CN111808408B - Photosensitive antibacterial biodegradable 3D printing wire and preparation method thereof - Google Patents
Photosensitive antibacterial biodegradable 3D printing wire and preparation method thereof Download PDFInfo
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- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- 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
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- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
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Abstract
The invention relates to the technical field of high polymer materials, in particular to a photosensitive antibacterial biodegradable 3D printing wire and a preparation method thereof. The composition comprises the following substances in parts by weight: 50-70 parts of polylactic acid, 0-40 parts of ester biodegradable plastic, 5-15 parts of cellulose nanocrystal, 2-5 parts of cross-linking agent, 2-12 parts of photosensitive color-changing powder, 2-12 parts of nano antibacterial agent, 0.1-1.5 parts of light stabilizer, 0.5-3 parts of antioxidant and 1-3 parts of lubricant. The method makes full use of the cellulose which is wide in source, low in price and renewable, can reduce the production cost of the biodegradable plastic 3D printing wire, and can achieve the purposes of being green, low-carbon and environment-friendly. High strength, high toughness, heat resistance and the like, and the size stability of the end product can be enhanced due to the existence of the semi-interpenetrating network structure. Has the characteristics of photosensitive color change and antibiosis, and is particularly suitable for the artistic creation of places such as home, offices, markets and the like.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a photosensitive antibacterial biodegradable 3D printing wire and a preparation method thereof.
Background
With the development of 3D printing technology, 3D printed products are not only limited to the fields of bioengineering, civil and architectural engineering, aerospace, etc., but also begin to enter people's daily life for creating some living appliances, ornaments, DIY artworks, etc. However, 3D printed products often need to meet the artistic design requirements of various colors, shapes, and the like in life, which puts higher demands on the development of 3D printed materials, and meanwhile, the performances such as degradability, toughness, strength, and the like are all to be further improved.
Biodegradable polymer materials, such as polylactic acid (PLA), Polyhydroxyalkanoate (PHA), polyglycolic acid (PGA), Polycaprolactone (PCL), polybutylene succinate (PBS), and the like, have been widely used for 3D printing products. Taking PLA as an example, PLA is popular because of its advantages of non-toxicity, no pungent smell, transparency, easy dyeing, biodegradability and the like. However, biodegradable polymer materials such as PLA generally have the problems of low thermal deformation temperature, strength and toughness to be improved, and the like, and also have the defect of thermal shrinkage, which severely restricts the development of biodegradable polymer materials for 3D printing.
Disclosure of Invention
The purpose of the invention is as follows: in order to provide a photosensitive antibacterial biodegradable 3D printing wire and a preparation method thereof with better effect, the specific purpose is to find a plurality of substantial technical effects of the specific implementation part.
In order to achieve the purpose, the invention adopts the following technical scheme:
the photosensitive antibacterial biodegradable 3D printing wire is characterized by comprising the following substances in parts by weight: 50-70 parts of polylactic acid, 0-40 parts of ester biodegradable plastic, 5-15 parts of cellulose nanocrystal, 2-5 parts of cross-linking agent, 2-12 parts of photosensitive color-changing powder, 2-12 parts of nano antibacterial agent, 0.1-1.5 parts of light stabilizer, 0.5-3 parts of antioxidant and 1-3 parts of lubricant.
The invention further adopts the technical scheme that the ester biodegradable plastic is any one or combination of polyhydroxy fatty acid ester, polyglycolic acid, polycaprolactone and polybutylene succinate.
The further technical proposal of the invention is that the cellulose nanocrystalline is extracted from plant fiber by at least one of acidolysis, cellulase hydrolysis and biological fermentation; the crosslinking agent is any one of peroxide crosslinking agents, isocyanate crosslinking agents, anhydride crosslinking agents, glycidyl crosslinking agents and allyl crosslinking agents.
The further technical proposal of the invention is that the peroxide cross-linking agent is any one of benzoyl peroxide and dicumyl peroxide; the isocyanate crosslinking agent is any one of triallyl isocyanurate, lysine triisocyanate, 2, 4-toluene diisocyanate and 4, 4-diphenylmethane diisocyanate; the anhydride crosslinking agent is maleic anhydride; the glycidyl cross-linking agent is triglycidyl isocyanurate; the allyl crosslinking agent is any one of polyalkyl butyl acrylate, trimethylolpropane triisobutenoate, pentaerythritol triacrylate and polyalkyl triisobutenoate.
