Polymers with long chain branching and receive

 

(57) Abstract:

The invention relates to thermoplastic polyolefins, with the ability to recycle and to methods for their preparation. Get a copolymer of monoolefins with only the polymerized by Ziegler-Natta connection, the second monomer with at least one polymerized by Ziegler-Natta communication and the third monomer with at least two polymerized by Zingaro-Natta links. The copolymer is characterized by the presence of at least one carbon-carbon links on srednekamennogo molecule, the activation energy of viscous flow for at least 1 kcal/mol higher than that of a copolymer containing a linear main chain, and derived from the same monomers, but not having at least two polymerized by Ziegler-Natta communication. The degree of crystallinity is 10-50%, and a value of MZ/MWat least the 1.7. The monomers are contacted with a catalyst of the Ziegler-Natta, its derivatives or their combinations under pressure of over 100 bar and at more than 60oC. Allocate the resulting copolymer. Also receive a copolymer of ethylene with polirom containing at least two polymerized by Ziegler-Natta double bond with at least 120oC using the technical result consists in the improved ability to processing in the melt in the specified range of crystallinity and adjustable degree of razvetvleniya copolymer. 3 S. and 14 C.p. f-crystals, 4 tab., 5 Il.

The technical field to which the invention relates

The invention relates to thermoplastic polymers, including polyolefins, characterized by an enhanced ability to process and variable degree of branching, as well as to methods for their preparation. These polymers are obtained from at least three monomers: one of the monomers is monoolefins, modernmami only the polymerized by Ziegler-Natta communication; the second monomer contains one or more of the polymerized by Ziegler - Natta relations, and the third monomer contains at least two polymerized by Ziegler-Natta communication, and these include remotemachine olefins, including at least six or at least seven carbon atoms, or cyclic olefins.

Background of the invention

Polyolefins are a versatile material that usually can be easily recycled and can be used in a variety of areas. However, despite the fact that, although polyolefins and characthe. Such undesirable characteristics include a high content of low molecular weight products, contributing to the formation of soot in the process of manufacturing products, high content of extractable materials and the possibility of leaching of such low molecular weight fractions of the molded polymer product or packaging. For many years was based polymers, different from the traditional low density polyethylene (LDPE), including such materials as linear low density polyethylene (LLDPE) and high density polyethylene (HDPE). Despite some improvement in the properties of these polymers, they are characterized by some of their own drawbacks, including difficulties in the processing, the tendency to the destruction of the extrusion flow and low melt strength.

The emergence of catalysis with a single plot (KEU), in particular metallocene catalysis type, made it possible to get an entirely new polymers with significantly narrowed molecular weight distribution (MMD) or polydispersity. This means that with the advent of the polymers produced using these catalysts, in fact, eliminated some of the problems associated with the presence of products with very viskoznosti of such materials in many applications. One of the methods which can improve the ability to process in the melt, consists in the introduction of the long side chains. According to the present invention, it was found that regulated the introduction of long side chains (different from the short side chains, which are formed in the copolymerization of olefin comonomers) in almost linear main molecular chain leads to noticeable changes in key rheological parameters, leading to improved ability during processing in the melt. According to the invention for this purpose, we developed a method, according to which there is a possibility to adjust the crystallinity of the polymer as a whole and trends during crystallization and simultaneous creation of additional points available residual unsaturated groups. They can remain in the polymer resin, to be recovered by hydrogenation, functionalized or used postformation curing of obtaining product on behavior in many ways reminiscent of thermosetting polymer, but has certain advantages in the processing, which is typical for traditional thermoplastic polyolefin.

Of engineering, ungu molecular chain changes the crystallinity and, therefore, the density of the material due to the reaction exerted on the ability of the polymer molecules to "packaging". Although such "short side chains" is effective in the destruction of the crystal structure, resulting in reduced density, they usually have little influence on the rheology of polymer melts. In this description are based on the technical problem to be solved by the present invention is directed, presents the changes in the structure of polymer molecules, which are reologicheskie significant. This description mainly covers the long side chains or branches from the main polymer molecular chains that are longer branches formed by copolymerization using easily obtainable available on the market olefinic monomers. The presence of such reologicheskie significant side groups usually affects the behavior of the polymer melt that is to increase the strength of the polymer melt, the weakening trend to the destruction of the extrusion flow and the increase of the activation energy Eandviscous condition or expiration. These rheological properties of the molten polymer is usually easy to quantify, which allows to distinguish what the R side chains of polymer molecules (for example, spectroscopic method) due to the inherent to this method disadvantages applicable only to a very limited extent.

Such long side chains usually improve the ability of polymer melt processing. This effect is particularly pronounced in polymers, characterized by a narrow MMD, including polymers that are obtained by catalysis with a single site, especially metallocene catalysis. These polymers with long side chains, usually characterized by improved properties melt flow for many applications (for example, those in which the benefit is higher melt strength) than similar polymers without long lateral chains.

The technical solutions described in the following publications, also belong to the above problem, however none of these solutions is not possible to achieve the same result and get the same unique combination of properties, and the present invention. However, in this direction, as follows from the following publications have already done a lot of work.

German patent 3240382 (firm Hoechst) refers to the use of small amounts of diolefins,lichnosti.

In European application-35242 (BASF) describes the copolymerization of ethylene with alpha, omega (,)- diolefine with obtaining custom made products.

In the European applications 273654, 273655 and 275676 (Exxon company) described the copolymerization of dienes. On page 9, lines 33-37 European application 275676 described the nature of the introduction.

In U.S. patent 3984610, issued in the name Elston, described a semi-crystalline polymers of ethylene and dienes or cyclic endometriotic dienes containing at least one norbornene ring. It is obvious that the polymer contains a long side chains obtained by the polymerization of a second unsaturated diene group. This description refers to polymers with a low residual content of unsaturated groups. On page 3, line 33, specify a limit that is less than one carbon-carbon double bonds per 1000 carbon atoms. In fact, the information contained in columns 7 and 8 indicates, apparently, that the greatest degree of unsaturation corresponds to a content of 0.7 carbon-carbon double bonds per 1000 carbon atoms, where thus, it is obvious that the purpose of this work was to provide really low content of residual unsaturated its high content of residual unsaturated groups, as illustrated in the examples. A higher content of residual unsaturated groups creates more opportunities for functionalization or postforming curing of the moulded/extruded products, thus providing a new balance between the ability to process in the melt and the target properties.

In U.S. patent 4404344 (European application 035242), issued in the name Sinn described the copolymerization of ethylene and alpha-olefins or dienes. Descriptions for these patents do not relate to the consideration of the advantages copolymerization of several monoolefins with polyene.

In U.S. patent 4668834 (European application 223394), issued in the name of the Rim, and others described low molecular weight copolymers of ethylene and alpha-olefin containing from three to twelve carbon atoms. This polymer is characterized by the presence vinylidene (end) unsaturated groups. These liquid polymers can be used in the curable compositions for electrical insulation and hermeticity.

In the work of Kaminsky and Drogemuller "Terpolymers of Ethylene, Propene and 1,5-Hexadiene synthesized unit with Zirconocene/Methyl-alumoxane", published in the journal Macromolecular Chemistry. Rapid Communications 11, 89-94 (1990) described ternary copolymerization 1,5-hexadiene with other ol is any information, related to the fact that it was found according to the present invention, namely a high propensity 1,5-hexadiene to cyclization with the formation of 5-membered ring structure cyclopentane type following the introduction of the chain in the 1,2-position. This property is caused, in General, inappropriate choice of 1.5-hexadiene to initiate branching with long lateral chains and bulky cyclic structure impede the achievement of the flexible circuit and the ability to crystallize. Diene residues, which are shorter or longer than 1.5-hexadiene, less prone to cyclization and, therefore, their use is more appropriate, as described below in the examples.

