CN104177551B - 3D prints with acefal homopolymer composite and preparation method thereof - Google Patents
3D prints with acefal homopolymer composite and preparation method thereof Download PDFInfo
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- CN104177551B CN104177551B CN201410425293.8A CN201410425293A CN104177551B CN 104177551 B CN104177551 B CN 104177551B CN 201410425293 A CN201410425293 A CN 201410425293A CN 104177551 B CN104177551 B CN 104177551B
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Abstract
The invention belongs to technical field of composite materials, relate to 3D printing acefal homopolymer composite and preparation method thereof.The feature of the preparation method of this acefal homopolymer composite is methylene diacrylamide and 2 butanone to be mixed, add ascorbic acid, it is stirred at room temperature, sequentially add azo two isobutyl imidazoline hydrochloride, vinyltrimethoxy silane, it is stirred at room temperature, it is subsequently adding acefal homopolymer granule, heated and stirred, cools down to obtain 3D printing acefal homopolymer composite.The invention have the advantage that 1, the acefal homopolymer composite of preparation can carry out 3D printing within the temperature range of 30 ~ 50 DEG C, will not block 3D printer head；2, preparation technology is simple, and production cost is low, it is simple to promotion and application；3, the material after printing shaping has the excellent performances such as endurance, resistance to creep, wear-resisting, heat-resisting, impact resistance.
Description
Technical field
The invention belongs to technical field of composite materials, relate to a kind of 3D printing acefal homopolymer composite and preparation side thereof
Method.
Background technology
The development origin of 3D printing technique can trace back to initial stage late 1970s to the eighties, Minnesota Mining and Manufacturing Company
Alan Hebert (1978), little beautiful elegant man (1980), the Charles Hull (nineteen eighty-two) of UVP company of the U.S. of Japan
This conception of species is the most independently proposed with ball paddy ocean two (nineteen eighty-three) four people of Japan.1986, Charles Hull took the lead in pushing away
Going out process for photocuring (stereo lithography apparatus, SLA), this is a mileage of 3D printing technique development
Upright stone tablet.In the same year, he has founded the 3D Systems company of first hand 3D printing device in the world.The said firm produced in 1988
First 3D printer SLA-250 in the world.1988, American Scott Crump invented another 3D and has printed skill
Art Fused Deposition Modeling (fused deposition modeling, FDM), and set up Stratasys company.At present,
This two company is only two 3D printing device manufacturing enterprises in Nasdaq's listing.Hereafter, Israelis Hanan
Gothait established Objet Geometries company in 1998, and was proposed in North America in 2000 and can be used for office
The commercialization 3D printer of environment.
Acefal homopolymer is a kind of linear polymer not having side chain, high density, high crystalline.By chemistry knot in its strand
The difference of structure, can be divided into acefal homopolymer and copolymerized methanal two kinds.Both important difference are: acefal homopolymer density, degree of crystallinity, molten
Point is the highest, but poor heat stability, processing temperature narrow range (about 10 DEG C), lower slightly to ph stability；And copolymerized methanal density, knot
Crystalline substance degree, fusing point, intensity are the most relatively low, but Heat stability is good, it being not easily decomposed, processing temperature wide ranges (about 50 DEG C), to ph stability
Property is preferable.It is the engineering plastics of the combination property with excellence.There are good physics, mechanically and chemically performance, especially have excellent
Different crocking resistance, is commonly called as matching steel or taking steel by force, for the third-largest general-purpose plastics.Be suitable to make anti-attrition wear part, driving parts,
And the part such as chemical industry, instrument.
It is an advantage of the current invention that: acefal homopolymer is made the molecule of 100～120 mesh by (1), makes acefal homopolymer and second
Thiazolinyl trimethoxy silane, methylene diacrylamide, 2-butanone etc. are compound, add ascorbic acid, azo two isobutyl imidazoline salt
The adjuvant such as hydrochlorate, are configured with the composite of certain viscosity, carry out 3D printing within the temperature range of 30～50 DEG C, multiple
Condensation material curing molding, obtains 3D printed product, can be used for the manufacture of gear, bearing, auto parts and components, lathe, instrument internals etc..
(2) the 3D printed material that prepared by the present invention is a kind of fluent material, and print procedure will not block 3D printer head, it is adaptable to existing
The most 3D printers having.(3) preparation technology is simple, and production cost is low, it is simple to promotion and application.
Composite prepared by the present invention may also be fabricated which various functional thin film, coating and composite, at information material
The fields such as material, energy and material and specific function material obtain application, wide market.
