JP2018145354A - Process for producing modified halogenated polyolefin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a modified halogenated polyolefin composition having greatly improved oil resistance while maintaining the excellent heat resistance of the halogenated polyolefin. SOLUTION: When an unsaturated monomer containing acrylonitrile and an acrylic compound is grafted to a halogenated polyolefin dissolved in a solvent using a radical initiator, the graft reaction is carried out by the presence of an aldehyde amine compound. The method for producing a modified halogenated polyolefin composition, which is carried out below. [Selection diagram] None

Description

  The present invention relates to a method for producing a modified halogenated polyolefin composition. More specifically, the present invention relates to a halogenated polyolefin dissolved in a solvent, an unsaturated monomer containing acrylonitrile and an acrylic compound, and a radical initiator. The present invention relates to a method for producing a modified halogenated polyolefin composition, wherein the graft reaction is performed in the presence of an aldehyde amine compound when the graft reaction is performed.

  Halogenated polyolefin is a general term for chlorosulfonated polyethylene, chlorinated polyethylene, etc., and has excellent heat resistance, weather resistance, ozone resistance, chemical resistance and light color, so various hoses and hose cover materials , Wire covering materials, packing, gaskets, rolls and escalator handrails. In addition, since chlorosulfonated polyethylene and chlorinated polyethylene contain chlorine groups, they have better oil resistance than natural rubber, styrene / butadiene rubber, and general-purpose rubber such as ethylene / propylene rubber. It is often used for required hoses and tubes.

  As a method for improving the oil resistance of the halogenated polyolefin, it is known to increase the halogen content. However, when the oil resistance is improved by this method, the glass transition temperature of the obtained halogenated polyolefin is increased, and the room temperature is increased. There is a problem that the hardness in the vicinity increases and the characteristics as a rubber material are lost. Therefore, in various hose application fields, there is a limit to improvement in oil resistance by increasing the halogen content, and it cannot be said that it is a preferable method for applications that require high oil resistance.

  In applications where high oil resistance is required, such as fuel hoses for automobiles and special hydraulic hoses for construction machinery, it is difficult to apply a single layer of halogenated polyolefin. The inner layer portion is made of acrylonitrile / butadiene rubber, hydrogenated acrylonitrile / butadiene rubber, acrylic rubber, or fluorine-based material with particularly excellent oil resistance, resulting in a situation where a multilayer structure must be formed ( For example, see Patent Documents 1 to 6.)

  However, in recent automobiles, the temperature in the engine room has risen due to the space saving and turbo of the engine room, and the heat resistance of acrylonitrile-butadiene rubber as the inner layer material may exceed the limit. In such a case, hydrogenated acrylonitrile / butadiene rubber, acrylic rubber, or fluorine-based material, which has better heat resistance than acrylonitrile / butadiene rubber, will be used, but these materials are compared to acrylonitrile / butadiene rubber. Therefore, a rubber material having a relatively low price and excellent balance between oil resistance and heat resistance is desired.

JP-A-5-193053 Japanese Patent Laid-Open No. 7-24961 JP 2001-206987 A Japanese Patent Application Laid-Open No. 2002-103412 JP 2007-269862 A JP 2014-231159 A

  The present invention has been made in view of the above problems, and its object is to produce a modified halogenated polyolefin composition having greatly improved oil resistance while maintaining the excellent heat resistance of the halogenated polyolefin. Is to provide.

  As a result of intensive studies to solve the above-described problems, the present inventor has completed the present invention. That is, the present invention provides a graft reaction of an unsaturated monomer containing acrylonitrile and an acrylic compound to a halogenated polyolefin dissolved in a solvent using a radical initiator. In the presence of a modified halogenated polyolefin composition.

  Hereinafter, the present invention will be described in more detail.

  In the present invention, when a graft reaction of an unsaturated monomer containing acrylonitrile and an acrylic compound to a halogenated polyolefin dissolved in a solvent using a radical initiator is performed, the graft reaction is performed in the presence of an aldehyde amine compound. It is the manufacturing method of the modified | denatured halogenated polyolefin composition characterized by performing below.

  For example, a halogenated polyolefin is dissolved in a solvent, an unsaturated monomer containing acrylonitrile and an acrylic compound is added all at once or continuously in the presence of an aldehyde amine compound, and graft polymerization is performed using a radical initiator. When a predetermined polymerization conversion rate is reached, an antioxidant can be added, and if necessary, the solvent or unreacted unsaturated monomer can be washed, removed under reduced pressure, and dried.

  Examples of the halogenated polyolefin include halogenated polyolefins obtained by chlorinating and chlorosulfonating a raw material polyolefin. In addition, halogenated polyolefins containing bromine or fluorine can be used as necessary. Examples of the raw material polyolefin include polyethylene, polypropylene, and the like. As the polyethylene, high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and very low density polyethylene (VLDPE). ), Fluorine-containing polyethylene and the like. These can be used alone or in combination, but high-density polyethylene (HDPE) is preferred in order to achieve both good physical properties and oil resistance.

