WO2020142031A2 - Waste polyurethane reinforced composite material - Google Patents

Waste polyurethane reinforced composite material Download PDF

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Publication number
WO2020142031A2
WO2020142031A2 PCT/TR2019/050982 TR2019050982W WO2020142031A2 WO 2020142031 A2 WO2020142031 A2 WO 2020142031A2 TR 2019050982 W TR2019050982 W TR 2019050982W WO 2020142031 A2 WO2020142031 A2 WO 2020142031A2
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WO
WIPO (PCT)
Prior art keywords
waste polyurethane
thermoplastic polymer
composite material
filament
poly
Prior art date
Application number
PCT/TR2019/050982
Other languages
French (fr)
Other versions
WO2020142031A3 (en
Inventor
Emre İNCEKARA
Original Assignee
Pi̇msa Otomoti̇v Anoni̇m Şi̇rketi̇
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Publication date
Application filed by Pi̇msa Otomoti̇v Anoni̇m Şi̇rketi̇ filed Critical Pi̇msa Otomoti̇v Anoni̇m Şi̇rketi̇
Publication of WO2020142031A2 publication Critical patent/WO2020142031A2/en
Publication of WO2020142031A3 publication Critical patent/WO2020142031A3/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D99/00—Subject matter not provided for in other groups of this subclass
    • B29D99/0078—Producing filamentary materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/203—Solid polymers with solid and/or liquid additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
    • 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
    • C08J2355/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00
    • C08J2355/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • 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
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • 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
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • 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
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • 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

  • Invention relates to waste polyurethane reinforced composite material and a method for production of it.
  • the invention particularly relates to a waste polyurethane composite material and filament for use in FDM type 3-dimension printers.
  • burrs occur on automotive parts made from thermoset plastics such as polyurethane in automotive sector.
  • the burrs are separated from the product parts by means of cutting and are shipped for discard after storing as waste.
  • the wastes occurring in high amounts are not used and the transport costs incurred during transfer are also high.
  • thermoset polyurethane burrs are not possible chemically. For that reason, said burrs are burnt for discarding. This causes damage onto environment.
  • WO2018123763 A1 discloses a material in form of filament obtained by mixing PLA with a polyamide copolymer at a proper rate. Said filament material is used as raw material for production of objects of improved flexibility and wearing at 3D printers.
  • thermoplastic elastomer is an olephenic elastomer and a styrene elastomer.
  • the present invention relates to polyurethane reinforced composite material, filament and production methods thereof meeting the needs mentioned above, eliminating all disadvantages and providing some additional advantages.
  • Primary aim of the invention is to produce raw material, supply simple and low cost raw material for use at 3 dimensioned printers of FDM (Fused deposition Modelling) type.
  • Another aim of the invention is to provide an environment-friendly method for recycling of waste polyurethane materials.
  • a further aim of the invention is to provide a composite material and filament with improved mechanical features for use at FDM type 3 dimensioned printers.
  • a further aim of the invention is to provide a composite material and filament with improved performance for use at FDM type 3 dimensioned printers.
  • the invention discloses a composite material for use to produced filament as raw material of an object to be configured with FDM type 3 dimensioned printers and said composite material comprises at least waste polyurethane support of a thermoplastic polymer and thermoset feature.
  • said composite material comprises thermoplastic polymer at 75 % to 90 % by weight, waste polyurethane support of 10 % to 25 % by weight wherein thermoplastic polymer and waste polyurethane rate is 100 % by weight in total.
  • said composite material comprises thermoplastic polymer in 90% by weight and polyurethane rate at 10 % by weight.
  • said composite material is in waste polyurethane reinforced powder form.
  • said waste polyurethane reinforced is in homogenous size range.
  • said waste polyurethane reinforced particulate size is about 100 pm.
  • thermoplastic polymer poly lactic acid is selected from acrylonotrile butadiene styrene, poly carbonate, poly ethylene terra phthalate and poly amide.
  • thermoplastic polymer is poly lactic acid.
