Patent Application
20240191014
The present invention relates to an ethylene-(meth)acrylate-based elastomer and a method for producing the same. More particularly, the present invention relates to an ethylene-(meth)acrylate-based elastomer that gives a vulcanizate having excellent heat resistance and molding processability, and a method for producing the same.
As a copolymer that gives a vulcanizate having excellent oil and heat resistance, Patent Document 1 has proposed a random copolymer comprising ethylene, methyl acrylate or ethyl acrylate, and 1,4-butenedioic acid monoalkyl ester as monomers. This copolymer is produced by polymerization at high pressure; however, due to the corrosive nature of 1,4-butenedioic acid monoalkyl ester, corrosion-resistant high-pressure equipment is required.
An object of the present invention is to provide an ethylene-(meth)acrylate-based elastomer that can give a vulcanizate having excellent heat resistance, and molding processability and to also provide a method for producing the same.
The above object of the present invention can be achieved by an ethylene-(meth)acrylate-based elastomer having a structure in which 40 to 79.9 mol % of ethylene, 20.0 to 50.0 mol % of an alkyl (meth)acrylate containing an alkyl group having 1 to 8 carbon atoms and/or an alkoxy (meth)acrylate containing an alkoxyalkyl group having 2 to 8 carbon atoms, 0.05 to 20.0 mol % of an unsaturated dicarboxylic acid monosaturated ester, and 0 to 20.0 mol % of an unsaturated dicarboxylic anhydride are copolymerized, and having a monosaturated esterification rate of the acid anhydride of 70% or more as measured by infrared absorption spectroscopy (IR).
The ethylene-(meth)acrylate-based elastomer is produced by subjecting, in a copolymer of ethylene, an alkyl (meth)acrylate containing an alkyl group having 1 to 8 carbon atoms and/or an alkoxy (meth)acrylate containing an alkoxyalkyl group having 2 to 8 carbon atoms, and an unsaturated dicarboxylic anhydride, the unsaturated dicarboxylic anhydride to monosaturated esterification modification treatment.
Vulcanizates obtained from the ethylene-(meth)acrylate-based elastomer according to the present invention have excellent heat resistance, and molding processability, and thus are effectively used as rubber parts in a wide range of fields, such as transportation equipment (such as automobiles), industrial machinery, general equipment, and electrical equipment. Examples of such rubber parts include hoses, and the like, such as O rings, various packings, oil seals, bearing seals, head cover gaskets, plug tube gaskets, engine head cover gaskets, oil filter packings, oil pan gaskets, anti-vibration parts, oil hoses, fuel hoses, air hoses, air duct hoses, turbocharger hoses, PCV hoses, EGR hoses, and intercooler hoses.
As the (meth)acrylate, at least one of an alkyl (meth)acrylate containing an alkyl group having 1 to 8 carbon atoms and an alkoxy (meth)acrylate containing an alkoxyalkyl group having 2 to 8 carbon atoms is used. These can be used singly or in combination of two or more thereof. Here, (meth)acrylate refers to acrylate or methacrylate.
Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, and the like. Alkyl groups having a longer chain length are generally advantageous in terms of cold resistance, but are disadvantageous in terms of oil resistance. Alkyl groups having a shorter chain length show an opposite tendency. In terms of the balance between oil resistance and cold resistance, methyl acrylate, ethyl acrylate and n-butyl acrylate are preferably used. More Preferably, methyl acrylate is used.
Moreover, examples of the alkoxyalkyl (meth)acrylate include methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, n-butoxyethyl (meth)acrylate, ethoxypropyl (meth)acrylate, methoxyethoxyethyl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, and the like.
The unsaturated dicarboxylic anhydride is a compound having one or more radically polymerizable unsaturated bonds and one or more acid anhydride groups in the molecule. Examples thereof include maleic anhydride, citraconic anhydride, itaconic anhydride, 2,3-dimethylmaleic anhydride, 2-(2-carboxyethyl)-3-methylmaleic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, phenylmaleic anhydride, 2,3-diphenylmaleic anhydride, allylsuccinic anhydride, (2-methyl-2-propenyl)succinic anhydride, 2-buten-1-ylsuccinic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride, and the like; preferably, maleic anhydride, itaconic anhydride, and citraconic anhydride are used. These can be used singly or in combination of two or more thereof.
