CN106397676B - The preparation method of silicate cultural relic protection gas permeability POSS basic ring oxygen graft copolymers - Google Patents
The preparation method of silicate cultural relic protection gas permeability POSS basic ring oxygen graft copolymers Download PDFInfo
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- CN106397676B CN106397676B CN201610825027.3A CN201610825027A CN106397676B CN 106397676 B CN106397676 B CN 106397676B CN 201610825027 A CN201610825027 A CN 201610825027A CN 106397676 B CN106397676 B CN 106397676B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F120/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
Abstract
The preparation method of silicate cultural relic protection gas permeability POSS basic ring oxygen graft copolymers, glycidyl methacrylate is polymerize obtained from polymer backbone (l PGMA) by solution polymerization first, then, it is reacted from the bromo acid of different moles via epoxy ring opening reaction, obtain the macromole evocating agent (l PGMA Br) for causing end containing different number, finally, it is macromole evocating agent in l PGMA Br, under CuCl/Bpy catalyst system and catalyzings, being caused by atom transferred free radical technology (ATRP) has seven isobutyl group polysilsesquioxane of monomethacrylate acyloxy (MA POSS), obtain white powder solid product, last PGMA g P (MA POSS) graft copolymer solidification；The present invention has process approach simple and quick, and manufacturing cost is low, and cementability is good, and the feature with obvious effects that has improved breathability.
Description
Technical field
The invention belongs to functional high molecule material and Techniques of Relics Protection field, more particularly to a kind of breathing epoxy bonding
Material --- the preparation method of silicate cultural relic protection gas permeability POSS basic ring oxygen graft copolymers.
Technical background
Polyhedral oligomeric silsesquioxane (Polyhedral oligomeric silsesquioxane, POSS) is by inorganic
The molecular level nano-organosilicon compound for a diameter of 1-3nm of one kind that Si-O-Si frames and peripheral organic group collectively constitute.By
In with the hollow cage being made of silica element, give the good gas permeability of POSS base modified materials.Glycidyl methacrylate
Glyceride (GMA) is the bifunctional compound with epoxy-functional and double bond, can be introduced into polymer, obtain
Material with good bonding performance.Therefore, in order to improve the weakness of PGMA autopolymer poor air permeabilities, introducing has hollow cage
The POSS of structure, copolymerization obtain having concurrently the hybrid material of gas permeability and cementability.Wherein, the inorganic kernels of POSS assign hybrid material
The performances such as good gas permeability, hardness, heat-resisting, weatherability, corrosion-resistant and high-low temperature resistant assign hydridization material after GMA curing reactions
Expect good adhesive property.So as historical relic's protection class gas permeability adhesives, there is important research significance and reality
With value, the blank of historical relic's protection special bonding material has been filled up.
Invention content
In order to overcome the defect of the above-mentioned prior art, the object of the present invention is to provide a kind of protections of silicate cultural relic
With the preparation method of gas permeability POSS basic ring oxygen graft copolymers, the preparation process of POSS basic ring oxygen graft copolymers be pass through through
Solution polymerization, epoxy ring opening reaction and the ATRP polymerization reaction of allusion quotation, successively obtained from polymer backbone (l-PGMA), macromolecular
Initiator (l-PGMA-Br) and PGMA-g-P (MA-POSS) graft copolymer have process approach simple and quick, manufacturing cost
Low, cementability is good, and the feature with obvious effects that has improved breathability.
In order to achieve the above object, the technical scheme is that：
The preparation method of silicate cultural relic protection gas permeability POSS basic ring oxygen graft copolymers, includes the following steps：
(1), the synthesis of l-PGMA polymer chains：L-PGMA polymer chains are synthesized by solution polymerization process, weigh GMA
Monomer, 4wt% AIBN initiators be dissolved in butanone solvent, three's mass ratio is 1:0.04:2, it is then added to and is placed with magnetic
In the round-bottomed flask of son, 5h is stirred to react at 65 DEG C, after completion of the reaction cooling down, and rotate out extra solvent to reaction solution
Present it is thick, then by reaction solution in excessive methanol precipitating, filter, vacuum drying for 24 hours, obtain white solid；
(2), the synthesis of l-PGMA-Br macromole evocating agents：Utilize the epoxy group and bromo acid BIBA in GMA
In carboxyl epoxy ring opening reaction occur introduce Br ends, generate ATRP macromole evocating agents, specific method is：Respectively by 1mmol
L-PGMA and the BIBA of 0.1-10.0mmol be dissolved in 5ml THF solvents, and pour into equipped with reflux condensate device and magneton
Round-bottomed flask in, react 30h under the conditions of 50 DEG C, when reaction to the end of, revolving remove excess of solvent, residual reaction liquid is in excessive second
Precipitating in ether obtains l-PGMA-Br white powders, and for 24 hours, the epoxy group and the ends Br that non-open loop is prepared respectively are rubbed for vacuum drying
You are than the l-PGMA-Br macromole evocating agents for 0.1-10；
Three, the ATRP synthesis of PGMA-g-P (MA-POSS) graft copolymer：According to following substances amount ratio by l-PGMA-Br,
CuCl, bipyridine (Bpy) ligand, MA-POSS monomers are added in eggplant type reaction bulb and seal, and mass ratio is followed successively by：1：(6-
56):(13.2-123):(30-280), vacuumizes, and leads to nitrogen, after recycling three times, injects cyclohexanone, cyclohexanone quality is MA-
2 times of POSS monomer masses, under nitrogen atmosphere, stirring at normal temperature 30min are warming up to 100 DEG C, react 8h；After reaction, stop
It only heats, and blowing air, excessive THF dilutions is added, stirring for 24 hours, makes the reaction was complete to terminate, then will be anti-after above-mentioned dilution
The oxidized aluminium column of liquid stream is answered, to remove ligand and copper ion therein, the colourless reaction solution concentrated by rotary evaporation of outflow, finally in excess
Methanol in precipitating, vacuum drying, obtain white powder solid product PGMA-g-P (MA-POSS) graft copolymer；
Four, the solidification of PGMA-g-P (MA-POSS) graft copolymer：P (GMA-MAPOSS) copolymer, triethylamine (TEA)
Curing agent, THF solvents are in mass ratio=1.5:1:3 are added in reaction bulb, and sustained response for 24 hours, obtains pre- solid under the conditions of 50 DEG C
Change liquid, as gas permeability POSS basic rings oxygen graft copolymer.
The structural characterization of gas permeability POSS basic ring oxygen graft copolymer basic ring oxygen graft copolymers prepared by the present invention with
Performance, applicating evaluating：
One, POSS basic ring oxygen graft copolymers are cured using atomic force microscope (AFM) and contact angle measurement (SCA)
Agent studies surface property before and after being added.The result shows that the addition of POSS makes film surface roughness be increased to
4.1nm is increased to 117 ° to the contact angle of water；Film surface roughness and the wettability to water are changed after solidification.Differential is swept
Calorimeter (DSC) and thermogravimetic analysis (TGA) (TGA) display are retouched, appropriate POSS can significantly improve the glass transition temperature of the total object of grafting
Degree and thermal stability finally make glass transition temperature since the formation of tridimensional network is to the increase effect of crosslink density
It is significantly improved before relatively curing with thermal stability.
Two, the bonding force after adhesive strength and humiture the cycle aging of material shows that adhesive strength is in hydrothermal aging mistake
Speed increase, slow smaller trend are presented in journey, but final adhesive strength is still better than blank sample.Bonding force is 216N-
333N.Therefore, PGMA-g-P (MA-POSS) graft copolymer has the advantages that heat and moisture aging resistance.
Three, the curing materials of PGMA-g-P (MA-POSS) graft copolymer of conventional epoxies and synthesis itself are compared
Back aperture is protected with for sandstone, it can be seen that after either curing materials itself are still protected for sandstone, with conventional epoxy
Resin is compared, and the gas permeability of PGMA-g-P (MA-POSS) graft copolymer is superior to conventional epoxies.
Specific implementation mode
The present invention is described in detail with reference to specific embodiment.
Embodiment one
The present embodiment gas permeability is bonded the preparation method of POSS basic ring oxygen graft copolymer PGMA-g-P (MA-POSS), packet
Include following steps：
(1), the synthesis of l-PGMA polymer chains：L-PGMA polymer chains are synthesized by solution polymerization process, weigh GMA
Monomer, 4wt% AIBN initiators be dissolved in butanone solvent, three's mass ratio is 1:0.04:2, it is then added to and is placed with magnetic
In the round-bottomed flask of son, 5h is stirred to react at 65 DEG C, after completion of the reaction cooling down, and rotate out extra solvent to reaction solution
Present it is thick, then by reaction solution in excessive methanol precipitating, filter, vacuum drying for 24 hours, obtain white solid；Yield is about
It is 85.02%, molecular weight is 8865gmol-1, PDI=1.34.
(2), the synthesis of l-PGMA-Br macromole evocating agents：Utilize the epoxy group and bromo acid BIBA in GMA
In carboxyl epoxy ring opening reaction occur introduce Br ends, generate ATRP macromole evocating agents, specific method is：Respectively by 1mmol
L-PGMA and the BIBA of 0.1mmol be dissolved in 5ml THF solvents, and pour into the round bottom equipped with reflux condensate device and magneton
In flask, 30h is reacted under the conditions of 50 DEG C, to the end of reaction, revolving removes excess of solvent, and residual reaction liquid sinks in excess diethyl ether
Analysis obtains l-PGMA-Br white powders, and for 24 hours, the epoxy group and the ends Br molar ratio that non-open loop is prepared respectively are for vacuum drying
10/1 l-PGMA-Br macromole evocating agents；
Three, the ATRP synthesis of PGMA-g-P (MA-POSS) graft copolymer：According to following substances amount ratio by l-PGMA-Br,
CuCl, bipyridine (Bpy) ligand, MA-POSS monomers are added in eggplant type reaction bulb and seal, and mass ratio is followed successively by：1:6:
13.2:30, it vacuumizes, leads to nitrogen, after recycling three times, inject cyclohexanone, cyclohexanone quality is 2 times of MA-POSS monomer masses,
Under nitrogen atmosphere, stirring at normal temperature 30min is warming up to 100 DEG C, reacts 8h；After reaction, stop heating, and blowing air, add
Entering excessive THF dilutions, stirring for 24 hours, makes the reaction was complete to terminate, the reaction solution after above-mentioned dilution is then flowed through alumina column,
To remove ligand and copper ion therein, the colourless reaction solution concentrated by rotary evaporation of outflow, finally precipitating, vacuum in excessive methanol
It is dry, obtain white powder solid product PGMA-g-P (MA-POSS) graft copolymer；
Four, the solidification of PGMA-g-P (MA-POSS) graft copolymer：P (GMA-MAPOSS) copolymer, triethylamine (TEA)
Curing agent, THF solvents are in mass ratio=1.5:1:3 are added in reaction bulb, and sustained response for 24 hours, obtains pre- solid under the conditions of 50 DEG C
Change liquid, as gas permeability POSS basic rings oxygen graft copolymer.
Effect performance：Atomic force microscope (AFM) result shows that film surface roughness is 0.14nm；Contact angle is
110.8°；The glass transition temperature of the total object of differential scanning calorimeter (DSC) result display grafting is 127.1 DEG C；Thermal weight loss point
It is 5.3% to analyse (TGA) result display thermal decomposition residual volume；Material is 216N to the adhesive strength of silicate substrate.
Embodiment two
The present embodiment gas permeability is bonded the preparation method and reality of POSS basic ring oxygen graft copolymer PGMA-g-P (MA-POSS)
It is identical to apply example one, only second and third step is different：
(2), the synthesis of l-PGMA-Br macromole evocating agents：Respectively by the molten of the l-PGMA of 1mmol and 1mmol BIBA
Solution is poured into 5ml THF solvents in the round-bottomed flask equipped with reflux condensate device and magneton, reacts 30h under the conditions of 50 DEG C.
To the end of reaction, excess of solvent is spun off, residual reaction liquid precipitating in excess diethyl ether obtains l-PGMA-Br white powders, vacuum
It is dry that it is 1/1 that the epoxy group of non-open loop and the ends Br molar ratio are prepared respectively for 24 hours, l-PGMA-Br macromole evocating agents.
(3), the ATRP synthesis of PGMA-g-P (MA-POSS) graft copolymer：According to following substances amount ratio by l-PGMA-
Br, CuCl, bipyridine (Bpy) ligand, MA-POSS monomers are added in eggplant type reaction bulb and seal, and mass ratio is followed successively by：1:
31:66:155, it vacuumizes, leads to nitrogen, after recycling three times, inject cyclohexanone, cyclohexanone quality is the 2 of MA-POSS monomer masses
Times, under nitrogen atmosphere, stirring at normal temperature 30min is warming up to 100 DEG C, reacts 8h；After reaction, stop heating, and logical sky
Gas, is added excessive THF dilutions, and stirring for 24 hours, makes the reaction was complete to terminate, the reaction solution after above-mentioned dilution is then flowed through oxidation
Aluminium column, to remove ligand and copper ion therein, the colourless reaction solution concentrated by rotary evaporation of outflow is finally sunk in excessive methanol
Analysis, vacuum drying, obtains white powder solid product PGMA-g-P (MA-POSS) graft copolymer.
Effect performance：Atomic force microscope (AFM) result shows that film surface roughness is increased to 0.19nm；Contact angle improves
To 118.1 °；The glass transition temperature of the total object of differential scanning calorimeter (DSC) result display grafting is increased to 135.7 DEG C；Heat
Zero-g aircraft (TGA) result display thermal decomposition residual volume is increased to 8.2%；Material arrives the adhesive strength promotion of silicate substrate
247N。
Embodiment three
The present embodiment gas permeability is bonded the preparation method and reality of POSS basic ring oxygen graft copolymer PGMA-g-P (MA-POSS)
It is identical to apply example one, only second and third step is different：
(2), the synthesis of l-PGMA-Br macromole evocating agents：Utilize the epoxy group and bromo acid BIBA in GMA
In carboxyl epoxy ring opening reaction occur introduce Br ends, generate ATRP macromole evocating agents, specific method is：Respectively by 1mmol
L-PGMA and the BIBA of 3mmol be dissolved in 5ml THF solvents, and pour into and burnt equipped with the round bottom of reflux condensate device and magneton
In bottle, 30h is reacted under the conditions of 50 DEG C, to the end of reaction, revolving removes excess of solvent, and residual reaction liquid sinks in excess diethyl ether
Analysis obtains l-PGMA-Br white powders, and for 24 hours, the epoxy group and the ends Br molar ratio that non-open loop is prepared respectively are for vacuum drying
1/3 l-PGMA-Br macromole evocating agents；
(3), the ATRP synthesis of PGMA-g-P (MA-POSS) graft copolymer：According to following substances amount ratio by l-PGMA-
Br, CuCl, bipyridine (Bpy) ligand, MA-POSS monomers are added in eggplant type reaction bulb and seal, and mass ratio is followed successively by：1:
46:101.2:230, it vacuumizes, leads to nitrogen, after recycling three times, inject cyclohexanone, cyclohexanone quality is MA-POSS monomer masses
2 times, under nitrogen atmosphere, stirring at normal temperature 30min is warming up to 100 DEG C, reacts 8h；After reaction, stop heating, and lead to
Air, is added excessive THF dilutions, and stirring for 24 hours, makes the reaction was complete to terminate, the reaction solution after above-mentioned dilution is then flowed through oxygen
Change aluminium column, to remove ligand and copper ion therein, the colourless reaction solution concentrated by rotary evaporation of outflow is finally sunk in excessive methanol
Analysis, vacuum drying, obtains white powder solid product PGMA-g-P (MA-POSS) graft copolymer.
Effect performance：Atomic force microscope (AFM) result shows that film surface roughness is increased to 0.63nm；Contact angle improves
To 120.7 °；The glass transition temperature of the total object of differential scanning calorimeter (DSC) result display grafting is 115.1 DEG C；Thermal weight loss
Analysis (TGA) result display thermal decomposition residual volume is increased to 8.4%；Material arrives the adhesive strength promotion of silicate substrate
275N。
Example IV
The present embodiment gas permeability is bonded the preparation method and reality of POSS basic ring oxygen graft copolymer PGMA-g-P (MA-POSS)
It is identical to apply example one, only second and third step is different：
(2), the synthesis of l-PGMA-Br macromole evocating agents：Utilize the epoxy group and bromo acid BIBA in GMA
In carboxyl epoxy ring opening reaction occur introduce Br ends, generate ATRP macromole evocating agents, specific method is：Respectively by 1mmol
L-PGMA and the BIBA of 10mmol be dissolved in 5ml THF solvents, and pour into the round bottom equipped with reflux condensate device and magneton
In flask, 30h is reacted under the conditions of 50 DEG C, to the end of reaction, revolving removes excess of solvent, and residual reaction liquid sinks in excess diethyl ether
Analysis obtains l-PGMA-Br white powders, and for 24 hours, the epoxy group and the ends Br molar ratio that non-open loop is prepared respectively are for vacuum drying
1/10 l-PGMA-Br macromole evocating agents；
(3), the ATRP synthesis of PGMA-g-P (MA-POSS) graft copolymer：According to following substances amount ratio by l-PGMA-
Br, CuCl, bipyridine (Bpy) ligand, MA-POSS monomers are added in eggplant type reaction bulb and seal, and mass ratio is followed successively by：1:
56:123:280, it vacuumizes, leads to nitrogen, after recycling three times, inject cyclohexanone, cyclohexanone quality is the 2 of MA-POSS monomer masses
Times, under nitrogen atmosphere, stirring at normal temperature 30min is warming up to 100 DEG C, reacts 8h；After reaction, stop heating, and logical sky
Gas, is added excessive THF dilutions, and stirring for 24 hours, makes the reaction was complete to terminate, the reaction solution after above-mentioned dilution is then flowed through oxidation
Aluminium column, to remove ligand and copper ion therein, the colourless reaction solution concentrated by rotary evaporation of outflow is finally sunk in excessive methanol
Analysis, vacuum drying, obtains white powder solid product PGMA-g-P (MA-POSS) graft copolymer.
Atomic force microscope (AFM) result shows that film surface roughness is increased to 14.4nm；Contact angle is increased to 122.9 °；
The glass transition temperature of the total object of differential scanning calorimeter (DSC) result display grafting is 96.3 DEG C；Thermogravimetic analysis (TGA) (TGA) is tied
Fruit display thermal decomposition residual volume is increased to 12.2%；Material promotes to 333N the adhesive strength of silicate substrate；Curing materials
Itself improves 80.3% relative to the aperture of pure epoxy curing materials itself；With with conventional epoxy protect sandstone after aperture phase
Than after PGMA-g-P (MA-POSS) graft copolymer protection sandstone that the present invention obtains, aperture improves 35.9%.
Claims (5)
1. the preparation method of silicate cultural relic protection gas permeability POSS basic ring oxygen graft copolymers, which is characterized in that including
Following steps：
(1), the synthesis of l-PGMA polymer chains：Synthesize l-PGMA polymer chains by solution polymerization process, weigh GMA monomers,
The AIBN initiators of 4wt% are dissolved in butanone solvent, and three's mass ratio is 1:0.04:2, it is then added to the circle for being placed with magneton
In the flask of bottom, it is stirred to react 5h at 65 DEG C, after completion of the reaction cooling down, and rotates out extra solvent and presented to reaction solution and glued
Thick shape, then by reaction solution in excessive methanol precipitating, filter, vacuum drying for 24 hours, obtain white solid；
(2), the synthesis of l-PGMA-Br macromole evocating agents：Using in the epoxy group and bromo acid BIBA in GMA
Carboxyl occurs epoxy ring opening reaction and introduces the ends Br, generates ATRP macromole evocating agents, and specific method is：Respectively by the l- of 1mmol
The BIBA of PGMA and 0.1-10.0mmol is dissolved in 5ml THF solvents, and pours into the circle equipped with reflux condensate device and magneton
In the flask of bottom, 30h is reacted under the conditions of 50 DEG C, to the end of reaction, revolving removes excess of solvent, and residual reaction liquid is in excess diethyl ether
Precipitating obtains l-PGMA-Br white powders, and for 24 hours, the epoxy group and the ends Br molar ratio that non-open loop is prepared are for vacuum drying
The l-PGMA-Br macromole evocating agents of 0.1-10；
(3), the ATRP synthesis of PGMA-g-P (MA-POSS) graft copolymer：According to following substances amount ratio by l-PGMA-Br,
CuCl, bipyridine (Bpy) ligand, MA-POSS monomers are added in eggplant type reaction bulb and seal, and mass ratio is followed successively by：1：(6-
56):(13.2-123):(30-280), vacuumizes, and leads to nitrogen, after recycling three times, injects cyclohexanone, cyclohexanone quality is MA-
2 times of POSS monomer masses, under nitrogen atmosphere, stirring at normal temperature 30min are warming up to 100 DEG C, react 8h；After reaction, stop
It only heats, and blowing air, excessive THF dilutions is added, stirring for 24 hours, makes the reaction was complete to terminate, then will be anti-after above-mentioned dilution
The oxidized aluminium column of liquid stream is answered, to remove ligand and copper ion therein, the colourless reaction solution concentrated by rotary evaporation of outflow, finally in excess
Methanol in precipitating, vacuum drying, obtain white powder solid product PGMA-g-P (MA-POSS) graft copolymer；
(4), the solidification of PGMA-g-P (MA-POSS) graft copolymer：PGMA-g-P (MA-POSS) graft copolymer, triethylamine
(TEA) curing agent, THF solvents are in mass ratio=1.5:1:3 are added in reaction bulb, and sustained response for 24 hours, obtains under the conditions of 50 DEG C
Precuring liquid, as gas permeability POSS basic rings oxygen graft copolymer.