  • Present invention also discloses a filament for use as raw material of an object to be configured with FDM type 3 dimensioned printer and characterized that said filament comprises a thermoplastic polymer and a waste polyurethane support of thermoset feature.
  • said filament comprises thermoplastic polymer at 75 % to 90 % by weight, waste polyurethane reinforced of 10 % to 25 % by weight wherein thermoplastic polymer and waste polyurethane reinforced is 100 % by weight in total.
  • said filament comprises thermoplastic polymer in 90 % by weight and polyurethane reinforced at 10 % by weight.
  • thermoplastic polymer poly lactic acid is selected from acrylonotrile butadiene styrene, poly carbonate, poly ethylene terra phthalate and poly amide.
  • thermoplastic polymer is poly lactic acid.
  • Present invention discloses a method for production of a waste poly urethane reinforced composite material for use to produce a filament as raw material of an object to be configured with FDM type 3 dimensioned printer and characterized that said method comprises step of mixing a thermoplastic polymer with a waste polyurethane reinforced in powder form with thermoset feature.
  • said method comprises preparation of waste polyurethane reinforced from waste polyurethane material before step of mixing said thermoplastic polymer and waste polyurethane support wherein waste polyurethane material is firstly brought into granulate form and then into powder in homogenous size range.
  • thermoplastic polymer poly lactic acid is selected from acrylonotrile butadiene styrene, poly carbonate, poly ethylene terra phthalate and poly amide.
  • thermoplastic polymer is poly lactic acid.
  • Present invention discloses a method for producing a filament for use as raw material of an object to be configured with FDM type 3 dimensioned printer and characterized that said method comprises process steps of mixing a thermoplastic polymer and a waste polyurethane reinforced in powder form of thermoset feature and obtaining a waste polyurethane reinforced composite material, heating and melting said composite material and obtaining filament by means of filament extrusion.
  • said method comprises preparation of waste polyurethane support from waste polyurethane before step of mixing said thermoplastic polymer and waste polyurethane reinforced wherein waste polyurethane support is firstly brought into granulate form and then into powder in homogenous size range.
  • said method comprises step of supply of obtained waste polyurethane reinforced composite material to filament extrusion system after step of mixing said thermoplastic polymer and waste polyurethane support.
  • FIG 1 is schematic view of steps of the method being subject of the invention
  • Present invention discloses a composite material for use to produce filament as a raw material of an object to configure with FDM (Fused Deposition Modelling) type 3 dimensioned printer.
  • Said composite material comprises at least a thermoplastic polymer and waste polyurethane reinforcement of thermoset feature.
  • FDM type 3 dimensioned printer is a 3-dimensoned printer configuring 3 dimension model (prototype or part) by casting a material in filament form into production table layer by layer through nozzle.
  • waste poly urethane material is made from polyurethane based products produced industrially. For instance, burrs remaining on product products in automotive sector during post production stage are cut and removed from product parts and thus waste polyurethane material is obtained.
  • waste poly urethane material is of thermoset feature.
  • Polyurethane materials having thermoset feature allows production of production of products having improved saturation expectation with 3D printers.
  • waste polyurethane reinforcement is obtained by means of bringing waste polyurethane material into powder form. Since the collected polyurethane materials are of various sizes and geometries, they are to be brought into granulates of 2 - 4 mm sizes at plastic crushing machines before use at plastic grinding devices of laboratory type. The obtained polyurethane waste granulates should be brought into micron sizes homogenously. Said granulates are brought into powder form by use of a plastic grinding device such as pulverised device. The obtained powder particulate sizes can be about 100 pm. Thus it will be easier to form a homogenous mixture of powders having similar sizes as well as powders of micron sizes provide effect of strengthening by composite approach in the mixture.
  • composite material or waste polyurethane reinforced composite material is obtained by means of adding said waste polyurethane support to thermoplastic polymer matrix.
  • Said waste polyurethane reinforcement can be added by means of thermoplastic polymer double screw extruder.
