CA2029708C - Stabilizer mixtures for elastomers - Google Patents
Stabilizer mixtures for elastomers Download PDFInfo
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- CA2029708C CA2029708C CA002029708A CA2029708A CA2029708C CA 2029708 C CA2029708 C CA 2029708C CA 002029708 A CA002029708 A CA 002029708A CA 2029708 A CA2029708 A CA 2029708A CA 2029708 C CA2029708 C CA 2029708C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5393—Phosphonous compounds, e.g. R—P(OR')2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/375—Thiols containing six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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Abstract
Novel compositions which contain an elastomer and a stabilizer mixture which consists of a) 2,4-bis(n-octylthiomethyl)-6-methylphenol, and b) at least one compound from the group consisting of tris(4-nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, 3,9-bis(stearyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5)undecane, tetrakis(3-dodecylthio-propionyioxymethyl)methane, bis[(3-(n-tridecyloxycarbonyt)ethyl]mercaptan, 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2,4-di-tert-butyl-6-phenylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]-undecane; are described.
Description
2~~~'~~~
A-17828 +
Stabilizer mixtures for elastomers The present invention relates to compositions containing an elastomer and a stabilizer mixture which consists of a bis-(alkylthiomethyl)-phenol and at least one P-or S-containing compound.
Alkylthiomethyl-containing phenols in mixtures with P- and/or S-containing compounds are known as stabilizers for elastomers. A 4-component mixture is thus described, for example, in EP-A-049,133. It consists of a diphenylamine, a triphenyl phosphite, a dialkylthio dipropionate and at least one alkylphenol or bisphenol, for example bis-(4-hydroxybenzyl) thioether.
A 3-component mixture for elastomers is known from US-A-3,658,743. It consists of a phenol or bisphenol, as mentioned previously in EP-A-049,133, an organic sulfide or dialkylthio dialkanoate and an epoxide or phosphite, for example a triphenyl phosphite.
A 2-component mixture consisting of a phenol and a phosphite is described in DE-A-2,334,163. The stabilizer mixture contains, for example, 2,6-dialkyl-substituted 4-(alkyhnercaptomethyl)phenol as the phenolic component and 4-alkyl- or 2,4-dialkyl-substituted triphenyl phosphite.
US-A-3,637,585 furthermore discloses a 2-component mixture which contains an alkylmercaptomethylphenol in which the alkyl radical carries two alkoxycarbonyl substituents, and a dialkylthio alkanoate.
The alkylthiomethyl-containing phenols themselves are likewise known as stabilizers for elastomers. Thus, for example, 2,4-bis-(mercaptomethyl)-6-alkylphenols are described as particularly active stabilizers in EP-A-0,165,209.
However, there continues to be a need for active stabilizers for elastomers which are sensitive towards oxidative degradation.
~~~)~'~~8 The present invention thus relates to a composition containing an elastomer and a stabilizer mixture of a) a phenol of the formula I
OH
Rt ~ CH2-S-R2 (I>>
and b) at least one compound of the formulae IIa, IIb and III to VI
C(CH3y3 C9Htg ~ ~ O P
(CHg)gC ~ ~ O P
A-17828 +
Stabilizer mixtures for elastomers The present invention relates to compositions containing an elastomer and a stabilizer mixture which consists of a bis-(alkylthiomethyl)-phenol and at least one P-or S-containing compound.
Alkylthiomethyl-containing phenols in mixtures with P- and/or S-containing compounds are known as stabilizers for elastomers. A 4-component mixture is thus described, for example, in EP-A-049,133. It consists of a diphenylamine, a triphenyl phosphite, a dialkylthio dipropionate and at least one alkylphenol or bisphenol, for example bis-(4-hydroxybenzyl) thioether.
A 3-component mixture for elastomers is known from US-A-3,658,743. It consists of a phenol or bisphenol, as mentioned previously in EP-A-049,133, an organic sulfide or dialkylthio dialkanoate and an epoxide or phosphite, for example a triphenyl phosphite.
A 2-component mixture consisting of a phenol and a phosphite is described in DE-A-2,334,163. The stabilizer mixture contains, for example, 2,6-dialkyl-substituted 4-(alkyhnercaptomethyl)phenol as the phenolic component and 4-alkyl- or 2,4-dialkyl-substituted triphenyl phosphite.
US-A-3,637,585 furthermore discloses a 2-component mixture which contains an alkylmercaptomethylphenol in which the alkyl radical carries two alkoxycarbonyl substituents, and a dialkylthio alkanoate.
The alkylthiomethyl-containing phenols themselves are likewise known as stabilizers for elastomers. Thus, for example, 2,4-bis-(mercaptomethyl)-6-alkylphenols are described as particularly active stabilizers in EP-A-0,165,209.
However, there continues to be a need for active stabilizers for elastomers which are sensitive towards oxidative degradation.
