Functionalised polymer and methods for production and use thereof

FIELD: chemistry.

SUBSTANCE: invention relates to polymers that are suitable for use in making rubber articles, such as tyre treads. The method of producing a functionalised polymer involves conducting a reaction between a polymer with an active terminal group, which contains a diene monomer moiety, and a compound which contains a disilylamino group and a group which is capable of reacting with polymers with an active terminal group selected from keto, thioketo, epoxy and epithio groups. The polymer contains a diene monomer moiety and a terminal moiety which contains a disilylamino group and a residue of a group which contains a heteroatom. Said terminal moiety has the general formula , where values of radicals are given in the claim. Also disclosed is a vulcanisate which contains said polymer, and an article made therefrom.

EFFECT: said polymers and articles made therefrom are characterised by improved tensile properties, improved wear resistance and fatigue resistance and low hysteresis loss.

15 cl, 7 tbl, 22 ex

 

The level of technology

Rubber products, such as the treads of the tires, are often made from elastomeric compositions that contain one or more reinforcing materials, such as, for example, dispersed carbon black and silica; see, for example, the publication of The Vanderbilt Rubber Handbook, 13th ed. (1990), str-604.

The main considerations taken into account in the manufacture of treads of the tires are good road grip and abrasion resistance; however, the problem of fuel economy of vehicles speaks in favor of minimizing their rolling resistance, which correlates with reduced hysteresis and heat during operation of the tire. Unfortunately, protectors, made from compositions designed to provide good traction with the road surface, usually characterized by increased rolling resistance.

The fillers (fillers), the polymer (polymers and additives are usually chosen in such a way as to achieve an acceptable compromise between these properties or their balance. Ensuring good dispersion of the reinforcing filler (filler) in the whole volume of the elastomeric material (materials) as improves processability, and performs the function of improving the physical properties. Dispergirovany is their fillers can be improved by increasing their interaction with the elastomer (elastomer). Examples of measures of this type include high temperature mixing in the presence of selective reactive promoters, surface oxidation of the materials composed of mixtures of surface inoculation and chemical modification of the polymer, usually in its end position.

Various elastomeric materials are often used in the production of vulcanizates, such as, for example, the components of tires. In addition to natural rubber, some of the more commonly used materials include polydiene characterized by a high content of CIS-links are often obtained by methods using catalysts, and Sterol/butadiene interpolymer, often obtained by methods using anionic initiators. Functionality that can be introduced in polydiene characterized by a high content of CIS-units, often can not be entered into anionic initiated styrene/butadiene interpolymer and Vice versa.

CIS-1,4-polydiene obtained when using catalysts based on lanthanides, often have a linear structure, which seems to be characterized by improved tensile property, improved abrasion resistance and fatigue resistance and reduced hysteresis loss. So, that is their CIS-1,4-polydiene are particularly suitable for use in components of tires, such as sidewalls and treads.

Disclosure of inventions

In one aspect of the proposed polymer containing terminal fragment, which includes decelerating. End fragment can be a radical of a compound that includes a group that includes at least one heteroatom in addition to giselelamanque (disillumination). In certain embodiments of the terminal fragment can be described by the formula

where each R independently represents a hydrogen atom or a substituted or unsubstituted monovalent organic (for example, hydrocarbonous) group; R1represents a substituted or unsubstituted divalent organic group, such as hydrocarbonate group, but not limited to; j represents O or S; and each R' independently represents R, or both groups R' together form a substituted or unsubstituted divalent organic group, which together with two Si atoms and the N atom of disillusionary is cyclic functionality.

In yet another aspect of the proposed functionalized polymer that includes the reaction product between the chain is active in end position (for example, carbanions or pseudo-living) polymer and a compound that includes the as disillusioned, and the group that can react with polymers with active end group, such as, for example, (thio)keto - or apachegroup (or S-similar, that is, epithiopropyl). Also suggests ways that are appropriate for use in obtaining this type of functional polymer. In certain embodiments of a compound which reacts with the polymer (herein also called "reactive compound") can have a structure, opisyvayuschaya following formula

where R, R' and R1defined above, and Q represents the containing heteroatom group which can react with polymers with terminal active group; in certain embodiments of Q can be described in either of the following two formulas

or

where R and J are defined above.

In one additional aspect of the proposed macromolecule, vpisivaushiesya following formula

where {p} is a chain polymer, a R, R', R1and J is defined above.

Regardless of the method of determining the characteristics of the polymer can interact with the dispersed filler, such as carbon black and silica. Also proposed compo is icii, including the vulcanizates that include dispersed fillers and such polymers, and methods of obtaining and using such compositions.

In each and every of these aspects, the polymer can include directly attributable aromatic side groups, can be essentially linear and/or may include unsaturation within the polymer chain and/or in the position of the side groups of the polymer chain. This unsaturation may be a result of the introduction of the unsaturated Monomeric units, and preferably is essentially statistically distributed along the polymer chain.

After reading the description of the illustrative implementation options that follows, specialists in the relevant field of technology will become apparent and other aspects of the invention. To facilitate understanding the description below are a few definitions. They are intended for use throughout the course of the presentation, unless the context would clearly indicate the opposite:

"polymer" refers to polymerization product of one or more monomers and include Homo-, co-, Ter-, terpolymer and the like;

"macromolecule" refers to a chemical compound, which in its structure includes two or more polymer chain;

"Monomeric fragment" or "Monomeric radio is on" means that portion of the polymer, which is produced from one molecule of the reagent (for example, ethylene Monomeric fragment described by the General formula-CH2CH2-);

"copolymer" means a polymer that includes monomer units produced from two reactants, typically monomers, and includes statistical, block, segmented, graft, and the like copolymers;

"interpolymer" refers to a polymer that comprises monomer units produced at least two reactants, typically monomers, and includes copolymers, terpolymers, terpolymer and the like;

"(thio)keto" refers to keto or taketo;

"substituted" means containing a heteroatom or functionality (for example, hydrocarbonous group), which do not prevent the implementation of the intended destination of the group under consideration;

"directly related" means covalently attached without any intermediate or embedded atoms or groups;

"Polian" refers to a molecule containing at least two double bonds located at the longest parts or circuits, and, in particular, includes dieny, Triana and the like;

"politian" refers to a polymer that comprises monomer units of one or more dienes;

"h/hundred hours of rubber" refers to mass parts (machine hours) 100 M.Ch. rubber;

"radical" means that part of a molecule that remains after entering into the reaction with another molecule, regardless of the acquisition or loss of any atoms in the passage of the reaction;

"gecoordineerde anion" denotes a sterically bulky anion which does not form coordination bonds, for example, with the active center of the catalyst system because of steric hindrance;

predecessor necoordonarea anion" refers to a compound which is capable of forming gecoordineerde anion in the reaction conditions; "end position" denotes the end of the polymer chain; and

"limit fragment" refers to a group or functionality located at the limit position.

Throughout the course of writing this document, all values are given in the form of percentage values represent the mass percentages, unless the context would clearly indicate the opposite.

The implementation of the invention

Functionalized macromolecular materials, collectively described previously, can be obtained by introducing at least one compound that includes at least one decelerating and a group that can react with polymers with terminal active group (hereinafter in us is oasam document "funktsionalismi agent"). The molar ratio between functionalityin agent (agents) and chains of the polymer can be adjusted to regulate the amount of functionalized polymers, although to achieve full or very close to full functionalization typically use excess funktsionaalsusega agent (agent).

The polymer may be an elastomer, and may include monomer units, which include unsaturation, such as those produced from a polyene, in particular, dienes and trienol. Illustrative polyene include C4-C12diene, in particular, conjugate diene, such as, but not limited to, the following: 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2,4-hexadiene and the like.

Depending on the intended final version of the application of one or more chains of the polymer may include aromatic side groups, which can be obtained, for example, in the introduction vinylaromatic Monomeric fragment, in particular, C8-C20vinylaromatic, such as styrene, α-methylsterols, p-methylsterol, vinyltoluene, vinylnaphthalene and the like. In the case of use in combination with one or more polyene monomer units having side aromaticity, which may range from ~1 to ~50%, from ~10 to ~45%, or from ~20 to ~35% of the polymer chain when calculating the total content of the Monomeric fragments; microstructure such interpolymers can be static, i.e., monomer units produced from each type of monomer component, do not form blocks, and instead included not essentially a repetitive way. Statistical microstructure can achieve special advantages in some areas of the final application, such as, for example, in the case of rubber compositions used in the manufacture of treads of tires.

Examples of elastomers include interpolymer one or more polyene and styrene, such as, for example, copoly(styrene-butadiene), also known as SBC.

The polyene can be included in the chain of the polymer by more than one method. The regulation of this method of inclusion may be desirable, particularly in the case of application for the treads of the tires. For certain choices of areas of end use may be desirable chain of the polymer, demonstrating the presence of total 1,2-microstructure in the range from ~10 to ~80%, optionally from ~25 to ~65%, for expressions through numerical percentage value when calculating the total levels of being. The polymer, which demonstrates the existence of joint 1,microstructure no more than ~50%, preferably not more than ~45%, more preferably not more than ~40%, even more preferably not more than ~35%, and most preferably not more than ~30%, when calculating the total levels of being, is essentially linear. For certain choices of areas of end use desired may be keeping even more low content of 1,2-connecting links, for example, less than about 7%, less than 5%, less than 2%, or less than 1%.

