• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Procedure to grant organic polymers the possibility of being detected. The present invention relates to a new method for giving thermoplastic, thermosetting or elastomeric polymers magnetic, electromagnetic, electrical, X-ray screening or density properties that allow the detection of these by means of existing equipment in the state of the art. technique dedicated to that purpose. The detection of thermoplastics, thermosets or elastomers in turn facilitates their location, their elimination or their separation. The procedure is based on the addition of specific alloys of iron and silicon with or without surface treatment. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2706662A1
    申请号:ES201930081
    申请日:2019-02-04
    公开日:2019-03-29
    发明作者:Cordon Julio Gomez；Jimenez Luis Otano；Martinez Javier Perez
    申请人:Avanzare Innovacion Tecnologica S L；
    IPC主号:
    专利说明:

    [0001]
    [0002] PROCEDURE TO OTHERWISE TO ORGANIC POLYMERS THE POSSIBILITY OF BEING DETECTED.
    [0003]
    [0004] SECTOR OF THE TECHNIQUE
    [0005]
    [0006] The present invention relates to a method for making plastic or elastomeric polymers easily detectable by means of magnetic, electromagnetic, electrical or X-ray systems.
    [0007]
    [0008] BACKGROUND OF THE INVENTION
    [0009]
    [0010] At present, magnetic, electromagnetic, electrical, X-ray or density detection applied to plastic or elastomeric polymers is of interest for many reasons since it allows:
    [0011]
    [0012] That manufacturers of food and pharmaceutical products can reduce the risk of contamination of these by the presence of plastics, elastomers or fragments from packaging, intermediate containers, conveyor belts, handling gloves, films or other.
    [0013]
    [0014] That the manufacturers of pipes for optical fiber or transport of fluids through the use of plastics or elastomers can confer the property of facilitating the detection of these tubes when repairs are necessary in them.
    [0015]
    [0016] That any manufacturer of plastics or elastomers facilitate recycling by separating different types of plastics or these and other components based on the possibility of magnetic, electromagnetic, electrical or X-ray detection or density of plastics or elastomers to be separated.
    [0017]
    [0018] To give these functions to plastics or elastomers, solid charges are added based on:
    [0019]
    [0020] Metals such as iron, pulverized austenitic steels, stainless steel 410SST or 17 4 as in patents US6113482, US6177113.
    [0021]
    [0022] Metal ferrites, including magnetic iron oxide as in the patent WO1992008923A1, WO2007012898A1, WO2006026823A1, DE4321612A1, JPH02166059A or US 2007/0205529 A1.
    [0023]
    [0024] Antiferromagnetic metal oxides such as MnO, FeO or MnS.
    [0025]
    [0026] The addition of compounds of iron or other metals such as oxides or others is that these compounds are not very effective in terms of their possibility of magnetic or electrical detection which requires the addition of large amounts of the iron compound for obtain the detection effect and this in turn leads to the loss of the physical, mechanical properties or the possibility of coloring them.
    [0027]
    [0028] On the other hand, the use of metallic iron or steel implies that the added metal is not stable over time because it is oxidized by the action of oxygen in the air, contaminating the plastic or object on which it has been added or causing it to lose its physical or mechanical properties so that the object no longer serves for what was built.
    [0029]
    [0030] The use of iron alloys commonly called stainless steels, prevent the problem of oxidation of the metal added to the polymer, but on the contrary to having alloyed the iron with sufficient amounts of chromium or nickel the resulting alloy loses magnetic properties and again it is necessary Add large amounts of said alloy to the polymer to achieve the effect of magnetic detection.
    [0031]
    [0032] OBJECT OF THE INVENTION
    [0033]
    [0034] The object of the present invention is to grant plastics and elastomers the possibility of being detected, located, eliminated or separated by magnetic, electromagnetic, electrical, X-ray or density means, by means of a process based on the addition of iron alloys and silicon prepared specifically for this purpose.
    [0035]
    [0036] DESCRIPTION
    [0037]
    [0038] Polymers, whether thermoplastic, thermosetting or elastomeric, can be detected by the use of magnetic, electromagnetic, electrical, X-ray or density detection equipment when they contain materials capable of producing some effect or change on the chosen detection system. The polymers can also be located, eliminated or separated. The methods of detection of metallic materials are based on several types of different technologies.
    [0039] The first type of metal detectors uses a balanced coil detection head. Detectors of this type can detect all types of metal contamination, including ferrous metals, non-ferrous metals and stainless steels through the electromagnetic and electrical effect produced by metals on the detection system.
    [0040] The second type of detector uses permanent magnets mounted on a ferrous metal detection head or magnetic stainless steels through the magnetic and electromagnetic effect produced by this type of metals on the detection system.
    [0041] The third group of technologies currently used for the detection, localization, elimination or separation of metallic materials is the X-ray inspection and that detects the shielding of these rays produced by high density materials, including metal.
