Method of inhibiting rubber mixture premature vulcanization

专利摘要:
Thio-substituted-1,3,5-triazine-diamines and-triamines having the formula …<CHEM>… in which R min is hydrogen or -SR, X is hydrogen chloro, alkoxy of 1-5 carbon atoms, alkylthio of 1-5 carbon atoms, NHR sec , N(R sec )2 where R sec is R or alkyl, NHSR, N(SR)2 or R, and R is alkyl or 1-12 carbon atoms or alkyl substituted by cyano, acetoxy, or alkoxycarbonyl of 2-5 carbon atoms, aralkyl of 7-10 carbon atoms, cycloalkyl of 5-8 carbon atoms, phenyl, or phenyl suhstituted by chloro, alkyl of 1-5 carbon atoms, or alkoxy of 1-5 carbon atoms, are useful as prevulcanization inhibitors in vulcanizable rubber compositions.
公开号:SU1209036A3
申请号:SU823503160
申请日:1982-10-18
公开日:1986-01-30
发明作者:Морита Эйичи
申请人:Монсанто Компани (Фирма)；
IPC主号:

专利说明:

one
The invention relates to the rubber industry, in particular, to a method for inhibiting vulcanisation of a rubber compound.
The purpose of the invention is to improve the inhibition of scorching the mixture (based on styrene-butadiene SCS or natural NK).
The invention is illustrated by examples.
Example 1. To a stirred solution consisting of 0.1 mol of 1,3,5-triazin-2,4,6-triamine (melamine), about 0.7 mol of triethyl amine and 125 ml of acetonitrile, for Approximately 2 hours at room temperature, a solution of 0.6 mol of 2-propanesulfenyl chloride in 300 ml of toluene is slowly added. The resulting slurry is stirred for another 1 hour. The secondary amine hydrochloride is filtered and a small amount of unreacted melamine is filtered off. The solvents are then evaporated, and the residue is washed with ether, and digested with ethanol. After recrystallization from ethanol, N, N, N, N, N, N-hex-saquis (isopropylthio) -1,3,5-triazin-2 4,6-triamine with m.p. 151-152 ° C.
Found %: S 33.75; N 14.72.
Sl (3 (.
Calculated,%: S 33.69 N 14.22.
According to the IR spectrum, there are no NH groups. The NMR spectrum shows a shift of C “only at 173.37 parts per million in terms of TMS n O, which means that all nitrogen atoms are completely replaced.
Examples 2-5. The method is carried out as in example 1, however, the following sulfenyl chloride component is prepared and the following compounds are obtained. Since the nitrogen atoms of the amino group are completely substituted, in chemical names for the purpose of simplification, the indication of six substituents of nitrogen is omitted,
2. Hexakis (phenylthio) -1,3,5-triazin-2,4,6-triamine, mp 156-157 ° C.
. Found: S 24.71, - N 10.94. CjjHjoNgSg. Calculated,%: S 24.82, N 10.84.
3. Hexakis (cyclohexin-1Tio) -1,3,5-triazin-2,4,6-triamine., T. Pl. 145 C.
 Found: S 22.67, N 10.22.
CsjHjjNeSg.
Calculated,%: S 23.71, N 10.36.
. Hexacis (4-chlorophenylthio) -1,3,5-riazin-2,4,6-triamine.t.pl ..
090362
Found,%: S 19.27. Cs Ng. ClNgSfi. Calculated,%: S 19,59.
5. Hexakis (4-methylphenylthio) -1,3,5-5 triazin-2,4,6-triamine, m.p. .
Found%: S 22.41.
1 С „5 HVL Nt Se
10, Calcd.,%: S 22.47.
Examples 6-13. These examples illustrate the preparation of 1,3,5-triazine-2,4-diamine derivatives by the reaction of sulfenyl chloride with
15 1,3,5-triazin-2,4, -diamine, 6-chloro--1,3,5-triazin-2,4-diamine, 6-phenyl--1,3,5-triazin-2, 4-diamine, 6- (diallylamino) -1,3,5-triazin-2,4-diamine or 6-methoxy-1,3,5-triazine-2,420-diamine. The method according to example 1 leads to the formation of a mixture of reaction products, from which it is possible to isolate the corresponding N, Ы -di (thio) - and N, N, N, N-tetra (thio) -derivatives.
25 Reaction temperatures of 100 or less, as well as an excess of the acid acceptor, contribute to the formation of the tetra-substituted product, while temperatures, 25 ° C reactions and the above contribute to the formation of the disubstituted product. Thus, the following compounds are obtained.
6.N, N, N, N -Tetra (phenylthio) - -1,3,5-triazin-2,4-diamine, mp. 117 C
Found,%: 323.81. CnHjiNjS. Calculated,%: S 23.58.
35
7. N, N
N
N-Tetra (phenylthio)
-6-methoxy-1,3,5-triazin-2,4-diamine, so pl. 140-141 s.
