CN105440199A - Polyacrylate-based 3D printing material and preparation method thereof - Google Patents
Polyacrylate-based 3D printing material and preparation method thereof Download PDFInfo
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- CN105440199A CN105440199A CN201510936726.0A CN201510936726A CN105440199A CN 105440199 A CN105440199 A CN 105440199A CN 201510936726 A CN201510936726 A CN 201510936726A CN 105440199 A CN105440199 A CN 105440199A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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Abstract
The invention discloses a polyacrylate-based 3D printing material and a preparation method thereof. The preparation method of the 3D printing material comprises the following steps: preparing an acrylic emulsion from 40-90 parts of a hard monomer, 10-60 parts of a soft monomer, 5-10 parts of a carboxyl group-containing monomer, 1-3 parts of an emulsifier and 0.2-1 part of an initiator, mixing the acrylic emulsion with inorganic compound powder, and grinding the obtained mixture. The polyacrylate resin emulsion is adsorbed to calcium sulfate and other inorganic compound powder, so the 3D printing material combining the high structural strength of the inorganic compound with the high flexibility of an organic polymer is prepared; a solid product printed by adopting the 3D printing material has good mechanical strength and mechanical performances, good flexibility and extremely wide application prospect; and water is used as a reaction medium and a bonding solution in the production and printing processes of the 3D printing material, so zero discharge of VOCs, environmental protection and safe operation are realized, and current low carbon and environmental protection demands are met.
Description
Technical field
The present invention relates to a kind of 3D printed material and preparation method thereof, specifically a kind of polyacrylate based 3D printed material and preparation method thereof.
Background technology
3D printing technique, based on digital model file, uses powdery metal or plastics etc. can jointing material, manufactures entity by the mode successively printed.3D printing technique, as the revolutionary manufacturing technology of new millennium across the epoch, has obtained in fields such as automobile, aerospace, education, civil engineering work, biologic medicals gradually and has applied more and more widely.
But current 3D printing technique is also faced with many problems.Wherein, the shortage of 3D printed material is one of maximum bottleneck of restriction 3D printing technique development.The 3D printed material that at present mainly to use with gypsum, photosensitive resin, plastics be matrix, there is the defects such as printing precision difference, entity product intensity is not enough, print speed is slow, manufacturing cost is high in them, is difficult to meet modern industry application.
Such as, Chinese invention patent CN201310420778.3 discloses a kind of 3D printed material based on edible wax, by its to print the physical strength of the entity finished product of preparation very poor, be not suitable for being applied to industrial use completely.Chinese invention patent CN201410458299.5 discloses a kind of inorganic powder class 3D printed material, although the physical strength printing the entity finished product of preparation by it is better, and snappiness extreme difference, and also print speed is slow, is therefore difficult to obtain practical application.Chinese invention patent CN201310091047.9 discloses a kind of by photopolymerization curing polyurethane acrylate prepolymer class 3D printed material, although the snappiness of the entity finished product manufactured by it is excellent, but physical strength is poor, and the manufacturing process of associated resin and Print Control technique quite complicated, manufacturing cost is high, moreover need to use many volatilizable industrial chemicals having certain toxicity, therefore this material is almost difficult to universal use.
Therefore, develop to print there is excellent physical strength and mechanical property, and the 3D printed material of better flexible entity finished product, be the current gordian technique difficult problem needing solution badly.
Summary of the invention
The object of the invention is to overcome the existing defect of above-mentioned technology, provide a kind of and can print the 3D printed material producing and have excellent mechanical strength and flexible entity finished product concurrently.
Another object of the present invention is to provide the preparation method of this 3D printed material.
For one of achieving the above object, the present invention by the following technical solutions:
A kind of polyacrylate based 3D printed material, according to parts by weight, described polyacrylate based 3D printed material makes ACRYLIC EMULSION by 40 ~ 90 parts of hard monomers, 10 ~ 60 parts of soft monomers, 5 ~ 10 parts of carboxyl group-containing monomers, 1 ~ 3 part of emulsifying agent, 0.2 ~ 1 part of initiator, then ACRYLIC EMULSION and mineral compound powder is mixed, grinds and obtain.
Further, described hard monomer is at least one in vinylbenzene, methyl acrylate and methyl methacrylate.
