CN102633700A - Preparation of water-soluble RAFT (reversible addition-fragmentation) chain transfer agent and synthesis method for polyacrylic acid with low molecular weight - Google Patents
Preparation of water-soluble RAFT (reversible addition-fragmentation) chain transfer agent and synthesis method for polyacrylic acid with low molecular weight Download PDFInfo
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- CN102633700A CN102633700A CN2012100931790A CN201210093179A CN102633700A CN 102633700 A CN102633700 A CN 102633700A CN 2012100931790 A CN2012100931790 A CN 2012100931790A CN 201210093179 A CN201210093179 A CN 201210093179A CN 102633700 A CN102633700 A CN 102633700A
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Abstract
The invention relates to preparation of active RAFT (reversible addition-fragmentation) chain transfer agent and a preparation method for polyacrylic acid with low molecular weight. The preparation method for the polyacrylic acid with the low molecular weight includes: in a reaction kettle, dispersing various reaction monomers into organic solvent and adding phase transfer catalyst to carry out a phase transfer reaction to synthesize trithiocarbonate RAFT reagent under the protection of gas; and carrying out free radical polymerization of acrylic monomers with prepared RAFT chain transfer agent and catalyst, and finally preparing the polyacrylic acid with the low molecular weight by controlling conditions such as reaction temperature, reaction time and the proportion of various substances. The preparation method for the polyacrylic acid has the advantages that water-soluble trithiocarbonate serving as the RAFT chain transfer agent is extremely easy in decomposition, therefore, chain transfer efficiency is high, free radical polymerization can be effectively controlled, yield of a product prepared by the phase transfer method is high, and the method is simple in process without excessive aftertreatment and easier to meet follow-up testing of an experiment. The prepared polyacrylic acid is low in relative molecular weight within the range of 30000-50000, narrow in molecular weight distribution and good in monodispersity.
Description
Technical field
The present invention relates to numerous areas such as household chemicals, coating, weaving, papermaking, agricultural, water treatment, especially relate to a kind of compound method of preparation and low-molecular-weight polypropylene acid of water-soluble RAFT chain-transfer agent.
Background technology
ROHM is because it has good water-solubility, and good dispersion, flocculation, thickening power, and be widely used this year.Characteristics such as that lightly crosslinked ROHM has is nontoxic, physiologically acceptable, environmental friendliness have broad application prospects at biomedicine field, and in addition, the characteristics that its thickening capabilities is strong, electric conductivity is high are greatly improved battery performance, cause great concern.Ultra-high molecular weight (10
7More than) be mainly used in water-retaining agent, HMW (10
6～10
7) be mainly used in flocculation aspect, intermediate molecular weight (10
4～10
6) having thickening effectiveness, lower molecular weight (500～5000) has the good distribution effect.In addition, ROHM also often is used as the Scale inhibitors of industrial circulating cooling water.
Mostly polyacrylic traditional preparation process method is solution polymerization, and radical polymerization directly takes place in water monomer.But because the polymerization activity of Acrylic Acid Monomer is big, can emit a large amount of heat usually in its polymerization process, the autoacceleration polymerization occur, cause polymerization system viscosity to raise, it is crosslinked to be prone to implode, and the ROHM relative molecular weight of generation is big and distribute very wide.Adopt " activity "/controllable free-radical polymerisation can realize monodispersed polyacrylic polymerization.Active free radical polymerization mainly contains at present: ATRP (ATRP), reversible addition-fragmentation chain transfer free radical polymerization (RAFT) and living free radical polymerization polymerization (NMP).Wherein the narrow and reaction conditions of living free radical polymerization monomer polymerized accommodation limits to some extent, seldom is used to the polymerization of acrylic monomer.
Lower molecular weight (5000～70,000) ROHM does not have ready-made commodity selling on market, the laboratory adopts RAFT radical polymerization to prepare voluntarily.The present invention has explored the RAFT legal system and has been equipped with low-molecular-weight polypropylene sour synthetic route and technology.The RAFT polymeric chain rate constant of propagation of vinylformic acid (AA) in the aqueous solution is very high, and very easily generates gel in the polymerization process, therefore wants to realize that controllable polymerization is very challenging.
