WO2022163360A1 - （メタ）アクリル酸エステル化合物の製造方法 - Google Patents

（メタ）アクリル酸エステル化合物の製造方法 Download PDF

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WO2022163360A1
WO2022163360A1 PCT/JP2022/000838 JP2022000838W WO2022163360A1 WO 2022163360 A1 WO2022163360 A1 WO 2022163360A1 JP 2022000838 W JP2022000838 W JP 2022000838W WO 2022163360 A1 WO2022163360 A1 WO 2022163360A1
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meth
group
formula
mol
acrylic
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French (fr)
Japanese (ja)
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直人 青柳
拓矢 魚谷
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Mitsubishi Gas Chemical Co Inc
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Mitsubishi Gas Chemical Co Inc
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Priority to US18/273,576 priority Critical patent/US20240166805A1/en
Priority to KR1020237027170A priority patent/KR20230133876A/ko
Priority to EP22745585.4A priority patent/EP4286361A4/en
Priority to JP2022578218A priority patent/JP7831321B2/ja
Priority to CN202280011657.0A priority patent/CN116806215B/zh
Publication of WO2022163360A1 publication Critical patent/WO2022163360A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/664—Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • C08G65/485—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54—Acrylic acid esters; Methacrylic acid 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
    • C08F122/00—Homopolymers 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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F122/10—Esters
    • C08F122/12—Esters of phenols or saturated alcohols
    • C08F122/14—Esters having no free carboxylic acid groups

Definitions

  • the present invention relates to a method for producing a (meth)acrylate compound.
  • Patent Document 2 discloses a curable composition
  • a curable composition comprising a capped poly(arylene ether) prepared by the reaction of an unblocked poly(arylene ether) with an anhydride capping agent and an olefinically unsaturated monomer, , a curable composition wherein the composition after curing has less than 1% by weight water absorption after 7 days at 85° C. and 85% relative humidity.
  • a blocking catalyst comprising a 4-dialkylaminopyridine.
  • Patent Document 3 describes that a predetermined polyphenylene oxide oligomer is reacted with 2-methacrylic anhydride (methacrylic anhydride) in the presence of sodium acetate to obtain a polyphenylene oxide oligomer having functionalized terminal groups. It is
  • JP 2011-105667 A Japanese translation of PCT publication No. 2007-507592 JP 2019-210451 A
  • the present invention solves such problems, and is a method for obtaining an ester compound produced by esterifying a phenol compound, which can be esterified at a high introduction rate and efficiently recovers the obtained ester compound.
  • An object of the present invention is to provide a method for producing a (meth)acrylic acid ester compound.
  • the inventors have found that the above problems can be solved by esterification using (meth)acrylic anhydride in the presence of a predetermined basic catalyst. Specifically, the above problems have been solved by the following means. ⁇ 1> comprising reacting a polymer having a structure represented by formula (1) with (meth)acrylic anhydride in the presence of at least one of potassium carbonate, rubidium carbonate and cesium carbonate; ) A method for producing an acrylic acid ester compound.
  • the method for producing the (meth)acrylate compound according to 1> ⁇ 3> ⁇ 1> or ⁇ 2>, wherein the polymer having the structure represented by the above formula (1) is further reacted with an acyl compound, and part of X after the reaction is an acyl group.
  • a method for producing the (meth)acrylic acid ester compound according to . (Metal ) A method for producing an acrylic acid ester compound. ⁇ 5> Any one of ⁇ 1> to ⁇ 4>, wherein the hydroxyl value, which is the mass per mole of hydroxyl groups of the polymer having the structure represented by the formula (1), is 100 to 5,000 g/mol.
  • ⁇ 6> 1.0 to 10.0 mol in total of at least one of potassium carbonate, rubidium carbonate and cesium carbonate per 1 mol of hydroxyl group of the polymer having the structure represented by the above formula (1), (meth) The method for producing a (meth)acrylate compound according to any one of ⁇ 1> to ⁇ 5>, wherein 1.0 to 10.0 mol of acrylic anhydride is used.
  • the polymer having the structure represented by formula (1) includes a polymer represented by formula (2) or formula (3)
  • R 11 to R 18 are each independently selected from a hydrogen atom and an alkyl group
  • R 9 and R 10 are each independently a hydrogen atom, an alkyl a group, an alkynyl group, a hydroxyl group, an amino group, an aryl group, or a heterocyclic group
  • R 9 and R 10 may be bonded together to form a ring structure
  • X is a hydrogen atom, At least part thereof reacts with (meth)acrylic anhydride to form a (meth)acrylic group
  • n is an integer of 0 or more
  • m is an integer of 0 or more
  • m+n is an integer of 1 or more is.
  • a method for obtaining an ester compound by esterifying a phenolic compound in which a (meth)acrylic ester compound can be esterified at a high introduction rate and the resulting ester compound can be efficiently recovered. method has been made available.
  • an "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • the notations that do not describe substituted and unsubstituted are preferably unsubstituted.
  • (meth)acryl represents both or either acryl and methacryl. Methacryl is preferred in the present invention. If the standards shown in this specification differ from year to year in terms of measurement methods, etc., they shall be based on the standards as of the time of filing unless otherwise specified.
  • the method for producing a (meth)acrylic acid ester compound of the present embodiment is a process in which a polymer having a structure represented by formula (1) is converted to carbonic acid. characterized by including reacting with (meth)acrylic anhydride in the presence of at least one of potassium, rubidium carbonate and cesium carbonate.
  • esterification can be performed at a high introduction rate, and the obtained (meth)acrylic acid ester compound can be efficiently recovered.
