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    • 专利摘要:
    MALEIC ANHYDRID COPOLYMERS AS SOLUBLE SUPPORT MATERIAL FOR PRINTER FOR Fused Deposition Modeling (FDM). The invention relates to a new support material for the fused deposition modeling process for the production of three-dimensional objects. The invention relates more particularly to a 3D printing process involving support materials that are easier to remove than in the prior art. The support materials according to the invention are maleic-styrene anhydride copolymers, for example.
    公开号:BR112013023429B1
    申请号:R112013023429-6
    申请日:2012-03-13
    公开日:2020-11-17
    发明作者:Florian Hermes；Stefan Bernhardt；Dirk Poppe；Gunter Schmitt；Markus Pridohl；Gerd Lohden
    申请人:Evonik Rohm Gmbh；
    IPC主号:
    专利说明:

    Technical Field
    [001] The invention relates to a new support material for the casting process for the production of three-dimensional objects. The invention relates more particularly to a 3D printing process involving support materials that are easier to remove than in the prior art. The support materials according to the invention are maleic-styrene anhydride copolymers, for example. Prior Art
    [002] The processes of rapid production or rapid prototyping are manufacturing processes designed to transpose the existing three-dimensional CAD data ideally without manual deviations or formation directly and quickly in parts.
    [003] Rapid prototyping processes have managed to be differentiated in various ways, which can be subdivided into two groups: laser-based processes and processes without the use of a laser.
    [004] Stereolithography (SLA) is the oldest and best known 3D laser printing process. It comprises a liquid composition of a radiation curable polymer to be cured with one laser layer per layer. This process is very limited in its entirety.
    [005] A similar process is the selective laser sintering process (SLS) in which a powdery raw material, for example, a thermoplastic, sand or a sinterable metal, is selectively synthesized with a laser layer per layer similar to the process of SLA. SLS is again only capable of making very specific 3D objects real. The same goes for the third laser-based process - production of a laminated object - in which the layers of plastic or paper coated with adhesive are successively glued together and cut using a laser.
    [006] The UV inkjet process is a well-known versatile 3D printing process. It is a three-step process in which a powdery material is applied to the thin layers, a UV-curable liquid is printed on it in the form of the specific layer of the last three-dimensional product, and finally the printed layer is cured with a UV source. The process steps are repeated layer by layer.
    [007] There is also the three-dimensional printing process (TDP). This process is similar to inkjet processes in the use of powdery materials, but these are preferably ceramic objects and are selectively saturated with a melt of a layer of layered thermoplastic polymer. After each printing layer, a new layer of the powdery material has to be applied. The thermoplastic solidifies to form the three-dimensional object. This process is expensive, inconvenient and very slow.
    [008] Fused deposition modeling (FDM), also known, with small variations, as selective deposition modeling (SDM), is the most economical process in terms of equipment and material needs for the production of three-dimensional objects through Printing.
    [009] In FDM, two different polymers are melted in the nozzles and selectively printed. One of the polymers is a support material that is needed as a temporary base, for example. This support material can later be removed, for example, through complete or partial dissolution in aqueous systems (in a basic or acidic medium, for example). The other polymer (the building material) forms the current 3D object. Again, printing occurs layer by layer. The FDM process was first described in US 5,121,329.
    [0010] In the first modality, ABS terpolymers were used equally as a support material and as a building material. After printing, the support material was then removed using the predetermined breaking points.
    [0011] A more recent development uses soluble polymers as a support material which are then dissolved as described above. Due to the thermal type of printing, the choice of possible support materials is very limited with respect to the melting or glass transition temperature.
    [0012] US 5,503,785 describes polyethylene oxides, polymers based on glycol or polyvinylpyrrolidone as soluble materials. In any case, these materials all have a very low softening temperature or very low solubility to ensure fast printing.
    [0013] EP 1,105,828 proposes poly (2-ethyl-2-oxazoline) for use as a support material. In any case, this material has a low glass transition temperature of only 58 ° C and as a result is poorly usable for a printing operation. Printing would have to be done that way at low temperatures using a similarly sensitive building material.
    [0014] EP 1 773 560 and EP 1 194 274 propose combinations of plasticizers and water soluble polymers, highly acid-containing. In any case, the formation of anhydride during printing at elevated temperatures adversely affects the solubility and melt viscosity of these support materials.
