JP5353677B2 - Method for producing cyclopentene ring-opening polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cyclopentene ring-opened polymer which excels in hot flowability, is thereby easy to produce, and excels in processability. <P>SOLUTION: A method for producing the cyclopentene ring-opened polymer by ring-opening polymerization of cyclopentene in the presence of a metathesis polymerization catalyst comprises reacting a cyclic olefin having 0.001-1 mol% vinyl group based on the cyclopentene and/or a compound having 3 or more vinyl groups with the cyclopentene. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a method for producing a cyclopentene ring-opening polymer having excellent hot flow properties.

In general, cyclopentene is a so-called Ziegler-Natta catalyst comprising a Group 6 transition metal compound of the periodic table such as WCl ₆ and MoCl ₅ and an organometallic activator such as triisobutylaluminum, diethylaluminum chloride, tetrabutyltin. Under the metathesis ring-opening polymerization, it is known to give unsaturated linear ring-opening polymers.

  Since such a cyclopentene ring-opening polymer is a rubber-like polymer at room temperature, attempts to use it as a rubber material have been made for a long time. In particular, among the cyclopentene ring-opened polymers, cyclopentene ring-opened polymers having a high trans ratio have been extensively studied as rubber properties, and cyclopentene ring-opened polymers having a high trans ratio have crystallinity at low temperatures. It has a green strength and high wear resistance, and is excellent in tackiness. However, since it has crystallinity, it has been known that there is a problem that it has poor rubber properties at low temperatures.

  In addition, the cyclopentene ring-opening polymer is a linear polymer that does not have a branched structure regardless of the cis / trans ratio. It has been known that there are problems that the polymer is aggregated when exposed to exposure, and that it is difficult to produce, and that it is difficult to blend various compounding agents into a rubber composition.

  For example, Patent Document 1 proposes a method in which cyclododecatriene or the like is copolymerized with cyclopentene in order to reduce crystallinity at low temperatures and thereby improve rubber properties at low temperatures. However, the cyclopentene ring-opening copolymer obtained by the method described in Patent Document 1 is a linear polymer having no branched structure, although the crystallinity at low temperature is lowered and the rubber properties at low temperature are improved. Therefore, there is a problem that the hot flow property is inferior.

  On the other hand, in order to improve the hot flow property of a cyclopentene ring-opening polymer, Non-Patent Document 1 reacts a polyfunctional aldehyde terminator with a living polymerization terminal polymerized by using a W alkylden complex catalyst, thereby producing cyclopentene. A method for introducing a branched structure into a ring-opening polymer is disclosed. However, in the method described in Non-Patent Document 1, a branched structure is introduced into the cyclopentene ring-opening polymer by utilizing a coupling reaction of living polymerization, but at most with respect to one polymer chain. Only one branched structure can be introduced, and the coupling rate is as low as about 50%. Therefore, a large number of linear polymers remain in the resulting polymer, resulting in hot flow properties. The improvement effect was not enough. Further, in the method described in Non-Patent Document 1, since a coupling reaction of living polymerization is used, there is a problem that an expensive living polymerization catalyst must be used in a large amount with respect to the obtained polymer. A large amount of catalyst residue remains in the polymer, and gelation occurs in the polymer due to the influence of the catalyst residue. As a result, the dispersibility with a compounding agent such as carbon black decreases, and rubber When used as a material, there is also a problem that the rubber properties are inferior.

International Publication No. 2008/048536

Polymer 37, pp 2547-2554, 1996

  An object of the present invention is to provide a cyclopentene ring-opening polymer that is excellent in hot flow property, and thus easy to manufacture and excellent in processability.

  As a result of diligent research to achieve the above object, the inventors of the present invention have found that when the cyclopentene is subjected to ring-opening polymerization in the presence of a metathesis polymerization catalyst, 0.001 to 1 mol% of a vinyl group is added to the cyclopentene. It is found that the above object can be achieved by reacting a compound having 3 or more cyclic olefins and / or vinyl groups with cyclopentene to introduce a plurality of branched structures per polymer chain. It came to complete.

That is, according to the present invention, there is provided a method for producing a cyclopentene ring-opening polymer in which cyclopentene is subjected to ring-opening polymerization in the presence of a metathesis polymerization catalyst, wherein the metathesis polymerization catalyst includes a periodic table group 6 transition metal compound and the following general formula: Using a compound containing the organoaluminum compound represented by (1) , 0.001 to 1 mol% of a cyclic olefin having a vinyl group and / or a compound having three or more vinyl groups, based on the cyclopentene, It reacts with the said cyclopentene, It is characterized by the above-mentioned.
(R ¹ ) _3-x Al (OR ² ) _x (1)
(In the general formula (1), R ¹ and R ² represent a hydrocarbon group having 1 to 20 carbon atoms, and x is 0 <x <3.)