Srednekislye molecular mass (Mnof the polymer is usually that the sample subjected to the quenching of the reaction will be characterized by a Mooney viscosity for unfilled rubber (ML4/100°C) in the range from ~2 to ~150, more often from ~2.5 to ~125, even more often from ~5 to ~100, and most often from ~10 to ~75.

The above types of polymers can be obtained by carrying out emulsion polymerization or solution polymerization, while the latter provides a greater degree of regulation in relation to such properties as disorder, microstructure, and the like. Solution polymerization was performed at approximately the middle of the 20th century, so that its General aspects of specialists in the relevant field of technology known; however, for convenience, used the I this document provides specific aspects.

Depending on the nature of the desired polymer concrete conditions of carrying out solution polymerization can vary considerably. In the discussion that follows will first be described anion-initiated (living) polymerization followed by a description of (pseudo living) polymerizate using coordination catalysts. After these descriptions will be discussed functionalization and processing of the thus obtained polymers.

Solution polymerization typically involves the initiator. Examples of initiators include organolithium compounds, in particular, derivatives alkylate. Examples of organolithium initiators include N-litigationrelated; n-utility; tributylamine-Li; derivative dialkylaminomethyl, such as dimethylaminomethyl, diethylaminomethyl, dipropylamine, dibutylamine and the like; derivatives of dialkylaminoalkyl, such as diethylaminopropylamine; and those derived trialkylamine, are C1-C12preferably C1-C4, alkyl groups.

Can also be used and multifunctional initiators, i.e., initiators, can result in polymers having more than one "live" end group. Examples of multifunctional initiators include, but are not limited to issleduyuschimi: 1,4-militiaman, 1,10-delithiation, 1,20-militiaman, 1,4-deliciousa, 1,4-desitination, 1,10-deletiondate, 1,2-delicio-1,2-diphenylethane, 1,3,5-teletypists, 1,5,15-militiaman, 1,3,5-trinitycollege, 1,3,5,8-tetraglycidyl, 1,5,10,20-TetraSociology, 1,2,4,6-tetrasociological and 4,4'-deleteoriginal.

In addition to the organolithium initiators suitable for use can also be a so-called functionalized initiators. They are included in the polymer chain, thus ensuring the presence of a functional group formed from the initiator end group of the chain. Examples of such materials include lityeraturnyye arylthioureas (see, for example, U.S. patent No. 7153919) and the reaction product between organolithium compounds and, for example, N-containing organic compounds, such as substituted aldimine, ketimine, secondary amines, and the like, if necessary, subjected to a preliminary reaction with a compound such as diisopropenylbenzene, (see, for example, U.S. patent No. 5153159 and 5567815).

Solvents suitable for anionic polymerization include various5-C12cyclic and acyclic alkanes, as well as their alkylated derivatives, some liquid aromatic compounds, and mixtures thereof. Experts in the relevant field of technology have presented the s and other appropriate options and combinations.

In the mortar polymerization as a disorder, and the vinyl content (i.e., 1,2-microstructure) can be increased by including in the ingredients for polymerization coordinator - usually polar compounds. One equivalent of initiator can be used up to 90 or more equivalents of the coordinator, this number depends on the required level of vinyl content, the content used politologe monomer, the reaction temperature and the nature of concrete used coordinator. Compounds suitable for use as coordinators include organic compounds that include a heteroatom having a disjoint pair of electrons (e.g., O or N). Examples include dialkylamide ethers of mono - and oligoarticular; crown ethers; tertiary amines, such as tetramethylethylenediamine; tetrahydrofuran (THF), THF oligomers; linear and cyclic oligomeric oxalanilide (see, for example, U.S. patent No. 4429091), such as 2,2-bis(2'-tetrahydrofuryl)propane, dipiperidide, hexamethylphosphoramide, N,N'-dimethylpiperazine, diazabicyclo, diethyl ether, tributylamine and the like.

Although experts in the relevant field of technology and have an idea about the conditions normally used in the races is fruitful polymerization, for convenience offered representative description. The following is based on a periodic way, although the range of capabilities of a specialist in the relevant field of technology gets the distribution of this description and paliperidone, continuous and similar methods.

Solution polymerization usually start with loading the mixture of monomer (monomers) and solvent to a suitable reaction vessel with subsequent addition of the coordinator (if using any) and the initiator, which are often added as part of the solution or mixture; alternatively, the monomer (monomers) and the coordinator can be added to the initiator. The method is usually implemented in anhydrous anaerobic conditions. The reactants can be heated to the temperature goes up to about 150°C, and mixed. After reaching the desired degree of reaction is the heat source (if using any) can be removed, and in the case of redundancy reaction vessel exclusively for polymerizati the reaction mixture is removed in postpolymerization capacity to conduct functionalization and/or quenching of the reaction.

In General, the polymers obtained in accordance with anionic ways, can be characterized by a value of Mnin the range from ~50,000 to ~500000 daltons, although the specific embodiments of srednekislye molecular weight may be in the range of ~75,000 to ~250,000 daltons, or even from ~90000 to ~150,000 daltons.

In certain embodiments of the areas of the final application requires polymers that have properties, which may be difficult or inefficient in the case of anionic (live) polymerizate. For example, in some applications desirable can be conjugated diene polymer, characterized by a high content of CIS-1,4-connecting links. Polydiene can be obtained by methods using catalysts (as opposed to the initiators used in living polymerization), and can exhibit pseudo-living characteristics.

Some systems catalysts preferably in the produce CIS-1,4-polydienes, while the other is preferably result in a TRANS - 1,4-polydienes. Experts in the relevant field of technology are familiar with examples of each type of system. The rest of this description is based on system-specific CIS-specific catalyst, although this is simply in order to bring the sample and is not considered a limitation of the way functionalization and connections.

Examples of systems coordination catalysts can use metals, the lanthanides, which, as you know, are suitable for use in the polymerization of conjugated diene monomers. In h is particularly system catalysts, which include the lanthanide compound, can be used to produce CIS-1,4-polydienes of one or more types of conjugated dienes.

Preferred compositions of the catalysts based on lanthanides are described in detail, for example, in U.S. patent No. 6699813 and patent documents cited therein. The term "catalyst composition" is intended to include a simple mixture of ingredients, a combination of various ingredients, the formation of which cause a physical or chemical forces of attraction, the product of a chemical reaction between some or all of the ingredients or combinations of the above options. For convenience and ease of use this document provides a concise description.

Examples of compositions lanthanoide catalysts include (a) a lanthanide compound, an alkylating agent and a halogenated compound (although in the case of a content of the halogen atom in the compound of a lanthanide and/or alkylating agent, the use of halogenated compounds is optional); (b) a lanthanide compound and alumoxane; or (c) a lanthanide compound, an alkylating agent and gecoordineerde anion or its predecessor.

Can be used various compounds of the lanthanides or mixtures thereof. These compounds are preferably soluble the mi in hydrocarbon solvents, such as aromatic hydrocarbons, e.g. benzene, toluene, xylenes, (di)ethylbenzene, mesitylene and the like; aliphatic hydrocarbons such as linear and branched C5-C10alkanes, petroleum ether, kerosene, white spirits, and the like; or cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, Methylcyclopentane, methylcyclohexane and the like; although insoluble in the hydrocarbon compounds of the lanthanides can be suspended in the polymerization medium. Preferred compounds of the lanthanides include those compounds that contain at least one atom Nd, La or Sm, or those that contain didyme (a commercial mixture of rare earth elements obtained from monazite sand). Atom (atoms) of the lanthanide in the compounds of lanthanides can be in any of several oxidation States, although usually use compounds containing a lanthanide atom in oxidation state +3. Examples of lanthanide compounds include carboxylates, organophosphates, organophosphate, organophosphonate, xanthates, carbamates, dithiocarbamates, β-diketonates, alkoxides, aryloxides, halides, pseudohalogen, oxychloride and the like; numerous examples of each of these types of lanthanide compounds can be found in the aforementioned U.S. patent No. 6699813.

Usually the lanthanide compound is used in combination with one or more alkylating agents, that is, ORGANOMETALLIC compounds, which can carry gidrolabilna group to another metal. Usually these agents are ORGANOMETALLIC compound electrophoretically metals, such as metals of groups 1, 2 and 3. Examples of alkylating agents include alyuminiiorganicheskikh connection and magyarkanizsa connection. The first include (1) compounds, vpisivaushiesya General formula AlR2nX3-nwhere n is an integer in the range from 1 to 3, inclusive, each R2independently represents a monovalent organic group (which may contain heteroatoms, such as N, O, Si, S, P and the like)connected to the Al atom via the C atom, and each X independently represents a hydrogen atom, a halogen atom, a carboxylate group, alkoxide group or Allexinno group; and (2) oligomeric linear or cyclic alumoxane, which can be obtained by carrying out the reaction between the derivative trihydrochloride and water. The latter include compounds vpisivaushiesya General formula MgR3yX2-ywhere X is defined above, y is an integer in the range from 1 to 2, inclusive, a R3is the same, and R2except that each monovalent organic the group linked via a C atom and an atom of Mg.

