CN109400780B - Method for free radical polymerization of electron-deficient olefin - Google Patents

Method for free radical polymerization of electron-deficient olefin Download PDF

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CN109400780B
CN109400780B CN201811299507.6A CN201811299507A CN109400780B CN 109400780 B CN109400780 B CN 109400780B CN 201811299507 A CN201811299507 A CN 201811299507A CN 109400780 B CN109400780 B CN 109400780B
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CN109400780A (en
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邓剑如
钟隆
崔敏
刘旭
张平安
刘思萌
李通情
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Hunan Yiming New Material Co.,Ltd.
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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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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    • C08F120/56—Acrylamide; Methacrylamide
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Abstract

The invention discloses a method for free radical polymerization of electron-deficient olefin, which comprises dissolving electron-deficient olefin monomer and chain transfer initiator in reaction solvent, adding H2O2As an initiator, carrying out free radical polymerization; the chain transfer initiator is one or a mixture of ferric chloride, ferric bromide, cupric chloride and cupric bromide. The reaction system only has four components, other additives are not needed, the reaction components are few, the application range is wide, the residual metal halide is easy to remove, and the polymer structure is clear and controllable; the raw materials are cheap and easy to obtain, the reaction can be carried out under water at normal temperature, harsh reaction conditions are not required, expensive ligands are not required, the preparation process is simple, and the production cost is obviously reduced; less side reaction, stable and controllable polymerization reaction and easier obtaining of the functional polymer with narrower molecular weight distribution.

Description

Method for free radical polymerization of electron-deficient olefin
Technical Field
The invention relates to a method for free radical polymerization of electron-deficient olefin, in particular to a novel initiation system for free radical polymerization, belonging to the technical field of polymer synthesis.
Background
Free radical polymerization is widely applied to the preparation of macromolecular polymers, the polymerization conditions are mild, the monomer application range is wide, the operation is simple, and the method is almost suitable for all polymerization implementation methods. However, due to the reaction characteristics of slow initiation, fast growth and fast termination of free radical polymerization, the phenomena of chain termination and chain transfer are easy to occur in the reaction process, so that the molecular weight and the distribution of polymer molecules are influenced, the molecular weight and the structure of the polymer are uncontrollable, and even phenomena such as crosslinking, branching and the like occur, and the performance of the polymer is seriously influenced.
Since the first Living Polymerization (Living Polymerization) concept proposed by Szwarc, a scientist in the United states, Otsu et al proposed the initiation of transfer terminator (Iniferter) in free radical Polymerization, and successfully applied lniferer to Living radical Polymerization of homogeneous systems of olefinic monomers, which resulted in a rapid development of Living/controlled radical Polymerization. In 1995, professor Matyjaszewski in the United states and professor Sawamoto in Japan successively reported a low-valent transition metal compound (e.g., CuCl, FeCl) using an organic halide (R-X) as an initiator2Etc.) and a proper complexing agent as a catalytic system, and performing active/controllable free radical polymerization by redox reaction-Atom Transfer Radical Polymerization (ATRP), wherein the molecular weight of the obtained polymer is 10 by utilizing the dynamic balance between active species and dormant species to inhibit chain termination and chain transfer reaction4-105g/mol，Mw/Mn1.05-1.5, the ATRP method can be used for synthesizing various polymers such as block, graft, hyperbranched and end group functionalization, and has become a research hotspot in the field of polymer synthesis in recent years. However, the initiation system is subject to rapid inactivation of oxygen and water, the reaction conditions are extremely harsh, and certain low-valence transition metals have high toxicity, so that the initiation system still has great limitation in large-scale industrial production.
To address this problem, Matyjaszewski, King mountain, and the like employ conventional free radical initiators (e.g., azobisisobutyronitrile AIBN) and high valence transition metal compounds (e.g., CuCl)2) The monomer is initiated to undergo atom transfer radical polymerisation with bipyridine bpy as ligand, a process known as reverse atom transfer radical polymerisation. The reverse atom transfer radical polymerization replaces organic halide with traditional radical polymerization initiator which is cheaper and easily obtained, and replaces low-valence transition metal which is sensitive to environment with high-valence transition metal halide which is more stable and safe, thereby having larger industrial application value compared with ATRP method.
The conventional ATRP and reverse ATRP methods usually need to introduce expensive ligands and a large amount of volatile organic solvents, the polymerization temperature is high, transition metals are difficult to remove, and the polymerization reaction conditions are harsh, so that the application of the ATRP and reverse ATRP in industrial production is greatly limited. Therefore, it is urgently needed to develop a novel active/controllable free radical polymerization method with simple preparation process, low cost, safety and environmental protection for preparing narrow distribution functional high molecular polymers.
Disclosure of Invention
The invention solves the technical problems that the molecular weight of the polymer obtained by the traditional free radical polymerization is uncontrollable, and the molecular weight distribution is wider; the traditional active/controllable free radical polymerization needs to be carried out under the anhydrous and oxygen-free conditions, expensive ligands and volatile organic solvents are needed, the preparation process is complex, and the cost is high.
The invention provides a method for free radical polymerization of electron-deficient olefin, which comprises dissolving electron-deficient olefin monomer and chain transfer initiator in reaction solvent, adding H2O2As an initiator, carrying out free radical polymerization; the chain transfer initiator is one or a mixture of ferric chloride, ferric bromide, cupric chloride and cupric bromide.
Equivalently, ferric chloride, ferric bromide, cupric chloride, cupric bromide may contain water of crystallization, and corresponding salt solutions may be used, and even combinations thereof may be used.
Preferably, the electron-deficient olefin monomer is any one of acrylonitrile, acrylic acid and acrylamide monomers.
Preferably, the electron-deficient olefin is selected from any one of acrylonitrile, acrylic acid, methacrylic acid and acrylamide.
Preferably, the molar ratio between the chain transfer initiator and the initiator is from 1:20 to 60.
Preferably, the molar ratio between the electron deficient olefin monomer, the chain transfer initiator and the initiator is 200-2000:1: 20-60.
Preferably, the reaction solvent is any one or a mixture of water, DMF and DMSO. More preferably water.
Preferably, the initiator is added in the following manner: dropwise addition of H2O2The solution is dripped for 15-30 min.
Equivalently, H2O2The addition may be in the form of a solution, such as an aqueous solution, or mixed with other reaction solvents, further reducing the reaction rate at which the initiator is added.
Preferably, the temperature of the free radical polymerization is from 25 to 70 ℃, more preferably from 30 to 50 ℃ and the reaction time is from 2 to 48 hours.
The polymerization method of the invention synthesizes polyacrylonitrile with the molecular weight of 2.0 x 10 under the conditions of lower chain transfer initiator concentration (0.2-1%) and lower reaction temperature (30-60℃)4-8.0×104The conversion rate can reach 94.1% after 1h of reaction. The molecular weight of the synthesized sodium polyacrylate can reach 2.0 multiplied by 10 at most6The sodium polymethacrylate can reach 2.7 multiplied by 105Polyacrylamide can reach 2.7X 107And all have a lower molecular weight distribution (M)w/Mn1.06-1.53) and better conversion rate(s) ((ii)>90%); using FeBr3、CuCl2Replacement of FeCl3Polymerization was carried out and similar results were found. From1The existence of terminal hydroxyl and terminal halogen in the synthesized polyacrylonitrile is found in an H nuclear magnetic spectrum, and the synthesized polyacrylonitrile is accompanied with FeX3Variation of the ratio the polymer molecular weight gradually changed, indicating that the polymerization reaction was subjected to H2O2And FeX3The combined action of the two components.
The hydrogen peroxide can be mixed with ferrous iron (such as FeSO)4) The polymerization of acrylonitrile is directly initiated by forming a redox initiation system, and the polymerization rate is still higher at 5 ℃, but the polymerization rate is still higher due to 1mol Fe2+Can only react with H2O21mol of hydroxyl free radical is generated in the reaction, and in order to reduce the dosage of ferrous iron, the system is usually required to be supplemented with Fe generated by the reduction of an organic reducing agent (such as ascorbic acid)3+Thereby increasing the production cost and making it difficult to obtain polymers with clear structures. The initiation system of the invention only needs to add a very small amount of H into the reaction system2O2/FeX3Using Fe3+-Fe2+The bidirectional reversible cycle regeneration can realize the continuous redox initiation in the reaction system, and the hydroxyl-terminated polypropylene with clear and controllable structure and higher conversion rate is obtainedNitrile, and can initiate the active/controllable free radical polymerization of electron-deficient olefins such as acrylic acid, methacrylic acid and the like in water to obtain a functional polymer with narrow molecular weight distribution.
