CN106397676A - Preparation method of breathable POSS-based epoxy grafted copolymer for silicate cultural relics - Google Patents
Preparation method of breathable POSS-based epoxy grafted copolymer for silicate cultural relics Download PDFInfo
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- CN106397676A CN106397676A CN201610825027.3A CN201610825027A CN106397676A CN 106397676 A CN106397676 A CN 106397676A CN 201610825027 A CN201610825027 A CN 201610825027A CN 106397676 A CN106397676 A CN 106397676A
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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 invention discloses a preparation method of breathable POSS-based epoxy grafted copolymer for silicate cultural relics. The preparation method includes: polymerizing glycidyl methacrylate through solution polymerization reaction to obtain an autopolymer main chain (l-PGMA); obtaining a macromolecular initiator (l-PGMA-Br) with initiating ends different in number through epoxy open-loop reaction and bromoisobutyric reaction different in molecular weight; under a CuCl/Bpy catalytic system with l-GMPA-Br as the macromolecular initiator, initiating monomethylacryloxy heptaisobutyl polysilsesquioxane (MA-POSS) through atom transfer radical polymerization (ATRP) to obtain a solid powder solid product; curing PGMA-g-P(A-POSS) grafted copolymer. The preparation method has the advantages of simple and quick process, low preparation method, high adhesiveness and obvious breathability improving effect.
Description
Technical field
The invention belongs to functional high molecule material and Techniques of Relics Protection field, particularly to a kind of breathing epoxy bonding
The material phyllosilicate historical relic's protection preparation method of gas permeability POSS basic ring oxygen graft copolymer.
Technical background
Polyhedral oligomeric silsesquioxane (Polyhedral oligomeric silsesquioxane, POSS) is by inorganic
The molecular level nano-organosilicon compound of a diameter of 1-3nm of a class that Si-O-Si framework collectively constitutes with peripheral organic group.By
In having the hollow cage being made up of silica element, give the material modified good gas permeability of POSS base.Glycidyl methacrylate
Glyceride (GMA) is the bifunctional compound with epoxy-functional and double bond, can be introduced in polymer, obtain
There is the material of good bonding performance.Therefore, in order to improve the weakness of PGMA autopolymer poor air permeability, introduce and there is hollow cage
The POSS of structure, copolymerization obtains having the hybrid material of gas permeability and cementability concurrently.Wherein, the inorganic kernel of POSS gives hybrid material
The performances such as good gas permeability, hardness, heat-resisting, weatherability, corrosion-resistant and high-low temperature resistant, give hydridization material after GMA curing reaction
Expect good adhesive property.So, as historical relic's protection class gas permeability adhesives, there is important Research Significance and reality
With being worth, fill up the blank of historical relic's protection special bonding material.
Content of the invention
In order to overcome the defect of above-mentioned prior art, object of the present invention is to provide a kind of protection of silicate cultural relic
With the preparation method of gas permeability POSS basic ring oxygen graft copolymer, the preparation process of POSS basic ring oxygen graft copolymer is by warp
The solution polymerization of allusion quotation, epoxy ring opening reaction and ATRP polymerization reaction, are derived from polymer backbone (l-PGMA), macromolecular successively
Initiator (l-PGMA-Br) and PGMA-g-P (MA-POSS) graft copolymer, it is simple and quick to have a process approach, preparation cost
Low, cementability is good, and the obvious feature of the effect that has improved breathability.