In addition to the above monomers, if necessary, other copolymerizable monomers can also be used as long as the characteristics are not impaired. Examples of such copolymerizable monomers include vinyl compounds, such as styrene, vinyl toluene, α-methylstyrene, vinyl naphthalene, acrylonitrile, methacrylonitrile, acetone acrylamide, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, chloroethyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, pentafluoropropyl (meth)acrylate, and trifluoroethyl (meth)acrylate; diene compounds, such as isoprene, pentadiene, and butadiene; and α-olefins, such as propylene, 1-butene, 1-hexene, and 1-octene. Furthermore, in order to improve kneading processability, extrusion processability, and other properties, a polyfunctional (meth)acrylate or oligomer can be further copolymerized. Examples thereof include di(meth)acrylates of alkylene glycols, such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, and 1,9-nonanediol; di(meth)acrylates, such as neopentyl glycol, tetraethylene glycol, tripropylene glycol, and polypropylene glycol; bisphenol A·ethylene oxide adduct diacrylate, dimethylol tricyclodecane diacrylate, glycerol methacrylate acrylate, 3-acryloyloxyglycerol monomethacrylate, and the like.
Method for producing the copolymer is not particularly limited, and various polymerization methods, such as radical solution polymerization (Patent Documents 2 and 3), can be suitably used. In general, the copolymer can be produced by utilizing high-pressure low-density polyethylene production equipment and technology. For example, the copolymer is produced by a bulk polymerization method at a polymerization pressure of 70 to 350 MPa, preferably 100 to 250 MPa, or by a radical polymerization method at a polymerization temperature of 100 to 300° C., preferably 150 to 270° C. If the polymerization pressure is less than 70 MPa, the molecular weight of the polymer becomes low, and moldability and the resin physical properties of the resin composition deteriorate. In contrast, a polymerization pressure exceeding-350 MPa just increases the production cost and is practically meaningless. Further, if the polymerization temperature is lower than 100° C., the polymerization reaction is not stable, and the conversion rate to the copolymer decreases, which is economically a problem. In contrast, if the polymerization temperature exceeds 300° C., the molecular weight of the copolymer is reduced, and the risk of runaway reactions arises at the same time.
Since radically polymerizable dicarboxylic anhydrides have poor polymerization stability, a high degree of homogenization in the reactor is required. Moreover, if necessary, multiple reactors can be connected in series or in parallel to carry out multistage polymerization. Further, more precise temperature control can be achieved by partitioning the inside of the reactor into multiple zones. It is also possible to adjust the polymerization reaction speed by adjusting the temperature of ethylene subjected to polymerization. The larger the temperature difference from the polymerization temperature is, the faster the polymerization reaction speed gets.
The polymerization reaction is carried out in the presence of at least one free radical polymerization initiator. As the free radical polymerization initiator used in radical polymerization, a compound that generates free radicals is selected. Examples thereof include oxygen; dialkyl peroxides, such as di-tert-butyl peroxide, tert-butyl cumyl peroxide, and dicumyl peroxide; diacyl peroxides, such as acetyl peroxide, isobutyl peroxide, and octanoyl peroxide; peroxydicarbonates, such as diisopropyl peroxydicarbonate and di(2-ethylhexylperoxy)dicarbonate; peroxyesters, such as tert-butyl peroxyisobutyrate, tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, and tert-butyl peroxylaurate; ketone peroxides, such as methyl ethyl ketone peroxide and cyclohexanone peroxide; peroxyketals, such as 1,1-bis-tert-butylperoxycyclohexane and 2,2-bis-tert-butylperoxyoctane; hydroperoxides, such as tert-butyl hydroperoxide and cumene hydroperoxide; azo compounds, such as 2,2-azobisisobutyronitrile; and the like.
The obtained ethylene-(meth)acrylate-based copolymer containing an acid anhydride is subjected to a monosaturated esterification modification treatment using a shear melt-kneading method under shear conditions, preferably using a roll kneader, a closed kneader, or a twin screw extruder.
