JP2534086B2 - Ring-opening copolymer hydrogenated product and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel ring-opening copolymer hydrogenated product having excellent heat resistance, optical properties and moldability, and more specifically,
The present invention relates to a hydrogenated product of a polycyclic norbornene ring-opening copolymer 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 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 discloses that a hydride of a ring-opening polymer of tetracyclododecenes or a ring-opening copolymer of tetracyclododecenes and norbornenes has high transparency, water resistance and heat resistance. It is described as being excellent. However, the hydride of a ring-opening polymer of tetracyclododecenes does not necessarily have good moldability, and it is hard to say that the birefringence value is so small that the required physical properties are sufficiently satisfied. Further, hydrides of ring-opening copolymers of tetracyclododecenes and norbornenes also have similar problems, and the above problems occur when the copolymerization ratio of norbornenes increases to about 40 to 50 mol%. Although it is somewhat improved, the glass transition temperature (Tg) is as low as 90 to 100 ° C, and the heat resistance is not always sufficient.

Further, JP-B-58-43412 describes that a hydride of a dicyclopentadiene ring-opening polymer can be easily subjected to hot melt molding to give a transparent and tough sheet, This hydride has a glass transition temperature (Tg) of about 95 ° C. and is insufficient in heat resistance for use as an optical disk.

On the other hand, even a polymer using a polycyclic norbornene-based monomer, which is not hydrogenated, is inferior in resistance to oxidative deterioration and is not suitable as an optical material.

Problems to be Solved by the Invention An object of the present invention is to provide a novel polymer material excellent in heat resistance, optical properties and moldability.

A further object of the present invention is to obtain a hydrogenated product of a polycyclic norbornene ring-opening copolymer which gives a molded product having a high glass transition temperature and a small optical strain.

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, tetracyclododecenes, dicyclopentadiene and / or Alternatively, the hydrogenated product of the ring-opening copolymer obtained by ring-opening copolymerization with dihydrodicyclopentadiene is a polymer that has excellent thermal properties and is less likely to cause optical distortion in the molded product, and also has good moldability. Therefore, the present invention has been completed based on the finding.

Means for Solving the Problems According to the present invention, (A) the repeating unit represented by the following general formula [I] or its alkyl-substituted product is 10 mol% or more, 50
Less than mol% and (B) the repeating unit represented by the following general formula [II] or its alkyl-substituted product exceeds 50 mol% and 90 mol% or less (provided that the repeating unit represented by the general formula [II] is repeated. The unit is 50% by weight or more in the copolymer.), And
Intrinsic viscosity [η] measured in toluene at 25 ℃ is 0.01-20
A polycyclic norbornene ring-opening copolymer hydrogenated product having a dl / g and having at least 50% of the (C ... C) bonds constituting the main chain is a single bond is provided.

(In the formula, ... represent a single bond or a double bond.) Further, according to the present invention, (A) a repeating unit represented by the following general formula [I '] or an alkyl-substituted compound thereof (10 mol) %
As described above, less than 50 mol% and (B) the repeating unit represented by the following general formula [II '] or its alkyl-substituted product exceeds 50 mol% and 90 mol% or less (provided that the general formula [II'] The repeating unit represented by is 50% by weight or more in the copolymer.) And the intrinsic viscosity [η] measured in toluene at 25 ° C is 0.01 to 20 dl / g. Part or all of the olefinically unsaturated groups contained in the copolymer are hydrogenated with hydrogen using a hydrogenation catalyst to convert at least 50% of the carbon-carbon double bonds constituting the main chain into single bonds. A method for producing a hydrogenated product of a polycyclic norbornene copolymer, characterized by comprising:

(However, in the formula, ... represents a single bond or a double bond.) The ring-opening copolymer used in the present invention, as a monomer,
(A) Tetracyclododecene, that is, tetracyclododecene and its alkyl-substituted compound (hereinafter referred to as “A component”)
And (B) dicyclopentadiene, that is, dicyclopentadiene and its alkyl-substituted product, and / or dihydrodicyclopentadiene,
That is, it uses 2,3-dihydrodicyclopentadiene and its alkyl-substituted product (hereinafter sometimes referred to as "component B"), and can be produced by a known ring-opening polymerization method for cyclic olefins. 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) Component A used in the present invention is tetracyclododecene represented by the following general formula [III] (hereinafter sometimes abbreviated as "TCD") and its alkyl-substituted product.

