WO2021049627A1 - Procédé de production de polymère et catalyseur de polymérisation - Google Patents

Procédé de production de polymère et catalyseur de polymérisation Download PDF

Info

Publication number
WO2021049627A1
WO2021049627A1 PCT/JP2020/034491 JP2020034491W WO2021049627A1 WO 2021049627 A1 WO2021049627 A1 WO 2021049627A1 JP 2020034491 W JP2020034491 W JP 2020034491W WO 2021049627 A1 WO2021049627 A1 WO 2021049627A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
polymerization catalyst
producing
iodine
polymerization
Prior art date
Application number
PCT/JP2020/034491
Other languages
English (en)
Japanese (ja)
Inventor
洋 新納
俊介 茶谷
書堯 許
後藤　淳
ジュン ジエ チャン
Original Assignee
三菱ケミカル株式会社
ナンヤン テクノロジカル ユニヴァーシティー
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 三菱ケミカル株式会社, ナンヤン テクノロジカル ユニヴァーシティー filed Critical 三菱ケミカル株式会社
Priority to JP2021545622A priority Critical patent/JP7523768B2/ja
Publication of WO2021049627A1 publication Critical patent/WO2021049627A1/fr

Links

Images

Classifications

    • 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
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • 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
    • C08F20/00—Homopolymers and copolymers 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
    • 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
    • C08F20/00—Homopolymers and copolymers 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/52—Amides or imides
    • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F20/56—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
    • C08F4/00—Polymerisation catalysts
    • C08F4/40—Redox systems

