JP2006117862A - Method for producing hydrogenated norbornene type ring-opened polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a hydrogenated norbornene type ring-opened polymer wherein a molecular weight distribution is narrow, a hydrogenation degree is high and a melt flow rate is well controlled in a high yield at a low cost. <P>SOLUTION: The method comprises (A) a process of ring-opening polymerization of a composition containing a tri-cyclic or higher cyclic norbornene monomer in the presence of a tungsten type metathesis catalyst and (B) a process of hydrogenation of the resulting ring-opened polymer, wherein, in the process (A), (1) the ratio of the tungsten type metathesis catalyst to 1 mole part of the norbornene monomer composition is 0.005-0.25 mmol. eq., (2) the content of alkenyl-substituted norbornene in the norbornene monomer composition is 0.7 wt% or less, and (3) the content of cyclopentadiene in the norbornene monomer composition is 0.015-0.035 wt%. A molded article is produced from the norbornene type ring-opened polymer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a norbornene-based ring-opening polymer hydride having a narrow molecular weight distribution, a high hydrogenation rate, and a controlled melt mass flow rate (MFR) at a low cost and in a high yield.

  Since the norbornene-based ring-opening polymer hydride is excellent in transparency, heat resistance, low birefringence, molding processability, etc., it is widely used as a molding material for various molded products such as optical materials and medical equipment.

Norbornene-based ring-opening polymer hydride is obtained by ring-opening polymerization of norbornene-based monomers in the presence of a metathesis polymerization catalyst and hydrogenating the carbon-carbon double bonds in the resulting norbornene-based ring-opening polymer. It is manufactured.
As a raw material for producing a norbornene-based ring-opening polymer hydride, a tricyclic or higher polycyclic norbornene-based monomer such as dicyclopentadiene is awarded because it is easily available industrially.

  By the way, this polycyclic norbornene-based monomer having three or more rings is usually cyclopentadiene (hereinafter sometimes referred to as “CPD”), 5-vinyl [2.2.1] for production reasons. Alkenyl-substituted norbornene such as hept-2-ene (hereinafter sometimes referred to as “VNB”) and 5-isopropenyl [2.2.1] hept-2-ene (hereinafter sometimes referred to as “IPN”) Contains a small amount. When ring-opening polymerization of this tricyclic or higher polycyclic norbornene monomer in the presence of a metathesis polymerization catalyst, if the norbornene monomer contains a large amount of CPD, the catalytic activity of the metathesis polymerization catalyst Is known to decrease. It is also known that the presence of alkenyl-substituted norbornene contained in a tricyclic or higher polycyclic norbornene monomer affects the physical properties of the resulting norbornene ring-opening polymer.

  Therefore, in order to obtain a norbornene-based ring-opening polymer having better physical properties, the content of CPD is reduced when ring-opening polymerization of tricyclic or higher polycyclic norbornene-based monomers in the presence of a metathesis polymerization catalyst. In the past, techniques for controlling the content of alkenyl-substituted norbornene have been proposed.

  For example, in Patent Document 1, dicyclopentadiene having an alkenyl group-substituted norbornene content of 4.1% by weight is heat-treated at 120 ° C. to 250 ° C., and an oily substance containing no alkenyl group-substituted norbornene and cyclopentadiene (dicyclopentadiene). There is obtained a method for producing a monomer composition having a high polymerization activity, wherein 76% by weight of pentadiene and 24% of a cyclopentadiene trimer or higher component are obtained, and the oil and, if necessary, a norbornene monomer are mixed. It is disclosed. It is also disclosed that when the monomer composition is subjected to bulk polymerization using 0.35 mmol of a tungsten catalyst, a thermosetting resin having excellent heat resistance can be obtained.

  In Patent Document 2, 10% by weight or more of dicyclopentadiene is contained in a crude norbornene monomer composition containing a polymerization inhibitor (for example, chain olefin, chain diolefin), and the crude norbornene monomer By heating the composition at 60 ° C. or higher, the CPD generated by the thermal decomposition of dicyclopentadiene and the chain olefin or chain diolefin are reacted to form IPN or VNB to form a norbornene-based monomer. It is described that the polymerization activity of the body composition is enhanced.

  Further, in Patent Document 3, a norbornene-based polymer is obtained in which a norbornene-based monomer composition containing a tricyclic or higher polycyclic norbornene-based monomer is subjected to ring-opening bulk polymerization in the presence of a molybdenum-based metathesis catalyst and a cocatalyst. In the method for producing a molded article made of a ring polymer, when the monomer composition contains 0.5 to 60 parts by weight of the alkenyl group-substituted norbornene with respect to 100 parts of the norbornene monomer, the pot life ( After mixing the norbornene-based monomer composition, the molybdenum-based metathesis catalyst and the cocatalyst, the viscosity of the mixed solution increases and the flow time becomes difficult to flow), and the smoking time (mixed product after mixing) It is described that the time until white smoke is generated from the surface of the glass can be shortened.

  Furthermore, Patent Document 4 discloses a norbornene-based monomer composition containing 30% by weight or more of dicyclopentadiene, and a monomer composition containing 0.01 to 2% by weight of alkenyl group-substituted norbornene. Norbornene ring-opening in which the content of alkenyl group-substituted norbornene is reduced by 20 wt% or more by heating at ~ 250 ° C for 0.5 to 20 hours, and the resulting monomer composition is polymerized in the presence of a ruthenium-based metathesis catalyst A method for producing a polymer is disclosed.

  However, all of the techniques described in Patent Documents 1 to 4 are for producing norbornene-based ring-opening polymers, and the norbornene-based ring-opening having more excellent physical properties obtained by further hydrogenation of the polymer. It was not a technique for producing polymer hydrides.

JP-A-63-234017 Japanese Patent Laid-Open No. 2-84428 Japanese Patent Laid-Open No. 3-146516 JP 2003-119254 A

  The present invention has been made in view of the above-described prior art, and a hydride of a norbornene-based ring-opening polymer having a narrow molecular weight distribution, a high hydrogenation rate, and a controlled melt mass flow rate (MFR), It is an object of the present invention to provide a method for producing at low cost and high yield.

