RU2355710C2 - Polymerisation methods involving hydrofluorocarbons - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention concerns novel polymerisation methods involving hydrofluorocarbons in polymer obtainment. Polymerisation method involves contact of at least one first source material flow and at least one second source material flow in reactor system, with contact time of approximately 30 seconds or less. Method involves dilutant containing one or more hydrofluorocarbons in reactor system.

EFFECT: novel polymerisation methods and reactor system constructions reducing particle agglomeration and reactor pollution without impairing technological parametres, conditions or components and/or without impairing efficiency/throughput, and/or with possible obtainment of high-molecular polymers.

36 cl, 3 tbl, 9 ex, 3 dwg

Description

FIELD OF THE INVENTION

The invention relates to new methods of polymerization using fluorocarbons to obtain polymers. Thus, in particular, the invention relates to new methods of polymerization using reactor systems with a turbulent flow, in which diluents, including fluorocarbons, are used to obtain polymers.

BACKGROUND OF THE INVENTION

Isoolefin polymers are obtained in the processes of carbocationic polymerization. Of particular importance is butyl rubber, which is a copolymer of isobutylene with a small amount of isoprene. Butyl rubber is obtained by low-temperature cationic polymerization, during which the production of high molecular weight butyl rubber usually requires isobutylene to have a degree of purity> 99.5 wt.%, And isoprene to have a degree of purity> 98.0 wt.%.

The carbocationic polymerization of isobutylene and its copolymerization with comonomers like isoprene is mechanically complex (see, for example, Organic Chemistry, sixth edition, Morrison and Boyd, Prentice-Hall, 1084-1085, Englewood Cliffs, New Jersey 1992, and K. Matyjaszewski, ed., Cationic Polymerizations. Marcel Dekker, Inc., New York, 1996). The catalytic system usually consists of two components: the initiator and the Lewis acid. Examples of Lewis acids include AlCl ₃ and BF ₃ . Examples of initiators include Bronsted acids such as HCl, RCOOH (in which R is an alkyl group) and H ₂ O. During the polymerization process, in what is commonly referred to as the initiation stage, isobutylene reacts with a Lewis acid / initiator pair to form a carbenium ion . After this, at the stage, which is usually called the stage of chain growth, additional monomer units are added to the formed carbenium ion. These steps are typically carried out in a diluent or solvent. The chemical mechanism of chain growth is influenced by temperature, polarity of the diluent, and counterions. Of these, thinner is generally considered important.

In industry, the use of the suspension polymerization method (with the production of butyl rubber, polyisobutylene, etc.) in methyl chloride as a diluent was widely recognized. In the polymerization process, methyl chloride is commonly used as a diluent for the reaction mixture at low temperatures, usually below -90 ° C. Methyl chloride is used for many reasons, including the fact that it dissolves monomers and an aluminum chloride catalyst, but not a polymer product. Methyl chloride also has freezing and boiling points that are acceptable to allow respectively low temperature polymerization and efficient separation from the polymer and unreacted monomers. Carrying out the suspension polymerization process in methyl chloride provides several additional advantages in that a polymer concentration of about 26 to 37 vol.% Can be achieved in the reaction mixture, as opposed to a concentration of only about 8 to 12% for solution polymerization. At the same time, an acceptable, relatively low viscosity of the polymerization mass is achieved, which makes it possible to more effectively remove polymerization heat due to surface heat transfer. Methods of suspension polymerization in methyl chloride are used in the preparation of high molecular weight isobutylene and isobutylene-isoprene butyl rubber polymers. Similarly, the polymerization of isobutylene and para-methylstyrene is also carried out using methyl chloride. In addition, star-butyl rubber is also obtained using methyl chloride.

However, there are a number of problems associated with polymerization in methyl chloride, for example, the tendency of polymer particles in the reactor to agglomerate with each other and to accumulate on the reactor wall, heat transfer surfaces, on the impeller (s) and agitator (s) / pump (s). As the reaction temperature rises, the agglomeration rate increases rapidly. Agglomerated particles tend to adhere, increase in size and form deposits on all surfaces with which they come in contact, in particular, discharge lines of the reactor, as well as any heat exchange equipment that is used to remove heat from the exothermic polymerization reaction, which is crucial because it is necessary to maintain low temperature reaction conditions.

Industrial reactors, which are usually used to produce these rubbers, are vessels with efficient mixing in a volume of more than 10 to 30 liters with a high circulation speed provided by the impeller of a centrifugal pump. Both the polymerization process and the pump generate heat, and in order to keep the suspension cold, the reaction system needs the ability to remove heat. An example of such a tank type reactor with a stirrer and continuous feed (“PMNPS”) is given in US Pat. No. 5,417,930, incorporated herein by reference, which is hereinafter collectively referred to as “reactor” or “butyl reactor”. In these reactors, the suspension circulates through the tubes of the heat exchanger under the influence of a pump, while boiling ethylene from the casing provides cooling, and the temperature of the suspension is determined by the temperature of the boiling ethylene, the necessary heat flux, and the total heat resistance. The polymer gradually accumulates on the suspension side of the surface of the heat exchanger, preventing heat transfer, as a result of which, apparently, there is a tendency to increase the temperature of the suspension. This often limits the practical concentration of the suspension, at which it can be used in most reactors, from 26 to 37 vol.% Relative to the total volume of the suspension, diluent and unreacted monomers. Several patents have been devoted to solving the problem of polymer accumulation (such as US Pat. Nos. 2,534,698, US 2,548415, US 2,464,809). However, these patents did not provide a means of satisfactorily resolving the myriad of problems associated with the agglomeration of polymer particles in order to develop the required industrial process.

In US patent No. 2534698, among other things, a polymerization method is described, comprising, in combination, the step of dispersing a mixture of isobutylene and a polyolefin containing from 4 to 14 carbon atoms per molecule, including a fluorine-substituted aliphatic hydrocarbon material in the mass without substantially dissolving in it in a proportion from half of up to 10 frequent a fluorine-substituted aliphatic hydrocarbon containing one to five carbon atoms per molecule, which is a liquid at the polymerization temperature, and polymerizing this dispersed mixture of isobutylene and a polyolefin containing four to fourteen carbon atoms per molecule, at temperatures ranging from -20 to - 164 ° C by introducing into it a Friedel-Crafts catalyst. However, US Pat. No. 2,534,698 suggests that, in the case of acceptable fluorocarbons, a two-phase system is formed with a monomer, comonomer, and catalyst substantially insoluble in fluorocarbon, and therefore their use is fraught with technological difficulties and is unsatisfactory.

US Pat. No. 2,548,415 describes, among other things, a continuous polymerization process for producing a copolymer, the steps of continuously feeding a stream to the polymerization reactors, comprising isobutylene and a small amount of isoprene as a main part; diluting this mixture using 1/2 to 10 volumes of ethylidene difluoride; copolymerization of a mixture of isobutylene with isoprene by continuously adding to the reaction mixture a liquid stream of a previously prepared polymerization catalyst, including boron trifluoride in solution in ethylidene difluoride, maintaining a temperature in the range from -40 to -103 ° С during the whole copolymerization reaction. US Pat. No. 2,548,415 teaches the use of boron trifluoride and its complexes as a Lewis acid as a catalyst and 1,1-difluoroethane as a preferred combination. This combination creates a system in which everything is soluble - the catalyst, monomer and comonomer, and provides a high degree of polymer insolubility, creating the benefits of reduced reactor fouling. However, boron trifluoride is not a preferred industrial catalyst for butyl polymers for many reasons.

In US patent No. 2644809, among other things, it refers to a polymerization method, comprising, in combination, the steps of mixing together the main part of a monoolefin containing from 4 to 8 inclusive carbon atoms per molecule, with a small amount of a multiolefin containing from 4 to 14 inclusive carbon atoms per molecule polymerizing the prepared mixture with the dissolved Friedel-Crafts catalyst in the presence of from 1 to 10 volumes (calculated as mixed olefins) of a liquid selected from the group consisting of dichlorodifluoromethane, dichloromethane, trich ormonoftormetan, dichloromonofluoromethane, dichlorotetrafluoroethane and mixtures thereof, wherein liquid is dissolved in said monoolefin and multiolefin, and conducting polymerization at a temperature ranging from -20 ° C to the freezing point of the liquid. US Pat. No. 2,464,809 describes the effectiveness of chlorofluorocarbons in maintaining ideal suspension characteristics and minimizing reactor fouling, but the introduction of a diolefin (i.e., isoprene) by adding chlorofluorocarbons (CFCs) is described. CFCs are known as ozone-depleting chemicals. However, government regulations strictly regulate the production and distribution of CFCs, making these materials unattractive for industrial processes.

Moreover, Thaler W.A., Buckley Sr., D.J. High Molecular-Weight, High Unsaturation Copolymers of Isobutylene and Conjugated Dienes, 49 (4) Rubber Chemical Technology, 960 (1976), among other things, describe cationic suspension polymerization to produce isobutylene-isoprene copolymers (butyl rubber) and using cyclopentadiene in heptane.

If, in particular, refer to some reactor systems, then links to the description of previously known technical solutions in the art include GB 2181145 A, the work of Berlin and others, The Macroscopic Kinetics of Rapid Processes of Polymerization in Turbulent Flows, Polym.-Plast . TechnolEng., 30 (2 & 3), 253-297 (1991). Minsker et al., Plug-Flow Tubular Turbulent Reactors: A New Type of Industrial Apparatus, Theoretical Foundations of Chemical Engineerig, Vol. 35, No. 2, 162-167 (2001), and US No. 5397179. These references describe, inter alia, polymerization processes applicable to what are commonly referred to in the industry as “ejector reactors” or tube turbulent reactors.

Such reactors have recently been commonly tested using chlorinated hydrocarbons. These polymerization processes in the art are well known for their low conversion, low polymer yield and / or large variations in molecular weight and molecular weight distribution of the polymer product. These characteristic features give rise to a number of complex tasks associated with the large-scale industrial implementation of such methods and designs of reactor systems.

So, for example, monomer addition reactions (chain growth and transverse chain growth) must be extremely fast, since many monomer additions (usually hundreds or more, and usually tens of thousands) must occur to form one polymer molecular chain. In addition, the kinetics of polymerization initiation should be so fast that the total reaction time is short and the polymerization proceeds uniformly.

Moreover, during a short reaction period, a large amount of exothermic polymerization heat must be removed from the reaction mass, and this is often associated with technological difficulties during polymerization reactions. For example, heat removal is associated with technological difficulties due to the high viscosity of the reaction mass (especially when polymers are formed in solution). High viscosity increases the overall thermal resistance of the reactor and gives rise to a tendency to deteriorate mixing and turbulence inside the reactor, making the properties of polymers suboptimal. Moreover, heat removal is associated with technological difficulties due to contamination of the reactor (especially when polymers form as a suspension in a diluent or as a suspension in monomers without a diluent). The polymer contamination layer also increases the overall thermal resistance of the reactor and leads to clogging, uneven mixing and flows within the reactor.

Moreover, due to the above two limiting factors, it is difficult to keep the temperature inside the reactor at a constant target. Temperature control during polymerization reactions is usually significant because it affects not only the kinetics of chain growth (chain formation reaction), but also the kinetics of transfer and / or termination (chain termination or stopping chain growth). Therefore, temperature affects everything: molecular weight, molecular weight distribution, comonomer incorporation rates, etc. In addition, the reaction temperature usually affects the activity of the catalyst.

Therefore, there is a need to develop new polymerization methods and new reactor system designs using alternative diluents or diluent mixtures to create new polymerization systems that reduce particle agglomeration and / or reduce the amount of chlorinated hydrocarbons such as methyl chloride. Such new polymerization methods and reactor system designs would reduce particle agglomeration and reactor fouling without compromising process parameters, conditions or components and / or without compromising performance / throughput and / or the possibility of producing high molecular weight polymers. Moreover, it would also be advisable to develop new polymerization methods and reactor system designs that use alternative diluents or diluent mixtures to create less complex structures compared to conventional systems and methods.