The photosensitive color-changing powder is any one or a combination of a plurality of commercially available stilbenes, spirocycles, norbornadienes, fulgides, triphenylmethane derivatives, salicylanilide compounds and pyran derivatives.
The invention further adopts the technical scheme that the nano antibacterial agent is at least one of nano metal oxides containing silver, zinc, cerium and titanium, organic guanidines, quaternary ammonium salts, phenol ethers, pyridines, imidazoles and isothiazolinone.
The further technical proposal of the invention is that the light stabilizer is bis-2, 2,6, 6-tetramethyl piperidine sebacate (light stabilizer 770), poly (4-hydroxyethyl-2, 2,6, 6-tetramethyl-1-piperidine ethanol) succinate (light stabilizer 622), bis (1,2,2,6, 6-pentamethyl-4-piperidinyl) sebacate (light stabilizer 292), poly { [6- [ (1,1,3, 3-tetramethylbutyl) amino ] ] -1,3, 5-triazine-2, 4- [ (2,2,6,6, -tetramethyl-piperidinyl) imino ] -1, 6-hexadiene [ (2,2,6, 6-tetramethyl-4-piperidinyl) imino ] } (light stabilizer 944) in any one or more combinations.
The invention further adopts the technical scheme that the antioxidant comprises any one or more of tea polyphenol, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, N' -bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine, 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid and diphenyl octyl phosphite; the lubricant comprises at least one of stearate, glyceryl stearate, silicate, pentaerythritol stearate and ethylene bis fatty acid amide.
The preparation method of the toughened heat-resistant polylactic acid 3D printing wire is characterized by comprising the following steps:
s1: putting polylactic acid, cellulose nanocrystalline, a cross-linking agent, a photosensitive color-changing powder, a nano antibacterial agent, a light stabilizer, an antioxidant and a lubricant in parts by weight into a high-speed mixer, and stirring for 5-10mmin to obtain a mixture; putting the polylactic acid slices into a double-screw extruder for melt blending and extruding to obtain polylactic acid slices;
s2: dry-mixing the polylactic acid slices and the ester biodegradable plastics in the S1 in a high-speed mixer, performing spinning on the mixture in a melt spinning machine through a spinneret plate, and performing drafting, cooling and winding to obtain nascent fibers;
s3: bundling the nascent fibers in the S2 through a buncher, and then performing melt molding, cooling and rolling by adopting a pultrusion process to obtain a 3D printing wire rod with the diameter of 1.75 mm;
the temperature of a charging barrel of the double-screw extruder is 160-210 ℃, the rotating speed of a main machine is 350-600r/min, and the feeding frequency is 7-16r/min in sequence;
the melt spinning process comprises the following steps: the melt spinning temperature is 170-220 ℃, the drafting temperature is 80-110 ℃, and the primary fiber fineness is 1.5-4.5 dtex;
further, the pultrusion process comprises the following steps: the temperature of the first section is 170 ℃ and 190 ℃, the temperature of the second section is 200 ℃ and 230 ℃, and the pultrusion speed is 0.2-1.5 m/min.
