CN115386209B - Long-acting fragrance-retaining PLA wire applied to 3D printing field and preparation method and application thereof - Google Patents
Long-acting fragrance-retaining PLA wire applied to 3D printing field and preparation method and application thereof Download PDFInfo
- Publication number
- CN115386209B CN115386209B CN202210988116.5A CN202210988116A CN115386209B CN 115386209 B CN115386209 B CN 115386209B CN 202210988116 A CN202210988116 A CN 202210988116A CN 115386209 B CN115386209 B CN 115386209B
- Authority
- CN
- China
- Prior art keywords
- pla
- essence
- poss
- wire
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000010146 3D printing Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000000843 powder Substances 0.000 claims abstract description 32
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000012745 toughening agent Substances 0.000 claims abstract description 14
- 230000000655 anti-hydrolysis Effects 0.000 claims abstract description 12
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 12
- 239000011707 mineral Substances 0.000 claims abstract description 12
- 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 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000001125 extrusion Methods 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 16
- -1 modified acrylic ester Chemical class 0.000 claims description 16
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 238000007639 printing Methods 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 14
- 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 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 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
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 7
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 7
- 238000006068 polycondensation reaction Methods 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 claims description 5
- 239000002304 perfume Substances 0.000 claims description 4
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229920004482 WACKER® Polymers 0.000 claims description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 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
- 230000035484 reaction time Effects 0.000 claims 2
- 229910052693 Europium Inorganic materials 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims 1
- 239000003112 inhibitor Substances 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 25
- 239000003205 fragrance Substances 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 15
- 239000002994 raw material Substances 0.000 abstract description 14
- 238000012545 processing Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 12
- 239000006185 dispersion Substances 0.000 abstract description 8
- 229920000642 polymer Polymers 0.000 abstract description 4
- 238000005034 decoration Methods 0.000 abstract description 3
- 229920000747 poly(lactic acid) Polymers 0.000 description 123
- 239000004626 polylactic acid Substances 0.000 description 122
- 239000000243 solution Substances 0.000 description 13
- 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
- 230000008859 change Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- 239000000498 cooling water Substances 0.000 description 4
- 229960004011 methenamine Drugs 0.000 description 4
- 238000007792 addition Methods 0.000 description 3
- 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 description 3
- 238000007664 blowing Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 230000005923 long-lasting effect Effects 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000003094 microcapsule Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 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
- 230000032683 aging Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- DEZRYPDIMOWBDS-UHFFFAOYSA-N dcm dichloromethane Chemical compound ClCCl.ClCCl DEZRYPDIMOWBDS-UHFFFAOYSA-N 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
- 238000005516 engineering process Methods 0.000 description 1
- VXDRQQWJEDPJLW-UHFFFAOYSA-N europium prop-2-enoic acid Chemical compound [Eu].C(C=C)(=O)O VXDRQQWJEDPJLW-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010096 film blowing Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229930002839 ionone Natural products 0.000 description 1
- 150000002499 ionone derivatives Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
-
- 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
-
- 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
-
- 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
Abstract
The invention provides a long-acting fragrance-retaining PLA wire applicable to the field of 3D printing and a preparation method thereof, wherein the PLA wire raw material comprises PLA, mineral powder, optional thermochromic powder, a toughening agent, an anti-hydrolysis agent and an essence modified POSS-PLA grafted polymer (vanPOSS-PLA). The vanPOSS-PLA introduces essence molecules into a polymer molecular chain, so that 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 truly ensured. The prepared PLA wire for 3D printing can be widely applied to scenes such as literature articles, home decoration parts and the like, and the interestingness and the 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-retaining PLA wire applied to the field of 3D printing and a preparation method thereof.
Background
3D printing (especially the material extrusion type 3D printing technology represented by FDM) has the advantages of low cost, simple operation and no toxic or harmful generation, and is widely applied to the industrial fields of industrial design, medical protection, automobile assembly, education, entertainment and the like.
Typical materials for FDM printing are PLA, ABS, PETG. The PLA has wide sources, low printing temperature, good biodegradability, good printing and forming effects, stable chemical stability and no reaction with common toner and filler, is widely applied, and gradually accelerates the daily life of people. Because of the limited mechanical properties of PLA, it is difficult to apply it to industrial structural parts in large quantities, and more to print some living appliances, ornaments, teaching demonstration products, artistic structures, etc. With the expansion of the market, PLA with different special functions or characteristics is gradually developed and applied, such as fragrance retention, temperature-sensitive color change and the like, and the interestingness and the functionality of the 3D printing material are more and more rich.
CN108912632a and CN114058166a respectively disclose a PLA wire rod with fragrance applied in the field of 3D printing and a preparation method thereof, wherein fragrance is realized by directly adding a fragrance agent. However, in practice, the 3D printing wire needs to be subjected to twin-screw granulation and single-screw extrusion, and needs to be melted again during printing, so that the final printing finished product model has no fragrance. The material is analyzed by TGA, the temperature is increased to 220 ℃ for multiple times, three processing processes are simulated, and as a result, more than 90% of added essence is decomposed after the second temperature increase, and the retention rate of residual essence is extremely low after the third temperature increase.
