CN1277852C - Process for preparing high molecular weight, narrow molecular weight distribution polystyrene and its copolymer - Google Patents
Process for preparing high molecular weight, narrow molecular weight distribution polystyrene and its copolymer Download PDFInfo
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- CN1277852C CN1277852C CN 200410066751 CN200410066751A CN1277852C CN 1277852 C CN1277852 C CN 1277852C CN 200410066751 CN200410066751 CN 200410066751 CN 200410066751 A CN200410066751 A CN 200410066751A CN 1277852 C CN1277852 C CN 1277852C
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Abstract
The present invention discloses a process for preparing high molecular weight, narrow molecular weight distribution polystyrene and a copolymer thereof. RAFT chain transfer reagents at the required quantity, co-stabilizers and a certain amount of styrene monomer are mixed to form uniform solution (a monomer flow 1); then, emulsifying agent water solution is added; after mixing is carried out for 10 minutes, ultrasonic dispersion is carried out for 15 minutes, and fine emulsion is prepared. The fine emulsion is transferred into a reactor which is provided with a mechanical stirring and condensing tube, an N2 inlet device and a feeding inlet, and water-bath heating is kept at the reaction temperature. After N2 oxygen removal, initiating agents are added; polymerization is initiated, and after polymerization is completed and the temperature of slow cooling is reduced to room temperature, discharging, emulsion breaking, washing and drying are carried out. When the present invention is used for preparing a high molecular weight polymer, molecular weight distribution is narrow; the content of the emulsifying agents and the co-stabilizers is low; the purity of polymerisates is greatly improved, and the time percentage of a complicated nucleation period in the integral polymerization process is effectively reduced in the RAFT fine emulsion polymerization process.
Description
Technical field
The present invention relates to a kind of high molecular, the preparation method of narrow molecular weight distributions polystyrene and multipolymer thereof.
Background technology
Radical polymerization has obtained owing to characteristics such as the monomer that is suitable for are in extensive range, the polymerizing condition gentleness using widely.The free crowd process has following characteristics: causes slowly, and fast the growth, speed stops.Thus, conventional radical polymerization can't synthesize the polymkeric substance that has such as: narrow molecular weight distribution (molecular weight distributing index is less than 1.5), high-purity fine-feature such as block.But since the last century the nineties, the living radical technical study makes a breakthrough.Formed living free radical polymerization polymerization (Nitroxide-Mediated Living RadicalPolymerizations, NMP), atom transfer radical polymerization (Atom Transfer RadicalPolymerization, ATRP) and reversible addition-fragmentation-chain transfer radical polymerization (Reversibleaddition-fragmentation chain transfer polymerization RAFT) waits three kinds of high-efficiency activated radical polymerization systems.Active free radical polymerization can prepare narrow molecular weight distribution polymer, segmented copolymer etc.Functional monomer and solvent very wide model (as: OH ,-COOH ,-CONR that the RAFT living polymerization is suitable for
2,-NR
2,-SO
3Na or the like).The RAFT active free radical polymerization is by Chiefari, J. etc. (Macromolecules 31,5559 (1998)) propose first, it has been realized polymerization process control by the reversible addition-chain transfer-fragmentation that increases between free radical and RAFT (two thioesters) chain-transfer agent, thus the polymerisate that can obtain having fine structure.The synthetic of RAFT reagent wherein has been disclosed among Chem.Commun.1044 (2001) and the WO.98/01478.
From the angle of industrial application, wish very much in letex polymerization, to implement the RAFT living polymerization.Existing many research reports about RAFT letex polymerization and mini-emulsion polymerization.The used polymerization process of these reports all is a batchwise polymerization.
Summary of the invention
The purpose of this invention is to provide a kind of high molecular, the preparation method of narrow molecular weight distributions polystyrene and multipolymer thereof.
