CN111607129A - Formaldehyde-removing 3D printing wire rod containing axial orientation pore structure and preparation method thereof - Google Patents
Formaldehyde-removing 3D printing wire rod containing axial orientation pore structure and preparation method thereof Download PDFInfo
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- 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
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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Abstract
The invention discloses a formaldehyde-removing 3D printing wire rod with an axial orientation pore structure and a preparation method thereof. The wire has an axially oriented pore structure, the length of the pores is 10-800 μm, and the width is 0.1-9 μm. The preparation method comprises placing cellulose/polylactic acid composite material into 0.1-30% activator water solution, stirring at 2000-15000 rpm at 10-80 deg.C for 0.1-5 hr, and filtering to obtain activated wire; and then placing the activated wire and the modifier into a solvent, stirring at 2000-15000 rpm for 0.1-5 hr, filtering, and drying in vacuum at 20-60 ℃ and under the condition of less than 10KPa to obtain the 3D printing wire. The method is simple and practical in process, does not affect the original normal use process of 3D printing, and obviously improves the air purification function effect.
Description
Technical Field
The invention belongs to the field of air purification and material forming processing, and particularly relates to a 3D printing wire rod containing an axial orientation pore structure and a preparation method thereof; in particular to a formaldehyde-removing 3D printing wire rod with an axial orientation pore structure and a preparation method thereof.
Background
Formaldehyde is a well-known indoor air pollutant and is one of carcinogens and teratogens identified by the World Health Organization (WHO). In recent years, the problem of indoor air pollution has become increasingly serious. Formaldehyde is a representative indoor contaminant, mainly from interior furniture paints, decorative materials, polymeric boards, adhesives, and chemical fiber carpets. China stipulates that: the indoor formaldehyde content should not exceed 0.08mg/m 3. High concentrations of formaldehyde can cause a range of symptoms including pharyngitis, rhinitis, emphysema, lung cancer, and even death. At present, the commonly used methods for removing formaldehyde from indoor air mainly include: thermal catalytic oxidation, green plant purification, catalytic oxidation, air anion, adsorption and the like. In these processes, the thermal catalytic oxidation requires very high temperature conditions (800 ℃ to 1000 ℃). Photocatalytic decomposition has a high demand for ultraviolet radiation. The adsorption method is the most common method at present, and the activated carbon is widely applied by virtue of the characteristics of large specific surface area, pore structure, rich oxygen-containing functional groups on the surface, easiness in obtaining, low price and the like. However, the use of the activated carbon has certain limitations, the activated carbon belongs to reversible adsorption, and when factors such as air temperature, humidity and the like change, desorption can be generated to cause secondary pollution.
Cellulose, the most abundant natural polymeric compound on earth, is also an important biodegradable and renewable biomass resource used to produce various products with different applications, especially green composites. The composite material of natural plant cellulose and biodegradable polylactic acid has become a common 3D printing material. But the cellulose material and formaldehyde only have weak and reversible hydrogen bonding action, the efficiency of removing aldehyde is low, and the cellulose material and formaldehyde are difficult to be directly used in the field of indoor air purification.
Through the search and discovery of the existing patent documents, patent document CN108822511A discloses a preparation method of a PLA nanocomposite wire for all-biomass 3D printing; the provided nano composite wire has stable performance and excellent mechanical property; however, the purpose of the compatibilizing modifier is to increase the thermal stability of the composite, among other things.
Patent document CN107737584A discloses a porous material with a micro-nano structure and a preparation method thereof; the prepared porous material has high porosity and controllable structure; however, its porous structure cannot achieve a specific orientation.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a formaldehyde-removing 3D printing wire with an axis-oriented pore structure and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme:
the invention relates to a 3D printing wire, which has an axial-oriented pore structure, wherein the length of a pore is 10-800 mu m, and the width of the pore is 0.1-9 mu m.