  In order to solve the above problems, the present inventors have conducted a ring-opening polymerization of a norbornene-based monomer composition in the presence of a tungsten-based metathesis catalyst having excellent polymerization activity as a metathesis polymerization catalyst, thereby producing a norbornene-based ring-opening polymer. After that, the present inventors have intensively studied a method for producing a hydride of a norbornene-based ring-opening polymer in which the carbon-carbon double bond of the ring-opening polymer is hydrogenated in the presence of a hydrogenation catalyst.

as a result,
(I) When a tungsten-based metathesis catalyst is used as the metathesis polymerization catalyst, the tungsten-based metathesis catalyst and its residue become catalyst poisons of the hydrogenation catalyst, so that the hydrogen of the norbornene-based ring-opening polymer with a smaller amount of hydrogenation catalyst. In order to efficiently perform the chemical reaction, it is preferable to reduce the amount of tungsten-based metathesis catalyst used as much as possible.
(ii) When the use amount of the tungsten-based metathesis catalyst is reduced, the polymerization conversion rate of the ring-opening polymerization decreases as the content of the alkenyl-substituted norbornene contained as an impurity in the norbornene-based monomer composition increases.
(iii) When the content of alkenyl-substituted norbornene is reduced and the use amount of the tungsten-based metathesis catalyst is reduced, the content of CPD contained in the norbornene-based monomer composition is the molecular weight of the resulting norbornene-based polymer. The knowledge that it has a big influence on distribution was obtained. And based on these knowledge, it came to complete this invention.

Thus, according to the first aspect of the present invention, a step (A) of ring-opening polymerization of a norbornene monomer composition containing a tricyclic or higher polycyclic norbornene monomer in the presence of a tungsten metathesis catalyst, and A process for producing a hydrogenated norbornene-based ring-opening polymer having a step (B) of hydrogenating the obtained ring-opening polymer, wherein in step (A),
(1) The ratio of the tungsten-based metathesis catalyst to 1 mol of the norbornene-based monomer composition is 0.005 to 0.25 mmol equivalent,
(2) The alkenyl group-substituted norbornene content in the norbornene-based monomer composition is 0.7% by weight or less, and
(3) Provided is a method for producing a hydride of a norbornene-based ring-opening polymer, wherein the content of cyclopentadiene in the norbornene-based monomer composition is in the range of 0.015 to 0.035% by weight. .
In the production method of the present invention, the tricyclic or higher polycyclic norbornene monomer is preferably dicyclopentadiene.
According to a second aspect of the present invention, a norbornene-based ring-opening polymer hydride obtained by the production method of the present invention is provided.
According to the third aspect of the present invention, there is provided a molded body obtained by molding the hydride of the norbornene-based ring-opening polymer of the present invention.

According to the production method of the present invention, it is possible to produce a norbornene-based ring-opening polymer hydride having a narrow molecular weight distribution, a high hydrogenation rate, and a controlled melt mass flow rate (MFR) at a low cost and in a high yield. it can.
The molded article of the present invention obtained from the hydride of norbornene-based ring-opening polymer of the present invention is excellent in strength, heat resistance and weather resistance.

Hereinafter, the present invention will be described in detail.
1) Method for producing hydride of norbornene-based ring-opening polymer The method for producing hydride of norbornene-based ring-opening polymer according to the present invention comprises a norbornene-based monomer composition containing a tricyclic or higher polycyclic norbornene-based monomer. A process for producing a hydrogenated norbornene-based ring-opening polymer comprising a step (A) of ring-opening polymerization of a product in the presence of a tungsten-based metathesis catalyst, and a step (B) of hydrogenating the resulting ring-opening polymer. In the step (A), (1) the ratio of the tungsten-based metathesis catalyst to 1 mol of the norbornene-based monomer composition is 0.005 to 0.25 mmol equivalent, and (2) the norbornene-based monomer composition The alkenyl group-substituted norbornene content is 0.7% by weight or less, and (3) the cyclopentadiene content in the norbornene-based monomer composition is 0.015-0.0. It is characterized by being in the range of 35% by weight.

(I) Step (A)
Step (A) is a step of ring-opening polymerization of a norbornene monomer composition containing a tricyclic or higher polycyclic norbornene monomer in the presence of a tungsten metathesis catalyst.

(1) Norbornene-based monomer composition The norbornene-based monomer composition used in the present invention is a mixture of monomers that undergo ring-opening polymerization in the presence of a metathesis polymerization catalyst, and is a tricyclic or higher polycyclic norbornene. It contains a system monomer.
The norbornene monomer is a compound having a norbornene ring in the molecule, and the polycyclic norbornene monomer having three or more rings is a norbornene ring in the molecule and one condensed with the norbornene ring. It is a norbornene-based monomer having the above ring. Specific examples thereof include monomers represented by the following formula (1) or formula (2).

(Wherein R ¹ and R ² are each independently a hydrogen atom; a halogen atom; an optionally substituted hydrocarbon group having 1 to 20 carbon atoms; or a substitution containing a silicon atom, an oxygen atom or a nitrogen atom) And R ³ is a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.

(Wherein R ^{4 to} R ⁷ are each independently a hydrogen atom; a halogen atom; an optionally substituted hydrocarbon group having 1 to 20 carbon atoms; or a substitution containing a silicon atom, an oxygen atom or a nitrogen atom) And R ⁴ and R ⁶ may be bonded to each other to form a ring, and m is 1 or 2.)

Specific examples of the monomer represented by the formula (1) include dicyclopentadiene, methyldicyclopentadiene, tricyclo [5.2.1.0 ^2,6 ] dec-8-ene. In addition, tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8] tetradec -3,5,7,12- tetraene, tetracyclo [10.2.1.0 ^2,11. Norbornene derivatives having an aromatic ring such as 0 ^4,9 ] pentadeca-4,6,8,13-tetraene can also be mentioned.

