CN104177551A - Polyoxymethylene homopolymer composite material for 3D printing and preparation method of composite material - Google Patents
Polyoxymethylene homopolymer composite material for 3D printing and preparation method of composite material Download PDFInfo
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- CN104177551A CN104177551A CN201410425293.8A CN201410425293A CN104177551A CN 104177551 A CN104177551 A CN 104177551A CN 201410425293 A CN201410425293 A CN 201410425293A CN 104177551 A CN104177551 A CN 104177551A
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Abstract
The invention discloses a polyoxymethylene homopolymer composite material for 3D printing and a preparation method of the composite material. The preparation method comprises the following steps: mixing methylene diacrylamide with 2-butanone, adding ascorbic acid, adding azobis[isobutylimidazolin]hydrochloride and vinyl trimethoxy silane in sequence, stirring at the room temperature, adding polyoxymethylene homopolymer particles, heating, stirring, and cooling to obtain the polyoxymethylene homopolymer composite material for 3D printing, wherein the weight percents of polyoxymethylene homopolymer, vinyl trimethoxy silane, methylene diacrylamide, 2-butanone, ascorbic acid and azobis[isobutylimidazolin]hydrochloride are 40%-50%, 5%-30%, 5%-20%, 15%-30%, 1%-3% and 2%-5% respectively. The polyoxymethylene homopolymer composite material provided by the invention can be used for 3D printing at 30-50 DEG C, a printed material has excellent performances such as fatigue resistance, creep resistance, wear resistance, heat resistance, impact resistance and the like, and the beneficial effect is remarkable.
Description
Technical field
The invention belongs to technical field of composite materials, relate to a kind of 3D and print with acefal homopolymer matrix material and preparation method thereof.
Background technology
The development origin of 3D printing technique can trace back to initial stage late 1970s to the eighties, and the Alan Hebert (1978) of Minnesota Mining and Manufacturing Company, the little beautiful elegant man (1980) of Japan, the Charles Hull (nineteen eighty-two) of UVP company of the U.S. and Japanese ball paddy ocean two (nineteen eighty-three) four people have independently proposed this conception of species separately.1986, Charles Hull took the lead in releasing process for photocuring (stereo lithography apparatus, SLA), and this is a milestone of 3D printing technique development.In the same year, he has founded the 3D Systems company of first hand 3D printing device in the world.The said firm has produced First 3D printer SLA-250 in the world in 1988.1988, American Scott Crump invented another 3D printing technique---Fused Deposition Modeling (fused deposition modeling, FDM), and set up Stratasys company.At present, Zhe Liang company is only two 3D printing device manufacturing concerns in Nasdaq's listing.After this, Israelis Hanan Gothait established Objet Geometries company in 1998, and had released the commercialization 3D printer that can be used for office environment in North America in 2000.
Acefal homopolymer is a kind of simple linear polymer that there is no side chain, high-density, high crystalline.By the difference of chemical structure in its molecular chain, can be divided into two kinds of acefal homopolymer and copolymerized methanals.Both important difference are: acefal homopolymer density, degree of crystallinity, fusing point are all high, but poor heat stability, processing temperature narrow range (approximately 10 DEG C), lower slightly to ph stability; And copolymerized methanal density, degree of crystallinity, fusing point, intensity are all lower, but Heat stability is good is difficult for decomposing, and processing temperature wide ranges (approximately 50 DEG C) is better to ph stability.The engineering plastics with excellent over-all properties.Having good physics, machinery and chemical property, especially have excellent crocking resistance, be commonly called as match steel or take steel by force, is the third-largest general-purpose plastics.Be suitable for making anti-attrition wear part, driving parts, and the part such as chemical industry, instrument.
Summary of the invention
The invention belongs to technical field of composite materials, relate to a kind of 3D and print with acefal homopolymer matrix material and preparation method thereof.Being characterized as of the preparation method of this acefal homopolymer matrix material mixes methylene diacrylamide with 2-butanone, add xitix, stirring at room temperature, add successively again azo two isobutyl imidazoline salt hydrochlorates, vinyltrimethoxy silane, stirring at room temperature, then add acefal homopolymer particle, heated and stirred, the cooling 3D of obtaining prints and uses acefal homopolymer matrix material.Acefal homopolymer matrix material Application Areas prepared by the present invention is extensive, can replace most of non-ferrous metal, first-class for automobile, lathe, instrument internals, bearing, fastening piece, gear, spring piece, pipeline, travelling belt accessory, electric water heater, pump case, device for water-dropping, the fire hose.
