CN103819679A - Preparation method for single-component POSS/addition type silicon resin nanocomposite - Google Patents
Preparation method for single-component POSS/addition type silicon resin nanocomposite Download PDFInfo
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- CN103819679A CN103819679A CN201410073582.6A CN201410073582A CN103819679A CN 103819679 A CN103819679 A CN 103819679A CN 201410073582 A CN201410073582 A CN 201410073582A CN 103819679 A CN103819679 A CN 103819679A
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title abstract description 6
- 229920005989 resin Polymers 0.000 title abstract description 6
- 239000011347 resin Substances 0.000 title abstract description 6
- 229910052710 silicon Inorganic materials 0.000 title abstract description 6
- 239000010703 silicon Substances 0.000 title abstract description 6
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000047 product Substances 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 125000000524 functional group Chemical group 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000006227 byproduct Substances 0.000 claims abstract description 11
- 239000003112 inhibitor Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 44
- 229920002050 silicone resin Polymers 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 125000003545 alkoxy group Chemical group 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 239000012752 auxiliary agent Substances 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 11
- FSIJKGMIQTVTNP-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C=C)C=C FSIJKGMIQTVTNP-UHFFFAOYSA-N 0.000 claims description 10
- -1 catalyzer Substances 0.000 claims description 10
- 230000006837 decompression Effects 0.000 claims description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 239000012265 solid product Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 5
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 4
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 4
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 3
- AUEJBKCWXPYRGZ-UHFFFAOYSA-N 1,1'-biphenyl diethoxysilane Chemical compound C(C)O[SiH2]OCC.C1(=CC=CC=C1)C1=CC=CC=C1 AUEJBKCWXPYRGZ-UHFFFAOYSA-N 0.000 claims description 2
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 claims description 2
- 239000012429 reaction media Substances 0.000 claims description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 abstract 3
- 230000002194 synthesizing effect Effects 0.000 abstract 2
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- 239000007787 solid Substances 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- 239000003643 water by type Substances 0.000 description 10
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000013339 polymer-based nanocomposite Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000003968 arylidene group Chemical group [H]C(c)=* 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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- Silicon Polymers (AREA)
Abstract
The invention provides a preparation method for a single-component POSS/addition type silicon resin nanocomposite. The method comprises the following steps: double-bond-contained polyhedral oligomeric silsesquioxane (POSS) is synthesized, a silanol mixed solution containing different functional groups is prepared, and the double-bond-contained polyhedral oligomeric silsesquioxane (POSS) reacts with the silanol mixed solution to generate the target product namely single-component POSS/addition type silicon resin nanocomposite. The method comprises the following steps: (1), synthesizing the double-bond-contained polyhedral oligomeric silsesquioxane (POSS); (2) synthesizing silanol; (3), adding the double-bond-contained polyhedral oligomeric silsesquioxane (POSS) with different content, which is obtained through the step (1), into the silanol mixed solution obtained through the step (2), and reacting continuously for a period of time, so that a POSS/ silicon resin nanocomposite prepolymer is obtained, then adding an end-capping agent, reducing pressure for removing low-molecular-weight by-products and absolute ethyl alcohol, and adding a cross-linking agent, a catalyst and an inhibitor auxiliary, so that the single-component POSS/addition type silicon resin nanocomposite is obtained.
Description
Technical field
The present invention relates to a kind of preparation method of single component POSS/ add-on type silicone resin nano composite material, belong to macromolecule photoelectric new material technology field.
Background technology
Polymer based nanocomposites combines the advantage of each component, not only has excellent mechanical property, but also has good thermostability, toughness and optics energy.In addition, the inorganic content in polymer based nanocomposites is controlled, lightweight, is convenient to processing, can effectively improve the physical and mechanical properties of polymkeric substance.
Polyhedral oligomeric silsesquioxane (POSS) is that the material that a class contains (RSiO1.5) n structure is the focus of studying in the last few years, and in molecular structure, R substituting group is hydrogen, alkyl, thiazolinyl, aryl, arylidene and their derivatives group.According to the difference of structure, silsesquioxane can be divided into random structure, ladder structure, cagelike structure and half cagelike structure.Its molecular structure easily designs, and by introducing reactive functional groups, makes the rear hybrid forming on molecular level in its access polymer molecular chain.
