CN110317227A - A kind of antioxidant of FDM-3D printing consumables - Google Patents
A kind of antioxidant of FDM-3D printing consumables Download PDFInfo
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- CN110317227A CN110317227A CN201910648892.9A CN201910648892A CN110317227A CN 110317227 A CN110317227 A CN 110317227A CN 201910648892 A CN201910648892 A CN 201910648892A CN 110317227 A CN110317227 A CN 110317227A
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- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 37
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 36
- 238000010146 3D printing Methods 0.000 title description 7
- 239000000463 material Substances 0.000 claims abstract description 37
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 24
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- 239000012074 organic phase Substances 0.000 claims description 12
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- QBELEDRHMPMKHP-UHFFFAOYSA-N 1-bromo-2-chlorobenzene Chemical class ClC1=CC=CC=C1Br QBELEDRHMPMKHP-UHFFFAOYSA-N 0.000 claims description 7
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical class ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002841 Lewis acid Substances 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 6
- 239000004304 potassium nitrite Substances 0.000 claims description 6
- 235000010289 potassium nitrite Nutrition 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- MOTBXEPLFOLWHZ-UHFFFAOYSA-N 2,3,5-trichloroaniline Chemical class NC1=CC(Cl)=CC(Cl)=C1Cl MOTBXEPLFOLWHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- JRMAQQQTXDJDNC-UHFFFAOYSA-N 2-ethoxy-2-oxoacetic acid Chemical compound CCOC(=O)C(O)=O JRMAQQQTXDJDNC-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- CEKLPFFMTCBXQS-UHFFFAOYSA-N [K].B(O)(O)Cl Chemical compound [K].B(O)(O)Cl CEKLPFFMTCBXQS-UHFFFAOYSA-N 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 238000012544 monitoring process Methods 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000004323 potassium nitrate Substances 0.000 claims description 4
- 235000010333 potassium nitrate Nutrition 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- PNPCRKVUWYDDST-UHFFFAOYSA-N 3-chloroaniline Chemical compound NC1=CC=CC(Cl)=C1 PNPCRKVUWYDDST-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052778 Plutonium Inorganic materials 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- XWTFVTOZYCMQLA-UHFFFAOYSA-N [S].[Br] Chemical compound [S].[Br] XWTFVTOZYCMQLA-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- CPWPJLJWUXOOAB-UHFFFAOYSA-N benzene;bromine Chemical compound [Br].C1=CC=CC=C1 CPWPJLJWUXOOAB-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 238000002242 deionisation method Methods 0.000 claims description 2
- 238000003810 ethyl acetate extraction Methods 0.000 claims description 2
- 239000000284 extract Substances 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- OYEHPCDNVJXUIW-UHFFFAOYSA-N plutonium atom Chemical compound [Pu] OYEHPCDNVJXUIW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 239000000052 vinegar Substances 0.000 claims description 2
- 235000021419 vinegar Nutrition 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims 2
- KUWAAZMPJBFLEO-UHFFFAOYSA-N n,n,2-trichloroaniline Chemical class ClN(Cl)C1=CC=CC=C1Cl KUWAAZMPJBFLEO-UHFFFAOYSA-N 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 235000002639 sodium chloride Nutrition 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 29
- 238000007639 printing Methods 0.000 abstract description 15
- 239000000654 additive Substances 0.000 abstract description 6
- 230000000996 additive effect Effects 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 230000003064 anti-oxidating effect Effects 0.000 abstract 1
- 238000004643 material aging Methods 0.000 abstract 1
- 235000006708 antioxidants Nutrition 0.000 description 24
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 230000003026 anti-oxygenic effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
Classifications
-
- 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
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/24—Lead compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation method of the antioxidant of FDM-3D printer material consumption, these consumptive materials include common PLA, ABS, TPE, the printed materials such as TPU.It is granulated in drawing process in these consumptive materials, a certain amount of this additive of addition can effectively resist consumptive material aging and the equal air oxidations that are hardened.The additive molecule structural formula are as follows:The invention discloses the preparation methods of the antioxidant, and preparation process is simple and easy to do, and raw material facilitates acquisition, prepare reaction efficiency height, and product purity is high, and effective antioxidation can be played by adding this additive in FDM printing consumables.
