WO2002024795A1 - Elastomeres thermoplastiques et polymeres obtenus a partir de caoutchouc et de plastique recycles - Google Patents
Elastomeres thermoplastiques et polymeres obtenus a partir de caoutchouc et de plastique recycles Download PDFInfo
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- WO2002024795A1 WO2002024795A1 PCT/US2001/029600 US0129600W WO0224795A1 WO 2002024795 A1 WO2002024795 A1 WO 2002024795A1 US 0129600 W US0129600 W US 0129600W WO 0224795 A1 WO0224795 A1 WO 0224795A1
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- 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
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/16—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with inorganic material
-
- 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
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
-
- 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
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
-
- 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
- C08J2321/00—Characterised by the use of unspecified rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/22—Mixtures comprising a continuous polymer matrix in which are dispersed crosslinked particles of another polymer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Definitions
- the invention relates to the novel thermoplastic materials and impact-modified plastics produced by blending recycled rubber with thermoplastics.
- thermosetting polymers such as rubbers
- grinding is one method to recycle a thermoset.
- the ground rubber can be used alone or mixed with thermoplastics to achieve the desired properties, such as impact modification.
- scrap rubbers present self-sustaining fire hazards, and as rubbers such as tires burn, they release toxic compounds into the atmosphere. Rubber piles and dumps are also considered to be a breeding ground for disease-carrying pests.
- thermoplastic elastomers have grown dramatically because ofthe ability to recycle and process these materials using conventional thermoplastics processing equipment.
- the unique characteristics of thermoplastic elastomers make them an attractive alternative to conventional elastomers in a variety of markets, such as the automotive industry. Consequently, conversion of a conventional elastomer (thermoset) into a thermoplastic elastomer through blending with thermoplastics has the potential to introduce new market applications for scrap rubber.
- thermoplastic elastomers Materials ranging from impact-modified thermoplastics to thermoplastic elastomers (TPE) can be obtained from blends of recycled thermoset rubber with thermoplastic polymers by varying the ratio of components in the blend, or by changing the components themselves.
- the rubber component may include carbon black, or other fillers and additives, and it may be selected from among a variety of thermoset rubbers, both natural and synthetic.
- the thermoset rubber component can be obtained from a rubber material recycled accordmg to a variety of known techniques.
- the thermoplastic component can be virtually any suitable polymer, the properties of which can be advantageously modified by combination with a rubber. Polyolefins are among the more preferred thermoplastic components.
- the present invention focuses on developing TPE materials from polyolefins (e.g., polypropylene) and recycled ground rubber.
- the components, particularly the rubber component are subjected to phase compatibility treatments that are effective to improve the quality ofthe scrap rubber/plastic blends in response to the structural requirements of several potential applications.
- the effect of rubber particle size, melt flow index (MFI) for the thermoplastic component, and weight percent ofthe - constituent fractions are also factors that can contribute to the physical properties of the resultant blends.
- the melt flow index of the thermoplastic component is one particularly significant variable that influences the mechanical properties of the resultant blends.
- materials made according to the invention are recreational and athletic surface and flooring materials, industrial flooring and footpaths, anti-static computer mats, mounting pads and shock absorbers, membrane protection, airfield runways and roadway surfaces, shoe soles, carpet underlay, automotive floor mats, mud flaps and molded protection strips, automotive door and window seals, gaskets, landscaping materials, watering systems, pipes and hose materials, and flower pots.
- materials made according to the invention are recreational and athletic surface and flooring materials, industrial flooring and footpaths, anti-static computer mats, mounting pads and shock absorbers, membrane protection, airfield runways and roadway surfaces, shoe soles, carpet underlay, automotive floor mats, mud flaps and molded protection strips, automotive door and window seals, gaskets, landscaping materials, watering systems, pipes and hose materials, and flower pots.
- Figure 1 illustrates possible reactions that take place during reactive blending.
- Figure 2 is a graph illustrating the break tensile strength of recycled EPDM/PP blends.
- Figure 3 is a graph illustrating the break elongation of recycled EPDM/PP blends.
- Figure 4 is a graph illustrating the crystallinity of recycled EPDM/PP blends.
- Figure 5 is a graph illustrating the dynamic mechanical analysis of an EPDM/PP blend (50/50 wt. %).
