CN116445172A - Triazophenylcarbazole-containing 4D printing shape memory resin material of discotic photo-curing liquid crystal, and preparation method and application thereof - Google Patents
Triazophenylcarbazole-containing 4D printing shape memory resin material of discotic photo-curing liquid crystal, and preparation method and application thereof Download PDFInfo
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- CN116445172A CN116445172A CN202310351090.8A CN202310351090A CN116445172A CN 116445172 A CN116445172 A CN 116445172A CN 202310351090 A CN202310351090 A CN 202310351090A CN 116445172 A CN116445172 A CN 116445172A
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- 238000007639 printing Methods 0.000 title claims abstract description 62
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 52
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 title claims abstract description 47
- 239000011347 resin Substances 0.000 title claims abstract description 26
- 229920005989 resin Polymers 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 21
- -1 imide diene Chemical class 0.000 claims abstract description 20
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004997 Liquid crystal elastomers (LCEs) Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 23
- 239000004985 Discotic Liquid Crystal Substance Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 239000003431 cross linking reagent Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical group CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229920001971 elastomer Polymers 0.000 claims description 4
- 239000000806 elastomer Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 238000001723 curing Methods 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- AYNNSCRYTDRFCP-UHFFFAOYSA-N triazene Chemical compound NN=N AYNNSCRYTDRFCP-UHFFFAOYSA-N 0.000 claims 2
- 230000004044 response Effects 0.000 abstract description 13
- 230000007704 transition Effects 0.000 abstract description 5
- 150000002148 esters Chemical class 0.000 abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 4
- ZISGLVMVAWKGRE-UHFFFAOYSA-N C1=CC=CC=2C3=CC=CC=C3NC12.N1=NN=CC=C1 Chemical compound C1=CC=CC=2C3=CC=CC=C3NC12.N1=NN=CC=C1 ZISGLVMVAWKGRE-UHFFFAOYSA-N 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 238000010146 3D printing Methods 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003446 memory effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002520 smart material Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3833—Polymers with mesogenic groups in the side chain
- C09K19/3842—Polyvinyl derivatives
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3833—Polymers with mesogenic groups in the side chain
- C09K19/3895—Polymers with mesogenic groups in the side chain containing two or more mesogenic groups per monomer unit, e.g. polyitaconates, polymaleates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention belongs to the technical field of materials, and discloses a 4D printing shape memory resin material containing a triazophenylcarbazole disk-like photo-curing liquid crystal, and a preparation method and application thereof; the invention adopts a large conjugated condensed ring structure with more sensitive photoelectric response performance, wherein the large conjugated condensed ring structure is directly connected with carbazole to replace the traditional ester-based interval benzene ring, and imide diene with more stable and higher photopolymerization efficiency is introduced to replace the traditional ester mono-olefin, so that a series of photopolymerization liquid crystal monomers with disc-shaped structures are prepared, and the high conjugated enhanced shape memory triazine carbazole disc-shaped liquid crystal elastomer material capable of being excited near room temperature is prepared. The problems that the photoelectric response of the traditional 4D printing phenyl ester liquid crystal elastomer material is slow, the photopolymerization efficiency is low, the mechanical strength is insufficient, the phase transition temperature is too high, the printing parameters are complicated to regulate and control and the like are solved.
Description
Technical Field
The invention belongs to the technical field of materials, relates to preparation of D printing materials, and in particular relates to a triazophenylcarbazole disc-shaped photo-curing liquid crystal monomer, a 4D printing shape memory resin material, and a preparation method and application thereof.
Background
Compared with the traditional mold forming technology, the additive manufacturing technology has key advantages for various complex fine structures and personalized customized products. Additive manufacturing techniques accumulate the formation of facets from point to point, and accumulate the formations from facet to facet, so that three-dimensional entities of any complex shape can be manufactured, and are therefore also known as 3D printing. In recent years, on the basis of 3D printing, by introducing special stimulus response intelligent materials, printed products can generate physical properties such as structures, shapes and the like which change with time. The method has important significance for modern intelligent drivers, sensors, soft robots and other applications.
