ES2343645T3 - OLEFINE COPOLYMER CONTAINING POLAR GROUP, PROCEDURE TO PREPARE THE SAME, COMPOSITION OF THERMOPLASTIC RESIN CONTAINING THE COPOLYMER, AND USES OF THE SAME. - Google Patents

Abstract

Olefin copolymer containing branched-type polar group comprising a constitutive unit represented by the following formula (1) and a constituent unit represented by the following formula (4), and optionally a constituent unit represented by the following formula (5), having a molecular weight distribution (Mw / Mn) not exceeding 3, and having an intensity ratio of Tαβ with respect to Tαα (Tαβ / Tαα), as determined from a 13C-NMR spectrum of said copolymer, not exceeding 1.0: ** (See formula) ** in which R1 is a hydrogen atom or a straight or branched chain aliphatic hydrocarbon group of 1 to 18 carbon atoms; R5 is a hydrocarbon group; R6 is a heteroatom or a group containing a heteroatom; r is 0 or 1; Z is a polymeric segment obtained by any one of anionic polymerization, ring opening polymerization and polycondensation; W is a hydroxyl group or an epoxy group; p is an integer from 1 to 3, q is 0, 1 or 2, and p + q <= q 3; when p is 2 or 3, each -OZ can be the same or different, and in this case, if r is 0, -OZ can be attached to the same atom or to a different atom of R5, and if r is 1, -OZ can be attached to the same atom or to an atom different from R6; when q is 2, each W can be the same or different, and in this case, if r is 0, W can be attached to the same atom or to an atom different from R5, and if r is 1, W can be attached to the same atom or to an atom other than R6; in the case of p> = q1 and q> = q1, if r is 0, W and -OZ can be attached to the same atom or to a different atom of R5, and if r is 1, W and -OZ can be attached to it atom or an atom other than R6; m is 0 or 1; n is an integer from 1 to 3; and when n is 2 or 3, each W can be the same or different, and in this case, if m is 0, W can be attached to the same atom or to a different atom of R5, and if m is 1, W can be attached to the same atom or to a different atom of R6.

Description

Olefin copolymer containing polar group, procedure for preparing the same resin composition thermoplastic containing the copolymer, and uses thereof.

Field of the Invention

The present invention relates to a copolymer of olefin containing polar group, to a procedure for prepare the copolymer, to a thermoplastic resin composition which contains the copolymer and uses thereof. Plus particularly, the invention relates to an olefin copolymer which contains polar group that has excellent properties of adhesion to metals or polar resins and excellent flexibility, to a process for preparing the copolymer, to a composition of thermoplastic resin that contains the copolymer and uses of the same.

Background of the invention

Polyolefins generally have advantages such as excellent moldability, thermal resistance, mechanical properties, hygienic qualities, resistance to water vapor permeation and appearance of molded articles of the same, and therefore widely used for molded articles by extrusion, blow molded articles and articles injection molded.

Polyolefins, however, do not contain no polar group in the molecule, so that they have a low compatibility with polar resins such as nylon and EVOH and low Adhesion properties to polar resins and metals. Therefore it is difficult to use polyolefins combining them or laminating them with these materials. In addition, molded products of polyolefins they have problems with poor surface hydrophilic properties and Bad antistatic properties.

To solve such problems, so far has widely used a method to graft monomers that contain polar group in polyolefins through polymerization by radicals to improve affinity for materials polar.

Technical plastics such as nylon have excellent strength and thermal resistance, and therefore are used for electronic / electrical components. Technical plastics such as nylon generally have a low resistance to impact, so that sometimes they are combined with copolymers of olefins to improve impact resistance.

Polyolefins, however, do not contain no polar group in the molecule and show low compatibility  with polar resins, and so far it has been used widely a method to graft polar monomers in the polyolefins to improve compatibility with resins polar.

In this method, however, intermolecular cross-linking of polyolefins and the breakdown of molecular chains take place with the graft reaction, and therefore it is difficult to match the viscosity of the graft polymer and the polar resin, and in some cases it is not You get satisfactory compatibility. In addition, a gel component produced by intermolecular crosslinking or a foreign matter (foreign matter attached to an edge of a nozzle)
produced by breaking molecular chains can produce a bad appearance of molded products.

In Japanese patent publications open for public consultation No. 259012/1989, No. 259012/1989,  No. 51510/1990, No. 51511/1990 and No. 177403/1991, a process comprising copolymerizing a α-olefin and a group containing monomer polar using a Ti catalyst or a V catalyst. According to this procedure, intermolecular crosslinking and rupture of molecular chains take place hard, but in the use of these polymerization catalysts, the resulting copolymer it has a non-uniform molecular structure such as a wide Molecular weight distribution or high investment content. Because of this, the orientation of the polar groups towards the interface between the copolymer and the polar material may not be satisfactory, and material adhesion properties polar and compatibility with them can be insufficient In use as a composition, the effects on Adhesion properties and compatibility are not shown unless that a graft copolymer is added in a large amount.

In order to improve hydrophilic properties surface and antistatic properties, a method of adding a small amount of a surfactant of Low molecular weight to polyolefin and mold the mixture. In this method, however, the added surfactant springs towards the surface, and after molding, the film surface has some Sometimes a bleaching problem. The surfactant that has sprouted towards the surface runs along with water drops adhered to it, so that the problem of that the effects of the surfactant do not last long.

The present inventors have studied the light of the above problems. As a result, they have found that a copolymer having a specific molecular structure and a composition containing the copolymer are excellent in compatibility with polar resins and adhesion properties to polar resins and metals, and have also found that the copolymer and composition have excellent hydrophilic properties of surface and antistatic properties. In addition, those present inventors have found that the copolymer and the composition can apply favorably to various uses.

As a procedure to prepare a polymer of olefin such as an ethylene homopolymer, a copolymer of ethylene / α-olefin, a homopolymer of propylene or a copolymer of propylene / α-olefin, so far it has been known a process comprising polymerizing an olefin in presence of a titanium catalyst comprising a component of solid titanium catalyst containing magnesium, halogen and an electron donor, and an organoaluminum compound, or a vanadium catalyst comprising a vanadium compound and a organoaluminum compound. In the copolymerization of a monomer polar using such a catalyst, there are problems in which the distribution of molecular weight or the distribution of the composition is wide and that the polymerization activity is low. As given to meet in Japanese patent publications open to public consultation No. 259012/1989, No. 51510/1990, No. 51511/1990 and No. 177403/1991, when an olefin and a monomer that contains polar group are copolymerized using a Ziegler catalyst to prepare, for example, a polyolefin containing a group polar, low temperature polymerization is carried out only, so that it is known that this procedure has a problem of low activity It is generally known that an olefin is polymerizes in the presence of a metallocene catalyst that comprises a transition metal compound such as zirconocene and an organoaluminum oxy compound (aluminoxane). It is also known that if the metallocene catalyst is used, it you get an olefin polymer that has a high molecular weight with high activity and the resulting olefin polymer has a narrow molecular weight distribution and narrow distribution of composition.

As a procedure to prepare a polyolefin which contains a polar group, a procedure is also known that use a metallocene catalyst. For example, it is known publicly that the polymerization of an olefin containing OH group is performed using a metallocene compound that has a uncrosslinked cyclopentadienyl group group ligand, group crosslinked or uncrosslinked bisindenyl, or indenyl group / group unsubstituted fluorenyl crosslinked with ethylene, as described in Macromolecules, 28, 5351 (1995), Macromolecules, 29, 5255 (1966), and Polymer Preprints, Japan, 49 (2), 215 (2000).

If it is publicly known that polymerization of an olefin having NR2 (R: alkyl group) as a group polar is performed using a metallocene compound that has a uncrosslinked cyclopentadienyl group ligand, bisindenyl group crosslinked or uncrosslinked, or indenyl group / cyclopentadienyl group unsubstituted crosslinked, as described in Macromolecules, 31, 2019 (1998) and Macromolecules, 32, 14 (1999).

A process is known publicly using an organometallic compound other than the metallocene compound, as described in Science, 287, 460 (2000), OCOP2000 in Oslo, and Books of Abstracts (CW Chien). These procedures, however, have the disadvantage of an extremely low polymerization activity.

Because of this, the protection of the polar group through a protective group. A method of protection is described in, for example, Macromolecules, 31, 2019 (1998), J. Am. Chem. Soc., 114, 9679 (1992), Polymer Preprints, Japan, 49 (2), 209 (2000).

In the previous procedures, however, the protective group is introduced, and after the reaction, it must be removed  the protective group, so that the operations are complicated

WO99 / 16851 refers to a copolymer comprising units of a dicarboxylic monomer unsaturated and to an ethylene macromer α-olefin.

WO 95/33806 refers to additives oil soluble dispersants comprising the product of reaction of a functionalized 1-butene copolymer and at least one nucleophilic reagent selected from amines, amino alcohols, alcohols and reactive metal compounds.

In such circumstances, those present inventors have studied and found that an olefin polymer that  contains a polar group can be prepared with a high activity of polymerization by copolymerizing an olefin and a monomer that contains polar group in the presence of a metal catalyst of transition in which a cyclopentadienyl group has been introduced or other special ligands, without using radical polymerization or a Ziegler polymerization catalyst. Based on the finding, the present invention has been carried out.

Until now a method of selectively introduce the polar group at only one end of the polymer chain or within the main chain and at one end of the main chain. So, the present inventors have found a method of selectively introducing the polar group in just one end of the polymer chain or inside the chain main and at one end of the main chain, and have led to Carry out the present invention.

Object of the invention

An objective of the present invention is provide an olefin copolymer containing polar group that It has excellent adhesion properties to metals or polar resins and excellent compatibility with them, a procedure for prepare the copolymer, a thermoplastic resin composition that It contains the copolymer and uses thereof.

The olefin copolymer containing group polar according to the present invention is a copolymer of type branched comprising a constitutive unit represented by the following formula (1) and a constitutive unit represented by the following formula (4), and optionally a constitutive unit represented by the following formula (5), which has a molecular weight distribution (Mw / Mn) not exceeding 3, and that has an intensity ratio of T?? With with respect to Tαα (Tαβ / Tαα), as determined from a spectrum of 13 C-NMR of said copolymer, not exceeding 1.0:

one

in which R1 is an atom of hydrogen or a straight chain aliphatic hydrocarbon group or branched from 1 to 18 carbon atoms; R 5 is a group hydrocarbon; R 6 is a heteroatom or group containing a heteroatom; r is 0 or 1; Z is a polymeric segment obtained by any one of anionic polymerization, polymerization by ring opening and polycondensation; W is a hydroxyl group or an epoxy group; p is an integer from 1 to 3, q is 0, 1 or 2, and p + q ≤ 3; when p is 2 or 3, each -O-Z can be same or different, and in this case, if r is 0, -O-Z it can be attached to the same atom or to an atom different from R 5, and if r is 1, -O-Z can be attached to the same atom or to an atom other than R 6; when q is 2, each W can be same or different, and in this case, if r is 0, W can be attached to the same atom or an atom different from R 5, and if r is 1, W can be bound to the same atom or to an atom different from R 6; at case of p \ geq1 and q \ geq1, if r is 0, W and -O-Z they can be attached to the same atom or to an atom different from R 5, and if r is 1, W and -O-Z can be attached to the same atom or to an atom different from R 6; m is 0 or 1; n is an integer from 1 to 3; and when n is 2 or 3, each W can be same or different, and in this case, if m is 0, W can be attached to the same atom or to an atom different from R 5 and if m is 1, W it can be attached to the same atom or to an atom different from R 6.

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In the present invention, it is preferred that, in the formula (4), r be 0 and Z be a polymeric segment obtained by anionic polymerization.

In the present invention, it is preferred that, in the formula (4), Z is a polymeric segment obtained by ring opening or polycondensation polymerization.

The first reference embodiment of the process for preparing an olefin copolymer containing polar group comprises copolymerizing at least one α-olefin selected from α-olefins of 2 to 20 carbon atoms and at minus a monomer containing polar group selected from a monomer containing polar group represented by the following formula (7) and a monomer containing polar group represented by the following formula (8) in the presence of a catalyst comprising:

(A) a compound of a transition metal selected from group 3 (including lantanoid and actinoid) at group 10 of the periodic table, and

(B) at least one compound selected from:

(B-1) a oxy-organoaluminum compound,

(B-2) a compound that reacts with the compound (A) to form an ionic pair, and

(B-3) a compound of organoaluminum;

2

in which R3 is a group hydrocarbon; R 4 is a heteroatom or group that contains a heteroatom; r is 0 or 1; X is a polar group selected from a alcoholic hydroxyl group, a phenolic hydroxyl group, a group carboxylic acid, a carboxylic ester group, an anhydride group of acid, an amino group, an amide group, an epoxy group and a group mercapto; p is an integer from 1 to 3; when p is 2 or 3, each X it can be the same or different, and in this case, if r is 0, X can be bound to the same atom or to an atom different from R3, and if r is 1, X can be attached to the same atom or to an atom different from R 4;

3

in which R 7 is a link direct or an aliphatic hydrocarbon group of 1 or more atoms of carbon; R 8 is a hydrogen atom, a direct bond or a aliphatic hydrocarbon group of 1 or more carbon atoms; And it is a polar group containing O and / or N; m and n are each a number integer from 0 to 2, and m + n is not 0; and s is 0 or one.

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In the first reference embodiment of the process for preparing an olefin copolymer containing polar group, it is preferred that the transition metal compound (A) is represented by any one of the following formulas (11), (12), (13), (14), (15) and (16) and the group-containing monomer polar is a monomer containing polar group of formula (7) in the that X is -OH or an amino group;

4

in which M1 is an atom of transition metal of group 4 of the periodic table; R 25, R 26, R 27 and R 28 may be the same or different and are each a hydrogen atom, a group containing nitrogen, a phosphorus-containing group, a hydrocarbon group of 1 to 20 atoms carbon, a halogenated hydrocarbon group of 1 to 20 atoms of carbon, a group that contains oxygen, a group that contains sulfur, a group containing silicon or a halogen atom; from the groups indicated by R 25, R 26, R 27 and R 28, a part of the neighboring groups with each other may be united forming a ring together with the carbon atoms to which those groups are united; X 1 and X 2 can be the same or different and are each a hydrocarbon group of 1 to 20 atoms carbon, a halogenated hydrocarbon group of 1 to 20 atoms of carbon, a group that contains oxygen, a group that contains sulfur, a group containing silicon, a hydrogen atom or a halogen atom; and Y1 is a divalent hydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbon group divalent of 1 to 20 carbon atoms, a group that contains divalent silicon, a group containing divalent germanium, a group containing divalent tin, -O-, -CO-, -S-, -SO-, -SO 2 -, -Ge-, -Sn-, -NR 21 -, -P (R 21) -, -P (O) (R 21) -, -BR 21 - or -AlR 21 - (each R 21 it can be the same or different and it is a hydrocarbon group from 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms, a hydrogen atom, a halogen atom or a nitrogen compound moiety in which one or two groups hydrocarbons of 1 to 20 carbon atoms are attached to the atom from nitrogen);

5

in which M1 is an atom of transition metal selected from group 4 of the periodic table; Cp is a cyclopentadienyl group or its derivative that is linked with a π link to M 1; Z1 is a ligand that contains a oxygen atom, a sulfur atom, a boron atom or an element from group 14 of the periodic table; Y1 is a ligand that it contains an atom selected from a nitrogen atom, an atom of  phosphorus, an oxygen atom and a sulfur atom; and every X1 it can be the same or different and it is a hydrogen atom, an atom of halogen, a hydrocarbon group that has 20 or less atoms of carbon and may contain 1 or more double bonds, a silyl group which contains 20 or less silicon atoms, a germyl group that it contains 20 or less germanium atoms or a boronyl group that contains 20 or less atoms of boron;

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6

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in which M1 is an atom of transition metal selected from group 4 of the periodic table; R 11 to R 14, R 17 to R 20, and R 41 can be same or different and are each a hydrocarbon group of 1 to 40 carbon atoms, a halogenated hydrocarbon group from 1 to 40 carbon atoms, a group that contains oxygen, a group that contains sulfur, a group containing silicon, a halogen atom or a hydrogen atom; of the groups indicated by R 11, R 12, R 13, R 14, R 17, R 18, R 19, R 20 and R 41, a part of the neighboring groups with each other can be united forming a ring together with the carbon atoms to those groups are united (except one case in which all R 11, R 12, R 13, R 14, R 17, R 18, R 19, R 20 and R 41 are hydrogen atoms and a case in which R 12 or R 13 is a tert-butyl group and the rest of R 11, R 12, R 13, R 14, R 17, R 18, R 19, R 20 and R 41 are hydrogen atoms); X 1 and X 2 may be the same or different and are each a hydrocarbon group of 1 to 20 carbon atoms, a group halogenated hydrocarbon of 1 to 20 carbon atoms, a group that it contains oxygen, a group that contains sulfur, a group that it contains silicon, a hydrogen atom or a halogen atom; and Y 1 is a divalent hydrocarbon group of 1 to 20 atoms of carbon, a divalent halogenated hydrocarbon group from 1 to 20 carbon atoms, a group containing divalent silicon, a group containing divalent germanium, a group containing tin divalent, -O-, -CO-, -S-, -SO-, -SO_ {2} -, -Ge-, -Sn-, -NR 21 -, -P (R 21) -, -P (O) (R 21) -, -BR 21 - or -AlR 21 - (each R 21 can be the same or different and is a hydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms, a hydrogen atom, a halogen atom or a compound residue of nitrogen in which one or two hydrocarbon groups of 1 to 20 carbon atoms are attached to the atom of nitrogen);

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7

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in which M1 is an atom of transition metal selected from group 4 of the periodic table; R 11, R 12, R 41 and R 42 may be the same or different and are each a hydrocarbon group of 1 to 40 atoms carbon, a halogenated hydrocarbon group of 1 to 40 atoms of carbon, a group that contains oxygen, a group that contains sulfur, a group containing silicon, a halogen atom or a hydrogen atom; of the groups indicated by R 11, R 12, R 41 and R 42, a part of the neighboring groups each other can be united forming a ring together with the atoms carbon to which these groups are attached; X 1 and X 2 they can be the same or different and they are each a group hydrocarbon of 1 to 20 carbon atoms, a hydrocarbon group halogenated from 1 to 20 carbon atoms, a group that contains oxygen, a group that contains sulfur, a group that contains silicon, a hydrogen atom or a halogen atom; and Y1 is a divalent hydrocarbon group of 1 to 20 carbon atoms (when all R 11, R 12, R 41 and R 42 are hydrogen atoms, Y1 is not ethylene), a hydrocarbon group divalent halogenated from 1 to 20 carbon atoms, a group that contains divalent silicon, a group that contains germanium divalent, a group containing divalent tin, -O-, -CO-, -S-, -SO-, -SO 2 -, -Ge-, -Sn-, -NR 21 -, -P (R 21) -, -P (O) (R 21) -, -BR 21 - or -AlR 21 - (each R 21 it can be the same or different and it is a hydrocarbon group from 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms, a hydrogen atom, a halogen atom or a nitrogen compound moiety in which one or two groups hydrocarbons of 1 to 20 carbon atoms are attached to the atom from nitrogen);

8

in which M1 is an atom of transition metal selected from group 4 of the periodic table; R 41 and R 42 may be the same or different and are each a hydrocarbon group of 1 to 40 carbon atoms, a group halogenated hydrocarbon of 1 to 40 carbon atoms, a group that it contains oxygen, a group that contains sulfur, a group that it contains silicon, a halogen atom or a hydrogen atom; from the groups indicated by R 41 and R 42, a part of the neighboring groups can be joined together forming a ring together with the carbon atoms to which these groups are attached; X 1 and X 2 may be the same or different and are each a hydrocarbon group of 1 to 20 carbon atoms, a group halogenated hydrocarbon of 1 to 20 carbon atoms, a group that it contains oxygen, a group that contains sulfur, a group that it contains silicon, a hydrogen atom or a halogen atom; and Y 1 is a divalent hydrocarbon group of 1 to 20 atoms of carbon, a divalent halogenated hydrocarbon group from 1 to 20 carbon atoms, a group containing divalent silicon, a group containing divalent germanium, a group containing tin divalent, -O-, -CO-, -S-, -SO-, -SO_ {2} -, -Ge-, -Sn-, -NR 21 -, -P (R 21) -, -P (O) (R 21) -, -BR 21 - or -AlR 21 - (each R 21 can be the same or different and is a hydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms, a hydrogen atom, a halogen atom or a compound residue of nitrogen in which one or two hydrocarbon groups of 1 to 20 carbon atoms are attached to the atom of nitrogen);

9

in which M1 is an atom of transition metal selected from group 4 of the periodic table; R 11, R 12, R 15 to R 20, and R 42 may be same or different and are each a hydrocarbon group of 1 to 40 carbon atoms, a halogenated hydrocarbon group from 1 to 40 carbon atoms, a group that contains oxygen, a group that contains sulfur, a group containing silicon, a halogen atom or a hydrogen atom; of the groups indicated by R 11, R 12, R 15, R 16, R 17, R 18, R 19, R 20 and R 42, a part of the neighboring groups with each other can be united forming a ring together with the carbon atoms to those groups are united; X 1 and X 2 can be same or different and are each a hydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbon group from 1 to 20 carbon atoms, a group that contains oxygen, a group that contains sulfur, a group that contains silicon, an atom of hydrogen or a halogen atom; and Y1 is a group divalent hydrocarbon of 1 to 20 carbon atoms (when all R 11, R 12, R 15, R 16, R 17, R 18, R 19, R 20 and R 42 are hydrogen atoms, Y 1 is not is ethylene), a divalent halogenated hydrocarbon group from 1 to 20 carbon atoms, a group containing divalent silicon, a group that contains divalent germanium, a group that contains tin divalent, -O-, -CO-, -S-, -SO-, -SO_ {2} -, -Ge-, -Sn-, -NR 21 -, -P (R 21) -, -P (O) (R 21) -, -BR 21 - or -AlR 21 - (each R 21 can be the same or different and is a hydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms, a hydrogen atom, a halogen atom or a compound residue of nitrogen in which one or two hydrocarbon groups of 1 to 20 carbon atoms are attached to the atom of nitrogen).

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In the first reference embodiment of the process for preparing an olefin copolymer containing polar group, it is preferred that the transition metal compound (A) is represented by any one of the above formulas (11), (12), (13), (14), (15) and (16) and that the monomer it contains polar group be a monomer containing polar group of the formula (7) above in which X is -NR'R '' (R 'and R' 'can be the same or different and are each a hydrogen atom or a group I rent).

The procedure for preparing a copolymer of olefin containing polar group according to the present invention comprises copolymerizing at least one α-olefin selected from α-olefins of 2 to 20 carbon atoms and at minus a monomer containing polar group selected from a monomer containing polar group represented by the following formula (7), a monomer containing polar group represented by the following formula (8) and a macromonomer represented by the following formula (9) in the presence of a catalyst comprising:

(A) a compound of a transition metal selected from group 3 (including lantanoid and actinoid) at group 10 of the periodic table, and

(B) at least one compound selected from:

(B-1) a oxy-organoaluminum compound,

(B-2) a compound that reacts with the compound (A) to form an ionic pair, and

(B-3) a compound of organoaluminum;

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10

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in which R 5 is a group hydrocarbon; R 6 is a heteroatom or group containing a heteroatom; r is 0 or 1; Z is a polymeric segment obtained by any one of anionic polymerization, polymerization by ring opening and polycondensation; W is a hydroxyl group or an epoxy group; p is an integer from 1 to 3, q is 0, 1 or 2, and p + q ≤ 3; when p is 2 or 3, each -O-Z can be same or different, and in this case, if r is 0, -O-Z it can be attached to the same atom or to an atom different from R 5, and if r is 1, -O-Z can be attached to the same atom or to an atom other than R 6; when q is 2, each W can be same or different, and in this case, if r is 0, W can be attached to the same atom or to an atom different from R 5, and if r is 1, W it can be attached to the same atom or to an atom different from R 6; and in the case of p \ geq1 and q \ geq1, if r is 0, W and -O-Z can each be attached to the same atom or to an atom different from R 5, and if r is 1, W and -O-Z can each be attached to the same atom or to an atom different from R 6.

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The thermoplastic resin composition according to the The present invention contains the olefin copolymer containing polar group

The adhesive resin according to the present invention comprises the olefin copolymer containing polar group or the thermoplastic resin composition.

The compatibilizing agent according to the present invention comprises the olefin copolymer containing group polar or thermoplastic resin composition.

The resin modifier according to the present invention comprises the olefin copolymer containing group polar or thermoplastic resin composition.

The loading dispersing agent according to the present invention comprises the olefin copolymer containing group polar or thermoplastic resin composition.

The dispersing agent according to the present invention comprises the olefin copolymer containing group polar or thermoplastic resin composition.

The film or sheet according to the invention comprises the olefin copolymer containing polar group or the thermoplastic resin composition.

Detailed description of the invention

The olefin copolymer containing group polar, the process for preparing the copolymer, the composition of thermoplastic resin containing the copolymer and its uses according to The invention is described in detail hereinbelow. document.

Olefin copolymer containing polar group

The first reference embodiment of the olefin copolymer containing polar group comprises a unit constitutive represented by the following formula (1) (also called "constituent unit (1)" below in the this document), a constitutive unit represented by the following formula (2) (also called "constitutive unit (2) "below in this document) and a unit constitutive represented by the following formula (3) (also called "constitutive unit (3)" below in the present document).

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eleven

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In the above formulas, R1 and R2 they can be the same or different and are each a hydrogen atom  or a linear or branched chain aliphatic hydrocarbon group from 1 to 18 carbon atoms.

Examples of hydrocarbon groups linear or branched chain aliphatics of 1 to 18 atoms of carbon include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, pentyl, neopentyl, n-hexyl, 1-ethyl-1-methylpropyl, 1,1-diethylpropyl, 2-ethylhexyl, octyl, decyl and dodecyl. Of these, groups are preferred hydrocarbons of 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms

R 3 is a hydrocarbon group, such as a saturated or unsaturated aliphatic hydrocarbon group, a group alicyclic hydrocarbon or an aromatic hydrocarbon group.

The saturated or unsaturated hydrocarbon group it is, for example, a linear chain hydrocarbon group or branched from 1 to 20 carbon atoms, and examples thereof include methylene, ethylene, trimethylene, methylethylene, tetramethylene, methyltrimethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene, heptadecamethylene, octadecamethylene, nonadecamethylene and eicosamethylene.

The alicyclic hydrocarbon group is preferably a group that has an alicyclic structure such as part of its structure and that has 3 to 20 carbon atoms, and Examples thereof include cyclopropylene, cyclopentylene, cyclohexylene and cyclooctylene.

The aromatic hydrocarbon group is preferably a group having an aromatic ring as part of  its structure and that has 6 to 20 carbon atoms, and examples thereof include -Ph-, -Ph-CH2 -, -Ph- (CH 2) 2 -, -Ph- (CH 2) 3 -, -Ph- (CH 2) 6 -, -Ph- (CH 2) 10 -, -Ph- (CH 2) 11 -, -Ph- (CH 2) 12 - and -Ph- (CH 2) 14 -.

When r is 1 and R 4 is attached to R 3, the Valence of R3 is 2. When r is 0 and each X of p is attached to R 3, the valence of R 3 is p + 1.

R 4 is a heteroatom or a group that It contains a heteroatom.

The heteroatom is, for example, an atom of oxygen, a nitrogen atom or a sulfur atom, preferably  an oxygen atom or a nitrogen atom.

The group containing a heteroatom is, for example, a group containing an oxygen atom, a nitrogen atom or a sulfur atom, and examples thereof include -O-, -C (= O) -, -C (= O) O-, -OC (= O) O-, -C (= O) NH-, -NH-, 12 (tertiary amine), -S-, and aliphatic, alicyclic or aromatic hydrocarbon groups containing these groups.

Specifically, structures can be mentioned such as those shown by way of example with respect to Last described monomers containing polar group.

The heteroatom in R4 or the carbon atom to which the heteroatom is attached is preferably attached to R3, and examples of such structures include -R3 -O-R-X, -R3 -C (= O) -R-X, -R3 -C (= O) O-R-X, -R3 -OC (= O) O-R-X, -R3 -C (= O) NH-R-X and -R 3 -S-R-X (R it is methylene, phenylene or cyclohexylene).

When R 4 contains a carbon atom, the number of carbon atoms to form R 4 is in the range of preferably from 1 to 20, more preferably from 1 to 10, particularly preferably from 1 to 5.

r is 0 or 1. When r is 0, X is attached to one any of the carbon atoms to form R3. When r is 1, X is attached to any one of the carbon atoms to form R 4.

X is a polar group selected from a group alcoholic hydroxyl, a phenolic hydroxyl group, an acidic group carboxylic, a carboxylic ester group, an anhydride group of acid, an amino group (primary, secondary and tertiary), a group Amide, an epoxy group and a mercapto group.

When X is an alcoholic hydroxyl group, the olefin copolymer containing polar group is excellent in coating properties, hydrophilic surface properties (anti-fogging properties), anti-static properties, adhesion properties to polar resins (urethane resin, resin epoxy, etc.), charge dispersibility properties, of moisture absorption, gas barrier properties (in the case of high content), water absorption properties (in the case of a high content of alcoholic hydroxyl group), water dispersibility and oil resistance (in the case of a high content of alcoholic hydroxyl group).

When X is a phenolic hydroxyl group, the olefin copolymer containing polar group is excellent in adhesion properties to polar resins (aromatic polymer, phenolic resin, etc.) and compatibility with polar resins (aromatic polymer, phenolic resin, etc.).

When X is a carboxyl group, the copolymer of olefin containing polar group is excellent in properties of adhesion to metals, dispersibility in water (particularly in the metal salt case), pigment dispersibility, dispersibility of load and resistance to oil (in the case of a high content in carboxyl group).

When X is a carboxylic ester group, the olefin copolymer containing polar group is excellent in adhesion properties to polar resins (nylon, EVOH, etc.), compatibility with polar resins (nylon, EVOH, etc.) and hydrophilic surface properties.

When X is an epoxy group, the copolymer of olefin containing polar group is excellent in properties of adhesion to metals, adhesion properties to polar resins (polyester, epoxy resin, nylon, EVOH, urea resin, etc.), compatibility with polar resins (polyester, epoxy resin, nylon, EVOH, urea resin, etc.), pigment dispersibility and coating properties

When X is an acid anhydride group, the olefin copolymer containing polar group is excellent in metal adhesion properties, resin adhesion properties polar (nylon, EVOH, polyester, etc.), resin compatibility polar (nylon, EVOH, polyester, etc.), dispersibility of pigment, charge dispersibility and water dispersibility (particularly in the case of metal salt).

When X is an amino group, the copolymer of olefin containing polar group is excellent in properties of adhesion to polar resins (epoxy resin, polyketone, polyurethane, etc.), coating properties, properties antifungal (in the case of ammonium salt), properties of ion exchange (in the case of ammonium salt), properties surface hydrophilic (particularly in the case of salt from ammonium), antistatic properties (particularly in the case of ammonium salt), pigment dispersibility and dispersibility of charge (particularly in the case of ammonium salt).

When X is an amide group, the copolymer of olefin containing polar group is excellent in properties of adhesion to polyamide and compatibility with polyamide.

When X is a mercapto group, the copolymer of olefin containing polar group is excellent in properties of adhesion to transition metals from the back of the table periodic such as Fe, Cu, Co, Ni, Cd and Zn, compatibility with polyamide and polyester, and polyamide adhesion properties and polyester.

p is an integer from 1 to 3, and when p is 2 or 3, each X can be the same or different. When p is 2 or 3 and r is 0, X can be attached to the same atom or to an atom different from R3, and when p is 2 or 3 and r is 1, X can be attached to it atom or to an atom other than R 4.

In the olefin copolymer containing group polar, the constitutive unit (1), the constitutive unit (2) and the constitutive unit (3) are usually randomly attached.

Copolymer composition

In the olefin copolymer containing group polar, the molar ratio ((1) + (2) :( 3)) among the total unit constitutive (1) and constitutive unit (2), and unity constitutive (3) is in the range of usually 99.99: 0.01 a 0.01: 99.99, preferably 99.95: 0.05 to 10:90, more preferably from 99.9: 0.1 to 30:70.

The molar ratio ((1) :( 2)) between the unit constitutive (1) and the constitutive unit (2) is in the range from usually 99.99: 0.01 to 0.01: 99.99, preferably from 99: 1 to 1:99, more preferably from 90:10 to 10:90.

The olefin copolymer containing group polar can contain two or more kinds of constituent units (1), may contain two or more classes of the constituent units (2), and may contain two or more kinds of units constitutive (3).

Other copolymerizable components

The olefin copolymer containing group polar may contain constituent units other than the unit constitutive (1), constitutive unit (2) and unity constitutive (3), within limits not harmful to Objectives of the present invention.

Examples of the constitutive units that may be contained include constituent units derived from cyclic olefins other than the polar group containing monomer represented by formula (8), unconjugated polyenes, ethylenically unsaturated compounds containing hydroxyl group, ethylenically unsaturated compounds containing amino group, ethylenically unsaturated compounds containing epoxy group, aromatic vinyl compounds, unsaturated carboxylic acids and its derivatives, vinyl ester compounds, and chloride vinyl.

When these constituent units are contained, the amount thereof is not more than 30 mol%, preferably no more than 20 mol%, more preferably no more 10% in moles, based on all constituent units to constitute the olefin copolymer containing group polar.

Copolymer properties

The weight average molecular weight (Mw) of olefin copolymer containing polar group is in the range usually 500 to 2,000,000, preferably 800 to 1,500,000, more preferably 1,000 to 1,300,000, and the molecular weight distribution (Mw / Mn) thereof is usually not more than 3, preferably not more than 2.8, more preferably not more of 2.7.

When the molecular weight distribution (Mw / Mn) is not more than 3, the olefin copolymer containing polar group It is excellent in the orientation of polar groups towards interface between said copolymer and a polar material and has excellent adhesion properties to a polar material and excellent compatibility with a polar material.

Mw and Mw / Mn were determined from data obtained by measuring at 140 ° C in a solvent of orthodichlorobenzene using CPG (permeation chromatography in gel).

Intensity ratio (T?? / T??) Of T?? With with respect to T? in the spectrum of 13 C-NMR of the olefin copolymer containing polar group is not more than 1.0, preferably not more than 0.8, more preferably not more than 0.5.

When the intensity ratio (Tαβ / Tαα) is not more than 1.0, the copolymer Olefin containing polar group is excellent in orientation of the polar groups towards the interface between said copolymer and a polar material

Tαα and Tαβ in the 13 C-NMR spectrum are each an intensity peak of CH2 present in the constituent unit derived from a α-olefin of 4 or more carbon atoms, and such As shown below, they mean two classes of CH_ {2} different in position with respect to tertiary carbon.

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13

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Intensity ratio Tαβ / Tαα can be determined from the Following way.

A spectrum of 13 C-NMR of the olefin copolymer containing polar group by using, for example, a device of NMR measurement from Japan Electron Optics Laboratory JEOL-GX270. The measurement is performed using a mixed solution of hexachlorobutadiene / d6-benzene (2/1, by volume) which has a sample concentration of 5% in weight under the conditions of 67.8 MHz, 25 ° C and d6-benzene as standard (128 ppm). The spectrum of 13 C-NMR measured is analyzed according to the proposals by Lindemann Adams (Analysis Chemistry 43, p. 1245 (1971)) and J.C. Randall (Review Macromolecular Chemistry Physics, C29, 201 (1989)) to determine the intensity ratio T?? / (T?? + T??).

Examples of the olefin copolymer containing polar group according to the first reference embodiment include the following olefin copolymers containing polar group (I) a (SAW).

Olefin copolymer containing polar group (I)

In the olefin copolymer containing group polar (I), it is preferred that R 1 in formula (1) and R 2 in the formula (2) is each a hydrogen atom or a methyl group and R1 and R2 are equal to each other.

In the olefin copolymer containing group polar (I), a preferred combination of the constituent unit (1), the constitutive unit (2) and the constitutive unit (3) is, by example, a combination of a constituent unit selected from the examples of the constituent units (1) shown in the table 1 and a constituent unit selected from the examples of the constituent units (3) shown in table 1. Examples specific to such combinations include combinations of 1-A, 1-B, 1-C, 1-D, 1-E, 1-F, 1-G, 1-H, 1-I, 1-J, 1-K, 1-L, 1-M, 2-A, 2-B, 2-C, 2-D, 2-E, 2-F, 2-G, 2-H, 2-I, 2-J, 2-K, 2-L and 2-M.

The above combinations are those in the that R1 and R2 are equal to each other, and the units Constitutive (1) include constitutive units (2).

In the combination examples mentioned previously, the numbers indicate examples of the units constitutive (1), and the letters indicate examples of the units constitutive (3).

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TABLE 1

14

fifteen

The olefin copolymer containing group polar (I) is excellent in material adhesion properties polar such as metals and polar resins, compatibility and flexibility.

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Olefin copolymer containing polar group (II)

In the olefin copolymer containing group polar (II), R1 in formula (1) and R2 in formula (2) They are different from each other.

In the olefin copolymer containing group polar (II), a preferred combination of the constitutive unit (1), the constitutive unit (2) and the constitutive unit (3) is, by example, a combination of a constituent unit selected from the examples of the constituent units (1) and the units constitutive (2) shown in table 2 and a constitutive unit selected from the examples of the constituent units (3) shown in table 2. Specific examples of such combinations include combinations of 1-A, 1-B, 1-C, 1-D, 1-E, 1-F, 1-G, 1-H, 1-I, 1-J, 1-K, 1-L, 1-M, 2-A, 2-B, 2-C, 2-D, 2-E, 2-F, 2-G, 2-H, 2-I, 2-J, 2-K, 2-L, 2-M, 3-A, 3-B, 3-C, 3-D, 3-E, 3-F, 3-G, 3-H, 3-I, 3-J, 3-K, 3-L, 3-M, 4-A, 4-B, 4-C, 4-D, 4-E, 4-F, 4-G, 4-H, 4-I, 4-J, 4-K, 4-L, 4-M, 5-A, 5-B, 5-C, 5-D, 5-E, 5-F, 5-G, 5-H, 5-I, 5-J, 5-K, 5-L, 5-M, 6-A, 6-B, 6-C, 6-D, 6-E, 6-F, 6-G, 6-H, 6-I, 6-J, 6-K, 6-L, 6-M, 7-A, 7-B, 7-C, 7-D, 7-E, 7-F, 7-G, 7-H, 7-I, 7-J, 7-K, 7-L and 7-M.

In the combination examples mentioned previously, the numbers indicate examples of the units constitutive (1) and (2), and the letters indicate examples of constitutive units (3).

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TABLE 2

16

17

It is preferred that the olefin copolymer which contains polar group (II) does not contain any other components copolymerizable mentioned above and that is formed from of only the constitutive unit (1), the constitutive unit (2) and the constitutive unit (3). Especially when X is a group alcoholic hydroxyl, a phenolic hydroxyl group or an amino group, the olefin copolymer containing polar group is formed of particularly preferable from only the unit constitutive (1), constitutive unit (2) and unity constitutive (3).

The olefin copolymer containing group Polar (II) is excellent in material adhesion properties polar such as metals and polar resins, compatibility and flexibility.

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Olefin copolymer containing polar group (III)

In the olefin copolymer containing group polar (III), R 3 in formula (3) is a hydrocarbon group of 11 or more carbon atoms.

In the olefin copolymer containing group polar (III), a preferred combination of the constitutive unit (1), the constitutive unit (2) and the constitutive unit (3) is, by example, a combination of a constituent unit selected from the examples of the constituent units (1) and (2) shown in the table 3 and a constituent unit selected from the examples of the constituent units (3) shown in table 3. Examples specific to such combinations include combinations of 1-A, 1-B, 1-C, 2-A, 2-B, 2-C, 3-A, 3-B, 3-C, 4-A, 4-B, 4-C, 5-A, 5-B, 5-C, 6-A, 6-B, 6-C, 7-A, 7-B, 7-C, 8-A, 8-B, 8-C, 9-A, 9-B, 9-C, 10-A, 10-B and 10-C

In table 3, the description of a class of a constitutive unit in the column of the constitutive units (1) and (2) means that R1 and R2 are equal to each other, and the description of three classes of constituent units in the column of the constituent units (1) and (2) means that two classes of the constituent units (1) or the constitutive units (2).

In the combination examples mentioned previously, the numbers indicate examples of the units constitutive (1) and (2), and the letters indicate examples of constitutive units (3).

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TABLE 3

18

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It is preferred that the olefin copolymer which contains polar group (III) does not contain any other components copolymerizable mentioned above and is formed from only the constitutive unit (1), the constitutive unit (2) and the constitutive unit (3). Especially when X is a group alcoholic hydroxyl, a phenolic hydroxyl group or an amino group, the olefin copolymer containing polar group is formed of particularly preferable from only the unit constitutive (1), constitutive unit (2) and unity constitutive (3).

The olefin copolymer containing group Polar (III) is excellent in material adhesion properties polar such as metals and polar resins and compatibility.

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Olefin copolymer containing polar group (IV)

In the olefin copolymer containing group polar (IV), X in formula (3) is a polar group selected from a phenolic hydroxyl group, a carboxylic ester group, a group acid anhydride, an amino group, an amide group, an epoxy group and a mercapto group.

In the olefin copolymer containing group polar (IV), a preferred combination of the constitutive unit (1), the constitutive unit (2) and the constitutive unit (3) is, by example, a combination of a constituent unit selected from the examples of the constituent units (1) shown in the table 4 and a constituent unit selected from the examples of the constituent units (3) shown in table 4. Examples specific to such combinations include combinations of 1-A, 1-B, 1-C, 1-D, 2-A, 2-B, 2-C, 2-D, 3-A, 3-B, 3-C, 3-D, 4-A, 4-B, 4-C, 4-D, 5-A, 5-B, 5-C, 5-D, 6-A, 6-B, 6-C, 6-D, 7-A, 7-B, 7-C, 7-D, 8-A, 8-B, 8-C, 8-D, 9-A, 9-B, 9-C, 9-D, 10-A, 10-B, 10-C and 10-D.

The above combinations are those in the that R1 and R2 are equal to each other, and the units Constitutive (1) include constitutive units (2).

In the combination examples mentioned previously, the numbers indicate examples of the units constitutive (1), and the letters indicate examples of the units constitutive (3).

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TABLE 4

19

The olefin copolymer containing group polar (IV) according to the invention is excellent in properties of adhesion to polar materials such as metals and polar resins and compatibility.

Olefin copolymer containing polar group (V)

In the olefin copolymer containing group polar (V), R 1 in the formula (1) and R 2 in the formula (2) they are each a hydrocarbon group of 2 or more carbon atoms, preferably from 2 to 18 carbon atoms, and the crystallinity of the copolymer, as determined by ray diffractometry X, is not less than 10%, preferably 15 to 80%, more preferably from 20 to 70%.

Crystallinity can be measured by X-ray diffractometry (according to S.L. AGGARWAL, J. Polymer Sci., 18,  17 (1955)).

The stereoregularity (isotacticity) of olefin copolymer containing polar group (V) is usually not less than 20%, preferably 30 to 100%, more preferably from 40 to 100%.

In the olefin copolymer containing group polar (V), a preferred combination of the constituent unit (1), the constitutive unit (2) and the constitutive unit (3) is, by example, a combination of a constituent unit selected from the examples of the constituent units (1) shown in the table 5 and a constituent unit selected from the examples of the constituent units (3) shown in table 5. Examples specific to such combinations include combinations of 1-A, 1-B, 1-C, 1-D, 1-E, 1-F, 1-G, 1-H, 1-I, 1-J, 1-K, 1-L, 1-M, 2-A, 2-B, 2-C, 2-D, 2-E, 2-F, 2-G, 2-H, 2-I, 2-J, 2-K, 2-L and 2-M.

The above combinations are those in the that R1 and R2 are equal to each other, and the units Constitutive (1) include constitutive units (2).

In the combination examples mentioned previously, the numbers indicate examples of the units constitutive (1), and the letters indicate examples of the units constitutive (3).

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TABLE 5

twenty

twenty-one

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The olefin copolymer containing group Polar (V) is excellent in material adhesion properties polar such as metals and polar resins, compatibility and rigidity.

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Olefin copolymer containing polar group (VI)

In the olefin copolymer containing group polar (VI), R1 in formula (1) and R2 in formula (2) they are each a hydrocarbon group of 2 or more carbon atoms, preferably from 2 to 18 carbon atoms, and the crystallinity of the copolymer, as determined by ray diffractometry X, is less than 10%, preferably not more than 5%, more preferably not more than 2%.