Summary of the invention
The invention belongs to technical field of composite materials, relate to a kind of 3D printing acefal homopolymer composite and preparation side thereof
Method.The feature of the preparation method of this acefal homopolymer composite is to be mixed with 2-butanone by methylene diacrylamide, adds anti-bad
Hematic acid, is stirred at room temperature, and sequentially adds azo two isobutyl imidazoline hydrochloride, vinyltrimethoxy silane, is stirred at room temperature, so
Rear addition acefal homopolymer granule, heated and stirred, cool down to obtain 3D printing acefal homopolymer composite.Homopolymerization first prepared by the present invention
Aldehyde composite application is extensive, can replace major part non-ferrous metal, for automobile, lathe, instrument internals, bearing, fastening
Part, gear, spring leaf, pipeline, conveyer belt accessory, electric water heater, pump case, device for water-dropping, the fire hose are first-class.
The 3D that the present invention proposes prints and uses acefal homopolymer composite, it is characterised in that:
1. it is made up of the raw material of following weight ratio:
Wherein the viscosity-average molecular weight of acefal homopolymer be 3-5 ten thousand, granule mesh number be 100～120 mesh.
2. preparation process is as follows:
1) acefal homopolymer that viscosity-average molecular weight is 3-5 ten thousand is ground into the granule of 100～120 mesh；
2) raw material is weighed by weight ratio；
3) under nitrogen atmosphere, methylene diacrylamide is mixed with 2-butanone, add ascorbic acid, be stirred at room temperature 30～
60 minutes, sequentially add azo two isobutyl imidazoline hydrochloride, vinyltrimethoxy silane, be stirred at room temperature 30～60 points
Clock, is subsequently adding acefal homopolymer granule, is heated to 70～80 DEG C, stirs 30～60 minutes, is cooled to room temperature, obtains 3D and prints with all
Polyformaldehyde composite material.
This material is carried out 3D printing at 30～50 DEG C, the density of material, hot strength, shrinkage factor and ratio after test molding
Rigidity.
Detailed description of the invention
The invention is further illustrated by the following examples
Embodiment 1
The acefal homopolymer that 50g viscosity-average molecular weight is 3-5 ten thousand is ground into the granule of 100～120 mesh；Under nitrogen atmosphere,
5g methylene diacrylamide is mixed with 30g 2-butanone, adds 1g ascorbic acid, be stirred at room temperature 30 minutes, sequentially add 2g
Azo two isobutyl imidazoline hydrochloride, 12g vinyltrimethoxy silane, be stirred at room temperature 30 minutes, be subsequently adding 50g homopolymerization
Formaldehyde particles, is heated to 80 DEG C, stirs 30 minutes, is cooled to room temperature, obtains 3D printing acefal homopolymer composite.
At 50 DEG C, this material is carried out 3D printing, and after molding, the density of material is 1.43g/cm3, hot strength is
5.1MPa, shrinkage factor is 1.62%, and specific stiffness is 2650MPa.
Embodiment 2
The acefal homopolymer that 40g viscosity-average molecular weight is 3-5 ten thousand is ground into the granule of 100～120 mesh；Under nitrogen atmosphere,
7g methylene diacrylamide is mixed with 15g 2-butanone, adds 3g ascorbic acid, be stirred at room temperature 60 minutes, sequentially add 5g
Azo two isobutyl imidazoline hydrochloride, 30g vinyltrimethoxy silane, be stirred at room temperature 60 minutes, is subsequently adding 40g homopolymerization first
Aldehyde granule, is heated to 70 DEG C, stirs 60 minutes, is cooled to room temperature, obtains 3D printing acefal homopolymer composite.
At 30 DEG C, this material is carried out 3D printing, and after molding, the density of material is 1.47g/cm3, hot strength is
3.8MPa, shrinkage factor is 2.12%, and specific stiffness is 2310MPa.
Embodiment 3
The acefal homopolymer that 40g viscosity-average molecular weight is 3-5 ten thousand is ground into the granule of 100～120 mesh；Under nitrogen atmosphere,
20g methylene diacrylamide is mixed with 30g 2-butanone, adds 2g ascorbic acid, be stirred at room temperature 50 minutes, sequentially add
3g azo two isobutyl imidazoline hydrochloride, 5g vinyltrimethoxy silane, be stirred at room temperature 40 minutes, be subsequently adding 40g homopolymerization
Formaldehyde particles, is heated to 75 DEG C, stirs 40 minutes, is cooled to room temperature, obtains 3D printing acefal homopolymer composite.
At 40 DEG C, this material is carried out 3D printing, and after molding, the density of material is 1.39g/cm3, hot strength is
4.1MPa, shrinkage factor is 2.31%, and specific stiffness is 2280MPa.
Embodiment 4
The acefal homopolymer that 45g viscosity-average molecular weight is 3-5 ten thousand is ground into the granule of 100～120 mesh；Under nitrogen atmosphere,
15g methylene diacrylamide is mixed with 20g 2-butanone, adds 1g ascorbic acid, be stirred at room temperature 40 minutes, sequentially add
4g azo two isobutyl imidazoline hydrochloride, 15g vinyltrimethoxy silane, be stirred at room temperature 40 minutes, be subsequently adding 40g homopolymerization
Formaldehyde particles, is heated to 70 DEG C, stirs 40 minutes, is cooled to room temperature, obtains 3D printing acefal homopolymer composite.
At 45 DEG C, this material is carried out 3D printing, and after molding, the density of material is 1.44g/cm3, hot strength is
4.8MPa, shrinkage factor is 2.01%, and specific stiffness is 2510MPa.
Embodiment 5
The acefal homopolymer that 42g viscosity-average molecular weight is 3-5 ten thousand is ground into the granule of 100～120 mesh；Under nitrogen atmosphere,
18g methylene diacrylamide is mixed with 24g 2-butanone, adds 3g ascorbic acid, be stirred at room temperature 40 minutes, sequentially add
3g azo two isobutyl imidazoline hydrochloride, 10g vinyltrimethoxy silane, be stirred at room temperature 50 minutes, be subsequently adding 40g homopolymerization
Formaldehyde particles, is heated to 80 DEG C, stirs 50 minutes, is cooled to room temperature, obtains 3D printing acefal homopolymer composite.
At 50 DEG C, this material is carried out 3D printing, and after molding, the density of material is 1.46g/cm3, hot strength is
5.3MPa, shrinkage factor is 2.71%, and specific stiffness is 2380MPa.
Claims (2)
1. a 3D prints and uses acefal homopolymer composite, it is characterised in that: it is made up of the raw material of following weight ratio:
Acefal homopolymer 40 ~ 50%,
Vinyltrimethoxy silane 5 ~ 30%,
Methylene diacrylamide 5 ~ 20%,
2-butanone 15 ~ 30%,
Ascorbic acid 1 ~ 3%,
Azo two isobutyl imidazoline hydrochloride 2 ~ 5%；
Wherein the viscosity-average molecular weight of acefal homopolymer be 3-5 ten thousand, granule mesh number be 100 ~ 120 mesh.
2. 3D described in claim 1 prints by the preparation method of acefal homopolymer composite, it is characterised in that: its step is as follows:
1) acefal homopolymer that viscosity-average molecular weight is 3-5 ten thousand is ground into the granule of 100 ~ 120 mesh；
2) raw material is weighed by weight ratio；
3) under nitrogen atmosphere, methylene diacrylamide is mixed with 2-butanone, add ascorbic acid, be stirred at room temperature 30 ~ 60 points
Clock, sequentially adds azo two isobutyl imidazoline hydrochloride, vinyltrimethoxy silane, is stirred at room temperature 30 ~ 60 minutes, then
Add acefal homopolymer granule, be heated to 70 ~ 80 DEG C, stir 30 ~ 60 minutes, be cooled to room temperature, obtain 3D printing acefal homopolymer multiple
Condensation material.
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| CN201410425293.8A CN104177551B (en) | 2014-08-26 | 2014-08-26 | 3D prints with acefal homopolymer composite and preparation method thereof |
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| CN104177551B true CN104177551B (en) | 2016-09-14 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2021126743A1 (en) | 2019-12-17 | 2021-06-24 | 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 |
| CN113895052B (en) * | 2021-09-02 | 2023-10-24 | 佛山智汇君彰新材料科技有限公司 | Method for preparing carbon fiber brake handle |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1793221A (en) * | 2005-11-25 | 2006-06-28 | 南京理工大学 | Process for preparing superfine oxide polyformol engineering plastic |
| CN102875737A (en) * | 2012-10-19 | 2013-01-16 | 上海纽克新材料科技有限公司 | In-situ remediated and compatibilized polyformaldehyde glass fiber composite composition and preparation thereof |
| CN103881289A (en) * | 2014-04-01 | 2014-06-25 | 上海材料研究所 | Modified polyformaldehyde supporting material for 3D printing and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CA2293005A1 (en) * | 1999-09-29 | 2001-03-29 | E.I. Du Pont De Nemours And Company | Polyoxymethylene resin compositions having improved molding characteristics |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1793221A (en) * | 2005-11-25 | 2006-06-28 | 南京理工大学 | Process for preparing superfine oxide polyformol engineering plastic |
| CN102875737A (en) * | 2012-10-19 | 2013-01-16 | 上海纽克新材料科技有限公司 | In-situ remediated and compatibilized polyformaldehyde glass fiber composite composition and preparation thereof |
| CN103881289A (en) * | 2014-04-01 | 2014-06-25 | 上海材料研究所 | Modified polyformaldehyde supporting material for 3D printing and preparation method thereof |
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