CN102675564B - Method for efficient graft polymerization of glycidyl methacrylate on surface of silica gel particle - Google Patents
Method for efficient graft polymerization of glycidyl methacrylate on surface of silica gel particle Download PDFInfo
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- CN102675564B CN102675564B CN201210135384.9A CN201210135384A CN102675564B CN 102675564 B CN102675564 B CN 102675564B CN 201210135384 A CN201210135384 A CN 201210135384A CN 102675564 B CN102675564 B CN 102675564B
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Abstract
The invention discloses a method for efficient graft polymerization of glycidyl methacrylate on the surface of a silica gel particle and relates to a graft polymerization method for efficient grafting PGMA on the surface of the silica gel particle. The method includes the following steps of conducting surface modification on active silica gel through gamma-mercaptopropyltrimethoxysilane so as to obtain a modified silica gel particle MPMS-SiO2 with the surface containing sulfhydryl; then mixing MPMS-SiO2, N, N-dimethylformamide and glycidyl methacrylate, adding initiator benzoyl peroxide (BPO) and conducting a graft polymerization reaction under the conditions of constant temperature and stirring so as to obtain a grafting particle PGMA/SiO2. The method utilizes graft polymerization initiated by a sulfhydryl-BPO system, due to the fact that an active site is arranged on the surface of a carrier, high graft degree is achieved, and efficient graft polymerization of oil soluble monomer glycidyl methacrylate (GMA) on the surface of the silica gel.
Description
Technical field
The present invention relates to the graft polymerization procedure at the efficient grafting PGMA of silica particle surface, relate in particular to a kind of sulfydryl-BPO redox initiation system that utilizes and realize glycidyl methacrylate in the method for the efficient graft polymerization of silica particle surface.
Background technology
Function macromole being grafted on to inorganic particles surface, the macromolecular physical and chemical performance functional and that inorganic particles is good of function is mutually combined, is to prepare at present the important channel of functional composite particles.At inorganic particles (micron order and nano level) surface grafting function macromole, can give particle many new characteristics, as absorption property, chemically reactive, biological activity, biocompatibility, optical activity and dispersibility etc., numerous scientific researches and the practical application area such as can be widely used in the immobilization of chromatographic stationary phases, heterogeneous catalysis, enzyme, the separation of biomacromolecule, high-performance sorbing material, sensor build and the enhancing of plastics is toughness reinforcing.
Glycidyl methacrylate (GMA) is a kind of vinyl monomer containing epoxy group(ing), by equal polymerization or copolymerization, can make the polymer macromolecule with epoxide group.Epoxide group is a kind of active group, can with carboxyl, hydroxyl and the multiple group generation ring-opening reaction such as amino, by GMA polymer transition, be various function macromole.Therefore, GMA is grafted on to solia particle surface, can form several functions grafting particulate, at numerous sciemtifec and technical spheres, be all widely used.Such as, prepare chelating material and sorbent material, for the isolation and purification of Solid-Phase Extraction, biomacromolecule, environmental improvement, as chromatographic stationary phases etc.; Prepare solid-supported catalyst, for heterogeneous catalysis; Prepare function carrier, for building the slow control delivery of medicine; Also can construct Host-guest system, for molecular recognition and structure biosensor etc.In a word, at solia particle surface grafting polymerization GMA, there is important scientific value.
Adopt chemical graft process in the macromolecular method of solia particle surface grafting, can be divided into " being grafted to " (Grafting onto) method and " picking out " (grafting from) method.The former is by the chemical reaction between polymer terminal group functional group and microparticle material surface active groups, and polymkeric substance coupling is grafted to microparticle surfaces, therefore the coupling grafting that is otherwise known as (coupling graft) method; Latter is that the avtive spot (or polymerizable double bond or initiating group) by can polymerization in the introducing of microparticle material surface makes monomer start to occur polymerization from microparticle surfaces, realizes graft polymerization.The method that " picks out " has advantages of that graft(ing) degree is high, therefore be widely used.
In " picking out " method, if introduce initiating group on solia particle surface, owing to causing species, be positioned at microparticle surfaces, therefore the efficiency of graft polymerization is higher.But, because the correctability group that solia particle surface has is often capped, must just can make these groups out exposed through special activation treatment, so will realize at solia particle surface introducing initiating group more difficult often.