  • thermoplastic polymer double screw extruder thus homogenous distribution and mixture of waste polyurethane support is provided in thermoplastic matrix.
  • Temperature profile of said double screw extruder should be adjusted according to fusing temperature of thermoplastic polymer used as binding matrix, For instance, for PLA having fusing temperature of 145° - 15513, temperature pro file from supply unit up to output should use screw speed of 115°- 170°- 180°- 175°- 14513 and 75 rpm.
  • thermoplastic polymers having current use as FDM type 3 dimensioned printers are used as matrix materials.
  • thermoplastic polymers such as acrylonitrile butadiene styrene (ABS) or poly (lactic acid) (PLA) pass through metal cap heated at temperature between 250 - 3000 13 of the filaments of 3 or 1.75 mm and their thickness goes under 1 mm and also collected area goes into a glassy phase. Thermolpastic material collected on plate in fuse phase forms three dimensioned object.
  • thermoplastic polymer poly lactic acid is selected from acrylonotrile butadiene styrene (ABS), poly carbonate (PC), poly ethylene terra phthalate (PET) and poly amide (PA).
  • ABS acrylonotrile butadiene styrene
  • PC poly carbonate
  • PET poly ethylene terra phthalate
  • PA poly amide
  • thermoplastic polymer is selected from poly lactic acid and acrylonotrile - butadiene styrene ABS).
  • said thermoplastic polymer is poly lactic acid.
  • composite material comprises thermoplastic polymer at 75 % to 90 % by weight, waste polyurethane reinforcement of 10 % to 25 % by weight wherein thermoplastic polymer and waste polyurethane reinforcement is 100 % by weight in total.
  • composite material comprises thermoplastic polymer in 90 % by weight and polyurethane reinforcement at 10 % by weight.
  • composite material comprises thermoplastic polymer in 90 % by weight and polyurethane reinforcement at 10 % by weight wherein thermoplastic polymer is poly lactic acid.
  • Composite material may contain different rates depending on particulate size of thermoplastic polymer and thermoplastic polymer or waste polyurethane reinforcement. For instance in case of grinding of polyurethane wastes at nano meter level, composite material of desired features can be obtained by use of polyurethane waste at 1 - 2 % by weight. It is known that major changes are provided at too little amounts in features provided that smooth distribution of supports of nano size is provided.
  • Present invention also discloses a filament for use as raw material of an object to be configured with FDM type 3 dimension printer.
  • Said composite material comprises at least a thermoplastic polymer and waste polyurethane reinforcement of thermoset feature.
  • filament is produced by a filament extrusion device.
  • Said filament is good for use as raw material of an object that can be configured with FDM type 3 dimensioned printer,
  • Composite material is supplied to filament extrusion device for production of filament and filament is obtained in fibre form in fixed radius. It is preferred to perform this process by use of profile of temperature same as double screw extruder.
  • the invention also discloses a method for production of a waste polyurethane reinforced composite material (6) for use to produce filament as raw material of an object to configure with FDM type 3 dimensioned printer. Said method in general comprises following process steps:
  • firstly waste polyurethane reinforcement is prepared from waste polyurethane material.
  • firstly waste polyurethane material is granulated into sizes ranging from 2 to 4 mm at preferably a plastic crushing machine (2).
  • granulates are brought into powder in micron sizes homogenously preferably at a plastic grinding machine (3). It will be easier to form a homogenous mixture of powders having similar sizes and powders of micron sizes provide effect of strengthening by composite approach in the mixture.
  • the obtained waste polyurethane support is added to thermoplastic polymer matrix and mixed until a homogenous mixture is obtained by means of preferably a double screw extruder and thus waste polyurethane reinforced composite material (6) is obtained.
  • Present invention also discloses a method for producing filament for use as raw material of an object to be configured with FDM type 3 dimension printer.
  • Said method in general comprises following step after the steps A, B and C described above.