  • the esterification reaction proceeds in the presence of at least one of potassium carbonate, rubidium carbonate and cesium carbonate. That is, it is presumed that potassium ions, rubidium ions, or cesium ions convert the phenolic hydroxyl (OX) sites in formula (1) to O 2 ⁇ and the reaction proceeds.
  • potassium ions, rubidium ions, and cesium ions are large in size as cations, so it is presumed that the phenoxy anions are likely to become free, and that the nucleophilic aggressiveness to the acylating agent can be increased.
  • sodium ions and lithium ions have a low ability to ionize OH to form O - , and even when ionized, the ionic bonding force between O - and sodium ions or lithium ions is strong, and the reactivity to the acylating agent is low. estimated to be lower.
  • Potassium hydrogen carbonate has a lower ionic radius and lower basicity compared to potassium carbonate due to the influence of hydrogen (H), and it is presumed to have lower reactivity because it has a lower ability to convert to O 2 ⁇ .
  • carbonate is also used. It is presumed that if a catalyst with stronger basicity than carbonate is used, the catalyst will attack the methacrylic anhydride. For example, potassium hydroxide and cesium hydroxide decompose methacrylic anhydride to methacrylic acid.
  • the carbonate is selected so as to preferentially activate the phenolic hydroxyl group (OX) site of formula (1).
  • OX phenolic hydroxyl group
  • the (meth)acrylic acid ester compound obtained by the production method of the present embodiment can have performance equivalent to that of conventional low dielectric resins. Furthermore, a resin having a high glass transition temperature can be obtained, and a material excellent in heat resistance can be obtained. Details of the manufacturing method of this embodiment will be described below.
  • the polymer having the structure represented by Formula (1) is reacted with (meth)acrylic anhydride to carry out an esterification reaction.
  • a (meth)acrylic acid ester compound in which a (meth)acrylic group is introduced into the phenolic hydroxyl group of the polymer having the structure represented by formula (1), that is, the X site of formula (1) is obtained.
  • a polymer having a structure represented by formula (1) is used as a raw material. By using such a resin, it becomes possible to produce a thermosetting resin having low dielectric properties and excellent heat resistance.
  • the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, preferably linear or branched, more preferably linear.
  • the alkyl group may or may not have a substituent, but preferably has no substituent.
  • the substituent is exemplified by a halogen atom, an alkenyl group, an alkynyl group, and an aryl group.
  • the alkyl group is preferably a methyl group, an ethyl group, or a propyl group, and more preferably a methyl group.
  • X is a hydrogen atom, at least a portion of which reacts with (meth)acrylic anhydride to form a (meth)acrylic group.
  • the ratio of X being a hydrogen atom after reacting with (meth)acrylic anhydride is preferably 15 mol% or less, more preferably 10 mol% or less. It is more preferably mol % or less, and even more preferably 3 mol % or less.
  • the lower limit of the proportion of hydrogen atoms in X is preferably 0 mol % or more. As will be described later in detail, part of X may react with an acyl compound or the like to form an acyl group or the like.
  • the polymer having the structure represented by formula (1) is not particularly defined as long as it has the structure represented by formula (1).
  • the structure represented by Formula (1) may be present at the terminal of the polymer, or may be present at a portion other than the terminal of the polymer.
  • One embodiment of the polymer having the structure represented by Formula (1) includes having the structure represented by Formula (1) at least at the ends (preferably at both ends).
  • a polyphenylene ether compound having the structure represented by Formula (1) is exemplified.
  • the polymer having the structure represented by the formula (1) is preferably a polymer represented by the following formula (2) or (3).
  • R 11 to R 18 are each independently selected from a hydrogen atom and an alkyl group
  • R 9 and R 10 are each independently a hydrogen atom, an alkyl a group, an alkynyl group, a hydroxyl group, an amino group, an aryl group, or a heterocyclic group
  • R 9 and R 10 may be bonded together to form a ring structure
  • X is a hydrogen atom, At least part thereof reacts with (meth)acrylic anhydride to form a (meth)acrylic group
  • n is an integer of 0 or more
  • m is an integer of 0 or more
  • the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, preferably linear or branched, more preferably linear.
  • the alkyl group may or may not have a substituent, but preferably has no substituent.
  • the substituent is exemplified by a halogen atom, an alkenyl group, an alkynyl group, and an aryl group.
  • the alkyl group is preferably a methyl group, an ethyl group, or a propyl group, and more preferably a methyl group.
  • R 11 , R 12 , R 13 and R 14 are preferably hydrogen atoms and the rest are alkyl groups (preferably methyl groups), R 13 and R 14 are hydrogen atoms, More preferably, R 11 and R 12 are alkyl groups (preferably methyl groups). 1 to 3 of R 15 , R 16 , R 17 and R 18 are preferably hydrogen atoms, the rest are preferably alkyl groups (preferably methyl groups), one or two of which are hydrogen atoms, More preferably, the remainder are alkyl groups.
  • R 9 and R 10 each independently represent a hydrogen atom, an alkyl group, an alkynyl group, a hydroxyl group, an amino group, an aryl group, or a heterocyclic group ; may be formed.
  • Alkyl groups, alkynyl groups, aryl groups, and heterocyclic groups may or may not have substituents, but preferably have no substituents.
  • substituents include halogen atoms, alkenyl groups, alkynyl groups, and aryl groups.
  • R 9 and R 10 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a hydroxyl group, an amino group, an aryl group having 6 to 12 carbon atoms, or a 5-membered It is preferably a ring or a 6-membered heterocyclic group, more preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a hydroxyl group, still more preferably a hydrogen atom or a methyl group, and a methyl group. More preferably.
  • X has the same definition as in formula (1).
  • n is an integer of 0 or more, preferably an integer of 1 or more, more preferably an integer of 5 or more, an integer of 50 or less, and more preferably an integer of 20 or less.
