WO2015194637A1 - シクロペンテン開環重合体およびその製造方法、重合体組成物、ならびに重合体架橋物 - Google Patents
シクロペンテン開環重合体およびその製造方法、重合体組成物、ならびに重合体架橋物 Download PDFInfo
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- C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
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- C08G2261/76—Post-treatment crosslinking
Definitions
- the present invention relates to a cyclopentene ring-opening polymer, a method for producing the same, and a polymer composition. More specifically, since it has a high affinity with fillers such as carbon black and silica, it is suitable as a material for a fuel-efficient tire.
- the present invention relates to a cyclopentene ring-opening polymer, a production method thereof, and a polymer composition, which can provide a polymer composition having excellent low heat build-up.
- Cyclopentene ring-opening polymers obtained by metathesis ring-opening polymerization of cyclopentene are widely known as rubber materials. For example, they are used as various rubber materials by blending fillers such as carbon black and silica.
- a cyclopentene ring-opening polymer is composed of a periodic table Group 6 transition metal compound such as WCl 6 and MoCl 5 and an organometallic compound such as an aluminum compound and a tin compound, as disclosed in, for example, Patent Document 1. They are produced by bulk polymerization or solution polymerization using a so-called Ziegler-Natta catalyst. In some cases, ⁇ -olefin is added as a molecular weight regulator.
- the cyclopentene ring-opened polymer thus obtained is composed of only carbon atoms and hydrogen atoms, the affinity for fillers such as carbon black and silica is low. For this reason, even if such a cyclopentene ring-opening polymer is blended with a filler to form a polymer composition, the effect of improving the mechanical properties by blending the filler is not sufficiently exhibited.
- Patent Document 2 discloses a ruthenium carbene in the presence of a compound having a functional group and an ethylenically unsaturated bond (for example, allyltrimethoxysilane).
- a method has been proposed in which cyclopentene is subjected to ring-opening polymerization using a complex as a catalyst, and a functional group is introduced to the cyclopentene ring-opening polymer chain end by a metathesis reaction between the cyclopentene ring-opening polymer chain end and the ethylenically unsaturated bond. ing.
- the cyclopentene ring-opening polymer having a functional group at the polymer chain end obtained by this method has a greatly improved affinity with a filler as compared with a polymer having no functional group.
- an alkoxysilyl group which is considered to have excellent performance as a functional group to be introduced to improve the affinity with a filler, for styrene butadiene rubber and the like that is currently widely used in tire applications, Even if it was introduced at the end of the cyclopentene ring-opening polymer chain by the method 2, the polymer composition thus obtained still had room for improvement in low heat generation.
- An object of the present invention is to provide a cyclopentene ring-opening polymer having improved affinity with a filler, which can provide a polymer composition having excellent low heat build-up, and to efficiently use such a cyclopentene ring-opening polymer.
- An object of the present invention is to provide a method for producing a cyclopentene ring-opening polymer, which can be produced well. Furthermore, it is providing the polymer composition which has the outstanding low exothermic property.
- the present inventors have reacted a cyclopentene ring-opening polymer having a halogen atom at the polymer chain end with a compound containing an alkoxysilyl group and an amino group in the molecule.
- the cyclopentene ring-opening polymer is superior in affinity with the filler, and the polymer composition obtained using this has excellent low heat generation It was found to have The present invention has been completed based on this finding.
- the polymer chain terminal has a structure in which a polymer chain and a group containing an alkoxysilyl group are bonded via —NH—, and has a weight average molecular weight of 100,000 to 1,000,000.
- a cyclopentene ring-opening polymer A cyclopentene ring-opening polymer, wherein the structure is a structure represented by the following general formula (1): pCP-Y 1 —NH—Y 2 —Si (OR 1 ) a (R 2 ) 3-a (1)
- pCP represents a cyclopentene ring-opened polymer chain
- Y 1 represents a divalent hydrocarbon group having 1 to 20 carbon atoms
- R 1 and R 2 represent carbon atoms having 1 to 20 carbon atoms.
- Y 2 represents a divalent hydrocarbon group having 1 to 20 carbon atoms in which —NH— may be interposed
- a is an integer of 1 to 3.
- the polymer component containing the cyclopentene ring-opening polymer according to [1] or [2] is added in an amount of 10 to 150 wt.
- Part of the polymer composition [5] For 100 parts by weight of a polymer component containing a cyclopentene ring-opening polymer having a halogen atom at the polymer chain end, A total amount of silica or silica and carbon black of 10 to 150 parts by weight, and 0.01 to 20 parts by weight of a compound containing an alkoxysilyl group and an amino group in the molecule are mixed and reacted.
- a polymer composition comprising a cyclopentene ring-opening polymer having a structure in which a polymer chain end and a group containing an alkoxysilyl group are bonded via —NH— at the polymer chain end,
- a polymer composition, wherein the structure is a structure represented by the following general formula (1): pCP-Y 1 —NH—Y 2 —Si (OR 1 ) a (R 2 ) 3-a (1)
- pCP represents a cyclopentene ring-opened polymer chain
- Y 1 represents a divalent hydrocarbon group having 1 to 20 carbon atoms
- R 1 and R 2 represent carbon atoms having 1 to 20 carbon atoms.
- Y represents a hydrogen group
- Y 2 represents a divalent hydrocarbon group having 1 to 20 carbon atoms which may be intervened by —NH—
- a is an integer of 1 to 3.
- a cyclopentene ring-opening polymer having improved affinity with a filler which can provide a polymer composition having excellent low exothermic properties, and such a cyclopentene ring-opening polymer can be efficiently used.
- a process for producing a cyclopentene ring-opening polymer that can be well produced is provided. Furthermore, a polymer composition having excellent low exothermic properties is provided.
- the cyclopentene ring-opening polymer of the present invention has a structure in which a polymer chain and a group containing an alkoxysilyl group are bonded to the end of the polymer chain via —NH—, and the weight average molecular weight is 100
- pCP represents a cyclopentene ring-opened polymer chain
- Y 1 represents a divalent hydrocarbon group having 1 to 20 carbon atoms
- R 1 and R 2 represent carbon atoms having 1 to 20 carbon atoms.
- Y represents a hydrogen group
- Y 2 represents a divalent hydrocarbon group having 1 to 20 carbon atoms which may be intervened by —NH—
- a is an integer of 1 to 3.
- the end of a polymer chain constituted by repeating units formed by ring-opening polymerization of cyclopentene and a group containing an alkoxysilyl group are bonded via —NH—.
- the group containing the alkoxysilyl group constituting the specific terminal structure of the cyclopentene ring-opening polymer of the present invention is a group represented by the following general formula (2). —Y 2 —Si (OR 1 ) a (R 2 ) 3-a (2) (In general formula (2), R 1 , R 2 , Y 2 and a are the same as in general formula (1).)
- the alkoxysilyl group contained in the group containing the alkoxysilyl group may be any of a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group as shown in the general formulas (1) and (2).
- the alkoxy group bonded to the silicon atom in the alkoxysilyl group (that is, the group represented by OR 1 in the general formulas (1) and (2)) is an alkoxy group having 1 to 20 carbon atoms, An alkoxy group having 1 to 10 carbon atoms is preferable, and a methoxy group or an ethoxy group is more preferable.
- a hydrocarbon group having 1 to 20 carbon atoms such as an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, more preferably methyl Group or ethyl group.
- alkoxysilyl group examples include trialkoxysilyl groups such as trimethoxysilyl group and triethoxysilyl group; dialkoxy such as dimethoxymethylsilyl group, diethoxymethylsilyl group, dimethoxyethylsilyl group and diethoxyethylsilyl group Examples thereof include, but are not limited to, alkylsilyl groups; monoalkoxydialkylsilyl groups such as methoxydimethylsilyl group, ethoxydimethylsilyl group, methoxydiethylsilyl group, and ethoxydiethylsilyl group.
- a group containing an alkoxysilyl group constituting the specific terminal structure is a bonding group (a group represented by Y 2 in the general formulas (1) and (2)) between the alkoxysilyl group and —NH—.
- -NH- contains a divalent hydrocarbon group having 1 to 20 carbon atoms which may be interposed.
- Such a linking group is more preferably a divalent hydrocarbon group having 1 to 10 carbon atoms in which —NH— may be interposed.
- Specific examples of the divalent hydrocarbon group having 1 to 20 carbon atoms that may be mediated by —NH— include —CH 2 CH 2 NH (CH 2 ) 3 —, —CH 2 CH 2 CH 2 —, and the like. Can be mentioned.
- Specific examples of the group containing an alkoxysilyl group include 2- (Trimethoxysilyl) ethyl group, 3- (trimethoxysilyl) propyl group, 4- (trimethoxysilyl) butyl group, 6- (trimethoxysilyl) hexyl group, 8- (trimethoxysilyl) octyl group, 2- (Triethoxysilyl) ethyl group, 3- (triethoxysilyl) propyl group, 4- (triethoxysilyl) butyl group, 6- (triethoxysilyl) hexyl group, 8- (triethoxysilyl) octyl group, 2- (Dimethoxymethylsilyl) ethyl group, 3- (dimethoxymethylsilyl) propyl group,
- the cyclopentene ring-opening polymer of the present invention has a group containing an alkoxysilyl group represented by the above general formula (2) at the end of the polymer chain. It has a structure formed by bonding to a polymer chain via —.
- the linking group for bonding the cyclopentene ring-opening polymer chain represented by pCP and —NH— that is, the group represented by Y 1 in the general formula (1) has a carbon number of 1 A divalent hydrocarbon group having 1 to 20 carbon atoms, and preferably a divalent hydrocarbon group having 1 to 10 carbon atoms.
- the cyclopentene ring-opening polymer of the present invention has a specific terminal structure at both polymer chain ends (both ends) even if a specific terminal structure is introduced only at one polymer chain end (one end). It may be introduced or a mixture of these. Furthermore, these may be mixed with a cyclopentene ring-opening polymer into which a specific terminal structure has not been introduced.
- the introduction rate of the specific terminal structure with respect to the polymer chain end is not particularly limited, but from the viewpoint of particularly improving the affinity between the cyclopentene ring-opening polymer and the filler,
- the percentage value of the number of cyclopentene ring-opening polymer chain ends / total number of cyclopentene ring-opening polymer chain ends into which the specific terminal structure has been introduced) is preferably 20% or more, more preferably 25% or more, More preferably, it is 30% or more.
- the introduction rate of the specific terminal structure with respect to the polymer chain terminal can be determined by 1 H-NMR spectrum measurement and gel permeation chromatography (GPC) measurement. Shows the integrated value of the peak derived from the proton of the carbon-carbon double bond existing in the main chain of the cyclopentene ring-opening polymer and the integrated value of the peak derived from the specific terminal structure, and GPC measurement by 1 H-NMR spectrum measurement Can be determined by comparing the number average molecular weight (Mn).
- the repeating unit constituting the main chain may consist only of a repeating unit obtained by ring-opening polymerization of cyclopentene, but other monomer capable of copolymerization with cyclopentene. It may contain repeating units derived from the body.
- the proportion of repeating units derived from other monomers is preferably 20 mol% or less, and preferably 15 mol% with respect to all repeating units. More preferably, it is more preferably 10 mol% or less.
- Examples of other monomers copolymerizable with cyclopentene include monocyclic olefins other than cyclopentene, monocyclic dienes, monocyclic trienes and polycyclic cyclic olefins, polycyclic cyclic dienes, and polycyclic cyclic trienes. .
- Examples of monocyclic olefins other than cyclopentene include cyclopentene having a substituent and cyclooctene which may have a substituent.
- Examples of the monocyclic diene include 1,5-cyclooctadiene which may have a substituent.
- Examples of the monocyclic triene include 1,5,9-cyclododecatriene which may have a substituent.
- Examples of the polycyclic olefin include norbornene compounds which may have a substituent.
- the molecular weight of the cyclopentene ring-opening polymer of the present invention is 100,000 to 1,000,000, preferably 150,000 to 900,000, more preferably 200 as the value of weight average molecular weight (Mw). , 000 to 800,000.
- Mw weight average molecular weight
- the ratio (Mw / Mn) of polystyrene-equivalent number average molecular weight (Mn) and weight average molecular weight (Mw) of the cyclopentene ring-opening polymer of the present invention measured by gel permeation chromatography is particularly limited. However, it is usually 4.0 or less, preferably 3.5 or less, and more preferably 3.0 or less. By having such Mw / Mn, a polymer composition having more excellent mechanical properties can be provided.
- the molecular weight of the cyclopentene ring-opening polymer is measured as a value in terms of polystyrene by gel permeation chromatography.
- the cis / trans ratio is not particularly limited, but is usually set in the range of 10/90 to 90/10. From the viewpoint of obtaining a cyclopentene ring-opening polymer that can provide a polymer composition exhibiting excellent properties at low temperatures, the range of 30/70 to 90/10 is preferred.
- the method for producing the cyclopentene ring-opening polymer of the present invention as described above is not particularly limited, but the production method suitably used is the method for producing the cyclopentene ring-opening polymer of the present invention described below.
- the method for producing a cyclopentene ring-opening polymer of the present invention comprises producing a cyclopentene ring-opening polymer having a halogen atom at the end of the polymer chain, and then the halogen atom, alkoxysilyl group and amino group of the cyclopentene ring-opening polymer. It reacts with the amino group of the compound which contains in the molecule
- a cyclopentene ring-opening polymer having a halogen atom at the polymer chain end is produced.
- a cyclopentene ring-opening polymer having a halogen atom at the end of the polymer chain may be produced by a known method, and the method is not particularly limited, but the ring-opening in the presence of an olefin compound having a halogen atom.
- a method of ring-opening polymerization of cyclopentene using a polymerization catalyst is preferred.
- the olefin compound having a halogen atom that can be used is a compound containing at least one ethylenically unsaturated bond and one halogen atom in the molecule. If it is, it will not be specifically limited.
- Specific examples of the olefin compound having a halogen atom include allyl chloride, allyl bromide, allyl iodide, crotyl chloride, 4-chloro-1-butene, 5-bromo-1-pentene, and 6-chloro-1-hexene.
- Olefin compounds containing a halogen atom on one side of an olefin such as 4-chlorostyrene and 4-bromostyrene; halogens on both sides of an olefin such as 1,4-dichloro-2-butene and 1,4-dibromo-2-butene Olefin compounds containing atoms; and the like.
- the olefin compound which has a halogen atom may be used individually by 1 type, and can also use 2 or more types together.
- a ruthenium carbene complex As a ring-opening polymerization catalyst that can be used in a method for ring-opening polymerization of cyclopentene in the presence of an olefin compound having a halogen atom, a ruthenium carbene complex can be exemplified.
- the ruthenium carbene complex is not particularly limited as long as it becomes a ring-opening polymerization catalyst for cyclopentene.
- Specific examples of ruthenium carbene complexes preferably used include bis (tricyclohexylphosphine) benzylidene ruthenium dichloride, bis (triphenylphosphine) -3,3-diphenylpropenylidene ruthenium dichloride, bis (tricyclohexylphosphine) t-butylvinylidene Ruthenium dichloride, bis (1,3-diisopropylimidazoline-2-ylidene) benzylidene ruthenium dichloride, bis (1,3-dicyclohexylimidazoline-2-ylidene) benzylidene ruthenium dichloride, (1,3-dimesityloimidazolin-2-ylidene ) (Tricyclohexylphos
- the amount of the ruthenium carbene complex used is not particularly limited, but the molar ratio of (metal ruthenium in the catalyst: monomer) is usually 1: 2,000 to 1: 2,000,000, preferably The range is from 1: 5,000 to 1: 1,500,000, more preferably from 1: 10,000 to 1: 1,000,000. If the amount used is too small, the polymerization reaction may not proceed sufficiently. On the other hand, if too much, removal of the catalyst residue from the resulting cyclopentene ring-opening polymer becomes difficult.
- the soot polymerization reaction may be carried out in the absence of a solvent or in a solution.
- the solvent used is inactive in the polymerization reaction and is not particularly limited as long as it is a solvent that can dissolve cyclopentene, a polymerization catalyst, etc. used in the polymerization, but a hydrocarbon solvent or a halogen solvent is used. It is preferable.
- hydrocarbon solvent examples include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; aliphatic hydrocarbons such as n-hexane, n-heptane, and n-octane; cyclohexane, cyclopentane, methylcyclohexane, and the like. And alicyclic hydrocarbons.
- halogen-based solvent examples include alkyl halogens such as dichloromethane and chloroform; aromatic halogens such as chlorobenzene and dichlorobenzene.
- the polymerization temperature is not particularly limited, but is usually set in the range of ⁇ 50 to 100 ° C.
- the polymerization reaction time is preferably 1 minute to 72 hours, more preferably 5 hours to 20 hours. After the polymerization conversion rate reaches a predetermined value, the polymerization reaction can be stopped by adding a known polymerization terminator to the polymerization system.
- a polymer solution containing a cyclopentene ring-opening polymer having a halogen atom at the end of the polymer chain can be obtained.
- the cyclopentene ring-opening polymer having a halogen atom at the polymer chain end may be recovered from the polymer solution and then subjected to a reaction with a compound containing an alkoxysilyl group and an amino group in the molecule. Can be directly subjected to a reaction with a compound containing an alkoxysilyl group and an amino group in the molecule.
- a known recovery method may be employed.For example, after separating the solvent by steam stripping, the solid is separated by filtration and further dried to obtain a solid state. A method for obtaining a polymer can be employed.
- the cyclopentene ring-opening polymer obtained using a ruthenium carbene complex tends to have a high ratio of trans structure in the double bond existing in the repeating unit, and therefore has crystallinity at a relatively low temperature.
- the characteristics as a rubber material may be inferior. From the viewpoint of preventing this, it is preferable to copolymerize cyclopentene with other monomers.
- Specific examples of other monomers that can be copolymerized with cyclopentene that can be used in this case include cyclooctene, 1,5-cyclooctadiene, and 1,5,9-cyclododecatriene.
- Examples of another ring-opening polymerization catalyst that can be used in the method of ring-opening polymerization of cyclopentene in the presence of an olefin compound having a halogen atom include molybdenum compounds and tungsten compounds.
- Specific examples of the molybdenum compound that can be used as the ring-opening polymerization catalyst include molybdenum pentachloride, molybdenum oxotetrachloride, and molybdenum (phenylimide) tetrachloride.
- Specific examples of the tungsten compound include tungsten hexachloride.
- an organic metal compound may be used in combination as a promoter.
- organometallic compound that can be used as the cocatalyst include organometallic compounds of Group 1, 2, 12, 13 or 14 metal atoms of the periodic table having a hydrocarbon group having 1 to 20 carbon atoms.
- organolithium compounds, organomagnesium compounds, organozinc compounds, organoaluminum compounds, and organotin compounds are preferably used, organolithium compounds, organotin compounds, and organoaluminum compounds are more preferred, and organoaluminum is particularly preferred. It is done.
- organomagnesium compound include butylethylmagnesium, butyloctylmagnesium, dihexylmagnesium, ethylmagnesium chloride, n-butylmagnesium chloride, allylmagnesium bromide, neopentylmagnesium chloride and neophyllmagnesium chloride.
- organic zinc compound include dimethyl zinc, diethyl zinc, and diphenyl zinc.
- organic tin compound examples include tetramethyltin, tetra (n-butyl) tin, and tetraphenyltin.
- organoaluminum compound examples include trialkylaluminum such as trimethylaluminum, triethylaluminum, and triisobutylaluminum; alkylaluminum halide such as diethylaluminum chloride, ethylaluminum sesquichloride, and ethylaluminum dichloride; in the following general formula (3) And the like.
- R 3 and R 4 represent a hydrocarbon group having 1 to 20 carbon atoms, and x is 0 ⁇ x ⁇ 3.
- specific examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R 3 and R 4 include methyl group, ethyl group, isopropyl group, n-propyl group, isobutyl group, n- Alkyl groups such as butyl, t-butyl, n-hexyl and cyclohexyl; aryls such as phenyl, 4-methylphenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl and naphthyl Group; and the like.
- the hydrocarbon groups having 1 to 20 carbon atoms represented by R 3 and R 4 may be the same or different, but are present in the repeating unit of the cyclopentene ring-opening polymer.
- the hydrocarbon group represented by R 4 has at least 4 carbon atoms. It is preferably an alkyl group formed by continuous bonding of at least one, and in particular, any of n-butyl group, 2-methyl-pentyl group, n-hexyl group, cyclohexyl group, n-octyl group and n-decyl group It is preferable that
- x is 0 ⁇ x ⁇ 3, but in the double bond existing in the repeating unit of the cyclopentene ring-opening polymer, the ratio of the cis structure is increased to obtain a rubber material. From the viewpoint of obtaining a cyclopentene ring-opening polymer having excellent characteristics, it is preferable to use an organoaluminum compound in which x in the general formula (3) is in the range of 0.5 ⁇ x ⁇ 1.5 as a promoter.
- the polymerization reaction conditions in the case of using a molybdenum compound or a tungsten compound as a ring-opening polymerization catalyst may be appropriately set within the range of the conditions described in the case of using a ruthenium carbene complex.
- the method for producing a cyclopentene ring-opening polymer according to the present invention includes, for example, producing a cyclopentene ring-opening polymer having a halogen atom at the polymer chain end as described above,
- the cyclopentene ring-opening polymer of the present invention is obtained by reacting an amino group of a compound containing a silyl group and an amino group in the molecule to form an —NH— bond.
- the hydrocarbon group derived from the olefin compound having a halogen atom described above constitutes Y 1 of the general formula (1).
- the compound containing an alkoxysilyl group and an amino group in the molecule used in the method for producing a cyclopentene ring-opening polymer of the present invention is a compound containing at least one alkoxysilyl group and an amino group in the molecule.
- Examples of the compound include a compound represented by the following general formula (4).
- R 5 and R 6 represent a hydrocarbon group having 1 to 20 carbon atoms
- Y 3 represents a divalent hydrocarbon group having 1 to 20 carbon atoms that may be interposed by —NH—.
- B is an integer of 1 to 3
- R 5 and R 6 are hydrocarbon groups having 1 to 20 carbon atoms, and examples thereof include alkyl groups having 1 to 20 carbon atoms and aryl groups having 6 to 20 carbon atoms.
- alkyl groups having 1 to 20 carbon atoms Preferably an alkyl group having 1 to 10 carbon atoms, more preferably a methyl group or an ethyl group.
- Y 3 is a divalent hydrocarbon group having 1 to 20 carbon atoms which may be intervened by —NH—, and 2 having 1 to 10 carbon atoms which may be intervened by —NH—.
- a valent hydrocarbon group is preferred.
- particularly preferred compounds include N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-amino.
- Conditions for reacting the halogen atom of the cyclopentene ring-opening polymer with the amino group of the compound containing an alkoxysilyl group and an amino group in the molecule are not particularly limited, and for example, 20 to 200 in a solvent or under no solvent. This can be done by heating to ° C.
- a solvent in the case of using a solvent the same solvent as the solvent used in the polymerization reaction can be used.
- the base catalyst represented by organic amines, such as a triethylamine and ethylenediamine, can be used.
- the reaction When the reaction is carried out in the absence of a solvent, the reaction may be carried out simultaneously with the kneading at the time of blending with the filler described later.
- a structure in which a polymer chain and a group containing an alkoxysilyl group are bonded via —NH— has “-NH 2 + (X ⁇ ) —”.
- An ammonium salt structure such as “is also included.
- X represents a halogen atom of a cyclopentene ring-opening polymer having a halogen atom at the end of the polymer chain.
- the structure represented by the general formula (1) includes a structure represented by the following general formula (5).
- the reaction ratio between the halogen atom of the cyclopentene ring-opening polymer and the amino group of the compound containing an alkoxysilyl group and an amino group in the molecule may be determined according to the introduction rate of the desired specific terminal structure, etc.
- the molar ratio of halogen atom: amino group is usually set in the range of 1: 1 to 1: 200, preferably in the range of 1: 1 to 1: 100.
- the cyclopentene ring-opening polymer of the present invention can be efficiently produced.
- anti-aging agents such as a phenol type stabilizer, a phosphorus type stabilizer, and a sulfur type stabilizer
- a cyclopentene ring-opened polymer is obtained as a polymer solution, a known recovery method may be employed to recover the polymer from the polymer solution.
- the polymer solution is poured into an excess poor solvent.
- a method of coagulating and recovering the polymer a method of separating the solvent by steam stripping and the like, filtering the solid, and drying it to obtain a solid polymer can be employed.
- the polymer composition of the present invention is a polymer composition comprising the cyclopentene ring-opening polymer of the present invention and silica or silica and carbon black as a filler.
- the nitrogen adsorption specific surface area of silica is preferably 50 to 400 m 2 / g, more preferably 100 to 220 m 2 / g.
- the pH of silica is preferably less than pH 7, more preferably pH 5 to 6.9. Within these ranges, the affinity between the cyclopentene ring-opening polymer and silica is particularly good.
- the blending amount of silica is not particularly limited, but is preferably 10 to 150 parts by weight, more preferably 20 to 120 parts by weight based on 100 parts by weight of the polymer component including the cyclopentene ring-opening polymer contained in the polymer composition. Part by weight, particularly preferably 40 to 100 parts by weight.
- silica When silica is used as the soot filler, it is preferable to add a silane coupling agent to the polymer composition for the purpose of improving the adhesion between the cyclopentene ring-opening polymer and silica.
- the silane coupling agent include vinyltriethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, bis (3- (triethoxysilyl) propyl) tetrasulfide, bis (3- (triethoxy Silyl) propyl) disulfide and the like, and tetrasulfides such as ⁇ -trimethoxysilylpropyldimethylthiocarbamyl tetrasulfide and ⁇ -trimethoxysilylpropylbenzothiazyl tetrasulfide described in JP-A-6-248116 Can be mentioned.
- silane coupling agents can be used alone or in combination of two or more.
- the amount of the silane coupling agent is preferably 0.1 to 30 parts by weight, more preferably 1 to 15 parts by weight with respect to 100 parts by weight of silica.
- the polymer composition of the present invention may further contain carbon black as a filler.
- carbon black that can be used in the polymer composition of the present invention include furnace black, acetylene black, thermal black, channel black, and graphite.
- furnace black is preferable, and specific examples thereof include SAF, ISAF, ISAF-HS, ISAF-LS, IISAF-HS, HAF, HAF-HS, HAF-LS, and FEF.
- SAF SAF
- ISAF-HS ISAF-HS
- ISAF-LS ISAF-LS
- IISAF-HS HAF, HAF-HS, HAF-LS, and FEF.
- the compounding amount of carbon black is usually 150 parts by weight or less with respect to 100 parts by weight of the polymer component including the cyclopentene ring-opening polymer contained in the polymer composition.
- the total amount of silica and carbon black is 10 to 10 parts by weight based on 100 parts by weight of the polymer component containing the cyclopentene ring-opening polymer contained in the polymer composition.
- the amount is preferably 150 parts by weight, and more preferably 30 to 150 parts by weight.
- the nitrogen adsorption specific surface area (N 2 SA) of carbon black is preferably 5 to 200 m 2 / g, more preferably 80 to 130 m 2 / g, and the dibutyl phthalate (DBP) adsorption amount is preferably 5 to 300 ml / g. 100 g, more preferably 80 to 160 ml / 100 g.
- N 2 SA nitrogen adsorption specific surface area
- DBP dibutyl phthalate
- the polymer composition of the present invention may further contain a rubber other than the cyclopentene ring-opening polymer of the present invention.
- rubbers other than the cyclopentene ring-opening polymer of the present invention include natural rubber (NR), polyisoprene rubber (IR), emulsion polymerization SBR (styrene-butadiene copolymer rubber), solution polymerization random SBR (bonded styrene 5 to 50% by weight, 1,2-bond content of butadiene part 10-80%), high trans SBR (trans bond content 70-95% of butadiene part), low cis BR (polybutadiene rubber), high cis BR, high Trans BR (trans bond content of butadiene part 70 to 95%), styrene-isoprene copolymer rubber, butadiene-isoprene copolymer rubber, emulsion polymerized styrene-acrylonitrile-butadiene copolymer
- the ratio of the cyclopentene ring-opening polymer is 10% by weight or more based on the total amount of the polymer components. It is preferably within the range of 20 to 90% by weight, more preferably within the range of 30 to 80% by weight. When the ratio of the cyclopentene ring-opening polymer of the present invention is too low, the physical properties of the polymer composition may be inferior.
- the polymer composition of the present invention contains a compounding agent such as a cross-linking agent, a cross-linking accelerator, a cross-linking activator, an anti-aging agent, an activator, a process oil, a plasticizer, a lubricant, etc. Each can be blended in the required amount.
- a compounding agent such as a cross-linking agent, a cross-linking accelerator, a cross-linking activator, an anti-aging agent, an activator, a process oil, a plasticizer, a lubricant, etc.
- crosslinking agents include sulfur such as powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur; sulfur halides such as sulfur monochloride and sulfur dichloride; dicumyl peroxide and ditertiary butyl peroxide.
- a polyhydric amine compound an alkylphenol resin having a methylol group; and the like.
- crosslinking agents are used alone or in combination of two or more.
- the blending amount of the crosslinking agent is preferably 0.1 to 15 parts by weight, more preferably 0.5 to 5 parts per 100 parts by weight of the polymer component including the cyclopentene ring-opening polymer contained in the polymer composition. Parts by weight.
- crosslinking accelerator examples include N-cyclohexyl-2-benzothiazylsulfenamide, Nt-butyl-2-benzothiazolesulfenamide, N-oxyethylene-2-benzothiazolesulfenamide, N- Sulfenamide-based crosslinking accelerators such as oxyethylene-2-benzothiazole sulfenamide and N, N′-diisopropyl-2-benzothiazole sulfenamide; guanidines such as diphenylguanidine, diortolylguanidine and orthotolylbiguanidine Thiourea crosslinking accelerators such as diethylthiourea; thiazole crosslinking accelerators such as 2-mercaptobenzothiazole, dibenzothiazyl disulfide, 2-mercaptobenzothiazole zinc salt; tetramethylthiuram monosulfide Thiuram-based cross-linking accelerators such as tetramethylthiuram dis
- crosslinking accelerators are used alone or in combination of two or more.
- the amount of the crosslinking accelerator is preferably 0.1 to 15 parts by weight, more preferably 0.5 to 100 parts by weight with respect to 100 parts by weight of the polymer component including the cyclopentene ring-opening polymer contained in the polymer composition. 5 parts by weight.
- cocoon crosslinking activator for example, higher fatty acids such as stearic acid or zinc oxide can be used.
- Zinc oxide preferably has a high surface activity particle size of 5 ⁇ m or less, and examples thereof include active zinc white having a particle size of 0.05 to 0.2 ⁇ m and zinc white having a particle size of 0.3 to 1 ⁇ m.
- zinc oxide what was surface-treated with an amine-based dispersant or wetting agent can also be used.
- the blending amount of the crosslinking activator is appropriately selected, but the blending amount of the higher fatty acid is preferably 0.1% with respect to 100 parts by weight of the polymer component including the cyclopentene ring-opening polymer contained in the polymer composition.
- the amount of zinc oxide is 100 parts by weight of the polymer component including the cyclopentene ring-opening polymer contained in the polymer composition.
- the amount is preferably 0.05 to 10 parts by weight, more preferably 0.5 to 3 parts by weight.
- Mineral oil or synthetic oil may be used as the process oil.
- mineral oil aroma oil, naphthenic oil, paraffin oil and the like are usually used.
- Other compounding agents include activators such as diethylene glycol, polyethylene glycol, and silicone oils; silica carbonates such as calcium carbonate, talc, and clay; fillers other than carbon black; tackifiers such as petroleum resins and coumarone resins; waxes, etc. Is mentioned.
- the polymer composition of the present invention can be obtained by kneading each component according to a conventional method.
- a compounding agent excluding a crosslinking agent and a crosslinking accelerator and a polymer (rubber) such as a cyclopentene ring-opening polymer are kneaded, and then the resulting mixture is mixed with a crosslinking agent and a crosslinking accelerator.
- the kneading temperature of the compounding agent excluding the crosslinking agent and crosslinking accelerator and the cyclopentene ring-opening polymer is preferably 80 to 200 ° C., more preferably 120 to 180 ° C., and the kneading time is preferably 30 seconds to 30 ° C. For minutes.
- Mixing of the crosslinking agent and the crosslinking accelerator is usually performed after cooling to 100 ° C. or lower, preferably 80 ° C. or lower.
- the polymer composition of the present invention has a total amount of silica or silica and carbon black of 10 to 150 with respect to 100 parts by weight of a polymer component containing a cyclopentene ring-opening polymer having a halogen atom at the polymer chain end. It may also be obtained by blending and reacting 0.01 to 20 parts by weight of a compound containing 0.01 part by weight and a compound containing an alkoxysilyl group and an amino group in the molecule.
- the polymer composition of the present invention comprises, as a polymer component, a polymer chain end and a group containing an alkoxysilyl group bonded to the end of the polymer chain via —NH—. It is a cyclopentene ring-opening polymer having a structure, and the structure contains a cyclopentene ring-opening polymer having a structure represented by the general formula (1).
- the ratio of the polymer is preferably 10% by weight or more, more preferably in the range of 20 to 90% by weight, and more preferably in the range of 30 to 80% by weight with respect to the total amount of the polymer components. More preferred.
- examples of the compound containing an alkoxysilyl group and an amino group in the molecule include the compound represented by the general formula (4) described above.
- the polymer composition of the present invention is usually used as a crosslinked polymer by crosslinking.
- the crosslinking method is not particularly limited, and may be selected according to the shape and size of the polymer crosslinked product.
- the mold may be filled with the polymer composition and heated to crosslink simultaneously with the molding, or the previously molded polymer composition may be heated to crosslink.
- the crosslinking temperature is preferably 120 to 200 ° C., more preferably 140 to 180 ° C., and the crosslinking time is usually about 1 to 120 minutes.
- the polymer composition of the present invention is excellent in affinity with silica and carbon black, it gives a crosslinked polymer having excellent low heat build-up. Therefore, various applications that make use of the characteristics, for example, use in tire parts such as treads, carcass, sidewalls, and bead parts, or rubber products such as hoses, window frames, belts, shoe soles, anti-vibration rubber, and automobile parts. Further, it can be used as a resin reinforced rubber such as impact-resistant polystyrene and ABS resin.
- tire tread for a fuel-efficient tire is excellent as a tire tread for a fuel-efficient tire, and is also suitable as a material for tire treads such as all-season tires, high-performance tires, studless tires, sidewalls, undertreads, carcass, and beat parts.
- a cyclopentene ring-opening polymer was measured with a gel permeation chromatography (GPC) system HLC-8220 (manufactured by Tosoh Corporation) using an H-type column HZ-M (manufactured by Tosoh Corporation) at 40 ° C. using tetrahydrofuran as a solvent.
- the number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were measured as polystyrene equivalent values.
- the vacuum-dried coagulated product was placed in a wire mesh basket and immersed in a large excess of toluene at 23 ° C. for 3 days to dissolve the cyclopentene ring-opening polymer not bonded to silica or carbon black.
- the coagulated material remaining in the basket was washed with toluene and then dried with a vacuum dryer, the weight after drying was measured, and the weight increased from a total of 1 part of the silica and carbon black used was determined. .
- This increased weight can be said to be a cyclopentene ring-opening polymer bonded to silica and / or carbon black, and the higher this value, the better the affinity for the filler.
- the polymer composition as a sample is press-crosslinked at 160 ° C. for 20 minutes to produce a crosslinked test piece, and a viscoelasticity measuring device (trade name “EPLEXOR”, manufactured by GABO) is used for the test piece. Used, tan ⁇ at 60 ° C. was measured under conditions of initial strain of 0.5%, dynamic strain of 1% and 10 Hz. This value was an index with the measured value of the sample of Comparative Example 4 as 100. It can be said that the smaller the index, the better the low heat build-up.
- the resulting cyclopentene ring-opening polymer (A1) had a weight average molecular weight (Mw) of 380,000, a molecular weight distribution (Mw / Mn) of 1.92, and a cis / trans ratio of 60/40. Further, the bromine atom introduction rate into the polymer chain terminal was 74%.
- the resulting cyclopentene ring-opening polymer (A2) had a weight average molecular weight (Mw) of 438,000, a molecular weight distribution (Mw / Mn) of 1.99, and a cis / trans ratio of 17/83. Further, the introduction rate of halogen atoms into the polymer chain terminal was 100%.
- Example 1 Under a nitrogen atmosphere, to a pressure-resistant glass reaction vessel equipped with a stirrer, 50 parts of a cyclopentene ring-opening polymer (A1) having a bromine atom at the polymer chain end obtained in Production Example 1 and 450 parts of tetrahydrofuran (THF) were added.
- the ring-opening polymer (A1) was dissolved in THF, and further 1.1 parts of 3-aminopropyltriethoxysilane and 0.51 parts of triethylamine were added, followed by stirring at 60 ° C. for 48 hours, so as to The bromine atom was reacted with the amino group of 3-aminopropyltriethoxysilane.
- a cyclopentene ring-opening polymer (A1-Si) having a specific terminal structure The resulting cyclopentene ring-opening polymer (A1-Si) had a weight average molecular weight (Mw) of 334,000 and a molecular weight distribution (Mw / Mn) of 2.45. Moreover, the introduction rate of the specific terminal structure to the polymer chain terminal was 75%. A part of the obtained cyclopentene ring-opening polymer (A1-Si) was used to evaluate the affinity for the filler.
- BHT 2,6-di-t-butyl-p-cresol
- cyclopentene ring-opening polymer (A1-Si), a commercially available styrene butadiene rubber (trade name “Nipol SBR 1723”, bound styrene content 23.5%, extension oil content 27.3%, ZEON CORPORATION 55 parts, and 10 parts of a commercially available polybutadiene rubber (trade name “Nipol® BR1220”, manufactured by Nippon Zeon Co., Ltd.) for 30 seconds in a Brabender type mixer, and then silica (trade name “Zeosil® 1165MP”, 50 parts by Rhodia), 5.6 parts of silane coupling agent (trade name “Si75”, bis (3- (triethoxysilyl) propyl) disulfide, manufactured by Degussa), and process oil (trade name “Fukkor Eromic 30”) (Manufactured by Nippon Oil Co., Ltd.) After kneading for 5 minutes, 10 parts
- the kneaded material was discharged from the mixer.
- the temperature of the kneaded product at the end of kneading was 150 ° C. After the kneaded product was cooled to room temperature, it was kneaded again in a Brabender type mixer at 80 ° C. for 2 minutes, and then the kneaded product was discharged from the mixer.
- Example 2 50 parts of the cyclopentene ring-opening polymer (A1) obtained in Production Example 1, a commercially available styrene butadiene rubber (trade name “Nipol SBR1723”, bound styrene content 23.5%, extended oil content 27.3%, Nippon Zeon 55 parts, commercially available polybutadiene rubber (trade name “Nipol BR1220”, manufactured by Nippon Zeon Co., Ltd.), 10 parts, and 1.1 parts of 3-aminopropyltriethoxysilane are kneaded in a Brabender type mixer for 30 seconds. Thus, a kneaded product was obtained.
- Example 1 the whole amount of the kneaded product obtained above was used for the production of the sheet-like polymer composition similar to Example 1 (the step after the step of kneading together with styrene butadiene rubber and polybutadiene rubber).
- a sheet-like polymer composition was produced. This polymer composition was evaluated for low heat build-up. The results of measurement and evaluation in Example 2 are shown in Table 1.
- the affinity evaluation for the filler was carried out by dissolving 1 part of the cyclopentene ring-opening polymer (A1) obtained in Production Example 1 in 18 parts of decalin, and then adding silica (trade name “Zeosil 1165MP”, Rhodia) 0.5 parts of carbon black (trade name “SEAST 7HM”, manufactured by Tokai Carbon Co., Ltd.), 0.022 parts of 3-aminopropyltriethoxysilane, and 6 parts at 150 ° C. Stir for hours. Thereafter, in the same manner as in [Affinity evaluation of cyclopentene ring-opening polymer for filler], the weight increased from a total of 1 part of the silica and carbon black used was determined.
- Example 3 Instead of 50 parts of the cyclopentene ring-opening polymer (A1) obtained in Production Example 1, 50 parts of the cyclopentene ring-opening polymer (A2) obtained in Production Example 2 was used, and 3-aminopropyltriethoxysilane Cyclopentene ring opening having a specific terminal structure in the same manner as in Example 1 except that 1.3 parts of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane was used instead of 1.1 parts. 50 parts of polymer (A2-Si) were obtained.
- the resulting cyclopentene ring-opening polymer (A2-Si) had a weight average molecular weight (Mw) of 378,000 and a molecular weight distribution (Mw / Mn) of 2.20. Moreover, the introduction rate of the specific terminal structure to the polymer chain terminal was 88%. A part of the obtained cyclopentene ring-opening polymer (A2-Si) was used to evaluate the affinity for the filler. Next, in the same manner as in Example 1 except that 50 parts of the resulting cyclopentene ring-opening polymer (A2-Si) was used instead of 50 parts of the cyclopentene ring-opening polymer (A1-Si), A polymer composition was prepared. This polymer composition was evaluated for low heat build-up. The results of measurement and evaluation in Example 3 are summarized in Table 1.
- the polymerization was stopped by adding excess isopropanol. When the resulting solution was poured into a large excess of isopropanol, polymer precipitation occurred. The precipitated polymer was collected, washed with isopropanol, and then vacuum-dried at 40 ° C. for 3 days, whereby a cyclopentene ring-opening polymer having a triethoxysilyl group introduced by a metathesis reaction at the polymer chain end ( A′1) 76 parts were obtained.
- the obtained polymer had a weight average molecular weight (Mw) of 338,000, a molecular weight distribution (Mw / Mn) of 2.05, and a cis / trans ratio of 60/40.
- the introduction rate of the triethoxysilyl group into the polymer chain terminal was 100%.
- a part of the obtained polymer was evaluated for affinity for the filler.
- 50 parts of the cyclopentene ring-opening polymer (A1-Si) 50 parts of the obtained cyclopentene ring-opening polymer (A′1) is used as it is, in the same sheet-like polymer composition as in Example 1.
- a sheet-like polymer composition was produced in the same manner as in Example 1 except that the composition was used for the production of This polymer composition was evaluated for low heat build-up.
- the results of measurement and evaluation in Comparative Example 3 are summarized in Table 1.
- Example 1 instead of 50 parts of the cyclopentene ring-opening polymer (A1-Si), 50 parts of the obtained cyclopentene ring-opening polymer was used for the production of a sheet-like polymer composition as in Example 1. Except for this, in the same manner as in Example 1, this polymer composition was evaluated for low heat buildup as a sheet-like polymer composition.
- Table 1 The results of measurement and evaluation in Comparative Example 4 are summarized in Table 1.
- a cyclopentene ring-opening polymer (B1) having a hydroxyl group at the polymer chain end and 630 parts of toluene are added to a pressure-resistant glass reaction vessel equipped with a stirrer in a nitrogen atmosphere, and the polymer is dissolved in toluene.
- a pressure-resistant glass reaction vessel equipped with a stirrer in a nitrogen atmosphere By adding 18 parts of-(triethoxysilyl) propyl isocyanate and stirring at 100 ° C. for 20 hours, the hydroxyl group at the end of the polymer chain reacts with the isocyanate group of 3- (triethoxysilyl) propyl isocyanate to give urethane.
- a linking group was formed.
- the resulting cyclopentene ring-opening polymer (B1-Si) had a weight average molecular weight (Mw) of 351,600 and a molecular weight distribution (Mw / Mn) of 1.95. Moreover, the introduction rate of the triethoxysilyl group through the urethane bond to the polymer chain terminal was 94%. A part of the obtained cyclopentene ring-opening polymer was used to evaluate the affinity for the filler. Then, in the same manner as in Example 1, except that 50 parts of the resulting cyclopentene ring-opening polymer (B1-Si) was used instead of 50 parts of the cyclopentene ring-opening polymer (A1-Si), A polymer composition was prepared. This polymer composition was evaluated for low heat build-up. The results of measurement and evaluation in Comparative Example 5 are summarized in Table 1.
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Abstract
Description
〔1〕重合体鎖末端に、重合体鎖とアルコキシシリル基を含有する基とが、-NH-を介して結合されてなる構造を有し、重量平均分子量が100,000~1,000,000である、シクロペンテン開環重合体であって、
前記構造が、下記の一般式(1)で表される構造である、シクロペンテン開環重合体、
pCP-Y1-NH-Y2-Si(OR1)a(R2)3-a (1)
(一般式(1)中、pCPはシクロペンテン開環重合体鎖を表し、Y1は炭素数1~20の2価の炭化水素基を表し、R1およびR2は炭素数1~20の炭化水素基を表し、Y2は-NH-が介在してもよい炭素数1~20の2価の炭化水素基を表し、aは1~3の整数である。)、
〔2〕前記アルコキシシリル基を含有する基が、トリアルコキシシリル基を含有する基である〔1〕に記載のシクロペンテン開環重合体、
〔5〕重合体鎖末端にハロゲン原子を有するシクロペンテン開環重合体を含む重合体成分100重量部に対して、
シリカもしくはシリカおよびカーボンブラックの合計量として10~150重量部、ならびに、アルコキシシリル基およびアミノ基を分子中に含有する化合物0.01~20重量部を配合し、反応させてなる、
重合体鎖末端に、重合体鎖末端とアルコキシシリル基を含有する基とが、-NH-を介して結合されてなる構造を有するシクロペンテン開環重合体を含む、重合体組成物であって、
前記構造が、下記の一般式(1)で表される構造である、重合体組成物、
pCP-Y1-NH-Y2-Si(OR1)a(R2)3-a (1)
(一般式(1)中、pCPはシクロペンテン開環重合体鎖を表し、Y1は炭素数1~20の2価の炭化水素基を表し、R1およびR2は炭素数1~20の炭化水素基を表し、Y2は-NH-が介在してもよい炭素数1~20の2価の炭化水素基を表し、aは1~3の整数である。)
〔7〕〔6〕に記載の重合体組成物を架橋してなる重合体架橋物。
pCP-Y1-NH-Y2-Si(OR1)a(R2)3-a (1)
(一般式(1)中、pCPはシクロペンテン開環重合体鎖を表し、Y1は炭素数1~20の2価の炭化水素基を表し、R1およびR2は炭素数1~20の炭化水素基を表し、Y2は-NH-が介在してもよい炭素数1~20の2価の炭化水素基を表し、aは1~3の整数である。)
-Y2-Si(OR1)a(R2)3-a (2)
(一般式(2)中、R1、R2、Y2、aは一般式(1)と同様。)
pCP-Y1-NH2 +(X-)-Y2-Si(OR1)a(R2)3-a (5)
この場合には、本発明の重合体組成物は、重合体成分として、重合体鎖末端に、重合体鎖末端とアルコキシシリル基を含有する基とが、-NH-を介して結合されてなる構造を有するシクロペンテン開環重合体であり、該構造が、上記一般式(1)で表される構造であるシクロペンテン開環重合体を含有することとなる。
ゲル・パーミエーション・クロマトグラフィー(GPC)システム HLC-8220(東ソー社製)で、HタイプカラムHZ-M(東ソー社製)を用い、テトラヒドロフランを溶媒として40℃で測定し、シクロペンテン開環重合体の数平均分子量(Mn)、重量平均分子量(Mw)および分子量分布(Mw/Mn)を、ポリスチレン換算値として測定した。
13C-NMRスペクトル測定により決定した。
1H-NMRスペクトル測定により、各種の官能基に由来するピーク積分値とシクロペンテン開環重合体主鎖中の炭素-炭素二重結合に由来するピーク積分値との比率を求め、このピーク積分値の比率とGPCによる数平均分子量(Mn)の測定値に基づいて、各種の官能基の導入率〔(官能基が導入されたシクロペンテン開環重合体鎖末端数/シクロペンテン開環重合体鎖末端全数)の百分率〕を計算した。
1H-NMRスペクトル測定により、アルコキシシリル基に由来するピーク積分値とシクロペンテン開環重合体主鎖中の炭素-炭素二重結合に由来するピーク積分値との比率を求め、このピーク積分値の比率とGPCによる数平均分子量(Mn)の測定値に基づいて、特定末端構造の導入率〔(特定末端構造が導入されたシクロペンテン開環重合体鎖末端数/シクロペンテン開環重合体鎖末端全数)の百分率〕を計算した。なお、1H-NMRスペクトル測定においては、3.8ppm付近に現れるアルコキシシリル基に由来するピークと、2.5~3.5ppm付近に現れる-NH-に隣接するメチレン基に由来するピークとの存在を確認することにより、特定末端構造の導入の確認を行なった。
試料となるシクロペンテン開環重合体1部をデカリン18部に溶解した後、この溶液にシリカ(商品名「Zeosil 1165MP」、ローディア社製)0.5部およびカーボンブラック(商品名「シースト7HM」、東海カーボン社製)0.5部を加え、150℃で6時間攪拌した。次に、この溶液を大過剰のイソプロパノールに加え、これにより生じた凝固物を回収して、40℃で2日間真空乾燥した。そして、真空乾燥した凝固物を金網かごに入れて、大過剰のトルエンに23℃で3日間浸漬することにより、シリカまたはカーボンブラックに結合していないシクロペンテン開環重合体を溶解させた。かごの中に残った凝固物については、トルエンで洗浄した後、真空乾燥機で乾燥し、乾燥後の重量を測定し、用いたシリカとカーボンブラックとの合計1部から増加した重量を求めた。この増加した重量は、シリカおよび/またはカーボンブラックに結合したシクロペンテン開環重合体であるといえ、この値が高いものほど、充填剤に対する親和性に優れるといえる。
試料となる重合体組成物を、160℃で20分間プレス架橋することで、架橋された試験片を作製し、この試験片について、粘弾性測定装置(商品名「EPLEXOR」、GABO社製)を用い、初期歪み0.5%、動的歪み1%、10Hzの条件で60℃におけるtanδを測定した。この値は、比較例4の試料の測定値を100とする指数とした。この指数が小さいものほど、低発熱性に優れるといえる。
窒素雰囲気下、攪拌機付き耐圧ガラス反応容器に、シクロペンテン200部およびトランス-1,4-ジブロモ-2-ブテン0.17部、トルエン800部を加えた。次に、2.5重量%のジイソブチルアルミニウムモノ(n-ヘキシルオキシド)/トルエン溶液4.3部を加え、続いて1.0重量%のWCl6/トルエン溶液8.7部を加えて、25℃で6時間重合反応を行った。6時間の重合反応後、耐圧ガラス反応容器に、過剰のイソプロパノールを加えて重合を停止した後、老化防止剤として、イルガノックス1520L(チバスペシャリティーケミカルズ社製)を得られた重合体100部に対して0.15部添加した後、スチームストリッピングにより溶媒を除去し、60℃で24時間真空乾燥して、176部の重合体鎖末端に臭素原子を有するシクロペンテン開環重合体(A1)を得た。得られたシクロペンテン開環重合体(A1)の重量平均分子量(Mw)は380,000、分子量分布(Mw/Mn)は1.92で、シス/トランス比は60/40であった。また、重合体鎖末端への臭素原子導入率は74%であった。
窒素雰囲気下、磁気攪拌子を入れた耐圧ガラス反応容器に、シクロペンテン200部および1,4-ジクロロ-2-ブテン(シス/トランス混合物)0.24部を加えた。次に、トルエン10部に溶解した(1,3-ジメシチルイミダゾリジン-2-イリデン)(トリシクロヘキシルホスフィン)ベンジリデンルテニウムジクロリド0.050部を加え、40℃で1時間重合反応を行った。重合反応後、過剰のビニルエチルエーテルを加えることにより重合を停止した後、得られた溶液を大過剰のイソプロパノールに注いだところ、重合体の沈殿が生じた。沈殿した重合体を回収し、イソプロパノールで洗浄した後、40℃で3日間、真空乾燥することにより、重合体鎖末端に塩素原子を有するシクロペンテン開環重合体(A2)98部を得た。得られたシクロペンテン開環重合体 (A2)の重量平均分子量(Mw)は438,000、分子量分布(Mw/Mn)は1.99で、シス/トランス比は17/83であった。また、重合体鎖末端へのハロゲン原子の導入率は100%であった。
窒素雰囲気下、攪拌機付き耐圧ガラス反応容器に、製造例1で得られた重合体鎖末端に臭素原子を有するシクロペンテン開環重合体(A1)50部およびテトラヒドロフラン(THF)450部を加えて、シクロペンテン開環重合体(A1)をTHFに溶解し、さらに3-アミノプロピルトリエトキシシラン1.1部およびトリエチルアミン0.51部を加えて、60℃で48時間攪拌することにより、重合体鎖末端の臭素原子と3-アミノプロピルトリエトキシシランのアミノ基とを反応させた。反応終了後、容器内の溶液を2,6-ジ-t-ブチル-p-クレゾール(BHT)を含む大過剰のイソプロパノールに注いだところ、重合体の沈殿が生じた。沈殿した重合体を回収し、イソプロパノールで洗浄した後、40℃で3日間、真空乾燥することにより、特定末端構造を有するシクロペンテン開環重合体(A1-Si)50部を得た。得られたシクロペンテン開環重合体(A1-Si)の重量平均分子量(Mw)は334,000、分子量分布(Mw/Mn)は2.45であった。また、重合体鎖末端への特定末端構造の導入率は75%であった。得られたシクロペンテン開環重合体(A1-Si)の一部を用いて、充填剤に対する親和性評価を行った。
製造例1で得られたシクロペンテン開環重合体(A1)50部、市販のスチレンブタジエンゴム(商品名「Nipol SBR1723」、結合スチレン量23.5%、伸展油含有量27.3%、日本ゼオン社製)55部、市販のポリブタジエンゴム(商品名「Nipol BR1220」、日本ゼオン社製)10部、および3-アミノプロピルトリエトキシシラン1.1部をブラベンダータイプミキサー中で30秒間素練りすることで、混練物を得た。
製造例1で得られたシクロペンテン開環重合体(A1)50部に代えて製造例2で得られたシクロペンテン開環重合体(A2)50部を用いたこと、および3-アミノプロピルトリエトキシシラン1.1部に代えてN-(2-アミノエチル)-3-アミノプロピルトリメトキシシラン1.3部を用いたこと以外は、実施例1と同様にして、特定末端構造を有するシクロペンテン開環重合体(A2-Si)50部を得た。得られたシクロペンテン開環重合体(A2-Si)の重量平均分子量(Mw)は378,000、分子量分布(Mw/Mn)は2.20であった。また、重合体鎖末端への特定末端構造の導入率は88%であった。得られたシクロペンテン開環重合体(A2-Si)の一部を用いて、充填剤に対する親和性評価を行った。次いで、シクロペンテン開環重合体(A1-Si)50部に代えて、得られたシクロペンテン開環重合体(A2-Si)50部を使用した以外は、実施例1と同様にして、シート状の重合体組成物を作製した。この重合体組成物について、低発熱性の評価を行った。実施例3における、それぞれの測定・評価結果は、表1にまとめて示した。
製造例1で得られた重合体鎖末端に臭素原子を有するシクロペンテン開環重合体(A1)の一部について、充填剤に対する親和性評価を行った。さらに、製造例1で得られたシクロペンテン開環重合体(A1)について、3-アミノプロピルトリエトキシシラン1.1部を加えなかったこと以外は、実施例2と同様にして、シート状の重合体組成物を作製した。この重合体組成物について、低発熱性の評価を行った。比較例1における、それぞれの測定・評価結果は、表1にまとめて示した。
製造例2で得られた重合体鎖末端に塩素原子を有するシクロペンテン開環重合体(A2)の一部について、充填剤に対する親和性評価を行った。さらに、製造例2で得られたシクロペンテン開環重合体(A2)について、3-アミノプロピルトリエトキシシラン1.1部を加えなかったこと以外は、実施例2と同様にして、シート状の重合体組成物を作製した。この重合体組成物について、低発熱性の評価を行った。比較例2における、それぞれの測定・評価結果は、表1にまとめて示した。
窒素雰囲気下、攪拌子の入ったガラス容器に、濃度1.0重量%のWCl6/トルエン溶液8.7部、および濃度2.5重量%のジイソブチルアルミニウムモノ(n-ヘキシルオキシド)/トルエン溶液4.3部を加え、15分間攪拌することにより、触媒溶液を得た。そして、窒素雰囲気下、攪拌機付き耐圧ガラス反応容器に、シクロペンテン150部およびビス(トリエトキシシリル)エチレン0.21部を加え、ここに、上記にて調製した触媒溶液13部を加えて、25℃で6時間重合反応を行った。重合反応後、過剰のイソプロパノールを加えることにより、重合を停止した。得られた溶液を大過剰のイソプロパノールに注いだところ、重合体の沈殿が生じた。沈殿した重合体を回収し、イソプロパノールで洗浄した後、40℃で3日間、真空乾燥することにより、重合体鎖末端に、メタセシス反応で導入されたトリエトキシシリル基を有するシクロペンテン開環重合体(A’1)76部を得た。得られた重合体の重量平均分子量(Mw)は338,000、分子量分布(Mw/Mn)は2.05で、シス/トランス比は60/40であった。また、重合体鎖末端へのトリエトキシシリル基の導入率は100%であった。得られた重合体の一部について、充填剤に対する親和性評価を行った。さらに、シクロペンテン開環重合体(A1-Si)50部に代えて、得られたシクロペンテン開環重合体(A’1)50部を、そのまま、実施例1と同様のシート状の重合体組成物の製造に供したこと以外は、実施例1と同様にして、シート状の重合体組成物を作製した。この重合体組成物について、低発熱性の評価を行った。比較例3における、それぞれの測定・評価結果は、表1にまとめて示した。
ビス(トリエトキシシリル)エチレン0.21部に代えて、1-ヘキセン0.090部を用いたこと以外は、比較例3と同様にして、重合体鎖末端に、官能基を有さないシクロペンテン開環重合体68部を得た。得られたシクロペンテン開環重合体の重量平均分子量(Mw)は291,100、分子量分布(Mw/Mn)は2.15で、シス/トランス比は61/39であった。得られたシクロペンテン開環重合体の一部について、充填剤に対する親和性評価を行った。さらに、シクロペンテン開環重合体(A1-Si)50部に代えて、得られたシクロペンテン開環重合体50部を、そのまま、実施例1と同様のシート状の重合体組成物の製造に供したこと以外は、実施例1と同様にして、シート状の重合体組成物として、この重合体組成物について、低発熱性の評価を行った。比較例4における、それぞれの測定・評価結果は、表1にまとめて示した。
1,4-ジクロロ-2-ブテン0.24部に代えて、2-ブテン-1,4-ジオール0.038部を用いたこと以外は、製造例2と同様にして重合を行い、重合体鎖末端に水酸基を有するシクロペンテン開環重合体(B1)130部を得た。得られたシクロペンテン開環重合体(B1)の重量平均分子量(Mw)は283,600、分子量分布(Mw/Mn)は1.90で、シス/トランス比は18/82であった。また、重合体鎖末端への水酸基の導入率は91%であった。次いで、窒素雰囲気下、攪拌機付き耐圧ガラス反応容器に、重合体鎖末端に水酸基を有するシクロペンテン開環重合体(B1)70部およびトルエン630部を加えて、重合体をトルエンに溶解し、さらに3-(トリエトキシシリル)プロピルイソシアネート18部を加えて、100℃で20時間攪拌することにより、重合体鎖末端の水酸基と3-(トリエトキシシリル)プロピルイソシアネートのイソシアネート基とを反応させて、ウレタン結合基を形成させた。反応終了後、容器内の溶液を2,6-ジ-t-ブチル-p-クレゾール(BHT)を含む大過剰のイソプロパノールに注いだところ、重合体の沈殿が生じた。沈殿した重合体を回収し、イソプロパノールで洗浄した後、40℃で3日間、真空乾燥することにより、ウレタン結合を介したトリエトキシシリル基を有するシクロペンテン開環重合体(B1-Si)70部を得た。得られたシクロペンテン開環重合体(B1-Si)の重量平均分子量(Mw)は351,600、分子量分布(Mw/Mn)は1.95であった。また、重合体鎖末端へのウレタン結合を介したトリエトキシシリル基の導入率は94%であった。得られたシクロペンテン開環重合体の一部を用いて、充填剤に対する親和性評価を行った。そして、シクロペンテン開環重合体(A1-Si)50部に代えて、得られたシクロペンテン開環重合体(B1-Si)50部を使用した以外は、実施例1と同様にして、シート状の重合体組成物を作製した。この重合体組成物について、低発熱性の評価を行った。比較例5における、それぞれの測定・評価結果は、表1にまとめて示した。
重合体鎖末端に、重合体鎖とアルコキシシリル基を含有する基とが-NH-を介して結合されてなる構造であって、一般式(1)で表される構造を有するシクロペンテン開環重合体はいずれもシクロペンテン開環重合体の充填剤に対する親和性が高く、低発熱性が良好となった(実施例1~3)。それに対して、実施例のような構造を有しない場合は、シクロペンテン開環重合体の充填剤に対する親和性が低くなり、低発熱性に劣る結果となった(比較例1~5)。
Claims (7)
- 重合体鎖末端に、重合体鎖とアルコキシシリル基を含有する基とが、-NH-を介して結合されてなる構造を有し、重量平均分子量が100,000~1,000,000である、シクロペンテン開環重合体であって、
前記構造が、下記の一般式(1)で表される構造である、シクロペンテン開環重合体。
pCP-Y1-NH-Y2-Si(OR1)a(R2)3-a (1)
(一般式(1)中、pCPはシクロペンテン開環重合体鎖を表し、Y1は炭素数1~20の2価の炭化水素基を表し、R1およびR2は炭素数1~20の炭化水素基を表し、Y2は-NH-が介在してもよい炭素数1~20の2価の炭化水素基を表し、aは1~3の整数である。) - 前記アルコキシシリル基を含有する基が、トリアルコキシシリル基を含有する基である請求項1に記載のシクロペンテン開環重合体。
- 請求項1または2に記載のシクロペンテン開環重合体を製造する方法であって、重合体鎖末端にハロゲン原子を有するシクロペンテン開環重合体を製造し、次いで、前記重合体鎖末端にハロゲン原子を有するシクロペンテン開環重合体のハロゲン原子と、アルコキシシリル基およびアミノ基を分子中に含有する化合物のアミノ基とを反応させることを特徴とする、シクロペンテン開環重合体の製造方法。
- 請求項1または2に記載のシクロペンテン開環重合体を含む重合体成分に、前記重合体成分100重量部に対して、シリカもしくはシリカおよびカーボンブラックの合計量として10~150重量部を配合した重合体組成物。
- 重合体鎖末端にハロゲン原子を有するシクロペンテン開環重合体を含む重合体成分100重量部に対して、
シリカもしくはシリカおよびカーボンブラックの合計量として10~150重量部、ならびに、アルコキシシリル基およびアミノ基を分子中に含有する化合物0.01~20重量部を配合し、反応させてなる、
重合体鎖末端に、重合体鎖末端とアルコキシシリル基を含有する基とが、-NH-を介して結合されてなる構造を有するシクロペンテン開環重合体を含む、重合体組成物であって、
前記構造が、下記の一般式(1)で表される構造である、重合体組成物。
pCP-Y1-NH-Y2-Si(OR1)a(R2)3-a (1)
(一般式(1)中、pCPはシクロペンテン開環重合体鎖を表し、Y1は炭素数1~20の2価の炭化水素基を表し、R1およびR2は炭素数1~20の炭化水素基を表し、Y2は-NH-が介在してもよい炭素数1~20の2価の炭化水素基を表し、aは1~3の整数である。) - 架橋剤をさらに含有してなる、請求項4または5に記載の重合体組成物。
- 請求項6に記載の重合体組成物を架橋してなる重合体架橋物。
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