CN109400780A - A kind of method of short of electricity subclass alkene free radical polymerization - Google Patents

A kind of method of short of electricity subclass alkene free radical polymerization Download PDF

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CN109400780A
CN109400780A CN201811299507.6A CN201811299507A CN109400780A CN 109400780 A CN109400780 A CN 109400780A CN 201811299507 A CN201811299507 A CN 201811299507A CN 109400780 A CN109400780 A CN 109400780A
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initiator
reaction
short
tra nsfer
chain tra
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CN109400780B (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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Hunan University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08F120/42—Nitriles
    • C08F120/44—Acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08F120/04—Acids; Metal salts or ammonium salts thereof
    • C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08F120/52—Amides or imides
    • C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F120/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation

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Abstract

The invention discloses a kind of methods of short of electricity subclass alkene free radical polymerization, and short of electricity subclass olefinic monomer, chain tra nsfer initiator are dissolved in reaction dissolvent, and H is added2O2As initiator, Raolical polymerizable is carried out；The chain tra nsfer initiator is the mixing of one or more of iron chloride, ferric bromide, copper chloride, copper bromide.Only there are four types of components in reaction system, are not necessarily to other additives, reactive component is few, and applied widely, residual metal halide easily removes, and polymer architecture is clearly controllable；Raw material is cheap and easy to get, and reaction can have underwater progress in room temperature, and without harsh reaction condition, without using expensive ligand, preparation process is simple, and production cost significantly reduces；Side reaction is few, and polymerization reaction is stably and controllable, it is easier to obtain the relatively narrow functionalized polymer of molecular weight distribution.

Description

A kind of method of short of electricity subclass alkene free radical polymerization
Technical field
The present invention relates to a kind of method of short of electricity subclass alkene free radical polymerization, in particular to a kind of free radical polymerization it is new Initiation system, belong to macromolecule synthesising technology field.
Background technique
Free radical polymerization is widely used in the preparation of macromolecule polyalcohol, and polymerizing condition is mild, and monomer is widely applicable, It is easy to operate, it is suitable for almost all polymerization implementation methods.But since free radical polymerization causes slowly, growth, speed terminate fastly Reaction characteristics cause it to be easy to appear chain termination and chain tra nsfer phenomenon during the reaction, to influence point of polymer molecule Son amount and its distribution seriously affect so that the molecular weight of polymer and structure are uncontrollable, or even phenomena such as crosslinking, branching occur The performance of polymer.
From American scientist Szwarc be put forward for the first time the concept of living polymerization (Living Polymerization) with Afterwards, Otsu etc. proposes the concept of iniferter agent (Iniferter) again in free radical polymerization, and by lniferter It is applied successfully to the active free radical polymerization of vinyl monomer homogeneous system, thus activity/controllable free-radical polymerisation obtains rapidly Development.Nineteen ninety-five, the Matyjaszewski professor in the U.S. and professor Sawamoto of Japan report one kind in succession with organic halogen Compound (R-X) is initiator, low-valent transition metals compound (such as CuCl, FeCl2Deng) and complexant appropriate be catalyst system, Activity/controllable free-radical polymerisation method-atom transfer radical polymerization (ATRP) is carried out by redox reaction, is utilized The dynamic equilibrium of reactive species and suspend mode inter-species, inhibits chain termination and chain transfer reaction, and obtained polymer molecular weight is 104- 105G/mol, Mw/Mn=1.05-1.5, it is a variety of that ATRP method can be used for synthesizing block, grafting, hyperbranched and end group functional etc. Polymer, it has also become the research hotspot in Polymer Synthesizing field in recent years.But the initiation system encounters oxygen and water rapid deactivation, Reaction condition is extremely harsh, and certain lower valency transition metal have larger toxicity, therefore still have in large-scale industrial production Biggish limitation.
