US3830860A

US3830860A - Stabilization of norbornenes

Info

Publication number: US3830860A
Application number: US00327125A
Authority: US
Inventors: T Nagase; F Masuko
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 1972-01-27
Filing date: 1973-01-26
Publication date: 1974-08-20
Anticipated expiration: 1991-08-20
Also published as: JPS4878153A; DE2303883A1; IT977687B; DE2303883C3; NL173392B; GB1403456A; NL7300966A; JPS5235666B2; GB1403455A; FR2169351B1; NL173392C; FR2169351A1; DE2303883B2

Abstract

A METHOD FOR STABILIZATION OF NORBORNENES WHICH COMPRISES INCORPORATING AT LEAST ONE PHENOL OF EITHER ONE OF THE FORMULAE:

4-((4-(HO-),R3,R4-PHENYL)-X-),R1,R2-PHENOL

2-((2-(HO-),R7,R8-PHENYL)-X''-),R5,R6-PHENOL AND

2-R9,3-R10,4-R11,5-R12,6-R13,7-R14,8-R15-1-NAPHTHOL

WHEREIN X AND X'' ARE EACH ALKYLIDENE HVING 1 TO 6 CARBON ATOMS, CYCLOALKYLIDENE HAVING 3 TO 6 CARBON ATOMS, THIO, SULFINYL OR SULFONYL, R1, R2, R3, R4, R5, R6, R7 AND R8 ARE EACH HYDROGEN, ALKYL HAVING 1 TO 9 CARBON ATOMS OR CYCLOALKYL HAVING 3 TO 6 CARBON ATOMS AND R9, R10, R11, R12, R13, R14 AND R15 ARE EACH HYDROGEN, ALKYL HAVEING 1 TO 9 CARBON ATOMS OR PHENYL INTO A NORBORNENE SELECTED FROM THE GROUP CONSISTING OF ALKENYLNORBORNENES AND ALKYLIDENENORBORNENES.

Description

and alkylidenenorbornenes.

United States Patent 12 Claims ABSTRACT OF THE DISCLOSURE A method for stabilization of norbornenes which comprises incorporating at least one phenol of either one of the formulae:

and

The present invention relates to a method for stabilization of norbornenes, particularly alkenylnorbornenes and alkylidenenorbornenes.

As is well known, norbornenes are very useful as one of the termonomers in the production of elastomers with ethylene and propylene (hereinafter referred to as EPDM). However, they are sensitive to air, metal oxides and the like and are apt to form rubbery materials on storage, whose presence is unfavorable, when the monomers are used for the production of terpolymer elastomers.

As the result of extensive studies, it has been found that some certain phenols are markedly effective for the stabilization of norbornenes.

According to the present invention, there is provided a method for stabilization of norbornenes which com- Patented Aug. 20, 1974 prises incorporating at least one phenol of either one of the formulae:

F HO OH ()H OH XI R5 i 4 Rs Ra R1 and [III] Iii: (|)H RHfOlRI Rn V io n l:

wherein X and X are each alkylidene having 1 to 6 carbon atoms, cycloalkylidene having 3 to 6 carbon atoms, thio, sulfinyl or sulfonyl, R R R R R R R and R are each hydrogen, alkyl having 1 to 9 carbon atoms or cycloalkyl having 3 to 6 carbon atoms and R R10, R R R R and R are each hydrogen, alkyl having 1 to 9 carbon atoms or phenyl into a norbornene selected from the group consisting of alkenylnobornenes alkylidenenorbornenes.

As the norbornenes which can be stabilized by the present invention, there are exemplified alkenylnorbornenes of the formula:

C=(l',-R wherein R R R and R are each hydrogen or alkyl having 1 to 6 carbon atoms and alkylidenenorbornenes of the formula:

(3R21 [13] R22 wherein R R and R are each hydrogen or alkyl having 1 to 6 carbon atoms.

Specific examples of the alkenylnorbornenes [A] are as follows:

5-vinyl-2-norbornene, S-propenyl-Z-norbornene, S-isopropenyl-2-norbornene,

5 (2'-methylpro penyl) -2-norbornene, 5-(1',2-dimethyl-1-propenyl)-2-norbornene, 5-vinyl-6-methyl-2-norbornene, etc.