Definitions

  • the present invention relates to a method for producing a polymer and a polymerization catalyst.
  • the present application claims priority based on Japanese Patent Application No. 2019-16772 filed on September 13, 2019, and Japanese Patent Application No. 2019-167783 filed on September 13, 2019. The contents are used here.
  • a radical polymerization method is well known as a method for obtaining a polymer by polymerizing a vinyl monomer.
  • the radical polymerization method has a problem that it is difficult to control the molecular weight of the obtained polymer.
  • the polymer obtained by the radical polymerization method is a mixture of polymers having various molecular weights, and has a problem that it is difficult to form a polymer having a narrow molecular weight distribution.
  • the living radical polymerization method is known as a method for solving the above-mentioned problems.
  • a living radical polymerization method called reversible complex formation-mediated polymerization (RCMP) has been developed (see, for example, Patent Document 1).
  • the RCMP method is an organic catalyst type living radical polymerization method in which an iodine atom is used as a protecting group for growth radicals in living radical polymerization and an amine is used as a polymerization catalyst.
  • a low molecular weight amine such as triethylamine (TEA) can be used as a polymerization catalyst. Therefore, as compared with other living radical polymerization methods using a transition metal complex as a polymerization catalyst, the polymerization catalyst has features such as low cost and high environmental safety.
  • a low molecular weight amine such as TEA
  • a purification step for removing the catalyst from the polymer which is a reaction product is required. Therefore, the RCMP method using a low molecular weight amine has a problem that the operation becomes complicated industrially.
  • a heterogeneous catalyst in which the catalyst is supported on a solid is generally used in order to easily remove the catalyst from the reaction product.
  • a polymerization system for example, an example of using a non-uniform copper catalyst in which a copper catalyst is supported on a polymer is known (Non-Patent Document 1).
  • Non-Patent Document 1 an example of using a non-uniform copper catalyst in which a copper catalyst is supported on a polymer is known (Non-Patent Document 1).
  • Non-Patent Document 1 an example of using a non-uniform copper catalyst in which a copper catalyst is supported on a polymer.
  • the activity and selectivity of the catalyst that was expressed in the catalyst before the support is changed, so that it has sufficient performance in the living radical polymerization of vinyl monomers so far. No heterogeneous catalyst was found.
  • a method of adding iodine to generate an amine-I 2 complex acting as an inactive agent is widely used.
  • iodine remains in the reaction product and causes coloring. Therefore, when iodine is added in the RCMP method, a purification step for removing iodine from the polymer which is a reaction product is required, and there is a problem that the operation becomes complicated industrially.
  • the present invention has been made in view of such circumstances, and provides a polymerization catalyst having high activity in living radical polymerization without using a transition metal-based catalyst and which can be removed by a simple method.
  • the purpose is to do.
  • Another object of the present invention is to provide a method for producing a polymer using the polymerization catalyst, in which the molecular weight and the molecular weight distribution can be sufficiently controlled, and the residual iodine amount and the catalyst amount can be reduced.
  • a method for producing a polymer which comprises a step of polymerizing a vinyl monomer to obtain a polymer in the presence of a polymerization catalyst composed of a polymer having a nitrogen-containing functional group and an organic iodine compound.
  • [6] The method for producing a polymer according to [5], wherein the polymer has a polystyrene skeleton or a polyacrylamide skeleton.
  • [7] The weight according to any one of [1] to [6], wherein the nitrogen-containing functional group is at least one selected from the group consisting of a secondary amino group, a tertiary amino group and a quaternary ammonium group. Manufacturing method of coalescence.
  • [8] The method for producing a polymer according to [7], wherein the nitrogen-containing functional group is a quaternary ammonium group.
  • the present invention it is possible to provide a polymerization catalyst that is highly environmentally safe and can be removed by a simple method. Further, in the method for producing a polymer using the polymerization catalyst, the molecular weight and the molecular weight distribution can be sufficiently controlled, and the residual iodine amount and the catalyst amount can be further reduced.
  • FIG. 1 is an XPS chart of the reaction product obtained in the production example of the example.
  • Vinyl monomer means a compound containing at least one vinyl group (carbon-carbon unsaturated double bond).
  • (Meta) acrylate means “acrylate” or “methacrylate”.
  • the "organoiodine compound” means a compound having a carbon-iodine bond in one molecule.
  • the method for producing a polymer of the present embodiment includes a step of polymerizing a vinyl monomer in the presence of a polymerization catalyst composed of a polymer having a nitrogen-containing functional group and an organic iodine compound to obtain a polymer. ..
  • a polymerization catalyst composed of a polymer having a nitrogen-containing functional group and an organic iodine compound to obtain a polymer. ..
  • a polymerizable composition containing a polymerization catalyst composed of a polymer having a nitrogen-containing functional group and a vinyl monomer is prepared, and the polymer is polymerized by polymerizing the vinyl monomer. obtain.
  • a polymerizable composition containing a polymerization catalyst composed of a polymer having a nitrogen-containing functional group and a vinyl monomer is prepared, and the polymer is polymerized by polymerizing the vinyl monomer. obtain.
  • the components contained in the polymerizable composition will be described.
  • the polymerization catalyst contains a polymer having a nitrogen-containing functional group.
  • the polymerization catalyst preferably contains a polymer having a nitrogen-containing functional group as a main component.
  • the polymerization catalyst may contain other components as long as the effects of the present invention are not significantly impaired.
  • the “main component” means that the ratio of the polymer to the entire polymerization catalyst exceeds 50% by mass. From the viewpoint of removing the polymerization catalyst from the reaction product, the polymer preferably contains 80% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more, based on the entire polymerization catalyst. ..
  • the polymers constituting the polymerization catalyst are synthetic polymers such as polystyrene, polyacrylamide, poly (meth) acrylic acid, and poly (meth) acrylic acid ester in the molecular skeleton, and naturally produced polysaccharides such as cellulose.
  • the polymer is preferably a polymer having a repeating unit of a vinyl monomer, and more preferably a polymer having a polystyrene skeleton or a polyacrylamide skeleton.
  • polystyrene skeleton means a molecular chain having a repeating unit derived from styrene or a repeating unit derived from a styrene derivative.
  • polyacrylamide skeleton means a molecular chain having a repeating unit derived from acrylamide or a repeating unit derived from an acrylamide derivative.
  • the polymer constituting the polymerization catalyst preferably contains 80 mol% or more of vinyl monomer, more preferably 90 mol% or more, and further preferably 95 mol% or more, based on all the repeating units of the polymer. preferable.
  • the polymer constituting the polymerization catalyst is a polymer having a polystyrene skeleton or a polyacrylamide skeleton. That is, "mainly" means that the ratio of the polystyrene skeleton or the polyacrylamide skeleton to all the repeating units of the polymer exceeds 50 mol%, preferably 80 mol% or more, and 90 mol% or more. Is more preferable, and 95 mol% or more is further preferable.
