CN102504071B - Preparation method of polymethylmethacrylate with high molecular weight and narrow molecular weight distribution - Google Patents
Preparation method of polymethylmethacrylate with high molecular weight and narrow molecular weight distribution Download PDFInfo
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- CN102504071B CN102504071B CN2011103310608A CN201110331060A CN102504071B CN 102504071 B CN102504071 B CN 102504071B CN 2011103310608 A CN2011103310608 A CN 2011103310608A CN 201110331060 A CN201110331060 A CN 201110331060A CN 102504071 B CN102504071 B CN 102504071B
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Abstract
The invention belongs to the field of chemical materials and discloses a preparation method of polymethylmethacrylate with high molecular weight and narrow molecular weight distribution, which includes mixing an RAFT chain transfer agent and a methyl methacrylate monomer to form even oil solution, adding the even oil solution into emulsifier water solution to obtain pre-emulsion, introducing nitrogen to for deoxidization, heating the pre-emulsion to the temperature ranging from 65 DEG C to 80 DEG C and adding initiator to trigger polymerization which lasts for 2 to 6 hours to obtain polymethylmethacrylate with high molecular weight and narrow molecular weight distribution. The preparation method successfully applying reversible addition/ breaking chain transfer free radical polymerization technology to a micro emulation system, has better control characteristic on micro emulation polymerization of methyl methacrylate, improves emulation stability in the polymerization process, and ensures that the prepared polymer has higher molecular weight and narrower molecular weight distribution. Simultaneously, content of emulsifier in the polymer is lower, and purity of the polymer is greatly improved.
Description
Technical field
The invention belongs to chemical material field, be specifically related to the preparation method of the polymethylmethacrylate of a kind of high molecular and narrow molecular weight distribution.
Background technology
Radical polymerization, due to it, to have an applicable monomer in extensive range, characteristics such as polymerizing condition gentleness and being widely used.Radical polymerization process has following characteristics: causes slowly, and fast the growth, speed stops.But conventional radical polymerization can't synthetic molecular weight narrowly distributing (molecular weight distributing index is less than 1.5) polymkeric substance.
Since the last century the nineties, the research of living radical polymerization technique has obtained breakthrough.Living free radical polymerization polymerization (Nitroxide-Mediated Living Radical Polymerization has appearred, NMP), atom transfer radical polymerization (Atom Transfer Radical Polymerization, ATRP) and the multiple efficient active free radical polymerization method such as reversible addition/fragmentation chain transfer free radical polymerization (Reversible addition-fragmentation chain transfer polymerization, RAFT).Can prepare high molecular thus, the polymkeric substance of narrow molecular weight distributions or block polymer, graftomer etc.
From the angle of industrial application, wish very much to implement the RAFT living polymerization in emulsion system, had at present much and reported about the research of RAFT letex polymerization and mini-emulsion polymerization, still in microemulsion, implement the report of RAFT living polymerization also seldom.
Microemulsion is a kind of isotropy, thermodynamically stable transparent or semitransparent colloidal dispersion system, and its dispersed phase size is 10～100 nanometers, shorter than visible light wavelength.The advantages such as micro-emulsion polymerization has low, the easy heat transfer of polymerization system viscosity, polymerization process and product and all take water as medium, and rate of polymerization is fast, and production process safety and environmental problem are less.But dense, the shortcoming that monomer concentration is very low that also there is emulsifying agent in polymerization system simultaneously.
Micro-emulsion polymerization has been widely used in traditional radical polymerization at present, yet the enforcement in active free radical polymerization is not but a lot.Micro-emulsion polymerization and RAFT active free radical polymerization are combined, can obtain all controllable polymer latexs of molecular weight and latex particle size.Simultaneously, the RAFT active free radical polymerization can improve widely rate of polymerization under the prerequisite of not losing the living polymerization feature, even the more important thing is under 100% monomer conversion, system still has fabulous polymerization activity feature, has good industrialization process prospect.
Summary of the invention
For the shortcoming and deficiency that overcomes prior art, the object of the present invention is to provide the preparation method of the polymethylmethacrylate of a kind of high molecular and narrow molecular weight distribution.
