JPH0832769B2 - Hydrogenated polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to ring-opening copolymerization consisting of a unit derived from a substituted or unsubstituted dimethanooctahydronaphthalene and a unit derived from a dicyclopentadiene. The present invention relates to a polymer having excellent heat resistance, transparency, and non-hygroscopicity, which is obtained by hydrogenating 80 mol% or more of an olefinically unsaturated group contained in a polymer.

[Conventional technology]

Conventionally superior resins having transparency are polymethylmethacrylate, polycarbonate, poly-4-methylpentene-1, etc., and optical recording materials such as optical discs, optical lenses, compact discs, video discs, computer discs, etc. It is used for the surface layer of

Generally, optical properties such as optical properties such as high light transmittance, homogeneity of refractive index, low birefringence, low water absorption, low hydrolyzability, heat deterioration resistance, solvent resistance are required as optical materials. Chemical characteristics such as, low thermal expansion coefficient, small temperature change of refractive index, thermal characteristics such as high thermal deformation temperature,
Mechanical properties such as impact strength and hardness, and easy moldability are included.

Looking at these characteristics of the above-mentioned transparent resin,
Polymethylmethacrylate is often used as a resin exhibiting the highest light transmittance, but it has problems such as deformation due to its low heat distortion temperature and high water absorption, or corrosion of the recording layer in an optical disc. is there.

Polycarbonate is also better than polymethylmethacrylate, but it still has problems due to water absorption, and has drawbacks such as high birefringence and low solvent resistance.

Although poly-4-methylpentene-1 is a crystalline polymer, it is a rare resin because of its high transparency, but since it is also crystalline, it has a large molding shrinkage ratio and the orientation remains in the molded product. It has a drawback that it is easy to cause warping and birefringence.

Regarding a method for obtaining a polymer having a relatively high glass transition temperature by ring-opening polymerization of a cycloolefin containing dicyclopentadiene, JP-A-53-17700 discloses a ring-opening copolymerization of a norbornene derivative and dicyclopentadiene. Then, a method for obtaining an amorphous polymer is presented. However, in this method, the dicyclopentadiene content is 50
The glass transition temperature is not sufficiently high because it is as high as more than 10% by weight, and since it has not been hydrogenated, double bonds remain in the polymer and there is a problem in heat resistance.

Further, JP-A-58-96623, JP-A-58-204023, and JP-A-SHO-5
8-204024 and the like have a proposal regarding a terpolymer of methylnorbornene, methyldimethanooctahydronaphthalene, dicyclopentadiene, etc.
96623 with dicyclopentadiene content of 50% by weight
Examples of are only described. However, also in this case, the HDT is as low as 98 ° C., and thus the glass transition temperature is low. Also, as in JP-A-53-17700, the double bond remains in the polymer, the thermal stability of the polymer is insufficient, and there are problems such as gelation during molding.

On the other hand, in Japanese Examined Patent Publication No. 46-14910, there is presented a dimethanooctahydronaphthalene homopolymer, and a copolymer of dimethanooctahydronaphthalene and norbornene,
Although a polymer having a high glass transition temperature has been obtained,
After all, since the polymer contains a double bond, it is difficult to avoid the problem of gelation, especially when performing molding processing such as injection molding or extrusion molding. Further, when kept under high temperature conditions for a long period of time, thermal oxidative deterioration occurs.

Further, JP-A-60-26024 discloses a polymer obtained by hydrogenating the above-mentioned polymer. Regarding dimethanooctahydronaphthalene homopolymer, a polymer having a high glass transition temperature can be obtained, but dimethanooctahydronaphthalene is expensive and insufficient in cost performance, and the homopolymer is Since the regularity of the molecular structure of the polymer is higher than that of the copolymer, crystallinity is likely to be exhibited, and therefore it is unsuitable as an optical material.

On the other hand, regarding the copolymer, norbornene is used as a monomer to be copolymerized with dimethanooctahydronaphthalene, but norbornene has a glass transition temperature lower than that of dicyclopentadiene used in the present application. If the amount of copolymerization is increased, a polymer having high heat resistance cannot be obtained. In terms of cost, norbornene is more expensive than dicyclopentadiene.

[Object of the Invention]

The present inventors have conducted extensive studies to obtain a resin in which these drawbacks of conventional transparent resins are improved, and as a result, a unit derived from a substituted or unsubstituted dimethanooctahydronaphthalene and dicyclopentadiene are obtained. The polymer obtained by hydrogenating 80 mol% or more of the olefinically unsaturated group contained in the ring-opening copolymer composed of the derived unit has a high glass transition temperature, is excellent in heat resistance, and is amorphous. As a result, they have found that the material is excellent in transparency and non-hygroscopicity, and thus reached the present invention.