It is preferred that the olefin copolymer which contains polar group (VI) does not contain any other components copolymerizable mentioned above and that is formed from of only the constitutive unit (1), the constitutive unit (2) and the constitutive unit (3). Especially when X is a group alcoholic hydroxyl, a phenolic hydroxyl group or an amino group, the olefin copolymer containing polar group is formed of particularly preferable from only the unit constitutive (1), constitutive unit (2) and unity constitutive (3).

In the olefin copolymer containing group polar (VI), a preferred combination of the constituent unit (1), the constitutive unit (2) and the constitutive unit (3) is, by example, a combination of a constituent unit selected from the examples of the constituent units (1) shown in the table 6 and a constituent unit selected from the examples of the constituent units (3) shown in table 6. Examples specific to such combinations include combinations of 1-A, 1-B, 1-C, 1-D, 1-E, 1-F, 1-G, 1-H, 1-I, 1-J, 1-K, 1-L, 1-M, 2-A, 2-B, 2-C, 2-D, 2-E, 2-F, 2-G, 2-H, 2-I, 2-J, 2-K, 2-L and 2-M.

The above combinations are those in the that R1 and R2 are equal to each other, and the units Constitutive (1) include constitutive units (2).

In the combination examples mentioned previously, the numbers indicate examples of the units constitutive (1), and the letters indicate examples of the units constitutive (3).

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TABLE 6

22

2. 3

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The olefin copolymer containing group Polar (VI) is excellent in material adhesion properties polar such as metals and polar resins, compatibility, stickiness and flexibility.

The olefin copolymer containing group Polar of the invention is an olefin copolymer containing branched-type polar group comprising a constitutive unit represented by the following formula (1) and a unit constitutive represented by the following formula (4) (also called "constituent unit (4)), and optionally a unit constitutive represented by the following formula (5) (also called "constitutive unit (5)).

24

The constitutive unit represented by the formula (1) is identical to the constituent unit (1) mentioned previously.

In formulas (4) and (5), R 5 is a group hydrocarbon, such as a saturated hydrocarbon group or unsaturated, an alicyclic hydrocarbon group or a group aromatic hydrocarbon, and examples of such groups hydrocarbons include the same groups as described above with respect to R 3 in the formula (3).

In formula (4), when r is 1 and R 6 is bound to R 5, the valence of R 5 is 2. When r is 0 and each -O-Z of p or each W of q is attached to R5, the Valence of R 5 is p + q + 1.

In formula (5), when m is 1 and R 6 is bound to R 5, the valence of R 5 is 2. When m is 0 and each W of n is attached to R 5, the valence of R 5 is n + 1.

Although R 5 in the formula (4) and R 5 in the formula (5) may be the same or different, preferably they are equal to each other.

In formulas (4) and (5), R 6 is a heteroatom or a group containing a heteroatom, and examples of heteroatoms and groups containing the heteroatom include the same atoms and groups as described above with with respect to R 4 in the formula (3).

In the formula (4), the heteroatom in R 6 or the carbon atom to which the heteroatom is attached is attached preferably at R 5, and examples of such structures include -R 5 -O-R-O-Z, -R 5 -C (= O) -R-O-Z, -R 5 -C (= O) O-R-O-Z, -R 5 -OC (= O) O-R-O-Z, -R 5 -C (= O) NH-R-O-Z Y -R 5 -S-R-O-Z (R is methylene, phenylene or cyclohexylene). The above examples are those in which p is 1 and q is 0 in formula (4), and what The same should apply to other cases.

In the formula (5), the heteroatom in R 6 or the carbon atom to which the heteroatom is attached is attached preferably at R 5, and examples of such structures include -R 5 -O-R-W, -R 5 -C (= O) -R-W, -R 5 -C (= O) O-R-W, -R 5 -OC (= O) O-R-X, -R 5 -C (= O) NH-R-W and -R 5 -S-R-W (R it is methylene, phenylene or cyclohexylene). The above examples are those in which n is 1 in formula (5), and the same must apply in other cases.

When R 6 contains a carbon atom in formulas (4) and (5), the number of carbon atoms to form R 6 is in the range of preferably 1 to 20, plus preferably from 1 to 10, particularly preferably from 1 to 5

Although R 6 in the formula (4) and R 6 in the formula (5) may be the same or different, preferably they are equal to each other.

In formula (4), r is 0 or 1. When r is 0, -O-Z is attached to any one of the atoms of carbon to form R5. When r is 1, -O-Z is attached to any one of the carbon atoms to form R 6.

In formula (5), m is 0 or 1. When m is 0, W is attached to any one of the carbon atoms to form R 5. When m is 1, W is attached to any one of the atoms of carbon to form R 6.

In formula (4), Z is a polymeric segment obtained by anionic polymerization, polymerization by ring opening or polycondensation.

Examples of polymer segments include segments obtained by anionic polymerization of one or more selected monomers of methyl methacrylate, methacrylate ethyl, butyl acrylate, acrylonitrile and acrylamide, segments obtained by lactone ring opening polymerization, lactide, siloxane, lactam, cyclic ether, oxazoline, oxide ethylene, propylene oxide, etc., and segments obtained by polycondensation of monomers, such as polycarboxylic acid and polyhydric alcohol, polycarboxylic acid and polyamine, or acid hydroxycarboxylic.

Examples of polar monomers used in the Polymeric segment formation include:

esters of (meth) acrylic acid, such as monoesters of monovalent alcohols and acrylic acid or acid methacrylic specifically

methyl acrylate, methyl methacrylate, ethyl acrylate, propyl methacrylate, butyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, Stearyl methacrylate, acrylate 1,1,1,3,3,3-hexafluoroisopropyl methacrylate 1,1,1,3,3,3-hexafluoroisopropyl acrylate 2,2,2-trifluoroethyl methacrylate 2,2,2-trifluoroethyl acrylate 1H, 1H, 2H, 2H-heptadecafluorodecyl, acrylate allyl, allyl methacrylate, cyclohexyl methacrylate, acrylate glycidyl, glycidyl methacrylate, acrylate tetrahydrofurfuryl, benzyl acrylate and methacrylate β-phenylethyl;

monoesters of divalent alcohols with a terminal end protected by an ether and acrylic acid bond or methacrylic acid, such as acrylate 2-methoxyethyl methacrylate 2-ethoxyethyl acrylate 2-phenoxyethyl acrylate 2-dicyclopentenyloxyethyl, methacrylate 1-methoxy-2-propyl, 3-methoxypropyl acrylate, methacrylate 4-ethoxybutyl acrylate 6-methoxyhexamethyl acrylate Methoxyethylene Glycol, Phenoxypropylene Glycol Methacrylate, ethoxytrypropylene glycol methacrylate, acrylate ethoxypolyethylene glycol and methoxy polypropylene glycol methacrylate;

polyvalent esters of a divalent alcohol or more and acrylic acid or methacrylic acid, such as diacrylate of ethylene glycol, ethylene glycol dimethacrylate, diacrylate propylene glycol, propylene glycol dimethacrylate, dimethacrylate 1,3-propanediol, diacrylate 1,4-butanediol, dimethacrylate 1,6-hexanediol, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, diethylene glycol diacrylate, dipropylene glycol dimethacrylate, dimethacrylate triethylene glycol, tripropylene glycol diacrylate, diacrylate polyethylene glycol, polypropylene glycol diacrylate, dimethacrylate polypropylene glycol, glycerin triacrylate, trimethacrylate glycerin, pentaerythritol tetramethacrylate, hexaacrylate dipentaerythritol, trimethylolpropane triacrylate, triacrylate poly (ethylene oxide) triol, poly (oxide of triacrylate) propylene) triol and poly (oxide oxide trimethacrylate) propylene) triol;

esters of alcohols having an ester and acrylic or methacrylic acid linkage, such as 2-benzoyloxyethyl acrylate, 2-benzoyloxyethyl methacrylate, 2-acetyloxy acrylate, 5-tetrahydrofurfuryloxycarbonylpentyl acrylate, 5-tetrahydrofurfurylxyl 2-methacryloxyl methacrylate, 2,6,6-tetramethyl-4-oxy-5-oxa-heptane-1,7-
say it

esters of alcohols having an acetal bond cyclic and acrylic acid or methacrylic acid, such as methacrylate from 2-tert-butyl-1,3-dioxycyclopentane-2'-yl and acrylate of 2-tert-Butyl-5-ethyl-5-vinylcarbonyloxymethyl-1,3-dioxycyclohexane-2 '(2) -yl;

esters of oxisuccinimide and acrylic acid or methacrylic, such as N-oxysuccinimido acrylate and N-oxysuccinimido methacrylate;

esters of an alcohol having an amino group secondary and acrylic acid or methacrylic acid, such as acrylate of 2-dimethylaminoethyl and methacrylate 2-ethylpropylaminoethyl; Y

esters of an alcohol that has a cyano group and acrylic acid or methacrylic acid, such as acrylate 2-cyanoethyl and methacrylate 2-cyanopropyl.

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Examples of (meth) acrylonitriles include acrylonitrile and methacrylonitrile.

Acrylamides include acrylamide, acrylamides N-monosubstituted or N, N-disubstituted, for example,

acrylamide;

N-monosubstituted acrylamides, such as N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-Butylacrylamide, N-octylacrylamide, N-phenylacrylamide, N-glycidyl acrylamide and N, N'-ethylenebisacrylamide;

N, N-disubstituted monoacrylamides, such as N, N-dimethylacrylamide, N-ethyl-N-methylacrylamide, N, N-diethylacrylamide, N, N-di-n-propylacrylamide, N, N-dioctylacrylamide, N, N-diphenylacrylamide , N-ethyl-N-glycidyl acrylamide, N, N-diglycidyl acrylamide, N-methyl-N- (4-glycidyloxybutyl) acrylamide, N-methyl-N- (5-glycidyloxypentyl) acrylamide, N-methyl-N- (6- glycidyloxyhexyl) acrylamide, N-acryloylpyrrolidine, N-acryloyl-L-prolinemethyl ester, N-acryloylpiperidine, N-acryloyl
morpholine and 1-acryloylimidazole; Y

bisacrylamides N, N'-disubstituted, such as N, N'-diethyl-N, N'-ethylenebisacrylamide, N, N'-dimethyl-N, N'-hexamethylene bisacrylamide  and di (N, N'-ethylene) bisacrylamide.

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Examples of vinylpyridines include pyridines vinyl- or isopropenyl-substituted, such as 2-vinylpyridine, 2-isopropenylpyridine and 4-vinylpyridine.

Examples of Maleimide N-substituted include:

N-rest maleimides aliphatic-substituted, such as N-methylmaleimide and N-ethylmaleimide; Y

N-rest maleimides aromatic-substituted, such as N-phenylmaleimide and N- (4-methylphenyl) maleimide.

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Examples of vinyl ketones include: methyl vinyl ketone, isopropenyl methyl ketone, ethyl vinyl ketone, ethyl Isopropenyl ketone, butyl vinyl ketone and phenyl vinyl ketone.

Examples of styrene derivatives include: p-methoxycarbonylstyrene, p-tert-butoxycarbonylstyrene and p-cyano styrene.

Examples of the polar monomer include compounds of alkylene oxide, for example, epoxy compounds, such as ethylene oxide, propylene oxide, 1,2-butylene, 2,3-butylene oxide, styrene oxide, cyclohexene oxide, epichlorohydrin, epibromhydrin, methylglycidyl ether, allylglycidyl ether and phenylglycidyl ether. Of these, ethylene oxide, oxide are preferred of propylene, 1,2-butylene oxide and styrene Highly preferable are propylene oxide and oxide of ethylene. Propylene oxide is extremely preferred.

Of these, polymer segments are preferred obtained by anionic ester polymerization (meth) acrylics and polymeric segments obtained by ring opening polymerization of ethylene oxide or oxide of propylene.

There is no specific limitation on the molecular weight of the polymer segment, and for example, the weight Average molecular weight is in the range of 200 to 1,000,000, preferably from 500 to 100,000.

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When Z is poly (ethylene oxide) or poly (propylene oxide), the olefin copolymer containing polar group is excellent in coating properties, surface hydrophilic properties (anti-fogging properties), antistatic properties, polar resin adhesion properties (urethane resin, epoxy resin, etc.), compatibility with polar resins, moisture absorption properties, water absorption properties (in the case of a high Z content), water dispersibility and oil resistance (in the case of a high content of
Z).

When Z is PMMA, the olefin copolymer that Contains polar group is excellent in surface hardness, properties  adhesion to metals, pigment dispersibility, dispersibility loading, oil resistance (in the case of a high content of Z), adhesion properties to polar resins (acrylic resin, Nylon, EVOH, etc.) and compatibility with polar resins.

When Z is polyacrylonitrile or polyacrylamide, the olefin copolymer containing polar group is excellent in surface hardness, surface hydrophilic properties (anti-fogging properties), anti-static properties, coating properties, metal adhesion properties, adhesion properties to polar resins (polyacrylonitrile, polyacrylamide, polyamide, polyester, etc.), compatibility with polar resins, water dispersibility, biocompatibility, stimulation response, moisture absorption properties and water absorption properties.

When Z is poly (ethyl methacrylate) or poly (butyl acrylate), the olefin copolymer that Contains polar group is excellent in adhesion properties to metals, adhesion properties to polar resins (resin acrylic, nylon, EVOH, etc.), resin compatibility polar and oil resistance.

When Z is polyamide (including polymer of lactam ring opening), the olefin copolymer that Contains polar group is excellent in adhesion properties to polar resins (polyamide, etc.), compatibility with resins polar, gas barrier properties and resistance to oil.

When Z is polyester (including polymer of lactam ring opening), the olefin copolymer that Contains polar group is excellent in adhesion properties to polar resins (polyester, etc.), compatibility with resins polar and gas barrier properties.

In formula (4), p is an integer from 1 to 3, and when p is 2 or 3, each -O-Z can be equal or different. When p is 2 or 3 and r is 0, -O-Z can be bound to the same atom or to an atom different from R5. When  p is 2 or 3 and r is 1, -O-Z can be attached to the same atom or an atom different from R 6.

In formulas (4) and (5), W is a group hydroxyl or an epoxy group.

Although W in the formula (4) and W in the formula (5) they can be the same or different, they are preferably the same between yes.

In formula (4), q is 0, 1 or 2, and when q is 2, each W can be the same or different. When q is 2 and r is 0, W it can be attached to the same atom or to an atom different from R5. When q is 2 and r is 1, W can be attached to the same atom or to a atom different from R 6.

In the case of p \ geq1 and q \ geq1, when r is 0, W and -O-Z can each be attached to it atom or to an atom other than R 5, and when r is 1, W and -O-Z can each be attached to the same atom or to a different atom of R 6, and

p + q \ leq 3.

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In formula (5), n is an integer from 1 to 3, and when n is 2 or 3, each W can be the same or different. When n is 2 or 3 and m is 0, W can be attached to the same atom or to an atom different from R 5. When n is 2 or 3 and m is 1, W can be bound to the same atom or to an atom different from R 6.

In the olefin copolymer containing group polar of the invention, the constituent unit (1), the unit constitutive (4), and optionally, the constitutive unit (5) are usually joined at random.

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Copolymer composition

In the olefin copolymer containing group polar of the invention, the molar ratio ((1) :( 4) + (5)) between the unit constitutive (1) and the total constitutive unit (4) and the constitutive unit (5) is in the range of usually 99.99: 0.01 to 0.01: 99.99, preferably 99.95: 0.05 to 10:90, more preferably from 99.9: 0.1 to 30:70. The molar ratio ((4) :( 5)) between the constitutive unit (4) and the constitutive unit (5) is in the range of usually 100: 0 to 0.01: 99.99, preferably of 100: 0 to 1:99, more preferably from 100: 0 to 10:90.

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The olefin copolymer containing group polar of the invention may contain two or more kinds of constituent units (1), may contain two or more kinds of constitutive units (4), and may contain two or more kinds of the constituent units (5).

In the present invention, a combination preferred of the constitutive unit (1), the constitutive unit (4) and the constituent unit (5) is, for example, a combination of a constitutive unit selected from the unit examples constitutive (1) shown in table 7, a constitutive unit selected from the examples of the parts -R 5 - (R 6) r -O- and examples of the parts Z of constituent units (4) shown in table 7, and a constituent unit selected from the examples of the constituent units (5) shown in table 7. Examples Specific to such combinations include combinations of:

1-A-Z1-a, 1-A-Z2-a, 1-A-Z3-a, 1-A-Z4-a, 1-A-Z5-a, 1-A-Z6-a, 1-A-Z7-a, 1-B-Z1-b, 1-B-Z2-b, 1-B-Z3-b, 1-B-Z4-b, 1-B-Z5-b, 1-B-Z6-b, 1-B-Z7-b, 1-C-Z1-c, 1-C-Z2-c, 1-C-Z3-c, 1-C-Z4-c, 1-C-Z5-c, 1-C-Z6-c, 1-C-Z7-c,

2-A-Z1-a, 2-A-Z2-a, 2-A-Z3-a, 2-A-Z4-a, 2-A-Z5-a, 2-A-Z6-a, 2-A-Z7-a, 2-B-Z1-b, 2-B-Z2-b, 2-B-Z3-b, 2-B-Z4-b, 2-B-Z5-b, 2-B-Z6-b, 2-B-Z7-b, 2-C-Z1-c, 2-C-Z2-c, 2-C-Z3-c, 2-C-Z4-c, 2-C-Z5-c, 2-C-Z6-c, 2-C-Z7-c,

3-A-Z1-a, 3-A-Z2-a, 3-A-Z3-a, 3-A-Z4-a, 3-A-Z5-a, 3-A-Z6-a, 3-A-Z7-a, 3-B-Z1-b, 3-B-Z2-b, 3-B-Z3-b, 3-B-Z4-b, 3-B-Z5-b, 3-B-Z6-b, 3-B-Z7-b, 3-C-Z1-c, 3-C-Z2-c, 3-C-Z3-c, 3-C-Z4-c, 3-C-Z5-c, 3-C-Z6-c, 3-C-Z7-c,

4-A-Z1-a, 4-A-Z2-a, 4-A-Z3-a, 4-A-Z4-a, 4-A-Z5-a, 4-A-Z6-a, 4-A-Z7-a, 4-B-Z1-b, 4-B-Z2-b, 4-B-Z3-b, 4-B-Z4-b, 4-B-Z5-b, 4-B-Z6-b, 4-B-Z7-b, 4-C-Z1-c, 4-C-Z2-c, 4-C-Z3-c, 4-C-Z4-c, 4-C-Z5-c, 4-C-Z6-c, 4-C-Z7-c,

5-A-Z1-a, 5-A-Z2-a, 5-A-Z3-a, 5-A-Z4-a, 5-A-Z5-a, 5-A-Z6-a, 5-A-Z7-a, 5-B-Z1-b, 5-B-Z2-b, 5-B-Z3-b, 5-B-Z4-b, 5-B-Z5-b, 5-B-Z6-b, 5-B-Z7-b, 5-C-Z1-c, 5-C-Z2-c, 5-C-Z3-c, 5-C-Z4-c, 5-C-Z5-c, 5-C-Z6-c, 5-C-Z7-c,

6-A-Z1-a, 6-A-Z2-a, 6-A-Z3-a, 6-A-Z4-a, 6-A-Z5-a, 6-A-Z6-a, 6-A-Z7-a, 6-B-Z1-b, 6-B-Z2-b, 6-B-Z3-b, 6-B-Z4-b, 6-B-Z5-b, 6-B-Z6-b, 6-B-Z7-b, 6-C-Z1-c, 6-C-Z2-c, 6-C-Z3-c, 6-C-Z4-c, 6-C-Z5-c, 6-C-Z6-c, 6-C-Z7-c,

7-A-Z1-a, 7-A-Z2-a, 7-A-Z3-a, 7-A-Z4-a, 7-A-Z5-a, 7-A-Z6-a, 7-A-Z7-a, 7-B-Z1-b, 7-B-Z2-b, 7-B-Z3-b, 7-B-Z4-b, 7-B-Z5-b, 7-B-Z6-b, 7-B-Z7-b, 7-C-Z1-c, 7-C-Z2-c, 7-C-Z3-c, 7-C-Z4-c, 7-C-Z5-c, 7-C-Z6-c, 7-C-Z7-c,

8-A-Z1-a, 8-A-Z2-a, 8-A-Z3-a, 8-A-Z4-a, 8-A-Z5-a, 8-A-Z6-a, 8-A-Z7-a, 8-B-Z1-b, 8-B-Z2-b, 8-B-Z3-b, 8-B-Z4-b, 8-B-Z5-b, 8-B-Z6-b, 8-B-Z7-b, 8-C-Z1-c, 8-C-Z2-c, 8-C-Z3-c, 8-C-Z4-c, 8-C-Z5-c, 8-C-Z6-c, 8-C-Z7-c,

9-A-Z1-a, 9-A-Z2-a, 9-A-Z3-a, 9-A-Z4-a, 9-A-Z5-a, 9-A-Z6-a, 9-A-Z7-a, 9-B-Z1-b, 9-B-Z2-b, 9-B-Z3-b, 9-B-Z4-b, 9-B-Z5-b, 9-B-Z6-b, 9-B-Z7-b, 9-C-Z1-c, 9-C-Z2-c, 9-C-Z3-c, 9-C-Z4-c, 9-C-Z5-c, 9-C-Z6-c and 9-C-Z7-c.

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In the combination examples mentioned previously, the numbers indicate examples of the units constitutive (1), A, B and C indicate examples of the parts -R 5 - (R 6) r -O- of the units constitutive (4), Z1 to Z7 indicate examples of the Z parts of the constituent units (4), and a, b and C indicate examples of the parts -R 5 - (R 6) m -W_n - of the constituent units (5).

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25

Other copolymerizable components

The olefin copolymer containing group branched-type polar of the invention may contain units constitutive other than the constitutive unit (1), the unit constitutive (4) and constitutive unit (5), within limits not detrimental to the objectives of the present invention.

Examples of the constitutive units that may be contained include derived constituent units of cyclic olefins other than the monomer containing polar group represented by the following formula (10), polyenes not conjugates, ethylenically unsaturated compounds containing hydroxyl group, ethylenically unsaturated compounds that contain amino group, ethylenically unsaturated compounds that contain epoxy group, aromatic vinyl compounds, acids unsaturated carboxylic acids and their derivatives, ester compounds vinyl, and vinyl chloride.

When these constituent units are contained, the amount thereof is not more than 30 mol%, preferably no more than 20 mol%, more preferably no more 10% in moles, based on all constituent units to constitute the olefin copolymer containing group polar.

Copolymer properties

The weight average molecular weight (Mw) of olefin copolymer containing polar group of the invention is in the range of usually 500 to 2,000,000, preferably of 1,000 to 1,500,000, more preferably 5,000 to 1,300,000, and the molecular weight distribution (Mw / Mn) thereof is usually not more than 3, preferably not more than 2.8, more preferably not more of 2.5.

When the molecular weight distribution (Mw / Mn) is not more than 3, the olefin copolymer containing polar group It is excellent in the orientation of polar groups towards interface between said copolymer and a polar material and has excellent adhesion properties to a polar material and excellent compatibility with a polar material.

Intensity ratio (T?? / T??) Of T?? With with respect to T? in the spectrum of 13 C-NMR of the olefin copolymer containing polar group is not more than 1.0, preferably not more than 0.8, more preferably not more than 0.5.

When the intensity ratio (Tαβ / Tαα) is not more than 1.0, the copolymer Olefin containing polar group is excellent in orientation of the polar groups towards the interface between said copolymer and a polar material

The second embodiment of the olefin copolymer containing polar group of the invention is excellent in adhesion properties to metals and polar materials such as polar resins, compatibility with them, properties surface hydrophilic, coating properties, printability, anti-fogging properties, properties antistatic, oil resistance, biocompatibility, water dispersibility, solvent dispersibility, pigment dispersibility, charge dispersibility, transparency, mechanical strength and moldability.

Procedure for preparing olefin copolymer containing polar group

The first reference embodiment of the process for preparing an olefin copolymer containing polar group comprises copolymerizing at least one α-olefin selected from α-olefins of 2 to 20 carbon atoms and at minus a monomer containing polar group selected from a monomer containing polar group represented by the following formula (7) and a monomer containing polar group represented by the following formula (8) in the presence of a olefin polymerization catalyst comprising:

(A) a compound of a transition metal selected from group 3 (including lantanoid and actinoid) at group 10 of the periodic table, and

(B) at least one compound selected from:

(B-1) a oxy-organoaluminum compound,

(B-2) a compound that reacts with the compound (A) to form an ionic pair (sometimes called "ionic ionization compound" below in this document), and

(B-3) a compound of organoaluminum

When a group containing monomer is used polar represented by the following formula (7) as a monomer containing polar group, the first embodiment of reference of olefin copolymer containing polar group mentioned above.

First the components are described to form the olefin polymerization catalyst used in the invention.

(A) Transition metal compound

The transition metal compound (A) for its use in the invention is a compound of a transition metal selected from group 3 (including lantanoid and actinoid) at group 10 of the periodic table.

Selected transition metal examples from group 3 (including lantanoid and actinoid) to group 10 of the Periodic table include scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, palladium, nickel, cobalt, rhodium, yttrium, chrome, molybdenum, tungsten, manganese, rhenium, iron and ruthenium. From these, scandium, titanium, zirconium, hafnium, vanadium, are preferred Niobium, tantalum, palladium, nickel, cobalt and rhodium. They prefer particularly titanium, zirconium and hafnium.

As a transition metal compound (A), no only the catalyst can be used in the invention Ziegler-Natta and a metallocene catalyst but also a known organometallic complex.

Examples of metal compounds of transition (A) used preferably are any compound represented by the following formulas (11) to (16).

The transition metal compound represented by the formula (11) described below.

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26

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In the above formula, M1 is an atom of Group 3 transition metal (including lanthanoid and actinoid) to group 10 of the periodic table, preferably a metal atom transition group 4, specifically zirconium, titanium or hafnium, preferably zirconium.

R 25, R 26, R 27 and R 28 can be the same or different and are each a hydrogen atom, a nitrogen containing group, a phosphorus containing group, a hydrocarbon group of 1 to 20 carbon atoms, a group halogenated hydrocarbon of 1 to 20 carbon atoms, a group that it contains oxygen, a group that contains sulfur, a group that It contains silicon or a halogen atom.

Examples of nitrogen containing groups include amino group; primary amino group; alkylamino groups, such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino and dicyclohexylamino; and arylamino groups or groups alkylamino, such as phenylamino, diphenylamino, ditolylamino, dynaphthylamino and methylphenylamino.

Examples of phosphorus-containing groups include phosphino groups, such as dimethylphosphine and diphenylphosphine

Examples of hydrocarbon groups 1 to 20 carbon atoms include alkyl groups, cycloalkyl groups, alkenyl groups, arylalkyl groups and aryl groups. Plus specifically, alkyl groups, such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl and eicosyl; cycloalkyl groups, such as cyclopentyl, cyclohexyl, norbornyl and adamantyl; alkenyl groups, such as vinyl, propenyl and cyclohexenyl; arylalkyl groups, such as benzyl, phenylethyl and phenylpropyl; and aryl groups, such as phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, antryl and phenanthryl

Examples of hydrocarbon groups halogenated from 1 to 20 carbon atoms include groups in which the hydrocarbon groups of 1 to 20 carbon atoms mentioned previously they are substituted with halogens.

Examples of oxygen containing groups include hydroxyl group; alkoxy groups, such as methoxy, ethoxy, propoxy and butoxy; aryloxy groups, such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy; and groups arylalkoxyl, such as phenylmethoxy and phenylethoxy.

Examples of sulfur-containing groups include groups in which oxygen is substituted with sulfur in the oxygen containing groups mentioned above; groups sulfonate, such as methylsulfonate, trifluoromethanesulfonate, phenylsulfonate, benzyl sulfonate, p-toluenesulfonate, trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate and pentafluorobenzenesulfonate; and sulphinate groups, such as methylsulphinate, phenylsulphinate, benzyl sulfate, p-toluenesulphinate, trimethylbenzenesulphinate and pentafluorobenzenesulphinate.

Examples of silicon containing groups include monohydrocarbon-substituted silyls, such as methylsilyl and phenylsilyl; silo dihydrocarbon-substituted, such as dimethylsilyl and diphenylsilyl; silo trihydrocarbon-substituted, such as trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl and trinaphthylsilyl; silyl silyl ethers hydrocarbon-substituted, such as trimethylsilyl ether; alkyl groups substituted with silicon, such as trimethylsilylmethyl; and silicon substituted aryl groups, such as trimethylsilylphenyl.

Examples of the halogen atoms include a fluorine atom, a chlorine atom, a bromine atom and an atom of iodine.

Of the groups indicated by R25, R 26, R 27 and R 28, a part of the neighboring groups each other can be united forming a ring together with the atoms of carbon to which these groups are attached.

R 25, R 26, R 27 and R 28 are each show in two positions, and for example, R 25 and R 25 may be the same or different groups. Of the groups indicated by R 25 to R 28, the groups with the same symbols are a preferred combination of groups that come together to form a ring

Examples of rings formed from a part of the neighboring groups taken from R 25, R 26, R 27 and R 28 together with carbon atoms to which those groups are bonded include condensed rings, such as benzene ring, naphthalene ring, acenaphthene ring and indene ring; Y groups in which hydrogen atoms in these rings are substituted by alkyl groups such as methyl, ethyl, propyl and butyl.

Of these, a hydrocarbon group of 1 to 20 carbon atoms or a hydrogen atom, and it is preferred particularly a hydrocarbon group of 1 to 4 carbon atoms such as methyl, ethyl, propyl or butyl, a benzene ring formed by the union of a hydrocarbon group, or a group in which a hydrogen atom in a benzene ring formed by joining a hydrocarbon group it is substituted with a alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl.

X 1 and X 2 can be the same or different and are each the same hydrocarbon group from 1 to 20 carbon atoms, halogenated hydrocarbon group of 1 to 20 atoms carbon, oxygen containing group, sulfur containing group, group containing silicon, hydrogen atom or halogen atom as described above with respect to R25, R 26, R 27 and R 28. Of these, an atom of halogen, a hydrocarbon group of 1 to 20 carbon atoms or a sulfonate group.

Y 1 is a divalent hydrocarbon group of 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group of 1 to 20 carbon atoms, a group containing divalent silicon, a group containing divalent germanium, a group containing tin divalent, -O-, -CO-, -S-, -SO-, -SO2 -, -Ge-, -Sn-, -NR21 -, -P (R21) -, -P (O) (R 21) -,
-BR 21 - or -AlR 21 - (each R 21 may be the same or different and is a hydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 atoms of carbon, a hydrogen atom or a halogen atom).

Examples of hydrocarbon groups divalents of 1 to 20 carbon atoms include alkylene groups, such as methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene and 1,4-cyclohexylene; and arylalkylene groups, such as diphenylmethylene and diphenyl-1,2-ethylene.

Examples of hydrocarbon groups divalent halogenates of 1 to 20 carbon atoms include groups in which divalent hydrocarbon groups of 1 to 20 atoms of carbon mentioned above are halogenated, such as chloromethylene

Examples of silicon containing groups divalents include alkylsilylene groups, such as silylene, methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene, di (p-tolyl) silylene and di (p-chlorophenyl) silylene; groups alkylarylsilylene; arylsilylene groups; alkyldisilylene groups, such as tetramethyl-1,2-disylylene and tetraphenyl-1,2-disylylene; groups alkylaryldisilylene; and aryldisilylene groups.

Examples of groups containing germanium divalents include groups in which silicon is substituted by germanium in the groups containing divalent silicon mentioned above.

Examples of tin containing groups divalents include groups in which silicon is substituted per tin in groups containing divalent silicon mentioned above.

R 21 is the same hydrocarbon group of 1 to 20 carbon atoms, halogenated hydrocarbon group from 1 to 20 carbon atoms or halogen atom as described above with respect to R 25, R 26, R 27 and R 28, or a nitrogen compound moiety in which one or two hydrocarbon groups of 1 to 20 carbon atoms are attached to the nitrogen atom

Of these, it is particularly preferred as And 1 a substituted silylene group, such as dimethylsilylene, diphenylsilylene or methylphenylsilylene.

Examples of metal compounds of transition represented by formula (11) include ethylene bis (indenyl) dimethyl zirconium,  dichloride ethylene bis (indenyl) zirconium, bis (trifluoromethanesulfonate) of ethylene bis (indenyl) zirconium, bis (methanesulfonate) of ethylene bis (indenyl) zirconium, bis (p-toluenesulfonate) of ethylene bis (indenyl) zirconium, bis (p-chlorobenzenesulfonate) of ethylene bis (indenyl) zirconium, dichloride from ethylene bis (4,5,6,7-tetrahydroindenyl) zirconium, dichloride isopropylidene-bis (cyclopentadienyl) fluorenylzirconium,  dichloride isopropylidene-bis (cyclopentadienyl) (methylcyclopentadienyl) zirconium, dichloride dimethylsilylene bis (cyclopentadienyl) zirconium,  dichloride dimethylsilylene bis (methylcyclopentadienyl) zirconium, dichloride dimethylsilylene bis (dimethylcyclopentadienyl) zirconium,  dichloride dimethylsilylene bis (trimethylcyclopentadienyl) zirconium, dichloride dimethylsilylene bis (indenyl) zirconium, bis (trifluoromethanesulfonate) of dimethylsilylene bis (indenyl) zirconium, dichloride dimethylsilylene bis (4,5,6,7-tetrahydroindenyl) zirconium,  dichloride dimethylsilylene bis (cyclopentadienyl) (fluorenyl) zirconium, dichloride diphenylsilylene bis (indenyl) zirconium, dichloride methylphenylsilylene bis (indenyl) zirconium, dichloride rac-dimethylsilylene-bis (2,3,5-trimethylcyclopentadienyl) zirconium,  dichloride rac-dimethylsilylene-bis (2,4,7-trimethylcyclopentadienyl) zirconium, dichloride rac-dimethylsilylene-bis (2-methyl-4-tert-butylcyclopentadienyl) zirconium,  dichloride isopropylidene- (cyclopentadienyl) (fluorenyl) zirconium, dichloride dimethylsilylene- (3-tert-butylcyclopentadienyl) (indenyl) zirconium, dichloride isopropylidene (4-methylcyclopentadienyl) (3-methylindenyl) zirconium,  dichloride isopropylidene (4-tert-butylcyclopentadienyl) (3-methylindenyl) zirconium, dichloride isopropylidene (4-tert-butylcyclopentadienyl) (3-tert-butylindenyl) zirconium,  dichloride dimethylsilylene- (4-methylcyclopentadienyl) (3-methylindenyl) zirconium, dichloride dimethylsilylene- (4-tert-butylcyclopentadienyl) (3-methylindenyl) zirconium,  dichloride dimethylsilylene- (4-tert-butylcyclopentadienyl) (3-tert-butylindenyl) zirconium, dichloride dimethylsilylene- (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium,  dichloride isopropylidene (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium, dichloride N, N-diphenylaminoboriliden-bis (cyclopentadienyl) zirconium,  dichloride N, N-dinaphthylaminoboriliden-bis (cyclopentadienyl) zirconium, dichloride N, N-dimethylaminoboriliden-bis (cyclopentadienyl) zirconium  and dichloride of N-methyl-N-phenylaminoboriliden-bis (cyclopentadienyl) zirconium.

Compounds are also available in those that zirconium is replaced by titanium or hafnium in the compounds mentioned above.

The transition metal compound represented by formula (11) it is more specifically a compound of transition metal represented by the following formula (11a) or (11b).

27

In the above formula, M1 is an atom of transition metal of group 4 of the periodic table, specifically zirconium, titanium or hafnium, preferably Zirconium

Each R31 may be the same or different and is a hydrocarbon group of 1 to 6 carbon atoms. Examples of such hydrocarbon groups include alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl and cyclohexyl; and alkenyl groups, such like vinyl and propenyl. Of these, alkyl groups are preferred whose carbon atoms attached to indenyl groups are atoms of primary carbon, alkyl groups of 1 to 4 are more preferable carbon atoms, and methyl and ethyl.

R 32, R 34, R 35 and R 36 can be the same or different and are each a hydrogen atom, a halogen atom or the same hydrocarbon group of 1 to 6 atoms of carbon as described above with respect to R 31.

Each R 33 can be the same or different and is a hydrogen atom or an aryl group of 6 to 16 carbon atoms. Examples of such aryl groups include phenyl, α-naphthyl, β-naphthyl, Antrile, phenanthryl, pyrenyl, acenaphthyl, phenalenyl, aceantrilenil, tetrahydronaphthyl, indanyl and biphenyl. Of these, phenyl, naphthyl, antryl and phenanthryl are preferred.

These aryl groups may be substituted. with:

halogen atoms, such as fluorine, chlorine, bromine and iodine;

hydrocarbon groups of 1 to 20 atoms of carbon, for example, alkyl groups, such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl, norbornyl and adamantyl; alkenyl groups, such as vinyl, propenyl and cyclohexenyl; arylalkyl groups, such as benzyl, phenylethyl and phenylpropyl; and aryl groups, such as phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, α- or β-naphthyl, methylnaphthyl, antryl, phenanthryl, benzylphenyl, pyrenyl, acenaphthyl, phenalenyl, aceantrilenyl, tetrahydronaphthyl, indanyl and biphenyl; Y

organosilyl groups, such as trimethylsilyl, triethylsilyl and triphenylsilyl.

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X 1 and X 2 can be the same or different and have the same meanings as those of X1 and X 2 in the formula (11). Of the mentioned atoms and groups above, a halogen atom or a group is preferred hydrocarbon of 1 to 20 carbon atoms.

Y1 has the same meaning as that of Y 1 in the formula (11). Of the groups mentioned above,  a group containing divalent silicon is preferred, a group that contains divalent germanium, a divalent alkylene group or a boronyl group containing divalent boron, a more preferable is group containing divalent silicon or an alkylene group divalent, and alkylsilylene is particularly preferred, alkylarylsilylene, arylsilylene, alkylalkylene or arylalkylene.

Examples of the transition metal compounds represented by the formula (11a) include rac-dimethylsilylene-bis [1- (2-methyl-4-phenylindenyl)] zirconium dichloride, rac-dimethylsilylene-bis [1- (2) dichloride -methyl-4 - (α-naphthyl) indenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-methyl-4 - (β-naphthyl) indenyl)] zirconium dichloride, rac-dimethylsilylene dichloride bis [1- (2-methyl-4- (1-antryl) indenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-methyl-4- (2-antryl) indenyl)] zirconium dichloride rac-dimethylsilylene-bis [1- (2-methyl-4- (9-antryl) indenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-methyl-4- (9-phenanthryl) indenyl)] dichloride zirconium, rac-dimethylsilylene-bis [1- (2-methyl-4- (p-fluorophenyl) indenyl)] zirconium dichloride, rac-dimethylsilylene-bis [1- (2-methyl-4- (pentafluorophenyl) indenyl dichloride )] zirconium, rac-dimethylsilylene-bis [1- (2-methyl-4- (p-chlorophenyl) indenyl) dichloride, zirconium, rac-dimethylsilylene-bis [1- (2-methyl-4- (m -chlorophenyl) indenyl)] zirconium, dichloride rac-dimethylsilylene-bis [1- (2-methyl-4- (o-chlorophenyl) indenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-methyl-4- (or, p-dichlorophenyl) phenylindenyl dichloride )] zirconium, rac-dimethylsilylene-bis [1- (2-methyl-4- (p-bromophenyl) indenyl) dichloride, zirconium, rac-dimethylsilylene-bis [1- (2-methyl-4- (p -tolyl) indenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-methyl-4- (m-tolyl) indenyl)] zirconium dichloride, rac-dimethylsilylene-bis [1- (2-methyl-) dichloride 4- (o-tolyl) indenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-methyl-4- (or, o'-dimethylphenyl) -1-indenyl)] zirconium dichloride, rac-dimethylsilylene dichloride -bis [1- (2-methyl-4- (p-ethylphenyl) indenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-methyl-4- (pi-propylphenyl) indenyl)] zirconium dichloride of rac-dimethylsilylene-bis [1- (2-methyl-4- (p-benzylphenyl) indenyl)] zir-
conium, rac-dimethylsilylene-bis [1- (2-methyl-4- (p-biphenyl) indenyl)] zirconium dichloride, rac-dimethylsilylene-bis [1- (2-methyl-4- (m-biphenylyl) dichloride ) indenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-methyl-4- (p-trimethylsilylephenyl) indenyl)] zirconium dichloride, rac-dimethylsilylene-bis [1- (2-methyl-4- dichloride) (m-trimethylsilylenephenyl) indenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-phenyl-4-phenylindenyl)] zirconium dichloride, rac-dimethylsilylene-bis [1- (2-methyl-4-phenylindenyl dichloride) )] zirconium, rac-di- (i-propyl) silylene-bis [1- (2-methyl-4-phenylindenyl)] zirconium dichloride, rac-di- (n-butyl) silylene-bis [1-] dichloride (2-methyl-4-phenylindenyl)] zirconium, rac-dicyclohexylsilylene-bis [1- (2-methyl-4-phenylindenyl) dichloride]]
zirconium, rac-methylphenylsilylene-bis [1- (2-methyl-4-phenylindenyl)] zirconium dichloride, rac-diphenylsilylene-bis [1- (2-methyl-4-phenylindenyl) dichloride] zirconium, rac- dichloride di (p-tolyl) silylene-bis [1- (2-methyl-4-phenylindenyl)] zirconium, rac-di (p-chlorophenyl) silylene-bis [1- (2-methyl-4-phenylindenyl)] dichloride zirconium, rac-methylene-bis [1- (2-methyl-4-phenylindenyl)] zirconium dichloride, rac-ethylene-bis [1- (2-methyl-4-phenylindenyl)] zirconium dichloride, rac- dichloride dimethylgermilen-bis [1- (2-methyl-4-phenylindenyl)] zirconium, rac-dimethylstannilen-bis [1- (2-methyl-4-phenylindenyl)] zirconium dichromide, rac-dimethylsilylene-bis [1- (2-methyl-4-phenylindenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-methyl-4-phenylindenyl)] zirconium-dimethyl, rac-dimethylsilylene-bis [1- (2-methyl-4-methylchloride] -phenylindenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-methyl-4-phenylindenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-methyl-4-phenylindenyl) chloride] [1- (2-methyl-4-phenylindenyl)] zirconium, rac-dimet dichloride ilsililen-bis [1- (2-ethyl-4-phenylindenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-ethyl-4-? -naphthyl) indenyl] zirconium dichloride, rac-dimethylsilylene- dichloride bis [1- (2-ethyl-4 - (β-naphthyl) indenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-ethyl-4- (2-methyl-1-naphthyl) indenyl) dichloride ] zirconium, rac-dimethylsilylene-bis [1- (2-ethyl-4- (5-acenaphthyl) indenyl) dichloride, zirconium, rac-dimethylsilylene-bis [1- (2-ethyl-4- (9- antrile) indenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-ethyl-4- (9-phenanthryl) indenyl)] zirconium dichloride, rac-dimethylsilylene-bis [1- (2-ethyl-4 dichloride) - (o-methylphenyl) indenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-ethyl-4- (m-methylphenyl) indenyl)] zirconium dichloride, rac-dimethylsilylene-bis [1- (2) dichloride -ethyl-4- (p-methylphenyl) indenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-ethyl-4- (2,3-dimethylphenyl) indenyl)] zirconium dichloride, rac-dimethylsilylene dichloride bis [1- (2-ethyl-4- (2,4-dimethylphenyl) indenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-ethyl-4- (2,5-d) dichloride imethylphenyl) indenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-ethyl-4- (2,4,6-trimethylphenyl) indenyl)] zirconium dichloride, rac-dimethylsilylene-bis [1- (2) dichloride -ethyl-4- (o-chlorophenyl) indenyl)]
zirconium, rac-dimethylsilylene-bis [1- (2-ethyl-4- (m-chlorophenyl) indenyl)] zirconium dichloride, rac-dimethylsilylene-bis [1- (2-ethyl-4- (p-chlorophenyl) dichloride ) indenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-ethyl-4- (2,3-dichlorophenyl) indenyl) dichloride, zirconium, rac-dimethylsilylene-bis [1- (2-ethyl-] dichloride 4- (2,6-Dichlorophenyl) indenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-ethyl-4- (3,5-dichlorophenyl) indenyl) dichloride, zirconium, rac-dimethylsilylene-bis dichloride [1- (2-ethyl-4- (2-bro-
mofenil) indenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-ethyl-4- (3-bromophenyl) indenyl)] zirconium dichloride, rac-dimethylsilylene-bis [1- (2-ethyl-4 dichloride) - (4-Bromophenyl) indenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-ethyl-4- (4-biphenylyl) indenyl)]] zirconium dichloride, rac-dimethylsilylene-bis [1- (2) dichloride -ethyl-4- (4-trimethylsilylphenyl) indenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-n-propyl-4-phenylindenyl)] zirconium dichloride, rac-dimethylsilylene-bis [1- ( 2-n-propyl-4 - (α-naphthyl) indenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-n-propyl-4 - (β-naphthyl) indenyl)] zirconium dichloride of rac-dimethylsilylene-bis [1- (2-n-propyl-4- (2-methyl-1-naphthyl) indenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-n-propyl-4) dichloride - (5-acenaphthyl) indenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-n-propyl-4- (9-antryl) indenyl) dichloride] zirconium, rac-dimethylsilylene-bis [1-] dichloride (2-n-propyl-4- (9-phenanthryl) indenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-i-propyl-4-phenyl) dichloride indenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-i-propyl-4 - (α-naphthyl) indenyl)] zirconium dichloride, rac-dimethylsilylene-bis [1- (2-i-) dichloride propyl-4 - (β-naphthyl) indenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-i-propyl-4- (8-methyl-9-naphthyl) indenyl)] zirconium dichloride rac-dimethylsilylene-bis [1- (2-i-propyl-4- (5-acenaphthyl) indenyl)]
zirconium, rac-dimethylsilylene-bis [1- (2-i-propyl-4- (9-antryl) indenyl)] zirconium dichloride, rac-dimethylsilylene-bis [1- (2-i-propyl-4- dichloride) (9-phenanthryl) indenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-s-butyl-4-phenylindenyl)] zirco- dichloride
Nio, rac-dimethylsilylene-bis [1- (2-s-butyl-4 - (α-naphthyl) indenyl)] zirconium dichloride, rac-dimethylsilylene-bis [1- (2-s-butyl-4 dichloride) - (β-naphthyl) indenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-s-butyl-4- (2-methyl-1-naphthyl) indenyl)] dichloride
zirconium, rac-dimethylsilylene-bis [1- (2-s-butyl-4- (5-acenaphthyl) indenyl)] zirconium dichloride, rac-dimethylsilylene-bis [1- (2-s-butyl-4- dichloride) (9-antryl) indenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-s-butyl-4- (9-phenanthryl) indenyl)] zirconium dichloride, rac-dimethylsilylene-bis [1- ( 2-n-pentyl-4-phenylindenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-n-pentyl-4 - (α-naphthyl) indenyl)] zirconium dichloride, rac-dimethylsilylene-bis dichloride [1- (2-n-Butyl-4-phenylindenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-n-butyl-4 - (α-naphthyl) indenyl) dichloride], zirconium, rac dichloride -dimethylsilylene-bis [1- (2-
n-butyl-4 - (β-naphthyl) indenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-n-butyl-4- (2-methyl-1-naphthyl) indenyl)] zir-
conium, rac-dimethylsilylene-bis [1- (2-n-butyl-4- (5-acenaphthyl) indenyl)] zirconium dichloride, rac-dimethylsilylene-bis [1- (2-n-butyl-4- dichloride) (9-antryl) indenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-n-butyl-4- (9-phenanthryl) indenyl)] dichloride
zirconium, rac-dimethylsilylene-bis [1- (2-i-butyl-4-phenylindenyl)] dichloride, rac-dimethylsilylene-bis [1- (2-i-butyl-4 - (α-naphthyl) dichloride ) indenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-i-butyl-4 - (β-naphthyl) indenyl)] zirconium dichloride, rac-dimethylsilylene-bis [1- (2-i -butyl-4- (2-methyl-1-naphthyl) indenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-i-butyl-4- (5-acenaphthyl) indenyl)] zirconium dichloride rac-dimethylsilylene-bis [1- (2-i-butyl-4- (9-antryl) indenyl)] zirco-
Nio, rac-dimethylsilylene-bis [1- (2-i-butyl-4- (9-phenanthryl) indenyl)] zirconium dichloride, rac-dimethylsilylene-bis [1- (2-neopentyl-4-phenylindenyl) dichloride ] zirconium, rac-dimethylsilylene-bis [1- (2-neopentyl-4 - (α-naphthyl) indenyl) dichloride] zirco-
nio, rac-dimethylsilylene-bis [1- (2-n-hexyl-4-phenylindenyl)] zirconium dichloride, rac-dimethylsilylene-bis [1- (2-n-hexyl-4 - (α-naphthyl) dichloride ) indenyl)] zirconium, rac-methylphenylsilylene-bis [1- (2-ethyl-4-phenylindenyl)] zirconium dichloride, rac-methylphenylsilylene-bis [1- (2-ethyl-4 - (α-naphthyl) dichloride ) indenyl)] zirconium, rac-methylphenylsilylene-bis [1- (2-ethyl-4- (9-antryl) indenyl)] zirconium dichloride, rac-methylphenylsilylene-bis [1- (2-ethyl-4- dichloride) (9-phenanthryl) indenyl)] zirconium, rac-diphenylsilylene-bis [1- (2-ethyl-4-phenylindenyl)] zirconium dichloride, rac-diphenylsilylene-bis [1- (2-ethyl-4- (dichloride) α-naphthyl) indenyl)] zirconium, rac-diphenylsilylene-bis [1- (2-ethyl-4- (9-antryl) indenyl)] zirconium dichloride, rac-diphenylsilylene-bis [1- (2- ethyl-4- (9-phenanthryl) indenyl)] zirconium, rac-diphenylsilylene-bis [1- (2-ethyl-4- (4-biphenylyl) indenyl) dichloride] zirco-
nio, rac-methylene-bis [1- (2-ethyl-4- (4-phenylindenyl)) zirconium dichloride, rac-methylene-bis [1- (2-ethyl-4 - (α-naphthyl) dichloride] indenyl)] zirconium, rac-ethylene-bis [1- (2-ethyl-4-phenylindenyl)] zirconium dichloride, rac-ethylene-bis [1- (2-ethyl-4 - (α-naphthyl) dichloride) indenyl)] zirconium, rac-ethylene-bis [1- (2-n-propyl-4 - (α-naphthyl) indenyl)] zirconium dichloride, rac-dimethylgermil-bis [1- (2-ethyl-] dichloride 4-phenylindenyl)] zirconium, rac-dimethylgermil-bis [1- (2-ethyl-4 - (α-naphthyl) indenyl)] dichloride
Zirconium and rac-dimethylgermil-bis [1- (2-n-propyl-4-phenylindenyl)] zirconium dichloride.