CN113136094a discloses a reversible thermochromic polylactic acid material and a preparation method thereof, wherein the thermochromic is realized by adding thermochromic powder microcapsules. The method reduces the dosage of thermochromic powder, and increases the difficulty of dispersing during processing. In addition, the compatilizer gradually ages and loses efficacy in the use process of the material, so that more precipitate exists on the surface of the material, and the appearance is poor.
Therefore, the method for preparing the 3D printing PLA wire rod with the temperature change and fragrance retaining functions still has great room for improvement and innovation.
Disclosure of Invention
The invention aims to provide a long-acting fragrance-retaining PLA wire applied to the field of 3D printing and a preparation method thereof. The long-acting fragrance-retaining/temperature-sensing color-changing PLA wire is prepared by preparing an essence modified POSS-PLA grafted polymer (vanPOSS-PLA), mixing the essence modified POSS-PLA grafted polymer with PLA, optional thermochromic powder and other auxiliary agents, melting and granulating. On one hand, the vanPOSS-PLA introduces essence molecules into a polymer molecular chain, and 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 truly 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 aim of the invention, the invention adopts the following technical scheme:
the long-acting fragrance-retaining PLA wire applied to the 3D printing field is prepared from the following components in percentage by weight:
s1, PLA,20% -80%, preferably 35% -60%;
s2, thermochromic powder, wherein the content of the thermochromic powder is 0-4%, preferably 0.5-2%;
s3, mineral powder, 1% -15%, preferably 2% -5%;
s4, an anti-hydrolysis agent, 0.05% -2%, preferably 0.5% -1%;
s5, a toughening agent, 0.05% -3%, preferably 0.5% -1.5%;
s6, essence modified POSS-PLA grafted 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 acrylic ester POSS (vanPOSS);
s8 and PLA are used in an amount of 0.8 to 1.5 times, preferably 1 to 1.2 times that of S7;
s9 and stannous octoate are used in an amount of 5% -30%, preferably 10% -20% of S7.
As a preferred preparation method, essence modified acrylic ester POSS and PLA are placed in a reaction tube, nitrogen is continuously introduced into a reaction device, after the mixture is heated to be 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 methylene dichloride, a large amount of precooled methanol is poured into the mixture, a precipitate is obtained after centrifugation, and the mixture is placed in an oven for drying after repeated washing, thus obtaining the essence modified POSS-PLA grafted polymer (vanPOSS-PLA).
Preferably, the reaction conditions are: the temperature is 150-170 ℃ and the time is 20-30h; drying conditions: the temperature is 40-60 ℃ and the time is 10-20h.
Wherein the perfume modified acrylate POSS (vanPOSS) is prepared by comprising the following components:
s12, acrylate POSS;
s13, essence, the dosage of which is 8-20 times, preferably 10-15 times of that of S12. The essence can be selected from natural or artificial essence such as vanillin, ionone, and jasmine essence.
As a preferred method of preparation, the acrylate POSS is dissolved in tetrahydrofuran and the perfume is dissolved in absolute ethanol. And heating the tetrahydrofuran solution, slowly stirring and dripping the ethanol solution, and carrying out reflux reaction. And then cooling to room temperature quickly, adding a large amount of pure water to precipitate 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, PLA wires with slight fragrance and temperature-sensitive color change function can be prepared by directly adding essence and thermochromic powder microcapsules, but the two defects are existed: on one hand, after the model is printed, the fragrance rate is extremely low, and the essence is seriously decomposed in the multiple processing processes; on the other hand, the temperature-sensitive color change uniformity is poor, and the appearance of the material is obviously deteriorated along with the prolonged service time, mainly due to the small use amount of the temperature-sensitive color change and the aging failure of the compatilizer. According to the invention, the essence modified POSS-PLA grafted polymer (vanPOSS-PLA) is prepared, 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 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 by 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 the 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.
In the invention, the thermochromic powder is one or more of nickel chloride hexamethylene tetramine hydrate, copper sulfate hexamethylene tetramine hydrate, cobalt sulfate hexamethylene tetramine hydrate, phenanthroline, acrylic acid europium complex, crystal violet lactone and bisphenol A, preferably one or more of nickel chloride hexamethylene tetramine 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, preferably calcium carbonate.
In the invention, the anti-hydrolysis agent is one or more of polymerization type and monomer 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 type temperature-sensitive color-changing PLA wire. The invention prepares essence modified acrylic ester POSS (vanPOSS) through co-thermal reflux and other process treatments, then adds PLA raw material and catalyst, prepares essence modified POSS-PLA grafted polymer (vanPOSS-PLA) through vacuum mixed melting and other process treatments, then mixes and melts the essence modified POSS-PLA grafted polymer with PLA, thermochromic powder and other auxiliary agents for granulation, and finally prepares the long-acting fragrance-retaining type thermochromic PLA wire.