The 3D that the present invention proposes prints and uses acefal homopolymer matrix material:
Raw material by following weight ratio forms:
Acefal homopolymer 40 ~ 50%,
Vinyltrimethoxy silane 5 ~ 30%,
Methylene diacrylamide 5 ~ 20%,
2-butanone 15 ~ 30%,
Xitix 1 ~ 3%,
Azo two isobutyl imidazoline salt hydrochlorates 2 ~ 5%.
Described 3D prints by the preparation method of acefal homopolymer matrix material as follows:
1) be that the acefal homopolymer of 3-5 ten thousand is ground into 100 ~ 120 object particles by viscosity-average molecular weight;
2) take by weight ratio raw material;
3) under nitrogen atmosphere, methylene diacrylamide is mixed with 2-butanone, add xitix, stirring at room temperature 30 ~ 60 minutes, then add successively azo two isobutyl imidazoline salt hydrochlorates, vinyltrimethoxy silane, stirring at room temperature 30 ~ 60 minutes, then add acefal homopolymer particle, be heated to 70 ~ 80 DEG C, stir 30 ~ 60 minutes, be cooled to room temperature, obtain 3D printing acefal homopolymer matrix material.
This material is carried out to 3D printing at 30 ~ 50 DEG C, density, tensile strength, shrinking percentage and the specific rigidity of material after test moulding.
Matrix material prepared by the present invention also can be made into various functional films, coating and matrix material, obtains application in fields such as information material, energy and material and specific function materials, and market outlook are wide.
Beneficial effect
Compared with prior art, the invention has the advantages that:
(1) acefal homopolymer is made to 100 ~ 120 object molecules, make acefal homopolymer and vinyltrimethoxy silane, methylene diacrylamide, 2-butanone etc. compound, add the auxiliarys such as xitix, azo two isobutyl imidazoline salt hydrochlorates, be configured to have the matrix material of certain viscosity, in the temperature range of 30 ~ 50 DEG C, carry out 3D printing, composite material solidification moulding, obtains 3D printed product, can be used for the manufacture of gear, bearing, automobile component, lathe, instrument internals etc.
(2) the 3D printed material that prepared by the present invention is a kind of fluid materials, and print procedure can not stop up 3D printer head, is applicable to existing most 3D printer.
(3) preparation technology is simple, and production cost is low, is easy to be extended and applied.
Embodiment
The invention is further illustrated by the following examples
embodiment 1
The acefal homopolymer that is 3-5 ten thousand by 50g viscosity-average molecular weight is ground into 100 ~ 120 object particles; Under nitrogen atmosphere, 5g methylene diacrylamide is mixed with 30g 2-butanone, add 1g xitix, stirring at room temperature 30 minutes, then add successively 2g azo two isobutyl imidazoline salt hydrochlorates, 12g vinyltrimethoxy silane, stirring at room temperature 30 minutes, then add 50g acefal homopolymer particle, be heated to 80 DEG C, stir 30 minutes, be cooled to room temperature, obtain 3D printing acefal homopolymer matrix material.
This material is carried out to 3D printing at 50 DEG C, and after moulding, the density of material is 1.43g/cm
3, tensile strength is 5.1MPa, and shrinking percentage is 1.62%, and specific rigidity is 2650MPa.
embodiment 2
The acefal homopolymer that is 3-5 ten thousand by 40g viscosity-average molecular weight is ground into 100 ~ 120 object particles; Under nitrogen atmosphere, 7g methylene diacrylamide is mixed with 15g 2-butanone, add 3g xitix, stirring at room temperature 60 minutes, then add successively 5g azo two isobutyl imidazoline salt hydrochlorates, 30g vinyltrimethoxy silane, stirring at room temperature 60 minutes, then add 40g acefal homopolymer particle, be heated to 70 DEG C, stir 60 minutes, be cooled to room temperature, obtain 3D printing acefal homopolymer matrix material.
This material is carried out to 3D printing at 30 DEG C, and after moulding, the density of material is 1.47g/cm
3, tensile strength is 3.8MPa, and shrinking percentage is 2.12%, and specific rigidity is 2310MPa.
embodiment 3
The acefal homopolymer that is 3-5 ten thousand by 40g viscosity-average molecular weight is ground into 100 ~ 120 object particles; Under nitrogen atmosphere, 20g methylene diacrylamide is mixed with 30g 2-butanone, add 2g xitix, stirring at room temperature 50 minutes, then add successively 3g azo two isobutyl imidazoline salt hydrochlorates, 5g vinyltrimethoxy silane, stirring at room temperature 40 minutes, then add 40g acefal homopolymer particle, be heated to 75 DEG C, stir 40 minutes, be cooled to room temperature, obtain 3D printing acefal homopolymer matrix material.
