CN113150190A - Copper wire-tertiary amine oxide redox initiation system suitable for unsaturated monomer free radical polymerization in aqueous solution and application - Google Patents
Copper wire-tertiary amine oxide redox initiation system suitable for unsaturated monomer free radical polymerization in aqueous solution and application Download PDFInfo
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- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
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Abstract
The invention belongs to the technical field of free radical polymerization, and particularly relates to a copper wire-tertiary amine oxide redox initiation system suitable for free radical polymerization of unsaturated monomers in an aqueous solution and application thereof, wherein the copper wire-tertiary amine oxide redox initiation system comprises a copper wire and tertiary amine oxide. The initiation system initiates free radical polymerization of acryloyl or N, N-dimethylacrylamide in aqueous solution at 50-70 ℃ in air atmosphere to obtain the high polymer. The invention has simple operation and low external requirement, and the used raw materials are cheaper and easy to purchase and are stable to air moisture. The polymerization is smooth and free of implosion or crosslinking. The copper wire is taken out after polymerization, the residual amount of copper ions in the solution or the polymerization product is low, and copper salt does not need to be removed.
Description
Technical Field
The invention belongs to the technical field of free radical polymerization, and particularly relates to a copper wire-tertiary amine oxide redox initiation system suitable for unsaturated monomer free radical polymerization in an aqueous solution and application thereof.
Background
Tertiary amine can be oxidized into tertiary amine oxide by oxygen, hydrogen peroxide and the like, and the latter can be generally used as a solvent (for example, a method for thermally pre-oxidizing a polymer by using a tertiary amine oxide solvent disclosed in Chinese patent CN 110923852A), an emulsifier (for example, a method for preparing hydrogenated rubber by using an adjustable reverse emulsion system disclosed in Chinese patent CN 111072793B), an anti-aging agent (for example, an anti-yellowing flame-retardant polyamide Composition disclosed in Chinese patent CN110229514A and a preparation method thereof), a dispersion stabilizer (for example, Composition stabilizing fine solid fibers disclosed in International patent PCTAT 9800147), a cellulose processing aid (for example, flame-retardant cellulose rayon disclosed in Chinese patent CN 111315924A; and a Process for making cellulose fibers, fibers or fibers disclosed in U.S. Pat. No. 20090127750A 1) and the like.
However, tertiary amine oxides, as a single oxygen-atom donor (OAT), may also participate in chemical reactions in some cases. For example, N-Dimethylaniline Oxide (DMAO) can form a redox initiation System with cobalt (II) acetate and p-toluenesulfonyl Chloride, respectively, to initiate free radical Polymerization to obtain a high molecular polymer (T.Sato and T Otsu Vinyl Polymerization initiator with dimethyl laniline N-Oxide and Metal Salts diene Makromolekulare Chemie 1969,125, 1-14; T.Sato and T Otsu Vinyl Polymerization initiator by the dimethyl laniline N-Oxide/Tosyl Chloride System Die methyl alcohol Chemical 1972,153,47-55.) certain transition Metal Salts can form an oxidative complex with high activity of tertiary amine Oxide OAT, catalytically oxidize hydrocarbons to alcohols, aldehydes, epoxy compounds, etc. (R.H.Holm Metal Oxide reaction 1449, reaction 1449).
Jixiujie et al adopt I2Tertiary amine oxide is a composite system, which catalyzes a series of benzyl alcohol oxidation of hydrogen peroxide into ketone or ether, and the tertiary amine oxide can play two roles of an emulsifier and a catalyst (Jixigj. o-nitro promoted selective deacylation and deacylation reaction and iodine, tertiary amine oxide double-catalyzed green new reaction of hydrogen peroxide benzyl alcohol preliminary research [ D]Tianjin university, 2007). While some long carbon chain tertiary amine oxides may play three roles as emulsifiers, co-initiators and free radical scavengers (Zhao Xin Lin, tertiary amine oxide active emulsions)Investigation of polymerization System [ D]University of great graduate, 2007 Zingiber zerumbet study of photoinitiated emulsion polymerization based on tertiary amine oxide [ D]University of major graduate, 2015).