In U.S. patent 5229478 (European application 0347129), issued in the name Hoel, describes a method for elastomers of ethylene, propylene and diene with at least one internal double bond. In this way it is easy to obtain a rubber having a good ability to process, and such material after molding can vulcanizates due to the cross linking internal double bonds. In this patent does not deal with diene with two available for polymerization by Ziegler-Natta double bonds, or the benefits of using the ethylene-propylene-norbornadiene terpolymer.

In the patent Canada 946997 described Quaternary copolymer of ethylene, propylene, 1,4-hexadiene and 1.7-octadiene.

In the Japan patent B-70727/1991 described terpolymer ethylene, propylene and 1.7-octadiene obtained by using as a catalyst MgCl2/TiCl4-Al(ISO-C4H9)3. Other descriptions include Quaternary polymers obtained from ethylene, propylene, 5-ethylidene-2-norbornene and 1.7-octadiene or 1.9-decadiene.

The introduction of comonomers with ethylene is known and used in practice for many years. In Yano and others in European application 0446013 described polyethylene, which contains many evenly placed methyl side groups or copolymerization with propylene, side groups which are located along the main polymer chain, and the way to obtain this polyethylene. However, this apparently does not provide any improvement of rheological properties.

Lai and others in the U.S. patents 5272236 and 5278272 (international application 93/08221) offer a way branching with long lateral chains. In these publications described a system in which support low monomer concentration and a high concentration of polymer, contributing to the fork, the cat is nymi side chains perform spectroscopic analysis, and, as indicated in this patent, a fork with long side chains does not depend on the molecular mass distribution. While there is no indication that the resulting polymers are characterized by improved residual unsaturated groups.

Summary of the invention

Polymerization of materials that have more than one polymerized by Ziegler-Natta communication, in particular diolefins primarily cyclic dienes or dienes with linear main molecular chain, together with other appropriate monomers, in particular with alpha-olefins, provides an effective method of controlled type long side groups in the main polymer chain. One of the polymerized by Ziegler-Natta relations enter into the growing polymer chain during polymerization. Other polymerized by Ziegler-Natta connection remains available for subsequent input to another growing polymer chain with the formation of the long side of the group. According to the present invention proposes a method of producing such polymers.

The use of materials containing at least one polymerized by Ziegler-Natta communication, in particular monoalkanolamines polymer in General and the tendency to crystallization separately from type long side groups. This allows to obtain products with improved ability to process in the melt over the entire range of crystallinity. For example, the possible range of crystallinity of the polymer and the ethylene-based ranges from slightly less than 10% to over 50%.

The advantage of the present invention is the ability of polymeric material, characterized by measurable and adjustable residual unsaturated groups. The practical implementation of the present invention allows to obtain polymers which, in the preferred embodiment contain at least one unsaturated carbon-carbon links per 1000 carbon atoms. The presence of such bonds creates a number of advantages, which can be used by the end user. This unsaturated bond can be left as is or used, for example, in the reaction functionalization, in which you can enter additional target chemical residues, or used to create cross-links in the finished product to get the product to the end properties of thermosetting resin type, but is capable of processing in the melt by the standard technology for thermoplastic resins to polyolef determine whether long side groups according to the schedule of dependence of the activation energy Eandviscous condition or expiration of content-olefin comonomer links.

In Fig. 2 mapped values of the molecular mass distribution of polymers obtained without the use of materials containing at least two polymerized by Ziegler-Natta connection (product No. 1, the control experiment), and polymers produced using such materials (product # 4). Molecular mass distribution, which is mentioned in this description, is a value obtained by gel chromatography (GPC). According to the observations of the polymers according to the present invention, obtained with the use of such materials are high molecular weight strip, directly caused by the presence of materials containing long side chains.

In Fig. 3 presents a plot of shear rate, measured in terms of inverse seconds (c-1at the start of the gap extrusion flow from srednevekovoi molecular weight (Mw) for polymers of the present invention and for a typical linear ethylene - -olefin polymers. These starting point for various molecular masses determined as the point marked change of slope on graymere. This technique has found wide application in the determination of the beginning of gap extrusion flow. At the same molecular weight Mw higher initial shear rate reflects improved characteristics of gap extrusion flow. Data were obtained from measurements in a capillary viscometer at 125oC.

In Fig. 4 illustrates a method of data evaluation the beginning of gap extrusion flow graphs of the dependence of shear stresses (PA), defined by measurements in a capillary viscometer, shear rate (c-1in the melt for a number of ethylene- -olefin polymers obtained without (control) and using the polymers of the present invention) materials containing at least two polymerized by Ziegler-Natta communication. These charts clearly noticeable change of slope, and very clearly you can define the start point of the gap extrusion flow mentioned in the description of Fig. 3. It should be noted that for a product number 1 (control experiment) start gap extrusion flow is 407 c-1while product N 4 the beginning of the extrusion gap flow is 867 c-1.

In Fig. 5 presents a plot of Kootenai mass Mw of the polymer of the present invention and a typical linear ethylene - -olefinic polymers. Line in Fig. 5 reflects the characteristics of the standard of polymers of ethylene- -olefin basis, obtained by catalysis with a single plot (polymers EXACT, manufactured by Exxon Chemical Company, Houston, pc. Texas). The ratio of the viscosity/shear rate received capillary viscosimetry. This ratio is a measure of the sensitivity to shear, and for any given values of Mw higher value of this ratio corresponds to a higher capacity for shear-thinning (i.e., improved behavior for many applications). In other words, with increasing shear stress, the polymers of the present invention become more fluid.

Detailed description of the invention

The polymers of the present invention are copolymers of three or more materials containing polymerized by Ziegler-Natta connection, preferably olefins. The polymerization can be conducted using the catalysts of the Ziegler-Natta, in particular catalysts with a single plot (KEU), preferably metallocene catalysts of the type. Metallocene give the product certain advantages, such as narrow the soap is measuring the main molecular chain, as well as simplifying overall, the inclusion of co monomer. Methods of obtaining such polymers comprise another object of the present invention.

According to one variant of the invention, the polymers can be described as copolymers derived from the following monomers:

a) at least one monomer containing a single polymerized by Ziegler-Natta communication,

b) a second monomer containing at least one polymerized by Ziegler-Natta communication, and

C) a third monomer containing at least two polymerized by Ziegler-Natta communication, and this monomer is:

I) premazepam with less than six or at least seven carbon atoms or

II) non-remotemachine, or

III) their combination, while preferably, this copolymer is characterized by:

g) the presence of at least approximately one carbon-carbon unsaturated communication srednekamennogo molecule,

d) activation energy (Eand) viscous expiration of at least 1 kcal/mol higher than that of a copolymer containing linear main molecular chain and derived from the same monomers, but does not include materials containing at least two znachenie Mz/Mw of at least about 1.7 molecular mass distribution by type Flory, achieved, generally, by using a catalyst with a single site, for example, metallocene-based, the value of Mz/Mw of approximately 1,5),

C) the value of Mw/Mn of at least approximately 2.2 (molecular mass distribution by type Flory achieved, generally, by using a catalyst with a single site, for example, metallocene-based, the value of Mw/Mn is approximately 2.0).

