CN102504071A - 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
- Publication number
- CN102504071A CN102504071A CN2011103310608A CN201110331060A CN102504071A CN 102504071 A CN102504071 A CN 102504071A CN 2011103310608 A CN2011103310608 A CN 2011103310608A CN 201110331060 A CN201110331060 A CN 201110331060A CN 102504071 A CN102504071 A CN 102504071A
- Authority
- CN
- China
- Prior art keywords
- molecular weight
- polymethylmethacrylate
- weight distribution
- preparation
- narrow molecular
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- QDKZXZUEEJSQCQ-UHFFFAOYSA-N N=C(NCC(c1ccccc1)=O)NCC(C1=CC=CCN=C1)=O Chemical compound N=C(NCC(c1ccccc1)=O)NCC(C1=CC=CCN=C1)=O QDKZXZUEEJSQCQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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 HMW and narrow molecular weight distribution.
Background technology
Radical polymerization, because that it has a suitable monomer is in extensive range, characteristics such as polymerizing condition gentleness and obtained using widely.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), ATRP (Atom Transfer Radical Polymerization; ATRP) and reversible addition/fragmentation chain transfer free radical polymerization (Reversible addition-fragmentation chain transfer polymerization, the multiple method of active free radical polymerization efficiently such as RAFT).Can prepare HMW thus, the polymkeric substance of narrow molecular weight distributions or block polymer, graftomer etc.
From the angle of industrial application, very hope can be implemented the RAFT living polymerization in emulsion system, had at present much and reported about the researchs of RAFT letex polymerization and mini-emulsion polymerization, but the report of enforcement RAFT living polymerization also seldom in microemulsion.
Microemulsion is a kind of isotropy, thermodynamically stable transparent or semitransparent colloidal dispersion system, and its dispersed phase size is 10～100 nanometers, and is shorter than wavelength of visible light.Advantages such as it is medium with water all that micro-emulsion polymerization has low, the easy heat transfer of polymerization system viscosity, polymerization process and product, 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 have simultaneously emulsifying agent in the polymerization system.
Micro-emulsion polymerization has been widely used in traditional radical polymerization at present, yet the enforcement in active free radical polymerization but is not a lot.Micro-emulsion polymerization and RAFT active free radical polymerization are combined, can obtain all controllable polymer latex of molecular weight and latex particle size.Simultaneously; The RAFT active free radical polymerization can improve rate of polymerization widely under the prerequisite of not losing the living polymerization characteristic, even the more important thing is under 100% monomer conversion; System still has fabulous polymerization activity characteristic, has favorable industrial metallization processes 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 HMW and narrow molecular weight distribution.
The object of the invention is realized through following technical proposals:
The preparation method of the polymethylmethacrylate of a kind of HMW and narrow molecular weight distribution may further comprise the steps:
The RAFT chain-transfer agent is mixed the even oil solution of formation with MMA MONOMER, join then in the emulsifier aqueous solution, make pre-emulsion, the drop of pre-emulsion is the 10-50 nanometer; Feed the nitrogen deoxygenation, and pre-emulsion is heated to its temperature is 65-80 ℃, adds the initiator initiated polymerization again, reacted 2-6 hour, obtain the polymethylmethacrylate of HMW and narrow molecular weight distribution;
Described RAFT chain-transfer agent accounts for the 0.03-0.32% of raw material total mass;
Described MMA 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 with material discharging, breakdown of emulsion, washing, drying, obtains the polymethylmethacrylate of HMW and narrow molecular weight distribution;
Described RAFT chain-transfer agent is the chain-transfer agent of reversible addition/fracture active free radical polymerization; Preferred S; S '-two (α, α '-methyl-α " acetate) trithiocarbonate, S, S '-two (α-methyl phenyl ketone) trithiocarbonate, S; a kind of in S '-dipropionic acid trithiocarbonate, S-propionic acid-S '-(Alpha-Methyl-α '-acetate) trithiocarbonate or S-propionic acid-S '-(α, α '-methyl-α " acetate) trithiocarbonate; Preferred especially S, and S '-two (α, α '-methyl-α " acetate) trithiocarbonate; The structural formula of RAFT chain-transfer agent is distinguished as follows:
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 polymethylmethacrylate that is obtained by method for preparing 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 for use; S '-two (α; α '-methyl-α " acetate) trithiocarbonate, compare with traditional micro-emulsion polymerization, the present invention successfully is applied to reversible addition/fracture chain transfer activity radical polymerization technique in the microemulsion system; the micro-emulsion polymerization to TEB 3K has better control characteristic, has improved the stability of emulsion of polymerization process; Guaranteed that the polymkeric substance for preparing has narrower MWD again when having higher molecular weight, the content of emulsifying agent is lower in the polymkeric substance simultaneously, has improved the purity of polymerisate widely.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail, but embodiment of the present invention is not limited thereto.
