CN102174141B - Method for preparing glass ionomer cement liquid with low dissolubility and acidity - Google Patents
Method for preparing glass ionomer cement liquid with low dissolubility and acidity Download PDFInfo
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- CN102174141B CN102174141B CN 201110068045 CN201110068045A CN102174141B CN 102174141 B CN102174141 B CN 102174141B CN 201110068045 CN201110068045 CN 201110068045 CN 201110068045 A CN201110068045 A CN 201110068045A CN 102174141 B CN102174141 B CN 102174141B
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- glass ionomer
- deionized water
- glycidyl methacrylate
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Abstract
The invention relates to a method for preparing glass ionomer cement liquid with low dissolubility and acidity, and belongs to the field of dental bonding repairing materials. The method comprises the following steps of: reacting 20 to 60 weight percent of alcohol amine compound and 40 to 80 weight percent of glycidyl methacrylate at the temperature of between 40 and 50 DEG C for 3 to 5 hours under heating and stirring to obtain a glycidyl methacrylate derivative; washing and extracting by using dichloromethane and deionized water; keeping a water phase, performing rotary evaporation, and putting in a dark place at normal temperature for later use; taking a derivative monomer, an acrylic acid monomer, an itaconic acid monomer, an initiator potassium persulfate or ammonium persulfate monomer, and an isopropanol monomer; and reacting 25 to 50 mass percent monomers under the condition that the deionized water is taken as a solvent at the temperature of between 60 and 120 DEG C for 5 to 15 hours under the protection of nitrogen and stirring, and purifying to obtain the glass ionomer cement liquid with the low dissolubility and acidity. In the method, conditions in the operation process are mild, and easy to control.
Description
Technical field
The present invention relates to liquor of the low acid glass ionomer of a kind of novel low-solubility and preparation method thereof.
Background technology
Glass ionomer (glass ionomer cement, GIC) is a kind of Novel toothed with broad prospects for development section bonding repair materials, comes out so far from 20 century 70s, has demonstrated very large potentiality in medical.It integrates the advantage of silicious dental cement, zinc phosphate cement and Research of Zinc Polycarboxylic Cement, and is multiplex in V-type hole filling, bonding, hole base lining, the treatment of dentin hypersensitiveness and the sealing of nest ditch etc. in clinical oral.Compare with other tooth dental repair material, glass ionomer have and tissue of tooth between the advantage such as good, the long-term Fluoride release preventing decayed tooth of chemical bonding, low, the attractive in appearance performance of thermal expansivity be good.
Glass ionomer has very important advantage as the tooth dental repair material.But for a long time, because physical strength is lower, wear no resistance and solidifying early stage moisture sensitivity, be not suitable for clinically bearing the place of larger snap-in force, during for example as the backteeth compaction material, ultimate compression strength deficiency and aesthetic property, acid resistance are relatively poor.The glass ionomer liquor is generally by the poly-acid copolymer of vinylformic acid and methylene-succinic acid or toxilic acid; Polymerisable monomer; Water forms.In recent years, research is both at home and abroad introduced the third functional monomer by grafting on multipolymer, copolymerization, as: modified amino acid, NVP, amphiphilic monomer obtain having the more modified glass ionomer cement liquor of high mechanical strength, abrasive wear resistance, cohesive strength or biocompatibility.
The existing glass ionomer that is widely used has the Fuji II of Japanese GC company, loose wind, and the 3M of the U.S. etc., wherein the range of application of Fuji II is the most extensive.Its liquor partly is the multipolymer of vinylformic acid and methylene-succinic acid, water, the compositions such as polymerisable monomer affect biocompatibility thereby its shortcoming is that easy embrittlement, water dissolution rate are large, compressive strength is not high enough, long-time placement can slowly release acid monomer in the oral cavity.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of glass ionomer liquor.The method operating process mild condition, the novel liquor that is easy to control, prepare have preferably water resistant solvability, the low acid and compressive strength suitable with Fuji II.