The step of method is as follows:
1) 0.1～10 part of RAFT chain-transfer agent and 1～20 part of co-stabilizer and 50～200 parts of vinyl monomers are mixed, form monomer flow 1 oil solution; 1～20 part of emulsifiers dissolve in 300～500 parts of water, is formed the aqueous solution; After monomer flow 1 oil solution and aqueous solution, under mechanical stirring, after the high shear field effect, pulverize, make miniemulsion;
2) miniemulsion is moved into reactor, feed nitrogen after 30～60 minutes, add the aqueous solution of water soluble starter, initiated polymerization, the temperature of polyreaction is 40～90 ℃, polyreaction is carried out under anoxic condition;
3) treat that monomer flow 1 transformation efficiency reaches at 40%～100% o'clock, based on every liter of step 2) reaction system, drip the monomer flow 2 of deoxygenation in advance continuously with 0.03～0.15 liter/hour speed, after monomer flow 2 dropwises, continue reaction 30～90 minutes, finish up to reaction.
The present invention with intermittence mini-emulsion polymerization compare, molecular weight distribution is narrower when the preparation high-molecular weight polymer, the content of emulsifying agent and co-stabilizer is lower in the polymkeric substance, improved the purity of polymerisate greatly, reduced the time branch rate that the nucleation period complicated in the RAFT mini-emulsion polymerization process accounts for whole polymerization process effectively, provide and adopted the synthetic method of mini-emulsion polymerization technology single stage method, thereby simplified the production technique of block polymer with block polymer of living features.
Embodiment
The present invention is the RAFT chain transfer agents with aequum, and co-stabilizer and a certain amount of styrene monomer mix formation homogeneous solution (monomer flow 1), add emulsifier aqueous solution then, stir after 10 minutes, and ultrasonication 15 minutes makes miniemulsion.Miniemulsion is moved into one mechanical stirring, prolong, N are housed
2In the reactor of inlet device and spout, heating in water bath remains on temperature of reaction.Logical N
2After the deoxygenation, add initiator, initiated polymerization, and under monomer flow 1 intended conversion rate, add residual monomer (monomer flow 2) continuously.After being added dropwise to complete, proceed polymerization, transform fully up to monomer, polymerization stops.After polymerization is finished, slowly cool to discharging after the room temperature, breakdown of emulsion, washing, drying, promptly get required polymkeric substance.
The general structure of RAFT chain-transfer agent of the present invention is as follows:
Wherein: the Z group is a Ben Yajiaji, and R comes from the optional alkyl or aryl that replaces.
Co-stabilizer is: long chain alkane or long chain aliphatic alcohol and hydrophobic polymers such as hexadecanol, stearyl alcohol such as n-Hexadecane, octadecane, eicosane, paraffin.Monomer flow 1 is one or more vinyl comonomer based on vinylbenzene.Comonomer is: any in vinyl-acetic ester, methyl acrylate, ethyl propenoate, n-butyl acrylate, the special butyl ester of vinylformic acid, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, dodecylacrylate, alpha-methyl styrene, isobornyl acrylate, Vinyl toluene, the t-butyl styrene or several mixtures.Emulsifying agent is: the compound of anionic emulsifier, cationic emulsifier, nonionic emulsifier or ionic emulsifying agent and nonionic emulsifier.Monomer flow 2 is: any in vinylbenzene or vinylbenzene and vinyl-acetic ester, methyl acrylate, ethyl propenoate, n-butyl acrylate, the special butyl ester of vinylformic acid, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, dodecylacrylate, alpha-methyl styrene, isobornyl acrylate, Vinyl toluene, the t-butyl styrene or several mixtures.
High shear field is to be provided by ultrasonic grinding machine, high-pressure homogenizer, super gravity field generating unit.