  • Filament extruder (8) or filament extrusion system is single screw extruder system with a body specifically designed for providing fixed filament diameter. Filament roller and filament rolling system are provided at extruder (8) output. In the said method, after preparation of waste polyurethane reinforced composite material, said composite material is heated and melted and then filament is obtained through filament extrusion.

Abstract

Present invention relates to a composite material for use as raw material of an object to be configured with FDM type 3 dimension printer. Said composite material comprises at least a thermoplastic polymer and waste polyurethane support of thermoset feature.

Description

WASTE POLYURETHANE REINFORCED COMPOSITE MATERIAL
Technical Field
Invention relates to waste polyurethane reinforced composite material and a method for production of it.
The invention particularly relates to a waste polyurethane composite material and filament for use in FDM type 3-dimension printers.
State of the Art
After production stage burrs occur on automotive parts made from thermoset plastics such as polyurethane in automotive sector. The burrs are separated from the product parts by means of cutting and are shipped for discard after storing as waste. The wastes occurring in high amounts are not used and the transport costs incurred during transfer are also high.
Basically, recycling of thermoset polyurethane burrs is not possible chemically. For that reason, said burrs are burnt for discarding. This causes damage onto environment.
Today at 3D printers having FDM (Fused Deposition Modelling) or FFM (Fused Filament Fabrication) technology having the most common use in 3D (three dimension) printer technologies and carried to a point where everybody can get with small budgets, objects are built by means of fusing raw materials called filament and casting thereof in layers. In general PLA (poly lactic acid) and ABS (acrylonitrile butadiene styrene) thermoplastics are used as raw material. In addition, raw materials such as PETG (Glycol modified poly ethylene terra phthalate), HIPS (High Impact Polystyrene), PVA (Poly vinyl alcohol), Nylon are also used. Generally mixed at rate of 30 - 40 % are also special materials such as wood, plant shell, bamboo, bronze, brass, copper, flexible PLA, PLA sensitive to heat and light, carbon fibre and antibacterial filaments.
Today development of plastic materials having improved features for use in 3D printer technology is continued. On the other hand, products obtained as a result of studies having high engineering costs have high costs too. Therefore, it is not likely to have spreading use of such products.
The document numbered WO2018123763 A1 discloses a material in form of filament obtained by mixing PLA with a polyamide copolymer at a proper rate. Said filament material is used as raw material for production of objects of improved flexibility and wearing at 3D printers.
The document numbered WO2018150599 A1 discloses a poly lactic acid and a thermoplastic elastomer composite contained to configure filaments used as a raw material of a printed article printed by a 3D printer using FDM. Said thermoplastic elastomer is an olephenic elastomer and a styrene elastomer.
Related art needs development of raw materials providing advantages over filament types such as conventional PLA and ABS in terms of mechanical features and also easy to produce and with lower cost.
In conclusion, because of above mentioned negativities and inadequacy of present solutions, it has been necessary to make a development in the related art in order to prevent and eliminate the problems related to recycling of polyurethane materials of waste thermoset feature as well as raw material and filaments used in 3D printers.
Aim of the Invention
The present invention relates to polyurethane reinforced composite material, filament and production methods thereof meeting the needs mentioned above, eliminating all disadvantages and providing some additional advantages.
Primary aim of the invention is to produce raw material, supply simple and low cost raw material for use at 3 dimensioned printers of FDM (Fused deposition Modelling) type.
Another aim of the invention is to provide an environment-friendly method for recycling of waste polyurethane materials.
A further aim of the invention is to provide a composite material and filament with improved mechanical features for use at FDM type 3 dimensioned printers. A further aim of the invention is to provide a composite material and filament with improved performance for use at FDM type 3 dimensioned printers.
In order to achieve above mentioned aims, the invention discloses a composite material for use to produced filament as raw material of an object to be configured with FDM type 3 dimensioned printers and said composite material comprises at least waste polyurethane support of a thermoplastic polymer and thermoset feature.
