JPH0477520A - Norbornene-based (co)polymer - Google Patents

Abstract

PURPOSE:To obtain the subject polymer without generating silver streak in injection molding and also suppressing generation of fish eyes by hydrogenating a polymer comprising a specific norbornene derivative and making gel content to a specific value. CONSTITUTION:The objecting polymer is composed of a hydrogenated polymer with <=1wt.% gel content, obtained by hydrogenation of a polymer derived from metathesis polymerization of (A) at least a species of norbornene derivative expressed by the formula [(n)is 0 or 1; at least one of X and Y is (CH2)mCOOR<1>, (CH2)mOCOR<2> or (CH2)mCN (R<1> and R<2> are 1-20C hydrocarbon; A, B and residual X and Y are H or 1-10C hydrocarbon] or (B) an unsaturated cyclic compound copolymerizable with the component A.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention eliminates the occurrence of silver streaks (linear marks) when injection molding is performed, and eliminates uneven transparency called fish eyes. This invention relates to a norbornene-based (co)polymer that has significantly fewer defects (molding defects), provides molded products with good appearance and transparency, and can be stably molded over a long period of time.

[Conventional technology]

Ring-opening polymerization of norbornene derivatives using a metathesis catalyst (
Resins with excellent thermal stability obtained by hydrogenating polymers subjected to metathesis polymerization are disclosed in, for example, JP-A-1-24051.
It has been proposed in Publication No. 7, etc.

However, hydrogenated polymers obtained by metathesis polymerizing norbornene derivatives and further hydrogenation tend to form gels when heated.

It is known that this tendency can be suppressed to some extent by increasing the hydrogenation rate (hydrogenation rate) or using an appropriate antioxidant. Hydrogenated polymers containing gel not only flow during injection molding, resulting in silver streaks, but also, in severe cases, give molded products containing areas of uneven transparency called fish eyes. Put it away. Such a phenomenon becomes a fatal defect especially in the case of molded products, optical disks, lenses, etc. where transparency is important.

[Problem to be solved by the invention]

The present invention was made against the background of the above-mentioned problems of the prior art, and not only improves molding defects caused by silver streaks and fish eyes during injection molding, but also prevents part of the surface of the molded product from adhering to the mold. The object of the present invention is to provide a norbornene-based (co)polymer which can be continuously molded into good molded products by suppressing the peeling phenomenon in which it peels off from the surface of the molded product and remains on the mold surface.

[Means for Solving the Problems] The present invention provides metathesis polymerization of at least one norbornene derivative represented by the following general formula (I) or an unsaturated cyclic compound copolymerizable with the norbornene derivative. A norbornene-based (co)polymer with excellent moldability, comprising a hydrogenated polymer obtained by hydrogenating the resulting polymer, and characterized in that the hydrogenated polymer has a gel content of 1% by weight or less. It provides integration.

(In the formula, n is O or 1, and at least one of X and Y is (CHt)lICOOR'(CH!
)l-0COR", L< is -(CH,)+-CN, where R' and R" represent a hydrocarbon group having 1 to 20 carbon atoms, and A, B and the remaining X or Y are , represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. ) In the general formula (1), specific examples of norbornene derivatives in which n's straight line is O include 5-methoxycarbonylbicyclo(2,2,1)hept-2-ene, 5-ethoxycarbonylbicyclo(2 ,2,1) hept-2-ene, 5-propoxycarbonylbicyclo(2,2,1]hept-2-ene, 5-isopropoxycarbonylbicyclo(2,2゜1)
hept-2-ene, 5-butoxycarbonylbicyclo[2,2,1]hept-2-ene, 5-(2-methylpropoxy)carbonylbicyclo(2
,2,1) hept-2-ene, 5-(1,2-dimethylethoxy)carbonylbicyclo(2,2,1)hept-2-ene, 5-cyclohexyloxycarbonylbicyclo(2,2,1 ) Hept-2-
ene, 5-(4'-1-butylcyclohexyloxy)carbonylbicyclo(2,2,1) to 7") -2-ene, 5-(1,2-dimethylethoxy)carbonylbicyclo(2,2,1) ) hept-2-ene, 5-phenoxycarbonylbicyclo(2,2,1)hept-2-ene, 5-methyl-5-methoxycarbonylbicyclo(2,2
,1) hept-2-ene, 5-methyl-5-ethoxycarbonylbicyclo(2,2
,1) hept-2-ene, 5-methyl-5-propoxycarbonylbicyclo(2,
2,1) hept-2-ene, 5-methyl-5-isopropoxycarbonylbicyclo(
2,2,1) hept-2-ene, 5-methyl-5-butoxycarbonylbicyclo(2,2,13hept-2-ene, 5-methyl-5-(2-methylpropoxy)carbonylbicyclo(2, 2,1) Hept-2-ene, 5-methyl-5-(1,2-dimethylethoxy)carbonylbicyclo(2,2,1) to 7't-2-ene, 5-methyl-5-cyclo xyloxycarbonylbicyclo(2,2,1)hept-2-ene, 5-methyl-5
-(4'-t-Butylcyclohexyloxy)carbonylbicycloC2,2,1)hept-2-ene, 5-methyl-5-(1,2-dimethylethoxy)carbonylbicyclo(2,2,1)hept- 2ene, 5-methyl-5-phenoxycarbonylbicyclo(2,
2,1) hept-2-ene, 5-cyanobicyclo(2,2,1)hept-2-ene, 5-methyl-5-cyanobicyclo(2,2,13hept-2-ene, etc.) It will be done.

