CN105504662A - Polyformaldehyde wire material for 3D printing and preparation method thereof - Google Patents
Polyformaldehyde wire material for 3D printing and preparation method thereof Download PDFInfo
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- CN105504662A CN105504662A CN201511010549.XA CN201511010549A CN105504662A CN 105504662 A CN105504662 A CN 105504662A CN 201511010549 A CN201511010549 A CN 201511010549A CN 105504662 A CN105504662 A CN 105504662A
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- polyoxymethylene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/05—Filamentary, e.g. strands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/30—Auxiliary operations or equipment
- B29C64/307—Handling of material to be used in additive manufacturing
- B29C64/314—Preparation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
Abstract
The invention relates to a polyformaldehyde wire material for 3D printing and a preparation method thereof. Polyethylene oxide is used for modifying the polyformaldehyde, so that the polyformaldehyde has good thermal-processing stability and flexibility, the wire forming characteristic of the polyformaldehyde is realized, thus the polyformladehyde is used as a wire material in 3D printing, and the application of the polyformaldehyde in the field of 3D printing is enlarged. Meanwhile, by adding the heat stabilizer and a formaldehyde absorbent, the heat stability of a composite material is guaranteed. Raw materials are mixed at a high speed and molten, plasticized, cut, modified, extruded and wire drawn by virtue of a dual-screw extruder to prepare the wire-shaped polyformaldehyde composite material. The wire material is good in stability, high in strength, good in flexibility and capable of meeting various requirements of the 3D printing on the powder material. An obtained product is excellent and stable in performance and good in machining performance.
Description
Technical field
The present invention relates to a kind of polyformaldehyde composite material and preparation method thereof, in particular, the present invention relates to a kind of 3D printing polyoxymethylene silk material and preparation method thereof, belong to 3D printed material field.
Background technology
3D prints, the i.e. one of rapid shaping technique, it is a kind of based on digital model file, use powdery metal or plastics etc. can jointing material, carried out the technology of constructed object by the mode successively printed, increase material manufacture also known as work, it manufactures fast, 3-D effect can be reproduced completely, product design and die production synchronously be carried out, realizes integrated manufacturing system (IMS).The material category that can be used for 3D printing device uses is extensive, comprises metallic substance, inorganic powder material, stupalith, macromolecular material, wax, paper etc.
At present, the 3D printing device technology used for macromolecular material rapid shaping mainly contains: fusion stacking forming technique (FDM), and it is for thread hot-melt plastic; Precinct laser sintering technology (SLS), it is for the rapid shaping of dusty material, is a kind of 3D printing technique that suitable material is maximum; Stereolithography apparatus technology (SLA), it is mainly used in the shaping of photosensitive resin, and raw material is liquid resin.
Fusion stacking shaping (FusedDepositionModeling, FDM) is by thread hot-melt plastic heating and melting, three-dimensional shower nozzle under control of the computer simultaneously, according to cross section profile information, material selectivity is applied on the table, form a layer cross section after cooling fast.After one formable layer completes, machine operation platform declines one deck under height (i.e. lift height) reshaping, until form whole solid modelling.FDM operating environment is clean, safety, does not have the danger of poison gas or chemical substance, does not use laser, can operate in an office environment.Starting material provide with the form of spool silk, and alternate material kind is many, and cost of raw and processed materials is lower, are easy to carrying and quick-replaceable, concise in technology.
Polyoxymethylene is that one does not have side chain, high-density, the linear polymer of high crystalline is one of five large general engineering plastic, there is excellent over-all properties, have the specific rigidity very close with metal and specific tenacity, be described as " supersteel " or " match steel ", it also has unique wear-resistant and self-lubrication, good electrical property, very high fatigue strength, creep resistance is good, use temperature a wider range.Polyoxymethylene is according to the difference of chemical structure in its molecular chain, be divided into the C-O key acefal homopolymer that is main chain and the copolymerized methanal that is main chain with C-C key, acefal homopolymer has higher degree of crystallinity compared with copolymerized methanal, therefore its density, fusing point and intensity are all higher, but thermostability is poor, easily produce decomposition, processing temperature scope is narrower, be difficult to meet 3D print and need carry out the requirements such as heating to material, therefore need to be improved its thermostability.In addition, polyoxymethylene also has obvious shortcoming, is exactly that its toughness is low, and notch sensitivity is large, and FDM technology consumptive material is thread, and the flexural strength of material, tensile strength and toughness are the keys of material ropiness, so will carry out toughening modifying to it.