Summary of the invention
The object of the invention is intended to be to overcome the shortcoming of above-mentioned prior art, provide a kind of simply, the compound method of preparation method and the low-molecular-weight polypropylene acid of water-soluble RAFT chain-transfer agent efficiently.
In the present invention; Three thioesters in traditional radical polymerization, have been added as chain-transfer agent; Through increasing the reversible chain transfer reaction between radical and the efficient chain-transfer agent, increase the concentration of radical in the controlled polymerization system, thereby realize " activity "/controlled purpose.And three thioesters have chain transfer effect preferably, and simple, the easy purifying of its preparation method.
Technical scheme of the present invention is following:
A kind of water-soluble RAFT chain-transfer agent preparation method, its step is following:
1) under the nitrogen protection, the adding mass fraction is in reaction kettle: 1～3 part of organic solvent, and 0.02～0.04 part of catalyzer adds reactant acetone, chloroform and dithiocarbonic anhydride, ice bath 1～3h;
2) after ice bath finishes, add 1～4 part of strong base solution, keep temperature to be no more than 25 ℃, stirring reaction 12h in this process;
3) add 5～10 parts of zero(ppm) water and 1～2 part of strong acid, continue to stir 0.5～1h;
4) collect product behind the filtration drying, after further purifying with acetone, obtain product;
Wherein: organic solvent is a kind of in benzene, hexanaphthene or the sherwood oil; Catalyzer is a kind of in Tetrabutyl amonium bromide or the TBAH;
The mass ratio of said reactant acetone, chloroform, dithiocarbonic anhydride is 3: 6: 2.
Described highly basic is preferably a kind of of KOH or NaOH.Described strong acid is preferably dense HCl or H
2SO
4A kind of.
Chain-transfer agent of the present invention prepares polyacrylic method, in reaction kettle, will be dissolved in 1～3 part of zero(ppm) water for 0.5～1 part in the Acrylic Acid Monomer of mass fraction, adds RAFT chain-transfer agent and 0.03～0.05 part of initiator of 0.05～0.1 part; At 65 ℃ of reaction 0.5～1h, be warming up to 80 ℃ of reaction 6～8h again under the nitrogen protection, obtain crude product, can obtain low-molecular-weight ROHM through the dialysis purifying.
Described initiator is preferably a kind of in Lucidol or the Diisopropyl azodicarboxylate.
Adopt water-soluble RAFT chain-transfer agent among the present invention; Very easily decompose, therefore have very high chain transfer efficiency, can control radical polymerization effectively; And the product productive rate that this phase transfer method makes is higher relatively; This method technology is simple, need not too much aftertreatment, more is prone to satisfy the follow-up test of this experiment.The ROHM relative molecular weight that makes is lower, and between 30000～5000, MWD is narrower, and monodispersity is better.
Description of drawings
Fig. 1: be the infrared spectrogram of PAA of preparation;
Fig. 2: be the GPC spectrogram of PAA.
Embodiment
Embodiment 1:
(1) preparation of RAFT chain-transfer agent
1) under the nitrogen protection, in reaction kettle, adds 1 part of benzene, 0.025 part of Tetrabutyl amonium bromide, 0.5 part in acetone, 1 part of chloroform, 0.3 part of dithiocarbonic anhydride, ice bath 1.5h.
2) after ice bath finishes, add 4 parts of NaOH solution, keep temperature to be no more than 25 ℃, stirring reaction 12h in this process.
3) add 10 parts of zero(ppm) water and 1 part of sulfuric acid, continue to stir 0.7h.
4) collect product behind the filtration drying, further obtain product behind the purification by liquid extraction.
(2) polyacrylic preparation
1) in reaction kettle, 1 part of Acrylic Acid Monomer is dissolved in 2 parts of zero(ppm) water, add RAFT chain-transfer agent and 0.04 part of initiator A IBN that 0.1 part of aforesaid method makes.
