Modifier for rubber mixtures (options) and how to obtain it (options)

 

The invention relates to multi-functional modifiers used in tire and rubber industry for rubber compounds based on unsaturated rubbers. Modifier for rubber compounds include 1,4-bis(trichloromethyl)benzene, contains as the target solid additives, petroleum waxes, chlorinated polyvinyl chloride and trialkyl, or dialkylated, or triarylphosphite or their mixture, or contains as special additives solid chlorinated paraffins with carbon chain length From18-C36and mass fraction of chlorine with 55.1 71.2 percent, trialkyl, or dialkylated, or triarylphosphite, or their mixture and surfactant ionic and nonionic type. Getting these modifiers include dissolution in the melt of 1,4-bis(trichloromethyl)benzene with mass fractions of the basic substance 95,0-99.5% and the above-mentioned phosphates or mixtures thereof, polyvinyl chloride or solid oil paraffins with carbon chain length From18-C36their chlorination with gaseous chlorine with the initiation process azobisisobutyronitrile, and then adding to the mixture of other components in the desired proportions. Modifier improves the properties of rubber compounds to improve PR the ways;">

The invention relates to multi-functional modifiers used in tire and rubber industry for rubber compounds based on unsaturated rubbers.

Known use as a modifier of the rubber mixtures of the product of the interaction of 1,4-bis(trichloromethyl)benzene and anhydrotetracycline taken in the ratio of 0.33 to 3.0:1, respectively [USSR Author's certificate 827498, CL 08 To 5/03, 5/18, 08 L 9/00, 1979].

It is also known the use in rubber compounds as a modifier of the interaction product of hexamethylenetetramine (urotropine) with 1,4-bis(trichloromethyl)benzene in the ratio of initial components 1: 3-3:1 [USSR Author's certificate 478017, class 08 With 11/24 08 D 13/28, 1975].

In addition, it is known the use of a modifier of rubber compounds based on 1,4-bis(trichloromethyl)benzene containing 1,5-3,0% solution dibenzylethylenediamine in wax in the amount of 20-30% [USSR Author's certificate 900619, CL 08 To 5/34, 08 L 9/00, 1982].

Widely used in tire and rubber industry is a multifunctional modifier for rubber mixtures Hexal ZVI, including 1,4-bis(trichloromethyl)benzene quantity 74-85 wt.%, the wax in the amount of 14.5-24 wt. % and the mixture -14, and hexamethylenetetramine in a mass ratio of 1: 1 in the amount of 0.5-2.0 wt. % [USSR author's certificate 1367437, C 08 K 5/00, 08 L 9/00, 1988].

Shortcomings listed modifiers are their tendency to caking and absorption of air moisture during transportation and storage, as well as a significant drop of activity modifiers during storage, leading to instability properties of rubber compounds derived from their use, and to reduce the level of physico-mechanical characteristics of rubber.

The prototype of the present invention is a modifier of rubber compounds based on unsaturated rubbers, including 1,4-bis(trichloromethyl)benzene and the following additives target: wax, chlorinated polyethylene and Las calcium General formula (CnH2n+1With6H4SO3)2Sa, where n=12-14, in the following ratio, wt.%: 1,4-Bis(trichloromethyl)benzene - 85,0-92.0 Wax - 3,5-5,0 Las calcium - 0,5-2,0 Chlorinated polyethylene - 4,0-11,0 Modifier prototype is obtained by mixing the components in the melt, and before mixing components carry out the chlorination of polyethylene with chlorine in the environment 1,4-bis(trichloromethyl)benzene at 115-125oWith up to pace is the group of components in the above ratio and the cooling composition in a thin film with a speed of 10-20oC/C to 15-25o[RF Patent 2131442, IPC 6 08 L 23/06 08 L 9/06, 08 K 5/00, 08 J 3/20, 1999].

The disadvantage of this modifier is modifying its relatively low activity, which determines the strength of bonding rubber with textile cord, as well as insufficient adhesion of rubbers obtained with its use.

Objectives of the invention are to improve the efficiency modifier for rubber compounds to improve the strength of rubber with textile cord and increase the stickiness of rubber and the creation of the production technology.

