JP2001278960A - Method for producing polymer having cyclic structure and polymerization reactor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing in large quantities and high efficiency the polymer having a cyclic structure with few possibilities of manufacturing a defective molding such as discoloring and a sink mark in the molding. SOLUTION: The monomer having a cyclic structure is polymerized by adding the monomer having a cyclic structure and the polymerization catalyst through the projecting supply port (42a) which is located inside the reactor (4).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polymer having a ring structure suitable as a molding material for optical parts, and a polymerization reactor used for the method.

[0002]

2. Description of the Related Art A polymer having a ring structure such as a norbornene-based polymer is excellent in transparency and is a material suitable for an optical material and the like. However, when the molecular weight distribution becomes large in the polymerization stage or the like, the molded product may be colored or the like due to the influence of the high molecular weight component. In addition, defects such as sink marks are likely to occur during molding due to a decrease in fluidity at the time of melting, and there is a problem that if the molding temperature is increased to prevent this, the molded product is colored.

As a method for reducing the molecular weight distribution of a norbornene-based polymer, there has been proposed a method of sequentially adding a part of a monomer or a polymerization catalyst used in a reaction to a reaction system (Japanese Patent Application Laid-Open No. 11-1548). . However, in the present technology, only a method relating to a reaction operation at an experimental level has been proposed, and it is disclosed as to how to perform the sequential addition in a case where a mass production reactor is actually used. There was no.

The sequential addition reaction is certainly effective in reducing the molecular weight distribution, but, for example, when a monomer or a polymerization catalyst to be added is dropped on the reaction solution along the inner wall of the reactor, a high molecular weight component is locally generated, Even if the apparent molecular weight distribution can be made small, there is a problem that coloring of a molded article is likely to occur.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and provides a method for producing a polymer having a ring structure suitable as an optical material and the like, which does not cause coloring during molding or molding defects such as sink marks. The purpose is to do.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, in the step of successively adding a monomer or a polymerization catalyst used in the reaction to produce a polymer having a ring structure, By providing the supply port of the monomer or catalyst to be added sequentially at the tip of the nozzle having a specific shape protruding from the inner wall of the reactor, a molded article molded using the polymer does not cause molding defects such as coloring and sink marks. I found that. In addition, by setting the length of the nozzle so that the supply port is always located above the liquid surface of the reaction solution from the start to the end of the sequential addition of the monomer and the like, coloring of a molded product, molding of a sink mark, etc. The present inventors have found that prevention of defects can be more effectively prevented, and have completed the present invention.

That is, in the method for producing a polymer having a ring structure according to the present invention, a monomer having a ring structure and / or a polymerization catalyst is successively added from a supply port protruding into the inside of a reactor body. It is characterized in that the structure-containing monomer is polymerized in the presence of a polymerization catalyst, and the produced polymer is hydrogenated as required.

The polymerization reactor according to the present invention is provided so as to protrude into the reactor main body and the inside of the reactor main body, and has a front end provided with a supply port for sequentially adding a monomer and / or a polymerization catalyst. And a nozzle formed in the portion.

Preferably, the projecting length of the supply port is at least 10 mm from the inner wall surface of the reactor main body, and the supply port is disposed above the liquid surface of the reaction solution during the polymerization reaction.

[0010] Preferably, the supply port is formed at a tip end portion of a cylindrical nozzle provided so as to protrude into the inside of the reactor main body, and has an elliptical cross section.

[0011]

Embodiments of the present invention will be described below.

The process for producing a ring-structure-containing polymer according to the present invention comprises at least a step of polymerizing a ring-structure-containing monomer, and if necessary, following the polymerization step, the obtained ring-structure-containing polymer. And a step of hydrogenating the union.

Polymerization Step The polymer containing a ring structure in the present invention has a cyclic structure such as a cycloalkene ring, a cycloalkane ring or an aromatic ring in its repeating unit. Although there is no particular limitation, it is usually 4 to 30, preferably 5 to 20, and more preferably 5 to 15, from the viewpoints of mechanical strength, heat resistance, and moldability.

The content of the repeating unit having a ring structure in the whole polymer repeating unit may be appropriately selected according to the purpose of use, but is usually 50% by weight or more, preferably 70% by weight or more.
% By weight or more, more preferably 90% by weight or more. If the proportion of the repeating unit having a ring structure is too small, transparency and heat resistance are poor. The remainder other than the repeating unit having a ring structure is not particularly limited, and is appropriately selected depending on the purpose of use.

The polymer containing a ring structure may be a homopolymer or a copolymer, and the copolymer may be a random copolymer or a block copolymer. Further, (co) polymers obtained by graft-modifying these may be used.

The ring-structure-containing monomer used in the polymerization step has a ring structure in the molecular structure. Examples thereof include a norbornene-based monomer and a monocyclic cyclic olefin-based monomer. , An alicyclic structure-containing monomer such as a cyclic conjugated diene-based monomer, a vinyl alicyclic hydrocarbon-based monomer, and an aromatic vinyl-based monomer. From the viewpoint of heat resistance
It is preferable to use a norbornene-based monomer, a vinyl alicyclic hydrocarbon-based monomer, and an aromatic vinyl-based monomer.