Embodiment 1
With 0.0187g RAFT reagent S, S '-two (α, α '-methyl-α " acetate) trithiocarbonate joins among the 4.35gMMA and mixes, and forms oil solution; The 6.0g cetyl trimethylammonium bromide is dissolved in the 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 fed nitrogen 30 minutes with deoxygenation, then 0.02175g initiator A IBN is joined in the system; Initiator system begins polymerization, stablize ten minutes approximately after, microemulsion is gradually by the light yellow translucent very shallow semi-transparent blue that transfers to; The expression reaction begins; Finish reaction after 5 hours, slowly cool to discharging after the room temperature, promptly obtain the polymethylmethacrylate of HMW and narrow molecular weight distribution.
Embodiment 2
With 0.0375g RAFT reagent S, S '-two (α, α '-methyl-α " acetate) trithiocarbonate joins among the 4.35gMMA and mixes, and forms oil solution; The 6.0g cetyl trimethylammonium bromide is dissolved in the 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 fed nitrogen 30 minutes with deoxygenation, then 0.02175g initiator A IBN is joined in the system; Initiator system begins polymerization, stablize ten minutes approximately after, microemulsion is gradually by the light yellow translucent very shallow semi-transparent blue that transfers to; The expression reaction begins; Finish reaction after 5 hours, slowly cool to discharging after the room temperature, promptly obtain the polymethylmethacrylate of HMW and narrow molecular weight distribution.
Embodiment 3
With 0.0750g RAFT reagent S, S '-two (α, α '-methyl-α " acetate) trithiocarbonate joins among the 4.35gMMA and mixes, and forms oil solution; The 6.0g cetyl trimethylammonium bromide is dissolved in the 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 fed nitrogen 30 minutes with deoxygenation, then 0.02175g initiator A IBN is joined in the system; Initiator system begins polymerization, stablize ten minutes approximately after, microemulsion is gradually by the light yellow translucent very shallow semi-transparent blue that transfers to; The expression reaction begins; Finish reaction after 2 hours, slowly cool to discharging after the room temperature, promptly obtain the polymethylmethacrylate of HMW and narrow molecular weight distribution.
Embodiment 4
With 0.1126g RAFT reagent S, S '-two (α, α '-methyl-α " acetate) trithiocarbonate joins among the 4.35gMMA and mixes, and forms oil solution; The 6.0g cetyl trimethylammonium bromide is dissolved in the 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 fed nitrogen 30 minutes with deoxygenation, then 0.02175g initiator A IBN is joined in the system; Initiator system begins polymerization, stablize ten minutes approximately after, microemulsion is gradually by the light yellow translucent very shallow semi-transparent blue that transfers to; The expression reaction begins; Finish reaction after 6 hours, slowly cool to discharging after the room temperature, promptly obtain the polymethylmethacrylate of HMW and narrow molecular weight distribution.
Embodiment 5
With 0.1500g RAFT reagent S, S '-two (α, α '-methyl-α " acetate) trithiocarbonate joins among the 4.35gMMA and mixes, and forms oil solution; The 6.0g cetyl trimethylammonium bromide is dissolved in the 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 fed nitrogen 30 minutes with deoxygenation, then 0.02175g initiator A IBN is joined in the system; Initiator system begins polymerization, stablize ten minutes approximately after, microemulsion is gradually by the light yellow translucent very shallow semi-transparent blue that transfers to; The expression reaction begins; Finish reaction after 3 hours, slowly cool to discharging after the room temperature, promptly obtain the polymethylmethacrylate of HMW and narrow molecular weight distribution.