~~~)~'~~8 The present invention thus relates to a composition containing an elastomer and a stabilizer mixture of a) a phenol of the formula I
OH
Rt ~ CH2-S-R2 (I>>
and b) at least one compound of the formulae IIa, IIb and III to VI
C(CH3y3 C9Htg ~ ~ O P
(CHg)gC ~ ~ O P
(aa) (IIb) _ / ~ \ _ R4 P\ /P R4 O O ' (III) C(CH3 C(CHg)3 (CH3~aC ~ ~ O p ~ ~ ~ ~ p p ~ ~ C(CHg)3 s ~/ 2 (IV) * Isomer mixture of Nonyl ~~~~'~~8 _3-CH2CH2-COORS CFi2-OOC-CH2CH2-S-RS
S~ ~ CH2-OOC-CH2CH2-S-RS
nr ~ CH2-OCR-CH2CH2-S-RS
CH2CH2-C;OORg CH2_ppC-CH2CH2-S-RS
cv) cvn in which Rt is Ct-C4alkyl, the radicals R2 independently of one another are C8-Cl2alkyl groups, R3 is hydrogen or methyl, R4 is C18H3~-O- or one of the groups IIIa or IIIb C(CHgY3 C(CHgy3 (CH3y3C ~ O CH3 ~ ~ O - , and C(CH3y3 (IIIa) (IIIb) Rg is Ct2-Clsalkyl.
Ct-C4alkyl Rt is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or t-butyl. Rt is preferably methyl or t-butyl.
C8-Ct2alkyl RZ is, for example, n-octyl, 2-ethylhexyl, n-decyl, 1,1,3,3-tetramethylbutyl, 1,1,3,3-tetramethylhexyl, n-undecyl, n-dodecyl or 1,1,3,3,5,5-hexamethylhexyl.
R2 is preferably n-octyl or n-dodecyl.
Ct2-CtBalkyl RS can be straight-chain or branched and is, for example, n-dodecyl, n-tridecyl, n-tetradecyl, 1,1,3,3-teuamethyloctyl, 2-ethylhexyl, 1,1,3,3,5,5-hexamethylhexyl, 1,1,5,5,9,9-hexamethyldecyl, n-hexadecyl or n-octadecyl. RS
is preferably n-dodecyl, n-tridecyl, n-tetradecyl or n-octadecyl.
Compositions in which Rt is methyl or t-butyl are preferred.
Compositions in which the radicals R2 are n-octyl or n-dodecyl are particularly preferred.
Compositions in which R4 is ClgHg~-O- are furthermore of interest.
z~J~~~s Compositions in which RS is n-dodecyl, n-tridecyl, n-tetradecyl or n-octadecyl are likewise of interest.
Compositions which are of particular importance are those in which in component a) Rl is methyl, R2 is n-octyl and R3 is hydrogen, and especially in which in component b) R4 is C18H37-O- or RS is n-dodecyl or n-tridecyl, or in which a compound of the formula IIa or IIb is employed as component b).
Examples of representatives of compounds of the formula I are the substances listed below:
2,4-bis(n-oetylthiomethyl)-6-methyl-phenol 2,4-bis(t-octylthiomethyl)-6-methyl-phenol, l 2,4-bis(t-dodecylthiomethyl)-6-methyl-phenol, 2 2,4-bis(n-octyl-thiomethyl)-3,6-dimethyl-phenol, 2,4-bis(2'-ethylhexylthiomethyl)-6-t-butyl-3-methyl-phenol, 2,4-bis(n-octylthiomethyl)-6-t-butyl-phenol, 2,4-bis(n-dodecylthiomethyl)-6-t-butyl-phenol, 2,4-bis(n-octylthiomethyl)-6-t-butyl-3-methyl-phenol, 2,4-bis(n-dodecylthiomethyl)-6-t-butyl-3-methyl-phemol.
Examples of representatives of compounds of the formulae II to VI are the following structures:
C(CH3)3 (CH3)3C ~ ~ O P C9H19 ~ ~ O P
O O
n-C1gH37 '-O- P\ ~P -' O' n-C18H37 O O
1 t-octyl is 1,1,3,3-tetramethylbutyl 2 t-dodecyl is a mixture of 1,1,3,3,5,5-hexamethylhexyl and 1,1,4,6,6-pentamethylhept-(4)-yl _S_ C(CHg)3 C (CH3)~
O O
\
(CH3~C ~ ~ O ~ p\ p -.~ O C(CH3)3 O ~_ O
C(CHg)3 C(CH3)3 O O
CH3 ~ ~ O _ p' \p _ O / \ CH3 O
C(CH~y3 C(CH3)~
C(CH3)3 C(CH3)3 (CH3)3C ~ ~ O p ~ ~ ~ ~ - p _ O ~ ~ C(CH3)3 CH2CH2-COO-n-C12H25 ~ _'H2CH2-COO-n-C13H27 CH2CH2-COO-n-C12H25 \CH2CH2-COO-n-ClgFi27 CH2CH2-COO-Ci4H29 /CH2CH2-COO-C1gH37 S S
CH2CH2-COO-Ci4H29 \CH2CH2-COO-C1gH37 CH2-COO-CH2CH2-S-C12H25 CH2-COO-CH2CH2-S-C18H~7 ~CH2-COO-CH2CH2-S-C12H25 ~CH2-COO-CH2CH2-S-Ci8H~7 CH2-COO-CH2CH2-S-C12N25 ~ CH2-COO-CH2CH2-S-CigH37 CH2-COO-CH2CH2-S-C12H25 CH2-C(~-CH2C'.H2-S-CigH37 -5a-According to one aspect of t:he present invention, there is provided a composition containing a.n elastomer and a stabilizer mixture of a) 2,4-bi.s(ra-octylth.iomethyl)-6-methylphenol, and b) at least one compound from the group consisting of tris(,4-nonylphenyl)phosphi.te, tris(2,4-di-tert-butylphenyl)phosphite, 3,9-bis(~;t~earyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, tetrakis(3-dodecylthio-propionyloxymethyl ) methane, bis [(3- (n-tridecyloxycarbonyl)ethyl]mercaptan, 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and 3,9-bis(2,4-di-tert-butyl-6-phenylphenoxy)-2,4,8,10-tet.raoxa-~,9-diphosphaspiro[5.5]-undecane.