Examples of the norbornene-based monomer include, for example,
Bicyclo [2.2.1] -hept-2-ene (common name:
Norbornene), 5-methyl-bicyclo [2.2.1]
-Hept-2-ene, 5,5-dimethyl-bicyclo
[2.2.1] -Hept-2-ene, 5-ethyl-bishi
Black [2.2.1] -hept-2-ene, 5-butyl-
Bicyclo [2.2.1] -hept-2-ene, 5-hex
Sil-bicyclo [2.2.1] -hept-2-ene, 5
-Octyl-bicyclo [2.2.1] -hept-2-e
5-octadecyl-bicyclo [2.2.1] -heptane
To-2-ene, 5-ethylidene-bicyclo [2.2.
1] -Hept-2-ene, 5-methylidene-bicyclo
[2.2.1] -Hept-2-ene, 5-vinyl-bishi
Black [2.2.1] -hept-2-ene, 5-propeni
Rubicyclo [2.2.1] -hept-2-ene, 5-
Methoxy-carbonyl-bicyclo [2.2.1] -hep
To-2-ene, 5-cyano-bicyclo [2.2.1]-
Hept-2-ene, 5-methyl-5-methoxycarboni
Rubicyclo [2.2.1] -hept-2-ene, 5-
Methoxycarbonyl-bicyclo [2.2.1] -hept
-2-ene, 5-ethoxycarbonyl-bicyclo [2.
2.1] -Hept-2-ene, 5-methyl-5-ethoxy
Cycarbonyl-bicyclo [2.2.1] -hept-2-
Ene, bicyclo [2.2.1] -hept-5-enyl-
2-methylpropionate, bicyclo [2.2.1]-
Hept-5-enyl-2-methyloctanatebicyclo
[2.2.1] -Hept-2-ene-5,6-dicarbo
Acid anhydride, 5-hydroxymethyl-bicyclo [2.
2.1] -Hept-2-ene, 5,6-di (hydroxy
Methyl) -bicyclo [2.2.1] -hept-2-e
5-hydroxy-i-propyl-bicyclo [2.
2.1] -Hept-2-ene, 5,6-dicarboxy-
Bicyclo [2.2.1] -hept-2-ene, bicyclo
[2.2.1] -Hept-2-ene-5,6-dicarbo
Acid imide, 5-cyclopentyl-bicyclo [2.2.
1] -Hept-2-ene, 5-cyclohexyl-bisic
B [2.2.1] -Hept-2-ene, 5-cyclohexyl
Senyl-bicyclo [2.2.1] -hept-2-ene,
5-phenyl-bicyclo [2.2.1] -hept-2-
Ene, tricyclo [4.3.0.1^2,5]-Deca-
3,7-diene (common name dicyclopentadiene), tri
Cyclo [4.3.0.1^2,5] -Dec-3-ene,
Tricyclo [4.4.0.1^2,5]-Undeca-
3,7-diene or tricyclo [4.4.0.1
^2,5] -Undeca-3,8-diene, and
Partially hydrogenated (or cyclopentadiene and cyclohexane
Tricyclo [4.4.0.1), which is an adduct of xen).
^2,5] -Undec-3-ene, tetracyclo [7.
4.0.0^2,7. 1^10,13] -Trideca-
2,4,6,11-tetraene (1,4-methano-1,
4,4a, 9a-tetrahydrofluorene),
Tetracyclo [8.4.0.0^3,8. 1
^11,14] -Tetradeca-3,5,7,12-tetra
Raen (1,4-methano-1,4,4a, 5,10,1
0a-hexahydroanthracene), tetracy
Black [4.4.0.1^2,5. 1^7,10]-Dodeca
-3-ene (also simply referred to as tetracyclododecene), 8
-Methyl-tetracyclo [4.4.0.1^2,5. 1
^7,10] -Dodeca-3-ene, 8-ethyl-tetracy
Black [4.4.0.1^2,5. 1^7,10]-Dodeca
-3-ene, 8-methylidene-tetracyclo [4.4.
0.1^2,5. 1^7,10] -Dodeca-3-ene, 8
-Ethylidene-tetracyclo [4.4.0.
1^2,5. 1^7,10] -Dodeca-3-ene, 8-bi
Nyl-tetracyclo [4.4.0.1^2,5. 1
^7,10] -Dodeca-3-ene, 8-propenyl-tet
Lacyclo [4.4.0.1^2,5 . 1^7,10]-Dode
Car-3-ene, 8-methoxycarbonyl-tetracyclo
[4.4.0.1^2,5. 1^7,10] -Dodeca-3
-Ene, 8-methyl-8-methoxycarbonyl-tetra
Cyclo [4.4.0.1^2,5. 1^7,10]-Dode
Car-3-ene, 8-hydroxymethyl-tetracyclo
[4.4.0.1^{2 , 5}. 1^7,10] -Dodeca-3
-Ene, 8-carboxy-tetracyclo [4.4.0.
1^2,5. 1^7,10] -Dodeca-3-ene, 8-si
Clopentyl-tetracyclo [4.4.0.1^2,5.
1^7,10] -Dodeca-3-ene, 8-cyclohexyl
-Tetracyclo [4.4.0.1^2,5.
1^7,10] -Dodeca-3-ene, 8-cyclohexene
Le-tetracyclo [4.4.0.1^2,5. 1
^7,10] -Dodeca-3-ene, 8-phenyl-tetra
Cyclo [4.4.0.1^2,5. 1^7,10]-Dode
Car-3-ene, pentacyclo [6.5.1.
1^3,6. 0^2,7. 0^9,13] -Pentadeca-
4,10-diene, pentacyclo [7.4.0.0
^2,7. 1^3,6. 1^10,13] -Pentadeca
-4,11-diene and the like are exemplified. Norvol
Nene monomers have a cycloalkyl group or an aryl group
Or a halogen atom, ester type residue,
Polar groups such as tell-type residues, cyano groups, pyridyl groups, etc.
May be provided.

The monocyclic cyclic olefin monomer includes:
For example, cyclohexene, cycloheptene, cyclooctene and the like are exemplified.

Examples of the cyclic conjugated diene monomer include cyclopentadiene and cyclohexadiene.

Examples of the vinyl cyclic hydrocarbon monomer include vinyl cyclohexene and vinyl cyclohexane.