  • m is an integer of 0 or more, preferably an integer of 1 or more, more preferably an integer of 5 or more, an integer of 50 or less, and more preferably an integer of 20 or less.
  • m+n is an integer of 1 or more, preferably an integer of 10 or more, more preferably an integer of 11 or more, an integer of 100 or less, and more preferably an integer of 30 or less.
  • R 21 is an alkyl group, a hydroxyl group, or an aryl group
  • Y 2 is —CH 2 —, —CH 2 O—, or —CH 2 OCH 2 —
  • X is a hydrogen atom, at least part of which reacts with (meth)acrylic anhydride to form a (meth)acrylic group
  • l is an integer of 1 or more
  • k is an integer of 2 or more
  • z is an integer of 0 to 3.
  • * is a bonding site with another structural unit or terminal group.
  • R 21 is an alkyl group, a hydroxyl group, or an aryl group, preferably an alkyl group.
  • the alkyl group is preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 2 to 10 carbon atoms, and more preferably an alkyl group having 3 to 7 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, preferably linear or branched, more preferably branched.
  • the alkyl group may or may not have a substituent, but preferably has no substituent. When having a substituent, the substituent is exemplified by a halogen atom, an alkenyl group, an alkynyl group, and an aryl group.
  • the alkyl group is preferably a methyl group, an ethyl group or a butyl group, more preferably a t-butyl group.
  • Aryl groups are preferably phenyl groups.
  • Y 2 is -CH 2 -, -CH 2 O-, or -CH 2 OCH 2 -, preferably -CH 2 -.
  • X has the same definition as in formula (1).
  • l is an integer of 1 or more, preferably an integer of 4 or more, more preferably an integer of 5 or more, an integer of 50 or less, and more preferably an integer of 20 or less.
  • k is an integer of 2 or more, preferably an integer of 3 or more, more preferably an integer of 6 or more, an integer of 50 or less, and more preferably an integer of 20 or less.
  • z is an integer of 0 to 3, preferably an integer of 0 or more, more preferably an integer of 1 or more, an integer of 3 or less, and more preferably an integer of 1 or less.
  • * is a bonding site with another structural unit or terminal group. Examples of terminal groups include hydrogen atoms and hydroxyl groups, with hydrogen atoms being preferred.
  • the polymer represented by formula (2) and the polymer represented by formula (3) may contain other structural units within the scope of the present invention.
  • the polymer represented by the formula (2) and the polymer represented by the formula (3) do not contain other structural units, or the proportion of other structural units is the weight represented by the formula (2). It is preferably 3% by mass or less (preferably 1% by mass or less) of the coalescence and the polymer represented by formula (3).
  • a polymer having a structure represented by formula (1) is usually a raw material. It accounts for 90 mass % or more of the polymer component, preferably 95 mass % or more.
  • the polymer having the structure represented by formula (1) preferably has a hydroxyl value, which is the mass of the polymer per mole of hydroxyl group, of 100 to 5,000 g/mol.
  • a hydroxyl value which is the mass of the polymer per mole of hydroxyl group, of 100 to 5,000 g/mol.
  • the hydroxyl value is more preferably 2000 g/mol or less, more preferably 1200 g/mol or less, more preferably 200 g/mol or more, and even more preferably 300 g/mol or more. .
  • the hydroxyl value is measured according to the description of the examples below.
  • the number average molecular weight of the polymer having the structure represented by formula (1) is preferably 1,000 to 10,000. When the content is within the above range, the resulting (meth)acrylic acid ester compound tends to exhibit well-balanced performance when cured. Specifically, low dielectric properties, heat resistance, ease of curing, and uniform film-forming properties tend to be superior.
  • the number average molecular weight is more preferably 1,200 or more, further preferably 1,500 or more, more preferably 6,000 or less, and further preferably 5,000 or less. Preferably, it is less than 4,000, and even more preferably 3,500 or less.
  • the number-average molecular weight (Mn) is measured according to the description of the examples below.
  • the polymer having the structure represented by formula (1) used in the present embodiment preferably satisfies both the number average molecular weight and the hydroxyl value. In such a case, the effects of the present invention are exhibited more effectively.
  • the molecular weight distribution (Mw/Mn) is more preferably 1.01 or more, further preferably 1.10 or more, and more preferably 10.0 or less, and 5.00 or less. is more preferably 3.00 or less.
  • hydroxyl groups can be appropriately esterified even when the molecular weight distribution (Mw/Mn) is 1.50 or more.
  • the weight-average molecular weight (Mw) is measured according to the description of the examples below.
  • the catalyst used in the production method of this embodiment will be described.
  • at least one catalyst of potassium carbonate, rubidium carbonate and cesium carbonate is used.
  • the reaction between the polymer having the structure represented by formula (1) and (meth)acrylic anhydride can be effectively accelerated.
  • the obtained (meth)acrylic acid ester compound can be recovered in high yield.
  • potassium carbonate, rubidium carbonate and cesium carbonate are preferred, and potassium carbonate is more preferred.
  • the forms of potassium carbonate, rubidium carbonate and cesium carbonate are not particularly limited, they are preferably in the form of powder. Further, the form of potassium carbonate, rubidium carbonate and cesium carbonate is preferably fine powder (average particle diameter of about 10 to 200 ⁇ m). Using a powdery one increases the specific surface area and enhances the reactivity.
  • the reactivity between the hydroxyl group of the polymer having the structure represented by formula (1) and (meth)acrylic anhydride tends to be further improved.
  • the content By making the content equal to or less than the above upper limit, there is a tendency that the effect of reducing the manufacturing cost is further improved.
  • only one of potassium carbonate, rubidium carbonate and cesium carbonate may be used, or two or more thereof may be used. When two or more kinds are used, the total amount is preferably within the above range.