Specific examples of the alkylidenenorbornenes [B] are as follows:

5-methylene-Z-norbornene,

5-ethylidene-Z-norbornene, S-isopropylidene-Z-norbornene, S-ethylidene-6-methyl-2-norbornene, S-isopropylidene-6-methyl-2-norbornene, etc.

Among the phenols [I] and [II], particularly preferred are those wherein the substituents on the benzene rings represented by the symbols R to R are hydrogen, methyl, ethyl, propyl, isopropyl, sec.-butyl, t-butyl, t-octyl, sec.- nonyl, cyclohexyl and/ or cyclohexylmethyl and the moiety bridging two benzene rings represented by the symbols X or X is methylene, ethylidene, isopropylidene, butylidene, cyclohexylidene, thio (S), sulfinyl (SO) or sulfonyl (SO Specific examples of the phenols [I] and [II] are as follows:

etc.

Of the phenols [III], the preferred ones are those wherein the substituents on the naphthalene ring represented by the symbols R to R are methyl, ethyl, propyl, isopropyl, butyl, sec.-btuyl, t-butyl, pentyl, isopentyl and/ or phenyl.

Specific examples of the phenols [III] are as follows:

l-n aphthol,

Z-methyll-naphthol, 3-methyl-1-naphthol,

4-methyll-naphthol,

S-methyl- 1 -naphthol, 7-methyl-1-naphthol, 4-methyl-3-phenyl-1-naphthol, 2-ethyl-1-naphthol, 4-ethyl-1-naphthol, 5-ethyl-4-methyll-naphthol, 7-ethyl-4-methyl- 1 -naphthl, 2,4-dimethyll-naphthol, 2,7-dimethyl-1-naphthol, 3,4-dimethyl-1-naphthol, 5,7-dimethyll -naphthol,

,8-dimethyll-naphthol, 2,4-diethyl-1-naphthol, 2,4,6-trimethyl-1 -naphthol, 2,4,7-trimethyl- 1 -naphthol, 3,4,6-trimethyl-l-naphthol, 6-ethyl-2,4-dimethyl l-naphthol, 6-ethyl-3 ,4-dirnethyll-naphthol, 7-ethyl-3,4-dimethyll-naphthol, Z-propyll-naphthol, 4-propyl-1-naphthol, 2-isopropyl-1-naphthol, 5-isopropyl-3, S-dimethyll-n aphthol, 2-butyll-naphthol,

4-butyll -naphthol,

4-t-butyl- 1 -n aphthol, 2-sec.-butyll-naphthol, 2-isopentyll -naphthol, 2-phenyl-1-naphthol,

4-phenyll-naphthol, 2,3-diphenyl- 1 -naphthol,

etc.

The concentration of the stabilizer, i.e. the phenol [I], [II] or [III], to be incorporated into the norbornene may be usually from about 20 p.p.m. to about 3000 p.p.m. or more. The preferred concentration is from 20 ppm. to 500 p.p.m. by weight, since at such concentrations the stabilizer need not be removed prior to use of the norbornene.

Practical and presently preferred embodiments of the present invention are illustratively shown in the following Examples wherein p.p.m. is by weight.

EXAMPLE 1 The desired quantity of stabilizer was added to freshly distilled 5-ethylidene-2-norbornene and charged in a glass ampoule. The ampoule without sealing was placed in an oil bath maintained at 54 C. After the elapse of a certain period of time, the ampoule was taken out from the oil bath and allowed to be cooled. S-Ethylidene-Z-norbornene was evaporated in vacuo, and the residual rubbery material Was weighed. The results are shown in Table 1, compared with the results of the blank test Without the addition of any stabilizer.

TABLE 1 Rubbery material (percent by weight based on 5- ethylidene2-norbornene) Concentration 184 397 533 Stabilizer (p.p.m hours hours hours None 5.2170 11.8421 14.9704 4,4-th1obis(3-methyl-6-tbutylphenol) 254 0.0209 0.1128 0.4629 2,2-methylene-bis(4-methyl- 6-t-butylphenol) 246 0.0178 0.0138 0.1944

In the same manner as above, the stabilization effect of a conventional stabilizer, i.e. p-t-butylcatechol, on 5- ethylidene-Z-norborncne was tested. The results are shown in Table A.