Examples of the aromatic vinyl monomer include an aromatic vinyl compound and an aromatic vinylidene compound, and an aromatic vinyl compound is preferable from the viewpoint of versatility.

Examples of the aromatic vinyl compound include styrene, α-methylstyrene, α-ethylstyrene, α
-Propylstyrene, α-isopropylstyrene, α-
t-butylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methyl Examples thereof include styrene, monochlorostyrene, dichlorostyrene, monofluorostyrene, and 4-phenylstyrene, and preferred examples include styrene, 2-methylstyrene, 3-methylstyrene, and 4-methylstyrene.

These ring structure-containing monomers can be used alone or in combination of two or more.

Polymerization method The above norbornene-based monomer is used, for example, in JP-A-3-148.
No. 82 or JP-A-3-122137, a norbornene-based polymer can be obtained by polymerization using a known method. As the obtained polymer,
Examples thereof include a ring-opening polymer, an addition polymer, and an addition copolymer with a vinyl compound. Among these, a ring-opening polymer is preferable from the viewpoint of heat resistance, transparency, and light resistance.

The ring-opening polymerization comprises a norbornene-based monomer as a ring-opening polymerization catalyst, a metal halide such as ruthenium, rhodium, palladium, osmium, iridium, platinum, a nitrate or acetylacetone compound, and a reducing agent. Catalyst system, or titanium, vanadium,
In the presence of a catalyst system comprising a halide or acetylacetone compound of a metal such as zirconium, tungsten or molybdenum and an organoaluminum compound, in an inert solvent, suitably, at a polymerization temperature of -50 to 100 ° C, 0 to 50 ° C.
The reaction can be performed at a polymerization pressure of kg / cm ² . In the catalyst system, molecular oxygen, alcohol, ether, peroxide, carboxylic acid, acid anhydride, acid chloride, ester, ketone, nitrogen-containing compound, sulfur-containing compound, halogen-containing compound, molecular iodine, other A third component such as a Lewis acid can be added to increase the polymerization activity and the selectivity of ring-opening polymerization.

The addition polymerization of a norbornene-based monomer or the addition copolymerization of a norbornene-based monomer and a vinyl-based compound is carried out, for example, by mixing a monomer component in a solvent with a titanium, zirconium, or vanadium compound and an organoaluminum. In the presence of a catalyst system comprising the compound, usually -50 to 1
It can be carried out by a method of copolymerizing at a polymerization temperature of 00 ° C. and a polymerization pressure of 0 to 50 kg / cm ² . The vinyl compound is not particularly limited as long as it can be copolymerized. For example, ethylene, propylene, 1-butene, 1-pentyne, 1-hexene, 3-methyl-1-butene, 8-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-
Hexene, 4,4-dimethyl-1-hexene, 4.4-
Dimethyl-1-pentene, 4-ethyl-1-hexene,
Carbon number 2 such as 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc.
A chain vinyl compound such as ethylene or α-olefin of from 20 to 20; 1,4-hexadiene, 4-methyl-1,4
-Hexadiene, 5-methyl-1,4-hexadiene,
Non-conjugated diene compounds such as 1,71-octadiene; and the like. These vinyl compounds can be used alone or in combination of two or more.

The polymerization of a monocyclic cyclic olefin monomer is carried out by
The addition polymerization can be carried out by a known method, for example, a method disclosed in JP-A-64-66216.

The polymerization of the cyclic conjugated diene monomer can be carried out by a known method, for example, as described in JP-A-6-13657 and JP-A-7-36057.
In the method disclosed in US Pat.
A polymer obtained by-or 1,4-addition polymerization can be obtained.

The polymerization of the vinyl alicyclic hydrocarbon monomer is carried out by
For example, the polymerization can be carried out by the method disclosed in JP-A-51-59989.

The polymerization of the aromatic vinyl monomer is, for example,
Polymerization can be carried out by a known method disclosed in JP-A-1-317728 or the like, and copolymerization can be carried out in combination with another monomer copolymerizable with an aromatic vinyl monomer.

Other monomers that can be copolymerized include:
Although there is no particular limitation, a chain vinyl compound and a chain conjugated diene compound are used. When a chain conjugated diene is used, the resulting hydrocarbon-based copolymer has excellent strength characteristics. Examples of the chain vinyl compound include the chain vinyl compounds copolymerizable with the norbornene-based monomer described above, and ethylene, propylene, and 1-butene are preferable. Examples of the chain conjugated diene include 1,3-butadiene,
Isoprene, 2,3-dimethyl-1,3-butadiene,
Examples include 1,3-pentadiene and 1,3-hexadiene. Among these chain vinyl compounds and chain conjugated dienes, chain conjugated dienes are preferred, and butadiene and isoprene are particularly preferred. These chain vinyl compounds and chain conjugated dienes can be used alone or in combination of two or more.

After completion of the polymerization, the polymer can be recovered by a known method, for example, a steam stripping method, a direct desolvation method,
An alcohol coagulation method and the like can be mentioned. When an inert solvent is used for the hydrogenation reaction during the polymerization, the polymer can be used as it is in the hydrogenation step without recovering the polymer from the polymerization solution.

The molecular weight of the ring structure-containing polymer is appropriately selected according to the purpose of use, but from the viewpoint of a balance between mechanical strength and moldability, a cyclohexane solution (a toluene solution when the polymer resin is not dissolved). The weight average molecular weight (Mw) in terms of polyisoprene (polystyrene in a toluene solution) measured by gel permeation chromatography is usually 5,000 or more, preferably 5,000 to 5,000.
500000, more preferably 3000-20000
0, particularly preferably 10,000 to 100,000.
If the molecular weight is excessively large, not only does the moldability deteriorate, but also in the case of performing hydrogenation described below, the progress of the hydrogenation reaction is slowed, and the hydrogenation rate is reduced. When the molecular weight is too small, the mechanical strength of the polymer becomes small.