A further technical solution of the present invention is that the present invention applies to the following mechanism:
the dispersion mechanism is as follows: shear force and stretching force along the silk thread direction are provided by means of melt spinning and drawing, so that the oriented arrangement and ordered dispersion of cellulose nanocrystals are promoted, and the uniform dispersion of auxiliaries such as a cross-linking agent, a photosensitive color-changing powder, a nano antibacterial agent and an antioxidant in a biodegradable plastic matrix is facilitated; meanwhile, after the plastic filaments with the micron scale are gathered, the plastic filaments are melted by a pultrusion process to form a wire with the millimeter scale, and the dispersion of the cellulose nanocrystals and the auxiliary agent in the plastic matrix is further promoted along with the shearing force and the stretching force;
the mechanism of induced crystallization: hydroxyl (-OH) in the cellulose nanocrystal and carbonyl (C ═ O) in PLA and ester biodegradable plastics can form hydrogen bonds, which is beneficial to the adhesion growth of plastic molecular chains such as PLA and the like at an interface and the induction of PLA heterogeneous nucleation crystallization, and the cellulose nanocrystal can be used as a nucleation point to refine PLA spherulites and improve the crystallization density and the crystallization temperature, so that the mechanical property and the thermal property of the PLA are improved; meanwhile, the biodegradable plastic wires are collected to form millimeter-scale wires through a pultrusion process, and the crystallization of plastics such as PLA and the like can be further improved along with the melting and cooling processes;
the mechanism of formation of the semi-interpenetrating network structure: active polyfunctional acid anhydride, isocyanate, glycidyl and other groups in the cross-linking agent can generate local chemical cross-linking with active hydrogen on the surfaces of PLA and ester biodegradable plastics and cellulose nanocrystals in a heating state, and finally form a semi-interpenetrating network structure with a linear plastic molecular chain, so that the mechanical property and the thermal property of a matrix can be further improved; in addition, the semi-interpenetrating network structure can restrain the oriented cellulose nanocrystals from scattering in the secondary crystallization process, and simultaneously further combs the molecular chain arrangement of the matrix under the action of shearing force and stretching force, thereby reducing the heat shrinkage defect of the product;
the strengthening and toughening mechanism is as follows: the cellulose nanocrystalline with higher modulus can be used as a nano reinforcing agent to improve the strength of a plastic matrix; meanwhile, the cellulose nanocrystal has a certain length-diameter ratio and can be used for synergistically toughening the plastic with a semi-interpenetrating network structure after spinning orientation.
Compared with the prior art, the invention adopting the technical scheme has the following beneficial effects: compared with the prior art, the invention has the following positive effects:
(1) the invention fully utilizes the cellulose which is wide in source, low in price and renewable, can reduce the production cost of the biodegradable plastic 3D printing wire rod, and can also realize the purposes of green, low carbon and environmental protection.
(2) The 3D printing wire rod disclosed by the invention has the characteristics of high strength, high toughness, heat resistance and the like, and the size stability of a terminal product can be enhanced due to the existence of a semi-interpenetrating network structure.
(3) The 3D printing wire rod disclosed by the invention has the characteristics of photosensitive discoloration and antibiosis, is particularly suitable for artistic creation of places such as homes, offices, markets and the like, and widens the application field of biodegradable high polymer materials.
Drawings
To further illustrate the present invention, further description is provided below with reference to the accompanying drawings:
FIG. 1 is Table 1, and Table 1 is a table of mechanical and thermal data for comparative and example samples.
Fig. 2 is table 2, and after the test of a color difference meter, it is found that the brightness of the biodegradable 3D printing wire is not changed much, but the corresponding color difference value is very large, and the visible photosensitive discoloration effect is obvious; meanwhile, the survival rate of escherichia coli shows that the antibacterial effect of the biodegradable 3D printing wire is obvious after the antibacterial agent is added.
Detailed Description
The present invention will be further illustrated with reference to the accompanying drawings and specific embodiments, which are to be understood as merely illustrative of the invention and not as limiting the scope of the invention.
The patent provides a plurality of parallel schemes, and different expressions belong to an improved scheme based on a basic scheme or a parallel scheme. Each solution has its own unique features. In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1:
s1: putting 55 parts of PLA2002D, 10 parts of cellulose nanocrystal, 2 parts of triallyl isocyanurate, 10 parts of photosensitive metamorphic powder MC #12 (colorless metamorphic purple, Shenzhen, Qiansheng new color material science and technology Co., Ltd.), 3 parts of nano silver, 0.5 part of light stabilizer 770, 1.5 parts of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 2 parts of zinc stearate into a high-speed mixer, and stirring for 8min to obtain a mixture; putting the mixture into a double-screw extruder for melt blending and extruding to obtain mixture slices;
s2: dry-mixing the polylactic acid slices in the S1 and 25 parts of polycaprolactone in a high-speed mixer, carrying out spinning on the mixed solution in a melt spinning machine through a spinneret plate, and carrying out drafting, cooling and winding on the spun solution to obtain nascent fibers;
s3: bundling the primary fibers in the S2 through a buncher, and then performing melt molding, cooling and rolling through a pultrusion process to obtain the 3D printing wire rod with the diameter of 1.75 +/-0.05 mm.
