CN115386209A - Long-acting odor-retaining PLA wire applied to the field of 3D printing, and preparation method and application thereof - Google Patents
Long-acting odor-retaining PLA wire applied to the field of 3D printing, and preparation method and application thereof Download PDFInfo
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- CN115386209A CN115386209A CN202210988116.5A CN202210988116A CN115386209A CN 115386209 A CN115386209 A CN 115386209A CN 202210988116 A CN202210988116 A CN 202210988116A CN 115386209 A CN115386209 A CN 115386209A
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- 238000010146 3D printing Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 36
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- 230000008569 process Effects 0.000 claims abstract description 17
- 238000002844 melting Methods 0.000 claims abstract description 7
- 230000008018 melting Effects 0.000 claims abstract description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 27
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- 229920000578 graft copolymer Polymers 0.000 claims description 24
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 21
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 238000007639 printing Methods 0.000 claims description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- 239000012745 toughening agent Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 10
- 239000011707 mineral Substances 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 230000000655 anti-hydrolysis Effects 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000006068 polycondensation reaction Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- 239000002304 perfume Substances 0.000 claims description 5
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229920004482 WACKER® Polymers 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims 6
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims 3
- 230000035484 reaction time Effects 0.000 claims 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims 1
- 229940044175 cobalt sulfate Drugs 0.000 claims 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims 1
- 229910000365 copper sulfate Inorganic materials 0.000 claims 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims 1
- JZZKGJOHPIBRDB-UHFFFAOYSA-K europium(3+) prop-2-enoate Chemical compound [Eu+3].[O-]C(=O)C=C.[O-]C(=O)C=C.[O-]C(=O)C=C JZZKGJOHPIBRDB-UHFFFAOYSA-K 0.000 claims 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims 1
- 239000000454 talc Substances 0.000 claims 1
- 229910052623 talc Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 24
- 238000012545 processing Methods 0.000 abstract description 13
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- 239000006185 dispersion Substances 0.000 abstract description 9
- 238000005034 decoration Methods 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 229920000747 poly(lactic acid) Polymers 0.000 description 127
- 239000004626 polylactic acid Substances 0.000 description 127
- 239000000243 solution Substances 0.000 description 17
- 239000002994 raw material Substances 0.000 description 14
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 12
- 235000012141 vanillin Nutrition 0.000 description 12
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000003205 fragrance Substances 0.000 description 9
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 239000008187 granular material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000000498 cooling water Substances 0.000 description 4
- 238000007792 addition Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 239000000796 flavoring agent Substances 0.000 description 3
- 235000019634 flavors Nutrition 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
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- 238000002845 discoloration Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 230000003179 granulation Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 230000005923 long-lasting effect Effects 0.000 description 2
- 239000003094 microcapsule Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000122205 Chamaeleonidae Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 235000010254 Jasminum officinale Nutrition 0.000 description 1
- 240000005385 Jasminum sambac Species 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- 238000000071 blow moulding Methods 0.000 description 1
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- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010096 film blowing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229930002839 ionone Natural products 0.000 description 1
- 150000002499 ionone derivatives Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- -1 modified acrylic ester Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Civil Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Structural Engineering (AREA)
- Composite Materials (AREA)
- Ceramic Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a long-acting fragrance-retaining PLA wire rod applicable to the field of 3D printing and a preparation method thereof. Compared with simple mixing, melting and granulating of the essence, the VanPOSS-PLA introduces essence molecules into a polymer molecular chain, greatly improves the heat resistance and the dispersion uniformity of the essence in the processing process, and really ensures the long-acting fragrance-retaining effect of the material. The prepared PLA wire for 3D printing can be widely applied to scenes such as articles for cultural wound, home decoration parts and the like, and the interestingness and functionality of the 3D printing material are expanded.
Description
Technical Field
The invention belongs to the field of 3D printing materials, and particularly relates to a long-acting fragrance-remaining PLA wire rod applied to the field of 3D printing and a preparation method thereof.
Background
3D printing (especially with FDM as the representative material extrusion formula 3D printing technology) has the advantage of with low costs, easy operation, no poisonous and harmful production, has obtained wide application in industry fields such as industrial design, medical protective equipment, automobile assembly, education, amusement.
Materials commonly used for FDM printing are PLA, ABS, PETG, etc. The PLA has wide sources, low printing temperature, good biodegradability, good printing and forming effects and stable chemical stability, is not reacted with common toner and filler, is widely applied and gradually accelerates to enter the daily life of people. Because of the limited mechanical property of PLA, PLA is difficult to be applied to industrial structural parts in large batch, and is more used for printing some living appliances, ornaments, teaching demonstration articles, artistic structures and the like. With the market expansion, PLA with different special functions or characteristics is gradually developed and applied, such as lasting fragrance, temperature discoloration, and the like, and the interest and functionality of the 3D printing material are more abundant.
