CA2147347C - Isomerization of cycloolefin from endo-form to exo-form and isomer mixture of cycloolefin - Google Patents
Isomerization of cycloolefin from endo-form to exo-form and isomer mixture of cycloolefin Download PDFInfo
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Abstract
Disclosed is a process for isomerizing an endo form of a cycloolefin to an exo form of the cycloolefin of the formula:
(see above formula) (wherein R1 to R18 are each hydrogen, halogen or hydrocarbon and a pair of some of them may form a ring, n is 0 or 1 and m is 0 or a positive integer, provided that m and n cannot be 0 simultaneously) in the presence of a solid acid catalyst;
and a resulting isomer mixture of up to 80 mol % of the endo form and at least 20 mol % of the exo form of the cycloolefin.
The cycloolefin isomer mixture is useful for the production of an ethylene-cycloolefin random copolymer which in turn is useful for the production of, for example, optical memory disks and fibers.
(see above formula) (wherein R1 to R18 are each hydrogen, halogen or hydrocarbon and a pair of some of them may form a ring, n is 0 or 1 and m is 0 or a positive integer, provided that m and n cannot be 0 simultaneously) in the presence of a solid acid catalyst;
and a resulting isomer mixture of up to 80 mol % of the endo form and at least 20 mol % of the exo form of the cycloolefin.
The cycloolefin isomer mixture is useful for the production of an ethylene-cycloolefin random copolymer which in turn is useful for the production of, for example, optical memory disks and fibers.
Description
This is a divisional application of Canadian Patent Application Serial No. 2,023,214 filed August 14, 1990.
FIELD 01: TIIE INVENTION
This invention relates to isomerization of a cycloolefin such as tetracyclododecene or pentacyclopen-tadecene from an endo form to an exo form and to copolymerization of a cycloolefin and ethylene.
The present applicant found that cycloolefin random copolymers obtained by copolymerization of ethyl-ene and tetracyclododecenes are synthetic resins having excellent transparency and well-balanced properties among heat resistance, thermal wing resistance, chemi-cal resistance, solvent resistance, dielectric proper-ties, mechanical properties and that such cycloolefin random copolymers exhibit excellent performance in a field of optical materials such as optical memory disks and fibers. Therefore, the present applicant already proposed such random copolymers in Japanese Laid-Open Patent Publications Nos. 168708/1985, 98780/1986, 115912/1986, 115916/1986, 120816/1986, and 252407/1987.
Tetracyclododecenes used for production of 2p such random copolymers are prepared by a Diels-Alder reaction between corrresponding norbornenes and cyclo-pentadienes.
In this Diels-Alder reaction, cis addition dominantly proceeds. for example, in a reaction between cyclopentadiene (a) and norbornene (b), tetracyclodode-cene having an endo form (c) is mainly formed as shown in the following reaction formula.
(a) (b) (c) 214' 3 4'~
,_... - 2 - 73997-2D
And tetracyclododecene having an exo ~orm (d) of the following formula is hardly formed.
,a, It is also known that cycloolefin random copolymers produced by copolymerizing tetracyclodode-Genes mainly having an endo form prepared by the above Diels-Alder reaction with ethylene exhibit excellent heat resistance and mechanical strength.
International Laid-Open Publication No.
W089/01950 describes that cycloolefin random copolymers obtained by copolymerization of ethylene with pentacy-clopentadecenes (cycloolefins) have excellent transpar-ency and are excellent not only in optical properties such as optical uniformity and small birefringence but also in other properties such as heat resistance, chemi-cal resistance, dimensional stability and mechanical properties.
Pentacyclopentadecenes used as a cycloolefin for production of such random copolymers are also pre-pared by a Diels-Alder reaction between corresponding dihydrodicyclopentadienes (partially hydrogenated products of dicyclopentadienes) and cyclopentadienes.
For example, in a reaction between eyclopenta-diene (a) and dihydrodicyclopentadiene (e), pentacyclo pentadecene having an endo form (f) is mainly formed as shown in the following reaction formula in the same manner as the preparation of tetracyclododecene.
(a) (e) (f ) And, pentacyclopentadecene having an exo form of the following formula (g) is hardly formed.
H
H H (g) I
The present applicant has made a diligent study to further improve heat resistance and mechanical strength of the above random copolymer of a cycloolefin and ethylene, and found the following. That is, when an isomer mixture containing a larger amount of a cycloole-fin having an exo form (sometimes called "exo-form cycloolefin" hereinbelow) is used as a cycloolefin, the resultant random copolymer has remarkably improved heat resistance and mechanical strength. And, the present applicant has found an industrially advantageous process for isomerization for the production of such an isomer mixture containing a large amount of an exo form cy-cloolefin.
SUMMARY OF THE INVENTION
A first aspect of this invention provides a process for the isomerization of a cycloolefin from an endo form to an exo form which comprises isomerizing an endo-form cycloolefin of the following formula (I) _R16 R R2 R7 R8 R11 R1 R17 (I) \ R18 R4 R5 a6l R10 I R14 n m (wherein Rl to Rl4 are independently a hydrogen atom, a halogen atom or a hydrocarbon group, R15 to R18 are independently a hydrogen atom, a halogen atom or a hydrocarbon group, or R15 or R16 and R17 or R18 may be bonded to each other to form a monocyclic or polycyclic group, or R15 and R16 or Rl7 and R18 may together form an alkylidene group, n is 0 or 1, and m is 0 or a positive integer, preferably 0, 1 or 2, provided 2~4'~3~.~
that m and n cannot be simultaneously zero), in the presence of a solid acid catalyst to convert its endo form into the corresponding exo form.
BRIEF DESCRIPTION OF DRAWINGS
Fig. 1 shows a relationship between a content (mol%) of tetracyclododecene-3 in each of ethylene-tetracyclododecene-3 copolymers obtained by copolymeri-zation of ethylene with each of four tetracyclodode-cene-3 isomer mixtures having a different endo-form cycloolefin/exo-form cycloolefin ratio and a TMA soften-ing temperature of each of the copolymers.
Fig. 2 shows a relationship between a content (mol%) of tetracyclododecene in the above ethylene/tetracyclododecene-3 copolymers and flexural modulus thereof.
DETAILED DESCRIPTION OF TIIE INVENTION
The starting material used in this invention is a cycloolefin having an endo form, and represented by the foregoing formula (I).
In the formula (I), each of R1 to R14, inde-pendently from each other, is a hydrogen atom, a halogen atom or a hydrocarbon group. Preferred examples oP the halogen atom are fluorine, chlorine and bromine. Pre-ferred examples of the hydrocarbon group are lower alkyl groups such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl and tert-butyl groups.
Further, in the formula (I), each of R15 to R18, independently from each other, is a hydrogen atom, a halogen atom or a hydrocarbon group. Examples of the halogen atom are as specified above. Preferred examples of the hydrocarbon group are alkyl groups such as methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, hexyl and stearyl groups, and cycloalkyl groups such as a cyclohexyl group.
R15 or R16 and R17 or R18 may be bonded to each other to form a monocyclic or polycyclic group, or R15 and R16 or, Rl7and R18 may form an alkylidene group together. As the monocyclic or polycyclic group, R15 or R16 and R17 or R18 may form, e.g. a cyclopentyl group, cyclopentenyl group, cyclohexyl group or the like to-gether with carbon atoms to which R15, R16~ R17 and R18 are bonded. And, preferred examples of the above alky-lidene group are ethylidene, propylidene, and isopropy-lidene groups.
The "n" is 0 or 1, and the "m" is 0 or a positive integer, provided that n and m cannot be zero at the same time.
In the above formula (I), when n is 0 and m is 1, the above formula (I) is represented by the following formula (I-A) .
R17 (I_A) wherein R7 to R18 are as defined in the above formula (I).
And, when n is 1 and m is 0, the above formula (I) is represented by the following formula (I-B) R17 (I-B) wherein R1 to R10 and R15 to R18 are as de-fined in the above formula (I).
Specific examples of the cycloolefin of the formula (I) (including the above formulae (I-A) and -- 214734?' (I-B)) are preferably as follows:
211 Tetracyclo[4,4,0,12~5,17,10~_3_dodecene (41 ~ 8), 8-methyltetracyclo(4,4,0,12~5,17,10~-3-dodecene, 8-methyl-tetracyclo[4,4,0,12~5,17,10~-3_ dodecene, 8-ethyltetracyclo[4,4,0,12~5,17,10~_3-dodecene, 8-propyltetracyclo(4,4,0,12~5,17,10~_3_ dodecene, 8-hexyltetracyclo[4,4,0,12~5,17,10~_3_ dodecene, 8-stearyltetracyclo[4,4,0,12~5,17,10~-3-dodecene, 8,9-dimethyltetracyclo[4,4,0,12~5,17,10~_ 3-dodecene, 8-methyl-9-ethyltetracyclo[4,4,0,12~5,17,10~_ 3-dodecene, 8-chlorotetracyclo[4,4,0,12~5,1~,10~-3-dodecene, 8-bromotetracyclo[4,4,0,12~5,17,10~-3-dodecene, 8-fluorotetracyclo[4,4,0,12~5,17,10~_3-dodecene, 8,9-dichlorotetracyclo[4,4,0,12~5,17,10~_ 3-dodecene, 8-cyclohexyltetracyclo(4,4,0,12~5,17,10~_ 3-dodecene, 8-isobutyltetracyclo[4,4,0,12~5,17,10~_3-dodecene, 8-butyltetracyclo[4,4,0,12~5,17,10~-3-dodecene, 8-ethylidenetetracyclo[4,4,0,12~5,17,10~_ 3-dodecene, 8-ethylidene-9-methyltetracyclo-214'734 _8_ [4,4,0,12~5,17,10)_3_dodecene, 8-ethylidene-9-ethyltetracyclo-[4,4,0,12~5,17,10]_3_dodecene, 8-ethylidene-9-isopropyl-tetracyclo-[4,4,0,12~5,17,10~-3_dodecene, 8-ethylidene-9-butyl-tetracyclo-[4,4,0,12~5,17.10~_g_dodecene, 8-n-propylidene-tetracyclo[4,4,0,12~5,17.10~_ 3-dodecene, 8-n-propylidene-9-methyltetracyclo-[4,4,0,12~5,17,10]_3_dodecene, 8-n-propylidene-9-ethyltetracyclo-[4,4,0,12~5,17,10]-3_dodecene, 8-n-propylidene-9-isopropyltetracyclo-[4,4,0,12 5,17,10]-3_dodecene, 8-n-propylidene-9-butyltetracyclo-[4,4,0,12~5,17,10~-3_dodecene, 8-isopropylidenetetracyclo[4,4,0,12~5,17.10~-3-dodecene, 8-isopropylidene-9-methyltetracyclo-[4,4,0,12~5,17,10~_3_dodecene, 8-isopropylidene-9-ethyltetracyclo-[4,4,0,12~5,17,10~_3_dodecene, 8-isopropylidene-9-isopropyltetracyclo-[4,4,0,12'5,17,10]_3_dodecene, 8-isopropylidene-9-butyltetracyclo-[4,4,0,12~5,17,10]_3_dodecene, 5,10-dimethyltetracyclo[4,4,0,12~5,17,10~_ 3-dodecene, 2,10-dimethyltetracyclo[4,4,0,12~5,17.10~_ 3-dodecene, 11,12-dimethyletracyclo[4,4,0,12~5,17.10~-3_ dodecene, 2,7,9-trimethyltetracyclo[4,4,0,12~5,17,10~-3-dodecene, 9-ethyl-2,7-dimethyltetracyclo-[4,4,0,12~5,17,10]-3-dodecene, 21 ~.'~~ 4'~
9-isobutyl-2,7-dimethyltetracyclo-[4,4,0,12~5,17,10~_g_dodecene, 9,11,12-trimethyltetracyclo-[4,4,0,12~5,17.10~_3_dodecene, 9-ethyl-11,12-dimethyltetracyclo-[4,4,0,12~5,17'10]_3_dodecene, 9-isobutyl-11,12-dimethyltetracyclo-[4,4,0,12'5,17,10]_3_dodecene, 5,8,9,10-tetramethyltetracyclo-[4.4,0,12~5,17.10~_3_dodecene;
pentacyclo[6,5,1,13~6,02.7~09,13~_ 4-pentadecene (51 ), 1,3-dimethyl-pentacyclo[6,5,1,13~6,p2.7~09,13~_ 4-pentadecene, 1,6-dimethyl-pemtacyclo[6,5,1,13~6,02,7,09,13~_ 4-pentadecene, 14,15-dimethyl-pentacyclo[6,5,1,13~6,02,7~09,13~_ 4-pentadecene, pentacyclo[6,6,1,13~6,p2,7~09,13~_4_pentadecene;
1,3-dimethyl-pentacyclo[6,6,1,13~6,02.7,09,14~_ 3CH~C1~3 3 4-hexadecene (4 ~ ~~~ ~12) , 1,6-dimethyl-pentacyclo[6,6,1,13~6,p2.7~09,14~-4-hexadecene, 15,16-dimethyl-pentacyclo[6,6,1,13~6,02,7~09,14~_ 4-hexadecene;
pentacyclo[6,5,1,13'6,02,7,09.13~penta-decadiene-4,10 ( 51 ,11 ) ' pentacyclo[4,7,0,12~5,19,12~08,13~_3-peritadeCene (3 ~ 2 1 13 X211 ) methyl-substituted pentacyclo--- 2~47~47 [4,7,0,12'5,19,12~08,13~_3_pentadecene, dimethyl-substituted pentacyclo-[4,7,0,125,19,12~08,13~_3_pentadecene, trimethyl-substituted pentacyclo-[4,7,0,12'5,19,12,08,13~_3_pentadecene;
heptacyclo-[7,8,0,13~6,110,17~112,15~01,9~
02,7~011,16~_4_eicosene( ~ 13 3 2 1 l~j trimethyl-substituted heptacyclo-[7,8,0,13'6,110,17~112,15~01,9~02,7~011,16~_ 4-eicosene, tetramethyl-substituted heptacyclo-(7,8,0,136,110,17~112,15~01,9~02,7~011,16~_ 4-eicosene, methyl-substituted heptacyclo-[7,8,0,13'6,110,17~112,15~01,9~02,7~011,16~_ 4-eicosene, dimethyl-substituted heptacyclo-[7,8,0,13'6,110,17~112,15~01,9~02,7~011,16~_ 4-eicosene; and nonacyclo[9,10,1,14~7,113,20~115,18~02,10~
03,8,012.21~014,19~_5_pentacosene 9 0 11 131 .LS
( 51 7 ) .
