CN104845031A - Preparation method for three-dimensional printing material - Google Patents
Preparation method for three-dimensional printing material Download PDFInfo
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- CN104845031A CN104845031A CN201510275913.9A CN201510275913A CN104845031A CN 104845031 A CN104845031 A CN 104845031A CN 201510275913 A CN201510275913 A CN 201510275913A CN 104845031 A CN104845031 A CN 104845031A
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Abstract
The invention discloses a preparation method for a three-dimensional printing material. The preparation method comprises the steps: adding an additive to ABS grafting powder and mixing with SAN grains; after mixing uniformly, extruding and pelletizing the mixture to obtain the three-dimensional printing material. The three-dimensional printing material is prepared from the following three raw materials in parts by weight: 40-70 parts of the ABS grafting powder, 5-10 parts of the additive, and 30-50 parts of the SAN grains; the additive is a mixture of polyphenyl ether, polycarbonate and modified polyacrylate. The preparation method has the advantages that the reaction conditions are tender and the operation is simple; the three-dimensional printing material prepared by the method has excellent thermal stability and low thermal deformation.
Description
Technical field
The invention belongs to technical field of macromolecules, be specifically related to a kind of preparation method of 3D printed material.
Background technology
3D printing is by microcomputer modelling and controls, and by heating power dissolved for reconstitution or laser formation technology, builds a process of three-dimensional object.Because process is similar to traditional prints, so be referred to as visually " 3D printing ".And so-called 3D printer is substantially identical with normal printer principle of work, just some difference of printed material, the printed material of normal printer is ink and paper, and 3D printer is built with different " printed material " such as metal, pottery, plastics, sand, out and out starting material, after printer is connected with computer, " printed material " can be stacked up from level to level by conputer controlled, finally the blueprint on computer be become in kind.
3D prints common used material nylon glass, wearing quality nylon material, gypsum material, aluminum, titanium alloy, stainless steel, silver-plated, gold-plated, rubber type of material.Modal is ABS material.The print temperature of this material is 210 ~ 240 DEG C, and the temperature of hot-plate is more than 80 DEG C.The glass transition temp (this plastics start the temperature of softening) of ABS is 105 DEG C.The properties of material, from the angle in hot junction, ABS plastic quite easily prints.No matter use which type of forcing machine, all can extruded material glidingly, blocking need not be worried or solidify.ABS resilient enough, is applicable to making furnishings, as long as print with suitable temperature, allow material layer by layer firmly stick, the intensity of ABS will become quite high.ABS has flexibility, also only can bend, can not fracture even if bear pressure.But this material has and meets the characteristic of cold events, from local shedding hot-plate, unsettled, can throw into question.
Summary of the invention
Goal of the invention: the preparation method that the object of this invention is to provide a kind of 3D printed material, can obtain the 3D printed material of better heat stability by the method.
Technical scheme: the preparation method that the invention provides a kind of 3D printed material, is characterized in that ABS grafting powder to add additive, mixes with SAN particle, after mixing, and extruding, granulation, obtains product; The proportioning of three kinds of described raw materials is: with weight parts, 40 ~ 70 parts, ABS grafting powder, additive 5 ~ 10 parts, SAN particle 30 ~ 50 parts; Described additive is benzothiazole or polyimide.
Described ABS grafting powder obtains by the following method: by the solution of emulsifying agent, mercaptan, Potassium Persulphate composition and polymerizing butadiene, temperature of reaction 90 ~ 93 degrees Celsius, in 15 ~ 18 hours reaction times, after reaction, cools with liquefied ammonia; Add third rare nitrile, α-methylstyrenemonomer, then add initiator, temperature of reaction is 90 ~ 95 degrees Celsius, 5 ~ 6 hours reaction times, condense after reaction terminates, condensation temperature 90 ~ 95 degrees Celsius, will the fine particle obtained be condensed, after washing, dry, obtain ABS grafting powder.Emulsifying agent described in this process is oleic acid potash soap; Described initiator is dicumyl peroxide; Described flocculation agent is dilute sulphuric acid or alum.
