CN101220052A - Method for preparing sesquialter siloxane with acid anhydride group on vertex angle - Google Patents
Method for preparing sesquialter siloxane with acid anhydride group on vertex angle Download PDFInfo
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Abstract
A preparation method of silsesquioxane with acid anhydride groups on the apex angles relates to a preparation method of a compound. The invention provides a method for preparation of silsesquioxane with acid anhydride groups on the apex angles, which adopts 'apex angle capping' and multi-step functional group transformation. The method includes the following procedures: dissolving trihydroxyl hepta-R hepta-polysiloxane 1 and triethylamine into tetrahydrofuran; adding tetrachloro silicane; removing triethylamine hydrochlorate and the solvent to get the product of chloro-heptaR octasilsesquioxane 2; adding THF/H2O, refluxing and removing the solvent to get the product of hydroxyl-heptaR octasilsesquioxane 3; mixing hydroxyl-heptaR octasilsesquioxane 3 with dimethyl chloro-silane and Et3N for reaction; removing Et3N HCl; dissolving the solid obtained after solvent is removed from the filtrate into THF; filtering the THF phase and removing the solvent to get dimethyl alkoxyl heptaR octasilsesquioxane 4; dissolving and catalyzing dimethyl alkoxyl heptaR octasilsesquioxane 4 and acid anhydride together in toluene; removing the solvent to obtain the precipitates and dissolving the precipitates into acetic acid and toluene; refluxing and removing solvent of the filtrate; and then the target product is obtained through drying.
Description
Technical field
The present invention relates to a kind of preparation method of compound, especially relate to the preparation method that a kind of drift angle has the silsesquioxane of anhydride group.
Background technology
Silsesquioxane has classical general formula of molecular structure: (RSiO
1.5) n, exist with different structure forms such as random, ladder type, bridge type, cage modles.The silsesquioxane that wherein has ladder structure and cagelike structure is by extensive concern, and the oligomeric cage-type silsesquioxane (POSS) that particularly has a hexahedron structure is the focus in research recent years especially.
POSS comprises polyhedron silicon-oxygen nanostructure skeleton, and its molecular structure is as follows:
According to the size of R group, the POSS size is about 1.5～3nm, and molecular weight about 1000 is cagelike structure.It has two distinguishing features: silicone atom number ratio is 1.5 in (1) POSS molecule, is between silicon-dioxide SiO
2With silicone resin R
2Class hybrid between the SiO; (2) POSS molecular dimension and polymer segment or ball of string size are suitable.
POSS is a kind of hybrid inorganic-organic materials, existing organic constituent and inorganic component high-performance separately, the characteristic that has both synergistic effects to produce again.When the reactionless activity of the organic group on the POSS (R), can be used as the strongthener of resin system, and POSS can reach the dispersion of molecular level in hybrid systems; When POSS has reactive functional, copolymerization or autohemagglutination can take place, generate the homopolymer or the multipolymer of organic inorganic hybridization.
At present, simple function group POSS compound synthetic mainly contains following two kinds of routes:
(1) " drift angle-attach the names of pre-determined candidates " method is meant chlorosilane and not complete hydrolysis POSS three silanols reaction to contain required functional group, obtains complete hydrolysis POSS." drift angle-attach the names of pre-determined candidates " method can be used to synthetic multiple functionalized POSS, and the reaction yield height, and the cycle is short, is important functionizing method.(Song Xiaoyan such as Song Xiaoyan, Li Qifang, synthetic and the sign of magnetic polyhedron oligomeric silsesquioxanes (POSS) and polystyrene thereof/POSS nano composite material, Ph D dissertation, Beijing University of Chemical Technology, 2006) be raw material with the cyclopentyl trichlorosilane, prepared trihydroxy-seven cyclopentyl seven polysiloxane (T through hydrolytic condensation
7).T
7Obtain 4-benzyl chloride basic ring amyl group POSS with 4-benzyl chloride base trichlorosilane by " drift angle-attach the names of pre-determined candidates " reaction, synthesized magnetic polyhedron oligomeric silsesquioxanes 4-(2-ferrocenyl the vinyl)-phenyl cyclopentanone-based compounds that contains metal and two keys simultaneously then with the triphenylphosphine reaction, and then with the ferrocene formaldehyde reaction.
