- hydroxy -3,5di-tert - butylbenzaldehyde as a stabilizer chain polymers
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(2-n, n-diethylaminoethyl)-4- hydroxy -3,5di-tert - butylbenzaldehyde as a stabilizer chain polymers

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IPC classes for russian patent (2-n, n-diethylaminoethyl)-4- hydroxy -3,5di-tert - butylbenzaldehyde as a stabilizer chain polymers (RU 2026859):
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(57) Abstract:

The invention relates to substituted bansilalpet, in particular (2-N,N-diethylaminoethyl) -4-hydroxy-for 3,5-di-tert-butylbenzaldehyde, which can be used as stabilizers chain polymers. Goal - the creation of new and more efficient connection of the specified class. Synthesis of lead by the reaction of Mannich bases of 2-Diethylaminoethanol at 120 - 130°C. with distillation of the excess aminothiol at 2 mm RT.article Yield 98%; mol.m. 346. The use of new substances in quantities of 1 wt.% in rubber SKS-30 AMIS provides a higher index of preserving the ductility in terms of thermal aging at 140°C for 30 min with 94 up to 96.9%. 2 Il., 6 table.

The invention relates to the field of production of stabilizers and protection chain polymers from aging.

Well-known and widely used different types of stabilizers to protect polymers from aging from a number of phenols, amines and sulfur compounds [1] . To obtain malaekahana or unpainted rubbers are widely used substituted phenols, such as 4-tert-octyl-2,6-di-tert-butylphenol (stabilizer Wangsta T, the firm "Goodyear") [2], 4 nonyl-2,6-di-tert-butylphenol (stabilizer VS-30A).

the tori phenolic number, hence their use in high dosages, leading to increased labor costs for their production and to a large consumption of reagents;
phenolic stabilizers are volatile, so a lot of them are lost in the production of rubbers;
phenolic stabilizers perform in the production of rubbers only one function - the protection of polymers against heat aging. They are not coagulants rubbers, so in the production of IC additionally spent coagulant - sodium chloride in the amount of 250 kg/ton of rubber. Astrotheme environmental issues require exceptions specified coagulant from rubber production.

Know the use of polyhexamethyleneguanidine (metacid) to improve the stability of the rubber under heat aging [3]. However, rubbers obtained by the use of metacid, have a high gel content.

The purpose of the invention is the obtaining of the stabilizer, with high efficiency protection of polymers from aging, have low volatility, which at the same time the rubber coagulant and paleocristiano rubber.

This goal is achieved using (2-N,N-diethylaminoethyl)-4I-hydroxy-3
The compound of formula (I) are not described in literature. It has the following advantages:
has a simple way to obtain;
has a high efficiency of the stabilizing action at low dosage of 0.5-2.0 kg per 1 ton of rubber;
possesses low volatility;
at the same time is a coagulant in the allocation of emulsion rubbers that allows you to completely eliminate the use of salt and eliminate or significantly reduce the use of protein coagulants in the production of rubbers;
the product is small stains rubbers;
is an individual product;
has a convenient product form is an oily liquid with low viscosity.

New stabilizer can be used both independently and in a mixture with known stabilizers of a number of amines, substituted phenol, phosphorus, proteins, polyamines.

The specified connection is produced by processing dialkylaminomethyl industrial 2,6-di-tert-butyl-4-dimethyl - aminomethylphenol (base manniche, THE 37.103368-87) or by condensation of dialkylaminomethyl with industrial 2,6-di-tert-butylphenol and formaldehyde. Dialkylaminomethyl are also available products. Rea is minoritie and Mannich bases of 1-2:1, respectively, or when the molar ratio of the substituted thiol, formaldehyde and 2,6-di-tert-butylphenol 1-2:1-1,5:1.

Dosage of stabilizer in the polymer depends on the nature of the polymer and the task and may be in the range of 0.05-3%.

The invention is illustrated by the following examples.

P R I m e R 1. In a three-neck flask equipped with a reflux condenser and a thermometer, loads of 53.6 g (0.2 mol) of Mannich bases (TU 38.103368-87) and 29.2 g (0.22 mol) of 2-Diethylaminoethanol (Catalog Handbook of Fine Chemicals, Aldrich Chemical Co. 1986-1987, R. 465; Sigma Price List, 1987, p. 508).

The reaction mixture is heated at 120-130aboutC for 5 h and evaporated the excess 2-diethylaminoethylamine in vacuum at 2 mm RT.article In the flask remains the finished product, representing an oily thin transparent mass laboratore color, yield 98%.

The compound obtained is a (2-N,N-diethylaminoethyl)-4I-hydroxy-3I,5Idi-tert-butylbenzaldehyde - product of the Navy-80.

Found, %: C 72,1; H 10,4; N 4,1; S 8,8.

Mol.weight 346.

Calculated, %: From 71.8; H 10,5; N 4,0; S 9,1.

