 is selected from linear or branched C1-C20 alkyl groups, preferably C1-C15; or represent an acetylacetonate group (acac); provided that when R1 and R2 represent a methyl group and X1, X2, X3 and X4 represent a chlorine atom, R3 and R4 are different from 2,6-di-isopropylphenyl.