CN103113592A - Multifunctional POSS (polyhedral oligomeric silsesquioxane) modified silicon rubber and preparation method thereof - Google Patents
Multifunctional POSS (polyhedral oligomeric silsesquioxane) modified silicon rubber and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
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- 238000004132 cross linking Methods 0.000 claims abstract description 26
- -1 polysiloxane Polymers 0.000 claims abstract description 26
- 125000000524 functional group Chemical group 0.000 claims abstract description 5
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- 238000006243 chemical reaction Methods 0.000 claims description 31
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- 238000000034 method Methods 0.000 claims description 25
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- 238000003756 stirring Methods 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 15
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
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- 239000003795 chemical substances by application Substances 0.000 claims description 8
- RCNRJBWHLARWRP-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane;platinum Chemical compound [Pt].C=C[Si](C)(C)O[Si](C)(C)C=C RCNRJBWHLARWRP-UHFFFAOYSA-N 0.000 claims description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 230000001588 bifunctional effect Effects 0.000 claims 5
- 238000002390 rotary evaporation Methods 0.000 claims 2
- YFTHPAKWQBTOLK-UHFFFAOYSA-N 2-ethenyloxane Chemical compound C=CC1CCCCO1 YFTHPAKWQBTOLK-UHFFFAOYSA-N 0.000 claims 1
- NBWMAFJESWSREJ-UHFFFAOYSA-N [Pt].C[SiH](C)O[SiH](C)C Chemical compound [Pt].C[SiH](C)O[SiH](C)C NBWMAFJESWSREJ-UHFFFAOYSA-N 0.000 claims 1
- 238000010276 construction Methods 0.000 claims 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims 1
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- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims 1
- 150000003376 silicon Chemical class 0.000 abstract description 47
- 239000000126 substance Substances 0.000 abstract description 15
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses multifunctional POSS (polyhedral oligomeric silsesquioxane) modified silicon rubber and a preparation method thereof. The invention is characterized in that through chemical copolymerization, POSSs containing one/two/three/four active functional groups are respectively introduced into a polysiloxane molecular chain, thus obtaining POSS modified silicon rubber taking the POSSs as pendant groups, blocks and cross-linking points. According to the POSS modified silicon rubber prepared by the invention, the POSSs are uniformly dispersed in a silicon rubber matrix on a real molecular level; and the POSS modified silicon rubber has excellent high temperature and low temperature resistance, mechanical property and dielectric property, and can be used in the aspects of automobiles, electronics and buildings as well as the sophisticated technical fields of space materials, national defense and aerospace.
Description
Technical field
The present invention relates to multifunctional POSS modified silicon rubber and preparation method thereof, particularly four kinds of multifunctional POSS modified silicon rubbers and preparation method thereof.The preparation field that belongs to functional high molecule material and nano composite material.
Background technology
The molecular level hollow cage modle Nano compound that the class diameter that polyhedral oligomeric silsesquioxane (POSS) consists of jointly inorganic Si-O framework and peripheral organic group is 1-3nm.The excellent properties that this organic-inorganic nano hollow cagelike structure is collected rice material, organic polymer material and inorganic materials is integrated, the designability of its molecule and with functional group, higher reactivity makes the POSS matrix material have the character of the cutting of being easy to, there is huge application prospect at numerous areas such as space material, photoelectric material, bio-medical, catalyzer.At present, the synthetic method of POSS mainly contains the hydrolytic condensation method, unfilled corner closed loop method, and functional group's conversion method, the method for POSS modified polyorganosiloxane mainly contains physical blending method and chemical copolymerization method.With silicone resin, compare, silicon rubber is that a kind of cross-linking density is less, molecule segment (M between cross-linking set
c) longer elastomer material, how to improve its thermotolerance and mechanical property, be a technical barrier of modified silicon rubber always.