The molecular weight distribution (Mw / M
n) is usually 7 or less, preferably 5 or less, more preferably 3.5 or less. When the molecular weight distribution is in the above range, the content of the high molecular weight component is small, there is no coloring of a molded article molded using the polymer, and also, the flowability of the molten resin during molding is improved, No molding defects such as sink marks on molded products do not occur.

Sequential Addition In the present invention, for polymerization of the monomer, for example, a polymerization reactor 2 shown in FIG. 1 can be used.

The polymerization reactor 2 shown in FIG. 1 has a reactor main body 4 made of, for example, metal or glass for performing a polymerization reaction. A rotatable and rotatable rotary shaft 6 made of, for example, a metal or a synthetic resin is disposed inside the reactor main body 4. The rotary shaft 6 is driven by a driving means (not shown) such as a motor, for example. Linked to A stirring blade 8 is attached to the rotating shaft 6, and by rotating the rotating shaft 6, the liquid content in the reactor main body 4 is stirred and mixed.

In this embodiment, a nozzle 42 is provided on the upper inner wall surface 4a of the reactor body 4 so as to protrude inside. However, the arrangement position of the nozzle 42 is
Not only the upper inner wall surface 4a but also the side inner wall surface 4b may be used.

The nozzle 42 may have a cylindrical shape,
Although it may be prismatic, it is preferably cylindrical from the viewpoint of the supply efficiency of the sequentially added portion (see FIG. 1). When the nozzle shape is cylindrical, the diameter of the cross section of the nozzle is usually 5 to 3
00 mmφ, preferably 10 to 200 mmφ.

The supply port 42a is not particularly limited as long as it has a shape such that the liquid is not sealed off by a liquid and has a good drainage shape. For example, a cylindrical nozzle such as the tip of a syringe needle in a syringe is obliquely cut. It is preferable to have such an elliptical cross-sectional shape.

The projecting length L of the supply port 42a is preferably 10 to 2000 m from the inner wall surface 4a of the reactor body 4.
m, more preferably 50 to 1500 mm, even more preferably 100 to 1000 mm or more.

In the present invention, during the polymerization reaction, the monomer having a ring structure and / or the polymerization catalyst is sequentially added from a supply port 42 a provided at the tip of the nozzle 42. Specifically, a part (initial charge) of the ring structure-containing monomer and / or the polymerization catalyst is charged in the reactor main body 4 in advance, and the temperature in the reaction system is adjusted to a predetermined temperature while the ring is adjusted. The remainder of the structure-containing monomer and / or polymerization catalyst (sequential addition) is continuously dropped from the supply port 42a.

Either one of the ring structure-containing monomer and the polymerization catalyst may be added successively, but it is preferable to add the two methods successively. It is most preferable to add sequentially from separate supply ports using the above nozzle. In this case, it is preferable to perform the sequential addition using the nozzle 44 having the supply port 44a shown in FIG. 1 in addition to the supply port 42a. The nozzle 44
The protrusion length L1 of the supply port 44a at
The protrusion length L may be set in the same range as the protrusion length L of 2a, and the protrusion lengths L and L1 may be the same length or different lengths.

When the sequential addition is performed using separate nozzles, the rate of each sequential addition is adjusted so that the start and end of the sequential addition of the cyclic structure-containing monomer and the polymerization catalyst are simultaneous. Is preferred. Further, by integrating the tip portions of the nozzle 42 and the nozzle 44 into one supply port, the ring structure-containing monomer and the polymerization catalyst can be mixed immediately before addition.

During the polymerization reaction, the stirring of the reaction system is usually continued.

As described above, the addition of the successively added components is performed from the supply port 42a disposed at a position protruding into the inside from the inner wall surface 4a of the reactor main body 4, whereby the added monomer and polymerization catalyst are added. Are uniformly dispersed in the reaction solution in a short time. For this reason, the molecular weight distribution of the obtained polymer becomes small. Further, the two successively added components substantially do not pass through the inner wall surface 4a of the reactor body 4 and are added to the reaction solution. For this reason,
The risk of local reactions occurring and the formation of high molecular weight components is reduced. As a result, the color tone of a molded article molded using the polymer obtained by the method of the present invention becomes good,
Molding defects such as sink marks do not occur.

It is preferable that the supply port 42a is not in contact with the reaction solution surface 10 from the start to the end of the polymerization reaction, that is, it is preferably arranged above the reaction solution surface 10. The supply port 42a is provided above the reaction liquid surface 10 and does not come into contact with the reaction liquid.
It is possible to more remarkably prevent a local reaction from occurring at the tip portion of the polymer to generate a high molecular weight component. As a result, similarly to the above, the color tone of a molded article molded using the obtained polymer is improved, and molding defects such as sink marks do not occur.

The amount of the cyclic structure-containing monomer to be sequentially added to the total amount used is usually 20 to 100% by weight, preferably 50 to 99.5% by weight, from the viewpoint of suppressing the formation of high molecular weight components and reducing the molecular weight distribution. %, More preferably 80 to 99% by weight, and the sequential addition amount based on the total amount of the polymerization catalyst used is:
Similarly, from the viewpoint of suppressing the production of high molecular weight components and reducing the molecular weight distribution, it is usually 10 to 100% by weight, preferably 2 to 100% by weight.
The content is 0 to 95% by weight, more preferably 30 to 90% by weight.

The cyclic structure-containing monomer and / or polymerization catalyst to be added sequentially is preferably a solvent solution so as to be uniformly dispersed in a short time after being dropped into the reaction solution. In the case of a monomer, a solution of 10 to 100% by weight is preferable, and in the case of a polymerization catalyst, a solution of 0.01 to 30% by weight is preferable.

