Elastomeric mixture containing polyfunctional organosilane as binding agent

FIELD: chemistry of polymers.

SUBSTANCE: invention relates to an elastomeric composition that can be used in making pneumotires or intermediate products for pneumotires. The composition is based on at least one diene elastomer, inorganic filling agent as an enhancing filling agent, polyfunctional organosilane, namely hydroxysilane of the general formula (I) given in the invention description as a binding agent (for system inorganic filling agent/diene elastomer) comprising at least two functional groups designated as "X" and "Y" that can be grafted to elastomer by one side using function X, and to inorganic filling agent by other side using function Y that represents hydroxysilyl function (≡Si-OH) and wherein organosilane is represented by hydroxysilane polysulfide of the general formula (I), and wherein the amount of inorganic enhancing filling agent is from 10 to 200wpe (weight parts per 100 weight parts of elastomer), and the amount of hydroxysilane polysulfide is in the range from 1 to 20wpe. Also, invention relates to a method for preparing the claimed elastomeric composition showing the improved kinetics of vulcanization by thermomechanical stirring components of the composition for one or two steps up to achievement of maximal temperature from 110 to 190°C. Also, invention relates to using this composition for manufacturing pneumotires or intermediate products designated for pneumotires, for example, protectors, sublayers, sides and so on, and to a pneumotire and an intermediate product for pneumotire containing such elastomeric composition, to a protector for pneumotire made of this composition and to pneumotire containing such protector. Also, invention relates to using a polyfunctional organosilane as a binding agent and to a method for binding inorganic and diene elastomer in an elastomeric composition by polyfunctional organosilane. The claimed elastomeric composition provides satisfactory reserve of safety with respect to the burning problem, it possesses a lower value of Mooney plasticity resulting to good ability for treatment in crude state and possesses the improved hysteresis properties and the improved the conversion constant rate and therefore vulcanization can be carried out for significant shorter time. Protectors made of the proposed composition possess low resistance to rolling motion and enhanced abrasion resistance.

EFFECT: improved and valuable properties of mixture.

32 cl, 2 tbl, 2 dwg

 

The present invention relates to compositions of diene elastomers, reinforced inorganic filler, suitable for use in the production of pneumasin or intermediates for pneumasin, particulars of protectors for pneumasin.

The invention in particular relates to binding agents suitable for binding the reinforcing inorganic filler and the diene elastomer in such elastomeric compositions.

It is known that usually, to obtain optimum reinforcing properties reported by the filler, the final form in which the filler will be present in the elastomeric matrix, should be the most finely chopped and at the same time more evenly distributed. However, such conditions can be fulfilled only in the case when the filler has a very good ability, on the one hand, be incorporated by mixing with the elastomer in the matrix and disagglomerated and, on the other hand, evenly dispergirujutsja in the matrix.

Very well known that such properties of carbon soot, which, as a rule, not typical inorganic fillers. Indeed, because of the mutual affinity of the particles of inorganic filler have an unpleasant tendency to aglomerirovanie with each other in an elastomeric matrix. Harmful what he effects of these interactions is they limit the dispersion of the filler and, consequently, decrease the reinforcing properties to a much lower level compared to the level that could be theoretically achieved if it were effectively implemented all of the links (in the system of the inorganic filler-elastomer), which could occur when blending operation. On the other hand, these interactions tend to increase the consistency of rubber compounds in the raw state and, hence, to impede processing (to deteriorate the processability) compared to processing in the presence of carbon black.

Since the fuel savings and the need to protect the environment has become a priority, found it necessary to produce pneumosinus with reduced rolling resistance without compromising their durability. This was, in particular, possible thanks to the discovery of new rubber (rubber) blends, reinforced special inorganic fillers referred to as "reinforcing", which can compete in quality amplifiers with traditional carbon black category for pneumasin", telling rubber mixtures lower hysteresis that is synonymous with lower rolling resistance containing these compounds pneumasin.

Such rubber mixtures containing increasing the possibility of inorganic fillers, silica or alumina type, were, in particular, are described in the patents and patent applications EP-A-0501227 (or US-A-5227425), EP-A-0735088 (or US-A-5852099), EP-A-0810258 (or US-A-5900449), EP-A-0881252, WO99/02590, WO99/02601, WO99/02602, WO99/28376, WO00/05300, WO00/05301.

It should in particular be mentioned document EP-A-0501227, EP-A-0735088 or EP-A-0881252 that reveal the diene rubber compound, reinforced with highly dispersed precipitated by silica with a high capacity for dispersion, which allow to produce treading pneumasin, with a significantly improved rolling resistance, without affecting other properties, in particular for traction, fatigue strength and wear resistance. Such a mixture having the above balance of mutually exclusive properties described in the applications EP-A-0810258 and WO99/28376, where as reinforcing inorganic fillers used special alumina fillers (aluminum oxide, oxide-aluminum hydroxide) with high dispersibility, or in applications WO00/73372 and WO00/73373, which describes a special titanium oxides with the reinforcing action.

The use of highly dispersible inorganic fillers as dominant or not dominant reinforcing filler has certainly reduced the difficulties in the application containing these fillers in rubber compounds, however, is the change of these mixtures still continues to be more difficult compared to conventional rubber compounds with carbon soot.

In particular, it is necessary to use a binding agent, also referred to as coupling agent, whose task is to provide communication between the surface of the particles of the inorganic filler and the elastomer, thus facilitating the dispersion of this inorganic filler within the elastomeric matrix.

Recall here that the term "binding agent" (for inorganic filler/elastomer) should, as usual, to understand the agent capable of sufficiently good communication chemical and/or physical nature, between the inorganic filler and the diene elastomer. Such binding agent, at least bifunctional, has, for example, the General formula Y-W-X, in which:

- Y represents a functional group (Y)capable of physically and/or chemically to contact with the inorganic filler, and such connection can be established, for example, between a silicon atom of a binding agent and hydroxyl groups (OH) of the surface of the inorganic filler (for example silanol surface groups, if we are talking about silica);

- X represents a functional group (X)capable of physically and/or chemically to contact with the diene elastomer, for example via a sulfur atom;

- W means a divalent group linking Y and X.

Connect the s agents should not in particular, to be confused with conventional coating agents for the inorganic filler, which, as is well known, can contain a function Y with activity against inorganic filler, but does not have a function of X, with activity against diene elastomer.

Binding agents, in particular for the system silica/diene elastomer, have been described in many documents, and the most famous of these agents are bifunctional organosilane having as functions of Y, at least one CNS function, and as a function of X at least one function capable of interacting with the diene elastomer, such as structuresa function.

Further, in patent applications FR-A-2094859 or GB-A-1310379 it was proposed to use for the manufacture of treading pneumasin mercaptohexadecanoic linking agent. This was quickly discovered and today it is well known that although mercaptohexanol and able to provide excellent communication silica-elastomer, but the industrial application of these binding agents is impossible because of the very high reactivity of serosoderjaschei groups such as thiol-SH (X)that in the preparation of rubber mixtures in a closed rubber mixer quickly leads to premature vulcanis the tion, also called the "burning" ("scorching"), to high viscosity in the raw state and, ultimately, to the rubber mixtures, which is almost impossible to work and to apply on an industrial scale. To illustrate this problem, you can refer to, for example, in documents FR-A-2206330, US-A-3873489, US-A-4002594.

To overcome the above drawback, it was proposed to replace mercaptohexanol polysulfide by alkoxysilane, in particular polysulfides bis(alkoxysilyl) such as those described in a very larger number of documents (see, for example, FR-A-2149339, FR-A-2206330, US-A-3842111, US-A-3873489, US-A-3997581, EP-A-680997 or US-A-5650457, EP-A-791622 or US-A-5733963, DE-A-19951281 or EP-A-1043357, WO00/53671). Of these polysulfides should, in particular, to call tetrasulfide bis(3-triethoxysilylpropyl) (abbreviated to TESPT) and disulfide bis(3-triethoxysilylpropyl) (abbreviated to TESPD).

These polysulfides of alkoxysilanes, in particular TESPT is generally regarded as the products which give the vulcanizates containing reinforcing inorganic filler, in particular silica, the best compromise between preventing burning, ease in applying and enhancing abilities. For this reason, these products are linking agents, the most widely used in rubber mixtures for pneumasin, even though they are the Xia relatively expensive and also often must be used in relatively large quantities.

However, these polysulfides of alkoxysilanes have a disadvantage consisting in that they significantly slow down the kinetics of vulcanization containing rubber mixtures in comparison with the kinetics of vulcanization traditional blends, reinforced carbon soot. Due to this increased duration of vulcanization may in some cases hinder the industrial use of such rubber compounds reinforced with inorganic fillers, and the use thereof rubber products.

At the same time, applicants when conducting their research unexpectedly found that some special organosilane possible to overcome the drawback associated with the kinetics of vulcanization, without sacrificing binding and, therefore, enhance the ability and giving, thus, the rubber mixtures improved balance of properties compared to the balance of properties achieved to date using polysulfide alkoxysilanes, in particular with TESPT.

These special organosilane not create besides the above-mentioned problems of premature burning and problems due to too high viscosity of rubber compounds in the cheese state - of shortcomings inherent in mercaptohexanol.