[Structure of Invention]

To illustrate the invention in more detail, the first starting monomer of the polymer of the invention is a substituted or unsubstituted dimethanooctahydronaphthalene. As these monomers, compounds represented by the following general formula are used.

(Here, R ¹ and R ² are hydrogen, an alkyl group or an alkenyl group, R ¹ and R ² may form a ring, and R ¹ and R ² may be the same or different.) R ¹ and R ² are preferably linear or branched alkyl groups having up to about 4 carbon atoms, or R ¹ and R ² are combined with two carbons of the dimethanooctahydronaphthalene ring,
It is preferable to form a monocyclic ring having 5 to 7 carbon atoms or a bicyclo ring.

Generally, sufficient heat resistance can be obtained by using a linear or branched alkyl group having up to about 4 carbon atoms.

Examples of such a monomer include dimethanooctahydronaphthalene, methyldimethanooctahydronaphthalene, isopropyldimethanooctahydronaphthalene, and dimethyloctahydronaphthalene.

Examples of R ¹ and R ² forming a ring include decahydrodimethanobenzindene, octahydrodimethanobenzindene, trimethanodecahydroanthracene and the like.

On the other hand, the monomer that is copolymerized with the substituted or unsubstituted dimethanooctahydronaphthalene is dicyclopentadiene.

Examples of the dicyclopentadiene include unsubstituted or alkyl-substituted dicyclopentadiene.

Preferably, these monomers are unsubstituted cyclopentadiene dimers, methylcyclopentadiene dimers in which the alkyl group is methyl, or a mixture of both.

When these monomers are used as one component of the copolymer, a polymer having a higher glass transition temperature can be obtained as compared with the case where other monomers such as norbornene are used, and the impact strength and the heat resistance are well balanced.

Catalysts ring-opening polymerization of these monomers is not particularly limited, for example, _{AlEt 3 -MoCl 5, Et 2 AlCl} -W
cl ₆ or MoCl ₅ ~ Et ₂ AlI ~ catalyst system in which a group IV to VII group metal compound such as tungsten, molybdenum, rhenium, titanium, vanadium, zirconium such as ethyl acetate and an organic aluminum compound are combined, or ruthenium, rhodium, palladium , Osmium, iridium, platinum, etc.
Combination of Group VIII metal halide etc. and alcohol,
Alternatively, various complexes of these metals can be cited.

Regarding the polymerization conditions, the temperature condition of -50 ℃ ~ 150 ℃,
In the presence or absence of an inert solvent, atmospheric pressure or 20
Polymerization is performed under pressure up to about kg / cm ² .

The produced copolymer is composed of structural units represented by the following formula.

(R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same as above. However, the unit derived from dicyclopentadiene is 50
% By weight. From the viewpoint of high glass transition temperature, it is preferable that the molar ratio of the unit derived from the dimethanooctahydronaphthalene derivative to the unit derived from the dicyclopentadiene is 1 or more, which means that the amorphousness is increased. From the viewpoint, a copolymer is preferable to a homopolymer. Therefore, the preferable content of the unit derived from dicyclopentadiene is 5
~ 50 mol%.

The molecular weight of the ring-opening copolymer of the present application is preferably adjusted with an acyclic monoolefin, or a non-conjugated, acyclic polyene, and such olefins include those on each double bond carbon atom. The one having at least one hydrogen and having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms is used. When these acyclic olefins are allowed to coexist in the polymerization system, they function as a molecular weight regulator and improve the melt fluidity of the polymer.

Examples of such acyclic olefin include 1-butene and 1
-Hexene, 4-methylpentene-1,3-methylbutene-1,2-pentene, 2-hexene, 1,6 hexadiene and the like can be mentioned. Preferred acyclic olefins include 1-olefins such as 1-butene and 1-hexene.

The amount of acyclic olefin present in the polymerization system is 0.0001 to 1 mol, preferably 0. 01 mol, based on 1 mol of the total of dimethanooctahydronaphthalene and dicyclopentadiene.
It is from 01 to 0.7 mol.

The viscosity number of the ring-opening copolymer thus obtained (ηsp /
c) is in the range of 0.1 to 15 and preferably 0.5 to 5 dl / g at a concentration of 0.25 g / dl at 25 ° C in a toluene solvent.