2. the preparation side of silicate cultural relic protection gas permeability POSS basic ring oxygen graft copolymers according to claim 1
Method, which is characterized in that
(2), the synthesis of l-PGMA-Br macromole evocating agents：Using in the epoxy group and bromo acid BIBA in GMA
Carboxyl occurs epoxy ring opening reaction and introduces the ends Br, generates ATRP macromole evocating agents, and specific method is：Respectively by the l- of 1mmol
The BIBA of PGMA and 0.1mmol is dissolved in 5ml THF solvents, and pours into the round-bottomed flask equipped with reflux condensate device and magneton
In, 30h is reacted under the conditions of 50 DEG C, to the end of reaction, rotates and removes excess of solvent, residual reaction liquid precipitating in excess diethyl ether,
L-PGMA-Br white powders are obtained, for 24 hours, it is 10/1 that the epoxy group of non-open loop and the ends Br molar ratio, which is prepared, for vacuum drying
L-PGMA-Br macromole evocating agents；
(3), the ATRP synthesis of PGMA-g-P (MA-POSS) graft copolymer：According to following substances amount ratio by l-PGMA-Br,
CuCl, bipyridine (Bpy) ligand, MA-POSS monomers are added in eggplant type reaction bulb and seal, and mass ratio is followed successively by：1:6:
13.2:30, it vacuumizes, leads to nitrogen, after recycling three times, inject cyclohexanone, cyclohexanone quality is 2 times of MA-POSS monomer masses,
Under nitrogen atmosphere, stirring at normal temperature 30min is warming up to 100 DEG C, reacts 8h；After reaction, stop heating, and blowing air, add
Entering excessive THF dilutions, stirring for 24 hours, makes the reaction was complete to terminate, the reaction solution after above-mentioned dilution is then flowed through alumina column,
To remove ligand and copper ion therein, the colourless reaction solution concentrated by rotary evaporation of outflow, finally precipitating, vacuum in excessive methanol
It is dry, obtain white powder solid product PGMA-g-P (MA-POSS) graft copolymer.
3. the preparation side of silicate cultural relic protection gas permeability POSS basic ring oxygen graft copolymers according to claim 1
Method, which is characterized in that
(2), the synthesis of l-PGMA-Br macromole evocating agents：Being dissolved in the l-PGMA of 1mmol and 1mmol BIBA respectively
It in 5ml THF solvents, and pours into the round-bottomed flask equipped with reflux condensate device and magneton, reacts 30h under the conditions of 50 DEG C；It waits for anti-
It should terminate, spin off excess of solvent, residual reaction liquid precipitating in excess diethyl ether obtains l-PGMA-Br white powders, vacuum drying
For 24 hours, the l-PGMA-Br macromole evocating agents that the epoxy group of non-open loop is 1/1 with the ends Br molar ratio are prepared；
(3), the ATRP synthesis of PGMA-g-P (MA-POSS) graft copolymer：According to following substances amount ratio by l-PGMA-Br,
CuCl, bipyridine (Bpy) ligand, MA-POSS monomers are added in eggplant type reaction bulb and seal, and mass ratio is followed successively by：1:31:
66:155, it vacuumizes, leads to nitrogen, after recycling three times, inject cyclohexanone, cyclohexanone quality is 2 times of MA-POSS monomer masses,
Under nitrogen atmosphere, stirring at normal temperature 30min is warming up to 100 DEG C, reacts 8h；After reaction, stop heating, and blowing air, add
Entering excessive THF dilutions, stirring for 24 hours, makes the reaction was complete to terminate, the reaction solution after above-mentioned dilution is then flowed through alumina column,
To remove ligand and copper ion therein, the colourless reaction solution concentrated by rotary evaporation of outflow, finally precipitating, vacuum in excessive methanol
It is dry, obtain white powder solid product PGMA-g-P (MA-POSS) graft copolymer.
4. the preparation side of silicate cultural relic protection gas permeability POSS basic ring oxygen graft copolymers according to claim 1
Method, which is characterized in that
(2), the synthesis of l-PGMA-Br macromole evocating agents：Using in the epoxy group and bromo acid BIBA in GMA
Carboxyl occurs epoxy ring opening reaction and introduces the ends Br, generates ATRP macromole evocating agents, and specific method is：Respectively by the l- of 1mmol
The BIBA of PGMA and 3mmol is dissolved in 5ml THF solvents, and pours into the round-bottomed flask equipped with reflux condensate device and magneton
In, 30h is reacted under the conditions of 50 DEG C, to the end of reaction, rotates and removes excess of solvent, residual reaction liquid precipitating in excess diethyl ether,
L-PGMA-Br white powders are obtained, for 24 hours, the l- that the epoxy group of non-open loop is 1/3 with the ends Br molar ratio is prepared in vacuum drying
PGMA-Br macromole evocating agents；
(3), the ATRP synthesis of PGMA-g-P (MA-POSS) graft copolymer：According to following substances amount ratio by l-PGMA-Br,
CuCl, bipyridine (Bpy) ligand, MA-POSS monomers are added in eggplant type reaction bulb and seal, and mass ratio is followed successively by：1:46:
101.2:230, it vacuumizes, leads to nitrogen, after recycling three times, inject cyclohexanone, cyclohexanone quality is the 2 of MA-POSS monomer masses
Times, under nitrogen atmosphere, stirring at normal temperature 30min is warming up to 100 DEG C, reacts 8h；After reaction, stop heating, and logical sky
Gas, is added excessive THF dilutions, and stirring for 24 hours, makes the reaction was complete to terminate, the reaction solution after above-mentioned dilution is then flowed through oxidation
Aluminium column, to remove ligand and copper ion therein, the colourless reaction solution concentrated by rotary evaporation of outflow is finally sunk in excessive methanol
Analysis, vacuum drying, obtains white powder solid product PGMA-g-P (MA-POSS) graft copolymer.
5. the preparation side of silicate cultural relic protection gas permeability POSS basic ring oxygen graft copolymers according to claim 1
Method, which is characterized in that
(2), the synthesis of l-PGMA-Br macromole evocating agents：Using in the epoxy group and bromo acid BIBA in GMA
Carboxyl occurs epoxy ring opening reaction and introduces the ends Br, generates ATRP macromole evocating agents, and specific method is：Respectively by the l- of 1mmol
The BIBA of PGMA and 10mmol is dissolved in 5ml THF solvents, and pours into the round-bottomed flask equipped with reflux condensate device and magneton
In, 30h is reacted under the conditions of 50 DEG C, to the end of reaction, rotates and removes excess of solvent, residual reaction liquid precipitating in excess diethyl ether,
L-PGMA-Br white powders are obtained, for 24 hours, it is 1/10 that the epoxy group of non-open loop and the ends Br molar ratio, which is prepared, for vacuum drying
L-PGMA-Br macromole evocating agents；
(3), the ATRP synthesis of PGMA-g-P (MA-POSS) graft copolymer：According to following substances amount ratio by l-PGMA-Br,
CuCl, bipyridine (Bpy) ligand, MA-POSS monomers are added in eggplant type reaction bulb and seal, and mass ratio is followed successively by：1:56:
123:280, it vacuumizes, leads to nitrogen, after recycling three times, inject cyclohexanone, cyclohexanone quality is 2 times of MA-POSS monomer masses,
Under nitrogen atmosphere, stirring at normal temperature 30min is warming up to 100 DEG C, reacts 8h；After reaction, stop heating, and blowing air, add
Entering excessive THF dilutions, stirring for 24 hours, makes the reaction was complete to terminate, the reaction solution after above-mentioned dilution is then flowed through alumina column,
To remove ligand and copper ion therein, the colourless reaction solution concentrated by rotary evaporation of outflow, finally precipitating, vacuum in excessive methanol
It is dry, obtain white powder solid product PGMA-g-P (MA-POSS) graft copolymer.
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| POSS-based hybrid cationic copolymers with low aggregation potential for efficient gene delivery;Shan Jiang, et al.;《RSC Advances》;20150817;第5卷(第87期);第71322-71328页 * |
| Self-assembly of POSS-containing block copolymers: Fixing the hierarchical structure in networks;Libor Matějka, et al.;《Polymer》;20131125;第55卷(第1期);第126-136页 * |
| Single-molecular hybrid nano-cylinders: Attaching polyhedral oligomeric silsesquioxane covalently to poly(glycidyl methacrylate) cylindrical brushes;Youyong Xu, et al.;《Polymer》;20091025;第50卷(第25期);第5933-5939页 * |
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