The TCDs can be obtained by subjecting cyclopentadiene and norbornene to a Diels-Alder reaction and separating the reaction mixture from the reaction mixture by a method such as distillation.

The TCDs may be a lower alkyl-substituted TCD such as methyl, ethyl, or propyl, and may have a plurality of alkyl substituents.

The 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, 4,7,7a-hexahydroindene '', hereinafter `` HDC
It may be abbreviated as "P").

The DCPs and HDCPs may be lower alkyl-substituted compounds such as methyl and ethyl, and these may be used alone or in an appropriate mixture.

In the present invention, in the copolymer, the repeating unit derived from the component A is 10 mol% or more and less than 50 mol% by weight,
It is preferably 20 mol% or more and less than 50 mol%, and the repeating unit derived from the component B has a ratio of more than 50 mol%, 90 mol% or less, preferably more than 50 mol%, 80 mol% or less, Use each ingredient. However, in the copolymer, B
The repeating unit derived from the component is 50% by weight or more.

The glass transition temperature rises as the proportion of the component A used increases, but if the glass transition temperature becomes too high, it becomes difficult to process and the birefringence index, which is important in optical characteristics, increases. On the contrary, when the amount of B component is large, the glass transition temperature is not sufficiently high, and the effect of improving the birefringence is relatively low.

In the present invention, in addition to the above-mentioned components A and B,
Other cycloolefins capable of ring-opening polymerization can be used within a range that does 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.

In addition, some polycyclic norbornene-based monomers have compounds having two or more reactive double bonds, but such compounds are liable to cause gelation of the polymer and should be removed as much as possible. Is preferred.

The monomer mixture used in the present invention can be prepared by mixing the A component and the B component prepared in advance, or can be directly synthesized by heating DCPs and norbornenes.

The heat treatment conditions include heating DCPs and norbornenes under an inert gas atmosphere such as nitrogen gas at a temperature of 120 to 250 ° C., preferably 150 to 230 ° C. for 0.5 to 20 hours, preferably 1 to 10 hours. There is a method of doing. 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.

Further, in the polymerization, in addition to the components A and B, butene-1, pentene-1, hexene-1, octene-1,
Chain monoolefins such as butene-2, pentene-2, 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 copolymer of these monomers is produced by a usual norbornene polymerization method.
For example, platinum group metal compounds such as ruthenium, rhodium, palladium, osmium, iridium and platinum (for example, Japanese Examined Patent Publication No. 46-14910), or transition metal compounds such as titanium, vanadium, molybdenum, and tungsten, and Periodic Table I. -Group IV organometallic compound systems, etc., and this catalyst system may be combined with a third component such as a tertiary amine (see, for example, JP-B-41-20111, JP-B-57-17883, JP-A-57-61044, JP-A-54-86600
No. 58-127728).

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 , VCBr ₃ , WBr ₂ , WBr ₄ , WBr ₆ , WCl ₂ , WCl ₄ , WCl ₅ , WCl ₆ , WF ₄ , WI ₂ , WI ₄ , WOBr ₄ , WOCl. ₄ , WOF ₄ , MoBr ₂ , MoBr ₃ , MoBr ₄ , MoCl ₄ , MoCl ₅ , MoF 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 ), (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 Mo = C (OC 2 H 5) (N (C 2 H 5) 2), There are tridecyl ammonium molybdate, tridecyl ammonium tungstate, and the like.

Organometallic compounds Organometallic compounds include Group I to IV of the periodic table.
Organometallic compounds up to the group, such as 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.

Examples of the organic tin compound include tetramethyltin, diethyldimethyltin, tetraethyltin, dibutylethyltin, tetrabutyltin, tetraisocumyltin, tetraphenyltin, triethyltin fluoride, triethyltin chloride, triethyltin bromide and 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. Specific examples include molecular oxygen, alcohol, ether, peroxide,
Carboxylic acid, acid anhydride, acid chloride, ester, ketone, nitrogen-containing compound, sulfur-containing compound, halogen-containing compound,
Examples include molecular iodine and other Lewis acids. Among them, aliphatic or aromatic tertiary amines are preferable,
Specific examples thereof include triethylamine, dimethylaniline, tri-n-butylamine, pyridine and α-picoline.

(Solvent) Although the ring-opening copolymer 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 tolchlorbenzene, and two or more kinds of these may be mixed and used.

