JPH07103221B2 - Ring-opening polymer and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention has excellent heat resistance, transparency, water resistance, and
The present invention relates to a novel ring-opening polymer in which various properties such as chemical resistance, solvent resistance, mechanical properties such as dielectric properties and rigidity are balanced, and more specifically, a polycyclic norbornene-based ring-opening polymer and a method for producing the same. Regarding

Conventional technology Conventionally, polymethylmethacrylate, polycarbonate, etc. have been used as optical polymer materials, but the former has problems such as water absorption and the latter has problems such as birefringence during injection molding. It is becoming difficult to meet the increasing demands.

In recent years, a polymer using a polycyclic norbornene-based monomer has been developed as a polymer material that has improved these drawbacks. For example, JP-A-60-26024 describes that a hydride of a ring-opening copolymer of tetracyclododecenes and norbornenes has excellent transparency, water resistance, and heat resistance. JP-A-60-168708 and 61-292601 disclose that an addition polymer of a tetracyclododecene or a polycyclic norbornene-based monomer having a higher content and an α-olefin is transparent,
It is disclosed that it has excellent heat resistance, chemical resistance, water resistance and the like. As described above, the polycyclic norbornene-based polymer has excellent properties as an optical polymer, but it is generally difficult to obtain a monomer, and has a drawback that it is very expensive, In addition, there is a problem that the type is still limited.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention Therefore, the inventors of the present invention have diligently studied to develop a novel synthetic resin suitable as an optical polymer or a raw material thereof using a polycyclic norbornene-based monomer that can be obtained at a lower cost. As a result, a ring-opening polymer obtained by ring-opening polymerization of a polycyclic monomer having a specific structure, that is, pentacyclopentadecadiene and / or pentacyclopentadecene, together with other comonomers, if necessary, is thermally It was found that it is a polymer with excellent properties and well balanced mechanical properties such as water resistance, transparency, chemical resistance, solvent resistance, dielectric properties and rigidity, and is useful as various molded products. The present invention has been completed.

Means for Solving the Problems The gist of the present invention is (1) a repeating unit represented by the following general formula [I]: 100 to
5 mol% and repeating unit 0 represented by the following general formula [II]
A polycyclic norbornene ring-opening polymer having an intrinsic viscosity [η] of 0.01 to 20 dl / g measured in toluene at 25 ° C. (However, in the formula Represents a single bond or a double bond. ) And (2) 4,9,5,8-dimethano-3a, 4,4a, 5,8,8a, 9,9a-octahydro-1H-benzoindene and / or 4,9,5,8
-Dimethano-2,3,3a, 4,4a, 5,8,8a, 9,9a-decahydro-1
H-benzoindene (hereinafter sometimes referred to as "A component") 100 to 5 mol% and dicyclopentadiene and / or dihydrodicyclopentadiene (hereinafter referred to as "B component")
0 to 95 mol% of a repeating unit represented by the above general formula [I], characterized by polymerizing in the presence of a ring-opening polymerization catalyst. A polycyclic norbornene ring-opening polymer containing 0 to 95 mol% of the repeating unit represented by the general formula [II] and having an intrinsic viscosity [η] of 0.01 to 20 dl / g measured in toluene at 25 ° C. The manufacturing method of the coalescence is in.

The ring-opening polymer of the present invention has a component A as an essential component and a component B as a comonomer as a monomer, and can be produced by a known ring-opening polymerization method of a cyclic olefin. .

Hereinafter, each component of the present invention will be described in detail.

(Monomer) Component A used in the present invention is selected from the following two types of monomers. The first monomer is represented by the following general formula [III] pentacyclopentadecadiene ("4,9,5,8-dimethano-3a, 4,4a, 5,8,8a, 9,9a- Octahydro-1H-benzoindene ”) (hereinafter, this monomer is abbreviated as“ PCDE ”).

This PCDE can be obtained by subjecting cyclopentadiene and dicyclopentadiene to a Diels-Alder reaction, and separating from the reaction mixture by a technique such as distillation.

The other monomer of the component A is pentacyclopentadecene (“4,9,5,8-dimethano-2,3,3a, 4,4a, 5,8” represented by the following general formula [IV]. , 8a, 9,9a-decahydro-1H-benzoindene ") (hereinafter, abbreviated as" PCPD ").

This compound can be produced by subjecting cyclopentene and cyclopentadiene to a Diels-Alder reaction, and then subjecting the product and cyclopentadiene to a Diels-Alder reaction again.

The above PCDE and PCPD may be used alone,
It is also possible to mix and use them at an arbitrary ratio.

