KR20070018930A - Process for the preparation of atactic 1-butene polymers - Google Patents

Abstract

Obtaining a hybrid array 1-butene polymer optionally comprising one or more comonomers selected from ethylene, propylene or alpha-olefins of formula CH ₂ = CHR wherein R is a linear or branched C ₃ -C ₂₀ alkyl group A process comprising: polymerizing 1-butene and optionally ethylene, propylene or the alpha-olefin in the presence of a catalyst system obtainable by contacting:

a) at least one metallocene compound of formula (I) in meso or meso-like form:

[Wherein M is an atom of a transition metal; p is an integer from 0 to 3; X is the same or different and is a hydrogen atom, a halogen atom or a hydrocarbon group; L is a divalent C ₁ -C ₄₀ hydrocarbon radical optionally containing heteroatoms belonging to groups 13-17 of the periodic table of elements; R ¹ and R ² are C ₁ -C ₄₀ hydrocarbon radicals; T is the same or different from one another and is a part of formula (IIa) or (IIb):

Wherein R ³ is a C ₁ -C ₄₀ hydrocarbon radical; R ⁴ and R ⁶ are hydrogen atoms or C ₁ -C ₄₀ hydrocarbon radicals; R ⁵ is a C ₁ -C ₄₀ hydrocarbon radical; R ⁷ and R ⁸ are the same as or different from each other, and are a hydrogen atom or a C ₁ -C ₄₀ hydrocarbon radical}]; And

b) compounds capable of forming alumoxanes, or alkyl metallocene cations.

Hybrid Arrays, 1-butene Polymers, Metallocene Catalysts, Meso Forms

Description

Process for producing hybrid array 1-butene polymer {PROCESS FOR THE PREPARATION OF ATACTIC 1-BUTENE POLYMERS}

The present invention relates to a process for preparing atactic and amorphous 1-butene polymers by polymerization of 1-butene and optionally alpha-olefins in the presence of isomeric meso or meso-like forms of metallocene catalyst components. It is about.

Polymers of amorphous 1-butene have been mainly used as sticking agents, improvers for crystalline polyolefins, and the like. These were obtained using different catalyst systems.

For example, US 6,288,192 is an ultra high molecular weight amorphous 1-butene polymer obtained using compounds such as dichloro {2,2'-thiobis [4-methyl-6- (tert-butyl) phenolato]} titanium. It is about. These compounds are completely different from metallocene compounds. The document describes 1-butene polymers having Mn of at least 200,000, preferably at least 300,000, more preferably at least 500,000. However, the Mn of the 1-butene polymer of its examples is much larger, especially in the range of about 1 million to about 35 million. In this document, it is mentioned that chain transfer agents such as hydrogen can be used for the control of molecular weight, but from WO 02/060963, the molecular weight of the polymer produced by thiobis (phenoxy) titanium dichloride is relatively hydrogen ratio. It is known to be sensitive. Therefore, it is not possible to lower the molecular weight of the 1-butene polymer to less than 1 million using hydrogen as the molecular weight modifier, and consequently the description of US 6,288,192 for Mn values of less than 1 million is considered impossible. In addition, US 6,288,192 discloses Journal of polymer Science: Part A: Polymer Chemistry, vol. 42,1107-1111 (2004), although not related to the NMR structure of the poly1-butenes obtained by the inventors, the inventors analyzed the polymers obtained according to the method described in the above US patents, so that the polybutenes obtained were It was found to be isotactic and had a mmmm pentad content of about 25%.

US patent application 2003/0069320 describes 1-butene polymers obtained using bicrosslinked metallocene compounds. The 1-butene mono- and copolymers thus obtained are not completely amorphous and are characterized by one or more melting points.

In Example 17 of EP 604908, dimethylsilanediylbis (9-fluorenyl) zirconium dichloride was used to obtain a polybutene polymer. However, this metallocene compound has C _2ν symmetry and therefore does not exhibit racemates and meso isomers. The molecular weight (IV) of the obtained polymer can be further increased, and the catalytic activity was low.

JP 11-193309 describes amorphous propylene / 1-butene copolymers by the use of metallocene compounds with one single cyclopentadienyl-substituent. The copolymer thus obtained is characterized by a high propylene content.

Macromol. Chem. Phys, 200, 1587-1594 (1999) discloses a 1-butene polymerization method in the presence of rac / meso Me ₂ Si (2-Me-Ind) ₂ ZrCl ₂ . However, the molecular weight of the hybrid arrangement fraction of the obtained polymers listed in Table 1 is very low.

Macromol. Rapid Commun. 18, 581-589, (1997), a rac and meso mixture of dimethylsilylenebis (2,3,5-trimethyl-cyclopentadienyl) zirconium dichloride was used for the polymerization of 1-butene. Also in this case, the molecular weight of the hybrid array fraction is very low.

Macromolecules 2000, 33, 1955-1959 describe three different metallocene compounds in 1-butene polymerization, namely Me ₂ Si (2-Me-4,5-BzoInd) ₂ ZrCl ₂ , Me ₂ Si (2). A rac meso mixture of -Me-4-PhInd) ₂ ZrCl ₂ and Me ₂ Si (Ind) ₂ ZrCl ₂ was tested. However, the molecular weight of the hybrid array polybutene and its activity may be further improved as shown in the comparative examples of the present application.

Therefore, there is a need for a new method that can obtain high molecular weight hybrid array and amorphous 1-butene polymers in high yield.

Subject of the invention is a hybrid arrangement optionally comprising one or more comonomers selected from ethylene, propylene or alpha-olefins of the formula CH ₂ = CHR wherein R is a linear or branched C ₃ -C ₂₀ alkyl group and A process for obtaining an amorphous 1-butene polymer, the process comprising polymerizing 1-butene and optionally ethylene, propylene or the alpha-olefin in the presence of a catalyst system obtainable by contacting:

a) at least one metallocene compound of formula (I) in meso or meso-like form:

[In the meal,

M is an atom of a transition metal selected from those belonging to groups 3, 4, 5, 6 or lanthanides or actinides of the periodic table of elements; Preferably M is titanium, zirconium or hafnium;

p is an integer from 0 to 3, preferably p is 2, which is equivalent to (formal oxidation state of metal M-2);

