JPH02227424A - Production of transparent polymer - Google Patents

Abstract

PURPOSE:To obtain a high-purity polymer by carrying out metathetic ring opening polymerization of a specific monomer or further a monomer copolymerizable therewith in a specified solvent in the presence of a metathetic polymerization catalyst, adding an alcohol thereto and separating the catalyst component and a low-molecular-weight substance as an alcoholic phase. CONSTITUTION:Metathetic ring opening polymerization of a tetracyclododecene derivative expressed by the formula (A and B are H or 1-10C hydrocarbon group; X and Y are H or 1-10C hydrocarbon group, etc.; m is 0 or 1) or further a monomer copolymerizable therewith in a mixed solvent of an alicyclic saturated hydrocarbon and/or aliphatic saturated hydrocarbon and a dialkyl glycol ether and/or in an aromatic hydrocarbon solvent in the presence of a metathetic polymerization catalyst and an alcohol is then added to the resultant polymerization reaction solution to separate an alcoholic phase. A polymer excellent in transparency, optical characteristics, heat, weather resistance, low water absorptivity, mechanical properties, etc., is obtained from the separated polymer solution phase.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a transparent polymer having excellent properties such as optical properties, heat resistance, weather resistance, low water absorption, and mechanical properties.

[Conventional technology]

In recent years, transparent polymers have been used not only as molding materials for automobile parts, lighting equipment, electrical parts, and miscellaneous goods that require normal transparency, but also as optical materials that place importance on optical properties. ing. Polymers used as optical materials are required to have not only transparency but also high-level properties such as heat resistance, weather resistance, low water absorption, and excellent mechanical properties.

Up to now, polymers that are suitable for optical materials include polymers obtained by hydrogenating tetracyclododecene-based hydrocarbon compounds alone or metasense-opening (co)polymers with norbornene-based hydrocarbon compounds. Tokukai Showa 6
0-26024), polymers obtained by metasense open polymerization of pentacyclopentadecene or hydrogenated polymers thereof (JP 63-145324), norbornene derivatives having polar substituents and/or tetracyclo (Co)polymer obtained by polymerizing and hydrogenating dodecene derivatives (Japanese Patent Publication No. 57-8815, Japanese Patent Application No. 1983)
2.-288528), etc. have been proposed.

[Problem to be solved by the invention]

In order to obtain the above-mentioned high-level properties in addition to transparency in polymers used as optical materials, the polymer must have a low content of metals and other impurities, and a low molecular weight such as unreacted monomers. It is necessary that the content of the body is low. For this reason, in the past, the polymerization reaction solution obtained by the metasense opening polymerization reaction was poured into a large amount of poor solvent to form a polymer precipitate, and this precipitate was further washed with the same poor solvent to remove the metal. The desired polymer is obtained by removing the catalyst components and low molecular weight components and then drying.When necessary, this polymer is further dissolved in an appropriate solvent and hydrogenated. It is taken.

However, in such a method, in order to precipitate and wash the polymer, a large amount of poor solvent, usually at least 10 times the weight of the polymerization reaction solution, is required, and the concentration of the polymerization reaction solution is often low. Since it is around 10%, it is actually necessary to use the poor solvent in an amount of 100 times or more the weight of the polymer. Therefore, in the industrial implementation of the above method, there have been major problems in that the equipment for recovering the solvent becomes large-scale and the utility load becomes heavy.

[Means to solve the problem]

The present invention was developed as a result of extensive research into the above problems.
When a metasense-opening polymerization reaction is carried out using a specific solvent, when alcohol is added to the resulting polymerization reaction solution, it separates into an alcohol phase and a polymer solution phase, and the catalyst components and unreacted components in the polymerization reaction solution are separated. Since low molecular weight substances such as monomers are extracted with high efficiency into the alcohol phase, it is possible to separate a polymer solution that substantially does not contain them, and it is sufficient to use a small amount of alcohol. This method was completed based on the discovery that the separated polymer solution can be directly subjected to the hydrogenation reaction when certain types of the above-mentioned specific solvents are used. be.

The method for producing a transparent polymer according to the present invention is characterized by at least one monomer represented by (1) below, or this monomer and other monomers copolymerizable therewith. Alcohol is added to the polymerization reaction solution obtained by ring-opening metasense polymerization using the following solvent A and/or solvent B in the presence of a metasense polymerization catalyst, and thereby,
The method is characterized in that an alcohol phase containing a catalyst component and a low molecular weight substance and a polymer solution phase are separated, and a polymer is obtained from the polymer solution of this polymer solution phase.

General formula (1) [wherein A and B are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, ] and Y are a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms,
Halogen atom, 1 to 1 carbon atoms substituted with halogen atom
0 hydrocarbon group, +cH2), C0OR', +CH2), 0COR', -
(CH,), OR', +CH,)1. C.N.

+cH2), C0NR2R', +CH2), C00Z.

+CH2), 0COZS+cH2), 02°+cH2)
. At least one of X and Y composed of W or
~20 hydrocarbon groups, Z is a hydrocarbon group substituted with a halogen atom, W is SiR'pDs-p (R' is a carbon number of 1-
10 hydrocarbon groups, D is a halogen atom, -0COR' or -OR'(R' represents a hydrocarbon group having 1 to 10 carbon atoms, p represents an integer of θ to 3), n is O to Indicates an integer of lO. ), and m is O or 1. ].