The compositions according to the invention can, for example, contain the following mat:ezials as elastomers:
1. Polydienes, for exam~>le polybutadiene, polyisoprene or polychloroprene; and block polymers, f:or example styrene/butadiene/styrene, styrene/isoprene/styrene and acrylonitrile/butadiene copolymers or styrene/butadiene copolymers.
2~fl?~'~~)~
2. Copolymers of mono- and diolefins with one another or with other vinyl monomers, for example etlhylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers and terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidenenorbornene.
3. Halogen-containing polymers, for example polychloroprene, chlorinated rubber, chlorinated or chlorosulfonated polyethylene, epichlorohydrin homo- and copolymers, chlorotrifluoroethylene copolymers and polymers of halogen-containing vinyl compounds, for example polyvinylidene chloride and polyvinylidene fluoride; and copolymers thereof, such as vinyl chloride-vinylidene chloride, vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate.
4. Polyurethanes which are derived on the one hand from polyethers, polyesters and polybutadiene having terminal hydroxyl groups and on the other hand from aliphatic or aromatic polyisocyanates, and intermediates thereof.
S~ ~ CH2-OOC-CH2CH2-S-RS
nr ~ CH2-OCR-CH2CH2-S-RS
CH2CH2-C;OORg CH2_ppC-CH2CH2-S-RS
cv) cvn in which Rt is Ct-C4alkyl, the radicals R2 independently of one another are C8-Cl2alkyl groups, R3 is hydrogen or methyl, R4 is C18H3~-O- or one of the groups IIIa or IIIb C(CHgY3 C(CHgy3 (CH3y3C ~ O CH3 ~ ~ O - , and C(CH3y3 (IIIa) (IIIb) Rg is Ct2-Clsalkyl.
Ct-C4alkyl Rt is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or t-butyl. Rt is preferably methyl or t-butyl.
C8-Ct2alkyl RZ is, for example, n-octyl, 2-ethylhexyl, n-decyl, 1,1,3,3-tetramethylbutyl, 1,1,3,3-tetramethylhexyl, n-undecyl, n-dodecyl or 1,1,3,3,5,5-hexamethylhexyl.
R2 is preferably n-octyl or n-dodecyl.
Ct2-CtBalkyl RS can be straight-chain or branched and is, for example, n-dodecyl, n-tridecyl, n-tetradecyl, 1,1,3,3-teuamethyloctyl, 2-ethylhexyl, 1,1,3,3,5,5-hexamethylhexyl, 1,1,5,5,9,9-hexamethyldecyl, n-hexadecyl or n-octadecyl. RS
is preferably n-dodecyl, n-tridecyl, n-tetradecyl or n-octadecyl.
Compositions in which Rt is methyl or t-butyl are preferred.
Compositions in which the radicals R2 are n-octyl or n-dodecyl are particularly preferred.
Compositions in which R4 is ClgHg~-O- are furthermore of interest.
z~J~~~s Compositions in which RS is n-dodecyl, n-tridecyl, n-tetradecyl or n-octadecyl are likewise of interest.
Compositions which are of particular importance are those in which in component a) Rl is methyl, R2 is n-octyl and R3 is hydrogen, and especially in which in component b) R4 is C18H37-O- or RS is n-dodecyl or n-tridecyl, or in which a compound of the formula IIa or IIb is employed as component b).
Examples of representatives of compounds of the formula I are the substances listed below:
2,4-bis(n-oetylthiomethyl)-6-methyl-phenol 2,4-bis(t-octylthiomethyl)-6-methyl-phenol, l 2,4-bis(t-dodecylthiomethyl)-6-methyl-phenol, 2 2,4-bis(n-octyl-thiomethyl)-3,6-dimethyl-phenol, 2,4-bis(2'-ethylhexylthiomethyl)-6-t-butyl-3-methyl-phenol, 2,4-bis(n-octylthiomethyl)-6-t-butyl-phenol, 2,4-bis(n-dodecylthiomethyl)-6-t-butyl-phenol, 2,4-bis(n-octylthiomethyl)-6-t-butyl-3-methyl-phenol, 2,4-bis(n-dodecylthiomethyl)-6-t-butyl-3-methyl-phemol.