- Figure 6 is a graph illustrating the influence of MFI on PP break tensile strength.
- Figure 7 is a graph illustrating the influence of MFI on PP break elongation.
- Figure 8 is a graph illustrating the influence of MFI of PP on degree of crystallinity.
- Figure 9 contains graphs illustrating the effect of wt.% rubber on tensile strength and ultimate elongation for surface treated ground EPDM - PP blends.
- Figure 10 contains graphs illustrating the effect of wt.% rubber on tensile strength and ultimate elongation for ground EPDM reactively blended with a radical initiator and blended with PP.
- Figure 11 contains graphs illustrating the effect of blending with high molecular weight PP on tensile strength and ultimate elongation for ground EPDM - PP blends.
- Figure 12 contains graphs illustrating the effect of wt.% rubber on tensile strength and ultimate elongation for ground SBR - phenolic modified PP blends.
- Figure 13 is a graph illustrating the effect of rubber particle size on breaking strain and breaking strength for EPDM - PP blends.
- Figure 14 contains graphs illustrating the effect of PP molecular weight on breaking strain and breaking strength for EPDM - PP blends.
- Figure 15 is a graph illustrating the effect of PP molecular weight on crystallinity for EPDM - PP blends.
- Figure 16 is a system diagram summarizing the influence of various factors on properties ofthe resulting blends. DETAILED DESCRIPTION OF THE INVENTION
- All publications and references cited herein are expressly incorporated herein by reference in their entirety.
- the invention provides novel thermoplastic elastomers and impact-modified thermoplastics as a result of a blend of a recycled thermoset rubber component with a thermoplastic polymer component. Apart from providing such new and useful materials with a variety of commercial applications, the invention helps contribute a solution to the environmental problems that can result from the disposal or attempted disposal of non- recycled rubbers by providing an effective way to recycle such materials.
- the invention provides a recycling technique for thermoset rubbers. In another aspect, it provides new materials that result from this recycling technique.
- thermoset rubbers are blended with thermoplastic polymers to yield thermoplastic elastomers (TPEs) and/or impact-modified thermoplastics.
- TPEs thermoplastic elastomers
- the thermoset rubber component can be used in the blend in an amount ranging from about 5 to 85 wt. % ofthe blend, and, more preferably, at about 10 to 80 wt. % ofthe blend.
- the thermoset rubber can be selected from among a variety of recycled thermoset rubber materials, including those having carbon black.
- Exemplary rubbers include natural rubber, styrene-butadiene rubber (SBR), ethylene-propylene-diene rubber (EPDM), ethylene propylene rubber (EPR), polychloropene, nitrile rubber, epi- chlorohydrin, fluoro-elastomer rubber, silicone rubber, butyl rubber, polyisoprene, and polybutadiene.
- Sources ofthe recycled rubber materials include a variety of materials such as tires, shoe soles, and roofing materials.
- Useful average particle sizes for the rubber component are in the range of about 500 microns or smaller. In one embodiment, the rubber component has a particle size in the range of about 40 to 500 microns.
- the thermoplastic component of the blend is present in the blend in an amount in the range of about 15 to 95 wt. % ofthe blend, and more preferably, at about 20 to 90 wt. % ofthe blend.
- the thermoplastic material preferably is, but need not be, a virgin thermoplastic.
- a variety of thermoplastic materials may be used according to the present invention, provided that they are compatible with recycled thermoset rubbers and that their properties and/or performance can be enhanced by the combination with such rubbers.
- thermoplastic materials include polyolefins, and polyolef ⁇ n-based compounds (including polyolefin-containing copolymers), polystyrenes and copolymers thereof, polyurethanes and copolymers thereof, polyesters and copolymers thereof, vinyl polymers and copolymers, polyamides and copolymers thereof.
- polyolefins particularly polypropylenes.
- the thermoplastic material has a melt flow index (MFI) in the range of about 0.45 to 20 g/10 minutes, and more preferably in the range of about 0.75 to 12 g/10 minutes.
- thermoplastics such as polypropylene
- Thermoplastics tend to be semi-crystalline materials while most rubbers are amorphous thermosets. Crystalline segments within the thermoplastic are resistant to intrusion of rubber segments. Crosslinking of the rubber makes it difficult for the thermoplastic to disperse during mixing. Therefore, compatiblizing techniques were found to be useful to obtain the desired physical properties.
