WO2013094767A1 - エチレン‐α‐オレフィン‐非共役ポリエン共重合体 - Google Patents
エチレン‐α‐オレフィン‐非共役ポリエン共重合体 Download PDFInfo
- Publication number
- WO2013094767A1 WO2013094767A1 PCT/JP2012/083375 JP2012083375W WO2013094767A1 WO 2013094767 A1 WO2013094767 A1 WO 2013094767A1 JP 2012083375 W JP2012083375 W JP 2012083375W WO 2013094767 A1 WO2013094767 A1 WO 2013094767A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ethylene
- olefin
- weight
- unit
- norbornene
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/905—Polymerization in presence of transition metal containing catalyst in presence of hydrogen
Definitions
- the present invention relates to an ethylene- ⁇ -olefin-nonconjugated polyene copolymer.
- radiator hose for cooling the engine
- drain hose for radiator overflow
- heater hose for indoor heating
- air conditioning drain hose wiper water hose
- roof drain hose for outdoor heating
- rubber hoses such as lactose hose are attached.
- raw material rubbers used for rubber hoses for example, Japanese Patent Application Laid-Open No. 2004-285324 and Japanese Patent Application Laid-Open No. 2011-174002 describe ethylene- ⁇ -olefin-nonconjugated polyene copolymers.
- the conventional ethylene- ⁇ -olefin-nonconjugated polyene copolymer has a roll kneading processability when the polymer and auxiliary materials are roll kneaded to prepare a polymer composition, and the polymer composition. Both were not fully satisfied with the extrudability at the time of extrusion molding into a molded body such as a hose. Under such circumstances, the problem to be solved by the present invention is to provide an ethylene- ⁇ -olefin-nonconjugated polyene copolymer excellent in roll kneading processability and extrusion processability.
- the present invention is an ethylene- ⁇ -olefin-nonconjugated polyene copolymer containing an ethylene unit, an ⁇ -olefin unit, and a nonconjugated polyene unit, which has the following requirements (A), (B), (C), (D ) And (E).
- An ethylene- ⁇ -olefin-nonconjugated polyene copolymer is satisfied.
- the present invention relates to an ethylene- ⁇ -olefin-nonconjugated polyene copolymer comprising an ethylene unit, an ⁇ -olefin unit and a nonconjugated polyene unit.
- the term “monomer name + unit” such as “ethylene unit”, “ ⁇ -olefin unit” and “non-conjugated polyene unit” means “monomer unit based on the monomer”.
- the ⁇ -olefin of the ethylene- ⁇ -olefin-nonconjugated polyene copolymer is preferably an ⁇ -olefin having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 1 -Linear ⁇ -olefins such as heptene, 1-octene, 1-nonene, 1-decene; branched such as 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene
- An ⁇ -olefin is exemplified. One or more of these are used.
- the ⁇ -olefin is preferably propylene or 1-butene, more preferably propylene.
- non-conjugated polyene of the ethylene- ⁇ -olefin-non-conjugated polyene copolymer examples include 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, and 6-methyl-1,5.
- non-conjugated dienes such as heptadiene and 7-methyl-1,6-octadiene; cyclohexadiene, dicyclopentadiene, methyltetraindene, 5-vinyl-2-norbornene, 5- (2-propenyl) -2-norbornene 5- (3-butenyl) -2-norbornene, 5- (4-pentenyl) -2-norbornene, 5- (5-hexenyl) -2-norbornene, 5- (5-heptenyl) -2-norbornene, 5 -(7-octenyl) -2-norbornene, 5-methylidene-2-norbornene, 5-ethylidene-2-norbornene, 5 Cyclic non-conjugated dienes such as propylidene-2-norbornene, 5-butylidene-2-norbornene, 6-chloromethyl-5
- the non-conjugated polyene is preferably 5-alkylidene-2-norbornene such as 5-methylidene-2-norbornene, 5-ethylidene-2-norbornene, 5-propylidene-2-norbornene, 5-butylidene-2-norbornene; 5-vinyl-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (3-butenyl) -2-norbornene, 5- (4-pentenyl) -2-norbornene, 5- (5-hexenyl) ) -2-norbornene, 5- (5-heptenyl) -2-norbornene, 5- (7-octenyl) -2-norbornene and the like are preferable, and 5-alkylidene-2-norbornene is more preferable. preferable.
- 5-alkylidene-2-norbornene such as 5-methylidene-2
- the ⁇ -olefin is propylene
- the nonconjugated polyene is selected from a compound group consisting of 5-alkylidene-2-norbornene and 5-alkenyl-2-norbornene.
- a copolymer that is at least one compound is preferred.
- Examples of the ethylene- ⁇ -olefin-nonconjugated polyene copolymer include ethylene-propylene-5-ethylidene-2-norbornene copolymer, ethylene-propylene-dicyclopentadiene copolymer, and ethylene-propylene-5-vinyl.
- the intrinsic viscosity [ ⁇ ] of the ethylene- ⁇ -olefin-nonconjugated polyene copolymer is 0.5 dl / g or more and 1.8 dl / g or less.
- the intrinsic viscosity [ ⁇ ] is preferably 1.0 dl / g or more, more preferably 1.3 dl / g or more, and further preferably 1.4 dl / g in order to improve roll kneading processability. .
- it is preferably 1.7 dl / g or less.
- the intrinsic viscosity [ ⁇ ] is measured at 135 ° C. in tetralin.
- the ethylene- ⁇ -olefin-nonconjugated polyene copolymer has an ethylene-based monomer unit (ethylene unit) content of 50 mol% to 90 mol%, and an ⁇ -olefin-based monomer unit ( ⁇ -olefin).
- the content of (unit) is 10 mol% or less and 50 mol% or more.
- the ethylene unit content is preferably 55 mol% or more, the ⁇ -olefin unit content is 45 mol% or less, and more preferably, the ethylene unit content is 58 mol%.
- the content of ⁇ -olefin units is 42 mol% or less, more preferably the content of ethylene units is 60 mol% or more, and the content of ⁇ -olefin units is 40 mol% or less.
- the ethylene unit content is preferably 80 mol% or less, the ⁇ -olefin unit content is 20 mol% or more, and more preferably, the ethylene unit content is 75 mol%.
- the content of ⁇ -olefin units is 25 mol% or more, more preferably the content of ethylene units is 70 mol% or less, and the content of ⁇ -olefin units is 30 mol% or more.
- the total of the ethylene unit content and the ⁇ -olefin unit content is 100 mol%.
- the content of ethylene units and the content of ⁇ -olefin units are measured by infrared spectrophotometry.
- the iodine value (unit: g / 100 g polymer) of the ethylene- ⁇ -olefin-nonconjugated polyene copolymer is 1 or more and 50 or less.
- the iodine value is preferably 5 or more, more preferably 10 or more, and more preferably 12 or more in order to improve roll kneading processability.
- it is 40 or less, More preferably, it is 35 or less, More preferably, it is 30 or less.
