CN113603817B - Copper wire-high molecular weight polymeric tertiary amine oxide redox initiation system and application - Google Patents
Copper wire-high molecular weight polymeric tertiary amine oxide redox initiation system and application Download PDFInfo
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Abstract
The invention belongs to the field of preparing high polymers, and relates to a copper wire-high molecular weight polymerization tertiary amine oxide redox initiation system and application thereof, wherein free radical polymerization of N, N-dimethylacrylamide is initiated at the temperature of 50-70 ℃ in an air atmosphere to obtain the high polymers, and the molecular weight of the obtained polymers is gradually increased along with the progress of polymerization and the improvement of monomer conversion rate. According to the redox system consisting of the high molecular weight polymeric tertiary amine oxide and the copper wire, whether the high molecular weight polymeric tertiary amine oxide participates in oxygen atom transfer or chain initiation or not in subsequent free radical polymerization, the high molecular weight polymeric tertiary amine oxide is a part of a high molecular chain, so that the toxicity can be greatly reduced.
Description
Technical Field
The invention belongs to the technical field of free radical polymerization, and particularly relates to a copper wire-high molecular weight polymeric tertiary amine oxide redox initiation system and application thereof.
Background
The small molecule tertiary amine can be oxidized into small molecule tertiary amine oxide by oxygen, hydrogen peroxide and the like, and forms a redox system with copper wires in aqueous solution to initiate the free radical polymerization of unsaturated monomers at 50-70 ℃ (Chinese patent application 202110389214.2). However, the initiating activity of the copper wire-tertiary amine oxide is low, so that a large excess amount of small-molecule tertiary amine oxide needs to be added, and a large amount of free small-molecule tertiary amine oxide or derivatives thereof (such as small-molecule tertiary amine with oxygen atoms removed) exist in a system after the polymerization reaction is finished. Small tertiary amines are generally toxic and therefore removal of the tertiary amine entrapped in the resulting polymer becomes necessary, which adds an additional process step.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a copper wire-high molecular weight polymeric tertiary amine oxide redox initiation system and application thereof. The invention firstly obtains high molecular weight polymeric tertiary amine, then the polymeric tertiary amine is oxidized by hydrogen peroxide to obtain an oxide thereof, which is marked as PDMAEMAO, and the oxide and copper wires form a redox initiation system. The redox initiation system initiates the polymerization of N, N-dimethylacrylamide (DMAAm) in aqueous solution to obtain a high molecular weight polymer. The copper wire is 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-high molecular weight polymeric tertiary amine oxide redox initiation system comprises a copper wire and PDMAEMAO, wherein the PDMAEMAO is prepared by the following methodObtaining: first, 2- (N, N-dimethylamino) ethyl methacrylate (DMAEMA) as a polymerizable tertiary amine was polymerized in an aqueous solution by radical polymerization to give a viscosity-average molecular weight of 3.0X 104-5.0×104Poly (2- (N, N-dimethylamino) ethyl methacrylate) (denoted PDMAEMA), which is subsequently oxidized with hydrogen peroxide to the corresponding high molecular weight polymeric tertiary amine oxide (denoted PDMAEMAO).
The application of the copper wire-high molecular weight polymeric tertiary amine oxide redox initiation system is used for initiating the free radical polymerization of N, N-dimethylacrylamide (DMAAm).
The specific method comprises the following steps:
n, N-dimethylacrylamide (DMAAm) was added to a reaction vessel containing deionized water, the copper-compatible high molecular weight polymeric tertiary amine oxide redox initiation system described above. To facilitate the determination of DMAAm conversion by gas chromatography, N-Dimethylformamide (DMF) may also be added and the reaction is carried out at an initiation temperature (preferably 50 to 70 ℃) with stirring.
Further, the amount of the high molecular weight polymeric tertiary amine oxide is 8.0 to 13.3% of the molar amount of DMAAm.
The reaction process of the invention is that copper wire and PDMAEMAO form an initiation system, and the homopolymerization of DMAAm is initiated in aqueous solution to obtain the copolymer of PDMAEMA-graft-PDMAAm (marked as PDMAEMA-g-PDMAAm).