Technical measures: adopt vinylformic acid and methylene-succinic acid and a small amount of new synthetic alkanolamine derivative monomer through the glycidyl methacrylate modification, deionized water do carry out under solvent, the thermal initiator initiation free-radical polymerized.Wherein the hydroxyl of hydramine can increase the wetting ability of cement, and in the weak acid environment of oral cavity, can not discharge acid small molecules, and the glycidyl methacrylate part can increase the chain length between the carboxyl unit, intramolecular hydrogen bond action weakens, thereby by so that calcium ion, aluminum ion that more effectively carboxyl participates in glass powder be combined, increase physical strength and the toughness of material, reduce fragility.
The present invention adopts the preparation method of the low acid glass ionomer liquor of a kind of low-solubility, it is characterized in that being prepared from by following proportioning raw materials and process:
(1) by weight percentage be the alcamine compound of 20%-60%, weight percentage is the glycidyl methacrylate derivative that 40%-80% glycidyl methacrylate (GMA) was prepared under 40-50 ℃ of heating in stirring reaction 3-5 hour; Wash, extract with methylene dichloride and deionized water; Keep water, revolve steaming, be placed on the normal temperature dark place for subsequent use;
(2) get the glycidyl methacrylate derivatives monomer that weight percentage is 5%-25%, weight percentage is the Acrylic Acid Monomer (AA) of 50%-55%, weight percentage is the methylene-succinic acid monomer (IA) of 10%-45%, weight percentage is initiator potassium persulfate or the ammonium persulphate monomer of 0.5%-2.5%, the Virahol monomer of weight percentage 0-5%; Above-mentioned monomer is reacted under deionized water is made solvent, and monomer mass percentage ratio concentration is between 25%-50%, and under 60 ℃ of-120 ℃ of nitrogen protections stirring reaction 5-15 hour, purifying obtained the low acid glass ionomer liquor of low-solubility.
Alcamine compound described in the preferred steps (1) has following formula
R in the formula
1Be H or pure alkyl, R
2Be H or pure alkyl or aralkyl.
Compared with prior art, liquor of the present invention has the following advantages:
1, larger easy embrittlement and the dissolving of small molecules in water that has reduced the cement material of molecular weight of synthetic liquor product overflowed, and reduced the solvability of material
2, introduce hydroxyl in the product structure, increased the wetting ability of material, so that more water molecules and carboxyl are reacted, improved biocompatibility and improved to a certain extent mechanical property.
3, amino introducing in the product structure, acid micromolecular the overflowing of having reduced material reduced the plup stimulus of material.
The evaluation and test mode that the glass ionomer liquor of the present invention's preparation adopts is that ultimate compression strength, pH value change and the suction dissolution rate, and evaluating method is as follows:
(1) compressive strength
Synthetic PAA-IA-GMA derivative is dissolved in is made into different concns solution in the deionized water, as the liquor component among the GIC.Get an amount of pulvis and liquor, transferring on the paper with toolsetting mediation about 1 minute, the glass ionomer that fully is in harmonious proportion is poured into rapidly in the mould that tetrafluoroethylene (PTFE) makes, and the mould that wherein is used for ultimate compression strength (CS) test is that 10mm is high, the 10mm diameter.Both mold ends covers sheet glass, pours into behind the cement gently to press, and removes bubble wherein.After solidifying 30 minutes, the sample piece is taken out from mould, put into 37 degree water-baths and continue test after 24 hours.During test, sample is lain on the Stage microscope, with the speed loading of 1mm/min, until sample breakage, record ultimate load value.Every assembly is than making 5 samples.
(2) the pH value changes
Method with reference to (1) prepares the sample piece, and mould is that 2mm is thick, the 10mm diameter.Sample is put into respectively pH=7.12 buffered soln place the changing conditions of measuring afterwards the pH value in 7 days, utilize the standard pH determination of electrode.Each result repeats 3 times, averages.
(3) suction dissolution rate (Wsl)
Method with reference to (1) prepares the sample piece, and the sample piece is placed for some time in vacuum drying oven, obtains constant weight m1.