3 2 1 21 2~9 18 Y
The endo form of a cycloolefin, when it is, e.g. tetracyclo[4,4,0,12~5,17,10~_3_dodecene, is repre-sented by the following formula (c) as described above.
(c) And, the end form of a cycloolefin, when it is, e.g.
pentacyclo-[4,7,0,12'5,08,13~19,12~_3_pentadecene, is 214734?
-~~-represented by the following formula (f) as described above.
(f) The stereostructure of the endo form of a cycloolefin is believed to be clear on the basis of the above-specified formulae.
In the process of this invention, the above-described cycloolefins having an endo form are converted into cycloolefins having the corresponding exo form by isomerization in the presence of a solid acid catalyst.
The stereostructure of the exo form cycloole-fin is believed to be clear on the basis of the follow-ing formulae. That is, for example, the exo form corre-sponding to the endo form of the formula (c) is reprent-ed by the following formula (d), and the exo form corresponding to the endo form of the formula (f) is represented by the following formula (g).
(g) In the process of this invention, preferred as a solid acid catalyst are oxides or sulfides of metals belonging to the groups 3 to 8 of the periodic table or organic solid acids. Preferred examples of the oxides and sulfides are those of A1, Si, P, Ti, V, Cr, Mo, W, 214.'x.3 4?
Mn, Fe or Co. Specific examples of such oxides and sulfides are silica-alumia (composed mainly of A1203 and Si02), alumina (composed mainly of A1203), zeolite (composed mainly of Na20, A1203 and Si02), activated clay, Cr203, P203, Ti02, A1203-xCr203. A1203-CoO, A1203-MnO, Cr203-Fe203, MoS, MoS2, Cr03, Cr02C12, Mo03, V203, and W02C12.
As is clear from the above-specified com-pounds, the scope of the oxides and sulfides used in this invention also include those containing an alkaline metal or a halogen atom.
Preferred as the organic solid acid are sul-fonic acid group-containing polymers, which are commer-cially available, e.g. under the trade-marks Amberlist 15, Amberlite XE-284 and Nafion-H.
The isomerization reaction is carried out by bringing a cycloolefin having an endo form into contact with a solid acid catalyst. In this case, the cycloole-fin may be directly brought into contact with a solid acid catalyst, or may be brought into contact with a solid acid catalyst in the presence of an organic sol-vent.
Specific examples of the organic solvent are cyclohexane, decalin, hexane, benzene, carbon tetrachlo-ride, 1,2-dichloroethane, and the like.
The isomerization reaction is carried out advantageously at -5 to 150'C, preferably at 0 to 50'C.
The reaction time depends on a reaction temperature and a concentration of the cycloolefin. However, it is preferably 0.5 to 200 hours, more preferably 1 to 100 hours.
The reaction may be carried out by a batch method or a continuous method. The reaction according to a batch method is specifically carried out, e.g. as follows.
A reaction vessel equipped with a stirrer is charged with predetermined amounts of a cycloolefin, an 214.737 organic solvent as required, and a solid acid, and the resultant mixture is stirred at a predetermined tempera-ture for a predetermined period of time. Thereafter, the resultant reaction mixture is separated into a solid phase and a liquid phase by filtration, and further, the cycloolefin and the organic solvent in the liquid phase are separated, e.g. by distillation.
The reaction is also carried out according to the following continuous method.
(i) The same apparatus as that used in the above batch method is continuously charged with a cy-cloolefin or a cycloolefin diluted with an organic solvent to bring it into contact with a solid acid catalyst present in the apparatus, and the cycloolefin or the cycloolefin diluted with an organic solvent is continuously withdrawn, or (ii) a cycloolefin or a cycloolefin diluted with an organic solvent is charged into one end of a column packed with a.solid acid catalyst, and continu-ously withdrawn from the other end.
In both of the above methods (i) and (ii), a distillation method is usable to separate the cycloole-fin from the organic solvent after the cycloolefin is brought into contact with a solid acid catalyst.
According to the above isomerization process of this invention, a cycloolefin can be converted from an endo form to an exo form. The structures of the endo form and the exo form and the molar ratio of the endo and exo forms in an isomer mixture can be determined by measuring lII-NMR or 13C-NMR.
According to this invention, there is further provided a process for the production of an isomer mixture rich with an exo-form cycloolefin, which com-prises sub,)ecting an isomer mixture rich with an endo-form cycloolefin of the formula (I) (including the formulae (I-A) and (I-B)) to an isomerization reaction in the presence of a solid acid catalyst by using the 21 ~.7 ~ ~.'~
above isomerization process.
In the above process, the isomer mixture rich with an endo-form cycloolefin preferably comprises, based on the total of endo-form and exo-form cycloole-fins, at least 85 mol%, preferably at least 90 mol%, particularly preferably at least 94 mol% of an endo-form cycloolefin and up to 15 mol%, preferably up to 10 mol%, particularly preferably up to 6 mol% of an exo-form cycloolefin. Further, the resultant isomer mixture rich with the exo-form preferably comprises, based on the total of endo-form and exo-form cycloolefins, up to 80 mol% of an endo-form cycloolefin and at least 20 mol% of an exo-form cycloolefin. More preferably, the isomer mixture comprises 70 to 5 mol% of an endo-form cycloole-fin and 30 to 95 mol% of an exo-form cycloolefin.
The above isomer mixture rich with an endo-form cycloolefin (starting material) can be easily prepared from the foregoing starting substance by a Diels-Alder reaction, whereas the isomer mixture rich with an exo-form cycloolefin can be provided according to the above process of this invention for the first time.
Therefore, according to this invention, there is further provided an isomer mixture of a cycloolefin of the formula (I) (including (I-A) and (I-B)), i.e. an isomer mixture comprising up to 80 mol% of an endo-form cycloolefin and at least 20 mol% of an exo-form cy-cloolefin, preferably, an isomer mixture comprising 70 to 5 mol% of an endo-form cycloolefin and 30 to 95 mol%
of an exo-form cycloolefin.
When the isomer mixture of this invention is copolymerized with ethylene, it gives a novel random copolymer having excellent heat resistance and mechani-cal strength.
The novel random copolymer of this invention has the following features:
(1) It is a random copolymer of an isomer mixture 214' 3 4'~
of up to 80 mol% of an endo-form cycloolefin of the formula (I) (including the formulae (I-A) and (I-B)) and at least 20 mol% of an exo-form cycloolefin thereof and ethylene.
(2) It comprises, based on the total of polymer units derived from the cycloolefin and polymer units derived from ethylene, 10 to 90 mol% of the polymer units derived from the cycloolefin and 90 to 10 mol% of the polymer units derived from ethylene.
(3) The polymer units derived from the cycloolefin are represented by the following formula (II) R1 R2 R7 R8 R11 R12 R1? (II) w R18 R4 R5 Rs~ R10 ~ R14 n 'm wherein R1 to R18, n and m are as defined as above.
(4) It has an intrinsic viscosity [n], meas-ured in decalin at 135'C, of 0.05 to 10 dl/g.
In the above random copolymer, when a cy-cloolefin of the formula (I-A) is used as an olefin of the formula (I), the polymer unit of the formula (II) is represented by the following formula (II-A) R8 R1 R12 R17 (II-A) ~ R18 wherein R7 to R18 are as defined above.
214.' ~ 4'7 And, when a cycloolefin of the formula (I-B) is similarly used, the polymer unit of the formula (II) is represented by the following formula (II-B).
R1? (II-B) wherein R1 to R10 and R15 to R18 are as de-fined above.
According to this invention, the above random copolymer can be produced by copolymerizing the above isomer mixture and ethylene in a hydrocarbon solvent or without any hydrocarbon solvent in the presence of a catalyst which is composed of a vanadium compound and an organoaluminum and soluble in the hydrocarbon solvent or a cycloolefin of the isomer mixture'.
Such a random-copolymer and the process for the production thereof will be explained in detail below.
In the production of the cycloolefin random copolymer, the copolymerization reaction between ethyl-ene and the cycloolefin is carried out in a hydrocarbon solvent or without any hydrocarbon solvent. Examples of the hydrocarbon solvent are aliphatic hydrocarbons such as hexane, heptane, octane and kerosine; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane;
and aromatic hydrocarbons such as benzene, toluene and xylene. These solvents may be used alone or in combina-tion.
The vanadium compound is specifically a com-pound of the general formula VO(OR)aXb or V(OR)cXd wherein R represents a hydrocarbon group, X represents a halogen atom, a and b are defined by Osa53, Osbs3, ..~ 214.'~34~
and 2sa+bs3, and c and d are defined by Oscs4, Osds4, and 3sc+ds4, or an adduct of this compound with an electron donor.
Specific examples of the vanadium compounds are VOC13, VO(OCZHS)C12, VO(OCZHS)2C1, VO(0-iso-C3H7)C12, VO(0-n-C4H9)C12, VO(OC2H5)3, VOBr2, VC14, VOC12, VO(0-n-C4II9)3 and VC13.2(C08H170H).