Compared with the prior art, the invention has the advantages that:
the redox system composed of the high molecular weight polymeric tertiary amine oxide and the copper wire provided by the invention has the advantages that in the subsequent free radical polymerization, the high molecular weight polymeric tertiary amine oxide is a part of a high molecular chain no matter whether the high molecular weight polymeric tertiary amine oxide participates in oxygen atom transfer or chain initiation, so that the toxicity can be greatly reduced. On the other hand, since the polymerization is initiated by the side chain of the high molecular weight tertiary amine, the newly formed polymer chain will become one side chain of the original high molecular weight tertiary amine. Thus, a graft polymer was obtained. After multiple initiation, a highly branched polymer will be obtained and a gradual increase in the molecular weight of the polymer obtained as the polymerization proceeds will be achieved. The invention has simple operation, low external requirement, cheap and easily purchased raw materials and stable moisture in the air. The polymerization is smooth and free of violent polymerization or crosslinking. The copper wire is taken out after polymerization, so that the residual amount of copper ions in the solution or the polymerization product is low, and copper salt removal is not needed. Because each PDMEMAO chain contains multiple tertiary amine-oxide groups, multiple PDMAAm side chains can be initiated and thus the molecular weight of the polymer can be increased to some extent as the polymerization proceeds.
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FIG. 1 shows the principle of PDMAEMAO preparation.
FIG. 2 shows the principle of DMAAm polymerization initiated by copper wire-PDMAEMAO.
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 of the present invention may be combined with each other without conflict.
The invention is described in more detail below with reference to the following examples:
the specific operation steps are as follows:
(1) Preparation of PDMAEMAO solution
30mL DMAEMA and 70mL deionized water are weighed and fully mixed, and 8.0mL sodium persulfate aqueous solution (marked as NaPS, [ NaPS ") is slowly added into the mixed solution in a dropwise manner at room temperature]0= 1.0M) while stirring the mixed solution. And stopping dripping the NaPS aqueous solution if the temperature of the solution is too high, continuing dripping the NaPS aqueous solution after the temperature is reduced, and finishing dripping within about 30 min. And (3) cooling the temperature of the reaction liquid to room temperature to obtain the PDMAEMA aqueous solution. The viscosity average molecular weight of the PDMAEMA prepared by the method is 3.0 multiplied by 104-5.0×104. An aqueous solution of PDMAEMA was transferred to a 250mL flask, following DMAEMA: h2O2Is 1.0:1.1 ratio of 30wt.% H2O2Aqueous solution, naHCO was added at 1wt.% of DMAEMA3Reacting for 6-7 h at 75 ℃ by using the catalyst to obtain PDMAEMAOAn aqueous solution. The process is shown in figure 1.
(2) DMAAm polymerization initiated by copper wire-PDMAEMAO
A50 mL round bottom flask is added with PDMAEMAO solution required by experiment, 10mL DMAAm, 5mL deionized water and 2mL N, N-Dimethylformamide (DMF), a magnetic stirrer is placed, the mixture is transferred to a constant temperature water bath magnetic stirrer, and fresh stripped copper wires (the diameter is 1.0 mm) with different lengths are added to react at 50 ℃, 60 ℃ or 70 ℃ for different times, and the reaction process is shown in figure 2. And stopping the reaction after the reaction is finished, measuring the monomer conversion rate by a gas chromatography internal standard method, and separating out and drying the polymer to obtain the polymer.
(3) Molecular weight measurement
The viscosity average molecular weight of the obtained polymer was measured by the viscometry. 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 40 ℃ 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 k =0.02, α =0.65 (M.Kurata, X Tsunashima, viscosity-molecular weight relationships and unperturbed dimensions of linear chain molecules, in Polymer Handbook,4th edition: ed. J.Brandrup, 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.
