WO2018096377A2 - Homogeneous polymer agglomerate containing ground rubber, reinforced thermoset plastic waste and thermoplastic waste - Google Patents
Homogeneous polymer agglomerate containing ground rubber, reinforced thermoset plastic waste and thermoplastic waste Download PDFInfo
- Publication number
- WO2018096377A2 WO2018096377A2 PCT/HU2017/050052 HU2017050052W WO2018096377A2 WO 2018096377 A2 WO2018096377 A2 WO 2018096377A2 HU 2017050052 W HU2017050052 W HU 2017050052W WO 2018096377 A2 WO2018096377 A2 WO 2018096377A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- rubber
- waste
- ground
- fiber reinforced
- reinforced thermoset
- Prior art date
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 64
- 239000005060 rubber Substances 0.000 title claims abstract description 62
- 239000002699 waste material Substances 0.000 title claims abstract description 61
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 33
- 229920000642 polymer Polymers 0.000 title claims abstract description 32
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 27
- 239000013502 plastic waste Substances 0.000 title abstract description 7
- 239000004416 thermosoftening plastic Substances 0.000 title abstract description 4
- 238000000034 method Methods 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 16
- 238000010924 continuous production Methods 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims description 46
- 239000000835 fiber Substances 0.000 claims description 32
- 239000004952 Polyamide Substances 0.000 claims description 21
- 229920002647 polyamide Polymers 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 16
- 238000005516 engineering process Methods 0.000 claims description 14
- 239000003677 Sheet moulding compound Substances 0.000 claims description 12
- 239000011888 foil Substances 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 11
- -1 polypropylene Polymers 0.000 claims description 11
- 229920000098 polyolefin Polymers 0.000 claims description 10
- 239000004412 Bulk moulding compound Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 229920000459 Nitrile rubber Polymers 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- 229920003051 synthetic elastomer Polymers 0.000 claims description 6
- 239000005061 synthetic rubber Substances 0.000 claims description 6
- 244000043261 Hevea brasiliensis Species 0.000 claims description 5
- 239000003365 glass fiber Substances 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- 229920003052 natural elastomer Polymers 0.000 claims description 5
- 229920001194 natural rubber Polymers 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 5
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 4
- 239000000356 contaminant Substances 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- 238000013016 damping Methods 0.000 claims description 3
- 230000020169 heat generation Effects 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000002557 mineral fiber Substances 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 3
- 235000010446 mineral oil Nutrition 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 229920001195 polyisoprene Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 229920002545 silicone oil Polymers 0.000 claims description 3
- 239000004753 textile Substances 0.000 claims description 3
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 3
- 239000000806 elastomer Substances 0.000 claims description 2
- 239000005340 laminated glass Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000004064 recycling Methods 0.000 abstract description 11
- 239000007858 starting material Substances 0.000 abstract 1
- 238000001746 injection moulding Methods 0.000 description 6
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000011151 fibre-reinforced plastic Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000010813 municipal solid waste Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002990 reinforced plastic Substances 0.000 description 2
- 229920002397 thermoplastic olefin Polymers 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IRLQAJPIHBZROB-UHFFFAOYSA-N buta-2,3-dienenitrile Chemical compound C=C=CC#N IRLQAJPIHBZROB-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- VEMKTZHHVJILDY-UHFFFAOYSA-N resmethrin Chemical compound CC1(C)C(C=C(C)C)C1C(=O)OCC1=COC(CC=2C=CC=CC=2)=C1 VEMKTZHHVJILDY-UHFFFAOYSA-N 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/0026—Recovery of plastics or other constituents of waste material containing plastics by agglomeration or compacting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/0026—Recovery of plastics or other constituents of waste material containing plastics by agglomeration or compacting
- B29B2017/0031—Melting the outer surface of compressed waste, e.g. for forming briquets by expelling the compressed waste material through a heated tool
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
- Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
-
- 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 combined recycling of ground rubber, fiber reinforced thermoset plastic waste and thermoplastic polymer waste. From these waste materials homogenous polymer agglomerate is prepared by a continuous process, in a single technology step.
- the invention relates to said process and to the wear and impact resistant, durable and flexible polymer agglomerate produced as well as to products prepared from such agglomerate.
- thermoset plastic wastes more particularly, rubber and fiber reinforced plastic wastes
- a well-known method for disposing of polyolefin wastes is constituted by recycling and recovering such waste materials, for which, these days, there aire quite a number of technological procedures to be applied.
- the reuse of rubber wastes represents a significantly harder problem. Since rubber has a cross-linked polymer structure, it does not melt when heated but decomposes and will have a distinctive burnt rubber smell. Furthermore, rubber has no reactive functional groups on the surface and this it possesses poor adhesive properties, further it has an uneven surface, therefore rubber cannot be easily blended with other polymers.
- ground rubber waste to rubber blends is limited since by acting only as inert filler, ground rubber impairs product quality.