X is the same or different and is a hydrogen atom, a halogen atom or a R, OR, OSO ₂ CF ₃ , OCOR, SR, NR ₂ or PR ₂ group, wherein R is linear or branched, cyclic or non Cyclic, C ₁ -C ₄₀ -alkyl, C ₂ -C ₄₀ alkenyl, C ₂ -C ₄₀ alkynyl, C ₆ -C ₄₀ -aryl, C ₇ -C ₄₀ -alkylaryl or C ₇ -C ₄₀ An arylalkyl radical, optionally including heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements, preferably R is a linear or branched C ₁ -C ₂₀ -alkyl radical; Or two X are optionally substituted or unsubstituted butadienyl radicals or OR'O groups, wherein R 'is C ₁ -C ₄₀ alkylidene, C ₆ -C ₄₀ arylidene, C ₇ -C ₄₀ alkyla Is a divalent radical selected from lilydene and C ₇ -C ₄₀ arylalkylidene radicals; Preferably X is a hydrogen atom, a halogen atom or an R group; More preferably X is a chlorine or C ₁ -C ₁₀ -alkyl radical; For example methyl or ethyl radicals;

L is a divalent C ₁ -C ₄₀ hydrocarbon radical optionally containing heteroatoms belonging to groups 13 to 17 of the Periodic Table of the Elements or divalent sillylidene radicals containing up to 5 silicon atoms; Preferably L is C ₁ -C ₄₀ alkylidene, C ₃ -C ₄₀ cycloalkylidene, C ₆ -C ₄₀ arylidene, C ₇ -C optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements _A divalent bridging group selected from a ₄₀ alkylarylidene, or a silyldene radical containing up to 5 silicon atoms such as C ₇ -C ₄₀ arylalkylidene radicals and SiMe ₂ , SiPh ₂ ; Preferably, L is a (Z (R ″) ₂ ) _n group, wherein Z is a carbon or silicon atom, n is 1 or 2, and R ″ optionally represents a heteroatom belonging to groups 13 to 17 of the periodic table of elements. Is a C ₁ -C ₂₀ hydrocarbon radical; preferably R ″ is a linear or branched, cyclic or acyclic C ₁ -C ₂₀ -alkyl optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₆ -C ₂₀ -aryl, C ₇ -C ₂₀ -alkylaryl or C ₇ -C ₂₀ -arylalkyl radical; more preferably (Z (R ″) ₂ ) _n group is Si (CH ₃ ) ₂ , SiPh ₂ , SiPhMe, SiMe (SiMe ₃ ), CH ₂ , (CH ₂ ) ₂ , and C (CH ₃ ) ₂ ;

R ¹ and R ² are the same or different from each other and are C ₁ -C ₄₀ hydrocarbon radicals optionally comprising heteroatoms belonging to groups 13 to 17 of the Periodic Table of the Elements; Preferably they are linear or branched, cyclic or acyclic C ₁ -C ₄₀ -alkyl, C ₂ -C ₄₀ alkenyl, C ₂ -C ₄₀ alkynyl, C ₆ -C ₄₀ -aryl, C ₇ -C ₄₀ -alkylaryl or C ₇ -C ₄₀ -arylalkyl radical; Optionally includes heteroatoms belonging to groups 13-17 of the periodic table of elements; More preferably R ¹ and R ² are linear or branched, saturated or unsaturated C ₁ -C ₂₀ -alkyl radicals; More preferably R ¹ and R ² are methyl or ethyl radicals;

T is the same or different from one another and is part of formula (IIa) or (IIb):

Wherein the atom indicated by the * symbol is bonded to the atom represented by the same symbol in the compound of formula (I);

R ³ is a C ₁ -C ₄₀ hydrocarbon radical optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; Preferably R ³ is linear or branched, cyclic or acyclic C ₁ -C ₄₀ -alkyl, C ₂ -C ₄₀ alkenyl, C ₂ -C ₄₀ alkynyl, C ₆ -C ₄₀ -aryl, C ₇ -C ₄₀ -arylalkyl or C ₇ -C ₄₀ -alkylaryl radical; Optionally includes heteroatoms belonging to groups 13-17 of the periodic table of elements; More preferably R ³ is a linear or branched C ₁ -C ₂₀ -alkyl, C ₆ -C ₄₀ -aryl, C ₇ -C ₄₀ -arylalkyl radical; Even more preferably R ³ is a C ₆ -C ₂₀ -aryl radical optionally substituted with one or more C ₁ -C ₁₀ alkyl groups;

R ⁴ and R ⁶ are the same or different from each other and are C ₁ -C ₄₀ hydrocarbon radicals which optionally contain a hydrogen atom or a heteroatom belonging to groups 13 to 17 of the periodic table of elements; Preferably R ⁴ and R ⁶ are the same or different from each other and are linear or branched, cyclic or acyclic C ₁ -C ₄₀ -optionally containing a hydrogen atom or a heteroatom belonging to groups 13 to 17 of the Periodic Table of the Elements. Alkyl, C ₂ -C ₄₀ alkenyl, C ₂ -C ₄₀ alkynyl, C ₆ -C ₄₀ -aryl, C ₇ -C ₄₀ -alkylaryl or C ₇ -C ₄₀ -arylalkyl radicals; Optionally includes heteroatoms belonging to groups 13-17 of the periodic table of elements; Preferably R ⁴ and R ⁶ are hydrogen atoms;

R ⁵ is a C ₁ -C ₄₀ hydrocarbon radical optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; Preferably R ⁵ is linear or branched, cyclic or acyclic C ₁ -C ₄₀ -alkyl, C ₂ -C ₄₀ alkenyl, C ₂ -C ₄₀ alkynyl, C ₆ -C ₄₀ -aryl, C ₇ -C ₄₀ -alkylaryl or C ₇ -C ₄₀ -arylalkyl radical; Optionally includes heteroatoms belonging to groups 13-17 of the periodic table of elements; More preferably R ⁵ is a linear or branched, saturated or unsaturated C ₁ -C ₂₀ -alkyl radical; Even more preferably R ⁵ is a methyl or ethyl radical;

R ⁷ and R ⁸ are the same or different from each other and are C ₁ -C ₄₀ hydrocarbon radicals which optionally comprise a hydrogen atom or a heteroatom belonging to groups 13 to 17 of the periodic table of elements; Preferably R ⁷ and R ⁸ are hydrogen atoms or linear or branched, cyclic or acyclic C ₁ -C ₄₀ -alkyl, C ₂ -C ₄₀ alkenyl, C ₂ -C ₄₀ alkynyl, C _6- A C ₄₀ -aryl, C ₇ -C ₄₀ -alkylaryl or C ₇ -C ₄₀ -arylalkyl radical; Optionally includes heteroatoms belonging to groups 13-17 of the periodic table of elements;

