CN102516102B - Preparation method of 3-(N-glucidol-N-methyl)-2-hydroxy-propyl methacrylate (GMHP) monomer - Google Patents
Preparation method of 3-(N-glucidol-N-methyl)-2-hydroxy-propyl methacrylate (GMHP) monomer Download PDFInfo
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- CN102516102B CN102516102B CN201110338887.1A CN201110338887A CN102516102B CN 102516102 B CN102516102 B CN 102516102B CN 201110338887 A CN201110338887 A CN 201110338887A CN 102516102 B CN102516102 B CN 102516102B
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Abstract
The invention discloses a preparation method of 3-(N-glucidol-N-methyl)-2-hydroxy-propyl methacrylate (GMHP). The method comprises the following steps of: (1) dropwise adding glucose methylamine into a solvent at the temperature of 20-60 DEG C for dissolving and reacting with a methacrylic acid glycidyl ester monomer containing a polymerization inhibitor, and stopping reacting 1-8 hours after dropwise adding; and (2) removing the solvent from a reaction product in a solvent removing process to obtain GMHP product. Compared with the prior art, the preparation method of the GMHP has the advantages of easiness, convenience and practicability for operating, mild preparation conditions, no use of high-risk solvents such as ether and the like, high product yield (the product yield is 91-95 percent in a process flow, and is reported as 84 percent), and the like.
Description
Technical field
The invention belongs to function monomer preparation and Application Areas, be specifically related to a kind of preparation method of glucose methylamine function acrylate monomer.
Technical background
Glucose methylamine function glycidyl methacrylate monomer GMHP (3-(N-glucidol-N-methyl)-2-hydroxy-propyl methacrylate, Chinese named is 3-(N-glucosyl group-N-methyl)-2-HPMA, and english abbreviation is GMHP) be Niyazi
what equal to prepare for 2000 a kind ofly has a very function acrylate monomer of high polymerization activity, in its molecular structure, have acrylate structural and glucose methylamine functional group, its acrylate structural can make it be polymerized to macromolecular material by polyreaction simultaneously; Its glucose methylamine functional group has splendid hydrophilicity, and can carry out selectable complex reaction to elements such as boron, arsenic, antimony, germanium, its tertiary amine structure makes this monomer can be by certain mode for the preparation of the polymer electrolyte with property in addition.Niyazi
deng prepared a kind of boron adsorption gel material of excellent property by the cross-linking polymerization of GMHP monomer, (its saturated boron loading capacity is in 2.12-2.18mmol/g left and right greatly for the saturated boron loading capacity that has of this gelatinous material, reached 85% of the theoretical adsorptive capacity of such boron sorbing material, for the maximum of all boron sorbing materials of bibliographical information at that time) and rate of adsorption fast (this material of 0.50g can be reduced to below 2ppm at the boron content that can make 80ml contain in the boric acid aqueous solution of 30.7ppm boron in 15min) and recycle the features such as performance excellence (resin adsorbing still can reach original adsorptive power after regenerative process).In US Patent No. 2010/0178358A1, related to and a kind of GMHP monomer is joined and in the materials such as timber, carries out in-situ polymerization, then added various auxiliary agents to improve the method that the environmental resistance of the materials such as timber can (as anti-insect performance, anti-fungal property, moisture resistant performance, flame retardant properties etc.).The method by material soakings such as timber in being dissolved with the solvent of GMHP monomer, add initiator to cause the home position polymerization reaction of GMHP monomer, add afterwards various auxiliary agents (as boric acid etc.) that itself and glucose methylamine functional group are combined by chemical bond, reach the object that improves the environment tolerances of material such as timber own.In the international macromolecular complex thing of the 14 the IUPAC discussion of holding for 2011, Dr.Julio Sanchez has done the synthetic of water miscible GMHP polymkeric substance and in the aqueous solution, has removed the report of application aspect arsenic element.In view of such functional polymer actual application value so widely, the preparation technology of exploitation glucose methylamine functional acrylic esters monomers GMHP has great basic meaning and economic worth.