Liquid crystals refer to a class of materials that have the fluidity of liquids, while retaining the anisotropic character of crystalline molecules, either over a range of temperatures or under some solvent conditions. Particularly for thermotropic liquid crystal, liquid crystal molecules are aligned and oriented under the action of light, electricity, magnetism and the like in a certain temperature range, so that the change of structural performance is realized. Therefore, liquid crystals are an ideal class of 4D printing smart materials. The 4D printing liquid crystal materials reported today are mainly focused on phenyl ester liquid crystals (Science Advances,2021,7, eabg3677.; ACS Applied Materials & Interfaces,2021,13,12698.; ACS Applied Materials & Interfaces,2020,12,15562.; advanced Materials,2018,30,1706164.; smart Materials and Structures,2018,27,125011.; advanced Functional Materials,2019,29,1806412.; nature Communications,2018,9,8502.). The preparation process and commercial products of the phenyl ester liquid crystal are mature and the products are easy to purchase due to the great commercial success in the liquid crystal display direction. However, when the display type liquid crystal structure is applied to 4D printing, various problems are generated, such as complex printing process, slow driving response performance of an acrylate crosslinked network, insufficient mechanical properties of products and the like caused by the excessively high phase transition temperature of liquid crystal. Even though the defects of printing temperature and strength are improved to a certain extent through chain extension and doping, new problems are caused, such as poor compatibility of a doping system, weak interfacial adhesion between layers, inconsistent orientation cooperativity and the like.
Therefore, starting from a 4D printing liquid crystal resin structure, novel liquid crystal molecules are designed and prepared, the performance is improved from the source of a modified material structure, and a series of liquid crystal resin materials with sensitive photoelectric response, photopolymerization efficiency, good mechanical properties and thermal properties are developed, so that the method has important significance for improving the research of 4D printing application.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a triazophenylcarbazole disk-shaped photo-curing liquid crystal monomer, a 4D printing shape memory resin material, and a preparation method and application thereof; the invention adopts a large conjugated condensed ring structure with more sensitive photoelectric response performance, wherein the large conjugated condensed ring structure is directly connected with carbazole to replace the traditional ester-based interval benzene ring, and imide diene with more stable and higher photopolymerization efficiency is introduced to replace the traditional ester mono-olefin, so that a series of photopolymerization liquid crystal monomers with disc-shaped structures are prepared, and the high conjugated enhanced shape memory triazine carbazole disc-shaped liquid crystal elastomer material capable of being excited near room temperature is prepared. The problems that the photoelectric response of the traditional 4D printing phenyl ester liquid crystal elastomer material is slow, the photopolymerization efficiency is low, the mechanical strength is insufficient, the phase transition temperature is too high, the printing parameters are complicated to regulate and control and the like are solved.
The invention is realized by the following technical scheme:
a disk-shaped photo-curing liquid crystal monomer of the triazophenylcarbazole has the following structural general formula:
wherein R is 1 、R 2 、R 3 Identical or different, selected from H, D, F, -CN, -NO 2 、-CF 3 Alkenyl, alkynyl, amino, acyl, amido, cyano, isocyano, alkoxy, hydroxyl, carbonyl, sulfonyl, substituted or unsubstituted alkyl with 1 to 30 carbon atoms;
X 1 、X 2 、X 3 identical or different, selected from H, D, F, -CN, -NO 2 、-CF 3 Alkenyl, alkynyl, amino, acyl, amido, cyano, isocyano, alkoxy, hydroxy, carbonyl, sulfonyl, substituted or unsubstituted alkyl having 1 to 30 carbon atoms, and X 1 、X 2 、X 3 At least one of which contains a photopolymerizable end group;
the photopolymerisable terminal groups are selected from the following structures:
the invention further improves the scheme as follows:
A4D printing shape memory resin material is prepared from the triazophenylcarbazole disk-shaped photo-curing liquid crystal monomer.