CN108912632A and CN114058166A respectively disclose a PLA wire rod with fragrance applied to the field of 3D printing and a preparation method thereof, wherein the fragrance is realized by directly adding a fragrance agent. But in reality, 3D printing wires need to be subjected to double-screw granulation and single-screw extrusion, and need to be melted again during printing, and finally, a printed finished product model has no fragrance. The material is analyzed by TGA, the temperature is raised to 220 ℃ for many times, three processing processes are simulated, and consequently, more than 90% of added essence is decomposed after the temperature is raised for the second time, and the retention rate of the residual essence is extremely low after the temperature is raised for the third time.
CN113136094A discloses a reversible thermochromic polylactic acid material and a preparation method thereof, wherein temperature-sensitive discoloration is realized by adding thermochromic powder microcapsules. The method reduces the consumption of the temperature-change toner, and increases the dispersion difficulty during processing. In addition, the compatilizer is aged and failed gradually during the use process of the material, so that more precipitates are formed on the surface of the material, and the appearance is poor.
Therefore, the method for preparing the 3D printing PLA wire with the temperature change and fragrance retaining functions still has great improvement and innovation space.
Disclosure of Invention
The invention aims to provide a long-acting fragrance-retaining PLA wire rod applied to the field of 3D printing and a preparation method thereof. The essence modified POSS-PLA graft polymer (vanPOSS-PLA) is prepared, then the essence modified POSS-PLA graft polymer is mixed with PLA, optional temperature-sensitive color-changing powder and other auxiliary agents to be melted and granulated, and finally the long-acting fragrance-retaining/temperature-sensitive color-changing PLA wire is prepared. On one hand, the van POSS-PLA introduces essence molecules into a polymer molecular chain, compared with simple essence mixing, melting and granulating, the heat resistance and the dispersion uniformity of the essence in the processing process are greatly improved, and the long-acting fragrance-retaining effect of the material is really ensured; on the other hand, the cage-shaped structure of the POSS can adsorb the temperature-sensitive toner, and the heat resistance and the dispersion uniformity of the temperature-sensitive toner in the processing process are improved, so that the 3D printing wire prepared from the material has a long-acting fragrance-retaining effect and a more stable reversible temperature change effect.
In order to achieve the purpose, the invention adopts the following technical scheme:
a long-acting odor-retaining type PLA wire applied to the field of 3D printing is prepared from the following components in percentage by weight:
s1, PLA,20% -80%, preferably 35% -60%;
s2, 0 to 4 percent of thermochromic powder, preferably 0.5 to 2 percent;
s3, 1% -15% of mineral powder, preferably 2% -5%;
s4, 0.05-2% of an anti-hydrolysis agent, preferably 0.5-1%;
s5, a toughening agent, 0.05% -3%, preferably 0.5% -1.5%;
s6, essence modified POSS-PLA graft polymer (vanPOSS-PLA), 10% -70%, preferably 30% -60%.
Wherein the perfume modified POSS-PLA graft polymer (vanPOSS-PLA) is prepared by comprising the following components:
s7, essence modified acrylate POSS (vanPOSS);
s8 and PLA, the dosage of which is 0.8 to 1.5 times of that of S7, preferably 1 to 1.2 times;
s9 and stannous octoate, the dosage of which is 5% -30% of that of S7, preferably 10% -20%.
As a preferred preparation method, the essence modified acrylate POSS and PLA are placed in a reaction tube, nitrogen is continuously introduced into a reaction device, the reaction device is heated until the mixture is completely melted, stannous octoate is added, the mixture is continuously reacted at high temperature, then the mixture is transferred into an ice bath, after the product is completely dissolved by dichloromethane, a large amount of precooled methanol is poured, a precipitate is obtained by centrifugation, the precipitate is repeatedly washed and then placed in an oven for drying, and the essence modified POSS-PLA graft polymer (vanPOSS-PLA) is prepared.
Preferably, the reaction conditions are: the temperature is 150-170 ℃, and the time is 20-30h; drying conditions are as follows: the temperature is 40-60 ℃ and the time is 10-20h.
Wherein the perfume modified acrylate POSS (vanPOSS) is prepared by comprising:
s12, acrylate POSS;
s13 and essence, the dosage is 8-20 times of S12, preferably 10-15 times. The essence can be natural or artificial essence such as vanillin, ionone, and jasmine essence.