The sequential addition time is from 0.1 to 10 hours, preferably from 0.1 to 10 hours, from the viewpoint of temperature control by removing reaction heat.
It is 5 to 7 hours, more preferably 0.2 to 5 hours.

The temperature in the reaction system during the sequential addition is from 0 to 100 ° C., preferably from 5 to 95 ° C., from the viewpoint of controlling the polymerization reaction rate.
° C, more preferably from 10 to 80 ° C.

From the viewpoint of controlling the rate of addition, for example, a pump feed or a pressure feed with an inert gas is suitable as a method for sequentially adding the monomer and the polymerization catalyst.

Hydrogenation Step In the present invention, the above-mentioned polymer having a ring structure, such as an alicyclic structure-containing polymer or an aromatic vinyl polymer, obtained by polymerizing a ring structure-containing monomer is used as the main chain and the main chain. And / or in the side chain,
When it has a carbon-carbon unsaturated bond (such as a non-conjugated unsaturated bond and / or an aromatic unsaturated bond), part or all of the unsaturated group can be hydrogenated to be saturated. Hydrogenation of the unsaturated group improves the heat deterioration resistance and light deterioration resistance of the ring structure-containing polymer.

When the polymer has an aromatic ring, the residual ratio of the aromatic ring is usually from 0 to 100%, preferably from 0 to 80%, more preferably from 0 to 50% from the viewpoint of light resistance and the like.

The hydrogenation rate of the non-conjugated unsaturated bond is usually 80
% Or more, preferably 90% or more, more preferably 95%
That is all. If the hydrogenation rate is low, oxidative deterioration and molecular breakage are likely to occur, resulting in poor tint, reduced transparency, and reduced mechanical strength. In addition, 1H-NM
By the analysis with R, the unsaturated bond in the aromatic ring structure can be recognized and distinguished from other unsaturated bonds.

The hydrogenation reaction is carried out according to a conventional method by bringing the polymer into contact with hydrogen in the presence of a hydrogenation catalyst. Examples of the hydrogenation catalyst include JP-A-58-43412 and JP-A-60-1984.
JP-A No. 26024, JP-A-64-24826, JP-A-1-138257, JP-A-7-41550 and the like can be used, and a homogeneous catalyst or a heterogeneous catalyst can be used. May be. Homogeneous catalysts are easy to disperse in the hydrogenation reaction solution, so they need to be added in a small amount.Also, they are active even without high temperature and pressure, so they do not cause polymer decomposition or gelation, resulting in low cost and quality. Excellent stability etc. Heterogeneous catalysts are highly active at high temperatures and pressures, can be hydrogenated in a short time, and are excellent in production efficiency such as being easily removed. Among them, a heterogeneous catalyst is preferable because it is easily removed.

Examples of the homogeneous catalyst include so-called Wilkinson complexes such as chlorotris (triphenylphosphine) rhodium (I); cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n-
A catalyst comprising a combination of a transition metal compound such as butyllithium, zirconocene dichloride / sec-butyllithium, tetrabutoxytitanate / dimethylmagnesium and an alkyl metal compound; and the like.

As the heterogeneous catalyst, for example, Ni, P
Examples include those in which a hydrogenation catalyst metal such as d, Pt, Ru, and Rh is supported on a carrier. In particular, when an adsorbent such as alumina or diatomaceous earth is used as the carrier, it is preferable because impurities are not mixed. These catalysts are used in an amount of ^{10-5 to} 0.5 parts by weight, preferably ^10-4 to 0.5 parts by weight, based on 1 part by weight of the polymer.
Used in the range of 0.3 parts by weight. The hydrogenation catalyst can be added to the polymerization reaction solution as it is, or added after removing the polymerization catalyst from the polymerization reaction solution to cause a reaction.

The hydrogenation reaction is usually carried out in an inert solvent. The inert solvent is not particularly limited as long as it is inert to the catalyst, and may be the same as the polymerization reaction solvent, or may be further added to the polymerization reaction solution. The amount of the inert solvent used for hydrogenation is usually 1 to 1 in weight ratio to the polymer in the polymerization reaction solution from the viewpoint of hydrogenation reaction efficiency.
100 times, preferably 1.5 to 20 times, more preferably 2 times
It is 10 times.

The hydrogenation reaction can be carried out according to a conventional method.
Although hydrogenation depends on the type of hydrogenation catalyst and reaction temperature
Rate can be changed, and the residual rate of aromatic ring can also be changed.
You. When the above hydrogenation catalyst is used, the aromatic ring is unsaturated.
In order to maintain a certain amount of bonds, lower the reaction temperature.
Decrease the hydrogen pressure, shorten the reaction time, etc.
May be performed. Complete aromatic ring structure in polymer
Non-conjugated unsaturation of the main chain while remaining without hydrogenation
In order to selectively increase the hydrogenation rate of the sum bond, hydrogen
Pressure is 0.1-50kg / cm², Preferably 0.5 to
40kg / cm ², More preferably 1 to 30 kg /
cm²And The reaction temperature of the hydrogenation
When used, it is usually −10 to 150 ° C., preferably 0 to 150 ° C.
To 130 ° C, more preferably 20 to 110 ° C.
When a heterogeneous catalyst is used, it is usually 0 to 300 ° C.
Preferably 100-250 ° C, more preferably 150-
Performed at 230 ° C.

The hydrogenation reaction can be stopped by stopping the supply of hydrogen. After the completion of the hydrogenation reaction, the polymer may be recovered by a known method in the same manner as after the completion of the polymerization.

The molecular weight of the hydride of the ring structure-containing polymer is as follows:
The weight-average molecular weight in terms of polyisoprene (polystyrene in a toluene solution) measured by gel permeation chromatography of a cyclohexane solution (a toluene solution if the polymer resin does not dissolve), which is appropriately selected according to the purpose of use. (Mw), usually 5000 or more, preferably 5000 to 500000, more preferably 8000.
To 200,000, particularly preferably 10,000 to 1,000
00.

