JPS6139326B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an improved method for making ring-opened polymers. More specifically, norbornene derivatives and/or norbornadiene derivatives, or mixtures thereof with cycloolefin compounds copolymerizable with them, are referred to as "unsaturated polymers containing a carbon-carbon double bond" (hereinafter referred to as "unsaturated polymers"). (A) an organometallic compound, (B) in the presence or absence of
An improved method for producing a ring-opening polymer, characterized in that ring-opening polymerization is carried out using a catalyst system obtained from a reaction product of a tungsten and/or molybdenum oxide and a Lewis acid and a halogenated compound of (C) metal. Regarding. Some of the inventors of the present invention have already proposed methods for producing the same ring-opened polymer in Japanese Patent Publication Nos. 50-23720 and 49-67999 and 49-77999. However, when ring-opened polymers are produced by the above-mentioned methods, the polymerization activity of these catalyst systems is not necessarily satisfactory. Furthermore, as a result of various searches to obtain a catalyst system with excellent catalytic activity, the present inventors have found that organic metal compounds, reaction products of oxides of tungsten and/or molybdenum with Lewis acids, and halogen compounds of metals The inventors have discovered that a ring-opening polymer can be obtained in high yield by carrying out ring-opening polymerization of a norbornene derivative or a norbornadiene derivative, or these and a small amount of a cycloolefin compound using the resulting catalyst system, and have arrived at the present invention. Since the catalyst system used in the present invention has a very high polymerization activity (catalytic activity), it is possible not only to reduce the amount of catalyst used, but also to increase the production efficiency of the polymerization apparatus. Furthermore, since the amount of catalyst used may be small, it is relatively easy to remove the catalyst residue remaining in the ring-opened polymer obtained after the polymerization is completed. Furthermore, since the catalyst system used in the present invention exhibits little decrease in activity due to the polar groups of the monomers, ring-opening polymerization can be continued for a long time. The norbornene derivative used in the present invention is a polar group or a hydrocarbon group having at most 20 carbon atoms substituted with 1 to 10 polar groups, or an aromatic hydrocarbon group having at most 20 carbon atoms. It is a norbornene derivative having a group. The above polar groups include "chlorine atom, bromine atom, cyano group (nitrile group), ester group and ether group having at most 20 carbon atoms, amide group,""containing at least one nitrogen atom in the heterocycle" Aromatic Character, edited by the Chemistry Dictionary, 'Chemistry Dictionary' Vol. 8, p. 601, 1964
Published by Kyoritsu Shuppansha, Reference) “Groups with heterocycles”
(hereinafter referred to as "aromatic nitrogen-containing heterocyclic group"), N-substituted amide group substituted with a hydrocarbon group having at most 20 carbon atoms, and aromatic nitrogen-containing heterocyclic group (hereinafter referred to as "aromatic nitrogen-containing heterocyclic group"). (referred to as "A group polar group"), refers to acid anhydride groups and imide groups. The general formulas of typical norbornene derivatives are shown by the following formulas [formula () and formula ()]. In the formula, W ¹ , X ¹ , Y ¹ and Z ¹ and
W ² , X ² , Y ² and Z ² may be the same or different;
Hydrocarbon groups having at most 20 carbon atoms selected from the group consisting of hydrogen atoms, alkyl, alkenyl, cycloalkyl, cycloalkyl substituted by alkyl groups, aryl and aralkyl groups, the above A group A polar group, the above-mentioned hydrocarbon group or imide group substituted with a group A polar group [the general formula is

[Formula] (where R ¹ is an alkylene group, alkenylene group or arylene group having at most 6 carbon atoms, n is 0,
1 or 2)], but
W ¹ , X ¹ , Y ¹ and Z ¹ or W ₂ , X ² , Y ² and Z ²
At least one of them is an A group polar group, A
a hydrocarbon group substituted by a group polar group;
It is an imide group or an aromatic hydrocarbon group. The general formulas of other typical norbornene derivatives are shown by the following formulas [formulas () and ()]. In the formula, W ³ and Z ³ and W ⁴ and Y ⁴
may be the same or different, and are a hydrogen atom, the above-mentioned hydrocarbon group, the above-mentioned ester group or ether group, or a hydrocarbon group substituted with an ester group or ether group, and A has the general formula -COOR ² -
R ³ −OOC−, −COOR ⁴ −, −R ⁵ OR ⁶ −, −R ⁷ O−,