Fluorocarbons (FUVs) are of interest since they are currently used as environmentally friendly refrigerants because they have a very low (even zero) ozone depleting potential. Their low ozone depleting potential is believed to be associated with a lack of chlorine. FUVs also typically have low flammability, in particular when compared with hydrocarbons and chlorinated hydrocarbons.

References to descriptions of other known technical solutions include WO 02/34794, which proposes a free radical polymerization process using fluorocarbons. References to descriptions of other known technical solutions include DE 10061727 A, WO 02/096964, WO 00/04061, US No. 5624878, US No. 5527870 and US No. 3470143.

SUMMARY OF THE INVENTION

The object of the present invention is a new polymerization system and methods using fluorocarbons to obtain polymers.

The object of the present invention are also polymerization methods, including contacting in a reactor under polymerization conditions of one or more monomers, a catalytic system in the presence of a diluent containing one or more fluorocarbons (FUV).

In particular, an object of the invention is a polymerization method, comprising contacting in the reactor system at least one first stream of starting materials and at least one second stream of starting materials for an effective time, which includes a diluent containing one or more fluorocarbons (HFCs).

The invention also relates to a polymerization process comprising contacting a catalyst system and at least one monomer for an effective contact time and at a flow velocity of from about 0.5 to about 400 m / s, which comprises a diluent containing at least one fluorocarbon (FUV )

However, in yet another embodiment of the invention, its object is a polymerization method, comprising contacting the catalytic system and one or more monomers in a microdroplet of a polymerization medium comprising one or more fluorocarbons (FUV).

In any of the preceding embodiments, the polymerization processes can be carried out using reactor systems with turbulent flows, in which there are streams of raw materials in contact during the contact periods indicated in the present description.

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 shows the design of the device of the injection head.

Figure 2 shows a diagram of a reactor system.

Figure 3 shows a diagram of the experimental setup described in the examples.

DETAILED DESCRIPTION OF THE INVENTION

The following describes the various specific options, versions and examples of carrying out the invention, including the preferred options and definitions that are presented in the present description in order to understand the essence of the claimed invention. To determine a violation of the scope of the “invention”, reference should be made to any one or more of the appended claims, including their equivalents and elements or limitations, which are equivalent to those listed.

Taking into account the objectives of the present invention and the claims, the term "catalytic system" refers to and encompasses any Lewis acid (s) or other complex (s) used to catalyze the polymerization of olefin monomers of the invention, as well as at least one initiator and optional another small catalytic component (s).

In one embodiment of the invention, there is provided a polymerization medium suitable for the polymerization of one or more monomers to produce a polymer, the polymerization medium comprising one or more Lewis acids, one or more initiators, and a diluent comprising one or more fluorocarbons.

In another embodiment, the invention provides a polymerization medium suitable for the polymerization of one or more monomers to produce a polymer, the polymerization medium comprising one or more Lewis acids and a diluent comprising one or more fluorocarbons (FUV), where one or more Lewis acids are not compounds represented by the formula MX ₃ , in which M represents a metal of group 13, and X represents a halogen atom.

The expression "acceptable for the polymerization of monomers to obtain a polymer" refers to the choice of polymerization conditions and components, which is within the competence of specialists in the art, necessary to obtain the target polymer, taking into account the technological parameters and properties of the components presented in the present description. There are numerous variations of the polymerization process and variations of the available polymerization components to achieve the characteristic features of the target polymer. In preferred embodiments, such polymers include isobutylene homopolymers, isobutylene-isoprene (butyl rubber) copolymers, isobutylene and para-methyl styrene copolymers, and star-shaped butyl rubber triple copolymers.

A diluent is a diluent or solvent. The term “diluent” is specifically defined as encompassing chemicals that can act as solvents for Lewis acids, other metal complexes, initiators, monomers, or other additives. In carrying out the invention, the diluent does not change the general nature of the components of the polymerization medium, i.e. components of the catalytic system, monomers, etc. However, it is known that interactions can occur between the diluent and the reactants. In preferred embodiments, the diluent does not interact to any extent with the components of the catalyst system, monomers, etc. In addition, the term “diluent” encompasses mixtures of at least two or more diluents.

A reactor is any vessel (vessels) in which a chemical interaction occurs.

A reactor system is any system that includes a reactor and all the necessary and optional equipment used in the preparation of polymers.

A turbulent flow reactor system is a reactor system in which the starting monomer and the catalyst system or components of the catalyst system (collectively starting materials or feed streams) are combined in such a way as to facilitate mixing at flow rates necessary to provide the desired turbulent mixing of the flows starting materials over a period of time, also known as contact time, required for the reaction to proceed. In some embodiments, the turbulent flow reactor system is called a reactor system including a reactor in which the Reynolds number (Perry's Chemical Engineers Handbook (7th edition) edited by RHPerry and DWGreen, 1977, McGraw Hill) of the reaction stream exceeds 10,000, which serves as an indication of the nature of the mixing occurring in the reaction stream.

The contact time is the time from the moment when the feed streams are combined to form the reaction stream, until the moment when the reaction stream comes into contact with the quenching medium, thus stopping the reaction. Effective contacting time is any period defined above and corresponding to information on polymerization processes and reactor systems described in the present description. In view of the objectives of the present invention, contact time and length of stay should be understood as equivalent concepts.

The contact periods used to carry out the present invention are, although not limited to, from less than 30 s, in another embodiment from less than 20 s, in another embodiment from less than 15 s, in another embodiment from less than 12 s, in another embodiment from less than 10 s, in another embodiment from less than 8 s, in another embodiment from less than 5, in another embodiment from less than 3 s, in another embodiment from less than 1 s, in another embodiment from less than 0.1 s, in another embodiment from less than 0.01 s and, in another embodiment, less than 0.001 s.

In one embodiment, the combination of feed streams passing through nozzles provided in the injection head causes the formation of a fine aerosol from microdroplets. A microdroplet is a fluid particle with a diameter of from about 0.4 to 1000 microns, although the scope of the present invention does not necessarily exclude larger particles.

In some embodiments, a droplet is called a fluid particle with a diameter of from about 0.4 to about 1000 microns, in another embodiment, a droplet is a fluid particle with a diameter of from about 1 to about 900 microns, in another embodiment, a fluid droplet is a fluid particle with a diameter of from about 10 to about 800 microns, in another embodiment, a microdroplet is a fluid particle with a diameter of from about 20 to about 600 microns, or in another embodiment, a microdroplet is a fluid particle with a diameter of from about 30 to about 400 microns.

In other embodiments, a microdroplet is a liquid particle with a diameter of 1000 μm or less, in another embodiment 600 μm or less, in another embodiment 400 microns or less, in another embodiment 100 microns or less, in another embodiment 50 microns or less, according to another embodiment 40 microns or less, in another embodiment 30 microns or less, in another embodiment 10 microns or less, or in another embodiment 1 micron or less.

In yet another embodiment, a microdroplet is a fluid particle with a diameter of 1000 microns or more.

The term "suspension" refers to the volume of the diluent, including polymers that precipitated from the diluent, monomers and catalyst system. The concentration of the suspension is expressed in volume percent of the partially or completely precipitated polymers in terms of the total volume of the suspension.

As a new numbering scheme for the groups of the Periodic table of elements in the present description, the scheme used is presented in Chemical and Engineering News, 63 (5), 27 (1985).

The term "polymer" can be used as encompassing homopolymers, copolymers, ternary copolymers, etc. Similarly, the term “copolymer” may refer to a polymer comprising units of at least two monomers, optionally with units of other monomers.

When a polymer is referred to as comprising a monomer, this monomer is contained in the polymer in the polymerized form of the monomer or in the form of a derivative of this monomer. Similarly, when the catalytic components are described as including components in neutral stable forms, it will be readily apparent to those skilled in the art that the ionic form of the component is the form in which it reacts with monomers to form polymers.

The term "isoolefin" refers to any olefin monomer having two substitutions on the same carbon atom.

The term "multiolefin" refers to any monomer having two double bonds.

The term "isobutylene-based polymer" refers to polymers comprising at least 80 mol% of repeating units of isobutylene.

The terms "elastomer" and "elastomeric composition", as used herein, refer to any polymer or polymer composition meeting the definition of ASTM D1566. These concepts can be used interchangeably with the term "rubber (rubbers)" used in the present description.

The term “alkyl” refers to a paraffinic hydrocarbon group that can be derivatized from an alkane by removing one or more hydrogen atoms from this compound, in particular, such as a methyl group (CH ₃ ), an ethyl group (CH ₃ CH ₂ ), etc.

The term “aryl” refers to a hydrocarbon group that forms a ring structure characteristic of aromatic compounds such as, for example, benzene, naphthalene, phenanthrene, anthracene, etc., and typically has an alternating double bond (“unsaturation” within its structure) "). Thus, an aryl group is a group derivatized from an aromatic compound by removing one or more hydrogen atoms from this compound, in particular such as phenyl or C ₆ H ₅ -.

By the term “substituted” is meant the substitution of at least one hydrogen group with at least one substituent selected, for example, from a halogen atom (chlorine, bromine, fluorine or iodine), an amino group, nitro, sulfoxy (sulfonate or alkyl sulfonate), thiol, alkylthiol and hydroxyl; alkyl, straight or branched, containing from 1 to 20 carbon atoms, examples of which include methyl, ethyl, propyl, tert-butyl, isopropyl, isobutyl, etc .; alkoxy, straight or branched alkoxy containing from 1 to 20 carbon atoms, examples of which include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, secondary butoxy, tertiary butoxy, pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy and decyloxy; haloalkyl, which is straight chain or branched alkyl containing from 1 to 20 carbon atoms, which is substituted by at least one halogen atom, examples of which include chloromethyl, bromomethyl, fluoromethyl, iodomethyl, 2-chloroethyl, 2-bromoethyl, 2-fluoroethyl, 3-chloropropyl, 3-bromopropyl, 3-fluoropropyl, 4-chlorobutyl, 4-fluorobutyl, dichloromethyl, dibromomethyl, difluoromethyl, diiodomethyl, 2,2-dichloroethyl, 2,2-dibromomethyl, 2,2-difluoroethyl, 3,3- dichloropropyl, 3,3-difluoropropyl, 4,4-dichlorobutyl, 4,4-difluorobutyl, trichloromethyl, 4,4-difluorobutyl, trichloromethyl, tr fluoromethyl, 2,2,2-trifluoroethyl, 2,3,3-trifluoropropyl, 1,1,2,2-tetrafluoroethyl, and 2,2,3,3-tetrafluoropropyl. Thus, in particular, examples of the “substituted styrene unit” include units of n-methyl styrene, n-ethyl styrene, etc.

In one embodiment, an object of the present invention is the use of fluorocarbons (fluorocarbons) or mixtures of fluorocarbons (fluorocarbons) with hydrocarbon (s) and / or chlorinated hydrocarbon (s) to form a polymer slurry that is less prone to contamination (i.e., in a reaction vessel) more glassy, less sticky particles with reduced adhesion to the walls of the vessel or to the impeller of the mixer, as well as reduced agglomeration of the particles between themselves) are also observed. More specifically, an object of the present invention is the use of fluorocarbon diluent (s) or mixtures of HFC diluents with hydrocarbons and / or mixtures of chlorinated hydrocarbons in the polymerization and copolymerization of isoolefins with dienes and / or alkyl styrenes to produce isoolefin homopolymers and copolymers with significantly reduced reactor fouling. Further, the present invention relates to the use of fluorocarbon diluent (s) or mixtures of diluents with hydrocarbons and / or mixtures of chlorinated hydrocarbons in the polymerization and copolymerization of isoolefins with dienes to produce isoolefin copolymers with significantly reduced reactor fouling and, consequently, a longer reactor operating period if Compare with conventional systems.