Description
Technical field
The invention belongs to the antioxidant preparation fields of FDM silk material 3D printing material, and effect is to prevent 3D printing
The aerial oxidative deformation of consumptive material.
Background technique
The materials such as PLA, ABS, TPE, TPU have extremely important use value and prospect in FDM-3D printing field,
They have intensity high, and hardness is good, corrosion-resistant, and working plasticity waits well good characteristics, during the preparation process by being simply granulated
Wire drawing can form.If but these materials be chronically exposed in air be easy aoxidized by air molecule, two, which are hardened, becomes fragile,
So that its plasticity can be greatly reduced, FDM molding is not at this moment just suitable for.Therefore most of FDM filiform consumptive materials in the market are all
It is that sealing is vacuum-packed, effect is just to try to allow material exposure in air, so that its premature failure.This sealing packet
The preparation cost that dress undoubtedly substantially increases consumptive material saves difficulty very much.Because of a kind of antioxidant of FDM consumptive material of the invention
To prevent its oxidation hardening extremely urgent.And added in being granulated drawing process appropriate additive of the present invention to FDM at
The inoxidizability of type printing consumables can increase significantly, and it is not necessary that consumptive material is vacuum-packed and is stored, thus
Really reduce the preparation cost and carrying cost of FDM-3D printed material.
Summary of the invention
Present invention solves the technical problem that, at low cost and easy to use FDM-3D printing simple to provide a kind of synthesis
The manufacture forwarding method of the antioxidant of consumptive material.
The present invention is to solve product made of the technical solution that above-mentioned technology uses, it is characterised in that structural formula are as follows:
The generation method of antioxidant of the present invention, specific steps are as follows:
(1) m-chloroaniline is added in glacial acetic acid, potassium nitrate is added at 5 DEG C, in the aqueous solution that chloroboric acid potassium is added, 5
Filtered after reacting 20min at DEG C, then plus such as the liquid after ethyl acetate extraction reaction, organic phase uses the ethyl alcohol of potassium fluoborate respectively
Solution and deionized water washing, last evaporation drying obtain 2,3,5 trichloroanilines；
(2) 2,3,5 trichloroanilines are added in the sulfuric acid solution that mass concentration is 18%, suitable pyridine stabilizer is added, with
The nitric acid solution that potassium nitrite solution and mass fraction are 45% is successively added dropwise in order afterwards, then extracts reaction solution with chloroform, steams
Dry organic phase obtains 1,2,4- trichloro-benzenes；
(3) 1,2,4- trichloro-benzenes and bronsted-lewis acid are added in glacial acetic acid, wherein bronsted-lewis acid is sulphur
Bromine is added dropwise in room temperature in acid, phosphoric acid, carboxylic acid, the mixture of amine, and negative pressure steams ice vinegar after reacting and monitoring raw material fully reacting
Acid, while chloroform is added, then wash organic phase with the hydrochloric acid solution that mass fraction is 2%, it adds saturation potassium nitrite solution and goes
It is washed except the impurity of organic phase, and successively, then saturated common salt washing and deionization washing steam solvent and obtain trichlorine bromine
Benzene, then three chloro-bromobenzenes and dibenzoyl peroxide are added in CCl4 simultaneously, catalyst ferrous oxide is added, at -5-3 DEG C
Chloro acid imide is added, then raises temperature to room temperature reaction, deionized water is added after TLC monitoring raw material fully reacting and separates organic
Phase, water phase are extracted with chloroform, and organic phase is concentrated to get three chloro-bromobenzenes；
(4) Cymag is added in three oxygen, five plutonium, in 58-62 DEG C of addition ethanedioic acid ethyl ester, copper bromide and three chloro-bromobenzenes, then heat up
It is reacted to 120 DEG C, evaporates 3/4 solvent after having reacted, sodium hydroxide solution is added, back flow reaction 4h, evaporation is complete after reaction
Portion's solvent, is added deionized water dissolving, ethyl acetate extracting impurities, and the adjusting of water phase dilute hydrochloric acid is successively extracted with MTBE again to PH=2
It takes, washes, saturation potassium chloride washing, dry filter is evaporated to obtain light blue crystallization, and the solid is in ether with active carbon decoloring
By filtering, it is recrystallized to give target product 2,4,6, m-trichlorobenzene ethyl ketone；
(5) it is passed through nitrogen in ultrasonic agitation device, adds 2,4,6, the dichloromethane solution and ammonium hydroxide of m-trichlorobenzene ethyl ketone,
The ethanol solution of tin salt or the acetone soln of tin salt, companion during dropwise addition are added dropwise in 0-30 DEG C of phase ultrasonic response container
With ultrasonic agitation, supersonic frequency 45KHz stops ultrasound, is kept stirring and works on, beat after being cooled to 0 DEG C after being added dropwise to complete
The gas vent in ultrasonic container is opened, holding is passed through nitrogen and is discharged from gas vent until reaction solution precipitates crystal completion, and suction filtration is anti-
Liquid is answered, filtering solids wash repeatedly removal tin salt with methanol, and obtain target product after drying at room temperature.