【formula】

【formula】

[expression] or

[Formula] [However, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹² may be the same or different, and are alkylene groups having at most 20 carbon atoms. R ² , R ⁸ , R ¹⁰ and R ¹¹ may be the same or different and are the above-mentioned hydrocarbon groups, and E has the general formula

[Formula] (However, B is a hydrocarbon having at most 20 carbon atoms, and D is oxygen or

[Formula] (wherein R is the above-mentioned hydrocarbon group, l and m are independently 0, 1 or 2, and q is 0 or 1)]. Representative examples of these norbornene derivatives are Japanese Patent Publication No. 50-23720, Japanese Patent Publication No. 49-67999, Japanese Patent Publication No. 49-49-
No. 77999, No. 50-71800, No. 50-75300, No. 50
-153100, No. 50-110000, No. 50-112500, and No. 50-160400, as well as Japanese Patent Application No. 129581/1981. Among these norbornene derivatives, particularly representative ones include 5-cyano-bicyclo[2,2,1]-heptene-2,5,5-dicyano-bicyclo[2,2,1]-heptene- 2, 5・
6-dicyanobicyclo[2.2.1]-heptene-2,5-cyano-5-methyl-bicyclo[2.
2.1]-heptene-2,5-cyano-6-methyl-bicyclo[2.2.1]-heptene-2,5
-cyano-5-ethyl-bicyclo[2.2.1]
-Heptene-2,5-cyanomethyl-bicyclo[2.2.1]-heptene-2,5-methoxycarbonyl-bicyclo[2.2.1]-heptene-
2,5-Methyl-5-methoxycarbonyl-bicyclo[2.2.1]-heptene-2,5.6-dimethoxycarbonyl-bicyclo[2.2.1]-
heptene-2,5-acetoxy-bicyclo[2.
2.1]-heptene-2,5-methoxy-bicyclo[2.2.1]-heptene-2,5-chloro-
Bicyclo[2,2,1]-heptene-2,5-chloromethyl-bicyclo[2,2,1]-heptene-2,5,6-bis(chloromethyl)-bicyclo[2,2,1]-heptene- 2,5-chloro-5-
Cyano-bicyclo[2.2.1]-heptene-
2,5-cyano-5-methoxycarbonyl-bicyclo[2.2.1]-heptene-2, N.N-dimethyl-bicyclo[2.2.1]-heptene-2
-Carbonamide-5,5-(2'-pyridyl)-bicyclo[2.2.1]-heptene-2,2-(2'-
pyridyl)-1.4; 5.8-dimethanol 1.
2,3,4,4a,5,8,8a-octahydronaphthalene, 3,6-methylene-1,2,3,6-tetrahydro-cis-phthalic anhydride, 1,4;
5,8-dimethano-1,2,3,4,4a,5.
8,8a-octahydronaphthalene-2,3-dicarboxylic anhydride, N-methyl-3,6-methylene-1,2,3,6-tetrahydro-cis-phthalimide, N-n-butyl-3,6 -methylene-
1,2,3,6-tetrahydro-cis-phthalimide, N-butyl-3,6-1-methyl-1.
2,3,6-tetrahydro-cis-phthalimide, 5-phenyl-bicyclo[2,2,1]-heptene-2 and 2-phenyl-1,4;5,8
-Dimethanol-1, 2, 3, 4, 4a, 5, 8, 8a-
One example is octahydronaphthalene. Norbornadiene derivatives include those in which one of the carbon-carbon double bonds in the norbornene nucleus is an aromatic double bond, and the norbornadiene derivatives represented by the following formula [() formula]. Derivatives are a typical example. In the formula, X ⁵ and Y ⁵ may be the same or different, and are a hydrogen atom, the aforementioned hydrocarbon group, an ester ^group , or a hydrocarbon group substituted by an ester ^group ; One is an ester group or a hydrocarbon group substituted by an ester group. Representative examples of these norbornadiene derivatives are described in the specifications of JP-A-50-61500 and JP-A-50-103600. Among these norbornadiene derivatives, 1,4-dihydro-
Examples include 1,4-methanonaphthalene, 5,8-diacetoxy-1,4-dihydro-1,4-methanonaphthalene and 2-methoxycarbonyl-bicyclo[2.2.1]-heptene-2,5-diene. . The cycloolefin compounds used for copolymerization in the present invention are monocyclic monoolefin compounds, non-conjugated cyclic polyene compounds, and polycyclic olefin compounds. The general formula of the monocyclic monoolefin compound is represented by the following formula [formula ()]. (However, n is an integer of 3 to 20.) Typical examples include cyclopentene, cycloheptene, cyclooctene, cyclodecene, cyclododecene, and these monocyclic monoolefin compounds containing an alkyl group with one or more carbon atoms and at most 10. , alkenyl group and allyl (aryl)
Examples include monocyclic monoolefin compounds substituted with a hydrocarbon group selected from the group consisting of: The general formula of the non-conjugated cyclic polyene compound is represented by the following formulas [formula () and formula ()].