Solvent A: A mixture of (1) an alicyclic saturated hydrocarbon and/or an aliphatic saturated hydrocarbon and (2) a dialkyl glycol ether Solvent B: Aromatic hydrocarbon The present invention will be specifically described below.

The polymer obtained by the method of the present invention has the above general formula (
Polymers obtained by opening-polymerizing the monomer represented by 1) alone, copolymers obtained by ring-opening copolymerizing the monomer with other monomers copolymerizable therewith, and copolymers thereof. It is a hydrogenated polymer obtained by hydrogenating a polymer or copolymer of Generally, the molecular weight of these polymers is
Weight average molecular weight in terms of polystyrene: 20.000
from 700,000, especially from 30.000 to 500.0
It is 00.

In the above general formula (1), a specific example of a tetracyclododecene derivative in which m has a value of 1 is 8-carboxymethyltetracyclo[4,4,0°12.5.17.1
°]-3-dodecene, 8-carboxyethyltetracyclo[4,4,0°1? , Il+] 3-dodecene, 8-carboxy n-propyltetracyclo[4°4.0
．． 1'・5.1'111]-3-dodecene, 8-carboxyisopropyltetracyclo[4°4.0.1''',
1""] -]3-dodecene 8-carboxy n-butyltetracyclo[4,4°0.1"', 1""] -3-
)'Dece7.8-carboxyinbutyltetracyclo[
4,4°0.12°', 1'10] -3-dodecene, 8-carboxy5ec-butyltetracyclo[4°4
．． 0.12″%, If, I@coco-dodecene,
8-carboxyt-butyltetracyclo[4,4°0.
12·s, it, 1°]-3-dodecene, 8-carboxyphenyltetracyclo[4,4,0°18°5.
11・10-3-dodecene, 8-methyl-8-carboxymethyltetracyclo[4,4,0,1”・5.11
・lCoke-dodecene, 8-methyl-8-carboxyethyltetracyclo[4,4,0,1"・5.1"1°co-3-dodecene, 8-methyl-8-carboxyn-probyltetracyclo 0 [4,4,0,1'-',1”IO
3-3-)'f-sen8-methyl-8-carboxyisopropyltetracyclo[4,4,0,1"・5.11・self6]-3-dodecene, 8-methyl-8-carboxyn-butyl Tetrasik O [
4,4,0,1"°', 1""] -3-Yy', 8-methyl-8-carboxy5ec-butyltetracyclo[4,4,O,l"-', 1'1° ]-3-Dodece8-methyl-8-carboxyt-butyltetracy9
CJ [4,4,0°1”', 1”lo] -3-dodecene, 8-carboxybutyl-9-7enyltetracy9
0 [4,4,0,1''-', l'・1o] -3-F
fl, 8,9-dicarboxymethyltetracyclo[4,
4゜0.12・5.1ff, 1゜]-3-dodecene,
8-carboxycyclohexyltetracyclo[4,4,
0,1'・', 1'10] -3-dodecene, 8-carboxy (4°-1-butylcyclohexyl) f )
5 Schif o [4,4,0,1",1'°"]-]3-
Dodecene 8-methyl-8-carboxycyclohexyltetracyclo[4,4,0,1'゛', l'1°co-3-dodecene, 8-methyl-8-carboxy(4'-t-butylcyclohexyl) Tetracyclo[4,4,0,1'='11
1°] 3-dodecene, 8-acetoxytetracyclo[4,4,0,12゛'1
""-3-dodecene, 8-cyanotetracyclo[4,4,0,12°5.11
・'6-3-dodecene, 9-methyl-8-cyanotetracyclo[4,4,0゜1
2°S, t? 1(1) 3-dodecene, 8-methyl-8-cyanotetracyclo[4,4,0°12·',
1””] -]3-dodecene8,9-dimethyl-8,9
-dicyanotetracyclo[4,4°0.12・', l”
"] -] 3-dodecene 8-carbamoyltetracyclo[4,4,0,1'='lff, lO] 3-dodecene, 8-N-methylcarbamoyltetracyclo[4°4.0
．． 1”°5.1ff, 1G] 3-dodecene, 8-
N,N-diethylcarbamoyltetrashift0 [4,4
, O, 12°5.11°la] 3-dodecene, N
, N, N', N'-tetramethyl-8,9-dicarbamoyltetracyclo[4,4,0,1'・5.11
・10]-3-dodecene, 8-chlorotetracyclo[4,4,0,1'・5.11
・10-3-dodecene, 8-methyl-8-chlorotetracyclo[4,4,0゜1
2.5゜17.'']-]3-dodecene8-chloromethylcarboxytetracyclo[4゜4.0.12.5.11
+ 1°] -3-dodecene, 8-dibrombrovir lupoxytetracyclo[4,4,0,1'', 5.17.
10-3-dodecene, 8-dichloropropylcarboxytetracyclo[4,4,0,1'',1''''] -3
-dodecene, 8-chloromethylcarboxytetracyclo[4,4,0,1".5.17."]-]3-dodecene, 8-monobromphenylcarboxytetracyclo[4,
4,0,1"°', l'10] -3-dodecene, 8
-tribromphenylcarboxytetrasif 0 [4,
4,0,1"', 1" 1o] -3-Ff'sen, 8
．． 9-dichlorotetracyclo[4,4,O,l'°51
7・”]-]3-dodecene8-bromotetracyclo[4,4,0,1”・S, I
t, I11]-3-dodecene, 8-bromomethyltetracyclo[4,4,0,1''11
1・”]-]3-dodecene8-tribromobenzyltetracyclo[4,4,0゜1
2.5.17.”]-]3-dodecenetetracyclo[4
,4,0,1'°S,l? jlO-3-dodecene-8
, 9-dicarboxylic anhydride, 8.9-dimethyl-tetracyclo[4,4,0,1'°
517.1°]-3-dodecene-8,9-dicarboxylic anhydride, tetracyclo[4,4,0,12°', 1'10]
-3-dodecene-8,9-dicarboxylic acid imide, N-phenyl-5-methyltetracyclo[4,4°0.
12°S, Iff, lit-co-3-dodecene-8,
9-Dicarboxylic acid imide, 5-trichlorosilyltetracyclo[4゜4.0912
・5.17・”]-]3-dodecene 5-(dimethylmethoxysilyl) Tetracyclo[4,4,0,1”1.1
'10-3-dodecene, 8-(dimethylacetylsilyl)tetracyclo[4,4,0,1'・5.11・I1
1] to 3-dodecene, 8-trimethylsilyltetracyclo[4,4,0°12°5.17·1lll]-3-dodecene, and the like.