POSS/ polymer composites is the nano composite material that recent development is got up, it is that oxide core take POSS is as inorganic components, in system, between inorganic phase and organic phase, pass through chemical bonds, do not have reunion and the weak problem of two-phase interface bonding force of inorganic particulate.Prepare nano composite material take POSS as core, its preparation method uniqueness, the composite property excellence of formation, as transparent, heat-resisting, fire-retardant, hardness is high, scrape resistant etc.To sum up measurable POSS and matrix material thereof will have broad application prospects in a lot of fields, as high temperature insulating material, advanced low-k materials, sensor and photoelectric component material etc.
Silicone resin is as a kind of thermosetting resin, and one of the most outstanding performance is excellent thermo-oxidative stability.This is mainly because silicone resin is that therefore decomposition temperature is high take Si-O-Si as skeleton, conventionally all stablizes below at 250 ℃.In addition, silicone resin is difficult to produce by UV-induced free radical reaction, also should not produce oxidizing reaction, so have outstanding weathering resistance.Even under ultraviolet acute irradiation, also unsuitable aging, resistance to yellowing simultaneously.These excellent characteristics make silicone resin be suitable as very much insulative water-proof protection, protection against corrosion and the high-temperaure coating of electron device.But because organosilicon Intermolecular Forces is little, effective crosslinking density is low, the physical strength (bending, stretching, impact etc.) that causes silicone resin a little less than, need to carry out reinforcement to it by other means.The present invention is take the synthesis mechanism of polymer nanocomposites as theoretical basis, first synthesize POSS nano material, in the middle of afterwards POSS being added to alkoxyl group organosilicon hydrolyzation product silanol mixing solutions, carry out cohydrolysis reaction, finally product is carried out to polycondensation end-blocking, decompression removes small molecule by-product and the solvent in system, adds the auxiliary agents such as linking agent, catalyzer, inhibitor can obtain target product high-temperature resistant one-component type POSS/ addition type polysiloxane nano composite material.
Summary of the invention
The object of the present invention is to provide the preparation method of the POSS/ add-on type silicone resin nano composite material of a kind of single component, high temperature resistant, corrosion-resistant, high transparent, excellent insulation performance.
Realizing technical scheme of the present invention is, first synthesize double bond containing cage-type silsesquioxane (POSS), then carry out cohydrolysis reaction as basis by the middle of itself and alkoxyl group organosilicon hydrolyzation product silanol mixing solutions take POSS, decompression removes small molecule by-product and the solvent in system, adds the auxiliary agents such as linking agent, catalyzer, inhibitor can obtain target product single component POSS/ add-on type silicone resin alkane nano composite material.
The inventive method comprises, synthetic double bond containing cage-type silsesquioxane (POSS), prepare the silanol mixing solutions containing different functional groups, double bond containing cage-type silsesquioxane (POSS) reacts with silanol mixing solutions and generates target product single component POSS/ add-on type silicone resin nano composite material; The step of described method is:
(1) double bond containing cage-type silsesquioxane (POSS) is synthetic: by the polycondensation that is hydrolyzed in sour environment of the alkoxyl group organosilicon (A) with trifunctional and tetraethoxy, after finishing, reaction obtains white solid product, the treated double bond containing cage-type silsesquioxane (POSS) that obtains afterwards;
(2) silanol is synthetic: by the alkoxyl group organosilicon (A) with trifunctional and the alkoxyl group organosilicon (B) with two functional groups under sour environment with deionized water generation hydrolysis reaction, using dehydrated alcohol as reaction medium, prepare the silanol mixing solutions containing different functional groups;
(3) the double bond containing cage-type silsesquioxane (POSS) of the step of different content (1) gained is added in the middle of the silanol mixing solutions of step (2) gained, continue reaction for some time under certain condition, obtain POSS/ silicone resin nano composite material performed polymer, add afterwards end-capping reagent divinyl tetramethyl disiloxane, decompression removes low molecule by product and dehydrated alcohol, adds the auxiliary agents such as linking agent, catalyzer, inhibitor can obtain target product POSS/ add-on type silicone resin nano composite material.