【formula】 [However, M is a metal from group A, A, B, B, A or B of the periodic table, and R is an alkyl group, alkenyl group, aryl group, or aralkyl group having at most 20 carbon atoms. , an organic group selected from the group consisting of an alkoxide group, a phenoxy group, and a cyclopentadienyl group, or a hydrogen atom or a halogen atom, which may be the same or different, but at least one of them is a hydrogen atom or the above-mentioned is an organic group, and n is the highest valence number of the metal or less.]

Other organometallic compounds include complexes of the above-mentioned organometallic compounds with equimolar amounts of pyridine, triphenylphosphine or diethyl ether, and reaction products of 1 mol of the above-mentioned organometallic compounds with at most 2.0 mol of water; Examples include double salts of the above-mentioned organometallic compounds. Typical examples include lithium, sodium, potassium, magnesium, calcium, zinc, boron, aluminum, gallium, titanium,
Organometallic compounds containing zirconium, silicon, germanium, and tin are preferred, particularly organometallic compounds of lithium, sodium, magnesium, zinc, aluminum, and tin, and organoaluminium-based compounds are particularly preferred. Typical examples of the organoaluminum compounds include triethylaluminum, triisobutylaluminum, trihexylaluminum, diethylaluminum chloride, di-n-butylaluminum chloride, ethylaluminum sesquichloride, diethylaluminum butoxy, and the reaction of triethylaluminum with water. The product [reaction ratio 1:0.5 (molar ratio)] is mentioned.
Other representative examples are JP 50-23720, JP 49-67999, JP 49-77999, JP 50-58200.
No. 50-61500, No. 50-71800 and No. 50-
It is described in each publication of No. 75300. Examples of other organoaluminum compounds include aluminum/siloxsalene compounds, aluminum/amide compounds, dialmoxalene compounds, and double salts containing the above organoaluminum compounds. Representative examples of other organometallic compounds are Japanese Patent Application No. 50-112068, No. 50-112534, No. 50-
This is clearly stated in the specifications of No. 116324, No. 50-117664, and No. 50-120317. In addition, the reaction product used to obtain the catalyst system used in the present invention is obtained by combining a "tungsten or molybdenum oxide" (hereinafter referred to as "oxide") and a Lewis acid in the absence of an inert organic solvent or It can be obtained by reacting in the presence of Representative examples of oxides include tungsten trioxide and molybdenum trioxide, as well as oxyhalides of tungsten or molybdenum (eg, tungsten dioxydichloride, tungsten oxytetrachloride, and molybdenum oxytrichloride). Typical examples of Lewis acids are described in JP-A-50-112500, but other examples include phosphorus pentahalide (e.g., phosphorus pentachloride, phosphorus pentabromide) and phosphorus oxytrihalide (e.g., Examples include phosphorus oxytrichloride and phosphorus oxytribromide).
Particularly preferred Lewis acids are phosphorus pentahalides and phosphorus oxyhalides. The ratio of Lewis acid to 1 mole of oxide is generally 0.01 to 100 mole, preferably 0.05 to 50 mole, particularly 0.1 mole, from the viewpoint of its reactivity and the catalytic activity (polymerization activity) of the resulting catalyst system. ~20 mol is preferred. Further, the reaction temperature is generally 0 to 500°C, preferably 40 to 300°C, and particularly preferably 60 to 250°C, in view of its reactivity. Furthermore, inert organic solvents do not react with oxides and Lewis acids and are liquid at the reaction temperature. In this reaction, each of the oxide, Lewis acid, and inert organic solvent (if used) may be used alone or in combination of two or more. The reaction time varies depending on the reaction temperature and reaction rate, but is generally from several minutes to more than ten hours.
