HRP20020059A2 - Recycling process of waste polyethylene for making articles of double-layer wall by rotational casting - Google Patents
Recycling process of waste polyethylene for making articles of double-layer wall by rotational casting Download PDFInfo
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- HRP20020059A2 HRP20020059A2 HR20020059A HRP20020059A HRP20020059A2 HR P20020059 A2 HRP20020059 A2 HR P20020059A2 HR 20020059 A HR20020059 A HR 20020059A HR P20020059 A HRP20020059 A HR P20020059A HR P20020059 A2 HRP20020059 A2 HR P20020059A2
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- polyethylene
- wall
- foaming
- additives
- mold
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- -1 polyethylene Polymers 0.000 title claims description 121
- 239000004698 Polyethylene Substances 0.000 title claims description 115
- 229920000573 polyethylene Polymers 0.000 title claims description 115
- 239000002699 waste material Substances 0.000 title claims description 18
- 238000000034 method Methods 0.000 title claims description 9
- 238000004064 recycling Methods 0.000 title description 6
- 238000010106 rotational casting Methods 0.000 title description 2
- 239000000654 additive Substances 0.000 claims description 34
- 238000005266 casting Methods 0.000 claims description 27
- 238000005187 foaming Methods 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 25
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 13
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 12
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Substances OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 10
- 239000006260 foam Substances 0.000 claims description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 239000012963 UV stabilizer Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003365 glass fiber Substances 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 229920001684 low density polyethylene Polymers 0.000 claims description 4
- 239000004702 low-density polyethylene Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 3
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004156 Azodicarbonamide Substances 0.000 claims description 2
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 2
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 2
- VJRITMATACIYAF-UHFFFAOYSA-N benzenesulfonohydrazide Chemical compound NNS(=O)(=O)C1=CC=CC=C1 VJRITMATACIYAF-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- JRZBPELLUMBLQU-UHFFFAOYSA-N carbonazidic acid Chemical class OC(=O)N=[N+]=[N-] JRZBPELLUMBLQU-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims description 2
- 239000003431 cross linking reagent Substances 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000008240 homogeneous mixture Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- DZCCLNYLUGNUKQ-UHFFFAOYSA-N n-(4-nitrosophenyl)hydroxylamine Chemical compound ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002667 nucleating agent Substances 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001451 organic peroxides Chemical class 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 2
- 238000009827 uniform distribution Methods 0.000 claims description 2
- 229940098697 zinc laurate Drugs 0.000 claims description 2
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 claims description 2
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 238000002474 experimental method Methods 0.000 description 9
- 238000001125 extrusion Methods 0.000 description 9
- 239000002861 polymer material Substances 0.000 description 6
- 229920001169 thermoplastic Polymers 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 229920000092 linear low density polyethylene Polymers 0.000 description 5
- 239000004707 linear low-density polyethylene Substances 0.000 description 5
- 229920001225 polyester resin Polymers 0.000 description 5
- 239000004645 polyester resin Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 235000019359 magnesium stearate Nutrition 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004706 High-density cross-linked polyethylene Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009750 centrifugal casting Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229920004932 high density cross-linked polyethylene Polymers 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000013502 plastic waste Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000002847 sound insulator Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Landscapes
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Description
Područje tehnike u koje spada izum The technical field to which the invention belongs
Prema Međunarodnoj klasifikaciji patenata (MKP), ovaj se izum može svrstati u klasu: According to the International Classification of Patents (IPC), this invention can be classified as:
B 29 C 41/04 Rotacijsko ili centrifugalno lijevanje, tj. prevlačenje unutarnje stranice kalupa vrtnjom kalupa B 29 C 41/04 Rotational or centrifugal casting, i.e. coating the inner side of the mold by rotating the mold
Tehnički problem Technical problem
Tehnički problem koji se rješava ovim izumom odnosi se na: The technical problem solved by this invention refers to:
- pripremu sirovine za dobivanje pjenastog (ekspandiranog) polietilena, bez obzira na vrstu i gustoću polietilena, umješavanjem aditiva za pjenjenje u polietilen dobiven recikliranjem iz razvrstanog ili nerazvrstanog polietilenskog otpada; - preparation of raw material for obtaining foamed (expanded) polyethylene, regardless of the type and density of polyethylene, by mixing additives for foaming into polyethylene obtained by recycling from sorted or unsorted polyethylene waste;
- pjenjenje polietilena dobivenog recikliranjem iz razvrstanog ili nerazvrstanog polietilenskog otpada, bez obzira na vrstu i gustoću polietilena, pomoću aditiva za pjenjenje koji je u njega (polietilen) umiješan, pri temperaturi koja se upotrebljava u rotacijskom lijevu polietilena; - foaming of polyethylene obtained by recycling from sorted or unsorted polyethylene waste, regardless of the type and density of polyethylene, using a foaming additive that is mixed into it (polyethylene), at the temperature used in the rotating polyethylene mold;
- izrada predmeta s dvoslojnom stijenkom tehnologijom rotacijskog lijeva, pri čemu je vanjska stijenka izrađena od nerecikliranog polietilena, a unutarnja stijenka od pjenastog (ekspandiranog) polietilena dobivenog recikliranjem iz razvrstanog ili nerazvrstanog polietilenskog otpada. - production of objects with a double-layered wall using rotary casting technology, where the outer wall is made of non-recycled polyethylene, and the inner wall is made of foamed (expanded) polyethylene obtained by recycling from sorted or unsorted polyethylene waste.
Stanje tehnike State of the art
Problem recikliranja otpada izrađenog od termoplastičnih polimernih materijala (polietilena, polipropilena, polivinil klorida, polietilen tereftalata itd., te njihovih smjesa i kopolimera) do danas nije zadovoljavajuće riješen, tako da većina plastičnog otpada izrađenog od navedenih termoplastičnih polimernih materijala završava na odlagalištu otpada. Recikliranje navedenih termoplastičnih polimernih materijala uglavnom je ograničeno na ekstruziju i injekcijsko prešanje, pri čemu se otpadni termoplastični polimerni materijal u određenom udjelu miješa s novom sirovinom, i kao takav ponovo iskorištava u procesu proizvodnje. Otpad izrađen od termoplastičnih polimernih materijala do sada se nije koristio (reciklirao) u rotacijskom lijevu. The problem of recycling waste made from thermoplastic polymer materials (polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, etc., and their mixtures and copolymers) has not been satisfactorily solved to date, so that the majority of plastic waste made from the aforementioned thermoplastic polymer materials ends up in landfills. The recycling of the aforementioned thermoplastic polymer materials is mainly limited to extrusion and injection molding, whereby the waste thermoplastic polymer material is mixed with a new raw material in a certain proportion, and reused as such in the production process. Waste made from thermoplastic polymer materials has not been used (recycled) in rotary casting until now.
Do sada se za ispunu šupljina predmeta dobivenih rotacijskim lijevom koristio uglavnom polistiren ili poliuretan. Until now, polystyrene or polyurethane was mainly used to fill the cavities of objects obtained by rotary left.
Izlaganje suštine izuma Presentation of the essence of the invention
Pod pojmom polietilena ovdje se podrazumijeva svaki polimerni materijal u kojem je udio polietilena veći od 50 %, bez obzira na vrstu i gustoću polietilena, primjerice: polietilen niske, srednje i visoke gustoće; linearni polietilen niske gustoće; mješavine (blendovi) polietilena različitih gustoća; mješavine (blendovi) polietilena i ostalih termoplastičnih polimera, u kojima je udio polietilena veći od 50 % (primjerice, mješavine polietilena i polipropilena, polietilena i polibutadiena, polietilena i etilen/vinil acetat kopolimera itd.); kopolimeri etilena i drugih monomera, u kojima je maseni udio etilenskih monomernih jedinica veći od 50 % (primjerice kopolimeri etilena i vinil acetata, etilena i propilena, etilena i butena itd.). The term polyethylene here means any polymer material in which the proportion of polyethylene is greater than 50%, regardless of the type and density of polyethylene, for example: low, medium and high density polyethylene; linear low density polyethylene; mixtures (blends) of polyethylene of different densities; mixtures (blends) of polyethylene and other thermoplastic polymers, in which the proportion of polyethylene is greater than 50% (for example, mixtures of polyethylene and polypropylene, polyethylene and polybutadiene, polyethylene and ethylene/vinyl acetate copolymer, etc.); copolymers of ethylene and other monomers, in which the mass fraction of ethylene monomer units is greater than 50% (for example, copolymers of ethylene and vinyl acetate, ethylene and propylene, ethylene and butene, etc.).
Primarni cilj izuma je iskorištavanje razvrstanog ili nerazvrstanog polietilenskog otpada za izradu sirovine za dobivanje pjenastog (ekspandiranog) polietilena, koji bi se koristio za oblaganje unutrašnjih stranica predmeta dobivenih tehnologijom rotacijskog lijeva ili ispunu predmeta, pri čemu je vanjski dio stijenke predmeta izrađen od nerecikliranog polietilena, a unutarnji dio stijenke predmeta od pjenastog recikliranog polietilena. The primary goal of the invention is the utilization of sorted or unsorted polyethylene waste for the production of raw materials for obtaining foamed (expanded) polyethylene, which would be used to cover the inner sides of objects obtained by rotary casting technology or to fill objects, whereby the outer part of the wall of the object is made of non-recycled polyethylene. and the inner part of the object wall is made of foam recycled polyethylene.
Sekundarni cilj izuma je povećavanje mehaničke čvrstoće stijenke takvih proizvoda te snižavanje njihove proizvodne cijene. The secondary goal of the invention is to increase the mechanical strength of the wall of such products and to lower their production cost.
Umješavanjem aditiva za pjenjenje u talinu polietilena, uključujući i polietilen iz razvrstanog ili nerazvrstanog polietilenskog otpada, proizvodi se sirovina za dobivanje pjenastog (ekspandiranog) polietilena. Pri temperaturi koja se koristi u rotacijskom lijevu dolazi do taljenja polietilena i termičkog raspada aditiva za pjenjenje, pri čemu se oslobađaju plinoviti produkti koji pjene (ekspandiraju) rastaljeni polietilen. Pjenasti polietilen koristi se kao supstituent polistirenu ili poliuretanu za ispunu šupljina unutar predmeta dobivenog rotacijskim lijevom, za povećanje debljine stijenke predmeta ili za ojačavanje stijenke predmeta. By mixing foaming additives into the polyethylene melt, including polyethylene from sorted or unsorted polyethylene waste, the raw material for obtaining foamed (expanded) polyethylene is produced. At the temperature used in the rotary mold, polyethylene melts and the foaming additive thermally decomposes, releasing gaseous products that foam (expand) the molten polyethylene. Polyethylene foam is used as a substitute for polystyrene or polyurethane to fill cavities inside the object obtained by rotary lamination, to increase the wall thickness of the object or to strengthen the wall of the object.
Umješavanje aditiva za pjenjenje u polietilen dobiven iz razvrstanog ili nerazvrstanog polietilenskog otpada izvodi se u talini, na temperaturi višoj od tališta polietilena, no nižoj od temperature na kojoj dolazi do termičkog raspada aditiva za pjenjenje. Ovisno o željenoj gustoći pjenastog polietilena, aditiv za pjenjenje dodaje se u količini od 0,25 do 7,5 masenih postotaka. Ovisno o vrsti polietilena i uporabljenog aditiva za pjenjenje (azodikarbonamid, benzensulfonil-hidrazid, dinitrozo-pentametilen-tetramin, hidrogenkarbonati alkalijskih i zemnoalkalijskih metala, toluensulfonil-hidrazid), temperatura na kojoj se vrši umješavanje aditiva za pjenjenje u talinu polietilena varira između 60 °C i 135 °C. Da bi se postigla jednolika raspodjela veličina pora prilikom formiranja pjenastog polietilena, pored aditiva za pjenjenje u polietilen se može umiješati i odgovarajuće sredstvo za nukleaciju (cinkov stearat, talk, kaolin i sl.) u količini od 0,5 do 5 masenih postotaka. Kod uporabe hidrogenkarbonata alkalijskih i zemnoalkalijskih metala kao aditiva za pjenjenje, primjerice natrijevog hidrogenkarbonata, poželjno je u smjesu dodati i promotor pjenjenja, tzv. koagens, primjerice limunsku ili stearinsku kiselinu u količini od 0,05 do 2,5 masena postotka. Po potrebi, ovisno o željenim svojstvima dobivenog pjenastog polietilena, u smjesu se može dodati i sredstvo za umrežavanje polietilena (izabrano iz skupine organskih peroksida, polisulfonazida, azidoformata ili kinondioksima, uobičajeno korištenih u struci), katalizator umrežavanja (cinkov stearat, cinkov oktanoat, cinkov laurat ili cinkov naftenat), punila (staklena vlakna, kalcijev karbonat, kaolin itd.), te ostali aditivi korišteni u struci (usporivači gorenja, UV stabilizatori i sl.). Dobivena homogena smjesa aditiva za pjenjenje te, po želji, drugih aditiva, s polietilenom iz razvrstanog ili nerazvrstanog polietilenskog otpada usitnjava se mljevenjem u mlinu do željene veličine čestica (obično manje od 1 mm) i u obliku praha koristi se kao sirovina za rotacijski lijev. The mixing of foaming additives into polyethylene obtained from sorted or unsorted polyethylene waste is performed in the melt, at a temperature higher than the melting point of polyethylene, but lower than the temperature at which the thermal decomposition of the foaming additives occurs. Depending on the desired density of the foamed polyethylene, the foaming additive is added in an amount of 0.25 to 7.5 percent by mass. Depending on the type of polyethylene and the foaming additive used (azodicarbonamide, benzenesulfonyl-hydrazide, dinitroso-pentamethylene-tetramine, hydrogen carbonates of alkali and alkaline earth metals, toluenesulfonyl-hydrazide), the temperature at which the foaming additive is mixed into the polyethylene melt varies between 60 °C and 135 °C. In order to achieve a uniform distribution of pore sizes during the formation of foamed polyethylene, in addition to foaming additives, a suitable nucleating agent (zinc stearate, talc, kaolin, etc.) can be mixed into the polyethylene in an amount of 0.5 to 5 percent by mass. When using hydrogen carbonates of alkali and alkaline earth metals as additives for foaming, for example sodium hydrogen carbonate, it is preferable to add a foaming promoter to the mixture, the so-called coagent, for example citric or stearic acid in an amount of 0.05 to 2.5 percent by mass. If necessary, depending on the desired properties of the obtained foamed polyethylene, a polyethylene crosslinking agent (chosen from the group of organic peroxides, polysulfonazides, azidoformates or quinonedioxime, commonly used in the field), a crosslinking catalyst (zinc stearate, zinc octanoate, zinc laurate or zinc naphthenate), fillers (glass fibers, calcium carbonate, kaolin, etc.), and other additives used in the profession (flame retardants, UV stabilizers, etc.). The obtained homogeneous mixture of foaming additives and, if desired, other additives, with polyethylene from sorted or unsorted polyethylene waste is crushed by grinding in a mill to the desired particle size (usually less than 1 mm) and in powder form is used as a raw material for rotary casting.
Za formiranje vanjskog dijela stijenke predmeta koji se izrađuje tehnologijom rotacijskog lijeva upotrebljava se nereciklirani polietilen, s dodatkom UV stabilizatora, pigmenata i ostalih aditiva korištenih u tehnologiji rotacijskog lijeva. Na taj način dobiva se glatka vanjska stijenka, debljina koje ovisi o masi polietilena i veličini (površini) kalupa. Takav polietilen usipava se u kalup u obliku slobodnog praha, tijekom zagrijavanja i rotacije kalupa prvi se sinterira uz stijenku kalupa i formira vanjski sloj stijenke predmeta. Non-recycled polyethylene is used to form the outer part of the wall of the object, which is made by rotary casting technology, with the addition of UV stabilizers, pigments and other additives used in rotary casting technology. In this way, a smooth outer wall is obtained, the thickness of which depends on the mass of polyethylene and the size (surface) of the mold. Such polyethylene is poured into the mold in the form of free powder, during the heating and rotation of the mold it is first sintered against the wall of the mold and forms the outer layer of the wall of the object.
Unutrašnji pjenasti (ekspandirani) sloj stijenke predmeta formira se od polietilena dobivenog iz razvrstanog ili nerazvrstanog polietilenskog otpada, u koji je (polietilen) dodan aditiv za pjenjenje, te ostali aditivi, ovisno o željenim svojstvima unutarnjeg sloja stijenke. Polietilenski prah od kojeg se sinteriranjem formira unutarnji pjenasti sloj stijenke predmeta u kalup se usipava nakon što je formiran (sinteriran) vanjski sloj stijenke predmeta. Druga je mogućnost da se polietilenski prah od kojeg će se formirati unutarnji sloj stijenke upakira u vrećice izrađene od polietilena niske gustoće, takve da je debljina stijenke vrećice manja od 0,2 mm, i u kalup stavi prije početka zagrijavanja i rotacije kalupa, zajedno s polietilenskim prahom koji formira vanjski sloj stijenke predmeta. Nakon što se sinterira vanjska stijenka predmeta, rastalit će se vrećice s polietilenskim prahom u koji je umiješan aditiv za pjenjenje, i taj će polietilenski prah, sinteriranjem na već formirani vanjski sloj stijenke predmeta, formirati pjenasti unutarnji sloj. The inner foam (expanded) layer of the object's wall is formed from polyethylene obtained from sorted or unsorted polyethylene waste, to which a foaming additive (polyethylene) has been added, and other additives, depending on the desired properties of the inner layer of the wall. Polyethylene powder, from which the inner foam layer of the object wall is formed by sintering, is poured into the mold after the outer layer of the object wall has been formed (sintered). Another possibility is that the polyethylene powder from which the inner layer of the wall will be formed is packed in bags made of low-density polyethylene, such that the thickness of the bag wall is less than 0.2 mm, and placed in the mold before the start of heating and rotation of the mold, together with the polyethylene with the powder that forms the outer layer of the object's wall. After the outer wall of the object is sintered, the bags with polyethylene powder mixed with a foaming additive will melt, and this polyethylene powder, by sintering on the already formed outer layer of the object wall, will form a foam inner layer.
Po želji, s polietilenskim prahom koji se koristi za formiranje unutarnjeg dijela stijenke predmeta mogu se pomiješati i sječena staklena, ugljična ili sintetička vlakna, u cilju ojačavanja unutarnjeg dijela stijenke proizvoda. Također, unutarnja stijenka predmeta može se ojačati metalnom armaturom, postupkom koji je uobičajen u struci. If desired, chopped glass, carbon or synthetic fibers can be mixed with the polyethylene powder used to form the inner part of the product wall, in order to strengthen the inner part of the product wall. Also, the inner wall of the object can be reinforced with metal reinforcement, a procedure that is common in the profession.
Po završetku rotacijskog lijeva dobivaju se predmeti glatkog ruba i glatke vanjske stijenke, koji su iznutra potpuno ili djelomično ispunjeni pjenastim polietilenom. S obzirom na manju gustoću ekspandiranog polietilena, u odnosu na neekspandirani polietilen, takvi predmeti imaju deblju stijenku od predmeta koji su izrađeni od neekspandiranog polietilena iste mase, te su stoga i čvršći. Osim veće čvrstoće stijenke, predmeti izrađeni opisanom tehnologijom odlikuju se i slabom provodnošću topline i zvuka (dobri su toplinski i zvučni izolatori). Upon completion of rotary casting, objects with a smooth edge and a smooth outer wall are obtained, which are completely or partially filled with foamed polyethylene from the inside. Due to the lower density of expanded polyethylene, compared to non-expanded polyethylene, such objects have a thicker wall than objects made of non-expanded polyethylene of the same mass, and are therefore stronger. In addition to greater wall strength, objects made with the described technology are characterized by low heat and sound conductivity (they are good heat and sound insulators).
Primjena kod izrade malih brodica Application in the construction of small boats
Komercijalna proizvodnja brodica do otprilike 20 m dužine danas se uglavnom bazira na poliesterskim smolama ojačanim staklenim ili ugljikovim vlaknima. Poliesterske smole ojačane vlaknima nisu skupe i dovoljno su čvrste za izradu korita i nadgrađa srednje velikih plovila, no posjeduju i neke negativne osobine: Today, the commercial production of boats up to approximately 20 m in length is mainly based on polyester resins reinforced with glass or carbon fibers. Fiber-reinforced polyester resins are not expensive and are strong enough to make the bottoms and superstructures of medium-sized vessels, but they also have some negative properties:
- Izrada plovila nanošenjem poliesterske smole sloj po sloj relativno je dugotrajna (primjerice, za brodice duljine oko 10 m izrada traje i do tjedan dana). To poskupljuje izradu jer onemogućuje serijsku proizvodnju, pa se izrada oslanja isključivo na ručni rad. - Crafting a boat by applying polyester resin layer by layer is relatively long-lasting (for example, for a boat about 10 m long, it takes up to a week). This makes production more expensive because it makes mass production impossible, so production relies exclusively on manual labor.
- Trupovi izrađeni od poliesterske smole ojačane vlaknima krti su i podložni osmozi. - Hulls made of fiber-reinforced polyester resin are fragile and subject to osmosis.
- Poliesterski otpad ne može se reciklirati i regenerirati. - Polyester waste cannot be recycled or regenerated.
Do sada je izrada plovila iz polietilena uspješno izvedena samo u slučaju malih plovila (sandoline, kajaci, kanui itd.). Ta plovila bila su lijevana od običnog (neekspandiranog) polietilena, iz jednog komada, a šupljine u njima bile su po potrebi naknadno ispunjene polistirenom ili poliuretanom. Until now, the production of polyethylene vessels has been successfully carried out only in the case of small vessels (sandolins, kayaks, canoes, etc.). These vessels were cast from ordinary (non-expanded) polyethylene, from one piece, and the cavities in them were subsequently filled with polystyrene or polyurethane if necessary.
Predmeti izrađeni rotacijskim lijevom iz ekspandiranog polietilena dobivenog iz razvrstanog ili nerazvrstanog polietilenskog otpada (posebice polietilen visoke gustoće te umreženi polietilen) u pogledu čvrstoće zadovoljavaju zahtjeve koji se postavljaju kod izrade plovila male i srednje veličine. Izrada trupa plovila iz ekspandiranog polietilena dozvoljava da se na jednom kalupu dnevno izradi više odljevaka, što omogućuje prijelaz s ručne proizvodnje na serijsku proizvodnju. Samim tim snižava se i cjena konačnog proizvoda, s obzirom da: Objects made by rotary left from expanded polyethylene obtained from sorted or unsorted polyethylene waste (especially high-density polyethylene and cross-linked polyethylene) in terms of strength meet the requirements set for the construction of small and medium-sized vessels. The production of vessel hulls from expanded polyethylene allows multiple castings to be made on one mold per day, which enables the transition from manual production to serial production. This also lowers the price of the final product, given that:
a) Regenerirani polietilen jeftiniji je od neregeneriranog polietilena. Pored toga, plovila izrađena od polietilena ekološki su prihvatljiva jer se, za razliku od plovila izrađenih od poliestera, mogu reciklirati. a) Regenerated polyethylene is cheaper than non-regenerated polyethylene. In addition, vessels made of polyethylene are environmentally friendly because, unlike vessels made of polyester, they can be recycled.
b) Velikoserijska proizvodnja snižava cijenu pojedinom odljevku b) Large-scale production lowers the price of an individual casting
c) Otpada dugotrajni i skupi specijalizirani ljudski ručni rad nanošenja poliesterskih smola i vlakana sloj po sloj, vezan uz pomno istiskivanje mjehurića zraka kako bi se moguća osmoza smanjila na najmanju moguću mjeru. c) The long-term and expensive specialized human manual work of applying polyester resins and fibers layer by layer, associated with the careful squeezing out of air bubbles in order to minimize possible osmosis, is eliminated.
d) Dobrim projektiranjem plovila se mogu raditi i iz više dijelova, tako da se dijelovi trupa ili nadgrađa posebno izrade rotacijskim ljevom. Prednost takvog postupka je i to, što se plovilo izrađeno od više dijelova može lakše transportirati, te sastaviti (primjerice zavarivanjem) u “brodogradilištima” na obali. Nadalje, opremanje brodova opremom i motorima lakše je dok dijelovi nisu međusobno spojeni, a i popravci oštećenog plovila mogu se izvršiti zamjenom samo oštećenog dijela. d) With good design, vessels can be made from several parts, so that parts of the hull or superstructure are specially made by rotary casting. The advantage of such a procedure is that a vessel made of several parts can be transported more easily and assembled (for example by welding) in "shipyards" on the coast. Furthermore, equipping ships with equipment and engines is easier until the parts are connected to each other, and repairs to a damaged vessel can be carried out by replacing only the damaged part.
PRIMJERI EXAMPLES
Da bi se utvrdio optimalan udio pojedinih aditiva koji se u polietilen dodaju kako bi se postigla njegova ekspanzija (pjenjenje) tijekom postupka rotacijskog lijeva, izrađeni su pokusni uzorci s različitim smjesama polietilena i aditiva. Pokusni uzorci izrađeni su u kalupima cilindričnog oblika, promjera 22 cm i visine 15 cm (kalup A), odnosno 60 cm (kalup B). Smjesa za koju je ustanovljeno da ima optimalan sastav korištena je u izradi pokusnog odljevka čamca u kalupu dužine 298 cm, visine 60 cm i širine (na polovici duljine trupa) 120 cm (kalup C). In order to determine the optimal proportion of certain additives that are added to polyethylene in order to achieve its expansion (foaming) during the rotary casting process, test samples were made with different mixtures of polyethylene and additives. Test samples were made in cylindrical molds with a diameter of 22 cm and a height of 15 cm (mould A) and 60 cm (mould B). The mixture that was found to have the optimal composition was used in the production of an experimental casting of a boat in a mold with a length of 298 cm, a height of 60 cm and a width (at half the length of the hull) of 120 cm (mould C).
Pokus 1 Experiment 1
Korištena je sirovina sljedećeg sastava: The raw material with the following composition was used:
linearni polietilen niske gustoće (RIGIDEX, BP) 10 kg linear low-density polyethylene (RIGIDEX, BP) 10 kg
natrijev hidrogenkarbonat 150 g sodium bicarbonate 150 g
Smjesa polietilena i natrijevog hidrogenkarbonata homogenizirana je u talini, ekstuzijom pri temperaturi od 125 °C. Nakon ekstruzije, homogenizirana smjesa poletilena i natrijevog hidrogenkarbonata samljevena je u prah čija je veličina čestica bila manja od 0,8 mm i taj je prah korišten kao sirovina za rotacijski lijev. U kalup A stavljeno je 0,75 kg dobivene praškaste sirovine, i kalup je 10 minuta rotiran biaksijalno, uz zagrijavanje na otvorenom plamenu. Dobiveni pokusni odljevak imao je oblik šupljeg cilindra s krutom stijenkom od ekspandiranog polietilena, gustoće 0,42 g/cm3. Veličina pora ekspandiranog polietilena bila je između 0,5 i 3 mm. Na stijenci predmeta bile su jasno uočljive deformacije u obliku nepravilnih ulegnuća dubine do 2 cm. The mixture of polyethylene and sodium hydrogen carbonate was homogenized in the melt, by extrusion at a temperature of 125 °C. After extrusion, the homogenized mixture of polyethylene and sodium hydrogencarbonate was ground into a powder whose particle size was less than 0.8 mm and this powder was used as raw material for rotary casting. 0.75 kg of the resulting powdered raw material was placed in mold A, and the mold was rotated biaxially for 10 minutes, with heating over an open flame. The obtained experimental casting had the shape of a hollow cylinder with a rigid wall made of expanded polyethylene, density 0.42 g/cm3. The pore size of the expanded polyethylene was between 0.5 and 3 mm. There were clearly visible deformations on the wall of the object in the form of irregular depressions up to 2 cm deep.
Pokus 2 Experiment 2
Korištena je sirovina sljedećeg sastava: The raw material with the following composition was used:
polietilen niske gustoće (OKITEN) 10 kg low density polyethylene (OKITEN) 10 kg
natrijev hidrogenkarbonat 150 g sodium bicarbonate 150 g
Smjesa polietilena i natrijevog hidrogenkarbonata homogenizirana je u talini, ekstuzijom pri temperaturi od 90 °C. Nakon ekstruzije, homogenizirana smjesa poletilena i natrijevog hidrogenkarbonata samljevena je u prah čija je veličina čestica bila manja od 0,8 mm i taj je prah korišten kao sirovina za rotacijski lijev. U kalup A stavljeno je 0,75 kg dobivene praškaste sirovine, i kalup je 10 minuta rotiran biaksijalno, uz zagrijavanje na otvorenom plamenu. Dobiveni pokusni odljevak imao je oblik šupljeg cilindra s elastičnom stijenkom od ekspandiranog polietilena, gustoće 0,45 g/cm3. Veličina pora ekspandiranog polietilena bila je između 0,5 i 3 mm. Na stijenci predmeta bile su jasno uočljive deformacije u obliku nepravilnih ulegnuća dubine do 2 cm. The mixture of polyethylene and sodium hydrogen carbonate was homogenized in the melt by extrusion at a temperature of 90 °C. After extrusion, the homogenized mixture of polyethylene and sodium hydrogencarbonate was ground into a powder whose particle size was less than 0.8 mm and this powder was used as raw material for rotary casting. 0.75 kg of the resulting powdered raw material was placed in mold A, and the mold was rotated biaxially for 10 minutes, with heating over an open flame. The resulting experimental casting had the shape of a hollow cylinder with an elastic wall made of expanded polyethylene, density 0.45 g/cm3. The pore size of the expanded polyethylene was between 0.5 and 3 mm. There were clearly visible deformations on the wall of the object in the form of irregular depressions up to 2 cm deep.
Pokus 3 Experiment 3
Korištena je sirovina sljedećeg sastava: The raw material with the following composition was used:
linearni polietilen niske gustoće (RIGIDEX) 10 kg linear low-density polyethylene (RIGIDEX) 10 kg
natrijev hidrogenkarbonat 150 g sodium bicarbonate 150 g
limunska kiselina 50 g citric acid 50 g
magnezijev stearat 75 g magnesium stearate 75 g
Smjesa polietilena i aditiva homogenizirana je u talini, ekstuzijom pri temperaturi od 115 °C. Nakon ekstruzije, homogenizirana smjesa poletilena i natrijevog hidrogenkarbonata samljevena je u prah čija je veličina čestica bila manja od 0,8 mm i taj je prah korišten kao sirovina za rotacijski lijev. U kalup B stavljeno je 2 kg dobivene praškaste sirovine, i kalup je 15 minuta rotiran biaksijalno, uz zagrijavanje na otvorenom plamenu. Dobiveni pokusni odljevak imao je oblik šupljeg cilindra s krutom stijenkom od ekspandiranog polietilena, gustoće 0,385 g/cm3. Veličina pora ekspandiranog polietilena bila je manja od 1 mm. Vanjska površina stijenke predmeta bila je glatka, bez vidljivih deformacija ili defekata. The mixture of polyethylene and additives is homogenized in the melt, by extrusion at a temperature of 115 °C. After extrusion, the homogenized mixture of polyethylene and sodium hydrogencarbonate was ground into a powder whose particle size was less than 0.8 mm and this powder was used as raw material for rotary casting. 2 kg of the obtained powdered raw material was placed in mold B, and the mold was rotated biaxially for 15 minutes, while heating on an open flame. The obtained experimental casting had the shape of a hollow cylinder with a rigid wall made of expanded polyethylene, density 0.385 g/cm3. The pore size of the expanded polyethylene was less than 1 mm. The outer surface of the object's wall was smooth, without visible deformations or defects.
Pokus 4 Experiment 4
Korištena je sirovina sljedećeg sastava: The raw material with the following composition was used:
polietilen visoke gustoće, 10 kg high density polyethylene, 10 kg
(dobiven iz otpada ambalaže /sanduka/ za boce za piće) (obtained from waste packaging / crates / for drinking bottles)
natrijev hidrogenkarbonat 250 g sodium bicarbonate 250 g
limunska kiselina 30 g citric acid 30 g
magnezijev stearat 75 g magnesium stearate 75 g
2,5-dimetil-2,5-di(t-butil-peroksi)heksan 25 cm3 2,5-dimethyl-2,5-di(t-butyl-peroxy)hexane 25 cm3
Smjesa polietilena i aditiva homogenizirana je u talini, ekstuzijom pri temperaturi od 115 °C. Nakon ekstruzije, homogenizirana smjesa poletilena i natrijevog hidrogenkarbonata samljevena je u prah čija je veličina čestica bila manja od 0,8 mm i taj je prah korišten kao sirovina za rotacijski lijev. U kalup B stavljeno je 2 kg dobivene praškaste sirovine, i kalup je 15 minuta rotiran biaksijalno, uz zagrijavanje na otvorenom plamenu. Dobiveni pokusni odljevak imao je oblik šupljeg cilindra s izrazito krutom stijenkom od ekspandiranog polietilena, gustoće 0,26 g/cm3. Veličina pora ekspandiranog polietilena bila je manja od 1 mm. Vanjska površina stijenke predmeta bila je glatka, bez vidljivih deformacija ili defekata. The mixture of polyethylene and additives is homogenized in the melt, by extrusion at a temperature of 115 °C. After extrusion, the homogenized mixture of polyethylene and sodium hydrogencarbonate was ground into a powder whose particle size was less than 0.8 mm and this powder was used as raw material for rotary casting. 2 kg of the obtained powdered raw material was placed in mold B, and the mold was rotated biaxially for 15 minutes, while heating on an open flame. The obtained experimental casting had the shape of a hollow cylinder with an extremely rigid wall made of expanded polyethylene, density 0.26 g/cm3. The pore size of the expanded polyethylene was less than 1 mm. The outer surface of the object's wall was smooth, without visible deformations or defects.
Pokus 5 Experiment 5
Korištena je sirovina jednakog sastava i načina pripreme kao i u pokusu 4. U kalup B stavljeno je 0,5 kg linearnog polietilena niske gustoće i 2 kg sirovine kao u pokusu 4, s time da je cijela masa sirovine za dobivanje ekspandiranog polietilena raspodijeljena u 4 tanke polietilenske vrećice, i u kalup stavljena zatvorena u te vrećice. Kalup je 18 minuta rotiran biaksijalno, uz zagrijavanje na otvorenom plamenu. Dobiveni pokusni odljevak imao je oblik šupljeg cilindra s krutom stijenkom koja se sastojala od dva oštro odijeljena sloja: vanjskog sloja od neekspandiranog polietilena, debljine oko 0,3 mm, i unutrašnjeg sloja od ekspandiranog polietilena, debljine oko 2 cm i gustoće 0,26 g/cm3. Veličina pora ekspandiranog polietilena bila je manja od 1 mm. Vanjska površina stijenke predmeta bila je glatka, bez vidljivih deformacija ili defekata. Raw material with the same composition and method of preparation as in experiment 4 was used. In mold B, 0.5 kg of linear low-density polyethylene and 2 kg of raw material were placed as in experiment 4, with the fact that the entire mass of raw material for obtaining expanded polyethylene was distributed into 4 thin polyethylene bags, and placed in a mold closed in those bags. The mold was rotated biaxially for 18 minutes, with heating over an open flame. The obtained experimental casting had the shape of a hollow cylinder with a rigid wall consisting of two sharply separated layers: an outer layer of non-expanded polyethylene, about 0.3 mm thick, and an inner layer of expanded polyethylene, about 2 cm thick and 0.26 g in density /cm3. The pore size of the expanded polyethylene was less than 1 mm. The outer surface of the object's wall was smooth, without visible deformations or defects.
Pokus 6 Experiment 6
U kalup C stavljeno je 20 kg linearnog polietilena niske gustoće i kalup je 20 minuta rotiran na otvorenom plamenu. Nakon što se sav polietilen sinterirao uz stijenku kalupa, kroz za to predviđen otvor u kalup je stavljeno 25 kg polietilena priređenog kao u pokusu 4. Kalup je nastavljen rotirati daljnjih 25 minuta. Dobiveni pokusni odljevak čamca imao je krutu stijenku koja se sastojala od dva oštro odijeljena sloja: vanjskog sloja od neekspandiranog polietilena, debljine oko 2 mm, i unutrašnjeg sloja od ekspandiranog polietilena, debljine oko 10 mm i gustoće 0,26 g/cm3. Veličina pora ekspandiranog polietilena bila je manja od 1 mm. Vanjska površina stijenke čamca bila je glatka, bez vidljivih deformacija ili defekata. 20 kg of linear low-density polyethylene was placed in mold C and the mold was rotated for 20 minutes over an open flame. After all the polyethylene was sintered against the wall of the mold, 25 kg of polyethylene prepared as in experiment 4 was placed in the mold through the opening provided for it. The mold continued to rotate for another 25 minutes. The resulting experimental casting of the boat had a rigid wall consisting of two sharply separated layers: an outer layer of unexpanded polyethylene, about 2 mm thick, and an inner layer of expanded polyethylene, about 10 mm thick and 0.26 g/cm3 density. The pore size of the expanded polyethylene was less than 1 mm. The outer surface of the boat wall was smooth, without visible deformations or defects.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HR20020059 HRPK20020059B1 (en) | 2002-01-24 | 2002-01-24 | Recycling process of waste polyethylene for making articles of double-layer wall by rotational casting |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HR20020059 HRPK20020059B1 (en) | 2002-01-24 | 2002-01-24 | Recycling process of waste polyethylene for making articles of double-layer wall by rotational casting |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| HRP20020059A2 true HRP20020059A2 (en) | 2003-08-31 |
| HRPK20020059B1 HRPK20020059B1 (en) | 2004-12-31 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| HR20020059 HRPK20020059B1 (en) | 2002-01-24 | 2002-01-24 | Recycling process of waste polyethylene for making articles of double-layer wall by rotational casting |
Country Status (1)
| Country | Link |
|---|---|
| HR (1) | HRPK20020059B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021222984A1 (en) * | 2020-05-05 | 2021-11-11 | Pact Group Industries (ANZ) Pty Ltd | Method and formulation for rotomoulding recycled polymer and products thereof |
-
2002
- 2002-01-24 HR HR20020059 patent/HRPK20020059B1/en not_active IP Right Cessation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021222984A1 (en) * | 2020-05-05 | 2021-11-11 | Pact Group Industries (ANZ) Pty Ltd | Method and formulation for rotomoulding recycled polymer and products thereof |
| EP4146450A1 (en) * | 2020-05-05 | 2023-03-15 | Pact Group Industries (ANZ) Pty Ltd | Method and formulation for rotomoulding recycled polymer and products thereof |
| EP4146450A4 (en) * | 2020-05-05 | 2024-05-15 | Pact Group Industries (ANZ) Pty Ltd | Method and formulation for rotomoulding recycled polymer and products thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| HRPK20020059B1 (en) | 2004-12-31 |
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