In the inventive method step (1), the mass ratio of alkoxyl group organosilicon (A), tetraethoxy and the deionized water of selected trifunctional is 1: (0.8-1.7): (5.5-7).
In the inventive method step (2), the mass ratio of the alkoxyl group organosilicon (A) of selected trifunctional, the alkoxyl group organosilicon (B) of two functional groups and deionized water is 1: (0.2-0.4): (5.1-9.8).
In the inventive method step (3), the amount of double bond containing cage-type silsesquioxane (POSS) is silanol massfraction 5-15%; It is 65 ℃ that bath temperature is set, react with this understanding 2h, obtain POSS/ silicone resin nano composite material performed polymer, add afterwards end-capping reagent divinyl tetramethyl disiloxane to continue reaction 1h, decompression afterwards removes dehydrated alcohol and low molecule by product, add auxiliary agent, can obtain high-temperature resistant one-component type POSS/ add-on type silicone resin nano composite material.
In the inventive method step (3), in selected divinyl tetramethyl disiloxane and step (2), the mass ratio of the alkoxyl group organosilicon (A) of trifunctional is (0.1-0.3): 1.
The alkoxyl group organosilicon (A) of trifunctional is preferably methyltrimethoxy silane, or the one in Union carbide A-162, phenyltrimethoxysila,e, phenyl triethoxysilane or vinyltriethoxysilane.
The alkoxyl group organosilicon (B) of two functional groups is preferably dimethoxydiphenylsilane, or the one in phenylbenzene diethoxy silane, dimethyldimethoxysil,ne or dimethyldiethoxysilane.
The polysiloxane that solidifying agent in the preparation method of the high-temperature resistant one-component type POSS/ add-on type silicone resin nano composite material that the present invention proposes is hydrogen bonds and the combination of platinum catalyst.
Auxiliary agent in the preparation method of one-pack type POSS/ add-on type silicone resin nano composite material that the present invention proposes is one or more combination of inhibitor, antiager, toughner, organosilicon reactive thinner.
Single component POSS/ add-on type silicone resin nano composite material prepared by the inventive method has the following advantages: (1) single component POSS/ add-on type of the present invention silicone resin nano composite material is made up of organopolysiloxane, POSS, linking agent and catalyzer, and the more former polysiloxane cured article of mechanics and resistance to elevated temperatures has significantly lifting; (2) single component POSS/ add-on type silicone resin nano composite material of the present invention has the advantage of organic inorganic materials concurrently, by the direct chemical bonding of functional group after the functional group siloxanes hydrolysis on POSS by POSS organically compound enter in the molecular structure of polysiloxane, system is transparent, does not exist and is separated and muddy phenomenon.(3) the single component POSS/ add-on type silicone resin nano composite material that prepared by the present invention has excellent thermostability, transparence, mechanical property, and synthesis technique is simply controlled, can be within the scope of-50-250 ℃ life-time service.
The inventive method is applicable to prepare single component POSS/ add-on type silicone resin nano composite material, and that this matrix material can be widely used as is electric, the high-temperature insulation protection of electronics, photoelectric material, is a kind of organic silicon nano matrix material of excellent combination property.
Embodiment
The specific embodiment of the invention is as follows: embodiment 1:
Get 30 grams of methyltrimethoxy silanes, 55.1 grams of tetraethoxys, inject respectively the there-necked flask that presets stirring and condensing equipment.Bath temperature is set to 50 ℃, and the pH value of adjusting system with concentrated hydrochloric acid is 3, under agitation in there-necked flask, slowly splashes into 25.8 grams of deionized waters, in 1 hour, dropwises.After reaction 3h, obtain white solid product, stopped reaction, adopt Büchner funnel that white solid is leached, with tetrahydrofuran (THF) washing white solid five times, finally the white solid of processing is put into vacuum drying oven, dry 24h at 100 ℃, the white solid powder obtaining is double bond containing cage-type silsesquioxane (POSS).