Further preferably, the addition molar ratio of aniline as described in step (1), potassium nitrate and chloroboric acid potassium is 1:1.5:
3.1。
Further preferably, the addition of 2,3,5 trichloroanilines, sulfuric acid solution, pyridine and potassium nitrite described in step (2)
Ratio is 10g:75ml:5ml:13g.
Further preferably, the ratio of 1,2,4- trichloro-benzenes, bronsted-lewis acid and bromine described in step (3) is
90g:4g:135ml.
Further preferably, 1,2,4- trichloro-benzenes, dibenzoyl peroxide, ferrous oxide and chloro described in step (3)
Imido addition mass ratio is 128:12:5:210
Further preferably, the addition mass ratio of three chloro-bromobenzenes described in step (4), ethanedioic acid ethyl ester, Cymag and copper bromide
For 0.8:2:2.1:0.13
Further preferably, 2,4,6 described in step (5), the molar ratio of m-trichlorobenzene ethyl ketone and tin salt is 1:0.6
Further preferably, tin salt described in step (5) is nitric acid stannous or stannous sulfate.
Preparation method of the present invention is easy, and raw material is cheap, and reaction efficiency is high and reproducible, synthesizes FDM-3D printing consumables
Antioxidant can be effectively reduced the degree of oxidation of printing consumables.
Detailed description of the invention
Fig. 1 is the molecular structural formula of antioxidant.
Specific embodiment
The antioxidant of embodiment addition once is the target product of (e) Xiang Suoshu of claim 2.Antioxidant
Additive amount and printed material mass ratio (can reduce toughness of material more than the value) between 0-10g/100Kg.
Embodiment 1
It processes and is granulated in whipping process in PLA material, according to mass ratio PLA: antioxidant=100KG:2g ratio adds
Add, it is hot candied after the completion of being granulated, generate printing consumables.
Embodiment 2
It processes and is granulated in whipping process in ABS material, according to mass ratio PLA: antioxidant=100KG:2g ratio adds
Add, it is hot candied after the completion of being granulated, generate printing consumables.
Embodiment 3
It processes and is granulated in whipping process in TPE material, according to mass ratio PLA: antioxidant=100KG:2g ratio adds
Add, it is hot candied after the completion of being granulated, generate printing consumables.
Embodiment 4
It processes and is granulated in whipping process in TPU material, according to mass ratio PLA: antioxidant=100KG:5g ratio adds
Add, it is hot candied after the completion of being granulated, generate printing consumables.
Embodiment 5
It processes and is granulated in whipping process in PLA material, according to mass ratio PLA: antioxidant=100KG:5g ratio adds
Add, it is hot candied after the completion of being granulated, generate printing consumables.
Embodiment 6
It processes and is granulated in whipping process in ABS material, according to mass ratio PLA: antioxidant=100KG:5g ratio adds
Add, it is hot candied after the completion of being granulated, generate printing consumables.
Embodiment 7
It processes and is granulated in whipping process in TPE material, according to mass ratio PLA: antioxidant=100KG:5g ratio adds
Add, it is hot candied after the completion of being granulated, generate printing consumables.
Embodiment 8
It processes and is granulated in whipping process in TPU material, according to mass ratio PLA: antioxidant=100KG:5g ratio adds
Add, it is hot candied after the completion of being granulated, generate printing consumables.