    [0015] WO 2010 045 147 describes impact modified terpolymers of styrene, methacrylic acid and butyl acrylate, commercially available from Innocycling GmbH & Co. KG under the name Belland® 88140. In any case, these materials also exhibit delayed solubility, not ideal, in combination with only insufficiently improved thermal stability.
    [0016] The support materials of the prior art are not one and at the same time meet the established requirements of a high glass transition temperature, high thermal stability and removability in relatively weak basic media, for example, at pH 8. Problem
    [0017] The problem addressed by the present invention was to provide a new 3D printing process by FDM. This process will include a suitable support material that is thermally stable and, on the other hand, is quickly and completely removable after printing by dissolving.
    [0018] The problem was more particularly that of providing a support material for this process that is stable at 200 ° C for at least 1 hour and during this time it does not change for an extended period of time in terms of the properties of solubility and mechanics. Printing will thus be possible above 100 ° C and the choice of construction materials will thus be expanded.
    [0019] Another problem addressed by the present invention was to provide an FDM process in which the support material can be removed under milder conditions - for example, with respect to pH and / or dissolution temperature - compared to the technique previous.
    [0020] The support material will also be distinctly faster to remove than in the prior art under comparable conditions.
    [0021] In this regard, the problem addressed by the present invention was more particularly that of providing, in specific modalities, a dissolution process at a pH ranging from 6 to 9, which is relatively non-critical for the printer user.
    [0022] Other problems addressed by the present invention and not mentioned explicitly should be evident from the general context of the examples, claims and description that follow. Solution
    [0023] The problems were solved through a new 3D printing process by FDM involving the use of a new support material. This support material is a formulation containing at least 60% by weight, preferably at least 80% by weight and more preferably at least 90% by weight of a copolymer containing 30% to 60% by weight of maleic anhydride and from 30% to 60% by weight of copolimerizable monomers with maleic anhydride. This support material is at least 60% by weight, preferably at least 80% by weight and more preferably at least 90% by weight soluble in aqueous medium at a pH between 6 and 14.
    [0024] It is rare for homopolymerization of maleic anhydride free radicals to lead to high conversions and molecular weights. In any case, maleic anhydride is copolymerizable with a multiplicity of vinyl monomers. In particular, high reaction rates, conversions and molar masses are obtainable in copolymerizations with electron-rich monomers. The monomers copolymerizable in maleic anhydride according to the invention are such electron-rich monomers. To assess whether a monomer is an electron-rich monomer, Alfred and Price's Q / e scheme, with which a person skilled in the art must be familiar, can be employed. The compounds in which e <0 are rich in electrons and consequently qualify, according to the invention, as copolimerizable monomers with maleic anhydride.
    [0025] Monomers copolymerizable with maleic anhydride are exclusively monomers that are copolymerizable with maleic anhydride alone without other monomers. Examples are styrene, isobutylene or isobutyl vinyl ether. Styrene and isobutylene are particularly preferred. Other examples are given in "Handbook of Polymer Synthesis - Part A" (edited by H.R. Kricheldorf), Marcel Dekker, Inc., New York, Basle, Hong Kong 1992 in the chapter "Maleic acid and related monomers".
    [0026] A 3D printing process by FDM for the purposes of this invention is a process in which at least one building material and at least one support material are each initially present as solid polymers and then fused and subsequently printed.
    [0027] A support material for the purposes of this invention is a material that is printed as described above to form, for example, the base structures or other auxiliary functions in the printing operation and after printing has been done, one more is removed through dissolution.
    [0028] This invention exclusively comprises the support materials of this definition for the 3D printing processes by FDM of the above definition.
    [0029] Surprisingly, these copolymers are found to be soluble at a pH as low as pH 8.
    [0030] In a first preferred embodiment, the support material is a copolymer of 50% to 60% by weight of styrene and 40% to 50% by weight of maleic anhydride.
    [0031] It is particularly preferable especially in view of the established FDM 3D printing processes and the temperatures employed in them for the glass transition temperatures of copolymer to differ from the glass transition temperatures of the specific building material employed for no more than 25 ° C, preferably not more than 10 ° C and more preferably 5 ° C. The glass transition temperatures for a 3D FDM printing process employing an ABS having a glass transition temperature of 108 ° C as a building material, for example, are between 83 and 133 ° C, more precisely between 98 and 118 ° C and especially between 103 and 113 ° C.