Examples of the monomer represented by the formula (2) include tetracyclododecenes in which m is 1 and hexacycloheptadecenes in which m is 2.
Specific examples of tetracyclododecenes include tetracyclododecene and 8-methyltetracyclododecene represented by m = 1, R ⁴ = R ⁵ = R ⁶ = R ⁷ = H in formula (2). , Tetracyclododecenes having an unsubstituted or alkyl group such as 8-ethyltetracyclododecene, 8-cyclohexyltetracyclododecene, and 8-cyclopentyltetracyclododecene; 8-methylidenetetracyclododecene, 8- Tetrayl having a double bond outside the ring, such as ethylidenetetracyclododecene, 8-vinyltetracyclododecene, 8-propenyltetracyclododecene, 8-cyclohexenyltetracyclododecene, 8-cyclopentenyltetracyclododecene, etc. Cyclododecenes; tetracyclodos having aromatic rings such as 8-phenyltetracyclododecene Sens; 8-methoxycarbonyltetracyclododecene, 8-methyl-8-methoxycarbonyltetracyclododecene, 8-hydroxymethyltetracyclododecene, 8-carboxytetracyclododecene, tetracyclododecene-8,9 -Tetracyclododecenes having a substituent containing an oxygen atom such as dicarboxylic acid, tetracyclododecene-8,9-dicarboxylic anhydride; 8-cyanotetracyclododecene, tetracyclododecene-8,9- Tetracyclododecenes having a substituent containing a nitrogen atom such as dicarboxylic imide; tetracyclododecenes having a substituent containing a halogen atom such as 8-chlorotetracyclododecene; 8-trimethoxysilyltetracyclod And tetracyclododecenes having a substituent containing a silicon atom such as decene It is done.

Specific examples of hexacycloheptadecenes include hexacycloheptadecene, 12-methylhexacycloheptadecene, represented by m = 2 and R ⁴ = R ⁵ = R ⁶ = R ⁷ = H in formula (2). , 12-methylhexacycloheptadecene, 12-cyclohexylhexacycloheptadecene, 12-cyclopentylhexacycloheptadecene, etc., or unsubstituted or alkyl-containing hexacycloheptadecenes; 12-methylidenehexacycloheptadecene, 12- Hexacycloheptene having a double bond outside the ring such as ethylidenehexacycloheptadecene, 12-vinylhexacycloheptadecene, 12-propenylhexacycloheptadecene, 12-cyclohexenylhexacycloheptadecene, 12-cyclopentenylhexacycloheptadecene, etc. Decenes: Hexacycloheptadecenes having an aromatic ring such as 12-phenylhexacycloheptadecene; 12-methoxycarbonylhexacycloheptadecene, 12-methyl-12-methoxycarbonylhexacycloheptadecene, 12-hydroxymethylhexacyclo Hexacycloheptadecene having a substituent containing an oxygen atom such as heptadecene, 12-carboxyhexacycloheptadecene, hexacycloheptadecene-12,13-dicarboxylic acid, hexacycloheptadecene-12,13-dicarboxylic anhydride A hexacycloheptadecene having a substituent containing a nitrogen atom such as 12-cyanohexacycloheptadecene or hexacycloheptadecene 12,13-dicarboxylic imide; a halogen such as 12-chlorohexacycloheptadecene Examples include hexacycloheptadecenes having a substituent containing an atom; hexacycloheptadecenes having a substituent containing a silicon atom such as 12-trimethoxysilylhexacycloheptadecene. These tricyclic or higher polycyclic norbornene monomers can be used singly or in combination of two or more.

  These tricyclic or higher polycyclic norbornene monomers include endo isomers and exo isomers, but the monomers used in the present invention may be a mixture of these isomers. .

  Further, the norbornene-based monomer composition includes, in addition to a tricyclic or higher polycyclic norbornene-based monomer, a norbornene-based monomer having no ring condensed with a norbornene ring in the molecule, the tricyclic It may contain other monomers capable of ring-opening copolymerization with the above polycyclic norbornene monomers.

  As the norbornene-based monomer having no ring condensed with the norbornene ring in the molecule, norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-hexylnorbornene, 5-decylnorbornene, 5- Norbornenes having an unsubstituted or alkyl group such as cyclohexyl norbornene and 5-cyclopentylnorbornene; norbornenes having an aromatic ring such as 5-phenylnorbornene; 5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene, 5-methyl-5- Methoxycarbonylnorbornene, 5-methyl-5-ethoxycarbonylnorbornene, norbornenyl-2-methylpropionate, norbornenyl-2-methyloctanoate, 5-hydroxymethylnorbornene, , 6-di (hydroxymethyl) norbornene, 5,5-di (hydroxymethyl) norbornene, 5-hydroxy-i-propylnorbornene, 5,6-dicarboxynorbornene, 5-methoxycarbonyl-6-carboxynorbornene, etc. Norbornenes having a polar group containing an oxygen atom; norbornenes having a polar group containing a nitrogen atom such as 5-cyanonorbornene; and the like.

  Examples of other monomers capable of ring-opening copolymerization with the tricyclic or higher polycyclic norbornene-based monomer include monocyclic olefins such as cyclohexene, cycloheptene, and cyclooctene, and derivatives thereof.

  Among these, in the present invention, it is industrially easy to obtain, and a ring-opened polymer hydride having excellent mechanical strength can be obtained easily and efficiently. As the norbornene monomer, dicyclopentadiene is preferable. Moreover, as a norbornene-type monomer composition to be used, what contains 70 weight% or more of dicyclopentadiene with respect to the whole composition is preferable, and what contains 80 weight% or more of dicyclopentadiene is more preferable.

  Dicyclopentadiene is obtained by, for example, dimerizing the remaining C5 distillate obtained by extracting isoprene from the C5 distillate by-produced during the thermal decomposition of naphtha, and distilling the resulting dicyclopentadiene-rich fraction. Can be obtained. In addition, dicyclopentadiene obtained by removing n-mer (n ≧ 3) of cyclopentadiene contained as an impurity by distillation or low-purity dicyclopentadiene is distilled by pyrolysis to obtain high purity. After obtaining cyclopentadiene, it can be dimerized again to form dicyclopentadiene, which can be obtained by distillation using a known rectifying apparatus.