The monosaturated esterification modification treatment using a shear melt-kneading method is carried out by reacting the ethylene-(meth)acrylate-based copolymer containing an acid anhydride with a saturated alcohol, preferably a primary saturated alcohol, while applying shear using a kneading machine. As the saturated alcohol, one suitable for the equipment used for the modification or for the treatment conditions, such as reaction temperature or catalyst type, is used. Examples thereof include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-butanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 3-methyl-1-butanol, 2-methyl-1-butanol, 2,2-dimethyl-1-propanol, 2-pentanol, 3-methyl-2-butanol, 2-methyl-2-butanol, cyclopentanol, 1-hexanol, 2-methyl-1-pentanol, 2-ethyl-1-butanol, 2-hexanol, 4-methyl-2-pentanol, cyclohexanol, 1-heptanol, 2-heptanol, 1-octanol, 2-ethyl-1-hexanol, methoxymethanol, ethoxymethanol, butoxymethanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, 2-(2-butoxyethoxy)ethanol, 2-[2-(2-methoxyethoxy)ethoxy]ethanol, 2-[2-(2-ethoxyethoxy)ethoxy]ethanol, 2-[2-(2-butoxyethoxy)ethoxy]ethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, and the like. Preferably, 1-butanol, 1-hexanol, or 2-[2-(2-methoxyethoxy)ethoxy]ethanol is used so that (number of moles of alcohol)/(number of moles of copolymerized maleic anhydride) is 1.6 or more. If this value is less than 1.6, the monoesterification rate does not reach 70% or more.
A monosaturated esterification catalyst can be also used to promote the monosaturated esterification. The monosaturated esterification modification treatment can be also performed without using any solvent; however, a small amount of solvent can be also used for the purpose of adjusting fluidity.
As the kneading machine that can be used in the monosaturated esterification modification treatment, for example, a roll kneader, a single screw extruder, a twin screw extruder, a kneader, a roll kneader, a Banbury mixer, a Brabender mixer, a reciprocating kneader (BUSS KNEADER), or the like can be used without limitation. Preferred are a roll kneader, a single screw extruder, a twin screw extruder, and a reciprocating kneader (BUSS KNEADER), which can continuously perform the monosaturated esterification modification treatment and are advantageous in terms of productivity; and more preferred in terms of the versatility of incidental equipment is a roll kneader or a twin screw extruder.
As the monosaturated esterification catalyst, an acid catalyst and a base catalyst can both be used. Examples of the acid catalyst include organic acids, such as benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, and trifluoroacetic acid; mineral acids, such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid; and heteropolyacids, such as heteropolyacids and heteropolyacid salts. Examples of base catalyst include inorganic bases, such as carbonates and hydroxides of alkali metals and alkaline earth metals, aliphatic or aromatic organic bases, fatty acid salts of alkali metals or alkaline earth metals, and the like; preferably, fatty acid salts of alkali metals and organic bases are used. Examples of the fatty acid salt of alkali metal include alkali metal salts of higher fatty acids, such as potassium stearate, potassium laurate, potassium myristate, lithium stearate, and sodium stearate; preferably alkali metal salts, such as potassium stearate and potassium laurate. Examples of the organic base include 1,8-diazabicyclo[5.4.0]undecene-7 or 1,5-diazabicyclo[4.3.0]nonene-5 and salts thereof, amine compounds, such as tertiary amines, imidazole, and the like. The monosaturated esterification catalyst is used at a ratio of about 0.01 to 10 parts by weight, preferably about 0.1 to 5 parts by weight, based on 100 parts by weight of the ethylene-(meth)acrylate-based copolymer. By the monosaturated esterification modification treatment, the dicarboxylic anhydride is converted to a monosaturated ester.
In addition, Patent Document 4 indicates that when an ethylene-alkyl (meth)acrylate-maleic anhydride-maleic acid ester quaternary copolymer is modified with an unsaturated amine or unsaturated alcohol, a half ester copolymer of maleic acid is performed by kneading with Labo Plastomill.
It is described that regarding the hydrolysis reaction or half-esterification reaction of the raw material terpolymer, the hydrolysis reaction is carried out in an organic solvent in the presence of a catalyst, such as a tertiary amine salt, and the half-esterification reaction is carried out by a similar solution or melting method and in the melting method kneading machines, such as Banbury mixers and extruders, are used; however, the solution method is used in all the examples.
After the monosaturated esterification modification treatment, an aging treatment is preferably performed in order to improve the monosaturated esterification rate. The aging temperature is about 0 to 100° C., and the aging time is suitably set depending on the aging temperature. For example, at room temperature of 23° C., the aging time is set to 1 day or more. If the aging temperature rises, it is possible to shorten the aging time according to the temperature rise; however, from an economic point of view, aging at room temperature is adopted.