Example 1:
taking 3mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 1cm of copper wire, reacting at 70 ℃ for 15min, wherein the DMAAm conversion rate is 3.0%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 5.29 multiplied by 105。
Example 2:
taking 3mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 1cm of copper wire, reacting for 30min at 70 ℃, enabling the DMAAm conversion rate to be 5.0%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 5.99 multiplied by 105。
Example 3:
measuring 3mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 1cm of copper wire, reacting for 60min at 70 ℃, wherein the DMAAm conversion rate is 36.0%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 6.86 multiplied by 105。
Example 4:
measuring 3mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 1cm of copper wire, reacting at 70 ℃ for 120min, wherein the DMAAm conversion rate is 53.5%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 7.76 multiplied by 105。
Example 5:
measuring 3mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 1cm of copper wire, reacting for 180min at 70 ℃, wherein the DMAAm conversion rate is 64.0%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 9.35 multiplied by 105。
Example 6:
measuring 3mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 1cm of copper wire, reacting at 70 ℃ for 240min, wherein the DMAAm conversion rate is 72.5%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 10.48 multiplied by 105。
Example 7:
measuring 3mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, and adding 1cm of the internal standardsReacting copper wire at 70 deg.C for 300min, DMAAm conversion rate of 74.0%, taking out polymer, oven drying, and determining molecular weight of PDMAAm by viscometry to obtain a product with molecular weight of 10.9 × 105。
Example 8:
measuring 4mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 1cm of copper wire, reacting at 70 ℃ for 15min, wherein the DMAAm conversion rate is 3.15%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 3.28 multiplied by 105。
Example 9:
measuring 4mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 1cm of copper wire, reacting for 30min at 70 ℃, enabling the DMAAm conversion rate to be 7.58%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 4.69 multiplied by 105。
Example 10:
measuring 4mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 1cm of copper wire, reacting for 60min at 70 ℃, wherein the DMAAm conversion rate is 34.07%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 5.72 multiplied by 105。
Example 11:
measuring 4mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 1cm of copper wire, reacting at 70 ℃ for 120min, wherein the DMAAm conversion rate is 57.77%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 6.56 multiplied by 105。
Example 12:
measuring 4mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 1cm of copper wire, reacting at 70 ℃ for 180min, wherein the DMAAm conversion rate is 68.49%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 7.77 x 105。
Example 13:
measuring 4mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 1cm of copper wire, reacting at 70 ℃ for 240min, wherein the DMAAm conversion rate is 75.44%, taking out the polymer, drying, and passing through the viscosityThe molecular weight of the PDMAAm is 8.18 × 105。
Example 14:
measuring 4mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 1cm of copper wire, reacting at 70 ℃ for 300min, wherein the DMAAm conversion rate is 77.47%, taking out the polymer, drying, and determining the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 8.62 multiplied by 105。
Example 15:
measuring 5mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 1cm of copper wire, reacting at 70 ℃ for 15min, wherein the DMAAm conversion rate is 3.5%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 2.82 multiplied by 105。
Example 16:
measuring 5mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 1cm of copper wire, reacting for 30min at 70 ℃, enabling the DMAAm conversion rate to be 6.54%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 2.72 multiplied by 105。
Example 17:
measuring 5mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 1cm of copper wire, reacting for 60min at 70 ℃, wherein the DMAAm conversion rate is 41.24%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 3.25 multiplied by 105。
Example 18:
measuring 5mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 1cm of copper wire, reacting at 70 ℃ for 120min, wherein the DMAAm conversion rate is 65.5%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 4.55 multiplied by 105。
Example 19:
measuring 5mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 1cm of copper wire, reacting for 180min at 70 ℃, wherein the DMAAm conversion rate is 78.69%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 7.12 multiplied by 105。
Example 20:
measuring 5mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 1cm of copper wire, reacting at 70 ℃ for 240min, wherein the DMAAm conversion rate is 84.3%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 7.45 multiplied by 105。
