JPH07121981B2 - Ring-opening polymer hydrogenated product and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel ring-opening polymer hydrogenation having excellent transparency, solvent resistance, chemical resistance, and balanced mechanical strength and flexibility. More particularly, it relates to a hydrogenated product of a polycyclic norbornene ring-opening polymer and a method for producing the same.

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 ever more sophisticated demands.

Further, examples of the soft transparent sheet having excellent flexibility include sheets of vinyl chloride resin, polyethylene, polypropylene and the like. However, the vinyl chloride resin sheet is
Since it contains a plasticizer, it has poor solvent resistance, and sheets such as polyethylene and polypropylene have poor transparency.

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, in JP-A-60-26024, a hydride of a ring-opening polymer of tetracyclododecenes or a ring-opening copolymer of tetracyclododecenes and norbornenes is transparent,
It is described that it is excellent in water resistance and heat resistance.

However, the hydride of a ring-opening polymer of tetracyclododecenes does not always have good moldability, and
A hydride of a ring-opening copolymer of tetracyclododecenes and norbornenes has an insufficient balance between mechanical strength and flexibility.

Further, Japanese Patent Publication No. 58-43412 discloses that a hydride of a dicyclopentadiene ring-opening polymer can be easily subjected to hot melt molding to give a transparent and tough sheet. Hydrides are tough but inferior in flexibility.

On the other hand, a norbornene ring-opening polymer (US Pat. No. 2,721,189
U.S. Pat. No. 2,932,630) and ring-opening copolymers of norbornene and dicyclopentadiene.
51-124189 gazette) and the like, but polymers or copolymers using polycyclic norbornene-based monomers are known, but none of them are hydrogenated, and are inferior in oxidation deterioration resistance, It is unsuitable as a material for use.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention An object of the present invention is to provide a novel ring-opening weight having excellent transparency, solvent resistance, chemical resistance, resistance to oxidative deterioration, and good balance between mechanical strength and flexibility. To provide a combined hydrogenated product.

The present inventors have conducted diligent research to develop a novel synthetic resin suitable as an optical polymer or a raw material thereof using a polycyclic norbornene-based monomer, and as a result, opened norbornenes or norbornenes and dicyclopentadiene The hydrogenated product of the ring-opening polymer obtained by polymerization is a polymer that is excellent in transparency, solvent resistance, chemical resistance, resistance to oxidative deterioration, and has a good balance of mechanical strength and flexibility. They have found the present invention and have completed the present invention based on the findings.

Means for Solving the Problems That is, the gist of the present invention is (1) (A) at least one repeating unit selected from the repeating unit represented by the following general formula [I], its alkyl-substituted or alkylidene-substituted A unit of 100 to 10 mol% and (B) a repeating unit represented by the following general formula [II] or an alkyl-substituted product thereof in an amount of 0 to 90 mol%, and the intrinsic viscosity measured in toluene at 25 ° C. [η ] Is 0.
01 to 20 dl / g and constitutes the main chain A polycyclic norbornene-based ring-opening polymer hydrogenated product in which at least 50% of is a single bond, and (However, in the formula Represents a single bond or a double bond. (2) (A) 100 to 10 mol% of a repeating unit represented by the following general formula [I ′], at least one repeating unit selected from its alkyl-substituted or alkylidene-substituted compounds, and (B) the following general formula Containing the repeating unit represented by [II '] or its alkyl-substituted 0-90 mol%, and having an intrinsic viscosity [η] measured in toluene at 25 ° C of 0.
The main chain is characterized in that some or all of the olefinic unsaturated groups contained in the polycyclic norbornene ring-opening polymer of 01 to 20 dl / g are hydrogenated with hydrogen using a hydrogenation catalyst. Do Of the polycyclic norbornene ring-opening polymer hydrogenated product having at least 50% of single bonds.

(However, in the formula Represents a single bond or a double bond. ) The ring-opening polymer used in the present invention is a monomer (A)
Unsubstituted or substituted norbornene (hereinafter sometimes referred to as “component A”) alone, or norbornenes and (B) dicyclopentadiene, that is, dicyclopentadiene and its alkyl-substituted product, and / or dihydrodicyclopentadiene That is, 2,3-dihydrodicyclopentadiene and its alkyl-substituted product (hereinafter sometimes referred to as "component B") are used as essential components, and they are produced by a known ring-opening polymerization method for cyclic olefins. You can Then, the hydrogenated products of these ring-opening polymers can be produced by using a usual hydrogenation reaction method.