The invention also relates to a preparation method of the 3D printing wire, which comprises the following steps:
s1, placing the cellulose/polylactic acid composite material unidirectional tensile wire into 0.1-30% of an activating agent aqueous solution, stirring at the temperature of 10-80 ℃, and filtering to obtain an activated wire;
s2, placing the activated wire and the modifier into a solvent, stirring, filtering, and drying in vacuum at 20-60 ℃ and below 10KPa to obtain the 3D printing wire with the aldehyde-removing function and the axial pore structure.
According to one embodiment of the invention, the cellulose/polylactic acid composite material unidirectional tensile wire is prepared by blending, extruding and drawing lignocellulose and polylactic acid according to a mass ratio of 1: 0.1-1 and a temperature of 150-190 ℃.
Furthermore, the stretching ratio is 2-8: 1.
According to one embodiment of the invention, the mass ratio of the cellulose/polylactic acid composite material unidirectional stretching wire rod, the activating agent aqueous solution, the modifying agent and the solvent is 1: 10-500: 0.8-10: 10-500.
In one embodiment of the present invention, in step S1, the stirring is performed at 2000 to 15000rpm for 0.1 to 5hr (hours).
In one embodiment of the present invention, in step S2, the stirring is performed at 2000 to 15000rpm for 0.1 to 5 hr.
As an embodiment of the present invention, the activating agent is selected from one or more of formic acid, acetic acid, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, sodium hydroxide, ammonia water and cellulase.
As an embodiment of the invention, the modifier is selected from one or more of chitosan, dopamine, aminopropyltriethoxysilane, tea polyphenol, triethylene tetramine, tetraethylene pentamine and ethanolamine.
As an embodiment of the present invention, the solvent is selected from one or more of water, ethanol, methanol, acetone, ethyl acetate and methyl ethyl ketone.
By adopting the scheme of the invention, in the cellulose/polylactic acid composite material, cellulose is a hydrophilic component and polylactic acid is a hydrophobic component, a micro interface exists between the cellulose and the polylactic acid, the interface tends to axial orientation during unidirectional stretching, activation and functional modification are carried out on the hydrophilic cellulose, and in the process, the penetration of reaction liquid causes the expansion of the cellulose component, so that the oriented micro interface is expanded, and a pore structure arranged in micron-scale axial orientation is formed (as shown in figure 1). The axially oriented pore structure is different from radially oriented or randomly oriented pores, and has little influence on the mechanical strength of the wire (meets the requirement of 3D printing); in addition, the specific surface area of the material is improved due to the pore structure, and the introduction of a group (functional modifier) which is beneficial to formaldehyde removal is facilitated, so that formaldehyde can be removed through chemical bonding reaction with formaldehyde in polluted air, and the air purification performance of the material is greatly improved.
Compared with the prior art, the invention has the following beneficial effects:
1) the process is simple and practical, and the original normal use process of 3D printing is not influenced;
2) the mechanical strength of the wire meets the requirement; measuring the tensile strength of the 3D printing wire with the formaldehyde-removing functional axial orientation pore structure according to the national standard GB/T1040.2-2006 'determination of plastic tensile property', wherein the measured value is more than 25 MPa;
3) the air purification function effect is obviously improved; according to the standard QB/T2761 + 2006 'method for measuring the purification effect of indoor air purification products' in the light industry. And measuring the formaldehyde purification efficiency of the 3D printing wire rod with the formaldehyde removing function axial orientation pore structure, wherein the measured value is more than 70%.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is an electron micrograph of the micron-scale axially oriented pore structure of example 1.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications, including any combination of examples, may occur to those skilled in the art without departing from the spirit of the invention.
Example 1
A formaldehyde-removing 3D printing wire with an axially oriented pore structure has an axially distributed pore structure with an average pore length of 200 μm and an average pore width of 3 μm. An electron micrograph of the micron-scale axially oriented pore structure is shown in FIG. 1.