Preferably R ⁸ is a hydrogen atom or a linear or branched, saturated or unsaturated C ₁ -C ₂₀ -alkyl radical; More preferably R ⁸ is a methyl or ethyl radical;

Preferably R ⁷ is C ₁ -C ₄₀ -alkyl, C ₆ -C ₄₀ -aryl or C ₇ -C ₄₀ -arylalkyl; More preferably R ⁷ is a group of formula (III):

(Wherein R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are the same or different from each other, a hydrogen atom or a linear or branched, cyclic or acyclic, C ₁ -C ₂₀ -alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₆ -C ₂₀ -aryl, C ₇ -C ₂₀ -alkylaryl or C ₇ -C ₂₀ -arylalkyl radical; optionally 13-17 of the Periodic Table of the Elements Heteroatoms belonging to the group; preferably R ⁹ and R ¹² are hydrogen atoms; R ¹⁰ , R ¹¹ and R ¹³ are preferably hydrogen atoms or linear or branched, cyclic or acyclic C ₁ -C ₁₀ -alkyl radical)}];

b) compounds capable of forming alumoxanes, or alkyl metallocene cations; And optionally

c) organoaluminum compounds.

For the purposes of the present invention the term "meso form" means that the same substituents on the two cyclopentadienyl moieties are present on the same side with respect to the plane comprising zirconium and the center of said cyclopentadienyl moiety.

“Meso-like form” means that the bulky substituents of the two cyclopentadienyl moieties on the metallocene compound are in the plane of the zirconium and in the center of the cyclopentadienyl moiety, as shown in the following compounds: On the same side as:

In one embodiment, the compound of formula (I) has the formula (IV)

Wherein M, X, p, L, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ have the meanings described above.

In another embodiment, compounds of Formula (I) have Formula (V)

Wherein M, X, p, L, R ¹ , R ² , R ⁷ and R ⁸ have the meanings described above.

Metallocene compounds of formula (I) are well known in the art and can be prepared according to known methods such as those described in WO 01/44318, WO 03/045964, PCT / EP02 / 13552 and DE 10324541.3. .

Alumoxanes used as component b) may be selected from the group consisting of water of the formula H _j AlU _3-j or H _j Al ₂ U _6-j {wherein the substituents U are the same or different and are hydrogen atoms, halogen atoms, optionally silicon or germanium A C ₁ -C ₂₀ -alkyl, C ₃ -C ₂₀ -cycloalkyl, C ₆ -C ₂₀ -aryl, C ₇ -C ₂₀ -alkylaryl or C ₇ -C ₂₀ -arylalkyl radical containing an atom, provided At least one U is not halogen and j is in the range of 0 to 1, which is also obtainable by reaction with an organo-aluminum compound of the non-integer number}. The Al / water molar ratio in this reaction is preferably comprised between 1: 1 and 100: 1.

Alumoxanes used in the process according to the invention are considered to be linear, branched or cyclic compounds comprising at least one group of the following types:

{Wherein the substituents U are the same or different and are defined above}.

In particular, for linear compounds, alumoxanes of the general formula can be used:

{Wherein n ¹ is 0 or an integer from 1 to 40 and the substituent U is defined as above}; Or in the case of cyclic compounds, alumoxanes of the general formula:

{Wherein n ² is an integer from 2 to 40 and the substituent U is defined as above}.

Examples of suitable alumoxanes for use in accordance with the invention are methylalumoxane (MAO), tetra- (isobutyl) alumoxane (TIBAO), tetra- (2,4,4-trimethyl-pentyl) alumoxane (TIOAO), Tetra- (2,3-dimethylbutyl) alumoxane (TDMBAO) and tetra- (2,3,3-trimethylbutyl) alumoxane (TTMBAO).

Particularly interesting cocatalysts are those described in WO 99/21899 and WO 01/21674, in which alkyl and aryl groups have specific branched patterns.

Non-limiting examples of aluminum compounds that can react with water to provide the appropriate alumoxane (b), described in WO 99/21899 and WO 01/21674, are the following: Tris (2,3,3-trimethyl-butyl) Aluminum, tris (2,3-dimethyl-hexyl) aluminum, tris (2,3-dimethyl-butyl) aluminum, tris (2,3-dimethyl-pentyl) aluminum, tris (2,3-dimethyl-heptyl) aluminum, Tris (2-methyl-3-ethyl-pentyl) aluminum, tris (2-methyl-3-ethyl-hexyl) aluminum, tris (2-methyl-3-ethyl-heptyl) aluminum, tris (2-methyl-3- Propyl-hexyl) aluminum, tris (2-ethyl-3-methyl-butyl) aluminum, tris (2-ethyl-3-methyl-pentyl) aluminum, tris (2,3-diethyl-pentyl) aluminum, tris (2 -Propyl-3-methyl-butyl) aluminum, tris (2-isopropyl-3-methyl-butyl) aluminum, tris (2-isobutyl-3-methyl-pentyl) aluminum, tris (2,3,3-trimethyl -Pentyl) aluminum, tris (2,3,3-trimethyl-hexyl Aluminum, tris (2-ethyl-3,3-dimethyl-butyl) aluminum, tris (2-ethyl-3,3-dimethyl-pentyl) aluminum, tris (2-isopropyl-3,3-dimethyl-butyl) Aluminum, tris (2-trimethylsilyl-propyl) aluminum, tris (2-methyl-3-phenyl-butyl) aluminum, tris (2-ethyl-3-phenyl-butyl) aluminum, tris (2,3-dimethyl-3 -Phenyl-butyl) aluminum, tris (2-phenyl-propyl) aluminum, tris [2- (4-fluoro-phenyl) -propyl] aluminum, tris [2- (4-chloro-phenyl) -propyl] aluminum, Tris [2- (3-isopropyl-phenyl) -propyl] aluminum, tris (2-phenyl-butyl) aluminum, tris (3-methyl-2-phenyl-butyl) aluminum, tris (2-phenyl-pentyl) aluminum , Tris [2- (pentafluorophenyl) -propyl] aluminum, tris [2,2-diphenyl-ethyl] aluminum and tris [2-phenyl-2-methyl-propyl] aluminum, and one of the hydrocarbyl groups The corresponding compound substituted with a hydrogen atom, and Roca Le one or two of those substituted with isobutylene of invoking.

