CN102675564A - 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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- CN102675564A CN102675564A CN2012101353849A CN201210135384A CN102675564A CN 102675564 A CN102675564 A CN 102675564A CN 2012101353849 A CN2012101353849 A CN 2012101353849A CN 201210135384 A CN201210135384 A CN 201210135384A CN 102675564 A CN102675564 A CN 102675564A
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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 graft polymerization procedure, relate in particular to a kind of sulfydryl-BPO redox initiation system that utilizes and realize the method for SY-Monomer G in the efficient graft polymerization of silica particle surface at the efficient grafting PGMA of silica particle surface.
Background technology
The function macromole being grafted on the inorganic particles surface, function macromolecular functional and the good physical and chemical performance of inorganic particles are mutually combined, is the important channel of the functional composite particles of preparation at present.At inorganic particles (micron order and nano level) surface grafting function macromole; Can give particle many new characteristics; Like absorption property, chemically reactive, biological activity, biocompatibility, optical activity and dispersibility etc., numerous scientific researches and practical application area such as separation, high-performance sorbing material, the transmitter that can be widely used in immobilization, the biomacromolecule of chromatographic stationary phase, heterogeneous catalysis, enzyme makes up and the enhancing of plastics is toughness reinforcing.
SY-Monomer G (GMA) is a kind of vinyl monomer that contains epoxy group(ing), can make the polymer macromolecule that has epoxide group through equal polymerization or copolymerization.Epoxide group is a kind of active group, can with multiple group generation ring-opening reactions such as carboxyl, hydroxyl and amino, be various function macromole with the GMA polymer transition.Therefore, GMA is grafted on the solia particle surface, can form multiple function grafting particulate, all be widely used at numerous sciemtifec and technical spheres.Such as, preparation chelating material and sorbent material are used for isolation and purification, the environmental improvement, equal as chromatographic stationary of SPE, biomacromolecule; The preparation solid-supported catalyst is used for heterogeneous catalysis; Prepare function carrier, be used to make up the slow control delivery of medicine; Also the host-guest system be can construct, molecular recognition and structure biosensor or the like are used for.In a word, has important scientific value at solia particle surface grafting polymerization GMA.
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 through the chemical reaction between polymer terminal group functional group and the microparticle material surface active groups, and the polymkeric substance coupling is grafted to microparticle surfaces, so the coupling grafting that is otherwise known as (coupling graft) method; The latter then is through making monomer begin to take place polymerization from microparticle surfaces by polymeric avtive spot (or polymerizable double bond or initiating group) in microparticle material surface introducing, realizing graft polymerization.The method that " picks out " has the high advantage of graft(ing)degree, so be widely used.
In " picking out " method,, be positioned at microparticle surfaces owing to cause species, so the efficient of graft polymerization is higher if introduce initiating group on the solia particle surface.But, because the correctability group that has of solia particle surface often is capped, must just can make these groups expose out through special activation treatment, to introduce initiating group relatively more difficult often so will be implemented in the solia particle surface.
Summary of the invention
The purpose of this invention is to provide a kind of method at the efficient graft polymerization SY-Monomer G of silica particle surface.
