CN118221713A - 1, 1' -Oxybis (2, 6, 7-trioxa-1-silicon bicyclo [ 2.2.2 ] octyl-4-amine) and synthetic method thereof - Google Patents
1, 1' -Oxybis (2, 6, 7-trioxa-1-silicon bicyclo [ 2.2.2 ] octyl-4-amine) and synthetic method thereof Download PDFInfo
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- CN118221713A CN118221713A CN202311808972.9A CN202311808972A CN118221713A CN 118221713 A CN118221713 A CN 118221713A CN 202311808972 A CN202311808972 A CN 202311808972A CN 118221713 A CN118221713 A CN 118221713A
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 17
- 239000010703 silicon Substances 0.000 title claims abstract description 17
- 238000010189 synthetic method Methods 0.000 title description 4
- -1 nitrogen-containing organosilicon compound Chemical class 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 14
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000706 filtrate Substances 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000004821 distillation Methods 0.000 claims abstract description 4
- 238000001308 synthesis method Methods 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 35
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000001816 cooling Methods 0.000 abstract description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006467 substitution reaction Methods 0.000 abstract description 4
- VCLQDVVELGHZMQ-UHFFFAOYSA-N bicyclo[2.2.2]octan-4-amine Chemical compound C1CC2CCC1(N)CC2 VCLQDVVELGHZMQ-UHFFFAOYSA-N 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- 239000012265 solid product Substances 0.000 description 9
- 239000003822 epoxy resin Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical group N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 150000003961 organosilicon compounds Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 229960001124 trientine Drugs 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
-
- 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
- C07F7/02—Silicon compounds
- C07F7/04—Esters of silicic acids
- C07F7/07—Cyclic esters
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
The invention relates to 1,1' -oxybis (2, 6, 7-trioxa-1-silicon bicyclo [2.2.2] octan-4-amine) and a synthesis method thereof. The method comprises the following steps: the silicon source and tris (hydroxymethyl) aminomethane were added to the solvent and reacted until completely dissolved after nitrogen substitution. Cooling after reduced pressure distillation, adding ethanol, heating and stirring, and filtering. Adding the filtrate into an organic solvent to precipitate solid, stirring, filtering, washing and drying to obtain the novel nitrogen-containing organosilicon compound.
Description
Technical Field
The invention belongs to the field of organic synthesis, in particular to synthesis of nitrogen-containing organosilicon compounds.
Background
As a material excellent in properties, an organosilicon material has been widely used in many fields, and the preparation of nitrogen-containing organosilicon compounds generally depends on other organosilicon compounds such as tetraethyl silicate and the like. Not only has complex process flow, but also has high raw material cost, and is not beneficial to industrial production. These limiting factors have hampered the development of nitrogen-containing organosilicon compounds. The nitrogen-containing organosilicon compound is a green nontoxic organosilicon compound due to the special structure, and has potential application value in the fields of novel materials and the like.
The invention prepares a novel nitrogen-containing organosilicon compound. The nitrogen-containing organosilicon compound is expected to be used as an epoxy resin curing agent and has a flame-retardant function.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to invent a novel nitrogen-containing organosilicon compound and a preparation method thereof. I.e., the reaction of a silicon source and tris (hydroxymethyl) aminomethane to directly synthesize 1, 1' -oxybis (2, 6, 7-trioxa-1-silabicyclo [ 2.2.2 ] oct-4-amine).
The molecular formula of the novel nitrogen-containing organosilicon compound is C 8H16O7N2Si2; chinese name 1, 1' -oxybis (2, 6, 7-trioxa-1-silabicyclo [ 2.2.2 ] oct-4-amine) [ H 2NC(CH2O)3SiOSi(OCH2)3CNH2 ]; the molecular structural formula is as follows:
。
The specific embodiment of the invention is as follows: adding a silicon source and tris (hydroxymethyl) aminomethane into a solvent, carrying out a reaction of 6-12 h until the silicon source and tris (hydroxymethyl) aminomethane are completely dissolved after nitrogen replacement, carrying out reduced pressure distillation after the reaction is completed, adding ethanol into residues, stirring for 1-2 h at 75-85 ℃, filtering, adding filtrate into an organic solvent, stirring at normal temperature, filtering, washing the organic solvent, and drying to obtain the novel nitrogen-containing organosilicon compound.