  • the polymer constituting the polymerization catalyst of the present embodiment may have a property of being difficult to dissolve in the solvent used in the radical polymerization, the dispersion medium, and the monomer used in the radical polymerization. As a result, the polymerization catalyst can be easily separated from the reaction solution after radical polymerization. “Difficult to dissolve” means that the solubility at 25 ° C. is 0 g / 100 mL to 0.3 g / 100 mL.
  • the upper limit of the solubility of the polymer constituting the polymerization catalyst in the solvent used for radical polymerization, the dispersion medium, and the monomer used for radical polymerization is preferably 0.2 g / 100 mL or less, and preferably 0.1 g / 100 mL or less. Is more preferable.
  • a number average molecular weight of 3000 or more is preferable because the polymer is difficult to dissolve in the reaction system of radical polymerization.
  • a polymer is a "crosslinked body", that is, a structure in which chemical bonds are formed between molecules of a chain polymer and are connected so as to bridge between the molecular chains of a chain polymer, that is, a crosslinked structure. It means that it is a polymer having.
  • the number average molecular weight of the polymer is 10,000 or more.
  • the upper limit of the number average molecular weight of the polymer is not particularly limited, but from a practical point of view, it is preferably 10,000,000 or less.
  • the polymer constituting the polymerization catalyst is preferably a crosslinked product, more preferably a crosslinked product having a repeating unit of a vinyl monomer, and a crosslinked product of a polymer having a polystyrene skeleton or a crosslinked polymer having a polyacrylamide skeleton.
  • the body is more preferred.
  • a crosslinked polymer may be referred to as a “crosslinked polymer”. In this sense, for example, a crosslinked polystyrene is sometimes referred to as “crosslinked polystyrene”.
  • the degree of cross-linking of the polymer is not particularly limited. Further, the molecular weight distribution of the polymer is not particularly limited.
  • the fact that the polymer is crosslinked can be confirmed by the fact that the sample remains undissolved when the sample of the polymer to be verified is immersed in a good solvent of the sample. At this time, it is preferable that the sample does not dissolve or only swells.
  • the "good solvent for the sample” can be selected by analyzing the sample by a commonly known method such as infrared spectroscopy or NMR, and inferring the molecular structure of the repeating unit of the sample from the obtained results.
  • the polymer according to this embodiment is not particularly limited in shape, form, size, etc., such as granular, fibrous, and film-like.
  • the granular polymer can be obtained by appropriately cutting or pulverizing the massive polymer.
  • the polymer constituting the polymerization catalyst has at least one nitrogen-containing functional group.
  • the nitrogen-containing functional group acts as a polymerization catalyst, and the nitrogen-containing functional group is covalently bonded to the polymer.
  • the nitrogen-containing functional group of the polymer is not particularly limited. Further, the nitrogen-containing functional group contained in the polymer may be contained in either the main chain or the side chain of the polymer, or may be contained in both the main chain and the side chain.
  • the polymerization catalyst may contain a low molecular weight compound having a nitrogen-containing functional group.
  • a low molecular weight compound having a nitrogen-containing functional group also functions as a part of the polymerization catalyst, but purification for removing the low molecular weight compound from the polymer which is a reaction product is required.
  • the ratio of the nitrogen-containing functional group covalently bonded to the polymer is more preferably 99.9 mol%.
  • the nitrogen-containing functional group examples include an amino group, a quaternary ammonium group, an amide group, an imide group, a nitrile group, and a pyridyl group.
  • the nitrogen-containing functional group is preferably an amino group or a quaternary ammonium group from the viewpoint of catalytic activity, and more preferably a secondary amino group, a tertiary amino group or a quaternary ammonium group from the viewpoint of ease of reaction. ..
  • the counter ion of the quaternary ammonium group is not particularly limited, and a halogen ion or a hydroxide ion can be adopted.
  • the counter ion is preferably a halogen ion, more preferably an iodine ion.
  • the quaternary ammonium group may be possessed by the polymerization catalyst before the polymerization reaction using the polymerization catalyst, and is generated by the reaction of the nitrogen-containing functional group of the polymerization catalyst in the reaction system of the polymerization reaction using the polymerization catalyst. You may. Nitrogen-containing functional groups can be identified by known analytical methods such as IR spectrum, NMR spectrum, UV spectrum, and mass spectrum.
  • the polymer constituting the polymerization catalyst has the repeating units shown in (1'-1) to (1'-6).
  • the polymer constituting the polymerization catalyst is preferably a crosslinked product.
  • R1 is an alkyl group having 1 to 4 carbon atoms
  • R2 to R4 are independently hydrogen atoms, an alkyl group having 1 to 20 carbon atoms, or the following formula. (1'-7) is shown.
  • R5 represents an alkyl group having 1 to 10 carbon atoms
  • n represents an integer of 1 to 10.
  • R1 to R5 when R1 to R5 are alkyl groups, R1 to R5 may have a substituent.
  • the substituent is at least one selected from the group consisting of a hydroxyl group, a carboxyl group, and an alkali metal salt of a carboxyl group.
  • polymers constituting the polymerization catalyst include polymers having repeating units as shown in the following formulas (1-1) to (1-10).
  • n represents an integer of 1 to 4. Further, in the equation (1-4), n represents an integer of 1 to 10.
  • Polymerization catalysts having the structures of the above formulas (1-1) to (1-10) are also available as commercially available ion exchange resins and chelate resins having completely different uses from the polymerization catalysts.
  • Examples of commercially available ion exchange resins include SA series, PA series, and HPA series of strongly basic anion exchange resins manufactured by Mitsubishi Chemical Co., Ltd., and WA series of weakly basic anion exchange resins. Examples thereof include SAF series and PAF series of low odor and low elution anion exchange resins.
  • Dow Chemical Company's Dowex Marathon (registered trademark) MSA Chloride, Amberlist (registered trademark) A21, and Amberlite (registered trademark) IRA-96 can be mentioned.
  • Examples of commercially available chelate resins include Mitsubishi Chemical's Diaion (registered trademark) iminodiacetic acid type and polyamine type CR series, and glucamine type CRB series.
  • polymer having a nitrogen-containing functional group can be obtained by, for example, the following method.
  • crosslinked polystyrene is obtained by copolymerization of styrene and divinylbenzene.
  • the above polymer may be used alone or in combination of two or more.
  • the polymerization catalyst preferably contains iodine (I 2 ) in addition to the above polymer.
  • Iodine functions as an inactive agent that suppresses the concentration of active species, which will be described later, and suppresses the termination reaction due to the binding and disproportionation of radical species.
  • Iodine can exist in a state of being physically adsorbed on the surface of the polymer. Iodine can be physically adsorbed on the surface of the polymer by a method such as mixing iodine in the polymerizable composition containing the polymer.
  • the polymerization catalyst may contain iodine atom-containing ions.
  • the "iodine atom-containing ion" is an iodide ion (I ⁇ ), a triiodide ion (I 3 ⁇ ), or a pentaiodide ion (I 5 ⁇ ).
  • the iodine atom-containing ion has a function of enhancing the catalytic performance of the above-mentioned polymer.