Found,% :. S 22.24.
 Si ,. Calculated,%: S 22.35.
8.N, N, N, N-Tetra (phenylthio) -6-phenyl-1,3,5-triazin-2,4-diamine, m.p. 112-113 ° C.
Found%: S 21, 17. SzzYgb-Y V. Calculated,%: S 20,69.
9.N, N-Di (phenylthio) -6-phenyl-1,3, 5-triazin-2,4-diamine, m.p. 183-1 85 p.
Found,%: S 16.61; N 17.38. C h N5 S g Calculated,%: S 15.89, N 17.35. 10.N, N-Di (phenylthio) -6-chloro-1,3,5-triazin-2,4-diamine, m.p.1b7 C (with different).
Found%: S 16.61. Ci5 H, 2 ClNsSj.
Calculated,%: S 17.72. 11.N, N-Di (cyclohexylthio) -6-chloro-1, 3,5-triazin-2,4-diamine, mp.183.
Found,%: S 17.24.
 Hj ClNsS ,.
Calculated,%: S 17.15. 12.N N -Di (isopropylthio) -6-chloro--1,3,5-triazin-2,4-diamine, m.p. 139 ° C
Found%: S 22.50.
Cj H, 6ClNsS.
Calculated,%: S 21, 81. 13.N, N, N, N -Tetra (isopropylthio) -b-chloro-1,3,5-triazin-2,4-diamine, mp, 97-98 C.
Found,%: S 28.50.
 Hjg ClNg Si ,.
Calculated,%: S 29.01.
Example 14. 0.2 mol of benzene-sulfenyl chloride in toluene at 10 ° C is slowly added to the solution consisting of 0.05 mol of N, N-diallyl--1,3,5-triazine-2,4,6-triamine , 0.22 moles of triethylamine and 100 ml of acetonitrile. The solids are filtered. The filtrate is then washed with water and dried with anhydrous sodium sulfate, filtered and distilled under vacuum to give 33.0 g of N, N-di- (allyl) -N, N, N, N-tetra (phenylthio) -1, 5- triazine-2,4,6-triamine with m.p.106.
Found,%: S 20.42.
sz b b Calculated,%: S 20,07.
Uterine mixtures of natural (natural β-CN) and styrene-butadium new-scs rubbers containing these components are prepared using conventional mixing methods. Control is the proportion of uterine mixtures that do not contain the inhibitor. A certain amount of the inhibitor is introduced into other lobes of the masterbatch. In addition, a vulcanization accelerator and sulfur are also introduced in order to form curable compositions. The properties of the vulcanizable compositions and vulcanizates are measured by known methods as described above. The Mooney (Moopeu) scorch time is determined at the indicated temperatures. Wu Canisates are obtained by vulcanization at 153 ° C. The time required to achieve optimum volcanoes
209036
the value is determined in accordance with the data of the plastometer. As the vulcanization accelerator used was N (t -butyl) -2- benzt iazolsulfenil- 5 amide (Santokur® NS, Cantocure® NS, benztiazolildisulfid (Tiofid ,, ® Thiof ide®), tetrametiltiuramdisul- feed (Tiurad, ® Thiurad®) and iinkdi - methyldithiocarbamate (Metasan®, Metha-JQ san, as an activator of volcanic-nadia — diphenylguanidine (DFG), and as an antioxidant — N- (1,3-dimethylbutythyl) -N — phenyl-paraphenylene-diamine (Santoflex®, Santoflex., 5 All of these products are registered trademarks of Monsanto Company and the results are shown in Tables 1-6.
Given in Table. 1-5, the 2Q data indicates that the proposed compounds are effective scavenger inhibitors and increase the resistance to scorching of the curable compositions containing these 25 compounds. In addition, they are effective in formulations that contain a vulcanizing system consisting of benzthiazyl disulfide and diphenylguanadine. Effective inhibitors are those that contain six groups of SR-additives30
dinene to the nitrogen atom dineni).
(.hexakiss table
Components, 35 ma.ch
The content of masterbatches, mach.
Smoked xits (NC) 100 SBR -1500 (SCS)
Gazov 40 soot
naphthenic oil - zircosol (Circosol) for filling rubber in the latex stage 10 Zinc oxide 5 Stearic acid 1 Wax 2
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2.5 2.5 2.5
1.0 1.0 1.0 0.1 0.21 0.41
tj MIN
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Impairment of cheek resistance.
eleven
Compiled by L.Reutova Editor M.Nedoluzhenko Tehred M.Nad Corrector G.Reshetnik
Order 311/62 Circulation .471 Subscription VNIIPI USSR State Committee
for inventions and discoveries 113035, Moscow, Zh-35, Raushsk nab., 4/5
Branch PPP Patent, Uzhgorod, st. Project, 4
Table 6 Composition and properties of mixtures
five
2

2.5
1.0 1.66
5.0 6.4
16.0 31.5
14
45
264
616

权利要求:
Claims (2)
[1]
1-2
1.3.5- triazine-2,4,6-triamine 'hexa (isopropylthio) -1, 3,5-triazine-
2.4.6-triamine, 'goksakis (4-chlorophenylgio) -1,3 ”5-triazine-2,4,6-triamine; hex; akis (4-methylphenylthio) -1,3,5-triazin-2, 4,6-triamine; hexakis (phenylthio) -1,3,5-triazine-2,4,6-triamine J Ν, Ν -di (cyclohexylthio) -6-chloro-1,
3.5- triazine-2,4-diamine; H, S, Ф, Ν-tetra (phenylthio) -1, 3,5-triazine-2,4-diamine Ν, Ν -di (phenylthio) -6-chloro-1 , 3,5triazin-2,4-diamine} N, N -di (phenylthio) -6-phenyl-1,3,5-triazine-2,4-diaμηη; Ν, Ν, Ν, Ν ^1- tetra (phenylthio ) -1,3,5 triazine-2,4-diamine; Ν, Ν -di (allyl) Ν *, N ', Ν, Ν ^Μ -tetra (phenylthio) -1,3,5-triazine-2,4,6-triamine', Ν, Ν, Ν ', Ν - tetra (phenylthio) -6-methoxy-1,3,5-triazine-2,4-diamine (Ν, Ν ¹ -di (cyclohexylthio) -6-chloro-1,3,5-triazine-2,4-dia - min; Ν, Ν, Ν, Ν '-' tetra (phenylthio) -6-phen-SS nyl-1,3,5-triazine-2,4-diamine N, Ν 'di (isopropylthio) -6-chloro 1,3,5-triazine-2,4-diamine; Ν, Ν, Ν, Ν'-tetra (isopropylthio) -6-chloro-1,3,5-triazin-2,
4.6- triamine;
in the following ratio of components, wt.H .:
Natural or styrene butadiene rubber Soot gas
Naphthenic oil
Zinc Oxide Stearic Acid
Sulfur
Vulcanization accelerator
Specified Inhibitor
SU „„ 1209036
100
40-50
3-12 'Σ-5' '
[2]
2.0-2.5
0.5-1.2 '0.1-1.66

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引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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US3382219A|1966-01-10|1968-05-07|Monsanto Co|Inhibiting pre-vulcanization of rubber with thioamines of phenylenediamine or dihydroquinoline|

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US3473667A|1968-01-08|1969-10-21|Monsanto Co|Certain n-thio-2-imidazolidinones|

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US3640976A|1970-03-09|1972-02-08|Monsanto Co|Certain cycloalkylsulfenamides as prevulcanization inhibitors|

---

US3817742A|1971-05-12|1974-06-18|Chevron Res|Substituted triazines|

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US4301260A|1980-05-12|1981-11-17|Monsanto Company|Vulcanizable rubber compositions scorch inhibited by 2--4,6-diamino-1,3,5-triazines|

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US4339577A|1980-05-12|1982-07-13|Monsanto Company|2--4,6-diamino-1,3,5-triazines|DE3610811A1|1986-04-01|1987-10-08|Degussa|USE OF SUBSTITUTED N-TRICHLORMETHYLTHIODICARBOXIMIDES IN COMBINATION WITH N; N'-SUBSTITUTED BIS--OLIGOSULFIDES IN VULCANIZABLE RUBBER RUBBERS|

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DE3610796A1|1986-04-01|1987-10-08|Degussa|USE OF SUBSTITUTED N-TRICHLORMETHYLTHIOHYDANTOINES IN COMBINATION WITH BIS--OLIGOSULFIDES IN VULCANIZABLE RUBBER BLENDS AND THESE RUBBER BLENDS|

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US6063873A|1997-12-31|2000-05-16|Bridgestone Corporation|Process to scavenge amines in polymeric compounds by treatment with triazine derivatives, and compositions therefrom|

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US6235819B1|1997-12-31|2001-05-22|Bridgestone Corporation|Process to scavenge amines in polymeric compounds by treatment with triazine derivatives and compositions therefrom|

法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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US06/312,572|US4380609A|1981-10-19|1981-10-19|Prevulcanization inhibitors of thio-triazine-amines for rubber|

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