With the scheme, the silicon source is one of silicic acid and white carbon black by a precipitation method.
In the above scheme, the solvent is ethylene glycol.
A catalyst is selectively added in the reaction process, wherein the catalyst is selected from imidazole and 1, 8-diazabicyclo [ 5.4.0 ] undec-7-ene (DBU); the catalyst is added in an amount of 0-5wt% relative to the mass fraction of the silicon source, wherein 0 is a technical scheme without adding the catalyst, and in some specific embodiments, the catalyst is often added in an amount of 1-5 wt%, such as any one of 1wt%, 2wt%, 3 wt%, 4 wt%, 5 wt%.
With the scheme, the molar ratio of the silicon source to the tris (hydroxymethyl) aminomethane is 1:0.8-1.5.
With the scheme, the reaction heating temperature is 190-210 ℃.
With the above scheme, the organic solvent is one or more of n-hexane, ethyl acetate, n-heptane and petroleum ether.
The method adopts SiO 2 to react with tris (hydroxymethyl) aminomethane, and is a one-step reaction. Tris (hydroxymethyl) aminomethane is dissolved in ethylene glycol, and ethylene glycol has a high boiling point, meeting the temperature required for the reaction. The reaction takes away the water generated in the reaction through the boiling reflux of the glycol and the molecular sieve, and promotes the reaction.
The invention has the beneficial effects that:
1. The invention adopts a one-step synthesis method to prepare a novel nitrogenous organosilicon compound, and the synthesis route is short.
2. The invention has low energy consumption and less byproducts.
Drawings
FIG. 1 is an infrared spectrum of 1, 1' -oxybis (2, 6, 7-trioxa-1-silabicyclo [ 2.2.2 ] oct-4-amine) prepared in example 1 and a synthetic method thereof.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of 1, 1' -oxybis (2, 6, 7-trioxa-1-silabicyclo [ 2.2.2 ] oct-4-amine) prepared in example 1 and a synthetic method thereof.
FIG. 3 is a high resolution mass spectrum of 1, 1' -oxybis (2, 6, 7-trioxa-1-silabicyclo [ 2.2.2 ] oct-4-amine) prepared in example 1 and a method for synthesizing the same.
Detailed Description
The present invention will be described in further detail below in order to enable those skilled in the art to better understand the technical scheme of the present invention.
Example 1
61.13 G ethylene glycol, 6.0 g silicic acid and 9.17. 9.17 g tris (hydroxymethyl) aminomethane were added to the dried two-necked flask, and after nitrogen substitution, the mixture was reacted at 200℃for 12 hours, and then distilled off under reduced pressure at 160 ℃. Cooling to 50deg.C, adding 20.02 g ethanol to the residue, stirring at 75deg.C for 1: 1h, filtering, adding the filtrate dropwise to 40.12: 40.12 g ethyl acetate, stirring at 25deg.C for 2: 2h, filtering, washing with ethyl acetate for 2 times, and oven drying at 60deg.C to obtain 4.60: 4.60 g solid product.
The infrared spectrum of the solid product is shown in figure 3. 1464 The bending vibration peak of methylene is at cm -1, the asymmetric stretching vibration peak of methylene is at 2942 and cm -1, the symmetric stretching vibration peak of methylene is at 2876 and cm -1, the stretching vibration peak of Si-O-C is at 1069 and cm -1 and 893 and cm -1, and the stretching vibration peak of C-O is at 1032 and cm -1. 1285 The C-N stretching vibration peak is at cm -1, and the O-H stretching vibration peak is at 3347 and cm -1. Preliminary evidence of the existence of the due characteristic peaks of the product.
The nmr hydrogen spectrum of the solid product is shown in fig. 2, with the single peaks at chemical shifts 3.23 ppm corresponding to the hydrogens of formulae 3, 5, 7, 11, 13, 15 and the single peaks at 4.32 ppm corresponding to the hydrogens of formulae 18, 19.