Examples of representatives of compounds of the formulae II to VI are the following structures:
C(CH3)3 (CH3)3C ~ ~ O P C9H19 ~ ~ O P
O O
n-C1gH37 '-O- P\ ~P -' O' n-C18H37 O O
1 t-octyl is 1,1,3,3-tetramethylbutyl 2 t-dodecyl is a mixture of 1,1,3,3,5,5-hexamethylhexyl and 1,1,4,6,6-pentamethylhept-(4)-yl _S_ C(CHg)3 C (CH3)~
O O
\
(CH3~C ~ ~ O ~ p\ p -.~ O C(CH3)3 O ~_ O
C(CHg)3 C(CH3)3 O O
CH3 ~ ~ O _ p' \p _ O / \ CH3 O
C(CH~y3 C(CH3)~
C(CH3)3 C(CH3)3 (CH3)3C ~ ~ O p ~ ~ ~ ~ - p _ O ~ ~ C(CH3)3 CH2CH2-COO-n-C12H25 ~ _'H2CH2-COO-n-C13H27 CH2CH2-COO-n-C12H25 \CH2CH2-COO-n-ClgFi27 CH2CH2-COO-Ci4H29 /CH2CH2-COO-C1gH37 S S
CH2CH2-COO-Ci4H29 \CH2CH2-COO-C1gH37 CH2-COO-CH2CH2-S-C12H25 CH2-COO-CH2CH2-S-C18H~7 ~CH2-COO-CH2CH2-S-C12H25 ~CH2-COO-CH2CH2-S-Ci8H~7 CH2-COO-CH2CH2-S-C12N25 ~ CH2-COO-CH2CH2-S-CigH37 CH2-COO-CH2CH2-S-C12H25 CH2-C(~-CH2C'.H2-S-CigH37 -5a-According to one aspect of t:he present invention, there is provided a composition containing a.n elastomer and a stabilizer mixture of a) 2,4-bi.s(ra-octylth.iomethyl)-6-methylphenol, and b) at least one compound from the group consisting of tris(,4-nonylphenyl)phosphi.te, tris(2,4-di-tert-butylphenyl)phosphite, 3,9-bis(~;t~earyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, tetrakis(3-dodecylthio-propionyloxymethyl ) methane, bis [(3- (n-tridecyloxycarbonyl)ethyl]mercaptan, 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and 3,9-bis(2,4-di-tert-butyl-6-phenylphenoxy)-2,4,8,10-tet.raoxa-~,9-diphosphaspiro[5.5]-undecane.
The compositions according to the invention can, for example, contain the following mat:ezials as elastomers:
1. Polydienes, for exam~>le polybutadiene, polyisoprene or polychloroprene; and block polymers, f:or example styrene/butadiene/styrene, styrene/isoprene/styrene and acrylonitrile/butadiene copolymers or styrene/butadiene copolymers.
2~fl?~'~~)~
2. Copolymers of mono- and diolefins with one another or with other vinyl monomers, for example etlhylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers and terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidenenorbornene.
3. Halogen-containing polymers, for example polychloroprene, chlorinated rubber, chlorinated or chlorosulfonated polyethylene, epichlorohydrin homo- and copolymers, chlorotrifluoroethylene copolymers and polymers of halogen-containing vinyl compounds, for example polyvinylidene chloride and polyvinylidene fluoride; and copolymers thereof, such as vinyl chloride-vinylidene chloride, vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate.
4. Polyurethanes which are derived on the one hand from polyethers, polyesters and polybutadiene having terminal hydroxyl groups and on the other hand from aliphatic or aromatic polyisocyanates, and intermediates thereof.
5. Natural rubber.
6. Mixtures (polyblends) of the abovementioned polymers.
7. Aqueous emulsions of natural or synthetic rubbers, for example natural rubber latex or latices of carboxylated styrene/butadiene copolymers.
If appropriate, these elastomers are in the form of latices and can be stabilized as such.
Compositions which contain a polydiene, such as polybutadiene rubber, a halogenated polymer, such as polyvinylidene fluoride, or a polyurethane as the elastorner are preferred.
Compositions which contain polybutadiene rubber as the elastomer are particularly preferred.
The compositions according to the invention advantageously contain 0.01-10 %
by weight of the stabilizer mixture of a) and b), based on the elastomer, in particular O.OS-5.0, for example 0.05-3 and especially 0.1-2 % by weight: Mixtures of stabilizers of the formula I
and/or of the formulae II to VI can likewise be employed. The ratio of the two components a) and b) to one another can vary within wide limits. The weight ratio a):b) is 2~?~'~~8 _7_ advantageously 9:1 to 1:9, for example 2:8 to 8:2 or 3:7 to 7:3. Preferred ratios are in the range from 2:1 to 1:2, in particular about 1:1 to 1:2.