(Polymerization temperature) The temperature condition for 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 copolymer of the present invention is prepared by hydrogenating the above-mentioned ring-opening copolymer to obtain its olefinic unsaturated group (double bond of main chain and double bond of unsaturated ring). It can be obtained by saturating a part or all of the polymer, and thereby, the heat deterioration resistance and the light deterioration resistance of the polymer can be further improved. The hydrogenation rate is theoretically in the range of 0 to 100% when 100% is assumed when all the double bonds of the ring-opening polymer are saturated by hydrogenation, and in practice, it is optional within that range. However, in order to improve the heat deterioration resistance and the light deterioration resistance, it is necessary that 50% or more of the main chain double bonds 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 a solid catalyst in which these metals are supported on a carrier such as carbon, silica, diatomaceous earth, alumina or titanium oxide, for example, nickel / silica, nickel / diatomaceous earth, palladium / Examples thereof include carbon, palladium / silica, palladium / diatomaceous earth, palladium / alumina and the like. 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 Periodic Tables I to I
Examples thereof include organic metal compounds of Group II metals, Rh compounds and the like.

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

(Ring-Opening Copolymer Hydrogenated Product) The ring-opening copolymer used in the present invention has an intrinsic viscosity [η] measured in toluene of 25 ° C. of 0.01 to 20 dl / g, preferably
0.1 to 10 dl / g, but the [η] of the hydrogenated product of the ring-opening copolymer of the present invention is also 0.01 to 20 dl / g, preferably 0.
It is 1 to 10 dl / g. When [η] is in the above range, heat resistance, water resistance, transparency, chemical resistance, solvent resistance, processability and mechanical properties are good.

A hydrogenated product of a ring-opening polymer having TCDs alone or a copolymerization ratio of TCDs extremely large has a high glass transition temperature and excellent heat resistance, but on the other hand, it has a problem that it is difficult to process. On the other hand, the hydrogenated product of the ring-opening copolymer of the present invention comprises the above-mentioned component A (TCDs) and the component B (DCPs, HDCPs).
By co-polymerizing the () with a specific ratio, the glass transition temperature of the polymer can be appropriately controlled and the heat resistance and the processability can be balanced. Specifically, the hydrogenated product of the present invention can appropriately control the glass transition temperature (Tg) in the range of about 110 ° C to about 150 ° C, and as a result, has good moldability.

Further, as is clear from the birefringence value, a molded product with little optical distortion can be obtained even in a region where Tg is high.

Furthermore, light transmittance, water resistance, chemical resistance, solvent resistance,
The mechanical strength and the like are highly balanced, and are particularly suitable as optical materials.

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 copolymer used.

(Molding) The hydrogenated ring-opening copolymer of the present invention can be molded by a well-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 has a high glass transition temperature and is excellent in heat deterioration resistance and light resistance deterioration as is apparent from the fact that the unsaturated group is hydrogenated. In addition, since it is a polymer having excellent optical properties and well-balanced transparency, water resistance, chemical resistance, and mechanical properties, it is useful in various fields as various molded products.

For example, optical lens, optical disk, optical fiber,
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 50 parts of tetracyclododecene (TCD) and 50 parts of dicyclopentadiene (DCP) were placed in a reactor which was sufficiently dried and purged with nitrogen.
Parts, 1 mol% of 1-hexene based on the total amount of monomers, and 300 parts of toluene. Then, 16 parts of a 1 molar solution of triethylaluminum in toluene, 4 parts of triethylamine and 3 parts of a 1 molar solution of titanium tetrachloride in toluene were added and reacted at 25 ° C. for 2 hours.

The reaction solution was added to acetone / isopropyl alcohol (1 /
1) was poured into to solidify the polymer, and the precipitate was separated by filtration and dried to obtain 74 parts of the polymer. The yield was 74%.

As a result of analysis by the proton NMR spectrum of the obtained polymer, the molar ratio of the TCD component and the DCP component in the polymer was
It was 45:55 (weight ratio 50:50). The intrinsic viscosity measured in toluene at 25 ° C was 0.62 dl / g.

Dissolve 50 parts of the above polymer in 500 parts of cyclohexane,
Using 5 parts of palladium-carbon catalyst, hydrogen pressure 60Kg
A hydrogenation reaction was carried out at a temperature of 140 ° C./cm ² 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 separated by filtration and dried to obtain 43 parts of a polymer.