In addition, in the above-decedent (1), specific examples of bicyclo[2,2,1]-2-heptene derivatives in which the value of m is 0 include 5-carboxymethylbicyclo[2,2,1]-2 -heptene, 5-carboxyethylbicyclo[2,2,1]-2-heptene, 5-carboxyn-propylbicyclo[2,2,1]-
2-heptene, 5-carboxyisopropylbicyclo[2,2,1]-
2-heptene, 5-carboxy n-butylbicyclo[2,2,1]-]
2-heptene 5-carboxyisobutylbicyclo[2,2,1]-]
2-heptene 5-carboxy5eC-butylbicyclo[2,2゜1]
-2-heptene, 5-carboxyt-butylbicyclo[2,2,1]-2
-heptene, 5-carboxyphenylbicyclo[2,2,1]-2-
Heptene, 5-methyl-5-carboxymethylbicyclo[2,2,
1-2-heptene, 5-carboxybutyl-6-7enylbicyclo[2,2
,1] -2-heptene, 5,6-dicarboxymethylbicyclo[2,2,1]-
2-heptene, 5-carboxycyclohexylbicyclo [2,2゜1]
-2-heptene, 5-carboxy-(4°-t-butylcyclohexyl)
Bicyclo[2,2,1]-2-heptene, 5-methyl-
5-carboxycyclohexylbicyclo[2,2,1]
-2-heptene, 5-methyl-5-carboxy (4°-
t-butylcyclohexyl)bicyclo[2,2,1]
-2-heptene, 5-acetoxybicyclo[2,2,1]-2-heptene, 5-cyanobicyclo[2,2,1]-2-heptene, 6
-Methyl-5-cyanobicyclo[2,2,1]-2-heptene, 5-methyl-5-cyanobicyclo[2,2,1]-2-
Heptene 5,6-dimethyl-5,6-dichlorobicyclo[2゜2
．． 1]-2-heptene, 5-carbamoylbicyclo[2,2,1]-2-heptene, 5-N-methylcarbamoylbicyclo[2,2,1]-
2-heptene, 5-N,N-diethylcarbamoylbicyclo[2°2.
1]-2-heptene, N, N, N', N'-tetramethyl-5,6-dicarpamoylbicyclo[2,2,1]-2-heptene,
5-Chlorbicyclo[2,2,1]-2-heptene, 5
-Methyl-5-chlorobicyclo[2,2,1]]2-heptene5-chloromethylcarboxybicyclo[2,R,1]-
2-heptene, 5-dibrombrovir lupoxybicyclo [2°2.1
]-2-heptene, 5-dichloropropylcarboxybicyclo [2°2.1
]-2-heptene, 5-chlorophenylcarboxybicyclo[2,2゜1]
-2-heptene, 5-monobromphenylcarboxybicyclo[2,2,
1]-2-heptene, 5-tribromphenylcarboxybicyclo[2,2,
1]-2-heptene, 5.6-dichlorobicyclo[2゜2.13-2-heptene, 5-bromomethylbicyclo[2,2,1]-2-heptene, 5-bromoethylbicyclo[2, 2,1]-2-heptene, 5-tribrobenzylpoxycyclo[2,2,
l]-2-heptene, bicyclo[2,2,1]-2-heptene-5,6-dicarboxylic acid anhydride, 5,6-cyanobicyclo[2,2,1]-2-heptene-5,6 -dicarboxylic anhydride bicyclo[2,2,1]-2-hebutene-5,6-dicarboxylic imide, N-phenyl-5-methylbicyclo[2,2,1]-2
-Heptene-dicarboxylic acid imide, 5-trichlorosilylbicyclo[2,2,l]-2-heptene, 5-(dimethylmethoxysilyl)bicyclo[2,2゜l
]-2-heptene, 5-(dimethylacetylsilyl)bicyclo[2,2゜l
Co-2-heptene, 5-trimethylsilylbicyclo[2,2,13-2-heptene, etc. can be mentioned.

These monomers are not limited to just one type (although two or more types can also be used).

Furthermore, other monomers that can be copolymerized with these tetracyclododecene derivatives and/or bicycloheptene derivatives include norbornene compounds that can be polymerized with a metasense polymerization catalyst, cyclic olefins, and carbon-carbons in the main chain of the polymer. Mention may be made of monomers having carbon double bonds.

