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  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
  • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
  • C07D233/06—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
• • 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
  • C08F2/12—Polymerisation in non-solvents
  • C08F2/16—Aqueous medium
  • C08F2/22—Emulsion polymerisation
  • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
  • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
  • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
  • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
• • 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
  • C08F2/12—Polymerisation in non-solvents
  • C08F2/16—Aqueous medium
  • C08F2/22—Emulsion polymerisation
  • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
• • 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
  • C08F20/10—Esters
• • 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
  • C08F220/00—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
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
• • 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
  • C08F4/04—Azo-compounds

Definitions

• the present invention relates to a cationic polymerization initiator.
• a water-soluble initiator is always required in the emulsion polymerization method, which is a general method for synthesizing a polymer particle emulsion.
• the cationic polymerization initiator is preferably used when synthesizing an emulsion of cationic particles.
• a cationic polymerization initiator having a quaternary ammonium structure has various advantages such as formation of particles having an antibacterial function.
• Patent Document 1 discloses a compound having a quaternary ammonium structure that functions as a cationic polymerization initiator, and further, a polymer particle emulsion was synthesized by emulsion polymerization using the compound. Is disclosed.
• the present invention provides a cationic polymerization initiator capable of reducing the amount of aggregation formed in emulsion polymerization.
• the present invention includes the following inventions.
• R 72 and R 73 may further independently represent adamantyl, or C 1-6 alkyl substituted with Si (OCH 3 ) 2 (CH 3 ), respectively.
• R 75 and R 76 , or R 77 and R 78 may be combined to form ⁇ (CH 2 ) 3-5 ⁇ .
• R 81 , R 82 , R 83 , and R 84 are substituents selected from the group consisting of C 1-4 alkyl, C 1-4 alkyl carbonyl, and C 1-3 alkoxy, wherein the C 1 is here.
• the -4 alkyl may be substituted with one C 1-3 alkoxy group, and R 71 and R 74 are independently C 1-3 alkyl groups, respectively.
• X f - is, Cl -, NO 3 -, Br -, I -, CH 3 SO 3 - and OH - is a counter anion selected from the group consisting of] A compound having the chemical structure of.
• X f - is, Cl -, NO 3 -, Br -, it - and CH 3 SO 3 - is a counter anion selected from the group consisting of The compound according to (1).
• the R 81 , R 82 , R 83 , and R 84 are independently selected from the group consisting of methyl, ethyl, methylcarbonyl, isobutyl, and 2-methyl-2-methoxy-propyl.
• R 71 , R 72 , R 73 , R 74 , R 81 , R 82 , R 83 and R 84 are methyl groups
• R 75 , R 76 , R 77 and R 78 are hydrogen atoms
• Y The compound according to any one of (1) to (3) above, wherein and Z are single bonds.
• a cationic polymerization initiator comprising the compound according to any one of (1) to (8) above.
• a method for producing a polymer particle emulsion which comprises carrying out an emulsion polymerization reaction using the cationic polymerization initiator according to (9) above and a monomer containing a carbon-carbon double bond. .. (11)
• the present invention since the aggregation of polymer particles in emulsion polymerization is reduced, it is possible to obtain a polymer particle emulsion having a high solid content concentration in a high yield.
• C 1-3 alkyl means a linear, branched, or cyclic alkyl group having 1 to 3 carbon atoms, and is methyl, ethyl, n-propyl, i-propyl, or cyclo. Contains propyl.
• C 1-4 alkyl means a linear, branched, cyclic or partially cyclic alkyl group having 1 to 4 carbon atoms, for example, methyl, ethyl, n-propyl. , I-propyl, n-butyl, s-butyl, i-butyl, t-butyl, cyclopropyl, cyclobutyl and the like, and also include, for example, C 1-3 alkyl and the like.
• C 1-6 alkyl means a linear, branched, cyclic or partially cyclic alkyl group having 1 to 6 carbon atoms, for example, methyl, ethyl, n-propyl.
• C 1-3 alkoxy means an alkyloxy group having an alkyl group having 1 to 3 carbon atoms, which has already been defined as an alkyl moiety, and includes, for example, methoxy, ethoxy, n-propoxy, and i-propoxy. And the like, for example, C 1-4 alkoxy and C 1-3 alkoxy and the like are also included.