Among the monosaturated esterification modification treated ethylene-(meth)acrylate-based elastomers, in terms of obtaining a vulcanizate having excellent heat resistance and molding processability, one having a structure in which 40 to 79.9 mol % of ethylene, 20.0 to 50.0 mol % of an alkyl (meth)acrylate containing an alkyl group having 1 to 8 carbon atoms and/or an alkoxy (meth)acrylate containing an alkoxyalkyl group having 2 to 8 carbon atoms, 0.05 to 20.0 mol % of an unsaturated dicarboxylic acid monosaturated ester, and 0 to 20.0 mol % of an unsaturated dicarboxylic anhydride are copolymerized, and having a monosaturated esterification rate of the acid anhydride measured by IR of 70% or more is selected. This elastomer is compounded with a vulcanizing agent to prepare an ethylene-(meth)acrylate-based elastomer composition.
If one having the monosaturated esterification rate of the acid anhydride measured by IR of less than 70% is used, the mixture of a composition obtained by compounding this with a vulcanizing agent has large ML min (125° C.) and short t5; therefore, it cannot be molded into a molded product. Further, the esterification rate measured by IR is calculated from the peak ratio (A1855/A4254) using a calibration curve of the IR absorbance ratio.
As the vulcanizing agent for the ethylene-(meth)acrylate-based elastomer, an amine-based vulcanizing agent or an organic peroxide crosslinking agent can be used.
Examples of the amine-based vulcanizing agents include aliphatic polyvalent amine compounds, such as hexamethylenediamine, hexamethylenediamine carbamate, N,N′-dicinnamylidene-1,6-hexanediamine, 4,4′-bis(aminocyclohexyl)methane, ethylenediamine, ethylenediamine carbamate, cyclohexanediamine, bis(hexamethylene)triamine, 3,3′-diaminopropylamine, cyclohexanetriamine, hexamethylenediamine-cinnamaldehyde adduct, hexamethylenediamine benzoate, and diamino-modified siloxane; alicyclic polyamine compounds, such as 4,4′-methylenebiscyclohexylamine, bis(4-amino-3-methyldicyclohexyl)methane, and 4,4′-methylenebiscyclohexylamine-cinnamaldehyde adduct; aromatic polyamine compounds, such as N,N′-dicinnamylidene-1,6-hexanediamine, 4,4′-(α,α-dimethylbenzyl)diphenylamine, 4,4′-methylenedianiline, m-phenylenediamine, 4,4′-diaminodiphenyl ether, p-phenylenediamine, p,p′-ethylenedianiline, 4,4′-(p-phenylenediisopropylidene)dianiline, 4,4′-(m-phenylenediisopropylidene)dianiline, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4′-bis(4-aminophenoxy)biphenol, bis[4-(4-aminophenoxy)phenyl]ether, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, m-xylylenediamine, p-xylylenediamine, 1,3,5-benzenetriamine, and 4,4′-diaminobenzanilide; and the like. Further, an aliphatic polyvalent amine with an amino group protected by an organic group can also be used.
The diurethane compound disclosed in Patent Document 5 etc. represented by the general formula:
R2(SO2)m(CH2)nOCONHR1NHCOO(CH2)n(SO2)mR2
(wherein R1 is a C1-C20 linear or branched divalent aliphatic alkylene group, a divalent alicyclic hydrocarbon group, or a divalent aromatic group; R2 is a group that can be decomposed by the action of a basic vulcanization accelerator to generate diamine when it has a carbamate structure, a C1-C20 alkyl group, an alkoxyl group, a phenoxy group, a haloalkyl group, an olefinic group, an aryl group or an aralkyl group, a fluorenyl-containing group, an S-containing group, an Si-containing group, an N-containing group, or a P-containing group, wherein the S-containing group or N-containing group is an aromatic or alicyclic heterocyclic group; n is 0, 1, or 2; and m is 0 or 1), preferably a diurethane compound obtained by di-substituting the amino group of alkylenediamine represented by the general formula H2N(CH2)lNH2 (l=4 to 6) with 9-fluorenylmethyl chloroformate [Fmoc], more preferably a diurethane compound [HMDA-Fmoc] obtained by di-substituting the amino group of hexamethylenediamine (l=6), i.e.
can also be used.
Such a polyamine compound vulcanizing agent is used at a ratio of about 0.1 to 5 parts by weight, preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the ethylene-(meth)acrylate-based elastomer. If the compounding amount of the vulcanizing agent is less than this range, vulcanization is insufficient, which leads to deterioration of the mechanical properties of the vulcanizate and decrease of the vulcanization rate. If the compounding amount of the vulcanizing agent is greater than this range, excessive vulcanization may progress to reduce the elasticity of the vulcanizate. In the vulcanization, a basic vulcanization accelerator, a thiuram-based crosslinking accelerator and a thiourea-based crosslinking accelerator are used in combination at a ratio of about 0.5 to 5 parts by weight, preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the ethylene-(meth)acrylate-based elastomer.
As the basic vulcanization accelerator, guanidine compounds or diazabicycloalkene compounds, such as 1,8-diazabicyclo[5.4.0]undecene-7 and 1,5-diazabicyclo[4.3.0]nonene-5, or organic acid salts or inorganic acid salts thereof are used. From the viewpoint of ahigher addition effect, 1,8-diazabicyclo[5.4.0]undecene-7[DBU] is preferably used. Moreover, a mixture of 1,8-diazabicyclo[5.4.0]undecene-7 and silica can also be used. In practice, for example, Vulcofac ACT55, produced by Safic Alcan and the like are used.
Examples of the compound that forms an organic acid salt or inorganic acid salt of the diazabicycloalkene compound include hydrochloric acid, sulfuric acid, carboxylic acid, sulfonic acid, phenol, and the like. Examples of the carboxylic acid include octylic acid, oleic acid, formic acid, orthophthalic acid, adipic acid, and the like. Further, examples of the sulfonic acid include benzenesulfonic acid, toluenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, and the like. These can be used singly or in combination of two or more thereof.
Usable examples of the guanidine compound include guanidine or substituted guanidine, such as aminoguanidine, 1,1,3,3-tetramethylguanidine, n-dodecylguanidine, methylolguanidine, dimethylolguanidine, 1-phenylguanidine, 1,3-diphenylguanidine, 1,3-di-o-tolylguanidine, triphenylguanidine, 1-benzyl-2,3-dimethylguanidine, cyanoguanidine, and the like. In addition, 1,6-guanidinohexane, guanylurea, biguanide, 1-o-tolylbiguanide, and the like can also be used.
Examples of the thiuram-based compound include tetramethylthiuram disulfide and the like, and examples of the thiourea-based compound include N,N′-diphenylthiourea and the like.
Examples of the organic peroxide include di-tert-butyl peroxide, dicumyl peroxide, di-tert-butyl cumyl peroxide, 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexin-3, 1,3-di(tert-butylperoxydiisopropyl)benzene, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, tert-butylperoxybenzoate, tert-butylperoxy isopropyl carbonate, n-butyl-4,4-di(tert-butylperoxy)valerate, and the like. Such an organic peroxide is used at a ratio of about 0.2 to 10 parts by weight, preferably about 0.75 to 2 parts by weight, based on 100 parts by weight of the ethylene-(meth)acrylate-based elastomer.
For the peroxide crosslinkable composition, a crosslinking aid for peroxide crosslinking comprising polyfunctional unsaturated compounds is preferably used in combination. Usable examples of the polyfunctional unsaturated compounds include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, triallyl(iso)cyanurate, trimethylolpropane tri(meth)acrylate, triallyl trimellitate, and bismaleimide compounds (e.g., N,N′-m-phenylenebismaleimide, N,N′-p-phenylenebismaleimide, N,N′-p-phenylene-(1-methyl)bismaleimide, N,N′-2,7-naphthalenebismaleimide, N,N′-m-phenylene-4-methylbismaleimide, and N,N′-m-phenylene(4-ethyl)bismaleimide). Preferably, N,N′-m-phenylenedimaleimide is used at a ratio of about 0.2 to 15 parts by weight, preferably about 1 to 10 parts by weight, based on 100 parts by weight of the copolymer.
To the ethylene-(meth)acrylate-based elastomer, if necessary, various additives, such as reinforcing agents, fillers, processing aids, plasticizers, softeners, antioxidants, coloring agents, stabilizers, adhesive aids, mold release agents, conductivity-imparting agents, thermal conductivity-imparting agents, surface non-adhesive agents, tackifiers, flexibility-imparting agents, heat resistance-improving agents, flame retardants, ultraviolet absorbers, oil resistance-improving agents, anti-scorching agents, and lubricants are appropriately added to be used.
Examples of the reinforcing agent and filler include silica, such as basic silica and acidic silica; metal oxides, such as magnesium oxide, zinc oxide, calcium oxide, titanium oxide, and aluminum oxide; metal hydroxides, such as magnesium hydroxide, aluminum hydroxide, and calcium hydroxide; metal carbonates, such as magnesium carbonate, aluminum carbonate, calcium carbonate, and barium carbonate; silicates, such as magnesium silicate, calcium silicate, sodium silicate, and aluminum silicate; sulfates, such as aluminum sulfate, calcium sulfate, and barium sulfate; synthetic hydrotalcite; metal sulfides, such as molybdenum disulfide, iron sulfide, and copper sulfide; diatomaceous earth, asbestos, lithopone (zinc sulfide/barium sulfide), graphite, carbon black (MT carbon black, SRF carbon black, FEF carbon black, HAF carbon black, etc.), fluorinated carbon, calcium fluoride, coke, quartz fine powder, zinc white, talc, mica powder, wollastonite, carbon fiber, aramid fiber, various whiskers, glass fiber, organic reinforcing agents, organic fillers, and the like.
Examples of the antioxidant include amine-based antioxidants, such as phenyl-α-naphthylamine, phenyl-β-naphthylamine, p-(p-toluenesulfonylamide)-diphenylamine, 4,4′-(α,α-dimethylbenzyl)diphenylamine, N,N-diphenyl-p-phenylenediamine, N-isopropyl-N′-phenyl-p-phenylenediamine, and butylaldehyde-aniline condensates; phenol antioxidants, such as styrenated phenols such as 2,6-di-tert-butylphenol, butylhydroxyanisole, 2,6-di-tert-butyl-α-dimethylamino-p-cresol, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and mono, di or tri (α-methylbenzyl)phenol, 2,2′-methylene-bis(6-α-methylbenzyl-p-cresol), 4,4′-methylenebis(2,6-di-tert-butylphenol), 2,2′-methylenebis(4-methyl-6-tert-butylphenol), alkylated bisphenol, butylated reaction products of p-cresol and dicyclopentadiene, 1,3,5-tris(3′,5′-di-tert-butyl-4′-hydroxybenzyl)isocyanurate, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, butylidenebis(methyl-butylphenol), n-octadecyl 3-(4′-hydroxy-3′,5′-di-tert-butylphenyl)propionate, pentaerythritol tetrakis[3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl)propionate], 2,2′-dimethyl-2,2′-(2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diyl)dipropane-1,1′-diylbis[3-(tert-butyl-4-hydroxy-5-methylphenyl)propanoate], 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, and 2,6-di-tert-butyl-4-methylphenol; phosphite-based antioxidants, such as 3,9-dioctadecan-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 2,4,8,10-tetra-tert-butyl-6-[(2-ethylhexan-1-yl)oxy]-12H-dibenzo[d,g][1,3,2]dioxaphosphosine, tris(2,4-di-tert-butylphenyl)phosphite, trisnonylphenyl phosphite, 2-ethylhexyl diphenyl phosphite, diphenyl isodecyl phosphite, triisodecyl phosphite, and triphenyl phosphite; other thiophenol-based antioxidants, sulfur ester-based antioxidants, imidazole-based antioxidants, quinoline-based antioxidants, hydroquinone-based antioxidants, and the like. These antioxidants can be used singly or in combination of two or more thereof.
Examples of the processing aid include higher fatty acids, such as stearic acid, oleic acid, palmitic acid, and lauric acid; higher fatty acid salts, such as sodium stearate and zinc stearate; higher fatty acid amides, such as amide stearate and amide oleate; higher fatty acid esters, such as ethyl oleate; petroleum-based waxes, such as carnauba wax and ceresin wax; polyglycols, such as ethylene glycol, glycerol, and diethylene glycol; aliphatic hydrocarbons, such as vaseline and paraffin; silicone-based oils, silicone-based polymers, low-molecular-weight polyethylene, phthalic acid esters, phosphoric acid esters, rosin, (halogenated) dialkyl amine, (halogenated) dialkyl sulfone, surfactants, and the like.
Examples of the plasticizer include epoxy resin and derivatives of phthalic acid and sebacic acid, and the like. Examples of the softener include lubricating oil, process oil, coal tar, castor oil, and calcium stearate, and the like.
The preparation of the composition is carried out by adding a reinforcing agent, a stabilizer, a processing aid, and the like to the ethylene-(meth)acrylate-based elastomer using an open roll or a closed kneader and thereafter further adding a vulcanizing agent and a vulcanization accelerator. Vulcanization molding is carried out by performing primary vulcanization at about 150 to 200° C. for about 1 to 30 minutes, optionally followed by oven vulcanization (secondary vulcanization) at about 150 to 200° C. for about 1 to 16 hours. For molding, known methods, such as press molding, transfer molding, injection molding, and extrusion molding, can be applied depending on the product.
The following describes the present invention with reference to Examples.
In Polymerization Example 1, high-pressure method low-density polyethylene plant equipment with a 5 L autoclave was used, and monomers were injected into a reactor where the monomer composition at the reactor inlet was 89.7 wt % of ethylene, 10.1 wt % of methyl acrylate, and 0.19 wt % of maleic anhydride. Di-(2-ethylhexyl peroxy)dicarbonate was used as a reaction initiator, and the polymerization was carried out under the conditions of a polymerization temperature of 165° C. (only Polymerization Example 4 at 155° C.) and a polymerization pressure of 140 MPa (only Polymerization Example 4 at 170 MPa). In other production examples, various copolymers shown in Table 1 were obtained by adjusting the monomer composition, polymerization temperature, and polymerization pressure.
Here, the copolymerization composition (mol %) of the terpolymer was calculated from the main monomer composition ratio (MA/E) and the MAH content.
Using each of the above components, a monosaturated esterification modification treatment was carried out using a roller blade closed kneader (Labo Plastomill R100, produced by Toyo Seiki Seisaku-sho, Ltd.) with a capacity of 100 ml in the following manner.
First, the kneader was preheated to 80 to 90° C., the polymer and the modification catalyst were supplied, and mastication was carried out at a rotation speed of 30 rpm for 2 minutes. Next, a specified amount of the alcohol was supplied, and the mixture was kneaded at a rotation speed of 30 rpm for 15 minutes and then discharged. Further, the discharged copolymer was cut into small pieces about 2 to 3 cm, followed by vacuum drying at a temperature of 60° C. for 24 hours. The pressure at this time was −0.1 MPa (pressure display of the vacuum dryer). The alcohol/MAH molar ratio was calculated by the following calculation formula using the amount of the saturated alcohol used in modification and the MAH content of the terpolymer.
Amount of Alcohol (Mol/100 g Copolymer)/MAH Content (Mol/100 g Copolymer) of Terpolymer
[(MAH content (mol %) of terpolymer−MAH content (mol %) after modification]/(MAH content (mol %) of terpolymer]×100
The cold resistance of the obtained monosaturated esterification modification treated copolymer was measured using MFR (melt flow rate; according to JIS K-7210 corresponding to ISO 1133, 190° C., 2.16 kg) and DSC. For DSC, using DSC6220 produced by SII, the temperature was raised from −100° C. to 100° C. at a heating rate of 10° C./min, and the temperature at which the differential peak of the DSC curve was obtained was regarded as Tg.
Each of the above components was kneaded using an 8 inch roll (produced by Otake Kikai Kogyo K.K.), thereby producing a composition for evaluating rubber physical properties. The obtained kneaded composition was subjected to primary vulcanization at 180° C. for 10 minutes and oven vulcanization (secondary vulcanization) at 175° C. for 4 hours, thereby molding a vulcanization sheet and a block for measuring compression set according to JIS.
The obtained composition and molded product were measured for each of the following items.
In Example 1, the amount of 1-butanol used in the monosaturated esterification modification treatment in the step (1) was changed to 12 parts by weight (alcohol/MAH molar ratio: 3.77).
In Example 1, the amount of 1-butanol used in the monosaturated esterification modification treatment in the step (1) was changed to 4 parts by weight (alcohol/MAH molar ratio: 1.25).
In Example 1, the monosaturated esterification modification treatment in the step (1) was not performed.
The results obtained in Examples 1 and 2, and Comparative Example 1 are shown in the following Table 2. However, in Comparative Example 1, the vulcanization sheet and the block for compression set could not be molded due to the large ML min and short t5 of the kneaded material, and the physical properties of the molded product could not be measured. Further, in Comparative Example 2, compound burning occurred during kneading, and the characteristics could not be measured.
In Example 1, the same amount (100 parts by weight) of the terpolymer obtained in Polymerization Example 2 was used as the terpolymer, and 18 parts by weight (alcohol/MAH molar ratio: 6.88) of 1-hexanol (b.p.: 157° C., Mw: 102.17) and 2.5 parts by weight of potassium laurate were used in the monosaturated esterification modification treatment in the step (1).
In Example 3, the amount of 1-hexanol used in the monosaturated esterification modification treatment in the step (1) was changed to 9 parts by weight (alcohol/MAH molar ratio: 3.44).
In Example 3, the amount of 1-hexanol used in the monosaturated esterification modification treatment in the step (1) was changed to 27 parts by weight (alcohol/MAH molar ratio: 10.33).
In Example 3, the amount of 1-hexanol used in the monosaturated esterification modification treatment in the step (1) was changed to 4 parts by weight (alcohol/MAH molar ratio: 1.53).
In Example 3, the monosaturated esterification modification treatment in the step (1) was not performed.
The results obtained in Examples 3 to 5 and Comparative Example 3 are shown in the following Table 3. However, in Comparative Example 3, the vulcanization sheet and the block for compression set could not be molded due to the large ML min and short t5 of the kneaded material, and the physical properties of the molded product could not be measured. Further, in Comparative Example 4, compound burning occurred during kneading, and the characteristics could not be measured.
In Example 3, the same amount (100 parts by weight) of the terpolymer (alcohol/MAH molar ratio: 9.45) obtained in Polymerization Example 3 was used as the terpolymer, a 1 L kneader (DS1-5MHB-E, produced by Moriyama) was used as the closed kneader for use in the monosaturated esterification modification treatment in the step (1), and potassium laurate was not used. Further, in the step (2), each of the components other than hexamethylenediamine carbamate (CHEMINOX AC-6) and DBU-dodecane dihydrochloride was kneaded using the 1 L kneader (DS1-5MHB-E, produced by Moriyama). Subsequently, using an 8 inch open roll (produced by Otake Kikai Kogyo K.K.), 1.2 parts by weight of hexamethylenediamine carbamate and 2 parts by weight of DBU-dodecane dihydrochloride (70% product) were compounded, followed by kneading, thereby producing a composition for evaluating rubber physical properties. The obtained kneaded composition was subjected to primary vulcanization at 180° C. for 10 minutes and oven vulcanization (secondary vulcanization) at 175° C. for 4 hours, thereby molding a vulcanization sheet and a block for measuring compression set according to JIS.
In Example 6, in the monosaturated esterification modification treatment in the step (1), 3 parts by weight of potassium laurate 50% master batch (metal soap product) was further used.
In Example 6, in the monosaturated esterification modification treatment in the step (1), 2 parts by weight of dimethylstearylamine (Farmin DM8098, produced by Kao Corporation) was further used.
In Example 6, in the monosaturated esterification modification treatment in the step (1), 1 parts by weight of 1,8-diazabicyclo[5.4.0]-7-undecene (DBU produced by San-Apro Ltd.) was further used.
In Example 6, in the monosaturated esterification modification treatment in the step (1), 3.3 parts by weight of dimethylstearylamine (Farmin D86, produced by Kao Corporation) was further used.
In Example 6, the monosaturated esterification modification treatment in the step (1) was not performed.
The results obtained in Examples 6 to 10 are shown in the following Table 4. However, in Comparative Example 5, compound burning occurred during kneading, and the characteristics could not be measured.
In Example 1, a 1 L kneader (DS1-5MHB-E, produced by Moriyama) was used as the closed kneader for use in the monosaturated esterification modification treatment, and the same amount (100 parts by weight) of a product obtained by drying the monosaturated esterification modification treated copolymer obtained in Polymerization Example 4 (alcohol/MAH molar ratio: 5.67) and then storing at 23° C. and 50% RH (relative humidity) for 4 weeks was used as the terpolymer. Moreover, the monoesterification rate was measured not only at the completion of drying, but also at 1-week and 4-week storage under the conditions of 23° C. and 50% RH (relative humidity) in order to confirm changes in the esterification rate due to aging.
In Example 11, 9 parts by weight of 1-hexanol (alcohol/MAH molar ratio: 6.17) and 2.5 parts by weight of potassium laurate were used in the monosaturated esterification modification treatment in the step (1).
In Example 11, 7 parts by weight of 2-[2-(2-methoxyethoxy)ethoxy]ethanol (Mw: 164.2) (alcohol/MAH molar ratio: 2.99) and 2 parts by weight of DBU-octylate (U-CAT SA102, produced by Safic-Alcan) were used in the monosaturated esterification modification treatment in the step (1).
The results obtained in Examples 11 to 13 are shown in the following Table 5.
In Example 11, in the monosaturated esterification modification treatment of the step (1), 18 parts by weight of 1-hexanol (alcohol/MAH molar ratio: 12.34) was used. Further, in the step (2), hexamethylenediamine carbamate and DBU-dodecane dihydrochloride were not used.
In Example 14, in the monosaturated esterification modification treatment in the step (1), 1 part by weight of 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) was further used.
The results obtained in Examples 14 and 15 are shown in the following Table 6.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2021-045929 | Mar 2021 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2022/012517 | 3/18/2022 | WO |