  • the iodine atom-containing ion can exist in a state of being ionically bonded to the polymer as a counter ion of a quaternary ammonium group possessed by the polymer.
  • vinyl monomer examples include, for example.
  • the vinyl monomer at least one selected from the group consisting of a styrene-based monomer, a (meth) acrylate-based monomer, and (meth) acrylonitrile is preferable from the viewpoint of polymerization control.
  • the vinyl monomer may be used alone or in combination of two or more.
  • an organic iodine compound (dormant species) having a carbon-iodine bond is present in the polymerizable composition, and iodine given to the growth chain from this organic iodine compound is used as a growth radical. Used as a protective radical for iodine.
  • the organic iodine compound is not particularly limited as long as it has at least one carbon-iodine bond in the molecule and acts as a dormant species.
  • a compound containing one or two iodine atoms in one molecule is preferable.
  • the organic iodine compound may be added as an organic iodine compound in the polymerizable composition, or may be produced by reacting a compound added as another compound in a reaction system.
  • an organic iodine compound is produced by reacting at least a part of each of the radical polymerization initiator described later with iodine in the process of polymerization.
  • organic iodine compound examples include iodotrichloromethane, dichlorodiiodomethane, iodotribromomethane, dibromodiiodomethane, bromotriiodomethane, iodoform, diiodomethane, methyl iodide, triiodoethane, ethyl iodide, and diiodopropane.
  • One type of organic iodine compound may be used alone, or two or more types may be used in combination.
  • At least one selected from the group consisting of -I, MAA-I, HEMA-I, AAm-I, EMA-II, EA-II, EMA-III, and IHE is preferred.
  • a radical polymerization initiator may be added to the polymerizable composition.
  • the radical polymerization initiator polymerizes a polymerizable composition containing a polymerization catalyst, a vinyl monomer, an organic iodine compound, and iodine
  • the radical polymerization initiator increases the radical concentration in the polymerizable composition and increases the polymerization rate. Used for the purpose of raising.
  • radical polymerization initiator known compounds such as an azo-based radical polymerization initiator and a peroxide-based radical polymerization initiator can be used.
  • the polymerization reaction can be carried out by using the above-mentioned polymerization catalyst, and a radical polymerization initiator may not be substantially used.
  • a radical polymerization initiator is used in the method for producing a polymer of the present embodiment, the polymerization rate can be improved and the polymerization time can be shortened as compared with the case where the radical polymerization initiator is not used.
  • azo radical polymerization initiator examples include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), and 2,2'-azobis (2,4-dimethyl). Valeronitrile) and 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile).
  • peroxide-based radical polymerization initiator examples include 2,4-dichlorobenzoyl peroxide, t-butyl peroxypivalate, o-methylbenzoyl peroxide, and bis-3,5,5-trimethylhexanoyl peroxide.
  • Octanoyl peroxide Octanoyl peroxide, t-butylperoxy-2-ethylhexanoate, cyclohexanone peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, lauroyl peroxide, diisopropylbenzene hydroperoxide, t-butyl hydro Examples include peroxides and di-t-butyl peroxides.
  • benzoyl peroxide 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,) 4-Dimethylvaleronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile) and 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile) are preferred in terms of availability. ..
  • the radical polymerization initiator may be used alone or in combination of two or more.
  • iodine In the method for producing a polymer of the present embodiment, iodine may be contained in the polymerization catalyst as described above, or may be added separately to the polymerizable composition. Iodine suppresses the concentration of active species, which will be described later, as an inactivating agent for the polymerization reaction, and suppresses the termination reaction due to the binding and disproportionation of radical species. Further, by using iodine and the above-mentioned radical initiator in combination, an organic iodine compound can be produced in the reaction system.
  • additives In the method for producing a polymer of the present embodiment, other additives can be added as needed. Examples of other additives include chain transfer agents.
  • Examples of the chain transfer agent include mercaptan.
  • an organic solvent can be used at the time of polymerization.
  • the organic solvent include hydrocarbon solvents such as toluene; ether solvents such as diethyl ether and tetrahydrofuran; halogenated hydrocarbon solvents such as dichloromethane and chloroform; ketone solvents such as acetone; alcohol solvents such as methanol; acetonitrile. And other nitrile solvents; vinyl ester solvents such as ethyl acetate; carbonate solvents such as ethylene carbonate; and supercritical carbon dioxide can be exemplified.
  • the organic solvent one type may be used alone, or two or more types may be used in combination.
  • the content of the solvent is preferably more than 0% by mass and 700% by mass or less when the total amount of the polymerizable composition excluding the solvent is 100% by mass.
  • composition of polymerizable composition An example of the polymerizable composition is a polymerizable composition containing the above-mentioned polymerization catalyst, vinyl monomer, organic iodine compound, and iodine.
  • a polymerizable catalyst containing a polymer having a nitrogen-containing functional group and iodine, a vinyl monomer, an organic iodine compound, and a radical polymerization initiator is mentioned.
  • the polymerizable composition there is a polymerizable composition containing a polymerization catalyst containing a polymer having a nitrogen-containing functional group and iodine, a vinyl monomer, and a radical polymerization initiator. ..
  • a polymerizable composition does not contain an organic iodine compound, but as described above, at least a part of each of the radical polymerization initiator and iodine reacts in the process of polymerization to form an organic iodine compound in the polymerizable composition. Generates and functions as a dormant species.
  • the content of the polymerization catalyst in the polymerizable composition is preferably 0.01% by mass or more and 50% by mass or less with respect to the total amount of the vinyl monomer and the polymerization catalyst.
  • the lower limit of the content of the catalyst with respect to the total amount of the vinyl monomer and the polymerization catalyst is more preferably 0.1% by mass or more, and further preferably 1% by mass or more.
  • the upper limit is more preferably 30% by mass or less, and further preferably 20% by mass or less.
  • the upper limit value and the lower limit value can be arbitrarily combined.
  • the molar equivalent ratio of nitrogen atoms contained in the polymerization catalyst is preferably 0.0001 or more and 0.5 or less, and more preferably 0.0005 or more and 0.1 or less with respect to the vinyl monomer.
  • the molar equivalent ratio of nitrogen atoms contained in the polymerization catalyst is preferably 0.001 or more and 1000 or less, and more preferably 0.01 or more and 180 or less with respect to the added organic iodine compound.
  • the above-mentioned upper limit value and lower limit value of the molar equivalent ratio can be arbitrarily combined.
  • the molar equivalent ratio of the nitrogen-containing functional group contained in the polymerization catalyst is preferably 0.001 or more and 200 or less with respect to the total of the added organic iodine compound and the radical polymerization initiator.
  • the lower limit of the molar equivalent ratio of the nitrogen-containing functional group is more preferably 0.005 or more, and further preferably 0.01 or more. Further, the upper limit is more preferably 100 or less. The above-mentioned upper limit value and lower limit value of the molar equivalent ratio can be arbitrarily combined.
  • the polymerization rate is sufficiently promoted, and the polymerization solution maintains an appropriate viscosity and is easy to handle.
  • the molar equivalent ratio of nitrogen atoms contained in the polymerization catalyst can be determined by an elemental analysis method.
  • the molar equivalent ratio of nitrogen atoms in the polymer contained in the polymerization catalyst can also be determined by the following method. First, the excess amount of the organic iodine compound having a known molecular weight is completely reacted with the polymer in the polymerization catalyst. Next, the amount of substance (mol) of the organic iodine compound that has reacted with the nitrogen-containing functional group is determined from the reaction rate of the organic iodine compound, and the amount of substance (mol) of the nitrogen-containing functional group is determined from the amount of substance of the reacted organic iodine compound. From the amount of substance of the obtained nitrogen-containing functional group, the molar equivalent ratio of nitrogen atoms is calculated.
  • the molar equivalent ratio of the nitrogen-containing functional groups contained in the polymerization catalyst can be calculated by, for example, the following method. 2.0 g of the polymerization catalyst and 1.21 g (5.61 mmol) of 1-iodohexane are mixed and uniformly dispersed in 8 ml of tetrahydrofuran. The dispersion solution is reacted in a reflux state for 24 hours with heating and stirring. An internal standard having a known concentration is added to the obtained reaction solution, 1 H-NMR is measured, and the amount of decrease in 1-iodohexane is determined from the amount of remaining 1-iodohexane. The molar equivalent ratio of 1-iodohexane decreased at this time is equal to the molar equivalent ratio of the nitrogen-containing functional groups contained in the polymerization catalyst.
  • the molar equivalent ratio of iodine contained in the polymerization catalyst is arbitrary.
  • the amount of the vinyl monomer is preferably 0.0001 or more and 0.5 or less, and more preferably 0.0005 or more and 0.1 or less.
  • the polymerization rate can be sufficiently promoted.
  • the molar equivalent ratio of iodine contained in the polymerization catalyst is a value obtained by elemental analysis of the polymerization catalyst or a value obtained from the amount charged when synthesizing the polymerization catalyst.
  • the content of the organic iodine compound in the polymerizable composition is arbitrary.
  • the content of the organic iodine compound in the polymerizable composition is preferably 0.001 mol or more and 0.5 mol or less per 1 mol of the vinyl monomer, and the amount is 0.002 mol or more and 0.1 mol or less. More preferred.
  • the content of the organic iodine compound in the polymerizable composition is within the above range, it is sufficient to provide the iodine atom as a protecting group from the organic iodine compound to the growth chain of the polymerization reaction, and the polymerization rate is extremely high. Do not lower.
  • the content of the radical polymerization initiator in the polymerizable composition is arbitrary.
  • the content of the radical polymerization initiator in the polymerizable composition is preferably 0.0001 mol or more and 0.05 mol or less, and 0.0002 mol or more and 0.02 mol or less per mol of the vinyl monomer. Is more preferable.
  • an appropriate polymerization rate can be obtained.
  • the nitrogen-containing functional group of the polymerization catalyst has an action of promoting a redox reaction in the living radical polymerization of a vinyl monomer having a carbon-iodine bond as a dormant species. Therefore, in the method for producing a polymer of the present embodiment, the polymerization catalyst extracts iodine atoms from the organic iodine compound to generate radicals derived from the organic iodine compound.
  • the method for producing the polymer of the present embodiment is not particularly bound by theory, but the presumed mechanism will be described below.
  • Scheme 1 shows the reaction formula of the RCMP method, which is generally known.
  • A is a polymerization catalyst having a redox ability
  • I is an iodine atom.
  • the polymerization catalyst A is in a reduced state on the left side of the reaction formula and in an oxidized state on the right side.
  • radicals of the polymer which is an active species are generated, and when the polymerization catalyst A is in the reducing state, the ends of the polymer are protected by iodine atoms.
  • Polymer-I on the left side is a dormant species in the reaction system, and "Polymer.” On the right side is an active species in the reaction system.
  • the polymerization catalyst A reversibly undergoes a redox reaction between the reduced state (left side) and the oxidized state (right side). Further, as shown in Scheme 1, Scheme 1 is an equilibrium reaction, and the equilibrium is biased to the left side. That is, active species are present in low concentrations in the reaction system.
  • the dormant species (Polymer-I) shown on the left side is protected at the end by an iodine atom and the reaction is stopped.
  • the active species (radicals of the polymer) shown on the right side radically polymerize with the vinyl monomer to generate a polymer.
  • the polymer terminal always keeps its activity (living room), and the molecular weight distribution can be made uniform.
  • the polymerization catalyst for example, when a crosslinked polymer having a tertiary amino group which is a nitrogen-containing functional group in the side chain of crosslinked polystyrene is used as the polymerization catalyst, the polymerization catalyst
  • the reaction formula for the reaction is considered to be as shown in Scheme 2 below. On the right side of the equation below, it can be in the state of a salt in which one electron is transferred between the tertiary amino group and the iodine atom, or in the state of a complex in which the partial charge is transferred between the tertiary amino group and iodine.
  • the polymerization catalyst is in an oxidized state because electrons are supplied from the nitrogen atom of the tertiary amino group to the radical of iodine on the right side of the following formula. In relative terms, the polymerization catalyst is in a reduced state on the left side.
  • the above formula is the above-mentioned "state of a salt in which one electron is transferred between a tertiary amino group and an iodine atom"
  • the lower formula after dimerization is the above-mentioned “class 3”.
  • a complex in which a partial charge is transferred between an amino group and iodine is shown.
  • the dimerization shown on the right side may occur between different nitrogen-containing functional groups existing in continuous molecular chains, or may occur between different nitrogen-containing functional groups existing in different molecular chains.
  • the polymerization catalyst reversibly undergoes a redox reaction between the reduced state (left side) and the oxidized state (right side), so that the radical of the polymer shown on the right side is a single amount of vinyl. It is considered that the polymer is polymerized with the body to obtain the desired polymer.
  • the polymerization method in the method for producing the polymer of the present embodiment is not particularly limited, and examples thereof include a massive polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method.
  • the polymerization reaction may be carried out in the presence of air, but from the viewpoint of the efficiency of radical polymerization, it is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon.
  • the polymerization temperature is preferably 0 ° C. or higher and 150 ° C. or lower because an appropriate polymerization rate can be easily obtained. Further, since polymerization control is easy, 20 ° C. or higher and 120 ° C. or lower is more preferable. Further, when the polymerization temperature is 120 ° C. or lower, the activity of the polymerization catalyst can be easily maintained, which is preferable.
  • the polymerization time is not particularly limited, and can be, for example, 0.5 hours or more and 24 hours or less.
  • the polymer produced by the method for producing a polymer of the present embodiment has an iodine atom at the end of the main chain.
  • I of "Polymer-I" shown in the above scheme 1 corresponds.
