CN103965384A - Preparation method of polymethyl methacrylate - Google Patents
Preparation method of polymethyl methacrylate Download PDFInfo
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- CN103965384A CN103965384A CN201410208532.4A CN201410208532A CN103965384A CN 103965384 A CN103965384 A CN 103965384A CN 201410208532 A CN201410208532 A CN 201410208532A CN 103965384 A CN103965384 A CN 103965384A
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- polymethylmethacrylate
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- polymethyl methacrylate
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Abstract
The invention relates to a preparation method of polymethyl methacrylate. The preparation method is as follows: adding a catalyst and refined methyl methacrylate into diphenylsulfoxide ionic compound liquor; controlling a temperature to 0 DEG C-50 DEG C in the presence of an anhydrous organic solvent, polymerizing and ending polymerization reaction; then, adding a precipitator into the liquor to separate out polymethyl methacrylate. The polymethyl methacrylate prepared by the method disclosed by the invention is white solid, and the method is beneficial to processing follow-up products of the polymethyl methacrylate; number-average molecular weight of the prepared polymethyl methacrylate is greater than 5000, and molecular weight dispersion index of the prepared polymethyl methacrylate is smaller than 2.0; and a used initiator is simple to prepare, gentle in polymerization condition and high in polymerization product yield.
Description
Technical field
The present invention relates to a kind of preparation method of polymethylmethacrylate.
Background technology
The density of polymethylmethacrylate (PMMA) is low, physical strength is higher, fusing point is lower, the performance of the more high excellence of transmittance, makes it become a kind of important polymkeric substance.Also many to the research of its polymerization process, except the polymethylmethacrylate that the method for traditional radical polymerization is produced, living polymer polymerization process ' group transfer polymerization ' can synthesize poly methyl methacrylate polymer.Compared with traditional free radical polymerisation process, the molecular weight distribution that this polymerization process obtains is narrow, and molecular size range is controlled, and molecular structure can design.The feature of this polymerization process is that (1) polymeric reaction temperature is low.(2) catalyst levels is few.(3) molecular weight is large, narrow molecular weight distribution.(4) transformation efficiency of monomer and initiator is higher.
US Patent No. P4417034 provides taking dimethyl ketene methyl trimethoxy base siloxy acetal as initiator, to contain F
-, HF
2 -, CN
-deng compound or suitable Lewis acid be catalyzer, carried out the group transfer polymerization method of methacrylate, CALCIUM ACRYLATE.
But the shortcoming of the polymerization process of this methacrylate is: polymeric reaction condition is harsher, need under the condition of anhydrous, anaerobic, operate.Initiator preparation is more complicated.
Summary of the invention
The preparation method who the object of the invention is to propose a kind of polymethylmethacrylate, its preparation method is simple, and raw material is easy to get, and reaction conditions gentleness.
The present invention solves the problems of the technologies described above adopted technical scheme: the preparation method of polymethylmethacrylate, it is characterized in that adding catalyzer and refining methyl methacrylate in thionyl benzene ionic compound solution, under anhydrous organic solvent exists, controlling temperature is 0 DEG C～50 DEG C, through polymerization, termination polyreaction, then in solution, add precipitation agent to isolate polymethylmethacrylate.
Press such scheme, the preparation method of described thionyl benzene ionic compound, include following steps: in reaction vessel, add successively tetrahydrofuran (THF), thionyl benzene and boron trifluoride and epoxy compounds, under normal temperature, stir 10～30 minutes, obtain thionyl benzene ionic compound solution.
Press such scheme, described epoxy compounds is any one in oxyethane, propylene oxide, butylene oxide ring, epoxy chloropropane, epoxy styrene, epoxy iso-butylene, oxirane ring hexene, single butadiene monoxide and bis-epoxy butylene.
Press such scheme, described polymethylmethacrylate, has the general structure that formula I represents:
Wherein, in formula, n is greater than 50 integer, and R is hydrogen, methyl, ethyl, chloromethyl, phenyl or sec.-propyl.