Compounds are also available in those that zirconium is replaced by titanium or hafnium in the compounds mentioned above.

In the present invention, a modification racemic transition metal compound represented by Formula (11a) is commonly used as a catalyst component, but the R form or the S form can also be used.

The transition metal compound represented by the formula (11a) it can be prepared according to the memory Descriptive and examples of European Patent A No. 0.320.762 described in Journal of Organometallic Chem., 288, p. 63-67 (1985).

The metal compound is described below. of transition represented by formula (11b).

28

In the above formula, M1 is an atom of transition metal of group 4 of the periodic table, specifically titanium, zirconium or hafnium, preferably Zirconium

R 37 and R 38 may be the same or different and are each a hydrogen atom or the same group containing nitrogen, group containing phosphorus, group hydrocarbon of 1 to 20 carbon atoms, hydrocarbon group halogenated with 1 to 20 carbon atoms, an oxygen-containing group, sulfur-containing group, silicon-containing group or atom of halogen as described above with respect to R 25, R 26, R 27 and R 28 in the formula (11).

R 37 is preferably a group hydrocarbon of 1 to 20 carbon atoms, so particularly preferably a hydrocarbon group of 1 to 3 atoms carbon such as methyl, ethyl or propyl.

R 38 is preferably an atom of hydrogen or a hydrocarbon group of 1 to 20 carbon atoms, of particularly preferably a hydrogen atom or a group hydrocarbon of 1 to 3 carbon atoms such as methyl, ethyl or propyl.

R 39 and R 40 may be the same or different and are each an alkyl group of 1 to 20 atoms of carbon. Examples of such alkyl groups include alkyl groups. straight chain or branched, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, cyclohexyl, octyl, nonyl, dodecyl and eicosyl; and groups cycloalkyl, such as norbornyl and adamantyl.

R 39 is preferably an alkyl group secondary or tertiary.

X 1 and X 2 can be the same or different and have the same meaning as those of X1 and X 2 in the formula (11).

Y1 has the same meaning as that of Y 1 in the formula (11).

Examples of the transition metal compounds represented by the formula (11b) include rac-dimethylsilylene-bis [1- (2,7-dimethyl-4-ethylindenyl)] zirconium dichloride, rac-dimethylsilylene-bis [1-] dichloride (2,7-dimethyl-4-n-propylindenyl)] zirconium, rac-dimethylsilylene-bis [1- (2,7-dimethyl-4-i-propylindenyl)] zirconium dichloride, rac-dimethylsilylene-bis [dichloride] 1- (2,7-dimethyl-4-n-butylindenyl)] zirconium, rac-dimethylsilylene-bis [1- (2,7-dimethyl-4-sec-butylindenyl)] zirconium dichloride, rac-dimethylsilylene dichloride bis [1- (2,7-dimethyl-4-t-butylindenyl)] zirconium, rac-dimethylsilylene-bis [1- (2,7-dimethyl-4-n-pentyldendenyl) dichloride] zirconium, rac- dichloride dimethylsilylene-bis [1- (2,7-dimethyl-4-n-hexylindenyl)] zirconium, rac-dimethylsilylene-bis [1- (2,7-dimethyl-4-cyclohexyldendenyl) dichloride] zirconium, rac- dichloride dimethylsilylene-bis [1- (2,7-dimethyl-4-methylcyclohexyldendenyl)] zirconium, rac-dimethylsilylene-bis [1- (2,7-dimethyl-4-phenylethylindenyl)] zirconium dichloride, ra dichloride c-dimethylsilylene-bis [1- (2,7-dimethyl-4-phenyldichloromethylindenyl)] zirconium, rac-dimethylsilylene-bis [1- (2,7-dimethyl-4-chloromethylindenyl)] zirconium dichloride, rac- dichloride dimethylsilylene-bis [1- (2,7-dimethyl-4-trimethylsilylmethylindenyl)] zirconium, rac-dimethylsilylene-bis [1- (2,7-dimethyl-4-trimethylsiloxymethylindenyl)] zirconium dichloride, rac-diethylsilylene dichloride bis [1- (2,7-dimethyl-4-i-propylindenyl)] zirconium, rac-di (i-propyl) silylene-bis [1- (2,7-dimethyl-4-i-propylindenyl)] dichloride zirconium, rac-di (n-butyl) silylene-bis [1- (2,7-dimethyl-4-i-propylindenyl)] zirconium dichloride, rac-di (cyclohexyl) silylene-bis [1- (2) dichloride , 7-dimethyl-4-i-propylindenyl)] zirconium, rac-methylphenylsilylene-bis [1- (2,7-dimethyl-4-i-propylindenyl) dichloride] zirconium, rac-methylphenylsilylene-bis [1-] dichloride (2,7-dimethyl-4-t-butylindenyl)] zirconium, rac-diphenylsilylene-bis [1- (2,7-dimethyl-4-t-butylindenyl)] zirconium dichloride, rac-diphenylsilylene-bis [dichloride] 1- (2,7-dimethyl-4-i-propylindenyl)] zirconium, dicl rac-diphenylsilylene-bis [1- (2,7-dimethyl-4-ethylindenyl)] zirconium, rac-di (p-tolyl) silylene-bis [1- (2,7-dimethyl-4-i) dichloride -propyldenyl)] zirconium, rac-di (p-chlorophenyl) silylene-bis [1- (2,7-dimethyl-4-i-propylindenyl)] zirconium dichromide, rac-dimethylsilylene-bis dibromide [1- (2 -methyl-4-i-propyl-7-ethylindenyl)] zirconium, rac-dimethylsilylene-bis [1- (2,3,7-trimethyl-4-ethylindenyl)] zirconium dichloride, rac-dimethylsilylene-bis [dichloride] 1- (2,3,7-trimethyl-4-n-propylindenyl)] zirconium, rac-dimethylsilylene-bis [1- (2,3,7-trimethyl-4-i-propylindenyl)] zirconium dichloride, dichloride rac-dimethylsilylene-bis [1- (2,3,7-trimethyl-4-n-butylindenyl)] zirconium, rac-dimethylsilylene-bis [1- (2,3,7-trimethyl-4-sec-butylindenyl) dichloride )] zirconium, rac-dimethylsilylene-bis [1- (2,3,7-trimethyl-4-t-butylindenyl) dichloride, zirconium, rac-dimethylsilylene-bis [1- (2,3,7-trimethyl) dichloride -4-n-pentylindenyl)] zirconium, rac-dimethylsilylene-bis [1- (2,3,7-trimethyl-4-n-hexylindenyl)] zirconium dichloride ac-dimethylsilylene-bis [1- (2,3,7-trimethyl-4-cyclohexyldenyl)] zirconium, rac-dimethylsilylene-bis [1- (2,3,7-trimethyl-4-methylcyclohexyldenyl) dichloride]]
zirconium, rac-dimethylsilylene-bis [1- (2,3,7-trimethyl-4-trimethylsilylmethylindenyl) dichloride, zirconium, rac-dimethylsilylene-bis [1- (2,3,7-trimethyl-4-trimethylsiloxymethylindenyl dichloride) )] zirconium, rac-dimethylsilylene-bis [1- (2,3,7-trimethyl-4-phenylethylindenyl) dichloride, zirconium, rac-dimethylsilylene-bis [1- (2,3,7-trimethyl-4 dichloride] -phenyldichloromethylindenyl)] zir-
conium, rac-dimethylsilylene-bis [1- (2,3,7-trimethyl-4-chloromethylindenyl)] zirconium dichloride, rac-diethylsilylene-bis [1- (2,3,7-trimethyl-4-i dichloride) -propyldenyl)] zirconium, rac-di (i-propyl) silylene-bis [1- (2,3,7-trimethyl-4-i-propylindenyl)] zirconium dichloride, rac-di (n-butyl) dichloride silylene-bis [1- (2,3,7-trimethyl-4-i-propylindenyl)] zirconium, rac-di (cyclohexyl) dichloride silylene-bis [1- (2,3,7-trimethyl-4-i -propyldendenyl)] zirconium, rac-methylphenylsilylene-bis [1- (2,3,7-trimethyl-4-i-propylindenyl)] zirconium dichloride, rac-methylphenylsilylene-bis [1- (2,3,7 -trimethyl-4-t-butylindenyl)] zirconium, rac-diphenylsilylene-bis [1- (2,3,7-trimethyl-4-t-butylindenyl) dichloride] zirconium, rac-diphenylsilylene-bis dichloride [1- (2,3,7-trimethyl-4-i-propylindenyl)] zirconium, rac-diphenylsilylene-bis [1- (2,3,7-trimethyl-4-ethylindenyl)] zirconium dichloride, rac-di ( p-tolyl) silylene-bis [1- (2,3,7-trimethyl-4-i-propylindenyl)] zirconium, rac-di (p-chlorophenyl) silylene-bis [1- (2,3,7 -trime til-4-i-propylindenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-methyl-4-i-propyl-7-methylindenyl)] zirconium-dimethyl, rac-dimethylsilylene-bis methyl chloride [1- ( 2-methyl-4-i-propyl-7-methylindenyl)] zirconium, bis (methanesulfonate) from rac-dimethylsilylene-bis [1- (2-methyl-4-i-propyl-7-methylindenyl)] zirconium, bis ( rac-dimethylsilylene-bis [1- (2-methyl-4-i-propyl-7-methylindenyl)] zirconium p-phenylsulphinate), rac-dimethylsilylene-bis [1- (2-methyl-3-methyl-] dichloride 4-i-propyl-7-methylindenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-methyl-4,6-di-i-propylindenyl) dichloride] zirconium, rac-dimethylsilylene-bis dichloride [1 - (2-ethyl-4-i-propyl-7-methylindenyl)] zirconium, rac-dimethylsilylene-bis [1- (2-phenyl-4-i-propyl-7-methylindenyl)] zirconium dichloride, rac dichloride -dimethylsilylene-bis [1- (2-methylindenyl)] zirconium, rac-ethylene-bis [1- (2,4,7-trimethylindenyl)] zirconium dichloride and rac-isopropylidene-bis [1- (2, 4,7-trimethylindenyl)] zirconium.

Compounds are also available in those that zirconium is replaced by titanium or hafnium in the compounds mentioned above.

Of the above compounds, preferred particularly compounds having a branched alkyl group, such as i-propyl, sec-butyl or tert-butyl, in position 4.

In the present invention, a modification racemic transition metal compound represented by Formula (11b) is commonly used as a catalyst component, but the R form or the S form can also be used.

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The transition metal compound represented by formula (11b) it can be synthesized from a indene derivative by a known procedure, for example, a procedure described in the Japanese patent publication open for consultation by the public # 268307/1992.

The metal compound is described below. of transition represented by formula (12).

29

In the above formula, M1 is an atom of transition metal selected from group 3 to group 10 of the periodic table, preferably a transition metal atom selected from group 4 of the periodic table, more preferably zirconium, titanium or hafnium, particularly preferably Zirconium

Cp is a cyclopentadienyl group or its derivative which is linked with a π link to M 1.

Z1 is a ligand that contains an atom of oxygen, a sulfur atom, a boron atom or an element of the group 14 of the periodic table, for example, -Si (R 22 2) -, -C (R 22 2) -, -Yes (R 22 2) Si (R 22 2) -, -C (R 22 2) C (R 22 2) -, -C (R 22 2) C (R 22 2) C (R 22) -, -C (R 22) = C (R 22) -, -C (R 22 2) Si (R 22 2) - or -Ge (R 22) -.

Y1 is a ligand that contains an atom of nitrogen, a phosphorus atom, an oxygen atom or an atom of sulfur, for example, -N (R 23) -, -O-, -S- or -P (R 23) -.

Z 1 and Y 1 can together form a ring condensed.

R 22 is a hydrogen atom, a group alkyl, aryl, silyl, halogenated alkyl or halogenated aryl which it has up to 20 atoms that are not hydrogen, or a combination of such groups. R 23 is an alkyl group of 1 to 10 atoms of carbon, an aryl group of 6 to 10 carbon atoms or a group aralkyl of 7 to 10 carbon atoms, or it can form a ring condensate of up to 30 non-hydrogen atoms together with one or more R 22.

Each X1 can be the same or different and is a hydrogen atom, a halogen atom, a hydrocarbon group which has 20 or less carbon atoms and can contain 1 or more double bonds, a silyl group containing 20 or less atoms of silicon, a germyl group that contains 20 or less germanium atoms or a boronyl group containing 20 or less boron atoms.

Examples of metal compounds of Transitions represented by formula (12) include dichloride  from (tert-butylamide) (tetramethyl- η 5 -cyclopentadienyl) -1,2-ethanediylzirconium, dichloride (tert-butylamide) (tetramethyl- η 5 -cyclopentadienyl) -1,2-ethanediylthitanium,  dichloride (methylamide) (tetramethyl- η 5 -cyclopentadienyl) -1,2-ethanediylzirconium, dichloride (methylamide) (tetramethyl- η 5 -cyclopentadienyl) -1,2-ethanediylthitanium, dichloride (ethylamide) (tetramethyl- η 5 -cyclopentadienyl) methylenenotitanium,  dichloride (tert-Butylamide) dimethyl (tetramethyl- η 5 -cyclopentadienyl) silanotitanium, dichloride (tert-Butylamide) dimethyl (tetramethyl- η 5 -cyclopentadienyl) silanozirconium, dichloride (benzylamide) dimethyl (tetramethyl- η 5 -cyclopentadienyl) silanotitanium  Y (phenylphosphide) dimethyl (tetramethyl- η 5 -cyclopentadienyl) silanozirconium dibenzyl.

The metal compound is described below. of transition represented by formula (13).

30

In the above formula, M1 is an atom of transition metal selected from group 3 to group 10 of the periodic table, preferably a transition metal atom selected from group 4 of the periodic table, more preferably titanium, zirconium or hafnium, particularly preferably Zirconium

R 11 to R 14, R 17 to R 20 and R 41 may be the same or different and are each a group hydrocarbon of 1 to 40 carbon atoms, a hydrocarbon group halogenated from 1 to 40 carbon atoms, a group that contains oxygen, a group that contains sulfur, a group that contains silicon, a halogen atom or a hydrogen atom; of the groups indicated by R 11, R 12, R 13, R 14, R 17, R 18, R 19, R 20 and R 41, a part of the neighboring groups can be joined together forming a ring together with the carbon atoms to which these groups are attached (Except a case in which all R 11, R 12, R 13, R 14, R 17, R 18, R 19, R 20 and R 41 are hydrogen atoms and a case in which R 12 or R 13 is a tert-butyl group and the remainder of R 11, R 12, R 13, R 14, R 17, R 18, R 19, R 20 and R 41 are hydrogen atoms).

Examples of hydrocarbons of 1 to 40 atoms of carbon are alkyl groups of 1 to 20 carbon atoms such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl and eicosyl;

aryl groups of 6 to 20 carbon atoms such such as phenyl, α- or β-naphthyl, biphenyl, antryl and phenanthryl;

arylalkyl groups of 7 to 40 carbon atoms such as benzyl, phenylethyl, phenylpropyl, phenanthrylmethyl, phenanthrylethyl and phenanthrylpropyl;

arylalkenyl groups of 8 to 40 carbon atoms such as vinylphenanthryl;

alkylaryl groups of 7 to 40 carbon atoms such as methylphenanthryl, ethylphenanthryl and propylphenanthryl; Y

alkenyl groups of 2 to 10 carbon atoms such as vinyl, propenyl and cyclohexenyl.

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Examples of hydrocarbon groups halogenated from 1 to 40 carbon atoms include groups in which the hydrocarbon groups of 1 to 40 carbon atoms mentioned previously they are substituted with halogens.

Examples of the groups that contain oxygen, sulfur-containing groups, groups that contain silicon and halogen atoms include the same groups and atoms which were described above with respect to R25, R 26, R 27 and R 28 in the formula (11).

X 1 and X 2 may be the same or different and have the same meanings as those of X 1 and X 2 in the formula (11).

Y1 has the same meaning as that of Y 1 in the formula (11).

Examples of the transition metal compounds represented by the formula (13) include isopropylidene- (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene- (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene dichloride- ( 3-tert-butylcyclopentadienyl) (fluorenyl) zirconium, iso- dichloride
propylidene- (cyclopentadienyl) (2,7-tert-butylfluorenyl) zirconium, dimethylsilylene- (2-methyl-cyclopentadienyl) dichloride
(2,7-tert-Butylfluorenyl) zirconium, dimethylsilylene- (2-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene- (cyclopentadienyl) dichloride (2,7-tert-butylfluorenyl) zirconium dichloride (isyl dichloride) 2-methyl-cyclopentadienyl)
(2,7-tert-Butylfluorenyl) zirconium, isopropylidene- (2-methyl-cyclopentadienyl) dichloride (3,6-tert-butylfluorenyl) zirconium, dimethylsilylene- (2-methyl-cyclopentadienyl) dichloride (3,6-tert -butylfluorenyl) zirconium and diphenylmethylene dichloride-
(cyclopentadienyl) (fluorenyl) zirconium.

Compounds are also available in those that zirconium is replaced by titanium or hafnium in the compounds mentioned above.

The metal compound is described below. of transition represented by the formula (14).

31

In the above formula, M1 is an atom of transition metal selected from group 3 to group 10 of the periodic table, preferably a transition metal atom selected from group 4 of the periodic table, more preferably titanium, zirconium or hafnium, particularly preferably Zirconium

R 11, R 12, R 41 and R 42 can be the same or different and are each a hydrocarbon group of 1 to 40 carbon atoms, a halogenated hydrocarbon group of 1 to 40 carbon atoms, a group that contains oxygen, a group that contains sulfur, a group containing silicon, a halogen atom or a hydrogen atom.

Examples of hydrocarbon groups of 1 at 40 carbon atoms include the same groups as described above with respect to R 11 to R 14, R 17 to R 20 and R 41 in the formula (13).

Examples of the groups that contain oxygen, the group that contains sulfur, the groups that contain silicon and halogen atoms include the same groups and atoms described above with respect to R25, R 26, R 27 and R 28 in the formula (11). Of the groups indicated by R 11, R 12, R 41 and R 42, a part of the neighboring groups with each other can be united forming a ring along with the carbon atoms to which those groups are United.

X 1 and X 2 can be the same or different and have the same meanings as those of X1 and X 2 in the formula (11).

Y1 has the same meaning as that of Y 1 in the formula (11), but when all R 11, R 12, R 41 and R 42 are hydrogen atoms, Y 1 is not It is ethylene.

Examples of the transition metal compounds represented by the formula (14) include ethylene [2-methyl-4 (9-phenanthryl) -1-indenyl] (9-fluorenyl) zirconium dichloride, ethylene [2-methyl dichloride] -4 (9-phenanthryl) -1-indenyl] (2,7-dimethyl-9-fluorenyl) zirconium, ethylene dichloride [2-methyl-4 (9-phenanthryl) -1-indenyl] (2,7-di -t-butyl-9-fluorenyl) zirconium, ethylene dichloride (2-methyl-4,5-benzo-1-indenyl) (9-fluorenyl) zirconium, ethylene dichloride (2-methyl-4,5-benzo- 1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium, ethylene dichloride (2-methyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium, ethylene dichloride (2-methyl-4,5-benzo-1-indenyl) (2,7-dibromo-9-fluorenyl) zirconium, ethylene dichloride (2,6-dimethyl-4,5-benzo-1 -indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium, ethylene dichloride (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-dibromo-9-fluorenyl) ) zirconium, ethylene (2-methyl-? -acenaphto-1-indenyl) (9-fluorenyl) zirconium dichloride, ethylene (2-methyl-? -acenaphtho-1-indenyl) dichloride (2,7-dimet il-9-fluorenyl) zirconium, ethylene dichloride (2-methyl-? -acenaphto-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium, dimethylsilylene dichloride [2-methyl- 4 (9-phenanthryl) -1-indenyl] (9-fluorenyl) zirconium, dimethylsilylene dichloride [2-n-propyl-4 (9-phenanthryl) -1-indenyl] (9-fluorenyl) zirconium, dimethylsilylene dichloride [ 2-methyl-4 (9-phenanthryl) -1-indenyl] (2,7-dimethyl-9-fluorenyl) zirconium, dimethylsilylene dichloride [2-methyl-4 (9-phenanthryl) -1-indenyl] (2, 7-di-t-butyl-9-fluorenyl) zirconium, dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (9-fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-4,5-dichloride) -benzo-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium, dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) dichloride (2,7-di-t-butyl-9 -fluorenyl) zirconium, dimethylsilylene (2-methyl-? -acenaphto-1-indenyl) (9-fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-? -acenaphtho-1-indenyl) dichloride (2,7 -dimethyl-9-fluorenyl) zirconium, dimethylsilylene (2-methyl-? -acenaphto-1-indenyl) dichloride (2,7-di-t -butyl-9-fluorenyl) zirconium, diphenylsilylene dichloride [2-methyl-4 (9-phenanthryl) -1-indenyl] (9-fluorenyl) zirconium, diphenylsilylene dichloride [2-methyl-4 (9-phenanthryl) - 1-indenyl] (2,7-dimethyl-9-fluorenyl) zirconium, diphenylsilylene dichloride [2-methyl-4 (9-phenanthryl) -1-indenyl] (2,7-di-t-butyl-9-fluorenyl) ) zirconium, diphenylsilylene (2-methyl-4,5-benzo-1-indenyl) dichloride (9-fluorenyl) zirconium, diphenylsilyl (2-methyl-4,5-benzo-1-indenyl) dichloride (2,7 -dimethyl-9-fluorenyl) zirconium, diphenylsilylene dichloride (2-methyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium, diphenylsilylene dichloride (2- methyl-? -acenaphto-1-indenyl) (9-fluorenyl) zirconium, diphenylsilylene dichloride (2-methyl-? -acenaphto-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium, dichloride diphenylsilylene (2-methyl-? -acenaphto-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium, methylphenylsilylene [2-methyl-4 (9-phenanthryl) -1-indenyl dichloride ] (9-fluorenyl) zirconium, methylphenylsilylene dichloride [2-methyl-4 (9-phenanthryl) -1-ind enyl] (2,7-dimethyl-9-fluorenyl) zirconium, methylphenylsilylene dichloride [2-methyl-4 (9-phenanthryl) -1-indenyl] (2,7-di-t-butyl-9-fluorenyl) zirconium , methylphenylsilylene (2-methyl-4,5-benzo-1-indenyl) (9-fluorenyl) zirconium dichloride, methylphenylsilylene (2-methyl-4,5-benzo-1-indenyl) dichloride (2,7-dimethyl -9-fluorenyl) zirconium, methylphenylsilylene dichloride (2-methyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium, methylphenylsilylene dichloride (2-methyl- α-acenaphtho-1-indenyl) (9-fluorenyl) zirconium, methylphenylsilylene dichloride (2-methyl-? -acenaphtho-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium, methylphenylsilylene dichloride ( 2-methyl-? -Acenaphto-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium, ethylene dichloride [3-methyl-4 (9-phenanthryl) -1-indenyl] ( 9-fluorenyl) zirconium, ethylene dichloride [3-methyl-4 (9-phenanthryl) -1-indenyl] (2,7-dimethyl-9-fluorenyl) zirconium, ethylene dichloride [3-methyl-4 (9- phenanthryl) -1-indenyl] (2,7-di-t-butyl-9-fluorenyl) zirconium, ethylene dichloride (3-methyl-4,5-benzo-1 -indenyl) (9-fluorenyl) zirconium, ethylene dichloride (3-methyl-4,5-benzo-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium, ethylene dichloride (3-methyl-4 , 5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium, ethylene (3-methyl-? -Acenaphto-1-indenyl) (9-fluorenyl) zirconium dichloride, ethylene (3-methyl-? -acenaphto-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, ethylene (3-methyl-? -acenaphto-1-indenyl) dichloride (2, 7-di-t-butyl-9-fluorenyl) zirconium, dimethylsilylene [3-methyl-4 (9-phenanthryl) -1-indenyl] (9-fluorenyl) zirconium dichloride, dimethylsilylene [3-methyl-4 (dichloride) 9-phenanthryl) -1-indenyl] (2,7-dimethyl-9-fluorenyl) zirconium, dimethylsilylene [3-methyl-4 (9-phenanthryl) -1-indenyl] dichloride (2,7-di-t- butyl-9-fluorenyl) zirconium, dimethylsilylene (3-methyl-4,5-benzo-1-indenyl) dichloride (9-fluorenyl) zirconium, dimethylsilylene (3-methyl-4,5-benzo-1-indenyl dichloride) ) (2,7-dimethyl-9-fluorenyl) zirconium, dimethylsilylene (3-methyl-4,5-benzo-1-indenyl) dichloride (2,7-di-t-butyl-9-fluorenyl) zirconium , dimethylsilylene (3-methyl-? -acenaphto-1-indenyl) (9-fluorenyl) zirconium dichloride, dimethylsilylene (3-methyl-? -acenaphtho-1-indenyl) dichloride (2,7-dimethyl-9 -fluorenyl) zirconium, dimethylsilylene (3-methyl-? -acenaphto-1-indenyl) dichloride (2,7-di-t-butyl-9-fluorenyl) zirconium, diphenylsilylene dichloride [3-methyl-4 (9 -phenanthryl) -1-indenyl] (9-fluorenyl) zirconium, diphenylsilylene dichloride [3-methyl-4 (9-phenanthryl) -1-indenyl] (2,7-dimethyl-9-fluorenyl) zirconium, diphenylsilylene dichloride [3-methyl-4 (9-phenanthryl) -1-indenyl] (2,7-di-t-butyl-9-fluorenyl) zirconium, diphenylsilylene dichloride (3-methyl-4,5-benzo-1-indenyl ) (9-fluorenyl) zirconium, diphenylsilylene dichloride (3-methyl-4,5-benzo-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium, diphenylsilylene dichloride (3-methyl-4,5 -benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium, diphenylsilyl dichloride (3-methyl-? -acenaphto-1-indenyl) (9-fluorenyl) zirconium, dichloride diphenylsilylene (3-methyl-? -acenaphto-1-indenyl) (2,7-dimethyl-9-fluorenyl) z irconium, diphenylsilylene (3-methyl-? -acenaphto-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, methylphenylsilylene [3-methyl-4 (9-phenanthryl) dichloride -1-indenyl] (9-fluorenyl) zirconium, methylphenylsilylene dichloride [3-methyl-4 (9-phenanthryl) -1-indenyl] (2,7-dimethyl-9-fluorenyl) zirconium, methylphenylsilylene dichloride [3- methyl-4 (9-phenanthryl) -1-indenyl] (2,7-di-t-butyl-9-fluorenyl) zirconium, methylphenylsilyl dichloride (3-methyl-4,5-benzo-1-indenyl) (9 -fluorenyl) zirconium, methylphenylsilylene (3-methyl-4,5-benzo-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, methylphenylsilylene (3-methyl-4,5-benzo- dichloride) 1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium, methylphenylsilylene dichloride (3-methyl-? -Acenaphto-1-indenyl) (9-fluorenyl) zirconium, methylphenylsilylene dichloride (3 -methyl-? -acenaphto-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium, methylphenylsilylene dichloride (3-methyl-? -acenaphto-1-indenyl) (2,7-di-t -butyl-9-fluorenyl) zirconium, ethylene dichloride (2-methyl-4,5-benzo-1 -indenyl) (2,7-ditrimethylsilyl-9-fluorenyl) zirconium, ethylene dichloride (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) ) zirconium, ethylene dichloride (2,7-dimethyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium, ethylene dichloride (2,7-dimethyl- 4,5- (2-methyl-benzo) -1-inde-
nil) (2,7-di-t-butyl-9-fluorenyl) zirconium, dimethylsilylene dichloride (2-methyl-4,5-benzo-1-indenyl) (2,7-dithrimethylsilyl-9-
fluorenyl) zirconium, dimethylsilylene bis (methanesulfonate) (2-methyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium, dimethyl silylene bis (trifluoromethanesulfonate) (2 -methyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium, dimethylsilylene dichloride (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-di (trimethylsilyl) -9-fluorenyl) zirconium, bis (methanesulfonate) dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-di (trimethylsilyl) -9 -fluorenyl) zirconium, dimethylsilylene bis (trifluoromethanesulfonate) (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-di (trimethylsilyl) -9-fluorenyl) zirconium, dimethylsilylene dichloride (2, 6-dimethyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium, dimethylsilylene dichloride (2,7-dimethyl-4,5-benzo-1-indenyl) ) (2,7-di-t-butyl-9-fluorenyl) zirconium, dimethylsilylene dichloride (2,7-dimethyl-4,5- (2-methyl-ben-
zo) -1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium, dimethylsilylene dichloride (2-methyl-4,5-benzo-1-indenyl) (2,7-dibromo-9 -fluorenyl) zirconium, dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-dibromo-9-fluorenyl) zirconium dichloride, dimethylsilylene (2-methyl-4,5- dichloride) benzo-1-indenyl) (2,7-di-t-butoxy-9-fluorenyl) zirconium, dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) dichloride (2,7-di- t-butoxy-9-fluorenyl) zirconium, dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) dichloride (2,7-diphenyl-9-fluorenyl) zirconium, dimethylsilylene (2,6-dimethyl dichloride) -4,5-benzo-1-indenyl) (2,7-diphenyl-9-fluorenyl) zirconium, dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) dichloride (2,7-di-i -propyl-9-fluorenyl) zirconium, dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) dichloride (2,7-di-i-propyl-9-fluorenyl) zirconium, dimethylsilylene dichloride ( 2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium, dimethylsilylene (2,6-dimethyl-4,5- (1-methyl-benzo) dichloride -1-indenyl) (2,7-di-t-butyl-9-fluor enyl) zirconium, dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di (trimethylsilyl) -9-fluorenyl) zirconium dichloride, dimethylsilylene dichloride ( 2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-dibromo-9-fluorenyl) zirconium, dimethylsilylene dichloride (2,7-dimethyl-4,5- ( 2-methyl-benzo) -1-indenyl) (2,7-di-t-butoxy-9-fluorenyl) zirconium, dimethylsilylene dichloride (2,7-dimethyl-4,5- (2-methyl-benzo) - 1-indenyl) (2,7-diphenyl-9-fluorenyl) zirconium, dimethylsilylene dichloride (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di- i-propyl-9-fluorenyl)
zirconium, dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, dimethyl silylene (2,7-dimethyl dichloride) -4,5- (1-methyl-benzo) -1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium, dimethylsilylene dichloride (2,7-dimethyl-4,5- (1 -methyl-benzo) -1-indenyl) (2,7-di (trimethylsilyl) -9-fluorenyl) zirconium, dimethylsilylene dichloride (2,7-dimethyl-4,5- (1-methyl-benzo) -1- indenyl) (2,7-dibromo-9-fluorenyl) zirconium, dimethylsilylene dichloride (2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7-di-t- butoxy-9-fluorenyl) zirconium, dimethylsilylene dichloride (2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7-diphenyl-9-fluorenyl) zirconium, dimethylsilylene dichloride (2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7-di-i-propyl-9-fluorenyl) zirconium, dimethylsilylene dichloride (2,7-dimethyl- 4,5- (1-methyl-benzo) -1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium, bis (methanesulfonate) dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-dibromo-9-fluorenyl) zirconium, dim bis (methanesulfonate) Ethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-dibromo-9-fluorenyl) zirconium, dimethylsilylene bis (methanesulfonate) (2-methyl-4,5-benzo-1- indenyl) (2,7-di-t-butoxy-9-fluorenyl) zirconium, dimethylsilylene bis (methanesulfonate) (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-di-t -butyloxy-9-fluorenyl) zirconium, dimethylsilylene bis (methanesulfonate) (2-methyl-4,5-benzo-1-indenyl) (2,7-diphenyl-9-fluorenyl) zirconium, dimethylsilylene bis (methanesulfonate) 2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-diphenyl-9-fluorenyl) zirconium, dimethylsilylene bis (methanesulfonate) (2-methyl-4,5-benzo-1-indenyl) (2,7-di-i-propyl-9-fluorenyl) zirconium, bis (methanesulfonate) dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-di-i-propyl -9-fluorenyl) zirconium, dimethylsilylene bis (methanesulfonate) (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium, dimethylsilylene bis (methanesulfonate) 2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di (trimethylsilyl) -9-fluorenyl) zirconium, bis (methanesulfonate) dimethylsilylene (2,7-dimeti l-4,5- (2-methyl-benzo) -1-indenyl) (2,7-dibromo-9-fluorenyl) zirconium, dimethylsilylene bis (methanesulfonate) (2,7-dimethyl-4,5- (2 -methyl-benzo) -1-indenyl) (2,7-di-t-butoxy-9-fluorenyl) zirconium, dimethylsilylene bis (methanesulfonate) (2,7-dimethyl-4,5- (2-methyl-benzo) ) -1-indenyl) (2,7-diphenyl-9-fluorenyl) zirconium, dimethylsilylene bis (methanesulfonate) (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2 , 7-di-i-propyl-9-fluorenyl) zirconium, bis (methanesulfonate) dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-dimethyl -9-fluorenyl) zirconium, dimethylsilylene bis (methanesulfonate) (2,7-dimethyl-4,5- (1-
methyl-benzo) -1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium, dimethylsilylene bis (methanesulfonate) (2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7-di (trimethylsilyl) -9-fluorenyl) zirconium, dimethylsilylene bis (methanesulfonate) (2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7-dibromo-9-fluorenyl) zirconium, dimethylsilylene bis (methanesulfonate) (2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7-di-t -butyloxy-9-fluorenyl) zirconium, dimethylsilylene bis (methanesulfonate) (2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7-diphenyl-9-fluorenyl) zirconium , dimethylsilylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7-di-i-propyl-9-fluorenyl) zirconium bis (methanesulfonate) bis, methanesulfonate ) dimethylsilylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium, dimethylsilylene dichloride (2-methyl-4,5 -benzo-1-indenyl) (2,7-dibromo-9- (4,5-methylenephenanthryl)) zirconium, dimethylsilylene dichloride (2,6-dimethyl-4,5-benzo-1-indenyl)
(2,7-dibromo-9- (4,5-methylenephenanthryl)) zirconium, dimethylsilylene dichloride (2-methyl-4,5-benzo-1-indenyl) (2,7-di-t-butoxy-9- (4,5-Methylenephenanthryl)) Zirconium, dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) dichloride (2,7-di-t-butoxy-9- (4,5-methylenephenanthryl) ) zirconium, dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) dichloride (2,7-diphenyl-9- (4,5-methylenephenanthryl)) zirconium, dimethylsilylene (2,6-dimethyl- dichloride) 4,5-benzo-1-indenyl) (2,7-diphenyl-9- (4,5-methylenephenanthryl))
zirconium, dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di-i-propyl-9- (4,5-methylenepheantryl)) zirconium, dimethylsilylene dichloride (2,6 -dimethyl-4,5-benzo-1-indenyl) (2,7-di-i-propyl-9- (4,5-methylenephenanthryl)) zirconium, dimethylsilylene dichloride (2,6-dimethyl-4,5- benzo-1-indenyl) (2,7-dimethyl-9- (4,5-methylenephenanthryl)) zirconium, dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl dichloride ) (2,7-di (trimethylsilyl) -9- (4,5-methylenephenanthryl)) zirconium, dichloride
dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-dibromo-9- (4,5-methylenephenanthryl)) zirconium, dimethylsilylene dichloride (2,7 -dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di-t-butoxy-9- (4,5-methylenephenanthryl)) zirconium, dichloride
of dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-diphenyl-9- (4,5-methylenephenanthryl)) zirconium, dimethylsilylene dichloride (2, 7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di-i-propyl-9- (4,5-methylenephenanthryl)) zirconium, dichloride
of dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-dimethyl-9- (4,5-methylenephenanthryl)) zirconium, dichloride
of dimethylsilylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7-di-t-butyl-9- (4,5-methylenephenanthryl)) zirconium, dichloride dimethylsilylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7-di (trimethylsilyl) -9- (4,5-methylenephenanthryl)) zirconium, dimethylsilylene dichloride ( 2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7-dibromo-9- (4,5-methylenephenanthryl)) zirconium, dimethylsilylene dichloride (2,7-dimethyl -4,5- (1-methyl-benzo) -1-indenyl) (2,7-di-t-butoxy-9- (4,5-methylenephenanthryl)) zirconium, dimethylsilylene dichloride (2,7-dimethyl- 4,5- (1-methyl-benzo) -1-indenyl) (2,7-diphenyl-9- (4,5-methylenephenanthryl)) zirconium, dimethylsilylene dichloride (2,7-dimethyl-4,5- ( 1-methyl-benzo) -1-indenyl) (2,7-di-i-propyl-9- (4,5-methylenephenanthryl)) zirconium, dimethylsilylene dichloride (2,7-dimethyl-4,5- (1 -methyl-benzo) -1-indenyl) (2,7-dimethyl-9- (4,5-methylenephenanthryl)) zirconium,
dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9- (4,5-methylenephenanthryl)) zirconium dichloride, dimethylsilylene (2-methyl-4 dichloride) , 5-benzo-1-indenyl) (2,7-di (trimethylsilyl) -9- (4,5-methylenephenanthryl)) zirconium, dimethylsilylene dichloride (2,6-dimethyl-4,5-benzo-1-indenyl ) (2,7-di-t-butyl-9- (4,5-methylenephenanthryl)) zirconium, dimethylsilylene dichloride (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-di (trimethylsilyl) -9- (4,5-methylenephenanthryl)) zirconium, dimethylsilylene dichloride
(2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di-t-butyl-9- (4,5-methylenephenanthryl)) zirconium, dimethylsilylene dichloride ( 2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di (trimethylsilyl) -9- (4,5-methylenephenanthryl)) zirconium, dimethylmethylene dichloride (2- methyl-4,5-benzo-1-indenyl) (2,7-dibromo-9-fluorenyl) zirconium, dimethylmethylene (2,6-dimethyl- dichloride)
4,5-benzo-1-indenyl) (2,7-dibromo-9-fluorenyl) zirconium, dimethylmethylene (2-methyl-4,5-benzo-1-indenyl) dichloride (2,7-di-t- butoxy-9-fluorenyl) zirconium, dimethylmethylene (2,6-dimethyl-4,5-benzo-1-indenyl) dichloride (2,7-di-t-butoxy-9-fluorenyl) zirconium, dimethylmethylene dichloride (2 -methyl-4,5-benzo-1-indenyl) (2,7-diphenyl-9-fluorenyl) zirconium, dimethylmethylene (2,6-dimethyl-4,5-benzo-1-indenyl) dichloride (2,7 -diphenyl-9-fluorenyl) zirconium, dimethylmethylene (2-methyl-4,5-benzo-1-indenyl) dichloride (2,7-di-i-propyl-9-fluorenyl) zirconium, dimethylmethylene dichloride (2, 6-dimethyl-4,5-benzo-1-indenyl) (2,7-di-i-propyl-9-fluorenyl) zirconium, dimethylmethylene (2,6-dimethyl-4,5-benzo-1-indenyl dichloride) ) (2,7-dimethyl-9-fluorenyl) zirconium, dimethylmethylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di (trimethylsilyl) - 9-fluorenyl) zirconium, dimethylmethylene dichloride (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-dibromo-9-fluorenyl) zirconium, dimethylmethylene dichloride (2 , 7-dimethyl-4,5- (2-methyl-ben zo) -1-indenyl) (2,7-di-t-butoxy-9-fluorenyl) zirconium, dimethylmethylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) dichloride (2,7-diphenyl-9-fluorenyl) zirconium, dimethylmethylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di-i-propyl-) dichloride 9-fluorenyl) zirconium, dimethylmethylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, dimethylmethylene dichloride (2 , 7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium, dimethylmethylene dichloride (2,7-dimethyl-4, 5- (1-methyl-benzo) -1-indenyl) (2,7-di (trimethylsilyl) -9-fluorenyl) zirconium, dimethylmethylene (2,7-dimethyl-4,5- (1-methyl-benzo) dichloride ) -1-indenyl) (2,7-dibromo-9-fluorenyl) zirconium, dimethylmethylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) dichloride (2,7- di-t-butoxy-9-fluorenyl) zirconium, dimethylmethylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1-in- dichloride
denyl) (2,7-diphenyl-9-fluorenyl) zirconium, dimethylmethylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7-di-i-) dichloride propyl-9-fluorenyl) zirconium, dimethylmethylene (2,7-dimethyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7-dimethyl-9- dichloride)
fluorenyl) zirconium, dimethylmethylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, dimethylmethylene (2-methyl-4,5-dichloride) -benzo-1-indenyl) (2,7-di (trimethylsilyl) -9-fluorenyl) zirconium, dimethylmethylene (2,6-dimethyl-4,5-benzo-1-indenyl) dichloride (2,7-di- t-butyl-9-fluorenyl) zirconium, dimethylmethylene (2,6-dimethyl-4,5-benzo-1-indenyl) dichloride (2,7-di (trimethylsilyl) -9-fluorenyl) zirconium, dimethylmethylene dichloride ( 2,7-dimethyl-4,5- (2-methyl-ben-
zo) -1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium, dimethylmethylene dichloride (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di (trimethylsilyl) -9-fluorenyl) zirconium, dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium- \ eta4-1-phenyl-1,3-pentadiene, dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di (trimethylsilyl) -9-fluorenyl)) zirco-
nio- η4-1,4-diphenylbutadiene, dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-dibromo-9-fluorenyl) zirconium- η4-2,4-
hexadiene, dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium- η4-1,4-diphenyl-1,3- butadiene, dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-di (trimethylsilyl) -9-fluorenyl)) zirconium- η4-3-methyl-1,3-penta-
diene, dimethylsilylene (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-dibromo-9-fluorenyl) zirconium- η4-2,4-hexadiene, diphenylsilylene dichloride (2-methyl- 4,5-benzo-1-indenyl) (2,7-ditrimethylsilyl-9-fluorenyl) zirconium, diphenylsilylene dichloride (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-di- t-butyl-9-fluorenyl) zirconium, diphenylsilylene dichloride (2,7-dimethyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium, diphenylsilylene dichloride (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium, methylphenylsilylene dichloride (2-methyl-4, 5-benzo-1-indenyl) (2,7-di (trimethyl) silyl-9-
fluorenyl)) zirconium, methylphenylsilylene dichloride (2,6-dimethyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl)) zirconium, methylphenylsilylene dichloride (2.7 -dimethyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl)) zirconium, methylphenylsilylene dichloride (2,7-dimethyl-4,5- (2-methyl- benzo) -1-indenyl) (2,7-di-t-butyl-9-fluorenyl)) zirconium, ethylene dichloride (2-methyl-7-trimethylsilyl-4,5-benzo-1-indenyl) (2, 7-di-t-butyl-9-fluorenyl) zirconium and dimethylsilylene dichloride (2-methyl-7-trimethylsilyl-4,5- (1-methyl-benzo) -1-indenyl) (2,7-di-t -butyl-9-fluorenyl) zirconium.