Described SAN particle obtains by the following method: carry out polyreaction after the material preheating be made up of α-methylstyrenemonomer, vinyl cyanide and N-phenyl maleimide imines, temperature is 120 ~ 150 degrees Celsius, pressure 0.196 ~ 0.294 MPa, volatiles is removed after reaction, obtain the resin of molten, cooling, extrusion, pelletizing, obtains SAN particle.The mass ratio of vinyl cyanide and α-methylstyrenemonomer is 3:7.N-phenyl maleimide imines accounts for 5% ~ 10% of monomer weight.
The concrete steps of removing volatiles are: after remove most of vinyl cyanide and part α-methylstyrenemonomer, N-phenyl maleimide imines from polymeric kettle material flash distillation under 0.196 MPa out, then be heated to 240 degrees Celsius, under 2.67 kpa pressures, remove remaining α-methylstyrenemonomer again.
Beneficial effect: preparation method provided by the invention, reaction conditions is gentle, and simple to operate, the 3D printed material utilizing present method to obtain has good thermostability, little by thermal deformation.
Embodiment:
Embodiment 1
The compounding agent solution of emulsifying agent oleic acid potash soap 1g, mercaptan 5g, Potassium Persulphate 0.5g composition is added in polymeric kettle together with divinyl 100g, temperature of reaction 90 degrees Celsius, 16 hours reaction times, after reaction, with liquefied ammonia cooling, obtain polybutadiene latex.The transformation efficiency 80% of divinyl.
By third rare nitrile 1g, α-methylstyrenemonomer 60g and polybutadiene latex 5g obtained above joins in reactor, take dicumyl peroxide as initiator, and temperature of reaction is 90 degrees Celsius, 5 hours reaction times, condense after reaction terminates, flocculation agent is dilute sulphuric acid or alum, condensation temperature 90 degrees Celsius, cohesion obtains fine particle, after washing, dry, obtain ABS grafting powder.Dried ABS grafting powder water content is less than 0.5%%.The transformation efficiency of monomer is 88%.
The material be made up of α-methylstyrenemonomer 70g, vinyl cyanide 30g and N-phenyl maleimide imines 7g enters polymeric kettle after preheating, polymeric reaction temperature is 120 degrees Celsius, pressure 0.196 MPa, removes most of vinyl cyanide and the volatiles such as part α-methylstyrenemonomer, N-phenyl maleimide imines from polymeric kettle material flash distillation under 0.196 MPa out after reaction.Then after being heated to 240 degrees Celsius, removing the volatiless such as remaining α-methylstyrenemonomer again, obtain the resin of molten under 2.67 kpa pressures, extrusion after cooling, pelletizing obtains SAN particle.
40 parts of ABS grafting powder and 30 parts of SAN particles are added that 10 parts of benzothiazoles mix in a mixer, then enters extruding pelletization in twin screw extruder.Obtain product.After testing, anti-impact level intensity reaches 165J/m.
Embodiment 2
The compounding agent solution of emulsifying agent oleic acid potash soap 2g, mercaptan 15g, Potassium Persulphate 1g composition is added in polymeric kettle together with divinyl 100g, temperature of reaction 93 degrees Celsius, 16 hours reaction times, after reaction, with liquefied ammonia cooling, obtain polybutadiene latex.The transformation efficiency 83% of divinyl.
By third rare nitrile 40g, α-methylstyrenemonomer 85g and polybutadiene latex 15g obtained above joins in reactor, take dicumyl peroxide as initiator, and temperature of reaction is 90 degrees Celsius, 6 hours reaction times, condense after reaction terminates, flocculation agent is dilute sulphuric acid or alum, condensation temperature 90 degrees Celsius, cohesion obtains fine particle, after washing, dry, obtain ABS grafting powder.Dried ABS grafting powder water content is less than 1%.The transformation efficiency of monomer is 88%.