Summary of the invention
The object of this invention is to provide a kind of method in the efficient graft polymerization glycidyl methacrylate of silica particle surface.
The present invention is according to the thinking of molecular designing, manage sulfydryl to introduce micron order silica gel microparticle surfaces, form sulfydryl-benzoyl peroxide (BPO) redox initiation system, in silica particle surface, produce free radical, realize the graft polymerization of glycidyl methacrylate (GMA) at Silica Surface, thereby made the composite particles PGMA/SiO of high graft(ing) degree
2.
The present invention is achieved by the following technical solutions:
A method in the efficient graft polymerization glycidyl methacrylate of silica particle surface, comprises the following steps:
(1) activated silica gel surface is sulfhydryl modified: 2-3g activated silica gel is joined in 125mL toluene, and add γ-mercaptopropyl trimethoxysilane (MPMS) of 2-3mL, at 110-115 ℃, react 10-12h, product after suction filtration toluene repetitive scrubbing, use again afterwards washing with alcohol, vacuum-drying, makes surface containing the modified silica-gel particulate MPMS-SiO of sulfydryl
2;
(2) graft polymerization of glycidyl methacrylate: add 1-2g MPMS-SiO in the four-hole boiling flask that electric mixer, reflux condensing tube and thermometer are housed
2add again 70mLN, dinethylformamide DMF and 7-9mL glycidyl methacrylate (monomer GMA), logical nitrogen 30min, with the air in eliminating system, then the temperature of system is risen to 55 ℃, add 0.08-0.09g initiator B PO, constant temperature also carries out graft polymerization reaction under agitation condition, after reaction finishes, and suction filtration, product particulate is used in Soxhlet extractor to acetone extracting 24h, to remove physical adsorption at the polymkeric substance of microparticle surfaces, then carry out vacuum-drying, obtain grafting particulate PGMA/SiO
2.
Under the effect of sulfydryl-BPO initiator system, the reaction process of monomer GMA surface Inducing Graft Polymerization is as shown in graphic 1.
Three kinds of particulate SiO
2, MPMS-SiO
2and PGMA/SiO
2infrared spectrogram as shown in Figure 2, as can be seen from the figure, with SiO
2infrared spectra compare, at modified granular MPMS-SiO
2infrared spectrum in, 3440cm
-1near the absorption peak relevant to silicon hydroxyl, greatly weakens, meanwhile at 2566cm
-1there is the stretching vibration absorption peak of sulfydryl S-H key in place, at 2920cm
-1the asymmetrical stretching vibration absorption peak of place's c h bond is obviously strengthened, and shows that coupling agent MPMS has occurred to react with silicon hydroxyl, has been bonded in silica particle surface, at grafting particulate PGMA/SiO
2infrared spectrum in, in 908cm
-1place and 1740cm
-1having there is respectively the epoxy group(ing) of PGMA and the charateristic avsorption band of ester carbonyl group in place, fully shows grafting particulate PGMA/SiO
2formation.
SiO
2particulate and grafting particulate PGMA/SiO
2stereoscan photograph as shown in Figure 3,4, from Fig. 3, see SiO before grafting
2particle surface is more coarse, uneven; And from Fig. 4, see SiO after grafting
2it is comparatively smooth that particle surface obviously becomes, and this is due to the filling up due to coating function of polystyrene that is grafted on Silica Surface.
Modified granular MPMS-SiO
2with grafting particulate PGMA/SiO
2thermal weight loss spectrogram as shown in Figure 5, adopt the general method of inorganic particles graft polymerization objects system thermal weight loss spectral line to analyze Fig. 5: as seen from the figure, modified granular MPMS-SiO
2with grafting particulate PGMA/SiO
2all near 140 ℃, obviously decompose weightless (being the volatile weight loss of planar water), modified granular is complete in 730 ℃ of decomposition before, and weightlessness 10.73%, corresponding to the bonded amount (coincideing with iodometric determination result) of coupling agent MPMS; Grafting particulate is complete in 750 ℃ of decomposition, and weightless 33.78%.
Compared with prior art, the present invention has the following advantages:
The graft polymerization that the present invention utilizes sulfydryl-BPO system to cause, because avtive spot is positioned at carrier surface, therefore have high graft(ing) degree, has realized the efficient graft polymerization of oil-soluble monomer GMA at Silica Surface.
