前苏联专利SU1526582A3 Method of producing substituted bis-(alkylthiomethyl)-phenols

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专利摘要:
1. Claims for the Contracting States : BE, CH, DE, FR, GB, IT, LI, NL A composition containing an elastomer or a tackifying resin and at least one compound of formula I see diagramm : EP0224442,P14,F2 wherein R1 is C1 -C8 alkyl or C5 -C12 cycloalkyl, the radicals R2 , each independently of the other, are C1 -C18 alkyl groups which are unsubstituted or substituted by 1 or 2 hydroxyl groups or by -OCO-R4 , -CO-OR5 or -CO-NR5 R6 , or they are phenyl or benzyl, R3 is hydrogen or methyl, with the proviso that, if R1 is other than methyl, then R3 is methyl, R4 is C1 -C17 alkyl, C2 -C8 alkenyl or a radical of formula Ia see diagramm : EP0224442,P14,F3 m is 0, 1 or 2, the radicals R', each independently of the other, have the meanings indicated for R1 , R5 is C1 -C20 alkyl which may be interrupted by -O-, -S- or -NR'-, and R6 is hydrogen or has one of the meanings indicated for R5 . 1. Claims for the Contracting States : ES A composition containing an elastomer or a tackifying resin and at least one compound of formula I see diagramm : EP0224442,P15,F2 wherein R1 is C1 -C8 alkyl or C5 -C12 cycloalkyl, the radicals R2 , each independently of the other, are C1 -C18 alkyl groups which are unsubstituted or substituted by 1 or 2 hydroxyl groups or by -OCO-R4 , -CO-OR5 or -CO-NR5 R6 , or they are phenyl or benzyl, R3 is hydrogen or methyl, with the proviso that, if R1 is other than methyl, then R3 is methyl, R4 is C1 -C17 alkyl, C2 -C8 alkenyl or a radical of formula Ia see diagramm : EP0224442,P15,F3 m is 0, 1 or 2, the radicals R', each independently of the other, have the meanings indicated for R1 , R5 is C1 -C20 alkyl which may be interrupted by -O-, -S- or -NR'-, and R6 is hydrogen or has one of the meanings indicated for R5 .
公开号:SU1526582A3
申请号:SU874203506
申请日:1987-10-23
公开日:1989-11-30
发明作者:Майер Ганс-Рудольф；КНОБЛОХ Геррит
申请人:Циба-Гейги Аг (Фирма)；
IPC主号:

专利说明:

The invention relates to methods for producing new substituted bis (alkylthiomethyl) phenols of the general formula
CHg-S-Ri I
l 2 5 1
where R is the same unbranched or branched alkyl with 8-12 carbon atoms, phenyl or benzyl,
which can be used as stabilizers of polymers, as well as synthetic oils.
The invention is the development of a process for the preparation of new substituted bis (alkylthiomethyl) phenols, which would have a more B1) 1 high stabilizing effect than the known, for example, 2,6-bis (three-butyl) -4-phenylthiomethyl (II) or 2,4-bis- (p-dodecylthiomethyl) -3,6-dimethylphenol (III).
Example 1. Getting 2,4-bis- (p-octylthiomethyl) -6-methylphenol (compound 1).
160.74 g (0.72 mol) of 2,4-bis- (dimethylaminomethyl) -6-methylphenol and 210.65 g (1.44 mol) of p-octanethiol are heated for 36 hours at 150 ° C in an apparatus with stirrer and intensive fridge, and with
ate yu
O5
cl
ace to
cm
53.2 bar dimethyl amine is continuously removed. 291.6 g (95%) of a yellow oil are obtained. Pure 2,4-bic- (n-octylthiomethyl) -6-methyphenol is obtained by column chromatography of the crude product on silica gel as a colorless oil.
Calculated,%: C, 70.69; H 10.44; S 15.09.
Found,%: C 70.85; H 10.42;
S 15.11.
And (CI) Clj; 100 MHz: data in 8 (m, d.), Correlated to TMS O, s - singlet): characteristic signals for Ar-CH S at 3.77 (s) and 3.8 (s).
In a similar manner, compounds of the formula I are prepared, presented in that bl. one .
Compounds 1 and 2 of Example 1 are tested for their stabilizing effect.
Example 2. Stabilization of polybutadiene rubber (aging in a kiln).
100 g of polybuta diene, which is pre-stabilized with 0.4% 2,6-di-tert-butyl-p-cresol, is mixed with 0.25% of the test compound on a mixing roll at 50 ° C for 6 minutes until homogeneous. Plates 10 mm thick are pressed from the product of rolling at 80 ° C. Another plate is prepared in the same way without a stabilizer.
The proposed compositions are aged by heating in an oven with air circulation at 80 ° C. The criterion is the appearance during the aging in the oven of the gel. This is determined as follows.
1 g of polybutadiene is dissolved in 100 ml of toluene overnight at room temperature. The solution is filtered through a glass filter (pore size 00) and the filtered solution is evaporated.
The gel content is determined by
formula gel --- x 100%
ll
where E is the sample (1 g).
A is the weight of the residue after insertion.
The gel content is increased by the induction period field. As an arbitrary definition of the induction period is the time after which the gel content of 2% is reached. This induction time is determined by periodic determination of the gel content. Thus, in the absence of a stabilizer, the induction time is 21 days, and with compound 2, the production time is 77 days.
Example 3. Stabilization of polybutadiene rubber (Brabender).
100 hours of polybutadiene, which is pre-stabilized with 0.4% 2,6-di-tert-butyl-p-cresol, is mixed with an additional 0.25% of the test stabilizer in a Brabender plastograph at 160 C and at 60 rpm in for 30 minutes From the course of the torque curve, the induction time is determined, i.e. mixing time (plasticization) in minutes up to the increase of the rotating moment by 100 tr after the minimum of the rotating moment.
The results are as follows:
25
Stabilizer
I
Induction time, min
Example 4. Absorption Test
5 oxygen in a thin film.
This test is a modified version of the oxidation test in a rotating bomb for mineral oils. As a test oil, a mineral oil-based motor oil is used, containing half the standard amount of zinc dithiophosphate (0.75%, zinc content 0.06% per motor oil).
5 Compound 1 is tested in engine oil in the presence of 2% water, a liquid, oxidized, nitrated fraction of motor gasoline as a catalyst (concentration 4%), liquid naphtha Nata metal as another catalyst. The test ends when the pressure-time chart is clearly broken.
A long time corresponds to a good stabilizing activity. 0.5% stabilizer concentration in oil.
In the absence of a stabilizer, a clear pressure drop was observed after 85 minutes; with Compound 1, after 134 minutes.
Example 5. Stabilizing a hydrogenated hydrocarbon resin (oven aging).
50 g of a resin that has been pre-stabilized with 0.15% 2,6-di-tert-butyl-p-cresol is melted in a glass flask at 170 ° C and 0.1% of the compound 1 is stirred in with stirring for 15 minutes Aluminum cups and Petri dishes are then filled with hot melt. The thickness of the layer of solidified resinous mass in aluminum cups is about 15 mm, and in petri dishes - 1 mm. The proposed composite is subjected to aging when heated in an oven with 1 air spin at 170 C. As a criterion, color change during aging in the oven serves as a criterion. It is determined in the following way: in the case of a sample of 1 mm yellowness index according to ASTM D 1925-70; in the case of samples in 15 mm, (Jardner-color according to DIN 6161.
Higher numbers mean a stronger color change.
The results are presented in Table B. 2
Example 6. Stabilization of polybutadiene rubber (aging in silicone oil).
100 g of polybutadiene, pre-stabilized with 0.4% 2,6-di-tert-butyl-p-cresol, are mixed to homogeneity with 0.1% of compound 3 in a two-roll roller machine for 6 minutes at 50 ° WITH. From the product of rolling, the plates with a thickness of 2 mm are pressed at 90 ° C. The obtained sample is aged by immersion in silicone oil and kept in this oil for 30 minutes at 160 ° C. The criterion for stabilizing action is undesirable gel formation during the aging process. The gel content is determined as follows.
After termination of the aging process, the sample is dissolved overnight at room temperature in 100 ml of toluene. The solution is passed according to the test ASTM E 11. t 400, through a sieve, and the residue is thoroughly washed and dried.
The gel content is determined as follows:
Gel, 100%
where f ,. - weight of the filter with gel; FO — filter weight without gel; E - the weight of the sample before the test
After 30 min at TbO C (Test, James), the measurement is 2.0% gel. In comparison with this, the sample with 0.1% compound 2 contains 3.2% gel.
Stabilization of polybutadiene rubber (Brabender, yellowing index determination).
70 g of polybutadiene, previously stabilized with 0.3% 2,6-di-tert-butyl-p-cresol, is mixed with 0.1% of compound 3 in the Nrabender plastograph at 60 rpm for 30 minutes at 160 with. Then the mixture is homogenized in a roller machine, and plates of a thickness of 2 mm are pressed from the product of rolling. The yellowness index of the sample (VI) is determined according to ASTM D 1925. After 30 minutes at 160 ° C, the yellowness index is determined 16. Compared to this, the sample with 0.1% of compound 2 has a yellowness index 19. The lower the yellowness index, the better stabilizing effect.
Example 7. TOST test (Mineral Oil Oxidation Characteristics Mobile 150 SS4).
The TOST test was performed according to ASTM D 934 as follows. The test oil in the presence of water, oxygen, a ferro-ice catalyst and 0.25% by weight of one of these compounds is heated to 95 ° C for 500 hours. Acidity and sludge are then determined. The values obtained indicate an oxidative breakdown of the oil. - Low values mean a low degree of decomposition. The results are shown in Table. 3

权利要求:
Claims (1)
[1]
Invention Formula
I
The method of obtaining the substituted bis- (alkylthiomethyl) -phenols of the general formula I
CHj-S-Rj
CH2-S-Rj
where are the same unbranched
or branched Cd-C, -alkyl, phenyl or benzyl,
characterized in that 2,4-bis- (dimethylaminomethyl) -6-methylphenol is reacted with mercartan of the general formula
R, -SH, where RJ 1 is greater than the indicated values.
Priority featured:
11/13/85 - the same unbranched or branched alkyl,
09/24/86 - the same unbranched or branched Cd-C, α-kil, phenyl or benzyl.
Table 1
ConnectionR, Characteristic
2n-2n T, 28 C
99-100 ° C / Liquid
5-С (СНз) -СН, -С (СН,) -СН2 -) {liquid-С (СН}),
6-С (СНз) 2-СН, g-С (СН,) h; Kidkoye
I
table 2
Stabilizer Index yellowing at 170 ° C. Gardner-coloring at 170 ° C after a while, after which time, h
О 12 30О 1 12 30
No 366126159
Connection 1361211-23--4
I
Table 3
500 hTOST stabilizer
Acidity, Sludge, mg mg KOH / g oil
Connection 1 0,1662
Compound 2 0.143
Connection 3 21000
Compiled by T.Vlasova Editor M.Tsitkina Tehred.Hodanich Proofreader S.Kravtsova
Order 7250/59 Circulation 352Subscription
VNIIPI State Committee for Inventions and Discoveries at the State Committee on Science and Technology of the USSR 113035, Moscow, Zh-35, Raushsk nab. 4/5
Production and publishing plant Patent, Uzhgorod, st. Gagarin, 101

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同族专利:

公开号 | 公开日

CA1289147C|1991-09-17|

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ES2014433B3|1990-07-16|

AU6517186A|1987-05-21|

CN1026107C|1994-10-05|

MX9202733A|1992-06-30|

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US2332376A|1941-02-28|1943-10-19|Stackpole Carbon Co|Method of making insulated resistors|

US3114713A|1959-07-24|1963-12-17|Ethyl Corp|Sulfur-containing phenolic compounds|

US3250712A|1959-07-24|1966-05-10|Ethyl Corp|Sulfur-containing phenolic compounds|

US3060121A|1960-04-04|1962-10-23|Ethyl Corp|Antioxidants|

US3227667A|1960-09-21|1966-01-04|Borden Co|Lignin, phenol, and aldehyde condensation process and product|

US3227677A|1962-01-02|1966-01-04|Phillips Petroleum Co|Polyolefins containing bis phenols as stabilizers|

DE1593821B1|1967-03-17|1971-08-05|Advance Prod Gmbh|Process for the preparation of dialkyl hydroxybenzyl sulfides|

US3903173A|1967-03-17|1975-09-02|Ciba Geigy Ag|Lower alkylthiomethylene containing phenols|

US3504012A|1967-04-07|1970-03-31|Nat Distillers Chem Corp|Hydroxyethyl-beta- alkanoate|

US3637863A|1967-11-22|1972-01-25|Nat Distillers Chem Corp|3 5-di-t-butyl-4-hydroxybenzyl phenyl sulfides|

US3590085A|1969-07-22|1971-06-29|Nat Distillers Chem Corp|3,5-di-t-butyl - 4 -hydroxybenzylthio-2,3-dihydroxypropane and the methyl and ethyl ethers thereof|

US3699152A|1969-12-10|1972-10-17|Carlisle Chemical Works|Sulfur containing esters of substituted hydroxyphenyl-alkanoic acids|

US3660352A|1970-06-04|1972-05-02|American Cyanamid Co|Hindered phenol sulfide antioxidants for polymers|

GB1331494A|1970-06-24|1973-09-26|British Oxygen Co Ltd|Evaporation system|

US4108831A|1975-06-02|1978-08-22|The Goodyear Tire & Rubber Company|Hydroxyalkylthio phenolic antioxidants|

DE2614875C2|1976-04-06|1978-06-15|Bayer Ag, 5090 Leverkusen|Process for the production of alkyl or arylthiomethylphenols|

DE2901837A1|1978-01-27|1979-08-02|Sandoz Ag|ORGANIC COMPOUNDS|

US4356616A|1980-02-25|1982-11-02|Rockwell International Corporation|Method of making rib structures for an airfoil|

EP0165209B1|1984-06-12|1989-07-19|Ciba-Geigy Ag|O,p-bifunctionalised, o'-substituted phenols|US4874885A|1986-12-24|1989-10-17|Ciba-Geigy Corporation|Process for the preparation of mercaptomethylphenols|

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US20080305055A1|2004-12-22|2008-12-11|Werner Baschong|Anti-Radical Agents|

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法律状态:

优先权:

申请号 | 申请日 | 专利标题

CH487185|1985-11-13|

CH382886|1986-09-24|

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