Press such scheme, described catalyzer is the mixture of boron trifluoride and aluminum chloride.
Press such scheme, described anhydrous organic solvent is process purified tetrahydrofuran.
Press such scheme, the temperature of described polyreaction is preferably 20 DEG C～35 DEG C.
Press such scheme, the time of described polyreaction is 65～120 hours.
Press such scheme, the churning time of described termination polyreaction is 20～50 minutes, and the temperature of termination reaction is carried out at 20 DEG C～50 DEG C.
Press such scheme, the terminator of described termination polyreaction is KOH, NaOH, Na
2cO
3or NaHCO
3water or alcoholic solution.
Reaction equation involved in the present invention is:
Compared with the prior art, the technique effect that the present invention has reached: the polymethylmethacrylate of preparing by method of the present invention is white solid, be conducive to the processing of its subsequent product, the number-average molecular weight of prepared polymethylmethacrylate is greater than 5000, molecular weight dispersion index is less than 2.0, the initiator preparation using is simple, polymerizing condition gentleness, and polymerisate productive rate is high.
Embodiment
For a better understanding of the present invention, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
Embodiment 1:
In the there-necked flask that stirrer is housed, add successively the refined tetrahydrofuran (THF) of 20ml, 0.1g thionyl benzene, 0.1g epoxy chloropropane and 0.5ml1M BF
3solution, stirs after 25 minutes under normal temperature, then adds 0.5ml1M BF
3solution, by 0.13gAlCl
3the solution that is dissolved in 5.15g methyl methacrylate joins in there-necked flask, 30 DEG C of keeping system temperature, reacted after 72 hours, added 20ml acetone, the aqueous solution that under agitation to drip massfraction that 2ml contains NaOH be 10% stirs termination reaction after 50 minutes at 20 DEG C.In the time of system cool to room temperature, add 50ml methanol extraction polymkeric substance.Then polymkeric substance separates.Vacuum-drying at 40 DEG C.Resulting polymers productive rate is 93%, to use polystyrene as standard specimen, in gel permeation chromatography (GPC) test that tetrahydrofuran (THF) (THF) is moving phase, obtain polymethylmethacrylate, number-average molecular weight is 49415, and molecular weight dispersion index is 1.56.
Embodiment 2:
In the there-necked flask that stirrer is housed, add successively the refined tetrahydrofuran (THF) of 15ml, 0.1g thionyl benzene, 0.1g propylene oxide and 0.5ml1M BF
3solution, stirs after 25 minutes under normal temperature, then adds 0.5ml1M BF
3solution, by 0.11gAlCl
3the solution that is dissolved in 5.06g methyl methacrylate joins in there-necked flask, and 30 DEG C of keeping system temperature were reacted after 96 hours, added 20ml acetone, under agitation dripped 2ml and contained NaHCO
3the massfraction aqueous solution that is 10%, at 50 DEG C, stir termination reaction after 30 minutes.In the time of system cool to room temperature, add 50ml methanol extraction polymkeric substance.Then polymkeric substance separates.Vacuum-drying at 40 DEG C.Resulting polymers productive rate is 62.4%, to use polystyrene as standard specimen, in gel permeation chromatography (GPC) test that tetrahydrofuran (THF) (THF) is moving phase, obtain polymethylmethacrylate, number-average molecular weight is 67741, and molecular weight dispersion index is 1.72.
Embodiment 3:
In the there-necked flask that stirrer is housed, add successively the refined tetrahydrofuran (THF) of 20ml, 0.1g thionyl benzene, 0.15g epoxy styrene and 0.5ml1M BF
3solution, stirs after 25 minutes, by 0.26gAlCl under normal temperature
3the solution that is dissolved in 5.16g methyl methacrylate joins in there-necked flask.30 DEG C of keeping system temperature, reacted after 96 hours, added 20ml acetone, and the aqueous solution that under agitation to drip massfraction that 2ml contains KOH be 10% stirs termination reaction after 60 minutes at 20 DEG C.In the time of system cool to room temperature, add 50ml methanol extraction polymkeric substance.Then polymkeric substance separates.Vacuum-drying at 40 DEG C.Resulting polymers productive rate is 37.1%, to use polystyrene as standard specimen, in gel permeation chromatography (GPC) test that tetrahydrofuran (THF) (THF) is moving phase, obtain polymethylmethacrylate, number-average molecular weight is 92935, and molecular weight dispersion index is 1.45.