- thermoset and thermoplastic components it is best to enhance the phase compatibility ofthe thermoset and thermoplastic components. This can be accomplished by reactive blending of the components or by surface treatment of the rubber component.
- Surface treatment ofthe rubber can be accomplished by dispersing the rubber particles in an aqueous solution together with an oxidizing agent.
- the rubber particles are added to an acetone solution (e.g., 10% acetone/90% water) and a quantity (e.g., about 1 to 20% by wt. of the rubber) of an oxidizing agent (e.g., potassium permanganate (KMn0 4 )) is added to the rubber suspension to oxidize the rubber surface.
- an oxidizing agent e.g., potassium permanganate (KMn0 4 )
- the by-product, MnO 2 is further oxidized for separation by 30% aqueous H 2 0 2 solution with 0.1% H 2 S0 4 dissolved into the H 2 O 2 solution.
- the rubber is then separated by filtration and washed with water until the filtrate is neutral.
- the treated rubber is then air dried. Following this process the rubber is blended with a thermoplastic.
- approximately 1 to 10% by wt. of a maleated polypropylene may be added to react with surface hydroxyl groups tp graft polypropylene to the rubber.
- oxidizing agents include hydrogen peroxide, osmium tetroxide, hydrogen peroxide urea complex, sodium percarbonate, sodium perchlorate, sodium perborate, potassium peroxymonosulfate, and a potassium permanganate/potassium periodate aqueous solution.
- Reactive blending involves blending the thermoplastic component with the rubber component and a free radical generating compound at a temperature at or above the activation or degradation temperature ofthe free radical generating compound.
- the free radical penetrating compound is a liquid
- the rubber and free radical generating compound are combined before blending the rubber with the thermoplastic component.
- the free radical generating compound may be added to the thermoplastic component concurrently with the rubber or it may be added after the addition ofthe rubber component to the thermoplastic component.
- the majority ofthe double bonds in the recycled EPDM are still available even though it is vulcanized.
- those double bonds can be utilized to graft polypropylene onto the rubber particle surface.
- This reaction leads .to better compatibilization between the polymer and rubber phases.
- the reactive blending with high rubber content may also promote crosslinking between rubber particles.
- Figure 1 shows the two possible reactions during a reactive blending procedure conducted at a temperature of about 200°C using t-butyl hydroperoxide with a half-life of 4.81 hrs at l75°C.
- the reactive blending process typically utilizes a free radical generating compound that is present at a range of about 0.5 to 5% by weight ofthe rubber component.
- the free radical generating compound may be combined with the rubber component before reactive blending with the thermoplastic material. This is particularly useful where the free radical generating compound is a liquid.
- the free radical generating compound and the rubber component can be combined at room temperature for a duration of about 1 minute to 1 hour.
- these two components can be combined at a variety of alternative temperatures, provided that the temperature is below the activation temperature for the free radical generating compound.
- the free radical generating compound is a peroxide.
- peroxide a variety of peroxides may be used for this reactive blending process provided that the peroxide is compatible with the rubber and the temperature range to be used. Further, the peroxides may be in either the solid or the liquid state. Exemplary peroxides include dibenzoyl peroxide; t-butyl hydroperoxide; and di-tert butyl peroxide.
- a variety of azo compounds can be used in the reactive blending step of the present invention, provided that the azo compounds are compatible with the rubber component and the temperature range to be used. Further, the azo compounds may be in either the solid or liquid state.
- Exemplary azo compounds include 1J '- azobis(cyclohexanecarbonitrile); azodicarbonamide; 2,2'-azobis(2,4- dimethylpentenenitrile); 2,2'-azobis(2-ethylpropanimidamide).2HCl ; 2,2'- azobis(isbutyronitrile); 2,2'-azobis(2-methyl-butanenitrile); 4,4'-azobis(4-cyanopentanoic acid); 2,2'-azobis(2-acetoxypropane); 2-(tert-butylazo)-4-methoxy-2,4- dimethylpentanenitrile; 2-(tert-butylazo)-2,4-dimethylpentanenitrile; 4-(tert-butylazo)-4- cyanopentanoic acid; 2-(tert-butylazo) isobutyronitrile; 2-(tert-butylazo)-2- methylbutanenitrile; 1 -(tert-a
- the azo compounds have the added benefit that they can be used to produce a foamed product in addition to promoting compatibilization.
