CN111542421A

CN111542421A - Thermoplastic material

Info

Publication number: CN111542421A
Application number: CN201880084441.0A
Authority: CN
Inventors: 翁贝托·基亚内塞
Original assignee: Weng BeituoJiyaneisai
Current assignee: Weng BeituoJiyaneisai
Priority date: 2017-10-30
Filing date: 2018-10-18
Publication date: 2020-08-14
Also published as: MA50500A; EP3703922A1; IT201700123195A1; WO2019086993A1

Abstract

The invention relates to a thermoplastic material and a preparation method thereof. In particular, the invention relates to a thermoplastic material based on a mixture of thermoplastic and non-thermoplastic polymers, preferably from recycled materials. One example of a high throughput is an End of Life Tire (ELT). In particular, the invention relates to a thermoplastic material comprising a non-thermoplastic phase comprising a mixture of natural and synthetic rubber and optionally a cross-linked polyurethane, and a thermoplastic phase comprising a thermoplastic polymer, wherein the thermoplastic material preferably comprises 10% to 40% by weight of the thermoplastic polymer, 0% to 30% by weight of the cross-linked polyurethane and 10% to 85% by weight of the mixture of natural and synthetic rubber, with the proviso that the weight of the non-thermoplastic phase is between 40% and 85%.

Description

Thermoplastic material

Technical Field

The invention relates to a thermoplastic material and a preparation method thereof. In particular, the invention relates to a thermoplastic material based on a mixture of thermoplastic and non-thermoplastic polymers, preferably from recycled materials. One example of a high throughput is an End of Life Tire (ELT).

Background

The reuse of industrial and domestic waste is a problem that has not yet been completely solved. The greatest problem occurs with thermosetting polymer-based materials, i.e. polymers that undergo a vulcanization or crosslinking process. Typical examples of such materials are polyurethanes and natural or synthetic rubbers, the first being the crosslinking reaction of the polyol with the polyisocyanate and the second being the so-called vulcanization reaction.

The polyurethane has wide application. The main uses of foam are in the refrigeration industry, in the construction industry (thermal and acoustic insulation) and in the shipbuilding industry, while compact elastic materials are the main materials for the manufacture of seals, soft parts for various purposes (telephones, toys, etc.), textile fibres and shoe soles.

Natural or synthetic rubbers are commonly used in the manufacture of tires, shoe soles, seals, and the like.

The main problem associated with the use of these two materials is precisely their nature as thermosetting polymers. This need is addressed by performing a cross-linking/vulcanisation process within the mould to form the article during the manufacturing step, but when the article has reached its useful life, the main problem is its recycling. Since crosslinked polyurethanes and tires are not thermoplastic materials, they cannot be remolded in new products.

Therefore, scrap tires, which constitute the largest single source of reclaimed rubber in quantity, are subjected to a grinding process, the result of which (rubber powder) is used for the manufacture of modified asphalt, insulation and urban furniture, and as a filler for artificial grass sports fields. In all of these applications, the rubber crumb is always visually distinguishable from the polymeric substrate containing the rubber crumb and has poor abrasion resistance to materials which are susceptible to chipping by friction.

The thermoset polyurethane may be ground and then used as a filler material.

The presence of processes for devulcanization of rubber or glycolysis of polyurethane makes it possible to recover the raw materials, but such processes are not economically advantageous.

To overcome these problems, thermoplastic elastomers (TPEs) have been proposed, which behave like tires but have the great advantage of being reshaped by molding due to their thermoplasticity. However, these materials do not completely replace rubber, in particular tire rubber or sole rubber, and there is still a need to find an economically advantageous use for these materials.

Disclosure of Invention

The above-mentioned drawbacks are at least partially solved by a thermoplastic material obtained according to a method which envisages the mixing of non-thermoplastic materials, preferably waste materials (such as natural and synthetic rubbers, optionally polyurethanes and relatively small amounts of thermoplastic polymers).

Polyurethanes and rubbers may also be unprocessed, but the economic advantages of the products of the invention and the processes for preparing the products result from the use of polyurethanes and waste rubbers.

It has been observed that the percentage by weight of thermoplastic material incorporated in the polyurethane/rubber compound varies from 10% to 40%, giving the material derived therefrom the thermoplastic characteristics, allowing its repeated use in the thermoforming process.

The thermoplastic material according to claim 1 and its preferred embodiments, claims 2 to 16 and 18, the text of which is an integral part of the present description, is therefore an object of the present invention.

Another object of the invention is a process according to claim 17 which makes it possible to obtain a final thermoplastic material in which the scrap rubber powder is visually indistinguishable and has improved mechanical properties (abrasion resistance, grip, etc.).

Detailed Description

The invention relates to a thermoplastic material obtained according to a process involving mixing a non-thermoplastic phase comprising a mixture of natural and synthetic rubber and optionally a cross-linked polyurethane with a relatively small amount of a thermoplastic polymer.

Thus, the thermoplastic material of the present invention comprises a non-thermoplastic phase comprising a mixture of natural and synthetic rubbers and optionally a cross-linked polyurethane, and a thermoplastic phase comprising a thermoplastic polymer.

The thermoplastic material of the invention preferably comprises 10% to 40% by weight of the thermoplastic polymer, 0% to 30% by weight of the crosslinked polyurethane, 10% to 85% by weight of the mixture of natural rubber and synthetic rubber, with the proviso that the weight of the non-thermoplastic phase is between 40% and 85%.

The thermoplastic material of the invention may also comprise crosslinked polymers or copolymers of various nature in a non-thermoplastic phase, derived from waste or recycled.

In a preferred embodiment, the thermoplastic material of the invention comprises 20% to 35% by weight of the thermoplastic polymer, 0% to 20% by weight of the crosslinked polyurethane and 30% to 60% by weight of the mixture of natural rubber and synthetic rubber. In a more preferred embodiment, the mixture of natural and synthetic rubbers includes vulcanized rubber, particularly rubber powders from used tires (ELT) and/or other manufacturing items.

The crosslinked polyurethane may be a polyurethane from polyether diols, a polyurethane from polyester diols or mixtures thereof, and is preferably, for example, waste from shoe making.

If present, the polyurethane is present in the form of an abrasive material, preferably having a particle size of 1 to 5 mm.

The mixture of natural rubber and synthetic rubber includes natural rubber or synthetic rubber and ethylene-propylene-diene monomer terpolymer (tri-EPDM). In a preferred embodiment, the mixture comprises 30 to 80% by weight EPDM and 70 to 20% by weight natural or synthetic rubber.

The natural rubber or synthetic rubber may be styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), isoprene rubber, butadiene rubber, chloroprene rubber (neoprene), acrylonitrile-butadiene-chloroprene rubber (NCR), isobutylene isoprene rubber (HR), polynorbornene rubber (PNR), transposition lacquer rubber, EPM rubber (ethylene propylene monomer), acrylic rubber (ACM), EAM rubber (ethylene-vinyl acetate), chlorosulfonated ethylene rubber, or a mixture thereof.

Preferably, the natural rubber or synthetic rubber is waste material.

The natural or synthetic rubber is in powder form, preferably with a particle size of 400 to 600 microns, for footwear applications, or in the building sector 1000 microns to 3.5 mm.

In a preferred embodiment, the ethylene-propylene-diene terpolymer (EPDM) is formed from about 45-75%, more preferably about 70%, ethylene, 13-43%, more preferably about 25%, propylene, and 2.5-12%, more preferably about 5%, diene. The diene is preferably Ethylidene Norbornene (ENB).

The thermoplastic polymer may be of various nature depending on the type of application for which the material is to be used. Such polymers impart specific technical properties to the materials of the invention and may be selected from the following non-exhaustive list, for example:

polyethylene (PE) homopolymers, in particular LDPE (low density PE), HDPE (high density PE), PE-HMW (high molecular weight PE), PE-UHMW (ultra high molecular weight PE), PE being a soft, flexible, semi-crystalline thermoplastic material and having the properties and structure to impart a large-scale chain branching of the innovative thermoplastic material with variable length, for example to promote blending during melting;

modified PEs, in particular PEX + PSAC (cross-linked PE + polysaccharide/starch compounds), chlorinated and chlorosulfonated PEs, PE-ULD (ultra light PE), EVA (polyvinyl ethyl acetate), EVAL (polyvinyl acetate), EEA (ethyl acrylate copolymer), EBA (butyl acrylate copolymer), EMA (methyl acrylate copolymer), EAA (ethylene-acrylic acid copolymer), EMAA (ethylene-methacrylic acid copolymer), E/P (ethylene-propylene copolymer), EIM (ethylene-ionomer copolymer), COC (cyclic polyolefin copolymer), ECB (ethylene-asphalt copolymer blend), ETFE (ethylene-tetrafluoroethylene copolymer);

PDCPD (polycyclopentadiene), vinyl polymers, PS (polystyrene), PMS (poly alpha-methylstyrene), TPU (thermoplastic polyurethane), TPS (styrene-based thermoplastic polymer), EPS (expanded polystyrene), PVC (polyvinyl chloride), PVC-P (plasticized polyvinyl chloride), homopolymers and copolymers of PVC, PVAL (polyvinyl alcohol), PVFM (polyvinyl alcohol), PVK (polyvinyl ketone), PTFE (polytetrafluoroethylene), PVDF (polyvinylidene fluoride), PVF (polyvinylidene fluoride), PCTFE (polychlorotrifluoroethylene), ECTFE (ethylene-chlorotrifluoroethylene copolymer), ETFE (ethylene-tetrafluoroethylene copolymer), FEP (polyfluoroethylene-propylene), TFEHFPVDF (tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer), FKM (fluorinated elastomer), EPDM (ethylene-propylene-diene elastomer), FFKM (perfluoroelastomer);

-PAE (polyacrylate), PAN (polyacrylonitrile), PMA (polymethylmethacrylate), PBA (butyl acrylate), ANBA (acrylonitrile-methyl methacrylate copolymer), ANMA (acrylonitrile-butadiene-acrylate copolymer), PMMA (polymethylmethacrylate), AMMA (acrylonitrile-methyl methacrylate copolymer), MABS (methyl methacrylate-acrylonitrile-butadiene-styrene copolymer), MBS (methacrylic acid-butadiene-styrene copolymer), PMMI (polymethylmethacrylate-methyl imide), PMMA-HI, MMA-EML (methyl methacrylate-EML), PMMA + ABS (polymethylmethacrylate + acrylonitrile-butadiene-styrene);

POM-H (polyoxymethylene-H), POM-R (polyoxymethylene-R), POM + PUR (polyoxymethylene + polyurethane);

PA (polyamide), AB, AA/BB, polyamide elastomer TPE-A, polyesteramide PEBA, PA-RIM, PMPI (poly-m-phenyleneisophthalamide), PPTA (poly-p-phenyleneterephthalamide);

SP (aromatic polyester), PC (bisphenol A polycarbonate), PC-BPA, PC-TMC/BPA, PPC (polyhydroxycarbonate);

polycarbonates based on aliphatic dicarboxylic acids and mixtures thereof, PC + ABS, ASA (acrylonitrile-styrene-acrylate copolymer), AES (acrylonitrile-ethylene-propylene-diene-styrene copolymer), PMMA + PS, PET (polyethylene terephthalate), PPE + SB (polyphenylene ether + styrene-butadiene copolymer), PS-HI (polystyrene-HI), PPE (polyphenylene ether), PP-cop (polypropylene copolymer), SMA (styrene-maleic anhydride copolymer), PTP, PBT (polybutylene terephthalate), PTT (polytrimethylene terephthalate), PET + PBT, MSB, PSU (polysulfone);

-a thermoplastic polyester elastomer;

polyesters of aromatic diols and carboxylic acids, PAR (polyarylate), PBN (polybutylenenaphthalate), PEN (polyethylenenaphthalate);

polyarylsulphides and polyarylsulphones, PPS (polyphenylene sulphide), PASU, PSU (polysulphone), PES (polyether sulphone), PPSU (polyphenylsulphone), PSU + ABS;

polyaryl ketones and derivatives, PAEK (polyaryl ketones), PEK (polyether ketones), PEEK (polyether ether ketones), PEEEK (polyether ether ketones), PEKK (polyether ketone ketones), PEEKK (polyether ether ketone ketones), PEEEK (polyether ether ketone ketones), PEKEEK (polyether ketone ether ketones), PAEK + PI (polyaryl ketones + polyimides);

-thermoplastic polyimides, PAI (polyamideimide), PEI (polyetherimide), PISO (polyimide sulfone), PMI (polymethacrylimide), PMMI (polymethacrylimide), PARI (polyarylimide), PESI (polyesterimide);

-thermoplastic polyurethane TPU;

unsaturated polyester resins based on unsaturated polyester UP;

-an epoxy resin EP;

natural polymers from cellulose and starch: CA (cellulose acetate), CTA (cellulose triacetate), CP (cellulose propionate), CAP (cellulose acetate), CAB (cellulose acetate butyrate), NC (cellulose nitrate), EC (ethyl cellulose), MC (methyl cellulose), CMC (carboxymethyl cellulose), CH (hydrated cellulose), PSAC (polysaccharide starch);

or mixtures thereof.

The thermoplastic material of the present invention may also include a plasticizer to increase the toughness of the material.

The plasticizer can be present in a quantity varying from 0% to 15% by weight, preferably from 2% to 12% by weight, relative to the total weight of the material.