A method of making the long-lasting fragrance-retaining temperature-sensitive color-changing PLA wire, the method comprising the steps of:
and mixing PLA, thermochromic powder, mineral powder, an anti-hydrolysis agent, a toughening agent and vanPOSS-PLA, adding into a double-screw extruder for melt extrusion, cooling, granulating, drying to obtain modified PLA particles, and adding into a single-screw extruder for melt extrusion to obtain the PLA wire.
As a preferred method, a method for preparing the long-lasting fragrance-retaining type temperature-sensitive color-changing PLA wire, the method comprising the steps of:
A. the acrylate POSS is dissolved in tetrahydrofuran, and the essence is dissolved in absolute ethyl alcohol. And heating the tetrahydrofuran solution, slowly stirring and dripping the ethanol solution, and carrying out reflux reaction. And then cooling to room temperature quickly, adding a large amount of pure water to precipitate a product, filtering and repeatedly washing to obtain the essence modified acrylate POSS (vanPOSS).
B. Placing essence modified acrylic ester POSS and PLA in a reaction tube, continuously introducing nitrogen into a reaction device, heating until the mixture is completely melted, adding stannous octoate, continuously carrying out reflux reaction at high temperature, transferring into an ice bath, completely dissolving a product by using methylene dichloride, pouring a large amount of precooled methanol, centrifuging to obtain a precipitate, repeatedly washing, and then placing into an oven for drying to obtain the essence modified POSS-PLA grafted polymer (vanPOSS-PLA).
C. And mixing PLA, thermochromic powder, mineral powder, an anti-hydrolysis agent, a toughening agent and vanPOSS-PLA, adding into a double-screw extruder for melt extrusion, cooling, granulating, drying to obtain modified PLA particles, and adding into a single-screw extruder for melt extrusion to obtain the PLA wire.
In the method of the invention, the reflux reaction condition of the step A is as follows: the temperature is 50-80 ℃, and the heating time is 2-5h.
In the method of the invention, the reflux reaction condition of the step B is as follows: the temperature is 150-170 ℃ and the time is 20-30h; drying conditions: the temperature is 40-60 ℃ and the time is 10-20h.
In the invention, in the step C, a high-speed mixer is adopted for mixing, 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 twin-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 cooling water after single screw extrusion is 40-50 ℃.
The wire diameter of the wire rod prepared by the invention is 1.75mm plus or minus 0.03mm, and the ellipticity is less than 0.05.
The PLA wire prepared by the method can be widely applied to the field of 3D printing materials, including scenes such as literature articles and home decoration parts, and the interestingness and the 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) The vanPOSS-PLA introduces essence molecules into a polymer molecular chain, so that 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 truly ensured.
2) In addition, the cage-shaped structure of the POSS can absorb 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 more stable reversible temperature change effect.
Detailed Description
The invention will now be further illustrated by means of specific examples which are given solely by way of illustration of the invention and do not limit the scope thereof.
In each of the examples and comparative examples, the main raw material sources were as follows:
| raw materials | Manufacturer' s |
| PLA(LX575)、PLA(LX175) | Tandal Bien polylactic acid Co., ltd |
| Thermochromic powder | Shenzhen color-changing technology Co., ltd |
| Calcium carbonate | SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd. |
| Hydrolysis resistance agent HY210 | RIANLON Corp. |
| Toughening agent Wacker2504 | Shanghai Kaiyin chemical Co., ltd |
| Stannous octoate | Sigma Aldrich trade Co.Ltd |
| Dichloromethane (dichloromethane) | Sigma Aldrich trade Co.Ltd |
| Methanol | SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd. |
| Acrylic ester POSS | Siemens Ji Yue Biotech Co.Ltd |
| Vanillin | Sigma Aldrich trade Co.Ltd |
| Tetrahydrofuran (THF) | SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd. |
| Ethanol | SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd. |
Other materials and reagents were obtained commercially, unless otherwise specified.
In each of the examples and comparative examples, the odor rating of the PLA wire and the model was as followsThe sample size was 600cm according to the standard GB/T35773-2017 test 2 The test conditions are that the test is carried out for 24 hours in the dark at the temperature of 23 ℃; samples were rated from low to high by odor, from 0 to 4; tensile strength, tensile modulus and elongation at break were tested according to standard ISO 527-1:2012; flexural Strength and flexural modulus were measured according to standard ISO 178:2019; the heat distortion temperature is tested according to standard ISO 306:2013; the total migration was tested according to standard GB 31604.1-2015.
The processing equipment used is as follows: a twin-screw extruder, keplong, model ZSK 26Mc 18, length-diameter ratio of 52, screw diameter of 26cm; a film blowing machine, model SCM 25, length-diameter ratio of 30 and screw diameter of 25cm; injection molding machine, claus Ma Fei, model KM130-380CX, length-diameter ratio 20.2 and screw diameter 35mm; a single screw extruder, haijiji, model HRJSJ- Φ45, screw diameter 45mm, die diameter 1.75mm.
