JP6926538B2 - Method for Producing Modified Halogenated Polyolefin Composition - Google Patents

Description

The present invention relates to a method for producing a modified halogenated polyolefin composition, and more specifically, an unsaturated monomer containing an acrylonitrile and an acrylic compound is added to a halogenated polyolefin dissolved in a solvent, and a radical initiator is used. The present invention relates to a method for producing a modified halogenated polyolefin composition, which comprises carrying out the graft reaction in the presence of an aldehyde amine compound.

Halogenized 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 resistance. Therefore, it is a cover material for various hoses and hoses. , Used in various applications such as wire coating materials, packings, gaskets, rolls and handrails for escalators. In addition, since chlorosulfonated polyethylene, chlorinated polyethylene, etc. contain chlorine groups, they have better oil resistance than general-purpose rubbers such as natural rubber, styrene-butadiene rubber, and ethylene-propylene rubber, and have better oil resistance. It is often used in required hoses and tubes.

It is known to increase the amount of halogen as a method for improving the oil resistance of the halogenated polyolefin. However, when the oil resistance is improved by this method, the glass transition temperature of the obtained halogenated polyolefin becomes high 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 the improvement of oil resistance by increasing the amount of halogen, and it cannot be said that this method is preferable for applications requiring high oil resistance.

In applications that require a high degree of oil resistance, such as fuel hoses for automobiles and special hydraulic hoses for construction machinery, it is difficult to apply a single layer of halogenated polyolefin, and the fuel etc. come into direct contact. Acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, acrylic rubber, or a fluorine-based material with particularly excellent oil resistance is used for the inner layer part, and there is a situation where there is no choice but to have a multi-layer structure ( For example, see Patent Documents 1 to 6).

However, in recent automobiles, the temperature inside the engine room is rising due to space saving and turbo conversion of the engine room, and the heat resistance of acrylonitrile-butadiene rubber as an inner layer material may exceed the limit. In such a case, hydrogenated acrylonitrile-butadiene rubber, acrylic rubber, or a fluorine-based material, which has better heat resistance than acrylonitrile-butadiene rubber, is used, but these materials are compared with acrylonitrile-butadiene rubber. Therefore, a rubber material having a relatively low price and an excellent balance between oil resistance and heat resistance is desired because the price is high and the material cost of hose products is significantly increased.

Japanese Unexamined Patent Publication No. 5-193053 Japanese Unexamined Patent Publication No. 7-24961 Japanese Unexamined Patent Publication No. 2001-206987 Japanese Unexamined Patent Publication No. 2002-103412 JP-A-2007-269862 Japanese Unexamined Patent Publication No. 2014-231159

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

The present inventor has completed the present invention as a result of diligent studies to solve the above problems. That is, in the present invention, when an unsaturated monomer containing acrylonitrile and an acrylic compound is grafted onto a halogenated polyolefin dissolved in a solvent using a radical initiator, the graft reaction is carried out by an aldehyde amine compound. It is a method for producing a modified halogenated polyolefin composition, which is characterized by being carried out in the presence of.

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

In the present invention, when an unsaturated monomer containing an acrylonitrile and an acrylic compound is grafted onto 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. It is a method for producing a modified halogenated polyolefin composition, which is characterized by being carried out below.

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

Examples of the halogenated polyolefin include halogenated polyolefins obtained by chlorinating and chlorosulfonizing the raw material polyolefin. Further, if necessary, halogenated polyolefins containing bromine or fluorine can also be used. Examples of the raw material polyolefin include polyethylene and polypropylene, and examples of polyethylene include high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and ultra-low-density polyethylene (VLDPE). ), Fluorine-containing polyethylene and the like. These can be used alone or in combination, but high density polyethylene (HDPE) is preferable in order to achieve both good physical characteristics and oil resistance.