Specific examples of such copolymerizable monomers include cycloolefins such as cyclopentene, cyclooctene, 1°5-cyclooctadiene, and 1.5.9-cyclooctadiene; bicyclo[2° 2.1]-2-heptene, tricyclo[5,2,1,0''' co-8-decene, tricyclo[5,2,1,0'']-3-decene, tricyclo[5,2,1, 0'-'] -3,8-
Decadiene, tricyclo[6,2°1.0'1]-9-
undecene, tricyclo[6,2,1,0'°0]-4
- undecene, tetracyclo[4,4,0,1″, 1.
1t16] -3-dodecene, pentacyclo[6,5,
1,1"・1.0′・1.03・13-4-pentadecene, pentacyclo[6,5,1,1"°602・1°O"-']-4,11-pentadecadiene, pentacyclo o [6, 6, 1, 1", 0"', 0' 14] -4
-Hexadecene, pentacyclo[6,5,1,1'・6
．． Examples include polycycloalkenes such as 02.7.0''.l-co-11-hentadecene.

Not only one type of these other copolymerizable monomers may be used, but two or more types thereof can also be used.

The above-mentioned metasense ring-opening polymerization reaction of the raw material monomers is carried out in a specific solvent described below in the presence of a metasense polymerization catalyst, usually in an inert atmosphere such as nitrogen, helium, or argon.

The temperature of this mecthesis open polymerization reaction is usually -30 to
200°C, preferably 0-150°C, more preferably 3
The range is 0 to IQQt.

The above-mentioned metasense polymerization catalyst is usually a catalyst consisting of a combination of the following components (a) and (b), but an activator described below may be further added to increase the catalytic activity.

(a) Component: At least one component selected from the compounds of W, Mo, and Re; IA of Deming's periodic table,! IA! I
B.

11[A, at least one compound selected from IVA or IVB group elements having at least one element-carbon bond or element-hydrogen bond;
Compounds of WSMO or Re suitable as component (a) above include halides of these, oxynodecogenides, alkoxyhalides, alkoxides, carboxylates, (oxy)acetylacetonates, carbonyl complexes, acetonitrile complexes, and hydrides. Among the complexes, derivatives thereof, or combinations thereof, compounds of W and MO, particularly halides, oxyhalides, and alkoxyhalides thereof, are preferred from the viewpoint of high polymerization activity and practicality. Alternatively, a mixture of two or more compounds that produce the above-mentioned compounds by reaction may be used. These compounds can be combined with a suitable complexing agent, such as P(CsH
s) may be complexed with s, Cs Hs N, etc.

Specific examples of preferably used component (a) include W cjs, W cJ! s,wcl,,W B r
@ , W F s, W I a, M o Cj s,
M o Cj ,, M o C1' s, Ra CJ
s, WOCla, Mo0c1s, Red(-It3
, ReOBr3, W(OCsHi)s, W(J*(OC
aHs)4, MO(OCaHs)*Cja, Mo(O
C2Hs>s, Mo O2(acac) t, W(OC
OR)s, W(Co), , MO(Co)i, Re2.
(COLo.

Re0Bra'P(CiHs)a, WCj's”P(
CsHa)s, WCl, -C%H%N, W(Co
)s-P(CsHs)3, W(Co)3・(CH,C
N), etc. Among these, particularly preferable compounds include MoG5, Mo(OC
aHs)2(Js, W(Ja, W(OCl
H,) can include h, etc.

(C) As a specific example of a suitable component, for example, n C4Hs L! Sn Cs H+ t N
a, C* Hs N a .

CH3MgI SCaHsMgBr, CH3MgBr,
n CzHtMgCJ, (CsHs)aAI.

t CH3MgI% CHa=CHCH2MgCI
'-(Cal(s)zZn, (Ca)Is)zcdSC
aZn(CtHsL, (CHl)sB, (C18%)3
B, (n-C4Hs)sB.

(CHs)aAI-(CHsLAAl(J, (CH3)!
AlIC4'3, CHsAICja, (CaHs)aA
I%LiA1(CaHs)*, (CiHs)sAl0(
CaHs)i, (CiHsLaAICI!, CaHsA
I(jt, (CtHa)iAIH.

(iso-CmHs)tAIH, (CtHshAIOC
aHs.

(iso CaHs)sAl, (CiHs)zAI
icJa, (CHs)*Ga-(CH,)ssn, (n
-CnH,)4Sn.

(CaHs)ssiHs (n C6H13)3A
+, (n C*H+t)sAl, LiH, Na)
lXB*) (s, N 1k B H4, A I Ha,
Examples include L i A I H4 and TiHm. It is also possible to use a mixture of two or more compounds that produce these compounds through reaction.

Among the above, particularly preferred compounds include (CH3)
3Al, (CH3)tAlc! ', (CHa)sAI*
(Ja, CH3A I cla, (C2Hs)sAl,
(CaHs)tA1c! '.

(CtHl)3AIa(Ja, CaHsAI(Jz,
(CsHs)*AIH, (CaHs)aAIOCsHs
-(CaHs)tAICN, (CsHt)aAI, (i
so-CnH, *)sAl, (iso-CaHsL
aAIHs(C8H17)AL (CsHtvLAI
, (CsHs)3A1, and the like.

The quantitative relationship between the above components (a) and (c) is such that the metal atomic ratio (a):(b) is in the range of 1:1 to 1:20, preferably 1:2 to 1:10. Ru.

The metasense polymerization catalyst prepared from the above-mentioned components (a) and (b) usually has high catalytic activity in the metasense ring-opening polymerization reaction of the raw material monomers used in the above-mentioned present invention. By adding an activator consisting of component (C) as listed above, it can be used as a catalyst with even higher activity.