In a preferred embodiment of the invention, said composite material comprises thermoplastic polymer at 75 % to 90 % by weight, waste polyurethane support of 10 % to 25 % by weight wherein thermoplastic polymer and waste polyurethane rate is 100 % by weight in total.
In another preferred embodiment of the invention said composite material comprises thermoplastic polymer in 90% by weight and polyurethane rate at 10 % by weight.
In another preferred embodiment of the invention, said composite material is in waste polyurethane reinforced powder form.
In a preferred embodiment of the invention, said waste polyurethane reinforced is in homogenous size range.
In another preferred embodiment of the invention, said waste polyurethane reinforced particulate size is about 100 pm.
In another embodiment of the invention, said thermoplastic polymer poly lactic acid is selected from acrylonotrile butadiene styrene, poly carbonate, poly ethylene terra phthalate and poly amide.
In another preferred embodiment of the invention, said thermoplastic polymer is poly lactic acid.
Present invention also discloses a filament for use as raw material of an object to be configured with FDM type 3 dimensioned printer and characterized that said filament comprises a thermoplastic polymer and a waste polyurethane support of thermoset feature. In a preferred embodiment of the invention, said filament comprises thermoplastic polymer at 75 % to 90 % by weight, waste polyurethane reinforced of 10 % to 25 % by weight wherein thermoplastic polymer and waste polyurethane reinforced is 100 % by weight in total.
In another preferred embodiment of the invention said filament comprises thermoplastic polymer in 90 % by weight and polyurethane reinforced at 10 % by weight.
In another embodiment of the invention, said thermoplastic polymer poly lactic acid (PLA) is selected from acrylonotrile butadiene styrene, poly carbonate, poly ethylene terra phthalate and poly amide.
In another preferred embodiment of the invention, said thermoplastic polymer is poly lactic acid.
Present invention discloses a method for production of a waste poly urethane reinforced composite material for use to produce a filament as raw material of an object to be configured with FDM type 3 dimensioned printer and characterized that said method comprises step of mixing a thermoplastic polymer with a waste polyurethane reinforced in powder form with thermoset feature.
In a preferred embodiment of the invention, said method comprises preparation of waste polyurethane reinforced from waste polyurethane material before step of mixing said thermoplastic polymer and waste polyurethane support wherein waste polyurethane material is firstly brought into granulate form and then into powder in homogenous size range.
In a preferred embodiment of the invention, thermoplastic polymer poly lactic acid is selected from acrylonotrile butadiene styrene, poly carbonate, poly ethylene terra phthalate and poly amide.
In a preferred embodiment of the invention, said thermoplastic polymer is poly lactic acid.
Present invention discloses a method for producing a filament for use as raw material of an object to be configured with FDM type 3 dimensioned printer and characterized that said method comprises process steps of mixing a thermoplastic polymer and a waste polyurethane reinforced in powder form of thermoset feature and obtaining a waste polyurethane reinforced composite material, heating and melting said composite material and obtaining filament by means of filament extrusion. In a preferred embodiment of the invention, said method comprises preparation of waste polyurethane support from waste polyurethane before step of mixing said thermoplastic polymer and waste polyurethane reinforced wherein waste polyurethane support is firstly brought into granulate form and then into powder in homogenous size range.
In a preferred embodiment of the invention, said method comprises step of supply of obtained waste polyurethane reinforced composite material to filament extrusion system after step of mixing said thermoplastic polymer and waste polyurethane support.
The structural and characteristics features of the invention and all advantages will be understood better in detailed descriptions with the figures given below and with reference to the figures, and therefore, the assessment should be made taking into account the said figures and detailed explanations.
