JP6159054B2 - POLYMER, COMPOSITE AND METHOD FOR PRODUCING POLYMER - Google Patents

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 inventors have obtained dicyclopentadiene in the presence of an oxysilane compound having an ethylenically unsaturated group in obtaining a ring-opening polymer of dicyclopentadiene. After the ring-opening polymerization, the resulting ring-opening polymer is hydrogenated to obtain a crystalline polymer, whereby a crystalline dicyclopentadiene ring-opening polymer hydride such as high heat resistance is obtained. It has been found that a polymer excellent in adhesiveness to other materials can be obtained while having the features inherently possessed. The present invention has been completed based on this finding.

  Thus, according to the present invention, a polymer chain containing a repeating unit represented by the following formula (1) as a main constituent unit is bonded to a group containing an oxysilyl group at the end of the polymer chain. Thus, a crystalline polymer having a weight average molecular weight of 10,000 to 100,000 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 the above polymer, the number of oxysilyl groups contained in one polymer chain is preferably 0.4 to 4.0.

  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 polymer, wherein a metal compound represented by the following formula (2) or a metal compound represented by the following formula (3) is used as a polymerization catalyst: Provided is a method for producing a polymer, in which after the ring-opening metathesis polymerization of dicyclopentadiene in the presence of an oxysilane compound having an ethylenically unsaturated group, the carbon-carbon double bond of the resulting ring-opening polymer is hydrogenated. Is done.

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.

（式（３）中、Ｍは周期律表第６族の遷移金属原子から選択される金属原子であり、Ｒ^４はアルキル基およびアリール基から選択される基であり、Ｒ^５およびＲ^６は、それぞれ独立に水素原子、アルキル基およびアリール基から選択される基であり、Ｒ^７およびＲ^１４は、それぞれ独立にアルキル基およびアリール基から選択される基であり、Ｒ^８〜Ｒ^１３は、それぞれ独立に水素原子、アルキル基およびアリール基から選択される基であり、Ｒ^７〜Ｒ^１４のうち２個以上が結合して環構造を形成していてもよい。Ｙは電子供与性の中性配位子であり、ｐは０〜２の整数である。）

(In Formula (3), M is a metal atom selected from transition metal atoms of Group 6 of the periodic table, R ⁴ is a group selected from an alkyl group and an aryl group, and R ⁵ and R ⁶ are , Each independently a group selected from a hydrogen atom, an alkyl group and an aryl group, R ⁷ and R ¹⁴ are each independently a group selected from an alkyl group and an aryl group, and R ^{8 to} R ¹³ are Each independently represents a group selected from a hydrogen atom, an alkyl group, and an aryl group, and two or more of R ^{7 to} R ¹⁴ may be bonded to form a ring structure. And p is an integer of 0 to 2.)

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

  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 structural unit, and a group containing an oxysilyl group is bonded to the terminal of the polymer chain. A polymer having crystallinity and having a weight average molecular weight of 10,000 to 100,000.

  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 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 an oxysilyl group to the end of a polymer chain containing the repeating unit represented by the formula (1) as the main constituent unit as described above. is there. The polymer of the present invention has excellent adhesion to other materials based on the fact that a group containing an oxysilyl group is bonded to the end of the polymer chain, and introduces such a functional group. However, since it is difficult to adversely affect the crystallinity exhibited by the polymer chain, it also has excellent heat resistance. The group containing an oxysilyl group is not particularly limited as long as it contains a silicon-oxygen bond. For example, hydrocarbyloxysilyl groups such as alkoxysilyl groups and aryloxysilyl groups, silanol groups, siloxane groups and these groups. And a group having 0 to 20 carbon atoms. Particularly preferred examples of the group containing an oxysilyl group include an oxysilyl group-containing group contained in a polymer chain terminal structure represented by the following formula (4).

hpDCPD-A- _{[Si (OR) n X 3-} n ] _m (4)
(In the formula (4), hpDCPD represents a polymer chain comprising the repeating unit represented by the formula (1) as a main structural unit, and A represents an (m + 1) -valent hydrocarbon group having 1 to 20 carbon atoms. R represents a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of groups represented by R are present, they may be the same group or different groups. X represents a group selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and a halogen atom, and when there are a plurality of groups represented by X, they are The same group may be sufficient, and different groups may be sufficient, n is an integer of 1-3, m is an integer of 1-3.)