Further, examples of the electron donor which may be used to prepare the soluble vanadium catalyst component are oxygen-containing electron donors such as an alcohol, phenols, a ketone, an aldehyde, a carboxylic acid, an ester of an organic or inorganic acid, an ether, an acid amide, an anhydride and an alkoxysilane;
and nitrogen-containing electron donors such as ammonia, an amine, a nitrile, and isocyanate. Specific examples of the electron donors are alcohols having 1 to 18 carbon atoms such as methanol, ethanol, propanol, penta-nol, hexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol and isopropylbenzyl alcohol; phenols having 6 to 20 carbon atoms, (which may have a lower alkyl group as a substituent), such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol and naphthol; ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone; aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, ben-zaldehyde, tolualdehyde and naphthaldehyde; organic acid esters having 2 to 30 carbons atoms such as methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacry-late, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl -- 214-7.3 ~'~
-~8-benzoate, benzyl benzoate, methyl toluylate, ethyl toluylate, amyl toluylate, ethyl ethylbenzoate, methyl anisate, n-butyl maleate, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl ester of Nadic acid, diisopropyl tetrahydrophthalate, diethyl r phthalate, diisobutyl phthalate, di-n-butyl phthalate, di-2-ethylhexyl phthalate, y - butyrolactone, 8-valero-lactone, coumarin, phthalide and ethylene carbonate;
acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride and anisic acid chloride; ethers having 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether; acid amides such as acetic amide, benzo-is amide and toluic amide; amines such as methyamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline and tetra-methylenediamine; nitriles such as acetonitrile, benzo-nitrile and tolunitrile; and alkoxysilanes such as ethyl silicate and diphenylmethoxysilane. These electron donors may be used in combination.
The organoaluminum compound as a component of the catalyst is a compound having at least one A1-carbon bond in the molecule. Examples of the organoaluminum compound are as follows.
(i) organoaluminum compounds of the general formula RlmAl(OR2)nHpXq wherein R1 and R2, same or different, each independently represent a hydrocarbon group having usually 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents halogen, and m, n, p and q are defined by Osms3, Osn<3, Osp<3, Osq<3 and m+n+p+q=3, and 214'~~47 (ii) complex ion alkyl compounds, formed from a metal belonging to the group 1 of the periodic table and aluminum, of the general formula wherein M1 is Li, Na or K, and R1 has the same meaning as above.
Examples of the organoaluminum compounds (i) are as follows.
Compounds of the formula RlmA1(OR2)3-m wherein R1 and R2 have the same meanings as above, and m is defined preferably by l.5sm<3.
Compounds of the formula RlmAlX3_m wherein R1 has the same meaning as above, X
represents halogen, and m is defined preferably by 0<m<3.
Compounds of the formula RlmAlfI3_m wherein R1 has the same meaning as above, and m is defined preferably by 2sm<3.
Compounds of the formula RlmA1(OR2)nXq wherein R1 and RZ have the same meaning as above, X represents halogen, and m, n and q are defined by 0<ms3, Osn<3, Osq<3 and m+n+q=3.
Specific examples of the organoaluminum com-pounds (i) are trialkylaluminum such as triethylaluminum and tributylaluminum; trialkenyl aluminum such as trii-sopropenylaluminum; dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide;
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partially alkoxylated alkylaluminum having an average composition of the formula R12.5A1(OR2)0.5 and alkylalu-minum sesquialkoxides such as ethylaluminum sesquietox-ide and butylaluminum sesquibutoxie; dialkylaluminum halides such as diethylaluminum chloride, dibutylalumi-num chloride and diethylaluminum bromide; alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesqui-bromide; partially halogenated alkylaluminum such as ethylaluminum dichloride, propylaluminum dichloride, and butylaluminum dibromide; partially hydrogenated alkyla-luminum such as dialkylaluminum hydrides, e.g. diethyla-luminum hydride and dibutylaluminum hydride and alkyla-luminum dihydrides, e.g. ethylaluminum dihydride and propylaluminum dihydrides; and partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxy-chloride, butylaluminum butoxychloride and ethylaluminum etoxybromide. Further, organoaluminum compounds which are similar to the compounds (i), e.g. organoaluminum compounds in which at least two aluminum atoms are bonded to each other through an oxygen or nitrogen atom are also usable. Specific examples of such compounds are (C2II5)2A10A1(C2II5)2, (C4I19)2A10A1(C4II9)2, and (C2II5)2A1NA1(C2II5)2~
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Examples of the organoaluminum compounds (ii) are LiAl(C2H5)4 and LiAl(C7Iil5)4~ Of these compounds, alkylaluminum halides and alkylaluminum dihalides or mixtures of these are preferred.
When the cycloolefinic random copolymer is Produced, it is preferable to carry out a copolymeriza-tion reaction of ethylene with a cycloolefin by a con-tinuous method. And, in this case, the concentration of the soluble vanadium compound to be fed in the polymeri-zation reaction system is usually not more than 10 times, preferably 1 to 7 times, more preferably 1 to 5 times as High as the concentration of the soluble vana-214.734.'1 dium compound in the polymerization reaction system.
The ratio of aluminum atoms to vanadium atoms (A1/V) in the polymerization reaction system is not less than 2, preferably 2 to 50, particularly preferably 3 to 20.
The soluble vanadium compound and the organoa-luminum compound are usually charged to the reaction system after they are respectively diluted with the above-specified hydrocarbon solvent or cycloolefin.
And, the soluble vanadium compound is preferably diluted to the above concentration before it is charged, and the organoaluminum compound is also diluted to a concentra-tion in the range of, e.g. not more than 50 times as high as the concentration thereof in the polymerization reaction system, and then charged to the polymerization reaction system.
When the cycloolefinic random copolymer is produced, the concentration, as a vanadium atom, of the soluble vanadium compound in the copolymerization system is usually 0.01 to 5 gram-atom/1, preferably 0.05 to 3 gram-atom/1.
The copolymerization reaction of ethylene with a cycloolefin is carried out at a temperature between -50' C and 100' C, preferably between -30' C and 80' C, more preferably between -20'C and 60'C.
The reaction time for the above copolymeriza-tion reaction (or an average residence time of a poly-merization reaction mixture in the case of a continuous polymerization) differs depending upon polymerization materials, concentration of catalyst components and temperatures. The reaction time is usually 5 minutes to 5 hours, preferably 10 minutes to 3 hours. The pressure for the copolymerization reaction is usually more than 0 and up to 50 kg/cm2, preferably more than 0 and up to 20 kg/cm2~
When the cycloolefin random copolymer is produced, the molar ratio of ethylene and cycloolefin 214"~~4~
to be fed is usually 90/10 to 10/90, preferably 85/15 to 40/60. The ethylene unit/cycloolefin unit constitution-al ratio in the resulting ethylene/cycloolefin copolymer is usually 90/10 to 40/60, preferably 85/15 to 50/50.
The above cycloolefinic random copolymer may contain other copolymerizable monomers, e.g. norbornenes other than the cycloolefin of the formula (I) or a-olefins other than ethylene in such an amount that does not impair the object of this invention or not more than 15 mol% based on the total polymer units.
The above copolymerization reaction of ethyl-ene with a cycloolefin gives a solution of a cycloolefin random copolymer in the hydrocarbon solvent or a solu-tion thereof in an unreacted cycloolefin. The concen-tration of the cycloolefinic random copolymer in such a solution is usually 2.0 to 200 g/lZ (g-polymer/.-polymer-ization liquid), preferably 40 to 100 g/~Q. The solution also contains the soluble vanadium compound component and the organoaluminum compound components of the cata-lyst.
The above solution of the cycloolefin random copolymer is usually subjected to a series of treatments starting with deashing and finishing with pelleting, whereby pellets of the cycloolefin random copolymer are obtained.
In the above cycloolefin random copolymer, the structural unit derived from the cycloolefin of the formula (I) is present in a structure shown in the following formula (II) ~ 14'~ 3 4'~
R3 ~ R9 ~ R13 R1~R2 ~I R7~,R8 ~R11,~R12~ R17 ( II ) R4 R5 R6~ R10 ~ R14 n ~ 'm wherein R1 to R18, n and m are as defined as above.
The above ethylene-cycloolefin random copoly-mer preferably has an intrinsic viscosity [r~), measured in decalin at 135'C, of 0.05 to 10 dl/g.
The above random copolymer produced from the isomer mixture of this invention has a high glass tran-sition point (Tg) or superior heat resistance and a high flexural modulus (FM) or superior mechanical strength as compared with any conventional cycloolefin random copol-ymer obtained by copolymerization of ethylene with an isomer mixture containing 85 mol% or more, 90 mol% or more, in many cases, or 94 mol% or more, further in many cases, of an endo-form cycloolefin of the formula (I) (naturally when the comparison is made on the same composition of ethylene and a cycloolefin). Therefore, when the isomer mixture according to this invention is used, it is possible to reduce the amount of expensive tetracyclododecenes and obtain a copolymer having an identical glass transition point (Tg) or a flexural modulus to that of any conventional copolymer.
This invention will be explained below by reference to Examples, which however shall not limit this invention.
Quantitative determination method (a) The endo-form cycloolefin/exo-form cy-cloolefin molar ratio of an isomer mixture of tetracy-clo[4,4,0,12'5,17,10)-3-dodecene (to be abbreviated as 21473~'~
TCD-3 hereinafter) was calculated as follows. TCD-3 was subjected to lII-NMR (in CDC13, room temperature, TMS
standard), and an integration strength ratio of olefin proton absorption peaks in the resultant spectrum was used as a basis for the calculation. Table 1 shows chemical shifts of olefin protons obtained by measure-ment of 1H-NMR of tetracyclo-[4,4,0,12'5,17.10]-3_dode-cene.
Table 1 also shows chemical shifts of carbons obtained by measurement of 13C-NMR of tetracyclo-[4,4,0,12~5,17,10~_g_dodecene.
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(b) The endo-form cycloolefin/exo-form cy-cloolefin molar ratio of an isomer mixture of pentacy-clo[4,7,0,12~5,10~12~08,3-3~-3-pentadecene (to be abbrevi-ated as PCPD hereinafter) was calculated similarly as follows. PCPD was sub,)ected to 1II-NMR (in CDC13, room temperature, TMS standard), and an integration strength spectrum was used as a basis for the calculation. Table 3 shows chemical shifts of olefin protons obtained by measurement of lII-NMR of PCPD.
Table 3 also shows chemical shifts of carbons obtained by measurement of 13C-NMR of PCPD. scs Table 4 shows chemical shifts of carbons obtained by measurement of 13C-NMR of an ethylene-PCPD
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Method of measurement of softening temperature Copolymers prepared in Polymerization Examples and Comparative Polymerization Examples were respective-1_y molded into sheet samples, and thermal deformation behavior tiuereof was measured by using a thermomechani-cal analyzer supplied by du Pont. That is, the soften-ing temperature is a temperature at which a quartz penetrat;or penetrated tl~e sample 0.635 mm deep under a load of 49 g at a temperature elevatlon rate of 5'C/mlnute (the softening temperature is referred to as TMA softening temperature hereinafter).
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Method of measurement of intrinsic viscosity Measurement was made in decaline at 135'C.
REC'ERENTIAL EXAMPLE 1 Norbornene and cyclopentadiene were sub,~ected to a Diels-Alder reaction according to a method de-scribed In Japanese Patent Publication No. 14910/1971 to synthesize tetracyclo[4,4,0,12~5,17~10]_g-dodecene (~).
The resultant tetracyclododecene-3 had 94.9 mol% of an endo form and 5.1 mol % of an exo form.
Table 5 shows the results.
RErERCNTIAL EXAMPLE 2 5-Ethyl-2-norbornene and cyclopentadiene were sub,~ected to a Diels-Alder reaction in the same way as in Referential Example 1 to synthesize 8-ethyl-tetracy-cto[4,4,0,12'5,17~10]_g-dodexene (~ ).
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The resultant 8-ethyl-tetracyclo-(4,4,0,12~5,17.10~-g_dodecene was measured by sub,)ecting it to lII-NMR to obtain an endo-form cycloole-fin/exo-form cycloolefin molar ratio. This compound had 97.3 mol% of an endo-form cyclooefin and 2.7 mol% of an exo-form cycloolefin.
Table 5 shows the results.
