CN103288867B - A kind of novel alkoxysilane group POSS and its preparation method and application - Google Patents
A kind of novel alkoxysilane group POSS and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of novel alkoxysilane group POSS and its preparation method and application, belong to chemical industry and high-molecular organic material field.The formula of this POSS is SixOyR1 nR2 x‑m‑ nR3 m, wherein, x is 8,10 or 12, y=1.5x, and n=0～(x 1), m=1～x, m+n≤x, m and n is integer.Its preparation method includes: takes POSS raw material and carries out hydrosilylation acquisition target product under hydrosilylation catalyst effect with silane containing hydrogen.The present invention is silica-based by introducing alcoxyl in POSS, the radical reactions such as the Si OH in alkoxyl and polymeric siloxane systems, Si H, Si OR are utilized to form Si O Si key, so that this alkoxysilane group POSS is when being added in condensed type silicones and room temperature vulcanized silicone rubber, silicones and the mechanical property of silicone rubber and hot property can be obviously improved.
Description
Technical field
The present invention relates to a kind of polyhedral oligomeric silsesquioxane (POSS) and preparation method thereof, particularly relate to a kind of novel alcoxyl
Base silane base POSS and its preparation method and application, belongs to chemical industry and high-molecular organic material field.
Background technology
Polyhedral oligomeric silsesquioxane (polyhedral oligomeric silsesquioxanes is called for short POSS) is that a class has
The oligosiloxane of the cage modle of three dimensional structure, formula is: (RSiO1.5)n, n=4,6,7,8,10,12 etc., R can
Think the groups such as hydrogen atom, chlorine atom, alkyl, aryl, thiazolinyl.At eighties of last century beginning of the nineties, Lichtenhan et al. endeavours
In the preparation copolymer material containing POSS, being used for making rocket propulsion thermal insulation layer, POSS causes the research interest of people.
2003, U.S.'s hydridization Plastics Company started the merchandized handling of various POSS monomer, promotes the rapid of POSS applied research
Development, all kinds of POSS sills constantly occur.
POSS is a class novel inorganic/organic hybrid nanometer that the inorganic skeleton constituted with Si O key is constituted with outside organic group
Level material, is also a class novel environmental friendly material.The cage diameter of POSS is between 1～3nm, and at its three dimension scale
Within nanometer range, therefore have the small-size effect of usual nanoparticle, surface and interfacial effect, quantum size effect,
The novel effect such as macro quanta tunnel effect.Due to above-mentioned special effects, thus show special hot property, mechanical property,
Optical property, dielectric properties, magnetic and acoustic properties, therefore introduce POSS in polymeric system and can be effectively improved polymer
Mechanical property, hot property, antioxygenic property, fire resistance etc..Because POSS has inorganic silica framing structure, therefore POSS
There is prominent thermostability, anti-flammability and radiation resistance.For POSS based polyalcohol, start when temperature is increased to matrix polymer
During the temperature melted, the molecular structure of POSS keeps constant；When temperature height to the organic molecule making its surface aoxidizes, POSS
Because oxidation stability can be fixed oxidized organic molecule, forming one layer of flame retardant coating and provide structure to support, protection base material enters one
Walk not oxidized；When temperature is increased to aoxidize POSS molecule of the skeleton further, POSS ablation becomes SiO2And cover base material
Surface, plays the effect of further heat-proof combustion-resistant.This kind of material not only maintains the original advantage of polymeric material, but also has
Having the performance of series of novel, as heat-resisting, pressure, fire-retardant and hardness is high, based on above advantage, POSS has widened poly-significantly
The range of application of compound base material.
POSS is incorporated in the way of blended in silicone rubber and silicones, due to polysiloxane backbone and the work of POSS molecule
The least, POSS molecule tends to self assemble crystallization, thus does not reaches enhancing mechanical property and the effect of hot property.
Summary of the invention
The primary and foremost purpose of the present invention is that the shortcoming overcoming prior art is with not enough, it is provided that a kind of novel alkoxysilane group POSS,
This novel alkoxysilane group POSS can be effectively improved POSS dispersive property in silicone rubber, silicones, is especially answering
When using in RTV silicone rubber and silicones, it is possible to strengthen silicone rubber and the mechanical property of silicones and hot property.
Another object of the present invention is to provide the preparation method of above-mentioned novel alkoxysilane group POSS.
It is still another object of the present invention to provide the application of above-mentioned novel alkoxysilane group POSS.
For achieving the above object, present invention employs following technical scheme:
A kind of novel alkoxysilane group POSS, its formula is SixOyR1 nR2 x-m-nR3 m, wherein, x be 8,10 or
12, y=1.5x, n=0～(x-1), m=1～x, m+n≤x, m and n is integer.
R1Be preferably containing the substituent group of double bond, including vinyl, pi-allyl, acryloxypropyl, methacryloxypropyl,
Acryloyloxymethyl, methacryloxymethyl, acrylyl oxy-ethyl, methylacryoyloxyethyl, 3-alkene butyl, 2-alkene fourth
Any one in base, 1-alkene butyl and methacrylic, but it is not limited to this.
R2It is preferably containing the saturated alkyl of 1～18 carbon, cyclopenta, methylcyclopentyl, ethylcyclopentyl, cyclohexyl, methyl
Cyclohexyl, ethylcyclohexyl, phenyl, second monomethacryloxypropyl, Acetoxyethyl, acetyl-o-methyl, aminomethyl, β-aminoethyl, γ-
Aminopropyl, brine alkyl, mercapto alkyl, N-(β-aminoethyl)-γ-aminopropyl, γ-2,3-epoxypropoxy, beta-hydroxyethyl, γ-hydroxypropyl,
4-hydroxyl butyl, 5-hydroxyl amyl group, N-phenyl-aminomethyl, N-phenyl-β-aminoethyl, N-phenyl-γ-aminopropyl, (N-perfluoro capryl sulphur
Acyl group)-aminopropyl, containing any one in fluoroalkyl, Carbimide. alkyl and cyanogen alkyl, but be not limited to this；Described brine alkyl
Molecular formula is X ' R-, and the molecular formula of described mercapto alkyl is HSR-, and the molecular formula of described Carbimide. alkyl is OCNR-, cyanogen alkyl
Molecular formula be that CNR-, R are preferably containing the alkyl of 1～18 carbon, X ' includes chlorine or bromine；The described molecular formula containing fluoroalkyl is
CxH2x+1-yFy, wherein x=1～18,0 < y < 2x+2, x, y be natural number.
R3It is preferably R1With the addition compound product of silane containing hydrogen monomer, described silane containing hydrogen monomer includes HSiX3、HSiX3、
HSiMeX2、HSiMeX2、HSiMeX2、HSiEtX2、HSiEtX2、HSiEtX2、HSiPhX2、HSiPhX2、HSiPhX2、
HSiMe2X、HSiEt2X、HSiPh2X、HSiMe2X、HSiEt2X、HSiPh2X、HSiMeEtX、HSiMeEtX、
Any one in HSiMePhX, HSiMePhX, HSiEtPhX and HSiEtPhX, wherein X includes Cl, Br or OR,
R is the alkyl containing 1～18 carbon.
Specifically, as 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: that taking POSS raw material urges at Si-H addition reaction
Carry out hydrosilylation under agent effect with above-mentioned silane containing hydrogen monomer and obtain novel alkoxysilane group POSS.
Preferably, the preparation method of described novel alkoxysilane group POSS, comprise the steps: to add POSS raw material
In the solvent containing Pt or Rh catalyst, add silane containing hydrogen monomer, to reaction completely, remove catalysts and solvents,
Obtain novel alkoxysilane group POSS.
It is furthermore preferred that the preparation method of described novel alkoxysilane group POSS, comprise the steps: POSS raw material
Join in the solvent containing Pt or Rh catalyst, then add silane containing hydrogen monomer by dropping mode, time for adding be 0～
10h, until reaction completely, then utilizes adsorbent to remove catalyst, and solvent evaporated, it is thus achieved that novel alkoxy silane
Base POSS.
The molecular formula of described POSS raw material includes Si8O12R1 n+mR2 8-m-n、Si10O15R1 n+mR2 10-m-nOr
Si12O18R1 n+mR2 12-m-n, wherein R1、R2, requirement and the above-mentioned novel alkoxysilane group POSS(formula of m, n
For SixOyR1 nR2 x-m-nR3 m) identical.
Described solvent be preferably absolute ether, acetone, dichloromethane, chloroform, benzene,toluene,xylene, oxolane,
Any one or two or more combination in dioxane, dichloroethanes.
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 0.1～4 times of double bond molal quantity in POSS raw material.
The consumption of described catalyst is preferably the 0.01～2% of POSS raw materials quality.
Above-mentioned novel alkoxysilane group POSS application in condensed type silicones and silicone rubber additive.
A kind of condensed type silicones and silicone rubber additive, comprise above-mentioned novel alkoxysilane group POSS.
Compared with prior art, the invention have the advantages that and effect: by introducing in POSS molecule, alcoxyl is silica-based or halogen
Silica-based, utilize alkoxyl or halogen is silica-based and the radical reaction such as Si-OH, Si-H, Si-OR in polymeric siloxane systems forms Si-O-Si
Key, so that this novel POSS is when being added in condensed type silicones and room temperature vulcanized silicone rubber, can be obviously improved
Silicones and the mechanical property of silicone rubber and hot property.
Detailed description of the invention
Below in conjunction with embodiment, the present invention done further detailed description, but embodiments of the present invention are not limited to this.
Embodiment 1
By absolute ether 500g, trimethoxy silane 4.88g(39.5mmol) and H2[PtCl6] (it is dissolved in isopropanol, dense
Degree 4wt%, takes 0.5g) and eight vinyl T8-POSS(Vinyl-POSS) 5.00g(7.90mmol, the molal quantity of double bond
For 63.20mmol) in the 1000mL there-necked flask that joins, react 8h at 35 DEG C, be cooled to 20 DEG C and continue stirring 15h.
After reaction terminates, add activated carbon, stir 0.5h at 35 DEG C, the black diethyl ether solution of gained is filtered through silica gel and kieselguhr,
Obtain clear liquid, gained clear liquid is concentrated, colourless oil liquid 9.78g can be obtained and be products therefrom Si8O12R1 3R3 5(R1=vinyl,
R3=trimethoxy silica ethyl), productivity 98.9%.The nuclear magnetic resonance, NMR characterization result of product is:1HNMR(CDCl3,ppm):δ
5.78-6.15(m,H2C=CH-,9H),3.55(s,-OCH3,45H),0.66(m,Si-CH2,20H)。
The commercially available 107# end hydroxyl silicone oil (60.00g) that viscosity is 80,000 cP is added in kneader, at 130 DEG C and 1kPa
Except water 2h under pressure, then it is cooled to room temperature, adds the above-mentioned novel alkoxysilane group POSS of 6g and 0.045g dibutyl two
Tin laurate curing catalysts, mediates 1h, is transferred in glue bottle by the mixture of gained.Side according to GB/T14683-2003
Method detection mechanical property, uses TG to test its hot property, and result is as shown in table 1.
Embodiment 2
By anhydrous tetrahydro furan (THF) 13g, triethoxysilane 3.90g(32.0mmol) and H2[PtCl6] (be dissolved in different
In propanol, concentration 4wt%, take 0.5g) and tetravinyl four cyclopenta T8-POSS(CAS Registry Number:
1228876-88-7) 6.4g(8.00mmol, the molal quantity of double bond is 32mmol) in the 100mL there-necked flask that joins,
65 DEG C of reaction 4h, after being cooled to, add activated carbon, 65 DEG C of stirring 0.5h, by the black diethyl ether solution of gained through silica gel and
Kieselguhr filters, and obtains clear liquid, is concentrated by gained clear liquid, can obtain colourless oil liquid 10.07g and be products therefrom Si8O12R2 4R3 4
(R2=cyclopenta, R3=triethoxy silica ethyl), productivity 97.8%.The nuclear magnetic resonance, NMR characterization result of product is:1HNMR
(CDCl3,ppm):δ3.75(m,-OCH2CH3, 24H), 1.4～1.72 (m ,-C5H9,36H),1.36(t,-OCH2CH336H),
0.61(q,Si-CH2,16H).
Condensed room temperature vulcanized silicone rubber is prepared, except novel alkoxysilane group POSS is this enforcement according to the method for embodiment 1
Outside product prepared by example, other formula is shown in Table 1 with embodiment 1, the performance of gained silicone rubber.
Embodiment 3
In 250mL there-necked flask add dichloromethane 50g, ten (3-(3-methacryloxypropyl) propyl group) T10-POSS(according to
Prepared by document: Dalton Trans., and 2010,39,3,239 32440) 9.50g(5.0mmol, the molal quantity of double bond is 50mmol)
It is dissolved in THF with benzyltriphenylphosphonium chloride rhodium catalyst 1.9g(, concentration 10wt%), after 40 DEG C of stirring 0.5h, drip dichloromethane
Alkane 100mL and dimethylchlorosilane 0.47g(5.0mmol) mixed solution, add in 2h, continue 40 DEG C reaction 4h,
After being cooled to, add activated carbon, 40 DEG C of stirring 0.5h, after filtration, the diethyl ether solution of gained filtered through silica gel and kieselguhr,
Gained clear liquid is concentrated, white solid 9.86g can be obtained and be products therefrom Si10O15R1R3 9(R1=3-(3-methacryloxypropyl)
Propyl group, R3=(CH3)2ClSiCH2CH2COOC3H6-), productivity 98.9%.The nuclear magnetic resonance, NMR characterization result of product is:1HNMR
(CDCl3, ppm): δ 6.3～6.4 (d ,-OCOC (CH3)=CH2,18H),4.25(t,-COOCH2CH2,20H),2.71(m,
-OCOCH(CH3)CH2Si-,1H),2.14(s,-OCOC(CH3)=CH2Si-,27H),1.72(m,-OCH2CH2CH2Si-,
20H),1.47(t,-OCOCH(CH3)CH2Si-,20H),1.34(d,-OCOCH(CH3)CH2Si-,3H),0.63(t,
-SiCH2CH2CH2O-,20H),0.44(s,Si-CH3,6H)。
Embodiment 4
Laurylene propyl group T12-POSS is prepared according to method disclosed in document (Dalton Trans., 2012,41,10585).250
Adding laurylene propyl group T12-POSS11.16g(10.0mmol in mL there-necked flask, the molal quantity of double bond is 120mmol),
Acetone 100g, dimethoxy-ethyl silane (CAS Registry Number:19753-84-5) 9.60g(80.0mmol) and
Karstedt catalyst 0.11g(is dissolved in THF, concentration 1wt%), react 6h at 56 DEG C, after being cooled to, add activity
Charcoal, stirs 0.5h at 56 DEG C, by filtrate silica gel and diatomite adsorption after filtration, refilters, and is concentrated by gained clear liquid, can obtain
Colourless oil liquid 20.35g is products therefrom Si12O12R1 4R3 8(R1=pi-allyl, R3=ethyl dimethoxy silicon propyl group),
Productivity 98.0%.The nuclear magnetic resonance, NMR characterization result of product is:1HNMR(CDCl3, ppm): δ 5.0～5.7 (m, CH2CHCH2Si,
12H),3.56(s,CH3OSi-,48H),1.37(m,-SiCH2CH2CH2Si-,16H),1.23(d,-SiCH2CHCH2,8H),
1.02(t,SiCH2CH3, 24H), 0.6～0.9 (m ,-SiCH2CH2CH2Si-,CH3CH2Si-,48H)。
Condensed room temperature vulcanized silicone rubber is prepared, except novel alkoxysilane group POSS is this enforcement according to the method for embodiment 1
Outside product prepared by example, other formula is shown in Table 1 with embodiment 1, the performance of gained silicone rubber.
Embodiment 5
With octaphenyl T8-POSS and vinyltrimethoxy silane as raw material, according to document (J.Am.Chem.Soc.1997,119,
Method disclosed in 3397-3398) prepares vinyl seven phenyl T8-POSS.By anhydrous tetrahydro furan (THF) 200g, phenyl first
Base chlorosilane 6.28g(40.0mmol), Karstedt catalyst 0.5g(be dissolved in THF, concentration 1wt%) and vinyl seven
Phenyl T8-POSS9.82g(10.00mmol, double bond 10.00mmol) in the 500mL there-necked flask that joins, 65 DEG C of reactions
6h, after being cooled to, adds activated carbon, and 65 DEG C of stirring 0.5h, by the black tetrahydrofuran solution of gained through silica gel and kieselguhr
Filtering, obtain clear liquid, concentrated by gained clear liquid, can obtain colourless oil liquid 11.08g, its Main Ingredients and Appearance is Si8O12R2 7R3 1(R2=
Phenyl, R3=phenyl methyl chlorine silica ethyl), productivity 97.3%.The nuclear magnetic resonance, NMR characterization result of product is:1HNMR(CDCl3,ppm):
δ 7.1～7.5 (m, C6H5-,,40H),1.18(t,PhSiCH2CH2Si-,2H),0.69(s,-SiCH3,3H),0.58(t,
-SiCH2CH2SiPh(Cl)(CH3),2H)。
Embodiment 6
With eight vinyl T8-POSS and phenyltrimethoxysila,e as raw material, according to document (J.Am.Chem.Soc.1997,119,
Method disclosed in 3397-3398) prepares seven ethenylphenyl T8-POSS.By anhydrous tetrahydro furan (THF) 300g, methyl two
Methoxy silane 5.30g(50.0mmol), Karstedt catalyst 0.5g(be dissolved in THF, concentration 1wt%) and seven ethylene
Base phenyl T8-POSS6.82g(10.00mmol, double bond 70mmol) in the 500mL there-necked flask that joins, 60 DEG C of reactions
6h, after being cooled to room temperature, adds activated carbon, is continuously heating to 60 DEG C of stirring 0.5h, by the black tetrahydrofuran solution of gained
Filter through silica gel and kieselguhr, obtain clear liquid, gained clear liquid is concentrated, colourless oil liquid 11.88g can be obtained, its Main Ingredients and Appearance
For Si8O12R1 2R2R3 5(R1=vinyl, R2=phenyl, R3=methyl dimethoxy epoxide silica ethyl), productivity 98.0%.The core of product
Magnetic resonance characterization result is:1HNMR(CDCl3,ppm):δ7.13-7.55(m,C6H5-,5H),5.8-6.1(m,-SiCH=CH2,
6H),3.5(s,-OCH3,30H),0.62(q,Si-CH2, 20H), 0.14 (s ,-SiCH3,15H)。
Condensed room temperature vulcanized silicone rubber is prepared, except novel alkoxysilane group POSS is this enforcement according to the method for embodiment 1
Outside product prepared by example, other formula is shown in Table 1 with embodiment 1, the performance of gained silicone rubber.
Embodiment 7
By anhydrous tetrahydro furan (THF) 300g, methyldiethoxysilane 16.20g(120.0mmol), Karstedt catalysis
Agent 0.5mL(is dissolved in THF, concentration 1wt%) and eight vinyl T8-POSS6.82g(10.00mmol, double bond 80.00
Mmol) in the 500mL there-necked flask joined, 60 DEG C of reaction 6h, after being cooled to, add activated carbon, 60 DEG C are stirred 0.5h,
The black tetrahydrofuran solution of gained is filtered through silica gel and kieselguhr, obtains clear liquid, gained clear liquid is concentrated, water white oil can be obtained
Shape liquid 22.27g, its Main Ingredients and Appearance is Si8O12R3 8(R3=methyl diethoxy silica ethyl), productivity 98.9%.The core of product
Magnetic resonance characterization result is:1HNMR(CDCl3,ppm):δ3.75(q,-OCH2CH3,32H),1.36(t,-OCH2CH3, 48H),
0.62(q,Si-CH2, 32H), 0.14 (s ,-SiCH3,24H)。
Condensed room temperature vulcanized silicone rubber is prepared, except novel alkoxysilane group POSS is this enforcement according to the method for embodiment 1
Outside product prepared by example, other formula is shown in Table 1 with embodiment 1, the performance of gained silicone rubber.
Embodiment 8
By absolute ether 100g, triethoxysilane 19.68g(120mmol) and H2[PtCl6] (it is dissolved in isopropanol, dense
Degree 1wt%, takes 0.5g) and eight vinyl T8-POSS(Vinyl-POSS) 6.32g(10.00mmol, double bond 80.00mmol)
In the 250mL there-necked flask joined, 66 DEG C of reaction 8h, it is cooled to 20 DEG C and continues stirring 15h.After reaction terminates, add and live
Property charcoal, 66 DEG C of stirring 0.5h, the black diethyl ether solution of gained is filtered through silica gel and kieselguhr, obtains clear liquid, by gained clear liquid
Concentrate, colourless oil liquid 25.67g can be obtained and be products therefrom Si8O12R3 8(R3=triethoxy silica ethyl), productivity 98.7%.
The nuclear magnetic resonance, NMR characterization result of product is:1HNMR(CDCl3,ppm):δ3.75(q,-OCH2CH3,48H),1.36(t,
-OCH2CH3, 72H), 0.60-0.72 (q, Si-CH2,32H)。
Condensed room temperature vulcanized silicone rubber is prepared, except novel alkoxysilane group POSS is this enforcement according to the method for embodiment 1
Outside product prepared by example, other formula is shown in Table 1 with embodiment 1, the performance of gained silicone rubber.
Embodiment 9
By absolute ether 100g, triethoxysilane 8.20g(50mmol) and H2[PtCl6] (be dissolved in isopropanol, concentration
1wt%, takes 0.5g) and eight vinyl T8-POSS(Vinyl-POSS) 6.32g(10.00mmol, double bond 80.00mmol)
In the 250mL there-necked flask joined, 50 DEG C of reaction 8h, it is cooled to 20 DEG C and continues stirring 15h.After reaction terminates, add and live
Property charcoal, 50 DEG C of stirring 0.5h, the black diethyl ether solution of gained is filtered through silica gel and kieselguhr, obtains clear liquid, by gained clear liquid
Concentrate, colourless oil liquid 14.11g can be obtained and be products therefrom Si8O12R1 3R3 5(R3=triethoxy silica ethyl), productivity
97.2%.The nuclear magnetic resonance, NMR characterization result of product is:1HNMR(CDCl3, ppm): δ 5.0～5.7 (m, CH2CHSi,9H),3.75
(q,-OCH2CH3,30H),1.36(t,-OCH2CH3, 45H), 0.60-0.72 (q, Si-CH2,20H)。
Condensed room temperature vulcanized silicone rubber is prepared, except novel alkoxysilane group POSS is this enforcement according to the method for embodiment 1
Outside product prepared by example, other formula is shown in Table 1 with embodiment 1, the performance of gained silicone rubber.
Embodiment 10
With eight vinyl T8-POSS and ethyl trimethoxy silane as raw material, according to document (J.Am.Chem.Soc.1997,119,
Method disclosed in 3397-3398) prepares ethyl seven vinyl T8-POSS.By absolute ether 100g, triethoxysilane 16.40
And H g(100mmol)2[PtCl6] (being dissolved in isopropanol, concentration 4wt%, take 0.5g) and ethyl seven vinyl T8-POSS
6.34g(10.00mmol, double bond 70.00mmol) in the 250mL there-necked flask that joins, 65 DEG C of reaction 8h, it is cooled to
20 DEG C are continued stirring 15h.After reaction terminates, add activated carbon, 65 DEG C of stirring 0.5h, the black diethyl ether solution of gained is passed through
Silica gel and kieselguhr filter, and obtain clear liquid, are concentrated by gained clear liquid, can obtain colourless oil liquid 22.15g and be products therefrom
Si8O12R2R3 7(R2=ethyl, R3=triethoxy silica ethyl), productivity 97.2%.The nuclear magnetic resonance, NMR characterization result of product is:1HNMR
(CDCl3,ppm):δ3.73(q,-OCH2CH3,30H),1.36(t,-OCH2CH3, 45H), 1.07 (t, SiCH2CH3,3H),
0.6～0.9 (m ,-SiCH2CH2Si-,CH3CH2Si-,30H)。
Condensed room temperature vulcanized silicone rubber is prepared, except novel alkoxysilane group POSS is this enforcement according to the method for embodiment 1
Outside product prepared by example, other formula is shown in Table 1 with embodiment 1, the performance of gained silicone rubber.
Embodiment 11
By absolute ether 100g, diethylamino phenyl TMOS (CAS:17872-93-4, Phenyldiethoxysilane) 23.52g(120
And H mmol)2[PtCl6] (being dissolved in isopropanol, concentration 4wt%, take 0.5g) and eight vinyl T8-POSS6.32g(10.00
Mmol, double bond 80.00mmol) in the 250mL there-necked flask that joins, 65 DEG C of reaction 10h, it is cooled to 20 DEG C and continues stirring
15h.After reaction terminates, adding activated carbon, 65 DEG C of stirring 0.5h, by the black diethyl ether solution of gained through silica gel and kieselguhr
Filter, obtain clear liquid, gained clear liquid is concentrated, colourless oil liquid 28.75g can be obtained and be products therefrom Si8O12R3 8(R3=benzene
Base diethoxy silica ethyl), productivity 96.3%.The nuclear magnetic resonance, NMR characterization result of product is:1HNMR(CDCl3,ppm):δ
7.1～7.5 (m, C6H5-,40H),3.76(q,-OCH2CH3,32H),1.36(t,-OCH2CH3, 48H), 0.6～0.9 (m,
-SiCH2CH2Si-,32H)。
Condensed room temperature vulcanized silicone rubber is prepared, except novel alkoxysilane group POSS is this enforcement according to the method for embodiment 1
Outside product prepared by example, other formula is shown in Table 1 with embodiment 1, the performance of gained silicone rubber.
Embodiment 12
With eight vinyl T8-POSS and 3-(2,3-epoxy the third oxygen), propyl trimethoxy silicane is for raw material, according to document (J.Am.
Chem.Soc.1997,119,3397-3398) method disclosed in prepares (3-(2,3-epoxy a third oxygen) propyl group seven vinyl T8-POSS.
By absolute ether 100g, methyldiethoxysilane 16.2g(120mmol) and H2[PtCl6] (be dissolved in isopropanol, concentration
2wt%, takes 0.5g) and (3-(2,3-epoxy the third oxygen) propyl group seven vinyl T8-POSS7.2g(10.00mmol, a double bond 70.00
Mmol) in the 250mL there-necked flask joined, 65 DEG C of reaction 10h, it is cooled to 20 DEG C and continues stirring 15h.After reaction terminates,
Add activated carbon, 65 DEG C of stirring 0.5h, the black diethyl ether solution of gained is filtered through silica gel and kieselguhr, obtains clear liquid, by institute
Obtain clear liquid to concentrate, colourless oil liquid 22.9g can be obtained and be products therefrom Si8O12R2R3 7(R2For 3-(2,3-epoxy the third oxygen) propyl group,
R3=methyl diethoxy silica ethyl), productivity 97.8%.The nuclear magnetic resonance, NMR characterization result of product is:1HNMR(CDCl3,ppm):
δ3.78(q,-OCH2CH3,28H),3.35(t,-OCH2CH2CH2Si-, 2H), 2.4-2.8 (m, epoxy ring hydrogen, 3H),
1.46(m,-OCH2CH2CH2Si-, 2H), 1.36 (t ,-OCH2CH3, 42H), 0.6～0.8 (m ,-SiCH2-,30H),0.12(s,
-SiCH3,21H)。
Condensed room temperature vulcanized silicone rubber is prepared, except novel alkoxysilane group POSS is this enforcement according to the method for embodiment 1
Outside product prepared by example, other formula is shown in Table 1 with embodiment 1, the performance of gained silicone rubber.
Embodiment 13
By absolute ether 150g, trimethoxy silane 14.64g(120mmol) and H2[PtCl6] (it is dissolved in isopropanol, dense
Degree 4wt%, takes 0.5g) and ten vinyl T10-POSS (preparing according to document: Dalton Trans., 2010,39,3,239 32440)
7.9g(10.00mmol, double bond 100.00mmol) in the 500mL there-necked flask that joins, 65 DEG C of reaction 10h, it is cooled to
20 DEG C are continued stirring 15h.After reaction terminates, add activated carbon, 65 DEG C of stirring 0.5h, the black diethyl ether solution of gained is passed through
Silica gel and kieselguhr filter, and obtain clear liquid, are concentrated by gained clear liquid, can obtain colourless oil liquid 22.12g and be products therefrom
Si8O12R2R3 7(R2For 3-(2,3-epoxy the third oxygen) propyl group, R3=trimethoxy silica ethyl), productivity 97.8%.The nuclear-magnetism of product is altogether
The characterization result that shakes is:1HNMR(CDCl3, ppm): δ 5.8～6.1 (m ,-SiCHCH2, 6H), 3.56 (q ,-OCH3,72H),0.67
(m,-SiCH2CH2Si-,32H)。
Condensed room temperature vulcanized silicone rubber is prepared, except novel alkoxysilane group POSS is this enforcement according to the method for embodiment 1
Outside product prepared by example, other formula is shown in Table 1 with embodiment 1, the performance of gained silicone rubber.
Comparative example 1
The commercially available 107# end hydroxyl silicone oil (60.00g) that viscosity is 80,000 cP is added in kneader, at 130 ° of C and 1kPa
Pressure under except water 2h, be then cooled to room temperature, add 6.00g MTMS and 0.045g dibutyl tin osmanthus
Acid stannum, mediates 1h, is transferred in glue bottle by the mixture of gained.Mechanical property is detected according to the method for GB/T14683-2003,
Using TG to test its hot property, result is as shown in table 1.
The mechanical property of table 1RTV silicone rubber and hot property
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention being not restricted to the described embodiments,
The change made under other any spirit without departing from the present invention and principle, modify, substitute, combine, simplify, all should
For equivalence substitute mode, within being included in protection scope of the present invention.
Claims (4)
1. an alkoxysilane group POSS, it is characterised in that the one in following compound:
Si8O12R1 3R3 5, R1=vinyl, R3=trimethoxy silica ethyl；
Si8O12R2 4R3 4, R2=cyclopenta, R3=triethoxy silica ethyl；
Si12O12R1 4R3 8, R1=pi-allyl, R3=ethyl dimethoxy silicon propyl group；
Si8O12R2 7R3 1, R2=phenyl, R3=phenyl methyl chlorine silica ethyl；
Si8O12R1 2R2R3 5, R1=vinyl, R2=phenyl, R3=methyl dimethoxy epoxide silica ethyl；
Si8O12R1 3R3 5, R1=vinyl, R3=triethoxy silica ethyl；
Si8O12R2R3 7, R2=ethyl, R3=triethoxy silica ethyl；
Si8O12R3 8, R3=diethylamino phenyl epoxide silica ethyl；
Si8O12R2R3 7, R2For 3-(2,3-epoxy the third oxygen) propyl group, R3=methyl diethoxy silica ethyl；
Si8O12R2R3 7, R2For 3-(2,3-epoxy the third oxygen) propyl group, R3=trimethoxy silica ethyl.
2. the preparation method of the alkoxysilane group POSS described in claim 1, it is characterised in that:
Described alkoxysilane group POSS is Si8O12R1 3R3 5, R1=vinyl, R3During=trimethoxy silica ethyl, it is prepared
Method comprises the steps: absolute ether 500g, trimethoxy silane 4.88g, is dissolved in the H of isopropyl alcohol concentration 4wt%2[PtCl6]
0.5g and the eight vinyl T8-POSS 5.00g that double bond molal quantity is 63.20mmol joins in 1000mL there-necked flask,
35 DEG C of reaction 8h, are cooled to 20 DEG C and continue stirring 15h；After reaction terminates, add activated carbon, stir 0.5h at 35 DEG C, will
The black diethyl ether solution of gained filters through silica gel and kieselguhr, obtains clear liquid, is concentrated by gained clear liquid, obtains colourless oil liquid i.e.
For Si8O12R1 3R3 5；
Described alkoxysilane group POSS is Si8O12R2 4R3 4, R2=cyclopenta, R3During=triethoxy silica ethyl, it is prepared
Method comprises the steps: THF 13g, triethoxysilane 3.90g, is dissolved in the H of isopropyl alcohol concentration 4wt%2[PtCl6]0.5
G and the tetravinyl four cyclopenta T8-POSS 6.4g that double bond molal quantity is 32mmol joins in 100mL there-necked flask, and 65
DEG C reaction 4h, after being cooled to, add activated carbon, 65 DEG C stirring 0.5h, by the black diethyl ether solution of gained through silica gel and silicon
Diatomaceous earth filters, and obtains clear liquid, is concentrated by gained clear liquid, obtains colourless oil liquid and be Si8O12R2 4R3 4；
Described alkoxysilane group POSS is Si12O12R1 4R3 8, R1=pi-allyl, R3During=ethyl dimethoxy silicon propyl group,
Its preparation method comprises the steps: to add the laurylene propyl group that double bond molal quantity is 120mmol in 250mL there-necked flask
T12-POSS 11.16g, acetone 100g, dimethoxy-ethyl silane 9.60g and be dissolved in the Karstedt of THF concentration 1wt%
Catalyst 0.11g, reacts 6h at 56 DEG C, after being cooled to, adds activated carbon, stirs 0.5h at 56 DEG C, by filtrate after filtration
With silica gel and diatomite adsorption, refilter, gained clear liquid is concentrated, obtains colourless oil liquid and be Si12O12R1 4R3 8；
Described alkoxysilane group POSS is Si8O12R2 7R3 1, R2=phenyl, R3During=phenyl methyl chlorine silica ethyl, it is prepared
Method comprises the steps: THF 200g, phenyl methyl chlorosilane 6.28g, is dissolved in the Karstedt of THF concentration 1wt%
Catalyst 0.5g and the vinyl seven phenyl T8-POSS 9.82g that double bond molal quantity is 10.00mmol joins 500mL tri-mouthfuls
In Ping, 65 DEG C of reaction 6h, after being cooled to, add activated carbon, 65 DEG C of stirring 0.5h, by the black tetrahydrofuran solution of gained
Filter through silica gel and kieselguhr, obtain clear liquid, gained clear liquid is concentrated, obtains colourless oil liquid and be Si8O12R2 7R3 1；
Described alkoxysilane group POSS is Si8O12R1 2R2R3 5, R1=vinyl, R2=phenyl, R3=methyl dimethoxy epoxide
During silica ethyl, its preparation method comprises the steps: THF 300g, methyl dimethoxysilane 5.30g, is dissolved in THF
The Karstedt catalyst 0.5g of concentration 1wt% and the seven ethenylphenyl T8-POSS 6.82g that double bond molal quantity is 70mmol
Join in 500mL there-necked flask, 60 DEG C of reaction 6h, after being cooled to room temperature, add activated carbon, be continuously heating to 60 DEG C of stirrings
0.5h, filters the black tetrahydrofuran solution of gained through silica gel and kieselguhr, obtains clear liquid, concentrated by gained clear liquid, obtain nothing
Color oily liquids is Si8O12R1 2R2R3 5；
Described alkoxysilane group POSS is Si8O12R1 3R3 5, R1=vinyl, R3During=triethoxy silica ethyl, it is prepared
Method comprises the steps: absolute ether 100g, triethoxysilane 8.20g, is dissolved in the H of isopropyl alcohol concentration 1wt%2[PtCl6]
0.5g and the eight vinyl T8-POSS 6.32g that double bond molal quantity is 80.00mmol joins in 250mL there-necked flask, 50 DEG C
Reaction 8h, is cooled to 20 DEG C and continues stirring 15h；After reaction terminates, adding activated carbon, 50 DEG C of stirring 0.5h, by gained
Black diethyl ether solution filters through silica gel and kieselguhr, obtains clear liquid, is concentrated by gained clear liquid, obtains colourless oil liquid and be
Si8O12R1 3R3 5；
Described alkoxysilane group POSS is Si8O12R2R3 7, R2=ethyl, R3During=triethoxy silica ethyl, its preparation side
Method comprises the steps: absolute ether 100g, triethoxysilane 16.40g, is dissolved in the H of isopropyl alcohol concentration 1wt%2[PtCl6]
0.5g and the ethyl seven vinyl T8-POSS 6.34g that double bond molal quantity is 70.00mmol joins in 250mL there-necked flask,
65 DEG C of reaction 8h, are cooled to 20 DEG C and continue stirring 15h；After reaction terminates, adding activated carbon, 65 DEG C of stirring 0.5h, by institute
The black diethyl ether solution obtained filters through silica gel and kieselguhr, obtains clear liquid, is concentrated by gained clear liquid, obtains colourless oil liquid and be
Si8O12R2R3 7；
Described alkoxysilane group POSS is Si8O12R3 8, R3During=diethylamino phenyl epoxide silica ethyl, its preparation method include as
Lower step: by absolute ether 100g, diethylamino phenyl TMOS 23.52g (120mmol), be dissolved in isopropyl alcohol concentration 1wt%
H2[PtCl6] 0.5g and the eight vinyl T8-POSS 6.32g that double bond molal quantity is 80.00mmol joins 250mL tri-mouthfuls
In Ping, 65 DEG C of reaction 10h, it is cooled to 20 DEG C and continues stirring 15h；After reaction terminates, adding activated carbon, 65 DEG C are stirred 0.5h,
The black diethyl ether solution of gained is filtered through silica gel and kieselguhr, obtains clear liquid, gained clear liquid is concentrated, obtains colourless oil liquid
It is Si8O12R3 8；
Described alkoxysilane group POSS is Si8O12R2R3 7, R2For 3-(2,3-epoxy the third oxygen) propyl group, R3=methyl diethoxy
During base silica ethyl, its preparation method comprises the steps: absolute ether 100g, methyldiethoxysilane 16.2g, is dissolved in
The H of isopropyl alcohol concentration 1wt%2[PtCl6] 0.5g and (3-(2,3-epoxy a third oxygen) propyl group seven that double bond molal quantity is 70.00mmol
Vinyl T8-POSS 7.2g joins in 250mL there-necked flask, 65 DEG C of reaction 10h, is cooled to 20 DEG C and continues stirring 15h；
After reaction terminates, add activated carbon, 65 DEG C of stirring 0.5h, the black diethyl ether solution of gained filtered through silica gel and kieselguhr,
Obtain clear liquid, gained clear liquid is concentrated, obtains colourless oil liquid and be Si8O12R2R3 7；
Described alkoxysilane group POSS is Si8O12R2R3 7, R2For 3-(2,3-epoxy the third oxygen) propyl group, R3=trimethoxy silicon
During ethyl, its preparation method comprises the steps: absolute ether 150g, trimethoxy silane 14.64g, is dissolved in isopropanol
The H of concentration 1wt%2[PtCl6] 0.5g and the ten vinyl T10-POSS 7.9g that double bond molal quantity is 100.00mmol joins
In 500mL there-necked flask, 65 DEG C of reaction 10h, it is cooled to 20 DEG C and continues stirring 15h；After reaction terminates, addition activated carbon, 65
DEG C stirring 0.5h, filters the black diethyl ether solution of gained through silica gel and kieselguhr, obtains clear liquid, concentrated by gained clear liquid,
Colourless oil liquid is Si8O12R2R3 7。
3. the application in condensed type silicones and silicone rubber additive of the alkoxysilane group POSS described in claim 1.
4. a condensed type silicones and silicone rubber additive, it is characterised in that comprise the alkoxysilane group described in claim 1
POSS。
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| CN104151763B (en) * | 2014-07-31 | 2016-10-05 | 中科院广州化学有限公司南雄材料生产基地 | A kind of vinyl POSS modified organic silicone resin and its preparation method and application |
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| CN108192455B (en) * | 2018-01-15 | 2020-04-24 | 湖北航泰科技有限公司 | Interpenetrating network structure polymer of silicon rubber-fluorocarbon coating and preparation method thereof |
| CN109354511B (en) * | 2018-11-21 | 2021-09-17 | 武汉绿凯科技有限公司 | Graphite mold antioxidant impregnation liquid and preparation method and application thereof |
| CN109749083A (en) * | 2018-12-10 | 2019-05-14 | 沈阳化工大学 | Eight (trimethoxy silica ethyl) poss silicone rubber crosslinking agent |
| CN109776804B (en) * | 2018-12-28 | 2021-05-18 | 广西大学 | Cross-linkable POSS reinforced polyurethane nano hybrid material and preparation method thereof |
| CN111253860A (en) * | 2020-02-09 | 2020-06-09 | 西北工业大学 | Ablation-resistant organic silicon resin coating material and preparation method thereof |
| CN113004704B (en) * | 2021-04-01 | 2023-11-21 | 湖北航泰科技有限公司 | Silicon rubber, preparation method thereof and silicon rubber elastic piece |
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| CN113637170B (en) * | 2021-08-13 | 2022-06-21 | 广东高士高科实业有限公司 | Synthesis method of polysilsesquioxane coupling agent for RTV (room temperature vulcanized) silicone rubber and deketoxime type silicone rubber |
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