The present invention is according to the thinking of molecular designing; Manage sulfydryl is introduced micron order silica gel microparticle surfaces; Constitute sulfydryl-Lucidol (BPO) redox initiation system; Produce radical in silica particle surface, realized the graft polymerization of SY-Monomer G (GMA), thereby make the composite particles PGMA/SiO of high graft(ing)degree on the silica gel surface
2
The present invention realizes through following technical scheme:
A kind of method at the efficient graft polymerization SY-Monomer G of silica particle surface may further comprise the steps:
(1) the activated silica gel surface is sulfhydryl modified: the 2-3g activated silica gel is joined in the 125mL toluene; And γ-mercaptopropyl trimethoxysilane (MPMS) of adding 2-3mL; React 10-12h down at 110-115 ℃, the product behind the suction filtration is used the toluene repetitive scrubbing, uses washing with alcohol afterwards again; Vacuum-drying promptly makes the modified silica-gel particulate MPMS-SiO that the surface contains sulfydryl
2
(2) graft polymerization of SY-Monomer G: in the four-hole boiling flask that electric mixer, reflux condensing tube and TM are housed, add 1-2g MPMS-SiO
2, add 70mLN again, dinethylformamide DMF and 7-9mL SY-Monomer G (monomer GMA); Logical nitrogen 30min, with the air in the eliminating system, the temperature with system rises to 55 ℃ then; Add 0.08-0.09g initiator B PO, constant temperature also carries out graft polymerization reaction under agitation condition, after reaction finishes; Suction filtration, with the product particulate in Soxhlet extractor with acetone extracting 24h, to remove the polymkeric substance of physical adsorption at microparticle surfaces; Carry out vacuum-drying then, promptly obtain grafting particulate PGMA/SiO
2
Under sulfydryl-BPO initiator system effect, monomer GMA surface initiation grafting polymeric reaction process is 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
2Ir spectra compare, at modified granular MPMS-SiO
2Infrared spectrum in, 3440cm
-1Near the absorption peak relevant with the silicon hydroxyl greatly weakens, meanwhile at 2566cm
-1The stretching vibration absorption peak of sulfydryl S-H key has appearred in the place, at 2920cm
-1The asymmetrical stretching vibration absorption peak of place's c h bond is obviously strengthened, and shows that reaction has taken place for coupling agent MPMS and silicon hydroxyl, has been bonded in silica particle surface, at grafting particulate PGMA/SiO
2Infrared spectrum in, in 908cm
-1Place and 1740cm
-1The epoxy group(ing) of PGMA and the charateristic avsorption band of ester carbonyl group have appearred respectively in the place, fully show grafting particulate PGMA/SiO
2Formation.
SiO
2Particulate and grafting particulate PGMA/SiO
2Stereoscan photograph like Fig. 3, shown in 4, from Fig. 3, see SiO before the grafting
2Particle surface is more coarse, and is uneven; And from Fig. 4, see SiO after the grafting
2It is comparatively smooth that particle surface obviously becomes, and this is filling up due to the coating effect owing to the PS that is grafted on the silica gel surface.
Modified granular MPMS-SiO
2With grafting particulate PGMA/SiO
2The thermal weight loss spectrogram as shown in Figure 5, adopt the general method of inorganic particles graft polymerization objects system thermal weight loss spectral line that Fig. 5 is analyzed: can find out modified granular MPMS-SiO by figure
2With grafting particulate PGMA/SiO
2All near 140 ℃, obviously decompose weightless (being the volatile weight loss of planar water), modified granular finishes in 730 ℃ of decomposition before, and weightlessness 10.73% is corresponding to the bonded amount (coincideing with the iodometric determination result) of coupling agent MPMS; The grafting particulate finishes 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, so have high graft(ing)degree, has realized the efficient graft polymerization of oil-soluble monomer GMA on the silica gel surface.
Description of drawings
Fig. 1 is the chemical reaction process of SY-Monomer G in the grafting process on silica gel surface;
Fig. 2 is three kinds of particulate SiO
2, MPMS-SiO
2And PGMA/SiO
2Infrared spectrogram;
Fig. 3 is SiO
2The ESEM of particulate;
Fig. 4 is grafting particulate PGMA/SiO
2ESEM;
Fig. 5 is modified granular MPMS-SiO
2With grafting particulate PGMA/SiO
2The thermal weight loss spectrogram.
Embodiment
Embodiment 1
A kind of method at the efficient graft polymerization SY-Monomer G of silica particle surface may further comprise the steps:
(1) the activated silica gel surface is sulfhydryl modified: the 2g activated silica gel is joined in the 125mL toluene; And γ-mercaptopropyl trimethoxysilane (MPMS) of adding 2mL; React 11h down at 110 ℃, the product behind the suction filtration is used the toluene repetitive scrubbing, uses washing with alcohol afterwards again; Vacuum-drying promptly makes the modified silica-gel particulate MPMS-SiO that the surface contains sulfydryl
2
(2) graft polymerization of SY-Monomer G: in the four-hole boiling flask that electric mixer, reflux condensing tube and TM are housed, add 1g MPMS-SiO
2, add 70mLN again, dinethylformamide DMF and 7.5mL SY-Monomer G (monomer GMA); Logical nitrogen 30min, with the air in the eliminating system, the temperature with system rises to 55 ℃ then; Add 0.08g initiator B PO, constant temperature also carries out graft polymerization reaction under agitation condition, after reaction finishes; Suction filtration, with the product particulate in Soxhlet extractor with acetone extracting 24h, to remove the polymkeric substance of physical adsorption at microparticle surfaces; Carry out vacuum-drying then, promptly 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.