- rubber waste comprises ingredients with valuable properties, and therefore instead of destructing them, it would be worth finding possibilities for recycling.
- a valuable ingredient of rubber waste is caoutchouc which has high tensile strength and high tearing strength and also shows very good dynamic properties.
- Different types of synthetic rubber comprise e.g. the butadiene styrene, butadiene nitrile or butyl rubber, which are capable of efficiently absorbing the deformation energy and has an excellent vibration damper effect.
- SMC bulk molding compound
- BMC bulk molding compound
- pre-preg pre-preg
- the above mentioned waste materials are blended by means of double-screw compounding extruders.
- the screw characteristics are determined in such way that by using force-feed devices, the ground rubber, polyolefin or polyamide waste materials, optionally SMC and other additives, such as master blends, are added to a polyolefin matrix melted by direct heating.
- melting is performed at such a high temperature where rubber and the SMC degrade, which is aggravated by a further increase in the temperature occurring due to the action of friction and that of shear forces produced when blending the components.
- the residence period in the compounding drum is 2-5 minutes further intensifies degradation. Consequently, this technology may not be properly controlled and gases having adverse effects on human health and the environment may also be evolved.
- Hungarian patent No. 226 636 discloses a thermoplastic polymer composition with flame retardation, vibration and noise reduction' properties, which composition may contain 1-20% tyre powder, this document however does not contain any related example.
- the composition is produced by homogenization in a blending equipment heated to 180°C for 10 minutes, and after solidification, the product is ground, and for molding the product it is heated up again to 170°C. Under such drastic conditions, significant degradation occurs, which is attempted to be lowered by adding 5-65% flame retardant.
- the production conditions applied are much gentler than those described above, where for recycling purposes the ground rubber waste and the fiber reinforced thermoset plastic waste are blended with wastes of thermoplastic polymers.
- the aforementioned components are not only processed without the worsening of their properties, but due to their mutual interaction, also their properties become improved, which results in a polymer agglomerate with surprisingly advantageous properties, and from these agglomerates products with similarly good properties can be produced. Consequently, the technical solution according to the invention offers a possibility for the production of high value-added products from such waste materials, the processing of which has so far represented problems.
- the invention relates to homogenous polymer agglomerates comprising the following components:
- ground rubber having particle size from 0.1 to 3 mm, which is ground natural rubber and/or ground synthetic rubber,
- thermoset plastic material having particle size of 10 mm, at most, thermoplastic polymer comprising polyolefm and/or polyamide, and which has particle size of 10 mm, at most, and
- thermoplastic polymer optionally, other additives and/or auxiliaries commonly used in the plastic industry, wherein the weight ratio of the total weight of ground rubber and fiber reinforced thermoset plastic relative to the weight of the thermoplastic polymer is up to 50:50,
- the particles of fiber reinforced thermoset plastic and the fibers contained in them are completely covered with the said polyamide.
- the homogenous polymer agglomerate contains 5-30 % by weight of ground rubber, 2-10 % by weight of fiber reinforced thermoset plastic and 60-93% by weight of thermoplastic polymer.
- the components of the homogenous polymer agglomerate are selected from:
- the ground rubber comprises ground tyre rubber or other ground rubber wastes of industrial origin, or a mixture thereof, comprising natural rubber (caoutchouc) or synthetic rubber, such as butadiene styrene rubber, nitrile butadiene rubber or butyl rubber, and optionally carbon black, mineral oil or silicone oil, cross-linking agent and other additives commonly used in the preparation of rubber products,
- thermoplastic polymer may comprise polyolefm waste and/or polyamide waste, such as coextruded polypropylene-polyamide foil waste, polypropylene waste or polyamide waste of automobile industry or electronics industry origin, or polyethylene waste, such as polyethylene foil waste, bottle cap and the like, or a mixture of two or more of these wastes, and
- the fiber reinforced thermoset plastic is ground sheet molding compound (SMC) or bulk molding compound (BMC), which comprise epoxy resin or polyester matrix and textile fibers, glass fibers, mineral fibers, carbon fibers or metal fibers and the like, or ground particles of hand laminated glass reinforced polyester materials, or pre-preg waste, for example which is left as contaminant residue in the waste of the aforementioned coextruded foil used for packaging pre-preg, or any mixture of two or more of said fiber reinforced thermoset plastics.
- SMC ground sheet molding compound
- BMC bulk molding compound
- the additives or auxiliaries optionally present in the agglomerate and in the product of the present invention may be for example coloring, gas absorbing or homogenizing additives.
- the polymer agglomerate according to the invention has a homogenous structure, further it is thermally stable, durable, has high wear resistance, has flexible elastomer properties or thermoplastic elastomer properties, excellent cold impact resistance and high damping coefficient.