The test equipment used was: leiffeit odor bottle in Germany, specification is 1L; ZWICK-Z010TE universal testing machine; zWICK-HIT25P pendulum impactor; CEAST-HV6M thermal deformation Vicat instrument; guangzhou western Tang Jidian-ERT-121B total migration and nonvolatile constant weight instrument.
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 absolute ethanol. Heating the tetrahydrofuran solution, slowly stirring and dripping the tetrahydrofuran solution into the ethanol solution, and carrying out reflux reaction at the temperature of 50 ℃ for 2 hours; and then cooling to room temperature quickly, adding a large amount of pure water to precipitate 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 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 150g of stannous octoate, and continuously reacting at a high temperature of 150 ℃ for 20h; and transferring the mixture into 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 for drying at the temperature of 40 ℃ for 10 hours to obtain the essence modified POSS-PLA grafted polymer (vanPOSS-PLA).
(2) The essence modified POSS-PLA graft polymer (vanPOSS-PLA) and the formula components in table 1 are taken 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, PLA and vanPOSS-PLA are respectively dried for 4 hours at 80 ℃ in an electrothermal blowing drying oven.
b) Mixing PLA, thermochromic powder, mineral powder, an anti-hydrolysis agent, a toughening agent and the vanPOSS-PLA uniformly in a high-speed mixer at a device mixing speed of 90rpm for 7min at a mixing temperature of 40 ℃.
c) After mixing, adding main feed of a double-screw extruder, and carrying out melt extrusion. The extrusion conditions were: the screw rotation speed is 300rpm, and the screw temperature is set as from the feed opening to the machine head section: 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 195 ℃.
d) And cooling the extruded material in an extruder water tank, granulating, and drying in a vacuum oven at 90 ℃ for 4 hours to obtain modified PLA granules.
e) The obtained PLA pellets were fed into a single screw extruder and melt extruded. The extrusion conditions were: the PLA wire was produced by setting the screw speed at 100rpm, the screw temperature from the feed opening to the head section at 160℃at 165℃at 170℃at 175℃at 180℃at 185℃at 190℃and the cooling water temperature after single screw extrusion at 40 ℃.
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 absolute ethanol. Heating the tetrahydrofuran solution, slowly stirring and dripping the tetrahydrofuran solution into the ethanol solution, and carrying out reflux reaction at 65 ℃ for 3 hours; and then cooling to room temperature quickly, adding a large amount of pure water to precipitate 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 in a reaction tube, wherein the PLA is PLA 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 25h; and transferring the mixture into 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 placing the precipitate into an oven for drying at 50 ℃ for 15 hours to obtain the essence modified POSS-PLA grafted polymer (vanPOSS-PLA).
(3) The essence modified POSS-PLA graft polymer (vanPOSS-PLA) and the formula components in table 1 are taken 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, PLA and vanPOSS-PLA are respectively dried for 4 hours at 80 ℃ in an electrothermal blowing drying oven.
b) Mixing PLA, thermochromic powder, mineral powder, an anti-hydrolysis agent, a toughening agent and the vanPOSS-PLA uniformly in a high-speed mixer at a device mixing speed of 90rpm for 7min at a mixing temperature of 40 ℃.
c) After mixing, adding main feed of a double-screw extruder, and carrying out melt extrusion. The extrusion conditions were: the screw rotation speed is 400rpm, and the screw temperature is set as from the feed opening to the machine head section: 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 195 ℃, 200 ℃.
d) And cooling the extruded material in an extruder water tank, granulating, and drying in a vacuum oven at 90 ℃ for 4 hours to obtain modified PLA granules.
e) The obtained PLA pellets were fed into a single screw extruder and melt extruded. The extrusion conditions were: the PLA wire was produced by setting the screw speed at 150rpm, the screw temperature from the feed opening to the head section at 160℃at 165℃at 170℃at 175℃at 180℃at 185℃at 190℃at 195℃and the cooling water temperature after single screw extrusion at 45 ℃.
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 absolute ethanol. Heating the tetrahydrofuran solution, slowly stirring and dripping the tetrahydrofuran solution into the ethanol solution, and carrying out reflux reaction at the temperature of 70 ℃ for 4 hours; and then cooling to room temperature quickly, adding a large amount of pure water to precipitate 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)
1000g of essence modified acrylate POSS and 1200g of PLA are placed in a reaction tube, the PLA is PLA by a direct polycondensation method, the melt index is 13.7g/10min (190 ℃,2.16 kg), the molecular weight is 60000g/mol, nitrogen is continuously introduced into a reaction device, after the mixture is heated to be completely melted, 200g of stannous octoate is added, and the mixture is continuously reacted at a high temperature of 170 ℃ for 30 hours; and transferring the mixture into 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 placing the precipitate into an oven for drying at the temperature of 60 ℃ for 20 hours to obtain the essence modified POSS-PLA grafted polymer (vanPOSS-PLA).