Then, leave standstill in the buffered soln of sample piece submergence pH=7.12, under 37 degree constant temperature, leave standstill and took out afterwards in 7 days.The sample piece is put into vacuum drying oven again until constant weight m3 after taking out.The volume of sample piece is V, and each value replicate measurement three times is averaged.The suction dissolution rate is Wsl.
Embodiment
Synthesizing of alcamines GMA derivative:
Embodiment 1: the 14g thanomin is dropped in the there-necked flask stir, be heated to 30 ℃, drip 56g GMA, mechanical stirring makes reaction carry out 40 ℃ of gentlenesses.Reaction was carried out after 3 hours, and solution becomes clarification again, finished reaction.Product is washed, extracts with methylene dichloride and deionized water.Keep water, revolve steaming, obtain product GMA ethanolamine derivant.Be connected with ammonium persulphate and the 97.5g deionized water that adds 0.234g in the four-hole boiling flask of nitrogen, 17.2g the mixture of AA, 7.8g IA, 7.47g GMA ethanolamine derivant and 1.95g Virahol is dropwise added in the four-hole boiling flask, reaction was carried out 13 hours in the mechanical stirring under 80 ℃ of conditions.Stop after reaction finishes stirring, obtain end product.The 2g product is added the 2g deionized water be made into 50% aqueous solution, mix by 2.7: 1 weight ratios of powder liquor ratio with Fuji II glass powder.Measure compressive strength, pH value according to above-mentioned evaluating method, and dissolution rate, the result is respectively 113Mpa, 7.30,60.77 μ g/mm
3
Embodiment 2: the 30g diethanolamine is dropped in the there-necked flask stir, be heated to 30 ℃, drip 40g GMA, mechanical stirring makes reaction carry out 45 ℃ of gentlenesses.Reaction was carried out after 4 hours, and solution becomes clarification again, finished reaction.Product is washed, extracts with methylene dichloride and deionized water.Keep water, revolve steaming, obtain product GMA ethanolamine derivative.Be connected with Potassium Persulphate and the 82.5g deionized water that adds 0.165g in the four-hole boiling flask of nitrogen, 15.5g AA, 5.5g IA, 6.875GMA ethanolamine derivative mixture are dropwise added in the four-hole boiling flask.Reaction was carried out 15 hours in the mechanical stirring under 60 degree conditions.Stop after reaction finishes stirring, obtain end product.The 2g product is added the 2g deionized water be made into 50% aqueous solution, mix by 2.7: 1 weight ratios of powder liquor ratio with Fuji II glass powder.Measure compressive strength, pH value according to above-mentioned evaluation and test method, and dissolution rate, the result is respectively 80Mpa, 7.21,30.12 μ g/mm
3
Embodiment 3: the 40g dipropanolamine is dropped in the there-necked flask stir, be heated to 30 ℃, drip 30g GMA, mechanical stirring makes reaction carry out 47 ℃ of gentlenesses.Reaction was carried out after 5 hours, and solution becomes clarification again, finished reaction.Product is washed, extracts with methylene dichloride and deionized water.Keep water, revolve steaming, obtain product GMA dipropanolamine derivative.Be connected with Potassium Persulphate and the 90g deionized water that adds 0.825g in the four-hole boiling flask of nitrogen, the mixture of 13.75g AA, 12.37g IA, 1.375g GMA dipropanolamine derivative is dropwise added in the four-hole boiling flask.The Virahol that adds 1.65g, reaction was carried out 5 hours in the mechanical stirring under 120 degree conditions.Stop after reaction finishes stirring, obtain end product.The 2g product is added the 2g deionized water be made into 50% aqueous solution, mix by 2.7: 1 weight ratios of powder liquor ratio with Fuji II glass powder.Measure compressive strength, pH value according to above-mentioned evaluation and test method, and dissolution rate, the result is respectively 95Mpa, 7.28,42.04 μ g/mm
3