As a preferred preparation method, the acrylate POSS is dissolved in tetrahydrofuran, and the essence is dissolved in absolute ethyl alcohol. Heating the tetrahydrofuran solution, slowly stirring and dripping the tetrahydrofuran solution into the ethanol solution to carry out reflux reaction. And then rapidly cooling to room temperature, adding a large amount of pure water to separate out a product, filtering, and repeatedly washing to obtain the essence modified acrylate POSS (vanPOSS). Preferably, the reaction conditions are: the temperature is 50-80 ℃, and the heating time is 2-5h.
In the modification process of PLA, essence and thermochromic powder microcapsules are directly added to prepare a PLA wire with slight fragrance and a thermochromic function, but the two defects exist: on one hand, after the model is printed, the fragrance rate is extremely low, mainly because the essence is seriously decomposed in the multiple processing processes; on the other hand, the temperature-sensitive color-changing uniformity is poor, and the material appearance is obviously poor along with the prolonging of the service time, mainly because the usage amount of the temperature-sensitive color-changing is small and the compatilizer is aged and loses efficacy. According to the invention, the essence modified POSS-PLA graft polymer (vanPOSS-PLA) is prepared firstly, so that essence molecules are fixed on a PLA matrix, and the high-temperature decomposition of the essence in the processing process is greatly reduced; and the cage-shaped structure of POSS can adsorb the temperature-sensitive toner, and the heat resistance and the dispersion uniformity of the temperature-sensitive toner in the processing process are improved, so that the 3D printing wire prepared from the material has a long-acting fragrance retaining effect and a more stable reversible temperature change effect.
In the invention, the PLA (polylactic acid) is one or more of ring-opening polymerization PLA and direct polycondensation PLA, preferably direct polycondensation PLA; preferably, the PLA has a melt index of 1 to 30g/10min (190 ℃,2.16 kg) and a molecular weight of 40000 to 100000g/mol.
In the present invention, the thermochromic powder is one or more of nickel chloride-hexamethylenetetramine hydrate, copper sulfate-hexamethylenetetramine hydrate, cobalt sulfate-hexamethylenetetramine hydrate, phenanthroline-europium acrylate complex, crystal violet lactone, and bisphenol a, and preferably one or more of nickel chloride-hexamethylenetetramine hydrate, crystal violet lactone, and bisphenol a.
In the invention, the mineral powder is one or more of talcum powder, calcium carbonate, wollastonite and mica, and calcium carbonate is preferred.
In the present invention, the anti-hydrolysis agent is one or more of a polymeric type and a monomeric type, preferably one or more of HY210, DSA10A, and K-1;
in the invention, the toughening agent is one or more of AX8900, wacker2504 and Wacker2505, preferably one or more of Wacker2504 and Wacker 2505.
Another object of the present invention is to provide a method for preparing the long-lasting fragrance-retaining temperature-sensitive color-changing PLA wire. According to the invention, essence modified acrylate POSS (vanPOSS) is prepared by carrying out co-heating reflux and other processes, then PLA raw materials and catalysts are added, and then essence modified POSS-PLA graft polymer (vanPOSS-PLA) is prepared by carrying out vacuum mixing and melting and other processes, and then the essence modified POSS-PLA graft polymer is mixed with PLA, temperature-sensitive color-changing powder and other additives for melting granulation, and finally the long-acting fragrance-remaining temperature-sensitive color-changing PLA wire rod is prepared.
A method for preparing the long-acting odor-remaining temperature-sensitive color-changing PLA wire rod comprises the following steps:
mixing PLA, a temperature-variable color powder, mineral powder, an anti-hydrolysis agent, a toughening agent and van POSS-PLA, adding the mixture into a double-screw extruder for melt extrusion, cooling, granulating and drying to obtain modified PLA particles, and adding the modified PLA particles into a single-screw extruder for melt extrusion to obtain the PLA wire.
As a preferred method, a method for preparing the long-lasting scent-retaining thermochromic PLA wire, comprising the steps of:
A. dissolving the POSS in tetrahydrofuran, and dissolving the essence in absolute ethyl alcohol. Heating the tetrahydrofuran solution, slowly stirring and dripping the tetrahydrofuran solution into the ethanol solution to carry out reflux reaction. And then rapidly cooling to room temperature, adding a large amount of pure water to separate out a product, filtering, and repeatedly washing to obtain the essence modified acrylate POSS (vanPOSS).
B. Placing the essence modified acrylate POSS and PLA into a reaction tube, continuously introducing nitrogen into a reaction device, heating until the mixture is completely melted, adding stannous octoate, continuously performing reflux reaction at high temperature, then transferring into an ice bath, completely dissolving the product with dichloromethane, pouring a large amount of precooled methanol, centrifuging to obtain a precipitate, repeatedly washing, and then placing into a drying oven for drying to obtain the essence modified POSS-PLA graft polymer (vanPOSS-PLA).
C. Mixing PLA, a temperature-variable color powder, mineral powder, an anti-hydrolysis agent, a toughening agent and van POSS-PLA, adding the mixture into a double-screw extruder for melt extrusion, cooling, granulating and drying to obtain modified PLA particles, and adding the modified PLA particles into a single-screw extruder for melt extrusion to obtain the PLA wire.
In the method of the invention, the reflux reaction conditions of the step A are as follows: the temperature is 50-80 ℃, and the heating time is 2-5h.
In the method of the invention, the reflux reaction conditions of the step B are as follows: the temperature is 150-170 ℃, and the time is 20-30h; drying conditions are as follows: the temperature is 40-60 ℃ and the time is 10-20h.
In the invention, a high-speed mixer is adopted for mixing in the step C, the rotating speed is 20-100 rpm, the temperature is 20-50 ℃, and the mixing time is 3-10 min. The screw temperature of the double-screw extruder is 150-210 ℃, and the rotating speed is 100-800rpm. The screw temperature of the single-screw extruder is 160-200 ℃, and the rotating speed is 100-200rpm. The temperature of the cooling water after single screw extrusion is 40-50 ℃.
The wire diameter of the wire rod prepared by the invention is 1.75mm +/-0.03 mm, and the ovality is less than 0.05.
The PLA wire prepared by the invention can be widely applied to the field of 3D printing materials, including scenes such as articles for cultural relics and home decoration parts, and the interestingness and functionality of the 3D printing materials are expanded. The prepared wire is applied to an FDM printer for printing, the printing temperature is 200-230 ℃, the temperature of a bottom plate is 55-65 ℃, and the printing speed is 20-80mm/s.
Compared with the prior art, the invention has the following technical advantages:
1) Compared with simple mixing, melting and granulating of the essence, the van POSS-PLA has the advantages that the heat resistance and the dispersion uniformity of the essence in the processing process are greatly improved, and the long-acting fragrance-retaining effect of the material is really guaranteed.
2) In addition, the cage-shaped structure of POSS can adsorb temperature-sensitive toner, and the heat resistance and the dispersion uniformity of the temperature-sensitive toner in the processing process are improved, so that the 3D printing wire prepared from the material has a more stable reversible temperature change effect.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.
In each of the examples and comparative examples, the main raw material sources were as follows:
| raw material | Manufacturer(s) of |
| PLA(LX575)、PLA(LX175) | Doudaro Bien polylactic acid Co Ltd |
| Color changing powder | Shenzhen chameleon science and technology Limited |
| Calcium carbonate | SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd. |
| Hydrolysis resistant agent HY210 | RIANLON Corp. |
| Toughening agent Wacker2504 | Shanghai Kayin chemical Co Ltd |
| Stannous octoate | Sigma Aldrich trade company |
| Methylene dichloride | Sigma Aldrich trade company |
| Methanol | SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd. |
| Acrylate POSS | Xian Ji Yue Biotechnology Ltd |
| Vanillin | Sigma Aldrich trade company, inc |
| Tetrahydrofuran (THF) | SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd. |
| Ethanol | SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd. |
Other raw materials and reagents were obtained from commercial sources unless otherwise specified.
In each of the examples and comparative examples, the odor ratings of the PLA strands and the model were measured according to the standard GB/T35773-2017, with a sample size of 600cm 2 The test condition is that the glass is placed for 24 hours at 23 ℃ in the dark; the samples were rated from low to high odor, 0-4; tensile strength, tensile modulus and elongation at break were tested according to standard ISO 527-1; the flexural strength and flexural modulus are tested according to the standard ISO178: 2019; the heat distortion temperature is tested according to the standard ISO306: 2013; the total migration was tested according to standard GB 31604.1-2015.
The processing equipment is as follows: a twin-screw extruder, koilong, model ZSK 26Mc 18, length-diameter ratio of 52, screw diameter of 26cm; a film blowing machine, a model SCM 25, a length-diameter ratio of 30 and a screw diameter of 25cm, of Yangtze river machinery Co., ltd, zhang Jia gang City; an injection molding machine, claus Ma Fei, a model KM130-380CX, a length-diameter ratio of 20.2 and a screw diameter of 35mm; single screw extruder, haiyujia, model HRJSJ- Φ 45, screw diameter 45mm, die diameter 1.75mm.
The test equipment used was: a German Leifheit odor bottle with the specification of 1L; ZWICK-Z010TE universal tester; ZWICK-HIT25P pendulum bob impactor; CEAST-HV6M thermal deformation Vicat instrument; guangzhou West Tang Jidian-ERT-121B total migration and non-volatile matter constant weight apparatus.
EXAMPLE 1 preparation of essence modified acrylate POSS (vanPOSS)
100g of acrylate POSS was dissolved in 2L tetrahydrofuran and 1200g of vanillin was dissolved in 10L of anhydrous ethanol. Heating the tetrahydrofuran solution, slowly stirring and dripping the tetrahydrofuran solution into the ethanol solution to perform reflux reaction at the temperature of 50 ℃ for 2 hours; and then rapidly cooling to room temperature, adding a large amount of pure water to separate out a product, filtering, and repeatedly washing to obtain the essence modified acrylate POSS (vanPOSS).
(1) Preparation of essence-modified POSS-PLA graft Polymer (vanPOSS-PLA)
Placing 1000g of essence modified acrylate POSS and 1000g of PLA in a reaction tube, wherein the PLA is PLA prepared by a direct polycondensation method, the melt index is 13.7g/10min (190 ℃,2.16 kg), the molecular weight is 60000g/mol, continuously introducing nitrogen into a reaction device, heating until the mixture is completely molten, adding 150g of stannous octoate, and continuously reacting at high temperature for 20 hours at 150 ℃; and then transferring the mixture to an ice bath, completely dissolving the product by using dichloromethane, pouring a large amount of precooled methanol, centrifuging to obtain a precipitate, repeatedly washing, and then putting the precipitate into a drying oven for drying at the temperature of 40 ℃ for 10 hours to obtain the essence modified POSS-PLA graft polymer (van POSS-PLA).
(2) Essence modified POSS-PLA graft polymer (vanPOSS-PLA) and formula components in Table 1 are used as raw materials, and PLA wires are prepared according to the following method by referring to the raw material dosage in Table 1:
a) Firstly, respectively drying PLA and vanPOSS-PLA in an electrothermal blowing drying oven for 4 hours at the temperature of 80 ℃.
b) Mixing PLA, the temperature-changing toner, the mineral powder, the hydrolysis-resistant agent, the toughening agent and the van POSS-PLA uniformly in a high-speed mixer, wherein the mixing speed of the equipment is 90rpm, the mixing time is 7min, and the mixing temperature is 40 ℃.
c) After mixing, adding the main feed of a double-screw extruder, and carrying out melt extrusion. The extrusion conditions were: the rotating speed of the screw is 300rpm, and the temperature of the screw is set from the feed opening to the machine head in a segmented mode as follows: 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 195 ℃.
d) And (3) cooling the extruded material in a water tank of an extruder, pelletizing, and drying in a vacuum oven at 90 ℃ for 4 hours to obtain the modified PLA granules.
e) And adding the obtained PLA granules into a single-screw extruder, and performing melt extrusion. The extrusion conditions were: the rotating speed of the screw is 100rpm, the temperature of the screw is set to be 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃ and 190 ℃ from the feed opening to the machine head in sections, and the temperature of cooling water after single screw extrusion is 40 ℃, so that the PLA wire rod is prepared.
Example 2
(1) Preparation of essence modified acrylate POSS (vanPOSS)
100g of acrylate POSS was dissolved in 2L tetrahydrofuran and 1000g of vanillin was dissolved in 10L of anhydrous ethanol. Heating the tetrahydrofuran solution, slowly stirring and dripping the tetrahydrofuran solution into the ethanol solution to perform reflux reaction at the temperature of 65 ℃ for 3 hours; and then rapidly cooling to room temperature, adding a large amount of pure water to separate out a product, filtering, and repeatedly washing to obtain the essence modified acrylate POSS (vanPOSS).
(2) Preparation of essence-modified POSS-PLA graft Polymer (vanPOSS-PLA)
Placing 1000g of essence modified acrylate POSS and 1100g of PLA into a reaction tube, wherein the PLA is PLA prepared by a direct polycondensation method, the melt index is 13.7g/10min (190 ℃,2.16 kg), the molecular weight is 60000g/mol, continuously introducing nitrogen into a reaction device, heating until the mixture is completely melted, adding 100g of stannous octoate, and continuously reacting at a high temperature of 160 ℃ for 25 hours; and then transferring the solution to an ice bath, completely dissolving the product by using dichloromethane, pouring a large amount of precooled methanol, centrifuging to obtain a precipitate, repeatedly washing, and then putting the precipitate into an oven to dry at the temperature of 50 ℃ for 15 hours to obtain the essence modified POSS-PLA graft polymer (vanPOSS-PLA).
(3) Essence modified POSS-PLA graft polymer (vanPOSS-PLA) and formula components in Table 1 are used as raw materials, and PLA wires are prepared according to the following method by referring to the raw material dosage in Table 1:
a) Firstly, respectively drying PLA and vanPOSS-PLA in an electrothermal blowing drying oven for 4 hours at the temperature of 80 ℃.
b) Uniformly mixing PLA, thermochromic powder, mineral powder, an anti-hydrolysis agent, a toughening agent and the van POSS-PLA in a high-speed mixer at the mixing speed of 90rpm for 7min at the mixing temperature of 40 ℃.
c) After mixing, adding the main feed of a double-screw extruder, and carrying out melt extrusion. The extrusion conditions were: the rotating speed of the screw is 400rpm, and the temperature of the screw is set from the feed opening to the machine head in a segmented mode as follows: 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 195 ℃ and 200 ℃.
d) And (3) cooling the extruded material in a water tank of an extruder, pelletizing, and drying in a vacuum oven at 90 ℃ for 4 hours to obtain modified PLA granules.
e) Adding the obtained PLA granules into a single-screw extruder, and carrying out melt extrusion. The extrusion conditions were: the screw rotating speed is 150rpm, the screw temperature is set to be 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃ and 195 ℃ from the feed opening to the machine head in sections, and the cooling water temperature is 45 ℃ after single screw extrusion, so that the PLA wire rod is prepared.
Example 3
(1) Preparation of essence modified acrylate POSS (vanPOSS)
100g of acrylate POSS was dissolved in 2L tetrahydrofuran and 1500g of vanillin was dissolved in 10L of anhydrous ethanol. Heating the tetrahydrofuran solution, slowly stirring and dripping the tetrahydrofuran solution into the ethanol solution to carry out reflux reaction at the temperature of 70 ℃ for 4 hours; and then rapidly cooling to room temperature, adding a large amount of pure water to separate out a product, filtering, and repeatedly washing to obtain the essence modified acrylate POSS (vanPOSS).
(2) Preparation of essence-modified POSS-PLA graft Polymer (vanPOSS-PLA)
Placing 1000g of essence modified acrylate POSS and 1200g of PLA in a reaction tube, wherein the PLA is PLA prepared by a direct polycondensation method, the melt index is 13.7g/10min (190 ℃,2.16 kg), the molecular weight is 60000g/mol, continuously introducing nitrogen into a reaction device, heating until the mixture is completely melted, adding 200g of stannous octoate, and continuously reacting at a high temperature of 170 ℃ for 30 hours; and then transferring the solution to an ice bath, completely dissolving the product by using dichloromethane, pouring a large amount of precooled methanol, centrifuging to obtain a precipitate, repeatedly washing, and then putting the precipitate into an oven to dry at the temperature of 60 ℃ for 20 hours to obtain the essence modified POSS-PLA graft polymer (vanPOSS-PLA).
(3) Essence modified POSS-PLA graft polymer (vanPOSS-PLA) and formula components in Table 1 are used as raw materials, and PLA wires are prepared according to the following method by referring to the raw material dosage in Table 1:
a) Firstly, respectively drying PLA and vanPOSS-PLA in an electrothermal blowing drying oven for 4 hours at the temperature of 80 ℃.
b) Uniformly mixing PLA, thermochromic powder, mineral powder, an anti-hydrolysis agent, a toughening agent and the van POSS-PLA in a high-speed mixer at the mixing speed of 90rpm for 7min at the mixing temperature of 40 ℃.
c) After mixing, adding the main feed of a double-screw extruder, and carrying out melt extrusion. The extrusion conditions were: the screw rotating speed is 500rpm, and the screw temperature is set from the feed opening to the machine head in a segmented mode as follows: 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃ and 205 ℃.
d) And (3) cooling the extruded material in a water tank of an extruder, pelletizing, and drying in a vacuum oven at 90 ℃ for 4 hours to obtain the modified PLA granules.
e) Adding the obtained PLA granules into a single-screw extruder, and carrying out melt extrusion. The extrusion conditions were: the screw rotating speed is 150rpm, the screw temperature is set to be 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 190 ℃, 195 ℃ and 200 ℃ from the feed opening to the machine head in sections, and the cooling water temperature is 50 ℃ after single screw extrusion, so that the PLA wire rod is prepared.
Comparative example 1
A PLA strand was prepared as in example 1, using commercially available vanillin as a starting material, without modification, except that the type of vanillin in table 1 was different.
Comparative example 2
A PLA wire was prepared by the method of example 1 using commercially available acrylate POSS as a raw material without modification, except that the acrylate POSS in table 1 was different in kind.
Comparative example 3
The PLA wire was prepared by the method of example 1 using commercially available vanillin and acrylate POSS as raw materials without modification, except that the types of vanillin and acrylate POSS in table 1 were different.
Comparative example 4
A PLA wire was prepared as in example 1 without the addition of vanillin and acrylate POSS, except that vanillin and acrylate POSS were not added.
Printing the PLA wire rods obtained in the examples 1-3 and the comparative examples 1-4 in an FDM printer, setting the temperature of a nozzle to be 210 ℃, the temperature of a bottom plate to be 60 ℃, the printing speed to be 60mm/s, printing the PLA wire rods into cuboid plates with the thickness of 2mm, and testing the odor grade; and (3) injection molding to obtain a standard sample strip, testing mechanical property and temperature resistance, blow molding to obtain a film sheet, and testing the surface migration and precipitation property, wherein the test results are shown in Table 2.
TABLE 1 raw materials and amounts (Kg) used in examples 1-3 (S1-S3) and comparative examples 1-4 (D1-D4)
| Raw material | S1 | S2 | S3 | D1 | D2 | D3 | D4 |
| LX175 | 35 | - | 60 | 90 | 90 | 90 | 95 |
| LX575 | - | 40 | - | - | - | - | - |
| Color changing powder | 1 | 1.5 | 2 | 1 | 1 | 1 | 1 |
| KL5 calcium carbonate | 2 | - | - | 2 | 2 | 2 | 2 |
| CC2500 calcium carbonate | - | 3.5 | 5 | - | - | - | - |
| Hydrolysis resistant agent HY210 | 1 | 0.5 | 1 | 1 | 1 | 1 | 1 |
| Toughening agent Wacker2504 | 1 | 0.5 | 2 | 1 | 1 | 1 | 1 |
| vanPOSS-PLA | 60 | 54 | 30 | - | - | - | - |
| Acrylate POSS | - | - | - | - | 5 | 2.5 | - |
| Vanillin | - | - | - | 5 | - | 2.5 | - |
TABLE 2 Performance test results for PLA wire-printed samples of examples 1-3 (S1-S3) and comparative examples 1-4 (D1-D4)
As can be seen from comparative examples 1-4 and example 1, in the modification process of PLA, the flavor is directly added to prepare the wire rod, and the 3D printed model has obviously lighter flavor and poor flavor durability. The invention firstly prepares essence modified acrylic ester POSS (vanPOSS), then prepares essence modified POSS-PLA graft polymer (vanPOSS-PLA), and finally prepares long-acting fragrance-remaining temperature-sensitive color-changing PLA wire rod. On one hand, the van POSS-PLA introduces essence molecules into a polymer molecular chain, compared with simple essence mixing, melting and granulating, the heat resistance and the dispersion uniformity of the essence in the processing process are greatly improved, and the long-acting fragrance-retaining effect of the material is really ensured; on the other hand, the cage-shaped structure of the POSS can adsorb the temperature-sensitive toner, and the heat resistance and the dispersion uniformity of the temperature-sensitive toner in the processing process are improved, so that the 3D printing wire prepared from the material has a long-acting fragrance-retaining effect and a more stable reversible temperature change effect. The prepared PLA wire for 3D printing can be widely applied to scenes such as articles for cultural wound, home decoration parts and the like, and the interestingness and functionality of the 3D printing material are expanded.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.
Claims (14)
1. The long-acting odor-retaining type PLA wire rod is applied to the field of 3D printing and is characterized in that the PLA wire rod is prepared from the following components in percentage by weight:
s1, PLA,20% -80%, preferably 35% -60%;
s2, 0% -4% of temperature-changing toner, preferably 0.5% -2%;
s3, 1% -15% of mineral powder, preferably 2% -5%;
s4, hydrolysis resistant agent, 0.05% -2%, preferably 0.5% -1%;
s5, a toughening agent, 0.05% -3%, preferably 0.5% -2%;
s6, 10-70% of essence modified POSS-PLA graft polymer, preferably 30-60%.
2. The PLA strand of claim 1, wherein the perfume modified POSS-PLA graft polymer is prepared by including:
s7, essence modified acrylate POSS;
s8 and PLA, the mass of which is 0.8-1.5 times of that of S7, preferably 1-1.2 times;
s9 and stannous octoate, the mass of which is 5-30 percent of that of S7, preferably 10-20 percent.
3. The PLA wire of claim 2, wherein the perfume modified acrylate POSS is prepared by including:
s12, acrylate POSS;
s13 and essence, the mass of which is 8-20 times of that of S12, preferably 10-15 times.
4. PLA wire according to any of the claims 1-3, wherein the PLA is one or more of a ring opening polymerization PLA and a direct polycondensation PLA, preferably the PLA has a melt index of 1-30g/10min (190 ℃,2.16 kg) and a molecular weight of 40000-100000g/mol.
5. The PLA wire according to any one of claims 1 to 4, wherein the thermochromic powder is one or more of nickel chloride hexamethylenetetramine hydrate, copper sulfate hexamethylenetetramine hydrate, cobalt sulfate hexamethylenetetramine hydrate, phenanthroline europium acrylate complex, crystal violet lactone, bisphenol A.
6. The PLA wire of any one of claims 1 to 5 wherein the mineral powder is one or more of talc, calcium carbonate, wollastonite, and mica; and/or the presence of a gas in the atmosphere,
the hydrolysis resistant agent is one or more of polymeric type and monomeric type, preferably one or more of HY210, DSA10A and K-1; and/or the presence of a gas in the gas,
the toughening agent is one or more of AX8900, wacker2504 and Wacker 2505.
7. A method of making the PLA wire of any one of claims 1-6, comprising the steps of:
mixing PLA, a temperature-changing toner, mineral powder, an anti-hydrolysis agent, a toughening agent and an essence modified POSS-PLA graft polymer, adding the mixture into a double-screw extruder for melt extrusion, cooling, granulating and drying to obtain modified PLA particles, adding the modified PLA particles into a single-screw extruder for melt extrusion, and cooling to obtain the PLA wire.
8. The preparation method of claim 7, wherein the preparation method of the perfume modified POSS-PLA graft polymer comprises the following steps: placing the essence modified POSS and PLA in a reaction tube, heating and melting in an inert atmosphere, adding stannous octoate for reaction, transferring the reaction product to an ice bath after the reaction is finished, pouring methanol after the product is completely dissolved by dichloromethane, centrifuging to obtain a precipitate, repeatedly washing and drying to obtain the essence modified POSS-PLA graft polymer.
9. The preparation method according to claim 8, wherein the PLA mass is 0.8-1.5 times, preferably 1-1.2 times of the essence modified acrylate POSS; and/or the mass of the stannous octoate is 5% -30% of that of the essence modified acrylate POSS, preferably 10% -20%; and/or the reaction temperature is 150-170 ℃ and the reaction time is 20-30h; and/or, drying conditions: the temperature is 40-60 deg.C, and the time is 10-20h.
10. The method of any one of claims 8-9, wherein the perfume-modified acrylate POSS is prepared by a method comprising the steps of: dissolving acrylate POSS in tetrahydrofuran, dissolving essence in absolute ethyl alcohol, heating the tetrahydrofuran solution, slowly stirring and dripping the ethanol solution into the tetrahydrofuran solution to perform reflux reaction, then cooling the tetrahydrofuran solution, adding a large amount of water to separate out a product, filtering the product, and repeatedly washing the product to obtain the essence modified acrylate POSS.
11. The process according to claim 10, wherein the reaction temperature is 50 to 80 ℃ and the reaction time is 2 to 5 hours; and/or the essence mass is 8-20 times, preferably 10-15 times that of the acrylate POSS.
12. The preparation method according to any one of claims 7 to 11, wherein a high speed mixer is used for mixing, the rotating speed is 20-100 rpm, the temperature is 20-50 ℃, and the mixing time is 3-10 min; and/or (b) a plurality of,
the screw temperature of the double-screw extruder is 150-210 ℃, and the rotating speed is 100-800rpm; and or (b) a,
the screw temperature of the single-screw extruder is 160-200 ℃, and the rotating speed is 100-200rpm; and/or the presence of a gas in the gas,
the cooling temperature after single screw extrusion is 40-50 ℃.
13. Use of a PLA wire according to any one of claims 1-6 or a PLA wire made by the manufacturing method of any one of claims 7-12 in the field of 3D printing.
14. Use according to claim 13, wherein the wire produced is used for printing in FDM printers at a temperature of 200-230 ℃, a soleplate temperature of 55-65 ℃ and a printing speed of 20-80mm/s.
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