A 30-liter reaction vessel equipped with stirrer and a reflux condenser was charged with 1 liter of the tetracyclo-[4,4,0,12'5,17.10]-3_dodecene (TCD-3) obtained in Referential Example 1 and 17 liters of cyclohexane, and the mixture was stirred. Twelve kilo-grams of zeolite (Zeolam F-9, trade name, a product of Tosoh Corporation, spherical forms, 1.8 to 2.4 mm~5, Na20.A1203.2.5Si02) was added to the resultant solution, and the mixture was stirred at room temperature for 6 hours to carry out an isomerization reaction from an endo-form cyclooefin to an exo-form cycloolefin.
After the reaction, the reaction mixture was filtered to separate the catalyst, and the resultant solution of TCD-3 in cyclohexane was distilled under a reduced pressure (50 mmHg) to give isomerized TCD-3.
Analysis of the TCD-3 by lII-NMR showed an endo-form cyclolefin/exo-form cycloolefin molar ratio of 44.2/55.8.
Table 5 shows the results.
Example 1 was repeated except that the reac-tion time was changed to 3 hours.
Table 5 shows the results.
Example 1 was repeated except that the cata-lyst was changed to silica-alumia (Sekado OW, a product of Shinagawa Refractories Co., Ltd., particulate, 0.5 to 2 mm~6, A1203.mSi02.nH20+A1(OII)3), that the amounts of the catalyst and cyclohexane were changed to 4.0 liters 21 ~.'~ 3 4'~
and 3 kg, respectively, and that the reaction time was changed to 96 hours.
Table 5 shows the results.
Example 1 was repeated except that the 8-ethyl-tetracyclo[4,4,0,12'5,17.10]-3-dodecene (8E-TCD-3 in short) obtained in Referential Example 2 was used.
Table 5 shows the results.
Example 4 was repeated except that the reac-tion time was changed to 3 hours.
Table 5 shows the results.
Example 4 was repeated except that the same silica-alumina as that used in Example 3 was used and that the reaction time was changed to 96 hours.
Table 5 shows the results.
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Separately, a reaction mixture was continuously with-drawn from the polymerizes bottom such that the'total amount of a polymerization liquid in the polymerizes was 1 liter and that the residence time thereof was 0.5 hours.
The above polymerization reaction was carried out at 10'C by circulating a refrigerant through a cooling ,packet externally provided to the polymerizes.
Under the above copolymerization reaction conditions, a polymerization reaction mixture containing an ethylene-TCD-3 random copolymer was obtained. The polymerization reaction was stopped by adding a small amount of isopropyl alcohol to the polymerization liquid withdrawn from the polymerizes bottom. Then, the poly-merization was charged into a mixer while the mixer containing acetone whose amount was about three times as large as the polymerization liquid was operated, whereby the copolymer was precipitated. The precipitated copol-ymer was recovered from the solution by filtration. The resultant copolymer was dispersed in acetone such that the concentration thereof was about 50 g/1, and the resultant mixture was further heat-treated at a boiling point of acetone. Thereafter, the copolymer was sepa-rated from the acetone by filtration, and dried under reduced pressure at 120'C for 24 hours.
The resultant ethylene-TCD-3 copolymer was 2147~4~' subjected to 13C-NMR to show that it had an ethylene content of 60.7 mol%. And, it had an intrinsic viscosi-ty [r~] of 0.37 dl/g and a TMA softening temperature of 18 0' C .
Table 6 shows the results. Further, Fig. 1 shows the relationship between a tetracyclododecene-3 content (mol%) in the ethylene-tetracyclododecene-3 copolymer obtained as above and a softening temperature thereof. And, Fig. 2 shows the relationship between a tetracyclododecene content (mol%) of the copolymer above and flexural modulus thereof.
The above copolymer was also subjected to 13C_NMR to show that it had an endo form cycloolefin/exo form cycloolefin molar ratio of 41/59, and this value hardly changed from that obtained before the polymeriza-tion.
EXAMPLES 8-14 (Polymerization Examples 2-8) and COMPARATIVE EXAMPLES 1 and 2 (Comparative Polymerization Examples 1 and 2) Copolymerization of ethylene and tetracyclo-dodecene was carried out in the same way as in Polymers-zation Example 1 by using materials (tetracyclododecene) shown in Table 6 under the conditions specified in Table 6.
Table 6 shows the results.
And, Fig. 1 shows the relationship between a tetracyclododecene-3 content (mol%) in the ethylene-tetracyclododecene-3 copolymer obtained as above and a softening temperature thereof. And, Fig. 2 shows the relationship between a tetracyclododecene content (mol%) of the copolymer above and flexural modulus thereof.
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EXAMPLES 15-17 (Polymerization Examples 9-11) and COMPARATIVE EXAMPLE 3 (Comparative Polymerization Example 3) Copolymerization of ethylene with 8-ethyl-tetracyclododecene-3 was carried out in the same way as in Example 7 by using materials (8-ethyl-tetracyclodode-cene-3) shown in Table 7.
Table 7 shows the results.
Table 7 shows that the copolymers obtained in Examples 15-17, using 8-ethyl-tetracyclododecene-3 having a large content of an exo form, are improved both in TMA softening temperature and flexural modulus as compared with the copolymer obtained in Comparative Example 3.
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FIELD 01: TIIE INVENTION
This invention relates to isomerization of a cycloolefin such as tetracyclododecene or pentacyclopen-tadecene from an endo form to an exo form and to copolymerization of a cycloolefin and ethylene.
The present applicant found that cycloolefin random copolymers obtained by copolymerization of ethyl-ene and tetracyclododecenes are synthetic resins having excellent transparency and well-balanced properties among heat resistance, thermal wing resistance, chemi-cal resistance, solvent resistance, dielectric proper-ties, mechanical properties and that such cycloolefin random copolymers exhibit excellent performance in a field of optical materials such as optical memory disks and fibers. Therefore, the present applicant already proposed such random copolymers in Japanese Laid-Open Patent Publications Nos. 168708/1985, 98780/1986, 115912/1986, 115916/1986, 120816/1986, and 252407/1987.
Tetracyclododecenes used for production of 2p such random copolymers are prepared by a Diels-Alder reaction between corrresponding norbornenes and cyclo-pentadienes.
In this Diels-Alder reaction, cis addition dominantly proceeds. for example, in a reaction between cyclopentadiene (a) and norbornene (b), tetracyclodode-cene having an endo form (c) is mainly formed as shown in the following reaction formula.
(a) (b) (c) 214' 3 4'~
,_... - 2 - 73997-2D
And tetracyclododecene having an exo ~orm (d) of the following formula is hardly formed.
,a, It is also known that cycloolefin random copolymers produced by copolymerizing tetracyclodode-Genes mainly having an endo form prepared by the above Diels-Alder reaction with ethylene exhibit excellent heat resistance and mechanical strength.
International Laid-Open Publication No.
W089/01950 describes that cycloolefin random copolymers obtained by copolymerization of ethylene with pentacy-clopentadecenes (cycloolefins) have excellent transpar-ency and are excellent not only in optical properties such as optical uniformity and small birefringence but also in other properties such as heat resistance, chemi-cal resistance, dimensional stability and mechanical properties.
Pentacyclopentadecenes used as a cycloolefin for production of such random copolymers are also pre-pared by a Diels-Alder reaction between corresponding dihydrodicyclopentadienes (partially hydrogenated products of dicyclopentadienes) and cyclopentadienes.
For example, in a reaction between eyclopenta-diene (a) and dihydrodicyclopentadiene (e), pentacyclo pentadecene having an endo form (f) is mainly formed as shown in the following reaction formula in the same manner as the preparation of tetracyclododecene.
(a) (e) (f ) And, pentacyclopentadecene having an exo form of the following formula (g) is hardly formed.
H
H H (g) I
The present applicant has made a diligent study to further improve heat resistance and mechanical strength of the above random copolymer of a cycloolefin and ethylene, and found the following. That is, when an isomer mixture containing a larger amount of a cycloole-fin having an exo form (sometimes called "exo-form cycloolefin" hereinbelow) is used as a cycloolefin, the resultant random copolymer has remarkably improved heat resistance and mechanical strength. And, the present applicant has found an industrially advantageous process for isomerization for the production of such an isomer mixture containing a large amount of an exo form cy-cloolefin.
SUMMARY OF THE INVENTION
A first aspect of this invention provides a process for the isomerization of a cycloolefin from an endo form to an exo form which comprises isomerizing an endo-form cycloolefin of the following formula (I) _R16 R R2 R7 R8 R11 R1 R17 (I) \ R18 R4 R5 a6l R10 I R14 n m (wherein Rl to Rl4 are independently a hydrogen atom, a halogen atom or a hydrocarbon group, R15 to R18 are independently a hydrogen atom, a halogen atom or a hydrocarbon group, or R15 or R16 and R17 or R18 may be bonded to each other to form a monocyclic or polycyclic group, or R15 and R16 or Rl7 and R18 may together form an alkylidene group, n is 0 or 1, and m is 0 or a positive integer, preferably 0, 1 or 2, provided 2~4'~3~.~
that m and n cannot be simultaneously zero), in the presence of a solid acid catalyst to convert its endo form into the corresponding exo form.
BRIEF DESCRIPTION OF DRAWINGS
Fig. 1 shows a relationship between a content (mol%) of tetracyclododecene-3 in each of ethylene-tetracyclododecene-3 copolymers obtained by copolymeri-zation of ethylene with each of four tetracyclodode-cene-3 isomer mixtures having a different endo-form cycloolefin/exo-form cycloolefin ratio and a TMA soften-ing temperature of each of the copolymers.
Fig. 2 shows a relationship between a content (mol%) of tetracyclododecene in the above ethylene/tetracyclododecene-3 copolymers and flexural modulus thereof.
DETAILED DESCRIPTION OF TIIE INVENTION
The starting material used in this invention is a cycloolefin having an endo form, and represented by the foregoing formula (I).
In the formula (I), each of R1 to R14, inde-pendently from each other, is a hydrogen atom, a halogen atom or a hydrocarbon group. Preferred examples oP the halogen atom are fluorine, chlorine and bromine. Pre-ferred examples of the hydrocarbon group are lower alkyl groups such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl and tert-butyl groups.
Further, in the formula (I), each of R15 to R18, independently from each other, is a hydrogen atom, a halogen atom or a hydrocarbon group. Examples of the halogen atom are as specified above. Preferred examples of the hydrocarbon group are alkyl groups such as methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, hexyl and stearyl groups, and cycloalkyl groups such as a cyclohexyl group.
R15 or R16 and R17 or R18 may be bonded to each other to form a monocyclic or polycyclic group, or R15 and R16 or, Rl7and R18 may form an alkylidene group together. As the monocyclic or polycyclic group, R15 or R16 and R17 or R18 may form, e.g. a cyclopentyl group, cyclopentenyl group, cyclohexyl group or the like to-gether with carbon atoms to which R15, R16~ R17 and R18 are bonded. And, preferred examples of the above alky-lidene group are ethylidene, propylidene, and isopropy-lidene groups.
The "n" is 0 or 1, and the "m" is 0 or a positive integer, provided that n and m cannot be zero at the same time.
In the above formula (I), when n is 0 and m is 1, the above formula (I) is represented by the following formula (I-A) .
R17 (I_A) wherein R7 to R18 are as defined in the above formula (I).
And, when n is 1 and m is 0, the above formula (I) is represented by the following formula (I-B) R17 (I-B) wherein R1 to R10 and R15 to R18 are as de-fined in the above formula (I).