Brief Description of the Drawings
Figure 1 is schematic view of steps of the method being subject of the invention,
Description of References
1. Polyurethane waste container
2. Plastic crushing machine
3. Plastic grinding machine
4. Thermoplastic polymer container
5. Double screw extruder
6. Composite Material
7. Filament extruder
8. Composite filament material
A- Collection of wastes from production lines and taking into polyurethane waste containers
(1 )
B- Making size of waste polyurethane material sizes smaller at plastic crushing machine (2) and granulating it, then bringing into powder form in homogenous size range at plastic grinding machine (3) and obtaining waste polyurethane reinforcement, C- Adding waste polyurethane support to thermoplastic polymer container (4) and obtaining polyurethane reinforced composite material (6) by means of double screw extruder (5),
D- Supply of obtained waste polyurethane reinforced composite material into filament extruder (7) and obtaining composite filament (8) in fibre form.
Detailed Description of the Invention
In this detailed description, waste polyurethane support composite material and filament and methods for production of them building being subject of this invention and the preferred embodiments have been disclosed solely for the purpose of better understanding of the subject and described in a manner not causing any restrictive effect.
Present invention discloses a composite material for use to produce filament as a raw material of an object to configure with FDM (Fused Deposition Modelling) type 3 dimensioned printer. Said composite material comprises at least a thermoplastic polymer and waste polyurethane reinforcement of thermoset feature.
Thus recycling is provided by reuse of polyurethane base wastes with waste polyurethane reinforcement and also FDM type 3-dimensioned printer raw material is reinforced.
According to the invention, FDM type 3 dimensioned printer is a 3-dimensoned printer configuring 3 dimension model (prototype or part) by casting a material in filament form into production table layer by layer through nozzle.
According to the invention, waste poly urethane material is made from polyurethane based products produced industrially. For instance, burrs remaining on product products in automotive sector during post production stage are cut and removed from product parts and thus waste polyurethane material is obtained.
According to present invention, waste poly urethane material is of thermoset feature. Polyurethane materials having thermoset feature allows production of production of products having improved saturation expectation with 3D printers.
According to present invention, waste polyurethane reinforcement is obtained by means of bringing waste polyurethane material into powder form. Since the collected polyurethane materials are of various sizes and geometries, they are to be brought into granulates of 2 - 4 mm sizes at plastic crushing machines before use at plastic grinding devices of laboratory type. The obtained polyurethane waste granulates should be brought into micron sizes homogenously. Said granulates are brought into powder form by use of a plastic grinding device such as pulverised device. The obtained powder particulate sizes can be about 100 pm. Thus it will be easier to form a homogenous mixture of powders having similar sizes as well as powders of micron sizes provide effect of strengthening by composite approach in the mixture.
According to present invention, composite material or waste polyurethane reinforced composite material is obtained by means of adding said waste polyurethane support to thermoplastic polymer matrix. Said waste polyurethane reinforcement can be added by means of thermoplastic polymer double screw extruder. Thus homogenous distribution and mixture of waste polyurethane support is provided in thermoplastic matrix.
Temperature profile of said double screw extruder should be adjusted according to fusing temperature of thermoplastic polymer used as binding matrix, For instance, for PLA having fusing temperature of 145° - 15513, temperature pro file from supply unit up to output should use screw speed of 115°- 170°- 180°- 175°- 14513 and 75 rpm.
A binding matrix is needed for binding waste polyurethane powders and enabling them to act as one single material in macro size. For that purpose thermoplastic polymers having current use as FDM type 3 dimensioned printers are used as matrix materials. In general thermoplastic polymers such as acrylonitrile butadiene styrene (ABS) or poly (lactic acid) (PLA) pass through metal cap heated at temperature between 250 - 3000 13 of the filaments of 3 or 1.75 mm and their thickness goes under 1 mm and also collected area goes into a glassy phase. Thermolpastic material collected on plate in fuse phase forms three dimensioned object.
In a preferred embodiment of the invention, said thermoplastic polymer poly lactic acid (PLA) is selected from acrylonotrile butadiene styrene (ABS), poly carbonate (PC), poly ethylene terra phthalate (PET) and poly amide (PA). Alternative filaments can be produced by use of different polymer types.