- the ratio of tan ⁇ at 100 ° C. and 2 cpm to tan ⁇ at 100 ° C. and 1000 cpm of the ethylene- ⁇ -olefin-nonconjugated polyene copolymer, ie tan ⁇ (100 ° C., 2 cpm) / tan ⁇ (100 ° C., 1000 cpm)) is 1.0 or more and 1.7 or less.
- the ratio is preferably 1.6 or less, and more preferably 1.5 or less, in order to improve the extrusion processability.
- tan ⁇ is the ratio of the shear loss modulus to the shear storage modulus (shear loss modulus / shear storage modulus), and is measured by a viscoelasticity measuring device at a temperature of 100 ° C. and a strain of 13.95%.
- the ratio of the Z-average molecular weight (Mz) to the number average molecular weight (Mn) of the ethylene- ⁇ -olefin-nonconjugated polyene copolymer, that is, Mz / Mn is 15 or more and 25 or less.
- Mz / Mn is preferably 17 or more in order to improve roll kneading processability, and preferably 22 or less in order to improve extrusion processability.
- Z-average molecular weight (Mz) and number average molecular weight (Mn) are measured by gel permeation chromatography (GPC).
- the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the ethylene- ⁇ -olefin-nonconjugated polyene copolymer, that is, Mw / Mn is 3 or more and 5 or less. Mw / Mn is preferably 4 or more in order to improve roll kneading processability.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured by a gel permeation chromatography (GPC) method.
- a polymerization catalyst using a vanadium compound and an organoaluminum compound as a polymerization catalyst component is used in a hydrocarbon compound solvent under the following conditions (a ), (B) and (c), and a method of copolymerizing ethylene, ⁇ -olefin and non-conjugated polyene.
- the polymerization temperature is 50 to 80 ° C.
- the amount of hydrogen supplied to the polymerization reactor is 0.001 to 0.1 NL per 1 kg of the solvent supplied to the polymerization reactor.
- the amount of the vanadium compound supplied to the polymerization reactor is 0.02 to 0.2 parts by weight per 100 parts by weight of the solvent supplied to the polymerization reactor.
- vanadium compound in the production process examples include VOCl 3, VO (OCH 3 ) 0.5 Cl 2.5, VO (OC 2 H 5) 0.5 C l2.5, VO (O (n-C 3 H 7 )) 0.5 Cl 2.5 , VO (O (n-C 4 H 9 )) 0.5 Cl 2.5 , VO (O (n-C 5 H 11 )) 0.5 Cl 2.5 , VO (O (n-C 6 H 13) ) 0.5 Cl 2.5 , VO (O (n—C 7 H 15 )) 0.5 Cl 2.5 , VO (O (n—C 8 H 17 )) 0.5 Cl 2.5 , VO (OCH 3) 0.8 Cl 2.2, VO (OC 2 H 5) 0.8 Cl 2.2, VO (O (n-C 3 H 7)) 0.8 Cl 2.2, VO (O (n-C 4 H 9) ) 0.8 Cl 2.2, VO (O (n-C 5 H 11)) 0.8 Cl 2.2, VO (O (n-
- VOCl 3 , VO (OC 2 H 5 ) 0.5 Cl 2.5 , VO (OC 2 H 5 ) 0.8 Cl 2.2 , VO (OC 2 H 5 ) Cl 2 , VO (OC 2 VO (OC 2 H 5 ) r Cl s such as H 5 ) 1.5 Cl 0.5 wherein r and s are numbers satisfying r + s 3, 1 ⁇ r ⁇ 3 and 0 ⁇ s ⁇ 2. It is. And more preferably VOCl 3 .
- organoaluminum compound in the above production method examples include (C 2 H 5 ) 2 AlCl, (n-C 4 H 9 ) 2 AlCl, (iso-C 4 H 9 ) 2 AlCl, and (n-C 6 H 13 ) 2.
- AlCl, (C 2 H 5 ) 1.5 AlCl 1.5 , (n-C 4 H 9 ) 1.5 AlCl 1.5 , (iso-C 4 H 9 ) 1.5 AlCl 1.5 , (n -C 6 H 13) 1.5 AlCl 1.5 , C 2 H 5 AlCl 2, (n-C 4 H 9) AlCl 2, (iso-C 4 H 9) AlCl 2, (n-C 6 H 13 ) R t AlCl u such as AlCl 2 [wherein R represents an alkyl group having 1 to 10 carbon atoms, and t and u satisfy t + u 3, 0 ⁇ t ⁇ 3 and 0 ⁇ u ⁇ 3 Is a number.
- the polymerization catalyst is preferably a catalyst obtained by contacting a vanadium compound and an organoaluminum compound in the absence of alcohol.
- hydrocarbon compound used for the solvent examples include aliphatic hydrocarbon compounds such as propane, butane, isobutane, pentane, hexane, heptane, and octane; and alicyclic hydrocarbon compounds such as cyclopentane and cyclohexane.
- the molar ratio of the amount of the organoaluminum compound used to the amount of the vanadium compound used is preferably 0.1 to 2.0, more preferably 0.8. It is 5 to 1.8, and more preferably 0.8 to 1.7.
- tan ⁇ 100 ° C., 2 cpm
- tan ⁇ 100 ° C., 1000 cpm
- Mz / Mn and Mw / Mn it is preferable to decrease the molar ratio.
- the polymerization temperature is preferably 50 to 80 ° C., more preferably 55 to 60 ° C. In order to reduce tan ⁇ (100 ° C., 2 cpm) / tan ⁇ (100 ° C., 1000 cpm), or to increase Mz / Mn and Mw / Mn, it is preferable to increase the polymerization temperature.
- the polymerization pressure is usually 0.1 to 10 MPa, preferably 0.1 to 5 MPa, more preferably 0.1 to 3 MPa.
- the amount of hydrogen supplied to the polymerization reactor is preferably 0.001 to 0.1 NL, more preferably 0.005 to 0.05 NL, even more preferably, per 1 kg of the solvent supplied to the polymerization reactor. Is 0.01 to 0.04 NL. In order to increase Mz / Mn or increase the intrinsic viscosity [ ⁇ ], it is preferable to reduce the supply amount of the hydrogen.
- the amount of the vanadium compound supplied to the polymerization reactor is preferably 0.02 to 0.2 parts by weight, more preferably 0.03 to 0.1 parts per 100 parts by weight of the solvent supplied to the polymerization reactor. Parts by weight.
- the ethylene- ⁇ -olefin-nonconjugated polyene copolymer of the present invention is suitably used as a material for vulcanized rubber.
- a method for preparing the vulcanized rubber there is a method in which an additive and / or a resin are blended with the ethylene- ⁇ -olefin-nonconjugated polyene copolymer as necessary, and vulcanized by heating, electron beam irradiation or the like. can give.
- additives examples include vulcanizing agents, vulcanizing aids, vulcanization accelerators, softeners, reinforcing agents, foaming agents, foaming aids, stabilizers, and antifoaming agents.
- sulfur As the vulcanizing agent, sulfur, a sulfur-based compound, an organic peroxide, or the like can be used.
- sulfur powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur and the like can be used.
- the amount of sulfur and sulfur-based compound used is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the ethylene- ⁇ -olefin-nonconjugated polyene copolymer. It is.
- organic peroxide examples include dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5 -Dimethyl-2,5- (tert-butylperoxy) hexyne-3, di-tert-butyl peroxide, di-tert-butyl peroxide-3,3,5-trimethylcyclohexane, and tert-butyl hydroperoxide .
- dicumyl peroxide di-tert-butyl peroxide, di-tert-butyl peroxide-3,3,5-trimethylcyclohexane, and more preferred is di-tert-butyl peroxide-3,3,5-trimethylcyclohexane.
- the amount of the organic peroxide used is preferably 0.1 to 15 parts by weight, more preferably 1 to 8 parts by weight, based on 100 parts by weight of the ethylene- ⁇ -olefin-nonconjugated polyene copolymer.
- vulcanization aids used with sulfur or sulfur compounds include metal oxides such as magnesium oxide and zinc oxide. Zinc oxide is preferable.
- the blending amount of these vulcanization aids is preferably 1 to 20 parts by weight, based on 100 parts by weight of the ethylene- ⁇ -olefin-nonconjugated polyene copolymer.
- vulcanization aids used with organic peroxides include triallyl isocyanurate, N, N′-m-phenylenebismaleimide, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, isodecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, polyethylene glycol mono Methacrylate, polypropylene glycol monomethacrylate, 2-ethoxy Tyl methacrylate, tetrahydrofurfuryl methacrylate
- the blending amount of these vulcanization aids is preferably 0.05 to 15 parts by weight, more preferably 0.1 to 8 parts by weight, based on 100 parts by weight of the ethylene- ⁇ -olefin-nonconjugated polyene copolymer. Part.
- vulcanization accelerator examples include tetramethyl thiuram disulfide, tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, dipentamethylene thiuram monosulfide, dipentamethylene thiuram disulfide, dipentamethylene thiuram tetrasulfide, N, N′-dimethyl-N, N′-diphenylthiuram disulfide, N, N′-dioctadecyl-N, N′-diisopropylthiuram disulfide, N-cyclohexyl-2-benzothiazole-sulfenamide, N-oxydiethylene-2-benzothiazole-sulfenamide, N, N -Diisopropyl-2-benzothiazolesulfenamide, 2-mercaptobenzothiazole, 2- (2,4-dinitrophenyl) mercaptobenz
- the blending amount of the vulcanization accelerator is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 8 parts by weight, based on 100 parts by weight of the ethylene- ⁇ -olefin-nonconjugated polyene copolymer. is there.
- softeners petroleum-based softeners such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt and petroleum jelly; coal-tar softeners such as coal tar and coal tar pitch; castor oil, linseed oil, rapeseed oil, Fatty oil softeners such as coconut oil; waxes such as tall oil, sub, beeswax, carnauba wax and lanolin; fatty acids and fatty acid salts such as ricinoleic acid, palmitic acid, barium stearate, calcium stearate and zinc laurate; petroleum Examples thereof include synthetic polymer substances such as resins, atactic polypropylene, and coumarone indene resins.
- the blending amount of the softening agent is preferably 1 to 300 parts by weight, more preferably 20 to 250 parts by weight, and further preferably 50, based on 100 parts by weight of the ethylene- ⁇ -olefin-nonconjugated polyene copolymer. ⁇ 200 parts by weight.
- reinforcing agents include carbon black, silica, calcium carbonate, fine powder talc, fine powder aluminum silicate and the like.
- examples of the carbon black include SRF, GPF, FEF, MAF, HAF, ISAF, SAF, FT, and MT. These carbon blacks may be surface-treated with a silane coupling agent or the like.
- the compounding amount of the reinforcing agent is preferably 1 to 300 parts by weight, more preferably 20 to 250 parts by weight, and still more preferably 50, based on 100 parts by weight of the ethylene- ⁇ -olefin-nonconjugated polyene copolymer. ⁇ 200 parts by weight.
- foaming agent examples include inorganic foaming agents such as sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, and ammonium nitrite; N, N′-dimethyl-N, N′-dinitrosotephthalamide, N, N′-di Nitroso compounds such as nitrosopentamethylenetetramine; azo compounds such as azodicarbonamide, azobisisobutyronitrile, azobiscyclohexylnitrile, azodiaminobenzene, barium azodicarboxylate; benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, P, P Sulfonyl hydrazide compounds such as' -oxybis (benzenesulfonylhydrazide) and diphenylsulfone-3,3'-disulfonylhydrazide; calcium azide, 4,4'-dip
- the blending amount of the foaming agent is preferably 0.01 to 15 parts by weight, more preferably 0.05 to 8 parts by weight, based on 100 parts by weight of the ethylene- ⁇ -olefin-nonconjugated polyene copolymer.
- foaming aids include organic acids such as salicylic acid, phthalic acid, stearic acid, and oxalic acid; urea or derivatives thereof.
- the blending amount of the foaming aid is preferably 0.01 to 15 parts by weight, more preferably 0.05 to 8 parts by weight, based on 100 parts by weight of the ethylene- ⁇ -olefin-nonconjugated polyene copolymer. .
- stabilizers include amine-based anti-aging agents, hindered phenol-based anti-aging agents, and sulfur-based anti-aging agents.
- the blending amount of the stabilizer is preferably 0.01 to 15 parts by weight, more preferably 0.05 to 8 parts by weight, based on 100 parts by weight of the ethylene- ⁇ -olefin-nonconjugated polyene copolymer.
- the antifoaming agent is calcium oxide.
- the blending amount of the antifoaming agent is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 8 parts by weight, based on 100 parts by weight of the ethylene- ⁇ -olefin-nonconjugated polyene copolymer. .
- Examples of the resin include polyethylene resin, polypropylene resin, polybutene, poly-4-methyl-pentene-1, polystyrene, polyester, polyamide, polyphenylene ether, and the like.
- Examples of the polyethylene resin include high density polyethylene, medium density polyethylene, low density polyethylene, and linear low density polyethylene.
- a method for preparing a polymer composition by blending an ethylene- ⁇ -olefin-nonconjugated polyene copolymer with an additive and / or a resin a known method can be used. For example, using an internal mixer such as a Banbury mixer, a kneader, or an intermix, a softener, a reinforcing agent, a stabilizer, and the like and an ethylene- ⁇ -olefin-nonconjugated polyene copolymer at a temperature of 80 to 170 ° C.
- an internal mixer such as a Banbury mixer, a kneader, or an intermix, a softener, a reinforcing agent, a stabilizer, and the like and an ethylene- ⁇ -olefin-nonconjugated polyene copolymer at a temperature of 80 to 170 ° C.
- the polymer composition can be prepared by kneading for 5 to 30 minutes.
- the kneading temperature in the internal mixer is lower than the decomposition temperature of the vulcanizing agent or blowing agent, the softening agent, reinforcing agent, stabilizer, etc., and the vulcanizing agent, blowing agent, etc. may be kneaded simultaneously. it can.
- heating means such as hot air, glass bead fluidized bed, UHF (ultra high frequency electromagnetic wave), steam, LCM (hot molten salt bath), etc.
- a heating tank having a mold can be used.
- the heating temperature is preferably 150 to 270 ° C., and the heating time is preferably 1 to 60 minutes.
- the energy of the electron beam is preferably 0.1 to 10 MeV, more preferably 0.3 to 2 MeV. . Further, it is preferable to irradiate the ethylene- ⁇ -olefin-nonconjugated polyene copolymer with an electron beam so that the absorbed dose is 0.5 to 35 Mrad, and the electron beam so that the absorbed dose is 0.5 to 10 Mrad. Is more preferably irradiated to the ethylene- ⁇ -olefin-nonconjugated polyene copolymer.
- Vulcanized rubber is suitably used for rubber hoses.
- the rubber hose include a radiator hose, a heater hose, a brake hose, and a brake reservoir hose.
- a softener As a method of manufacturing a rubber hose having a layer made of vulcanized rubber, a softener, a reinforcing agent, a stabilizer, a vulcanizing agent, a vulcanization accelerator, a vulcanization aid are added to an ethylene- ⁇ -olefin-nonconjugated polyene copolymer.
- a polymer composition containing an additive such as an agent is molded into a molded body having a desired shape by a known molding machine (for example, an extrusion molding machine), and the molded body is formed simultaneously with or after the molding.
- Ethylene unit amount and propylene unit amount The copolymer was formed into a film having a thickness of about 0.1 mm with a hot press machine, and the infrared of the film was measured with an infrared spectrophotometer (IR-810, manufactured by JASCO Corporation). Absorption spectrum was measured. From the infrared absorption spectrum, literature (characterizing polyethylene by infrared absorption spectrum, Takayama, Usami et al. And Die Makromolekulare Chemie, 177, 461 (1976) Mc Rae, MA, Madam S, WF, etc. ) The ethylene unit amount and the propylene unit amount were determined according to the method described.
- the copolymer was formed into a film having a thickness of about 0.5 mm by a hot press.
- the intensity of the peak derived from 5-ethylidene-2-norbornene (absorption peak at 1688 cm ⁇ 1) of the film was measured with an infrared spectrophotometer.
- the molar content of the double bond was determined from the peak intensity, and the iodine value was calculated from the molar content.
- step (2) of preparing polymer compositions in Examples and Comparative Examples the presence or absence of bagging during roll kneading was observed. Those with no bagging were evaluated as “good” and those with bagging were evaluated as “bad”.
- Example 1 (Preparation of copolymer) The temperature of a stainless steel polymerization tank equipped with a stirrer is kept at 60 ° C., and 0.461 kg / (hr ⁇ L) of hexane and 31.6 g of ethylene per unit time / unit volume of the polymerization tank are stored in the polymerization tank. / (Hr ⁇ L), propylene was fed at a rate of 169 g / (hr ⁇ L).
- VOCl 3 was supplied to the polymerization tank at a rate of 230 mg / (hr ⁇ L), ethylaluminum sesquichloride (EASC) at 341 mg / (hr ⁇ L), and hydrogen at a rate of 0.013 NL / (hr ⁇ L). Further, 5-ethylidene-2-norbornene was supplied to the polymerization tank at a rate of 2.8 g / (hr ⁇ L). The polymerization solution was extracted from the polymerization tank so that the amount of the polymerization solution in the polymerization tank was constant. The solvent was removed from the extracted polymerization solution to obtain a copolymer (hereinafter referred to as EPDM-A).
- EPDM-A copolymer
- the ethylene unit amount / propylene unit amount (molar ratio) of EPDM-A was 0.61 / 0.39, and the iodine value was 14.4 (g / 100 g polymer).
- Mz / Mn was 19.1
- Mw / Mn was 4.2
- intrinsic viscosity was 1.60 dl / g
- tan ⁇ 100 ° C., 2 cpm
- tan ⁇ 100 ° C., 1000 cpm
- Example 2 (Preparation of copolymer) The temperature of a stainless steel polymerization tank equipped with a stirrer is kept at 60 ° C., and 1.13 kg / (hr ⁇ L) of hexane and 30.0 g of ethylene per unit time / unit volume of the polymerization tank. / (Hr ⁇ L), propylene was supplied at a rate of 160 g / (hr ⁇ L). VOCl 3 was supplied to the polymerization tank at a rate of 266 mg / (hr ⁇ L), ethylaluminum sesquichloride (EASC) at 399 mg / (hr ⁇ L), and hydrogen at a rate of 0.001 NL / (hr ⁇ L).
- EASC ethylaluminum sesquichloride
- 5-ethylidene-2-norbornene was fed to the polymerization tank at a rate of 9.2 g / (hr ⁇ L).
- the polymerization solution was extracted from the polymerization tank so that the amount of the polymerization solution in the polymerization tank was constant.
- the solvent was removed from the extracted polymerization solution to obtain a copolymer (hereinafter referred to as EPDM-B).
- EPDM-B ethylene unit amount / propylene unit amount (molar ratio) of EPDM-B was 0.62 / 0.38, and the iodine value was 25.1 (g / 100 g polymer).
- Mz / Mn was 17.4, Mw / Mn was 4.0, intrinsic viscosity was 1.41 dl / g, and tan ⁇ (100 ° C., 2 cpm) / tan ⁇ (100 ° C., 1000 cpm) was 1.51.
- a polymer composition was prepared in the same manner as in “Preparation of polymer composition” in Example 1, except that EPDM-B was used instead of EPDM-A, and the roll kneading processability of the polymer composition was The extrusion processability was evaluated.
- the evaluation results of the polymer composition are shown in Table 1.
- Comparative Example 1 (Preparation of copolymer) In a polymerization tank made of stainless steel equipped with a stirrer and maintained at 60 ° C., 0.458 kg / (hr ⁇ L) of hexane and 32.3 g / (hr ⁇ L) of ethylene per unit time / unit volume of the polymerization tank. L) and propylene were fed at a rate of 173 g / (hr ⁇ L).
- VOCl 3 was supplied to the polymerization tank at a rate of 140 mg / (hr ⁇ L), ethylaluminum sesquichloride (EASC) at 307 mg / (hr ⁇ L), and hydrogen at a rate of 0.010 NL / (hr ⁇ L). Further, 5-ethylidene-2-norbornene was fed to the polymerization tank at a rate of 1.9 g / (hr ⁇ L). The polymerization solution was extracted from the polymerization tank so that the amount of the polymerization solution in the polymerization tank was constant. The solvent was removed from the extracted polymerization solution to obtain a copolymer (hereinafter referred to as EPDM-C).
- EPDM-C copolymer
- the ethylene unit amount / propylene unit amount (molar ratio) of EPDM-C was 0.61 / 0.39, and the iodine value was 9.6 (g / 100 g polymer).
- Mz / Mn was 13.4, Mw / Mn was 3.8, intrinsic viscosity was 1.75 dl / g, and tan ⁇ (100 ° C., 2 cpm) / tan ⁇ (100 ° C., 1000 cpm) was 1.65.
- a polymer composition was prepared in the same manner as in “Preparation of polymer composition” in Example 1, except that EPDM-C was used instead of EPDM-A, and the roll kneading processability of the polymer composition was The extrusion processability was evaluated.
- the evaluation results of the polymer composition are shown in Table 1.
- Comparative Example 2 (Preparation of copolymer) In a polymerization tank made of stainless steel equipped with a stirrer and maintained at 55 ° C., 0.458 kg / (hr ⁇ L) of hexane and 32.4 g / (hr ⁇ L) of hexane per unit time / unit volume of the polymerization tank. L) and propylene were fed at a rate of 173 g / (hr ⁇ L).
- VOCl3 was supplied to the polymerization tank at a rate of 108 mg / (hr ⁇ L), ethylaluminum sesquichloride (EASC) at 237 mg / (hr ⁇ L), and hydrogen at a rate of 0.028 NL / (hr ⁇ L). Further, 5-ethylidene-2-norbornene was fed to the polymerization tank at a rate of 1.9 g / (hr ⁇ L). The polymerization solution was extracted from the polymerization tank so that the amount of the polymerization solution in the polymerization tank was constant. The solvent was removed from the extracted polymerization solution to obtain a copolymer (hereinafter referred to as EPDM-D).
- EPDM-D copolymer
- ethylene unit amount / propylene unit amount (molar ratio) of EPDM-D was 0.61 / 0.39
- iodine value was 10.3 (g / 100 g polymer)
- Mz / Mn was 11.5
- Mw / Mn was 3.2
- intrinsic viscosity was 1.65 dl / g
- tan ⁇ 100 ° C., 2 cpm
- tan ⁇ 100 ° C., 1000 cpm
- a polymer composition was prepared in the same manner as in “Preparation of polymer composition” in Example 1, except that EPDM-D was used instead of EPDM-A, and the roll kneading processability of the polymer composition was The extrusion processability was evaluated.
- the evaluation results of the polymer composition are shown in Table 1.
- Comparative Example 3 (Preparation of copolymer) In a polymerization tank made of stainless steel equipped with a stirrer and maintained at 45 ° C., 0.458 kg / (hr ⁇ L) of hexane and 32.3 g / (hr ⁇ L) of ethylene per unit time / unit volume of the polymerization tank. L) and propylene were fed at a rate of 173 g / (hr ⁇ L).
- VOCl 3 was supplied to the polymerization tank at a rate of 58.4 mg / (hr ⁇ L), ethylaluminum sesquichloride (EASC) at 128 mg / (hr ⁇ L), and hydrogen at a rate of 0.076 NL / (hr ⁇ L). Further, dicyclopentadiene was supplied to the polymerization tank at a rate of 2.1 g / (hr ⁇ L). The polymerization solution was extracted from the polymerization tank so that the amount of the polymerization solution in the polymerization tank was constant. The solvent was removed from the extracted polymerization solution to obtain a copolymer (hereinafter referred to as EPDM-E).
- EPDM-E copolymer
- the ethylene unit amount / propylene unit amount (molar ratio) of EPDM-E was 0.62 / 0.38, and the iodine value was 9.5 (g / 100 g polymer).
- Mz / Mn was 10.6, Mw / Mn was 3.4, intrinsic viscosity was 1.52 dl / g, and tan ⁇ (100 ° C., 2 cpm) / tan ⁇ (100 ° C., 1000 cpm) was 1.78.
- a polymer composition was prepared in the same manner as in “Preparation of polymer composition” in Example 1, except that EPDM-E was used instead of EPDM-A, and the roll kneading processability of the polymer composition was The extrusion processability was evaluated.
- the evaluation results of the polymer composition are shown in Table 1.
- an ethylene- ⁇ -olefin-nonconjugated polyene copolymer excellent in roll kneading processability and extrusion processability can be provided.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Abstract
Description
ゴムホースに用いられる原料ゴムとして、例えば、特開2004−285324号公報や特開2011−174002号公報には、エチレン−α−オレフィン−非共役ポリエン共重合体が記載されている。
かかる状況のもと、本発明が解決しようとする課題は、ロール混練加工性と押出加工性に優れたエチレン−α−オレフィン−非共役ポリエン共重合体を提供することにある。
(A):極限粘度[η]が0.5~1.8dl/gである。
(B):エチレン単位の含有量とα−オレフィン単位の含有量との総量を100モル%とするとき、エチレン単位の含有量が50~90モル%であり、α−オレフィン単位の含有量が50~10モル%である。
(C):よう素価が1~50である。
(D):100℃および1000cpmでのtanδに対する100℃および2cpmでのtanδの比が1.0~1.7である。
(E):数平均分子量に対するZ−平均分子量の比が15~25であり、数平均分子量に対する重量平均分子量の比が3~5である。
エチレン−α−オレフィン−非共役ポリエン共重合体のα−オレフィンとしては、好ましくは、炭素原子数3~20のα−オレフィンであり、プロピレン、1−ブテン、1−ペンテン、1−ヘキセン、1−ヘプテン、1−オクテン、1−ノネン、1−デセン等の直鎖状α−オレフィン;3−メチル−1−ブテン、3−メチル−1−ペンテン、4−メチル−1−ペンテン等の分岐状α−オレフィンがあげられる。これらは、1種以上使用される。
α−オレフィンとしては、好ましくは、プロピレン、1−ブテンであり、より好ましくはプロピレンである。
(a)バナジウム化合物の使用量に対する有機アルミニウム化合物の使用量のモル比(有機アルミニウム化合物のモル数/バナジウム化合物のモル数)が0.1~2.0である。
(b)重合温度が50~80℃である。
(c)重合反応器に供給される水素の量が、重合反応器に供給される溶媒の量1kgあたり、0.001~0.1NLである。
(d)重合反応器に供給されるバナジウム化合物の量が、重合反応器に供給される溶媒100重量部あたり、0.02~0.2重量部である。
)0.5Cl2.5、VO(O(n−C7H15))0.5Cl2.5、VO(O(n−C8H17))0.5Cl2.5、VO(OCH3)0.8Cl2.2、VO(OC2H5)0.8Cl2.2、VO(O(n−C3H7))0.8Cl2.2、VO(O(n−C4H9))0.8Cl2.2、VO(O(n−C5H11))0.8Cl2.2、VO(O(n−C6H13))0.8Cl2.2、VO(O(n−C7H15))0.8Cl2.2、VO(O(n−C8H17))0.8Cl2.2、VO(OCH3)Cl2、VO(OC2H5)Cl2、VO(O(n−C3H7))Cl2、VO(O(n−C4H9))Cl2、VO(O(n−C5H11))Cl2、VO(O(n−C6H13))Cl2、VO(O(n−C7H15))Cl2、VO(O(n−C8H17))Cl2、VO(OCH3)1.5Cl0.5、VO(OC2H5)1.5Cl0.5、VO(O(n−C3H7))1.5Cl0.5、VO(O(n−C4H9))1.5Cl0.5、VO(O(n−C5H11))1.5Cl0.5、VO(O(n−C6H13))1.5Cl0.5、VO(O(n−C7H15))1.5Cl0.5、VO(O(n−C8H17))1.5Cl0.5、等のVO(OR)mCln[式中、Rは炭素原子数1~10のアルキル基を表し、mおよびnは、m+n=3、0≦m<3および0<n≦3を充足する数である。]で表される化合物をあげることができる。好ましくは、VOCl3、VO(OC2H5)0.5Cl2.5、VO(OC2H5)0.8Cl2.2、VO(OC2H5)Cl2、VO(OC2H5)1.5Cl0.5等のVO(OC2H5)rCls[式中、rおよびsは、r+s=3、1≦r<3および0<s≦2を充足する数である。]で表される化合物であり、より好ましくはVOCl3である。
(1)エチレン単位量およびプロピレン単位量
共重合体をホットプレス機により厚み約0.1mmのフィルムに成形し、赤外分光光度計(日本分光工業社製 IR−810)により該フィルムの赤外吸収スペクトルを測定した。該赤外吸収スペクトルから、文献(赤外吸収スペクトルによるポリエチレンのキャラクタリゼーション 高山、宇佐美 等著 及び Die Makromolekulare Chemie,177,461(1976)Mc Rae,M.A.,MadamS,W.F.等著)記載の方法に従って、エチレン単位量およびプロピレン単位量を求めた。
共重合体をホットプレス機により厚み約0.5mmのフィルムに成形した。赤外分光光度計により該フィルムの5−エチリデン−2−ノルボルネン由来のピーク(1688cm−1の吸収ピーク)の強度を測定した。該ピーク強度から二重結合のモル含量を求め、該モル含量からヨウ素価を算出した。
ゲル・パーミエイション・クロマトグラフ(GPC)法によって、下記の条件(1)~(9)で、共重合体のZ−平均分子量(Mz)と数平均分子量(Mn)及び重量平均分子量(Mw)を測定し、Mz/Mn及びMw/Mnを求めた。
(1)装置:Waters製150C
(2)分離カラム:昭和電工社製Shodex Packed ColumnA−80M (3)測定温度:140℃
(4)キャリア:オルトジクロロベンゼン
(5)流量:1.0mL/分
(6)試料濃度:約1mg/1mL
(7)試料注入量:400μL
(8)検出器:示差屈折
(9)分子量標準物質:標準ポリスチレン
ウベローデ型粘度計を用い、135℃のテトラリン溶液中で極限粘度を測定した。
粘弾性測定装置(ALPHA TECHNOLOGIES社製 RUBBER PROCESS ANALYZER RPA2000P)を用い、温度100℃、歪み13.95%で、周波数を変更して、共重合体のtanδ(せん断損失弾性率とせん断貯蔵弾性率の比:せん断損失弾性率/せん断貯蔵弾性率)を測定した。周波数が2cpmでのtanδと周波数が1000cpmでのtanδの比を算出した。
実施例及び比較例における重合体組成物の調製の工程(2)において、ロール混練時のバギングの発生の有無を観察した。バギングの発生が無いものを『良好』、バギングの発生があるものを『不良』と評価した。
L/D=16の45mmφベント式押出機(中田造機社製)に、押出ダイとしてASTM D2230−90の5.2 Die−ASTM Extrusion Dieに規定のガーベタイプ押出ダイ(Garvey−type extrusion die)をセットし、スクリュー温度40℃、シリンダー温度60℃、ダイ温度80℃、スクリュー回転数60rpmにて、重合体組成物をダイから押出し、重合体組成物の押出速度(cm/min)を測定した。当該速度が速いほど、押出加工性に優れる。なお、押し出された細長い重合体組成物の単位時間(min)あたりの長さ(cm)を押出速度(cm/min)とした。
(共重合体の調製)
攪拌機を備えたステンレススチール製の重合槽の温度を60℃に保ち、当該重合槽に、単位時間・重合槽の単位容積あたり、ヘキサンを0.461kg/(hr・L)、エチレンを31.6g/(hr・L)、プロピレンを169g/(hr・L)の速度で供給した。VOCl3を230mg/(hr・L)、エチルアルミニウムセスキクロライド(EASC)を341mg/(hr・L)、水素を0.013NL/(hr・L)の速度で重合槽に供給した。更に5−エチリデン−2−ノルボルネンを2.8g/(hr・L)の速度で重合槽に供給した。
重合槽からは、重合槽内の重合溶液の量が一定となるように、重合溶液を抜き出した。
抜き出した重合溶液から溶媒を除去して、共重合体(以下、EPDM−Aと記す。)を得た。
EPDM−Aを分析したところ、EPDM−Aのエチレン単位量/プロピレン単位量(モル比)は0.61/0.39であり、ヨウ素価は14.4(g/100g重合体)であり、Mz/Mnは19.1、Mw/Mnは4.2、極限粘度は1.60dl/g、tanδ(100℃,2cpm)/tanδ(100℃,1000cpm)は1.40であった。
工程(1)
100重量部のEPDM−Aと、5重量部の酸化亜鉛と、1重量部のステアリン酸と、90重量部のFEFカーボンブラック(旭カーボン社製 旭60G)と、5重量部のパラフィン系オイル(出光興産社製 ダイアナPW380)と、2重量部のポリエチレングリコール(PEG4000)と、2重量部の加工助剤(シル+ザイラッハ社製 ストラクトールWB212)と、1重量部の2−メルカプトベンゾイミダゾール(住友化学社製 スミライザーMB)とをバンバリーミキサーで混練して、混練物を得た。混練においては、混練開始時のバンバリーミキサーの温度を80℃とし、ローター回転数を60rpmとし、混練時間を5分間とした。
上記混練物と、該混練物中のEPDM−A 100重量部あたり、5重量部のα,α’−ビス(t−ブチルペロキシ)ジイソプロピルベンゼン(日油社製 ペロキシモンF(40)有効成分60%)、0.5重量部のイオウとを、ロール温度50℃の8インチの一対のロールであって、オープンロール(関西ロール社製)により、ロールギャップ4mmにて回転速度フロントロール15rpm、バックロール18rpmの条件でバックロール側に巻きつけながら混練して、重合体組成物を得、そして、重合体組成物のロール混練加工性を評価した。次に、該重合体組成物の押出加工性を評価した。評価結果を表1に示す。
(共重合体の調製)
攪拌機を備えたステンレススチール製の重合槽の温度を60℃に保ち、当該重合槽に、単位時間・重合槽の単位容積あたり、ヘキサンを1.13kg/(hr・L)、エチレンを30.0g/(hr・L)、プロピレンを160g/(hr・L)の速度で供給した。VOCl3を266mg/(hr・L)、エチルアルミニウムセスキクロライド(EASC)を399mg/(hr・L)、水素を0.001NL/(hr・L)の速度で重合槽に供給した。更に5−エチリデン−2−ノルボルネンを9.2g/(hr・L)の速度で重合槽に供給した。
重合槽からは、重合槽内の重合溶液の量が一定となるように、重合溶液を抜き出した。抜き出した重合溶液から溶媒を除去して、共重合体(以下、EPDM−Bと記す。)を得た。
EPDM−Bを分析したところ、EPDM−Bのエチレン単位量/プロピレン単位量(モル比)は0.62/0.38であり、ヨウ素価は25.1(g/100g重合体)であり、Mz/Mnは17.4、Mw/Mnは4.0、極限粘度は1.41dl/g、tanδ(100℃,2cpm)/tanδ(100℃,1000cpm)は1.51であった。
EPDM−AにかえてEPDM−Bを用いた以外は、実施例1の「重合体組成物の調製」と同様にして、重合体組成物を調製し、該重合体組成物のロール混練加工性と押出加工性を評価した。該重合体組成物の評価結果を表1に示す。
(共重合体の調製)
攪拌機を備えたステンレススチール製の温度を60℃に保った重合槽に、単位時間・重合槽の単位容積あたり、ヘキサンを0.458kg/(hr・L)、エチレンを32.3g/(hr・L)、プロピレンを173g/(hr・L)の速度で供給した。VOCl3を140mg/(hr・L)、エチルアルミニウムセスキクロライド(EASC)を307mg/(hr・L)、水素を0.010NL/(hr・L)の速度で重合槽に供給した。更に5−エチリデン−2−ノルボルネンを1.9g/(hr・L)の速度で重合槽に供給した。
重合槽からは、重合槽内の重合溶液の量が一定となるように、重合溶液を抜き出した。
抜き出した重合溶液から溶媒を除去して、共重合体(以下、EPDM−Cと記す。)を得た。
EPDM−Cを分析したところ、EPDM−Cのエチレン単位量/プロピレン単位量(モル比)は0.61/0.39であり、ヨウ素価は9.6(g/100g重合体)であり、Mz/Mnは13.4、Mw/Mnは3.8、極限粘度は1.75dl/g、tanδ(100℃,2cpm)/tanδ(100℃,1000cpm)は1.65であった。
EPDM−AにかえてEPDM−Cを用いた以外は、実施例1の「重合体組成物の調製」と同様にして、重合体組成物を調製し、該重合体組成物のロール混練加工性と押出加工性を評価した。該重合体組成物の評価結果を表1に示す。
(共重合体の調製)
攪拌機を備えたステンレススチール製の温度を55℃に保った重合槽に、単位時間・重合槽の単位容積あたり、ヘキサンを0.458kg/(hr・L)、エチレンを32.4g/(hr・L)、プロピレンを173g/(hr・L)の速度で供給した。VOCl3を108mg/(hr・L)、エチルアルミニウムセスキクロライド(EASC)を237mg/(hr・L)、水素を0.028NL/(hr・L)の速度で重合槽に供給した。更に5−エチリデン−2−ノルボルネンを1.9g/(hr・L)の速度で重合槽に供給した。
重合槽からは、重合槽内の重合溶液の量が一定となるように、重合溶液を抜き出した。
抜き出した重合溶液から溶媒を除去して、共重合体(以下、EPDM−Dと記す。)を得た。
EPDM−Dを分析したところ、EPDM−Dのエチレン単位量/プロピレン単位量(モル比)は0.61/0.39であり、ヨウ素価は10.3(g/100g重合体)であり、Mz/Mnは11.5、Mw/Mnは3.2、極限粘度は1.65dl/g、tanδ(100℃,2cpm)/tanδ(100℃,1000cpm)は1.96であった。
EPDM−AにかえてEPDM−Dを用いた以外は、実施例1の「重合体組成物の調製」と同様にして、重合体組成物を調製し、該重合体組成物のロール混練加工性と押出加工性を評価した。該重合体組成物の評価結果を表1に示す。
(共重合体の調製)
攪拌機を備えたステンレススチール製の温度を45℃に保った重合槽に、単位時間・重合槽の単位容積あたり、ヘキサンを0.458kg/(hr・L)、エチレンを32.3g/(hr・L)、プロピレンを173g/(hr・L)の速度で供給した。VOCl3を58.4mg/(hr・L)、エチルアルミニウムセスキクロライド(EASC)を128mg/(hr・L)、水素を0.076NL/(hr・L)の速度で重合槽に供給した。更にジシクロペンタジエンを2.1g/(hr・L)の速度で重合槽に供給した。
重合槽からは、重合槽内の重合溶液の量が一定となるように、重合溶液を抜き出した。
抜き出した重合溶液から溶媒を除去して、共重合体(以下、EPDM−Eと記す。)を得た。
EPDM−Eを分析したところ、EPDM−Eのエチレン単位量/プロピレン単位量(モル比)は0.62/0.38であり、ヨウ素価は9.5(g/100g重合体)であり、Mz/Mnは10.6、Mw/Mnは3.4、極限粘度は1.52dl/g、tanδ(100℃,2cpm)/tanδ(100℃,1000cpm)は1.78であった。
EPDM−AにかえてEPDM−Eを用いた以外は、実施例1の「重合体組成物の調製」と同様にして、重合体組成物を調製し、該重合体組成物のロール混練加工性と押出加工性を評価した。該重合体組成物の評価結果を表1に示す。
Claims (2)
- エチレン単位、α−オレフィン単位および非共役ポリエン単位を含むエチレン−α−オレフィン−非共役ポリエン共重合体であって、下記要件(A)、(B)、(C)、(D)及び(E)を充足するエチレン−α−オレフィン−非共役ポリエン共重合体。
(A):極限粘度[η]が0.5~1.8dl/gである。
(B):エチレン単位の含有量とα−オレフィン単位の含有量との総量を100モル%とするとき、エチレン単位の含有量が50~90モル%であり、α−オレフィン単位の含有量が50~10モル%である。
(C):よう素価が1~50である。
(D):100℃および1000cpmでのtanδに対する100℃および2cpmでのtanδの比が1.0~1.7である。
(E):数平均分子量に対するZ−平均分子量の比が15~25であり、数平均分子量に対する重量平均分子量の比が3~5である。 - α−オレフィンがプロピレンであり、非共役ポリエンが、5−アルキリデン−2−ノルボルネンおよび5−アルケニル−2−ノルボルネンからなる化合物群から選ばれる少なくとも1種の化合物である第1項に記載のエチレン−α−オレフィン−非共役ポリエン共重合体。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201280063094.6A CN103998478A (zh) | 2011-12-21 | 2012-12-18 | 乙烯-α-烯烃-非共轭多烯共聚物 |
DE112012005368.0T DE112012005368T5 (de) | 2011-12-21 | 2012-12-18 | Ethylen-alpha-Olefin-nichtkonjugiertes Polyencopolymer |
US14/363,352 US8962776B2 (en) | 2011-12-21 | 2012-12-18 | Ethylene-α-olefin-nonconjugated polyene copolymer |
KR1020147019946A KR101889132B1 (ko) | 2011-12-21 | 2012-12-18 | 에틸렌-α-올레핀-비공액 폴리엔 공중합체 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011-279373 | 2011-12-21 | ||
JP2011279373 | 2011-12-21 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013094767A1 true WO2013094767A1 (ja) | 2013-06-27 |
Family
ID=48668644
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2012/083375 WO2013094767A1 (ja) | 2011-12-21 | 2012-12-18 | エチレン‐α‐オレフィン‐非共役ポリエン共重合体 |
Country Status (6)
Country | Link |
---|---|
US (1) | US8962776B2 (ja) |
JP (1) | JP5956919B2 (ja) |
KR (1) | KR101889132B1 (ja) |
CN (1) | CN103998478A (ja) |
DE (1) | DE112012005368T5 (ja) |
WO (1) | WO2013094767A1 (ja) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017206008A1 (en) * | 2016-05-30 | 2017-12-07 | Dow Global Technologies Llc | Ethylene/alpha-olefin/diene interpolymer |
US20210371559A1 (en) * | 2018-11-07 | 2021-12-02 | Sumitomo Chemical Company, Limited | Ethylene-alpha-olefin-nonconjugated polyene copolymer rubber and rubber composition |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS50129690A (ja) * | 1974-03-25 | 1975-10-14 | ||
JPS61261306A (ja) * | 1985-05-03 | 1986-11-19 | エクソン・ケミカル・パテンツ・インク | ケイ酸塩で改良したepdm触媒系及び方法 |
JP2002507228A (ja) * | 1997-06-27 | 2002-03-05 | ディーエスエム エヌ.ブイ. | 弾性共重合体及びその製造方法 |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6030326B2 (ja) * | 1978-08-17 | 1985-07-16 | 三井化学株式会社 | エチレン共重合ゴムの製造方法 |
JPS56157412A (en) * | 1980-05-09 | 1981-12-04 | Sumitomo Chem Co Ltd | Production of olefin copolymer |
JP3684626B2 (ja) * | 1995-07-25 | 2005-08-17 | Jsr株式会社 | エチレン系ランダム共重合体およびその組成物 |
SG67536A1 (en) * | 1997-08-13 | 1999-09-21 | Mitsui Chemicals Inc | Curable rubber composition |
KR100553488B1 (ko) * | 1999-04-02 | 2006-02-20 | 미쓰이 가가쿠 가부시키가이샤 | 에틸렌·α-올레핀·비공액폴리엔 공중합체 고무, 실링용고무 조성물, 실링용 고무 성형체 및 상기 성형체의 제조방법 |
JP2002249623A (ja) | 2000-12-21 | 2002-09-06 | Sumitomo Chem Co Ltd | ブレーキホース用ゴム組成物及び加硫ゴム組成物 |
JP2004197080A (ja) * | 2002-12-03 | 2004-07-15 | Sumitomo Chem Co Ltd | エチレン−α−オレフィン−非共役ジエン共重合ゴム |
US7005492B2 (en) * | 2002-12-03 | 2006-02-28 | Sumitomo Chemical Company, Limited | Copolymer rubber, and foamed article, vulcanized rubber, profile extrusion molded rubber and hose for water comprising said copolymer rubber |
JP2004285324A (ja) | 2003-03-06 | 2004-10-14 | Sumitomo Chem Co Ltd | 水系ホース |
KR20060069264A (ko) * | 2004-12-16 | 2006-06-21 | 스미또모 가가꾸 가부시끼가이샤 | 고무 조성물, 그것의 제조 방법, 가황 고무 조성물을함유하는 성형품의 제조 방법, 및 방진성 물질 |
JP4742724B2 (ja) * | 2005-02-08 | 2011-08-10 | 住友化学株式会社 | 防振材 |
US20100222445A1 (en) * | 2009-02-27 | 2010-09-02 | Sumitomo Chemical Company, Limited | Copolymer rubber composition, rubber foamed product, and automotive sealant |
JP2011174003A (ja) * | 2010-02-25 | 2011-09-08 | Sumitomo Chemical Co Ltd | パッキン用ゴム組成物及びパッキン |
JP2011174002A (ja) | 2010-02-25 | 2011-09-08 | Sumitomo Chemical Co Ltd | ゴムホース用ゴム組成物及びゴムホース |
-
2012
- 2012-12-13 JP JP2012272054A patent/JP5956919B2/ja active Active
- 2012-12-18 DE DE112012005368.0T patent/DE112012005368T5/de not_active Ceased
- 2012-12-18 US US14/363,352 patent/US8962776B2/en active Active
- 2012-12-18 KR KR1020147019946A patent/KR101889132B1/ko active IP Right Grant
- 2012-12-18 CN CN201280063094.6A patent/CN103998478A/zh active Pending
- 2012-12-18 WO PCT/JP2012/083375 patent/WO2013094767A1/ja active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS50129690A (ja) * | 1974-03-25 | 1975-10-14 | ||
JPS61261306A (ja) * | 1985-05-03 | 1986-11-19 | エクソン・ケミカル・パテンツ・インク | ケイ酸塩で改良したepdm触媒系及び方法 |
JP2002507228A (ja) * | 1997-06-27 | 2002-03-05 | ディーエスエム エヌ.ブイ. | 弾性共重合体及びその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
JP5956919B2 (ja) | 2016-07-27 |
KR101889132B1 (ko) | 2018-08-16 |
CN103998478A (zh) | 2014-08-20 |
JP2013147637A (ja) | 2013-08-01 |
US20140316091A1 (en) | 2014-10-23 |
US8962776B2 (en) | 2015-02-24 |
DE112012005368T5 (de) | 2014-10-02 |
KR20140107498A (ko) | 2014-09-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5743013B2 (ja) | 共重合体ゴム組成物、ゴム発泡体及び自動車用シール材 | |
JP5768916B2 (ja) | 共重合体ゴム組成物、成形体及び自動車用シール材 | |
JP5682271B2 (ja) | 防振ゴム用ゴム組成物及び防振ゴム | |
JP4742724B2 (ja) | 防振材 | |
JP2011174004A (ja) | 電気絶縁体用ゴム組成物及び電気絶縁体 | |
JP4088429B2 (ja) | 加硫可能なゴム組成物 | |
JP5956919B2 (ja) | エチレン−α−オレフィン−非共役ポリエン共重合体 | |
JP5065924B2 (ja) | 加硫可能なゴム組成物 | |
JP5560765B2 (ja) | エチレン−α−オレフィン−非共役ポリエン系共重合体ゴム組成物の製造方法 | |
JP2011174003A (ja) | パッキン用ゴム組成物及びパッキン | |
JP2012153773A (ja) | ゴムロール用ゴム組成物及びゴムロール | |
JP2011174002A (ja) | ゴムホース用ゴム組成物及びゴムホース | |
JP4667660B2 (ja) | 加硫可能なゴム組成物 | |
EP3085735B1 (en) | Rubber composition and molded article | |
JP7257176B2 (ja) | ゴム組成物およびゴム成形体の製造方法 | |
JP5006158B2 (ja) | 加硫可能なゴム組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12858952 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14363352 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1120120053680 Country of ref document: DE Ref document number: 112012005368 Country of ref document: DE |
|
ENP | Entry into the national phase |
Ref document number: 20147019946 Country of ref document: KR Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 12858952 Country of ref document: EP Kind code of ref document: A1 |