RU2044001C1 - POLY-N-VINYLPHENYL-β-NAPHTHYLAMINE - Google Patents

Abstract

FIELD: organic chemistry. SUBSTANCE: product: poly-N-vinylphenyl-b-naphthylamine of the general formula

Description

 The invention relates to the production of poly-N-vinyl-phenyl-β-naphthylamine, which can be used in the production of stabilized compositions for various purposes.

It is known that phenol antioxidants, for example, 2 ¹ , 2 ^1- methylene-bis-6-tert-butyl-4-methylphenyl), amino-containing antioxidants, for example phenyl-β-naphthylamine, are used as a thermal stabilizer of polyolefins.

 However, due to the low molecular weight, stabilizers are prone to sweating out of the polymer, especially during processing, and thus do not provide him with the level of necessary stability.

 A known method of producing poly-N-alkenyldiphenylamines by the interaction of diphenylamine and aliphatic aldehydes in the presence of anhydrous magnesium perchlorate.

 However, the oligomer based on phenyl-β-naphthylamine with a linear structure cannot be obtained due to the strong resinification of the product.

 The purpose of the invention is the synthesis of a new oligomer having a stabilizing effect, devoid of these disadvantages.

The goal is achieved in that the obtained poly-N-β-naphthylamine vinilfenil- (PVFNA) by reacting phenyl-β-naphthylamine viniliruyuschim agent such as vinyl butyl ether, in the presence of boron trifluoride etherate catalyst at 20-40 ° ^C.

PRI me R 1. In a three-necked flask equipped with a reflux condenser, a mechanical stirrer and a thermometer load of 10.3 g (0,047 M / phenyl-β-naphthylamine, analytical grade GOST 39-79 dissolved in 50 ml of acetone, was added 0.4 mL of boron trifluoride etherate (8% phenyl-β-naphthylamine) and gradually added with stirring 10 ml (0.078 mol) vinyl butyl ether (TU 6-09-39-37-75). Synthesis was carried out ^at 40 ° C. within 3 hours. The reaction is monitored chromatographically (TLC, silofol, benzene: hexane: chloroform 6: 3: 1). The reaction is carried out until the phenyl-β-naphthyl stain disappears completely. after the completion of the reaction, the cooled solution is poured into 300 ml of methanol (ethanol), the precipitated precipitate of the oligomer is filtered off, washed with alcohol until the phenyl-β-naphthylamine stain disappears, 8.6 g (75%) of a white (pinkish) oligomer are obtained with T _pl 130-150 ^о С. ММ1200 (cryoscopy, naphthalene). It is highly soluble in most organic solvents. Elemental analysis:
Found, C 88.72; H 6.98; N, 5.05.

Calculated, C 88.16; H, 6.12; N, 5.7 (C ₁₈ H ₁₅ N).

IR (UR-20, CCl ₄ ): 1600, 1500 cm ^-1 (C arom), 710-760 cm ^-1 (CH arom), 3400 cm ^-1 (NH).

где n 3-4.The IR spectra of oligomers contain bands characterizing the presence of a free amino group and substitution along aromatic rings. The content of NH-groups in the oligomer molecule is 20%. The degree of polymerization is n 3-4. From this it follows that the synthesized oligomer has the following structure:

where n is 3-4.

 PRI me R 2. Obtaining poly-N-vinyl-phenyl-β-naphthylamine.

In a three-necked flask equipped with a reflux condenser, a mechanical stirrer and a thermometer, 21.9 g (0.1 M) of phenyl-β-naphthylamine and 35 ml (0.6 M) of acetaldehyde are charged. After the phenyl-β-naphthylamine is completely dissolved in acetaldehyde in small portions, 3.3 g (0.015 M) of anhydrous magnesium perchlorate are added in the first 5 minutes. The synthesis was carried out at 20-25 ° ^C. Monitoring of the reaction is carried out by chromatography (TLC Silufol, benzene: hexane: chloroform 6: 3: 1). The reaction is carried out until the phenyl-β-naphthylamine stain on the chromatogram completely disappears, and the reaction time is about 2 hours. At the end of the reaction, a viscous mass of polymer is dissolved in 200 ml of acetone and ethanol: water is precipitated in 2.5 l of the mixture (3: 1 ) The precipitate formed is filtered off, washed on the filter with the same aqueous-alcoholic mixture. It obtained 16.4 g (66.6%) of polymer with a _{melting point} of 128-138 ^{° C} and a molecular weight of 1100.