In one embodiment, the object of the present invention is the creation of new polymerization systems using diluents containing fluorocarbons. These diluents effectively dissolve the selected catalyst system and monomers, but are relatively poor solvents for the polymer product. Polymerization systems that use these diluents are less prone to the formation of contaminants due to the agglomeration of polymer particles with each other and their deposition on polymerization equipment. In addition, an object of the present invention is the use of these diluents in polymerization systems for the production of high molecular weight polymers and copolymers at temperatures that are equivalent or higher than the polymerization temperatures using only chlorinated hydrocarbon diluents such as methyl chloride.

In another embodiment, the object of the present invention is the creation of new polymerization systems using fluorinated aliphatic hydrocarbons capable of dissolving the catalyst system. These polymerization systems are also beneficial for the suspension polymerization of isoolefins and to obtain a polymer suspension, which is less prone to the formation of contaminants and at the same time allows the monomer, comonomer and technically preferred alkylaluminohalide catalysts to be dissolved. In addition, an object of the present invention is the use of these diluents to obtain high molecular weight polymers and copolymers at higher polymerization temperatures, when compared with polymerization systems that use only chlorinated hydrocarbon diluents, such as methyl chloride.

However, in yet another embodiment, an object of the present invention is to provide isoolefin homopolymers and copolymers, primarily the polymerization reaction, necessary to produce the isobutylene-isoprene form of butyl rubber and isobutylene / p-alkyl styrene copolymers. More specifically, an object of the invention is a method for the polymerization and copolymerization of isoolefins by a suspension polymerization method using fluorocarbon diluents or mixtures of fluorocarbons and chlorinated hydrocarbon diluents like methyl chloride.

In another embodiment, the polymerization systems of the present invention provide for the copolymerization of an isomonoolefin containing from 4 to 7 carbon atoms and para-alkyl styrene monomers. In accordance with a preferred embodiment of the invention, such a system provides copolymers containing in the range of about 80 to 99.5% by weight of an isoolefin, such as isobutylene, and in the range of about 0.5 to 20%, of para-alkyl styrene, such like para-methyl styrene. However, in another embodiment, which also produces glass-like or plastic materials, the copolymers include in the range of about 10 to 99.5% by weight of isoolefin or isobutylene and about 0.5 to 90% by weight of para-alkyl styrene, such as para-methyl styrene.

In a preferred embodiment of the present invention, its object is a method for producing polymers from cationically polymerizable monomer (s), comprising contacting in the reactor the monomer (s), Lewis acid and initiator in the presence of an HFC diluent at a temperature of 0 ° C or lower, preferably -10 ° C or lower, more preferably -20 ° C or lower, more preferably -30 ° C or lower, preferably -40 ° C or lower, preferably -50 ° C or lower, preferably -60 ° C or lower, preferably -70 ° C or lower preferably −80 ° C. or lower, preferably −90 ° C. or lower, preferably −100 ° C. or lower, preferably from 0 ° C. to the freezing point of the polymerization medium, such as a diluent and a monomer mixture.

Monomers and Polymers

Monomers that can be polymerized in this system include any hydrocarbon monomer that can be polymerized using the present invention. Preferred monomers include one or more olefins, alpha olefins, disubstituted olefins, isoolefins, conjugated dienes, non-conjugated dienes, styrenes and / or substituted styrenes and vinyl ethers. Styrene can be substituted (in the ring) with an alkyl, aryl, halide or alkoxide group. In a preferred embodiment, the monomer contains from 2 to 20 carbon atoms, more preferably from 2 to 9, even more preferably from 3 to 9 carbon atoms. Examples of preferred olefins include styrene, para-alkyl styrene, para-methyl styrene, alpha-methyl styrene, divinylbenzene, diisopropenylbenzene, isobutylene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-pentene, isoprene, butadiene, 2,3-dimethyl-1,3-butadiene, β-pinene, myrcene, 6,6-dimethylfulvene, hexadiene, cyclopentadiene, piperylene, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether and the like. Combinations of two or more monomers may also serve as monomer. Styrene block copolymers can also be used as monomers. Preferred block copolymers include copolymers of styrenes such as styrene, para-methyl styrene, alpha-methyl styrene, and C ₄ to C ₃₀ diolefins such as isoprene, butadiene, and the like. Particularly preferred combinations of monomers include 1) isobutylene and para-methylstyrene, 2) isobutylene and isoprene, as well as isobutylene homopolymers.

Moreover, preferred monomers include those that are capable of cationically polymerizing, as described in Cationic Polymerization of Olefins, A Critical Inventory, Joseph Kennedy, Wiley Interscience, New York 1975. Monomers include any monomer that is capable of cationically polymerizing, such as those monomers that are capable of stabilizing a cation or chain growth center, since the monomer contains an electron-donating group. For a detailed discussion of cationic catalysis, it is recommended that Cationic Polymerization of Olefins, A Critical Inventory, Joseph Kennedy, Wiley Interscience, New York 1975.

Monomers can be contained in the polymerization medium in an amount in the range from 75 to 0.01 wt.% In one embodiment, in another embodiment from 60 to 0.1 wt.%, In another embodiment from 40 to 0.2 wt.% , in another embodiment, from 30 to 0.5 wt.%, in another embodiment, from 20 to 0.8 wt.% and from 15 to 1 wt.% in another embodiment.

Preferred polymers include homopolymers from any of the monomers listed in this section. Examples of homopolymers include polyisobutylene, poly-para-methylstyrene, polyisoprene, polystyrene, poly-alpha-methylstyrene, polyvinyl ethers (such as polymethyl vinyl ether, polyethyl vinyl ether).

Preferred polymers also include copolymers of 1) isobutylene and alkylstyrene and 2) isobutylene and isoprene.

In one embodiment, butyl polymers are prepared by reacting in a comonomer mixture, a mixture comprising at least (1) a C ₄ to C ₆ isoolefin monomer component, such as isobutene, with a (2) multi-olefin or conjugated diene monomer component. The isoolefin is contained in the range from 70 to 99.5 wt.% By weight of the entire mixture of comonomers in one embodiment, from 85 to 99.5 wt.% In another embodiment. However, in yet another embodiment, the isoolefin is in the range of 92 to 99.5% by weight. The conjugated diene component is contained in a mixture of comonomers in an amount of from 30 to 0.5 wt.% In one embodiment and from 15 to 0.5 wt.% In another embodiment. However, in another embodiment, from 8 to 0.5 wt.% Of the mixture of comonomers falls on the conjugated diene. The C ₄ to C ₆ isoolefin may be one or more of isobutene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene and 4-methyl-1-pentene. The C ₄ to C ₁₄ conjugated diene such as isoprene, butadiene, 2,3-dimethyl-1,3-butadiene, β-pinene, myrcene, 6,6-dimethylfulvene, hexadiene, cyclopentadiene and piperylene can serve as a multiolefin. One embodiment of the butyl rubber polymer of the invention is prepared by reacting from 85 to 99.5% by weight of isobutylene and from 15 to 0.5% by weight of isoprene, or in another embodiment by reacting from 95 to 99.5% by weight of isobutylene and from 5 , 0 to 0.5 wt.% Isoprene. The following table illustrates how the above amounts in wt.% Would be expressed in molar%.

IP ₄ ^a , mol% IP ₄ , mol% IP ₅ ^b , mol% IP ₅ , mol% 70 73.9 0.5 0.4 85 87.3 5 4.2 92 93.3 8 6.7 95 95.9 fifteen 12.7 99.5 99.6 thirty 26.1

but. IP ₄ stands for isobutylene.

b. IP ₅ stands for Isoprene.

In addition, an object of the present invention are ternary copolymers and quaternary copolymers, including any combination of monomers listed above. Preferred ternary copolymers and quaternary copolymers include polymers containing isobutylene, isoprene and divinylbenzene, polymers containing isobutylene, para-alkyl styrene (preferably para-methyl styrene) and isoprene, polymers containing cyclopentadiene, isobutylene and para-alkyl styrene (preferably para-methyl styrene), polymers of isobutylene, cyclopentadiene and isoprene, polymers containing cyclopentadiene, isobutylene and methylcyclopentadiene, polymers containing isobutylene, para-methylstyrene and cyclopentadiene.

Lewis Acid

Any Lewis acid based on metals of Groups 4, 5, 13, 14 and 15 of the Periodic Table of the Elements, including boron, aluminum, gallium, indium, titanium, zirconium, tin, vanadium, can serve as a Lewis acid (also called a co-initiator or catalyst). arsenic, antimony and bismuth. It will be apparent to those skilled in the art that certain elements are better suited to carrying out the invention. In one embodiment, such metals are aluminum, boron and titanium, the target being aluminum. Illustrative examples include AlCl ₃ , (alkyl) AlCl ₂ , (C ₂ H ₅ ) ₂ AlCl and (C ₂ H ₅ ) ₃ Al ₂ Cl ₃ , BF ₃ , SnCl ₄ , TiCl ₄ .

Moreover, the Lewis acids can be any of those that can be used in the process of cationic polymerization to produce isobutylene copolymers, including aluminum trichloride, aluminum tribromide, ethylaluminodichloride, ethylaluminosesquichloride, diethylaluminochloride, methylaluminodichloride, tetrachloride, dimethylchloride, dimethyl chloride, tetrachloride, dimethylchloride, dimethylchloride, dimethylchloride, dimethyl chloride. e., and ethylaluminodichloride and ethylaluminosesquichloride are preferred.

Considering the essence of the invention, acceptable Lewis acids are also Lewis acids such as methylaluminoxane (MAO) and specially designed weakly coordinating Lewis acids, such as B (C ₆ F ₅ ) ₃ .

As is known to those skilled in the art, the above list of Lewis acids is not exhaustive, but is presented for illustration. For additional information regarding Lewis acids in polymerization processes, please refer, for example, to international applications No. PCT / US 03/40903 and PCT / US 03/40340.

Initiator

The initiators that can be used in carrying out the present invention are those initiators that are capable of complexing in an acceptable diluent with the selected Lewis acid, resulting in a complex that rapidly interacts with the olefin, thereby forming a growing polymer chain. Illustrative examples include Bronsted acids such as H ₂ O, HCl, RCOOH (where R is an alkyl group), and alkyl halides such as (CH ₃ ) ₃ CCl, C ₆ H ₅ C (CH ₃ ) ₂ Cl and (2- chloro-2,4,4-trimethylpentane). Later, to initiate the polymerization of isobutylene, transition metal complexes, such as metallocenes and other such materials, which can act as catalytic systems with a single site, in particular, when they are activated by weakly coordinating Lewis acids or Lewis acid salts, were used.

In one embodiment, the initiator includes one or more of hydrogen halide, carboxylic acid, carboxylic acid halide, sulfonic acid, alcohol, phenol, tertiary alkyl halide, tertiary aralkyl halide, tertiary aliphatic ester, tertiary araliphatic ester, tertiary aliphatic ether, tertiary aliphatic ether, ether, alkyl halide, aryl halide, alkyl aryl halide and arylaliphatic acid halide.

As is known to a person skilled in the art, the above list of initiators is not exhaustive, but is presented for illustration. For additional information about the initiator (s) in the polymerization processes, you should refer, for example, to international applications No. PCT / US 03/40903 and PCT / US 03/40340.

Fluorocarbons

In a preferred embodiment, fluorocarbons are used as diluents in carrying out the present invention (alone or in combination with other fluorocarbons or in combination with other diluents). In view of the objectives of the present invention and the claims, fluorocarbons (“HFCs”) are understood to mean saturated or unsaturated compounds consisting essentially of hydrogen, carbon and fluorine atoms, provided that they contain at least one carbon atom, at least one hydrogen atom and at least one fluorine atom.