Further, described soft monomer is at least one in ethyl propenoate, butyl acrylate and butyl methacrylate.
Further, described carboxyl group-containing monomer is vinylformic acid and/or methacrylic acid.
Further, described emulsifying agent is at least one in sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, alkylphenol polyoxyethylene, sapn, tween and fatty alcohol-polyoxyethylene ether.
Further, described initiator is at least one in ammonium persulphate, Potassium Persulphate and Sodium Persulfate.
Further, described mineral compound powder is anhydrous calciumsulphate and/or hydration two calcium sulfate.
Further, the mass ratio of described ACRYLIC EMULSION and mineral compound powder is 1:20 ~ 200.
The preparation method of foregoing polyacrylate based 3D printed material, comprises the following steps:
S1, employing semi-continuous emulsion polymerizing technique, through copolyreaction acrylic acid synthesizing emulsion;
S2, prepared ACRYLIC EMULSION and mineral compound powder to be mixed, and be fully ground to particle diameter and be not less than 2000 orders, i.e. obtained 3D printed material.
Further, described step S1 is specially: first hard monomer, soft monomer and carboxyl group-containing monomer are mixed, then the mix monomer of 1/5 ~ 1/3 and emulsifying agent are joined in reactor and also fully stir, reactor be warming up to 70 ~ 85 DEG C again and start respectively to drip initiator solution and remaining mix monomer, control time for adding is 1 ~ 3h; Insulation reaction 3 ~ 6h afterwards, is finally cooled to room temperature and extracts remaining unreacted monomer completely, i.e. obtained ACRYLIC EMULSION.
Hard monomer Main Function is to provide the performance such as hardness, intensity (as ultimate compression strength, tensile strength etc.), water tolerance of entity finished product.But hard monomer consumption is too much, can reduce the bonding force of ACRYLIC EMULSION and mineral compound powder, thus reduce the cohesive strength of entity finished product.
Soft monomer Main Function is to provide the flexibility of entity finished product and the bonding force to mineral compound powder thereof.But soft monomer consumption is too much, can make the surfaces of tacky of entity finished product, easily stain and set-off.
The Main Function of carboxylic monomer provides some amount-COOH for acrylic resin macromolecular chain, it not only can improve the bonding force of ACRYLIC EMULSION and mineral compound powder, can be slightly swelling when the more important thing is and make printed material meet water (namely as bonding solution) in print procedure, thus formation entity finished product wrapped around one another.But carboxyl group-containing monomer consumption is too much, when can make that printed material meets water in print procedure, the degree of swelling aggravation of acrylic resin, directly causes printing precision and resolving power to be deteriorated rapidly.
In emulsifying agent, better, the preferred range of both mass ratios is 1 ~ 3:1 for anionic emulsifier and the composite result of use of nonionic emulsifier.Emulsifier is very few, and emulsion polymerization is difficult to control, and even produces the phenomenons such as implode, layering and even gel; Emulsifier is too much, and by causing, the water-intake rate of entity finished product is higher, be long placed in easily absorb moisture in air and can deform, expand, the adverse consequences such as jaundice.
The effect of initiator is to provide free radical, guides polymerization to occur; Its consumption can not be too low, can not be too high.
Anhydrous calciumsulphate and hydration two calcium sulfate not only pore texture and surface can absorbing propenoic acid emulsions, and they are owing to can react with water, thus make acrylic resin be adsorbed on their surfaces securely.The major function of mineral compound is for entity finished product provides sufficiently high physical strength and mechanical property, but its consumption too much just can cause the snappiness of entity finished product not enough.
The present invention has following beneficial effect:
1, polyacrylate resin emulsion is adsorbed in the mineral compound powder such as calcium sulfate by the present invention, thus the obtained 3D printed material having the high structural strength of mineral compound and the high-flexibility of organic polymer concurrently; Adopt the entity finished product that 3D printed material of the present invention prints not only to have more excellent physical strength and mechanical property, and have good snappiness, efficiently solve the shortcoming of current 3D printed material, therefore application prospect is very wide.
2, in the production and print procedure of 3D printed material respectively using water as reaction medium and bonding solution, Diamond Search discharge, not only environmental protection, and operational safety, meet the demand of current low-carbon environment-friendly.