  In the formula (4), n is more preferably 2 or 3, and m is more preferably 1. In the formula (4), particularly preferred examples of the hydrocarbon group represented by A include a methylene group, an ethylene group, a propylene group, and a butylene group. Among them, a methylene group is particularly preferred. . Furthermore, in the formula (4), the hydrocarbon group represented by R is preferably a methyl group, an ethyl group, an isopropyl group, or a phenyl group, and the group represented by X is a hydrogen atom or a carbon number of 1 An alkyl group having ˜20 or an aryl group having 6 to 20 carbon atoms is preferable, and among them, a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, and a phenyl group are preferable.

  Among the oxysilyl groups contained in the polymer chain terminal structure represented by the above formula (4), a trialkoxysilyl group can be mentioned as a particularly preferable one. Specific examples of the group bonded to the end of the polymer chain containing the particularly preferred oxysilyl group include a 2-trimethoxysilylethyl group, a 3-trimethoxysilylpropyl group, and a trimethoxysilylmethyl group. These oxysilyl group-containing groups may be present alone or in combination of two or more at the end of the polymer chain of the polymer of the present invention.

  Even if the polymer of the present invention consists of a polymer chain in which a group containing an oxysilyl group is bonded only to one polymer chain end (one end), both polymer chain ends (both ends) It may be composed of a polymer chain having a group containing an oxysilyl group bonded thereto, or may be a mixture of these. Furthermore, these and a polymer chain to which a group containing an oxysilyl group is not bonded may be present.

In the polymer of the present invention, the amount of the group containing an oxysilyl group with respect to the end of the polymer chain is not particularly limited, but the balance between the adhesion of the polymer to other materials and the heat resistance is particularly good. From the viewpoint, the number of oxysilyl groups contained in one polymer chain (the number of silicon atoms to which at least one oxygen atom is bonded) is preferably 0.4 to 4.0, 0.5 It is preferable that it is -2.0 pieces. In the present invention, the number of oxysilyl groups contained per polymer chain 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 an oxysilyl group and the number average molecular weight (Mn) by GPC measurement.

  The polymer of the present invention needs to have a weight average molecular weight of 10,000 to 100,000 as a value in terms of polystyrene measured by gel permeation chromatography (GPC), and 15,000 to 90, 000 is preferable, and 20,000 to 80,000 is more preferable. By having such a weight average molecular weight, the polymer of the present invention 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.

  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 240 ° C. or higher, and preferably has a melting point of 245 to 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 the polymer of the present invention is the above-described method for producing the polymer of the present invention, which is a metal compound represented by the following formula (2) or a metal represented by the following formula (3). The compound is used as a polymerization catalyst, and after the ring-opening metathesis polymerization of dicyclopentadiene in the presence of an oxysilane compound having an ethylenically unsaturated group, the carbon-carbon double bond of the resulting ring-opened polymer is hydrogenated. It is a manufacturing method of a polymer.

  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.

  The polymerization catalyst used in the method for producing a polymer of the present invention is a metal compound represented by the following formula (2) or a transition metal compound represented by the following formula (3). By using the metal compound represented by the formula (2), it is possible to impart syndiotactic regularity to the polymer chain of the resulting ring-opening polymer, and the metal represented by the formula (3) By using a compound, it is possible to impart isotactic regularity to the resulting 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.

（式（３）中、Ｍは周期律表第６族の遷移金属原子から選択される金属原子であり、Ｒ^４はアルキル基およびアリール基から選択される基であり、Ｒ^５およびＲ^６は、それぞれ独立に水素原子、アルキル基およびアリール基から選択される基であり、Ｒ^７およびＲ^１４は、それぞれ独立にアルキル基およびアリール基から選択される基であり、Ｒ^８〜Ｒ^１３は、それぞれ独立に水素原子、アルキル基およびアリール基から選択される基であり、Ｒ^７〜Ｒ^１４のうち２個以上が結合して環構造を形成していてもよい。Ｙは電子供与性の中性配位子であり、ｐは０〜２の整数である。）

(In Formula (3), M is a metal atom selected from transition metal atoms of Group 6 of the periodic table, R ⁴ is a group selected from an alkyl group and an aryl group, and R ⁵ and R ⁶ are , Each independently a group selected from a hydrogen atom, an alkyl group and an aryl group, R ⁷ and R ¹⁴ are each independently a group selected from an alkyl group and an aryl group, and R ^{8 to} R ¹³ are Each independently represents a group selected from a hydrogen atom, an alkyl group, and an aryl group, and two or more of R ^{7 to} R ¹⁴ may be bonded to form a ring structure. And p is an integer of 0 to 2.)