- the rubber and thermoplastic components are blended at elevated temperatures (e.g., 180-220°C) to yield the desired recycled material.
- elevated temperatures e.g. 180-220°C
- the processing temperature should be at or above the activation or decomposition temperature ofthe free radical generating compound, and ultimately this temperature will vary depending on the thermoplastic component utilized.
- a variety of effective blending techniques can be used. By way of example, however, exemplary blending techniques are described below.
- thermoplastic e.g., polypropylene, maleated polypropylene, and phenolic-treated polypropylene
- PP polypropylene
- thermoset rubbers and thermoplastic polymers may be used, in accordance with the discussion above.
- recycled EPDM rubber at 80 mesh and 170 mesh particle sizes (available from Erickson Inc.) was blended with polypropylene having a melt flow index of 0.75 g/10 min and 12 g/10 min in a Rheocord System 40 (available from Haake Buechler). Prior to blending the EPDM was combined with t-butyl hydroperoxide at about 0.5-1.0 wt. % ofthe EPDM at room temperature for about 30 minutes.
- thermoplastic material After equilibrium temperature (200°C) and a rotor speed of 30 rpm was reached, the thermoplastic material was added.
- the EPDM rubber component was blended in after the plastic material was completely melted, as indicated by a stabilized torque reading, which was usually obtained after 4 to 5 minutes. Mixing ofthe blend was stopped after a specified time (two to ten minutes), or when the torque became constant.
- the rubber-plastic composite was removed and then ground using a laboratory mill (Thomas Wiley, model 4) with a 40-mesh screen. It is desirable to obtain particles that are not greater in size than 40 mesh in order to optimize the efficiency of compression molding. Further, it is desirable to avoid air gaps or voids between larger particle sizes to optimize mechanical properties.
- thermoplastic and rubber components can be conducted substantially concurrently with the incorporation ofthe free radical generating compound.
- An 80 mesh recycled EPDM rubber (available from Rouse) was blended with a polypropylene (available from Fina) having a number average molecular weight (M N ) of 84 and 40 in a Haake Polylab system at a temperature of about 180-200°C.
- the polypropylene material was added to the system first and allowed to melt. After the PP was fully melted, as indicated by a stabilized torque reading, which was usually obtained in four to five minutes, untreated EPDM rubber was added to the mixer.
- One minute after EPDM addition the appropriate azo compound was added to the mixture at 4.3 wt. % ofthe rubber and the mixture was blended for one minute.
- the rubber-plastic composite was removed and ground using a laboratory mill (Thomas Wiley, model 4) with 40-mesh screen.
- the properties ofthe resulting recycled materials can be evaluated by first molding test specimens from the recycled product and then subjecting the specimens to a variety of standard tests.
- compression molding of an EPDM-modified PP can be performed in a heated press (e.g., Carver, Model C).
- the machine should first be preheated to equilibrium at about 225°C.
- Rubber test specimen sheets can be prepared using a square-shaped aluminum frame (90 mm x 150 mm) with a thickness of 1.5 mm is then sandwiched by two aluminum plates to form the mold.
- materials should be preheated for about 5 minutes, then compressed to about 3.4 to 30 MPa for 5 minutes. Pressure is then slowly ramped up to about 8 to 100 MPa during a 5-minute period.
- Sheets can be cooled to room temperature under about an 8 to 100 MPa load using a Schrader cooling press. The sheets can then be removed and die-cut into test specimens.
- Tensile specimens were prepared using a !/_ scale ASTM D412 die. Tensile testing was performed using an Instron 6025 with attached computer operating system and a crosshead speed of 5 cm/min. Elongation was determined using crosshead displacement and the gage section as the original length.
- Dynamic Mechanical Analysis (DMA) was accomplished in forced dynamic shear using a rectangular torsion specimen in a Rheometrics 605. Temperature sweeps were performed over the range from -100°C to 50°C with heating rate of 3°C/min.
- the data presented below was generated using a blend of recycled EPDM and polypropylene.
- the samples that were subjected to reactive blending were processed as described above using t-butyl hydroperoxide as the free radical generating compound.