When the reaction is carried out in an inert organic solvent, the indication for completion of this reaction is when the supernatant liquid of the reaction liquid turns reddish-purple to reddish-brown; , supernatant liquid), a catalyst system with high polymerization activity can be obtained. In addition, if the supernatant liquid or oral fluid is collected and used from this reaction liquid,
Although a homogeneous catalyst system is obtained, there is no problem in using a reaction solution that still contains insoluble parts. The metal halogen compounds in the present invention include Group A, Group B, Group A, Group B, Group A,
B group, A group, B group, A group, B group, A
halides, oxyhalides and hydroxyhalides of Group B, Group A and Group metals. Among the metal halides used in the present invention, chlorides include LiCl, NaCl, KCl,
CuCl, _CuCl2 , _BeCl2 , _MgCl2 , _CaCl2 , _SrCl2 ,
BaCl ₂ , ZnCl ₂ , HgCl, HgCl ₂ , BCl ₃ , AlCl ₃ ,
_TiCl3 , _TiCl4 , _ZrCl4 , _SiCl4 , _SnCl2 , _SnCl4 ,
PbCl ₂ , VCl ₃ , VCl ₄ , SbCl ₃ , , SbCl ₅ , MnCl ₂ ,
Chlorides such as FeCl ₂ , FeCl ₃ , CoCl ₂ and NiCl ₂ may be mentioned. Furthermore, fluoride, bromide, and iodide may be used in place of chlorine in these chlorides, in which fluorine, bromine, or iodine is substituted. Furthermore, as metal oxyhalides,
VOCl ₃ is mentioned. Furthermore, examples of metal hydroxyhalides include magnesium hydroxychloride. Furthermore, double salts of these metal halides, metal oxyhalides and metal hydroxyhalides may be used. Some of these metal halogen compounds include hydrates as well as anhydrides, and any of these may be used. Generally, anhydrides are desirable because they provide catalyst systems with excellent polymerization activity. In the present invention, the organometallic compound and the metal halogen compound may be used alone or in combination of two or more. In carrying out the present invention, the ratio of the organic compound to 1 atomic equivalent of tungsten and/or molybdenum contained in the reaction product is generally from 0.1 to 0.1, in view of the polymerization activity of the resulting catalyst system.
100 mol, preferably 0.3 to 40 mol, particularly,
0.5 to 20 moles are preferred. Furthermore, the ratio of the metal halogen compound to 1 atomic equivalent of tungsten and/or molybdenum is generally from 0.01 to
100 mol, preferably 0.05 to 80 mol, particularly preferably 0.1 to 50 mol. A method of using a metal halogen compound is simply adding it to the organometallic compound and the reaction product as the third component of the catalyst, or the reaction product and the metal halogen compound in the presence or absence of an inert organic solvent. and a method of heat-treating a mixture of an organometallic compound, a reaction product, and a metal halogen compound. In these cases, suitable temperatures are generally below 300°C, preferably between -20 and 200°C. Furthermore, although the catalyst system used in the present invention differs depending on its type, the proportion of the reaction product used is 0.001 to 100 atomic equivalents of tungsten or molybdenum metal per 1000 moles of monomer. Yes, from the standpoint of polymerization activity and catalyst removal.
0.005 to 50 atomic equivalents are preferred, especially 0.01 to 10
Atomic equivalents are preferred. The object of the present invention can be achieved by carrying out ring-opening homopolymerization or ring-opening copolymerization of monomers in the presence of the above catalyst system and in the absence of an inert organic solvent. Ring-opening polymerization may be carried out in an organic solvent. Examples of inert organic solvents include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, and ethers. When carrying out the present invention in an inert organic solvent, these inert organic solvents may be used alone or as a mixture of two or more. When ring-opening polymerization is carried out in the organic solvent, the proportion of the organic solvent used per 1 part by volume of the monomer is generally at most 20 parts by volume, and preferably 10 parts by volume or less. The polymerization temperature is generally -100 to +250°C,