From another point of view is proposed according to the invention polymers can be described as copolymers derived from monomers including:

a) at least one monomer containing a single polymerized by Ziegler-Natta communication,

b) a second monomer containing at least one polymerized by Ziegler-Natta communication, and

C) a third monomer containing at least two polymerized by Ziegler-Natta communication, and this monomer is:

I) premazepam with less than six or at least seven carbon atoms or

II) non-remotemachine, this copolymer is characterized by:

g) the value of Mz/Mw of at least about 1.7 molecular mass distribution by type Flory achieved, giving Mz/Mw is approximately 1.5),

d) the presence of more than one unsaturated carbon-carbon links on srednekamennogo molecule,

e) activation energy (Eand) viscous expiration of more than 1 kcal/mol higher than that of a copolymer containing linear main molecular chain and derived from the same monomers, but does not include materials containing at least two polymerized by Ziegler-Natta communication, and

f) degree of crystallinity of from 10 to 40%.

An important feature of the present invention is also getting these copolymers. You can use different ways to obtain a polymer, most of which can be thought of as a way of copolymerization:

a) at least one monomer containing a single polymerized by Ziegler-Natta communication,

b) a second monomer containing at least one polymerized by Ziegler-Natta communication, and

C) a third monomer containing at least two polymerized by Ziegler-Natta communication, and this monomer is:

I) premazepam with less than six or at least seven carbon atoms or

II) non-remotemachine, and this method includes the following stages:

g) introduction temperature and pressure, sufficient for polymerization, and

d) isolation of the copolymer.

One such method, which is particularly suitable for use, include the implementation stage contact under pressure greater than about 100 bar, preferably in excess of 500 bar and at a temperature of more than approximately 60oC, more preferably about 100oC. This process can be performed at high-pressure equipment, including autoclaves and tubular reactors.

Another such method involves the polymerization of ethylene and polyene containing at least two polymerized by Ziegler double bond at a temperature of at least 120oC using a catalyst derived from a transition metal compounds containing a bulky ancillary ligand. This method can be used to obtain, for example, ethylene copolymer, the ratio of melt indexes (SIR) which is at least 25, and the activation energy is equal to at least 9.0 kcal/mol.

From this description for any expert in the art of the obvious various modifications of each of the above objects. This is before the ptx2">

The main component (in the above description of at least one monomer") polymers of the present invention, generally, is ethylene. Its share is normally about 75 to 98 mol.%, more preferably 78-96 mol.% and most preferably 80-93 mol.% the polymer.

As the second monomer can be any monomer containing at least one polymerized by Ziegler-Natta communication. Typically, it represents an easily accessible monoolefins, such as propylene, butene-1, penten-1, hexene-1, hepten-1, octene-1, nonen-1, mission 1, undecene-1, dodecene-1, hexadecene-1, octadecene-1 and 4-methylpentene-1. Although, if you take into account their availability, preferred simple linear olefins, but can also be used many other products as the material of the main building blocks of such polymers. These usually include the corresponding cyclic and substituted olefins, including those that may contain many unsaturated (internal) groups. The content of groups of the second monomer, typically approximately 2 to 25 mol.%, more preferably from 4 to 22 mol.% and most preferably 7-20 mol.% the polymer. Specialists in this is to regulirovanie crystallinity, the density and other properties of this polymer.

According to the present invention to the materials containing at least two polymerized by Ziegler-Natta communications are those that represent remotemachine materials, containing less than six or at least seven carbon atoms, and cyclic and branched materials. Their detailed description is given below.

Materials containing at least two polymerized by Ziegler-Natta communication

Such materials can be cyclic or acyclic, including, obviously, the materials that are remotemachine and branched. In the case of cyclic materials to "the polymerized by Ziegler-Natta relations" are:

I) internal bonds between the two secondary carbon atoms (called carbon atoms linked to two other carbon atoms),

II) unsaturated end groups derived from C1-C20- hydrocarbonrich of substituents in the cyclic group, and

III) combinations thereof.

In these cases, the primary cyclic group may be fully saturated (type II), partially saturated (type I or type III) or aromatizer-Natta links are:

- containing unsaturated groups such as (I):

< / BR>
norbornadiene

- containing unsaturated groups of types (I) and (II):

< / BR>
vinylnorbornene

- containing unsaturated groups type II)

< / BR>
1,2,4-trivinylcyclohexane

Acyclic materials can include linear or branched C1-C20- gidrolabilna residues containing unsubstituted - and - group, where the carbon - atoms (penultimate) are secondary.

Examples of acyclic materials with at least two polymerized by Ziegler-Natta links are:

- linear: 1,7-octadien

< / BR>
- extensive: 3-methyl-1,4-pentadien

< / BR>
Usually the "materials containing at least two polymerized by Ziegler-Natta communication" includes teeny. However, in many cases those teeny, which are paired and mated dieny, except 1,3-butadiene, are not preferred.

As materials containing at least two polymerized by Ziegler-Natta communication", the preferred polyene. In this case, the polyene include Monomeric material containing at least two double bonds available for catalysis in C is a 6-heptadien, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadien, 1,11 - dodecadien. To an acceptable cyclic dianam can be attributed to various alkylated variants, isomers and combinations thereof, such as cyclohexadiene, cyclooctadiene, cyclodextrin, vinylcyclohexane, trivinylcyclohexane, hexahydrotriazine, polyvinylether, diphenyltrichloroethane, Dicyclopentadiene, etc. are Most suitable cyclic materials include compounds with the structure of the norbornene type, in particular norbornadiene and vinylnorbornene.

The use of linear materials with six carbon atoms less suitable for practical implementation of the present invention, it is preferable to exclude them, because in the implementation of the present invention they give the products some undesirable characteristics. In Kaminsky and Drogmuller described the use of 1,5-hexadiene in the polymerization of ethylene and propylene. The results they obtained, by which a conclusion was made about the presence of long side chains, consistent with the results obtained according to the present invention. In addition to branching with long side chains further analysis obtained according to the invention the product shows significant is ricotta these cyclic structures reduces the flexibility of the chain increases Tcthe glass transition temperature) and the ability to crystallization. Remotemachine diolefin with six carbon atoms provides, apparently, the greatest probability of being included in the main polymer chain in the form of cicletanine fragments. The presence of less than six or at least seven carbon atoms provides a good inclusion remotemachine dienes, the target residual unsaturated groups and a minimum cyclization of diene (or other material containing at least two polymerized by Ziegler-Natta communication) in the polymerization process. So, for example, 1,4-pentadien (less than six carbon atoms) and 1.9-decadien (more than six carbon atoms) well polymerize without significant cyclization observed in the case of 1,5-hexadiene.

Preferred polymers of the present invention are usually obtained from ethylene and at least one monomer selected from the group consisting of butene-1, hexene-1, octene-1, mission-1, dodecene-1, octadecene-1 and 4-methylpentene-1, and at least one material containing at least two polymerized by Ziegler communication and selected from the group consisting of 1,4-pentadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-deck of cyclodecane.

The molecular weight of the polymers of the present invention is compatible with the requirements of the processing in the melt when the target application (typically, during processing by injection molding or extrusion). The molecular weight of the preferred polymers processed in the melt using conventional techniques of manufacturing products made of thermoplastics (Mw according to GPC) is from 20000 to 120000.