For this problem, using conventional radical initiator, (such as azo two is different again by Matyjaszewski, Wang Jinshan etc. Butyronitrile AIBN) and high-valence state transistion metal compound (such as CuCl2) under the case where bipyridyl bpy makees ligand cause monomer into Row atom transfer radical polymerization, such polymerization are known as reverse atom transfer radical polymerization.Reversed atom transfer is free Base polymerization replaces organic halogen with conventional free radical polymerization initiator more cheap and easy to get, with more stable safe high-valence state mistake Metal halide is crossed instead of environmentally sensitive lower valency transition metal, there is bigger industrial application value compared with ATRP method.
Conventional ATRP and reverse ATRP method usually requires to introduce expensive ligand and largely volatile organic Solvent, polymerization temperature is higher, and transition metal is also difficult to remove, and polymeric reaction condition is harsh, significantly limits it and is industrializing Application in production.Therefore, need to develop that a kind of preparation process is simple, novel active low in cost and safety and environmental protection/controllable Free radical polymerisation process is used to prepare narrow ditribution functional polymer polymer.
Summary of the invention
Present invention solves the technical problem that being, the molecular weight for the polymer that conventional free radical polymerize is uncontrollable, molecule Measure wider distribution；Traditional activated/controllable free-radical polymerisation need to carry out under the conditions of anhydrous and oxygen-free, need to use expensive ligand And volatile organic solvent, preparation process complexity, higher cost.
The technical scheme is that a kind of method of short of electricity subclass alkene free radical polymerization is provided, by short of electricity subclass alkene Hydrocarbon monomer, chain tra nsfer initiator are dissolved in reaction dissolvent, and H is added2O2As initiator, Raolical polymerizable is carried out；The chain Transfer initiator is the mixing of one or more of iron chloride, ferric bromide, copper chloride, copper bromide.
Equally, iron chloride, ferric bromide, copper chloride, copper bromide can contain the crystallization water, and it is molten that corresponding salt also can be used Liquid, it might even be possible to be the composition containing above-mentioned substance.
Preferably, the short of electricity subclass olefinic monomer be vinyl cyanide, it is acrylic compounds, any in acrylamide monomers It is a kind of.
Preferably, the short of electricity subclass alkene is any in acrylonitrile, acrylic acid, methacrylic acid, acrylamide It is a kind of.
Preferably, the molar ratio between the chain tra nsfer initiator and initiator is 1:20-60.
Preferably, the molar ratio between the short of electricity subclass olefinic monomer, chain tra nsfer initiator and initiator is 200- 2000:1:20-60。
Preferably, the reaction dissolvent is water, any one or a few mixture in DMF, DMSO.More preferably water.
Preferably, the adding manner of initiator are as follows: H is added dropwise2O2Solution, time for adding 15-30min.
Equally, H2O2It can be added as a solution, such as aqueous solution, or mix addition with other reaction dissolvents, into One step reduces reaction rate when initiator is added.
Preferably, the temperature of Raolical polymerizable be 25-70 DEG C, more preferable 30-50 DEG C, reaction time 2-48h.
Polymerization of the present invention, in lower chain tra nsfer initiator concentration (0.2%-1%) and lower reaction temperature It spends under (30 DEG C -60 DEG C), the polyacrylonitrile molecular weight of synthesis is 2.0 × 104-8.0×104Between, react conversion ratio highest after 1h Up to 94.1%.The Sodium Polyacrylate molecular weight of synthesis reaches as high as 2.0 × 106, sodium polymethacrylate is up to 2.7 × 105, Polyacrylamide is up to 2.7 × 107, and all have lower molecular weight distribution (Mw/Mn=1.06-1.53) and preferable conversion Rate (> 90%)；Use FeBr3、CuCl2Substitute FeCl3It is polymerize, discovery obtains similar result.From1It is sent out in H nuclear magnetic spectrogram There is the presence of terminal hydroxy group and end group halogen in the polyacrylonitrile now synthesized, and with FeX3The variation polymer molecular weight of ratio by Gradual change illustrates polymerization reaction by H2O2And FeX3Collective effect.
