CS252993B1 - A method of preparing a sole composition - Google Patents

Abstract

The method of preparation of the sole mixture, in which the segregation of its components does not occur, so that in the first phase, the batch is prepared by homogenizing 40 to 65% of the mass. block copolymer styrene-butadiene-styrene, 15 to 35 wt.% inorganic fillers, 5 to 15 wt.% paraffinic and/or naltenic oil, 0.2 to 0.6 wt.% χ-aminopropyltriethoxysilane, 0.5 to 0.8 wt.% antioxidant and accounts for up to 25% of the mass. rubber regenerated or up to 20% by mass. of rubber crumb, related to the total amount of beech, in a high-pressure kneading machine at a temperature of 380 to 460 °K for 18 to 28 minutes, and then the beech is calendered at a temperature of 355 to 390° K for 2 to 10 minutes and granulated, in the second phase 20 to 40% by mass is homogenized. of styrene-butadiene-styrene copolymer, 8 to 15 wt.% paraffinic and/or naphthenic oil, 0.01 to 5 wt.% pigments, 0.1 to 2 wt.% of antioxidant, 8 to 20 wt.% polystyrene, 0.5 to 3 wt.% ethylene vinyl acetate copolymer, with a vinyl acetate content of 10 to 30% by weight, based on the total amount of the mixture, in a drum mixer for 5 to 10 minutes at a temperature of 293 to 308 °K or in a fluid mixer for 0.5 to 1.5 minutes at a temperature of 313 to 328 degrees K.

Description

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BACKGROUND OF THE INVENTION The present invention relates to a process for the preparation of a suture composition consisting of styrene-butadiene-styrene block copolymers, oil, polystyrene, ethylene-vinyl acetate copolymer, pigments, antioxidants, lubricants, and norganic fillers and optionally rubber or rubber crumbs, mixing and kneading devices. Nowadays, in order to achieve good properties of the shoe parts prepared by the technology of injection molding or intrusion of the molten mixture into the mold cavity from a mixture based on styrene-butadiene-styrene block copolymers, it is necessary to provide a high degree of homogeneity and dispersion of all components in the matrix of styrene-block copolymers. buta-diene-styrene. In practice, high concentrations of one or more additives, such as, for example, carbon black, bent pigment and the like, are used in the preparation of such sublingual compositions. It is known to prepare a sole material based on a physical mixture of polyvinyl chloride and a powdered butadiene acrylonitrile elastomer based on a two-stage homogenization of the mixture in a mixer, characterized in that it is initially dispensed into a 353-368 K-heated environment. zinc oxide polyvinyl chloride thermoplastic, into which the softener and stabilizer are successively mixed until a 40 to 60% by weight blend is formed. of the total amount of butadiene-acrylonitrile elastomer. The mixture is stirred until the temperature rises to 388-398 ° K, then the mixture is passed into a cold mixing environment in which 313-318 ° K is cooled, the remaining 40-60% by weight is added. the butadiene-acrylonitrile elastomer together with the calcium carbonate, the entire contents are stirred in a cold environment until a temperature of 301-305 ° is reached to form the final lumpy mixture. Another known multistage process for the preparation of a subcutaneous polyvinyl chloride based material is that the premix of acrylonitrile butadiene styrene terpolymer is prepared by separating the first phase with acrylonitrile butadiene ether and di-octyl phthalate and homogenizes in the second phase after cooling the premix with a dose of polyvinyl chloride and additives, especially a scavenger. It is also known to produce a styrene-butadiene-styrene block copolymer material comprising from 5 to 30% by weight. filler particles in the form of spherical bodies having a diameter of 0.2 to 1.7 mm from butadiene styrene elastomer vulcanizates or from 10 to 53 centres. wt. The preparation is carried out by homogenizing the components on the homogenization lines. A disadvantage of this preparation is the relatively low degree of dispersion of inorganic fillers in the copolymer matrix, which is achieved by one or two-screw extrusion or injection molding machines currently used. With a higher content of inorganic fillers with high oil adsorption, it increases the likelihood of segregation of the components of the composition during storage, transport and, in particular, in the hoppers of processing plants. Also disadvantageous is the construction of the machines currently in use, which guarantee the high shear stress required for the agglomeration of the filler particles to be broken down and the uniform dispersion in the polymeric matrix of the block copolymers of styrene-butadiene-styrene in a relatively short residence time in the injection molding or extruding machines. thereby also affecting the subsequent physico-mechanical properties of the sublingual composition.