    [0032] After printing, the support material is preferably dissolved in an aqueous medium at a pH between 6 and 14 and more preferably between 7 and 9. What is surprising here is that a sufficient rate of dissolution can be obtained for a support material mechanically and thermally suitable at pH values between 6 and 9, which are not critical for the user.
    [0033] The pH values established in the context of the invention refer to the medium of the solution before the dissolution of the support material. It should be noted that this pH must change during dissolution. To counteract this change to some extent, at least, the solution medium can alternatively be in a buffered state.
    [0034] The molecular weight Mw of the copolymer used as a support material is generally between 25,000 and 500,000, preferably between 50,000 and 300,000 and more preferably between 100,000 and 200,000.
    [0035] It was another surprise to find that these previously suitable materials can also be improved, particularly in terms of flexibility and processing temperature, through the addition of other comonomers. Two particularly preferred embodiments have been found for these.
    [0036] In the particularly preferred first embodiment, the copolymers additionally include between 2% and 20% by weight of (meth) acrylic acid. The copolymer in this case is preferably more particularly prepared from 40% to 55% by weight, in particular between 44 and 51% by weight, of styrene, from 35% to 50% by weight and more particularly between 39% and 46% by weight. weight of maleic anhydride and from 3% to 18% by weight and more particularly from 4% to 16% by weight of (meth) acrylic acid.
    [0037] In the second particularly preferred embodiment, the copolymers additionally include from 2% to 40% by weight of a methoxy polyethylene glycol methacrylate having a molecular weight Mw between 250 and 2000 and preferably between 400 and 800. The copolymer in this case it is particularly preferably prepared from 35% to 55% by weight and more particularly between 37% and 51% by weight of styrene, 30% to 50% by weight and more particularly between 32% and 46% by weight of maleic anhydride and from 3% to 35% by weight and more particularly 4% to 32% by weight of methoxy polyethylene glycol methacrylate.
    [0038] Regardless of the modality, copolymers are obtainable through solution or volumetric polymerization. A volumetric polymerization process can be a continuous process carried out in a mixer or an extruder. Preferably, the copolymers of the current invention for use in or as a support material are produced by polymerizing the solution with subsequent removal of the solvent.
    [0039] Furthermore, copolymers may contain up to 40% by weight and preferably not more than 20% by weight of other copolymerizable monomers not functionalized with styrene. Preferably, these are alkyl acrylates, such as ethyl acrylate, propyl acrylate or butyl acrylate.
    [0040] In a first embodiment, the copolymer in the support materials is more particularly a copolymer of 50% to 60% by weight of styrene or isobutylene and 40% to 50% by weight of maleic anhydride.
    [0041] In a second embodiment, the copolymer in the support materials is more particularly a copolymer of 40% to 55% by weight of styrene or isobutylene, from 35% to 50% by weight of maleic anhydride and from 4% to 16% by weight of (meth) acrylic acid.
    [0042] In a third embodiment, the copolymer in the support materials is more particularly a copolymer of 35% to 55% by weight of styrene or isobutylene, from 30% to 50% by weight of maleic anhydride and from 4% to 35% by weight of methoxy polyethylene glycol methacrylate.
    [0043] The support materials may additionally contain the rheological modifiers, stabilizers, pyrogenic or precipitated silicas, plasticizers, pigments and / or impact modifiers. Other additives are conceivable depending on the intended use, and must be evident from the processing conditions in each case.
    [0044] Pigments can have the advantage that the support material is easier to distinguish from the construction material before printing or during printing.
    [0045] Rheological modifiers can be used to adjust the melt viscosity during printing to specific values.
    [0046] Pyrogenic or precipitated silicas also serve to adjust the melt viscosity, for example, to increase pseudoplasticity.
    [0047] Plasticizers are useful for adjusting the flexibility and viscosity of the melting of the support material to specific values. Typical plasticizers should be known to a person skilled in the art, and include, but are not limited to, esters and / or ethers of citric, aliphatic, cycloaliphatic or aromatic phthalates, adipic acid esters, aryl and / or aryl phosphates, polyethers, glycerol esters and their combinations. Plasticizers can be used in the amounts of 0% by weight to 20% by weight, preferably from 3% by weight to 15% by weight and even more preferably between 5% by weight and 10% by weight, based on total mass of support material.