Hydrogen peroxide can be with ferrous iron (such as FeSO4) polymerization that redox initiation system directly causes acrylonitrile is constituted, 5 Still there is higher rate of polymerization at DEG C, but due to 1molFe2+It can only be with H2O2Reaction generates 1mol hydroxyl radical free radical, to reduce by two The dosage of valence iron usually requires in system to add the Fe that organic reducing agent (such as ascorbic acid) reduction generates3+, to increase life Produce cost, it is also difficult to obtain polymer clear in structure.Initiation system of the present invention need to only be added seldom in the reaction system The H of amount2O2/FeX3, utilize Fe3+-Fe2+Bidirectional reversible circular regeneration, can be realized in reaction system continued oxidation reduction Cause, obtains hydroxy terminated polypropylene nitrile clear in structure controllable and with higher conversion, while can also cause acrylic acid, methyl Activity/the controllable free-radical polymerisation of the shorts of electricity subclass such as acrylic acid alkene in water, obtains the relatively narrow functional poly of molecular weight distribution Close object.
Specifically, the present invention is first by chain tra nsfer initiator such as FeX3(X represents Cl or Br) is dissolved in reaction dissolvent (such as Deionized water) in, to FeX3A certain proportion of olefin monomer is added after being completely dissolved, (certain monomers at a temperature of 30-50 DEG C Need polymerization temperature slightly higher) hydrogen peroxide 15-20min is added dropwise, (present invention is not needed using heating back for reflux after being added dropwise Stream, cause the reason of flowing back to be: initial reaction stage temperature is higher, and solvent volatilization is generated and flowed back, and heating condition-such as water-bath, still protects Hold at 25-70 DEG C, with the progress of reaction, temperature is gradually steady controllable) reaction 2-48h, causes water-soluble monomer in water with this In activity/controllable free-radical polymerisation.This method is easy to operate, safety and environmental protection, reliable in quality, is suitable for industrialized production.Its In, reaction dissolvent is preferably water, and not only environmentally friendly, cost is relatively low, and the molecular weight distribution of obtained product is narrower, and yield is more It is high.
In the present invention, chain tra nsfer initiator belongs to custom words.According to the effect of four kinds of substances in chain tra nsfer initiator Mechanism, theoretically, it is similar that other have the function of that the halogen of the metal ion of high and low variable valence all has, but these objects Matter is not common, and price is higher, is unfavorable for reducing production cost.Meanwhile the specific effect of reaction is also likely to be present some differences.
Compared with prior art, the present invention by adopting the above technical scheme can be realized it is following the utility model has the advantages that
(1) there was only initiator H in reaction system2O2, chain tra nsfer initiator (FeCl3), solvent (H2) and totally four kinds of monomer O Component is not necessarily to other additives, and reactive component is few, and applied widely, residual metal halide easily removes, and polymer architecture is clear Controllably；
(2)H2O2、FeCl3Cheap and easy to get, reaction can have underwater progress in room temperature, without harsh reaction condition, without making With expensive ligand, preparation process is simple, and production cost significantly reduces；
(3) using water as main medium, reaction heat is easily removed, and side reaction is few, and polymerization reaction is stably and controllable, it is easier to be divided The functionalized polymer of son amount narrow distribution.
Detailed description of the invention
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of monohydroxy polyacrylonitrile.
Fig. 2 is that acroleic acid polymerization reacts different phase GPC elution curve figure.
Fig. 3 is sodium polymethacrylate molecular weight with conversion ratio variation relation figure.(note: Fig. 3 abscissa is monomer conversion Rate；Left ordinate is polymer molecular weight, corresponding ● symbol；Right ordinate is molecular weight distribution index, correspondence ▲ symbol.)
Fig. 4 is that sodium polymethacrylate conversion ratio changes over time relational graph.(note: Fig. 4 abscissa is the reaction time；It is left Ordinate is monomer conversion, correspondence ▲ symbol；Right ordinate is ln (C0 M/CM), corresponding ■ symbol.)
Specific embodiment
Further detailed description is made to the present invention below in conjunction with specific embodiment.Discussed below is only this hair Bright preferred embodiment, is not intended to restrict the invention, and for those skilled in the art, the present invention can have respectively Kind change and variation.All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should all wrap It is contained in protection scope of the present invention.