In some embodiments, the diluent includes fluorocarbons represented by the formula: C _x H _y F _z in which x represents an integer from 1 to 40, in another embodiment from 1 to 30, in another embodiment from 1 to 20, in another embodiment from 1 to 10, in another embodiment from 1 to 6, in another embodiment from 2 to 20, in another embodiment from 3 to 10, in another embodiment from 3 to 6, most preferably from 1 to 3, and in which y and z are integers comprising at least one.

Illustrative examples include fluoromethane, difluoromethane, trifluoromethane, fluoroethane, 1,1-difluoroethane, 1,2-difluoroethane, 1,1,1-trifluoroethane, 1,1,2-trifluoroethane, 1,1,1,2-tetrafluoroethane, 1 , 1,2,2-tetrafluoroethane, 1,1,1,2,2-pentafluoroethane, 1-fluoropropane, 2-fluoropropane, 1,1-difluoropropane, 1,2-difluoropropane, 1,3-difluoropropane, 2,2 -difluoropropane, 1,1,1-trifluoropropane, 1,1,2-trifluoropropane, 1,1,3-trifluoropropane, 1,2,2-trifluoropropane, 1,2,3-trifluoropropane, 1,1,1,2 -tetrafluoropropane, 1,1,1,3-tetrafluoropropane, 1,1,2,2-tetrafluoropropane, 1,1,2,3-tetrafluoropropane, 1,1,3,3-tetrafluoropropane, 1,2,2,3 -tetrafluoropropane, 1,1,1,2,2-pentafluoropropane, 1,1,1,2,3 pentafluoropropane, 1,1,1,3,3-pentafluoropropane, 1,1,2,2,3-pentafluoropropane, 1,1,2,3,3-pentafluoropropane, 1,1,1,2,2,3 -hexafluoropropane, 1,1,1,2,3,3-hexafluoropropane, 1,1,1,3,3,3,3-hexafluoropropane, 1,1,1,2,2,3,3-heptafluoropropane, 1,1 , 1,2,3,3,3-heptafluoropropane, 1-fluorobutane, 2-fluorobutane, 1,1-difluorobutane, 1,2-difluorobutane, 1,3-difluorobutane, 1,4-difluorobutane, 2,2-difluorobutane , 2,3-difluorobutane, 1,1,1-trifluorobutane, 1,1,2-trifluorobutane, 1,1,3-trifluorobutane, 1,1,4-trifluorobutane, 1,2,2-trifluorobutane, 1,2 , 3-trifluorobutane, 1,3,3-trifluorobutane, 2,2,3-trifluorobutane, 1,1,1,2-tetrafluorobutane, 1,1,1,3-tetrafluorobutane, 1,1,1,4-tetrafluorobutane 1,1,2,2-tetrafluorobuta 1,1,2,3-tetrafluorobutane, 1,1,2,4-tetrafluorobutane, 1,1,3,3-tetrafluorobutane, 1,1,3,4-tetrafluorobutane, 1,1,4,4-tetrafluorobutane , 1,2,2,3-tetrafluorobutane, 1,2,2,4-tetrafluorobutane, 1,2,3,3-tetrafluorobutane, 1,2,3,4-tetrafluorobutane, 2,2,3,3-tetrafluorobutane 1,1,1,2,2-pentafluorobutane 1,1,1,2,3-pentafluorobutane 1,1,1,2,4-pentafluorobutane 1,1,1,3,3-pentafluorobutane 1 1,1,3,4-pentafluorobutane 1,1,1,4,4-pentafluorobutane 1,1,2,2,3-pentafluorobutane 1,1,2,2,4-pentafluorobutane 1,1 , 2,3,3-pentafluorobutane, 1,1,2,4,4-pentafluorobutane, 1,1,3,3,4-pentafluorobutane, 1,2,2,3,3-pentafluorobutane, 1,2,2 , 3,4-pentafluorobutane, 1,1,1,2,2,3-hexafluorobutane, 1,1,1,2,2,4-hexafluorobutane, 1,1,1,2,3,3- exafluorobutane, 1,1,1,2,3,4-hexafluorobutane, 1,1,1,2,4,4-hexafluorobutane, 1,1,1,3,3,4-hexafluorobutane, 1,1,1, 3,4,4-hexafluorobutane, 1,1,1,4,4,4-hexafluorobutane, 1,1,2,2,3,3-hexafluorobutane, 1,1,2,2,3,4-hexafluorobutane, 1,1,2,2,4,4-hexafluorobutane, 1,1,2,3,3,4-hexafluorobutane, 1,1,2,3,4,4-hexafluorobutane, 1,2,2,3, 3,4-hexafluorobutane, 1,1,1,2,2,3,3-heptafluorobutane, 1,1,1,2,2,4,4-heptafluorobutane, 1,1,1,2,2,3, 4-heptafluorobutane, 1,1,1,2,3,3,4-heptafluorobutane, 1,1,1,2,3,4,4-heptafluorobutane, 1,1,1,2,4,4,4- heptafluorobutane, 1,1,1,3,3,4,4-heptafluorobutane, 1,1,1,2,2,3,3,4-octafluorobutane, 1,1,1,2,2,3,4, 4-octafluorobutane, 1,1,1,2,3,3,4,4-octafluorobutane, 1,1,1,2,2,4,4,4-octafluorobutane, 1,1,1,2,3, 4,4,4-octa torbutane, 1,1,1,2,2,3,3,4,4-nonafluorobutane, 1,1,1,2,2,3,4,4,4-nonafluorobutane, 1-fluoro-2-methylpropane, 1,1-difluoro-2-methylpropane, 1,3-difluoro-2-methylpropane, 1,1,1-trifluoro-2-methylpropane, 1,1,3-trifluoro-2-methylpropane, 1,3-difluoro- 2- (fluoromethyl) propane, 1,1,1,3-tetrafluoro-2-methylpropane, 1,1,3,3-tetrafluoro-2-methylpropane, 1,1,3-trifluoro-2- (fluoromethyl) propane, 1,1,1,3,3-pentafluoro-2-methylpropane, 1,1,3,3-tetrafluoro-2- (fluoromethyl) propane, 1,1,1,3-tetrafluoro-2- (fluoromethyl) propane, fluorocyclobutane, 1,1-difluorocyclobutane, 1,2-difluorocyclobutane, 1,3-difluorocyclobutane, 1,1,2-trifluorocyclobutane, 1,1,3-trifluorocyclobutane, 1,2,3-trifluorocyclobutane, 1,1, 2,2-tetrafluorocyclobutane, 1,1,3,3-tetrafluorocyclobutane, 1,1,2,2,3-pentafluorocyclobutane, 1,1,2,3,3-pentafluorocyclobutane, 1,1,2,2,3, 3-hexafluorocyclobutane, 1,1,2,2,3,4-hexafluorocyclobutane, 1,1,2,3,3,4-hexafluorocyclobutane, 1,1,2,2,3,3,4-heptafluorocyclobutane and mixtures thereof , including mixtures of unsaturated FEV presented below. Particularly preferred HFCs include difluoromethane, trifluoromethane, 1,1-difluoroethane, 1,1,1-trifluoroethane, fluoromethane and 1,1,1,2-tetrafluoroethane.

Illustrative examples of unsaturated fluorocarbons include vinyl fluoride, 1,1-difluoroethene, 1,2-difluoroethene, 1,1,2-trifluoroethene, 1-fluoropropene, 1,1-difluoropropene, 1,2-difluoropropene, 1,3-difluoropropene, 2 , 3-difluoropropene, 3,3-difluoropropene, 1,1,2-trifluoropropene, 1,1,3-trifluoropropene, 1,2,3-trifluoropropene, 1,3,3-trifluoropropene, 2,3,3-trifluoropropene , 3,3,3-trifluoropropene, 1-fluoro-1-butene, 2-fluoro-1-butene, 3-fluoro-1-butene, 4-fluoro-1-butene, 1,1-difluoro-1-butene , 1,2-difluoro-1-butene, 1,3-difluoropropene, 1,4-difluoro-1-butene, 2,3-difluoro-1-butene, 2,4-difluoro-1-butene, 3.3 difluoro-1-butene, 3,4-difluoro-1-butene, 4,4-difluoro-1-butene, 1,1,2-trift p-1-butene, 1,1,3-trifluoro-1-butene, 1,1,4-trifluoro-1-butene, 1,2,3-trifluoro-1-butene, 1,2,4-trifluoro- 1-butene, 1,3,3-trifluoro-1-butene, 1,3,4-trifluoro-1-butene, 1,4,4-trifluoro-1-butene, 2,3,3-trifluoro-1- butene, 2,3,4-trifluoro-1-butene, 2,4,4-trifluoro-1-butene, 3,3,4-trifluoro-1-butene, 3,4,4-trifluoro-1-butene, 4,4,4-trifluoro-1-butene, 1,1,2,3-tetrafluoro-1-butene, 1,1,2,4-tetrafluoro-1-butene, 1,1,3,3-tetrafluoro- 1-butene, 1,1,3,4-tetrafluoro-1-butene, 1,1,4,4-tetrafluoro-1-butene, 1,2,3,3-tetrafluoro-1-butene, 1,2, 3,4-tetrafluoro-1-butene, 1,2,4,4-tetrafluoro-1-butene, 1,3,3,4-tetrafluoro-1-butene, 1,3,4,4-tetrafluoro-1- butene, 1,4,4,4-tetrafluoro-1-butene, 2,3,3,4-tetrafluoro-1-butene, 2,3,4,4-tetrafluoro-1-butene ene, 2,4,4,4-tetrafluoro-1-butene, 3,3,4,4-tetrafluoro-1-butene, 3,4,4,4-tetrafluoro-1-butene, 1,1,2, 3,3-pentafluoro-1-butene, 1,1,2,3,4-pentafluoro-1-butene, 1,1,2,4,4-pentafluoro-1-butene, 1,1,3,3, 4-pentafluoro-1-butene, 1,1,3,4,4-pentafluoro-1-butene, 1,1,4,4,4-pentafluoro-1-butene, 1,2,3,3,4- pentafluoro-1-butene, 1,2,3,4,4-pentafluoro-1-butene, 1,2,4,4,4-pentafluoro-1-butene, 2,3,3,4,4-pentafluoro- 1-butene, 2,3,4,4,4-pentafluoro-1-butene, 3,3,4,4,4-pentafluoro-1-butene, 1,1,2,3,3,4-hexafluoro- 1-butene, 1,1,2,3,4,4-hexafluoro-1-butene, 1,1,2,4,4,4-hexafluoro-1-butene, 1,2,3,3,4, 4-hexafluoro-1-butene, 1,2,3,4,4,4-hexafluoro-1-butene, 2,3,3,4,4,4-hexafluoro -! - butene, 1,1,2, 3,3,4,4-heptafluoro-1-butene, 1,1,2,3,4,4,4-heptafluoro-1-b ten, 1,1,3,3,4,4,4-heptafluoro-1-butene, 1,2,3,3,4,4,4-heptafluoro -! - butene, 1-fluoro-2-butene, 2-fluoro-2-butene, 1,1-difluoro-2-butene, 1,2-difluoro-2-butene, 1,3-difluoro-2-butene, 1,4-difluoro-2-butene, 2, 3-difluoro-2-butene, 1,1,1-trifluoro-2-butene, 1,1,2-trifluoro-2-butene, 1,1,3-trifluoro-2-butene, 1,1,4- trifluoro-2-butene, 1,2,3-trifluoro-2-butene, 1,2,4-trifluoro-2-butene, 1,1,1,2-tetrafluoro-2-butene, 1,1,1, 3-tetrafluoro-2-butene, 1,1,1,4-tetrafluoro-2-butene, 1,1,2,3-tetrafluoro-2-butene, 1,1,2,4-tetrafluoro-2-butene, 1,2,3,4-tetrafluoro-2-butene, 1,1,1,2,3-pentafluoro-2-butene, 1,1,1,2,4-pentafluoro-2-butene, 1,1, 1,3,4-pentafluoro-2-butene, 1,1,1,4,4-pentafluoro-2-butene, 1,1,2,3,4-pentafluoro-2-butene, 1,1,2, 4,4-penta tor-2-butene, 1,1,1,2,3,4-hexafluoro-2-butene, 1,1,1,2,4,4-hexafluoro-2-butene, 1,1,1,3, 4,4-hexafluoro-2-butene, 1,1,1,4,4,4-hexafluoro-2-butene, 1,1,2,3,4,4-hexafluoro-2-butene, 1,1, 1,2,3,4,4-heptafluoro-2-butene, 1,1,1,2,4,4,4-heptafluoro-2-butene and mixtures thereof, including mixtures of the saturated PVFs presented above.