Methyltrimethoxy silane and 17.5 grams of dimethyldimethoxysil,ne constant pressure funnel of getting 60 grams slowly splash in the there-necked flask that is added with in advance 150 grams of dehydrated alcohols, 67.4 grams of deionized waters, adjustment system pH value is 4, bath temperature is set to 40 ℃, after isothermal reaction 3h, can obtain silanol solution.
Take silanol massfraction 5-15%(2.7-8.2 gram) POSS add in the middle of above-mentioned silanol mixing solutions, it is 65 ℃ that bath temperature is set, react with this understanding 2h, obtain POSS/ silicone resin nano composite material performed polymer, add afterwards 21.3 grams of divinyl tetramethyl disiloxane to continue reaction 1h, decompression removes low molecule by product and dehydrated alcohol, finally add the auxiliary agents such as linking agent hydrogen containing siloxane, platinum catalyst, inhibitor 1-ethynylcyclohexanol, can obtain target product: single component POSS/ add-on type silicone resin nano composite material.
Embodiment 2:
Get 30 grams of Union carbide A-162s, 27.8 grams of tetraethoxys, inject respectively the there-necked flask that presets stirring and condensing equipment.Bath temperature is set to 50 ℃, and the pH value of adjusting system with concentrated hydrochloric acid is 3, under agitation in there-necked flask, slowly splashes into 13.1 grams of deionized waters, in 1 hour, dropwises.After reaction 3h, obtain white solid product, stopped reaction, adopt Büchner funnel that white solid is leached, with tetrahydrofuran (THF) washing white solid five times, finally the white solid of processing is put into vacuum drying oven, dry 24h at 100 ℃, the white solid powder obtaining is double bond containing cage-type silsesquioxane (POSS).
Union carbide A-162 and 10.9 grams of dimethyldiethoxysilane constant pressure funnel of getting 60 grams slowly splash in the there-necked flask that is added with in advance 150 grams of dehydrated alcohols, 34 grams of deionized waters, adjustment system pH value is 4, bath temperature is set to 40 ℃, after isothermal reaction 3h, can obtain silanol solution.
Take silanol massfraction 5-15%(1.9-5.8 gram) POSS add in the middle of above-mentioned silanol mixing solutions, it is 65 ℃ that bath temperature is set, react with this understanding 2h, obtain POSS/ silicone resin nano composite material performed polymer, add afterwards 21.3 grams of divinyl tetramethyl disiloxane to continue reaction 1h, decompression removes low molecule by product and dehydrated alcohol, finally add the auxiliary agents such as linking agent hydrogen containing siloxane, platinum catalyst, inhibitor 1-ethynylcyclohexanol, can obtain target product: single component POSS/ add-on type silicone resin nano composite material.
Embodiment 3:
Get 30 grams of phenyltrimethoxysila,e, 37.8 grams of tetraethoxys, inject respectively the there-necked flask that presets stirring and condensing equipment.Bath temperature is set to 50 ℃, and the pH value of adjusting system with concentrated hydrochloric acid is 3, under agitation in there-necked flask, slowly splashes into 17.7 grams of deionized waters, in 1 hour, dropwises.After reaction 3h, obtain white solid product, stopped reaction, adopt Büchner funnel that white solid is leached, with tetrahydrofuran (THF) washing white solid five times, finally the white solid of processing is put into vacuum drying oven, dry 24h at 100 ℃, the white solid powder obtaining is double bond containing cage-type silsesquioxane (POSS).
Phenyltrimethoxysila,e and 14.8 grams of dimethyldiethoxysilane constant pressure funnel of getting 60 grams slowly splash in the there-necked flask that is added with in advance 90 grams of dehydrated alcohols, 46.3 grams of deionized waters, adjustment system pH value is 4, bath temperature is set to 40 ℃, after isothermal reaction 3h, can obtain silanol solution.