Patent 201410130006.0 provides a kind of modified polyacetal propping material and preparation method thereof that can be used for 3D and print, the raw material of following component and weight percent content is adopted to prepare: polyoxymethylene 80-100%, tensio-active agent 0-7%, filler 0-13%, wherein, the content of polyoxymethylene is less than 100%, the content of tensio-active agent and filler is greater than 0, pre-composition is obtained after above-mentioned raw materials being placed in plastic mixer mixing 1-2min, again pre-composition is placed in single screw extrusion machine or twin screw extruder carries out extruding wire drawing, controlling silk material diameter is 1.75mm, obtain the modified polyacetal propping material that can be used for 3D printing.This patent modified filler is powder calcium carbonate or talcum powder, does not also add all kinds of stablizer, does not reach and improves formaldehyde thermostability, toughness reguirements, only prints propping material for 3D.
Patent 201410183557.3 discloses a kind of 3D printing high molecular weight polyoxymethylene powder, and it is characterized in that, each feed composition is counted by weight: trioxymethylene 100 weight part; Comonomer 2-5 weight part; Initiator 0.005-1 weight part; Molecular weight regulator 0.1-0.5 weight part; Oxidation inhibitor 0.1-0.5 weight part; Formaldehyde absorbent 0.1-0.5 weight part; Fomic acid absorber 0.1-0.5 weight part.Polyoxymethylene powder provided by the invention, weight-average molecular weight can reach 8-15 ten thousand, melt temperature 160-180 DEG C, and particle diameter 20-100 micron, for precinct laser sintering technology.
Therefore, develop a kind of good heat stability, intensity be high, the polyformaldehyde composite material of good toughness, meeting 3D, to print the thread matrix material of polyoxymethylene of FDM technology demand significant.
Summary of the invention
The present invention is directed to the requirements of 3D printing technique to filamentary material, and polyoxymethylene poor heat stability, easily decompose, processing temperature narrow range, property is crisp, and resistance to impact shock is low, the defects such as poor toughness, the present invention adopts polyethylene oxide to polyoxymethylene modified, by screw extrusion press fusion plastification wire drawing preparation, and the filamentary material excellent heat stability obtained, intensity is high, good toughness, can meet 3D and print FDM technology to the requirement of filamentary material, significant to the development of 3D printed material.
Technical scheme of the present invention is as follows:
A kind of 3D prints with polyoxymethylene silk material, and it is characterized in that the filamentary material be prepared from by following feed composition melt drawing, feed composition comprises by weight:
Polyformaldehyde resin 60 ~ 80 weight part,
Polyethylene oxide 10 ~ 20 weight part,
Toughner 5 ~ 10 weight part,
Thermo-stabilizer 0.1 ~ 0.5 weight part,
Formaldehyde absorbent 0.1 ~ 1 weight part;
Wherein, described polyformaldehyde resin is acefal homopolymer resin.
Described toughner is one or more in polyurethane elastomer, nitrile rubber.
Described thermo-stabilizer is trolamine or tri-isopropanolamine.
Described formaldehyde absorbent is one or more in Dyhard RU 100, trimeric cyanamide.
A preparation method for 3D printing polyoxymethylene silk material, is characterized in that: after feed composition high speed is blended, by the modification of screw extrusion press fusion plastification, extrudes wire drawing preparation;
Preparation method comprises the following steps:
1) 60 ~ 80 parts by weight of polyoxymethylene resins, 10 ~ 20 weight part polyethylene oxides, 5 ~ 10 weight part toughner, 0.1 ~ 0.5 weight part thermo-stabilizer, 0.1 ~ 1 parts by weight of formaldehyde absorption agent are joined in high-speed mixer, high-speed stirring mixing 10 ~ 20 minutes, obtains mixture;
2) mixture step 1) obtained sends into meshing co rotating twin screw extrusion fusion plastification, shears modification, extrudes wire drawing, controls material filament diameter at 1.75mm, obtains thread polyformaldehyde composite material.