  According to the production method of the present invention, it is possible to produce a cyclopentene ring-opening polymer excellent in hot flow properties, and thereby provide a cyclopentene ring-opening polymer which is easy to produce and excellent in processability. be able to.

  The method for producing a cyclopentene ring-opening polymer according to the present invention comprises, when ring-opening polymerization of cyclopentene in the presence of a metathesis polymerization catalyst, 0.001 to 1 mol% of a cyclic olefin having a vinyl group with respect to the cyclopentene and A compound having 3 or more vinyl groups is reacted with the cyclopentene.

(Cyclic olefin having vinyl group and / or compound having 3 or more vinyl groups)
In the present invention, when cyclopentene is subjected to ring-opening polymerization in the presence of a metathesis polymerization catalyst, a cyclopentene-opening obtained by reacting a cycloolefin having a vinyl group and / or a compound having three or more vinyl groups with cyclopentene. It is possible to introduce a plurality of branched structures (a plurality of long chain branched structures) per polymer chain into the ring polymer, thereby making the cyclopentene ring-opening polymer excellent in hot flow properties. Can do.

  The cyclic olefin containing a vinyl group is not particularly limited as long as it is a cyclic olefin having at least one vinyl group. For example, monocyclic olefins having a vinyl group such as 4-vinylcyclopentene and 5-vinylcyclooctene; And norbornenes having a vinyl group such as 5-vinylnorbornene, 5-propenylnorbornene, and 5-styrylnorbornene.

  In addition, examples of the compound containing three or more vinyl groups include compounds having three vinyl groups such as 1,2,4-trivinylcyclohexane and 1,3,5-trivinylcyclohexane; divinylbenzene oligomers, 1, And compounds having four or more vinyl groups such as 2-polybutadiene oligomer.

  The amount of the cyclic olefin having a vinyl group and / or the compound having 3 or more vinyl groups used in the present invention is 0.001 to 1 mol%, preferably 0.002 to 0.9 mol, based on cyclopentene. It is mol%, More preferably, it is 0.005-0.8 mol%. Here, the hot flow property of the cyclopentene ring-opening polymer produced according to the present invention is not limited to the amount of the cyclic olefin having a vinyl group and / or the compound having three or more vinyl groups, and the resulting cyclopentene ring-opening polymer. The amount of the cyclic olefin having a vinyl group and / or the compound having three or more vinyl groups depends on the molecular weight and hot flow property of the target cyclopentene ring-opening polymer. Is preferably adjusted within the above range. If the amount of the cyclic olefin having a vinyl group and / or the compound having three or more vinyl groups is too small, the effect of improving the hot flow of the resulting cyclopentene ring-opening polymer tends to be small, while the amount used is large. If it is too high, gelation of the resulting cyclopentene ring-opening polymer may occur.

(Metathesis polymerization catalyst)
The metathesis polymerization catalyst used in the present invention is not particularly limited, and a conventionally known metathesis polymerization catalyst can be used. For example, a transition metal compound containing atoms such as Mo, W, Nb, Ta, and Ru In the present invention, those containing a Group 6 transition metal compound of the periodic table as the main catalyst and an organometallic compound as the cocatalyst are preferred.

  Although it does not specifically limit as a periodic table group 6 transition metal compound as a main catalyst, The halide of the periodic table 6 group transition metal atom, an alcoholate, an arylate, an oxydide etc. are mentioned, Among these, polymerization activity From the viewpoint of high, a halide is preferable. The periodic table (long-period periodic table, the same shall apply hereinafter) Group 6 transition metal atom is preferably Mo or W.

  Specific examples of such a periodic table Group 6 transition metal compound include molybdenum compounds such as molybdenum pentachloride, molybdenum oxotetrachloride, and molybdenum (phenylimide) tetrachloride; tungsten hexachloride, tungsten oxotetrachloride, tungsten (phenyl). Imido) tetrachloride, monocatecholate tungsten tetrachloride, tungsten compounds such as bis (3,5-ditertiarybutyl) catecholate tungsten dichloride, bis (2-chloroetherate) tetrachloride, tungsten oxotetraphenolate; It is done.

  The use amount of the Group 6 transition metal compound of the periodic table is usually 1: 100 to 1: 200,000, preferably 1: 200 to 1 in terms of the molar ratio of “Group 6 transition metal atom in the polymerization catalyst: cyclopentene”. : 150,000, more preferably in the range of 1: 500 to 1: 100,000. When there is too little usage-amount of a periodic table group 6 transition metal compound, a polymerization reaction may not fully advance. On the other hand, if the amount is too large, removal of the catalyst residue from the resulting cyclopentene ring-opening polymer becomes difficult, and the heat resistance and cold resistance of the resulting cyclopentene ring-opening polymer may be lowered.

  Examples of the organometallic compound as a promoter include organometallic compounds of Group 1, 2, 12, 13, and 14 metal atoms of a periodic table having a hydrocarbon group having 1 to 20 carbon atoms. Among these, organic lithium, organic magnesium, organic zinc, organic aluminum, and organic tin are preferable, organic lithium, organic tin, and organic aluminum are more preferable, and organic aluminum is particularly preferable.

  Examples of the organic lithium include n-butyllithium, methyllithium, phenyllithium, neopentyllithium, and neophyllithium.

  Examples of the organic magnesium include butylethylmagnesium, butyloctylmagnesium, dihexylmagnesium, ethylmagnesium chloride, n-butylmagnesium chloride, allylmagnesium bromide, neopentylmagnesium chloride, neophyllmagnesium chloride, and the like.

  Examples of the organic zinc include dimethyl zinc, diethyl zinc, and diphenyl zinc.

  Examples of the organic tin include tetramethyltin, tetra (n-butyl) tin, and tetraphenyltin.

Examples of organic aluminum include trialkylaluminum such as trimethylaluminum, triethylaluminum, and triisobutylaluminum; alkylaluminum halide such as diethylaluminum chloride, ethylaluminum sesquichloride, and ethylaluminum dichloride; The compound which is made is mentioned.
(R ¹ ) _3-x Al (OR ² ) _x (1)
(In the general formula (1), R ¹ and R ² represent a hydrocarbon group having 1 to 20 carbon atoms, and x is 0 <x <3.)

In the general formula (1), specific examples of R ¹ and R ² include methyl group, ethyl group, isopropyl group, n-propyl group, isobutyl group, n-butyl group, t-butyl group, and n-hexyl group. And alkyl groups such as cyclohexyl group; aryl groups such as phenyl group, 4-methylphenyl group, 2,6-dimethylphenyl group, 2,6-diisopropylphenyl group, naphthyl group; and the like. R ¹ and R ² may be the same or different. In the present invention, R ¹ and R 2 can be used because the cis ratio of the resulting cyclopentene ring-opening polymer can be increased. of the ^two, at least R ² is preferably an alkyl group formed by bonding continuously carbon atoms 4 or more, in particular, n- butyl group, 2-methyl - pentyl, n- hexyl, cyclohexyl Group, n-octyl group and n-decyl group are preferred.

In the general formula (1), x is 0 <x <3. That is, in the general formula (1), the composition ratio between R ¹ and OR ² can take any value in the ranges of 0 <3-x <3 and 0 <x <3, respectively. However, x is preferably 0.5 <x <1.5 because the polymerization activity can be increased and the cis ratio of the resulting cyclopentene ring-opening polymer can be increased.

Such an organoaluminum compound (B) represented by the above general formula (1) can be synthesized, for example, by a reaction of a trialkylaluminum and an alcohol as shown in the following general formula (2).
_{^{(R 1) 3 Al + xR}} 2 OH → (R 1) 3-x Al (OR 2) x + (R 1) x H (2)
In the general formula (1), x can be arbitrarily controlled by defining the reaction ratio of the corresponding trialkylaluminum and alcohol as shown in the general formula (2).

（上記一般式（３）において、Ｒ^３〜Ｒ^６は炭素数１〜２０、好ましくは４〜２０の炭化水素基を表し、ｎは、１〜２０の整数である。） Alternatively, aluminoxane may be used as the organic aluminum. The aluminoxane is represented by the following general formula (3), for example.

(In the general formula (3), R ^{3 to} R ⁶ represent a hydrocarbon group having 1 to 20 carbon atoms, preferably 4 to 20 carbon atoms, and n is an integer of 1 to 20).

  Examples of such an aluminoxane include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and the like.

  In the production method of the present invention, the cis ratio of the obtained cyclopentene ring-opening polymer can be increased, whereby the cyclopentene ring-opening polymer is amorphous at low temperature, cold flow property and low temperature. It is preferable to use a combination of a periodic table group 6 transition metal compound and an organoaluminum as a metathesis polymerization catalyst, particularly at room temperature. Among the organoaluminum compounds, the compound represented by the above general formula (1) is preferable because the cis ratio of the resulting cyclopentene ring-opening polymer can be 30% or more. Or the aluminoxane represented by the said General formula (3) is more preferable, and the compound represented by the said General formula (1) is especially preferable.

  The amount of the organometallic compound used varies depending on the type of organometallic compound used, but is preferably 0.1 to 100 times the periodic table Group 6 transition metal atom constituting the Periodic Table Group 6 transition metal compound. The molar ratio is more preferably 0.2 to 50 times mol, and still more preferably 0.5 to 20 times mol. If the amount of the organometallic compound used is too small, the polymerization activity may be insufficient. If the amount is too large, side reactions tend to occur during ring-opening polymerization.

  Moreover, as a polymerization catalyst used by this invention, in addition to the periodic table group 6 transition metal compound and organometallic compound mentioned above, what further contains an oxygen atom containing hydrocarbon compound may be used. By further containing an oxygen atom-containing hydrocarbon compound, the polymerization activity can be improved, and the molecular weight of the resulting cyclopentene ring-opening polymer can be improved. The oxygen atom-containing hydrocarbon compound is not particularly limited as long as it is a hydrocarbon compound having an oxygen atom, but an ester, ketone or ether compound having 2 to 30 carbon atoms which may have a halogen atom as a substituent From the viewpoints of improving the polymerization activity at room temperature or higher and having a high effect of increasing the molecular weight, esters, ketones or ethers having 4 to 10 carbon atoms are preferable. Such an ester, ketone or ether compound may be a cyclic ester, ketone or ether, or a compound containing a plurality of ester bonds, ketone bonds or ether bonds in one molecule. It may be.

Specific examples of the ester compound include ethyl acetate, butyl acetate, amyl acetate, octyl acetate, 2-chloroethyl acetate, methyl acetyl acrylate, ε-caprolactone, dimethyl glutarate, σ-hayanolactone, diacetoxyethane, and the like. It is done.
Specific examples of the ketone compound include acetone, ethyl methyl ketone, acetyl acetone, acetophenone, cyclohexyl phenyl ketone, 1′-acetonaphthone, methyl 2-acetylbenzoate, 4′-chloroacetophenone, and the like.
Specific examples of the ether compound include diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, ethylene glycol diethyl ether, 1,4-dioxane and the like.

  The amount of the oxygen atom-containing hydrocarbon compound to be used varies depending on the type of the oxygen atom-containing hydrocarbon compound to be used, but is preferably relative to the periodic table group 6 transition metal atom constituting the periodic table group 6 transition metal compound. The ratio is 0.1 to 100 times mol, more preferably 0.2 to 50 times mol, and still more preferably 0.5 to 20 times mol. If the amount of the oxygen atom-containing hydrocarbon compound used is too small, the effect of adding the oxygen atom-containing hydrocarbon compound tends to be difficult to obtain, and if too large, the polymerization activity may be insufficient.

(Method for producing cyclopentene ring-opening polymer)
The method for producing a cyclopentene ring-opening polymer according to the present invention uses a cyclic olefin having a vinyl group and / or a compound having three or more vinyl groups when cyclopentene is subjected to ring-opening polymerization in the presence of a metathesis polymerization catalyst. The cyclopentene ring-opening polymer is obtained by reacting a cyclic olefin having a vinyl group and / or a compound having three or more vinyl groups.

  In the present invention, the method for reacting a cycloolefin having a cyclic olefin having a vinyl group and / or three or more vinyl groups with cyclopentene is not particularly limited. For example, after mixing a cyclopentene before polymerization with a cycloolefin having a cyclic olefin having a vinyl group and / or 3 or more vinyl groups and cyclopentene, by bringing them into contact with a metathesis polymerization catalyst, together with a ring-opening polymerization reaction, Cyclopentene can be reacted with a cyclic olefin having a vinyl group and / or a compound having three or more vinyl groups. Alternatively, after cyclopentene and a metathesis polymerization catalyst are brought into contact with each other and subjected to a ring-opening polymerization reaction to obtain a polymer, a cyclic olefin having a vinyl group and / or a compound having three or more vinyl groups is added, and these are added. You may make it react.

  In addition, in the method for producing a cyclopentene ring-opening polymer of the present invention, in addition to cyclopentene and a cyclic olefin having a vinyl group and / or a compound having three or more vinyl groups, other cyclic compounds copolymerizable with cyclopentene are available. Olefin (excluding cyclic olefin having a vinyl group) may be used. However, from the viewpoint of improving the properties of the obtained cyclopentene ring-opening polymer, the structural unit derived from cyclopentene in the cyclopentene ring-opening polymer is 90% by weight or more, more preferably 95% by weight or more, and still more preferably. Is 96% by weight or more. Examples of other copolymerizable cyclic olefins include monocyclic olefins such as cyclooctene and cyclooctadiene, and polycyclic cyclic olefins such as a norbornene compound which may have an arbitrary substituent.

  In the method for producing a cyclopentene ring-opening polymer of the present invention, the ring-opening polymerization reaction may be performed in the absence of a solvent or in a solution. As a solvent used when the ring-opening polymerization reaction is performed in a solution, a compound which is inactive in the polymerization reaction, a cyclopentene used for the ring-opening polymerization, a cyclic olefin having a vinyl group and / or three or more vinyl groups, metathesis The solvent is not particularly limited as long as it is a solvent capable of dissolving the polymerization catalyst, and examples thereof include hydrocarbon solvents and halogen solvents. Specific examples of the hydrocarbon solvent include, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; aliphatic hydrocarbons such as n-hexane, n-heptane, and n-octane; cyclohexane, cyclopentane, and methyl And alicyclic hydrocarbons such as cyclohexane. Specific examples of the halogen-based solvent include alkyl halogens such as dichloromethane and chloroform; aromatic halogens such as chlorobenzene and dichlorobenzene.

  In the method for producing a cyclopentene ring-opening polymer of the present invention, an olefin compound or a diolefin compound may be used to adjust the molecular weight of the resulting cyclopentene ring-opening polymer, and this may be added to the polymerization reaction system.

  The olefin compound is not particularly limited as long as it is an organic compound having an ethylenically unsaturated bond. For example, α-olefins such as 1-butene, 1-pentene, 1-hexene, 1-octene; styrene, vinyltoluene Styrenes such as: halogen-containing vinyl compounds such as allyl chloride; vinyl ethers such as ethyl vinyl ether and i-butyl vinyl ether; silicon-containing vinyl compounds such as allyltrimethoxysilane, allyltriethoxysilane, allyltrichlorosilane, and styryltrimethoxysilane Disubstituted olefins such as 2-butene and 3-hexene;

  Examples of the diolefin compound include 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 2-methyl-1,4-pentadiene, 2,5-dimethyl-1,5- Non-conjugated diolefins such as hexadiene are listed.

  Of these, α-olefins or styrenes are preferable in that the polymerization activity is high and the molecular weight adjustment is excellent.

  The addition amount of these olefin compounds and diolefin compounds may be appropriately selected according to the target molecular weight, but is preferably in the range of 0.01 to 10 mol% with respect to the cyclopentene used for polymerization.

  In the method for producing a cyclopentene ring-opening polymer of the present invention, the polymerization temperature is preferably −100 ° C. or higher and lower than 100 ° C., more preferably −50 ° C. or higher and lower than 90 ° C., further preferably −40 ° C. or higher and 80 ° C. It is less than ℃, particularly preferably -30 ℃ or more and less than 60 ℃. If the polymerization temperature is too high, the molecular weight and cis ratio of the resulting cyclopentene ring-opening polymer may be low, and if the polymerization temperature is too low, the polymerization rate may be slow, resulting in poor productivity.

  The polymerization reaction time is preferably 1 minute to 100 hours, more preferably 10 minutes to 50 hours.

  In the process for producing a cyclopentene ring-opening polymer of the present invention, ring-opening polymerization is started, and after the polymerization conversion rate reaches a predetermined value, a known polymerization terminator is added to the polymerization system to stop the cyclopentene. Ring-opening polymers can be produced.

  Moreover, in this invention, you may add anti-aging agents, such as a phenol type stabilizer, a phosphorus type stabilizer, a sulfur type stabilizer, to the obtained ring-opening polymer depending on necessity. What is necessary is just to determine suitably the addition amount of an anti-aging agent according to the kind etc. Further, in the present invention, an extension oil may be blended as desired.

  Furthermore, when a polymerization reaction is performed, a solvent is used, and when the polymerization reaction is performed in a solution, a method for obtaining the polymer from the polymer solution may be a known method, and is not particularly limited. For example, after separating the solvent by steam stripping or the like, it is possible to employ a method in which a solid is filtered and further dried to obtain a solid rubber.

  The cyclopentene ring-opening polymer obtained by the production method of the present invention has a polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography, preferably 10,000 to 1,000,000, More preferably, it is 20,000-900,000, More preferably, it is 40,000-800,000. If the molecular weight is too low, rubber properties may be deteriorated. On the other hand, if the molecular weight is too high, production and handling may be difficult.

  Further, the cyclopentene ring-opening polymer obtained by the production method of the present invention has a molecular weight distribution which is a ratio of a number average molecular weight (Mn) in terms of polystyrene and a weight average molecular weight (Mw) measured by gel permeation chromatography. (Mw / Mn) is preferably 2.0 to 8.0. Here, if cyclopentene is subjected to metathesis polymerization in the presence of a metathesis polymerization catalyst, an equilibrium reaction between ring-opening polymerization and depolymerization occurs. Therefore, when the polymerization reaction reaches equilibrium, depolymerization and repolymerization occur, and Since the molecular weight converges to a certain value, the molecular weight distribution becomes narrow, and usually a linear polymer having a molecular weight distribution (Mw / Mn) of less than 2.0 is generally used. On the other hand, in the present invention, when ring-opening polymerization of cyclopentene, by using a cyclic olefin having a vinyl group and / or a compound having three or more vinyl groups, a plurality of polymers per polymer chain are used. Since the branched structure is introduced, the molecular weight distribution of the obtained polymer tends to be relatively wide. However, on the other hand, if the branched structure becomes too large and the molecular weight distribution (Mw / Mn) becomes too large, a three-dimensional cross-linked polymer may be generated and an insoluble gel may be generated. And the rubber properties are unfavorable. Therefore, molecular weight distribution (Mw / Mn) becomes like this. Preferably it is 2.0-8.0, More preferably, it is 2.2-7.0, More preferably, it is 2.3-6.0. The cyclopentene ring-opening polymer obtained by the production method of the present invention has a gel content of preferably 1.0% by weight or less, more preferably 0.5% by weight or less, and further preferably 0.1% by weight. It is as follows.

Moreover, the cyclopentene ring-opening polymer obtained by such a production method has preferably 1.1 to 10 branched structures per polymer chain, more preferably 1.2 to The number is 8, more preferably 1.3 to 5. If the number of branched structures is too small, the hot flow property is inferior, the polymer may be agglomerated when exposed to a high temperature in the production process, or the dispersibility may be inferior when various compounding agents are blended. On the other hand, if the number of branched structures is too large, gelation occurs, and fluidity is lost during production, making it impossible to produce, or when various compounding agents are blended, it may not be dispersed at all.
The number of branched structures per polymer chain of the obtained cyclopentene ring-opening polymer is the number average molecular weight (Mn) of the polymer and the cyclic olefin and / or vinyl group having a vinyl group introduced into the polymer. It is calculated | required from the quantity of the compound which has 3 or more. The amount of the cyclic olefin having a vinyl group and / or the compound having 3 or more vinyl groups introduced into the polymer is 3% of the cyclic olefin and / or vinyl group having a vinyl group remaining in the reaction liquid after the polymerization reaction. A method for determining the amount of a compound having at least one from gas chromatography or a method for determining the amount of a cyclic olefin having a vinyl group introduced into a polymer chain and / or a compound having at least three vinyl groups from a ¹ H-NMR spectrum It is calculated | required by the method to do.

  Further, the cyclopentene ring-opening polymer obtained by the production method of the present invention has a cis ratio of preferably 30% or more, more preferably 35% or more, and further preferably 40% or more. A cis ratio of 30% or more is preferable because the cyclopentene ring-opening polymer becomes amorphous at low temperatures and is excellent in rubber properties at low temperatures.

  According to the present invention, when cyclopentene is subjected to ring-opening polymerization in the presence of the above-described metathesis polymerization catalyst, a cyclic olefin having a vinyl group and / or a compound having three or more vinyl groups is reacted with cyclopentene. A plurality of branched structures per polymer chain are introduced into the resulting cyclopentene ring-opening polymer, whereby the resulting cyclopentene ring-opening polymer can be made excellent in hot flow properties. As a result, the polymer can be effectively prevented from agglomerating when exposed to high temperatures in the production process, the production of the cyclopentene ring-opening polymer can be facilitated, and the resulting cyclopentene ring-opening weight can be obtained. The coalescence can be made excellent in dispersibility in rubbers other than various compounding agents and cyclopentene ring-opening polymers.

(Rubber composition)
The cyclopentene ring-opening polymer obtained by the production method of the present invention can be made into a rubber composition by adding rubbers other than various compounding agents and cyclopentene ring-opening polymers. Although it does not specifically limit as a compounding agent, For example, inorganic particles, such as a silica and carbon black, are mentioned. Examples of the rubber other than the cyclopentene ring-opening polymer include natural rubber (NR), polyisoprene rubber (IR), styrene-butadiene copolymer rubber (SBR), and polybutadiene rubber (BR). In particular, the cyclopentene ring-opening polymer obtained by the production method of the present invention has a plurality of branched structures per polymer chain, and thus has excellent hot flow properties. It is easy to mix with rubbers other than the ring polymer, and therefore a rubber composition containing them can be easily produced.

  Furthermore, in addition to the above components, the rubber composition of the present invention includes other compounding agents commonly used in the rubber processing field, such as a crosslinking agent, a crosslinking accelerator, a crosslinking activator, an anti-aging agent, an activator, Process oils, plasticizers, lubricants, fillers and the like can be blended. As the compounding amount of these compounding agents, an amount corresponding to the compounding purpose can be appropriately adopted.

  The cyclopentene ring-opening polymer obtained by the production method of the present invention, and the rubber composition obtained by using the cyclopentene ring-opening polymer are excellent in hot flow properties, and thereby easy to produce and processability And excellent dispersibility in rubbers other than various compounding agents and cyclopentene ring-opening polymers. Therefore, the cyclopentene ring-opening polymer obtained by the production method of the present invention and the rubber composition obtained using the cyclopentene ring-opening polymer can be used for a wide range of applications by taking advantage of the above characteristics. Specifically, use for adhesives such as sealants, sealants, adhesives, and adhesives; use for thermoplastic elastomers; tire parts such as treads, carcass, sidewalls, and bead parts Use for rubber products such as hoses, window frames, belts, shoe soles, anti-vibration rubbers, and automobile parts; use as resin-reinforced rubber such as impact-resistant polystyrene and ABS resin.

  Hereinafter, although this invention is demonstrated based on a more detailed Example, this invention is not limited to these Examples. In the following, “part” is based on weight unless otherwise specified. The test and evaluation were as follows.

<Molecular weight>
By gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, the number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the cyclopentene ring-opening polymer are converted into polystyrene values. It was measured.

<Cis / trans ratio>
The cis / trans ratio of the cyclopentene ring-opening polymer was determined from ¹³ C-NMR spectrum measurement.

<Number of branched structures per polymer chain>
The polymer solution after the polymerization reaction was subjected to gas chromatography measurement, and the amount of the cyclic olefin having a vinyl group and / or the compound having three or more vinyl groups introduced into the polymer was determined. And from the amount of the cyclic olefin having a vinyl group introduced into the polymer and / or the compound having three or more vinyl groups, and the number of cyclopentene monomer units determined from the number average molecular weight (Mn), determined by the above method. The number of branched structures per polymer chain was calculated.

<Amount of catalyst metal residue>
The amount of metathesis polymerization catalyst metal remaining in the cyclopentene ring-opening polymer was determined by the ICP-AES method.

<Long-term storage stability>
The cyclopentene ring-opening polymer was cut into 2 mm squares, placed in an oven at 80 ° C. (fan type), and the gel content (%) after 240 hours was measured. The gel content (%) was determined by dissolving 2 parts of a cyclopentene ring-opened polymer after 240 hours at 80 ° C. in 200 parts of toluene, followed by filtration through a 200-mesh wire mesh, and then sufficiently filling the wire mesh with toluene. After washing, the wire mesh was vacuum dried at 80 ° C. for 5 hours, and the increase in weight of the wire mesh after vacuum drying was calculated.

<Hot flow evaluation>
The cyclopentene ring-opening polymer was molded into a tensile test piece No. 3 dumbbell in accordance with JIS K6301, and one end of the obtained No. 3 dumbbell was fixed in a high temperature bath at 105 ° C. The hot flow property was evaluated by hanging the end with a weight and measuring the time until the center of the dumbbell extended 100 mm. The longer the time until the center of the dumbbell extends 100 mm (the larger the value of the hot flow property), the less hot the flow is and the better judgment can be made.

<Cold flow evaluation>
The cyclopentene ring-opened polymer was kept at 50 ° C., sucked with a glass tube having an inner diameter of 5.3 mm for 10 minutes under a differential pressure of 0.005 MPa, the weight of the polymer sucked into the glass tube was measured, and the polymer sucked per minute Cold flow property was evaluated by determining the amount (mg / min). The smaller the amount of the sucked polymer (the smaller the value of the cold flow property), the harder the cold flow, and a favorable judgment can be made.

<Melting point (Tm)>
The melting point (Tm) of the cyclopentene ring-opening polymer was measured using a differential scanning calorimeter (DSC) at a temperature increase of 10 ° C./min.

Example 1
Under a nitrogen atmosphere, add 10 parts of a 2.0 wt% WCl ₆ / toluene solution and 2.2 parts of a 15 wt% diisobutylaluminum monoisobutoxide / n-hexane solution to a glass container containing a stir bar, and stir for 15 minutes. Then, 0.044 part of 1,4-dioxane was added to obtain a catalyst solution.

  Next, 100 parts of cyclopentene and 0.18 parts of 5-vinylnorbornene (0.1 mol% with respect to cyclopentene) were charged in a pressure-resistant glass reaction vessel equipped with a stirrer under a nitrogen atmosphere, and then the catalyst solution prepared above. And polymerized at 25 ° C. for 16 hours. And after adding excess isopropanol to the pressure | voltage resistant glass reaction container and stopping superposition | polymerization, it poured into the large excess isopropanol containing 2, 6-di-t-butyl-p-cresol (BHT). The precipitated polymer was collected, washed with isopropanol, and vacuum dried at 40 ° C. for 3 days to obtain 75 parts of a cyclopentene ring-opening polymer. For the obtained cyclopentene ring-opening polymer, the number average molecular weight (Mn), the weight average molecular weight (Mw), the molecular weight distribution (Mw / Mn), the cis / trans ratio, and the branching per polymer chain are determined according to the above method. The number of structures, the amount of catalyst metal residue, long-term storage stability, hot flow properties, cold flow properties, and melting points (Tm) were evaluated and measured. The results are shown in Table 1.

Example 2
Instead of 0.044 part of 1,4-dioxane, 0.085 part of ethyl acetate was used, and the blending amount of 5-vinylnorbornene was changed from 0.18 part to 0.09 part (0.05 parts per cyclopentene). Polymerization was conducted in the same manner as in Example 1 except that the amount was changed to (mol%) to obtain 54 parts of a cyclopentene ring-opening polymer. And about the obtained cyclopentene ring-opening polymer, each measurement was performed similarly to Example 1. The results are shown in Table 1.

<< Reference Example 1 >>
Under a nitrogen atmosphere, a pressure-resistant glass reaction vessel equipped with a stirrer was charged with 100 parts of cyclopentene and 0.09 part of 5-vinylnorbornene (0.05 mol% based on cyclopentene), and then 0.092 of 1-hexene as a molecular weight regulator. Parts, followed by 10.0 parts of a diisobutylaluminoxane / toluene solution (3.3 × 10 ⁻² mol / liter in terms of Al) prepared from triisobutylaluminum and water, and 1.6 wt% WCl ₆ / toluene 7 parts of the solution was added and polymerized at 25 ° C. for 6 hours. Then, excess isopropanol was added to terminate the polymerization, and then poured into a large excess of isopropanol containing 2,6-di-t-butyl-p-cresol (BHT). Then, the precipitated polymer was collected, washed with isopropanol, and vacuum dried at 40 ° C. for 3 days to obtain 58 parts of a cyclopentene ring-opening polymer. And about the obtained cyclopentene ring-opening polymer, each measurement was performed similarly to Example 1. The results are shown in Table 1.

<< Reference Example 2 >>
Polymerization was carried out in the same manner as in Reference Example 1 except that 0.12 part of 1,2,4-trivinylcyclohexane (0.05 mol% based on cyclopentene) was used instead of 0.018 part of 5-vinylnorbornene. To obtain 54 parts of a cyclopentene ring-opening polymer. And about the obtained cyclopentene ring-opening polymer, each measurement was performed similarly to Example 1. The results are shown in Table 1.

<< Comparative Example 1 >>
78 parts of a cyclopentene ring-opening polymer was obtained in the same manner as in Example 1 except that 5-vinylnorbornene was not blended. And about the obtained cyclopentene ring-opening polymer, each measurement was performed similarly to Example 1. The results are shown in Table 1.

<< Comparative Example 2 >>
56 parts of cyclopentene ring-opening polymer were obtained in the same manner as in Example 2 except that 5-vinylnorbornene was not blended. And about the obtained cyclopentene ring-opening polymer, each measurement was performed similarly to Example 1. The results are shown in Table 1.

<< Comparative Example 3 >>
In a nitrogen atmosphere, a pressure-resistant glass reaction vessel equipped with a stirrer was charged with 100 parts of cyclopentene and 100 parts of toluene, and after cooling the pressure-resistant glass reaction vessel to -45 ° C, 5% by weight of 2,6-diisopropylphenylimide-neophylidene (T-Butyl)] 20 parts of a molybdenum / toluene solution was added and polymerized at -45 ° C for 24 hours. A small amount of the polymerization reaction solution was sampled, and the polymerization was stopped with excess isopropanol. The obtained polymer was Mn = 57,500, Mw = 66,100, and Mw / Mn = 1.15.
Next, 0.28 part of 1,3,5-benzenetricarboxaldehyde dissolved in 10 parts of toluene (amount equivalent to molybdenum atom) was added to the polymerization reaction solution obtained above, and the coupling reaction was performed for 3 hours. went. Subsequently, it is poured into a large excess of isopropanol containing 2,6-di-t-butyl-p-cresol (BHT), and the precipitated polymer is recovered, washed with isopropanol, and vacuum-dried at 40 ° C. for 3 days. As a result, 50 parts of a cyclopentene ring-opening polymer was obtained. And about the obtained cyclopentene ring-opening polymer, each measurement was performed similarly to Example 1. The results are shown in Table 1.

As shown in Table 1, when cyclopentene is subjected to ring-opening polymerization in the presence of a metathesis polymerization catalyst, when a cyclic olefin having a vinyl group and / or a compound having three or more vinyl groups are added, the resulting cyclopentene Each of the ring polymers contains an appropriate number of branched structures per polymer chain, has excellent hot flow properties and cold flow properties, and excellent rubber properties (the gel content during long-term storage is 0%) The rubber properties can be kept good) (Examples 1 and 2 ).

On the other hand, when neither a cyclic olefin having a vinyl group nor a compound having three or more vinyl groups is used, the resulting cyclopentene ring-opening polymer does not have a long-chain branched structure, It was inferior to hot flow property and cold flow property (Comparative Examples 1 and 2).
In addition, when 2,6-diisopropylphenylimide-neophylidene [di (t-butyl)] molybdenum is used and a branched structure is introduced by a coupling reaction of living polymerization, the resulting cyclopentene ring-opening polymer is a polymer chain. The number of branched structures per one is as low as 0.35, the hot flow property and the cold flow property are insufficient, the amount of the catalyst metal is large, and the gel content during long-term storage is 25 due to the influence of the catalyst metal. %, And the rubber properties were inferior.

Claims (1)

A process for producing a cyclopentene ring-opening polymer comprising ring-opening polymerization of cyclopentene in the presence of a metathesis polymerization catalyst,
As the metathesis polymerization catalyst, a catalyst containing a group 6 transition metal compound of the periodic table and an organoaluminum compound represented by the following general formula (1) is used.
A cyclopentene ring-opening polymer, wherein 0.001 to 1 mol% of a cyclic olefin having a vinyl group and / or a compound having three or more vinyl groups is reacted with the cyclopentene with respect to the cyclopentene. Production method.
(R ¹ ) _3-x Al (OR ² ) _x (1)
(In the general formula (1), R ¹ and R ² represent a hydrocarbon group having 1 to 20 carbon atoms, and x is 0 <x <3.)