CN1332963C - Amino phenyl cage type sesqui siloxane and its preparing method - Google Patents
Amino phenyl cage type sesqui siloxane and its preparing method Download PDFInfo
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- CN1332963C CN1332963C CNB2004100011021A CN200410001102A CN1332963C CN 1332963 C CN1332963 C CN 1332963C CN B2004100011021 A CNB2004100011021 A CN B2004100011021A CN 200410001102 A CN200410001102 A CN 200410001102A CN 1332963 C CN1332963 C CN 1332963C
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Abstract
The present invention relates to amino phenyl cage type sesquisiloxane and a preparation method thereof. Industrialized phenyl trichlorosilane is used as primary raw materials; firstly, cage type sesquisiloxane containing phenyl is prepared by synthesizing the industrialized phenyl trichlorosilane; then, the phenyl is nitrified; finally, the amino phenyl cage type sesquisiloxane is prepared by amino functionalization. The step of functional trichlorosilane prepared from trichlorohydro silicide is omitted, the present invention has the advantages of simple preparation process and low cost, and modified properties of epoxy resin are enhanced.
Description
Technical field:
The present invention relates to a kind of aminophenyl cage-type silsesquioxane and preparation method thereof.
Background technology:
Along with the development of social informatization, information processing and information are propagated high speed, urgently are desirable to provide a kind of electron recombination material with superior heat resistance.Resins, epoxy is owing to have the electron recombination material that characteristics such as good processability, low price, ample supply and prompt delivery, over-all properties be outstanding become present widespread use, but existing pure epoxy resin resistance toheat is poor, can not satisfy the service requirements of some high-temperature electron recombination material, having only the method that adopts modification that Resins, epoxy is had becomes a kind of cost benefit ideal electron recombination material.
Generally speaking, plastics only just can have favorable mechanical performance and dimensional stability below second-order transition temperature, improve the thermotolerance of material, must improve its second-order transition temperature.Glass transition is that polymkeric substance is from the secondary transition of vitreous state to elastomeric state.In the second-order transition temperature process, polymer segment thaws, and its specific heat and specific volume are undergone mutation, and thermal expansivity increases rapidly.If introduce huge rigid radical on main polymer chain or side chain, because huge rigid radical hinders the segmental free movement, glass transition that can sluggish polymkeric substance improves second-order transition temperature (Tg), and then the resistance toheat of material is improved.Therefore, the performance resins matrix generally is designed to contain a large amount of huge rigid chain segments to obtain high Tg and thermotolerance.Therefore, the performance resins matrix generally is designed to contain a large amount of huge rigid chain segments to obtain high Tg and thermotolerance.But the resin matrix cycle of development of new is long, cost is high, still select in the present industrial production to have press down combustion character brominated bisphenol A Resins, epoxy as base material, the method by modification improves the heat resisting temperature of Resins, epoxy to be used as cheap electron recombination material.
The method that improves the Resins, epoxy heat resisting temperature at present has multiple, as adopt high performance cyanate resin modifier (Zhao Lei, beam state just waits, the application of cyanate ester resin in the aerospace matrix material. aerospace process materials 2000 (2): 17-21), fibre modification, powder-modified, glass microballon modification etc., though above-mentioned method of modifying increases to some extent for second-order transition temperature and thermostability, but simultaneously because negative factors such as the mechanical property that has expensive raw material price and influence base material and dielectric properties, feasible more than the use of each method limited to.
Cage-type silsesquioxane is meant that general formula is (RSiO
1.5)
nThe one class polyhedron compound of (n 〉=4, R=H, alkyl, aryl or organo-functional group) is because of its shape is called as cagelike silsesquioxane like cage.When n=8, the structure of cagelike silsesquioxane is a regular cube, and the Si atom is positioned at cubical 8 drift angles, and per two adjacent Si atoms are connected by an O atom and (are called for short T
8), the size of cagelike structure is more than 1.5nm.Nearest studies show that T
8Siloxanes is equivalent to the secondary structure of crystalline silica or zeolite framework, and the material that is made of it is expected to have high rigidity and high thermal stability.
But non-functionalized cage-type silsesquioxane exists with crystalline form, has only the functionalized dispersion that could realize molecular level of cage-type silsesquioxane, could really embody the nano-meter characteristic of cage-type silsesquioxane.