  In the present invention, a norbornene-based monomer composition having an alkenyl group-substituted norbornene content of 0.7% by weight or less is used.

  In the past, alkenyl group-substituted norbornene was considered not to suppress the polymerization activity of tungsten-based metathesis catalysts. Therefore, in ring-opening polymerization of norbornene-based monomers, the content of alkenyl group-substituted norbornene has not been reduced in order to prevent the polymerization activity of the tungsten metathesis catalyst from decreasing. However, when the amount of the tungsten-based metathesis catalyst used is reduced to 0.005 to 0.25 mmol equivalent to 1 mol of the norbornene-based monomer composition, the alkenyl group-substituted norbornene in the norbornene-based monomer composition is used. It has been found that alkenyl group-substituted norbornene suppresses the polymerization activity of the tungsten-based metathesis catalyst when the content of exceeds 0.7% by weight. Therefore, in the present invention, a norbornene-based monomer composition having an alkenyl group-substituted norbornene content of 0.7% by weight or less is used.

  Alkenyl group-substituted norbornene is an impurity contained in a polycyclic norbornene monomer having three or more rings such as dicyclopentadiene as a Diels-Alder adduct of a chain conjugated diene such as butadiene, isopropene, piperylene and cyclopentadiene. is there. Specific examples thereof include 5-vinyl [2.2.1] hept-2-ene (hereinafter referred to as “VNB”) and 5-isopropenyl [2.2.1] hept-2-ene ( Hereinafter, it may be referred to as “IPN”), 5-propenyl [2.2.1] hept-2-ene (hereinafter also referred to as “PN”), and the like.

  As a method for obtaining a norbornene monomer having an alkenyl group-substituted norbornene content of 0.7% by weight or less, for example, a tricyclic or higher polycyclic norbornene monomer such as dicyclopentadiene is obtained by distillation or Examples thereof include a method for obtaining a norbornene-based monomer composition in which the content of alkenyl group-substituted norbornene is 0.7% by weight or less by purification by a known purification method such as a decomposition dimerization method.

In the present invention, a norbornene-based monomer composition having a CPD content in the range of 0.015 to 0.035% by weight is used.
By adjusting the content of CPD contained in the norbornene-based monomer composition to be in a specific range, the amount of tungsten-based metathesis catalyst used can be reduced, the molecular weight distribution is small, and the hydrogenation rate Can be obtained.

In the method for producing a hydride of norbornene-based ring-opening polymer according to the present invention, a hydride of norbornene-based ring-opening polymer having a desired MFR is obtained by adjusting the content of CPD within the above range. be able to.
The MFR needs to be appropriately changed depending on the conditions for molding the molding material containing the norbornene-based ring-opening polymer hydride, the shape of the resulting molded body, and the required physical properties.
In the method for producing a hydride of norbornene-based ring-opening polymer according to the present invention, MFR decreases when the content of CPD contained in the norbornene-based monomer composition is increased, and MFR increases when the content of CPD is decreased. Tend to.

  Although it does not specifically limit as a method of adjusting content of CPD contained in a norbornene-type monomer composition in the range of 0.015-0.035 weight%, (a) The polycyclic norbornene type | system | group of 3 or more rings to be used A method of adjusting distillation purification conditions of the monomer, (b) a method of blending CPD with a tricyclic or higher polycyclic norbornene monomer having a low CPD content, and (c) a tricyclic or higher with a low CPD content. And a method of mixing a tricyclic or higher polycyclic norbornene monomer having a high CPD content and the like.

(2) Tungsten-based metathesis catalyst In the present invention, a tungsten-based metathesis catalyst is used as the metathesis polymerization catalyst. The tungsten-based metathesis catalyst is a tungsten compound that catalyzes a ring-opening polymerization reaction of a norbornene-based monomer composition.

  Examples of the tungsten (W) compound include tungsten halides, oxyhalides, alkoxyhalides, alkoxides, carboxylates, (oxy) acetylacetonates, carbonyl complexes, and the like.

Among these, tungsten halides such as WBr ₂ , WBr ₃ , WBr ₆ , WCl ₂ , WCl ₄ , WCl ₅ , WCl ₆ , WF ₂ , WF ₄ , WF ₆ , WI ₂ , WI ₄ , WI _6, etc .; WOBr ₄ , tungsten oxyhalides such as WOCl ₄ and WOF ₄ ; WO ₂ ; tungsten such as H ₂ WO ₄ , NaWO ₄ , K ₂ WO ₄ , (NH ₄ ) ₂ WO ₄ , CaWO ₄ , CuWO ₄ , MgWO ₄ Acid or salt thereof; (CO) ₅ WC (OCH ₃ ) (CH ₃ ), (CO) ₅ WC (OC ₂ H ₅ ) (CH ₃ ), (CO) ₅ WC (OC ₂ H ₅ ) (C ₂ H ₅ )) or the like.
These tungsten-based metathesis catalysts can be used alone or in combination of two or more.

The use ratio of the tungsten-based metathesis catalyst is 0.005 to 0.25 mmol equivalent to 1 mol of the norbornene-based monomer composition. Among them, the use ratio of the tungsten-based metathesis catalyst is preferably in the range of 0.01 to 0.20 mmol equivalent to the norbornene-based monomer composition, and is preferably in the range of 0.01 to 0.15 mmol equivalent. And more preferred. When the usage ratio of the tungsten metathesis catalyst is larger than 0.20 mmol equivalent, the cost is inferior, the hydrogenation rate of the norbornene ring-opening polymer hydride is lowered, and the molecular weight distribution is widened. When the use ratio of the tungsten-based metathesis catalyst is less than 0.01 mmol equivalent, the polymerization conversion rate of the norbornene-based ring-opening polymer is low, and the amount of outgas of the resulting molded body increases.
When the proportion of the tungsten-based metathesis catalyst used is in this range, the polymerization conversion rate of the norbornene-based ring-opening polymer, the hydrogenation rate of the norbornene-based ring-opening polymer hydride, the molecular weight distribution, and the cost are excellent.