PRI me R 3. According to the method described in example 2, from 6.57 g (0.03 M) of phenyl-β-naphthylamine and 9 ml (0.15 M) of acetaldehyde, 1 g (0.0045 M ) anhydrous magnesium perchlorate in 2 hours receive 5.2 g (71%) of an amorphous powder with T _PL 120-140 ^about C and a molecular weight of 1200. The synthesis is carried out in argon.

 Thus, the proposed methods allow to obtain poly-N-vinyl-β-naphthylamine with a yield of 70-80% In table. 1 shows the reaction conditions and characteristics of the obtained oligomers.

 Poly-N-vinyl-phenyl-β-naphthylamine is a pale pink powder with a molecular weight of 1100-1200, has good solubility in most organic solvents. The oligomer does not contain an impurity of phenyl-β-naphthylamine; it combines well with polyolefins.

 PVFNA was used as a thermal stabilizer of polyolefins in the following ratio of components, wt. polyolefin 99.5-99.8; PVFNA 0.2-0.5.

EXAMPLE EXAMPLE 4. The composition based on high density polyethylene (HDPE) was prepared by mixing 1000 g of LDPE with 2 g (0.2 wt.) PVFNA on rollers at 160 ^C. Evaluation was carried out by the stabilizing effect of a change in mechanical properties in test process, tensile yield strength (σ _RT , Pa): tensile strength (σ _pp , Pa): elongation at break (ε), melt flow rate (MFR, g / 10 min) and dielectric loss tangent tan δ ^. 10 ⁴ according to GOST 1.6337-77.

 The results are presented in table. 2.

 PRI me R s 5-6. Compositions based on LDPE are prepared and tested analogously to Example 4; 0.1 and 0.3 wt.% Are added to the stabilizer. (tab. 2).

 PRI me R 7 (prototype). LDPE-based compositions are prepared and used analogously to Example 4, but phenyl-β-naphthylamine is added as a stabilizer (Table 2).

PRI me R s 8-11. Compositions were prepared based on poly-4-methylpentene-1 (PMP), which contain PVFNA as a heat stabilizer. The polymer with the additive is mixed in a high-speed mixer at room temperature for 10 minutes. The mixture was then extruded on a single screw extruder with chervyachkovom ratio of length to diameter of screw of 20: 1 at temperatures 270-260-150 ^{° C} in zones. From the granules at 220-240 ^{° C} and a pressure of 1000 kg / cm cast discs of 1 mm thick. Evaluation of the stabilizing effect is carried out by measuring the melt flow rate (MFR) during fivefold extrusion and the time of disk oxidation at 150 ^about C (table. 3).

 PRI me R 12. Prepared and tested compositions based on PMP analogously to example 8, but as thermostabilizing additives used phenyl-β-naphthylamine (prototype).

PRI me R s 13-18. Compositions based on polypropylene was prepared by mixing (polypropylene and a heat stabilizer) in a high-speed mixer at room temperature for 10 min followed by extrusion on a single screw extruder at chervyachkovom temperatures 170-160-150 ^{° C} in the zones of the cylinder. Evaluation of additives stabilizing steps were carried out by measuring the melt flow index in the process of extrusion and five times by the destruction of the plates of 1 mm thickness at 150 ° ^C (tab. 4).

 The additive stabilizer in the composition of less than 0.2 wt. does not provide the necessary thermal stability to the polymer, and more than 0.5 wt. it is not economically feasible, since with increasing concentration, the stabilization effect increases slightly.

 From the above table. 2, 3, 4 of the data shows that the proposed composition based on polyolefins containing PVFNA as thermostabilizer in stability is 7 or more times superior to the compositions prepared according to the prototype.

Claims (1)

POLY-N-VINYLPHENYL-β-NAPHTHILAMINE of general formula

where n = 3,4.

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