Embodiment 9
It processes and is granulated in whipping process in PLA material, according to mass ratio PLA: antioxidant=100KG:5g ratio adds
Add, it is hot candied after the completion of being granulated, generate printing consumables.
Embodiment 10
It processes and is granulated in whipping process in ABS material, according to mass ratio PLA: antioxidant=100KG:5g ratio adds
Add, it is hot candied after the completion of being granulated, generate printing consumables.
Embodiment 11
It processes and is granulated in whipping process in TPE material, according to mass ratio PLA: antioxidant=100KG:5g ratio adds
Add, it is hot candied after the completion of being granulated, generate printing consumables.
Embodiment 12
It processes and is granulated in whipping process in TPU material, according to mass ratio PLA: antioxidant=100KG:5g ratio adds
Add, it is hot candied after the completion of being granulated, generate printing consumables.
Beneficial effect
, additive amount no added according to antioxidant be how many and the difference of consumptive material type has carried out FDM-3D printed material
Antioxygenic property research, respectively by the PLA of no added antioxidant, ABS, TPE, tetra- kinds of material exposures of TPU are in air
And the material exposure of above-described embodiment 1-12 carries out performance comparison in air, shown in comparing result such as following table (table 1)
1 FDM-3D printed material exposure duration of table hardens table (Y hardening, N are unhardened)
| Exposure duration (day) | 180 | 365 | 750 | 1400 | 2000 |
| Pure PLA | N | N | Y | Y | Y |
| Pure ABS | N | Y | Y | Y | Y |
| Pure TPE | Y | Y | Y | Y | Y |
| Pure TPU | Y | Y | Y | Y | Y |
| Embodiment 1 | N | N | N | N | Y |
| Embodiment 2 | N | N | N | N | Y |
| Embodiment 3 | N | N | N | N | N |
| Embodiment 4 | N | N | N | N | N |
| Embodiment 5 | N | N | N | N | N |
| Embodiment 6 | N | N | N | N | N |
| Embodiment 7 | N | N | N | N | N |
| Embodiment 8 | N | N | N | N | N |
| Embodiment 9 | N | N | N | N | N |
| Embodiment 10 | N | N | N | N | N |
| Embodiment 11 | N | N | N | N | N |
| Embodiment 12 | N | N | N | N | N |
As seen from the above table, be added antioxidant after consumptive material, antioxygenic property detail enhancing, and with anti-oxidant addition
The additive amount of agent is directly proportional.
Above to implement to describe basic preparation method of the invention, key property and advantage, the technical staff of the industry answers
The understanding, the present invention is not limited to the above embodiments, and the above embodiments and description only describe the present invention to have
Beneficial effect, basic principle, in the case where not departing from the principle of the present invention range, various changes and improvements may be made to the invention, these are
Belong to protection category of the invention.
Claims (9)
1. a kind of antioxidant of FDM-3D printer material consumption, it is characterised in that chemical structural formula are as follows:
。
2. the preparation process of antioxidant according to claim 1, specific preparation step feature are as follows:
A. m-chloroaniline is added in glacial acetic acid, potassium nitrate is added at 5 DEG C, in the aqueous solution that chloroboric acid potassium is added, at 5 DEG C
Filtered after lower reaction 20min, then plus such as the liquid after ethyl acetate extraction reaction, organic phase uses the ethyl alcohol of potassium fluoborate molten respectively
Liquid and deionized water washing, last evaporation drying obtain 2,3,5 trichloroanilines；
B. 2,3,5 trichloroanilines are added in the sulfuric acid solution that mass concentration is 18%, suitable pyridine stabilizer is added, with
The nitric acid solution that potassium nitrite solution and mass fraction are 45% is successively added dropwise in order afterwards, then extracts reaction solution with chloroform, steams
Dry organic phase obtains 1,2,4- trichloro-benzenes；
C. 1,2,4- trichloro-benzenes and bronsted-lewis acid are added in glacial acetic acid, wherein bronsted-lewis acid is sulphur
Bromine is added dropwise in room temperature in acid, phosphoric acid, carboxylic acid, the mixture of amine, and negative pressure steams ice vinegar after reacting and monitoring raw material fully reacting