When performing metathesis polymerization, it is common to use a co-catalyst together with the tungsten-based metathesis catalyst.
Examples of the cocatalyst include organoaluminum compounds and organotin compounds, with organoaluminum compounds being preferred. Specific examples of the organoaluminum compound include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, and triisobutylaluminum, and alkylhalide aluminum such as diethylaluminum chloride and ethylaluminum dichloride. . Of these, triethylaluminum, triisobutylaluminum, and diethylaluminum chloride are preferable.

  These promoters can be used alone or in combination of two or more. The amount of the cocatalyst used is usually 0.01 to 30 mol, preferably 0.1 to 20 mol, more preferably 1 to 10 mol, per 1 mol of the metathesis catalyst. When the amount of the cocatalyst used is within these ranges, the generation of gel and high molecular weight components is small, the polymerization activity is high, and the molecular weight is easily controlled, which is preferable.

(3) Ring-opening polymerization of norbornene-based monomer composition The ring-opening polymerization reaction of the norbornene-based monomer composition is usually performed by diluting the norbornene-based monomer composition with a solvent.
Examples of the solvent to be used include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as n-pentane, hexane and heptane; aliphatic alicyclic hydrocarbons such as cyclopentane, cyclohexane and cyclooctane; Preferably, they are toluene, cyclohexane, cyclooctane, etc., More preferably, they are toluene and cyclohexane. These solvents can be used alone or in combination of two or more, and the amount used is usually 10 to 1000 parts by weight, preferably 50 to 700 parts by weight, per 100 parts by weight of the monomer composition, More preferably, it is the range of 100-500 weight part.

  In the ring-opening polymerization, a molecular weight regulator can be added to the reaction system. The molecular weight of the resulting ring-opening polymer can be adjusted by adding a molecular weight regulator. It does not specifically limit as a molecular weight regulator to be used, A conventionally well-known thing can be used.

Examples of the molecular weight regulator include chain α-olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene.
The proportion of the molecular weight regulator used can be arbitrarily selected in the range of 0.1 to 10 millimole equivalents per 1 mol of norbornene monomer composition, depending on the molecular weight of the target ring-opening polymer. .

  The polymerization temperature is usually in the range of 0 to 150 ° C., preferably 10 to 100 ° C., more preferably 30 to 60 ° C. When the temperature is within this range, formation of low molecular weight components and formation of gels and high molecular weight components Can be well balanced. The polymerization time is usually in the range of 30 minutes to 10 hours, preferably 1 to 7 hours, more preferably 2 to 5 hours.

In the polymerization reaction, the polymerization conversion rate is preferably 90 mol% or more, more preferably 99 mol% or more, and particularly preferably 100 mol%.
When the polymerization conversion rate is within this range, the amount of outgas of the obtained molded product is small, which is preferable.

  The weight average molecular weight of the obtained ring-opening polymer is usually 5,000 to 1,000,000, preferably 7,000 to 500,000, more preferably 8,000 to 400,000. If the molecular weight is too small, the mechanical strength is weak, and if it is too high, the polymerization solution becomes highly viscous, making handling difficult. In the present invention, the weight average molecular weight of the ring-opening polymer is a value measured by gel permeation chromatography.

(II) Step (B)
Step (B) is a step of obtaining a hydrogenated norbornene-based ring-opening polymer by hydrogenating the norbornene-based ring-opening polymer obtained in step (A). The hydrogenation reaction performed in this step is a reaction in which hydrogen is introduced in the presence of a hydrogenation catalyst to convert a carbon-carbon double bond in the main chain of the norbornene-based ring-opening polymer into a single bond.

  The step (B) can be carried out after once isolating the norbornene-based ring-opening polymer after completion of the ring-opening polymerization reaction in the step (A), or the reaction obtained by the ring-opening polymerization reaction in the step (A). It can also be carried out continuously by adding a hydrogenation catalyst to the solution. The latter is preferable from the viewpoint of production efficiency.

The hydrogenation catalyst to be used is not particularly limited, and a catalyst generally used for hydrogenation reaction of olefin compounds may be appropriately used. For example, combinations of transition metal compounds and alkali metal compounds such as cobalt acetate and triethylaluminum, nickel acetylacetonate and triisobutylaluminum, titanocene dichloride and n-butyllithium, zirconocene dichloride and sec-butyllithium, tetrabutoxytitanate and dimethylmagnesium Ziegler catalyst comprising: dichlorotris (triphenylphosphine) rhodium, JP-A-7-2929, JP-A-7-149823, JP-A-11-209460, JP-A-11-158256, JP-A-11 Noble metal complex catalyst comprising a ruthenium compound described in JP-A No. 193323, JP-A No. 11-209460, etc .; homogeneous catalyst; nickel, palladium, platinum, rhodium, ruthenium The metal, carbon, silica, diatomaceous earth, alumina, was supported supported heterogeneous catalysts on a carrier such as titanium oxide; and the like.
These hydrogenation catalysts can be used alone or in combination of two or more.

Among these, a supported heterogeneous catalyst is preferable because the hydrogenation catalyst can be easily removed by filtering the reaction solution after the hydrogenation reaction.
Specific examples of the supported heterogeneous catalyst include nickel / silica, nickel / diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, and palladium / alumina.

  The amount of the hydrogenation catalyst used is usually 0.01 to 100 parts by weight, preferably 0.1 to 50 parts by weight, more preferably 0.3 to 10 parts by weight, especially 100 parts by weight of the norbornene-based ring-opening polymer. Preferably it is the range of 0.5-2.0 weight part. In the present invention, since the use amount of the tungsten-based metathesis catalyst which is a catalyst poison is small, the hydrogenation reaction can proceed efficiently even if the use amount of the hydrogenation catalyst is reduced.