(3) The essence modified POSS-PLA graft polymer (vanPOSS-PLA) and the formula components in table 1 are taken 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, PLA and vanPOSS-PLA are respectively dried for 4 hours at 80 ℃ in an electrothermal blowing drying oven.
b) Mixing PLA, thermochromic powder, mineral powder, an anti-hydrolysis agent, a toughening agent and the vanPOSS-PLA uniformly in a high-speed mixer at a device mixing speed of 90rpm for 7min at a mixing temperature of 40 ℃.
c) After mixing, adding main feed of a double-screw extruder, and carrying out melt extrusion. The extrusion conditions were: the screw rotation speed is 500rpm, and the screw temperature is set as from the feed opening to the machine head section: 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃.
d) And cooling the extruded material in an extruder water tank, granulating, and drying in a vacuum oven at 90 ℃ for 4 hours to obtain modified PLA granules.
e) The obtained PLA pellets were fed into a single screw extruder and melt extruded. The extrusion conditions were: the PLA wire was produced by setting the screw speed at 150rpm, the screw temperature from the feed opening to the head section at 160℃at 165℃at 170℃at 175℃at 180℃at 190℃at 195℃at 200℃and the cooling water temperature after single screw extrusion at 50 ℃.
Comparative example 1
PLA wire rods were prepared as in example 1, using commercially available vanillin as a raw material, without modification, except that the vanillin species in table 1 were different.
Comparative example 2
PLA wires were produced, without modification, using commercially available acrylic acid ester POSS as a starting material, in the manner described in example 1, except that the acrylic acid ester POSS species in Table 1 were different.
Comparative example 3
PLA wire was produced without modification from commercially available vanillin and acrylate POSS as raw materials in the manner of example 1, except that the vanillin and acrylate POSS species in Table 1 were different.
Comparative example 4
PLA wire was produced as in example 1 without the addition of vanillin and acrylate POSS, except that vanillin and acrylate POSS were not added.
Printing the PLA wires obtained in examples 1-3 and comparative examples 1-4 in an FDM printer, setting the nozzle temperature to 210 ℃, the bottom plate temperature to 60 ℃, the printing speed to 60mm/s, printing into a cuboid plate with the thickness of 2mm, and testing the odor grade; standard bars were injection molded, mechanical properties and temperature resistance were tested, film sheets were blow molded, surface migration and precipitation properties were tested, and test results are shown in table 2.
TABLE 1 raw materials and amounts (Kg) in examples 1 to 3 (S1 to S3) and comparative examples 1 to 4 (D1 to D4)
| Raw materials | S1 | S2 | S3 | D1 | D2 | D3 | D4 |
| LX175 | 35 | - | 60 | 90 | 90 | 90 | 95 |
| LX575 | - | 40 | - | - | - | - | - |
| Thermochromic powder | 1 | 1.5 | 2 | 1 | 1 | 1 | 1 |
| KL5 calcium carbonate | 2 | - | - | 2 | 2 | 2 | 2 |
| CC2500 calcium carbonate | - | 3.5 | 5 | - | - | - | - |
| Hydrolysis resistance 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 | - | - | - | - |
| Acrylic ester POSS | - | - | - | - | 5 | 2.5 | - |
| Vanillin | - | - | - | 5 | - | 2.5 | - |
TABLE 2 test results of the print sample properties of PLA wire 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, the 3D printed model was significantly lighter in flavor and poor in flavor persistence by directly adding the essence to prepare the strands during the modification of PLA. According to the invention, the essence modified acrylic ester POSS (vanPOSS) is firstly prepared, then the essence modified POSS-PLA grafted polymer (vanPOSS-PLA) is prepared, and finally the long-acting fragrance-retaining type temperature-sensitive color-changing PLA wire is prepared. On one hand, the vanPOSS-PLA introduces essence molecules into a polymer molecular chain, and 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 truly 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 literature articles, home decoration parts and the like, and the interestingness and the functionality of the 3D printing material are expanded.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.
Claims (18)
1. The long-acting fragrance-retaining PLA wire applied to the 3D printing field is characterized in that the PLA wire is prepared from the following components in percentage by weight:
S1、PLA，20％-80％；
s2, 0% -4% of thermochromic powder;
s3, mineral powder, 1% -15%;
s4, 0.05% -2% of an anti-hydrolysis agent;
s5, 0.05% -3% of a toughening agent;
s6, an essence modified POSS-PLA grafted polymer, 10% -70%;
the essence modified POSS-PLA grafted polymer is prepared by comprising the following components:
s7, essence modified acrylic ester POSS;
s8, PLA, the mass of which is 0.8-1.5 times of that of S7;
s9, stannous octoate, wherein the mass of the stannous octoate is 5% -30% of that of the S7;
the essence modified acrylic ester POSS is prepared from the following components:
s12, acrylate POSS;
s13, essence, wherein the mass of the essence is 8-20 times of that of the S12.