In an aqueous solution system, due to the limitation of a redox initiation system, unsaturated monomer polymerization has the defects of implosion and difficult control of molecular weight, such as PAAm and PDMAAm prepared by polymerization of AAm and DMAAm in an aqueous solution, and concrete thickener prepared by copolymerization of unsaturated amide small monomer, unsaturated hydroxy ester small monomer and unsaturated sulfonic acid small monomer.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a copper wire-tertiary amine oxide redox initiation system suitable for unsaturated monomer free radical polymerization in aqueous solution and application thereof. In the invention, the most common water-soluble aliphatic tertiary amine, N, N-Dimethylaminoethanol (DMAE), is oxidized by hydrogen peroxide to obtain an aqueous solution of an oxide thereof, which is marked as DMAEO, and the aqueous solution and a copper wire form a redox initiation system. The redox initiation system initiates free radical polymerization of unsaturated small monomers such as acrylamide (AAm), N-dimethylacrylamide (DMAAm) or Methyl Methacrylate (MMA) in an aqueous solution, and a high molecular weight polymer can be obtained through reaction. The method can obtain the polymer with only amino end groups, the copper wires are taken out after the reaction, and the residual catalyst in the reaction solution or the polymer can be ignored.
In order to realize the purpose of the invention, the adopted technical scheme is as follows: a copper wire-tertiary amine oxide redox initiation system suitable for unsaturated monomer free radical polymerization in aqueous solution comprises copper wire and tertiary amine oxide.
Use of a copper wire-tertiary amine oxide redox initiation system as described above suitable for the free radical polymerisation of unsaturated monomers in aqueous solution, said unsaturated monomers not being polymers containing double bonds.
Further, the method comprises the step of carrying out free radical polymerization reaction on the unsaturated monomer in an aqueous solvent under the combined action of a redox initiation system consisting of copper wires and tertiary amine oxide.
A method of free radical polymerization of unsaturated monomers comprising the steps of:
the aqueous solution of the unsaturated monomer is added into a reaction vessel containing an aqueous solvent and the copper wire-tertiary amine oxide redox initiation system suitable for radical polymerization of the unsaturated monomer in the aqueous solution, and the mixture is reacted at an initiation temperature while stirring.
Further, the amount of the tertiary amine oxide is 15-45% of the total molar amount of the unsaturated monomers.
Further, the unsaturated monomer is one of acrylamide or N, N-dimethylacrylamide.
Further, if the unsaturated monomer is a solid at normal temperature, such as acrylamide, it is prepared into an aqueous solution; if the unsaturated monomer is liquid at normal temperature, for example, N-dimethylacrylamide, the unsaturated monomer can be directly used, and the unsaturated monomer is added into the reaction system at one time.
The reaction process of the invention is that copper wire and DMAEO form an initiation system, and AAm and DMAAm are initiated to polymerize in aqueous solution to obtain PAAm and PDMAAm.
Compared with the prior art, the invention has the advantages that: the invention has simple operation and low external requirement, and the used raw materials are cheaper and easy to purchase and are stable to air moisture. The polymerization is smooth and free of implosion or crosslinking. The copper wire is taken out after polymerization, the residual amount of copper ions in the solution or the polymerization product is low, and copper salt does not need to be removed.
Drawings
FIG. 1 shows the principle of the DMAEO preparation of the invention.
Detailed Description
The present invention is not limited to the following embodiments, and those skilled in the art can implement the present invention in other embodiments according to the disclosure of the present invention, or make simple changes or modifications on the design structure and idea of the present invention, and fall into the protection scope of the present invention. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The invention is described in more detail below with reference to the following examples:
when AAm or DMAAm is used as a polymerization monomer, the reaction temperature is 50-70 ℃.