The molecular weight distribution Mw / Mn of the hydride of the ring structure-containing polymer is usually 7 or less, preferably 5 or less, more preferably 3.5 or less.

The glass transition temperature (Tg) of the hydride of the ring structure-containing polymer is usually 50 to 250 ° C., preferably 7 to 250 ° C.
The temperature is 0 to 220 ° C, more preferably 80 to 200 ° C.

Inert Solvent The inert solvent used in the above-mentioned polymerization reaction and hydrogenation reaction can sufficiently dissolve the ring structure-containing monomer, the ring structure-containing polymer, and the hydride of the ring structure-containing polymer, and It does not inhibit polymerization reaction or hydrogenation reaction. Examples of such an inert solvent include alkanes such as pentane, hexane, heptane, octane, nonane, and decane; cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane,
Diethylcyclohexane, trimethylcyclohexane,
Cycloalkanes such as cycloheptane, cyclooctane, decalin, norbornane, methylnorbornane, ethylnorbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene Compounds such as halogenated alkanes and aryls such as dibromide, chlorobenzene, chloroform and tetrachloroethylene; and the like. Among them, from the viewpoint of solubility and the like, cycloalkanes or aromatic hydrocarbons are preferable, and cycloalkanes are more preferable.
These inert solvents can be used alone or in combination of two or more.

The amount of the inert solvent is not particularly limited, but is usually 0 to 100 parts by weight of the ring structure-containing monomer in consideration of the balance between the stirring efficiency and the productivity.
It is 2,000 parts by weight, preferably 40 to 1000 parts by weight, more preferably 100 to 600 parts by weight.

Additives The polymer containing a ring structure (including hydrides) obtained by the method of the present invention may be added , if necessary, with one or more other polymers, various compounding agents and fillers. Is also good.

Other polymers include elastomers such as polybutadiene, polyisoprene, SBS, SIS and SEBS; polystyrene, poly (meth) acrylate, polycarbonate, polyester, polyether,
Resins such as polyamide, polyimide, and polysulfone; and the like. These other polymers can be used alone or in combination of two or more.

The compounding agent is not particularly limited as long as it is generally used in thermoplastic resin materials. Examples thereof include antioxidants, ultraviolet absorbers, light stabilizers, near infrared absorbers, dyes and pigments. And colorants, lubricants, plasticizers, antistatic agents, optical brighteners, flame retardants, antiblocking agents, leveling agents and the like. Among them, it is preferable to add an antioxidant, and as such an antioxidant, a phenolic antioxidant, a phosphorus-based antioxidant,
And sulfur-based antioxidants.

Examples of the organic or inorganic filler include silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, basic magnesium carbonate, dowamite, calcium oxide, calcium carbonate, calcium sulfate, and the like. Minerals such as potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica and asbestos; fibers such as glass fiber, boron fiber, silicon carbide fiber, polyethylene fiber, polypropylene fiber, polyester fiber, polyamide fiber; glass flake, glass Examples include beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, and the like.

These fillers can be added alone or in combination of two or more. The compounding ratio of the filler can be appropriately determined according to each function and purpose of use as long as the object of the present invention is not impaired.

In order to avoid elution from the ring-structure-containing polymer molded article obtained in the present invention, those additives and resins having a higher molecular weight are more preferable.

Molding The polymer having a ring structure (including a hydride) obtained by the method of the present invention is kneaded in a molten state using a twin-screw extruder or the like after production, and
It can be used as pellets. And well-known methods, for example, injection molding, extrusion molding, cast molding,
It can be formed by inflation molding, blow molding, vacuum molding, press molding, compression molding, rotational molding, calendar molding, rolling molding, cutting molding, or the like.

Applications The polymer having a ring structure (including hydrides) obtained by the method of the present invention is useful in a wide range of fields as various molded articles including optical materials.

For example, an optical disk, an optical lens, a prism, a light diffusion plate, an optical card, an optical fiber, an optical mirror,
Optical materials such as liquid crystal display element substrates, light guide plates, polarizing films, retardation films, etc .; liquid medicine containers for injections, ampules, vials, prefilled syringes, bags for infusions,
Liquid, powder or solid medicine containers such as sealed medicine bags, press-through packages, solid medicine containers, eye drop containers, food containers, blood test sampling test tubes, medicine container caps, blood collection tubes, specimen containers, etc. Sampling containers, medical instruments such as syringes, sterile containers such as scalpels, forceps, gauze, contact lenses and other medical instruments, experiment and analysis instruments such as beakers, petri dishes, flasks, test tubes, centrifuge tubes,
Medical optical parts such as plastic lenses for medical examinations, medical infusion tubes, piping materials such as pipes, joints, valves, etc., medical equipment such as artificial organs such as denture bases, artificial hearts, artificial roots and the like; Trays, carriers, containers for processing or transfer such as cases, carrier tapes, protective materials such as separation films, pipes, tubes, valves, pipes such as sipper flow meters, filters, pumps, sampling containers, bottles, ampoule bags Equipment for processing electronic components such as liquid containers, etc .; Covering materials for electric wires and cables; OA equipment such as consumer / industrial electronic equipment, copying machines, computers, printers, etc .; Board, flexible printed circuit board,
Circuit boards such as multilayer printed wiring boards, especially high-frequency circuit boards for satellite communication equipment that require high-frequency characteristics; bases for transparent conductive films such as liquid crystal substrates, optical memories, and surface heating elements such as automobile and aircraft defrosters Material, transistor, I
Sealing materials and parts for electric and conductors such as C, LSI, LED, etc., sealing materials for electric and electronic parts such as motors, capacitors, switches and sensors, body materials such as TVs and video cameras, parabolic antennas, flat antennas, radar Electrical insulating materials such as dome structural members; and the like.