The polymers of the present invention are semi-crystalline, and to quantify the degree of crystallinity can be applied a method based on x-ray diffraction. The x-ray diffraction is one of the fundamental methods of measuring the crystallinity of the polymers. This method allows to determine the relative amounts of crystalline and amorphous fractions in the polymer by separating the contribution of these two structural components in x-rays (see L. E. Alexander, X-ray Diffraction Methods in Polymer Science. 1969, Wiley/Interscience, New York). Fluoroscopic values of crystallinity of the polymer of the present invention comprise from about 10 to about 50%. The preferred degree of crystallinity is from about 10 to about 40%. For polymers on the ethyl is UP>. The crystalline nature of the polymer of the present invention determines the tensile strength, impact strength (impact strength) and durability. As a consequence, the polymers of the present invention can be used in areas where the preferred "pure" polymers (i.e., without significant amounts of modifiers or fillers), such as the production of transparent molded and extruded profiled materials for medical purposes. In contrast, typical elastomers, such as EP and EPDM rubbers, with x-ray crystallinity <7% to achieve acceptable values of key physical properties (e.g. tensile strength, wear resistance and so on), as well as an acceptable capacity for processing in the melt usually require fillers. Thus, with regard to systems for ethylene-based polymers of the present invention go beyond the typical EP and EPDM elastomers. Depending on the density value (or degree of crystallinity) of the polymers of the present invention could be attributed to plastomers (interval density of more than about 0,875 to about to 0.900 g/cm3), the ethylene polymer of the density (spacing density of more than about 0,915 to about 0,940 g/cm3). It should be called the U.S. patent 5266392 (Land and others), in which we are talking about the properties of blastomeres and their difference from the typical elastomers.

The purpose of the present invention, according to which receive the offer of polymers using catalysts and comonomers, can be achieved in any of several ways, including the use of an acceptable method for the polymerization of olefins, such as methods of gas-phase, liquid-phase, suspension polymerization or polymerization under high pressure. High pressure system is one example of a preferred variant of the process.

In the methods of polymerization according to the present invention can be used any catalyst of the Ziegler-Natta or a combination of such catalysts. The preferred catalysts of the Ziegler-Natta with a single plot, and among them, preferred metallocene catalysts including catalysts of the type di-Cp and type with only Cp and heteroatom; must also be workable varieties containing at least two amide or group was associated with the transition metal. All of these catalysts can have a bridging group between two obyazanyi silyl, germylenes and hydrocarbonyl bridges di-Cp mono-Cf/heteroatom and bisamine or was material. It is obvious that such catalysts can be used individually or in combination. These catalysts can be used alone, but it is preferable to combine or to enter into reaction with socialization or activator, with a cleaning agent or with their combinations. Generally preferred are those catalysts that use system metallocene-type activator, representing alumoxane, bulky mobile anionic material, or a mixture thereof. For additional efficiency in such a system it is possible to add an appropriate cleansing agent, such as, for example, alumoxane. Selected catalysts, including the whole catalytic system or any part thereof, may be used alone, in dissolved, suspended, supported on a carrier, in the form of terpolymerization system or combinations thereof. If the catalyst supported on a carrier, the preferred medium in the polymerization system is usually inert. Examples of such inert carriers include silica, alumina, zirconium dioxide, which are used individually or in coccolithophore for practical implementation of the present invention, described, for example, in European patent application A-129368, which is incorporated into this description by reference under U.S. law for the purposes of the description of the patent office of the United States. In this application describes the use of cyclopentadienyls compounds of transition metals to catalyze the polymerization of olefins.

At Turner and Hlatky in European applications A-277003 and A-277004 and in U.S. patent 5153157 that in accordance with the laws of the United States is included in the

the present description as reference, describes a discrete catalytic systems, where used chemistry metallocene type, but are anionic activators. Canich in U.S. patent 5055438, 5096867 and 5264405, enabled by the laws of the United States in the present description as reference, describes catalysis polymerization of olefins using the modified catalysts of the metallocene type, in which the metallocene compounds of previous generations replaced by a system monocytopoiesis/transition metal compound with a heteroatom.

Hlatky, Turner and Canich in the international application 92/00333, also included in the present description by reference under U.S. law, describe the use of ionic activators of the olefins.

Specific metallocene catalysts of the type that can be used to obtain isotactic olefin polymers can be found in European applications A-485820, A-485821, A-485822 and A-485823 filed by Winter and others, and in U.S. patent 5017714 and 5120867, issued in the name Welborn, and 5026798, issued in the name Canich. These publications included in the present description as links under the patent laws of the United States.

In various publications describe the application of catalytic systems on the material of the carrier and the use of prepared catalysts on carriers. These publications include U.S. patents 5006500, 4925821, 4937217, 4953397, 5086025, 4913075 and 4937301, issued in the name of Chang, U.S. patent 4808561, 4897455 and 5057475, issued in the name Canich, U.S. patent 5077255, 5124418, 5227440 and 4701432, issued in the name Welborn, application for U.S. patent 926006 and application for U.S. patent 08/155313, filed November 19, 1993, all of which are included in the present description as links under U.S. law. Additional information related to the technique of the media and the use of catalysts on carriers can be found in U.S. patent 5240894, issued in the name Burkhardt.

Indicator definition the width of the distribution (PSRS) or measure the width of the distribution of the peculiar chain of the finished polymer. This information allows to obtain a measurement technique that is well known and used in industry. Definition PSRS the elution fractions with increasing temperature (APPT) is well known in the art, and the method itself is described in Wild and others in the Journal of Polymer Science. Polymer Physics Edition, volume 20, page 441 (1982), in U.S. patent 5008204 and international application 93/03093. In the international application 93/03093 also describes a device for determining PSRR.

Direct determination of long chain branching (e.g., using spektroskopiya) is a complex method, which is applicable only to a limited extent. One reason is the difficulty in efficient and accurate differentiation of the side chains with six longitudinally spaced carbon atoms and side chains with more than six carbon atoms, even with such an effective instrument spectroscopic determination, as13C-NMR spectrograph. In addition, it is difficult to distinguish actually the long side chain in the surrounding background, which create numerous short side chains, such as contained after copolymerization with the typical used - the olefinic comonomers, in particular butene-1, hexene-1 willow polymer, therefore, the analysis and quantitative determination of the rheological behavior of the melt creates a unique opportunity to characterize long-chain branching. Within the classification of methods of studying the rheology of the melt for the characterization of long chain branching according to the invention the selected method for measuring the activation energy of the viscoelastic expiration (Eand). It is well known that with increasing temperature the viscosity of polymer melts, as reologicheskie simple liquids is reduced. In the literature a variety of ratios that determine this temperature dependence (see J. D. Ferry, Viscoelastic Properties of Polymers, edition 3rd, 1980, John Wiley and Sons, new York). At elevated temperatures (T>Tc+100oC, where Tcdenotes the glass transition temperature) the temperature dependence best expresses the equation type equation of the Arrhenius equation:

Viscosity (0) = Aexp(Ea/RT)

or in relation to the comparative temperature Tcf< / BR>
(0)T/(0Tcp= exp[(Ea/R)(1/T-1/Tcp)],

where R denotes the gas constant. The activation energy of viscous expiration of Eandit is relatively easy to determine with good accuracy, as described in visiprise the tours branching of the polymer.