3, manufacturing process of the present invention is simple, low production cost.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further:
The mark of following examples all refers to weight part.
embodiment 1
A kind of polyacrylate based 3D printed material, is prepared from according to following steps:
1, first 40 parts of methyl methacrylates, 10 parts of butyl acrylates and 5 parts of vinylformic acid are mixed, then the mix monomer of 1/5 and 1 part of sodium lauryl sulphate are joined in reactor and also fully stir, reactor be warming up to 70 DEG C again and start respectively to drip 0.2 part of Sodium Persulfate solution and remaining mix monomer, control time for adding is 1h; Insulation reaction 3h afterwards, is finally cooled to room temperature and extracts remaining unreacted monomer completely, i.e. obtained ACRYLIC EMULSION;
2, prepared ACRYLIC EMULSION and anhydrous calciumsulphate are mixed according to the mass ratio of 1:200, and be fully ground to particle diameter and be not less than 2000 orders, be i.e. obtained 3D printed material 1#.
embodiment 2
A kind of polyacrylate based 3D printed material, is prepared from according to following steps:
1, first 40 parts of methyl methacrylates, 50 parts of vinylbenzene, 10 parts of butyl acrylates, 50 parts of butyl methacrylate and 5 parts of vinylformic acid, 5 parts of methacrylic acids are mixed, then the mix monomer of 1/3 and composite emulsifier (2 parts of sodium lauryl sulphate and 1 part of alkylphenol polyoxyethylene OP-10 composite) to be joined in reactor and fully to stir, reactor be warming up to 85 DEG C again and start respectively to drip initiator (0.2 part of Sodium Persulfate, 0.8 part of ammonium persulphate) solution and remaining mix monomer, control time for adding is 3h; Insulation reaction 6h afterwards, is finally cooled to room temperature and extracts remaining unreacted monomer completely, i.e. obtained ACRYLIC EMULSION;
2, prepared ACRYLIC EMULSION and hydration two calcium sulfate are mixed according to the mass ratio of 1:20, and be fully ground to particle diameter and be not less than 2000 orders, be i.e. obtained 3D printed material 2#.
embodiment 3
A kind of polyacrylate based 3D printed material, is prepared from according to following steps:
1, first by 30 parts of methyl methacrylates, 20 parts of vinylbenzene, 20 parts of methyl acrylates, 30 parts of butyl acrylates, 10 parts of butyl methacrylate, 10 parts of ethyl propenoates and 4 parts of vinylformic acid, 3 parts of methacrylic acids mix, then the mix monomer of 1/4 and composite emulsifier (1.5 parts of sodium lauryl sulphate and 0.5 part of alkylphenol polyoxyethylene OP-10 composite) to be joined in reactor and fully to stir, again reactor be warming up to 80 DEG C and start respectively to drip initiator (0.1 part of Sodium Persulfate, 0.1 part of ammonium persulphate, 0.1 part of Potassium Persulphate) solution and remaining mix monomer, control time for adding is 2h, insulation reaction 4h afterwards, is finally cooled to room temperature and extracts remaining unreacted monomer completely, i.e. obtained ACRYLIC EMULSION,
2, prepared ACRYLIC EMULSION and mineral compound powder (anhydrous calciumsulphate, hydration two calcium sulfate) are mixed according to the mass ratio of 1:100, and be fully ground to particle diameter and be not less than 2000 orders, be i.e. obtained 3D printed material 3#.
embodiment 4
A kind of polyacrylate based 3D printed material, is prepared from according to following steps:
1, first 30 parts of vinylbenzene, 30 parts of methyl acrylates, 30 parts of butyl methacrylate and 7 parts of methacrylic acids are mixed, then the mix monomer of 1/4 and composite emulsifier (1 part of sodium laurylsulfonate and 1 part of fatty alcohol-polyoxyethylene ether AEO-7 composite) to be joined in reactor and fully to stir, reactor be warming up to 75 DEG C again and start respectively to drip 0.5 part of ammonium persulfate solution and remaining mix monomer, control time for adding is 2h; Insulation reaction 5h afterwards, is finally cooled to room temperature and extracts remaining unreacted monomer completely, i.e. obtained ACRYLIC EMULSION;
2, prepared ACRYLIC EMULSION and mineral compound powder (anhydrous calciumsulphate, hydration two calcium sulfate) are mixed according to the mass ratio of 1:50, and be fully ground to particle diameter and be not less than 2000 orders, be i.e. obtained 3D printed material 4#.