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

(Monomer) The component A used in the present invention is an unsubstituted or substituted norbornene (hereinafter sometimes abbreviated as “NB”). As substituted norbornene, 5-methyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5-ethyl-
There are alkyl-substituted norbornenes such as 2-norbornene, 5-butyl-2-norbornene, or alkylidene-substituted norbornenes such as ethylidene norbornene.

The component B used in the present invention includes dicyclopentadiene (hereinafter sometimes abbreviated as “DCP”) and 2,3-dihydrodicyclopentadiene (“4,7-methano-2,3,3a, 4,7”). , 7a−
“Hexahydroindene”, hereinafter sometimes abbreviated as “HDCP”), and alkyl substitution products thereof such as methyl, ethyl, propyl and butyl.

Each of these monomer components may be used alone or in an appropriate mixture.

In the present invention, the component A is used in a proportion of 100 to 10 mol%, preferably 90 to 20 mol%, and the component B is 0 to 90 mol%, preferably 10 to 80 mol%.

The mechanical strength increases as the use ratio of the B component increases, but if it is too much, the improvement of the mechanical strength becomes insufficient and the flexibility tends to decrease.

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 a reactive double bond such as cyclopentene, cyclooctene, or 5,6-dihydrodicyclopentadiene.
Examples thereof include compounds having individual groups.

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.

Further, in the polymerization, in addition to the components A and B, butene-1, pentene-1, hexene-1, octene-
Chain monoolefins such as 1, butene-2, pentene-2, and 1,4-hexadiene, and chain 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 Examined Patent Publication No. 46-14910) or transition metal compounds such as titanium, vanadium, molybdenum, and tungsten, and systems of group I-IV organometallic compounds The catalyst system may be combined with a third component such as a tertiary amine (see, for example, JP-B-41-20111, JP-B-5711).
-17883, JP-B-57-61044, JP-A-54-86600,
JP-A-58-127728, etc.).

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 , (N
H ₄ ) ₂ WO ₄ , CaWO ₄ , CuWO ₄ , MgWO ₄ , (CO) ₅ WC (OCH ₃ ).
(CH ₃ ), (CO) 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 M
o = C (OC ₂ H ₅ ) (N (C ₂ H ₅ ) ₂ ), tridecyl ammonium molybdate, tridecyl ammonium tungstate, and the like.

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 sesquibromide, isobutyl aluminum sesquichloride, ethyl aluminum dichloride, ethyl aluminum dibromide, propyl aluminum dichloride, isobutyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum diiodide and the like.

As the organic tin compound, tetramethyltin, diethyldimethyltin, tetraethyltin, dibutyldiethyltin, tetrabutyltin, tetraisocumyltin, tetraphenyltin, triethyltin fluoride, triethyltin chloride, triethyltin bromide, triethyltin iodide. , Diethyltin difluoride, diethyltin dichloride, diethyltin bromide, diethyltin diiodide, ethyltin trifluoride, ethyltin trichloride, ethyltin tribromide, ethyltin triiodide and the like. 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) Although the ring-opening polymer used in the present invention can be polymerized without using a solvent, it can be polymerized 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 .

(Hydrogenation) The hydrogenated product of the ring-opening polymer of the present invention is prepared by hydrogenating the above-mentioned ring-opening polymer or ring-opening copolymer to obtain an olefinic unsaturated group (double bond and unsaturated ring It can be obtained by saturating a part or all of the double bond), whereby the heat deterioration resistance and light deterioration resistance of the polymer can be further improved. Hydrogenation rate is 100% when all double bonds of ring-opening polymer are saturated by hydrogenation
Then, theoretically, there is a range of 0 to 100%, and in practice, it can be arbitrarily selected within that range, but in order to improve the heat deterioration resistance and the light deterioration resistance, 50% of the main chain double bond is required. % Or more must be hydrogenated. The hydrogenation reaction of this ring-opening copolymer is carried out by a usual method. The hydrogenation catalyst can be used as long as it is generally used for hydrogenating an olefin compound, and is not particularly limited, but examples thereof include the following. As the heterogeneous catalyst, nickel, palladium, platinum or these metals are carbon, silica, diatomaceous earth, alumina,
Examples include solid catalysts supported on a carrier such as titanium oxide, such as nickel / silica, nickel / diatomaceous earth, palladium / carbon, palladium / silica, palladium / diatomaceous earth, and palladium / alumina. Further, as the homogeneous catalyst, those based on a metal of Group VIII of the periodic table, for example, nickel naphthenate / triethylaluminum, cobalt octenoate / n-butyllithium, nickel acetylacetonate / triethylaluminum, etc. , Co compounds and organometallic compounds of metals of groups I to III of the periodic table, or Rh compounds.