Wherein the temperature of a charging barrel of the double-screw extruder is 165 ℃, the rotating speed of a main machine is 400r/min, and the feeding frequency is 11r/min in sequence; the melt spinning temperature is 190 ℃, the drafting temperature is 100 ℃, and the primary fiber fineness is 2.0 dtex; the temperature of the first section of the pultrusion die is 175 ℃, the temperature of the second section is 215 ℃, and the pultrusion speed is 0.6 m/min.
Example 2:
s1: putting 50 parts of PLA2002D, 10 parts of cellulose nanocrystal, 3 parts of triallyl isocyanurate, 8 parts of photosensitive metamorphic powder MC #12 (colorless metamorphic purple, Shenzhen, Qiansheng new color material science and technology Co., Ltd.), 5 parts of nano zinc oxide, 0.4 part of light stabilizer 770, 1.5 parts of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 2.5 parts of zinc stearate into a high-speed mixer, and stirring for 8min to obtain a mixture; putting the mixture into a double-screw extruder for melt blending and extruding to obtain mixture slices;
s2: dry-mixing the polylactic acid slices in the S1 and 35 parts of polyhydroxyalkanoate in a high-speed mixer, performing spinning on the mixed polylactic acid slices and 35 parts of polyhydroxyalkanoate in a melt spinning machine through a spinneret plate, and performing drafting, cooling and winding to obtain nascent fibers;
s3: bundling the primary fibers in the S2 through a buncher, and then performing melt molding, cooling and rolling through a pultrusion process to obtain a 3D printing wire rod with the diameter of 1.75 mm.
Wherein the temperature of a charging barrel of the double-screw extruder is 170 ℃, the rotating speed of a main machine is 450r/min, and the feeding frequency is 10r/min in sequence; the melt spinning temperature is 190 ℃, the drafting temperature is 100 ℃, and the primary fiber fineness is 2.0 dtex; the temperature of the first section of the pultrusion die is 175 ℃, the temperature of the second section is 215 ℃, and the pultrusion speed is 0.6 m/min.
Example 3:
s1: putting 60 parts of PLA2002D, 12 parts of cellulose nanocrystal, 2.5 parts of triallyl isocyanurate, 11 parts of photosensitive discoloring powder MC #12 (colorless discoloring purple, Shenzhen Qiansheng new color material science and technology Co., Ltd.), 3 parts of nano silver, 0.8 part of light stabilizer 770, 1.9 parts of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 2.1 parts of zinc stearate into a high-speed mixer, and stirring for 9min to obtain a mixture; putting the mixture into a double-screw extruder for melt blending and extruding to obtain mixture slices;
s2: dry-mixing the polylactic acid slices in the S1 and 15 parts of polyhydroxyalkanoate in a high-speed mixer, performing spinning on the mixed polylactic acid slices and 15 parts of polyhydroxyalkanoate in a melt spinning machine through a spinneret plate, and performing drafting, cooling and winding to obtain nascent fibers;
s3: bundling the primary fibers in the S2 through a buncher, and then performing melt molding, cooling and rolling through a pultrusion process to obtain a 3D printing wire rod with the diameter of 1.75 mm.
Wherein the temperature of a charging barrel of the double-screw extruder is 165 ℃, the rotating speed of a main machine is 400r/min, and the feeding frequency is 11r/min in sequence; the melt spinning temperature is 190 ℃, the drafting temperature is 100 ℃, and the primary fiber fineness is 2.0 dtex; the temperature of the first section of the pultrusion die is 175 ℃, the temperature of the second section is 215 ℃, and the pultrusion speed is 0.6 m/min.