In one embodiment, the diluent includes non-perfluorinated compounds, or the diluent is a non-perfluorinated diluent, wherein the perforated compounds are those that include carbon and fluorine atoms. However, in another embodiment, when the diluent comprises a mixture, the mixture may contain a perfluorinated compound. In a preferred embodiment, the catalyst, monomer and diluent are contained in a single phase or the above components are capable of mixing with the diluent as described in further detail below. In another embodiment, the mixture may also include chlorofluorocarbons (CFCs) or those compounds that contain chlorine, fluorine and carbon atoms.

In another embodiment, when higher weight average molecular weights (Mw) are required (typically Mw greater than 10,000, preferably Mw greater than 50,000, more preferably Mw greater than 100,000), suitable diluents include fluorocarbons with a dielectric constant at -85 ° C greater than 10, preferably greater 15, more preferably more than 20, more preferably more than 25, more preferably 40 or more. In embodiments where lower molecular weights are required (typically Mw less than 10,000, preferably Mw less than 5,000, more preferably Mw less than 3,000), the dielectric constant may be less than 10 or, when the dielectric constant exceeds 10, more significant amounts of initiator or regulator are added degree of polymerization. The dielectric constant of the diluent ε _D is determined by measuring the electric capacitance of a plate capacitor immersed in the diluent [measure the value of C _D ] in a reference fluid with a known dielectric constant ε _R [measure the value of C _R ] in air (ε _A = 1 ) [measure the value of _{A A} ]. In each case, the value of the electric capacitance C _M is determined by the equation C _M = εC _C + C _S , where ε denotes the dielectric constant of the fluid into which the capacitor is immersed, C _C denotes the electric capacitance of the cell, and C _S denotes the parasitic electric capacitance. According to the results of these measurements, ε _D is determined by the formula ε _D = ((C _D -C _A ) ε _R + (C _R -C _D )) / (C _R -C _A ). Alternatively, a specially made instrument such as the BIC-870 from Brookhaven Instrument Corporation can be used to directly measure the dielectric constant of diluents. A comparison of the dielectric constant (s) of several selected diluents at -85 ° C is presented below.

Diluent ε at -85 ° C Methyl chloride 18.34 Difluoromethane 36.29 1,1-difluoroethane 29.33 1,1,1-trifluoroethane 22.18 1,1,1,2-tetrafluoroethane 23.25 1,1,2,2-tetrafluoroethane 11.27 1,1,1,2,2-pentafluoroethane 11.83

In other embodiments, one or more HEMs is used in combination with another diluent or mixtures of diluents. Suitable additional diluents include hydrocarbons, mainly hexanes and heptanes, halogenated hydrocarbons, mainly chlorinated hydrocarbons, and the like. Specific examples include, although not limited to, propane, isobutane, pentane, methylcyclopentane, isohexane, 2-methylpentane, 3-methylpentane, 2-methylbutane, 2,2-dimethylbutane, 2,3-dimethylbutane, 2-methylhexane, 3 -methylhexane, 3-ethylpentane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpentane, 2-methylheptane, 3-ethylhexane, 2,5-dimethylhexane, 2,2,4 trimethylpentane, octane, heptane, butane, ethane, methane, nonane, decane, dodecane, undecane, hexane, methylcyclohexane, cyclopropane, cyclobutane, cyclopentane, methylcyclopentane, 1,1-dimethylcyclopentane, cis-1,2-dime tilcyclopentane, trans-1,2-dimethylcyclopentane, trans-1,3-dimethylcyclopentane, ethylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ortho-xylene, para-xylene, meta-xylene and halogenated versions of all of the above substances, preferably chlorinated variants of the above substances, more preferably fluorinated variants of all of the above substances. Can also be used brominated variants of the above substances. Specific examples include methyl chloride, methylene chloride, ethyl chloride, propyl chloride, butyl chloride, chloroform and the like.

In another embodiment, non-reactive olefins can be used as diluents in combination with HF. Examples include, although not limited to, ethylene, propylene, and the like.

In one embodiment, the HFCs are used in combination with a chlorinated hydrocarbon such as methyl chloride. Additional options include the use of FUV in combination with hexanes or methyl chloride and hexanes. In yet another embodiment, the CFCs are used in combination with one or more polymerization inert gases, such as carbon dioxide, nitrogen, hydrogen, argon, neon, helium, krypton, xenon and / or other inert gases, which when entering the reactor are preferably in a liquid state. Preferred gases include carbon dioxide and / or nitrogen.

In another embodiment, FUVs are used in combination with one or more nitrated alkanes, including nitrated linear, cyclic and branched alkanes C ₁ through C ₄₀ . Preferred nitrated alkanes include, but are not limited to, nitromethane, nitroethane, nitropropane, nitrobutane, nitropentane, nitrohexane, nitroheptane, nitrooctane, nitrodecane, nitrononane, nitrodecodane, nitrodecane, nitrocyclopentane, nitrocyclopentane, nitrocyclopropane nitrocyclooctane, nitrocyclodecane, nitrocyclononane, nitrocyclododecane, nitrocycloundecane, nitrobenzene, as well as di and trinitrovariants of the above substances. The preferred option is FUV mixed with nitromethane.

FUV, as a rule, is contained in an amount from 1 to 100 vol.% In terms of the total volume of diluents, according to another variant, from 5 to 100 vol.%, According to another variant, from 10 to 100 vol.%, According to another variant in the range from 15 to 100 vol%, according to another variant in the range from 20 to 100 vol%, according to another variant in the range from 25 to 100 vol%, according to another variant in the range from 30 to 100 volume%, according to another option ranging from 35 to 100 vol.%, another option ranging from 40 to 100 vol.%, another option ranging from 45 to 100 vol.%, another option ranging from 50 to 100 vol.% , about another option in the range from 55 to 100 vol.%, according to another option in the range from 60 to 100 vol.%, according to another option in the range from 65 to 100 vol.%, according to another option in the range from 70 to 100 vol. %, in another embodiment, in the range of 75 to 100 vol.%, in another embodiment, in the range of 80 to 100 vol.%, in another embodiment, in the range of 85 to 100 vol.%, in another embodiment, in the range of 90 to 100 vol.%, in another embodiment, in the range of 95 to 100 vol.%, in another embodiment, in the range of 97 to 100 vol.%, in another embodiment, in the range of 98 to 100 vol.%, in another embodiment, in the range of 99 up to 100 vol.%. In a preferred embodiment, the FUV is mixed with one or more chlorinated hydrocarbons. In another preferred embodiment, the CFCs are selected from the group consisting of difluoromethane, trifluoromethane, 1,1-difluoroethane, 1,1,1-trifluoroethane, 1,1,1,2-tetrafluoroethane, and mixtures thereof.

In another embodiment, a diluent or mixture of diluents is selected based on their solubility in the polymer. Some diluents are soluble in the polymer. Preferred diluents have low to no solubility in the polymer. The solubility in the polymer is determined by forming a film from the polymer with a thickness ranging from 50 to 100 μm, then soaking it in a diluent (sufficient to cover the film) for 4 hours at -75 ° C. The film is removed from the diluent, kept at room temperature for 90 s to evaporate the excess diluent from the surface of the film and weighed. The weight gain is determined as a percentage increase in film weight after soaking. The diluent or mixture of diluents is chosen so that the polymer has a weight gain of less than 4 wt.%, Preferably less than 3 wt.%, Preferably less than 2 wt.%, Preferably less than 1 wt.%, More preferably less than 0.5 wt.%.

In a preferred embodiment, the diluent or mixture of diluents is chosen so that the difference between the set glass transition temperature Tg of the polymer with less than 0.1 wt.% Of any diluent, unreacted monomers and additives is within 15 ° C of the Tg of the polymer established after it a film is molded with a thickness ranging from 50 to 100 μm, which is pre-soaked in a diluent (sufficient to cover the film) for 4 hours at -75 ° C. The glass transition temperature is determined by differential scanning calorimetry (DSC). Methods are well represented in the literature, for example, in B. Wunderlich, "The Nature of the Glass Transition and its Determination by Thermal Analysis", in Assignment of the Glass Transition. ASTM STP 1249, R.J.Seyler, Ed., American Society for Testing and Materials, Philadelphia, 1994, pp. 17-31. The sample is prepared as described above, immediately after soaking, it is sealed in the sample tray of the DSC device and kept at a temperature below -80 ° C immediately until it is determined using DSC. In a preferred embodiment, the Tg values are within 12 ° C relative to each other, preferably within 11 ° C relative to each other, preferably within 10 ° C relative to each other, preferably within 9 ° C relative to each other, preferably within 8 ° With respect to each other, preferably within 7 ° C relative to each other, preferably within 6 ° C relative to each other, preferably within 5 ° C relative to each other, preferably within 4 ° C relative to each other, ochtitelno within 3 ° C of each other, preferably within 2 ° C with respect to each other, preferably within 1 ° C with respect to each other.

Polymerization process

The invention can be carried out by conducting continuous, semi-continuous or batch processes. In addition, the invention can be carried out in a piston flow reactor and / or in a tank type reactor with a stirrer, where the contact time of the monomer and catalyst flows is, although not limited to, less than 30 s, in another embodiment, less than 20 s , in another variant, from less than 15 s, in another variant, from less than 12 s, in another variant, from less than 10 s, in another variant, from less than 8 s, in another variant, from less than 5, in another variant, from less than 3 s, otherwise option from less than 1 s, according to another option from less than 0.1 s, p about another option from less than 0.01 s and in another option from less than 0.001 s.

Thus, in particular, the present invention can be carried out in “butyl reactors”. Illustrative examples include any reactor selected from the group consisting of a tank type reactor with a stirrer and continuous feed, a piston stream reactor, a movable belt or drum reactor, an ejector or nozzle reactor, a tubular reactor, and a boiling type self-cooling pool reactor.

In one embodiment, in polymerization processes characterized by reaction rates with short periods of contact in a turbulent flow reactor system, one or more fluorocarbons is used. In some embodiments, the system operates in accordance with the drawings. So, in particular, figure 1 provides an injection head. The injection head of the experimental setup includes two injection nozzles 3, 5 oriented at an angle of 7. Both nozzles are connected to a suitable stable support structure 9, 11, capable of maintaining a predetermined angle 7. These injection nozzles supply monomer flows and the catalyst system or catalyst system components to the reactor head and form a stream 1 as a result of collision with each other of these streams to obtain a reaction stream.

The angle 7 between the nozzles can be set in order to maximize local turbulence and mixing, which depends on the flow rates and nozzle diameters used in the reactor. This angle can have any value that causes the flows to collide with each other, including from a separation of 1 or 2 ° to a separation of 180 °, when the flows of the raw materials are directly opposed to each other. In one embodiment, the separation angle is from about 20 to about 160 °, and in another embodiment, from about 30 to about 120 °.

Nozzles suitable for the reactor system should ensure that the outflow rates of the feed monomer and catalyst are sufficient to create aerosol flows from the microdroplets around the collision point. In some embodiments, microdroplets are formed partly as a result of high local turbulence and intense mixing. Although microdroplet formation may be necessary, it is an optional requirement.