    [0042]
    [0043] Finally, it is possible to detect, differentiate and / or separate polymeric materials by the increase in density in the mass of the object or fragment that produces the addition of a high density material on them.
    [0044]
    [0045] The detection of polymers or their fragments is the initial phase that facilitates or allows their elimination, location, repair, separation, recycling or recovery among others.
    [0046] The problem of adding metal alloys of iron to plastics is the reduction of the useful life of the same ones due to the fact that iron metal alloys are oxidized in a very short time, so that the object manufactured with iron ends up losing its utility.
    [0047]
    [0048] The addition of stainless steels has the problem that these have less effect on the detection systems because they have worse magnetic properties for detection.
    [0049]
    [0050] Surprisingly it has been shown that by applying a specific procedure it is possible to give thermoplastic, thermosetting or elastomeric polymers the property of being detectable by magnetic, electric, X-ray or density methods by adding iron and silicon alloys to the polymers. that maintain the magnetic properties by making the amount necessary to be added to achieve the detection of the set very low and also these alloys of iron and silicon do not oxidize or transform into other products during the useful life of polymer to which they have been added.
    [0051]
    [0052] The iron and silicon alloys that provide the detection effect by magnetic, electromagnetic, electrical, X-ray or density means are:
    [0053] Those whose silicon content of the alloys with iron can range between 0.2% and 75%, preferably between 5% and 50% and more preferably between 12 and 20%.
    [0054]
    [0055] In addition, the iron and silicon alloys may contain other chemical elements in maximum proportions equal to the silicon content in the alloy such as Cr, Ni, Co, Mo, Ti, Al, Mg, Ca, Sr, Ba, B, C, P , S, Cu, Zn, Zr, Nb, Sn, Ta, W, Bi, Ce, La, rare earths and their mixtures.
    [0056]
    [0057] The manufacture of iron and silicon alloys is done by: Primary methods are those that are based on the reduction of mixtures of iron and silicon compounds, mainly oxides of these elements, which are usually treated by the thermal action and reducing the carbon in an oven. In addition to these two main components may contain other components.
    [0058]
    [0059] Secondary methods when starting from iron metal or its alloys to which silicon metal or its alloys is added, and the rest of the components, if any, to finally melt everything that is going to form the alloy.
    [0060]
    [0061] Both primary and secondary methods can achieve iron and silicon contents in the final alloy within the range of those proposed in this invention, in addition to achieving the presence of other secondary components such as Cr, Ni, Co, Mo, Ti, Al, Mg, Ca, Sr, Ba, B, C, P, S, Cu, Zn, Zr, Nb, Sn, Ta, W, Bi, Ce, Rare earths and their mixtures.
    [0062]
    [0063] The shape of the material that is added to the polymer can be spherical, prismatic, in the form of wires, flat or irregular.
    [0064]
    [0065] The size of the materials to be added ranges between 10 nm and 5 mm, preferably between 1 micron and 300 microns and more preferably between 30 microns and 110 microns, although the size thereof will depend on the processing of the polymer. Thus, for example, for spinning or filament, the size of the materials will oscillate between 10 nm and 10 microns.
    [0066] The required amount of iron and silicon alloy to be added to the polymer, for the proposed materials, can range between 0.1% and 95%, preferably between 1.5% and 50% and more preferably between 3% and 20%.
    [0067]
    [0068] To obtain appropriate mechanical qualities in the final product and reduce the corrosion risk of the silicon-containing iron alloys of the present invention, the proposed materials may receive a surface treatment or functionalization prior to or during their mixing, based on the use of silane coupling agents, known in the state of the art. The silanes to be used can be one or a mixture of the following silanes:
    [0069]
    [0070] Vinyl silanes that include silanes of the formula:
    [0071]
    [0072] A-Yes (R2 MOR1) 3-x (1)
    [0073]
    [0074] where R1, as well as R2, independently of each other, represent a linear or branched alkyl group with 1 to 4 carbon atoms and generally R1 represents methyl and / or ethyl, and x is equal to 0 or 1, and A represents a vinyl group or functional propylvinyl. Examples of this type of silanes can be: vinyltrimethoxysilane, vinyltrietoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriisobutoxysilane, vinylacetoxysilane, vinyltriisobutoxy silane, vinylbutyltrimethoxysilane, vinylmethyltrimethoxysilane, vinylethyltrimethoxysilane, vinylpropyltrimethoxysilane, vinylbutyltriethoxysilane and vinylpropyltriethoxysilane.
    [0075]
    [0076] Aminosilanes that include silanes of the formula:
    [0077]
    [0078] A-Yes (R2) x (ORVx (2)
    [0079]
    [0080] where R1, as well as R2, independently of each other, represent a linear or branched alkyl group with 1 to 4 carbon atoms and generally R1 represents methyl and / or ethyl, and x is equal to 0 or 1, and A represents an amino-functional group of the formula 2a
    [0081] - (CH2) i- [NH (CH2) f] gNH [(CH2) f * NH] g * - (CH3) (2a),
    [0082] where i, f, f *, gog * are the same or different, with i = 1,2, 3 or 4, fy / of * = 1 or 2, g and / or g * = 0 or 1, preferably with i equal to 3 , as well as gyg * equal to 0.