In particular, -50 to +180°C is preferable, especially 0 to +180°C.
150°C is preferred. If the polymerization temperature is -100°C or lower, there is no sufficient polymerization activity, so the polymerization rate is very slow, and furthermore, the monomer or the mixture of the monomer and the inert organic solvent may solidify. On the other hand, when the polymerization temperature is 250°C or higher, it is often difficult to sufficiently control the polymerization. Although the target ring-opening polymer of the present invention can be obtained by ring-opening polymerization according to the above method, it is also possible to obtain a ring-opening polymer having at most 15 carbon atoms.
Olefins (e.g. ethylene, hexene)
1, octene-1), internal olefins having at most 20 carbon atoms (e.g. hexene-2, octene-2), conjugated diolefins having at most 20 carbon atoms or their halogen substitutions (e.g. butadiene, chloroprene) , non-conjugated diolefins having at most 20 carbon atoms (for example, 1,4-hexadiene) and JP-A-50-56494, JP-A-50-56495
The molecular weight of the resulting ring-opening polymer can be adjusted by adding the compounds described in the following publications as molecular weight regulators to the ring-opening polymerization system. can. monomer
The addition ratio of the molecular weight regulator to 100 moles is
Generally, the amount is at most 20 moles, preferably 10 moles or less, and particularly preferably 5 moles or less. In carrying out the present invention, it may be carried out in a homogeneous system, but it may also be carried out in a heterogeneous system. Moreover, a batch method or a continuous method may be used. Since the catalyst system of the present invention is unstable to oxygen and moisture, it is desirable to operate under an atmosphere of inert gas such as argon and nitrogen. Although the present invention can achieve its objectives by ring-opening polymerization in the absence of an unsaturated polymer, it can also be carried out in the presence of an unsaturated polymer. Unsaturated polymers contain carbon-carbon double bonds, and include butadiene-based rubbers containing butadiene as a main component (for example, butadiene monopolymer rubber, styrene-butadiene copolymer rubber, acrylonitrile-butadiene). copolymer rubber), chloroprene rubber, isoprene rubber, natural rubber, ethylene-propylene-dien terpolymer (generally referred to as EPT or EPDM), and cycloolefin rubber. . When carrying out the present invention in the presence of the unsaturated polymer, the Mooney viscosity of the unsaturated polymer is generally between 10 and 200.
20 to 150 is desirable, especially 30 to 150.
130 is preferred. Furthermore, it is preferable that the carbon-carbon double bond is at least one carbon-carbon double bond per 1000 total carbon-carbon bonds, and more preferably 10 or more carbon-carbon double bonds. The proportion of unsaturated polymer used per 1 part by weight of monomer is generally at most 10 parts by weight and 5 parts by weight.
It is preferably at most 3 parts by weight, particularly preferably at most 3 parts by weight. If the amount is 10 parts by weight or more based on 1 part by weight of the monomer, a polymer exhibiting the characteristics of the monomer used in the present invention cannot be obtained. When carrying out ring-opening polymerization in the presence of an unsaturated polymer, the unsaturated polymer is generally dissolved in advance in the monomer or the monomer and an inert organic solvent described below, or suspended (dispersed). It is used with Further, the ring-opening polymerization, graft polymerization, block polymerization, or