Purpose of the present invention is achieved through the following technical solutions:
The preparation method of the polymethylmethacrylate of a kind of high molecular and narrow molecular weight distribution comprises the following steps:
RAFT chain-transfer agent and methyl methacrylate monomer are mixed to form to even oil solution, then join in emulsifier aqueous solution, make pre-emulsion, the drop of pre-emulsion is the 10-50 nanometer; Pass into the nitrogen deoxygenation, and pre-emulsion is heated to its temperature is 65-80 ℃, then adds the initiator initiated polymerization that reaction 2-6 hour obtains the polymethylmethacrylate of high molecular and narrow molecular weight distribution;
Described RAFT chain-transfer agent accounts for the 0.03-0.32% of raw material total mass;
Described methyl methacrylate monomer accounts for the 7.18-7.20% of raw material total mass;
Described emulsifying agent accounts for the 9.90-9.95% of raw material total mass;
Described initiator accounts for the 0.035-0.036% of raw material total mass;
Particularly, polyreaction treats that material is cooled to room temperature after finishing, and by material discharging, breakdown of emulsion, washing, drying, obtains the polymethylmethacrylate of high molecular and narrow molecular weight distribution;
The chain-transfer agent that described RAFT chain-transfer agent is reversible addition/fracture active free radical polymerization, preferred S, S '-bis-(α, α '-methyl-α " acetic acid) trithiocarbonate, S; S '-bis-(α-methyl phenyl ketone) trithiocarbonate, S; a kind of in S '-dipropionic acid trithiocarbonate, S-propionic acid-S '-(Alpha-Methyl-α '-acetic acid) trithiocarbonate or S-propionic acid-S '-(α, α '-methyl-α " acetic acid) trithiocarbonate; S particularly preferably, and S '-bis-(α, α '-methyl-α " acetic acid) trithiocarbonate; The structural formula of RAFT chain-transfer agent is as follows respectively:
Described emulsifying agent is alkyl sulphate type anionic emulsifier or alkyl quaternary amine salt type cationic emulsifier, preferred alkyl quaternary ammonium salt cation emulsifying agent cetyl trimethylammonium bromide.
Described initiator is Diisopropyl azodicarboxylate (AIBN).
Its molecular weight of the polymethylmethacrylate prepared by aforesaid method is 1-9 ten thousand, and molecular weight distributing index is 1.0-2.5.
The present invention has following advantage and effect with respect to prior art:
The present invention selects the chain-transfer agent S of suitable reversible addition/fracture chain transfer activity radical polymerization, S '-bis-(α, α '-methyl-α " acetic acid) trithiocarbonate; with traditional micro-emulsion polymerization, compare; the present invention successfully is applied to reversible addition/fracture chain transfer activity radical polymerization technique in microemulsion system; the micro-emulsion polymerization to methyl methacrylate has better control characteristic, has improved the stability of emulsion of polymerization process; Guaranteed that the polymkeric substance prepared has again narrower molecular weight distribution when having higher molecular weight, in polymkeric substance, the content of emulsifying agent is lower simultaneously, has improved widely the purity of polymerisate.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
By 0.0187g RAFT reagent S, S '-bis-(α, α '-methyl-α " acetic acid) trithiocarbonate joins in 4.35gMMA and mixes, and forms oil solution; The 6.0g cetyl trimethylammonium bromide is dissolved in 50g water, forms the aqueous solution; Oil solution and aqueous solution is even, form even translucent pre-emulsion.Pre-emulsion is stirred and is warmed up to 70 ℃, system is passed into to nitrogen 30 minutes with deoxygenation, then 0.02175g initiator A IBN is joined in system, initiator system starts polymerization, and after approximately stablizing ten minutes, microemulsion is gradually by the light yellow translucent very shallow semi-transparent blue that transfers to, mean that reaction starts, finish reaction after 5 hours, slowly cool to discharging after room temperature, obtain the polymethylmethacrylate of high molecular and narrow molecular weight distribution.
Embodiment 2
By 0.0375g RAFT reagent S, S '-bis-(α, α '-methyl-α " acetic acid) trithiocarbonate joins in 4.35gMMA and mixes, and forms oil solution; The 6.0g cetyl trimethylammonium bromide is dissolved in 50g water, forms the aqueous solution; Oil solution and aqueous solution is even, form even translucent pre-emulsion.Pre-emulsion is stirred and is warmed up to 70 ℃, system is passed into to nitrogen 30 minutes with deoxygenation, then 0.02175g initiator A IBN is joined in system, initiator system starts polymerization, and after approximately stablizing ten minutes, microemulsion is gradually by the light yellow translucent very shallow semi-transparent blue that transfers to, mean that reaction starts, finish reaction after 5 hours, slowly cool to discharging after room temperature, obtain the polymethylmethacrylate of high molecular and narrow molecular weight distribution.