Embodiment 1
(co-stabilizer HD) adds the mixture that 20.0 gram vinylbenzene, 0.3 restrain the two thioesters (PEPDTA, RAFT reagent) of phenylacetic acid-1-phenylethyl alcohol, mixes the formation oil solution under magnetic agitation with 1.0 n-Hexadecanes that restrain; 1.0 gram sodium lauryl sulphate (SDS) are dissolved in the 75 gram water, form the aqueous solution; With oil solution and aqueous solution, stir after 10 minutes, give birth to KS-600 ultrasonic cell disruptor ultrasonication 15 minutes (70% output rating) with Ningbo section, make miniemulsion.Miniemulsion is moved into one mechanical stirring, prolong, N are housed
2In the reactor of inlet device and charging opening, reactor is placed water-bath, bath temperature remains on about 75 ℃.Logical N
2After the deoxygenation 0.5 hour, add the aqueous solution (0.08 gram Potassium Persulphate is dissolved in 5 gram water) of Potassium Persulphate, initiated polymerization.Treat that this stage transformation efficiency reaches at 45% o'clock, 42 gram deoxygenations 30 minutes vinylbenzene are dripped with the speed of 6.0 milliliters/hour (0.06 liters/hour, based on reaction system) enter reactor, monomer dropping finishes, continue reaction 60 minutes, slowly cool to discharging after the room temperature.
Embodiment 2
(co-stabilizer HD) adds the mixture that 20.0 gram vinylbenzene, 0.3 restrain the two thioesters (PEPDTA, RAFT reagent) of phenylacetic acid-1-phenylethyl alcohol, mixes the formation oil solution under magnetic agitation with 1.0 n-Hexadecanes that restrain; 1.0 gram sodium lauryl sulphate (SDS) are dissolved in the 75 gram water, form the aqueous solution; With oil solution and aqueous solution, stir after 10 minutes, give birth to KS-600 ultrasonic cell disruptor ultrasonication 15 minutes (70% output rating) with Ningbo section, make miniemulsion.Miniemulsion is moved into one mechanical stirring, prolong, N are housed
2In the reactor of inlet device and charging opening, reactor is placed water-bath, bath temperature remains on about 75 ℃.Logical N
2After the deoxygenation 0.5 hour, add the aqueous solution (0.08 gram Potassium Persulphate is dissolved in 5 gram water) of Potassium Persulphate, initiated polymerization.Treat that this stage transformation efficiency reaches at 62% o'clock, 42 gram deoxygenations 30 minutes vinylbenzene are dripped with the speed of 7.0 milliliters/hour (0.07 liters/hour, based on reaction system) enter reactor, monomer dropping finishes, continue reaction 60 minutes, slowly cool to discharging after the room temperature.
Embodiment 3
(co-stabilizer HD) adds the mixture that 20.0 gram vinylbenzene, 0.3 restrain the two thioesters (PEPDTA, RAFT reagent) of phenylacetic acid-1-phenylethyl alcohol, mixes the formation oil solution under magnetic agitation with 1.0 n-Hexadecanes that restrain; 1.0 gram sodium lauryl sulphate (SDS) are dissolved in the 75 gram water, form the aqueous solution; With oil solution and aqueous solution, stir after 10 minutes, give birth to KS-600 ultrasonic cell disruptor ultrasonication 15 minutes (70% output rating) with Ningbo section, make miniemulsion.Miniemulsion is moved into one mechanical stirring, prolong, N are housed
2In the reactor of inlet device and charging opening, reactor is placed water-bath, bath temperature remains on about 75 ℃.Logical N
2After the deoxygenation 0.5 hour, add the aqueous solution (0.08 gram Potassium Persulphate is dissolved in 5 gram water) of Potassium Persulphate, initiated polymerization.Treat that this stage transformation efficiency reaches at 80% o'clock, 72.3 gram deoxygenations 30 minutes vinylbenzene are dripped with the speed of 11.0 milliliters/hour (0.11 liters/hour, based on reaction system) enter reactor, monomer dropping finishes, continue reaction 60 minutes, slowly cool to discharging after the room temperature.