Take silanol massfraction 5-15%(2.8-8.5 gram) POSS add in the middle of above-mentioned silanol mixing solutions, it is 65 ℃ that bath temperature is set, react with this understanding 2h, obtain POSS/ silicone resin nano composite material performed polymer, add afterwards 14.7 grams of divinyl tetramethyl disiloxane to continue reaction 1h, decompression removes low molecule by product and dehydrated alcohol, finally add linking agent hydrogen containing siloxane, platinum catalyst, the auxiliary agents such as inhibitor 1-ethynylcyclohexanol, can obtain target product: high-temperature resistant one-component type POSS/ add-on type silicone resin nano composite material.
Embodiment 4:
Get 30 grams of phenyl triethoxysilanes, 55.1 grams of tetraethoxys, inject respectively the there-necked flask that presets stirring and condensing equipment.Bath temperature is set to 50 ℃, and the pH value of adjusting system with concentrated hydrochloric acid is 3, under agitation in there-necked flask, slowly splashes into 14.6 grams of deionized waters, in 1 hour, dropwises.After reaction 3h, obtain white solid product, stopped reaction, adopt Büchner funnel that white solid is leached, with tetrahydrofuran (THF) washing white solid five times, finally the white solid of processing is put into vacuum drying oven, dry 24h at 100 ℃, the white solid powder obtaining is double bond containing cage-type silsesquioxane (POSS).
Phenyl triethoxysilane and 12.2 grams of dimethyldiethoxysilane constant pressure funnel of getting 60 grams slowly splash in the there-necked flask that is added with in advance 150 grams of dehydrated alcohols, 38.2 grams of deionized waters, adjustment system pH value is 4, bath temperature is set to 40 ℃, after isothermal reaction 3h, can obtain silanol solution.
Take silanol massfraction 5-15%(2.3-7.0 gram) POSS add in the middle of above-mentioned silanol mixing solutions, it is 65 ℃ that bath temperature is set, react with this understanding 2h, obtain POSS/ silicone resin nano composite material performed polymer, add afterwards 12.1 grams of divinyl tetramethyl disiloxane to continue reaction 1h, decompression removes low molecule by product and dehydrated alcohol, finally add the auxiliary agents such as linking agent hydrogen containing siloxane, platinum catalyst, inhibitor 1-ethynylcyclohexanol, can obtain target product: single component POSS/ add-on type silicone resin nano composite material.
Embodiment 5:
Get 30 grams of vinyltriethoxysilanes, 12.5 grams of tetraethoxys, inject respectively the there-necked flask that presets stirring and condensing equipment.Bath temperature is set to 50 ℃, and the pH value of adjusting system with concentrated hydrochloric acid is 3, under agitation in there-necked flask, slowly splashes into 18.4 grams of deionized waters, in 1 hour, dropwises.After reaction 3h, obtain white solid product, stopped reaction, adopt Büchner funnel that white solid is leached, with tetrahydrofuran (THF) washing white solid five times, finally the white solid of processing is put into vacuum drying oven, dry 24h at 100 ℃, the white solid powder obtaining is double bond containing cage-type silsesquioxane (POSS).
Vinyltriethoxysilane and 17.5 grams of dimethyldimethoxysil,ne constant pressure funnel of getting 60 grams slowly splash in the there-necked flask that is added with in advance 150 grams of dehydrated alcohols, 48.2 grams of deionized waters, adjustment system pH value is 4, bath temperature is set to 40 ℃, after isothermal reaction 3h, can obtain silanol solution.
Take silanol massfraction 5-15%(2.3-7.0 gram) POSS add in the middle of above-mentioned silanol mixing solutions, it is 65 ℃ that bath temperature is set, react with this understanding 2h, obtain POSS/ silicone resin nano composite material performed polymer, add afterwards 15.2 grams of divinyl tetramethyl disiloxane to continue reaction 1h, decompression removes low molecule by product and dehydrated alcohol, finally add the auxiliary agents such as linking agent hydrogen containing siloxane, platinum catalyst, inhibitor 1-ethynylcyclohexanol, can obtain target product: single component POSS/ add-on type silicone resin nano composite material.