Further, in the general formula (1), as a specific example of a norbornene derivative in which the value of n is 1, 8-methoxycarbonyltetracyclo (4,4°0.12°S, 17+l
ll:l Dodec-3-ene, 8-ethoxycarbonyltetracycloC4,4°0.1! ,S,I'l
, 10) Dodec-3-ene, 8-isopropoxycarbonyltetracyclo[4°4.0.1”°5.17.
+(+) Dodec-3-ene, 8-propoxycarbonyltetracyclo(4,4°o, 1!, 5.1f
f, +63 dodec-3-ene, 8-butoxycarbonyltetracyclo(4,4°0.11°5.17°10
) Dodec-3-ene, 8-(2-methylpropoxy)carbonyltetracyclo(4,4,0,1''', 17
・10) Dodeca-3-ene, 8-(1-methylpropoxy)carbonyltetrashif0
[4,4,0,1"-',1'°") Horse chestnut; h3
-ene, 8-(2,2-dimethylethoxy)carbonyltetracyclo(4,4,0,1”°5.17°10) dodeca-
3-ene, 8-cyclohexyloxycarbonyltetracyclo(4
,4,0,1"°Jff,l11) dodec-3ene, 8-(4'-t-butylcyclohexyloxy)carbonyltetracyclo(4,4,0,1"='17°1
0) Dodec-3-ene, 8-phenoxycarbonyltetracyclo(4,4°0.
1!・S, l? +1 (+) Dodeca-3-ene, 8-
Methyl-8-methoxycarbonyltetracyclo(4,4
,0,1"・5.17・10] dodeca-3ene, 8-methyl-8-ethoxycarbonyltetracyclo(4
,4,0,1”°S,lff+1(+) Dodeka-3
ene, 8-methyl-8-isopropoxycarbonyltetracyclo(4,4,0,1'',1'・10) dodeca-3
-ene, 8-methyl-8-propoxycarbonyltetracyclo(
4,4,0,1”%, 1?10) Dodec-3-ene, 8-methyl-8-butoxycarbonyltetracyclo[4
,4,0,1"-',1'・10) dodec-3-ene, 8-methyl-8-(2-methylpropoxy)carbonyltetracyclo(4,4,0,1"□51but16) Dodec-3-ene, 8-methyl-8-(l-methylpropoxy)carbonyltetracyclo(4,4,0,1"・51"") Dodec-3-ene, 8-methyl-8-(2, 2-dimethylethoxy)carbonyltetracyclo(4,4,0,1"='17, +o)
Dodec-3-ene, 8-methyl-8-cyclohexyloxycarbonyltetracyclo(4,4,0,1”°5.17.10) Dodec-3-ene, 8-methyl-8-(4' -t-butylcyclohexyloxy)carbonyltetracyclo(4,4°0.12°
5.17・10) Dodec-3-ene, 8-methyl-
8-phenoxyltetracyclot:I (4,4
, 0, 1”', 1'゛lo]) = 7'car 3-
ene, 8-cyanotetracyclo(4,4,0,1"517.I
O) Dodec-3-ene, 8-methyl-8-cyanotetracyclo (4,4°0.1
2°S, lff+IO) dodec-3-ene, and the like.

These norbornene derivatives may be used alone or in combination of two or more, and
When the heat resistance of the obtained hydrogenated polymer [norbornene (co)polymer] is important, tetracyclo [4°4.0.1”°5.17.10] is used as the norbornene derivative.
Preferably, dodec-3-ene derivatives are primarily used.

On the other hand, when emphasis is placed on the moldability of the hydrogenated polymer [norbornene-based (co)polymer], the tetrashift t:l (4
,4,0,1''',1'°Io,l In addition to toticar-3-ene derivatives, bicyclo(2,2,1)hept-2
-Ene derivatives are preferably used in combination.

Further, a copolymer can be prepared by using an unsaturated cyclic compound copolymerizable with the norbornene derivative in an amount of about 95 mol% or less, preferably about 50 mol% or less. Examples of such unsaturated cyclic compounds include cyclobutene, cyclopentene, cyclooctene, 1.5-cyclooctadiene, 1°5.9-cyclododecatriene, norbornene, 4-ethylidenenorbornene, 5-methylnorbornene, dicyclo Pentagene, tetracyclo(4,4
, 1", 1"", 0") dodeca-3-ene, 8
-ethylidene-tetracyclo(4,4゜12"S,
17+I0. □t°6) Dodec-3-ene and the like can be mentioned.

These norbornene derivatives or mixtures of unsaturated cyclic compounds copolymerizable with the norbornene derivatives include, for example, (a) W,
At least one compound selected from M o , Re and Ta, and (c) Deming's periodic table Ia, IIa
, nb, ma, IVa or IVb group elements having at least one element-carbon bond or element-hydrogen bond.