  When performing the reaction of chlorinating and chlorosulfonating the polyolefin, which is a raw material, examples of the solvent include aromatic organic solvents such as benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, fluorobenzene, dichlorodifluorobenzene, Chlorinated organic solvents such as carbon chloride, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, tetrachloroethane, trichlorofluoroethane, and the like. Can be used alone or in combination of two or more, but it is preferable to use only a chlorinated organic solvent inert to the chlorination reaction.

  The reaction process for chlorination and chlorosulfonation of polyolefins was carried out by dissolving or suspending chlorine and sulfurous acid gas, chlorine and sulfuryl chloride, sulfuryl chloride alone, chlorine, sulfurous acid gas and sulfuryl chloride in a solvent using a radical generator as a catalyst. React with polyolefin. It is also possible to change some or all of the chlorine to bromine for bromination. When carrying out the chlorosulfonation reaction, amino compounds such as pyridine and quinoline can be added as a co-catalyst as necessary. The reaction temperature is not particularly limited as long as the chlorination reaction and the chlorosulfonation reaction proceed, and is, for example, 40 to 150 ° C., which is preferable for the appropriate chlorination reaction and chlorosulfonation reaction to proceed. Is in the range of 60-130 ° C. The reaction pressure is not particularly limited as long as the chlorination reaction and the chlorosulfonation reaction proceed. For example, the reaction pressure is 0 to 1.0 MPa, so that an appropriate chlorination reaction and chlorosulfonation reaction proceed. Is preferably 0 to 0.7 MPa.

  The radical generator used in the reaction of chlorinating and chlorosulfonating the polyolefin as a raw material is not particularly limited as long as the chlorination reaction and the chlorosulfonation reaction proceed. Examples thereof include compounds and organic peroxides. Examples of the azo compound include α, α′-azobisisobutyronitrile, azobiscyclohexanecarbonitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), and organic peroxides. Examples thereof include benzoyl peroxide, acetyl peroxide, t-butyl peroxide, and t-butyl perbenzoate. An azo compound is preferred because of its high handling stability, and α, α'-azobisisobutyronitrile is particularly preferred for the appropriate chlorination and chlorosulfonation reactions to proceed.

  Chlorine and sulfurous acid gas, chlorine and sulfuryl chloride, sulfuryl chloride alone, chlorine, sulfurous acid gas and sulfuryl chloride, and radical generators in the reaction process for chlorination and chlorosulfonation are chlorination and chlorosulfurization. Although it is not particularly limited as long as the sulfonation reaction proceeds, for light color, before adding a radical generator, chlorine and sulfurous acid gas, chlorine and sulfuryl chloride, sulfuryl chloride alone, chlorine, sulfurous acid gas and sulfuryl chloride, etc. It is preferable to add it first. At the end of the reaction process, after the addition of the radical generator is stopped, it is preferable to stop the addition of chlorine and sulfurous acid gas, chlorine and sulfuryl chloride, sulfuryl chloride alone, chlorine, sulfurous acid gas and sulfuryl chloride, etc. You may use together.

  The amount of chlorine in the halogenated polyolefin used in the production of the modified halogenated polyolefin composition is not particularly limited, but is preferably in the range of 15.0 to 50.0% by weight in consideration of oil resistance and mechanical properties, and further has low temperature properties. Is considered to be in the range of 20.0 wt% to 40.0 wt%. The amount of sulfur in the case where the halogenated polyolefin is chlorosulfonated polyethylene obtained by chlorinating and chlorosulfonated polyolefin is not particularly limited, but is preferably in the range of 0.3 to 7.0% by weight, and further has low temperature properties. Is considered, it is preferable that it is the range of 0.5 to 5.0 weight%.

  In order to perform the graft reaction step in a uniform solution state, it is preferable to use a solvent in which the halogenated polyolefin and the monomers as raw materials and the resulting modified halogenated polyolefin composition are soluble. Solvents include aromatic organic solvents such as benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, fluorobenzene, dichlorodifluorobenzene, carbon tetrachloride, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, Chlorinated organic solvents such as 1,1,1-trichloroethane, 1,1,2-trichloroethane, tetrachloroethane, trichlorofluoroethane and the like can be mentioned, and these can be used alone or in combination of two or more.

  Examples of aldehyde amine compounds include n-butyraldehyde amine, a reaction product of formaldehyde and aniline, a reaction product of acetaldehyde and aniline, a reaction product of propyl aldehyde and aniline, a reaction product of n-butyraldehyde and aniline, and a reaction product of isobutyraldehyde and aniline. Examples include reactants, reactants of cyclohexanecarbaldehyde and aniline, and reactants of benzaldehyde and aniline. These can be used alone or in combination of two or more. By carrying out the grafting reaction in the presence of an aldehyde amine compound, the grafting reaction can proceed even if a radical initiator having a high decomposition temperature is used. Furthermore, acrylonitrile and acrylic compound in the graft copolymer It is possible to increase the weight ratio (graft selectivity) between the copolymer of acrylonitrile and the copolymer of acrylonitrile and an acrylic compound not bonded to the halogenated polyolefin. The addition amount of the aldehyde amine compound is preferably 0.5 to 3 times the number of moles of the radical initiator added. When the addition amount of the aldehyde amine compound is less than 0.5 times the number of moles of the radical initiator added, the graft reaction does not proceed sufficiently when using a radical initiator with a high decomposition temperature, The total content of the copolymer of acrylonitrile and the acrylic compound not bonded to the halogenated polyolefin in the modified halogenated polyolefin composition and the copolymer of the acrylonitrile and the acrylic compound in the graft copolymer is lowered. When the added amount of the aldehyde amine compound exceeds 3 times the number of added moles of the radical initiator, coloring of the resulting modified halogenated polyolefin composition becomes remarkable. As an addition method of the aldehyde amine-based compound, it can be added all at once in the initial stage of the grafting reaction, a part thereof is added, and the remainder is continuously added, or mixed with an unsaturated monomer to be continuously added. The copolymerization of the acrylonitrile and the acrylic compound not sufficiently bonded to the halogenated polyolefin in the modified halogenated polyolefin composition and the copolymer of the acrylonitrile and the acrylic compound in the graft copolymer are allowed to proceed sufficiently. In order to increase the total content, it is preferable to add them all at the beginning of the reaction.