Various compounds can be used as the component (C), and particularly preferably used compounds include the following.

(1) Elemental boron, BF3, B(j,, B(On C
nHs)s, BFsO(CHsh, BF,0(Cs
Hs)s, BF30(n CaHs)a, BF3・2
csHsOH, BF3・2CH3COOH.

B Fs・Urea, BF3・Triethanolamine, B
Fs”piperidine, B Fa ・Ca Hs N H
2, B, 03, boron compounds such as Hs B Os, 5
i(OCiHs)*, Si (J), silicon compounds such as 4, (2) alcohols, hydroperoxides and peroxides, (3) water, (4) !II elements, (5) aldehydes and ketones, etc. Carbonyl compounds and their oligomers or polymers, (6) cyclic ethers such as ethylene oxide, epichlorohydrin, oxetane, (7) amides such as N,N-diethylformamide, N,N-dimethylacetamide, aniline, morpholine, piperidine. amines such as and azo compounds such as azobenzene, (8) N-nitrone compounds such as N-nidrone dimethylaine and N-nitron diphenylamine, (9) trichloromelamine, N-chlorsuccinoimide, phenylsulfonyl chloride, etc. In addition, the quantitative relationship between component (a) and component (C) varies greatly depending on the type of component (C) added, so it is uniformly defined. (C)
/ (a) (% ratio) value is 0.005 to 10,
It is preferably used in a range of 0.05 to 3.0.

In the metasense ring-opening polymerization reaction, the molecular weight of the resulting polymer can be adjusted by changing reaction conditions such as the type and concentration of the metasense polymerization catalyst, the polymerization temperature, the type and amount of the solvent, and the monomer concentration. However, it is usually preferable to adjust the molecular weight of the ring-opened polymer by adding an appropriate amount of a suitable molecular weight regulator to the polymerization reaction system. Such molecular weight regulators include α-olefins, α, ω
- Compounds having at least one carbon-carbon double bond or carbon-carbon triple bond in the molecule, such as diolefins or acetylenes, or polar allyl compounds such as allyl chloride, allyl acetate, trimethylallyloxysilane, etc. .

In the present invention, the following solvent A, solvent B, or a mixture thereof is used as the solvent for the above metasense polymerization reaction.

Solvent A consists of a mixture of solvent component (1) and solvent component (2).

As the solvent component (1), alicyclic saturated hydrocarbons and /l or aliphatic saturated hydrocarbons having 10 or less carbon atoms, preferably 5 to 8 carbon atoms are used. Here, specific examples of alicyclic saturated hydrocarbons include cyclopentane, methylcyclobencune, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, cycloheptane, decalin, etc. Specific examples of hydrogen include n-pentane, isopenkune, n-hexane, n-hebutane, and n-octane.

Dialkyl glycol ether is used as the solvent component (2). Specific examples include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, and triethylene glycol dimethyl ether.

The mixing ratio of solvent component (1) and solvent component (2) in the solvent is usually 95:5 to 30 by weight and 0. The ratio is preferably 90:10 to 40:60. Solvent component (1
) is too large, the solubility of solvent A in the produced polymer will be insufficient; on the other hand, if this ratio is too small, the reaction activity of the metasense ring-opening polymerization reaction will be low, resulting in a high degree of polymerization. It is not possible to obtain a polymer of

Solvent B consists of an aromatic hydrocarbon having 6 to 10 carbon atoms. Specific examples include benzene, toluene, xylene, and ethylbenzene. Not only one type of aromatic hydrocarbon, but also two or more types can be used.

In the metasense opening polymerization reaction carried out using the above-mentioned solvent, the monomer concentration is usually 10 to 40% by weight.

It is preferable to add a decatalyst agent to the obtained polymerization reaction solution after the end of this metasense opening polymerization reaction and before performing the extraction separation operation using alcohol, which will be described later. Thereby, the content of the catalyst component in the polymer solution to be separated can be reduced, so that a polymer with a low content of the catalyst component can be obtained.

Such decatalysts include triethanolamine, jetanolamine, monoethanolamine, triethylamine, diethylamine, tripropylamine, tributylamine, dibutylamine, ethylenediamine, hexamyl diamine, polyethylenediamine, pyridine,
Examples include organic amines such as tetramethylammonium hydroxide; inorganic alkalis such as sodium hydroxide, potassium hydroxide, and sodium carbonate.

The amount of the decatalytic agent added varies depending on the type, but is usually 1 to 1 mol per mole of the metasense polymerization catalyst used.
000 mol, preferably 5 to 100 mol.

In the present invention, alcohol is added to the polymerization reaction solution obtained as described above, and extraction and separation is thereby performed.

That is, alcohol is added to the polymerization reaction solution and stirred,
Thereafter, by allowing the mixture to stand still, it is separated into an upper alcohol phase and a lower polymer solution phase.

Examples of alcohols include those having 1 to 10 carbon atoms, such as methanol, ethanol, impropatol, butanol, etc.
．． Preferably 1 to 4 alcohols are used. Not only one type of alcohol can be used, but two or more types can also be used.

The amount of alcohol to be added varies depending on the type of solvent used, the type of alcohol added, the concentration of the polymerization reaction solution, and the temperature of the polymer solution at the time of addition, but it is used for one extraction and separation operation. The amount of alcohol used is usually 0.1 to 5 times the weight of the solvent used, preferably 0.2 to 2 times the weight of the solvent used, in order to suitably achieve this liquid-liquid two-phase separation. be. If the amount of alcohol used is less than 0.1 times by weight, there is a risk that the desired separation will not be carried out, while if it is more than 5 times by weight, the polymer will tend to precipitate, making it difficult to achieve suitable extraction and separation. Can not.