  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; and the like, and further, substituents present in at least two positions of the 3, 4, and 5 positions are bonded to each other. 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. .

  The metal atom (M in formula (3)) constituting the metal compound represented by formula (3) is selected from group 6 transition metal atoms (chromium, molybdenum, tungsten) in the periodic table. Among these, molybdenum or tungsten is preferably used, and molybdenum is particularly preferably used.

The metal compound represented by the formula (3) comprises a ligand having a biphenoxy structure coordinated to a metal atom as represented by the formula (3). In the ligand having the biphenoxy structure, the groups at the 3rd and 3 ′ positions of the carbon atom forming the biphenoxy structure (R ⁷ and R ¹⁴ in the formula (3)) must be an alkyl group or an aryl group. . Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. Specific examples of the aryl group include a phenyl group. Can be mentioned. Among them, a branched alkyl group or a phenyl group can be mentioned as a particularly preferable group represented by R ⁷ and R ¹⁴ in the formula (3). Groups on other carbon atoms in the ligand having a biphenoxy structure (R ^{8 to} R ¹³ in formula (3)) are groups independently selected from a hydrogen atom, an alkyl group, and an aryl group. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. Specific examples of the aryl group include a phenyl group. Can be mentioned. Further, two or more groups represented by R ^{7 to} R ¹⁴ in the formula (3) may be bonded to form a ring structure such as an alicyclic structure or an aromatic ring structure. As a particularly preferable group as a group constituting the ligand having a biphenoxy structure which the metal compound represented by the formula (3) has, 5,5 ′, 6,6′-tetramethyl-3,3′-di- t-butyl-1,1′-biphenyl-2,2′-dioxy group, 5,5 ′, 6,6′-tetramethyl-3,3′-diisopropyl-1,1′-biphenyl-2, 2′-dioxy group, 5,5 ′, 6,6 ′, 7,7 ′, 8,8′-octahydro-3,3′-di-t-butyl-1,1′-bi-2-naphthoxy group 3,3′-diphenyl- [2,2′-binaphthalene] -1,1′-dioxy group.

The metal compound represented by Formula (3) includes a metal imide bond. The substituent on the nitrogen atom constituting the metal imide bond (R ⁴ in formula (3)) is a group selected from an alkyl group and an aryl group. Specific examples of this alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, and cyclohexyl group. The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and is selected from, for example, a phenyl group or a 1 to 5 substituted phenyl group having a substituent at any of the 2, 3, 4, 5, and 6 positions. The

The metal compound represented by the formula (3) further includes a carbene ligand coordinated to a metal atom. The substituents on the carbene carbon atom constituting the carbene ligand (R ⁵ and R ^{6 in} formula (3)) are each independently selected from a hydrogen atom, an alkyl group and an aryl group. Specific examples of this alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, and cyclohexyl group. The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and is selected from, for example, a phenyl group or a 1 to 5 substituted phenyl group having a substituent at any of the 2, 3, 4, 5, and 6 positions. The

  The metal compound represented by the formula (3) may have one or two electron-donating neutral ligands per molecule. As a specific example of this electron-donating neutral ligand (Y in formula (3)), the metal compound represented by formula (2) was given as a specific example of L in formula (2). Things.

  As the metal compound represented by the formula (3), a metal compound represented by the following formula (5) or the formula (6) can be particularly preferably used.