  The acrylic compound grafted to the halogenated polyolefin is not limited as long as it is a compound containing an acryloyl group or a methacryloyl group. For example, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid n -Butyl, 2-ethylhexyl (meth) acrylate, n-pentyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, n-octadecyl (meth) acrylate, (meth ) Fluorine-containing (meth) acrylic acid type such as (meth) acrylic acid ester such as 2-methoxyethyl acrylate, (meth) acrylic acid 2-ethoxyethyl, (meth) acrylic acid 2,2,2-trifluoroethyl, etc. Examples of compounds, epoxy group-containing (meth) acrylic acid compounds such as glycidyl (meth) acrylate These may be used alone or in combination of two or more, but in order to maintain good physical properties and oil resistance, methyl acrylate, ethyl acrylate, 2-methoxyethyl acrylate, n-acrylate It is desirable to use butyl alone or in combination.

  In addition to acrylonitrile and acrylic compounds, other monomers may be graft-polymerized as long as the properties of the modified halogenated polyolefin are not impaired. For example, alkyl vinyl ketone compounds such as methyl vinyl ketone, alkyl vinyl ether compounds such as vinyl ethyl ether, allyl ether compounds such as allyl methyl ether, vinyl aromatic compounds such as styrene, α-methyl styrene, chlorostyrene, vinyl toluene, vinyl naphthalene, etc. , Vinyl nitrile compounds such as methacrylonitrile, vinyl acetate, vinyl chloroacetate, acrylamide, propylene, butadiene, isoprene, pentadiene, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl propionate, maleic anhydride, anhydrous Examples thereof include citraconic acid and itaconic anhydride. These monomers are preferably added at a ratio of 20% by weight or less in the total unsaturated monomers used for graft polymerization.

  As the radical initiator used in the method for producing the modified halogenated polyolefin composition of the present invention, peroxides, azo compounds and the like can be used. Peroxides include ketone peroxides such as methyl-ethyl ketone peroxide, cyclohexanone peroxide, acetylacetone peroxide, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butyl). Peroxy) cyclohexane, 2,2-di (t-butylperoxy) butane, n-butyl-4,4-di (t-butylperoxy) valeric acid and other peroxyketals, p-menthane-hydroper Hydroperoxides such as oxide, diisopropylbenzene-hydroperoxide, 1,1,3,3-tetramethylbutyl-hydroperoxide, cumene-hydroperoxide, t-butyl-hydroperoxide, di (2-t -Butylperoxyisopropyl) benzene Dicumyl-peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butyl-cumyl-peroxide, di-t-hexyl-peroxide, di-t-butyl-peroxide Oxides, dialkyl peroxides such as 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, diisobutyryl-peroxide, di (3,5,5-trimethylhexanoyl) peroxide, Diazyl peroxides such as dilauroyl-peroxide, disuccinic acid-peroxide, dibenzoyl-peroxide, di (4-methylbenzoyl) peroxide, di-n-propyl-peroxydicarbonate, diisopropyl-peroxydicarbonate Di (4-t-butylcyclohexyl) peroxydi -Peroxydicarbonates such as bonate, di (2-ethylhexyl) peroxydicarbonate, di-sec-butyl-peroxydicarbonate, cumyl-peroxyneodecanoic acid, 1,1,3,3-tetramethylbutyl- Peroxyneodecanoic acid, t-hexyl-peroxyneodecanoic acid, t-butyl-peroxyneodecanoic acid, t-butyl-peroxyneoheptanoic acid, t-hexyl-peroxypivalic acid, t-butyl-peroxypivalic acid, 1,1 , 3,3-tetramethylbutyl-peroxy-2-ethylhexanoic acid, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hexyl-peroxy-2-ethylhexanoic acid , T-butyl-peroxy-2-ethylhexanoic acid, t-hexyl-pero Xyl-isopropyl-monocarbonate, t-butyl-peroxy-maleic acid, t-butyl-peroxy-3,5,5-trimethylhexanoic acid, t-butyl-peroxylauric acid, t-butyl-peroxyisopropyl monocarbonate , T-butyl-peroxy-2-ethylhexyl-monocarbonate, t-hexyl-peroxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, t-butyl -Peroxyesters such as peroxybenzoate. As the azo compound, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2- Methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl) azo] formamide, dimethyl-2,2′-azobis (2-methyl) Propionate), 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2,4,4-trimethylpentane), 2,2′-azobis {2-methyl-n- [1 , 1′-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2, 2'-azobis [2- (imidazolin-2-yl) propane] disulfate dihydrate, 2,2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane } Dihydrochloride, 2,2′-azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride, 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2 ′ -Azobis [n- (2-carboxyethyl) -2-methylpropionamidine] tetrahydrate and the like. These radical initiators can be used alone or in combination. In some cases, ferrous salts such as ferrous sulfate, hydrosulfite sodium, ascorbic acid, erythorbic acid, aniline, tertiary amines, etc. Graft polymerization can also be carried out by adding a reducing agent.