    [0083]
    [0084] Bisaminosilanes including silanes of the formula:
    [0085]
    [0086] (OR1) 3Si-A-Si (OR1) 3 (3)
    [0087]
    [0088] where the groups R1 are the same or different and R1 represents a linear or branched alkyl group with 1 to 4 C atoms and preferably R1 represents methyl and / or ethyl, as well as, optionally, at least one other silicon compound of the tetraalkoxysilane series, alkylalkoxysilane, mercaptoalkylalkoxysilane, aminoalkylalkoxysilane, carboxyalkylalkoxysilane, ureidoalkylalkoxysilane, thiocyanatoalkylalkoxysilane and the silica sols, and A represents a bisaminofunctional group of the formula 3a.
    [0089]
    [0090] - (CH2) i- [NH (CH2) f] gNH [(CH2) f * NH] g * - (CH2) i * - (3a)
    [0091] where i, i *, f, f *, gog * are the same or different, with i and / oi * = 1, 2, 3 or 4, fy / of * = 1 or 2, g / og * = 0 or 1, Examples of this type of silane can be: bis- (trimethoxysilylpropyl) amine, bis- (triethoxysilylpropyl) amine, bis- (triethoxysilylpropyl) ethylene diamine, N- [ 2- (vinylbenzylamino) ethyl] -3-aminopropyltrimethoxy silane, and aminoethyl-aminopropyltrimethoxy silane.
    [0092]
    [0093] Silanes with epoxy or glycidoxy functional groups with formula:
    [0094]
    [0095] A-Yes (R2) x (OR1) 3-x (4)
    [0096]
    [0097] where A represents a 2- (3,4-epoxycyclohexyl) ethyl, 1-glycidyloxymethyl, 2-glycidyloxyethyl, 3-glycidyloxypropyl or 3-glycidyloxybutyl group, R 1, as well as R 2, independently of each other, represent a linear or branched alkyl group with 1 to 4 carbon atoms and preferably R 1 represents methyl and / or ethyl, and x is equal to 0 or 1. For example 3-gilcidyloxypropyltrimethoxysilane.
    [0098] Bisilanes with sulfur functional groups:
    [0099]
    [0100] (OR1) 3Si-A-Si (OR1) 3 (5)
    [0101]
    [0102] where the groups R1 are the same or different and R1 represents a linear or branched alkyl group with 1 to 4 C atoms and preferably R1 represents methyl and / or ethyl, as well as, optionally, at least one other silicon compound of the tetraalkoxysilane series, alkylalkoxysilane, mercaptoalkylalkoxysilane, aminoalkylalkoxysilane, carboxyalkylalkoxysilane, ureidoalkylalkoxysilane, thiocyanatoalkylalkoxysilane and the silica sols, and A represents a polysulfide group (5a):
    [0103]
    [0104] - (S) i- (5a)
    [0105]
    [0106] where i can take values from 1 to 10.
    [0107]
    [0108] Silanes with different functional groups such as:
    [0109]
    [0110] A-Yes (R2) x (OR1) 3-x (6)
    [0111]
    [0112] where A represents a group mercaptopropyl, thiocyanatopropyl, ureidopropyl, isocyanatopropyl, methacryloxypropyl, acryloxypropyl (...) and R1, as well as R2, independently of each other, represent a linear or branched alkyl group with 1 to 4 carbon atoms and preferably R1 represents methyl and / or ethyl, and x is equal to 0 or 1.
    [0113]
    [0114] Silanes with alkyl chains that include:
    [0115]
    [0116] A-Yes (R2) x (OR1) 3-x (7)
    [0117]
    [0118] where R1, as well as R2, independently of each other, represent a linear or branched alkyl group with 1 to 4 carbon atoms and generally R1 represents methyl and / or ethyl, and x is equal to 0 or 1, and A represents an alkyl group with 1 to 50 straight or branched carbon atoms, a cycloalkyl group which may be branched, a phenyl group or a phenylalkyl group with alkyl chains between 1 to 50 linear or branched carbon atoms.
    [0119]
    [0120] Bisilanes with alkyl chains:
    [0121]
    [0122] (OR1) 3Si-A-Si (OR1) 3 (8)
    [0123]
    [0124] where the groups R1 are the same or different and R1 represents a linear or branched alkyl group with 1 to 4 carbon atoms and preferably R1 represents methyl and / or ethyl and A represents an alkyl chain with 1 to 50 carbon atoms. Example of this type of silanes can be Bistriethoxysilylethane (BTSE).
    [0125] The ratio of silane to be added in mass / mass percentage to the iron alloy with silicon content may be between 0.01 and 10% silane. Preferably between 0.1 and 3% and more preferably between 0.2 and 2%.
    [0126]
    [0127] The preparation of the silanized materials is carried out before or during any mixing process involving the iron and silicon alloy.
