Rubber mixture for tyres with improved vulcanising agent

FIELD: chemistry.

SUBSTANCE: invention relates to rubber mixture for production of pneumatic tyres. Rubber mixture contains, at least, one vulcanising diene caoutchouc, 35-300 parts of, at least, one active filling agent, selected from soot, silicon dioxide, filling agents, based on silicon and metal oxides, from 0.1·10-3 to 42·10-3 moles per a hundred parts of vulcanising agent caoutchouc, which is cross-linked with functionality higher than 4, and from 0.1 to 20 parts of, at least, one vulcanisation accelerator. Vulcanising agent has sulphur-containing structure, including hydrocarbon and/or heterohydrocarbon, and/or siloxane group, with functionality higher than 4. Soot or silicon dioxide, or their combination constitutes, at least, 10 parts of active filling agents. Mixture also contains 0-250 parts of other additional additives. Said rubber mixture has glass-transition temperature Tg (E" max.) in accordance with DIN 53 513, at least -80°C and not higher than 0°C.

EFFECT: tyres, manufactured with application of said mixture possess Shore A hardness in accordance with DIN 53 505 and ASTM D2240 not less than 40 ShA and not higher than 95 ShA with specified temperature range from -80°C to +80°C and specified compression of about 10+0,2% at 10 Hz.

12 cl, 2 dwg, 6 tbl

 

The invention relates to a rubber mixture, in particular for tires with improved abrasion and improved fatigue strength.

There is a large variety of additives that are injected into the mix to influence the characteristics of the mixtures and of the vulcanizate, and/or for the use of special polymers. As examples of such additives here you can specify the fillers (e.g. carbon black), plasticizers, antioxidants and systems stitching, which consist of sulphur, accelerators and activators. However, if by altering the mix improve one characteristic, it is often correlated with the deterioration of other characteristics, and thus, there are certain conflicts of goals. Examples of such conflicts of goals in mixtures for the tyre tread can be found in conjunction with wear resistance, fatigue strength and high heat release, resulting in the deterioration elasticity to rebound and deterioration of rolling resistance. A special method is used to resolve these conflicts purposes, lies in the variation of properties of the mixture and, in particular, also in changing or modifying additives, it strives to provide a superior level of performance, which usually show a correlation in the opposite direction.

To an important group add the to, which have an impact on the rate of vulcanization and on the physical characteristics of the vulcanizate is a group of vulcanization accelerators. There are different groups of vulcanization accelerators which can be used for the production of tires and known in the art, and these accelerators can also be used in combination with each other, and in some cases, there are synergistic effects.

These vulcanization accelerators are used for activation of sulfur, which is used as a vulcanizing agent. The introduction of sulfur and corites vulcanization in this case agree individually tailored to achieve the desired characteristics of the rubber mixtures for the production of tires. These characteristics depend on the mesh structure, which is formed during vulcanization, for example, between the properties of the polymer chains or polymers and fillers, and for this reason, the type and degree of crosslinking from the viewpoint of the physical properties of the vulcanizate attach great importance.

Of particular importance is the structure of the staple, which is well known to the person skilled in the art. The distribution chains of sulfur affects the fatigue properties.

The prior art in conjunction with vulcanizing systems or systems stitching will be hereinafter described in more detail in the examples using the-W the following publications:

(D1) DE 60303203 T2

(D2) US 5342900

(D3) US 2002/0058760A1

(D4) EP 0530590 B1

(D2) US 7189866

In document D1 describes polysulfide siloxane, which can be used as a crosslinking agent, and a method thereof. The stapling system described here contains polysulfide siloxane and at least one primary accelerator of vulcanization. Polysulfide siloxane used in such a composition based on a diene elastomer and a reinforcing filler. Described here diene elastomer contains several components, as described here fillers include, in particular, silicon dioxide and soot, and each of these examples relates to a rubber mixture, which consists of natural rubber as the sole polymer and carbon black as the sole filler.

In document D2 describes vulcanized diene rubber, and the vulcanization is carried out in the presence of a crosslinking agent, which contains benzyl group, sulfur and mercaptoethanol, and sulfenamides the accelerator.

In document D3 describes the method of forming protective equipment, in particular, one which is able to sufficiently connect the polymeric sheet and frothy part of the site protective equipment and to simultaneously place both in the form without any of adhesion the th periphery.

In document D4 describes the method for the production of vulcanizates diene rubber, which have a very high resistance to aging and resistance to reversion. In this case, the vulcanizates of diene rubber containing 1-2,5 parts of mercaptopyridine or 0.2 to 0.8 part sulfenamide accelerator or 0.3 to 2.5 parts of mercaptopyridine and 0.1 to 0.8 part sulfenamide accelerator. Also used and 0.1-0.2 parts of sulfur per 100 parts of rubber, preferably oil-filled butadiene rubber.

Document D5 relates to a crosslinking agent used for crosslinking the elastomeric grids, in particular, in the manufacture of tires or semi-finished products for tires. In the examples described the implementation of the method with cyclic polysulfonyl tetramethyldisiloxane. This method shows that it is possible to sew a rubber composition without making sulfur. It was established that the improvement of thermal stability (characteristic reversion) mixtures, which is based on polysulfide.

Elemental sulfur is used, generally, as a vulcanizing agent for unsaturated organic polymers. Bridge ties that sulfur forms with organic polymer, represent a primary polysulfide bridge connection, which reduce thermal stand is here vulcanizate. The use of organic compounds which include sulfur-containing reactive group, known to specialists as a vulcanizing agent for diene rubber. These sulfur-containing compounds include often only two groups of dithiocarbamate or thiosulfonate sodium, which are chemically bonded to forming the bridges group. A small number of points of contact with the crosslinking unsaturated diene polymers is inefficient and forms vulcanizates with good balance of abrasion resistance and breaking strength. It would be desirable to obtain a new type of cross-linking agent for elastomers, which would improve the fatigue characteristics, abrasion resistance and tensile strength and at the same time would preserve the hardness.

Usually the rubber mixture vulcanized with cross-linking agent, which creates two connection points, which theoretically has a cross-linking functionality of 4, which means that 4 polymer site are bridged connection, see figure 1. In the method, the density of crosslinking in the crosslinked rubber mixture is approximately in the range from 10∙10-5up to 25∙10-5mol/cm3(definition of equilibrium swelling in unfilled joints rubber).

The present of the invention is directed to creation of rubber compounds for tires, which the mouth of anal or at least reduces the above disadvantages. Essentially should be improved and the abrasion resistance and the energy gap of rubber compounds, while the rest of the characteristics of the rubber mixture should remain at a similar level.

The concept of "rubber tire", "tire mixture or composition for tires" in this description are used as synonyms. If you use only the term "rubber compound", in this case, if not otherwise noted, it refers to the tires.

The above problem is solved by providing the composition for tires with the following structure.

Composition for tires with hardness shore a according to DIN 53 505 and ASTM D2240 not less than 40 ShA and not more than 95 ShA and glass transition temperature Tg (E” max) according to DIN 53 513 at a given temperature range -80°C to +80°C and a given compression 10+0.2% at 10 Hz is not less than -80°C. and not more than 0°C., and the composition contains:

- at least one vulcanizes diene rubber selected from natural rubbers, synthetic branch, Rubezhnoe, Ukraine rubbers, polyisobutylene rubbers, polybutadiene rubbers, and butadiene-styrene rubbers;

- 35-300 phr (parts per 100 parts of rubber)of at least one active filler selected from the types of carbon black, silicon dioxide, fillers based on silicon and metal oxides, of which at least 10 phr should be CA is a, silicon dioxide or a combination thereof;

- 0-250 phr or other additional additives;

from 0.1·10-3up to 42·10-3mhr (mol per hundred parts of rubber) vulcanizing agent, which is sewn with a functionality greater than 4; and

- 0.1 to 20 phr of at least one vulcanization accelerator.

In the present description indicator phr (parts per hundred parts of rubber by weight) in the production of rubber compounds is a measure used to specify the number of mixture formulations. At this dosage weight parts of separate substances is always relative to 100 weight parts of total mass of all contained in a mixture of rubbers.

Used in the present description indicator mhr (mol per hundred parts of rubber) is thus another indicator quantities for recipes mixture correlated to pray. At this dosage molar parts of individual substances is always relative to 100 weight parts of total mass of all contained in a mixture of rubbers.