  The method for adding the unsaturated monomer and the radical initiator is not particularly limited, and is a method of adding all of the unsaturated monomer and / or the radical initiator at the initial stage of the graft reaction. And a method of continuously injecting the remaining unsaturated monomers and / or radical initiators, and a method of continuously injecting all unsaturated monomers and / or radical initiators.

  In order to adjust the molecular weight of the copolymer and to suppress intermolecular crosslinking, a molecular weight modifier may be added during the graft reaction. Examples of the molecular weight regulator include diisopropyl xanthogen disulfide, diethyl xanthogen disulfide, diethyl thiuram disulfide, 2,2′-dithiopropionic acid, 3,3′-dithiopropionic acid, 4,4′-dithiodibranic acid, 2,2 ′. -Disulfides such as dithiobisbenzoic acid, n-dodecyl mercaptan, octyl mercaptan, t-butyl mercaptan, thioglycolic acid, thiomalic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiosalicylic acid, 3-mercaptobenzoic acid, Mercaptans such as thiomaleic anhydride, dithiomaleic acid, thioglutaric acid, cysteine, homocysteine, 6-mercaptotetrazoleacetic acid, 3-mercapto-1-propanesulfonic acid, diphenylethylene p- chloro diphenylethylene, p- cyano-diphenyl ethylene, alpha-methyl styrene dimer, benzyl dithio benzoate, organic tellurium compounds, sulfur and the like, can be used alone or in combination.

  The antioxidant is not particularly limited, and is generally used as an antioxidant for polymers. For example, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′- Methylenebis (4-ethyl-6-tert-butylphenol), 2,2-bis [{[3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] oxy} methyl] propane-1,3 -Diol, 1,3-bis [3- (t-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (3-methyl-6-t-butylphenol), triethylene glycol-bis [3- (3-t-butyl-5-methyl-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-l Loxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylaniline) -1,3,5-triazine, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ], Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide) ), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5- -T-butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 2,4-bis [(octylthio) methyl] -ortho-cresol, Isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 3, 9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) -propionoxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5 · 5] Phenol antioxidants such as undecane, 2,2-hydroxy-5-methylphenyl-benzotriazole, 4,4′-bis- (2,2- Amine-based antioxidants such as dimethylbenzyl) diphenylamine, bis (1,2,2,5,6-pentamethyl-4-piperidyl) decanedionate, dilauryl 3,3′-thiodipropionate, dimyristyl-3,3 '-Thiodipropionate, distearyl-3,3'-dithiopropionate, pentaerythrityl-tetrakis (3-laurylthiopropionate) ditridecyl-3,3'-thiodipropionate, 2-mercaptobenzimidazole, etc. Sulfur antioxidants such as trisnonylphenyl phosphite, triphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, 2,2,6,6-tetra And stable radical antioxidants such as methylpiperidine-1-oxyl.

  The reaction temperature and reaction pressure of the graft reaction are not particularly limited, but the reaction temperature is preferably 50 to 150 ° C., and the reaction pressure is preferably in the range of 0 to 1.0 MPa.

  After completion of the reaction, the desired modified halogenated polyolefin composition is obtained by precipitation with an insoluble solvent such as methanol, concentration and drying using a drum dryer, an extruder with a vent, or the like.

  A feature of the present invention is that a modified halogenated polyolefin composition excellent in physical properties and oil resistance can be obtained by introducing acrylonitrile and an acrylic compound into a halogenated polyolefin by a graft reaction in the presence of an aldehyde amine compound. Is a point.

  The modified halogenated polyolefin composition obtained by the present invention includes a copolymer of acrylonitrile and an acrylic compound bonded to the halogenated polyolefin in the graft copolymer and a halogenated polyolefin as derived from acrylonitrile and an acrylic compound. There is a copolymer of acrylonitrile and an acrylic compound that is not bonded to the. There is no particular limitation on the weight ratio (graft selectivity) of the copolymer of acrylonitrile and acrylic compound in the graft copolymer and the copolymer of acrylonitrile and acrylic compound not bonded to the halogenated polyolefin, In order to achieve both the mechanical properties and oil resistance of the resulting modified halogenated polyolefin composition, the weight ratio is preferably in the range of 30/70 to 70/30.

  In the modified halogenated polyolefin composition used in the present invention, the total content of the copolymer of acrylonitrile and acrylic compound not bonded to the halogenated polyolefin and the copolymer of acrylonitrile and acrylic compound in the graft copolymer The ratio is preferably in the range of 20% by weight to 75% by weight in order to achieve both excellent physical properties and oil resistance while maintaining the properties as the halogenated polyolefin composition. More preferably, it is in the range of 40% to 65% by weight. The remaining components are components derived from the halogenated polyolefin in the graft copolymer.

  Acrylonitrile contained in the copolymer of acrylonitrile and acrylic compound not bonded to the halogenated polyolefin in the modified halogenated polyolefin composition used in the present invention, and in the copolymer of acrylonitrile and acrylic compound in the graft copolymer The polymerization ratio of the components derived from the acrylic compound is preferably in the range of 3/97 to 70/30, more preferably in the range of 3/97 to 50/50. When the weight ratio of acrylonitrile in the copolymer is 3% or more, the tensile strength of the resulting modified halogenated polyolefin vulcanizate is maintained. On the other hand, when the weight ratio of acrylonitrile is 70% or less, the viscosity of the resulting modified halogenated polyolefin composition does not increase and the moldability is good. Moreover, from the viewpoint of improving the cold resistance of the modified halogenated polyolefin, the weight ratio of acrylonitrile is preferably as low as possible without impairing the oil resistance, and is in the range of 3/97 to 50/50.

  In the present invention, the modified halogenated polyolefin composition is used as a vulcanizate. As a method of obtaining a vulcanized product of the modified halogenated polyolefin composition of the present invention, the modified halogenated polyolefin composition and various compounding agents are blended or kneaded with a roll or a Banbury mixer, and then press vulcanized, steam vulcanized, High frequency (UHF) vulcanization or electron beam vulcanization is performed. Although there is no restriction | limiting in particular in vulcanization temperature, it is 130-200 degreeC, Preferably it is 150-180 degreeC. Moreover, it is also possible to perform secondary vulcanization as needed. Secondary vulcanization conditions are performed in a heating oven in the range of 140 to 180 ° C. for 2 to 6 hours. Examples of various compounding agents include vulcanizing agents, vulcanization accelerators, acid acceptors, plasticizers, reinforcing agents, fillers, processing aids, anti-aging agents, and the like, and they are used as necessary.

  Examples of the vulcanizing agent include inorganic vulcanizing agents such as sulfur, organic vulcanizing agents such as thiuram polysulfides, dithiocarbamates, oximes, nitroso compounds, and organic peroxides. Examples of the vulcanization accelerator include thioureas, guanidines, thiazoles, sulfenamides, thiurams, dithiocarbamates, xanthates, and the like. Examples of the acid acceptor include magnesium oxide, zinc oxide, hydrotalcite, and resurge. Examples of the plasticizer include mineral oil softeners, vegetable oil softeners, synthetic softeners, and synthetic plasticizers. Examples of the reinforcing material include carbon black and white carbon. Examples of the filler include calcium carbonates, basic magnesium carbonates, silicic acid and silicates. Processing aids include fatty acids, fatty acid esters, fatty acid metal salts, hydrocarbon waxes, and the like. Examples of the anti-aging agent include amine-based anti-aging agents, phenol-based anti-aging agents, sulfur-based anti-aging agents, phosphorus-based anti-aging agents, and waxes.

  The vulcanized composition obtained by vulcanizing the modified halogenated polyolefin composition of the present invention can be used for various hoses, various sealing materials, packing, and the like that particularly require oil resistance.

  According to the method for producing a modified halogenated polyolefin composition of the present invention, it becomes possible to provide a modified halogenated polyolefin having both good flame retardancy, physical properties and oil resistance, and various hoses particularly requiring oil resistance. It can be used for various sealing materials and packings.

  Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples.

  The values used in the following examples and the like are those measured by the following measurement methods.

<Conversion rate of unsaturated monomer>
The conversion rate of the unsaturated monomer is obtained by collecting a small amount of the solution after completion of the reaction and measuring the amount of the unreacted unsaturated monomer using gas chromatography (GC-2025, manufactured by Shimadzu Corporation). It was.

<Content of copolymer>
In the modified halogenated polyolefin composition, the total content of the copolymer of acrylonitrile and acrylic compound not bonded to the halogenated polyolefin and the copolymer of acrylonitrile and acrylic compound in the graft copolymer is The weight was calculated from the weight of the halogenated polyolefin as a raw material, the amount of unsaturated monomers (acrylonitrile and acrylic compound) charged, and the weight of reacted unsaturated monomers determined from the conversion rate of each unsaturated monomer.

Content = {weight of unsaturated monomer reacted / (weight of halogenated polyolefin + weight of unsaturated monomer reacted)} × 100
<Weight ratio of acrylonitrile and acrylic compound in copolymer>
Acrylonitrile and acrylic contained in a copolymer of acrylonitrile and an acrylic compound not bonded to the halogenated polyolefin and a copolymer of acrylonitrile and an acrylic compound in a graft copolymer in the modified halogenated polyolefin composition The weight ratio of the component derived from the system compound was calculated from the polymerization rate of the unsaturated monomer.

Acrylonitrile weight ratio = (reacted acrylonitrile weight / reacted unsaturated monomer weight) × 100
Acrylic compound weight ratio = (reacted acrylic compound weight / reacted unsaturated monomer weight) × 100
<Graft selectivity>
Weight ratio of copolymer of acrylonitrile and acrylic compound bonded to halogenated polyolefin and copolymer of acrylonitrile and acrylic compound not bonded to halogenated polyolefin in the modified halogenated polyolefin composition (graft selection) The rate was determined by the following method.
1) The obtained modified halogenated polyolefin composition is extracted with acetone, and each of the acetone extract and the acetone extraction residue is dried and precisely weighed.

Acetone extract weight [A]
Acetone extraction residue weight [B]
3) The chlorine content in the acetone extract and the acetone extract residue is measured.

Chlorine content of raw halogenated polyolefin [C]
Chlorine content of acetone extract [D]
Chlorine content of acetone extraction residue [E]
Copolymer content in acetone extract [F] = ([C] − [D]) × 100 / [C]
Copolymer content in acetone extraction residue [G] = ([C] − [E]) × 100 / [C]
Graft selectivity = ([B] × [G]) × 100 / ([A] × [F] + [B] × [G])
<Measurement of chlorine content>
Chlorine content is measured first by acetone extract or acetone extraction of raw halogenated polyolefin or modified halogenated polyolefin composition in a combustion flask containing 15.0 ml of 1.7% by weight hydrazinium sulfate aqueous solution as an absorbing solution. 30.0 mg of the residue was combusted according to the oxygen combustion method and left to stand for 30 minutes. Next, this absorption solution was washed out with 100.0 ml of pure water, and the chloride ion was determined by potentiometric titration with a 0.05N silver nitrate aqueous solution.

<Measurement of sulfur content>
The sulfur content is measured by first using an acetone extract of the raw halogenated polyolefin or modified halogenated polyolefin composition in a combustion flask containing 10.0 ml of 3.0% by weight hydrogen peroxide as an absorbent. 30.0 mg of acetone extraction residue was burned according to the oxygen combustion method and allowed to stand for 30 minutes. Next, this absorbing solution was washed out with about 40.0 ml of pure water, and then 1 ml of acetic acid, 100.0 ml of 2-propyl alcohol, and 0.47 ml of arsenazo III were added. This was determined by quantifying sulfate ion by a photometric titration method with a 0.01N concentration barium acetate solution.

<Physical property evaluation>
The modified halogenated polyolefin composition was kneaded in accordance with JIS-K-6299 (2012 version) with the prescribed formulation described in Table 1, and the obtained sample was vulcanized with a 2 mm thick mold. . Thereafter, tensile strength (TB), elongation at break (EB), and 100% tensile stress (M100) were evaluated according to JIS-K-6251 (2012 edition) under conditions of a tensile speed of 500 mm / min and 23 ° C. .

＜耐油性評価＞
得られた加硫物をＪＩＳ−Ｋ−６２５８（２０１２年度版）に従い、試験用潤滑油のＮｏ．３油を用い、１００℃で７２時間浸漬した後の体積変化率を測定することにより評価した。

<Oil resistance evaluation>
According to JIS-K-6258 (2012 version), the obtained vulcanized product was tested with a lubricating oil No. Three oils were used for evaluation by measuring the volume change rate after being immersed at 100 ° C. for 72 hours.

Example 1
Graft reaction using TOSOH-CSM TS-530 (Chlorosulfonated polyethylene manufactured by Tosoh Corporation, chlorine content 35.6% by weight, sulfur content 1.03% by weight, Mooney viscosity ML1 + 4 = 56) as halogenated polyolefin. Carried out.

  Under a nitrogen atmosphere, a 4-liter glass flask was charged with 150 g of chlorosulfonated polyethylene and 2.0 kg of 1,1,2-trichloroethane, the inside was replaced with nitrogen, and the mixture was heated to 110 ° C. to dissolve the chlorosulfonated polyethylene. After cooling the internal temperature to 65 ° C., 86.9 g of acrylonitrile, 213.1 g of 2-methoxyethyl acrylate, radical initiator (Perbutyl O manufactured by NOF Corporation; t-butyl-peroxy-2-ethylhexanoate) ) 7.0 g was added, and a solution in which 2.0 g of n-butyraldehydeamine (Noxeller 8 manufactured by Ouchi Shinsei Chemical Co., Ltd.) dissolved in 144 g of 1,1,2-trichloroethane was added dropwise over 5 hours. The reaction was carried out. Thereafter, stirring was continued for 1 hour, and the resulting reaction solution was dried with a drum dryer to obtain a modified halogenated polyolefin composition.

  The resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 42.8% by weight, and the acrylonitrile-acrylic acid 2-methoxyethyl copolymer acrylonitrile / acrylic acid 2- The methoxyethyl ratio was 40/60. The physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 2.

実施例２
ハロゲン化ポリオレフィンとして、実施例１記載のクロロスルホン化ポリエチレンを用いて、グラフト反応を実施した。

Example 2
The graft reaction was carried out using the chlorosulfonated polyethylene described in Example 1 as the halogenated polyolefin.

  Under a nitrogen atmosphere, a 4-liter glass flask was charged with 150 g of chlorosulfonated polyethylene and 2.0 kg of 1,1,2-trichloroethane, the inside was replaced with nitrogen, and the mixture was heated to 110 ° C. to dissolve the chlorosulfonated polyethylene. After cooling the internal temperature to 65 ° C., 86.9 g of acrylonitrile, 213.1 g of 2-methoxyethyl acrylate, 2.0 g of n-butyraldehyde amine (Noxeller 8 manufactured by Ouchi Shinsei Chemical Co., Ltd.) are added, A solution of 7.0 g of dissolved radical initiator dissolved in 144 g of 1,1,2-trichloroethane (Perbutyl O; manufactured by NOF Corporation; t-butyl-peroxy-2-ethylhexanoate) was added dropwise over 5 hours. The reaction was carried out. Thereafter, stirring was continued for 1 hour, and the resulting reaction solution was dried with a drum dryer to obtain a modified halogenated polyolefin composition.

  The resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 32.1% by weight, and the acrylonitrile-acrylic acid 2-methoxyethyl copolymer acrylonitrile / acrylic acid 2- The methoxyethyl ratio was 49/51. The physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 2.

Example 3
The graft reaction was carried out using the chlorosulfonated polyethylene described in Example 1 as the halogenated polyolefin.

  Under a nitrogen atmosphere, a 4-liter glass flask was charged with 150 g of chlorosulfonated polyethylene and 2.0 kg of 1,1,2-trichloroethane, the inside was replaced with nitrogen, and the mixture was heated to 110 ° C. to dissolve the chlorosulfonated polyethylene. After cooling the internal temperature to 65 ° C., 39.8 g of acrylonitrile, 213.1 g of 2-methoxyethyl acrylate, 2.0 g of n-butyraldehyde amine (Noxeller 8 manufactured by Ouchi Shinsei Chemical Co., Ltd.) were added, A 7.0 g solution of dissolved radical initiator dissolved in 288 g of 1,1,2-trichloroethane (Perfu O manufactured by NOF Corporation; t-butyl-peroxy-2-ethylhexanoate) was added dropwise over 10 hours. The reaction was carried out. Thereafter, stirring was continued for 1 hour, and the resulting reaction solution was dried with a drum dryer to obtain a modified halogenated polyolefin composition.

  The resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 45.1% by weight, and the acrylonitrile-acrylic acid 2-methoxyethyl copolymer acrylonitrile / acrylic acid 2- The methoxyethyl ratio was 39/61. The physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 2.

Example 4
The graft reaction was carried out using the chlorosulfonated polyethylene described in Example 1 as the halogenated polyolefin.

  Under a nitrogen atmosphere, a 4-liter glass flask was charged with 150 g of chlorosulfonated polyethylene and 2.0 kg of 1,1,2-trichloroethane, the inside was replaced with nitrogen, and the mixture was heated to 110 ° C. to dissolve the chlorosulfonated polyethylene. After cooling the internal temperature to 65 ° C., 86.9 g of acrylonitrile, 213.1 g of 2-methoxyethyl acrylate, 2.0 g of n-butyraldehyde amine (Noxeller 8 manufactured by Ouchi Shinsei Chemical Co., Ltd.) are added, A solution of 14.0 g of dissolved radical initiator dissolved in 288 g of 1,1,2-trichloroethane (Perfu O manufactured by NOF Corporation; t-butyl-peroxy-2-ethylhexanoate) was added dropwise over 10 hours. The reaction was carried out. Thereafter, stirring was continued for 1 hour, and the resulting reaction solution was dried with a drum dryer to obtain a modified halogenated polyolefin composition.

  The resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 52.3% by weight, and the acrylonitrile-acrylic acid 2-methoxyethyl copolymer acrylonitrile / acrylic acid 2- The methoxyethyl ratio was 30/70. The physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 2.

Comparative Example 1
A modified halogenated polyolefin composition was obtained in the same manner as in Example 1 except that n-butyraldehydeamine (Noxeller 8 manufactured by Ouchi Shinsei Chemical Co., Ltd.) was not added.

  The resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 7.4% by weight, and the polymerization conversion of unsaturated monomers was extremely low. This is because the one-hour half-life temperature of the radical initiator is 92.1 ° C., and when the reaction temperature is 65 ° C., generation of radical species due to decomposition of the radical initiator was insufficient. Therefore, graft selectivity and formulation evaluation were not performed.

Comparative Example 2
A modified halogenated polyolefin composition was obtained in the same manner as in Example 3, except that n-butyraldehydeamine (Noxeller 8 manufactured by Ouchi Shinsei Chemical Co., Ltd.) was not added.

  The resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 6.1% by weight, and the polymerization conversion of unsaturated monomers was extremely low. This is because the one-hour half-life temperature of the radical initiator is 92.1 ° C., and when the reaction temperature is 65 ° C., generation of radical species due to decomposition of the radical initiator was insufficient. Therefore, graft selectivity and formulation evaluation were not performed.

Comparative Example 3
After adding 21.6 kg of 1,1,2-trichloroethane, density of 960 kg / cm ³ , and melt flow rate (MFR) of 5.0 g / 10 min to 3 kg of 40 liter glass-lined autoclave, Steam was passed through the reactor jacket to uniformly dissolve the polyethylene at 110 ° C. During this time, nitrogen gas was introduced into the reactor at a flow rate of 10.0 liters / minute to remove air in the reactor. As a radical generator, a solution of 5.0 g of α, α′-azobisisobutyronitrile dissolved in 1.0 liter of 1,1,2-trichloroethane at a flow rate of 4.0 ml / min, 6.5 kg Sulfuryl chloride was continuously added to the reactor from each separate inlet at a flow rate of 25.0 ml / min. During the reaction, the pressure of the reactor was kept at 0.2 MPa. After completion of the reaction, the pressure in the reaction system was reduced to normal pressure, and then nitrogen was blown under normal pressure to discharge hydrogen chloride and sulfurous acid gas dissolved in the solution out of the system. Thereafter, the product was isolated with a drum dryer to obtain chlorosulfonated polyethylene.

  The resulting chlorosulfonated polyethylene contained 35.3% by weight chlorine and 0.22% by weight sulfur.

  Next, a graft reaction was performed using the obtained chlorosulfonated polyethylene.

  Under a nitrogen atmosphere, 200 g of chlorosulfonated polyethylene and 2.0 kg of 1,1,2-trichloroethane were charged into a 4-liter glass flask, the inside was replaced with nitrogen, and the mixture was heated to 110 ° C. to dissolve the chlorosulfonated polyethylene. After cooling the internal temperature to 65 ° C., 49.7 g of acrylonitrile and 121.8 g of 2-methoxyethyl acrylate were added, and a radical initiator dissolved in 144 g of 1,1,2-trichloroethane (Perroyl manufactured by NOF Corporation) A solution in which 3.7 g of OPP (di-2-ethylhexyl-peroxydicarbonate) was dissolved was dropped over 5 hours to carry out the reaction. Thereafter, stirring was continued for 1 hour, and the resulting reaction solution was dried with a drum dryer to obtain a modified halogenated polyolefin composition.

  The resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 30.2% by weight, and the acrylonitrile-acrylic acid 2-methoxyethyl copolymer acrylonitrile / acrylic acid 2- The methoxyethyl ratio was 29/71. The physical properties were evaluated according to the formulation of formulation 2. The evaluation results are shown in Table 2.

Comparative Example 4
Modified halogenated polyolefin in the same manner as in Comparative Example 3 except that the amount of chlorosulfonated polyethylene charged in the graft reaction was changed to 180 g, and the unsaturated monomer was changed to 69.3 g of acrylonitrile and 85.0 g of 2-methoxyethyl acrylate. A composition was obtained.

  The resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 28.8% by weight, and the acrylonitrile-acrylic acid 2-methoxyethyl copolymer acrylonitrile / acrylic acid 2- The methoxyethyl ratio was 49/51. The physical properties were evaluated according to the formulation of formulation 2. The evaluation results are shown in Table 2.

Comparative Example 5
A modified halogenated polyolefin composition was obtained in the same manner as in Comparative Example 3 except that the unsaturated monomer was changed to 134.8 g of acrylonitrile and 165.3 g of 2-methoxyethyl acrylate.

  The resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 50.2% by weight, and the acrylonitrile-acrylic acid 2-methoxyethyl copolymer acrylonitrile / acrylic acid 2- The methoxyethyl ratio was 49/51. The physical properties were evaluated according to the formulation of formulation 2. The evaluation results are shown in Table 3.

Claims (8)

When grafting an unsaturated monomer containing acrylonitrile and an acrylic compound to a halogenated polyolefin dissolved in a solvent using a radical initiator, the grafting reaction is performed in the presence of an aldehyde amine compound. A method for producing a modified halogenated polyolefin composition. The method for producing a modified halogenated polyolefin composition according to claim 1, wherein the halogenated polyolefin is a chlorosulfonated polyolefin. The modified halogenated polyolefin composition according to claim 1 or 2, wherein the addition amount of the aldehyde amine compound is 0.5 to 3 times the number of moles of the radical initiator added. Manufacturing method. The method for producing a modified halogenated polyolefin composition according to any one of claims 1 to 3, wherein the aldehyde amine compound is added in an amount before the start of the grafting reaction. The modified halogenated polyolefin composition contains a graft copolymer in which a copolymer of acrylonitrile and an acrylic compound is bonded to the halogenated polyolefin, and a copolymer of acrylonitrile and an acrylic compound that is not bonded to the halogenated polyolefin. The weight ratio of the copolymer of acrylonitrile and acrylic compound in the graft copolymer to the copolymer of acrylonitrile and acrylic compound not bonded to the halogenated polyolefin is in the range of 30/70 to 70/30. The method for producing a modified halogenated polyolefin composition according to any one of claims 1 to 4, wherein: The total content of the copolymer of acrylonitrile and acrylic compound not bonded to the halogenated polyolefin in the modified halogenated polyolefin composition and the copolymer of acrylonitrile and acrylic compound in the graft copolymer is 20% by weight. The method for producing a modified halogenated polyolefin composition according to any one of claims 1 to 5, wherein the range is from 75 to 75% by weight. The weight ratio of the components derived from acrylonitrile and the acrylic compound contained in the copolymer of acrylonitrile and the acrylic compound not bonded to the halogenated polyolefin and the graft copolymer is in the range of 3/97 to 70/30. A process for producing a modified halogenated polyolefin composition according to any one of claims 1 to 6. The method for producing a modified halogenated polyolefin composition according to any one of claims 1 to 7, wherein the acrylic compound is 2-methoxyethyl acrylate.