In the same manner as in Example 1, the stabilization effect of the phenol as shown in Table 2 on 5-vinyl-2- norbornene was tested. The results are shown in Table 2, compared with that in case of the blank test.

TABLE 2 Rubbery material (percent by weight based on 5-viny1-2-norbornene) Concentration 233 492 785 978 Stabilizer (p.p.m.) hours hours hours hours None 4l4 thiobis (a 2 6761 6 2194 8 7498 13. 3175 methyl-fi-t-butylphenol) 206 0. 0603 0. 0890 0. 1717 0. 1945 2,2-methylene-b1s- (4-methyl-6-tbutylphenol) 161 0. 0403 0. 0472 0. 1565 0. 1619 EXAMPLE 3 In the same manner as in Example 1, the stabilization effect of the phenol as shown in Table 3 or S-isopropenyl- 2-norbornene was tested. The results are shown in Table 3, compared with that in case of the blank test.

TABLE 3 TABLE 7 Robbery material (percent by weight Rubbery material (percent based on 5-isopropenyl-2-norborby weight based on 5- nene) ethylldene-2-n0rbori1ene) co n. CODCGH- tration 245 483 725 973 5 tration 266 4113 718 Stabilizer (p.p.m.) hours hours hours hours Stabilizer (p.p.m.) hours hours hours 2 0.013 9.731 15.425 10.4903 13.0052 21.7987 fg i ffiffi 2 75 l-naphthoL- 482 0. 0701 0.1886 0. 5505 2-nephthol 301 7. 4271 15.3423 23.7220

plieiiyl) 235 0.003 0.092 0.168 0.205

mdfgfgthglegigis 19s 048 0 05s 0 173 0 217 EXAMPLE 8 buy p In the same manner as in Example 1, the stabilization EXAMPLE 4 effect of the phenol as shown in Table 8 on 5-vinyl-2- norbornene was tested. The results are shown in Table 8, In the same manner as 1 E p 1, the stjablhzatloP 15 compared with that in case of using 2-naphthol and that effect of the phenol as shown in Table 4 on 5-isop1'opyl1- in case of the blank test dene-Z-norbornene was tested. The results are shown in TABLE 8 Table 4, compared with that in case of the blank test.

. Rubbery material (percent TABLE 4 Concenby weight based on fi-vinyl- Rubbei'y material (percent by weight 323; zmrbomene) based on 5-isopropylidene-2-n0rbor- 247 479 791 Comm 119119) Stabilizer hours hours hours tration 179 403 529 971 None 2. 7842 5 9834 s 9718 Stabilizer (p.p.m.) hours hours hours hours -napgglgoh 347 0. 0045 011731 012523 None 4.071 9.753 12. 392 10. 352 368 1-9521 4.3 18 7.5421 3ifi 3 tl EXAMPLE 9 9 ll p tieii l) 238 0.023 0.124 0. 47s 2. 471 g iigl ggl cle-gilbls- In the same manner as in Example 1, the stabilization butylph'enol)-- 225 0.019 0.024 0.213 1.354 effect of the phenol as shown in Table 9 on 5-isopropenyl- 2-norbornene was tested. The results are shown in EXAMPLE 5 Table 9, compared with that in case of using Z-naphthol In the same manner as in Example 1, the stabilization and that 111 case of the nk test. effect of the phenol as shown in Table 5 on 5-ethylidene-2- TABLE 9 norbornene was tested. The results are shown in Table 5, Rubbers. material (percent compared with that in case of the blank test. by wei ht based on 5- isopropenyl-2-n0rbornene) TABLE 5 Concenration 243 475 731 Robbery material (percent Stabilizer (p.p.m.) hours hours hours by weight based on 5 ethylideiie-2-norbornene) Non 2.689 5.972 9. 816 Concen- 1-naphthol 353 0.075 0.143 0.306 tmtion 191 402 538 2-naphthol 371 1. 874 4.932 s. 592 Stabilizer (p.p.m.) hours hours hour 5 None 5. 3243 12. 0431 15.0025 EXANIPLE 1O 2,2-thiobis(4-t-butyl-6 methylphenol)--- 238 0.0213 0.1117 0.3419 In the same manner as in Example 1, the stabilization I fi g f 213 0.0227 Q0324 0.1869 effect of the phenol as shown in Table 10 on 5-1sopropyl- 4,4-methylene-bis 1dene-2-norbornene was tested. The results are shown in 6-t-butylphel10l) 199 0.0197 0. 0248 03809 T M 0 mqsopmpyhdene a e 1 ,rompared with that in case of using Z-naphthol u y i 205 @0252 1043 2642 and that in case of the blank test.