Specific examples of the cycloolefin of the formula (I) (including the above formulae (I-A) and -- 214734?' (I-B)) are preferably as follows:
211 Tetracyclo[4,4,0,12~5,17,10~_3_dodecene (41 ~ 8), 8-methyltetracyclo(4,4,0,12~5,17,10~-3-dodecene, 8-methyl-tetracyclo[4,4,0,12~5,17,10~-3_ dodecene, 8-ethyltetracyclo[4,4,0,12~5,17,10~_3-dodecene, 8-propyltetracyclo(4,4,0,12~5,17,10~_3_ dodecene, 8-hexyltetracyclo[4,4,0,12~5,17,10~_3_ dodecene, 8-stearyltetracyclo[4,4,0,12~5,17,10~-3-dodecene, 8,9-dimethyltetracyclo[4,4,0,12~5,17,10~_ 3-dodecene, 8-methyl-9-ethyltetracyclo[4,4,0,12~5,17,10~_ 3-dodecene, 8-chlorotetracyclo[4,4,0,12~5,1~,10~-3-dodecene, 8-bromotetracyclo[4,4,0,12~5,17,10~-3-dodecene, 8-fluorotetracyclo[4,4,0,12~5,17,10~_3-dodecene, 8,9-dichlorotetracyclo[4,4,0,12~5,17,10~_ 3-dodecene, 8-cyclohexyltetracyclo(4,4,0,12~5,17,10~_ 3-dodecene, 8-isobutyltetracyclo[4,4,0,12~5,17,10~_3-dodecene, 8-butyltetracyclo[4,4,0,12~5,17,10~-3-dodecene, 8-ethylidenetetracyclo[4,4,0,12~5,17,10~_ 3-dodecene, 8-ethylidene-9-methyltetracyclo-214'734 _8_ [4,4,0,12~5,17,10)_3_dodecene, 8-ethylidene-9-ethyltetracyclo-[4,4,0,12~5,17,10]_3_dodecene, 8-ethylidene-9-isopropyl-tetracyclo-[4,4,0,12~5,17,10~-3_dodecene, 8-ethylidene-9-butyl-tetracyclo-[4,4,0,12~5,17.10~_g_dodecene, 8-n-propylidene-tetracyclo[4,4,0,12~5,17.10~_ 3-dodecene, 8-n-propylidene-9-methyltetracyclo-[4,4,0,12~5,17,10]_3_dodecene, 8-n-propylidene-9-ethyltetracyclo-[4,4,0,12~5,17,10]-3_dodecene, 8-n-propylidene-9-isopropyltetracyclo-[4,4,0,12 5,17,10]-3_dodecene, 8-n-propylidene-9-butyltetracyclo-[4,4,0,12~5,17,10~-3_dodecene, 8-isopropylidenetetracyclo[4,4,0,12~5,17.10~-3-dodecene, 8-isopropylidene-9-methyltetracyclo-[4,4,0,12~5,17,10~_3_dodecene, 8-isopropylidene-9-ethyltetracyclo-[4,4,0,12~5,17,10~_3_dodecene, 8-isopropylidene-9-isopropyltetracyclo-[4,4,0,12'5,17,10]_3_dodecene, 8-isopropylidene-9-butyltetracyclo-[4,4,0,12~5,17,10]_3_dodecene, 5,10-dimethyltetracyclo[4,4,0,12~5,17,10~_ 3-dodecene, 2,10-dimethyltetracyclo[4,4,0,12~5,17.10~_ 3-dodecene, 11,12-dimethyletracyclo[4,4,0,12~5,17.10~-3_ dodecene, 2,7,9-trimethyltetracyclo[4,4,0,12~5,17,10~-3-dodecene, 9-ethyl-2,7-dimethyltetracyclo-[4,4,0,12~5,17,10]-3-dodecene, 21 ~.'~~ 4'~
9-isobutyl-2,7-dimethyltetracyclo-[4,4,0,12~5,17,10~_g_dodecene, 9,11,12-trimethyltetracyclo-[4,4,0,12~5,17.10~_3_dodecene, 9-ethyl-11,12-dimethyltetracyclo-[4,4,0,12~5,17'10]_3_dodecene, 9-isobutyl-11,12-dimethyltetracyclo-[4,4,0,12'5,17,10]_3_dodecene, 5,8,9,10-tetramethyltetracyclo-[4.4,0,12~5,17.10~_3_dodecene;
pentacyclo[6,5,1,13~6,02.7~09,13~_ 4-pentadecene (51 ), 1,3-dimethyl-pentacyclo[6,5,1,13~6,p2.7~09,13~_ 4-pentadecene, 1,6-dimethyl-pemtacyclo[6,5,1,13~6,02,7,09,13~_ 4-pentadecene, 14,15-dimethyl-pentacyclo[6,5,1,13~6,02,7~09,13~_ 4-pentadecene, pentacyclo[6,6,1,13~6,p2,7~09,13~_4_pentadecene;
1,3-dimethyl-pentacyclo[6,6,1,13~6,02.7,09,14~_ 3CH~C1~3 3 4-hexadecene (4 ~ ~~~ ~12) , 1,6-dimethyl-pentacyclo[6,6,1,13~6,p2.7~09,14~-4-hexadecene, 15,16-dimethyl-pentacyclo[6,6,1,13~6,02,7~09,14~_ 4-hexadecene;
pentacyclo[6,5,1,13'6,02,7,09.13~penta-decadiene-4,10 ( 51 ,11 ) ' pentacyclo[4,7,0,12~5,19,12~08,13~_3-peritadeCene (3 ~ 2 1 13 X211 ) methyl-substituted pentacyclo--- 2~47~47 [4,7,0,12'5,19,12~08,13~_3_pentadecene, dimethyl-substituted pentacyclo-[4,7,0,125,19,12~08,13~_3_pentadecene, trimethyl-substituted pentacyclo-[4,7,0,12'5,19,12,08,13~_3_pentadecene;
heptacyclo-[7,8,0,13~6,110,17~112,15~01,9~
02,7~011,16~_4_eicosene( ~ 13 3 2 1 l~j trimethyl-substituted heptacyclo-[7,8,0,13'6,110,17~112,15~01,9~02,7~011,16~_ 4-eicosene, tetramethyl-substituted heptacyclo-(7,8,0,136,110,17~112,15~01,9~02,7~011,16~_ 4-eicosene, methyl-substituted heptacyclo-[7,8,0,13'6,110,17~112,15~01,9~02,7~011,16~_ 4-eicosene, dimethyl-substituted heptacyclo-[7,8,0,13'6,110,17~112,15~01,9~02,7~011,16~_ 4-eicosene; and nonacyclo[9,10,1,14~7,113,20~115,18~02,10~
03,8,012.21~014,19~_5_pentacosene 9 0 11 131 .LS
( 51 7 ) .
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The endo form of a cycloolefin, when it is, e.g. tetracyclo[4,4,0,12~5,17,10~_3_dodecene, is repre-sented by the following formula (c) as described above.
(c) And, the end form of a cycloolefin, when it is, e.g.
pentacyclo-[4,7,0,12'5,08,13~19,12~_3_pentadecene, is 214734?
-~~-represented by the following formula (f) as described above.
(f) The stereostructure of the endo form of a cycloolefin is believed to be clear on the basis of the above-specified formulae.
In the process of this invention, the above-described cycloolefins having an endo form are converted into cycloolefins having the corresponding exo form by isomerization in the presence of a solid acid catalyst.
The stereostructure of the exo form cycloole-fin is believed to be clear on the basis of the follow-ing formulae. That is, for example, the exo form corre-sponding to the endo form of the formula (c) is reprent-ed by the following formula (d), and the exo form corresponding to the endo form of the formula (f) is represented by the following formula (g).
(g) In the process of this invention, preferred as a solid acid catalyst are oxides or sulfides of metals belonging to the groups 3 to 8 of the periodic table or organic solid acids. Preferred examples of the oxides and sulfides are those of A1, Si, P, Ti, V, Cr, Mo, W, 214.'x.3 4?
Mn, Fe or Co. Specific examples of such oxides and sulfides are silica-alumia (composed mainly of A1203 and Si02), alumina (composed mainly of A1203), zeolite (composed mainly of Na20, A1203 and Si02), activated clay, Cr203, P203, Ti02, A1203-xCr203. A1203-CoO, A1203-MnO, Cr203-Fe203, MoS, MoS2, Cr03, Cr02C12, Mo03, V203, and W02C12.
As is clear from the above-specified com-pounds, the scope of the oxides and sulfides used in this invention also include those containing an alkaline metal or a halogen atom.
Preferred as the organic solid acid are sul-fonic acid group-containing polymers, which are commer-cially available, e.g. under the trade-marks Amberlist 15, Amberlite XE-284 and Nafion-H.
The isomerization reaction is carried out by bringing a cycloolefin having an endo form into contact with a solid acid catalyst. In this case, the cycloole-fin may be directly brought into contact with a solid acid catalyst, or may be brought into contact with a solid acid catalyst in the presence of an organic sol-vent.
Specific examples of the organic solvent are cyclohexane, decalin, hexane, benzene, carbon tetrachlo-ride, 1,2-dichloroethane, and the like.
The isomerization reaction is carried out advantageously at -5 to 150'C, preferably at 0 to 50'C.
The reaction time depends on a reaction temperature and a concentration of the cycloolefin. However, it is preferably 0.5 to 200 hours, more preferably 1 to 100 hours.
The reaction may be carried out by a batch method or a continuous method. The reaction according to a batch method is specifically carried out, e.g. as follows.
A reaction vessel equipped with a stirrer is charged with predetermined amounts of a cycloolefin, an 214.737 organic solvent as required, and a solid acid, and the resultant mixture is stirred at a predetermined tempera-ture for a predetermined period of time. Thereafter, the resultant reaction mixture is separated into a solid phase and a liquid phase by filtration, and further, the cycloolefin and the organic solvent in the liquid phase are separated, e.g. by distillation.
The reaction is also carried out according to the following continuous method.
(i) The same apparatus as that used in the above batch method is continuously charged with a cy-cloolefin or a cycloolefin diluted with an organic solvent to bring it into contact with a solid acid catalyst present in the apparatus, and the cycloolefin or the cycloolefin diluted with an organic solvent is continuously withdrawn, or (ii) a cycloolefin or a cycloolefin diluted with an organic solvent is charged into one end of a column packed with a.solid acid catalyst, and continu-ously withdrawn from the other end.
In both of the above methods (i) and (ii), a distillation method is usable to separate the cycloole-fin from the organic solvent after the cycloolefin is brought into contact with a solid acid catalyst.
According to the above isomerization process of this invention, a cycloolefin can be converted from an endo form to an exo form. The structures of the endo form and the exo form and the molar ratio of the endo and exo forms in an isomer mixture can be determined by measuring lII-NMR or 13C-NMR.
According to this invention, there is further provided a process for the production of an isomer mixture rich with an exo-form cycloolefin, which com-prises sub,)ecting an isomer mixture rich with an endo-form cycloolefin of the formula (I) (including the formulae (I-A) and (I-B)) to an isomerization reaction in the presence of a solid acid catalyst by using the 21 ~.7 ~ ~.'~
above isomerization process.
In the above process, the isomer mixture rich with an endo-form cycloolefin preferably comprises, based on the total of endo-form and exo-form cycloole-fins, at least 85 mol%, preferably at least 90 mol%, particularly preferably at least 94 mol% of an endo-form cycloolefin and up to 15 mol%, preferably up to 10 mol%, particularly preferably up to 6 mol% of an exo-form cycloolefin. Further, the resultant isomer mixture rich with the exo-form preferably comprises, based on the total of endo-form and exo-form cycloolefins, up to 80 mol% of an endo-form cycloolefin and at least 20 mol% of an exo-form cycloolefin. More preferably, the isomer mixture comprises 70 to 5 mol% of an endo-form cycloole-fin and 30 to 95 mol% of an exo-form cycloolefin.
The above isomer mixture rich with an endo-form cycloolefin (starting material) can be easily prepared from the foregoing starting substance by a Diels-Alder reaction, whereas the isomer mixture rich with an exo-form cycloolefin can be provided according to the above process of this invention for the first time.
Therefore, according to this invention, there is further provided an isomer mixture of a cycloolefin of the formula (I) (including (I-A) and (I-B)), i.e. an isomer mixture comprising up to 80 mol% of an endo-form cycloolefin and at least 20 mol% of an exo-form cy-cloolefin, preferably, an isomer mixture comprising 70 to 5 mol% of an endo-form cycloolefin and 30 to 95 mol%
of an exo-form cycloolefin.
When the isomer mixture of this invention is copolymerized with ethylene, it gives a novel random copolymer having excellent heat resistance and mechani-cal strength.