Component B used in the present invention is dicyclopentadiene (hereinafter sometimes abbreviated as “DCP”) and / or 2,3
-Dihydrodicyclopentadiene ("4,7-methano-2,
3,3a, 4,4a, 7,7a-hexahydroindene '', hereinafter `` HD
"CP" is sometimes abbreviated). These may be used alone or in an appropriate mixture.

In the present invention, the component A is 100 to 5 mol%, preferably 90 to 10 mol%, more preferably 80 to 20 mol% and the component B is 0 to 95 mol%, preferably 10 to 90 mol%, and further preferably Is used in a proportion of 20 to 80 mol%. Although the glass transition temperature rises as the use ratio of the component A rises, if the glass transition temperature becomes too high, there arises a problem that processing becomes difficult. Further, the glass transition temperature does not become sufficiently high unless the component A is used, and particularly when the polymer is hydrogenated for the purpose of improving the heat deterioration resistance and the light deterioration resistance, the glass transition temperature is significantly increased as compared with the original polymer. Decreases, which causes a problem in practical use.

In the present invention, other cycloolefins capable of ring-opening polymerization can be used in addition to the components A and B as long as they do not substantially impair the effects of the present invention. Specific examples of cycloolefins that can be used include, for example, cyclopentene, 5-methyl-2-norbornene, 5,
6-dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, ethylidene norbornene, 1,2-dihydrodicyclopentadiene, tetracyclodecene, methyltetracyclodecene, etc. A compound having one double bond is exemplified. These may be used usually in the range of up to 30% by weight based on the total monomers.

Further, among polycyclic norbornene-based monomers, there are compounds having two or more reactive double bonds, but in the case of such a compound, gelation of the polymer is likely to occur,
It is preferable to remove as much as possible.

The monomer mixture used in the present invention can be prepared by mixing the components A and B prepared in advance, or can be directly synthesized by heat treatment of DCP or heat treatment of DCP in the presence of cyclopentene. The conditions of heat treatment include DCP alone or DCP and cyclopentene under an inert gas atmosphere such as nitrogen gas at 120 to 250 ° C., preferably 15
A method of heating at a temperature of 0 to 230 ° C. for 0.5 to 20 hours, preferably 1 to 10 hours can be mentioned. The reaction form of the treatment may be either batch type or continuous type, and an inert solvent may be present in the reaction system.

The heat treated product is oily or waxy,
When only DCP is heat treated, unreacted DCP, PCDE
(Trimer of cyclopentadiene) as a main component, and a small amount of a symmetrical trimer of cyclopentadiene, that is, 1,4,5,8-dimethano-1,4 represented by the following formula [V]: 4a, 5,8,8
a, 9a-octahydro-9H-fluorene (hereinafter referred to as "DOF"
Abbreviated).

Such a heat-treated product can be used as it is, but when an insoluble component is present, it is preferable to remove the insoluble component by means such as filtration, and the composition of DCP and PCDE can be appropriately adjusted by distillation. It can also be used.

Further, from the heat-treated product of dicyclopentadiene and cyclopentene, a product containing unreacted DCP, the above-mentioned cyclopentadiene trimer, PCPD as a main component, and further unreacted cyclopentene is obtained in some cases. .
In this case as well, DCP can be used as it is, as is the case with DCP alone, or can be used after appropriately removing cyclopentene and DCP.

However, since the above DOF [V] produced as a by-product during heat treatment has two highly reactive double bonds, it cross-links during polymerization and causes gelation. ,
It is desirable to purify it to preferably 10% by weight or less, more preferably 5% by weight or less.

Further, in the heat treatment, components such as olefins such as propylene and butene, cycloolefins such as dihydrodicyclopentadiene, dienes such as styrenes, putadiene and isoprene can be made to coexist. In this case, various norbornene-based compounds are produced as by-products in addition to PCDE, but if their ratio is 30% by weight or less based on the total monomers, they are included in the scope of the present invention.

Further, in the polymerization, in addition to the components A and B, chain monoolefins such as butene-1, pentene-1, hexene-1, octene-1, butene-2, pentene-2, 1,4-hexadiene The chain-like non-conjugated diolefins may be added in the range of up to about 10 mol% for controlling the molecular weight.