Thus, the first object of the invention is an elastomer to notice based on at least one diene elastomer, inorganic filler as reinforcing filler and a polyfunctional of organosilane as a binding agent (for inorganic filler/diene elastomer)having at least two functions, denoted by "X" and "Y"which can be grafted, on the one hand, to the elastomer by using a function of X, and, on the other hand, to the inorganic filler with the function Y, and this composition is characterized by the fact that called the function Y is gidroksietilimino function (Si-OH). In other words, the mentioned polyfunctional organosilane classified hidroxizina.

As far as known to applicants, organosilane that meets this definition, never up to the present time is not used as a binding agent in rubber compounds reinforced inorganic filler, and even were not synthesized because of the strong bias against the known instability organosilanes having hydroxyl functions. It is appropriate here to remind you that this instability is due to the high propensity gidroksilnyh groups (Si-OH), in particular in the presence of strong acids (formed during the synthesis organosilanes from halogenosilanes), samarangense with the formation of the relations Si-O-Si, or as they are called, siloxane linkages. On the other hand, this mechanism is used for the synthesis of polysiloxanes (see, for example, the following works: "The Chemistry of organic silicon compounds", S. Patai and Z. Rappoport, John Wiley & Sons, 1989, Part I, 722-725; "Siloxane polymers", S.I. Clarson, S.J.Semlyen, Ellis Horwood Pretice-Hall, Elgelwood Cliffs N.J., 1993, 577-578; 597).

The object of the invention is also the use of elastomer compositions according to the invention for the production of pneumasin or for the production of intermediates intended for these pneumasin, and these intermediates include, in particular, to the group, which includes protectors, sublayers, for example, for placing them under these protectors, the upper, side, frame layers, contour, protective layers, an air chamber and an inner sealing rubber for tubeless pneumasin.

The object of the invention is also the above pneumosinus and intermediates containing elastomer composition according to the invention, and these pneumosinus can be, in particular, intended for cars and industrial vehicles from trucks, heavy vehicles, i.e. underground, buses, road transport vehicles (lorries, tractors, tugs), off-road vehicles, agricultural or construction machinery, aircraft and other transport and handling equipment.

The invention in particular relates to the prot the factors named pneumasin, which can be used in the production of new pneumasin or to impose new protectors worn on newmachine. Thanks to the compositions according to the invention, these protectors have both low rolling resistance, very good traction, high abrasion resistance, and improved kinetics of vulcanization.

The rubber mixtures according to the invention with improved kinetics of vulcanization can be prepared by using method, characterized in that at least one diene elastomer is injected at least one inorganic filler as reinforcing filler and a polyfunctional organosilane as a binding agent (for inorganic filler/diene elastomer)having at least two functions, denoted by "X" and "Y"which can be grafted, on the one hand, to the elastomer by using a function of X and, on the other hand, to the inorganic filler with the function Y, and this function Y is gidroksietilimino function (Si-OH), and the fact that the thus obtained mixture is subjected to a thermomechanical mixing in one or several stages before reaching the maximum temperature in the range from 110 to 190aboutC.

The subject of the invention is also the use of a binding agent (for systememergency filler/diene elastomer) in the composition based on a diene elastomer, reinforced inorganic filler, and a certain higher polyfunctional of hidroxizina.

The object of the invention is also a method of binding the inorganic filler and the diene elastomer in the elastomeric composition, characterized in that at least one diene elastomer is injected at least one inorganic filler as reinforcing filler and a polyfunctional organosilane having at least two functions, denoted by "X" and "Y"which can be grafted, on the one hand, to the elastomer by using a function of X and, on the other hand, to the inorganic filler with the function Y, and the function Y is gidroksietilimino function (Si-OH), and the fact that the thus obtained mixture is subjected to a thermomechanical mixing in one or several stages before reaching the maximum temperature in the range from 110 to 190aboutC.

The invention and its advantages will become clearer from the following description and examples of embodiment of the invention, and corresponding to these examples of drawings which represent:

- figure 1: rogramme (vulcanization curves), registered for rubber mixtures, relevant or not relevant to the invention;

- figure 2: curves module from elongation for these compounds.

I. USE ISAWANYA MEASUREMENTS AND TESTS

Rubber compounds were characterized before and after curing, as indicated below.

1-1. The Mooney plasticity

Used an oscillating consistometer as described in the French standard NF T 43-005 (1991). The measurement of the Mooney plasticity is performed in accordance with the following method: mix in a raw state (i.e. before curing) is moulded in a cylindrical vessel, heated to 100aboutC. After preheating for 1 min give effect to an inside of the sample rotor with a speed of 2 rpm and measure the torque required to maintain the rotor after 4 minutes of rotation. The Mooney plasticity (ML 1+4) is expressed in "Mooney units" (UM, where UM=0.83 Nm).

I-2. Time burning

The measurements were carried out at 130aboutIn accordance with French standard NF T 43-005 (1991). The time dependence consistencychecking index allows you to find the time burning rubber compounds, measured in accordance with the above standard, using the parameter T5 (in the case of a large rotor), expressed in minutes, and defined as the time required to obtain increase consistencychecking index (expressed in UM) up to 5 units above the minimum value measured for this indicator.

I-3. Tensile test

These tests allow to determine the voltage of elasticity and its the tion at break. Unless otherwise noted, these tests are conducted in accordance with French standard NF T 46-002 from September 1988 Measured in second elongation (i.e. after an accommodation cycle with a degree of elongation provided for the measurement) nominal secant modules (or apparent stresses, in MPa) with elongation of 10% (denoted M10), when the elongation of 100% (denoted M100) and the elongation of 300% (denoted M300). Also measured stress at break (MPa) and elongation at break (in %). All measurements stretching is carried out in conditions of normal temperature and humidity in accordance with French standard NF T 40-101 (December 1979).

The data processing extension also allows you to build a curve based module from lengthening (see attached figure 2), where used by the module is the true secant modulus, measured at the first stretching, designed not for the initial cut, as was done above for the nominal modules, and for real segment of the sample.

I-4. Dynamic properties

Dynamic properties measured on the analyzer viscosity (Metravib VA4000) in accordance with ASTM D5992-96. Record the reaction of a sample of vulcanized mixture (cylindrical sample thickness of 4 mm and 400 mm2in cross section)is subjected to a sinusoidal load with a simple alternating shear stress with h which depends 10 Hz at normal temperature (23 about(C) in accordance with ASTM D 1349-99. Produce a scan amplitude of deformation from 0.1 to 50% (move forward) and then from 50 to 1% (reverse), registering at flybacks the maximum value observed for loss tangent tg(δ), denoted tg(δ)max.

I-5. Rheological measurements

Measurement is carried out at 150aboutWith oscillating rheometer chamber in accordance with the standard DIN 53529-part 3 (June 1983). The time dependence rheometrical torque is characterized by an increased stiffness of the mixture in the reaction vulcanization (see attached figure 1). The measured data is processed in accordance with standard DIN 53529 - part 2 (March 1983). The minimum and maximum torques measured in decanewton·m (Nam·m)denote, respectively, Cminand Cmax; timean induction time, i.e. the time needed for the start of vulcanization; tα(for example t99means the time required to achieve the conversion α%, α% (e.g. 99%) of the difference between the minimum and maximum torques. Measure the difference, denoted by ΔKrom. (DNM), between the minimum and maximum torques, as well as the rate constant for the conversion To (min-1), which allows to evaluate the kinetics of vulcanization.

II. The TERMS and THE implementation of INVENTIONS

The rubber mixtures according to the invention are based on at least each of the following components:

(i) at least one diene elastomer;

(ii) at least one inorganic filler as reinforcing filler;

(iii) at least one polyfunctional organosilane as a binding agent (for inorganic filler/diene elastomer)having at least two functions("X" and "Y"), which can be grafted, on the one hand, to the elastomer by using a function of X and, on the other hand, to the inorganic filler by using gidroksietilimino function Y (Si-OH).

Of course, the phrase "based" should be understood composition comprising the mixture and/or reaction product in situ different components used, where some of these main components is capable of or designed to communicate among themselves, at least partly, in different phases of preparation of the composition, in particular during the vulcanization process.

II-1. Diene elastomer

Under the "diene" elastomer or rubber, as is well known, means the elastomer obtained at least in part (i.e. which homopolymer or a copolymer) from diene monomers (monomers having two conjugate or non-conjugate double bond carbon-carbon).

By "substantially nanosys is authorized" diene elastomer usually mean a diene elastomer, at least partially derived from conjugated diene monomers, diene content of the original links (conjugated dienes) above 15% (molar %).

Thus, for example, diene elastomers such as butylketone or copolymers of dienes with alpha-olefins of the type EPDM, do not fit under the preceding definition and may, in particular, be classified as "essentially saturated" diene elastomers (low or very low content of the original diene units, which in any case below 15%).

Within the category of "essentially unsaturated" diene elastomers, in particular, under the "highly unsaturated" diene elastomer mean a diene elastomer with the original content of diene units (conjugated dienes) above 50%.

