CN103204870A - Multi-arm sulfur-containing bridged silsesquioxane monomer, its preparation method and application - Google Patents
Multi-arm sulfur-containing bridged silsesquioxane monomer, its preparation method and application Download PDFInfo
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Abstract
The invention discloses a multi-arm sulfur-containing bridged silsesquioxane monomer, its preparation method and application. The multi-arm sulfur-containing bridged silsesquioxane monomer is shown as formula (I), wherein R is alkyl of the multi-arm compound, R1, R2 and R3 are all selected from the following groups: methoxyl, ethoxyl, methyl and phenyl, m is a natural number of 1-10, and n is a natural number of 3-24. The invention provides the preparation method of the multi-arm sulfur-containing bridged silsesquioxane monomer, and the method includes the step of: reacting a multi-arm alkenyl-terminated compound with mercaptosilane shown in formula (II) under illumination. The invention also provides another preparation method of the multi-arm sulfur-containing bridged silsesquioxane monomer, and the method includes the step of: reacting a multi-arm mercapto compound with alkenyl-terminated silane shown in formula (III) under illumination. The molecular chain of the bridged silsesquioxane monomer provided in the invention contains sulfur atoms with good flexibility, and the bridged silsesquioxane monomer can be further used to prepare bridged polysilsesquioxane and aerogel. The aerogel provided by the invention has excellent elasticity.
Description
Technical field
The present invention relates to a kind of multi-arm sulfur-bearing bridging silsesquioxane monomer and preparation method thereof and application, belong to bridging silsesquioxane technical field.
Background technology
Bridging silsesquioxane monomer is a kind of small molecules that comprises variable organic bridge linkage group and two or more trialkoxysilane groups, the hydrolytic condensation of this small molecules process alkoxyl group can prepare the novel organic-inorganic hybrid material of bridging polysilsesquioxane-a kind of chemically stable and thermal stability excellence, and this material has inorganics and organic characteristic concurrently.The flexibility and changeability of organic bridge linkage group has been given bridging polysilsesquioxane molecular diversity, add flexibility of operation widely such as gentle sol-gel condition and this material preparation sheet material, film, fiber, make it become a class critical material in the advanced material science and technology.
The diversity of this class material and many special performances all derive from the organic group of bridging, these organic groups by Si-C with the form bond of covalent linkage on the trialkoxy silane polymkeric substance.The composition of organic group, length, rigidity, substituent geometrical dimension and functional group's degree all can be adjusted according to the actual requirements.These organic bridge linkage groups are inherent integral parts of hybrid material, so its variation just provides possibility for the overall performance of regulating such as materials such as porosity, thermostability, specific refractory power, optical property, chemical resistant properties, hydrophobic nature and specific inductivity, also can avoid organic phase occurring being separated than big scale with inorganic.Adjustable flexibly on material monolithic chemistry and the physical properties makes this type of material become the excellent candidate material in the Application Areass such as optics manufacturing, support of the catalyst and ceramic precursor.Wherein, sulfur-containing polymer has the high refractive index characteristics, and the transparency is good and have good thermotolerance concurrently, and because sulphur atom can be given molecular chain with kindliness, so the sulfur-containing polymer material also has snappiness preferably usually.
The method for preparing the bridging monomer is a lot, and wherein the most frequently used have three kinds of methods: the 1. metallization of aromatic base, alkyl, alkynyl presoma, and then with the silane reaction of four senses; 2. the hydrosilylation of dienes (polyenoid class), or the diine class that is of little use, but 3. the organic group of two functionality reacts with the organic trialkyl silane that has reactive functionality.1. method needs to adopt Grignard reagent, organolithium or metal hydride that trialkoxy silane is handled, and makes the synthesis technique complexity, severe reaction conditions; 2. method will adopt noble metal catalyst usually, waits the addition reaction of the Si-H group of trichlorosilane on the catalysis carbon-carbon double bond or trialkoxy silane as Platinic chloride, Karsted catalyzer.3. method refers to can react with the organic molecule that has nucleophilic group when trialkoxy silane has an electrophilic group, and the bridging monomer that obtains by this method generally has only 6 alkoxyl groups.
In sum, existing method is mainly used metal catalyst, has complex process, severe reaction conditions, and the not high shortcoming of reaction conversion ratio.
Summary of the invention
The purpose of this invention is to provide a kind of multi-arm sulfur-bearing bridging silsesquioxane monomer and preparation method thereof and application.
The silsesquioxane of multi-arm sulfur-bearing bridging shown in the formula provided by the invention (I) monomer,
R is the alkyl of multi-arm compound, R
1, R
2And R
3All be selected from following radicals: methoxyl group, oxyethyl group, methyl and phenyl; M is the natural number between 1～10, and n is the natural number between 3～24.
In the above-mentioned multi-arm sulfur-bearing bridging silsesquioxane monomer, R specifically can be formula (I-1), (I-2) and (I-3) in arbitrary described group; M is 1～10 natural number, and n is 3 or 8;
In the above-mentioned multi-arm sulfur-bearing bridging silsesquioxane monomer, R specifically can be formula (I-4), (I-5) and (I-6) in arbitrary described group; M is 2～10 natural number, and n is 3,4 or 8,
In the formula (I-5), p is the integer between 0～100.
The invention provides the preparation method of above-mentioned multi-arm sulfur-bearing bridging silsesquioxane monomer, comprise the steps: that hydrosulphonyl silane reacts namely shown in multi-arm end alkenyl compound and the formula (II) under illumination;
In the formula (II), R
1, R
2And R
3All be selected from following radicals: methoxyl group, oxyethyl group, methyl and phenyl, m are the integer between 1～10.
Among the above-mentioned preparation method, described multi-arm end alkenyl compound specifically can be arbitrary described compound among formula (I-1 '), (I-2 ') and (I-3 ');
Among the above-mentioned preparation method, the temperature of described reaction can be 15 ℃～30 ℃, specifically can be 15 ℃, 20 ℃ or 25 ℃; The intensity of described illumination can be 2～300mW/cm
2, specifically can be 10mW/cm
2Or 100mW/cm
2, wavelength is 360～370nm (except the sunlight initiation); The time of described reaction can be 5min～48h, specifically can be 3h or 4h; Described reaction can be carried out under the condition that light trigger exists; The consumption of described light trigger can be 0.05%～5% of hydrosulphonyl silane amount of substance shown in the formula (II); as 1%; described light trigger specifically can be benzophenone; thioxanthone; the thioxanthone acid amides; camphorquinone; (2; 4; the 6-trimethylbenzoyl) diphenyl phosphine oxide; benzoin dimethylether; Diisopropyl azodicarboxylate; 2,2'-Azobis(2,4-dimethylvaleronitrile); benzoyl peroxide; Potassium Persulphate; hydroxy-2-methyl-1-phenyl-acetone; 1-hydroxy-cyclohexyl phenyl ketone; 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio group) phenyl]-1-acetone; 2; 4; 6-trimethylbenzoyl-diphenyl phosphine oxide; 2; 4,6-trimethylbenzoyl phenyl-phosphonic acid ethyl ester; 2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl) phenyl]-the 1-butanone; 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl]-at least a in 1-acetone and the methyl benzoylformate.
The present invention also provides the preparation method of another kind of above-mentioned multi-arm sulfur-bearing bridging silsesquioxane monomer, comprises the steps: that the thiazolinyl of end shown in multi-arm sulfhydryl compound and the formula (III) silane reacts namely under illumination;
In the formula (III), R
1, R
2And R
3All be selected from following radicals: methoxyl group, oxyethyl group, methyl and phenyl, q are the integer between 0～8.
Among the above-mentioned preparation method, described multi-arm sulfhydryl compound specifically can be arbitrary described compound among formula (I-4 '), (I-5 ') and (I-6 ');
Formula (I-5 ') in, p is the integer between 0～100.
Among the above-mentioned preparation method, the temperature of described reaction can be 15 ℃～30 ℃, specifically can be 20 ℃, 25 ℃ or 30 ℃; The intensity of described illumination can be 2～300mW/cm
2, specifically can be 5mW/cm
2, 200mW/cm
2Or 280mW/cm
2, wavelength 360～370nm (except the sunlight initiation); The time of described reaction can be 5min～48h, specifically can be 10min, 30min or 5h; Described reaction can be carried out under the condition that light trigger exists; The consumption of described light trigger can be sulfydryl in described many sulfhydryl compounds amount of substance 0.05%～5%; as 0.6%; 1.25% or 1.7%; described light trigger specifically can be benzophenone; thioxanthone; the thioxanthone acid amides; camphorquinone; (2; 4; the 6-trimethylbenzoyl) diphenyl phosphine oxide; benzoin dimethylether; Diisopropyl azodicarboxylate; 2,2'-Azobis(2,4-dimethylvaleronitrile); benzoyl peroxide; Potassium Persulphate; hydroxy-2-methyl-1-phenyl-acetone; 1-hydroxy-cyclohexyl phenyl ketone; 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio group) phenyl]-1-acetone; 2; 4; 6-trimethylbenzoyl-diphenyl phosphine oxide; 2; 4,6-trimethylbenzoyl phenyl-phosphonic acid ethyl ester; 2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl) phenyl]-the 1-butanone; 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl]-at least a in 1-acetone and the methyl benzoylformate.
The present invention also provides a kind of multi-arm sulfur-bearing bridging polysilsesquioxane, is to be prepared through sol-gel method by above-mentioned multi-arm sulfur-bearing bridging silsesquioxane monomer, can comprise the step of hydrolysis and condensation, gelation and ageing.
The present invention further provides the application of above-mentioned multi-arm sulfur-bearing bridging polysilsesquioxane in the preparation aerogel.
A kind of aerogel provided by the invention can be obtained by above-mentioned multi-arm sulfur-bearing bridging polysilsesquioxane drying step provided by the invention, as conventional drying steps such as supercritical co drying, constant pressure and dry or lyophilizes.
The method for preparing multi-arm bridging silsesquioxane monomer provided by the invention, raw materials used being easy to obtains, synthetic method is simple, the technology gentleness, the reaction-ure conversion-age height, no coupling product can be prepared the bridging monomer with 6-36 alkoxyl group, the number of alkoxyl group can by initial feed choose control the product yield height; Contain the good sulphur atom of kindliness in the bridging silsesquioxane monomer molecule chain provided by the invention, it can further prepare bridging polysilsesquioxane and aerogel, and aerogel provided by the invention has excellent elasticity.
Description of drawings
Fig. 1 is the sulfur-bearing bridging silsesquioxane monomer of embodiment 1 preparation
1The HNMR spectrogram.
Fig. 2 is the photo of the aerogel of embodiment 1 preparation.
Fig. 3 is the compression process stress-strain(ed) curve of the aerogel of embodiment 1 preparation.
Embodiment
Employed experimental technique is ordinary method if no special instructions among the following embodiment.
Used material, reagent etc. if no special instructions, all can obtain from commercial channels among the following embodiment.
Compound is all purchased in Sigma-Aldrich company and Alfa-Aesar company shown in used formula among the following embodiment (I-1 '), (I-2 '), (I-4 ') and (I-5 ').
Compound is prepared as follows shown in used among the following embodiment (I-3 '):
The 15mL vinyltrimethoxy silane is dissolved in the 360mL methyl alcohol, adds 30mL concentrated hydrochloric acid (massfraction 37%), stir 24h down at 90 ℃, obtain white thickness throw out; Use the cold methanol washing precipitate to remove the unreacted small molecules three times, with the methylene dichloride dissolving, wash three times then, use anhydrous sodium sulfate drying methylene dichloride phase, filter back evaporate to dryness filtrate and namely obtain vinyl octahedron cage-type silsesquioxane shown in (I-3 ').
Compound is prepared as follows shown in used among the following embodiment (I-6 '):
The 15mL mercaptopropyl trimethoxysilane is dissolved in the 360mL methyl alcohol, adds 30mL concentrated hydrochloric acid (massfraction 37%), stir 24h down at 90 ℃, obtain white thickness throw out; Use the cold methanol washing precipitate to remove the unreacted small molecules three times, the back wash three times with the methylene dichloride dissolving, uses anhydrous sodium sulfate drying methylene dichloride phase, filters back evaporate to dryness filtrate and namely obtains I-6 ') shown in mercapto propyl group octahedron cage-type silsesquioxane.
Preparation and the application thereof of embodiment 1, multi-arm sulfur-bearing bridging silsesquioxane monomer
(shown in (II), wherein, m is 3, R with the 0.3mol mercaptopropyl trimethoxysilane
1, R
2And R
3Be methoxyl group) and 0.1mol formula (I-2 ') shown in compound add in the single port flask, add Diisopropyl azodicarboxylate 0.003mol (be mercaptopropyl trimethoxysilane molar mass 1%), magnetic agitation, 25 ℃ and UV-irradiation (100mW/cm
2) descend reaction to obtain colourless bridging monomer after 4 hours, shown in (I), wherein, m is 3, n is 3, R
1, R
2And R
3Be OCH
3, R is group shown in the formula (I-2).
Sulfur-bearing bridging silsesquioxane shown in the formula (I)
1The HNMR spectrogram as shown in Figure 1; As seen from the figure, vinyl and sulfydryl all react completely, prove that the structure of the product that obtains is correct.
The above-mentioned 0.004mol bridging monomer that obtains is dissolved in the 10mL ethanol, adds 0.014mol hydrochloric acid, place at 50 ℃ and can obtain multi-arm bridging polysilsesquioxane in 24 hours.
Often press dry the above-mentioned multi-arm bridging polysilsesquioxane that obtains dry: the solvent that uses the poly-silsesquioxane gel inside of normal hexane displacement bridging, configuration 10% (v/v) trimethylchlorosilane/hexane solution, with the gel submergence wherein, 55 ℃ of constant temperature 24h, clean 2 times with normal hexane then, 60 ℃ of oven dry get final product aerogel, its photo is as shown in Figure 2; Its stress under compression strain curve as shown in Figure 3.
Preparation and the application thereof of embodiment 2, multi-arm sulfur-bearing bridging silsesquioxane monomer
(shown in (II), wherein, m is 3, R with the 0.3mol mercaptopropyl trimethoxysilane
1, R
2And R
3Be methoxyl group) and 0.1mol formula (I-1 ') shown in compound add in the single port flask, magnetic agitation obtains the bridging monomer behind the reaction 2h under 20 ℃ and the solar light irradiation, shown in (I), wherein, m is that 3, n is 3, R
1, R
2And R
3Be OCH
3, R is group shown in the formula (I-1).
The above-mentioned 0.004mol bridging monomer that obtains is dissolved in the 10mL ethanol, adds 0.014mol hydrochloric acid, place at 50 ℃ and can obtain multi-arm bridging polysilsesquioxane in 24 hours.
Through the supercritical co drying, Gan Zao pressure is 7.29Mpa as can be known with the above-mentioned multi-arm bridging polysilsesquioxane that obtains, 31 ℃ of temperature and time 1h, get final product aerogel.
Preparation and the application thereof of embodiment 3, multi-arm sulfur-bearing bridging silsesquioxane monomer
(shown in (II), wherein, m is 3, R with the 0.8mol mercaptopropyl trimethoxysilane
1, R
2And R
3Be methoxyl group) and 0.1mol formula (I-3 ') shown in compound add in the single port flask, the quinone 0.008mol that camphorates (for the molar mass of mercaptopropyl trimethoxysilane 1%), magnetic agitation, 15 ℃ and UV-irradiation (10mW/cm
2) reaction obtains the bridging monomer behind the 3h, shown in (I), wherein, m is that 3, n is 8, R
1, R
2And R
3Be OCH
3, R is group shown in the formula (I-3).
The above-mentioned 0.004mol bridging monomer that obtains is dissolved in the 10mL ethanol, adds 0.014mol hydrochloric acid, place at 50 ℃ and can obtain multi-arm bridging polysilsesquioxane in 24 hours.
Often press dry the above-mentioned multi-arm bridging polysilsesquioxane that obtains dry: the solvent that uses normal hexane displacement bridging polysilsesquioxane gel inside, configuration 10% (v/v) trimethylchlorosilane/hexane solution, with the gel submergence wherein, 55 ℃ of constant temperature 24h, clean 2 times with normal hexane then, 60 ℃ of oven dry get final product aerogel.
Preparation and the application thereof of embodiment 4, multi-arm sulfur-bearing bridging silsesquioxane monomer
With compound shown in the 0.1mol formula (I-4 ') and 0.3mol vinyltriethoxysilane (shown in (III), R wherein
1, R
2And R
3Be oxyethyl group, q is 0) mix to add in the single port flask, add shown in the benzophenone 0.005mol (be formula (I-4 ') in the compound 1.7% of the molar mass of sulfydryl), magnetic agitation, 30 ℃ and UV-irradiation (5mW/cm
2) reaction obtains the bridging monomer behind the 5h, shown in (I), wherein, m is that 2, n is 3, R
1, R
2And R
3Be OCH
2CH
3, R is group shown in the formula (I-4).
The above-mentioned 0.004mol bridging monomer that obtains is dissolved in the 10mL ethanol, adds 0.014mol hydrochloric acid, place at 50 ℃ and can obtain multi-arm bridging polysilsesquioxane in 24 hours.
With the above-mentioned multi-arm bridging polysilsesquioxane that obtains through lyophilize, the dry temperature of control be-50 ℃ with time 8h, get final product aerogel.
Preparation and the application thereof of embodiment 5, multi-arm sulfur-bearing bridging silsesquioxane monomer
With compound (wherein, p is 2) shown in the 0.1mol formula (I-5 ') and 0.4mol vinyltrimethoxy silane (shown in (III), R wherein
1, R
2And R
3Be methoxyl group, q is 0) mix to add in the single port flask, add shown in the benzoyl peroxide 0.005mol (be formula (I-5 ') in the compound 1.25% of the molar mass of sulfydryl), magnetic agitation, 20 ℃ and UV-irradiation (200mW/cm
2) obtain the bridging monomer behind the reaction 10min down, shown in (I), wherein, m is 2, n is 4, R
1, R
2And R
3Be OCH
3, R is group shown in the formula (I-5).
The above-mentioned 0.004mol bridging monomer that obtains is dissolved in the 10mL ethanol, adds 0.014mol hydrochloric acid, place at 50 ℃ and can obtain multi-arm bridging polysilsesquioxane in 24 hours.
Often press dry the above-mentioned multi-arm bridging polysilsesquioxane that obtains dry: the solvent that uses normal hexane displacement bridging polysilsesquioxane gel inside, configuration 10% (v/v) trimethylchlorosilane/hexane solution, with the gel submergence wherein, 55 ℃ of constant temperature 24h, clean 2 times with normal hexane then, 60 ℃ of oven dry get final product aerogel.
Preparation and the application thereof of embodiment 6, multi-arm sulfur-bearing bridging silsesquioxane monomer
With compound shown in the 0.1mol formula (I-6 ') and 0.8mol vinyltriethoxysilane (shown in (III), R wherein
1, R
2And R
3Be oxyethyl group, q is 0) mix to add in the single port flask, add shown in the Potassium Persulphate 0.005mol (be formula (I-6 ') in the compound 0.6% of the molar mass of sulfydryl), magnetic agitation, 25 ℃ and UV-irradiation (280mW/cm
2) obtain the bridging monomer behind the reaction 30min down, shown in (I), wherein, m is 2, n is 8, R
1, R
2And R
3Be OCH
2CH
3, R is group shown in the formula (I-6).
The above-mentioned 0.004mol bridging monomer that obtains is dissolved in the 10mL ethanol, adds 0.014mol hydrochloric acid, place at 50 ℃ and can obtain multi-arm bridging polysilsesquioxane in 24 hours.
With the above-mentioned multi-arm bridging polysilsesquioxane that obtains through the supercritical co drying, control pressure 7.29Mpa, 31 ℃ of temperature and time 1h, get final product aerogel.
Claims (12)
1. the silsesquioxane of multi-arm sulfur-bearing bridging shown in the formula (I) monomer,
R is the alkyl of multi-arm compound, R
1, R
2And R
3All be selected from following radicals: methoxyl group, oxyethyl group, methyl and phenyl; M is the natural number between 1～10, and n is the natural number between 3～24.
2. multi-arm sulfur-bearing bridging silsesquioxane monomer according to claim 1 is characterized in that: R be formula (I-1), (I-2) and (I-3) in arbitrary described group; M is 1～10 natural number, and n is the natural number between 3～8;
3. multi-arm sulfur-bearing bridging silsesquioxane monomer according to claim 1 is characterized in that: R be formula (I-4), (I-5) and (I-6) in arbitrary described group; M is 2～10 natural number, and n is the natural number between 3～8.
In the formula (I-5), p is 0～100 integer.
4. the preparation method of claim 1 or 2 described multi-arm sulfur-bearing bridging silsesquioxane monomers comprises the steps: that hydrosulphonyl silane reacts namely shown in multi-arm end alkenyl compound and the formula (II) under illumination;
In the formula (II), R
1, R
2And R
3All be selected from following radicals: methoxyl group, oxyethyl group, methyl and phenyl, m are the integer between 1～10.
5. method according to claim 4 is characterized in that: described multi-arm end alkenyl compound is arbitrary described compound among formula (I-1 '), (I-2 ') and (I-3 ');
6. according to claim 4 or 5 described methods, it is characterized in that: the temperature of described reaction is 15 ℃～30 ℃; The intensity of described illumination is 2～300mW/cm
2The time of described reaction is 5min～48h; Described being reflected under the condition that light trigger exists carried out; The consumption of described light trigger is 0.05%～5% of hydrosulphonyl silane amount of substance shown in the formula (II).
7. the preparation method of claim 1 or 3 described multi-arm sulfur-bearing bridging silsesquioxane monomers comprises the steps: that the thiazolinyl of end shown in multi-arm sulfhydryl compound and the formula (III) silane reacts namely under illumination;
In the formula (III), R
1, R
2And R
3All be selected from following radicals: methoxyl group, oxyethyl group, methyl and phenyl, q are the integer between 0～8.
8. method according to claim 7 is characterized in that: described multi-arm sulfhydryl compound is arbitrary described compound among formula (I-4 '), (I-5 ') and (I-6 ');
Formula (I-5 ') in, p is 0～100 integer.
9. according to claim 7 or 8 described methods, it is characterized in that: the temperature of described reaction is 15 ℃～30 ℃; The intensity of described illumination is 2～300mW/cm
2The time of described reaction is 5min～48h; Described being reflected under the condition that light trigger exists carried out; The consumption of described light trigger be sulfydryl in described many sulfhydryl compounds amount of substance 0.05%～5%.
10. a multi-arm sulfur-bearing bridging polysilsesquioxane is prepared through sol-gel method by arbitrary described multi-arm sulfur-bearing bridging silsesquioxane monomer among the claim 1-3.
11. the application of arbitrary described multi-arm sulfur-bearing bridging polysilsesquioxane in the preparation aerogel among the claim 1-3.
12. an aerogel is obtained by the described multi-arm sulfur-bearing of claim 10 bridging polysilsesquioxane drying step.
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| RU2659077C1 (en) * | 2017-12-13 | 2018-06-28 | Федеральное государственное бюджетное учреждение науки Институт элементоорганических соединений им. А.Н. Несмеянова Российской академии наук (ИНЭОС РАН) | Method for producing flexible siloxane aerogels |
| CN111892819A (en) * | 2020-02-17 | 2020-11-06 | 杭州师范大学 | Preparation method and application of UV (ultraviolet) curing transparent material |
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| RU2659077C1 (en) * | 2017-12-13 | 2018-06-28 | Федеральное государственное бюджетное учреждение науки Институт элементоорганических соединений им. А.Н. Несмеянова Российской академии наук (ИНЭОС РАН) | Method for producing flexible siloxane aerogels |
| CN111892819A (en) * | 2020-02-17 | 2020-11-06 | 杭州师范大学 | Preparation method and application of UV (ultraviolet) curing transparent material |
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