Among the aluminum compounds, trimethylaluminum (TMA), triisobutylaluminum (TIBA), tris (2,4,4-trimethyl-pentyl) aluminum (TIOA), tris (2,3-dimethylbutyl) aluminum (TDMBA) and Tris (2,3,3-trimethylbutyl) aluminum (TTMBA) is preferred.

A non-limiting example of a compound capable of forming an alkylmetallocene cation is a compound of formula D ⁺ E ^-wherein D ⁺ can provide a proton and with the substituents X of the metallocene of formula (I) Bronsted acid capable of irreversibly reacting, E ⁻ is a compatible anion that is capable of stabilizing the active catalytic species resulting from the reaction of the two compounds and is sufficiently unstable to be removed by the olefinic monomers. Preferably, the anion E ⁻ comprises at least one boron atom. More preferably, the anion E ⁻ is an anion of the formula BAr ₄ ⁽⁻⁾ , wherein the substituents Ar may be the same or different and may be aryl such as phenyl, pentafluorophenyl or bis (trifluoromethyl) phenyl. It is a radical. As described in WO 91/02012, tetrakis-pentafluorophenyl borate is a particularly preferred compound. It is also possible to conveniently use the compound of the formula BAr ₃ . Compounds of this type are described, for example, in international patent application WO 92/00333.

Another example of a compound capable of forming an alkylmetallocene cation is a compound of the formula BAr ₃ P, wherein P is a substituted or unsubstituted pyrrole radical. These compounds are described in WO 01/62764. Compounds containing boron atoms can conveniently be supported according to the descriptions of DE-A-19962814 and DE-A-19962910. All of these compounds comprising boron atoms may comprise a molar ratio comprised between about 1: 1 and about 10: 1 between the boron and metallocene metal; Preferably 1: 1 to 2: 1; More preferably, it can be used in a molar ratio of about 1: 1.

Non-limiting examples of compounds of formula D ⁺ E ^- are:

Triethylammonium tetra (phenyl) borate,

Tributylammonium tetra (phenyl) borate,

Trimethylammonium tetra (tolyl) borate,

Tributylammonium tetra (tolyl) borate,

Tributylammonium tetra (pentafluorophenyl) borate,

Tributylammonium tetra (pentafluorophenyl) aluminate,

Tripropylammonium tetra (dimethylphenyl) borate,

Tributylammonium tetra (trifluoromethylphenyl) borate,

Tributylammonium tetra (4-fluorophenyl) borate,

N, N-dimethylbenzylammonium-tetrakispentafluorophenylborate,

N, N-dimethylhexylammonium-tetrakispentafluorophenylborate,

N, N-dimethylanilinium tetra (phenyl) borate,

N, N-diethylanilinium tetra (phenyl) borate,

N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate,

N, N-dimethylanilinium tetrakis (pentafluorophenyl) aluminate,

N, N-dimethylbenzylammonium-tetrakispentafluorophenylborate,

N, N-dimethylhexylammonium-tetrakispentafluorophenylborate,

Di (propyl) ammonium tetrakis (pentafluorophenyl) borate,

Di (cyclohexyl) ammonium tetrakis (pentafluorophenyl) borate,

Triphenylphosphonium tetrakis (phenyl) borate,

Triethylphosphonium tetrakis (phenyl) borate,

Diphenylphosphonium tetrakis (phenyl) borate,

Tri (methylphenyl) phosphonium tetrakis (phenyl) borate,

Tri (dimethylphenyl) phosphonium tetrakis (phenyl) borate,

Triphenylcarbenium tetrakis (pentafluorophenyl) borate,

Triphenylcarbenium tetrakis (pentafluorophenyl) aluminate,

Triphenylcarbenium tetrakis (phenyl) aluminate,

Ferrocenium tetrakis (pentafluorophenyl) borate,

Ferrocenium tetrakis (pentafluorophenyl) aluminate,

Triphenylcarbenium tetrakis (pentafluorophenyl) borate, and

N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.

The organoaluminum compound used as compound c) is a compound of the formula H _j AlU _3-j or H _j Al ₂ U _6-j as described above.

The polymerization process of the invention can be carried out in the liquid phase or in the gas phase, optionally in the presence of an inert hydrocarbon solvent. The hydrocarbon solvent may be aromatic (such as toluene) or aliphatic (such as propane, hexane, heptane, isobutane, cyclohexane and 2,2,4-trimethylpentane). Preferably, the polymerization process of the invention is carried out using liquid 1-butene as the polymerization medium. It is preferably carried out in bulk.

The polymerization temperature is preferably in the range of 0 ° C to 250 ° C; Preferably from 20 ° C. to 150 ° C., more particularly from 40 ° C. to 90 ° C .;

The molecular weight distribution can be varied by using a mixture of different metallocene compounds or by carrying out the polymerization in several stages at which the polymerization temperature and / or the concentration of the molecular weight regulator and / or the monomer concentration differ. Performing a polymerization process using a combination of two different metallocene compounds of formula (I) produces polymers given a wide range of melting points.

In addition, surprisingly, 1-butene is polymerized in the presence of at least one comonomer selected from ethylene, propylene or an alpha-olefin of the formula CH ₂ = CHR wherein R is a linear or branched C ₃ -C ₂₀ alkyl group. When found, the activity of the catalyst system was found to be increased. Thus, even small additions of ethylene, propylene or comonomers selected from the above alpha-olefins can increase the activity of the process of the invention. Preferably, 1-butene is polymerized in the presence of at least 60 mol%, preferably at most 50 mol%, more preferably 5 to 30 mol% of one or more of the comonomers. In a particularly preferred embodiment, the comonomer is propylene, 1-pentene, 1-hexene, or 1-octene; More preferably the comonomer is propylene.

By the process of the present invention, high molecular weight hybrid arrays and amorphous 1-butene homopolymers and copolymers can be obtained in high yields.

Particularly in the 1-butene polymers obtained according to the invention, the molten enthalpy is not detectable by differential scanning calorimetry (DSC), which is completely amorphous. The atacticity of the 1-butene polymers obtainable by the process of the present invention is indicated by particularly low values of mmmm pentads; In particular, the value of mmmm pentad for the homopolymer is less than 20.

