WO2008048132A1 - Procédé pour fabriquer une matière hautement dispersée, prioritairement pour la fabrication de revêtements hydro-isolants, antibruits et de sports - Google Patents

Procédé pour fabriquer une matière hautement dispersée, prioritairement pour la fabrication de revêtements hydro-isolants, antibruits et de sports Download PDF

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Publication number
WO2008048132A1
WO2008048132A1 PCT/RU2006/000537 RU2006000537W WO2008048132A1 WO 2008048132 A1 WO2008048132 A1 WO 2008048132A1 RU 2006000537 W RU2006000537 W RU 2006000537W WO 2008048132 A1 WO2008048132 A1 WO 2008048132A1
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WO
WIPO (PCT)
Prior art keywords
rubber
crumb
thermoplastic
mixture
processing
Prior art date
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PCT/RU2006/000537
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English (en)
Russian (ru)
Inventor
Vadim Gennadievich Nikol'skii
Irina Aleksandrovna Krasotkina
Tatiana Vladimirovna Dudareva
Original Assignee
Institut Himicheskoy Fiziki Im. N.N.Semenova Rossiyskoy Akademii Nauk
Obschestvo S Ogranichennoy Otvetstvennostju 'noviy Kauchuk'
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
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Application filed by Institut Himicheskoy Fiziki Im. N.N.Semenova Rossiyskoy Akademii Nauk, Obschestvo S Ogranichennoy Otvetstvennostju 'noviy Kauchuk' filed Critical Institut Himicheskoy Fiziki Im. N.N.Semenova Rossiyskoy Akademii Nauk
Priority to PCT/RU2006/000537 priority Critical patent/WO2008048132A1/fr
Publication of WO2008048132A1 publication Critical patent/WO2008048132A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L19/00—Compositions of rubbers not provided for in groups C08L7/00 - C08L17/00
    • C08L19/003—Precrosslinked rubber; Scrap rubber; Used vulcanised rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds

Definitions

  • the invention relates to the field of processing of polymeric materials, in particular to methods for producing compositions of macromolecular substances, and can be used to obtain highly dispersed material based on rubber crumb and thermoplastics, suitable for the manufacture of various materials, including waterproofing, soundproofing and sports coatings.
  • the composition contains components in the following ratio, wt.%: Styrene-butadiene rubber 5-15, low-density polyethylene 5-20, petroleum bitumen 8-30, carbon black 10-20, mineral filler 3-15, rubber flour 10- 45, petroleum softener PH-6PI 5-15, stearic acid 0-5, resin 0-10, paraffin 0-4. (Patent of the Russian Federation N ° 2 142969C1, published on December 20, 1999.). The method of preparation of the composition allows to simplify the technological scheme of obtaining a waterproofing material without improving the technical properties of insulating materials.
  • this method provides a composition in a batch mode, which reduces its effectiveness.
  • the preparation of the composition is carried out at very low shear stresses, which negatively affects the uniformity of mixing and, therefore, the physico-mechanical properties of waterproofing materials obtained on the basis of this composition.
  • the particle size of rubber flour is not specified, but it is well known that the particle size of rubber has a decisive influence on the properties of the composition.
  • the composition contains rubber crumb with particle size predominantly up to 1.0 mm and a polyolefin or a mixture of polyolefins with the following content of components per 10 parts per hour, the main composition: rubber crumb - 40-90 parts by mass, polyolefin (mixture of polyolefins) 10-part.
  • the preparation of the composition is carried out by mixing the components at a temperature in the range from (Tm + 5) ° C to (Tm + 55) ° C, where Tm is the melting temperature of the thermoplastic. Then, the resulting composition is molded to obtain a roll stock of material for protective coatings. (Patent of the Russian Federation N ° 2 129133C1, published on 04/20/1999.).
  • the method allows for the possibility of introducing into the composition of the material the most massive polymer waste: secondary polyolefins and products of processing depreciated tires and to obtain materials with sufficiently high operational or consumer properties.
  • this method of obtaining the composition is carried out by mechanical mixing of the components of the composition at very low shear stresses in a paddle mixer at a temperature when the polyolefin is in a melt state and the rubber particles freely move in the mass of the molten polyolefin and do not change in structure.
  • the consequence of this is the insufficient adhesion strength of the rubber and polyolefin particles due to the small contact area, which negatively affects the physicomechanical characteristics of the coatings obtained on the basis of this composition: tensile strength is only 3.4 MPa, and elongation at break is 90% .
  • thermoplastic composition comprising a mixture of 10-90 parts by weight milled vulcanized rubber with a particle size of less than 1.5 mm and 90-10 wt.h. one or more polyolefins and at least 0.5 parts by weight an alpha olefin copolymer, wherein said alpha olefin copolymer is present in an amount sufficient to increase the ultimate tensile elongation of the pressed composition by 25%.
  • US patent 6031009 published 02.29.2000.
  • the preparation of the composition is carried out using a device that provides sufficiently effective mixing of the components at the required temperature, for example using a Banbury mixer or extruder.
  • the mixing of the components of this composition is carried out at sufficiently low shear stresses, the contact area of the polyolefin with rubber particles does not increase, since the surface of the rubber particles does not change during mixing in the molten polyolefin.
  • An increase in the ultimate elongation at break of the pressed composition by 25% is due to the introduction of the third component, the alpha olefin copolymer, which has an affinity for both rubber and polyolefins, into the specified composition.
  • an increase of this indicator by 25% is not very significant.
  • the closest to the proposed method is a method of producing a rubber mixture to obtain a waterproofing material.
  • waste rubber vulcanizates and a primary polyolefin selected from the group are used: polyethylene, polypropylene, 1,4-cis-polybutadiene, 1,4-cis-polyisoprene.
  • the primary polyolefin and waste rubber vulcanizates are taken in a quantitative ratio (20-10) :( 80-90) wt.%, Respectively, and the process of obtaining the mixture is carried out by grinding it into powder in an extrusion apparatus under the influence of compression, shear and temperature. (Patent of the Russian Federation N ° 2 123935C1, published on December 27, 1998.).
  • the prepared rubber mixture is formed by calendering.
  • the disadvantages of this method include low strength (not more than 5 MPa), as well as low deformability (not more than 200%) of the materials obtained by molding mixtures. The most likely reason for this is too low shear stress in the extrusion apparatus used.
  • the production of high-strength materials based on mixtures of the indicated type with a polyolefin content of more than 10-15 mass% cannot, in principle, be carried out by single-stage shear grinding. Grinding high-strength rubber in a polyolefin medium at low shear stresses leads to simple crushing of rubber crumb without the formation of an active particle surface. As a result, the resulting mixtures are characterized by insufficient uniformity in particle size, weak adhesion at smooth contact boundaries, which leads to insufficient high physical, mechanical and operational characteristics of the final material.