  The hydrogenation reaction is usually carried out in an organic solvent. The organic solvent can be appropriately selected depending on the solubility of the hydride to be produced, but it is preferable to use an organic solvent similar to the organic solvent used in the ring-opening polymerization reaction. This is because after the ring-opening polymerization reaction, the hydrogenation catalyst can be added and reacted as it is without replacing the solvent.

What is necessary is just to select hydrogenation reaction conditions suitably according to the kind of hydrogenation catalyst to be used.
The reaction temperature is usually -20 to + 250 ° C, preferably -10 to + 220 ° C, more preferably 0 to 200 ° C. If it is less than −20 ° C., the reaction rate becomes slow. On the other hand, if it exceeds 250 ° C., side reactions may occur.

  The hydrogen pressure is a gauge pressure, and is usually 0.01 to 10.0 MPa, preferably 0.05 to 8.0 MPa, more preferably 0.1 to 5.0 MPa. When the hydrogen pressure is less than 0.01 MPa, the hydrogenation rate is slow, and when it exceeds 10.0 MPa, a high pressure reactor is required.

  Although reaction time will not be specifically limited if it is time which can achieve a desired hydrogenation rate, Usually, it is the range of 0.1 to 50 hours. The hydrogenation rate of the ring-opening polymer is usually 90% or more, preferably 95% or more, more preferably 99% or more, and most preferably 99.9% or more.

  After completion of the reaction, the desired norbornene-based ring-opening polymer hydride can be isolated by carrying out ordinary post-treatment operations. For example, when a heterogeneous catalyst is used, after the hydrogenation reaction, the hydrogenation catalyst is removed by filtration, and then obtained by a solidification drying method or a direct drying method using a thin film dryer or the like. Can do. When a homogeneous catalyst is used as the hydrogenation catalyst, alcohol or water is added after the hydrogenation reaction to deactivate the catalyst, insolubilized in a solvent, and then filtered to remove the catalyst. The norbornene-based ring-opening polymer hydride can be usually obtained in a powder form or a pellet form.

  According to the method for producing a norbornene ring-opening polymer hydride of the present invention, a norbornene ring-opening polymer hydride having a narrow molecular weight distribution, a high hydrogenation rate, and a controlled melt mass flow rate (MFR) is obtained. It can be manufactured with good yield at low cost.

2) Norbornene-based ring-opening polymer hydride The molecular weight of the norbornene-based ring-opening polymer hydride of the present invention obtained as described above is the weight average molecular weight (Mw) measured by gel permeation chromatography. It is 5,000 to 1,000,000, preferably 7,000 to 500,000, more preferably 8,000 to 400,000. If the molecular weight is too small, the mechanical strength is weak, and if it is too large, the solution becomes highly viscous, making handling difficult.

  The molecular weight distribution (Mw / Mn) of the norbornene-based ring-opening polymer hydride of the present invention is usually 1 to 8, preferably 1.5 to 5, and more preferably 2 to 2.7. Thus, since the norbornene-type ring-opening polymer hydride of the present invention has a narrow molecular weight distribution, the obtained molded article is excellent in strength and heat resistance. In addition, the norbornene ring-opening polymer hydride of the present invention has a high hydrogenation rate and a small amount of residual monomers.

The melt mass flow rate (MFR) of the norbornene-based ring-opening polymer hydride of the present invention is the conditions for molding a molding material containing the norbornene-based ring-opening polymer hydride, and the shape and requirements of the resulting molded body. Although it is appropriately selected depending on the physical properties, it is usually 5 g / 10 min to 25 g / 10 min.
In the present invention, MFR is a value measured at 230 ° C. and a load of 2.16 kg based on JIS K 6719.

The norbornene-based ring-opening polymer hydride of the present invention can be made into a molding material by containing known additives as long as the effects of the invention are not impaired, if necessary.
Known additives include other polymers, fillers, antioxidants, release agents, flame retardants, antibacterial agents, wood flour, coupling agents, plasticizers, colorants, lubricants, silicone oils, foaming agents, interfaces. Activators, light stabilizers, lubricants and dispersion aids, heat stabilizers, UV absorbers, antistatic agents, dispersants, chlorine scavengers, crystallization nucleating agents, antifogging agents, organic matter fillers, neutralizing agents, decomposition Agents, metal deactivators, antifouling materials, thermoplastic elastomers and the like. These additives can be used alone or in admixture of two or more.

  As a method for producing a molding material, a method for obtaining a pellet-shaped molding material by kneading a hydride of a norbornene-based ring-opening polymer and an additive to be added as necessary; a norbornene-based material in an appropriate solvent Examples thereof include a method of obtaining a molding material by mixing a ring-opened polymer hydride and an additive to be added as necessary, and removing the solvent.

  For kneading, a melt kneader such as a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader, or a feeder ruder can be used. The kneading temperature is preferably in the range of 200 to 400 ° C, and more preferably in the range of 240 to 350 ° C. Further, when kneading, the components may be added together and kneaded, or may be kneaded while adding in several times.

  The molding material can be formed into a molded body using a known molding means such as an injection molding method, a compression molding method, an extrusion molding method or the like. The shape of the molded body can be appropriately selected depending on the application.

  Since the molded product of the present invention has a high polymerization conversion rate of the norbornene-based ring-opening polymer to be used, the residual monomer component is small and the outgas amount is small. Moreover, since the molecular weight distribution of the norbornene-based ring-opening polymer hydride to be used is narrow, the heat resistance is excellent, and since the hydrogenation rate is high, the weather resistance is excellent.

