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US3830860A - Stabilization of norbornenes - Google Patents

Stabilization of norbornenes Download PDF

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Publication number
US3830860A
US3830860A US00327125A US32712573A US3830860A US 3830860 A US3830860 A US 3830860A US 00327125 A US00327125 A US 00327125A US 32712573 A US32712573 A US 32712573A US 3830860 A US3830860 A US 3830860A
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US
United States
Prior art keywords
naphthol
norbornene
carbon atoms
phenol
methyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US00327125A
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English (en)
Inventor
T Nagase
F Masuko
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/20—Use of additives, e.g. for stabilisation

Definitions

  • the present invention relates to a method for stabilization of norbornenes, particularly alkenylnorbornenes and alkylidenenorbornenes.
  • norbornenes are very useful as one of the termonomers in the production of elastomers with ethylene and propylene (hereinafter referred to as EPDM).
  • EPDM ethylene and propylene
  • 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.
  • 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.
  • alkenylnorbornenes of the formula:
  • R R R and R are each hydrogen or alkyl having 1 to 6 carbon atoms and alkylidenenorbornenes of the formula:
  • R R and R are each hydrogen or alkyl having 1 to 6 carbon atoms.
  • alkenylnorbornenes [A] are as follows:
  • alkylidenenorbornenes [B] are as follows:
  • 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.
  • 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.
  • 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.
  • EXAMPLE 8 buy p
  • 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,
  • 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.
  • a method for stabilization of norbornenes which comprises incorporating at least one phenol of either one of the formulae:
  • alkenylnorbornenes are those of the formula:
  • alkylidenenorbornenes are those of the formula:
  • R R and R are each hydrogen or alkyl having 1 to 6 carbon atoms.
  • 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.
  • 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
  • R11 is wherein R R R and R are each hydrogen or alkyl having 1 to 6 carbon atoms.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Water Supply & Treatment (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
US00327125A 1972-01-27 1973-01-26 Stabilization of norbornenes Expired - Lifetime US3830860A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP47010383A JPS5235666B2 (it) 1972-01-27 1972-01-27

Publications (1)

Publication Number Publication Date
US3830860A true US3830860A (en) 1974-08-20

Family

ID=11748591

Family Applications (1)

Application Number Title Priority Date Filing Date
US00327125A Expired - Lifetime US3830860A (en) 1972-01-27 1973-01-26 Stabilization of norbornenes

Country Status (7)

Country Link
US (1) US3830860A (it)
JP (1) JPS5235666B2 (it)
DE (1) DE2303883C3 (it)
FR (1) FR2169351B1 (it)
GB (2) GB1403455A (it)
IT (1) IT977687B (it)
NL (1) NL173392C (it)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4294712A (en) * 1979-08-29 1981-10-13 Bando Chemical Industries, Ltd. Self-lubricating bearing

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4880548A (it) * 1972-02-03 1973-10-29
JPS5857682U (ja) * 1981-10-15 1983-04-19 三菱電機株式会社 冷凍冷蔵庫
JPH02247478A (ja) * 1989-03-17 1990-10-03 Mitsubishi Electric Corp 冷凍冷蔵庫

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1225899A (fr) * 1958-03-12 1960-07-06 Ethyl Corp Composés thio-biphénoliques et leur procédé de préparation
US3043775A (en) * 1959-07-24 1962-07-10 Thomas H Coffield Organic material containing a 4, 4'-methylenebis phenol
US3100229A (en) * 1960-04-01 1963-08-06 Ethyl Corp Sulfur bridged cyclohexyl phenols
GB1168053A (en) * 1968-07-09 1969-10-22 Union Carbide Corp Stabilization of Alkylidenebicycloheptenes

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4294712A (en) * 1979-08-29 1981-10-13 Bando Chemical Industries, Ltd. Self-lubricating bearing

Also Published As

Publication number Publication date
DE2303883B2 (de) 1981-01-15
NL173392B (nl) 1983-08-16
FR2169351A1 (it) 1973-09-07
JPS4878153A (it) 1973-10-20
JPS5235666B2 (it) 1977-09-10
DE2303883C3 (de) 1981-09-03
IT977687B (it) 1974-09-20
DE2303883A1 (de) 1973-08-02
NL7300966A (it) 1973-07-31
FR2169351B1 (it) 1976-04-09
NL173392C (nl) 1984-01-16
GB1403455A (en) 1975-08-28
GB1403456A (en) 1975-08-28

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