Compounds are also available in those that zirconium is replaced by titanium or hafnium in the compounds mentioned above.

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The metal compound is described below. of transition represented by the formula (15).

32

In the above formula, M1 is an atom of transition metal selected from group 3 to group 10 of the periodic table, preferably a transition metal atom selected from group 4 of the periodic table, more preferably titanium, zirconium or hafnium, particularly preferably Zirconium

R 41 and R 42 may be the same or different and are each a hydrocarbon group of 1 to 40 atoms carbon, a halogenated hydrocarbon group of 1 to 40 atoms of carbon, a group that contains oxygen, a group that contains sulfur, a group containing silicon, a halogen atom or a hydrogen atom

Examples of hydrocarbon groups of 1 at 40 carbon atoms include the same groups as described above with respect to R 11 to R 19, R 17 to R 20 and R 41 in the formula (13).

Examples of the groups that contain oxygen, the group that contains sulfur, the groups that contain silicon and halogen atoms include the same groups and atoms described above with respect to R25, R 26, R 27 and R 28 in the formula (11). Of the groups indicated by R 41 and R 42, a part of the groups neighbors to each other can be united forming a ring along with the carbon atoms to which these groups are attached forming a ring along with the carbon atoms to which those groups They are united.

X 1 and X 2 can be the same or different and have the same meanings as those of X1 and X 2 in the formula (11).

Y1 has the same meaning as that of Y 1 in the formula (11).

Examples of metal compounds of transition represented by formula (15) include ethylene bis (fluorenyl) dimethyl zirconium,  dichloride ethylene bis (fluorenyl) zirconium, bis (trifluoromethanesulfonate) of ethylene bis (fluorenyl) zirconium, bis (methanesulfonate) of ethylene bis (fluorenyl) zirconium, dichloride dimethylsilylene bis (fluorenyl) zirconium,  bis (trifluoromethanesulfonate) of dimethylsilylene bis (fluorenyl) zirconium, dichloride diphenylsilylene bis (fluorenyl) zirconium,  dichloride dimethylmethylene bis (fluorenyl) zirconium, dichloride dimethylmethylene-bis (2,7-tert-butylfluorenyl) zirconium,  dichloride dimethylsilylene-bis (2,7-tert-butylfluorenyl) zirconium, dichloride dimethylmethylene bis (3,6-tert-butylfluorenyl) zirconium,  dichloride dimethylsilylene bis (3,6-tert-butylfluorenyl) zirconium and dichloride of N, N-diphenylaminoboriliden-bis (fluorenyl) zirconium.

The metal compound is described below. of transition represented by the formula (16).

33

In the above formula, M1 is an atom of transition metal selected from group 4 of the periodic table, specifically titanium, zirconium or hafnium, preferably Zirconium

R 11, R 12, R 15 to R 20 and R 42 may be the same or different and are each a group hydrocarbon of 1 to 40 carbon atoms, a hydrocarbon group halogenated from 1 to 40 carbon atoms, a group that contains oxygen, a group that contains sulfur, a group that contains silicon, a halogen atom or a hydrogen atom.

Examples of hydrocarbon groups of 1 at 40 carbon atoms include the same groups as described above with respect to R 11 to R 14, R 17 to R 20 and R 41 in the formula (13).

Examples of the groups that contain oxygen, the group that contains sulfur, the groups that contain silicon and halogen atoms include the same groups and atoms described above with respect to R25, R 26, R 27 and R 28 in the formula (11). Of the groups indicated by R 11, R 12, R 15, R 16, R 17, R 18, R 19, R 20 and R 42, a part of the neighboring groups can be joined together forming a ring along with the carbon atoms to which those groups are United.

X 1 and X 2 can be the same or different and have the same meanings as those of X1 and X 2 in the formula (11).

Y1 has the same meaning as that of Y 1 in the formula (11).

Examples of metal compounds of Transitions represented by formula (16) include same compounds as exemplified above with respect to the compounds of formula (11a) or (11b).

Compounds are also available in those that zirconium is replaced by titanium or hafnium in the compounds mentioned above.

The transition metal compounds (A) mentioned above can be used individually or in combination of two or more classes.

(B-1) Oxy-compound of organoaluminum

The oxy-compound of organoaluminum (B-1) for use in the invention it can be conventional aluminoxane (also called "alumoxane") or an oxy-compound of Benzene insoluble organoaluminum of this type as shows by way of example in the Japanese patent publication open for consultation by the public No. 78687/1990.

Conventional aluminoxane can be prepared by, for example, the following procedures, and obtained generally as a solution in hydrocarbon solvent.

(1) An organoaluminum compound is added such as trialkylaluminum to a suspension of hydrocarbon medium of a compound containing adsorption water or a salt containing Crystallization water, for example, hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, sulfate of hydrated nickel or hydrated waxy chloride, to allow the organoaluminum compound reacts with the adsorption water or Crystallization water.

(2) Water, ice or water vapor is allowed act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.

(3) An organotin oxide is allowed such How dimethyltin oxide or dibutyltin oxide react with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of an organometallic component. In addition, it is possible remove by distillation of the recovered aluminoxane solution the solvent or the unreacted organoaluminum compound and re-dissolve the rest in a solvent.

Examples of organoaluminum compounds used to prepare aluminoxane include

trialkylaluminiums, such as trimethylaluminum, triethyl aluminum, tripropyl aluminum, triisopropyl aluminum, tri-n-butylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum and tridecylaluminum;

tricycloalkylaluminiums, such as tricyclohexylaluminum and tricyclooctylaluminum;

dialkylaluminum halides, such as chloride dimethylaluminum, diethyl aluminum chloride, bromide diethylaluminum and diisobutylaluminium chloride;

dialkylaluminum hydrides, such as hydride of diethylaluminum and diisobutylaluminum hydride;

dialkylaluminum alkoxides, such as dimethylaluminum methoxide and diethyl aluminum ethoxide; Y

dialkylaluminum aryloxides, such as diethylaluminium phenoxide.

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Of these, trialkylaluminiums and tricycloalkylaluminiums.

Additionally, the examples of the compounds of organoaluminum used to prepare aluminoxane include isoprenylaluminum represented by the formula (i-C 4 H 9) x Al y (C 5 H 10) z  (where x, y and z are each a positive number, and z \ geq2x).

Organoaluminum compounds are used. individually or in combination of two or more classes.

Examples of solvents used for prepare the aluminoxane include aromatic hydrocarbons, such like benzene, toluene, xylene, cumene and cimeno; hydrocarbons aliphatics, such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane; alicyclic hydrocarbons, such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane; oil fractions, such as gasoline, kerosene and diesel; Y halogenated products of these aromatic, aliphatic hydrocarbons and alicyclics (for example, chlorinated or brominated products of same). Ethers such as ethyl ether and tetrahydrofuran. Of the solvents, particularly preferred aromatic hydrocarbons.

The oxy-compound of Organoaluminum for use in the invention is, for example, a oxy-organoaluminum compound containing boron and represented by the following formula (17):

3. 4

in which R 8 is a group hydrocarbon of 1 to 10 carbon atoms; and each R 9 can be same or different and is a hydrogen atom, a halogen atom or a hydrocarbon group of 1 to 10 atoms of carbon.

(B-2) Ionizing ionic compound

Examples of the compound (B-2) which reacts with the transition metal compound (A) to form an ionic pair (sometimes referred to as "ionic compound ionizing "hereinafter), which is used in the invention, they include Lewis acid, an ionic compound, a borane compound and a carbonate compound, which are described in national publications of international patents no. 501950/1989 and No. 502036/1989, patent publications Japanese open for consultation by the public No. 179005/1991, No. 179006/1991, No. 207703/1991 and No. 207704/1991, and the patent U.S. 5,321,106. They are also available a heteropolicomposed and an isopolycomposed.

Examples of Lewis acid include acid of Lewis containing magnesium, Lewis acid containing Lewis acid and aluminum containing boron. Of these, it is preferred Lewis acid containing boron. The ionic compound is a salt which comprises a cationic compound and an anionic compound. He anion reacts with the transition metal compound to convert the transition metal compound into cationic and from that way to form an ionic pair, whereby the cationic species of transition metal. Examples of such anions include the organoboro compound anion, anion of organoarsenic compound and organoaluminum compound anion. Those that are relatively bulky and are preferred stabilize cationic transition metal species.

Lewis acids that contain boron atoms they are, for example, compounds represented by the following formula (18);

... (18) BR'R''R '' '

in which R ', R' 'and R' '' can be same or different and are each a fluorine atom or a group phenyl which can have a substituent such as a fluorine atom, a methyl group or a group trifluoromethyl.

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Examples of compounds represented by the formula (18) include trifluoroboro, triphenylboro, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron and tris [3,5-di (trifluoromethylphenyl)] boron. Of these, the tris (pentafluorophenyl) boron.

The ionic compound is a salt comprising a cationic compound and an anionic compound. It reacts a anion with the previous transition metal compound to do so cationic and form an ionic pair that has the function of stabilize the cationic species of the metal compound of transition. Examples of such anions include the anion of organic boron compound, anion of organic arsenic compound and anion of organic aluminum compound, and the relatively bulky and that can stabilize species cationic transition metal. The cations include the cation metal, organic metal cation, carbon cation, cation tropilio, oxisonio cation, sulfonio cation, phosphonium cation and cation ammonium and, more in detail, triphenylcarbenium cation, cation tributylammonium, cation N, N-dimethylammonium and cation ferrocenium

Of these, preferred anions are compounds ionic containing boron compounds as an anion.

Examples of ammonium salts trialkyl substituted include;

triethylammoniotetra (phenyl) boron, tripropylammoniotetra (phenyl) boron, tri (n-butyl) amoniotetra (phenyl) boron, trimethylammoniotetra (p-tolyl) boron, trimethylammoniotetra (o-tolyl) boron, tributylammoniotetra (pentafluorophenyl) boron, tripropylammoniotetra (or, p-dimethylphenyl) boron, tributylammoniotetra (m, m-dimethylphenyl) boron, tributylammoniotetra (p-trifluoromethylphenyl) boron, tri (n-butyl) amoniotetra (o-tolyl) boron  Y tri (n-butyl) amoniotetra (4-fluorophenyl) boron.

Examples of salts of N, N-dialkylanilinium include N, N-dimethylaniliniotetra (phenyl) boron, N, N-diethylaniliniotetra (phenyl) boron and N, N-2,4,6-pentamethylaniliniotetra (phenyl) boron.

Examples of dialkylammonium salts include di (n-propyl) amoniotetra (pentafluorophenyl) boron and dicyclohexylammoniotetra (phenyl) boron.

Examples of triarylphosphonium salts include triphenylphosphoniotetra (phenyl) boron, tri (methylphenyl) phosphonotetra (phenyl) boron Y tri (dimethylphenyl) phosphonotetra (phenyl) boron.

They can also be used as ionic compounds containing boron tetrakis (pentafluorophenyl) borate triphenylcarbenium, tetrakis (pentafluorophenyl) borate N, N-dimethylanilinium complex tetra (pentafluorophenyl) borate ferrocenium-triphenylcarbeniopentaphenylcyclopentadienyl,  complex of N, N-diethylaniliniopentaphenylcyclopentadienyl and a boron compound represented by the following formula (19) or (twenty):

35

They can also be used as ionic compounds The following compounds have a boron atom. (In the following ionic compounds, the counterion is tri (n-butyl) ammonium but it is not restricted).

Examples of anion salts include Nonaborate of bis [tri (n-butyl) ammonium], Decaborate of bis [tri (n-butyl) ammonium], undecaborate of bis [tri (n-butyl) ammonium], dodecaborate of bis [tri (n-butyl) ammonium], Decachlorodecaborate bis [tri (n-butyl) ammonium], dodecachlorodecaborate of bis [tri (n-butyl) ammonium], 1-carbadecaborate tri (n-butyl) ammonium, 1-carbaundecaborate tri (n-butyl) ammonium, 1-Carbohydrate tri (n-butyl) ammonium, 1-trimethylsilyl-1-carbadecaborate of tri (n-butyl) ammonium and Bromo-1-Carbadodecaborate tri (n-butyl) ammonium.

Examples of salts of borane compounds, Carbranium complex and carbonate anion compounds include

Decaboran (14), 7,8-dicarbaundecaborane (13), 2,7-dicarbaundecaborane (13), undecahydride-7,8-dimethyl-7,8-dicarbaundecaborane, dodecahydride-11-methyl-2,7-dicarbaundecaborane, 6-carbadecaborate (14) of tri (n-butyl) ammonium, 6-carbadecaborate (12) of tri (n-butyl) ammonium, 7-carbaundecaborate (13) of tri (n-butyl) ammonium, 7,8-dicarbaundecaborate (12) of tri (n-butyl) ammonium, 2,9-dicarbaundecaborate (12) of tri (n-butyl) ammonium, dodecahydride-8-methyl-7,9-dicarbaundecaborate of tri (n-butyl) ammonium, undecahydride-8-ethyl-7,9-dicarbaundecaborate of tri (n-butyl) ammonium, undecahydride-8-butyl-7,9-dicarbaundecaborate  of tri (n-butyl) ammonium, undecahydride-8-allyl-7,9-dicarbaundecaborate of tri (n-butyl) ammonium, undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate  of tri (n-butyl) ammonium and undecahydride-4,6-dibromo-7-carbaundecaborate of tri (n-butyl) ammonium.

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Examples of salts of carboran compounds and carboran include

4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecaborane (14), dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane Y undecahydride-1,3-dimethyl-1,3-dicarbanonaborane.

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They can also be used as ionic compounds containing the following carbonate salts of a boron atom metallic and metallic borane anion. (In the following compounds ionic, the counterion is tri (n-butyl) ammonium but it is not restricted).

Tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) ferrate (III), bis ( undecahydride-7,8-dicarbaundecaborate) tri (n-butyl) ammonium cobaltate (III), tri (n-butyl) ammonium bis (undecahydrate-7,8-dicarbaundecaborate), bis (undecahydride-7, bis) Tri (n-butyl) ammonium 8-dicarbaundecaborate) tri (n-butyl) ammonium, tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) aurate (III) bis (nonahydride-7,8-dimethyl-) 7,8-dicarbaundecaborate) tri (n-butyl) ammonium, ((nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) chromate (III) tri (n-butyl) ammonium bis (III) bis ( Tribromooctahydride-7,8-dicarbaundecaborate) tri (n-butyl) ammonium cobaltate (III), bis (do-decahydridodicatecaborate) cobaltate
(III) tri (n-butyl) ammonium, bis [tri (n-butyl) ammonium bis (dodecahydridododecaborate) bis (tri (n-butyl) ammonium], tris [tri (n) bis (undecahydride-7-carbaundecaborate) chromate (III) -butyl) ammonium], bis [tri (n-butyl) ammonium bis (undecahydride-7-carbaundecaborate) bis (tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) bis [tri (n-butyl) bis (undecahydride) ) ammonium] and bis (tri (n-butyl) ammonium) bis (undecahydride-7-carbaundecaborate) nickel (IV).

Additional examples of the compounds Ionic containing a boron atom include the following compounds such as tetrakis [(2,3,5,6-tetrafluoro-4-triisopropylsilyl) phenyl] borate of triphenylcarbenium, tetrakis [(2,3,5,6-tetrafluoro-4-triisopropylsilyl) phenyl] borate of N, N-dimethylanilinium, tetrakis [(2,3,5,6-tetrafluoro-4-dimethyl-t-butylsilyl) phenyl] borate  of triphenylcarbenium, tetrakis [(2,3,5,6-tetrafluoro-4-dimethyl-t-butylsilyl) phenyl] borate of N, N-dimethylanilinium, bis (octafluorobiphenylene) triphenylcarbenium borate, bis (octafluorobiphenylene) borate N, N-dimethylanilinium, triphenylcarbeniobis (octafluoro-1,1'-spiro) biboronol Y N, N-dimethylaniliniobis (octafluoro-1,1'-spiro) biboronol.

The heteropolycomposite comprises an atom Selected from silicon, phosphorus, titanium, germanium, arsenic or tin and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. Examples of such compounds include phosphovanadic acid, germanovanic acid, arsenovanic acid, phosphoniotic acid, germanoniobic acid, silicomolibic acid, phosphomolibic acid, titanomolibic acid, germanomolibic acid, arsenomolibic acid, stanomolibic acid, acid phosphotungstic, germanotungstic acid, stannotungstic acid, phosphomolibdovanadic acid, phosphotungstovanic acid, acid Germanotungstovanadic acid, phosphomolibdotungstovanadic acid, acid germanomolibdotungstovanadic acid, phosphomolibdotungstic acid, acid phosphomolibdonióbico, salts of these acids, specifically, salts of these acids, for example with metals of group 1 or 2 of the periodic table such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium and barium and organic salts of the above acids such as with triphenylethyl salt.

Ionizing ionic compounds can be used individually or in combination of two or more classes.

(B-3) Organoaluminum compound

Organoaluminum compounds (B-3) used in the present invention can represented by the following formula (21):

... (21) R a {{n}} AlX_ {3-n}

in which R a is a group hydrocarbon of 1 to 12 carbon atoms, X is an atom of halogen or a hydrogen atom and n is 1 to 3.

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In the above formula (21), R a is a group hydrocarbon of 1 to 12 carbon atoms, for example, a group alkyl, a cycloalkyl group or an aryl group. The examples include a methyl group, ethyl group, group n-propyl, isopropyl group, isobutyl group, group pentyl, hexyl group, octyl group, cyclopentyl group, group cyclohexyl, phenyl group and tolyl group.

Examples of organoaluminum compounds include

trialkylaluminiums, such as trimethylaluminum, triethylaluminum, triisopropyl aluminum, triisobutylaluminum, trioctylaluminum and tri-2-ethylhexylaluminum;

alkenyl aluminum, such as isoprenylaluminum;

dialkylaluminum halides, such as chloride dimethylaluminum, diethyl aluminum chloride, diisopropyl aluminum, diisobutyl aluminum chloride and bromide dimethylaluminum;

alkylaluminum sesquihalides, such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride and ethylaluminum sesquibromide,

alkyl aluminum dihalides, such as Methyl Aluminum Dichloride, Ethyl Aluminum Dichloride, Dichloride isopropylaluminum and ethyl aluminum dibromide; and

alkylaluminum hydrides, such as hydride of diethylaluminum and diisobutylaluminum hydride.

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In addition organoaluminum compounds (B-3) can also be represented by following formula (22):

... (22) R {a} {} n AlY_ {3-n}

in which R a is equal to how described above, Y is a group -OR b, group -OSiR c 3, group -OAlR d 2, group -NR e 2, group -SiR f 3 or group -N (R g) AlR h 2, n is 1 to 2, and R b, R c, R d and R h are each a methyl group, group ethyl, isopropyl group, isobutyl group, cyclohexyl group and group phenyl, R e is hydrogen, a methyl group, ethyl group, group isopropyl, phenyl group and trimethyl group, and R f and R g are each a methyl group and group ethyl.

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Examples of organoaluminum compounds include

(i) compounds represented by R a n Al (OR b) 3-n such as dimethyl aluminum methoxide, diethyl aluminum ethoxide and diisobutylaluminum methoxide;

(ii) compounds represented by R a n Al (OSiR c 3) 3-n such as (C 2 H 5) 2 Al (OSi (CH 3) 3), (iso-C 4 H 9) 2 Al (OSi (CH 3) 3) and (iso-C 4 H 9) 2 Al (OSi (C 2 H 5) 3);

(iii) compounds represented by R a n Al (OAlR d 2) 3-n such as (C 2 H 5) 2 Al (OAl (C 2 H 5) 2)  and (iso-C 4 H 9) 2 Al (OAl (iso-C 4 H 9) 2);

(iv) compounds represented by R a n Al (NR e 2) 3-n such as (CH 3) 2 Al (N (C 2 H 5) 2),  (C 2 H 5) 2 Al (NH (CH 3)), (CH 3) 2 Al (NH (C 2 H 5)), (C 2 H 5) 2 Al [N (Si (CH 3) 3) 2]  and (iso-C 4 H 9) 2 Al [N (Si (CH 3) 3) 2]; Y

(v) compounds represented by R a n Al (SiR f 3) 3-n such as (iso-C 4 H 9) 2 Al (Si (CH 3) 3).

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In the present invention, of these, preferred organoaluminum compounds represented by R a 3 Al,  R a n Al (OR b) 3-n and R a n Al (OAl R d 2) 3-n. Compounds in which R a is a particularly preferred isoalkyl group and n = 2.

Organoaluminum compounds can be used in combination of two or more classes.

The olefin polymerization catalyst used in the present invention comprises the metal compound of transition (A) and at least one compound selected from the group that consists of the organoaluminum oxy compound (B-1), the ionizing ionic compound (B-2) and the organoaluminum compound (B-3). For example, in the case that the compound transition metal (A) contains a ligand that has a main structure of cyclopentadienyl, the catalyst comprises said compound (A) and the oxy-compound of organoaluminum (B-1) and / or the ionic compound ionizing (B-2) and, optionally, the compound of organoaluminum (B-3).

The olefin polymerization catalyst for use in the invention it can be a solid catalyst in the that the transition metal compound (A) and at least one component selected from the organoaluminum oxy compound (B-1), the ionizing ionic compound (B-2) and the organoaluminum compound (B-3) are supported on a particle holder, or a prepolymerized catalyst comprising a support of particles, the transition metal compound (A), the oxy-organoaluminum compound (B-1) (or the ionizing ionic compound (B-2)), an olefin polymer produced by prepolymerization and, if necessary, the organoaluminum compound  (B-3).

A particulate support used in the catalyst solid and the prepolymerized catalyst is an inorganic compound or organic in the form of a granulated or particulate solid that has a particle diameter of 10 to 300 µm, preferably 20 at 200 µm.

Preferable examples of inorganic support are porous oxides, inorganic chlorides, clay, clay minerals and stratified ion exchange compounds. The examples of Porous oxides include SiO2, Al2O3, MgO, ZrO, TiO 2 B 2 O 3, CaO, ZnO, BaO, ThO 2 and mixtures that contain these oxides, such as SiO2 -MgO, SiO 2 - Al 2 O 3, SiO_ {2} -TiO_ {}, SiO 2 -V 2 O 5, SiO_ {2} -Cr_ {2} O_ {3} and SiO_ {2} -TiO_ {-MgO}. Of these, Compounds containing SiO2 and / or are preferred Al_ {2} O_ {3} as the main component.

Inorganic oxides may contain small amounts of carbonate, sulfate, nitrate and oxide components, such as Na 2 CO 3, K 2 CO 3, CaCO 3, MgCO 3, Na 2 SO 4, Al 2 (SO 4) 3, BaSO 4, KNO 3, Mg (NO 3) 2, Al (NO 3) 3, Na 2 O, K 2 O and Li 2 O.

Although particulate media differ in their properties depending on the type and process of preparation of themselves, the particulate support preferably has an area specific surface area of 50 to 1,000 m 2 / g, preferably of 100 to 700 m2 / g, and a pore volume of 0.3 to 2.5 cm3 / g. If necessary, the particulate support can be calcined at 100 to 1,000 ° C, preferably 150 to 700 ° C, before use.

In addition, the particulate vehicle is, for example, a granulated or particulate solid organic compound having a particle diameter of 10 to 300 µm. Examples of such Organic compounds include (co) polymers produced using an α-olefin of 2 to 14 atoms of carbon such as ethylene, propylene, 1-butene or 4-methyl-1-pentene as the main component and (co) polymers produced using vinylcyclohexane or styrene as the main component.

Examples of inorganic chlorides that may be employed in the invention include MgCl2, MgBr2, MnCl2 and MnBr2. Inorganic chloride can be used such which, or can be used after spraying by, for example, a ball mill or an oscillating mill. Inorganic chloride too can be used as fine particles of a product obtained dissolving inorganic chloride in a solvent such as alcohol and then precipitating using a precipitating agent.

The clay is usually composed mainly of clay minerals. The compounds ion exchange stratified are compounds that have a crystalline structure in which the planes formed by bonding ionic or similar are laminated in parallel with each other with a force weak link, and the ions contained therein are interchangeable Most clay minerals are stratified ion exchange compounds. The clay, the clay minerals and stratified exchange compounds ionic which can be used in the invention are not limited to the natural ones but include the synthetic ones.

Examples of such clay, minerals from clay and ion exchange stratified compounds include clay, clay minerals and ionic crystalline compounds that they have stratified crystalline structures such as the type of packing closer to hexagon, antimony type, type CdCl2 and type CdI2.

Particular examples of clay and Clay minerals include kaolin, bentonite, Kibushi clay, Gairome clay, allophane, hisingerite, pyrophyllite, mica, Montmorillonite, vermiculite, chlorite, paligorskite, kaolinite, Nacrite, dickite and haloisite. The particular examples of stratified ion exchange compounds include salts of crystalline acid of polyvalent metals, such as α-Zr (HAsO 4) 2 • H 2 O,  α-Zr (HPO 4) 2, α-Zr (KPO 4) 2 • 3 O, α-Ti (HPO 4) 2, α-Ti (HAsO 4) 2 • H 2 O, α-Sn (HPO 4) 2 • H 2 O, γ-Zr (HPO 4) 2, γ-Ti (HPO 4) 2 and γ-Ti (NH 4 PO 4) 2 • H 2 O.

Clay, clay minerals and stratified ion exchange compounds are preferably those that have a pore volume, measured in pores that have a radius not less than 20 Å by a penetration method of mercury, not less than 0.1 cc / g, and particularly preferred those with a pore volume of 0.3 to 5 cc / g. The volume of pore is measured in the pores that have a radius of 20 to 3x10 4 ? A by a method of mercury penetration using a mercury porosimeter.

If a compound that has a pore volume, measured in pores that have a radius of not less than 20 \ A {,} less than 0.1 cc / g is used as a vehicle, it tends to be difficult obtain a high polymerization activity.

It is also preferred that clay and Clay minerals undergo chemical treatments. May any of the surface treatments be used, for example, to remove impurities adhered to the surface and to influence the crystalline structure of the clay.

Examples of such chemical treatments include acid treatment, alkali treatment, treatment with salt and treatment with organic substance. Treatment with acid can contribute not only to remove impurities from the surface but also to elute cations such as Al, Fe and Mg present in the crystalline structure to increase the area superficial. Alkali treatment can destroy the structure crystalline clay to produce a change in structure of clay. Salt treatment and treatment with organic substance can make for example materials ionic compounds, molecular compounds or derivatives organic change the surface area or distance between layers.

The stratified ion exchange compound it can be a stratified compound in which ions interchangeable between the layers have been exchanged for other ions large and bulky using ion exchange properties to increase the distance between the layers. The bulky ion plays a role similar to a pillar to support the structure of layers and is generally called "pillar". The introduction of other substances between the layers of a stratified compound are called "interleaving." The examples of the compounds host to be intercalated include inorganic compounds cationic, such as TiCl 4 and ZrCl 4; alkoxides metallic, such as Ti (OR) 4, Zr (OR) 4, PO (OR) 3 and B (OR) 3 (R is a hydrocarbon group or the like); and metal hydroxide ions, such as [Al 13 O 4 (OH) 24] 7+, [Zr 4 (OH) 14] 2+ and [Fe 3 O (OCOCH 3) 6] +. The compounds mentioned above can be used individually or in combination of two or more classes.

The intercalation of the compounds can be carried out in the presence of polymers obtained by means of hydrolysis of metal alkoxides such as Si (OR) 4, Al (OR) 3 and Ge (OR) 4 (R is a hydrocarbon group or the like) or in the presence of colloidal inorganic compounds such as SiO_ {2}. Examples of the pillars include oxides produced by intercalating metal hydroxide ions mentioned above between the layers, followed by dehydration with heating.

Clay, clay minerals and Ion exchange stratified compounds mentioned previously they can be used as is, or they can be used after undergo ball grinding, sieving or Similary. In addition, they can be used after undergoing water adsorption or dehydration with heating. The clay, the minerals of clay and ion exchange stratified compounds can be used individually or in combination of two or more classes.

Of the materials mentioned above, it they prefer clay and clay minerals, and they prefer particularly Montmorillonite, Vermiculite, Hectorite, Taeniolite and synthetic mica.

The olefin polymerization catalyst for use in the invention may contain the following compound of organosilicon (C) and / or the following dialkylzinc compound (D).

(C) Organosilicon compound

The organosilicon compound (C) that is used Optionally it is represented by the following formula (22):

(22) R 1 R 2 R 3 SiH

wherein R 1, R 2 and R 3 may be the same or different and are each an atom of hydrogen, an alkyl group of 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl, an aryl group of 6 to 12 atoms of carbon, such as phenyl or tolyl, a alkylaryl group of 7 to 20 carbon atoms, such as ethylphenyl or ethyltolyl, a group arylalkyl of 7 to 20 carbon atoms, such as phenylethyl or benzyl, an alkoxy group of 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy or butoxy, a fluorinated alkyl group from 3 to 6 carbon atoms, such as 3,3,3-trifluoropropyl, a dialkylamino group that contains an alkyl group of 1 to 4 carbon atoms, such as dimethylamino, or a diorganopolysiloxane chain containing 1 to 10 units of siloxane and represented by R 6 SiO (SiR 6 O 2) n - (R 6 is methyl, phenyl, 3,3,3-trifluoropropyl, methoxy or ethoxy, and n is an integer from 0 to 9).

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Of these, a hydrogen atom is preferred, methyl, ethyl, isopropyl, isobutyl, 3,3,3-trifluoropropyl dimethylamino or a group represented by R 6 3 SiO (SiR 6 2 O) n -.

Preferred examples of the compounds of Organosilicon represented by formula (22) include phenylsilane, diphenylsilane, phenylmethylsilane, pentamethyldisiloxane, methylsilane and dimethylsilane.

The organosilicon compounds mentioned previously they can be used individually or in combination of two or more classes

(D) Dialkylzinc Compound

The dialkylzinc compound (D) used Optionally it is represented by the following formula (23):

(23) ZnR 4 R 5

wherein R 4 and R 5 can be the same or different and are each an alkyl group of 1 to 20 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, octyl, nonyl, decyl, dodecyl or Eicosyl

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Of these, an alkyl group of 1 to 12 is preferred carbon atoms, and an alkyl group of 1 to 6 is more preferred carbon atoms

Preferred examples of the compounds of dialkylzinc represented by the formula (23) include diethylzinc, diisobutylzinc and di-n-decilzinc. Of these, it particularly prefers diethylzinc.

The dialkylzinc (D) compounds mentioned previously they can be used individually or in combination of two or more classes

The organosilicon compound (C) and the compound of dialkylzinc (D) can each be used as an agent of chain transfer in combination with hydrogen. When is it used the organosilicon compound (C) as transfer agent of chain, an olefin polymer having a silyl group is obtained To the extreme.

The examples of α-olefins of 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene,  4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicoseno. Of these, a α-olefin selected from ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene.

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The following describes in more detail the monomer containing polar group represented by the formula (7) later.

36

Where R 3, R 4, r, X and p have the same meanings as those of R 3, R 4, r, X and p, respectively, in the formula (3).

Examples of monomers containing polar group include:

compounds of formula (7) in which X is a alcoholic hydroxyl group, specifically

ga-alkenyl alcohols, such as allyl alcohol, 4-penten-1-ol, 5-hexen-1-ol, 6-hepten-1-ol, 7-octen-1-ol, 8-nonen-1-ol, 9-decen-1-ol, 10-undecen-1-ol and 11-dodecen-1-ol;

alcohols having a hydrocarbon group of linear chain, such as 5-hexen-2-ol, 6-hepten-2-ol, 7-octen-2-ol, 8-nonen-2-ol, 9-decen-2-ol, 10-undecen-2-ol, 6-hepten-3-ol, 7-octen-3-ol, 8-nonen-3-ol, 9-decen-3-ol, 10-undecen-3-ol, 11-dodecen-3-ol, 7-octen-4-ol, 8-nonen-4-ol, 9-decen-4-ol, 10-undecen-4-ol, 8-nonen-5-ol, 9-decen-5-ol and 10-undecen-5-ol;

alcohols that have a hydrocarbon group branched, such as 2-ethyl-5-hexen-1-ol, 3-methyl-6-hepten-1-ol, 3-methyl-7-octen-1-ol, 4-methyl-8-nonen-1-ol, 3-ethyl-9-decen-1-ol, 2-methyl-10-undecen-2-ol, 2,2-dimethyl-7-octen-1-ol, 3-ethyl-2-methyl-8-nonen-1-ol, 2,2,3-trimethyl-9-decen-1-ol Y 2,3,3,4-tetramethyl-10-undecen-2-ol;

diols, such as 9-decen-1,2-diol, 10-undecen-1,2-diol, 11-dodecen-1,2-diol Y 11-dodecen-1,2-diol; Y

triols, such as 10-undecen-1,2,3-triol;

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compounds of formula (7) in which X is a carboxylic acid group, specifically

acids ? -alkenylcarboxylic acids, such as acid 3-butenoic acid, 5-hexenoic acid, 6-heptenoic acid, acid 7-octenoic acid, 8-nonenoic acid, 9-Decenoic acid, acid 10-undecenoic acid 11-dodecenoic;

alkenylcarboxylic acids having a group linear chain hydrocarbon, such as acid 2-methyl-5-hexenoic,  acid 2-methyl-6-heptenoic, acid 2-methyl-7-octenoic, acid 2-methyl-8-nonenoic, acid 2-methyl-9-decene,  acid 2-methyl-10-undecenoic, acid 2-methyl-11-dodecenoic, acid 2-ethyl-5-hexenoic, acid 2-ethyl-6-heptenoic,  acid 2-ethyl-7-octenoic, acid 2-ethyl-8-nonenoic, acid 2-ethyl-9-decene, acid 2-ethyl-10-undecenoic,  acid 2-propyl-5-hexenoic, acid 2-propyl-6-heptenoic, acid 2-propyl-7-octenoic, acid 2-propyl-8-nonenoic,  acid 2-propyl-9-decenoic, acid 2-propyl-10-undecenoic, acid 2-butyl-5-hexenoic, acid 2-butyl-6-heptenoic,  acid 2-butyl-7-octenoic, acid 2-butyl-8-nonenoic, acid 2-butyl-9-decene and acid 2-butyl-10-undecenoic;  Y

alkenylcarboxylic acids having a group branched hydrocarbon, such as acid 2-isopropyl-5-hexenoic,  acid 2-isopropyl-6-heptenoic, acid 2-isopropyl-7-octenoic, acid 2-isopropyl-8-nonenoic, acid 2-Isopropyl-9-Decanoic,  acid 2-isopropyl-10-undecenoic, acid 2-isobutyl-5-hexenoic, acid 2-t-butyl-6-heptenoic, acid 2-Isopropyl-3-methyl-7-octenoic,  acid 2-methyl-3-isopropyl-8-nonenoic, acid 3-isobutyl-3-methyl-9-decenoic, acid 2,2-dimethyl-10-undecenoic  and acid 2,3,3-trimethyl-11-dodecenoic;

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compounds of formula (7) in which X is a carboxylic acid ester, specifically

acid esters ? -alkenylcarboxylic acids, such as Methyl 3-butenoate, 5-hexenoate of methyl, methyl 6-heptenoate, Methyl 7-octenoate, 8-nonenoate of methyl, methyl 9-decanoate, Methyl 10-undecenoate, Methyl 11-dodecenoate, Ethyl 5-hexenoate, 6-heptenoate ethyl, ethyl 7-octenoate, Ethyl 8-Nonenoate, 9-Decanoate ethyl, ethyl 10-undecenoate, Ethyl 11-dodecenoate, 5-hexenoate of isopropyl, isopropyl 6-heptenoate, Isopropyl 7-octenoate, Isopropyl 8-Nonenoate, Isopropyl 9-Decanoate, Isopropyl 10-undecenoate, Isopropyl 11-dodecenoate, Butyl 5-hexenoate, 6-heptenoate of butyl, butyl 7-octenoate, Butyl 8-Nonenoate, 9-Decanoate of butyl, butyl 10-undecenoate, Butyl 11-dodecenoate, Pentyl 5-hexenoate, 6-heptenoate pentyl, pentyl 7-octenoate, Phenyl 8-Nonenoate, 9-Decanoate of pentyl, pentyl 10-undecenoate and Pentyl 11-dodecenoate;

esters of alkenylcarboxylic acids that they have a linear chain hydrocarbon group, such as 2-methyl-5-hexenoate of methyl, 2-methyl-6-heptenoate of methyl, 2-methyl-7-octenoate of ethyl, 2-methyl-8-nonenoate of methyl, 2-methyl-9-decanoate of butyl, 2-methyl-10-undecenoate of ethyl, 2-ethyl-5-hexenoate of butyl, 2-ethyl-6-heptenoate of ethyl, 2-ethyl-7-octenoate of isopropyl, 2-ethyl-8-nonenoate of ethyl, 2-ethyl-9-decanoate of methyl, 2-ethyl-10-undecenoate of ethyl, 2-propyl-5-hexenoate of methyl, 2-propyl-6-heptenoate of methyl, 2-propyl-7-octenoate of ethyl, 2-propyl-9-decanoate  of methyl, 2-propyl-10-undecenoate of ethyl, 2-butyl-7-octenoate of methyl, 2-butyl-8-nonenoate of methyl, 2-Butyl-9-Decanoate of methyl and 2-butyl-10-undecenoate of methyl; Y

alkenylcarboxylic acids having a group branched hydrocarbon, such as 2-isopropyl-5-hexenoate  of butyl, 2-isopropyl-6-heptenoate of ethyl, 2-isopropyl-7-octenoate of methyl, 2-isopropyl-8-nonenoate of methyl, 2-Isopropyl-9-Decanoate of butyl, 2-isopropyl-10-undecenoate of methyl, 2-isobutyl-5-hexenoate of methyl, 2-t-butyl-6-heptenoate of methyl, 2-Isopropyl-3-methyl-7-octenoate of ethyl and 3-isobutyl-3-methyl-9-decenoate  of propyl;

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compounds in which X in the formula (7) is a acid anhydride group, such as anhydride (2,7-octadienyl) succinic, anhydride pentapropenylsuccinic and compounds in which the acid group carboxylic acid is substituted by a carboxylic anhydride group in compounds shown by way of example above in which X is a carboxylic acid group;

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compounds of formula (7) in which X is a amino group, specifically

? -alkenylamines, such as allylamine, 5-hexenamine, 6-heptenamine, 7-octenamine, 8-nonenamine, 9-decenamine, 10-undecenamine and 11-dodecenamine;

alkenylamines that have a group linear chain hydrocarbon, such as 2-methyl-5-hexenamine, 2-methyl-6-heptenamine, 2-methyl-7-octenamine, 2-methyl-8-nonenamine, 2-methyl-9-decenamine, 2-methyl-10-undecenamine, 2-methyl-11-dodecenamine, 2-ethyl-5-hexenamine, 2-ethyl-6-heptenamine, 2-ethyl-7-octenamine, 2-ethyl-8-nonenamine, 2-ethyl-9-decenamine, 2-ethyl-10-undecenamine, 2-propyl-5-hexenamine, 2-propyl-6-heptenamine, 2-propyl-5-hexenamine, 2-propyl-6-heptenamine, 2-propyl-7-octenamine, 2-propyl-8-nonenamine, 2-propyl-9-decenamine, 2-propyl-10-undecenamine, 2-butyl-5-hexenamine, 2-butyl-6-heptenamine, 2-butyl-7-octenamine, 2-butyl-8-nonenamine, 2-butyl-9-decenamine Y 2-butyl-10-undecenamine;

alkenylamines that have a group branched hydrocarbon, such as 2-isopropyl-5-hexenamine, 2-isopropyl-6-heptenamine, 2-isopropyl-7-octenamine, 2-isopropyl-8-nonenamine, 2-isopropyl-9-decenamine, 2-isopropyl-10-undecenamine, 2-isobutyl-5-hexenamine, 2-t-butyl-6-heptenamine, 2-Isopropyl-3-methyl-7-octenamine, 2-methyl-3-isopropyl-8-nonenamine, 3-isobutyl-3-methyl-9-decenamine, 2,2-dimethyl-10-undecenamine Y 2,3,3-trimethyl-11-dodecenamine;