Monomeric or polymeric plasticizers may be used. The plasticizer may be selected from organic phosphates, such as tributyl phosphate, tri (2-ethylhexyl) phosphate or trioctyl phosphate; triphenyl phosphate, and cresyldiphenyl phosphate; adipates, sebacates or fatty acid esters, such as diethylhexylbutyl adipate or dioctyl adipate, methylcyclohexyl adipate, sebacate, butyl sebacate, 2-ethylhexyl acrylate or sebacate, octyl benzylsebacate and amyl stearate; dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dimethyl phthalate, diisooctyl phthalate or dioctyl phthalate, diisooctyl phthalate; dimethylcyclohexyl phthalate, dimethoxyethylene phthalate and dibutoxyethyl isodecyl phthalate; diacetin and triacetin.

Preferably, the plasticizer is selected from DOA (dioctyl adipate) and DIDP (diisodecyl phthalate).

The thermoplastic material of the invention may also comprise other additives, preferably selected from among sliding agents, lubricants, stabilizers, antistatic agents, flame retardants, dyes, toughening agents, fillers, reinforcing agents and blowing agents, depending on the intended use of the material. These additives may be chosen from those commonly used in the sector, either organic or inorganic.

The blowing agent may be endothermic or exothermic and will be selected with the molding technique depending on whether a closed cell foam or an open cell foam is desired.

Such additives may be included in total weight percentages ranging from 0% to 15%, preferably from 3% to 13% of the total weight of the material.

In a preferred embodiment, the thermoplastic material comprises a thermoplastic polymer selected from the group consisting of polyolefins, styrene polymers or copolymers, TPU or mixtures thereof in an amount of 15 to 35% by weight, the above-mentioned crosslinked waste polyurethane in an amount of 0 to 20% by weight, and the natural and synthetic rubber mixture in an amount of 30 to 60% by weight. More preferably, the polyolefin is selected from the group consisting of polypropylene, polyethylene, and HDPE; the styrene polymer or copolymer is selected from polystyrene and SBS; the natural or synthetic waste rubber is ELT rubber powder and/or other products.

The thermoplastic material of the invention can be obtained by a process comprising the following steps:

a) grinding the crosslinked polyurethane (if any);

b) grinding natural rubber or synthetic rubber into powder;

c) intimately hot mixing the powder of step b) with EPDM to obtain a homogeneous compound having a content of between 30% and 80% by weight of EPDM;

d) mixing the homogeneous compound of step c) and, if appropriate, the ground crosslinked polyurethane with a thermoplastic polymer until a homogeneous mixture is formed;

e) optionally, adding a liquid component (e.g., a plasticizer) to the mixture of step d and further mixing in a turbine mixer to absorb the liquid;

f) extruding the mixture of step d) or e).

In step c), the fine mixing of the natural or synthetic rubber powder with the EPDM may be carried out in a Banbury mixer. The fine temperature can reach about 100 ℃.

The homogeneous compound obtained in step c) is preferably ground to a fine particle size by means of a cutter before subsequent mixing with the thermoplastic polymer.

Depending on the extruder used for the end use of the material, the extruded material may be recovered in the form of pellets (using a cutter downstream of the extruder) or as a cake.

The mixture may be extruded from a single screw extruder, a dosing extruder, a cascade or tandem extruder, a rapid thermal extruder, a planetary extruder, a melt separation screw extruder, a barrier screw extruder, or a twin screw extruder. As a non-limiting example, the extrusion process of a single screw extruder is briefly described: feeding the extrudate through a hopper onto a screw rotating within a cylinder having a heated zone; the plastic material is here melted mainly by friction, partly by conduction, optionally degassed, and then homogenized by cutting and compression. The conveying effect comes from the friction force exerted by the screw and the cylinder surface on the extruded object. The temperatures required for extrusion were as follows:

-below the hopper: the temperature of the mixture is between 80 and 270 ℃,

-a central screw: from 80 c to 270 c,

-in the vicinity of the degassing zone: from 80 c to 270 c,

from the outlet to the cutter: from 80 ℃ to 270 ℃.

The extrusion speed varies according to the characteristics desired to be attributed to the innovative thermoplastic material and therefore also according to the set temperature. The unit of measurement of the speed is usually kilograms or volume ratio of extruded mass per hour.

As a non-limiting example, for a thermoplastic material, the mixture of which is suitable for making shoe soles, it is preferable, but not necessary, to use a single screw extruder with a length of 5 to 6 meters, progressive or progressive addition, with a 90mm diameter screw. The extrusion mass is inserted into a hopper, the temperature below the hopper must be 140 ℃, the screw speed programmed for 500kg/h extrusion, the temperature in the centre of the screw must be 150 °/160 ℃, the temperature near the degassing zone is 120 °/130 ℃, and the temperature at the exit of the cutter is 100 °/110 ℃.

By way of non-limiting example, for a thermoplastic material, the mixture of which is suitable for the manufacture of bricks or flooring both indoors and outdoors and also for floating, thermal/acoustic panels used in the construction industry, it is preferable, but not necessary, to use a twin-screw extruder of length 5 to 6 meters, the screws being of the co-rotating type and having a diameter of 115 mm.

The extrusion mass was inserted into a hopper, the temperature below the hopper had to be 160 °/170 ℃, the screw speed was programmed to 500/600kg/h of extrusion, the temperature in the centre of the screw had to be 180 °/190 ℃, the temperature was 160 ℃ near the degassing zone and the temperature was 150 ℃ at the exit of the cutter.

It is therefore clear that the type of extruder used can vary, although not in a limiting way, as a function of the mixture used as mass to be extruded, and the characteristics attributed to the thermoplastic material of the invention.

The particle size of the powder or granules used in the above method can be determined, for example, by sieving.

In a particular embodiment, the thermoplastic material comprises 15 to 25% by weight of Thermoplastic Polyurethane (TPU) or SBS, 10 to 20% by weight of cross-linked waste polyurethane, particles having a particle size of 1 to 5mm, 25 to 60% by weight of a mixture of waste rubber powder having a particle size of 400 to 600 microns and EPDM, 8 to 10% by weight of a plasticizer, preferably DIDP, 1 to 3% by weight of a dye, 4 to 6% by weight of silica and 2 to 4% by weight of a lubricant.

This material is particularly suitable for making soles, and it is therefore another object of the invention to make soles made of this material.

In other particular embodiments, the thermoplastic material comprises 15% to 35% by weight of polyolefin, preferably polypropylene or polystyrene, 5% to 15% by weight of crosslinked waste polyurethane, 25% to 60% by weight of a mixture of waste rubber powder having a particle size of 1-5mm, a particle size of 400 microns to 3.5mm and EPDM, 3-7% by weight of plasticizer, preferably dioctyl adipate, 1-3% by weight of dye, 4-6% by weight of silica, and 2-4% by weight of lubricant.

This material is particularly suitable for use in the construction sector, and therefore another object of the invention is a block made of this material, a floor for the exterior and interior, an insulating/soundproofing panel for buildings.

In yet another particular embodiment, the thermoplastic material comprises 20% to 35% by weight of polyolefin, preferably HDPE, or PVC (polyvinyl chloride), in an amount of 10% to 20% by weight, crosslinked waste polyurethane of 1-5mm particle size, a weight percentage of a mixture of waste rubber powder with particle size of 400 to 600 microns with EPDM, a plasticizer (preferably dioctyl adipate, in an amount of 2-4% by weight), a dye (in an amount of 1-3% by weight), silica (in an amount of 4-6% by weight) and a lubricant (in an amount of 2-4% by weight) is 25% to 60%.

An intumescent material is added to the mixture to impart lightweight and thermal/acoustic insulation properties to the inventive thermoplastic material.

Plastic foamed materials are known and are generally used to impart greater thermal insulation capability to the plastic materials because they create a plurality of cells therein. Known types of foamed materials fall into two broad categories, exothermic and endothermic.

The first generates heat and generates a gas, typically nitrogen, during the expansion process (e.g., azodicarbonamide, also known as carbamoylsemicarbazide, encapsulated isopentane, 5-phenyltetrazole, and benzenesulfonylhydrazide); these types of foamed materials, when heated, explain the exotherm and gases, such as nitrogen, carbon dioxide and ammonia. The decomposition reaction continues due to the heat generated by the gas release and cannot be interrupted by simple cooling measures.

The endothermic foam absorbs heat, degrading and producing neutral gases (e.g., carbon dioxide, but the most well known ingredients are carbonates and carboxylic acids). They have the advantage that when the heat supply is interrupted, the natural gas production will be stopped and resumed if further heat is supplied. Therefore, the endothermic foaming material is easier to handle during processing.

The foam material (if present) is included in the mixture at a weight percentage of 5% to 10%.

The thermoplastic material of the invention thus solves the problem initially presented of manufacturing thermoplastic formers in a wide range of application fields (shoes, buildings, car parts, packaging, clothing, toys, etc., in all fields where the material is to be used) an unlimited number of times at low cost, the waste being recyclable only for limited use.

It is also noteworthy that the material according to the invention, if compared with the thermoplastic polymer materials commonly used in the above applications (for example SBS-based polymers used in the shoe soles and in the construction sector) and containing rubber powders, shows improved mechanical properties.

