JP2006016428A - Piperidyl group-containing high-molecular-weight polymer or copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer or a copolymer having high-molecular-weight piperidyl group in which the molecular weight and molecular weight distribution are controlled. <P>SOLUTION: The piperidyl group-containing high-molecular-weight polymer or copolymer is composed of a unit represented by general formula (I) and has ≥30,000 number-average molecular weight. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to high molecular weight polymers and copolymers having piperidyl groups, and methods for producing the polymers and copolymers. The polymer and the copolymer are useful as a resin weather resistance improver, a polymerization inhibitor and the like.

  Polymers having piperidyl groups, particularly nitroxide radicals, are known as polymers that are stable under various conditions, and are used as resin weather resistance improvers and the like. Non-Patent Document 1 and Patent Document 1 include a polymer having a nitroxide radical produced using a radical polymerization reaction, and Non-Patent Document 2 includes a polymer having a nitroxide radical produced using an anionic polymerization reaction. Each is listed.

  However, it is difficult to control the molecular weight and molecular weight distribution by the radical polymerization method, and the conventional anionic polymerization method has a problem that the yield is low and a high molecular weight polymer cannot be obtained. It was.

Polym. J. et al. , 14 (5), 363 (1982) J. et al. Polym. Sci. , Polym. Chem. Ed. , 10, 3295 (1972) JP 2002-313344 A

  Accordingly, an object of the present invention is to provide a polymer or copolymer having a high molecular weight piperidyl group with a controlled molecular weight and molecular weight distribution, and a method for producing the same.

  As a result of intensive studies in order to solve the above-mentioned problems, the present inventors have found that a specific piperidyl group-containing polymer can achieve the above object, and have completed the present invention.

  That is, the present invention relates to a piperidyl group-containing high molecular weight polymer or copolymer having a number average molecular weight of 30,000 or more, which is composed of structural units represented by the following general formula (I), and the piperidyl produced by an anionic polymerization reaction. The present invention provides a method for producing a group-containing high molecular weight polymer or copolymer.

  According to the present invention, it is possible to provide a high molecular weight piperidyl group-containing polymer or copolymer that is hardly soluble or insoluble in a solvent such as THF.

  Hereinafter, the piperidyl group-containing high molecular weight polymer and the piperidyl group-containing high molecular weight copolymer of the present invention will be described in detail based on preferred embodiments.

  In the general formula (I), the alkyl group having 1 to 10 carbon atoms represented by R includes methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, sec-butyl, isobutyl, amyl, isoamyl, Triamyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, Nonyl, isononyl, decyl and the like are mentioned, and examples of the alkoxy group having 1 to 10 carbon atoms represented by R include methyloxy, ethyloxy, propyloxy, isopropyloxy, butyloxy, sec-butyloxy, tert-butyloxy, isobutyloxy , Amyloxy, isoamyloxy, tertiary amylo Shi, hexyloxy, cyclohexyloxy, heptyloxy, iso heptyloxy, tert-heptyloxy, n- octyloxy, iso-octyloxy, tert-octyloxy, 2-ethylhexyl-oxy and the like.

  In the piperidyl group-containing high molecular weight polymer or copolymer of the present invention, when the number of the structural units is m, at least two groups represented by X in the general formula (I) are the above general formula (II). And the remaining (m−2) pieces are Li. m is a number that gives a number average molecular weight of 30,000 or more, preferably 150 to 5,000. The number of Li is preferably 0 to 1000.

  As preferred specific examples of the piperidyl group-containing high molecular weight polymer or copolymer of the present invention composed of the structural unit represented by the general formula (I), the following compound No. 1-No. 5 is mentioned.

  The molecular weight of the piperidyl group-containing high molecular weight polymer or copolymer of the present invention has a number average molecular weight of 30,000 or more, preferably 40,000 to 1,000,000, more preferably 60,000 to 500, 000. In addition, this number average molecular weight shows the molecular weight converted into standard polystyrene by gel permeation chromatography.

  The piperidyl group-containing high molecular weight polymer or copolymer of the present invention is obtained by further copolymerizing a polymer or copolymer composed of the structural unit represented by the general formula (I) with a copolymerizable crosslinking agent. It is also possible to adopt a crosslinked structure.