On a more preferred embodiment of the invention, said thermoplastic polymer is selected from poly lactic acid and acrylonotrile - butadiene styrene ABS). In a more preferred embodiment of the invention, said thermoplastic polymer is poly lactic acid. In a preferred embodiment of the invention, composite material comprises thermoplastic polymer at 75 % to 90 % by weight, waste polyurethane reinforcement of 10 % to 25 % by weight wherein thermoplastic polymer and waste polyurethane reinforcement is 100 % by weight in total.
In another more preferred embodiment of the invention composite material comprises thermoplastic polymer in 90 % by weight and polyurethane reinforcement at 10 % by weight.
In the most preferred embodiment of the invention composite material comprises thermoplastic polymer in 90 % by weight and polyurethane reinforcement at 10 % by weight wherein thermoplastic polymer is poly lactic acid.
Composite material may contain different rates depending on particulate size of thermoplastic polymer and thermoplastic polymer or waste polyurethane reinforcement. For instance in case of grinding of polyurethane wastes at nano meter level, composite material of desired features can be obtained by use of polyurethane waste at 1 - 2 % by weight. It is known that major changes are provided at too little amounts in features provided that smooth distribution of supports of nano size is provided.
Present invention also discloses a filament for use as raw material of an object to be configured with FDM type 3 dimension printer. Said composite material comprises at least a thermoplastic polymer and waste polyurethane reinforcement of thermoset feature. Thus Thermoplastic filaments of high performance with recycled polyurethane support strengthening that can be used in FDOM type 3 dimension printers by use of a recycling approach not seen before.
According to present invention, filament is produced by a filament extrusion device. Said filament is good for use as raw material of an object that can be configured with FDM type 3 dimensioned printer, Composite material is supplied to filament extrusion device for production of filament and filament is obtained in fibre form in fixed radius. It is preferred to perform this process by use of profile of temperature same as double screw extruder.
Temperature profile should be selected carefully in order to not degrade thermoplastic polymer. In addition, considering than the materials used therein are of humidity sensitive, storing conditions should be paid attention and if required, should be subjected to pre-drying at drying oven. In reference to figure 1 the invention also discloses a method for production of a waste polyurethane reinforced composite material (6) for use to produce filament as raw material of an object to configure with FDM type 3 dimensioned printer. Said method in general comprises following process steps:
A- Collection of wastes from production lines and taking into polyurethane waste containers
(1 )
B- Making size of waste polyurethane material sizes smaller at plastic crushing machine (2) and granulating it, then bringing into powder form in homogenous size range at plastic grinding machine (3) and obtaining waste polyurethane reinforcement,
C- Adding waste polyurethane support to thermoplastic polymer container (4) and obtaining polyurethane reinforced composite material (6) by means of double screw extruder (5),
In said method firstly waste polyurethane reinforcement is prepared from waste polyurethane material. According to it, firstly waste polyurethane material is granulated into sizes ranging from 2 to 4 mm at preferably a plastic crushing machine (2). Then granulates are brought into powder in micron sizes homogenously preferably at a plastic grinding machine (3). It will be easier to form a homogenous mixture of powders having similar sizes and powders of micron sizes provide effect of strengthening by composite approach in the mixture. Finally, the obtained waste polyurethane support is added to thermoplastic polymer matrix and mixed until a homogenous mixture is obtained by means of preferably a double screw extruder and thus waste polyurethane reinforced composite material (6) is obtained.
Present invention also discloses a method for producing filament for use as raw material of an object to be configured with FDM type 3 dimension printer. Said method in general comprises following step after the steps A, B and C described above.
D- Supply of obtained waste polyurethane reinforced composite material into filament extruder (7) and obtaining composite filament (8) in fibre form.
Filament extruder (8) or filament extrusion system is single screw extruder system with a body specifically designed for providing fixed filament diameter. Filament roller and filament rolling system are provided at extruder (8) output. In the said method, after preparation of waste polyurethane reinforced composite material, said composite material is heated and melted and then filament is obtained through filament extrusion.

Claims

1. A composite material for use to produce a filament as raw material of an object to be configured with FDM type 3 dimensioned printer, characterized by comprising; at least a thermoplastic polymer and a waste polyurethane reinforced of thermoset feature.