    [0048] Stabilizers can be used to additionally improve thermal stability, for example. Stabilizers to improve storage stability, such as UV stabilizers, for example, can also be added.
    [0049] In addition, the support materials can contain up to 40% by weight and preferably and not more than 30% by weight of the components to improve flexibility. These components can be impact modifiers as well as plasticizers.
    [0050] The components, in general, used as impact modifiers have found application in various building materials, particularly PVC and PMMA, but also the copolymers of maleic-styrene anhydrides, and must be familiar to a person skilled in the art . For the purposes of the present invention, it is particularly suitable to use water-dispersible, at least water-soluble components that find general use as impact modifiers. In any case, due to the fine dispersion within the support material, even the completely water-insoluble components that are in general use when impact modifiers are also suitable for this purpose.
    [0051] Impact modifiers based on olefins are listed in a possible modality. A person skilled in the art should know that the copolymers of maleic-styrene anhydrides that have been modified with the olefins have improved impact resistance. Various compositions and methods of preparation are described in DE 2246726. The presence of rubber during polymerization provides covalent bonding to the maleic-styrene anhydride copolymer. Suitable rubbers preferably contain at least 65% by weight of butadiene.
    [0052] Preferred substrates are butadiene homopolymers or block copolymers of form A-B or A-B-A consisting of styrene and butadiene.
    [0053] WO 2005 016 978 describes the use of α-olefin copolymers and polymers, for example, copolymers and polymers of butylene, ethylene and propylene, as impact modifiers for maleic-styrene anhydride copolymers. These impact modifiers have the advantage of greater thermal stability. This feature is also known for hydrogenated block copolymers of styrene and butadiene.
    [0054] The polymerization of maleic anhydride copolymers according to the invention preferably takes place in the presence of rubbers. What is advantageous is a reaction temperature above the softening point of the rubber or in the presence of a solvent for the rubber. This can be, for example, styrene in the case of volumetric polymerization. The reaction is initiated by thermal initiation or by adding the initiators that form free radicals.
    [0055] Suitable impact modifiers also include functional copolymers, such as functionalized epoxy polyolefins or maleic acid based on polyethylene or polypropylene, for example. Copolymers of glycidyl and ethylene methacrylates or maleic anhydride are specifically related. These components can also contain (meth) acrylates. These components are preferably dispersed through the composition in an extruder, for example. Another possibility is to polymerize the maleic anhydride copolymers of the present invention in the presence of functionalized polyolefins.
    [0056] The core-coating particles are an additional group of impact modifiers. The core of the core-coating particles generally consists of elastomers or engineering thermoplastics, which are grafted with a second component. Preference is given to the production of the core-coating particles through the polymerization of the two-stage emulsion. The core material employed typically comprises amorphous copolymers having a glass transition temperature below 0 ° C, such as ethylhexyl acrylate or butyl, for example. The coating generally consists of a hard component having a glass transition temperature above 70 ° C. These polymers are more particularly known as PMMA or PVC as components, generally used as impact modifiers. Suitable particle sizes of these emulsion polymers range from 25 nm to 1000 nm, preferably from 50 nm to 600 nm and more preferably from 80 nm to 400 nm.
    [0057] The coating of the core-coating particles consists, for example, of a copolymer of styrene, or polystyrene-co-methacrylate of methoxy polyethylene glycol, which makes good compatibility with the copolymer which is the main component of the support material . Preferably, the core and / or coating of the particle is in a cross-linked state. This leads to a stabilization of the particles and consequently to distinctly improve the properties of the components generally employed as impact modifiers.
    [0058] The core-coating particles are preferably dispersed through the mechanical composition in a single or two helix extruder, for example. In yet another embodiment, the core-coating particles are dispersed in a solvent and the maleic anhydride copolymer is polymerized in its presence.
    [0059] The components generally employed as impact modifiers can be used in the amounts of 3% by weight to 30% by weight, preferably 8% by weight and 22% by weight and even more preferably between 10% by weight and 15% by weight, based on the total mass of the support material.