    [0128]
    [0129] The addition of the silane to the iron-silicon alloy before mixing the material with the organic polymer is carried out by methods known in the state of the art and which are based on treatments in aqueous liquid medium or organic solvent such as alcohols. , ketones, their mixtures and / or their mixtures in water containing between 1 and 90% of the silane and in addition may contain additives to catalyze the silanization reaction of the surface of the magnetic material, for example those that produce an acidic pH, basic or are Lewis acids or bases, such as acetic acid, ammonia or tin acetate among others. After carrying out the treatment, the product obtained is dried between room temperature and 200 ° C, at atmospheric or vacuum pressure, to eliminate the liquid media and the by-products, catalysts and additives used in the silanization of the surface.
    [0130]
    [0131] The surface coating of the magnetic material of this invention can also be carried out by the addition of the silanes in the gas phase by methods such as physical vapor deposition (PVD), chemical vapor deposition (CVD) plasma and other methods known in the state of the art for functionalization other inorganic or metallic materials.
    [0132]
    [0133] To coat the surface of the material it is also possible to directly add the silane to the base organic polymer and simultaneously or later the magnetic material is added continuing the process with the whole mixture to obtain the active organic polymer, producing the silanization of the surface in the own polymer.
    [0134] Once the surface of the silane material has been coated, by means of this silane, coupling to the organic polymer takes place by the formation of covalent bonds, dipolar, self-assembly, electrostatic or van der Waals forces.
    [0135]
    [0136] The polymers to which the iron and silicon alloys proposed in this invention can be added to give them the possibility of being detected are: Polyolefins of any type such as polyethylene, polypropylene, polybutylene, copolymers with different monomers, EVA copolymers, ethylene-butyl methacrylate or others, polystyrenes, PVC and vinyl plastics, PET, polymethacrylates, polyacrylates, polyamides, PLA, PVDF, Teflon, polycarbonates, ABS, polyurethanes, natural rubber, SBR, NBR, chloroprene, EPDM, polybutadiene, butyl rubbers, silicones, rubbers acrylics, ionomers, latex, resins epoxy, unsaturated polyester, epoxy vinyl ester, gel coats of the previous two, coats acrylic gel, coats polyurethane gel, polyurethane resins, polyurea resins, urea formaldehyde, melamine-formaldehyde, phenol-formaldehyde, their mixtures and other organic polymers
    [0137]
    [0138] The process of adding materials to organic polymers includes several possibilities:
    [0139]
    [0140] Mixture of solid powders, which can be obtained by mixing the material of this invention with polymer powders of size between 10 nm and 10 mm by convective movement, mixed by diffusion or shear mixing. The mixing by convective movement consists of the inversion of the complete dust bed, in the case of tumbling mixers or it can be produced by dragging by means of a propeller, by means of a worm or other techniques. The diffusion mixture can be carried out by applying vibratory movement to the powders. The shear mixing can be performed during the grinding of the organic polymer, to which the material of this invention is added. These processes are known in the state of the art and are carried out by loads or continuously. Subsequently the obtained solid mixture can be used for molding or they can be extruded by melting or cold to obtain polymer pellets.
    [0141]
    [0142] Mixing in which the material of this invention is added to a molten solid comprising, among others:
    [0143]
    [0144] The inclusion of the material of this invention in the organic polymer directly by melting the polymer and blending, referred to in the state of the art as extrusion or melt mixing. The melting of the polymer can be carried out by heating in a single-screw, twin-screw, planetary extruder or with an internal mixer. The inclusion of the material of this invention in the organic polymer by the addition of the material of this invention in the form of a premix thereof with the same polymer or with other polymers, known in the state of the art as addition of a concentrate or masterbatch . The final melting and mixing can be carried out by heating in a single-screw, twin-screw, planetary or internal mixer extruder.
    [0145]
    [0146] Mixing in which the solid material of this invention is added over a monomer, dispersed by agitation, diffusion, shear, vibration, ultrasound or other and simultaneously or subsequently the monomer is polymerized in situ.
    [0147]
    [0148] Mixed in which the solid material of this invention is added to a solid polymer that has previously been dissolved in a solvent. The mixture of solid and liquid is dispersed by agitation, diffusion, shear, vibration, ultrasonic or other and simultaneous or the solvent is subsequently removed by vacuum, distillation or any other method applicable in the state of the art for the mixing of inorganic or metallic fillers.
    [0149]
    [0150] Mixture of the material of this invention or a concentrate or masterbatch thereof with the solid organic polymer in a blender closed by type Bambury, Sigma or similar, known in the state of the art for the mixing of inorganic or metallic fillers.
    [0151]
    [0152] Mixture of the material of this invention or a concentrate thereof, with the organic polymer in a roller mill or calender, known in the state of the art for mixing inorganic or metallic fillers.
    [0153]
    [0154] Mixture of the material of this invention or a concentrate or masterbatch thereof with a one or two component organic resin such as unsaturated polyesters, epoxy vinyl ester, gel coats of these polymers, epoxy resins, polyurethane resins, polyurea resins, urea-formaldehyde , melamine-formaldehyde, phenol-formaldehyde in which its components are liquid or pasty and which are mixed by any method of mixing or dispersion such as agitation, vibration, ultrasound or others.
    [0155]
    [0156] Any other method of the state of the art that allows to add a solid material to an organic polymer, whether this solid or liquid.
    [0157]
    [0158] Once the material of this invention has been added to the organic polymer, the final manufactured object can be shaped using any technique of the state of the art to obtain objects from organic polymers such as injection, extrusion, coextrusion, fiber manufacture, rotomolding, pressing, pressing. of hot plates, open molding, casting, sintering, film, fiber manufacture, SMC, BMC, lamination or other methods known in the state of the art.
    [0159]
    [0160] The final polymers can contain those other additives necessary in their manufacture as antioxidants, UV protectors, plasticizers, antistatics, electrical conductors, antiblocking agents, accelerators, catalysts, thermal stabilizers, flame retardants, mineral or organic fillers or other additives, depending on the properties that the final polymer, which may be added, be required before or after mixing with the material that gives the detection property.
    [0161]
    [0162] In addition, both thermoplastic and thermoset plastics or detectable elastomers may contain varying amounts of different pigments and dyes to give color to the plastic or elastomer, which can be added, before during or after mixing with the material that gives the detection property.
    [0163]
    [0164] In order to improve the mechanical and strength properties of the proposed final polymers, coupling agents such as polyethylene-maleic, polypropylene-maleic, polyethylene-acrylic acid and / or other polymers known in the prior art can be added thereto. improve the dispersion of solid charges in plastics or generate bonds between the solid charge and the polymer.
    [0165]
    [0166] The material used to confer the detection properties can be mixed or bound to any of the other additives, fillers or components that the polymer will carry, prior to mixing with the polymer.
    [0167]
    [0168] EXAMPLES
    [0169]
    [0170] Examples of coating by silanes of the silicon iron alloys of the present invention:
    [0171]
    [0172] Example R1: It starts from 1 kg of iron alloy with a silicon content of 15%. It is placed in a polyethylene drum with gas outlet. A mixture of 10 g of vinyltrimethoxysilane, 20 g of water and 1 g of acetic acid is added. The drum is turned at 25 rpm for 3 hours. The resulting volatiles are removed by vacuum.
    [0173]
    [0174] Example R2: Starting from 1 kg of iron alloy with a silicon content of 15%. It is placed in a polyethylene drum with gas outlet. A mixture of 10 g of aminopropyltrimethoxysilane and 10 g of water is added. The drum is turned at 25 rpm for 1 hour. The resulting volatiles are removed by vacuum.
    [0175]
    [0176] Example R3: It starts with 1 Kg of iron alloy with a silicon content of 15%. It is placed in a polyethylene drum with gas outlet. A mixture of 10 g of Bis [3- (triethoxysilyl) propyl] tetrasulfide is commercially added, Evonik Si-69, 10 g of water and 1 g of acetic acid. The drum is turned at 25 rpm for 3 hours. The resulting volatiles are removed by vacuum.
    [0177]
    [0178] Examples of use of the silicon iron alloys with or without functionalization or coating of the present invention:
    [0179]
    [0180] The substrates used referred to in the following examples are test pieces of polymers obtained by injection of the corresponding thermoplastic polymer after having been added thereto, by extrusion, the proposed material. The polymers contain antioxidants Irganox 10100.2% and Irgafos 1680.02%. Once the specimens are obtained, a square of 2 mm x 2 mm x 1 mm in height is cut out and tested on four types of detectors:
    [0181]
    [0182]
    [0183]
    [0184] The substrates referred to in the following examples are polymers obtained by rotomoulding powders of the corresponding thermoplastic polymer after being added thereto, the proposed material. For the addition of the solid, the polymer is first extruded with iron and silicon alloy powder to obtain pellets which are then ground to a maximum grain size of 150 p, m. The polymers contain antioxidants Irganox 1010 0.2% and Irgafos 168 0.02% and blue pigment. The conformed by rotomolding. Once the test specimen is obtained, a square of 2 mm x 2 mm x 1 mm in height is cut out and tested on four types of detectors:
    [0185]
    [0186]
    [0187]
    [0188]
    [0189] The substrates used referred to in the following examples are test pieces of polymers obtained by injection of the corresponding thermoplastic polymer after being added thereto, the material proposed by melt extrusion to obtain pellets.
    [0190] Once the specimens are obtained, a square of 2 mm x 2 mm x 1 mm in height is cut out and tested on four types of detectors:
    [0191]
    [0192]
    [0193]
    [0194]
    [0195] The substrates used referred to in the following examples are test pieces of polymers obtained by pressing hot plates of the corresponding elastomer, after having been added to the same material proposed in closed mixer type Bambury. The elastomers have been vulcanized by conventional accelerator systems known in the state of the art, for rubbers by the addition of sulfur 2.8 phr, mercaptobenzothiazole 0.3 phr, mercaptobenzothiazole disulfide 0.9 phr, zinc oxide 3.5 phr , stearic acid 1 phr, tetramethylhydroquinoline polymer 0.5 phr, naphthenic process oil 10 phr and kaolin 20 phr. For the silicone crosslinking by peroxides by adding 2% dichlorobenzoyl peroxide and for the silicone curing by platinum by the addition of platinum complex diviniltetramethyldisiloxane. Once the specimens are obtained, a square of 2 mm x 2 mm x 1 mm in height is cut out and tested on the four types of detectors:
    [0196]
    [0197]
    [0198] The substrates used referred to in the following examples are test pieces of polymers obtained by casting the corresponding thermoset, after having been added to the proposed material. The thermostable types of unsaturated polyester and epoxyvinyl ester have been crosslinked by means of conventional accelerator and catalyst systems known in the state of the art by adding 0.2% cobalt naphthenate accelerator and 1% methyl isobutyl ketone peroxide. Once the specimens are obtained, a square of 2 mm x 2 mm x 1 mm in height is obtained and tested on four types of detectors:
    [0199]
    [0200]
    [0201]
    [0202]
    [0203] The substrates used referred to in the following examples are polymer samples obtained by casting the corresponding thermoset. First it is added to In addition, in this case, 2% methacryloxypropyltrimethoxysilane was added, then the proposed silicon iron alloy was added. The material is mixed and the thermoset has been crosslinked by conventional accelerator and catalyst systems known in the state of the art by the addition of 0.2% cobalt naphthenate and 1% methyl isobutyl ketone peroxide. Once the specimens are obtained, a square of 2 mm x 2 mm x 1 mm in height is obtained and tested on four types of detectors:
    [0204]
    [0205]
    [0206]
    [0207] The separation by density of the organic polymers is carried out by flotation of the polymer directly in water. Test pieces of polymers of size 10 mm x 10 mm x 2 mm in thickness with or without the contents of the materials contemplated in this invention are manufactured and placed in a tank with water so that they separate due to the fact that the specimens float in the water or not.
    [0208]
    [0209]
    权利要求:
    Claims (15)
    [1]
    A method for making thermoplastic, thermosetting or elastomeric polymers detectable or separable by magnetic, electromagnetic, electrical, X-ray or density means and consisting of at least two components:
    a) The thermoplastic, thermoset or elastomeric polymer
    b) An iron-silicon alloy that may contain other chemical elements in maximum proportions equal to the silicon content in the alloy such as Cr, Ni, Co, Mo, Ti, Al, Mg, Ca, Sr, Ba, B, C, P, S, Cu, Zn, Zr, Nb, Sn, Ta, W, Bi, Ce, La, rare earths and their mixtures.
    [2]
    2. A method for making detectable or separable by magnetic, electromagnetic, electrical, X-ray or density means the thermoplastic, thermosetting or elastomeric polymers according to claim 1 in the polymers can be: Polyolefins of any type such as polyethylene, polypropylene, polybutylene , copolymers with different monomers, EVA copolymers, ethylene-butyl methacrylate or others, polystyrenes, PVC and vinyl plastics, PET, polymethacrylates, polyacrylates, polyamides, PLA, PVDF, Teflon, polycarbonates, ABS, polyurethanes, natural rubber, SBR, NBR, chloroprene, EPDM, polybutadiene, butyl rubbers, silicones, acrylic rubbers, ionomers, latex, epoxy resins, unsaturated polyester, epoxy vinyl ester, gel coats of the previous two, acrylic coats gel, coats polyurethane gel, polyurethane resins, resins of polyurea, urea-formaldehyde, melamine-formaldehyde, phenol-formaldehyde, their mixtures and other organic polymers .
    [3]
    3. A process for making detectable or separable by magnetic, electromagnetic, electrical, X-ray or density means the thermoplastic, thermosetting or elastomeric polymers according to claims 1 to 2, wherein the iron and silicon alloys have a silicon content that it may range between 0.2% and 75%, preferably between 5% and 50% and more preferably between 12 and 20%.
    [4]
    4. A method for making detectable or separable by magnetic, electromagnetic, electrical, X-ray or density means the thermoplastic, thermosetting or elastomeric polymers according to claims 1 to 3 wherein the iron and silicon alloys have a size between 10 nm and 1 mm, preferably between 1 micron and 300 microns and more preferably between 30 microns and 110 microns.
    [5]
    5. A method for making detectable or separable by magnetic, electromagnetic, electrical, X-ray or density means the thermoplastic, thermosetting or elastomeric polymers according to claims 1 to 4 wherein the alloys of iron and silicon are added in amounts ranging from 0.1% to 90%, preferably from 1.5% to 50% and more preferably from 3% to 20%.