Above-mentioned polyoxymethylene silk material, is characterized in that: acefal homopolymer resin and polyethylene oxide resin form matrix material, and matrix material form, for being easy to into silk, can directly be applied as 3D printed material.
A kind of 3D of the present invention prints with polyoxymethylene silk material and preparation method thereof, by polyethylene oxide to polyoxymethylene modified, polyoxymethylene is made to have good hot-work stability and toughness, achieve polyoxymethylene and become silk characteristic, thus be used for 3D printing as silk material, expand polyoxymethylene prints field application at 3D.Add the thermostability of thermo-stabilizer and formaldehyde absorbent guarantee matrix material simultaneously.By twin screw extruder fusion plastification after raw material high-speed mixing, shear modification, extrude wire drawing and be prepared into thread polyformaldehyde composite material, silk material good stability, intensity is high, good toughness, 3D can be met and print requirements to powder body material, resulting product excellent performance, stable, good processability.
The present invention has following outstanding feature and beneficial effect:
1, the present invention's acefal homopolymer has higher degree of crystallinity and intensity, is ensured the thermostability of polyformaldehyde composite material by mixing polyethylene oxide and thermo-stabilizer, formaldehyde absorbent, meets the requirement of 3D printing to material thermal characteristics.
2, the present invention is by handling flexibly, overcomes polyoxymethylene and easily produces decomposition, processing temperature narrow range, is difficult to into the defect of silk, meets 3D and prints FDM technology to the requirement of material, obtain high-precision printed product.
3, pass through twin screw extruder fusion plastification after preparation method's raw material high-speed mixing of the present invention, shear modification, extrude wire drawing and be prepared from, degree of mixing is high, and modified effect is good, and production technique is simple, with low cost.
Specific embodiments
Below by way of embodiment, the present invention is described in further detail, but this should be interpreted as scope of the present invention is only limitted to following example.When not departing from aforesaid method thought of the present invention, the various replacement made according to ordinary skill knowledge and customary means or change, all should be within the scope of the present invention.
Embodiment 1
A kind of 3D prints with polyoxymethylene silk material, the filamentary material be prepared from by following feed composition melt drawing, and feed composition comprises by weight:
Polyformaldehyde resin 60 weight part,
Polyethylene oxide 10 weight part,
Polyurethane elastomer toughner 5 weight part,
Trolamine thermo-stabilizer 0.1 weight part,
Dyhard RU 100 formaldehyde absorbent 0.1 weight part;
Preparation method comprises the following steps:
1) join in high-speed mixer by 60 parts by weight of polyoxymethylene resins, 10 weight part polyethylene oxides, 5 weight part toughner, 0.1 weight part thermo-stabilizer, 0.1 parts by weight of formaldehyde absorption agent, high-speed stirring mixing 10 ~ 20 minutes, obtains mixture;
2) mixture step 1) obtained sends into meshing co rotating twin screw extrusion fusion plastification, shears modification, extrudes wire drawing, controls material filament diameter at 1.75mm, obtains thread polyformaldehyde composite material.
Embodiment 2
A kind of 3D prints with polyoxymethylene silk material, and it is characterized in that the filamentary material be prepared from by following feed composition melt drawing, feed composition comprises by weight:
Polyformaldehyde resin 80 weight part,
Polyethylene oxide 15 weight part,
Nitrile rubber toughner 10 weight part,
Tri-isopropanolamine thermo-stabilizer 0.5 weight part,
Melamino-formaldehyde absorption agent 0.5 weight part;
Preparation method comprises the following steps:
1) join in high-speed mixer by 80 parts by weight of polyoxymethylene resins, 15 weight part polyethylene oxides, 10 weight part toughner, 0.5 weight part thermo-stabilizer, 0.5 parts by weight of formaldehyde absorption agent, high-speed stirring mixing 10 ~ 20 minutes, obtains mixture;
2) mixture step 1) obtained sends into meshing co rotating twin screw extrusion fusion plastification, shears modification, extrudes wire drawing, controls material filament diameter at 1.75mm, obtains thread polyformaldehyde composite material.
Embodiment 3
A kind of 3D prints with polyoxymethylene silk material, and it is characterized in that the filamentary material be prepared from by following feed composition melt drawing, feed composition comprises by weight:
Polyformaldehyde resin 65 weight part,
Polyethylene oxide 20 weight part,
Polyurethane elastomer toughner 8 weight part,
Tri-isopropanolamine thermo-stabilizer 0.3 weight part,
Dyhard RU 100 formaldehyde absorbent 0.1 weight part;
Preparation method comprises the following steps:
1) join in high-speed mixer by 65 parts by weight of polyoxymethylene resins, 20 weight part polyethylene oxides, 8 weight part toughner, 0.3 weight part thermo-stabilizer, 0.1 parts by weight of formaldehyde absorption agent, high-speed stirring mixing 10 ~ 20 minutes, obtains mixture;
2) mixture step 1) obtained sends into meshing co rotating twin screw extrusion fusion plastification, shears modification, extrudes wire drawing, controls material filament diameter at 1.75mm, obtains thread polyformaldehyde composite material.
Embodiment 4
A kind of 3D prints with polyoxymethylene silk material, and it is characterized in that the filamentary material be prepared from by following feed composition melt drawing, feed composition comprises by weight:
Polyformaldehyde resin 80 weight part,
Polyethylene oxide 10 weight part,
Nitrile rubber toughner 5 weight part,
Trolamine thermo-stabilizer 0.5 weight part,
Melamino-formaldehyde absorption agent 0.1 weight part;
Preparation method comprises the following steps:
1) join in high-speed mixer by 80 parts by weight of polyoxymethylene resins, 10 weight part polyethylene oxides, 5 weight part toughner, 0.5 weight part thermo-stabilizer, 0.1 parts by weight of formaldehyde absorption agent, high-speed stirring mixing 10 ~ 20 minutes, obtains mixture;
2) mixture step 1) obtained sends into meshing co rotating twin screw extrusion fusion plastification, shears modification, extrudes wire drawing, controls material filament diameter at 1.75mm, obtains thread polyformaldehyde composite material.
Claims (5)
1. 3D prints with a polyoxymethylene silk material, and it is characterized in that the filamentary material be prepared from by following feed composition melt drawing, feed composition comprises by weight:
Polyformaldehyde resin 60 ~ 80 weight part,
Polyethylene oxide 10 ~ 20 weight part,
Toughner 5 ~ 10 weight part,
Thermo-stabilizer 0.1 ~ 0.5 weight part,
Formaldehyde absorbent 0.1 ~ 1 weight part;
Wherein, described polyformaldehyde resin is acefal homopolymer resin.
2. a kind of 3D printing polyoxymethylene silk material according to claim 1, is characterized in that: described toughner is one or more in polyurethane elastomer, nitrile rubber.
3. a kind of 3D printing polyoxymethylene silk material according to claim 1, is characterized in that: described thermo-stabilizer is trolamine or tri-isopropanolamine.
4. a kind of 3D printing polyoxymethylene silk material according to claim 1, is characterized in that: described formaldehyde absorbent is one or more in Dyhard RU 100, trimeric cyanamide.