    [0060] Additional additives can be additives for preventing the preparation of the static or for modifying the surface properties, for example. They can also be adhesion promoters to improve adhesion to the construction material. Examples Assessment methods Drying of the synthesized samples:
    [0061] The samples were dried for 6 hours at 50 ° C and then overnight at 150 ° C in a vacuum drying oven. GPC:
    [0062] The weighted average molecular weights were determined by means of gel permeation chromatography (GPC) using polystyrene standards (manufacturer: Polymer Laboratories Ltd.). The evaluations were carried out at an oven temperature of 35 ° C. The following column combination was used: Guard Column PL, 10 pm, 5 cm, 7.5 mm in diameter, PLgel 106A, 10 pm, 30 cm, 7.5 mm in diameter, PLgel 105A, 10 pm, 30 cm, 7.5 mm in diameter, PLgel 104 A, 5 pm, 30 cm, 7.5 mm in diameter, PLgel 103 A, 5 pm, 30 cm, 7.5 mm in diameter (manufacturer: Polymer Laboratories Ltd.) - The eluent used was THF with 0.1% by volume of trifluoroacetic acid. DSC
    [0063] DSC evaluations were performed on a METTLER TOLEDO DSC1 in the atmosphere of 5.0 nitrogen.
    [0064] The glass transition temperatures were determined according to DIN ISO 11357. melt flow index (MFI)
    [0065] The MFI was determined on a Gottfert fusion flow index tester, type MPS-D. Matrix diameter = 1 mm. Unless otherwise stated, the evaluation was carried out at a temperature of 200 ° C and a weight placed of 10 kg. The samples were dried by the method described above before being evaluated. Determination of solubility:
    [0066] 50 mg of the dry substance by the above method was added under stirring to 10 ml of solutions heated to 75 ° C (pH 8: Na2HPO4 * 2 H2O phosphate buffer; c = 0.2 mol / L; pH 14: NaOH, 0.1 molar).
    [0067] At the time of complete solubility, either a clear homogeneous solution is present, or there is a milky dispersion. Starting materials used
    [0068] Styrene, for synthesis, stabilized with 10-20 ppm 2,6-di-tert-butyl-4-methylphenol
    [0069] Maleic anhydride, dilauroyl peroxide, 2-butanone and other monomers, for synthesis of Bisomer MPEG550MA, from Cognis UK Ltd. (a methoxy polyethylene glycol methacrylate with a molecular weight of 550 g / mol for the polyethylene portion glycol) 2-ethylhexyl thioglycolate, Dr. Spiess Chemische Fabrik, 99.8% pure Example 1
    [0070] In a double-wrap container equipped with a thermometer, reflux condenser and nitrogen inlet tube, 273 g of 2-butanone, 66 g of styrene and 59 g of maleic anhydride were initially charged and heated under an atmosphere of N2 to an internal temperature of 75 ° C over 30 minutes with stirring. Therefore, 199 g of styrene, 176 g of maleic anhydride, 228 g of 2-butanone, 5 g of dilauroyl peroxide and 2.5 g of 2-ethylhexyl thioglycolate were dosed in the reactor for 3 hours at a constant rate. Finally, the batch was then reacted at an internal temperature of 75 ° C for 3 hours and cooled to room temperature. Example 2
    [0071] In a double-wrap container equipped with a thermometer, reflux condenser and nitrogen inlet tube, 383 g of 2-butanone, 56 g of styrene and 50 g of maleic anhydride and 19 g of Bisomer MPEG550MA were initially loaded and heated under an atmosphere of N2 to an internal temperature of 75 ° C over a period of 30 minutes with stirring. Therefore, 169 g of styrene, 150 g of maleic anhydride, 56 g of Bisomer MPEG550MA, 118 g of 2-butanone, 5 g of dilauroyl peroxide and 1 g of 2-ethylhexyl thioglycolate were dosed in the reactor for 3 hours in a constant rate. Finally, the batch was then reacted at an internal temperature of 75 ° C for 3 hours and cooled to room temperature. Example 3
    [0072] In a double-wrap container equipped with a thermometer, reflux condenser and nitrogen inlet tube, 373 g of 2-butanone, 56 g of styrene and 56 g of maleic anhydride, 19 g of Bisomer MPEG550MA and 6 g of Methacrylic acid was initially charged and heated under an atmosphere of isha to an internal temperature of 75 ° C over a period of 30 minutes with stirring. Therefore, 169 g of styrene, 169 g of maleic anhydride, 56 g of Bisomer MPEG550MA, 19 g of methacrylic acid, 379 g of 2-butanone, 5 g of dilauroyl peroxide and 2.5 g of 2-ethylhexyl thioglycolate were dosed in the reactor for 3 hours at a constant rate. Finally, the batch was then reacted at an internal temperature of 75 ° C for 3 hours and cooled to room temperature. Example 4