The high resolution mass spectrum of the solid product is shown in FIG. 3, and the molecular weight of the solid product is 308.05 (the detection method is ESI anion detection, wherein one hydrogen ion is removed and then sodium is added to the solid product to be 330).
The product was identified as nitrogen-containing organosilicon compound 1, 1' -oxybis (2, 6, 7-trioxa-1-silabicyclo [ 2.2.2 ] oct-4-amine) [ H 2NC(CH2O)3SiOSi(OCH2)3CNH2 ] by combining the results of FTIR, 1 H-NMR and HRMS analyses.
Example 2
59.63 G ethylene glycol, 5.98 g silicic acid and 9.12 g tris (hydroxymethyl) aminomethane were added to the dried two-necked flask, and after nitrogen substitution, the mixture was reacted at 204℃for 10 hours, and the ethylene glycol was distilled off under reduced pressure at 160 ℃. Cooling to 50 ℃, adding 22.01 g ethanol into the residue, stirring at 75 ℃ for 1: 1h, filtering, dripping the filtrate into 40.56: 40.56 g petroleum ether, stirring at 25 ℃ for 2: 2h, filtering, washing with petroleum ether for 2 times, and drying at 60 ℃ to obtain 4.63: 4.63 g solid product, which is the same as in example 1.
Example 3
59.63 G ethylene glycol, 5.98 g silicic acid and 9.12 g tris (hydroxymethyl) aminomethane were added into a dry two-necked flask, stirred uniformly, then 0.25 g imidazole was added, after nitrogen substitution, the mixture was reacted at 204℃for 10 hours, and the ethylene glycol was distilled off under reduced pressure at 160 ℃. Cooling to 50 ℃, adding 22.01 g ethanol to the residue, stirring at 75 ℃ for 1: 1h, filtering, dripping the filtrate into 40.56: 40.56 g petroleum ether, stirring at 25 ℃ for 2: 2h, filtering, washing with petroleum ether for 2 times, and drying at 60 ℃ to obtain 7.63: 7.63 g solid product, which is the same as in example 1.
Example 4
To the two-necked flask dried, 62.01 g ethylene glycol, 6.10 g precipitated silica and 9.85 g tris (hydroxymethyl) aminomethane were added, and after stirring uniformly, 0.3 g of 1, 8-diazabicyclo [ 5.4.0 ] undec-7-ene (DBU) nitrogen was added for replacement, followed by reaction at 201℃for 8 hours and distillation under reduced pressure at 160℃to remove ethylene glycol. Cooling to 50 ℃, adding 20.11 g ethanol to the residue, stirring at 75 ℃ for 1: 1h, filtering, dropwise adding the filtrate into 40.34 g n-hexane, stirring at 25 ℃ for 2: 2h, filtering, washing with n-hexane for 2 times, and drying at 60 ℃ to obtain 8.66: 8.66 g solid product, which is the same as in example 1.
Example 5
The present example provides the use of a novel nitrogen-containing organosilicon compound as a curing agent for epoxy resins.
47.70 G bisphenol A epoxy resin (E51) and 5.91 g triethylene tetramine are added into a dry two-mouth bottle, uniformly stirred, subjected to vacuum defoaming of 10 min, poured into a spline, and cured at 100 ℃ for 2h after solidification, so as to obtain a sample 1. 1.23 g of the nitrogen-containing organosilicon compound 3 obtained in the example 1 is taken and dissolved in 5.91 g of triethylene tetramine, and added into 47.70 g of bisphenol A type epoxy resin (E51) to be stirred uniformly, the mixture is defoamed in vacuum by 10 min, a spline is poured, and after solidification, the mixture is solidified by 2h at 100 ℃ to obtain a sample 2.