In order to achieve the above object, the technical scheme is that：
The silicate cultural relic protection preparation method of gas permeability POSS basic ring oxygen graft copolymer, comprises the following steps：
(1), the synthesis of l-PGMA polymer chain：L-PGMA polymer chain is synthesized by solution polymerization process, weighs GMA
Monomer, the AIBN initiator of 4wt% are dissolved in butanone solvent, and three's mass ratio is 1:0.04:2, it is then added to be placed with magnetic
In the round-bottomed flask of son, stirring reaction 5h at 65 DEG C, cooling down after completion of the reaction, and revolving goes out unnecessary solvent to reactant liquor
Present thick, then by reactant liquor in excessive methanol precipitating, filter, be vacuum dried 24h, obtain white solid；
(2), the synthesis of l-PGMA-Br macromole evocating agent：Using the epoxide group in GMA and bromo acid BIBA
In carboxyl occur epoxy ring opening reaction to introduce Br end, generate ATRP macromole evocating agent, concrete grammar is：Respectively by 1mmol
The BIBA of l-PGMA and 0.1-10.0mmol be dissolved in 5ml THF solvent, and pour into equipped with reflux condensate device and magneton
Round-bottomed flask in, react 30h under the conditions of 50 DEG C, question response terminates, revolving removes excess of solvent, and residual reaction liquid is in excessive second
Precipitating in ether, obtains l-PGMA-Br white powder, is vacuum dried 24h, prepares the epoxy radicals of non-open loop respectively and rub in Br end
You are than the l-PGMA-Br macromole evocating agent for 0.1-10；
3rd, the ATRP synthesis of PGMA-g-P (MA-POSS) graft copolymer：According to following substances amount ratio by l-PGMA-Br,
CuCl, bipyridine (Bpy) part, MA-POSS monomer are added in eggplant type reaction bulb and seal, and mass ratio is followed successively by：1：(6-
56):(13.2-123):(30-280), vacuumize, logical nitrogen, after circulating three times, inject cyclohexanone, cyclohexanone quality is MA-
2 times of POSS monomer mass, under nitrogen atmosphere, stirring at normal temperature 30min, it is warming up to 100 DEG C, react 8h；After reaction terminates, stop
Only heat, and blowing air, add excessive THF dilution, stir 24h, so that reaction is fully completed, then will be anti-after above-mentioned dilution
Answer liquor stream oxidized aluminium post, to remove part therein and copper ion, the colourless reactant liquor concentrated by rotary evaporation of outflow, finally in excess
Methyl alcohol in precipitating, vacuum drying, obtain white powder solid product PGMA-g-P (MA-POSS) graft copolymer；
4th, the solidification of PGMA-g-P (MA-POSS) graft copolymer：P (GMA-MAPOSS) copolymer, triethylamine (TEA)
Curing agent, THF solvent in mass ratio=1.5:1:3 are added in reaction bulb, sustained response 24h under the conditions of 50 DEG C, obtain pre- solid
Change liquid, as gas permeability POSS basic ring oxygen graft copolymer.
The structural characterization of gas permeability POSS basic ring oxygen graft copolymer basic ring oxygen graft copolymer prepared by the present invention with
Performance, applicating evaluating：
First, utilize AFM (AFM) and contact angle measurement (SCA) that POSS basic ring oxygen graft copolymer is solidified
Agent is studied to surface property before and after adding.Result shows, the addition of POSS makes film surface roughness bring up to
4.1nm, brings up to 117 ° to the contact angle of water；Film surface roughness and the wettability to water is changed after solidification.Differential is swept
Retouch calorimeter (DSC) and thermogravimetic analysis (TGA) (TGA) display, appropriate POSS can significantly improve the glass transition temperature of the common thing of grafting
Degree and heat endurance, due to the increase effect being formed to crosslink density of tridimensional network, finally make glass transition temperature
It is significantly improved before relatively solidifying with heat endurance.
2nd, the adhesive strength of material and humiture circulation aging after bonding force show, adhesive strength is in hydrothermal aging mistake
Assume speed increase, slowly less trend 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 wet and heat ageing resistant performance.
3rd, the curing materials itself of PGMA-g-P (MA-POSS) graft copolymer of contrast conventional epoxies and synthesis
With for sandstone protect back aperture it can be seen that either curing materials itself or be used for sandstone protect after, with conventional epoxy
Resin is compared, and the gas permeability of PGMA-g-P (MA-POSS) graft copolymer is all superior to conventional epoxies.
Specific embodiment
With reference to being embodied as example, the present invention is done with detailed narration.
