WO2023090656A1 - Procédé de préparation de polymère - Google Patents

Procédé de préparation de polymère Download PDF

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Publication number
WO2023090656A1
WO2023090656A1 PCT/KR2022/015813 KR2022015813W WO2023090656A1 WO 2023090656 A1 WO2023090656 A1 WO 2023090656A1 KR 2022015813 W KR2022015813 W KR 2022015813W WO 2023090656 A1 WO2023090656 A1 WO 2023090656A1
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polymer
raft
group
flow reactor
reactor
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PCT/KR2022/015813
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English (en)
Korean (ko)
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김기범
정연준
최민혁
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(주)경인양행
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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
    • C08F2/00—Processes of polymerisation
    • C08F2/001—Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer
    • 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
    • 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
    • C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
    • 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
    • C08F2438/00—Living radical polymerisation
    • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]

Definitions

  • the present invention relates to a method for preparing a polymer capable of efficiently removing a functional group derived from a RAFT material from a polymer prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization.
  • RAFT reversible addition-fragmentation chain transfer
  • the decomposition point of the initiator is widely distributed from the start to the end of the polymerization, and the composition of the monomer is polymerized non-uniformly for each polymer chain due to the difference in the reactivity of the monomer, and the termination reaction between the polymer chains affects a wide molecular weight distribution (PDI) ) to obtain a polymer with
  • PDI wide molecular weight distribution
  • RAFT polymerization can be used to improve the disadvantages of the existing free radical polymerization and polymerize a polymer having a uniform monomer composition and a low PDI.
  • RAFT polymerization is one of the living radical polymerization methods that can precisely control the desired molecular weight and molecular weight distribution when synthesizing polymers. A method for synthesizing polymers.
  • RAFT polymerization is generally known to proceed according to the mechanism shown in Scheme 1 below.
  • Initiator represents a kind of initiator generating reactive radicals by being decomposed by receiving light or heat, and R is a reactive radical initiated and generated from the initiator.
  • M is a monomer that generates a polymer by a reactive radical and includes a reactive ethylene group;
  • it is a monomer typically containing a vinyl group or a (meth)acrylate group.
  • RAFT material containing a trithiocarbonate group, a dithiocarbamate group, a dithioester group, and a thiocarbonylthio group; wherein Z and A are, for example, alkyl, alkenyl, alkynyl, acyl, aralkyl, aryl, amino, heteroaralkyl, heteroaryl, cycloalkyl, aminoalkyl, alkoxyalkyl, hydroxyalkyl, heterocyclyl, alkyl carbonate, alkylcarboxylic acid, alkene carbonate, alkenecarboxylic acid, alkylcarboxylthio, alkylthio, arylthio, acylthio, arylacyl, arylcarbocyclyl, alkenyloxyaryl, alkylthioaryl, Alkenylthioaryl, arylthioaryl, arylheteroarylthio, carbocyclylthio group
  • P x and P y are polymers whose molecular weight is increasing in the propagation step, and P x+y is a polymer whose reaction has been completed by the termination step.
  • S represents a sulfur atom.
  • RAFT polymerization proceeds in the presence of a RAFT material, which is a material containing a sulfur-containing functional group, for example, a trithiocarbonate group, a dithiocarbamate group, a dithioester group, a thiocarbonylthio group, and the like. That is, since RAFT materials contain sulfur atoms, polymers produced by RAFT polymerization contain sulfur-containing functional groups attached to polymer chains or terminals.
  • a RAFT material which is a material containing a sulfur-containing functional group, for example, a trithiocarbonate group, a dithiocarbamate group, a dithioester group, a thiocarbonylthio group, and the like. That is, since RAFT materials contain sulfur atoms, polymers produced by RAFT polymerization contain sulfur-containing functional groups attached to polymer chains or terminals.
  • Sulfur-containing functional groups included in polymer chains or terminals may cause unintended color development by light absorption, which may limit their use, and may cause odor by decomposition over time.
  • an object of the present invention is to provide a method capable of efficiently removing a functional group derived from a RAFT material, for example, a trithiocarbonate group, a thiocarbonylthio group, and the like, from a chain of a polymer polymerized through a RAFT reaction.
  • a functional group derived from a RAFT material for example, a trithiocarbonate group, a thiocarbonylthio group, and the like
  • the present invention in order to solve the above technical problem,
  • RAFT reversible addition-fragmentation chain transfer
  • a method for producing a polymer comprising the step of precipitating by dropwise adding a reaction solution obtained from a continuous flow reactor to a non-solvent.