N-alkyl-? -Alkenylamines, such as N-methyl-5-hexenamine, N-methyl-6-heptenamine, N-methyl-7-octenamine, N-methyl-8-nonenamine, N-methyl-9-decenamine, N-methyl-10-undecenamine, N-methyl-11-dodecenamine, N-ethyl-5-hexenamine, N-ethyl-6-heptenamine, N-ethyl-7-octenamine, N-ethyl-8-nonenamine, N-ethyl-9-decenamine, N-ethyl-10-undecenamine  Y N-ethyl-11-dodecenamine;

N-alkylalkenylamines that they have a linear chain hydrocarbon group, such as N-methyl-6-hepten-2-amine, N-ethyl-7-octen-2-amine, N-methyl-8-nonen-2-amine, N-ethyl-9-decen-2-amine, N-methyl-10-undecen-2-amine, N-ethyl-8-nonen-3-amine, N-methyl-9-decen-3-amine, N-ethyl-10-undecen-3-amine, N-ethyl-8-nonen-9-amine, N-methyl-9-decen-4-amine Y N-ethyl-10-undecen-4-amine;

N-alkylalkenylamines that they have a branched hydrocarbon group, such as N-methyl-2-methyl-5-hexenamine, N-ethyl-2-methyl-6-heptenamine, N-methyl-2-methyl-7-octenamine, N-ethyl-2-methyl-8-nonenamine, N-ethyl-2-methyl-9-decenamine, N-methyl-2-methyl-10-undecenamine, N-methyl-2-ethyl-7-octenamine, N-ethyl-2-ethyl-9-decenamine Y N-methyl-2-ethyl-10-undecenamine;

N, N-dialkyl-? -Alkenylamines, such as N, N-dimethyl-5-hexenamine, N, N-dimethyl-6- heptenamine, N, N-dimethyl-7-octenamine, N, N-dimethyl-8-nonenamine, N, N-dimethyl-9-decenamine, N, N-dimethyl-10-undecenamine, N, N-dimethyl-11-dodecenamine, N, N-diethyl-5-hexenamine, N, N-diethyl-6-heptenamine, N, N-diethyl-7-octenamine, N, N-diethyl-8-nonenamine, N, N-diethyl-9-decenamine, N, N-diethyl-10-undecenamine Y N, N-diethyl-11-dodecenamine;

N, N-dialkylalkenylamines that they have a linear chain hydrocarbon group, such as N, N-dimethyl-6-hepten-2-amine, N, N-diethyl-7-octen-2-amine, N, N-dimethyl-8-nonen-2-amine, N, N-diethyl-9-decen-2-amine, N, N-dimethyl-10-undecen-2-amine, N, N-diethyl-8-nonen-3-amine, N, N-dimethyl-9-decen-3-amine, N, N-diethyl-10-undecen-3-amine, N, N-diethyl-8-nonen-4-amine, N, N-dimethyl-9-decen-4-amine Y N, N-diethyl-10-undecen-4 amine; Y

N, N-dialkylalkenylamines that they have a branched hydrocarbon group, such as N, N-dimethyl-2-methyl-5-hexenamine, N, N-diethyl-2-methyl-6-heptenamine, N, N-dimethyl-2-methyl-7-octenamine, N, N-diethyl-2-methyl-8-nonenamine, N, N-diethyl-2-methyl-9-decenamine, N, N-dimethyl-2-methyl-10-undecenamine, N, N-dimethyl-2-ethyl-7-octenamine, N, N-diethyl-2-ethyl-9-decenamine Y N, N-dimethyl-2-ethyl-10-undecenamine;

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compounds of formula (7) in which X is a amido group, specifically

? -alkenyl amides, such as allylamide, 5-hexenamide, 6-heptenamide, 7-octenamide, 8-nonenamide, 9-decenamide, 10-undecenamide and 11-dodecenamide;

alkenyl amides having a group linear chain hydrocarbon, such as 6-hepten-2-amide, 7-octen-2-amide, 8-nonen-2-amide, 9-decen-2-amide, 10-undecen-2-amide, 8-nonen-3-amide, 9-decen-3-amide, 10-undecen-3-amide, 11-dodecen-3-amide, 8-nonen-4-amide, 9-decen-4-amide, 10-undecen-4-amide, 11-dodecen-4-amide, 9-decen-5-amide and 10-undecen-5-amide;

N-alkyl-? -Alkenyl amides, such as N-methyl-5-hexenamide, N-methyl-6-heptenamide, N-methyl-7-octenamide, N-methyl-8-nonenamide, N-methyl-9-decenamide, N-methyl-10-undecenamide, N-methyl-11-dodecenamide, N-ethyl-5-hexenamide, N-ethyl-6-heptenamide, N-ethyl-7-octenamide, N-ethyl-8-nonenamide, N-ethyl-9-decenamide, N-ethyl-10-undecenamide  Y N-ethyl-11-dodecenamide;

N, N-dialkyl-? -Alkenyl amides, such as N, N-dimethyl-5-hexenamide, N, N-dimethyl-6-heptenamide, N, N-dimethyl-7-octenamide, N, N-dimethyl-8-nonenamide, N, N-dimethyl-9-decenamide, N, N-dimethyl-10-undecenamide, N, N-dimethyl-11-dodecenamide, N, N-diethyl-5-hexenamide, N, N-diethyl-6-heptenamide, N, N-diethyl-7-octenamide, N, N-diethyl-8-nonenamide, N, N-diethyl-9-decenamide, N, N-diethyl-10-undecenamide Y N, N-diethyl-11-dodecenamide;

alkenyl amides having a group branched hydrocarbon, such as 2-methyl-5-hexenamide, 2-methyl-6-heptenamide, 2-methyl-7-octenamide, 2-methyl-8-nonenamide, 2-methyl-9-decenamide, 2-methyl-10-undecenamide, 2-ethyl-5-hexenamide, 2-ethyl-6-heptenamide, 2-ethyl-7-octenamide, 2-ethyl-8-nonenamide, 2-ethyl-9-decenamide, 2-ethyl-10-undecenamide, 2-ethyl-11-dodecenamide, 2-propyl-5-hexenamide, 2-propyl-6-heptenamide, 2-propyl-7-octenamide, 2-propyl-8-nonenamide, 2-propyl-9-decenamide, 2-propyl-10-undecenamide, 2-propyl-11-dodecenamide, 2-butyl-5-hexenamide, 2-butyl-6-heptenamide, 2-butyl-7-octenamide, 2-butyl-8-nonenamide, 2-butyl-9-decenamide Y 2-butyl-10-undecenamide;

N, N-dialkylalkenyl amides which they have a branched hydrocarbon group, such as N, N-dimethyl-2-methyl-5-hexenamide, N, N-diethyl-2-methyl-6-heptenamide, N, N-dimethyl-2-methyl-7-octenamide, N, N-diethyl-2-methyl-8-nonenamide, N, N-diethyl-2-methyl-9-decenamide, N, N-diethyl-2-methyl-10-undecenamide, N, N-dimethyl-2-ethyl-7-octenamide, N, N-diethyl-2-ethyl-9-decenamide Y N, N-dimethyl-2-ethyl-10-undecenamide;

alkenyliamides, such as 6-hepten-1,2-diamide, 7-octen-1,2-diamide, 8-nonen-1,2-diamide, 9-decen-1,3-diamide, 10-undecen-1,3-diamide Y 11-dodecen-1,3-diamide;

alkenyltriamides, such as 9-decen-1,2,3-triamide Y 10-undecen-1,2,3-triamide; Y

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compounds of formula (7) in which X is a epoxy group, specifically

ome-alkenyl epoxides, such as 5-hexene epoxide, epoxy 6-heptene, 7-octene epoxide, 8-noneno epoxide, epoxy 9-decene, 10-undecene epoxide and 11-dodecene epoxide; Y

ome-alkenyl epoxides having a branched hydrocarbon group, such as epoxy 2-methyl-5-hexene, epoxy of 2-methyl-6-heptene, epoxy of 2-methyl-7-octene, epoxy of 2-methyl-8-noneno, epoxy of 2-methyl-9-decene and epoxy of 2-methyl-10-undecene; Y

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compounds in which X in the formula (7) is a mercapto group, such as CH 2 = CH-CH 2 -CH 2 -CH 2 -CH 2 -O-Ph-SH.

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Other examples of monomers containing polar group include the compounds represented by the following  formulas

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37

38

39

40

Are also available n-nonyl-1-ol, acid n-nonyl-1-carboxylic acid, n-nonyl-1-carboethoxy, 1,2-epoxy-nonyl anhydride (6-hexen-1-yl) succinic, n-undecil-1-ol, acid n-dodecyl-1-carboxylic, n-dodecyl-1-carboethoxy,  4-hexenyloxyphenol, 4-hexenyloxy-thiophenol, n-nonyl-1-carboxamide, n-nonyl-1-amino and n-nonyl-1-N-methylamino.

In the process to prepare the copolymer of olefin containing polar group according to the first embodiment of the invention, the monomer containing polar group represented by formula (7) it can be the group containing monomer polar represented by the following formula (7 ');

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41

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where R 3 ', p and X' have the same meanings as those of R 3 ', p and X', respectively, in the formula (3').

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Examples of group containing monomers polar of formula (7 ') in which X' is -OR include:

? -alkoxy-? -olefins, such as 3-methoxy-1-propene, 5-methoxy-1-pentene, 6-methoxy-1-hexene, 7-methoxy-1-heptene, 8-methoxy-1-octene, 9-methoxy-1-noneno, 10-methoxy-1-decene, 11-methoxy-1-undecene, 5-ethoxy-1-pentene, 6-ethoxy-1-hexene, 7-ethoxy-1-heptene, 8-ethoxy-1-octene, 9-ethoxy-1-noneno, 10-ethoxy-1-decene, 11-ethoxy-1-undecene, 5-propoxy-1-pentene,  6-propoxy-1-hexene, 7-propoxy-1-heptene, 8-propoxy-1-octene, 9-propoxy-1-noneno, 10-propoxy-1-decene, 11-propoxy-1-undecene,  5-butoxy-1-pentene, 6-butoxy-1-hexene, 7-butoxy-1-heptene, 8-butoxy-1-octene, 9-butoxy-1-noneno, 10-butoxy-1-decene Y 11-butoxy-1-undecene;

ethers having a hydrocarbon group branched, such as 7-methoxy-7-methyl-1-heptene, 8-methoxy-8-methyl-1-octene, 9-methoxy-8-methyl-1-noneno, 10-methoxy-9-methyl-1-decene, 11-methoxy-7-ethyl-1-undecene, 7-ethoxy-6-methyl-1-heptene, 8-ethoxy-6-ethyl-1-octene, 9-ethoxy-7-ethyl-1-noneno, 10-ethoxy-ethyl-1-decene, 11-ethoxy-8-propyl-1-undecene, 6-propoxy-6-methyl-1-hexene, 7-propoxy-7-methyl-1-heptene, 8-propoxy-8,8-dimethyl-1-octene, 9-propoxy-9-methyl-1-noneno, 10-propoxy-9,9-dimethyl-1-decene, 11-propoxy-10-methyl-1-undecene, 5-butoxy-5-ethyl-1-pentene, 6-butoxy-6,6-dimethyl-1-hexene, 7-butoxy-6-methyl-1-heptene, 8-butoxy-6-ethyl-1-octene, 9-butoxy-9-methyl-1-noneno, 10-butoxy-8,8-dimethyl-1-decene Y 11-butoxy-8,9-diethyl-1-undecene;

dialkoxy-? -olefins, such as 9,10-dimethoxy-1-dodecene Y 10,11-dimethoxy-1-undecene; Y

trialkoxy-α-olefins, such as 9,10,11-trimethoxy-1-undecene.

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Examples of the group containing monomer polar of formula (7 ') in which X' is -COOR include:

esters of? -alkenylcarboxylic acid, such as methyl 5-hexenoate, methyl 6-heptenoate, methyl 7-octenoate, methyl 8-nonenoate, methyl 9-denonoate, methyl 10-undecenoate, 11-dodecenoate methyl, ethyl 5-hexenoate, ethyl 6-heptenoate, ethyl 7-octenoate, ethyl 8-nonenoate, ethyl 9-denonoate, ethyl 10-undecenoate, ethyl 11-dodecenoate, isopropyl 5-hexenoate, Isopropyl 6-heptenoate, isopropyl 7-octenoate, isopropyl 8-nonenoate, isopropyl 9-denonoate, isopropyl 10-undecenoate, isopropyl 11-dodecenoate, butyl 5-hexenoate, butyl 6-heptenoate, 7- butyl octenoate, butyl 8-nonenoate, butyl 9-denonoate, butyl 10-undecenoate, butyl 11-dodecenoate, pentyl 5-hexenoate, pentyl 6-heptenoate, pentyl 7-octenoate, 8-nonenoate pentyl, pentyl 9-denonoate, pentyl 10-undecenoate and 11-dodecenoate
pentyl;

esters of alkenylcarboxylic acid having a linear chain hydrocarbon group, such as 2-methyl-5-hexenoate of methyl, 2-methyl-6-heptenoate of methyl, 2-methyl-7-octenoate of ethyl, 2-methyl-8-nonenoate of methyl, 2-methyl-9-decanoate of butyl, 2-methyl-10-undecenoate of ethyl, 2-ethyl-5-hexenoate of butyl, 2-ethyl-6-heptenoate of ethyl, 2-ethyl-7-octenoate of isopropyl, 2-ethyl-8-nonenoate of ethyl, 2-ethyl-9-decanoate of methyl, 2-ethyl-10-undecenoate of ethyl, 2-propyl-5-hexenoate of methyl, 2-propyl-6-heptenoate of methyl, 2-propyl-7-octenoate of ethyl, 2-propyl-9-decanoate  of methyl, 2-propyl-10-undecenoate of ethyl, 2-butyl-7-octenoate of methyl, 2-butyl-8-nonenoate of methyl, 2-Butyl-9-Decanoate of methyl and 2-butyl-10-undecenoate of methyl; Y

alkenylcarboxylic acids having a group branched hydrocarbon, such as 2-isopropyl-5-hexenoate  of butyl, 2-isopropyl-6-heptenoate of ethyl, 2-isopropyl-7-octenoate of methyl, 2-isopropyl-8-nonenoate of methyl, 2-Isopropyl-9-Decanoate of butyl, 2-isopropyl-10-undecenoate of methyl, 2-isobutyl-5-hexenoate of methyl, 2-t-butyl-6-heptenoate of methyl, 2-Isopropyl-3-methyl-7-octenoate of ethyl and 3-isobutyl-3-methyl-9-decenoate  of propyl.

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Examples of group containing monomers polar of formula (7 ') in which X' is -CRO include:

alkenyl ketone having a hydrocarbon group linear chain, such as 5-hexen-2-one, 6-hepten-2-one, 7-octen-2-one, 8-nonen-2-one, 9-decen-2-one, 10-undecen-2-one, 11-dodecen-2-one, 6-hepten-3-one, 7-octen-3-one, 8-nonen-3-one, 9-ten-3-one, 10-undecen-3-one, 11-dodecen-3-one, 7-octen-4-one, 8-nonen-4-one, 9-ten-4-one, 10-undecen-4-one, 11-dodecen-4-one, 9-ten-5-one, 10-undecen-5-one and 11-dodecen-5-one;

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alkenyl ketone having a hydrocarbon group branched as 3-methyl-6-hepten-2-one, 3-methyl-7-octen-2-one, 3-methyl-8-nonen-2-one, 3-methyl-9-decen-2-one, 3-ethyl-10-undecen-2-one, 3-methyl-11-dodecen-2-one, 2-methyl-7-octen-3-one, 2-methyl-8-nonen-3-one, 2-methyl-9-decen-3-one, 2-methyl-10-undecen-3-one, 3-methyl-7-octen-4-one, 3-ethyl-8-nonen-4-one, 3-ethyl-9-decen-4-one, 3-ethyl-10-undecen-4-one, 3-ethyl-11-dodecen-4-one, 3-ethyl-9-decen-5-one, 3-ethyl-10-undecen-5-one  Y 3-ethyl-11-dodecen-5-one;

alkenyl ketone, such as 8-nonen-2,4-one, 9-decen-2,4-one and 10-undecen-2,4-one; Y

alkenyltricetone, such as 10-undecen-2,4,6-one Y 11-dodecen-2,4,6-one.

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Examples of the group containing monomer polar of formula (7 ') in which X' is -NR'R '' (R 'and R' 'can be same or different and are a hydrogen atom and / or a group hydrocarbon) include:

? -alkenylamines, such such as 5-hexenamine, 6-heptenamine, 7-octenamine, 8-nonenamine, 9-decenamine, 10-undecenamine and 11-dodecenamine;

alkenylamines that have a group linear chain hydrocarbon, such as 2-methyl-5-hexenamine, 2-methyl-6-heptenamine, 2-methyl-7-octenamine, 2-methyl-8-nonenamine, 2-methyl-9-decenamine, 2-methyl-10-undecenamine, 2-methyl-11-dodecenamine, 2-ethyl-5-hexenamine, 2-ethyl-6-heptenamine, 2-ethyl-7-octenamine, 2-ethyl-8-nonenamine, 2-ethyl-9-decenamine, 2-ethyl-10-undecenamine, 2-propyl-5-hexenamine, 2-propyl-6-heptenamine, 2-propyl-5-hexenamine, 2-propyl-6-heptenamine, 2-propyl-7-octenamine, 2-propyl-8-nonenamine, 2-propyl-9-decenamine, 2-propyl-10-undecenamine, 2-butyl-5-hexenamine, 2-butyl-6-heptenamine, 2-butyl-7-octenamine, 2-butyl-8-nonenamine, 2-butyl-9-decenamine Y 2-butyl-10-undecenamine;  Y

alkenylamines that have a group branched hydrocarbon, such as 2-isopropyl-5-hexenamine, 2-isopropyl-6-heptenamine, 2-isopropyl-7-octenamine, 2-isopropyl-8-nonenamine, 2-isopropyl-9-decenamine, 2-isopropyl-10-undecenamine, 2-isobutyl-5-hexenamine, 2-t-butyl-6-heptenamine, 2-Isopropyl-3-methyl-7-octenamine, 2-methyl-3-isopropyl-8-nonenamine, 3-isobutyl-3-methyl-9-decenamine, 2,2-dimethyl-10-undecenamine Y 2,3,3-trimethyl-11-dodecenamine.

       \ vskip1.000000 \ baselineskip
    

Can also be used

N-alkyl-? -Alkenylamines, such as N-methyl-5-hexenamine, N-methyl-6-heptenamine, N-methyl-7-octenamine, N-methyl-8-nonenamine, N-methyl-9-decenamine, N-methyl-10-undecenamine, N-methyl-11-dodecenamine, N-ethyl-5-hexenamine, N-ethyl-6-heptenamine, N-ethyl-7-octenamine, N-ethyl-8-nonenamine, N-ethyl-9-decenamine, N-ethyl-10-undecenamine  Y N-ethyl-11-dodecenamine;

N-alkylalkenylamines that they have a linear chain hydrocarbon group, such as N-methyl-6-hepten-2-amine, N-ethyl-7-octen-2-amine, N-methyl-8-nonen-2-amine, N-ethyl-9-decen-2-amine, N-methyl-10-undecen-2-amine, N-ethyl-8-nonen-3-amine, N-methyl-9-decen-3-amine, N-ethyl-10-undecen-3-amine, N-ethyl-8-nonen-4-amine, N-methyl-9-decen-4-amine Y N-ethyl-10-undecen-4-amine;

N-alkylalkenylamines that they have a branched hydrocarbon group, such as N-methyl-2-methyl-5-hexenamine, N-ethyl-2-methyl-6-heptenamine, N-methyl-2-methyl-7-octenamine, N-ethyl-2-methyl-8-nonenamine, N-ethyl-2-methyl-9-decenamine, N-methyl-2-methyl-10-undecenamine, N-methyl-2-ethyl-7-octenamine, N-ethyl-2-ethyl-9-decenamine Y N-methyl-2-ethyl-10-undecenamine;

N, N-dialkyl-? -Alkenylamines, such as N, N-dimethyl-5-hexenamine, N, N-dimethyl-6-heptenamine, N, N-dimethyl-7-octenamine, N, N-dimethyl-8-nonenamine, N, N-dimethyl-9-decenamine, N, N-dimethyl-10-undecenamine, N, N-dimethyl-11-dodecenamine, N, N-diethyl-5-hexenamine, N, N-diethyl-6-heptenamine, N, N-diethyl-7-octenamine, N, N-diethyl-8-nonenamine, N, N-diethyl-9-decenamine, N, N-diethyl-10-undecenamine Y N, N-diethyl-11-dodecenamine;

N, N-dialkylalkenylamines that they have a linear chain hydrocarbon group, such as N, N-dimethyl-6-hepten-2-amine, N, N-diethyl-7-octen-2-amine, N, N-dimethyl-8-nonen-2-amine, N, N-diethyl-9-decen-2-amine, N, N-dimethyl-10-undecen-2-amine, N, N-diethyl-8-nonen-3-amine, N, N-dimethyl-9-decen-3-amine, N, N-diethyl-10-undecen-3-amine, N, N-diethyl-8-nonen-4-amine, N, N-dimethyl-9-decen-4-amine Y N, N-diethyl-10-undecen-4-amine; Y

N, N-dialkylalkenylamines that they have a branched hydrocarbon group, such as N, N-dimethyl-2-methyl-5-hexenamine, N, N-diethyl-2-methyl-6-heptenamine, N, N-dimethyl-2-methyl-7-octenamine, N, N-diethyl-2-methyl-8-nonenamine, N, N-diethyl-2-methyl-9-decenamine, N, N-dimethyl-2-methyl-10-undecenamine, N, N-dimethyl-2-ethyl-7-octenamine, N, N-diethyl-2-ethyl-9-decenamine Y N, N-dimethyl-2-ethyl-10-undecenamine.

       \ global \ parskip1.000000 \ baselineskip
    

Examples of group containing monomers polar of formula (7 ') in which X' is -CONR 2 (R is an atom of hydrogen or a hydrocarbon group) include:

? -alkenyl amides, such such as 5-hexenamide, 6-heptenamide, 7-octenamide, 8-nonenamide, 9-decenamide, 10-undecenamide and 11-dodecenamide;

alkenyl amides having a group linear chain hydrocarbon, such as 6-hepten-2-amide, 7-octen-2-amide, 8-nonen-2-amide, 9-decen-2-amide, 10-undecen-2-amide, 8-nonen-3-amide, 9-decen-3-amide, 10-undecen-3-amide, 11-dodecen-3-amide, 8-nonen-4-amide, 9-decen-4-amide, 10-undecen-4-amide, 11-dodecen-4-amide, 9-decen-5-amide and 10-undecen-5-amide;

N-alkyl-? -Alkenyl amides, such as N-methyl-5-hexenamide, N-methyl-6-heptenamide, N-methyl-7-octenamide, N-methyl-8-nonenamide, N-methyl-9-decenamide, N-methyl-10-undecenamide, N-methyl-11-dodecenamide, N-ethyl-5-hexenamide, N-ethyl-6-heptenamide, N-ethyl-7-octenamide, N-ethyl-8-nonenamide, N-ethyl-9-decenamide, N-ethyl-10-undecenamide  Y N-ethyl-11-dodecenamide;

N, N-dialkyl-? -Alkenyl amides, such as N, N-dimethyl-5-hexenamide, N, N-dimethyl-6-heptenamide, N, N-dimethyl-7-octenamide, N, N-dimethyl-8-nonenamide, N, N-dimethyl-9-decenamide, N, N-dimethyl-10-undecenamide, N, N-dimethyl-11-dodecenamide, N, N-diethyl-5-hexenamide, N, N-diethyl-6-heptenamide, N, N-diethyl-7-octenamide, N, N-diethyl-8-nonenamide, N, N-diethyl-9-decenamide, N, N-diethyl-10-undecenamide Y N, N-diethyl-11-dodecenamide;

alkenyl amides having a group branched hydrocarbon, such as 2-methyl-5-hexenamide, 2-methyl-6-heptenamide, 2-methyl-7-octenamide, 2-methyl-8-nonenamide, 2-methyl-9-decenamide, 2-methyl-10-undecenamide, 2-ethyl-5-hexenamide, 2-ethyl-6-heptenamide, 2-ethyl-7-octenamide, 2-ethyl-8-nonenamide, 2-ethyl-9-decenamide, 2-ethyl-10-undecenamide, 2-ethyl-11-dodecenamide, 2-propyl-5-hexenamide, 2-propyl-6-heptenamide, 2-propyl-7-octenamide, 2-propyl-8-nonenamide, 2-propyl-9-decenamide, 2-propyl-10-undecenamide, 2-propyl-11-dodecenamide, 2-butyl-5-hexenamide, 2-butyl-6-heptenamide, 2-butyl-7-octenamide, 2-butyl-8-nonenamide, 2-butyl-9-decenamide Y 2-butyl-10-undecenamide;

N, N-dialkylalkenyl amides which they have a branched hydrocarbon group, such as N, N-dimethyl-2-methyl-5-hexenamide, N, N-diethyl-2-methyl-6-heptenamide, N, N-dimethyl-2-methyl-7-octenamide, N, N-diethyl-2-methyl-8-nonenamide, N, N-diethyl-2-methyl-9-decenamide, N, N-diethyl-2-methyl-10-undecenamide, N, N-dimethyl-2-ethyl-7-octenamide, N, N-diethyl-2-ethyl-9-decenamide Y N, N-dimethyl-2-ethyl-10-undecenamide;

alkenyliamides, such as 6-hepten-1,2-diamide, 7-octen-1,2-diamide, 8-nonen-1,2-diamide, 9-decen-1,3-diamide, 10-undecen-1,3-diamide and 11-dodecenamide; Y

alkenyltriamides, such as 9-decen-1,2,3-triamide Y 10-undecen-1,2,3-triamide.

       \ vskip1.000000 \ baselineskip
    

Examples of the group containing monomer polar of formula (7 ') in which X' is -OCOR (R is a group hydrocarbon) are:

acid carboxylic-? -alkenyl, such as formic acid-5-hexenyl acid formic-6-heptenyl acid formic-7-octenyl acid formic-8-nonenyl acid formic-9-decenyl acid formic-10-undecenyl acid formic-11-dodecenyl acid acetic-5-hexenyl acid acetic-6-heptenyl acid acetic-7-octenyl acid acetic-8-nonenyl acid acetic-9-decenyl acid acetic-10-undecenyl acid acetic-11-dodecenyl acid propionic-5-hexenyl acid propionic-6-heptenyl acid propionic-7-octenyl acid propionic-8-nonenyl acid propionic-9-decenyl acid propionic-10-undecenyl acid propionic-11-dodecenyl acid butyric-5-hexenyl acid butyric-6-heptenyl acid butyric-7-octenyl acid butyric-8-nonenyl acid butyric-9-decenyl acid butyric-10-undecenyl and acid butyric-11-dodecenyl; Y

acid carboxylic-? -alkenyl which has a branched hydrocarbon group, such as acid formic-2-methyl-5-hexenyl,  acid formic-2-methyl-6-heptenyl, acid formic-3-ethyl-7-octenyl, acid formic-2-methyl-8-nonenyl, acid formic-3-ethyl-9-decenyl, acid formic-2-methyl-10-undecenyl, acid formic-2-methyl-11-dodecenyl, acid acetic-2-methyl-5-hexenyl, acid acetic-2-methyl-6-heptenyl, acid acetic-3-ethyl-7-octenyl, acid acetic-2-methyl-8-nonenyl,  acid acetic-3-ethyl-9-decenyl, acid acetic-2-methyl-10-undecenyl, acid acetic-3-ethyl-11-dodecenyl,  acid propionic-2-methyl-5-hexenyl, acid propionic-2-methyl-6-heptenyl, acid propionic-2-methyl-7-octenyl,  acid propionic-2-methyl-8-nonenyl, acid propionic-2-methyl-9-decenyl, acid propionic-2-methyl-10-undecenyl,  acid propionic-2-methyl-11-dodecenyl, acid butyric-2-methyl-5-hexenyl, acid butyric-2-methyl-6-heptenyl,  acid butyric-2-methyl-7-octenyl, acid butyric-3-methyl-8-nonenyl, acid butyric-3-methyl-9-decenyl, acid butyric-4-methyl-10-undecenyl and acid butyric-3-methyl-11-dodecenyl.

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Examples of the group containing monomer polar of formula (7 ') in which X' is -CN include:

? -alkenylnitriles, such as 5-hexenonitrile, 6-heptenonitrile, 7-octenonitrile, 8-nonenonitrile, 9-decenonitrile, 10-undecenonitrile and 11-dodecenonitrile;

alkenylnitriles that have a group linear chain hydrocarbon, such as 2-methyl-5-hexenonitrile, 2-methyl-6-heptenonitrile, 2-methyl-7-octenonitrile, 2-methyl-8-nonenonitrile, 2-methyl-9-decenonitrile, 2-methyl-10-undecenonitrile, 2-methyl-11-dodecenonitrile, 2-ethyl-5-hexenonitrile, 2-ethyl-6-heptenonitrile, 2-ethyl-7-octenonitrile, 2-ethyl-8-nonenonitrile, 2-ethyl-9-decenonitrile, 2-ethyl-10-undecenonitrile, 2-propyl-5-hexenonitrile, 2-propyl-6-heptenonitrile, 2-propyl-7-octenonitrile, 2-propyl-8-nonenonitrile, 2-propyl-9-decenonitrile, 2-propyl-10-undecenonitrile, 2-butyl-5-hexenonitrile, 2-butyl-6-heptenonitrile, 2-butyl-7-octenonitrile, 2-butyl-8-nonenonitrile, 2-butyl-9-decenonitrile Y 2-butyl-10-undecenonitrile;

alkenylnitriles that have a group branched hydrocarbon, such as 2-isopropyl-5-hexenonitrile, 2-isopropyl-6-heptenonitrile, 2-isopropyl-7-octenonitrile, 2-isopropyl-8-nonenonitrile, 2-isopropyl-9-decenonitrile, 2-isopropyl-10-undecenonitrile, 2-isobutyl-5-hexenonitrile, 2-t-butyl-6-heptenonitrile, 2-Isopropyl-3-methyl-7-octenonitrile, 2-methyl-3-isopropyl-8-nonenonitrile, 3-isobutyl-3-methyl-9-decenonitrile, 2,2-dimethyl-10-undecenonitrile Y 2,3,3-trimethyl-11-dodecenonitrile;

alkenyl nitrile, such as 10-undecen-1,2-dinitrile Y 11-dodecen-1,2-dinitrile; Y

alkenyltrinitrile, such as 10-undecen-1,2,3-trinitrile.

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Examples of monomers containing polar group of formula (7 ') in which X' is -OH include:

ga-alkenyl alcohols, such as 4-penten-1-ol, 5-hexen-1-ol, 6-hepten-1-ol, 7-octen-1-ol, 8-nonen-1-ol, 9-decen-1-ol, 10-undecen-1-ol and 11-dodecen-1-ol;

alcohols having a hydrocarbon group of linear chain, such as 5-hexen-2-ol, 6-hepten-2-ol, 7-octen-2-ol, 8-nonen-2-ol, 9-decen-2-ol, 10-undecen-2-ol, 6-hepten-3-ol, 7-octen-3-ol, 8-nonen-3-ol, 9-decen-3-ol, 10-undecen-3-ol, 11-dodecen-3-ol, 7-octen-4-ol, 8-nonen-4-ol, 9-decen-4-ol, 10-undecen-4-ol, 8-nonen-5-ol, 9-decen-5-ol and 10-undecen-5-ol;

alcohols that have a hydrocarbon group branched, such as 2-ethyl-5-hexen-1-ol, 3-methyl-6-hepten-1-ol, 3-methyl-7-octen-1-ol, 4-methyl-8-nonen-1-ol, 3-ethyl-9-decen-1-ol, 2-methyl-10-undecen-2-ol, 2,2-dimethyl-7-octen-1-ol, 3-ethyl-2-methyl-8-nonen-1-ol, 2,2,3-trimethyl-9-decen-1-ol Y 2,3,3,4-tetramethyl-10-undecen-2-ol;

diols, such as 9-decen-1,2-diol, 10-undecen-1,2-diol, 11-dodecen-1,2-diol Y 11-dodecen-1,2-diol; Y

triols, such as 10-undecen-1,2,3-triol.

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Examples of the group containing monomer polar of formula (7 ') in which X' is -CHO include:

\ omega-alkenyl aldehydes, such as 5-hexenal, 6-heptenal, 7-octenal, 8-nonenal, 9-decennial, 10-undecenal and 11-dodecenal;

alkenyl aldehydes that have a group linear chain hydrocarbon, such as 2-methyl-5-hexenal, 2-methyl-6-heptenal, 2-methyl-7-octenal, 2-methyl-8-nonenal, 2-methyl-9-decennial, 2-methyl-10-undecenal, 2-methyl-11-dodecenal, 2-ethyl-5-hexenal, 2-ethyl-6-heptenal, 2-ethyl-7-octenal, 2-ethyl-8-nonenal, 2-ethyl-9-decennial, 2-ethyl-10-undecenal, 2-propyl-5-hexenal, 2-propyl-6-heptenal, 2-propyl-7-octenal, 2-propyl-8-nonenal, 2-propyl-9-decennial, 2-propyl-10-undecenal, 2-butyl-5-hexenal, 2-butyl-6-heptenal, 2-butyl-7-octenal, 2-butyl-8-nonenal, 2-butyl-9-decennial and 2-butyl-10-undecenal; Y

alkenyl aldehydes that have a group branched hydrocarbon, such as 2-isopropyl-5-hexenal, 2-isopropyl-6-heptenal, 2-isopropyl-7-octenal, 2-isopropyl-8-nonenal, 2-isopropyl-9-decennial, 2-isopropyl-10-undecenal, 2-isobutyl-5-hexenal, 2-t-butyl-6-heptenal, 2-Isopropyl-3-methyl-7-octenal, 2-methyl-3-isopropyl-8-nonenal, 3-isobutyl-3-methyl-9-decennial, 2,2-dimethyl-10-undecenal Y 2,3,3-trimethyl-11-dodecenal.

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Examples of monomers containing polar group of formula (7 ') in which X' is -COOH include:

acids ? -alkenylcarboxylic acids, such as acid acrylic, 5-hexenoic acid, acid 6-heptenoic acid, 7-octenoic acid, 8-nonenoic acid, acid 9-Decenoic, 10-undecenoic acid and 11-dodecenoic acid;

alkenylcarboxylic acids having a group linear chain hydrocarbon, such as acid 2-methyl-5-hexenoic,  acid 2-methyl-6-heptenoic, acid 2-methyl-7-octenoic, acid 2-methyl-8-nonenoic, acid 2-methyl-9-decene,  acid 2-methyl-10-undecenoic, acid 2-methyl-11-dodecenoic, acid 2-ethyl-5-hexenoic, acid 2-ethyl-6-heptenoic,  acid 2-ethyl-7-octenoic, acid 2-ethyl-8-nonenoic, acid 2-ethyl-9-decene, acid 2-ethyl-10-undecenoic,  acid 2-propyl-5-hexenoic, acid 2-propyl-6-heptenoic, acid 2-propyl-7-octenoic, acid 2-propyl-8-nonenoic,  acid 2-propyl-9-decenoic, acid 2-propyl-10-undecenoic, acid 2-butyl-5-hexenoic, acid 2-butyl-6-heptenoic,  acid 2-butyl-7-octenoic, acid 2-butyl-8-nonenoic, acid 2-butyl-9-decene and acid 2-butyl-10-undecenoic;  Y

alkenylcarboxylic acids having a group branched hydrocarbon, such as acid 2-isopropyl-5-hexenoic,  acid 2-isopropyl-6-heptenoic, acid 2-isopropyl-7-octenoic, acid 2-isopropyl-8-nonenoic, acid 2-Isopropyl-9-Decanoic,  acid 2-isopropyl-10-undecenoic, acid 2-isobutyl-5-hexenoic, acid 2-t-butyl-6-heptenoic, acid 2-Isopropyl-3-methyl-7-octenoic,  acid 2-methyl-3-isopropyl-8-nonenoic, acid 3-isobutyl-3-methyl-9-decenoic, acid 2,2-dimethyl-10-undecenoic  and acid 2,3,3-trimethyl-11-dodecenoic.

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Examples of the group containing monomer polar of formula (7 ') in which X' is an epoxy group include:

ome-alkenyl epoxides, such as 5-hexene epoxide, epoxy 6-heptene, 7-octene epoxide, 8-noneno epoxide, epoxy 9-decene, 10-undecene epoxide and 11-dodecene epoxide; Y

alkenyl epoxides having a group branched hydrocarbon, such as epoxy 2-methyl-5-hexene, epoxy of 2-methyl-6-heptene, epoxy of 2-methyl-7-octene, epoxy of 2-methyl-8-noneno, epoxy of 2-methyl-9-decene and epoxy of 2-methyl-10-undecene.

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42

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where R 7, R 8, Y, m, n and s have the same meanings as those of R 7, R 8, Y, m, n and s, respectively, in the formula (6).

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In the formula (8) above, R 7 and R 8 are preferably a direct bond or a hydrocarbon group of 1 to 10 carbon atoms and Y is preferably -OR, -COOR, -CRO, -NR 2, an epoxy group, 43 (R is a hydrogen atom or a hydrocarbon group), -C? N, -OH, -COOH or -NH2.

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Examples of the group containing monomer polar represented by the formula (8) in which Y is -OR (R is a hydrogen atom or a hydrocarbon group) include

bicyclic monoethers such as

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44

Four. Five

46

       \ vskip1.000000 \ baselineskip
    

       \ vskip1.000000 \ baselineskip
    

such bicyclic diesters how

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47

       \ newpage
    

tetracyclic monoethers such how

       \ vskip1.000000 \ baselineskip
    

48

       \ vskip1.000000 \ baselineskip
    

tetracyclic diesters such how

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49

       \ newpage
    

Examples of the group containing monomer polar represented by the formula (8) in which Y is -COOR (R is a hydrogen atom or a hydrocarbon group) include

esters of bicyclic carboxylic acids such how

fifty

51

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       \ vskip1.000000 \ baselineskip
    

esters of dicarboxylic acids bicyclics such how

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52

       \ newpage
    

esters of monocarboxylic acids tetracyclics such how

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53

       \ vskip1.000000 \ baselineskip
    

       \ vskip1.000000 \ baselineskip
    

esters of dicarboxylic acids tetracyclics such how

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54

       \ newpage
    

acid anhydrides such how

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55

       \ vskip1.000000 \ baselineskip
    

Examples of the group containing monomer polar represented by the formula (8) in which Y is -CRO (R is a hydrocarbon group) include

bicyclic ketones such as

       \ vskip1.000000 \ baselineskip
    

56

57

       \ newpage
    

such bicyclic diketones how

58

       \ vskip1.000000 \ baselineskip
    

       \ vskip1.000000 \ baselineskip
    

tetracyclic ketones such how

59

       \ newpage
    

tetracyclic diketones such how

       \ vskip1.000000 \ baselineskip
    

60

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Examples of the group containing monomer polar represented by the formula (8) in which Y is -NR2 (R is a hydrogen atom or a hydrocarbon group) include

bicyclic amines such as

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61

62

       \ vskip1.000000 \ baselineskip
    

       \ vskip1.000000 \ baselineskip
    

such bicyclic diamines how

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63

       \ newpage
    

tetracyclic amines such how

       \ vskip1.000000 \ baselineskip
    

64

       \ vskip1.000000 \ baselineskip
    

       \ vskip1.000000 \ baselineskip
    

tetracyclic diamines such how

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65

       \ newpage
    

Examples of the polar group containing monomer represented by the formula (8) in which Y is 66 (R is a hydrogen atom or a hydrocarbon group) include

bicyclic amides such as

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67

68

       \ vskip1.000000 \ baselineskip
    

       \ vskip1.000000 \ baselineskip
    

such bicyclic diamides how

       \ vskip1.000000 \ baselineskip
    

69

       \ newpage
    

tetracyclic amides such how

       \ vskip1.000000 \ baselineskip
    

70

       \ vskip1.000000 \ baselineskip
    

tetracyclic diamides such how

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71

       \ newpage
    

Examples of the polar group containing monomer represented by the formula (8) in which Y is 72 (R is a hydrogen atom or a hydrocarbon group) include

bicyclic esters such as

       \ vskip1.000000 \ baselineskip
    

73

74

       \ vskip1.000000 \ baselineskip
    

such bicyclic diesters how

75

       \ newpage
    

tetracyclic esters such how

       \ vskip1.000000 \ baselineskip
    

76

       \ vskip1.000000 \ baselineskip
    

tetracyclic diesters such how

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77

       \ newpage
    

Examples of the group containing monomer polar represented by the formula (8) in which Y is -C \ equiv N include

bicyclic nitriles such as

78

79

       \ vskip1.000000 \ baselineskip
    

such bicyclic dinitriles how

80

       \ newpage
    

tetracyclic nitriles such how

       \ vskip1.000000 \ baselineskip
    

81

       \ vskip1.000000 \ baselineskip
    

tetracyclic dinitriles such how

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82

       \ newpage
    

Examples of the group containing monomer polar represented by the formula (8) in which Y is -OH include

bicyclic alcohols such as

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83

84

such bicyclic diols how

85

tetracyclic alcohols such how

86

87

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tetracyclic diols such how

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88

       \ vskip1.000000 \ baselineskip
    

       \ vskip1.000000 \ baselineskip
    

Examples of the group containing monomer polar represented by the formula (8) in which Y is -COOH include

bicyclic monocarboxylic acids such how

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89

90

91

bicyclic dicarboxylic acids such how

92

tetracyclic carboxylic acids such how

93

94

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tetracyclic dicarboxylic acids such how

       \ vskip1.000000 \ baselineskip
    

95

       \ vskip1.000000 \ baselineskip
    

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Examples of the group containing monomer polar represented by the formula (8) in which Y is -CHO include

bicyclic aldehydes such as

96

97

98

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such bicyclic dialdehydes how

99

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tetracyclic aldehydes such how

100

101

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tetracyclic dialdehydes such how

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102

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Examples of the group containing monomer polar represented by the formula (8) in which Y is -NH2 include

bicyclic monoamines such as

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103

104

105

such bicyclic diamines how

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106

tetracyclic monoamines such how

107

108

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tetracyclic diamines such how

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109

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In this invention, it is also possible copolymerize polyenes with the α-olefins and monomers containing polar group. The polyenes shown to exemplary are olefins that have an aliphatic ring or a aromatic ring, such as cyclopentene, cycloheptene, 2-methyl-1,4,5,8-dimethane-1,2,3,4,4a, 5,8,8a-octahydronaphthalene,  styrene and vinylcyclohexane; a chain or cyclic diene, such as butadiene, isoprene, 1,4-hexadiene, dicyclopentadiene, 5-ethyliden-2-norbornene, 7-methyl-1,6-octadiene; a chain or cyclic triene, such as 6,10-dimethyl-1,5,9-undecatriene  Y 5,9-dimethyl-1,4,8-decatriene; and a chain or cyclic tetraene, such as 6,10,14-trimethyl-1,5,9,13-pentadecatetraen  Y 5,9,13-trimethyl-1,4,8,12-tetradecatetraen.

In a procedure to prepare a copolymer containing polar group according to the first reference embodiment,  at least one olefin selected from the α-olefin of 2 to 20 carbon atoms mentioned above is polymerized with a monomer containing polar group represented by formula (7) and / or a monomer containing polar group represented by formula (8) in presence of the mentioned olefin polymerization catalyst previously under the following polymerization conditions.

When the polar group containing monomer is a monomer such that X in the formula (7) is -OH and Y in the formula (8) is -OH, it is preferred to use a transition metal compound (A) represented by any one of the formulas (11) to (16), more preferably a transition metal compound (A) represented by any one of the formulas (11) to (15). When the polar group-containing monomer is a monomer such that X in formula (7) is -NR'R '' (R 'and R''can be the same or different from each other and are a hydrogen atom and an alkyl group ) and Y in the formula (8) is -NR2 (R is hydrogen or an alkyl group), it is preferred to use a transition metal compound (A) represented by any one of the formulas (11) to (16 ), more preferably a transition metal compound (A) represented by any one of formulas (11), (12), (14), (15) and
(16).

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In the process to prepare a copolymer containing polar group according to the first reference embodiment,  a polar group can be introduced selectively at one end terminal of a polymer chain or within the main chain by selecting the type of polar group and the conditions of reaction. In addition, the characteristics of the polymer it contains Polar group can be diversified using two or more kinds of olefins in polymerization.

Deactivation of the catalyst by monomer containing functional group can be made as low as it is possible by previously contacting the metal compound transition (A) and / or the monomer containing polar group with the organoaluminum compound.

To contact the monomers that contain polar group with the organoaluminum compound, there is a method of contacting them before adding them to the polymerization system and a method of adding the two components successively to the polymerization system, and any of these methods is useful.