  • the esterification reaction can be performed without using 4-dimethylaminopyridine (DMAP), which has been commonly used. That is, in the production method of the present embodiment, the esterification reaction can proceed in a state in which DMAP is substantially absent.
  • DMAP 4-dimethylaminopyridine
  • “Substantially absent” means that the amount of DMAP present is preferably 0.1 mol or less, and preferably 0.05 mol or less, relative to 1.0 mol of the total amount of potassium carbonate, rubidium carbonate and cesium carbonate. is more preferably 0.03 mol or less, and even more preferably 0.01 mol or less. The lower limit is 0 mol.
  • an esterification catalyst other than potassium carbonate, rubidium carbonate and cesium carbonate is substantially absent.
  • substantially absent means that the amount of an esterification catalyst other than potassium carbonate, rubidium carbonate, and cesium carbonate is 0.1 mol or less with respect to 1.0 mol of the total amount of potassium carbonate, rubidium carbonate, and cesium carbonate. is preferably 0.05 mol or less, more preferably 0.03 mol or less, and even more preferably 0.01 mol or less. The lower limit is 0 mol. By setting it as such a range, a (meth)acrylic-ester compound can be isolated with a higher yield.
  • a polymer having a structure represented by formula (1) is reacted with (meth)acrylic anhydride.
  • (Meth)acrylic anhydride is methacrylic anhydride and/or acrylic anhydride, preferably methacrylic anhydride.
  • the proportion of X in the polymer having the structure represented by formula (1) substituted with (meth)acrylic groups is preferably 85 mol % or more, more preferably 90 mol % or more, still more preferably 93 mol % or more, and even more preferably 97 mol % or more.
  • the upper limit is ideally 100 mol %, but practically 99.9 mol % or less.
  • the esterification reaction it is preferable to use 1.0 mol or more of (meth)acrylic anhydride, and 1.1 mol or more is used per 1 mol of the hydroxyl group of the polymer having the structure represented by formula (1). is more preferable.
  • the (meth)acrylic anhydride is preferably 10.0 mol or less, more preferably 8.0 mol or less, per 1 mol of the hydroxyl group of the polymer having the structure represented by formula (1).
  • the polymer having the structure represented by formula (1) is further reacted with an acyl compound, and a part of X after the reaction is an acyl group, good too.
  • the polymer having the structure represented by formula (1) used in the production method of the present embodiment contains many phenolic hydroxyl groups, reacting only (meth)acrylic anhydride produces many (meth)acrylic groups. be introduced.
  • the (meth)acrylic acid ester compound obtained by the production method of the present embodiment is used as a low dielectric material, if more (meth)acrylic groups than necessary are introduced into the (meth)acrylic acid ester compound, the dielectric may increase the dielectric constant and dielectric loss tangent.
  • a polymer having a structure represented by formula (1) is reacted with an acyl compound in addition to (meth)acrylic anhydride, and part of X after the reaction is ( A desired low dielectric material can be obtained by using a meth)acrylic group and the other part being an acyl group.
  • the acyl compound when the acyl compound is reacted in addition to the (meth)acrylic anhydride, the (meth)acrylic anhydride and the acyl compound may be reacted simultaneously, or one of them may be reacted first.
  • the acyl compound after reacting the (meth)acrylic anhydride.
  • a polymer having a suitable amount of (meth)acrylic groups for the production of low dielectric materials and a low residual hydroxyl group ratio is obtained. be able to.
  • the acylation reaction using an acyl compound is preferably carried out in the same reaction system, but may be carried out in a reaction system substantially free of potassium carbonate, rubidium carbonate and cesium carbonate.
  • the reaction product after reacting a polymer having a structure represented by formula (1) with (meth)acrylic anhydride, the reaction product may be recovered and reacted with an acyl compound in another reaction system. .
  • acyl compound is not particularly specified, but acetic anhydride is preferable from the viewpoint of production cost.
  • acetic anhydride was reacted to substitute methacrylic groups and acetyl groups at a molar ratio of 1:1, but substitution may be made at an arbitrary ratio in consideration of the hydroxyl equivalent weight of the raw material resin to be reacted. can be made
  • the proportion of X in the polymer having the structure represented by formula (1) substituted with an acyl group is preferably 5 mol% or more. , more preferably 10 mol % or more.
  • the proportion of X in the polymer having the structure represented by formula (1) that is substituted with an acyl group is preferably 90 mol % or less, more preferably 80 mol % or less.
  • the esterification reaction it is preferable to use 0.1 mol or more, more preferably 0.2 mol or more, of the acyl compound per 1 mol of the hydroxyl group of the polymer having the structure represented by formula (1).
  • the amount of the acyl compound is preferably 10 mol or less, more preferably 5 mol or less, per 1 mol of the hydroxyl group of the polymer having the structure represented by formula (1).
  • One type of acyl compound may be used, or two or more types may be used. When two or more are used, the total amount is preferably within the above range.
  • the esterification reaction in the presence of a solvent.
  • a solvent when the polymer having the structure represented by formula (1) is liquid, a solvent may not be used, but the polymer having the structure represented by formula (1) When is non-liquid, a solvent is usually used.
  • a solvent By using a solvent, the ionization of potassium carbonate, rubidium carbonate and cesium carbonate, and the ionization of the phenolic hydroxyl group of the polymer having the structure represented by formula (1) can be effectively advanced.
  • the solvent used in the production method of the present embodiment can be used without particular limitation as long as the polymer having the structure represented by formula (1) dissolves and the esterification reaction in the present embodiment is not significantly inhibited.
  • Aprotic solvents are preferred, and at least one of aromatic hydrocarbon solvents and ethereal solvents are more preferred.