It is well known that the activation energy of viscous expiration for linear polyethylene (HDPE) is approximately 6 kcal/mol, whereas for conventional LDPE it is equal to approximately 12 kcal/mol. It is a fact that this difference is primarily due to the presence of long chain branching in the final material. To a lesser extent the value of Eandalso depends on the availability of short-chain branching. Thus, taking into account the objectives of the present invention, determine the value of Ea. The value of Eacorresponds to the subtraction component determined by the content of short-chain polymer side groups, resulting in the residual value of the activation energy corresponds to a quantitative measure of the component of long-chain branching.

Methods of characterization of long chain branching by determining the rheological characteristics of the activation energy of viscous expiration (Eand)

Based on the methodology in General terms above, experimental method of assessing the presence of long chain branching in the sample olefin polymer and to determine the degree of long chain razvetvlenii the s shear stress under vibration (sinusoidal) parallel plates, the use of appropriate equipment, such as a Rheometrics RMS-800, RDS System or IV, in the following terms:

the polymer sample, properly stabilized before the test (for example, containing about 500 to 1000 parts per million parts thermal/oxidative stabilizer, such as product lrganox 1076 supplied by the company Ciba-Geigy);

- frequency range: 0.01 to 100 rad/s, preferably not less than five points, data on tens;

- temperature: 150, 170, 190, 220oC;

- the maximum amplitude of deformation is set by the operator to obtain the best signal in the linear viscoelastic range), as a rule, is 20%.

The processed data includes:

- the horizontal alignment of complex modulus G*the graphs of the dependence log G*from the log (frequency) for comparative temperature 190oC using the appropriate software, focusing on low-frequency combination;

- enter the obtained coefficients offset in the Arrhenius equation to determine the Eandfrom

andT=exp (Eand/RT)=exp[(Eand/R)/T-1/Tcf)];

- visual playback data for the base curve and G' and G", moduli of elasticity and viscosity depending on the frequency ().andwith the result for a polymer with an equivalent linear circuit (i.e. with the same degree of short chain branching due to the polymerization of - olefins co monomer, but without long chain branching). The presence of long chain branching clearly indicates the fact, when the activation energy of expiration (Eand) studied polymer minus the activation energy of the expiration of the equivalent linear polymer is greater than or equal to 1 kcal/mol. This is equivalent to the linear polymer has the same degree of short chain branching, but does not contain any long side chains. When expressed in equation form, this is the last indicates the presence of long chain branching, when Ea= [measured (Eand) - linear (Eand)] 1 kcal/mol. In Fig. 1 sample A (without DCR) compared with sample B (with DCR). Eafor sample a is <1.0, which indicates the absence of an appreciable degree of DCR. Eafor sample B is significantly greater than 1.0, which indicates DCR. The curve represents a linear ethylene-alpha-olefin copolymers. For different-olefin comonomers characteristic probably different dependence of Eafrom the content of the co monomer,

comparison of the curves G is Owlery whether high values of Eandobtained by the measurement, only long-chain branching or, alternatively, the formation of crosslinked structures (in this case, G' and G" are combined).

Molecular mass and molecular mass distribution of polymers according to the present invention was determined by gel chromatography (GPC) using a device for high-temperature GPC 150oC company Waters Associates (Milford, PCs Minnesota). The measurements were carried out at a temperature of 145oC using trichlorobenzene as solvent at a flow rate of 1.0 CC/min In an amount of 0.6 g per liter of solvent used antioxidant Santonox R supplied by the company Monsanto Chemical Co., St. Louis, PCs Missouri. As the sample in the device was injected to 0.30 CC of a solution of polymer in solvent concentration of 0.1 wt.%. For the separation was applied three columns with mixed attachment under the name Shodex AT-80 M/S firm Showa Denko K. K., Japan. Data collection and analysis were performed with the use of the software firms Waters. Used calibration curve for molecular weight consisted of the following three areas:

1. Low-molecular area (up to the value 703) calibrated for a range of monodisperse n-alkanes (C18C24C36, the Wali using polystyrene standards with narrow molecular weight distribution, for which the molecular weight polyethylene equivalent was calculated in comparison with the product SRM 1475, wide standard linear polyethylene from the National Institute of Standards and Technology (Gaithersburg, PCs Maryland). To calculate the molecular weights of polyethylene equivalents" peak elution of each polystyrene standard was compared with data for a specific layer when tested polyethylene standard in identical conditions. The list of standard data for the molecular weight of the specific layer as a function of the cumulative percentage elyuirovaniya weight polyethylene can be found in the National Bureau of Standards in NBS Special Publication 260-42 ("The Characterization of Linear Polyethylene SRM 1475").

3. The curve for high molecular weight (>1000000) was calibrated by polystyrene standards with narrow molecular weight distribution, the molecular weight of which is transformed in molecular weight polyethylene equivalent using the following coefficients of the Mark-Houwink:

< / BR>
The calibration curve as a whole is built in the form of a graph of the dependence of molecular weight from the time of elution and the corresponding data points are sequentially connected to each other.

For calculation of the average LVEF is by far the moment when the elution of molecules highest molecular weight, to the zone in which the newly restored linearity. Using data for a specific layer by a standard method was obtained mean values of various molecular masses. To assess the presence of long chain branching in the polymers of the present invention when processing data, no corrections were made.

The expression of molecular weight in terms of Mn (srednekislye), Mw (srednevekovaja) and Mz (z-average) is a common practice, which in this case is used to refer to polymers of the present invention. Value ratios above mean values serve as a measure of polydispersity or the width of the molecular mass distribution. So, for example, linear polymers obtained with the use of catalysts with a single site, such as metallocene catalysts on the basis of, have characteristic molecular mass distribution by type Flory parameters Mw/Mn of 2.0 and Mz/Mw of 1.5. The introduction of long chain branching in accordance with the method of the present invention violates characteristic type Flory distribution for metallocene catalysts on the basis of that result is. the IG. 1). The value of the ratio Mz/Mw is the most suitable option towards creating materials containing long chain branching, as she emphasizes the changes in the macromolecular part of the spectrum of molecular weights.

The content of unsaturated groups in the polymers of the present invention was determined using standard techniques1H-NMR and IR spectrometry Fourier transform (ICFP), and the results determine the number of unsaturated groups were expressed as the number of parcels unsaturated groups per 1000 C-atoms. Alternatively, this number was converted using srednekamennogo molecular weight Mn to display the number of unsaturated groups in a number of unsaturated sites on the average number of molecules.

To a person skilled in the art it is obvious that the present invention includes the possibility of mixing the above-described polymers with other polymers, fillers and additives to obtain a finished product having the desired set of characteristics.

Examples

Below the invention is explained in more detail in the experimental examples of the polymerization, which should not be considered as ogrr refers to the ratio of the melt indexes I21/I2at 190oC; Eanddetermine the measurements of the shear stress under vibration parallel plates at different temperatures; and the number of unsaturated groups define1H-NMR or ECFP-analysis.

The first two experiments conducted liquid-phase polymerization. The following is a description of these experiments. In example 1 described the polymerization of a copolymer of ethylene and hexene-1 (control experiment), while in example 2 described polymerization to obtain the polymer of the present invention, copolymer of ethylene, hexene-1 and 1.4 - pentadiene.