Embodiment 3
By 0.0750g RAFT reagent S, S '-bis-(α, α '-methyl-α " acetic acid) trithiocarbonate joins in 4.35gMMA and mixes, and forms oil solution; The 6.0g cetyl trimethylammonium bromide is dissolved in 50g water, forms the aqueous solution; Oil solution and aqueous solution is even, form even translucent pre-emulsion.Pre-emulsion is stirred and is warmed up to 80 ℃, system is passed into to nitrogen 30 minutes with deoxygenation, then 0.02175g initiator A IBN is joined in system, initiator system starts polymerization, and after approximately stablizing ten minutes, microemulsion is gradually by the light yellow translucent very shallow semi-transparent blue that transfers to, mean that reaction starts, finish reaction after 2 hours, slowly cool to discharging after room temperature, obtain the polymethylmethacrylate of high molecular and narrow molecular weight distribution.
Embodiment 4
By 0.1126g RAFT reagent S, S '-bis-(α, α '-methyl-α " acetic acid) trithiocarbonate joins in 4.35gMMA and mixes, and forms oil solution; The 6.0g cetyl trimethylammonium bromide is dissolved in 50g water, forms the aqueous solution; Oil solution and aqueous solution is even, form even translucent pre-emulsion.Pre-emulsion is stirred and is warmed up to 65 ℃, system is passed into to nitrogen 30 minutes with deoxygenation, then 0.02175g initiator A IBN is joined in system, initiator system starts polymerization, and after approximately stablizing ten minutes, microemulsion is gradually by the light yellow translucent very shallow semi-transparent blue that transfers to, mean that reaction starts, finish reaction after 6 hours, slowly cool to discharging after room temperature, obtain the polymethylmethacrylate of high molecular and narrow molecular weight distribution.
Embodiment 5
By 0.1500g RAFT reagent S, S '-bis-(α, α '-methyl-α " acetic acid) trithiocarbonate joins in 4.35gMMA and mixes, and forms oil solution; The 6.0g cetyl trimethylammonium bromide is dissolved in 50g water, forms the aqueous solution; Oil solution and aqueous solution is even, form even translucent pre-emulsion.Pre-emulsion is stirred and is warmed up to 70 ℃, system is passed into to nitrogen 30 minutes with deoxygenation, then 0.02175g initiator A IBN is joined in system, initiator system starts polymerization, and after approximately stablizing ten minutes, microemulsion is gradually by the light yellow translucent very shallow semi-transparent blue that transfers to, mean that reaction starts, finish reaction after 3 hours, slowly cool to discharging after room temperature, obtain the polymethylmethacrylate of high molecular and narrow molecular weight distribution.
Embodiment 6
By 0.1876g RAFT reagent S, S '-bis-(α, α '-methyl-α " acetic acid) trithiocarbonate joins in 4.35gMMA and mixes, and forms oil solution; The 6.0g cetyl trimethylammonium bromide is dissolved in 50g water, forms the aqueous solution; Oil solution and aqueous solution is even, form even translucent pre-emulsion.Pre-emulsion is stirred and is warmed up to 70 ℃, system is passed into to nitrogen 30 minutes with deoxygenation, then 0.02175g initiator A IBN is joined in system, initiator system starts polymerization, and after approximately stablizing ten minutes, microemulsion is gradually by the light yellow translucent very shallow semi-transparent blue that transfers to, mean that reaction starts, finish reaction after 5 hours, slowly cool to discharging after room temperature, obtain the polymethylmethacrylate of high molecular and narrow molecular weight distribution.
The molecular weight and molecualr weight distribution index of the polymethylmethacrylate that embodiment 1-6 prepares is in Table 1.The molecular weight of polymkeric substance and distribution thereof are measured by Waters 1515 type gel permeation chromatographs.