As a result of analysis by a proton NMR spectrum of this polymer, it was confirmed that the absorption of protons due to the double bond disappeared and the polymer was almost completely hydrogenated (hydrogenation rate 100%).

The intrinsic viscosity of this hydrogenated polymer measured in toluene at 25 ° C. was 0.60 dl / g. The glass transition temperature of the hydrogenated polymer as measured by DSC was 127 ° C.

This hydrogenated polymer was injection molded at 350 ° C and an injection pressure of 2,000 Kg / cm ² to make an optical disk plate with a diameter of 13 cm and a thickness of 1.2 mm, and the light transmittance (measured at 830 nm) and the birefringence value (double pass, 633 nm And the water absorption (weight change rate after immersion at 25 ° C. for 24 hours) were measured. As a result, light transmittance: 91
%, Birefringence value (inner circumference to outer circumference of optical disc plate): 20 to 6
It was 0 nm and the water absorption rate was 0.1% or less.

Regarding the solvent resistance, the above optical disk plate was immersed in ethyl acetate and acetone at room temperature for 20 hours, and the change in appearance was observed.
Regarding chemical resistance, changes in appearance were observed by immersing in 97.6% sulfuric acid and 28% ammonia water for 20 hours at room temperature. as a result,
No change in appearance was observed in either case.

From the above results, it is understood that the ring-opening copolymer hydrogenated product of the present invention is excellent in heat resistance and optical properties, and also has various physical properties such as water resistance and solvent resistance.

Examples 2 and 3 Ring-opening copolymerization, hydrogenation and injection 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.

Table 1 shows the physical properties of the obtained polymer and optical disc plate measured in the same manner as in Example 1.

Comparative Examples 1 to 3 For comparison, TCD only, DCP only, and the case of using TCD and norbornene (NB) as the monomers,
Polymers and optical disk plates were obtained in the same manner as in Example 1, and their physical properties were measured and shown in Table 1.

As is clear from Table 1, the ring-opening copolymer hydrogenated product of the present invention has Tg in a suitable range of 110 to 150 ° C., and has a good birefringence value even in a relatively high Tg region. It has excellent optical characteristics. It is also a well-balanced polymer with high water resistance and chemical resistance.

EFFECTS OF THE INVENTION The novel ring-opening copolymer hydrogenated product of the present invention is a polymer having excellent heat resistance and optical properties, and having a well-balanced transparency, water resistance, chemical resistance, solvent resistance and the like. There
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 Natsumi Io Natsumi 1-2-1 Kawasaki-ku, Kawasaki-shi, Kanagawa Japan Zeon Corporation Research and Development Center (56) Reference JP-A 64-24826 (JP, A) )

Claims (2)

(57) [Claims] 1. A repeating unit represented by the following general formula [I] or its alkyl-substituted product: 10 mol% or more, 50 mol%
And (B) the repeating unit represented by the following general formula [II] or its alkyl-substituted product exceeds 50 mol% and 90 mol% or less (however, the repeating unit represented by the general formula [II] is , 50% by weight or more in the copolymer), and the intrinsic viscosity [η] measured in toluene at 25 ° C is 0.
A hydrogenated product of a polycyclic norbornene ring-opening copolymer having a content of 01 to 20 dl / g and at least 50% of the (C ... C) bonds constituting the main chain are single bonds. (However, in the formula, ... indicates a single bond or a double bond.) 2. A repeating unit represented by the following general formula [I '] or its alkyl-substituted product is 10 mol% or more and less than 50 mol%, and (B) is represented by the following general formula [II']. A repeating unit or an alkyl-substituted product thereof in an amount of more than 50 mol% and not more than 90 mol% (however, the repeating unit represented by the general formula [II ′] is
It is 50% by weight or more in the copolymer. ), And the intrinsic viscosity [η] measured in toluene at 25 ° C is 0.
Carbon which constitutes the main chain by hydrogenating some or all of the olefinic unsaturated groups contained in the polycyclic norbornene ring-opening copolymer of 01 to 20 dl / g with hydrogen using a hydrogenation catalyst. A method for producing a hydrogenated polycyclic norbornene copolymer, which comprises converting at least 50% of carbon double bonds into single bonds. (However, in the formula, ... indicates a single bond or a double bond.)