JPH0597978A - Hydrogenated polymer - Google Patents

Abstract

(57) [Summary] [Structure] (1) 0.01 to 5 of an oligomer having a weight average molecular weight of 2000 or less, which is obtained by further hydrogenating a polymer obtained by ring-opening polymerization of a specific norbornene derivative is used.
Hydrogenated polymer containing wt%. [Effect] It is easy to control the viscosity during molding, has a low birefringence and is excellent in heat resistance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrogenated polymer suitable as a heat-resistant optical material having a low birefringence, whose viscosity can be easily controlled during molding.

[0002]

2. Description of the Related Art In recent years, plastic has been adopted as a lens material instead of glass in terms of workability and weight saving. In particular, the mainstream material for plastic aspherical lenses is polymethylmethacrylate. Polymethylmethacrylate has a high light transmittance, it is easy to control the viscous behavior of the resin during molding, there is almost no birefringence, and the cost is low. It is used. However, polymethylmethacrylate has a heat resistance of about 80 ° C., which is insufficient depending on the application, has a large saturated water absorption rate, and is inferior in reliability to a glass lens.

[0003]

The present invention solves the above problems, has a high light transmittance, is easy to control the viscous behavior of the resin during molding, has almost no birefringence, has a large saturated water absorption, and has a high heat resistance. A polymer suitable for use as an optical material having excellent properties is also provided.

[0004]

That is, the present invention is obtained by ring-opening polymerization of at least one norbornene derivative represented by the following general formula (I) or the norbornene derivative and a monomer copolymerizable therewith. Which is a hydrogenated polymer having an intrinsic viscosity of 0.35 to 0.8 and further having a weight average molecular weight of 2000 or less in an amount of 0.01 to 5% by weight. Hydrogenated polymer characterized by having general formula (I)

[0005]

[Chemical 2] (In the formula, A and B are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, X and Y are a hydrogen atom, a halogen atom or a monovalent organic group, and m is 0 or 1. ) Is provided. Hereinafter, the present invention will be specifically described.

The hydrogenated polymer of the present invention comprises a monomer comprising the norbornene derivative represented by the general formula (I) (hereinafter referred to as "specific monomer") alone or a specific monomer. It is a hydrogenated polymer obtained by ring-opening copolymerization using a metathesis polymerization catalyst together with a copolymerizable monomer copolymerizable with, and is referred to as a “hydrogenated polymer” below. In the present invention, among the specific monomers, X or Y in the general formula (I) is represented by the formula — (CH
₂ ) The specific monomer which is a group represented by _n COOR ¹ is
It is preferable that the obtained polymer has a high glass transition temperature and low hygroscopicity. Moreover, the formula - (CH _{2) n}
It is preferable that one group represented by COOR ¹ be contained per molecule of the specific monomer, since the resulting polymer has low hygroscopicity.

Further, among the groups represented by the formula — (CH ₂ ) _n COOR ¹ , the smaller the value of n, the higher the glass transition temperature of the polymer obtained, which is preferable.
The specific monomer in which is 0 is easy to synthesize,
It is also preferable in that the obtained polymer can have good characteristics. In the above formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, and it is preferable that the carbon number increases so that the hygroscopicity of the resulting polymer decreases. However, from the viewpoint of the balance with the glass transition temperature of the obtained polymer, a chain alkyl group having 1 to 4 carbon atoms or a chain alkyl group having 5 or more carbon atoms (many)
It is preferably a cyclic alkyl group, and particularly preferably a methyl group. Moreover, the formula - (CH _{2) n} COO
The specific monomer in which the hydrocarbon group having 1 to 10 carbon atoms is simultaneously bonded as a substituent to the carbon atom to which the group represented by R ¹ is bonded does not lower the glass transition temperature of the obtained polymer. It is preferable because it lowers hygroscopicity. And
In particular, the specific monomer having a methyl group as the substituent is preferable because the synthesis thereof is easy.