Embodiment 6
With 0.1876g RAFT reagent S, S '-two (α, α '-methyl-α " acetate) trithiocarbonate joins among the 4.35gMMA and mixes, and forms oil solution; The 6.0g cetyl trimethylammonium bromide is dissolved in the 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 fed nitrogen 30 minutes with deoxygenation, then 0.02175g initiator A IBN is joined in the system; Initiator system begins polymerization, stablize ten minutes approximately after, microemulsion is gradually by the light yellow translucent very shallow semi-transparent blue that transfers to; The expression reaction begins; Finish reaction after 5 hours, slowly cool to discharging after the room temperature, promptly obtain the polymethylmethacrylate of HMW and narrow molecular weight distribution.
The molecular weight and the molecular weight distributing index of the polymethylmethacrylate that embodiment 1-6 prepares are seen table 1.The molecular weight of polymkeric substance and distribution thereof are measured by Waters 1515 type gel permeation chromatographs.
The molecular weight and the molecular weight distributing 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 |
The foregoing description is a preferred implementation of the present invention; But embodiment of the present invention is not restricted to the described embodiments; Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (7)
1. the preparation method of the polymethylmethacrylate of HMW and narrow molecular weight distribution is characterized in that may further comprise the steps:
The RAFT chain-transfer agent is mixed the even oil solution of formation with MMA MONOMER, join then in the emulsifier aqueous solution, make pre-emulsion; Feed the nitrogen deoxygenation, and pre-emulsion is heated to its temperature is 65-80 ℃, adds the initiator initiated polymerization again, reacted 2-6 hour, obtain the polymethylmethacrylate of HMW and narrow molecular weight distribution.
2. the preparation method of the polymethylmethacrylate of HMW according to claim 1 and narrow molecular weight distribution is characterized in that:
Described RAFT chain-transfer agent accounts for the 0.03-0.32% of raw material total mass;
Described MMA 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.
3. the preparation method of the polymethylmethacrylate of HMW according to claim 1 and 2 and narrow molecular weight distribution; It is characterized in that: described RAFT chain-transfer agent is S; S '-two (α; α '-methyl-α " acetate) trithiocarbonate, S; S '-two (α-methyl phenyl ketone) trithiocarbonate, S, a kind of in S '-dipropionic acid trithiocarbonate, S-propionic acid-S '-(Alpha-Methyl-α '-acetate) trithiocarbonate or S-propionic acid-S '-(α, α '-methyl-α " acetate) trithiocarbonate.
4. the preparation method of the polymethylmethacrylate of HMW according to claim 1 and 2 and narrow molecular weight distribution is characterized in that: described RAFT chain-transfer agent is S, and S '-two (α, α '-methyl-α " acetate) trithiocarbonate.
5. the preparation method of the polymethylmethacrylate of HMW according to claim 1 and 2 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.
6. the preparation method of the polymethylmethacrylate of HMW according to claim 1 and 2 and narrow molecular weight distribution is characterized in that: described alkyl quaternary amine salt type cationic emulsifier is a cetyl trimethylammonium bromide.