Group experiments AND

An example of polymerization of 1

Polymerization was performed in a one-liter autoclave reactor equipped with a paddle stirrer, an external water jacket for temperature control, means a regulated supply of dry nitrogen, ethylene, propylene, butene-1 and hexene-1 and membrane inlet device for the input of other solvents or comonomers, solutions of compounds of the transition metal and alumoxane. Before using the reactor thoroughly dried and was degirolami. The typical process was loaded into the reactor 200 ml of toluene, 10 ml of 1-hexene and 1,5 ml of MAO concentration of 10 wt.%. Then the reactor is 0.25 ml of a solution of 13.4 mg Me2Si(Me4C5)(N-cyclo-C12H23) TiCl2in 10 ml of toluene]. Then enter ethylene pressure in the reactor brought up to 450 kPa (65 psi) and the reaction was carried out for 15 min, followed by a sharp cooling and ventilation system. The solvent of the polymer evaporated with a stream of nitrogen. In this way received 17.9 g of a copolymer of ethylene and hexene-1 (Mw were 248200 of 9.5 mol.% parts of hexene-1, the estimated value of Eandwas 8,54 kcal/mol, Eandaccording to the observations of 9.89 kcal/mol, Eaof 1.35 kcal/mol).

An example of polymerization of 2

Using a reactor of the same design and the same General method, the reactor was introduced 200 ml of toluene, 10 ml of hexene-1, 0.05 ml of 1,4-pentadiene and 3.0 ml of MAO concentration of 10 wt.%. The reactor was heated up to 80oC and it was added to 0.67 mg Me2Si(Me4C5)(N-cyclo-C12H23) TiCl2[0.5 ml of a solution of 13.4 mg Me2Si(Me4C5)(N-cyclo-C12H23) TiCl2in 10 ml of toluene]. Then enter ethylene pressure in the reactor brought up to 450 kPa (65 psi) and the reaction was carried out for 15 min, followed by a sharp cooling and ventilation system. After evaporation of the solvent was received of 24.7 g of a copolymer of ethylene, hexene-1 and 1.4-pentadiene (Mw SOS is eniam 12.5 kcal/mol, Ea3,91 kcal/mol).

It may be noted that in the control experiment, example 1, which did not use Dien, Eaamounted to 1.35 kcal/mol, while in example 2 (with 1,4-pentadiene) Eawas 3,91 kcal/mol. By itself, the control sample was probably required by the present invention, the value of Eamore than 1 kcal/mol. This phenomenon may at first glance seem as inconsistent with the present invention, but the reason becomes clear if we turn to issued in the name of Lai and other U.S. patent 5272236, where the rows 35-39 column 6 States that the catalysts according to the U.S. patent 5026798 fully effective in the practical implementation of the proposed in this patent the way of long-chain branching. The catalyst was used as a control in example 1 according to the present invention, as well as in the experiment with input diene, was a catalytic system mono-Cf/heteroatom, which is described in U.S. patent 5026798. Thus, the conditions created in this experiment, similar to those described by Lai and others Therefore, it can be expected that in such circumstances there is a certain oligomerization, followed by an introduction to docterines improved ability to process due to long chain branching. However, it is clear that in example 2 with the introduction of 1,4-pentadiene Easignificantly more than 1 kcal/mol, thereby surpassing the polymer obtained from the same monomers, excluding materials containing at least two polymerized by Ziegler-Natta communication (in this case ,- diene, 1,4-pentadien), which are characteristic of the polymers of the present invention.

Group of experiments I-IV

In the autoclave reactor pilot plant size did a few other various polymerization processes for promotion of long chain branching by introducing various diene. These processes included the copolymerization of 1.5-hexadiene with ethylene and butene-1 for comparative purposes; 1,9-decadiene with ethylene and butene-1 and vinylnorbornene with ethylene and hexene-1. Such a copolymerization reaction was performed using known in the art catalysts with a single active site.

The description of the experiment polymerization below. Used 1500-ml steel autoclave reaction vessel with a stirrer, a suitably equipped for carrying out continuous polymerization by Ziegler-Natta under pressure up to 2500 bar and the constant monitoring of temperature and pressure, and means for continuous supply of purified compressed monomers (such as ethylene, butene-1 and dienes). Were provided by the equipment for continuous input feed stream of a solution of a catalyst under high pressure and equipment for quick ventilation and abrupt cessation of the reaction, and collecting the polymer product removed from the reaction medium. The polymerization was performed without adding outside of any solvent. When carrying out the polymerization, the reactor was continuously stirred with a speed of 1500 Rev/min the Temperature in the reactor was set and maintained at a target level by the injection into it of the catalyst solution with injection pump high-pressure continuous action. After polymerization was measured output polymerized product and perform the analysis for quality control (at least the melt index and density of the product). In this reaction system was provided by polymerization reagents for one cycle, without recirculation of unreacted monomers and their return in the reaction system.

Table I presents the conditions of polymerization and the reaction conditions for groups of experiments I-IV. Group I includes what yenom; group III includes the polymerization of ethylene and 1-hexene with vinylnorbornene; and group IV includes the polymerization of ethylene and 1-hexene with vinylnorbornene, but using catalyst with the only site you used in the group III. In the experiments of group III (but not groups I, II and IV) to regulate Mw in the reactor was continuously introduced hydrogen gas with a flow rate of 20 l/h

Table II lists some of the characteristics of products, certain measurements during testing of the polymers obtained in the experiments of groups I-IV. In each group of experiments with increasing amounts of input materials with at least two polymerized by Ziegler-Natta links has been an increase in the activation energy Eand. This indicated a higher degree of long chain branching. The first product in each group (i.e., a control sample obtained without materials with at least two polymerized by Ziegler-Natta bonds") were characterized by a certain measurements of the activation energy of the expiration of Eandcomparable to that which was expected to enter the number of units of an alpha-olefin co monomer, which led to the achievement of znacheniya control samples did not contain any appreciable long-chain branching. Subsequent products in each group was characterized by the increase of Ea(i.e., > 1 kcal/mol), indicating that the increase in the degree of long chain branching.

The presence of long chain branching in the polymers of the present invention were also found in these molecular weights are presented in table II. Control samples in each group (prepared without use of materials having at least two polymerized by Ziegler-Natta communication"), which was obtained by polymerization using the so-called catalysts for the sole areas, is known in the art, characterized by a typical molecular weight distribution by type Flory. Characteristics of such include distribution Mw/Mn (i.e., the ratio between srednevekovoi and srednekamennogo molecular masses of ~ 2.0 and Mz/Mw (i.e., the ratio of medium-Z and srednevekovoi molecular masses) ~1,5. According to the observations of the actual measurement data contained in table II, for the control samples were generally close to these characteristic parameters. For the other products of each group a clear increase of the values of the ratio Mw/Mn and Mz/Mw accompanying increase alicecullen using a GPC molecular weight distribution for products produced using materials that had at least two polymerized by Ziegler-Natta communication", and without them (see Fig. 2) clearly showed the formation of high-molecular strips that were directly caused by the presence of materials containing long chain branching.

The polymers of the present invention showed a high content of residual unsaturated groups, which is evident from the data presented in table II. Products with long-chain branching in each group had a significantly higher total content of unsaturated groups in comparison with control. These unsaturated groups are available for use by postpolymerization with the formation of cross-links and retrieve the material that behavior is reminiscent of thermosetting polymer or functionalized, or for other purposes.