  • the solution containing the RAFT polymer containing the RAFT polymer
  • the RAFT polymer may be polymerized by reacting at least one selected from the group consisting of a monomer having a reactive ethylene group, a free radical initiator, and a RAFT material.
  • the RAFT material may be a material having a thiocarbonylthio group or a trithiocarbonate group.
  • the solution containing the RAFT polymer is based on the total weight
  • the (iii) non-alcoholic solvent is one selected from the group consisting of tetrahydrofuran, methyl ethyl ketone, toluene, xylene, ethyl acetate, hexane, cyclohexane, heptane, methylene chloride, and chloroform may be ideal
  • the (iv) alcohol is a group consisting of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, pentanol, isopentanol, hexanol, heptanol, ethylene glycol and propylene glycol It may be one or more selected from.
  • the non-solvent may be at least one selected from the group consisting of hexane, cyclohexane, heptane, methanol, ethanol, propanol, isopropyl alcohol, diethyl ether, and distilled water.
  • the continuous flow reactor may be a tubular flow reactor, a microchannel flow reactor, or a capillary flow reactor.
  • the continuous flow reactor may be heated to a temperature of 50 °C to 150 °C.
  • the continuous flow reactor may have a back pressure of 5 bar to 30 bar.
  • a functional group derived from a RAFT material for example, a trithiocarbonate group, a thiocarbonylthio group, etc.
  • a RAFT polymer polymerized by RAFT polymerization can be efficiently removed from a RAFT polymer polymerized by RAFT polymerization, and a polymer from which impurities are removed without a separate purification process Since powder can be obtained, it is possible to solve problems such as deterioration of physical properties of RAFT polymer or odor due to change over time without additional time and cost.
  • Figure 1 shows the UV spectrum results before and after carrying out the method according to the present invention.
  • a method for removing a functional group derived from a RAFT material for example, a trithiocarbonate group or a thiocarbonylthio group from a RAFT polymer, and a method for preparing a polymer from which impurities are removed through a precipitation process.
  • a functional group derived from a RAFT material for example, a trithiocarbonate group or a thiocarbonylthio group from a RAFT polymer
  • RAFT reversible addition-fragmentation chain transfer
  • the RAFT polymer used in the method of the present invention is a polymer polymerized by a generally known RAFT polymerization method, and the method is not particularly limited.
  • a monomer containing a generally known reactive ethylene group which is not limited to a polymerization method using a batch reactor or a flow reactor; For example, if it is a polymer polymerized using a monomer containing a vinyl group or a (meth)acrylate group, a radical initiator, and a RAFT material containing a thiocarbonylthio group or a trithiocarbonate group, the method according to the present invention is carried out without limitation can do.
  • the expression '(meth)acrylate group' refers to an acrylate group or a methacrylate group.
  • the process of the present invention uses a continuous flow reactor.
  • the continuous flow reactor includes tubular flow reactors, microchannel flow reactors, capillary flow reactors, etc., and refers to a series of flow reactors in which a material or mixture is injected into the reactor and a result is obtained after a series of processes. is to do
  • metal materials such as stainless steel or Hastelloy (trade name) may be used, and perfluoroalkoxy (PFA) resin, polytetrafluoroethylene (PTFE) resin, and polyether ether ketone (PEEK) may be used.
  • PFA perfluoroalkoxy
  • PTFE polytetrafluoroethylene
  • PEEK polyether ether ketone
  • a non-metallic material such as resin or glass may also be used, and an appropriate material may be selected and used without being limited to the examples.
  • the line of the continuous flow reactor is not limited in its shape, and the solution is continuously injected and flowed through the line so that the reaction proceeds and the reaction liquid is continuously discharged and collected. It can be used by modifying the structure.
  • the continuous flow reactor can control the back pressure, it is possible to prevent the solvent from boiling inside the reactor even if the reaction temperature rises, so that the reaction temperature is not limited by the boiling point of the solvent. It is better to remove
  • the back pressure applied to the continuous reactor may be adjusted to 5 to 30 bar, for example, 7 bar or more or 10 bar or more, and 25 bar or less or 20 bar or less. By doing so, boiling of the solvent in the reactor can be prevented.
  • the RAFT polymer solution used in the reaction of the present invention contains (i) one or more RAFT polymers, (ii) one or more free radical initiators, (iii) one or more non-alcoholic solvents, and (iv) one or more alcohols. to include
  • the RAFT polymer used in the present invention is a polymer polymerized by a generally known method, and the method is not particularly limited. For example, polymerization using a batch reactor or a flow reactor is not limited thereto. And if it is a polymer polymerized using a monomer containing a generally known reactive ethylene group, for example, a monomer containing a vinyl group or a (meth)acrylate group, a radical initiator, and a RAFT material, the method according to the present invention is carried out without limitation can do.
  • the RAFT material may be a material having a thiocarbonylthio group or a trithiocarbonate group.
  • the content of the RAFT polymer relative to the total weight of the RAFT polymer solution is 1% to 50% by weight, for example, 2% by weight or more, 3% by weight or more, 4% by weight or more, or 5% by weight or more , and may be 50 wt% or less, 30 wt% or less, 20 wt% or less, or 10 wt% or less.
  • the free radical initiator used in the present invention is 2,2'-azobisisobutyronitrile, 4,4'-azobis (4-cyanovaleic acid), 2,2'-azobis (2-methylbutyro nitrile), 2,2'-azobis (dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1'-azobis (cyclohexane) carbonitrile), dimethyl 2,2-azobis (2-methylpropionate), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2'- Azobis[N-(2-propenyl)-2-methylpropionamide], 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, 2,2' -Azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis(2-methylpropionamidine)dihydrochloride
  • the content of the free radical initiator relative to the total weight of the RAFT polymer solution is 1% to 10% by weight, for example, 1% by weight or more, or 2% by weight or more, and 10% by weight or less, 8% by weight % or less, 6% or less, or 4% or less.
  • the non-alcoholic solvent is preferably at least one selected from the group consisting of tetrahydrofuran, methyl ethyl ketone, toluene, xylene, ethyl acetate, hexane, cyclohexane, heptane, methylene chloride, and chloroform.
  • the content of the non-alcoholic solvent is 20 to 80% by weight, for example, 30% by weight or more, 40% by weight or more, or 50% by weight or more, and 70% by weight or less or 60% or less by weight.
  • the alcohol is preferably at least one selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, pentanol, isopentanol, hexanol, heptanol, ethylene glycol, and propylene glycol. .
  • the alcohol content may be 10 to 50% by weight, for example, 20% by weight or more or 30% by weight or more, and 45% by weight or less or 40% by weight or less. .
  • RAFT polymer free radical initiator, non-alcoholic solvent, alcohol, etc. are not limited to the types described above, and appropriate components may be selected and used as needed.
  • RAFT polymer and an alcohol when a RAFT polymer and an alcohol are mixed in a non-alcoholic solvent in the presence of a free radical initiator and reacted in a flow reactor, the alcohol participates in the reaction as a hydrogen donor to form a thiocarbonylthio group or trithio group in the RAFT polymer. The carbonate group is removed.
  • the temperature of the reactor may be increased to promote the reaction of the solution injected into the flow reactor.
  • the temperature of the reactor may be maintained at 50 °C to 150 °C, for example, 70 °C or higher or 100 °C or higher, for example, 150 °C or lower, or 130 °C or lower.
  • a pipe may be installed in the middle of the flow reactor to additionally inject an initiator to further promote the reaction.
  • the flow rate of reactants in the continuous flow reactor can be from 0.1 to 1 ml/min, for example, 0.2 ml/min or more or 0.3 ml/min or more, and 0.9 ml/min or less, 0.8 ml/min or less, 0.7 ml /min or less, 0.6 ml/min or less, or 0.5 ml/min.
  • reaction time may be 0.5 to 5 hours, for example, 1 hour or more, or 1.5 hours or more, and 4 hours or less, 3 hours or less, or 2.5 hours or less.
  • a purification step may be included through a process of precipitating using a non-solvent to remove by-products from the reaction-completed solution and process the polymer into a powder form.
  • the non-solvent may be used by selecting a solvent having no or very low solubility in the polymer, for example, 1 selected from the group consisting of hexane, cyclohexane, heptane, methanol, ethanol, propanol, isopropyl alcohol, diethyl ether and distilled water More than one species is preferred.
  • the amount of non-solvent can be used in a volume ratio of 3 to 10 times the reaction solution, and for example, it is preferable to use it in a volume ratio of 4 times or more, 5 times or more, 6 times or more, and 9 times or less or 8 times or less. can do.
  • Methyl methacrylate and butyl methacrylate were purchased from TCI, and methyl ethyl ketone, 2,2'-azobisisobutyronitrile and methanol were purchased from Daejung Chemical & Gold and used without further purification.
  • methyl methacrylate 11.3g, butyl methacrylate 13.2g, methyl ethyl ketone 60.86ml, azobisisobutyronitrile 0.095g, 4-cyano-4-(phenylcarbonothioylthio)penta 1.424 g of noic acid was added, mixed by stirring, and degassed by nitrogen circulation for 30 minutes.
  • the polymerization was performed by putting the reactor in a water bath containing mineral oil heated to 85° C., followed by a reflux reaction for 8 hr, and then cooled. After the reaction, a pink viscous liquid was obtained, which was precipitated in methanol and filtered to obtain a pink polymer powder.
  • the conversion rate, average molecular weight and molecular weight distribution of the polymer were measured by GPC.
  • the 1,1′-azobiscyclohexanecarbonitrile used in the examples was purchased from Sigma-Aldrich, and dimethyl 2,2-azobis(2-methylpropionate) (trade name V-601), 2,2′- Azobis(dimethylvaleronitrile) (trade name V-65) was purchased from Wako and used without further purification.
  • Methyl ethyl ketone, methanol, isopropyl alcohol, butanol, and tert-butanol were purchased from Daejung Chemical Gold and used without further purification.
  • the flow rate was set at 0.333 ml/min so that the reaction could proceed through the reactor coil for 120 minutes, and a 15 bar back pressure regulator was installed at the end of the coil to prevent the solvent from boiling inside the reactor.
  • the reaction-completed solution was measured by GPC to measure the conversion rate, and was added dropwise to 7-fold methanol to precipitate, and after filtration, a white polymer powder was obtained.
  • the obtained polymer powder was measured for average molecular weight and molecular weight distribution by GPC.
  • the flow rate was set at 0.333 ml/min so that the reaction could proceed through the reactor coil for 120 minutes, and a 15 bar back pressure regulator was installed at the end of the coil to prevent the solvent from boiling inside the reactor.
  • the conversion rate of the reaction-completed solution was measured by GPC, precipitated by dropwise addition to 7-fold methanol, and after filtration, a white polymer powder was obtained.
  • the obtained polymer powder was measured for average molecular weight and molecular weight distribution by GPC.
  • Polymer 1b 1.5g, 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65, Wako) 0.486g, tetrahydrofuran 12.133g, isopropyl alcohol 7.514g were added to a 100ml 3-neck reactor. After the addition, the mixture was degassed by nitrogen circulation and dissolved by stirring for 30 minutes. After confirming that all of the solution was dissolved, the solution was filtered through a 0.45 ⁇ m micro filter. The filtered solution was reacted using a Vapourtec R flow reactor. The reactor was a set composed of four 10 ml coils made of stainless steel connected to a total capacity of 40 ml, and each coil was heated to 100 ° C in a glass reaction tube.
  • the reactor was set at a flow rate of 0.333 ml/min so that the reaction could proceed through the reactor coil for 120 minutes, and a 15 bar back pressure regulator was installed at the end of the coil to prevent the solvent from boiling inside the reactor.
  • the conversion rate of the reaction-completed solution was measured by GPC, precipitated by dropwise addition to 7-fold methanol, and after filtration, a white polymer powder was obtained.
  • the obtained polymer powder was measured for average molecular weight and molecular weight distribution by GPC.
  • Polymer 1b 1.5g, 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65, Wako) 0.486g, tetrahydrofuran 12.133g, isopropyl alcohol 7.514g were added to a 100ml 3-neck reactor. After the addition, the mixture was degassed by nitrogen circulation and dissolved by stirring for 30 minutes. After confirming that all of the solution was dissolved, the solution was filtered through a 0.45 ⁇ m micro filter. The filtered solution was reacted using a Vapourtec R flow reactor. The reactor was a set composed of four 10 ml coils made of stainless steel connected to a total capacity of 40 ml, and each coil was heated to 100 ° C in a glass reaction tube.
  • the reactor was set at a flow rate of 0.333 ml/min so that the reaction could proceed through the reactor coil for 120 minutes, and a 15 bar back pressure regulator was installed at the end of the coil to prevent the solvent from boiling inside the reactor.
  • the reaction-completed solution was measured for conversion by GPC, added dropwise to 7-fold methanol, precipitated, and filtered to obtain a white polymer powder.
  • the obtained polymer powder was measured for average molecular weight and molecular weight distribution by GPC.
  • the reactor was set at a flow rate of 0.333 ml/min so that the reaction could proceed through the reactor coil for 120 minutes, and a 15 bar back pressure regulator was installed at the end of the coil to prevent the solvent from boiling inside the reactor.
  • the conversion rate of the reaction-completed solution was measured by GPC, precipitated by dropwise addition to 7-fold methanol, and after filtration, a white polymer powder was obtained.
  • the obtained polymer powder was measured for average molecular weight and molecular weight distribution by GPC.
  • the reactor was set at a flow rate of 0.333 ml/min so that the reaction could proceed through the reactor coil for 120 minutes, and a 15 bar back pressure regulator was installed at the end of the coil to prevent the solvent from boiling inside the reactor.
  • the conversion rate of the reaction-completed solution was measured by GPC, precipitated by dropwise addition to 7-fold methanol, and after filtration, a white polymer powder was obtained.
  • the obtained polymer powder was measured for average molecular weight and molecular weight distribution by GPC.
  • Table 1 summarizes the contents of the components of the polymer solutions used in Examples 1 to 6.
  • GPC Using a Waters GPC e2695 separation module, tetrahydrofuran as a mobile phase was flowed through a column at a rate of 1.0 ml/min, followed by separation and measurement with a Waters 2414 RI detector.
  • the columns used for the separation were Shodex KF-803, KF-802.5, KF802, and KF-801 connected in series, and the column temperature was set at 40 °C.
  • Mw and PDI of the obtained spectrum were calculated using a calibration curve verified by Shodex standard polystyrene kit SM-105.
  • ICP measured using an Agilent Technologies 5100 ICP-OES instrument. The samples were pretreated by acid decomposition and then sulfur and phosphorus elements were measured.
  • Table 2 shows the results of measuring polymer properties before and after removing the RAFT material.

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

Abstract

La présente invention concerne un procédé dans lequel un polymère obtenu par polymérisation à l'aide d'un matériau RAFT est injecté dans un réacteur à flux continu pour éliminer un groupe thiocarbonylthio ou un groupe trithiocarbonate d'une chaîne polymère, et un procédé de préparation d'un polymère, dans lequel, en permettant à une réaction de se produire dans une solution polymère dans laquelle un polymère RAFT, un initiateur radicalaire, un solvant non alcoolique et de l'alcool sont mélangés, dans un réacteur à flux continu, un matériau RAFT est éliminé d'une chaîne polymère.
PCT/KR2022/015813 2021-11-18 2022-10-18 Procédé de préparation de polymère WO2023090656A1 (fr)

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Citations (4)

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Publication number Priority date Publication date Assignee Title
JP2006002096A (ja) * 2004-06-18 2006-01-05 Toho Chem Ind Co Ltd 高分子末端基の変換
KR20070051778A (ko) * 2004-05-12 2007-05-18 이 아이 듀폰 디 네모아 앤드 캄파니 황-함유 말단기의 제거 방법
KR20140102728A (ko) * 2011-12-14 2014-08-22 커먼웰쓰 사이언티픽 앤드 인더스트리얼 리서치 오가니제이션 Raft 폴리머
KR20190064794A (ko) * 2017-12-01 2019-06-11 현대자동차주식회사 메타크릴계 블록 공중합체의 제조 방법

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Publication number Priority date Publication date Assignee Title
KR20070051778A (ko) * 2004-05-12 2007-05-18 이 아이 듀폰 디 네모아 앤드 캄파니 황-함유 말단기의 제거 방법
JP2006002096A (ja) * 2004-06-18 2006-01-05 Toho Chem Ind Co Ltd 高分子末端基の変換
KR20140102728A (ko) * 2011-12-14 2014-08-22 커먼웰쓰 사이언티픽 앤드 인더스트리얼 리서치 오가니제이션 Raft 폴리머
KR20190064794A (ko) * 2017-12-01 2019-06-11 현대자동차주식회사 메타크릴계 블록 공중합체의 제조 방법

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Title
HORNUNG CHRISTIAN H.; POSTMA ALMAR; SAUBERN SIMON; CHIEFARI JOHN: "Sequential flow process for the controlled polymerisation and thermolysis of RAFT-synthesised polymers", POLYMER, ELSEVIER, AMSTERDAM, NL, vol. 55, no. 6, 1 January 1900 (1900-01-01), AMSTERDAM, NL, pages 1427 - 1435, XP028630349, ISSN: 0032-3861, DOI: 10.1016/j.polymer.2014.01.023 *

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