Sample 1 and sample 2 were tested for impact strength according to GB/T1843-2008 using a pendulum impact tester (HIT 50, zwick, germany), flexural strength according to GB/T9341-2008 using a TCS-2000 test, limiting Oxygen Index (LOI) according to GB/T2406-93 using an FTA II oxygen index meter (Hampshire rheology Co., UK), thermogravimetric analysis (TGA) using Germany Netzsch STA449F3 in a nitrogen atmosphere, gas flow rate of 20 mL/min, heating rate of 10 ℃/min, heating range of 30-800 ℃, vicat softening point temperature according to GB/T1634-1979 using a Jinan Tian Vicat softening point temperature meter (XWY-300B), and test results are shown in Table 1. According to the test results, the strength properties of the epoxy resin are almost unchanged at the addition amount of 2.2%, the limiting oxygen index is increased by 3%, the temperature is also increased by 1.8 ℃ at the maximum decomposition rate, the residual mass is 1.17% more, and the Vicat softening point temperature is not greatly different, and the nitrogen-containing organosilicon compound can be used as a curing agent to be added into the epoxy resin to improve the flame retardant property thereof through evaluation.
Table 1: each test result of two samples
Claims (8)
1.1,1' -Oxybis (2, 6, 7-trioxa-1-silabicyclo [ 2.2.2 ] oct-4-amine), characterized in that the novel nitrogen-containing organosilicon compound has the molecular formula C 8H16O7N2Si2; the molecular structural formula is as follows:
。
The synthesis method of the 2, 1' -oxybis (2, 6, 7-trioxa-1-silicon bicyclo [2.2.2] octyl-4-amine) is characterized by comprising the following specific steps: adding a silicon source and tris (hydroxymethyl) aminomethane into a solvent, heating for reaction until the silicon source and tris (hydroxymethyl) aminomethane are completely dissolved after nitrogen replacement, adding ethanol into residues after reduced pressure distillation, stirring for 1-2 hours at 75-85 ℃, filtering, adding filtrate into an organic solvent, stirring, filtering, washing a filter cake, and drying to obtain 1,1' -oxybis (2, 6, 7-trioxa-1-silicon bicyclo [2.2.2] oct-4-amine).
3. The method for synthesizing 1, 1' -oxybis (2, 6, 7-trioxa-1-silabicyclo [ 2.2.2 ] oct-4-amine) according to claim 2, wherein the silicon source is one of silicic acid and precipitated silica.
4. The method for synthesizing 1, 1' -oxybis (2, 6, 7-trioxa-1-silabicyclo [ 2.2.2 ] oct-4-amine) according to claim 2, wherein the solvent is ethylene glycol.
5. The method for synthesizing 1, 1' -oxybis (2, 6, 7-trioxa-1-silabicyclo [ 2.2.2 ] oct-4-amine) according to claim 2, characterized in that a catalyst is optionally added during the reaction, said catalyst being selected from imidazole, 1, 8-diazabicyclo [ 5.4.0 ] undec-7-ene (DBU); the addition amount of the catalyst is 0-5wt% relative to the mass fraction of the silicon source.
6. The method for synthesizing 1, 1' -oxybis (2, 6, 7-trioxa-1-silabicyclo [ 2.2.2 ] oct-4-amine) according to claim 2, wherein the molar ratio of the silicon source to tris (hydroxymethyl) aminomethane is 1:0.8 to 1.5.
7. The method for synthesizing 1, 1' -oxybis (2, 6, 7-trioxa-1-silabicyclo [ 2.2.2 ] oct-4-amine) according to claim 2, wherein the heating reaction time is 6-12 h.
8. The method for synthesizing 1, 1' -oxybis (2, 6, 7-trioxa-1-silabicyclo [ 2.2.2 ] oct-4-amine) according to claim 1, wherein the organic solvent is one or more of n-hexane, ethyl acetate, n-heptane, petroleum ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311808972.9A CN118221713A (en) | 2023-12-26 | 2023-12-26 | 1, 1' -Oxybis (2, 6, 7-trioxa-1-silicon bicyclo [ 2.2.2 ] octyl-4-amine) and synthetic method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311808972.9A CN118221713A (en) | 2023-12-26 | 2023-12-26 | 1, 1' -Oxybis (2, 6, 7-trioxa-1-silicon bicyclo [ 2.2.2 ] octyl-4-amine) and synthetic method thereof |
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| CN118221713A true CN118221713A (en) | 2024-06-21 |
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