a combination of graft and block polymerization may be used. Graft products and block polymers obtained by the above method have excellent impact resistance, and are therefore particularly promising in fields where impact resistance is desired. After completion of the ring-opening polymerization, the resulting polymer can be recovered by several methods. As an example of the recovery method, a method for removing the catalyst and recovering the polymer that is generally used in solution polymerization of isoprene, butadiene, etc. may be applied. Other purification (post-treatment) methods include Japanese Patent Publication No. 50-23720 and Japanese Patent Publication No. 49-67999;
−77999, No. 49-130500 and No. 50-58200
No. 50-71800, No. 50-75300, No. 50-
It is described in the following publications: No. 103600, No. 50-153100, No. 50-159598, and No. 50-160400. According to the invention, ring-opened polymers with good properties such as mechanical properties (for example, impact resistance, low-temperature impact resistance, etc.), moldability and transparency or with good adhesive properties or Ring-opened polymers useful as ion exchange resins or flocculants can be produced. In addition, since the polymerization activity of the catalyst is very high, the production amount of ring-opening polymer per unit amount of catalyst is high. Purification of the ring-opened polymers obtained can be very simple or even omitted. As described above, the ring-opened polymer obtained by the present invention has excellent properties and can be used as is, but it is also compatible with the ring-opened polymer and graft and/or block polymers. Graft polymerization of styrene, acrylonitrile, vinyl chloride, methyl methacrylate, etc. to a rubber-like material described below Resin-like products such as grafted products, as well as butadiene-based rubber products, chlorinated polyethylene-based rubber products, acrylic acid ester-based rubber products, ethylene-vinyl acetate copolymer rubber products, and chloroprene-based rubber products. One or more kinds of rubber-like materials such as rubber-like materials can also be blended. Furthermore, stabilizers against light (ultraviolet rays), heat, oxygen, and ozone, flame retardants, lubricants, fillers, reinforcing agents, and impact modifiers (for example, carbon By incorporating additives such as metal salts of acids), colorants, antistatic agents, and foaming agents, the effect can be further enhanced. The ring-opening polymer, graft product and/or block polymer obtained by the present invention, and the above-mentioned compound can be used as they are, but compression molding, extrusion molding, injection molding methods used for general synthetic resins, By applying a molding method such as a blow molding method, it can be molded into various shapes such as pellets, films, sheets, pipes, rods, and containers. In addition, the ring-opening polymer, graft product and/or block polymer, and the blend include styrene,
It is also possible to use vinyl compounds such as vinyl chloride, acrylonitrile, and methyl methacrylate by graft polymerization, and it is also possible to use them by performing a so-called polymer reaction. As described above, the ring-opened polymer and its composition obtained by the present invention can be molded into any shape by various molding methods, and therefore can be used in a wide variety of fields. Examples include containers such as bottles, films and their secondary products (e.g. bags, packaging materials), daily necessities,