Embodiment 4: 26g two butanolamines are dropped in the there-necked flask stir, be heated to 30 ℃, drip 35g GMA, mechanical stirring makes reaction carry out 50 ℃ of gentlenesses.Reaction was carried out after 4 hours, and solution becomes clarification again, finished reaction.Product is washed, extracts with methylene dichloride and deionized water.Keep water, revolve steaming, obtain product GMA two butanolamine derivatives.Be connected with ammonium persulphate and the 100g deionized water that adds 0.585g in the four-hole boiling flask of nitrogen, 15.9g AA, 6.6g IA, 7.5g GMA two butanolamine derivative mixtures are dropwise added in the four-hole boiling flask, reaction was carried out 10 hours in the mechanical stirring under 86 degree conditions.Stop after reaction finishes stirring, obtain end product.The 2g product is added the 2g deionized water be made into 50% aqueous solution, mix by 2.7: 1 weight ratios of powder liquor ratio with Fuji II glass powder.Measure compressive strength, pH value according to above-mentioned evaluating method, and dissolution rate, the result is respectively 104Mpa, 7.32,56.90 μ g/mm
3
Comparative example: the pulvis of the Fuji II cement of GC company and liquor mix with 2.7: 1 weight ratio, measure its ultimate compression strength, pH value and suction dissolution rate with reference to evaluating method, and the result is respectively 89Mpa, 6.75,57.11 μ g/mm
3
Claims (2)
1. the preparation method of the low acid glass ionomer liquor of a low-solubility is characterized in that being prepared from by following proportioning raw materials and process:
(1) by weight percentage be 20%-60% alcamine compound, weight percentage is 40%-80% glycidyl methacrylate glycidyl methacrylate derivative that stirring reaction was prepared from 3-5 hours under 40-50 ° of C heating; Wash, extract with methylene dichloride and deionized water; Keep water, revolve steaming, be placed on the normal temperature dark place for subsequent use;
(2) getting weight percentage is 5%-25% glycidyl methacrylate derivatives monomer, weight percentage is 50%-55% Acrylic Acid Monomer, weight percentage is 10%-45% methylene-succinic acid monomer, weight percentage is 0.5%-2.5% initiator potassium persulfate or ammonium persulphate monomer, the Virahol monomer of weight percentage 0-5%; Above-mentioned monomer under making solvent, deionized water is reacted; monomer mass percentage ratio concentration is between 25%-50%; stirring reaction is 5-15 hours under 60 ° of C-120 ° C nitrogen protection; purification obtains the low acid glass ionomer liquor of low-solubility, and the weight percentage sum of above-mentioned all components is 100%.
2. preparation method according to claim 1 is characterized in that the alcamine compound described in the step (1) has following formula
R in the formula
1Be H or pure alkyl, R
2Be H or pure alkyl or aralkyl.
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| CN103286898A (en) * | 2013-06-27 | 2013-09-11 | 东南大学 | Preparation method of dental cement material bar-shaped sample as well as mold thereof |
| CN108245433A (en) * | 2017-12-21 | 2018-07-06 | 中国科学院兰州化学物理研究所 | A kind of novel mouth section glass ionomer/fluorinated graphene composite material |
| CN113367995B (en) * | 2021-05-08 | 2023-03-21 | 华南理工大学 | Dental glass ion cement composite |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3245939A (en) * | 1962-11-30 | 1966-04-12 | Wacker Chemie Gmbh | Process for the preparation of cationactive polymer dispersions |
| CN1679466A (en) * | 2005-02-01 | 2005-10-12 | 中国科学院长春应用化学研究所 | Liquid of light curing glass ion cement and preparation thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3245939A (en) * | 1962-11-30 | 1966-04-12 | Wacker Chemie Gmbh | Process for the preparation of cationactive polymer dispersions |
| CN1679466A (en) * | 2005-02-01 | 2005-10-12 | 中国科学院长春应用化学研究所 | Liquid of light curing glass ion cement and preparation thereof |
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