Chemical reagent used: acrylonitrile (AN), AR；Acrylic acid (AA), AR；Methacrylic acid (MAA), AR；Acrylamide (AM), AR；Ferric chloride (FeCl36H2O) (FeCl3·6H2O), AR；30% hydrogen peroxide (H2O2), AR；Deionized water；N, N- dimethyl Formamide (DMF), AR；Dimethyl sulfoxide (DMSO), AR；Ethyl acetate, AR；Toluene, AR；Sodium hydroxide (NaOH), AR；
Embodiment 1: the continuous precipitation polymerization of acrylonitrile in water.
In 500ml three-necked flask, acrylonitrile (26.50g, 0.500mol), FeCl is added3·6H2O (0.54g, 0.002mol) and 75mlH2O, stirring are warming up to 60 DEG C；Hydrogen peroxide-aqueous solution 25g (wt.%=is added dropwise with d/1s speed 3.4%, 0.025mol), until being added dropwise, react 1h；In reaction process, reaction solution is gradually muddy finally to there is solid suspension Object；Crude product is obtained by filtration in reaction solution, is washed with deionized 3 times, dry, obtains 24.94g white powder, yield 94.1%. Its1H-NMR (400MHz, DMSO) spectrogram is as shown in Figure 1.
Embodiment 2: activity/controllable free-radical polymerisation of the acrylonitrile in DMF.
In 500ml three-necked flask, acrylonitrile (26.50g, 0.500mol), FeCl is added3·6H2O (0.54g, 0.002mol) and 75mlDMF, stirring are warming up to 60 DEG C；Hydrogen peroxide-DMF solution 25g (wt.%=is added dropwise with d/1s speed 3.4%, 0.025mol), until being added dropwise to complete, back flow reaction 2h；Reaction solution aqueous precipitation, is obtained by filtration crude product, spend from Sub- water washing 3 times, it is dry, obtain 25.76g white powder, yield 97.2%.
Embodiment 3: activity/controllable free-radical polymerisation of the acrylonitrile in DMSO.
In 500ml three-necked flask, acrylonitrile (26.50g, 0.500mol), 0.27gFeCl is added3·6H2O (0.27g, 0.001mol) and 75mlDMSO, stirring are warming up to 60 DEG C；Hydrogen peroxide-DMSO solution 25g (wt.%=is added dropwise with d/1s speed 4.1%, 0.030mol), until being added dropwise to complete, react 2h；Reaction solution aqueous precipitation, is obtained by filtration crude product, uses deionized water Washing 3 times, it is dry, obtain 25.20g white powder, yield 95.1%.
Embodiment 4: the activity/controllable free-radical polymerisation of acrylic acid in water.
In 500ml three-necked flask, acrylic acid (28.80g, 0.400mol), FeCl is added3·6H2O (0.27g, 0.001mol) and 75ml deionized water, stirring are warming up to 45 DEG C；Hydrogen peroxide-aqueous solution 25g (wt.% is added dropwise with d/1s speed =4.1%, 0.030mol), until being added dropwise to complete, reaction is for 24 hours；Reaction solution adds toluene to extract Hou Qu lower layer water phase clear liquid, adds NaOH is neutralized to pH=9-10, is filtered to remove Fe (OH)3With Fe (OH)2Precipitating, obtains Sodium Polyacrylate after filtrate is dried, and gathers Polyacrylic acid can be obtained after sodium acrylate metering acidification, drying.The GPC elution curve figure of its polymerization reaction different phase product is as schemed Shown in 2.
Embodiment 5: the activity/controllable free-radical polymerisation of methacrylic acid in water.
In 500ml three-necked flask, methacrylic acid (30.10g, 0.350mol), FeCl is added3·6H2O (0.27g, 0.001mol) and 75ml deionized water, stirring are warming up to 45 DEG C；Hydrogen peroxide-aqueous solution 25g (wt.% is added dropwise with d/1s speed =4.1%, 0.030mol), until being added dropwise to complete, react 48h；Reaction solution is precipitated in ethyl acetate after taking out, is stood, mistake Filter, after dry plus NaOH solution is neutralized to pH=9-10, is filtered to remove Fe (OH)3With Fe (OH)2Precipitating, after filtrate is dried To sodium polymethacrylate, polymethylacrylic acid can be obtained after sodium polymethacrylate metering acidification, drying.