Accompanying drawing explanation
Fig. 1 is that glycidyl methacrylate is at the chemical reaction process of the grafting process of Silica Surface;
Fig. 2 is three kinds of particulate SiO
2, MPMS-SiO
2and PGMA/SiO
2infrared spectrogram;
Fig. 3 is SiO
2the scanning electron microscope of particulate;
Fig. 4 is grafting particulate PGMA/SiO
2scanning electron microscope;
Fig. 5 is modified granular MPMS-SiO
2with grafting particulate PGMA/SiO
2thermal weight loss spectrogram.
Embodiment
Embodiment 1
A method in the efficient graft polymerization glycidyl methacrylate of silica particle surface, comprises the following steps:
(1) activated silica gel surface is sulfhydryl modified: 2g activated silica gel is joined in 125mL toluene, and add γ-mercaptopropyl trimethoxysilane (MPMS) of 2mL, at 110 ℃, react 11h, product after suction filtration toluene repetitive scrubbing, use again afterwards washing with alcohol, vacuum-drying, makes surface containing the modified silica-gel particulate MPMS-SiO of sulfydryl
2;
(2) graft polymerization of glycidyl methacrylate: add 1g MPMS-SiO in the four-hole boiling flask that electric mixer, reflux condensing tube and thermometer are housed
2add again 70mLN, dinethylformamide DMF and 7.5mL glycidyl methacrylate (monomer GMA), logical nitrogen 30min, with the air in eliminating system, then the temperature of system is risen to 55 ℃, add 0.08g initiator B PO, constant temperature also carries out graft polymerization reaction under agitation condition, after reaction finishes, and suction filtration, product particulate is used in Soxhlet extractor to acetone extracting 24h, to remove physical adsorption at the polymkeric substance of microparticle surfaces, then carry out vacuum-drying, obtain grafting particulate PGMA/SiO
2.
Adopt thermogravimetry to record grafting particulate PGMA/SiO
2the graft(ing) degree of surface PGMA is 24.4g/100g.
A method in the efficient graft polymerization glycidyl methacrylate of silica particle surface, comprises the following steps:
(1) activation of silica gel: it is 8% the methanesulfonic aqueous solution that the aerosil particles of getting 30g is placed in 150mL concentration, stir-activating 8h under reflux temperature, the silica gel after activation with distilled water repetitive scrubbing to neutral, suction filtration, vacuum-drying, obtains activated silica gel;
(2) activated silica gel surface is sulfhydryl modified: 3g activated silica gel is joined in 125mL toluene, and add γ-mercaptopropyl trimethoxysilane (MPMS) of 3mL, at 115 ℃, react 12h, product after suction filtration toluene repetitive scrubbing, use again afterwards washing with alcohol, vacuum-drying, makes surface containing the modified silica-gel particulate MPMS-SiO of sulfydryl
2;
(3) graft polymerization of glycidyl methacrylate: add 2g MPMS-SiO in the four-hole boiling flask that electric mixer, reflux condensing tube and thermometer are housed
2add again 70mLN, dinethylformamide DMF and 9mL glycidyl methacrylate (monomer GMA), logical nitrogen 30min, with the air in eliminating system, then the temperature of system is risen to 55 ℃, add 0.09g initiator B PO, constant temperature also carries out graft polymerization reaction under agitation condition, after reaction finishes, and suction filtration, product particulate is used in Soxhlet extractor to acetone extracting 24h, to remove physical adsorption at the polymkeric substance of microparticle surfaces, then carry out vacuum-drying, obtain grafting particulate PGMA/SiO
2.
Embodiment 3
A method in the efficient graft polymerization glycidyl methacrylate of silica particle surface, comprises the following steps:
(1) activation of silica gel: it is 5% the methanesulfonic aqueous solution that the aerosil particles of getting 30g is placed in 150mL concentration, stir-activating 10h under reflux temperature, the silica gel after activation with distilled water repetitive scrubbing to neutral, suction filtration, vacuum-drying, obtains activated silica gel;
(2) activated silica gel surface is sulfhydryl modified: 2.5g activated silica gel is joined in 125mL toluene, and add γ-mercaptopropyl trimethoxysilane (MPMS) of 2mL, at 113 ℃, react 10h, product after suction filtration toluene repetitive scrubbing, use again afterwards washing with alcohol, vacuum-drying, makes surface containing the modified silica-gel particulate MPMS-SiO of sulfydryl
2;
(3) graft polymerization of glycidyl methacrylate: add 1.5g MPMS-SiO in the four-hole boiling flask that electric mixer, reflux condensing tube and thermometer are housed
2add again 70mLN, dinethylformamide DMF and 8mL glycidyl methacrylate (monomer GMA), logical nitrogen 30min, with the air in eliminating system, then the temperature of system is risen to 55 ℃, add 0.08g initiator B PO, constant temperature also carries out graft polymerization reaction under agitation condition, after reaction finishes, and suction filtration, product particulate is used in Soxhlet extractor to acetone extracting 24h, to remove physical adsorption at the polymkeric substance of microparticle surfaces, then carry out vacuum-drying, obtain grafting particulate PGMA/SiO
2.
Embodiment 4
A method in the efficient graft polymerization glycidyl methacrylate of silica particle surface, comprises the following steps:
(1) activated silica gel surface is sulfhydryl modified: 2.5g activated silica gel is joined in 125mL toluene, and add γ-mercaptopropyl trimethoxysilane (MPMS) of 2mL, at 115 ℃, react 10h, product after suction filtration toluene repetitive scrubbing, use again afterwards washing with alcohol, vacuum-drying, makes surface containing the modified silica-gel particulate MPMS-SiO of sulfydryl
2;
(2) graft polymerization of glycidyl methacrylate: add 1.5g MPMS-SiO in the four-hole boiling flask that electric mixer, reflux condensing tube and thermometer are housed
2add again 70mLN, dinethylformamide DMF and 7mL glycidyl methacrylate (monomer GMA), logical nitrogen 30min, with the air in eliminating system, then the temperature of system is risen to 55 ℃, add 0.08g initiator B PO, constant temperature also carries out graft polymerization reaction under agitation condition, after reaction finishes, and suction filtration, product particulate is used in Soxhlet extractor to acetone extracting 24h, to remove physical adsorption at the polymkeric substance of microparticle surfaces, then carry out vacuum-drying, obtain grafting particulate PGMA/SiO
2.
Claims (1)
1. in a method for the efficient graft polymerization glycidyl methacrylate of silica particle surface, it is characterized in that comprising the following steps:
(1) activated silica gel surface is sulfhydryl modified: 2-3g activated silica gel is joined in 125mL toluene, and add γ-mercaptopropyl trimethoxysilane of 2-3mL, at 110-115 ℃, react 10-12h, product after suction filtration toluene repetitive scrubbing, use again afterwards washing with alcohol, vacuum-drying, makes surface containing the modified silica-gel particulate MPMS-SiO of sulfydryl
2;
(2) graft polymerization of glycidyl methacrylate: add 1-2g MPMS-SiO in the four-hole boiling flask that electric mixer, reflux condensing tube and thermometer are housed
2, then add 70mLN, dinethylformamide DMF and 7-9mL glycidyl methacrylate, logical nitrogen 30min, with the air in eliminating system, then rises to 55 ℃ by the temperature of system, add 0.08-0.09g initiator B PO, constant temperature also carries out graft polymerization reaction under agitation condition, after reaction finishes, and suction filtration, product particulate is used in Soxhlet extractor to acetone extracting 24h, to remove physical adsorption at the polymkeric substance of microparticle surfaces, then carry out vacuum-drying, obtain grafting particulate PGMA/SiO
2.
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| CN105175653A (en) * | 2015-09-14 | 2015-12-23 | 中北大学 | Method for preparing PHEMA/SiO2 by surface-initiated graft polymerization in non-aqueous medium |
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Inventor after: Du Ruikui Inventor after: Xu Chunju Inventor after: An Fuqiang Inventor after: Gao Baojiao Inventor after: Li Yanbin Inventor after: Wang Ruixin Inventor after: Shi Xuejun Inventor before: Gao Baojiao Inventor before: An Fuqiang Inventor before: Du Ruikui Inventor before: Li Yanbin Inventor before: Wang Ruixin Inventor before: Shi Xuejun |
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