(2) functional group's conversion method is meant that the POSS that will contain functional group is converted into the method for required functional group through the organic chemistry method, and this method adopts different synthetic methods because of the difference of required functional group, and productive rate also has nothing in common with each other.Because of some contain the POSS commercialization of common functional group, so this kind method has become the functionalized main method of present POSS.Zhang Lipei (Zhang Lipei, Li Qifang, synthetic and the sign and the epoxy resin composite material performance study thereof of functionalized cage-type silsesquioxane (POSS), Master's thesis, Beijing University of Chemical Technology, 2004) synthesized 1-phenyl-3,5,7,9,11,13,15-seven cyclopentyl five rings-[9.5.1.13.9.15,15.17.13] eight polysilsesquioxanes, again through the nitrated 1-(2 (4) nitrophenyl)-3,5 that obtains of nitrosonitric acid, 7,9,11,13,15-seven cyclopentyl five rings-[9.5.1.13.9.15,15.17.13] eight polysilsesquioxanes.
But above-mentioned two kinds of methods generally can only be synthesized the POSS that drift angle has alkalescence or neutral group.
Summary of the invention
The drift angle that purpose of the present invention aims to provide a kind of employing " drift angle-attach the names of pre-determined candidates " and multistep functional group conversion method has the preparation method of the silsesquioxane of anhydride group.
Synthetic route of the present invention is as follows:
Concrete steps of the present invention are as follows:
1) under the exsiccant nitrogen atmosphere, with trihydroxy-seven R base seven polysiloxane 1 and triethylamine (Et
3N) be dissolved in the tetrahydrofuran (THF) (THF), add tetrachloro silicane (SiCl
4), remove triethylamine hydrochloride (Et
3NHCl), vacuumize and desolventize, white precipitate is collected in dry back, obtains product one chlorine seven R base eight polysilsesquioxanes (POSS-Cl) 2; In molar ratio, trihydroxy-seven R base seven polysiloxane: tetrachloro silicane: triethylamine is 1: (1～2): (3～3.5);
2) chlorine seven R base eight polysilsesquioxanes (POSS-Cl) 2 are added THF/H
2Reflux among the O and stir, solvent removed in vacuo obtains product hydroxyl seven R base eight polysilsesquioxanes (POSS-OH) 3; By volume, the volume ratio of THF and deionized water is 2: 1;
3) under vacuum or the nitrogen protection, with hydroxyl seven R base eight polysilsesquioxanes (POSS-OH) 3, chlorodimethyl silane (ClSi (CH
3)
2H) and Et
3The N hybrid reaction removes by filter Et
3NHCl, the solid that obtains after filtrate vacuumizing desolventizes is dissolved in THF, uses deionized water, HCl, NaCl solution washing more respectively, and behind the separatory, THF uses MgSO mutually
4Drying is filtered, and filtrate vacuumizes to remove and desolvates, and obtains product dimethyl-silicon alcoxyl base seven R base eight polysilsesquioxanes 4; In molar ratio, hydroxyl seven R base eight polysilsesquioxanes: chlorodimethyl silane: triethylamine is 1: (1～2): (1～2);
4) under argon shield, dimethyl-silicon alcoxyl base seven R base eight polysilsesquioxanes 4 are dissolved together with acid anhydrides in toluene, after adding 0.2mol%Karstedt ' s reagent carries out catalyzed reaction, vacuumize and remove solvent, remove unreacted acid anhydrides, behind the washing with acetone, obtain solid precipitation, throw out is dissolved in anhydrous acetic acid and toluene, adding gac refluxes, filter, filtrate vacuumizing desolventizes, and drying obtains dimethyl-silicon alcoxyl base seven R base eight polysilsesquioxanes 5 that final product has anhydride group; In molar ratio, dimethyl-silicon alcoxyl base seven R base eight polysilsesquioxanes:: acid anhydrides is 1: (1～1.5).