However, even if a small amount of precipitation occurs, the effects of the present invention will not be impaired as long as the fluidity of the polymer solution phase is maintained, and therefore it should not be understood as being outside the scope of the present invention.

Furthermore, the extraction and separation operation by adding alcohol is not limited to one time, but is preferably repeated. In this case, it is preferable to replenish the polymer solution each time with a corresponding amount of solvent A or B transferred from the polymer solution to the alcohol phase.

There is no particular restriction on the temperature of the polymerization reaction solution when adding the alcohol, but since the state of separation may change depending on the temperature, it is usually preferable to carry out the addition at a temperature of 10 to 80°C.

By the above extraction and separation operation using alcohol, low molecular weight polymers such as catalyst components and unreacted monomers in the polymerization reaction solution are extracted into the alcohol phase with high separation efficiency, and as a result, the polymerization of the separated polymer solution phase is The combined solution has a very low content of catalyst components and low molecular weight substances, and as a result, a single polymer solution substantially free of these impurities is obtained.

A polymer can be obtained from this polymer solution by removing the solvent by a conventional method, such as steam stripping, and further drying if necessary. The polymer obtained here has an extremely low content of catalyst components and low molecular weight substances, and is therefore extremely suitable as, for example, an optical material.

On the other hand, by hydrogenating the produced polymer,
- Hydrogenated polymers with excellent layer properties can be obtained. This hydrogenation method is preferably carried out as follows depending on the type of solvent used in the metasense opening polymerization reaction.

b) When only solvent A is used, solvent A undergoes changes in the hydrogenation reaction and does not impair the reaction activity of the hydrogenation reaction, so it is itself a suitable solvent for the hydrogenation reaction. It is possible. Therefore, the polymer solution obtained by the extraction and separation operation using alcohol can be directly subjected to the hydrogenation reaction. According to this method, it is not necessary to coagulate and recover the polymer from the polymer solution and to dissolve the polymer in a hydrogenation solvent, and therefore it is possible to produce a hydrogenated polymer very advantageously. Can be done.

■) When using solvent B Solvent B is an aromatic hydrocarbon, and the double bonds of its aromatic rings undergo hydrogenation, so the polymer solution obtained by the above extraction and separation operation with alcohol is directly subjected to the hydrogenation reaction. cannot be provided. Therefore, the solvent B is removed from the polymer solution to recover the polymer, and the polymer is dissolved in another solvent suitable for the hydrogenation reaction to perform the hydrogenation reaction.

In the hydrogenation reaction, a hydrogenation catalyst is added to the polymer solution,
This is carried out by applying hydrogen gas at normal pressure to 300 atm, preferably 2 to 150 atm, at 0 to 200°C, preferably 20 to 180°C.

As the hydrogenation catalyst, those used in ordinary hydrogenation reactions of olefinic compounds can be used.

As this hydrogenation catalyst, heterogeneous catalysts and constrained catalysts are known.

Heterogeneous catalysts include palladium, platinum, nickel,
Catalysts such as rhodium and ruthenium m1wc Solid catalysts supported on carriers such as carbon, silica, alumina, and titania can be used. In addition, as a homogeneous catalyst, nickel naphthenate/triethylaluminum,
Nickel acetylacetonate/triethylaluminum, cobalt octenoate/n-butyllithium, titanocene dichloride/diethylaluminium monochloride,
Examples include rhodium such as rhodium acetate and chlorotris(triphenylphosphine) rhodium.

The hydrogenation reaction is preferably carried out such that the hydrogenation rate of the obtained hydrogenated polymer is 50% or more, preferably 70% or more, more preferably 80% or more. This is because, in general, the higher the hydrogenation rate, the higher the thermal stability and weather resistance. For example, hydrogenated polymers with a hydrogenation rate of less than 50% may lack practicality in terms of thermal stability and weather resistance;
Depending on the application, it may be necessary to use a hydrogenated polymer with a hydrogenation rate of 100%.

The polymer solution that has undergone the hydrogenation reaction is subjected to post-treatment depending on the type of catalyst, but if a solid catalyst is used, the catalyst is removed by filtration, etc., and then it is sent to a concentrator, evaporator, or ventruder. A hydrogenated polymer is obtained by removing the solvent using an apparatus such as -. Hydrogenated polymers can also be obtained by steam stripping and coagulation in conventional poor solvents.

In the method of the present invention, various additives such as antioxidants can be added as necessary after completion of the metasense opening polymerization reaction or completion of the hydrogenation reaction. Examples of this antioxidant include, for example, 2,6-T
-Butyl-4-methylphenol, 2.2°-dioxy-3,3°-di-t-butyl-5.5”-dimethyldiphenylmethane, phenyl-β-naphthylamine, pentaerythrityl-tetrakis[3-(3, 5-di-t-butyl-4-hydroxyphenyl) propionate, tris(2,4-di-t-butylphenyl)phosphite, bis-(2,6-di-t-butyl-4-methylphenyl) Examples include pentaerythritol diphosphite.