Example 21:
measuring 5mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 1cm of copper wire, reacting at 70 ℃ for 300min, wherein the DMAAm conversion rate is 85.04%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 7.86 multiplied by 105。
Example 22:
measuring 4mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 1cm of copper wire, reacting at 50 ℃ for 15min, wherein the DMAAm conversion rate is 3.23%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 3.76 multiplied by 105。
Example 23:
measuring 4mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 1cm of copper wire, reacting for 30min at 50 ℃, wherein the DMAAm conversion rate is 8.6%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 5.55 multiplied by 105。
Example 24:
measuring 4mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 1cm of copper wire, reacting for 60min at 50 ℃, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 6.63 x 105。
Example 25:
measuring 4mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 1cm of copper wire, reacting at 50 ℃ for 120min, wherein the DMAAm conversion rate is 16.78%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 7.61 multiplied by 105。
Example 26:
4mL of PDMAEMAO aqueous solution, 10mL of DMAAm and 5m of DMAAm are measuredL deionized water and 2mL DMF as internal standard, adding 1cm copper wire, reacting at 50 deg.C for 180min, DMAAm conversion rate is 19.48%, taking out polymer, oven drying, and determining molecular weight of PDMAAm by viscosity method to obtain PDMAAm with molecular weight of 8.51 × 105。
Example 27:
taking 4mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 1cm of copper wire, reacting at 50 ℃ for 240min, wherein the DMAAm conversion rate is 26.67%, taking out the polymer, drying, and determining the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 9.08 multiplied by 105。
Example 28:
measuring 4mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 1cm of copper wire, reacting at 50 ℃ for 300min, wherein the DMAAm conversion rate is 31.67%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 10.41 multiplied by 105。
Example 29:
measuring 4mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 1cm of copper wire, reacting at 60 ℃ for 15min, wherein the DMAAm conversion rate is 3.4%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 2.38 multiplied by 105。
Example 30:
measuring 4mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 1cm of copper wire, reacting for 30min at 60 ℃, wherein the DMAAm conversion rate is 7.96%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 2.99 multiplied by 105。
Example 31:
measuring 4mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 1cm of copper wire, reacting for 60min at 60 ℃, wherein the DMAAm conversion rate is 21.03%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 4.59 multiplied by 105。
Example 32:
measuring 4mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 1cm of copper wire, reacting for 120min at 60 ℃, wherein the DMAAm conversion rate is34.8 percent, taking out the polymer, drying the polymer, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to be 6.57 multiplied by 105。
Example 33:
measuring 4mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 1cm of copper wire, reacting for 180min at 60 ℃, wherein the DMAAm conversion rate is 43.23%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 8.29 multiplied by 105。
Example 34:
measuring 4mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 1cm of copper wire, reacting at 60 ℃ for 240min, wherein the DMAAm conversion rate is 58.47%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 8.79 multiplied by 105。
Example 35:
measuring 4mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 1cm of copper wire, reacting at 60 ℃ for 300min, wherein the DMAAm conversion rate is 65.17%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 9.10 multiplied by 105。
Example 36:
measuring 4mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 0.5cm of copper wire, reacting at 70 ℃ for 15min, wherein the DMAAm conversion rate is 2.75%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 2.75 multiplied by 105。
Example 37:
measuring 4mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 0.5cm of copper wire, reacting for 30min at 70 ℃, wherein the DMAAm conversion rate is 6.97%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 3.17 x 105。
Example 38:
measuring 4mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 0.5cm of copper wire, reacting for 60min at 70 ℃, wherein the DMAAm conversion rate is 23.59%, taking out the polymer, drying, and determining the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 3.59105。
Example 39:
measuring 4mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 0.5cm of copper wire, reacting at 70 ℃ for 120min, wherein the DMAAm conversion rate is 36.01%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 6.01 multiplied by 105。
Example 40:
measuring 4mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 0.5cm of copper wire, reacting at 70 ℃ for 180min, wherein the DMAAm conversion rate is 48.43%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 8.43 multiplied by 105。
Example 41:
measuring 4mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 0.5cm of copper wire, reacting at 70 ℃ for 240min, wherein the DMAAm conversion rate is 58.85%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 8.85 × 105。
Example 42:
measuring 4mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 0.5cm of copper wire, reacting at 70 ℃ for 300min, wherein the DMAAm conversion rate is 62.7%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 9.21 x 105。
Example 43:
measuring 4mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 2.0cm of copper wire, reacting at 70 ℃ for 15min, wherein the DMAAm conversion rate is 4.41%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 1.41 multiplied by 105。
Example 44:
measuring 4mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 2.0cm of copper wire, reacting for 30min at 70 ℃, wherein the DMAAm conversion rate is 6.29%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 3.20 multiplied by 105。
Example 45:
measuring 4mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 2.0cm of copper wire, reacting for 60min at 70 ℃, wherein the DMAAm conversion rate is 32.81%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 4.0 x 105。
Example 46:
measuring 4mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 2.0cm of copper wire, reacting at 70 ℃ for 120min, wherein the DMAAm conversion rate is 64.80%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 4.8 multiplied by 105。
Example 47:
measuring 4mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 2.0cm of copper wire, reacting at 70 ℃ for 180min, wherein the DMAAm conversion rate is 75.59%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 5.59 multiplied by 105。
Example 48:
measuring 4mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 2.0cm of copper wire, reacting at 70 ℃ for 240min, wherein the DMAAm conversion rate is 80.08%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 6.08 multiplied by 105。
Example 49:
measuring 4mL of PDMAEMAO aqueous solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF as internal standards, adding 2.0cm of copper wire, reacting at 70 ℃ for 300min, wherein the DMAAm conversion rate is 82.7%, taking out the polymer, drying, and measuring the molecular weight of the obtained PDMAAm by a viscosity method to obtain the PDMAAm with the molecular weight of 6.17 x 105。
Comparative example 1:
4mL of PDMAEMAO solution, 10mL of DMAAm, 5mL of deionized water and 2mL of DMF are taken as internal standards, 0.1g of copper powder is added, and the solution is reacted for 5.0h at 70 ℃ and becomes blue, but the conversion rate is 0.
Comparative example 2:
4mL of PDMAEMAO solution, 10mL of acrylamide aqueous solution (the concentration is 5.0M) and 2mL of DMF are taken as internal standards, 1.0cm of copper wire is added, and the reaction is carried out at 70 ℃ for 5.0h, wherein the conversion rate is 0.
Comparative example 3:
4mL of PDMAEMAO solution and 10mL of sodium acrylate aqueous solution (concentration: 1.0M) were weighed, 1.0cm of copper wire was added, and the mixture was reacted at 70 ℃ for 5.0 hours with a conversion of 0.
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 (5)
1. A copper wire-high molecular weight polymeric tertiary amine oxide redox initiation system is characterized in that: comprising copper wires and a high molecular weight polymeric tertiary amine oxide, wherein the high molecular weight polymeric tertiary amine oxide is prepared by the following method: first, 2- (N, N-dimethylamino) ethyl methacrylate was subjected to radical polymerization in an aqueous solution to obtain a polymer having a viscosity-average molecular weight of 3.0X 104-5.0×104And then oxidizing the poly (2- (N, N-dimethylamino) ethyl methacrylate) into a high molecular weight polymeric tertiary amine oxide with hydrogen peroxide.
2. Use of the copper wire-high molecular weight polymeric tertiary amine oxide redox initiation system of claim 1, characterized in that: for initiating free radical polymerization of N, N-dimethylacrylamide (DMAAm).
3. Use of a copper wire-high molecular weight polymeric tertiary amine oxide redox initiation system according to claim 2, characterized in that: the specific application method is as follows:
adding N, N-dimethylacrylamide into a reaction vessel filled with deionized water and a copper wire-high molecular weight polymeric tertiary amine oxide redox initiation system, and stirring for reaction at an initiation temperature.
4. Use of a copper wire-high molecular weight polymeric tertiary amine oxide redox initiation system according to claim 3, characterized in that: the initiation temperature is 50-70 ℃.
5. Use of the copper wire-high molecular weight polymeric tertiary amine oxide redox initiation system according to claim 2, characterized in that: the dosage of the high molecular weight polymeric tertiary amine oxide is 8.0 to 13.3 percent of the molar weight of DMAAm.
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