The incorporation into the elastomers can be carried out, for example, by mixing in of the substances of the formulae I-VI and if appropriate further additives, for example vulcanization accelerators, fillers, plasticizers or pigments, by the methods customary in the art, before or during shaping, or by application of the dissolved or dispersed compounds to the polymer, if appropriate with subsequent evaporation of the solvent. The compounds of the formulae I-VI can also be added to the plastics to be stabilized in the form of a masterbatch which contains these compounds, for example, in a concentration of 2.S to 25 % by weight.
The compounds of the formulae I-VI are prepared by methods which are known per se, such as are described, for example, in EP-A-0,165,209 and in US-A-3,227,677 in respect of the formula I. However, they can also be obtained by reaction of a phenol of the formula Ia OH
(Ia) in which Rt and R3 have the abovementioned meaning, with formaldehyde or a compound which liberates formaldehyde under the reaction conditions and with at least one mercaptan Rz-SH in the presence of a base, the base being mono-, di- or trimethylamine or mono- or diethylamine.
All the starting substances are known compounds and can be prepared by known processes. Some of them are also commercially available.
The following examples illustrate the invention in more detail. Percentages and parts in the examples are percentages by weight and parts by weight.
2~~~'~4~8 PREPARA'I°ION EXAMPLES
Example 1: Preparation of 2,4-bis(n-octylthiomethyl)-6-methylphenol OH
CHg ~ CH2-S-n-CgHl7 CH2-S-n-C8H 17 160.74 g (0.72 mol) of 2,4-bis(dimethylaminomethyl)-6-methylphenol and 210.65 g (1.44 mol) of n-octanethioi are heated at 150°C in an apparatus having a stirrer and intensive cooler for 36 hours, dimethylamine being stripped off continuously under 53.2 bar.
291.6 g (95 %) of a yellow oil are obtained. Pure 2,4-bis(n-octylthiomethyl)-6-methylphenol is obtained as a colourless oil by column chromatography of the crude product on silica gel.
Analysis values:
Calculated 70.69 % C Found 70.85 % C
10.44%H 10.42%H
15.09%S 15.11%S
Example 2: Preparation of 2,4-bis(n-octylthiomethyl)-6-t-butylphenol OH
(CHgy3C / CH2-S-n-C8H17 CHZ-S-n-C8H17 A mixture of 22.5 g of 6-t-butylphenol, 18.0 g of parafozmaldehyde , 43.9 g of n-octanethiol, 4.0 g of 33 % ethanolic dimethylamine and 23 ml of N,N-dimethylformamide is refluxed under nitrogen in a sulfonating flask having a reflux condenser and mechanical stirrer for 3 hours. The internal temperature is 110°C. The 2~9~~'~~8 crude product is taken up in 150 ml of ethyl acetate and the mixture is washed with 100 ml of water. After evaporation of the organic phase to dryness, 51 g (97 % of theory) of 2,4-bis-(n-actylthiomethyl)-6-t-butyl-phenol are obtained as a colourless oil.
Analysis values:
Calculated: 13.74 % S
Found: 13.44 % S.
USE EXAMPLES
Example 3: Stabilization of polybutadiene rubber (silicone oil ageing) 100 g of polybutadiene which is prestabilized with 0.4 % of 2,6-di-t-butyl-p-cresol are mixed homogeneously with 0.15 % of stabilizer component a) and 0.3 % of stabilizer component b) on a mixing mill at 50°C for 6 minutes. Sheets 2 mm thick are pressed from the rolled hide at 80°C. Anather sheet without stabilizer is produced in the same manner.
The test specimens are aged by immersion in silicone oil at 160°C for 30 minutes. The criterion is the gel content at the end of ageing. The gel content is determined as follows:
After ageing, the sample is dissolved in 100 ml of toluene at room temperature. After 24 hours, the solution is filtered through a wire sieve (in accordance with ASTM
E 11 No.
400) and the residue is carefully washed and dried. The gel content is obtained from Fg - Fo Gel = x 100 (%) E
Fg = weight of the filter with the gel Fo = weight of the empty filter E = weight of the sample The results are summarized in the following Table 1.
~~,'~~'~~)8 - lo-Table 1 StabilizerStructure Gel content (%) None - 10.2 A 2,4-Bis(n-octylthiomethyl)-6-methylphenol2.4 B A + Tris(4-nonylphenyl) phosphite1.0 A + Tris(2,4-di-t-butylphenyl)p,g phosphite D A + 3,9-Bis(stearyloxy)-2,4,8,10-tetraoxa-1.1 3,9-diphosphaspiro[5,5]undecane E A + Tetrakis(3-dodecylthio-propionyl-0.4 oxymethyl)-methane F A + Bis[ (3 -(n-tridecyloxycarbonyl)ethyl]-1.2 mercaptan If stabilizer A in the above preparation example is replaced by 2,4-bis(n-octylthiomethyl)-6-t-butylphenol from Example 2, similarly good stabilization values are obtained with the analogous stabilizer combinations.