Available vulcanizing agent, which has a functionality greater than 4. If the functionality will be, for example, 6, see figure 2, introduces three bridge connection on each molecule in the polymer matrix instead of two-bridge links, i.e. the functionality of 4, as is known, in accordance with the latest technology. Newly formed centers school is for prevent the formation of cracks, and the elasticity of these centers absorbs energy and thus prevents the formation of gaps rubber compound. Curing agent according to the present invention is hereinafter also referred to as a crosslinking agent.

As an example, the present invention solves the problem in the following way. In the rubber compound made by the builders, which have a higher performance compared with the prior art. It is necessary to take into account that, for example, three conventional bridging ties provide the functionality of four compared to the two bridge bonds, which provide a rubber compound functionality and six provides the same stiffness and the analytical density of the stitching. When fully implemented in the rubber mixture is added approximately between 6.6·10-5to 18·10-5mol/cm3bridging ties with the functionality of six.

Structured in the Central unit may also consist of related items or elements of any other chemical nature, for example, hydrocarbons (e.g., siloxane). Already a partial implementation of the functional elements described above leads to the desired effect.

The advantages of this invention include:

1. Creating links in 3 points instead of 2 points.

2. Providing flexible structurate.

3. Create a second mesh structure in the polymer matrix.

The following technical problem which is solved according to the present invention is to improve the dynamic stability/strength of rubber compounds, which increases the durability of the tire and to improve the wear resistance of the tire, for example, improving energy gap (figure HSTE).

The advantages of the present invention and its technical distinguishing characteristics are manifested in the production of tires with improved durability of the tread, for example, in a superior characteristic in relation to the known, so-called peeling and chipping. When using mixtures of the frame, that is, for mixtures that are used in the internal structural parts of the tyre, not protectors, is improved strength and improved fatigue strength.

Vulcanizing agent preferably contains the structure of the chemical nature of the hydrocarbons and siloxanes.

In particular, the curing agent includes, preferably, sulfur-containing structure of the General formula:

G[CaH2a-CH2-SxY]n,

where G is a polyvalent cyclic hydrocarbon group, and/or multivalent heterophenomenology group, and/or multivalent siloxane group which contains from 1 to 100 at the MOU; where Y is independently selected from rubber active group and where a, x and n are integers, for which independently is true: a is 0-6; x is 0-8 and n is 3-5.

Vulcanizing agent includes, preferably, sulfur-containing cyclic structure of the General formula:

G[CaH2a-CH2-SxY]n,

where G is a polyvalent cyclic hydrocarbon group, and/or polyvalent cyclic heterophenomenology group, and/or polyvalent cyclic siloxane group which contains from 1 to 30 atoms in a cyclic structure; where each Y is independently selected from rubber active group, which includes sulfur-containing functionality, and where a, x and n are integers, for which independently is true: a is 0-6; x is 0-8 and n is 3-5.

In the preferred embodiment, G is a polyvalent cyclic hydrocarbon group containing 5-7 carbon atoms and each Y is independently selected from rubber active group, which includes sulfur-containing functionality, and a, x and n are integers, for which independently is true: a is 0-6; x is 0-8 and n is 3-5.

Particularly preferred vulcanizing agent include sulfur-containing cyclic aliphatic hydrocarbons of the General formula:

G[Ca H2a-CH2-SxY]n,

where G is a polyvalent cyclic hydrocarbon group which contains from 5 to 7 carbon atoms; each Y is independently selected from thiosulfonate group, dithiocarbamate group, a thiocarbonyl group, mercaptopropyl, a hydrocarbon group and from the group thiosulfonate sodium (salt group Rebellion); and a, x and n are integers, for which independently is true: a is 0-6; x is 0-8 and n is 3-5.

In a particularly preferred embodiment, Y is independently selected from thiosulfonate group or dithiocarbamate group.

In a preferred embodiment, the curing agent composition for a tire includes a custom made, containing polysulfide cycloaliphatic compound of the General formula:

[(CaH2a)mG1(-CbH2bSx)n-m]o[CcH2c-G2-CdH2dSy]p[R]q,

where G1represents a saturated, monocyclic, aliphatic group with a valency of n, which consists of 5-12 carbon atoms and optionally at least one halogen; G2is a saturated bivalent cyclic aliphatic group with a valency of 2, which includes 5-12 carbon atoms and optionally at least one halogen; each R independent is selected from the group consisting of hydrogen, monovalent hydrocarbon of up to 20 carbon atoms and halogen atom; each of a, b, c, d, m, n, o, p, q, x and y independently is an integer while true: a is 2 to 6; b is 2 to 6; C is 1 to 6; d is 1 to 6; m is 1 or 2; n = 3-5; o is a positive integer, p is 0 or a positive integer, q is a positive integer; x is 1-10 and y is 1-10, provided that

(i) at least one x is 2-10;

(ii) the ratio of p and o less than 1-5 and

(iii) q is equal to the sum of open valences groups

(CaH2a-)mG1(-CbH2bSx)n-mand CcH2c-G2-CdH2dSy-.

Another preferred variant implementation exists, if the vulcanizing agent include sulfur-containing structure of the following General formula, or a mixture thereof:

,

or

,

or

,

or

,

where G is a polyvalent hydrocarbon, and/or heteroploid, and/or siloxane group, which contains 1-100 atoms; and each a, a', a”, b, b', b”, c, c', c”, k, j, o, x, x', x”, x”' and x”represents an integer, which independently is true: a, a', a”, b, b', b”, c, c'c” equal 0-8; o, k, j are positive CE is diversified numbers and x, x', x”, x”', x" is equal to 2-8; where each R', R” are independently selected from the group consisting of a hydrogen atom, monovalent hydrocarbon of up to 20 carbon atoms and halogen atom.

In the preferred embodiment, G is a cyclic polyvalent hydrocarbon, and/or heterophenomenology, and/or siloxane group containing 1-30 atoms in a cyclic structure; and each a, a', a”, b, b', b”, c, c', c”, k, j, o, x, x', x”, x”' and x”represents an integer, which independently is true: a, a', a”, b, b', b, c, c', c” equal 0-8; o, k, j are positive integers and x, x', x”, x”', x" is equal to 2-8; where each R', R” are independently selected from the group consisting of a hydrogen atom, monovalent hydrocarbon of up to 20 carbon atoms and one atom of halogen.

In a particularly preferred embodiment, G is a polyvalent cyclic hydrocarbon group containing 5-7 carbon atoms; and each a, a', a”, b, b', b”, c, c', c”, k, j, o, x, x', x”, x”' and x”represents an integer, which independently is true: a, a', a”, b, b', b”, c, c', c” equal 0-8 o, k, j are positive integers; and x, x', x”, x”', x" is equal to 2-8; where each R', R” are independently selected from the group consisting of a hydrogen atom, monovalent hydrocarbon of up to 20 carbon atoms and one atom of halogen.

Vulcanizing agent site which preferably contains

,

where each of n, o, k, j, and x is an integer, which independently is true: m is 0-2; o, k, j are integers and x is 2 to 8; where each R', R” are independently selected from the group consisting of a hydrogen atom, monovalent hydrocarbon of up to 20 carbon atoms and one atom of halogen.

Vulcanizing agent preferably contains

,

where each k, o, j, x, x' and x” is an integer, which independently is true: x, x', x” is equal to 2-8; o, k and j are positive integers; and where each R', R” are independently selected from the group consisting of a hydrogen atom, monovalent hydrocarbon of up to 20 carbon atoms and one atom of halogen.

Vulcanizing agent contains:

,

where G is a cyclic structure, and each Y is independently selected from rubber active group; and each x and n represents an integer, which independently is true: x is 0-8 and n is 3-8.

A particularly preferred curing agent contains:

,

where each Y is independently selected from rubber active group; and each x and n represents an integer, which independently is true: x is 0-8 and n is 3-6. In the preferred embodiment to implement the Oia rubber active group is a rubber active group, which includes sulfur-containing functionality. This rubber is an active group, which includes sulfur-containing functionality that may be chosen from thiosulfonate group, dithiocarbamate group, thiocarbonyl group, the group of hydrogen and a hydrocarbon group, however, is not limited to them, though dithiocarbamate group or thiosulfonate group is given special preference.

Particularly preferred, if the curing agent contains

,

where each Y is independently selected from rubber active group and each x is an integer, which independently is true: x is 0-8.

Vulcanizing agent preferably contains

,

where each Y is independently selected from rubber active group, which includes sulfur-containing functionality, and each x is an integer, which independently is true: x is 0-8.

Sulfur-containing rubber active group Y is preferably selected from thiosulfonate group, dithiocarbamate group, thiocarbonyl group, the group of hydrogen and a hydrocarbon group, however, is not limited, although dithiocarbamate group or thiosulfonate group is given special preference.

Specialists in this field there are several the ways of manufacturing vulcanizing agent.

However, the next will outline several ways, although there are other ways in which you can make vulcanizing agents.

A method of manufacturing a cycloaliphatic curing agents containing a polysulfide, includes the following steps:

a) turning polyalkene-substituted cycloalkane ciocalteu in the presence of a source of free radicals to obtain politicalsocial-substituted alkylcyclohexane;

b) transforming politicalsocial-substituted alkylcyclohexane debateroom agent to receive free polymercaptan-functional alkylcyclohexane;

c) the transformation of free polymercaptan-functional alkylcyclohexane oxidizing agent selected from halogenated sulfur-containing compounds, for which the General formula is:

X1SzX2,

where X1represents a chlorine atom, bromine or iodine, X2is a X1hydrogen or a hydrocarbon of up to 12 carbon atoms and z is independently an integer; and z is 1-10; peroxide; hydroperoxide and oxygen,

to get stitched cycloaliphatic curing agent containing a polysulfide.

Containing mercaptan cycloaliphatic curing agent obtained by a method which includes the following floor is dust:

a) turning polyalkene-substituted cycloalkane ciocalteu in the presence of a source of free radicals to obtain politicalsocial-substituted alkylcyclohexane and

b) transforming politicalsocial-substituted alkylcyclohexane debateroom agent to receive free polymercaptan-functional alkylcyclohexane.

Another method of obtaining sulfur-containing cycloaliphatic curing agents includes the following steps:

a) turning polyalkene-substituted cycloalkane ciocalteu in the presence of a source of free radicals to obtain politicalsocial-substituted alkylcyclohexane;

b) transforming politicalsocial-substituted alkylcyclohexane debateroom agent to receive free polymercaptan-functional alkylcyclohexane;

c) the transformation of free polymercaptan-functional alkylcyclohexane halogenation agent to obtain polysulfonamide-functional cycloalkane and

d) transforming polysulfonamide-functional alkylcyclohexane alkali metal salt having the formula R-S(=O)b-M+where R is a monovalent hydrocarbon of up to 20 carbon atoms; M+represents a cation of an alkali metal and b represents an integer of 1 or 2, to obtain seroter Amigo cycloaliphatic compounds;

or

d) transforming polysulfonamide-functional alkylcyclohexane alkali metal salt having the formula R2NC(=S)S-M+where R is a monovalent hydrocarbon of up to 20 carbon atoms; M+represents a cation of an alkali metal, to obtain thiocarbamoylation-functional cycloaliphatic compound.

Composition for tires is a composition that contains at least one vulcanizes rubber selected from natural rubber (NR), synthetic branch, Rubezhnoe, Ukraine rubbers (IR), polyisobutylene rubber (PIB), polybutadiene rubber (BR) and styrene-butadiene rubbers (SBR, S-SBR E-SBR), and active fillers selected from the types of carbon black, silicon dioxide, fillers based on silicon and metal oxides, the total number of which is at least 35 phr, and from them should be at least 10 phr of carbon black, silica or combinations thereof. These compounds have a shore a hardness according to DIN 53 505 and ASTM D2240 not less than 40 ShA and not more than 95 ShA and the glass transition temperature Tg (E” max) according to DIN 53 513 in temperature range from -80°C to +80°C and at a given compression 10+0.2% at 10 Hz is not less than -80°C. and not more than 0°C.

These compounds are used mainly for the production and development of components of the tire and/or tire.

Composition for tires, FAV is preferably, contains 30 to 100 phr, of at least one diene rubber.

For the tyre tread of passenger cars preferred, for example: SBR/BR: 0-50 phr;

NR: 0-50 phr, preferably 0-30 phr

and particularly preferably 0 to 20 phr.

Choose at least one diene rubber from the group consisting of natural polyisoprene, and/or synthetic polyisoprene and/or polybutadiene, and/or butadiene-styrene copolymer, and/or polymerized in a solution of butadiene-styrene copolymer, and/or polymerized in emulsion butadiene-styrene copolymer, and/or butadiene-isoprene copolymer and/or styrene-isoprene-butadiene terpolymer, and/or butyl rubber, and/or galobutilovomu. The polymers can be defunctionalization or functionalized, it is also possible and a mixture of functionalized and defunctionalizing polymers.

For tires used in various fields (protectors/body, tires for passenger cars and tires for trucks), use different preferred polymer compositions.

Protectors for passenger car tyres

Composition for tire contains, preferably, at least one styrene-butadiene rubber (SBR, preferably polymerized in solution styrene-butadiene rubber (SSBR)).

Treads for tires truck

Composition for tire contains, preferably, 40 to 100 phr of natural rubber, 0-50 phr butadiene rubber, 0-60 phr SBR, preferably polymerized in solution SBR (SSBR).

Frame

Composition for tire contains, preferably, 20 to 100 phr of natural rubber, 0-80 phr butadiene rubber, 0-50 phr SBR.

Composition for tires according to the invention includes additional features, and the fillers include silica, other metal oxides, metal salts (for example, carbonates, sulfates, etc.), the microgel or soot.

The term "silica" is used in this case as a synonym of silicic acid, silicic acid filler or amorphous silicic acid, in the form in which it is used in the rubber industry. The proportion of fillers is 35-300 phr, preferably 40 to 150 phr, of at least one known active filler, such as silicon dioxide, other mineral fillers, or modified polymer microgels, or soot.

In that case, if silicon dioxide is used as the main component of the filler, it in this case would be to have a standard specific surface area in the range from 100 to 300 m2/g, as measured by the BET surface (nitrogen absorption), preferably 120-250 m2/g and particularly preferably 140-220 m2/, In that case, if the OS is ESD component used soot, its coefficient of absorption of iodine will be 25-300 g/kg, preferably 70-200 g/kg when used for protectors, 40-90 g/kg when used for the frame and its coefficient DBP will be 50-300 cm3/100 g, preferably 70-150 cm3/100, But you can also use a combination consisting of silicon dioxide with the mentioned characteristics and soot with the mentioned characteristics as the main component of the filler.

For various applications also use various preferred total shares fillers: for the tyre tread of passenger cars between 50 and 200 phr, preferably 60 to 150 phr, for the tyre tread trucks 40 to 70 phr, preferably 40-65 phr; for the frame preferably 35-80 phr.

Composition for tire together with silicon dioxide and/or soot optionally contain other fillers, such as aluminum hydroxide, phyllosilicate, chalk, starch, magnesium oxide, titanium oxide, rubber gels, short fibers, etc. in any combination.

In that case, when using silicon dioxide, it can be activated by organosilane, as it is used in the rubber industry.

As examples, which, however, is not limited to data, can be called TESPD, TESPT or given in the descriptions of the inventions to patents US 11/617683, 11/617649, 11/617663, 11/617653, organosilane and the types and NXT silanes, NXT-low-VOC, NXT-Z from MPM (Momentive Performance Materials), which are mentioned in the description of the patent US 2006/0161015 or WO 2008/003514.

Composition for tire contains 0.1 to 20 phr, preferably 0.1 to 15 phr, particularly preferably 0.1 to 10 phr of at least one vulcanization accelerator selected from the group consisting of titlevii accelerator, mercaptanes accelerator, sulfenamide accelerator, a guanidine accelerator, turnby accelerator, a dithiocarbamate accelerator, amine accelerators, thiourea and/or other known accelerator.

The quantitative proportion of the vulcanization accelerator is preferably 0.1 to 6 phr, and in this case, preference is given to at least one accelerator selected from the group sulfenamide accelerators, and preference is given to N-tert-butyl-2-benzothiazolesulfenamide (TBBS) or cyclohexylbenzothiazole (CBS). The mixture may optionally also include donors sulfur-containing crosslinking agents that supply the mesh structure of sulfur, as is well known to specialists in this field or, for example, as described in reference Hofmann & Gupta: Handbuch der Kautschuktechnologie, Gupta-Verlag (2001), Chapter 7, for example, turondale, preferably TBzTD or dithiophosphate, for example, DipDis (bis-(aminobutiramida)thiophosphorylated), SDT (for example, Rhenocure SDT 50, Rheinchemie GmbH), cancelcellediting (ZDT) (for example, Rhenocure ZT/S, Rheinchemie GmbH).