The hydrogenation reaction is a homogeneous system or a heterogeneous system, depending on the type of catalyst, under a hydrogen pressure of 1 to 150 atm, 0 to 180 ° C., preferably
It is carried out at 20-100 ° C. The hydrogenation rate can be arbitrarily adjusted by changing the hydrogen pressure, the reaction temperature, the reaction time, the catalyst concentration and the like, but in order for the hydrogenated product to exhibit excellent heat deterioration resistance and light deterioration resistance, It is necessary that 50% or more of the main chain double bonds in the
The hydrogenation rate is 80% or more, more preferably 90% or more.

(Ring-Opening Polymer Hydrogenated Product) The ring-opening polymer used in the present invention has an intrinsic viscosity [η] measured at 25 ° C. in toluene of 0.01 to 20 dl / g, preferably 0.1.
However, the [η] of the ring-opening polymer hydrogenated product of the present invention is also 0.01 to 20 dl / g, preferably 0.1 to 10 d.
l / g. When [η] is in the above range, heat resistance, water resistance, transparency, chemical resistance, solvent resistance, processability and mechanical properties are good.

Hydrogenated products of homopolymers of dicyclopentadiene (DCPs) have excellent toughness but poor flexibility. Further, even if the norbornenes (NBs) and the tetracyclododecenes (TCDs) are copolymerized, the mechanical strength is insufficiently improved and the flexibility is impaired.

On the other hand, the hydrogenated product of the ring-opening polymer of the present invention is a homopolymer of the A component (NBs) or a component and a B component (DCP).
, HDCPs), it is possible to balance mechanical strength and flexibility.

Specifically, the hydrogenated product of the present invention has a tensile strength of about 500K.
g / cm ² or more, the bending can be properly controlled in the range of elastic modulus from about 7,000 to about 11,000Kg / cm ^2, and are balanced therebetween.
Therefore, the tensile strength is not improved and only the flexural modulus is increased without impairing the balance between mechanical strength and flexibility.

Furthermore, it is also excellent in light transmittance, water resistance, chemical resistance, solvent resistance, etc., and is used for optical materials, transparent sheets, films,
It is suitable as a coating agent and the like.

Further, the hydrogenated product of the ring-opening polymer of the present invention has further improved heat deterioration resistance and light deterioration resistance as compared with the ring-opening polymer used.

(Molding) The hydrogenated product of 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 hydrogenated product of the ring-opening copolymer of the present invention is excellent in heat deterioration resistance and light deterioration resistance, as is clear from the fact that unsaturated groups are hydrogenated, and also has transparency and water resistance. Since it is a polymer having excellent chemical resistance and having well-balanced mechanical strength and flexibility, it is useful in various fields as various molded articles.

For example, optical lenses, optical disks, optical fibers,
Optical fields such as glass window applications, water tanks for electric irons, microwave oven products, substrates for liquid crystal displays, printed circuit boards,
High frequency circuit boards, electrical fields such as transparent conductive sheets and films, medical fields such as syringes, pipettes and animal gauges, chemical fields, camera bodies, various instrument housings,
It can be used in various fields such as films, sheets and helmets.

EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Parts are based on weight unless otherwise specified.

Example 1 In a reactor that had been sufficiently dried and purged with nitrogen, norbornene (N
B) 100 parts and 300 parts of toluene were charged. Then 1
Molar concentration of triethylaluminum in toluene 16
Parts, 4 parts of triethylamine and 3 parts of a toluene solution of titanium tetrachloride having a molar concentration of 1 were added and reacted at 20 ° C. for 2 hours. The reaction solution was poured into acetone / isopropyl alcohol (1/1) to coagulate the polymer, which was filtered and dried to obtain 70 parts of polymer. The intrinsic viscosity of this polymer measured at 25 ° C. in toluene was 1.37 dl / g.

20 parts of the above polymer was dissolved in 480 parts of cyclohexane, and 2 parts of palladium-carbon catalyst was used, and the hydrogen pressure was 80 kg / c.
Hydrogenation reaction was carried out at m ² and temperature of 140 ° C. for 4 hours. The obtained polymer solution was filtered to remove the catalyst, then poured into acetone / isopropyl alcohol (1/1) to coagulate, and the precipitate was filtered and dried to obtain 17 parts of a hydrogenated polymer.