The synthetic cage-type silsesquioxane is a chlorosilane at present, the hydrolysate of organoalkoxysilane, have a plurality of cyclopentyl on its drift angle more, cyclohexyl, groups such as isobutyl-or trimethoxy are silica-based, if will never complete condensation seven gather three silanols and the synthetic functionalized cage-type silsesquioxane of trichlorosilane warp " drift angle-attach the names of pre-determined candidates " method, at first functionalized to trichlorosilane, make route complicated because of trichlorosilane is inflammable and explosive, the operational condition harshness, not high (the F.J.Feher of yield, K.J.Weller, J.J.Schwab, Organometallics 1995,14 (4), and 2009); And want that synthesizing nitryl is functionalized, the cage-type silsesquioxane of aminofunctional, above route is infeasible.U.S. hybrid plastics company has synthesized aliphatic amide silsesquioxane (1-(3-aminopropyl)-3 through ammonification with 3-chloropropyl trichloro-silane and seven poly-three silanols again through " drift angle-attach the names of pre-determined candidates " method, 5,7,9,11,13,15-heptacyclohexylpentacycol-[9.5.1.13.9.15,15.17.13] octasiloxane) (
Www.hybridplastics.com), this route only is suitable for the synthetic fatty amine silsesquioxane, and productive rate is low, the purifying technique complexity.Simultaneously, with the reaction of Resins, epoxy in, the reactive behavior of aliphatic amide is low, speed of response is slow, its modifying function is not as good as aromatic amine.And be not reported at present about aminophenyl cage-type silsesquioxane and preparation method thereof.
Summary of the invention:
The invention provides a kind of aminophenyl cage-type silsesquioxane and preparation method thereof, with industrialized phenyl-trichloro-silicane is the synthetic cage-type silsesquioxane that has phenyl of primary raw materials, then phenyl is carried out nitrated and aminofunctional, saved the step that begins to prepare corresponding functionalized trichlorosilane by trichlorosilane, promptly can simplify preparation process, reduce cost, can improve the modification performance of Resins, epoxy again.
The invention main points:
A kind of aminophenyl cage-type silsesquioxane, its structural formula is as follows:
R is cyclopentyl, cyclohexyl or isobutyl-in the formula, and amino is a contraposition or a position on phenyl ring.
The preparation method of above-mentioned aminophenyl cage-type silsesquioxane comprises the preparation (phenyl cage-type silsesquioxane nitrated) of synthetic, the nitrophenyl cage-type silsesquioxane of phenyl cage-type silsesquioxane, three steps of preparation of aminophenyl cage-type silsesquioxane; Specific as follows:
(1) seven poly-silanetriols is dissolved in volume ratio 20: 1-40: in 1 the tetrahydrofuran (THF) and the mixed solvent of pyridine, under 0-5 ℃ of agitation condition, adding molar weight is seven poly-silanetriol 1-1.2 phenyl-trichloro-silicanes doubly, then 10-30 ℃ of reaction 4-10 hour, collect product, obtain the phenyl cage-type silsesquioxane;
(2) the phenyl cage-type silsesquioxane that step (1) is obtained join carry out in the nitrated system that trichloromethane or tetracol phenixin and concentration expressed in percentage by weight form greater than 96% concentrated nitric acid nitrated, the volume ratio of trichloromethane or tetracol phenixin and concentrated nitric acid is 1: 3-1: 6,-5-10 ℃ following the reaction 4-8 hour, collect product, obtain the nitrophenyl cage-type silsesquioxane;
(3) the nitrophenyl cage-type silsesquioxane that step (2) is obtained joins volume ratio 4: 1-8: in the system that 1 tetrahydrofuran (THF) and triethylamine are formed; adding Pd weight percentage is 5% Pd/C catalyzer; the add-on of catalyzer is that to make the mol ratio of Pd and nitrophenyl cage-type silsesquioxane be 1/10-1/50; at 60 ℃ to reflux temperature; under protection of inert gas; dripping volume ratio is the formic acid of triethylamine 20-50%; reacted 5-10 hour; collect product, obtain the aminophenyl cage-type silsesquioxane.Usually used rare gas element is a nitrogen, and it is better to drip excessive formic acid usually.
The collection product process of mentioning in above-mentioned three steps comprises filtration, washing, drying, is the method known of chemistry (particularly organic synthesis field) field.Collect in the process of product in step (3), for preventing the oxidation in air of aminophenyl cage-type silsesquioxane, preferably with product at rotary evaporation below 30 ℃, remove solvent, after filtration, vacuum-drying at normal temperatures obtains the finished product after the washing.
The chemical equation of aminophenyl cage-type silsesquioxane its preparation method of the present invention is as follows:
R is cyclopentyl, cyclohexyl or isobutyl-in the formula, and THF is a tetrahydrofuran (THF), Et
3N is a triethylamine, and Pyridine is a pyridine.
Aminophenyl cage-type silsesquioxane of the present invention is when modified epoxy, and its nano level cagelike structure is connected on the Resins, epoxy chain with the form of chemical bond, is similar to " hammer ".Because the existence of its relative bulky structure, the motion of seriously having blocked the Resins, epoxy chain makes the glass epoxy transformation postpone, and heat resisting temperature can increase substantially.
Adopt institute of the present invention synthetic aminophenyl cage-type silsesquioxane modified epoxy, can under less consumption and low-cost condition, improve the heat resisting temperature of Resins, epoxy significantly by simple technology, because of the molecular level dispersiveness and the high dielectric property of silsesquioxane, also can promote the mechanical property and the dielectric properties of base material simultaneously.
In addition, synthetic method of the present invention is raw material because of using industrialized phenyl-trichloro-silicane, and has saved the step that is begun to prepare corresponding functionalized trichlorosilane by trichlorosilane, has simplified process, can reduce cost greatly.Method of the present invention also has the characteristics of high yield, and yield is usually greater than 90%.
Embodiment:
Embodiment 1
The poly-cage-type silsesquioxanes of aminophenyl seven cyclopentyl eight (1-(2 (4)-aminophenyl)-3,5,7,9,11,13,15-heptacyclopentylpentacycol-[9.5.1.1 3.9.15,15.17.13] octasiloxane) synthetic.
(1) add the poly-silanetriols of 8.22g (9.41mmol) exsiccant seven cyclopentyl seven, 200mL tetrahydrofuran (THF) successively in the 500mL round-bottomed flask, the 5mL pyridine stirs under 0 ℃, injects 2.0g (9.41mmol) phenyl-trichloro-silicane ((C
6H
5) SiCl
3).Afterwards, be warmed up to 10 ℃, reacted 4 hours.The elimination insolubles is evaporated to the surplus 10mL of solvent with filtrate with rotatory evaporator, and the adularescent solid is separated out, and suction filtration, filter cake are used acetone, water washing respectively, and drying obtains white crystalline powder 8.45g (8.66mmol), is phenyl cage-type silsesquioxane (C
6H
5) (C
5H
9)
7Si
8O
12Productive rate: 92%.Analyze (following and embodiment 2,3 described characterization datas all adopt same analytical procedure to obtain) through NMR (Nuclear Magnetic Resonance) spectrum (NMR) and infrared absorption spectrum (FTIR), characterization data is:
29Si NMR (119MHz, CDCl
3, 300K, acetone-d
6, ppm)-79.8 ,-66.5 ,-66.1,1:3:4;
1H NMR (600MHz, CDCl
3, 300K, ppm) 7.70 (d, 2H), 7.41 (m, 3H), 1.53-1.79 (m, 56H), 1.02 (m, 7H); FTIR (cm
-1, KBr) 2950 (ν
As C-H), 2865 (ν
S C-H), 1451 (ν
C=C), 1248 (β
=CH), 1099 (ν
Si-O-Si), 731 (γ
=CH).
(2) under the ice bath cooling conditions, in the 1000mL round-bottomed flask, add 100mL CCl earlier
4, under agitation condition, slowly add the 600mL concentrated nitric acid of being fuming again, slowly add synthetic 8.45g (8.66mmol) phenyl seven cyclopentyl eight polysilsesquioxanes several times, continuously stirring 8 hours, 10 ℃ of temperature of reaction.Reaction finishes, and in reaction solution impouring trash ice, leaves standstill.Tell organic phase, be washed to neutrality.Rotary evaporation falls CCl
4, suction filtration, filter cake are used acetone, water washing respectively, get white crystalline powder 7.94g (7.73mmol), are nitrophenyl seven cyclopentyl eight poly-cage-type silsesquioxane ((C
6H
4NO
2) (C
5H
9)
7Si
8O
12).Warp
29Si NMR turns out to be the mixture that its phenyl ring replaces (a), adjacent (b) position, and content is 1: 1.Total recovery is 94%.Characterization data is:
29Si NMR (119MHz, CDCl
3, 300K, acetone-d
6, ppm)-81.32 (Si links to each other with ortho position nitro substituted-phenyl) ,-84.67 (Si links to each other with the para-orientation nitrophenyl) ,-65.70 (2a) ,-66.20 (2b) ,-66.45,1:1:3:3:8;
1H NMR (600MHz, CDCl
3, 300K, ppm) 7.57-8.54 (m, 8H), 1.70-1.47 (m, 112H), 1.07 (m, 14H); FTIR (cm
-1, KBr) 2958 (ν
As C-H), 2860 (ν
S C-H), 1535 (ν
As-NO2), 1440 (ν
C=C), 1353 (ν
S-NO2), 1240 (β
=CH), 1080 (ν
Si-O-Si), 917 (γ
=CH).
(3) adding the poly-cage-type silsesquioxanes of 7.94g (7.73mmol) nitrophenyl seven cyclopentyl eight, 280mL tetrahydrofuran (THF), 70mL triethylamine, Pd weight percentage successively in the 1000mL four-hole bottle is 5% Pd/C catalyzer 1.6429g (0.773mmol).N
2Protection is temperature rising reflux down; slowly drip 15mL 85% formic acid; afterreaction finished in 5 hours, filtered, and filtrate is at rotary evaporation below 30 ℃; remove and desolvate; suction filtration is used acetone and water washing filter cake respectively, vacuum-drying under the normal temperature; white crystalline powder 7.29g (7.42mmol), be the mixture ((C of phenyl ring to the amino cage-type silsesquioxane that replaces in, ortho position
6H
4NH
2) (C
5H
9)
7Si
8O
12).Characterization data is:
29Si NMR (CDCl
3, acetone-d
6, ppm, 300K)-65.4 (Si links to each other with p-aminophenyl) ,-65.9 (Si links to each other with adjacent aminophenyl) ,-66.3 ,-78.0 (a) ,-80.0 (b);
1H NMR (600MHz, 300K, ppm) 6.63-7.48 (m, 8H), 1.45-1.77 (m, 112H), 1.03 (m, 14H); FTIR (cm
-1, KBr), 2954 (ν
As C-H), 2868 (ν
S C-H), 1440 (ν
C=C), 1245 (β
=CH), 1110 (ν
Si-O-Si), 917 (γ
=CH).
Embodiment 2
Aminophenyl seven cyclohexyl cage modles eight polysilsesquioxanes (1-(2 (4)-aminophenyl)-3,5,7,9,11,13,15-heptacyclohexylpentacycol-[9.5.1.13.9.15,15.17.13] octasiloxane) synthetic.
(1) in the 500mL round-bottomed flask, add incomplete condensation seven cyclohexyl of 6.52g (6.71mmol) exsiccant seven poly-silanetriols, 150mL tetrahydrofuran (THF) successively, the 5mL pyridine, 5 ℃ stir, and inject 1.56g (7.38mmol) phenyl-trichloro-silicane, stir.Afterwards, be warmed up to 30 ℃, reacted 8 hours.Then with the reaction soln vacuum filtration, filtrate is evaporated to the surplus 15mL of solvent with rotatory evaporator, the adularescent solid is separated out, suction filtration, filter cake are used acetone, water washing, drying respectively, obtain white crystalline powder 7.45g (6.94mmol), be cage-type silsesquioxane ((C
6H
5) (C
6H
11)
7Si
8O
12).The calculating productive rate is: 94%.Characterization data:
29Si NMR (119MHz, CDCl
3, acetone-d
6, ppm)-79.3 ,-66.7 ,-66.0,1:3:4;
1H NMR (ppm) 7.74 (d, 2H), 7.39 (m, 3H), 1.44-1.79 (m, 64H), 1.08 (m, 13H); FTIR (cm
-1, KBr) 2955 (ν
As C-H), 2863 (ν
S C-H), 1447 (ν
C=C), 1240 (β
=CH), 1109 (ν
Si-O-Si), 735 (γ
=CH).
(2) bathe under the cooling conditions in cryosel, in the 500mL round-bottomed flask, add 60mL CHCl earlier
3, under agitation condition, slowly add the 180mL nitrosonitric acid again, slowly add phenyl seven cyclohexyl eight polysilsesquioxane 6.78g (6.31mmol) several times ,-5 ℃ of following continuously stirring 4 hours.Reaction finishes, and in reaction solution impouring trash ice, leaves standstill.Tell organic phase, wash and be neutral.Rotary evaporation falls CHCl
3, suction filtration, filter cake are used acetone, water washing respectively, get white crystalline powder 6.57g (5.87mmol), are nitrophenyl seven cyclohexyl eight poly-cage-type silsesquioxane ((C
6H
4NO
2) (C
6H
11)
7Si
8O
12), warp
29Si NMR turns out to be the mixture that its phenyl ring replaces (a), adjacent (b) position, and content is 1: 1.Overall yield is: 93%.Characterization data is:
29Si NMR (119MHz, CDCl
3, 300K, acetone-d
6) δ-81.55 (Si links to each other with the para-orientation phenyl) ,-84.60 (Si links to each other with the ortho position substituted-phenyl) ,-65.71 (a) ,-66.33 (b) ,-66.52,1:3:4;
1H NMR (600MHz, CDCl
3, 300K, ppm) 7.42-8.44 (m, 8H), 1.48-1.77 (m, 128H), 1.05 (m, 26H); FTIR (cm
-1, KBr) 2959 (ν
As C-H), 2860 (ν
S C-H), 1533 (ν
As-NO2), 1448 (ν
C=C), 1353 (ν
S-NO2), 1240 (β
=CH), 1089 (ν
Si-O-Si), 911 (γ
=CH).
(3) 6.57g (5.87mmol) nitrophenyl seven cyclohexyl eight poly-cage-type silsesquioxanes, 120mL tetrahydrofuran (THF), 15mL triethylamine join in the 500mL four-hole boiling flask successively, after the stirring and dissolving, add the Pd weight percentage again and be 5% Pd/C catalyzer 0.2487g (0.117mmol).N
2Be protected in temperature rising reflux; slow Dropwise 5 mL 85% formic acid; react after 8 hours, filter, filtrate is at rotary evaporation below 30 ℃; remove and desolvate; suction filtration is used acetone and water washing filter cake respectively, vacuum-drying under the normal temperature; white crystalline powder 6.01g (5.52mmol), be the mixture (C of phenyl ring to the amino cage-type silsesquioxane that replaces in, ortho position
6H
4NH
2(C
6H
11)
7Si
8O
12).
29Si NMR confirm two kinds of isomer the content ratio be about 1: 1.Total yield:94%.Characterization data is:
29Si NMR (119MHz, CDCl
3, 300K, acetone-d
6) δ-65.2 (Si links to each other with the para-orientation phenyl) ,-65.9 (Si links to each other with the ortho position substituted-phenyl) ,-65.9 ,-78.8 (a) ,-80.4 (b);
1H NMR (600MHz, CDCl
3, 300K) 7.40-6.59 (m, 8H), 1.35-1.82 (m, 128H), 1.09 (m, 26H); FTIR (cm
-1, KBr) 2952 (ν
As C-H), 2872 (ν
S C-H), 1450 (ν
C=C), 1247 (β
=CH), 1115 (ν
Si-O-Si), 917 (γ
=CH).
Claims (3)
1. aminophenyl cage-type silsesquioxane, its structural formula is as follows:
R is cyclopentyl, cyclohexyl or isobutyl-in the formula, and amino is a contraposition or a position on phenyl ring.
2. the preparation method of an aminophenyl cage-type silsesquioxane comprises synthetic, the preparation of nitrophenyl cage-type silsesquioxane of phenyl cage-type silsesquioxane, three steps of preparation of aminophenyl cage-type silsesquioxane; Specific as follows:
(1) seven poly-silanetriols is dissolved in volume ratio 20: 1-40: in 1 the tetrahydrofuran (THF) and the mixed solvent of pyridine, under 0-5 ℃ of agitation condition, adding molar weight is seven poly-silanetriol 1-1.2 phenyl-trichloro-silicanes doubly, then 10-30 ℃ of reaction 4-10 hour, collect product, obtain the phenyl cage-type silsesquioxane;
(2) the phenyl cage-type silsesquioxane that step (1) is obtained join carry out in the nitrated system that trichloromethane or tetracol phenixin and concentration expressed in percentage by weight form greater than 96% concentrated nitric acid nitrated, the volume ratio of trichloromethane or tetracol phenixin and concentrated nitric acid is 1: 3-1: 6,-5-10 ℃ following the reaction 4-8 hour, collect product, obtain the nitrophenyl cage-type silsesquioxane;
(3) the nitrophenyl cage-type silsesquioxane that step (2) is obtained joins volume ratio 4: 1-8: in the system that 1 tetrahydrofuran (THF) and triethylamine are formed; adding Pd weight percentage is 5% Pd/C catalyzer; the add-on of catalyzer is that to make the mol ratio of Pd and nitrophenyl cage-type silsesquioxane be 1/10-1/50; at 60 ℃ to reflux temperature; under protection of inert gas; dripping volume ratio is the formic acid of triethylamine 20-50%; reacted 5-10 hour; collect product, obtain the aminophenyl cage-type silsesquioxane.
3. according to the preparation method of claim 2, it is characterized in that: the process that step (3) is collected product is, product is removed solvent at rotary evaporation below 30 ℃, after filtration, vacuum-drying at normal temperatures obtains the finished product after the washing.
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| CN100344636C (en) * | 2005-12-13 | 2007-10-24 | 浙江大学 | Synthesis method for substituting sesquialter siloxane by non-functional alkyl |
| CN100430406C (en) * | 2006-09-21 | 2008-11-05 | 北京理工大学 | Method for preparing octamido phenyl silsesquixanes |
| CN1944441B (en) * | 2006-10-30 | 2012-01-25 | 北京化工大学 | Sesqui-siloxane containing benzoxazinyl group and its composition and preparing method |
| CN100471897C (en) * | 2006-11-30 | 2009-03-25 | 南京大学 | Preparing method of cage anilino methyl sesquisiloxane octamer |
| CN101629010B (en) * | 2009-08-07 | 2011-12-14 | 厦门大学 | Epoxy/POSS/carbon fiber nanometer composite material for light sports equipment and preparation method thereof |
| CN102834404B (en) * | 2010-03-01 | 2016-03-09 | 赢创德固赛有限公司 | The part of polyhedral oligomeric silsesquioxane (POSS)-connection |
| CN102443099B (en) * | 2011-09-16 | 2013-11-27 | 陕西科技大学 | Preparation method of (sesqui) siloxane hybrid modified fluorinated polyacrylate emulsion |
| CN103254562B (en) * | 2012-02-17 | 2015-04-15 | 王克范 | Polyhedral oligomeric silsesquioxane modified intercalated hybrid polymerization material and preparation method thereof |
| CN102643304B (en) * | 2012-03-30 | 2015-07-29 | 山东大学 | A kind of preparation method of cage modle phenyl sesquisiloxane |
| JP6021605B2 (en) * | 2012-11-19 | 2016-11-09 | 新日鉄住金化学株式会社 | Cage type silsesquioxane compound, curable resin composition and resin cured product using the same |
| CN104194264B (en) * | 2014-08-20 | 2019-04-05 | 东莞上海大学纳米技术研究院 | PCB high heat resistance POSS base epoxy nanocomposite and preparation method thereof |
| CN105294754B (en) * | 2015-11-11 | 2018-06-29 | 上海交通大学 | The synthetic method of diamines phenyl double plate cage-type silsesquioxane |
| CN106188127B (en) * | 2016-07-11 | 2020-04-07 | 北京理工大学 | Preparation method of ring-trapezoid nitrophenyl silsesquioxane |
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