embodiment 5
Above-mentioned produced 3D printed material 1# ~ 4#, 3Dsystems company of the import powder bonded class 3D printed material Nis-AP12(U.S. are produced) and Stratasy company of the BM-5(U.S. produce) prepared the entity finished product of 10mm × 10mm × 10mm by 3D printer, carry out dependence test again, result is as shown in table 1.
Table 13D prints the test result of entity finished product
| Test index | 1# | 2# | 3# | 4# | Nios-AP12 | BM-5 |
| Flexural strength (MPa) | 1.1 | 1.2 | 1.0 | 1.1 | 1.1 | 0.9 |
| Ultimate compression strength (MPa) | 8.3 | 8.2 | 7.6 | 8.0 | 7.9 | 8.4 |
| Unit elongation (%) | 54 | 50 | 56 | 54 | 47 | 48 |
3D prints experiment condition: Z310 type 3D printer (ZCorporation company of the U.S.), piezoelectricity intermittent type printing head totally 128 holes (diameter is about 0.05mm), thickness is set to 0.175mm, saturation ratio is set to 0.7.(the bonding solution that 1# ~ 4# uses is deionized water, and Nis-AP12 and BM-5 uses genuine to carry supporting bonding solution).
As shown in Table 1,3D printed material of the present invention has higher flexural strength and ultimate compression strength and unit elongation by the physical components that 3D prints, and shows its good toughness, and mechanical property is strong, and correlated performance has reached external similar commodity.In addition, 3D printed material manufacturing process of the present invention is simple, with low cost, and water only need be used as bonding solution, environmental protection.Therefore, technology of the present invention application and industrialization prospect very wide.
The above; be only the specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, anyly belongs to those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claim.
Claims (10)
1. a polyacrylate based 3D printed material, it is characterized in that, according to parts by weight, described polyacrylate based 3D printed material makes ACRYLIC EMULSION by 40 ~ 90 parts of hard monomers, 10 ~ 60 parts of soft monomers, 5 ~ 10 parts of carboxyl group-containing monomers, 1 ~ 3 part of emulsifying agent, 0.2 ~ 1 part of initiator, then ACRYLIC EMULSION and mineral compound powder is mixed, grinds and obtain.
2. polyacrylate based 3D printed material according to claim 1, is characterized in that, described hard monomer is at least one in vinylbenzene, methyl acrylate and methyl methacrylate.
3. polyacrylate based 3D printed material according to claim 1, is characterized in that, described soft monomer is at least one in ethyl propenoate, butyl acrylate and butyl methacrylate.
4. polyacrylate based 3D printed material according to claim 1, is characterized in that, described carboxyl group-containing monomer is vinylformic acid and/or methacrylic acid.
5. polyacrylate based 3D printed material according to claim 1, it is characterized in that, described emulsifying agent is at least one in sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, alkylphenol polyoxyethylene, sapn, tween and fatty alcohol-polyoxyethylene ether.
6. polyacrylate based 3D printed material according to claim 1, is characterized in that, described initiator is at least one in ammonium persulphate, Potassium Persulphate and Sodium Persulfate.
7. polyacrylate based 3D printed material according to claim 1, is characterized in that, described mineral compound powder is anhydrous calciumsulphate and/or hydration two calcium sulfate.
8. polyacrylate based 3D printed material according to claim 1, is characterized in that, the mass ratio of described ACRYLIC EMULSION and mineral compound powder is 1:20 ~ 200.
9. the preparation method of the polyacrylate based 3D printed material described in above-mentioned any one claim, is characterized in that, comprise the following steps:
S1, employing semi-continuous emulsion polymerizing technique, through copolyreaction acrylic acid synthesizing emulsion;
S2, prepared ACRYLIC EMULSION and mineral compound powder to be mixed, and be fully ground to particle diameter and be not less than 2000 orders, i.e. obtained 3D printed material.