To contact metal compounds of transition with the organoaluminum compound, there is a method of contact them before adding them to the system polymerization and a method of adding the two components successively to the polymerization system in a manner similar to above, and any of these methods is useful.

In polymerization, the metal compound of transition (A) is used in an amount usually of about 0.00005 to 0.1 mmol, preferably of approximately 0.0001 to 0.05 mmol, as for the metal atom of transition, based on 1 liter of the volume of polymerization.

The oxy-compound of Organoaluminum (B-1) is used in an amount such that the amount of the aluminum atom usually becomes of about 1 to 10,000 moles, preferably 10 to 5,000 moles, based on 1 mole of the transition metal atom.

The ionizing ionic compound (B-2) is used in an amount such that the amount of the boron atom usually becomes about 0.5 to 500 moles, preferably 1 to 100 moles, based on 1 mole of transition metal atom.

The organoaluminum compound (B-3) is used in an amount such that the amount of the aluminum atom usually becomes about 10 to 500 moles, preferably about 20 to 200 moles, based on 1 mol of the transition metal atom.

When the oxy compound is used of organoaluminum (B-1) and the compound of organoaluminum (B-3) in combination, the compound Organoaluminum (B-3) is used when necessary in an amount usually from about 0 to 200 moles, preferably about 0 to 100 moles, based on 1 mole of the aluminum atom in the oxy-compound of organoaluminum (B-1). When the compound is used ionic ionic (B-2) and compound organoaluminum (B-3) in combination, the compound of Organoaluminum (B-3) is used when necessary in an amount usually of about 0 to 1000 moles, preferably from about 0 to 500 moles, based on 1 mole of the boron atom in the ionizing ionic compound (B-2).

When the organosilicon compound (C) is used, This compound is used in an amount of 1 to 10,000 moles, preferably 10 to 5000 moles, based on 1 mole of the atom of transition metal

When the dialkylzinc compound (D) is used, This compound is used in an amount of 1 to 10,000 moles, preferably 10 to 5000 moles, based on 1 mole of the atom of transition metal

When hydrogen is used, hydrogen is used in an amount of 10-5 at 1 mole, preferably 10-4 at 10-1 mol, based on 1 mol of the total olefin and the monomer containing polar group used in the polymerization.

Although there is no specific limitation on the ratio between the monomer containing polar group and the atom of transition metal, the molar ratio of monomer containing group polar / transition metal atom is in the range of usually 1/100 to 10000/1, preferably 1/10 to 5000/1.

The copolymerization of an olefin and the monomer which contains polar group can be carried out by any liquid phase polymerization process such as suspension polymerization or solution polymerization, a gas phase polymerization process and a process to high pressure.

In the liquid phase polymerization, an inert hydrocarbon medium is used, and examples thereof include aliphatic hydrocarbons, such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; alicyclic hydrocarbons, such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons, such as benzene, toluene and xylene; and halogenated hydrocarbons, such as ethylene chloride, chlorobenzene and dichloromethane. Olefin itself can be used as a solvent. These solvents can be used
in combination.

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When polymerization is performed in suspension, the polymerization temperature is usually at the range of -50 to 100 ° C, preferably 0 to 90 ° C; when performs the polymerization in solution, the temperature of polymerization is usually in the range of 0 to 300 ° C, preferably from 20 to 250 ° C; when polymerization is performed In the gas phase, the polymerization temperature is usually  in the range of 0 to 120 ° C, preferably 20 to 100 ° C; Y when the procedure is performed at high pressure, the temperature polymerization is usually in the range of 50 to 1000 ° C, preferably from 100 to 500 ° C. The polymerization pressure is usually in the atmospheric pressure range at 100 kg / cm2, preferably at atmospheric pressure at 50 kg / cm2. In the case of the high pressure procedure, the pressure  is usually in the range of 100 to 10,000 kg / cm2, preferably from 500 to 5000 kg / cm2. The reaction of polymerization can be carried out by any of the discontinuous, semi-continuous and continuous procedures. Besides, the polymerization can be carried out in two or more stages in Different reaction conditions.

The molecular weight of the olefin copolymer that contains the resulting polar group can be regulated by controlling the amount of hydrogen, organosilicon compound or compound of dialkylzinc or by changing the polymerization temperature or the polymerization pressure.

In the process to prepare a copolymer containing polar group according to the first reference embodiment,  an α-olefin of 2 to 20 is copolymerized carbon atoms and a monomer containing polar group represented by the following formula (7 '') and / or (8 ') in the presence of a catalyst comprising:

(A) the transition metal compound, and

(B) at least one compound selected from:

(B-1) a oxy-organoaluminum compound,

(B-2) a compound that reacts with the compound (A) to form an ionic pair, and

(B-3) a compound of organoaluminum

(7 '') CH 2 = CH-R 3 '' - X '' p

where R 3 '' is a group hydrocarbon of 2 or more carbon atoms, X '' is -OR, -COOR, -CRO, -C (O) NR2, -OC (O) R (R is a hydrogen atom or a hydrocarbon group), an epoxy group, -C \ equivN or -NH_ {2} and p is a positive integer from 1 to 3.

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The monomer that contains polar group represented by the formula (7 '') is, for example, the monomer containing polar group represented by the formula (7 ') mentioned above in which X is another group other than -OH and -NR_ {2}.

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110

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in which R 7 is a link direct or an aliphatic hydrocarbon group of 1 or more atoms of carbon, R 8 is a hydrogen atom, a direct bond or a aliphatic hydrocarbon group of 1 or more carbon atoms, Y 'is -OR, -COOR, -CRO, -C (O) NR2, -OC (O) R (R is a hydrogen atom or a hydrocarbon group), an epoxy group, -C = N or -NH_ {2}, m and n are each an integer from 0 to 2, m + n it is not 0 and s is 0 or one.

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The monomer that contains polar group represented by the formula (8 ') is, for example, the monomer containing polar group represented by formula (8) mentioned above in which Y is another group other than -OH and -NR_ {2}.

Such monomers containing polar group can be used individually or in combination of two or more classes.

The polymerization conditions are the same than previously used.

The procedure is described below. to prepare an olefin copolymer containing polar group according to the invention.

The procedure for preparing a copolymer of olefin containing polar group according to the invention comprises copolymerize at least one α-olefin selected from α-olefins of 2 to 20 atoms carbon, a macromonomer represented by the formula (9) following and at least one monomer containing polar group selected from a monomer containing represented polar group by the formula (7) above and a group containing monomer polar represented by the formula (8) above in the presence of olefin polymerization catalyst comprising:

(A) a compound of a transition metal selected from group 3 (including lantanoid and actinoid) at group 10 of the periodic table, preferably a compound of transition metal represented by any one of the formulas (11) to (15) above,

Y

(B) at least one compound selected from:

(B-1) a oxy-organoaluminum compound,

(B-2) a compound that reacts with the compound (A) to form an ionic pair, and

(B-3) a compound of organoaluminum;

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111

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in which R 5, R 6, Z, W, p, q and r have the same meanings as those of R 5, R 6, Z, W, p, q and r in formula (4), respectively.

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When a group containing monomer is used polar represented by the formula (7) as a monomer that Contains polar group in the invention, the copolymer of olefin containing polar group mentioned above of the invention.

Examples of macromonomers represented by formula (9) include the following macromonomers.

112

1120

The macromonomer can be prepared by use of, for example, the polar monomer (described below) and, specifically, the macromonomer can be prepared by producing a polymer segment from the polar group of the monomer that contains polar group through anionic polymerization, ring opening or polycondensation polymerization so similar to the following procedure (i).

The copolymerization of the α-olefin of 2 to 20 carbon atoms and the macromonomer represented by the formula (9) is carried out using the same olefin polymerization catalyst that is used in the copolymerization of an α-olefin of 2 at 20 carbon atoms and the monomer containing polar group represented by formula (10) in the following procedure (i) under the same conditions that are used in the copolymerization of an α-olefin of 2 to 20 carbon atoms and the polar group containing monomer represented by the formula (10) in the following procedure (i).

In the process to prepare a copolymer containing polar group according to the invention, at least one olefin selected from the α-olefin of 2 to 20 atoms carbon mentioned above, a macromonomer represented by formula (9) and at least one monomer containing group polar selected from the group consisting of a monomer that contains polar group represented by formula (7) and a monomer containing polar group represented by the formula (8) polymerize in the presence of the polymerization catalyst of olefins mentioned above under the same conditions of polymerization than in the process for preparing the copolymer of olefin containing polar group according to the first embodiment of reference.

Thermoplastic resin composition

The thermoplastic resin composition of the invention can be formed from two or more copolymers selected from olefin copolymers containing group polar or can be formed from the olefin copolymer which It contains a polar group and a thermoplastic resin other than olefin copolymer containing polar group.

Thermoplastic resin

The thermoplastic resin preferably used in the invention is a thermoplastic resin class selected from polyolefin, polyamide, polyester, polyacetal, polystyrene, acrylonitrile / butadiene / styrene copolymer (ABS), polymethacrylate, polycarbonate, poly (phenylene oxide), poly (vinyl chloride), poly (vinylidene chloride), poly (vinyl acetate), ethylene / ester copolymer (met) acrylic and diene rubber.

Examples of polyolefins include olefin homopolymers, such as polyethylene, polypropylene, poly-1-butene, polymethylpentene and polymethylbutene; and olefin copolymers, such as a copolymer random ethylene / α-olefin, a terpolymer of ethylene / propylene / diene, a random copolymer of propylene / ethylene, a random copolymer of propylene / α-olefin and a terpolymer of propylene / ethylene / α-olefin. Of these, it they prefer polyethylene, polypropylene, a random copolymer of ethylene / α-olefin, a terpolymer of ethylene / propylene / diene, a random copolymer of propylene / ethylene and a random copolymer of propylene / α-olefin. If the polyolefin is a polyolefin obtained from an olefin of 3 or more atoms carbon, this polyolefin can be an isotactic polymer or It can be a syndiotactic polymer.

As a catalyst for the preparation of polyolefin, any of a catalyst can be used Ziegler-Natta, a metallocene catalyst and a known catalyst

Examples of polyamides include aliphatic polyamides, such as nylon-6, nylon-66, nylon-10, nylon-12 and nylon-46; and polyamides aromatics prepared from aliphatic and acidic diamines aromatic dicarboxylic. Of these, it is preferred Nylon-6

Examples of polyesters include aromatic polyesters, such as poly (terephthalate ethylene), poly (ethylene naphthalate) and poly (butylene terephthalate); polycaprolactone; Y polyhydroxybutyrate. Of these, poly (terephthalate) is preferred of ethylene).

Examples of polyacetals include polyformaldehyde (polyoxymethylene), polyacetaldehyde, polypropionaldehyde and polybutyl aldehyde. Of these, it is preferred polyformaldehyde

Polystyrene can be a homopolymer of styrene or it can be a copolymer of styrene and acrylonitrile, methyl methacrylate, α-methylstyrene, such as an acrylonitrile / styrene copolymer.

As ABS, ABS is preferably used which comprises constituent units derived from acrylonitrile in amounts of 20 to 35 mol%, constituent units derived of butadiene in amounts of 20 to 30% in moles and units constituents derived from styrene in amounts of 40 to 60% in moles

As polymethacrylate, it is preferred poly (methyl methacrylate) (PMMA).

Examples of polycarbonates include the obtained from bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (9-hydroxyphenyl) propane Y 2,2-bis (4-hydroxyphenyl) butane. Of these, polycarbonate obtained from 2,2-bis (9-hydroxyphenyl) propane.

As poly (phenylene oxide), it is preferred poly (oxide of 2,6-dimethyl-1,4-phenylene).

The polyvinyl chloride can be a homopolymer of vinyl chloride or it can be a copolymer of vinyl chloride and vinylidene chloride, acrylic ester, acrylonitrile, propylene.

As polyvinylidene chloride, it is used a copolymer comprising vinylidene chloride and vinyl, acrylonitrile, (meth) acrylic ester, allyl ester, unsaturated ether, styrene or the like and generally containing units of vinylidene chloride in quantities not less than 85%

The polyvinyl acetate can be a vinyl acetate homopolymer or it can be a copolymer of vinyl acetate and ethylene or vinyl chloride. Of these, it Prefer an ethylene / vinyl acetate copolymer.

As ethylene / ester copolymer (meth) acrylic, an ethylene / acrylate copolymer is preferred of methyl, an ethylene / ethyl acrylate copolymer, a ethylene / methyl methacrylate copolymer or a copolymer of ethylene / ethyl methacrylate.

Examples of diene rubbers include conjugated polydiene such as polybutadiene, polyisoprene, a known styrene / butadiene copolymer of elastomer type as SBR (styrene / butadiene rubber). In the diene rubbers, at least a part of the double bonds of the molecule can be hydrogenated

The thermoplastic resins mentioned previously they can be used individually or in combination of two or more classes

Of thermoplastic resins, it is used preferably polyolefin, polyester, polyamide or polystyrene.

The thermoplastic resin composition of the invention can be prepared by combining the olefin copolymer that contains polar group with thermoplastic resin using, for example, a belt mixer, a rotary mixer or a Henschel mixer.

The thermoplastic resin composition of the invention can also be prepared by melting the copolymer  of olefin containing polar group and thermoplastic resin by using a melt kneading device, by for example, a kneader such as a joint kneader, a Banbury mixer, a Brabender, an extruder press of a single spindle or a twin screw extruder press, a stirrer horizontal such as a double surface replacement machine spindle or a multi-spindle dual disc device, or a vertical stirrer such as a double band stirrer propeller.

Additives

To the olefin copolymer composition that contains polar group and thermoplastic resin according to the invention may be added, within limits not harmful to Objectives of the invention, additives such as inorganic filler, organic load, nucleating agent, term stabilizer, stabilizer against weathering, agent antistatic, coloring, lubricant, flame retardant e gloss loss inhibitor.

Inorganic filler

Examples of inorganic fillers include silica, diatomaceous earth, alumina, titanium oxide, oxide magnesium, pumice powder, pumice ball, hydroxide aluminum, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, calcium titanate, barium sulfate, calcium sulphite, talc, clay, mica, asbestos, fiberglass, glass flakes, glass beads, calcium silicate, Montmorillonite, Bentonite, Graphite, Aluminum Powder and Sulfide molybdenum.

Among these, compounds are preferred stratified and clay minerals are particularly preferred which have swelling and exfoliation properties in dispersion for use. Clay minerals are classified generally in a type of two-layer structure consisting of a tetrahedral layer of silica and an octahedral layer containing aluminum or magnesium as the central metal provided in the layer tetrahedral, and a type of three-layer structure consisting of tetrahedral layers of silica and an octahedral layer containing aluminum or magnesium as the central metal interspersed between the layers tetrahedral. The type of two-layer structure (first type) is, for example, a kaolinite group or an antigorite group, and the type of three-layer structure (last type) is, for example, a smectite group, a vermiculite group or a group of mica that They are grouped according to the number of interlaminar cations.

Specific examples of clay minerals include kaolinite, dickite, nacrite, haloisite, antigorite, chrysotile, pyrophyllite, montmorillonite, beidelite, nontronite, saponite, sauconite, estevensite, hectorite, tetrasilicic mica, sodium taeniorite, muscovite, margarita, talcum powder, vermiculite, phylopite, xanthophyllite and chlorite

Clay minerals that have been treated with organic materials (sometimes referred to as "minerals from organically modified clay ") can also be used as inorganic stratified compounds. (On the minerals of clay that have been treated with organic materials, see "Dictionary of Clay" by Asakura Shoten.)

Of the clay minerals above, it they prefer a smectite group, a vermiculite group and a group of mica, and a group of smectite is more preferable, from the points view of the swelling properties or the properties of exfoliation. Examples of clay minerals from the group of smectite include montmorillonite, beidelite, nontronite, saponite, sauconite, estevensite and hectorite.

Examples of dispersion media for swell or exfoliate inorganic stratified compounds in the case of the natural swelling of clay minerals are water; alcohols, such as methanol, ethanol, propanol, isopropanol, ethylene glycol and diethylene glycol; dimethylformamide; dimethylsulfoxide and acetone. Of these, water and an alcohol such as methanol

In the case of modified clay minerals organically, aromatic hydrocarbons may be mentioned, such as benzene, toluene and xylene; ethers, such as ethyl ether and tetrahydrofuran; ketones, such as acetone, methyl ethyl ketone and methyl isobutyl ketone; aliphatic hydrocarbons, such as n-pentane, n-hexane and n-octane; halogenated hydrocarbons, such as chlorobenzene, carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane and perchlorethylene; acetate ethyl; methyl methacrylate (MMA); dioctyl phthalate (PDO); dimethylformamide; dimethylsulfoxide; methyl cellosolve and oil silicone.

Nucleating agent

As nucleating agents, various are used known nucleation agents to date without limitation specific. Examples of nucleating agents include the following aromatic phosphoric ester salt, benzylidensorbitol, aromatic carboxylic acid and rosin nucleating agent.

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Examples of aromatic phosphoric ester salt are compounds represented by the following formula (A).

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In the above formula, R 11 is an atom of oxygen, a sulfur atom or a hydrocarbon group of 1 to 10 carbon atoms; R 12 and R 13 are each hydrogen or a hydrocarbon group of 1 to 10 carbon atoms and can be same or different, and R 12, R 13 or R 12 and R 13 may be linked together to form a ring; Month a metal atom that has a valence of 1 to 3; and n is a number integer from 1 to 3.

The concrete examples of the compounds represented by formula (A) above include

2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate of sodium,

2,2'-ethyliden-bis (4,6-di-t-butylphenyl) phosphate of sodium,

2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate lithium

2,2'-ethyliden-bis (4,6-di-t-butylphenyl) phosphate lithium

2,2'-ethyliden-bis (4-i-propyl-6-t-butylphenyl) phosphate of sodium,

2,2'-methylene-bis (4-methyl-6-t-butylphenyl) phosphate lithium

2,2'-methylene-bis (4-ethyl-6-t-butylphenyl) phosphate lithium

bis [2,2'-thiobis (4-methyl-6-t-butylphenyl) phosphate] of calcium,

bis [2,2'-thiobis (4-ethyl-6-t-butylphenyl) phosphate] of calcium,

bis [2,2'-thiobis (4,6-di-t-butylphenyl) phosphate] of calcium,

bis [2,2'-thiobis (4,6-di-t-butylphenyl) phosphate] of magnesium,

bis [2,2'-thiobis (4-t-octylphenyl) phosphate] of magnesium,

2,2'-butylidene-bis (4,6-di-methylphenyl) phosphate of sodium,

2,2'-butylidene-bis (4,6-di-t-butylphenyl) phosphate of sodium,

2,2'-t-octylmethylene-bis (4,6-dimethylphenyl) phosphate of sodium,

2,2'-t-octylmethylene-bis (4,6-di-t-butylphenyl) phosphate of sodium,

bis [2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate] of calcium,

bis [2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate] of magnesium,

bis [2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate] of barium,

2,2'-methylene-bis (4-methyl-6-t-butylphenyl) phosphate of sodium,

2,2'-methylene-bis (4-ethyl-6-t-butylphenyl) phosphate of sodium,

(4,4'-dimethyl-5,6'-di-t-butyl-2,2'-biphenyl) phosphate of sodium,

bis - [(4,4'-dimethyl-6,6'-di-t-butyl-2,2'-biphenyl) phosphate] of calcium,

2,2'-ethyliden-bis (4-m-butyl-6-t-butylphenyl) phosphate of sodium,

2,2'-methylene-bis (4,6-di-methylphenyl) phosphate of sodium,

2,2'-methylene-bis (4,6-di-ethylphenyl) phosphate of sodium,

2,2'-ethyliden-bis (4,6-di-t-butylphenyl) phosphate of potassium,

bis [2,2'-ethyliden-bis (4,6-di-t-butylphenyl) phosphate] of calcium,

bis [2,2'-ethyliden-bis (4,6-di-t-butylphenyl) phosphate] of magnesium,

bis [2,2'-ethyliden-bis (4,6-di-t-butylphenyl) phosphate] of barium,

tris [2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate] aluminum and tris [2,2'-ethyliden-bis (4,6-di-t-butylphenyl) phosphate]  of aluminum, and mixtures of two or more thereof. It preferred particularly the 2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate  of sodium.

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Examples of aromatic phosphoric ester salt are compounds represented by the following formula (B).

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In the above formula, R 14 indicates hydrogen or a hydrocarbon group of 1 to 10 carbon atoms; M it is a metal atom that has a valence of 1 to 3; and n is a integer from 1 to 3.

The concrete examples of the compounds represented by formula (B) above include

bis (4-t-butylphenyl) phosphate of sodium,

bis (4-methylphenyl) phosphate of sodium,

bis (4-ethylphenyl) phosphate of sodium,

bis (4-i-propylphenyl) phosphate of sodium,

bis (4-t-octylphenyl) phosphate of sodium,

bis (4-t-butylphenyl) phosphate of potassium,

bis (4-t-butylphenyl) phosphate of calcium,

bis (4-t-butylphenyl) phosphate of magnesium,

bis (4-t-butylphenyl) phosphate lithium

bis (4-t-butylphenyl) phosphate aluminum, and

mixtures of two or more thereof. It preferred particularly bis (4-t-butylphenyl) phosphate of sodium.

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As an example benzylidensorbitol is a compound represented by the following formula (C).

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In the formula, each R 15 can be the same or different and indicates a hydrogen atom or a hydrocarbon group 1 to 10 carbon atoms, and m and n are each an integer from 0 to 5.

Examples of the compounds represented by formula (C) include

1,3,2,4-dibenzylidensorbitol, 1,3-benzylidene-2,4-p-methylbenzylidensorbitol, 1,3-benzylidene-2,4-p-ethylbenzylidensorbitol, 1,3-p-methylbenzylidene-2,4-benzylidensorbitol, 1,3-p-ethylbenzylidene-2,4-benzylidensorbitol, 1,3-p-methylbenzylidene-2,4-p-ethylbenzylidensorbitol, 1,3-p-ethylbenzylidene-2,4-p-methylbenzylidensorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3,2,4-di (p-ethylbenzylidene) sorbitol, 1,3,2,4-di (p-n-propylbenzylidene) sorbitol, 1,3,2,4-di (p-i-propylbenzylidene) sorbitol, 1,3,2,4-di (p-n-butylbenzylidene) sorbitol, 1,3,2,4-di (p-s-butylbenzylidene) sorbitol, 1,3,2,4-di (p-t-butylbenzylidene) sorbitol, 1,3,2,4-di (2 ', 4'-dimethylbenzylidene) sorbitol, 1,3,2,4-di (p-methoxybenzylidene) sorbitol, 1,3,2,4-di (p-ethoxybenzylidene) sorbitol, 1,3-benzylidene-2-4-p-chlorobenzylidensorbitol, 1,3-p-chlorobenzylidene 2-4-benzylidensorbitol, 1,3-p-chlorobenzylidene-2-4-p-methylbenzylidensorbitol, 1,3-p-chlorobenzylidene-2-4-p-ethylbenzylidensorbitol, 1,3-p-methylbenzylidene-2-4-p-chlorobenzylidensorbitol, 1,3-p-ethylbenzylidene 2-4-p-chlorobenzylidensorbitol, 1,3,2,4-di (p-chlorobenzylidene) sorbitol,  and mixtures of two or more of these compounds. Of these, they are preferred 1,3,2,4-dibenzylidensorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3,2,4-di (p-ethylbenzylidene) sorbitol, 1,3-p-chlorobenzylidene-2-4-p-methylbenzylidensorbitol, 1,3,2,4-di (p-chlorobenzylidene) sorbitol,  and mixtures of two or more of these compounds.

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Of the previous benzylidensorbitols, prefer a compound represented by the following formula (D).

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In the formula, each R 15 can be the same or different and indicates a methyl group or an ethyl group.

The aromatic carboxylic acid is, for example, hydroxidipara-t-butyl benzoate of aluminum represented by the following formula (E).

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The rosin-like nucleating agent is, for example, a metal salt of a rosin acid, and the salt metal of a rosin acid is a reaction product of a rosin acid and a metal compound. The examples of rosin acids include natural rosins, such as gum rosin, rosin resin oil and rosin wood; various modified rosins, such as rosin disproportionate, hydrogenated rosin, dehydrogenated rosin, polymerized rosin and carboxylic acid modified rosin α, β-ethylenically unsaturated; purified products of natural rosins; and products purified from the modified rosins. The examples of unsaturated carboxylic acids used to prepare rosins modified with carboxylic acid α, β-ethylenically unsaturated include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, acrylic acid and acid methacrylic Of the foregoing rosins, at least one rosin acid selected from the group consisting of a natural rosin, a modified rosin, a purified product of a natural rosin and a purified product of a rosin modified Rosin acid comprises multiple acids of resin selected from pimaric acid, sandarapimaric acid, acid palústrico, isopimaric acid, abietic acid, acid dehydroabiético, neoabiético acid, dihidropimáric acid, acid dihydroabietic and tetrahydroabietic acid.

The metal compound that reacts with the acid of rosin to form a metal salt is, for example, a compound comprising a metallic element, such as sodium, potassium and magnesium, and forms a salt together with the acid from rosin. Examples of metal salts include chlorides, nitrates, acetates, sulfates, carbonates, oxides and hydroxides of metals previous.

Other examples of nucleating agents include high melting polymers, metal salts of aromatic carboxylic acids or aliphatic carboxylic acids, and inorganic compounds

Examples of high melting point polymers include polyvinylcycloalkanes, such as polyvinylcyclohexane and polyvinylcyclopentane; poly-3-methyl-1-pentene, poly-3-methyl-1-butene and polyalkenylsilanes.

Examples of metal salts of acids aromatic carboxylic or aliphatic carboxylic acids include aluminum benzoate, aluminum p-t-butylbenzoate, sodium adipate, sodium thiophenecarboxylate and pyrrolcarboxylate of sodium.

Molding method

The olefin copolymer containing group polar and thermoplastic resin composition of the invention they can be produced by various molding methods such as calendering extrusion molding, injection molding, molding by blowing, pressure molding and stamping.

The olefin copolymer containing group Polar and thermoplastic resin composition can be molded to give sheets or films (not stretched) by molding extrusion.

Stretched films can be obtained by stretching extruded sheets or extruded films (not stretched) by rameado (stretched longitudinal-transverse, stretched transverse-longitudinal), biaxial orientation Simultaneous or stretched monoaxial. Movies can also be produced of insufflation from the olefin copolymer containing polar group or the thermoplastic resin composition of the invention.

Filaments can be produced by, for example, extrusion of a molten composition through a nozzle  to spin The filaments can be produced by a method of meltblown

Injection molded products can produced by injection molding the composition to give Various ways by using injection molding machines known to date under known conditions. The injection molded products obtained from the copolymer of olefin containing polar group or resin composition thermoplastic of the invention are barely electrostatically charged and have excellent rigidity, thermal resistance, resistance to impact, surface gloss, chemical resistance and abrasion resistance, so that they can be used in lines generals such as car interior trim, car exterior trims, mechanism covers electrical, containers and the like.

Blow molded products can occur through the use of blow molding machines known to date under known conditions.

In the injection and blow molding method, the olefin copolymer containing polar group or composition thermoplastic resin of the invention are injected into a mold of preform bulb at a resin temperature of 100 to 300 ° C to form a preform, then the preform is kept in a mold of desired shape, and air is blown into the preform to fix the preform in the mold, whereby a product can be obtained blow molded.

The pressure molded product is, for example, A mold stamping product.

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Applications

The olefin copolymer containing group polar and thermoplastic resin composition according to the invention they can be applied to various uses, for example, uses following.

(1) Film and sheet

A film and a sheet comprising the olefin copolymer containing polar group or the composition of thermoplastic resin according to the invention has excellent flexibility, transparency, adhesion properties, properties anti-fogging, thermal resistance and properties of separation.

(2) Laminated material

A laminated material that contains at least one layer comprising the group containing olefin copolymer polar or thermoplastic resin composition according to the invention It is, for example, agricultural film, wrap film, film retractable, protective film, separation film such as blood plasma separation film or film vaporization of selective water permeability, or film of selective separation such as ion exchange membrane, optical resolution film or battery separation.

(3) The olefin copolymer containing group polar or thermoplastic resin composition according to the invention Can be used for microcapsules, PTP containers, chemical bulbs and drug delivery system.

(4) Modifier

When the olefin copolymer it contains polar group or thermoplastic resin composition according to the invention are used as resin modifier, can be obtained modifying effects on impact resistance, fluidity, coating properties, crystallizability, properties of adhesion, transparency, etc.

When the olefin copolymer it contains polar group or thermoplastic resin composition according to the invention are used as a rubber modifier, can be obtained modifying effects on weather resistance, thermal resistance, adhesion properties, oil resistance, etc.

Examples of rubbers include rubbers crosslinked, such as natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene / butadiene rubber (SBR), chloroprene rubber (CR), acrylonitrile / butadiene rubber (NBR), butyl rubber (IIR), ethylene / propylene rubber (EPM, EPDM), chlorosulfonated polyethylene (CSM), acrylic rubber (ACM, ANM, etc.), epichlorohydrin rubber (CO, ECO, etc.), silicone rubber (Q) and fluorine rubber (FKM, etc.); and thermoplastic rubbers, such as styrene type rubbers, olefin type, urethane type, type ester, amide type and vinyl chloride type.

The olefin copolymer containing group polar and thermoplastic resin composition of the invention can be used as a modifier for lubricating oils, such as gasoline engine oil, diesel engine oil, naval engine, gear oil, metalworking oil, engine oil, machine oil, spindle oil and oil insulating. They can also be used as a viscosity modifier or freezing point reducer of these lubricating oils.

When the olefin copolymer it contains polar group or thermoplastic resin composition of the invention  they are used as a modifier for waxes, an improvement in Adhesiveness, fluidity and hardness. Examples of waxes include waxes minerals, such as Montana wax, peat wax, wax ozoquerite / ceresin and petroleum wax; synthetic waxes, such such as polyethylene, Fischer-Tropsch wax, chemically modified hydrocarbon and substituted amide wax; vegetable waxes and animal waxes.

When the olefin copolymer it contains polar group or thermoplastic resin composition of the invention  they are used as a cement modifier, an improvement can be achieved in the moldability and hardness.

Examples of cement include cement from air hardening, such as lime, gypsum and magnesia cement; water hardening cement, such as Roman cement, cement Natural, Portland cement, alumina cement and cement with high sulfuric salt slag; and special cements, such as cement acid resistant, refractory cement, glass cement soluble and dental cement.

(5) Viscosity modifier, improver of moldability

The olefin copolymer containing group polar and thermoplastic resin composition of the invention can be used as a viscosity modifier or improver moldability for inks and paints, such as printing ink Typographic, lithographic printing ink, flexographic ink, gravure ink, oil paint, paint derived from cellulose, synthetic resin paint, water paint, paint Water powder and Japanese lacquer.

(6) Construction material, engineering material civil

The olefin copolymer containing group polar and thermoplastic resin composition of the invention can be used for construction / civil engineering resins and molded construction / civil engineering products, such as flooring material, tiles, floor sheet, sheet sound insulation, thermal insulation panel, material cushioning, decorative foil, skirting board, asphalt modifier, gaskets, sealing material, roof sheet and sheet cut.

(7) Automobile exterior or interior trim, Gasoline tank

The exterior or interior trim of automobiles and gasoline tanks comprising the copolymer that contains polar group or thermoplastic resin composition of the The present invention has excellent rigidity, resistance to shocks, oil resistance and thermal resistance.

(8) Electrical or electronic parts

The olefin copolymer containing group polar and thermoplastic resin composition of the invention They can be used for electrical or electronic parts. Examples of the electrical or electronic parts include insulation materials electrical, instruments for treating electronic parts, means of magnetic recording, joining parts of recording media magnetic, electrical circuit sealing materials, materials  of household electrical appliances, basic materials of containers such as electronic oven containers, films for electronic ovens, materials with base polymer electrolyte and alloy based materials conductive

Parts are also shown by way of example electrical or electronic, such as connector, plug, resistor  electric, relay coil with relay case, capacitor, variable capacitor case, optical electromagnetic reader, optical connector, vibrator, various terminal assemblies, transformer, plug, printed circuit board, tuner, speaker, microphone, headset, small engine, base magnetic head, power module, protective cover, semiconductor, parts of liquid crystal displays, support FDD, FDD chassis, HDD parts, motor brush holder, antenna satellite dish and parts associated with computers; recorder parts video, TV parts, iron, dryer, rice cooker parts, electronic oven parts, acoustic instrument parts, parts of audio devices such as compact disc or laser disc of audio, parts of household or office electrical appliances, such as parts of luminous accessories, parts of refrigerator, parts of air conditioning, typewriter parts and parts of text processor; parts associated with office computers, parts associated with telephones, parts associated with fax, parts associated with photocopiers, parts associated with material electromagnetic shield, speaker cone material and element Vibrating for the speaker.

(9) Aqueous emulsion

An aqueous emulsion comprising the copolymer of olefin containing polar group or resin composition thermoplastic of the invention can be used as an adhesive for Polyolefins with excellent heat sealing properties.

(10) Coating base

A solvent dispersion containing the olefin copolymer containing polar group or the composition of thermoplastic resin according to the invention has an excellent dispersion stability in a solvent and shows excellent adhesion properties when metals or polar resins are bonded to polyolefins

(11) Medical or hygienic material

The olefin copolymer containing group polar and thermoplastic resin composition of the invention can be used for medical items, such as non-textile material woven, non-woven textile material laminate, electret, medical tube, medical container, transfusion bag, syringe and prefilled syringe, medical materials, organs artificial, artificial muscles, filter films, articles sanitation / food sanitation, hermetic flexible bags and films to maintain freshness.

(12) Miscellaneous articles

The olefin copolymer containing group polar and thermoplastic resin composition of the invention can be used for stationery, such as protective desk, cutting mat, ruler, pen holder, grip of pens, pen cap, scissors grip, blade, magnetic sheet, pen case, paper holder, folder, sticker, tape and white board; miscellaneous items for daily use, such as clothes, curtains, sheets, carpets, door mats, bath mats, cubes, hoses, bags, pots, air conditioning filters, filters of extractor, dishes, trays, cups, lunch boxes, filters coffee makers, eyeglass frames, containers, storage cases, hangers, ropes and net for washing; sporting goods, such as shoes, goggles, skis, rackets, balls, shops campaign, swimming goggles, swimming fins, fishing rods, portable refrigerator, picnic tablecloths and sports nets; toys, such as blocks and cards; containers, such as can of kerosene, drum, detergent bottle and shampoo bottle; Y display items, such as bulletin boards, towers and plastic chains

(13) Load modifier

The olefin copolymer containing group polar and thermoplastic resin composition of the invention they can be used favorably as an additive to prepare a load dispersibility improver or a load of improved dispersibility

(14) Compatibility agent

The olefin copolymer containing group polar or thermoplastic resin composition according to the invention can be used as a compatibilizing agent. When the olefin copolymer containing polar group of the invention, a polyolefin and a thermoplastic resin can be mixed which It contains a polar group in an arbitrary mixing ratio. He olefin copolymer containing polar group of the invention has  a main chain of a polyolefin and a side chain that it has a polar group, so that by using it, they can compatibilize components that are inherently incompatible. Therefore, the elongation of breakage can be significantly improved compared to the case in which the copolymer of olefin containing polar group or resin composition thermoplastic

The following describes in more detail the uses of the olefin copolymer containing polar group and the thermoplastic resin composition according to the invention.

Adhesive resin

When the olefin copolymer it contains polar group or thermoplastic resin composition of the invention  they are used as adhesive resin, X in formula (3) is preferably an acid anhydride group, an epoxy group, a amino group or a hydroxyl group, and Y in the formula (6) is preferably an epoxy group, an amino group or a group hydroxyl

If X is a hydroxyl group and R3 in the formula (3) is a straight chain aliphatic hydrocarbon group or branched of 9 or less carbon atoms, a adhesive resin that has an excellent balance between fluidity and adhesion properties.

If X is a hydroxyl group and R3 in the formula (3) is a straight chain aliphatic hydrocarbon group or branched of 11 or more carbon atoms, a resin can be obtained adhesive that has adhesion properties particularly excellent.

The adhesive resin of the invention comprises the olefin copolymer containing polar group or the composition of thermoplastic resin, so that it shows excellent properties of adhesion to metals, such as iron and aluminum, and polymers containing polar group, such as polyamide, polyester, polyacetal, polystyrene, copolymer of acrylonitrile / butadiene / styrene (ABS), polymethacrylate, polycarbonate, poly (phenylene oxide), poly (chloride of vinyl), poly (vinylidene chloride), poly (acetate) vinyl), polyvinyl alcohol, saponification product complete or partial ethylene / vinyl acetate copolymer, and ethylene / ester copolymer of (meth) acrylic acid. Further, because the main structure is a structure of polyolefin, the adhesive resin of the invention has excellent adhesion properties also to polyolefins and can be used as adhesive resin between polar materials or polar material and a polyolefin.

Compatibility Agent

When the olefin copolymer it contains polar group or thermoplastic resin composition of the invention  they are used as a compatibilizing agent, a mixture can be mixed polyolefin and a thermoplastic resin containing polar group in An arbitrary mixing reason. The olefin copolymer that contains polar group or thermoplastic resin composition of the invention have a main chain of a polyolefin and a side chain that has a polar group, and therefore, can make compatible with each other components that are inherently incompatible Therefore, the break elongation compared to the case in which it is not use the olefin copolymer containing polar group or the thermoplastic resin composition.

In use as a compatibility agent, X in formula (3) is preferably an acid anhydride group, a epoxy group, an amino group, a carboxylic acid group, a group carboxylic acid ester or a hydroxyl group, so particularly preferably an acid anhydride group, a group epoxy, an amino group or a carboxylic acid ester group, and Y in Formula (6) is preferably an epoxy group, an amino group or a hydroxyl group.

If X is a hydroxyl group and R3 is a group hydrocarbon of 9 or less carbon atoms, preferably 8 or less carbon atoms, more preferably 7 or less atoms of carbon, in formula (3), the compatibilizing agent shows An excellent balance between fluidity and compatibility.

If X is a hydroxyl group and R3 is a group hydrocarbon of 11 or more carbon atoms, preferably 12 or more carbon atoms, more preferably 13 or more atoms of carbon, in the formula (3), the Effects of improved compatibility.

Resin modifier

When the olefin copolymer it contains polar group or thermoplastic resin composition of the invention  they are used as a resin modifier, effects of modification in hydrophilic nature, antistatic properties, coating properties, printability, etc.

In use as a nature improver hydrophilic or antistatic properties improver, X in the formula (3) is preferably a hydroxyl group, an acidic group carboxylic, an amide group, an amino group, an anhydride group of acid or a carboxylic ester group.

In the use as an improver of the properties of coating or printability improver, X in formula (3) it is preferably a hydroxyl group, a carboxylic acid group, an amide group, an amino group, an epoxy group or an anhydride group of acid, and Y in formula (6) is preferably an epoxy group, an amino group or a hydroxyl group.

When the olefin copolymer it contains polar group or thermoplastic resin composition are used as improver of the coating properties or improver of the printability and when X is a hydroxyl group and R3 is a aliphatic hydrocarbon group of 9 or less carbon atoms, preferably 8 or less carbon atoms, more preferably 7 or less carbon atoms, in formula (3), the improver shows an excellent balance between fluidity and the properties of coating or printability. When X is a hydroxyl group and R 3 is an aliphatic hydrocarbon group of 11 or more atoms of carbon, preferably 12 or more carbon atoms, more preferably 13 or more carbon atoms, in the formula (3), the effects of improvement in the coating properties and printability.

Load dispersing agent

The olefin copolymer containing group polar and thermoplastic resin composition of the invention can be used favorably as a dispersing agent to improve the dispersibility of a filler or additive to Prepare a load that has improved dispersibility.

For example, the charge dispersing agent is Use when mixing a thermoplastic resin with a filler. Examples of thermoplastic resins include resins thermoplastics mentioned above, and the polyolefins

Examples of the charges used in the invention include fibers, such as all aromatic polyamide fibers,  aliphatic polyamide fibers, polyester fibers and fibers of cellulose; organic fillers, such as fine polyamide dispersion or liquid polyester, and the inorganic fillers mentioned previously.

There is no specific limitation on the quantity of the load used, and for example, the load is used in an amount from 0.01 to 100 parts by weight, preferably from 0.1 to 20 parts in weight, based on 100 parts by weight of the resin thermoplastic

The loading dispersing agent of the invention It has a high affinity with a load and can improve the dispersibility of a load. When using a booster load dispersibility of this type, the mechanical properties of a thermoplastic resin composition that It contains a load such as stiffness, hardness, thermal resistance, impact resistance and elongation.

The loading dispersant can be used to a thermoplastic resin or a thermosetting resin using a filler, and is preferably used for a polyolefin.

The olefin copolymer containing group polar and thermoplastic resin composition containing the loading dispersing agent of the invention can be molded by any known procedure, for example, the procedures mentioned above.

Molded products obtained through such Procedures apply to wide uses such as items Domestic to industrial items. Product Examples moldings obtained by such procedures include parts electrical, electronic parts, auto parts, parts of mechanical mechanisms, food containers, films, sheets and fibers More specifically, supplies of office and global, such as printers, personal computers, word processors, keyboards, PDA (portable data terminal), telephones, fax, photocopiers, ECR (electronic cash register), electronic calculators, electronic notebooks, dictionaries electronics, cards, media and stationery; gadgets electric, such as washing machines, refrigerators, vacuum cleaners, ovens electronics, light installations, video game consoles, irons and foot warmers; AV equipment, such as TV, recorders video, camcorders, cassettes, tape recorders, mini discs, CD players, speakers and glass screens liquid; and electrical or electronic parts and equipment communication, such as connectors, relays, capacitors, switches, printed circuit boards, coils, materials semiconductor sealants, electrical wires, cables, transformers, diversion yokes, cabinet panels and appliances of watchmaking.

Other examples include materials for automobiles, ships and airplanes and building materials, such as seats (padding, cover), belts, lining roof foam, convertible ceilings, armrests, Door trims, rear trays, carpets, mats, parasols, hubcaps, mattress covers, air bags, materials insulators, hooks, hand clamps, materials Cable coating, electrical insulation materials, coatings, coating materials, materials siding, floor materials, corner wall, panel screen, covers, plywood, ceiling panels, separation panels, side walls, carpets, papers walls, wall trim materials, materials exterior trim, interior trim materials, roof materials, sound insulation materials, thermal insulation materials and window materials; Y daily or sports articles, such as clothes, curtains, sheets, plywood, synthetic fiber boards, rugs, Doormats, sheets, buckets, hoses, containers, glasses, bags, covers, goggles, skis, rackets, shops and musical instruments.

Shampoo bottles are also mentioned and detergent, condiment bottles such as cooking oil and soy sauce, bottles of drinks such as mineral water and juice, heat resistant food containers such as lunch boxes and bowls for cooking, dishes such as plates and chopsticks, various other food containers, packaging films and packaging bags

Dispersion

The olefin copolymer containing group polar or thermoplastic resin composition of the invention they can be used as dispersion of aqueous resin by dispersing them in water or can be used as solvent dispersion by dispersing them in a solvent

Aqueous resin dispersion

The aqueous resin dispersion of the invention comprises water and the olefin copolymer containing polar group or the thermoplastic resin composition dispersed therein.

The aqueous resin dispersion of the invention may contain a modified polyolefin and / or a surfactant  when needed, within the limits not harmful to Objectives of the invention.

The modified polyolefin is a polyolefin obtained by graft modification of a polymer of a α-olefin of 2 to 20 carbon atoms with a ethylenically unsaturated carboxylic acid compound.

The average molecular weight in viscosity of the polyolefin (starting polyolefin) which is a material of the modified polyolefin is normally in the range of 1,000 to 50,000, preferably 2,000 to 30,000, more preferably 5,000 to 10,000. To obtain properties from excellent emulsion, the melt viscosity thereof, as measured at 180 ° C, is normally in the range of 10 to 5,000 cps, preferably from 20 to 2,000 cps, more preferably from 30 to 1,000 cps

To prepare the starting polyolefin, they can adapt various procedures known to date. By For example, a process in which polymerization is available an α-olefin so that the weight is obtained desired molecular using a transition metal catalyst such as a known metallocene catalyst and a process in the that a prepared high molecular weight polyolefin is heated by using a transition metal catalyst to Perform degradation.

Examples of carboxylic acid compounds ethylenically unsaturated for use in modification by graft of a starting polyolefin include compounds that have an ethylenically unsaturated bond in their molecule and they contain a carboxylic acid or a carboxylic anhydride, and their derivatives.