The hydrogenation reaction of the olefinically unsaturated group contained in this polymer can be carried out by a usual method.

Examples of the catalyst used include Wilkinson's complex RhCl (PPh ₃ ) ₃ , RuH (Cl) (PPh ₃ ) ₃ , cobalt acetate + triethylaluminum, nickel acetylacetonate-triisobutylaluminum, etc. As the system catalyst, a group VIII metal such as Pd-activated carbon, Ru-activated carbon or Ni-diatomaceous earth supported on a carrier such as activated carbon, silica, diatomaceous earth or alumina is used.

The hydrogenation reaction varies depending on the catalyst, but normal pressure to 100 kg / cm
It is carried out under a hydrogen pressure of ² at a temperature of 0 to 150 ° C, preferably 20 to 150 ° C.

The hydrogenation rate is 80% or more, preferably 90% or more. When the hydrogenation rate is at least the above value, the heat resistance and photodegradability of the obtained polymer will be sufficient.

In addition, hydrogenation also improves the resistance to organic solvents and makes them sparingly soluble in aromatic solvents such as benzene and toluene.

The viscosity number of the hydrogenated polymer is decalin solvent 135 ℃, concentration 0.2
At 5 g / dl, it is 0.3-10 dl / g, preferably 0.8-8 dl / g.

The hydrogenated polymer of the present invention is amorphous and therefore has good transparency. The crystallinity in X-ray diffraction is 0, no melting point is observed in DSC, and only the inflection point of the DSC curve based on the glass transition is recognized. This inflection point is between 100 ° C. and higher, and often up to 200 ° C., and the polymer of the present invention has high heat resistance.

In addition, the present polymer is excellent in dielectric properties and chemical resistance originally possessed by polyolefin resin, and various optical materials such as optical discs, optical fibers, optical lenses,
Besides, it is useful in various fields as a transparent engineering plastic.

The polymer of the present invention can be molded by a known method, such as extrusion molding, injection molding, blow molding, vacuum / pressure molding and the like.

Additives are added as necessary during molding.
Examples of such additives include heat stabilizers, light stabilizers, antistatic agents, slip agents, antiblocking agents, and the like.

For engineering plastics applications, fillers such as glass fiber, mica, talc and calcium carbonate can be used.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples as long as the gist thereof is not exceeded.

In the following examples, the viscosity of the ring-opening polymer is a viscosity number (viscocity number) measured by an Ubbelohde viscometer under the conditions of 25 ° C., a toluene solvent and a concentration of 0.25 g / dl.

The viscosity of the hydrogenated polymer is the viscosity number measured under the conditions of 135 ° C. and decalin solvent concentration of 0.25 g / dl.

The glass transition temperature of the polymer is 16 ° C with DuPont 9900 type DSC
It was measured at a temperature rising rate of minutes.

The X-ray diffraction measurement of the polymer was carried out on a powdery sample using a "turbo molecular motor type, 12KW X-ray apparatus". The light transmittance was measured with a light beam of 780 nm using a U-3400 type Hitachi self-recording spectrophotometer for a sample having a thickness of 0.1 mm.

NMR and IR spectra were measured by JEOL JNM GX-270 type nuclear magnetic resonance apparatus and JASCO A202 type infrared spectrophotometer, respectively.

 The water absorption rate was measured according to JIS K6911.

Example-1 In a 4-necked flask of 1, 360 ml of toluene, 51 mmol
Dimethanooctahydronaphthalene, 18 mmol dicyclopentadiene, 3.6 mmol 1-hexene, 0.0 as catalyst
Polymerization was initiated by adding 7 mmol of MoCl ₅ , 0.27 mmol of diethyl aluminum iodide and 4.2 mmol of ethyl acetate.

The polymerization temperature was 27 to 29 ° C, the polymerization time was 10 min, the reaction was stopped with methanol, and the catalyst and unreacted reagents were removed to obtain a ring-opening polymer having a viscosity number η of 2.9.

Figures 1 and 2 show the IR and NMR diagrams of this polymer. The composition ratio of the ring-opening polymer obtained from this figure was dimethanooctahydronaphthalene: dicyclopentadiene = 70/30 (molar ratio).

1.5 g of this polymer, 300 ml of toluene as a solvent, and 0.43 g of Wilkinson complex RhCl (PPh ₃ ) ₃ as a catalyst were charged,
Hydrogenation reaction was carried out at 100 ° C. and H ₂ pressure of 30 kg / cm ² for 5 hours.