The ring-opening polymer relating to the hydrogenated polymer used in the present invention may be a ring-opening polymer of a specific monomer alone. It may be a compound obtained by ring-opening copolymerization with the body. When the copolymerizable monomer is used as described above, the proportion of the specific monomer in the ring-opening polymer is 5 mol% or more, preferably 20 mol% or more. Examples of the copolymerizable monomer used include monomers that can be ring-opening polymerized by a metathesis polymerization catalyst, and partially polymerized low polymers having a carbon-carbon double bond in the main chain of the polymer. be able to. Among the above specific monomers, m is 1 in the general formula (I).
The tetracyclododecene derivative of is preferable in that a polymer having a high glass transition point can be obtained. Among the tetratoclododecene derivatives in which m is 1 in the general formula (I), preferred compounds include 8-carboxymethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyl-8-carboxymethyltetracyclo [4.4.0.1 ^2,5 . 1, ^{7, 10} ] -3-dodecene, 5-
Carboxymethyl-bicyclo [2.2.1] -2-heptene and the like can be mentioned.

The specific monomer can also be copolymerized with a cyclic olefin compound. Specific examples of the cyclic olefin compound include cyclopentene, cyclooctene, 1,
Cycloolefins such as 5-cyclooctadiene and 1,5,9-cyclododecatriene; bicyclo [2.2.
1] -2-heptene, tricyclo [5.2.1.
0 ^2,6 ] -8-decene, tricyclo [5.2.1.0]
^2,6 ] -3-decene, tricyclo [6.2.1.
0 ^1,8 ] -9-undecene, tricyclo [6.2.1.
0 ^1,8 ] -4-undecene, tetracyclo [4.4.
0.1 ^2,5 . 1 ^{7, 10} ] -3-dodecene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] -4-pentadecene, pentacyclo [6.6.1.1 ^3,6. 0 ^2,7 .
0 ^9,14] -4-Hekisadesesen, pentacyclo [6.
5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -11-pentadecene, dicyclopentadiene, pentacyclo [6.5.
1.1 ^3,6 . 0 ^2,7 . 0 ^{9, 13]} - pentadeca -4,11
Mention may be made of polycycloalkenes such as dienes.

Further, the specific monomer is a polymer such as polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-propylene non-conjugated diene copolymer rubber, polynorbornene, polypentenamer, and the like.
Ring-opening polymerization can also be carried out in the presence of an unsaturated hydrocarbon polymer containing a carbon double bond. For the ring-opening polymerization method and the hydrogenation method of the specific monomer and the copolymerizable monomer copolymerizable therewith, the same method as the method described in JP-A-1-132626 can be mentioned. You can The hydrogenation rate of the obtained hydrogenated polymer is usually 50% or more, preferably 70% or more, more preferably 80% or more. A polymer having a hydrogenation rate of less than 50% has poor light resistance.

The hydrogenated polymer of the present invention is a hydrogenated polymer having an intrinsic viscosity of 0.35 to 0.8 obtained by further hydrogenating a ring-opening polymer obtained by ring-opening polymerization of the above-mentioned specific monomer. It is united. As the specific monomer, the same ones as in the above can be mentioned, and the preferable ones are also the same. The hydrogenated polymer of the present invention contains 0.01 to 5% by weight, preferably 0.01 to 4% by weight, and more preferably 0.02 to 3% by weight of a polymer having a weight average molecular weight of 2000 or less. Is. Here, if the polymer having a weight average molecular weight of 2000 or less is less than 0.01% by weight, the birefringence cannot be lowered, and if it exceeds 5% by weight, the molded product has a poor appearance.
In the present invention, the polymer having a weight average molecular weight of 2000 or less is preferably polymerized separately and then added to the normally polymerized polymer. In the metathesis ring-opening polymerization reaction, the molecular weight and molecular weight distribution of the hydrogenated polymer are adjusted by changing the reaction conditions such as the type and concentration of the metathesis polymerization catalyst, the polymerization temperature, the type and amount of the solvent, and the monomer concentration. .. Usually, it is preferable to adjust the molecular weight of the ring-opening polymer by adding an appropriate amount of an appropriate molecular weight regulator to the polymerization reaction system. Examples of the molecular weight regulator include compounds having at least one carbon-carbon double bond or carbon-carbon triple bond in the molecule such as α-olefins, α, ω-diolefins and acetylenes, allyl chloride, and allyl acetate. , A polar allyl compound such as trimethylacryloxysilane. Also, the molecular weight distribution can be narrowed by changing the catalyst.

[0012]

EXAMPLES Method for producing hydrogenated polymer (a-1) having a wide molecular weight distribution 8-methyl-8-carboxymethyltetracyclo [4.4.0.1 ^{2, 5} ． 1
^7,10 ] -3-dodecene (500 g), 1,2-dichloroethane (2000 ml), 1-hexene (3.8 g) as a molecular weight regulator, and a hexachlorobenzene solution having a concentration of 0.05 M / liter of tungsten hexachloride as a catalyst 91. 6 ml
And 1,2 with a paraaldehyde concentration of 0.1 M / liter
68.7 ml of a dichloroethane solution and a toluene solution of triisobutylaluminum having a concentration of 0.5 M / liter 3
7 ml was added and reacted at 60 ° C. for 10 hours to obtain 450 g of a ring-opening polymer. This ring-opening polymer was
It is dissolved in tetrahydrofuran (ml) and the palladium concentration is 5
45% by weight of palladium-alumina catalyst was added, and hydrogen gas was charged so that the pressure became 100 kg / cm ² , and 1
Hydrogenation reaction was carried out at 50 ° C. for 5 hours. After the hydrogenation reaction,
The catalyst was filtered off, and the filtrate was poured into a large excess of hydrochloric acid-acidified methanol to prepare hydrogenated polymer a-1.
The hydrogenation rate of this polymer a-1 was substantially 100%. Further, η _{inh of} the polymer is 0.56, and Mw / Mn =
It was 6.02.

Method for producing oligomer In a reaction vessel purged with nitrogen under a nitrogen atmosphere, 8
-Methyl-8-carboxymethyltetracyclo [4.
4.0.1 ^2,5 . 1, ^{7, 10} ] -3-800 g of dodecene,
2400 g of 1-hexene and a solution of WCl _{6 as} a catalyst in a concentration of 0.05 M / litryl in dimethoxyethane 34.5
ml and diethylaluminum chloride concentration 1.0M
/ Liter of n-hexane solution 3.45 ml was added, and
The reaction was carried out at 0 ° C. for 3 hours to obtain a polymerization solution.

Methanol is added to the upper portion of the polymerization solution which has been separated into two layers, and the mixture is shaken well and then allowed to stand to recover the upper layer portion. This operation was repeated 3 times, and the collected upper layer was concentrated again. This upper layer concentrated liquid was added with a palladium / alumina hydrogenation catalyst in an autoclave to obtain a hydrogen pressure of 40 kg / c.
Hydrogenation was carried out at m ³ and a temperature of 160 ° C. After filtering the hydrogenated catalyst, it was isolated from the catalyst to obtain an oligomer. The average molecular weight was 1100. When M = 1300 of GPC, it was 53% by weight M = 1000 〃 27% by weight M = 780 〃 16% by weight M = 550 〃 4% by weight (peak value).

The physical properties of the obtained lens were measured by the following methods. Total light transmittance (ASTM D-1003) (%) Double bending (Ellipsometer 633nm) (nm) Tensile strength (ASTM D-638) (kg / cm ² ) Stretch (ASTM D-638) (%) Resistance Thermal property (DSC Tg) (℃)

[0016]

[Table 1] Examples 1 to 3, Comparative Examples 1 and 2 A hydrogenated polymer obtained by varying the amount of the oligomer as shown in Table 1 with respect to 100 parts by weight of the hydrogenated polymer (a-1) was injection-molded at 305 ° C. A lens having a thickness of 2 mm was produced.
(Table 1) Examples 4 and 5 Samples were prepared by changing the amount of oligomer to those having different intrinsic viscosities, and molded articles were prepared using these. (Table 1)

[0017]

[Table 1]

[0018]

INDUSTRIAL APPLICABILITY According to the present invention, a hydrogenated polymer having an intrinsic viscosity within a certain range and a sharp molecular weight distribution, and a composition obtained by adding an oligomer to a polymer having an inherent viscosity within a certain range can control viscosity during molding. Easy and low birefringence. Therefore, heat-resistant optical parts such as plastic lenses, spherical lenses, aspherical lenses, copier lenses, video camera converter lenses, LBP lenses, optical disc pickup lenses, contact lenses, optical disks, vehicle parts lenses, optical fibers, etc. Is effective for.

Claims (1)

[Claims] 1. At least one norbornene derivative represented by the following general formula (I) or a ring-opening polymer obtained by ring-opening polymerization of the norbornene derivative and a monomer copolymerizable therewith is further hydrogenated. Intrinsic viscosity obtained by
A hydrogenated polymer having a weight average molecular weight of 2,000 or less in a proportion of 0.01 to 5% by weight. General formula (I): (In the formula, A and B are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, X and Y are a hydrogen atom, a halogen atom or a monovalent organic group, and m is 0 or 1. )