CN109880180A - Nano-cellulose/cellulose composite, enhancing polylactic acid 3D printing material and preparation method thereof - Google Patents
Nano-cellulose/cellulose composite, enhancing polylactic acid 3D printing material and preparation method thereof Download PDFInfo
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- CN109880180A CN109880180A CN201910186916.3A CN201910186916A CN109880180A CN 109880180 A CN109880180 A CN 109880180A CN 201910186916 A CN201910186916 A CN 201910186916A CN 109880180 A CN109880180 A CN 109880180A
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 139
- 239000001913 cellulose Substances 0.000 title claims abstract description 138
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 57
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 57
- 239000000463 material Substances 0.000 title claims abstract description 56
- 238000010146 3D printing Methods 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 230000002708 enhancing effect Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000001125 extrusion Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 238000012545 processing Methods 0.000 claims abstract description 4
- 235000010980 cellulose Nutrition 0.000 claims description 81
- 239000007788 liquid Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 229920001046 Nanocellulose Polymers 0.000 claims description 14
- 239000000835 fiber Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 12
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 11
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 10
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 10
- 239000002086 nanomaterial Substances 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 238000000703 high-speed centrifugation Methods 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000004014 plasticizer Substances 0.000 claims description 8
- 239000012745 toughening agent Substances 0.000 claims description 8
- 238000013517 stratification Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002070 nanowire Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000008188 pellet Substances 0.000 claims description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 238000005453 pelletization Methods 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 claims description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 claims description 2
- 239000000806 elastomer Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 229920001169 thermoplastic Polymers 0.000 claims description 2
- 239000004416 thermosoftening plastic Substances 0.000 claims description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 2
- 206010023126 Jaundice Diseases 0.000 claims 1
- 239000005062 Polybutadiene Substances 0.000 claims 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- 150000007524 organic acids Chemical class 0.000 claims 1
- 229920002857 polybutadiene Polymers 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 6
- 238000007639 printing Methods 0.000 abstract description 5
- 238000005034 decoration Methods 0.000 abstract description 2
- 238000005491 wire drawing Methods 0.000 abstract description 2
- 241001465382 Physalis alkekengi Species 0.000 abstract 1
- 239000008236 heating water Substances 0.000 abstract 1
- 238000002203 pretreatment Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 229920000742 Cotton Polymers 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000011056 performance test Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 241000208202 Linaceae Species 0.000 description 3
- 235000004431 Linum usitatissimum Nutrition 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Substances ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 244000198134 Agave sisalana Species 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000011173 biocomposite Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000013081 microcrystal Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000005476 size effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 240000000491 Corchorus aestuans Species 0.000 description 1
- 235000011777 Corchorus aestuans Nutrition 0.000 description 1
- 235000010862 Corchorus capsularis Nutrition 0.000 description 1
- 241001343274 Dichrostachys spicata Species 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- 229920002594 Polyethylene Glycol 8000 Polymers 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
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- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- -1 element Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011174 green composite Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
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- 238000001764 infiltration Methods 0.000 description 1
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- 230000003993 interaction Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
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Abstract
The invention belongs to polymer composites and 3D printing Material Field, and in particular to a kind of nano-cellulose/cellulose composite that can be used for polylactic acid 3D printing material and related enhancing 3D printing material.The present invention obtains nano-cellulose/cellulose composite and its enhancing polylactic acid 3D printing material by water bath with thermostatic control reaction, blending extrusion using native cellulose, acid, silane coupling agent, polylactic acid as raw material.Preparation process is raw material pre-treatment, mixing, heating water bath, drying, blending extrusion, wire drawing etc., entire preparation process is simple, repeatability is high, prepared 3D printing material is compared to pure polylactic acid, its mechanical property is obviously improved, processing performance is good, then transparency is high compared to common native cellulose enhancing polylactic acid 3D printing material, printing when be not easy plug and alice, have higher application value in fields such as household, decoration, lamps and lanterns, art and modellings.
Description
Technical field
The invention belongs to polymer composites and 3D printing Material Field, and in particular to a kind of nano-cellulose/fiber
Plain compound, enhancing polylactic acid 3D printing material and preparation method thereof.