The synthetic method of the GMHP function monomer of bibliographical information only has a kind of at present: take N-Methyl pyrrolidone as solvent, make the glycidyl methacrylate of equimolar amount react 4-7h under heating at 60 ℃-70 ℃ with glucose methylamine, obtain the N-Methyl pyrrolidone solution of GMHP monomer; React complete and first add a large amount of ether to make GMHP product be deposited to the bottom of system, remove supernatant liquid, lower sediment thing adds methyl alcohol makes its dissolving; Again add a large amount of ethyl acetate precipitation product, remove supernatant liquid, finally throw out is revolved to steam and remove ethyl acetate solvent and obtain GMHP product.The method has following shortcoming:
1) the method temperature of reaction is higher, and the reaction times is longer, causes glycidyl methacrylate raw material monomer and GMHP function monomer product polymerization reaction take place, affects quality product;
2) the method post-processing step is loaded down with trivial details, get up trouble but also affect the ultimate yield of product of actually operating not only, and used the comparatively dangerous solvents such as ether;
3) methanol solvate adding in the method last handling process heating revolve in the process of steaming can and function monomer product generation transesterification reaction generation methyl methacrylate;
Summary of the invention
The object of the invention is the portioned product polymerization in reaction process existing in current glucose methylamine function acrylate monomer GMHP technology of preparing, product post-processing step is loaded down with trivial details and use the dangerous solvents such as ether, the deficiency of using alcoholic solvent to cause quality product to decline, the preparation method of a kind of new glucose methylamine function acrylate monomer GMHP is provided, the method adopts lower temperature of reaction, the reaction solvent that boiling point is lower, simple and direct and rational product post-processing step, there is reaction conditions gentleness, operation is simple, good product quality, the advantage that yield is high.
Technical scheme of the present invention is:
A preparation method of glucose methylamine function acrylate monomer GMHP, the structural formula of this monomer is as follows:
Preparation process is:
1) glucose methylamine is joined in solvent and dissolved, in 20-60 ℃ of temperature range, drip the glycidyl methacrylate monomer reaction contain stopper, react complete after dropwising 1-8h;
Wherein, glycidyl methacrylate monomer and glucose methylamine equimolar amount, solvent load is 300-1000ml solvent/mol glycidyl methacrylate monomer; Stopper add-on is the 500-1000ppm of glycidyl methacrylate monomer and glucose methylamine total mass;
2) react complete product through solvent removal process desolvation, obtain glucose methylamine function acrylate monomer GMHP product.
Described solvent is DMF, dimethyl sulfoxide (DMSO), water/acetone, water/tetrahydrofuran (THF) or water/Isosorbide-5-Nitrae-dioxane.
Described stopper is p methoxy phenol or Resorcinol.
Described solvent removal process, when being N for reaction solvent, during the reaction system of dinethylformamide or dimethyl sulfoxide (DMSO), first vacuum rotary steam is removed most of solvent, vacuum rotary steam temperature range 50-65 ℃, vacuum tightness 0.001MPa, add again the residual high boiling solvent in inert (ethyl acetate or tetrahydrofuran (THF)) cleaning product, again the product vacuum rotary steam after washing is removed to low boiling point solvent, vacuum rotary steam temperature range 30-50 ℃, vacuum tightness 0.001MPa; When being the reaction system of water/acetone, water/tetrahydrofuran (THF) or water/Isosorbide-5-Nitrae-dioxane for reaction solvent, directly vacuum rotary steam removes the solvent in product, vacuum rotary steam temperature range 30-50 ℃, vacuum tightness 0.001MPa.
The preparation method of glucose methylamine function acrylate monomer of the present invention can prepare the GMHP monomer that possesses bibliographical information performance completely, compare with the method for bibliographical information, there is easy to operation, the advantage such as preparation condition is gentle, do not use the solvent of the high-risk such as ether, product yield high (this operational path product yield 91-95%, bibliographical information value is 84%).
Accompanying drawing explanation
Fig. 1. the hydrogen nuclear magnetic resonance spectrogram of the GMHP monomer product of the embodiment of the present invention 1 preparation;
Fig. 2. the infrared spectra light figure of the GMHP monomer product of the embodiment of the present invention 1 preparation.