The specific operation steps are as follows:
(1) DMAEO solution preparation (see FIG. 1)
DMAE is oxidized by catalyzing oxydol at 60-70 ℃ through ethylenediaminetetraacetic acid tetrasodium (EDTA & 4Na), and a DMAEO aqueous solution with the concentration of 40 wt.% is obtained.
(2) Separation of polymerization process from polymer
Taking a set amount of DMAEO aqueous solution prepared in the step (1) as an initiator mother solution, adding the DMAEO aqueous solution into a 50mL flask, adding deionized water, 1mL of N, N-Dimethylformamide (DMF) as an internal standard, and adding an AAm aqueous solution ([ AAm ]]05M) or DMAAm, adding copper wire (diameter is 1.0mm) and a magnetic rotor, reacting in a water bath at a set temperature, stopping the reaction after the reaction is finished, measuring the monomer conversion rate by a gas chromatography internal standard method, separating out a polymer, and drying to obtain PAAm or PDMAAm.
(3) Molecular weight measurement
For PAAm and PDMAAm, the viscosity average molecular weight of the polymer is determined by the viscosity method. The molecular weight of the obtained copolymer sample is measured by a single-point viscosity method, and the method comprises the following specific steps: 0.50-0.70g of the dried polymer was weighed, dissolved in deionized water to prepare 100mL of an aqueous polymer solution, and the flow-out times of the deionized water and the polymer solution were measured at a water bath temperature of 30 ℃ using an Ubbelohde viscometer, respectively. The intrinsic viscosity ([ eta ]) of the polymer was calculated according to the following formula:
the polymer viscosity average molecular weight was then calculated from the Mark-Houwink equation as follows:
[η]＝kMν α (2)
wherein for PAAm the test temperature is 30 ℃, k is 0.00631mL g-1, α is 0.8; for PDMAAm, the test temperature was 40 ℃, k 0.02, α 0.65(M.Kurata, X Tsunashima, Viscosity-molecular weight relationships and unperturbed dimensions of line chain molecules, in Polymer Handbook,4th Edition; eds: J.Brandrep, E.H.Immergut, E.A.Grulke; Wiley, Pergamon, 2003; VII/10).
The present invention is further described in detail below with reference to specific examples, which are intended to illustrate the invention and not to limit or narrow the scope thereof.
The DMAEO solutions in the following examples were prepared in step (1) above, the copper wires having a diameter of 1 cm.
Example 1:
measuring 2mL of DMAEO solution, 10mL of AAm aqueous solution, 4mL of deionized water and 1mL of DMF as internal standards, adding 1cm of copper wire, reacting for 4.5h at 60 ℃, wherein the conversion rate is 82%, taking out the polymer, drying, and determining the PAAm to be 6.38 multiplied by 10 by a viscosity method4。
Example 2:
measuring 4mL of DMAEO solution, 10mL of AAm aqueous solution, 2mL of deionized water and 1mL of DMF as internal standards, adding 1cm of copper wire, reacting for 4.5h at 60 ℃, wherein the conversion rate is 85%, taking out the polymer, drying, and determining the PAAm to be 6.17 × 10 by a viscosity method4。
Example 3:
6mL of DMAEO solution, 10mL of AAm aqueous solution, 0mL of deionized water and 1mL of DMF are measured as internal standards, 1cm of copper wire is added, the mixture reacts for 4.5 hours at the temperature of 60 ℃, the conversion rate is 93 percent, and the polymer is taken out to be detected. PAAm 5.80 × 10 determined by viscosity method4。
Example 4:
measuring 4mL of DMAEO solution, 10mL of AAm aqueous solution, 2mL of deionized water and 1mL of DMF as internal standards, adding 0.5cm of copper wire, reacting for 5.0h at 60 ℃, wherein the conversion rate is 96%, taking out the polymer, drying, and determining the PAAm to be 6.52 x 10 by a viscosity method4。
Example 5:
measuring and measuring4mL of DMAEO solution, 10mL of AAm aqueous solution, 2mL of deionized water and 1mL of DMF as internal standards, 0.2cm of copper wire is added, the mixture reacts for 5.0h at the temperature of 60 ℃, the conversion rate is 87 percent, and the PAAm obtained by taking out and drying the polymer and determining the PAAm by a viscosity method is 8.23 multiplied by 104。
Example 6:
measuring 4mL of DMAEO solution, 10mL of AAm aqueous solution, 2mL of deionized water and 1mL of DMF as internal standards, adding 0.1cm of copper wire, reacting for 5.0h at 60 ℃, wherein the conversion rate is 89%, taking out the polymer, drying, and determining the PAAm to be 9.43 x 10 by a viscosity method4。
Example 7:
measuring 4mL of DMAEO solution, 10mL of AAm aqueous solution, 2mL of deionized water and 1mL of DMF as internal standards, adding 1.0cm of copper wire, reacting for 5.0h at 50 ℃, wherein the conversion rate is 51%, taking out the polymer, drying, and determining the PAAm to be 9.91 multiplied by 10 by a viscosity method4。
Example 8:
measuring 4mL of DMAEO solution, 10mL of AAm aqueous solution, 2mL of deionized water and 1mL of DMF as internal standards, adding 1.0cm of copper wire, reacting for 5.0h at 70 ℃, wherein the conversion rate is 87%, taking out the polymer, drying, and determining the PAAm to be 4.79 multiplied by 10 by a viscosity method4。
Example 9:
measuring 4mL of DMAEO solution, 10mL of DMAAm, 2mL of deionized water and 1mL of DMF as internal standards, adding 1.0cm of copper wire, reacting for 5.0h at 60 ℃, wherein the conversion rate is 81%, taking out the polymer, drying, and determining by a viscosity method to obtain 2.15 multiplied by 10 PDAAm5。
Example 10:
measuring 6mL of DMAEO solution, 10mL of DMAAm, 0mL of deionized water and 1mL of DMF as internal standards, adding 1.0cm of copper wire, reacting for 5.0h at 60 ℃, obtaining a conversion rate of 86%, taking out the polymer, drying, and determining by a viscosity method to obtain 1.05 multiplied by 10 PDAAm5。
Example 11:
6mL of DMAEO solution, 10mL of DMAAm, 0mL of deionized water and 1mL of DMF are measured and taken as internal standards, 1.0cm of copper wire and 25 mu M of CuSO are added4Reacting tri- (N, N-dimethylaminoethyl) amine at 60 ℃ for 5.0h with the conversion rate of 65 percent, taking out the polymer and dryingThe PDAAm obtained by measuring by a viscosity method is 1.07 multiplied by 105。
Comparative example 1:
4mL of DMAEO solution, 10mL of AAm aqueous solution, 2mL of deionized water and 1mL of DMF are taken as internal standards and reacted for 5.0h at 60 ℃, and the conversion rate is 0.
Comparative example 2:
4mL of DMAE solution, 10mL of AAm aqueous solution, 2mL of deionized water and 1mL of DMF are measured as internal standards, and hydrogen peroxide aqueous solution ([ H ]2O2]00.01M), reaction at 60 ℃ for 5.0h, conversion 0.
Comparative example 3:
4mL of DMAE solution, 10mL of AAm aqueous solution, 2mL of deionized water and 1mL of DMF are measured as internal standards, and hydrogen peroxide aqueous solution ([ H ]2O2]00.01M), 1.0cm copper wire, at 60 ℃ for 5.0h, with a conversion of 0.
Comparative example 4:
6mL of DMAEO solution, 10mL of MMA and 8mL of ethanol were measured, 5.0cm of copper wire was added, and the reaction was carried out at 60 ℃ for 6 hours with a conversion of about 0.
Comparative example 5:
6mL of DMAEO solution, 10mL of MMA and 8mL of ethanol were weighed out, and 5.0cm of copper wire was added to the mixture to react at 80 ℃ for 6 hours. The precipitated polymer was dried and weighed to give a conversion of about 10%, and the number average molecular weight of the PMMA thus obtained was measured to be 4.70X 104Weight average molecular weight of 9.72X 104The polydispersity was 2.07.