Another subject of the invention is a hybrid array amorphous 1-butene homopolymer having the following characteristics:

(i) an intrinsic viscosity (I.V.) measured in tetrahydronaphthalene (THN) at 135 ° C. is at least 1.30 dL / g; Preferably said intrinsic viscosity is greater than 1.80 dL / g; More preferably greater than 2.0 dL / g;

(ii) the molecular weight distribution Mw / Mn is less than 4; Preferably less than 3.5; More preferably greater than 2.5 and less than 3.5;

(iii) no melt enthalpy detectable by differential scanning calorimetry (DSC);

(iv) less than 20%, preferably less than 15%, of the same array pentad (mmmm); More preferably less than 10%.

As described above, by the process of the present invention, 1-butene copolymer can be obtained in high yield. The copolymer is characterized by the fact that it is completely hybrid, that is, even the 1-butene block in the polymer chain is hybrid. The main effect of the comonomers is therefore to increase the yield of the process and to prevent destruction of the crystallinity of the resulting polymers, which usually occurs when copolymerizing 1-butene using a catalyst system to prepare crystalline polymers.

Another subject of the invention is 51 mole% derived from ethylene, propylene or an alpha-olefin of the formula CH ₂ = CHR, wherein R is a linear or branched C ₃ -C ₁₀ alkyl group. Hereinafter, a hybrid array amorphous 1-butene copolymer comprising preferably up to 50 mol% of comonomer units, preferably comprising 5 to 30 mol% of ethylene, propylene or said alpha-olefin:

(i) intrinsic viscosity (I.V.) measured in tetrahydronaphthalene (THN) at 135 ° C. is from 1.00 to 2.50 dl / g, preferably from 1.79 to 2.31 dl / g;

(ii) molecular weight distribution Mw / Mn is less than 4; Preferably less than 3.5; More preferably less than 3;

(iii) No melt enthalpy detectable by differential scanning calorimetry (DSC).

Preferably the comonomer derived units are selected from propylene, 1-pentene, 1-hexene, or 1-octene; Even more preferably the comonomer unit is propylene.

The hybrid array amorphous 1-butene copolymer of the present invention preferably has an intrinsic viscosity (IV) measured in tetrahydronaphthalene (THN) at 135 ° C. of 1.00 to 2.50 dl / g, preferably 1.79 to 2.31 dl / g. ego; Provided that the viscosity is not 1.78 to 1.79 dl / g, or 2.31 to 2.32 dl / g.

The hybrid array amorphous 1-butene copolymer of the present invention preferably has a r1xr2 reactivity ratio measured as described in the above examples ranging from 0.80 to 1.20; Preferably in the range of 0.90 to 1.10; More preferably it is in the range of 0.95 to 1.05.

When the intrinsic viscosity (I.V.) of the 1-butene copolymer of the present invention exceeds 2.50 dl / g, since the fluidity of the molten polymer suddenly decreases, the processability of the copolymer decreases below an acceptable value. If the intrinsic viscosity is less than 1.00 dl / g, the hybrid array amorphous 1-butene copolymer of the present invention becomes unacceptably tacky.

Hybrid-array amorphous 1-butene mono- and copolymers obtainable by the process of the invention can be used as components for the polymer composition. In particular, because of their high molecular weight, they can be used in compositions containing homo-array polypropylene single or copolymers.

The following examples are provided for purposes of illustration and do not limit the invention.

Intrinsic viscosity (IV) was measured in tetrahydronaphthalene (THN) at 135 degreeC.

Mw and Mn were calculated using the following empirical formula:

Mw = 59403 (IV) ² + 137760 (IV)

Mn = 32996 (IV) ² + 53607 (IV)

The melting point (T _m ) of the polymer was measured by differential scanning calorimetry (DSC) on a Perkin Elmer DSC-7 instrument according to standard methods. Weighed samples (5-10 mg) obtained by polymerization were sealed in aluminum pans and heated to 180 ° C. at a scanning rate corresponding to 10 ° C./min. The sample was held at 180 ° C. for 5 minutes to allow melting of all the crystals to be complete. It was then cooled to 20 ° C. at a scanning rate corresponding to 10 ° C./min, then left at 20 ° C. for 2 minutes, and then the sample was secondly heated to 180 ° C. at a scanning rate corresponding to 10 ° C./min. In the second heating operation, the peak temperature was taken as the melting temperature (T _m ) and the area was taken as the melting enthalpy (ΔH _f ).

Molecular weight parameters and molecular weight distribution for all samples were determined using a Waters 150C ALC / GPC instrument (Waters, Milford, Massachusetts, USA) equipped with four mixed-gel columns PLgel 20 μm Mixed-A LS (Polymer Laboratories, Church Stretton, United Kingdom). ) Was measured. The dimension of the column was 300 × 7.8 mm. The solvent used was TCB and the flow rate was maintained at 1.0 mL / min. The solution concentration was 1.0 g / dL in 1,2,4-trichlorobenzene (TCB). 0.1 g / L of 2,6-di-t-butyl-4-methyl phenol (BHT) was added to prevent degradation and the injection volume was 300 μl. All measurements were performed at 135 ° C. The GPC calibration is complicated because a well characterized narrow molecular weight distribution standard reference material is not available for 1-butene polymers. Thus, a universal calibration curve was obtained using 12 polystyrene standard samples with molecular weights ranging from 580 to 13,200,000. The K value of the Mark-Houwink relation was estimated to be: K _PS = 1.21 × 10 ⁻⁴ dL / g and K _PB = 1.78 × 10 ⁻⁴ dL / g for polystyrene and poly-1-butene, respectively. Mark-Houwink index α was estimated to be 0.706 for polystyrene and 0.725 for poly-1-butene. In this approach, the molecular parameters obtained are only estimates of the hydrodynamic volume of each chain, but they allow for relative comparison.

NMR analysis . ¹³ C-NMR spectra were obtained on a DPX-400 spectrometer operating at 100.61 MHz in Fourier conversion mode at 120 ° C. Samples were dissolved in 1,1,2,2-tetrachloroethane-d2 at 120 ° C. at a concentration of 8% wt / v. Each spectrum was obtained at 90 ° pulses and delayed 15 seconds between pulses and CPD (waltz16) to remove ¹ H- ¹³ C coupling. About 3,000 transients were stored at 32 K data points using a 6,000 Hz spectrum window. Isoarrangement of the metallocene PB is measured by ¹³ C NMR and is defined as the relative intensity of the mmmm pentad peak of the diagnostic methylene of the ethylene branch. The peak at 27.73 ppm was used as internal standard. Pentad assignments are provided according to Macromolecules , 1992, 25, 6814-6817.