The polymers of the present invention, containing long-chain side groups, are presented in table II, had an improved characterization of gap extrusion flow. The widely used technique of mapping trends to gap extrusion flow related polymers is to visually control the shear rate at the beginning of the RNA graph of dependence of shear stress on the shear velocity measurements, performed in a capillary viscometer at a given temperature of the melt (125oC) (see Fig. 4). Higher initial speed shift reflected the improved characteristics of gap extrusion flow. In Fig. 3, which presents a plot of the initial velocity shift from the molecular weight Mw, illustrated characteristics for polymers with long chain branching of the present invention, i.e., the product of 4 and 12, and their respective control samples, i.e., products I and II (characteristic details in table II). Line in Fig. 3 reflects the basic features of standard polymers of ethylene-olefin basis, obtained using catalysts with the only site identified in this group of experiments (the EXACT productsTM3014, 3026, 3027, 4001, 4002, 4003, 4015 and 4040, covering a range of molecular weights Mw 38000-94000 and supplied to the market by the company Exxon Chemical Company, Houston, pc. Texas). Data for the control samples, i.e., products 1 and 11, are along the baseline, while for the corresponding polymers with long chain branching, i.e., the product of 4 and 12, they are much above this baseline (higher initial shear rate), accounted for the effect of the polymers of the present invention, presented in table II, showed a higher sensitivity of the melt to shift. Sensitivity to shift according to the results of capillary realtionship measurements at a given temperature of the melt is associated with quantitative reducing viscosity, which was reached at higher shear rates compared to the viscosity at low shear rates. If you compare related polymers, a significant reduction in viscosity indicates a higher sensitivity to shear and easier extraterrest melt. In Fig. 5 shows a plot of the ratio between the values of viscosity at the shear rate of 14 c-1(low shear rate) and 69 c-1(high shear rate) of molecular weight Mw. This ratio is used as an indicator of sensitivity to shear, and a higher ratio corresponds to a higher shear-thinning, which is necessary for many applications. Line in Fig. 5 reflects the characteristics of the baseline standard of polymers of ethylene- -olefin basis, obtained using catalysts with the only site identified in this group of experiments. Point for the control sample, i.e. produktlinie, is much above the baseline, reflecting a higher sensitivity to shift.

The group of experiments V

Most of the processes of polymerization was performed using a reaction system described in groups of experiments I-IV. In this system was provided by polymerization reagents for one cycle without recirculation of unreacted monomers and their return in the reaction system. In group V the polymerization under high pressure were carried out in a more large (4-quart) adiabatic pressure reactor with stirrer, which is generally operated in a manner similar to the above reactor and which was additionally equipped with a recirculation system for return of unreacted components after passing through the condenser and the compressor in the autoclave reactor together with fresh monomers instead spent their quantities. The diene used in this experiment represented norbornadiene (NBD).

In table III summarizes the polymerization conditions and the reaction conditions for the group of experiments V.

Table IV presents the measurement data of some of the final parameters of the obtained polymers. As in the previous experimental whom and with at least two polymerized by Ziegler-Natta bonds") the difference between the values of Eand, i.e., Eawas significantly > 1 kcal/mol, reflecting the presence of materials containing long-chain branching. Increased molecular weight distribution in comparison with the characteristic value of the Flory for the control sample, which was another indication of long-chain branching.

For specialists in the art it is obvious that the above description is an example of preferred embodiments of the present invention. According to the invention may exercise other options that are not necessarily covered by any specific examples or preferred option, described above. Scope of the present invention is limited only by the attached claims.

1. The copolymer obtained from at least three monomers comprising: a) one monoolefins containing only the polymerized by Ziegler-Natta communication; b) a second monomer containing at least one polymerized by Ziegler-Natta communication, and C) a third monomer containing at least two polymerized by Ziegler-Natta communication, and this monomer is: (I) premazepam with less than six or at least steripulse: g) the presence of at least one carbon-carbon unsaturated communication srednekamennogo molecule; d) activation energy (Eand) viscous expiration of at least 1 kcal/mol higher than that of a copolymer containing a linear main chain and derived from the same monomers, but does not include materials containing at least two polymerized by Ziegler-Natta communication; (e) degree of crystallinity in the range from 10 to 50% W) the value of Mz/Mw of at least 1,7.

2. The copolymer under item 1, where monoolefins containing at least one polymerized by Ziegler-Natta communication, represents ethylene.

3. The copolymer according to any one of the preceding paragraphs, where the third monomer is a diene.

4. The copolymer according to any one of the preceding paragraphs, where the diene is chosen from the group comprising 1,3-butadiene, 1,4-pentadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadien, 1,11-dodecadien or cyclohexadiene, cyclooctadiene, norbornadiene, vinylnorbornene.

5. The copolymer according to any one of the preceding paragraphs, where the material containing at least one polymerized by Ziegler-Natta bond, selected from a group comprising propylene, butene-1, penten-1, hexene-1, hepten-1, octene-1, nonen-1, mission 1, undecene-1, dodecene-1, hexadecene-1, octadecene-1 and 4-methylpentene-1.

6. The copolymer of gruppy, includes propylene, butene-1, penten-1, hexene-1, hepten-1, octene-1, nonen-1, mission 1, undecene-1, dodecene-1, hexadecene-1, octadecene-1 and 4-methylpentene-1, and b) a third monomer selected from the group including: (I) 1,3-butadiene, 1,4-pentadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadien, 1,11-dodecadien or II) norbornadiene, vinylnorbornene, cyclohexadiene, cyclooctadiene, cyclohexadien or branched acyclic diene.

7. The copolymer according to any one of the preceding paragraphs, containing 1-7,6 unsaturated carbon-carbon linkages per 1000 carbon atoms.

8. The method of copolymerization: a) at least one monoolefins containing only the polymerized by Ziegler-Natta communication, b) a second monomer containing at least one polymerized by Ziegler-Natta communication, and C) a third monomer containing at least two polymerized by Ziegler-Natta communication, and this monomer is: (I) premazepam with less than six or at least seven carbon atoms, (II) non-remotemachine or III) a combination thereof, the method includes the following stages: g) contacting the monomers with a catalyst of the Ziegler-Natta, its derivatives or their combinations under pressure is merisalu carried out at pressures above 500 bar.

10. The method according to any of paragraphs.8 and 9, where monoolefins selected from the group including ethylene and propylene, the second monomer is chosen from the group comprising butene-1, penten-1, hexene-1, octene-1, mission 1, dodecene-1, octadecene-1 and 4-methylpentene-1, and a monomer containing at least two polymerized by Ziegler-Natta communication selected from a group including a 1.7-octadiene, 1,9-decadiene, 1,11-dodecadien, norbornadiene, vinylnorbornene, cyclohexadiene, cyclooctadiene and cyclodecane.

11. The method according to any of paragraphs.8 - 10, where the monomer containing at least two polymerized by Ziegler-Natta communication selected from a group including a 1.7-octadiene, 1,9-decadiene, norbornadiene and vinylnorbornene.

12. The method according to any of paragraphs.8 to 11, where the diene is chosen from the group comprising 1,3-butadiene, 1,4-pentadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadien, 1,11-dodecadien or cyclohexadiene, cyclooctadiene, norbornadiene, vinylnorbornene and branched acyclic diene.