Embodiment 2
A kind of method at the efficient graft polymerization SY-Monomer G of silica particle surface may further comprise the steps:
(1) activation of silica gel: it is 8% the methanesulfonic aqueous solution that the aerosil particles of getting 30g places 150mL concentration, stir-activating 8h under reflux temperature, the silica gel after the activation with the zero(ppm) water repetitive scrubbing to neutral, suction filtration, vacuum-drying obtains activated silica gel;
(2) the activated silica gel surface is sulfhydryl modified: the 3g activated silica gel is joined in the 125mL toluene; And γ-mercaptopropyl trimethoxysilane (MPMS) of adding 3mL; React 12h down at 115 ℃, the product behind the suction filtration is used the toluene repetitive scrubbing, uses washing with alcohol afterwards again; Vacuum-drying promptly makes the modified silica-gel particulate MPMS-SiO that the surface contains sulfydryl
2
(3) graft polymerization of SY-Monomer G: in the four-hole boiling flask that electric mixer, reflux condensing tube and TM are housed, add 2g MPMS-SiO
2, add 70mLN again, dinethylformamide DMF and 9mL SY-Monomer G (monomer GMA); Logical nitrogen 30min, with the air in the eliminating system, the temperature with system rises to 55 ℃ then; Add 0.09g initiator B PO, constant temperature also carries out graft polymerization reaction under agitation condition, after reaction finishes; Suction filtration, with the product particulate in Soxhlet extractor with acetone extracting 24h, to remove the polymkeric substance of physical adsorption at microparticle surfaces; Carry out vacuum-drying then, promptly obtain grafting particulate PGMA/SiO
2
A kind of method at the efficient graft polymerization SY-Monomer G of silica particle surface may further comprise the steps:
(1) activation of silica gel: it is 5% the methanesulfonic aqueous solution that the aerosil particles of getting 30g places 150mL concentration, stir-activating 10h under reflux temperature, the silica gel after the activation with the zero(ppm) water repetitive scrubbing to neutral, suction filtration, vacuum-drying obtains activated silica gel;
(2) the activated silica gel surface is sulfhydryl modified: the 2.5g activated silica gel is joined in the 125mL toluene; And γ-mercaptopropyl trimethoxysilane (MPMS) of adding 2mL; React 10h down at 113 ℃, the product behind the suction filtration is used the toluene repetitive scrubbing, uses washing with alcohol afterwards again; Vacuum-drying promptly makes the modified silica-gel particulate MPMS-SiO that the surface contains sulfydryl
2
(3) graft polymerization of SY-Monomer G: in the four-hole boiling flask that electric mixer, reflux condensing tube and TM are housed, add 1.5g MPMS-SiO
2, add 70mLN again, dinethylformamide DMF and 8mL SY-Monomer G (monomer GMA); Logical nitrogen 30min, with the air in the eliminating system, the temperature with system rises to 55 ℃ then; Add 0.08g initiator B PO, constant temperature also carries out graft polymerization reaction under agitation condition, after reaction finishes; Suction filtration, with the product particulate in Soxhlet extractor with acetone extracting 24h, to remove the polymkeric substance of physical adsorption at microparticle surfaces; Carry out vacuum-drying then, promptly obtain grafting particulate PGMA/SiO
2
Embodiment 4
A kind of method at the efficient graft polymerization SY-Monomer G of silica particle surface may further comprise the steps:
(1) the activated silica gel surface is sulfhydryl modified: the 2.5g activated silica gel is joined in the 125mL toluene; And γ-mercaptopropyl trimethoxysilane (MPMS) of adding 2mL; React 10h down at 115 ℃, the product behind the suction filtration is used the toluene repetitive scrubbing, uses washing with alcohol afterwards again; Vacuum-drying promptly makes the modified silica-gel particulate MPMS-SiO that the surface contains sulfydryl
2
(2) graft polymerization of SY-Monomer G: in the four-hole boiling flask that electric mixer, reflux condensing tube and TM are housed, add 1.5g MPMS-SiO