Specifically, acids may be mentioned ethylenically unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, acid endocis-bicyclo [2.2.1] hept-5-eno-2,3-dicarboxylic  (nadic? acid) and acid methyl-endocis-bicyclo [2.2.1] hept-5-eno-2,3-dicarboxylic (methylnadic? acid); and carboxylic acid derivatives ethylenically unsaturated, such as acid halides, amides, imides, acid anhydrides and esters of the above acids. Specific examples of carboxylic acid derivatives ethylenically unsaturated include maleic acid dichloride, Maleimide, maleic anhydride, citraconic anhydride, maleate monomethyl and dimethyl maleate.

Of these, acrylic acid, acid are preferable. methacrylic, maleic anhydride, methyl acrylate, acrylate ethyl, methyl methacrylate and ethyl methacrylate.

Carboxylic acid compounds ethylenically unsaturated can be used individually or in combination of two or more classes, or can be used in combination with other monomers within limits not detrimental to the effects of the present invention.

Examples of monomers that can be used in combination with the ethylenically carboxylic acid compound unsaturated include ethylenically unsaturated compounds that contain amino group, such as dimethylaminoethyl acrylate, acrylamine, aminomethyl methacrylate, methacrylate dimethylaminoethyl, aminopropyl methacrylate, N, N-dimethylaminopropylacrylamide and amino styrene; ethylenically unsaturated compounds containing group hydroxyl, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, methacrylate 2-hydroxyethyl and allyl alcohol; and compounds styrene type hydrocarbons, such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, m-ethylstyrene, p-ethylstyrene, o-isopropylstyrene, m-isopropylstyrene and p-isopropylstyrene. The proportion of the compound of ethylenically unsaturated carboxylic acid contained in all Graft monomer components is preferably not less than fifty.

The modified polyolefin can be prepared according to a known procedure, for example, a described procedure in Japanese Patent Publication No. 22988/1977. Specifically, the starting polyolefin is heated to a temperature above the melting point to melt, and it add the ethylenically carboxylic acid compound unsaturated and a peroxide at the same time or successively with stirring, to perform the copolymerization reaction by graft.

The viscosimetric average molecular weight of the modified polyolefin is normally in the range of 1,000 to 50,000, preferably 2,000 to 20,000, more preferably 5,000 to 10,000.

The amount of the carboxylic acid compound ethylenically unsaturated content in the modified polyolefin is normally found in the range of 1.0x10 -3 to 0.2 molar equivalents, preferably from 5.0x10 -3 to 0.15 molar equivalents, more preferably 0.01 to 0.1 equivalents molars, based on 100 g of the modified polyolefin.

Modified polyolefins can be used individually or in combination of two or more classes.

Examples of the surfactants include anionic surfactants of sulfonic acid or carboxylic acid type, such as alkyl naphthalenesulfonic acid salt, Na salt of naphthalenesulfonic acid formaldehyde condensate, Cresol Shaffer formaldehyde condensate Na salt, salt Na of alkyldiphenyl ether disulfonic acid, Ca salt of lignin sulfonic acid, Na salt of sulphonic acid of melanin resin, salt of special polyacrylic acid, gluconic acid salt, olefin copolymer / maleic acid salt, Na salt of carboxymethyl cellulose, metallic soap (Zn, Al, Na or K salt), K salt of oleic acid, Na salt of oleic acid, K salt of stearic acid, Na salt of stearic acid, K salt of K acid beef tallow, Na salt from beef tallow acid and triethanolestearatoamine salt; non-ionic surfactants, such as fatty acid monoglyceride, sorbitan fatty acid ester, partial sugar fatty acid ester, poly (glycerine fatty acid partial ester), poly (oxyethylene alkyl ether), poly (oxyethylene alkylphenyl ether), poly (oxyethylene sorbitan fatty acid partial ester), poly (oxyethylene sorbitol fatty acid partial ester), poly (oxyethylene glycerin fatty acid partial ester), poly (oxyethylene fatty amine), poly (oxyethylene castor oil) ( hydrogenated), poly (oxyethylene glycol fatty acid ester), polyoxyethylene-polyoxypropylene block polymer, hydroxyethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone and methylcellulose; cationic surfactants, such as alkylammonium chloride, trimethylalkylammonium bromide and alkylpyridinium chloride; and amphoteric surfactants, such as dimethylalkylbetaine and
alkylglycine

Of these, agents are preferably used anionic surfactants because a dispersion of more stable aqueous resin. Of these, acids are more preferable. higher fatty acids, acid salts are even more preferable saturated or unsaturated higher fatty acids of 1 to 20 atoms of carbon, and metal salts are particularly preferable alkaline thereof.

More specifically, salts of alkali metal of capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, margarine acid, acid stearic acid, arachidic acid, lindane acid, Thujic acid, acid petroselinic, oleic acid, linoleic acid, linolenic acid, arachidonic acid and beef tallow acid.

Surfactants can be used individually or in combination of two or more classes.

The aqueous resin dispersion of the invention can be prepared by, for example, dispersion of the copolymer of olefin containing polar group or resin composition thermoplastic, and optionally, the modified polyolefin, the surfactant and various additives in a dispersion medium aqueous. Specifically, the following are available procedures (1) and (2).

(1) The olefin copolymer that dissolves contains polar group or thermoplastic resin composition in a organic solvent such as toluene or xylene to prepare a solution having a concentration of 10 to 50% by weight. Then, the solution is added to water together with a solvent hydrophilic, such as methyl alcohol, ethyl alcohol or alcohol isopropyl, and an emulsifying agent, and stirred with a homogenizer or similar to obtain an emulsion. Then I know remove the organic solvent and the emulsifying agent from the emulsion by means of an evaporator.

(2) The copolymer of olefin containing polar group or resin composition thermoplastic, and water is added to the molten kneaded product. Then, a stage of kneading the resin and water in a state in which the resin is still molten and a stage of add a basic substance if the modified polyolefin is not neutralized at the same time or successively.

Of the above procedures, it is used preferably the process (2) for preparing the dispersion of aqueous resin The procedure (2) is described below in more detail

In the first place, the olefin copolymer containing polar group or the composition of thermoplastic resin The temperature in the molten kneaded product is higher than the melting point of the olefin copolymer that contains polar group or higher than the melting point of a resin that it has the highest melting point between the resins contained in the thermoplastic resin composition, preferably a temperature such that the melt viscosity does not become higher at 10 5 poise.

Then, water is added to the kneaded product molten, and the resin and water are kneaded in a state in which the resins are still molten so that resin solids are They return scattered particles. If a polyolefin is used, no neutralized and / or non-saponified, a substance can be added basic at this stage to neutralize polyolefin.

Examples of basic substances include substances that function as a base in water, such as metals alkaline, alkaline earth metals, ammonia and amines; substances which function as a base in water, such as oxides, hydroxides, salts of weak acids or alkali metal hydrides, and oxides, hydroxides, salts of weak acids or metal hydrides alkaline earths; and alkoxides of these metals. Then you provide specific examples of such substances.

Examples of alkali metals include sodium and potassium; Examples of alkaline earth metals include calcium, strontium and barium; Examples of amines include inorganic amines. such as hydroxylamine and hydrazine, methylamine, ethylamine, ethanolamine and cyclohexylamine; examples of oxides, hydroxides and alkali metal hydrides and alkaline earth metals include sodium oxide, sodium peroxide, potassium oxide, peroxide potassium, calcium oxide, strontium oxide, barium oxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydride; examples of salts of weak acid from alkali metals and alkaline earth metals include sodium carbonate, potassium carbonate, hydrogen carbonate sodium, potassium hydrogen carbonate, calcium hydrogen carbonate, sodium acetate, potassium acetate and calcium acetate; and examples of ammonia compound and amine include ammonium compounds quaternary such as ammonium hydroxide and hydroxide tetramethylammonium

Although the basic substance can be added as such, is preferably added as an aqueous solution.

The stage of forming dispersed particles of the resin solids and the step of neutralizing polyolefin modified non-neutralized and / or non-saponified may lead to out successively or at the same time.

Although melting kneading can be carried carried out by any known method, preferred examples of Melt kneading media include a kneader, a mixer Banbury and a multi-spindle extruder press.

Then it cools to room temperature of natural or artificial way the aqueous dispersion, which is obtained successively adding water and molten kneaded product and in the that the molten resin is dispersed. At this time, it harden the dispersed particles to obtain a dispersion of stable aqueous resin.

It is common that, in the preparation of the aqueous resin dispersion of the invention, can be used in combination of various secondary materials that can be used normally for aqueous resin dispersions, such as stabilizer, wetting agent, foaming agent, agent antifoam, coagulating agent, gelatinizing agent anti-aging, plasticizer, filler, dye, agent flavoring, anti-blocking agent and release agent.

The dispersed particles contained in the aqueous resin dispersion of the invention obtained above They are generally spherical, but do not always need to be spherical. The average diameter of the dispersed particles is not limited specifically, but is usually in the range of 1 at 20 µm, preferably 5 to 15 µm. The concentration of particles (solids concentration) of the resin dispersion aqueous is not specifically limited, but it is found normally in the range of 5 to 40% by weight.

The aqueous resin dispersion of the invention It is suitable for joining polyolefins that have been difficult to bind, such as polyethylene and polypropylene, and the dispersion is useful for bind a polyolefin to a polyolefin or a polyolefin to another material.

Like the other material, a arbitrary material such as cloth, fibers, plastic, paper or metal.

Examples of fabrics or fibers include natural fibers such as cotton and hemp; inorganic fibers, such as fiberglass, carbon fiber, asbestos fiber and metallic fiber; regenerated fibers, such as viscose rayon and cupra; semi-synthetic fibers, such as di or triacetate fiber; nylon-6, nylon-66 and fibers polyester (poly (ethylene terephthalate); and polyamide fiber aromatic, acrylic fiber, polyvinyl chloride fiber, polyolefin fiber, and polyvinyl alcohol fiber insolubilized or moderately solubilized. Can be applied short fibers to the adhesion joint by flocking.

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As plastics, not only are available polyolefins but also other arbitrary plastics, such as poly (vinyl chloride), ABS, polyester, polyamide, polycarbonate and an epoxy resin. The molded product of plastic to be attached can have any shape, such as sheet, film or other form.

Adhesion bonding can take place applying the aqueous resin dispersion of the invention to a adherent surface similar to an aqueous dispersion conventional adhesive type and then heating the dispersion until dry when needed.

Solvent dispersion

The solvent dispersion of the invention comprises an organic medium and the olefin copolymer containing polar group or thermoplastic resin composition dispersed therein In a solid state.

Examples of organic media that are good solvents for polyolefins include aromatic hydrocarbons,  such as benzene, toluene and xylene; Aliphatic hydrocarbons, such as hexane, heptane, octane and decane; hydrocarbons alicyclics, such as cyclohexane, cyclohexene and methylcyclohexane; aliphatic alcohols, such as ethanol and isopropanol; solvents ketone, such as acetone, methyl isobutyl ketone and methyl ethyl ketone; and halogenated hydrocarbons, such as trichlorethylene, dichloroethylene and chlorobenzene.

Examples of organic media that are bad solvents for polyolefins include alcohols, ketones, ethers, esters and cellosolves. Specifically, they can be mentioned methanol, ethanol, propanol, butanol, pentanol, hexanol, propanediol, phenol, diethyl ether, dipropyl ether, dibutyl ether, anisole, dioxane, tetrahydrofuran, acetone, methyl ethyl ketone, methyl isobutyl ketone, pentanone, hexanone, isophorone, acetophenone, acetic acid anhydrous, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, butyl formate, ethyl cellosolve and methyl cellosolve.

Organic media can be used individually or in combination of two or more classes, and it is preferable to use a mixture of a good solvent and a bad solvent from the viewpoints of fluidity at low temperature and dispersion stability. There is no limitation. specific to the reason between a good solvent and a bad solvent

To the solvent dispersion of the invention, known additives, such as pigment, filler and stabilizer, when needed, within limits not detrimental to the objects of the invention.

In the preparation of the solvent dispersion of the invention, for example, the olefin copolymer is mixed containing polar group or thermoplastic resin composition with the organic medium and heated until dissolved by full. The temperature for the melt is found normally in the range of 100 to 150 ° C. Then, the solution to precipitate the olefin copolymer containing Polar group or thermoplastic resin composition. With the purpose of precipitate the copolymer or composition in the range of temperature from 60 to 100 ° C, it is preferable to set the composition of the organic medium and adjust the speed of average cooling at 1 to 20ºC / h, preferably 2 to 10ºC / h. It is possible to dissolve the olefin copolymer containing polar group or thermoplastic resin composition in a medium organic composed only of a good solvent, add a bad solvent after completion of precipitation and then Perform additional precipitation.

The dispersed particles contained in the solvent dispersion of the invention obtained as previously they are generally spherical, but they don't have to be always spherical The average diameter of the dispersed particles does not it is specifically limited, but is normally found in the range of 1 to 20 µm, preferably 5 to 15 µm. The particle concentration (solids concentration) of the solvent dispersion is not specifically limited, but it normally found in the range of normally 5 to 40% in weight.

The resin dispersion used as an adhesive for the union of metal to metal, polyolefin to polyolefin or metal to polyolefin shows excellent adhesion properties, and therefore effectively used as an adhesive for conditioning in PTP ("Paper Thin Package") of medicines, a laminating adhesive, a coating material or a primer layer.

Film and sheet

The film and sheet comprising the olefin copolymer containing polar group or the composition of thermoplastic resin can be a stretched or unstretched, and they can be produced by an appropriate known method. Examples of the methods for producing the film and sheet of the invention include extrusion molding, injection molding, molding insufflation, blow molding, extrusion and blow molding, injection and blow molding, pressure molding, vacuum molding, calendering and blow molding.

When the film and sheet are produced that they comprise the olefin copolymer containing polar group or the thermoplastic resin composition by extrusion molding, an extrusion molding device can be adopted and known molding conditions to date. For example, using a single screw extruder press, an extruder press kneader, a piston extruder press, an extruder press gear, the olefin copolymer containing group is extruded molten polar or molten thermoplastic resin composition to from a T-shaped nozzle, whereby you can produce an unstretched film or sheet.

The film and sheet of the invention can be those produced by blow molding. When the film and sheet of the invention comprising the copolymer of olefin containing polar group or resin composition Thermoplastics are produced by blow molding, barely produces stretch contraction.

When the film and the sheet of the invention comprising the olefin copolymer containing polar group or The thermoplastic resin composition are produced by molding by injection, a molding device can be adopted by injection and molding conditions known so far. He olefin copolymer containing polar group or the composition of thermoplastic resin can be injection molded to give a film or sheet having the desired shape and thickness. They can stretch the film or sheet obtained by molding by injection.

The stretched film or sheet can be obtained stretching an unstretched film or sheet such as the film or extruded sheet mentioned above by a method of stretched known such as rameado (stretched longitudinal-transverse, stretched transverse-longitudinal), stretched with orientation Simultaneous biaxial or stretched monoaxial.

In the stretch of the film or sheet without stretch, it is desired that the stretching ratio is normally found in the range of 20 to 70 times in the case of biaxial orientation and normally 2 to 10 times in the case of monoaxial stretching, although it depends on the thickness of the unstretched film or sheet. He film thickness or stretched sheet is found preferably in the range of 5 to 200 µm, although it depends of the use of the film or sheet.

Next, the film and sheet of the invention having two or more layers of different compositions (sometimes referred to as "material (s) laminate (s) "hereinafter).

The film or sheet of a structure of multiple layers according to the invention is a film or a sheet of a multilayer structure consisting of two or more layers that have different compositions, and at least one layer of those layers may be formed from the olefin copolymer that It contains polar group. The film or sheet of the invention are a film or sheet of a multilayer structure that It consists of two or more layers that have different compositions, and at least one layer of those layers may be formed from the thermoplastic resin composition.

The film or sheet of a structure of multiple layers according to the invention also preferably consists in (a) a layer comprising the olefin copolymer containing polar group and (b) a thermoplastic resin layer, or also preferably it consists of (b) a thermoplastic resin layer and (c) a layer comprising the resin composition thermoplastic

The laminate of the invention is a film or sheet of a multilayer structure consisting of in two or more layers that have different compositions, and at least a layer of those layers may be formed from the copolymer of olefin containing polar group or resin composition thermoplastic

The laminated material consists desirably in:

(to)

a layer comprising the olefin copolymer that contains polar group, and

(b)

a layer of thermoplastic resin,

or

(b)

a layer of thermoplastic resin, and

(C)

a layer comprising the resin composition thermoplastic

Examples of thermoplastic resins for form the thermoplastic resin layer (b) in the film or the sheet of a multilayer structure include used resins for the thermoplastic resin composition above mentioned, such as polyolefin, polyamide, polyester, polyacetal, polystyrene, copolymer of acrylonitrile / butadiene / styrene (ABS), polycarbonate, poly (oxide phenylene), polyacrylate and polyvinyl chloride. These thermoplastic resins can be used individually or in combination.

The thermoplastic resin layer (b) comprises preferably a thermoplastic resin containing at least one selected resin of polyolefin, polyamide, polyester, polyacetal, polyvinyl chloride, polystyrene, acrylonitrile / butadiene / styrene copolymer (ABS) and polycarbonate, and more preferably comprises a resin thermoplastic selected from polyolefin, a vinyl copolymer containing polar / ethylene group, polyester, polycarbonate and polyamide.

Polyester resin is a polyester formed by units of dihydroxy compounds and acid units dicarboxylic The dihydroxy compounds are derived from aliphatic glycols, such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol and hexamethylene glycol, alicyclic glycols, such as cyclohexanedimethanol, aromatic dihydroxy compounds, such as bisphenol, or derivatives of two or more dihydroxy compounds selected from these compounds. The dicarboxylic acid units are derived from acids aromatic dicarboxylic acids, such as terephthalic acid, acid isophthalic and 2,6-naphthalenedicarboxylic acid, aliphatic dicarboxylic acids, oxalic acid, succinic acid, adipic acid, sebacic acid and undecadicarboxylic acid, acids alicyclic dicarboxylic acids, such as hexahydroterephthalic acid, or derivatives of two or more dicarboxylic acids selected from these acids. The polyester resin can be modified with a small amount of a trivalent or higher polyhydroxy compound or a polycarboxylic acid, such as triol or acid tricarboxylic.

As the thermoplastic polyester resin, it preferably use poly (ethylene terephthalate), poly (butylene terephthalate), a copolymer of poly (ethylene terephthalate / isophthalate).

As the polycarbonate resin, it can be used any of various polycarbonates and copolycarbonates obtained allowing dihydroxy compounds to react with phosgene or diphenyl carbonate by known procedures.

Examples of dihydroxy compounds include hydroquinone, resorcinol, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylethane, 4,4'-dihydroxydiphenyl-n-butane, 4,4'-dihydroxydiphenylheptane, 4,4'-dihydroxydiphenylphenyl, 4,4 4'-dihydroxydiphenyl-2,2-propane (bisphenol A), 4,4'-dihydroxy-3,3'-dimethyldiphenyl-2,2-propane, 4,4'-dihydroxy-3,3'-diphenylphenyl-2 , 2-propane, 4,4'-dihydroxydichlorodiphenyl-2,2-propane, 4,4'-dihydroxydiphenyl-1,1-cyclopentane, 4,4'-dihydroxydiphenyl-1,1-cyclohexane, 4,4'-dihydroxydiphenylmethylphenylmethane , 4,4'-dihydroxydiphenylethylphenylmethane, 4,4'-dihydroxydiphenyl-2,2,2-trichloro-1,1-ethane, 2,2'-dihydroxydiphenyl, 2,6-dihydroxynaphthalene, 4,4'-dihydroxydiphenyl ether, 4,4'-dihi-
droxy-, 3,3'-dichlorodiphenyl ether and 4,4'-dihydroxy-2,5-diethoxyphenyl ether.

It is preferable to use the polycarbonate you use 4,4'-dihydroxydiphenyl-2,2-propane (bisphenol A) of the above compounds for their excellent mechanical properties and transparency.

As the polyamide resin, it can be used any of the various polyamides and copolyamides obtained by caprolactam ring opening polymerization or polycondensation reaction of diamines with dicarboxylic acids by known procedures. Of these are preferably used nylon-6, nylon-6.6 or a polymer of condensation of adipic acid / m-xylenediamine.

Examples of polyolefins include a (co) ethylene polymer, a (co) propylene polymer, a (co) butene polymer, a (co) polymer of 4-methyl-1-pentene, a (co) polymer of 3-methyl-1-butene and a (co) hexene polymer. Of these, a (co) ethylene polymer, a (co) propylene polymer or a (co) polymer of 4-methyl-1-pentene. As the (co) ethylene polymer, a ethylene / vinyl acetate copolymer or a product of saponification of ethylene / vinyl acetate copolymer.

It is desired that the ethylene content of the ethylene / vinyl acetate copolymer is in the range of 15 60 mol%, preferably 25 to 50 mol%. The melt flow rate of ethylene / acetate copolymer Vinyl, as measured at 190 ° C, is in the range of 0.1 to 500 g / 10 min., Preferably 0.1 to 400 g / 10 min., More preferably 0.1 to 300 g / 10 min.

As the copolymer saponification product ethylene / vinyl acetate is preferably used one obtained by saponification of an ethylene / acetate copolymer of vinyl that has an ethylene content of 15 to 60 mol%, preferably 25 to 50 mol%, such that the degree of saponification should not be less than 50%, preferably not less than 90%. When ethylene content is in the previous interval, the saponification product barely thermally decomposes, easily molded into molten and has excellent extensibility, water resistance and resistance to gas permeation. When the degree of saponification is not less than 50%, the saponification product has an excellent resistance to gas permeation and is preferable.

In the laminated material of the invention, enter the thermoplastic resin layer (b) and the copolymer layer of olefin with polar group (a) or the resin composition layer thermoplastic (c) can be intercalated, for example, a (co) ethylene polymer or a propylene polymer that has been graft copolymerized with maleic anhydride.

The film and the sheet of a structure of multiple layers (laminated material) according to the invention can occur by any procedure. For example, the materials for forming layers are subjected to an integrated molding such as coextrusion to form a film or sheet, or a material to form a multilayer structure layer to form a film or sheet, followed by molding a material to form another layer on it to form a sheet or a film, or the materials to form layers are molded each one to obtain films or sheets, followed by lamination of the same by contact bonding, fusion bonding, joint bonding adhesion or similar.

The laminated material of the invention consists of desirable manner in the olefin copolymer layer containing polar group (a) or the thermoplastic resin composition layer (c), and the thermoplastic resin layer (b). To produce a laminated material of this type, a process of coextrusion molding in which a thermoplastic resin for form the thermoplastic resin layer (b) and the copolymer of olefin containing polar group or resin composition thermoplastic melt independently by different extruder presses, then feed to a nozzle structure of two layers or three layers and is coextruded so that the copolymer of olefin containing polar group or resin composition adhesive form an intermediate layer, or a procedure of interleaved lamination in which the thermoplastic resin layer (b), and the olefin copolymer layer containing polar group (a) or the thermoplastic resin composition layer (c) is they form each one previously and between these layers it is molten extruded An adhesive resin composition.

Of the above procedures, the coextrusion molding process from the point of view of interlaminar resistance. The molding process by Coextrusion includes a procedure with a T-shaped nozzle that uses a flat nozzle and an insufflation procedure that uses a circular nozzle As a flat nozzle, any one can be used the type of single collector that uses a black box and the type with Multiple collectors As a mouthpiece for the procedure of insufflation, any known nozzle can be used.

The appropriateness can be determined thickness of each layer of the laminated material according to the use of the material  laminate. When the laminated material is obtained as a sheet or film, the thermoplastic resin layer (b) has a thickness of usually 0.01 to 1 mm, the adhesive layer that functions as a adhesive has a thickness of usually 0.005 to 1 mm, and the layer of the olefin copolymer containing polar group (a) or layer of the thermoplastic resin composition (c) is usually 0.01 to 5 mm

When the laminated material of the invention it comprises, for example, the olefin copolymer layer that contains polar group (a) and the thermoplastic resin layer (b), the structure of the laminated material can be a structure of two layers, that is, (a) / (b), a structure in which the layer (a) is disposes on each side, that is, (a) / (b) / (a), or a structure in the that another layer (x), such as a polyolefin layer, is added is say, (a) / (b) / (x) / (b) / (a), (x) / (a) / (b) or (x) / (b) / (a).

The film or sheet of the invention in the that at least one layer is the olefin copolymer layer that Contains polar group (a) or resin composition layer thermoplastic (c) is used favorably as a sheet or film protective, retractable, wrap or agricultural. Besides, the film or sheet of the invention can be used in a manner favorable as selective separation film, such as film Blood plasma separation, vaporization film selective water permeability, ion exchange membrane, Optical resolution film or battery separation.

The sheet or film of the invention can apply to various uses such as an administration system of drugs, chemical flask, PTP packaging and microcapsule.

Effect of the invention

The olefin copolymer containing group polar or thermoplastic resin composition according to the invention They are excellent in the properties of adhesion to polar materials such as metals and polar resins, compatibility and flexibility.

Example

The present invention is further described. with reference to the following examples, but should be interpreted that the invention is not limited in any way to those examples.

In the examples, various were measured Properties as follows.

Adhesion properties Film production

On a press plate, they overlapped in this order an aluminum foil that was 0.1 mm thick, a polyimide sheet and an aluminum sheet that had a 100 µm thickness from whose center a square had been trimmed 20 cm x 20 cm, and in the center (trimmed part) 4.0 g were placed of a sample (olefin copolymer containing polar group). So, they overlapped on it in this order a polyimide sheet, an aluminum sheet and a plate press.

The interposed sample was placed between the plates press in a hot press at 190 ° C and preheated for approximately 5 minutes In order to remove bubbles from the sample, the operations of pressurization (50 kg / cm2 -G) and release of Pressure. Subsequently, the pressure was increased to 100 kg / cm2 -G, and the sample was heated for 5 minutes under pressure. After pressure release, the press plates of the pressing machine and transferred to a different pressing machine maintaining a compression section at 20 ° C, followed by cooling for 5 minutes at a pressure of 100 kg / cm2 -G. After the pressure release, it He extracted the sample. From the resulting movie (movie from olefin copolymer containing polar group), a part that had a thickness of about 150 to 170 µm to Measure adhesion strength.

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Measurement of adhesion resistance to Al

The copolymer film of olefin containing polar group between two aluminum sheets 20 cm x 20 cm squares (thickness: 50 µm), and the sheets were laminated aluminum sheets and the olefin copolymer film that contains polar group under the same pressing conditions as in the "Movie production" above. The material was cut resulting laminate to obtain a strip that had a width of 15 mm, and the aluminum foil and the film of the olefin copolymer containing polar group of one another in the adhesive contact surface with a detachment angle of 180º, to measure the resistance to detachment.

Measurement of PET adhesion resistance

The copolymer film of olefin containing polar group between two films of 20 cm x homopoly (ethylene terephthalate) (PET) 20 cm (thickness: 100 µm), and the PET films were laminated and the olefin copolymer film containing polar group in the same pressing conditions as in the "Production of the film "above, except when the temperature of pressed at 280 ° C and the preset press temperature was changed cooling to -8 ° C. The resulting laminate was cut to obtain a strip that was 15 mm wide, and peeled the PET film and the copolymer film from olefin containing polar group from one another on the surface of adhesive contact with a 180º detachment angle, for measure the resistance to detachment.

Ny adhesion resistance measurement

The copolymer film of olefin containing polar group between two nylon 6 films 20 cm x 20 cm squares (thickness: 100 µm), and the sheets were laminated 6 nylon films and the olefin copolymer film that contains polar group under the same pressing conditions as in the "Movie production" above, except when it was changed the pressing temperature up to 250 ° C. The material was cut resulting laminate to obtain a strip that had a width of 15 mm, and the nylon 6 film and the film of the olefin copolymer containing polar group of one another in the adhesive contact surface with a detachment angle of 180º, to measure the resistance to detachment.

EVOH adhesion resistance measurement

The copolymer film of olefin containing polar group between two copolymer films 20 cm x 20 cm square ethylene / vinyl alcohol (thickness: 100 um), and the copolymer films of ethylene / vinyl alcohol and the olefin copolymer film that contains polar group under the same pressing conditions as in the "Movie Production" above, except that the pressing temperature changed to 200 ° C. The material was cut resulting laminate to obtain a strip that had a width of 15 mm, and the copolymer film of ethylene / vinyl alcohol and olefin copolymer film which contains polar group of each other on the contact surface adhesive with a 180º detachment angle, to measure the shedding resistance

Impact resistance test, tensile test Izod impact resistance (notched)

Impact resistance at 23 ° C was measured according to ASTM D 256.

Tensile test

A punch-shaped sample (" dumbbell ") of a pressed sheet was subjected to a tensile test under conditions of a temperature of 23 ° C, a wingspan of 30 mm and a tensile speed of 30 mm / min. according to ASTM D 638, to measure tensile strength and elongation at break.

Anti-fogging properties Film production

On a press plate, they overlapped in this order a PET sheet and an aluminum sheet that had a 100 µm thickness from whose center a square had been trimmed 20 cm x 20 cm, and in the center (cut-out part) they put 3.3 g of a sample (olefin copolymer containing polar group). So, they overlapped on it in this Order a PET sheet, an aluminum sheet and a plate press.

The interposed sample was placed between the plates press in a hot press at 200 ° C and preheated for approximately 7 minutes In order to remove bubbles from the sample, the operations of pressurization (50 kg / cm2 -G) and release of Pressure. Subsequently, the pressure was increased to 100 kg / cm2 -G, and the sample was heated for 2 minutes under pressure. After pressure release, the press plates of the pressing machine and transferred to a different pressing machine maintaining a compression section at 0 ° C, followed by cooling for 4 minutes at a pressure of 100 kg / cm2 -G. After the pressure release, it He extracted the sample. The olefin copolymer film was used which contains resulting polar group to evaluate the properties anti-fog initials.

Evaluation of the initial anti-fogging properties

In a 100 cc beaker, it they put 70 cc of water and covered the top of the glass of precipitated with the sample film. Then he put the glass of precipitates in a constant temperature water bath at 50 ° C, and the water bath was allowed to remain at a temperature constant environment of 20ºC. After 24 hours, the degree of fogging on the inner surface of the film sample.

Evaluation Criteria :

AA: Droplets are seen running through the film surface and no drop adheres to the surface of the movie.

BB: large droplets adhere to some parts from the surface of the film.

CC: thin droplets adhere to almost all of the film surface.

Coating properties Cross section adhesion test

A sample provided with cuts was prepared cross-sections according to the cross-section adhesion test described in JIS K5400. It was applied to the Cellotape sample (trade name, available from Nichiban Co., Ltd.). So he Cellotape quickly detached at an angle of 90º and from this mode separated from the sample. The number of cuts was counted transverse the coating film remaining on the themselves and was taken as an indication of the properties of accession.

Load dispersibility Montmorillonite preparation conferred organicity

They were dispersed in 1000 ml of distilled water at 70 ° C, 40 g of montmorillonite of type Na. In the suspension resulting a solution obtained by mixing 20 g of 12-aminododecanoic acid and 2 ml of acid hydrochloric in 100 ml of distilled water, and stirred at 70 ° C for 2 hours to exchange the metal ions present between the layers of montmorillonite by organic cations. So, the precipitate obtained was filtered, washed sufficiently with water hot to perform a purification, then lyophilized and pulverized to obtain 27 g of montmorillonite which had been conferred organicity.

Preparation of a sample for the evaluation of properties

To a mixture of 92 parts by weight of a propylene / ethylene block copolymer (ethylene content: 5.6 mol%, MFR: 25 g / 10 min.), 5 parts by weight of the montmorillonite to which organicity was obtained above and 3 parts by weight of the olefin copolymer which contains polar group obtained in each example, Irganox 1010?, Irgaphos 168 ™ and calcium stearate each in an amount of 0.1 parts by weight, and the resulting resin was melted by means of a double screw extruder with a diameter of 20 mm at a cylinder temperature of 200 ° C in an atmosphere of nitrogen to prepare granules. The granules were molded by injection under the conditions of a cylinder temperature of 200 ° C, a mold temperature of 40 ° C and an injection pressure 1000 kg / cm2 to obtain samples for the evaluation of various properties Samples were kept at 23 ° C for 168 hours and then underwent the tests.

Flexural modulus (FM)

The flexural modulus was measured according to the standard ASTM D 638 using an injection molded sample that had a length of 5 inches, a width of 1/2 inches and a thickness of 1/8 inch

Izod impact resistance (IZ)

Izod impact resistance at 23 ° C was measured according to ASTM D 258 using a sample (with notch rear) which was 1/4 inch thick.

Heat Distortion Temperature (HDT)

Heat distortion temperature was measured according to ASTM D 648 using an injection molded sample which had a length of 5 inches, a width of 1/4 inches and a thickness of 1/2 inches.

Water dispersibility Preparation of water dispersion

They were mixed at room temperature with 40 g of olefin copolymer containing polar group obtained, 4 g of polypropylene with maleic anhydride graft (propylene / ethylene: 98/2 mol, maleic anhydride content: 4.0% by weight, weight Average molecular viscosimeter: 17,000, density: 0.919 g / cm3, melting point: 136 ° C, softening point: 143 ° C, melt viscosity (180 ° C): 500 cps) as polyolefin modified and 1.2 g of potassium oleate as a surfactant. TO the mixture was then kneaded for 5 minutes using a Labo-plastomill mixer (temperature preset: 200ºC). Then, 1.4 g was added to the kneaded product of an 18.7% aqueous solution of potassium hydroxide, followed Kneading in melt for another 5 minutes. Subsequently extracted the contents of the mill, and the viscous emulsion was dispersed resulting in hot water at 60 ° C to obtain a dispersion of aqueous resin

Measurement of the diameter of the dispersed particles

The diameter of the particles was measured dispersed using a Honeywell Microtrack analyzer Co.

Dispersion stability

The aqueous resin dispersion obtained was placed in each example in a glass bottle that could be closed, and it Let it stand at room temperature. After one month, the separation between the aqueous phase and the phase of resin.

Heat sealing resistance to Al

Each dispersion was applied on a sheet of Aluminum (50 µm) by a bar coater, dried on air and then heated for 10 seconds in an air oven preset at 200 ° C to obtain a coated sheet that had a uniform coating film. The sheet was joined by heat coated and a sheet of LLDPE (available from Akosu Kogyo K.K., thickness: 300 µm) at a temperature of 180 ° C for 1 second at a pressure of 1 kg / cm2 by the method according to the JIS standard Z1707, and then cut to get a sample that had a width of 15 mm. The sample was subjected to a test of 180 ° detachment with a measuring temperature of 23 ° C for measure adhesion resistance (tensile speed: 300 mm / min.)

Solvent dispersibility Preparation of solvent dispersion

They were put in a 1 liter glass autoclave equipped with a stirrer, 55 g of the olefin copolymer that contains polar group obtained and 495 g of toluene, and were heated up to 130 ° C to completely dissolve the resin. Later cooled the solution to 85 ° C for a period of 1 hour, then cooled from 85 ° C to 40 ° C over a period of 4.5 hours and then it was cooled from 40 ° C to 30 ° C for a period of 30 minutes, to obtain a resin dispersion.

Measurement of the diameter of the dispersed particles

The diameter of the particles was measured dispersed using a Honeywell Microtrack analyzer Co.

Dispersion stability

The dispersion was obtained in solvent obtained in each example in a glass bottle that could be closed, and left to remain at rest at room temperature. After a month, the separation between the aqueous phase and the phase of resin.

Heat sealing resistance to Al

Each dispersion was applied on a sheet of Aluminum (50 µm) by a bar coater, dried on air and then heated for 10 seconds in an air oven preset at 200 ° C to obtain a coated sheet that had a uniform coating film. The sheet was joined by heat coated and a sheet of LLDPE (available from Akosu Kogyo K.K., thickness: 300 µm) at a temperature of 180 ° C for 1 second at a pressure of 1 kg / cm2 by the method according to the JIS standard Z1707, and then cut to get a sample that had a width of 15 mm. The sample was subjected to a test of 180 ° detachment with a measuring temperature of 23 ° C for measure adhesion resistance (tensile speed: 300 mm / min.)

Examples 34 to 39 are according to the invention. All other examples are reference examples.

Example 1

In a glass polymerization reactor of 1000 ml meticulously purged with nitrogen, 400 ml were put of n-dean, then nitrogen was passed to its through at a rate of 20 l / h, and the content was maintained at 130 ° C for 10 minutes. Then, 0.6 mmol of triisobutylaluminum, followed by the additional addition of 0.48 mmoles of undecen-1-ol (having drying on activated alumina) represented by the following formula.

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118

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Then, 1,100 were additionally added mmoles of methylaluminoxane, and the passage of nitrogen stopped, followed by the passage of ethylene at a speed of 12.5 l / h. Finally, a suspension solution of toluene in which 0.002 mmol of dichloride dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di-tert-butylfluorenyl) zirconium  and 0.500 mmol of methylaluminoxane at room temperature for 10 minutes to start the polymerization. After the polymerization at 130 ° C for 1 hour at atmospheric pressure, added a small amount of isobutyl alcohol to finish the polymerization. Then, 100 ml of a solution of isobutyl alcohol containing 1 ml of an aqueous solution of concentrated hydrochloric acid, followed by heating at 75 ° C in An atmosphere of nitrogen. The polymer solution was introduced obtained in a large excess of methanol to precipitate a polymer and then dried under vacuum at 80 ° C for 12 hours. As a result, 3.73 g of a polymer were obtained.

The properties of the olefin copolymer that Contains resulting polar group are set out in Table 8.

The adhesion strength (a Al) of the olefin copolymer containing polar group by the method previously mentioned. The result is shown in table 9.

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Example 2

In a glass polymerization reactor of 1000 ml meticulously purged with nitrogen, 400 ml were put of toluene, then nitrogen was passed through it to a 20 l / h rate, and the content was maintained at 90 ° C for 10 minutes Then, 0.6 mmol of triisobutylaluminum was added, followed by the additional addition of 0.48 mmol of 1,2-epoxy-9-decene (having dried on silica-alumina) represented by the following formula.

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119

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Then, 1,100 mmol of methylaluminoxane, and the passage of nitrogen was stopped, followed by the ethylene passage at a speed of 12.5 l / h. Finally it was added a toluene suspension solution in which they had contacted 0.002 mmol of dichloride from dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di-tert-butylfluorenyl) zirconium  and 0.500 mmol of methylaluminoxane at room temperature for 10 minutes to start the polymerization. After having been done the polymerization at 90 ° C for 1 hour at atmospheric pressure, is added a small amount of isobutyl alcohol to finish the polymerization. Then, 100 ml of a solution of isobutyl alcohol containing 1 ml of an aqueous solution of concentrated hydrochloric acid, followed by heating at 75 ° C in An atmosphere of nitrogen. The polymer solution was introduced obtained in a large excess of methanol to precipitate a polymer and then dried under vacuum at 80 ° C for 12 hours. As a result, 3.64 g of a polymer were obtained.

The properties of the olefin copolymer that Contains resulting polar group are set out in Table 8.

The adhesion resistance (to PET) of the olefin copolymer containing polar group by the method previously mentioned. The result is shown in table 9.

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Example 3

In a glass polymerization reactor of 1000 ml meticulously purged with nitrogen, 400 ml were put of n-dean, then nitrogen was passed to its through at a rate of 20 l / h, and the content was maintained at 90 ° C for 10 minutes. Then, 0.6 mmol of triisobutylaluminum, followed by the additional addition of 0.48 mmoles of anhydride (2,7-octadien-1-yl) succinic (having dried on activated alumina) represented by the following formula

120

Then, 1,100 mmol of methylaluminoxane, and the passage of nitrogen was stopped, followed by the ethylene passage at a speed of 12.5 l / h. Finally it was added a toluene suspension solution in which they had contacted 0.002 mmol of dichloride from dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di-tert-butylfluorenyl) zirconium  and 0.500 mmol of methylaluminoxane at room temperature for 10 minutes to start the polymerization. After the polymerization at 130 ° C for 1 hour at atmospheric pressure, added a small amount of isobutyl alcohol to finish the polymerization. Then, 100 ml of a solution of isobutyl alcohol containing 1 ml of an aqueous solution of concentrated hydrochloric acid, followed by heating at 75 ° C in An atmosphere of nitrogen. The polymer solution was introduced obtained in a large excess of methanol to precipitate a polymer and then dried under vacuum at 80 ° C for 12 hours. As a result, 3.18 g of a polymer were obtained.

The properties of the olefin copolymer that Contains resulting polar group are set out in Table 8.

Adhesion strength (a Ny) of the olefin copolymer containing polar group by the method previously mentioned. The result is shown in table 9.

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Example 4

The propylene copolymerization was carried out and a monomer containing polar group in the same way as in the Example 1, except that 0.00075 mmol of dichloride of dimethylsilylene (2-methyl-4-phenanthryl-1-indenyl) zirconium  instead of dichloride of dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di-tert-butylfluorenyl) zirconium,  Pentapropenylsuccinic anhydride represented by the following formula as a monomer containing polar group, and carried out the polymerization at 60 ° C for 30 minutes with the passage of propylene instead of ethylene.

121

The properties of the olefin copolymer that Contains resulting polar group are set out in Table 8.

The adhesion resistance (to EVOH) of the olefin copolymer containing polar group by the method previously mentioned. The result is shown in table 9.

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Example 5

Polymerization thereof was carried out. so as in example 4, except because it was used 1,2-epoxy-9-decene instead of pentapropenils succinic anhydride. The properties of olefin copolymer containing resulting polar group is set out in table 8.

At 20% by weight of the olefin copolymer which contains polar group obtained above, 80% was added in weight of nylon 6 (relative viscosity: 2.35 dl / g), and the mixture is kneaded by means of a twin screw extruder with a diameter of 20 mm at 250 ° C to prepare a resin composition thermoplastic The thermoplastic resin composition was subjected to an impact resistance test and a tensile test by the methods mentioned above. The results are set out in table 9.

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Example 6

At 10% by weight of the olefin copolymer which contains polar group obtained in example 4, a 30% by weight of nylon 6 (relative viscosity: 2.35 dl / g) and 60% in weight of a propylene homopolymer (MFR (230 ° C, load of 2.16 kg): 2.2 g / 10 min.), and the mixture was kneaded by melting twin screw extruder with a diameter of 20 mm at 250 ° C to prepare a thermoplastic resin composition. The thermoplastic resin composition was subjected to a test of impact resistance and tensile test through methods mentioned above. The results are shown in the table 9.

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Comparative example one

At 70% by weight of a propylene homopolymer (MFR (230 ° C, 2.16 kg load): 2.2 g / 10 min.), 30% was added by weight of nylon 6 (relative viscosity: 2.35 dl / g), and the mixture is kneaded by means of a twin screw extruder with a diameter of 20 mm at 250 ° C to prepare a resin composition  thermoplastic The thermoplastic resin composition was subjected to an impact resistance test and a tensile test by the methods mentioned above. The results are set out in table 9.

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Example 7

From the olefin copolymer containing polar group obtained in example 1, a film of the way mentioned above. Using the film, they were evaluated anti-fogging properties. The result is stated in the table 9.

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Example 8

Polymerization thereof was carried out. so in example 1, except that delta was used 12-tridecenol represented by the following formula instead of undecen-1-ol and Propylene was used instead of ethylene.

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The properties of the olefin copolymer that Contains resulting polar group are set out in Table 8.

Coating properties were evaluated of the olefin copolymer containing polar group by the method mentioned above. The result is shown in the table 9.

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Example 9

Using the olefin copolymer it contains polar group obtained in example 4, the dispersibility was evaluated of the load by the method mentioned above. He result is shown in table 9.

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Comparative example 2

The dispersibility of the load of the same way as in example 9, except because it was not used olefin copolymer containing polar group. The result is set out in table 9.

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Example 10

Using the olefin copolymer it contains polar group obtained in example 1, a dispersion in water in the manner mentioned above, and the water dipersability by the method mentioned above. The result is shown in table 9.

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Example 11

The copolymerization of ethylene and a monomer containing polar group in the same way as in the Example 1, except that represented undecylenic acid was used using the following formula instead of undecen-1-ol.

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The properties of the olefin copolymer that Contains resulting polar group are set out in Table 8.

Using the olefin copolymer it contains polar group thus obtained, a water dispersion of the manner mentioned above, and dispersibility was assessed in water by the method mentioned above. The result is set out in table 9.

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Example 12

Using the olefin copolymer it contains polar group obtained in example 3, a dispersion in solvent in the manner mentioned above, and the solvent dispersibility by the mentioned method previously. The result is shown in table 9.