2) under the nitrogen protection at 65 ℃ of reaction 1h, be warming up to 80 ℃ of reaction 6h again, obtain crude product, molecular weight cut-off is that 100 dialysis tubing is removed small molecular weight impurity, the dialysis purifying obtains final product.
The ROHM sample of preparation appears faint yellow to khaki color, and strong thiol smell is arranged.Relative molecular weight is lower, and between 5000～10000, MWD is narrower, and monodispersity is better.
Embodiment 2:
(1) preparation of RAFT chain-transfer agent
1) under the nitrogen protection, in reaction kettle, adds 1.5 parts of benzene, 0.02 part of TBAH, 0.5 part in acetone, 1 part of chloroform, 0.3 part of dithiocarbonic anhydride, ice bath 1h.
2) after ice bath finishes, add 1 part of KOH solution, keep temperature to be no more than 25 ℃, stirring reaction 12h in this process.
3) add 5 parts of zero(ppm) water and 1 part of concentrated hydrochloric acid, continue to stir 1h.
4) collect product behind the filtration drying, further obtain product behind the purification by liquid extraction.
(2) polyacrylic preparation
1) in reaction kettle, 0.5 part of Acrylic Acid Monomer is dissolved in 2 parts of zero(ppm) water, add RAFT chain-transfer agent and 0.05 part of initiator B PO that 0.1 part of aforesaid method makes.
2) under the nitrogen protection at 65 ℃ of reaction 0.5h, be warming up to 80 ℃ of reaction 8h again, obtain crude product, molecular weight cut-off is that 100 dialysis tubing is removed small molecular weight impurity, the dialysis purifying obtains final product.
The ROHM sample of preparation appears faint yellow to khaki color, and strong thiol smell is arranged.Relative molecular weight is lower, and between 5000～10000, MWD is narrower, and monodispersity is better.
Embodiment 3:
(1) preparation of RAFT chain-transfer agent
1) under the nitrogen protection, in reaction kettle, adds 3 parts of benzene, 0.04 part of TBAH, 0.5 part in acetone, 1 part of chloroform, 0.3 part of dithiocarbonic anhydride, ice bath 3h.
2) after ice bath finishes, add 1 part of NaOH solution, keep temperature to be no more than 25 ℃, stirring reaction 12h in this process.
3) add 9 parts of zero(ppm) water and 2 parts of sulfuric acid, continue to stir 0.5h.
4) collect product behind the filtration drying, further obtain product behind the purification by liquid extraction.
(2) polyacrylic preparation
1) in reaction kettle, 0.75 part of Acrylic Acid Monomer is dissolved in 3 parts of zero(ppm) water, add RAFT chain-transfer agent and 0.05 part of initiator A IBN that 0.05 part of aforesaid method makes.
2) under the nitrogen protection at 65 ℃ of reaction 1h, be warming up to 80 ℃ of reaction 7h again, obtain crude product, molecular weight cut-off is that 100 dialysis tubing is removed small molecular weight impurity, the dialysis purifying obtains final product.
The ROHM sample of preparation appears faint yellow to khaki color, and strong thiol smell is arranged.Relative molecular weight is lower, and between 12000～16000, MWD is narrower, and monodispersity is better.
Embodiment 4:
(1) preparation of RAFT chain-transfer agent
1) under the nitrogen protection, in reaction kettle, adds 1 part of hexanaphthene, 0.025 part of TBAH, 0.5 part in acetone, 1 part of chloroform, 0.3 part of dithiocarbonic anhydride, ice bath 1h.
2) after ice bath finishes, add 2 parts of NaOH solution, keep temperature to be no more than 25 ℃, stirring reaction 12h in this process.
3) add 10 parts of zero(ppm) water and 1.5 parts of concentrated hydrochloric acids, continue to stir 0.7h.
4) collect product behind the filtration drying, further obtain product behind the purification by liquid extraction.
(2) polyacrylic preparation
1) in reaction kettle, 1 part of Acrylic Acid Monomer is dissolved in 1 part of zero(ppm) water, add RAFT chain-transfer agent and 0.04 part of initiator B PO that 0.075 part of aforesaid method makes.