  • the iodine atom at the terminal can be removed by treating at a high temperature.
  • a functional group derived from the nucleophile can be introduced by reacting the iodine atom at the terminal with the nucleophile.
  • the molecular weight distribution (Mw / Mn) of the polymer obtained by a known typical controlled polymerization is generally less than 1.5.
  • Mw is a weight average molecular weight
  • Mn is a number average molecular weight.
  • the Mw / Mn of the obtained polymer can be less than 1.5.
  • the molecular weight may be larger than the target Mw / Mn depending on the dispersed state of the polymerization catalyst.
  • Mw / Mn can be reduced by satisfactorily dispersing the polymerization catalyst in the reaction system.
  • Examples of a method for satisfactorily dispersing the polymerization catalyst in the reaction system include a method of adding a solvent to reduce the viscosity, an increase in the stirring speed, and a method of reducing the particle size of the polymer constituting the polymerization catalyst.
  • the method for producing the polymer of the present embodiment causes a redox reaction similar to the case where the organic compound catalyst used in the generally known RCMP method is used.
  • the method for producing a polymer of the present embodiment can control the molecular weight and obtain a polymer having a narrow molecular weight distribution.
  • the polymerization catalyst used in the method for producing a polymer of the present embodiment does not contain a transition metal, is inexpensive, and has high environmental safety. On the other hand, there is a concern that the residual polymerization catalyst may cause coloring or deterioration of durability due to remaining in the polymer. Therefore, it is preferable to remove the polymerization catalyst from the reaction product.
  • the conventional organic compound catalyst can be dissolved during the reaction not only as a solvent-soluble organic compound catalyst but also as an organic compound catalyst supported on a carrier. Therefore, it was difficult to remove the organic compound catalyst from the reaction product.
  • the polymerization catalyst used in the method for producing a polymer of the present embodiment contains a polymer having a nitrogen-containing functional group. Since such a polymer is difficult to dissolve in the reaction system in which the polymerization reaction is carried out, it is difficult to remain in the reaction product.
  • the polymerization catalyst used can be easily removed from the reaction product after the polymerization reaction by a simple method. That is, in the method for producing a polymer of the present embodiment, it is preferable to have a step of removing the polymerization catalyst after the polymerization reaction of the vinyl monomer is carried out. Examples of the removal method include centrifugation and filtration.
  • the polymerization catalyst removed from the reaction product by the above method can be reused as a polymerization catalyst by appropriately washing with an organic solvent and drying.
  • the organic solvent used for cleaning includes a hydrocarbon solvent such as toluene; an ether solvent such as diethyl ether and tetrahydrofuran; a halogenated hydrocarbon solvent such as dichloromethane and chloroform; a ketone solvent such as acetone; an alcohol solvent such as methanol.
  • a hydrocarbon solvent such as toluene
  • an ether solvent such as diethyl ether and tetrahydrofuran
  • a halogenated hydrocarbon solvent such as dichloromethane and chloroform
  • a ketone solvent such as acetone
  • an alcohol solvent such as methanol.
  • examples thereof include a solvent; a nitrile solvent such as acetonitrile; a vinyl ester solvent such as ethyl acetate; a carbonate solvent such as ethylene carbonate; and supercritical carbon dioxide.
  • organic solvent used for cleaning one type may be used alone, or two or more types may be used in combination.
  • polymerization catalyst it is possible to provide a polymerization catalyst having high activity in living radical polymerization without using a transition metal-based catalyst and which can be removed by a simple method.
  • the polymer produced by the method for producing a polymer of the present embodiment is not particularly limited in use because the polymerization catalyst that causes coloring and deterioration of durability can be removed by a simple method as described above. Specific examples thereof include dispersants, resin additives, coating compositions, and lithographic polymers.
  • the molecular weight distribution (Mw / Mn) was calculated using Mn and Mw obtained by the above method.
  • the monomer conversion rate (%) of Examples and Comparative Examples is a measured value of 1 H-NMR measurement using a nuclear magnetic resonance apparatus (Bruker, "BBF0400", 400 MHz) and CDCl 3 as a measurement solvent. I asked for it. Specifically, using the integrated value of the peak derived from the residual monomer and the integrated value of the peak derived from the produced polymer, the amount of the produced polymer relative to the total amount of the residual monomer amount and the produced polymer amount. Calculated as a ratio.
  • Iodine or iodine atom-containing ions contained in the polymerization catalyst were detected by XPS (X-ray photoelectron spectroscopy, SPECS, "Phoibos 100", monochromatic X-ray light source) measurement.
  • XPS X-ray photoelectron spectroscopy, SPECS, "Phoibos 100", monochromatic X-ray light source
  • HP-20 is a polymer having a repeating unit represented by the following formula (2-1) and does not have a nitrogen-containing functional group.
  • MMA Methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • EHMA 2-ethylhexyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • LMA Lauryl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • ⁇ Radical polymerization initiator (D)> AIBN: 2,2'-azobis (isobutyronitrile) (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • V-65 2,2'-azobis (2,4-dimethylvaleronitrile) (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • Iodine manufactured by Tokyo Chemical Industry Co., Ltd.
  • Benzene (manufactured by Tokyo Chemical Industry Co., Ltd.) was precisely added to the obtained reaction solution as an internal standard, and the amount of 1-iodohexane in tetrahydrofuran was compared before and after the reaction to determine the reaction rate.
  • the reaction rate of iodine was 83% (4.74 mmol).
  • the molar equivalent of nitrogen atom can be calculated from the amount of 1-iodohexane reacted per 1 g of WA-30.
  • FIG. 1 is an XPS chart of the obtained reaction product.
  • the chart on the left shown in FIG. 1 shows the result of wide scan analysis, and the chart on the right shows the result of narrow scan analysis.
  • reaction product was recovered by filtration, washed repeatedly with tetrahydrofuran, and then dried under reduced pressure.
  • the obtained product will be referred to as "quaternized WA-30".
  • the obtained quaternized WA-30 has a number average molecular weight of 10,000 or more.
  • Example 1 A quaternized WA-30 as the polymerization catalyst (A), MMA as the vinyl monomer (B), and CP-I as the organic iodine compound (C) were weighed with the compositions shown in Table 1 to prepare a polymerizable composition. ..
  • composition unit (eq / mass%) of the polymerization catalyst (A) shown in Table 1 is the mass of the polymerization catalyst with respect to the equivalent number of nitrogen atoms contained in the polymerization catalyst and the total mass of the polymerization catalyst and the vinyl monomer (B). Means ratio. The same applies to Tables 2 and 3 described later.
  • the obtained polymerizable composition was transferred to a glass reaction vessel, the gas phase was replaced with nitrogen, and then the polymerization reaction was carried out at 70 ° C. for the time shown in Table 1 with stirring, and then the polymer was filtered.
  • the amounts of the polymerization catalyst (A), the organic iodine compound (C), and the radical polymerization initiator (D) shown in Table 1 mean the molar equivalents used with respect to 8000 molar equivalents of the vinyl monomer (B). .. Further, the molar equivalent ratio of the nitrogen-containing functional group contained in the polymerization catalyst means the molar equivalent ratio to the total of the added organic iodine compound and the radical polymerization initiator. The same applies to Table 2 described later.