The flow rate is the ratio of the fluid flow rate, expressed as volume per unit time, to the nozzle cross-sectional area, expressed in units of square of length. The flow rates that can be used to carry out the present invention are, although their list is not limited to, from about 0.5 to about 400 m / s in one embodiment, in another embodiment from about 1 to about 100 m / s, in another embodiment, from about 1 to about 50 m / s; and in another embodiment, from about 1 to about 20 m / s.

In the examples of the construction, on a scale taken for the purpose of convenience for laboratory work, effective nozzles have internal diameters that are in the range from 0.1 to 0.8 mm when using flow rates of the initial catalyst and monomer from 20 to 200 ml / min. The selection of nozzle diameters and flow rates of the starting materials is carried out in order to maintain average flow velocities from about 1 to about 400 m / s. The adaptation of these scales to industrial and / or large-scale production is within the competence of a person skilled in the art, taking into account the information presented in the present description.

Turning to FIG. 2, it proposes an embodiment of a turbulent reactor system. The conveyor lines 23 through the control valves 19 to control the flow of raw materials and the cooling circuits 15 to cool the starting materials from pressure storage tanks 17, which contain the starting materials, monomer and catalyst starting materials are sent to the injection head 13. The pressure is maintained at the level of the predetermined pressure in the head by supplying inert gas, such as nitrogen, through the valves 21. One assembly option is used in the examples; it is described in more detail below and is illustrated in FIG.

In another embodiment, in order to ensure the formation of colliding flows of monomeric and catalytic starting materials with the achievement of the required mixing intensity, the convergence / divergence of the flows and / or nozzles are used. If the reaction is exothermic, it is also necessary to provide means for removing the heat of the reaction (by re-cooling the reagents below the target reaction temperature and / or removing heat through sensitive heat transfer through the reactor vessel or by evaporative heat transfer when the reaction medium is partially evaporated inside the reactor).

The total contact time in the reactor can be varied depending, for example, on the activity and concentration of the catalyst, monomer concentration, injection rate of the feed, productivity, reaction temperature and target molecular weight, it usually ranges from about a few microseconds to tens of seconds, and usually ranging from 0.001 to 30 s. Variable parameters affecting the contact time include injection rates of the starting monomer and diluent and the total reactor volume.

For information on previously known technical solutions and general principles, you should refer, for example, to GB 2181145 A, the work of Berlin and others. The Macroscopic Kinetics of Rapid Processes of Polymerization in Turbulent Flows, Polym.-Plast. TechnoI.Eng., 30 (2 & 3), 253-297 (1991), Minsker et al., Plug-Flow Tubular Turbulent Reactors: A New Type of Industrial Apparatus, Theoretical Foundations of Chemical Engineerig, Vol. 35, No. 2 , 162-167 (2001), and US No. 5397179.

As discussed in the BACKGROUND OF THE INVENTION section, the latest information poses many complex challenges in the implementation of such polymerization processes and reactor system designs. However, the polymerization methods and reactor systems that use diluents comprising the HFCs described herein have at least one or more advantages.

For example, the polymerization of isobutylene in polar fluorocarbons occurs at extremely high speeds and, therefore, is able to ensure the formation of the polymer of the target molecular weight within a very short reaction time, usually within seconds. Moreover, the overall reaction rate during the polymerization of isobutylene in fluorocarbons is much higher than in methyl chloride (MeCl), which increases the efficiency (monomer conversion and yield) of the reactor.

The choice of a particular fluorocarbon or a mixture of fluorocarbons and monomers makes it possible to plan the temperature of evaporation of the polymerization mixture. Such evaporation of the fluorocarbon mixture during polymerization allows the heat of polymerization to be effectively removed and the reaction temperature can be controlled. Everything is locally influencing the local temperature in the reactor: the composition of the polymerization mixture, local pressure and degree of polymerization. The choice of fluorocarbon, which is much more volatile than monomeric reagents, allows fluorocarbon diluents to evaporate during the reaction with the removal of reaction heat, but without the entrainment of a large proportion of isobutylene and comonomers.

Moreover, suspensions of isobutylene polymer obtained in fluorocarbons were probably found not to form contaminants due to the reduced swelling of the polymer in the monomers and diluent (compared to MeCl). Consequently, the tendency to contaminate the reactor is reduced, and therefore good mixing and stable hydrodynamics of polymerization are maintained in the reactor system.

In some embodiments, the invention is carried out using a suspension polymerization method. The polymerization methods of the invention may be cationic polymerization methods.

In some embodiments, polymerization is carried out in which the catalyst, monomer and diluent are in the same phase. In a preferred embodiment, the polymerization is carried out as a continuous polymerization process in which the catalyst, monomer (s) and diluent are contained in a single phase. In suspension polymerization, monomers, catalyst (s), initiator (s) are all capable of being mixed in a diluent or mixture of diluents, i.e. make up one phase, while the polymer precipitates from the diluent with good separation from the diluent. In a suitable embodiment, a reduced "swelling" of the polymer or its absence is manifested, as indicated by a weak or lack of suppression of Tg of the polymer and / or small or absence of weight gain of the diluent. Thus, the polymerization in diluents of the present invention provides the ability to handle the polymer in high concentration at low viscosity and with good heat transfer, reduced reactor fouling, homogenization of the polymerization process and / or the convenience of subsequent reactions directly in the resulting polymer mixture.

The reacted monomers inside the reactor or microdroplet form part of the suspension. In one embodiment, the concentration of dry matter in the suspension is equal to or greater than 10 vol.%. In another embodiment, the concentration of dry matter in the suspension that is contained in the reactor is equal to or greater than 25 vol.%. However, in yet another embodiment, the concentration of dry matter in the suspension is less than or equal to 75 vol.%. However, in another embodiment, the concentration of dry matter in the suspension, which is contained in the reactor, is from 1 to 70 vol.%. However, in another embodiment, the concentration of dry matter in the suspension, which is contained in the reactor, is from 5 to 70 vol.%. However, in yet another embodiment, the concentration of dry matter in the suspension, which is contained in the reactor, is from 10 to 70 vol.%. However, in another embodiment, the concentration of dry matter in the suspension, which is contained in the reactor, is from 15 to 70 vol.%. However, in another embodiment, the concentration of dry matter in the suspension, which is contained in the reactor, is from 20 to 70 vol.%. However, in another embodiment, the concentration of dry matter in the suspension, which is contained in the reactor, ranges from 25 to 70 vol.%. However, in yet another embodiment, the concentration of dry matter in the suspension, which is contained in the reactor, is from 30 to 70 vol.%. However, in yet another embodiment, the concentration of dry matter in the suspension, which is contained in the reactor, is from 40 to 70 vol.%.

In some embodiments, the feed stream is substantially free of materials forming silicon cations. By practically free of materials forming silicon cations, we understand the flow of the starting material, which contains no more than 0.0005 wt.% Of such silicon materials, calculated on the total weight of the monomers. Typical examples of silicon cation forming materials are haloalkyl silicon compounds of the formula R ₁ R ₂ R ₃ SiX or R ₁ R ₂ SiX ₂ , etc., where “R” is alkyl and “X” is a halogen atom. Usually create such reaction conditions in which the target temperature, pressure and length of stay are effective to keep the reaction medium in a liquid state and to obtain the target polymers with the desired characteristics. The monomer-containing feed stream is typically substantially free of any impurity that, under polymerization conditions, exhibits an undesired reactivity with respect to the catalyst. Thus, for example, in some embodiments, the preferred monomer feed should be substantially free of bases (such as caustic soda), sulfur-containing compounds (such as H ₂ S, COS and organomercaptans, for example methyl mercaptan, ethyl mercaptan), nitrogen-containing bases, oxygen-containing bases, such like alcohols, etc. However, the monomer feed may be less pure, as a rule it contains not less than 95% of the total olefin component, more preferably not less than 98%, not less than 99%. In preferred embodiments, the impurities are contained in an amount of less than 10,000 ppm (by weight), more preferably less than 500 ppm, preferably less than 250 ppm, preferably less than 150 ppm, preferably less than 100 ppm.

Usually the reaction time, temperature, concentration, nature of the reagents, etc. factors determine the molecular weights of products. The temperature during the polymerization reaction, it is advisable to choose taking into account the target molecular weight of the polymer and the monomer to be polymerized, as well as standard process variables and economic considerations, such as speed, temperature control, etc. The temperature during polymerization is below 0 ° C, preferably is between -10 ° C and the freezing point of the suspension in one embodiment and from -25 to -120 ° C in another embodiment. However, in yet another embodiment, the polymerization temperature is from -40 to -100 ° C and from -70 to -100 ° C in another embodiment. However, in yet another suitable embodiment, this temperature range is from -80 to -100 ° C. Therefore, under different reaction conditions, products with different molecular weights are usually obtained. Therefore, the synthesis of the target reaction product can be carried out by monitoring the progress of the reaction by examining samples taken periodically during the reaction: a technique widely used in the art.

In a preferred embodiment, the polymerization temperature is within 10 ° C above the freezing point of the diluent, preferably within 8 ° C above the freezing point of the diluent, preferably within 6 ° C above the freezing point of the diluent, preferably within 4 ° C above the freezing point of the diluent, preferably within 2 ° C. above the freezing point of the diluent, preferably within 1 ° C. above the freezing point of the diluent. Taking into account the objectives of the present invention and the claims, when the expression “within X ° C above the freezing point of the diluent” is used, the freezing point of the diluent plus X ° C is meant. So, for example, if the freezing point of the diluent is -98 ° C, then the temperature 10 ° C above the freezing point of the diluent is -88 ° C.

The reaction pressure is usually from above 0 to 14000 kPa in one embodiment (where 0 kPa corresponds to full vacuum), from 7 to 12000 kPa in another embodiment, from 100 to 2000 kPa in another embodiment, from 200 to 1500 kPa in another embodiment, from 200 to 1200 kPa in another embodiment, and yet from 200 to 1000 kPa in another embodiment, from 7 to 100 kPa in another embodiment, from 20 to 70 kPa in another embodiment, however, from 40 to 60 kPa in another variant, from 1000 to 14000 kPa in another embodiment, from 3000 to 10000 kPa in another embodiment, and yet from 3000 to 6000 kPa in another embodiment.

The order of the introduction of a monomer-containing stream of the starting material, catalyst, initiator and diluent into contact with each other can be varied when switching from one variant to another.

In another embodiment, the initiator and Lewis acid are introduced into preliminary contact by mixing with each other in the selected diluent for a prescribed amount of time, in the range from 0.01 s to 10 hours, and then injected into the continuous reactor through a catalyst nozzle or injection device. However, in yet another embodiment, the Lewis acid and initiator are introduced separately into the reactor. In another embodiment, before injection in the reactor, the initiator is mixed with the starting monomers. Suitably, before the monomers enter the reactor, the monomer is not brought into contact with a Lewis acid or a Lewis acid combined with an initiator.

In one embodiment of the invention, prior to injection into the reactor, the Lewis initiator and acid provide the opportunity for preliminary contacting by mixing with each other in the selected diluent at temperatures ranging from -40 to the freezing point of the diluent, with contact duration ranging from 0.01 s to several hours and in the range of 0.1 s to 5 minutes, preferably less than 3 minutes, preferably in the range of 0.2 s to 1 minute.

In another embodiment, the initiator and the Lewis acid are provided with the opportunity for preliminary contacting by mixing with each other in the selected diluent at temperatures ranging from -80 to -150 ° C, usually in the range from -40 to -98 ° C.

The created ratio between the catalyst (Lewis acid) and the monomer is common in the art for carbocationic polymerization processes. In one embodiment of the invention, the molar ratios between the monomer and the catalyst are typically from 500 to 10,000 and in the range from 2,000 to 6,500 in another embodiment. However, in another target embodiment, the ratio between the Lewis acid and the initiator is from 0.5 to 10, or from 0.75 to 8. The total concentration of initiator in the reactor, as a rule, is from 5 to 300 ppm or from 10 up to 250 ppm In one embodiment, the initiator concentration in the catalytic feed stream is typically from 50 to 3,000 ppm. Another way to reflect the amount of initiator in a reactor is to indicate its amount relative to the polymer. In one embodiment, it is from 0.25 to 20 moles of polymer / mole of initiator and from 0.5 to 12 moles of polymer / mole of initiator in another embodiment.