In light of the above definitions under diene elastomer suitable for use in compositions according to the invention, in particular, include:

(a) any homopolymer obtained by polymerization of the conjugated diene monomer having from 4 to 12 carbon atoms;

(b) any copolymer obtained by copolymerization of one or more conjugated dienes with each other or with one or more aromatic vinyl compounds having from 8 to 20 carbon atoms;

(c) any ternary copolymer obtained by copolymerization of ethylene, α-olefin, it is found from 3 to 6 carbon atoms, with non-conjugate diene monomer having from 6 to 12 carbon atoms, such as, for example, the elastomers obtained from ethylene and propylene with a non-conjugate diene monomer of the abovementioned type, such as, in particular, 1,4-hexadiene, ethylidene-norbornene, Dicyclopentadiene;

(d) any copolymer of isobutylene with isoprene (butyl rubber), as well as halogenated, for example, chlorine - or brominated versions of the copolymer of this type.

Although the present invention applies to any type of diene elastomer, the specialist wheel pneumatic tyres clear that in the case when the rubber compound is designed, in particular, to tread pneumatiky, the invention is implemented primarily with essentially unsaturated diene elastomers, in particular of the type specified above (a) or (b).

As conjugated dienes suitable, in particular, 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di(C1-C5-alkyl)-1,3-BUTADIENES such as 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-isopropyl-1,3-butadiene, an aryl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene.

As vinylaromatic compounds are suitable, for example, styrene, o-, m - and p-methylstyrene, sales mix "vinyltoluene", p-tert-butalbiral, methoxystyrene, chloresterol, minimization, divinylbenzene, WinInet the lean.

The copolymers can contain from 99 to 20 % by weight. diene units and from 1 to 80 wt.%. vinylaromatic links. The copolymers may have any microstructure, depending on the use conditions of polymerization, in particular from the presence or absence of a modifying and/or randomizing agent and the used amounts of modifying and/or randomizing agent. The elastomers can be, in particular, block, statistical, block-ordered and micropartitioning and can be obtained in dispersion or in solution. They can be connected in pairs and/or in the form of stars or functionalized with a binding and/or zvezdoobraznogo and/or functionalizing agent. Mostly are suitable polybutadienes and they are particularly suitable are those in which the content of the links -1,2 ranges from 4 to 80%, or those in which the content of CIS-1,4 above 80%, polyisoprenes, butadiene-styrene copolymers, in particular those in which the styrene content is from 5 to 50 % wt. and preferably from 20 to 40%, the content of links -1,2 butadiene part of between 4 to 65%, the content of the links of the TRANS-1,4 within 20%to 80%; butadiene-spredovye copolymers, in particular those in which the content of isoprene is from 5 to 90 wt.%. and the glass transition temperature (Tg is measured in accordance with ASTM D418-82) in the range of -40 to -80 aboutS; isoprene-styrene copolymers, in particular those in which the styrene content is from 5 to 50 % wt. and Tg in the range from -25 to -50aboutC.

In the case of butadiene-styrene-isoprene copolymers are suitable, in particular, those in which the styrene content is from 5 to 50 % wt. and, more preferably, from 10 to 40%, the content of isoprene in the range from 15 to 60 % wt. and, more preferably, from 20 to 50%, the content of butadiene in the range of 5 to 50 % wt. and, more preferably, from 20 to 40%, the content of the links -1,2 butadiene part of between 4%to 85%, the content of the links -1,4 butadiene portion in the range from 6 to 80%, the content of the links -1,2 plus -3,4 isoprene part of between 5% to 70% and the content of the links -1,4 isoprene part of between 10 to 50% and more often than any butadiene-styrene-isoprene copolymer has a Tg from -20 to -70aboutC.

According to one of preferred embodiments of the invention, the diene elastomer of the composition according to the invention are selected from the group diene highly unsaturated elastomers which consists of polybutadienes (BR), synthetic polyisoprene (IR), natural rubber (NR), butadiene-styrene copolymers (SBR), butadiene-isoprene copolymers (BIR), butadiene-Acrylonitrile copolymers (NBR), isoprene-styrene copolymers (SIR), butadiene-styrene-isoprene copolymers (SBIR) and the mixture is quiet elastomers.

The composition according to the invention is intended, in particular, to tread pneumasin, both new and worn (the imposition of new protectors).

When this protector is designed, for example, for pneumasin passenger transport, diene isomer is predominantly a SBR or a mixture of SBR/BR, SBR/NR (or SBR/IR), or BR/NR (or BR/IR). In the case of SBR elastomer is used, in particular, SBR styrene content in the range from 20 to 30 wt.%, the content of vinyl bonds in butadiene part of between 15 to 65%, a content of the relations of TRANS-1,4 ranging from 15 to 75% and a Tg ranging from -20 to -55aboutWith, and this copolymer SBR made mainly in solution (SSBR), can also be used in a mixture with a polybutadiene (BR), which is mainly more than 90% of relationships CIS-1,4.

In the case when the protector is designed to pneumosinus vehicles utilitarian purpose, such as heavy vehicles, the diene elastomer is mainly isoprene elastomer. Under "isoprene elastomer" usually refers to a homopolymer or copolymer of isoprene, in other words a diene elastomer selected from the group comprising natural rubber (NR), synthetic polyisoprene (IR), the various copolymers of isoprene and mixtures of these elastomers. From copolymers of isoprene, in particular, to call sprinklers which measures the isobutene-isoprene (butyl rubber - IIR), isoprene-styrene (SIR), isoprene-butadiene (BIR) and isoprene-butadiene-styrene (SBIR). Isoprene elastomer is predominantly a natural rubber or synthetic CIS-1,4. Synthetic polyisoprene used mainly polyisoprene content (mol.%) ties CIS-1,4 above 90%, preferably above 98%. Of course, the diene elastomer may also partly consist of another highly unsaturated elastomer such as SBR elastomer.

According to another preferred variant of the invention, in particular when it is intended to sidewall pneumatiky, the composition according to the invention may contain at least one essentially saturated diene elastomer, in particular at least one EPDM copolymer, which, for example, may or may not be used in a mixture with one or more of the above mentioned highly unsaturated diene elastomers.

The composition according to the invention may contain only a single diene elastomer or a mixture of several diene elastomers, or which can be used in combination with synthetic nadirovym elastomer of any type, and in some cases, polymers are elastomers, for example thermoplastic polymers.

II-2. Reinforcing filler

White carbon black, or REORG the organic filler, used as a reinforcing filler, may be the whole amount or only part of the total amount of reinforcing filler, combined in the latter case, for example, with carbon black.

The rubber mixtures according to the invention the reinforcing inorganic filler is predominantlythe amount, i.e. more than 50% by weight of the total reinforcing filler, preferably 80% by weight of the total reinforcing filler.

In this application under "inorganic reinforcing filler" implies, as is customary inorganic or mineral filler, whatever its colour and origin (natural or synthetic), also known as the white (or sometimes bright) soot, juxtaposing it thus carbon soot, and such inorganic filler capable one, without any other agent, except for acts as an intermediary, linking agent, to reinforce the rubber compound, designed for the production of pneumasin, in other words capable of replacing as traditional amplifier amplifier - carbon soot categories "for pneumasin".

Inorganic reinforcing filler is predominantly a mineral filler siliceous type, in particular (SiO2), or alumina is IPA, in particular, aluminum oxide (Al2O3), or oxide-hydroxides of aluminum, or a mixture of these different fillers.

Used silica may be silica of any well-known specialists of the type, in particular any precipitated or pyrogenic silica having a BET surface, as well as specific surface area CTAB, less than 450 m2/year, mainly from 30 to 400 m2/, Preferred precipitated silica with a high capacity for dispersion (so-called "HD"), in particular in the case where the invention is applied for manufacturing pneumasin with low rolling resistance tires. Under the silica with a high capacity for dispersing means, as is customary, any silica having a high ability to disagglomerated and dispergirujutsja in an elastomeric matrix that is observed in a known manner using electronic or optical microscopy on thin sections. As not limiting the invention, examples of such preferred silicas with a high capacity for dispersion can be called the silicas Ultrasil 7000 and Ultrasil 7005 company Degussa, the silicas Zeosil 1165MP, 1135MP and 1115MP company Rhodia, the silica Hi-Sil EZ150Q company PPG, the silicas Zeopol 8715, and 8755 Huber, and treated precipitated silicas such as, for example, as described in the aforementioned application EP-A-735088 silica, "doped" with aluminum.

Mainly used reinforcing alumina is alumina with a high capacity for dispersion, having a BET surface of from 30 to 400 m2/g, preferably from 60 to 250 m2/g, average particle size of not more than 500 nm, preferably not more than 200 nm, such as described in the aforementioned application EP-A-0810258. As not limiting the invention, examples of such reinforcing silicas can, in particular, to call the silicas "Baikalox A-125 or CR 125" (firm Bankowski"), "APA-100RDX" (firm Condea), "Aluminoxid C" (company Degussa) "AKP-G015" (Sumitomo Chemicals).

As other examples of the inorganic reinforcing filler, suitable for use in rubber mixtures of the invention may be also named oxide-hydroxides of aluminum or special titanium oxides described in the aforementioned applications WO99/28376, WO00/73372 and WO00/73373.

The physical state in which it is applied inorganic reinforcing filler, it doesn't matter: it can be in the form of powder, microbuses, granules, or beads. Needless to say that under inorganic reinforcing filler is assumed to be also a mixture of different inorganic reinforcing filler, in particular silica and/or alumina fillers with high dispersibility, which were described above.

In the case when the and the rubber mixtures according to the invention are used as protectors of pneumasin, used inorganic reinforcing filler, in particular if it is silica has a BET surface in the range from 60 to 250 m2/g, preferably from 80 to 200 m2/year

Inorganic reinforcing filler can also be applied in a mixture with carbon black. As carbon soot suit all carbon, in particular carbon black of the type HAF, ISAF, SAF, which is traditionally used in the wheel pneumatic tyres and, in particular, in the tyre tread. As not limiting the invention, examples of such soot can be called carbon black N115, N134, N234, N339, N347, N375. The amount of carbon black contained in the entire reinforcing filler may vary within wide limits, and the number of carbon predominantly less than the number contained in the rubber mixture of the inorganic reinforcing filler.

In the compositions according to the invention is preferred, however, to use carbon black in combination with inorganic reinforcing filler in a small proportion, mainly from 2 to 20 CSA, preferably in the range from 5 to 15 CSA (the weight. parts per 100 weight. parts of elastomer). These limits are provided coloring properties (agent black staining) and UV-protective properties of carbon soot without prejudice to the typical performance characteristics reported inorganic reinforcing Agay is that namely, low hysteresis (low rolling resistance) and increased grip with wet surfaces and snow-covered or icy surface.

The total content of reinforcing filler (inorganic reinforcing filler plus, in some cases, carbon black) is preferably from 10 to 200 CSA, preferably from 20 to 150 CSA (the weight. parts per 100 weight. parts of elastomer). The optimal content depends on the intended application. Indeed, the degree of amplification required, for example, for Cycling pneumosinus known to significantly lower the degree of amplification required for pneumatiky suitable for rolling in long supported high speed, for example pneumosinus motorcycle, pneumosinus cars or pneumosinus vehicles utilitarian purpose, such as heavy vehicles.

For treading pneumasin suitable for rolling in long supported high speed, the amount of the inorganic reinforcing filler, in particular if it is silica, is preferably from 30 to 120 CSE, preferably from 30 to 110 CSA.

In this presentation, the specific surface of the BOARD is determined using the known method of Brunauer-Emmet-Teller, described in the Journal of the American Chemical Society, Vl.60, p.309, February 1938, and in accordance with French standard NF T 45-007 (November 1987). Specific surface area is BECOMING an outer surface, determined in accordance with the same standard NF T 45-007.

Finally, the experts it is clear that as filler equivalent to those described in this paragraph inorganic reinforcing filler, could be used for reinforcing organic filler type, in particular carbon black for pneumasin (see, for example, WO99/28380)at least partially covered with an inorganic layer, requiring, in turn, to provide communication with the elastomer, as is well known, the use of bonding agent.

II-3. Binding agent

Used in rubber mixtures of the invention the binding agent is, as stated, at least bifunctional organosilanes providing a link between the diene elastomer and an inorganic reinforcing filler which contains in the molecule:- on the one hand, at least one functional group (X)capable of forming a stable bond with the diene elastomer;

on the other hand, and this is the essential feature of the invention, as a function of Y at least one hydroxyl group (OH) at each atom of silicon is a function called gidroksietilimino (Si-OH), allowing the PR is anusilan to be grafted to the inorganic reinforcing filler.

Without limiting the following definitions of the invention, note that the composition of the invention are mainly used with solifidianism hidroxizina, i.e. hidroxizina having as functions of X structureas functional group, in particular polysulfide group Sx(x2, i.e. including disulfide group).

As preferred examples of polysulfides hidroxizina can, in particular, to call polysulfides hidroxizina that meet the following General formula (I):

(I)

(HO)aR(3-a)Si―R'―Sx―R'―SiR(3-b)(OH)b

in which:

the radicals R, identical or different, denote a hydrocarbon group containing predominantly from 1 to 15 carbon atoms;

the radicals R', identical or different, denote divalent group designed to connect polysulfide group with two silicon atoms, mainly containing from 1 to 18 carbon atoms;a and b are the same or different, is 1 or 2;

- x is greater than or equal to 2.

In the above formula (I), the function X linking agent is a polysulfide function of Sxconnected to two silicon atoms via the radicals R', while the function Y is gidroksietilimino function (Si-OH)attached to each end of the chain.

The radicals R, identical or different, linear is or branched, mainly containing from 1 to 15 carbon atoms, selected mainly from Akilov, cycloalkyl and allow, in particular from C1-C6-Akilov,5-C8-cycloalkyl and the phenyl radical. Of these radicals can as give examples radicals selected from the group comprising methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, 2-ethylhexyl, n-octyl, isooctyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, phenyl, tolyl and benzyl.

More preferred radicals R, identical or different, are1-C3-alkilani (namely methyl, ethyl, n-propyl and isopropyl) and the most preferred radicals selected from methyl and ethyl.

The radicals R', identical or different, substituted or unsubstituted, are predominantly saturated or unsaturated hydrocarbon radicals containing from 1 to 18 carbon atoms, and the hydrocarbon chains of these radicals R' may be embedded at least one heteroatom such as O, S or N. Suitable are, in particular, alkylene group1-C18or6-C12-allenbyi group, more specifically With1-C10-alkylene, in particular With1-C4in particular chosen from methylene, ethylene and propylene.

In other words, the invention of the advantages to the public by using polysulfide (symmetrical or asymmetrical about the nature of the radicals R and R') bis(hydroxy-C 1-C18-alkylsilane-C1-C15-alkyl), meet the above General formula I, in particular polysulfide bis(hydroxy-C1-C3-alkylsulphonyl), in which the silicon atom has one or two hydroxyl group (plus, respectively, two or one alkyl group).

Mainly used monohydroxyl, i.e. hidroxizina containing one hydroxyl function (IT) on the silicon atom (a=b=1).

Thus, compounds of the above formula I, the invention is primarily used polysulphide of monohydroxybenzene, i.e. a connection that meets the following General formula (II):

Particularly preferred organosilane formula II are organosilane, in which the radicals R are C1-C3-alkali, the radicals R' are1-C4-alkylene and x is greater than or equal to 2.

From the latter, in particular, to call polysulfides bis(C1-C4-alkyl-dimethylsilanol), i.e., polysulfides, in which R is Me (methyl), meet the following individual to the formula II-1

in which x is greater than or equal to 2 and the radicals R' are1-C4-alkylene, in particular methylene, ethylene or propylene, preferably propylene.

As an example, izopet is of predominantly carried out using polysulfide bis(propyltrimethoxysilane) with a specific formula

The number of sulfur atoms x in these hidroxizina may vary within wide limits, for example from 2 to 9, depending on the specific conditions of synthesis of hidroxizina, however, the value of x is mainly chosen in the range from 2 (disulfides) to 6 (hexachloride), including appropriate trisulfide (x=3), tetrasulfide (x=4) and pentasulfide (x=5). Even more preferred x is selected in the range of 2 to 4.

The above polysulfide monohydroxybenzene above formula II (namely, II-1 and II-2) can be obtained by the method of synthesis comprising the following stages (R and R' have the above values):

- proceed from the halogenated organosilane (product A) formula And Hal means halogen)

this halogenated organosilane may be optionally subjected to alcoholysis with an alcohol (R-OH) in the presence of an organic base designed for binding formed halogenation acid, obtaining monopolkommission (hereinafter product) formula B

- carry out the hydrolysis in an inert organic solvent using donor hydroxyl:

product And in the presence of (in this case) organic basis for linking the resulting g is loginoptions acid, using as donor hydroxyl water;

or (if desired) of the product, using as a donor hydroxyl mineral base and organic solvent is a polar solvent,

getting monohydroxyethyl (product) formula

in conclusion, exercise stage sulfatirovnie product using polysulfide, obtaining the target product of formula II.

Some stages (alcoholysis, sulfatirovnie) this way, at least in their General features, have been used for the synthesis of serosoderjaschei of alkoxysilanes, such as mercaptohexanol or polysulfide alkoxysilane ( see, for example, FR-A-2149339 or US-A-4076550, FR-A-2206330, EP-A-0694552 or US-A-5405985). However, as far as known to applicants, the above stages have never been described in combination to obtain polysulfide monohydroxyethyl.

The halogen (Hal) source of silane (product A) may be the same or different and they are mainly chosen from bromine and chlorine, using preferably chlorine. In the General case, the source halogenosilanes (products) and their intermediate derivatives (products b or C) are liquid products and, therefore, can be used at various stages of the method according to the invention as such or as diluted with a suitable solvent.

<> The first, optional, stage of alcoholism is, therefore, the replacement of the halogen (Hal) at the silicon atom in the product And CNS group (OR") of the alcohol in the presence of an organic base designed for binding formed during the reaction halogenation acid. The hydrocarbon radical R ' of an alcohol (R"OH) primarily contains from 1 to 8 carbon atoms. It is chosen mainly from C1-C6-Akilov, preferably from1-C3-Akilov and, mainly, from methyl or ethyl. As an organic base designed for binding formed halogenation acid, you can use Amin, mainly tertiary amine such as triethylamine. For the best binding halogenation acid alcoholysis is carried out at a temperature below 15aboutWith, preferably below 10aboutC.

Stage hydrolysis can be carried out directly with the source halogenosilanes (product A) with water in an inert organic solvent, such as ether, in the presence of an organic base, designed as above, for binding formed halogenation acid.

However, the source haagensen prefer before hydrolysis is subjected to alcoholysis. This hydrolysis product is carried out in a polar organic will dissolve the Le, mainly in alcohol, by the action of an inorganic base in aqueous solution, and the inorganic base is mainly the hydroxide of an alkaline or alkaline-earth metal, in particular sodium hydroxide (NaOH). The base is used mainly in small surplus at the end of the reaction is neutralized with a weak acid, such as potassium dihydrophosphate. The polar organic solvent is mostly alcohol With1-C6preferably With1-C3and, mainly methanol.

For the final stage of sulfatirovnie can be used polysulphide (x2) ammonium or metal formula M2Sxor M Sx(M means an alkali metal or NH4; M' means Zn or alkaline earth metal). Examples of such compounds are polysulfides Na, K, Cs, Rb, Ca, Mg, Zn and NH4and x is predominantly in the range of 2 to 6, preferably from 2 to 4. Used mainly polysulfide of sodium Na2Sxin particular Na2S2, Na2S3, Na2S4, Na2S5, Na2S6and this polysulphide mainly formed by the action of sulfur (S8) in Na2S. Obtaining ammonium polysulfides or metals carried out in a known manner in an organic or inorganic solvent, such example is, as water, alcohols, ketones and ethers, in which the reactive agent is partially or completely soluble.

However, in order to exclude any risk of formation of side products such as polysulfides of alkoxysilanes in the adverse reaction of alcoholysis silanol functions of the product, prefer to carry out stage sulfatirovnie in the absence of any alcohol. In this case, working predominantly in the aqueous phase, preferably in a two-phase medium water/organic solvent (for example toluene, xylene, benzene, heptane and the like), as described in the aforementioned document EP-A-0694552 or US-A-5405985 in relation to the synthesis of polysulfide alkoxysilanes. The reaction sulfatirovnie in this case carried out in a known manner in the presence of a catalyst phase transition and the salt of the formula M"Hal " or " M"SO4(M" selected from Li, Na, K; Hal is selected from F, Cl and Br). Used salt mainly selected from NaCl, NaBr and Na2SO4preferring NaCl. The amount of salt can vary, for example, from 10% by weight aqueous solution until complete saturation of the solution. The catalyst for the phase transition is, for example, tetrabutylammonium (TBAB).

Stage sulfatirovnie perform primarily in the atmosphere of inert gas such as argon. The temperature of the reaction medium is not critical: m is tenderly, for example, to operate at room temperature, however, to increase the rate of reaction still prefer to work under heating, for example from 60 to 100aboutWith and in some cases up to the boiling point of the solvent. The molar ratio of hidroxizina (product) polysulfide (ammonium or metal) pick up mainly so that to have a slight excess of polysulfide in relation to its stoichiometric amount.

If sulfatirovnie is carried out in the organic phase, the product itself is preferably pre-diluted with an inert organic solvent, such as alcohol, ketone or ether. When the reaction is finished, remove the filter formed salt (metal halide) and a clear filtrate from the solvent by distillation in vacuum. If sulfatirovnie in the aqueous phase or two-phase system (water/organic solvent) organic phase containing the product D can be selected, and then the excess solvent is distilled off in vacuum.

Polysulfide hidroxizina synthesized in accordance with the above-described way, are actually mixtures of polysulfides (for example with x equal to from 2 to 9), resulting in the average value of x is not a value. The desired average value of x lies predominantly in the range of 2 to 6 and preferably is e from 2 to 4.

As a rule, the content of hidroxizina in the rubber mixtures according to the invention mainly above 1 CSA, preferably in the range from 2 to 20 CSA. Below these minimums, the effect may be insufficient, while when exceeding the recommended maximum usually improve the binding is not observed, while the cost of the mixture increases. For these various reasons, the content of hidroxizina predominantly in the range of 3 to 12 CSA.

The specialist will be able to select the contents of hidroxizina depending on the intended applications, in particular depending on the part pneumatiky, which is the rubber mixture according to the invention, from the nature of diene elastomer and the number of used inorganic reinforcing filler. Naturally, in order to reduce the cost of rubber compounds, it is desirable to use them in a smaller quantity, i.e. in that it is the amount needed for adequate communication between the diene elastomer and an inorganic reinforcing filler. The effectiveness of hidroxizina allows in most cases to use it in the preferred amounts comprising from 0.5 to 20 % wt. from the amount of the inorganic reinforcing filler, while most preferably the content of hydroc is Vilana below 15% and even more preferably below 10%.

The above hidroxizina were by themselves sufficient for the binding of diene elastomer with an inorganic reinforcing filler such as silicon. Without limiting this invention, it can be argued that they can successfully perform the role only of a binding agent contained in the rubber mixtures according to the invention.

Finally, the experts it is clear that the above hidroxizina can be pre-coated or to the diene elastomer (through function X) of the mixture according to the invention or, preferably, inorganic reinforcing filler (through Y), and such "pre-bound" inorganic filler can then be connected to the diene elastomer via free function of X.

II-4. Different additives

Needless to say, that the rubber mixtures according to the invention also contain fully or partially additives commonly used in rubber mixtures containing isoprene elastomer and intended for the production of pneumasin or protectors for pneumasin, in particular plasticizers, protective agents, such as protivosokove waxes, chemical antiozonants, antioxidants, protivooskolochnye agents, amplifiers adhesion, cross-linking system type systems on the basis of either sulfur or sulfur donors and/or peroxide and/or bis is maleimido, the vulcanization accelerators, vulcanization activators, etc. Inorganic reinforcing filler can be optionally supplemented traditional little or no reinforcing inorganic filler, such as particles of clay, bentonite, talc, chalk, kaolin, normal (non-amplifying) of titanium oxide.

The rubber mixtures according to the invention can also, in addition to the above hydroxymidazolam linking agents, contain top agents for inorganic reinforcing filler containing only a function of Y, or, more usually, auxiliary agents, have a certain ability, due to the improved dispersion of the inorganic filler in the rubber matrix and of a lowering in the viscosity of the mixtures to improve their suitability for processing in a wet state, and such agents can be, for example, alkylalkoxysilane, in particular allyltriethoxysilane, such as 1-octyl-triethoxysilane supplied to the sale by the company Degussa-HÜls under the name Dynasylan Octeo or 1-hexadecyl-triethoxysilane supplied to the sale by the company Degussa-HÜls called Si216, polyols, polyethers (for example polyethylene glycols), primary, secondary or tertiary amines (for example trialkanolamines), gidroksilirovanii or capable of either hydrolyzed polyorganosiloxanes, such as the er, α,ω-dihydroxy-polyorganosiloxanes (in particular α,ω-dihydroxy-polydimethylsiloxane).

II-5. Preparation of rubber mixtures

The mixture is prepared in suitable mixers, using two well-known specialists successive working phases: the first working phase, or thermomechanical mixing (sometimes called "unproductive"phase)at high temperature to the maximum temperature (denoted Tmaxin the range of 110 to 190aboutC, preferably from 130 to 180aboutWith, followed by a second mechanical working phase (sometimes referred to as "productive"phase) at lower temperature, typically below 110aboutWith, for example, from 40 to 100aboutWith, which is the final phase, during which introduces cross-linking or vulcanization system. Such phases have been described, for example, in the aforementioned application EP-A-0501227, EP-A-0735088, EP-A-0881252, WO99/28376, WO00/05300, WO00/05301.

The method of preparation of the mixtures according to the invention is characterized in that the first, the so-called non-productive, phase in the diene elastomer is injected with mixing at least an inorganic reinforcing filler and hidrociclonului linking agent, or, in other words, is introduced into the mixer and subjected to a thermomechanical mixing in one or more stages at least named OS is ESD up to maximum temperature in the range from 110 to 190 aboutWith, preferably in the range from 130 to 180aboutC.

As an example: the first phase (unproductive) is carried out in a single thermomechanical stage during which, in a suitable mixer, such as a conventional indoor rubber mixer, enter all required basic components, and may cover or auxiliary agents and various other additives with the exception of the vulcanization system. In the same closed rubber mixer after shrinkage of the mixture and the intermediate cooling (cooling temperature mainly below 100about(C) may be carried out optionally, the second thermo-mechanical working stage, in order to subject a mixture of additional thermomechanical treatment, in particular to further improve the dispersion of the inorganic reinforcing filler and its binding agent in the elastomeric matrix. The total duration of mixing in this non-productive phase is mainly from 2 to 10 minutes.

After cooling, the thus obtained mixture is injected at a low temperature vulcanizing system, usually in the outer rubber mixer of the type drum of the mixer. The contents of the mixer are mixed (productive phase) for several minutes, for example within 5-15 minutes

After this, the thus obtained end-see the camping rolled in the form of a sheet, plate or ekstragiruyut, for example, with the formation of the rolling rubber profile for the manufacture of intermediates, such as protectors, the upper, side, frame layers, contour, protective layers, an air chamber and an inner sealing rubber for tubeless pneumasin.

The vulcanization (boiling) is conducted in a known manner at a temperature generally in the range from 130 to 200aboutC for a sufficient time which may vary, for example, from 5 to 90 min and depends, in particular, on the temperature vulcanization used vulcanizing system, the kinetics of vulcanization of the mixture, and the amount newmachine.

Actually vulcanizing system is based mainly on the sulfur and a primary vulcanization accelerator, in particular sulfenamide type. To this base vulcanization system during the first non-productive phase and/or during the productive phase add various known secondary accelerators or vulcanization activators, such as zinc oxide, stearic acid, guanidine derivatives (in particular diphenylguanidine) etc. Sulfur is used mainly in the amount of 0.5 to 10 CSA, preferably from 0.5 to 5.0 CSA, for example from 0.5 to 3.0 CSE in the case where the invention is applied to the tread newmachine. The primary accelerator volcano is the form used mainly in the amount of from 0.5 to 10 CSA, preferably from 0.5 to 5.0 CSA in the case where the invention is applied to the tread newmachine.

Needless to say, the invention relates to the above-described rubber mixtures in the state called "raw" (i.e. before curing)and in the state called "cooked", or vulcanized (i.e. after cross-linking or vulcanization).

The mixture according to the invention can be used as such or in combination with any other rubber mixture, suitable for use for the production of pneumasin.

III. EXAMPLES of carrying out the INVENTION

The following examples of implementation of the invention is carried out with polysulfide bis(propyltrimethoxysilane) of the formula II-2:

III-1. Synthesis of polysulfide monohydrochloride

In this experiment describes the synthesis of polysulfide above formula II-2 (referred to as product D) the process is carried out in two or three stages, based on chlorpropyl-dimethylchlorosilane (hereinafter called the product) through chlorpropyl-dimethylethoxysilane (hereinafter called the product; optional path) and chlorophenyl-dimethylsilanol (hereinafter called the product).

Applied the following synthesis scheme:

a) Obtaining chlorpropyl-dimethylethoxysilane (product)

First the stage is in the United States, you can replace chlorine in the silicon atom of the product And ethoxyline group (EtO) ethanol by the reaction in the presence of triethylamine, intended to bind released during the reaction of hydrochloric acid.

A 2-l three-neck flask (previously dried in a drying Cabinet for 24 hours, which is equipped with a refrigerator and which is equipped with a magnetic stirrer, is injected with a syringe in a stream of nitrogen 950 ml of ethanol (bulleted Normapur) and then 288 ml of triethylamine (2,07 mol or 209 g). The mixture is then cooled to a temperature of approximately 5aboutAnd then using a peristaltic pump to add a product And (237,7 g, or 1.38 mol - product firms ABCR supplied on sale under the name SIC2336.0), in which the released hydrochloric acid immediately associated with triethylamine with the formation of triethylamine hydrochloride.

As soon as the fill is terminated (after approximately 8 hours, the ice bath is removed and continue stirring at room temperature in a stream of argon over night. After eight hours analysis using GFH (gas phase chromatography) indicates the disappearance of the peak corresponding to the original product And and education chlorpropyl-dimethylethoxysilane (product). Reaction medium was then filtered on a funnel push, acceleartor In ethanol from triethylamine hydrochloride.

The filtrate containing the product, evaporated and then distilled in vacuum (2 mm Hg, the temperature of the oil bath 70aboutTemperatures top of the column 45about(C) in order to remove excess of free of triethylamine and highlight the product in a pure state.

End up with 160 g of colorless liquid, NMR analysis and mass spectrometry which reliably confirm that we are talking about the desired product, corresponding to the following formula:

b) Receiving chlorpropyl-dimethylsilanol (product)

This stage (the second) is the hydrolysis obtained above ethoxysilane (in methanol solution) to obtain hidroxizina. The reaction is carried out by acting in an aqueous solution of NaOH. After the reaction is introduced initially, the excess base was neutralized with potassium dihydrophosphate.

In equipped with a magnetic stirrer, 100-ml three-neck flask is installed on the refrigerator impose 2,62 g of sodium hydroxide (65 mmol, or 2.4 equivalent with respect to the product, which is dissolved in 15 ml of demineralized water. After complete dissolution and return temperature of the solution to room add 20 ml of methanol and then, using a dropping funnel, the product obtained above In (5 g, 27.7 mmol), diluted with 35 ml of methanol. After this, the reaction medium is stirred for 90 min, and poured into water shall actor of potassium dihydrophosphate (16 g KH 2PO4in 200 ml of water). The resulting solution having a pH of 7, stirred a few minutes and then mixed with 200 ml of ether for the purpose of extraction of the formed product C. the two-phase environment then stirred for approximately 30-45 minutes and placed in a separating funnel. The separated organic phase is washed once with water and dried on MgSO4, and then filtered and evaporated in vacuum.

Chromatogram GFH collected thus the crude reaction product has three peaks that can be attributed to (i) chlorophenyl-dimethylethoxysilane formed, apparently, in the reaction of methanol with the product (about 2% of structural units based on the1H NMR), (ii) the target product, which is essentially dominated (85% of structural units based on the1H NMR), and (iii) bis(chloropropyl)tetramethyldisiloxane (present in 13% of structural units). Distillation in vacuum, performed on a column with ball extension (Kügelrohr), allows you to select the product C. during distillation keep the temperature in the column mainly below 45aboutTo reduce the risk of condensation product in the appropriate disiloxane. After removal of chlorpropyl-dimethylethoxysilane under a vacuum of 1.3 mbar and a temperature of 35aboutTo distinguish the product in the vacuum with 1 IBA and heated to 40 aboutWith, while the higher boiling bis(chloropropyl)tetramethyldisiloxane remains in the distillation flask.

As a result, there 2,48 g clear, colourless liquid, NMR analysis and mass spectrometry which confirms receipt of the product, corresponding to the following formula:

As mentioned above, the above product may also be obtained directly by hydrolysis of the raw product And in an inert organic solvent (ether) in the presence of water as a donor hydroxyl and triethylamine intended to bind the released hydrochloric acid. The water is preferably introduced in excess, thereby creating more favorable conditions for the desired reaction and avoiding the reaction of condensation of silanol formed from the insertion of CHLOROSILANES. The use of a small excess of triethylamine provides full binding hydrochloric acid, and the remaining triethylamine is distilled off after reactiile specifically, the reaction is carried out as follows: equipped with a magnetic stirrer, a 500-ml three-neck flask is installed on the refrigerator impose 9,78 ml of triethylamine (70,1 mmol, 1.5 equivalent relative to the product of (A), 3,36 g of water (187 mmol, 4 equivalents with respect to the product) and then 150 ml of ether. Received the initial solution is cooled in an ice bath (temperature < 10aboutC) and slowly added a solution of the product (8.0 g, or to 46.7 mmol in 80 ml of ether). Immediately seeing the emergence of a white precipitate, the corresponding hydrochloride of triethylamine. Upon completion of the addition product And the reaction medium was continued to stir for additional 30 min, keeping the temperature below 10aboutC. the precipitate is removed after filtration, the filtrate is collected and dried over magnesium sulfate, filtered and evaporated in vacuum. Excess triethylamine are removed by distillation. The result of 6.1 g of a bright yellow liquid, which according to NMR analysis and mass spectrometry corresponds to the target product (product purity above 95%).

C) obtaining polysulfide of hidroxizina (product D)

On this last stage, the sodium polysulfide formed by introducing sulfur in sodium sulfide, Na2S in the aquatic environment, replaces the chlorine atom of two molecules of the product in toluene solution. The reaction is carried out in the presence of a catalyst phase transition (TBAB) and sodium chloride NaCl.

In equipped with a magnetic stirrer, a 250 ml three-neck flask is installed on the refrigerator impose 3,50 (14.5 mmol) of Na2S·9H2O, and 1.40 g (43,7 mmol) of sulfur, which is dissolved in 40 ml of an aqueous solution of NaCl (5.0 g, or to 85.8 mmol) and 8 ml of toluene. This mixture is heated to 85aboutWith watching while under the mA temperature color change of the reaction medium from yellow to dark red.

After reaching the desired temperature is injected at one time of 0.25 g TAV (0.77 mmol) and begin to add dropwise the product (4,60 g, or 28.6 mmol), dissolved in 30 ml of toluene. In the process of adding toluene has a bright red color, which gradually passes into orange, while the aqueous phase, at first bright red, pale, becoming after the termination of addition, the product is colorless and transparent. The reaction continued for 75 minutes at a temperature of 85aboutS, after which the reaction medium is cooled in an argon atmosphere.

Reaction medium was then poured into a separating funnel to separate the toluene phase, which was washed with water and dried over magnesium sulfate. The organic phase is then filtered, absorb ether and distilled on a column with ball extensions (40about(C) to remove residual chlorophenyl-dimethylsilanol (product).

In total receive 3,82 g of a viscous red-orange liquid, NMR analysis and mass spectrometry reliably confirm that it contains (in mol.%):

approximately 95% of the polysulfide bis(propyltrimethoxysilane) of the formula II-2:

approximately 5% of a cyclic siloxane compound of the following formula (II-3):

The synthesized product D before the hat is the distribution of polysulfides from disulfide (x=2) to execuled (x=6) with the average value of x=3.7V. The content of the disulfide S2determined by NMR, approximately 18% of the polysulfide chains.