(Polymerization catalyst) A ring-opening polymer of these monomers is produced by a usual method for polymerizing norbornenes. Examples of the polymerization catalyst include ruthenium, rhodium, palladium, osmium,
Platinum group metal compounds such as iridium and platinum (for example, Japanese Patent Publication No. 46-14910), titanium, vanadium,
Examples include systems of transition metal compounds such as molybdenum and tungsten and organometallic compounds of Group I-IV of the periodic table,
A third component such as a tertiary amine may be combined with this catalyst system (for example, JP-B-41-20111 and JP-B-57-17883).
No. 57-61044, JP-A-54-86600, JP-A-58-1
No. 27728).

The polymerization catalyst is not particularly limited as long as it is a metal compound capable of ring-opening polymerization of these monomers, but is preferably a catalyst system containing a transition metal compound such as titanium tetrahalide and an organometal such as an organoaluminum compound. Alternatively, it is a catalyst system in which a third component such as an aliphatic or aromatic tertiary amine is combined.

Below, the specific example of a polymerization catalyst is given.

Transition metal compound As the metal compound, transition metal compounds such as titanium, vanadium, tungsten and molybdenum are preferable, and specifically, there are halides, oxyhalides, oxides, carbonyl compounds, organic ammonium salts and the like of these transition metals. .

Specific examples include TiCl ₄ , TiBr ₄ , VOCl ₃ , VOBr ₃ , WBr ₂ , WBr ₄ , WBr ₆ , WC
l ₂ , WCl ₄ , WCl ₅ , WCl ₆ , WF ₄ , WI ₂ , WI ₄ , WOBr ₄ , WOC
l ₄ , WOF ₄ , MoBr ₂ , MoBr ₃ , MoBr ₄ , MoCl ₄ , MoCl ₅ , Mo
F ₄ , MoOCl ₄ , MoOF ₄ , WO ₂ , H ₂ WO ₄ , NaWO ₄ , K ₂ WO ₄ , (NH ₄ ).
₂ WO ₄ , CaWO ₄ , CuWO ₄ , MgWO ₄ , (CO) ₅ WC (OCH ₃ ) (CH ₃ ), (C
O) ₅ WC (OC ₂ H ₅ ) (CH ₃ ), (CO) ₅ WC (OC ₂ H ₅ ) (C ₄ H ₅ ), (CO) ₅ MoC
(OC ₂ H ₅ ) (CH ₃ ), (CO) ₅ Mo = C (OC ₂ H ₅ ) (N (C ₂ H ₅ ) ₂ ), tridecyl ammonium molybdate,
Examples include tridecyl ammonium tungstate.

Examples of the organometallic compound include organometallic compounds of groups I to IV of the periodic table, for example, organoaluminum compounds, organotin compounds or lithium, sodium,
There are compounds such as magnesium, zinc, cadmium and boron.

Examples of the organic aluminum compound include trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, triphenyl aluminum, tribenzyl aluminum, diethyl aluminum monochloride, di- n-pyropyr aluminum monochloride,
Di-isobutyl aluminum monochloride, di-n-butyl aluminum monochloride, diethyl aluminum monobromide, diethyl aluminum monoiodide, diethyl aluminum monohydride, di-n-propyl aluminum monohydride, diisobutyl aluminum monohydride, methyl aluminum sesquichloride , Ethyl aluminum sesquibrolide, isobutyl aluminum sesquichloride, ethyl aluminum dichloride, ethyl aluminum dibromide, propyl aluminum dichloride, isobutyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum diiodide and the like.

Examples of the organic tin compound include tetramethyltin, diethyldimethyltin, tetraethyltin, dibuethyldiethyltin, tetrabutyltin, tetraisocumyltin, tetraphenyltin, triethyltin fluoride, triethyltin chloride, triethyltin bromide and triethyltinio. Examples thereof include zido, diethyltin difluoride, diethyltin dichloride, diethyltin bromide, diethyltin iodide, ethyltin trifluoride, ethyltin trichloride, ethyltin tribromide and ethyltin triiodide. Other n-butyllithium, n
-Pentyl sodium, methyl magnesium iodide,
Ethylmagnesium bromide, methylmagnesium bromide, n-propylmagnesium chloride, t-butylmagnesium chloride, allylmagnesium chloride,
Examples include diethyl zinc, diethyl cadmium, trimethyl boron, triethyl boron, tri-n-butyl-boron and the like.

Third Component A third component can be added to the above catalyst system to enhance the polymerization activity and improve the selectivity of ring-opening polymerization. As specific examples, molecular oxygen, alcohol, ether, peroxide, carboxylic acid, acid anhydride, acid chloride, ester, ketone,
Examples thereof include nitrogen-containing compounds, sulfur-containing compounds, halogen-containing compounds, molecular iodine, and other Lewis acids. Among them, aliphatic or aromatic tertiary amines are preferable, and specific examples thereof include triethylamine, dimethylaniline, tri-n-butylamine, pyridine, α-picoline and the like.