  Examples of the copolymerizable crosslinking agent include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, glycerin di (meth) acrylate, tetraethylene glycol di (meth) acrylate, ethylene di (meth) acrylate, 2,4 -Di (meth) acrylate compounds such as pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycidyl di (meth) acrylate and bisphenol A di (meth) acrylate; N, N'-methylenebis Bis (meth) acrylamide compounds such as acrylamide; divinyl compounds such as divinylbenzene, divinyltoluene, butadiene, 1,4-pentadiene, 1,5-hexadiene, and the like. Among these, di (meth) acrylate compounds It is preferred.

  The copolymerizable crosslinking agent is usually 0 to the total amount of the portion composed of the structural unit represented by the general formula (I) in the piperidyl group-containing high molecular weight polymer or copolymer of the present invention. It can be used in the range of 10% by weight, preferably 0 to 5% by weight.

  The piperidyl group-containing high molecular weight polymer or copolymer of the present invention includes those that are insoluble in tetrahydrofuran (THF) solvent. The factors include high degree of polymerization and steric rules of the polymer main chain. High crystallinity and high molecular weight by copolymerization with a crosslinking agent.

  The piperidyl group-containing high molecular weight polymer or copolymer of the present invention can be produced by anionic polymerization reaction of a monomer compound.

  The polymerization initiator that can be used in the anionic polymerization reaction can be selected from the usual initiators for anionic polymerization, such as alkali metals such as lithium, sodium, potassium, cesium; alkylated products of the alkali metals, Organic alkali metals such as allylates, arylates, etc .; Alkaliates of alkali metal earths, organic alkaline earth metals such as allylates, arylates; organoaluminums; Grignard reagents; sodium amides; metal hydroxides; Can be mentioned. These polymerization initiators can be used alone or in admixture of two or more, and a Grignard reagent is particularly preferably used. The polymerization initiator is preferably used in a proportion of 0.01 to 0.5 mol with respect to 1 mol of the monomer compound.

  Examples of the organic alkali metal include ethyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium, ethyl sodium, n-butyl sodium, lithium biphenyl, lithium naphthalene, lithium triphenyl, sodium naphthalene, potassium naphthalene, α -Methylstyrene sodium dianion, 1,1-diphenylhexyl lithium, 1,1-diphenyl-3-methylpentyl lithium, 1,4-dilithio-2-butene, 1,6-dilithiohexane, polystyryl lithium, cumyl potassium, Cumyl cesium, diphenylmethyl sodium, diphenylmethyl potassium, diphenylmethyl lithium, 1,1-diphenylhexyl lithium, 1,1-diphenyl-3-methylpentyl lithium, etc. Kill.

  Examples of the organic alkaline earth metal include n-butyl magnesium, n-hexyl magnesium, ethoxy calcium, calcium stearate, t-butoxy strontium, ethoxy barium, isopropoxy barium, ethyl mercapto barium, t-butoxy barium, phenoxy barium, diethylamino Examples include barium, barium stearate, ketyl barium, and the like.

  Examples of the organic aluminum include trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, and the like; dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride, methyl Alkyl aluminum chlorides such as aluminum dichloride, ethyl aluminum dichloride, propyl aluminum dichloride, isobutyl aluminum dichloride, hexyl aluminum dichloride; dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, diisobutyl aluminum hydride, dihexyl Alkyl aluminum hydrides such as luminium hydride; methyl bis (2,6-di-t-butylphenoxy) aluminum, ethyl bis (2,6-di-t-butylphenoxy) aluminum, isobutyl bis (2,6-di-t-butyl) And alkyl aluminum alkoxides such as (-4-methylphenoxy) aluminum.

  The Grignard reagent is generally a compound represented by the following general formula (III), and preferred specific examples include t-butylmagnesium chloride, t-butylmagnesium bromide, and phenylmagnesium bromide.

  The polymerization solvent that can be used in the anionic polymerization reaction is not particularly limited as long as it is a solvent that does not participate in the polymerization reaction and is compatible with the polymer or copolymer. Specifically, diethyl ether, tetrahydrofuran Ether solvents such as benzene, dioxane and trioxane; saturated hydrocarbon solvents such as pentane, cyclopentane, n-hexane, cyclohexane, methylcyclohexaneheptane, octane, decane and dodecane; aromatic carbonization such as toluene, benzene, xylene and ethylbenzene Hydrogenated solvents: Halogenated hydrocarbon solvents such as chloroform can be exemplified, and tetrahydrofuran and toluene are particularly preferred. These solvents can be used alone or as a mixed solvent of two or more. When these solvents are used, the amount used can be appropriately adjusted according to the type of polymerization initiator used, the molecular weight of the target polymer or copolymer, the type of solvent, etc. In general, it is preferable to use a solvent within a range of 200 to 3000 parts by weight with respect to 100 parts by weight of the total amount of monomer compounds from the viewpoint of progress and the like.

  In the anionic polymerization reaction, it is desirable to prevent water from being mixed into the reaction system as much as possible. Therefore, it is preferable to use a chemical substance supplied to the system such as a monomer compound and other arbitrary chemical substances (for example, an organic solvent) that does not contain water as much as possible. Deaeration and dehydration can be performed in advance. The reaction is preferably performed in an atmosphere of an inert gas such as nitrogen, argon or helium.

  Furthermore, the anionic polymerization reaction is preferably performed under sufficient stirring conditions, for example, so that the reaction conditions in the reaction system become uniform.

  In the above anionic polymerization reaction, the temperature of the reaction system is not particularly limited, and a suitable temperature condition may be appropriately selected according to the type of polymerization initiator, the type of monomer compound, etc. Is preferable, and -20 ° C to 20 ° C is more preferable. Usually, the time required for the reaction is in the range of 10 seconds to 72 hours.

  The piperidyl group-containing high molecular weight polymer or copolymer of the present invention is a light resistance imparting agent, an aqueous coating material, and a resin weather resistance improving agent used for heat sensitive recording materials, pressure sensitive recording materials, ink jet recording materials, thermal transfer sheet recording materials and the like. In addition, it can be used for various uses such as a polymerization inhibitor and an oxidation catalyst, and the use is not particularly limited.

  Further, when the piperidyl group-containing high molecular weight polymer or copolymer of the present invention is used, a hindered amine light stabilizer (HALS), an ultraviolet absorber, a phosphorus-based, phenol-based, or sulfur-based antioxidant is optionally used. , Nucleating agent, flame retardant, metal soap, processing aid, filler, dispersant, emulsifier, lubricant, coloring dye, coloring pigment, antistatic agent, antiseptic, antibacterial agent, antifungal agent, plasticizer, antifoam Well-known and commonly used additives such as an agent, a viscosity modifier, a leveling agent, a surfactant, a fluorescent brightener, a pH adjuster, a thickener, an aggregation inhibitor, and a fragrance can be used in combination.

  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-pentamethyl-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) bis (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) bis (Tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-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 / dibromoethane polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro- -Morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 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-triazine-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-triazine -6-ylamino] undecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino-s-triazine- 6-ylamino] undecane, 3,9-bis [1,1-dimethyl-2- [tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy] ethyl] -2, 4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2- [tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl] Oxy) butylcarbonyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane and the like.

  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 such as 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5 -Dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-th Octyl-6-benzotriazolylphenol), polyethylene glycol ester of 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole, 2- [2-hydroxy-3- (2-acryloyloxy) Ethyl) -5-methylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] benzotriazole, 2- [2-hydroxy-3- (2- Methacryloyloxyethyl) -5-tert-octylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] -5-chlorobenzotriazole, 2- [2 -Hydroxy-5- (2-methacryloyloxyethyl) phenyl] benzene Zotriazole, 2- [2-hydroxy-3-tert-butyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-amyl-5- (2-methacryloyloxy) Ethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-butyl-5- (3-methacryloyloxypropyl) phenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-4- (2- Methacryloyloxymethyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxypropyl) 2- (2-hydroxypheny) such as phenyl] benzotriazole B) benzotriazoles; 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6 -Diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [ 2-hydroxy-4- (3-C12-13 mixed alkoxy-2-hydroxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2- Hydroxy-4- (2-acryloyloxyethoxy) phenyl] -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxy-3-allylphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4,6-tris (2-hydroxy-3-methyl-4-hexyloxyphenyl) -1,3 2- (2-hydroxyphenyl) -4,6-diaryl-1,3,5-triazines such as 5-triazine; phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-3,5- Di-tert-butyl-4-hydroxybenzoate, octyl (3,5-di-tert-butyl-4-hydroxy) benzoate, dodecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, tetradecyl (3,5- Ditert-butyl-4-hydroxy) benzoate, hexadecyl (3,5-ditert-butyl-4-hydroxy) benzoate, octadecyl (3,5-ditert Benzoates such as butyl-4-hydroxy) benzoate, behenyl (3,5-ditert-butyl-4-hydroxy) benzoate; 2-ethyl-2′-ethoxyoxanilide, 2-ethoxy-4′-dodecyloxy Substituted oxanilides such as zanilides; cyanoacrylates such as ethyl-α-cyano-β, β-diphenyl acrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; various metal salts Alternatively, metal chelates, particularly nickel or chromium salts or chelates may be mentioned.

  Examples of the phosphorus antioxidant include triphenyl phosphite, tris (2,4-ditertiarybutylphenyl) phosphite, tris (2,5-ditertiarybutylphenyl) phosphite, and tris (nonylphenyl). ) Phosphite, tris (dinonylphenyl) phosphite, tris (mono, dimixed nonylphenyl) phosphite, diphenyl acid phosphite, 2,2'-methylenebis (4,6-ditert-butylphenyl) octyl phosphite , Diphenyldecyl phosphite, diphenyloctyl phosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite , Dibutyl acid phosphite, dilauryl acid phosphite, trilauryl trithiophosphite, bis (neopentylglycol) 1,4-cyclohexanedimethyldiphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol di Phosphite, bis (2,5-ditert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-dic (Milphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tetra (C12-15 mixed alkyl) -4,4'-isopropylidene diphenylphosphite, bis [2,2'-methylenebis (4,6- Diamylphenyl)], isop Pyridene diphenyl phosphite, tetratridecyl 4,4'-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) 1,1,3-tris (2-methyl-5-tert Tributyl-4-hydroxyphenyl) butane triphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, tris (2-[(2,4,7,9-tetrakis tert-butyldibenzo [ d, f] [1,3,2] dioxaphosphin-6-yl) oxy] ethyl) amine, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2 -Butyl-2-ethylpropanediol, 2,4,6-tritert-butylphenol monophosphite and the like.

  Examples of the phenol-based antioxidant include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-4- Hydroxyphenyl) propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, tridecyl 3,5-ditert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-tert-butyl) -4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3-bi (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4′-butylidenebis (2,6-ditert-butylphenol), 4,4′-butylidenebis (6-tert-butyl- 3-methylphenol), 2,2′-ethylidenebis (4,6-ditert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy -4-tert-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, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] Isocyanurate, tetrakis [methylene-3- (3 ′, 5′-ditert-butyl-4′-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acroyloxy- 3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [2- (3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl] -2 , 4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] And the like.

  Examples of the sulfur antioxidant include dialkyl thiodipropionates such as dilauryl, dimyristyl, myristyl stearyl, and distearyl esters of thiodipropionic acid, and polyols such as pentaerythritol tetra (β-dodecyl mercaptopropionate). [Beta] -alkyl mercaptopropionic acid esters.

EXAMPLES Hereinafter, although an Example etc. are given and this invention is demonstrated further in detail, this invention is not limited to these Examples etc.
Examples 1-3 show the Example of the polymer of this invention comprised from 1 type of the structural unit represented by the said general formula (I), Examples 4-6 are 2 types of the said structural unit. Examples of the copolymer of the present invention composed of the following: Examples 7 to 8 are examples of the copolymer of the present invention (crosslinked polymer) composed of one of the above structural units and a copolymerizable crosslinking agent. An example is shown. Comparative Example 1 is an example of a low molecular weight polymer that is composed of the same structural units as in Example 1 but has a number average molecular weight of 30000 or less. In each of Evaluation Examples 1 and 2, performance evaluation as a resin weather resistance improver and a polymerization inhibitor was performed for the polymer or copolymer of the present invention and the comparative compound.

Example 1 Compound no. Synthesis of 1
In a nitrogen atmosphere, 102.1 g (0.425 mol) of 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl (TMA) was charged, and 584 ml of dry toluene was added and dissolved. Cooled to ° C. While vigorously stirring at −7 to −3 ° C., 10.7 ml (0.021 mol) of t-butylmagnesium chloride THF solution (2M) was gradually added dropwise and stirred for 5 hours. Then, stirring was stopped and it was left to stand at room temperature for 10 hours. After adding 440 ml of N, N-dimethylformamide and stirring at 80 to 90 ° C. for 15 minutes and cooling to 40 ° C., the obtained slurry was gradually stirred into a mixed solution of 7800 ml of methanol, 160 ml of water and 30 ml of acetic acid while stirring vigorously. It was dripped. The precipitated solid was filtered off and dried under reduced pressure at 120 ° C. to obtain 16.3 g (yield 16%) of orange powder. The number average molecular weight was 57,000.

About the obtained powder, IR measurement was performed and it confirmed that it was the target object. Further, the NO radical equivalent was measured by an electron spin resonance (ESR) method. The measurement results are shown below.
IR (cm ⁻¹ ):
2975, 2938, 1726, 1465, 1363, 1240, 1175, 1147, 1006, 983, 965, 754
NO radical equivalent: 241.5

Example 2 Compound No. Synthesis of 1 2
Under a nitrogen atmosphere, 102.1 g (0.425 mol) of TMA was charged, 584 ml of dry toluene was added and dissolved, and the mixture was cooled to -5 ° C. While vigorously stirring at −7 to −3 ° C., 7.1 ml (0.021 mol) of phenylmagnesium bromide ether solution (3M) was gradually added dropwise and stirred for 5 hours. Then, stirring was stopped and it was left to stand at room temperature for 10 hours. After adding 440 ml of N, N-dimethylformamide and stirring at 80 to 90 ° C. for 15 minutes and cooling to 40 ° C., the obtained slurry was gradually stirred into a mixed solution of 7800 ml of methanol, 160 ml of water and 30 ml of acetic acid while stirring vigorously. It was dripped. The precipitated solid was separated by filtration and dried under reduced pressure at 120 ° C. to obtain 63.7 g (yield 62%) of an orange powder. Since the obtained powder was insoluble in THF solvent, the number average molecular weight could not be measured, but the number average molecular weight was more than 57,000.

About the obtained powder, IR measurement was performed and it confirmed that it was the target object. Further, the NO radical equivalent was measured by an electron spin resonance (ESR) method. The measurement results are shown below.
IR (cm ⁻¹ ):
2976, 2939, 1726, 1465, 1363, 1240, 1178, 1147, 1008, 965, 937, 754
NO radical equivalent: 240.8

Example 3 Compound no. Synthesis of 2 In a nitrogen atmosphere, 96.2 g (0.425 mol) of 4-acryloyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl (TA) was charged, and 584 ml of dry toluene was added and dissolved. , Cooled to -5 ° C. While vigorously stirring at −7 to −3 ° C., 7.1 ml (0.021 mol) of phenylmagnesium bromide ether solution (3M) was gradually added dropwise and stirred for 5 hours. Then, stirring was stopped and it was left to stand at room temperature for 10 hours. After adding 440 ml of N, N-dimethylformamide and stirring at 80 to 90 ° C. for 15 minutes and cooling to 40 ° C., the obtained slurry was gradually stirred into a mixed solution of 7800 ml of methanol, 160 ml of water and 30 ml of acetic acid while stirring vigorously. It was dripped. The precipitated solid was separated by filtration and dried under reduced pressure at 120 ° C. to obtain 39.4 g (yield 41%) of an orange powder. Since the obtained powder was insoluble in THF solvent, the number average molecular weight could not be measured, but the number average molecular weight was more than 57,000.

About the obtained powder, IR measurement was performed and it confirmed that it was the target object. Further, the NO radical equivalent was measured by an electron spin resonance (ESR) method. The measurement results are shown below.
IR (cm ⁻¹ ):
2976, 2937, 1728, 1464, 1364, 1233, 1167, 1009, 983, 959, 752
NO radical equivalent: 228.6

Example 4 Compound no. Synthesis of 3
Under a nitrogen atmosphere, 40.9 g (0.170 mol) of TMA and 57.7 g (0.255 mol) of TA were charged and dissolved by adding 584 ml of dry toluene, and cooled to -5 ° C. While vigorously stirring at −7 to −3 ° C., 7.1 ml (0.021 mol) of phenylmagnesium bromide ether solution (3M) was gradually added dropwise and stirred for 5 hours. Then, stirring was stopped and it was left to stand at room temperature for 10 hours. After adding 440 ml of N, N-dimethylformamide and stirring at 80 to 90 ° C. for 15 minutes and cooling to 40 ° C., the obtained slurry was gradually stirred into a mixed solution of 7800 ml of methanol, 160 ml of water and 30 ml of acetic acid while stirring vigorously. It was dripped. The precipitated solid was filtered off and dried under reduced pressure at 120 ° C. to obtain 25.6 g (yield 26%) of an orange powder. Since the obtained powder was insoluble in THF solvent, the number average molecular weight could not be measured, but the number average molecular weight was more than 57,000.

About the obtained powder, IR measurement was performed and it confirmed that it was the target object. Further, the NO radical equivalent was measured by an electron spin resonance (ESR) method. The measurement results are shown below.
IR (cm ⁻¹ ):
2976, 2938, 1730, 1465, 1364, 1234, 1167, 1008, 962, 937, 754
NO radical equivalent: 233.1

Example 5 Compound no. Synthesis of 3
Under a nitrogen atmosphere, 97.0 g (0.404 mol) of TMA and 4.7 g (0.021 mol) of TA were charged, 584 ml of dry toluene was added and dissolved, and the mixture was cooled to -5 ° C. While vigorously stirring at −7 to −3 ° C., 7.1 ml (0.021 mol) of phenylmagnesium bromide ether solution (3M) was gradually added dropwise and stirred for 5 hours. Then, stirring was stopped and it was left to stand at room temperature for 10 hours. After adding 440 ml of N, N-dimethylformamide and stirring at 80 to 90 ° C. for 15 minutes and cooling to 40 ° C., the obtained slurry was gradually stirred into a mixed solution of 7800 ml of methanol, 160 ml of water and 30 ml of acetic acid while stirring vigorously. It was dripped. The precipitated solid was separated by filtration and dried under reduced pressure at 120 ° C. to obtain 61.0 g (yield 60%) of an orange powder. Since the obtained powder was insoluble in THF solvent, the number average molecular weight could not be measured, but the number average molecular weight was more than 57,000.

About the obtained powder, IR measurement was performed and it confirmed that it was the target object. Further, the NO radical equivalent was measured by an electron spin resonance (ESR) method. The measurement results are shown below.
IR (cm ⁻¹ ):
2976, 2938, 1730, 1465, 1363, 1234, 1167, 1009, 962, 937, 754
NO radical equivalent: 240.1

Example 6 Compound no. Synthesis of 4 Under a nitrogen atmosphere, 99.1 g (0.412 mol) of TMA and 4.7 g (0.030 mol) of trimethylsilyloxymethacrylate were charged, 584 ml of dry toluene was added and dissolved, and the mixture was cooled to -5 ° C. While vigorously stirring at −7 to −3 ° C., 7.1 ml (0.021 mol) of phenylmagnesium bromide ether solution (3M) was gradually added dropwise and stirred for 5 hours. Then, stirring was stopped and it was left to stand at room temperature for 10 hours. After adding 440 ml of N, N-dimethylformamide and stirring at 80 to 90 ° C. for 15 minutes and cooling to 40 ° C., the obtained slurry was gradually stirred into a mixed solution of 7800 ml of methanol, 160 ml of water and 30 ml of acetic acid while stirring vigorously. It was dripped. The precipitated solid was filtered off and dried under reduced pressure at 120 ° C. to obtain 73.1 g of an orange powder. The obtained solid was dissolved in 60 g of THF and added dropwise with good stirring to a mixture of 200 ml of methanol, 200 ml of water and 4 g of lithium hydroxide. Obtained. Since the obtained powder was insoluble in THF solvent, the number average molecular weight could not be measured, but the number average molecular weight was more than 57,000.

About the obtained powder, IR measurement was performed and it confirmed that it was the target object. Further, the NO radical equivalent was measured by an electron spin resonance (ESR) method. The measurement results are shown below.
IR (cm ⁻¹ ):
3426, 2976, 2938, 1726, 1597, 1465, 1363, 1240, 1178, 1148, 1007, 966, 937, 755
NO radical equivalent: 233.4

[Example 7] Synthesis of cross-linked polymer (copolymer of TMA and ethylene glycol dimethacrylate) 1
Under a nitrogen atmosphere, 97.4 g (0.405 mol) of TMA and 1.6 g (0.008 mol) of ethylene glycol dimethacrylate were charged and dissolved by adding 584 ml of dry toluene, and cooled to -5 ° C. While vigorously stirring at −7 to −3 ° C., 7.1 ml (0.021 mol) of phenylmagnesium bromide ether solution (3M) was gradually added dropwise and stirred for 5 hours. Then, stirring was stopped and it was left to stand at room temperature for 10 hours. After adding 440 ml of N, N-dimethylformamide and stirring at 80 to 90 ° C. for 15 minutes and cooling to 40 ° C., the obtained slurry was gradually stirred into a mixed solution of 7800 ml of methanol, 160 ml of water and 30 ml of acetic acid while stirring vigorously. It was dripped. The precipitated solid was collected by filtration and dried under reduced pressure at 120 ° C. to obtain 66.3 g (yield 67%) of an orange powder. Since the obtained powder was insoluble in THF solvent, the number average molecular weight could not be measured, but the number average molecular weight was more than 57,000.

About the obtained powder, IR measurement was performed and it confirmed that it was the target object. Further, the NO radical equivalent was measured by an electron spin resonance (ESR) method.
IR (cm ⁻¹ ):
2936, 2974, 1725, 1464, 1363, 1240, 1144, 1007, 966, 753
NO radical equivalent: 233.4

[Example 8] Synthesis of cross-linked polymer (copolymer of TMA and ethylene glycol dimethacrylate) 2
Under a nitrogen atmosphere, 97.4 g (0.405 mol) of TMA and 1.6 g (0.008 mol) of ethylene glycol dimethacrylate were charged and dissolved by adding 584 ml of dry toluene, and cooled to -20 ° C. While vigorously stirring at −10 ° C., 10.7 ml (0.021 mol) of t-butylmagnesium chloride ether solution (2M) was gradually added dropwise and stirred for 5 hours. Then, stirring was stopped and it was left to stand at room temperature for 10 hours. After adding 440 ml of N, N-dimethylformamide and stirring at 80 to 90 ° C. for 15 minutes and cooling to 40 ° C., the obtained slurry was gradually stirred into a mixed solution of 7800 ml of methanol, 160 ml of water and 30 ml of acetic acid while stirring vigorously. It was dripped. The precipitated solid was collected by filtration and dried under reduced pressure at 120 ° C. to obtain 66.3 g (yield 67%) of an orange powder. Since the obtained powder was insoluble in THF solvent, the number average molecular weight could not be measured, but the number average molecular weight was more than 57,000.

About the obtained powder, IR measurement was performed and it confirmed that it was the target object. Further, the NO radical equivalent was measured by an electron spin resonance (ESR) method.
IR (cm ⁻¹ ):
2938, 2975, 1725, 1465, 1363, 1240, 1147, 1006, 965, 754
NO radical equivalent: 242.5

[Comparative Example 1] Compound No. 1 Synthesis of low molecular weight compound composed of the same structural unit as 1 Under a nitrogen atmosphere, 95.6 g (0.425 mol) of 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine was charged, and 300 ml of THF was added. After dissolution, 1.38 g of azoisobutyronitrile was added and stirred at 80 ° C. for 5 hours. After cooling to room temperature, the reaction mixture was gradually added dropwise to 3.8 l of n-hexane with vigorous stirring and stirred for 30 minutes. The precipitated solid was filtered off to obtain 81.3 g of a white solid. The obtained solid was dissolved in 250 ml of dichloromethane, cooled to 5 ° C., 170 g (0.638 mol) of m-chloroperbenzoic acid (purity 65%) was added, and the mixture was stirred for 1 hour. The precipitated solid was separated by filtration, and the organic layer was washed 3 times with 50 ml of 5% aqueous sodium carbonate solution, further washed with water, and dried over sodium sulfate. The solvent was distilled off and dried under reduced pressure at room temperature to obtain 77.0 g of orange powder (yield 76%). The number average molecular weight was 18,000.

About the obtained powder, IR measurement was performed and it confirmed that it was the target object. Further, the NO radical equivalent was measured by an electron spin resonance (ESR) method.
IR (cm ⁻¹ ):
2976, 2939, 1726, 1465, 1363, 1240, 1178, 1147, 1008, 965, 937, 754
NO radical equivalent: 343.0

[Evaluation Examples 1-1 to 1-5 and Comparative Evaluation Examples 1-1 to 1-2]
Tolylene diisocyanate (148 g) was added to 850 g of polypropylene glycol having an average molecular weight of 3000 and stirred for 12 hours at 80 ° C. to obtain a urethane prepolymer containing 3.6% by weight of isocyanate groups. 100 parts by weight of the obtained urethane prepolymer, 15 parts by weight of polypropylene glycol, 10 parts by weight of 4,4′-methylenebis (2-chloroaniline), 58.4 parts by weight of calcium carbonate, 15 parts by weight of dioctyl phthalate, lead octylate 0.8 parts by weight and a piperidyl group-containing polymer or copolymer (described in Table 1) are added and kneaded, and the surface of the kneaded product is placed in a container of 20 mm (w) × 100 mm (l) × 10 mm (d). The product was filled so as to be smooth and cured at room temperature for 3 days to obtain a cured product. The obtained cured product was used as a test piece, and the test piece was exposed with a sunshine weatherometer (manufactured by Suga Test Instruments Co., Ltd.) at 63 ° C. under conditions of repeating a cycle of 2 hours without rain and 18 minutes with rain, The color difference (ΔE) after 100 hours and 500 hours from the start of exposure was measured to evaluate the weather resistance. The color difference was measured according to JIS-K7105, based on that before ultraviolet irradiation, and was determined by Hunter's color difference formula. The results are shown in Table 1.

[Evaluation Examples 2-1 to 2-6 and Comparative Evaluation Examples 2-1 to 2-2]
To 2-hydroxyethyl acrylate, compound No. 1 which is a piperidyl group-containing polymer or copolymer is added. 1, no. 3 or No. 4 (described in Table 2) was added in the addition amount shown in Table 2, placed in a glass tube, sealed, and then shaken at 100 ° C. for 3 hours (Evaluation Examples 2-1 to 2-5). About the contents of the glass tube after shaking, the amount of residual double bonds was calculated | required by IR analysis, and the decreasing rate was made into the polymerization rate. Moreover, the polymer was recovered by filtration from the contents of the glass tube after shaking in Evaluation Example 2-3, and the polymerization rate was determined by the same method as above using the recovered polymer (Evaluation Example 2). -6). These results are shown in Table 2.

  For comparison, the above polymer or copolymer was not added to 2-hydroxyethyl acrylate (Comparative Evaluation Example 2-1), Comparative compound 2,2,6,6-tetramethyl-4-hydroxypiperidine- The polymerization rate was determined in the same manner for the sample to which N-oxyl was added (Comparative Evaluation Example 2-2). The results are shown in Table 2.

The piperidyl group-containing polymer or copolymer of the present invention synthesized by an anionic polymerization reaction has lower solubility in a solvent and a high molecular weight than those synthesized by a conventional radical polymerization reaction (Examples 1 to 1). 8 and Comparative Example 1). As is apparent from the results in Table 1, when the piperidyl group-containing high molecular weight polymer or copolymer of the present invention was added to a synthetic resin, the conventional piperidyl group-containing low molecular weight polymer or copolymer was added. It was possible to impart superior weather resistance to the synthetic resin. Further, as is apparent from the results in Table 2, the piperidyl group-containing high molecular weight polymer or copolymer of the present invention can be confirmed to exhibit excellent performance when used as a polymerization inhibitor, and by filtration. It was also confirmed that it could be easily removed and recovered and reused.

Claims (6)

A piperidyl group-containing high molecular weight polymer or copolymer having a number average molecular weight of 30,000 or more, which is composed of structural units represented by the following general formula (I).

  The piperidyl group-containing high molecular weight polymer or copolymer according to claim 1, which has a number average molecular weight of 40,000 or more.   The piperidyl group-containing high molecular weight polymer or copolymer according to claim 1 or 2, wherein R in the general formula (II) is an oxygen free radical.   A piperidyl group-containing crosslinkable high molecular weight copolymer obtained by further copolymerizing a copolymerizable crosslinking agent with the piperidyl group-containing high molecular weight polymer or copolymer according to any one of claims 1 to 3.   The piperidyl group-containing crosslinkable high molecular weight copolymer according to claim 4, wherein the copolymerizable crosslinker is a di (meth) acrylate compound.   The manufacturing method of the piperidyl group containing high molecular weight polymer or copolymer in any one of Claims 1-5 by anionic polymerization reaction.