  • an aprotic solvent By using an aprotic solvent, the action on O 2 - derived from phenolic hydroxyl groups tends to proceed effectively.
  • Specific examples of solvents include toluene (Toluene), dimethylacetamide (DMAC), cyclopentyl methyl ether (CPME), 4-methyltetrahydropyran (MTHP), and 1,4-dioxane (Dioxane).
  • the solvent is preferably toluene from the viewpoint that it has low polarity, is a good solvent for the polymer having the structure represented by formula (1), and has a boiling point suitable for the esterification reaction.
  • cyclopentyl methyl ether which is highly hydrophobic and hardly generates peroxides
  • the solvent is preferably a dehydrated solvent.
  • the amount thereof is preferably 0.1 mL or more, and 1.0 mL or more, relative to 1 g of the polymer having the structure represented by formula (1). is more preferable, and 2.0 mL or more is even more preferable. By making it equal to or higher than the above lower limit, it is possible to effectively ensure the fluidity for allowing the esterification reaction to proceed smoothly.
  • the amount of the solvent is preferably 200 mL or less, more preferably 100 mL or less, and even more preferably 50 mL or less, per 1 g of the polymer having the structure represented by formula (1).
  • the content is equal to or less than the above upper limit, the concentration for smoothly advancing the esterification reaction can be maintained, and the effect of reducing the production cost tends to be further improved.
  • one solvent may be used, or two or more solvents may be used. When two or more are used, the total amount is preferably within the above range.
  • the (meth)acrylic acid ester compound obtained in the present embodiment may be either a methacrylic acid ester compound or an acrylic acid ester compound, but is preferably a methacrylic acid ester compound.
  • the reaction temperature of the esterification reaction is preferably ⁇ 20° C. or higher, more preferably 0° C. or higher, and even more preferably 20° C. or higher. By making it equal to or higher than the above lower limit, the esterification reaction proceeds smoothly, and at a high rate, the hydroxyl groups of the polymer having the structure represented by formula (1) tend to be converted to (meth)acrylic groups. .
  • the reaction temperature of the esterification reaction is preferably 200° C. or lower, more preferably 180° C. or lower, and even more preferably 150° C. or lower.
  • the reaction time for the esterification reaction is preferably 0.5 hours or longer, more preferably 1.0 hours or longer, and even more preferably 2.0 hours or longer.
  • the reaction time of the esterification reaction is preferably 120 hours or less, more preferably 72 hours or less, and even more preferably 48 hours or less.
  • the esterification may be carried out in a normal atmosphere (in the presence of air) or in an inert gas atmosphere. Manufacturing costs can be further reduced by carrying out under a normal atmosphere.
  • the esterification reaction can proceed in a non-aqueous, deoxygenated system, and the esterification can proceed more effectively.
  • the (meth)acrylic acid ester compound can be recovered with a high recovery rate by one filtration.
  • the diameter of the filter for filtration in this embodiment is preferably 0.2 to 7.0 ⁇ m.
  • Filtration is preferably performed after cooling to about room temperature (eg, 20 to 40° C.) after the esterification reaction.
  • the filtered reaction solution is preferably vacuum-dried, and more preferably vacuum-dried after most of the reaction solvent is distilled off.
  • the (meth)acrylic acid ester compound can be isolated with a high recovery rate only by the filtration operation. It goes without saying that purification operations may also be carried out.
  • the amount of (meth)acrylic acid as an impurity is preferably less than 1 mol% with respect to 1 mol of the polymer having the structure represented by formula (1). It is more preferably 0.8 mol % or less, still more preferably 0.6 mol % or less, and even more preferably 0.4 mol % or less.
  • the lower limit of the amount of (meth)acrylic acid, which is an impurity is ideally 0 mol %, but is practically 0.01 mol % or more.
  • the amount of impurities derived from the acyl compound is It is preferably less than 1 mol%, more preferably 0.8 mol% or less, and preferably 0.6 mol% or less relative to 1 mol of the polymer having the structure represented by (1). More preferably, it is 0.4 mol % or less.
  • the lower limit of the amount of the impurity derived from the acyl compound, which is the impurity is 0 mol %, but it is practically 0.01 mol % or more.
  • An impurity derived from an acyl compound is, for example, acetic acid when the acyl compound is acetic anhydride.
  • the (meth)acrylic acid ester compound obtained by the production method of the present embodiment may be used as it is, or may be used as a resin composition containing other curable compounds and additives.
  • Other curable compounds are exemplified by compounds having carbon-carbon unsaturated bond groups and epoxy resins.
  • Additives include flame retardants, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, flow control agents, lubricants, antifoaming agents, and dispersants. agents, leveling agents, brighteners, polymerization inhibitors and the like.
  • the (meth)acrylic acid ester compound obtained by the production method of the present embodiment or the resin composition containing the (meth)acrylic acid ester compound is preferably cured and used as a cured product. Since such a cured product has excellent heat resistance and excellent dielectric properties, it can be suitably used as an insulating layer for printed wiring boards and a semiconductor package material.
  • the number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) of the starting resin were calculated using gel permeation chromatography (GPC) and converted to standard polystyrene.
  • the apparatus used was an integrated LC (LC-2010 HT manufactured by SHIMADZU) and an RI detector (RID-20A manufactured by SHIMADZU).
  • LC-2010 HT manufactured by SHIMADZU
  • RID-20A manufactured by SHIMADZU
  • KF-801, KF-802, KF-803, KF-804 Four standard columns (KF-801, KF-802, KF-803, KF-804) are connected in series.
  • a sample dissolved in THF was passed under the conditions of THF as an eluent, a flow rate of 1.0 mL, and 40° C. for measurement.