After the reaction, the catalyst was removed and the physical properties of the obtained white polymer were measured.

IR and NMR of the obtained polymer are shown in Fig. 3 and Fig. 4. From the comparison between Fig. 3, Fig. 4 and Fig. 1, Fig. 2, it can be seen that the hydrogenation reaction is sufficiently advanced. it is obvious. Table 2 shows the physical property measurement results. Figure 5 shows the DSC measurement results.

Moreover, FIG. 6 is a DSC measurement result of the unhydrogenated product of Comparative Example-1. As described above, the unhydrogenated product has very poor thermal stability as compared with the hydrogenated product as shown in FIG. 6 of Example-1.

Further, FIG. 7 shows an X-ray diffraction pattern of the polymer powder in comparison with that of polycarbonate (amorphous). From this figure it can be seen that the polymer is amorphous.

Example-2 In Example-1, ring-opening polymerization and hydrogenation reaction were performed in the same manner as in Example-1, except that 62 mmol of dimethanooctahydronaphthalene, 7 mmol of dicyclopentadiene, and 5.2 mmol of 1-hexene were used. It was The results are shown in Tables-1 and 2.

Example-3 In Example-1, 51 mmol of dimethanooctahydronaphthalene was mixed with 35 mm of methyldimethanooctahydronaphthalene.
ol, dicyclopentadiene, 1-hexene 18mmo each
Example 1 except that l, 3.6 mmol was changed to 34 mmol, 5.0 mmol
The ring-opening polymerization and hydrogenation reaction were carried out in the same manner as in.

 The results are shown in Tables-1 and 2.

Comparative Example-1 Polymerization and hydrogenation reaction were carried out in the same manner as in Example-1 except that dimethanooctahydronaphthalene was not used and the scale was increased.

 The results are shown in Tables-1 and 2.

Comparative Example-2 In Example-3, except that the amount of methyldimethanooctahydronaphthalene was changed to 38 mmol, dicyclopentadiene was replaced with methylnorbornene, and the amounts were changed as described in Table-1, the same as Example-3. Polymerization and hydrogenation reaction were performed in the same manner to obtain a polymer having a glass transition temperature of 100 ° C.

For comparison, polymethylmethacrylate (PMM
A), the physical properties of polycarbonate were also measured, and
It is also shown in 2.

[Effects of the Invention] As can be seen from Table 2, the polymer of the present invention has heat resistance,
It has excellent transparency and non-hygroscopicity, and because it is completely amorphous, it has a low shrinkage factor during molding.

Also, since dicyclopentadiene is used as a monomer to be copolymerized in combination with dimethanooctahydronaphthalene, compared to the case of using another monomer,
A polymer having a good balance of heat resistance and moldability and being inexpensive can be obtained.

[Brief description of drawings]

1 and 2 are IR and NMR diagrams of the polymer before hydrogenation in Example 1, respectively. Further, FIG. 3, FIG. 4 and FIG. 5 are graphs showing IR, NMR and DSC measurement results of the hydrogenated polymer of the present invention obtained in Example 1. FIG. 6 shows the DSC measurement results of the unhydrogenated product of Comparative Example 1, and FIG. 7 is an X-ray diffraction diagram of the powder of the hydrogenated polymer and polycarbonate resin of Example 1.

Claims (3)

[Claims] 1. An olefinic unsaturated group contained in a copolymer comprising a unit derived from a substituted or unsubstituted dimethanooctahydronaphthalene and a unit derived from a dicyclopentadiene represented by the following formula: A hydrogenated polymer having a glass transition temperature of 100 ° C. or higher and a viscosity of 0.3 to 10 dl / g measured at 135 ° C. and a concentration of 0.25 g / dl decalin, which is obtained by hydrogenation by mol% or more. (In the formula, R ¹ and R ² are a hydrogen atom, an alkyl group or an alkenyl group, and R ¹ and R ² may be bonded to each other to form a ring. R ³ to ⁶ are a methyl group or hydrogen. Is an atom,
If one of R ⁴ , R ⁵ and R ⁶ is a methyl group, the other 2
One is a hydrogen atom. However, the unit derived from dicyclopentadiene is 50% by weight or less in the copolymer. ) 2. The copolymer according to claim 1, wherein the copolymer is obtained by ring-opening polymerization of a substituted or unsubstituted dimethanooctahydronaphthalene and dicyclopentadiene. Hydrogenated polymer. 3. The hydrogenated polymer according to claim 1, wherein R ¹ and R ² are linear or branched alkyl groups having up to 4 carbon atoms.