  The amount of the metal compound represented by the formula (2) or the formula (3) used as the polymerization catalyst is such that the molar ratio of (metal compound: whole monomer used) is usually 1: 100 to 1: 2,000, 000, preferably 1: 500 to 1,000,000, more preferably 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 the metal compound represented by Formula (2) as a polymerization catalyst, the metal compound can be used alone, but from the viewpoint of increasing the polymerization activity, the metal compound, the organometallic reducing agent, It is preferable to use together. 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 is preferably used, and organoaluminum or organotin is 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. The amount of the organometallic reducing agent used is preferably 0.1 to 100 moles, more preferably 0.2 to 50 moles, and more preferably 0.5 to 20 moles relative to the metal compound represented by the formula (2). Double is particularly preferred. 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, an oxysilane 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, by the presence of an oxysilane compound having an ethylenically unsaturated group, a chain transfer reaction occurs between the growth terminal of the polymer and the ethylenically unsaturated group of the oxysilane compound having an ethylenically unsaturated group, A group containing an oxysilyl group can be introduced at the end of the polymer chain. The oxysilane 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 an oxysilyl group in the molecule.

  Specific examples of the oxysilane compound having an ethylenically unsaturated group include vinyltrimethoxysilane, allyltrimethoxysilane, styrylethyltrimethoxysilane, styryltrimethoxysilane, 10-undecenyltrimethoxysilane, vinyltriethoxysilane, allyl. Oxysilane compounds having a terminal olefin group such as triethoxysilane, vinylmethyldimethoxysilane, vinylphenyldimethoxysilane, vinyldimethylmethoxysilane, allyldiethylethoxysilane, 1,4-bis (trimethoxysilyl) -2-butene, An internal olefin compound containing oxysilyl groups such as, 6-bis (trimethoxysilyl) -3-hexene on both sides of the carbon-carbon double bond can be mentioned. In addition, the oxysilane compound which has an ethylenically unsaturated group may be used individually by 1 type, and can also use 2 or more types together. When an oxysilane compound having a terminal olefin group is used as the oxysilane compound having an ethylenically unsaturated group, the oxysilyl group is introduced only at one polymer chain end (one end), and the oxysilyl group is converted into a carbon-carbon double. When using an internal olefin compound contained on both sides of the bond, an oxysilyl group is introduced at both polymer chain ends (both ends).

  The oxysilane compound having an ethylenically unsaturated group functions as a chain transfer agent in the ring-opening polymerization reaction system, and can function as a molecular weight modifier. Therefore, the amount of the oxysilane compound having an ethylenically unsaturated group should be determined in consideration of the strength of the function as the molecular weight modifier exhibited by the compound and the molecular weight of the target dicyclopentadiene ring-opening polymer. Good. The specific amount used is not particularly limited, but is usually selected in the range of 0.1 to 50 mol, preferably 0.2 to 20 mol, per mol of the monomer used in the polymerization reaction. Selected by range. As the molecular weight modifier, only an oxysilane compound having an ethylenically unsaturated group can be used alone, but if necessary, a compound having an ethylenically unsaturated group not having an oxysilyl group may be used in combination. Good. A compound having an ethylenically unsaturated group that does not have an oxysilyl group works as a molecular weight modifier, but does not introduce an oxysilyl group into the polymer chain end. Even when it is desired to reduce the introduction rate of the oxysilyl group, a polymer having a desired molecular weight can be obtained.

  In the method for producing a polymer of the present invention, it is particularly preferable to use a compound having a vinyl group directly bonded to a silicon atom of an oxysilyl group as the oxysilane compound having an ethylenically unsaturated group. By using such an oxysilane compound having an ethylenically unsaturated group, it becomes possible to reduce the amount of the compound used compared to the case of using an oxysilane compound having another ethylenically unsaturated group, and as a result, The stereoregularity of the polymer chain of the resulting ring-opening polymer can be increased. Therefore, it can be said that the heat resistance of the finally obtained polymer (ring-opened polymer hydride) is particularly high. Particularly preferred examples of the oxysilane compound having a vinyl group bonded directly to the silicon atom of the oxysilyl group include vinyltrimethoxysilane and vinyltriethoxysilane.

  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. , Hexahydroindene, cyclooctane and other alicyclic hydrocarbons; benzene, toluene, xylene and other aromatic hydrocarbons; dichloromethane, chloroform, 1,2-dichloroethane and other halogenated aliphatic hydrocarbons; chlorobenzene, dichlorobenzene, etc. 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 initiated by mixing the monomer, the metal compound represented by formula (2) or formula (3), 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 a ring-opening polymer, you may add molecular weight modifiers other than the oxysilane compound which has an ethylenically unsaturated group to a 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.