In step 1), the R group in trihydroxy-seven R base seven polysiloxane can be methyl, ethyl, propyl group, isobutyl-, phenyl, cyclohexyl, cyclopentyl or vinyl etc.; Add tetrachloro silicane (SiCl
4) after preferably stir 10～16h.
In step 3), with hydroxyl seven R base eight polysilsesquioxanes (POSS-OH) 3, chlorodimethyl silane (ClSi (CH
3)
2H) and Et
3The temperature of N hybrid reaction is preferably 60 ℃, and the time of reaction is preferably 16～20h; The concentration of HCl is preferably 1mol/L, and NaCl solution is preferably saturated NaCl solution.
In step 4), acid anhydrides can be Tetra Hydro Phthalic Anhydride, MALEIC ANHYDRIDE, methyl tetrahydrophthalic anhydride, methyl carbic anhydride or chlorendic anhydride etc.; The temperature of catalyzed reaction is preferably 75 ℃, and the time of catalyzed reaction is preferably 20～26h; Vacuumize and preferably be warming up to 200 ℃ after removing solvent, remove unreacted acid anhydrides again; The time that adds the gac backflow is preferably 2～3h.
The present invention adopts " drift angle-attach the names of pre-determined candidates " and multistep functional group conversion method, and adopts Karstedt ' s reagent to carry out the addition reaction of silicon hydrogen as catalyzer, and proceed step by step is repeatedly purified.Institute's synthetic drift angle has the POSS-acid anhydrides of anhydride group, can be used as the solidifying agent of epoxy-resin systems, the effect of playing curing, nanometer is toughness reinforcing and improves the Resins, epoxy heat decomposition temperature.
Embodiment
The invention will be further described below by embodiment.
Embodiment 1
Step 1, trihydroxy-seven phenyl seven polysiloxane 0.930g are put into two-mouth bottle, sealing vacuumizes, logical nitrogen repeatedly, replaces 3 times.0.303gEt
3N is dissolved in and is expelled among the 20mlTHF in the two-mouth bottle, slowly adds 0.170gSiCl under the room temperature
4Under the room temperature, behind the stirring 12h, remove by filter triethylamine hydrochloride (Et
3NHCl) 1, filtrate vacuumizing desolventizes, and white precipitate is collected in dry back, obtains product one chlorine seven phenyl eight polysilsesquioxanes.
Step 2, above-mentioned product one chlorine seven phenyl eight polysilsesquioxanes are added 30mlTHF/H
2Among the O, reflux and stir 18h, solvent removed in vacuo obtains product hydroxyl seven phenyl eight polysilsesquioxanes.Wherein the volume ratio of THF and deionized water is 2: 1.
Step 3, get another two-mouth bottle, above-mentioned product hydroxyl seven phenyl eight polysilsesquioxanes are placed in one, sealing vacuumizes, logical nitrogen, replaces repeatedly 3 times.0.095gClSi (CH
3)
2H and 0.101gEt
3N, 20mlTHF mix, and slowly are expelled in the two-mouth bottle.60 ℃ are reacted 18h down, remove by filter Et
3NHCl, the solid that obtains after filtrate vacuumizing desolventizes is dissolved in THF, and HCl and the saturated NaCl solution with deionized water, 1mol/L washs respectively again, and behind the separatory, THF uses MgSO mutually
4Drying dewaters, and filters, and solvent removed in vacuo obtains product dimethyl-silicon alcoxyl base seven phenyl eight polysilsesquioxanes.
Step 4, reaction product dimethyl-silicon alcoxyl base seven phenyl eight polysilsesquioxanes are placed another two-mouth bottle, sealing vacuumizes, logical argon gas, replaces repeatedly 3 times.Slowly be expelled in the 20ml toluene in the two-mouth bottle 0.152g Tetra Hydro Phthalic Anhydride is dissolved in, add 0.2mol%Karstedt ' s catalyzer with microsyringe.After reacting 24h under 75 ℃, vacuumize and remove solvent, be warming up to 200 ℃ and remove unreacted acid anhydrides, obtain solid precipitation behind the washing with acetone, throw out is dissolved in anhydrous acetic acid and toluene, adds gac backflow 2h, filters, filtrate vacuumizing desolventizes, and drying obtains dimethyl-silicon alcoxyl base seven phenyl eight polysilsesquioxanes that final product has anhydride group.
