JP3455937B2 - Norbornene-based hydrogenated polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] TECHNICAL FIELD The present invention relates to a norbornene-based water
For more details on the element-added polymer,
Contains polymer and has excellent birefringence, transparency and heat resistance
, A new norbornene soluble in non-halogen solvents
The present invention relates to a hydrogenated copolymer. [0002] 2. Description of the Related Art A resin having excellent birefringence and transparency is used as a resin.
Limethyl methacrylate (PMMA), polycarbonate
(PC) and norbornene-based resins. these
Resin has excellent transparency, birefringence and electrical properties
It has the ability to take advantage of these characteristics,
For a wide range of applications such as electric / electronic parts, optical parts, and building materials
It has been. However, in recent years, due to environmental regulations,
The use of logogenic solvents has begun to be regulated. On the other hand, the above-mentioned resins and the like are cast-filled.
Like binders, varnishes, adhesives, etc.
When manufacturing after dissolving in
Is the use of a gen-based solvent a hygienic or environmental measure?
It is necessary to provide local exhaust equipment. Also, large amounts of solvent
When using a
Since it cannot be released, it is necessary to recover the solvent.
It becomes important. Therefore, to use a halogenated solvent,
It is necessary to make a fair capital investment. Use adhesives, etc.
Local exhaust may not be possible depending on the location
It has become. [0005] PMMA, PC, norbornene resin, etc.
Are halogenated solvents (methylene chloride, chloroform, etc.)
Is relatively well soluble in non-halogen solvents.
There is another problem that is difficult to melt. Norvol
In the case of nene-based resins, ether-based and aromatic-based solvents
Some resins are soluble, but these have additional problems.
You. That is, ether solvents are acutely toxic (narcotic)
At present, it is difficult to use. Benze
Is carcinogenic, and toluene can be used as a sole solvent.
Causes acute and chronic poisoning and is difficult to use. Also,
It is difficult to use such as Siren because it has a high boiling point. In particular,
In order to produce a strike film, a relatively low boiling, non-halo
Transparent, low birefringence, heat-resistant
Resins with excellent properties (having a high glass transition temperature)
Instead, such resins have been desired. [0006] The problem to be solved by the present invention is that
In order to solve the above-mentioned drawbacks of resin, non-halogen
A resin that dissolves in the system solvent, and the resin
Excellent refraction, transparency and heat resistance (high glass transition temperature)
To provide a novel resin. [0007] SUMMARY OF THE INVENTION The present invention relates to a conventional resin.
As a result of intensive research to solve these shortcomings,
(A) a monomer represented by the following general formula (I) and the following general formula
Or (b) a monomer represented by the following general formula:
A monomer represented by (I) and a monomer represented by the following general formula (II)
A monomer (II) and a monomer copolymerizable with these monomers;
Is non-halo obtained by ring-opening copolymerization and further hydrogenation.
Provided is a hydrogenated polymer that is soluble in a gen-based solvent. [0008] Embedded image (In the formula (I), E¹, F¹, G¹, J¹Is
Represents a hydrogen atom, a halogen atom, or a monovalent organic group,
Or linked together to form a monocyclic or polycyclic group
And the monocyclic or polycyclic group has a double bond
And E¹, F¹, G¹, J¹2 out of
One is a group containing an alkoxycarbonyl group, and k is 0 or
Or a positive integer of 3 or less, and q is 0 or 1. ) [0010] Embedded image In the formula (II), E^Two, F^Two, G^Two, J^TwoIs
A hydrogen or halogen atom or a monovalent organic group.
Or even when linked together to form a monocyclic or polycyclic group
Well and the monocyclic or polycyclic group has a double bond
And E^Two, F^Two, G^Two, J^TwoOne of
Is a group containing an alkoxycarbonyl group, and k is 0 or
Is a positive integer of 3 or less, and q is 0 or 1. ) [0012] BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be specifically described.
I will tell. The formula (I) used in the present invention is represented by the following formula:
(Hereinafter referred to as “monomer (1)”).
The alkoxy carboxy represented by the following general formula (III)
Norbornene-based compounds containing two groups containing a nyl group
Can be used. [0014] Embedded image Wherein n is 0 or a positive integer;¹
Is a hydrocarbon group having 1 to 12 carbon atoms. ) In the general formula (III), R¹Has 1 to 1 carbon atoms
12 hydrocarbon groups, preferably an alkyl group, for example,
Methyl, ethyl, propyl, butyl, octyl
Group, decyl group, dodecyl group and the like. Also, n is 0 or
Is a positive integer. The smaller the value of n, the higher the opening
Preferred because the glass transition temperature of the ring copolymer is high,
Further, the monomer (I) wherein n is 0 can be easily synthesized.
At some point, also the glass transition temperature of the resulting ring-opened copolymer
It is preferable in that the degree becomes high. The general formula (III)
Preferred specific examples of the alkoxycarbonyl group represented by
Are methoxycarbonyl group, ethoxycarbonyl
Group, n-propyloxycarbonyl group, isopropyl
Xycarbonyl group, n-butoxycarbonyl group and the like.