The molecular weight and molecualr weight distribution index of the polymethylmethacrylate that table 1 embodiment 1-6 prepares
| Embodiment | Transformation efficiency, % | Number-average molecular weight | Molecular weight distributing index |
| 1 | 96.8 | 84000 | 2.39 |
| 2 | 85.5 | 43000 | 1.89 |
| 3 | 82.4 | 33000 | 1.62 |
| 4 | 80.8 | 24000 | 1.43 |
| 5 | 74.2 | 17000 | 1.32 |
| 6 | 64.3 | 12000 | 1.28 |
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (2)
1. the preparation method of the polymethylmethacrylate of a high molecular and narrow molecular weight distribution is characterized in that comprising the following steps:
RAFT chain-transfer agent and methyl methacrylate monomer are mixed to form to even oil solution, then join in emulsifier aqueous solution, make pre-emulsion, the drop of pre-emulsion is the 10-50 nanometer; Pass into the nitrogen deoxygenation, and pre-emulsion is heated to its temperature is 65-80 ℃, then adds the initiator initiated polymerization that reaction 2-6 hour obtains the polymethylmethacrylate of high molecular and narrow molecular weight distribution;
Described RAFT chain-transfer agent accounts for the 0.03-0.32% of raw material total mass;
Described methyl methacrylate monomer accounts for the 7.18-7.20% of raw material total mass;
Described emulsifying agent accounts for the 9.90-9.95% of raw material total mass;
Described initiator accounts for the 0.035-0.036% of raw material total mass;
Described RAFT chain-transfer agent is S, S '-bis-(α, α '-methyl-α ' '-acetic acid) trithiocarbonate, S, S '-bis-(α-methyl phenyl ketone) trithiocarbonate, S, a kind of in S '-dipropionic acid trithiocarbonate, S-propionic acid-S '-(Alpha-Methyl-α '-acetic acid) trithiocarbonate or S-propionic acid-S '-(α, α '-methyl-α ' '-acetic acid) trithiocarbonate.
2. the preparation method of the polymethylmethacrylate of high molecular according to claim 1 and narrow molecular weight distribution, it is characterized in that: described RAFT chain-transfer agent is S, S '-bis-(α, α '-methyl-α ' '-acetic acid) trithiocarbonate.
3, the preparation method of the polymethylmethacrylate of high molecular according to claim 1 and narrow molecular weight distribution is characterized in that: described emulsifying agent is alkyl sulphate type anionic emulsifier or alkyl quaternary amine salt type cationic emulsifier.
4, the preparation method of the polymethylmethacrylate of high molecular according to claim 3 and narrow molecular weight distribution is characterized in that: described alkyl quaternary amine salt type cationic emulsifier is cetyl trimethylammonium bromide.
5, the preparation method of the polymethylmethacrylate of high molecular according to claim 1 and narrow molecular weight distribution is characterized in that: described initiator is Diisopropyl azodicarboxylate.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016182711A1 (en) * | 2015-05-08 | 2016-11-17 | The Lubrizol Corporation | Water soluble chain transfer agents |
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| CN104086684A (en) * | 2014-07-09 | 2014-10-08 | 天津大学 | Preparation method of poly 2-acrylic acid-2(2-methoxy ethoxy) ethyl ester in narrow molecular-weight distribution |
| CN104497182B (en) * | 2015-01-15 | 2016-11-23 | 长春工业大学 | The preparation method of Narrow Molecular Weight Distribution polymethyl methacrylate |
| CN112940160B (en) * | 2021-03-03 | 2022-09-27 | 威海金合思化工有限公司 | Method for synthesizing ultra-high molecular weight polymethyl methacrylate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1687153A (en) * | 2005-04-05 | 2005-10-26 | 苏州大学 | Polmerization method of catalysis chain transfer for methyl methacrylate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1687153A (en) * | 2005-04-05 | 2005-10-26 | 苏州大学 | Polmerization method of catalysis chain transfer for methyl methacrylate |
Non-Patent Citations (2)
| Title |
|---|
| 崔秀峰.甲基丙烯酸甲酯的可逆加成断裂链转移（RAFT）的乳液聚合.《中国优秀博硕士学位论文全文数据库 (硕士) 工程科技Ⅰ辑》.2006,(第6期),第26-28页. * |
| 陈智等.三硫代碳酸醋存在下MMA 乳液/悬浮体系的RAFT聚合研究.《2007年全国高分子学术论文报告会论文摘要集(上册)》.2007,第78页. * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016182711A1 (en) * | 2015-05-08 | 2016-11-17 | The Lubrizol Corporation | Water soluble chain transfer agents |
| US10280101B2 (en) | 2015-05-08 | 2019-05-07 | The Lubrizol Corporation | Water soluble chain transfer agents |
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