- the present invention also relates to a process for preparing the homogenous polymer agglomerate according to the invention, during which the components are fed into an agglomerating apparatus, and in a single technology step using continuous process the components are converted into homogeneous blend at a temperature range of 130-150°C in 10-30 secundum (sec),
- the said temperature range of 130-150°C is achieved by indirect heat generation that occurs during the mixing of the added components by means of high searing force, and their friction.
- the invention also relates to products prepared from the homogenous polymer agglomerate according to the invention or from the agglomerate prepared by the process according to the invention, optionally by adding further additives and auxiliaries commonly used in the plastic industry.
- the product may be a basement tai king sheet, flexible paving, flexible road safety deflector, or sheets for other purposes, such as standing aid carpets used in electrical industry and other workplaces.
- the invention relates to the combined recycling of hardly processible industrial wastes, namely, ground rubber and ground reinforced thermoset plastic, with thermoplastic polymer, more particularly poly olefin and/or polyamide, under gentle technological conditions. Consequently, during processing the aforementioned components are capable of retaining their beneficial properties and the rubber will not burn, in addition, the thermal stability of thermoplastic components increases in the presence of the thermosetting plastic.
- beneficial properties are not only the sum of properties of components, but due to the beneficial interaction between them, a polymer agglomerate with more superior properties than those of the components is obtained, and from this agglomerate products with similarly good properties can be produced. More particularly, the agglomerate and the product according to the invention are durable, thermally stable and usable in a wide temperature range, show good abrasion resistance and flexible thermoplastic elastomer property, and have high cold resistance to impact and high damping coefficient.
- ground rubber refers to ground tyre rubber or other ground rubber wastes of industrial origin or a mixture thereof, which may contain natural rubber or synthetic rubber, such as butadiene styrene rubber, nitrile butadiene rubber or butyl rubber, and optionally carbon black, mineral oil or silicone oil, cross- linking agent and other additives commonly used in the production of rubber products. Rubber waste is used in the form of ground rubber with particle size from 0.1 to 3 mm.
- the thermoplastic polymer comprises mainly polyolefin and/or polyamide waste materials, such as coextruded polypropylene-polyamide foil waste, polypropylene or polyamide waste of automobile industry or electronics industry origin, or polyethylene waste materials, such as polyethylene foil waste or even bottle caps and the like, or the mixture of two or more of these. Additionally, other thermoplastic polymers may be present in smaller amounts, such as additives, in the thermoplastic polymer.
- the terms fiber reinforced thermoset plastic and reinforced thermoset and reinforced plastic refer to for example sheet molding compound (SMC), bulk molding compound (BMC), which comprise epoxy resin or polyester matrix and, as enforcer fibers, e.g. textile fibers, glass fibers, mineral fibers, carbon fibers or metal fibers and the like.
- the fiber reinforced plastic waste may be a hand-laminated fiberglass polyester material originating for example from hull materials, or any other similar waste material.
- the reinforced plastic may as well be fiberglass containing resin, such as pre-preg, which is left for example as contaminant residue in the waste of the coextrucled foil used for its packaging, the said foil generally contains about 3% pre-preg as contaminant.
- the pre-preg is a pre-impregnated fiber reinforced composite material comprising partially cross-linked matrix material (such as epoxy resin or unsaturated polyester). By cross-linking (hardening) of pre-preg, fiber reinforced plastic is produced.
- pre-preg is used in the agglomerate according to the invention, in the process according to the invention the pre-preg will harden, and also a chemical reaction occurs between the unsaturated epoxy compound present in the pre-preg and the polyamide, which further improves the product properties without causing any significant increase in its elastic modulus.
- thermoplastic polymers or fiber reinforced thermoset plastics i.e. their longest dimension is 10 mm, at most. Due to the grinding method used, the aforementioned plastic particles are basically of irregular shape, and in the case of grinding plastic sheet waste, the particles may have irregular sheet-shape, where the size of the sheet particles is 10 mm, at most.
- the homogenous polymer agglomerate contains 5-30 % by weight of ground rubber, 2-10 % by weight of fiber reinforced thermoset plastic particles and 60-93% by weight of thermoplastic polymer particles.
- the ratios may be modified by considering the exposure to weather and the requirements of mechanical load.
- the outstanding properties of the agglomerate according to the invention are ensured by the new production technology developed by the inventor.
- This technology is based on the dry agglomeration technology commonly used in recycling polyethylene foils.
- the ground waste materials are pressed between a fixed disc and a rotating disc by using an auger. Between said discs the frictional force heats up the material causing it to melt, and from the grooves machined on the external edges of the discs a cylindrical object with a diameter of approximately 1.5-4 mm will emerge, from which granulates with up to the length of 1 -5 mm will be formed by post grinding.
- This technology was modified so that it is suitable for converting the present multi- component system into a blend.
- the present modified technology even five or more waste components can be processed in a single step at the relatively low temperature range of 130-150°C applied.
- thermosetting components i.e. ground rubber and fiber reinforced plastic
- the weight ratio of thermosetting components to the thermoplastic polymer may reach the ratio of 50:50.
- the process according to the invention is highly productive and does not require water washing.
- force-feed technology devices are used for the purpose of the accurate feeding of material flows.
- the aforementioned process temperature is ensured by the use of adequately-sized agglomerating, grinding discs. Between the discs indirect heat generation takes place as a result of the high shearing forces and friction that occur during the blending of added components.
- the utilization of the indirectly generated heat is not only a cost-effective option from the energetic point of view, but it also allows the production temperature to be kept within the said specific narrow limits. The precise observation of temperature limits is of great importance, since above 150°C rubber would get burned, which would in turn result in lower-quality product.
- Another important characteristic of the technical solution according to the invention is the use of ground rubber with particle size from 0.1 to 3 mm. The small particle dimension and the associated large specific surface area facilitate the homogenous blending of such particles with the thermoplastic polyolefin and their welding together enhances the formation of a rubber-flexible product.
- 20 parts by weight ground tyre with a particle size from 0.1 to 3 mm, 10 parts by weight ground SMC with a particle size of maximum 10 mm and 70 parts by weight mixed thermoplastic polymer waste with particle size of maximum 10 mm are fed into an agglomerating apparatus and converted to a homogenous agglomerate in a single technological step by using continuous process at the temperature range of 130-150°C in 10-30 sec.
- Homogenous polymer agglomerate 20 parts by weight ground tyre with a particle size from 0.1 to 3 mm and 70 parts by weight pre-preg contaminated coextruded propylene-polyamide foil waste with particle size of maximum 10 mm are fed into an agglomerating apparatus and converted to homogenous agglomerate in a single technological step by using continuous process at the temperature range of 130-150°C in 10-30 sec.
- Standing aid carpets are prepared from the homogenous polymer agglomerate of example 1 by injection molding.
- the thus produced standing aid carpet has excellent ground resonance filter and geothermal insulating properties.
- Paving elements are prepared from the homogenous polymer agglomerate of example 1 by injection molding.
- Deflector profiles are prepared from the homogenous polymer agglomerate of example 1 by extrusion.
- Trash containers are prepared from the homogenous polymer agglomerate of example 2 by injection molding. 8.
Abstract
The invention relates to recycling ground rubber along with reinforced thermoset plastic waste and thermoplastic waste to obtain useful starting materials. From said waste materials polymer agglomerate is prepared by a continuous process, in one step. The invention covers said process, the obtained polymer agglomerate and the product prepared therefrom.
Description
Homogenous polymer agglomerate containing ground rubber, reinforced thermoset plastic waste and thermoplastic waste
Field of the invention
The invention relates to the combined recycling of ground rubber, fiber reinforced thermoset plastic waste and thermoplastic polymer waste. From these waste materials homogenous polymer agglomerate is prepared by a continuous process, in a single technology step. The invention relates to said process and to the wear and impact resistant, durable and flexible polymer agglomerate produced as well as to products prepared from such agglomerate.
Background of the Invention
In this day and age the disposal of high quantities of accumulated, environmentally hazardous industrial wastes, especially thermoset plastic wastes, more particularly, rubber and fiber reinforced plastic wastes, represents an ever-growing problem.
A well-known method for disposing of polyolefin wastes is constituted by recycling and recovering such waste materials, for which, these days, there aire quite a number of technological procedures to be applied. The reuse of rubber wastes represents a significantly harder problem. Since rubber has a cross-linked polymer structure, it does not melt when heated but decomposes and will have a distinctive burnt rubber smell. Furthermore, rubber has no reactive functional groups on the surface and this it possesses poor adhesive properties, further it has an uneven surface, therefore rubber cannot be easily blended with other polymers.
When being processed, rubber waste is ground by classic or cryogen grinding and part of the fine powder is used in rubber blends. The ground rubber with larger particle size (of 3-4 mm) is panelized with polyurethane glue to form e.g. floor tiles. Devolcanization or utility of energetic purpose represent additional alternatives. In the latter case the ground tyre is burned in cement factories at very low energy balance, which may also be accompanied with significant environmental pollution.
The addition of ground rubber waste to rubber blends is limited since by acting only as inert filler, ground rubber impairs product quality. However, rubber waste comprises ingredients with valuable properties, and therefore instead of destructing them, it would be worth finding possibilities for recycling. A valuable ingredient of rubber waste is
caoutchouc which has high tensile strength and high tearing strength and also shows very good dynamic properties. Different types of synthetic rubber comprise e.g. the butadiene styrene, butadiene nitrile or butyl rubber, which are capable of efficiently absorbing the deformation energy and has an excellent vibration damper effect.
Processes for recycling fiber reinforced plastics, e.g. sheet molding compound
(SMC), bulk molding compound (BMC) and pre-preg are already known, such processes were published by the present inventor in WO2013/084014 and WO2015/177580. However, these processes are not yet in widespread use, therefore these waste materials are also primarily used for energetic purposes. Fiber reinforced thermoset plastics also have beneficial properties, such as extremely high strength and durability, therefore the recycling of these materials is also desirable.
In the presently known processes for recycling rubbers and polyolefms, the above mentioned waste materials are blended by means of double-screw compounding extruders. With respect to these, the screw characteristics are determined in such way that by using force-feed devices, the ground rubber, polyolefin or polyamide waste materials, optionally SMC and other additives, such as master blends, are added to a polyolefin matrix melted by direct heating. However, melting is performed at such a high temperature where rubber and the SMC degrade, which is aggravated by a further increase in the temperature occurring due to the action of friction and that of shear forces produced when blending the components. The fact that in such technologies the residence period in the compounding drum is 2-5 minutes further intensifies degradation. Consequently, this technology may not be properly controlled and gases having adverse effects on human health and the environment may also be evolved.
Hungarian patent No. 226 636 discloses a thermoplastic polymer composition with flame retardation, vibration and noise reduction' properties, which composition may contain 1-20% tyre powder, this document however does not contain any related example. The composition is produced by homogenization in a blending equipment heated to 180°C for 10 minutes, and after solidification, the product is ground, and for molding the product it is heated up again to 170°C. Under such drastic conditions, significant degradation occurs, which is attempted to be lowered by adding 5-65% flame retardant.
In the technical solution according to the invention, the production conditions applied are much gentler than those described above, where for recycling purposes the ground rubber waste and the fiber reinforced thermoset plastic waste are blended with
wastes of thermoplastic polymers. In the polymer agglomerate prepared by using the process according to the invention, the aforementioned components are not only processed without the worsening of their properties, but due to their mutual interaction, also their properties become improved, which results in a polymer agglomerate with surprisingly advantageous properties, and from these agglomerates products with similarly good properties can be produced. Consequently, the technical solution according to the invention offers a possibility for the production of high value-added products from such waste materials, the processing of which has so far represented problems. Summary of the invention
The invention relates to homogenous polymer agglomerates comprising the following components:
ground rubber having particle size from 0.1 to 3 mm, which is ground natural rubber and/or ground synthetic rubber,
fiber reinforced thermoset plastic material having particle size of 10 mm, at most, thermoplastic polymer comprising polyolefm and/or polyamide, and which has particle size of 10 mm, at most, and
optionally, other additives and/or auxiliaries commonly used in the plastic industry, wherein the weight ratio of the total weight of ground rubber and fiber reinforced thermoset plastic relative to the weight of the thermoplastic polymer is up to 50:50,
wherein the surface of ground rubber particles are molten together with the said polyolefm, and the ground rubber particles are embedded in and welded with the said polyolefm, and
the particles of fiber reinforced thermoset plastic and the fibers contained in them are completely covered with the said polyamide.
In certain embodiments of the invention, the homogenous polymer agglomerate contains 5-30 % by weight of ground rubber, 2-10 % by weight of fiber reinforced thermoset plastic and 60-93% by weight of thermoplastic polymer.
In certain embodiments of the invention, the components of the homogenous polymer agglomerate are selected from:
the ground rubber comprises ground tyre rubber or other ground rubber wastes of industrial origin, or a mixture thereof, comprising natural rubber (caoutchouc) or synthetic rubber, such as butadiene styrene rubber, nitrile butadiene rubber or butyl rubber, and
optionally carbon black, mineral oil or silicone oil, cross-linking agent and other additives commonly used in the preparation of rubber products,
the thermoplastic polymer may comprise polyolefm waste and/or polyamide waste, such as coextruded polypropylene-polyamide foil waste, polypropylene waste or polyamide waste of automobile industry or electronics industry origin, or polyethylene waste, such as polyethylene foil waste, bottle cap and the like, or a mixture of two or more of these wastes, and
the fiber reinforced thermoset plastic is ground sheet molding compound (SMC) or bulk molding compound (BMC), which comprise epoxy resin or polyester matrix and textile fibers, glass fibers, mineral fibers, carbon fibers or metal fibers and the like, or ground particles of hand laminated glass reinforced polyester materials, or pre-preg waste, for example which is left as contaminant residue in the waste of the aforementioned coextruded foil used for packaging pre-preg, or any mixture of two or more of said fiber reinforced thermoset plastics.
The additives or auxiliaries optionally present in the agglomerate and in the product of the present invention may be for example coloring, gas absorbing or homogenizing additives.
The polymer agglomerate according to the invention has a homogenous structure, further it is thermally stable, durable, has high wear resistance, has flexible elastomer properties or thermoplastic elastomer properties, excellent cold impact resistance and high damping coefficient.
The present invention also relates to a process for preparing the homogenous polymer agglomerate according to the invention, during which the components are fed into an agglomerating apparatus, and in a single technology step using continuous process the components are converted into homogeneous blend at a temperature range of 130-150°C in 10-30 secundum (sec),
during said process the surface of rubber particles becomes molten and merges with the polyolefm being in a partially molten state, and thus the said polyolefm surrounds the ground rubber and welds together with it, and the polyamide completely covers the surface of the fiber reinforced thermoset plastic particles,
and the blend is cooled to obtain homogenous polymer agglomerate.
In an embodiment of the invention the said temperature range of 130-150°C is achieved by indirect heat generation that occurs during the mixing of the added
components by means of high searing force, and their friction.
The invention also relates to products prepared from the homogenous polymer agglomerate according to the invention or from the agglomerate prepared by the process according to the invention, optionally by adding further additives and auxiliaries commonly used in the plastic industry.
In certain embodiments the product may be a basement tai king sheet, flexible paving, flexible road safety deflector, or sheets for other purposes, such as standing aid carpets used in electrical industry and other workplaces. Detailed description of the invention
As has been demonstrated above, the invention relates to the combined recycling of hardly processible industrial wastes, namely, ground rubber and ground reinforced thermoset plastic, with thermoplastic polymer, more particularly poly olefin and/or polyamide, under gentle technological conditions. Consequently, during processing the aforementioned components are capable of retaining their beneficial properties and the rubber will not burn, in addition, the thermal stability of thermoplastic components increases in the presence of the thermosetting plastic. Thus the above mentioned beneficial properties are not only the sum of properties of components, but due to the beneficial interaction between them, a polymer agglomerate with more superior properties than those of the components is obtained, and from this agglomerate products with similarly good properties can be produced. More particularly, the agglomerate and the product according to the invention are durable, thermally stable and usable in a wide temperature range, show good abrasion resistance and flexible thermoplastic elastomer property, and have high cold resistance to impact and high damping coefficient.
In the present description the term ground rubber refers to ground tyre rubber or other ground rubber wastes of industrial origin or a mixture thereof, which may contain natural rubber or synthetic rubber, such as butadiene styrene rubber, nitrile butadiene rubber or butyl rubber, and optionally carbon black, mineral oil or silicone oil, cross- linking agent and other additives commonly used in the production of rubber products. Rubber waste is used in the form of ground rubber with particle size from 0.1 to 3 mm.
The thermoplastic polymer comprises mainly polyolefin and/or polyamide waste materials, such as coextruded polypropylene-polyamide foil waste, polypropylene or polyamide waste of automobile industry or electronics industry origin, or polyethylene
waste materials, such as polyethylene foil waste or even bottle caps and the like, or the mixture of two or more of these. Additionally, other thermoplastic polymers may be present in smaller amounts, such as additives, in the thermoplastic polymer.
In the present invention the terms fiber reinforced thermoset plastic and reinforced thermoset and reinforced plastic refer to for example sheet molding compound (SMC), bulk molding compound (BMC), which comprise epoxy resin or polyester matrix and, as enforcer fibers, e.g. textile fibers, glass fibers, mineral fibers, carbon fibers or metal fibers and the like. Furthermore, the fiber reinforced plastic waste may be a hand-laminated fiberglass polyester material originating for example from hull materials, or any other similar waste material. Additionally, in certain embodiments of the invention, the reinforced plastic may as well be fiberglass containing resin, such as pre-preg, which is left for example as contaminant residue in the waste of the coextrucled foil used for its packaging, the said foil generally contains about 3% pre-preg as contaminant.
The pre-preg is a pre-impregnated fiber reinforced composite material comprising partially cross-linked matrix material (such as epoxy resin or unsaturated polyester). By cross-linking (hardening) of pre-preg, fiber reinforced plastic is produced.
If pre-preg is used in the agglomerate according to the invention, in the process according to the invention the pre-preg will harden, and also a chemical reaction occurs between the unsaturated epoxy compound present in the pre-preg and the polyamide, which further improves the product properties without causing any significant increase in its elastic modulus.
The particle size of thermoplastic polymers or fiber reinforced thermoset plastics, i.e. their longest dimension is 10 mm, at most. Due to the grinding method used, the aforementioned plastic particles are basically of irregular shape, and in the case of grinding plastic sheet waste, the particles may have irregular sheet-shape, where the size of the sheet particles is 10 mm, at most.
In certain embodiments of the invention the homogenous polymer agglomerate contains 5-30 % by weight of ground rubber, 2-10 % by weight of fiber reinforced thermoset plastic particles and 60-93% by weight of thermoplastic polymer particles. The ratios may be modified by considering the exposure to weather and the requirements of mechanical load.
The outstanding properties of the agglomerate according to the invention are ensured by the new production technology developed by the inventor. This technology is based on
the dry agglomeration technology commonly used in recycling polyethylene foils. During this technology the ground waste materials are pressed between a fixed disc and a rotating disc by using an auger. Between said discs the frictional force heats up the material causing it to melt, and from the grooves machined on the external edges of the discs a cylindrical object with a diameter of approximately 1.5-4 mm will emerge, from which granulates with up to the length of 1 -5 mm will be formed by post grinding.
This technology was modified so that it is suitable for converting the present multi- component system into a blend. By using the present modified technology even five or more waste components can be processed in a single step at the relatively low temperature range of 130-150°C applied.
The aforementioned temperature range of 130-150°C and the very short blending time of 10-30 sec ensure the beneficial properties of the agglomerate according to the invention. Under these conditions the rubber particles will not get burnt, it is only their surface layer that suffers decomposition which results in the surface transforming into a molten state. At the same time polyolefin transforms into a partially molten state and completely covers the ground rubber during blending. The molten polyolefin will merge with the surface melt of the ground rubber and they weld together, and the polyamide completely covers the surface of the fiber reinforced thermoset plastic particles. This technology enables the thermoplastic polymer to take up the thermosetting components, i.e. ground rubber and fiber reinforced plastic, in an amount that may as well be equal with its own weight. In the agglomerate according to the invention the weight ratio of thermosetting components to the thermoplastic polymer may reach the ratio of 50:50.
The process according to the invention is highly productive and does not require water washing. To ensure constant product quality, force-feed technology devices are used for the purpose of the accurate feeding of material flows.
In one embodiment the aforementioned process temperature is ensured by the use of adequately-sized agglomerating, grinding discs. Between the discs indirect heat generation takes place as a result of the high shearing forces and friction that occur during the blending of added components. The utilization of the indirectly generated heat is not only a cost-effective option from the energetic point of view, but it also allows the production temperature to be kept within the said specific narrow limits. The precise observation of temperature limits is of great importance, since above 150°C rubber would get burned, which would in turn result in lower-quality product.
Another important characteristic of the technical solution according to the invention is the use of ground rubber with particle size from 0.1 to 3 mm. The small particle dimension and the associated large specific surface area facilitate the homogenous blending of such particles with the thermoplastic polyolefin and their welding together enhances the formation of a rubber-flexible product.
In the further processing carried out by molding or extruding of the homogenous polymer agglomerate containing ground rubber embedded in and welded with thermoplastic polyolefin, the rubber does not suffer degradation, the unpleasant rubber smell experienced in the prior art recycling technologies will not emerge. Furthermore, polyamide will completely cover the particles of fiber reinforced thermoset plastic as well as the fibers on its surface.
Of course, in the process according to the invention, newly produced materials may also be used as the components of the polymer blend, agglomerate or product, by which products with similarly excellent properties may as well be produced, and these products also fall within the scope of protection of the present invention. However, since the present work was aimed at finding a solution to the management of dangerous plastic waste materials, recycled plastic waste materials are preferably used in the technical solution according to the invention.
The following examples illustrate the present invention, however the examples should not be considered as limiting the scope of the invention.
Examples
1. Example
Homogenous polymer agglomerate
20 parts by weight ground tyre with a particle size from 0.1 to 3 mm, 10 parts by weight ground SMC with a particle size of maximum 10 mm and 70 parts by weight mixed thermoplastic polymer waste with particle size of maximum 10 mm are fed into an agglomerating apparatus and converted to a homogenous agglomerate in a single technological step by using continuous process at the temperature range of 130-150°C in 10-30 sec.
2. Example
Homogenous polymer agglomerate
20 parts by weight ground tyre with a particle size from 0.1 to 3 mm and 70 parts by weight pre-preg contaminated coextruded propylene-polyamide foil waste with particle size of maximum 10 mm are fed into an agglomerating apparatus and converted to homogenous agglomerate in a single technological step by using continuous process at the temperature range of 130-150°C in 10-30 sec.
3. Example
Standing aid carpet
Standing aid carpets are prepared from the homogenous polymer agglomerate of example 1 by injection molding. The thus produced standing aid carpet has excellent ground resonance filter and geothermal insulating properties.
4. Example
Basement tanking sheet
Basement tanking sheets with a thickness adjusted between 1 mm and 10 mm are prepared from the homogenous polymer agglomerate of example 1 by extrusion.
5. Example
Flexible paving
Paving elements are prepared from the homogenous polymer agglomerate of example 1 by injection molding.
6. Example
Flexible road safety deflector
Deflector profiles are prepared from the homogenous polymer agglomerate of example 1 by extrusion.
7. Example
Municipal trash containers
Trash containers are prepared from the homogenous polymer agglomerate of example 2 by injection molding.
8. Example
Municipal trash containers
5 parts by weight ground tyre with particle size from 0.1 to 3 mm, 5 parts by weight ground SMC with particle size of maximum 10 mm and 90 parts by weight mixed thermoplastic polymer waste with particle size of maximum 10 mm are agglomerated at the temperature range of 130-150°C for 10-30 sec. From the basic material thus obtained trash containers are prepared by injection molding.
9. Example
Wall formwork system for building industry (DOKA )
5 parts by weight ground tyre with particle size from 0.1 to 3 mm, 5 parts by weight glass fiber thermoset plastics with particle size of maximum 10 mm and 90 parts by weight mixed thermoplastic polymer waste with particle size of maximum 10 mm are agglomerated at the temperature range of 130-150°C for 10-30 sec. From the basic material thus obtained shutter boards with board thickness of 25 mm are prepared by injection molding.
10. Example
Snow and wind shield boards
20 parts by weight ground tyre with particle size from 0.1 to 3 mm, 10 parts by weight glass fiber thermoset plastics with particle size of maximum 10 mm and 70 parts by weight mixed thermoplastic polymer waste with particle size of maximum 10 mm are agglomerated at the temperature range of 130-150°C for 10-30 sec. From the basic material thus obtained sheets are prepared by injection molding.
Claims
1. Homogenous polymer agglomerate containing the following components:
ground rubber having particle size from 0.1 to 3 mm, which is ground natural rubber and/or ground synthetic rubber,
fiber reinforced thermoset plastic material having particle size of 10 mm, at most, thermoplastic polymer comprising polyolefm and/or polyamide, and which has particle size of 10 mm, at most, and
optionally, other additives and/or auxiliaries commonly used in the plastic industry, wherein the weight ratio of the total weight of ground rubber and fiber reinforced thermoset plastic relative to the weight of the thermoplastic polymer is up to 50:50,
wherein the surface of ground rubber particles are molten together with the said polyolefm, and the ground rubber particles are embedded in and welded with the said polyolefm, and
the particles of fiber reinforced thermoset plastic and the fibers contained in them are completely covered with the said polyamide.
2. The homogenous polymer agglomerate according to claim 1, which comprises 5-30 % by weight of ground rubber, 2-10 % by weight of fiber reinforced thermoset plastic and 60-93% by weight of thermoplastic polymer.
3. Homogenous polymer agglomerate according to claim 1 or 2, wherein
the ground rubber comprises ground tyre rubber or other ground rubber wastes of industrial origin, or a mixture thereof, comprising natural rubber (caoutchouc) or synthetic rubber, such as butadiene styrene rubber, nitrile butadiene rubber or butyl rubber, and optionally carbon black, mineral oil or silicone oil, cross-linking agent and other additives commonly used in the preparation of rubber products,
the thermoplastic polymer may comprise polyolefin waste and/or polyamide waste, such as coextruded polypropylene-polyamide foil waste, polypropylene waste or polyamide waste of automobile industry or electronics industry origin, or polyethylene waste, such as polyethylene foil waste, bottle cap and the like, or a mixture of two or more of these wastes, and
the fiber reinforced thermoset plastic is ground sheet molding compound (SMC) or bulk molding compound (BMC), which comprise epoxy resin or polyester matrix and textile fibers, glass fibers, mineral fibers, carbon fibers or metal fibers and the like, or ground particles of hand laminated glass reinforced polyester materials, or pre-preg waste, for example which is left as contaminant residue in the waste of the aforementioned coextruded foil used for packaging pre-preg, or any mixture of two or more of said fiber reinforced thermoset plastics.
4. The homogenous polymer agglomerate according to any of claims 1 to 3, which is thermally stable, durable, has high wear resistance, has flexible elastomer properties or thermoplastic elastomer properties, excellent cold impact resistance and high damping coefficient.
5. Process for preparing the homogenous polymer agglomerate according to claim 1 characterized in that the components are fed into an agglomerating apparatus, and in a single technology step using continuous process the components are converted into homogeneous blend at a temperature range of 130-150°C in 10-30 sec,
during said process the surface of rubber particles becomes molten and merges with the polyolefin being in a partially molten state, and the said polyolefin surrounds the ground rubber and welds together with it, and the polyamide completely covers the surface of the fiber reinforced thermoset plastic particles,
and the blend is cooled to obtain homogenous polymer agglomerate.
6. The process according to claim 5 characterized in that the said temperature range of I30-150°C is achieved by indirect heat generation occurring during the mixing of the added components by means of high searing force, and their friction.
7. A product prepared from the homogenous polymer agglomerate according to any of claims 1 to 4 or from the agglomerate prepared by the process according to claim 5 or 6, optionally by adding further additives and auxiliaries commonly used in the plastic industry.
8. The product according to claim 7, which is a basement tanking sheet, a flexible
paving, a flexible road safety deflector, or sheets for other purposes, such as standing aid carpets used in electrical industry and other workplaces.
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| WO2019236377A1 (en) * | 2018-06-05 | 2019-12-12 | Dow Global Technologies Llc | Method for recycling epoxy-fiber composites into polyolefins |
| FR3096922A1 (en) | 2019-06-07 | 2020-12-11 | Nicolas Cahlik | Manufacturing process of a plastic-based part |
| WO2023106097A1 (en) * | 2021-12-09 | 2023-06-15 | Dic株式会社 | Reactive adhesive, laminated film, and packaging |
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| WO2018096377A3 (en) | 2018-07-19 |
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