  • Example 2 A polymer was obtained in the same manner as in Example 1 except that the composition of the polymerizable composition was set to the composition shown in Table 1 and a polymerization catalyst containing a polymer having a nitrogen-containing functional group and iodine was used.
  • Examples 3 to 4 A polymer was obtained in the same manner as in Example 2 except that the composition of the polymerizable composition was the composition shown in Table 1 and V-65 was used as the radical polymerization initiator (D).
  • Example 5 A polymer was obtained in the same manner as in Example 3 except that the composition of the polymerizable composition was the composition shown in Table 1 and AIBN was used as the radical polymerization initiator (D).
  • Example 7 to 8 A polymer was obtained in the same manner as in Example 5 except that the composition of the polymerizable composition was the composition shown in Table 1 and toluene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a solvent.
  • composition unit (mass%) of the solvent shown in Table 1 means the ratio of the solvent when the total amount including the solvent is 100% by mass. The same applies to Tables 2 and 3 described later.
  • Example 9 A polymer was obtained in the same manner as in Example 7 except that the composition of the polymerizable composition was the composition shown in Table 1 and EHMA was used as the vinyl monomer (B).
  • Example 11 to 12 A polymer was obtained in the same manner as in Example 7 except that the composition of the polymerizable composition was the composition shown in Table 1 and LMA was used as the vinyl monomer (B).
  • Examples 13 to 15 A polymer was obtained in the same manner as in Example 7 except that the composition of the polymerizable composition was the composition shown in Table 2 and WA-30 was used as the polymerization catalyst (A).
  • Example 16 to 17 A polymer was obtained in the same manner as in Example 11 except that the composition of the polymerizable composition was the composition shown in Table 2 and EPh-I was used as the organic iodine compound (C).
  • Example 18 A polymer was obtained in the same manner as in Example 7 except that the composition of the polymerizable composition was the composition shown in Table 2.
  • Example 19 The quaternized WA-30 used in Example 18 was recovered by centrifugation. The solid content was washed three times, with the recovery of the recovered solid content in 10 ml of tetrahydrofuran and then recovery by centrifugation as one wash. Then, the recovered solid content was dried under reduced pressure to obtain quaternized WA-30 (first reuse).
  • the polymer was prepared in the same manner as in Example 7 except that the composition of the polymerizable composition was the composition shown in Table 2 and the quaternized WA-30 (first reuse) was used as the polymerization catalyst (A). Obtained.
  • Example 20 The quaternized WA-30 used in Example 19 was recovered by centrifugation, washed three times in the same manner as in Example 19, and then dried under reduced pressure to obtain the quaternized WA-30 (second reuse). Obtained.
  • the polymer was prepared in the same manner as in Example 7 except that the composition of the polymerizable composition was the composition shown in Table 2 and the quaternized WA-30 (second reuse) was used as the polymerization catalyst (A). Obtained.
  • Example 21 The quaternized WA-30 used in Example 20 was recovered by centrifugation, washed three times in the same manner as in Example 19, and then dried under reduced pressure to obtain the quaternized WA-30 (third reuse). Obtained.
  • the polymer was prepared in the same manner as in Example 7 except that the composition of the polymerizable composition was the composition shown in Table 2 and the quaternized WA-30 (third reuse) was used as the polymerization catalyst (A). Obtained.
  • Example 22 The quaternized WA-30 used in Example 21 was recovered by centrifugation, washed three times in the same manner as in Example 19, and then dried under reduced pressure to obtain the quaternized WA-30 (fourth reuse). Obtained.
  • the polymer was prepared in the same manner as in Example 7 except that the composition of the polymerizable composition was the composition shown in Table 2 and the quaternized WA-30 (fourth reuse) was used as the polymerization catalyst (A). Obtained.
  • Example 23 A polymer was obtained in the same manner as in Example 11 except that the composition of the polymerizable composition was the composition shown in Table 2 and PMMA-I was used as the organic iodine compound (C). The obtained polymer was a block copolymer composed of PMMA and PLMA (polylauryl methacrylate).
  • Example 24 A polymer was obtained in the same manner as in Example 7 except that the composition of the polymerizable composition was the composition shown in Table 3 and a mixture of MSA Chloride and iodine was used as the polymerization catalyst (A).
  • Example 25 A polymer was obtained in the same manner as in Example 7 except that the composition of the polymerizable composition was the composition shown in Table 3 and a mixture of A21 and iodine was used as the polymerization catalyst (A).
  • Example 26 A polymer was obtained in the same manner as in Example 7 except that the composition of the polymerizable composition was the composition shown in Table 3 and a mixture of IRA-96 and iodine was used as the polymerization catalyst (A).
  • Example 27 Examples except that the composition of the polymerizable composition was the composition shown in Table 3, the polymerization catalyst (A) was changed to a mixture of WA-21J and iodine, and the amount of iodine was the amount shown in Table 3. A polymer was obtained in the same manner as in 1.
  • composition of the polymerizable composition was set to the composition shown in Table 2, and the same procedure as in Example 7 was carried out except that the quaternized WA-30 was not used.
  • composition of the polymerizable composition was the composition shown in Table 2, and the same procedure as in Example 7 was carried out except that HP-20 was used as the polymerization catalyst (A).
  • composition of the polymerizable composition was the composition shown in Table 3, and the same procedure as in Example 1 was carried out except that BNI was used as the polymerization catalyst (A) and toluene was used as the solvent.
  • Tables 1 to 3 show the measurement results of the composition, polymerization conditions, Mn, Mw / Mn, monomer conversion rate and YI of the polymerizable compositions of each Example and Comparative Example.
  • Examples 1 to 3 obtained by polymerizing a vinyl monomer (B) in the presence of an organic iodine compound using a polymer having a nitrogen-containing functional group as a polymerization catalyst (A). For 18 and 23 to 26, a constant monomer conversion rate could be obtained within a predetermined polymerization time. Further, in the obtained polymer, the molecular weight and the molecular weight distribution were controlled, and Mw / Mn became a small value.
  • Examples 1 to 18 and 23 to 26 are heterogeneous catalysts that can be easily removed.
  • a polymer having a molecular weight and a molecular weight distribution controlled in the same manner as when a low molecular weight catalyst is used is obtained.
  • Example 17 a polymer having a lower YI and a lower coloration was obtained as compared with Comparative Example 3.
  • Example 23 Further, from the results of Example 23, it was shown that a polymerization catalyst composed of a polymer having a nitrogen-containing functional group is also useful for the production of block copolymers.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne : un catalyseur de polymérisation formé à partir d'un polymère ayant des groupes fonctionnels contenant de l'azote ; et un procédé de production de polymère comprenant une étape d'obtention d'un polymère par polymérisation de monomères vinyliques en présence d'un composé d'iode organique.
PCT/JP2020/034491 2019-09-13 2020-09-11 Procédé de production de polymère et catalyseur de polymérisation WO2021049627A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2021545622A JP7523768B2 (ja) 2019-09-13 2020-09-11 重合体の製造方法および重合触媒