Examples include parts for machinery, parts for electrical appliances and lighting equipment, pipes, agricultural equipment and their parts. In addition, ring-opening polymers, graft products, and/or block polymers can be used as they are or by polymeric reaction to produce ion exchange resins, flocculants, adhesives, and paints. The polymers have improved oil resistance and mechanical properties compared to the unsaturated polymers. Hereinafter, the present invention will be explained in more detail with reference to Examples. In the examples, the reduced viscosity was measured using dimethylformamide as a solvent at a concentration of 0.1 g/dl and a temperature of 30°C. Furthermore, the polymerization activity was expressed relative to a certain amount (g) of the metal tungsten or molybdenum used as the reaction product. Example 1 35.1 g (0.152 mol) of tungsten trioxide, 37.9 g (0.182 mol) of phosphorus pentachloride, and 100 ml of orthodichlorobenzene were placed in a 500 ml three-necked flask that was completely purged with nitrogen, and the reaction system was heated to 150°C. After raising the temperature, the reaction was carried out at this temperature for 30 minutes with vigorous stirring. The solution portion (supernatant) turned from colorless to deep red before the reaction, and a considerable amount of yellow precipitate remained at the bottom of the flask. The tungsten concentration in this solution was measured using fluorescent X-rays and was found to be 0.40 mol/mol. In a glass autoclave with a volume of 1 that was completely purged with nitrogen, 1.0 ml of the supernatant liquid of the reaction product obtained by the above method and magnesium chloride [a commercially available product dried under reduced pressure at 200°C for 5 hours] were placed. , hereinafter referred to as "Compound (A)"] was charged and stirred vigorously at 75°C for 2 hours. Next, 500 ml of 1,2-dichloroethane, 400 g of 5-cyano-bicyclo[2.2.1]-heptene-2 (as a monomer,
3.36 mol) and 6.0 ml of a 1.2-dichloroethane solution having a concentration of 1.0 mol/diethylaluminum chloride were added, and polymerization was carried out at 85°C for 60 minutes with thorough stirring. After the polymerization was completed, the polymerization system was allowed to cool to approximately room temperature, 150 ml of 1,2-dichloroethane was added, and insoluble matter was removed by filtration using a glass filter.
Add 0.5 g of bis(2-hydroxy-3
-Tertiary-butyl-5-methylphenyl)methane was added, and the mixture was poured into methyl alcohol of about 5 times the amount of 1,2-dichloroethane to precipitate a polymer. After the polymer was filtered and separated, it was thoroughly washed with methyl alcohol, and the polymer was dried under reduced pressure at 50°C overnight. As a result, 283 g of a slightly yellow polymer was obtained. Polymerization activity is 3.845g/g-
W. Time. The reduced viscosity of this polymer is
It was 1.40. Examples 2 to 15 Instead of compound (A) used as the metal halogen compound in Example 1, aluminum chloride [hereinafter referred to as "compound (B)"], lithium chloride [hereinafter referred to as "compound (C)"] ], cupric chloride [hereinafter referred to as ``compound (D)''], zinc chloride [hereinafter referred to as ``compound (D)''],
(E)], cerium trifluoride (hereinafter referred to as "compound
(F)], aluminum fluoride (hereinafter referred to as "compound (G)"), titanium trichloride (hereinafter referred to as "compound (G)"),
(H)], tin dichloride (hereinafter referred to as "Compound (J)"), panadium oxychloride (hereinafter referred to as "Compound (K)"), magnesium hydroxychloride (hereinafter referred to as "Compound (L)"). ], antimony trichloride [hereinafter referred to as ``compound (M)''], chromium hexachloride [hereinafter referred to as ``compound (N)''], tellurium tetrachloride [hereinafter referred to as ``compound (P)''], and manganese chloride. [Hereinafter referred to as "compound (Q)"] was used in the amount shown in Table 1, and the reaction product of tungsten trioxide and phosphorus pentachloride was treated (prepared) at the treatment temperature shown in Table 1. Other than that,
The reaction product was prepared and polymerized in the same manner as in Example 1. The results are shown in Table 1.