As a result of analysis by ¹ H-NMR spectrum of this hydrogenated polymer, absorption of protons due to double bond disappeared,
It was confirmed that hydrogenation was almost complete (hydrogenation rate 100%).

The intrinsic viscosity of this hydrogenated polymer was 1.34 dl / g when measured in toluene at 25 ° C.

This hydrogenated polymer was compression molded at 130 ° C. to prepare a plate having a diameter of 10 cm and a thickness of 2 mm. The formed plate was flexible. The tensile strength (measured according to ASTM D638) was 500 Kg / cm ² , and the flexural modulus (measured according to ASTM D790) was 7,000 Kg / cm ² . The light transmittance of this molded plate (measured at 830 nm) is 85%.
And was excellent. The water absorption rate (weight change rate after immersion at 25 ° C. for 24 hours) was measured and found to be 0.1% or less.

Regarding the solvent resistance, the appearance of the plate after immersing the molded plate in Freon R113, acetone and ethyl acetate at 25 ° C. for 24 hours was observed. As a result, no change in appearance was observed.

From the above results, the ring-opening polymer hydrogenated product of the present invention is a polymer in which mechanical strength and flexibility are well balanced, and further, various physical properties such as transparency, water resistance, and solvent resistance. It turns out that is good.

Examples 2 to 4 Ring-opening copolymerization of NB and dicyclopentadiene (DCP), hydrogenation and compression molding were carried out in the same manner as in Example 1 except that the composition ratios of the monomers were changed to those shown in Table 1. Was done.

The composition ratio (mol%) of the units derived from each component of NB and DCP in the ring-opening copolymer was calculated based on the result of analysis by proton NMR spectrum and the analysis of the amount of residual monomer after polymerization by gas chromatography. did.

Physical properties of the obtained polymer and molded plate measured in the same manner as in Example 1 are shown in Table 1. Table 1 also shows the physical property values in Example 1.

Comparative Examples 1-2 For comparison, also in the case of using only DCP as a monomer and NB and tetracyclododecene (TCD), a polymer and a molded plate were obtained in the same manner as in Examples 1 to 4 and their physical properties were obtained. The values were measured and are shown in Table 1.

As is clear from Table 1, the hydrogenated ring-opening polymer of the present invention has a good balance between tensile strength and flexural modulus. On the other hand, DCP homopolymer is excellent in toughness, but inferior in flexibility, and when TCD is used as a comonomer instead of DCP, there is no improvement in tensile strength and only the flexural modulus is increased. It is increased and the mechanical strength and flexibility are not balanced.

Advantageous Effects of Invention The novel ring-opening polymer hydrogenated product of the present invention is a polymer having excellent transparency, water resistance, solvent resistance, and the like, and has a good balance between mechanical strength and flexibility. Because it is a polymer,
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) Io Natsuume Io 1-2-1 Nikko, Kawasaki-ku, Kawasaki-shi, Kanagawa Nihon Zeon Co., Ltd. Research and Development Center (56) Reference JP-A-1-168725 (JP, 168725) A) JP-A 1-168724 (JP, A) JP-A 1-158029 (JP, A) JP-A 64-24826 (JP, A) JP-A 63-218726 (JP, A) JP-A 51 -80400 (JP, A)

Claims (2)

[Claims] (A) 100 to 10 mol% of at least one repeating unit selected from the repeating unit represented by the following general formula [I], its alkyl-substituted or alkylidene-substituted compound, and (B) the following general formula: Containing the repeating unit represented by [II] or its alkyl-substituted 0 to 90 mol%, and having an intrinsic viscosity [η] measured at 25 ° C. in toluene of 0.
01 to 20 dl / g and constitutes the main chain A hydrogenated product of a polycyclic norbornene ring-opening polymer, in which at least 50% of is a single bond. (However, in the formula Represents a single bond or a double bond. ) 2. (A) 100 to 10 mol% of a repeating unit represented by the following general formula [I '], at least one repeating unit selected from its alkyl-substituted or alkylidene-substituted compounds, and (B) the following general It contains a repeating unit represented by the formula [II ′] or an alkyl-substituted product thereof in an amount of 0 to 90 mol%, and has an intrinsic viscosity [η] measured in toluene at 25 ° C. of 0.
The main chain is characterized in that some or all of the olefinic unsaturated groups contained in the polycyclic norbornene ring-opening polymer of 01 to 20 dl / g are hydrogenated with hydrogen using a hydrogenation catalyst. Do A method for producing a hydrogenated product of a polycyclic norbornene ring-opening polymer having at least 50% of single bonds. (However, in the formula Represents a single bond or a double bond. )