  By using the ring-opening polymerization catalyst containing the metal compound represented by the formula (2) as described above, the ring-opening polymerization reaction of the monomer under the above-described conditions, the syndiotactic stereoregularity is achieved. The ring-opening polymer of the monomer can be obtained under the conditions as described above using the ring-opening polymerization catalyst containing the metal compound represented by the formula (3) as described above. By carrying out the reaction, a ring-opening polymer having isotactic stereoregularity can be obtained. If the conditions of the hydrogenation reaction are set to appropriate conditions as described later, the tacticity of the ring-opening polymer will not change during the hydrogenation reaction, so the ring-opening polymers having these stereoregularities will be hydrogenated. By subjecting to the reaction, the target polymer which is a ring-opening polymer hydride having crystallinity based on the stereoregularity is maintained. The degree of stereoregularity of the ring-opening polycopolymer 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 subjected to the hydrogenation reaction is not particularly limited, but is preferably 10,000 to 100,000 in terms of polystyrene. More preferably, it is 000-80,000. 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.

  The molecular weight distribution of the ring-opening polymer to be subjected to the hydrogenation reaction [ratio of polystyrene-equivalent number average molecular weight and weight average molecular weight (Mw / Mn) measured by gel permeation chromatography] is not particularly limited. It is 5-4.0, Preferably it is 1.6-3.5. 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, 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.
(1) Molecular weight of the ring-opening polymer (weight average molecular weight and number average molecular weight)
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) Molecular weight (weight average molecular weight and number average molecular weight) of crystalline polymer (ring-opening polymer hydride)
Using gel permeation chromatography (GPC) system SSC-7100 (manufactured by Senshu Kagaku), GPC3506 column (manufactured by Senshu Kagaku) was used and measured at 210 ° C. using 1-chloronaphthalene as a solvent, and converted into polystyrene. Asked.
(3) Number of oxysilyl groups per polymer chain The peak area derived from oxysilyl groups and ring opening polymerization of dicyclopentadiene obtained by measuring ¹ H-NMR of the ring-opened polymer before hydrogenation Based on the peak area derived from the repeating unit, the oxysilyl group content for all repeating units was determined, and then calculated from the number average molecular weight.
(4) Hydrogenation rate of ring-opening polymer
^It calculated | required based on < ¹ > H-NMR measurement.
(5) Melting point (or glass transition temperature) of polymer and heat of fusion Using a differential scanning calorimeter, the temperature was raised at 10 ° C./min and measured.
(6) Polymer meso / racemo dyad ratio Using ortho-dichlorobenzene-d4 as a solvent and applying an inverse-gate decoupling method at 150 ° C., ¹³ C-NMR measurement was performed, and 127.5 ppm of orthodichlorobenzene-d4 was obtained. 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.
(7) 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-like 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” (manufactured by Nichiban Co., Ltd.) (Registered trademark) No. 405 ") was attached, 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 fully dried, nitrogen-substituted glass pressure-resistant reaction vessel is charged with 40 parts of a 75% cyclohexane solution of dicyclopentadiene (endo content 99% or more) (30 parts as the amount of dicyclopentadiene) and allyltrimethoxysilane. 3.66 parts were added, and 76 parts of cyclohexane was further added. Subsequently, 0.46 part of a 19% n-hexane solution of diethylaluminum ethoxide was added and stirred. Next, a solution in which 0.11 part of 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 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 molecular weight, < ¹³ > C-NMR, the measurement of 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 shows the molecular weight of the ring polymer, the molecular weight of the crystalline polymer, the number of oxysilyl groups per polymer chain, the meso / racemo-dyad ratio of the polymer, the melting point, the heat of fusion, and the adhesion test results. Are summarized in

[Example 2]
In the ring-opening polymerization reaction, the ring-opening polymerization reaction and the hydrogenation reaction were performed in the same manner as in Example 1 except that 4.62 parts of allyltriethoxysilane were used instead of 3.66 parts of allyltrimethoxysilane. A crystalline polymer was obtained. The yield of the ring-opening polymer was 29 parts (yield 97%). The obtained ring-opening polymer and crystalline polymer were measured and tested in the same manner as in Example 1. The hydrogenation rate of the ring-opened polymer determined from the results of each measurement is substantially 100%, and the molecular weight of the ring-opened polymer, the molecular weight of the crystalline polymer, and the oxysilyl per polymer chain The number of groups, polymer meso / racemo dyad ratio, melting point, heat of fusion, and adhesion test results are summarized in Table 1.