Embodiment 6: the activity/controllable free-radical polymerisation of acrylamide in water.
In 500ml three-necked flask, acrylamide (28.40g, 0.400mol), FeCl is added3·6H2O (0.27g, 0.001mol) and 75ml deionized water, stirring are warming up to 30 DEG C；Hydrogen peroxide-aqueous solution 25g (wt.% is added dropwise with d/1s speed =4.1%, 0.030mol), until being added dropwise to complete, react 30h；Reaction solution precipitates in acetone after taking out, stands, filters, and does Required polymer can be obtained after dry.
Comparative example 1: influence of the different chain tra nsfer initiators to polyacrylonitrile.
Using 75ml water as solvent, respectively by acrylonitrile (26.50g, 0.500mol) and corresponding chain tra nsfer initiator (FeCl3·6H2O、CuCl2、FeBr3) be added in 500ml three-necked flask, hydrogen peroxide-aqueous solution 25g is added dropwise with d/1s speed (wt.%=3.4%, 0.025mol), until being added dropwise to complete, back flow reaction 1h；Crude product is obtained by filtration in reaction solution, uses deionization Water washing 3 times, required polymer is obtained after dry.
By using different chain tra nsfer initiators, the variation of polymer molecular weight and conversion ratio is investigated, as a result such as the following table 1 It is shown.
Influence of the different chain tra nsfer initiators of table 1. to polymerization reactiona
aPolymerizing condition: T=60 DEG C；
bRatio=[AN]0/ [chain tra nsfer initiator]0/[H2O2]0；
cMolecular weight is viscosity-average molecular weight, by Ubbelohde viscometer formulaIt is calculated that (polyacrylonitrile is dissolved in DMF is at 20 ± 0.05 DEG C, K=3.07 × 10-2, α=0.76).
dConversion ratio=polymer quality/monomer gross mass × 100%.
As it can be seen from table 1 three kinds of chain tra nsfer initiators all can be with H in the continuous aqueous phase precipitation polymerization of acrylonitrile2O2 Effect causes the polymerization of acrylonitrile, and all has higher conversion ratio；But copper chloride environmental pollution is larger, ferric bromide property compared with It is unstable, therefore the present invention selects more environmentally protective iron chloride to draw as the chain tra nsfer of acrylonitrile continuous aqueous phase precipitation polymerization Send out agent.
Comparative example 2: influence of the chain tra nsfer initiator amount to polyacrylonitrile molecular weight.
Using 75ml water as solvent, respectively by acrylonitrile (26.50g, 0.500mol) and corresponding FeCl3·6H2O (0.27g, 0.001mol；0.54g, 0.002mol；0.81g, 0.003mol；1.08g 0.004mol；1.35g, 0.005mol) It is added in 500ml three-necked flask, hydrogen peroxide-aqueous solution 25g (wt.%=3.4%, 0.025mol) is added dropwise with d/1s speed, Until being added dropwise to complete, back flow reaction 1h；Crude product is obtained by filtration in reaction solution, is washed with deionized 3 times, needed for obtaining after dry Polymer.
By using the chain tra nsfer initiator of different proportion, the variation of polymer molecular weight and conversion ratio is investigated, as a result such as Shown in the following table 2.
Influence of the different chain tra nsfer initiator amounts of table 2. to polymerization reactiona
aPolymerizing condition: T=60 DEG C；
bRatio=[AN]0/[FeCl3·6H2O]0/[H2O2]0；
cMolecular weight is viscosity-average molecular weight, by Ubbelohde viscometer formulaIt is calculated that (polyacrylonitrile is dissolved in DMF is at 20 ± 0.05 DEG C, K=3.07 × 10-2, α=0.76).
dConversion ratio=polymer quality/monomer gross mass × 100%.