Embodiment 2: similar to Example 1, its difference is to change the reactant of step 1 into trihydroxy-seven ethyls seven polysiloxane, and add-on is 0.594g, and all the other conditions are constant.
Embodiment 3
Step 1, trihydroxy-seven isobutyl-s seven polysiloxane 0.790g are put into two-mouth bottle, sealing vacuumizes, logical nitrogen repeatedly, replaces 3 times.0.354gEt
3N is dissolved in and is expelled among the 20mlTHF in the two-mouth bottle, slowly adds 0.204gSiCl under the room temperature
4Under the room temperature, behind the stirring 10h, remove by filter Et
3NHCl, filtrate vacuumizing desolventizes, and white precipitate is collected in dry back, obtains product one chlorine seven isobutyl-s eight polysilsesquioxanes.
Step 2, above-mentioned product one chlorine seven isobutyl-s eight polysilsesquioxanes are added 30mlTHF/H
2Among the O, reflux and stir 10h, solvent removed in vacuo gets product hydroxyl seven isobutyl-s eight polysilsesquioxanes.Wherein the volume ratio of THF and deionized water is 2: 1.
Step 3, get another two-mouth bottle, above-mentioned product hydroxyl seven isobutyl-s eight polysilsesquioxanes are placed in one, sealing vacuumizes, logical nitrogen, replaces repeatedly 3 times.0.095gClSi (CH
3)
2H and 0.101gEt
3N, 20mlTHF mix, and slowly are expelled in the two-mouth bottle.60 ℃ are reacted 16h down, remove by filter Et
3NHCl, the solid that obtains after filtrate vacuumizing desolventizes is dissolved in THF, and HCl and the saturated NaCl solution with deionized water, 1mol/L washs respectively again, and behind the separatory, THF uses MgSO mutually
4Drying dewaters, and filters, and solvent removed in vacuo obtains product dimethyl-silicon alcoxyl base seven isobutyl-s eight polysilsesquioxanes.
Step 4, reaction product dimethyl-silicon alcoxyl base seven isobutyl-s eight polysilsesquioxanes are placed another two-mouth bottle, sealing vacuumizes, logical argon gas, replaces repeatedly 3 times.Slowly be expelled in the 20ml toluene in the two-mouth bottle 0.164g the methyl carbic anhydride is dissolved in, add 0.2mol%Karstedt ' s catalyzer with microsyringe.After reacting 20h under 75 ℃, vacuumize and remove solvent, be warming up to 200 ℃ and remove unreacted acid anhydrides, obtain solid precipitation behind the washing with acetone, throw out is dissolved in anhydrous acetic acid and toluene, adds gac backflow 2h, filters, filtrate vacuumizing desolventizes, and drying obtains dimethyl-silicon alcoxyl base seven isobutyl-s eight polysilsesquioxanes that final product has anhydride group.
Embodiment 4: similar to Example 3, its difference is to change the reactant of step 1 into trihydroxy-seven methyl seven polysiloxane, and add-on is 0.496g, and all the other conditions are constant.
Embodiment 5
Step 1, trihydroxy-seven cyclohexyl seven polysiloxane 0.972g are put into two-mouth bottle, sealing vacuumizes, logical nitrogen repeatedly, replaces 3 times.0.303gEt
3N is dissolved in and is expelled among the 20mlTHF in the two-mouth bottle, slowly adds 0.170gSiCl under the room temperature
4Under the room temperature, behind the stirring 16h, remove by filter Et
3NHCl, filtrate vacuumizing desolventizes, and white precipitate is collected in dry back, obtains product one chlorine seven cyclohexyl eight polysilsesquioxanes.
Step 2, above-mentioned product one chlorine seven cyclohexyl eight polysilsesquioxanes are added 30mlTHF/H
2Among the O, reflux and stir 20h, solvent removed in vacuo obtains product hydroxy-cyclohexyl silsesquioxane.Wherein the volume ratio of THF and deionized water is 2: 1.
Step 3, get another two-mouth bottle, above-mentioned product hydroxyl seven cyclohexyl eight polysilsesquioxanes are placed in one, sealing vacuumizes, logical nitrogen, replaces repeatedly 3 times.0.189gClSi (CH
3)
2H and 0.101gEt
3N, 20mlTHF mix, and slowly are expelled in the two-mouth bottle.60 ℃ are reacted 20h down, remove by filter Et
3NHCl, the solid that obtains after filtrate vacuumizing desolventizes is dissolved in THF, and HCl and the saturated NaCl solution with deionized water, 1mol/L washs respectively again, and behind the separatory, THF uses MgSO mutually
4Drying dewaters, and filters, and solvent removed in vacuo obtains product dimethyl-silicon alcoxyl base seven cyclohexyl eight polysilsesquioxanes.
Step 4, reaction product dimethyl-silicon alcoxyl base seven cyclohexyl eight polysilsesquioxanes are placed another two-mouth bottle, sealing vacuumizes, logical argon gas, replaces repeatedly 3 times.Slowly be expelled in the 20ml toluene in the two-mouth bottle 0.660g MALEIC ANHYDRIDE is dissolved in, add 0.2mo1%Karstedt ' s catalyzer with microsyringe.After reacting 26h under 75 ℃, vacuumize and remove solvent, be warming up to 200 ℃ and remove unreacted acid anhydrides, obtain solid precipitation behind the washing with acetone, throw out is dissolved in anhydrous acetic acid and toluene, adds gac, backflow 2h, filter, filtrate vacuumizing desolventizes, and drying obtains dimethyl-silicon alcoxyl base seven cyclohexyl eight polysilsesquioxanes that final product has anhydride group.
Embodiment 6: similar to Example 5, its difference is to change the reactant of step 1 into trihydroxy-seven cyclopentyl seven polysiloxane, and add-on is 0.874g, and all the other conditions are constant.
Embodiment 7
Step 1, trihydroxy-seven vinyl seven polysiloxane 0.580g are put into two-mouth bottle, sealing vacuumizes, logical nitrogen repeatedly, replaces 3 times.0.303gEt
3N is dissolved in and is expelled among the 20mlTHF in the two-mouth bottle, slowly adds 0.170gSiCl under the room temperature
4Under the room temperature, behind the stirring 14h, remove by filter Et
3NHCl, filtrate vacuumizing desolventizes, and white precipitate is collected in dry back, obtains product one chlorine seven vinyl eight polysilsesquioxanes.
Step 2, above-mentioned product one chlorine seven vinyl eight polysilsesquioxanes are added 30mlTHF/H
2Among the O, reflux and stir 18h, solvent removed in vacuo obtains product hydroxyl seven vinyl silsesquioxanes.Wherein the volume ratio of THF and deionized water is 2: 1.
Step 3, get another two-mouth bottle, above-mentioned product hydroxyl seven vinyl eight polysilsesquioxanes are placed in one, sealing vacuumizes, logical nitrogen, replaces repeatedly 3 times.0.095gClSi (CH
3)
2H and 0.101gEt
3N, 20mlTHF mix, and slowly are expelled in the two-mouth bottle.60 ℃ are reacted 18h down, remove by filter Et
3NHCl, the solid that obtains after filtrate vacuumizing desolventizes is dissolved in THF, and HCl and the saturated NaCl solution with deionized water, 1mol/L washs respectively again, and behind the separatory, THF uses MgSO mutually
4Drying dewaters, and filters, and solvent removed in vacuo obtains product dimethyl-silicon alcoxyl base seven vinyl eight polysilsesquioxanes.
Step 4, reaction product dimethyl-silicon alcoxyl base seven vinyl eight polysilsesquioxanes are placed another two-mouth bottle, sealing vacuumizes, logical argon gas, replaces repeatedly 3 times.Slowly be expelled in the 20ml toluene in the two-mouth bottle 0.361g chlorendic anhydride is dissolved in, add 0.2mol%Karstedt ' s catalyzer with microsyringe.After reacting 24h under 75 ℃, vacuumize and remove solvent, be warming up to 200 ℃ and remove unreacted acid anhydrides, obtain solid precipitation behind the washing with acetone, throw out is dissolved in anhydrous acetic acid and toluene, adds gac, backflow 3h, filter, filtrate vacuumizing desolventizes, and drying obtains dimethyl-silicon alcoxyl base seven vinyl eight polysilsesquioxanes that final product has anhydride group.
Embodiment 8: similar to Example 7, its difference is to change the reactant of step 1 into trihydroxy-seven propyl group seven polysiloxane, and add-on is 0.692g, and the acid anhydrides in the step 4 changes methyl tetrahydrophthalic anhydride into, and add-on is 0.166g, and all the other conditions are constant.
Claims (9)
1. a drift angle has the preparation method of the silsesquioxane of anhydride group, it is characterized in that its synthetic route is as follows:
Its concrete steps are as follows:
1) under the exsiccant nitrogen atmosphere, trihydroxy-seven R base seven polysiloxane 1 and triethylamine are dissolved in the tetrahydrofuran (THF), add tetrachloro silicane, remove triethylamine hydrochloride, vacuumize and desolventize, white precipitate is collected in dry back, obtains product one chlorine seven R base eight polysilsesquioxanes 2; In molar ratio, trihydroxy-seven R base seven polysiloxane: tetrachloro silicane: triethylamine is 1: 1～2: 3～3.5;
2) chlorine seven R base eight polysilsesquioxanes 2 are added THF/H
2Reflux among the O and stir, solvent removed in vacuo obtains product hydroxyl seven R base eight polysilsesquioxanes 3; By volume, the volume ratio of THF and deionized water is 2: 1;
3) under vacuum or the nitrogen protection, with hydroxyl seven R base eight polysilsesquioxanes 3, chlorodimethyl silane and Et
3The N hybrid reaction removes by filter Et
3NHCl, the solid that obtains after filtrate vacuumizing desolventizes is dissolved in THF, uses deionized water, HCl, NaCl solution washing more respectively, and behind the separatory, THF uses MgSO mutually
4Drying is filtered, and filtrate vacuumizes to remove and desolvates, and obtains product dimethyl-silicon alcoxyl base seven R base eight polysilsesquioxanes 4; In molar ratio, hydroxyl seven R base eight polysilsesquioxanes: chlorodimethyl silane: triethylamine is 1: 1～2: 1～2;
4) under argon shield, dimethyl-silicon alcoxyl base seven R base eight polysilsesquioxanes 4 are dissolved together with acid anhydrides in toluene, after adding 0.2mol%Karstedt ' s reagent carries out catalyzed reaction, vacuumize and remove solvent, remove unreacted acid anhydrides, behind the washing with acetone, obtain solid precipitation, throw out is dissolved in anhydrous acetic acid and toluene, adding gac refluxes, filter, filtrate vacuumizing desolventizes, and drying obtains dimethyl-silicon alcoxyl base seven R base eight polysilsesquioxanes 5 that final product has anhydride group; In molar ratio, dimethyl-silicon alcoxyl base seven R base eight polysilsesquioxanes:: acid anhydrides is 1: 1～1.5.
2. a kind of drift angle as claimed in claim 1 has the preparation method of the silsesquioxane of anhydride group, it is characterized in that in step 1) the R group in trihydroxy-seven R base seven polysiloxane is selected from methyl, ethyl, propyl group, isobutyl-, phenyl, cyclohexyl, cyclopentyl or vinyl.
3. a kind of drift angle as claimed in claim 1 has the preparation method of the silsesquioxane of anhydride group, it is characterized in that in step 1), stirs 10～16h behind the adding tetrachloro silicane.
4. a kind of drift angle as claimed in claim 1 has the preparation method of the silsesquioxane of anhydride group, it is characterized in that in step 3), with the temperature of hydroxyl seven R base eight polysilsesquioxanes 3, chlorodimethyl silane and triethylamine hybrid reaction is 60 ℃, and the time of reaction is 16～20h.