Embodiment 4:
In the there-necked flask that stirrer is housed, add successively the refined tetrahydrofuran (THF) of 20ml, 0.1g thionyl benzene, 0.13g butylene oxide ring and 0.5ml1M BF
3solution, stirs after 25 minutes under normal temperature, then adds 0.5ml1M BF
3solution, by 0.13gAlCl
3the solution that is dissolved in 5.16g methyl methacrylate joins in there-necked flask, keeping system temperature 50 C, reacted after 72 hours, added 20ml acetone, the aqueous solution that under agitation to drip massfraction that 2ml contains NaOH be 10% stirs termination reaction after 40 minutes at 30 DEG C.In the time of system cool to room temperature, add 50ml methanol extraction polymkeric substance.Then polymkeric substance separates.Vacuum-drying at 40 DEG C.Resulting polymers productive rate is 43.3%, to use polystyrene as standard specimen, in gel permeation chromatography (GPC) test that tetrahydrofuran (THF) (THF) is moving phase, obtain polymethylmethacrylate, number-average molecular weight is 103368, and molecular weight dispersion index is 1.34.
Embodiment 5:
In the there-necked flask that stirrer is housed, add successively the refined tetrahydrofuran (THF) of 20ml, 0.1g thionyl benzene, 0.12g epoxy chloropropane and 0.5ml1M BF
3solution, stirs after 25 minutes under normal temperature, then adds 0.5ml1M BF
3solution, by 0.13gAlCl
3the solution that is dissolved in 10.0g methyl methacrylate joins in there-necked flask, and 30 DEG C of keeping system temperature were reacted after 72 hours, added 30ml acetone, under agitation dripped 2ml and contained Na
2cO
3the massfraction aqueous solution that is 10%, at 50 DEG C, stir termination reaction after 50 minutes.In the time of system cool to room temperature, add 100ml methanol extraction polymkeric substance.Then polymkeric substance separates.Vacuum-drying at 40 DEG C.Resulting polymers productive rate is 52.5%, to use polystyrene as standard specimen, in gel permeation chromatography (GPC) test that tetrahydrofuran (THF) (THF) is moving phase, obtain polymethylmethacrylate, number-average molecular weight is 3244, and molecular weight dispersion index is 1.53.
Embodiment 6:
In the there-necked flask that stirrer is housed, add successively the refined tetrahydrofuran (THF) of 20ml, 0.1g thionyl benzene, 0.1g epoxy chloropropane and 0.5ml1M BF
3solution, stirs after 25 minutes under normal temperature, then adds 0.5ml1M BF
3solution, by 0.13gAlCl
3the solution that is dissolved in 5.10g methyl methacrylate joins in there-necked flask, and 20 DEG C of keeping system temperature were reacted after 72 hours, added 20ml acetone, under agitation dripped 2ml and contained Na
2cO
3the massfraction aqueous solution that is 10%, at 50 DEG C, stir termination reaction after 50 minutes.In the time of system cool to room temperature, add 50ml methanol extraction polymkeric substance.Then polymkeric substance separates.Vacuum-drying at 40 DEG C.Resulting polymers productive rate is 93%, to use polystyrene as standard specimen, in gel permeation chromatography (GPC) test that tetrahydrofuran (THF) (THF) is moving phase, obtain polymethylmethacrylate, number-average molecular weight is 108041, and molecular weight dispersion index is 1.54.