From table 2 it can be seen that in the continuous precipitation polymerization of acrylonitrile, with FeCl3·6H2The increase of O dosage, poly- third Alkene nitrile molecular weight is gradually reduced, and monomer conversion illustrates this polymerization system industrial utilization valence with higher 92% or more Value.
Comparative example 3: influence of the different monomers dosage to polyacrylic acid (sodium) molecular weight and conversion ratio.
Using 75ml water as solvent, respectively by acrylic acid (28.80g, 0.400mol) and corresponding FeCl3·6H2O (0.135g, 0.5mmol；0.270g, 1mmol；0.405g, 1.5mmol) it is added in 500ml three-necked flask, with d/1s speed drop Add hydrogen peroxide-aqueous solution 25g (wt.%=2.0%, 0.015mol；Wt.%=4.1%, 0.030mol；Wt.%= 6.1%, 0.045mol), until being added dropwise to complete, react 12-24h；Reaction solution takes subnatant after adding toluene to extract, and adds in NaOH With to pH=9-10, it is filtered to remove Fe (OH)3With Fe (OH)2Precipitating, obtains required polymer after drying.
By using the acrylic monomers of different proportion, the change of polymer molecular weight, conversion ratio and molecular weight distribution is investigated Change, as a result as shown in table 3 below.
Influence of the 3. different monomers dosage of table to polymerization reactiona
aPolymerizing condition: T=45 DEG C；
bRatio=[AA]0/[FeCl3·6H2O]0/[H2O2]0；.
From table 3 it can be seen that 1, No. 2 comparison, polymerization time increases, molecular weight of product in the polymerization process of acrylic acid Increase；2,3, No. 5 comparisons, with [AA]0/[FeCl3·6H2O]0Ratio increase to 1200/1.5 by 400/1.5, gained is poly- The molecular weight for closing object is gradually increased, but molecular weight distribution broadens, this is primarily due to the increase with monomer concentration, and system generates The relative amount of free radical tails off, and system controllability is deteriorated, to affect the molecular weight distribution of polymer.
Comparative example 4: shadow of the different chain tra nsfer initiator amounts to polymethylacrylic acid (sodium) molecular weight and conversion ratio It rings.
Using 75ml water as solvent, respectively by methacrylic acid (30.10g, 0.350mol) and corresponding FeCl3· 6H2O (0.135g, 0.5mmol；0.270g, 1mmol；0.405g, 1.5mmol) it is added in 500ml three-necked flask, with d/1s speed Hydrogen peroxide-aqueous solution 25g (wt.%=4.1%, 0.030mol) is added dropwise in degree, until being added dropwise to complete, back flow reaction 48h；Reaction Liquid is precipitated in ethyl acetate after taking out, stands, is filtered, and after dry plus NaOH is neutralized to pH=9-10, is filtered to remove Fe (OH)3 With Fe (OH)2Precipitating, obtains sodium polymethacrylate after filtrate is dried.
By using the chain tra nsfer initiator of different proportion, polymer molecular weight, conversion ratio and molecular weight distribution are investigated Variation, as a result as shown in table 4 below.
Influence of the different chain tra nsfer initiator amounts of table 4. to polymerization reactiona
aPolymerizing condition: T=45 DEG C；
bRatio=[MAA]0/[FeCl3·6H2O]0/[H2O2]0；
From table 4, it can be seen that in the polymerization process of methacrylic acid, it is single with the increase of chain tra nsfer initiator amount Transformation rate first increases and then decreases, as [MAA]0/[FeCl3·6H2O]0/[H2O2]0Ratio be 350/1.0/30 when, monomer turn Rate is higher, and molecular weight distribution is relatively narrow, this is because when chain tra nsfer initiator is less, monomer radical can not completely and FeCl3 Complexing is formed, the living radical of generation is less；Transition metal ions when chain tra nsfer initiator is more, in chain tra nsfer initiator Inhibition can be generated to the growth of chain again, influence polymerization rate.