Background technique
Cellulose is a kind of multiduty boiomacromolecule, cannot be dissolved in Conventional solvents, only the chlorination of high concentration
The crystal structure that zinc aqueous solution, copper ammon solution, ionic liquid etc. are likely to destroy cellulose makes it dissolve, and cellulosic structure
Complexity, there are a variety of interactions, therefore, are still faced by the research that the monomer that cellulose derives synthesizes high molecular material many
It is difficult.High-specific surface area, high Young's modulus, high mechanical strength and high-biocompatibility that nano material has with it etc. are special
Performance and nanometer size effect become the forward position direction of Materials.Since nano-cellulose has good fluffy three-dimensional network
Structure can promote polymeric matrix and filler to reach combination mechanically, thus enhance the performance of polymer, therefore, as fibre
Tieing up the nano-cellulose that plain material of main part is amplified out is even more the trend for meeting the development of High-performance green composite material.
Chinese patent CN108239379A discloses a kind of preparation method of nano-cellulose composite material, and the patent is by day
A nanometer fento is made in right cotton, then injected plastics material is made with polylactic acid blend, but during preparing nano-cellulose with cotton,
Highly basic, hydrogen peroxide boiling are used, then with being centrifugated after the oxidation of TEMPO oxidation system, the process is various and high using reagent
It is expensive, process is longer, while gained nano-cellulose yield is lower, and a large amount of native celluloses are wasted.Chinese patent
CN104292439A discloses a kind of preparation method of sisal cellulose nano whisker/polylactic acid Biocomposite material, utilizes sword
Flaxen fiber element nano whisker surface grafting polylactic acid low polymer makes it form the good interface knot of compatibility between polylactic acid
It closes, and sisal cellulose nano whisker/polylactic acid Biocomposite material is prepared using in-situ compound technology, use reagent in method
It is safe, environmentally protective, but need the conditions such as 400 DEG C of high temperature, vacuum cooled, vacuum distillations, polymerization process the high requirements on the equipment.In
State patent CN108219404A discloses a kind of preparation method of nano micro crystal cellulose enhancing polylactic acid 3D printing material, by needle
Leaf lignose 98% sulfuric acid solution, ultrasonic treatment, high speed centrifugation, add that zinc oxide is high-pressure homogeneous to be made dispersion liquid, finally
Wire drawing preparation is blended with polylactic acid-chloroform soln.The material have good mobility and mechanical property, but 98% sulfuric acid,
Danger level is high in process of production for the toxic hazardous agents such as chloroform, requires production equipment and storage facilities high, it is difficult to
Large-scale serial production, while production process can cause larger pollution to environment.
In FDM type 3D printing technique, theoretically cellulose can be dispersed in high score by doping as natural long fibre
In subbase body, increase intrinsic silicon frictional force, to improve the mechanical property of materials especially tensile property, promotes material application valence
Value.But not only molecular weight is very big for untreated cellulose, and surface hydroxyl is more, and structure is also extremely stable, tend not to it is polymer-based
Body is compatible to instead result in its destruction polymeric inner ordered structure, and overall mechanical properties decline instead.It is incompatible with matrix simultaneously
Cellulose be easy to reunite and deposit in printing head during 3D printing, cause printing have some setbacks, plug phenomena such as, make to beat
Print cannot continue to carry out.Nano-cellulose size is small, molecular weight is relatively low, active higher, can have with macromolecule matrix well
Infiltration combine, but nano-cellulose generally requires to isolate and purify during preparation, and the required period is long, higher cost.
Summary of the invention
In order to overcome cellulose in the prior art and high molecular polymer poor compatibility, nano-cellulose preparation process is numerous
It is trivial, be difficult to the disadvantages of making full use of and insufficient, the primary purpose of the present invention is that: it is a series of more simple by being carried out to cellulose
Single and safety process, it is multiple to prepare a kind of nano-cellulose/cellulose that can be used for enhancing polylactic acid 3D printing material
Close object.It is achieved through the following technical solutions:
A kind of nano-cellulose/cellulose composite, is made of the method comprising the following steps:
(1) after crushing a certain amount of cellulose, (under the conditions of 45-60 DEG C of water bath with thermostatic control) is extremely molten with mineral acid treatment (1-5 h)
Liquid turn to be yellow until, then with (10-20 times of volume of acquired solution) water dilute, stratification Hou Qu lower layer containing it is wadding fibrous element mix
Liquid is spare；
(2) by mixed liquid (with 8000-12000 r/min) high speed centrifugation (5-20 min) containing wadding fibrous element obtained by step (1),
Collect upper layer turbid, will bottom it is wadding fibrous element in plus water mixing become cloudy after be centrifuged again, so repeatedly circulation (until
After separation in the wadding fibrous element in bottom plus until water mixing does not become cloudy), merge gained turbid, as stable nano-cellulose
Colloidal sol；
(3) a certain amount of cellulose is crushed, sieving, obtains the crystallite of (uniform particle sizes') cellulose powder or commercially available same partial size
Cellulose powder, it is spare as cellulose powder；Take nano cellulose sol obtained by a certain amount of step (2) and the cellulose powder
Material is uniformly mixed；
(4) mixture made from step (3) is first placed into (0.5-1 h) under 75-85 DEG C of water bath condition to constant temperature, then plus
Entering with cellulose powder mass ratio is (1-10): the silane coupling agent of (1-10), (under constant temperature air-proof condition) are stirred to react 4-5
H obtains product precipitating；Products therefrom (with water) is washed into filtering, the substances such as silane coupling agent remaining in the reaction is removed, obtains
To nano-cellulose/cellulose composite, (at 80 DEG C) drying.
Preferably, inorganic acid described in step (1) is the hydrochloric acid of mass fraction 20-38%, the sulfuric acid of 50-64%, oleic acid, phosphorus
One of acid or a variety of mixing；The cellulose can be fine for cotton, flax, jute, needlebush, leaf wood and filter paper paper pulp
Tie up one of element or a variety of mixing；
Preferably, cellulose powder particle size described in step (3) is 50-250 mesh, more preferably 100-150 mesh.
Preferably, the mass ratio of nano cellulose sol described in step (3) and cellulose powder is (10-500): 1；
Preferably (50-100): 1.
Preferably, silane coupling agent described in step (4) is KH series silane coupling agent, more preferable gamma-amino propyl three
Ethoxysilane (KH550), γ-glycidyl ether oxygen propyl trimethoxy silicane (KH560) and γ-(methacryloxypropyl) third
One of base trimethoxy silane (KH570), most preferably γ aminopropyltriethoxy silane (KH550).
Another object of the present invention is to provide a kind of nano-cellulose/cellulose composite enhancing polylactic acid 3D printing material
Material is keeping the excellent 3D printing performance of PLA simultaneously, is significantly improving bending property, tensile property and the shock resistance of material.
A kind of enhancing polylactic acid 3D printing material, raw material include above-mentioned nano-cellulose/cellulose composite, preferably with
Polylactic acid, inorganic nano material, toughener, plasticizer are blended and are obtained.
Preferably, the enhancing polylactic acid 3D printing material includes the raw material of following mass percent: nano-cellulose/fibre
Tie up plain compound 0.1-2%, polylactic acid 90-98%, inorganic nano material 0.1-3%, toughener 0.1-5% and plasticizer 0.1-5%.
It is furthermore preferred that the molecular weight of the polylactic acid is 1.0 × 106-3.0×106.The inorganic nano material is nanometer
One of silica, nano-titanium dioxide, nano zirconium dioxide, nanometer calcium carbonate.The toughener is SEBS(benzene second
Alkene-butadiene-embedding the copolymer of benzene second), SBS(thermoplastic polystyrene-polybutadienes-polystyrene block copolymer), TPU
One of (thermoplastic polyurethane elastomer), TPEE(thermoplastic polyester elastomer).The plasticizer is polyethylene glycol
(PEG), molecular weight 1000-20000.
The preparation method of above-mentioned enhancing polylactic acid 3D printing material, comprising the following steps:
(1) in proportion by the nano-cellulose/cellulose composite and polylactic acid, inorganic nano material, toughener, plasticizer
Blend composition is formed through mixed at high speed；
(2) by gained blend composition by double screw extruder melting extrusion and pelletizing, 1-6 sections of temperature of extruder are respectively 170-
175 DEG C, 170-177 DEG C, 175-180 DEG C, 180-185 DEG C, 180-185 DEG C and 185-190 DEG C, obtain pellet, fill in 80-85 DEG C
Divide drying；
(3) gained pellet squeezed out by single screw extrusion machine, drawn, 3D printing wire rod, the 1-4 section of extruder are processed into coiling
Temperature is respectively 170-180 DEG C, 175-185 DEG C, 180-190 DEG C, 180-190 DEG C, and hauling speed is 50-60mm/s to get institute
Obtaining gauge or diameter of wire is about 1.75mm or 3mm, and diameter error is within ± 5%.
The present invention has following positive beneficial effect:
Nano-cellulose/cellulose composite of the present invention and polylactic acid compatibility are good.The existing natural big cellulose of the compound
Long fibre shape structure, and have the Large ratio surface and nanometer size effect of nano-cellulose.It is different from general fibre element, it mixes on a small quantity
It can be obviously improved its mechanical performance among heteromeric lactic acid, high performance 3 d printing wire rod is made, while can make to keep polylactic acid again
3D printing material transparent or translucent appearance can be applied to the necks such as macromolecule 3D printing field especially 3D printing decoration
Domain.
(1) for cellulose as natural biomass, source is wide, easily obtains, native cellulose that the present invention uses, microcrystalline cellulose
The raw materials such as element, silane coupling agent, inorganic nano material, toughener, plasticizer all belong to technical grade, safe and non-toxic, to ingredient requirement
It is not high.And short preparation period, repeatability are high, application easy to produce.
(2) will be compound with cellulose again after cellulose sized nanostructures, so that it is attached to native cellulose surface, using receiving
The shortcomings that rice dimensional effect improves cellulose and polylactic acid poor compatibility, while silane coupling agent also can be reduced what its surface was rich in
Hydroxyl further promotes the two compatibility, can enhance polylactic acid 3D printing wire rod mechanical strength and print product
Journey is not susceptible to plug phenomenon.
(3) gained nano-cellulose solution reacts in next step without isolating and purifying to may participate in present invention process, and not
Its performance is influenced, reduce traditional acidolysis nano-cellulose needs dialyse required long period and Gao Chengben after centrifugation.
(4) 3D printing material of the present invention is made of cellulose, polylactic acid, is all environmentally friendly degradation material, will not
The secondary pollutions such as white pollution are generated, can be decomposed after simple process under optimum conditions.
Detailed description of the invention
Fig. 1 nano-cellulose/Microcrystalline cellulose composite amplifies 1200 times of SEM figure.
Fig. 2 nano-cellulose/Microcrystalline cellulose composite amplifies 12000 times of SEM figure.
Fig. 3 nano-cellulose/Microcrystalline cellulose composite amplifies 65000 times of SEM figure.
Fig. 4 nano-cellulose/Microcrystalline cellulose composite enhances polylactic acid 3D printing wire rod.
Fig. 5 enhances polylactic acid 3D printing wire rod printout model.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Reagent used in the embodiment of the present invention is all commercially available conventional reagent or raw material unless stated otherwise, and embodiment makes
Test method is all conventional method in that art unless stated otherwise.The specific method of Mechanics Performance Testing is carried out to material
As follows: tension test is executed referring to national standard GB/T 1040-2006 standard, tensile speed 5mm/min；Bend test is referring to state
It marks GB/T 9341-2008 standard to execute, rate of bending 5mm/min；Nick break test is referring to national standard GB/T 1043-2008
Standard executes.
Embodiment 1
A kind of enhancing polylactic acid 3D printing material, is prepared from the following steps:
(1) acid being mixed into after crushing 2g cotton cellulose with+25 ml oleic acid of 25 ml, 64% sulfuric acid is in 50 DEG C of waters bath with thermostatic control
It handles 2h to turn to be yellow to solution, be diluted after stopping reaction with 500 ml water；Mixed liquid of the stratification Hou Qu lower layer containing wadding fibrous element
It is spare；
(2) the mixed liquid containing wadding fibrous element was collected into upper layer turbid with 8000 r/m high speed centrifugation 15 minutes, by the cotton-shaped fibre in bottom
It ties up in element plus water is mixed after becoming cloudy and is centrifuged again, so multiple circulation, until adding in the wadding fibrous element in bottom after separating
Until water mixing does not become cloudy, merge gained turbid, for stable nano cellulose sol liquid；
(3) 2g cotton cellulose is crushed, crosses 150 meshes, obtains 150 mesh cellulose powders；
(4) the made nano cellulose sol liquid of 200ml is taken to be uniformly mixed with 2g cellulose powder；
(5) mixture made from step (4) is first placed to 0.5h under 80 DEG C of water bath condition to constant temperature, then adds at this temperature
The Silane coupling agent KH550 for entering 1g stirs under constant temperature air-proof condition, reacts 5h；
(6) stop can observe mixed liquor after reacting by turbid change clearly, then the product that step (5) is reacted was washed with water and is filtered dry
Only, the substances such as silane coupling agent remaining in the reaction are removed, after obtaining nano-cellulose/cellulose composite, at 80 DEG C
Drying, cellulose utilization rate is up to 86.2%.Obtained nano-cellulose/cellulose composite scanning electron microscope (SEM) photograph is shown in that specification is attached
Fig. 1；
It (7) is by mass percentage respectively 0.5 % of nano-cellulose/cellulose composite, polylactic acid 98%, nano silica
0.5 %, SEBS 0.5 % and PEG-10000 0.5% ratio weigh, be put into togerther in high-speed mixer after mixing 5 min and take
Out, mixture is obtained；
(8) then the mixture prepared in step (7) is squeezed out through double screw extruder and is blended, pelletizing obtains compound after being cooled by water
Material master batch, it is dry at 80 DEG C to seal afterwards for 24 hours spare, each area's temperature setting of extruder is respectively 170 DEG C, 170 DEG C, 175 DEG C,
180 DEG C, 180 DEG C, 185 DEG C, host and feeder revolving speed are respectively 20 r/min and 10 r/min；
(9) after the pellet prepared in step (8) being dried, single screw extrusion machine, the feeding section of extruder, compression are added to
The temperature of section, metering section and cylinder is respectively set as 170 DEG C, 175 DEG C, 180 DEG C and 185 DEG C；The melt of extrusion is through water-carrying groove
Cooling air-drying is prepared into diameter using dragger and is about the monofilament of 1.75 mm or 3.0 mm, and winds；
(10) monofilament after winding is tested after printing standard batten by FDM type 3D printer, and print temperature (nozzle) is 200 DEG C
(can adjust according to the actual situation), nozzle diameter 0.4mm, print speed 60mm/min, print platform temperature are not fixed.
Mechanics Performance Testing, Nanowire manufactured in the present embodiment are carried out according to national standards to material standard batten obtained
Dimension element/cellulose composite enhancing polylactic acid 3D printing material mechanical property and 3D printing performance test results are shown in Table 1.
Embodiment 2
A kind of enhancing polylactic acid 3D printing material, is prepared from the following steps:
(1) it is slightly turned to be yellow in 45 DEG C of water bath with thermostatic control processing 1h to solution after crushing 2g flax fiber element with 64% sulfuric acid of 35ml
Until, it is diluted after stopping reaction with 700ml water；Mixed liquid of the stratification Hou Qu lower layer containing wadding fibrous element is spare；
(2) the mixed liquid containing wadding fibrous element was collected into upper layer turbid with 8000 r/m high speed centrifugation 20 minutes, by the cotton-shaped fibre in bottom
It ties up in element plus water is mixed after becoming cloudy and is centrifuged again, so multiple circulation, until adding in the wadding fibrous element in bottom after separating
Until water mixing does not become cloudy, merge gained turbid, for stable nano cellulose sol liquid；
(3) 2g flax fiber element is crushed, crosses 150 meshes, obtains 150 mesh cellulose powders；
(4) the made nano cellulose sol liquid of 200ml is taken to be uniformly mixed with 2g cellulose powder；
(5) mixture made from step (4) is first placed to 0.5h under 75 DEG C of water bath condition to constant temperature, then adds at this temperature
The silane coupling agent KH560 for entering 1g, is stirred under constant temperature air-proof condition, reacts 5h；
(6) stop can observe mixed liquor after reacting by turbid change clearly, then the product that step (5) is reacted was washed with water and is filtered dry
Only, the substances such as silane coupling agent remaining in the reaction are removed, after obtaining nano-cellulose/cellulose composite, at 80 DEG C
Drying, cellulose utilization rate is up to 85.3%；
It (7) is by mass percentage respectively 0.5 % of nano-cellulose/cellulose composite, 97 % of polylactic acid, nano silica
0.5 %, SEBS 1 % and PEG-10000 1% ratio weigh, be put into togerther in high-speed mixer after mixing 5 min and take out, obtain
Mixture；Remaining steps (8), (9), (10) are same as Example 1.
Mechanics Performance Testing, Nanowire manufactured in the present embodiment are carried out according to national standards to material standard batten obtained
Dimension element/cellulose composite enhancing polylactic acid 3D printing material mechanical property and 3D printing performance test results are shown in Table 1.
Embodiment 3
A kind of enhancing polylactic acid 3D printing material, is prepared from the following steps:
(1) it is slightly turned to be yellow in 60 DEG C of water bath with thermostatic control processing 1h to solution after crushing 2g tossa element with 30% hydrochloric acid of 40ml
Until, it is diluted after stopping reaction with 600ml water；Mixed liquid of the stratification Hou Qu lower layer containing wadding fibrous element is spare；
(2) the mixed liquid containing wadding fibrous element was collected into upper layer turbid with 12000 r/m high speed centrifugation 10 minutes, bottom is cotton-shaped
In cellulose plus water is mixed after becoming cloudy and is centrifuged again, is so repeatedly recycled, until after separating in the wadding fibrous element in bottom
Until adding water mixing not become cloudy, merge gained turbid, for stable nano cellulose sol liquid；
(3) 2g tossa element is crushed, crosses 150 meshes, obtains 150 mesh cellulose powders.
(4) the made nano cellulose sol liquid of 200ml is taken to be uniformly mixed with 2g cellulose powder；
(5) mixture made from step (4) is first placed to 0.5h under 80 DEG C of water bath condition to constant temperature, then adds at this temperature
The silane coupling agent KH570 for entering 1g, is stirred under constant temperature air-proof condition, reacts 5h；
(6) stop can observe mixed liquor after reacting by turbid change clearly, then the product that step (5) is reacted was washed with water and is filtered dry
Only, the substances such as silane coupling agent remaining in the reaction are removed, after obtaining nano-cellulose/cellulose composite, at 80 DEG C
Drying, cellulose utilization rate is up to 86.7%；
It (7) is by mass percentage respectively 0.5 % of nano-cellulose/cellulose composite, 96 % of polylactic acid, nano-titanium dioxide
0.5 %, SEBS 1.5 % and PEG-8000 1.5% ratio weigh, be put into togerther in high-speed mixer after mixing 5 min and take
Out, mixture is obtained；Remaining (8), (9), the experimental procedure of (10) are identical as embodiment 1.
Mechanics Performance Testing, Nanowire manufactured in the present embodiment are carried out according to national standards to material standard batten obtained
Dimension element/cellulose composite enhancing polylactic acid 3D printing material mechanical property and 3D printing performance test results are shown in Table 1.This reality
The 3D printing wire rod and printout for applying example preparation are shown in Figure of description 2.
Embodiment 4
A kind of enhancing polylactic acid 3D printing material, is prepared from the following steps:
(1) 1h are handled until solution slightly turns to be yellow in 45 DEG C of waters bath with thermostatic control with 40ml phosphoric acid after crushing 2g microcrystalline cellulose,
It is diluted after stopping reaction with 400ml water；Mixed liquid of the stratification Hou Qu lower layer containing wadding fibrous element is spare；
(2) the mixed liquid containing wadding fibrous element was collected into upper layer turbid with 10000 r/m high speed centrifugation 15 minutes, bottom is cotton-shaped
In cellulose plus water is mixed after becoming cloudy and is centrifuged again, is so repeatedly recycled, until after separating in the wadding fibrous element in bottom
Until adding water mixing not become cloudy, merge gained turbid, for stable nano cellulose sol liquid；
(3) 2g microcrystalline cellulose is crushed, is sieved with 100 mesh sieve, obtain 100 mesh cellulose powders；
(4) the made nano cellulose sol liquid of 200ml is taken to be uniformly mixed with 2g microcrystal cellulose powder；
(5) mixture made from step (4) is first placed to 0.5h under 80 DEG C of water bath condition to constant temperature, then adds at this temperature
The Silane coupling agent KH550 for entering 1g stirs under constant temperature air-proof condition, reacts 5h；
(6) stop can observe mixed liquor after reacting by turbid change clearly, then the product that step (5) is reacted was washed with water and is filtered dry
Only, the substances such as silane coupling agent remaining in the reaction are removed, after obtaining nano-cellulose/Microcrystalline cellulose composite, 80
It is dried at DEG C, cellulose utilization rate is up to 90.5%；
It (7) is by mass percentage respectively 0.5 % of nano-cellulose/cellulose composite, 96 % of polylactic acid, nano-titanium dioxide
0.5 %, SEBS 1.5 % and PEG-4000 1.5% ratio weigh, be put into togerther in high-speed mixer after mixing 5 min and take
Out, mixture is obtained；Remaining (8), (9), the experimental procedure of (10) are identical as embodiment 1.
Mechanics Performance Testing, Nanowire manufactured in the present embodiment are carried out according to national standards to material standard batten obtained
Dimension element/cellulose composite enhancing polylactic acid 3D printing material mechanical property and 3D printing performance test results are shown in Table 1.
Embodiment 5
A kind of enhancing polylactic acid 3D printing material, is prepared from the following steps:
(1) acid being mixed into after crushing 2g needle-leaved wood fibre element with+20 ml oleic acid of 20 ml phosphoric acid is at 50 DEG C of waters bath with thermostatic control
1h is managed until solution slightly turns to be yellow, is diluted after stopping reaction with 400 ml water；Stratification Hou Qu lower layer contains wadding fibrous element
Mixed liquid it is spare；
(2) the mixed liquid containing wadding fibrous element was collected into upper layer turbid with 8000 r/m high speed centrifugation 15 minutes, by the cotton-shaped fibre in bottom
It ties up in element plus water is mixed after becoming cloudy and is centrifuged again, so multiple circulation, until adding in the wadding fibrous element in bottom after separating
Until water mixing does not become cloudy, merge gained turbid, for stable nano cellulose sol liquid；
(3) 2g filter paper paper cellulose is crushed, crosses 150 meshes, obtains 150 mesh cellulose powders.
(4) the made nano cellulose sol liquid of 200ml is taken to be uniformly mixed with 2g cellulose powder.
(5) mixture made from step (4) is first placed into 0.5h under 85 DEG C of water bath condition to constant temperature, then the temperature
The lower silane coupling agent KH570 that 1g is added, is stirred under constant temperature air-proof condition, reacts 5h.
(6) it can observe mixed liquor after stopping reaction and become clear by turbid, then the product that step (5) is reacted was washed with water
It is filtered dry only, the substances such as silane coupling agent remaining in the reaction is removed, after obtaining nano-cellulose/cellulose composite, 80
It is dried at DEG C, cellulose utilization rate is up to 90.6%；
It (7) is by mass percentage respectively 0.5 % of nano-cellulose/cellulose composite, 96 % of polylactic acid, nano-titanium dioxide
0.5 %, SEBS 1.5 % and PEG-400 1.5% ratio weigh, be put into togerther in high-speed mixer after mixing 5 min and take out,
Obtain mixture；Remaining (8), (9), the experimental procedure of (10) are identical as embodiment 1.
Mechanics Performance Testing, Nanowire manufactured in the present embodiment are carried out according to national standards to material standard batten obtained
Dimension element/cellulose composite enhancing polylactic acid 3D printing material mechanical property and 3D printing performance test results are shown in Table 1.
Comparative example 1
This comparative example (nano-cellulose/cellulose other than filler is the 150 mesh microcrystalline celluloses without modifying nanometer cellulose
Compound is substituted for 150 mesh microcrystalline celluloses), remaining process conditions and step are same as Example 1.This comparative example is prepared micro-
Crystalline cellulose enhancing polylactic acid 3D printing material mechanical performance and 3D printing results of property are shown in Table 1.
Comparative example 2
(nano-cellulose/cellulose composite is substituted for commercially available this comparative example other than filler is commercially available cotton nano-cellulose
Cotton nano-cellulose), remaining process conditions and step are same as Example 1.The cotton nano-cellulose of this comparative example preparation
Enhancing polylactic acid 3D printing material mechanical performance and print performance the results are shown in Table 1.
1 gained nano-cellulose of table/cellulose polylactic acid 3D printing material appearance and printout performance
。
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of nano-cellulose/cellulose composite, which is characterized in that be made of the method comprising the following steps:
(1) water bath with thermostatic control acidolysis processing is carried out after crushing cellulose, then rear stratification is diluted with water, and takes lower layer containing cotton-shaped fibre
The mixed liquid for tieing up element is spare；
(2) the mixed liquid obtained by step (1) containing wadding fibrous element is carried out multiple high speed centrifugation, separation plus water to mix, is merged every
Secondary gained upper layer turbid, as stable nano cellulose sol；
(3) nano cellulose sol obtained by step (2) is uniformly mixed with a certain amount of cellulose powder；
(4) silane coupling agent is added into mixture made from step (3), reaction is precipitated, then washing and drying, as nanometer
Cellulose/cellulose composite.
2. nano-cellulose/cellulose composite according to claim 1, it is characterised in that: cellulose and fiber used
Plain powder is native cellulose or microcrystalline cellulose；Acid used is one of inorganic acid, middle strong acid, organic acid or a variety of；
The silane coupling agent is KH series silane coupling agent.
3. nano-cellulose/cellulose composite according to claim 1, it is characterised in that: constant temperature used in step (1)
Water bath condition is 45-60 DEG C；Thinned water amount is 10-20 times of volume of acquired solution；Acidolysis is handled until solution jaundice；Step
Suddenly (2) high speed centrifugation is to be centrifuged 5-20 min every time with 8000-12000 r/min, until after separation in the wadding fibrous element in bottom
Until adding water mixing not become cloudy；Mixture is first placed to constant temperature, so under 75-85 DEG C of water bath condition in step (4) reaction
Being added afterwards with cellulose powder mass ratio is (1-10): the silane coupling agent of (1-10) is stirred to react under constant temperature air-proof condition
4-5 h。
4. nano-cellulose/cellulose composite according to claim 2, it is characterised in that: acid used is quality point
One of the number hydrochloric acid of 20-38%, the sulfuric acid of 50-64%, oleic acid, phosphoric acid or a variety of mixing.
5. nano-cellulose/cellulose composite according to claim 2, it is characterised in that: the silane coupling agent is
γ aminopropyltriethoxy silane, γ-glycidyl ether oxygen propyl trimethoxy silicane and γ-(methacryloxypropyl) third
One of base trimethoxy silane.
6. nano-cellulose/cellulose composite according to claim 1, it is characterised in that: nanometer used in step (3)
The mass ratio of cellulose sol and cellulose powder is (10-500): 1.
7. a kind of enhancing polylactic acid 3D printing material, which is characterized in that its raw material includes any one of claim 1-6 nanometer
Cellulose/cellulose composite and polylactic acid.
8. enhancing polylactic acid 3D printing material according to claim 7, which is characterized in that its raw material includes: the Nanowire
Tie up element/cellulose composite 0.1-2%, polylactic acid 90-98%, inorganic nano material 0.1-3%, toughener 0.1-5% and plasticizer
0.1-5%。
9. enhancing polylactic acid 3D printing material according to claim 7, which is characterized in that the molecular weight of the polylactic acid is
1.0×106-3.0×106；The inorganic nano material is nano silica, nano-titanium dioxide, nano zirconium dioxide, receives
One of rice calcium carbonate；The toughener is styrene-butadiene-embedding copolymer of benzene second, thermoplastic polystyrene-polybutadiene
One of alkene-polystyrene block copolymer, thermoplastic polyurethane elastomer, thermoplastic polyester elastomer；The plasticizer
For polyethylene glycol, molecular weight 1000-20000.
10. enhancing the preparation method of polylactic acid 3D printing material described in claim 8, it is characterised in that: the following steps are included:
(1) in proportion by the nano-cellulose/cellulose composite and polylactic acid, inorganic nano material, toughener, plasticizer
Blend composition is formed through mixed at high speed；
(2) by gained blend composition by double screw extruder melting extrusion and pelletizing, 1-6 sections of temperature of extruder are respectively 170-
175 DEG C, 170-177 DEG C, 175-180 DEG C, 180-185 DEG C, 180-185 DEG C and 185-190 DEG C, obtain pellet, fill in 80-85 DEG C
Divide drying；
(3) gained pellet squeezed out by single screw extrusion machine, drawn, 3D printing wire rod, the 1-4 section of extruder are processed into coiling
Temperature is respectively 170-180 DEG C, 175-185 DEG C, 180-190 DEG C, 180-190 DEG C, hauling speed be 50-60mm/s to get.
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