  • the objective of the invention is to develop a method for producing highly dispersed material based on rubber crumb and thermoplastic in a wide range of component ratios with a high degree of homogeneity of the mixture, suitable for producing mainly waterproofing, soundproofing and sports coatings with high physical, mechanical and operational characteristics.
  • the problem is solved by the method of obtaining highly dispersed material based on rubber crumb and thermoplastics, including the processing of rubber crumb with thermoplastics in a rotary type device for high-temperature shear grinding during heating by simultaneously applying shear stress and pressure to the processed material. Processing is carried out in two stages. First, at the first stage, rubber crumb or a mixture of rubber crumb is processed with at least one thermoplastic with a ratio of rubber lining: thermal layer (mixture of thermoplastics) (mass%) equal to (99.5-90.0) :( 0.5 -10.0), under conditions providing high-temperature shear grinding of rubber crumb.
  • the processing of the product obtained at the first stage is carried out in the presence of a thermoplastic or a mixture of thermoplastics with the ratio obtained at the first stage of the product-thermoplast (mixture of thermoplastics) (mass%), equal to (2-90): (98-10), conditions providing high-temperature shear grinding of thermoplastics (mixture of thermoplastics).
  • the particle size of the processed rubber crumb and / or thermoplastic, in at least one dimension can be no more than 10 mm.
  • processing in the first stage can be carried out with a shear stress of 10-70 N / mm, and in the second stage with a shear stress of 0.5-25 N / mm 2 .
  • rubber crumb a crumb of rubber from waste rubber products based on isoprene, butadiene, butadiene-styrene, butadiene-nitrile, natural, carboxylate, silicone, polyisobutylene, polychloroprene rubber, as well as mixtures thereof.
  • rubber crumb of tire rubber based on isoprene, butadiene-styrene or natural rubber, and also mixtures thereof, including crumb rubber from worn tires reinforced with synthetic cord can be used as rubber crumb, and the processing at the first stage can be carried out at a temperature of 140-190 0 C.
  • crumb from rubber waste based on ethylene propylene diene rubber can be used as rubber crumb, and at the same time, processing at the first stage can be carried out at a temperature of 180-250 0 C.
  • thermoplastic in the method, low pressure polyethylene, high pressure polyethylene, polypropylene, divinyl styrene copolymer, polyvinyl chloride, polystyrene, ethylene vinyl acetate copolymer, mixtures or wastes thereof can be used, and at the same time, processing in the second stage can be carried out at a temperature 70-150 0 C.
  • thermoplastics in the form of granules, crushed chips, chopped film, tangled fibers can be used.
  • a rotary type device for high-temperature shear grinding a device can be used according to RF Patent JNs 2173634 or RF Patent JC ° 2173635 or RF Patent JVb 2198788, as well as some types of twin-screw extruders.
  • the processing of rubber crumb or a mixture of rubber crumb with at least one thermoplastic in the first and / or second stage can be carried out in the presence of target additives, and mineral filler, plasticizer, dye and other additives can be used as target additives.
  • a rotary type device for high temperature shear grinding (Engineering Engineering. 1998. JVa 4 (18), c.c.94-101) implements the process of grinding rubber and other polymeric materials in a continuous mode.
  • the device contains a grinding unit with a working body grinding
  • the rotor which is installed in relation to the camera body of the node used grinding with an annular gap.
  • the processed material is subjected to compression, deformation by shear and heating in the indicated annular gap.
  • the values of pressure, shear stress and temperature reach optimal critical values, multiple cracking of the material occurs, its destruction and transformation into a finely divided powder.
  • the proposed method for producing highly dispersed material based on rubber crumb and thermoplastics is carried out in two stages as follows.
  • rubber crumb or a mixture of rubber crumb and thermoplastic (mixture of thermoplastics) in the ratio of rubber cover: thermoplastic (mixture of thermoplastics) (mass%) equal to (99.5-90.0) is poured into the loading hole of a device for high-temperature shear grinding; : (0.5-10.0).
  • the components of the mixture can be poured at the same time using a two-armed dosimeter, or a coarse heterogeneous mixture can be prepared in advance in any mixer for dry mixing.
  • the material that is poured into the loading hole is subjected to shear stress and pressure at the same time, as a result of which the material is heated, and the material is processed under conditions that provide high-temperature shear grinding of crumb rubber. Then, the product obtained at the first stage and thermoplastic (or a mixture of thermoplastics) in the ratio (2-90) :( 98-10) (mass%) simultaneously and uniformly using a two-strand dosing device (or by preparing a rough heterogeneous mixture in advance in a dry mixing apparatus) fall asleep in the loading hole of the device for high-temperature shear grinding.
  • thermoplastics thermoplastics mixture
  • the result is a highly dispersed composite material, characterized by a high degree of homogeneity of the mixture, and the powder particles of this material have a highly developed surface.
  • the processing of rubber crumb or a mixture of rubber crumb with at least one thermoplastic can be carried out in the presence of target additives, which are used as mineral filler, plasticizer, dye.
  • target additives which are used as mineral filler, plasticizer, dye.
  • Such additives can be introduced into the loading opening of the device for high-temperature shear grinding, either using an additional metering device, or a mixture of this additive with any component of the mixture is preliminarily prepared.