The novel random copolymer of this invention has the following features:
(1) It is a random copolymer of an isomer mixture 214' 3 4'~
of up to 80 mol% of an endo-form cycloolefin of the formula (I) (including the formulae (I-A) and (I-B)) and at least 20 mol% of an exo-form cycloolefin thereof and ethylene.
(2) It comprises, based on the total of polymer units derived from the cycloolefin and polymer units derived from ethylene, 10 to 90 mol% of the polymer units derived from the cycloolefin and 90 to 10 mol% of the polymer units derived from ethylene.
(3) The polymer units derived from the cycloolefin are represented by the following formula (II) R1 R2 R7 R8 R11 R12 R1? (II) w R18 R4 R5 Rs~ R10 ~ R14 n 'm wherein R1 to R18, n and m are as defined as above.
(4) It has an intrinsic viscosity [n], meas-ured in decalin at 135'C, of 0.05 to 10 dl/g.
In the above random copolymer, when a cy-cloolefin of the formula (I-A) is used as an olefin of the formula (I), the polymer unit of the formula (II) is represented by the following formula (II-A) R8 R1 R12 R17 (II-A) ~ R18 wherein R7 to R18 are as defined above.
214.' ~ 4'7 And, when a cycloolefin of the formula (I-B) is similarly used, the polymer unit of the formula (II) is represented by the following formula (II-B).
R1? (II-B) wherein R1 to R10 and R15 to R18 are as de-fined above.
According to this invention, the above random copolymer can be produced by copolymerizing the above isomer mixture and ethylene in a hydrocarbon solvent or without any hydrocarbon solvent in the presence of a catalyst which is composed of a vanadium compound and an organoaluminum and soluble in the hydrocarbon solvent or a cycloolefin of the isomer mixture'.
Such a random-copolymer and the process for the production thereof will be explained in detail below.
In the production of the cycloolefin random copolymer, the copolymerization reaction between ethyl-ene and the cycloolefin is carried out in a hydrocarbon solvent or without any hydrocarbon solvent. Examples of the hydrocarbon solvent are aliphatic hydrocarbons such as hexane, heptane, octane and kerosine; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane;
and aromatic hydrocarbons such as benzene, toluene and xylene. These solvents may be used alone or in combina-tion.
The vanadium compound is specifically a com-pound of the general formula VO(OR)aXb or V(OR)cXd wherein R represents a hydrocarbon group, X represents a halogen atom, a and b are defined by Osa53, Osbs3, ..~ 214.'~34~
and 2sa+bs3, and c and d are defined by Oscs4, Osds4, and 3sc+ds4, or an adduct of this compound with an electron donor.
Specific examples of the vanadium compounds are VOC13, VO(OCZHS)C12, VO(OCZHS)2C1, VO(0-iso-C3H7)C12, VO(0-n-C4H9)C12, VO(OC2H5)3, VOBr2, VC14, VOC12, VO(0-n-C4II9)3 and VC13.2(C08H170H).
Further, examples of the electron donor which may be used to prepare the soluble vanadium catalyst component are oxygen-containing electron donors such as an alcohol, phenols, a ketone, an aldehyde, a carboxylic acid, an ester of an organic or inorganic acid, an ether, an acid amide, an anhydride and an alkoxysilane;
and nitrogen-containing electron donors such as ammonia, an amine, a nitrile, and isocyanate. Specific examples of the electron donors are alcohols having 1 to 18 carbon atoms such as methanol, ethanol, propanol, penta-nol, hexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol and isopropylbenzyl alcohol; phenols having 6 to 20 carbon atoms, (which may have a lower alkyl group as a substituent), such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol and naphthol; ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone; aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, ben-zaldehyde, tolualdehyde and naphthaldehyde; organic acid esters having 2 to 30 carbons atoms such as methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacry-late, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl -- 214-7.3 ~'~
-~8-benzoate, benzyl benzoate, methyl toluylate, ethyl toluylate, amyl toluylate, ethyl ethylbenzoate, methyl anisate, n-butyl maleate, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl ester of Nadic acid, diisopropyl tetrahydrophthalate, diethyl r phthalate, diisobutyl phthalate, di-n-butyl phthalate, di-2-ethylhexyl phthalate, y - butyrolactone, 8-valero-lactone, coumarin, phthalide and ethylene carbonate;
acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride and anisic acid chloride; ethers having 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether; acid amides such as acetic amide, benzo-is amide and toluic amide; amines such as methyamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline and tetra-methylenediamine; nitriles such as acetonitrile, benzo-nitrile and tolunitrile; and alkoxysilanes such as ethyl silicate and diphenylmethoxysilane. These electron donors may be used in combination.
The organoaluminum compound as a component of the catalyst is a compound having at least one A1-carbon bond in the molecule. Examples of the organoaluminum compound are as follows.
(i) organoaluminum compounds of the general formula RlmAl(OR2)nHpXq wherein R1 and R2, same or different, each independently represent a hydrocarbon group having usually 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents halogen, and m, n, p and q are defined by Osms3, Osn<3, Osp<3, Osq<3 and m+n+p+q=3, and 214'~~47 (ii) complex ion alkyl compounds, formed from a metal belonging to the group 1 of the periodic table and aluminum, of the general formula wherein M1 is Li, Na or K, and R1 has the same meaning as above.
Examples of the organoaluminum compounds (i) are as follows.
Compounds of the formula RlmA1(OR2)3-m wherein R1 and R2 have the same meanings as above, and m is defined preferably by l.5sm<3.
Compounds of the formula RlmAlX3_m wherein R1 has the same meaning as above, X
represents halogen, and m is defined preferably by 0<m<3.
Compounds of the formula RlmAlfI3_m wherein R1 has the same meaning as above, and m is defined preferably by 2sm<3.
Compounds of the formula RlmA1(OR2)nXq wherein R1 and RZ have the same meaning as above, X represents halogen, and m, n and q are defined by 0<ms3, Osn<3, Osq<3 and m+n+q=3.
Specific examples of the organoaluminum com-pounds (i) are trialkylaluminum such as triethylaluminum and tributylaluminum; trialkenyl aluminum such as trii-sopropenylaluminum; dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide;
21 ~.'~ 3 ~.'~
partially alkoxylated alkylaluminum having an average composition of the formula R12.5A1(OR2)0.5 and alkylalu-minum sesquialkoxides such as ethylaluminum sesquietox-ide and butylaluminum sesquibutoxie; dialkylaluminum halides such as diethylaluminum chloride, dibutylalumi-num chloride and diethylaluminum bromide; alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesqui-bromide; partially halogenated alkylaluminum such as ethylaluminum dichloride, propylaluminum dichloride, and butylaluminum dibromide; partially hydrogenated alkyla-luminum such as dialkylaluminum hydrides, e.g. diethyla-luminum hydride and dibutylaluminum hydride and alkyla-luminum dihydrides, e.g. ethylaluminum dihydride and propylaluminum dihydrides; and partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxy-chloride, butylaluminum butoxychloride and ethylaluminum etoxybromide. Further, organoaluminum compounds which are similar to the compounds (i), e.g. organoaluminum compounds in which at least two aluminum atoms are bonded to each other through an oxygen or nitrogen atom are also usable. Specific examples of such compounds are (C2II5)2A10A1(C2II5)2, (C4I19)2A10A1(C4II9)2, and (C2II5)2A1NA1(C2II5)2~
CsHS
Examples of the organoaluminum compounds (ii) are LiAl(C2H5)4 and LiAl(C7Iil5)4~ Of these compounds, alkylaluminum halides and alkylaluminum dihalides or mixtures of these are preferred.
When the cycloolefinic random copolymer is Produced, it is preferable to carry out a copolymeriza-tion reaction of ethylene with a cycloolefin by a con-tinuous method. And, in this case, the concentration of the soluble vanadium compound to be fed in the polymeri-zation reaction system is usually not more than 10 times, preferably 1 to 7 times, more preferably 1 to 5 times as High as the concentration of the soluble vana-214.734.'1 dium compound in the polymerization reaction system.
The ratio of aluminum atoms to vanadium atoms (A1/V) in the polymerization reaction system is not less than 2, preferably 2 to 50, particularly preferably 3 to 20.
The soluble vanadium compound and the organoa-luminum compound are usually charged to the reaction system after they are respectively diluted with the above-specified hydrocarbon solvent or cycloolefin.
And, the soluble vanadium compound is preferably diluted to the above concentration before it is charged, and the organoaluminum compound is also diluted to a concentra-tion in the range of, e.g. not more than 50 times as high as the concentration thereof in the polymerization reaction system, and then charged to the polymerization reaction system.
When the cycloolefinic random copolymer is produced, the concentration, as a vanadium atom, of the soluble vanadium compound in the copolymerization system is usually 0.01 to 5 gram-atom/1, preferably 0.05 to 3 gram-atom/1.
The copolymerization reaction of ethylene with a cycloolefin is carried out at a temperature between -50' C and 100' C, preferably between -30' C and 80' C, more preferably between -20'C and 60'C.
The reaction time for the above copolymeriza-tion reaction (or an average residence time of a poly-merization reaction mixture in the case of a continuous polymerization) differs depending upon polymerization materials, concentration of catalyst components and temperatures. The reaction time is usually 5 minutes to 5 hours, preferably 10 minutes to 3 hours. The pressure for the copolymerization reaction is usually more than 0 and up to 50 kg/cm2, preferably more than 0 and up to 20 kg/cm2~
When the cycloolefin random copolymer is produced, the molar ratio of ethylene and cycloolefin 214"~~4~
to be fed is usually 90/10 to 10/90, preferably 85/15 to 40/60. The ethylene unit/cycloolefin unit constitution-al ratio in the resulting ethylene/cycloolefin copolymer is usually 90/10 to 40/60, preferably 85/15 to 50/50.
The above cycloolefinic random copolymer may contain other copolymerizable monomers, e.g. norbornenes other than the cycloolefin of the formula (I) or a-olefins other than ethylene in such an amount that does not impair the object of this invention or not more than 15 mol% based on the total polymer units.
The above copolymerization reaction of ethyl-ene with a cycloolefin gives a solution of a cycloolefin random copolymer in the hydrocarbon solvent or a solu-tion thereof in an unreacted cycloolefin. The concen-tration of the cycloolefinic random copolymer in such a solution is usually 2.0 to 200 g/lZ (g-polymer/.-polymer-ization liquid), preferably 40 to 100 g/~Q. The solution also contains the soluble vanadium compound component and the organoaluminum compound components of the cata-lyst.
The above solution of the cycloolefin random copolymer is usually subjected to a series of treatments starting with deashing and finishing with pelleting, whereby pellets of the cycloolefin random copolymer are obtained.
In the above cycloolefin random copolymer, the structural unit derived from the cycloolefin of the formula (I) is present in a structure shown in the following formula (II) ~ 14'~ 3 4'~
R3 ~ R9 ~ R13 R1~R2 ~I R7~,R8 ~R11,~R12~ R17 ( II ) R4 R5 R6~ R10 ~ R14 n ~ 'm wherein R1 to R18, n and m are as defined as above.
The above ethylene-cycloolefin random copoly-mer preferably has an intrinsic viscosity [r~), measured in decalin at 135'C, of 0.05 to 10 dl/g.
The above random copolymer produced from the isomer mixture of this invention has a high glass tran-sition point (Tg) or superior heat resistance and a high flexural modulus (FM) or superior mechanical strength as compared with any conventional cycloolefin random copol-ymer obtained by copolymerization of ethylene with an isomer mixture containing 85 mol% or more, 90 mol% or more, in many cases, or 94 mol% or more, further in many cases, of an endo-form cycloolefin of the formula (I) (naturally when the comparison is made on the same composition of ethylene and a cycloolefin). Therefore, when the isomer mixture according to this invention is used, it is possible to reduce the amount of expensive tetracyclododecenes and obtain a copolymer having an identical glass transition point (Tg) or a flexural modulus to that of any conventional copolymer.
This invention will be explained below by reference to Examples, which however shall not limit this invention.
Quantitative determination method (a) The endo-form cycloolefin/exo-form cy-cloolefin molar ratio of an isomer mixture of tetracy-clo[4,4,0,12'5,17,10)-3-dodecene (to be abbreviated as 21473~'~
TCD-3 hereinafter) was calculated as follows. TCD-3 was subjected to lII-NMR (in CDC13, room temperature, TMS
standard), and an integration strength ratio of olefin proton absorption peaks in the resultant spectrum was used as a basis for the calculation. Table 1 shows chemical shifts of olefin protons obtained by measure-ment of 1H-NMR of tetracyclo-[4,4,0,12'5,17.10]-3_dode-cene.
Table 1 also shows chemical shifts of carbons obtained by measurement of 13C-NMR of tetracyclo-[4,4,0,12~5,17,10~_g_dodecene.
214.73~.'~
bN bN a~
a~ ~
i M ~ a c ci a +
c~ .~
c~ r~
--- -_ _--- _--_- -_-a~ c.
a~ a~ N
~
a~ ~
~
b ~ .ate ~ o b . _-- -- -_-- -_--- --- o r.
.
w t- 4. c- - c~
c~ ~--I
of ed '~N
~' A U
H U
--- -- ---- ----- -_-x ~ ~ x o o 'x .x N
~
c ~
--- _- -_-- ---_- _-- x co a ~
a. ~ o~ .r-, oo M
hD 60 M
E~ a.~ +~
--_ -- _--- __--_ -__ b b U O h h G G
O O
~f M U U
H W
s~ ~
- - _ - - _ - - ~ U
_ - - - --U d rl ..-I ..-1 it i.n ~ N
a a U - .-I - rl td v1 .G .~ c7 ~C ~
C~
E U U
- - - - - - - - - - -- _ - _ - -U td Z 0.' O
1 ,t. m--I ~ O~
t-U z G, M I CD ,~ L!7 x c c ~
- -- - -- -- ---- -_--- ---x I .'., x o ~c s, p ao a c. p +~ o c.
U 4-~ O
a vw w tr O
i ~
c ~ W ,x a~ w U~
b b w 21 473 7 Further, Table 2 shows chemical shifts of carbon atoms obtained by measurement of 13C-NMR of a TCD-3 copolymer.
2147~4'~
_ 2~ _ _ __ __o__________o___ b~ b ° ~~ o __o__________o___ b b ~~ ~~ b _________________ I
woo wrr ~
cou°~ w~ o _________ ______ o. x °° ~r ri G1 I O
a, c~ x '~' V ~ .-i ca c~ ~ °' N O
I _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ A
H ~~ C7 ~n d' CL
I
x N ~ CD e~~ h0 ~ U
M
_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ p H ~ N ca ..
qC ltd C
M O
_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ .d w ..-i l~ ..-~ O C
O
~ rl U
.C ch ~ N
_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ O
e0 U
U E
~'i N
E
U
U
U
~.-I
.,.
1 v, c~
w~ ~ o w E3 U w x ~ O
co. x ~ o ~ o ''"' a~ b o c W U W
U
N
N x N
U x ~i U
I U N I
N ~ x N
U x i~ V
I U I
_ _ _ _ _ _ ,~ _ _ _ _ _ _ _ _ _ _ _ _ _ _ I
(b) The endo-form cycloolefin/exo-form cy-cloolefin molar ratio of an isomer mixture of pentacy-clo[4,7,0,12~5,10~12~08,3-3~-3-pentadecene (to be abbrevi-ated as PCPD hereinafter) was calculated similarly as follows. PCPD was sub,)ected to 1II-NMR (in CDC13, room temperature, TMS standard), and an integration strength spectrum was used as a basis for the calculation. Table 3 shows chemical shifts of olefin protons obtained by measurement of lII-NMR of PCPD.
Table 3 also shows chemical shifts of carbons obtained by measurement of 13C-NMR of PCPD. scs Table 4 shows chemical shifts of carbons obtained by measurement of 13C-NMR of an ethylene-PCPD
copolymer.
z i ~.~~ ~~
b ~n b o~
M M
. ,~ . r-, U U
U~ UO
U
a O
_ _ -_ _ - - - _ - - - -- - - - --w o~ w co ~ a, ' ' ' ~ a s ~
s~
- - - - - - _ --- - - _ - _ - _ -o o p C N p ~ ~ it m - - - - - -- -_ _ - - M
- - -- - _ _ H z p ~ U
A
I U U
~ U ,~ a0 ,~ a0 _ Gl i M p ).r p ~ r - .-I
~
~ ' C .a x x q -__-_ ---__-- x -_---_ -- c~
r1 ~
O M O a~
M G1, U G4 ---_- -_-- C R
_ - - - _ - O O
- - _ -~-I .1 ' p O
~
f E" O
.-I
xr~ xr~ c c w O O
U U
_ - - - - _ - - --_ _ - ' - _ ~
_ - - _ U
p O
U
.- 2' ~ '~ it f-i C~ N p p C1. ,~ t V
p .C I O
.~ c U x C
.
U
rY- r~
I O
- _ _ - - _ - - _ - _ _ _ - -- - - -- -x .
, x z I
x ' ~ a w o ''' w U
O
p t ~ O
..
Cf1C
.b p .b 2147~4'~
.-a o~
b~ b~
r'.
ci o~ ti cc ------ -----_ -__- ----o~ o, ~r a~
b co b o o r~
C pa is A
------ --_--_ ---- -__-U
E-~ W O W In t-~ ~d a1 C
O
- - - _ _ - - - - - -- - - _ _ - - _ -N
o r~ r~ z G~ C G I
O _ U
U E3 OC C~
CL ~ _ - - - - - - - - - -- - - _ _ - - - -A G.
Cs. _ 1 E7 U ~ U v~
L7r C9 - N - N C
I .-I .C eh .C cr O
O
C +~
d' ~ a0 00 ..a O
r~ c7 ~, b c~
d ~a C
r-I r-I 'i O
.C
i-~ U
c~ -_---- ------ --_- ----O
H +.~
C d' d' C
..1 C~ C~ C
+~ O
.,.. p ", C _ - _ _ - _ - - ' - - C
- - - - - - - _ -a 'n A O
fs. -O -O
U x c~ x c9 O
- -- ----_-- ----- _---- -__ W
x -- x U
O
U a~ f3 i..~ it OC C O La ~ W O
x U W
I C O
U t- m C O
+~ C i~
rl Cn C W G W
Method of measurement of softening temperature Copolymers prepared in Polymerization Examples and Comparative Polymerization Examples were respective-1_y molded into sheet samples, and thermal deformation behavior tiuereof was measured by using a thermomechani-cal analyzer supplied by du Pont. That is, the soften-ing temperature is a temperature at which a quartz penetrat;or penetrated tl~e sample 0.635 mm deep under a load of 49 g at a temperature elevatlon rate of 5'C/mlnute (the softening temperature is referred to as TMA softening temperature hereinafter).
Method of measurement of flexural modulus Measurement was made according to ASTM-D790 at 2 3' C .
Method of measurement of intrinsic viscosity Measurement was made in decaline at 135'C.
REC'ERENTIAL EXAMPLE 1 Norbornene and cyclopentadiene were sub,~ected to a Diels-Alder reaction according to a method de-scribed In Japanese Patent Publication No. 14910/1971 to synthesize tetracyclo[4,4,0,12~5,17~10]_g-dodecene (~).
The resultant tetracyclododecene-3 had 94.9 mol% of an endo form and 5.1 mol % of an exo form.
Table 5 shows the results.
RErERCNTIAL EXAMPLE 2 5-Ethyl-2-norbornene and cyclopentadiene were sub,~ected to a Diels-Alder reaction in the same way as in Referential Example 1 to synthesize 8-ethyl-tetracy-cto[4,4,0,12'5,17~10]_g-dodexene (~ ).
CZHS
2147~4'~
The resultant 8-ethyl-tetracyclo-(4,4,0,12~5,17.10~-g_dodecene was measured by sub,)ecting it to lII-NMR to obtain an endo-form cycloole-fin/exo-form cycloolefin molar ratio. This compound had 97.3 mol% of an endo-form cyclooefin and 2.7 mol% of an exo-form cycloolefin.
Table 5 shows the results.
A 30-liter reaction vessel equipped with stirrer and a reflux condenser was charged with 1 liter of the tetracyclo-[4,4,0,12'5,17.10]-3_dodecene (TCD-3) obtained in Referential Example 1 and 17 liters of cyclohexane, and the mixture was stirred. Twelve kilo-grams of zeolite (Zeolam F-9, trade name, a product of Tosoh Corporation, spherical forms, 1.8 to 2.4 mm~5, Na20.A1203.2.5Si02) was added to the resultant solution, and the mixture was stirred at room temperature for 6 hours to carry out an isomerization reaction from an endo-form cyclooefin to an exo-form cycloolefin.
After the reaction, the reaction mixture was filtered to separate the catalyst, and the resultant solution of TCD-3 in cyclohexane was distilled under a reduced pressure (50 mmHg) to give isomerized TCD-3.
Analysis of the TCD-3 by lII-NMR showed an endo-form cyclolefin/exo-form cycloolefin molar ratio of 44.2/55.8.
Table 5 shows the results.
Example 1 was repeated except that the reac-tion time was changed to 3 hours.
Table 5 shows the results.
Example 1 was repeated except that the cata-lyst was changed to silica-alumia (Sekado OW, a product of Shinagawa Refractories Co., Ltd., particulate, 0.5 to 2 mm~6, A1203.mSi02.nH20+A1(OII)3), that the amounts of the catalyst and cyclohexane were changed to 4.0 liters 21 ~.'~ 3 4'~
and 3 kg, respectively, and that the reaction time was changed to 96 hours.
Table 5 shows the results.
Example 1 was repeated except that the 8-ethyl-tetracyclo[4,4,0,12'5,17.10]-3-dodecene (8E-TCD-3 in short) obtained in Referential Example 2 was used.
Table 5 shows the results.
Example 4 was repeated except that the reac-tion time was changed to 3 hours.
Table 5 shows the results.
Example 4 was repeated except that the same silica-alumina as that used in Example 3 was used and that the reaction time was changed to 96 hours.
Table 5 shows the results.
214.7~4~' o ~.
+~ w ~. ew o 00 ~ o a~ M ao --O m \ ltd In ~ co N ~ c0 B \ \ \ \ \ \ \ \
..~I F O ~ CV CO O M .-I l - N Bbl cn o w ~r ~ u~i M t~ o o~ r o ~n a~ mn M a~ ~ M
N
U O W O
- - _ - - - - _ - - - - - - _ - - - - -O O
O _ cd E3 ~ O M ~ CG M ~ d' U
N i-~
U
'.i O
U ~ CD c0 M ~ tp CD t0 m U ~ ..1 p ~
i.r ~ +- ~
a "C1 U .C i-> ~ T!
O F~ ~U U .C'» id C r-I
-~-r cd ~0 t, ~.-~ U ~r-i c~
In ~..~ _ E3 iw ~ U
U N C ~ SO O e--1 C r-1 ~ir O
r-I ~.i c~ r-1 ~ ..i ~ ~ cd O of ~ cd U U
fr O v .~.-~ U U ~ ~.~ U U
c0 U 'L7 v~ a7 ~ ~ cd i-~ ~ +~ c~ GL u7 H 6 C N ~.-i ~.~1 U cb ~.-~i ~r-1 U to U
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c0 w e~ ~ ed a! 4.. cd cd O cd Pe a~ ~e o~ oe o-e a~ ~e ~e ~e w xw w w wxw w w w w ;a 214734' ,.... _ EXAMPLE 7 (Polymerization Example 1) A two-liter glass polymerizes having a stirrer was continuously charged, from its top, with a solution of the TCD-3 obtained in Example 1 in cyclohexane, a solution of VO(OC2II5)C12 as a catalyst in cyclohexane and a solution of ethylaluminum sesquichloride (Al(C2II5)1.5C11.5) such that the concentrations thereof in the polymerizes were 60 g/1, 0.5 mmol/1 and 4.0 mmol/1, respectively. And, the polymerizes was also charged from its top with ethylene at a rate of 15 liters/hour and hydrogen at a rate of 0.5 liter/hour.