7. the preparation method of the polymethylmethacrylate of HMW according to claim 1 and 2 and narrow molecular weight distribution is characterized in that: described initiator is a Diisopropyl azodicarboxylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103310608A CN102504071B (en) | 2011-10-27 | 2011-10-27 | Preparation method of polymethylmethacrylate with high molecular weight and narrow molecular weight distribution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103310608A CN102504071B (en) | 2011-10-27 | 2011-10-27 | Preparation method of polymethylmethacrylate with high molecular weight and narrow molecular weight distribution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102504071A true CN102504071A (en) | 2012-06-20 |
| CN102504071B CN102504071B (en) | 2013-12-04 |
Family
ID=46216210
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011103310608A Expired - Fee Related CN102504071B (en) | 2011-10-27 | 2011-10-27 | Preparation method of polymethylmethacrylate with high molecular weight and narrow molecular weight distribution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102504071B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104497182A (en) * | 2015-01-15 | 2015-04-08 | 长春工业大学 | Preparation method of polymethyl methacrylate with narrow molecular weight distribution |
| CN107835801A (en) * | 2015-05-08 | 2018-03-23 | 路博润公司 | water-soluble chain transfer agent |
| 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 |
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 |
-
2011
- 2011-10-27 CN CN2011103310608A patent/CN102504071B/en not_active Expired - Fee Related
Patent 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 |
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》 * |
| 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）》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104497182A (en) * | 2015-01-15 | 2015-04-08 | 长春工业大学 | Preparation method of polymethyl methacrylate with narrow molecular weight distribution |
| CN107835801A (en) * | 2015-05-08 | 2018-03-23 | 路博润公司 | water-soluble chain transfer agent |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102504071B (en) | 2013-12-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101955555B (en) | Implementation method of reversible addition fragmentation chain emulsion polymerization | |
| CN104530302B (en) | A kind of Ludox/polyacrylate dispersion of high silicon content and preparation method thereof | |
| CN103073679B (en) | Method for producing polyacrylamide microsphere water shutoff agent | |
| CN110483687B (en) | Fracturing fluid thickening agent and preparation method thereof | |
| CN102504071B (en) | Preparation method of polymethylmethacrylate with high molecular weight and narrow molecular weight distribution | |
| CN102115514B (en) | Preparation method of acid liquor thickening agent | |
| CN103739777A (en) | Core-shell type cationic/anionic polyacrylamide profile control oil displacing microsphere and preparation method thereof | |
| CN103937484B (en) | Shale gas well slickwater fracturing fluid system high-efficiency emulsion quick water-soluble drag reducer | |
| CN103694428B (en) | A kind of Tri-phosphor block copolymer type white phosphor powder and preparation method thereof | |
| CN104153222A (en) | Direct injection ink-jet printing dispersion ink and preparation method thereof | |
| CN105566516B (en) | A kind of structure directing type composite initiator system and acrylamide polymer and its preparation method and application | |
| CN101591403A (en) | The preparation method of reversible addition-fragmentation chain transfer emulsion polymerization | |
| CN101591405B (en) | Method for preparing high molecular weight and segmented polymers by reversible addition-fragmentation chain transfer emulsion polymerization | |
| CN105601804A (en) | Hydrophobic associated polymer and preparation method thereof | |
| CN105418839A (en) | Preparation method of anion water-in-water type polyacrylamide | |
| CN105399897A (en) | Heatproof salt-resistant polyacrylamide polymer and preparation method thereof | |
| CN103694379B (en) | A kind of have di-block copolymer of light and pH response characteristic and preparation method thereof | |
| CN104356292B (en) | A kind of preparation method of PAMC aqueous emulsion product | |
| CN104628940B (en) | A kind of acrylamide copolymer and its preparation method and application | |
| CN102808360A (en) | Temperature-resistant water-based gloss oil for high-gloss paper products and preparation method of temperature-resistant water-based gloss oil | |
| CN104829793A (en) | Preparation method of temperature and pH sensitive organic/inorganic hybrid material POSS/PDMAEMA-b-PNIPAM | |
| CN106519092B (en) | The method for preparing polymer nanocomposites as the Pickering lotion of emulsifier using organically-modified magadiite | |
| CN102070730B (en) | A kind of method of preparing emulsion with multivariate particle size distribution in situ | |
| CN104031214A (en) | St/MAH-g-MMA (styrene/maleic anhydride-grafted-methyl methacrylate) graft copolymer, and preparation method and application thereof | |
| CN104152130A (en) | AM /NaAA/NIDA hydrophobic association polymer oil displacement agent and synthetic method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131204 Termination date: 20151027 |
|
| EXPY | Termination of patent right or utility model |