[Table] Comparative Example 1 Polymerization was carried out in the same manner as in Example 1, except that compound (A) was not used. As a result, 132 g of polymer was obtained. In other words, the polymerization activity is 1.793g/g
-W・Time. Example 16 A reaction product was produced and polymerized in the same manner as in Example 1, except that 21.9 g (0.152 mol) of molybdenum trioxide was used. As a result, 126 g of polymer was obtained. In other words, the polymerization activity is 3.281g/g
−Mo・time. Examples 17 to 26 Polymerization was carried out in the same manner as in Example 1, except that 400 g of each of the monomers shown in Table 2 was used. The results are shown in Table 2.

[Table] Examples 27 to 31 Polymerization was carried out in the same manner as in Example 1, except that the organoaluminum compounds or reaction products thereof shown in Table 3 were used (however, the concentrations of the organoaluminum compounds used were different from each other). Same number of moles of aluminum concentration as Example 1). The results are shown in Table 3.

【table】

[Table] Examples 32 to 35 250 g of 5-cyano-bicyclo[2.2.1]-heptene-2 and each of the monomers shown in Table 4
Copolymerization was carried out in the same manner as in Example 1, except that 150 g was used. The results are shown in Table 4.

[Table] Examples 36 and 37 Polymerization was carried out in the same manner as in Example 1, except that after adding the monomers, 1.0 mol% of each of the molecular weight regulators shown in Table 5 was added to the monomers. Summer. The results are shown in Table 5.

[Table] Example 38 Dried cis-1,4-polybutadiene [manufactured by Japan Synthetic Rubber Co., Ltd., trade name JSR BR-01, Mooney viscosity (ML ₁₊₄ 100℃) 45, cis-1,4 content 97.5
%] was placed in a glass autoclave (No. 1) purged with nitrogen, and 500 ml of 1,2-dichloroethane was added and stirred to completely dissolve. To this solution was added 30.0 g of 5-cyano-bicyclo[2.2.1]-heptene-2 as a monomer and mixed well. Example 1 in a nitrogen-substituted autoclave No. 1
4.0 ml of the supernatant liquid of the reaction product of tungsten trioxide and phosphorus pentachloride used in 1, 20 ml of 1,2-dichloroethane, and 5.0 g of compound (A) were charged.
After heating and stirring at 70°C for 2 hours, 10.0 ml of a 1,2-dichloroethane solution containing the above-mentioned mixture of polybutadiene and monomer and diethylaluminichloride having a concentration of 1.0 mol/cm were added, and the mixture was stirred at 70°C for 2 hours. Polymerization was carried out. As a result, 48.0g
A polymer was obtained. When this polymer was subjected to infrared absorption spectrum analysis, both the characteristic absorption of 5-cyanobicyclo[2.2.1]-heptene-2 and the characteristic absorption of polybutadiene were observed.
The resulting polymer is a solvent for polybutadiene.
- When an extraction operation was performed using heptane, almost no extract was observed. Further, while the obtained polymer is soluble in toluene, the ring-opened polymer of 5-cyano-bicyclo[2.2.1]-heptene-2 is not soluble. From these facts, the polymer obtained in this example is a copolymer of 5-cyano-bicyclo[2.2.1]-heptene-2 and polybutadiene, or a copolymer of 5-cyano-bicyclo[2.2.1]-heptene-2 and polybutadiene. It is clear that cyano-bicyclo[2.2.1]-heptene-2 was grafted and/or block copolymerized. Comparative Example 2 5-cyanobicyclo[2.2.1]-heptene- Polymerization of 2 was carried out.
After the polymerization was completed, the polymer was precipitated, filtered, separated, washed and dried in the same manner as in Example 1. As a result, 73 g of polymer was obtained.

Claims (1)

[Scope of Claims] 1 Norbornene derivatives having at least one polar group or aromatic hydrocarbon group and/or
or a norbornadiene derivative or a mixture of these and at most 50 mol % of a cycloolefin compound in the absence or presence of an unsaturated polymer containing a carbon-carbon double bond (A) of the periodic table. A, A, B, B, an organometallic compound containing at least one metal selected from the group consisting of A and B group metals; (B) a reaction product of a tungsten and/or molybdenum oxide and a Lewis acid; and (C) an improved method for producing a ring-opening polymer, characterized in that ring-opening polymerization is carried out using a catalyst system obtained from a metal halogen compound.