The above-mentioned drawbacks are overcome by the process of the invention, which is characterized in that in the first phase, the pumped product is prepared by homogenisation of 40 to 65% by weight. styrene-butadiene-styrene block copolymer, 15 to 35 pairs. wt. % of inorganic fillers, 5 to 15 wt. % paraffinic and / or naphthenic oil, 0.2 to 0.6 wt. % amine propyl trioxysilane, 0.5 to 0.8 wt. up to 25% by weight of antioxidant; % rubber re-generation or up to 20 wt. gumdrates, referring to the total amount of bake, in a high-pressure kneader at 380 to 460 ° K for 18 to 28 minutes onwards, calenders at 355 to 390 ° C for 2 to 10 minutes and granulated, in the second phase homogenized 20 to 40 wt. % of the so prepared bw with 38 to 55 wt. a styrene-butadiene-styrene block copolymer or styrene-butadiene-styrene block copolymer blend, 8 to 15 wt. % paraffinic and / or naphthenic oil, 0.01 to 5 wt. % pigments, 0.1 to 2 wt. % antioxidant, 8 to 20 wt. % polystyrene, 0.5 to 3 wt. e-ethylene vinyl acetate copolymer, with a vinyl acetate content of 10 to 30% by weight; referring to the total amount of the mixture, in a tumbler mixer for 5 to 10 minutes at 293 to 308 ° C or in a fluid mixer for 0.5 to 1.5 minutes at 313 to 328 ° K.

The technical effect of the invention is to increase the degree of dispersion of the norganic fillers in the copolymer of styrene-butadiene-styrene. The segregation of the components of the mixture is reduced, the shear stress of the mixture is increased, and hence the overall homogeneity. At the same time, the average energy intensity of the preparation is reduced while maintaining the utility properties of the sole composition.

The preparation methods of the invention will be more fully understood by way of example, in which all amounts of the components are given in percentages by weight. Example 1

A Banbury-Bridge kneader with a working chamber content of 0.160 m3 heated to 403 ° K was charged with a gradual 63% styrene-butacliene-styrene block copolymer (sty: bu 40: 60, containing 25% naphthenic oil], 30% hydrated silica, 6% naphthenic oil, 0.3% γ-aminopropyltriethoxysilane and 0.7% 2-mercaptobenzimidazole. on the control sensor to 433 ° K, after reaching this temperature, the carbon discharged to the 365 ° K heated twin cylinder from which it was granulated after 4 minutes of mixing and wrapping. % was added to the drum mixer with a working chamber content of 0.150 m 3, in which the mixture was pre-prepared and mixed by homogenizing 46% block copolymer styrene-butadiene-styrene (30% styrene content), 10.9% polystyrene, 2.5% copolymer e thylene vinyl acetate (18% vinylacetate), 13.8% naphthenic oil, 1% ferric oxide, 0.3% dllauryl thiodipropionate and 0.5% stearin. The mixture was homogenized at 300 ° K for 6 minutes and then the sole mixture was subjected to further processing into injection or extrusion machines. Example 2