• C 1-6 alkoxy means an alkyloxy group having an alkyl group having 1 to 6 carbon atoms, which has already been defined as an alkyl moiety, and for example, methoxy, ethoxy, n-propoxy, i-propoxy.
• N-butoxy, s-butoxy, i-butoxy, t-butoxy, n-pentoxy, 3-methylbutoxy, 2-methylbutoxy, 1-methylbutoxy, 1-ethylpropoxy, n-hexyloxy, 4-methylpen Includes toxi, 3-methylpentoxy, 2-methylpentoxy, 1-methylpentoxy, 3-ethylbutoxy, cyclopentyloxy, cyclohexyloxy, cyclopropylmethyloxy and the like, eg, C 1-4 alkoxy and C 1 -3 Alkoxy and the like are also included.
• examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
• C 1-4 alkyl carbonyl represents a group-CO (C 1-4 alkyl), wherein the C 1-4 alkyl is as already defined.
• C 1-6 alkyl carbonyl represents a group-CO (C 1-6 alkyl), wherein the C 1-6 alkyl is as defined above.
• the copolymer is an aggregate of polymer chains formed by mixing the monomers corresponding to each unit and carrying out a polymerization reaction.
• the polymer refers to a polymer chain in which monomer units are bonded and connected.
• the compound of the present invention has the general formula (I): [During the ceremony, Y represents a single bond or CHR 85 , Z represents a single bond or CHR 86 R 72 , R 73 , R 75 , R 76 , R 77 , R 78 , R 85 and R 86 are independent hydrogen atoms, C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkyl, respectively.
• R 72 and R 73 may further independently represent adamantyl, or C 1-6 alkyl substituted with Si (OCH 3 ) 2 (CH 3 ), respectively.
• R 75 and R 76 , or R 77 and R 78 may be combined to form ⁇ (CH 2 ) 3-5 ⁇ .
• R 81 , R 82 , R 83 , and R 84 are substituents selected from the group consisting of C 1-4 alkyl, C 1-4 alkyl carbonyl, and C 1-3 alkoxy, wherein the C 1 is here.
• the -4 alkyl may be substituted with one C 1-3 alkoxy group, and R 71 and R 74 are independently C 1-3 alkyl groups, respectively.
• X f - is, Cl -, NO 3 -, Br -, I -, CH 3 SO 3 - and OH - is a counter anion selected from the group consisting of] Has the chemical structure of.
• X f - is, Cl -, NO 3 -, Br -, I - and CH 3 SO 3 - are - is selected from the group consisting of, more preferably Cl.
• Y and Z in formula (I) represent a single bond.
• R 81 , R 82 , R 83 and R 84 of formula (I) are independently methyl, ethyl, methylcarbonyl, isobutyl, and 2-methyl-2-methoxy-, respectively. Selected from the group consisting of propyl.
• R 71 and R 74 of formula (I) are methyl groups.
• R 72 , R 73 , R 75 , R 76 , R 77 , R 78 , R 85 , and R 86 of formula (I) are independently hydrogen atoms, C 1 It is selected from the group consisting of -6 alkyl, C 1-6 alkoxy, C 1-6 alkyl carbonyl, phenyl and hydroxy.
• R 75 and R 76 of formula (I) or R 77 and R 78 may together are - (CH 2) 4 - to form a.
• 74 represents the same substituent
• Y and Z represent the same substituent, or both represent a single bond.
• R 71 , R 72 , R 73 , R 74 , R 81 , R 82 , R 83 , and R 84 of the formula (I) are methyl groups, and R 75 , R. 76 , R 77 , and R 78 are hydrogen atoms, and Y and Z are single bonds.
• the compound of formula (I) can be synthesized, for example, according to the method described in International Publication No. 2017/043484.
• the counter anion can be exchanged, for example, by passing it through a silica-based anion exchange column in methanol.
• the compound of the present invention can be used as a cationic polymerization initiator in the production of a polymer by radical polymerization.
• the cationic polymerization initiator of the present invention reduces the aggregation of polymer particles in the production of a polymer particle emulsion by emulsion polymerization, and makes it possible to produce a polymer particle emulsion in a high yield.
• the amount of the polymerization initiator used can be selected within the range of the concentration at which the polymerization reaction proceeds, and is not particularly limited. For example, 0.01 mol% or more based on the monomer used. It can be used in an amount of 0.1 mol% or more, more preferably 0.5 mol% or more.
• the monomer used as the raw material for the polymerization reaction any compound having a carbon-carbon double bond can be used.
• the present invention has an advantage that agglomeration of the polymer is less likely to occur even when a polymer that is hardly soluble in water is synthesized in emulsion polymerization, and an emulsion having a high polymer concentration can be synthesized. Therefore, in one preferred embodiment of the present invention, it is a monomer used for emulsion polymerization using water as a solvent.
• Examples of such a monomer include methacrylate, acrylate, styrene, a styrene derivative, vinyl acetate and the like, and examples of the most general-purpose monomer include methyl methacrylate (MMA) and styrene.
• MMA methyl methacrylate
• a cross-linking agent can be used in the polymerization reaction.
• the cross-linking agent is not particularly limited as long as it is a monomer containing two or more vinyl groups in the molecule and is usually used as a cross-linking agent.
• Specific examples of the cross-linking agent include N, N'-methylene bisacrylamide, N, N'-ethylene bisacrylamide, N, N'-methylene bismethacrylamide, N, N'-ethylene bismethacrylate, and ethylene glycol. Examples thereof include diacrylate and ethylene glycol dimethacrylate.
• the reaction solvent used in the polymerization reaction is not particularly limited, and examples thereof include water, ethanol, acetone, dioxane, dimethylformamide, dimethyl sulfoxide, and any mixture thereof. According to a preferred embodiment of the present invention, the reaction solvent is a mixture of ethanol and water or a mixture of acetone and water.
• the temperature and time of the polymerization reaction are not particularly limited, but for example, at a reaction temperature of 0 to 100 ° C., preferably 50 to 80 ° C., for example, 1 to 48 hours, preferably 1 to 16 hours, more preferably 1 to 10 hours. It can be done in reaction time.
• the diameter of the synthesized particles is the hydrodynamic particle diameter (Z-Ave) measured by the Zetasizer Nano ZSP (Malburn) by the dynamic light scattering method.
• PdI represents a polydispersity index, and the width of the particle size distribution can be evaluated.
• a distribution with a PdI value of 0.1 or less is commonly referred to as a monodisperse, while a dispersion with a value between 0.1 and 0.3 is considered to have a narrow diameter distribution.
• the zeta potential was measured with the Zetasizer Nano ZSP (Malvern).
• Example 1 Inhibition effect of emulsion polymerization caused by counterions (verification of problems) Ultrapure water and acetone were replaced with nitrogen.
• MMA methyl methacrylate
• EGDMA ethylene glycol dimethacrylate
• a polymerization initiator with a final concentration of 4.4 mM: 2,2'-azobis.
• VA-044, CAS RN.27776-21-2 Dihydrochloride
• Acetone was added until the final volume was 30 mL. Further, a salt having a final concentration of 8.8 mM (shown in the table below) was added to each sample, and the polymerization reaction was carried out at 75 ° C. for 3 hours while being sealed and stirred with a stirrer.
• Table 1 shows the diameter of the particles of the emulsion synthesized by adding each salt, the degree of polydispersity, and the results of the presence or absence of aggregation (precipitation).
• the counter anion is a divalent anion of sulfate ions (OG606, SO 4 2-), triflate ion among monovalent anion (OG602, CF 3 SO 3 - ) If, without the addition of salt (OG598 ), It was found to cause aggregation. Salt concentration of 8.8mM, the other monovalent counter anion Cl - (OG604), Br - (OG605) and NO 3 - (OG607) is a low concentration to the extent that agglomeration is not observed in. It is known from the DVLO theory that divalent ions are easily aggregated, but it was found that even monovalent anions include triflate ions as ions that aggregate at a low concentration.
• Example 2 Synthesis of cationic polymerization initiator (compound of formula (I)) in which the counter anion was exchanged
• the ADIP was dissolved in methanol cooled to ⁇ 20 ° C. to prepare a 50 mg / mL ADIP solution.
• An InertSep SAX2 column (filler 5 g, 0.3 meq / g loading, pre-conditioned with 15 mL MeOH) was loaded with 6 mL of ADIP solution and treated with 300 mg of ADIP. Next, 6 mL of ice-cold MeOH was added to the column to give a total of 12 mL of pass-through fraction. By repeating this, a total of 15 g of ADIP was processed.
• ADIP-Cl in which the counter anion was replaced with a chloride ion from a triflate ion could be synthesized in a yield of 100%.
• the decomposition rate of ADIP at 70 ° C. was 12.6 ⁇ 10 -4 (/ s)
• there was no difference in the decomposition rate which is one of the initiator's abilities.
• Example 3 Synthesis of Stable Cationic PMMA Emulsion by Using ADIP-Cl Ultrapure water and acetone were replaced with nitrogen.
• MMA methyl methacrylate
• EGDMA ethylene glycol dimethacrylate
• a polymerization initiator with a final concentration of 4.4 mM: VA-044, 2, 2'-azobis (2-methylpropionamidine) dihydrochloride (abbreviation V-50, CAS RN. 2997-92-4)
• ADIP or ADIP-Cl synthesized in Example 2 was added, and the acetone concentration was 40 v /.
• Water and acetone were added to a final volume of 30 mL so as to be v%, and the polymerization reaction was carried out at 75 ° C. for 3 hours while sealing and stirring with a stirrer.
• ADIP causes aggregation.
• ADIP contains triflate ions equivalent to 8.8 mM, which is the same concentration as the salt used in Example 1. Since no aggregation was observed in OG825 in which triflate ion was replaced with chloride ion, it was found that a stable emulsion could be synthesized by using a cationic polymerization initiator having no triflate ion.
• the diameter of OG825 was 125 nm, the PdI was 0.102, and the zeta potential was 60 mV, indicating that cationic particles could be synthesized.
• Example 4 Synthesis of high-concentration polystyrene (PS) emulsion using ADIP-Cl All ultrapure water was used after nitrogen bubbling while rotating a stirrer to expel dissolved oxygen for 30 minutes or more. 12 mL of ethanol was added to a 30 mL clear vial. After adding 3.45 mL of styrene to the vial so that the monomer concentration becomes 1000 mM, add the polymerization initiator ADIP or ADIP-Cl dissolved in 1 mL of ultrapure water to the vial so that the final concentration becomes 10 mM. did. After adding ultrapure water to adjust the total volume to 30 mL, set the vial in a hot water bath at 60 ° C. and use a strong stir bar (1-6618-02, strong stir bar, ⁇ 4.5 ⁇ 12 mm). The mixture was stirred using and synthesized for a total of 6 hours.
• PS high-concentration polystyrene
• Example 5 Aggregation effect of polymethylmethacrylate (PMMA) particles and polystyrene (PS) particles by pair ions
• PMMA particle suspension OG1024 was synthesized. Specifically, the synthesis was performed according to the following procedure. First, ultrapure water was replaced with nitrogen. In a vial (30 mL volume), a final concentration of 1000 mM methyl methacrylate and a final concentration of 2 mM polymerization initiator: 2,2'-azobis (2-methylpropionamidine) dihydrochloride (abbreviated as V-50, CAS RN.
• V-50 2,2'-azobis (2-methylpropionamidine) dihydrochloride
• PS particle suspension YT085 was synthesized. Specifically, the synthesis was performed according to the following procedure. First, ultrapure water was replaced with nitrogen. To a vial (30 mL volume), add styrene with a final concentration of 1000 mM and a polymerization initiator V-50 with a final concentration of 10 mM, add a 30 v / v% aqueous ethanol solution until the final volume reaches 30 mL, seal tightly, and use a stirrer. The polymerization reaction was carried out at 80 ° C. for 6 hours with stirring. The sample cooled to room temperature was vacuum dried to calculate the particle solid content concentration. The particle solid content concentration was adjusted to 0.14 mg / ml, and the concentration of each added salt was adjusted to 50 mM, and the mixture was sealed and mixed with a vortex mixer to prepare a sample for DLS measurement.

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• 2019
  • 2019-11-20 JP JP2019209812A patent/JP7356875B2/ja active Active
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