Claims (7)
1. the preparation method of a single component POSS/ add-on type silicone resin nano composite material, it is characterized in that, described method comprises, synthetic double bond containing cage-type silsesquioxane (POSS), prepare the silanol mixing solutions containing different functional groups, double bond containing cage-type silsesquioxane (POSS) reacts with silanol mixing solutions and generates target product single component POSS/ add-on type silicone resin nano composite material; The step of described method is:
(1) double bond containing cage-type silsesquioxane (POSS) is synthetic: will have the polycondensation that is hydrolyzed of the alkoxyl group organosilicon of trifunctional and tetraethoxy in sour environment, after finishing, reaction obtains white solid product, the treated double bond containing cage-type silsesquioxane (POSS) that obtains afterwards;
(2) silanol is synthetic: by the alkoxyl group organosilicon with trifunctional and the alkoxyl group organosilicon with two functional groups under sour environment with deionized water generation hydrolysis reaction, using dehydrated alcohol as reaction medium, prepare the silanol mixing solutions containing different functional groups;
(3) the double bond containing cage-type silsesquioxane (POSS) of the step of different content (1) gained is added in the middle of the silanol mixing solutions of step (2) gained, continue reaction for some time under certain condition, obtain POSS/ silicone resin nano composite material performed polymer, add afterwards end-capping reagent divinyl tetramethyl disiloxane, decompression removes low molecule by product and dehydrated alcohol, adds linking agent, catalyzer, inhibitor auxiliary agent can obtain target product single component POSS/ add-on type silicone resin nano composite material.
2. the preparation method of a kind of single component POSS/ add-on type silicone resin nano composite material according to claim 1, it is characterized in that, in described step (1), the mass ratio of alkoxyl group organosilicon, tetraethoxy and the deionized water of selected trifunctional is 1: (0.8-1.7): (5.5-7).
3. the preparation method of a kind of single component POSS/ add-on type silicone resin nano composite material according to claim 1, it is characterized in that, in described method steps (2), the mass ratio of the alkoxyl group organosilicon of selected trifunctional, the alkoxyl group organosilicon of two functional groups and deionized water is 1: (0.2-0.4): (5.1-9.8).
4. the preparation method of a kind of single component POSS/ add-on type silicone resin nano composite material according to claim 1, it is characterized in that, in described method steps (3), it is the 5-15% of silanol massfraction that cage-type silsesquioxane (POSS) adds the amount of silanol mixing solutions; In described divinyl tetramethyl disiloxane and step (2), the organosilyl ratio of alkoxyl group of trifunctional is (0.1-0.3): 1.
5. the preparation method of a kind of single component POSS/ add-on type silicone resin nano composite material according to claim 1, it is characterized in that, the alkoxyl group organosilicon of described trifunctional is preferably methyltrimethoxy silane, or the one in Union carbide A-162, phenyltrimethoxysila,e, phenyl triethoxysilane or vinyltriethoxysilane.
6. the preparation method of a kind of single component POSS/ add-on type silicone resin nano composite material according to claim 1, it is characterized in that, the alkoxyl group organosilicon of described two functional groups is preferably dimethoxydiphenylsilane, or the one in phenylbenzene diethoxy silane, dimethyldimethoxysil,ne or dimethyldiethoxysilane.
7. the preparation method of a kind of single component POSS/ add-on type silicone resin nano composite material according to claim 1, is characterized in that, the polysiloxane that described solidifying agent is hydrogen bonds and the combination of platinum catalyst.
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Application publication date: 20140528 Assignee: Jiangxi Hangyu Electronic Material Co.,Ltd. Assignor: JIANGXI PROVINCE HANGYU NEW MATERIAL Co.,Ltd. Contract record no.: X2023980052595 Denomination of invention: A preparation method for single component POSS/addition molded silicone resin nanocomposites Granted publication date: 20160921 License type: Common License Record date: 20231215 |