Embodiment 4
(co-stabilizer HD) adds the mixture that 20.0 gram vinylbenzene, 0.3 restrain the two thioesters (PEPDTA, RAFT reagent) of phenylacetic acid-1-phenylethyl alcohol, mixes the formation oil solution under magnetic agitation with 1.0 n-Hexadecanes that restrain; 1.0 gram sodium lauryl sulphate (SDS) are dissolved in the 75 gram water, form the aqueous solution; With oil solution and aqueous solution, stir after 10 minutes, give birth to KS-600 ultrasonic cell disruptor ultrasonication 15 minutes (70% output rating) with Ningbo section, ⊙ makes miniemulsion.Miniemulsion is moved into one mechanical stirring, prolong, N are housed
2In the reactor of inlet device and charging opening, reactor is placed water-bath, bath temperature remains on about 50 ℃.Logical N
2After the deoxygenation 0.5 hour, add the aqueous solution (0.08 gram Potassium Persulphate is dissolved in 5 gram water) of Potassium Persulphate, initiated polymerization.Treat that this stage transformation efficiency reaches at 80% o'clock, 38.0 gram deoxygenations 30 minutes vinylbenzene are dripped with the speed of 4.0 milliliters/hour (0.04 liters/hour, based on reaction system) enter reactor, monomer dropping finishes, continue reaction 60 minutes, slowly cool to discharging after the room temperature.
Embodiment 5
(co-stabilizer HD) adds 7.0 gram vinylbenzene, and the mixture of 13.0 gram methyl methacrylates and 0.3 gram phenylacetic acid-1-phenylethyl alcohol pair thioesters (PEPDTA, RAFT reagent) mixes under magnetic agitation, forms oil solution with 1.0 n-Hexadecanes that restrain; 1.0 gram sodium lauryl sulphate (SDS) are dissolved in the 75 gram water, form the aqueous solution; With oil solution and aqueous solution, stir after 10 minutes, give birth to KS-600 ultrasonic cell disruptor ultrasonication 15 minutes (70% output rating) with Ningbo section, make miniemulsion.Miniemulsion is moved into one mechanical stirring, prolong, N are housed
2In the reactor of inlet device and charging opening, reactor is placed water-bath, bath temperature remains on about 60 ℃.Logical N
2After the deoxygenation 0.5 hour, add the aqueous solution (0.08 gram Potassium Persulphate is dissolved in 5 gram water) of Potassium Persulphate, initiated polymerization.Treat that this stage transformation efficiency reaches at 100% o'clock, 41.3 gram deoxygenations 30 minutes vinylbenzene are dripped with the speed of 6.0 milliliters/hour (0.06 liters/hour, based on reaction system) enter reactor, monomer dropping finishes, continue reaction 60 minutes, slowly cool to discharging after the room temperature.
Embodiment 6 (Comparative Examples)
(co-stabilizer HD) adds the mixture that 20.0 gram vinylbenzene, 0.09 restrain the two thioesters (PEPDTA, RAFT reagent) of phenylacetic acid-1-phenylethyl alcohol, mixes the formation oil solution under magnetic agitation with 1.0 n-Hexadecanes that restrain; 1.0 gram sodium lauryl sulphate (SDS) are dissolved in the 75 gram water, form the aqueous solution; With oil solution and aqueous solution, stir after 10 minutes, give birth to KS-600 ultrasonic cell disruptor ultrasonication 15 minutes (70% output rating) with Ningbo section, make miniemulsion.Miniemulsion is moved into one mechanical stirring, prolong, N are housed
2In the reactor of inlet device and charging opening, reactor is placed water-bath, bath temperature remains on about 75 ℃.Logical N
2After the deoxygenation 0.5 hour, add the aqueous solution (0.03 gram Potassium Persulphate is dissolved in 5 gram water) of Potassium Persulphate, initiated polymerization.After polymerization finished, slowly cool to discharging after the room temperature.
Polymer performance
| Embodiment | (* 10 for the product number-average molecular weight 4g/mol) | The molecular weight of product distribution coefficient | The remaining % of SDS/HD in the product |
| 1 | 4.2 | 1.33 | 1.7/1.7 |
| 2 | 6.0 | 1.28 | 1.8/1.8 |
| 3 | 8.0 | 1.33 | 1.5/1.5 |
| 4 | 4.9 | 1.28 | 1.5/1.5 |
| 5 | 5.0 | 1.31 | 1.8/1.8 |
| 6 | 5.10 | 2.05 | 5/5 |
Wherein: molecular weight and molecular weight distribution are that standard specimen records by the gel chromatography polystyrene.