Comparative example 5: influence of the reaction time to polymethylacrylic acid (sodium) molecular weight and conversion ratio.
Using 75ml water as solvent, respectively by methacrylic acid (30.10g, 0.350mol), FeCl3·6H2O (0.270g, 1mmol) be added 500ml three-necked flask in, with d/1s speed be added dropwise hydrogen peroxide-aqueous solution 25g (wt.%=4.1%, 0.030mol), until being added dropwise to complete, 6-48h is reacted；Reaction solution is precipitated in ethyl acetate after taking out, stands, is filtered, dry Afterwards plus NaOH is neutralized to pH=9-10, is filtered to remove Fe (OH)3With Fe (OH)2Precipitating, obtains polymethyl after filtrate is dried Sour sodium, polymerization reaction front and back conversion ratio and the change of molecular weight are as shown in Figure 3,4.
By controlling the different reaction time, the variation of polymer molecular weight, conversion ratio and molecular weight distribution is investigated, as a result As shown in table 5 below.
Influence of the 5. differential responses time of table to polymerization reactiona
aPolymerizing condition: T=45 DEG C；[MAA]0/[FeCl3·6H2O]0/[H2O2]0=350/1.0/30；
As can be seen from Table 5, in the polymerization process of methacrylic acid, with the progress of reaction, monomer conversion is gradually Increase, polymer molecular weight also gradually increases, and all has preferable molecular weight distribution, and react under lower temperature (45 DEG C) just It is available more excellent as a result, illustrating H2O2/FeCl3Primosome system has controllable living polymerization ability well in water, is applicable in completely In the activity/controllable free-radical polymerisation of the water-soluble alkene such as acrylic acid, methacrylic acid in water.
In summary, the present invention is by using H2O2/FeCl3·6H2Two kinds of raw materials of O constitute a kind of novel initiation system, at Function realizes the activity/controllable free-radical polymerisation of the water-soluble monomers such as acrylic acid, methacrylic acid in water, while realizing third The continuous aqueous phase precipitation polymerization of alkene nitrile in water and activity/controllable free-radical polymerisation in DMSO.Compared with traditional activated/controllable Free radical polymerization, initiation system of the present invention is without using expensive ligand and volatile organic solvent, experiment condition Mildly, simple process, it is environmentally protective, for short of electricity subclass alkene activity/controllable free-radical polymerisation provide it is a kind of more green Method.

Claims (10)

1. a kind of method of short of electricity subclass alkene free radical polymerization, which is characterized in that draw short of electricity subclass olefinic monomer, chain tra nsfer Hair agent is dissolved in reaction dissolvent, and H is added2O2As initiator, Raolical polymerizable is carried out；The chain tra nsfer initiator is chlorine Change the mixing of one or more of iron, ferric bromide, copper chloride, copper bromide.
2. the method as described in claim 1, which is characterized in that the short of electricity subclass olefinic monomer is vinyl cyanide, acrylic acid Any one in class, acrylamide monomers.
3. the method as described in claim 1, which is characterized in that the short of electricity subclass alkene is selected from acrylonitrile, acrylic acid, methyl Any one in acrylic acid, acrylamide.
4. the method as described in claim 1, which is characterized in that the molar ratio between the chain tra nsfer initiator and initiator It is 1: 20-60.
5. method as claimed in claim 4, which is characterized in that the short of electricity subclass olefinic monomer, chain tra nsfer initiator and draw Sending out the molar ratio between agent is 200-2000: 1: 20-60.
6. the method as described in claim 1, which is characterized in that the reaction dissolvent is water, any one in DMF, DMSO Or several mixtures.
7. the method as described in claim 1, which is characterized in that the adding manner of initiator are as follows: H is added dropwise2O2Solution, when dropwise addition Between be 15-30min.
8. the method as described in claim 1, which is characterized in that the temperature of Raolical polymerizable is 25-70 DEG C.
9. the method as described in claim 1, which is characterized in that the temperature of Raolical polymerizable is 30-50 DEG C.
10. the method as described in claim 1, which is characterized in that the time of Raolical polymerizable is 2-48h.
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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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