[0075]

The present invention will be specifically described below with reference to examples and comparative examples. In the following Examples and Comparative Examples, parts and% are by weight unless otherwise specified.

The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured by high performance liquid chromatography (in terms of polystyrene) using cyclohexane as a mobile layer, unless otherwise specified. The hydrogenation rate is ¹ H
-Measured by NMR.

Example 1 In a nitrogen atmosphere, 1150 parts of dehydrated cyclohexane was added to
As a monomer for polymerization, 8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodeca-3
After 5 parts of -ene (ethyltetracyclododecene, hereinafter referred to as ETCD), 2.7 parts of 1-hexene, 0.6 part of isobutyl alcohol and 1.6 parts of triisobutylaluminum are mixed at room temperature in a polymerization reactor. While maintaining the temperature at 40 ° C., 50 parts of a 0.65% solution of tungsten hexachloride in cyclohexane was added to carry out an initial polymerization reaction.

Sequential addition polymerization reaction using an inner nozzle Then, 115 parts of a 0.65% solution of tungsten hexachloride in cyclohexane and 495 parts of a monomer (ETCD) were introduced into the reactor body to a length of 200 mm and a diameter of 12 mm. The polymerization reaction was carried out while successively adding using a cylindrical nozzle. The discharge port at the tip of the nozzle used had an elliptical shape obtained by diagonally cutting the cylinder.
Separate nozzles were used for the sequential addition of tungsten hexachloride and monomer, and the addition was adjusted so that the addition started and ended simultaneously, and the addition was performed so that the time from the start to the end was 2 hours 30 minutes. The speed was adjusted. Further, from the start to the end of the sequential addition, the tip of the nozzle did not touch the liquid surface of the reaction solution.

[0079] 1.4 parts of propylene oxide and 1.5 parts of isopropyl alcohol were added to the polymerization solution to inactivate the polymerization catalyst and terminate the polymerization reaction. The polymerization conversion of the obtained ETCD ring-opened polymer was almost 100%, Mn was 120,000, Mw was 25,000, and molecular weight distribution (Mw /
Mn) was 2.1.

To 100 parts of the above ring-opening polymer solution, 270 parts of cyclohexane, 5 parts of a nickel-alumina catalyst (manufactured by JGC Corporation) as a hydrogenation catalyst were added, and the mixture was pressurized to 50 kg / cm ² with hydrogen and stirred. Temperature 2
After heating to 00 ° C, the reaction was carried out for 4 hours to obtain a ring-opened polymer hydrogenated polymer solution (polymer content: 20%).

Removal of Catalyst and Removal of Solvent Next, the reaction solution having a polymer content of 20% was subjected to pressure filtration at a pressure of 2.5 kg / cm ² using a pressure filter (Funda filter, manufactured by Ishikawajima-Harima Heavy Industries, Ltd.). The first filtration step) gave a colorless and transparent solution (solution 1). Radiolight # 500 was used as a filtration bed. This solution 1
Using a cylindrical concentrating dryer (manufactured by Hitachi, Ltd.), the operating conditions were changed to the first step: temperature 270 ° C., pressure 100 Torr.
r, second step: removing at a temperature of 270 ° C. under a pressure of 5 Torr (drying step), and removing a solvent (cyclohexane) 430
And the ring-opening polymer hydrogenated polymer 17
0 parts were obtained.

Mn of the obtained hydrogenated polymer was 180.
00, Mw was 37,500, (Mw / Mn) was 2.1, and the hydrogenation rate was 99.9% or more.

To 100 parts of the obtained hydrogenated ring-opening polymer,
Anti-aging agent (Irganox 101 manufactured by Ciba-Geigy)
0) 0.2 part and a soft polymer (ToughTech H manufactured by Asahi Kasei Corporation)
1052) 0.2 parts were added, and a twin-screw kneader (TEM-35B, manufactured by Toshiba Machine Co., screw diameter 37 mm, L / D = 3)
2. Screw rotation speed 250 rpm, resin temperature 210
At a feed rate of 10 kg / hour) and extruded into pellets.

The above-mentioned pellets were injected into a side gate mold type injection molding apparatus (product number IS4 manufactured by Toshiba Machine Co., Ltd.).
50), the length is 280 mm and the width is 1 by injection molding.
A flat plate having a thickness of 90 mm and a thickness of 2 mm was formed. The molding conditions are
The mold temperature was 80 ° C, the cylinder temperature was 280 ° C, and the nozzle temperature was 260 ° C.

The coloring degree and moldability of the obtained flat plate were evaluated. As a result, the obtained flat plate was colorless and transparent without coloring, and was good without observing molding defects such as sink marks and silver streaks. The results are shown in Table 1.

The degree of coloring of the flat plate was determined by the difference in yellowing index (△
YI). ΔYI indicates the yellowness index (YI; yellow index) of the test solution obtained by dissolving a part of the formed flat plate in a soluble solvent at a concentration of 15% by weight according to JIS-K7103. Using an analyzer, measurement optical path 10 mm; blank: measured as a solvent for dissolution, and a value obtained by subtracting the YI value of only the blank solvent from the measured YI value was determined as a ΔYI value derived from a flat plate. In addition, the measurement was performed three times and evaluated using the average value. Also, whether the solution was completely dissolved was determined by filling the syringe into a syringe with a 0.5 μm PTFE filter attached to the tip, and discharging all the liquid from the filter tip without resistance when the piston was pressed. confirmed. The case where ΔYI is less than 0.7 is “非常 (very good)”, and the case where ΔYI is 0.7 or more and less than 1.0 is “○”.
(Good) ”,“ 場合 (somewhat bad) ”when ΔYI is 1.0 or more and less than 1.5,“ × ”when ΔYI is 1.5 or more.
(Poor) ".