Mol. mass 351.

The refractive index (nD20equal GBPUSD crossed over 1.5100.

PMR - spectrum (see Fig. 1) is cleared on the NMR spectrometer EM-390 "Varian" work is where curve 1 - the basis of manniche; 2 - g-30A, 3 - Wangsta T; 4-Navy-80) was determined by the method [4]. The test temperature 100aboutC. the Disks of filter paper impregnated with solutions of antioxidants, kept at the test temperature and determined the loss of these compounds during a certain time.

The proposed stabilizer Navy-80 has a lower volatility compared with stabilizers SU-30A, Winsteam T and the base of manniche. So, after 30 min of the test is lost only 5% of product weight Navy-80, and products all-30A, Winglee T and the base of manniche lost 65, 62, 5, and 79 wt.% respectively.

P R I m m e R 2. Mix 29,2 g (0.22 mol) of 2-Diethylaminoethanol, 22 g (0.22 mole on formaldehyde) 30%-aqueous solution of formaldehyde, and then the mixture is added in by 41.2 g (0.2 mol) of 2,6-di-tert-butylphenol. The reaction is carried out at 100aboutC for 6 hours Receive a product of the Navy-80 exit 61%.

P R I m e R 3. To examine the effectiveness to stabilize polymers against aging used method of determining the stability of the rubber index save plasticity (SP) [5], and also assessed the effect of stabilizers on the gel content in the rubber by the method of [4].

In the best choice latex rubber-30A, Winglee T, Mannich bases, Navy-80 and metacid. Rubber produce coagulation of the latex with sodium chloride acidification with 1% sulfuric acid solution. Crumb rubber is washed and dried in a drying Cabinet at 60aboutC. the Dried polymer is subjected to tests under heat aging at 140aboutC for 30 min followed by the measurement of the index of conservation of plasticity (COI) on a fast plastometer Wallace and the determination of the gel content in the rubber.

The results of the tests are presented in table. 1.

P R I m e R 4. The experiments are performed according to example 3 of the description, using oil-filled rubber SKS-ARKM-15.

After separating and drying the rubber is tested for stability against heat aging at 140aboutC for 30 min, followed by measurement of COI on plastometer Wallace.

The results are given in table. 2.

P R I m e R 5. The experiments are performed according to example 3, using the best choice and methylsterols latex rubber SKS-ARKM-27 (-methylstyrene) SCMS-ARK. The results of tests of rubber on the stability under heat aging are presented in table. 3.

From the results table. 2 and 3 shows that the resistance to thermal starane the Cove, seasoned stabilizers by Winsteam T, base, manniche, SU-30 and received using metacid.

P R I m e R 6. The experience is conducted according to example 3 description using on BNR latex rubber BOC-ANK.

The rubber was isolated calcium chloride, washed, dried and tested for stability under heat aging at 140aboutC for 2 h with subsequent determination of COI and gel formation in the rubber. The results of the tests are presented in table. 4.

P R I m e R 7. In polybutadiene rubber SKD enter a variable number of the investigated stabilizers (Wangsta T, the basis of manniche, SU-30A and Navy-80). Rubber allocate water degassing, washed with water and dried in a drying Cabinet at 60aboutC. the Finished polymer is subjected to heat aging at 140aboutC for 60 min and then determine the COI and the gel formation in the rubber. The results are shown in table. 5.

P R I m e R 8. In the best choice latex rubber stamps SCS-ARK and SCS-ARKM-15 enters a different dosing Navy-80, Winglee T, the basis of manniche and SU-30A and produce rubber with protein coagulant Navy-100A [6] upon acidification with 1% sulfuric acid solution.

Obtained the olanta, required for full selection of rubber latex, and the stability of the rubber to heat ageing.

Presented in table. 6 the results show that the product of the Navy-80 is simultaneously effective stabilizer and rubber coagulant, while the other studied compounds (Wangsta T, the basis of manniche and SU-30A) have only one function stabilization of rubbers and are not coagulants. Moreover, the COI rubbers dressed proposed stabilizer Navy-80, significantly higher than for rubbers dressed these products. The dosage of the Navy-80, 0.05 and 0.1% rubber consumption of protein coagulant Navy-100A decreased in 4 and 10 times, respectively, and at a dosage of 0.2% on the polymer Navy-80 rubber was distinguished with the addition of only one acid.

Thus, the obtained results confirm the possibility of excluding additional coagulants (NaCl and protein products) from the process of obtaining emulsion rubbers with the application of the proposed stabilizer Navy-80.

In comparison with the known stabilizer - metaldom - offer (Navy-80) allows to obtain resins with greater resistance to heat aging (significantly reduced the content of gel in caacupe POLYMERS.

(2-N,N-diethylaminoethyl)-4'-hydroxy-3',5'-di-tert-butylbenzaldehyde formula
as a stabilizer chain polymers.

 

 

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