Guirong Pan and Y.R. Liu are respectively by solution blending (Guirong Pan; James E. Mark; Dale W. J. Polym. Sci., Part B:Polym. Phys., 2003,41 (24): 3314-3323.) and melt blending (Y.R. Liu; Y.D. Huang; L. Liu. Compos. Sci. Tech., 2007,67 (13): 2864-2876.) prepared the POSS modified silicone resin.Because POSS easily assembles in the polysiloxane matrix, be difficult to dispersed, thereby make the mechanical property variation of silicone resin.In Blending Processes, adopt supersound process can make POSS be dispersed in polysiloxane, ultimate compression strength is improved significantly, but POSS very easily separates out from system, makes silicone resin bad stability (James P Lewicki; Mogon Patel; Paul Morrell; John Liggat; Julian Murphy; Richard Pethrick.Sci. Technol. Adv. Mater. 9 (2008) 024403).
Y.R. Liu adopts the condensation polymerization method, has prepared to take two kinds of POSS modified methyl silicone resin (Y.R. Liu that trihydroxy-POSS is the body that dangles as cross-linking set and monohydroxy POSS; Y.D. Huang; L. Liu. Compo. Sci. Tech., 2007,67 (13): 2864 – 2876.), find that POSS can improve the thermostability of material.It is linking agent that Dongzhi Chen be take the derivative of octavinyl-POSS, adopts polycondensation to prepare room curing silicon rubber (Dongzhi Chen; Jiaorong Nie. Polymer Degradation and Stability, 2010,95 (4): 618-626.), result shows that POSS can improve its tensile strength by increasing crosslink density.Hyun-Soo Ryu utilizes silicon hydrogen additive process to prepare to take POSS modified silicone resin (the Hyun-Soo Ryu that POSS is the body that dangles; Dong-Gyun Kim; Jong-Chan Lee. Polymer, 2010,51 (11): 2296 – 2304.), find that the introducing of POSS can improve the thermostability of silicone resin.
A large amount of research work both at home and abroad show: during with the physical modification polysiloxane, due to the nano effect of POSS, very easily reunite, be easy to produce macroface and separate; Even control the blending technology condition, make it dispersed, POSS also very easily separates out from system.Connect and can make POSS be evenly dispersed in polymeric matrix with molecular level by chemical bond, and system structure is stable, can effectively improve mechanical property, thermostability, thermotolerance and the flame retardant resistance of polymeric matrix.At present the report of POSS modified silicone resin is more, but it is less successfully to prepare the report of POSS modified silicon rubber by chemical copolymerization, and technological line is also comparatively single.
Summary of the invention
The objective of the invention is provides technological line of multifunctional POSS modified silicon rubber and preparation method thereof for the deficiencies in the prior art, be characterized in polymeric matrix, disperseing inhomogeneous in order to overcome POSS in physical blending, easily reunion even produces the macroface separation, thereby the structural instability that causes polymkeric substance, performance is easy to deteriorated shortcoming.By chemical copolymerization, cage modle POSS is introduced in the polysiloxane molecule chain, make by chemical bond, to be connected between POSS and polysiloxane matrix, not only improved the consistency of POSS and polysiloxane matrix, effectively solved POSS and disperseed an inhomogeneous difficult problem in the polysiloxane matrix, significantly improved the structural stability of composite silicone rubber, obtained the POSS modified silicon rubber with excellent properties simultaneously.
Purpose of the present invention is achieved by following technical measures, and wherein said raw material umber, except specified otherwise, is parts by weight.