〔effect〕

According to the method of the present invention, in order to carry out the metasense opening polymerization reaction of a specific cyclic monomer using a specific solvent, the alcohol is separated from the polymer solution phase by adding alcohol to the resulting polymer solution. Catalytic components and low molecular weight substances are extracted from the phase with high efficiency, and as a result, a polymer solution that substantially does not contain them can be separately separated and recovered, and only a small amount of alcohol is needed for extraction. Therefore, the desired transparent polymer can be produced very advantageously.

In addition, especially when certain types of the above-mentioned specific solvents are used as the solvent for the metasense opening polymerization reaction, the hydrogenation reaction may be carried out directly on the separated polymer solution. It is possible to produce composites and is therefore very industrially advantageous.

Since the transparent polymer produced by the method of the present invention has extremely high purity, it has particularly good optical properties, heat resistance, weather resistance,
In addition to general molding materials that have excellent mechanical properties and other properties, they are also used in optical video discs, audio discs, document file discs, memory discs,
It can be suitably used as an optical material for camera lenses, laser beam lenses, etc.

The polymer produced according to the present invention can also be used with known resin materials such as styrene resin, acrylic resin, polyester resin, polyamide resin, polycarbonate resin, polyphenylene oxide resin, polyphenylene sulfide 1llL=ttlJ ether sulfone resin, polysulfone resin. , polyimide resin, polybutadiene resin,
It can be blended with ABS resin, ABS resin, etc. to obtain properties that are insufficient with individual resins.

[Example 1] Examples of the present invention will be described below, but the present invention is not limited thereto.

Example 1 Monomer represented by the structural formula (8-methyl-8-carboxymethyltetracyclo[4,4,0,1'·5.17·”]-
] A solvent prepared by mixing 8.0 g (34.5 mol) of 3-dodecene, cyclohexane from which water has been removed, and ethylene glycol dimethyl ether in a weight ratio of 8=2 (hereinafter referred to as "solvent A") ) 24.0 g and 580 g (6.9 mol) of 1-hexene, which is a molecular weight regulator, were charged into a reactor with a capacity of 501, which was purged with nitrogen gas. /1 chlorobenzene solution of tungsten hexachloride, 137 g;
143 g of a toluene solution of diethylaluminium chloride with a concentration of 0.96 mol/l and 34 g of a toluene solution of paraldehyde with a concentration of 0.2 mol/l were added, and a polymerization reaction was carried out at 80° C. for 3 hours.

The monomer conversion rate in this polymerization reaction was determined to be 97.5% by gas chromatography analysis of the resulting polymerization reaction solution.
Met.

The polymerization reaction solution obtained as above was cooled to 40°C and transferred to a container with a capacity of 2,001 kg, and 2 g of triethanolamine was added thereto and stirred for 30 minutes.
Kg was added to dilute the mixture, and in this state, 20 g of methanol was added to the mixture, stirred, and then allowed to stand for 30 minutes, resulting in separation into upper and lower layers.

Collect g of polymer solution 39 from the lower phase and transfer it to another container, add g to solvent A 20 and g to methanol IO to perform a second extraction separation, and collect the polymer solution from the lower phase. 42
To this, g was further added to the solvent to perform a third extraction and separation by adding g to 18 and g to methanol 9, and g was recovered from the lower phase to a polymer solution 40.

A part of the obtained polymer solution was collected and this was added to the TS.
As a result of analysis using C method, gas chromatography method, fluorescent X-ray method, atomic absorption method, etc., the amount of polymer in the polymer solution was found to be equivalent to 6.4 g, and the amount of remaining unreacted monomers. 0.1% by weight or less based on the polymer;
It was found that both the tungsten content and the aluminum content were 5 ppm or less. This polymer state is substantially free of catalyst components and unreacted monomers.

The total amount of methanol used in the above three extractions was 4.9 times the weight of the monomer used.

Add 24 grams of solvent A to the polymer solution obtained by the above three extraction and separation operations to obtain a polymer solution with a polymer concentration of 10% by weight, and add this polymer solution and a hydrogenation catalyst. The autoclave was charged with 1.28 kg of 5% palladium/alumina catalyst into a 1,001 capacity autoclave purged with nitrogen, and heated under hydrogen gas pressure of 100 g/c IIlf.
The temperature was raised to 5°C and a hydrogenation reaction was carried out for 4 hours. Thereafter, the reaction solution was cooled, and the hydrogenation catalyst was filtered through a 1 m filter and
．． The residue was removed by filtration using a 2 mm filter) No. 17, followed by steam stripping to remove the solvent, followed by vacuum drying to obtain pure white hydrogenated polymers 6.3 and 8.

The weight average molecular weight in terms of polystyrene obtained by analyzing this hydrogenated polymer by gel vermiacetic chromatography was 155.000, and the H-NMR
Further analysis showed that the hydrogenation rate was 99% or more.

This hydrogenated polymer was very suitable as a transparent polymer for optical materials.

Example, 2 Monomer 8-methyl-8-carboxymethyltetracyclo[4,4,0,1''·5.17·′ used in Example 1.

]-3-dodecene (6.4 g), and the monomer 5-methyl-5-carboxymethylbicyclo[2,2,11-2-heptene (1.6 g) represented by the structural formula of Example 1. A metasense opening polymerization reaction, a total of three extraction and separation operations using methanol, and a hydrogenation reaction were carried out in the same manner as in Example 1 except that the monomer was used in place of the monomer, to give a pure white hydrogenated polymer 6.1 g. I got it.

As a result of analysis of the finally separated polymer solution, the monomer remaining in the polymer was 0.1% by weight or less, and the tungsten content and aluminum content were both 5 ppm or less. In addition, the weight average molecular weight of the hydrogenated polymer is 1
45,000, and the hydrogenation rate was 99% or more.