Embodiment
In being housed, the 250ml four-hole boiling flask of mechanical stirring, reflux condensing tube, dropping funnel, thermometer adds 9.75g (0.05mol) glucose methylamine, and add 30mlN, dinethylformamide, be heated to 60 ℃ and make its dissolving, and the glycidyl methacrylate 7.10g (0.05mol) that slowly dropping contains 0.01g stopper p methoxy phenol at this temperature, time for adding 30min, dropwises after 1h the glycidyl methacrylate in high performance liquid chromatography detection system and disappears and think that reaction is complete.Product is revolved rapidly at 50 ℃ to steaming (vacuum tightness 0.001MPa) except desolventizing N, dinethylformamide, treat N, dinethylformamide adds 50ml ethyl acetate cleaning product after no longer steaming, pour out and residuum is revolved rapidly at 40 ℃ to steaming (vacuum tightness 0.001MPa) after ethyl acetate washings and remove ethyl acetate, obtain yellow transparent solid dope 15.61g, yield 92%.
Description of drawings 1, be in the hydrogen nuclear magnetic resonance spectrogram of product, each peak shape and peak position of organizing hydrogen atom is correct, signal integration area numerical value is in the reasonable scope: it is obvious that chemical shift δ=6.1 (i) and δ=5.6 (j) locates olefinic double bonds hydrogen atom signal, and the integral area ratio of the methyl hydrogen atom (b) of the two and metacrylic acid ester structure is 1.00: 1.00: 3.01 (theoretical value 1: 1: 3), illustrates that acrylate structural does not have polymerization reaction take place substantially; In addition, each organizes the integral area ratio at peak, i: j: (g+f+h): (c+d+e): b: a=1.00: 1.00: 14.13: 7.08: with theoretical value (1: 1: 14: 7: 3: 1) substantially conform at 3.01: 0.98, the glycidyl methacrylate of equimolar amount and the GMHP monomer product that glucose methylamine generation ring-opening reaction has generated desired structure are described.Description of drawings 2,, in the infrared spectrogram of product, each peak-to-peak shape and peak position are correct, and each characteristic peak of GMHP product structure is (as 3600cm
-1-3200cm
-1hydroxyl stretching vibration peak, 3000cm
-1-2800cm
-1methyl and methylene radical C-H stretching vibration, 1716cm
-1the ester carbonyl group C=O of place stretching vibration peak, 1636cm
-1carbon-carbon double bond C=C stretching vibration peak) obviously.Fig. 1 and Fig. 2 prove the target product that can obtain having required chemical structure by this operational path.
In being housed, the 250ml four-hole boiling flask of mechanical stirring, reflux condensing tube, dropping funnel, thermometer adds 9.75g (0.05mol) glucose methylamine, and add 15ml dimethyl sulfoxide (DMSO), be heated to 50 ℃ and make its dissolving, and the glycidyl methacrylate 7.10g (0.05mol) that slowly dropping contains 0.01g hydroquinone of polymerization retarder at this temperature, time for adding 30min, dropwises after 2h the glycidyl methacrylate in high performance liquid chromatography detection system and disappears and think that reaction is complete.Product is revolved rapidly at 65 ℃ to steaming (vacuum tightness 0.001MPa) except desolventizing dimethyl sulfoxide (DMSO), after no longer steaming, dimethyl sulfoxide (DMSO) adds 50ml tetrahydrofuran (THF) cleaning product, pour out residuum to be revolved rapidly at 40 ℃ steam after tetrahydrofuran (THF) washings again and remove tetrahydrofuran (THF), obtain yellow transparent solid dope 15.34g, yield 91%.
In being housed, the 250ml four-hole boiling flask of mechanical stirring, reflux condensing tube, dropping funnel, thermometer adds 9.75g (0.05mol) glucose methylamine, add 30ml water/acetone mixed solvent (water/acetone volume ratio is 1: 2) to make its dissolving, the lower glycidyl methacrylate 7.10g (0.05mol) dripping containing 0.01g stopper p methoxy phenol of normal temperature (20 ℃-30 ℃), time for adding 30min, the glycidyl methacrylate after 6h in high performance liquid chromatography detection system disappears and thinks that reaction is complete.Product is revolved rapidly at 30-40 ℃ to steaming (vacuum tightness 0.001MPa) except desolventizing, obtain water white transparency solid dope 16.03g, yield 95%.
In being housed, the 250ml four-hole boiling flask of mechanical stirring, reflux condensing tube, dropping funnel, thermometer adds 9.75g (0.05mol) glucose methylamine, add 40ml water/tetrahydrofuran (THF) mixed solvent (water/tetrahydrofuran (THF) volume ratio is 1: 1) to make its dissolving, the lower glycidyl methacrylate 7.10g (0.05mol) dripping containing 0.01g hydroquinone of polymerization retarder of normal temperature (20 ℃-30 ℃), time for adding 1h, the glycidyl methacrylate after 8h in high performance liquid chromatography detection system disappears and thinks that reaction is complete.Product is revolved rapidly at 30-40 ℃ to steaming (vacuum tightness 0.001MPa) except desolventizing, obtain water white transparency solid dope 16.10g, yield 95%.
In being housed, the 250ml four-hole boiling flask of mechanical stirring, reflux condensing tube, dropping funnel, thermometer adds 9.75g (0.05mol) glucose methylamine, add 50ml water/1,4-dioxane mixed solvent (water/1,4-dioxane volume ratio is 1: 1) make its dissolving, the lower glycidyl methacrylate 7.10g (0.05mol) dripping containing 0.01g hydroquinone of polymerization retarder of normal temperature (20 ℃-30 ℃), time for adding 1h, the glycidyl methacrylate after 8h in high performance liquid chromatography detection system disappears and thinks that reaction is complete.Product is revolved rapidly at 40-50 ℃ to steaming (vacuum tightness 0.001MPa) except desolventizing, obtain water white transparency solid dope 16.05g, yield 95%.
In sum, operational path described in this patent can be prepared the GMHP monomer product with required chemical structure, and compare with document route, advantages such as (this operational path product yield 91-95%, bibliographical information value is 84%) that this operational path has is easy to operation, preparation condition is gentle, do not use solvent, good product quality, the yield of the high-risk such as ether high.
Claims (2)
1. a preparation method for glucose methylamine function acrylate monomer, this monomer is 3-(N-glucosyl group-N-methyl)-2-HPMA, its structural formula is as follows:
It is characterized by step as follows:
1) glucose methylamine is joined in solvent and dissolved, in 20-60 ℃ of temperature range, drip the glycidyl methacrylate monomer reaction contain stopper, react complete after dropwising 1-8h;
Wherein, glycidyl methacrylate monomer and glucose methylamine equimolar amount, solvent load is 300-1000ml solvent/mol glycidyl methacrylate monomer; Stopper add-on is the 500-1000ppm of glycidyl methacrylate monomer and glucose methylamine total mass;
2) react complete product through solvent removal process desolvation, obtain glucose methylamine function acrylate monomer 3-(N-glucosyl group-N-methyl)-2-HPMA;
Described solvent is DMF, dimethyl sulfoxide (DMSO), water/acetone, water/tetrahydrofuran (THF) or water/Isosorbide-5-Nitrae-dioxane;
Described stopper is p methoxy phenol or Resorcinol.
2. the preparation method of glucose methylamine function acrylate monomer as claimed in claim 1, it is characterized by described solvent removal process, when being N for reaction solvent, during the reaction system of dinethylformamide or dimethyl sulfoxide (DMSO), first vacuum rotary steam is removed most of solvent, vacuum rotary steam temperature range 50-65 ℃, vacuum tightness 0.001MPa, add again the residual high boiling solvent in inert cleaning product, again the product vacuum rotary steam after washing is removed to low boiling point solvent, vacuum rotary steam temperature range 30-50 ℃, vacuum tightness 0.001MPa; When being the reaction system of water/acetone, water/tetrahydrofuran (THF) or water/Isosorbide-5-Nitrae-dioxane for reaction solvent, directly vacuum rotary steam removes the solvent in product, vacuum rotary steam temperature range 30-50 ℃, vacuum tightness 0.001Mpa;
Described inert is ethyl acetate or tetrahydrofuran (THF).
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