  Although it does not specifically limit as a use of the molded object of this invention, Optical, such as an optical disk, an optical lens, a prism, a light diffusing plate, an optical card, an optical fiber, an optical mirror, a liquid crystal display element substrate, a light guide plate, a polarizing film, a phase difference film Materials: Liquid, powder, or solid medicine containers (liquid medicine containers for injection, ampoules, vials, prefilled syringes, infusion bags, sealed medicine bags, press-through packages, solid medicine containers, eye drops containers, etc.), Sampling containers (sampling test tubes for blood tests, caps for chemical containers, blood collection tubes, specimen containers, etc.), medical instruments (syringes, etc.), sterile containers for medical instruments (for scalpels, forceps, gauze, contact lenses, etc.) ), Experimental / analytical instruments (beakers, petri dishes, flasks, test tubes, centrifuge tubes, etc.), medical optical components (plastic lenses for medical examination Etc.), pipe material (medical infusion tube, pipe, fittings, valves, etc.), artificial organs or any part definition (Hayuka, artificial hearts, equipment for medical artificial tooth roots, etc.) and the like;

  Containers for food such as bottles, returnable bottles, baby bottles, films, shrink films; containers for processing or transfer (tanks, trays, carriers, cases, etc.), protective materials (carrier tapes, separation films, etc.), piping ( Pipes, tubes, valves, flow meters, filters, pumps, etc.), electronic parts processing equipment for liquid containers (sampling containers, bottles, ampoules bags, etc.); covering materials (for electric wires, cables, etc.), consumer Electrical insulating materials such as industrial electronic equipment housings (copiers, computers, printers, televisions, video decks, video cameras, etc.), structural members (parabolic antenna structural members, flat antenna structural members, radar dome structural members, etc.);

  Circuit boards such as general circuit boards (rigid printed boards, flexible printed boards, multilayer printed wiring boards, etc.), high frequency circuit boards (circuit boards for satellite communication devices, etc.); transparent conductive films (liquid crystal boards, optical memories, surface heating elements) Etc.) substrate; semiconductor encapsulant (transistor encapsulant, IC encapsulant, LSI encapsulant, LED encapsulant, etc.), electrical / electronic component encapsulant (motor encapsulant, capacitor encapsulant) Materials, switch sealing materials, sensor sealing materials, etc .; automotive interior materials such as room mirrors and meter covers; automotive exterior materials such as door mirrors, fender mirrors, beam lenses, and light covers; Is mentioned.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples. Unless otherwise indicated, parts and% in the examples are based on weight.

(1) The content of alkenyl group-substituted norbornene (content of IPN and PN) contained in the norbornene monomer composition was determined by analyzing the norbornene monomer composition by gas chromatography.
(2) The polymerization conversion rate was determined by analyzing the polymerization reaction solution by gas chromatography.
(3) The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the norbornene-based ring-opening polymer hydride are polyisoprene converted values by gel permeation chromatography (GPC) using cyclohexane as a solvent, or It was measured and determined as a polystyrene equivalent value by GPC using toluene as a solvent.
(4) The hydrogenation rate of the norbornene-based ring-opening polymer hydride was calculated from the change in peak area related to unsaturated bonds by measuring ¹ H-NMR of the polymer before hydrogenation and the polymer after hydrogenation. .
(5) Melt mass flow rate (MFR) of norbornene-based ring-opening polymer hydride was measured at 230 ° C. and a load of 2.16 kg based on JIS K 6719.

Examples 1 to 6 Preparation of Norbornene-Based Ring-Opening Polymer Hydride 1 to 6 Tricyclo [4.3.0.1 ² containing IPN and PN and CPD in amounts shown in Table 1 under a nitrogen atmosphere. ^{, 5} ] dec-3-ene (DCP) and tetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10} ] dodec-3-ene (TCD) in a ratio of 85:15 by weight, 100 parts by weight of norbornene monomer composition is dissolved in 300 parts by weight of cyclohexane to obtain a molecular weight regulator. As a result, 0.97 parts by weight of 1-hexene was added. Furthermore, a mixture of 0.97 parts by weight of a 10% by weight cyclohexane solution of triisobutylaluminum and 0.035 parts by weight of isobutyl alcohol was added to this solution.

While maintaining this reaction solution at 50 ° C., 90 parts by weight of the norbornene monomer composition and 0.6% by weight of tungsten hexachloride (hereinafter abbreviated as “W catalyst”) in the amount shown in Table 1. The cyclohexane solution was added dropwise over 2 hours, and the reaction was further continued for 30 minutes after completion of the addition.
To the polymerization reaction solution, 0.048 parts by weight of butylene oxide and 0.26 parts by weight of isopropyl alcohol were added to inactivate the polymerization catalyst.
The obtained polymerization reaction solution was analyzed to determine the polymerization conversion rate. The results are shown in Table 1.

  Next, to 100 parts by weight of the polymerization reaction solution obtained above, 1.5 parts by weight of a diatomaceous earth-supported nickel catalyst (G-96D, manufactured by Nissan Gardler, nickel support rate: 58% by weight) and 10 parts by weight of cyclohexane were added, and pressure resistance reaction was performed. In the vessel, a hydrogenation reaction was performed at 170 ° C. and a hydrogen pressure of 4.4 MPa for 2 hours.

This solution was filtered with a pressure filter (made by Ishikawajima-Harima Heavy Industries Co., Ltd., leaf filter) equipped with a polypropylene filter cloth to separate the catalyst. The obtained reaction solution containing the polymer hydride was poured into 400 parts by weight of isopropyl alcohol with stirring to precipitate the hydride, which was collected by filtration. Furthermore, after washing | cleaning with 200 weight part of acetone, it dried at 100 degreeC in the vacuum dryer decompressed to 1.33 hPa or less for 24 hours, and obtained the norbornene-type ring-opening polymer hydrides 1-6, respectively.
The hydrogenation rate, weight average molecular weight (Mw) and molecular weight distribution of the obtained norbornene-based ring-opening polymer hydrides 1 to 6 were measured. The measurement results are shown in Table 1.

(Comparative Examples 1-6) Preparation of Norbornene-Based Ring-Opening Polymer Hydride 7-12 Tricyclo [4.3.0.1 ^2,5 ] deca containing alkenyl group-substituted norbornene and CPD in the amounts shown in Table 1 -3-ene (DCP) and tetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10} ] dodec-3-ene (TCD) in a weight ratio of 85:15 and a norbornene monomer composition containing 0.6 wt. An operation was carried out in the same manner as in Examples 1 to 6 except that a% cyclohexane solution was used to obtain norbornene-based ring-opening polymer hydrides 7 to 12.
The hydrogenation rate, weight average molecular weight (Mw) and molecular weight distribution of the obtained norbornene-based ring-opening polymer hydrides 7 to 12 were measured. The measurement results are shown in Table 1.