5. the preparation method of a kind of 3D printing polyoxymethylene silk material described in any one of claim 1 ~ 4, is characterized in that: after feed composition high speed is blended, by the modification of screw extrusion press fusion plastification, extrudes wire drawing preparation;
Preparation method comprises the following steps:
1) 60 ~ 80 parts by weight of polyoxymethylene resins, 10 ~ 20 weight part polyethylene oxides, 5 ~ 10 weight part toughner, 0.1 ~ 0.5 weight part thermo-stabilizer, 0.1 ~ 1 parts by weight of formaldehyde absorption agent are joined in high-speed mixer, high-speed stirring mixing 10 ~ 20 minutes, obtains mixture;
2) mixture step 1) obtained sends into meshing co rotating twin screw extrusion fusion plastification, shears modification, extrudes wire drawing, controls material filament diameter at 1.75mm, obtains thread polyformaldehyde composite material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201511010549.XA CN105504662A (en) | 2015-12-30 | 2015-12-30 | Polyformaldehyde wire material for 3D printing and preparation method thereof |
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| CN201511010549.XA CN105504662A (en) | 2015-12-30 | 2015-12-30 | Polyformaldehyde wire material for 3D printing and preparation method thereof |
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| CN105504662A true CN105504662A (en) | 2016-04-20 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105924882A (en) * | 2016-05-20 | 2016-09-07 | 黑龙江鑫达企业集团有限公司 | Support material capable of being used for 3D printing and preparation method thereof |
| CN107459760A (en) * | 2017-09-21 | 2017-12-12 | 上海中镭新材料科技有限公司 | A kind of polyformaldehyde material and preparation method thereof |
| WO2018108639A1 (en) | 2016-12-13 | 2018-06-21 | Basf Se | Filaments for use as a support material in fused deposition modeling |
| CN109337282A (en) * | 2018-10-10 | 2019-02-15 | 万华化学集团股份有限公司 | A kind of high thermal stability acetal resin and preparation method thereof |
| CN111649665A (en) * | 2020-06-18 | 2020-09-11 | 西南石油大学 | Cobweb-shaped flexible strain sensor capable of identifying strain direction and preparation method thereof |
| JP2021531396A (en) * | 2018-07-13 | 2021-11-18 | ビーエイエスエフ・ソシエタス・エウロパエアBasf Se | Method for Producing Stable Polyoxymethylene Copolymer (cPOM) |
| US11661521B2 (en) | 2019-12-17 | 2023-05-30 | Ticona Llc | Three-dimensional printing system employing a thermotropic liquid crystalline polymer |
| EP4077375A4 (en) * | 2019-12-17 | 2023-12-20 | Ticona LLC | Feed material for three-dimensional printing containing a polyoxymethylene polymer |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105924882A (en) * | 2016-05-20 | 2016-09-07 | 黑龙江鑫达企业集团有限公司 | Support material capable of being used for 3D printing and preparation method thereof |
| CN110073040B (en) * | 2016-12-13 | 2022-05-10 | 巴斯夫欧洲公司 | Filaments for use as support materials in fused deposition modeling |
| WO2018108639A1 (en) | 2016-12-13 | 2018-06-21 | Basf Se | Filaments for use as a support material in fused deposition modeling |
| US11434587B2 (en) | 2016-12-13 | 2022-09-06 | Basf Se | Filaments for use as a support material in fused deposition modeling |
| CN110073040A (en) * | 2016-12-13 | 2019-07-30 | 巴斯夫欧洲公司 | Fibril as the backing material in fused glass pellet |
| CN107459760A (en) * | 2017-09-21 | 2017-12-12 | 上海中镭新材料科技有限公司 | A kind of polyformaldehyde material and preparation method thereof |
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| JP7425795B2 (en) | 2018-07-13 | 2024-01-31 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for producing stable polyoxymethylene copolymer (cPOM) |
| JP2021531396A (en) * | 2018-07-13 | 2021-11-18 | ビーエイエスエフ・ソシエタス・エウロパエアBasf Se | Method for Producing Stable Polyoxymethylene Copolymer (cPOM) |
| CN109337282B (en) * | 2018-10-10 | 2021-03-09 | 万华化学集团股份有限公司 | High-thermal-stability polyformaldehyde resin and preparation method thereof |
| CN109337282A (en) * | 2018-10-10 | 2019-02-15 | 万华化学集团股份有限公司 | A kind of high thermal stability acetal resin and preparation method thereof |
| EP4077375A4 (en) * | 2019-12-17 | 2023-12-20 | Ticona LLC | Feed material for three-dimensional printing containing a polyoxymethylene polymer |
| US11661521B2 (en) | 2019-12-17 | 2023-05-30 | Ticona Llc | Three-dimensional printing system employing a thermotropic liquid crystalline polymer |
| CN111649665A (en) * | 2020-06-18 | 2020-09-11 | 西南石油大学 | Cobweb-shaped flexible strain sensor capable of identifying strain direction and preparation method thereof |
| CN111649665B (en) * | 2020-06-18 | 2022-03-18 | 西南石油大学 | Cobweb-shaped flexible strain sensor capable of identifying strain direction and preparation method thereof |
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