The invention further improves the scheme as follows:
a method for preparing a 4D printed shape memory resin material, comprising the steps of:
(1) Adding the triazophenylcarbazole photo-curing discotic liquid crystal monomer, a cross-linking agent and a photoinitiator into a solvent to prepare a precursor solution of 4D printing resin;
(2) The precursor solution obtained by photo-curing printing is utilized to obtain a carbazole liquid crystal elastomer material with a three-dimensional structure;
(3) And (3) re-solidifying the obtained three-dimensional structure triazophenylcarbazole discotic liquid crystal elastomer material, and then performing vacuum drying to obtain the 4D printing shape memory resin material.
Further, the mass ratio of the triazaphenylcarbazole photo-curing discotic liquid crystal monomer to the crosslinking agent to the photoinitiator is 1:0.001-0.1:0.01-0.5.
Preferably, the mass ratio of the triazaphenylcarbazole photo-curing discotic liquid crystal monomer to the crosslinking agent to the photoinitiator is 1:0.01-0.03:0.1-0.3.
Further, the cross-linking agent is n-butylamine.
Further, the photoinitiator is 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinophenyl) butanone.
Further, the solvent is one or more of water, tetrahydrofuran or ethanol.
Further, the printing temperature in the step (2) is 20-60 ℃; the temperature of the photo-curing in the step (3) is 20-60 ℃.
Preferably, the printing temperature in the step (2) is 20-40 ℃; the temperature of the photo-curing in the step (3) is 20-40 ℃.
The invention further improves the scheme as follows:
application of the 4D printing shape memory resin material in the fields of drivers, soft robots or sensors
Compared with the prior art, the invention has the beneficial effects that:
current 4D printing devices mainly include Fused Deposition (FDM), direct Ink Writing (DIW), ink-jet printing (Ink-jet), digital Light Processing (DLP), and the like. In the existing printing technology, DLP is a novel 4D printing technology based on photo-curing, utilizes photo-polymerization materials to construct a three-dimensional structure, is not limited by the physical size of a nozzle (100-200 mu m) in the traditional printing mode, can be used for preparing a complex structure with superfine characteristics, has the precision of several micrometers to hundreds of nanometers, and is an ideal high-precision 4D printing technology. The invention realizes high-precision 4D printing of the photo-curing discotic liquid crystal monomer containing the triazophenylcarbazole by utilizing a DLP 4D printing technology.
The invention adopts a large conjugated condensed ring structure with more sensitive photoelectric response performance, wherein the large conjugated condensed ring structure is directly connected with the carbazole to replace the traditional ester-based interval benzene ring, and introduces imide diene with more stability and higher photopolymerization efficiency to replace the traditional ester-based monoene, so as to prepare a series of photopolymerization liquid crystal monomers with disc-shaped structures.
The invention prepares the high conjugated enhanced shape memory tri-azophenylcarbazole discotic liquid crystal elastomer material which can be excited near room temperature by the tri-azophenylcarbazole photo-curing discotic liquid crystal monomer, and the material has the advantages of quicker photoelectric response, higher photo-curing efficiency, better mechanical property and thermal property. The problems that the photoelectric response of the traditional 4D printing phenyl ester liquid crystal elastomer material is slow, the photopolymerization efficiency is low, the mechanical strength is insufficient, the phase transition temperature is too high, the printing parameters are complicated to regulate and control and the like are solved.