The formability of the flat plate was evaluated according to the following criteria by visually judging the obtained flat plate. 10
No appearance failure such as sink marks, silver streaks, etc. in the first injection molding "◎", 10 or more injection moldings showing the above molding failure in 1 to 2 samples "○", 10 injection moldings in 3 injection moldings △ indicates that the molding failure was observed in 4 samples, and “X” indicates that the molding failure was observed in 5 or more samples after 10 injection moldings.

Example 2 A polymerization reaction was carried out in the same manner as in Example 1 except that the tip of the polymerization monomer addition nozzle was immersed in the reaction solution for 15 minutes immediately before the end of the sequential addition of the polymerization monomer and the polymerization catalyst. As a result, the polymerization conversion of the obtained polymer was almost 100%.
However, Mn was 12,000, Mw was 28,000, and molecular weight distribution (Mw / Mn) was 2.4, and the molecular weight distribution was slightly larger than that in Example 1.

Next, a hydrogenation reaction was carried out in the same manner as in Example 1. As a result, the obtained polymer hydride had Mn of 18,000, Mw of 41,000, and (Mw / Mn) of 2.
4. The hydrogenation rate was 99.8%, and the hydrogenation rate was slightly lower than that of Example 1.

Thereafter, pellets were produced in the same manner as in Example 1, and a flat plate was formed using the pellets. As a result, no defective molding such as sink marks and silver streaks was observed in the obtained flat plate. (Yellow). The results are shown in Table 1.

Example 3 A polymerization reaction was carried out in the same manner as in Example 1 except that the protrusion length of the inner nozzle was changed to 5 mm. As a result, the polymerization conversion of the obtained polymer was almost 100%. Is 1150
0, Mw was 26,500, and molecular weight distribution (Mw / Mn) was 2.3, and the molecular weight distribution was slightly larger than that in Example 1.

Then, a hydrogenation reaction was carried out in the same manner as in Example 1. As a result, the obtained polymer hydride had Mn of 17000, Mw of 39500, and (Mw / Mn) of 2.
3. The hydrogenation rate was 99.8%, and the hydrogenation rate was slightly lower than that of Example 1.

Thereafter, pellets were produced in the same manner as in Example 1, and a flat plate was formed using the pellets. As a result, although no defective molding such as sink marks and silver streaks was observed, the obtained flat plate was slightly colored. (Yellow). The results are shown in Table 1.

Comparative Example 1 A polymerization reaction was carried out in the same manner as in Example 1 except that the inner nozzle of Examples 1 to 4 was not used and a polymerization reactor having a supply port provided on the inner wall of the reactor body was used. As a result, the polymerization conversion of the obtained polymer was almost 100%, but Mn was 11,000, Mw was 29,500, and the molecular weight distribution (Mw / M
n) was 2.7, and the molecular weight distribution was larger than that in Example 1.

Next, a hydrogenation reaction was carried out in the same manner as in Example 1. As a result, the obtained polymer hydride had Mn of 16,500, Mw of 44500, and (Mw / Mn) of 2.
7. The hydrogenation rate was 99.8%, and the hydrogenation rate was lower than in Example 1.

Thereafter, pellets were produced in the same manner as in Example 1, and a flat plate was formed using the pellets. As a result, the obtained flat plate was colored (yellow), and sink marks were observed. Thereby, the superiority of Examples 1-4 was confirmed.
The results are shown in Table 1.

Comparative Example 2 A flat plate was molded in the same manner as in Comparative Example 1 except that the cylinder temperature (molding temperature) at the time of injection molding was set at 320 ° C. As a result, a slight sink mark was observed on the obtained flat plate. , Was quite colored (yellow). Thereby, the superiority of Examples 1-4 was confirmed. The results are shown in Table 1.

[0098]

[Table 1]

[0099]

As described above, according to the present invention, a ring structure-containing polymer capable of efficiently producing a large amount of a ring structure-containing polymer which is less likely to cause molding defects such as coloring and sink marks on a molded article. A method for producing a coalescence and a polymerization reactor can be provided.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a main part showing one embodiment of a polymerization reactor according to the present invention.

[Explanation of symbols]

 2 polymerization reactor 4 reactor body 4a upper inner wall surface 4b side inner wall surface 42, 44 nozzle 42a, 44a supply port 6 rotating shaft 8 stirring blade

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J011 BA06 BA09 BB05 BB13 BB17 DA04 DB12 DB16 DB19 DB21 4J032 CA25 CA34 CE03 4J100 AB02P AB03P AB04P AB07P AB08P AB10P AR02P AR05P AR11P AR17P AR18P BC43P CA01 CA04 FA19 FA

Claims (4)

[Claims] 1. A ring structure-containing monomer and / or a polymerization catalyst are sequentially added from a supply port protruding into a reactor main body to polymerize the ring structure-containing monomer in the presence of a polymerization catalyst. And a method for producing a polymer having a ring structure, which comprises hydrogenating the produced polymer, if necessary. 2. The projecting length of the supply port is 10 mm or more from the inner wall surface of the reactor main body, and the supply port is disposed above a liquid surface of a reaction solution during a polymerization reaction. The production method of the polymer having a ring structure according to the above. 3. The reactor according to claim 1, wherein the supply port is formed at a tip portion of a cylindrical nozzle provided so as to protrude into the reactor main body, and has an elliptical cross section. The method for producing a polymer having a ring structure of the above. 4. A nozzle having a reactor body and a supply port formed at a tip end thereof so as to protrude into the interior of the reactor body and for sequentially adding a monomer and / or a polymerization catalyst. A polymerization reactor having: