The rubber mixture

 

(57) Abstract:

The invention relates to the field of production of rubber mixtures tire purpose. The rubber mixture comprises a copolymer of butadiene or butadiene and styrene-methylstyrene) methyl ether methacrylate(acrylic) acid, or oxitropium, or oxypropylene, or -(N,N-dimethylamino)ethyl, or (N,N-diethylamino)or ethyl (N,N-dimethylamino)propyl, or N,N-diethylamino)propyl esters of methacrylic acid at a mass ratio of the corresponding monomers butadiene:styrene(-methylsterol):the ether 99,5-40,0:0-40,0:0,5-20,0 accordingly, 2-10 wt.h. aminocellulose agent combinations from groups:-aminoethoxyethanol, the product of the interaction of monoethanolamine with tetraethoxysilane, or polyphenylacetylene, or polyethoxysiloxane at mass ratio of 1:1-4, respectively, or a mixture aminocellulose agent combination from a group with bis(3-triethoxysilylpropyl)tetrasulfide mass ratio of 1-10:1, respectively, 5-80 wt.h. silica filler, 0-80 wt.h. technical carbon, 10-45 wt.h. special additives. Additives are plasticizers, sulfur, accelerators and sulfur vulcanization activators, dispersants, antioxidants. Volcanically, low heat buildup. table 2.

The invention relates to the field of production of rubber mixtures tire purpose, containing silica fillers and fabricate tires with enhanced performance properties, specifically rubber compounds based on unsaturated rubbers containing silica fillers and agents of the combination, providing education colophony structures between silica fillers and macromolecules rubber.

Known vulcanicola rubber mixture comprising an unsaturated rubber such as butadiene-styrene rubber, emulsion polymerization, 5-100 wt.h. filler - oxide silicon - on 100 wt.h. rubber, 0.1 to 15.0 wt.h. organic agent combinations containing functional groups, one of which structuresa mercaptopropyl able to join the rubber and the other is a nitrogen - containing (isocyanate, carbodiimide, imino or amino group), and a nitrogen-containing group of the amine type, the agent combinations contains at least two such groups [U.S. patent 3884285, the IPC 60 5/100, 08 With 11/10, 11/12 08 With, publ. 20.05.1975,], for example, this agent combination is the product of the interaction of polyethylenepolyamine with tx2">However, it has significant drawbacks - high viscosity of the unvulcanized mixtures, low strength at 300% elongation. Also used in the rubber compound products produced from highly toxic compounds - polyethylenepolyamine, tylenchida substances of the 1st and 2nd hazard class.

Also known rubber compound comprising 100 wt.h. natural or synthetic rubber or mixture of rubbers, 0,75-35.00 wt.h. triazole type benzotriazol, tolyltriazole, aftertreated or other similar connection, 2-35 wt.h. powder brass, or conductive carbon black, or mixtures thereof, silica filler and silane agent combinations selected from the group of 3,3'-bis(triethoxysilylpropyl)tetrasulfide, 3-mercaptopropyl-ethoxysilane [U.S. patent 6014998, IPC From 08 To 003/34, 60 011/00, 60 001/00, publ. 18.01.2000,].

This rubber compound provides high speed vulcanization, increased hardness and strength properties, high dynamic modules rubbers based on it.

The disadvantages of rubber mixtures are high tendency to podocarpaceae, the need for addition of aminecontaining and silane agents combination of advanced brass-particulate pooga powder and 4.8 wt.h. 3,3'-bis(triethoxysilylpropyl)tetrasulfide.

Also known rubber compound comprising 100 wt.h. diene rubber or mixture of rubbers, of which at least one is a diene rubber, 5-100 wt.h. filler consisting of precipitated silica and carbon black, where the precipitated silica is in the amount of 10-80 wt.h. on 100 wt.h. rubber, listeriosis agent combination of N,N'-dithiobis(benzosulfimide), or a combination 95-25% by weight of sulfonamida and 5-75 wt.% 3,3'-bis(triethoxysilylpropyl)tetrasulfide, and the mass ratio of agent combinations and silicon dioxide are from 0.01:1 to 0.20:1 [U.S. patent 5981633, the IPC 60 011/00, publ. 9.11.1999,].

This rubber compound enables the vulcanization as a separate diene rubber, and a mixture of rubber, resulting in a gain vulcanizates with good uprugoopticheskii properties, low tangent of mechanical loss and good endurance.

The disadvantages of rubber compounds include the following: not enough high strength of the vulcanizate when using large quantities of silica filler and a single agent combination - sulfonamida; synthesis of N,N'-dithiobis(sulfonamida) is a complex, multi-stakeholder who nicesly essence and the achieved result to the present invention is a rubber compound, containing 100 wt.h. at least one vulcanizing grey rubber selected from the group of polymers of conjugated dienes or diene copolymers and vinylaromatic compounds, 10-250 wt.h. precipitated silicon dioxide, 0.05 to 10.00 wt.h. aminosilane General formula I:

where R1, R2and R3- CNS radical containing 1-8 carbon atoms, R4- Allenova group containing 1-18 carbon atoms or arisen or alkylenediamine group with 6-10 carbon atoms, R5is hydrogen or an alkyl group, 0.05 to 10.00 wt.h. serosoderjaschei organosiloxane General formula II or III:

where n=2-8, R1, R2, R3- alkoxyalkyl with 1-3 carbon atoms, R4- Allenova group with 1-3 carbon atoms, with the rubber mixture comprises a rubber selected from the group of natural rubber, polychloroprene, polyisoprene, polybutadiene, butadiene-styrene copolymer, Acrylonitrile-isoprene copolymer, butadiene-nitrile rubber, ethylene-propylene-diene rubber, methyl methacrylate-butadiene copolymer, methyl methacrylate-isoprenoid copolymer, or mixtures thereof; rubber mixture may also include carbon black, silicates [U.S. patent No. 5698619, the military tetrasulfide and aminecontaining silanes provides the manufacture of rubbers with improved resistance to wear and tear, high elasticity and low hysteresis losses. In addition, the introduction of rubber compound of aminoalkylsilane allows you to reduce the dosage of polysulfide silane agent combinations. For example, you can use aminopropyltriethoxysilane at a dose of 2.0 wt.h. and product Si-69 (bis(3-triethoxysilylpropyl)tetrasulfide) at a dose of 6 wt.h.

The disadvantage of this rubber compound is the need to use aminoalkylsilanes, since compounds of this class are hard-expensive products. For example, the synthesis of aminopropyltriethoxysilane (most, judging by the description of known technical solutions, the optimal product) is carried out by interaction of allylamine with triethoxysilane in a mixture of isopropyl alcohol and allylglycidyl ether in the presence of a catalyst is hexachloroplatinic acid.

The technical object of the present invention to provide a rubber mixture with the use of aminosilanes agent combinations, synthesized by a simple technique of low-toxic products available, the vulcanizates on the basis of which possess good uprugoopticheskii characteristics, lovati the inventive rubber mixture for rubber tire purpose.

The technical problem is solved by the fact that the rubber mixture comprising a copolymer of diene and ester, unsaturated carboxylic acid, silica filler, aminosilanes agent combinations and targeted supplements, as diene copolymer and ester, unsaturated carboxylic acid contains a copolymer of butadiene or butadiene and styrene-methylstyrene) methyl ether methacrylate (acrylic) acid, or oxitropium a methacrylic acid, or oxypropylene a methacrylic acid, or (N,N-dimethylamino)ethyl ester, methacrylic acid, or (N,N-diethylamino)ethyl ester of methacrylic acid, or (N,N-dimethylamino)propyl ester, methacrylic acid, or (N,N-diethylamino)propyl ester, methacrylic acid at a mass ratio of the corresponding monomers in the specified copolymer of butadiene:styrene(-methylsterol):the specified ester, unsaturated carboxylic acid 99,5-40,0:0-40,0:0,5-20,0 accordingly, and as aminosilanes agent combinations mixture contains a product selected from the group-aminoethoxyethanol, the product of the interaction of monoethanolamine with tetraethoxysilane, or polyphenylacetylene, or polyethoxysiloxane at mass ratio of 1:1-4 soutourina mass ratio of 1-10:1, respectively, and may contain carbon black with the following content of components in the rubber mixture, wt.h.:

The specified copolymer of butadiene or butadiene and styrene-methylstyrene) with ether, unsaturated carboxylic acid 100

Silica filler 5-80

Carbon 0-80

Specified aminosilanes agent combination or said mixture aminocellulose agent in combination with a bis(3-triethoxysilylpropyl)tetrasulfide 2-10

Targeted supplements 10-45

As the silica filler in the rubber compound is finely dispersed precipitated silicon oxide, for example BS-120 GOST 18307-78 (made in Russia), Ultrasil VN3(produced by Ron Pulinc); HiSil (company PPG Industries).

The use of silica filler in combination with technical carbon allows you to manage uprugoopticheskii and dynamic properties of the vulcanizates. In the preparation of the rubber mixtures according to the examples use carbon black mark P-234 according to GOST 7885-86.

The inventive rubber mixture contains also the target additives, plasticizers, sulfur, accelerators and activators of sulfur vulcanization, dispersing agents, antioxidants, etc. as antioxidants using N,N'-diphenylethylenediamine, N-isopropyl-N'-phenyl-n-phenylenediamine or the La (-methylstyrene) with ether, unsaturated acid is obtained by aqueous emulsion polymerization using as an initiator redox iron-Trilon-regalitos system, as the emulsifier mixture was washed infolevin and fatty acids. The temperature of polymerization IS, the reaction time is 10-16 hours, the conversion of monomers into polymer 60-70%. A method of producing a copolymer of butadiene, styrene and methyl methacrylate described in the patent of the Russian Federation No. 2115664. Degassed rubber isolated from the latex mixture of electrolytes: salt+acid. Rubber press against moisture and dried in an air dryer. Monomeric composition rubbers are shown in table 1.

In example 10 describes a method of producing a copolymer of isoprene and methyl methacrylate used for the preparation of rubber mixtures in examples 31, 32 of the prototype.

Example 11.

A mixture of 416 g of tetraethoxysilane and 122 g of monoethanolamine (mass ratio of 3.4:1) heated to a temperature of 90-160S when mixed with continuous distillation of the liberated in the reaction of ethanol. The reaction time is 2.5 hours. Receive 446 g of the target product of aminoethoxyethanol. The composition and structure of the product proven methods of elemental and spectral analysis. The nitrogen content obtained by the method of kildala, 6.7% as calculated by 6.3%). In the H1 NMR spectrum contains bands with chemical shift: 1,0-1,12 M. D. (protons of CH3group); 3,67-to 3.73 M. D. (CH3-group), 2,7 M. D. (NH2-group). In the IR spectrum of the m-1(N-H).

Example 12.

Aminosilanes agent combinations are given as described in example 11, but the mass ratio of tetraethoxysilane and monoethanolamine is 2:1.

Example 13.

Aminosilanes agent combinations are given as described in example 11, but the mass ratio of tetraethoxysilane and monoethanolamine is 4:1.

Examples 14 and 15.

In accordance with example 11 receive the products of the interaction of polyphenylacetylene with monoethanolamine at mass ratios of polyphenylacetylene and amerosport 2:1 and 4:1. As polyphenylacetylene use industrial products PES-50 or PES-80 (TU 6-01-20-52-90).

Examples 16-18.

In accordance with example 11 receive the products of interaction of polyethoxysiloxane with monoethanolamine at different mass ratios of siloxane and amerosport - 2:1, 3:1 and 4:1. As polyethoxysiloxane use industrial products ethyl silicate-32, ethyl silicate-40, ethyl silicate-50 (GOST-84).

Example 19.

Preparing a rubber mixture based rubber obtained in example 1, representing an emulsion copolymer containing 81.5% of butadiene, 14% styrene and 4.5% of methyl methacrylate.

As garimara 11.

The mixture of components is carried out in two stages, the first stage in a rubber mixer, and the second in the mill. The following is the mode of preparation of the rubber mixture of:

The mixture discharged from the rubber mixer at the 11th minute and cooled to S in the mill.

The rubber mixture is removed from rolls on the 9th minute.

Full recipe rubber compound are shown in table 2.

Physico-mechanical properties of rubber mixtures and vulcanizates is determined according to GOST 23492-83, abrasion resistance - according to GOST 23509-79.

Properties of rubber mixtures and vulcanizates are also given in table 2.

The rubber mixture has a fairly good technological properties, the normal parameters of vulcanization, vulcanizer is characterized by high uprugoopticheskii properties, high elasticity and good dynamic characteristics.

Examples of 20-30.

Rubber compound is prepared analogously to example 19, using different ways of rubbers, different dosages and combinations of fillers, agents, combinations and other ingredients. The composition and properties of the rubber mixtures is given in table 2.

Examples 31, 32 (the prototype).

Preparing a rubber mixture based on copoly the mixture comprises bis(3-triethoxysilylpropyl)tetrasulfide (product Si-69, production company "Degussa"), and aminopropyltriethoxysilane (product of AGM-9, production of JSC "Khimprom", , Slavgorod, THE RF P-8-62).

Preparation of rubber mixtures is performed in example 19. The full formulation of the rubber mixtures and their properties are shown in table 2.

As can be seen from the data presented in examples 1-32 and tables 1, 2, the set of essential features of the claimed invention can solve the technical problem is getting the rubber compound using aminosilanes agent combinations, synthesized by a simple technique of low-toxic products available, the vulcanizates on the basis of which possess good uprugoopticheskii characteristics, high elasticity and wear resistance, low heat buildup.

Rubber mixture comprising a copolymer of diene and ester, unsaturated carboxylic acid, silica filler, aminosilanes agent combination and the target additives, characterized in that as a copolymer of diene and ester, unsaturated carboxylic acid compound contains a copolymer of butadiene or butadiene and styrene-methylstyrene) methyl ether methacrylate (acrylic) is (N,N-dimethylamino)ethyl ester, methacrylic acid, or (N,N-detemine)ethyl ester, methacrylic acid, or (N,N-dimethylamino)propyl ester, methacrylic acid, or (N,N-diethylamino)propyl ester, methacrylic acid at a mass ratio of the corresponding monomers in the specified copolymer of butadiene:styrene (-methylsterol): the specified ester, unsaturated acid 99,5-40,0:0-40:0,5-20,0, and as aminosilanes agent combination of the rubber mixture contains a product selected from the group-aminoethoxyethanol, the product of the interaction of monoethanolamine with tetraethoxysilane, or polyphenylacetylene, or polyethoxysiloxane at mass ratio of 1:2-4, respectively, or a mixture aminocellulose agent combinations of the specified group with bis(3-triethoxysilylpropyl)tetrasulfide mass ratio of 1-10:1, respectively, and may contain carbon black with the following content of components in the rubber mixture, wt.h.:

the specified copolymer of butadiene or butadiene and styrene

(-methylstyrene) with ether, unsaturated carboxylic acid 100

silica filler 5-80

carbon 0-80

specified aminosilanes agent combination or

the specified mix aminocellulose agent combination is

 

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