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2019-167782 2019-09-13
JP2019-167783 2019-09-13
JP2019167783 2019-09-13
JP2019167782 2019-09-13

Publications (1)

Publication Number Publication Date
WO2021049627A1 true WO2021049627A1 (fr) 2021-03-18

Family

ID=74865988

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/034491 WO2021049627A1 (fr) 2019-09-13 2020-09-11 Procédé de production de polymère et catalyseur de polymérisation

Country Status (2)

Country Link
JP (1) JP7523768B2 (fr)
WO (1) WO2021049627A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011016166A1 (fr) * 2009-08-06 2011-02-10 国立大学法人京都大学 Catalyseur pour polymérisation radicalaire vivante et procédé de polymérisation
JP2019094453A (ja) * 2017-11-24 2019-06-20 三菱ケミカル株式会社 重合体及びその製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011016166A1 (fr) * 2009-08-06 2011-02-10 国立大学法人京都大学 Catalyseur pour polymérisation radicalaire vivante et procédé de polymérisation
JP2019094453A (ja) * 2017-11-24 2019-06-20 三菱ケミカル株式会社 重合体及びその製造方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LI BIN, SHI YAN, FU ZHIFENG: "Schiff Base as a Novel Kind of Catalyst for Reversible Complexation-Mediated Radical Polymerization of Methyl Methacrylate", JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY, vol. 57, 29 June 2019 (2019-06-29), pages 1653 - 1663, XP055805650 *
WANG CHEN-GANG, CHANG JUN JIE, FOO ELLENDEA YONG JING, NIINO HIROSHI, CHATANI SHUNSUKE, HSU SHU YAO, GOTO ATSUSHI: "Recyclable Solid-Supported Catalysts for Quaternary Ammonium Iodide-Catalyzed Living Radical Polymerization", MACROMOLECULES, vol. 53, 19 December 2019 (2019-12-19), pages 51 - 58, XP055805652 *

Also Published As

Publication number Publication date
JPWO2021049627A1 (fr) 2021-03-18
JP7523768B2 (ja) 2024-07-29

Similar Documents

Publication Publication Date Title
JP6800827B2 (ja) 制御されたラジカル重合プロセスの改良された制御
KR101943539B1 (ko) 리빙 라디칼 중합을 위한 촉매 및 중합 방법
US8378044B2 (en) Living radical polymerization method using alcohol as catalyst
Shen et al. Atom Transfer Radical Polymerization of Methyl Methacrylate Mediated by Copper Bromide− Tetraethyldiethylenetriamine Grafted on Soluble and Recoverable Poly (ethylene-b-ethylene glycol) Supports
US8575285B2 (en) Catalyst for living radical polymerization
EP2147936B1 (fr) Nouveau procédé de polymérisation radicalaire vivante utilisant un composé du phosphore ou un composé de l'azote en tant que catalyseur
US8742045B2 (en) Polymerization initiator for living radical polymerization
WO2000056795A1 (fr) Procedes catalytiques de polymerisation controlee de monomeres (co)polymerisables par des radicaux libres et systemes de polymeres fonctionnels prepares de la sorte
US8642711B2 (en) Living radical polymerization method
WO2013043573A2 (fr) Mélanges de résine extrêmement fonctionnalisés
WO2015122404A1 (fr) Catalyseur de polymérisation radicalaire vivante, et procédé de production de polymères l'utilisant
Liu et al. Visible light‐induced controlled radical polymerization of methacrylates with perfluoroalkyl iodide as the initiator in conjugation with a photoredox catalyst fac‐[Ir (ppy)] 3
JP2002532579A (ja) 置換および未置換のα−メチレン−γ−ブチロラクトンのオリゴメリゼーション、重合および共重合およびそれらの生成物
JP2010059231A (ja) ブロック共重合体の製造法
Zhao et al. Synthesis of Poly (methyl acrylate) Grafted onto Silica Particles by Z‐supported RAFT Polymerization
CN101128491B (zh) 聚合催化剂组合物及聚合物的制造方法
WO2021049627A1 (fr) Procédé de production de polymère et catalyseur de polymérisation
EP1637550B1 (fr) Procédé catalytique pour la polymérisation contrôlée des monomères polymérisables par des radicaux, et leurs systèmes polymériques fonctionnels
Lin et al. Grafting well-defined polymers onto unsaturated PVDF using thiol-ene reactions
Pan et al. Iron-mediated (dual) concurrent ATRP–RAFT polymerization of water-soluble poly (ethylene glycol) monomethyl ether methacrylate
Temel et al. Synthesis of H‐shaped complex macromolecular structures by combination of atom transfer radical polymerization, photoinduced radical coupling, ring‐opening polymerization, and iniferter processes
Zhou et al. Zero‐valent bimetallic iron/copper catalyzed SET‐LRP: A dual activation by zero‐valent iron
US12065519B2 (en) Synthesis of polymer under conditions of enhanced catalyzed radical termination
WO2004078811A1 (fr) Solvant destine a une reaction de polymerisation et procede de production de polymere
WO2024010011A1 (fr) Générateur de radicaux contenant un groupe alcoxy, polymère radicalaire, composition et procédé de production de polymère radicalaire

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20863195

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2021545622

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20863195

Country of ref document: EP

Kind code of ref document: A1