Example 4: Stabilization of polybutadiene rubber (silicone oil ageing) The experiment is carried out in a manner analogous to that described in Example 3, but the ageing takes place in silicone oil at 160°C for 45 minutes. The results are listed in the following Table 2.
2~~~'~~8 Table 2 StabilizerStructure Gel conten None 22.05 A 2,4-Bis(n-octylthiomethyl)-6-methylphenol3.75 C A + Tris(2,4-di-t-butylphenyl)2.30 phosphite G A + 3,9-Bis(2,4-di-t-butylphenoxy)-2.55 2,4,8,10-tetraoxa-3,9-diphosphaspiro-[5,5]undecane H A + 3,9-Bis(2,4-di-t-butyl-6-methylphenoxy-1.98 2,4,8,10-tetraoxa-3,9-diphosphaspiro-[5,5]undecane
If appropriate, these elastomers are in the form of latices and can be stabilized as such.
Compositions which contain a polydiene, such as polybutadiene rubber, a halogenated polymer, such as polyvinylidene fluoride, or a polyurethane as the elastorner are preferred.
Compositions which contain polybutadiene rubber as the elastomer are particularly preferred.
The compositions according to the invention advantageously contain 0.01-10 %
by weight of the stabilizer mixture of a) and b), based on the elastomer, in particular O.OS-5.0, for example 0.05-3 and especially 0.1-2 % by weight: Mixtures of stabilizers of the formula I
and/or of the formulae II to VI can likewise be employed. The ratio of the two components a) and b) to one another can vary within wide limits. The weight ratio a):b) is 2~?~'~~8 _7_ advantageously 9:1 to 1:9, for example 2:8 to 8:2 or 3:7 to 7:3. Preferred ratios are in the range from 2:1 to 1:2, in particular about 1:1 to 1:2.
The incorporation into the elastomers can be carried out, for example, by mixing in of the substances of the formulae I-VI and if appropriate further additives, for example vulcanization accelerators, fillers, plasticizers or pigments, by the methods customary in the art, before or during shaping, or by application of the dissolved or dispersed compounds to the polymer, if appropriate with subsequent evaporation of the solvent. The compounds of the formulae I-VI can also be added to the plastics to be stabilized in the form of a masterbatch which contains these compounds, for example, in a concentration of 2.S to 25 % by weight.
The compounds of the formulae I-VI are prepared by methods which are known per se, such as are described, for example, in EP-A-0,165,209 and in US-A-3,227,677 in respect of the formula I. However, they can also be obtained by reaction of a phenol of the formula Ia OH
(Ia) in which Rt and R3 have the abovementioned meaning, with formaldehyde or a compound which liberates formaldehyde under the reaction conditions and with at least one mercaptan Rz-SH in the presence of a base, the base being mono-, di- or trimethylamine or mono- or diethylamine.
All the starting substances are known compounds and can be prepared by known processes. Some of them are also commercially available.
The following examples illustrate the invention in more detail. Percentages and parts in the examples are percentages by weight and parts by weight.
2~~~'~4~8 PREPARA'I°ION EXAMPLES
Example 1: Preparation of 2,4-bis(n-octylthiomethyl)-6-methylphenol OH
CHg ~ CH2-S-n-CgHl7 CH2-S-n-C8H 17 160.74 g (0.72 mol) of 2,4-bis(dimethylaminomethyl)-6-methylphenol and 210.65 g (1.44 mol) of n-octanethioi are heated at 150°C in an apparatus having a stirrer and intensive cooler for 36 hours, dimethylamine being stripped off continuously under 53.2 bar.
291.6 g (95 %) of a yellow oil are obtained. Pure 2,4-bis(n-octylthiomethyl)-6-methylphenol is obtained as a colourless oil by column chromatography of the crude product on silica gel.
Analysis values:
Calculated 70.69 % C Found 70.85 % C
10.44%H 10.42%H
15.09%S 15.11%S
Example 2: Preparation of 2,4-bis(n-octylthiomethyl)-6-t-butylphenol OH
(CHgy3C / CH2-S-n-C8H17 CHZ-S-n-C8H17 A mixture of 22.5 g of 6-t-butylphenol, 18.0 g of parafozmaldehyde , 43.9 g of n-octanethiol, 4.0 g of 33 % ethanolic dimethylamine and 23 ml of N,N-dimethylformamide is refluxed under nitrogen in a sulfonating flask having a reflux condenser and mechanical stirrer for 3 hours. The internal temperature is 110°C. The 2~9~~'~~8 crude product is taken up in 150 ml of ethyl acetate and the mixture is washed with 100 ml of water. After evaporation of the organic phase to dryness, 51 g (97 % of theory) of 2,4-bis-(n-actylthiomethyl)-6-t-butyl-phenol are obtained as a colourless oil.
Analysis values:
Calculated: 13.74 % S
Found: 13.44 % S.
USE EXAMPLES
Example 3: Stabilization of polybutadiene rubber (silicone oil ageing) 100 g of polybutadiene which is prestabilized with 0.4 % of 2,6-di-t-butyl-p-cresol are mixed homogeneously with 0.15 % of stabilizer component a) and 0.3 % of stabilizer component b) on a mixing mill at 50°C for 6 minutes. Sheets 2 mm thick are pressed from the rolled hide at 80°C. Anather sheet without stabilizer is produced in the same manner.
The test specimens are aged by immersion in silicone oil at 160°C for 30 minutes. The criterion is the gel content at the end of ageing. The gel content is determined as follows:
After ageing, the sample is dissolved in 100 ml of toluene at room temperature. After 24 hours, the solution is filtered through a wire sieve (in accordance with ASTM
E 11 No.
400) and the residue is carefully washed and dried. The gel content is obtained from Fg - Fo Gel = x 100 (%) E
Fg = weight of the filter with the gel Fo = weight of the empty filter E = weight of the sample The results are summarized in the following Table 1.
~~,'~~'~~)8 - lo-Table 1 StabilizerStructure Gel content (%) None - 10.2 A 2,4-Bis(n-octylthiomethyl)-6-methylphenol2.4 B A + Tris(4-nonylphenyl) phosphite1.0 A + Tris(2,4-di-t-butylphenyl)p,g phosphite D A + 3,9-Bis(stearyloxy)-2,4,8,10-tetraoxa-1.1 3,9-diphosphaspiro[5,5]undecane E A + Tetrakis(3-dodecylthio-propionyl-0.4 oxymethyl)-methane F A + Bis[ (3 -(n-tridecyloxycarbonyl)ethyl]-1.2 mercaptan If stabilizer A in the above preparation example is replaced by 2,4-bis(n-octylthiomethyl)-6-t-butylphenol from Example 2, similarly good stabilization values are obtained with the analogous stabilizer combinations.
Example 4: Stabilization of polybutadiene rubber (silicone oil ageing) The experiment is carried out in a manner analogous to that described in Example 3, but the ageing takes place in silicone oil at 160°C for 45 minutes. The results are listed in the following Table 2.
2~~~'~~8 Table 2 StabilizerStructure Gel conten None 22.05 A 2,4-Bis(n-octylthiomethyl)-6-methylphenol3.75 C A + Tris(2,4-di-t-butylphenyl)2.30 phosphite G A + 3,9-Bis(2,4-di-t-butylphenoxy)-2.55 2,4,8,10-tetraoxa-3,9-diphosphaspiro-[5,5]undecane H A + 3,9-Bis(2,4-di-t-butyl-6-methylphenoxy-1.98 2,4,8,10-tetraoxa-3,9-diphosphaspiro-[5,5]undecane
Claims (5)
1. A composition containing an elastomer and a stabilizer mixture of a) 2,4-bis(n-octylthiomethyl)-6-methylphenol, and b) at least one compound from the group consisting of tris(4-nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, 3,9-bis(stearyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, tetrakis(3-dodecylthio-propionyloxymethyl)methane, bis [.beta.- (n-tridecyloxycarbonyl) ethyl] mercaptan, 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and 3,9-bis(2,4-di-tert-butyl-6--phenylphenoxy)-
2,4,8,10-tetraoxa-3,9-diphosphaspiro(.5.5]undecane.
2. The composition according t.a claim 1, in which the elastomer is a polydiene, a halogen-containing polymer or a polyurethane.
2. The composition according t.a claim 1, in which the elastomer is a polydiene, a halogen-containing polymer or a polyurethane.
3. The composition according to claim 1, in which the elastomer is polybutadiene rubber.
4. The composition according to any one of claims 1 to 3, containing 0.05-5.0% by weight of the stabilizer mixture of a) and b) based on the weight of the elastomer.
5. A process for stabilizing elastomers, which comprises (i) incorporating a mixture of components a) and b) defined in claim 1 into the elastomers, or (ii) applying said mixture to the elastomers.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH4089/89-9 | 1989-11-14 | ||
| CH408989 | 1989-11-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2029708A1 CA2029708A1 (en) | 1991-05-15 |
| CA2029708C true CA2029708C (en) | 2003-07-29 |
Family
ID=4269619
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002029708A Expired - Lifetime CA2029708C (en) | 1989-11-14 | 1990-11-09 | Stabilizer mixtures for elastomers |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0428973B1 (en) |
| JP (1) | JP3099127B2 (en) |
| KR (1) | KR0172941B1 (en) |
| BR (1) | BR9005755A (en) |
| CA (1) | CA2029708C (en) |
| CZ (1) | CZ284773B6 (en) |
| DE (1) | DE59009983D1 (en) |
| ES (1) | ES2081335T3 (en) |
| SK (1) | SK279833B6 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011031031A1 (en) * | 2009-09-10 | 2011-03-17 | Korea Kumho Petrochemical Co., Ltd. | Novel thio compounds and preparing method of the same |
| CN106905206A (en) * | 2017-03-03 | 2017-06-30 | 湘潭大学 | The preparation of 2 methyl 4,6 pairs (n-octyl sulfidomethyl) phenol |
| US11407720B2 (en) | 2017-11-17 | 2022-08-09 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Compounds having a stabilizing effect, method for producing said compounds, composition containing said stabilizing compounds, and uses of the compounds |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09208783A (en) * | 1996-01-31 | 1997-08-12 | Kureha Chem Ind Co Ltd | Vinylidene fluoride resin composition and molded product |
| US6843948B2 (en) | 1996-01-31 | 2005-01-18 | Kureha Chemical Industry Co., Ltd. | Vinylidene fluoride resin compositions and articles molded therefrom |
| US6512032B1 (en) | 1997-07-28 | 2003-01-28 | Kureha Chemical Industry Co., Ltd. | Vinylidene fluoride resin compositions and articles molded therefrom |
| GB2355463B (en) | 1999-10-18 | 2001-12-05 | Ciba Sc Holding Ag | Stabilisers for emulsion crude rubbers, synthetic latex and natural rubber latex |
| BRPI0912632B1 (en) * | 2008-05-15 | 2019-10-01 | Basf Se | COMPOSITION UNDERSTANDING ACRILONITRIL-BUTADIEN RUBBER IN RAW EMULSION, AND METHOD FOR STABILIZING AN ACRILONITRIL-BUTADIEN RUBBER IN RAW EMULSION |
| JP5278179B2 (en) * | 2009-06-09 | 2013-09-04 | 信越化学工業株式会社 | Adhesive composition, and adhesive sheet and coverlay film using the same |
| KR101146246B1 (en) * | 2009-12-17 | 2012-05-16 | 금호석유화학 주식회사 | Anti-oxidants for rubber and Synthetic rubber with thereof |
| US8729169B2 (en) | 2011-04-08 | 2014-05-20 | Korea Kumho Petrochemical Co., Ltd. | Synthetic rubber with anti-oxidants for rubber |
| KR101195233B1 (en) * | 2011-05-19 | 2012-10-29 | 금호석유화학 주식회사 | Heat resistant dopes for polymer resin and polymer resin composition comprising the same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0224442B1 (en) * | 1985-11-13 | 1990-05-16 | Ciba-Geigy Ag | Use of substituted phenols as stabilizers |
-
1990
- 1990-11-09 CA CA002029708A patent/CA2029708C/en not_active Expired - Lifetime
- 1990-11-12 EP EP90121610A patent/EP0428973B1/en not_active Expired - Lifetime
- 1990-11-12 ES ES90121610T patent/ES2081335T3/en not_active Expired - Lifetime
- 1990-11-12 DE DE59009983T patent/DE59009983D1/en not_active Expired - Lifetime
- 1990-11-13 SK SK5601-90A patent/SK279833B6/en not_active IP Right Cessation
- 1990-11-13 CZ CS905601A patent/CZ284773B6/en not_active IP Right Cessation
- 1990-11-13 BR BR909005755A patent/BR9005755A/en not_active IP Right Cessation
- 1990-11-14 KR KR1019900018383A patent/KR0172941B1/en not_active IP Right Cessation
- 1990-11-14 JP JP02308443A patent/JP3099127B2/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011031031A1 (en) * | 2009-09-10 | 2011-03-17 | Korea Kumho Petrochemical Co., Ltd. | Novel thio compounds and preparing method of the same |
| CN102574982A (en) * | 2009-09-10 | 2012-07-11 | 锦湖石油化学株式会社 | Novel thio compounds and preparing method of the same |
| RU2509762C2 (en) * | 2009-09-10 | 2014-03-20 | Корея Кумхо Петрокемикал Ко., Лтд. | Novel thio compounds and method for production thereof |
| CN102574982B (en) * | 2009-09-10 | 2014-08-13 | 锦湖石油化学株式会社 | Novel thio compounds and preparing method of the same |
| CN106905206A (en) * | 2017-03-03 | 2017-06-30 | 湘潭大学 | The preparation of 2 methyl 4,6 pairs (n-octyl sulfidomethyl) phenol |
| CN106905206B (en) * | 2017-03-03 | 2018-08-14 | 湘潭大学 | The preparation of bis- (n-octyl sulfidomethyl) phenol of 2- methyl -4,6- |
| US11407720B2 (en) | 2017-11-17 | 2022-08-09 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Compounds having a stabilizing effect, method for producing said compounds, composition containing said stabilizing compounds, and uses of the compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2029708A1 (en) | 1991-05-15 |
| JPH03177442A (en) | 1991-08-01 |
| KR0172941B1 (en) | 1999-03-30 |
| SK560190A3 (en) | 1999-04-13 |
| KR910009837A (en) | 1991-06-28 |
| CZ560190A3 (en) | 1998-11-11 |
| EP0428973B1 (en) | 1995-12-20 |
| EP0428973A1 (en) | 1991-05-29 |
| CZ284773B6 (en) | 1999-02-17 |
| BR9005755A (en) | 1991-09-24 |
| JP3099127B2 (en) | 2000-10-16 |
| ES2081335T3 (en) | 1996-03-01 |
| SK279833B6 (en) | 1999-04-13 |
| DE59009983D1 (en) | 1996-02-01 |
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