The reactor typically includes sufficient amounts of the catalyst system of the present invention to catalyze the polymerization of a monomer-containing feed stream, whereby a sufficient amount of polymer having the desired characteristics is obtained. In one embodiment, the feed stream contains monomers in a total concentration of more than 20 wt.% (In terms of the total weight of monomers, diluent and catalyst system), more than 25 wt.% In another embodiment. However, in yet another embodiment, the feed stream typically contains monomers in a concentration of 30 to 50% by weight, based on the total weight of the monomer, diluent, and catalyst system.

The efficiency of the catalyst (based on Lewis acid) in the reactor is maintained in the range of 10,000 to 300 pounds of polymer / pound of catalyst, and it is advisable in the range of 4,000 to 1,000 pounds of polymer / pound of catalyst by controlling the molar ratio between the Lewis acid and initiator.

AREAS OF INDUSTRIAL APPLICATION

The polymers of the invention exhibit chemical and physical characteristics due to which they are very useful in a wide variety of applications. The low degree of permeability to gases explains the widest application of these polymers, namely the manufacture of chambers and inner shells of tires. These same properties are also important in the manufacture of pneumatic gaskets, air springs, bellows-type air cylinders, battery packs and pharmaceutical sealing devices. The resistance to thermal aging of the polymers according to the invention makes them ideal materials for the manufacture of diaphragms for vulcanizer formators, hoses for operation at high temperatures and conveyor belts for handling hot materials.

These polymers exhibit high damping and have uniquely wide damping and damping ranges in both temperature and frequency. They can be used in the manufacture of molded rubber parts and are widely used in automotive suspension bumpers, suspension for exhaust pipes and supports for bodies.

The polymers of the present invention can also be used in rubber compounds for sidewalls and tire treads. In the sidewalls, the polymer characteristics give good ozone resistance, resistance to the growth of cracks and cuts and appearance. The polymers of the invention can also be mixed. Excellent mixes are made from suitably formulated mixtures with rubbers with a high content of diene units that exhibit phase continuity. Using the polymers of the present invention, high-performance tires can achieve improvements in skid resistance on wet, snowy and icy road surfaces and grip on dry surfaces without compromising abrasion and rolling resistance.

Mixtures of the polymers of the invention with thermoplastic resins are used to harden these materials. High density polyethylene and isotactic polypropylene are often modified by the addition of 5 to 30 wt.% Polyisobutylene. In some applications, the proposed polymers provide a highly elastic mixture that can be processed in thermoplastics molding equipment. The polymers of the present invention can also be mixed with polyamides to produce materials for other industrial applications.

The polymers of the present invention can also be used as adhesives, sealants, sealants and putties for glazing.

They can also be used as plasticizers in rubber compounds with butyl rubber, BSK and natural rubber. In blends with linear low density polyethylene (LLDPE), they induce stickiness in stretch wrapping films. They are also widely used in lubricants as dispersants and in materials for compounding and filling electrical cables.

The polymers according to the invention are also effective in some applications, such as chewing gum, as well as for medical purposes, in particular in pharmaceutical sealing devices, and technology for the manufacture of paint rollers.

The following examples reflect embodiments of the invention, which should not be construed as limiting the scope of the invention.

EXAMPLES

Injection head

Injection nozzles (FIG. 1) were ordered from Valco Instrument Co. Inc. and used as supplied. These nozzles are 1/16 inch pre-cut stainless steel nozzles 5 cm long and 0.02 inch inner diameter. Two nozzles of the same inner diameter were fixed on a piece of metal and oriented relative to each other at an angle of 90 °.

Reactor design

The reactor consists of 4 parts (FIG. 2): I. Chemical storage vessels 17 (monomeric and catalytic starting materials), the vessels were ordered from Baytown Valve & Fitting and used as supplied. These vessels are Swagelok 304L stainless steel 300 ml sampling cylinders. II. 23 1/4 inch pipe for transporting chemicals; 1/4 inch x 0.049 inch stainless steel pipe. III. 15 1/16 inch coil refrigerators for cooling the starting materials before entering the injection head; the coil cooler nozzle was ordered from Valco Instrument Co. Inc. and bent in the form of a coil in the laboratory. They were pre-cut from a 1/16 inch stainless steel tube 100 cm long and 0.040 inch inside diameter. IV. The injection head 13 for mixing chemicals (see figure 1).

Experimental setup

The entire experimental setup is shown in FIG. The temperature of the monomer and catalytic starting materials was controlled by immersing the entire reactor in a cold bath 25 at a target temperature. The vessels 37 for the monomer and the catalyst were equipped with means for feeding into the reactor using the pipe 35. The starting materials were cooled using coil refrigerators 33 immersed in a cold bath 25. To reach the temperature of the bath before mixing, the reactor was placed in a cold bath for a period of 15 to 20 min . After the injection head 31, to quench the polymerization and collect the polymer, a 500 ml glass vessel 27 with 30 ml of 2-propanol was placed in a cold bath 25.

Chemicals

Solvents

Before use, liquid methyl chloride was passed through a molecular sieve column and a silica gel column, then dried by TE-A1 (aluminum triethyl) and distilled. TE-A1 was ordered from Akzo Nobel and used as supplied.

Methylene chloride was ordered from Aldrich, before use CaH _{2 was} dried and distilled. CaH _{2 was} ordered from Aldrich and used as supplied.

Liquid 1,1,1,2-tetrafluoroethane was used as supplied, without any purification.

Difluoromethane was ordered from SynQuest Laboratories, Incorporated. In some experiments, liquid difluoromethane was used as it was, without any purification. For comparison, in some experiments, difluoromethane was dried with TE-A1 and distilled.

Monomers

Gaseous isobutylene was supplied by ExxonMobil Chemical Plant in Beiton, Texas, before being used, it was passed through a drying tower. Isoprene was ordered from Aldrich and distilled under vacuum before use.

Catalyst

A 20 wt.% Catalyst feed solution was prepared in the laboratory by mixing pure ethyl aluminum dichloride with ULB hexane. Ethylaluminium dichloride was ordered from Akzo Nobel and used as supplied. Before use, ExxonMobil ULB hexane was preliminarily dried with a 4 Å molecular sieve.

Cocatalyst

TMPCh (2-chloro-2,4,4-trimethylpentane) was prepared by hydrochlorination of an isobutylene dimer and dried CaH ₂ before use and distilled under vacuum. HCl was pre-dissolved at a constant temperature in the target solvent and used immediately thereafter. The concentration of HCl in the solvent was determined by titration.

The following method was carried out in all experiments: the reactor was placed in a cold bath at a target temperature. Isobutylene and isoprene at the target temperature were mixed with a pure solvent in a 250 ml graduated cylinder. The total volume of the monomer solution was approximately 150 ml. The mixed monomer solution was transferred to a 300 ml monomer vessel. The HCl feed solution was diluted with 250 ml of purified solvent and activated with 20% by weight of EDC / hexane ULB. The activated catalyst was transferred to another 300 ml vessel. In both vessels during the reaction, an increased pressure of gaseous N _{2 was created} in the range from 690 to 795 kPa. To a pre-cooled 2-necked 500 ml round bottom flask was added 25 ml of 2-propanol and the flask was immersed in a cold bath to quench the polymerization reaction and collect the polymer.

An injection head was placed over a round bottom flask. For improved mixing of the quenching agent with the obtained polymer, a mechanical stirrer was used in the collector. The reaction was started initially by feeding an activated catalyst stream followed by a feed of the starting monomer solution. Flows of chemicals exited injection nozzles at high speed and mixed, intersecting each other with the formation of very fine droplets of liquid. Polymerization proceeds inside the finely divided droplets of liquid. Polymerization continues until droplets in the collection reach 2-propanol. The polymerization by mixing droplets with 2-propanol is apparently stopped. The polymerization time in each droplet is less than a second. The polymerization was continued until both vessels were empty. The total reaction time in each experiment was approximately 2 minutes. The polymers were dried in a vacuum oven, which allowed us to calculate the conversion for each polymerization. The molecular weight of the polymer was checked by GPC.

Methyl Chloride (MeCl)

As comparative examples, polymerization processes were tried in methyl chloride using HCl as an initiator. Due to the short residence time when using methyl chloride as a solvent, no polymer was formed.

Methylene Chloride (CH ₂ Cl ₂ )

For experiments with methylene chloride, the experimental method was modified. Instead of loading the pre-activated catalyst into the catalyst vessel, before the reaction, TMPC was added to the monomer solution and loaded into the monomer vessel. Polymerization in methylene chloride was also different from processes in other solvents, since the polymer was dissolved in a solvent. According to their characteristics, the polymerization processes in methylene chloride were more reminiscent of solution polymerization processes than suspension polymerization processes. Polymerization processes in methyl chloride are comparative examples.

1,1,1,2-Tetrafluoroethane (CH ₂ FCF ₃ )

The polymer formed immediately after mixing and insisting in suspension after quenching the reaction with 2-propanol.

Difluoromethane (CH ₂ F ₂ )

The polymer formed immediately after mixing and insisting in suspension after quenching the reaction with 2-propanol.

Table 1 lists the results of polymerization processes carried out at a monomer concentration of 10 wt.% Using different solvents at -95 ° C. As an initiator in examples 1, 2 and 3 used HCl. Examples 1, 2 and 3 are examples of the present invention. As the initiator in example 4 used TMPl (2-chloro-2,4,4-trimethylpentane). Example 4 is a comparative example.

Table 1 Example Diluent The conversion (wt.%) M _n × 10 ^-3 M _w × 10 ^-3 M _w / M _n EADC / initiator molar ratio one CH ₂ FCF ₃ 33.6 97 286 2.9 3.0 2 CH ₂ F ₂ 20,4 55 217 3.9 3.0 3 ^a CH ₂ F ₂ 56.2 96 319 3.3 3.0 4 ^b CH ₂ Cl ₂ 31,4 10 17 1.7 3.0

a: before applying CH ₂ F _2, dried TE-A1 and distilled.

b: before applying CH ₂ Cl ₂ dried CaH ₂ and distilled.

Table 2 lists the results of polymerization processes carried out at a monomer concentration of 10 wt.% Using different solvents at -55 ° C. As the initiator in examples 5 and 6 used HCl. Examples 5 and 6 are examples of the present invention. TMPLC (2-chloro-2,4,4-trimethylpentane) was used as an initiator in Example 7. Example 7 is a comparative example.

table 2 Example Diluent The conversion (wt.%) M _n × 10 ^-3 M _w × 10 ^-3 M _w / M _n EADC / initiator molar ratio 5 CH ₂ FCF ₃ 22.4 57 129 2.2 6.0 6 CH ₂ F ₂ 5.7 45 107 2,4 6.0 7 ^a CH ₂ Cl ₂ 53.6 10 17 1.7 6.0

a: before use, CH ₂ Cl _{2 was} dried CaH ₂ and distilled.

Table 3 lists the results of polymerization processes carried out at a monomer concentration of 5 wt.% Using different solvents at -95 ° C. HCl was used as an initiator in Examples 8 and 9.

Table 3 Example Diluent The conversion (wt.%) M _n × 10 ^-3 M _w × 10 ^-3 M _w / M _n EADC / initiator molar ratio 8 CH ₂ FCF ₃ 70.3 83 221 2.7 3.0 9 CH ₂ F ₂ 13.6 109 290 2.6 3.0

The above examples illustrate some embodiments of the present invention. The polymerization in fluorocarbon proceeds quickly enough to achieve acceptable both the conversion and the molecular weight of the resulting polymer. Polymerization processes using chlorohydrocarbons were either impossible, i.e. under comparative reaction conditions, the reaction did not proceed, or when conversion to a polymer was achieved, the molecular weights of the products obtained were significantly lower than in comparative reactions in fluorocarbon.