Example 3 Monomer 8-methyl-8-carboxyl used in Example 1
chill f) 5 cyclo[4,4,0,)”',1””
]-3-dodecene6,4Kg and tricyclo[5,2,
1,0”.

“] -3,8-decadiene (dicyclopentadiene)
In the same manner as in Example 1 except that 1.6 kg of the monomer in Example 1 was used, a metasense opening polymerization reaction, a total of three extraction separation operations with methanol, and a hydrogenation reaction were carried out to obtain pure white hydrogen. 6.0 g of added polymer was obtained.

As a result of analysis of the finally separated polymer solution, the monomer remaining in the polymer was 0.1% by weight or less, and the tungsten content and aluminum content were both 5 ppm or less. In addition, the weight average molecular weight of the hydrogenated polymer is 1
60,000. The hydrogenation rate was 99% or more.

Example 4 A metasense open-circuit polymerization reaction was carried out in the same manner as in Example 1, except that toluene was used instead of solvent A. Analysis of the obtained polymerization reaction solution revealed that the monomer conversion rate was 98.5%.

To the resulting polymerization reaction solution, 2g of triethanolamine was added and stirred, further diluted by adding 16kg of toluene, and extracted and separated by adding 30g of methanol, resulting in separation into two layers, upper and lower. did.

g is collected from the lower phase into a polymer solution 42, and a second extraction separation is performed by adding 20 g to toluene and 20 g to methanol, and g is collected from the lower phase into a polymer solution 45. A third extraction separation was carried out by adding 18 g of toluene and 18 Kg of methanol, and 44 Kg of the polymer solution was extracted from the lower phase.
i was collected.

Analysis of this polymer solution revealed that the monomer remaining in the polymer was 0.1% by weight or less, and the tungsten content and aluminum content were both 5 ppm or less.

The total amount of methanol used in the above three extractions was 8.5 times the weight of the monomer used.

The obtained polymer solution was subjected to steam stripping and vacuum drying to obtain 6.8 kg of polymer.

This polymer was dissolved in 61 kg of a solvent Δ■, 1.36 g of a hydrogenation catalyst consisting of 5% palladium/alumina was added, and a hydrogenation reaction was carried out in the same manner as in Example 1 to obtain a pure white hydrogenated polymer 6. I got & on .7.

The weight average molecular weight of the hydrogenated polymer obtained here is 1i-
160,000, and the hydrogenation rate was over 99%.

Comparative Example 1 A metasense opening polymerization reaction was carried out using toluene as a solvent in the same manner as in Example 4. After adding 2 kg of triethanolamine to the obtained polymerization reaction solution and stirring, 47 kg of toluene was added to adjust the polymer concentration. The polymer was adjusted to 10% and poured into 800g of methanol to coagulate the polymer.

The resulting slurry liquid was filtered through a 200-mesh wire mesh, and then the polymer powder was washed with 200 kg of methanol and vacuum-dried to obtain 7.0 g of polymer.

When this polymer was analyzed, the remaining monomer was found to be 0.2
The content of tungsten was 18 ρPms and the content of aluminum was 15 ppm.

The total amount of methanol used in Comparative Example 1 was 125 times the weight of the monomer used.

By comparing Comparative Example 1 and each Example, it is clear that according to the method of the present invention, the extraction separation operation using alcohol is performed on the polymer solution of the metasense ring-opening polymerization reaction, so that the obtained polymer It is clear that the amounts of catalyst components and low molecular weight substances present are very small and that the amount of alcohol used is small.

Claims (1)

[Scope of Claims] 1) At least one monomer represented by the following general formula (I) or this monomer and another monomer copolymerizable therewith are mixed in the following solvent A and/or Alcohol is added to the polymerization reaction solution obtained by carrying out ring-opening polymerization of metasense in the presence of a metasense polymerization catalyst using solvent B, and thereby,
1. A method for producing a transparent polymer, which comprises separating an alcohol phase containing a catalyst component and a low molecular weight substance from a polymer solution phase, and obtaining a polymer from the polymer solution of the polymer solution phase. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are included ▼ [In the formula, A and B are hydrogen atoms or hydrocarbon groups having 1 to 10 carbon atoms, and hydrocarbon group,
Halogen atom, 1 to 1 carbon atoms substituted with halogen atom
0 hydrocarbon group, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ composed of X and Y. At least one of Y is a group other than a hydrogen atom and a hydrocarbon group (here, R^1, R^2,
R^3 and R^4 are hydrocarbon groups having 1 to 20 carbon atoms, Z
is a hydrocarbon group substituted with a halogen atom, W is SiR^
5_pD_3_-_p (R^5 is a hydrocarbon group having 1 to 10 carbon atoms, D is a halogen atom, -OCOR^6 or -O
R^6 (R^6 represents a hydrocarbon group having 1 to 10 carbon atoms)
, p represents an integer of 0 to 3), n represents an integer of 0 to 10. ), and m is 0 or 1. ]. Solvent A: A mixture of (1) alicyclic saturated hydrocarbon and/or aliphatic saturated hydrocarbon and (2) dialkyl glycol ether Solvent B: Aromatic hydrocarbon 2) Solvent A as a solvent for the metasense ring-opening polymerization reaction 2. The method for producing a transparent polymer according to claim 1, wherein the hydrogenated polymer is obtained by directly subjecting the separated polymer solution to a hydrogenation reaction.