Example 3
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 0.50 part of vinyltrimethoxysilane was used instead of 3.66 parts of allyltrimethoxysilane. A crystalline polymer was obtained. The yield of the ring-opening polymer was 29 parts (yield 97%). The obtained ring-opening polymer and crystalline polymer were measured and tested in the same manner as in Example 1. The hydrogenation rate of the ring-opened polymer determined from the results of each measurement is substantially 100%, and the molecular weight of the ring-opened polymer, the molecular weight of the crystalline polymer, and the oxysilyl per polymer chain The number of groups, polymer meso / racemo dyad ratio, melting point, heat of fusion, and adhesion test results are summarized in Table 1.

Example 4
In the ring-opening polymerization reaction, a ring-opening polymerization reaction and a hydrogenation reaction were carried out in the same manner as in Example 1 except that 0.86 part of vinyltriethoxysilane was used instead of 3.66 parts of allyltrimethoxysilane. A crystalline polymer was obtained. The yield of the ring-opening polymer was 29 parts (yield 97%). The obtained ring-opening polymer and crystalline polymer were measured and tested in the same manner as in Example 1. The hydrogenation rate of the ring-opened polymer determined from the results of each measurement is substantially 100%, and the molecular weight of the ring-opened polymer, the molecular weight of the crystalline polymer, and the oxysilyl per polymer chain The number of groups, polymer meso / racemo dyad ratio, melting point, heat of fusion, and adhesion test results are summarized in Table 1.

Example 5
In the ring-opening polymerization reaction, in the same manner as in Example 1 except that instead of 3.66 parts of allyltrimethoxysilane, a mixture of 0.33 part of vinyltrimethoxysilane and 0.95 part of 1-hexene was used. A ring-opening polymerization reaction and a hydrogenation reaction were performed to obtain a crystalline polymer. The yield of the ring-opening polymer was 30 parts (yield 100%). The obtained ring-opening polymer and crystalline polymer were measured and tested in the same manner as in Example 1. The hydrogenation rate of the ring-opened polymer determined from the results of each measurement is substantially 100%, and the molecular weight of the ring-opened polymer, the molecular weight of the crystalline polymer, and the oxysilyl per polymer chain The number of groups, polymer meso / racemo dyad ratio, melting point, heat of fusion, and adhesion test results are summarized in Table 1.

Example 6
In the ring-opening polymerization reaction, the ring-opening polymerization reaction and the hydrogenation reaction were performed in the same manner as in Example 1 except that 5.69 parts of styrylethyltrimethoxysilane was used instead of 3.66 parts of allyltrimethoxysilane. Thus, a crystalline polymer was obtained. The yield of the ring-opening polymer was 30 parts (yield 100%). The obtained ring-opening polymer and crystalline polymer were measured and tested in the same manner as in Example 1. The hydrogenation rate of the ring-opened polymer determined from the results of each measurement is substantially 100%, and the molecular weight of the ring-opened polymer, the molecular weight of the crystalline polymer, and the oxysilyl per polymer chain The number of groups, polymer meso / racemo dyad ratio, melting point, heat of fusion, and adhesion test results are summarized in Table 1.

Example 7
In the ring-opening polymerization reaction, the reaction was performed in the same manner as in Example 1, except that 6.73 parts of 1,4-bis (trimethoxysilyl) -2-butene was used instead of 3.66 parts of allyltrimethoxysilane. A ring polymerization reaction and a hydrogenation reaction were performed to obtain a crystalline polymer. The yield of the ring-opening polymer was 28 parts (yield 95%). The obtained ring-opening polymer and crystalline polymer were measured and tested in the same manner as in Example 1. The hydrogenation rate of the ring-opened polymer determined from the results of each measurement is substantially 100%, and the molecular weight of the ring-opened polymer, the molecular weight of the crystalline polymer, and the oxysilyl per polymer chain The number of groups, polymer meso / racemo dyad ratio, melting point, heat of fusion, and adhesion test results are summarized in Table 1.