2. PLA wire as claimed in claim 1, characterized in that it is made by a composition comprising the following weight percentages:
S1、PLA，35％-60％；
s2, 0.5% -2% of thermochromic powder;
s3, mineral powder, 2% -5%;
s4, 0.5% -1% of an anti-hydrolysis agent;
s5, 0.5% -2% of a toughening agent;
s6, an essence modified POSS-PLA grafted polymer, 30% -60%;
the essence modified POSS-PLA grafted polymer is prepared by comprising the following components:
s7, essence modified acrylic ester POSS;
s8, PLA, the mass of which is 1-1.2 times of that of S7;
s9, stannous octoate, wherein the mass of the stannous octoate is 10% -20% of that of S7;
the essence modified acrylic ester POSS is prepared from the following components:
s12, acrylate POSS;
s13, essence, wherein the mass of the essence is 10-15 times of that of the S12.
3. The PLA wire of claim 1, wherein the PLA is one or more of ring-opening polymerization PLA and direct polycondensation PLA.
4. A PLA wire as in claim 3 wherein the PLA is a direct polycondensation PLA.
5. A PLA strand as in claim 3, wherein the PLA has a melt index of 1-30g/10min and a molecular weight of 40000-100000g/mol at 190 ℃ and 2.16 kg.
6. The PLA strand according to any of claims 1 to 5, wherein the thermochromic powder is one or more of nickel chloride hexamethylenetetramine hydrate, copper sulphate hexamethylenetetramine hydrate, cobalt sulphate hexamethylenetetramine hydrate, phenanthroline acrylic europium complex, crystal violet lactone, bisphenol a.
7. The PLA strand according to any of claims 1 to 5, wherein the mineral powder is one or more of talc, calcium carbonate, wollastonite, and mica; and/or the number of the groups of groups,
the anti-hydrolysis agent is one or more of a polymerization type and a monomer type; and/or the number of the groups of groups,
the toughening agent is one or more of AX8900, wacker2504 and Wacker 2505.
8. The PLA wire of claim 7, wherein the hydrolysis inhibitor is one or more of HY210, DSA10A, and K-1.
9. A method of making the PLA wire of any of claims 1-5, comprising the steps of:
and mixing PLA, thermochromic powder, mineral powder, an anti-hydrolysis agent, a toughening agent and an essence modified POSS-PLA grafted polymer, adding into a double-screw extruder for melt extrusion, cooling, granulating, drying to obtain modified PLA particles, adding into a single-screw extruder for melt extrusion, and cooling to obtain the PLA wire.
10. The preparation method of the essence modified POSS-PLA grafted polymer according to claim 9, comprising the following steps: and (3) placing the essence modified acrylic ester POSS and PLA in a reaction tube, heating and melting under an inert atmosphere, adding stannous octoate for reaction, transferring to an ice bath after the reaction is finished, completely dissolving a product by using dichloromethane, pouring methanol, centrifuging to obtain a precipitate, repeatedly washing, and drying to obtain the essence modified POSS-PLA grafted polymer.
11. The preparation method according to claim 10, wherein the mass of PLA is 0.8 to 1.5 times that of essence modified acrylate POSS; and/or the mass of stannous octoate is 5% -30% of that of essence modified acrylic ester POSS; and/or the reaction temperature is 150-170 ℃ and the reaction time is 20-30h; and/or, drying conditions: the temperature is 40-60 ℃ and the time is 10-20h.
12. The method of claim 11, wherein the PLA is 1 to 1.2 times the mass of the perfume modified acrylate POSS; and/or the mass of stannous octoate is 10% -20% of that of essence modified acrylic ester POSS.
13. The preparation method according to any one of claims 10 to 12, wherein the preparation method of the essence modified acrylate POSS comprises the following steps: dissolving acrylic ester POSS in tetrahydrofuran, dissolving essence in absolute ethyl alcohol, heating the tetrahydrofuran solution, slowly stirring and dripping the tetrahydrofuran solution into the ethanol solution, carrying out reflux reaction, then cooling, adding a large amount of water to precipitate a product, filtering and repeatedly washing to obtain the essence modified acrylic ester POSS.
14. The preparation method according to claim 13, wherein the reaction temperature is 50-80 ℃ and the reaction time is 2-5h; and/or the essence is 8-20 times of the acrylic ester POSS.
15. The method of claim 14, wherein the essence is 10-15 times the mass of the acrylate POSS.
16. The preparation method according to claim 9, wherein the mixing is carried out by using a high speed mixer at a rotation speed of 20-100 rpm and a temperature of 20-50 ℃ for 3-10 min; and/or, the number of the groups,
the screw temperature of the double screw extruder is 150-210 ℃ and the rotating speed is 100-800rpm; and/or, the number of the groups,
the screw temperature of the single screw extruder is 160-200 ℃ and the rotating speed is 100-200rpm; and/or the number of the groups of groups,
the cooling temperature after single screw extrusion is 40-50 ℃.
17. Use of the PLA wire according to any one of claims 1-8 or the PLA wire made by the method of preparation of any one of claims 9-16 in the field of 3D printing.