Can be In the general formula (I), a halogen atom
Examples of the child include fluorine, chlorine, bromine and iodine.
Preferably, a fluorine atom is a monovalent organic group,
Group, substituted or unsubstituted alkyl group, substituted or unsubstituted
And substituted alkoxy groups. Unsubstituted alk
Methyl group, ethyl group, n-propyl group,
Isopropyl group, n-butyl group, sec-butyl group, t
tert-butyl group, hexyl group, octyl group, decyl
Group, dodecyl group and the like. Unsubstituted alkoxy group
Is a methoxy group, an ethoxy group, a propyloxy group,
Examples include an isopropyloxy group and a butoxy group. A substituent of an alkyl group or an alkoxy group;
And halogen atoms such as fluorine, chlorine, bromine and iodine;
And a hydroxyl group. As the substituted alkyl group, full
Oromethyl group, difluoromethyl group, trifluoromethyl
Group, pentafluoromethyl group, heptafluoroisop
Examples thereof include a propyl group and a pentafluoropropyl group.
Further, as the substituted alkoxy group, fluoromethoxy
Group, trifluoromethoxy group, pentafluoroethoxy
Group, pentafluoropropyloxy group, heptafluoro
And a propyloxy group. In the general formula (I), two alkoxy groups
Groups containing a carbonyl group are the same carbon source on the norbornene ring.
Is preferably not bonded to the
The atom is a hydrogen atom or an alkyl group, especially a methyl group.
It is preferable that they are compatible from the viewpoint of easy production. Also, E¹, G¹, F¹, J¹Are connected to each other
When taken together to form a monocyclic or polycyclic group,
Groups are, for example, cyclohexyl, 1-cyclohexene
Mono, naphthyl, octahydronaph
It may be a polycyclic group such as tyl. Specific examples of the monomer (1) include 8,9-
Dimethoxycarbonyltetracyclo [4.4.0.1
^2,5. 1^7,10] -3-dodecene, 8,8-dimethoxyca
Rubonyltetracyclo [4.4.0.1^2,5. 1^7,10]
-3-dodecene, 8-methoxycarbonyl-9-ethoxy
Cycarbonyltetracyclo [4.4.0.1^2,5. 1
^7,10] -3-dodecene, 8-methoxycarbonyl-8-
Ethoxycarbonyltetracyclo [4.4.0.
1^2,5. 1^7,10] -3-dodecene, 8,9-diethoxy
Carbonyltetracyclo [4.4.0.1^2,5.
1^7,10] -3-dodecene, 8,8-diethoxycarboni
Letetracyclo [4.4.0.1^2,5. 1^7,10] -3-
Dodecene, 8,9-di-n-propyloxycarbonyl
Tetracyclo [4.4.0.1^2,5. 1^7,10] -3-do
Decene, 8,8-di-n-propyloxycarbonyl
Toracyclo [4.4.0.1^2,5. 1^7,10] -3-Dode
Sen, 8,9-diisopropyloxycarbonyltetra
Cyclo [4.4.0.1^2,5. 1^7,10] -3-Dodece
, 8,8-diisoproxycarbonyltetracyclo
[4.4.0.1^2,5. 1^{7, Ten}-3-dodecene, 8,
9-di-n-butoxycarbonyltetracyclo [4.
4.0.1.^2,5. 1^7,10] -3-dodecene, 8,8-di
-N-butoxycarbonyltetracyclo [4.4.0.
1^2,5. 1^7,10] -3-dodecene, 5,6-dimethoxy
Carbonylbicyclo [2.2.1] hept-2-ene,
5-methyl-5,6-dimethoxycarbonylbicyclo
[2.2.1] Hept-2-ene, 5-methyl-5,6
-Diethoxycarbonylbicyclo [2.2.1] hept
-2-ene, 5,5-dimethoxycarbonylbicyclo
[2.2.1] Hept-2-ene, 5,6-diethoxy
Carbonylbicyclo [2.2.1] hept-2-ene,
5,6-diisopropyloxycarbonylbicyclo
[2.2.1] Hept-2-ene, 5,6-di-n-butyl
Toxylcarbonylbicyclo [2.2.1] hept-2-
And the like. Even when these monomers (1) are used alone,
Alternatively, two or more kinds may be used in combination. The formula (II) used in the present invention is represented by the following formula:
The monomer (hereinafter, referred to as “monomer (2)”) is
The alkoxycarbol group represented by the general formula (III) is
It is a norbornene-based compound containing one contained group. In the general formula (II), the alkoxycarbo
Carbon atom on the norbornene ring to which the group containing the phenyl group is bonded
Has a hydrogen atom or an alkyl group, especially a methyl group,
Is preferable from the viewpoint of easy production. E^Two, F^Two, G^Two, I^TwoTwo groups of
Are bonded to each other to form a monocyclic or polycyclic group
The monocyclic and polycyclic groups are the same as in the aforementioned general formula (I). The skeleton of the ring of the monomer (2) is
B [2.2.1] hept-2-ene, tetracyclo
[4.4.0.1^2,51^7,10] -3-Dodecene is especially
preferable. Specific examples of the monomer (2) include 5-methoxy
Xycarbonylbicyclo [2.2.1] hept-2-e
5-methyl-5-methoxycarbonylbicyclo
[2.2.1] Hept-2-ene, 5-methyl-5-e
Toxylcarbonylbicyclo [2.2.1] hept-2-
Ene, 5-methyl-5-isopropyloxycarbonyl
Bicyclo [2.2.1] hept-2-ene, 5-methyl
-5-butoxycarbonylbicyclo [2.2.1] hep
To-2-ene, 8-methoxycarbonyltetracyclo
[4.4.0.1^2,5. 1^7,10] -3-dodecene, 8-
Ethoxycarbonyltetracyclo [4.4.0.
