JP4667087B2 - Piperidyl group-containing polymer or copolymer and method for producing the (co) polymer - Google Patents

Description

  The present invention relates to a piperidyl group-containing (co) polymer and a method for producing the polymer, and the piperidyl group-containing (co) polymer of the present invention is not only excellent in conductivity or weather resistance itself. It has excellent performance as a light stabilizer for imparting weather resistance and a battery electrode material.

Derivatives having a 2,2,6,6-tetramethylpiperidine structure have a radical scavenging ability and are therefore widely used as weather resistance imparting agents or polymerization inhibitors for organic polymer materials. In addition to these resin weatherability improver applications, the derivatives possessed can also be expected to have specific electrical characteristics. Non-Patent Document 1 and Non-Patent Document 2 describe acetylene monomers and polymerization of acetylene monomers.
However, nitroxy radicals are consumed during the polymerization, and a polymer having a high NO content has not been obtained.
Patent Document 1 and Patent Document 2 describe that a nitroxy radical polymer having a hydroxyl group is effective as an electrode active material of a battery. However, these polymers have a low nitroxy radical content, and a method for producing a polymer having a high nitroxy content has been demanded.

J.S.Miller et al., Chemistry of Materials, 1990, 2, 60 L, Dulog et al., Macromol Chem, Rapid Commun. 1993, 14, 147 JP 2003-132891 A JP 2004-207249 A

  Accordingly, an object of the present invention is to provide a piperidyl group-containing polymer having a high NO content useful as a weather-resistant conductive material, a high weather-resistant polymer material, a light stabilizer for plastics or a battery positive electrode material, and a method for producing the polymer. It is to provide.

  As a result of intensive studies, the present inventors have found that a piperidyl group-containing polymer synthesized by polymerizing an acetylene monomer or propargyl ether monomer having a specific structure with a Pd salt catalyst can achieve the above object. I found out.

That is, the present invention has been made on the basis of the above findings, and a compound selected from at least one of the compounds represented by the following general formula (1), general formula (2) or general formula (3) is palladium. A piperidyl group-containing polymer or a piperidyl group-containing copolymer having a high NO content containing the structural unit represented by the following general formula (4) or general formula (5), characterized by being polymerized with a catalyst consisting only of a salt. A method for producing a polymer is provided.

(Wherein R or R ₁ each independently represents an oxygen free radical or a carbamoyloxy group, R ₂ represents a hydrogen atom or a hydroxyl group, X represents a direct bond or an oxygen atom, Y represents a direct bond or methylene) And n and m each represent a number of 1 to 100.)

  Since the piperidyl group-containing polymer of the present invention has a high NO content, it can be used as a highly weather-resistant conductive material, and is useful as a light stabilizer by being added to a synthetic resin as a polymer-type weathering agent. Further, it can be expected to be useful as a battery positive electrode material.

  Hereinafter, the present invention having the above gist will be described in detail.

In the piperidyl group-containing compound represented by the general formula (1) to the general formula (5), the carbamoyloxy group represented by R or R ₁ is a group represented by —O—CO—NH—R _3. And R ₃ is a monovalent organic group. In the general formulas (1) to (3), a compound in which R and R ₁ are OH and an isocyanate compound are reacted to form an N-substituted carbamoyloxy group, and then polymerized to polymerize the general formula (4) or ( The carbamoyloxy group-containing polymer represented by 5) can be obtained.

  The isocyanate compound is not particularly limited, and examples thereof include aliphatic (mono) diisocyanate, aromatic (mono) diisocyanate, and alicyclic (mono) diisocyanate.