18. The use according to claim 17, wherein the wire is used in FDM printers for printing at a printing temperature of 200-230 ℃, a floor temperature of 55-65 ℃ and a printing speed of 20-80mm/s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210988116.5A CN115386209B (en) | 2022-08-17 | 2022-08-17 | Long-acting fragrance-retaining PLA wire applied to 3D printing field and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210988116.5A CN115386209B (en) | 2022-08-17 | 2022-08-17 | Long-acting fragrance-retaining PLA wire applied to 3D printing field and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115386209A CN115386209A (en) | 2022-11-25 |
| CN115386209B true CN115386209B (en) | 2023-12-19 |
Family
ID=84119800
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210988116.5A Active CN115386209B (en) | 2022-08-17 | 2022-08-17 | Long-acting fragrance-retaining PLA wire applied to 3D printing field and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115386209B (en) |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090084144A (en) * | 2008-01-31 | 2009-08-05 | 금오공과대학교 산학협력단 | Pla/poss-pla including poss-pla and method for preparing the same |
| KR20100131228A (en) * | 2009-06-05 | 2010-12-15 | 금오공과대학교 산학협력단 | Polylactide-based nanocomposites with rapid crystallization rate and method for preparing the same |
| CN107686638A (en) * | 2017-07-21 | 2018-02-13 | 宁夏共享模具有限公司 | A kind of PLA for 3D printing is material modified and preparation method |
| CN107880269A (en) * | 2017-11-15 | 2018-04-06 | 华东理工大学 | Containing half times of silicone-based compound of polyhedral oligomeric and application thereof |
| CN108084442A (en) * | 2017-12-14 | 2018-05-29 | 华东理工大学 | Containing half times of siloxy group thiourea derivative of polyhedral oligomeric and its application in nano controlled-release fragrance is prepared |
| CN111821221A (en) * | 2020-07-09 | 2020-10-27 | 广州美茵生物科技有限公司 | Micelle with essence wrapped by self-assembly of hydrophilic and hydrophobic structure polymer and preparation method thereof |
| CN111978906A (en) * | 2020-08-07 | 2020-11-24 | 丽水市优力新材料有限公司 | MS sealant with insect expelling and ultraviolet aging resisting functions and preparation method thereof |
| CN113136094A (en) * | 2020-01-20 | 2021-07-20 | 武汉金发科技有限公司 | Reversible thermochromic polylactic acid material and preparation method thereof |
| CN113214616A (en) * | 2021-06-15 | 2021-08-06 | 万华化学（宁波）有限公司 | Low-odor biodegradable PLA alloy applied to food contact field and preparation method thereof |
| CN113736088A (en) * | 2021-09-18 | 2021-12-03 | 万华化学（宁波）有限公司 | Polysilsesquioxane, PLA alloy and straw material |
| CN113999500A (en) * | 2021-11-30 | 2022-02-01 | 万华化学（宁波）有限公司 | Degradable composite material with lasting fragrance, preparation method and application |
| CN114058166A (en) * | 2021-11-22 | 2022-02-18 | 苏州聚复高分子材料有限公司 | PLA (polylactic acid) fragrant wire for 3D (three-dimensional) printing and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA986068B (en) * | 1997-07-11 | 1999-02-24 | Rhodia Chimie Sa | Process for preparing polyorganosiloxanes (poss) having thiol functional groups poss capable of being obtained by this process and their use especially in the field of rubber materials |
| WO2009032199A1 (en) * | 2007-08-31 | 2009-03-12 | The Board Of Trustees Operating | Beta-cyclodextrins as nucleating agents for poly(lactic acid) |
| JP5756344B2 (en) * | 2011-05-30 | 2015-07-29 | 東レ・ダウコーニング株式会社 | Novel liquid organopolysiloxane and use thereof |
| WO2015165363A1 (en) * | 2014-04-30 | 2015-11-05 | 中国科学院化学研究所 | Material for 3d printing and preparation method therefor and product thereof |
-
2022
- 2022-08-17 CN CN202210988116.5A patent/CN115386209B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090084144A (en) * | 2008-01-31 | 2009-08-05 | 금오공과대학교 산학협력단 | Pla/poss-pla including poss-pla and method for preparing the same |
| KR20100131228A (en) * | 2009-06-05 | 2010-12-15 | 금오공과대학교 산학협력단 | Polylactide-based nanocomposites with rapid crystallization rate and method for preparing the same |
| CN107686638A (en) * | 2017-07-21 | 2018-02-13 | 宁夏共享模具有限公司 | A kind of PLA for 3D printing is material modified and preparation method |
| CN107880269A (en) * | 2017-11-15 | 2018-04-06 | 华东理工大学 | Containing half times of silicone-based compound of polyhedral oligomeric and application thereof |
| CN108084442A (en) * | 2017-12-14 | 2018-05-29 | 华东理工大学 | Containing half times of siloxy group thiourea derivative of polyhedral oligomeric and its application in nano controlled-release fragrance is prepared |