The material be made up of α-methylstyrenemonomer 70g, vinyl cyanide 30g and N-phenyl maleimide imines 7g enters polymeric kettle after preheating, polymeric reaction temperature is 150 degrees Celsius, pressure 0.294 MPa, removes most of vinyl cyanide and the volatiles such as part α-methylstyrenemonomer, N-phenyl maleimide imines from polymeric kettle material flash distillation under 0.196 MPa out after reaction.Then after being heated to 240 degrees Celsius, removing the volatiless such as remaining α-methylstyrenemonomer again, obtain the resin of molten under 2.67 kpa pressures, extrusion after cooling, pelletizing obtains SAN particle.
50 parts of ABS grafting powder and 40 parts of SAN particles are added that 10 parts of polyimide mix in a mixer, then enters extruding pelletization in twin screw extruder.Obtain product.After testing, anti-impact level intensity reaches 171J/m.
Embodiment 3
The compounding agent solution of emulsifying agent oleic acid potash soap 1g, mercaptan 5g, Potassium Persulphate 0.5g composition is added in polymeric kettle together with divinyl 100g, temperature of reaction 90 degrees Celsius, 16 hours reaction times, after reaction, with liquefied ammonia cooling, obtain polybutadiene latex.The transformation efficiency 80% of divinyl.
By third rare nitrile 1g, α-methylstyrenemonomer 60g and polybutadiene latex 5g obtained above joins in reactor, take dicumyl peroxide as initiator, and temperature of reaction is 90 degrees Celsius, 5 hours reaction times, condense after reaction terminates, flocculation agent is dilute sulphuric acid or alum, condensation temperature 90 degrees Celsius, cohesion obtains fine particle, after washing, dry, obtain ABS grafting powder.Dried ABS grafting powder water content is less than 0.5%%.The transformation efficiency of monomer is 88%.
The material be made up of α-methylstyrenemonomer 70g, vinyl cyanide 30g and N-phenyl maleimide imines 7g enters polymeric kettle after preheating, polymeric reaction temperature is 150 degrees Celsius, pressure 0.294 MPa, removes most of vinyl cyanide and the volatiles such as part α-methylstyrenemonomer, N-phenyl maleimide imines from polymeric kettle material flash distillation under 0.196 MPa out after reaction.Then after being heated to 240 degrees Celsius, removing the volatiless such as remaining α-methylstyrenemonomer again, obtain the resin of molten under 2.67 kpa pressures, extrusion after cooling, pelletizing obtains SAN particle.
50 parts of ABS grafting powder and 40 parts of SAN particles are added that 10 parts of polyimide mix in a mixer, then enters extruding pelletization in twin screw extruder.Obtain product.After testing, anti-impact level intensity reaches 172J/m.
Claims (7)
1. a preparation method for 3D printed material, is characterized in that ABS grafting powder to add additive, mixes with SAN particle, after mixing, and extruding, granulation, obtains product;
The proportioning of three kinds of described raw materials is: with weight parts, 40 ~ 70 parts, ABS grafting powder, additive 5 ~ 10 parts, SAN particle 30 ~ 50 parts; Described additive is benzothiazole or polyimide.
2. the preparation method of 3D printed material as claimed in claim 1, it is characterized in that described ABS grafting powder obtains by the following method: by the solution of emulsifying agent, mercaptan, Potassium Persulphate composition and polymerizing butadiene, temperature of reaction 90 ~ 93 degrees Celsius, 15 ~ 18 hours reaction times, after reaction, cool with liquefied ammonia;
Add third rare nitrile, α-methylstyrenemonomer, then add initiator, temperature of reaction is 90 ~ 95 degrees Celsius, 5 ~ 6 hours reaction times, condense after reaction terminates, condensation temperature 90 ~ 95 degrees Celsius, will the fine particle obtained be condensed, after washing, dry, obtain ABS grafting powder.
3. the preparation method of 3D printed material as claimed in claim 2, is characterized in that described emulsifying agent is oleic acid potash soap; Described initiator is dicumyl peroxide; Described flocculation agent is dilute sulphuric acid or alum.
4. the preparation method of 3D printed material as claimed in claim 1, it is characterized in that described SAN particle obtains by the following method: after the material preheating be made up of α-methylstyrenemonomer, vinyl cyanide and N-phenyl maleimide imines, carry out polyreaction, temperature is 120 ~ 150 degrees Celsius, pressure 0.196 ~ 0.294 MPa, removes volatiles after reaction, obtains the resin of molten, cooling, extrusion, pelletizing, obtains SAN particle.
5. the preparation method of 3D printed material as claimed in claim 4, is characterized in that the mass ratio of vinyl cyanide and α-methylstyrenemonomer is 3:7.
6. the preparation method of 3D printed material as claimed in claim 4, is characterized in that N-phenyl maleimide imines accounts for 5% ~ 10% of monomer weight.
7. the preparation method of 3D printed material as claimed in claim 1, it is characterized in that removing the concrete steps of volatiles is: after remove most of vinyl cyanide and part α-methylstyrenemonomer, N-phenyl maleimide imines from polymeric kettle material flash distillation under 0.196 MPa out, then be heated to 240 degrees Celsius, under 2.67 kpa pressures, remove remaining α-methylstyrenemonomer again.
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| CN201510275913.9A CN104845031A (en) | 2015-05-26 | 2015-05-26 | Preparation method for three-dimensional printing material |
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| CN201510275913.9A CN104845031A (en) | 2015-05-26 | 2015-05-26 | Preparation method for three-dimensional printing material |
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| CN104845031A true CN104845031A (en) | 2015-08-19 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105994391A (en) * | 2016-05-25 | 2016-10-12 | 江苏浩宇电子科技有限公司 | Insect trapping and killing 3D printed product with micropore structure and preparation method thereof |
| CN105994404A (en) * | 2016-05-25 | 2016-10-12 | 江苏浩宇电子科技有限公司 | Insect trapping and killing 3D printed product with micropore structure and preparation method thereof |
| CN108264602A (en) * | 2018-01-05 | 2018-07-10 | 长春工业大学 | A kind of terpolymer and its preparation method and application |
| JP7299399B1 (en) | 2022-10-24 | 2023-06-27 | テクノＵｍｇ株式会社 | Graft copolymers, resin compositions for plating, molded products and plated products |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104559034A (en) * | 2015-01-09 | 2015-04-29 | 机械科学研究总院先进制造技术研究中心 | Modified ABS resin for 3D printing as well as preparation method of modified ABS resin |
-
2015
- 2015-05-26 CN CN201510275913.9A patent/CN104845031A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104559034A (en) * | 2015-01-09 | 2015-04-29 | 机械科学研究总院先进制造技术研究中心 | Modified ABS resin for 3D printing as well as preparation method of modified ABS resin |
Non-Patent Citations (1)
| Title |
|---|
| 黄伯琴: "《当代石油和石化工业技术普及读本 合成树脂》", 31 October 2000 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105994391A (en) * | 2016-05-25 | 2016-10-12 | 江苏浩宇电子科技有限公司 | Insect trapping and killing 3D printed product with micropore structure and preparation method thereof |
| CN105994404A (en) * | 2016-05-25 | 2016-10-12 | 江苏浩宇电子科技有限公司 | Insect trapping and killing 3D printed product with micropore structure and preparation method thereof |
| CN108264602A (en) * | 2018-01-05 | 2018-07-10 | 长春工业大学 | A kind of terpolymer and its preparation method and application |
| CN108264602B (en) * | 2018-01-05 | 2021-03-02 | 长春工业大学 | Terpolymer and preparation method and application thereof |
| JP7299399B1 (en) | 2022-10-24 | 2023-06-27 | テクノＵｍｇ株式会社 | Graft copolymers, resin compositions for plating, molded products and plated products |
| JP2024062147A (en) * | 2022-10-24 | 2024-05-09 | テクノＵｍｇ株式会社 | Graft copolymer, plating resin composition, molded product, and plated product |
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Application publication date: 20150819 |