A Banbury Bridge kneader of 0.160 m 3 working chamber heated to 393 ° K was charged with a gradual 45% styrene-butadiene-styrene block copolymer (ratio: 40: 60 to 25% naphthenic oil), 20% rubber hydrate, 25% silicon dioxide hydrate, 9% paraffinic oily, 0.4% ω-amino-propyltriethoxysilane, and 0.6%. 2-mercaptobenzimidazole. The mixture was homogenized for 25 minutes while the temperature of the homogenized mixture rose to 443 ° K. Upon reaching this temperature, the mixture was discharged to a twin cylinder, heated to 378 ° K, where it was calendered for 7 minutes, and after o-banding the mixture was granulated. The granulated pellet prepared in this way was fed at a rate of 30% to a fluid mixer with a working chamber content of 0.160 m 3, in which a mixture was prepared in the form of homogenization of β 30.5% of a styrene-buta-diene-styrene block copolymer (with a styrene content of 40%). ), 10.5per. styrene-butadiene-styrene block copolymer (30% styrene content), 9.5% paraffin oil, 3% zinc oxide, 0.5% tin oxide, 0.2% phthalocyanate pigment, 15% polystyrene and 0% , 8% calcium stearate. The mixture was homogenized at 335 ° C for 1.5 minutes at 750 rpm. After the end temperature of the mixture was 434 ° K, the mixture was discharged and the resulting dry-blend outsole was subjected to further processing into injection or extrusion machines. Example 3

A Banbury-Bridge huetccie machine with a working chamber content of 0.160 m 3 heated to 403 JK was charged with a sequential 50% styrene-buta-diene-styrene block copolymer (ratio: 40: 60, with a content of 25% naphthenic oil), 20.7% hydrated silica, 4.3% floated calcium carbonate, 15% rubber grade with a particle size of less than 1 mm, 9% naphthenic oil, 0.25% 2-mercaptobenzene of imidazole, 0.45% of a technical mixture of phenylethylphenols and 0.3% of ω-aminopropyltriethoxysilane. The mixture was homogenized for a minimum of 20 minutes while the temperature of the homogenised mixture rose to 433 ° K. Upon reaching this temperature, the mixture was discharged to a temperature of 365 ° K, which, after stirring for 9 minutes, was stripped into a granulating machine. The granule prepared in this way was added to a drum mixer at 35% in which a mixture was prepared beforehand by homogenizing a 35% styrene-butadiene-styrene block copolymer (30% styrene content), 14% polystyrene, 1.5 % copolymer of stylene vinyl acetate (25% vinyl acetate content), 12.5% naphthenic oil, 0.3% phthalocyanine pigment, 0.7% stearin, 0.6% dilauryl thiodipropionate and 0.4 calcium stearate. The mixture was homogenized at a temperature of 295 ° K for 5 minutes and then the outsole was further processed into injection or extrusion machines.

Claims (1)

SUBJECT Process for preparing a sole mixture consisting of block copolymers of styrene-butadiene-styrene, oils, polystyrene, ethylene-vinyl acetate copolymer, pigments, antioxidants, lubricants, inorganic fillers and, optionally, a rubber regenerate or rubber pulp, characterized in that it is prepared in a first stage. 40 to 65 wt. styrene-butadiene-styrene block copolymer, 15 to 35 wt. % of inorganic fillers, 5 to 15 wt. paraffinic and / or naphthenic oil, 0.2 to 0.6 pens. wt. χ-aminopropyltriethoxysilane, 0.5 to 0.8 wt. % of antioxidant and up to 25 wt. % of rubber regenerate or up to 20 wt. rubber crumb, based on the total amount of bull, in a high-pressure kneading machine at a temperature of 380 to 460 ° We claim: K for 18 to 28 minutes and datoj is calendered at 355 to 390 ° K for 2 to 10 minutes and granulated, in a second phase 20 to 40 wt. by weight of the thus prepared soda with 38 to 55 wt. % styrene-butadiene-styrene block copolymer or styrene-butadiene-styrene block copolymer blends, 8 to 15 wt. paraffinic and / or naphthenic oil, 0.01 to 5 pens. wt. 0.1 to 2 wt. % antioxidant, 8 to 20 wt. % polystyrene, 0.5 to 3 wt. % ethylene vinyl acetate copolymer, having a vinyl acetate content of 10 to 30 wt. based on the total amount of the mixture in a drum mixer for 5 to 10 minutes at 293 to 308 ° K or in a fluid mixer for 0.5 to 1.5 minutes at a temperature of 313 to 328 ° K. Severography, n. p. Race 7, Most Price 2,40 KCs