A common quantitative portion of the supplemental or other additives is 0-250 phr, preferably 10-220 phr, and particularly preferably 10-200 phr. Additives include, for example, an auxiliary components vulcanization, which do not represent accelerators, sulfur donors and sulfur and well-known experts in this field, for example, ZnO, stearic acid, resin, etc. Other additives include one or more auxiliaries that facilitate processing, one or more plasticizers, one or more antiozonants and one or more antioxidants. If necessary, you can make other additives that are well known in the rubber industry.

Supplements include 0-60 phr of additional components, preferably 0-40 phr, for example, antiozonant wax, resin, ZnO, antioxidant, etc.

In addition, additives contain 0-120 phr, preferably 0 to 90 phr, and particularly preferably 0-80 phr, of at least one plasticizer, and the plasticizer is an oil plasticizer, such as mineral oil selected from the group that contains the DAE (Distillated Aromatic Extracts (distilled aromatic extracts)), and/or RAE (Residual Aromatic Extract (residual aromatic extract), and/or TDAE (Treated Distillated Aromatic Extracts (treated distilled aromatic extracts)), and/MES (Extracted Mild Solvents (soft extracted solvents)), and/or naphthenic oil.

Also in the mix for tires can be 0-80 phr of at least one other additional plasticizer. This other plasticizer may be a synthetic plasticizer, and/or fatty acid, and/or derived fatty acids and/or resin and/or factis, and/or a polymer with a low molecular weight, and/or vegetable oil and/or mineral oils and/or esters and/or oil from liquefaction of biomass, and/or mixtures thereof.

As a result of making according to this invention the elementary level linking agent with a functionality greater than 4, you can achieve surprisingly good indicator of strength. In fact, the result is a better indicator of strength, while other physical properties also remain at the same level.

This allows you to unleash the conflict of goals, which exists, for example, between rolling resistance and durability. This applies not only to tread, but also other structural elements of the tire, for example, a side wall of the tire or other frame of mixtures.

Composition for tires according to the present invention is used mainly for the manufacture of tires. This can be a massive bus or a pneumatic tyre. A particularly important application in this case is the application of the protector p is aumatically tires and frame in a mixture of pneumatic tires. The notion of frame as a mixture, include here the side wall, the inner layer, top, belt, shoulder, the profile of the tread, the rubber ribbon, "skeleton" and/or reinforcement, however, is not limited.

Composition for tires according to the present invention can also be used for the production of technical rubber products, for example, hoses, air springs, housings absorbers and/or of transmission belts.

So, for example, used the following processes of mixing and the following equipment for mixing to obtain the described compounds, but can also be used and other equipment for mixing and mixing processes, which are known to experts in the industry. Connect all of the examples were mixed in the mixer OOC-BANBURY® (Farrell Corp.) with the volume of the chamber 158 cubic inches (2600 cm3). The mixing of the rubber produced in three stages. The stirrer was turned at a speed of rotation of the agitator 80.min and when the cooling water temperature of 71°C. the Rubber polymers were loaded into the mixer and mixed for 30 seconds with the implementation of the stamp. Fillers and silane, if applicable, were loaded into the mixer and mixed for 30 seconds with the implementation of the stamp. Other components in masterbatches from table 1, except oils, were loaded into mesalc and was stirred for 60 seconds with the implementation of the stamp. The mixing speed was reduced to about 65./min and then into the mixer with the mother mixture added oil, and mixed for 60 seconds with the implementation of the stamp. The neck mixer threshed and the components were mixed with the implementation of the stamp until a temperature of 150°C. After that, the components continued to stir for another 3 minutes and 30 seconds. The mixing speed was regulated so that the temperature was maintained in the range from 150 to 155°C. the Rubber was overturned (unloaded from the mixer), and then at a temperature of 85°-90°C. in a roll mill manufactured band, then allowed it to cool to ambient temperature.

In the second stage uterine mixture was again loaded into the mixer. The speed of the mixer was about 80./min, cooling water was set at 71°C and the pressure piston put on 25 pounds per square inch. Uterine mixture was stirred for 150 seconds with the implementation of compacting, the temperature masterbatches brought to 150°C and then the speed of the mixer was reduced to about 50./minutes of the Rubber was stirred for 40 seconds at a temperature of 150-155°C. After mixing, the rubber was overturned (unloaded from the mixer), and then at a temperature of 85°-90°C. in a roll mill manufactured band. The rubber was allowed to cool to ambient temperature.

the and the third stage, the speed of the stirrer was set at 50 rpm./min, cooling water was set at 71°C and the pressure piston put on 25 pounds per square inch. Rubber uterine mixture and vulcanizing the reagents were stirred for 190 seconds with the implementation of the stamp, and the temperature of the mixture was brought to 115°C. After mixing, the rubber was overturned (unloaded from the mixer), and then at a temperature of 85°-90°C. in a roll mill manufactured band and then allowed to cool to ambient temperature. The binding occurred at 160°C for 20 minutes.

Hereinafter the invention is explained in more detail in the comparative examples and examples according to the invention, which are compared in the following tables. Tables based on various formulations containing different components, which in turn depend on the class of silane and application connections.

Table 1 shows the composition of the mixture and the related results of laboratory tests, and, in addition, it contains test results, which were obtained directly on the bus.

Composition for tires C1 is a reference mixture, which contains only sulfur, while the compositions for tires E1 was vulcanizable according to this invention with sulfur and adding curing agent according to the present invention.

All of the examples of mixtures which are listed in the face, quantitative proportion given in parts by weight per 100 weight fractions of the total weight of the rubber.

The preparation of the laboratory mixtures were produced in a laboratory tangential mixer. All mixtures used for the preparation of samples for testing using vulcanization, and they have been manufactured under such conditions of vulcanization, which specialist in this field are known, and these samples for tests were used to determine typical characteristics of materials for the rubber industry. For tests on the samples used the following testing methods:

- Hardness shore a at room temperature and 70°C according to DIN 53 505.

- Ball rebound resilience at room temperature and 70°C according to DIN 53 512.

The ultimate tensile strength at room temperature according to DIN 53 504.

- Breaking elongation at room temperature according to DIN 53 504.

Module voltage at 300% static stretching at room temperature according to DIN 53 504.

Is the coefficient of wear resistance according to DIN 53 516.

- Abrasion by a Penny, according to Grosch, K. A., the 131th ACS Rubber Div. Meeting, No. 97 (1987) and Grosch, K.A. et al., Kautschuk Gummi Kunststoffe, 50, 841 (1997).

- The tensile strength of the specimen with notch on Greyvzu at room temperature according to DIN 53 515.

Fatigue strength as the number of load changes to razrusheny the sample in the form of dumbbells in the case of constantly recurring cycle load with a frequency of 104±8 min -1defined by the device for testing Monsanto Fatigue to Failure Tester (FTF) at a load of 136% and at a temperature of 60°C.

- High energy gap (HSTE) according to DIN 53 448 or ASTM D 624-86.

- Life cycle analysis (LTA) at 30%load.

- Podocarpaceae Mooney according to ASTM D1646.

The Mooney viscosity according to ASTM 1646.

Of memory/the loss modulus according to DIN 53 513.

- Rheometer (MDR2000) according to DIN 53 529.

Pneumatic tyre size 205/55/R16 was made with the protector, which consisted of mixtures listed in table 1, and tires were used for testing braking with moistened pads on the asphalt (low µ) and the concrete (high µ), and also to aquaplaning, and rolling resistance. Also measured the wear. The characteristics of the bus, which used a mixture of C1 were taken as 100, and the values more than 100 for a mixture of E1 mean improvement in relevant characteristics. The results are given in table 1.

It was found that the reference mixture of C1, which was vulcanizable standard by introducing elemental sulfur, in the results of laboratory tests, compare table 1, showed approximately 15% higher wear (wear DIN), and therefore their characteristics abrasion were significantly worse. This trend is also manifested at the respective test tires, see table 1. Other physical the environmental characteristics were about the same level not only when tested in the laboratory, see table 1, but also when the test bus, see table 1.