Embodiment 7:
In the there-necked flask that stirrer is housed, add successively the refined tetrahydrofuran (THF) of 20ml, 0.1g diphenyl sulfoxide, 0.1g epoxy chloropropane and 0.5ml1MBF
3solution, stirs after 25 minutes, by 0.13gAlCl under normal temperature
3the solution that is dissolved in 5.15g methyl methacrylate joins in there-necked flask.30 DEG C of keeping system temperature.React after 65 hours, add 20ml acetone, under agitation drip 2ml and contain Na
2cO
3the massfraction aqueous solution that is 10%, at 50 DEG C, stir termination reaction after 50 minutes.In the time of system cool to room temperature, add 50ml methanol extraction polymkeric substance.Then polymkeric substance separates.Vacuum-drying at 40 DEG C.Resulting polymers productive rate is 33%, to use polystyrene as standard specimen, in gel permeation chromatography (GPC) test that tetrahydrofuran (THF) (THF) is moving phase, obtain polymethylmethacrylate, number-average molecular weight is 185045, and molecular weight dispersion index is 1.77.
Embodiment 8:
In the there-necked flask that stirrer is housed, add successively the refined tetrahydrofuran (THF) of 20ml, 0.1g diphenyl sulfoxide, 0.1g epoxy chloropropane and 0.75ml1MBF
3solution, stirs after 25 minutes, by 0.21gAlCl under normal temperature
3the solution that is dissolved in 5.15g methyl methacrylate joins in there-necked flask.30 DEG C of keeping system temperature.React after 72 hours, add 20ml acetone, under agitation drip 2ml and contain Na
2cO
3the massfraction aqueous solution that is 10%, at 50 DEG C, stir termination reaction after 50 minutes.In the time of system cool to room temperature, add 50ml methanol extraction polymkeric substance.Then polymkeric substance separates.Vacuum-drying at 40 DEG C.Resulting polymers productive rate is 24%, to use polystyrene as standard specimen, in gel permeation chromatography (GPC) test that tetrahydrofuran (THF) (THF) is moving phase, obtain polymethylmethacrylate, number-average molecular weight is 135089, and molecular weight dispersion index is 1.65.
Embodiment 9:
In the there-necked flask that stirrer is housed, add successively the refined tetrahydrofuran (THF) of 20ml, 0.1g diphenyl sulfoxide, 0.1g epoxy chloropropane and 0.75ml1MBF
3solution, stirs after 25 minutes, by 0.13gAlCl under normal temperature
3the solution that is dissolved in 5.15g methyl methacrylate joins in there-necked flask.30 DEG C of keeping system temperature.React after 72 hours, add 20ml acetone, under agitation drip 2ml and contain NaHCO
3the massfraction aqueous solution that is 10%, at 50 DEG C, stir termination reaction after 50 minutes.In the time of system cool to room temperature, add 50ml methanol extraction polymkeric substance.Then polymkeric substance separates.Vacuum-drying at 40 DEG C.Resulting polymers productive rate is 17.2%, to use polystyrene as standard specimen, in gel permeation chromatography (GPC) test that tetrahydrofuran (THF) (THF) is moving phase, obtain polymethylmethacrylate, number-average molecular weight is 132056, and molecular weight dispersion index is 1.57.
Claims (10)
1. the preparation method of polymethylmethacrylate, it is characterized in that adding catalyzer and refining methyl methacrylate in thionyl benzene ionic compound solution, under anhydrous organic solvent exists, controlling temperature is 0 DEG C～50 DEG C, through polymerization, termination polyreaction, then in solution, add precipitation agent to isolate polymethylmethacrylate.
2. by the preparation method of polymethylmethacrylate claimed in claim 1, it is characterized in that the preparation method of described thionyl benzene ionic compound, include following steps: in reaction vessel, add successively tetrahydrofuran (THF), thionyl benzene and boron trifluoride and epoxy compounds, under normal temperature, stir 10～30 minutes, obtain thionyl benzene ionic compound solution.
3. by the preparation method of polymethylmethacrylate claimed in claim 1, it is characterized in that described epoxy compounds is any one in oxyethane, propylene oxide, butylene oxide ring, epoxy chloropropane, epoxy styrene, epoxy iso-butylene, oxirane ring hexene, single butadiene monoxide and bis-epoxy butylene.