2) under the nitrogen protection at 65 ℃ of reaction 0.5h, be warming up to 80 ℃ of reaction 6h again, obtain crude product, molecular weight cut-off is that 100 dialysis tubing is removed small molecular weight impurity, the dialysis purifying obtains final product.
The ROHM sample of preparation appears faint yellow to khaki color, and strong thiol smell is arranged.Relative molecular weight is lower, and between 20000～24000, MWD is narrower, and monodispersity is better.
Embodiment 5:
(1) preparation of RAFT chain-transfer agent
1) under the nitrogen protection, in reaction kettle, adds 1.5 parts of hexanaphthenes, 0.02 part of Tetrabutyl amonium bromide, 0.5 part in acetone, 1 part of chloroform, 0.3 part of dithiocarbonic anhydride, ice bath 3h.
2) after ice bath finishes, add 4 parts of KOH solution, keep temperature to be no more than 25 ℃, stirring reaction 12h in this process.
3) add 5 parts of zero(ppm) water and 1 part of concentrated hydrochloric acid, continue to stir 1h.
4) collect product behind the filtration drying, further obtain product behind the purification by liquid extraction.
(2) polyacrylic preparation
1) in reaction kettle, 0.75 part of Acrylic Acid Monomer is dissolved in 1 part of zero(ppm) water, add RAFT chain-transfer agent and 0.03 part of initiator A IBN that 0.05 part of aforesaid method makes.
2) under the nitrogen protection at 65 ℃ of reaction 0.5h, be warming up to 80 ℃ of reaction 8h again, obtain crude product, molecular weight cut-off is that 100 dialysis tubing is removed small molecular weight impurity, the dialysis purifying obtains final product.
The ROHM sample of preparation appears faint yellow to khaki color, and strong thiol smell is arranged.Relative molecular weight is lower, and between 10000～14000, MWD is narrower, and monodispersity is better.
Embodiment 6:
(1) preparation of RAFT chain-transfer agent
1) under the nitrogen protection, in reaction kettle, adds 3 parts of hexanaphthenes, 0.04 part of Tetrabutyl amonium bromide, 0.5 part in acetone, 1 part of chloroform, 0.3 part of dithiocarbonic anhydride, ice bath 1.5h.
2) after ice bath finishes, add 2 parts of KOH solution, keep temperature to be no more than 25 ℃, stirring reaction 12h in this process.
3) add 9 parts of zero(ppm) water and 2 parts of sulfuric acid, continue to stir 0.5h.
4) collect product behind the filtration drying, further obtain product behind the purification by liquid extraction.
(2) polyacrylic preparation
1) in reaction kettle, 0.5 part of Acrylic Acid Monomer is dissolved in 3 parts of zero(ppm) water, add RAFT chain-transfer agent and 0.03 part of initiator B PO that 0.075 part of aforesaid method makes.
2) under the nitrogen protection at 65 ℃ of reaction 1h, be warming up to 80 ℃ of reaction 7h again, obtain crude product, molecular weight cut-off is that 100 dialysis tubing is removed small molecular weight impurity, the dialysis purifying obtains final product.
The ROHM sample of preparation appears faint yellow to khaki color, and strong thiol smell is arranged.Relative molecular weight is lower, and between 27000～30000, MWD is narrower, and monodispersity is better.
Embodiment 7:
(1) preparation of RAFT chain-transfer agent
1) under the nitrogen protection, in reaction kettle, adds 1 part of sherwood oil, 0.025 part of TBAH, 0.5 part in acetone, 1 part of chloroform, 0.3 part of dithiocarbonic anhydride, ice bath 1h.
2) after ice bath finishes, add 2 parts of KOH solution, keep temperature to be no more than 25 ℃, stirring reaction 12h in this process.
3) add 5 parts of zero(ppm) water and 2 parts of concentrated hydrochloric acids, continue to stir 1h.
4) collect product behind the filtration drying, further obtain product behind the purification by liquid extraction.