This material is carried out to 3D printing at 40 DEG C, and after moulding, the density of material is 1.39g/cm
3, tensile strength is 4.1MPa, and shrinking percentage is 2.31%, and specific rigidity is 2280MPa.
embodiment 4
The acefal homopolymer that is 3-5 ten thousand by 45g viscosity-average molecular weight is ground into 100 ~ 120 object particles; Under nitrogen atmosphere, 15g methylene diacrylamide is mixed with 20g 2-butanone, add 1g xitix, stirring at room temperature 40 minutes, then add successively 4g azo two isobutyl imidazoline salt hydrochlorates, 15g vinyltrimethoxy silane, stirring at room temperature 40 minutes, then add 40g acefal homopolymer particle, be heated to 70 DEG C, stir 40 minutes, be cooled to room temperature, obtain 3D printing acefal homopolymer matrix material.
This material is carried out to 3D printing at 45 DEG C, and after moulding, the density of material is 1.44g/cm
3, tensile strength is 4.8MPa, and shrinking percentage is 2.01%, and specific rigidity is 2510MPa.
embodiment 5
The acefal homopolymer that is 3-5 ten thousand by 42g viscosity-average molecular weight is ground into 100 ~ 120 object particles; Under nitrogen atmosphere, 18g methylene diacrylamide is mixed with 24g 2-butanone, add 3g xitix, stirring at room temperature 40 minutes, then add successively 3g azo two isobutyl imidazoline salt hydrochlorates, 10g vinyltrimethoxy silane, stirring at room temperature 50 minutes, then add 40g acefal homopolymer particle, be heated to 80 DEG C, stir 50 minutes, be cooled to room temperature, obtain 3D printing acefal homopolymer matrix material.
This material is carried out to 3D printing at 50 DEG C, and after moulding, the density of material is 1.46g/cm
3, tensile strength is 5.3MPa, and shrinking percentage is 2.71%, and specific rigidity is 2380MPa.
Claims (2)
1. 3D prints and uses an acefal homopolymer matrix material, it is characterized in that: the raw material by following weight ratio forms:
Acefal homopolymer 40 ~ 50%,
Vinyltrimethoxy silane 5 ~ 30%,
Methylene diacrylamide 5 ~ 20%,
2-butanone 15 ~ 30%,
Xitix 1 ~ 3%,
Azo two isobutyl imidazoline salt hydrochlorates 2 ~ 5%.
2. described in claim 1,3D prints the preparation method with acefal homopolymer matrix material, it is characterized in that: its preparation process is as follows:
1) be that the acefal homopolymer of 3-5 ten thousand is ground into 100 ~ 120 object particles by viscosity-average molecular weight;
2) take by weight ratio raw material;
3) under nitrogen atmosphere, methylene diacrylamide is mixed with 2-butanone, add xitix, stirring at room temperature 30 ~ 60 minutes, then add successively azo two isobutyl imidazoline salt hydrochlorates, vinyltrimethoxy silane, stirring at room temperature 30 ~ 60 minutes, then add acefal homopolymer particle, be heated to 70 ~ 80 DEG C, stir 30 ~ 60 minutes, be cooled to room temperature, obtain 3D printing acefal homopolymer matrix material.
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| Application Number | Priority Date | Filing Date | Title |
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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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| Application Number | Priority Date | Filing Date | Title |
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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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| CN104177551A true CN104177551A (en) | 2014-12-03 |
| CN104177551B CN104177551B (en) | 2016-09-14 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113895052A (en) * | 2021-09-02 | 2022-01-07 | 佛山智汇君彰新材料科技有限公司 | Method for preparing carbon fiber brake handle |
| US11661521B2 (en) | 2019-12-17 | 2023-05-30 | Ticona Llc | Three-dimensional printing system employing a thermotropic liquid crystalline polymer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001023473A1 (en) * | 1999-09-29 | 2001-04-05 | E.I. Du Pont De Nemours And Company | Polyoxymethylene resin compositions having improved molding characteristics |
| 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 |
-
2014
- 2014-08-26 CN CN201410425293.8A patent/CN104177551B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001023473A1 (en) * | 1999-09-29 | 2001-04-05 | E.I. Du Pont De Nemours And Company | Polyoxymethylene resin compositions having improved molding characteristics |
| 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11661521B2 (en) | 2019-12-17 | 2023-05-30 | Ticona Llc | Three-dimensional printing system employing a thermotropic liquid crystalline polymer |
| CN113895052A (en) * | 2021-09-02 | 2022-01-07 | 佛山智汇君彰新材料科技有限公司 | Method for preparing carbon fiber brake handle |
| 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 |
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| CN104177551B (en) | 2016-09-14 |
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