1^2,5. 1^7,103-dodecene, 8-n-propylo
Xycarbonyltetracyclo [4.4.0.1^2,5. 1
^7,10] -3-dodecene, 8-isopropyloxycarbo
Nyltetracyclo [4.4.0.1^2,5. 1^7,10] -3
-Dodecene, 8-n-butoxycarbonyltetracyclo
[4.4.0.1^2,5. 1^7,10] -3-dodecene, 8-
Methyl-8-methoxycarbonyltetracyclo [4.
4.0.1.^2,5. 1 ^7,10] -3-dodecene, 8-methyl
-8-ethoxycarbonyltetracyclo [4.4.0.
1^2,5. 1^7,10] -3-dodecene, 8-methyl-8-n
-Propyloxycarbonyltetracyclo [4.4.
0.1^2,5. 1^7,10] -3-dodecene, 8-methyl-8
-Isopropyloxycarbonyltetracyclo [4.
4.0.1.^2,5. 1^7,10] -3-dodecene, 8-methyl
-8-n-butoxycarbonyltetracyclo [4.4.
0.1^2,5. 1^7,10] -3-dodecene, 8- (2,2,
2-trifluoroethoxycarbonyl) tetracyclo
[4.4.0.1^2,5. 1^7,10] -3-dodecene, 8-
Methyl-8- (2,2,2-trifluoroethoxycal
Bonyl) tetracyclo [4.4.0.1^2,5. 1^7,10]
-3-dodecene and the like. These monomers may be used alone or
May be used in combination of two or more. The monomer (1) used in the present invention and the monomer (1)
Examples of the monomer (3) copolymerizable with the monomer (2) include nor
There are compounds having a bornene structure. Norbo like this
As a linen derivative, a linear polymer can be obtained.
, Specifically one double bond in the ring in one molecule
Is preferably used. Preferred among the monomers (3) are the following
Not containing an alkoxycarbonyl group represented by the formula (IV)
Monomer. [0030] Embedded image In the formula (IV), E^Three, F^Three, G^Three, J^ThreeIs
Hydrogen atom, halogen atom or monovalent organic group (alcohol
Excluding a group containing a xycarbonyl group) or
May combine to form a monocyclic or polycyclic group,
The monocyclic or polycyclic group may have a double bond.
K is a positive integer of 0 or 3 or less, and q is 0 or 1.
You. ) In the general formula (IV), a halogen atom and a monovalent organic
Examples of the group include those similar to the aforementioned general formula (I).
Can be. In this case, E^Three, F^Three, G^Three, J^ThreeIs
Each is preferably a hydrogen atom or an alkyl group.
When it is an alkyl group, a methyl group is particularly preferred. Also, E^Three, F^Three, G^Three, J^ThreeAre those
Two of which combine with each other to form a monocyclic or polycyclic group
When, for example, cyclohexyl, 1-cyclohexyl
Monocyclic groups such as phenyl and phenyl, naphthyl,
It may be a polycyclic group such as dronaphthyl. Alternatively, E^Three, F^Three, G^Three, J^ThreeNozomi
Reka and R¹Examples of the alkylidene group formed by
Are, for example, methylidene, ethylidene, isopropyl
A denene group and a butylidene group. Specific examples of the monomer (3) include tetracy
Black [4.4.0.1^2,5. 1^7,10-3-dodecene,
8-ethylidenetetracyclo [4.4.0.1^2,5. 1
^7,10] -3-dodecene, 8-ethyltetracyclo [4.
4.0.1.^2,5. 1^7,10] -3-dodecene, 8-methyl
Tetracyclo [4.4.0.1^2,5. 1^7,10] -3-do
Decene, pentacyclo [6.5.1.1^3,6. 0^3,7.
0^9,13] -4-pentadecene, hexacyclo [6.6.
1.1^3,6. 1^10,13. 0^2,7. 0^9,14] -4-hepta
Decene, heptacyclo [8.7.0.1^2,9. 1^4,7.
1^11,17. 0^3,8. 0^12,16] -5-eicosene, ok
Tacyclo [8.8.0.1^2,9. 1^4,7. 1^11,18. 1
^13,16. 0^3,8. 0^12,17] -5-Docosene, 5-methyl
Rubicyclo [2.2.1] hept-2-ene, 5-cia
Novicyclo [2.2.1] hept-2-ene, 8-methyl
Letetracyclo [4.4.0.1^2,5. 1^7,10] -3-
Dodecene, pentacyclo [7.4.0.1^2,5.