When the reaction of chlorinating and chlorosulfonatening the raw material polyolefin is carried out, the solvent includes aromatic organic solvents such as benzene, toluene and xylene, monochlorobenzene, dichlorobenzene, fluorobenzene, dichlorodifluorobenzene and four. Examples thereof include chlorine-based organic solvents such as carbon chloride, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, tetrachloroethane, and trichlorofluoroethane. Can be used alone or in combination of two or more, but it is preferable to use only a chlorine-based organic solvent that is inactive against the chlorination reaction.

In the reaction step of chlorinating and chlorosulfonated polyolefin, chlorine and sulfurous acid gas, chlorine and sulfuryl chloride, sulfyl chloride alone, chlorine and sulfurous acid gas and sulfyl chloride were dissolved or suspended 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 the chlorosulfonate reaction is carried out, an amino compound such as pyridine or quinoline can be added as a co-catalyst, if necessary. The reaction temperature is not particularly limited as long as it is within the range in which the chlorination reaction and the chlorosulfonate reaction proceed, and is, for example, 40 to 150 ° C., which is preferable for the appropriate chlorination reaction and the chlorosulfonate reaction to proceed. Is in the range of 60 to 130 ° C. The reaction pressure is not particularly limited as long as it is within the range in which the chlorination reaction and the chlorosulfonate reaction proceed, and is, for example, 0 to 1.0 MPa, in order for the appropriate chlorination reaction and the chlorosulfonate reaction to proceed. Is preferably 0 to 0.7 MPa.

The radical generator used when carrying out the reaction of chlorinating and chlorosulfonizing the raw material polyolefin is not particularly limited as long as the chlorination reaction and the chlorosulfonation reaction proceed, and is, for example, an azo-based agent. Examples 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, t-butyl perbenzoate and the like. Since it is highly stable in handling, it is preferably an azo compound, and it is particularly preferably α, α'-azobisisobutyronitrile in order for an appropriate chlorination reaction and chlorosulfonate reaction to proceed.

Chlorine and sulfite gas, chlorine and sulfuryl chloride, sulfuryl chloride alone, chlorine and sulfite gas, sulfyl chloride, and radical generators are added in the reaction steps for chlorination and chlorosulfonate. It is not particularly limited as long as the sulfonate reaction proceeds, but for light color, chlorine and sulfite gas, chlorine and sulfyl chloride, sulfryl chloride alone, chlorine and sulfite gas and sulfyl chloride, etc. are added before adding the radical generator. It is preferable to add it first. At the end of the reaction step, it is preferable to stop the addition of chlorine and sulfurous acid gas, chlorine and sulfuryl chloride, sulfuryl chloride alone, chlorine and sulfurous acid gas and sulfuryl chloride, etc. after stopping the addition of the radical generator. May be used 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 low temperature. In consideration of the above, it is preferably in the range of 20.0% by weight to 40.0% by weight. When the halogenated polyolefin is a chlorosulfonated polyethylene obtained by chlorinating and chlorosulfonated the polyolefin, the amount of sulfur is not particularly limited, but is preferably in the range of 0.3 to 7.0% by weight, and further has a low temperature property. In consideration of the above, it is preferably in the range of 0.5 to 5.0% by weight.

In order to carry out the graft reaction step in a uniform solution state, it is preferable to use a solvent in which the halogenated polyolefin and the monomer as raw materials and the obtained modified halogenated polyolefin composition are soluble. Examples of the solvent include aromatic organic solvents such as benzene, toluene and xylene, monochlorobenzene, dichlorobenzene, fluorobenzene, dichlorodifluorobenzene, carbon tetrachloride, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, and the like. Examples thereof include chlorine-based organic solvents such as 1,1,1-trichloroethane, 1,1,2-trichloroethane, tetrachloroethane, and trichlorofluoroethane, 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 isobutyl aldehyde and aniline. Examples thereof include a reaction product, a reaction product of cyclohexanecarbaldehyde and aniline, and a reaction product of benzaldehyde and aniline, and these can be used alone or in combination of two or more. By performing the graft reaction in the presence of an aldehyde amine compound, the graft reaction can be allowed to proceed even if a radical initiator having a high decomposition temperature is used, and further, the acrylonitrile and the acrylic compound in the graft copolymer can be allowed to proceed. It is possible to increase the weight ratio (graft selectivity) of the copolymer of Acrylonitrile and the copolymer of the acrylic compound which is not bonded to the halogenated polyolefin. The amount of the aldehyde amine compound added is preferably 0.5 to 3 times the number of moles added to the radical initiator. When the amount of the aldehyde amine compound added is less than 0.5 times the number of moles of the radical initiator added, the graft reaction does not proceed sufficiently when the radical initiator having a high decomposition temperature is used. The total content of the copolymer of the 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 reduced. When the amount of the aldehyde amine compound added exceeds three times the number of moles of the radical initiator added, the resulting modified halogenated polyolefin composition becomes significantly colored. As a method of adding the aldehyde amine compound, it can be added all at once at the initial stage of the graft reaction, a part of the compound can be added continuously, or the rest can be continuously added, or mixed with an unsaturated monomer to be continuously added. After the graft reaction is sufficiently advanced, 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 In order to increase the total content, it is preferable to add them all at once at the initial stage of the reaction.

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

In addition to acrylonitrile and acrylic compounds, other monomers may be graft-polymerized as long as the characteristics 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-methylstyrene, chlorostyrene, vinyltoluene and vinylnaphthalene. , Vinyl nitrile compounds such as methacrylonitrile, vinyl acetate, vinyl acetate, acrylamide, propylene, butadiene, isoprene, pentadiene, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl propionate, maleic anhydride, anhydrous Citraconic acid, itaconic anhydride and the like can be exemplified. These above-mentioned monomers are preferably added in a proportion of 20% by weight or less in the total unsaturated monomer used for graft polymerization.

Peroxides, azo compounds and the like can be used as the radical initiator used in the method for producing the modified halogenated polyolefin composition of the present invention. Peroxides include ketone peroxides such as methyl-ethylketone peroxide, cyclohexanone peroxide, and acetylacetone peroxide, 1,1-di (t-hexylperoxy) cyclohexane, and 1,1-di (t-butyl). Peroxyketals such as peroxy) cyclohexane, 2,2-di (t-butylperoxy) butane, n-butyl-4,4-di (t-butylperoxy) valerate, p-menthan-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, dialkyl peroxides such as 2,5-dimethyl-2,5-di (t-butylperoxy) hexin-3, diisobutyryl-peroxide, di (3,5,5) Diazil peroxides such as -trimethylhexanoyl) peroxide, dilauroyl-peroxide, disuccinic acid-peroxide, dibenzoyl-peroxide, di (4-methylbenzoyl) peroxide, di-n-propyl-peroxydi Peroxydicarbonates such as carbonate, diisopropyl-peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, di-sec-butyl-peroxydicarbonate, etc. Class, cumyl-peroxyneodecanic acid, 1,1,3,3-tetramethylbutyl-peroxyneodecanic acid, t-hexyl-peroxyneodecanic acid, t-butyl-peroxyneodecanic acid, t-butyl-peroxy Neoheptanoic 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-Ethylhexanoyl peroxy) hexane, t-hexyl-peroxy-2-ethylhexanoic acid, t-butyl-peroxy-2-ethylhexanoic acid, t-hexyl-pao Xy-isopropyl-monocarbonate, t-butyl-peroxy-maleic acid, t-butyl-peroxy-3,5,5-trimethylhexaneic 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 can be mentioned. Examples of the azo compound include 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), and 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-methylpropion amidine] Tetrahydrate and the like can be mentioned. These radical initiators can be used alone or in combination, and in some cases, ferrous salts such as ferrous sulfate, hydrosulfite sodium, ascorbic acid, erythorbic acid, aniline, tertiary amines and the like. Graft polymerization can also be carried out by adding a reducing agent.

The method for adding the unsaturated monomer and the radical initiator described above is not particularly limited, and a method of adding the unsaturated monomer and the radical initiator all at once in the initial stage of the graft reaction, and a method of adding some unsaturated monomers and / or the radical initiator to the graft reaction. Examples include a method of adding at the initial stage of the above and continuously injecting the remaining unsaturated monomer and / or radical initiator, and a method of continuously injecting all unsaturated monomers and / or radical initiator.

Further, in order to adjust the molecular weight of the copolymer and to suppress intermolecular cross-linking, a molecular weight adjusting agent may be added at the time of the graft reaction. Examples of the molecular weight modifier include diisopropylxanthogen disulfide, diethylxanthogen disulfide, diethylthiuram disulfide, 2,2'-dithiopropionic acid, 3,3'-dithiopropionic acid, 4,4'-dithiodibranoic acid, and 2,2'. -Disulfides such as dithiobis benzoic acid, n-dodecyl mercaptan, octyl mercaptan, t-butyl mercaptan, thioglycolic acid, thioapple acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiosalicylic acid, 3-mercapto benzoic acid, Mercaptans such as thiomaleic acid anhydride, dithiomaleic acid, thioglutaric acid, cysteine, homocysteine, 6-mercaptotetrazole acetate, 3-mercapto-1-propanesulfonic acid, diphenylethylene, p-chlorodiphenylethylene, p-cyanodiphenyl Examples thereof include ethylene, α-methylstyrene dimer, benzyl dithiobenzoate, organic tellurium compound, sulfur and the like, and these 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-t-butylphenol), 2,2'-. Methylenebis (4-ethyl-6-t-butylphenol), 2,2-bis [{[3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] oxy} methyl] propane-1,3 -Dioyl, 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-hydroxyphenyl) propionate], 2,4 -Bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylaniline) -1,3,5-triazine, pentaerythrityl-tetrakis [3- (3,5-di) -T-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-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-di-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-t-butyl-) 4-Hydroxy-5-methylphenyl) -propionioxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] Phenolic antioxidants such as undecane, 2, 2-Hydroxy-5-methylphenyl-benzotriazole, 4,4'-bis- (2,2- Didimethylbenzyl) Diphenylamine, bis (1,2,2,5,6-pentamethyl-4-piperidyl) amine-based antioxidants such as decandionate, dilaurilu 3,3'-thiodipropionate, dimyristyl-3,3 '-Thiodipropionate, distearyl-3,3'-dithiopropionate, pentaerythrityl-tetrakis (3-laurylthiopropionate) ditridecyl-3,3'-thiodipropionate, 2-mercaptobenzimidazole, etc. Sulfur-based antioxidants, trisnonylphenyl phosphite, triphenylphosphite, phosphorus-based antioxidants such as tris (2,4-di-t-butylphenyl) phosphite, 2,2,6,6-tetra Examples thereof include stable radical antioxidants such as methylpiperidin-1-oxyl.

The reaction temperature and reaction pressure of the graft reaction are not particularly limited, but the reaction temperature is preferably in the range of 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 can be 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 having excellent physical characteristics and oil resistance can be obtained by introducing an acrylonitrile and an acrylic compound into a halogenated polyolefin by a graft reaction in the presence of an aldehyde amine compound. It is a point.

The modified halogenated polyolefin composition obtained in 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 the acrylonitrile and the acrylic compound. There is a copolymer of acrylonitrile and an acrylic compound that is not bonded to. The weight ratio (graft selectivity) of the copolymer of acrylonitrile and the acrylic compound in the graft copolymer and the copolymer of the acrylonitrile and the acrylic compound not bonded to the halogenated polyolefin is not particularly limited. In order to achieve both mechanical properties and oil resistance of the obtained modified halogenated polyolefin composition, the weight ratio thereof is preferably in the range of 30/70 to 70/30.

The total content of the copolymer of acrylonitrile and acrylic compound not bonded to halogenated polyolefin and the copolymer of acrylonitrile and acrylic compound in the graft copolymer in the modified halogenated polyolefin composition used in the present invention. 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 of the halogenated polyolefin composition. More preferably, it is in the range of 40% by weight to 65% by weight. The remaining components are components derived from the halogenated polyolefin in the graft copolymer.

Acrylonitrile contained in a copolymer of acrylonitrile and an acrylic compound not bonded to the halogenated polyolefin in the modified halogenated polyolefin composition used in the present invention and a copolymer of acrylonitrile and an acrylic compound in a graft copolymer. The polymerization ratio of the components derived from the acrylic compound is preferably in the range of 3/97 to 70/30, and 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 obtained modified halogenated polyolefin vulcanized product is maintained. On the other hand, when the weight ratio of acrylonitrile is 70% or less, the viscosity of the obtained modified halogenated polyolefin composition does not increase, and the molding processability is good. 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 vulcanized product. As a method for obtaining a vulcanized product of the modified halogenated polyolefin composition of the present invention, after blending or kneading the modified halogenated polyolefin composition and various compounding agents with a roll or a Banbury mixer or the like, press vulcanization, steam vulcanization, etc. High frequency (UHF) vulcanization, electron beam vulcanization, etc. are performed. The vulcanization temperature is not particularly limited, but is 130 to 200 ° C, preferably 150 to 180 ° C. It is also possible to carry out secondary vulcanization if necessary. The conditions of the secondary vulcanization are carried out in a heating oven in the range of 140 to 180 ° C. for 2 hours to 6 hours. Examples of various compounding agents include vulcanizing agents, vulcanization accelerators, acid receiving agents, plasticizers, reinforcing agents, fillers, processing aids, antiaging agents, etc., which are used as necessary.

Examples of the vulcanizing agent include inorganic vulcanizing agents such as sulfur, thiuram polysulfides, dithiocarbamate salts, oximes, nitroso compounds, and organic vulcanizing agents such as organic peroxides. Examples of the vulcanization accelerator include thiourea, guanidine, thiazole, sulfenamide, thiuram, dithiocarbamate, xanthogenate and the like. Examples of the antacid include magnesium oxide, zinc oxide, hydrotalcite, and litharge. Examples of the plasticizer include mineral oil-based softeners, vegetable oil-based softeners, synthetic softeners, synthetic plasticizers, and the like. 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. Examples of the processing aid include fatty acids, fatty acid esters, fatty acid metal salts, and hydrocarbon waxes. 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, waxes and the like.

The vulcanized composition obtained by vulcanizing the modified halogenated polyolefin composition of the present invention can be used for various hoses, various sealing materials, packings and the like, which are particularly required to have oil resistance.

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

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

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

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

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

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

Acrylonitrile weight ratio = (weight of reacted acrylonitrile / weight of reacted unsaturated monomer) x 100
Acrylic compound weight ratio = (Weight of reacted acrylic compound / Weight of reacted unsaturated monomer) x 100
<Graft selectivity>
Weight ratio of copolymer of acrylonitrile and acrylic compound bonded to halogenated polyolefin in modified halogenated polyolefin composition and copolymer of acrylonitrile and acrylic compound not bonded to halogenated polyolefin (graft selection) 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 weighed.

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

Chlorine content of raw material halogenated polyolefin [C]
Chlorine content of acetone extract [D]
Chlorine content of acetone extraction residue [E]
Copolymer content in acetone extract [F] = ([C]-[D]) x 100 / [C]
Copolymer content in acetone extraction residue [G] = ([C]-[E]) x 100 / [C]
Graft selectivity = ([B] x [G]) x 100 / ([A] x [F] + [B] x [G])
<Measurement of chlorine content>
The chlorine content is first measured in an acetone extract or acetone extract of the raw material halogenated or modified halogenated polyolefin composition in a combustion flask containing 15.0 ml of a 1.7 wt% hydrazinium sulfate aqueous solution as an absorbent. 30.0 mg of the residue was burned according to the oxygen combustion method and allowed to stand for 30 minutes. Next, this absorption liquid was washed out with 100.0 ml of pure water, and chloride ions were quantified by a potentiometric titration method with a silver nitrate aqueous solution having a concentration of 0.05 N.

<Measurement of sulfur content>
The sulfur content is first measured in a combustion flask containing 10.0 ml of 3.0 wt% hydrogen peroxide solution as an absorbent, in which an acetone extract of the raw material halogenated polyolefin or modified halogenated polyolefin composition or 30.0 mg of the acetone extraction residue was burned according to the oxygen combustion method and allowed to stand for 30 minutes. Next, this absorption liquid 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 ions in a barium acetate solution having a concentration of 0.01 N by a photometric titration method.

<Physical characterization>
The modified halogenated polyolefin composition was kneaded according to JIS-K-6299 (2012 version) according to the predetermined formulation shown in Table 1, and the obtained sample was vulcanized in a mold having a thickness of 2 mm. .. After that, the tensile strength (TB), elongation at break (EB), and 100% tensile stress (M100) were evaluated according to JIS-K-6251 (2012 version) under the 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>
The obtained vulcanized product was subjected to No. 2 of the test lubricating oil according to JIS-K-6258 (2012 edition). It was evaluated by measuring the volume change rate after immersion in 3 oils 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. Was carried out.

150 g of chlorosulfonated polyethylene and 2.0 kg of 1,1,2-trichloroethane were charged in a 4 liter glass flask under a nitrogen atmosphere, 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 Nichiyu Co., Ltd .; 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 Shinko Kagaku Kogyo Co., Ltd.) dissolved in 144 g of 1,1,2-trichloroethane was added dropwise over 5 hours. The reaction was carried out. Then, stirring was continued for 1 hour, and the obtained reaction solution was dried in a drum dryer to obtain a modified halogenated polyolefin composition.

The acrylonitrile-2-methoxyethyl acrylate copolymer content of the obtained modified halogenated polyolefin composition was 42.8% by weight, and the acrylonitrile / 2-methoxyethyl acrylate copolymer of the acrylonitrile-2-methoxyethyl copolymer was acrylate. The methoxyethyl ratio was 40/60. Physical characteristics were evaluated using the combination 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.

150 g of chlorosulfonated polyethylene and 2.0 kg of 1,1,2-trichloroethane were charged in a 4 liter glass flask under a nitrogen atmosphere, 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, and 2.0 g of n-butyraldehyde amine (Noxeller 8 manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) were added. A 7.0 g solution of a dissolved radical initiator (perbutyl O manufactured by Nichiyu Co., Ltd .; t-butyl-peroxy-2-ethylhexanoate) dissolved in 144 g of 1,1,2-trichloroethane was added dropwise over 5 hours. The reaction was carried out. Then, stirring was continued for 1 hour, and the obtained reaction solution was dried in a drum dryer to obtain a modified halogenated polyolefin composition.

The acrylonitrile-2-methoxyethyl acrylate copolymer content of the obtained modified halogenated polyolefin composition was 32.1% by weight, and the acrylonitrile / 2-methoxyethyl acrylate copolymer of the acrylonitrile-2-methoxyethyl copolymer was acrylate. The methoxyethyl ratio was 49/51. Physical characteristics were evaluated using the combination 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.

150 g of chlorosulfonated polyethylene and 2.0 kg of 1,1,2-trichloroethane were charged in a 4 liter glass flask under a nitrogen atmosphere, 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, and 2.0 g of n-butyraldehyde amine (Noxeller 8 manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) were added. A 7.0 g solution of a dissolved radical initiator (perbutyl O manufactured by Nichiyu Co., Ltd .; t-butyl-peroxy-2-ethylhexanoate) dissolved in 288 g of 1,1,2-trichloroethane was added dropwise over 10 hours. The reaction was carried out. Then, stirring was continued for 1 hour, and the obtained reaction solution was dried in a drum dryer to obtain a modified halogenated polyolefin composition.

The acrylonitrile-2-methoxyethyl acrylate copolymer content of the obtained modified halogenated polyolefin composition was 45.1% by weight, and the acrylonitrile / 2-methoxyethyl acrylate copolymer of the acrylonitrile-2-methoxyethyl copolymer was acrylate. The methoxyethyl ratio was 39/61. Physical characteristics were evaluated using the combination 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.

150 g of chlorosulfonated polyethylene and 2.0 kg of 1,1,2-trichloroethane were charged in a 4 liter glass flask under a nitrogen atmosphere, 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, and 2.0 g of n-butyraldehyde amine (Noxeller 8 manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) were added. A 14.0 g solution of a dissolved radical initiator (perbutyl O manufactured by Nichiyu Co., Ltd .; t-butyl-peroxy-2-ethylhexanoate) dissolved in 288 g of 1,1,2-trichloroethane was added dropwise over 10 hours. The reaction was carried out. Then, stirring was continued for 1 hour, and the obtained reaction solution was dried in a drum dryer to obtain a modified halogenated polyolefin composition.

The content of the acrylonitrile-2-methoxyethyl acrylate copolymer of the obtained modified halogenated polyolefin composition was 52.3% by weight, and the acrylonitrile / 2-methoxyethyl acrylate copolymer of the acrylonitrile-2-methoxyethyl acrylate copolymer had a content of 52.3% by weight. The methoxyethyl ratio was 30/70. Physical characteristics were evaluated using the combination 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 Shinko Kagaku Kogyo Co., Ltd.) was not added.

The content of the acrylonitrile-2-methoxyethyl acrylate copolymer of the obtained modified halogenated polyolefin composition was 7.4% by weight, and the polymerization conversion rate of the unsaturated monomer was remarkably low. This is because the 1-hour half-life temperature of the radical initiator was 92.1 ° C., and when the reaction temperature was 65 ° C., the generation of radical species by the decomposition of the radical initiator was insufficient. Therefore, graft selectivity and compounding property 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 Shinko Kagaku Kogyo Co., Ltd.) was not added.

The content of the acrylonitrile-2-methoxyethyl acrylate copolymer of the obtained modified halogenated polyolefin composition was 6.1% by weight, and the polymerization conversion rate of the unsaturated monomer was remarkably low. This is because the 1-hour half-life temperature of the radical initiator was 92.1 ° C., and when the reaction temperature was 65 ° C., the generation of radical species by the decomposition of the radical initiator was insufficient. Therefore, graft selectivity and compounding property evaluation were not performed.

Comparative Example 3
After adding 21.6 kg of 1,1,2-trichloroethane, a density of 960 kg / cm ³ , and a melt flow rate (MFR) of 5.0 g / 10 minutes of high density polyethylene 3 kg to a 40 liter glass-lined autoclave, Steam was passed through the jacket of the reactor to uniformly dissolve the polyethylene at 110 ° C. During this period, nitrogen gas was introduced into the reactor at a flow rate of 10.0 liters / minute to remove the air in the reactor. As a radical generator, a solution of 5.0 g of α, α'-azobisisobutyronitrile in 1.0 liter of 1,1,2-trichloroethane was dissolved in 1.0 liter of 1,1,2-trichloroethane at a flow rate of 4.0 ml / min and 6.5 kg. Sulfuryl chloride was continuously added to the reactor at a flow rate of 25.0 ml / min from different inlets. The pressure in the reactor was maintained at 0.2 MPa during the reaction. After completion of the reaction, the pressure of the reaction system was lowered to normal pressure, and then nitrogen was blown under normal pressure to discharge hydrogen chloride and sulfur dioxide gas dissolved in the solution to the outside of the system. The product was then isolated in a drum dryer to give chlorosulfonated polyethylene.

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

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

200 g of chlorosulfonated polyethylene and 2.0 kg of 1,1,2-trichloroethane were charged in a 4 liter glass flask under a nitrogen atmosphere, 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 (Parloyl manufactured by Nichiyu Co., Ltd.). A solution in which 3.7 g of OPP; di-2-ethylhexyl-peroxydicarbonate) was dissolved was added dropwise over 5 hours to carry out the reaction. Then, stirring was continued for 1 hour, and the obtained reaction solution was dried in a drum dryer to obtain a modified halogenated polyolefin composition.

The acrylonitrile-2-methoxyethyl acrylate copolymer content of the obtained modified halogenated polyolefin composition was 30.2% by weight, and the acrylonitrile / 2-methoxyethyl acrylate copolymer of the acrylonitrile-2-methoxyethyl copolymer was acrylate. The methoxyethyl ratio was 29/71. Physical characteristics were evaluated using the combination 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. The composition was obtained.

The acrylonitrile-2-methoxyethyl acrylate copolymer content of the obtained modified halogenated polyolefin composition was 28.8% by weight, and the acrylonitrile / 2-methoxyethyl acrylate copolymer of the acrylonitrile-2-methoxyethyl copolymer was acrylate. The methoxyethyl ratio was 49/51. Physical characteristics were evaluated using the combination 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 content of the acrylonitrile-2-methoxyethyl acrylate copolymer of the obtained modified halogenated polyolefin composition was 50.2% by weight, and the acrylonitrile / 2-methoxyethyl acrylate copolymer of the acrylonitrile-2-methoxyethyl copolymer of acrylate was 2-methoxyethyl acrylate. The methoxyethyl ratio was 49/51. Physical characteristics were evaluated using the combination formulation of Formulation 2. The evaluation results are shown in Table 3.

Claims (6)

A chlorosulfonated polyolefin dissolved in a chlorine-based organic solvent, acrylonitrile, and one or more acrylic compounds selected from the group consisting of methyl acrylate, ethyl acrylate, 2-methoxyethyl acrylate and n-butyl acrylate. When a unsaturated monomer containing a compound (hereinafter referred to as the acrylic compound) is subjected to a graft reaction using a radical initiator, the graft reaction is characterized in that the graft reaction is carried out in the presence of an aldehyde amine compound. The weight ratio of the acrylonitrile not bonded to the chlorosulfonated polyolefin and the copolymer of the acrylic compound and the component derived from the acrylonitrile and the acrylic compound contained in the graft copolymer is in the range of 3/97 to 70/30. A method for producing a modified chlorosulfonated polyolefin composition. The production of the modified chlorosulfonated polyolefin composition according to claim 1, wherein the amount of the aldehyde amine compound added is 0.5 to 3 times the number of moles of the radical initiator added. Method. The method for producing a modified chlorosulfonated polyolefin composition according to claim 1 or 2 , wherein the method for adding the aldehyde amine compound is to add the entire amount before the start of the graft reaction. Modified chlorosulfonated polyolefin composition, the graft copolymer a copolymer of acrylonitrile chlorosulfonated polyolefin and the acrylic compound is bound, unbound to chlorosulfonated polyolefin acrylonitrile co of the acrylic compound containing polymer, a copolymer of the graft copolymer of acrylonitrile and the acrylic compound in a weight ratio of the copolymer of acrylonitrile not bound to the chlorosulfonated polyolefin and the acrylic compound 30/70 The method for producing a modified chlorosulfonated polyolefin composition according to any one of claims 1 to 3 , which is in the range of ~ 70/30. The total content of the copolymer of the copolymer and acrylonitrile and the acrylic compound in the graft copolymer of the chlorosulfonated polyolefin modified chlorosulfonated polyolefin composition not bound acrylonitrile with the acrylic compound The method for producing a modified chlorosulfonated polyolefin composition according to any one of claims 1 to 4 , wherein the amount is in the range of 20% by weight to 75% by weight. The method for producing a modified chlorosulfonated polyolefin composition according to any one of claims 1 to 5, wherein the acrylic compound is 2-methoxyethyl acrylate.