- Figure 2 presents the tensile strengths of the EPDM/PP blends both with and without reactive blending processing. Two observations are readily apparent. First, the stress capability ofthe blend decreases as the rubber content goes up. Basically, this can be explained through a volume rule of additivity where the higher strength PP molecules are gradually replaced by the lower strength EPDM phase. Secondly, reactive blending dramatically enhanced the stress capability of all the blends. Percentage increases as great as 80% at the highest rubber content were observed.
- Figure 3 shows the elongational capability results that corresponds to the breaking stresses reported in Figure 2.
- Reactive blending utilizing t-butyl hydroperoxide again provided significant improvement in all cases. Samples without reactive blending did not even provide rubber-like properties. Specifically, elongational capabilities of the reactive blends of 105% and 110% were obtained at 50 and 80% rubber content, respectively.
- the low temperature dispersion peak for G" occurs at -60°C, closely approximating the glass transition temperature (T g ) of the pure EPDM. Similarly, the other peak in G" occurs near -2°C, or the T g of the PP.
- processing conditions can also affect the properties of the blends.
- DOE design of experiments
- a second important factor identified from the DOE is the size of the rubber particles. Specifically, the smaller the rubber particle, the greater the elongational capability.
- the polypropylene was added to a Haake Polylab after an equilibrium temperature (180°C) and a 30 rpm rotor was reached.
- the EPDM was added to the polypropylene melt and blended for about 1 minute. Thereafter, the appropriate free, radical generating compound was added and blending continued for approximately an additional minute. Following blending the recycled material was collected, ground using a laboratory mill with a 40-mesh screen, and molded into test specimens. A variety of tests were performed and the data are displayed below in Table 2.
- the polypropylene was added to a Haake Polylab and processed until melted (about 5 minutes). The system was operated at a rotor speed of about 30 rpm and at temperatures specified below.
- the EPDM was added to the polypropylene melt and blended for about 1 minute. Thereafter, the appropriate free radical generating compound was added and blending continued for approximately an additional minute. Following blending the recycled material was collected and processed into test specimens. Tensile strength was evaluated after cooling for 30 minutes at 81°F and 20 hours in air at room temperature. The data obtained is shown in Table 3. Table 3
- FRG free radical generating compound
- FRG free radical generating compound Azo: Azodicarbonamide Benz: Dibenzoyl peroxide
- FRG free radical generating compound Azo: Azodicarbonamide Benz: Dibenzoyl peroxide
- Recycled EPDM rubber 80 mesh particles (available from Erickson, Inc) were dispersed in an aqueous acetone solution (10% acetone) and were oxidized by adding 2% by weight KMn0 . After 24 hours, the purple color of the KMn0 4 disappeared, indicating the completion of the reaction. The by-product, MnO 2 , was further oxidized for separation by 30% H 2 0 2 with 0.1% H 2 S0 aqueous solution. The rubber was washed with water until the filtrate was neutral. Finally, the treated rubber was air-dried.
- Reactive blending was accomplished by the addition of t-butyl hydroperoxide either to the blend immediately after the addition of rubber, or by soaking the rubber in the t-butyl hydroperoxide prior to blending. Mixing of the blend was stopped after a specified time (two to ten minutes), or when the torque became constant. The rubber-plastic composite was removed and then ground using a laboratory mill (Thomas Wiley, model 4) with a 40-mesh screen. The data obtained are shown in Figures 10 and 11.