Embodiment one
The preparation method of the present embodiment gas permeability bonding POSS basic ring oxygen graft copolymer PGMA-g-P (MA-POSS), bag
Include following steps：
(1), the synthesis of l-PGMA polymer chain：L-PGMA polymer chain is synthesized by solution polymerization process, weighs GMA
Monomer, the AIBN initiator of 4wt% are dissolved in butanone solvent, and three's mass ratio is 1:0.04:2, it is then added to be placed with magnetic
In the round-bottomed flask of son, stirring reaction 5h at 65 DEG C, cooling down after completion of the reaction, and revolving goes out unnecessary solvent to reactant liquor
Present thick, then by reactant liquor in excessive methanol precipitating, filter, be vacuum dried 24h, obtain white solid；Yield is about
For 85.02%, molecular weight is 8865g mol-1, PDI=1.34.
(2), the synthesis of l-PGMA-Br macromole evocating agent：Using the epoxide group in GMA and bromo acid BIBA
In carboxyl occur epoxy ring opening reaction to introduce Br end, generate ATRP macromole evocating agent, concrete grammar is：Respectively by 1mmol
The BIBA of l-PGMA and 0.1mmol be dissolved in 5ml THF solvent, and pour the round bottom equipped with reflux condensate device and magneton into
In flask, under the conditions of 50 DEG C, react 30h, question response terminates, and revolving removes excess of solvent, and residual reaction liquid is heavy in excess diethyl ether
Analysis, obtains l-PGMA-Br white powder, is vacuum dried 24h, prepares the epoxy radicals of non-open loop respectively and Br end mol ratio is
10/1 l-PGMA-Br macromole evocating agent；
3rd, the ATRP synthesis of PGMA-g-P (MA-POSS) graft copolymer：According to following substances amount ratio by l-PGMA-Br,
CuCl, bipyridine (Bpy) part, MA-POSS monomer are added in eggplant type reaction bulb and seal, and mass ratio is followed successively by：1:6:
13.2:30, vacuumize, logical nitrogen, after circulating three times, inject cyclohexanone, cyclohexanone quality is 2 times of MA-POSS monomer mass,
Under nitrogen atmosphere, stirring at normal temperature 30min, is warming up to 100 DEG C, reacts 8h；After reaction terminates, stop heating, and blowing air, plus
Enter excessive THF dilution, stir 24h, so that reaction is fully completed, then the reactant liquor after above-mentioned dilution is flowed through alumina column,
To remove part therein and copper ion, the colourless reactant liquor concentrated by rotary evaporation of outflow, finally precipitating, vacuum in excessive methyl alcohol
It is dried, obtain white powder solid product PGMA-g-P (MA-POSS) graft copolymer；
4th, the solidification of PGMA-g-P (MA-POSS) graft copolymer：P (GMA-MAPOSS) copolymer, triethylamine (TEA)
Curing agent, THF solvent in mass ratio=1.5:1:3 are added in reaction bulb, sustained response 24h under the conditions of 50 DEG C, obtain pre- solid
Change liquid, as gas permeability POSS basic ring oxygen graft copolymer.
Effect performance：AFM (AFM) result display film surface roughness is 0.14nm；Contact angle is
110.8°；The glass transition temperature of the common thing of differential scanning calorimeter (DSC) result display grafting is 127.1 DEG C；Thermal weight loss divides
Analysis (TGA) result display thermal decomposition residual volume is 5.3%；Material is 216N to the adhesive strength of silicate substrate.
Embodiment two
The preparation method of the present embodiment gas permeability bonding POSS basic ring oxygen graft copolymer PGMA-g-P (MA-POSS) and reality
Apply example one identical, only second and third step is different：
(2), the synthesis of l-PGMA-Br macromole evocating agent：Respectively that the l-PGMA of 1mmol and 1mmol BIBA is molten
Solution is in 5ml THF solvent, and pours in the round-bottomed flask equipped with reflux condensate device and magneton, reacts 30h under the conditions of 50 DEG C.
Question response terminates, and spins off excess of solvent, residual reaction liquid precipitating in excess diethyl ether, obtains l-PGMA-Br white powder, vacuum
24h is dried, preparing the epoxy radicals of non-open loop respectively with Br end mol ratio is 1/1, l-PGMA-Br macromole evocating agent.