The preparation method comprises the following steps:
placing 1 g of cellulose/polylactic acid composite material unidirectional tensile wire in 100 g of 5% sulfuric acid aqueous solution, stirring at 30 ℃ and 8000rpm for 1hr, and filtering to obtain activated wire; and then placing the activated wire and 3 g of dopamine in 100 g of acetone, stirring at 8000rpm for 1hr, filtering, and vacuum drying at 40 ℃ and 5KPa to obtain the 3D printing wire with the aldehyde-removing function and the axial pore structure.
The cellulose/polylactic acid composite material unidirectional tensile wire is prepared by mixing lignocellulose and polylactic acid according to the mass ratio of 1: 0.2, 170 ℃ and 3 of the stretching ratio.
The 3D printing wire with the aldehyde-removing axial pore structure in the embodiment has the tensile strength of 33MPa (GB/T1040.2-2006) and the formaldehyde purification efficiency of 81% (QB/T2761-2006).
In this example, when dopamine is not impregnated, the tensile strength of the wire is 29MPa (GB/T1040.2-2006) and the formaldehyde purification efficiency is 16% (QB/T2761-2006).
Example 2
A formaldehyde-removing 3D printing wire with an axially oriented pore structure has an axially distributed pore structure, the average length of the pores is 10 μm, and the average width of the pores is 0.1 μm.
The preparation method comprises the following steps:
placing 1 g of cellulose/polylactic acid composite material unidirectional tensile wire in 10 g of 30% phosphoric acid aqueous solution, stirring at the temperature of 10 ℃ and the rotating speed of 2000rpm for 0.1hr, and filtering to obtain an activated wire; and then placing the activated wire and 0.8 g of triethylene tetramine in 10 g of water, stirring at 2000rpm for 0.1hr, filtering, and carrying out vacuum drying at 20 ℃ under the condition of 1KPa to obtain the 3D printing wire with the aldehyde-removing function and the axial pore structure.
The cellulose/polylactic acid composite material unidirectional tensile wire is prepared by mixing lignocellulose and polylactic acid according to the mass ratio of 1:0.1, 150 ℃ and 2 of stretching ratio.
The 3D printing wire with the shaft-oriented pore structure with the formaldehyde removing function in the embodiment has the tensile strength of 35MPa (GB/T1040.2-2006) and the formaldehyde purification efficiency of 96% (QB/T2761-2006).
Example 3
A formaldehyde-removing 3D printing wire with an axially oriented pore structure has an axially distributed pore structure, the average length of the pores is 800 μm, and the average width of the pores is 9 μm.
The preparation method comprises the following steps:
placing 1 g of cellulose/polylactic acid composite material unidirectional tensile wire in 500 g of 0.1% ammonia water solution, stirring at the temperature of 80 ℃ and the rotating speed of 15000rpm for 5 hours, and filtering to obtain an activated wire; and then placing the activated wire and 10 g of aminopropyltriethoxysilane in 500 g of ethanol, stirring at the rotating speed of 15000rpm for 5 hours, filtering, and carrying out vacuum drying at 60 ℃ and 9KPa to obtain the 3D printing wire with the aldehyde-removing function and the axial pore structure.
The cellulose/polylactic acid composite material unidirectional tensile wire is prepared by mixing lignocellulose and polylactic acid according to the mass ratio of 1: 1. the temperature is 190 ℃, and the mixture is extruded and stretched unidirectionally with the stretch ratio of 8.
The 3D printing wire with the shaft-oriented pore structure with the formaldehyde removing function in the embodiment has the tensile strength of 31MPa (GB/T1040.2-2006) and the formaldehyde purification efficiency of 79 percent (QB/T2761-2006).
Comparative example 1
A3D printing wire with a random orientation pore structure is prepared by pouring a dichloromethane solution from lignocellulose and a polylactic acid material according to a mass ratio of 1:0.1, wherein the average pore size is 50 mu m, the measured tensile strength is only 5MPa (GB/T1040.2-2006), and the formaldehyde purification efficiency is 11% (QB/T2761-2006).
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.
