CN117698113A - Method for improving interlayer adhesive force of melt extrusion deposition 3D printing product - Google Patents
Method for improving interlayer adhesive force of melt extrusion deposition 3D printing product Download PDFInfo
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- CN117698113A CN117698113A CN202410027203.3A CN202410027203A CN117698113A CN 117698113 A CN117698113 A CN 117698113A CN 202410027203 A CN202410027203 A CN 202410027203A CN 117698113 A CN117698113 A CN 117698113A
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- printing
- polylactic acid
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- hyperbranched polyester
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- 238000010146 3D printing Methods 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000011229 interlayer Substances 0.000 title claims abstract description 22
- 230000008021 deposition Effects 0.000 title claims abstract description 21
- 238000001125 extrusion Methods 0.000 title claims abstract description 16
- 239000000853 adhesive Substances 0.000 title abstract description 7
- 230000001070 adhesive effect Effects 0.000 title abstract description 7
- 238000007639 printing Methods 0.000 claims abstract description 49
- 150000003949 imides Chemical class 0.000 claims abstract description 38
- 229920006150 hyperbranched polyester Polymers 0.000 claims abstract description 34
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 30
- 239000004626 polylactic acid Substances 0.000 claims abstract description 30
- 239000000654 additive Substances 0.000 claims abstract description 14
- 230000000996 additive effect Effects 0.000 claims abstract description 12
- 238000000151 deposition Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 11
- 239000000155 melt Substances 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- 229920005862 polyol Polymers 0.000 claims description 8
- 150000003077 polyols Chemical class 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 8
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- 150000005846 sugar alcohols Polymers 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- KQIGMPWTAHJUMN-UHFFFAOYSA-N 3-aminopropane-1,2-diol Chemical compound NCC(O)CO KQIGMPWTAHJUMN-UHFFFAOYSA-N 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 235000011837 pasties Nutrition 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 2
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 claims description 2
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 2
- KJJPLEZQSCZCKE-UHFFFAOYSA-N 2-aminopropane-1,3-diol Chemical compound OCC(N)CO KJJPLEZQSCZCKE-UHFFFAOYSA-N 0.000 claims description 2
- BLFRQYKZFKYQLO-UHFFFAOYSA-N 4-aminobutan-1-ol Chemical compound NCCCCO BLFRQYKZFKYQLO-UHFFFAOYSA-N 0.000 claims description 2
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 2
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 2
- 229940102253 isopropanolamine Drugs 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 238000012986 modification Methods 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 21
- 239000000047 product Substances 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 15
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 229920003055 poly(ester-imide) Polymers 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000013590 bulk material Substances 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- CYOIAXUAIXVWMU-UHFFFAOYSA-N 2-[2-aminoethyl(2-hydroxyethyl)amino]ethanol Chemical compound NCCN(CCO)CCO CYOIAXUAIXVWMU-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- -1 hydroxyl ortho-methylene Chemical group 0.000 description 2
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 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
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/30—Auxiliary operations or equipment
- B29C64/307—Handling of material to be used in additive manufacturing
- B29C64/314—Preparation
-
- 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
- B33Y10/00—Processes of additive manufacturing
-
- 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
- B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
- B33Y40/10—Pre-treatment
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
- B29K2067/04—Polyesters derived from hydroxycarboxylic acids
- B29K2067/046—PLA, i.e. polylactic acid or polylactide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2079/00—Use of polymers having nitrogen, with or without oxygen or carbon only, in the main chain, not provided for in groups B29K2061/00 - B29K2077/00, as moulding material
- B29K2079/08—PI, i.e. polyimides or derivatives thereof
- B29K2079/085—Thermoplastic polyimides, e.g. polyesterimides, PEI, i.e. polyetherimides, or polyamideimides; Derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Optics & Photonics (AREA)
Abstract
The invention discloses a method for improving interlayer adhesive force of a fused extrusion deposition 3D printing product, which is characterized in that hyperbranched polyester imide additive and commercially available polylactic acid are fused and blended, modified polylactic acid is manufactured into a fused printing wire, and finally 3D printing is carried out on conventional fused extrusion deposition printing equipment. In the field of melt extrusion deposition printing, the additive content used in the present invention is the lowest of the currently known solutions on the market. The ultra-low addition amount not only can maintain the original physicochemical properties of the base material, but also can greatly reduce the modification cost, thereby being very beneficial to large-scale popularization and use. In addition, the invention aims at modifying the material, can realize the effect of the invention by utilizing the conventional printing condition, has the advantages of strong applicability, simplicity, convenience, low cost and the like, and has extremely high application value.
Description
Technical Field
The invention belongs to the technical field of polymer melt extrusion deposition 3D printing, and particularly relates to a method for improving interlayer acting force of a melt extrusion deposition 3D printing product.
Background
Today, 3D printing is a very promising additive manufacturing technology in recent years, which drastically changes the traditional material forming method. It can produce various products with minimum waste in a short time. Based on the advantages of flexible programmability and high precision, 3D has been widely used in various fields such as bionics, medical products, food manufacturing, intelligent sensors, electronics, automobiles, aerospace, etc. Among them, polymer fused deposition printing has been popularized as the most commonly used 3D printing method due to its advantages of high precision, low maintenance cost, short cycle time, easy use, etc. The working process of polymer fused deposition printing is as follows: under the control of computer programming, the filiform hot-melt polymer material in the spray pipe moves in the nozzle according to a preset track, is heated and melted, the temperature is slightly higher than the melting point, the fuse wire is extruded through the nozzle, the deposited layer is completed, and the extrusion material nozzle starts to solidify. And rapidly depositing the next layer on the nozzle, melting the next layer and the previous layer, stacking the repeatedly melted layers, and completing three-dimensional printing according to a preset pattern. However, during printing, the forces between layers differ significantly from the forces within a single layer, i.e. the strength in the printing direction (transverse strength) differs from the strength perpendicular to the printing direction (longitudinal strength), and is known in the industry as isotropic (or anisotropic). The longitudinal strength is usually far lower than the transverse strength due to weak interlayer adhesion, and the great strength difference can lead the 3D printing product to not exert the strength characteristics of the original materials due to the wooden barrel effect, so that the application of the device is severely limited. Therefore, if the interlayer adhesion of fused deposition 3D printing is improved, it is one of the difficulties that need to be solved in the field.
Currently, there is a great deal of effort devoted to solving the problem of the anisotropy of 3D printed products. For example, attempts to improve interlayer adhesion have been made by strictly controlling printing conditions (printing speed, nozzle temperature, interlayer thickness, melting temperature, etc.), but the improvement effect is not very remarkable, and the severe printing conditions limit the range of applications thereof. Attempts have also been made to post-age the article, which, while improving interlayer forces, is cumbersome and time consuming. The mode is an improvement on the 3D printing process, the operation steps are complex, the application range is narrow, and the effect is not ideal. More recently, the incorporation of adjuvants into materials has begun, with polymer modification, to achieve high interlayer adhesion. The reported effective auxiliary agents include talcum powder, glass fiber, carbon fiber, low molecular weight polylactic acid, polyether and the like, and for example, the isotropy of a 3D printing product can be improved to 95.6% by adding 5% of carbon fiber. Patent CN201910304504.5 provides a method for improving interlayer bonding force of a fused deposition 3D printing polymer device by using low molecular weight polylactic acid, but when the addition amount is as low as 0.2%, the isotropy is less than 75%. In the existing scheme, more auxiliary agents are needed, and excessive auxiliary agents not only affect other properties of the bulk material, but also increase the manufacturing cost of the finished product. Therefore, greatly improving interlayer adhesion of fused deposition 3D printed products at very low additive levels is one of the most desirable solutions.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a method for improving the interlayer adhesive force of a fused extrusion deposition 3D printing product, so that the interlayer adhesive force of the fused deposition 3D printing product is greatly improved under the condition of extremely low addition amount of auxiliary agents.
The aim of the invention is realized by the following technical scheme:
the invention provides a method for improving interlayer adhesion of a fused extrusion deposition 3D printing product, which comprises the following steps:
s1, melt blending a hyperbranched polyester imide additive and polylactic acid;
s2, manufacturing the polylactic acid modified in the step S1 into a melt printing wire rod, and performing 3D printing by adopting a melt extrusion deposition method.
As an embodiment of the present invention, the polylactic acid is a polylactic acid resin, including, but not limited to, 4032D of nature works, LX175 of dadel in thailand, revole 711 in the ocean of Zhejiang.
As an embodiment of the present invention, the hyperbranched polyester imide additive is prepared by a process comprising the steps of:
a1, under the condition of nitrogen atmosphere and stirring, firstly adding monoamino polyalcohol, polyol with or without the monoamino polyalcohol and monoamino monoalcohol with or without the monoamino polyalcohol into a polyester synthesis reactor, then adding trimellitic anhydride monomers in batches, and stirring the mixture until the mixture is pasty;
a2, heating to enable the pasty feed liquid to simultaneously carry out a molten polyester reaction and an imidization reaction at a high temperature; and cooling the melt after the reaction is completed to obtain the hyperbranched polyester imide additive.
In the system, the hyperbranched polyester imide improves the contact area between polylactic acid deposition layers in a mode of reducing the melt viscosity of the bulk material, promotes the diffusion and entanglement of polylactic acid molecular chains among layers, and greatly improves the interlayer adhesive force. In this process, the hyperbranched polyester imide does not significantly affect other properties of the bulk material, such as strength and modulus and crystallization properties of the injection molded article, due to the lower amount used.
As an embodiment of the present invention, the monoamino polyol is one or more of 3-amino-1, 2-propanediol, 2-amino-1, 3-propanediol, 2-amino-2-methyl-1, 3-propanediol.
As one embodiment of the present invention, the polyol is one or more of ethylene glycol, glycerol, diethylene glycol, pentaerythritol.
As an embodiment of the present invention, the monoaminomonoalcohol is one or more of ethanolamine, propanolamine, isopropanolamine, butanolamine, isobutanolamine, diglycolamine, pentanolamine, hexanolamine.
As one embodiment of the present invention, in step A1, the molar ratio of trimellitic anhydride, monoaminopolyol, polyol to monoaminomonoalcohol is 10:1 to 11:0 to 1:0 to 10.
In step A2, a condensing tube is arranged at the steam outlet of the reactor, the reaction pressure is controlled, water as a byproduct is collected, and the reaction progress is judged according to the water yield.
As an embodiment of the present invention, the additive is added in the blend of step S1 in a proportion of 0.01wt% to 3wt%, preferably 0.01wt% to 1wt%, more preferably 0.05wt% to 0.5wt%. The hyperbranched polyester imide has more obvious effect of improving the interlayer acting force of the 3D printing product.
As an embodiment of the invention, the 3D printing employs a fused extrusion deposition 3D printing apparatus, including but not limited to Creaty CR-5060pro.
Compared with the prior art, the invention has the following beneficial effects:
1) When the polylactic acid resin modified by adding the hyperbranched polymer is used for fused deposition 3D printing, the contact area between polylactic acid deposition layers can be increased by a very small amount of additives, the diffusion and entanglement of polylactic acid molecular chains among layers can be promoted, the interlayer adhesive force is greatly improved, and the highest isotropy rate of the polylactic acid resin can reach 96%, so that the comprehensive performance of a device is improved.
2) In the field of melt extrusion deposition printing, the content of additives used in the present invention is the lowest of the currently known solutions on the market, while ensuring high interlayer adhesion. The ultra-low addition amount not only can maintain the original physicochemical properties of the base material, but also can greatly reduce the modification cost, thereby being very beneficial to large-scale popularization and use.
3) In addition, the invention aims at modifying the material, can realize the effect of the invention by utilizing the conventional printing condition, has the advantages of strong applicability, simplicity, convenience, low cost and the like, and has extremely high application value.
Drawings
Other features, objects and advantages of the present invention will become more apparent upon reading of the detailed description of non-limiting embodiments, given with reference to the accompanying drawings in which:
FIG. 1 is a schematic illustration of various test spline processes;
FIG. 2 is a nuclear magnetic resonance spectrum of hyperbranched polyesterimide polymer 1;
FIG. 3 is an infrared spectrum of hyperbranched polyesterimide polymer 1;
FIG. 4 is a MOLDI-TOF diagram of hyperbranched polyester imide polymer 1.
FIG. 5 is a nuclear magnetic resonance spectrum of hyperbranched polyesterimide polymer 2;
FIG. 6 is an infrared spectrum of hyperbranched polyester imide polymer 2;
FIG. 7 is a MOLDI-TOF diagram of hyperbranched polyester imide polymer 2.
Detailed Description
The present invention will be described in detail with reference to examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that several modifications and improvements can be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
Example 1
Synthesis of hyperbranched polyester imide 1. 160g of N, N-bis (2-hydroxyethyl) ethylenediamine is added into a polyester synthesis kettle with mechanical stirring, nitrogen is replaced for three times, and oxygen in the kettle is removed; stirring is started, 208g of trimellitic anhydride in total is added in batches under the nitrogen atmosphere, heating of heat conduction oil is started, the temperature of a reaction system is ensured to be 100 ℃, and stirring is carried out for 60 minutes at normal pressure at the temperature; and a second step of: the temperature of the heat conduction oil is raised to 230 ℃ and the reaction is carried out for 60min under normal pressure, and meanwhile, byproduct water is collected. And pouring out the melt when the reaction is hot after the reaction is finished, and cooling to obtain the hyperbranched polyester imide 1, wherein the product is light yellow transparent solid.
The nuclear magnetic hydrogen spectrum (figure 2) shows that the peak at 4.56-4.67 ppm is the methylene combined proton special on the branching unitCharacterization peaks, 3.78ppm of proton characteristic peaks of terminal hydroxyl ortho-methylene, 3.84ppm of proton characteristic peaks of hydroxyl ortho-methylene on linear units, and the branching degree of the peaks can be calculated to be 0.66 according to the ratio of the peaks; infrared spectrum (FIG. 3) shows 713cm -1 、1078cm -1 、1365cm -1 The peak at the wavenumber is characteristic of an imide ring, 1720cm -1 The nearby peak is the characteristic peak of the stretching vibration of the carbonyl group on the ester group and the imide. Two test results show that the target polymer is formed by connecting imide and ester bonds. MALDI-TOF measurement showed a number average molecular weight of 2000 (FIG. 4) and a molecular weight distribution of 1.14. The structural formula is shown as formula (I):
example 2
Synthesis of hyperbranched polyester imide 2. The first step: 160g of 3-amino-1, 2-propanediol is added into a polyester synthesis kettle with mechanical stirring, nitrogen is replaced for three times, and oxygen in the kettle is removed; stirring is started, and 340g of flaky trimellitic anhydride is added in batches under the nitrogen atmosphere; heating heat conducting oil, ensuring the temperature of the reaction system to be 100 ℃, and stirring for 60min at normal pressure at the temperature; and a second step of: the temperature of the heat conduction oil is raised to 230 ℃ and the reaction is carried out for 60min under normal pressure, and meanwhile, byproduct water is collected. And pouring out the melt when the reaction is hot after the reaction is finished, and cooling to obtain the final polyester imide polymer 2, wherein the product is light yellow transparent solid.
The nuclear magnetic resonance hydrogen spectrum (figure 5) shows that peaks at 3.61ppm and 3.83ppm are proton characteristic peaks of terminal methylene and methylene, peaks at two positions near 4.20ppm and 4.28ppm are proton characteristic peaks of methylene and methylene on a linear unit, and peaks near 4.35ppm are combined proton characteristic peaks of methylene and methylene on a branching unit, and the branching degree can be calculated to be 0.58 according to the ratio of the peaks; infrared spectrum (FIG. 6) shows 713cm -1 、1078cm -1 、1365cm -1 The peak at the wavenumber is characteristic of an imide ring, 1720cm -1 The nearby peak being an ester groupAnd a characteristic peak of stretching vibration of carbonyl group on imide. Two test results show that the target polymer is formed by connecting imide and ester bonds. MALDI-TOF test results showed (FIG. 7) that the molecular weight of the target polymer was 2000. All of the above results demonstrate the correctness of the structure represented by formula (II).
In the method, in the process of the invention,representing repeat units not shown.
Example 3
Synthesis of hyperbranched polyester imide 3. In this example, 7.7g of glycerin was added to the system, and the other conditions were the same as in example 1, and the product was hyperbranched polyester imide 3, which had a pale yellow transparent solid, a yield of 90%, a degree of branching of 0.56, and a molecular weight of 1900.
Example 4
Synthesis of hyperbranched polyester imide 4. The molar ratio of trimellitic anhydride, 3-amino-1, 2-propanediol, ethanolamine and glycerol in this example was 2:1:1:0.09, the other conditions were the same as in example 1, the product was hyperbranched polyesterimide 4, the appearance was a pale yellow transparent solid, the yield was 90%, the degree of branching was 0.23, and the molecular weight was 1900.
Example 5
Synthesis of hyperbranched polyester imide 5. The molar ratio of trimellitic anhydride to tris (hydroxymethyl) aminomethane in this example was 1:1, the other conditions were the same as in example 1, the product was hyperbranched polyester imide 5, the appearance was a pale yellow transparent solid, the yield was 90%, the degree of branching was 0.34, and the molecular weight was 2000.
Comparative example 1
4032D of commercially available polylactic acid NaturewWorks was previously dried, 0.5wt% of hyperbranched polyester imide 1 was added, and then 1.75mm standard wire was extruded for 3D printing by twin screw blending. The printing equipment was Creaty CR-5060pro, nozzle temperature 200 ℃, printing speed 50mm/min, printing layer thickness 0.2mm, and two kinds of bars shown in FIG. 1 were printed.
Comparative example 2
4032D of commercially available polylactic acid NaturewWorks was previously dried, 0.5wt% of hyperbranched polyester imide 5 was added, and then 1.75mm standard wire was extruded for 3D printing by twin screw blending. The printing equipment was Creaty CR-5060pro, nozzle temperature 200 ℃, printing speed 50mm/min, printing layer thickness 0.2mm, and two kinds of bars shown in FIG. 1 were printed.
Comparative example 3
4032D of commercial polylactic acid NaturewWorks was previously dried, 0.5wt% of hyperbranched polyester bolton H20 was added, followed by twin-screw blending to extrude 1.75mm standard strands for 3D printing. The printing equipment was Creaty CR-5060pro, nozzle temperature 200 ℃, printing speed 50mm/min, printing layer thickness 0.2mm, and two kinds of bars shown in FIG. 1 were printed.
Comparative example 4
4032D of commercially available polylactic acid NaturewWorks was previously dried and 1.75mm standard strands were extruded through a twin screw for 3D printing. The printing equipment was Creaty CR-5060pro, nozzle temperature 200 ℃, printing speed 50mm/min, printing layer thickness 0.2mm, and two kinds of bars shown in FIG. 1 were printed. Wherein 90 ° represents the print direction perpendicular to the spline direction and 0 ° represents the print direction parallel to the spline direction.
Example 6
4032D of commercially available polylactic acid NaturewWorks was previously dried, 0.01wt% of hyperbranched polyester imide 4 was added, and then 1.75mm standard wire was extruded for 3D printing by twin screw blending. The printing equipment was Creaty CR-5060pro, nozzle temperature 200 ℃, printing speed 50mm/min, printing layer thickness 0.2mm, and two kinds of bars shown in FIG. 1 were printed.
Example 7
4032D of commercially available polylactic acid NaturewWorks was previously dried, 0.5wt% of hyperbranched polyester imide 4 was added, and then 1.75mm standard wire was extruded for 3D printing by twin screw blending. The printing equipment was Creaty CR-5060pro, nozzle temperature 200 ℃, printing speed 50mm/min, printing layer thickness 0.2mm, and two kinds of bars shown in FIG. 1 were printed.
Example 8
4032D of commercially available polylactic acid NaturewWorks was previously dried, 1wt% of hyperbranched polyester imide 4 was added, and then 1.75mm standard strands were extruded for 3D printing by twin screw blending. The printing equipment was Creaty CR-5060pro, nozzle temperature 200 ℃, printing speed 50mm/min, printing layer thickness 0.2mm, and two kinds of bars shown in FIG. 1 were printed.
Example 9
4032D of commercially available polylactic acid NaturewWorks was previously dried, 2wt% of hyperbranched polyester imide 4 was added, and then 1.75mm standard strands were extruded for 3D printing by twin screw blending. The printing equipment was Creaty CR-5060pro, nozzle temperature 200 ℃, printing speed 50mm/min, printing layer thickness 0.2mm, and two kinds of bars shown in FIG. 1 were printed.
Example 10
4032D of commercially available polylactic acid NaturewWorks was previously dried, 3wt% of hyperbranched polyester imide 4 was added, and then 1.75mm standard strands were extruded for 3D printing by twin screw blending. The printing equipment was Creaty CR-5060pro, nozzle temperature 200 ℃, printing speed 50mm/min, printing layer thickness 0.2mm, and two kinds of bars shown in FIG. 1 were printed.
Example 11
4032D of commercially available polylactic acid NaturewWorks was previously dried, 0.5wt% of hyperbranched polyester imide 2 was added, and then 1.75mm standard strands were extruded for 3D printing via twin screw blending. The printing equipment was Creaty CR-5060pro, nozzle temperature 200 ℃, printing speed 50mm/min, printing layer thickness 0.2mm, and two kinds of bars shown in FIG. 1 were printed.
Example 12
4032D of commercially available polylactic acid NaturewWorks was previously dried, 0.5wt% of hyperbranched polyester imide 3 was added, and then 1.75mm standard wire was extruded for 3D printing by twin screw blending. The printing equipment was Creaty CR-5060pro, nozzle temperature 200 ℃, printing speed 50mm/min, printing layer thickness 0.2mm, and two kinds of bars shown in FIG. 1 were printed.
The tensile strength of the samples prepared in the above comparative examples 1 to 4 and examples 6 to 12, test standard according to GB/T-1040.1-2018; the data are detailed in Table 1:
TABLE 1
It is known from the table that compared with the commercial hyperbranched polyester H20, the hyperbranched polyester imide with a partial structure can significantly improve the interlayer adhesion of the polylactic acid 3D printing product, but the hyperbranched polyester imide synthesized from N, N-bis (2-hydroxyethyl) ethylenediamine or tris (hydroxymethyl) aminomethane does not show an improvement effect on the interlayer adhesion.
The foregoing describes specific embodiments of the present invention. It is to be understood that the invention is not limited to the particular embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the claims without affecting the spirit of the invention.
Claims (10)
1. A method of improving interlayer adhesion of a melt extrusion deposited 3D printed article, the method comprising the steps of:
s1, melt blending a hyperbranched polyester imide additive and polylactic acid;
s2, manufacturing the polylactic acid modified in the step S1 into a melt printing wire rod, and performing 3D printing by adopting a melt extrusion deposition method.
2. The method of claim 1, wherein the polylactic acid is a polylactic acid resin, including, but not limited to, 4032D of nature works, LX175 of dall in thailand, revole 711 in the ocean of Zhejiang.
3. The method of claim 1, wherein the hyperbranched polyester imide additive is prepared by a process comprising the steps of:
a1, under the condition of nitrogen atmosphere and stirring, firstly adding monoamino polyalcohol, polyol with or without the monoamino polyalcohol and monoamino monoalcohol with or without the monoamino polyalcohol into a polyester synthesis reactor, then adding trimellitic anhydride monomers in batches, and stirring the mixture until the mixture is pasty;
a2, heating to enable the pasty feed liquid to simultaneously carry out a molten polyester reaction and an imidization reaction at a high temperature; and cooling the melt after the reaction is completed to obtain the hyperbranched polyester imide additive.
4. A method according to claim 3, wherein the monoamino polyol is one or more of 3-amino-1, 2-propanediol, 2-amino-1, 3-propanediol, 2-amino-2-methyl-1, 3-propanediol.
5. A method according to claim 3, wherein the polyol is one or more of ethylene glycol, glycerol, diethylene glycol, pentaerythritol.
6. A method according to claim 3, wherein the monoaminomonoalcohol is one or more of ethanolamine, propanolamine, isopropanolamine, butanolamine, isobutanolamine, diglycolamine, pentanolamine, hexanolamine.
7. A process according to claim 3, wherein in step A1 the molar ratio of trimellitic anhydride, monoaminopolyol, polyol to monoaminomonoalcohol is from 10:1 to 11:0 to 1:0 to 10.
8. A method according to claim 3, wherein in step A2, a condenser is provided at the steam outlet of the reactor, the reaction pressure is controlled, and the by-product water is collected, and the progress of the reaction is judged based on the amount of water produced.
9. The method of claim 1, wherein the additive is added to the blend of step S1 in a proportion of 0.01wt% to 3wt%.
10. The method of claim 1, wherein the 3D printing employs a fused extrusion deposition 3D printing device, including but not limited to Creality CR-5060pro.
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