If the abrasion in the form of laboratory data specified in absolute values (mm3), it represents the loss in weight during the test, which means that lower numbers mean improvement in all tables with the physical data. In the case of relative numbers (%) relative to the wear characteristics of the tire higher values always mean better performance.

Other examples are shown in tables 2 through 6 indicate the use of different samples, which correspond to different cross-linking agents with functionality more than 4 in a variety of compositions for tires. The results of laboratory studies constantly reflect the improved fatigue properties, and/or explosive properties and/or characteristics abrasion, while at the same time other characteristics of the material remain largely unchanged.

It should be understood that although shown and described only a few examples of carrying out the invention, it is not limited.

The compositions of the 'C' represent the control compositions, and the compositions 'E' represent the compositions according to the invention.

The structure of a single vulcanizing agents according to the present invention, abbreviated MFXL (multifunctional cross-sshi is non agent), have the following form:

,

where m is 0-2, k, o and j are positive integers.

Table 1
The improvement of the characteristics of fatigue, tear, and abrasion/wear of the tyre tread of passenger cars compared to control cross-linking agent and a multifunctional cross-linking agent
The tyre tread for a passenger vehicleC1E1
NR20,00020,000
BR35,00035,000
SSBR45,00045,000
Silicon dioxide85,00085,000
The plasticizer 45,00045,000
The aging inhibitor6,0006,000
Zinc oxide2,5002,500
Stearic acid2,5002,500
TESPT6,7546,754

TBBS1,8101,810
Vulcuren VP KA 91882,544-
MFXL 1phr-2,640
MFXL 1mhr0,0027
Mooney (ML1+4)Unit Mooney43,543,8
MDR 2000 160°C
The length (degree of cure)-10min2,542,59
The length (degree of cure)-95min15,2514,42
MLDNM1,791,85
MHFDNM19,0419,54
MHF-MLDNM17,2517,69
The distance between the mesh nodes polymernm7,97,8
The density at room temperature g/cm31,1641,165
Hardness shore a at room temperatureShore a58,6to 58.1
Elasticity at room temperaturepercentage42,542,1
Elasticity at 70°Cpercentage54,1of 54.8
The tensile strength at room temperature
The tensile strengthMPa15,915,3
Elongation at breakpercentage550558
Tension (elongation)-50MPa1,021,09
Tension (elongation)-100MPa1,851,3

Tension (elongation)-200MPa4,34,24
Tension (elongation)-300MPa7,587,44
Abrasion on Penny%100109
Abrasion on DIN53516 at room temperaturemm349,2342,9
Tg (E”)°C-52-52
The test tire*)
Shore And at room temperatureto 58.159
Braking with moistened pads (low µ) with anti-lock device (ABS)%100102
Braking with moistened pads (high µ) with anti-lock device (ABS)%10099,9
Braking with dry pads%100100
Management in the dry state%100100,6
Aquaplaning%100100
Traction on snow%10098
Artificial ice%10098,5
Rolling resistance%10099
Wear %100108
*) Higher numbers mean better performance.

td align="left"> 59,5
Table 2
The improvement of the characteristics of fatigue, tear, and abrasion/wear of the tyre tread trucks compared to control cross-linking agent and a multifunctional cross-linking agent
Treads of tires for trucksC 2C3
C6-T2
E 2
MFXL
NRphr100,000100,000100,000
N 220phr43,50043,50043,500
The aging inhibitorphr6,0006,0006,000
Zinc oxide directlyphr,000 3,0003,000
Stearic acidphr2,0002,0002,000
TBBSphr1,1001,1001,100
Sulfurphr1,8001,6021,100
C6-T2phr-0,946-
MFXL 2phr--2,780
MFXL 2mhr0,00382
Mooney ML (1+4) 100°CUnit Mooney6059,360,3
Mooney ML (1+4)
MDR 2000 160°C
The length (degree of cure)-10min2,412,22,28
The length (degree of cure)-95minof 5.926,057,6
MLDNM2,522,53to 2.67
MHFDNMbr15.1516,115,12
MHF-MLDNM12,6313,5712,45
The density at room temperatureg/cm31,091,091,09
Hardness shore a at room temperatureShore a56,960,9
Hardness shore a at 70°CShore a51,655,354,6
Elasticity at room temperaturepercentageof 45.746,843,6
Elasticity at 70°Cpercentage56,957,952,4
The test of tensile strength at room temperature
The tensile strengthMPa20,923,321,7
Elongation at breakpercentage559562571
Tension (elongation)-50MPa0,961,11,07
Tension (elongation)-300MPa8,8710,169,02
The energy density at fractureJ/cm342,248,545,3
HSTEMJ/m310,139,1813,03
Graves 100°CN/mm60,0260,5273,20
The approximate temperature range 50/30N T (E“ max)Celsius-61,3-61,2-61,2

Table 3
The improvement of the characteristics of fatigue, tear, and abrasion/wear for connection "skeleton" (the layer of the breaker) compared to control cross-linking agent and a multifunctional cross-linking agent
The mixture breaker 4E 3E 4E 5
NRphr80,00080,00080,00080,000
BRphr20,00020,00020,00020,000
Silicon dioxidephr56,50056,50056,50056,500
Resinphr7,5007,5007,5007,500
The aging inhibitorphr3,7503,7503,7503,750
Ko saltphr0,3600,3600,3600,360
Auxiliary substances is a, to facilitate processingphr1,5001,5001,5001,500
ZnOphr8,0008,0008,0008,000
TESPTphr8,5008,5008,5008,500
N 339phr2,0002,0002,0002,000
HMMM resin 65%phr3,8503,8503,8503,850
DCBSphr1,6001,6001,6001,600
SULFURphr6,0005,7005,1003,600
mhr0,001900,003800,00760
MFXL 3phr-0,6801,3602,720
Mooney (ML1+4)Unit Mooney90,691,2of 92.789,8
MDR 2000 160°C
The length (degree of cure)-10min0,930,840,830,83
The length (degree of cure)-95min15,55accounted for 14.4513,8613,95
MLDNM 3,73,843,843,71
MHFDNM37,6838,6436,8331,38
MHF-MLDNMto 33.9834,832,9927,67
The density at room temperatureg/cm31,211,2111,2111,204
Hardness shore a at room temperatureShore a7879,878,6575,9
Hardness shore a at 70°CShore a75,176,6577,0572,9
Elasticity at room temperaturePercentage43,944,7 4442,5
Elasticity at 70°CPercentage53,356,955,152,9
The test of tensile strength at room temperature (R1)
The tensile strengthMPa18,518,215,519,0
Elongation at breakPercentage412408363477
Tension (elongation)-50MPa2,22,32,31,9
Tension (elongation)-300MPa14,114,213,812,1
Graves 100°CN/mm51,156,262,257,3

td align="center"> 2,4
Table 4
The improvement of the characteristics of fatigue, tear, and abrasion/wear for connection "skeleton" (the layer of the breaker) compared to control cross-linking agent and a multifunctional cross-linking agent
The mixture breaker5E 6E 7E. 8
NRphr100,000100,000100,000100,000
N 326phr55,00055,00055,00055,000
Silicon dioxidephr9,8009,8009,8009,80
Resin, plasticizerphr9,8009,8009,8009,800
The aging inhibitorphr2,5002,5002,5002,500
Ko saltphr2,0002,0002,0002,000
ZnOphr8,0008,0008,0008,000
N 339phr2,0002,0002,0002,000
HMMM RESIN 65%phr2,0002,0002,0002,000
DCBSphr1,3001,300 1,3001,300
INSOLUBLE SULFURphr5,5205,3304,3003,900
MFXL 3phr-0,6801,3602,720
MFXL 3mhr0,00190,00380,0076
Mooney (ML1+4)Unit Mooneyan 80.280,982,382,9
MDR 2000 160°C
The length (degree of cure)-10min1,591,671,731,78
Continue italmost (degree of cure)-95 min10,3810,429,39,26
MLDNM3,183,193,353,43
MHFDNM32,0831,4329,1628,02
MHF-MLDNM28,928,2425,8124,59
The density at room temperatureg/cm31,2041,2021,2021,203
Hardness shore a at room temperatureShore a77,5of 76.875,175,6
Hardness shore a at 70°CShore a753,7 71,571,35
Elasticity at room temperaturePercentage39,139,3a 38.537,6
Elasticity at 70°CPercentage53,352,551,9a 50.5
The test of tensile strength at room temperature
The tensile strengthMPato 19.919,819,519,3
Elongation at breakPercentage360362375377
Tension (elongation)-50MPa2,72,62,5
Tension (elongation)-300MPa18,218,0of 17.016,7
The energy density of destructionJ/cm331,9of 31.832,232,1
Graves 100°CN/mm48,9553,5559,2863,37