(3), the ATRP synthesis of PGMA-g-P (MA-POSS) graft copolymer：According to following substances amount than by l-PGMA-
Br, CuCl, bipyridine (Bpy) part, MA-POSS monomer are added in eggplant type reaction bulb and seal, and mass ratio is followed successively by：1:
31:66:155, vacuumize, logical nitrogen, after circulating three times, inject cyclohexanone, cyclohexanone quality is the 2 of MA-POSS monomer mass
Times, under nitrogen atmosphere, stirring at normal temperature 30min, it is warming up to 100 DEG C, react 8h；After reaction terminates, stop heating, and logical sky
Gas, adds excessive THF dilution, stirs 24h, so that reaction is fully completed, then the reactant liquor after above-mentioned dilution is flowed through oxidation
Aluminium post, to remove part therein and copper ion, the colourless reactant liquor concentrated by rotary evaporation of outflow, finally sinks in excessive methyl alcohol
Analysis, vacuum drying, obtain white powder solid product PGMA-g-P (MA-POSS) graft copolymer.
Effect performance：AFM (AFM) result display film surface roughness brings up to 0.19nm；Contact angle improves
To 118.1 °；The glass transition temperature of the common thing of differential scanning calorimeter (DSC) result display grafting brings up to 135.7 DEG C；Heat
Zero-g aircraft (TGA) result display thermal decomposition residual volume brings up to 8.2%；Material rises to the adhesive strength of silicate substrate
247N.
Embodiment three
The preparation method of the present embodiment gas permeability bonding POSS basic ring oxygen graft copolymer PGMA-g-P (MA-POSS) and reality
Apply example one identical, only second and third step is different：
(2), the synthesis of l-PGMA-Br macromole evocating agent：Using the epoxide group in GMA and bromo acid BIBA
In carboxyl occur epoxy ring opening reaction to introduce Br end, generate ATRP macromole evocating agent, concrete grammar is：Respectively by 1mmol
The BIBA of l-PGMA and 3mmol be dissolved in 5ml THF solvent, and the round bottom poured into equipped with reflux condensate device and magneton burns
In bottle, under the conditions of 50 DEG C, react 30h, question response terminates, and revolving removes excess of solvent, and residual reaction liquid is heavy in excess diethyl ether
Analysis, obtains l-PGMA-Br white powder, is vacuum dried 24h, prepares the epoxy radicals of non-open loop respectively and Br end mol ratio is
1/3 l-PGMA-Br macromole evocating agent；
(3), the ATRP synthesis of PGMA-g-P (MA-POSS) graft copolymer：According to following substances amount than by l-PGMA-
Br, CuCl, bipyridine (Bpy) part, MA-POSS monomer are added in eggplant type reaction bulb and seal, and mass ratio is followed successively by：1:
46:101.2:230, vacuumize, logical nitrogen, after circulating three times, inject cyclohexanone, cyclohexanone quality is MA-POSS monomer mass
2 times, under nitrogen atmosphere, stirring at normal temperature 30min, be warming up to 100 DEG C, react 8h；After reaction terminates, stop heating, and lead to
Air, adds excessive THF dilution, stirs 24h, so that reaction is fully completed, then the reactant liquor after above-mentioned dilution is flowed through oxygen
Change aluminium post, to remove part therein and copper ion, the colourless reactant liquor concentrated by rotary evaporation of outflow, finally sink in excessive methyl alcohol
Analysis, vacuum drying, obtain white powder solid product PGMA-g-P (MA-POSS) graft copolymer.
Effect performance：AFM (AFM) result display film surface roughness brings up to 0.63nm；Contact angle improves
To 120.7 °；The glass transition temperature of the common thing of differential scanning calorimeter (DSC) result display grafting is 115.1 DEG C；Thermal weight loss
Analysis (TGA) result display thermal decomposition residual volume brings up to 8.4%；Material rises to the adhesive strength of silicate substrate
275N.
Example IV
The preparation method of the present embodiment gas permeability bonding POSS basic ring oxygen graft copolymer PGMA-g-P (MA-POSS) and reality
Apply example one identical, only second and third step is different：
(2), the synthesis of l-PGMA-Br macromole evocating agent：Using the epoxide group in GMA and bromo acid BIBA
In carboxyl occur epoxy ring opening reaction to introduce Br end, generate ATRP macromole evocating agent, concrete grammar is：Respectively by 1mmol
The BIBA of l-PGMA and 10mmol be dissolved in 5ml THF solvent, and pour the round bottom equipped with reflux condensate device and magneton into
In flask, under the conditions of 50 DEG C, react 30h, question response terminates, and revolving removes excess of solvent, and residual reaction liquid is heavy in excess diethyl ether
Analysis, obtains l-PGMA-Br white powder, is vacuum dried 24h, prepares the epoxy radicals of non-open loop respectively and Br end mol ratio is
1/10 l-PGMA-Br macromole evocating agent；
(3), the ATRP synthesis of PGMA-g-P (MA-POSS) graft copolymer：According to following substances amount than by l-PGMA-
Br, CuCl, bipyridine (Bpy) part, MA-POSS monomer are added in eggplant type reaction bulb and seal, and mass ratio is followed successively by：1:
56:123:280, vacuumize, logical nitrogen, after circulating three times, inject cyclohexanone, cyclohexanone quality is the 2 of MA-POSS monomer mass
Times, under nitrogen atmosphere, stirring at normal temperature 30min, it is warming up to 100 DEG C, react 8h；After reaction terminates, stop heating, and logical sky
Gas, adds excessive THF dilution, stirs 24h, so that reaction is fully completed, then the reactant liquor after above-mentioned dilution is flowed through oxidation
Aluminium post, to remove part therein and copper ion, the colourless reactant liquor concentrated by rotary evaporation of outflow, finally sinks in excessive methyl alcohol
Analysis, vacuum drying, obtain white powder solid product PGMA-g-P (MA-POSS) graft copolymer.
AFM (AFM) result display film surface roughness brings up to 14.4nm；Contact angle brings up to 122.9 °；
The glass transition temperature of the common thing 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 brings up to 12.2%；Material rises to 333N to the adhesive strength of silicate substrate；Curing materials
Itself improve 80.3% with respect to the pure epoxy curing materials aperture of itself；With with conventional epoxy protect sandstone after aperture phase
After PGMA-g-P (MA-POSS) the graft copolymer protection sandstone that the present invention obtains, aperture improves 35.9% to ratio.
Claims (5)
1. silicate cultural relic protection uses the preparation method of gas permeability POSS basic ring oxygen graft copolymer it is characterised in that including
Following steps：
(1), the synthesis of l-PGMA polymer chain：By solution polymerization process synthesize l-PGMA polymer chain, weigh GMA monomer,
The AIBN initiator of 4wt% is dissolved in butanone solvent, and three's mass ratio is 1:0.04:2, it is then added to be placed with the circle of magneton
In the flask of bottom, stirring reaction 5h at 65 DEG C, cooling down after completion of the reaction, and revolving go out unnecessary solvent to reactant liquor present viscous
Thick shape, then by reactant liquor in excessive methanol precipitating, filter, be vacuum dried 24h, obtain white solid；
(2), the synthesis of l-PGMA-Br macromole evocating agent：Using in the epoxide group in GMA and bromo acid BIBA
Carboxyl occurs epoxy ring opening reaction to introduce Br end, generates ATRP macromole evocating agent, and concrete grammar is：Respectively by the l- of 1mmol
The BIBA of PGMA and 0.1-10.0mmol is dissolved in 5ml THF solvent, and pours the circle equipped with reflux condensate device and magneton into
In the flask of bottom, under the conditions of 50 DEG C, react 30h, question response terminates, and revolving removes excess of solvent, and residual reaction liquid is in excess diethyl ether
Precipitating, obtains l-PGMA-Br white powder, is vacuum dried 24h, prepares epoxy radicals and the Br end mol ratio of non-open loop respectively
L-PGMA-Br macromole evocating agent for 0.1-10；
3rd, the ATRP synthesis of PGMA-g-P (MA-POSS) graft copolymer：According to following substances amount ratio by l-PGMA-Br,
CuCl, bipyridine (Bpy) part, MA-POSS monomer are added in eggplant type reaction bulb and seal, and mass ratio is followed successively by：1：(6-
56):(13.2-123):(30-280), vacuumize, logical nitrogen, after circulating three times, inject cyclohexanone, cyclohexanone quality is MA-
2 times of POSS monomer mass, under nitrogen atmosphere, stirring at normal temperature 30min, it is warming up to 100 DEG C, react 8h；After reaction terminates, stop
Only heat, and blowing air, add excessive THF dilution, stir 24h, so that reaction is fully completed, then will be anti-after above-mentioned dilution
Answer liquor stream oxidized aluminium post, to remove part therein and copper ion, the colourless reactant liquor concentrated by rotary evaporation of outflow, finally in excess
Methyl alcohol in precipitating, vacuum drying, obtain white powder solid product PGMA-g-P (MA-POSS) graft copolymer；
4th, the solidification of PGMA-g-P (MA-POSS) graft copolymer：P (GMA-MAPOSS) copolymer, triethylamine (TEA) solidifies
Agent, THF solvent in mass ratio=1.5:1:3 are added in reaction bulb, and sustained response 24h under the conditions of 50 DEG C obtains precuring liquid,
It is gas permeability POSS basic ring oxygen graft copolymer.
2. the silicate cultural relic protection according to claim 1 preparation side of gas permeability POSS basic ring oxygen graft copolymer
Method it is characterised in that
(2), the synthesis of l-PGMA-Br macromole evocating agent：Using in the epoxide group in GMA and bromo acid BIBA
Carboxyl occurs epoxy ring opening reaction to introduce Br end, generates ATRP macromole evocating agent, and concrete grammar is：Respectively by the l- of 1mmol
The BIBA of PGMA and 0.1mmol is dissolved in 5ml THF solvent, and pours the round-bottomed flask equipped with reflux condensate device and magneton into
In, react 30h under the conditions of 50 DEG C, question response terminates, revolving removes excess of solvent, residual reaction liquid precipitating in excess diethyl ether,
Obtain l-PGMA-Br white powder, be vacuum dried 24h, preparing the epoxy radicals of non-open loop and Br end mol ratio respectively is 10/
1 l-PGMA-Br macromole evocating agent；
(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) part, MA-POSS monomer are added in eggplant type reaction bulb and seal, and mass ratio is followed successively by：1:6:
13.2:30, vacuumize, logical nitrogen, after circulating three times, inject cyclohexanone, cyclohexanone quality is 2 times of MA-POSS monomer mass,
Under nitrogen atmosphere, stirring at normal temperature 30min, is warming up to 100 DEG C, reacts 8h；After reaction terminates, stop heating, and blowing air, plus
Enter excessive THF dilution, stir 24h, so that reaction is fully completed, then the reactant liquor after above-mentioned dilution is flowed through alumina column,
To remove part therein and copper ion, the colourless reactant liquor concentrated by rotary evaporation of outflow, finally precipitating, vacuum in excessive methyl alcohol
It is dried, obtain white powder solid product PGMA-g-P (MA-POSS) graft copolymer.
3. the silicate cultural relic protection according to claim 1 preparation side of gas permeability POSS basic ring oxygen graft copolymer
Method it is characterised in that
(2), the synthesis of l-PGMA-Br macromole evocating agent：Being dissolved in the l-PGMA of 1mmol and 1mmol BIBA respectively
In 5ml THF solvent, and pour in the round-bottomed flask equipped with reflux condensate device and magneton, under the conditions of 50 DEG C, react 30h.Treat anti-
Should terminate, spin off excess of solvent, residual reaction liquid precipitating in excess diethyl ether, obtain l-PGMA-Br white powder, vacuum drying
24h, preparing the epoxy radicals of non-open loop respectively with Br end mol ratio is 1/1, l-PGMA-Br macromole evocating agent.
(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) part, MA-POSS monomer are added in eggplant type reaction bulb and seal, and mass ratio is followed successively by：1:31:
66:155, vacuumize, logical nitrogen, after circulating three times, inject cyclohexanone, cyclohexanone quality is 2 times of MA-POSS monomer mass,
Under nitrogen atmosphere, stirring at normal temperature 30min, is warming up to 100 DEG C, reacts 8h；After reaction terminates, stop heating, and blowing air, plus
Enter excessive THF dilution, stir 24h, so that reaction is fully completed, then the reactant liquor after above-mentioned dilution is flowed through alumina column,
To remove part therein and copper ion, the colourless reactant liquor concentrated by rotary evaporation of outflow, finally precipitating, vacuum in excessive methyl alcohol
It is dried, obtain white powder solid product PGMA-g-P (MA-POSS) graft copolymer.
4. the silicate cultural relic protection according to claim 1 preparation side of gas permeability POSS basic ring oxygen graft copolymer
Method it is characterised in that
(2), the synthesis of l-PGMA-Br macromole evocating agent：Using in the epoxide group in GMA and bromo acid BIBA
Carboxyl occurs epoxy ring opening reaction to introduce Br end, generates ATRP macromole evocating agent, and concrete grammar is：Respectively by the l- of 1mmol
The BIBA of PGMA and 3mmol is dissolved in 5ml THF solvent, and pours the round-bottomed flask equipped with reflux condensate device and magneton into
In, react 30h under the conditions of 50 DEG C, question response terminates, revolving removes excess of solvent, residual reaction liquid precipitating in excess diethyl ether,
Obtain l-PGMA-Br white powder, be vacuum dried 24h, preparing the epoxy radicals of non-open loop and Br end mol ratio respectively is 1/3
L-PGMA-Br macromole evocating agent；
(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) part, MA-POSS monomer are added in eggplant type reaction bulb and seal, and mass ratio is followed successively by：1:46:
101.2:230, vacuumize, logical nitrogen, after circulating three times, inject cyclohexanone, cyclohexanone quality is the 2 of MA-POSS monomer mass
Times, under nitrogen atmosphere, stirring at normal temperature 30min, it is warming up to 100 DEG C, react 8h；After reaction terminates, stop heating, and logical sky
Gas, adds excessive THF dilution, stirs 24h, so that reaction is fully completed, then the reactant liquor after above-mentioned dilution is flowed through oxidation
Aluminium post, to remove part therein and copper ion, the colourless reactant liquor concentrated by rotary evaporation of outflow, finally sinks in excessive methyl alcohol
Analysis, vacuum drying, obtain white powder solid product PGMA-g-P (MA-POSS) graft copolymer.
5. the silicate cultural relic protection according to claim 1 preparation side of gas permeability POSS basic ring oxygen graft copolymer
Method it is characterised in that
(2), the synthesis of l-PGMA-Br macromole evocating agent：Using in the epoxide group in GMA and bromo acid BIBA
Carboxyl occurs epoxy ring opening reaction to introduce Br end, generates ATRP macromole evocating agent, and concrete grammar is：Respectively by the l- of 1mmol
The BIBA of PGMA and 10mmol is dissolved in 5ml THF solvent, and pours the round-bottomed flask equipped with reflux condensate device and magneton into
In, react 30h under the conditions of 50 DEG C, question response terminates, revolving removes excess of solvent, residual reaction liquid precipitating in excess diethyl ether,
Obtain l-PGMA-Br white powder, be vacuum dried 24h, preparing the epoxy radicals of non-open loop and Br end mol ratio respectively is 1/
10 l-PGMA-Br macromole evocating agent；
(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) part, MA-POSS monomer are added in eggplant type reaction bulb and seal, and mass ratio is followed successively by：1:56:
123:280, vacuumize, logical nitrogen, after circulating three times, inject cyclohexanone, cyclohexanone quality is 2 times of MA-POSS monomer mass,
Under nitrogen atmosphere, stirring at normal temperature 30min, is warming up to 100 DEG C, reacts 8h；After reaction terminates, stop heating, and blowing air, plus
Enter excessive THF dilution, stir 24h, so that reaction is fully completed, then the reactant liquor after above-mentioned dilution is flowed through alumina column,
To remove part therein and copper ion, the colourless reactant liquor concentrated by rotary evaporation of outflow, finally precipitating, vacuum in excessive methyl alcohol
It is dried, obtain white powder solid product PGMA-g-P (MA-POSS) graft copolymer.
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