Comparative example 6:
6mL of DMAEO solution, 10mL of MMA and 8mL of dimethyl sulfoxide were measured, 5.0cm of copper wire was added, and the reaction was carried out at 60 ℃ for 6 hours with a conversion of about 0.
Comparative example 7:
6mL of DMAEO solution, 10mL of MMA and 8mL of dimethyl sulfoxide were measured, 5.0cm of copper wire was added, and the reaction was carried out at 80 ℃ for 6 hours with a conversion of about 0.
In addition, experiments prove that the copper wire is an essential additive in the oxygen reduction initiation system provided by the invention, and if the copper wire is only a DMAEO solution, the free radical polymerization reaction is not initiated. When copper wires are replaced by copper powder, only the oxidation reaction of DMAEO on the copper powder occurs, the color quickly turns blue, but the free radical polymerization reaction is not initiated.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and their concepts should be equivalent or changed within the technical scope of the present invention.
Claims (7)
1. A copper wire-tertiary amine oxide redox initiation system suitable for unsaturated monomer free radical polymerization in aqueous solution is characterized in that: including copper wires and tertiary amine oxides.
2. Use of a copper wire-tertiary amine oxide redox initiation system suitable for radical polymerization of unsaturated monomers in aqueous solution according to claim 1, characterized in that: for the free-radical polymerization of unsaturated monomers in aqueous solution, which are not polymers containing double bonds.
3. Use of a copper wire-tertiary amine oxide redox initiation system suitable for radical polymerization of unsaturated monomers in aqueous solution according to claim 2, characterized in that: comprises the step of carrying out free radical polymerization reaction on the unsaturated monomer under the combined action of a redox initiation system consisting of copper wires and tertiary amine oxide in water.
4. A process for the free radical polymerization of unsaturated monomers, characterized by: the method comprises the following steps:
a process for radical polymerization of unsaturated monomers in aqueous solution, comprising adding an aqueous solution of said unsaturated monomers to a reaction vessel containing water and a redox initiation system for copper wire-tertiary amine oxide suitable for radical polymerization of unsaturated monomers in aqueous solution according to claim 1, and carrying out the radical polymerization reaction at an initiation temperature while stirring.
5. The unsaturated monomer radical polymerization process of claim 4, characterized in that: the amount of the tertiary amine oxide is 15-45% of the total molar amount of the unsaturated monomers.
6. The unsaturated monomer radical polymerization process of claim 4, characterized in that: the unsaturated monomer is one of acrylamide or N, N-dimethylacrylamide.
7. The unsaturated monomer radical polymerization process of claim 4, characterized in that: preparing an unsaturated monomer which is solid at normal temperature into an aqueous solution, and adding the aqueous solution into a reaction system at one time; the unsaturated monomer which is liquid at normal temperature is directly used and added into the reaction system at one time.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130245216A1 (en) * | 2010-07-23 | 2013-09-19 | The Trustees Of The University Of Pennsylvania | Set-lrp polymerization of acrylates in the presence of acids |
| CN103497293A (en) * | 2013-10-10 | 2014-01-08 | 河北工业大学 | Method for preparing DMAEMA based amphiphilic block copolymer through single electron transfer living free radical polymerization |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20130245216A1 (en) * | 2010-07-23 | 2013-09-19 | The Trustees Of The University Of Pennsylvania | Set-lrp polymerization of acrylates in the presence of acids |
| CN103497293A (en) * | 2013-10-10 | 2014-01-08 | 河北工业大学 | Method for preparing DMAEMA based amphiphilic block copolymer through single electron transfer living free radical polymerization |
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| 汤鑫焱等: "一种新的活性自由基聚合：单电子转移-活性自由基聚合", 《高分子通报》, no. 8, 31 August 2010 (2010-08-31), pages 85 - 91 * |
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| CN113603817A (en) * | 2021-08-16 | 2021-11-05 | 常州大学 | Copper wire-high molecular weight polymeric tertiary amine oxide redox initiation system and application |
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