The copolymer composition was measured from divalent as follows:

PP = [Sαα (47.5-45.9 ppm) / ∑ (Sαα)] x100

PB = [Sαα (44.1-42.8 ppm) / ∑ (Sαα)] x100

BB = [Sαα (39.93-40.31 ppm) / ∑ (Sαα)] x100

(Sαα) = sum of Sαα peak areas = Sαα (47.5-45.9 ppm) + Sαα (44.1-42.8 ppm) + Sαα (39.93-40.31 ppm)

P = PP + O.5PB

B = BB + 0.5 PB

Determination of the product of reactivity ratio r1xr2

The product of the reactive ratios is obtained from the ¹³ C NMR triad distribution using the following formula according to CJ Carman, RA Harrington and CE Wilkes, Macromolecules , 10 , 536 (1977).

Butene / propylene copolymer:

Metallocene compound

Meso dimethylsilanediylbis-6- [2,5-dimethyl-3- (2'-methyl-phenyl) cyclopentadienyl- [1,2-b] -thiophene] zirconium di according to WO 01/44318 Chloride (A-1) was prepared.

Rac dimethylsilylbis (2,4,6 trimethyl-indenyl) zirconium dichloride (A-2rac) is prepared according to the Journal of Polymer Science: Part A: polymer chemistry, vol 38,4299-4307 (2000). It was.

Dimethylsilylbis (2,4,6 trimethyl-indenyl) zirconium dichloride (A-2) was prepared according to the following procedure, which is obtained in a rac meso 60:40 mixture:

Me ₂ Si (2,4,6-trimethylindenyl) ₂ ZrCl ₂  Synthesis of

Synthesis of 2,4,6-trimethyl-indan-1-one

A 500 mL, three-neck round bottom flask equipped with a magnetic stir bar and a reflux condenser was charged with nitrogen atmosphere and charged with 71.16 g of AlCl ₃ (0.53 mol, 2.3 equiv) dissolved in 240 mL of chlorobenzene. 28.38 mL of m -xylene (0.23 mol, 1 equiv) was added dropwise at room temperature to give a bright yellow suspension. The flask was then cooled to 0 ° C. and 28.68 mL of 2-bromoisobutyryl bromide (0.23 mol, 1 equiv) was added slowly. A dark red slurry was obtained at the end of the addition. The reaction mixture was then allowed to warm to room temperature and stirred for 2 hours. Thereafter, it was transferred to a flask containing a solution of ice / HCl 37% = 3/1. The organic phase was extracted with Et ₂ O (3 × 200 mL): The combined organic phases were dried over Na ₂ SO ₄ , filtered and the solvent removed in vacuo. An orange oil was obtained as a product (37.48 g, yield 93.5%). The latter was used as such in the next step without further purification.

Synthesis of 2,4,6-trimethylindan-1-ol

37.48 g of 2,4,6-trimethyl-indan-1-one (0.215 mol) was dissolved in 200 mL of EtOH in a 500 mL, 3-neck round bottom flask equipped with a magnetic stir bar, thermometer and reflux condenser. Thereafter, NaBH ₄ (15.01 g, 0.394 mol, 1.6 equiv) was slowly added while maintaining the temperature below 20 ° C. The light yellow suspension was stirred at rt for 18 h. Thereafter, 100 mL of acetone was carefully added, and then the solvent was removed to obtain a white solid. The latter was treated with 100 mL of water and extracted with toluene (2 x 150 mL). The water phase was further extracted with toluene, the organic phases were combined and washed with 10% aqueous NH ₄ Cl solution. After washing, the organic phase was dried over Na ₂ S0 ₄ , filtered and evaporated to give 35.57 g of a viscous yellow solid, which was two parts mixed by 5 wt% of starting indanone by NMR analysis. It was found to be the desired product as a 1.4 / 1 mixture of stereoisomers (yield 89.2%). The product was used as such in the next step without further purification.

Synthesis of 2,4,6-trimethyl-indene

2,4,6-trimethyl-indan-1-ol (35.57 g, 0.192 mol) prepared as described above, 0.5 g of p -toluenesulfonic acid monohydrate and 160 mL of toluene were prepared with a magnetic stir bar, Dean-Star. It was placed in a 500 mL, three-neck round bottom flask equipped with a dean-Stark unit and a reflux condenser. The reaction mixture was heated at 80 ° C. for 3 hours and 3.5 mL of water was collected. The reaction mixture was then cooled to room temperature and treated with saturated aqueous NaHCO ₃ solution: the organic layer was separated, the aqueous layer was extracted with Et ₂ O and the organic phase was collected. After drying with Na ₂ S0 ₄ , the solvent was evaporated in vacuo to give 28.46 g of orange oil, which was 2.0% by weight, derived from the 2,4,6-trimethylindan-1-ol step. Indanone was found to be the hybrid desired product (purity 93.7%, measured by GC-MS) (yield 87.8%). The product was used as such in the next step without further purification.

Me ₂ Si (2,4,6-trimethylindenyl) ₂ ZrCl ₂  Synthesis of

5 g of 2,4,6-trimethylindene (31.6 mmol) are dissolved in 100 mL of Et ₂ O and the solution is cooled to 0 ° C., and then to a 2.5 M BuLi solution in 13.27 mL of hexane (33.2 mmol, 1.05 equiv) was added dropwise. The ice bath was removed and the reaction mixture was stirred for 1 hour. The creamy yellow slurry thus obtained was cooled to 0 ° C., and thereto was added dropwise 1.92 mL (16.5 mmol) of Me ₂ SiCl ₂ in 20 mL of THF. After warming to room temperature, the yellow slurry was stirred for 1 hour 30 minutes, then the solvent was removed under reduced pressure, the residue was dissolved in toluene, filtered through G4 frit, and the filtrate was colorless. The residue was washed with additional toluene (total 300 mL of toluene). The filtrate was dried in vacuo and evaporated to yield 5.8 g of brown oil, which was identified as the desired ligand by proton NMR analysis. This product (15.56 mmol) was dissolved in 100 mL of Et ₂ O, cooled to 0 ° C., and then 12.6 mL (31.5 mmol) of BuLi 2.5 M in hexane was added dropwise. At the end of the dropwise addition, the red solution was allowed to come to room temperature, stirred for a further 1 hour, and then cooled to 0 ° C. To this was added dropwise a slurry of 3.67 g ZrCl ₄ (15.75 mmol) in 50 mL of toluene. The ice bath was removed and stirred at room temperature for 2 hours, then the dark yellow suspension was dried, dissolved in toluene and filtered through G4 frit. The dark filtrate was analyzed by proton NMR, dried, slurried in a mixture of Et ₂ O (20 mL) and toluene (20 mL), filtered and the solid residue (1.7 g) was purified by proton NMR. Analyzes: The above analysis confirmed that the desired metallocene was formed at a meso: rac ratio of 60:40.