All patents and patent applications referred to herein, test methods (such as ASTM methods) and other documents are incorporated by reference in their entirety to the extent that they do not comply with the present invention, in all jurisdictions that such inclusion is allowed.

When numerical lower limits and numerical upper limits are indicated herein, ranges from any lower limit to any upper limit are contemplated.

Although the invention has been described and illustrated with reference to specific embodiments, various other modifications are obvious to those skilled in the art that can be easily implemented without departing from the spirit and scope of the invention. Therefore, there are no intentions to limit the scope of the attached claims to the examples and illustrations given in the present description previously, since the claims should be construed as encompassing all the features of the claimed novelty that are inherent in the present invention, including all the distinguishing features that are specialists in this field the technology to which the invention relates would be construed as their equivalents.

Claims (36)

1. The method of polymerization, comprising contacting at least one first stream of starting materials and at least one second stream of starting materials with a contact time of about 30 s or less, comprising a diluent containing in the reactor system one or more fluorocarbons (HFCs) of the formula : C _x H _y F _z in which x is an integer from 1 to 40 and y and z are integers of one or more, where at least one first feed stream includes a catalyst system or a component nt of the catalyst system, and at least one second feed stream includes one or more monomers independently selected from the group consisting of olefins, alpha olefins, disubstituted olefins, isoolefins, conjugated dienes, non-conjugated dienes, styrenes, substituted styrenes, vinyl ethers and mixtures thereof. 2. The polymerization method according to claim 1, in which the components of the catalytic system include one or more Lewis acids or one or more initiators. 3. The polymerization method according to one of claims 1 and 2, which includes one or more Lewis acids independently selected from the group consisting of titanium tetrachloride, titanium tetrabromide, vanadium tetrachloride, tin tetrachloride, zirconium tetrachloride, titanium bromide trichloride, titanium dibromide dichloride, titanium bromide dichromide , tin chloride trifluoride, benzyl titanium trichloride, dibenzyl titanium dichloride, benzyl zirconium trichloride, dibenzyl zirconium dibromide, methyl titan trichloride, dimethyl titan difluoride, dimethyl tin dichloride, phenyl vanadium trichloride, methoxy titanium trichloride, n-butoksititantrihlorid, di (isopropoxy) titanium dichloride, fenoksititantribromid, fenilmetoksitsirkoniytriftorid, metilmetoksititandihlorid, metilmetoksiolovodihlorid, benzilizopropoksivanadiydihlorid, atsetoksititantrihlorid, benzoiltsirkoniytribromid, benzoiloksititantriftorid, izopropoiloksiolovotrihlorid, metilatsetoksititandihlorid, benzilbenzoiloksivanadiyhlorid, vanadium oxytrichloride, aluminum trichloride, boron trifluoride, boron trichloride, gallium trifluoride, indium, ethylaluminium dichloride , methylaluminodichloride, benzylaluminodichlor id, izobutilgalliydihlorid, dietilalyumohlorid, dimetilalyumohlorid, etilalyumoseskvihlorid, metilalyumoseskvihlorid, trimethylaluminum, triethylaluminum, metoksialyumodihlorid, etoksialyumodihlorid, 2,6-di-tert-butilfenoksialyumodihlorid, metoksimetilalyumohlorid, 2,6-di-tert-butilfenoksimetilalyumohlorid, izopropoksigalliydihlorid, fenoksimetilindiyftorid, atsetoksialyumodihlorid, benzoiloksialyumodibromid, benzoiloksigalliydiftorid, metilatsetoksialyumohlorid, isopropyloxyindium trichloride, antimony hexachloride, antimony hexafluoride, pentaphtho arsenic chloride, antimony chloride pentafluoride, arsenic trifluoride, bismuth trichloride, arsenic fluoride tetrachloride, antimony tetraphenyl dichloride, antimony triphenyl dichloride, tetrachloromethoxysimmon 4. The polymerization method according to one of claims 1 and 2, which includes one or more initiators, including hydrogen halide, carboxylic acid, carboxylic acid halide, sulfonic acid, alcohol, phenol, polymer halide, tertiary alkyl halide, tertiary aralkyl halide, tertiary aliphatic complex ether, tertiary araliphatic ester, tertiary aliphatic ether, tertiary araliphatic ether, alkyl halide, aryl halide, alkyl aryl halide, H ₂ O and an aryl aliphatic halide acids. 5. The polymerization method according to one of claims 1 and 2, which includes one or more initiators, including a weakly coordinated anion. 6. The polymerization method according to one of claims 1 and 2, in which the polymerization process is carried out practically in the absence of water. 7. The polymerization method according to one of claims 1 and 2, in which the first stream of starting materials includes 30 ppm or more water (in terms of weight). 8. The polymerization method according to one of claims 1 and 2, in which the diluent comprises from 15 to 100 vol.% FUV, calculated on the total volume of the diluent. 9. The polymerization process according to one of claims 1 and 2, wherein the diluent further comprises a hydrocarbon, a non-reactive olefin and / or an inert gas. 10. The polymerization method according to claim 9, in which the hydrocarbon is a halogenated hydrocarbon other than the HEM. 11. The polymerization process of claim 10, wherein the halogenated hydrocarbon is methyl chloride. 12. The polymerization method according to one of claims 1 and 2, wherein the diluent contains methyl chloride and one or more fluorocarbons independently selected from the group consisting of difluoromethane, 1,1-difluoroethane and 1,1,1,2-tetrafluoroethane. 13. The polymerization method according to one of claims 1 and 2, in which the flow rate is from about 0.5 to about 400 m / s. 14. The polymerization method according to one of claims 1 and 2, in which a reactor system is used, comprising at least one device for storing the catalyst system or components of the catalyst system, at least one device for storing one or more monomers, at least one a device for cooling the catalyst system and / or components of the catalyst system and one or more monomers and at least one injection head. 15. The polymerization method according to one of claims 1 and 2, in which the polymerization process is a suspension polymerization process. 16. The polymerization method according to one of claims 1 and 2, in which the polymerization process is a cationic polymerization process. 17. The polymerization process according to one of claims 1 and 2, wherein the polymerization process is a continuous polymerization process. 18. The polymerization process according to one of claims 1 and 2, wherein the polymerization process is a polymerization process to produce isobutylene-based polymers. 19. A polymerization process comprising contacting a catalyst system and one or more monomers independently selected from the group consisting of olefins, alpha olefins, disubstituted olefins, isoolefins, conjugated dienes, non-conjugated dienes, styrenes, substituted styrenes, vinyl ethers and mixtures thereof with the contact times of about 30 seconds or less in microdroplets polymerization medium comprising a diluent comprising one or more ftrouglevodorodov (CCF) corresponding to the formula C _x H _y F _z, wherein x denotes purposes e integer from 1 to 40 and y and z are integers of one or more. 20. The polymerization method according to claim 19, in which the microdroplet has a diameter of from about 0.4 to about 1000 microns. 21. The polymerization method according to one of claims 19 and 20, which includes one or more Lewis acids independently selected from the group consisting of titanium tetrachloride, titanium tetrabromide, vanadium tetrachloride, tin tetrachloride, zirconium tetrachloride, titanium bromide trichloride, titanium dibromide dichloride, titanium bromide dichromide , tin chloride trifluoride, benzyl titanium trichloride, dibenzyl titanium dichloride, benzyl zirconium trichloride, dibenzyl zirconium dibromide, methyl titan trichloride, dimethyl titan trifluoride, dimethyl tin dichloride, phenyl vanadium trichloride, methoxy ntrihlorid, n-butoksititantrihlorid, di (isopropoxy) titanium dichloride, fenoksititantribromid, fenilmetoksitsirkoniytriftorid, metilmetoksititandihlorid, metilmetoksiolovodihlorid, benzilizopropoksivanadiydihlorid, atsetoksititantrihlorid, benzoiltsirkoniytribromid, benzoiloksititantriftorid, izopropoiloksiolovotrihlorid, metilatsetoksititandihlorid, benzilbenzoiloksivanadiyhlorid, vanadium oxytrichloride, aluminum trichloride, boron trifluoride, boron trichloride, gallium trifluoride, indium, ethylaluminium dichloride , methylaluminodichloride, benzylaluminodichl chloride, izobutilgalliydihlorid, dietilalyumohlorid, dimetilalyumohlorid, etilalyumoseskvihlorid, metilalyumoseskvihlorid, trimethylaluminum, triethylaluminum, metoksialyumodihlorid, etoksialyumodihlorid, 2,6-di-tert-butilfenoksialyumodihlorid, metoksimetilalyumohlorid, 2,6-di-tert-butilfenoksimetilalyumohlorid, izopropoksigalliydihlorid, fenoksimetilindiyftorid, atsetoksialyumodihlorid, benzoiloksialyumodibromid, benzoiloksigalliydiftorid, metilatsetoksialyumohlorid, isopropyloxyindium trichloride, antimony hexachloride, antimony hexafluoride, pentaf Orido arsenic hloridpentaftorid antimony, arsenic trifluoride, bismuth trichloride, ftoridtetrahlorid arsenic, antimony tetrafenilhlorid, trifenildihlorid antimony tetrahlormetoksisurmu, dimetoksitrihlorsurmu, dihlormetoksiarsin, hlordimetoksiarsin, diftormetoksiarsin, atsetotetrahlorsurmu, benzoatotetrahlorsurmu atsetohlorid and bismuth. 22. The polymerization method according to one of paragraphs.19 and 20, which includes one or more initiators, including hydrogen halide, carboxylic acid, carboxylic acid halide, sulfonic acid, alcohol, phenol, polymer halide, tertiary alkyl halide, tertiary aralkyl halide, tertiary aliphatic complex ether, tertiary araliphatic ester, tertiary aliphatic ether, tertiary araliphatic ether, alkyl halide, aryl halide, alkyl aryl halide, H ₂ O and an aryl aliphatic halide acids. 23. The polymerization method according to one of paragraphs.19 and 20, which includes one or more initiators, including a weakly coordinated anion. 24. The polymerization method according to one of paragraphs.19 and 20, in which the polymerization process is carried out in the absence of water. 25. The polymerization process according to one of claims 19 and 20, wherein the first feed stream comprises 30 ppm or more water (based on weight). 26. The polymerization method according to one of paragraphs.19 and 20, in which the diluent comprises from 15 to 100 vol.% FUV in terms of the total volume of diluent. 27. The polymerization process according to one of claims 19 and 20, wherein the diluent comprises a hydrocarbon, a non-reactive olefin and / or an inert gas. 28. The polymerization method according to one of paragraphs.19 and 20, in which the hydrocarbon is a halogenated hydrocarbon other than FUV. 29. The polymerization process of claim 28, wherein the halogenated hydrocarbon is methyl chloride. 30. The polymerization method according to one of claims 19 and 20, wherein the diluent comprises methyl chloride and one or more fluorocarbons independently selected from the group consisting of difluoromethane, 1,1-difluoroethane and 1,1,1,2-tetrafluoroethane. 31. The polymerization process according to one of claims 19 and 20, wherein the flow rate is from about 0.5 to about 400 m / s. 32. The polymerization method according to one of claims 19 and 20, in which a reactor system is used, comprising at least one device for storing the catalyst system or components of the catalyst system, at least one device for storing one or more monomers, at least one a device for cooling the catalyst system and / or components of the catalyst system and one or more monomers and at least one injection head. 33. The polymerization process according to one of claims 19 and 20, wherein the polymerization process is a suspension polymerization process. 34. The polymerization process according to one of claims 19 and 20, wherein the polymerization process is a cationic polymerization process. 35. The polymerization process according to one of claims 19 and 20, wherein the polymerization process is a continuous polymerization process. 36. The polymerization process according to one of claims 19 and 20, wherein the polymerization process is a polymerization process to produce isobutylene-based polymers.

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