Thus, this product represents, as it takes place, in particular, in the case of polysulfides of alkoxysilanes, such as TESPT, the distribution of polysulfides, the average value of x which blico to 4. It is clear that changing the synthesis conditions could produce a different distribution of polysulfides with different average values of x, but predominantly in the range of 2 to 6 and mainly from 2 to 4.

III-2. Preparation of rubber mixtures

Carried out the following sequence of tests: These compounds are prepared as known method: fill in 70% indoor rubber mixer with the initial temperature in the tank approximately 60aboutTo enter the diene elastomer (or in some cases, the mixture of diene elastomers, reinforcing filler, binding agent and then the various other ingredients, with the exception of the vulcanization system. After this exercise the first thermo-mechanical operation (non-productive phase) in one or two stages (the total duration of mixing is approximately 7 min) before reaching the maximum temperature of the "shrinkage"equal 165aboutC. Unload the thus obtained mixture cool and add sulfur and sulfenamide acce is spruce external rubber mixer (final homogenizer) at 30 aboutWith stirring mixer (productive phase) for 3-4 minutes

Thus obtained mixture is then rolled in the form of plates (2-3 mm thick) or thin sheets of rubber to measure their physical or mechanical properties or ekstragiruyut in the form of rolled profiles, suitable for direct application (after cutting and/or assembling to the desired dimensions, in particular as treading pneumasin.

III-3. Characterization

The purpose of this test is to confirm the improved characteristics of the mixture according to the invention in comparison with the traditional mixture, which is used TESPT.

With this purpose, prepare two reinforced silica rubber (SBR and BR), denoted by C-1 and C-2, which are designed for treading pneumasin for passenger transport. These two mixtures are the same, except used a binding agent:

a mixture of s-1: TESPT

a mixture of S-2: synthesized above product D.

Both tested aminosilane used in quantities less than 8 CSA that is less than 10 % wt. in relation to the amount of the inorganic reinforcing filler. Recall that TESPT is tetrasulfide bis(3-triethoxysilylpropyl) of the formula [(C2H5O)3Si(CH2)3S2]2. It supplies sale, nab is emer, the company Degussa under the name Si69 (or X50S in the case when it is applied in the amount of 50 % wt. carbon soot) or by the company Witco under the name Silquest A1289 (in both cases, a commercial mixture of polysulfides Sx with a mean of x, which is close to 4).

Below is expanded formula TESPT (Et means ethyl):

Note that the structure is very similar to the structure of hidroxizina formula II-2, which differs only by the presence of hydroxyl group and two metrov instead of the three traditional CNS groups.

In tables 1 and 2 shows the composition of the two mixtures (table 1: contents of the different products expressed in CSE - weight. parts per 100 weight. parts of elastomer), and their properties before and after curing (approximately 30 min at 150aboutC); break system consists of sulfur and sulfenamide accelerator. Two tested mixtures contain, in addition (not shown in table 1), a small amount of carbon black N330 (6 CSE), used as a black pigmentation agent against ultraviolet radiation.

The attached Fig. 1 and 2 reproduce, respectively, rogramme (the dependence of the torque in the Nam·m on the duration of vulcanization in min) and curves of modulus (in MPa) elongation (%); these curves in figure 1 are denoted by C1 and C2, 2 C1' and C2', appropriate to estua in both cases, the compounds C-1 and C-2, respectively.

Study of the various results of table 2 leads to the following reasons:

the mixture according to the invention C-2 is characterized by the time of burning, shorter than the mixture of comparing s-1, but this time, T5, remains large enough to provide a satisfactory margin of safety in relation to the problem of burning;

values of the Mooney plasticity remain low (85-90 UM) in all cases, at the same time, the lowest value was recorded for a mixture of C-2, which is a very good indicator of the suitability of mixtures according to the invention for processing in raw, at least as good as traditional mixtures, which are used polysulfides of alkoxysilanes;

after the vulcanization of a mixture of C-2 according to the invention when compared to the control mixture has very similar values to the module when there is a strong strain (M100 and M300) and the ratio M300/M100, which are sufficient for the specialist quality characteristics of the gain attributed to the inorganic filler and binding agent;

- hysteresis properties are slightly improved for the mixture according to the invention, as evidenced by a lower tg value(δ)max(synonymous with low rolling resistance);

- finally, and perhaps most importantly, it is noted that the mixture is according to the invention in an unexpected way is the rate constant of the conversion of K, which is more than double the rate constant for the conversion of the control mixture or, in other words, the vulcanization of the mixture may be effected in a much shorter time.

Rogramme on the attached figure 1 well confirmed the advantage of a mixture of C-2, containing hidroxizina, according to the invention: induction time is close to the time of induction of the control mixture; maximum torque is identical to the maximum torque of the mixture of comparison, but is achieved in a much shorter time; constant speed conversion K higher.

Figure 2 also confirms the previous considerations: the curve C2' (a mixture of C-2) and the curve C1' (control mixture (C-1) are nearly identical, especially when the biggest movements that are characteristic of gain and, consequently, the ability of a rubber compound for durability.

In conclusion, we should say that in General, the behavior of a mixture of C-2 according to the invention exhibits not only good quality link (connection) between the inorganic reinforcing filler and the diene elastomer, at least the same, what is achieved with conventional polysulfides of alkoxysilanes, such as TESPT, but also, unexpectedly, significantly improved the ability to be vulcanized.

Replacement of these alkoxysilanes hydroxycinnamic both of which also provides a significant benefit from the point of view of ecology and allocation problems VOC (volatile organic compounds). In particular, CNS group these alkoxysilane (such as ethoxyline group TESPT) are indeed the reason for the selection of alcohol (ethanol) as if preparing themselves to rubber mixtures, and in the process of vulcanization of products from rubber, comprising these compounds.

The invention is particularly useful in rubber compounds suitable for use in the manufacture of treads for pneumasin having a low rolling resistance and high wear resistance, especially in those cases where the protectors are designed for pneumasin passenger transport or for industrial transport type of heavy vehicles.

Table 1
Blend # S-1C-2
SBR (1)7575
BR (2)2525
silica (3)8080
the alkoxysilane (4)6,4-
product D (5)-4,6
DPG (6)1,51,5
ZnO

stearic acid

antioxidant (7)
2,5

2

1,9
2,5

2

1,9
Sulfur 1,11,1
accelerator (8)22

(1) SBR with 59,5% links polybutadiene 1-2; 26.5% of styrene; supplemented by 37.5% aromatic oil (37.5 CSE oil 100 CSA dry SBR); Tg = -29aboutC; per dry SBR;

(2) BR from 4.3% 1-2; 2.7% of TRANS; 93% CIS 1-4 (Tg = -106aboutC);

(3) silica type "HD" - "Zeosil 1165MP" company Rhodia in the form microbasin (BET and CTAB: approximately 150-160 m2/g);

(4) TESPT ("Si69" by the company DEGUSSA-HÜLS);

(5) the synthesized product D (polysulphide bis(propyl-dimethylsilanol), 95 mol.%);

(6) diphenylguanidine ("Vulcacit D" Bayer);

(7) N-1,3-dimethylbutyl-N-phenyl-p-phenylenediamine ("Santoflex 6-PPD" company Flexsys);

(8) N-cyclohexyl-2-benzothiazyl-sulfenamid ("Santocure CBS" company Flexsys).

Table 2
Blend # S-1C-2
Properties to vulcanization:
ML1+4 (UM)9085
T5 (min)2013
ti(min)97
t99(min)4121
K (min-1)0,140,32
t99-ti(min)3214
Δ torque17,819,6
Properties after vulcanization:
M10 (MPa)7,06,8
M100 (MPa)2,62,8
M300 (MPa)4,44,3
M300/M1001,71,6
tg(δ)max0,3100,299
Stress at break (MPa)20,620,8
Elongation at break (%)416443

1. The elastomeric composition based on at least one diene elastomer, an inorganic filler as reinforcing filler, a polyfunctional of organosilane as a binding agent (for inorganic filler/diene elastomer)having at least two functional groups, denoted X and Y, which can be grafted, on the one hand, to the elastomer using X and, on the other hand, to the inorganic filler with the function Y, characterized in that the named function Y is gidroksietilimino function (≡Si-OH), specified organosilane is a polysulfide hidroxizina General formula (I)

in which the radicals R, identical or different, denote a hydrocarbon group containing predominantly from 1 to 15 carbon atoms;

the radicals R′, identical or different, denote divalent linking group, mainly containing from 1 to 18 carbon atoms;

a and b, identical or different, are equal to 1 or 2;

x is greater than or equal to 2, and the amount of the inorganic reinforcing filler is from 10 to 200 CSA (the weight. hours at 100 weight. including elastomer), the amount of polysulfide of hidroxizina is in the range from 1 to 20 CSA.

2. The composition according to claim 1, in which the diene elastomer is chosen from the group which consists of polybutadienes, natural rubber, synthetic polyisoprene, copolymers of butadiene, copolymers of isoprene and mixtures of these copolymers.

3. The composition according to claim 2, for which the copolymers of butadiene and copolymers of isoprene selected from butadiene-styrene copolymers, butadiene-isoprene copolymers, isoprene-styrene copolymers, butadiene-Acrylonitrile copolymers, butadiene-styrene-isoprene copolymers and mixtures of these copolymers.

4. Composition according to any one of claims 1 to 3, in which hidroxizina is monohydroxyethyl (a=b=1).

5. Composition according to any one of claims 1 to 4, in which the radicals R are selected from C1-C6-Akilov,5-C8-cycloalkyl and radical f the Nile, and the radicals R′ selected from C1-C18-alkylene and C6-C12allenov.

6. The composition according to claim 5, in which the radicals R are selected from C1-C6-Akilov, and the radicals R′ C1-C10-alkylene.

7. The composition according to claim 6, in which the polysulfide of hidroxizina is a polysulfide of monohydroxybenzene formula (II)

in which the radicals R mean C1-C3-alkali, mainly methyl; the radicals R′ mean1-C4-alkylene, preferably methylene, ethylene or propylene; and x is greater than or equal to 2.

8. The composition according to claim 7, in which the polysulfide of hidroxizina is polysulfide bis(propyltrimethoxysilane) of the formula (II-2)

9. Composition according to any one of claims 1 to 8, in which the amount of the polysulfide of hidroxizina is from 0.5 to 20 wt.% from the amount of the inorganic reinforcing filler.

10. Composition according to any one of claims 1 to 9, in which the majority of the inorganic reinforcing filler is silica.

11. Composition according to any one of claims 1 to 10, in which the inorganic reinforcing filler is all the amount of reinforcing filler.

12. Composition according to any one of claims 1 to 10, containing, besides carbon soot.

13. The composition according to item 12, in which ug is erdna carbon black is contained in an amount of from 2 to 20 CSA.

14. The composition according to item 13, in which carbon black is contained in an amount of 5 to 15 CSA.

15. Composition according to any one of claim 2 to 14, in which the diene elastomer is a butadiene-styrene copolymer (SBR) styrene content in the range from 20 to 30 wt.%, the content of vinyl bonds in butadiene part of between 15 to 65%, a content of the relations of TRANS-1,4 within 20 to 75% and a glass transition temperature ranging from -20 to -55°C.

16. The composition according to item 15, in which the butadiene-styrene copolymer is a copolymer obtained in solution.

17. The composition according to item 15 or 16, in which the butadiene-styrene copolymer is used in a mixture with a polybutadiene.

18. The composition according to 17, in which the polybutadiene has a 90% relations CIS-1,4.

19. Composition according to any one of claim 2 to 14, in which the diene elastomer is an isoprene elastomer, mainly synthetic polyisoprene or natural rubber.

20. Composition according to any one of claims 1 to 19, characterized in that it is in the vulcanized state.

21. The method of obtaining the elastomeric compositions with improved kinetics of vulcanization, characterized in that at least one diene elastomer is injected at least one inorganic filler as reinforcing filler and a polyfunctional organosilane as a binding agent (for reorgan the ical filler/diene elastomer), having at least two functional groups, denoted X and Y, which can be grafted, on the one hand, to the elastomer using X and, on the other hand, to the inorganic filler with the function Y, which is gidroksietilimino function (≡Si-OH), specified organosilane is a polysulfide of hidroxizina General formula (I)

in which the radicals R, identical or different, denote a hydrocarbon group containing predominantly from 1 to 15 carbon atoms;

the radicals R′, identical or different, denote divalent linking group, mainly containing from 1 to 18 carbon atoms;

a and b, identical or different, are equal to 1 or 2;

x is greater than or equal to 2, and the amount of the inorganic reinforcing filler is from 10 to 200 CSA (the weight. hours at 100 weight. including elastomer), and the number of polysulfide of hidroxizina is in the range from 1 to 20 CSA, and the resulting mixture is stirred thermomechanical in one or two stages before reaching the maximum temperature of from 110 to 190°C.

22. The method according to item 21, in which hidroxizina is monohydroxyethyl (a=b=1).

23. The elastomeric composition according to any one of claims 1 to 20 for producing pneumasin or for the production of intermediates intended for these stump Mosin, these intermediates include, in particular, to the group, which includes protectors, sublayers, the upper, side, frame layers, contour, protective layers, an air chamber and an inner sealing rubber for tubeless pneumasin.

24. PNEVMATIKA containing elastomer composition according to any one of claims 1 to 20.

25. Intermediate for pneumatiky containing elastomer composition according to any one of claims 1 to 20, related in particular to the group, which includes protectors, sublayers for the protectors, the upper, side, frame layers, contour, protective layers, an air chamber and an inner sealing rubber for tubeless pneumasin.

26. Intermediate on A.25 representing protector for pneumatiky.

27. Protector for pneumatiky described in p made from a rubber composition according to any one of PP-19.

28. PNEVMATIKA containing protector on item 27.

29. Application (for inorganic filler/diene elastomer), a composition based on a diene elastomer, reinforced inorganic filler, polyfunctional of organosilane having at least two functions, denoted X and Y, which can be grafted, on the one hand, to the elastomer using X and, on the other hand, to the inorganic filler with the function Y, which is gidroksietilimino funk the Oia (≡ Si-OH)in which ogranicenom is a polysulfide of hidroxizina General formula (I)

in which the radicals R, identical or different, denote a hydrocarbon group containing predominantly from 1 to 15 carbon atoms;

the radicals R′, identical or different, denote divalent linking group, mainly containing from 1 to 18 carbon atoms;

a and b, identical or different, are equal to 1 or 2;

x is greater than or equal to 2, as a binding agent.

30. The application of clause 29, in which hidroxizina is monohydroxyethyl (a=b=1).

31. The method of binding inorganic and diene elastomer in the elastomeric composition, characterized in that at least one diene elastomer is injected at least one inorganic filler as reinforcing filler and a polyfunctional organosilane having at least two functions, denoted X and Y, which can be grafted, on the one hand, to the elastomer using X and, on the other hand, to the inorganic filler with the function Y, which is gidroksietilimino function (≡Si-OH)in which organosilane is a polysulfide of hidroxizina General formula (I)

in which the radicals R, odinakovije different, denote hydrocarbon groups, mainly containing from 1 to 15 carbon atoms;

the radicals R′, identical or different, denote divalent linking group, mainly containing from 1 to 18 carbon atoms;

a and b, identical or different, are equal to 1 or 2;

x is greater than or equal to 2, the amount of the inorganic reinforcing filler is from 10 to 200 CSA (the weight. hours at 100 weight. including elastomer), and the number of polysulfide of hidroxizina is in the range from 1 to 20 CSA, and the resulting mixture is stirred thermomechanical in one or two stages before reaching the maximum temperature of from 110 to 190°C.

32. The method according to p in which hidroxizina is monohydroxyethyl (a=b=1).



 

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50 cl, 4 ex, 5 tbl, 2 dwg

Rubber compound // 2318842

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14 tbl, 13 ex

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4 tbl, 1 ex

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43 cl, 2 tbl, 8 ex

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1 tbl, 8 ex

FIELD: rubber industry; other industries; production of the rubber mixture on the basis of the non-saturated carbon-chain caoutchouck.

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3 tbl, 2 ex

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28 cl, 4 ex

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4 tbl, 7 ex

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4 ex

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2 cl, 2 ex

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2 tbl, 2 ex

Rubber composition // 2235741
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The rubber mixture // 2235740
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2 tbl

FIELD: biologically active polymer materials.

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3 cl, 5 tbl, 4 ex

Rubber compound // 2318842

FIELD: rubber industry.

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EFFECT: improved complex of technological and user's properties of rubber compound: strength, elasticity, and tear resistance.

14 tbl, 13 ex

FIELD: chemical industry; production of the halogenated interpolymers of polyolefines and isoolefines.

SUBSTANCE: the invention is pertaining to the halogenated having the low content of the gel and the high molecular mass interpolymers of polyolefines and isoolefines. The invention presents the halogenated and having the low content of gel and the high molecular weight interpolymer of isoolefine, with the content of multiolefine exceeding 2.5 % mole and the molecular mass Мь exceeding 240 kg/mole and the gel content - less, than 1.2 mass %; the method of its production, the composition and the vulcanized composition for the rubber products containing the indicated halogenated interpolymer. The technical result of the invention consists, that it allows to produce the halogenated interpolymers of isoolefine with multiolefine with the high molecular mass, which have the increased content of the double bonds and simultaneously - the low content of the gel; the compositions containing the indicated halogenated interpolymer possess the improved properties.

EFFECT: the invention ensures production of the halogenated interpolymers of isoolefine with multiolefine with the high molecular mass, having the increased content of the double bonds and simultaneously - the low content of the gel; the compositions containing the indicated halogenated interpolymer possess the improved properties.

11 cl, 2 tbl, 1 dwg, 5 ex

FIELD: materials technology of polymeric composites.

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EFFECT: higher efficiency.

14 ex, 2 tbl

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EFFECT: improved physico-mechanical parameters of vulcanizers; reduction of deficiency of rubber phase in ebonite; utilization of used ion-exchange resins.

2 tbl

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