(Solvent) The ring-opening polymerization of the present invention can be carried out without using a solvent, but can also be carried out in an inert organic solvent.

Specific examples include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as n-pentane, hexane and heptane, alicyclic hydrocarbons such as cyclohexane, methylene dichloride, dichloroethane, dichloroethylene and tetrachloro. Examples thereof include halogenated hydrocarbons such as ethane, chlorobenzene, dichlorobenzene, and trichlorobenzene, and two or more kinds of these may be mixed and used.

(Polymerization temperature) The temperature condition of the ring-opening polymerization is not particularly limited,
It is usual to select any temperature from 20 ° C to 100 ° C.

(Polymerization pressure) Generally, it is preferable to select the polymerization pressure condition from the range of 0 to 50 kg / cm ² .

(Ring-opening polymer) The novel ring-opening polymer has an intrinsic viscosity [η] measured at 25 ° C in toluene of 0.01 to 20 dl / g, preferably 0.1 to 10 dl / g. When [η] is in the above range, heat resistance, water resistance, transparency, chemical resistance, workability, mechanical properties and the like are good.

The ring-opening polymer of the present invention has a high glass transition temperature and excellent heat resistance, but the B component is 0 to 95 mol% relative to the A component.
Glass transition temperature of about 14
It can be controlled in the range of 0 ° C to 200 ° C, preferably 150 ° C to 180 ° C.

(Molding) The ring-opening polymer of the present invention can be molded by a known method. Further, in the molding process, various additives such as inorganic and organic fillers, stabilizers, antistatic agents and lubricants may be added.

(Use) The ring-opening polymer of the present invention has excellent heat resistance as is clear from the fact that it has a high glass transition temperature, and has a well-balanced transparency, chemical resistance and mechanical properties. Therefore, it is useful in various fields as various molded products.

If the ring-opening polymer is hydrogenated by a conventional method, it is possible to obtain a polymer having improved heat deterioration resistance and light deterioration resistance in addition to the above characteristics. The ring-opening polymer and the hydrogenated product thereof of the present invention are, for example, optical fields such as optical lenses, optical disks, optical fibers, glass window applications, water tanks for electric irons, microwave oven products, substrates for liquid crystal displays, printed circuit boards, It can be used in various fields such as high frequency circuit boards, electric fields such as transparent conductive sheets and films, medical fields such as syringes, pipettes and animal gauges, chemical fields, camera bodies, various instrument housings, films, sheets and helmets.

Examples The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 15 g of PCDE represented by the general formula (III) and 60 parts of toluene were placed in a 500 ml separable flask that was sufficiently dried and purged with nitrogen.
ml was added. Continue to triethylaluminum 1.5m
mol and titanium tetrachloride (0.30 mmol) were added, and the mixture was reacted at 25 ° C. for 4 hours with stirring. Then, the target product was precipitated with acetone / isopropyl alcohol (1/1), filtered, and then dissolved again in toluene. By further precipitating with an acetone / isopropyl alcohol (1/1) solvent, filtering, and drying,
I got the object. The yield was 18%. As a result of proton NMR analysis of the obtained polymer, absorption due to the olefin double bond proton and the 5-membered cycloolefin in-ring double bond proton was observed between δ = 5.0 to 5.5 ppm,
On the other hand, no absorption (δ = 5.6 to 6.0 ppm) due to the double bond proton in the norbornene ring was observed. further,
Since the double bond-related proton absorption intensity with respect to the absorption intensity derived from all protons was almost the same as the theoretical value (22.2%), it was confirmed that the above polymer was subjected to ring-opening polymerization. The glass transition temperature (by DSC) of this ring-opening polymer is 2
The intrinsic viscosity measured at 25 ° C in toluene is 0.1 ° C.
It was 30 dl / g. The polymer was soluble in benzene, toluene, cyclohexane, carbon tetrachloride and carbon disulfide at room temperature.

Example 2 To a well-dried, nitrogen-substituted 500 ml separable flask, 80 g of the monomer mixture shown in Table 1 was added, and 220 g of toluene and 1-hexene were added to 1.
0 mol%, 12 mmol of triethylaluminum, 36 mmol of triethylamine, 2.4 mmol of titanium tetrachloride are sequentially added, and
After reacting for 2 hours at ℃, it was precipitated and washed with acetone / isopropyl alcohol (1/1), and dried to obtain the target polymer.