TABLE 10 EXAMPLE 6 Rilibbery 1itiaferia (pegcent y weig ass on -iso- In the same manner as in Example 1, the stabilization propyudemamorbomene) eflect of the phenol as shown m Table 6 on 5-viny1-2-norg 193 415 627 T8 101]. bomene d 33113151 2 1 1 2:; m Table Stabilizer (p.p.m.) hours hours hours i a in case 0 e an compare wt ieone 3.1 314 13. 713 -nap o 182 0.563 TABLE 6 2naphthol 341 3.374 2.040 12. 74s

Rubbery material (percent by weight based on 5- vinyl-2-norbornene EXAMPLE 11 ctongpn- 235 511 790 In th E 1 1 h b 1 re 1011 0 e same manner as in xamp e t e sta iization h s h s hours stabhm (p pm) our our effect of the phenol as shown in Table 11 on S-ethyhdene- Non 2-6873 6-3015 3-3102 2-norbornene was tested. The results are shown in Table 135 M613 0,0917 ,184 11, compared with that in case of the blank test.

203 0.0598 0.0895 0.1739 TABLE 11 179 0.0517 0.0749 0.1921 R b ,4-is i 1 y 195 0 0652 0 0825 0 1642 y v eig l i b a s ed if g bullylphenol) ethylideiie-2-norbornene) Concentration 273 461 722 EXAMPLE 7 stabihzer (p.p.m.) hours hours hours None 10.5213 13. 7145 21.8095 In the same manner as in Example 1, the stabilization 2 methy1 1 uaphthol 395 M814 0.2135 0. 6148 effect of the phenol as shown in Table 7 on S-ethyhdene- Hu ng-113 11111 1 1 419 0.0903 0. 2418 0.6719 2-norbornen1e 1.77:;1 tasted. The resiglts are szhownhtilrli 'llablg jj fg t i ffigfi 2 88823 8 Q3143 W1 2 in case 0 usin -na 0 an 11 ymp 0. 521 compare g p 4-phenyl-1-naphthol 410 0.0869 0. 2931 0. 0902 that in case of the blank test.

7 What is claimed is: 1. A method for stabilization of norbornenes which comprises incorporating at least one phenol of either one of the formulae:

(|)H (|)BI R I l Rs and wherein X and X are each alkylidene having 1 to 6 carbon atoms, cycloalkylidene having 3 to 6 carbon atoms, thio, sulfinyl or sulfonyl, R R R R R R R and R are each hydrogen, alkyl having 1 to 9 carbon atoms or cycloalkyl having 3 to 6 carbon atoms and R R R R R R and R are each hydrogen, alkyl having 1 to 9 carbon atoms or phenyl into a norbornene selected from the group consisting of alkenylnorbornenes and alkylidenenorbornenes.

2. The method according to claim 1, wherein the alkenylnorbornenes are those of the formula:

wherein R R R and R are each hydrogen or alkyl having 1 to 6 carbon atoms.

3. The method accOrding to claim 1, wherein the alkylidenenorbornenes are those of the formula:

wherein R R and R are each hydrogen or alkyl having 1 to 6 carbon atoms.

4. The method according to claim 1, wherein the concentration of the phenol to be incorporated is from 20 p.p.m. to 3000 p.p.m.

5. The method according to claim 4, wherein the concentration of the phenol to be incorporated is from 20 ppm. to 500 ppm.

6. The method according to claim 1, wherein the phenol is selected from the group consisting of 4,4-methylenebisphenol,

4,4isopropylidenebisphenol,

4,4-cyclohexylidenebisphenol,

4,4-thiobisphenol,

4,4'-methylenebis(Z-t-butylphenol),

4,4'-methylenebis 3-methyl-6-t-butylphenol) 4,4'-isopropylidenebis 2-t-butylphenol 4,4-butylidenebis (2-methylphenol 4,4-thiobis (Z-ethylphenol) 4,4'-sulfonebis 2- cyclohexylphenol 4,4-butylidenebis(3-methy1-6-t-butylphenol) 4,4'-thiobis(3-methyl-6-t-butylphenol),

4,4-methylenebis (3 ,5 -di-t-butylphenol) 8 4,4'-methylenebis 3 -methyl-5-t-butylphenol 2,2'-methylenebisphenol, 2,2'-isopropylidenebisphenol, 2,2'-thiobisphenol, 2,2'-methylenebis(4-t-butylphenol), 2,2'-thiobis(4-t-octylpheno1), 2,2'-methylenebis (4-methyl-6-t-butylphenol 2,2-thiobis(4 t-butyl-6-methylphenol), 2,2-methylenebis (4,6-di-t-butylphenol) 2,2'-sulfonebis(4-t-butyl-6-methylphenol), and 2,2'-butylidenebis-( 4-t-butyl-6-methylphenol 7. The method according to claim 1, wherein the phenol selected from the group consisting of l-naphthol, 2-methyl-1-naphthol, 3-methyl-1-naphthol, 4-methyl-l-naphthol, 5-methyl-1-naphthol, 7-methyl-1-naphthol, 4-methyl-3-phenyl-1-naphthol, 2-ethyl-1-naphthol, 4-ethyl-1-naphthol, 5-ethyl-4-methyl-l-naphthol, 7-ethyl-4-methyl-l-naphthol, 2,4-dimethyl-1-naphthol, 2,7-dimethyl-1-naphthol, 3,4-dimethyl-1-naphthol, 5,7-dimethyl-1-naphthol, 5,8-dimethyl-1-naphthol, 2,4-diethy1-1-naphthol, 2,4,6-trimethyl-l-naphthol, 2,4,7-trimethyl-l-naphthol, 3,4,6-trimethyl-l-naphthol, 6-ethyl-2,4-dimethyl-l-naphthol, 6-ethyl-3,4-dimethyl-l-naphthol, 7-ethyl-3,4-dimethyl-1-naphthol, 2-propyl-1-naphthol, 4-propyl-1-naphthol, 2-isopropyl-1-naphthol, 5-isopropyl-3,S-dimethyl-l-naphthol, 2-butyl-l-naphthol, 4-butyl-1-naphthol, 4-t-butyl-1-naphthol, 2-sec.-butyl-l-naphthol, Z-isopentyl-l-naphthol, 2-phenyl-1-naphthol, 4-phenyl-l-naphthol, and 2,3-diphenyl-1-naphthol. 8. A composition of matter comprising an alkenylnorbornene or an alkylidenenorbornene and a stabilizing amount of at least one phenol of either one of the and wherein X and X are each alkylidene having 1 to 6 carbon atoms, cycloalkylidene having 3 to 6 carbon atoms,

$20-12, R11 is wherein R R R and R are each hydrogen or alkyl having 1 to 6 carbon atoms.

10. A composition of matter in accordance with claim 8, wherein the alkylidenenorbornene has the formula:

wherein R2 R and R are each hydrogen or alkyl having 1 to 6 carbon atoms.

11. A composition of matter in accordance with claim 8, wherein the stabilizing amount of phenol in said composition is from 20 ppm. to 3000 p.p.m.

12. A composition of matter in accordance with claim 8, wherein the stabilizing amount of phenol in said composition is from 20 p.p.m. to 500 p.p.m.

References Cited UNITED STATES PATENTS 3,409,683 11/ 1968 Britton et a1. 260-6665 3,487,044 12/ 1969 Tholstrup 260-45.85 3,527,822 9/1970 Benson 260-6665 3,660,352 5/1972 Song 260-6665 DELBERT E. GANTZ, Primary Examiner J. M. NELSON, Assistant Examiner US. Cl. X.R. 260-666 A