  Examples of the aliphatic monoisocyanate include methylsulfonyl isocyanate, butyl isocyanate, hexadecyl isocyanate, octadecyl isocyanate and the like. Examples of the aliphatic diisocyanate include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dipropyl ether diisocyanate, 2,2-dimethylpentane diisocyanate, and 3-methoxyhexane diisocyanate. , Octamethylene diisocyanate, 2,2,4-trimethylpentane diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, 3-butoxyhexane diisocyanate, 1,4-butylene glycol dipropyl ether diisocyanate, thiodihexyl diisocyanate, metaxylylene diisocyanate, para Xylylene diisocyanate Titanate, tetramethyl xylylene diisocyanate.

Examples of the aromatic monoisocyanate include phenyl isocyanate, tolyl isocyanate, isocyanic acid-3,4-dichlorophenyl, m-nitrophenyl isocyanate, and toluenesulfonyl isocyanate.
Examples of aromatic diisocyanates include metaphenylene diisocyanate, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, dimethylbenzene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, tolidine diisocyanate, and 1,4-naphthalene. Examples include diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, 2,6-naphthalene diisocyanate, and 2,7-naphthalene diisocyanate.

  Examples of the alicyclic monoisocyanate include cyclohexyl isocyanate.

  Specific examples of the piperidyl group-containing polymer containing the structural unit represented by the general formula (4) or the general formula (5) include the following compound No. 1-No. 4 is mentioned.

The polymer represented by the general formula (4) of the present invention is obtained by polymerizing the acetylene monomer compound represented by the general formula (1) with a palladium salt catalyst to obtain a piperidyl group-containing polymer.
Further, the polymer represented by the general formula (5) polymerizes the propargyl ether monomer compound represented by the general formula (2) or the acetylene monomer represented by the general formula (3) with a palladium salt catalyst. As a result, a piperidyl-containing polymer is obtained.

Palladium chloride (PdCl ₂ ) is preferably used as the kind of the palladium salt catalyst, but palladium bromide (PdBr ₂ ), bis (acetylacetonato) palladium (Pd (acac) ₂ ), trans -Dichlorobis (triphenylphosphine) palladium, dinitrodiamminepalladium (II), palladium (II) acetate (Pd (OAc) ₂ ).

  The production of the polymer of the present invention is not particularly limited, but it can be easily carried out in an organic solvent (or without a solvent) using a Pd salt catalyst or the like. Polymerization may be used. The polymer can be a homopolymer obtained by polymerizing only the monomer, or can be a copolymer (copolymer) of the monomer and a conventionally known monomer.

  Other polymerizable monomers to be copolymerized include 1,4-diethynylbenzene, 1,3-diethynylbenzene, dipropargyl ether, dipropargylamine, propargylpropionate, propargylpropenoate, propargyl An acetate etc. are mention | raise | lifted and you may copolymerize with 1 type (s) or 2 or more types of monomers.

  Although the polymer containing the structural unit represented by the general formula (4) or (5) of the present invention can be obtained by polymerization reaction in a solvent or without a solvent, it is preferably carried out in a solvent. As a kind of solvent used for the polymerization reaction of the polymer represented by the general formula (4) or (5), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N- Amide solvents such as methylpyrrolidone; ether solvents such as tetrahydrofuran, dioxane, trioxane and the like can be exemplified, and N, N-dimethylacetamide is preferably used. The amount of the solvent used is preferably in the range of 50 to 3000 parts by mass with respect to 100 parts by mass of the raw material monomer.

  Furthermore, the reaction temperature of the polymerization reaction is 20 to 150 ° C., preferably 40 to 70 ° C. in the catalytic reaction. The reaction time is 1 hour to 7 days, more preferably 10 hours to 150 hours, and the reaction is performed in a nitrogen atmosphere or in a closed system.

  As for the molecular weight in the polymer of the present invention, the average molecular weight is preferably from 400 to 100,000. More preferably, 500 or more is more preferable. When the molecular weight is 400 or less, there is a problem that the retention is poor. On the other hand, if the average molecular weight exceeds 100,000, the viscosity is too high and there is a problem in workability. In addition, an average molecular weight is a number average molecular weight, and shows the molecular weight converted into standard polystyrene by gel permeation chromatography.

  Furthermore, the use of the compound of the present invention includes a high weather resistance conductive material, and a use as a light stabilizer or a battery positive electrode material added to a synthetic resin as a polymer type weather resistance agent.

  When the polymer of the present invention is used as a stabilizer for organic materials, the synthetic resin to be blended includes polypropylene, high density polyethylene, low density polyethylene, linear low density polyethylene, polybutene-1, poly-3-methylpentene, and the like. Α-olefin polymers or polyolefins such as ethylene-vinyl acetate copolymers and ethylene-propylene copolymers and their copolymers, polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride , Rubber chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic ester Copolymer, vinyl chloride-maleic acid ester copolymer Body, halogen-containing resin such as vinyl chloride-cyclohexylmaleimide copolymer, petroleum resin, coumarone resin, polystyrene, polyvinyl acetate, acrylic resin, styrene and / or α-methylstyrene and other monomers (for example, anhydrous maleic acid) Acid, phenylmaleimide, methyl methacrylate, butadiene, acrylonitrile, etc.) (for example, AS resin, ABS resin, MBS resin, heat-resistant ABS resin, etc.), polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, Linear polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyamides such as polyphenylene oxide, polycaprolactam and polyhexamethylene adipamide, polylactone (polylactic acid), polycarbonate, Thermoplastic resins such as carbonate / ABS resin, branched polycarbonate, polyacetal, polyphenylene sulfide, polyurethane, and fiber-based resin, and blends thereof, or heat of phenol resin, urea resin, melamine resin, epoxy resin, unsaturated polyester resin, etc. A curable resin can be mentioned. Furthermore, elastomers such as isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, and styrene-butadiene copolymer rubber may be used.

  The piperidyl group-containing polymer of the present invention is a phenolic antioxidant, a phosphorus antioxidant, a thioether antioxidant, an ultraviolet absorber, a hindered amine light stabilizer, as it is or when processing a synthetic resin. Further stabilization can be achieved by adding an agent or the like.

  Examples of the phenolic antioxidant include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-ditert-butyl-4). -Hydroxybenzyl) phosphonate, 1,6-hexamethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide], 4,4'-thiobis (6-tert-butyl-m-cresol ), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-butylidenebis (6-tert-butyl) -M-cresol), 2,2'-ethylidenebis (4,6-ditert-butylphenol), 2,2'-ethylidenebis (4-secondarybutyl-6-tert-butylphenol) Nol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tertiary) Butylbenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4- Hydroxybenzyl) -2,4,6-trimethylbenzene, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, stearyl (3,5- Ditertiarybutyl-4-hydroxyphenyl) propionate, tetrakis [methyl 3- (3,5-ditertiarybutyl-4-hydroxyphenyl) propionate] methane, thiodiethyleneglycol Bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], bis [3 3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methyl) Benzyl) phenyl] terephthalate, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 3,9-bis [1,1-dimethyl-2- {(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] Ndecane, triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like, and 0.001 to 10 parts by mass, more preferably 100 parts by mass of the synthetic resin. 0.05 to 5 parts by mass is used.

  Examples of the phosphorus antioxidant include trisnonylphenyl phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl]. Phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di Tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritert-butylphenyl) pentaerythritol diphosphite Phosphite, bis (2,4-dicumylphenyl) pen Erythritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) -4,4′-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1 , 1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane triphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, 9,10-dihydro-9 -Oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis (4,6-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2'-methylenebis (4,6- Tributylphenyl) -octadecyl phosphite, 2,2′-ethylidenebis (4 6-ditert-butylphenyl) fluorophosphite, tris (2-[(2,4,8,10-tetrakis tert-butyldibenzo [d, f] [1,3,2] dioxaphosphine-6 -Yl) oxy] ethyl) amine, phosphite of 2-ethyl-2-butylpropylene glycol and 2,4,6-tritert-butylphenol, etc., and 0.001 to 100 parts by mass of synthetic resin 10 mass parts, More preferably, 0.05-5 mass parts is used.

  Examples of the thioether-based antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, and pentaerythritol tetra (β-alkylmercaptopropionate esters). 0.001 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the synthetic resin.

  Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone). 2-hydroxybenzophenones; 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) -5-chloro Benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-5′-tert. Octylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-dicumylphenyl) benzotriazole, 2, 2- (2 such as' -methylenebis (4-tert-octyl-6- (benzotriazolyl) phenol), 2- (2'-hydroxy-3'-tert-butyl-5'-carboxyphenyl) benzotriazole '-Hydroxyphenyl) benzotriazoles; phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, 2,4-ditert-amylphenyl- Benzoates such as 3,5-ditert-butyl-4-hydroxybenzoate and hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate; 2-ethyl-2′-ethoxyoxanilide, 2-ethoxy- Substituted oxanilides such as 4′-dodecyl oxanilide; ethyl-α-cyano-β, β-diphenylacrylate And cyanoacrylates such as methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4 -Di-tert-butylphenyl) -s-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-s-triazine, 2- (2-hydroxy-4-propoxy-5-methylphenyl) ) -4,6-bis (2,4-ditertiarybutylphenyl) -s-triazine and the like, and triaryltriazines, and 0.001 to 30 parts by mass relative to 100 parts by mass of the synthetic resin. Preferably, 0.05 to 10 parts by mass are used.

  Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2, 6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-tetramethyl-4-piperidyl) Sebacate, bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4 -Butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2, 6,6-tetramethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) di (Tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,4,4-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditertiary Butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2, 2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl- 4-piperidylamino) Xanthane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,6 , 6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis ( N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8-12-tetraazadodecane, 1,6 , 11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] aminoundecane, 1,6 , 11-tris [2,4-bis (N-butyl-N- (1,2,2 And hindered amine compounds such as 6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] aminoundecane, and 0.001 to 30 parts by mass, more preferably 100 parts by mass of synthetic resin. 0.05 to 10 parts by mass is used.

  The synthetic resin composition containing the above-mentioned piperidyl group-containing polymer may further comprise a nucleating agent such as p-tert-butylaluminum benzoate, aromatic phosphate metal salt, dibenzylidene sorbitols, Inhibitor, metal soap, hydrotalcite, triazine ring-containing compound, metal hydroxide, phosphate flame retardant, other inorganic phosphorus, halogen flame retardant, silicon flame retardant, filler, pigment, lubricant, anti-aggregation agent, A foaming agent or the like may be added.

  The piperidyl group-containing polymer of the present invention can be expected to be used as a battery electrode material. For example, in a secondary battery having a positive electrode, a negative electrode, and an electrolyte as constituents, a secondary battery having a high capacity and stable in a charge / discharge cycle can be obtained by incorporating the polymer of the present invention in at least one of the positive electrode and the negative electrode. I can expect it. Furthermore, in a secondary battery using a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte, it can be expected that heat or ignition due to overcharging can be prevented by including the polymer of the present invention in the electrode or separator. The amount of the piperidyl group-containing polymer of the present invention added to the battery material is 0.01% by mass to 20% by mass with respect to the positive electrode (if necessary, the negative electrode, separator, etc.), preferably It is 0.05 mass%-10 mass%. When the amount is less than 0.01% by mass, the effect of improving battery characteristics is small. When the amount exceeds 20% by mass, the charge / discharge characteristics of the battery may be insufficient.

  EXAMPLES Hereinafter, although a synthesis example and an Example demonstrate this invention concretely, this invention is not restrict | limited by a following example.

(Synthesis Example 1) Synthesis of acetylene monomer

    Li acetylide was added to the 2,2,6,6-tetramethyl-4-piperidone (TAA) under the conditions of 45 ° C. and 4.5 hours, and the precipitate deposited after decomposition with water was washed with filtered water to obtain ETA. It was. ETA was dehydrated with phosphorus oxychloride (1 hour, refluxed) to obtain dehydrated intermediate EEA. EEA was quantitatively reacted with m-CPBA (3-chloroperbenzoic acid) in a short time (5 ° C., 0.5 hour), and EENO was obtained as a dark red liquid.

Synthesis Example 2 Synthesis of propargyl ether monomer

    4-Hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy (TMPNO) was reacted with NaH in tetrahydrofuran to obtain the above TMPNO-Na. Further, propargyl bromide was reacted, and after the reaction, ethyl acetate was added and washed with saturated brine to obtain PGNO. Further, it was washed with saturated saline 6 times and recrystallized from hexane to obtain a high purity product.

    Synthesis Example 3 Synthesis of hydroxyacetylene monomer

    ETA was oxidized with m-CPBA at 5 ° C. for 1 hour to obtain acetylene monomer ETNO in high yield.

(Example 1) Polymerization of acetylene monomer

In a four-necked flask equipped with a stirrer, 195 mg (1.1 mmol) of palladium chloride was added and dried under reduced pressure by heating. 9.8 g (55 mmol) of acetylene monomer (EENO) obtained in Synthesis Example 1 and N, N-dimethylacetamide were obtained. (DMAc) 80 ml is added, and it is made to react at 55 degreeC under nitrogen atmosphere for 130 hours after deaeration under reduced pressure. 3 ml of methanol is added, and the reaction solution is gradually added dropwise to 800 ml of a diethyl ether / hexane 1: 2 mixture with stirring to precipitate a polymer. After filtration, the precipitate was dried under reduced pressure to obtain 8.31 g (46.8 mmol) of a brown polymer. (Yield 85.1%)
The following analysis confirmed that it was the target polymer.

IR (cm ⁻¹ ): 2777, 2933 (methyl), 1647 (conjugated olefin), 1361 (N-oxyl)
Electronic spectrum (THF, nm): 300 to 600 (conjugated olefin)
Number average molecular weight (THF, PS conversion): 950
NO radical equivalent: NO radical equivalent is 181.3 as measured by high-sensitivity magnetic susceptibility measurement using a SQUID element.

(Example 2) Piperidyl group-containing copolymer In the same manner as in Example 1, 6.2 g (35 mmol) of the acetylene monomer (EENO) and 0.23 g (1.8 mmol) of 1,4-diethynylbenzene were charged. The reaction was carried out at 60 ° C. for 87 hours. Post-treatment gave 3.3 g (19.1 mmol) of brown polymer. (Yield 51.4%)

The following analysis confirmed that it was the desired copolymer.
IR (cm ⁻¹ ):
2777, 2933 (methyl), 1635 (conjugated olefin), 1361 (N-oxyl)
Electronic spectrum (THF, nm): 300 to 600 (conjugated olefin)
Number average molecular weight (THF, converted to PS): 1100
NO radical equivalent: NO radical equivalent is 189.6 by highly sensitive magnetic susceptibility measurement by SQUID element.

    Example 3 Polymerization of Hydroxyacetylene Monomer

    In the same manner as in Example 1, 10.8 g (55 mmol) of hydroxyacetylene monomer (ETNO) obtained in Synthesis Example 3 above was used instead of acetylene monomer (EENO), and reacted at 60 ° C. for 130 hours. 0.7 g (3.7 mmol) of polymer was obtained. (Yield 6.8%)

The following analysis confirmed that it was the target polyacetylene.
IR (cm ⁻¹ ):
2975, 2935 (methyl), 1624 (conjugated olefin), 1363 (N-oxyl)
Electronic spectrum (THF, nm): 300 to 600 (conjugated olefin)
Number average molecular weight (THF, PS conversion): 900
NO radical equivalent: NO radical equivalent is 201.3 by highly sensitive magnetic susceptibility measurement by SQUID element.

Example 4 Polymerization of propargyl ether monomer

    In the same manner as in Example 1, 7.7 g (37 mmol) of propargyl ether monomer (PGNO) obtained in Synthesis Example 2 was charged instead of EENO and reacted at 63 ° C. for 16 hours. (2.8 mmol) was obtained. (Yield 74.4%)

The following analysis confirmed that it was the target polyacetylene.
IR (cm ⁻¹ ):
2974, 2937 (methyl), 1713, 1674 (conjugated olefin), 1362 (N-oxyl), 1083 (ether)
Electronic spectrum (THF, nm): 300 to 600 (conjugated olefin)
Number average molecular weight (THF, converted to PS): 1660
NO radical equivalent: NO radical equivalent is 208.2 by highly sensitive magnetic susceptibility measurement by SQUID element.

(Example 5) Polymerization of acetylene monomer In the same manner as in Example 1, a polymerization liquid was prepared and reacted at 80 ° C for 24 hours. The post-treatment gave 47.2 g of brown polymer. (Yield 85.8%)

According to the following analysis, a polyacetylene polymer having an increased molecular weight was obtained, but in high temperature polymerization, radical decomposition was observed during the polymerization. IR (cm ⁻¹ ):
2975, 2935 (methyl), 1624 (conjugated olefin), 1363 (N-oxyl)
Electronic spectrum (THF, nm): 300 to 600 (conjugated olefin)
Number average molecular weight (THF, PS conversion): 1220
NO radical equivalent: NO radical equivalent is 494.8 by highly sensitive magnetic susceptibility measurement with SQUID element.

(Example 6) Polymerization of carbamoyloxy group-containing acetylene monomer

  Add 0.5 equivalents of diethylhydroxylamine (DEHA) to acetylene monomer EENO at room temperature in ethyl acetate solvent and stir for 0.5 hours to reduce to hydroxylamine form (EENOH) and 1.1 equivalents of nOH without isolation. -Butyl isocyanate (BuNCO) was added dropwise and reacted at room temperature for 1 hour and recrystallized from hexane to obtain an acetylene monomer EEBC. (Yield 74.1%, purity 96.0%).

In the same manner as in Example 1, 15.3 g (55 mmol) of EEBC was charged instead of EENO and reacted at 60 ° C. for 130 hours. After treatment, 11.8 g (3.7 mmol) of a brown polymer was obtained. (Yield 76.8%)
The following analysis confirmed that it was the target polyacetylene.
IR (cm ⁻¹ ):
3387 (NH), 2964, 2933, 2874 (methyl, methylene), 1726, 1500 (carbamate), 1637 (conjugated olefin), 1363 (N-oxyl)
Electronic spectrum (THF, nm): 300 to 600 (conjugated olefin)
Number average molecular weight (THF, PS conversion): 1100

(Comparative Example 1)
In the same manner as in Example 1, 436 mg (1.1 mmol) of tungsten (VI) chloride was used in place of palladium chloride and reacted at 80 ° C. for 24 hours, and 1.7 g of a brown polymer was obtained by post-treatment. (Yield 17.0%)
Polyacetylene was obtained by the following analysis, but radicals almost disappeared during polymerization.
IR (cm ⁻¹ ):
2975, 2935 (methyl), 1624 (conjugated olefin)
Electronic spectrum (THF, nm): 300 to 600 (conjugated olefin)
Number average molecular weight (THF, PS conversion): 740
Radical equivalent: 3360

(Comparative Example 2)
In the same manner as in Example 1, titanium tetrachloride-triethylaluminum (0.4M) benzene solution 2.75 ml (1.1 mmol) was used instead of palladium chloride, and toluene was used instead of DMAc for 5 hours at 25 ° C. However, no polymer was obtained.

(Evaluation Example 1) Comparison of NO radical equivalents The results of NO radical equivalents of the polymers or copolymers obtained in Examples 1 to 5, Comparative Example 1 and Comparative Example 2 are shown in Table 1 below.

From the results shown in Table 1, the piperidyl group-containing polymer or copolymer produced by the production method of the present invention has a high NO radical content and is effective as a light stabilizer that imparts weather resistance when added to a synthetic resin or the like. It was confirmed that there was. Specifically, Compound No. When the evaluation example 1-1 in which the polymer represented by 1 was synthesized and the evaluation comparative example 1-2 were compared, the NO radical content of the polymer of the present invention was about 18 compared with the polymer of the evaluation comparative example. It was confirmed that NO radicals were contained more than twice. Further, comparing Evaluation Example 1-5 and Evaluation Comparative Example 1-1 in which the polymerization reaction temperature and the reaction time are the same, the polymer of the present invention contains about 6 times or more of NO radicals. I was able to confirm.
Moreover, from the result of the said Table 1, it has also confirmed that temperature was preferable in the range of 40-70 degreeC as polymerization reaction conditions, and the solvent was preferable N, N- dimethylacetamide (DMAc).

(Evaluation Example 2) Redox Performance Test Redox performance was evaluated by cyclic voltammogram (CV) measurement of PEENO obtained in Example 1 above. A reversible wave as shown in FIG. 1 was obtained.
(DMF: 5.6 mM, TBAP salt, 50 mV / sec, reference electrode Ag / Ag ⁺ , E _1/2 )
Further, as shown in FIG. 2, the 10 times and 20 times scans in the 20 times repetition cycle (200 mV / sec) coincided, and the repetition characteristics were also good.
Table 1 shows the measurement results of the oxidation-reduction potential.

From the results of Table 2 above, PEENO having a double bond conjugated with the polyacetylene main chain in the ring and having high planarity exhibits a unique oxidation-reduction behavior, a high oxidation-reduction potential (E _1/2 ), and between peaks. It was confirmed that the current value of was high. From this, it can be expected that the polymer of the present invention has excellent performance when used as a battery electrode material.

FIG. 1 shows a reversible wave by cyclic voltammogram (CV) measurement measured in Evaluation Example 2-1. FIG. 2 shows the results of scanning 10 to 20 times in 20 repetition cycles (200 mV / sec) measured in Evaluation Example 2.

Claims (5)

A compound selected from at least one of the compounds represented by the following general formula (1), general formula (2) or general formula (3) is polymerized with a catalyst consisting only of a palladium salt. The manufacturing method of the piperidyl group containing polymer or piperidyl group containing copolymer containing the structural unit represented by General formula (4) or General formula (5).
(Wherein R or R ₁ each independently represents an oxygen free radical or a carbamoyloxy group, R ₂ represents a hydrogen atom or a hydroxyl group, X represents a direct bond or an oxygen atom, Y represents a direct bond or methylene) And n and m each represent a number of 1 to 100.) The catalyst consisting only of the palladium salt is selected from any of palladium chloride, palladium bromide, bis (acetylacetonato) palladium, trans-dichlorobis (triphenylphosphine) palladium, dinitrodiamminepalladium (II), and palladium (II) acetate. The manufacturing method of the piperidyl group containing polymer or piperidyl group containing copolymer of Claim 1.   The method for producing a piperidyl group-containing polymer or piperidyl group-containing copolymer according to claim 1 or 2, wherein the solvent used in the polymerization reaction is N, N-dimethylacetamide.   The method for producing a piperidyl group-containing polymer or a piperidyl group-containing copolymer according to any one of claims 1 to 3, wherein a temperature condition of the polymerization reaction is in a range of 40 to 70 ° C. Following general formula (4) containing a constitutional unit represented by the piperidyl group-containing polymer or piperidyl group-containing copolymer.
(In the formula, R represents an oxygen free group or a carbamoyloxy group, and n represents a number of 1 to 100.)