13. The method according to any of paragraphs.8 - 12, where the second monomer is chosen from the group comprising propylene, butene-1, penten-1, hexene-1, hepten-1, octene-1, nonen-1, mission 1, undecene-1, dodecene-1, hexadecene-1, octadecene-1 and 4-methylpentene-1.

14. The method according to any of the persons according to any one of paragraphs.8 - 14, where the activator to metallocene catalytic systems use activator comprising alumoxane, bulky mobile anionic material, or a mixture thereof.

16. The method according to PP.8 - 15, which together with the metallocene catalyst system is a mixture of activator and cleansing agent.

17. The process comprising the copolymerization of ethylene and polyene containing at least two polymerized by Ziegler-Natta double bond at a temperature of at least 120oC using a catalyst prepared from the compound of the transition metal containing bulky ancillary ligand, to obtain the ethylene copolymer, the ratio of the indices of the melt which is at least 25, and the activation energy is equal to at least 9.0 kcal/mol.

 

Same patents:

The invention relates to the synthesis of low molecular weight branched polyethylene in the presence of efficient homogeneous catalytic systems based on metallocene or pseudometallic complexes IVC group, alyuminiiorganicheskikh compounds and perftoralkil borates

The invention relates to the components of the catalyst for polymerization of olefins comprising the product obtained by the reaction of compounds of the transition metal M selected from Ti, Zr, HF containing at least one M--communication with the porous polymer carrier, representing a prepolymer obtained by polymerization of one or more olefins of the General formula CH2=CHR, in which R is hydrogen or alkyl with 1-12 carbon atoms, with a complex catalyst comprising the product obtained by contacting connection Ti with a halide of magnesium in the form of particles with an average crystallite size below 300it called the halide of magnesium contained in the above-mentioned prepolymer in amounts of between 50 and 50000 h

The invention relates to the chemistry of polymers, and to methods of producing stereoregular polypropylene, and can be used in the chemical industry in the manufacture of plastics

The invention relates to copolymers of ethylene with propylene, optionally with a minimum number of polyene and method of production thereof

The invention relates to antioxidants, which can be polymerized with other monomers to form copolymers, giving the antioxidative properties of polymers, and to oxidizing agents and methods for use in the creation of such polymers

FIELD: chemistry.

SUBSTANCE: invention relates to production of synthetic rubber, particularly ethylene-propylene rubber and can be used in petrochemical industry. Method involves copolymerisation of ethylene and propylene in a medium of hydrocarbon solvent in the presence of a cyclic diene comonomer or without it and a catalyst complex based on an organoaluminium compound, vanadium chloride or chloro-oxyvanadium V and a reactivator. During the process, hexachloroparaxylene (HCPX) and a catalyst as a reactivator are simultaneously added to the reaction mixture in a hydrocarbon solvent in such an amount that, molar ratio V:HCPX equals 1:1-1:10.

EFFECT: increased catalyst activity, reduced catalyst consumption, reduced output of cross-linked and branched structures in the ready polymer with retention of its wear resistance.

1 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: described is a method of producing ethylene-propylene rubber via copolymerisation of ethylene and propylene in the medium of a hydrocarbon solvent. Copolymerisation takes place in the presence of a cyclic diene comonomer or without, while using a catalyst system based on an organoaluminium compound, vanadium chloride or vanadium oxychloride, a catalyst reactivator and a chain-terminating agent. The method also involves washing, stabilising, degassing and drying the polymer. The copolymerisation reaction is interrupted by adding to the reaction mixture a monoester of a diatomic alcohol in such an amount that, the molar ratio of said monoester to the total amount of metals in the catalyst system is in the range of 0.48-0.8:1.

EFFECT: high degree of extraction of variable-valence metals from the polymer solution and low fraction of uncontrolled branching of the ready cyclic diene.

1 tbl, 15 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing ethylene, propylene and diene copolymers, also known as SKEPT rubber, having high molecular weight and a narrow molecular-weight distribution. The catalyst used is a vanadium compound of formula: Z1, Z2 is a heteroatom which can be selected from O, S, N; B is a heteroatom which can be selected from O, S; X is a halogen which can be selected F, Cl, Br, I, preferably CI, Br; A is a carbon-containing fragment which can be selected from C1-C10 aliphatic series, preferably or C6-C24 aromatic series, preferably , or a C1-C10 heteroaromatic compound with one or three N atoms; A1 is a carbon-containing fragment which can be selected from the C1-C10 aliphatic series, preferably CH3, C2H5, C3H7, C4H9, or a C6-C24 aliphatic series, preferably C6-C12; A2 is a carbon-containing fragment which can be selected from a C1-C10 aliphatic series, preferably CH3; C2H5, C3H7, C4H9, or a C6-C24 aromatic series, preferably C6-C12; k=0 or 1; m=3 or 4; n=1 or 2. The invention also describes other versions of a vanadium catalyst system and a method of producing an ethylene, propylene and diene copolymer.

EFFECT: high output of copolymer on 1 g of metal.

22 cl, 1 tbl, 23 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing olefin/diene copolymers on a homogeneous metallocene catalyst system. Described is a method of producing copolymers of monomers by polymerisation of olefins or a mixture of olefins and linear or cyclic dienes in the presence of a homogeneous catalyst system. The catalyst system consists of dialkyl bridged bis-indenyl metallocene complexes of group IVB metals and aluminium trialkyls.

EFFECT: formation of copolymers with a controlled composition, the lowest compositional and fractional non-uniformity and preventing simultaneous formation of homopolymers.

1 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: method includes polymerising the mixture of monomers containing ethylene, at least one C3-12 α-olefin and optionally at least one unconjugated C4-20 diene in a suspension in the presence of a catalyst system. The catalyst system contains the suspension of a catalyst selected from a number comprising vanadium compounds in oil, a cocatalyst selected in the absence of organic solvents from a number comprising aluminium compounds, an activator selected in the absence of an organic solvent from a number comprising chlorine compounds.

EFFECT: obtaining elastomeric polymers having low gel content.

19 cl, 1 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to use of isobutyl aluminium aryloxides of composition: AliBux(OAr)3-x as activators of dialkyl metallocene catalysts of transition metals of IVB Group in homopolymerisation of ethylene, propylene, copolymerisation of ethylene, propylene and triple copolymerisation of ethylene, propylene and dienes. Invention also relates to development of an effective method of producing homopolymers of ethylene, propylene, copolymers of ethylene with propylene and ternary copolymers of ethylene with propylene and dienes. Present method provides controlled synthesis of composite and fractionally homogeneous polymers with controlled microstructure, molecular weight and controlled content of comonomers in copolymer. Introduction of phenol antioxidants is provided at step of washing polymer by hydrolysis aryloxide alkylaluminium activator. Advantages of isobutyl aluminium aryloxides are: simplicity and safety of synthesis, high activating capacity at low molar ratio Al/Zr (≈102 mol/mol), stability during storage, ability to purify reaction medium from impurities of moisture without use of additional cleaning reagents and special preparation of reactor for polymerisation, as well as possibility of producing polymers containing stabilisers-antioxidants, role which is performed by phenols, formed by hydrolysis in situ during decomposition of an organoaluminium component of catalyst systems at step of washing polymer with water-alcohol solution.

EFFECT: invention relates to a method of stabilising homo- and copolymers of olefin and dienes by hydrolysis with a water-alcohol solution of isobutyl aluminium aryloxide contained in disclosed homogeneous catalyst system, at polymer washing step.

4 cl, 1 tbl, 28 ex

OAr=

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