Claims (10)
1. A3D printing wire is characterized by having an axis-oriented pore structure, wherein the length of each pore is 10-800 micrometers, and the width of each pore is 0.1-9 micrometers.
2. A method for preparing a 3D printing wire according to claim 1, characterized in that it comprises the following steps:
s1, placing the cellulose/polylactic acid composite material unidirectional tensile wire into 0.1-30% of an activating agent aqueous solution, stirring at the temperature of 10-80 ℃, and filtering to obtain an activated wire;
s2, placing the activated wire and the modifier into a solvent, stirring, filtering, and drying in vacuum at 20-60 ℃ and below 10KPa to obtain the 3D printing wire with the aldehyde-removing function and the axial pore structure.
3. The preparation method of the 3D printing wire rod according to claim 2, wherein the cellulose/polylactic acid composite material unidirectional stretching wire rod is prepared by blending, extruding and unidirectional stretching lignocellulose and polylactic acid according to a mass ratio of 1: 0.1-1 and a temperature of 150-190 ℃.
4. The preparation method of the 3D printing wire rod as claimed in claim 2, wherein the unidirectional stretching is performed at a stretch ratio of 2-8: 1.
5. The preparation method of the 3D printing wire rod according to claim 2, wherein the mass ratio of the cellulose/polylactic acid composite material unidirectional stretching wire rod, the activating agent aqueous solution, the modifying agent and the solvent is 1: 10-500: 0.8-10: 10-500.
6. The method for preparing a 3D printing wire according to claim 2, wherein in step S1, the stirring is performed at 2000-15000 rpm for 0.1-5 hr.
7. The method for preparing a 3D printing wire according to claim 2, wherein in step S2, the stirring is performed at 2000-15000 rpm for 0.1-5 hr.
8. The method for preparing a 3D printing wire according to claim 2, wherein the activating agent is one or more selected from formic acid, acetic acid, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, sodium hydroxide, ammonia water and cellulase.
9. The method for preparing a 3D printing wire according to claim 2, wherein the modifier is one or more selected from chitosan, dopamine, aminopropyltriethoxysilane, tea polyphenols, triethylene tetramine, tetraethylene pentamine and ethanolamine.
10. The method for preparing a 3D printing wire according to claim 2, wherein the solvent is one or more selected from water, ethanol, methanol, acetone, ethyl acetate and methyl ethyl ketone.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106633596A (en) * | 2016-11-25 | 2017-05-10 | 安徽省春谷3D打印智能装备产业技术研究院有限公司 | 3D (three-dimensional) printing wire and method for preparing same |
| CN107841100A (en) * | 2016-09-18 | 2018-03-27 | 黑龙江鑫达企业集团有限公司 | A kind of 3D printing poly-lactic acid material and preparation method thereof |
| CN108219404A (en) * | 2016-12-15 | 2018-06-29 | 天津青创众联新材料科技有限公司 | A kind of preparation method of the 3D printing material of nano micro crystal cellulose enhancing |
| CN108912629A (en) * | 2018-06-01 | 2018-11-30 | 湖南国盛石墨科技有限公司 | A kind of polylactic acid 3D printing material and its preparation method and application |
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- 2020-05-29 CN CN202010477287.2A patent/CN111607129B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107841100A (en) * | 2016-09-18 | 2018-03-27 | 黑龙江鑫达企业集团有限公司 | A kind of 3D printing poly-lactic acid material and preparation method thereof |
| CN106633596A (en) * | 2016-11-25 | 2017-05-10 | 安徽省春谷3D打印智能装备产业技术研究院有限公司 | 3D (three-dimensional) printing wire and method for preparing same |
| CN108219404A (en) * | 2016-12-15 | 2018-06-29 | 天津青创众联新材料科技有限公司 | A kind of preparation method of the 3D printing material of nano micro crystal cellulose enhancing |
| CN108912629A (en) * | 2018-06-01 | 2018-11-30 | 湖南国盛石墨科技有限公司 | A kind of polylactic acid 3D printing material and its preparation method and application |
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