Example 8
After fully drying, in a pressure-resistant reaction vessel made of nitrogen-substituted glass, 40 parts of a 75% cyclohexane solution (30 parts as the amount of dicyclopentadiene) of dicyclopentadiene (endo content 99% or more) and vinyltrimethoxysilane 0.55 part was charged, and 76 parts of cyclohexane was further added and stirred. A solution obtained by dissolving 0.034 parts of the molybdenum complex represented by the above formula (5) 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 molecular weight, < ¹³ > C-NMR, the measurement of 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 shows the molecular weight of the ring polymer, the molecular weight of the crystalline polymer, the number of oxysilyl groups per polymer chain, the meso / racemo-dyad ratio of the polymer, the melting point, the heat of fusion, and the adhesion test results. Shown together.

[Comparative Example 1]
In the ring-opening polymerization reaction, except that 1.90 parts of 1-hexene was used instead of 3.66 parts of allyltrimethoxysilane, a ring-opening polymerization reaction and a hydrogenation reaction were performed in the same manner as in Example 1, A crystalline polymer was obtained. The yield of the ring-opening polymer was 28 parts (yield 95%). The obtained ring-opening polymer and crystalline polymer were measured and tested in the same manner as in Example 1. The hydrogenation rate of the ring-opened polymer determined from the results of each measurement is substantially 100%. Also, the molecular weight of the ring-opened polymer, the number of oxysilyl 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 fully dried, nitrogen-substituted glass pressure-resistant reaction vessel is charged with 40 parts of a 75% cyclohexane solution of dicyclopentadiene (endo content 99% or more) (30 parts as the amount of dicyclopentadiene) and allyltrimethoxysilane. 0.55 part was charged, and 76 parts of cyclohexane was further added and stirred. Next, a solution in which 0.019 part of a ruthenium complex represented by the following formula (7) 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 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). 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 to 8) exhibit a high melting point and a large heat of fusion, and hardly cause peeling of the tape in the adhesion test. It can be said that it is excellent in heat resistance and adhesion to other materials. Among them, a polymer obtained by using vinyltrimethoxysilane or vinyltriethoxysilane having a vinyl group directly bonded to a silicon atom of an oxysilyl group as an oxysilane compound (molecular weight modifier) having an ethylenically unsaturated group ( Examples 3 to 5 and 8) are particularly excellent in heat resistance because they exhibited particularly high melting points and particularly large heats of fusion. On the other hand, the crystalline polymer (Comparative Example 1) in which a group containing an oxysilyl group is not bonded to the end of the polymer chain was excellent in heat resistance, but caused tape peeling in an adhesion test. It was inferior in adhesiveness with other materials as compared with the polymer of the present invention. In addition, although a polymer having an oxysilyl group at the end of 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 (4)

It has a polymer chain comprising a repeating unit represented by the following formula (1) as a main structural unit, and the ratio of racemo dyad to the repeating unit represented by the formula (1) is 60% or more or 30% or less, the polymer at the end of the chain Ri Na is bonded group containing a oxysilyl group, the number of oxysilyl groups contained per the polymer chain one is 0.5 to 2.0 or A polymer having crystallinity and having a weight average molecular weight of 20,000 to 80,000 .

A composite obtained by applying a curable resin to a molded body obtained by molding the polymer according to claim 1 and curing it. It is a manufacturing method of the polymer of Claim 1, Comprising: The metal compound represented by following formula (2) or the metal compound represented by following formula (3) is used as a polymerization catalyst, and it is ethylenic unsaturated. A method for producing a polymer, comprising subjecting dicyclopentadiene to ring-opening metathesis polymerization in the presence of an oxysilane compound having a group, and then hydrogenating a carbon-carbon double bond of the resulting ring-opening polymer.

(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.

(In Formula (3), M is a metal atom selected from transition metal atoms of Group 6 of the periodic table, R ⁴ is a group selected from an alkyl group and an aryl group, and R ⁵ and R ⁶ are , Each independently a group selected from a hydrogen atom, an alkyl group and an aryl group, R ⁷ and R ¹⁴ are each independently a group selected from an alkyl group and an aryl group, and R ^{8 to} R ¹³ are Each independently represents a group selected from a hydrogen atom, an alkyl group, and an aryl group, and two or more of R ^{7 to} R ¹⁴ may be bonded to form a ring structure. And p is an integer of 0 to 2.) The method for producing a polymer according to claim 3 , wherein the oxysilane compound having an ethylenically unsaturated group has a vinyl group directly bonded to a silicon atom of an oxysilyl group.