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TABLE 9

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Example 13

In a 2 liter stainless steel autoclave (SUS) meticulously purged with nitrogen, 120 g of 1-butene, 880 ml of Mitsui hexane and 1.50 mmol of triisobutylaluminum. The SUS autoclave was heated to 150 ° C and 1,140 mmol of methylaluminoxane were added, followed by additional addition of 1,350 mmol of undecen-1-ol (having dried on activated alumina and then vacuum distillate) represented by the following formula. Maintaining the temperature at 150 ° C, the autoclave was pressurized with ethylene so that the total pressure it became 30 kg / cm2 -G.

127

Separately, in a 20 ml glass flask meticulously purged with nitrogen, a nitrogen was injected with solution-suspension of toluene in which they had contacted 0.00075 mmol of dichloride dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di-tert-butylfluorenyl) zirconium and 0.4300 mmol of methylaluminoxane at room temperature for 10 minutes, and 600 Nml of hydrogen were also injected. During the 10 minute period after injection, the temperature was maintained of the autoclave at 150 ° C and the pressure was maintained therein immediately after injection by pressurization with ethylene. Then, a small amount of isobutyl alcohol was added to finish the polymerization. The solution of polymer obtained in a large excess of methanol to precipitate a polymer and then dried under vacuum at 80 ° C for 12 hours. How result, 10.40 g of a polymer were obtained. The activity of polymerization was 83 kg / mmol • Zoth.

The properties of the olefin copolymer that Contains the resulting polar group are shown in Table 10.

Coating properties were evaluated of the olefin copolymer containing polar group by the method mentioned above. The result is shown in the table eleven.

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Example 14

Ethylene was polymerized, 1-butene and a monomer containing polar group of the same way as in example 13, except because acid was used undecylenic represented by the following formula instead of undecen-1-ol.

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The properties of the olefin copolymer that Contains the resulting polar group are shown in Table 10.

The adhesion resistance (a Al) of the olefin copolymer containing polar group by the method previously mentioned. The result is shown in table 11.

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Example 15

Ethylene was polymerized, 1-butene and a monomer containing polar group of the same way as in example 13, except because it was used 1,2-epoxy-9-decene represented by the following formula instead of undecen-1-ol and 550 Nml of hydrogen.

129

The properties of the olefin copolymer that Contains the resulting polar group are shown in Table 10.

At 20% by weight of the olefin copolymer which contains polar group obtained above, 80% was added in weight of nylon 6 (relative viscosity: 2.35 dl / g), and the mixture is kneaded by means of a twin screw extruder with a diameter of 20 mm at 250 ° C to prepare a resin composition thermoplastic The thermoplastic resin composition was subjected to an impact resistance test and a tensile test by the methods mentioned above. The results are set out in table 11.

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Example 16

Ethylene was polymerized, 1-butene and a monomer containing polar group of the same way as in example 13, except because it was used anhydride (2,7-octadien-1-yl) succinic represented by the following formula instead of undecen-1-ol and 550 Nml of hydrogen.

130

The properties of the olefin copolymer that Contains the resulting polar group are shown in Table 10.

At 20% by weight of the olefin copolymer which contains polar group obtained above, 80% was added in weight of nylon 6 (relative viscosity: 2.35 dl / g), and the mixture is kneaded by means of a twin screw extruder with a diameter of 20 mm at 250 ° C to prepare a resin composition thermoplastic The thermoplastic resin composition was subjected to an impact resistance test and a tensile test by the methods mentioned above. The results are set out in table 11.

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Example 17

Ethylene, propylene and a polymer were polymerized monomer containing polar group in the same way as in the Example 16, except that propylene was injected at a pressure initial partial of 3 kg / cm2 instead of 1-butene, hydrogen was not added, and the polymerization at a polymerization temperature of 80 ° C.

The properties of the olefin copolymer that Contains the resulting polar group are shown in Table 10.

At 20% by weight of the olefin copolymer which contains polar group obtained above, 80% was added in weight of nylon 6 (relative viscosity: 2.35 dl / g), and the mixture is kneaded by means of a twin screw extruder with a diameter of 20 mm at 250 ° C to prepare a resin composition thermoplastic The thermoplastic resin composition was subjected to an impact resistance test and a tensile test by the methods mentioned above. The results are set out in table 11.

131

TABLE 11

132

Example 18

In a glass polymerization reactor of 1000 ml meticulously purged with nitrogen, 400 ml were put of n-dean, then nitrogen was passed to its through at a rate of 20 l / h, and the content was maintained at 130 ° C for 10 minutes. Then, 0.6 mmol of triisobutylaluminum, followed by additional 0.48 mmol addition delta 12-tridecenol (having dried over activated alumina and then vacuum distillate) represented by The following formula.

133

Then, 1,100 mmol of methylaluminoxane, and the passage of nitrogen was stopped, followed by the ethylene passage at a speed of 12.5 l / h. Finally it was added a toluene suspension solution in which they had contacted 0.002 mmol of dichloride from dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di-tert-butylfluorenyl) zirconium  and 0.500 mmol of methylaluminoxane at room temperature for 10 minutes to start the polymerization. After the polymerization at 130 ° C for 1 hour at atmospheric pressure, added a small amount of isobutyl alcohol to finish the polymerization. Then, 100 ml of a solution of isobutyl alcohol containing 1 ml of an aqueous solution of concentrated hydrochloric acid, followed by heating at 75 ° C in An atmosphere of nitrogen. The polymer solution was introduced obtained in a large excess of methanol to precipitate a polymer and then dried under vacuum at 80 ° C for 12 hours. As a result, 3.44 g of a polymer were obtained.

The properties of the olefin copolymer that Contains resulting polar group are set out in Table 12.

Coating properties were evaluated of the olefin copolymer containing polar group by the method mentioned above. The result is shown in the table 13.

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Example 19

Propylene and a monomer were copolymerized which contains polar group in the same way as in example 18, except that 0.00075 mmol of dichloride of dimethylsilylene (2-methyl-4-phenanthryl-1-indenyl) zirconium  instead of dichloride of dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di-tert-butylfluorenyl) zirconium  and polymerization was performed at 60 ° C for 30 minutes with passage of propylene instead of ethylene.

The properties of the olefin copolymer that Contains resulting polar group are set out in Table 12.

Coating properties were evaluated of the olefin copolymer containing polar group by the method mentioned above. The result is shown in the table 13.

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Example 20

In a 2 liter stainless steel autoclave (SUS) meticulously purged with nitrogen, 120 g of 1-butene, 950 ml of Mitsui hexane and 1.50 mmol of triisobutylaluminum. The SUS autoclave was heated to 150 ° C and 1,140 mmol of methylaluminoxane were added, followed by additional addition of 1,350 mmol delta 12-tridecenol (having dried over silica-alumina and then vacuum distillate) represented by the above formula. Keeping the temperature at 150 ° C, the autoclave was pressurized with ethylene so that the total pressure became 30 kg / cm2 -G. Separately, in a glass flask 20 ml meticulously purged with nitrogen, injected with nitrogen a solution-suspension of toluene in the who had contacted 0.00075 mmol of dichloride from dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di-tert-butylfluorenyl) zirconium  and 0.4300 mmol of methylaluminoxane at room temperature for 10 minutes, and 600 Nml of hydrogen were also injected. During the 10 minute period after injection, the temperature was maintained of the autoclave at 150 ° C and the pressure was maintained therein immediately after injection by pressurization with ethylene. Then, a small amount of alcohol was added isobutyl to terminate the polymerization. The polymer solution obtained in a large excess of methanol to precipitate a polymer and then dried under vacuum at 80 ° C for 12 hours. As a result, 10.40 g of a polymer was obtained. The polymerization activity was 83 kg / mmol • Zoth.

The properties of the olefin copolymer that Contains resulting polar group are set out in Table 12.

Coating properties were evaluated of the olefin copolymer containing polar group by the method mentioned above. The result is shown in the table 13.

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Example 21

Ethylene and a monomer were copolymerized which contains polar group in the same way as in example 18, except because acid was used pentadec-14-enoico represented using the following formula instead of delta 12-tridecenol.

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The properties of the olefin copolymer that Contains resulting polar group are set out in Table 12.

The adhesion resistance (a Al) of the olefin copolymer containing polar group by the method previously mentioned. The result is shown in table 13.

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Example 22

Propylene and a monomer were copolymerized which contains polar group in the same way as in example 19, except that pentapropenylsuccinic anhydride represented was used using the following formula instead of delta 12-tridecenol.

135

The properties of the olefin copolymer that Contains resulting polar group are set out in Table 12.

The adhesion resistance (a Al) of the olefin copolymer containing polar group by the method previously mentioned. The result is shown in table 13.

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TABLE 13

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Example 23

In a glass polymerization reactor of 1000 ml meticulously purged with nitrogen, 400 ml were put of toluene, then nitrogen was passed through it to a 20 l / h rate, and the content was maintained at 60 ° C for 10 minutes Then, 0.6 mmol of triisobutylaluminum was added, followed by the additional addition of 0.48 mmol of anhydride (2,7-octadien-1-yl) succinic represented by the following formula.

138

Then, 1,100 mmol of methylaluminoxane, and the passage of nitrogen was stopped, followed by the propylene step at a speed of 12.5 l / h. Finally it was added a toluene suspension solution in which had contacted 0.0075 mmol of dichloride dimethylsilylene (2-methyl-4-phenanthryl-1-indenyl) zirconium  and 0.500 mmol of methylaluminoxane at room temperature for 10 minutes to start the polymerization. After the polymerization at 60 ° C for 30 minutes at atmospheric pressure, added a small amount of isobutyl alcohol to finish the polymerization. Then, 100 ml of a solution of isobutyl alcohol containing 1 ml of an aqueous solution of concentrated hydrochloric acid, followed by heating at 75 ° C in An atmosphere of nitrogen. The polymer solution was introduced obtained in a large excess of methanol to precipitate a polymer and then dried under vacuum at 80 ° C for 12 hours. As a result, 1.75 g of a polymer were obtained.

The properties of the olefin copolymer that Contains resulting polar group are set out in Table 14.

The adhesion resistance (a Al) of the olefin copolymer containing polar group by the method previously mentioned. The result is shown in table 15.

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Example 24

In a glass polymerization reactor of 1000 ml meticulously purged with nitrogen, 400 ml were put of toluene, then nitrogen was passed through it to a 20 l / h rate, and the content was maintained at 90 ° C for 10 minutes Then, 0.6 mmol of triisobutylaluminum was added, followed by the additional addition of 0.48 mmol of 1,2-epoxy-9-decene (having dried on silica-alumina) represented by the following formula.

139

Then, 1,100 mmol of methylaluminoxane and stopped the passage of nitrogen, followed by the ethylene passage at a speed of 12.5 l / h. Finally it was added a toluene suspension solution in which they had contacted 0.002 mmol of dichloride from dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di-tert-butylfluorenyl) zirconium  and 0.500 mmol of methylaluminoxane at room temperature for 10 minutes to start the polymerization. After completion the polymerization at 90 ° C for 1 hour at atmospheric pressure, is added a small amount of isobutyl alcohol to finish the polymerization. Then, 100 ml of a solution of isobutyl alcohol containing 1 ml of an aqueous solution of concentrated hydrochloric acid, followed by heating at 75 ° C in An atmosphere of nitrogen. The polymer solution was introduced obtained in a large excess of methanol to precipitate a polymer and then dried under vacuum at 80 ° C for 12 hours. As a result, 3.08 g of a polymer were obtained.

The properties of the olefin copolymer that Contains resulting polar group are set out in Table 14.

The adhesion resistance (a Al) of the olefin copolymer containing polar group by the method previously mentioned. The result is shown in table 15.

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Example 25

Ethylene and a monomer were copolymerized which contains polar group in the same way as in example 24, except because it was used 4-hex-5-enyloxy-phenol represented by the following formula instead of 1,2-epoxy-9-decene.

140

The properties of the olefin copolymer that Contains resulting polar group are set out in Table 14.

The adhesion resistance (to PET) of the olefin copolymer containing polar group by the method previously mentioned. The result is shown in table 15.

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TABLE 15

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Example 26

In a glass polymerization reactor of 1000 ml meticulously purged with nitrogen, 400 ml were put of toluene, then nitrogen was passed through it to a 20 l / h rate and the content was maintained at 0 ° C for 10 minutes Then, 0.6 mmol of triisobutylaluminum was added, followed by the additional addition of 0.48 mmol of undecen-1-ol represented by The following formula.

143

Then, 1,100 mmol of methylaluminoxane and stopped the passage of nitrogen, followed by the 1-butene step at a speed of 12.5 l / h. Finally, a suspension solution of toluene in which 0.0020 mmol of dichloride dimethylsilylene (2-methyl-4-phenanthryl-1-indenyl) zirconium  and 0.500 mmol of methylaluminoxane at room temperature for 10 minutes to start the polymerization. After the polymerization at 0 ° C for 60 minutes at atmospheric pressure, added a small amount of isobutyl alcohol to finish the polymerization. Then, 100 ml of a solution of isobutyl alcohol containing 1 ml of an aqueous solution of concentrated hydrochloric acid, followed by heating at 75 ° C in An atmosphere of nitrogen. The polymer solution was introduced obtained in a large excess of methanol to precipitate a polymer and then dried under vacuum at 80 ° C for 12 hours. As a result, 0.25 g of a polymer was obtained.

The properties of the olefin copolymer that Contains the resulting polar group are shown in Table 16.

Coating properties were evaluated of the olefin copolymer containing polar group by the method mentioned above. The result is shown in the table 17.

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Example 27

1-butene and a polymer were polymerized monomer containing polar group in the same way as in the example 26, except because it was used 1,2-epoxy-9-decene represented by the following formula instead of undecen-1-ol.

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The properties of the olefin copolymer that Contains the resulting polar group are shown in Table 16.

The adhesion resistance (to PET) of the olefin copolymer containing polar group by the method previously mentioned. The result is shown in table 17.

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Example 28

1-butene and a polymer were polymerized monomer containing polar group in the same way as in the Example 26, except that 1.35 mmol of acid were used undecylenic represented by the following formula instead of undecen-1-ol and 1.5 mmol were used of triisobutylaluminum.

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The properties of the olefin copolymer that Contains the resulting polar group are shown in Table 16.

The adhesion resistance (a Al) of the olefin copolymer containing polar group by the method previously mentioned. The result is shown in table 17.

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Example 29

1-butene and a polymer were polymerized monomer containing polar group in the same way as in the example 26, except that anhydride was used (2,7-octadien-1-yl) succinic represented by the following formula instead of undecen-1-ol.

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The properties of the olefin copolymer that Contains the resulting polar group are shown in Table 16.

The adhesion resistance (a Al) of the olefin copolymer containing polar group by the method previously mentioned. The result is shown in table 17.

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TABLE 17

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Example 30

In a 300 glass polymerization reactor ml meticulously purged with nitrogen, 40 ml of 1-octene, then nitrogen was passed to its through at a rate of 20 l / h and the content was maintained at 60 ° C for 10 minutes. Then, 0.6 mmol of triisobutylaluminum, followed by the additional addition of 0.48 undemo-1-ol mmoles represented by the following formula.

149

Then, 1,100 mmol of methylaluminoxane and 40 ml of 1-octene. Finally I know added a toluene suspension solution in the that 0.002 mmol of dichloride had been contacted dimethylsilylene (2-methyl-4-phenanthryl-1-indenyl) zirconium  and 0.500 mmol of methylaluminoxane at room temperature for 10 minutes to start the polymerization. After the polymerization at 20 ° C for 60 minutes at atmospheric pressure, added a small amount of isobutyl alcohol to finish the polymerization. Then, 100 ml of a solution of isobutyl alcohol containing 1 ml of an aqueous solution of concentrated hydrochloric acid, followed by heating at 75 ° C in An atmosphere of nitrogen. The polymer solution was introduced obtained in a large excess of methanol to precipitate a polymer and then dried under vacuum at 80 ° C for 12 hours. As a result, 0.25 g of a polymer was obtained.

The properties of the olefin copolymer that Contains resulting polar group are set out in Table 18.

Coating properties were evaluated of the olefin copolymer containing polar group by the method mentioned above. The result is shown in the table 19.

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Example 31

1-octene and a polymer were polymerized monomer containing polar group in the same way as in the example 30, except because it was used 1,2-epoxy-9-decene represented by the following formula instead of undecen-1-ol.

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The properties of the olefin copolymer that Contains resulting polar group are set out in Table 18.

The olefin copolymer containing group polar underwent an impact resistance test and a tensile test by the methods mentioned above. The results are shown in table 19.

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Example 32

1-octene and a polymer were polymerized monomer containing polar group in the same way as in the Example 30, except that 1.35 mmol of acid were used undecylenic represented by the following formula instead of undecen-1-ol and 1.5 mmol were used of triisobutylaluminum.

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The properties of the olefin copolymer that Contains resulting polar group are set out in Table 18.

The olefin copolymer containing group polar underwent an impact resistance test and a tensile test by the methods mentioned above. The results are shown in table 19.

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Example 33

1-octene and a polymer were polymerized monomer containing polar group in the same way as in the example 30, except that anhydride was used (2,7-octadien-1-yl) succinic represented by the following formula instead of undecen-1-ol.

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The properties of the olefin copolymer that Contains resulting polar group are set out in Table 18.

The olefin copolymer containing group polar underwent an impact resistance test and a tensile test by the methods mentioned above. The results are shown in table 19.

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TABLE 19

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In the following examples 34 to 39, the sample preparation and property measurements mechanics were performed as follows.

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Sample Preparation

A graft copolymer obtained in the example using a 55 injection molding machine tons (IS55EPN manufactured by Toshiba Machine Co., Ltd.) to one cylinder temperature of 200 ° C and a mold temperature of 40 ° C

In the following examples 34 to 39, the Measurements of the flexural modulus, Rockwell hardness and hardness at pencil, and the calculation of (4) / (5) using 1 H-NMR They were performed as follows.

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Flex module

The flexural modulus was measured using a sample which was 1/8 inch thick under the conditions of a wingspan of 51 mm and a bending speed of 20 mm / min. according ASTM C790.

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Rockwell hardness (HR)

Rockwell hardness was measured using a plate 2 mm square (thickness) x 120 mm (length) x 130 mm (width) according to ASTM D785.

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Pencil hardness

Pencil hardness was measured using a sample which was 1/8 inch thick under the conditions of a temperature of 23ºC according to JIS K5401.

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Calculation of (4) / (5) by 1 H-NMR

Device: JOEL type nuclear magnetic resonance device GFX400

Core of observation: 1 H

Frequency observation: 400 MHz

Width pulse: 45º

Time of repetition: 5.0 seconds

Number of times Integration: 8000

Temperature of measurement: 115ºC

Solvent measurement: orthodichlorobenzene

Measurement: It dissolved the resulting polymer from 25 to 40 mg in orthodichlorobenzene and the NMR was measured under the measurement conditions previous.

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Example 34

In a glass polymerization reactor of 1000 ml meticulously purged with nitrogen, 400 ml were put of toluene, then nitrogen was passed through it to a 20 l / h rate, and the content was maintained at 90 ° C for 10 minutes Then, 2.0 mmol of triisobutylaluminum were added, followed by the additional addition of 1.88 mmol of undecen-1-ol (having dried on activated alumina and then vacuum distillate) represented by the following formula.

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Then, 1,100 mmol of methylaluminoxane and stopped the passage of nitrogen, followed by the ethylene passage at a speed of 5 l / h. Finally, a toluene solution-suspension in which had contacted 0.008 mmol of dichloride from dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di-tert-butylfluorenyl) zirconium  and 2.00 mmol of methylaluminoxane at room temperature for 10 minutes to start polymerization. After the polymerization at 90 ° C for 1 hour at atmospheric pressure, added a small amount of isobutyl alcohol to finish the polymerization. Then, 100 ml of a solution of isobutyl alcohol containing 1 ml of an aqueous solution of concentrated hydrochloric acid, followed by heating at 75 ° C in An atmosphere of nitrogen. The polymer solution was introduced obtained in a large excess of methanol to precipitate a polymer and then dried under vacuum at 80 ° C for 12 hours. As a result, 12.21 g of a polymer having a molar ratio of 99.2 / 0.8 ethylene / side chain monomer.

A 1500 ml autoclave equipped with a thermometry tube, a pressure gauge, a stirrer and a pipe feed alkylene oxide with 12.0 g of the copolymer of ethylene / side chain monomer (ethylene / chain monomer lateral = 99.2 / 0.8 mol), 31.0 mg of hydroxide tetrakis [tris (dimethylamino) -phosphoranylidenamino] phosphonium  ([(Me 2 N) 3 P = N] 4 P + OH -) synthesized in the same way as described in the document EP0791600, p. 32 and 800 g of tetralin. Then, the content up to 125 ° C and allowed to undergo a reaction to the same temperature for 12 hours with intermittent power 3.1 g of ethylene oxide so that the pressure was maintained at 0.9 MPa (absolute pressure). Subsequently, it was removed by distillation the ethylene oxide that had not reacted remaining in the autoclave at the same temperature under reduced pressure. Then, the content was cooled to room temperature and poured into 800 ml of methanol. The soft solid precipitate was separated by filtration, and additionally added to solid 20 ml of methanol, followed by heating under reflux for 30 minutes The mixture was subjected to hot filtration, and dried the resulting solid at 60 ° C under reduced pressure, obtaining 10.1 g of a graft copolymer in which they were polymerized by grafting approximately 13 units of ethylene oxide based on a hydroxyl group.

The properties of the olefin copolymer branched containing resulting polar group are exposed in the table 20.

In addition, the properties were evaluated anti-fogging of a film obtained from the copolymer of  branched olefin containing polar group by the method previously mentioned. The result is shown in table 21. The measurement of the ratio (4) / (5) of the polymer by 1 H-NMR resulted in 100/0.

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Example 35

In a glass polymerization reactor of 1000 ml meticulously purged with nitrogen, 400 ml were put of toluene, then nitrogen was passed through it to a 20 l / h rate and the content was maintained at 90 ° C for 10 minutes Then, 1.08 mmol of triisobutylaluminum were added, followed by the additional addition of 0.90 mmol of undecen-1-ol (having dried on activated alumina and then vacuum distillate). Also I know they added 1,100 mmol of methylaluminoxane and the passage of nitrogen, followed by the passage of ethylene at a speed of 100 l / h Finally, a suspension solution was added of toluene in which 0.008 mmol of dichloride dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di-tert-butylfluorenyl) zirconium  and 2.00 mmol of methylaluminoxane at room temperature for 10 minutes to start polymerization. After the polymerization at 90 ° C for 1 hour at atmospheric pressure, added a small amount of isobutyl alcohol to finish the polymerization. Then, 100 ml of a solution of isobutyl alcohol containing 1 ml of an aqueous solution of concentrated hydrochloric acid, followed by heating at 75 ° C in An atmosphere of nitrogen. The polymer solution was introduced obtained in a large excess of methanol to precipitate a polymer and then dried under vacuum at 80 ° C for 12 hours. As a result, 14.83 g of a polymer having a molar ratio of 99.75 / 0.25 ethylene / side chain monomer.

Then, polymerization of in the same manner as in example 34, except that 12.0 were used g of the polymer obtained above and 15.1 g of oxide was used ethylene. As a result, 11.8 g of a copolymer of graft in which approximately 65 were polymerized by grafting ethylene oxide units based on a hydroxyl group.

The properties of the olefin copolymer branched containing resulting polar group are exposed in the table 20.

In addition, the properties were evaluated anti-fogging of a film obtained from the copolymer of  branched olefin containing polar group by the method previously mentioned. The result is shown in the table twenty-one.

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Example 36

The procedure of example 34 was repeated, except that 5.0 g of propylene oxide was used instead of ethylene oxide. As a result, 10.3 g of a graft copolymer in which they were polymerized by grafting approximately 10 units of propylene oxide based on a hydroxyl group.

The properties of the olefin copolymer branched containing resulting polar group are exposed in the table 20.

In addition, the properties were evaluated anti-fogging of a film obtained from the copolymer of  branched olefin containing polar group by the method previously mentioned. The result is shown in table 21. The measurement of the ratio (4) / (5) of the polymer by 1 H-NMR resulted in 99/1.

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Example 37

Using the ethylene polymer / chain monomer lateral (ethylene / side chain monomer = 99.75 / 0.25 mol) prepared in example 35, polymerization was carried out with intermittent feeding of 3.1 g of ethylene oxide. How result, 11.8 g of a graft copolymer in the which were graft polymerized approximately 13 oxide units of ethylene based on a hydroxyl group.

The properties of the olefin copolymer branched containing resulting polar group are exposed in the table 20.

In addition, the properties were evaluated anti-fogging of a film obtained from the copolymer of  branched olefin containing polar group by the method previously mentioned. The result is shown in the table twenty-one.

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Example 38

The procedure of example 34 was repeated, except that additional 7.75 g of α-hydroxyisopropyl phenyl ketone in addition to Starting materials, the pressure was changed to 0.2 MPa from 0.9 MPa, 5.8 g of methyl methacrylate was used instead of ethylene and tetrahydrofuran was used instead of methanol. How result, 11.3 g of a graft copolymer in the that approximately 20 units of polymerization were grafted methyl methacrylate based on a hydroxyl group.

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The properties of the olefin copolymer branched containing resulting polar group are exposed in the table 20.

In addition, the mechanical properties were evaluated of the branched olefin copolymer containing polar group by the method mentioned above. The result is exposed in table 21.

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Example 39

In a 2 liter stainless steel autoclave (SUS) meticulously purged with nitrogen, 105 g of 1-octene, 895 ml of Mitsui hexane and 1.50 mmol of triisobutylaluminum. The SUS autoclave was heated to 150 ° C and 1,140 mmol of methylaluminoxane were added, followed by additional addition of 1,350 mmol of undecen-1-ol (having dried on activated alumina and then vacuum distillate). Keeping the temperature at 150 ° C, the autoclave was pressurized with ethylene so that the total pressure became 30 kg / cm2 -G. Separately, in a glass flask 20 ml meticulously purged with nitrogen, injected with nitrogen a solution-suspension of toluene in which had been contacted 0.00075 mmol of dichloride dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di-tert-butylfluorenyl) zirconium and 0.4300 mmol of methylaluminoxane at room temperature for 10 minutes, and 600 Nml of hydrogen were also injected. During the 10 minute period after injection, the temperature was maintained of the autoclave at 150 ° C and the pressure was maintained therein immediately after injection by pressurization with ethylene. Then, a small amount of isobutyl alcohol was added to finish the polymerization. The solution of polymer obtained in a large excess of methanol to precipitate a polymer and then dried under vacuum at 80 ° C for 12 hours. How result, 8.45 g of a polymer were obtained.

Using 8 g of this polymer, the polymerization with intermittent feeding of 3.1 g of oxide ethylene similar to example 34. As a result, obtained 11.8 g of a graft copolymer in which graft polymerized approximately 13 oxide units of ethylene based on a hydroxyl group.

The properties of the olefin copolymer branched containing resulting polar group are exposed in the table 20.

In addition, the dispersibility of the branched olefin copolymer containing polar group in water by the method mentioned above. The result is exposed in table 21.

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156

TABLE 21

157

Example 40

In a 500 glass polymerization reactor ml meticulously purged with nitrogen, 400 ml of toluene, then nitrogen was passed through it to a 20 l / h rate and the content was maintained at 75 ° C for 10 minutes Then, 0.8000 mmol of methylaluminoxane were added, followed by the additional addition of 0.1000 mmol of undecen-1-ol (having dried on silica-alumina and then vacuum distillate). Then, the nitrogen passage was stopped and ethylene was passed to its through at a speed of 100 l / h.

Finally, 0.0008 mmol of dichloride isopropylidene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium  to start the polymerization. After polymerization has been carried out at 75 ° C for 15 minutes at atmospheric pressure, a small amount of isobutyl alcohol to finish the polymerization. The polymer solution obtained was introduced into a large excess of methanol to precipitate a polymer and then it dried under vacuum at 80 ° C for 12 hours. As a result, they were obtained 0.90 g of a polymer. The polymerization activity was 4.5 kg / mmol \ zd \ cdoth, and the melting point of the polymer was 129.0 ° C.

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Example 41

In a 500 glass polymerization reactor ml meticulously purged with nitrogen, 400 ml of toluene, then nitrogen was passed through it to a 20 l / h rate and the content was maintained at 75 ° C for 10 minutes Then, 1,1000 mmol of methylaluminoxane were added, followed by the additional addition of 0.15 mmol of undecen-1-ol (having dried on silica-alumina and then vacuum distillate). Then, the nitrogen passage was stopped and ethylene was passed to its through at a speed of 100 l / h.

Finally, a solution-suspension of toluene in which they had put in contact 0.0160 mmol of dichloride diphenylmethylene (cyclopentadienyl) - (fluorenyl) zirconium and 1,1000 mmol of methylaluminoxane at room temperature for 10 minutes to start polymerization. After the polymerization at 75 ° C for 30 minutes at atmospheric pressure, added a small amount of isobutyl alcohol to finish the polymerization. The polymer solution obtained was introduced into a large excess of methanol to precipitate a polymer and then it dried under vacuum at 80 ° C for 12 hours. As a result, they were obtained 6.67 g of a polymer. The polymerization activity was 0.83 kg / mmol • Zoth •, and [η] of the polymer was 3.82 dl / g.

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Example 42

In a 500 glass polymerization reactor ml meticulously purged with nitrogen, 400 ml of toluene, then nitrogen was passed through it to a 20 l / h rate and the content was maintained at 75 ° C for 10 minutes Then, 1,1000 mmol of methylaluminoxane were added, followed by the additional addition of 0.20 mmol of undecen-1-ol (having dried on silica-alumina and then vacuum distillate). Then, the nitrogen passage was stopped and ethylene was passed to its through at a speed of 100 l / h. Finally, a solution-suspension of toluene in which they had put in contact 0.0160 mmol of dichloride (tert-butylamido) dimethyl- (tetramethylcyclopentadienyl) silanotitanium and 1,1000 mmol of methylaluminoxane at room temperature during 10 minutes to start the polymerization. After the polymerization at 75 ° C for 1 hour at atmospheric pressure, added a small amount of isobutyl alcohol to finish the polymerization. The polymer solution obtained was introduced into a large excess of methanol to precipitate a polymer and then it dried under vacuum at 80 ° C for 12 hours. As a result, they were obtained 2.54 g of a polymer. The polymerization activity was 0.03 kg / mmol-Zr-h, [η] of the polymer it was 3.55 dl / g, the melting point was 129 ° C and the polar group introduction ratio thereof, as measured by 1 H-NMR, it was 0.25 mol%.

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Example 43

In a 500 glass polymerization reactor ml meticulously purged with nitrogen, 400 ml of toluene, then nitrogen was passed through it to a 20 l / h rate and the content was maintained at 75 ° C for 10 minutes Then, 1.1400 mmol of methylaluminoxane were added, followed by the additional addition of 0.20 mmol of undecen-1-ol (having dried on silica-alumina and then vacuum distillate). Then, the nitrogen passage was stopped and ethylene was passed to its through at a speed of 100 l / h.

Finally, a solution-suspension of toluene in which they had contacted 0.0008 mmol of dichloride dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di-tert-butylfluorenyl) zirconium and 0.4300 mmol of methylaluminoxane at room temperature for 10 minutes to start the polymerization. After the polymerization at 75 ° C for 5 minutes at atmospheric pressure, added a small amount of isobutyl alcohol to finish the polymerization. The polymer solution obtained was introduced into a large excess of methanol to precipitate a polymer and then it dried under vacuum at 80 ° C for 12 hours. As a result, they were obtained 3.23 g of a polymer. The polymerization activity was 48.45 kg / mmol • Zoth •, and [η] of the polymer was 9.37 dl / g.

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Example 44

In a 500 glass polymerization reactor ml meticulously purged with nitrogen, 400 ml of toluene, then nitrogen was passed through it to a 20 l / h rate and the content was maintained at 75 ° C for 10 minutes Then, 1.1400 mmol of methylaluminoxane were added, followed by the additional addition of 0.30 mmol of undecen-1-ol (having dried on silica-alumina and then vacuum distillate). Then, the nitrogen passage was stopped and ethylene was passed to its through at a speed of 100 l / h.

Finally, a solution-suspension of toluene in which they had brought into contact 0.0016 mmol of dichloride dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di-tert-butylfluorenyl) zirconium and 0.4300 mmol of methylaluminoxane at room temperature for 10 minutes to start the polymerization. After the polymerization at 75 ° C for 5 minutes at atmospheric pressure, added a small amount of isobutyl alcohol to finish the polymerization. The polymer solution obtained was introduced into a large excess of methanol to precipitate a polymer and then it dried under vacuum at 80 ° C for 12 hours. As a result, they were obtained 2.46 g of a polymer. The polymerization activity was 18.45 kg / mmol • Zoth, and [η] of the polymer was 7.89 dl / g.

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Example 45

In a 500 glass polymerization reactor ml meticulously purged with nitrogen, 400 ml of toluene, then nitrogen was passed through it to a 20 l / h rate and the content was maintained at 75 ° C for 10 minutes Then, a solution of 0.480 toluene was added triethylaluminum mmoles and 0.480 mmoles of undecen-1-ol (having dried on silica-alumina and then vacuum distillate) which had been pretreated at room temperature for 10 minutes, followed by the additional addition of 1.1400 mmol of methylaluminoxane. Then, the passage of nitrogen was stopped and made pass ethylene through it at a speed of 100 l / h.

Finally, a solution-suspension of toluene in which they had contacted 0.0020 mmol of dichloride dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di-tert-butylfluorenyl) zirconium and 0.4300 mmol of methylaluminoxane at room temperature for 10 minutes to start the polymerization. After the polymerization at 75 ° C for 2 minutes at atmospheric pressure, added a small amount of isobutyl alcohol to finish the polymerization. The polymer solution obtained was introduced into a large excess of methanol to precipitate a polymer and then it dried under vacuum at 80 ° C for 12 hours. As a result, they were obtained 3.63 g of a polymer. The polymerization activity was 36.3 kg / mmol • Zoth, and [η] of the polymer was 4.97 dl / g.

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Example 46

In a 500 glass polymerization reactor ml meticulously purged with nitrogen, 400 ml of toluene, then nitrogen was passed through it to a 20 l / h rate and the content was maintained at 75 ° C for 10 minutes Then, 0.480 mmol of triisobutylaluminum was added, followed by the additional addition 0.48 mmol of undecen-1-ol (having dried on silica-alumina and then vacuum distillate). After stirring for 3 minutes, 1.1400 mmol of methylaluminoxane, then the passage of nitrogen was stopped and made pass ethylene through it at a speed of 100 l / h.

Finally, a solution-suspension of toluene in which they had contacted 0.0017 mmol of dichloride dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di-tert-butylfluorenyl) zirconium and 0.4300 mmol of methylaluminoxane at room temperature for 10 minutes to start the polymerization. After the polymerization at 75 ° C for 2.5 minutes at atmospheric pressure, added a small amount of isobutyl alcohol to finish the polymerization. The polymer solution obtained was introduced into a large excess of methanol to precipitate a polymer and then it dried under vacuum at 80 ° C for 12 hours. As a result, they were obtained 3.00 g of a polymer. The polymerization activity was 42.3 kg / mmol \ zd \ cdoth.

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Example 47

In a 500 glass polymerization reactor ml meticulously purged with nitrogen, 400 ml of toluene, then nitrogen was passed through it to a 20 l / h rate and the content was maintained at 75 ° C for 10 minutes Then, 0.750 mmol of triisobutylaluminum were added, followed by the additional addition of 0.48 mmol of undecen-1-aldehyde (having dried on silica-alumina and then distilled to empty). After stirring for 3 minutes, 1.1400 mmol of methylaluminoxane, then the passage of nitrogen was stopped and made pass ethylene through it at a speed of 100 l / h.

Finally, a solution-suspension of toluene in which they had contacted 0.0017 mmol of dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di-tert-butylfluorenyl) zirconium and 0.4300 mmol of methylaluminoxane at room temperature for 10 minutes to start the polymerization. After the polymerization at 75 ° C for 2.5 minutes at atmospheric pressure, added a small amount of isobutyl alcohol to finish the polymerization. The polymer solution obtained was introduced into a large excess of methanol to precipitate a polymer and then it dried under vacuum at 80 ° C for 12 hours. As a result, they were obtained 4.50 g of a polymer. The polymerization activity was 63.5 kg / mmol \ zd \ cdoth.

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Example 48

In a 500 glass polymerization reactor ml meticulously purged with nitrogen, 400 ml of toluene, then nitrogen was passed through it to a 20 l / h rate and the content was maintained at 75 ° C for 10 minutes Then, 0.480 mmol of triisobutylaluminum was added, followed by the additional addition of 0.48 mmol of decen-1-amine (having dried on silica-alumina and then vacuum distillate). After stirring for 3 minutes, 1.1400 mmol of methylaluminoxane, then the passage of nitrogen was stopped and made pass ethylene through it at a speed of 100 l / h.

Finally, a solution-suspension of toluene in which they had contacted 0.0017 mmol of dichloride dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di-tert-butylfluorenyl) zirconium and 0.4300 mmol of methylaluminoxane at room temperature for 10 minutes to start the polymerization. After the polymerization at 75 ° C for 2.5 minutes at atmospheric pressure, added a small amount of isobutyl alcohol to finish the polymerization. The polymer solution obtained was introduced into a large excess of methanol to precipitate a polymer and then it dried under vacuum at 80 ° C for 12 hours. As a result, they were obtained 0.80 g of a polymer. The polymerization activity was 11.3 kg / mmol \ zd \ cdoth.

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Examples 49, 50, 51, 52, 53, 54, 55, 56, 57 and 58

Olefin copolymers were prepared which contain polar group under the same conditions as in the example 40, except that the types and quantities of the α-olefin and the group containing monomer polar, the type and amount of the trialkylaluminum compound and the polymerization temperature and the polymerization time are changed as shown in table 22. The results are set out in table 22.

158

Comparative example 3

In a 500 glass polymerization reactor ml meticulously purged with nitrogen, 400 ml of toluene, then nitrogen was passed through it to a 20 l / h rate and the content was maintained at 75 ° C for 10 minutes Then, 0.480 mmol of sesquichloride of ethylaluminum, followed by the additional addition of 0.48 mmol of decen-1-amine (having dried on silica-alumina and then vacuum distillate). After stirring for 3 minutes, 1.1400 mmol of ethylaluminum sesquichloride, then the passage of nitrogen and ethylene was passed through it at a speed of 100 l / h

Finally, a solution-suspension of toluene in which they had contacted 20,0017 mmol of VO (OC 2 H 5) Cl and 0.4300 mmol of sesquichloride of ethyl aluminum at room temperature for 10 minutes to Start the polymerization. After polymerization at 75 ° C for 2.5 minutes at atmospheric pressure, a small was added amount of isobutyl alcohol to complete the polymerization. Be introduced the polymer solution obtained in a large excess of methanol to attempt the precipitation of a polymer, however, no polymer was obtained.

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Example 59

In a 2 liter stainless steel autoclave (SUS) meticulously purged with nitrogen, 120 g of 1-butene, 880 ml of Mitsui hexane and 1.50 mmol of triisobutylaluminum. The SUS autoclave was heated to 150 ° C and 1,140 mmol of methylaluminoxane were added, followed by additional addition of 1,350 mmol of undecen-1-ol (having dried on activated alumina and then vacuum distillate) represented by the following formula. Maintaining the temperature at 150 ° C, the autoclave was pressurized with ethylene so that the total pressure it became 2.9 MPa-G (30 kg / cm2 -G).

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159

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Separately, in a 20 ml glass flask meticulously purged with nitrogen, a nitrogen was injected with solution-suspension of toluene in which they had contacted 0.00075 mmol of dichloride dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di-tert-butylfluorenyl) zirconium and 0.4300 mmol of methylaluminoxane at room temperature for 10 minutes, and 600 Nml of hydrogen were also injected. During the 10 minute period after injection, the temperature was maintained of the autoclave at 150 ° C and the pressure was maintained therein immediately after injection by pressurization with ethylene. Then, a small amount of isobutyl alcohol was added to finish the polymerization. The solution of polymer obtained in a large excess of methanol to precipitate a polymer and then dried under vacuum at 80 ° C for 12 hours. How result, 10.40 g of a polymer were obtained. The activity of polymerization was 83 kg / mmol \ cdotZr \ cdoth.

The properties of the olefin copolymer that Contains the resulting polar group are shown in Table 23.

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Example 60

Ethylene was polymerized, 1-butene and a monomer containing polar group of in the same manner as in example 59, except that acid was used undecylenic represented by the following formula instead of undecen-1-ol.

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160

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The properties of the olefin copolymer that Contains the resulting polar group are shown in Table 23.

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Example 61

Ethylene was polymerized, 1-butene and a monomer containing polar group of the same way as in example 59, except because it was used 1,2-epoxy-9-decene represented by the following formula instead of undecen-1-ol and 550 Nml of hydrogen.

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161

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The properties of the olefin copolymer that Contains the resulting polar group are shown in Table 23.

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Example 62

Ethylene was polymerized, 1-butene and a monomer containing polar group of the same way as in example 59, except because it was used anhydride (2,7-octadien-1-yl) succinic represented by the following formula instead of undecen-1-ol and 550 Nml of hydrogen.

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162

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The properties of the olefin copolymer that Contains the resulting polar group are shown in Table 23.

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Example 63

Ethylene, propylene and a polymer were polymerized monomer containing polar group in the same way as in the Example 62, except that propylene was injected at a pressure initial partial of 3 kg / cm2 instead of 1-butene, hydrogen was not added and the polymerization was performed at a polymerization temperature of 80 ° C

The properties of the olefin copolymer that Contains the resulting polar group are shown in Table 23.

163

Claims (16)

1. Olefin copolymer containing group branched-type polar comprising a constitutive unit represented by the following formula (1) and a unit constitutive represented by the following formula (4), and optionally a constitutive unit represented by the following formula (5), which has a molecular weight distribution (Mw / Mn) not exceeding 3, and having an intensity ratio of T?? With respect to T?? (Tαβ / Tαα), as determined from of a 13 C-NMR spectrum of said copolymer, not more than 1.0: 164 in which R1 is an atom of hydrogen or a straight chain aliphatic hydrocarbon group or branched from 1 to 18 carbon atoms; R 5 is a group hydrocarbon; R 6 is a heteroatom or group containing a heteroatom; r is 0 or 1; Z is a polymeric segment obtained by any one of anionic polymerization, polymerization by ring opening and polycondensation; W is a hydroxyl group or an epoxy group; p is an integer from 1 to 3, q is 0, 1 or 2, and p + q ≤ 3; when p is 2 or 3, each -O-Z can be same or different, and in this case, if r is 0, -O-Z it can be attached to the same atom or to an atom different from R 5, and if r is 1, -O-Z can be attached to the same atom or to an atom other than R 6; when q is 2, each W can be same or different, and in this case, if r is 0, W can be attached to the same atom or an atom different from R 5, and if r is 1, W can be bound to the same atom or to an atom different from R 6; at case of p \ geq1 and q \ geq1, if r is 0, W and -O-Z they can be attached to the same atom or to an atom different from R 5, and if r is 1, W and -O-Z can be attached to the same atom or to an atom different from R 6; m is 0 or 1; n is an integer from 1 to 3; and when n is 2 or 3, each W can be same or different, and in this case, if m is 0, W can be attached to the same atom or to an atom different from R 5, and if m is 1, W it can be attached to the same atom or to an atom different from R 6. 2. Olefin copolymer containing group branched-type polar according to claim 1, wherein, in formula (4), r is 0 and Z is a polymeric segment obtained by anionic polymerization. 3. Olefin copolymer containing group branched-type polar according to claim 1, wherein, in Formula (4), Z is a polymeric segment obtained by ring opening or polycondensation polymerization. 4. Thermoplastic resin composition that contains the olefin copolymer containing polar group according to a  any of claims 1 to 3. 5. Adhesive resin comprising the copolymer of olefin containing polar group according to any one of the claims 1 to 3. 6. Compatibilizing agent comprising the olefin copolymer containing polar group according to any one of claims 1 to 3. 7. Resin modifier comprising the olefin copolymer containing polar group according to any one of claims 1 to 3. 8. Load dispersing agent comprising the olefin copolymer containing polar group according to any one of claims 1 to 3. 9. Dispersion comprising the copolymer of olefin containing polar group according to any one of the claims 1 to 3. 10. Film or sheet comprising the olefin copolymer containing polar group according to any one of claims 1 to 3. 11. Adhesive resin comprising the composition of thermoplastic resin according to claim 4. 12. Compatibilizing agent comprising the thermoplastic resin composition according to claim 4. 13. Resin modifier comprising the thermoplastic resin composition according to claim 4. 14. Load dispersing agent comprising the thermoplastic resin composition according to claim 4. 15. Dispersion comprising the composition of thermoplastic resin according to claim 4. 16. Film or sheet comprising the thermoplastic resin composition according to claim 4.