The large conjugated condensed ring structure directly connected with the tri-nitrogen benzene and the carbazole replaces the traditional ester group interval benzene ring, so that not only is the mechanical property improved, but also a liquid crystal structure in a disk-like phase state is formed. Compared with the traditional nematic or smectic phenyl ester liquid crystal, the distance between the disk layers of the disk-shaped liquid crystal is more compact, and the large plane conjugation derived from the triazophenylcarbazole is very beneficial to realizing the improvement of carrier transmission and photoelectric response. Meanwhile, the N-position on the carbazole unit is convenient for introducing an alkyl chain, and is used for regulating and controlling the liquid crystal phase transition temperature and the photo-curing printing temperature. In addition, the invention adopts the imide diene to replace the traditional ester mono-olefin, thereby realizing a more stable and more efficient photo-curing process.
The invention adopts a high-precision DLP 4D printing mode, and prepares the enhanced 4D printing shape memory triazocarbazole discotic liquid crystal elastomer material capable of being excited near room temperature (20-40 ℃) by regulating and controlling parameters such as the photo-curing discotic liquid crystal monomer, the cross-linking agent, the initiator, the photo-curing printing temperature, the solvent type and the like and optimizing the photoelectric response performance, the photo-curing efficiency, the mechanical property, the thermal property and the like of the material.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Adding a certain proportion of triazophenylcarbazole photo-curing liquid crystal (NBCLC for short), n-butylamine, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinophenyl) butanone (I-369 for short) and the like into a certain amount of solvent to prepare the 4D printing resin precursor solution. The three-dimensional structure was printed out by DLP method, then the sample was photo-cured for 5-20 minutes, and finally the product was dried in vacuum overnight. The shape memory structure which can be excited near room temperature is obtained.
Example 1
Preparation of the Triazophenylcarbazole photo-curing liquid Crystal monomer (NBCLC-1)
The reaction scheme is as follows:
synthesis of intermediate (3)
To a 500mL flask under nitrogen protection were added intermediate (1) (10 g,20.74 mmol) and boric acid intermediate (2) (21.99 g,62.24 mmol) while 250mL toluene was added as a solvent, and the apparatus was mounted. Potassium carbonate (8.59 g,62.24 mmol) was taken and completely dissolved with 30ml of water and added to the flask. Pd (PPh 3) 4 (1.43 g,1.24 mmol) was then added to the flask, air was removed from the flask by an oil pump, nitrogen was introduced, and the mixture was heated at constant temperature for reflux reaction for 12 hours, followed by cooling. Transferring the reaction solution into a rotary evaporation bottle, evaporating most of the solvent by rotary evaporation, extracting with dichloromethane, washing with water for three times, drying with anhydrous magnesium sulfate, filtering, drying by rotary evaporation, and purifying to obtain the intermediate (3) with the yield of 78%.
Synthesis of intermediate (4)
A500 mL flask was placed in an ice bath under nitrogen and intermediate (3) (10 g,8.57 mmol) and 200mL dichloromethane were added. Boron tribromide (25.71 mL,25.71mmol,1 mol/L) was then added dropwise. The resulting solution was warmed to room temperature of 25℃and stirred for 12 hours. The reaction solution was poured into 200mL of ice water and stirred for 1 hour, followed by extraction with ethyl acetate, washing with water three times, drying over anhydrous magnesium sulfate, filtration and spin-drying, and purification to give intermediate (4) in 68% yield.
Synthesis of liquid Crystal Compound (NBCLC-1)
To a 500mL flask under nitrogen protection were added intermediate (4) (10 g,8.88 mmol) and potassium carbonate (3.68 g,26.64 mmol) while 250mLN, N-dimethylformamide were added, and the reaction was continued for 24 hours after heating to 90℃for 12 hours, and then intermediate (5) (8.43 g,26.64 mmol) was added. The reaction solution was poured into water, extracted with methylene chloride, washed with water three times, dried over anhydrous magnesium sulfate, filtered and dried by spin, and purified to give a liquid crystal compound (NBCLC-1) in 65% yield.
