CN103881289A - Modified polyformaldehyde supporting material for 3D printing and preparation method thereof - Google Patents

Modified polyformaldehyde supporting material for 3D printing and preparation method thereof Download PDF

Info

Publication number
CN103881289A
CN103881289A CN201410130006.0A CN201410130006A CN103881289A CN 103881289 A CN103881289 A CN 103881289A CN 201410130006 A CN201410130006 A CN 201410130006A CN 103881289 A CN103881289 A CN 103881289A
Authority
CN
China
Prior art keywords
polyoxymethylene
printing
active agent
filler
content
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201410130006.0A
Other languages
Chinese (zh)
Other versions
CN103881289B (en
Inventor
李小慧
顾哲明
金石磊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Material Research Institute Co ltd
Original Assignee
Shanghai Institute of Materials
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Institute of Materials filed Critical Shanghai Institute of Materials
Priority to CN201410130006.0A priority Critical patent/CN103881289B/en
Publication of CN103881289A publication Critical patent/CN103881289A/en
Application granted granted Critical
Publication of CN103881289B publication Critical patent/CN103881289B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92609—Dimensions
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92695—Viscosity; Melt flow index [MFI]; Molecular weight

Abstract

The invention relates to a modified polyformaldehyde supporting material for 3D printing and a preparation method thereof. According to the method, the modified polyformaldehyde supporting material is prepared from the following raw materials by weight percent: 80-100 percent of polyformaldehyde, 0-7 percent of surface active agent and 0-13 percent of packing, wherein the content of polyformaldehyde is smaller than 100 percent, and the content of the surface active agent and the packing is larger than zero; the raw materials are put in a plastic mixer and mixed for 1-2 minutes to obtain a premix, the premix is put in a single screw extruder or a double screw extruder for extrusion and wire drawing by controlling the diameter of wires at 1.75 mm, so that the modified polyformaldehyde supporting material for 3D printing is obtained. Compared with the prior art, the invention provides the novel application and novel development of the modified polyformaldehyde, the modified polyformaldehyde material prepared according to the method has the characteristic of dissolving in an acidic liquid or gas decomposition, and has certain mechanical strength through modification treatment.

Description

A kind of modified polyacetal propping material that can be used for 3D printing and preparation method thereof
Technical field
The invention belongs to field of new, especially relate to modified polyacetal propping material of a kind of 3D of can be used for printing and preparation method thereof.
Background technology
Fusion stacking forming technique (FDM) during 3D prints is the characteristic of utilizing near engineering plastics silk (as ABS, PLA etc.) fusible accumulation fusing point, prints three-dimensional article.When occurring in goods caving in, when hollow structure, select propping material to print moulding, then impregnated in specific solution or atmosphere, propping material is fully dissolved, obtain the goods of special construction.Propping material plays important effect in the printing of shaped piece, is related to the application that 3D prints.The propping material of market only has modified ABS one at present, and depends on external import.
Its molecular formula of polyoxymethylene (POM) is-[CH 20] n-, because its molecular chain has smooth profile, thereby thering is good self lubricity, frictional coefficient is low.Again because of the flexible line style high crystallinity polymer connecting in fact, degree of crystallinity is high, bond energy is large, be difficult for to flour milling is shifted, intrinsic good wear resistance and high strength, be that in all plastics, specific tenacity comparatively approaches one of resin kind of metal, be widely used in manufacturing various parts in fields such as machinery, automobile, electronic apparatuss.Application number is that 201310412518.1 Chinese patent discloses a kind of inotropic modified polyformaldehyde material of polyformaldehyde material and preparation method thereof that improves, raw material comprises polyoxymethylene raw material, alkali free glass fibre, oxidation inhibitor, tinting material, ultraviolet absorbers, photostabilizer, dispersed lubricant, glass compatilizer etc., can be for fields such as electronic apparatus, machinery, instrument, daily light industry, automobile, building materials, but openly polyoxymethylene can not be applied in 3D printing technique in prior art.
Summary of the invention
Object of the present invention is exactly that a kind of characteristic that can dissolve at acidic liquid/decomposing gas is provided in order to overcome the defect that above-mentioned prior art exists, by modification, prepare and there is certain mechanical strength and can be used for modified polyacetal propping material and preparation method thereof that 3D prints.
Object of the present invention can be achieved through the following technical solutions:
Can be used for the modified polyacetal propping material that 3D prints, adopt the raw material of following component and weight percent content to prepare:
Polyoxymethylene 80-100%, tensio-active agent 0-7%, filler 0-13%;
Wherein, the content of polyoxymethylene is less than or equal to 100%, and the content of tensio-active agent and filler is more than or equal to 0.
Preferably adopt the raw material of following component and weight percent content to prepare: polyoxymethylene 85-90%, tensio-active agent 2-4%, filler 8-11%.
Described polyoxymethylene be kematal or homopolymerization polyoxymethylene its, melting index 1-60g/10min.
Described tensio-active agent table is selected from one or more in silicone oil, paraffin or titanic acid ester.
Described filler is calcium carbonate or talcous single powder or mixture.
The preparation method who can be used for the modified polyacetal propping material of 3D printing, adopts following steps:
(1) get the raw materials ready according to following component and weight percent content:
Polyoxymethylene 80-100%, tensio-active agent 0-7%, filler 0-13%, wherein, the content of polyoxymethylene is less than or equal to 100%, and the content of tensio-active agent and filler is more than or equal to 0;
(2) obtain pre-composition after above-mentioned raw materials being placed in to plastic mixer mixing 1-2min, again pre-composition is placed in to single screw extrusion machine or twin screw extruder is extruded wire drawing, controlling silk material diameter is 1.75mm, obtains can be used for the modified polyacetal propping material that 3D prints.
Described single screw extrusion machine or the extruder temperature of twin screw extruder are 170-190C.
Pure polyoxymethylene is under acidity effect, first can cause molecular chain C=O to react, produce small molecules formic acid COOH, along with the cracking of formic acid from polyoxymethylene chain, reaction can further occur on other corresponding groups of molecular chain, final polyoxymethylene thoroughly decomposes, and therefore pure polyoxymethylene can be used for being 3D and print propping material.Adding of filler makes modified polyacetal have better mechanical strength and dimensional stability, realizes filler and good the mixing of polyformaldehyde resin by the coupled action of tensio-active agent.Compared with prior art, the present invention is new application and new expansion of modified polyacetal, and the characteristic that the modified polyformaldehyde material preparing can dissolve at acidic liquid/decomposing gas, by modification, has certain mechanical strength.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
By 8 kilograms of the polyoxymethylene of drying in advance, 0.7 kilogram of silicone oil, 1.3 kilograms, calcium carbonate mixes discharging 1 minute in plastic mixer.By the blend granulation in list/twin screw extruder of mixed material, extruder temperature is set in 180 ℃, makes the propping material of printing for 3D.When printing, the polyoxymethylene silk of the 1.75mm of preparation or 3mm is placed in to the magazine of 3D printer, printhead set temperature can be at 200-220 ℃, hott bed temperature can be at 50-90 ℃, print speed is arranged on 25-75mm/s, and head to be printed and hott bed rise to after design temperature, start printing shaping, after printing, printing goods are placed in to dilute hydrochloric acid solution, after about 30min, polyoxymethylene printing shaping part is solubilization.
Embodiment 2
By 8.5 kilograms of the polyoxymethylene of drying in advance, 0.4 kilogram, paraffin, 1.1 kilograms of talcum powder mix discharging 1 minute in plastic mixer.By the blend granulation in list/twin screw extruder of mixed material, extruder temperature is set in 170 ℃, makes the propping material of printing for 3D, can in acidic solution, dissolve.When printing, the polyoxymethylene silk of the 1.75mm of preparation or 3mm is placed in to the magazine of 3D printer, printhead set temperature can be at 200-220 ℃, hott bed temperature can be at 50-90 ℃, print speed is arranged on 25-75mm/s, and head to be printed and hott bed rise to after design temperature, start printing shaping, after printing, printing goods are placed in to dilute hydrochloric acid solution, after about 30min, polyoxymethylene printing shaping part is solubilization.
Embodiment 3
By 9 kilograms of the polyoxymethylene of drying in advance, 0.2 kilogram of titanic acid ester, totally 0.8 kilogram of calcium carbonate and talcum powder mix discharging 2 minutes in plastic mixer.By the blend granulation in twin screw extruder of mixed material, extruder temperature is set in 185 ℃, makes the propping material of printing for 3D, can in sour gas, decompose.When printing, the polyoxymethylene silk of the 1.75mm of preparation or 3mm is placed in to the magazine of 3D printer, printhead set temperature can be at 200-220 ℃, hott bed temperature can be at 50-90 ℃, print speed is arranged on 25-75mm/s, and head to be printed and hott bed rise to after design temperature, start printing shaping, after printing, printing goods are placed in to dilute hydrochloric acid solution, after about 30min, polyoxymethylene printing shaping part is solubilization.
Embodiment 4
By 10 kilograms of the polyoxymethylene of drying in advance, or add a small amount of pigment, in plastic mixer, mix discharging 2 minutes.By the blend granulation in single screw extrusion machine of mixed material, extruder temperature is set in 185 ℃, makes the propping material of printing for 3D.When printing, the polyoxymethylene silk of the 1.75mm of preparation or 3mm is placed in to the magazine of 3D printer, printhead set temperature can be at 200-220 ℃, hott bed temperature can be at 50-90 ℃, print speed is arranged on 25-75mm/s, and head to be printed and hott bed rise to after design temperature, start printing shaping, after printing, printing goods are placed in to dilute hydrochloric acid solution, after about 30min, polyoxymethylene printing shaping part is solubilization.
Embodiment 5
By 10 kilograms of the polyoxymethylene of drying in advance, in twin screw extruder, extrude wire drawing, extruder temperature is set in 185 ℃, makes the propping material of printing for 3D.When printing, the polyoxymethylene silk of the 1.75mm of preparation or 3mm is placed in to the magazine of 3D printer, printhead set temperature can be at 200-220 ℃, hott bed temperature can be at 50-90 ℃, print speed is arranged on 25-75mm/s, and head to be printed and hott bed rise to after design temperature, start printing shaping, after printing, printing goods are placed in to dilute hydrochloric acid solution, after about 30min, polyoxymethylene printing shaping part is solubilization.

Claims (7)

1. can be used for the modified polyacetal propping material that 3D prints, it is characterized in that, adopt the raw material of following component and weight percent content to prepare:
Polyoxymethylene 80-100%, tensio-active agent 0-7%, filler 0-13%;
Wherein, the content of polyoxymethylene is less than or equal to 100%, and the content of tensio-active agent and filler is more than or equal to 0.
2. a kind of modified polyacetal propping material that 3D prints that can be used for according to claim 1, it is characterized in that, preferably adopt the raw material of following component and weight percent content to prepare: polyoxymethylene 85-90%, tensio-active agent 2-4%, filler 8-11%.
3. a kind of modified polyacetal propping material that 3D prints that can be used for according to claim 1 and 2, is characterized in that, described polyoxymethylene is kematal or homopolymerization polyoxymethylene, its melting index 1-60g/10min.
4. a kind of modified polyacetal propping material that 3D prints that can be used for according to claim 1 and 2, is characterized in that, described tensio-active agent table is selected from one or more in silicone oil, paraffin or titanic acid ester.
5. a kind of modified polyacetal propping material that 3D prints that can be used for according to claim 1 and 2, is characterized in that, described filler is calcium carbonate or talcous single powder or mixture.
6. the preparation method of the modified polyacetal propping material that can be used for 3D printing as described in any one in claim 1-5, is characterized in that, the method adopts following steps:
(1) get the raw materials ready according to following component and weight percent content:
Polyoxymethylene 80-100%, tensio-active agent 0-7%, filler 0-13%, wherein, the content of polyoxymethylene is less than or equal to 100%, and the content of tensio-active agent and filler is more than or equal to 0;
(2) obtain pre-composition after above-mentioned raw materials being placed in to plastic mixer mixing 1-2min, again pre-composition is placed in to single screw extrusion machine or twin screw extruder is extruded wire drawing, controlling silk material diameter is 1.75mm, obtains can be used for the modified polyacetal propping material that 3D prints.
7. the preparation method of a kind of modified polyacetal propping material that can be used for 3D printing according to claim 6, is characterized in that, described single screw extrusion machine or the extruder temperature of twin screw extruder are 170-190 ℃.
CN201410130006.0A 2014-04-01 2014-04-01 A kind of modified polyacetal backing material that can be used for 3D printing and preparation method thereof Active CN103881289B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410130006.0A CN103881289B (en) 2014-04-01 2014-04-01 A kind of modified polyacetal backing material that can be used for 3D printing and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410130006.0A CN103881289B (en) 2014-04-01 2014-04-01 A kind of modified polyacetal backing material that can be used for 3D printing and preparation method thereof

Publications (2)

Publication Number Publication Date
CN103881289A true CN103881289A (en) 2014-06-25
CN103881289B CN103881289B (en) 2016-10-12

Family

ID=50950437

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410130006.0A Active CN103881289B (en) 2014-04-01 2014-04-01 A kind of modified polyacetal backing material that can be used for 3D printing and preparation method thereof

Country Status (1)

Country Link
CN (1) CN103881289B (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104139472A (en) * 2014-08-05 2014-11-12 成都思维智造科技有限公司 Waste recycling device and method for 3D printer
CN104177551A (en) * 2014-08-26 2014-12-03 太仓碧奇新材料研发有限公司 Polyoxymethylene homopolymer composite material for 3D printing and preparation method of composite material
CN105504662A (en) * 2015-12-30 2016-04-20 成都新柯力化工科技有限公司 Polyformaldehyde wire material for 3D printing and preparation method thereof
CN106521681A (en) * 2016-11-15 2017-03-22 中山大学惠州研究院 High strength 3D printing support material with fast water solubility 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
CN109311092A (en) * 2016-02-16 2019-02-05 亚利桑那州立大学董事会 Metal or ceramic component are made with the dissolvable carrier of different materials using 3D printing

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115135668A (en) * 2019-12-17 2022-09-30 提克纳有限责任公司 Feed for three-dimensional printing comprising a polyoxymethylene polymer

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1421488A (en) * 2002-12-17 2003-06-04 四川大学 Nano composite polyformaldehyde material and its prepn
CN101724222A (en) * 2009-11-30 2010-06-09 中国蓝星（集团）股份有限公司 High wear-resistence self-lubricating polyformaldehyde compound and preparation method thereof
CN102634162A (en) * 2012-05-09 2012-08-15 四川大学 Heat-conduction polyformaldehyde composite material and preparation method thereof
CN103509314A (en) * 2013-09-11 2014-01-15 青岛颐世保塑料有限公司 Modified polyformaldehyde material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1421488A (en) * 2002-12-17 2003-06-04 四川大学 Nano composite polyformaldehyde material and its prepn
CN101724222A (en) * 2009-11-30 2010-06-09 中国蓝星（集团）股份有限公司 High wear-resistence self-lubricating polyformaldehyde compound and preparation method thereof
CN102634162A (en) * 2012-05-09 2012-08-15 四川大学 Heat-conduction polyformaldehyde composite material and preparation method thereof
CN103509314A (en) * 2013-09-11 2014-01-15 青岛颐世保塑料有限公司 Modified polyformaldehyde material

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104139472A (en) * 2014-08-05 2014-11-12 成都思维智造科技有限公司 Waste recycling device and method for 3D printer
CN104177551A (en) * 2014-08-26 2014-12-03 太仓碧奇新材料研发有限公司 Polyoxymethylene homopolymer composite material for 3D printing and preparation method of composite material
CN104177551B (en) * 2014-08-26 2016-09-14 太仓碧奇新材料研发有限公司 3D prints with acefal homopolymer composite and preparation method thereof
CN105504662A (en) * 2015-12-30 2016-04-20 成都新柯力化工科技有限公司 Polyformaldehyde wire material for 3D printing and preparation method thereof
CN109311092A (en) * 2016-02-16 2019-02-05 亚利桑那州立大学董事会 Metal or ceramic component are made with the dissolvable carrier of different materials using 3D printing
CN106521681A (en) * 2016-11-15 2017-03-22 中山大学惠州研究院 High strength 3D printing support material with fast water solubility and preparation method thereof
CN106521681B (en) * 2016-11-15 2019-02-05 中山大学惠州研究院 A kind of high-intensitive 3D printing backing material and preparation method thereof with immediate water-solubility energy
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

Also Published As

Publication number Publication date
CN103881289B (en) 2016-10-12

Similar Documents

Publication Publication Date Title
CN103881289A (en) Modified polyformaldehyde supporting material for 3D printing and preparation method thereof
CN104650587B (en) It is a kind of suitable for modified polyphenylene sulfide resin material of 3D printing and its preparation method and application
CN108424605B (en) Polyether-ether-ketone 3D printing material and 3D printing forming method thereof
CN103073819A (en) Ultra-thin walled semi-rigid polyvinyl chloride cable material and preparing technology thereof
CN105504662A (en) Polyformaldehyde wire material for 3D printing and preparation method thereof
CN105504713A (en) Polylactic acid microspherical modified material for 3D printing and preparation method thereof
CN103788603B (en) A kind of poly(lactic acid) two-way stretch frosted film and preparation method thereof
CN101838444B (en) Primer-free polyester material for decorating pieces and method for preparing same
CN107955348A (en) A kind of environmentally-friendly plastic Masterbatch and its manufacture method
KR20010022995A (en) Continuous Method for Producing Amino- and/or Phenoplasts
CN102807688B (en) Compound stabilizer for plastic bubble tube and preparation method thereof
CN103059530B (en) Composite material for producing disposable plastic products and preparation method of composite material
CN109206832A (en) A kind of ABS material and preparation method thereof of the extremely low warpage of 3D printing without cracking
CN106221290A (en) A kind of inorganic material surface treatment technology and the method for preparation carrier-free masterbatch
CN104974450A (en) Polyvinyl chloride plastic composition
CN106633582A (en) A polypropylene composition used for 3D printing and a preparing method thereof
CN107001766B (en) Lignin resin composition, solidfied material and molding
CN108384089B (en) Modified high-density polyethylene material and preparation method thereof
CN105504724A (en) Automobile interior material added with tourmaline powder
CN106589862A (en) Wood-imitation material for 3D printing and preparation method thereof
CN111349265A (en) Modified nylon 6 for 3D printing and preparation method thereof
CN108003582B (en) A kind of polylactic acid wood plastics composite wire rod and its preparation method and application
CN101293985B (en) Polystyrene composition capable of marking with laser and preparation thereof
CN103044853B (en) Abrasion-resistance and low-warpage polyformaldehyde material as well as preparation method and application thereof
CN108976738A (en) High-performance starch/Biodegradable high molecular composite material and product manufacturing method

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CP01 Change in the name or title of a patent holder

Address after: 200437 No. 99, Handan Road, Shanghai, Hongkou District

Patentee after: Shanghai Material Research Institute Co.,Ltd.

Address before: 200437 No. 99, Handan Road, Shanghai, Hongkou District

Patentee before: SHANGHAI Research Institute OF MATERIALS

CP01 Change in the name or title of a patent holder