Specifically, the present invention begins with a chain transfer initiator such as FeX3(X represents Cl or Br) is dissolved in a reaction solvent (such as deionized water) to obtain FeX3After the monomers are completely dissolved, adding a certain proportion of olefin monomers, dropwise adding hydrogen peroxide for 15-20min at the temperature of 30-50 ℃ (some monomers need higher polymerization temperature), and refluxing after dropwise adding (the invention does not need heating reflux, and the reason for refluxing is that the temperature is higher in the initial stage of reaction, the solvent volatilizes, and the reflux is generated, while the heating condition, such as water bath, is still kept at 25-70 ℃, and the temperature is gradually stable and controllable along with the reaction) for reacting for 2-48h, so as to initiate the activity/controllable free radical polymerization of the water-soluble monomers in water. The method is simple to operate, safe, environment-friendly and reliable in quality, and is suitable for industrial production. Wherein, the reaction solvent is preferably water, which not only is environment-friendly and low in cost, but also can obtain a product with narrower molecular weight distribution and higher yield.
In the present invention, the chain transfer initiator belongs to a custom word. According to the action mechanism of four substances in the chain transfer initiator, theoretically, other halogen salts of metal ions with high and low variable valence have similar functions, but the substances are not common and have higher price, so that the reduction of the production cost is not facilitated. At the same time, there may be some differences in the specific effects of the reaction.
Compared with the prior art, the invention adopting the technical scheme can realize the following beneficial effects:
(1) only initiator H in the reaction system2O2Chain transfer initiator (FeCl)3) Solvent (H)2O) and a monomer, no other additive is needed, reaction components are few, the application range is wide, residual metal halide is easy to remove, and the polymer structure is clear and controllable;
(2)H2O2、FeCl3cheap and easily available, the reaction can be carried out under water at normal temperature, harsh reaction conditions are not required, expensive ligands are not required,the preparation process is simple, and the production cost is obviously reduced;
(3) the water is used as a main medium, the reaction heat is easy to remove, the side reaction is less, the polymerization reaction is stable and controllable, and the functionalized polymer with narrower molecular weight distribution can be more easily obtained.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of monohydroxy polyacrylonitrile.
FIG. 2 is a GPC outflow graph of acrylic acid polymerization at various stages.
FIG. 3 is a graph of the molecular weight of sodium polymethacrylate as a function of conversion. (Note: FIG. 3 abscissa is monomer conversion, left ordinate is polymer molecular weight corresponding to ● symbols, right ordinate is molecular weight distribution coefficient corresponding to a symbol.)
FIG. 4 is a graph of sodium polymethacrylate conversion as a function of time. (Note: FIG. 4 abscissa is reaction time; left ordinate is monomer conversion rate, corresponding to a-solidup-symbol; right ordinate is ln (C)0 M/CM) Corresponding to the ■ notation. )
Detailed Description
The present invention is described in further detail below with reference to specific examples. The following description is of the preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
The chemical reagents used: acrylonitrile (AN), AR; acrylic Acid (AA), AR; methacrylic acid (MAA), AR; acrylamide (AM), AR; ferric chloride hexahydrate (FeCl)3·6H2O), AR; 30% hydrogen peroxide (H)2O2) AR; deionized water; n, N-Dimethylformamide (DMF), AR; dimethyl sulfoxide (DMSO), AR; ethyl acetate, AR; toluene, AR; sodium hydroxide (NaOH), AR;
example 1: continuous precipitation polymerization of acrylonitrile in water.