In particular, the material of the invention, in compact form, has a specific weight of about 1g/cm³(determined by the method of ISO 2781: 2008), wear (abrasion resistance determined by the UNI EN 12770:2001 method) results in a volume loss of 100 to 150mm³And a tear strength (determined by the ISO 20872 method) of between 15 and 20N/mm.

The material of the invention, in its foamed form, has a specific weight of about 0.60g/cm³(determined by the method of ISO 2781: 2008), the wear results in a volume loss (wear resistance determined by the UNI EN 12770:2001 method) of between 150 and 190mm³And a tear strength (determined by the ISO 20872 method) of between 10 and 15N/mm.

For example, in the field of shoe solesConventional materials used, based on compact SBS (specific gravity about 1 g/cm)³) And foam type SBS (specific gravity about 0.65 g/cm)³) Having a thickness of about 250mm³And about 400mm³The wear volume loss (abrasion resistance by UNI EN 12770:2001 method) and the tear strength (determined by ISO 20872 method) were about 9N/mm and 8N/mm, respectively.

As a non-limiting example, some formulations according to the invention are listed below (percentages are by weight).

Example 1 sole

-polyurethane waste 20%

50% of a mixture of rubber powder and EPDM

-TPU thermoplastic waste 25%

-dye 5%.

Example 2-sole

Polyurethane waste 10%

50% of a mixture of rubber powder and EPDM

-SBS rubber 35%

-dye 5%.

Example 3 foam sole

Polyurethane waste 10%

50% of a mixture of rubber powder and EPDM

-30% of TPU thermoplastic waste or SBS rubber

-dye 5%

5% of blowing agent.

The blowing agent may be, for example, Expancel 930du/mb 120.

The additive added to the mixture of Expancel 930du/mb 120 (closed cell endothermic blowing agent) allows the gas inside the microspheres in thermal contact to expand and then expand the innovative thermoplastic material giving it 0.50/0.55g/dm³The specific weight of (c).

Example 4-building Material (floor)

Polyurethane waste 10%

50% of a mixture of rubber powder and EPDM

-PVC 35％

-dye 5%.

Example 5 building Material (floor)

Polyurethane waste 10%

50% of a mixture of rubber powder and EPDM

-PVC 30％

-dye 5%

5% of blowing agent.

The blowing agent may be, for example, Expancel 930du/mb 120.

The additive added to the mixture of Expancel 930du/mb 120 (closed cell endothermic blowing agent) allows the gas inside the microspheres in thermal contact to expand and then expand the innovative thermoplastic material giving it 0.25/0.30g/dm³The specific weight of (c).

Example 6-building Material (thermal and acoustical Panel)

Polyurethane waste 10%

50% of a mixture of rubber powder and EPDM

-polypropylene 35%

-dye 5%.

Example 7-construction Material (thermal and acoustical Panel)

-polyurethane waste 5%

50% of a mixture of rubber powder and ethylene propylene rubber

-polypropylene 30%

-dye 5%

10% of blowing agent.

Example 8-Pallet Material

-polyurethane waste 15%

50% of a mixture of rubber powder and ethylene propylene rubber

-HDPE 30％

-dye 5%.

It is worth noting that the variation in the percentage of blowing agent determines the corresponding variation in the specific gravity of the innovative thermoplastic material obtained.

It is also noteworthy that exothermic blowing agents can achieve the same foaming effect, but endothermic blowing agents are preferred for the reasons mentioned above.

It is clear that only some specific embodiments of the invention have been described, and that all changes required to adapt these embodiments to specific applications will be able to be made by those skilled in the art without thereby departing from the scope of protection of the invention.

Claims

1. A thermoplastic material comprising a non-thermoplastic phase comprising a mixture of natural and synthetic rubber and optionally a cross-linked polyurethane, and a thermoplastic phase comprising a thermoplastic polymer.

2. Thermoplastic material according to claim 1, characterized in that it comprises 10% to 40% by weight of thermoplastic polymer, 0% to 30% by weight of crosslinked polyurethane, 10% to 85% by weight of a mixture of natural rubber and synthetic rubber, with the proviso that the amount of non-thermoplastic phase is between 40% and 85% by weight.

3. Thermoplastic material according to claim 1 or 2, characterized in that it comprises 20% to 35% by weight of thermoplastic polymer, 0% to 20% by weight of cross-linked polyurethane, 30% to 60% by weight of cross-linked polyurethane of a mixture of natural rubber and synthetic rubber (if any), the scrap being a mixture of natural rubber and synthetic rubber consisting of ground rubber of used tires (ELT) or other scrap.