4. by the preparation method of polymethylmethacrylate claimed in claim 1, it is characterized in that described polymethylmethacrylate, there is the general structure that formula I represents:
Wherein, in formula, n is greater than 50 integer, and R is hydrogen, methyl, ethyl, chloromethyl, phenyl or sec.-propyl.
5. by the preparation method of polymethylmethacrylate claimed in claim 1, it is characterized in that described catalyzer is the mixture of boron trifluoride and aluminum chloride.
6. by the preparation method of polymethylmethacrylate claimed in claim 1, it is characterized in that described anhydrous organic solvent is for process purified tetrahydrofuran.
7. by the preparation method of polymethylmethacrylate claimed in claim 1, it is characterized in that the temperature of described polyreaction is 20 DEG C～35 DEG C.
8. by the preparation method of polymethylmethacrylate claimed in claim 1, it is characterized in that the time of described polyreaction is 65～120 hours.
9. by the preparation method of polymethylmethacrylate claimed in claim 1, it is characterized in that the churning time of described termination polyreaction is 20～50 minutes, the temperature of termination reaction is carried out at 20 DEG C～50 DEG C.
10. by the preparation method of polymethylmethacrylate claimed in claim 1, it is characterized in that the terminator of described termination polyreaction is KOH, NaOH, Na
2cO
3or NaHCO
3water or alcoholic solution.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104497182A (en) * | 2015-01-15 | 2015-04-08 | 长春工业大学 | Preparation method of polymethyl methacrylate with narrow molecular weight distribution |
| CN105541889A (en) * | 2016-01-23 | 2016-05-04 | 武汉工程大学 | Preparation method for boron difluoride diphenyl sulphur tetrafluoroborate compound |
| CN112940160A (en) * | 2021-03-03 | 2021-06-11 | 威海金合思化工有限公司 | Method for synthesizing ultra-high molecular weight polymethyl methacrylate |
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| CN101701063A (en) * | 2009-11-18 | 2010-05-05 | 武汉工程大学 | Preparation method of polyepichlorohydrin |
| CN102174185A (en) * | 2011-01-31 | 2011-09-07 | 武汉工程大学 | Synthesis technology of hydroxyl terminated polyepichlorohydrin |
| CN103403035A (en) * | 2011-04-15 | 2013-11-20 | 赢创德固赛有限公司 | Novel initiation process for polymerization with activation using ionic liquids |
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2014
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101701063A (en) * | 2009-11-18 | 2010-05-05 | 武汉工程大学 | Preparation method of polyepichlorohydrin |
| CN102174185A (en) * | 2011-01-31 | 2011-09-07 | 武汉工程大学 | Synthesis technology of hydroxyl terminated polyepichlorohydrin |
| CN103403035A (en) * | 2011-04-15 | 2013-11-20 | 赢创德固赛有限公司 | Novel initiation process for polymerization with activation using ionic liquids |
Non-Patent Citations (2)
| Title |
|---|
| SHENGMIN GONG等: "Atom transfer radical polymerization of methyl methacrylate induced by an initiator derived from an ionic liquid", 《POLYMER INTERNATIONAL》, vol. 55, no. 12, 26 June 2006 (2006-06-26), pages 1420 - 1425, XP055033627, DOI: doi:10.1002/pi.2095 * |
| 王国建: "《高分子现代合成方法与技术》", 31 July 2013, article "基团转移聚合", pages: 40-41 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104497182A (en) * | 2015-01-15 | 2015-04-08 | 长春工业大学 | Preparation method of polymethyl methacrylate with narrow molecular weight distribution |
| CN105541889A (en) * | 2016-01-23 | 2016-05-04 | 武汉工程大学 | Preparation method for boron difluoride diphenyl sulphur tetrafluoroborate compound |
| CN112940160A (en) * | 2021-03-03 | 2021-06-11 | 威海金合思化工有限公司 | Method for synthesizing ultra-high molecular weight polymethyl methacrylate |
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