1^9,12. 0^8,13] -3-pentadecene, pentacyclo
[8.4.0.1^2,5. 1^9,12. 0^8,13] -3-Hexa
Decene, heptacyclo [8.7.0.1^3,6.
1^10,17. 1^12,15. 0^2,7. 0^11,16] -4-eiko
Sen, heptacyclo [8.8.0.1^4,7. 1^11,18.
1^13,16. 0^3,8. 0^12,17-5-heneikosen,
5-ethylidenebicyclo [2.2.1] hept-2-e
5-fluorobicyclo [2.2.1] hept-2-
Ene, 5-fluoromethylbicyclo [2.2.1] hep
To-2-ene, 5-trifluoromethylbicyclo [2.
2.1] Hept-2-ene, 5-pentafluoroethyl
Bicyclo [2.2.1] hept-2-ene, 5,5-di
Fluorobicyclo [2.2.1] hept-2-ene,
5,6-difluorobicyclo [2.2.1] hept-2
-Ene, 5,5-bis (trifluoromethyl) bicyclo
[2.2.1] Hept-2-ene, 5,6-bis (tri
Fluoromethyl) bicyclo [2.2.1] hept-2-
Ene, 5-methyl-5-trifluoromethylbicyclo
[2.2.1] Hept-2-ene, 5,5,6-triff
Fluorobicyclo [2.2.1] hept-2-ene, 5,
5,6-tris (fluoromethyl) bicyclo [2.2.
1] Hept-2-ene, 5,5,6,6-tetrafluoro
Lobicyclo [2.2.1] hept-2-ene, 5,5
6,6-tetrakis (trifluoromethyl) bicyclo
[2.2.1] Hept-2-ene, 5,5-difluoro
-6,6-bis (trifluoromethyl) bicyclo [2.
2.1] Hept-2-ene, 5,6-difluoro-5,
6-bis (trifluoromethyl) bicyclo [2.2.
1] Hept-2-ene, 5,5,6-trifluoro-5
-Trifluoromethylbicyclo [2.2.1] hept-
2-ene, 5-fluoro-5-pentafluoroethyl-
6,6-bis (trifluoromethyl) bicyclo [2.
2.1] Hept-2-ene, 5,6-difluoro-5-
Heptafluoroisopropyl-6-trifluoromethyl
Bicyclo [2.2.1] hept-2-ene, 5-chloro
-5,6,6-trifluorobicyclo [2.2.1] f
Put-2-ene, 5,6-dichloro-5,6-bis (to
(Fluoromethyl) bicyclo [2.2.1] hept-2
-Ene, 5,5,6-trifluoro-6-trifluoro
Methoxybicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-6-heptafluoropropyl
Luxybicyclo [2.2.1] hept-2-ene, 8
-Fluorotetracyclo [4.4.0.1^2,5.
1^7,10] -3-Dodecene, 8-fluoromethyltetracy
Black [4.4.0.1^2,5. 1^7,10-3-dodecene,
8-difluoromethyltetracyclo [4.4.0.1
^2,5. 1^7,10] -3-Dodecene, 8-trifluoromethyl
Letetracyclo [4.4.0.1^2,5. 1^7,10] -3-
Dodecene, 8-pentafluoroethyltetracyclo
[4.4.0.1^2,5. 1^7,10-3-dodecene, 8,
8-difluorotetracyclo [4.4.0.1^2,5. 1
^7,10] -3-dodecene, 8,9-difluorotetracycline
B [4.4.0.1^2,5. 1^7,10-3-dodecene,
8,8-bis (trifluoromethyl) tetracyclo
[4.4.0.1^2,5. 1^7,10-3-dodecene, 8,
9-bis (trifluoromethyl) tetracyclo [4.
4.0.1.^2,5. 1^7,10] -3-dodecene, 8-methyl
-8-trifluoromethyltetracyclo [4.4.0.
1^2,5. 1^7,10] -3-dodecene, 8,8,9-triff
Fluorotetracyclo [4.4.0.1^2,5. 1^7,10]-
3-dodecene, 8,8,9-tris (trifluoromethyl
Le) tetracyclo [4.4.0.1^2,5. 1^7,10] -3
-Dodecene, 8,8,9,9-tetrafluorotetracy
Black [4.4.0.1^2,5. 1^7,10-3-dodecene,
8,8,9,9-tetrakis (trifluoromethyl) te
Toracyclo [4.4.0.1^2,5. 1^7,10] -3-Dode
Sen, 8,8-difluoro-9,9-bis (trifluoro
Romethyl) tetracyclo [4.4.0.1^2,5.
1^7,10] -3-dodecene, 8,9-difluoro-8,9
-Bis (trifluoromethyl) tetracyclo [4.4.