(2) polyacrylic preparation
1) in reaction kettle, 0.5 part of Acrylic Acid Monomer is dissolved in 2 parts of zero(ppm) water, add RAFT chain-transfer agent and 0.05 part of initiator B PO that 0.1 part of aforesaid method makes.
2) under the nitrogen protection at 65 ℃ of reaction 0.5h, be warming up to 80 ℃ of reaction 8h again, obtain crude product, molecular weight cut-off is that 100 dialysis tubing is removed small molecular weight impurity, the dialysis purifying obtains final product.
Fig. 1 is the infrared spectrogram of the PAA of preparation, and the vibration peak of C=O is near 1700cm-1, and various CHx vibration performances peak is near 2910～2520cm-1,1450cm-1 and 1230cm-1; Two key stretching vibration absorption peaks at 1640cm-1 place and two bond bending vibration absorption peaks at 990cm-1 place a little less than, explain that double-bond polymerization is more complete, the product that the RAFT polymerization obtains is a ROHM.
Fig. 2 is the GPC spectrogram of PAA, can be drawn by figure: Mn=11013, and PDI=1.0707, the relative molecular weight distribution basic controlling of the ROHM aqueous solution is in 1.0～1.1 scope, and monodispersity is very good.
Embodiment 8:
(1) preparation of RAFT chain-transfer agent
1) under the nitrogen protection, in reaction kettle, adds 1.5 parts of sherwood oils, 0.025 part of Tetrabutyl amonium bromide, 0.5 part in acetone, 1 part of chloroform, 0.3 part of dithiocarbonic anhydride, ice bath 1.5h.
2) after ice bath finishes, add 2 parts of NaOH solution, keep temperature to be no more than 25 ℃, stirring reaction 12h in this process.
3) add 9 parts of zero(ppm) water and 1 part of concentrated hydrochloric acid, continue to stir 0.5h.
4) collect product behind the filtration drying, further obtain product behind the purification by liquid extraction.
(2) polyacrylic preparation
1) in reaction kettle, 0.75 part of Acrylic Acid Monomer is dissolved in 1 part of zero(ppm) water, add RAFT chain-transfer agent and 0.03 part of initiator A IBN that 0.05 part of aforesaid method makes.
2) under the nitrogen protection at 65 ℃ of reaction 0.5h, be warming up to 80 ℃ of reaction 8h again, obtain crude product, molecular weight cut-off is that 100 dialysis tubing is removed small molecular weight impurity, the dialysis purifying obtains final product.
The ROHM sample of preparation appears faint yellow to khaki color, and strong thiol smell is arranged.Relative molecular weight is lower, and between 22000～26000, MWD is narrower, and monodispersity is better.
Embodiment 9:
(1) preparation of RAFT chain-transfer agent
1) under the nitrogen protection, in reaction kettle, adds 3 parts of sherwood oils, 0.025 part of TBAH, 0.5 part in acetone, 1 part of chloroform, 0.3 part of dithiocarbonic anhydride, ice bath 3h.
2) after ice bath finishes, add 4 parts of NaOH solution, keep temperature to be no more than 25 ℃, stirring reaction 12h in this process.
3) add 10 parts of zero(ppm) water and 1.5 parts of sulfuric acid, continue to stir 0.7h.
4) collect product behind the filtration drying, further obtain product behind the purification by liquid extraction.
(2) polyacrylic preparation
1) in reaction kettle, 1 part of Acrylic Acid Monomer is dissolved in 1 part of zero(ppm) water, add RAFT chain-transfer agent and 0.04 part of initiator B PO that 0.075 part of aforesaid method makes.
2) under the nitrogen protection at 65 ℃ of reaction 0.5h, be warming up to 80 ℃ of reaction 6h again, obtain crude product, molecular weight cut-off is that 100 dialysis tubing is removed small molecular weight impurity, the dialysis purifying obtains final product.
The ROHM sample of preparation appears faint yellow to khaki color, and strong thiol smell is arranged.Relative molecular weight is lower, and between 18000～22000, MWD is narrower, and monodispersity is better.