| CN113136094A (en) * | 2020-01-20 | 2021-07-20 | 武汉金发科技有限公司 | Reversible thermochromic polylactic acid material and preparation method thereof |
| CN111821221A (en) * | 2020-07-09 | 2020-10-27 | 广州美茵生物科技有限公司 | Micelle with essence wrapped by self-assembly of hydrophilic and hydrophobic structure polymer and preparation method thereof |
| CN111978906A (en) * | 2020-08-07 | 2020-11-24 | 丽水市优力新材料有限公司 | MS sealant with insect expelling and ultraviolet aging resisting functions and preparation method thereof |
| CN113214616A (en) * | 2021-06-15 | 2021-08-06 | 万华化学（宁波）有限公司 | Low-odor biodegradable PLA alloy applied to food contact field and preparation method thereof |
| CN113736088A (en) * | 2021-09-18 | 2021-12-03 | 万华化学（宁波）有限公司 | Polysilsesquioxane, PLA alloy and straw material |
| CN114058166A (en) * | 2021-11-22 | 2022-02-18 | 苏州聚复高分子材料有限公司 | PLA (polylactic acid) fragrant wire for 3D (three-dimensional) printing and preparation method and application thereof |
| CN113999500A (en) * | 2021-11-30 | 2022-02-01 | 万华化学（宁波）有限公司 | Degradable composite material with lasting fragrance, preparation method and application |
Non-Patent Citations (6)
| Title |
|---|
| New benzoxazines containing polyhedral oligomeric silsesquioxane from eugenol, guaiacol and vanillin;Thirukumaran Periyasamy等;《New J. Chem.》;正文第1691-1702页 * |
| PLA/PBSA纳米活性包装薄膜的性能研究;许耀之;李硕;林肯;杜蓉;蒋金勇;李立;;包装工程(15);正文第86-91页 * |
| 基于纳米尺寸低聚硅倍半氧烷潜香体的合成、表征及其香料醛分子缓释性能研究;韩建伟;薛陈伟;张志昂;王利民;王成云;肖作兵;朱为宏;;中国科学:化学(04);正文第31-40页 * |
| 用于3D打印的改性聚乳酸丝材的制备与研究;陈卫;汪艳;傅轶;;工程塑料应用(08);正文第28-31页 * |
| 聚乳酸改性及在包装领域的应用;晋慧斌;;工程塑料应用(12);正文第139-142页 * |
| 薄荷油香精缓释聚乳酸多孔微球的制备探究;胡世荣;陈小春;林晓霓;;闽南师范大学学报(自然科学版)(01);正文第82-85页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115386209A (en) | 2022-11-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102443256B (en) | High-heat-resistance polycarbonate (PC)/acrylonitrile styrene acrylate copolymer (ASA) alloy material and preparation method thereof | |
| CN103601976B (en) | Fiber glass reinforced polypropylene material of a kind of ladder of swimming pool pedal and preparation method thereof | |
| CN101942146B (en) | Controllable rheological high-gloss polypropylene resin and preparation method thereof | |
| CN101445638B (en) | PMMA/ABS modified resin and method for forming particles thereof | |
| CN105440613A (en) | PLA 3D printing material and product thereof | |
| CN103756240A (en) | Stress whitening resistance ABS (Acrylonitrile Butadiene Styrene) composite material as well as preparation method and application thereof | |
| CN103709704A (en) | PC/ABS (Polycarbonate/Acrylonitrile-Butadiene-Styrene) alloy with low odor and low emission and preparation method of PC/ABS alloy | |
| CN109836786A (en) | A kind of PC/ASA/PBT alloy material and preparation method thereof for 3D printing | |
| JPH09104795A (en) | Syndiotactic polystyrene improved in impact resistance | |
| CN115386209B (en) | Long-acting fragrance-retaining PLA wire applied to 3D printing field and preparation method and application thereof | |
| CN102686664B (en) | Thermoplastic resin composition and molded product using same | |
| CN111171542B (en) | High CTI flame-retardant polycarbonate alloy material and preparation method and application thereof | |
| JP6515189B2 (en) | Thermoplastic resin, method for producing the same, and thermoplastic resin composition containing the same | |
| CN108342050A (en) | A kind of ABS modified materials that can be used for 3D printing | |
| CN114773810B (en) | High-performance polylactic acid-based 3D printing wire rod and preparation method thereof | |
| CN101870797B (en) | Polyacrylonitrile-butadiene-styrene modified compound and preparation method thereof | |
| CN109912981A (en) | A kind of silicone masterbatch and preparation method thereof | |
| KR101674243B1 (en) | Thermoplastic resin composition and plated molded product | |
| CN107540799B (en) | Hydrogenated styrene-b-styrene/butadiene-b-styrene copolymer and elastomer wire material, and preparation method and application thereof | |
| CN115926415A (en) | PC/PMMA/ASA ternary alloy material and preparation method and application thereof | |
| CN101067038B (en) | Environment friendly fire retardant no-halogen PC composite material and its preparation method | |
| CN112724514A (en) | PP composite material suitable for extruded sheet plastic uptake and preparation method and application thereof | |
| JPS6326774B2 (en) | ||
| CN110293643A (en) | A kind of silicon rubber inner pattern releasing agent applicable and preparation method thereof | |
| CN107266808A (en) | A kind of high glaze toughness reinforcing AS composites and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |