JP2013249432A - Polymer, composite, and method for producing polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cycloolefin polymer-based crystalline polymer excellent in heat resistance and adhesivity with other materials.SOLUTION: A crystalline polymer is obtained by: subjecting dicyclopentadiene to a ring-opening metathesis polymerization using a specific metal compound as a polymerization catalyst and in the presence of an siloxane compound having an ethylenically unsaturated group; and hydrogenating the resultant, wherein the crystalline polymer has a polymer chain including a repeating unit originated from dicyclopentadiene, and the polymer chain is bonded by a group containing a siloxane group.

Description

  The present invention relates to a polymer, a composite, and a method for producing a polymer. More specifically, the present invention relates to a cycloolefin polymer-based crystalline polymer excellent in heat resistance and adhesion to other materials, a method for producing the same, The present invention relates to a composite using a polymer.

  For example, dicyclopentadiene ring-opening polymer hydride as described in Patent Document 1 is a kind of so-called cycloolefin polymer, and is excellent in transparency, low birefringence, molding processability, and the like. It is used as a material applicable to various uses.

  As is also the case described in Patent Document 1, the ring-opening polymer hydride of dicyclopentadiene is generally obtained as an amorphous polymer having an atactic structure. However, the amorphous dicyclopentadiene ring-opened polymer hydride having an atactic structure may have insufficient heat resistance, mechanical strength, solvent resistance and the like depending on its use. Thus, as a technique for improving these performances, it has been proposed to impart crystallinity by imparting stereoregularity to the ring-opening polymer hydride of dicyclopentadiene.

  For example, in Non-Patent Document 1, by using a tungsten or molybdenum complex in which two biphenoxy groups are coordinated as a polymerization catalyst, the proportion of meso-dyad exceeds 50%, that is, has an isotactic structure. It is disclosed that a ring-opening polymer hydride of crystalline dicyclopentadiene can be obtained. In Patent Document 2 and Patent Document 3, by using a tungsten complex having an imide group having a substituent of a specific structure on a nitrogen atom as a polymerization catalyst, the ratio of racemo dyad is 51% or more, that is, It is disclosed that a crystalline ring-opening polymer hydride of dicyclopentadiene having a syndiotactic structure can be obtained.

Japanese Patent Laid-Open No. 11-124429 JP 2005-89744 A JP 2006-52333 A

Proceedings of the Society of Polymer Science, 2002, Vol. 8, p. 1629-1630

  For example, a dicyclopentadiene ring-opened polymer hydride having crystallinity as described in Patent Document 2 and Patent Document 3 is a polymer having excellent heat resistance. It became clear that it also has the property that it is difficult to adhere. If the adhesion with other materials is insufficient, it will be difficult to apply as a material for forming a composite with other materials. I can say that.

  Therefore, the present invention has improved the heat resistance and the adhesiveness with other materials while maintaining the high heat resistance that is the original feature of the crystalline dicyclopentadiene ring-opened polymer hydride. An object of the present invention is to provide a cycloolefin polymer-based crystalline polymer having excellent adhesion to other materials.

  As a result of intensive investigations to achieve the above object, the present inventor obtained dicyclopentadiene in the presence of a siloxane compound having an ethylenically unsaturated group to obtain a ring-opening polymer of dicyclopentadiene. After the ring polymerization, the resulting ring-opened polymer is hydrogenated to obtain a crystalline polymer, whereby a crystalline dicyclopentadiene ring-opened polymer hydride such as high heat resistance is obtained. It has been found that a polymer having excellent characteristics and excellent adhesion to other materials can be obtained. The present invention has been completed based on this finding.

Thus, according to the present invention, the polymer chain has a repeating unit represented by the following formula (1) as a main structural unit, and a group containing a siloxane group is bonded to the polymer chain. A polymer having crystallinity is provided.

  In the polymer, in the polymer chain, the ratio of the racemo dyad with respect to the repeating unit represented by the formula (1) is preferably 60% or more or 30% or less.

  In said polymer, it is preferable that the number of groups containing the siloxane group contained per polymer molecule is 0.4-2.0.

  Moreover, according to this invention, the composite_body | complex obtained by apply | coating and hardening a curable resin to the molded object formed by shape | molding said polymer is provided.

  Furthermore, according to the present invention, there is provided a method for producing the above polymer, wherein a metal compound represented by the following formula (2) is used as a polymerization catalyst in the presence of a siloxane compound having an ethylenically unsaturated group. There is provided a method for producing a polymer, in which after the ring-opening metathesis polymerization of dicyclopentadiene, the carbon-carbon double bond of the resulting ring-opening polymer is hydrogenated.

M (NR ¹ ) X _4-a (OR ² ) _a · L _b (2)
(In the formula (2), M is a metal atom selected from Group 6 transition metal atoms in the periodic table, and R ¹ has a substituent at at least one of the 3, 4, and 5 positions. Or a group represented by —CH ₂ R ³ , wherein R ² is a group selected from an optionally substituted alkyl group and an optionally substituted aryl group X is a group selected from a halogen atom, an alkyl group, an aryl group and an alkylsilyl group, L is an electron-donating neutral ligand, a is 0 or 1, and b is 0 And R ³ is a group selected from a hydrogen atom, an alkyl group which may have a substituent, and an aryl group which may have a substituent.

  Furthermore, according to the present invention, there is provided a method for producing the above polymer, wherein the metal atom selected from the transition metal atoms of Group 6 of the periodic table is substituted with a halogen atom or a substituent at the 2nd and 6th positions. A phenoxy group having a hydrocarbon group having 4 or more carbon atoms which may have a substituent as a substituent, or a hydrocarbon having 4 or more carbon atoms which may have a halogen atom or a substituent at the 3rd and 3 'positions Ring-opening metathesis polymerization of dicyclopentadiene in the presence of a siloxane compound having an ethylenically unsaturated group using a metal compound formed by bonding a biphenoxy group having a group as a substituent as a polymerization catalyst. Provided is a method for producing a polymer in which the carbon-carbon double bond of the polymer is hydrogenated.

  In the polymer production method, the siloxane compound having an ethylenically unsaturated group preferably has a vinyl group bonded directly to a silicon atom of the siloxane group.

  In the method for producing the polymer, the weight average molecular weight of the ring-opened polymer before hydrogenating the carbon-carbon double bond is preferably 10,000 to 100,000.

  ADVANTAGE OF THE INVENTION According to this invention, the crystalline polymer of a cycloolefin polymer type | system | group excellent in heat resistance and adhesiveness with another material is provided.

  The polymer of the present invention has a polymer chain containing a repeating unit represented by the following formula (1) as a main constituent unit, and a group containing a siloxane group is bonded to the polymer chain. A polymer having crystallinity.

  The repeating unit represented by the formula (1) is a repeating unit that can be obtained by hydrogenating all the carbon-carbon double bonds of a repeating unit obtained by ring-opening polymerization of dicyclopentadiene. The content of the repeating unit in the polymer chain constituting the polymer of the present invention is not particularly limited as long as the repeating unit is a main constituent unit of the polymer chain and the target polymer has crystallinity. However, it is preferable that it is 90 mol% or more with respect to all the repeating units of a polymer chain, and it is more preferable that it is 95 mol% or more. When there is too little content of this repeating unit, there exists a possibility that the heat resistance of a polymer may become inadequate. The “all repeating units of the polymer chain” does not include a group containing a siloxane group when introduced at the terminal of the polymer chain.

  The polymer chain constituting the polymer of the present invention may consist only of the repeating unit represented by the formula (1), but the repeating unit represented by the formula (1) is the main constituent unit, As long as the polymer has crystallinity, it may contain other repeating units. The repeating unit other than the repeating unit represented by the formula (1) that can be contained in the polymer chain constituting the polymer of the present invention includes a repeating unit obtained by ring-opening polymerization of dicyclopentadiene (all carbons). -Carbon double bond not hydrogenated), a repeating unit obtainable by hydrogenating a part of the carbon-carbon double bond of the repeating unit obtained by ring-opening polymerization of dicyclopentadiene, And repeating units derived from monomers other than dicyclopentadiene.

  The content of the repeating unit other than the repeating unit represented by the formula (1) in the polymer chain constituting the polymer of the present invention is not particularly limited, but is preferably 10 mol% or less, preferably 5 mol%. The following is more preferable. When there is too much content of repeating units other than the repeating unit represented by Formula (1), there exists a possibility that adhesiveness and heat resistance with other materials of a polymer may become inadequate.

The presence or absence of stereoregularity of the polymer chain constituting the polymer of the present invention is not particularly limited as long as the polymer has crystallinity, but it is imparted to the polymer with heat resistance. From the viewpoint of having excellent properties, it is preferable that the material has stereoregularity (that is, other than an atactic structure). More specifically, the ratio of the racemo dyad for the repeating unit represented by the formula (1) is preferably 60% or more or 30% or less, and more preferably 65% or more or 25% or less. Preferably, it is 70% or more or 20% or less. When the ratio of racemo dyad exceeds 50%, it can be said that the polymer chain has syndiotactic regularity. When the ratio of racemo dyad is less than 50%, the polymer chain is It can be said that it has isotactic regularity. The higher the stereoregularity of the polymer chain (that is, the farther the racemo dyad ratio is from 50%), the higher the heat resistance polymer having a high melting point. In addition, the ratio of the racemo dyad about the repeating unit represented by Formula (1) can be measured and quantified by < ¹³ > C-NMR spectrum analysis. As a specific quantitative method, ortho-dichlorobenzene-d4 was used as a solvent and an inverse-gated decoupling method was applied at 150 ° C. to perform ¹³ C-NMR measurement, and a 127.5 ppm peak of orthodichlorobenzene-d4 was obtained. As a reference shift, a method of determining the ratio of racemo dyad from the intensity ratio of 43.35 ppm signal derived from meso dyad and 43.43 ppm signal derived from racemo dyad can be mentioned.

  The polymer of the present invention is obtained by bonding a group containing a siloxane group to a polymer chain containing the repeating unit represented by the formula (1) as the main constituent unit as described above. The polymer of the present invention has excellent adhesion to other materials based on the fact that a group containing a siloxane group is bonded to the polymer chain, and even if such a functional group is introduced. Since it is difficult to adversely affect the crystallinity exhibited by the polymer chain, it also has excellent heat resistance.

  In the polymer of the present invention, the position at which the group containing a siloxane group is bonded to the polymer chain comprising the repeating unit represented by formula (1) as the main constituent unit is not particularly limited. However, from the viewpoint of obtaining a polymer having high crystallinity and particularly good heat resistance, the terminal of the polymer chain is preferable. The term “end of the polymer chain” as used herein means the end of the polymer chain in a state before the group containing the siloxane group (siloxane group-containing group) is bonded. That is, when one siloxane group-containing group is bonded to two or more polymer chains at the ends of the polymer chains, the siloxane group-containing group is not located at the end when viewed as a whole polymer molecule. Even if it exists, the polymer shall be what the "end of the polymer chain" couple | bonded with the siloxane group containing group.

  The group containing a siloxane group in the polymer of the present invention is not particularly limited as long as it is a group containing a silicon-oxygen-silicon bond structure, but as a preferred group containing a siloxane group, the following formula (3 The siloxane group containing group contained in the polymer chain bond structure represented by this can be mentioned.

（式（３）中、ＨＰＤＣＰは式（１）で表される繰り返し単位を主たる構成単位として含んでなる重合体鎖であり、Ａは炭素数１〜２０の２価の炭化水素基である。Ｒ^４〜Ｒ^１２は、それぞれ独立に、炭素数１〜２０の炭化水素基、−Ａ−ＨＰＤＣＰ、およびオキシ基から選択される基であり、Ｒ^４〜Ｒ^１２のいずれかがオキシ基である場合にはＲ^４〜Ｒ^１２から選択される２つの基が一つの酸素原子に置き換わって環構造を形成する。ｐは０〜２０の整数であり、ｑは０〜２０の整数であり、ｒは１〜２０の整数である。）

(In Formula (3), HPDCP is a polymer chain containing the repeating unit represented by Formula (1) as a main structural unit, and A is a C1-C20 divalent hydrocarbon group. R ^{4 to} R ¹² are each independently a group selected from a hydrocarbon group having 1 to 20 carbon atoms, —A-HPDCP, and an oxy group, and any one of R ^{4 to} R ¹² is an oxy group. In some cases, two groups selected from R ^{4 to} R ¹² are replaced with one oxygen atom to form a ring structure, p is an integer of 0 to 20, q is an integer of 0 to 20, and r Is an integer from 1 to 20.)

  In the formula (3), p and q are each an integer of 0 to 20, and particularly preferably 0 or 1. r is an integer of 1 to 20, but is particularly preferably an integer of 1 to 10. In the formula (3), particularly preferable examples of the divalent hydrocarbon group having 1 to 20 carbon atoms represented by A include a methylene group, an ethylene group, a propylene group, a butylene group, and a phenylene group. Among them, a methylene group is particularly preferable.

In Formula (3), the groups represented by R ^{4 to} R ¹² are each independently selected from a hydrocarbon group having 1 to 20 carbon atoms, —A-HPDCP, and an oxy group. When the group represented by R ^{4 to} R ¹² is a hydrocarbon group having 1 to 20 carbon atoms, preferred groups include a methyl group, an ethyl group, an isopropyl group, and a phenyl group. Among them, a methyl group Is particularly preferred. In addition, the group represented by R ^{4 to} R ¹² is —A-HPDCP, that is, a structural unit mainly composed of a repeating unit represented by the formula (1) via a divalent hydrocarbon group having 1 to 20 carbon atoms. The polymer chain comprising as may be bonded. Furthermore, the group represented by R ^{4 to} R ¹² may be an oxy group (—O—). However, when any of R ^{4 to} R ¹² is an oxy group, two groups selected from R ^{4 to} R ¹² are replaced with one oxygen atom to form a ring structure.

  The molecular structure of the polymer of the present invention is a structure in which a polymer chain comprising a repeating unit represented by the formula (1) as a main constituent unit and a group containing a siloxane group (siloxane group-containing group) are bonded. As long as it has, it is not particularly limited. For example, a structure in which a siloxane group-containing group is bonded to one end of one polymer chain, a structure in which a siloxane group-containing group is bonded to both ends of one polymer chain, and two or more polymer chains Any structure such as a structure in which the terminal is bonded to one siloxane group-containing group may be used. The polymer of the present invention may be a mixture of polymers having different molecular structures.

The content of the group containing a siloxane group in the polymer of the present invention is not particularly limited, but from the viewpoint of particularly improving the balance between the adhesion between the polymer and other materials and the heat resistance, the polymer 1 The number of groups containing a siloxane group contained per molecule is preferably 0.4 to 2, and more preferably 0.5 to 2. In the present invention, the number of groups containing a siloxane group contained per molecule of the polymer can be determined by ¹ H-NMR spectrum measurement and gel permeation chromatography (GPC) measurement. Specifically, an integrated value of a peak derived from a proton of a carbon-carbon double bond existing in a polymer chain by measurement of ¹ H-NMR spectrum (or an integrated value of a peak derived from a proton of a saturated hydrocarbon) and It can be determined by comparing the integrated value of the peak derived from a group containing a siloxane group and the number average molecular weight (Mn) by GPC measurement.

  Although the weight average molecular weight of the polymer of this invention is not specifically limited, As a value of polystyrene conversion measured by a gel permeation chromatography (GPC), it is 10,000-100,000 normally, and 15,000-90. 20,000 is preferable, and 20,000 to 80,000 is more preferable. When the polymer of the present invention has such a weight average molecular weight, it has an excellent balance between heat resistance and molding processability. In addition, since the polymer of the present invention is difficult to dissolve in a solvent, it is difficult to apply GPC measurement under general conditions, but using a GPC apparatus capable of measurement at high temperature, GPC measurement can be performed by measuring under high temperature conditions (for example, 200 ° C. or higher).

  The molecular weight distribution of the polymer of the present invention [ratio of polystyrene-equivalent number average molecular weight and weight average molecular weight (Mw / Mn) measured by gel permeation chromatography] is not particularly limited, but is usually 1.5 to 5 0.0, preferably 1.6 to 4.0, more preferably 1.6 to 3.5. The polymer of the present invention has particularly excellent mechanical strength by having such a molecular weight distribution in this range.

  The polymer of the present invention only needs to have crystallinity, that is, any polymer having a melting point exceeding normal temperature (23 ° C.). However, from the viewpoint of particularly improving the heat resistance of the polymer, the polymer preferably has a melting point of 250 ° C. or higher, more preferably has a melting point of 255 to 290 ° C. It is particularly preferable that it has a melting point of 290 ° C.

  The method for obtaining the polymer of the present invention is not particularly limited as long as it is a method for obtaining a polymer having a target structure having crystallinity, but the method for producing the polymer of the present invention described below is preferred. It is. That is, the method for producing a polymer of the present invention is the above-described method for producing a polymer of the present invention, wherein at least one of two kinds of metal compounds each having a specific configuration is used as a polymerization catalyst. This is a method for producing a polymer, in which dicyclopentadiene is subjected to ring-opening metathesis polymerization in the presence of a siloxane compound having a group, and then a carbon-carbon double bond of the resulting ring-opening polymer is hydrogenated.

  In the method for producing a polymer of the present invention, dicyclopentadiene is used as a monomer for ring-opening metathesis polymerization. In dicyclopentadiene, there are stereoisomers of endo and exo, both of which can be used as monomers, and either isomer may be used alone, or endo and It is also possible to use an isomer mixture in which an exo isomer is present in an arbitrary ratio. However, from the viewpoint of improving the crystallinity of the finally obtained polymer and making the heat resistance particularly good, it is preferable to increase the ratio of one stereoisomer, for example, an endo-form or an exo-form. The ratio is preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more. In addition, it is preferable that the stereoisomer which makes a ratio high is an end body from a viewpoint of synthetic | combination ease.

  In the method for producing a polymer of the present invention, a monomer other than dicyclopentadiene may be included in dicyclopentadiene used as a monomer without departing from the present invention. Examples of monomers other than dicyclopentadiene include norbornene compounds other than dicyclopentadiene, monocyclic olefins, cyclic dienes, and derivatives thereof.

  One of the two types of metal compounds that can be used as a polymerization catalyst in the polymer production method of the present invention is a metal compound represented by the following formula (2). By using the metal compound represented by the formula (2), syndiotactic regularity can be imparted to the polymer chain of the obtained ring-opening polymer.

M (NR ¹ ) X _4-a (OR ² ) _a · L _b (2)
(In the formula (2), M is a metal atom selected from Group 6 transition metal atoms in the periodic table, and R ¹ has a substituent at at least one of the 3, 4, and 5 positions. Or a group represented by —CH ₂ R ³ , wherein R ² is a group selected from an optionally substituted alkyl group and an optionally substituted aryl group X is a group selected from a halogen atom, an alkyl group, an aryl group and an alkylsilyl group, L is an electron-donating neutral ligand, a is 0 or 1, and b is 0 And R ³ is a group selected from a hydrogen atom, an alkyl group which may have a substituent, and an aryl group which may have a substituent.

  The metal atom (M in the formula (2)) constituting the metal compound represented by the formula (2) is selected from group 6 transition metal atoms (chromium, molybdenum, tungsten) in the periodic table. Among these, molybdenum or tungsten is preferably used, and tungsten is particularly preferably used.

The metal compound represented by the formula (2) includes a metal imide bond. The substituent on the nitrogen atom constituting the metal imide bond (R ¹ in the formula (2)) is a phenyl group which may have a substituent at at least one of the 3, 4, and 5 positions, or- A group represented by CH ₂ R ³ (wherein R ³ is a group selected from a hydrogen atom, an alkyl group which may have a substituent and an aryl group which may have a substituent); It is. Examples of the substituent that the phenyl group which may have a substituent at at least one of the 3, 4, and 5 positions include an alkyl group such as a methyl group and an ethyl group; a fluorine atom, a chlorine atom, and a bromine atom A halogen atom such as; an alkoxy group such as a methoxy group, an ethoxy group, and an isopropoxy group; Also good. Specific examples of the phenyl group which may have a substituent at at least one of the 3, 4, and 5 positions include an unsubstituted phenyl group, a 4-methylphenyl group, a 4-chlorophenyl group, and 3-methoxyphenyl. Groups, monosubstituted phenyl groups such as 4-cyclohexylphenyl group, 4-methoxyphenyl group; 3,5-dimethylphenyl group, 3,5-dichlorophenyl group, 3,4-dimethylphenyl group, 3,5-dimethoxyphenyl group Disubstituted phenyl groups such as 3,4,5-trimethylphenyl groups, 3,4,5-trichlorophenyl groups and the like; 2-naphthyl groups, 3-methyl-2-naphthyl groups, 4-methyl 2-naphthyl group which may have a substituent such as a 2-naphthyl group;

In the metal compound represented by the formula (2), in the group represented by —CH ₂ R ³ which can be used as a substituent on the nitrogen atom (R ¹ in the formula (2)), R ³ is a hydrogen atom Represents a group selected from an alkyl group which may have a substituent and an aryl group which may have a substituent. The number of carbon atoms of the alkyl group which may be a substituent and can be a group represented by R ³ is not particularly limited, but is usually 1 to 20, preferably 1 to 10. The alkyl group may be linear or branched. Although the substituent which this alkyl group may have is not specifically limited, For example, the phenyl group which may have substituents, such as a phenyl group and 4-methylphenyl group; Alkoxyl groups, such as a methoxy group and an ethoxy group; Can be mentioned.

In the metal compound represented by the formula (2), an aryl group which may be used as a substituent on the nitrogen atom (R ¹ in the formula (2)) and may have a substituent includes a phenyl group, Examples include 1-naphthyl group, 2-naphthyl group, and aryl groups in which hydrogen atoms of these groups are replaced with other substituents. Further, the substituent of this aryl group is not particularly limited, but for example, a phenyl group which may have a substituent such as a phenyl group or a 4-methylphenyl group; an alkoxyl group such as a methoxy group or an ethoxy group; Can be mentioned.

In the metal compound represented by the formula (2), the group represented by R ³ includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, and a hexyl group. Alkyl groups having 1 to 20 carbon atoms such as octyl group and decyl group are particularly preferably used.

  The metal compound represented by the formula (2) has 3 or 4 groups selected from a halogen atom, an alkyl group, an aryl group, and an alkylsilyl group per molecule. That is, in the formula (2), X represents a group selected from a halogen atom, an alkyl group, an aryl group, and an alkylsilyl group. In the metal compound represented by the formula (2), the groups represented by X may be bonded to each other.

  Examples of the halogen atom that can be a group represented by X include a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a neopentyl group, a benzyl group, and a neophyll group. Examples of the aryl group include a phenyl group, a 4-methylphenyl group, a 2,6-dimethylphenyl group, a 1-naphthyl group, and a 2-naphthyl group. Examples of the alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, and a t-butyldimethylsilyl group.

The metal compound represented by the formula (2) may have one metal alkoxide bond or one metal aryloxide bond per molecule. The substituent on the oxygen atom constituting this metal alkoxide bond or metal aryloxide bond (R ² in formula (2)) may have an alkyl group which may have a substituent and a substituent. It is a group selected from good aryl groups. The alkyl group which may have a substituent and the aryl group which may have a substituent which can be a group represented by R ² are the same as those in the group represented by R ³ described above. Can be used.

  The metal compound represented by the formula (2) may have one or two electron-donating neutral ligands per molecule. Examples of the electron-donating neutral ligand (L in the formula (2)) include an electron-donating compound containing an atom of Group 14 or Group 15 of the periodic table. Specific examples thereof include phosphines such as trimethylphosphine, triisopropylphosphine, tricyclohexylphosphine, and triphenylphosphine; ethers such as diethyl ether, dibutyl ether, 1,2-dimethoxyethane, and tetrahydrofuran; trimethylamine, triethylamine, pyridine, And amines such as lutidine; Of these, ethers are particularly preferably used.

As a polymerization catalyst used in the method for producing a polymer of the present invention, a metal compound represented by the formula (2) which is particularly preferably used is a tungsten compound having a phenylimide group (M in the formula (2) is a tungsten atom). And a compound in which R ¹ is a phenyl group), among which a tetrachlorotungsten phenylimide (tetrahydrofuran) complex is particularly suitable.

  The metal compound represented by the formula (2) is an oxyhalide of a Group 6 transition metal and phenyl isocyanates optionally having a substituent at at least one of the 3, 4, and 5 positions, or Mixing monosubstituted methyl isocyanates with an electron-donating neutral ligand (L) and, if necessary, alcohols, metal alkoxides, metal aryloxides (for example, JP-A-5-345817) Can be synthesized by the method described in 1). The synthesized metal compound represented by the formula (2) may be purified and isolated by crystallization or the like, or the catalyst synthesis solution can be used as a polymerization catalyst as it is without purification. .

  Another one of the two types of metal compounds that can be used as a polymerization catalyst in the method for producing a polymer of the present invention is a 2-position of a metal atom selected from transition metal atoms of Group 6 of the periodic table and A phenoxy group having a halogen atom or a hydrocarbon group having 4 or more carbon atoms which may have a substituent at the 6-position as a substituent, or a halogen atom or a substituent at the 3-position and the 3'-position It is a metal compound formed by bonding a biphenoxy group having a good hydrocarbon group having 4 or more carbon atoms as a substituent. The metal atom constituting the metal compound is selected from chromium, molybdenum, and tungsten. Among them, molybdenum or tungsten is preferably used, and tungsten is particularly preferably used. Then, by using this metal compound, it is possible to impart isotactic regularity to the polymer chain of the resulting ring-opening polymer.

  The phenoxy group having a halogen atom or a hydrocarbon group having 4 or more carbon atoms which may have a halogen atom or a substituent at the 2-position and the 6-position as the substituent that the metal compound may have is not particularly limited. Although not present, a phenoxy group represented by the formula (4) is preferred.

（式（４）中、Ｒ^１３およびＲ^１７は、それぞれ、ハロゲン原子または置換基を有していてもよい炭素数４以上の炭化水素基であり、Ｒ^１４〜Ｒ^１６は、それぞれ、水素原子、ハロゲン原子、アルキル基およびアリール基から選択される基である。）

(In the formula (4), R ¹³ and R ¹⁷ are each a halogen atom or a hydrocarbon group having 4 or more carbon atoms which may have a substituent, and R ^{14 to} R ¹⁶ are each a hydrogen atom. , A group selected from a halogen atom, an alkyl group and an aryl group.)

（式（５）中、Ｒ^１８およびＲ^２５は、それぞれ、ハロゲン原子または置換基を有していてもよい炭素数４以上の炭化水素基であり、Ｒ^１９〜Ｒ^２４は、それぞれ、水素原子、ハロゲン原子、アルキル基およびアリール基から選択される基である。） In addition, biphenoxy groups having a halogen atom or a hydrocarbon group having 4 or more carbon atoms, which may have a halogen atom or a substituent at the 3 and 3 ′ positions, that the metal compound may have as a substituent are also particularly limited. Although not intended, a biphenoxy group represented by formula (5) is preferred.

(In Formula (5), R ¹⁸ and R ²⁵ are each a halogen atom or a hydrocarbon group having 4 or more carbon atoms which may have a substituent, and R ^{19 to} R ²⁴ are each a hydrogen atom. , A group selected from a halogen atom, an alkyl group and an aryl group.)

In formula (4) and formula (5), the groups represented by R ¹³ , R ¹⁷ , R ¹⁸ and R ²⁵ are each a hydrocarbon having 4 or more carbon atoms which may have a halogen atom or a substituent. It is a group. Preferable examples of the halogen atom include a bromine atom and an iodine atom. Examples of the hydrocarbon group having 4 or more carbon atoms that may have a substituent include t-butyl group, 2-methyl-2-butyl group, phenyl group, naphthyl group, and hydrocarbon groups thereof. And a group in which a part of the hydrogen atom is replaced with an arbitrary substituent. In this case, the substituent is not particularly limited, and examples thereof include a methyl group, an ethyl group, and an isopropyl group.

In Formula (4) and Formula (5), the groups represented by R ^{14 to} R ¹⁶ and R ^{19 to} R ²⁴ are groups selected from a hydrogen atom, a halogen atom, an alkyl group, and an aryl group, respectively. is there. Preferable examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom. Preferred examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a neopentyl group, a benzyl group, and a neophyll group. Preferable examples of the aryl group include a phenyl group, a 4-methylphenyl group, a 2,6-dimethylphenyl group, a 1-naphthyl group, and a 2-naphthyl group. Further, when the groups represented by R ^{14 to} R ¹⁶ and R ^{19 to} R ²⁴ in the formulas (4) and (5) are alkyl groups or aryl groups, two or more of them are bonded to form a ring structure. May be formed.

  Such a metal compound in which the specific phenoxy group or biphenoxy group is bonded to a metal atom selected from group 6 transition metal atoms in the periodic table is an oxyhalide or imide of group 6 transition metal. And a lithiated compound having the specific phenoxy group or a biphenoxy lithiated compound having the specific biphenoxy group (see, for example, Polymer Journal, 2011, Vol. 68, No. 5, p. 199-209) and the like. The synthesized metal compound may be purified and isolated by crystallization or the like, or the catalyst synthesis solution can be used as it is as a polymerization catalyst without purification.

  A phenoxy having, as a substituent, a hydrocarbon atom having 4 or more carbon atoms, which may have a halogen atom or a substituent at the 2-position and the 6-position, on a metal atom selected from group 6 transition metal atoms of the periodic table As a metal compound that is particularly preferably used as a metal compound formed by bonding a group, a metal compound represented by the following formula (6) or formula (7) can be given.

  In addition, a metal atom selected from group 6 transition metal atoms in the periodic table is substituted with a halogen atom or a hydrocarbon group having 4 or more carbon atoms, which may have a halogen atom or a substituent at the 3 and 3 ′ positions. As a metal compound formed by bonding a biphenoxy group as a particularly preferable metal compound, a metal compound represented by the following formula (8), formula (9) or formula (10) can be given.

  The amount of the metal compound used as the polymerization catalyst is such that the molar ratio of (metal compound: whole monomer used) is usually from 1: 100 to 1: 2,000,000, preferably from 1: 500 to 1,000,000. More preferably, it is used in an amount of 1: 1,000 to 1: 500,000. If the amount of catalyst is too large, it may be difficult to remove the catalyst. If the amount is too small, sufficient polymerization activity may not be obtained.

  In addition, when using a metal compound as a polymerization catalyst, the metal compound can be used alone, but it is preferable to use the metal compound and an organometallic reducing agent in combination from the viewpoint of increasing the polymerization activity. Examples of the organometallic reducing agent that can be used include organometallic compounds of Groups 1, 2, 12, 13, and 14 of the periodic table having a hydrocarbon group having 1 to 20 carbon atoms. Among these, organolithium, organomagnesium, organozinc, organoaluminum, or organotin are preferably used, and organolithium, organoaluminum, or organotin are particularly preferably used. Examples of the organic lithium include n-butyl lithium, methyl lithium, and phenyl lithium. Examples of the organic magnesium include butylethylmagnesium, butyloctylmagnesium, dihexylmagnesium, ethylmagnesium chloride, n-butylmagnesium chloride, and allylmagnesium bromide. Examples of the organic zinc include dimethyl zinc, diethyl zinc, and diphenyl zinc. Examples of organic aluminum include trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum ethoxide, diisobutylaluminum isobutoxide, ethylaluminum diethoxide, isobutylaluminum diisobutoxide, etc. Can be mentioned. Examples of the organic tin include tetramethyltin, tetra (n-butyl) tin, and tetraphenyltin. 0.1-100 mol times is preferable with respect to a metal compound, as for the usage-amount of an organometallic reducing agent, 0.2-50 mol times is more preferable, and 0.5-20 mol times is especially preferable. If the amount used is too small, the polymerization activity may not be improved, and if it is too much, side reactions may easily occur.

  In the method for producing a polymer of the present invention, a siloxane compound having an ethylenically unsaturated group is present in the polymerization reaction system when ring-opening metathesis polymerization of dicyclopentadiene using the metal compound as described above as a polymerization catalyst. Let Thus, the presence of the siloxane compound having an ethylenically unsaturated group causes a chain transfer reaction between the growth terminal of the polymer and the ethylenically unsaturated group of the siloxane compound having an ethylenically unsaturated group, A group containing a siloxane group can be introduced at the end of the polymer chain. The siloxane compound having an ethylenically unsaturated group used at this time is not particularly limited as long as it is a compound containing at least one ethylenically unsaturated group and a siloxane group in the molecule.

  As the siloxane compound having an ethylenically unsaturated group used in the method for producing a polymer of the present invention, a siloxane compound represented by the formula (11) is particularly preferably used.

（式（１１）中、Ａ’は単結合または炭素数１〜１９の２価の炭化水素基であり、Ｒ^２６〜Ｒ^３４は、それぞれ独立に、炭素数１〜２０の炭化水素基およびオキシ基から選択される基であり、Ｒ^２６〜Ｒ^３４のいずれかがオキシ基である場合にはＲ^２６〜Ｒ^３４から選択される２つの基が一つの酸素原子に置き換わって環構造を形成する。ｓは０〜２０の整数であり、ｔは０〜２０の整数であり、ｕは１〜２０の整数である。）

(In Formula (11), A ′ is a single bond or a divalent hydrocarbon group having 1 to 19 carbon atoms, and R ^{26 to} R ³⁴ are each independently a hydrocarbon group having 1 to 20 carbon atoms and an oxy group. When any of R ^{26 to} R ³⁴ is an oxy group, two groups selected from R ^{26 to} R ³⁴ are replaced with one oxygen atom to form a ring structure. S is an integer from 0 to 20, t is an integer from 0 to 20, and u is an integer from 1 to 20.)

In the formula (11), A ′ is a single bond or a divalent hydrocarbon group having 1 to 19 carbon atoms. Particularly preferable examples of A ′ include a single bond, a methylene group, an ethylene group, a propylene group, and a phenylene group. Among them, a single bond is particularly preferable. In formula (11), R ^{26 to} R ³⁴ are each independently a group selected from a hydrocarbon group having 1 to 20 carbon atoms and an oxy group. Siloxane compound represented by formula (11) having only one ethylenically unsaturated group per molecule (that is, having a hydrocarbon group containing an ethylenically unsaturated group as the group represented by R ^{26 to} R ³⁴ ). In this case, one polymer chain is bonded to one molecule of the siloxane compound. Specific examples of such siloxane compounds include tris (trimethylsiloxy) vinylsilane, tris (trimethylsiloxy) allylsilane, tris (trimethylsiloxy) styrylsilane, tris (trimethylsiloxy) -5-hexenylsilane, and tris (triethylsiloxy) vinylsilane. , Tris (triethylsiloxy) allylsilane, bis (trimethylsiloxy) (methyl) vinylsilane, bis (trimethylsiloxy) (methyl) allylsilane, dimethyl (trimethylsiloxy) vinylsilane, dimethyl (trimethylsiloxy) allylsilane, etc. in one molecule A siloxane compound having one of the following: in formula (11), A ′ is a single bond, R ^{26 to} R ³⁴ are methyl groups, and s, t, and u are each 2 to 10 vinyl groups -Containing dimethylsiloxane oligomer or terminal vinyldimethylsiloxane in which A 'is a single bond, R ²⁸ and R ^{31 to} R ³³ are methyl groups, R ³⁴ is a butyl group, s and t are 0, and u is 1 to 10 And siloxane oligomers having terminal olefin groups such as oligomers.

In addition, a siloxane compound represented by the formula (11) having two or more ethylenically unsaturated groups per molecule (that is, a hydrocarbon group containing an ethylenically unsaturated group as a group represented by R ^{26 to} R ³⁴⁾ When a siloxane compound having at least one is used, a chain transfer reaction occurs between each ethylenically unsaturated group and the polymer chain, so that two or more polymer chains per molecule of the siloxane compound. Combined. Therefore, the obtained polymer has a branched or star-like molecular structure. Specific examples of such siloxane compounds include 1,3-divinyltetramethyldisiloxane, 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane, 1,5-divinyl-3,3. -2 terminal olefin groups in one molecule such as diphenyl-1,1,5,5-tetramethyltrisiloxane, 1,5-divinyl-3-diphenylpentamethyltrisiloxane, divinyltetrakis (trimethylsiloxy) disiloxane In formula (11), A ′ is a single bond, R ²⁸ and R ^{31 to} R ³³ are methyl groups, R ³⁴ is a vinyl group, s and t are 0, u is 1 to 10 A vinyldimethylsiloxane oligomer at both ends or A ′ is a single bond, R ^{27 to} R ³¹ and R ³⁴ are methyl groups, and R ²⁶ and R ^{29 are} Mention may be made of a siloxane oligomer having two or more terminal olefin groups in one molecule, such as a vinylmethylsiloxane-dimethylsiloxane copolymer, which is a nyl group or a methyl group, u is 0, and s and t are 1 to 10 it can.

In the formula (11), the group represented by R ^{26 to} R ³⁴ may be an oxy group (—O—). However, when any of R ^{26 to} R ³⁴ is an oxy group, two groups selected from R ^{26 to} R ³⁴ are replaced with one oxygen atom to form a ring structure. Specific examples of the siloxane compound represented by the formula (11) having such a ring structure include 1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane, 1,3,5,7- Formulas (11) such as tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentavinyl-1,3,5,7,9-pentamethylcyclopentasiloxane In which R ³¹ and R ³⁴ are replaced by one oxygen atom, octavinyl octasilsesquioxane, monovinyl heptabutyl octasyl racesquioxane, monovinyl heptacyclohexyl octasyl racesquioxane, monoallyl hepta Silsesquioxane compounds consisting of multiple ring structures such as cyclopentyl octasilsesquioxane It can be mentioned.

  As the siloxane compound having an ethylenically unsaturated group used in the method for producing a polymer of the present invention, a siloxane compound having a vinyl group directly bonded to a silicon atom of the siloxane group is particularly preferably used. By using such a siloxane compound, it becomes easy to efficiently bond a group containing a siloxane group to the polymer chain. Among them, a siloxane compound represented by the formula (11), in which A ′ is a single bond, is preferably used, and among them, at least one of s and t in the formula (11) is 0. A certain siloxane compound is more preferably used, and among them, a siloxane compound in which both s and t in the formula (11) are 0 is particularly preferably used. By using such a siloxane compound, bonding of a group containing a siloxane group to the polymer chain is particularly efficiently performed, and a polymer having more excellent heat resistance can be obtained.

  In the method for producing a polymer of the present invention, examples of the siloxane compound having an ethylenically unsaturated group include 1,4-bis [tris (trimethylsiloxy) silyl] -2-butene and 1,6-bis [tris]. An internal olefin compound containing siloxane groups such as (trimethylsiloxy) silyl] -3-hexene on both sides of the carbon-carbon double bond can also be used. When a siloxane compound having a terminal olefin group is used as the siloxane compound having an ethylenically unsaturated group, the siloxane group is introduced only at one polymer chain end (one end). When an internal olefin compound contained on both sides of the double bond is used, a siloxane group is introduced at both polymer chain ends (both ends).

  In addition, in the manufacturing method of the polymer of this invention, the siloxane compound which has an ethylenically unsaturated group may be used individually by 1 type, and can also use 2 or more types together.

  In the method for producing a polymer of the present invention, a siloxane compound having an ethylenically unsaturated group can function as a chain transfer agent in a ring-opening polymerization reaction system and can function as a molecular weight modifier. Therefore, the amount of the siloxane compound having an ethylenically unsaturated group may be determined in consideration of the strength of the function as a molecular weight modifier exhibited by the compound and the molecular weight of the target dicyclopentadiene ring-opening polymer. Good. Although the specific usage-amount is not specifically limited, It is normally selected in 0.001-0.5 mol with respect to 1 mol of monomers used for a polymerization reaction, Preferably it is 0.002-0. It is selected in the range of 2 moles. As the molecular weight modifier, only a siloxane compound having an ethylenically unsaturated group can be used alone, but if necessary, a compound having an ethylenically unsaturated group not having a siloxane group may be used in combination. Good. A compound having an ethylenically unsaturated group that does not have a siloxane group works as a molecular weight modifier, but does not introduce a siloxane group into the polymer chain end. Even when it is desired to reduce the introduction rate of the siloxane group, a polymer having a desired molecular weight can be obtained.

  The polymerization reaction for obtaining the ring-opened polymer is usually carried out in an organic solvent. The organic solvent to be used is not particularly limited as long as the resulting ring-opening polymer or a hydrogenated product thereof can be dissolved or dispersed under predetermined conditions and does not inhibit the polymerization reaction or the hydrogenation reaction. Specific examples of the organic solvent include aliphatic hydrocarbons such as pentane, hexane, and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, and tricyclodecane. , Alicyclic hydrocarbons such as hexahydroindene and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated aliphatic hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; chlorobenzene and dichlorobenzene Halogen-containing aromatic hydrocarbons; nitrogen-containing hydrocarbon solvents such as nitromethane, nitrobenzene and acetonitrile; ethers such as diethyl ether and tetrahydrofuran; Others can be mixtures of these solvents. Of these solvents, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, and ethers are preferably used.

  The ring-opening polymerization reaction can be started by mixing a monomer, a metal compound used as a catalyst, and, if necessary, an organometallic reducing agent. The order in which these components are added is not particularly limited. For example, when a metal compound represented by formula (2) is used as a polymerization catalyst and an organic metal reducing agent is used in combination, a mixture of the metal compound represented by formula (2) and the organometallic reducing agent is added. The mixture of the monomer and the metal compound represented by the formula (2) may be added to the organometallic reducing agent and mixed, or the monomer and the organometallic reducing agent may be mixed. The metal compound represented by the formula (2) may be added to and mixed with the mixture. Moreover, when mixing each component, the whole quantity of each component may be added at once, may be added in multiple times, and it is continuous over a comparatively long time (for example, 1 minute or more). It can also be added.

  The concentration of the monomer during the polymerization reaction in the organic solvent is not particularly limited, but is preferably 1 to 50% by weight, more preferably 2 to 45% by weight, and particularly 3 to 40% by weight. preferable. If the monomer concentration is too low, the productivity of the polymer may be deteriorated. If it is too high, the solution viscosity after polymerization is too high, and the subsequent hydrogenation reaction may be difficult.

  An activity regulator may be added to the polymerization reaction system. The activity adjusting agent can be used for the purpose of stabilizing the polymerization catalyst, adjusting the polymerization reaction rate and the molecular weight distribution of the polymer. The activity regulator is not particularly limited as long as it is an organic compound having a functional group, but is preferably an oxygen-containing, nitrogen-containing, or phosphorus-containing organic compound. Specifically, ethers such as diethyl ether, diisopropyl ether, dibutyl ether, anisole, furan and tetrahydrofuran; ketones such as acetone, benzophenone and cyclohexanone; esters such as ethyl acetate; nitriles such as acetonitrile benzonitrile; triethylamine , Triisopropylamine, quinuclidine, amines such as N, N-diethylaniline; pyridines such as pyridine, 2,4-lutidine, 2,6-lutidine, 2-t-butylpyridine; triphenylphosphine, tricyclohexylphosphine Phosphines such as triphenyl phosphate and trimethyl phosphate; triphenyl phosphine, tricyclohexyl phosphine, triphenyl phosphate, trimethyl phosphate - phosphines such as preparative; phosphine oxides such as triphenylphosphine oxide; but like, but not limited to. These activity regulators can be used singly or in combination of two or more. The amount of the activity regulator to be added is not particularly limited, but it is usually selected from 0.01 to 100 mol% with respect to the metal compound used as the polymerization catalyst.

  Moreover, in order to adjust the molecular weight of the ring-opening polymer, a molecular weight adjusting agent other than the siloxane compound having an ethylenically unsaturated group may be added to the polymerization reaction system. Examples of the molecular weight modifier include α-olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene; aromatic vinyl compounds such as styrene and vinyltoluene; ethyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether, Oxygen-containing vinyl compounds such as allyl acetate, allyl alcohol and glycidyl methacrylate; halogen-containing vinyl compounds such as allyl chloride; nitrogen-containing vinyl compounds such as acrylamide; 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, Non-conjugated dienes such as 1,6-heptadiene, 2-methyl-1,4-pentadiene, 2,5-dimethyl-1,5-hexadiene; 1,3-butadiene, 2-methyl-1,3-butadiene, 2 , 3-Dimethyl-1,3-butadiene 1,3-pentadiene, a conjugated diene such as 1,3-hexadiene; can be mentioned.

  Although there is no restriction | limiting in particular in superposition | polymerization temperature, Usually, it is the range of -78 degreeC-+200 degreeC, Preferably it is the range of -30 degreeC-+180 degreeC. The polymerization time is not particularly limited and depends on the reaction scale, but is usually in the range of 1 minute to 1000 hours.

  As described above, a ring-opening polymer having stereoregularity is obtained in the course of the method for producing a polymer of the present invention. And if the conditions of the hydrogenation reaction are set to appropriate conditions as described later, the stereoregularity of the ring-opening polymer will not change in the hydrogenation reaction. By subjecting it to a hydrogenation reaction, the desired polymer which is a ring-opening polymer hydride having crystallinity based on having the stereoregularity can be obtained. The degree of stereoregularity of the ring-opening polymer can be adjusted by selecting the type of polymerization catalyst.

  The weight average molecular weight (Mw) measured by gel permeation chromatography of the ring-opening polymer (ring-opening polymer before hydrogenating the carbon-carbon double bond) subjected to the hydrogenation reaction is not particularly limited, It is preferably 10,000 to 100,000 in terms of polystyrene, and more preferably 15,000 to 80,000. By subjecting the ring-opening polymer having such a weight average molecular weight to a hydrogenation reaction, a polymer having an excellent balance between molding processability and heat resistance can be obtained. The weight average molecular weight of the ring-opening polymer can be adjusted by adjusting the amount of the molecular weight modifier used during polymerization.

  Molecular weight distribution of ring-opened polymer to be subjected to hydrogenation reaction (ring-opened polymer before hydrogenating carbon-carbon double bond) [number average molecular weight and weight average molecular weight in terms of polystyrene measured by gel permeation chromatography] The ratio (Mw / Mn)] is not particularly limited, but is usually 1.5 to 4.0, preferably 1.6 to 3.5. By subjecting the ring-opening polymer having such a molecular weight distribution to a hydrogenation reaction, a polymer particularly excellent in molding processability can be obtained. The molecular weight distribution of the ring-opening polymer can be adjusted by the monomer addition method and the monomer concentration during the polymerization reaction.

  Hydrogenation reaction of a ring-opening polymer (hydrogenation of double bonds existing in a polymer main chain and a repeating unit derived from dicyclopentadiene) is carried out in the presence of a hydrogenation catalyst in the reaction system. This can be done by supplying. Any hydrogenation catalyst can be used as long as it is generally used in the hydrogenation of olefin compounds, and is not particularly limited. Examples thereof include the following.

  As the homogeneous catalyst, a catalyst system comprising a combination of a transition metal compound and an alkali metal compound, such as cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride / sec- Examples include butyl lithium, tetrabutoxy titanate / dimethyl magnesium, and the like. Further, noble metal complex catalysts such as dichlorobis (triphenylphosphine) palladium, chlorohydridocarbonyltris (triphenylphosphine) ruthenium, bis (tricyclohexylphosphine) benzilidineruthenium (IV) dichloride, chlorotris (triphenylphosphine) rhodium, etc. Can do.

  As the heterogeneous catalyst, nickel, palladium, platinum, rhodium, ruthenium, or a solid catalyst in which these metals are supported on a support such as carbon, silica, diatomaceous earth, alumina, titanium oxide, for example, nickel / silica, nickel / Examples of the catalyst system include diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, and palladium / alumina.

  The hydrogenation reaction is usually performed in an inert organic solvent. Examples of such inert organic solvents include aromatic hydrocarbons such as benzene and toluene; aliphatic hydrocarbons such as pentane and hexane; alicyclic hydrocarbons such as cyclohexane and decahydronaphthalene; tetrahydrofuran, ethylene glycol dimethyl ether, and the like. Ethers; and the like. The inert organic solvent is usually the same as the solvent used in the polymerization reaction, and the hydrogenation catalyst may be added to the polymerization reaction solution as it is and reacted.

  Although the suitable range of conditions varies depending on the hydrogenation catalyst system used, the reaction temperature is usually -20 ° C to + 250 ° C, preferably -10 ° C to + 220 ° C, more preferably 0 ° C to 200 ° C. . If the hydrogenation temperature is too low, the reaction rate may be too slow, and if it is too high, side reactions may occur. The hydrogen pressure is usually 0.01 to 20 MPa, preferably 0.05 to 15 MPa, and more preferably 0.1 to 10 MPa. If the hydrogen pressure is too low, the hydrogenation rate may be too slow, and if it is too high, there will be restrictions on the apparatus in that a high pressure reactor is required. Although reaction time will not be specifically limited if it can be set as the desired hydrogenation rate, Usually, it is 0.1 to 10 hours. After the hydrogenation reaction, the target polymer may be recovered according to a conventional method. In recovering the polymer, the catalyst residue can be removed by a technique such as filtration.

  The hydrogenation rate (ratio of hydrogenated main chain double bonds) in the hydrogenation reaction of the ring-opening polymer is not particularly limited, but is preferably 98% or more, more preferably 99% or more, and particularly preferably 99.99. 5% or more. The higher the hydrogenation rate, the better the heat resistance of the finally obtained polymer.

  For example, the polymer of the present invention that can be obtained as described above has excellent processability inherent to the cycloolefin polymer, and is further improved in heat resistance and adhesion to other materials. Therefore, it can be suitably used as a material for various applications. The form of use of the polymer of the present invention is not particularly limited, but from the viewpoint of utilizing the property of excellent adhesion to other materials, a composite of the molded product of the polymer of the present invention and other materials It is preferable to use as a composite obtained by applying a curable resin to a molded product obtained by molding the polymer of the present invention and curing it.

  The method for molding the polymer of the present invention is not particularly limited, but melt molding methods such as injection molding, extrusion molding, press molding, blow molding, and calendar molding are suitable. Moreover, when obtaining a molded object, you may mix | blend various additives with a polymer as needed. Specific examples of additives include antioxidants, nucleating agents, fillers, flame retardants, flame retardant aids, pigments, colorants, antistatic agents, plasticizers, ultraviolet absorbers, light stabilizers, and near infrared absorbers. And a lubricant.

  In the case of obtaining a composite, examples of the curable resin that is applied to the molded body and cured are curable silicone resin, curable epoxy resin, curable epoxy silicone hybrid resin, curable acrylic resin, and curable polyimide resin. Can be mentioned. Among these, a curable silicone resin or a curable epoxy resin is particularly preferable. The curing method of the curable resin is not particularly limited, and any method such as thermosetting or photocuring may be used, but a thermosetting resin is particularly preferable.

  The use of the composite obtained from the polymer molded product of the present invention and the curable resin is not particularly limited, but the polymer molded product is used as a light reflector, the curable resin is used as a sealing agent, and the LED is used. It is particularly preferably used for constructing. In this case, the polymer is titanium oxide, white lead, zinc white, barium sulfate, calcium sulfate, basic lead sulfate, lithopone, zinc sulfide, lead titanate, zirconium oxide, barite, barium carbonate, chalk, precipitated calcium carbonate. The light reflectivity can be improved by adding white pigments such as stone kou, magnesium carbonate, alumina, clay, talc powder, and diatomaceous earth.

  Moreover, the polymer of this invention is excellent also in the adhesiveness with respect to inorganic fibers, such as glass fiber and carbon fiber. Therefore, the composition comprising the polymer of the present invention and inorganic fibers can be suitably used as a so-called engineering plastic for applications requiring heat resistance, such as home appliance parts and automobile parts.

  Moreover, since the polymer of this invention is excellent also in adhesiveness with a metal, it can be used suitably also as a material of electronic components, such as an electronic circuit board and a flexible printed circuit board. When the polymer of the present invention is used for such an application, it can be used as a composite of the molded product of the polymer of the present invention and a metal such as gold, silver, nickel, copper, and aluminum.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In addition, unless otherwise indicated, the part and% in each example are a basis of weight.

Moreover, the measurement and evaluation in each example were performed by the following methods.
Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In addition, unless otherwise indicated, the part and% in each example are a basis of weight.

Moreover, the measurement and evaluation in each example were performed by the following methods.
(1) Molecular weight of the ring-opening polymer (weight average molecular weight and molecular weight distribution)
Using a gel permeation chromatography (GPC) system HLC-8220 (manufactured by Tosoh Corporation), an H-type column (manufactured by Tosoh Corporation) was measured at 40 ° C. using tetrahydrofuran as a solvent, and was determined as a polystyrene equivalent value.
(2) Number of groups containing a siloxane group per molecule of polymer Peak area derived from a group containing a siloxane group, obtained by measuring ¹ H-NMR for a ring-opened polymer before hydrogenation, and Based on the peak area derived from the repeating unit formed by ring-opening polymerization of dicyclopentadiene, the content of the group containing the siloxane group with respect to all the repeating units is obtained, and the measured value and the number of ring-opening polymers before hydrogenation Calculations were based on average molecular weight measurements.
(3) Hydrogenation rate of ring-opening polymer
^It calculated | required based on < ¹ > H-NMR measurement.
(4) Melting point (or glass transition temperature) of polymer and heat of fusion Using a differential scanning calorimeter, the temperature was raised to 330 ° C., and then the cooled sample was heated at a rate of 10 ° C./min.
(5) Polymer meso / racemo dyad ratio Using ortho-dichlorobenzene-d4 as a solvent, an inverse-gated decoupling method was applied at 150 ° C. to perform ¹³ C-NMR measurement, and 127.5 ppm of orthodichlorobenzene-d4. Based on the intensity ratio of the 43.35 ppm signal derived from meso dyad and the 43.43 ppm signal derived from racemo dyad, the meso / racemo dyad ratio was determined.
(6) Adhesion Test with Thermosetting Silicone Resin The polymer powder obtained in each example was vacuum hot pressed to prepare a 30 mm × 30 mm × 1 mm test plate. Next, a thermosetting silicone resin (a mixture of “OE-6636A” and “OE-6636B” manufactured by Toray Dow Corning Co., Ltd. at a weight ratio of 1: 2) was applied to the test plate at a thickness of 0.05 mm. The thermosetting silicone resin was cured by placing it in an oven and heating at 100 ° C. for 1 hour, followed by heating at 150 ° C. for 1 hour. Then, 3 × 3 grid cuts are made in a 5 mm square grid shape on the cured silicone resin film on the test plate, and an adhesive tape (“NICHIBAN cello tape No. .405 "), a 90 ° peel test was performed, and the number of peeled grids was counted. The smaller the number of peeled lattices, the better the adhesion.

[Example 1]
After sufficiently drying, a nitrogen-substituted glass pressure-resistant reaction vessel was charged with 40 parts of a 75% cyclohexane solution (30 parts as the amount of dicyclopentadiene) of dicyclopentadiene (endo content 99% or more) and tris (trimethylsiloxy). ) 2.9 parts of vinyl silane was added, and 76 parts of cyclohexane was further added. Subsequently, 0.23 part of a 19% n-hexane solution of diethylaluminum ethoxide was added and stirred. Next, a solution in which 0.055 part of a tetrachlorotungstenphenylimide (tetrahydrofuran) complex was dissolved in 2 parts of toluene was added and heated to 50 ° C. to initiate a ring-opening polymerization reaction. After 3 hours, a small amount of isopropanol was added to stop the polymerization reaction, and then the polymerization reaction solution was poured into a large amount of isopropanol to solidify the ring-opened polymer. The solidified ring-opening polymer was separated from the solution by filtration and collected, and then dried at 40 ° C. for 20 hours under vacuum. The yield of the obtained ring-opening polymer was 30 parts (yield 100%). Also, the resulting ring-opening polymer was subjected to measurement of molecular weight and ^{1 H-NMR.} Next, 10 parts of the obtained ring-opening polymer and 44 parts of cyclohexane were added to a pressure-resistant reaction vessel and stirred to dissolve the ring-opening polymer in cyclohexane, and then chlorohydridocarbonyltris (triphenylphosphine) ruthenium. A hydrogenation catalyst solution prepared by dissolving 0065 parts in 6 parts of toluene was added, and a hydrogenation reaction was performed at a hydrogen pressure of 4 MPa and 160 ° C. for 5 hours. The obtained hydrogenation reaction liquid was poured into a large amount of isopropyl alcohol to completely precipitate the polymer, washed by filtration and then dried under reduced pressure at 60 ° C. for 24 hours to obtain a crystalline polymer. About the obtained polymer, the measurement of < ¹³ > C-NMR and differential scanning calorific value, and the adhesiveness test with a thermosetting silicone resin were done. The hydrogenation rate of the ring-opened polymer determined from the results of each measurement is substantially 100% (the content of unhydrogenated carbon-carbon double bonds below the detection limit). Table 1 summarizes the molecular weight of the ring polymer, the number of groups containing siloxane groups per polymer molecule, the meso / racemo dyad ratio of the polymer, the melting point, the heat of fusion, and the adhesion test results. It was.

[Example 2]
In the ring-opening polymerization reaction, the ring-opening polymerization reaction was performed in the same manner as in Example 1 except that 1.1 parts of bis (trimethylsiloxy) (methyl) vinylsilane was used instead of 2.9 parts of tris (trimethylsiloxy) vinylsilane. And a hydrogenation reaction was performed to obtain a crystalline polymer. The yield of the ring-opening polymer was 30 parts (yield 100%). The obtained ring-opening polymer and polymer were subjected to the same measurements and tests as in Example 1. The hydrogenation rate of the ring-opening polymer determined from the results of each measurement is substantially 100%, and the molecular weight of the ring-opening polymer and the number of groups containing siloxane groups per polymer molecule. The results of the meso / racemo dyad ratio, melting point, heat of fusion, and adhesion test of the polymer are summarized in Table 1.

Example 3
In the ring-opening polymerization reaction, the ring-opening polymerization reaction was performed in the same manner as in Example 1 except that 0.36 part of 1,3-divinyltetramethyldisiloxane was used instead of 2.9 parts of tris (trimethylsiloxy) vinylsilane. And a hydrogenation reaction was performed to obtain a crystalline polymer. The yield of the ring-opening polymer was 29 parts (yield 97%). The obtained ring-opening polymer and polymer were subjected to the same measurements and tests as in Example 1. The hydrogenation rate of the ring-opening polymer determined from the results of each measurement is substantially 100%, and the molecular weight of the ring-opening polymer and the number of groups containing siloxane groups per polymer molecule. The results of the meso / racemo dyad ratio, melting point, heat of fusion, and adhesion test of the polymer are summarized in Table 1.

Example 4
In the ring-opening polymerization reaction, instead of 2.9 parts of tris (trimethylsiloxy) vinylsilane, polydimethylsiloxane having vinyl groups at both ends (A ′ in the formula (11) is a single bond, R ²⁸ and R ^{31 to} R ³³ is a methyl group, R ³⁴ is a vinyl group, s and t are 0, and siloxane compound represented by the formula (11) in which u is 4.2 on average, molecular weight 500), “DMS-V03 A ring-opening polymerization reaction and a hydrogenation reaction were carried out in the same manner as in Example 1 except that 0.91 part (manufactured by Gerest) was used to obtain a crystalline polymer. The yield of the ring-opening polymer was 29 parts (yield 97%). The obtained ring-opening polymer and polymer were subjected to the same measurements and tests as in Example 1. The hydrogenation rate of the ring-opening polymer determined from the results of each measurement is substantially 100%, and the molecular weight of the ring-opening polymer and the number of groups containing siloxane groups per polymer molecule. The results of the meso / racemo dyad ratio, melting point, heat of fusion, and adhesion test of the polymer are summarized in Table 1.

Example 5
In the ring-opening polymerization reaction, instead of 2.9 parts of tris (trimethylsiloxy) vinylsilane, polydimethylsiloxane having vinyl groups at both ends (A ′ in the formula (11) is a single bond, R ²⁸ and R ^{31 to} R Siloxane compound represented by formula (11), wherein ³³ is a methyl group, R ³⁴ is a vinyl group, s and t are 0, and u is 8.3 on average, molecular weight 800) “DMS-V05” (Gerest Except for using 1.27 parts), a ring-opening polymerization reaction and a hydrogenation reaction were carried out in the same manner as in Example 1 to obtain a crystalline polymer. The yield of the ring-opening polymer was 29 parts (yield 97%). The obtained ring-opening polymer and polymer were subjected to the same measurements and tests as in Example 1. The hydrogenation rate of the ring-opening polymer determined from the results of each measurement is substantially 100%, and the molecular weight of the ring-opening polymer and the number of groups containing siloxane groups per polymer molecule. The results of the meso / racemo dyad ratio, melting point, heat of fusion, and adhesion test of the polymer are summarized in Table 1.

Example 6
In the ring-opening polymerization reaction, 0.78 parts of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane was used instead of 2.9 parts of tris (trimethylsiloxy) vinylsilane. Except that, a ring-opening polymerization reaction and a hydrogenation reaction were carried out in the same manner as in Example 1 to obtain a crystalline polymer. The yield of the ring-opening polymer was 29 parts (yield 97%). The obtained ring-opening polymer and polymer were subjected to the same measurements and tests as in Example 1. The hydrogenation rate of the ring-opening polymer determined from the results of each measurement is substantially 100%, and the molecular weight of the ring-opening polymer and the number of groups containing siloxane groups per polymer molecule. The results of the meso / racemo dyad ratio, melting point, heat of fusion, and adhesion test of the polymer are summarized in Table 1.

Example 7
In the ring-opening polymerization reaction, instead of 2.9 parts of tris (trimethylsiloxy) vinylsilane, cyclic polyvinylmethylsiloxane (wherein R ³¹ and R ³⁴ in formula (11) are replaced by one oxygen atom to form a ring structure) , A ′ is a single bond, R ²⁸ , R ³⁰ and R ³³ are methyl groups, R ²⁹ and R ³² are vinyl groups, s is 0, and the sum of t and u is 3, 4 or 5 (11) A mixture of siloxane compounds represented by (11)) A ring-opening polymerization reaction and a hydrogenation reaction were carried out in the same manner as in Example 1 except that 0.78 part of "VMS-005" (manufactured by Gerest) was used. A crystalline polymer was obtained. The yield of the ring-opening polymer was 29 parts (yield 97%). The obtained ring-opening polymer and polymer were subjected to the same measurements and tests as in Example 1. The hydrogenation rate of the ring-opening polymer determined from the results of each measurement is substantially 100%, and the molecular weight of the ring-opening polymer and the number of groups containing siloxane groups per polymer molecule. The results of the meso / racemo dyad ratio, melting point, heat of fusion, and adhesion test of the polymer are summarized in Table 1.

Example 8
After sufficiently drying, in a pressure-resistant reaction vessel made of nitrogen-substituted glass, 40 parts of a 75% cyclohexane solution of dicyclopentadiene (endo content 99% or more) (30 parts as the amount of dicyclopentadiene) and 1,3- Divinyltetramethyldisiloxane (0.36 part) was charged, and further 76 parts of cyclohexane was added and stirred. A solution in which 0.035 part of the molybdenum complex represented by the above formula (8) was dissolved in 2 parts of toluene was added and heated to 50 ° C. to initiate a ring-opening polymerization reaction. After 3 hours, a small amount of isopropanol was added to stop the polymerization reaction, and then the polymerization reaction solution was poured into a large amount of isopropanol to solidify the ring-opened polymer. The solidified ring-opening polymer was separated from the solution by filtration and collected, and then dried at 40 ° C. for 20 hours under vacuum. The yield of the obtained ring-opening polymer was 29 parts (yield 97%). Also, the resulting ring-opening polymer was subjected to measurement of molecular weight and ^{1 H-NMR.} Next, 10 parts of the obtained ring-opening polymer and 44 parts of cyclohexane were added to a pressure-resistant reaction vessel and stirred to dissolve the ring-opening polymer in cyclohexane, and then chlorohydridocarbonyltris (triphenylphosphine) ruthenium. A hydrogenation catalyst solution prepared by dissolving 0065 parts in 6 parts of toluene was added, and a hydrogenation reaction was performed at a hydrogen pressure of 4 MPa and 160 ° C. for 5 hours. The obtained hydrogenation reaction liquid was poured into a large amount of isopropyl alcohol to completely precipitate the polymer, washed by filtration and then dried under reduced pressure at 60 ° C. for 24 hours to obtain a crystalline polymer. About the obtained polymer, the measurement of < ¹³ > C-NMR and differential scanning calorific value, and the adhesiveness test with a thermosetting silicone resin were done. The hydrogenation rate of the ring-opened polymer determined from the results of each measurement is substantially 100% (the content of unhydrogenated carbon-carbon double bonds below the detection limit). Table 1 summarizes the molecular weight of the ring polymer, the number of groups containing siloxane groups per polymer molecule, the meso / racemo dyad ratio of the polymer, the melting point, the heat of fusion, and the adhesion test results. It was.

[Comparative Example 1]
In the ring-opening polymerization reaction, a ring-opening polymerization reaction and a hydrogenation reaction were performed in the same manner as in Example 1 except that 1.90 parts of 1-hexene was used instead of 2.9 parts of tris (trimethylsiloxy) vinylsilane. Thus, a crystalline polymer was obtained. The yield of the ring-opening polymer was 28 parts (yield 95%). The obtained ring-opening polymer and polymer were subjected to the same measurements and tests as in Example 1. The hydrogenation rate of the ring-opening polymer determined from the results of each measurement is substantially 100%. Also, the molecular weight of the ring-opening polymer, the number of siloxane groups per polymer, The meso / racemo dyad ratio, melting point, heat of fusion, and adhesion test results are summarized in Table 1.

[Comparative Example 2]
After sufficiently drying, in a pressure-resistant reaction vessel made of nitrogen-substituted glass, 40 parts of a 75% cyclohexane solution of dicyclopentadiene (endo content 99% or more) (30 parts as the amount of dicyclopentadiene) and 1,3- Divinyltetramethyldisiloxane (0.36 part) was charged, and further 76 parts of cyclohexane was added and stirred. Next, a solution in which 0.019 part of a ruthenium complex represented by the following formula (12) was dissolved in 2 parts of toluene was added and heated to 50 ° C. to initiate a ring-opening polymerization reaction. After 3 hours, a small amount of isopropanol was added to stop the polymerization reaction, and then the polymerization reaction solution was poured into a large amount of isopropanol to solidify the ring-opened polymer. The solidified ring-opening polymer was separated from the solution by filtration and collected, and then dried at 40 ° C. for 20 hours under vacuum. The yield of the obtained ring-opening polymer was 29 parts (yield 97%). Also, the resulting ring-opening polymer was subjected to measurement of molecular weight and ^{1 H-NMR.} Next, 10 parts of the obtained ring-opening polymer and 44 parts of cyclohexane were added to a pressure-resistant reaction vessel and stirred to dissolve the ring-opening polymer in cyclohexane, and then chlorohydridocarbonyltris (triphenylphosphine) ruthenium. A hydrogenation catalyst solution prepared by dissolving 0065 parts in 6 parts of toluene was added, and a hydrogenation reaction was performed at a hydrogen pressure of 4 MPa and 160 ° C. for 5 hours. The obtained hydrogenation reaction solution is poured into a large amount of isopropyl alcohol to completely precipitate the polymer, washed by filtration and dried under reduced pressure at 60 ° C. for 24 hours to obtain a polymer (hydrogenated ring-opened polymer). It was. About the obtained polymer, the measurement of < ¹³ > C-NMR and differential scanning calorific value, and the adhesiveness test with a thermosetting silicone resin were done. The hydrogenation rate of the ring-opened polymer determined from the results of each measurement is substantially 100% (the content of unhydrogenated carbon-carbon double bonds below the detection limit). The molecular weight of the ring polymer, the meso / racemo dyad ratio of the polymer, and the results of the adhesion test are summarized in Table 1. In addition, since the obtained polymer (ring-opening polymer hydride) did not have crystallinity, when the glass transition temperature was determined in the differential scanning calorimetry, the glass transition temperature was 98 ° C. Met.

  As can be seen from the results shown in Table 1, the polymers of the present invention (Examples 1-8) having polymer chains to which groups containing siloxane groups are bonded exhibit a high melting point and a large heat of fusion, and In the adhesion test, since the tape is hardly peeled off, it can be said to be excellent in heat resistance and adhesion to other materials. Among them, as a siloxane compound (molecular weight modifier) having an ethylenically unsaturated group, a siloxane compound (vinyl) represented by the formula (11) in which A ′ in the formula (11) is a single bond, and s and t are 0. Since the polymers (Examples 3 to 5 and 8) obtained using the dimethylsiloxane compound) exhibited particularly high melting points, it can be said that they are particularly excellent in heat resistance. On the other hand, a crystalline polymer (Comparative Example 1) in which a group containing a siloxane group is not bonded was excellent in heat resistance, but causes tape peeling in an adhesion test, Compared with the polymer of this invention, it was inferior to adhesiveness with another material. In addition, although a polymer having a siloxane group in the polymer chain is bonded, the polymer having no crystallinity (Comparative Example 2) exhibited a relatively low glass transition temperature. It can be said that it was inferior to.

Claims (8)

A polymer having crystallinity, comprising a polymer chain comprising a repeating unit represented by the following formula (1) as a main constituent unit, and a group containing a siloxane group bonded to the polymer chain. .

  2. The polymer according to claim 1, wherein in the polymer chain, the ratio of the racemo dyad with respect to the repeating unit represented by the formula (1) is 60% or more or 30% or less.   The polymer according to claim 1 or 2, wherein the number of groups containing a siloxane group contained in one molecule of the polymer is 0.4 to 2.0.   The composite_body | complex obtained by apply | coating and hardening a curable resin to the molded object formed by shape | molding the polymer in any one of Claims 1-3. It is a manufacturing method of the polymer in any one of Claims 1-3, Comprising: In presence of the siloxane compound which has an ethylenically unsaturated group using the metal compound represented by following formula (2) as a polymerization catalyst. Then, after the ring-opening metathesis polymerization of dicyclopentadiene, the carbon-carbon double bond of the resulting ring-opening polymer is hydrogenated.
M (NR ¹ ) X _4-a (OR ² ) _a · L _b (2)
(In the formula (2), M is a metal atom selected from Group 6 transition metal atoms in the periodic table, and R ¹ has a substituent at at least one of the 3, 4, and 5 positions. Or a group represented by —CH ₂ R ³ , wherein R ² is a group selected from an optionally substituted alkyl group and an optionally substituted aryl group X is a group selected from a halogen atom, an alkyl group, an aryl group and an alkylsilyl group, L is an electron-donating neutral ligand, a is 0 or 1, and b is 0 And R ³ is a group selected from a hydrogen atom, an alkyl group which may have a substituent, and an aryl group which may have a substituent.   It is a manufacturing method of the polymer in any one of Claims 1-3, Comprising: A halogen atom or a substituent is provided in the 2nd-position and the 6-position to the metal atom selected from the transition metal atom of the periodic table group 6 A phenoxy group having a hydrocarbon group having 4 or more carbon atoms which may have as a substituent, or a hydrocarbon group having 4 or more carbon atoms which may have a halogen atom or a substituent at the 3rd and 3 'positions Is used as a polymerization catalyst, and after the ring-opening metathesis polymerization of dicyclopentadiene in the presence of a siloxane compound having an ethylenically unsaturated group, the resulting ring-opening weight is obtained. A method for producing a polymer, wherein a carbon-carbon double bond of a coalescence is hydrogenated.   The method for producing a polymer according to claim 5 or 6, wherein the siloxane compound having an ethylenically unsaturated group has a vinyl group directly bonded to a silicon atom of the siloxane group.   The method for producing a polymer according to any one of claims 5 to 7, wherein the ring-opening polymer before hydrogenating the carbon-carbon double bond has a weight average molecular weight of 10,000 to 100,000.