    [0073] In a double-wrap container equipped with a thermometer, reflux condenser and nitrogen inlet tube, 349 g of 2-butanone, 44 g of styrene and 40 g of maleic anhydride and 36 g of Bisomer MPEG550MA were initially loaded and heated under Nza atmosphere to an internal temperature of 75 ° C over 30 minutes with stirring. Therefore, 178 g of styrene, 158 g of maleic anhydride, 144 g of Bisomer MPEG550MA, 251 g of 2-butanone, 5 g of dilauroyl peroxide and 3 g of 2-ethylhexyl thioglycolate were dosed in the reactor for 3 hours in a constant rate. Finally, the batch was then reacted at an internal temperature of 75 ° C for 3 hours and cooled to room temperature. Example 5
    [0074] In a double-wrap container equipped with a thermometer, reflux condenser and nitrogen inlet tube, 349 g of 2-butanone, 54 g of styrene, 48 g of maleic anhydride and 18 g of acrylic acid were initially loaded and heated under an atmosphere of N2 to an internal temperature of 75 ° C over a period of 30 minutes with stirring. Consequently, 216 g of styrene, 192 g of maleic anhydride, 72 g of acrylic acid, 251 g of 2-butanone, 6 g of dilauroyl peroxide and 3 g of 2-ethylhexyl thioglycolate were dosed in the reactor for 3 hours in a constant rate. Finally, the batch was then reacted at an internal temperature of 75 ° C for 3 hours and cooled to room temperature. Example 6
    [0075] In a double-wrap container equipped with a thermometer, reflux condenser and nitrogen inlet tube, 334 g of 2-butanone, 53 g of isobutyl vinyl ether and 49 g of maleic anhydride were initially charged and heated under atmosphere isphea at an internal temperature of 75 ° C over a period of 30 minutes with stirring. Accordingly, 214 g of isobutyl vinyl ether, 198 g of maleic anhydride, 181 g of 2-butanone, 5 g of dilauroyl peroxide and 2.5 g of 2-ethylhexyl thioglycolate were dosed in the reactor for 3 hours at a rate constant. Finally, the batch was then reacted at an internal temperature of 75 ° C for 3 hours and cooled to room temperature. Precursors to Examples 7 and 8
    [0076] In a Witt pot equipped with a blade stirrer, thermometer and reflux condenser of 75 g of ethylene-propylene copolymer (55:45, BUNA® EP G 2050, Lanxess) and 252 g of butyl acetate are initially loaded, stirred at 280 revolutions per minute, heated to 110 ° C and devolatilized with dry ice. After 2 hours, 1.5 g of tert-butyl peroctoate are added to the initial charge and then the addition of 148 g of methyl methacrylate, 148 g of butyl methacrylate and 4.5 g of tert-butyl peroctoate, when a mixture is started. After 3 hours of extra time and 1 hour after the final addition, 0.6 g of tert-butyl peroctoate is added and the temperature is maintained at 105-110 ° C for an additional 7 hours. Throughout the complete reaction time a constant flow of nitrogen gas is passed over the batch. The solution cooled to room temperature after the polymerization is finished is diluted with about 35% with butyl acetate. The product is bluish, milky cloudy. The viscosity (about 35% strength) is about 1000-2000 mPa s. Example 7
    [0077] In a double-wrap container equipped with a thermometer, reflux condenser and nitrogen inlet tube, 195 g of 2-butanone and 274 g of the precursor above were initially charged and heated under an N2 atmosphere to an internal temperature of 75 ° C within 30 minutes with stirring. Consequently, 142 g of styrene, 127 g of maleic anhydride, 115 g of Bisomer MPEG550MA, 347 g of 2-butanone, 4 g of dilauroyl peroxide and 2 g of 2-ethylhexyl thioglycolate were dosed in the reactor for 3 hours in a constant rate. Finally, the batch was then reacted at an internal temperature of 75 ° C for 3 hours and cooled to room temperature. Example 8
    [0078] In a double-wrap container equipped with a thermometer, reflux condenser and nitrogen inlet tube, 284 g of 2-butanone and 137 g of the precursor described above were initially charged and heated under an N2 atmosphere to an internal temperature of 75 ° C within 30 minutes with stirring. Therefore, 160 g of styrene, 143 g of maleic anhydride, 130 g of Bisomer MPEG550MA, 347 g of 2-butanone, 4.5 g of dilauroyl peroxide and 2.2 g of 2-ethylhexyl thioglycolate were dosed in the reactor during 3 hours at a constant rate. Finally, the batch was then reacted at an internal temperature of 75 ° C for 3 hours and cooled to room temperature. Example 9
    [0079] In a double-wrapped container equipped with a thermometer, reflux condenser and nitrogen inlet tube, 349 g of 2-butanone, 54 g of styrene, 48 g of maleic anhydride and 18 g of ethyl acrylate were initially loaded and heated under an atmosphere of N2a to an internal temperature of 75 ° C over a period of 30 minutes with stirring. Therefore, 216 g of styrene, 192 g of maleic anhydride, 72 g of ethyl acrylate and 251 g of 2-butanone, 6 g of dilauroyl peroxide and 3 g of 2-ethylhexyl thioglycolate were dosed in the reactor for 3 hours in a constant rate. Finally, the batch was then reacted at an internal temperature of 75 ° C for 3 hours and cooled to room temperature. Table 1: Examples
    权利要求:
    Claims (6)
    [0001]
    1. Support material for the 3D printing process by molten deposition modeling (FDM), characterized by the fact that it contains: at least 60% by weight of a copolymer containing 30% to 60% by weight of maleic anhydride, and from 30% to 60% by weight of copolimerizable monomers with maleic anhydride, and the support material is at least 60% by weight soluble in aqueous medium at a pH between 6 and 14.
    [0002]
    2. Support material according to claim 1, characterized by the fact that it contains: at least 60% by weight of a copolymer containing from 30% to 60% by weight of styrene, and from 30% to 60% by weight of maleic anhydride.
    [0003]
    Support material according to claim 1 or 2, characterized in that the copolymer additionally includes from 2% to 20% by weight of (meth) acrylic acid.
    [0004]
    Support material according to at least one of claims 1 to 3, characterized in that the copolymer additionally includes from 2% to 40% by weight of a methoxy polyethylene glycol methacrylate having a molecular weight Mw between 250 and 2000.
    [0005]
    Support material according to at least one of claims 1 to 4, characterized in that the copolymer has a glass transition temperature, which differs by no more than 25 ° C from the glass transition temperature of the construction material used.
    [0006]
    Support material according to at least one of claims 1 to 5, characterized in that the copolymer
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    同族专利:
    公开号 | 公开日
    CN103380156B|2016-01-20|
    CN103380156A|2013-10-30|
    US8822590B2|2014-09-02|
    CA2833752A1|2012-10-26|
    EP2699611B1|2015-05-06|
    RU2013151313A|2015-05-27|
    JP5893128B2|2016-03-23|
    AU2012244499A1|2013-07-25|
    US20130317164A1|2013-11-28|
    JP2014511933A|2014-05-19|
    EP2514775A1|2012-10-24|
    BR112013023429A2|2016-12-13|
    IL227363A|2016-09-29|
    KR20140009442A|2014-01-22|
    WO2012143182A1|2012-10-26|
    EP2699611A1|2014-02-26|
    IL227363D0|2013-09-30|
    AU2012244499B2|2015-05-21|
    CA2833752C|2019-05-14|
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    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-03-31| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2020-08-04| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-11-17| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 13/03/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP11163199.0|2011-04-20|
    EP11163199A|EP2514775A1|2011-04-20|2011-04-20|Maleic anhydride copolymers as soluble support material for fused deposition modellingprinter|
    PCT/EP2012/054306|WO2012143182A1|2011-04-20|2012-03-13|Maleic anhydride copolymers as soluble support material for fused deposition modellingprinter|
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