Example 4:
s1: 50 parts of PLA4032D, 10 parts of cellulose nanocrystal, 2 parts of triglycidyl isocyanurate, 10 parts of photosensitive color-changing powder MC #17 (colorless to orange), 3 parts of nano titanium dioxide, 0.5 part of light stabilizer 944, 1.5 parts of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 2 parts of magnesium stearate are put into a high-speed mixer and stirred for 8min to obtain a mixture; putting the mixture into a double-screw extruder for melt blending and extruding to obtain mixture slices;
s2: dry-mixing the polylactic acid slices in the S1 and 20 parts of polycaprolactone in a high-speed mixer, carrying out spinning on the mixed solution in a melt spinning machine through a spinneret plate, and carrying out drafting, cooling and winding on the spun solution to obtain nascent fibers;
s3: bundling the primary fibers in the S2 through a buncher, and then performing melt molding, cooling and rolling through a pultrusion process to obtain a 3D printing wire rod with the diameter of 1.75 mm.
Wherein the temperature of a charging barrel of the double-screw extruder is 165 ℃, the rotating speed of a main machine is 400r/min, and the feeding frequency is 11r/min in sequence; the melt spinning temperature is 190 ℃, the drafting temperature is 100 ℃, and the primary fiber fineness is 2.0 dtex; the temperature of the first section of the pultrusion die is 175 ℃, the temperature of the second section is 215 ℃, and the pultrusion speed is 0.6 m/min.
Example 5:
s1: putting 55 parts of PLA2002D, 10 parts of cellulose nanocrystal, 3.0 parts of maleic anhydride, 5 parts of photosensitive color-changing powder MC #12 (colorless to purple), 5 parts of photosensitive color-changing powder MC #19 (colorless to red), 3.5 parts of polyhexamethylene guanidine phosphate, 0.5 part of light stabilizer 292, 1.5 parts of N, N' -bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine and 2 parts of glyceryl stearate into a high-speed mixer, and stirring for 8min to obtain a mixture; putting the mixture into a double-screw extruder for melt blending and extruding to obtain mixture slices;
s2: dry-mixing the polylactic acid slices in the S1 and 27 parts of polybutylene succinate in a high-speed mixer, performing spinning on the mixed polylactic acid slices and 27 parts of polybutylene succinate in a melt spinning machine through a spinneret plate, and performing drafting, cooling and winding to obtain nascent fibers;
s3: bundling the primary fibers in the S2 through a buncher, and then performing melt molding, cooling and rolling through a pultrusion process to obtain a 3D printing wire rod with the diameter of 1.75 mm.
Wherein the temperature of a charging barrel of the double-screw extruder is 165 ℃, the rotating speed of a main machine is 400r/min, and the feeding frequency is 11r/min in sequence; the melt spinning temperature is 190 ℃, the drafting temperature is 100 ℃, and the primary fiber fineness is 2.0 dtex; the temperature of the first section of the pultrusion die is 175 ℃, the temperature of the second section is 215 ℃, and the pultrusion speed is 0.6 m/min.
Example 6:
s1: 70 parts of PLA4032D, 12 parts of cellulose nanocrystal, 2.6 parts of polyalkyl butyl acrylate, 2 parts of photosensitive color-changing powder MC #12 (colorless to purple), 2 parts of photosensitive color-changing powder MC #14 (colorless to blue), 2 parts of photosensitive color-changing powder MC #16 (colorless to yellow), 2 parts of photosensitive color-changing powder MC #17 (colorless to orange), 2 parts of photosensitive color-changing powder MC #19 (colorless to red), 3 parts of 2-methyl-4-isothiazolin-3-one, 0.5 part of light stabilizer 662, 1.5 parts of diphenyl octyl phosphite and 2.1 parts of pentaerythritol stearate are put into a high-speed mixer and stirred for 8min to obtain a mixture; putting the mixture into a double-screw extruder for melt blending and extruding to obtain mixture slices;
s2: carrying out spinning on the polylactic acid slices in the S1 in a melt spinning machine through a spinneret plate, and carrying out drafting, cooling and winding to obtain nascent fibers;
s3: bundling the primary fibers in the S2 through a buncher, and then performing melt molding, cooling and rolling through a pultrusion process to obtain a 3D printing wire rod with the diameter of 1.75 mm.