Preparing a 4D printing shape memory resin material:
triazophenylcarbazole photo-curing liquid crystal (NBCLC-1, 10g for short), n-butylamine (1 g) and initiator I-369 (0.1 g) were added to tetrahydrofuran (100 mL) solvent. And (3) adding the mixture into a Digital Light Processing (DLP) 3D printer after shaking and mixing uniformly, performing photo-curing printing, printing out a three-dimensional structure by using a DLP method, performing photo-curing on a sample for 5-20 minutes, and finally drying the product in vacuum overnight.
Example 2
Preparation of the Triazophenylcarbazole photo-curing liquid Crystal monomer (NBCLC-2)
NBCLC-2
The reaction scheme is as follows:
synthesis of liquid Crystal Compound (NBCLC-2)
To a 500mL flask under nitrogen protection were added intermediate (4) (10 g,8.88 mmol) and potassium carbonate (3.68 g,26.64 mmol) while 250mLN, N-dimethylformamide were added, and the reaction was continued for 24 hours after heating to 90℃for 12 hours, followed by addition of intermediate (5) (8.08 g,26.64 mmol). The reaction solution was poured into water, extracted with methylene chloride, washed with water three times, dried over anhydrous magnesium sulfate, filtered and dried by spin, and purified to give a liquid crystal compound (NBCLC-2) in 61% yield.
Preparing a 4D printing shape memory resin material:
triazophenylcarbazole photo-curing liquid crystal (NBCLC-2, 10g for short), n-butylamine (1 g), initiator I-369 (0.1 g) were added to tetrahydrofuran (100 mL) solvent. And (3) adding the mixture into a Digital Light Processing (DLP) 3D printer after shaking and mixing uniformly, performing photo-curing printing, printing out a three-dimensional structure by using a DLP method, performing photo-curing on a sample for 5-20 minutes, and finally drying the product in vacuum overnight.
Comparative example 1
A conventional phenyl ester photo-curing liquid crystal monomer (RM 82 for short, structure shown below, 10 g), n-butylamine (1 g) and an initiator I-369 (0.1 g) are added into a tetrahydrofuran (100 mL) solvent. And adding the mixture into a Digital Light Processing (DLP) 3D printer after shaking and mixing uniformly, and performing photo-curing printing.
For comparative study of the photocuring crosslinking properties of imidodienes and acrylic esters, the present invention utilizes OmniCure S2000 spot UV curing system equipment, and the uv flux settings select S2000 apecture and UV exposure timing settings and OmniCure R2000 UV spot curing radiometer systems. The wavelength of ultraviolet light is 365nm, and the flux of ultraviolet light is 600J/cm 2 . The liquid crystal materials of examples and comparative examples were dissolved in chlorobenzene to prepare 10mg/cm 3 Then spin-coated on the surface of the oxygen plasma-treated glass substrate at 2000rpm with an acceleration of 2000units for 30 seconds.
In order to compare the influence of the triazophenylcarbazole photo-curing discotic liquid crystal and the phenyl ester photo-curing nematic liquid crystal on 4D printing process parameters and product performance, the invention compares the excitation temperature, the driving voltage and the tensile strength of the shape memory effect of the printed product, and the comparison result is shown in the following table:
the discotic liquid crystal has six groups of photo-polymerizable olefin double bonds, has higher photo-curing efficiency than the acrylic ester with two groups of double bonds in the comparative example, has higher stability than ester groups in the reaction process, and has high-efficiency performance in the preparation of a 4D printing structure and the photo-curing crosslinking process.
The invention has the advantages of high conjugated condensed ring structure directly connected by the tri-nitrogen benzene and carbazole, chemically stable high-efficiency photopolymerized imide dienyl group, ordered molecular structure arranged discotic liquid crystal, and the combination of the advantages is favorable for carrier transmission, thereby realizing lower driving voltage and improving the photoelectric response performance of the 4D printing structure. The liquid crystal with the rigid large conjugated structure provides higher tensile strength and mechanical property for the 4D printing structure, and meanwhile, the shape memory effect driving near the room temperature of the 4D printing structure is realized by a plurality of long flexible alkyl chains led out by carbazole units.
The foregoing embodiments are merely illustrative of the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and to implement the same, not to limit the scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (9)
1. A4D printing shape memory resin material containing a triazene carbazole disc-shaped photo-curing liquid crystal is characterized by being prepared from a triazene carbazole disc-shaped photo-curing liquid crystal monomer;
the structural general formula of the triazophenylcarbazole disk-shaped photo-curing liquid crystal monomer is shown as follows:
wherein R is 1 、R 2 、R 3 Identical or different, selected from H, D, F, -CN, -NO 2 、-CF 3 Alkenyl, alkynyl, amino, acyl, amido, cyano, isocyano, alkoxy, hydroxyl, carbonyl, sulfonyl, substituted or unsubstituted alkyl with 1 to 30 carbon atoms;
X 1 、X 2 、X 3 identical or different, selected from H, D, F, -CN, -NO 2 、-CF 3 Alkenyl, alkynyl, amino, acyl, amido, cyano, isocyano, alkoxy, hydroxy, carbonyl, sulfonyl, substituted or unsubstituted alkyl having 1 to 30 carbon atoms, and X 1 、X 2 、X 3 At least one of which contains a photopolymerizable end group;
the photopolymerisable terminal groups are selected from the following structures:
2. the preparation method of the 4D printing shape memory resin material containing the triazophenylcarbazole disc-shaped photo-curing liquid crystal is characterized by comprising the following steps of:
(1) Adding the triazophenylcarbazole photo-curing discotic liquid crystal monomer, a cross-linking agent and a photoinitiator into a solvent to prepare a precursor solution of the 4D printing resin;
(2) The precursor solution obtained by photo-curing printing is utilized to obtain a carbazole liquid crystal elastomer material with a three-dimensional structure;
(3) And (3) re-solidifying the obtained three-dimensional structure triazophenylcarbazole discotic liquid crystal elastomer material, and then performing vacuum drying to obtain the 4D printing shape memory resin material.
3. The method for preparing the 4D printing shape memory resin material containing the triazophenylcarbazole disc-like photo-curing liquid crystal according to claim 2, wherein the method comprises the following steps: the mass ratio of the triazophenylcarbazole photo-curing discotic liquid crystal monomer to the cross-linking agent to the photoinitiator is 1:0.001-0.1:0.01-0.5.
4. The method for preparing a 4D printing shape memory resin material containing a triazophenylcarbazole discotic photo-curing liquid crystal according to claim 3, wherein the method comprises the following steps: the mass ratio of the triazophenylcarbazole photo-curing discotic liquid crystal monomer to the cross-linking agent to the photoinitiator is 1:0.01-0.03:0.1-0.3.
5. The method for preparing the 4D printing shape memory resin material containing the triazophenylcarbazole disc-like photo-curing liquid crystal according to claim 2, wherein the method comprises the following steps: the cross-linking agent is n-butylamine.
6. The method for preparing the 4D printing shape memory resin material containing the triazophenylcarbazole disc-like photo-curing liquid crystal according to claim 2, wherein the method comprises the following steps: the photoinitiator is 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinophenyl) butanone.
7. The method for preparing the 4D printing shape memory resin material containing the triazophenylcarbazole disc-like photo-curing liquid crystal according to claim 2, wherein the method comprises the following steps: the solvent is one or more of water, tetrahydrofuran or ethanol.
8. The method for preparing the 4D printing shape memory resin material containing the triazophenylcarbazole disc-like photo-curing liquid crystal according to claim 2, wherein the method comprises the following steps: the printing temperature in the step (2) is 20-60 ℃; the curing temperature in the step (3) is 20-60 ℃.
9. Use of a 4D printed shape memory resin material comprising a triazophenylcarbazole discotic photo-curable liquid crystal as claimed in claim 1 in the field of drivers, soft robots or sensors.
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