10. preparation method according to claim 9, it is characterized in that, described step S1 is specially: first hard monomer, soft monomer and carboxyl group-containing monomer are mixed, then the mix monomer of 1/5 ~ 1/3 and emulsifying agent are joined in reactor and also fully stir, reactor be warming up to 70 ~ 85 DEG C again and start respectively to drip initiator solution and remaining mix monomer, control time for adding is 1 ~ 3h; Insulation reaction 3 ~ 6h afterwards, is finally cooled to room temperature and extracts remaining unreacted monomer completely, i.e. obtained ACRYLIC EMULSION.
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| CN106674433A (en) * | 2016-11-25 | 2017-05-17 | 安徽省春谷3D打印智能装备产业技术研究院有限公司 | 3d printing powder and preparation method thereof |
| CN106749854A (en) * | 2016-12-16 | 2017-05-31 | 北方华锦化学工业集团有限公司 | A kind of preparation method of new 3D printing polyacrylic resin |
| EP3235867A1 (en) * | 2016-04-20 | 2017-10-25 | Evonik Röhm GmbH | Polymer beads from hard phase with domains of a soft phase |
| CN107446078A (en) * | 2017-08-01 | 2017-12-08 | 安徽原动力生产力促进中心有限公司 | A kind of 3D gypsum printing technology |
| CN109070445A (en) * | 2016-04-12 | 2018-12-21 | 赢创罗姆有限公司 | For filling the soft phase emulsion polymer of the spray drying in the gap in pearl polymerisation nitride layer in adhesive injection method |
| ES2732766A1 (en) * | 2018-05-24 | 2019-11-25 | Consejo Superior Investigacion | Procedure for obtaining a piece by thread deposition modeling molten (Machine-translation by Google Translate, not legally binding) |
| US10688718B2 (en) | 2016-09-28 | 2020-06-23 | Evonik Operations Gmbh | Production and use of porous bead polymers in 3D printing using the binder jetting method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109070445A (en) * | 2016-04-12 | 2018-12-21 | 赢创罗姆有限公司 | For filling the soft phase emulsion polymer of the spray drying in the gap in pearl polymerisation nitride layer in adhesive injection method |
| US10695978B2 (en) | 2016-04-12 | 2020-06-30 | Evonik Operations Gmbh | Spray-dried soft-phase emulsion polymer for filling the gussets in bead polymer layers in a binder jetting method |
| CN109070445B (en) * | 2016-04-12 | 2021-03-30 | 赢创罗姆有限公司 | Spray-dried soft-phase emulsion polymers for filling gaps in bead polymer layers in adhesive spray processes |
| EP3235867A1 (en) * | 2016-04-20 | 2017-10-25 | Evonik Röhm GmbH | Polymer beads from hard phase with domains of a soft phase |
| WO2017182364A1 (en) * | 2016-04-20 | 2017-10-26 | Evonik Röhm Gmbh | Bead polymer made of hard phase with domains of a soft phase |
| US10793731B2 (en) | 2016-04-20 | 2020-10-06 | Evonik Operations Gmbh | Bead polymer made of hard phase with domains of a soft phase |
| AU2017253536B2 (en) * | 2016-04-20 | 2020-12-03 | Evonik Operations Gmbh | Bead polymer made of hard phase with domains of a soft phase |
| US10688718B2 (en) | 2016-09-28 | 2020-06-23 | Evonik Operations Gmbh | Production and use of porous bead polymers in 3D printing using the binder jetting method |
| CN106674433A (en) * | 2016-11-25 | 2017-05-17 | 安徽省春谷3D打印智能装备产业技术研究院有限公司 | 3d printing powder and preparation method thereof |
| CN106749854A (en) * | 2016-12-16 | 2017-05-31 | 北方华锦化学工业集团有限公司 | A kind of preparation method of new 3D printing polyacrylic resin |
| CN107446078A (en) * | 2017-08-01 | 2017-12-08 | 安徽原动力生产力促进中心有限公司 | A kind of 3D gypsum printing technology |
| ES2732766A1 (en) * | 2018-05-24 | 2019-11-25 | Consejo Superior Investigacion | Procedure for obtaining a piece by thread deposition modeling molten (Machine-translation by Google Translate, not legally binding) |
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