Wherein the temperature of a charging barrel of the double-screw extruder is 165 ℃, the rotating speed of a main machine is 400r/min, and the feeding frequency is 11r/min in sequence; the melt spinning temperature is 190 ℃, the drafting temperature is 100 ℃, and the primary fiber fineness is 2.1 dtex; the temperature of the first section of the pultrusion die is 175 ℃, the temperature of the second section is 215 ℃, and the pultrusion speed is 0.6 m/min.
Comparative example 1
The raw material proportion and the steps in the embodiment 1 are changed into:
s1: putting 55 parts of PLA2002D, 0.5 part of light stabilizer 770, 1.5 parts of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 2 parts of zinc stearate into a high-speed mixer, and stirring for 8min to obtain a mixture; putting the mixture into a double-screw extruder for melt blending and extruding to obtain mixture slices;
s2: dry-mixing the polylactic acid slices in the S1 and 25 parts of polycaprolactone in a high-speed mixer, carrying out spinning on the mixed solution in a melt spinning machine through a spinneret plate, and carrying out drafting, cooling and winding on the spun solution to obtain nascent fibers;
s3: bundling the primary fibers in the S2 through a buncher, and then performing melt molding, cooling and rolling through a pultrusion process to obtain a 3D printing wire rod with the diameter of 1.75 mm.
Wherein the temperature of a charging barrel of the double-screw extruder is 165 ℃, the rotating speed of a main machine is 400r/min, and the feeding frequency is 11r/min in sequence; the melt spinning temperature is 190 ℃, the drafting temperature is 100 ℃, and the primary fiber fineness is 2.0 dtex; the temperature of the first section of the pultrusion die is 175 ℃, the temperature of the second section is 215 ℃, and the pultrusion speed is 0.6 m/min.
Comparative example 2
The raw material proportion and the steps in the embodiment 1 are changed into:
s1: putting 55 parts of PLA2002D, 10 parts of cellulose nanocrystal, 2 parts of triallyl isocyanurate, 10 parts of photosensitive metamorphic powder MC #12 (colorless metamorphic purple, Shenzhen, Qiansheng new color material science and technology Co., Ltd.), 3 parts of nano silver, 0.5 part of light stabilizer 770, 1.5 parts of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 2 parts of zinc stearate into a high-speed mixer, and stirring for 8min to obtain a mixture; putting the mixture into a double-screw extruder for melt blending and extruding to obtain mixture slices; wherein the temperature of a charging barrel of the double-screw extruder is 165 ℃, the rotating speed of a main machine is 400r/min, and the feeding frequency is 11 r/min.
S2: after the polylactic acid chips of S1 and 25 parts of polycaprolactone were dry-blended in a high-speed mixer, PLA-based 3D printing wires having a diameter of 1.75mm were directly prepared through a linear extruder.
And adding the cut and dried wire rods into an injection molding machine for injection molding to obtain tensile, impact and DSC test samples, and testing and observing the survival rate of escherichia coli by adopting a color difference meter.
As can be seen from Table 1, the strength, toughness and heat resistance of the modified PLA are remarkably improved through the formula design and preparation process of the invention. As can be seen from table 2, after the color difference meter tests, it is found that the brightness of the biodegradable 3D printing wire is not greatly changed, but the corresponding color difference value is very large, and the visible light-sensitive color-changing effect is obvious; meanwhile, the survival rate of escherichia coli shows that the antibacterial effect of the biodegradable 3D printing wire is obvious after the antibacterial agent is added.