Some compositions of the catalysts may contain compounds having one or more movable halogen atoms. Preferably halogenated compounds are soluble in hydrocarbon solvents, such as those that were previously described in connection with the compounds of the lanthanides, although insoluble in the hydrocarbon compounds can be suspended in the polymerization medium. Suitable halogen-containing compounds include elemental Halogens, mixed Halogens, hydrogen halides), organic halides, inorganic halides, halides of metals, ORGANOMETALLIC halides and mixtures of any two or more of the aforementioned compounds.

Other compositions of the catalysts contain gecoordineerde anion or predecessor necoordonarea anion. Examples necoordonarea anions include anions tetraarylborates acid, in particular, the anions of fluorinated tetraarylborates acid, and ionic compounds containing coordinarussia anions and proteotion, (for example, tetrakis(pentafluorophenyl)borate triphenylarsine). Examples predecessors necoordonarea anions include boron compounds, which include a strong electron-withdrawing group.

The composition of the catalysts belonging to the just described type have a very high catalytical the second activity towards the polymerization of conjugated dienes with obtaining stereospecific Polivanov in a wide range of concentrations and ratios, although polymers having the most desirable properties are usually obtained from systems that use a relatively narrow range of concentrations and ratios of ingredients. In addition, the ingredients of the catalyst appears to interact with the formation of the active catalyst particles, so that the optimal concentration of each ingredient may depend on the concentration of other ingredients. The following molar ratios are relatively typical for a wide range of different systems on the basis of the above ingredients:

alkylating agent to the lanthanide compound (alkylating agent/Ln):

from ~1:1 ~200:1, preferably from about 2:1 to about 100:1, more preferably from about 5:1 to about 50:1;

halogen-containing compound to the lanthanide compound (halogen atom/Ln): from ~1:2 to about 20:1, preferably from about 1:1 to about 10:1, more preferably from about 2:1 to about 6:1;

alumoxane to the connection of the lanthanide, in particular, the equivalents of aluminum atoms in alumoxane to the equivalents of lanthanide atoms in the lanthanide compound (Al/Ln): from ~50:1 to ~50000:1, preferably from ~75:1 to ~30000:1, more preferably from about 100:1 to about 1,000:1; and

gecoordineerde anion or its predecessor to the lanthanide compound (An/Ln): from ~1:2 to about 20:1, preferably from about 3:4 to ~10:1, more preferably from about 1:1 to about 6:1.

The molecular weight of policie is s, obtained when using catalysts based on lanthanides, can be adjusted in the adjustment of the amount used of the catalyst and/or values of the concentrations of socialization in the catalyst; thus, can be obtained polydiene characterized by a wide range of molecular masses. In General, increasing the concentration of catalyst and socializaton reduces the molecular weight of the resulting polydiene, although very low polydiene (for example, liquid polydiene) require the use of extremely high concentrations of catalyst.

The inclusion of one or more of Ni-containing compounds in the composition of catalysts based on lanthanides allows best way to make an easy regulation of the molecular weight of the resulting polydiene without any significant negative impact on the catalyst activity and polymer microstructure. Can be used in various Ni-containing compounds or mixtures thereof. Ni-containing compounds are preferably soluble in hydrocarbon solvents, such as those presented earlier, although to obtain a catalytically active particles insoluble in hydrocarbons Ni-containing compounds can be suspended in olymerization environment.

The Ni atom in the Ni-containing compounds can be in any of several oxidation States, including oxidation States 0, +2, +3 and +4, although in the General case, preferred are divalent compounds of Ni, where the Ni atom is in oxidation state +2. Examples of Ni compounds include carboxylates, organophosphates, organophosphate, organophosphonate, xanthates, carbamates, dithiocarbamates, β-diketonates, alkoxides, aryloxides, halides, pseudohalogen, oxychloride, michelangelesque compounds (i.e. compounds containing at least one bond C-Ni, such as, for example, nickelocene, geometrician and the like) and the like.

The molar ratio between Ni-containing compound and a compound of a lanthanide (Ni/Ln) generally is in the range from ~1:1000 to about 1:1, preferably from about 1:200 to about 1:2, and more preferably from about 1:100 to about 1:5.

These types of compositions of the catalysts can be obtained using any of the following ways:

(1) the Receipt in place. The ingredients of the catalyst are added to a solution containing the monomer and the solvent (or just a monomer in weight). The addition can be carried out Paladino or simultaneously. In the latter case, it is preferable to first add an alkylating agent and then adding in the order specified, soy is inane of lanthanide, Nickel compounds (if using any) and (if using any) halogenated compounds or necoordonarea anion or predecessor necoordonarea anion.

(2) Pre-mixing. Ingredients prior to paired the diene monomer (monomers) can be mixed outside the polymerization system, generally at a temperature in the range from approximately 20° to approximately 80°C.

(3) Pre-receipt in the presence of monomer (monomers). The ingredients of the catalyst is stirred in the presence of a small amount of the conjugated diene monomer (monomers) at a temperature in the range from approximately 20° to approximately 80°C. the Amount of conjugated diene monomer may be in the range from ~1 to ~500 moles, preferably from ~5 to ~250 moles, and more preferably from ~10 to ~100 moles, to one mole of the compounds of the lanthanide. The resulting composition of the catalyst is added to the remainder of the polymerized conjugated diene monomer (monomers).

(4) two-Stage method.

(a) Alkylating agent combined with the lanthanide compound in the absence of conjugated diene monomer or in the presence of a small amount of conjugated diene monomer at a temperature in the range of the approximately 20° to about 80°C.

(b) the Above mixture and the remaining components of the load to the rest of the polymerized conjugated diene monomer (monomers) or Paladino, or both.

(Ni-containing compound in the case of such can be included at any stage).

In the case of a solution of one or more ingredients of the catalyst in the above ways outside the polymerization system is preferably will be to use an organic solvent or carrier. Suitable organic solvents include those mentioned previously.

Obtaining CIS-1,4-polydiene carried out in the polymerization of the conjugated diene monomer (monomers) in the presence of a catalytically effective amount of the composition of the catalyst. The total concentration of the catalyst used in the mass polymerization depends on the interaction of various factors such as the degree of purity of ingredients, temperature of polymerization, the desired rate of polymerization and the degree of transformation required molecular weight and many other factors; in accordance with this specific total concentration of the catalyst cannot be cast definitely except, say, the requirements that must be used catalytically effective to the number of relevant ingredients of the catalyst. The amount used of the compounds of the lanthanide in the General case is in the range from ~0.01 to ~2 mmol, preferably from ~0.02 to ~1 mmol, and more preferably from ~0.05 to ~0.5 mmol, per 100 g of the conjugated diene monomer. All other ingredients in General added in amounts that are based on the number of connections of lanthanide (see the various ratios shown earlier).

The polymerization is preferably carried out in an organic solvent, i.e., in the form of a solution or precipitation polymerization when the monomer is in the condensed phase. The ingredients of the catalyst preferably solubilizers or suspended in the organic liquid. The amount of monomer (wt.%), present in the polymerization medium at the beginning of the polymerization, generally is in the range from ~3 to ~80%, preferably from ~5 to ~50%, and more preferably from ~10% to ~30%. (Polymerization can also be carried out using polymerization in mass, held either in the condensed liquid phase or in the gas phase).

Regardless of the use of periodic, continuous or properities method, the polymerization is preferably carried out with stirring in the range from moderate to intense anaerobic conditions in the presence of inert shielding the Aza, such as the N2, Ar or He. The temperature of polymerization may vary within wide limits, although usually use a temperature in the range from ~20° ~90°C; heat can be abstracted using external cooling and/or cooling through evaporation of monomer or solvent. Used pressure polymerization may vary within wide limits, although usually use a pressure in the range from approximately 0.1 to approximately 1 MPa.

In the case of the polymerization of 1,3-butadiene obtained CIS-1,4-polybutadiene in General is characterized by a value of Mnaccording to the definition by GPC method using polystyrene standards in the range from ~5000 to ~200,000 daltons, from ~25,000 to ~150,000 daltons, or from about 50000 to ~to 120,000 daltons. The polydispersity of the polymers in General is in the range from ~1.5 to ~5,0, usually from ~2.0 to ~4,0.

The resulting polydiene can mainly be characterized by a content of CIS-1,4-units, equal to at least ~60%, at least about ~75%, at least about ~90% and even at least about ~95%, and a content of 1,2-connecting links, less than ~7%, less than ~ 5%, less than ~2%, and even less than ~1%, in both cases, when calculating the total number of entered diene.

Both of the described method of polymerization mainly the result of chains of the polymer, are active (living or pseudo-living) end groups, which can be additionally introduced into the reaction with one or more functionalitywith agents to obtain functionalized polymers. As described earlier, the functionalization can improve the interaction between the polymer and dispersed fillers in rubber mixtures, thereby improving the mechanical and dynamic properties of the resulting vulcanizates.

Funktsionalismi agent in the General case includes disillusioned and containing a heteroatom group or functionality that can react with polymers with terminal active group; non-limiting examples of such groups include groups (thio)isocyanate, (thio)aldehyde, imine, amide, trihydroxybenzophenone, esters (thio)carboxylic acids and their salts, anhydrides of carboxylic acids and acid halides, dihydrocarvone esters of carbonic acid, (thio)keto-, epoxy - and epithiopropyl. Specific examples of some of these compounds include those shown previously in formula (II), in which each R' independently can represent R, or alternatively, both groups R' together may form a substituted or unsubstituted divalent organic group, which together with two at the Mami Si and the N atom of disillusionary is cyclic functionality; the second of these possibilities can be represented by the following structure:

Preferred compounds vpisivaushiesya formula (II)include those in which Q is determined as in formula (II-a), while J represents O. within this group a preferred subset includes those compounds in which R1represents fenelonov group. Specific examples of this preferred subset of compounds include N,N-bis(trimethylsilyl)-2-aminobenzophenone, N,N-bis(trimethylsilyl)-3-aminobenzophenone, N,N-bis(trimethylsilyl)-4-aminobenzophenone (abbreviated hereinafter referred to as BTNSUB), N,N-bis(trimethylsilyl)-2-aminoacetophenone, N,N-bis(trimethylsilyl)-3-aminoacetophenone, N,N-bis(trimethylsilyl)-4-aminoacetophenone, N,N-bis(trimethylsilyl)-2-aminobenzaldehyde, N,N-bis(trimethylsilyl)-1-aminoanthracene, N,N-bis(trimethylsilyl)-2-aminoanthracene, N,N-bis(trimethylsilyl)-6-aminopropan, N,N-bis(trimethylsilyl)-7-aminopropan, N,N-bis(trimethylsilyl)-1-amino-9-fluorenone, N,N-bis(trimethylsilyl)-2-amino-9-fluorenone, N,N-bis(trimethylsilyl)-3-amino-9-fluorenone, N,N-bis(trimethylsilyl)-4-amino-9-fluorenone, N,N-bis(trimethylsilyl)-3-aminocoumarin, N,N-bis(trimethylsilyl)-7-amino-2-methylchromone, N,N-bis(trimethylsilyl)-7-amino-4-methylcoumarin, N,N,N',N'-tetrakis(trimethylsilyl)-1,2-diaminoethane, N,N,N',N'-tetracy the(trimethylsilyl)-1,4-diaminoanthraquinone, N,N,N',N'-tetrakis(trimethylsilyl)-1,5-diaminoanthraquinone, N,N,N',N'-tetrakis(trimethylsilyl)-2,6-diaminoanthraquinone, N,N,N',N'-tetrakis(trimethylsilyl)-1,3-diaminooctane, N,N,N',N'-tetrakis(trimethylsilyl)-2,2'-diaminobenzophenone (abbreviated hereinafter referred to as TSDB), N,N,N',N'-tetrakis(trimethylsilyl)-3,3'-diaminobenzophenone, N N,N',N'-tetrakis(trimethylsilyl)-4,4'-diaminobenzophenone, N,N,N',N'-tetrakis(trimethylsilyl)-2,3-diaminobenzophenone, N,N,N',N'-tetrakis(trimethylsilyl)-2,4-diaminobenzophenone, N,N,N',N'-tetrakis(trimethylsilyl)-3,4-diaminobenzophenone, N,N,N',N'-tetrakis(trimethylsilyl)-2,7-diamino-9-fluorenone, N,N,N',N'-tetrakis(trimethylsilyl)-1,4-diaminoanthraquinone, N,N,N',N'-tetrakis(trimethylsilyl)-1,8-diaminoanthraquinone and N,N,N',N'-tetrakis(trimethylsilyl)-1,4-diaminoanthraquinone.

Other preferred compounds vpisivaushiesya formula (II)include those in which Q is determined as in formula (II-b), while J represents O. within this group a preferred subset includes those compounds in which R1represents a C1-C6alkylenes group. One specific example of this preferred subset of compounds is represented by N,N-bis(trimethylsilyl)glycodelin (abbreviated hereinafter referred to as BTMGA).

The reaction between such functionalityin agent (agents) and polymers with reactive the end group can be carried out relatively quickly (within a period of time ranging from several minutes to several hours) as a result of simple mixing at moderate temperatures (for example, in the range from 0° to 75°C). In General use from ~ 0.01 to ~200 moles, preferably from ~0.1 to ~150 moles, and more preferably from ~0.25 to ~75 moles funktsionaalsusega agent (agents) to one mole of the compounds of the lanthanide. If necessary, the functionalization reaction may be carried out in a polymerization vessel.

This functionalization reaction may produce a macromolecule having the structure, opisyvayuschaya formula (III), which can also be described as the product of the reaction between the polymer and, in particular, carbanions or pseudo-living polymer, and a compound that includes decelerating and at least one functionality that can react with reactive end group of the polymer or to accede to it. Non-limiting examples of functionalities that can react with reactive end group of the polymer, include (thio)keto-, epoxy - and epithiopropyl. In certain embodiments of a compound may also contain one, two or even more aromatic (e.g. phenyl) groups, and in certain embodiments of each of the aromatic groups may contain at least one atom of N, associated with one of its C atoms of the ring; in certain preferred embodiments of everyone at the m N similarbut group, which contains C1-C6the alkyl chain. In other embodiments of the epoxy - or pitifullest can be attached to giselelamanque through C1-C6alkylenes group. The connection just described type, in the General case can be determined in accordance with the structure, opisyvayuschaya formula (II).

Upon completion of the reaction functionalization for decontamination of any residual reactive polymer chains and composition of the catalyst to the polymer may be added to the agent extinguishing reaction. Agent extinguishing reaction may be one or more proton compounds, such as, for example, alcohols, carboxylic acids, inorganic acids, water and the like. To add, simultaneously with or after addition of the agent quenching the reaction may be added antioxidantsoto used antioxidant may be in the range from ~0.2 to ~1% when calculating the weight of the polymer product.

The functionalized polymer can be isolated from the polymerization mixture by conventional methods such as drying in a drum dryer, drying in the extruder, vacuum drying and the like, which may be combined with coagulogram water, alcohol or steam. In the case of coagulase the project may be desirable drying in the oven.

Functionalized polymers can possess particularly advantageous properties in the case of the preparation of these compounds, among others, reinforcing fillers such as carbon black and silica. They can be used in the filled mixture sidewall or tread, or can be mixed with any commonly used rubber tread mixture comprising natural rubber and/or defunctionalization synthetic rubbers, such as, for example, one or more Homo - and interpolymers that include only produced from the polyene monomer units, (for example, poly(butadiene), poly(isoprene) and copolymers comprising butadiene, isoprene and the like), SBC, butyl rubber, neoprene, ethylene/propylene rubber, ethylene/propylene/diene rubber, acrylic nitril/butadiene rubber, silicone rubber, forecaster, ethylene/acrylic rubber, ethylene/vinyl acetate interpolymer, epichlorhydrine rubbers, chlorinated polyethylene rubbers, chlorosulphurized polyethylene rubbers, hydrogenated nitrile rubber, tetrafluoroethylene/propylene rubber and the like. In the case of mixing the functionalized polymer (polymers) with the usual rubber (rubber) number can range from approximately 5 to approximately 99% of total is aucuba, thus ordinary caoutchouc (rubber) will be the remainder of the total rubber. The minimum number largely depends on the desired level of reduction of the hysteresis.

Elastomeric mixture is usually filled up to a volume fraction, which represents the total amount of added fillers (fillers), divided by the total volume of an elastomer mixture, often equal to ~25%; typical (combined) number of reinforcing fillers are in the range of from about 30 to about 100 hours/one hundred hours of rubber, the upper limit of the range is mainly determined by how well the process equipment can cope with higher viscosities obtained in the case of the use of such fillers.

Suitable fillers include various forms of carbon, including but not limited to the following: furnace carbon black, variations of channel gas soot and varieties of lamp black. More specifically, examples of types of carbon black include varieties sverhsekretnoj furnace black varieties resistant furnace black varieties restrospective furnace black varieties of fine furnace black, variations of speed furnace black varieties poluostrova oven with the LM, varieties sredneobrazovatel channel gas sags variety of difficult-to-channel gas soot, varieties conductive channel gas soot and varieties of acetylene black; can be used mixtures of two or more of them. Preferred are varieties of carbon black (EMSA), characterized by a specific surface area equal to at least 20 m2/g, preferably at least about 35 m2/g; the values of the specific surface area can be determined by ASTM D-1765 using the methods with the use of bromide of cetyltrimethylammonium (BCTA). Types of carbon black may have a granular form, or a form of flocculent mass, although in the form of carbon black may be preferred for use in certain faucets.

The amount of carbon black can reach up to approximately 50 hours/one hundred hours of rubber, with the usual amount is in the range from approximately 5 to approximately 40 hours/one hundred hours of rubber.

The filler can also be used amorphous silicon dioxide (SiO2). Varieties of silicon dioxide in the General case when classification refers to the varieties of hydrate dioxide, PU glue, which I obtained by the wet method, because they receive as a result of chemical reactions in the water from which they precipitated in the form of ultramontanism spherical particles. The data of the primary particles are associated and durable aggregates, which, in turn, are combined into a less strong agglomerates. "Vysokodispersnom the silicon dioxide" is any of silicon dioxide, having a pronounced ability to deagglomerate and dispergirujutsja in an elastomeric matrix, which can be observed by the method lincosamines microscopy.

The specific surface area is a reliable measure of reinforcing nature of the various types of silicon dioxide; accepted method of determining the specific surface area is the method of brunauer, Emmett and teller ("BET") (described in the publication J. Am. Chem. Soc, vol. 60, p.309 et seq.). Defined by BET method, the specific surface area of the varieties of silicon dioxide in the General case are less than 450 m2/g, usually in the range from ~32 to ~400 m2/g or from ~100 to ~250 m2/g or from ~150 to ~220 m2/year

The pH of the filler is silicon dioxide (if using any) in the General case is in the range from about 5 to about 7 or more, preferably from about 5.5 to CA is approximately 6,8.

Commercially available varieties of silicon dioxide include various brands of powdered and granular varieties of the silica Hi-Sil™ (PPG Industries, Inc.; Pittsburgh, Pennsylvania). Other suppliers of commercially available silicon dioxide include Grace Davison (Baltimore, Maryland), Degussa Corp.(Parsippany, NJ), Rhodia Silica Systems (Cranbury, new Jersey) and J. M. Huber Corp.(Edison, NJ).

Silicon dioxide can be used in amounts in the range from approximately 1 to approximately 100 hours/one hundred hours of rubber, preferably in amounts in the range from approximately 5 to approximately 80 hours/one hundred hours of rubber. If used together with the technical carbon number of silicon dioxide can be reduced to only approximately 1 h/hundred hours of rubber; at least reduce the amount of silicon dioxide can be used for smaller quantities of additives and additional silane in the case of using such.

In the case of silicon dioxide will often add sizing, such as silane, which provides good mixing and interaction with the elastomer (elastomer). In General, the amount of silane that is added is in the range of about 4 to 20% based on the weight of the filler is silicon dioxide that is present in elastome the Noah mixture.

The coupling agents can be described by the General formula A-T-G, in which A represents a functional group capable of physically and/or chemically contact group on the surface of the filler is silicon dioxide (for example, with surface silanol groups); T represents the connecting link in the form of a hydrocarbon group; G represents a functional group capable of contact with the elastomer (for example, through the sulfur-containing connecting group). Such coupling agents include organosilane, in particular, polysulfone alkoxysilane (see, for example, U.S. patents№№3873489, 3978103, 3997581, 4002594, 5580919, 5583245, 5663396, 5684171, 5684172, 5696197 and the like) or polyorganosiloxanes having the above-mentioned functionality G and A. Sample sizing is a bis[3-(triethoxysilyl)propyl]tetrasulfide.

To reduce the number of used silane can be used adding processing AIDS. See, for example, U.S. patent No. 6525118 in the description of fatty acid esters of Sugars that are used as additives. Additional excipients used as additives include, but are not limited to, the following: mineral fillers such as clay (water aluminum silicate), talc (water magnesium silicate and mica, and that the same remineralise fillers, such as urea and sodium sulfate. Preferred varieties of mica mainly containing alumina, silica and potash, despite the possibility of using other options. Additional fillers can be used in a number that goes up to ~40 hours/one hundred hours of rubber, usually up to ~20 hours/one hundred hours of rubber.

Can also be added and other conventional additives to the rubber. They include, for example, process oils, plasticizers, antioxidants, such as antioxidants and protivostaritel, hardeners and the like.

All the ingredients can be mixed using standard equipment, such as, for example, a Banbury mixer or Brabender. Typically, the mixing is carried out in two or more stages. During the first stage (often called stage masterbatches) mixing usually start at temperatures in the range from ~120° to ~130°C, and the temperature increases until it reaches the so-called temperature dropping, usually equal to ~165°C.

In the case of formulation into silicon dioxide to separate add the silane component (components) often use a separate stage of Pereverzeva. This stage is often carried out at temperatures similar to those used at the stage of masterbatches, though often the smaller of them, that is, linearly varying from ~90°C to the temperature dropping to ~150°C.

Reinforced rubber mixture is usually utverjdayut when using from about 0.2 to about 5 hours/one hundred hours of rubber of one or more of the known presses, such as, for example, system hardening on or sulfuric peroxide basis. For a General description of suitable presses the interested reader is directed to review, such as the one presented in Kirk-Othmer, Encyclopedia of Chem. Tech., 3d ed., (Wiley Interscience, New York, 1982), vol. 20, str-468. The vulcanizers, accelerators and the like add to final mixing. To reduce the chances of unwanted podocarpaceae and/or premature start of vulcanization this stage stirring often carried out at lower temperatures, for example, starting with values ranging from ~60°C to ~65°C and not exceeding the values in the range of ~105°C to ~110°C.

Then the composed mixture is processed (e.g., rolls), receiving the sheets, then profiles in the form of any of a wide range of components, and then vulcanized, which is usually carried out at a temperature above the highest temperature used during the stages of mixing, the value in the range from ~5°C ~15°C, most often equal priblizitelen is 170°C.

The following non-limiting illustrative examples provide the reader with a detailed description of the conditions and materials that may be suitable for use in the practice of the present invention.

EXAMPLES

Example 1: TMDB

In a round-bottom reaction flask, cooled in an ice bath, stirred approximately 5.1 g of 4,4'-diaminobenzophenone, 10.7 g of triethylamine and 10 ml of toluene. To this mixture paypalno mode was added a solution of 23.5 g trimethylsilyltrifluoromethane in 50 ml of toluene.

Before removing the vacuum toluene and unreacted reagents, the resulting mixture for 2 days was stirred at room temperature. The residue was extracted using 100 ml of hexane. Evaporation of the hexane layer in vacuum at 40°C resulted in the receipt of ~of 11.0 g (yield 92%) of yellow solid.

According to the confirmation data spectroscopy1H NMR (C6D6, 25°C, pattern matching with tetramethylsilane was) structure has the form

that matches the structure opisyvayuschaya the earlier formula (II), each of R and R' represents a methyl group, R1represents fenelonov group, and Q is described by formula (II-a), and J represents O, and R is fenelonov the th group, replaced by disillumination.

Example 2: BTNSUB

In a round-bottom reaction flask, cooled in an ice bath, stirred approximately 12.0 g of 4-aminobenzophenone, 13.5 g of triethylamine and 15 ml of toluene (15 ml). To this mixture paypalno mode solution was added to 29.7 g trimethylsilyltrifluoromethane in 50 ml of toluene.

Before removing the vacuum toluene and unreacted reagents, the resulting mixture for 2 days was stirred at room temperature. The residue was extracted using 100 ml of hexane. Evaporation of the hexane layer in vacuum at 50°C resulted in the receipt of ~19.3 g (yield 93%) of a viscous brownish-yellow liquid.

According to the confirmation data spectroscopy1H NMR (C6D6, 25°C, pattern matching with tetramethylsilane was) structure has the form

that matches the structure opisyvayuschaya the earlier formula (II), each of R and R' represents a methyl group, R1represents fenelonov group, and Q is described by formula (II-a), and J represents O; R represents a phenyl group.

Example 3: BTMGA

In a flask equipped with a reflux condenser, stirred approximately 10.4 g of epichlorohydrin and 112 ml solution in THF bis(trimethylsilyl)amide lithium concentration of 10 mol/L. The mixture for approximately one hour was heated on boiling.

The solvent from the reaction mixture were removed in the evaporation in vacuum at room temperature. The remaining reaction mixture was distilled in vacuum, obtaining ~of 12.1 g (yield 50%) as a colourless liquid.

According to the confirmation data spectroscopy1H NMR (C6D6, 25°C, pattern matching with tetramethylsilane was) structure has the form

that matches the structure opisyvayuschaya the earlier formula (II), each of R and R' represents a metal group, R1represents a methylene group, and Q is described by formula (II-b), and J represents O, and each R represents N.

Example 4: Synthesis of (unmodified) CIS-1,4-polybutadiene

In a reactor equipped with turbine blades mixing device, added 1,403 kg of hexane and 3,083 kg of a solution of 1,3-butadiene in hexane with a concentration of 20.6% (mass).

Pre-obtained catalyst was obtained by mixing of 7.35 ml methylalumoxane in toluene with a concentration 4,32 mol/l, 1.66 g of the above solution of butadiene, of 0.59 ml of versatate neodymium in cyclohexane concentration 0,537 mol/l, to 6.67 ml hydride diisobutylaluminum in hexane with a concentration of 1.0 mol/and of 1.27 ml of a solution of chloride diethylamine in hexane with a concentration of 1.0 mol/L. The catalyst before it is loaded into the reactor was subjected to aging for ~15 minutes.

The temperature of the reactor jacket was exposed to 65°C, and after ~53 minutes after adding the catalyst, the polymerization mixture was cooled to room temperature. The resulting polymer mass coagulate when using 12 l of isopropanol containing 5 g of 2,6-di-tert-butyl-4-METHYLPHENOL, and then dried in a drum dryer.

Example 5: Synthesis of the second (unmodified) CIS-1,4-polybutadiene

Essentially repeating the process of example 4, with quantities of used reagents and catalyst components, are summarized in the following next table.

a solution of 1,3-butadiene in hexane with a concentration of 22.4% (mass.)
Table 1
Number
Polymer
hexane1,651 kg
a solution of 1,3-butadiene in hexane with a concentration of 22.4% (mass.)2,835 kg
Catalyst
the solution methylalumoxane in toluene with a concentration 4,32 mol/l6,10 ml
1.27 g
the solution versatate neodymium in cyclohexane concentration 0,537 mol/l0,49 ml
the solution of the hydride diisobutylaluminum in hexane with a concentration of 1.0 mol/lof 5.53 ml
the chloride solution diethylamine in hexane with a concentration of 1.0 mol/l1,05 ml

After about 72 minutes after adding the catalyst, the polymerization mixture was cooled to room temperature. The resulting polymer mass coagulate and dried in a drum dryer as in example 4.

The control properties of the polymers of examples 4 and 5 were compiled in the following table 3.

Examples 6-9: Modified CIS-1,4-polybutadienes

Essentially repeating the process of example 4. To the reactor was added 1,526 kg of hexane and 2,940 kg of a solution of 1,3-butadiene in hexane with a concentration of 18.8% (mass).

Pre-obtained catalyst was obtained and was subjected to aging as described in example 4.

The temperature of the reactor jacket was exposed to 65°C, and after ~60 minutes after adding the catalyst, the polymerization mixture was cooled to on the th temperature.

Portions of the polymer mass was transferred into four flasks, blown with the use of N2brought into reaction with various functionalitywith materials. Details are provided in the following next table.

Table 2
The amount of polymer massThe way functionalization
Example 6423 g8,88 ml TMDAB (from example 1) in cyclohexane concentration 0,200 mol/l
Example 7 (comparative)425 g6,07 ml solution of 4,4'-bis(diethylamino)benzophenone in toluene with a concentration of 0,294 mol/l
Example 8433 gthe 6.06 ml BTNSUB (from example 2) in cyclohexane concentration 0,300 mol/l
Example 9 (comparative)422 gof 5.06 ml solution of 4-(diethylamino)benzophenone in toluene with a concentration 0,350 mol/l

Each flask for ~30 minutes which was in a water bath, maintained at 65°C. the Polymer in each flask coagu Aravali when using 3 l of isopropanol, containing 0.5 g of 2,6-di-tert-butyl-4-METHYLPHENOL, and then dried in a drum dryer.

The properties of these functionalized polymers are summarized below in table 3.

Example 10: CIS-1,4-polybutadiene modified when using BTMGA

Essentially repeating the method of example 4. To the reactor was added 1,512 kg of hexane and 2,954 kg of a solution of 1,3-butadiene in hexane with a concentration of 21.5% (mass).

Pre-obtained catalyst was obtained and was subjected to aging as described in example 4.

The temperature of the reactor jacket was exposed to 65°C, and after ~55 minutes after adding the catalyst, the polymerization mixture was cooled to room temperature.

A portion of the polymer mass in 435 g was transferred into the flask, purged when using the N2, and introduced into a reaction from 5.26 ml BTMGA (from example 3) in hexane with a concentration of 0,463 mol/L. This flask was treated in the same way that the bulb of examples 6-9.

The properties of the polymers obtained in examples 4-10, presented below in tabular form. The values of the Mooney viscosity for the unfilled rubber (ML1+4) was determined using the Mooney viscometer Monsanto™ (large rotor) using time warming up in one minute and time in four minutes; the molecular weight was determined by the method of the GPC using polystyrene standards; and the levels of 1,2-, CIS-1,4 and TRANS-1,4 - units was determined by the results of IR spectroscopic analysis.

Table 3:
The properties of the polymers of examples 4-10
45678910
Mn(kg/mol)116,9130,7110,9107,8108,8111,0115,5
Mw/Mnto 1.861,991,831,871,851,841,93
ML1+4at 100°C for unfilled rubber29,444,221,621,820,9of 21.91,7
The levels of CIS-1,4-units (%)94,595,094,394,394,394,394,3
The content of TRANS-1,4-units (%)5,04,55,25,25,25,25,2
The content of 1,2-units (%)0,50,50,50,50,50,50,5

Examples 11-13: Synthesis of styrene/butadiene copolymers

In a reactor equipped with turbine blades mixing device, added 5,100 kg of hexane, 1,278 kg of a solution of styrene (33,0% (mass.) in hexane) and 7,670 kg of a solution of 1,3-butadiene in hexane with a concentration of 22.0% (mass). The reactor was loaded 11,98 ml n-utility (1.6 mol/l in hexane) and 3.95 ml 2,2-bis(2'-tetrahydrofuryl)propane (1.6 mol/l in hexane). The jacket of the reactor was heated and immediately after reaching the temperature of the batch to 50°C Ruba is ku reactor was cooled with cold water.

In the flask, purged when using the N2the reaction in portions of the polymer mass 420 g extinguished when using 3 ml of isopropanol containing 0.3 g of 2,6-di-tert-butyl-4-METHYLPHENOL, and then spent coagulating (~3 liters of isopropanol containing 0.5 g of 2,6-di-tert-butyl-4-METHYLPHENOL) and drying in a drum dryer. In the following next table this case is identified as example 11.

In another flask, purged when using the N2that portion of the polymer mass 416 g were introduced into a reaction with ~5,1 ml BTMGA (from example 3) in hexane with a concentration of 0.50 mol/liter Flask within ~30 minutes which was in a water bath, maintained at 50°C. the Resulting mixture to coagulate and dried in a drum dryer, as before. Further, this case is identified as example 13.

For the purposes of determining the second initial experimental points on the following figure 2 received another unmodified SBC (identified hereinafter as example 12). In the smaller reactor equipped with turbine blades mixing device, added 1,597 kg of hexane, 0,399 kg of a solution of styrene (34,0 wt.% in hexane) and 2,440 kg of a solution of 1,3-butadiene in hexane with a concentration of 22.3 wt.%. The reactor was loaded 2,58 ml n-utility (1.6 mol/l in hexane) and 0,85 ml 2,2-bis(2'-tetrahydrofuryl)propane (1.6 m is l/l in hexane). The jacket of the reactor was heated and immediately after reaching the temperature of party 55°C jacket of the reactor was cooled with cold water. This polymer adhesive from the reactor were removed and coagulate in isopropanol containing 2,6-di-tert-butyl-4-METHYLPHENOL, and dried in a drum dryer.

Table 4:
The properties of the polymers from examples 11-13
111213
Mn(kg/mol)106,1185,5to 112.2
Mw/Mn1,031,051,16
ML1+4at 100°C for unfilled rubber8,749,515,2
Tg (°C)-32-31-32
The content of styrene (%)of 21.220,0of 21.2
The content of 1,2-units (%)56,255,556,2

Examples 14-22: Obtaining and testing of vulcanizates When using the recipes below are from polybutadienes of examples 4-10 and styrene/butadiene copolymers from examples 11-13 got filled with the mixture, with quantities expressed in hours/one hundred hours of rubber.

Table 5:
Songs filled with mixtures
CIS-1,4-polydiene (examples 14-20)SBC (examples 21-23)
the synthesized polymer80100
polyisoprene200
carbon black (type N343)5050
Oil (low content of polycyclic aromatics (PCA)1010
wax22
10,95
ZnO2,52,5
stearic acid22
accelerators1,31,3
sulfur1,51,5
Total170,3170,25

The values of the Mooney viscosity (ML1+4) was determined at 130°C for examples 14-20 (polybutadienes) and 100°C for examples 21-23 (SBC) using a Mooney viscometer Alpha Technologies™ (large rotor) using time warming up in 1 minute and operating time of 4 minutes.

The vulcanizates obtained from each of the mixtures within ~15 minutes utverjdali at 171°C. the Mechanical tensile properties were determined using the methods described in the document ASTM-D412. Data on the effect Payne (ΔG') and hysteresis (tan δ) was obtained in the experiment on the sweep dynamic deformation carried out in accordance with the conditions shown in table 6.

The table is 6:
Experiments on the sweep deformation
CIS-1,4-polydiene (examples 14-20)SBC (examples 21-23)
temperature (°C)5060
frequency (Hz)110
scan for deformation0,1%-20%0,25%-15%
strain values for ΔG'0.1% and 20%0.25% and 14%
strain values for tan δ3%5%

Physical data properties of the vulcanizates are compiled in the following table 6, where Tbis the limit tensile stress at the moment of rupture, and Ebrepresents the percentage elongation at the moment of rupture, respectively.

53,6
Table 7:
Physical properties of mixtures and vulcanizates
Polim is p (example) ML1+4mixtureTbat 23°C (MPa)Ebat 23°C (%)ΔG' (MPa)tan δ
14454,612,34242,99is 0.135
15567,213,14352,560,124
16665,611,53361,780,100
17757,812,6373Damount of 0.118
18858,212,83802,330,121
19914,24103,000,137
201068,6the 13.43502,110,101
211131,715,54744,030,249
2212of 89.117,65291,75of) 0.157
231356,318,34680,720,131

Data from table 7, among other things, demonstrate that the vulcanizates obtained from mixtures using CIS-1,4-polybutadienes, functionalized compounds having disillusionary, (examples 16, 18 and 20), in comparison with the vulcanizates obtained using unmodified CIS-1,4-polybutadienes, lead to decrease the structure value of tan δ at 50°C (figure reduced hysteresis) and ΔG' (indicator reduce the effects of pain due to improved interaction between polymer and filler technical carbon). Examples 17 and 19 (comparative) was obtained when using polymers, functionalized compounds having dialkylamino, one of them (example 19) showed no reduction of hysteresis and the effect of Payne in comparison with the vulcanizates obtained using unmodified polymers, while the other (example 17) demonstrated a reduced hysteresis and reduced the effect Payne, respectively, but to a lesser extent in comparison to what is achieved by the use of appropriate desilylation analogue (example 16).

As interpolymers SBC, vulcanizer, obtained from a mixture using SBC modified when using BTMGA, (example 23) showed a low value of tan δ at 60°C (indicator of low hysteresis and low value ΔG' (an indicator of reduced effect Payne due to a more significant degree of interaction between SBC and filler particles of carbon black) in comparison with the vulcanizate obtained from mixtures using defunctionalization control SBC polymers (examples 21-22).

1. A method of obtaining a functionalized polymer comprising the reaction between the polymer with the active end group, which contains a diene monomer fragment and connection, which is cancel disillusioned and group able to react with polymers with active end group selected from keto, tyketto-, epoxy -, epithio group.

2. The method according to claim 1, wherein said group capable to react with polymers with active end group, is ketogroup.

3. The method according to claim 2, in which the said connection further includes at least two aromatic groups, each of which optionally contains at least one nitrogen atom which is directly related to the atom With the aromatic ring.

4. The method according to claim 1, in which each Si atom mentioned disillusionary associated with C1-C6alkyl group.

5. The method according to claim 1 in which the said compound includes more than one disillusioned.

6. The method according to claim 5, in which the N atom each of these more than one disillusionary directly linked to an atom of an aromatic ring.

7. The method according to claim 1 in which the said polymer is characterized by a content of CIS-1,4-units, equal to at least 95%.

8. The method according to claim 1, in which said reaction is carried out in a solvent system that contains a liquid aliphatic hydrocarbon.

9. The polymer containing diene monomer fragment and an end piece which includes decelerating and the rest of the group containing gets what roath, these terminal fragment described by the General formula

where each R independently represents a hydrogen atom or a substituted or unsubstituted monovalent organic group; J represents an atom of O or S;
R1represents a substituted or unsubstituted divalent organic group; and each R' independently represents R, or both groups R' together form a substituted or unsubstituted divalent organic group, which together with two Si atoms and the N atom of dissimilatory form a cyclic functionality.

10. The polymer according to claim 9, in which the group R attached to the atom is a methyl group, and R1represents a C1-C6alkylenes group.

11. The polymer according to claim 9, in which the group R attached to the atom, represents a substituted phenyl group, and R' represents fenelonov group.

12. The polymer according to claim 9, in which R' represents R, and each R, is attached to each Si atom, and independently represents a C1-C6alkyl group.

13. The polymer according to claim 9, characterized by a content of CIS-1,4-units, equal to at least 95%.

14. Vulcanizer, containing at least one type of dispersion of the filler and the polymer according to any one of PP-13.

15. The product containing vulcanizer at 14.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to varnish-and-paint material, modified by nano-dispersive layered silicates, dispersed in solution of highly molecular compound by means of ultrasonic processing. Varnish is applied for procession of products and constructions from concrete, metal, wood, bricks and other materials. Varnish base represents bitumen of brand G and solvent, which represents mixture of xylene and white spirit in ratio 1:1. Bituminous varnish additionally contains organophilic nano-dispersive layered silicates, distributed in solution of bituminous resin. Ratio of bitumen of brand G, xylene, white spirit and organophilic nano-dispersive layered silicates constitutes respectively 1-1.12:0.58-0.65 0.58-0.65:0.03.

EFFECT: modified in such way varnish-and-paint material has improved characteristics, in particular, increased moisture-protecting properties, and this does not require fundamental changes of the technological process of its production.

1 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to rubber-technical, tyre, footwear industry and other fields of technology, in particular, to rubber mixtures based on diene and ethylenepropylene elastomers, filled with silica white or its combination with technical carbon. Rubber mixture includes diene or ethylenepropylene caoutchouc, silica white with caoutchouc interaction promoter. As promoter mixture contains two-component composition. First component of composition - alkoxysilane, contains unsaturated hydrocarbon substituent at silicon atom, selected from group-gamma- methacryloxypropyl-trimethoxysilane and vinyl trimethoxysilane in quantity 1-6 wt.fr. per 100 wt.fr. of caoutchouc. Second component of composition is polyorganosiloxane with content of hydridesilane groups -1.0-1.7% and is selected from group methylhydridesiloxane and methyl(methyloctyl)hydridesiloxane in quantity 1.0-2.2 wt.fr per 100 wt.fr. of caoutchouc.

EFFECT: invention makes it possible to improve properties of rubber mixture and its vulcanisers, as well as to increase temperature of mixture preparation above 150°C without risk of scorching.

5 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: claimed invention relates to method of obtaining functionalised polymer, which is applied in manufacturing rubber products, such as tire treads. method includes the following stages: (a) application of catalytic system based on lanthanides for polymerisation of one or greater number of polyenes with obtaining active by terminal groups polymer, (b) reaction of said active by terminal groups polymer with polyiso(thio)cyanate with formation of polymer with terminal iso(thio)cyanate functional group, and (c) reaction of said polymer with terminal iso(thio)cyanate functional group with nucleophile, which has one of the following general formulas: H2NR"Si(OR3)3 or HSR"Si(OR3)3, where R" represents substituted or non-substituted divalent aliphatic group, substituted or non-substituted aromatic group or group, which contains heteroatom, and R3 represents hydrogen atom or substituted or non-substituted alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, allyl, aralkyl, alkaryl or alkinyl group, to obtain functionalised polymer.

EFFECT: obtaining functionalised polymer, application of which contributes to demonstration by filled compositions for tyre treads of improved wet traction in addition to reduction of hysteresis, as well as increased tensile strength and considerable reduction of Payne effect.

2 cl, 3 tbl, 12 ex

Nitrile rubbers // 2491296

FIELD: chemistry.

SUBSTANCE: invention relates to nitrile rubber, method of its obtaining and products, obtained from it. Claimed nitrile rubber contains structure repeat units of, at least, one α,β- unsaturated nitrile and, at least, one conjugated diene, and has ion indicator in range 0-60 ppm×mole/g. Nitrile rubber is obtained by emulsion polymerisation. Obtained latex, which contains nitrile rubber, is subjected to coagulation, and then coagulated nitrile rubber is washed. Polymerisation is carried out in presence of, at least, one alkylthiolate. Before coagulation value of latex pH is set at level, at least, 6, and then is coagulated in presence of, at least, one magnesium salt. Temperature of latex before adding at least one salt of magnesium is set at value 45°C. Obtained nitrile rubber is applied for obtaining capable of vulcanisation mixtures, which contain claimed rubber, at least, one linking agent and, if necessary, additional target additives to rubbers. Capable of vulcanisation mixtures are vulcanised by casting with obtaining cast products.

EFFECT: claimed nitrile rubbers have exclusive speed of vulcanisation, as well as exclusive properties of vulcanisates.

24 cl, 13 tbl, 17 ex

FIELD: construction.

SUBSTANCE: method includes mixing of bitumen and rubber crumb of tyre wastes, their temperature treatment and mixture plasticising. Bitumen and rubber crumb in the composition are used at the following ratio, wt %: rubber crumb - 13.0-31.0, bitumen - balance. At the same time rubber crumb is added into bitumen pre-heated up to 160°C in portions with mixing, besides, after loading of its last portion the mixture is mixed for around 10 minutes. Then, while the mixture is being mixed, it is treated with ultrasound, upon completion of which the mixture is mixed for around 10 minutes.

EFFECT: rubber and bitumen compositions have higher values of softening and brittleness temperatures preserved in severe climatic conditions under higher mechanical loads.

5 cl, 1 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: bitumen-polymer paste contains bitumen, a polymer additive, ethyl silicate and mineral filler. The polymer additive used is atactic polypropylene, the filler used is flue ash from Krasnoyarsk TPP-2, and the ethyl silicate is ethyl silicate-32. Components are in the following ratio, wt %: bitumen - 86-40; atactic polypropylene - 2-10; ethyl silicate-32 - 2-10; flue ash from Krasnoyarsk TPP-2 - the balance.

EFFECT: high heat resistance, frost resistance and low water saturation of the paste.

6 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: composition includes a mixture of asphalt and aggregates in a system of additives distributed therein, said system of additives including: i) from about 10 to 60 wt % amine or modified amine surfactant and ii) from about 20 to 90% asphalt rheology modifying components. Said asphalt rheology modifying component includes: i) at least one wax component, ii) optionally one or more infusible components that are insoluble in asphalt and ii)at least one resinous component, and mixtures and combinations thereof. The amount of said system of additives in the asphalt composition ranges from 0.2 to 10 wt % per content of asphalt in said composition. The invention also relates to a method of improving water-resistance properties of a hot asphalt mixture containing aggregates. Said method involves adding an effective amount of said system of additives to said asphalt.

EFFECT: system of additives affects adhesion and cohesion properties of asphalt by considerably improving resistance of hot asphalt mixtures to damage caused by moisture.