    [6]
    6. A method for making detectable or separable by magnetic, electromagnetic, electrical, X-ray or density means the thermoplastic, thermosetting or elastomeric polymers according to claims 1 to 5 in which the iron and silicon alloys have been treated or functionalized superficially by silanes that can be one of these or the mixture of several:
    Vinyl silanes that include silanes of the formula:
    A-Yes (R2 MOR1) 3-x (1)
    where R1, as well as R2, independently of each other, represent a linear or branched alkyl group with 1 to 4 carbon atoms and generally R1 represents methyl and / or ethyl, and x is equal to 0 or 1, and A represents a vinyl group or functional propylvinyl.
    Aminosilanes that include silanes of the formula:
    A-Yes (R2) x (OR1) s.x (2)
    where R1, as well as R2, independently of each other, represent a linear or branched alkyl group with 1 to 4 carbon atoms and generally R1 represents methyl and / or ethyl, and x is equal to 0 or 1, and A represents an amino-functional group of the formula 2a
    - (CH2) i- [NH (CH2) f] gNH [(CH2) f * NH] g .- (CH3) (2a),
    where i, f, f *, gog * are the same or different, with i = 1,2, 3 or 4, fy / of * = 1 or 2, g and / or g * = 0 or 1, preferably with i equal to 3 , as well as gyg * equal to 0.
    Bisaminosilanes including silanes of the formula:
    (OR1) 3Si-A-Si (OR1) 3 (3)
    where the groups R1 are the same or different and R1 represents a linear or branched alkyl group with 1 to 4 C atoms and preferably R1 represents methyl and / or ethyl, as well as, optionally, at least one other silicon compound of the tetraalkoxysilane series, alkylalkoxysilane, mercaptoalkylalkoxysilane, aminoalkylalkoxysilane, carboxyalkylalkoxysilane, ureidoalkylalkoxysilane, thiocyanatoalkylalkoxysilane and the silica sols, and A represents a bisaminofunctional group of the formula 3a.
    - (CH2) i- [NH (CH2) f] gNH [(CH2) f * NH] g * - (CH2) i * - (3a)
    where i, i *, f, f *, gog * are the same or different, with i and / oi * = 1, 2, 3 or 4, fy / of * = 1 or 2, g / og * = 0 or 1, preferably with iei * equal to 3, as well as gyg * equal to 0.
    Silanes with epoxy or glycidoxy functional groups with formula:
    A-Yes (R2) x (OR1) 3-x (4)
    where A represents a 2- (3,4-epoxycyclohexyl) ethyl, 1-glycidyloxymethyl, 2-glycidyloxyethyl, 3-glycidyloxypropyl or 3-glycidyloxybutyl group, R 1, as well as R 2, independently of each other, represent a linear or branched alkyl group with 1 to 4 carbon atoms and preferably R 1 represents methyl and / or ethyl, and x is equal to 0 or 1. For example 3-gilcidyloxypropyltrimethoxysilane.
    Bisilanes with sulfur functional groups:
    (OR1) 3Si-A-Si (OR1) 3 (5)
    where the groups R1 are the same or different and R1 represents a linear or branched alkyl group with 1 to 4 C atoms and preferably R1 represents methyl and / or ethyl, as well as, optionally, at least one other silicon compound of the tetraalkoxysilane series, alkylalkoxysilane, mercaptoalkylalkoxysilane, aminoalkylalkoxysilane, carboxyalkylalkoxysilane, ureidoalkylalkoxysilane, thiocyanatoalkylalkoxysilane and the silica sols, and A represents a polysulfide group (5a):
    - (S) i- (5a)
    where i can take values from 1 to 10.
    Silanes with different functional groups such as:
    A-Yes (R2) x (OR1) 3-x (6)
    where A represents a group mercaptopropyl, thiocyanatopropyl, ureidopropyl, isocyanatopropyl, methacryloxypropyl, acryloxypropyl (...) and R1, as well as R2, independently of each other, represent a linear or branched alkyl group with 1 to 4 carbon atoms and preferably R1 represents methyl and / or ethyl, and x is equal to 0 or 1.
    Silanes with alkyl chains that include:
    A-Yes (R2) x (OR1) 3-x (7)
    where R1, as well as R2, independently of each other, represent a linear or branched alkyl group with 1 to 4 carbon atoms and generally R1 represents methyl and / or ethyl, and x is equal to 0 or 1, and A represents an alkyl group with 1 to 50 straight or branched carbon atoms, a cycloalkyl group which may be branched, a phenyl group or a phenylalkyl group with alkyl chains between 1 to 50 linear or branched carbon atoms.
    Bisilanes with alkyl chains:
    (OR1) 3Si-A-Si (OR1) 3 (8)
    where the groups R1 are the same or different and R1 represents a linear or branched alkyl group with 1 to 4 carbon atoms and preferably R1 represents methyl and / or ethyl and A represents an alkyl chain with 1 to 50 carbon atoms.