Claims (6)
1. high molecular, the preparation method of narrow molecular weight distributions polystyrene and multipolymer thereof is characterized in that, the step of method is as follows:
1) 0.1～10 part of RAFT chain-transfer agent and 1～20 part of co-stabilizer and 50～200 parts of styrene monomers are mixed, form monomer flow 1 oil solution; 1～20 part of emulsifiers dissolve in 300～500 parts of water, is formed the aqueous solution; After monomer flow 1 oil solution and aqueous solution, under mechanical stirring, after the high shear field effect, pulverize, make miniemulsion;
2) miniemulsion is moved into reactor, feed nitrogen after 30～60 minutes, add the aqueous solution of water soluble starter, initiated polymerization, the temperature of polyreaction is 40～90 ℃, polyreaction is carried out under anoxic condition;
3) treat that monomer flow 1 transformation efficiency reaches at 40%～100% o'clock, based on every liter of step 2) reaction system, drip the monomer flow 2 of deoxygenation in advance continuously with 0.03～0.15 liter/hour speed, after monomer flow 2 dropwises, continue reaction 30～90 minutes, finish up to reaction.
2. a kind of high molecular according to claim 1, the preparation method of narrow molecular weight distributions polystyrene and multipolymer thereof is characterized in that, the general structure of said RAFT chain-transfer agent is as follows:
Wherein: the Z group is a Ben Yajiaji, and R comes from the optional alkyl or aryl that replaces.
3. a kind of high molecular according to claim 1, the preparation method of narrow molecular weight distributions polystyrene and multipolymer thereof is characterized in that, said co-stabilizer is: n-Hexadecane, octadecane, eicosane, paraffin, hexadecanol or stearyl alcohol.
4. a kind of high molecular according to claim 1, the preparation method of narrow molecular weight distributions polystyrene and multipolymer thereof, it is characterized in that said emulsifying agent is: the compound of anionic emulsifier, cationic emulsifier, nonionic emulsifier or ionic emulsifying agent and nonionic emulsifier.
5. a kind of high molecular according to claim 1, the preparation method of narrow molecular weight distributions polystyrene and multipolymer thereof, it is characterized in that said monomer flow 2 is: vinylbenzene or vinylbenzene and vinyl-acetic ester, methyl acrylate, ethyl propenoate, n-butyl acrylate, the special butyl ester of vinylformic acid, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, dodecylacrylate, alpha-methyl styrene, isobornyl acrylate, Vinyl toluene, in the t-butyl styrene any or several mixtures.
6. a kind of high molecular according to claim 1, the preparation method of narrow molecular weight distributions polystyrene and multipolymer thereof is characterized in that, said high shear field is that ultrasonic grinding machine, high-pressure homogenizer or super gravity field generating unit provide.
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| US20100136353A1 (en) | 2007-04-05 | 2010-06-03 | Michael Arnoldus Jacobus Schellekens | Aqueous oligomer / polymer emulsion with cationic functionality |
| CN101880364A (en) * | 2010-06-25 | 2010-11-10 | 浙江大学 | Styrene/butadiene amphiphilic block copolymer nano rubber latex and preparation method thereof |
| CN106281147B (en) * | 2016-08-15 | 2018-02-02 | 浙江大学 | A kind of water base binders for electrodes and preparation method |
| CN106433530B (en) * | 2016-09-19 | 2018-04-27 | 浙江大学 | A kind of sulphur cathode water base binders for electrodes and preparation method |
| CN109722190B (en) * | 2018-12-25 | 2021-01-19 | 浙江中科立德新材料有限公司 | Preparation method of lithium battery silicon-based negative electrode binder and binder thereof |
| CN113999614A (en) * | 2021-11-29 | 2022-02-01 | 国网山东省电力公司电力科学研究院 | High-solid anticorrosive paint with adjustable film forming property, and preparation method and application thereof |
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