The structural formula of multifunctional POSS modified silicon rubber is as follows:
(1) structural formula of simple function POSS graft modification silicon rubber is
(2) structural formula of difunctionality POSS block copolymerization modified silicon rubber is
(3) POSS is as the modified silicon rubber of cross-linking set
(i) trifunctional POSS as the structural formula of cross-linking set modified silicon rubber is
(ii) four sense POSS as the structural formula of cross-linking set modified silicon rubber are
The preparation method of multifunctional POSS modified silicon rubber comprises the following steps:
(1) preparation of simple function POSS graft modification silicon rubber
(i) prepare the chemical equation of POSS graft polysiloxane oligopolymer as follows:
And prepare by following processing step and processing parameter:
Count by weight, by contents of ethylene 0.5 ~ 10wt %, molecular weight 10000 ~ 100000g.mol
-1100 parts of vinyl silicone oils and seven alkyl hydrogen POSS 0.1 ~ 50 containing an active functional group, add and be equipped with agitator, in the reactor of thermometer and reflux exchanger, under nitrogen protection, inject 100～800 parts of toluene in reactor, start to stir, after being heated to reflux temperature, add again 0.002～0.02 part 1, 3-divinyl-1, 1, 3, 3-tetramethyl disiloxane platinum, back flow reaction 1～72h, revolve the steaming desolvation 50～90 ℃ of temperature, obtain POSS and be positioned at the polysiloxane side chain, POSS-polysiloxane oligomer containing vinyl, it is POSS graft modification polysiloxane oligomer,
(ii) prepare the chemical equation of simple function POSS graft modification silicon rubber as follows:
And prepare by following processing step and processing parameter:
Count by weight, by 100 parts of POSS polysiloxane oligomer, with hydrogen richness 0.5%, molecular weight 3000 g.mol
-1after 3～15 parts of containing hydrogen silicone oils mix, add 1,3-divinyl-1,1,3,0.01～0.04 part, 3-tetramethyl disiloxane platinum, be uniformly mixed the mould that rear injection scribbles releasing agent, 50～170 ℃ of temperature, solidifies 5～100min; The demoulding, obtain the simple function POSS graft modification silicon rubber of POSS as the body that dangles;
(2) preparation of difunctionality POSS block copolymerization modified silicon rubber
(i) chemical equation of the POSS that preparation contains two oxyethyl groups is as follows:
And by following processing step and processing parameter preparation
Count by weight, by 100 parts of two hydrogen POSS, add and be equipped with agitator, in the reactor of thermometer and reflux exchanger, under nitrogen protection, to injecting 10～50 parts of 300～1000 parts of tetrahydrofuran (THF)s and Vinyldimethylethoxysilanes in reactor, start to stir, after being heated to reflux temperature, add 1, 3-divinyl-1, 1, 3, 0.01～0.1 part, 3-tetramethyl disiloxane platinum, back flow reaction 1～96h, steam desolvation at 50～85 ℃ of backspins of temperature, add again 200～500 parts of normal hexane washings to remove impurity, filter, filtrate is 40～80 ℃ of temperature, vacuum-drying 1～10h, the POSS(DE-POSS that acquisition contains two oxyethyl groups),
(ii) prepare the chemical equation of POSS-polysiloxane block oligopolymer as follows:
And by following processing step and processing parameter preparation
Count by weight, by molecular weight 30000 ~ 100000g
.mol
-1100 parts and 300 ~ 800 parts toluene of end hydroxyl silicone oil add and are equipped with agitator, in the reactor of thermometer and reflux exchanger, 0.1～50 part of the POSS that will contain two oxyethyl groups is dissolved in 50～200 parts of toluene, be warmed up to 100 ℃ and start to drip two oxyethyl group POSS-toluene solutions later, difunctionality POSS is mixed with end hydroxyl silicone oil, then 0.1～4 part of stannous octoate is dissolved in to 5～100 parts of toluene, and be added drop-wise in reaction system, in 50 ~ 110 ℃ of reaction 5～180min of temperature, the copolymerization product obtained steams desolvation at 70～95 ℃ of temperature backspins, obtain hydroxy-end capped POSS-polysiloxane block oligopolymer,
(iii) prepare the chemical equation of difunctionality POSS modified silicon rubber by POSS-polysiloxane block oligopolymer as follows:
And prepare by following processing step and processing parameter:
Count by weight, 1～7 part of the composite vulcanizing agent of 100 parts of POSS-polysiloxane block oligopolymers and 0～1 part of 0～1 part+stannous octoate of 1～3 part+vinyl tributyl ketoximyl silane of methyl tributanoximo silane, 0～2 part+Y-aminopropyl triethoxysilane is mixed to rear injection mould, self-vulcanizing 1～72h; The demoulding, obtain difunctionality POSS modified silicon rubber.