Meso dimethylsilylbis (2-methyl-4,5 benzo-indenyl) zirconium dichloride (C-1) was prepared according to USP 5,830,821.

Meso dimethylsilylbis (2-methyl-4-phenyl-indenyl) zirconium dichloride (C-2) was prepared according to USP 5,786,432.

Cocatalyst methylalumoxane (MAO) is commercially available and used as received: For Examples 1-6 and Comparative Examples 1-2, Crompton AG, 10% wt / vol toluene solution, in Al 1.7 M; For Examples 7 to 9, Albemarle, 30% wt./wt. In toluene.

Examples 1 to 6 and Comparative Examples 1 to 2

The metallocenes in the amounts listed in Table 1 were dissolved in 4-8 mL of toluene together with the appropriate amounts of MAO solution (Al (MAO) / Zr ratios are listed in Table 1) to give a solution, which was obtained at room temperature. After stirring for 10 minutes, the mixture was injected into an autoclave to prepare a catalyst mixture.

6 mmol of Al ( i- Bu) ₃ (TIBA) (as a 1 M solution in hexane) and 1350 g of 1-butene at room temperature, equipped with a magnetically driven stirrer and a 35-mL stainless steel-steel vial and thermostat for temperature control A 4-L jacketed stainless steel-steel autoclave connected to a thermostat was charged, pre-washed with a solution of Al ( i- Bu) ₃ in hexane and dried at 50 ° C. in nitrogen vapor. The autoclave was then adjusted to the polymerization temperature reported in Table 1 and the catalyst system prepared as reported above was injected into the autoclave through a stainless-steel vial using nitrogen pressure. The polymerization was carried out at constant temperature for 1 hour. Thereafter, stirring was stopped; The pressure in the autoclave was raised to 20 bar-g with nitrogen. The bottom discharge valve was opened and the 1-butene / poly-1-butene mixture was discharged into a heated steel tank containing 70 ° C. water. The tank heat switch was turned off and supplied with nitrogen at a flow of 0.5 bar-g. Cool to room temperature, open the steel tank and collect the wet polymer. The wet polymer was dried in an oven at 70 ° C. under reduced pressure.

The polymerization conditions and the characteristic data of the obtained polymer are recorded in Table 1.

In Examples 5 and 6, instead of A-2 in pure meso form, a mixture of 60 meso form and 40 racemates was used. We tested the racemate of A-2 (A-2rac) and found that it is inert to butene polymerization. Thus in Examples 5 and 6, activity is calculated for pure meso. This is an additional advantage of the present invention when using compound A-2, because the racemate is inert and there is no need to separate the racemate and meso form, and the metallocene compound is used as it is without purification. Because it is possible.

Examples 7-9

Catalyst / cocatalyst mixture by pre-reacting 5.2 mL of MAO 30% by weight in toluene with triisobutylaluminum (TIBA) (110 g / L solution-Al _MAO / Al _TIBA = _2/1 mol / mol) in isododecane To prepare; The mixture was stirred at rt for 1 h.

Additional isododecane was added to bring the total content of organometallic compound to 100 g / L, then toluene / isododecane solution was slowly added to the metallocene at room temperature and stirred for 10 minutes to give a clear red-orange color (red -orange) catalyst solution was obtained. The concentration of A-1 in the catalyst solution was 1.64 mg / l.

6 mmol of Al ( i- Bu) ₃ (as a 1M solution in hexane) and the amounts of monomers listed in Table 2 were prepared at room temperature, equipped with a magnetically driven stirrer and a 35-mL stainless steel-steel vial and thermostat for temperature control. Charged into a 4-L jacketed stainless steel-steel autoclave connected to), purified by washing with Al ( i- Bu) ₃ solution in hexanes beforehand and dried at 50 ° C. in nitrogen vapor. No further monomer was fed during the polymerization.

The autoclave is then adjusted to a polymerization temperature of 60 ° C., the solution containing the catalyst / cocatalyst mixture is injected into the autoclave through a stainless-steel vial using nitrogen pressure, and the polymerization is brought to a constant temperature. Was carried out for 1 hour. Thereafter, stirring was stopped; The pressure in the autoclave was elevated to 20 bar-g with nitrogen. The bottom release valve was opened and the 1-butene / 1-butene copolymer mixture was discharged into a heated steel tank containing 70 ° C. water. The tank heat switch was turned off and supplied with nitrogen at a flow of 0.5 bar-g. After cooling to room temperature, the steel tank was opened and the wet polymer was collected. The wet polymer was dried in an oven at 70 ° C. under reduced pressure.

Claims (17)

Obtaining a hybrid array 1-butene polymer optionally comprising one or more comonomers selected from ethylene, propylene or alpha-olefins of formula CH ₂ = CHR wherein R is a linear or branched C ₃ -C ₂₀ alkyl group A process comprising: polymerizing 1-butene and optionally ethylene, propylene or the alpha-olefin in the presence of a catalyst system obtainable by contacting: a) at least one metallocene compound of formula (I) in meso or meso-like form:

[In the meal, M is an atom of a transition metal selected from those belonging to groups 3, 4, 5, 6 or lanthanides or actinides of the periodic table of elements; p is an integer from 0 to 3, which is equal to (formal oxidation state of metal M-2); X is the same or different and is a hydrogen atom, a halogen atom or a R, OR, OSO ₂ CF ₃ , OCOR, SR, NR ₂ or PR ₂ group, wherein R is linear or branched, cyclic or non Cyclic, C ₁ -C ₄₀ -alkyl, C ₂ -C ₄₀ alkenyl, C ₂ -C ₄₀ alkynyl, C ₆ -C ₄₀ -aryl, C ₇ -C ₄₀ -alkylaryl or C ₇ -C ₄₀ An arylalkyl radical, optionally including heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; Or two X are substituted or unsubstituted butadienyl radicals or OR'O groups, wherein R 'is C ₁ -C ₄₀ alkylidene, C ₆ -C ₄₀ arylidene, C ₇ -C ₄₀ alkylaryl Optionally a divalent radical selected from den and a C ₇ -C ₄₀ arylalkylidene radical; L is a divalent C ₁ -C ₄₀ hydrocarbon radical optionally containing heteroatoms belonging to groups 13 to 17 of the Periodic Table of the Elements or divalent sillylidene radicals containing up to 5 silicon atoms; R ¹ and R ² are the same or different from each other and are C ₁ -C ₄₀ hydrocarbon radicals optionally comprising heteroatoms belonging to groups 13 to 17 of the Periodic Table of the Elements; T is the same or different from one another and is part of formula (IIa) or (IIb):

Wherein the atom indicated by the * symbol is bonded to the atom represented by the same symbol in the compound of formula (I); R ³ is a C ₁ -C ₄₀ hydrocarbon radical optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; R ⁴ and R ⁶ are the same or different from each other and are C ₁ -C ₄₀ hydrocarbon radicals which optionally contain a hydrogen atom or a heteroatom belonging to groups 13 to 17 of the periodic table of elements; R ⁵ is a C ₁ -C ₄₀ hydrocarbon radical optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; R ⁷ and R ⁸ are the same or different from each other and are a C ₁ -C ₄₀ hydrocarbon radical optionally containing a hydrogen atom or a heteroatom belonging to groups 13 to 17 of the Periodic Table of the Elements}]; And b) compounds capable of forming alumoxanes, or alkyl metallocene cations. The method of claim 1, wherein the catalyst system further comprises c) an organoaluminum compound. A compound according to claim 1, wherein M in the compound of formula (I) is titanium, zirconium or hafnium; X is a hydrogen atom, a halogen atom or an R group wherein R is defined as in claim 1; p is 2; L is C ₁ -C ₄₀ alkylidene, C ₃ -C ₄₀ cycloalkylidene, C ₆ -C ₄₀ arylidene, C ₇ -C ₄₀ alkyla, optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements ylidene, or C ₇ -C ₄₀ arylalkyl method alkylidene radical and lily yarn divalent bridging group selected from the DEN radicals containing silicon atoms of 5 or less. 4. The compound of claim 1, wherein L is a (Z (R ″) ₂ ) _n group, wherein Z is a carbon or silicon atom, n is 1 or 2, and R ″ is an element A C ₁ -C ₂₀ hydrocarbon radical optionally containing heteroatoms belonging to groups 13-17 of the periodic table. The compound of claim 1, wherein R ¹ and R ² are linear or branched, saturated or unsaturated C ₁ -C ₂₀ -alkyl radicals; R ³ is a linear or branched C ₁ -C ₂₀ -alkyl, C ₆ -C ₄₀ -aryl, C ₇ -C ₄₀ -arylalkyl radical; R ⁴ and R ⁶ are hydrogen atoms; R ⁵ is a linear or branched, saturated or unsaturated C ₁ -C ₂₀ -alkyl radical; R ⁸ is a hydrogen atom or a linear or branched, saturated or unsaturated C ₁ -C ₂₀ -alkyl radical; R ⁷ is a C ₁ -C ₄₀ -alkyl, C ₆ -C ₄₀ -aryl or C ₇ -C ₄₀ -arylalkyl radical. The method of claim 5, wherein R ⁷ is a group of formula (III):

Wherein R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are the same or different from each other, and are a hydrogen atom or a linear or branched, cyclic or acyclic, C ₁ -C ₂₀ -alkyl, C _2- A C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₆ -C ₂₀ -aryl, C ₇ -C ₂₀ -alkylaryl or C ₇ -C ₂₀ -arylalkyl radical; Optionally heteroatoms belonging to groups 13 to 17 of the Periodic Table of the Elements. The method according to claim 1, wherein said metallocene compound in meso or meso-like form has the formula (IV):

Wherein M, X, p, L, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ have the meanings described in claim 1. The method according to claim 1, wherein the metallocene compound in meso or meso-like form has the formula (V):

Wherein M, X, p, L, R ¹ , R ² , R ⁷ and R ⁸ R ⁶ have the meaning described in claim 1. The process of claim 1, wherein the 1-butene is ethylene, propylene or an alpha-olefin of the formula CH ₂ = CHR, wherein R is a linear or branched C ₃ -C ₂₀ alkyl group. Copolymerizing in the presence of at least one comonomer selected from 10. The process of claim 9, wherein the 1-butene is polymerized in the presence of propylene. Hybrid array amorphous 1-butene homopolymers having the following characteristics: (i) an intrinsic viscosity (I.V.) measured in tetrahydronaphthalene (THN) at 135 ° C. is at least 1.30 dl / g; (ii) the molecular weight distribution Mw / Mn is less than 4; (iii) no melt enthalpy detectable by differential scanning calorimetry (DSC); (iv) Coarse pentad (mmmm) is less than 20%. The method of claim 9, wherein the molecular weight distribution Mw / Mn is less than 3.5; Hybrid-array amorphous 1-butene homopolymer with isotactic pentad (mmmm) of less than 15%. Comprising up to 51 mole percent comonomer units derived from ethylene, propylene or alpha-olefins of the formula CH ₂ = CHR, wherein R is a linear or branched C ₃ -C ₁₀ alkyl group Hybrid Array Amorphous 1-butene Copolymer: (i) intrinsic viscosity (I.V.) measured in tetrahydronaphthalene (THN) at 135 ° C., between 1.00 and 2.50 dl / g; (ii) molecular weight distribution Mw / Mn is less than 4; Preferably less than 3.5; More preferably less than 3; (iii) No melt enthalpy detectable by differential scanning calorimetry (DSC). The hybrid array amorphous 1-butene copolymer according to claim 13, comprising up to 50 mol% comonomer units. 15. The hybrid array amorphous 1-butene copolymer of claim 14, comprising from 5 to 30 mole% of comonomer units. The hybrid array amorphous 1-butene copolymer according to any one of claims 13 to 15, wherein the comonomer unit is propylene. 17. The hybrid array amorphous 1-butene copolymer according to any one of claims 13 to 16, wherein the r1xr2 reactivity ratio is in the range from 0.8 to 1.2.