(a) Component WSMo, Re or Ta compound is
Halides, oxyhalides, alkoxyhalides, alkoxides, carboxylates, (oxy)acetylacetonates, carbonyl complexes, acetonitrile complexes, hydride complexes, and derivatives thereof, or combinations thereof, but W and Mo compounds In particular, these alkoxides, halides, oxyhalides, and alkoxyhalides are preferred from the standpoint of polymerization activity and practicality.These compounds can also be used in the presence of a suitable complexing agent, such as P(ChHs)s, It may be complexed with C5H5N or the like.

Specific examples of component (a) include WClh, WCl5,
WB rl,, WF6, W16, MoCf3, Mo
CAg, MoC1,, ReCf, WOCL, Re0C
12, Re0Bra, W (OCb Hs)b, W
Clz (OCb Hs )a, Mo (OCz Hs )z C1z, Mo (QC!
Hs )S, Moot (acac)z, W (O
COR)s, W(CO)b, Mo(Co)b,
Rez (Co)Ill, Re0Br+ P (C
aH%)3, WCR7! s P (Cb
Hs)z, WClb Cs Hs N, W
(CO)s P (C6H5)! W (CO), (
CH, CN), etc.

In addition, component (b) is Deming's periodic table 1a, IIa
, nb, nla, IVa or IVb group elements and hydrides.

(b) Specific examples of components include n-C, H, Li, n
Cs HzNa, cs Hs Na, CH3Mg l
5ct Hs MgBr, CH3MgBr, n C3
H7M g Cl, t C4H9M g Cl.

CH,=CHCHz MgC1, (Cz H5)! Zn, (CfHs)tCd,
CaZn(CzHs), (CH,)3B.

(Cz Hs)z B, (n Ca H9) x
B, (CH3)! A7! , CCHz )t AI! ,(
,1,,(CHs) z A 41! z Clx, (
CHs ) A I Cl z, (Cz Hs ) 3
A1, L iAj! (Cg Hs ) 4, (Cz Hs ) 3 AIO(C2H5)
z, (Cz Hs)z AN Cl2. C
z Hs AI C1z, (Cz Hs)
t A I Hl (i C2Hq )z AfH
l(cz Hs)! Af Ocz Hs
, (I Ca Hq ) 3 AN, (Cz
Hs ):l Al22 C1y, (CH3
)4 Ga, (CH3)4 3N, (n Ca
HQ)4Sn, (CzHs):I
5iH1(SC6Hl3): l Al, (
n Cs HIy)s Al, LiH, NaH
.

Bz H4, N@ BH4, Al2H3, L 1A
Examples include ffHs, BiHa, TiH4, and the like.

It is also possible to use a mixture of two or more compounds that produce these compounds through reaction.

Particularly preferred component (b) is: (CH3)3Af, (CH3)z AlCl.

(CH:l)+,sAl21. s, CH3ANC
1z, (CzHs)3Al, CCz Hs ) z A
12 Cl, (C2H5) +, s AI Cf+,
s, Cz Hs AI Cff, CCt Hs)
z A j2 H.

(Cz Hs) 2 A I OCm H5, (cz
H5)! Ai CN, (C3H7) 3
Al2, (i Ca Hq ) 3 Al
2, (i C4Hq ) z Al2H1C
Cb HI:l)s Al, (Cs Hl7)
:I A', (CbHs)sAl, etc.

The quantitative relationship between component (a) and component (1) is that the metal atomic ratio of (a):(b) is 1:1 to 1:40, preferably 1:2.
It is used in the range of ~1:20.

The catalyst prepared from the two components (a) to (a) above shows high activity for metathesis polymerization reactions, but it can be further improved by adding component (C) (activator) as listed below. Highly active catalysts can also be obtained.

Various compounds can be used as component (C), but the following compounds can give particularly good results: ■ Elemental boron, BF3, BCl23, B (On C4H9) z, (Cz Hs O) z BF, BZ 03, H
Nonorganic metal compounds of boron such as 3BO3, nonorganic metal compounds of silicon such as Si (OCt H5)4, ■alcohols, ■water, ■oxygen, ■carbonyl compounds and their polymers such as aldehydes, esters, and ketones, ■Cyclic enals such as ethylene oxide, epichlorohydrin, and oxetane; ■Amides such as N,N-diethylformamide and N,N-dimethylacetamide; amines such as aniline, morpholine, and piperidine; and azo compounds such as azobenzene; ■N- N-nitroso compounds such as nitrosodimethylamine and N-nitrosodiphenylamine; (2) compounds containing a 5-C4,N-(l group such as trichloromelamine, N-chlorsuccinoimide, and phenylsulfenyl chloride); and the like.

In addition, the quantitative relationship between component (a) and component (C) cannot be uniformly defined because it varies greatly depending on the type of component (C) added, but in many cases, (C)/(a) (
molar ratio) is 0.005 to 10, preferably 0.005
It is used in the range of ~2.0.

The polymerization solvent is not particularly limited as long as it dissolves the monomer (norbornene derivative or an unsaturated cyclic compound copolymerizable with the norbornene derivative) and the resulting polymer and does not inhibit metathesis polymerization.

Examples of solvents suitable for such purposes include the following compounds.

That is, examples of saturated hydrocarbon solvents include pentane, hexane, heptane, cyclopentane, cyclohexane,
Decalin etc. can be used.

Examples of aromatic solvents include benzene, toluene, xylene, and ethylbenzene.

Examples of the halogenated solvent include methylene chloride, chloroform, 1,2-dichloroethane, 1,1,2°2-tetrachloroethane, and chlorobenzene.

Ether solvents include diethyl ether, 1,2-dimethoxyethane, 1,2-jethoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 1,4-butanediol diethyl ether, tetrahydrofuran, tetrahydrobilane, 1
．． Examples include 4-dioxane and anisole.

As the ester solvent, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, etc. are used.

As the polymerization solvent, a mixture of the above-mentioned solvents can also be used. Among the above solvents, particularly preferred solvents for producing the polymer of the present invention are cyclohexane,
Mention may be made of benzene, toluene, xylene, 1,2-dimethoxyethane, butyl acetate and mixtures thereof.

The polymer used in the present invention can be synthesized to have a desired molecular weight by using a suitable molecular weight regulator. Ethylene, propene, -butene, 1-pentene, 1-hexene, and 1-heptene are preferably used as the molecular weight regulator.

The molecular weight of the polymer used in the present invention is determined by the solution viscosity ([η), nh) measured at 30°C in chloroform.
More preferably, it is in the range of 0.4 to 1.5.

In the polymer thus obtained, the carbon-carbon unsaturated bonds in the polymer are hydrogenated using a suitable hydrogenation catalyst. As the hydrogenation catalyst, commonly used catalysts can be used as they are.

Examples of heterogeneous catalysts include solid catalysts in which noble metal catalysts such as palladium, platinum, nickel, rhodium, and ruthenium are supported on carriers such as carbon, silica, alumina, titania, and silica magnesia. The form of the catalyst may be powder or granules. Further, the reaction may be carried out in a fixed bed or in a suspended bed.

In addition, homogeneous catalysts include nickel naphthenate/triethylaluminum, nickel acetylacetonate/
Triethylaluminum, cobalt octenoate/n-butyllithium, titanocene dichloride/diethylaluminum monochloride, rhodium acetate, chlorotris (
Examples include rhodium catalysts such as triphenylphosphine) rhodium.

The hydrogenation reaction is carried out at normal pressure to 300 atmospheres, preferably 3 to 2
0 to 200°C in a hydrogen gas atmosphere of 00 atmospheres
1 Preferably, it can be carried out at 20 to 180°C.

As the solvent used in the hydrogenation reaction, among the solvents used in the polymerization, a solvent having no carbon-carbon unsaturated bond can be used as is. However, depending on the hydrogenation catalyst, the halogen element acts as an inhibitor, so in that case, the use of a halogen-containing solvent must be avoided.

Preferred solvents for the hydrogenation reaction include ether solvents, such as tetrahydrofuran and ethylene glycol dimethyl ether, hydrocarbon solvents, such as hexane, cyclohexane, and decalin, and mixed solvents thereof.

By hydrogenating in this way, the resulting hydrogenated polymer has excellent thermal stability, and its properties are prevented from deteriorating due to heating during molding or use as a product. .

The hydrogenation rate is 95% or more, preferably 98% or more, more preferably 99% or more as measured by 'H-NMR at 60MHz. If the hydrogenation rate is less than 95%, the effect of improving thermal stability will be insufficient.

The norbornene (co)polymer of the present invention is characterized in that the hydrogenated polymer thus obtained has a low gel content of 1% by weight or less. If the gel content exceeds 1% by weight, no matter how the molding conditions are changed in injection molding, it will not be possible to prevent silver streaks or fish eyes from forming on the surface of the molded product. As the gel content becomes less than 1% by weight, these molding defects can be reduced by controlling the injection molding conditions. In particular, when the gel content is suppressed to 0.1% by weight or less, injection molding can be performed under severe conditions such as higher temperature and higher injection speed. When molding more precise optical parts, it is preferable to suppress the gel content to 0.01% by weight or less, more preferably 0.001% by weight or less. On the other hand, in the case of extrusion molding to produce a transparent sheet as a molded product, the upper limit of the gel content that causes poor appearance due to fish eyes is stricter than that of injection molding, and even under normal molding conditions, the gel content is 0.1 weight It must be less than %.

Examples of methods for obtaining such hydrogenated polymers with low gel content include the following methods.

■A method in which all finishing (removal of solvent) processes are performed under an inert atmosphere.

Since this finishing step, particularly the removal of the solvent, is performed under heating, it is desirable to operate under a nitrogen atmosphere to prevent gelation. Specifically, all handling of the (hydrogenated) polymer solution before entering the finishing step is performed under a nitrogen atmosphere. Even when removing the solvent under reduced pressure,
In addition to reducing leaks from the equipment as much as possible, measures include installing the entire equipment in a nitrogen atmosphere so that even if there is a leak, it will be nitrogen rather than air.

(2) A method in which a suitable antioxidant is added, for example, after the hydrogenation step of the polymer.

Here, as the antioxidant that can be used to prevent the formation of gel, generally well-known antioxidants such as phenol type antioxidants can be used. Specifically, pentaerythritol-tetrakis (3-(3-di-L-
butyl-4-hydroxyphenyl)propionate),
1,3.5 trimethyl-2,4,6-tris (35-t
-butyl-4-hydroxybenzyl)benzene, 3.9
-bis[2-(3-CL-butyl-4-hydroxy-5
-methylphenyl)propionyloxy)-1,1-dimethylethyl)2,4,810-tetraoxaspiro(
5,5) undecane, tris-(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, l,
3.5 Tris (4-t-butyl-3-hydroxy-2゜6-dimethylbenzylisocyanurate, etc.) These phenolic antioxidants are further used in combination with a phosphorus antioxidant. For example, as the phosphorus antioxidant, bis(2,6-di-butyl-4-methylphenyl)pentaerythritol diphosphite, tris(2,4-di-t-butylphenylphosphite) ), 3.5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester, and the like.

■How to lower the temperature during finishing (removal of solvent) as much as possible.

Examples of this method include the following methods (a) to (c).

(a) Use a solvent with as low a boiling point as possible.

However, if a solvent with a very low boiling point is used, the internal pressure during polymerization and hydrogenation will increase, making it necessary to increase the pressure resistance of the equipment, and other factors must be taken into account, such as the solvent itself becoming expensive. Must be.

(b) Removal of the solvent is performed under reduced pressure. This method can be expected to be sufficiently effective.

(c) Use an apparatus that allows the (hydrogenated) polymer solution to be treated to form a film as thin as possible so that the solvent can be efficiently volatilized.

According to the method described above, the temperature during solvent removal is preferably maintained at 300° C. or lower when no antioxidant is used. Furthermore, when an appropriate antioxidant is used, it is preferable to maintain the temperature at 380°C or less.

In addition, if a gel is generated even after using methods ① to ① above, or if gel is generated when methods ① to ① above are not performed, it may be removed by filtration. good.

The generated gel is removed by filtration in the following manner. That is, the (hydrogenated) polymer is mixed with a suitable good solvent.
It is dissolved to a concentration of 0% by weight or less, preferably 15% by weight or less, and this solution is filtered through a filter with a pore size of about 1 μm. If you need to remove the gel more completely, use 0
．． A filter of about 5 μm can be used.

In the present invention, any of these methods can be effectively utilized, and it is even more effective to produce the hydrogenated polymer (C-norbornene (co)polymer) by combining these methods.

The norbornene-based (co)polymer of the present invention has a water content of 300p in the hydrogenated polymer obtained as described above.
When the amount is kept below pm, occurrence of silver streaks and fish eyes during injection molding, peeling of the surface of the molded product, etc. are further suppressed, and more stable molding can be performed.

When injection molding is performed under severe conditions such as higher temperatures and higher injection speeds, the water content of the hydrogenated polymer should be reduced to 1100 pp.
Good results can be obtained by keeping it below.

Furthermore, if it is desired to perform stable molding over a long period of time, it is desirable to suppress the water content of the hydrogenated polymer to 50 ppm or less.

As described above, methods for obtaining hydrogenated polymers with low water content include methods used for drying general polymers, such as vacuum drying and flash drying using dry air or dry nitrogen. Can be mentioned.

In particular, when oxidative deterioration of the hydrogenated polymer is to be avoided, a vacuum drying method or a flash drying method using dry nitrogen is preferable.

In addition, when the norbornene-based (co)polymer of the present invention has a halogen content contained in the hydrogenated polymer obtained as described above, which is suppressed to 1100 pp or less, the norbornene-based (co)polymer during heating It can give good results against gel formation and coloring of polymers. In particular, better heat resistance can be obtained when the halogen content is suppressed to 50 ppm or less, more preferably 20 ppm or less.

Methods for obtaining hydrogenated polymers with low halogen content include: ■ Method for obtaining (hydrogenated) polymers using catalysts and solvents that do not contain halogen atoms (hereinafter referred to as "method ■"); (additional) A method that incorporates a step for removing halogen atoms during polymer production (for example, an extraction method and/or an adsorption method to a hydrogenation catalyst, hereinafter referred to as "Method Ⅰ").

The method (2) above is the simplest, and the halogen atom is essentially (
Hydrogenated) It is highly effective because it is not incorporated into the polymer. However, method (2) also has problems such as an expensive catalyst. The catalyst used in this method is:
The (a) component may be an alkoxy derivative of tungsten or molybdenum, and the (oral) component may be an organolithium compound, an organomagnesium compound, an organozinc compound, a trialkylaluminum derivative, a tetraalkyltin compound, or the like. In addition, as the polymerization solvent in method (2), aromatic hydrocarbons such as toluene, xylene, pentane, cyclopenkune, hexane, cyclohexane, and decalin, ether solvents such as 1,2-dimethoxyethane, dimethylene glycol dimethyl ether, and anisole, and acetic acid are used. Examples include ester solvents such as methyl, ethyl acetate, propyl acetate, and butyl acetate.

These polymerization solvents can also be used as a mixed system.

Furthermore, as the solvent for the hydrogenation reaction in method (2), all solvents that are preferred for use in the polymerization, excluding aromatic compounds that are at risk of being hydrogenated, can be used.

On the other hand, the extraction method in method
As disclosed in Publication No. 24, there is a method of recovering a (hydrogenated) polymer by adding a poor solvent for the (hydrogenated) polymer to a (hydrogenated) polymer solution after polymerization or hydrogenation. Can be mentioned. When removing halogen atoms using this extraction method, use lower alcohols such as methanol, ethanol, propatool, esters of lower alcohols such as methyl formate, ethyl formate, methyl acetate, and ethyl acetate, acetone, methyl ethyl ketone, etc. as a poor solvent. Ketones and the like are preferred.

These poor solvents can also be used in combination.

In addition, the adsorption method to a hydrogenation catalyst in the method This is a method to remove halogen atoms inside. At this time, the metal catalyst is
It is preferable to use it by supporting it on a carrier.

Examples of the carrier include carbon, silica, alumina, silica magnesia, titania, zirconia, zeolite, and silica-alumina.

The supporting rate is 0.01 to 20% by weight, preferably 0.1 to 20% by weight.
It is 10% by weight, more preferably 0.2 to 7% by weight. Among these metal catalysts, palladium is particularly preferred because of its high chlorine removal rate. Further, as the carrier, alumina, silica, and silica magnesia are preferable in terms of specific gravity, catalyst, and ease of preparation.

For details of this method of adsorption onto the hydrogenation catalyst, please refer to Japanese Patent Application No.
-244659 specification.

The norbornene-based (co)polymer of the present invention is composed of the hydrogenated polymer described above, but it can be further stabilized by adding known antioxidants, ultraviolet absorbers, etc. thereto. Additionally, additives used in conventional resin processing, such as lubricants, may be added to improve processability.

Furthermore, in order to improve impact resistance, chemical resistance, abrasion resistance, etc., we use ethylene-α-olefin rubbery polymers; ethylene-α-olefin-polyene copolymer rubber; ethylene-methyl methacrylate. , copolymers of ethylene and unsaturated carboxylic acid esters such as ethylene-butyl acrylate; copolymers of ethylene and fatty acid vinyl such as ethylene-vinyl acetate; ethyl acrylate, butyl acrylate, hexyl acrylate, acrylic acid 2-
Polymers of acrylic acid alkyl esters such as ethylhexyl and lauryl acrylate; polybutadiene, polyisoprene, styrene-butadiene or styrene-isoprene random copolymers, acrylonitrile-butadiene copolymers, butadiene-isoprene copolymers, butadiene-( meth)acrylic acid alkyl ester copolymer,
Diene rubbers such as butadiene-(meth)acrylic acid alkyl ester-acrylonitrile copolymer, butadiene-(meth)acrylic acid alkyl ester-acrylonitrile-styrene copolymer; butylene-isoprene copolymer, styrene-butadiene block copolymer Aromatic vinyl-conjugated diene block copolymers such as polymers, hydrogenated styrene-butadiene block copolymers, styrene-isoprene block copolymers, and hydrogenated styrene-isoprene block copolymers; low-crystalline polybutadiene resins , ethylene-propylene elastomer, styrene-grafted ethylene-propylene elastomer thermoplastic polyester elastomer, ethylene ionomer resin, acrylonitrile-butadiene-styrene resin (ABS resin), acrylonitrile-ethylene-propylene-styrene resin (ABS resin), methyl methacrylate-butadiene −
Styrene resin (MBS resin), acrylonitrile-butadiene-methyl methacrylate-styrene resin (ABM
S resin), acrylonitrile n-butyl acrylate
Styrene resin (AASI resin), rubber modified polystyrene (
High impact polystyrene), styrene resin, vinyl chloride resin, acrylic resin, polyphenylene ether resin, polyarylene sulfide resin, polycarbonate resin, polyester resin, polyamide resin, polyether sulfone resin, polysulfone resin, polyimide resin, etc. It can also be used in combination with other polymers.

The norbornene (co)polymer of the present invention can be made into a molded article by applying various known molding methods, such as injection molding, compression molding, and extrusion molding.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples.

In the examples, parts and percentages are based on weight unless otherwise specified.

Further, various measurements in the examples are as follows.

GeJ]L11 At a temperature of 25°C, 50g of the hydrogenated polymer was dissolved in chloroform to a one-layer concentration, the weight of this solution was measured in advance, and the solution was filtered through a membrane filter with a pore size of 0.5μm.
The gel content was calculated from the increase in weight of the filter after drying the filter.

Moisture 1 Karl Fischer moisture measuring device (manufactured by Mitsubishi Kasei, CA
-5, VA-21), the amount of water generated by heating the hydrogenated polymer to 200°C under a stream of dry nitrogen was determined.

Using an extruder with a diameter of 30III11, the hydrogenated polymer was passed through a T-die with a width of 20mm and a thickness of 1+m to
It was formed into a sheet at a temperature of 80°C. The amount of fish eyes on the obtained sheet depends on the number of fish eyes in a certain area.
Evaluation was made with and ×.

220～
After pelletizing at a temperature of 280°C, a disk of 130 m + φ was continuously molded in 30 seconds at a temperature of 340 to 380°C using a DI SK5MIII injection molding machine manufactured by Sumitomo Heavy Industries. The obtained disks were visually inspected for the occurrence of silver streaks and fish eyes, and for the presence or absence of peeling.

The ease of occurrence of silver streaks, fish eyes, and peeling was determined by O1Δ and ×.

Reference example 1 8-methyl-8-methoxycarbonyltetracyclo(4
, 4,0,1"°5.1?, 1g + 3dodeca-3-ene (hereinafter referred to as "compound 1") 10g, 1°2-dimethoxyethane 6g, cyclohexane 24g 11-hexene 2
．． 5g, and diethylaluminum chloride 0.9
6 moles/! 0.34 m of toluene solution, internal volume 100
d into a pressure-resistant glass bottle.

Meanwhile, in another flask, add 0.05 g of tungsten hexachloride.
Mol/! 1.2-dimethoxyethane solution 2- and 0.1 mol/! of paraaldehyde! 1°2-dimethoxyethane solution of 17111! were mixed.

0.49 id of this mixed solution was added to the mixture in the pressure glass bottle. After sealing, heat the mixture to 80°C and
Stirring was performed for hours.

To the obtained polymer solution, a mixed solvent of 2/8 (weight ratio) of 1,2-dimethoxyethane and cyclohexane was added to make the polymer/solvent ratio 1/10 (weight ratio), and then 2 g of triethanolamine was added. was added and stirred for 10 minutes.

50 g of methanol was added to this polymerization solution, stirred for 30 minutes, and allowed to stand still. The upper layer separated into two layers was removed, methanol was added again, and the mixture was stirred and allowed to stand, and then the upper layer was removed. The same operation was performed two more times, and the resulting lower layer was mixed with cyclohexane and
The mixture was appropriately diluted with 1,2-dimethoxyethane to obtain a cyclohexane-1,2-dimethoxyethane solution having a polymer concentration of 10%.

Add 2 g of palladium/silica magnesia (manufactured by JGC Chemical ■, palladium amount = 5%) to this solution, react in an autoclave at 165°C under a hydrogen pressure of 40 kg/ciil for 4 hours, and then filter the hydrogenation catalyst. was removed to obtain a hydrogenated polymer solution A.

Further, this hydrogenated polymer solution A was coagulated using methanol to obtain hydrogenated polymer A.

Reference Example 2 Instead of Compound 1 in Reference Example 1, 4 g of Compound 1, 8-
Ethylidene-tetracyclo (4,4,0°12°5.1
7"10] Hydrogenated polymer solution B and hydrogenated polymer B were obtained by carrying out the same operation as in Reference Example 1, except that 6 g of dodec-3-ene (hereinafter referred to as "compound 2j") was used.

Reference Example 3 Instead of Compound 1 in Reference Example 1, 8 g of Compound 1, 5-
Methyl-5-methoxycarbonylbicyclo(2,2,1
) 2g of hept-2-ene (hereinafter referred to as "Compound 3")
A hydrogenated polymer solution C and a hydrogenated polymer C were obtained by carrying out the same operation as in Reference Example 1, except for using the following.

Reference Example 4 Instead of Compound I in Reference Example 1, 8 g of Compound I was added to tetracyclo[4,3,1'°5.01°6]-3,7-zocadien (dicyclopentadiene, hereinafter referred to as "compound 4j" ) was used, but the same operation as in Reference Example 1 was performed to obtain a hydrogenated polymer solution and a hydrogenated polymer solution.

Example 1 Hydrogenated polymer solution A was subjected to solvent removal at 280°C under reduced pressure. The molten resin was pelletized using an extruder in a nitrogen atmosphere, and its moldability was confirmed by forming it into a sheet by injection molding and extrusion molding. The results are shown in Table 1.

Example 2 The antioxidant pentaerythrityl-tetrakis (3-(3,5-di-t-butyl-4-
After adding 0.1% of hydroxyphenyl propionate to the hydrogenated polymer, the solvent was removed under reduced pressure at 380°C.

The molten resin was pelletized using an extruder in a nitrogen atmosphere, and its moldability was confirmed by forming it into a sheet by injection molding and extrusion molding. The results are shown in Table 1.

Example 3 Hydrogenated polymer solution B was subjected to solvent removal at 280°C under reduced pressure. The molten resin was pelletized using an extruder in a nitrogen atmosphere, and its moldability was confirmed by forming it into a sheet by injection molding and extrusion molding. The results are shown in Table 1.

Example 4 The antioxidant pentaerythrityl-tetrakis (3-(3,5-di-t-butyl-4
-hydroxyphenyl)propionate] to the hydrogenated polymer. After adding 1%, the solvent was removed under reduced pressure at 380°C.

The molten resin was pelletized using an extruder in a nitrogen atmosphere, and its moldability was confirmed by forming it into a sheet by injection molding and extrusion molding.

The results are shown in Table 1.

Example 5 The hydrogenated polymer solution was subjected to solvent removal at 280°C under reduced pressure. The molten resin was pelletized using an extruder in a nitrogen atmosphere, and its moldability was confirmed by forming it into a sheet by injection molding and extrusion molding. The results are shown in Table 1.

Example 6 Hydrogenated polymer solution A was filtered through a filter with a pore size of 0.5 μm, and the hydrogenated polymer was precipitated by methanol coagulation.

The moldability of this hydrogenated polymer was confirmed by forming it into a sheet by injection molding and extrusion molding. The results are shown in Table 1.

Example 7 Hydrogenated polymer solution A was subjected to solvent removal at 380°C under reduced pressure. The molten resin was pelletized using an extruder in a nitrogen atmosphere, and its moldability was confirmed by forming it into a sheet by injection molding and extrusion molding. The results are shown in Table 1.

Example 8 Hydrogenated polymer solution A was subjected to solvent removal at 280°C under reduced pressure. The molten resin was pelletized using an extruder in an air atmosphere, and its moldability was confirmed by forming it into a sheet by injection molding and extrusion molding.

The results are shown in Table 1.

Example 9 Hydrogenated polymer solution C was subjected to solvent removal at 380°C under reduced pressure. The molten resin was pelletized using an extruder under a nitrogen atmosphere, and its moldability was confirmed by forming it into a sheet by injection molding and extrusion molding. The results are shown in Table 1.

Comparative Example 1 Polymer solution A was desolventized at 380° C. under reduced pressure, but since the degree of reduced pressure was 50+aa+Hg, the residence time was about 30 minutes, which was about twice as long as in Example 2. The molten resin was pelletized by an extruder in an air atmosphere, and its moldability was confirmed by forming it into a sheet by injection molding and extrusion molding.

The results are shown in Table 1.

Comparative Example 2 Polymer solution A was desolvented at 280°C under reduced pressure in the same manner as in Example 1, but since the degree of reduced pressure was 50 mHg,
The residence time was approximately 30 minutes, approximately twice that of Example 1. The molten resin was pelletized by an extruder in an air atmosphere, and its moldability was confirmed by forming it into a sheet by injection molding and extrusion molding. The results are shown in Table 1.

Comparative Example 3 Polymer solution C was desolventized at 380°C under reduced pressure, but since the degree of reduced pressure was 50 aHg, the residence time was approximately 30
This is about twice as long as in Example 2. The molten resin is pelletized by an extruder in an air atmosphere,
Formability was confirmed by sheeting by injection molding and extrusion molding.

The results are shown in Table 1.

Example 10 Hydrogenated polymer A was dried in a vacuum dryer at 100° C. for 4 hours, then pelletized in an extruder in a nitrogen atmosphere, and moldability was confirmed by injection molding. The results are shown in Table 2.

Example 11 Hydrogenated polymer A was dried in a vacuum dryer at 120° C. for 4 hours, then pelletized in an extruder in a nitrogen atmosphere, and moldability was confirmed by injection molding. The results are shown in Table 2.

Example I2 Hydrogenated polymer A was dried in a vacuum dryer at 120° C. for 8 hours, then pelletized using an extruder in a nitrogen atmosphere, and moldability was confirmed by injection molding. The results are shown in Table 2.

Example 13 Hydrogenated polymer A was dried for 10 minutes using a flash dryer in a nitrogen atmosphere.
After drying at 0° C. for 24 hours, pelletization was performed using an extruder in a nitrogen atmosphere, and moldability was confirmed by injection molding. The results are shown in Table 2.

Examples 14-16 Hydrogenated polymer B (Example 14), hydrogenated polymer C (Example 1)
5) and hydrogenated polymer D (Example 16) in Example 1, respectively.
It was dried in the same manner as above, pelletized, and its moldability was confirmed by injection molding.

The results are shown in Table 2.

Example 17 Example 10 except that hydrogenated polymer A was used and no drying was performed.
Injection molding was carried out in the same manner.

The results are shown in Table 2.

Examples 18-20 Hydrogenated polymer B (Example 158, Hydrogenated polymer C (Example 1)
9) and injection molding were carried out in the same manner as in Example 17, except that hydrogenated polymer D (Example 20) was used. The results are shown in Table 2.

(The following is a blank space) [Effects of the invention] The norbornene-based (co)polymer of the present invention exhibits good moldability because it has a low gel content, and when the water content in S/P is low, the moldability is better. improves. Therefore, the norbornene-based (co)polymer of the present invention suppresses the occurrence of silver streaks and fish eyes during molding, and also prevents part of the surface of the molded product from adhering to the mold. The peeling phenomenon that remains on the mold surface is also suppressed.
Good molded products can be continuously molded.

Taking advantage of this characteristic, the norbornene-based (co)polymer of the present invention can be used in optical materials such as lenses, optical disks, optical fibers, guiding waveguides, and plastic mirrors.
It can be used in a wide variety of applications, including automobile parts such as headlamp covers and tail lamp covers, building materials such as resin sheets for window glass, carport roofing materials, and housing materials for electrical products.

Patent applicant: Japan Synthetic Rubber Co., Ltd. Agent Patent Attorney Takashi Shirai

Claims (2)

[Claims] (1) Water obtained by hydrogenating a polymer obtained by metathesis polymerization of at least one norbornene derivative represented by the following general formula (I) or an unsaturated cyclic compound copolymerizable with the norbornene derivative 1. A norbornene-based (co)polymer comprising an additive polymer, wherein the hydrogenated polymer has a gel content of 1% by weight or less. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, n is 0 or 1, and at least one of X and Y is -(CH_2)_mCOOR^1, -(CH_
2)_mOCOR^2 or -(CH_2)_mC
N, where R^1 and R^2 represent a hydrocarbon group having 1 to 20 carbon atoms, and A, B and the remaining X or Y represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. . ) (2) The norbornene-based (co)polymer according to claim 1, which has a water content of 300 ppm or less.