CN106188127B - Preparation method of ring-trapezoid nitrophenyl silsesquioxane - Google Patents
Preparation method of ring-trapezoid nitrophenyl silsesquioxane Download PDFInfo
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- 125000006501 nitrophenyl group Chemical group 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 30
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000012065 filter cake Substances 0.000 claims abstract description 22
- KBXJHRABGYYAFC-UHFFFAOYSA-N octaphenylsilsesquioxane Chemical compound O1[Si](O2)(C=3C=CC=CC=3)O[Si](O3)(C=4C=CC=CC=4)O[Si](O4)(C=5C=CC=CC=5)O[Si]1(C=1C=CC=CC=1)O[Si](O1)(C=5C=CC=CC=5)O[Si]2(C=2C=CC=CC=2)O[Si]3(C=2C=CC=CC=2)O[Si]41C1=CC=CC=C1 KBXJHRABGYYAFC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 11
- 239000012153 distilled water Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000005457 ice water Substances 0.000 claims description 14
- 239000012295 chemical reaction liquid Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims 1
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 238000005905 alkynylation reaction Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- -1 amino-substituted phenyl Chemical group 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- 239000012467 final product Substances 0.000 description 6
- 238000006396 nitration reaction Methods 0.000 description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 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 compound 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
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 229910020381 SiO1.5 Inorganic materials 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920003255 poly(phenylsilsesquioxane) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
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- 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
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
The invention relates to a preparation method of cyclo-trapezoidal nitrophenyl silsesquioxane, belonging to the field of preparation of amino-substituted phenyl silsesquioxaneIn the technical field of organic-inorganic hybrid materials. Adding cyclotrapezoidal phenyl silsesquioxane and a solvent into a reactor, stirring, controlling the temperature of the reactor to be 0-10 ℃, dropwise adding nitric acid, acetic anhydride and acetic acid in sequence, heating the reactor to 25-35 ℃ after dropwise adding, and reacting for 4-8 hours to obtain a reaction solution; the reaction solution is rotary evaporated, filtered and sequentially added with saturated Na2CO3Washing the solution, distilled water and ethanol, drying the filter cake at 40-100 ℃ to obtain the cyclo-trapezoidal nitrophenyl silsesquioxane. The method has the characteristics of mild reaction conditions, good repeatability, high yield, short period and simple operation, and is suitable for expanded production; the obtained product can be further subjected to ammoniation, alkynylation and other reactions to synthesize the novel cycloladder-shaped silsesquioxane derivative.
Description
Technical Field
The invention relates to a preparation method of cyclo-trapezoidal nitrophenyl silsesquioxane (PNPSQ), belonging to the field of organic-inorganic hybrid material science.
Background
Polyhedral oligomeric silsesquioxane (POSS) refers to a compound having the formula (RSiO)1.5)nThe POSS molecular structure not only contains a framework structure of inorganic siloxane, but also can introduce organic groups through a side group. The inorganic silicon-containing inner core with higher density can inhibit the chain motion of the inorganic silicon-containing inner core to endow the inorganic silicon-containing inner core with good heat resistance, and the corresponding organic side group endows the inorganic silicon-containing inner core with good toughness and processability, so that the typical inorganic-organic hybrid material has the basic characteristics of both organic polymers and inorganic ceramics. Polyphenylsilsesquioxanes (PPSQ) with a regular structure have excellent properties of POSS, excellent film-forming properties, and good solubility in organic solvents, and have been used for flame-retardant materials, superhydrophobic materials, ablation-resistant materials, low dielectric materials, photosensitive materials, and the like
Phenyl silsesquioxane (CL-PPSQ) with a trapezoid structure has good reinforcing and flame-retardant effects as a polymer auxiliary agent due to structural regularity. Further improvement of PPSQ compatibility with organic polymers is one of the major issues in current research, the most important of which is the preparation of derivatives of PPSQ. One of the important derivatization chemistry of PPSQ is the nitration of benzene rings.
The research of the existing trapezoid phenyl silsesquioxane is just started, and the existing nitration process of the cage-type oligophenylsilsesquioxane is referred, wherein fuming nitric acid with higher concentration is adopted to realize heterogeneous dispersion with the phenyl silsesquioxane under vigorous stirring, and the cage-type oligophenylsilsesquioxane is synthesized after reaction for 20-24 h. According to the invention, through the introduction of the solvent, homogeneous dispersion is realized, and simultaneously through the improvement of the nitrating agent, the use of high-concentration fuming nitric acid is avoided, so that the safety is greatly improved, and the synthesis time is shortened to 4-8 h.
Disclosure of Invention
The invention aims to provide a preparation method of ring-trapezoid nitrophenyl silsesquioxane, which is a novel polyphenyl silsesquioxane derivative, contains nitrogen and silicon elements, has the structural characteristics of a POSS molecular framework and a nitro group, and can be used for preparing various POSS derivatives containing functional groups.
The purpose of the invention is realized by the following technical scheme.
The invention relates to a preparation method of ring-trapezoid nitrophenyl silsesquioxane, which comprises the following specific preparation steps:
1) adding cyclotrapezoidal phenyl silsesquioxane and a solvent into a reactor, stirring, controlling the temperature of the reactor to be 0-10 ℃ by cooling means such as an ice water bath and the like, dropwise adding nitric acid, acetic anhydride and acetic acid in sequence, heating the reactor to 25-35 ℃ after dropwise adding, and reacting for 4-8 hours to obtain a reaction solution;
2) adding the reaction liquid obtained in the step 1) into ice water, removing the solvent in the reaction liquid by rotary evaporation, separating out yellow solid, performing suction filtration to obtain a product, and sequentially using saturated Na2CO3Washing the solution, distilled water and ethanol, drying the filter cake at 40-100 ℃ to obtain the cyclo-trapezoidal nitrophenyl silsesquioxane.
The inert gas in the step 1) is nitrogen or argon.
The solvent in the step 1) is one or a mixture of acetone, acetonitrile, dichloromethane, chloroform, dioxane, tetrahydrofuran, pyridine, dimethylformamide and dimethylacetamide, and the solvent is preferably dichloromethane; the ratio of the trapezoid phenyl silsesquioxane to the solvent is 1 g: 2-10 mL;
the ratio of the cyclotrapezoidal phenyl silsesquioxane to the nitric acid in the step 1) is 1 g: 1-5 mL;
the ratio of the cyclotrapezoidal phenyl silsesquioxane to the acetic anhydride in the step 1) is 1 g: 2-10 mL;
the ratio of the cyclotrapezoidal phenyl silsesquioxane to the acetic acid in the step 1) is 1 g: 0.5-2.5 mL;
the ring-trapezoid nitrophenyl silsesquioxane prepared by the method contains 10-30 nitrophenyl groups, and typical structural formulas of the nitrobenzene and the nitrobenzene are shown as formulas (1) and (2):
the material is a three-dimensional ring trapezoid organic-inorganic hybrid material with nano size, and the nitrophenyl with higher reaction activity can be further reacted and converted into chemical groups such as amino, alkynyl and the like.
Advantageous effects
The method has the characteristics of mild reaction conditions, good repeatability, high yield, short period and simple operation, and is suitable for expanded production; the structural stability of the product is good, and the ring trapezoidal structure is maintained on the basis of complete phenyl mononitration; the obtained product can be further subjected to ammoniation, alkynylation and other reactions.
Drawings
FIG. 1 shows PPSQ-NO prepared in example 12FT-IR spectrum of (1);
FIG. 2 shows PPSQ-NO prepared in example 12Is/are as follows1H NMR spectrum;
FIG. 3 shows PPSQ-NO prepared in example 12XRD spectrogram of PPSQ before nitration;
FIG. 4 shows PPSQ-NO prepared in example 12A GPC spectrum of PPSQ before nitration;
Detailed Description
The invention is further illustrated by the following examples, which do not limit the scope of the invention.
Example 1
1) Adding 4g of cyclo-trapezoidal phenyl silsesquioxane (PPSQ) and 20mL of dichloromethane into a 250mL three-neck flask with a reflux condenser tube, a constant-pressure dropping funnel, a temperature control device, nitrogen protection and magnetic stirring, controlling the temperature of an ice-water bath to be 0 ℃, slowly dropping 20mL of 80% nitric acid, 40mL of acetic anhydride and 10mL of acetic acid in sequence, completing dropping for about 1 hour, heating to 30 ℃ after the dropping is completed, and reacting for 6 hours to obtain a reaction solution.
2) Pouring the reaction liquid obtained in the step 1) into 50mL of ice water, performing rotary evaporation on the mixed liquid to remove dichloromethane, separating out yellow solid, performing suction filtration to obtain a filter cake, and sequentially using saturated Na2CO3Washing the solution until the filter cake is bubble-free, washing the filter cake with distilled water until the filtrate is neutral, washing with ethanol, and drying the filter cake in a vacuum oven at 50 ℃ for 10 hours to obtain the final product of the cyclo-trapezoidal nitrophenyl silsesquioxane with the yield of about 92.8 percent; FIG. 1 shows FT-IR spectra of cyclic ladder-type nitrophenyl silsesquioxane, 1530 and 1350cm-1The absorption peak is unique to nitro, 1595, 1484 and 1434cm-11078cm as vibration absorption peak of benzene ring skeleton-1Is a vibration absorption peak of Si-O-Si bond. FIG. 2 is a view of a cyclic trapezoidal nitrophenyl silsesquioxane1H NMR spectrum due to-NO2The electron-withdrawing action of the compound enables the hydrogen of the benzene ring to shift to a low field, the ortho-position shift ratio is larger than the meta-position, the vibration peak at 7.5-8.0 ppm is the vibration peak of the hydrogen proton at the nitro-meta position on the benzene ring, and the vibration peak at 8.0-8.5 ppm is the vibration peak of the hydrogen proton at the nitro-ortho position on the benzene ring. The area ratio of the two is about 1:1, and the product contains one nitro group on each benzene ring and most of nitration occurs in-SiO1.5And (4) contraposition.