Polyacrylic molecular weight and molecular weight distributing index that embodiment is made use gel chromatograph (GPC) to test.Test finds that the relative molecular weight distribution basic controlling of the ROHM aqueous solution is in 1.0～1.1 scope, and monodispersity is very good, has proved once more also that this reacts to be living polymerization.
Claims (6)
1. water-soluble RAFT chain-transfer agent preparation method is characterized in that step is following:
1) under the nitrogen protection, the adding mass fraction is in reaction kettle: 1～3 part of organic solvent, and 0.02～0.04 part of catalyzer adds reactant acetone, chloroform and dithiocarbonic anhydride, ice bath 1～3h;
2) after ice bath finishes, add 1～4 part of strong base solution, keep temperature to be no more than 25 ℃, stirring reaction 12h in this process;
3) add 5～10 parts of zero(ppm) water and 1～2 part of strong acid, continue to stir 0.5～1h;
4) collect product behind the filtration drying, after further purifying with acetone, obtain product;
Wherein: organic solvent is a kind of in benzene, hexanaphthene or the sherwood oil; Catalyzer is a kind of in Tetrabutyl amonium bromide or the TBAH.
2. chain-transfer agent Preparation Method as claimed in claim 1 is characterized in that described highly basic is a kind of of KOH or NaOH.
3. chain-transfer agent Preparation Method as claimed in claim 1, the mass ratio that it is characterized in that said reactant acetone, chloroform and dithiocarbonic anhydride is 3: 6: 2.
4. chain-transfer agent Preparation Method as claimed in claim 1 is characterized in that described strong acid is dense HCl or H
2SO
4A kind of.
5. adopt the chain-transfer agent of claim 1 to prepare polyacrylic method; It is characterized in that in reaction kettle; To be dissolved in 1～3 part of zero(ppm) water for 0.5～1 part in the Acrylic Acid Monomer of mass fraction, add RAFT chain-transfer agent and 0.03～0.05 part of initiator of 0.05～0.1 part; At 65 ℃ of reaction 0.5～1h, be warming up to 80 ℃ of reaction 6～8h again under the nitrogen protection, obtain crude product, can obtain low-molecular-weight ROHM through the dialysis purifying.
6. the polyacrylic method of preparation as claimed in claim 5 is characterized in that described initiator is a kind of in Lucidol or the Diisopropyl azodicarboxylate.
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Cited By (6)
| 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 |
| JPWO2015052804A1 (en) * | 2013-10-09 | 2017-03-09 | 株式会社 資生堂 | Low thread thickener and cosmetics containing the thickener |
| JP2019011380A (en) * | 2018-10-30 | 2019-01-24 | 株式会社 資生堂 | Low-stringiness thickener and cosmetic material admixed with said thickener |
| CN113929606A (en) * | 2021-09-23 | 2022-01-14 | 武汉海翎化学工业有限公司 | Trithioester chain transfer agent, low-molecular-weight sodium polyacrylate obtained by using same, application and preparation |
| CN114573122A (en) * | 2022-03-29 | 2022-06-03 | 广东天祺环保科技有限公司 | Preparation method of composite corrosion and scale inhibitor for water treatment |
| CN116217767A (en) * | 2023-02-07 | 2023-06-06 | 浙江理工大学 | Method for controlling linear luminous high molecular material with fluorescence and afterglow emission capability |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2015052804A1 (en) * | 2013-10-09 | 2017-03-09 | 株式会社 資生堂 | Low thread thickener and cosmetics containing the thickener |
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| CN113929606A (en) * | 2021-09-23 | 2022-01-14 | 武汉海翎化学工业有限公司 | Trithioester chain transfer agent, low-molecular-weight sodium polyacrylate obtained by using same, application and preparation |
| CN114573122A (en) * | 2022-03-29 | 2022-06-03 | 广东天祺环保科技有限公司 | Preparation method of composite corrosion and scale inhibitor for water treatment |
| CN116217767A (en) * | 2023-02-07 | 2023-06-06 | 浙江理工大学 | Method for controlling linear luminous high molecular material with fluorescence and afterglow emission capability |
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Application publication date: 20120815 |