  • thermoplastics mixture of thermoplastics loaded in the second stage
  • a highly dispersed composite material is formed (maximum particle size less than 300 microns), characterized by a high NOSTA mixture.
  • Each powder particle of the obtained highly dispersed mixed material is an agglomerate, consisting of very fine fragments of rubber and thermoplastic well mixed with each other (mixture of thermoplastics). Moreover, such a particle is characterized by a fairly strong contact interaction between these fragments.
  • the resulting highly dispersed mixed material is easily processed to obtain any film, roll materials or products based on it. So, for example, to obtain waterproofing, soundproofing and sports coatings, the obtained finely dispersed composite material is subjected to molding by pressing or followed by slow cooling under pressure, or by calendering on a cascade of several calendars with a gradual decrease in temperature from 150 to 80 0 C, or a finely dispersed mixed material is dissolved in hot bitumen, followed by molding. Coatings obtained on the basis of a highly dispersed mixed material have high physical, mechanical and operational characteristics.
  • Example 1 The following are examples that illustrate but do not exhaust the proposed method for producing highly dispersed materials based on crumb rubber and thermoplastics.
  • Example 1 The following are examples that illustrate but do not exhaust the proposed method for producing highly dispersed materials based on crumb rubber and thermoplastics.
  • the specified mixture is processed at a shear stress of 37 N / mm 2 . Under these conditions, the processed material is heated and crushed at a temperature of 170 ° C.
  • LDPE thermoplastic PTP 2g / 10min is introduced into the product obtained at the first stage in the ratio of the obtained product / thermoplastic 20/80 (mass%) and processed in a device for high-temperature shear grinding at a shear stress of 10 N / mm
  • the components of the processed material are heated, mixed and co-milled at a temperature of 95 ° C.
  • a highly dispersed mixed material based on crumb rubber and LDPE with a temperature of 34 ° C is poured out of the discharge opening of the specified device, which after sieving on a sieve with a mesh size of 0.3 mm gives residue less than 2 mass%.
  • the obtained highly dispersed mixed composite material is characterized by a high homogeneity of the components, and the powder particles of this material have a highly developed surface. Then the obtained material is subjected to pressing at a temperature of 150 0 C and a pressure of 10 MPa followed by slow cooling under pressure.
  • the molded material has the following physical and mechanical characteristics: tensile strength of 8.2 MPa and elongation of 300%. Examples 2-15.
  • the preparation of finely dispersed material is carried out analogously to example 1. Pressing the obtained material is also carried out under the conditions of example 1.
  • the name of the processed material, the ratio of rubber crumb and thermoplastic, the parameters of the process in the first and second stages (shear stress, temperature), as well as physico-mechanical characteristics of the pressed fine material are given in the table.
  • the proposed method for producing a highly dispersed composite material based on crumb rubber and thermoplastic allows to obtain a mixed material in a wide range of component ratios with a high degree of mixture uniformity.
  • the finely dispersed material obtained by the proposed method makes it possible to produce high-quality coatings on its basis, mainly waterproofing, soundproofing and sports coatings, with high physical, mechanical and other operational characteristics.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un procédé de transformation de matières polymères et peut s'utiliser pour obtenir une matière hautement dispersée à base de miettes de caoutchouc et de thermoplastes qui convient à la fabrication de revêtements, de préférence de revêtements hydro-isolants, anti-bruits et de sports. Le procédé pour fabriquer une matière hautement dispersée, prioritairement pour la fabrication de revêtements hydro-isolants, anti-bruits et de sports comprend la transformation des miettes de caoutchouc avec des thermoplastes dans un dispositif de type rotor à des fins d'un broyage par cisaillement haute température pendant le réchauffement grâce à une action simultanée sur le matériau traiter par pression et par cisaillement. La transformation s'effectue en deux stades. Au premier stade, les miettes de caoutchouc ou le mélange de miettes de caoutchouc avec au moins un thermoplaste possédant le rapport entre les miettes de caoutchouc et le thermoplaste (le mélange de thermoplastes) (en % en masse) de 99,5-90,0 : 0,5-10,0 est traité dans des conditions assurant un broyage par cisaillement haute température des miettes de caoutchouc. Au deuxième stade, la transformation du produit obtenu au premier stade s'effectue en présence d'un thermoplaste ou d'un mélange de thermoplastes avec le rapport suivant des produits obtenus au premier stade : thermoplaste (ou mélange de thermoplastes) (en % en masse) de 2-90 : 98-10, le tout étant traité dans des conditions assurant un broyage par cisaillement haute température du thermoplaste ou du mélange de thermoplastes. Le procédé permet d'obtenir un mélange hautement dispersé dans une vase gamme de rapports entre les composants miettes de caoutchouc : thermoplaste, avec un degré élevé d'homogénéité du mélange. Les revêtements obtenus sur la base du matériau hautement dispersé sont caractérisés par leurs caractéristiques d'exploitation physico-mécaniques et autres élevées.
PCT/RU2006/000537 2006-10-18 2006-10-18 Procédé pour fabriquer une matière hautement dispersée, prioritairement pour la fabrication de revêtements hydro-isolants, antibruits et de sports WO2008048132A1 (fr)