It should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (8)
1. The photosensitive antibacterial biodegradable 3D printing wire is characterized by comprising the following substances in parts by weight: 50-70 parts of polylactic acid, 0-40 parts of ester biodegradable plastic, 5-15 parts of cellulose nanocrystal, 2-5 parts of cross-linking agent, 2-12 parts of photosensitive color-changing powder, 2-12 parts of nano antibacterial agent, 0.1-1.5 parts of light stabilizer, 0.5-3 parts of antioxidant and 1-3 parts of lubricant;
the preparation method comprises the following steps:
s1: putting polylactic acid, cellulose nanocrystalline, a cross-linking agent, a photosensitive color-changing powder, a nano antibacterial agent, a light stabilizer, an antioxidant and a lubricant in parts by weight into a high-speed mixer, and stirring for 5-10min to obtain a mixture; putting the polylactic acid slices into a double-screw extruder for melt blending and extruding to obtain polylactic acid slices;
s2: dry-mixing the polylactic acid slices and the ester biodegradable plastics in the S1 in a high-speed mixer, performing spinning on the mixture in a melt spinning machine through a spinneret plate, and performing drafting, cooling and winding to obtain nascent fibers;
s3: bundling the nascent fibers in the S2 through a buncher, and then performing melt molding, cooling and rolling by adopting a pultrusion process to obtain a 3D printing wire rod with the diameter of 1.75 mm;
the temperature of a charging barrel of the double-screw extruder is 160-210 ℃, the rotating speed of a main machine is 350-600r/min, and the feeding frequency is 7-16r/min in sequence;
the melt spinning process comprises the following steps: the melt spinning temperature is 170-220 ℃, the drafting temperature is 80-110 ℃, and the primary fiber fineness is 1.5-4.5 dtex;
the pultrusion process comprises the following steps: the temperature of the first section is 170 ℃ and 190 ℃, the temperature of the second section is 200 ℃ and 230 ℃, and the pultrusion speed is 0.2-1.5 m/min.
2. A photosensitive antibacterial biodegradable 3D printing wire as claimed in claim 1, wherein said ester type biodegradable plastic is any one or combination of polyhydroxyalkanoate, polyglycolic acid, polycaprolactone, polybutylene succinate.
3. The photosensitive antibacterial biodegradable 3D printing wire according to claim 1, wherein the cellulose nanocrystals are extracted from plant fibers by at least one of acid hydrolysis, cellulose hydrolysis and biological fermentation; the crosslinking agent is any one of peroxide crosslinking agents, isocyanate crosslinking agents, anhydride crosslinking agents, glycidyl crosslinking agents and allyl crosslinking agents.
4. The photosensitive antibacterial biodegradable 3D printing wire material according to claim 3, wherein the peroxide cross-linking agent is any one of benzoyl peroxide and dicumyl peroxide; the isocyanate crosslinking agent is any one of triallyl isocyanurate, lysine triisocyanate, 2, 4-toluene diisocyanate and 4, 4-diphenylmethane diisocyanate; the anhydride crosslinking agent is maleic anhydride; the glycidyl cross-linking agent is triglycidyl isocyanurate; the allyl crosslinking agent is any one of polyalkyl butyl acrylate, trimethylolpropane triisobutenoate, pentaerythritol triacrylate and polyalkyl triisobutenoate.
5. The photosensitive antibacterial biodegradable 3D printing wire material according to claim 1, wherein the photosensitive color-changing powder is any one or more of commercially available stilbenes, spirocycles, norbornadienes, fulgides, triphenylmethane derivatives, salicylanilides and pyrans.
6. The photosensitive antibacterial biodegradable 3D printing wire according to claim 1, wherein the nano antibacterial agent is at least one of nano metal oxides containing silver, zinc, cerium and titanium, organic guanidines, quaternary ammonium salts, phenol ethers, pyridines, imidazoles and isothiazolinones.
7. The photosensitive antibacterial biodegradable 3D printing wire material according to claim 1, the light stabilizer is any one or more of bis-2, 2,6, 6-tetramethylpiperidyl sebacate, poly-4-hydroxyethyl-2, 2,6, 6-tetramethyl-1-piperidyl succinate, bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate, poly { [6- [ (1,1,3, 3-tetramethylbutyl) amino ] ] -1,3, 5-triazine-2, 4- [ (2,2,6,6, -tetramethyl-piperidyl) imino ] -1, 6-hexamethylene [ (2,2,6, 6-tetramethyl-4-piperidyl) imino ] }.
8. The photo-sensitive, antibacterial, and biodegradable 3D printing wire as claimed in claim 1, wherein the antioxidant comprises any one or more combination of tea polyphenols, pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N' -bis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine, 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, and diphenyl octyl phosphite; the lubricant comprises at least one of stearate, glyceryl stearate, silicate, pentaerythritol stearate and ethylene bis fatty acid amide.
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