0.1^2,5. 1^7,10] -3-dodecene, 8,8,9-
Trifluoro-9-trifluoromethyltetracyclo
[4.4.0.1^2,5. 1^7,10-3-dodecene, 8,
8,9-trifluoro-9-trifluoromethoxytet
Lacyclo [4.4.0.1^2,5. 1^7,10] -3-Dodece
8,8,9-trifluoro-9-pentafluorop
Ropyloxytetracyclo [[4.4.0.1^2,5. 1
^7,10] -3-dodecene, 8-fluoro-8-pentaful
Oroethyl-9,9-bis (trifluoromethyl) tet
Lacyclo [4.4.0.1^2,5. 1^7,10] -3-Dodece
, 8,9-difluoro-8-heptafluoroisopro
Pill-9-trifluoromethyltetracyclo [4.4.
0.1^2,5. 1^7,10] -3-Dodecene, 8-chloro-
8,9,9-trifluorotetracyclo [4.4.0.
1^2,5. 1^7,10] -3-dodecene, 8,9-dichloro-
8,9-bis (trifluoromethyl) tetracyclo
[[4.4.0.1^2,5. 1^7,10] -3-dodecene, etc.
Can be mentioned. As a specific example of the monomer (3),
Methanooctahydronaphthalene, ethyl tetracyclod
Decene, 6-ethylidene-2-tetracyclododecene,
Use of trimethanooctahydronaphthalene etc.
Can be. These monomers may be used alone.
Alternatively, two or more kinds may be used as a mixture. The above-mentioned monomer (1), monomer (2), monomer
Body (3) is composed of dicyclopentadiene (DCP) and various
Diels-Alder reaction with monomer having double bond group
Can be synthesized by The monomers (1) and (2) of the present invention
The composition ratio (weight ratio) of the polymer is monomer (1): monomer
(2) = 99: 1 to 1:99 is preferred, and 80:20 to
20:80 is more preferred. Monomer of composition ratio (1):
Even if the monomer (2) is larger than 99: 1,
Monomer (1): monomer (2) is less than 1:99
In each case, the final hydrogenated polymer is non-halo
Hardly soluble in gen-based solvents. The monomer (3) and the monomer used in the present invention
The composition ratio (weight ratio) with the total amount of (1) + monomer (2) is
Monomer (3): {monomer (1) + monomer (2)} = 0:
It is preferably from 100 to 50:50, more preferably O:
100 to 40:60. Monomer (3): {Monomer (1) + Monomer
(2) If the composition ratio of｝ is greater than = 50: 50, the final
The resulting hydrogenated polymer is dissolved in a non-halogen solvent.
Hateful. The hydrogenated polymer of the present invention comprises the above monomer
Together with (1) and monomer (2) or these monomers
And a monomer (3) copolymerizable with these monomers
Ring-opening copolymerization in organic solvent using metathesis polymerization catalyst
The ring-opened copolymer obtained by the
This is a hydrogenated polymer obtained by addition. The method used to produce the hydrogenated polymer of the present invention
Specific examples of the thesis polymerization catalyst include molybdenum (M
o), tungsten (W), ruthenium (Ru), reni
Halo of metals such as U (Re) and tantalum (Ta)
Genides, oxyhalides, oxides, organic ammonium
And the like. Also, the metathesis polymerization catalyst
As the catalyst, alkyl aluminum halide, alcohol
Xyalkylaluminum halide, aryloxya
Alkyl aluminum, organotin compounds, etc.
You. The amount of the metathesis polymerization catalyst used is
0.01 to 20 mm per mole of the monomer
Mole, preferably used in the range of 0.1 to 10 mmol.
It is. The cocatalyst is 1 to 50 with respect to the metathesis polymerization catalyst.
(Molar ratio). The metathesis polymerization catalyst is modified beforehand.
It may be a modified metal compound. The solvent used for producing the hydrogenated polymer of the present invention is
As the medium, pentane, hexane, heptane, octa
Alkanes such as cyclohexane, nonane and decane, cyclohexa
, Cycloheptane, cyclooctane, decalin, nor
Cycloalkanes such as bornane, benzene, and toluene
Aromatic charcoal such as benzene, xylene, ethylbenzene, cumene
Hydrogen chloride, chlorobutane, bromohexane, methyl chloride
, Dichloroethane, hexamethylene dibromide,
Robenzene, chloroform, tetrachloroethylene, etc.
Compounds such as halogenated alkanes and aryls,
Chill, n-butyl acetate, iso-butyl acetate, propio
Saturated carboxylic acids such as methyl phosphate and dimethoxyethane
Stels, dibutyl ether, tetrahydrofuran, di
Examples include ethers such as methoxyethane.
These can be used alone or as a mixture
You. Of these, aromatic hydrocarbons are preferred. The amount of the solvent used is as follows: "solvent: monomer
(Weight ratio) is usually 1: 1 to 10: 1.
The amount is preferably 1: 1 to 5: 1. In the present invention, the molecular weight of the ring-opening copolymer is
Adjustments are also made depending on the polymerization temperature, catalyst type and solvent type.
In the present invention, a molecular weight regulator can be used.
It can be adjusted by coexisting in the reaction system. Examples of suitable molecular weight regulators include, for example,
For example, ethylene, propene, 1-butene, 1-pentene,
1-hexene, 1-heptene, 1-octene, 1-none
Α-olefins such as 1,1-decene, 1,3-butane
Dienes such as diene and 1,3-pentadiene;
Tylene and the like.
Ten, 1-hexene is particularly preferred. These molecular weight regulators may be used alone or
Two or more kinds can be used as a mixture. The amount of the molecular weight modifier used may be as follows.
0.005 to 1.0 mol, preferably 0.1 to 1.0 mol per mol.
02 to 0.7 mol. The polymerization temperature of the ring-opening copolymerization reaction is from 40 to
The temperature is set to 120 ° C, preferably 50 to 100 ° C. The ring-opened copolymer obtained as described above
Can be hydrogenated using a hydrogenation catalyst. The hydrogenation reaction is carried out in a usual manner, that is,
A hydrogenation catalyst is added to the ring copolymer solution,
300 atm, preferably 3 to 200 atm of hydrogen gas
To 200 ° C, preferably 20 to 180 ° C.
And done by As the hydrogenation catalyst, the usual olefinic
It is possible to use those used for hydrogenation of compounds
it can. As this hydrogenation catalyst, a heterogeneous catalyst and
Homogeneous catalysts are known. As the heterogeneous catalyst, palladium, white
Noble metal catalysts such as gold, nickel, rhodium and ruthenium
Substances such as carbon, silica, alumina, titania, etc.
Examples include a solid catalyst supported on a carrier. Ma
As a homogeneous catalyst, nickel naphthenate / trie
Chill aluminum, nickel acetylacetonate / g
Liethylaluminum, cobalt octenoate / n-butyl
Lithium, titanocene dichloride / diethylaluminum
Ummonochloride, rhodium acetate, chlorotris (tri
Phenylphosphine) rhodium, dichlorotristrif
Phenylphosphine ruthenium, chlorohydrocarbonyl
List tristriphenyl phosphine ruthenium, etc.
be able to. The form of the catalyst may be powdery or granular. These hydrogenation catalysts are prepared by using a ring-opening copolymer: water
The oxidation catalyst (weight ratio) is 1: 1 × 10^-Five~ 1: 2
Used in proportions. Thus, by hydrogenation, the obtained
Hydrogenated polymers have excellent thermal stability.
Depending on the heating during molding and product use.
Its characteristics do not deteriorate. Where the hydrogenation rate
Is usually at least 50%, preferably at least 70%, more preferably
Or 90% or more. If the hydrogenation rate is lower than 50%
The resulting resin has poor heat resistance and turns yellow when heated.
It is not preferable because it is colored or becomes brittle. The molecular weight of the hydrogenated polymer of the present invention is
Weight average molecular weight in terms of styrene, usually 20,000
0 to 700,000, especially 30,000 to 500,00
It is preferably 0. Molecular weight less than 20,000
The resulting resin is brittle and greater than 700,000
And it becomes difficult to manufacture. The hydrogenated polymer of the present invention has a known oxidation
Inhibitors such as 2,6-di-tert-butyl-4-methylphenyl
Enol, 2,2'-dioxy-3,3'-di-t-butyl
Tyl-5,5'-dimethyldiphenylmethane, tetrakis
[Methylene-3- (3,5-di-t-butyl-4-hi
Droxyphenyl) propionate] methane; UV absorption
Collectors, for example 2,4-dihydroxybenzophenone, 2
-Hydroxy-4-methoxybenzophenone etc. are added
Can be stabilized. Also processing
Add additives such as lubricants for the purpose of improving lubricity
Can also. Dissolving the hydrogenated polymer of the present invention
Possible solvents include relatively low boiling ester solvents,
Ketone solvents, hydrocarbon solvents, aromatic solvents and the like.
Or a mixed solvent thereof. As ester solvents, methyl formate,
Ethyl acid, butyl formate, amyl formate, methyl acetate, acetic acid
Ethyl, propyl acetate, isopropyl acetate, butyl acetate
, Isobutyl acetate, secondary amyl acetate, isoamido acetate
, Methyl amyl acetate, and ketone solvents
, Methyl acetone, methyl ethyl ketone, methylpro
Pill ketone, diethyl ketone, methyl butyl ketone,
Butyl isobutyl ketone, ethyl butyl ketone, butyro
Cyclohexane and hexane as hydrocarbon solvents
, Isohexane, methylpentane, heptane, isohexane
Butane, octane, isooctane, isooctene, nona
And the like. Solvent price, ease of use, poison
Methyl acetate due to its solubility, solubility and volatility of the hydrogenated polymer
, Ethyl acetate, propyl acetate, isopropyl acetate, vinegar
Acetone, methylacetone,
Methyl ethyl ketone, methyl propyl ketone, diethyl
Cyclohexane and hexane as ketone and hydrocarbon solvents
Sun, isohexane, methylpentane, heptane, iso
Heptane, octane, isooctane, aromatic solvents
, Toluene, xylene, etc. and their mixed solvents
And the like. More preferably, methyl acetate, vinegar
Ethyl acid, propyl acetate, isopropyl acetate, ketone
Acetone, methylacetone, methylethyl as solvents
Ketone, methyl propyl ketone, diethyl ketone,
Mixed solvents of toluene with these solvents and the like
You. The use of the hydrogenated polymer of the present invention is particularly limited.
Is not intended to be used over a wide range
For example, general camera lens, video camera
Lens, telescope lens, spectacle lens, laser beam laser
Lenses, optical video discs, audio
Disk, document file disk, memory disk, etc.
Optical discs, optical materials such as optical fibers, image receiving
Transfer sheets and various films, adhesives, varnishes, sheets,
Especially as sealant, binder of inorganic or organic compounds
It can be suitably used. The composition comprising the hydrogenated polymer of the present invention is
Inorganic compounds, silane coupling agents, etc.
Which organic silicon compound, acrylic resin, vinyl resin
Fat, melamine resin, epoxy resin, fluorine resin, silicone
Forming a hard coat layer made of cone resin, etc.
Can be. As a means for forming the hard coat layer, thermosetting
Method, ultraviolet curing method, vacuum deposition method, sputtering method,
Known methods such as the on-plating method
it can. As a result, the heat resistance, optical properties,
Improves chemical properties, abrasion resistance and moisture permeability
it can. Hereinafter, embodiments of the present invention will be described.
However, the present invention is not limited thereby. (Example 1) (A) polymerization (A) Monomer 4 of the chemical structural formula shown in Tables 1 and 3
0 parts by weight and 60 parts by weight of the monomer represented by the chemical structural formula (B)
Parts by weight, 13 parts of 1-hexene as a molecular weight regulator and
200 parts of ene were charged into a reaction vessel purged with nitrogen,
Heated to ° C. In addition to this, the polymerization catalyst triethyl alcohol
0.51 parts of a toluene solution of minium (1.5 mol / l)
And 3.0 parts of a WCl6 solution (concentration: 0.05 mol / l)
In addition, the mixture was heated and stirred at 80 ° C. for 3 hours to obtain a polymer solution A.
Was. The polymerization conversion rate in this polymerization reaction was 97%.
Met. (B) Hydrogenation A hydrogenation catalyst was added to 400 parts of the polymer solution obtained above.
Chlorohydrocarbonyl trisphenylphosphine
Add 0.075 parts of ruthenium and place in autoclave
And hydrogen gas pressure 100kg / cm^TwoAt a temperature of 165 ° C
By heating for 4 hours under the conditions, the hydrogenation reaction is initiated.
became. In the obtained hydrogenated polymerization solution, the hydrogenation rate is
Substantially 100%. (C) Contact, coagulation and drying 400 parts of the hydrogenated polymerization solution obtained above and toluene
100 parts were charged in a reaction vessel, and 0.71 part of lactic acid and water were added.
And stirred at 60 ° C. for 30 minutes.
Then, add 260 parts of methanol,
Stirred for hours. After that, cool the inside of the reaction vessel to room temperature,
Poor solvent phase (methanol phase) and good solvent phase (polymer-containing phase)
And only the poor solvent phase was extracted. Then pull out
Methanol equivalent to 4.5% by weight of the poor solvent
Add 55% by weight of toluene to the reaction vessel
Then, the mixture was stirred at 60 ° C for 1 hour. Cool down to room temperature again,
Separate the poor and good solvent phases and extract only the poor solvent phase
did. Repeat the extraction operation with methanol once more.
Water phase after separating the good solvent phase and removing residual metals, etc.
The element-added polymer was recovered. After coagulating this solution with methanol, vacuum
After drying in a dryer at 80 ° C for 12 hours, polymer (hydrogenation weight)
Combined 1) was obtained. Its weight average molecular weight (Mw) is 20,000
there were. (D) Film production The above hydrogenated polymer was treated with a non-halogen solvent (ethyl acetate /
Dissolved in toluene = 90/10 wt%) and dissolved in 20 wt%
Solution, and transfer the solution from a fixed width die to Teflon.
Extruded on film (carrier) and air-dried
Thereafter, the carrier is peeled off from the carrier, and further, a vacuum dryer, 80
℃, dried over 12 hours, cast 150μm thick
A film was obtained. Evaluation method Total light transmittance, glass transition temperature (Tg), birefringence and
The solubility was measured or evaluated by the following method. Total light transmittance: several films are stacked
And make it 3.2mm thick, and use a haze meter to AST
It measured according to MD1003. Birefringence: The film was measured using an ellipsometer
633 nm). Glass transition temperature: DSC (differe
neutral Scanning Calorimeter
r), measured at a temperature rise condition of 20 ° C./min.
Was. Solubility: Ethyl acetate / toluene =
85/15 (wt% ratio)
Was. Table 3 shows the results. Soluble in solvent, Tg
High hydrogenation polymer with good transparency and birefringence
It is understood that it is. (Examples 2 and 3) As shown in Tables 1 and 3.
Example 1 by changing the composition ratio of (A) monomer and (B) monomer
Polymerized in the same way as in
Got Lum. The polymerization of the polymers of Examples 2 and 3
The conversion rates were 98% and 95%, respectively, of the hydrogenated polymer.
Mw was 19000 and 20000, respectively. Table 2 shows the results. (A) with a monomer
(B) Soluble in solvent even when the ratio of monomers is changed, and high Tg
And a hydrogenated polymer with good transparency and birefringence can be obtained.
You can see that. (Example 4) As shown in Tables 1 and 3.
(A) monomer and (B) monomer and copolymer
A polymerizable monomer was added and polymerized in the same manner as in Example 1.
A film was obtained through addition, decontact, coagulation and drying. The result
The results are shown in Table 2. The weights of the polymers of Examples 4, 5 and 6 were
The inversion rates were 94%, 95% and 96%, respectively.
The Mw of the hydrogenated polymer was 19000 and 2000, respectively.
0 and 20,000. In addition to the monomers (A) and (B),
Hydrogenated polymer that can be solvent even when polymerizable monomer is added
Is obtained. (Examples 5 and 6) Tables 1 and 3
Use two or more monomers (1) and (2)
Can be used to obtain a solvent-soluble hydrogenated product
You. Examples 7 to 10 are shown in Tables 1 and 3.
Even when such a monomer is used, polymerization and water
A film was obtained through addition of element, decontact, coagulation and drying. result
Are shown in Table 2. The polymerization of Examples 7, 8, 9 and 10
The polymerization conversion of the product was 92%, 92%, 96%, respectively.
And 95%, the Mw of the hydrogenated polymer was 150
00, 20000, 19000 and 20000
Was. Using monomers as shown in Tables 1 and 3
However, it can be seen that a hydrogenated polymer that can be solvent is obtained.
Call (Examples 11 to 13) Tables 2 and 3 show
Even when such a monomer is used, polymerization is performed in the same manner as in Example 1.
A film was obtained through hydrogenation, decontact, coagulation and drying. Conclusion
The results are shown in Table 3. The polymerization of Examples 11, 12 and 13
The polymerization conversion of the product was 91%, 92% and 9%, respectively.
2%, Mw of the hydrogenated polymer was 16000, 2
0000 and 18000. Using monomers as shown in Tables 2 and 3
However, it can be seen that a hydrogenated polymer that can be solvent is obtained.
Call (Comparative Examples 1 and 2) Tables 1 and 3
Perform only (A) monomer or (B) monomer only
Polymerized in the same manner as in Example 1 and subjected to hydrogenation, desorption, coagulation, and drying.
A film was obtained. However, the solvent used during film production is
Roholm was used. The polymerization inversion of the polymers of Comparative Examples 1 and 2
The conversion rates were 92% and 92%, respectively,
The body Mw was 15,000 and 20,000, respectively.
Was. The results are shown in Table 4. (A) monomer only,
Or (B) hydrogenation by polymerization and hydrogenation of monomer only
Polymer has high Tg, good transparency and good birefringence
Is insoluble in the solvent. (Comparative Examples 3 and 4) Polymethyl methacrylate
Rate and polycarbonate use chloroform.
Lum manufactured. Table 4 shows the evaluation results. Polymethyl methacrylate has a low Tg.
And does not dissolve in solvents. Polycarbonate is birefringent
It turns out that the fold is large and that it is insoluble in the solvent. [0096] [Table 1] [0097] [Table 2][0098] [Table 3][0099] [Table 4][0100] The hydrogenated polymer of the present invention is a non-halogenated polymer.
Because it is soluble in system solvents, there is no environmental pollution in the manufacturing process.
Especially cast films, varnishes, adhesives, binders
-Suitable for applications that require a dissolution process, such as applications
it can. Moreover, the hydrogenated polymer of the present invention has a glass transition
High quality polymer with high temperature, transparency and birefringence
It is.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 61/00-61/12

Claims (1)

(57) [Claim 1] (A) A monomer represented by the following general formula (I) and a monomer represented by the following general formula (II) or (B) A) ring-opening copolymerization of a monomer represented by the following general formula (I), a monomer represented by the following general formula (II), and a monomer copolymerizable with these monomers; Further, the weight average molecular weight in terms of polystyrene obtained by hydrogenation is 20,000.
~ 700,000 hydrogenated polymers. Embedded image (In the formula (I), E ¹ , F ¹ , G ¹ , and J ^{1 each} represent a hydrogen atom, a halogen atom, or a monovalent organic group, or may be bonded to each other to form a monocyclic or polycyclic group. And the monocyclic or polycyclic group may have a double bond, and two of E ¹ , F ¹ , G ¹ and J ¹ are groups containing an alkoxycarbonyl group; Is a positive integer of 0 or 3 or less, and q is 0 or 1.) (In the formula (II), E ² , F ² , G ² , and J ^{2 each} represent a hydrogen atom or a halogen atom, a monovalent organic group, or may be bonded to each other to form a monocyclic or polycyclic group. And the monocyclic or polycyclic group may have a double bond,
Further, one of E ² , F ² , G ² and J ^{2 is} a group containing an alkoxycarbonyl group, k is a positive integer of 0 or 3 or less, and q is 0 or 1. )