CN104151765A - Preparation method of silica-based nano hybrid material for protecting silicate cultural relics - Google Patents
Preparation method of silica-based nano hybrid material for protecting silicate cultural relics Download PDFInfo
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Abstract
The invention relates to a preparation method of a silica-based nano hybrid material for protecting silicate cultural relics. The method comprises the following steps: 1. in a nitrogen protective atmosphere, adding a THF (tetrahydrofuran) solution containing bis-hydroxy silicon oil HO-PDMS (polydimethylsiloxane)-OH, TEA (triethanolamine hydrochloride), and DMAP (dimethylaminopyridine) into a reaction bulb, adding bromoisobutyryl bromide (BiBB) with an injector, and treating to obtain a high-polymer initiator bis-bromo silicon oil Br-PDMS-Br; 2. preparing a triblock polymer MMA-PDMS-MMA (methyl methacrylate) by ATRP (atom transfer radical polymerization) by using the high-polymer initiator obtained in the step 1; 3. reacting the product MMA-PDMS-MMA in the step 2 with methylacryloyloxypropyltrimethoxy silane and MPS (modified polystyrene) to prepare a siliceous pentablock copolymer PDMS-b-(PMMA-b-PMPS); 4. adding TEOS (ethyl orthosilicate) and ethanol into a reaction bulb according to the mole ratio of 1:10, adding a HCl solution to regulate the pH value, and prehydrolyzing for 1 hour; and 5. preparing the required end product silica-based nano hybrid material by a sol-gel process. The method has the characteristics of simple and quick process, low preparation cost and obvious protection effect.
Description
Technical field
The present invention relates to cultural artifact surface conservation treatment, particularly the preparation method of the silicon-base nanometer hybrid material of protection silicate cultural relic.
Technical background
Silica-based organic/inorganic nano-hybrid materials has organic and overall merit inorganic materials concurrently, has caused in recent years the extensive concern of novel material science.Because this class hybrid material can be realized the homodisperse of nanoscale; can solve the compatibility issue of matched coefficients of thermal expansion between matrix; also there is excellent chemical stability simultaneously; the performances such as uvioresistant, anti-fog, antimicrobial, water-fast, scratch resistance, wet-heat resisting; therefore, silicon-based hybrid nano coating film metrial has very great meaning to ecology, environment and historical relic's protection field.Existing relevant report or patent in historical relic's protection field at present, but it is little to be aimed at the relevant protecting materials of silicate cultural relic.And there is poor water resistance in existing protecting materials; not ageing-resistant and humid; the defects such as bad mechanical property; easily cause surface color and the structure distortion of silicate cultural relic; the problem such as top layer easily comes off and guard time persistence is poor; therefore, prepare a kind of silicon-base nanometer hybrid material, the protection to historical relic and the improvement of ecotope are significant.There is the advantages such as high rigidity, chemical stability, corrosion-resistant, high-low temperature resistant, wet-heat resisting based on inorganic nano silicon-dioxide, can be used as silicate cultural relic matrix reinforcement material; And organosilicon has the characteristics such as good toughness, retractility, corrosion-resistant, resistance to solvent, high-low temperature resistant, low surface energy; and type siloxane hydrolysis can further be cross-linked combination with phyllosilicate matrix; there is good bonding strength and perviousness, can be used for reinforcing and bonding protection.Therefore; silica-based organic/inorganic nano-hybrid materials can be realized it is carried out to scientific and reasonable protection under the prerequisite that does not change the original form of silicates basal body own and information, and the hybrid nano-material that becomes current silicates cultural heritage protection is needed the problem of solution badly.
Summary of the invention
In order to overcome the defect of above-mentioned prior art, the object of the present invention is to provide the preparation method of the silicon-base nanometer hybrid material of protection silicate cultural relic, there is process approach simple and quick, preparation cost is low, and the feature of protection successful.
In order to achieve the above object, technical scheme of the present invention comprises the following steps:
The preparation method of the silicon-base nanometer hybrid material of protection silicate cultural relic, comprises the following steps:
One, under nitrogen protection, in reaction flask, add the THF solution that contains two hydroxy silicon oil HO-PDMS-OH, triethylamine TEA and Dimethylamino pyridine DMAP, then add bromo isobutyl acylbromide BiBB with syringe, four mol ratios are HO-PDMS-OH:TEA:DMAP:BiBB=1:2:3:2; Room temperature reaction 24h after ice bath 2-3h, obtains macromole evocating agent-bis-bromo silicone oil Br-PDMS-Br after processing;
Two, the macromole evocating agent that utilizes the first step to obtain, adopt atomic radical to shift (ATRP) legal system for triblock polymer MMA-PDMS-MMA: by macromole evocating agent Br-PDMS-Br, methyl methacrylate MMA, CuCl, TMEDA 1:250:1:2 in molar ratio, under nitrogen protection, join in the reaction eggplant-shape bottle that contains pimelinketone, the mol ratio of pimelinketone and methyl methacrylate MMA is 1:1, sustained reaction 24h under 80 DEG C of conditions, obtains white powdery solid product MMA-PDMS-MMA after processing;
Three, utilize second step product MMA-PDMS-MMA and methacryloxypropyl trimethoxy silane, the siliceous five segmented copolymer PDMS-b-(PMMA-b-PMPS) of MPS reaction preparation
2: under nitrogen protection; containing in pimelinketone reaction eggplant-shape bottle; add the mixing solutions of PMMA-b-PDMS-b-PMMA, CuCl, MPS and TMEDA; pimelinketone, PMMA-b-PDMS-b-PMMA, CuCl, MPS and TMEDA mol ratio are 25:1:1:25:2; at 120 DEG C, react 24h, after processing, obtain white powdery solid product P DMS-b-(PMMA-b-PMPS)
2;
Four, by tetraethoxy (TEOS) and ethanol in molar ratio 1:10 join in reaction flask, add the HCl solution of appropriate 0.1mol/L, regulating pH value is prehydrolysis 1h at 4,50 DEG C;
Five, sol-gel method is prepared required final product silicon-base nanometer hybrid material, and concrete mode is:
Step 5.1, the dry powdered solid product obtaining in step 3 is added in THF solvent, be made into the THF solution of mass percent 5%, be moved in reaction flask, pass into N
2, add the HCl solution of 0.1mol/L, regulating pH value is prehydrolysis 30min at 4,50 DEG C;
Step 5.2, get product in step 4 and join in step 5.1 product, the PDMS-b-(PMMA-b-PMPS) in TEOS and step 5.1 in step 4
2both mol ratios are=1:(2-10), react 1h at 50 DEG C, promote the carrying out of condensation reaction, obtain hybrid material SiO
2/ PDMS-b-(PMMA-b-PMPS)
2.
Described step 5 sol-gel method is prepared required final product silicon-base nanometer hybrid material, can also adopt following steps preparation:
Steps A, the dry powdered solid product obtaining in step 3 is added in THF solvent, be made into the THF solution of mass percent 5%, be moved in reaction flask, pass into N
2, stir 30min, THF after then adding methyl alcohol: methyl alcohol mol ratio=9:1, promotes the formation of polymkeric substance assembly;
In step B, the assembly solution that obtains in steps A, add the HCl solution of 0.1mol/L, regulating pH value is prehydrolysis 30min at 4,50 DEG C;
Step C, get product in step 4 and join in step B product, the polymkeric substance assembly mol ratio of prehydrolysis in the TEOS in step 4 and step B is polymkeric substance: TEOS=(2-10): 1, under 50 DEG C of conditions, react 1h, the carrying out that promotes condensation reaction, obtains hybrid material PDMS-b-(PMMA-b-PMPS)
2/ SiO
2.
The aging resistance analysis of the prepared two kinds of silica-based organic/inorganic nano-hybrid materials of the present invention
One. the aging resistance analysis of silica-based organic/inorganic nano-hybrid materials
Two kinds of silicon-based hybrid material SiO
2/ PDMS-b-(PMMA-b-PMPS)
2and PDMS-b-(PMMA-b-PMPS)
2/ SiO
2damp and hot circulation after water contact angle and bonding force analysis show, PDMS-(PMMA-b-PMPS)
2/ SiO
2and SiO
2/ PDMS-(PMMA-b-PMPS)
2reducing of film surface contact angle is comparatively slow, after hydrothermal aging 936h, drops to more than 90 °, illustrates that these materials also can be at the long-term hydrophobic performance that keeps in strong humidity environment.Hybrid material PDMS-(PMMA-b-PMPS)
2/ SiO
2and SiO
2/ PDMS-(PMMA-b-PMPS)
2aging frontly have very strong bonding force to matrix, reaches respectively 463.2N and 358.39N.Aging 1392 as a child can reach 121.58N and 138.17N to matrix bonding force afterwards, and no longer with digestion time decay, illustrated after decay and still have higher bonding force.
The effect evaluation of silica-based organic/inorganic nano-hybrid materials
Utilize hybrid material PDMS-(PMMA-b-PMPS)
2/ SiO
2or SiO
2/ PDMS-(PMMA-b-PMPS)
2ultraviolet light and aging and surface chromatic aberration, contact angle, capillary water absorption, water vapor transmission and the salt tolerant circulation etc. carried out after sandstone and ceramic silicate sample piece simulation protection are evaluated.
The data of aberration, in table 1 and table 2, show PDMS-(PMMA-b-PMPS)
2/ SiO
2(table 1) and SiO
2/ PDMS-(PMMA-b-PMPS)
2(table 2) hybrid material colour-change degree in ultraviolet ageing process is relatively little, has good resistant function for uviolizing.
The not same piece ultraviolet ageing chromatic aberration of table 1 conservation treatment
The not same piece ultraviolet ageing chromatic aberration of table 2 conservation treatment
Through PDMS-(PMMA-b-PMPS)
2/ SiO
2or SiO
2/ PDMS-(PMMA-b-PMPS)
2the vapor permeability of the sandstone sample piece that hybrid material was processed is less, illustrates that it makes ventilation property variation in water resistant.
Through salt corrosion, do not protect the damage intensity of blank sample large, mass loss is about 30%, through hybrid material PDMS-(PMMA-b-PMPS)
2/ SiO
2or SiO
2/ PDMS-(PMMA-b-PMPS)
2the sample piece of conservation treatment does not change substantially, and it is-0.63% that its mass loss rate becomes negative value, and presentation of results is outstanding through the lifting of the salt resistant character of the sample piece of hybrid material conservation treatment.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment mono-
The preparation method of the present embodiment, comprises the following steps:
One, through 3-5 time vacuumize and logical condition of nitrogen gas under, in reaction flask, add the THF solution that contains two hydroxy silicon oil HO-PDMS-OH, triethylamine TEA and Dimethylamino pyridine DMAP, then add bromo isobutyl acylbromide BiBB with microsyringe, four mol ratios are HO-PDMS-OH:TEA:DMAP:BiBB=1:2:3:2; Room temperature reaction 24h after ice bath 2.5h, after filtration with rotary evaporation processing, after obtain the two bromo silicone oil (Br-PDMS-Br) of macromole evocating agent;
Two, the macromole evocating agent that utilizes the first step to obtain, adopt ATRP legal system for triblock polymer MMA-PDMS-MMA: by macromole evocating agent Br-PDMS-Br, methyl methacrylate (MMA), CuCl, TMEDA is 1:250:1:2 in molar ratio, joins in the reaction eggplant-shape bottle that contains pimelinketone, and the mol ratio of pimelinketone and methyl methacrylate MMA is 1:1, eggplant-shape bottle passes through 3-5 time vacuumizing and logical nitrogen, sustained reaction 24h under 80 DEG C of conditions in advance; After neutral alumina pillar is removed part, rotary evaporation and the processing of methyl alcohol precipitating, obtain white powdery solid product MMA-PDMS-MMA;
Three, utilize second step product MMA-PDMS-MMA and methacryloxypropyl trimethoxy silane, the siliceous five segmented copolymer PDMS-b-(PMMA-b-PMPS) of MPS reaction preparation
2: under nitrogen protection; containing in pimelinketone reaction eggplant-shape bottle; add the mixing solutions of PMMA-b-PDMS-b-PMMA, CuCl, MPS and TMEDA; pimelinketone, PMMA-b-PDMS-b-PMMA, CuCl, MPS and TMEDA mol ratio are 25:1:1:25:2; at 120 DEG C, react 24h, after processing, obtain white powdery solid product P DMS-b-(PMMA-b-PMPS)
2; After neutral alumina pillar is removed part, precipitating processing in rotary evaporation and methyl alcohol, obtains white powdery solid product P DMS-b-(PMMA-b-PMPS)
2;
Four, by tetraethoxy (TEOS) and ethanol in molar ratio 1:10 join in reaction flask, add the HCl solution of appropriate 0.1mol/L, regulating pH value is prehydrolysis 1h at 4,50 DEG C;
Five, sol-gel method is prepared required final product silicon-base nanometer hybrid material, and concrete mode is:
Step 5.1, the dry powdered solid product obtaining in step 3 is added in THF solvent, be made into the THF solution of mass percent 5%, be moved in reaction flask, pass into N
2, add the HCl solution of 0.1mol/L, regulating pH value is prehydrolysis 30min at 4,50 DEG C;
Step 5.2, get product in step 4 and join in step 5.1 product, the PDMS-b-(PMMA-b-PMPS) in TEOS and step 5.1 in step 4
2both mol ratios are=1:10, react 1h at 50 DEG C, promote the carrying out of condensation reaction, obtain hybrid material SiO
2/ PDMS-b-(PMMA-b-PMPS)
2.
By the present embodiment gained hybrid material SiO
2/ PDMS-b-(PMMA-b-PMPS)
2through contact angle test, result shows organic/inorganic hybridization material SiO
2/ PDMS-(PMMA-b-PMPS)
2have good hydrophobicity, aging 1392h can remain on more than 90 °.
By the present embodiment gained hybrid material SiO
2/ PDMS-b-(PMMA-b-PMPS)
2through capillary water absorption test, result shows through SiO
2/ PDMS-(PMMA-b-PMPS)
2the capillary water absorption degree of the sandstone sample piece that hybrid material was processed is little of negligible: the water-intake rate of the sample piece of process protecting materials processing is 0.66wt%, and blank sample piece is 6.02wt%.
Embodiment bis-
The present embodiment preparation method is identical with embodiment mono-, only step 5.2 difference in step 5:
Step 5.2, get product in step 4 and join in step 5.1 product, the PDMS-b-(PMMA-b-PMPS) in TEOS and step 5.1 in step 4
2both mol ratios are=1:5, react 1h at 50 DEG C, promote the carrying out of condensation reaction, obtain hybrid material SiO
2/ PDMS-b-(PMMA-b-PMPS)
2.
Embodiment tri-
The present embodiment preparation method is identical with embodiment mono-, only step 5.2 difference in step 5:
Step 5.2, get product in step 4 and join in step 5.1 product, the PDMS-b-(PMMA-b-PMPS) in TEOS and step 5.1 in step 4
2both mol ratios are=1:2, react 1h at 50 DEG C, promote the carrying out of condensation reaction, obtain hybrid material SiO
2/ PDMS-b-(PMMA-b-PMPS)
2.
Embodiment tetra-
The preparation method of the present embodiment, comprises the following steps:
One, through 3-5 time vacuumize and logical condition of nitrogen gas under, in reaction flask, add the THF solution that contains two hydroxy silicon oil HO-PDMS-OH, triethylamine TEA and Dimethylamino pyridine DMAP, then add bromo isobutyl acylbromide BiBB with microsyringe, four mol ratios are HO-PDMS-OH:TEA:DMAP:BiBB=1:2:3:2; Room temperature reaction 24h after ice bath 2.5h, after filtration with rotary evaporation processing, after obtain the two bromo silicone oil (Br-PDMS-Br) of macromole evocating agent;
Two, the macromole evocating agent that utilizes the first step to obtain, adopt ATRP legal system for triblock polymer MMA-PDMS-MMA: by macromole evocating agent Br-PDMS-Br, methyl methacrylate (MMA), CuCl, TMEDA is 1:250:1:2 in molar ratio, joins in the reaction eggplant-shape bottle that contains pimelinketone, and the mol ratio of pimelinketone and methyl methacrylate MMA is 1:1, eggplant-shape bottle passes through 3-5 time vacuumizing and logical nitrogen, sustained reaction 24h under 80 DEG C of conditions in advance.After neutral alumina pillar is removed part, rotary evaporation and the processing of methyl alcohol precipitating, obtain white powdery solid product MMA-PDMS-MMA;
Three, utilize second step product MMA-PDMS-MMA and methacryloxypropyl trimethoxy silane, the siliceous five segmented copolymer PDMS-b-(PMMA-b-PMPS) of MPS reaction preparation
2: under nitrogen protection; containing in pimelinketone reaction eggplant-shape bottle; add the mixing solutions of PMMA-b-PDMS-b-PMMA, CuCl, MPS and TMEDA; pimelinketone, PMMA-b-PDMS-b-PMMA, CuCl, MPS and TMEDA mol ratio are 25:1:1:25:2; at 120 DEG C, react 24 h, after processing, obtain white powdery solid product P DMS-b-(PMMA-b-PMPS)
2; After neutral alumina pillar is removed part, precipitating processing in rotary evaporation and methyl alcohol, obtains white powdery solid product P DMS-b-(PMMA-b-PMPS)
2;
Four, by tetraethoxy (TEOS) and ethanol in molar ratio 1:10 join in reaction flask, add the HCl solution of appropriate 0.1mol/L, regulating pH value is prehydrolysis 1h at 4,50 DEG C;
Five, sol-gel method is prepared required final product silicon-base nanometer hybrid material, and concrete mode is:
Steps A, the dry powdered solid product obtaining in step 3 is added in THF solvent, be made into the THF solution of mass percent 5%, be moved in reaction flask, pass into N
2, stir 30min, THF after then adding methyl alcohol: methyl alcohol mol ratio=9:1, promotes the formation of polymkeric substance assembly;
In step B, the assembly solution that obtains in steps A, add the HCl solution of 0.1mol/L, regulating pH value is prehydrolysis 30min at 4,50 DEG C,
Step C, get product in step 4 and join in step B product, the polymkeric substance assembly mol ratio of prehydrolysis in the TEOS in step 4 and step B is polymkeric substance: TEOS=5:1, under 50 DEG C of conditions, react 1h, the carrying out that promotes condensation reaction, obtains hybrid material PDMS-b-(PMMA-b-PMPS)
2/ SiO
2.
By the present embodiment gained hybrid material PDMS-b-(PMMA-b-PMPS)
2/ SiO
2through contact angle test, result shows organic/inorganic hybridization material PDMS-b-(PMMA-b-PMPS)
2/ SiO
2have good hydrophobicity, aging 1392h can remain on more than 90 °.
By the present embodiment gained hybrid material PDMS-b-(PMMA-b-PMPS)
2/ SiO
2through capillary water absorption test, result shows through PDMS-b-(PMMA-b-PMPS)
2/ SiO
2the capillary water absorption degree of the sandstone sample piece that hybrid material was processed is little of negligible: the water-intake rate of the sample piece of process protecting materials processing is 0.76wt%, and blank sample piece is 5.82wt%.
Embodiment five
The present embodiment preparation method is identical with embodiment tetra-, only the step C difference in step 5:
Step C, get product in step 4 and join in step B product, the polymkeric substance assembly mol ratio of prehydrolysis in the TEOS in step 4 and step B is polymkeric substance: TEOS=2:1, under 50 DEG C of conditions, react 1h, the carrying out that promotes condensation reaction, obtains hybrid material PDMS-b-(PMMA-b-PMPS)
2/ SiO
2.
Embodiment six
The present embodiment preparation method is identical with embodiment tetra-, only the step C difference in step 5:
Step C, get product in step 4 and join in step B product, the polymkeric substance assembly mol ratio of prehydrolysis in the TEOS in step 4 and step B is polymkeric substance: TEOS=10:1, under 50 DEG C of conditions, react 1h, the carrying out that promotes condensation reaction, obtains hybrid material PDMS-b-(PMMA-b-PMPS)
2/ SiO
2.
Claims (8)
1. the preparation method of the silicon-base nanometer hybrid material of protection silicate cultural relic, is characterized in that, comprises the following steps:
One, under nitrogen protection, in reaction flask, add the THF solution that contains two hydroxy silicon oil HO-PDMS-OH, triethylamine TEA and Dimethylamino pyridine DMAP, then add bromo isobutyl acylbromide BiBB with syringe, four mol ratios are HO-PDMS-OH:TEA:DMAP:BiBB=1:2:3:2; Room temperature reaction 24h after ice bath 2-3h, obtains macromole evocating agent-bis-bromo silicone oil Br-PDMS-Br after processing;
Two, the macromole evocating agent that utilizes the first step to obtain, adopt atomic radical to shift (ATRP) legal system for triblock polymer MMA-PDMS-MMA: by macromole evocating agent Br-PDMS-Br, methyl methacrylate MMA, CuCl, TMEDA 1:250:1:2 in molar ratio, under nitrogen protection, join in the reaction eggplant-shape bottle that contains pimelinketone, the mol ratio of pimelinketone and methyl methacrylate MMA is 1:1, sustained reaction 24h under 80 DEG C of conditions, obtains white powdery solid product MMA-PDMS-MMA after processing;
Three, utilize second step product MMA-PDMS-MMA and methacryloxypropyl trimethoxy silane, the siliceous five segmented copolymer PDMS-b-(PMMA-b-PMPS) of MPS reaction preparation
2: under nitrogen protection; containing in pimelinketone reaction eggplant-shape bottle; add the mixing solutions of PMMA-b-PDMS-b-PMMA, CuCl, MPS and TMEDA; pimelinketone, PMMA-b-PDMS-b-PMMA, CuCl, MPS and TMEDA mol ratio are 25:1:1:25:2; at 120 DEG C, react 24h, after processing, obtain white powdery solid product P DMS-b-(PMMA-b-PMPS)
2;
Four, by tetraethoxy (TEOS) and ethanol in molar ratio 1:10 join in reaction flask, add the HCl solution of appropriate 0.1mol/L, regulating pH value is prehydrolysis 1h at 4,50 DEG C;
Five, sol-gel method is prepared required final product silicon-base nanometer hybrid material, and concrete mode is:
Step 5.1, the dry powdered solid product obtaining in step 3 is added in THF solvent, be made into the THF solution of mass percent 5%, be moved in reaction flask, pass into N
2, add the HCl solution of 0.1mol/L, regulating pH value is prehydrolysis 30min at 4,50 DEG C;
Step 5.2, get product in step 4 and join in step 5.1 product, the PDMS-b-(PMMA-b-PMPS) in TEOS and step 5.1 in step 4
2both mol ratios are=1:(2-10), react 1h at 50 DEG C, promote the carrying out of condensation reaction, obtain hybrid material SiO
2/ PDMS-b-(PMMA-b-PMPS)
2.
2. the preparation method of the silicon-base nanometer hybrid material of protection silicate cultural relic according to claim 1, is characterized in that, step 5 sol-gel method is prepared required final product silicon-base nanometer hybrid material, adopts following steps preparation:
Steps A, the dry powdered solid product obtaining in step 3 is added in THF solvent, be made into the THF solution of mass percent 5%, be moved in reaction flask, pass into N
2, stir 30min, THF after then adding methyl alcohol: methyl alcohol mol ratio=9:1, promotes the formation of polymkeric substance assembly;
In step B, the assembly solution that obtains in steps A, add the HCl solution of 0.1mol/L, regulating pH value is prehydrolysis 30min at 4,50 DEG C,
Step C, get product in step 4 and join in step B product, the polymkeric substance assembly mol ratio of prehydrolysis in the TEOS in step 4 and step B is polymkeric substance: TEOS=(2-10): 1, under 50 DEG C of conditions, react 1h, the carrying out that promotes condensation reaction, obtains hybrid material PDMS-b-(PMMA-b-PMPS)
2/ SiO
2.
3. the preparation method of the silicon-base nanometer hybrid material of protection silicate cultural relic according to claim 1; it is characterized in that; step 5.2, get product in step 4 and join in step 5.1 product, the PDMS-b-(PMMA-b-PMPS) in TEOS and step 5.1 in step 4
2both mol ratios are=1:10, react 1h at 50 DEG C, promote the carrying out of condensation reaction, obtain hybrid material SiO
2/ PDMS-b-(PMMA-b-PMPS)
2.
4. the preparation method of the silicon-base nanometer hybrid material of protection silicate cultural relic according to claim 1; it is characterized in that; step 5.2, get product in step 4 and join in step 5.1 product, the PDMS-b-(PMMA-b-PMPS) in TEOS and step 5.1 in step 4
2both mol ratios are=1:5, react 1h at 50 DEG C, promote the carrying out of condensation reaction, obtain hybrid material SiO
2/ PDMS-b-(PMMA-b-PMPS)
2.
5. the preparation method of the silicon-base nanometer hybrid material of protection silicate cultural relic according to claim 1; it is characterized in that; step 5.2, get product in step 4 and join in step 5.1 product, the PDMS-b-(PMMA-b-PMPS) in TEOS and step 5.1 in step 4
2both mol ratios are=1:2, react 1h at 50 DEG C, promote the carrying out of condensation reaction, obtain hybrid material SiO
2/ PDMS-b-(PMMA-b-PMPS)
2.
6. the preparation method of the silicon-base nanometer hybrid material of protection silicate cultural relic according to claim 2; it is characterized in that; step C, get product in step 4 and join in step B product; the polymkeric substance assembly mol ratio of prehydrolysis in the TEOS in step 4 and step B is polymkeric substance: TEOS=5:1; under 50 DEG C of conditions, react 1h; the carrying out that promotes condensation reaction, obtains hybrid material PDMS-b-(PMMA-b-PMPS)
2/ SiO
2.
7. the preparation method of the silicon-base nanometer hybrid material of protection silicate cultural relic according to claim 2; it is characterized in that; step C, get product in step 4 and join in step B product; the polymkeric substance assembly mol ratio of prehydrolysis in the TEOS in step 4 and step B is polymkeric substance: TEOS=2:1; under 50 DEG C of conditions, react 1h; the carrying out that promotes condensation reaction, obtains hybrid material PDMS-b-(PMMA-b-PMPS)
2/ SiO
2.
8. the preparation method of the silicon-base nanometer hybrid material of protection silicate cultural relic according to claim 2; it is characterized in that; step C, get product in step 4 and join in step B product; the polymkeric substance assembly mol ratio of prehydrolysis in the TEOS in step 4 and step B is polymkeric substance: TEOS=10:1; under 50 DEG C of conditions, react 1h; the carrying out that promotes condensation reaction, obtains hybrid material PDMS-b-(PMMA-b-PMPS)
2/ SiO
2.
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| CN105542065A (en) * | 2016-02-02 | 2016-05-04 | 浙江大学 | Multifunctional amphiphilic comb-type polymer modifier, and preparation method and application thereof |
| CN106397676A (en) * | 2016-09-14 | 2017-02-15 | 西安交通大学 | Preparation method of breathable POSS-based epoxy grafted copolymer for silicate cultural relics |
| CN108101582A (en) * | 2017-11-30 | 2018-06-01 | 中冶建筑研究总院（深圳）有限公司 | A kind of hybrid inorganic-organic concrete impregnating agent and preparation method |
| CN113372016A (en) * | 2021-06-24 | 2021-09-10 | 中国科学院兰州化学物理研究所 | Wear-resistant and renewable polymer brush initiator coating and preparation method and application thereof |
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| CN105542065A (en) * | 2016-02-02 | 2016-05-04 | 浙江大学 | Multifunctional amphiphilic comb-type polymer modifier, and preparation method and application thereof |
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| CN108101582A (en) * | 2017-11-30 | 2018-06-01 | 中冶建筑研究总院（深圳）有限公司 | A kind of hybrid inorganic-organic concrete impregnating agent and preparation method |
| CN113372016A (en) * | 2021-06-24 | 2021-09-10 | 中国科学院兰州化学物理研究所 | Wear-resistant and renewable polymer brush initiator coating and preparation method and application thereof |
| CN113372016B (en) * | 2021-06-24 | 2022-05-27 | 中国科学院兰州化学物理研究所 | Wear-resistant and renewable polymer brush initiator coating and preparation method and application thereof |
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