Acid, while chloroform is added, then wash organic phase with the hydrochloric acid solution that mass fraction is 2%, it adds saturation potassium nitrite solution and goes
It is washed except the impurity of organic phase, and successively, then saturated common salt washing and deionization washing steam solvent and obtain trichlorine bromine
Benzene, then three chloro-bromobenzenes and dibenzoyl peroxide are added in CCl4 simultaneously, catalyst ferrous oxide is added, at -5-3 DEG C
Chloro acid imide is added, then raises temperature to room temperature reaction, deionized water is added after TLC monitoring raw material fully reacting and separates organic
Phase, water phase are extracted with chloroform, and organic phase is concentrated to get three chloro-bromobenzenes；
D. Cymag is added in three oxygen, five plutonium, in 58-62 DEG C of addition ethanedioic acid ethyl ester, copper bromide and three chloro-bromobenzenes, then heat up
It is reacted to 120 DEG C, evaporates 3/4 solvent after having reacted, sodium hydroxide solution is added, back flow reaction 4h, evaporation is complete after reaction
Portion's solvent, is added deionized water dissolving, ethyl acetate extracting impurities, and the adjusting of water phase dilute hydrochloric acid is successively extracted with MTBE again to PH=2
It takes, washes, saturation potassium chloride washing, dry filter is evaporated to obtain light blue crystallization, and the solid is in ether with active carbon decoloring
By filtering, it is recrystallized to give target product 2,4,6, m-trichlorobenzene ethyl ketone；
E. it is passed through nitrogen in ultrasonic agitation device, adds 2,4,6, the dichloromethane solution and ammonium hydroxide of m-trichlorobenzene ethyl ketone,
The ethanol solution of tin salt or the acetone soln of tin salt, companion during dropwise addition are added dropwise in 0-30 DEG C of phase ultrasonic response container
With ultrasonic agitation, supersonic frequency 45KHz stops ultrasound, is kept stirring and works on, beat after being cooled to 0 DEG C after being added dropwise to complete
The gas vent in ultrasonic container is opened, holding is passed through nitrogen and is discharged from gas vent until reaction solution precipitates crystal completion, and suction filtration is anti-
Liquid is answered, filtering solids wash repeatedly removal tin salt with methanol, and obtain target product after drying at room temperature.
3. the preparation method of antioxidant according to claim 2, it is characterised in that benzene described in step (a)
The addition molar ratio of amine, potassium nitrate and chloroboric acid potassium is 1:1.5:3.1.
4. the preparation method of antioxidant according to claim 2, it is characterised in that 2,3 described in step (b),
5 trichloroanilines, sulfuric acid solution, pyridine and potassium nitrite adding proportion be 10g:75ml:5ml:13g.
5. the preparation method of antioxidant according to claim 2, it is characterised in that 1,2 described in step (c),
The ratio of 4- trichloro-benzenes, bronsted-lewis acid and bromine is 90g:4g:135ml.
6. the preparation method of antioxidant according to claim 2, it is characterised in that 1,2 described in step (c),
4- trichloro-benzenes, dibenzoyl peroxide, ferrous oxide and the imido addition mass ratio of chloro are 128:12:5:210.
7. the preparation method of antioxidant according to claim 2, it is characterised in that trichlorine described in step (d)
Bromobenzene, ethanedioic acid ethyl ester, Cymag and copper bromide addition mass ratio be 0.8:2:2.1:0.13.
8. the preparation method of antioxidant according to claim 2, it is characterised in that 2,4 described in step (e),
6, the molar ratio of m-trichlorobenzene ethyl ketone and tin salt is 1:0.6.
9. the preparation method of antioxidant according to claim 2, it is characterised in that stannous described in step (e)
Salt is nitric acid stannous or stannous sulfate.
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| CN107383418A (en) * | 2017-08-18 | 2017-11-24 | 侯茜茜 | A kind of unioresistant plastic additive and preparation method thereof |
| CN109721979A (en) * | 2019-01-23 | 2019-05-07 | 江西省科学院应用物理研究所 | A kind of PLA matrix that can be fluoresced is used for the composite material preparation of 3D printing |
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