2. A composite material according to claim 1 , characterized by comprising; thermoplastic polymer at 75 % to 90 % by weight, waste polyurethane reinforcement of 10 % to 25 % by weight wherein thermoplastic polymer and waste polyurethane reinforcement rate is 100 % by weight in total.
3. A composite material according to claim 2, characterized by comprising; thermoplastic polymer at 90 % by weight and waste polyurethane reinforcement of 10 % by weight.
4. A composite material according to any one of preceding claims, characterized by comprising; waste polyurethane reinforcement is in powder form.
5. A composite material according to claim 4, characterized by comprising; waste polyurethane reinforcement is in homogenous size range.
6. A composite material according to claim 5, characterized by comprising; waste polyurethane reinforcement particulate size is about 100 pm.
7. A composite material according to any one of preceding claims characterized by comprising; said thermoplastic polymer poly lactic acid is selected from acrylonotrile butadiene styrene, poly carbonate, polyethylene terra phthalate and poly amide.
8. A composite material according to claim 7, characterized by comprising; said thermoplastic polymer is poly lactic acid.
9. A filament for use as raw material of an object to be configured with FDM type 3 dimensioned printer characterized by comprising; a thermoplastic polymer and a waste polyurethane reinforcement of thermoset feature.
10. A filament according to claim 9 and comprises thermoplastic polymer at 75 % to 90 % by weight, waste polyurethane reinforced of 10 % to 25 % by weight wherein thermoplastic polymer and waste polyurethane reinforcement rate is 100 % by weight in total.
1 1. A filament according to claim 10, characterized by comprising; thermoplastic polymer at 90 % by weight and waste polyurethane support of 10 % by weight.
12. A filament according to claim 10 or 11 claim, characterized by comprising; said thermoplastic polymer poly lactic acid (PLA) is selected from acrylonotrile butadiene styrene, poly carbonate, poly ethylene terra phthalate and poly amide.
13. A filament according to claim 12, characterized by comprising; said thermoplastic polymer is poly lactic acid.
14. A method for production of a waste poly urethane reinforced composite material for use to produce a filament as raw material of an object to be configured with FDM type 3 dimensioned printer, characterized by comprising; step of mixing a thermoplastic polymer with a waste polyurethane support in powder form with thermoset feature.
15. A method according to claim 14 characterized by comprising; said method comprises preparation of waste polyurethane reinforcement from waste polyurethane material before step of mixing said thermoplastic polymer and waste polyurethane reinforcement wherein waste polyurethane material is firstly brought into granulate form and then into powder in homogenous size range.
16. A method according to claim 14 or claim 15, characterized by comprising; said thermoplastic polymer poly lactic acid is selected from acrylonotrile butadiene styrene, poly carbonate, poly ethylene terra phthalate and poly amide.
17. A method according to claim 16 characterized by comprising; said thermoplastic polymer is poly lactic acid.
18. A method for producing a filament for use as raw material of an object to be configured with FDM type 3 dimensioned printer characterized by comprising; said method comprises process steps of mixing a thermoplastic polymer and a waste polyurethane reinforcement in powder form of thermoset feature and obtaining a waste polyurethane reinforcement composite material, heating and melting said composite material and obtaining filament by means of filament extrusion.
19. A method according to claim 18 characterized by comprising; said method comprises preparation of waste polyurethane reinforcement from waste polyurethane before step of mixing said thermoplastic polymer and waste polyurethane reinforcement wherein waste polyurethane reinforcement is firstly brought into granulate form and then into powder in homogenous size range.
20. A method according to claim 18 characterized by comprising; step of supply of obtained waste polyurethane reinforced composite material to filament extrusion system after step of mixing said thermoplastic polymer and waste polyurethane reinforcement.
PCT/TR2019/050982 2018-12-31 2019-11-22 Waste polyurethane reinforced composite material WO2020142031A2 (en)

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