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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)
- Life Sciences & Earth Sciences (AREA)
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Abstract
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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AU2002211248A AU2002211248A1 (en) | 2000-09-21 | 2001-09-21 | Thermoplastic elastomers and polymers derived from recycled rubber and plastics |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US23425600P | 2000-09-21 | 2000-09-21 | |
US60/234,256 | 2000-09-21 |
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WO2002024795A1 true WO2002024795A1 (fr) | 2002-03-28 |
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PCT/US2001/029600 WO2002024795A1 (fr) | 2000-09-21 | 2001-09-21 | Elastomeres thermoplastiques et polymeres obtenus a partir de caoutchouc et de plastique recycles |
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AU (1) | AU2002211248A1 (fr) |
WO (1) | WO2002024795A1 (fr) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006012912A1 (fr) * | 2004-08-04 | 2006-02-09 | Pirelli & C. S.P.A. | Élastomère thermoplastique et processus de fabrication |
WO2007032659A1 (fr) * | 2005-09-12 | 2007-03-22 | Looi Wan Bew Loo On Bew | Procédé pour convertir un plastique thermodurci en plastique recyclable et réutilisable |
FR2894923A1 (fr) * | 2005-12-20 | 2007-06-22 | Plastic Omnium Cie | Pare-boue de vehicule automobile comprenant une zone souple, procede de fabrication d'un tel pare-boue |
US7652101B2 (en) | 2003-03-31 | 2010-01-26 | Pirelli & C. S.P.A. | Thermoplastic material comprising a vulcanized rubber in a subdivided form |
GB2476576A (en) * | 2009-12-22 | 2011-06-29 | Crumb Rubber Ltd | Composition for use in components requiring a surface appearance of cast iron |
WO2019233873A1 (fr) * | 2018-06-08 | 2019-12-12 | Brgm | Procédé de traitement d'un mélange de plastiques par oxydation ménagée |
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DE1960281A1 (de) * | 1968-12-03 | 1970-11-19 | Saiag Soc Per Az Ind Articoli | Waelzmembrane |
US5969053A (en) * | 1992-02-27 | 1999-10-19 | Composite Particles, Inc. | Higher modulus compositions incorporating particulate rubber |
US6015861A (en) * | 1997-12-17 | 2000-01-18 | The Standard Products Company | Method for manufacture of elastomeric alloys using recycled rubbers |
US6139447A (en) * | 1997-10-24 | 2000-10-31 | Sumitomo Rubber Industries Limited | Rubber composition for golf ball and golf ball produced using the same |
US6207723B1 (en) * | 1998-01-26 | 2001-03-27 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Rubber composition and method for producing the same |
-
2001
- 2001-09-21 WO PCT/US2001/029600 patent/WO2002024795A1/fr active Application Filing
- 2001-09-21 AU AU2002211248A patent/AU2002211248A1/en not_active Abandoned
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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DE1960281A1 (de) * | 1968-12-03 | 1970-11-19 | Saiag Soc Per Az Ind Articoli | Waelzmembrane |
US5969053A (en) * | 1992-02-27 | 1999-10-19 | Composite Particles, Inc. | Higher modulus compositions incorporating particulate rubber |
US6139447A (en) * | 1997-10-24 | 2000-10-31 | Sumitomo Rubber Industries Limited | Rubber composition for golf ball and golf ball produced using the same |
US6015861A (en) * | 1997-12-17 | 2000-01-18 | The Standard Products Company | Method for manufacture of elastomeric alloys using recycled rubbers |
US6207723B1 (en) * | 1998-01-26 | 2001-03-27 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Rubber composition and method for producing the same |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
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US7652101B2 (en) | 2003-03-31 | 2010-01-26 | Pirelli & C. S.P.A. | Thermoplastic material comprising a vulcanized rubber in a subdivided form |
WO2006012912A1 (fr) * | 2004-08-04 | 2006-02-09 | Pirelli & C. S.P.A. | Élastomère thermoplastique et processus de fabrication |
WO2007032659A1 (fr) * | 2005-09-12 | 2007-03-22 | Looi Wan Bew Loo On Bew | Procédé pour convertir un plastique thermodurci en plastique recyclable et réutilisable |
FR2894923A1 (fr) * | 2005-12-20 | 2007-06-22 | Plastic Omnium Cie | Pare-boue de vehicule automobile comprenant une zone souple, procede de fabrication d'un tel pare-boue |
GB2476576A (en) * | 2009-12-22 | 2011-06-29 | Crumb Rubber Ltd | Composition for use in components requiring a surface appearance of cast iron |
GB2476576B (en) * | 2009-12-22 | 2014-09-17 | Crumb Rubber Ltd | Composition for use in components requiring a surface appearance of cast iron |
WO2019233873A1 (fr) * | 2018-06-08 | 2019-12-12 | Brgm | Procédé de traitement d'un mélange de plastiques par oxydation ménagée |
FR3082206A1 (fr) * | 2018-06-08 | 2019-12-13 | Brgm | Procede de traitement d'un melange de plastiques par oxydation menagee |
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