4. Thermoplastic material according to any of claims 1 to 3, characterized in that the cross-linked polyurethane (if any) is selected from polyether diol polyurethanes, polyester diol polyurethanes or mixtures thereof, preferably in ground form with a particle size between 1 and 5 mm.

5. Thermoplastic material according to any of claims 1 to 4, characterized in that the mixture of natural rubber and synthetic rubber comprises natural rubber or synthetic rubber and EPDM (ethylene-propylene-diene monomer terpolymer).

6. Thermoplastic material according to claim 5, wherein the mixture of natural and synthetic rubber comprises 30 to 80% by weight of EPDM and 70 to 20% by weight of natural or synthetic rubber.

7. Thermoplastic material according to any one of claims 1 to 6, characterized in that said natural or synthetic rubber is selected from styrene-butadiene rubber (SBR), nitrile-butadiene rubber (NBR), isoprene rubber, butadiene rubber, chloroprene rubber

Nitrile Chloroprene Rubber (NCR), Isobutylene Isoprene Rubber (IIR), bornyl rubber (PNR), skim coat rubber, EPM (ethylene-propylene monomer) rubber, acrylic rubber (ACM), EAM (ethylene-vinyl acetate) rubber, ethylene-chlorosulfonated rubber or mixtures thereof, preferably in powder form, the particle size of the footwear article is 400 to 600 microns, the particle size of the construction industry is 1000 microns to 3.5 millimeters.

8. Thermoplastic material according to claim 6 or 7, characterized in that the ethylene-propylene-diene terpolymer (EPDM) consists of 45-75% or about 70%, ethylene, 13-43% or about 25%, propylene and 2.5-12% or about 5% of a diene, wherein the diene is preferably Ethylidene Norbornene (ENB).

9. Thermoplastic material according to any of claims 1 to 8, characterized in that said thermoplastic polymer is selected from:

polyethylene (PE) homopolymers, in particular LDPE (low density PE), HDPE (high density PE), PE-HMW (high molecular weight PE), PE-UHMW (ultra high molecular weight PE);

modified PEs, in particular PEX + PSAC (cross-linked polyethylene + polysaccharide/starch compounds), chlorinated and chlorosulfonated PEs, PE-ULD (ultra light PE), EVA (polyvinyl ethyl acetate), EVAL (polyvinyl vinyl alcohol), EEA (ethyl acrylate copolymer), EBA (butyl acrylate copolymer), EMA (methyl acrylate copolymer), EAA (ethylene-acrylic acid copolymer), EMAA (ethylene-methacrylic acid copolymer), E/P (ethylene-propylene copolymer), EIM (ethylene-ionomer copolymer), COC (cyclic polyolefin copolymer), ECB (ethylene-asphalt copolymer blend), ETFE (ethylene-tetrafluoroethylene copolymer);

PDCPD (polycyclopentadiene), vinyl polymers, PS (polystyrene), PMS (poly alpha-methylstyrene), TPU (thermoplastic polyurethane), TPS (styrene-based thermoplastic polymer), EPS (expanded polystyrene), PVC (polyvinyl chloride), PVC-P (plasticized polyvinyl chloride), homopolymers and copolymers of PVC, PVAL (polyvinyl alcohol), PVFM (polyvinyl alcohol), PVK (polyvinyl ketone), PTFE (polytetrafluoroethylene), PVDF (polyvinylidene fluoride), PVF (polyvinyl fluoride), PCTFE (polychlorotrifluoroethylene), ECTFE (ethylene-chlorotrifluoroethylene copolymer), ETFE (ethylene-tetrafluoroethylene copolymer), FEP (polyvinyl fluoride-propylene), TFEHFPVDF (tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer), FKM (fluorinated elastomer), EPDM (ethylene-propylene-diene elastomer), FFKM (perfluoroelastomer);

POM-H (polyoxymethylene-H), POM-R (polyoxymethylene-R), POM (polyoxymethylene + polyurethane);

polycarbonates based on aliphatic dicarboxylic acids and mixtures thereof, PC + ABS, ASA (acrylonitrile-styrene-acrylate copolymer), AES (acrylonitrile-ethylene-propylene-diene-styrene copolymer), PMMA + PS, PET (polyethylene terephthalate), PPE + SB (polyphenylene ether + styrene-butadiene copolymer), PS-HI (polystyrene-HI), PPE (polyphenylene ether), PP-cop (polypropylene copolymer), SMA (styrene-maleic anhydride copolymer), PTP, PBT (polyisoprene), PTT (trimethyl terephthalate), PET + PBT, MSB, PSU (polysulfone);