As a result of H ¹ -NMR analysis, the absorption due to the double bond of the norbornene ring (δ = 5.6 to 6.0 ppm) disappeared, and the absorption due to the 5-membered ring and the olefin main chain (δ = 5.0 to 5.5 ppm)
It was concluded that the polymer according to this example was a ring-opening polymer because it was confirmed that the polymer was all shifted to.

The physical properties of the obtained polymer are shown in Table 1. The repeating unit content in the polymer was calculated based on the absorption peak area of the double bond proton in H ¹ -NMR. The light transmittance was measured at 830 nm using a 15 μ-thick thin film prepared by the casting method. The solvent resistance was determined by immersing the above thin film in ethyl acetate or acetone at room temperature for 20 hours and observing whether there was a change in appearance. Further, regarding the chemical resistance, the above thin film was immersed in 28% ammonia water at room temperature for 20 hours, and the change in its appearance was observed.

For comparison, Table 1 shows the physical properties of the obtained polymer when only dicyclopentadiene was used as the monomer.

Example 3 600 g of dicyclopentadiene was placed in an autoclave equipped with a stirrer having a capacity of 1, the inside of the reactor was replaced with nitrogen, the temperature was raised to 180 ° C. with stirring, and the heat treatment reaction was carried out for 4 hours, followed by vacuum distillation. . 263 g of CPD trimer was obtained at 2 torr and 110 to 120 ℃. As a result of analysis by gas chromatography, the composition of the CPD trimer was PCDE84.5% by weight, DOF1
4.7% by weight and 0.8% by weight for others.

In a 500 ml separable flask that was thoroughly dried and purged with nitrogen, 40 g of the above trimer monomer and 260 ml of toluene were added, and 12 mmol of triethylaluminum and 36 mmo of triethylamine
1, titanium tetrachloride (2.4 mmol) were added, and the mixture was reacted at room temperature for 2 hours. After that, acetone / isopropyl alcohol (1 /
The target substance was precipitated in 1), filtered, and then redissolved in toluene. In addition, acetone / isopropyl alcohol (1 /
1) The desired product was obtained by precipitation with a solvent, filtration, and drying. The yield was 25g. The glass transition temperature (by DSC) of this ring-opening polymer was 203 ° C., and the intrinsic viscosity measured in toluene at 25 ° C. was 0.21 dl / g. The polymer was soluble in benzene, toluene, cyclohexane, carbon tetrachloride and carbon disulfide at room temperature.

EFFECTS OF THE INVENTION The novel ring-opening polymer of the present invention is a polymer having excellent heat resistance and having mechanical balance such as transparency, water resistance, chemical resistance, solvent resistance, dielectric properties and rigidity. Therefore, it has an excellent effect that it can be used in a wide range of fields including the optical field.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshimata Matsui 1-2-1 Nikko, Kawasaki-ku, Kawasaki-shi, Kanagawa Zeon Corporation R & D Center (72) Io Natsume Io Kawasaki-ku, Kawasaki-shi, Kanagawa Night light 1-2-1 Nihon Zeon Co., Ltd. Research and Development Center (56) Reference JP-A-63-145324 (JP, A)

Claims (3)

[Claims] 1. A repeating unit represented by the following general formula [I]:
100 to 5 mol% and 0 to 95 mol% of the repeating unit represented by the following general formula [II], and the intrinsic viscosity [η] measured in toluene at 25 ° C. is 0.01 to 20 dl / g. Ring norbornene ring-opening polymer. (However, in the formula Represents a single bond or a double bond. ) 2. 4,9,5,8-Dimethano-3a, 4,4a, 5,8,8a, 9,9a
-Octahydro-1H-benzoindene and / or 4,
9,5,8-Dimethano-2,3,3a, 4,4a, 5,8,8a, 9,9a-decahydro-1H-benzoindene 100 to 5 mol% and dicyclopentadiene and / or dihydrodicyclopentadiene 100 to 5 mol% of the repeating unit represented by the following general formula [I] characterized by polymerizing a monomer or a monomer mixture containing 0 to 95 mol% in the presence of a ring-opening polymerization catalyst and the following general formula [II ] 0 to 95% by weight of repeating unit
And a method for producing a polycyclic norbornene ring-opening polymer having an intrinsic viscosity [η] of 0.01 to 20 dl / g measured in toluene at 25 ° C. (However, in the formula Represents a single bond or a double bond. ) 3. The polycyclic norbornene according to claim (2), wherein the ring-opening polymerization catalyst is an organoaluminum compound and titanium tetrahalide, or a combination of these catalysts and a tertiary amine. For producing a ring-opening polymer.