Wherein the spectrogram data is as follows:
FT-IR(KBr，cm-1)：1530，1350(-NO2) 1595, 1484, 1434 (benzene), 1078 (Si-O-Si);1HNMR(Acetone-d6δ, ppm, TMS): 7.5-8.0 (1H, H at the position of a nitro meta-position on a benzene ring), 8.0-8.5 (1H, H at the position of a nitro ortho-position on the benzene ring); calcd for (NO)2C6H4SiO1.5)2n：C(41.34％)；H(2.30％)；N(8.04％)；found：C(41.30％)；H(2.41％)；N(7.89％)。
Fig. 3 shows XRD patterns of cyclic trapezoidal nitrophenylsilsesquioxane, with diffraction peaks corresponding to the width between the two trapezoidal backbones of the PPSQ ring at 2 θ ═ 7.3 °. The width between the main chains calculated according to the Bragg equation is 1.22nm, and the nano-sized three-dimensional structure is proved to be provided. GPC results of the cyclic ladder nitrophenyl silsesquioxane and the cyclic ladder phenylsilsesquioxane showed that the number average molecular weight of the starting material was about 3053, the polydispersity index was 1.362, the number average molecular weight of the nitrated product was 4110, and the polydispersity index was 1.472, and it was found that structural destruction such as chain scission did not occur, and the nitration degree was also high.
Example 2
1) Adding 8g of cyclo-trapezoidal phenyl silsesquioxane (PPSQ) and 40mL of dichloromethane into a 500mL three-neck flask with a reflux condenser tube, a constant-pressure dropping funnel, a temperature control device, nitrogen protection and magnetic stirring, controlling the temperature of an ice-water bath to be 0 ℃, slowly dropping 40mL of 80% nitric acid, 80mL of acetic anhydride and 20mL of acetic acid in sequence, completing dropping for about 1 hour, heating to 30 ℃ after the dropping is completed, and reacting for 7 hours to obtain a reaction solution.
2) Pouring the reaction liquid obtained in the step 1) into 100mL of ice water, performing rotary evaporation on the mixed liquid to remove dichloromethane, separating out yellow solid, performing suction filtration to obtain a filter cake, and sequentially using saturated Na2CO3Washing the solution until the filter cake is bubble-free, washing the filter cake with distilled water until the filtrate is neutral, washing with ethanol, and drying the filter cake in a vacuum oven at 50 ℃ for 10 hours to obtain the final product of the ring-trapezoid nitrophenyl silsesquioxane with the yield of about 91.7%.
Example 3
1) Adding 8g of cyclo-trapezoidal phenyl silsesquioxane (PPSQ) and 60mL of dichloromethane into a 500mL three-neck flask with a reflux condenser tube, a constant-pressure dropping funnel, a temperature control device, nitrogen protection and magnetic stirring, controlling the temperature of an ice-water bath to be 0 ℃, slowly dropping 40mL of 75% nitric acid, 80mL of acetic anhydride and 20mL of acetic acid in sequence, completing dropping for about 1 hour, heating to 35 ℃ after the dropping is completed, and reacting for 6 hours to obtain a reaction solution.
2) Pouring the reaction liquid obtained in the step 1) into 100mL of ice water, performing rotary evaporation on the mixed liquid to remove dichloromethane, separating out yellow solid, performing suction filtration to obtain a filter cake, and sequentially using saturated Na2CO3Washing with distilled water until the filter cake is bubble-freeWashing the filtrate until the filtrate is neutral, washing the filtrate with ethanol, and drying the filter cake in a vacuum oven at 50 ℃ for 12 hours to finally obtain the cyclo-trapezoidal nitrophenyl silsesquioxane with the yield of about 90.2 percent.
Example 4
1) Adding 12g of cyclo-trapezoidal phenyl silsesquioxane (PPSQ) and 80mL of dichloromethane into a 500mL three-neck flask with a reflux condenser tube, a constant-pressure dropping funnel, a temperature control device, nitrogen protection and magnetic stirring, controlling the temperature of an ice-water bath to be 0 ℃, slowly dropwise adding 50mL of 75% nitric acid, 100mL of acetic anhydride and 30mL of acetic acid in sequence, completing dropwise adding within about 1.5 hours, heating to 30 ℃ after completing dropwise adding, and reacting for 8 hours to obtain a reaction solution.
2) Pouring the reaction liquid obtained in the step 1) into 150mL of ice water, performing rotary evaporation on the mixed liquid to remove dichloromethane, separating out yellow solid, performing suction filtration to obtain a filter cake, and sequentially using saturated Na2CO3Washing the solution until the filter cake is bubble-free, washing the filter cake with distilled water until the filtrate is neutral, washing with ethanol, and drying the filter cake in a vacuum oven at 50 ℃ for 16 hours to obtain the final product, wherein the yield of the final product is about 92.1%.
Example 5
1) Adding 12g of cyclo-trapezoidal phenyl silsesquioxane (PPSQ) and 100mL of dichloromethane into a 500mL three-neck flask with a reflux condenser tube, a constant-pressure dropping funnel, a temperature control device, nitrogen protection and magnetic stirring, controlling the temperature of an ice-water bath to be 0 ℃, slowly dropping 60mL of 85% nitric acid, 120mL of acetic anhydride and 30mL of acetic acid in sequence, completing dropping for about 2 hours, heating to 35 ℃ after the dropping is completed, and reacting for 8 hours to obtain a reaction solution.
2) Pouring the reaction liquid obtained in the step 1) into 200mL of ice water, performing rotary evaporation on the mixed liquid to remove dichloromethane, separating out yellow solid, performing suction filtration to obtain a filter cake, and sequentially using saturated Na2CO3Washing the solution until the filter cake is bubble-free, washing the filter cake with distilled water until the filtrate is neutral, washing with ethanol, and drying the filter cake in a vacuum oven at 60 ℃ for 12 hours to obtain the final product, wherein the yield of the final product is about 93.2%.
Claims (5)
1. A preparation method of the ring-trapezoid nitrophenyl silsesquioxane is characterized by comprising the following steps:
1) adding cyclotrapezoidal phenyl silsesquioxane and a solvent into a reactor, stirring, controlling the temperature of the reactor to be 0-10 ℃ by using an ice-water bath cooling means, dropwise adding nitric acid, acetic anhydride and acetic acid in sequence, heating the reactor to 25-35 ℃ after dropwise adding, and reacting for 4-8 hours to obtain a reaction solution;
2) adding the reaction liquid obtained in the step 1) into ice water, removing the solvent in the reaction liquid by rotary evaporation, separating out yellow solid, performing suction filtration to obtain a product, and sequentially using saturated Na2CO3Washing the solution, distilled water and ethanol, drying the filter cake at 40-100 ℃ to obtain the cyclo-trapezoidal nitrophenyl silsesquioxane;
the ratio of the cyclotrapezoidal phenyl silsesquioxane to the solvent in the step 1) is 1 g: 2-10 mL; the ratio of the ring ladder-shaped phenyl silsesquioxane to the nitric acid is 1 g: 5 mL; the ratio of the trapezoid phenyl silsesquioxane to the acetic anhydride was 1 g: 10 mL; the ratio of the trapezoid phenyl silsesquioxane to acetic acid was 1 g: 2.5 mL;
the solvent in the step 1) is one or a mixture of acetone, acetonitrile, dichloromethane, trichloromethane, dioxane, tetrahydrofuran, pyridine, dimethylformamide and dimethylacetamide;
the general structural formula is shown as formula (1) and formula (2):
2. the method for preparing cyclo-trapezoidal nitrophenyl silsesquioxane according to claim 1, wherein: the reactor in the step 1) is provided with a temperature control device, a condensation reflux device, inert gas protection and a magnetic stirring device.
3. The method for preparing cyclo-trapezoidal nitrophenyl silsesquioxane according to claim 2, wherein: the inert gas is nitrogen or argon.
4. The method for preparing cyclo-trapezoidal nitrophenyl silsesquioxane according to claim 1, wherein: the concentration of the nitric acid is 65-85%.
5. The method for preparing cyclo-trapezoidal nitrophenyl silsesquioxane according to claim 1, wherein: the solvent is dichloromethane.
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| CN1844126A (en) * | 2006-05-19 | 2006-10-11 | 北京化工大学 | Process for preparing amino phenyl silsesquioxane |
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| CN1844126A (en) * | 2006-05-19 | 2006-10-11 | 北京化工大学 | Process for preparing amino phenyl silsesquioxane |
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