-a thermoplastic polyester elastomer;

polyesters of aromatic diols and carboxylic acids, PAR (polyarylate), PBN (polybutylenenaphthalate), PEN (polyethylene naphthalate);

polyaryl ketones and derivatives, PAEK (polyaryl ketones), PEK (polyether ketones), PEEK (polyether ether ketones), PEEEK (polyether ether ketones), PEKK (polyether ketone ketones), PEEKK (polyether ether ketone ketones), PEEEK (polyether ether ketones), PEKEEK (polyether ketone ether ketones), PAEK + PI (polyaryl ketones + polyimides);

-thermoplastic polyurethane TPU;

-resins based on unsaturated polyesters UP;

-an epoxy resin EP;

or mixtures thereof.

10. Thermoplastic material according to any one of claims 1 to 9, characterized in that it comprises a plasticizer, preferably contained in a weight percentage lower than 15% of the total weight of the material, more preferably between 2 and 12% by weight;

and/or additives selected from slip agents, lubricants, stabilizers, antistatic agents, flame retardants, dyes, toughening agents, fillers, reinforcing agents and blowing agents, preferably contained in a total weight percentage lower than 15% of the total weight of the material, more preferably between 3 and 13% by weight.

11. Thermoplastic material according to any of claims 1 to 10, characterized in that it comprises 15% to 35% by weight of thermoplastic polymer selected from polyolefins, styrene polymers or copolymers, TPU or mixtures thereof, 0% to 20% by weight of crosslinked waste polyurethane, 30% to 60% by weight of natural rubber and synthetic rubber mixtures, wherein preferably the polyolefin is selected from polypropylene, polyethylene and HDPE; the styrene polymer or copolymer is selected from polystyrene and SBS; natural or synthetic rubber scrap is an ELT rubber powder and/or other articles.

12. Thermoplastic material according to any of claims 1 to 10, characterized in that it comprises 15 to 25% by weight of Thermoplastic Polyurethane (TPU) or SBS, 10 to 20% by weight of crosslinked waste polyurethane particles having a particle size of 1-5mm, a mixture of waste rubber powder having a particle size of 400 to 600 microns with EPDM, plasticizer (preferably DIDP, 8-10% by weight), dye (1-3% by weight), silica (4-6% by weight) and lubricant (2-4% by weight), 25 to 60% by weight.

13. Thermoplastic material according to any of claims 1 to 10, characterized in that it comprises an amount of crosslinked waste polyurethane (5 to 15% by weight) in polyolefin (preferably polypropylene) or polystyrene (15 to 35% by weight) or 1-5mm particles, a weight percentage of a mixture of waste rubber powder with a particle size of 400 micrometers to 3.5 millimeters with EPDM, a plasticizer (preferably dioctyl adipate, content 3-7% by weight), a dye (content 1-3% by weight), silica (content 4-6% by weight) and a lubricant (content 2-4% by weight) being 25 to 60%.

14. Thermoplastic material according to any of claims 1 to 10, comprising 20 to 35% by weight of a polyolefin, preferably HDPE, or PVC (polyvinyl chloride), 10 to 20% by weight of a crosslinked waste polyurethane with a particle size of 1-5mm, 25 to 60% by weight of a mixture of waste rubber powder with a particle size of 400 to 600 microns and EPDM, 2 to 4% by weight of a plasticizer, preferably dioctyl adipate, 1 to 3% by weight of a dye, 4 to 6% by weight of silica and 2 to 4% by weight of a lubricant.

15. A sole for a shoe made from the material of claim 12.

16. A building material made of the material according to claim 13, characterized in that the building material is preferably a brick, also raised outdoor and indoor floor or sound/heat insulating coated board.

17. A method of manufacturing a thermoplastic material according to any one of claims 1 to 16, comprising the steps of:

a) grinding the crosslinked polyurethane (if any);

b) grinding natural rubber or synthetic rubber into powder;

f) extruding the mixture of step d) or e).

18. A thermoplastic material obtainable according to the process of claim 17, having the following characteristics:

i) for dense materials

A specific gravity of about 1g/cc (determined by method ISO 2781: 2008),

volume loss due to abrasion (abrasion resistance determined by the UNI EN 12770:2001 method) in the range of 100 to 150mm³Between

A tear strength (determined by ISO 20872 method) between 15 and 20N/mm,

ii) for foams

A specific weight of about 0.60g/cc (determined according to method ISO 2781: 2008),

volume loss due to abrasion (abrasion resistance determined by the UNI EN 12770:2001 method) in the range of 150 to 190mm³Between

Tear strength (determined by ISO 20872 method) between 10 and 15N/mm.