This technical result is achieved by the fact that the modifier for rubber compounds based on unsaturated rubbers, including 1,4-bis(trichloromethyl)benzene, contains as the target solid additives, petroleum waxes, chlorinated polyvinyl chloride and trialkylphosphine or dialkylammonium, or triarylphosphite, or their mixture, in the following ratio, wt.%: 1,4-Bis(trichloromethyl)benzene - 87,0-94,0 Solid petroleum waxes - 0,8-3,7 Chlorinated polyvinyl chloride - 5,0-9,0 Trialkylphosphates, or dialkylammonium, or triarylphosphite, or a mixture of 0.2-0.3
The above technical result is also achieved by the fact that the rubber modifier is additives solid chlorinated paraffins with carbon chain length From18-C36and mass fraction of chlorine within 55,1 71.2 percent, trialkylphosphates, or dialkylammonium, or triarylphosphite, or their mixture and surfactant ionic or nonionic type in the following ratio, wt.%:
1,4-Bis(trichloromethyl)benzene - 87,0-94,0
Surface-active agent of the ionic or nonionic type - 0,2-0,4
Chlorinated paraffin waxes with carbon chain length From18-C36and mass fraction of chlorine within 55,1 71.2 percent - 5,6-12,6
Trialkylphosphates, or dialkylammonium, or triarylphosphite, or a mixture - 0,2-0,4
The modifier in the first embodiment is obtained by dissolving at 112-115oC a 4.1-8.0 wt.% polyvinyl chloride (PVC) in the melt of 1,4-bis(trichloromethyl)benzene with mass fractions of the basic substance within 95,0-99.5% pure, containing of 0.21 and 0.35 wt.% trialkylphosphine, or dialkyldithiophosphate, or triarylphosphine, or mixtures thereof, chlorination of polyvinyl chloride with gaseous chlorine at 115-125oC initiate azobisisobutyronitrile, taken in an amount of 0.01-0.1% by weight of the mixture, to a temperature dropping point of the reaction mass within 95-105oC with subsequent Stripping acid gas at 110-120oWith, by dissolving in a mixture at 110-125oSolid is rmutil)benzene 87,0-94,0
Solid petroleum waxes - 0,8-3,7
Chlorinated polyvinyl chloride - 5,0-9,0
Trialkylphosphates, or dialkylammonium, or triarylphosphite, or a mixture of 0.2-0.3
The modifier according to the second variant is obtained by dissolution in the melt of 1,4-bis(trichloromethyl)benzene with mass fractions of the basic substance within 95,0-99.5% pure, containing 0.2-0.5 wt.% trialkylphosphine, or dialkyldithiophosphate, or triarylphosphine, or their mixtures, of 2.0 to 5.1 wt.% solid oil paraffins with carbon chain length From18-C36and their chlorination at 112-125oWith gaseous chlorine with the initiation process azobisisobutyronitrile, taken in an amount of 0.02-0.1 percent by weight of the mixture, to a temperature dropping mixture within 94-105oWith and receiving chlorinated paraffin waxes with a mass fraction of chlorine within 55,1 71.2 percent, followed by Stripping acid gas at 110-120oWith, by dissolving in a mixture at 110-120oWith surfactants of ionic or nonionic type and receiving modifier in the following ratio, wt.%:
1,4-Bis(trichloromethyl)benzene - 87,0-94,0
Surface-active agent of the ionic or nonionic type - 0,2-0,4
Chlorinated paraffin waxes with a carbon chain length WithCarrying out the chlorination of PVC or solid paraffin oil in the melt of 1,4-bis(trichloromethyl)benzene at temperatures above 125oWith technically and economically feasible, and at temperatures below 112oWith technically difficult, because the melting point of 1,4-bis(trichloromethyl)benzene containing 0,21-0,35 (0,2-0,5)% by weight the above phosphate is 108-110oC.

Chlorination above PVC (4,1-8.0 wt.%) in the environment of 1,4-bis(trichloromethyl)benzene to the temperature dropping mixture in the range of 95-105oWith an optimal condition for obtaining chlorinated PVC, possessing properties of high adhesion additives target and prevent caking of the product. At the same time provides the chlorinated PVC optimal technical properties of the modifier is the number average of 5.0-9.0% of mass of the target composition.

Chlorination of specified quantities of solid paraffin oil (2.0 to 5.1 wt.%) in the environment of 1,4-bis(trichloromethyl)benzene to the temperature dropping mixture within 94-105oWith and receiving chlorinated paraffins with a mass fraction of chlorine within 55,1 71.2 percent is the optimal condition for obtaining vysokooplachivaemoi product. This ensures getting these chlorinated paraffins in optimal technical properties of the modifier quantity, that is, 5,6-12.6% of the mass of the target composition.

The possibility of using the proposed methods, 1,4-bis(trichloromethyl)benzene with mass fractions of the basic substance within 95,0-99,5% due to the fact that in the conditions of the chlorination of polyvinyl chloride or solid paraffin oil in the environment 1,4-bis(trichloromethyl)benzene is dharitvena the impurity 4-dichlorocarbanilide and 1,4-bis(dichloromethyl)benzene in the target product.

As solid paraffin oil according to the first variant of the proposed modifier and method of its production can be any solid saturated hydrocarbons of petroleum origin as individual, for example n-octadecan18H38or n-eicosan20H42and industrial produce a mixture, for example paraffin oil firm different grades according to GOST 23683-89 match or paraffin, which is a mixture of paraffin waxes from C18H38and above. The length of the carbon chain used paraffin is limited to only the lower limit of the C18because the lowest paraf ogandaga or nonionic type according to the second variant of the proposed modifier and method of its production may be used any compounds of these classes, which are stable under the described circumstances obtain composition and sufficiently inert to the components of the modifier. In particular, it is possible to use alkylbenzenesulfonates calcium or sodium, ethoxylated mono - and dialkylphenols (for example, emulsifiers OP-7 and OP-10, neonols different brands), calcium stearate, alkyl sulphonates or reinoculated sodium or various mixtures of these substances.

Below are examples illustrating the proposed variants of the modifier and the methods for their preparation.

Example 1.

In a glass chetyrehpolnye reactor equipped with a thermometer, dropping funnel with a bypass gas-feeding tube with porous glass bubbler, mechanical stirrer and reflux condenser with gas outlet tube connected to the absorption flask, placed 188,31 g of 1,4-bis(trichloromethyl)benzene containing 95,0-of 99.5 wt.% the basic substance and 0.35 wt.% cresyldiphenyl or dibutyltindilaurate, heated to 112-125oC. In the resulting melt at a specified temperature and stirring dissolve 15,1 g PVC or 8.0% by weight of 1,4-bis(trichloromethyl)benzene. After complete dissolution add to the mix a few drops of 12-13%-aqueous solution in which sup>oWith, adding every 15-20 minutes 2-4 drops of a solution of the initiator and feeding chlorine with a speed of 12 to 14 g per hour. The total amount of initiator used is 0.02-0.2 g or 0.01-0.1 % by weight of the initial mixture. Chlorination stop when the temperature dropping mixture in the range of 95-105o(In this example, 101oC) and the weight of the reaction mass or 4.31 g, which corresponds to the receiving 19,41 g chlorinated PVC, after which the reaction mass is blown with an inert gas at 110-120oFor removal of acid gases. Then she injected 7.98 g of paraffin oil firm (according to GOST 23683-89) or match paraffin. The mixture is stirred until a homogeneous mass at 110-125oWith and then fed to the mold roller. Get 215,7 g modifier with temperatures dropping 99oC. the modifier Composition, wt.%:
1,4-Bis(trichloromethyl)benzene - 87,0
Solid, petroleum waxes or match paraffin - 3,7
Chlorinated polyvinyl chloride 9,0
Cresyldiphenyl or dibutyltindilaurate - 0,3
Example 2.

In the reactor described in example 1 is placed 188.4 g of 1,4-bis(trichloromethyl)benzene containing 95,0-of 99.5 wt.% the basic substance and 0.21 wt. % (0.4 g) of tributyl phosphate or dibutyltindilaurate, heated to 115-125o and 115-125oC initiate azobisisobutyronitrile, taken in an amount of 0.01-0.1% by weight of the mixture and used in the form of 12-13% solution in chloroform, feeding chlorine with a speed of 10 to 12 g per hour. Chlorination stop when the temperature dropping mixture 105oAnd weight gain of 2.2 g, which corresponds to obtain 10.0 g of chlorinated PVC. After Stripping acid gas at 115-120oWith injected into the melt 1.6 g match paraffin or paraffin oil solid and stirred the mixture until a homogeneous mass at 110-120oC. the Target composition is cooled and crystallized in a thin film. Get 200 g of the modifier with the dropping temperature 105oC. the modifier Composition, wt.%:
1,4-Bis(trichloromethyl)benzene - 94,0
Solid, petroleum waxes or match paraffin - 0,8
Chlorinated polyvinyl chloride 5,0
Tributyl phosphate or dibutyltindilaurate - 0,2
As can be seen from the examples, when the chlorination of 4.1 to 8.0 wt.% PVC is obtained chlorinated PVC in the amount of 5.0-9.0% of mass of the target composition, the content of esters of orthophosphoric acid was slightly reduced from 0.21 and 0.35 wt.% 1,4-bis(trichloromethyl)benzene to 0.2-0.3% by weight of the composition, respectively.

Example 3 (standard method).

In the reactor, the op is wt.% (0.84 g) of tributyl phosphate or dibutyltindilaurate, and dissolve in it when 112-125oFrom 9.37 g or 5.0% of the mass of the initial 1,4-bis(trichloromethyl)benzene paraffin oil with solid carbon chain length With18-C36. Added to the melt a few drops of 12-13% solution azobisisobutyronitrile in chloroform and glorious the mixture at the specified temperature with gaseous chlorine. The total number used in the process of azobisisobutyronitrile is 0.04-0.20 g or 0.02 to 0.1% by weight of the mixture. Chlorination stop when the temperature dropping mixture within 94-105oWith and gain the reaction mass in the range of 11.0-17.0 g, which ensures the production of chlorinated paraffin waxes with a mass fraction of chlorine within 55,1 71.2 percent. In this example, the dropping temperature of the mixture 94oWith, the gain is 11,03 g, which corresponds to the receiving 20,34 g of chlorinated paraffin wax with a mass fraction of chlorine 55.1 per cent. From the reaction mass otdovat dry nitrogen acid gases at 115-120oC for 20-30 minutes, after which it added 0.84 g of surface-active substances (surfactants) ionic type, such as alkylsulfonate sodium or Las sodium or calcium. The mixture was stirred at 110-120oTo obtain a homogeneous composition, which serves to Crist is Katara, wt.%:
1,4-Bis(trichloromethyl)benzene - 89,5
Chlorinated paraffin waxes with carbon chain length From18-C36and mass fraction of chlorine 55,1% and 9.7
Tributyl phosphate or dibutyltindilaurate - 0,4
Alkylsulfonate sodium or Las sodium or calcium - 0,4
Example 4.

Synthesis is carried out according to the method described in example 3, on the basis of 188,12 g of 1,4-bis(trichloromethyl)benzene containing 95,0 wt.% the basic substance and 0.2 wt.% or 0.4 g of a mixture of cresyldiphenyl and dirtypantylover, 5,15 g or 2.7% by weight of 1,4-bis(trichloromethyl)benzene solid oil paraffins with carbon chain length From18-C36and 0.04 g of azobisisobutyronitrile used in the form of a 12% solution in chloroform. Chlorination complete when the temperature dropping 104oAnd weight gain reaction mass 6,07 g, which corresponds to the receiving 11,18 g of chlorinated paraffins with a mass fraction of chlorine 55.1 per cent. After Stripping acid gas in the reaction mass contribute 0.4 g of surfactant nonionic type, for example emulsifier OP-7 or OP-10, or neonol FBA-10, stirred at 110-120oTo obtain a homogeneous composition, which is then crystallized in a thin film. Get 199,7 g modifier with dropping temperature of 104.5o18-C36and mass fraction of chlorine 55,1% and 5.6
The mixture cresyldiphenyl and dirtypanties - 0,2
Emulsifier OP-7 or OP-10, or neonol FBA-10 - 0,2
Example 5.

Synthesis is carried out according to the method described in example 3, on the basis of 188,09 g of 1,4-bis(trichloromethyl)benzene, containing of 99.5 wt.% the basic substance and 0.23 wt. % (0,43 g) dibutyltindilaurate or its mixture with tributyl phosphate, of 8.37 g of solid paraffin oil With18-C36and 0.2 g of azobisisobutyronitrile used in the form of a 13% solution in chloroform. Chlorination complete when the temperature dropping, the reaction mass 105oWith and gain mass 18,85 g, which corresponds to the receiving 27.18 per g of chlorinated paraffin wax with a mass fraction of chlorine 71.2 percent. After Stripping acid gas in the melt contribute 0,43 g-ionic surfactant or non-ionic type, such as calcium stearate or neonol FBA-12. Stir the mixture at 110-120oTo obtain a homogeneous composition, which crystallized as described above. Get 215,7 g modifier with dropping temperature 105oC. the modifier Composition, wt.%:
1,4-Bis(trichloromethyl)benzene - 87,0
Chlorinated paraffin waxes with carbon chain length From18-C36and mass fraction of chlorine 71,2% - 12,6
Dibutylphtalate the chlorination of 2.0 to 5.1 wt.% paraffins obtained these chlorinated paraffin wax in the amount of 5.6-12.6% of the weight of the composition, the content of esters of orthophosphoric acid decreases slightly: from 0.2 to 0.5. % 1,4-bis(trichloromethyl)benzene to 0.2-0.4% by weight of the target composition.

All obtained by the proposed methods samples modifiers well celuyutsya, stable when stored at 20 to 40oWith over 8 months, are good, have a low specific smell, have a dropping point in the range 95-105oWith that determines the ease of dosing and effective dispersion of the modifier in the rubber mixtures.

The effectiveness of the samples modifiers of various compositions were tested in rubber mixtures based on 100 SKI-3, used now in tire factories for textile lining fabric frame truck radial tires. The rubber mixtures were produced in a laboratory rubber mixer with a capacity of camera 2 DM3in two-stage mode. The modifier was introduced in the second stage of mixing. The composition of the rubber mixtures is given in table 1.

Properties of rubber mixtures and vulcanizates are shown in table 2 (the content of the modifier of 1.00 wt.h.).

As can be seen from table 2, the rubber containing 1.00 wt.h. suggested modifiers, superior rubber with modifier 300% 0.4-1.2 MPa, the tear resistance 4-7 kN/m and the strength of rubber cord 23 science and technology committees on 18-29 N. On other indicators of rubber with prototype modifier or equivalent, or superior to rubber with the modifier of the prototype.

Thus, the tests indicate a greater efficiency of the proposed modifiers compared with modifier prototype - serial hexoloy KPI.


Claims

1. Modifier for rubber compounds based on unsaturated rubbers, including 1,4-bis(trichloromethyl)benzene and additives target, wherein the target contains additives solid petroleum waxes, chlorinated polyvinyl chloride and trialkylphosphine or dialkylammonium, or triarylphosphite, or their mixture in the following ratio, wt. %:
1,4-Bis(trichloromethyl) benzene - 87,0 - 94,0
Solid petroleum waxes - 0,8 - 3,7
Chlorinated polyvinyl chloride - 5,0 - 9,0
Trialkylphosphine or dialkylammonium, or triarylphosphite, or a mixture of 0.2 - 0.3
2. Modifier for rubber compounds based on unsaturated rubbers, including 1,4-bis(trichloromethyl)benzene and additives target, wherein the target additives within 55,1 71.2 percent, trialkylphosphine or dialkylammonium, or triarylphosphite, or their mixture and surfactant ionic or nonionic type in the following ratio, wt. %:
1,4-Bis(trichloromethyl)benzene - 87,0 - 94,0
Surface-active agent of the ionic or nonionic type - 0,2 - 0,4
Chlorinated paraffin waxes with carbon chain length From18-C36and mass fraction of chlorine within 55,1 71.2 percent - 5,6 - 12,6
Trialkylphosphates, or dialkylammonium, or triarylphosphite, or a mixture - 0,2 - 0,4
3. A method of obtaining a modifier on p. 1 by mixing the components in the melt, followed by cooling the composition in a thin film, characterized in that the melt of 1,4-bis(trichloromethyl)benzene with mass fractions of the basic substance within 95,0-99.5% pure, containing of 0.21 and 0.35 wt. % trialkylphosphine, or dialkyldithiophosphate, or triarylphosphine, or mixtures thereof, at 112-125oTo dissolve a 4.1-8.0 wt. % polyvinyl chloride, carry out its chlorination with gaseous chlorine at 115-125oC initiate azobisisobutyronitrile, taken in an amount of 0.01-0.1% by weight of the mixture, to a temperature dropping point of the reaction mass within 95-105oWith subsequent Stripping acid gas at 110-120oWith eating the ratio of the components, wt. %:
1,4-Bis(trichloromethyl)benzene - 87,0 - 94,0
Solid petroleum waxes - 0,8 - 3,7
Chlorinated polyvinyl chloride - 5,0 - 9,0
Trialkylphosphates, or dialkylammonium, or triarylphosphite, or a mixture of 0.2 - 0.3
4. A method of obtaining a modifier on p. 2 by mixing the components in the melt, followed by cooling in a thin film, characterized in that the melt of 1,4-bis(trichloromethyl)benzene with mass fractions of the basic substance within 95,0-99.5% pure, containing 0.2-0.5 wt. % trialkylphosphine, or dialkyldithiophosphate, or triarylphosphine, or mixtures thereof, dissolved 2.0 to 5.1 wt. % solid oil paraffins with carbon chain length From18-C36and implement them chlorination with gaseous chlorine at 112-125oC initiate azobisisobutyronitrile, taken in an amount of 0.02-0.1 percent by weight of the mixture, to a temperature dropping mixture within 94-105oWith and receiving chlorinated paraffin waxes with a mass fraction of chlorine within 55,1 71.2 percent, followed by Stripping acid gas at 110-120oS, after which the mixture is dissolved at 110-120oWith a surface-active agent of the ionic or nonionic type and get the modifier in the following ratio, wt. %:
1,4-Bis(trichloromethyl)be solid paraffins with carbon chain length From18-C36and mass fraction of chlorine within 55,1 71.2 percent - 5,6 - 12,6
Trialkylphosphates, or dialkylammonium, or triarylphosphite, or a mixture of 0.2 - 0.4

 

Same patents:

The invention relates to a process of manufacturing rubber ebonite products can be used in aviation, engineering, agriculture, medicine and everyday life

The invention relates to the rubber industry, and is intended for installation between parts and sub-assemblies of internal combustion engines

The invention relates to curing agents for diene rubbers, vulcanizing grey, and can be used in tire and rubber industry

The invention relates to woodworking industry and can be used in the manufacture of finished fiberboard, and finished wood-fibre products
The invention relates to a solid composition having a bending strength of at least 0.5 N/mm2including solid particles and hydrocarbon binder containing the calculation on all the binder (i) 15 to 95 wt

The invention relates to methods for powdery bulk polymeric materials and can be used in construction as a component of dry mortars, bonding agents, primers and as a modifying additive in mortars

The invention relates to woodworking and can be preferably used in technological processes of production of chipboard for furniture and construction

The invention relates to the field of road construction materials and can be used as a putty for pavement repair

The invention relates to the production of cationic surfactants for the preparation of cationic bitumen emulsions

The invention relates to compositions based on suspension of polyvinyl chloride for the production of window and door profiles to be used when carrying out construction and repair work

Polymer composition // 2211229
The invention relates to the creation of the plasticized compositions based on suspension of polyvinyl chloride, which can be used to obtain a film materials

The invention relates to polyvinyl chloride compositions using dye substances for the manufacture of materials, mainly construction, and can be used for the production of moldings of specialized products for Windows and doors in the construction and repair of buildings

The invention relates to the finishing of artificial leather in order to give her the technological and hygienic properties by increasing the permeability and can be used as a finishing layer to interior parts of the vehicle, as well as a noise-absorbing layer in the premises of the special purpose

The invention relates to the production technology of artificial leather-based polyvinyl chloride polymer resins and may find application in the manufacture of material to cover the floors of vehicles (cars and trucks, agricultural vehicles, passenger vehicles)

The invention relates to the field of polymer chemistry, in particular to a method for obtaining graft copolymer of (meth)acrylic monomer in the copolymer of butadiene with styrene modifier for polyvinyl chloride (PVC), and can be used to create composite materials based on plasticized and unplasticized PVC, recyclable, for example, profiles, films, sheets, etc

The invention relates to plasticized and stabilized compositions based on suspension of polyvinyl chloride (PVC) and can be used for producing the adhesive film without adhesive

The invention relates to the production of compositions based on thermoplastic resins

The invention relates to polymeric compositions based on polyvinyl chloride to obtain a film materials and artificial leather
Up!