  Table 1 shows the following. Step (A) of ring-opening polymerization of a norbornene-based monomer composition containing a tricyclic or higher polycyclic norbornene-based monomer in the presence of a tungsten-based metathesis catalyst, and hydrogenating the resulting ring-opened polymer A process for producing a hydride of a norbornene-based ring-opening polymer, wherein in step (A), the ratio of (1) tungsten metathesis catalyst to 1 mol of norbornene-based monomer composition is 0. 0.002 to 0.25 mmol equivalent, (2) the norbornene-based monomer composition has an alkenyl substituent norbornene content of 0.7% by weight or less, and (3) a norbornene-based monomer composition The process for producing a hydride of a norbornene-based ring-opening polymer characterized in that the cyclopentadiene content in the product is in the range of 0.015 to 0.035% by weight has a high polymerization conversion rate, water Can be rate is high, to obtain a narrow molecular weight distribution ring-opened norbornene polymer hydrides (Examples 1-6).

On the other hand, when the content of alkenyl substituent norbornene in the norbornene-based monomer composition is more than 0.7% by weight, the polymerization conversion rate is low and the hydrogenation rate is low (Comparative Example 1).
When the ratio of the tungsten-based metathesis catalyst to the norbornene-based monomer is more than 0.25 mmol equivalent and the alkenyl substituent norbornene content in the norbornene-based monomer composition is more than 0.7% by weight, the polymerization conversion rate And the hydrogenation rate is low (Comparative Example 2).
When the ratio of the tungsten-based metathesis catalyst to the norbornene-based monomer is more than 0.25 mmol equivalent and the cyclopentadiene content in the norbornene-based monomer composition is more than 0.035% by weight, the polymerization conversion rate is low. The hydrogenation rate is low (Comparative Examples 3 and 4).
When the content of cyclopentadiene in the norbornene monomer composition is less than 0.015% by weight, the molecular weight distribution is wide (Comparative Examples 5 and 6).

(Examples 7 to 9)
Tricyclo [4.3.0.1 ^2,5 ] dec-3-ene (containing 0.7% by weight of alkenyl group-substituted norbornene and CPD in the amount shown in Table 2 under a nitrogen atmosphere. DCP) and tetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10} ] dodec-3-ene (TCD) in a ratio of 85:15 by weight, 100 parts by weight of norbornene monomer composition is dissolved in 300 parts by weight of cyclohexane to obtain a molecular weight regulator. As a result, 0.97 parts by weight of 1-hexene was added. Furthermore, a mixture of 0.97 parts by weight of a 10% by weight cyclohexane solution of triisobutylaluminum and 0.035 parts by weight of isobutyl alcohol was added to this solution.

While maintaining this reaction liquid at 50 ° C., 90 parts by weight of the norbornene-based monomer composition and 9.67 parts by weight of a 0.6 wt% cyclohexane solution of W catalyst were dropped over 2 hours, and the dropping was completed. The reaction was further continued for 30 minutes.
To the polymerization reaction solution, 0.048 parts by weight of butylene oxide and 0.26 parts by weight of isopropyl alcohol were added to inactivate the polymerization catalyst.
As a result of analyzing the obtained polymerization reaction solution, the polymerization conversion rate was 100%.

  Next, to 100 parts by weight of the polymerization reaction solution obtained above, 1.2 parts by weight of a diatomaceous earth-supported nickel catalyst (G-96D, manufactured by Nissan Zodo Chemie, 58% by weight of nickel support) and 10 parts by weight of cyclohexane were added, and pressure resistance reaction was performed. In the vessel, a hydrogenation reaction was performed at 170 ° C. and a hydrogen pressure of 4.4 MPa for 2 hours.

  This solution was filtered with a pressure filter (made by Ishikawajima-Harima Heavy Industries Co., Ltd., leaf filter) equipped with a polypropylene filter cloth to separate the catalyst. The obtained reaction solution containing the polymer hydride was poured into 400 parts by weight of isopropyl alcohol with stirring to precipitate the hydride, which was collected by filtration. Furthermore, after washing | cleaning with 200 weight part of acetone, it was made to dry at 100 degreeC in the vacuum dryer decompressed to 1.33 hPa or less for 24 hours, and the norbornene-type ring-opening polymer hydrides 13-15 were obtained, respectively.

  The melt mass flow rate (MFR) of the obtained norbornene-based ring-opening polymer hydrides 13 to 15 was measured. The measurement results are shown in Table 2.

  From Table 2, it can be seen that the MFR decreases as the CPD content increases. That is, it was found that by controlling the CPD content contained in the norbornene-based monomer composition, the norbornene-based ring-opening polymer hydride having the target MFR can be efficiently obtained.

Claims (4)

Step (A) of ring-opening polymerization of a norbornene-based monomer composition containing a tricyclic or higher polycyclic norbornene-based monomer in the presence of a tungsten-based metathesis catalyst, and hydrogenating the resulting ring-opened polymer A process for producing a hydride of a norbornene-based ring-opening polymer having the step (B), wherein in the step (A),
(1) The ratio of the tungsten-based metathesis catalyst to 1 mol of the norbornene-based monomer composition is 0.005 to 0.25 mmol equivalent,
(2) The alkenyl group-substituted norbornene content in the norbornene monomer composition is 0.7% by weight or less, and
(3) A process for producing a hydride of a norbornene-based ring-opening polymer, wherein the cyclopentadiene content in the norbornene-based monomer composition is in the range of 0.015 to 0.035% by weight.   The method for producing a hydride of a norbornene-based ring-opening polymer according to claim 1, wherein the tricyclic or higher polycyclic norbornene-based monomer is dicyclopentadiene.   A norbornene-based ring-opening polymer hydride obtained by the production method according to claim 1 or 2.   The molded object obtained by shape | molding the norbornene-type ring-opening polymer hydride of Claim 3.