Separately, a reaction mixture was continuously with-drawn from the polymerizes bottom such that the'total amount of a polymerization liquid in the polymerizes was 1 liter and that the residence time thereof was 0.5 hours.
The above polymerization reaction was carried out at 10'C by circulating a refrigerant through a cooling ,packet externally provided to the polymerizes.
Under the above copolymerization reaction conditions, a polymerization reaction mixture containing an ethylene-TCD-3 random copolymer was obtained. The polymerization reaction was stopped by adding a small amount of isopropyl alcohol to the polymerization liquid withdrawn from the polymerizes bottom. Then, the poly-merization was charged into a mixer while the mixer containing acetone whose amount was about three times as large as the polymerization liquid was operated, whereby the copolymer was precipitated. The precipitated copol-ymer was recovered from the solution by filtration. The resultant copolymer was dispersed in acetone such that the concentration thereof was about 50 g/1, and the resultant mixture was further heat-treated at a boiling point of acetone. Thereafter, the copolymer was sepa-rated from the acetone by filtration, and dried under reduced pressure at 120'C for 24 hours.
The resultant ethylene-TCD-3 copolymer was 2147~4~' subjected to 13C-NMR to show that it had an ethylene content of 60.7 mol%. And, it had an intrinsic viscosi-ty [r~] of 0.37 dl/g and a TMA softening temperature of 18 0' C .
Table 6 shows the results. Further, Fig. 1 shows the relationship between a tetracyclododecene-3 content (mol%) in the ethylene-tetracyclododecene-3 copolymer obtained as above and a softening temperature thereof. And, Fig. 2 shows the relationship between a tetracyclododecene content (mol%) of the copolymer above and flexural modulus thereof.
The above copolymer was also subjected to 13C_NMR to show that it had an endo form cycloolefin/exo form cycloolefin molar ratio of 41/59, and this value hardly changed from that obtained before the polymeriza-tion.
EXAMPLES 8-14 (Polymerization Examples 2-8) and COMPARATIVE EXAMPLES 1 and 2 (Comparative Polymerization Examples 1 and 2) Copolymerization of ethylene and tetracyclo-dodecene was carried out in the same way as in Polymers-zation Example 1 by using materials (tetracyclododecene) shown in Table 6 under the conditions specified in Table 6.
Table 6 shows the results.
And, Fig. 1 shows the relationship between a tetracyclododecene-3 content (mol%) in the ethylene-tetracyclododecene-3 copolymer obtained as above and a softening temperature thereof. And, Fig. 2 shows the relationship between a tetracyclododecene content (mol%) of the copolymer above and flexural modulus thereof.
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EXAMPLES 15-17 (Polymerization Examples 9-11) and COMPARATIVE EXAMPLE 3 (Comparative Polymerization Example 3) Copolymerization of ethylene with 8-ethyl-tetracyclododecene-3 was carried out in the same way as in Example 7 by using materials (8-ethyl-tetracyclodode-cene-3) shown in Table 7.
Table 7 shows the results.
Table 7 shows that the copolymers obtained in Examples 15-17, using 8-ethyl-tetracyclododecene-3 having a large content of an exo form, are improved both in TMA softening temperature and flexural modulus as compared with the copolymer obtained in Comparative Example 3.
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Claims (26)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the isomerization of a cycloolefin from an endo form to an exo form which comprises isomerizing an endo-form cycloolefin of the following formula (I) (wherein R1 to R14 are independently a hydrogen atom, a halogen atom or a lower alkyl group, R15 to R18 are independently a hydrogen atom, a halogen atom, or a cycloalkyl group, or R15 or R16 and R17 or R18 may be bonded to each other to form a cyclopentyl, cyclopentenyl or cyclohexyl group, or R15 and R16 or R17 and R18 may together form an ethylidene, propylidene or isopropylidene group, n is 0 or 1, and m is 0, 1 or 2, provided that m and n cannot be simultaneously zero), in the presence of a solid acid catalyst to convert its endo form into the corresponding exo form.
-44a-
-44a-
2. A process according to claim 1, wherein the cycloolefin has the following formula (I-A) (wherein R7 to R18 are as defined in claim 1).
3. A process according to claim 1, wherein the cycloolefin has the following formula (I-B) (wherein R1 to R10 and R15 to R18 are as defined in claim 1).
4. A process according to claim 1, wherein the solid acid catalyst is at least one member selected from the group consisting of oxides or sulfides of a metal belonging to the groups 3 to 8 of the periodic table and organic solid acids.
5. A process according to claim 1, wherein the solid acid catalyst is at least one member selected from the group consisting of oxides or sulfides of Al, Si, P, Ti, V, Cr, Mo, W, Mn, Fe or Co and sulfonic acid group-containing crosslinked polymers.
6. A process for the production of an isomer mixture rich with a cycloolefin having an exo form, which comprises subjecting an isomer mixture rich with a cycloolefin having an endo form to an isomerization reaction in the presence of a solid acid catalyst to form the isomer mixture rich with a cycloolefin having an exo form, the cycloolefin having the following formula (I) (wherein R1 to R14 are independently a hydrogen atom, a halogen atom or a lower alkyl group, R15 to R18 are independently a hydrogen atom, a halogen atom an alkyl or a cycloalkyl group, or R15 or R16 and R17 or R18 may be bonded to each other to form a cyclopentyl, cyclopentenyl or cyclohexyl group, or R15 and R16 or R17 and R18 may together form an ethylidene, propylidene or iospropylidene group, n is 0 or 1, and m is 0, 1 or 2, provided that m and n cannot be simultaneously zero).
7. A process according to claim 6, wherein the isomer mixture rich with a cycloolefin having an endo form comprises, based on endo-form and exo-form cycloolefins in total, at least 85 mol% of a cycloolefin having an endo form and up to 15 mol % of a cycloolefin having an exo form.
8. A process according to claim 6, wherein the isomer mixture rich with a cycloolefin having an exo form comprises, based on endo-form and exo-form cycloolefins in total, up to 80 mol% of a cycloolefin having an endo form and at least 20 mol% of a cycloolefin having an exo form.
-46a-
-46a-
9. A process according to claim 6, wherein the cycloolefin has the following formula (I-A) (wherein R7 to R18 are as defined in claim 6).
10. A process according to claim 6, wherein the cycloolefin has the following formula (I-B) (wherein R1 to R10 and R15 to R18 are as defined in claim 6).
11. A process according to claim 6, wherein the solid acid catalyst is at least one member selected from the group consisting of oxides or sulfides of a metal belonging to the groups 3 to 8 of the periodic table and organic solid acids.
12. A process according to claim 6, wherein the solid acid catalyst is at least one member selected from the group consisting of oxides or sulfides of Al, Si, P, Ti, V, Cr, Mo, W, Mn, Fe or Co and sulfonic acid group-containing crosslinked polymers.
13. An isomer mixture of a cycloolefin of the formula (I) as defined in claim 1 which comprises, based on the cycloolefin having an endo form and the cycloolefin having an exo form in total, up to 80 mol% of the cycloolefin having an endo form and at least 20 mol% of the cycloolefin having an exo form.
14. An isomer mixture of a cycloolefin of the formula (I-A) as defined in claim 9 which comprises, based on the cycloolefin having an endo form and the cycloolefin having an exo form in total, up to 80 mol% of the cycloolefin having an endo form and at least 20 mol% of the cycloolefin having an exo form.
15. An isomer mixture of a cycloolefin of the formula (I-B) as defined in claim 10 which comprises, based on the cycloolefin having an endo form and the cycloolefin having an exo form in total, up to 80 mol% of the cycloolefin having an endo form and at least 20 mol% of the cycloolefin having an exo form.
16. Use of an isomer mixture of claim 13, 14 or 15, for the production of an ethylene-cycloolefin random copolymer.
17. A process according to any one of claims 1 to 3 and 6 to 10, wherein the solid acid catalyst is a member selected from the group consisting of silica-alumina, alumina, zeolite (composed mainly of Na2O, A12O3 and S1O2), activated clay, Cr2O3, P2O3, T1O2, A12O3-xCr2O3, A12O3-CoO, A12O3-MnO, Cr2O3-Fe2O3, MoS, MoS2, CrO3, CrO2C12, MoO3, V2O3 and WO2C12.
18. A process according to any one of claims 1 to 3 and 6 to 10, wherein the solid acid catalyst is zeolite composed mainly of Na2O, A12O3 and S1O2.
19. A process according to any one of claims 1 to 3 and 6 to 10, wherein the solid acid catalyst is silica-alumina.
20. A process according to claim 1, wherein the cycloolefin is tetracyclo-(4.4Ø1 2,5.1 7,10]-3-dodecene.
21. A process according to claim 20, wherein the solid acid catalyst is a member selected from the group consisting of silica-alumina, alumina, zeolite (composed mainly of Na2O, A1 2O3 and S1O2), activated clay, Cr2O3, P2O3, T1O2, A12O3-xCr2O3, A12O3-CoO, A12O3-MnO, Cr2O3-Fe2O3, MoS, MoS2, CrO3, CrO2C1 2, MoO3, V2O3 and WO2C1 2.
22. A process according to claim 21, wherein the solid acid catalyst is silica-alumina or zeolite composed mainly of Na2O, A1 2O3 and S1O2.
23. An isomer mixture according to claim 14, wherein R7 through R18 in the formula (I-A) are each hydrogen or lower alkyl.
24. An isomer mixture according to claim 23, wherein the cycloolefin is tetracyclo[4.4Ø1 2,5.1 7,10]-3-dodecene or 8-ethyltetracyclo[4.4Ø1 2,5.1 7,10]-3-dodecene.
25. An isomer mixture according to claim 15, wherein R1 through R10 and R15 through R18 are each hydrogen or lower alkyl.
26. An isomer mixture according to claim 25, wherein the cycloolefin is pentacyclo[4.7Ø1 2,5.1 9,12.0 8,13]-3-pentadecene.
Applications Claiming Priority (13)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21044989 | 1989-08-15 | ||
| JP210,448/89 | 1989-08-15 | ||
| JP210,449/89 | 1989-08-15 | ||
| JP21044889 | 1989-08-15 | ||
| JP244,493/89 | 1989-09-20 | ||
| JP244,494/89 | 1989-09-20 | ||
| JP1244494A JPH03106909A (en) | 1989-09-20 | 1989-09-20 | Cycloolefin random copolymer and its production |
| JP1244493A JPH03106832A (en) | 1989-09-20 | 1989-09-20 | Isomerization of endo isomer of pentacyclopentadecene to exo isomer, mixture of pentacyclopentadecene isomers and production thereof |
| JP275,715/89 | 1989-10-23 | ||
| JP27571589A JP2795486B2 (en) | 1989-08-15 | 1989-10-23 | Cyclic olefin random copolymer and method for producing the same |
| JP1275714A JP2848869B2 (en) | 1989-08-15 | 1989-10-23 | Method for Isomerizing Tetracyclododecene Endo Form into Exo Form, Tetracyclododecene Isomer Mixture, and Method for Producing the Same |
| JP275,714/89 | 1989-10-23 | ||
| CA002023214A CA2023214C (en) | 1989-08-15 | 1990-08-14 | Copolymer of cycloolefin and ethylene |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002023214A Division CA2023214C (en) | 1989-08-15 | 1990-08-14 | Copolymer of cycloolefin and ethylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2147347A1 CA2147347A1 (en) | 1991-02-16 |
| CA2147347C true CA2147347C (en) | 2000-07-04 |
Family
ID=27560957
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002147347A Expired - Fee Related CA2147347C (en) | 1989-08-15 | 1990-08-14 | Isomerization of cycloolefin from endo-form to exo-form and isomer mixture of cycloolefin |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2147347C (en) |
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1990
- 1990-08-14 CA CA002147347A patent/CA2147347C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CA2147347A1 (en) | 1991-02-16 |
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