CN103288867A - Novel alkoxy silane based POSS (polyhedral oligomeric silsesquioxanes) as well as preparation method and application thereof - Google Patents
Novel alkoxy silane based POSS (polyhedral oligomeric silsesquioxanes) as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses novel alkoxy silane based POSS (polyhedral oligomeric silsesquioxanes) as well as a preparation method and application thereof, belonging to the fields of chemical industry and organic polymer materials. The POSS has a general molecular formula of SixOyR1nR2x-m-nR3m, wherein x is 8, 10 or 12, y=1.5x, n=0-(x-1), m=1-x, m+n is less than or equal to x, and m and n are integers. The preparation method comprises the following steps of: taking POSS raw materials, and performing a hydrosilation reaction on the POSS raw materials and hydrogen-containing silane under the action of a hydrosilation catalyst to obtain a target product. According to the preparation method, an alkoxy silane base is introduced into the POSS, and radicals including Si-OH, Si-H, Si-OR and the like in the alkoxy silane base and a polysiloxane system are used for reacting to form a Si-O-Si bond, so that the alkoxy silane based POSS can obviously promote mechanical properties and thermal properties of silicon resin and silicon rubber when added into condensed type silicon resin and room temperature vulcanized silicon rubber.
Description
Technical field
The present invention relates to a kind of polyhedral oligomeric silsesquioxane (POSS) and preparation method thereof, relate in particular to a kind of novel alkoxysilane group POSS and its preparation method and application, belong to chemical industry and organic polymer material field.
Background technology
Polyhedral oligomeric silsesquioxane (polyhedral oligomeric silsesquioxanes is called for short POSS) is the oligosiloxane that a class has the cage modle of three-dimensional structure, and the general molecular formula is: (RSiO
1.5)
n, n=4,6,7,8,10,12 etc., R can be groups such as hydrogen atom, chlorine atom, alkyl, aryl, thiazolinyl.At eighties of last century beginning of the nineties, people such as Lichtenhan are devoted to prepare the copolymer material that contains POSS, are used for making the rocket propulsion thermofin, and POSS causes people's research interest.2003, U.S.'s hydridization Plastics Company began the commercialization production of various POSS monomers, had promoted developing rapidly of POSS applied research, and all kinds of POSS sills constantly occur.
POSS is with the inorganic skeleton of Si-O key formation and class novel inorganic/organic hybrid nanometer materials that outside organic group constitutes, and also is the friendly section bar material of a class novel environmental.The cage diameter of POSS is between 1～3nm, and its three dimension scale is within the nanometer range, therefore has the novel effects such as small-size effect, surface and interfacial effect, quantum size effect, macro quanta tunnel effect of common nanoparticle.Because above-mentioned special effects, thereby show special thermal characteristics, mechanical property, optical property, dielectric properties, magnetic and acoustic properties, therefore the mechanical property that can effectively improve polymkeric substance in the POSS introducing polymeric system, thermal characteristics, antioxidant property, flame retardant properties etc.Because POSS has inorganic silica skeleton structure, so POSS has outstanding thermotolerance, flame retardant resistance and radioresistance.For the POSS based polyalcohol, when temperature was elevated to the temperature that matrix polymer begins to melt, the molecular structure of POSS remained unchanged; When temperature is high when making its surperficial organic molecule oxidation, POSS is because fixing oxidized organic molecule to oxidation stability, and formation one deck flame retardant coating also provides support structure, protects base material further not oxidized; When temperature further was increased to energy oxidation POSS molecule of the skeleton, POSS ablated into SiO
2And cover substrate surface, play the effect of further heat-proof combustion-resistant.This class material has not only kept the original advantage of polymer materials, but also has the performance of a series of novelties, and as heat-resisting, withstand voltage, fire-retardant and hardness is high, based on above advantage, POSS has widened the range of application of polymeric substrate greatly.
POSS is incorporated in silicon rubber and the silicone resin in the mode of blend, because the reactive force of polysiloxane backbone and POSS molecule is very little, the POSS molecule tends to self accumulative crystallization, thereby does not reach the effect that strengthens mechanical property and thermal characteristics.
Summary of the invention
Primary and foremost purpose of the present invention is to overcome the shortcoming of prior art with not enough, a kind of novel alkoxysilane group POSS is provided, this novel alkoxysilane group POSS can effectively improve the dispersing property of POSS in silicon rubber, silicone resin, especially in the time of in being applied to RTV silicon rubber and silicone resin, can strengthen mechanical property and the thermal characteristics of silicon rubber and silicone resin.
Another object of the present invention is to provide the preparation method of above-mentioned novel alkoxysilane group POSS.
A further object of the present invention is to provide the application of above-mentioned novel alkoxysilane group POSS.
For achieving the above object, the present invention has adopted following technical scheme:
A kind of novel alkoxysilane group POSS, its general molecular formula is Si
xO
yR
1 nR
2 X-m-nR
3 m, wherein, x is 8,10 or 12, y=1.5x, n=0～(x-1), and m=1～x, m+n≤x, m and n are integer.
R
1Be preferably the substituting group that contains two keys, comprise in vinyl, allyl group, acryloyl-oxy propyl group, methacryloxypropyl, acryloyl-oxy methyl, methacryloxypropyl methyl, acrylyl oxy-ethyl, methylacryoyloxyethyl, 3-alkene butyl, 2-alkene butyl, 1-alkene butyl and the methacrylic any one, but be not limited thereto.
R
2Be preferably the saturated alkyl that contains 1～18 carbon, cyclopentyl, methylcyclopentyl, the ethyl cyclopentyl, cyclohexyl, methylcyclohexyl, the ethyl cyclohexyl, phenyl, acetyl oxygen propyl group, acetyl oxygen ethyl, acetyl-o-methyl, aminomethyl, β-aminoethyl, γ-aminopropyl, brine alkyl, the mercapto alkyl, N-(β-aminoethyl)-γ-aminopropyl, γ-2, the 3-epoxypropoxy, beta-hydroxyethyl, γ-hydroxypropyl, 4-hydroxyl butyl, 5-hydroxyl amyl group, N-phenyl-aminomethyl, N-phenyl-β-aminoethyl, N-phenyl-γ-aminopropyl, (N-perfluorooctyl sulfonyl)-aminopropyl, contain fluoroalkyl, in isocyanic acid alkyl and the cyanogen alkyl any one, but be not limited thereto; The molecular formula of described brine alkyl is X ' R-, and the molecular formula of described mercapto alkyl is HSR-, and the molecular formula of described isocyanic acid alkyl is OCNR-, and the molecular formula of cyanogen alkyl is CNR-, and R is preferably the alkyl that contains 1～18 carbon, and X ' comprises chlorine or bromine; The described molecular formula that contains fluoroalkyl is C
xH
2x+1-yF
y, x=1～18,0＜y＜2x+2 wherein, x, y are natural number.
R
3Be preferably R
1With the adduct of silane containing hydrogen monomer, described silane containing hydrogen monomer comprises HSiX
3, HSiX
3, HSiMeX
2, HSiMeX
2, HSiMeX
2, HSiEtX
2, HSiEtX
2, HSiEtX
2, HSiPhX
2, HSiPhX
2, HSiPhX
2, HSiMe
2X, HSiEt
2X, HSiPh
2X, HSiMe
2X, HSiEt
2X, HSiPh
2Among X, HSiMeEtX, HSiMeEtX, HSiMePhX, HSiMePhX, HSiEtPhX and the HSiEtPhX any one, wherein X comprises Cl, Br or OR, R is the alkyl that contains 1～18 carbon.
Particularly, when x=8, then the structural formula of described novel alkoxysilane group POSS is as follows:
The preparation method of above-mentioned novel alkoxysilane group POSS comprises the steps: to get the POSS raw material and carries out addition reaction of silicon with hydrogen with above-mentioned silane containing hydrogen monomer obtain novel alkoxysilane group POSS under the effect of silicon hydrogen addition catalyst.
Preferably, the preparation method of described novel alkoxysilane group POSS comprises the steps: the POSS raw material is joined in the solvent that contains Pt or Rh catalyzer, add the silane containing hydrogen monomer again, after reacting completely, remove catalyzer and solvent, obtain novel alkoxysilane group POSS.
Preferred, the preparation method of described novel alkoxysilane group POSS, comprise the steps: the POSS raw material is joined in the solvent that contains Pt or Rh catalyzer, add the silane containing hydrogen monomer by the dropping mode again, the dropping time is 0～10h, until reacting completely, then utilizes adsorbents adsorb to remove catalyzer, and solvent evaporated, obtain novel alkoxysilane group POSS.
The molecular formula of described POSS raw material comprises Si
8O
12R
1 N+mR
2 8-m-n, Si
10O
15R
1 N+mR
2 10-m-nOr Si
12O
18R
1 N+mR
2 12-m-n, R wherein
1, R
2, m, n requirement and above-mentioned novel alkoxysilane group POSS(general molecular formula be Si
xO
yR
1 nR
2 X-m-nR
3 m) identical.
Described solvent is preferably any one or the two or more combinations in anhydrous diethyl ether, acetone, methylene dichloride, chloroform, benzene,toluene,xylene, tetrahydrofuran (THF), dioxane, the ethylene dichloride.
The consumption of described solvent is preferably 2～100 times of POSS raw materials quality.
The consumption of described silane containing hydrogen monomer is preferably in the POSS raw material 0.1～4 times of two key mole numbers.
Described catalyst consumption is preferably 0.01～2% of POSS raw materials quality.
The application of above-mentioned novel alkoxysilane group POSS in condensed type silicone resin and silicon rubber additive.
A kind of condensed type silicone resin and silicon rubber additive comprise above-mentioned novel alkoxysilane group POSS.
Compared with prior art, the present invention has following advantage and effect: silica-based or halogen is silica-based by introduce alcoxyl in the POSS molecule, utilize radical reactions such as Si-OH, Si-H in the silica-based and polysiloxane system of alkoxyl group or halogen, Si-OR to form the Si-O-Si key, thereby when making this novel POSS in being added into condensed type silicone resin and room temperature vulcanized silicone rubber, can obviously promote mechanical property and the thermal characteristics of silicone resin and silicon rubber.
Embodiment
Do further detailed description below in conjunction with the present invention of embodiment, but embodiments of the present invention are not limited thereto.
Embodiment 1
With anhydrous diethyl ether 500g, Trimethoxy silane 4.88g(39.5mmol) and H
2[PtCl
6] (be dissolved in the Virahol, concentration 4wt% gets 0.5g) and eight vinyl T8-POSS(Vinyl-POSS) 5.00g(7.90mmol, the mole number of two keys is 63.20mmol) in the 1000mL there-necked flask that joins, at 35 ℃ of reaction 8h, be cooled to 20 ℃ and continue to stir 15h.After reaction finishes, add gac, stir 0.5h at 35 ℃, black diethyl ether solution process silica gel and diatomite filtration with gained get clear liquid, and the gained clear liquid is concentrated, and can get colourless oil liquid 9.78g and be products therefrom Si
8O
12R
1 3R
3 5(R
1=vinyl, R
3=trimethoxy silica ethyl), productive rate 98.9%.The nucleus magnetic resonance characterization result of product is:
1HNMR (CDCl
3, ppm): δ 5.78-6.15 (m, H
2C=CH-, 9H), 3.55 (s ,-OCH
3, 45H), 0.66 (m, Si-CH
2, 20H).
Be that the commercially available 107# end hydroxyl silicone oil (60.00g) of 80,000 cP adds in the kneader with viscosity, 2h dewaters under the pressure of 130 ℃ and 1kPa, be cooled to room temperature then, add the above-mentioned novel alkoxysilane group POSS of 6g and 0.045g dibutyl tin dilaurate curing catalysts, mediate 1h, the mixture of gained is transferred in the glue bottle.Method according to GB/T14683-2003 detects mechanical property, adopts TG to test its thermal characteristics, and the result is as shown in table 1.
Embodiment 2
With anhydrous tetrahydro furan (THF) 13g, triethoxyl silane 3.90g(32.0mmol) and H
2[PtCl
6] (be dissolved in the Virahol, concentration 4wt% gets 0.5g) and tetrem thiazolinyl Fourth Ring amyl group T8-POSS(CAS Registry Number:1228876-88-7) 6.4g(8.00mmol, the mole number of two keys is 32mmol) in the 100mL there-necked flask that joins, 65 ℃ of reaction 4h, after being cooled to, add gac, 65 ℃ are stirred 0.5h, black diethyl ether solution process silica gel and diatomite filtration with gained, get clear liquid, the gained clear liquid is concentrated, can get colourless oil liquid 10.07g and be products therefrom Si
8O
12R
2 4R
3 4(R
2=cyclopentyl, R
3=triethoxy silica ethyl), productive rate 97.8%.The nucleus magnetic resonance characterization result of product is:
1HNMR (CDCl
3, ppm): δ 3.75 (m ,-OCH
2CH
3, 24H), 1.4～1.72 (m ,-C
5H
9, 36H), 1.36 (t ,-OCH
2CH
336H), 0.61 (q, Si-CH
2, 16H).
Method according to embodiment 1 prepares condensed room temperature vulcanized silicone rubber, and except novel alkoxysilane group POSS was the product of present embodiment preparation, other was filled a prescription with embodiment 1, and the performance of gained silicon rubber sees Table 1.
Embodiment 3
In the 250mL there-necked flask, add methylene dichloride 50g, ten (3-(3-methacryloxypropyl) propyl group) T10-POSS(prepares according to document: Dalton Trans., 2010,39,3239 – 32440) 9.50g(5.0mmol, the mole number of two keys is 50mmol) and triphenyl rhodium chloride catalyzer 1.9g(be dissolved among the THF, concentration 10wt%), behind 40 ℃ of stirring 0.5h, drip dichloromethane 100mL and dimethylchlorosilane 0.47g(5.0mmol) mixing solutions, add in the 2h, continue 40 ℃ of reaction 4h, after being cooled to, add gac, 40 ℃ are stirred 0.5h, with diethyl ether solution process silica gel and the diatomite filtration of gained, the gained clear liquid is concentrated after the filtration, can get white solid 9.86g and be products therefrom Si
10O
15R
1R
3 9(R
1=3-(3-methacryloxypropyl) propyl group, R
3=(CH
3)
2ClSiCH
2CH
2COOC
3H
6-), productive rate 98.9%.The nucleus magnetic resonance characterization result of product is:
1HNMR (CDCl
3, ppm): δ 6.3～6.4 (d ,-OCOC (CH
3)=CH
2, 18H), 4.25 (t ,-COOCH
2CH
2, 20H), 2.71 (m ,-OCOCH (CH
3) CH
2Si-, 1H), 2.14 (s ,-OCOC (CH
3)=CH
2Si-, 27H), 1.72 (m ,-OCH
2CH
2CH
2Si-, 20H), 1.47 (t ,-OCOCH (CH
3) CH
2Si-, 20H), 1.34 (d ,-OCOCH (CH
3) CH
2Si-, 3H), 0.63 (t ,-SiCH
2CH
2CH
2O-, 20H), 0.44 (s, Si-CH
3, 6H).
Embodiment 4
Prepare laurylene propyl group T12-POSS according to document (Dalton Trans., 2012,41,10585) disclosed method.In the 250mL there-necked flask, add laurylene propyl group T12-POSS11.16g(10.0mmol, the mole number of two keys is 120mmol), acetone 100g, dimethoxy-ethyl silane (CAS Registry Number:19753-84-5) 9.60g(80.0mmol) and Karstedt catalyzer 0.11g(be dissolved among the THF, concentration 1wt%), at 56 ℃ of reaction 6h, after being cooled to, add gac, stir 0.5h at 56 ℃, after the filtration filtrate is used silica gel and diatomite adsorption, refilter, the gained clear liquid is concentrated, can get colourless oil liquid 20.35g and be products therefrom Si
12O
12R
1 4R
3 8(R
1=allyl group, R
3=ethyl dimethoxy silicon propyl group), productive rate 98.0%.The nucleus magnetic resonance characterization result of product is:
1HNMR (CDCl
3, ppm): δ 5.0～5.7 (m, CH
2CHCH
2Si, 12H), 3.56 (s, CH
3OSi-, 48H), 1.37 (m ,-SiCH
2CH
2CH
2Si-, 16H), 1.23 (d ,-SiCH
2CHCH
2, 8H), 1.02 (t, SiCH
2CH
3, 24H), 0.6～0.9 (m ,-SiCH
2CH
2CH
2Si-, CH
3CH
2Si-, 48H).
Method according to embodiment 1 prepares condensed room temperature vulcanized silicone rubber, and except novel alkoxysilane group POSS was the product of present embodiment preparation, other was filled a prescription with embodiment 1, and the performance of gained silicon rubber sees Table 1.
Embodiment 5
Be raw material with octaphenyl T8-POSS and vinyltrimethoxy silane, according to document (J.Am.Chem.Soc.1997,119,3397-3398) disclosed method prepares vinyl seven phenyl T8-POSS.With anhydrous tetrahydro furan (THF) 200g, phenyl methyl chlorosilane 6.28g(40.0mmol), Karstedt catalyzer 0.5g(is dissolved among the THF, concentration 1wt%) and vinyl seven phenyl T8-POSS9.82g(10.00mmol, two key 10.00mmol) in the 500mL there-necked flask that joins, 65 ℃ of reaction 6h, after being cooled to, add gac, 65 ℃ are stirred 0.5h, black tetrahydrofuran solution process silica gel and diatomite filtration with gained, get clear liquid, the gained clear liquid is concentrated, can get colourless oil liquid 11.08g, its major ingredient is Si
8O
12R
2 7R
3 1(R
2=phenyl, R
3=phenyl methyl chlorine silica ethyl), productive rate 97.3%.The nucleus magnetic resonance characterization result of product is:
1HNMR (CDCl
3, ppm): δ 7.1～7.5 (m, C
6H
5-,, 40H), 1.18 (t, PhSiCH
2CH
2Si-, 2H), 0.69 (s ,-SiCH
3, 3H), 0.58 (t ,-SiCH
2CH
2SiPh (Cl) (CH
3), 2H).
Embodiment 6
Be raw material with eight vinyl T8-POSS and phenyltrimethoxysila,e, according to document (J.Am.Chem.Soc.1997,119,3397-3398) disclosed method prepares seven ethenylphenyl T8-POSS.With anhydrous tetrahydro furan (THF) 300g, methyl dimethoxysilane 5.30g(50.0mmol), Karstedt catalyzer 0.5g(is dissolved among the THF, concentration 1wt%) and seven ethenylphenyl T8-POSS6.82g(10.00mmol, two key 70mmol) in the 500mL there-necked flask that joins, 60 ℃ of reaction 6h, after being cooled to room temperature, add gac, continue to be warming up to 60 ℃ and stir 0.5h, black tetrahydrofuran solution process silica gel and diatomite filtration with gained get clear liquid, and the gained clear liquid is concentrated, can get colourless oil liquid 11.88g, its major ingredient is Si
8O
12R
1 2R
2R
3 5(R
1=vinyl, R
2=phenyl, R
3=methyl dimethoxy oxygen base silica ethyl), productive rate 98.0%.The nucleus magnetic resonance characterization result of product is:
1HNMR (CDCl
3, ppm): δ 7.13-7.55 (m, C
6H
5-, 5H), 5.8-6.1 (m ,-SiCH=CH
2, 6H), 3.5 (s ,-OCH
3, 30H), 0.62 (q, Si-CH
2, 20H), 0.14 (s ,-SiCH
3, 15H).
Method according to embodiment 1 prepares condensed room temperature vulcanized silicone rubber, and except novel alkoxysilane group POSS was the product of present embodiment preparation, other was filled a prescription with embodiment 1, and the performance of gained silicon rubber sees Table 1.
Embodiment 7
With anhydrous tetrahydro furan (THF) 300g, methyldiethoxysilane 16.20g(120.0mmol), Karstedt catalyzer 0.5mL(is dissolved among the THF, concentration 1wt%) and eight vinyl T8-POSS6.82g(10.00mmol, two key 80.00mmol) in the 500mL there-necked flask that joins, 60 ℃ of reaction 6h, after being cooled to, add gac, 60 ℃ are stirred 0.5h, black tetrahydrofuran solution process silica gel and diatomite filtration with gained get clear liquid, and the gained clear liquid is concentrated, can get colourless oil liquid 22.27g, its major ingredient is Si
8O
12R
3 8(R
3=methyl diethoxy silica ethyl), productive rate 98.9%.The nucleus magnetic resonance characterization result of product is:
1HNMR (CDCl
3, ppm): δ 3.75 (q ,-OCH
2CH
3, 32H), 1.36 (t ,-OCH
2CH
3, 48H), 0.62 (q, Si-CH
2, 32H), 0.14 (s ,-SiCH
3, 24H).
Method according to embodiment 1 prepares condensed room temperature vulcanized silicone rubber, and except novel alkoxysilane group POSS was the product of present embodiment preparation, other was filled a prescription with embodiment 1, and the performance of gained silicon rubber sees Table 1.
Embodiment 8
With anhydrous diethyl ether 100g, triethoxyl silane 19.68g(120mmol) and H
2[PtCl
6] (be dissolved in the Virahol, concentration 1wt% gets 0.5g) and eight vinyl T8-POSS(Vinyl-POSS) 6.32g(10.00mmol, two key 80.00mmol) in the 250mL there-necked flask that joins, 66 ℃ of reaction 8h are cooled to 20 ℃ and continue to stir 15h.After reaction finishes, add gac, 66 ℃ are stirred 0.5h, and black diethyl ether solution process silica gel and diatomite filtration with gained get clear liquid, and the gained clear liquid is concentrated, and can get colourless oil liquid 25.67g and be products therefrom Si
8O
12R
3 8(R
3=triethoxy silica ethyl), productive rate 98.7%.The nucleus magnetic resonance characterization result of product is:
1HNMR (CDCl
3, ppm): δ 3.75 (q ,-OCH
2CH
3, 48H), 1.36 (t ,-OCH
2CH
3, 72H), 0.60-0.72 (q, Si-CH
2, 32H).
Method according to embodiment 1 prepares condensed room temperature vulcanized silicone rubber, and except novel alkoxysilane group POSS was the product of present embodiment preparation, other was filled a prescription with embodiment 1, and the performance of gained silicon rubber sees Table 1.
Embodiment 9
With anhydrous diethyl ether 100g, triethoxyl silane 8.20g(50mmol) and H
2[PtCl
6] (be dissolved in the Virahol, concentration 1wt% gets 0.5g) and eight vinyl T8-POSS(Vinyl-POSS) 6.32g(10.00mmol, two key 80.00mmol) in the 250mL there-necked flask that joins, 50 ℃ of reaction 8h are cooled to 20 ℃ and continue to stir 15h.After reaction finishes, add gac, 50 ℃ are stirred 0.5h, and black diethyl ether solution process silica gel and diatomite filtration with gained get clear liquid, and the gained clear liquid is concentrated, and can get colourless oil liquid 14.11g and be products therefrom Si
8O
12R
1 3R
3 5(R
3=triethoxy silica ethyl), productive rate 97.2%.The nucleus magnetic resonance characterization result of product is:
1HNMR (CDCl
3, ppm): δ 5.0～5.7 (m, CH
2CHSi, 9H), 3.75 (q ,-OCH
2CH
3, 30H), 1.36 (t ,-OCH
2CH
3, 45H), 0.60-0.72 (q, Si-CH
2, 20H).
Method according to embodiment 1 prepares condensed room temperature vulcanized silicone rubber, and except novel alkoxysilane group POSS was the product of present embodiment preparation, other was filled a prescription with embodiment 1, and the performance of gained silicon rubber sees Table 1.
Embodiment 10
Be raw material with eight vinyl T8-POSS and ethyl trimethoxy silane, according to document (J.Am.Chem.Soc.1997,119,3397-3398) disclosed method prepares ethyl seven vinyl T8-POSS.With anhydrous diethyl ether 100g, triethoxyl silane 16.40g(100mmol) and H
2[PtCl
6] (be dissolved in the Virahol, concentration 4wt% gets 0.5g) and ethyl seven vinyl T8-POSS6.34g(10.00mmol, two key 70.00mmol) in the 250mL there-necked flask that joins, 65 ℃ of reaction 8h are cooled to 20 ℃ and continue to stir 15h.After reaction finishes, add gac, 65 ℃ are stirred 0.5h, and black diethyl ether solution process silica gel and diatomite filtration with gained get clear liquid, and the gained clear liquid is concentrated, and can get colourless oil liquid 22.15g and be products therefrom Si
8O
12R
2R
3 7(R
2=ethyl, R
3=triethoxy silica ethyl), productive rate 97.2%.The nucleus magnetic resonance characterization result of product is:
1HNMR (CDCl
3, ppm): δ 3.73 (q ,-OCH
2CH
3, 30H), 1.36 (t ,-OCH
2CH
3, 45H), 1.07 (t, SiCH
2CH
3, 3H), 0.6～0.9 (m ,-SiCH
2CH
2Si-, CH
3CH
2Si-, 30H).
Method according to embodiment 1 prepares condensed room temperature vulcanized silicone rubber, and except novel alkoxysilane group POSS was the product of present embodiment preparation, other was filled a prescription with embodiment 1, and the performance of gained silicon rubber sees Table 1.
Embodiment 11
With anhydrous diethyl ether 100g, diethylamino phenyl TMOS (CAS:17872-93-4, Phenyldiethoxysilane) 23.52g(120mmol) and H
2[PtCl
6] (be dissolved in the Virahol, concentration 4wt% gets 0.5g) and eight vinyl T8-POSS6.32g(10.00mmol, two key 80.00mmol) in the 250mL there-necked flask that joins, 65 ℃ of reaction 10h are cooled to 20 ℃ and continue to stir 15h.After reaction finishes, add gac, 65 ℃ are stirred 0.5h, and black diethyl ether solution process silica gel and diatomite filtration with gained get clear liquid, and the gained clear liquid is concentrated, and can get colourless oil liquid 28.75g and be products therefrom Si
8O
12R
3 8(R
3=diethylamino phenyl oxygen base silica ethyl), productive rate 96.3%.The nucleus magnetic resonance characterization result of product is:
1HNMR (CDCl
3, ppm): δ 7.1～7.5 (m, C
6H
5-, 40H), 3.76 (q ,-OCH
2CH
3, 32H), 1.36 (t ,-OCH
2CH
3, 48H), 0.6～0.9 (m ,-SiCH
2CH
2Si-, 32H).
Method according to embodiment 1 prepares condensed room temperature vulcanized silicone rubber, and except novel alkoxysilane group POSS was the product of present embodiment preparation, other was filled a prescription with embodiment 1, and the performance of gained silicon rubber sees Table 1.
Embodiment 12
Be raw material with eight vinyl T8-POSS and 3-(2,3-epoxy, third oxygen) propyl trimethoxy silicane, according to document (J.Am.Chem.Soc.1997,119,3397-3398) disclosed method prepares (3-(2,3-epoxy, third oxygen) propyl group seven vinyl T8-POSS.With anhydrous diethyl ether 100g, methyldiethoxysilane 16.2g(120mmol) and H
2[PtCl
6] (be dissolved in the Virahol, concentration 2wt% gets 0.5g) and one (3-(2,3-epoxy third oxygen) propyl group seven vinyl T8-POSS7.2g(10.00mmol, two key 70.00mmol) in the 250mL there-necked flask that joins, 65 ℃ of reaction 10h are cooled to 20 ℃ and continue to stir 15h.After reaction finishes, add gac, 65 ℃ are stirred 0.5h, and black diethyl ether solution process silica gel and diatomite filtration with gained get clear liquid, and the gained clear liquid is concentrated, and can get colourless oil liquid 22.9g and be products therefrom Si
8O
12R
2R
3 7(R
2Be 3-(2,3-epoxy, third oxygen) propyl group, R
3=methyl diethoxy silica ethyl), productive rate 97.8%.The nucleus magnetic resonance characterization result of product is:
1HNMR (CDCl
3, ppm): δ 3.78 (q ,-OCH
2CH
3, 28H), 3.35 (t ,-OCH
2CH
2CH
2Si-, 2H), 2.4-2.8 (m, the epoxy ring hydrogen, 3H), 1.46 (m ,-OCH
2CH
2CH
2Si-, 2H), 1.36 (t ,-OCH
2CH
3, 42H), 0.6～0.8 (m ,-SiCH
2-, 30H), 0.12 (s ,-SiCH
3, 21H).
Method according to embodiment 1 prepares condensed room temperature vulcanized silicone rubber, and except novel alkoxysilane group POSS was the product of present embodiment preparation, other was filled a prescription with embodiment 1, and the performance of gained silicon rubber sees Table 1.
Embodiment 13
With anhydrous diethyl ether 150g, Trimethoxy silane 14.64g(120mmol) and H
2[PtCl
6] (be dissolved in the Virahol, concentration 4wt%, get 0.5g) and ten vinyl T10-POSS (prepare according to document: Dalton Trans., 2010,39,3239 – 32440) 7.9g(10.00mmol, two key 100.00mmol) in the 500mL there-necked flask that joins, 65 ℃ of reaction 10h are cooled to 20 ℃ and continue to stir 15h.After reaction finishes, add gac, 65 ℃ are stirred 0.5h, and black diethyl ether solution process silica gel and diatomite filtration with gained get clear liquid, and the gained clear liquid is concentrated, and can get colourless oil liquid 22.12g and be products therefrom Si
8O
12R
2R
3 7(R
2Be 3-(2,3-epoxy, third oxygen) propyl group, R
3=trimethoxy silica ethyl), productive rate 97.8%.The nucleus magnetic resonance characterization result of product is:
1HNMR (CDCl
3, ppm): δ 5.8～6.1 (m ,-SiCHCH
2,, 6H), 3.56 (q ,-OCH
3, 72H), 0.67 (m ,-SiCH
2CH
2Si-, 32H).
Method according to embodiment 1 prepares condensed room temperature vulcanized silicone rubber, and except novel alkoxysilane group POSS was the product of present embodiment preparation, other was filled a prescription with embodiment 1, and the performance of gained silicon rubber sees Table 1.
Comparative Examples 1
Be that the commercially available 107# end hydroxyl silicone oil (60.00g) of 80,000 cP adds in the kneader with viscosity, 2h dewaters under the pressure of 130 ° of C and 1kPa, be cooled to room temperature then, add 6.00g methyltrimethoxy silane and 0.045g dibutyl tin dilaurate, mediate 1h, the mixture of gained is transferred in the glue bottle.Method according to GB/T14683-2003 detects mechanical property, adopts TG to test its thermal characteristics, and the result is as shown in table 1.
Mechanical property and the thermal characteristics of table 1RTV silicon rubber
Above-described embodiment is preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. a novel alkoxysilane group POSS is characterized in that the general molecular formula is Si
xO
yR
1 nR
2 X-m-nR
3 m, wherein, x is 8,10 or 12, y=1.5x, n=0～(x-1), and m=1～x, m+n≤x, m and n are integer;
R
1For containing the substituting group of two keys;
R
2For containing the saturated alkyl of 1～18 carbon, cyclopentyl, methylcyclopentyl, the ethyl cyclopentyl, cyclohexyl, methylcyclohexyl, the ethyl cyclohexyl, phenyl, acetyl oxygen propyl group, acetyl oxygen ethyl, acetyl-o-methyl, aminomethyl, β-aminoethyl, γ-aminopropyl, brine alkyl, the mercapto alkyl, N-(β-aminoethyl)-γ-aminopropyl, γ-2, the 3-epoxypropoxy, beta-hydroxyethyl, γ-hydroxypropyl, 4-hydroxyl butyl, 5-hydroxyl amyl group, N-phenyl-aminomethyl, N-phenyl-β-aminoethyl, N-phenyl-γ-aminopropyl, (N-perfluorooctyl sulfonyl)-aminopropyl, contain fluoroalkyl, in isocyanic acid alkyl and the cyanogen alkyl any one;
R
3Be R
1Adduct with the silane containing hydrogen monomer.
2. novel alkoxysilane group POSS according to claim 1 is characterized in that:
The described substituting group that contains two keys comprises any one in vinyl, allyl group, acryloyl-oxy propyl group, methacryloxypropyl, acryloyl-oxy methyl, methacryloxypropyl methyl, acrylyl oxy-ethyl, methylacryoyloxyethyl, 3-alkene butyl, 2-alkene butyl, 1-alkene butyl and the methacrylic;
The molecular formula of described brine alkyl is X ' R-, and the molecular formula of described mercapto alkyl is HSR-, and the molecular formula of described isocyanic acid alkyl is OCNR-, and the molecular formula of cyanogen alkyl is CNR-, and R is the alkyl that contains 1～18 carbon, and X ' comprises chlorine or bromine; The described molecular formula that contains fluoroalkyl is C
xH
2x+1-yF
y, x=1～18,0＜y＜2x+2 wherein, x, y are natural number;
Described silane containing hydrogen monomer comprises HSiX
3, HSiX
3, HSiMeX
2, HSiMeX
2, HSiMeX
2, HSiEtX
2, HSiEtX
2, HSiEtX
2, HSiPhX
2, HSiPhX
2, HSiPhX
2, HSiMe
2X, HSiEt
2X, HSiPh
2X, HSiMe
2X, HSiEt
2X, HSiPh
2Among X, HSiMeEtX, HSiMeEtX, HSiMePhX, HSiMePhX, HSiEtPhX and the HSiEtPhX any one, wherein X comprises Cl, Br or OR, R is the alkyl that contains 1～18 carbon.
3. novel alkoxysilane group POSS according to claim 1, it is characterized in that: when x=8, its structural formula is as follows:
4. the preparation method of each described novel alkoxysilane group POSS of claim 1-3 is characterized in that comprising the steps: to get the POSS raw material and carries out addition reaction of silicon with hydrogen with above-mentioned silane containing hydrogen monomer obtain novel alkoxysilane group POSS under the effect of silicon hydrogen addition catalyst.
5. the preparation method of novel alkoxysilane group POSS according to claim 4, it is characterized in that comprising the steps: the POSS raw material is joined in the solvent that contains Pt or Rh catalyzer, add the silane containing hydrogen monomer again, after reacting completely, remove catalyzer and solvent, obtain novel alkoxysilane group POSS.
6. the preparation method of novel alkoxysilane group POSS according to claim 4, it is characterized in that comprising the steps: the POSS raw material is joined in the solvent that contains Pt or Rh catalyzer, add the silane containing hydrogen monomer by the dropping mode again, the dropping time is 0～10h, until reacting completely, then utilize adsorbents adsorb to remove catalyzer, and solvent evaporated, novel alkoxysilane group POSS obtained.
7. the preparation method of novel alkoxysilane group POSS according to claim 4 is characterized in that:
The molecular formula of described POSS raw material comprises Si
8O
12R
1 N+mR
2 8-m-n, Si
10O
15R
1 N+mR
2 10-m-nOr Si
12O
18R
1 N+mR
2 12-m-n
Described solvent is any one or the two or more combination in anhydrous diethyl ether, acetone, methylene dichloride, chloroform, benzene,toluene,xylene, tetrahydrofuran (THF), dioxane, the ethylene dichloride.
8. the preparation method of novel alkoxysilane group POSS according to claim 4 is characterized in that:
The consumption of described solvent is 2～100 times of POSS raw materials quality;
The consumption of described silane containing hydrogen monomer is 0.1～4 times of two key mole numbers in the POSS raw material;
Described catalyst consumption is 0.01～2% of POSS raw materials quality.
9. each described novel alkoxysilane group POSS application in condensed type silicone resin and silicon rubber additive of claim 1-3.
10. a condensed type silicone resin and silicon rubber additive is characterized in that comprising each described novel alkoxysilane group POSS of claim 1-3.
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