(3) POSS is as the preparation of the modified silicon rubber of cross-linking set
(i) trifunctional POSS is as follows as the chemical equation of cross-linking set modified silicon rubber:
And prepare by following processing step and processing parameter:
Count by weight, by molecular weight 30000～100000g
.mol
-1100 parts and 0.1～2 part POSS that contains three silanol groups of end hydroxyl silicone oil is dissolved in 500～1000 parts of tetrahydrofuran (THF)s, mechanical stirring 5～60min or ultrasonic dispersion 5～60min, make it to mix, then add 0.1～0.8 part of stannous octoate, be injected in mould self-vulcanizing 1～72h; The demoulding, obtain the POSS modified silicon rubber of trifunctional POSS as cross-linking set;
(ii) four sense POSS are as follows as the chemical equation of cross-linking set modified silicon rubber:
And prepare by following processing step and processing parameter:
Count by weight, by molecular weight 30000～100000g
.mol
-1100 parts and 0.1～1.8 part POSS that contains four silanol groups of end hydroxyl silicone oil is dissolved in 500～1000 parts of tetrahydrofuran (THF)s, stir 5～60min or ultrasonic dispersion 5～60min, make it to mix, add 0.1～0.8 part of stannous octoate, be injected in mould self-vulcanizing 1～72h; The demoulding, obtain the POSS modified silicon rubber of four sense POSS as cross-linking set.
Multifunctional POSS modified silicon rubber is for technical fields such as automobile, electronics, building aspect and space flight and aviation.
Performance test
1 adopts infrared spectra to the test spectrogram of the simple function SH-POSS that contains an active silicon hydrogen as shown in Figure 1
2 adopt
29si-NMR to the test spectrogram of the simple function SH-POSS that contains an active silicon hydrogen as shown in Figure 2
3 adopt infrared spectras to the test spectrogram of the difunctionality DE-POSS that contains two active oxyethyl groups as shown in Figure 3
4 adopt
29si-NMR to the test spectrogram of the difunctionality DE-POSS that contains two active oxyethyl groups as shown in Fig. 4
5 adopt infrared spectroscopies to the test spectrogram of the TrS-POSS that contains three active silanol groups as shown in Figure 5
6 adopt
29si-NMR to the test spectrogram of the TrS-POSS that contains three active silanol groups as shown in Fig. 6
7 adopt infrared spectroscopies to the test spectrogram of the TeS-POSS that contains four active silanol groups as shown in Figure 7
8 adopt
29si-NMR to the test spectrogram of the TeS-POSS that contains four active silanol groups as shown in Fig. 8
The present invention has following advantage:
1, the present invention by chemical reaction, will contain respectively single/bis-/POSS of tri-/tetra-active function groups is incorporated in the polysiloxane matrix, by the strong chemical bond combination between organic phase and inorganic phase, overcome that inorganic nano-particle is easily reunited and general matrix material in a little less than two-phase interface, while reaching physical blending, POSS is difficult to homodisperse problem in polymeric matrix, make the POSS with hollow nano cagelike structure really realize the dispersed of molecular level in polysiloxane, obtain structure and excellent performance and stable POSS modified silicon rubber.
2, the invention provides and comprise difunctionality POSS---POSS modified silicon rubber of four kinds of different structures such as two oxyethyl group POSS (DEPOSS) and preparation method thereof, enriched the kind of POSS modified silicon rubber, widened the range of application of POSS, the new way of POSS modified silicon rubber is provided simultaneously.
The accompanying drawing explanation
The infared spectrum of Fig. 1 simple function SH-POSS
Fig. 2 simple function SH-POSS's
29the Si-NMR collection of illustrative plates
The infared spectrum of Fig. 3 difunctionality DE-POSS
Fig. 4 difunctionality DE-POSS's
29the Si-NMR collection of illustrative plates
The infared spectrum of Fig. 5 trifunctional TrS-POSS
Fig. 6
?trifunctional TrS-POSS's
29the Si-NMR collection of illustrative plates
The infared spectrum of Fig. 7 tetra-sense TeS-POSS
Fig. 8 tetra-sense TeS-POSS's
29the Si-NMR collection of illustrative plates
Embodiment
Below by embodiment, the present invention is specifically described; be necessary to be pointed out that at this present embodiment only is used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
The preparation of embodiment 1 simple function POSS graft modification silicon rubber
By 0.1 part of SH-POSS and 100 parts of vinyl silicone oils (contents of ethylene 0.5%, molecular weight 100000g
.mol
-1) add in the three-necked bottle that is equipped with agitator, thermometer and reflux exchanger, under nitrogen protection, in three-necked bottle, inject 300 parts of toluene; start to stir; after being heated to reflux temperature, then add 0.002 part 1,3-divinyl-1; 1; 3,3-tetramethyl disiloxane platinum (Pt(dvs)), back flow reaction 12h; the graft product obtained revolves the steaming desolvation 90 ℃ of temperature, obtains POSS and be the dangle POSS-polysiloxane oligomer of body of polysiloxane.
By 100 parts of above-mentioned grafting oligopolymers and hydrogen richness 0.5%, molecular weight 3000g
.mol
-1after 3 parts of containing hydrogen silicone oils mix, add 0.01 part 1,3-divinyl-1,1,3,3-tetramethyl disiloxane platinum (Pt(dvs)), be uniformly mixed the mould that rear injection scribbles releasing agent, at 110 ℃ of curing 5min of temperature, then be warmed up to 170 ℃ and solidify again 10min, the demoulding, obtain simple function POSS modified silicon rubber.
The preparation of embodiment 2 simple function POSS graft modification silicon rubber
By 2 parts of SH-POSS and 100 parts of vinyl silicone oils (contents of ethylene 3%, molecular weight 50000g
.mol
-1) add band to be equipped with in the three-necked bottle of agitator, thermometer and reflux exchanger; under nitrogen protection; inject 300 parts of toluene in there-necked flask, start to stir, after being heated to reflux temperature; add 0.01 part 1; 3-divinyl-1,1,3; 3-tetramethyl disiloxane platinum (Pt(dvs)), back flow reaction 36h.The graft product obtained is revolved to the steaming desolvation 80 ~ 90 ℃ of temperature, obtain POSS and be the dangle POSS-polysiloxane oligomer of body of polysiloxane.
By 100 parts of above-mentioned grafting oligopolymers and hydrogen richness 0.5%, molecular weight 3000g
.mol
-1after 10 parts of containing hydrogen silicone oils mix, add 1,3-divinyl-1,1,3,0.02 part, 3-tetramethyl disiloxane platinum, after being uniformly mixed, inject the mould that scribbles releasing agent, at 110 ℃ of curing 5min of temperature, then be warmed up to 160 ℃ of curing 10min, the demoulding, obtain simple function POSS modified silicon rubber.
The preparation of embodiment 3 simple function POSS graft modification silicon rubber
By 50 parts of SH-POSS and 100 parts of vinyl silicone oils (contents of ethylene 5%, molecular weight 30000g
.mol
-1) add in the three-necked bottle that is equipped with agitator, thermometer and reflux exchanger, under nitrogen protection, in three-necked bottle, inject 800 parts of toluene, start to stir; after being heated to reflux temperature, add 0.02 part 1,3-divinyl-1,1; 3,3-tetramethyl disiloxane platinum, backflow 72h is to reacting completely.The graft product obtained is steamed to desolvation at 70 ~ 80 ℃ of temperature backspins, the POSS-polysiloxane oligomer that acquisition POSS is the polysiloxane pendant groups.
By 100 parts of above-mentioned grafting oligopolymers and hydrogen richness 0.5%, molecular weight 3000g
.mol
-containing hydrogen silicone oil
115 parts mix after, add 0.04 part 1,3-divinyl-1,1,3,3-tetramethyl disiloxane platinum (Pt(dvs)), be uniformly mixed the mould that rear injection scribbles releasing agent, at 110 ℃ of curing 5min of temperature, then be warmed up to 150 ℃ of curing 10min, the demoulding, obtain simple function POSS modified silicon rubber.
4 couples of oxyethyl group POSS(DE-POSS of embodiment) preparation
Add band to be equipped with agitator 100 parts of DH-POSS, in the three-necked bottle of thermometer and reflux exchanger, under nitrogen protection, inject 10 parts of Vinyldimethylethoxysilanes and 300 parts of tetrahydrofuran (THF)s in three-necked bottle, start to stir, after being heated to reflux temperature, add 1, 3-divinyl-1, 1, 3, 3-tetramethyl disiloxane platinum (Pt(dvs)) 0.01 part, back flow reaction 24h, revolve the steaming desolvation at temperature 70 C, add 200 parts of normal hexane washings, filter, filtrate is dried in the vacuum drying oven that is 70 ℃ in temperature, obtain two oxyethyl group POSS(DE-POSS).
5 couples of oxyethyl group POSS(DE-POSS of embodiment) preparation
100 parts of DH-POSS are added and are equipped with agitator, in the three-necked bottle of thermometer and reflux exchanger, under nitrogen protection, inject 50 parts of Vinyldimethylethoxysilanes and 1000 parts of tetrahydrofuran (THF)s in there-necked flask, start to stir, after being heated to reflux temperature, add 1, 3-divinyl-1, 1, 3, 3-tetramethyl disiloxane platinum (Pt(dvs)) 0.04 part, back flow reaction 72h, revolve the steaming desolvation 50 ~ 75 ℃ of temperature, add 500 parts of normal hexane washings, filter, in the vacuum drying oven that filtrate is 70 ℃ in temperature, dry, obtain two oxyethyl group POSS(DE-POSS).
The preparation of embodiment 6 difunctionality POSS modified silicon rubbers
By 100 parts of molecular weight, be 100000g.mol
-1end hydroxyl silicone oil and 300 parts of toluene add in the three-necked bottle that is equipped with agitator, thermometer and reflux exchanger, 0.1 part of DE-POSS is dissolved in to 50 parts of toluene, start to stir, start to drip the DE-POSS-toluene solution after being warmed up to 100 ℃, DE-POSS is mixed with end hydroxyl silicone oil, then 0.1 part of stannous octoate is dissolved in to 5 parts of toluene, is added drop-wise in reaction system, in 110 ℃ of reaction 20min.The copolymerization product obtained steams desolvation at 90 ℃ of backspins, obtains hydroxy-end capped POSS-polysiloxane block oligopolymer.
By 3 parts of 100 parts of above-mentioned copolymerization products and methyl tributanoximo silanes, 2 parts of vinyl tributyl ketoximyl silanes, 0.5 part of 1 part of Y-aminopropyl triethoxysilane (KH550 silane coupling agent) and stannous octoate mix rear injection mould, self-vulcanizing 30h, the demoulding, obtain difunctionality POSS modified silicon rubber.
The preparation of embodiment 7 difunctionality POSS modified silicon rubbers
By 100 parts of molecular weight, be 50000g
.mol
-1300 ~ 800 parts of end hydroxyl silicone oil and toluene add in the three-necked bottle that is equipped with agitator, thermometer and reflux exchanger, 10 parts of DE-POSS are dissolved in to 50 parts of toluene, start to stir, after being warmed up to 100 ℃, start to drip the DE-POSS-toluene solution, DE-POSS is mixed with end hydroxyl silicone oil, then 1 part of stannous octoate is dissolved in to 30 parts of toluene, be added drop-wise in reaction system, in 100 ℃ of reaction 90min of temperature.The copolymerization product obtained steams desolvation at 80 ℃ of backspins of temperature, obtains hydroxy-end capped POSS-polysiloxane block oligopolymer.
By 00 part of above-mentioned copolymer 1,2 parts of methyl tributanoximo silanes, 1 part of vinyl tributyl ketoximyl silane, 0.5 part of Y-aminopropyl triethoxysilane (KH550 silane coupling agent) mixes rear injection mould, self-vulcanizing 48h, the demoulding, obtain difunctionality POSS modified silicon rubber.
The preparation of embodiment 8 difunctionality POSS modified silicon rubbers
By 100 parts of molecular weight, be 30000g.mol
-1end hydroxyl silicone oil and 800 parts of toluene add in the three-necked bottle that is equipped with agitator, thermometer and reflux exchanger, 50 parts of DE-POSS are dissolved in to 200 parts of toluene, start to stir, start to drip the DE-POSS-toluene solution after being warmed up to 100 ℃, DE-POSS is mixed with end hydroxyl silicone oil.Then 4 parts of stannous octoates are dissolved in to 100 parts of toluene, are added drop-wise in reaction system, in 100 ℃ of reaction 180min of temperature.The copolymerization product obtained revolves the steaming desolvation 50 ~ 75 ℃ of temperature, obtains hydroxy-end capped POSS-polysiloxane block oligopolymer.
By 100 parts of above-mentioned copolymerization products, 2 parts of methyl tributanoximo silanes, 1 part of vinyl tributyl ketoximyl silane, mix rear injection mould, self-vulcanizing 72h, the demoulding, obtain difunctionality POSS modified silicon rubber.
Embodiment 9 POSS are as the preparation of the trifunctional POSS modified silicon rubber of cross-linking set
By molecular weight 100000g
.mol
-10.1 part of 100 parts of end hydroxyl silicone oils and the TrS-POSS that contains three active silanol groups are dissolved in respectively in 500 parts of solvents, ultrasonic mixing 30min, after adding 0.1 part of stannous octoate to mix, be injected in mould, self-vulcanizing 72h, the demoulding, obtain the trifunctional POSS modified silicon rubber of POSS as cross-linking set.
By molecular weight 30000g
.mol
-12 parts of 100 parts of end hydroxyl silicone oils and the TrS-POSS that contain three active silanol groups are dissolved in respectively in 1000 parts of tetrahydrofuran solvents, powerful mechanical stirring 60min, after adding 0.8 part of stannous octoate to mix, be injected in mould, self-vulcanizing 24h, the demoulding, obtain the trifunctional POSS modified silicon rubber of POSS as cross-linking set.
Embodiment 11 POSS are as the preparation of four sense POSS modified silicon rubbers of cross-linking set
By molecular weight 100000g
.mol
-1100 parts of end hydroxyl silicone oils and contain four active silanol groups TeS-POSS0.1 ~ 1.8 part and be dissolved in respectively in 500 parts of tetrahydrofuran (THF)s, ultrasonic mixing 20min, after adding 0.1 part of stannous octoate to mix, be injected in mould, self-vulcanizing 72h, the demoulding, obtain the four sense POSS modified silicon rubbers of POSS as cross-linking set.
Embodiment 12 POSS are as the preparation of four sense POSS modified silicon rubbers of cross-linking set
By molecular weight 30000g
.mol
-11.8 parts of 100 parts of end hydroxyl silicone oils and the TeS-POSS that contain four active silanol groups are dissolved in respectively in 1000 parts of tetrahydrofuran solvents, powerful mechanical stirring 60min, make it to mix, after adding 0.8 part of stannous octoate to mix, be injected in mould, self-vulcanizing 12h, the demoulding, obtain the four sense POSS modified silicon rubbers of POSS as cross-linking set.
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-
2013
- 2013-01-07 CN CN201310004033.9A patent/CN103113592B/en active Active
Non-Patent Citations (5)
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