    [7]
    7. A process for making thermoplastic, thermosetting or elastomeric polymers detectable or separable by magnetic, electromagnetic, electrical, X-ray or density means in which the iron and silicon alloys have been surface treated by silanes according to claim 6 and wherein the ratio of silane versus iron and silicon alloys can be between 0.01 and 10% add as a percentage mass / mass. Preferably between 0.1 and 3% and more preferably between 0.2 and 2%.
    [8]
    8. A process for making thermoplastic, thermosetting or elastomeric polymers detectable or separable by magnetic, electromagnetic, electrical, X-ray or density means in which the iron and silicon alloys have been surface treated by silanes according to claim 7 in Those in which the treatment of the surface of iron and silicon alloys with a silane, when these are in solid state and is done by adding a liquid medium containing the silane.
    [9]
    9. A process for making thermoplastic, thermosetting or elastomeric polymers detectable or separable by magnetic, electromagnetic, electrical, X-ray or density means in which the iron and silicon alloys have been surface treated by silanes according to claim 7 in those in which the treatment of the surface of iron and silicon alloys with a silane, when these are in solid state is done by the addition of a gaseous medium containing the silane, by techniques such as PVD, CVD, plasma or others.
    [10]
    10. A process for making thermoplastic, thermosetting or elastomeric polymers detectable or separable by magnetic, electromagnetic, electrical, X-ray or density means in which the iron and silicon alloys have been surface treated by silanes according to claim 7 in those in which the treatment of the surface of iron and silicon alloys with a silane is carried out during mixing with the polymer, to which the silane has been added.
    [11]
    11. A method of preparing blends of the thermoplastic, thermosetting or elastomeric polymer and the iron-silicon alloy according to claims 1 to 10 is carried out by methods for mixing solids with solids as a mixture of powders, a mixture of solids with molten polymers, mixing powders with elastomeric polymers or mixing powders with liquids.
    [12]
    12. The preparation of articles according to claims 1 to 11 by injection, extrusion, coextrusion, fiber manufacture, rotomolding, pressing, hot plate pressing, open molding, casting, sintering, film, fiber making, SMC, BMC, laminate or other methods known in the state of the art.
    [13]
    13. A process by which the iron and silicon alloys are added to the polymers according to claims 1 to 12 to allow the detection of thermoset polymers, thermoplastics, elastomers or their fragments present in other products such as food, medicines, materials and powders for industrial use, liquids or others.
    [14]
    14. A process by which the iron and silicon alloys are added to the polymers according to claims 1 to 12 to allow the detection of pipes, pipes, manholes or structures made of thermoplastic, thermosetting or elastomeric polymers that are buried or hardly accessible.
    [15]
    15. A process by which the iron and silicon alloys are added to the polymers according to claims 1 to 12 to allow the separation of different thermoplastics, thermosets or elastomers or for the separation of these from other materials by detection of the presence of these or by separation based on different density.
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    同族专利:
    公开号 | 公开日
    IL283018D0|2021-06-30|
    WO2020161373A1|2020-08-13|
    US20220002503A1|2022-01-06|
    ES2706662B2|2020-04-17|
    EP3862174A1|2021-08-11|
    EP3862174A4|2022-01-05|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    EP0038730A1|1980-04-18|1981-10-28|Rhone-Poulenc Specialites Chimiques|Latex of magnetic polymers and process for their preparation|
    US5036210A|1989-12-18|1991-07-30|Gas Research Institute|Magnetically detectable plastic pipe|
    US20050042340A1|2001-11-29|2005-02-24|May Donald Bruce|Moulding composition|
    EP2929941A1|2014-04-08|2015-10-14|State of Oregon acting by and through The State Board of Higher Education on Behalf of the University of Oregon|Magnetic plastic or fiberboard waste separation|
    JPH02166059A|1988-12-14|1990-06-26|Dainippon Printing Co Ltd|Packaging material|
    US4956011A|1990-01-17|1990-09-11|Nippon Steel Corporation|Iron-silicon alloy powder magnetic cores and method of manufacturing the same|
    WO1992008923A1|1990-11-15|1992-05-29|Tamaqua Cable Products Corporation|Locatable magnetic plastic duct and process of making same|
    DE4321612A1|1993-06-24|1995-01-05|Wenzel Martin Prof Dr|Method of separating plastic parts in waste|
    US6177113B1|1995-06-27|2001-01-23|Apv Crepaco, Inc.|Process for detecting plastic or elastomeric contaminants in food processing|
    US6113482A|1999-06-10|2000-09-05|Marlen Research Corporation|Metal-detectable elastomeric material for piston seals and the like|
    CN101022931A|2004-09-09|2007-08-22|格伦达·费伊·贝尔|Separation of plastic and elastomers for food and pharmaceutical products|
    GB2428629A|2005-07-27|2007-02-07|B S Teasdale & Son Ltd|Magnetically detectable bag|
    CN108172356A|2018-01-30|2018-06-15|广州新莱福磁电有限公司|A kind of double property magnetic materials and preparation method thereof|
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