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PCT/RU2006/000537 WO2008048132A1 (fr) 2006-10-18 2006-10-18 Procédé pour fabriquer une matière hautement dispersée, prioritairement pour la fabrication de revêtements hydro-isolants, antibruits et de sports

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PCT/RU2006/000537 WO2008048132A1 (fr) 2006-10-18 2006-10-18 Procédé pour fabriquer une matière hautement dispersée, prioritairement pour la fabrication de revêtements hydro-isolants, antibruits et de sports

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3689935A1 (fr) 2019-01-30 2020-08-05 Politechnika Gdanska Composite thermoplastique polyuréthane-caoutchouc et procédé permettant d'obtenir un composite thermoplastique polyuréthane-caoutchouc
RU2736088C1 (ru) * 2020-05-21 2020-11-11 Юрий Николаевич Дубов Гидроизоляционное покрытие

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1178158A (en) * 1966-04-14 1970-01-21 Rexall Drug Chemical Process for the Production of Polymer Powder
SU1434663A1 (ru) * 1983-06-22 1990-09-15 Всесоюзный Научно-Исследовательский Институт "Композит" Научно-Производственного Объединения "Норпласт" Способ измельчени полимерного материала
RU2123935C1 (ru) * 1997-04-09 1998-12-27 Минираис Марванович Усманов Способ получения безосновного гидроизоляционного материала
RU2173634C1 (ru) * 2000-08-23 2001-09-20 Балыбердин Владимир Николаевич Способ получения порошка из полимерного материала и устройство для его осуществления (варианты)

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1178158A (en) * 1966-04-14 1970-01-21 Rexall Drug Chemical Process for the Production of Polymer Powder
SU1434663A1 (ru) * 1983-06-22 1990-09-15 Всесоюзный Научно-Исследовательский Институт "Композит" Научно-Производственного Объединения "Норпласт" Способ измельчени полимерного материала
RU2123935C1 (ru) * 1997-04-09 1998-12-27 Минираис Марванович Усманов Способ получения безосновного гидроизоляционного материала
RU2173634C1 (ru) * 2000-08-23 2001-09-20 Балыбердин Владимир Николаевич Способ получения порошка из полимерного материала и устройство для его осуществления (варианты)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3689935A1 (fr) 2019-01-30 2020-08-05 Politechnika Gdanska Composite thermoplastique polyuréthane-caoutchouc et procédé permettant d'obtenir un composite thermoplastique polyuréthane-caoutchouc
RU2736088C1 (ru) * 2020-05-21 2020-11-11 Юрий Николаевич Дубов Гидроизоляционное покрытие
WO2021235975A1 (fr) * 2020-05-21 2021-11-25 Юрий Николаевич ДУБОВ Revêtement d'isolation hydraulique

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