Table 5
The improvement of the characteristics of fatigue, tear, and abrasion/wear of the tyre tread trucks compared to control cross-linking agent and a multifunctional cross-linking agent
The tyre tread truck6E 97E 108E 11
NRphr100,000100,000100,000100,000100,000100,000
Work No. 121phr48,00046,00046,00046,00046,00046,000
Excipients that facilitate processingphr6,9002,4002,4002,4002,4002,400
The aging inhibitorphr1,0001,0001,0001,0001,0001,000
Stearic acidphr2,0002,0002,0002,0002,0002,000
phr3,0003,0003,0003,0003,0003,000
TBBSphr0.800 to0.800 to1,2001,2002,6002,600
Sulfurphr1,6001,0401,2000,8700,5500,450
MFXL3phr-4,078-4,078-1,359
MFXL3mhr0,01140,01140,0038
MDR 2000 160°C
The length (degree of cure)-10min2,6622,992,05with 3.272,8
The length (degree of cure)-90min6,396,646,166,728,03scored 8.38
MLDNM2,682,842,662,742,46to 2.57
MHFDNM16,0213,6216,0214,7415,2614,96
MHF-MLDNM 13,3410,78made 13.361212,8KZT 12.39
The density at room temperatureg/cm31,0981,1011,0971,0991,0951,096
Hardness shore a at room temperatureShore a61,359,160,260,159,5559,05
Hardness shore a at 70°CShore a56,2won with 51.7555,0553,2553,9553
Elasticity at room temperaturepercentage44,642,144,642,6of 45.744,1
Elasticity at 70°Cpercentage59,352,960,255,157,358
The test of tensile strength at room temperature
The tensile strengthMPa24,720,524,522,123,623,
Elongation at breakpercentage525508522508498511
Tension 50%MPa1,171,071,141,131,05 1,05
The tension of 300%MPa12,7010,7512,6811,8312,7812,41
HSTEMJ/m3to 7.6713,387,5810,337,148,5
Graves 100°CN/mm64,2074,1765,9381,3862,2385,18

8,5
Table 6
The improvement of the characteristics of fatigue, tear, and abrasion/wear of the tyre tread trucks compared to control cross-linking agent and a multifunctional cross-linking agent (control means)
The tyre tread truckC9 E12E13C10E13C11E14
NRphr100,000100,000100,000100,000100,000100,000100,000
Work No. 121phr48,00048,00048,00048,00048,00048,00048,000
Excipients that facilitate processingphr2,4002,4002,4002,4002,4002,4002,400
The aging inhibitorphr6,0001,0001,0001,0001,000 1,0001,000
Stearic acidphr2,0002,0002,0002,0002,0002,0002,000
ZnOphr3,0003,0003,0003,0003,0003,0003,000
TBBSphr0.800 to0.800 to0.800 to1,2001,2002,6002,600
SULFURphr1,6001,2501,2501,2001,0800,5500,460
MFXL4phr-1,016 1,484-1,016-1,016
MFXL4mhr0,0030,0040,0030,003
MDR 2000 160°C
The length (degree of cure)-10minutes2,62,852,862,973,013,253,29
The length (degree of cure)-90minutes6,366,48to 6.436,096,188,04
MLDNM2,772,642,612,682,542,472,4
MHFDNM15,9814,3314of 16.0515,0815,3113,7
MHF-MLDNM13,21of 11.69is 11.3913,3712,5412,8411,3
Temperature (Celsius)160160160160160160160
Duration (min)10101010 101515
The density at room temperatureg/cm31,0991,0981,0981,0971,0971,0951,095
Hardness shore a at room temperatureShore a60,2to 58.157,2560,55of 58.959,4558,45
Hardness shore a at a temperature of 70°CShore a55,752,2551,454,7553,154,2551,5
Elasticity at room temperaturepercentage46,3to 43.143,646,844,446, 42,3
Elasticity at a temperature of 70°Cpercentage59,156,758,260,458,35955,2
The test of tensile strength at room temperature
The tensile strengthMPa25,423,723,625,124,624,522,2
Elongation at breakpercentage537,3556,3555,6527,0549,2from 517.2521,0
Tension 50% 1,1631,0070,9951,141,0481,0580,948
Tension 100%MPa2,0671,7091,6882,0281,8141,9081,62
The tension of 200%MPa6,1825,0925,0716,2645,5756,1845,097
The tension of 300%MPa12,610,810,712,9the 11.612,811,0
The energy density at fractureJ/cm351,948,848,850,45,8 47,642,1
HSTEMJ/m3of 7.69at 10.6410,957,539,716,7910,04
Graves 100°CN/mm61,5566,4873,9072,3276,3054,0257,75

1. Composition for tires with hardness shore a according to DIN 53 505 and ASTM D2240 not less than 40 and not more than 95 and a glass transition temperature Tg (E" max) according to DIN 53 513 and the specified temperature range from -80°C to +80°C and the specified compression 10+0.2% at 10 Hz is not less than -80°C. and not more than 0°C, characterized in that it contains
- at least one vulcanizes diene rubber selected from the group of natural rubber, synthetic branch, Rubezhnoe, Ukraine rubbers, polyisobutylene rubbers, polybutadiene rubbers, and butadiene-styrene rubbers;
- 35-300 parts per 100 parts rubber parts by weight of at least one active filler selected from the types of carbon black, silica, the filler is silicon-based and metal oxides, of which at least 10 parts should be carbon black, silicon dioxide, or a combination;
- 0-250 parts other or additional additives;
from 0.1·10-3up to 42·10-3moles per 100 parts of rubber vulcanizing agent, which is sewn with a functionality greater than 4; and
is 0.1 to 20 parts of at least one vulcanization accelerator, where the curing agent comprises the chemical structure of the hydrocarbon type or heterorhabditis, or siloxanes and includes sulfur-containing structure with the following General formula:
G[CaH2a-CH2-SxY]n,
where G is a polyvalent hydrocarbon group, and/or heterophenomenology group, and/or siloxane group which contains from 1 to 100 atoms; each Y is independently selected from thiosulfonate group, dithiocarbamate group, a thiocarbonyl group, mercaptopropyl, hydrocarbon groups and groups thiosulfonate sodium (salt group Rebellion); each lower variables a, x and n represents an integer, which independently is true: a is 0-6; x is 0-8 and n is 3-5.

2. Composition for tires according to claim 1, wherein the vulcanizing agent include sulfur-containing cyclic structure with the following General formula:
G[CaH2a-CH2-SxY]n,
where G represents megavalanche the cyclic hydrocarbon group and/or heterophenomenology group, and/or cyclic siloxane group which contains from 5 to 8 atoms in the cyclic structure; each Y is independently selected from thiosulfonate group, dithiocarbamate group, a thiocarbonyl group, mercaptopropyl, hydrocarbon groups and groups thiosulfonate sodium (salt group Rebellion) and each of a, x and n represents an integer, which independently is true: a is 0-6; x is 0-8 and n is 3-5.

3. Composition for tires according to claim 1, wherein the vulcanizing agent include sulfur-containing cyclic aliphatic hydrocarbon with the following General formula:
G[CaH2a-CH2-SxY]n,
where G is a polyvalent cyclic hydrocarbon group which contains from 5 to 7 carbon atoms; each Y is independently selected from thiosulfonate group, dithiocarbamate group, a thiocarbonyl group, mercaptopropyl, hydrocarbon groups and groups thiosulfonate sodium (salt group Rebellion); and each a, x, and n is an integer, which independently is true: a is 0-6; x is 0-8 and n is 3-5.

4. Composition for tires according to claim 1, characterized in that it comprises 30-100 parts, at least one diene rubber.

5. Composition for tires according to claim 1, wherein the additional additives include plasticizers.

6. Composition for tires according to claim 1, characterized in that it is engages 0.1 to 15 parts, at least one vulcanization accelerator.

7. Composition for tires according to claim 1, characterized in that it includes 10-220 parts additional additives.

8. Composition for tires according to claim 1, characterized in that the filler is at least one of amorphous silicon dioxide.

9. Composition for tires according to claim 1, characterized in that the filler comprises amorphous silicon dioxide and soot.

10. Composition for tires according to claim 1, characterized in that the filler is at least one soot.

11. Applying a composition for tires according to claim 1 for the manufacture of tires.

12. Applying a composition for tires according to claim 11 for the manufacture of the tire tread or inner element of the tire.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to production of a fire-resistant rubber mixture and can be used in oil extraction, oil processing and mining industry. The rubber mixture contains the following ingredients, pts.wt (per 100.00 pts.wt rubber): butadiene-nitrile rubber - 100,00; thiuram D - 1.5; N,N'-dithiodimorpholine - 2.0; sulphenamide C - 2.0; naphtham-2 - 1.5; diaphene FP - 1.0; stearine - 1,0; colophony - 5.0; N-nitrosodiphenylamine - 1.0; chalk - 30.0; technical carbon P 701 - 55.0; technical carbon P 514 - 20.0; zinc oxide - 5.0; antimony trioxide - 4.0; chlorinated paraffin CP-1100 - 20.0; trichloroethylphosphate - 15.0; barium borate - 5.0.

EFFECT: obtaining a fire-resistant rubber mixture with high resistance to aggressive media and improved elasticity and strength properties.

2 tbl

FIELD: process engineering.

SUBSTANCE: invention relates to rubber mix. Rubber mix comprises soot to be mixed with rubber mix. Said soot is produced in kiln including continuous zones: kiln gas formation zone, reaction zone and reaction outage zone. High-temperature kiln gas is produced by combustion of hydrocarbons, spraying and injecting of raw stock in said high-temperature kiln gas in reaction zone. Fast cooling of high-temperature kiln gas in reaction outage zone produces aforesaid soot by adjustment of definite characteristics. Rubber mix contains produced soot in amount of 10-250 wt % per 100 wt % of rubber component (A). Rubber component A contains diene-based rubber with conjugated dual bonds.

EFFECT: well-balanced rolling and wear resistance of proposed tire.

8 cl, 1 dwg, 3 tbl, 25 ex

FIELD: chemistry.

SUBSTANCE: polymeric casting composition based on styrene-ethylene-butylene-styrene blockcopolymer contains antioxidant tetrakismethylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)methane, polypropylene, filler - microcalcite with average size of particle 2.1 mcm, naphthenic softener, polyphenyloxide, which increases size of end blocks of polystyrene, modified montmorillonite and superconcentrate of black pigment with the following component ratio (wt.p): styrene-ethylene-butylene-styrene blockcopolymer 100, Naphthenic softener 114-115, Polyphenyloxide 29-30, Polypropylene 44-45, Superconcentrate of black pigment 9-9.5, Filler - microcalcite 22-61, modified montmorillonite 1-5, tetrakismethylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)methane 1.8-1.9.

EFFECT: obtaining products with high level of physical and mechanical characteristics.

3 ex

FIELD: chemistry.

SUBSTANCE: composition contains a cross-linked interpolymer containing one or more monomer links based on diene and cross-linked with a tetraalkoxysilane cross-linking agent. The cross-linked interpolymer (A) contains less than 30 ppm halide from the total weight of the cross-linked interpolymer and (B) molecular-weight distribution ranges from 2.0 to 2.4.

EFFECT: invention reduces corrosion and contamination of equipment.

15 cl, 2 dwg, 2 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to the rubber industry and can be used in making industrial rubber articles. The butadiene-methylstyrene rubber based rubber mixture contains sulphur, diphenyl guanidine, a vulcanisation accelerator, technical carbon, zinc oxide, stearic acid, an anti-ageing agent and a modifier. The vulcanisation accelerator used is sulphenamide Ts, the anti-ageing agent and modifier are 2-(dibutylaminomethyl)-4-methyl-6-(1,7,7-trimethylbicyclo[2.2.1]hept-exo-2-yl)phenol.

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3 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to high-strength composite polymer materials for deck and floor coatings. The composite polymer material, which is a rubber mixture processed by a moulding technique, contains a polymer matrix, a vulcanising system consisting of thiuram, altax, zinc oxide and stearic acid, filler and process additives. The polymer matrix used is a petrol-, oil- and ozone-resistant polymer which is modified with polyvinyl chloride and contains 26-34 wt % acrylonitrile, and additionally sulphur, sulphenamide and polymerised 2,2,4-trimethyl 1,2- dihydroquinoline. The filler consists of BS-100 silicon dioxide, pigment titanium dioxide, natural hydrophobic chalk in weight ratio of 35-115:4-20:5-50 pts.wt, respectively. The process additives include TGM-3 oligoester acrylate plasticiser and antipyrenes which contain antimony trioxide and zinc borate in ratio of 3-20:5-25, and N-cyclohexyl thiophthalimide.

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2 cl, 2 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a rubber mixture, particularly for vehicle tyres. The rubber mixture contains 30-100 pts.wt of at least one diene rubber per 100 pts.wt rubber, 20-200 pts.wt of at least one filler per 100 pts.wt rubber, 0-200 pts.wt, of additional additives per 100 pts.wt rubber, a sulphur-containing vulcanisation system which includes free sulphur, a sulphur donor and silane, with sulphur concentration due to said ingredients between 0.025 and 0.08 mol per 100 pts.wt rubber, of which elementary sulphur accounts for 0-70%, the sulphur donor accounts for 5-30% and the silane accounts for 20-95%, and 0.1-10 pts.wt of at least one vulcanisation accelerator per 100 pts.wt rubber.

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22 cl, 11 tbl, 27 ex

FIELD: chemistry.

SUBSTANCE: invention relates to rubber industry and can be used in making wear-resistant rubber articles for construction purposes, operating in conditions of intense wear, low temperatures and aggressive media. The oil-and-petrol resistant rubber mixture contains butadiene-nitrile rubber BNKS-40AMN, isoprene rubber SKI-3, methyl styrene rubber SKMS-30 ARKM-15, sulphur, sulphenamide Ts, stearine, technical carbon P324, zinc oxide, regenerate RShT, thiuram D, kaolin, petroleum bitumen, naphtham-2, oil I-8A, N-nitrosodiphenylamine, and process additives - dispractol KS and a mixture of diphenyl carbonate and dimethyl carbonate resin DFK-1.

EFFECT: invention reduces the cost of the rubber mixture owing to use of cheaper process additives, and increases nominal tensile strength and breaking elongation, and reduces the abrasion index.

2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a fire-resistant rubber mixture and can be used in car, oil and industrial rubber industry. The fire-resistant rubber mixture contains synthetic isoprene and diene rubber, polyvinyl chloride, sulphur, sulphenamide Ts, zinc oxide, stearine, technical carbon, monoethanolamine, naphtham-2, diaphene FP, N-nitrosodiphenylamine, oxanol KD-6, antimony trioxide, chlorinated paraffin XP-70, chlorinated paraffin XP-470 and borates.

EFFECT: invention improves physical and mechanical properties, especially fire-resistance, tensile strength and breaking elongation.

3 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: composite material for outer lining of rubber-fabric conveyor belts based on stereoregular cis-1,4-polyisoprene with content of cis-1,4 units of at least 96% - SKI-3 contains ultrahigh molecular weight polyethylene modified with carboxyl with subsequent mechanical activation in amount of 5 pts.wt per 100 pts.wt SKI-3.

EFFECT: invention increases wear resistance, improves frost resistance of the composite material while preserving physical and mechanical properties, lowers the cost of the composite material.

2 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a composition of a water-redispersible polymer powder based on at least one synthetic polymer and at least one natural latex and which is used in compositions of construction materials. The composition of said polymer powder contains at least one water-insoluble synthetic polymer, preferably about up to 90 wt %, at least one modified natural latex, preferably about up to 90 wt %. The natural latex is obtained by mixing and reacting it, in aqueous phase, with at least one radical initiator and/or oxidising agent. The water-insoluble synthetic polymer is obtained using emulsion, suspension, microemulsion and/or inverted emulsion polymerisation. The composition also contains preferably about 0-50 wt % of at least one protective colloid, about 2-50 wt % of at least one filler and/or anti-caking agent. The composition also optionally contains additives. Modified latex, which is subsequently dried, is mixed with the synthetic polymer. The synthetic polymer is added before, during and/or after adding at least one radical initiator and/or oxidising agent. The synthetic polymer is added and/or in form of water-redispersible polymer powder.

EFFECT: invention enables to obtain redispersible polymer powder with improved water repellence and reduced water absorption.

15 cl, 4 tbl, 15 ex

Rubber mixture // 2502754

FIELD: chemistry.

SUBSTANCE: rubber mixture contains the following, pts.wt: soluble butadiene-styrene rubber with addition of TDAE oil with low content of polycyclic aromatic hydrocarbons 90-100, rubber with a cis-butadiene linear structure with high content of cis-links on a neodymium catalyst 10-20, natural rubber 5-8, insoluble sulphur 2-3, vulcanising group 3-8, silica filler with specific surface area of 165 m2/g 70-80, microcrystalline wax-based stabiliser 1-2, antiaging agents 3-5, process additive 1-3, binding agent - bis[3-(triethoxy)-silylpropyl]-tetrasulphide 10-15.

EFFECT: improved adhesion on a wet road with lower rolling loss and obtaining fuel-efficient tyres.

1 dwg, 3 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a redispersible, water-soluble polymer powder based on at least one modified natural latex. The modified natural latex can be obtained by mixing natural latex with at least one radical initiator and/or oxidising agent. The latex can also be obtained by mixing and reacting natural latex with at least one unsaturated olefin monomer and with at least one radical initiator. The polymer powder contains up to about 95 wt % of least one natural latex, about 0 to 50 wt % of at least one protective colloid, about 2 to 70 wt % of at least one filler and/or anti-caking agent, as well as optionally further additives.

EFFECT: invention increases looseness of the polymer powder, the powder does not cake over a long period of time at high temperature, compositions containing said polymer powder have high water repellence or low water absorption.

10 cl, 5 tbl, 17 ex

Pneumatic tyre // 2496809

FIELD: chemistry.

SUBSTANCE: rubber mixture contains per 100 pts.wt of a rubber component which contains at least one of natural rubber or synthetic rubber based on diene, 20-150 pts.wt precipitated silicon dioxide as filler and 1-25 pts.wt of a defined sulphur-containing silane compound as silane binder; silicon dioxide has cetyltrimethylaluminium bromide (CTAB) adsorption specific surface area (m2/g) and mode Aas of diameter (nm) of primary aggregates, determined by acoustic measurement of particle size distribution satisfying the equation (A), and for which the difference between loss of mass during calcination (wt % loss during calcination at 750°C for 3 hours) and loss of mass when heating (wt % loss during heating at 105°C for 2 hours) satisfies the equation (B) :Aas ≥ -0.76 × (CTAB) + 274 (a) (loss during calcination) - (loss during heating) ≤ 3 (B).

EFFECT: invention improves technological effectiveness of processing a rubber mixture and obtain tyres with low heat release and improved wear resistance.

12 cl, 3 tbl, 46 ex

Rubber mixture // 2495888

FIELD: chemistry.

SUBSTANCE: invention relates to a rubber mixture based on a combination of natural and synthetic cis-butadiene rubber, containing silica filler and can be used in the tyre industry for non-studded winter tyre treads. The rubber mixture contains the following, pts.wt: natural rubber SVR-70-80, cis-butadiene rubber - 20-30, sulphur - 1-2, vulcanising group - 8-9, active technical carbon - 5-10, silica filler with specific surface area of 165 m2/g - 30-50, stabiliser based on microcrystalline wax - 1-3, anti-ageing agents - 2-4, process additive - 1-3, softeners - 18-20, binding agent - bis-[3-(triethoxy-silylpropyl]-7-9.

EFFECT: invention increases adhesion of non-studded tyres to an ice-covered and snow-covered surface in a wide temperature range and reduces hysteresis losses.

6 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to methods of producing elastomeric composites and composites obtained using said methods. The method involves mixing a first aqueous fluid medium containing elastomeric latex with a second aqueous fluid medium containing filler particles; stimulating coagulation of the elastomeric latex to obtain mother batch crumbs; bringing the level of water content of the mother batch crumbs to a value ranging from about 1 wt % to about 20 wt % to obtain an anhydrous coagulum; removing water from the anhydrous coagulum by exposing the anhydrous coagulum to mechanical energy, resulting in heating of the anhydrous coagulum due to friction, wherein the anhydrous coagulum reaches temperature from about 130°C to about 190°C, where the level of water content is reduced to a value from about 0.5% to about 3%, and where the entire reduction of the level of water content is achieved by evaporation to obtain a plasticised mother batch; and exposing the plasticised mother batch to mechanical energy of at least 0.3 MJ/kg, with further reduction of the level of water content.

EFFECT: invention reduces viscosity of mother batches, improves filler dispersion, simplifies preparation of mother batches for producing a vulcanised rubber product.

48 cl, 6 dwg, 22 tbl, 13 ex

FIELD: chemistry.

SUBSTANCE: invention relates to rubber-cord composites and can be used in the tyre and industrial rubber industry. The rubber-cord composite consists of a layer of textile cord which is saturated with a latex-resorcinol-formaldehyde composition based on latex DBA-1 - a copolymer of butadiene, butyl acrylate, methacrylic acid amide or based on latex with vinyl pyridine links, optionally with another latex and optionally containing blocked E-caprolactam polyisocyanate, and a rubber layer. The rubber layer is made from a composition based on unsaturated rubber, with the following ratio of components of the rubber layer, pts.wt: unsaturated rubber - 100; ground technical sulphur - 0.5-0.8; polymeric sulphur - 1.0-1.5; sulphamide TS 0.2-0.4; altax - 0.4-0.7; technical carbon N 550 - 50-55; stearic acid - 1-2; oil-softener - 7-16; resin Pikar - 0.5-2.0; diaphene FP-1-2.5; pine rosin -1-3; zinc oxide - 5-6; modifier RU-D - 1-4 or resin modifier R-17-34 -0.8-1.5; white soot - 5-10; kaolin KR-1- 1-4.

EFFECT: invention increases strength of the textile cord-rubber bond.

2 tbl, 12 ex

FIELD: chemistry.

SUBSTANCE: neutral carbon source used is glucose, which is converted to aniline under the action of Escherichia coli or Streptomyces griseus bacteria. The glucose is obtained from plants. The stabiliser, vulcanisation accelerator or modified natural rubber is prepared from aniline obtained as described above.

EFFECT: invention improves environmental friendliness of methods of preparing a stabiliser, vulcanisation accelerator and modified natural rubber, which saves oil resources.

6 cl, 3 dwg, 5 ex

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

FIELD: chemistry.

SUBSTANCE: mixture contains a rubber component which contains a natural rubber component consisting of at least either natural rubber or epoxidated natural rubber. The mixture also contains inorganic filler containing at least silicon dioxide. Content of said inorganic filler ranges from 50 pts.wt to 80 pts.wt per 100 pts.wt said rubber component when the rubber mixture is used to obtain rubber for the clinch, and from 60 pts.wt to 100 pts.wt per 100 pts.wt said rubber component when the rubber mixture is used to obtain rubber for the sidewall filler. Content of soot in the rubber mixture ranges from 2 pts.wt to 5 pts.wt pr 100 pts.wt said rubber component. If the rubber mixture is used for the sidewall filler, the inorganic filler contains silicon dioxide and clay, the amount of clay in the mixture being equal to 5-40 pts.wt per 100 pts.wt rubber component and the total amount of silicon dioxide and clay is at least 65 pts.wt per 100 pts.wt rubber component. The result is reducing the amount of materials derived from oil resources when producing the rubber mixture.

EFFECT: improved operational characteristics.

8 cl, 1 dwg, 5 tbl, 16 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a rubber mixture, particularly for vehicle tyres. The rubber mixture contains 30-100 pts.wt of at least one diene rubber per 100 pts.wt rubber, 20-200 pts.wt of at least one filler per 100 pts.wt rubber, 0-200 pts.wt, of additional additives per 100 pts.wt rubber, a sulphur-containing vulcanisation system which includes free sulphur, a sulphur donor and silane, with sulphur concentration due to said ingredients between 0.025 and 0.08 mol per 100 pts.wt rubber, of which elementary sulphur accounts for 0-70%, the sulphur donor accounts for 5-30% and the silane accounts for 20-95%, and 0.1-10 pts.wt of at least one vulcanisation accelerator per 100 pts.wt rubber.

EFFECT: invention improves wearing characteristics of a vulcanised rubber mixture.

22 cl, 11 tbl, 27 ex

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