2, add 70mLN again, dinethylformamide DMF and 7mL SY-Monomer G (monomer GMA); Logical nitrogen 30min, with the air in the eliminating system, the temperature with system rises to 55 ℃ then; Add 0.08g initiator B PO, constant temperature also carries out graft polymerization reaction under agitation condition, after reaction finishes; Suction filtration, with the product particulate in Soxhlet extractor with acetone extracting 24h, to remove the polymkeric substance of physical adsorption at microparticle surfaces; Carry out vacuum-drying then, promptly obtain grafting particulate PGMA/SiO
2
Claims (1)
1. method at the efficient graft polymerization SY-Monomer G of silica particle surface is characterized in that may further comprise the steps:
(1) the activated silica gel surface is sulfhydryl modified: the 2-3g activated silica gel is joined in the 125mL toluene; And γ-mercaptopropyl trimethoxysilane of adding 2-3mL; React 10-12h down at 110-115 ℃, the product behind the suction filtration is used the toluene repetitive scrubbing, uses washing with alcohol afterwards again; Vacuum-drying promptly makes the modified silica-gel particulate MPMS-SiO that the surface contains sulfydryl
2
(2) graft polymerization of SY-Monomer G: in the four-hole boiling flask that electric mixer, reflux condensing tube and TM are housed, add 1-2g MPMS-SiO
2, add 70mLN again, dinethylformamide DMF and 7-9mL SY-Monomer G, logical nitrogen 30min; With the air in the eliminating system, the temperature with system rises to 55 ℃ then, adds 0.08-0.09g initiator B PO, and constant temperature also carries out graft polymerization reaction under agitation condition; After reaction finishes, suction filtration, with the product particulate in Soxhlet extractor with acetone extracting 24h; To remove the polymkeric substance of physical adsorption at microparticle surfaces, carry out vacuum-drying then, promptly obtain grafting particulate PGMA/SiO
2
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Cited By (8)
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|---|---|---|---|---|
| CN103172804A (en) * | 2012-12-27 | 2013-06-26 | 中北大学 | Preparation method of theophylline molecular surface printing material |
| CN103342787A (en) * | 2013-06-28 | 2013-10-09 | 中北大学 | Preparation method of chromate adsorbing material |
| 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 |
| CN109701503A (en) * | 2018-11-20 | 2019-05-03 | 中北大学 | A kind of pair of anthocyanidin has the preparation method of the functional particles of strong adsorption ability |
| US10695744B2 (en) | 2015-06-05 | 2020-06-30 | W. R. Grace & Co.-Conn. | Adsorbent biprocessing clarification agents and methods of making and using the same |
| US11229896B2 (en) | 2014-01-16 | 2022-01-25 | W.R. Grace & Co.—Conn. | Affinity chromatography media and chromatography devices |
| US11389783B2 (en) | 2014-05-02 | 2022-07-19 | W.R. Grace & Co.-Conn. | Functionalized support material and methods of making and using functionalized support material |
| US11628381B2 (en) | 2012-09-17 | 2023-04-18 | W.R. Grace & Co. Conn. | Chromatography media and devices |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11628381B2 (en) | 2012-09-17 | 2023-04-18 | W.R. Grace & Co. Conn. | Chromatography media and devices |
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| CN103342787A (en) * | 2013-06-28 | 2013-10-09 | 中北大学 | Preparation method of chromate adsorbing material |
| US11229896B2 (en) | 2014-01-16 | 2022-01-25 | W.R. Grace & Co.—Conn. | Affinity chromatography media and chromatography devices |
| US11389783B2 (en) | 2014-05-02 | 2022-07-19 | W.R. Grace & Co.-Conn. | Functionalized support material and methods of making and using functionalized support material |
| US10695744B2 (en) | 2015-06-05 | 2020-06-30 | W. R. Grace & Co.-Conn. | Adsorbent biprocessing clarification agents and methods of making and using the same |
| 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 |
| CN109701503A (en) * | 2018-11-20 | 2019-05-03 | 中北大学 | A kind of pair of anthocyanidin has the preparation method of the functional particles of strong adsorption ability |
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