5. a kind of drift angle as claimed in claim 1 has the preparation method of the silsesquioxane of anhydride group, it is characterized in that in step 3), and the concentration of HCl is 1mol/L, and NaCl solution is saturated NaCl solution.
6. a kind of drift angle as claimed in claim 1 has the preparation method of the silsesquioxane of anhydride group, it is characterized in that in step 4) acid anhydrides is selected from Tetra Hydro Phthalic Anhydride, MALEIC ANHYDRIDE, methyl tetrahydrophthalic anhydride, methyl carbic anhydride or chlorendic anhydride.
7. a kind of drift angle as claimed in claim 1 has the preparation method of the silsesquioxane of anhydride group, it is characterized in that in step 4), and the temperature of catalyzed reaction is 75 ℃, and the time of catalyzed reaction is 20～26h.
8. a kind of drift angle as claimed in claim 1 has the preparation method of the silsesquioxane of anhydride group, it is characterized in that in step 4), vacuumizes to be warming up to 200 ℃ after removing solvent, removes unreacted acid anhydrides again.
9. a kind of drift angle as claimed in claim 1 has the preparation method of the silsesquioxane of anhydride group, it is characterized in that in step 4), and the time that adds the gac backflow is 2～3h.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102019738A (en) * | 2010-10-11 | 2011-04-20 | 厦门大学 | POSS (polyhedral oligomeric silsesquioxanes) modified high barrier three-layer co-extrusion packaging film and preparation method thereof |
| CN101629010B (en) * | 2009-08-07 | 2011-12-14 | 厦门大学 | Epoxy/POSS/carbon fiber nanometer composite material for light sports equipment and preparation method thereof |
| CN105111470A (en) * | 2015-08-13 | 2015-12-02 | 四川大学 | Reversible covalent crosslinking polysiloxane elastomer, preparation method therefor and application thereof |
| CN107652434A (en) * | 2017-10-16 | 2018-02-02 | 德清舒华泡沫座椅有限公司 | A kind of preparation method of organosilicon polyalcohol |
| CN112250878A (en) * | 2020-09-28 | 2021-01-22 | 厦门大学 | Thermally self-repairing recyclable epoxy resin and preparation method thereof |
| CN116572603A (en) * | 2023-07-13 | 2023-08-11 | 浙江葆润应用材料有限公司 | Composite heat insulation material and application thereof |
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2007
- 2007-12-29 CN CNA2007101441548A patent/CN101220052A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101629010B (en) * | 2009-08-07 | 2011-12-14 | 厦门大学 | Epoxy/POSS/carbon fiber nanometer composite material for light sports equipment and preparation method thereof |
| CN102019738A (en) * | 2010-10-11 | 2011-04-20 | 厦门大学 | POSS (polyhedral oligomeric silsesquioxanes) modified high barrier three-layer co-extrusion packaging film and preparation method thereof |
| CN102019738B (en) * | 2010-10-11 | 2013-04-17 | 厦门大学 | POSS (polyhedral oligomeric silsesquioxanes) modified high barrier three-layer co-extrusion packaging film and preparation method thereof |
| CN105111470A (en) * | 2015-08-13 | 2015-12-02 | 四川大学 | Reversible covalent crosslinking polysiloxane elastomer, preparation method therefor and application thereof |
| CN105111470B (en) * | 2015-08-13 | 2017-12-01 | 四川大学 | A kind of THERMALLY REVERSIBLE COVALENT silicone elastomer and preparation method and application |
| CN107652434A (en) * | 2017-10-16 | 2018-02-02 | 德清舒华泡沫座椅有限公司 | A kind of preparation method of organosilicon polyalcohol |
| CN112250878A (en) * | 2020-09-28 | 2021-01-22 | 厦门大学 | Thermally self-repairing recyclable epoxy resin and preparation method thereof |
| CN116572603A (en) * | 2023-07-13 | 2023-08-11 | 浙江葆润应用材料有限公司 | Composite heat insulation material and application thereof |
| CN116572603B (en) * | 2023-07-13 | 2023-09-22 | 浙江葆润应用材料有限公司 | Composite heat insulation material and application thereof |
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Application publication date: 20080716 |