WO2008026312A1 - Composé vinyl éther ayant un groupe acétoacétoxy, polymère dudit composé et leurs procédés de fabrication - Google Patents

Composé vinyl éther ayant un groupe acétoacétoxy, polymère dudit composé et leurs procédés de fabrication Download PDF

Info

Publication number
WO2008026312A1
WO2008026312A1 PCT/JP2007/000913 JP2007000913W WO2008026312A1 WO 2008026312 A1 WO2008026312 A1 WO 2008026312A1 JP 2007000913 W JP2007000913 W JP 2007000913W WO 2008026312 A1 WO2008026312 A1 WO 2008026312A1
Authority
WO
WIPO (PCT)
Prior art keywords
vinyl
polymer
ether
vinyl ether
copolymer
Prior art date
Application number
PCT/JP2007/000913
Other languages
English (en)
Japanese (ja)
Inventor
Shinji Sugihara
Isao Ikeda
Original Assignee
Maruzen Petrochemical Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Maruzen Petrochemical Co., Ltd. filed Critical Maruzen Petrochemical Co., Ltd.
Publication of WO2008026312A1 publication Critical patent/WO2008026312A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C07C69/716—Esters of keto-carboxylic acids or aldehydo-carboxylic acids
    • C07C69/72—Acetoacetic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • 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
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether

Definitions

  • Vinyl ether compounds having a acetoacetoxy group having a acetoacetoxy group, polymers thereof and methods for producing them
  • the present invention relates to a novel vinyl ether compound having a acetoacetoxy group useful as a chelate resin, a polymer thereof, and a process for producing them.
  • 2-acetoacetoxyl methacrylate and its (co) polymer are useful compounds known as chelating agents and hybrid materials.
  • the polymerization of this compound is limited to anion polymerization or radical polymerization, and a polymer cannot be produced by cationic polymerization. Therefore, it is a cationic polymerization monomer, and an alkenyl ether that can produce a polymer only by force thione polymerization. It was difficult to produce this copolymer.
  • vinyl ethers having a acetoacetoxy group are vinyl ethers that have been found so far because these compounds have a reactive methylene group and also exhibit keto-enol tautomerism to cause side reactions.
  • a method called living cationic polymerization in particular, has a relatively narrow molecular weight distribution of the resulting polymer, and the degree of polymerization can be adjusted arbitrarily, so that the desired polymer or copolymer can be obtained. This is an advantageous method for producing with good yield.
  • alkenyl ether has specific functions such as highly sensitive stimulus response ability and gelation ability, a cationically polymerizable monomer having a metal chelate ability capable of copolymerizing with these has been demanded.
  • An object of the present invention is to provide a novel acetocetoxy group-containing vinyl ether compound that can be polymerized by cationic polymerization and is useful as a chelate resin, a polymer thereof, or It is to provide a copolymer.
  • the present inventor has made various studies on vinyl ethers having a new acetoacetoxy group. As a result, tert-butyl acetoacetate and 2-hydroxy acetyl vinyl ether are reacted to produce 2-aceto acetoxiecetate. It has been found that chill vinyl ether can be produced. Further investigations have shown that 2-acetoacetoxylbinyl ether has a keto-enol tautomer, but is stable as a keto form in the solvent. For example, the inventors have found that a polymer or copolymer can be quantitatively produced in high yield by force thione polymerization without causing side reactions, and the present invention has been completed.
  • the present invention provides 2-acetocetoxysilane vinyl ester represented by the following formula:
  • the present invention also provides a polymer or copolymer having a repeating unit represented by the following:
  • the present invention further comprises reacting tert-butyl acetate acetate with 2-hydroxyethyl vinyl ether.
  • the present invention provides a method for producing a 2-acetoacetoxyl vinyl ether which is characterized.
  • the present invention relates to 2-acetoacetoxyl vinyl ester, Lewis
  • the present invention provides a method for producing a 2-acetocetoxychetyl vinyl ether polymer, characterized in that living cationic polymerization is carried out in the presence of an acid.
  • the present invention relates to 2-acetoxetoxyl vinyl ester and other monomers capable of cationic polymerization in the presence of a Lewis acid.
  • the present invention provides a method for producing 2-acetocetoxychetyl vinyl ether copolymer characterized by subjecting to living cationic polymerization.
  • a polymer or copolymer of a vinylacetoxy group-containing vinyl ether compound useful as a chelate resin can be quantitatively produced with high yield by cationic polymerization.
  • the compound of the present invention can be copolymerized with an alkenyl ether monomer.
  • the alkenyl ether copolymer further possesses metallic properties and metal catalyst recovery ability. Coalescence can be obtained.
  • FIG 1 is a diagram showing a 2- ⁇ Seto ⁇ Se Toki Chez chill vinyl E one ether structure and 1 .eta. New Micromax R measurements of.
  • FIG. 2 is a graph showing the results of 1 ⁇ - ⁇ MR measurement of poly (2-acetocetoxychetyl vinyl ether).
  • FIG. 3 is a view showing gelation of poly (2-acetoxetoxyl vinyl ether) by zinc. Before the zinc chloride was added on the left side, the right side was taken after taking out the gelled portion by adding zinc chloride.
  • FIG. 4 is a diagram showing an absorption spectrum measured by an ultraviolet-visible spectrometer (JASCOV-5550) during the chelate formation of poly (2-acetocetoxychetyl vinyl ether) and iron.
  • JASCOV-5550 ultraviolet-visible spectrometer
  • the monomer to be copolymerized with the compound (1) includes a compound (1)
  • the monomer is not particularly limited as long as it is a monomer capable of cationic polymerization with 1).
  • an alkenyl ether represented by the following general formula (A) is preferable.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a monovalent organic group
  • Examples of the monovalent organic group represented by R 2 include a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms; a halogenated alkyl group; an alkoxyalkyl group; an alkoxyalkoxyalkyl group; a hydroxyalkyl group; An arylalkyl group; an aryloxyalkyl group; an arylcarbonylalkyl group optionally substituted by a halogen atom or an alkoxy group; an aryloxycarbonylalkyl group; an aryl group; a halogen atom Optionally substituted aryloxy group; amine, amide, imide, urethane or urine An alkyl group having an elementary bond; an alkyl group having a hydroxy group, an alkyl group having a carboxylic acid or phosphoric acid which may have an aryl group; (meth) acrylic carbonyloxychetyl group, styrylcarbonyloxychetyl group
  • the compound (1) of the present invention can be produced by reacting 2-hydroxyethyl vinyl ether with t-butyl acetate acetate as shown in the following reaction formula.
  • the reaction between 2-hydroxyethyl vinyl ester and t-butyl acetate salt is carried out in a solvent.
  • the solvent used in the reaction is not particularly limited, and examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene; ethers such as jetyl ether, tetrahydrofuran, and dioxane. Of these, toluene is preferred.
  • the ratio of 2-hydroxyethyl vinyl ether and t-butyl vinyl acetate is 0.5 mol of t_butyl vinyl acetate per 1 mol of 2-hydroxy ethyl vinyl ester. It is preferable to use ⁇ 1 mol.
  • the reaction temperature and reaction time are not particularly limited, and are 90 to 15 ° C for 4 to 8 hours, preferably 90 to 120 ° C for 4 to 5 hours. During the reaction, it is preferable to sequentially remove t-butyl alcohol to be formed.
  • the polymer or copolymer of the compound of the present invention (1) is a Lewis acid in a suitable solvent. It can be obtained by living cationic polymerization in the presence.
  • the solvent used in the reaction is not particularly limited, but ester solvents such as ethyl acetate are preferred. By using an ester solvent, the polymerization system can be stabilized and the living polymerization reaction can be controlled.
  • the Lewis acid is an initiator and needs not to react with a acetoacetoxy group.
  • Lewis acid include boron trifluoride ether complex, boron trichloride, boron tribromide, aluminum trichloride, aluminum tribromide, tin tetrachloride, zinc dichloride and the like.
  • boron which is so-called a semimetal, is preferably used, and boron trifluoride ether complex is particularly preferably used.
  • the use ratio of the Lewis acid is preferably 1/200 to 1/20 mol with respect to 1 mol of monomer.
  • the polymerization reaction is preferably performed by adding an initiating species.
  • the starting species used include compounds that generate protons such as water, alcohol, and protonic acid, and compounds that generate a carbocation such as halogenated alkyl.
  • Examples of such a compound that generates a carbocation include 1-alkoxyethyl acetate, such as 1_isobutoxyethyl acetate.
  • the use ratio of the starting species is preferably from 1/50 to 1/600 mol per 1 mol of monomer.
  • the polymerization conditions of the present invention include a reaction temperature of 70 to 60 ° C, preferably 130 to 40 ° C, and a reaction time of 1 minute to 1 hour, preferably 5 minutes to 30 minutes.
  • the concentration of 2-acetoxetoxyl vinyl ester in the polymerization system is generally 10 to 30% by weight, preferably 10% by weight.
  • the amount of 2_acetoacetoxyvinyl ether exceeds 30% by weight, the molecular weight is controlled. It becomes difficult.
  • the polymerization is stopped by adding a lower alcohol solution to which a lower alcohol such as methanol and a basic compound such as ammonia and amine are added in a very small amount as required.
  • a lower alcohol such as methanol and a basic compound such as ammonia and amine are added in a very small amount as required.
  • the polymer or copolymer can be obtained by removing the unreacted monomer and solvent by using the product as it is or by reprecipitation with methanol, thin film evaporation, or the like.
  • the molecular weight (number average molecular weight) of the polymer or copolymer measured by gel permeation chromatography (GPC) is preferably from 1,000 to 20,000, particularly from 5,000 to 20,000. Is preferred.
  • the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn), which is an index of molecular weight distribution measured by GPC, is preferably 1.1 to 1.6.
  • the polymer or copolymer having the compound (2) of the present invention as a repeating unit thus obtained has a acetoacetoxy group, it can form a chelate with various metals.
  • the chelate resin of the present invention is used, for example, as a metal ion scavenger used to recover a trace amount of metal contained in an organic solvent, or as a metal gelling agent, a dispersant containing a metal, an ink paint, a crosslinking agent, etc.
  • the target metal is not limited as long as it is classified as a metal in the periodic table.
  • silver, copper, platinum, zinc, mercury, lead, tin, iron, thallium, cesium, cobalt examples include magnesium, force domium, nickel, palladium, calcium, barium, strontium, selenium, tantalum, titanium, neodymium, samarium, vanadium, chromium, manganese, ruthenium, molybdenum, and antimony.
  • tert_butylacetoacetate (hereinafter abbreviated as tBAA) 9 Om L and 242 ml of toluene as solvent, (Abbreviated as H O V E) 44 mL was added, and H O V E was added dropwise when the temperature in the flask reached 90 to 120 ° C.
  • HBAA tert_butylacetoacetate
  • H O V E was added dropwise when the temperature in the flask reached 90 to 120 ° C.
  • the target acetoacetoxychetyl vinyl ester was synthesized while constantly removing t BAA by distillation (yield 62.3 mL with respect to raw material H OV E, yield 79.5%).
  • the synthesized 2-acetocetoxychetyl vinyl ether was purified by distillation under reduced pressure. The boiling point was 76 ° C at 2 mm Hg.
  • Fig. 1 shows the 1 H-NMR measurement results of the 2-acetocetoxycylvinyl ester obtained.
  • a glass reaction vessel fitted with a three-way stopcock was heated in a nitrogen gas stream to dry the interior sufficiently.
  • OmM 2 -acetocetoxyl vinyl ether
  • ethyl acetate into the container.
  • Polymerization was initiated by adding 5 mL (2 OmM).
  • the polymerization rate (namely, monomer conversion) of the obtained polymer was determined by a gravimetric method.
  • the weight average molecular weight Mw and the number average molecular weight Mn were measured at a temperature of 38 ° C. using gel filtration chromatography (GPC) using polystyrene gel and THF as an eluent. Furthermore, the ratio of Mw and Mn obtained was calculated and used as an index of molecular weight distribution.
  • Fig. 2 shows the 1 H NMR measurement results of the poly (2-acetocetoxysilane vinyl ester) obtained.
  • Figure 3 shows the gelation. As is clear from FIG. 3, it was confirmed that the polymer of the present invention has a metal ion scavenging property.
  • Figure 4 shows the absorption spectrum measured by the UV-visible spectrometer (JASCO V-550).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un nouveau composé vinyl éther contenant un groupe acétoacétoxy, qui peut être polymérisé par polymérisation cationique et qui est utile en tant que résine chélatante. L'invention concerne également un polymère ou copolymère d'un tel composé vinyl éther. L'invention concerne particulièrement le 2-acétoacétoxyéthyl vinyl éther représenté par la formule suivante (1).
PCT/JP2007/000913 2006-09-01 2007-08-27 Composé vinyl éther ayant un groupe acétoacétoxy, polymère dudit composé et leurs procédés de fabrication WO2008026312A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006237891A JP5088925B2 (ja) 2006-09-01 2006-09-01 アセトアセトキシ基を有するビニルエーテル化合物、その重合体及びそれらの製造方法
JP2006-237891 2006-09-01

Publications (1)

Publication Number Publication Date
WO2008026312A1 true WO2008026312A1 (fr) 2008-03-06

Family

ID=39135602

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2007/000913 WO2008026312A1 (fr) 2006-09-01 2007-08-27 Composé vinyl éther ayant un groupe acétoacétoxy, polymère dudit composé et leurs procédés de fabrication

Country Status (2)

Country Link
JP (1) JP5088925B2 (fr)
WO (1) WO2008026312A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08295825A (ja) * 1995-04-25 1996-11-12 Dainippon Ink & Chem Inc 水性硬化性組成物
JPH09501457A (ja) * 1993-08-05 1997-02-10 ゼネカ・リミテッド 重合体エマルジョンの製造
JP2005113049A (ja) * 2003-10-09 2005-04-28 Maruzen Petrochem Co Ltd 新規な脂環式ビニルエーテル類の重合体
JP2006131805A (ja) * 2004-11-08 2006-05-25 Maruzen Petrochem Co Ltd 脂環式ビニルエーテル共重合体

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09501457A (ja) * 1993-08-05 1997-02-10 ゼネカ・リミテッド 重合体エマルジョンの製造
JPH08295825A (ja) * 1995-04-25 1996-11-12 Dainippon Ink & Chem Inc 水性硬化性組成物
JP2005113049A (ja) * 2003-10-09 2005-04-28 Maruzen Petrochem Co Ltd 新規な脂環式ビニルエーテル類の重合体
JP2006131805A (ja) * 2004-11-08 2006-05-25 Maruzen Petrochem Co Ltd 脂環式ビニルエーテル共重合体

Also Published As

Publication number Publication date
JP2008056852A (ja) 2008-03-13
JP5088925B2 (ja) 2012-12-05

Similar Documents

Publication Publication Date Title
JP5187825B2 (ja) ハイパーブランチポリマー及びその製造方法
JP2017527667A (ja) １つ以上の１，１−二置換アルケン化合物を含む溶液ポリマー、溶液重合方法、及びポリマー組成物
JP5268644B2 (ja) ハイパーブランチポリマー及びその製造方法
CN104151483B (zh) 一种端羟基超支化聚丙烯酸酯的制备方法
JP5661600B2 (ja) ニトリルオキシド化合物、変性高分子材料並びにその製造方法及び成形体
EP3129416B1 (fr) Régulation d'une polymérisation radicalaire contrôlée d'acrylates par la lumière
JP6000249B2 (ja) 鎖末端近傍に湿気硬化性官能基クラスターを有する硬化性組成物
JP5077888B2 (ja) ジビニルエーテル誘導体ポリマー並びにその製造方法及び用途
CN112585176B (zh) 新型胺官能化聚合物及制备方法
Selvamalar et al. Copolymerization of 4-benzyloxycarbonylphenyl methacrylate with glycidyl methacrylate: synthesis, characterization, reactivity ratios and application as adhesives
Yamago et al. Synthesis of structurally well-controlled ω-vinylidene functionalized poly (alkyl methacrylate) s and polymethacrylonitrile by organotellurium, organostibine, and organobismuthine-mediated living radical polymerizations
JP5630957B2 (ja) ハイパーブランチポリマー及びその製造方法
JP2017521515A (ja) アルコキシシラン官能化炭化水素化合物、その中間体、およびその製造方法
Kumar et al. Synthesis, characterization of poly (4-benzyloxyphenylmethacrylate) and its copolymer with butyl methacrylate and determination of monomer reactivity ratios
WO2008026312A1 (fr) Composé vinyl éther ayant un groupe acétoacétoxy, polymère dudit composé et leurs procédés de fabrication
Krieg et al. Tailor Made Side‐Chain Functionalized Macromolecules by Combination of Controlled Radical Polymerization and Click Chemistry
Barboiu et al. Reactions on Polymers with Amine Groups. II. Reactions of Poly (N-Vinylimidazole) and Its Model Compound with Unsaturated Carboxylic Acids
JP6991541B2 (ja) 分子サイズ認識可能な新規ケミカルプローブおよびその製造方法
JP2018024818A (ja) Ｎ−ビニルイミダゾリジン−２−オン化合物とビニルエステル類とのランダム共重合体およびそれを用いた細胞培養用材料
JP5164056B2 (ja) Ｎ−メタクリロイルアゼチジン系ブロック共重合体
JP7218857B2 (ja) 共重合体及び温度感受性高分子
JPH05229990A (ja) ２官能（メタ）アクリレート
CN112166131B (zh) 利用自由基聚合来制造含有烃基的乙烯基醚聚合物的方法
Altomare et al. Synthesis and photobehaviour of hydrophilic acrylic polymers containing azobenzene groups
Popescu et al. Multifunctional Polymethacrylates Obtained Via ATRP of Functional and Reactive Monomers Followed by Polymer Analogous Reaction with Functional Amines

Legal Events

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

Ref document number: 07790397

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 07790397

Country of ref document: EP

Kind code of ref document: A1