Into a 500ml three-necked flask, acrylonitrile (26.50g, 0.500 m) was chargedol)、FeCl3·6H2O (0.54g, 0.002mol) and 75ml H2O, stirring and heating to 60 ℃; dropwise adding 25g (wt.%) of hydrogen peroxide-water solution (0.025 mol) at the speed of d/1s until the dropwise adding is finished, and reacting for 1 h; in the reaction process, the reaction solution is gradually turbid, and solid suspended matters finally appear; the reaction solution was filtered to obtain a crude product, which was washed 3 times with deionized water and dried to obtain 24.94g of a white powder with a yield of 94.1%. It is composed of1The H-NMR (400MHz, DMSO) spectrum is shown in FIG. 1.
Example 2: living/controlled radical polymerization of acrylonitrile in DMF.
Into a 500ml three-necked flask, acrylonitrile (26.50g, 0.500mol) and FeCl were charged3·6H2O (0.54g, 0.002mol) and 75ml of DMF, stirring and heating to 60 ℃; dropwise adding 25g (weight percent is 3.4%, and 0.025mol) of hydrogen peroxide-DMF solution at the speed of d/1s until the dropwise adding is completed, and carrying out reflux reaction for 2 h; the reaction solution was precipitated by adding water, filtered to obtain a crude product, washed 3 times with deionized water, and dried to obtain 25.76g of a white powder with a yield of 97.2%.
Example 3: living/controlled radical polymerization of acrylonitrile in DMSO.
Into a 500ml three-necked flask, acrylonitrile (26.50g, 0.500mol) and 0.27g of FeCl were charged3·6H2O (0.27g, 0.001mol) and 75ml DMSO, stirring and heating to 60 ℃; dropwise adding 25g (wt.%) of hydrogen peroxide-DMSO solution at the speed of d/1s until the dropwise adding is completed, and reacting for 2 h; the reaction solution was precipitated by adding water, filtered to obtain a crude product, washed 3 times with deionized water, and dried to obtain 25.20g of a white powder with a yield of 95.1%.
Example 4: living/controlled radical polymerization of acrylic acid in water.
In a 500ml three-necked flask, acrylic acid (28.80g, 0.400mol), FeCl was added3·6H2O (0.27g, 0.001mol) and 75ml of deionized water, and stirring and heating to 45 ℃; dropwise adding 25g (wt.%) of hydrogen peroxide-water solution at the speed of d/1s until the dropwise adding is completed, and reacting for 24 h; extracting the reaction solution with toluene, collecting the lower layer water phase clear solution, adding NaOH to neutralize to pH 9-10, filtering to remove Fe (OH)3And Fe (OH)2Precipitation ofDrying the filtrate to obtain sodium polyacrylate, metering, acidifying and drying the sodium polyacrylate to obtain polyacrylic acid. The GPC outflow curve of the product at different stages of the polymerization is shown in FIG. 2.
Example 5: living/controlled radical polymerization of methacrylic acid in water.
Into a 500ml three-necked flask, methacrylic acid (30.10g, 0.350mol), FeCl, was charged3·6H2O (0.27g, 0.001mol) and 75ml of deionized water, and stirring and heating to 45 ℃; dropwise adding 25g (wt.%) of hydrogen peroxide-water solution (0.030 mol) at the speed of d/1s until the dropwise adding is completed, and reacting for 48 h; taking out the reaction solution, precipitating in ethyl acetate, standing, filtering, drying, adding NaOH solution to neutralize to pH 9-10, filtering to remove Fe (OH)3And Fe (OH)2Precipitating, drying the filtrate to obtain sodium polymethacrylate, metering, acidifying and drying the sodium polymethacrylate to obtain the polymethacrylic acid.
Example 6: living/controlled radical polymerization of acrylamide in water.
Into a 500ml three-necked flask, acrylamide (28.40g, 0.400mol), FeCl, was added3·6H2O (0.27g, 0.001mol) and 75ml of deionized water, and stirring and heating to 30 ℃; dropwise adding 25g (wt.%) of hydrogen peroxide-water solution at the speed of d/1s until the dropwise adding is completed, and reacting for 30 h; taking out the reaction solution, precipitating in acetone, standing, filtering, and drying to obtain the desired polymer.
Comparative example 1: the effect of different chain transfer initiators on polyacrylonitrile.
Acrylonitrile (26.50g, 0.500mol) and the corresponding chain transfer initiator (FeCl) were each dissolved in 75ml of water3·6H2O、CuCl2、FeBr3) Adding the mixture into a 500ml three-neck flask, dropwise adding 25g (weight percent is 3.4%, and 0.025mol) of hydrogen peroxide-water solution at the speed of d/1s until the dropwise adding is finished, and carrying out reflux reaction for 1 h; the reaction solution is filtered to obtain a crude product, the crude product is washed for 3 times by deionized water, and the required polymer is obtained after drying.
The changes in the molecular weight and the conversion of the polymer were examined by using different chain transfer initiators, and the results are shown in table 1 below.
TABLE 1 Effect of different chain transfer initiators on the polymerizationa
Figure BDA0001851975210000061
aThe polymerization condition is that T is 60 ℃;
bratio [ AN]0/[ chain transfer initiator]0/[H2O2]0；
cMolecular weight is viscosity average molecular weight, and is calculated by the Ubbelohde viscometer
Figure BDA0001851975210000062
Calculated to obtain (polyacrylonitrile dissolved in DMF at 20 +/-0.05 ℃, K is 3.07 multiplied by 10)-2，α＝0.76)。
dConversion rate is polymer mass/total monomer mass × 100%.
As can be seen from Table 1, in the continuous aqueous precipitation polymerization of acrylonitrile, all three chain transfer initiators can be reacted with H2O2The polymerization of acrylonitrile is initiated by the action, and the acrylonitrile has higher conversion rate; but the copper chloride has larger environmental pollution and the ferric bromide has instable property, so the invention selects the more environment-friendly ferric chloride as the chain transfer initiator for the continuous aqueous phase precipitation polymerization of the acrylonitrile.
Comparative example 2: the effect of the amount of chain transfer initiator on the molecular weight of polyacrylonitrile.
Acrylonitrile (26.50g, 0.500mol) and the corresponding FeCl were each dissolved in 75ml of water as solvent3·6H2O (0.27g, 0.001 mol; 0.54g, 0.002 mol; 0.81g, 0.003 mol; 1.08g, 0.004 mol; 1.35g, 0.005mol) is added into a 500ml three-neck flask, 25g (wt.% 3.4%, 0.025mol) of hydrogen peroxide-water solution is dropwise added at the speed of d/1s until the dropwise addition is completed, and the reflux reaction is carried out for 1 h; the reaction solution is filtered to obtain a crude product, the crude product is washed for 3 times by deionized water, and the required polymer is obtained after drying.
By using different proportions of chain transfer initiator, the changes in polymer molecular weight and conversion were examined and the results are shown in table 2 below.
TABLE 2 influence of different amounts of chain transfer initiator on the polymerizationa
Figure BDA0001851975210000063
aThe polymerization condition is that T is 60 ℃;
bratio [ AN]0/[FeCl3·6H2O]0/[H2O2]0；
cMolecular weight is viscosity average molecular weight, and is calculated by the Ubbelohde viscometer
Figure BDA0001851975210000071
Calculated to obtain (polyacrylonitrile dissolved in DMF at 20 +/-0.05 ℃, K is 3.07 multiplied by 10)-2，α＝0.76)。
dConversion rate is polymer mass/total monomer mass × 100%.
As can be seen from Table 2, in the continuous precipitation polymerization of acrylonitrile, FeCl was accompanied3·6H2The increasing of the dosage of O, the gradual decrease of the molecular weight of polyacrylonitrile and the monomer conversion rate are all above 92 percent, which shows that the polymer system has higher industrial utilization value.
Comparative example 3: the influence of different monomer amounts on the molecular weight and conversion of polyacrylic acid (sodium).
Acrylic acid (28.80g, 0.400mol) and corresponding FeCl were each added with 75ml of water as solvent3·6H2O (0.135g, 0.5 mmol; 0.270g, 1 mmol; 0.405g, 1.5mmol) is added into a 500ml three-neck flask, 25g (2.0% by weight, 0.015 mol; 4.1% by weight, 0.030 mol; 6.1% by weight, 0.045mol) of hydrogen peroxide-water solution is added dropwise at the speed of d/1s until the dropwise addition is completed, and the reaction is carried out for 12-24 h; extracting the reaction solution with toluene, collecting the supernatant, adding NaOH to neutralize to pH 9-10, filtering to remove Fe (OH)3And Fe (OH)2Precipitating and drying to obtain the required polymer.
By using different proportions of acrylic monomers, variations in polymer molecular weight, conversion, and molecular weight distribution were examined, and the results are shown in table 3 below.
TABLE 3 Effect of different monomer amounts on the polymerizationa
Figure BDA0001851975210000072
aThe polymerization condition is that T is 45 ℃;
bratio of [ AA]0/[FeCl3·6H2O]0/[H2O2]0；。
Figure BDA0001851975210000073
As can be seen from Table 3, in the polymerization process of acrylic acid, comparison Nos. 1 and 2 shows that the polymerization time is increased and the molecular weight of the product is increased; 2. comparison Nos. 3 and 5, followed by [ AA ]]0/[FeCl3·6H2O]0The molecular weight of the obtained polymer is gradually increased when the ratio of (2) to (1) is increased from 400/1.5 to 1200/1.5, but the molecular weight distribution is widened, mainly because the relative content of free radicals generated by the system is reduced along with the increase of the concentration of the monomer, the controllability of the system is deteriorated, and the molecular weight distribution of the polymer is influenced.
Comparative example 4: the effect of different amounts of chain transfer initiator on the molecular weight and conversion of poly (sodium methacrylate).
Methacrylic acid (30.10g, 0.350mol) and the corresponding FeCl were each dissolved in 75ml of water3·6H2O (0.135g, 0.5 mmol; 0.270g, 1 mmol; 0.405g, 1.5mmol) is added into a 500ml three-neck flask, 25g (wt.%: 4.1%, 0.030mol) of hydrogen peroxide-water solution is added dropwise at the speed of d/1s until the dropwise addition is finished, and the reflux reaction is carried out for 48 h; taking out the reaction solution, precipitating in ethyl acetate, standing, filtering, drying, adding NaOH for neutralizationTo pH 9-10, Fe (OH) was removed by filtration3And Fe (OH)2Precipitating, and drying the filtrate to obtain the sodium polymethacrylate.
By using different proportions of chain transfer initiators, the changes in polymer molecular weight, conversion and molecular weight distribution were examined and the results are shown in table 4 below.
TABLE 4 influence of different amounts of chain transfer initiator on the polymerizationa
Figure BDA0001851975210000081
aThe polymerization condition is that T is 45 ℃;
bratio [ MAA ]]0/[FeCl3·6H2O]0/[H2O2]0；
Figure BDA0001851975210000082
As can be seen from Table 4, in the polymerization of methacrylic acid, the monomer conversion rate increased and then decreased as the amount of the chain transfer initiator increased, when [ MAA ]]0/[FeCl3·6H2O]0/[H2O2]0The ratio of (A) to (B) of 350/1.0/30 is higher in monomer conversion and narrower in molecular weight distribution, since the monomer free radical cannot completely react with FeCl when the chain transfer initiator is small3Complex formation is carried out, and generated active free radicals are less; when the chain transfer initiator is more, the transition metal ions in the chain transfer initiator can generate polymerization inhibition on the growth of the chain, and the polymerization reaction rate is influenced.
Comparative example 5: the effect of reaction time on the molecular weight of poly (sodium methacrylate) and the conversion.
Methacrylic acid (30.10g, 0.350mol) and FeCl were separately added with 75ml of water as a solvent3·6H2O (0.270g, 1mmol) was charged in a 500ml three-necked flask, and 25g (wt.%) of an aqueous hydrogen peroxide solution (4.1%, 0%) was added dropwise at a rate of d/1s030mol) until the dropwise addition is finished, and reacting for 6-48 h; taking out the reaction solution, precipitating in ethyl acetate, standing, filtering, drying, adding NaOH to neutralize to pH 9-10, filtering to remove Fe (OH)3And Fe (OH)2Precipitating, and drying the filtrate to obtain sodium polymethacrylate, wherein the conversion rate and molecular weight change before and after polymerization are shown in figures 3 and 4.
By controlling the reaction time, the changes of the polymer molecular weight, the conversion rate and the molecular weight distribution were examined, and the results are shown in the following table 5.
TABLE 5 Effect of different reaction times on the polymerizationa
Figure BDA0001851975210000091
aThe polymerization condition is that T is 45 ℃; [ MAA]0/[FeCl3·6H2O]0/[H2O2]0＝350/1.0/30；
Figure BDA0001851975210000092
As can be seen from Table 5, in the polymerization of methacrylic acid, the monomer conversion rate gradually increased and the polymer molecular weight gradually increased with the progress of the reaction, both having better molecular weight distribution, and the reaction gave better results at lower temperature (45 ℃ C.), indicating that H2O2/FeCl3The initiation system has good controllable activity polymerization capability in water, and is completely suitable for the activity/controllable free radical polymerization of water-soluble olefins such as acrylic acid, methacrylic acid and the like in water.
In summary, the present invention is achieved by using H2O2/FeCl3·6H2The two raw materials form a novel initiation system, successfully realizes the active/controllable free radical polymerization of water-soluble monomers such as acrylic acid, methacrylic acid and the like in water, and simultaneously realizes the continuous aqueous phase precipitation polymerization of acrylonitrile in water and the active/controllable free radical polymerization in DMSO.Compared with the traditional active/controllable free radical polymerization, the initiation system does not need expensive ligand and volatile organic solvent, has mild experimental conditions, simple process and environmental protection, and provides a more green method for the active/controllable free radical polymerization of electron-deficient olefins.

Claims (9)

1. A free radical polymerization process for preparing the electron-deficient olefin includes such steps as dissolving the electron-deficient olefin monomer and chain transfer initiator in solvent, adding H2O2As an initiator, carrying out free radical polymerization; the chain transfer initiator is one or a mixture of 2 of ferric chloride and ferric bromide containing crystal water;
the reaction solvent is water or DMF;
the reaction system only has initiator H2O2、Chain transfer initiator, reaction solvent and electron-deficient olefin monomer.
2. The method of claim 1, wherein the electron deficient olefin monomer is any one of a group consisting of acrylonitrile, acrylic, and acrylamide monomers.
3. The method of claim 1, wherein the electron deficient olefin is selected from any one of acrylonitrile, acrylic acid, methacrylic acid, and acrylamide.
4. The method of claim 1, wherein the molar ratio of chain transfer initiator to initiator is from 1:20 to 60.
5. The method of claim 4, wherein the molar ratio between the electron deficient olefin monomer, the chain transfer initiator and the initiator is 200-2000:1: 20-60.
6. The method of claim 1, wherein the initiator is added by: dropwise addition of H2O2The solution is dripped for 15-30 min.
7. The process of claim 1, wherein the temperature of the free radical polymerization reaction is from 25 ℃ to 70 ℃.
8. The process of claim 1, wherein the temperature of the free radical polymerization reaction is from 30 ℃ to 50 ℃.
9. The process of claim 1, wherein the free radical polymerization reaction time is from 2 to 48 hours.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1515596A (en) * 2003-08-28 2004-07-28 上海交通大学 Iron-contained type load catalyst polymerized by utilizing reverse atom to transfer free radical and its application
WO2015024236A1 (en) * 2013-08-22 2015-02-26 Henkel Corporation High molecular weight polymers having high olefin content
CN106397652A (en) * 2016-09-14 2017-02-15 济南大学 Method for preparing super-macroporous high-specific-area polymer

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1515596A (en) * 2003-08-28 2004-07-28 上海交通大学 Iron-contained type load catalyst polymerized by utilizing reverse atom to transfer free radical and its application
WO2015024236A1 (en) * 2013-08-22 2015-02-26 Henkel Corporation High molecular weight polymers having high olefin content
CN106397652A (en) * 2016-09-14 2017-02-15 济南大学 Method for preparing super-macroporous high-specific-area polymer

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