21 cl, 2 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: method involves adding a composition of a hydrogen sulphide scavenger to asphalt. The hydrogen sulphide scavenger contains a polyaliphatic amine of formula 1: H2NRNH - (RNH)n - H (1), where R is an aliphatic radical and ranges from 0 to about 15 and a catalyst of formula 2: R1R2R3R4N+X- (2), where each of R1, R2, R3 and R4 independently represents an alkyl group containing 1-20 carbon atoms, a hydroxyalkyl group containing 1-20 carbon atoms, or an aryl group containing 6-20 carbon atoms and X represents a halide or methyl sulphate. Asphalt is treated with said composition.

EFFECT: low content of hydrogen sulphide in asphalt.

25 cl, 2 dwg, 2 ex

FIELD: construction.

SUBSTANCE: asphalt-concrete mixture contains oil bitumen, limestone crushed stone with fraction of 5-20 mm, sand with fraction of up to 5 mm, mineral powder and polymer additive, besides, the polymer additive is liquid divinyl piperylene rubber SKDP-N and additionally ethyl silicate-40 at the following ratio of components, wt %: oil bitumen - 4.9-6.6, crushed limestone of specified fraction - 25-40, sand of specified fraction - 43-64.5, mineral powder - 5-10, liquid rubber SKDP-N - 0.1-0.7, ethyl silicate-40 - 0.1-0.7.

EFFECT: increased strength limit, frost resistance, water resistance and reduced water saturation.

6 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to polyamide-elastomer mixtures for making moulded articles. The polyamide-elastomer mixture contains components in the following ratios, wt %: a) 30 to 95 of at least one partially crystalline polyamide having a solution viscosity greater than or equal to 1.75 (measured in m-cresol solution, 0.5 wt %, 20°C.), b) 5 to 50 of at least one elastomer produced by emulsion polymerisation of at least one conjugated diene, at least one α,β-unsaturated nitrile and, optionally, one or more additional copolymerisable monomers and subsequent spray drying of the latex obtained during emulsion polymerisation, c) optionally, 0 to 20 of one or more polyamides having a solution viscosity of less than 1.75 (measured in m-cresol solution, 0.5 wt %, 20°C.), relative to the total amount of components (a) to (c), and relative to 100 parts by weight of components (a) to (c), from 0 to 100 parts by weight of one or more additives. The disclosed polyamide-elastomer mixtures can be processed into moulded articles which are used, for example, in the motor car industry, particularly as channel conducting media.

EFFECT: good flexibility of polyamide-based materials and improved resistance to hydrolysis and oil swell.

33 cl, 4 dwg, 2 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: flame-extinguishing polymer composition contains a combustible polymer mixed with a bromated flame-extinguishing additive selected from one or more compounds given below: (i) a copolymer containing styrene and 2,3-dibromopropylmaleimide repeating units; (ii) a bromated polyester containing bromine atoms bonded with aliphatic groups; (iii) an allyl ether which is bromated on a novolac resin ring; (iv) 3-bromo-2-hydroxypropyl ether of novolac resin; (v) 2,3-dibromopropyl ether cresol-novolac resin, and (vi) a bromated polymer or a copolymer obtained via ROMP.

EFFECT: stability of the flame-extinguishing additive at high temperatures, low toxicity and avoiding significant loss of physical properties of the polymer during use thereof.

7 cl, 10 ex

Polymer composition // 2477297

FIELD: chemistry.

SUBSTANCE: invention relates to composite polymer materials based on a highly processable butadiene-acrylonitrile elastomer, which can be used to produce vulcanisates with high tensile strength, tear resistance, good dynamic properties and heat-ageing resistance. The polymer composition based on butadiene-acrylonitrile elastomer (SKN-26) and polyvinyl chloride (PVC) is modified with aluminium oxide nanoparticles. The polymer composition based on butadiene-acrylonitrile elastomer (SKN-26) polyvinyl chloride (PVC) contains sulphur, captax, thiuram, stearin and aluminium oxide.

EFFECT: improved operational characteristics: strength and dynamic mechanical properties.

1 tbl, 17 dwg

FIELD: chemistry.

SUBSTANCE: composition contains (A) about 10-80 wt % soft rubber-like resin based on a vinyl aromatic copolymer, (B) about 4-60 wt % rubber-modified resin based on a vinyl aromatic copolymer and (C) about 5-80 wt % resin based on a vinyl aromatic-vinyl cyanide copolymer. Resin (A) contains as a dispersion phase rubber particles with content of graft polymer of about 40-90%, and average particle diameter of about 6-20 mcm. The moulded article is made by moulding from said thermoplastic resin composition and has a soft surface touch with average surface roughness of about 400-800 nm.

EFFECT: invention enables to obtain moulded articles with a pleasant low lustre and high impact viscosity.

16 cl, 5 dwg, 2 tbl, 10 ex

FIELD: chemistry.

SUBSTANCE: composition contains (A) a bisphenol-based homopolycarbonate in amount of 10-90% of the weight of the composition (weight parts), B) 10-90 pt.wt first graft (co)polymer containing a graft copolymerisation base selected from a group consisting of polyurethane, ethylene-vinyl acetate, silicone, ethylene-propylene-diene rubber, ethylene-propylene rubber, acrylate rubber, diene rubber and polychloroprene. When the first graft copolymer contains 3-50% rubber component, and when the graft phase contains 49-96% polymerised monovinyl diene aromatic monomer and 1-48% monoethylene unsaturated polar monomer, wherein the percentage relates to the weight of the first graft (co)polymer. The composition also contains 1-20 pts.wt linear polymer (C) with glycidyl ester functional groups, containing repeating units based on one or more glycidyl ester monomers. The composition contains 1-20 pts.wt second graft (co)polymer (D) containing a nucleus and a shell. The molecular structure of the nucleus includes an all-permeating mesh structure made from poly(meth)alkyl acrylate. The shell is made by polymerising methyl methacrylate.

EFFECT: low light-reflecting power and high impact strength at low temperatures.

17 cl, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a thermoplastic moulding composition which is flame retardant and impact resistant. The thermoplastic moulding composition for making moulded articles contains aromatic polyester carbonate, polyalkylene terephthalate, graft copolymer having a nucleus-shell morphology, having a graft shell which contains polymerised alkyl(meth)acrylate, and a nucleus made from composite rubber which contains interpenetrating and inseparable polyorganosiloxane and poly(meth)alkyl acrylate components in form of particles having size from 0.05 to 5 mcm and glass transition temperature lower than 0°C, and where the weight ratio polyorganosiloxane/poly(meth)alkyl acrylate/hard shell equals 70-90/5-15/5-15, and a phosphorus-containing compound (IVa), where R1, R2, R3 and R4 denote phenyl, R5 denotes hydrogen, n equals 1, q ranges from 1 to 2, Y denotes C(CH3)2 and fluorinated polyolefin.

EFFECT: high resistance to inflammation and impact strength.

8 cl, 1 tbl

FIELD: chemistry.

SUBSTANCE: composition contains the following in %: a) 35-78% aromatic polycarbonate, b) 6-55% thermoplastic polyester - polyethylene terephthalate, c) 5-15% halogenated acrylate, d) 3-15% impact resistance modifier, e) 2-15% phosphate-containing compound and f) 0.05-0.5% fluorinated polyolefin. The acrylate contains repeating structural units of the following formula: in which R1, R2, R3, R4 and R5 denote hydrogen, alkyl or aryl, n ranges from 0 to 5, m ranges from 10 to 10000, and R denotes halogen. The phosphate-containing compound is selected from a compound of formula (III) O-P-[-OCH2C(CH2Br)3]3 (III) and compounds of formula , in which R1, R2, R3 and R4 denote C1-C8-alkyl, C5-C6-cycloalkyl, C6-C20-aryl or C7-C12-aralkyl, unsubstituted or substituted with alkyl, n equals 0 or 1, N equals 0.1-30, X denotes a mono- or polycyclic aromatic residue with C6-C30 or a linear or branched aliphatic residue with C2-C30.

EFFECT: invention enables to obtain a composition with higher impact resistance and fire resistance.

3 cl, 1 tbl, 4 ex

The invention relates to the chemistry of polymers, namely to stable compositions based resin plant (ABS) copolymers, which are structural materials

The invention relates to a method for producing a resin plant (ABS) resins

The invention relates to the production of thermoplastic rubber compositions and can be used in rubber industry

The invention relates to the field of thermoplastic rubber compositions and can be used in rubber and rubber industry

FIELD: chemistry.

SUBSTANCE: invention relates to an aramid particle containing a peroxide radical chain polymerisation initiator, wherein the particle contains 3-40 wt % of a radical chain polymerisation initiator with respect to the weight of the aramid particle. The peroxide initiator is introduced into the aramid particle by saturating the aramid particle with a solution of the peroxide initiator in an organic solvent with subsequent evaporation of the latter. The aramid particle is fibre, crushed fibre, staple fibre, fibrid, fibril, powder or granules. Also described is an elastomer composition with aramid particles, an article made from skimmed latex which contains the elastomer composition with aramid particles, an industrial rubber article and a method of curing an elastomer in the presence of an aramid particle.

EFFECT: reduced Payne effect and hysteresis of rubber or other elastomeric articles, improved adhesion properties.

12 cl, 16 tbl, 3 ex

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