  • Example 1 According to the following scheme, using toluene (8 mL) as a solvent, oligophenylene ether having hydroxyl groups at both ends (SABIC, SA-90, na + ma in the group R a is about 12.) 828 mg (hydroxyl group amount 1 mmol) is reacted with 185 mg (1.2 mmol) of methacrylic anhydride (MAA) in the presence of 691 mg (5 mmol) of potassium carbonate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., average particle size of 150 ⁇ m or less) at 100 ° C. for 6 hours.
  • MAA methacrylic anhydride
  • the methacrylic rate (OH modification rate) and residual methacrylic acid rate (percentage of impurities) of the polymer were calculated based on the results of proton nuclear magnetic resonance spectrum ( 1 H NMR) analysis.
  • AVANCE III500 500 MHz manufactured by BRUKER was used as a nuclear magnetic resonance apparatus. Specifically, 0.5 mL of the reaction solution was air-cooled, filtered through a 0.45 ⁇ m filter, and the filtrate was vacuum-dried (pressure of less than 1 hPa, 40° C.) for 1 hour. This was dissolved in heavy chloroform and subjected to 1 H NMR analysis at 25°C.
  • FIG. 1 shows the 1 H NMR spectrum (range of 4 ppm to 7 ppm) of SA-90, which is an oligophenylene ether with hydroxyl groups on both ends.
  • SA-90 is an oligophenylene ether with hydroxyl groups on both ends.
  • the theoretical value of the integral ratio should be 2.0, but it was actually observed to be 1.8.
  • the protons of the hydroxyl group tend to undergo proton exchange in solution, resulting in a broad peak that is difficult to observe.
  • Example 2 In Example 1, the catalyst was changed from 5mmol of potassium carbonate to 5mmol of cesium carbonate (1.63 g), and the rest was carried out in the same manner. It was confirmed that methacrylic groups were introduced into the hydroxyl groups of the oligophenylene ether having hydroxyl groups at both ends at a high conversion rate of 96 mol %. The methacrylic rate and residual methacrylic acid rate were measured in the same manner as in Example 1.
  • Example 3 In Example 1, the solvent was changed to dimethylacetamide (DMAC), and the others were carried out in the same manner. It was confirmed that methacrylic groups were introduced into the hydroxyl groups of the oligophenylene ether having hydroxyl groups at both ends at a high conversion rate of 90 mol %. The methacrylic rate and residual methacrylic acid rate were measured in the same manner as in Example 1.
  • DMAC dimethylacetamide
  • Example 4 In Example 1, the solvent was changed to 1,4-dioxane, and the rest was the same. It was confirmed that methacrylic groups were introduced into the hydroxyl groups of the oligophenylene ether having hydroxyl groups at both ends at a high conversion rate of 99 mol %. The methacrylic rate and residual methacrylic acid rate were measured in the same manner as in Example 1.
  • Example 5 In Example 1, the solvent was changed to cyclopentyl methyl ether (CPME), and the others were carried out in the same manner. It was confirmed that methacrylic groups were introduced into the hydroxyl groups of the oligophenylene ether having hydroxyl groups at both ends at a high conversion rate of more than 99 mol %.
  • FIG. 2 shows the 1 H NMR spectrum (range of 4 ppm to 7 ppm) of the resulting oligophenylene ether with methacrylic groups on both ends. Assuming that the integral ratio of protons (d 1 , d 2 ) of the double bond of the methacrylic group near 5.7 to 5.8 ppm and near 6.3 to 6.4 ppm in FIG.
  • CPME cyclopentyl methyl ether
  • Example 6 In Example 1, the solvent was changed to 4-methyltetrahydropyran (MTHP), and the rest was the same. It was confirmed that methacrylic groups were introduced into the hydroxyl groups of the oligophenylene ether having hydroxyl groups at both ends at a high conversion rate of 99 mol %. The methacrylic rate and residual methacrylic acid rate were measured in the same manner as in Example 1.
  • MTHP 4-methyltetrahydropyran
  • Example 7 In Example 1, OPE-2000 (Mitsubishi Gas Chemical Co., Ltd., nb + mb is about 12 in the group R b .) 821 mg ( The amount of hydroxyl groups was changed to 1 mmol), and the other operations were carried out in the same manner. It was confirmed that methacrylic groups were introduced into the hydroxyl groups of the oligophenylene ether at a high conversion rate of 95 mol %. The methacrylic rate and residual methacrylic acid rate were measured in the same manner as in Example 1.
  • Example 8 In Example 7, the solvent was changed to cyclopentyl methyl ether (CPME), and the rest was the same. It was confirmed that methacrylic groups were introduced into the hydroxyl groups of the oligophenylene ether at a high conversion rate of 98 mol %. The methacrylic rate and residual methacrylic acid rate were measured in the same manner as in Example 1.
  • CPME cyclopentyl methyl ether
  • Example 9 According to the following scheme, using cyclopentyl methyl ether (CPME) (8 mL) as a solvent, p-tert-butyl-modified xylene resin (Xy-PTBP) (manufactured by Mitsubishi Gas Chemical Company, nc is about 6 and mc is about 4). ) 3.46 g (hydroxyl group amount 10 mmol) is reacted with 6 mmol (925 mg) of methacrylic anhydride (MAA) in the presence of 50 mmol (6.91 g) of potassium carbonate at 100 ° C. for 6 hours, and further 32 mmol (3.27 g) of acetic anhydride (Ac 2 O) at 100° C. for 6 hours.
  • CPME cyclopentyl methyl ether
  • Xy-PTBP p-tert-butyl-modified xylene resin
  • MAA methacrylic anhydride
  • Comparative example 1 In Example 1, the potassium carbonate was changed to 0.2 mmol of 4-dimethylaminopyridine (DMAP), and the rest was carried out in the same manner. The introduction rate of methacrylic groups into the hydroxyl groups of the hydroxyl oligophenylene ether was 92 mol %. Unlike the case of Examples, most of DMAP (37% per polymer molecule) and by-produced methacrylic acid (137% per polymer molecule) remained even after filtration after the reaction. Moreover, since DMAP is expensive, it is disadvantageous in terms of cost as compared with the potassium carbonate method.
  • DMAP 4-dimethylaminopyridine
  • a 1 H NMR spectrum (range of 4 ppm to 7 ppm) of the oligophenylene ether with methacrylic groups on both ends obtained in Comparative Example 1 is shown in FIG.
  • Hydroxyl protons (a) around 4.1 to 4.6 ppm were not observed due to proton exchange with methacrylic acid present in large amounts in the solution. Instead, some peaks with unknown structures were observed.
  • Comparative example 2 In Example 1, the potassium carbonate was changed to 5 mmol of sodium carbonate, and the others were carried out in the same manner. The rate of introduction of methacrylic groups into the hydroxyl groups of the hydroxyl oligophenylene ether was 21 mol %. The methacrylic rate and residual methacrylic acid rate were measured in accordance with Comparative Example 1.
  • Comparative example 3 In Example 1, the potassium carbonate was changed to 5 mmol of lithium carbonate, and the others were carried out in the same manner. The rate of introduction of methacrylic groups into the hydroxyl groups of the hydroxyl oligophenylene ether was 5 mol %. The methacrylic rate and residual methacrylic acid rate were measured in accordance with Comparative Example 1.
  • Comparative example 4 In Example 1, the potassium carbonate was changed to 5 mmol of calcium carbonate, and the others were carried out in the same manner. The rate of introduction of methacrylic groups into the hydroxyl groups of the hydroxyl oligophenylene ether was 3 mol %. The methacrylic rate and residual methacrylic acid rate were measured in accordance with Comparative Example 1.
  • Comparative example 5 In Example 1, the potassium carbonate was changed to 5 mmol of potassium hydrogencarbonate, and the others were carried out in the same manner. The rate of introduction of methacrylic groups into the hydroxyl groups of the hydroxyl oligophenylene ether was 7 mol %. The methacrylic rate and residual methacrylic acid rate were measured in accordance with Comparative Example 1.
  • Comparative example 6 In Example 1, the potassium carbonate was changed to 5 mmol of potassium hydroxide, and the others were carried out in the same manner. Introduction of a methacryl group to the hydroxyl group of the hydroxyl oligophenylene ether was not observed. The methacrylic rate and residual methacrylic acid rate were measured in accordance with Comparative Example 1.
  • Comparative example 8 According to the following scheme, using a reactor equipped with a Dean-Stark apparatus, using paraxylene (20 mL) as a solvent, oligophenylene ether having hydroxyl groups at both ends (SA-90, manufactured by SABIC) 2.07 g (hydroxyl group amount 2.5 mmol) was reacted with 5 mmol of methacrylic acid (MA) in the presence of 0.5 mmol of B(OH) 3 /H 2 SO 4 with azeotropic distillation at 130° C. for 24 hours. After 0.5 mL of the reaction solution was air-cooled, it was filtered through a 0.45 ⁇ m filter and vacuum-dried (pressure of less than 1 hPa, 40° C.) for 1 hour.
  • SA-90 oligophenylene ether having hydroxyl groups at both ends
  • Comparative example 9 In Comparative Example 8, instead of B(OH) 3 /H 2 SO 4 , p-Me-C 6 H 4 SO 3 H.H 2 O (para-toluenesulfonic acid monohydrate, PTSA-H 2 O) 0.25 mmol was used and the amount of methacrylic acid (MA) was changed from 5 mmol to 12.5 mmol, otherwise the procedure was the same.
  • the introduction ratio of methacrylic groups to the hydroxyl groups of the oligophenylene ether having hydroxyl groups at both ends was 6 mol %.
  • the methacrylic rate and residual methacrylic acid rate were measured in accordance with Comparative Example 1.
  • Comparative example 10 In Comparative Example 8, AMBERLYST (registered trademark) 15 (manufactured by Sigma-Aldrich) was used instead of B(OH) 3 /H 2 SO 4 , and oligophenylene ether having hydroxyl groups at both ends (manufactured by SABIC, SA-90 ) was used, and the amount of methacrylic acid (MA) was changed from 5 mmol to 12.5 mmol. The introduction ratio of methacrylic groups to the hydroxyl groups of the oligophenylene ether having hydroxyl groups at both ends was 6 mol %.
  • Example 10 As shown in the scheme below, in Example 8, the same procedure was performed on a 25-fold scale. It was confirmed that methacrylic groups were introduced into the hydroxyl groups of the oligophenylene ether at a high conversion rate of 95 mol %. The obtained compound was in the form of a beige powder and had a residual hydroxyl group content of 5 mol %.
  • Example 1 the type of catalyst was changed to sodium acetate (AcONa), the amount of catalyst and the type of solvent were changed as shown in Table 5, and the rest was carried out in the same manner. Table 5 shows the results.
  • Examples 1-9 and Comparative Examples 1-13 are summarized below.
  • the impurity indicates methacrylic acid (MA) unless otherwise indicated.
  • AcOH indicates acetic acid.
  • the reason why the amount of impurities may exceed 100 mol % is that, for example, when 1.2 mmol of methacrylic anhydride is used for 1 mmol of hydroxyl group, methacrylic anhydride is added to 1 molecule of the polymer. This is because 240 mol % is added.
  • the values of residual hydroxyl groups and introduced methacrylic groups differ for each example and comparative example, making comparison difficult. .
  • the "100-OH modification ratio" corresponds to "the ratio (mol%) of X in formula (1) being a hydrogen atom".
  • ND indicates not detected.
  • the hydroxyl value unit (g/mol) indicates the mass of the polymer (raw material resin) per mole of hydroxyl group.
  • mol/mol-OH indicates the addition amount (mol) per 1 mol of hydroxyl group of the starting resin (polymer having the structure represented by formula (1)).
  • Example 11 The (meth)acrylic acid ester compound (OPE-2MA) obtained in Example 10 was thermally cured to prepare a resin. Specifically, 1 part by mass of Perbutyl (registered trademark) P was added to OPE-2MA obtained in Example 10, the temperature was raised at a rate of 3 ° C./min, and the pressure was 1.92 MPa. and 200° C. for 2 hours to obtain a cured product having a thickness of 1.2 mm. The obtained resin was measured for dielectric constant, dielectric loss tangent and glass transition temperature.
  • Perbutyl (registered trademark) P was added to OPE-2MA obtained in Example 10
  • the temperature was raised at a rate of 3 ° C./min, and the pressure was 1.92 MPa. and 200° C. for 2 hours to obtain a cured product having a thickness of 1.2 mm.
  • the obtained resin was measured for dielectric constant, dielectric loss tangent and glass transition temperature.
  • the glass transition temperature of the cured product was defined as the peak temperature of the dynamic elastic modulus obtained by measuring the dynamic viscoelasticity of the obtained cured product cut into 5 mm wide and 40 mm long pieces.
  • the unit is °C.
  • the dielectric constant and dielectric loss tangent of the cured product were measured at 10 GHz by the cavity resonance perturbation method on the obtained cured product cut into a piece having a thickness of 1.2 mm, a width of 0.8 mm and a length of 100 mm.
  • the obtained cured product had a dielectric constant (D k ) of 2.461 (10 GHz), a dielectric loss tangent (D f ) of 0.00423 (10 GHz), and a glass transition temperature (T g ) of 155° C. (10 Hz). rice field.
  • the physical properties (D k , D f , T g ) of the thermosetting resin of OPE-2MA were equivalent to those of a general cured product of polyphenylene ether with methacrylic groups on both ends.

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20240136237A (ko) 2023-03-06 2024-09-13 닛테츠 케미컬 앤드 머티리얼 가부시키가이샤 비닐 수지의 제조 방법

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50139840A (https=) * 1974-04-27 1975-11-08
WO2005035625A1 (en) * 2003-10-03 2005-04-21 General Electric Company Capped poly(arylene ether) composition and process
JP2011105667A (ja) 2009-11-19 2011-06-02 Mitsubishi Rayon Co Ltd フェニルエステルの製造方法
CN109970519A (zh) * 2018-06-05 2019-07-05 台湾中油股份有限公司 含双环戊二烯之官能化聚(2,6-二甲基苯醚)寡聚物、其制造方法及其用途
CN110437439A (zh) * 2019-08-27 2019-11-12 广东省石油与精细化工研究院 一种烯基封端聚苯醚的合成方法
CN110628013A (zh) * 2019-08-28 2019-12-31 河北健馨生物科技有限公司 双官能化含磷聚苯醚及其制备方法与应用
CN113603882A (zh) * 2020-05-04 2021-11-05 台湾中油股份有限公司 寡聚(2,6-二甲基苯醚)、其制备方法与固化物
CN113603723A (zh) * 2020-05-04 2021-11-05 台湾中油股份有限公司 磷系（2,6-二甲基苯醚）寡聚物及其制备方法与固化物

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010090258A1 (ja) * 2009-02-05 2010-08-12 三菱レイヨン株式会社 （メタ）アクリル酸エステルの製造方法
JP2014105264A (ja) * 2012-11-27 2014-06-09 Mitsubishi Rayon Co Ltd ポリエステル（メタ）アクリレートの製造方法
CN106565951B (zh) * 2015-10-08 2019-01-29 长春人造树脂厂股份有限公司 磷系聚(2,6二甲基苯醚)寡聚物及其制备方法和热固化物

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50139840A (https=) * 1974-04-27 1975-11-08
WO2005035625A1 (en) * 2003-10-03 2005-04-21 General Electric Company Capped poly(arylene ether) composition and process
JP2011105667A (ja) 2009-11-19 2011-06-02 Mitsubishi Rayon Co Ltd フェニルエステルの製造方法
CN109970519A (zh) * 2018-06-05 2019-07-05 台湾中油股份有限公司 含双环戊二烯之官能化聚(2,6-二甲基苯醚)寡聚物、其制造方法及其用途
JP2019210451A (ja) 2018-06-05 2019-12-12 台湾中油股▲フン▼有限公司 ジシクロペンタジエンを有する官能化ポリ（２，６−ジメチルフェニレンオキシド）オリゴマー及びその製造方法、並びにその用途
CN110437439A (zh) * 2019-08-27 2019-11-12 广东省石油与精细化工研究院 一种烯基封端聚苯醚的合成方法
CN110628013A (zh) * 2019-08-28 2019-12-31 河北健馨生物科技有限公司 双官能化含磷聚苯醚及其制备方法与应用
CN113603882A (zh) * 2020-05-04 2021-11-05 台湾中油股份有限公司 寡聚(2,6-二甲基苯醚)、其制备方法与固化物
CN113603723A (zh) * 2020-05-04 2021-11-05 台湾中油股份有限公司 磷系（2,6-二甲基苯醚）寡聚物及其制备方法与固化物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4286361A4

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20240136237A (ko) 2023-03-06 2024-09-13 닛테츠 케미컬 앤드 머티리얼 가부시키가이샤 비닐 수지의 제조 방법

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