Method of obtaining polyphenylene ether ketone oxymate

FIELD: chemistry.

SUBSTANCE: described is a method of obtaining polyphenylene ether ketone oxymate, consisting in the interaction of dioxymate anions of 4,4'-diacetyldiphenyloxide with 4,4'-dihalogenbenzophenone at higher temperatures in the aprotonic dipolar solvent dimethylsulphoxide, characterised by the fact that the synthesis of polyphenylene ether ketone oxymate is carried out in two stages: at the first stage with the reaction of potassium dioxymate of 4,4'-diacetyldiphenyloxide with 4,4'-dichlorobenzophenone with a molar ratio of 1:0.5 and the concentration of a solution C=1 mol/l in terms of dioxymate for 1 hour at a temperature of 165°C in the presence of a solid powder-like KOH obtained is a dioxymate anion of the following structure -O-N=C(CH3)-C6H4-O-C6H4-C(CH3)=N-O-C6H4-CO-C6H4-O-N=C(CH3)-C6H4-O-C6H4-C(CH3)=N-O-, at the second terminating stage of the process a mixture of 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone and crushed and annealed K2CO3 in molar ratios of 0.5:0.005:0.15, counted per 1 mol of the initial diketoxime of 4,4'-diacetyldiphenyloxide, in a water-free DMSO, with an additional volume of the water-free DMSO being taken in such an amount that the concentration of the solution by each of the monomers at the second oligopolymer stage of the synthesis becomes equal to 0.5 mol/l, the total time of carrying out the reaction is 6 hours at a temperature of 165°C.

EFFECT: intensification, optimisation and cheapening of the process of obtaining polyphenylene ether ketone oxymate.

3 ex

 

The invention relates to a method for simple aromatic polyesters by the reaction of nucleophilic substitution in aprotic dipolar solvents (ADPR), particularly to a method of producing polymers containing in the main chain between the phenyl nuclei ether linkages, keto groups and ketoxime fragments.

Known polyphenylenevinylene by RF patent no.2466153 simple link:

[-O-N=C(CH3)-C6H4-O-C6H4- (CH3)=N-O-C6H4-CO-C6H4-]n

the viscosity of 0.4-0.5 DL/g, a molecular mass MW40800-51000.

It is obtained in anhydrous dimethyl sulfoxide (DMSO) in collaboration equimolar quantities (0.5 mol/l) 4,4'-diftorbenzofenon and potassium of dioxamate 4,4'-diacetyldiphenylurea at a temperature of 165°C. according to the following scheme:

The disadvantages of this method of production is the high cost 4,4'-diftorbenzofenon that affects the value of polyphenylenevinylene.

The objective of the invention is to intensify, optimization and reduce the process of getting polyphenylenevinylene based dihalogen-benzophenone (4,4'-dichloro - 4,4'-differenzierung) and potassium of dioxamate 4,4'-diacetyldiphenylurea with preservation of the physical-mechanical characteristics inherent in this is the polymer.

The method is that the reaction of interaction of potassium dioxalate 4,4'-diacetyldiphenylurea with dehalogenation in dimethyl sulfoxide (DMSO) (tKip=189°C) is conducted as a continuous process in two stages.

At the first stage of the process from digitoxin 4,4'-diacetyldiphenylurea and features of non-CON (molar ratio 1:2), we obtain the solution of potassium dioxalate 4,4'-diacetyldiphenylurea in anhydrous DMSO. The reaction of condensation of potassium dioxalate 4,4'-diacetyldiphenylurea with 4,4'-dichlorobenzophenone (molar ratio 1:0.5) with carry, when the concentration of the solution of potassium to dioxamate 4,4'-diacetyldiphenylurea 1 mol/L. After azeotropic distillation of water the reaction is finished after 1 hour at 165°C., thereby forming oximetry dianion the following structure:

-O-N=C(CH3)-C6H4-O-C6H4- (CH3)=N-O-C6H4-CO-C6H4-O-N=C(CH3)-C6H4-O-C6H4- (CH3)=N-O-.

At the second stage of the process, add a mixture of 4,4'-diftorbenzofenon, 4,4'-dichlorobenzophenone and K2CO3(crushed and calcined), in a molar ratio of 0.5:0,005:0.15 in terms of 1 mol of the original digitoxin 4,4'-diacetyldiphenylurea in anhydrous DMSO (additional volume of anhydrous DMSO is taken from the calculation that the concentration of rest the RA for each of the monomers in the second oligoprimers the synthesis phase will be equal to 0.5 mol/l). Thus, the total molar ratio digitoxin 4,4'-diacetyldiphenylurea, mixtures of 4,4'-debtor - and 4,4'-dichlorobenzophenone and CON, TO2CO3the sum of the two phases was 1:1,005:2:0,15. The formation of the polymer after azeotropic distillation of the water - 6 hours. The polymer has a reduced viscosity ηCR=0.5 to 0.6 DL/g, the molecular mass MW≈51000-56000.

The method is illustrated by the following examples:

Example 1. The synthesis was performed in chetyrehkolkoy flask, purged with dried and purified from oxygen, nitrogen, equipped with a stirrer, a thermometer, a tube for supplying nitrogen and nozzle Dean-stark for azeotropic distillation of water. In the course of the synthesis temperature was maintained with an accuracy of ±0,2°C. In the flask under vigorous stirring was dissolved 2,844 g (0.01 mol) digitoxin 4,4'-diacetyldiphenylurea in 10 ml of dimethyl sulfoxide (reagent-grade) (this corresponds to C=1.0 mol/l in digitoxin), was added 1,122 g (0.02 mol) features of non-powdered KOH (reagent-grade).

For azeotropic distillation formed during the reaction water in the flask was added dry toluene, the volume of which was taken from the calculation of its permanent return from the trap Dean-stark in the reaction flask, which leads to its economy. After azeotropic distillation of water and residues of toluene at a temperature of 150°C in flask was loaded 1,2556 g (0,005 mol) of 4,41-dichlorobenzophenone. Those which the temperature was raised to 165°C., and the reaction mixture was stirred at this temperature for 1 hour.

Further, in the second stage of the reaction flask was added a mixture of 0,2073 g (0,0015 mol) pre-calcined and crushed To2CO3(CHP), 1,091 g (0,005 mol) 4,4'-diftorbenzofenon and 0,0126 g (0,00005 mol) 4,4'-dichlorobenzophenone in 10 ml of DMSO (CHP). Thus the concentration of the reaction mixture at the second oligo-polymer phase in terms of digitoxin 4,4'-diacetyldiphenylurea was 0.5 mol/L. Total molar ratio digitoxin 4,4'-diacetyldiphenylurea, mixtures of 4,4'-debtor - and 4,4'-dichlorobenzophenone and CON, TO2CO3the sum of the two phases was 1:1,005:2:0,15. In the second stage, the temperature was maintained at 165°C with accuracy ±0.2°C. the formation of the polymer after azeotropic distillation of the water - 6 hours.

The resulting polymer was besieged in acidified distilled water, washed with distilled water, dried with a gradual increase in temperature to 100°C. the polymer was Then dried under vacuum. Received 4.4 g of polyphenylenevinylene (exit 96%) with ηCR=of 0.64 DL/g

Example 2. As in example 1, except that the reaction was carried out without adding To2CO3. Got to 4.16 g of polyphenylenevinylene (output - 90%) with a viscosity ηCR=value of 0.52 DL/g

Example 3. As in example 1, except that the reaction was conducted for 5 hours. Received 4.3 g of polyphenylenevinylene is one of (output - 93%) with a viscosity ηCR=of 0.45 DL/g

Polyphenylenevinylene dissolved in chloroform, dimethylsulfoxide, dimethylacetamide.

The structure of the synthesized polymer is confirmed by elemental analysis and IR and PMR spectroscopy.

Elemental analysis data:

[-O-N=C(CH3)-C6H4-O-C6H4- (CH3)=N-O-C6H4-CO-C6H4-]n.

Found. %: C=75,61; H=4,89; N=OF 5.92.

Calculated for C29H22N2O4IN %: C=75,32; N=4,76; N=6,06.

In the IR spectra of the polymers has an absorption band in the region of 690 cm-1(aromatic ring), 1665 cm-1(>=0), 1365 cm-1(-CH3sym.), 1406-1412 cm-1corresponding to C=N-groups, and 1242 cm-1corresponding connection (Ph O-Ph).

According to PMR-spectroscopy, for digitoxin observed signals in the region of 2.3 M. D. (6N, S., CH3C=N), 1.8 m D. (H, s, C=N-OH). In polyphenyleneoxides signal in the region of 2.3 M. D. (6N, S., CH3C=N) remains, while the signal in the region of 1.8 M. D. (H, s, C=N-OH) disappears, which indicates that the bond formation (N-O-Ph).

Thus, we propose a new method for the synthesis of polyphenylenevinylene, allowing to reduce twice the consumption of expensive 4,4'-di-fermentation, replacing it with a cheaper 4,4'-dichlorobenzophenone.

In addition, in the reaction can be used potassium hydroxide, containing approx the si carbonate, if you know the percentage. In this case, the allocation for the required amount of KOH and2CO3.

The method of receiving polyphenylenevinylene, which consists in the interaction dioxamate anions 4,4'-diacetyldiphenylurea with 4,4'-dehalogenation at elevated temperatures in an aprotic dipolar solvent, dimethyl sulfoxide, characterized in that the synthesis of polyphenylenevinylene carried out in two stages: the first stage reaction of potassium dioxalate 4,4'-diacetyldiphenylurea with 4,4'-dichlorobenzophenone at a molar ratio of 1:0.5 and the solution concentration C=1 mol/l for dioxamate for 1 hour at a temperature of 165°C. in the presence of solid powdered KOH receive dioxamate anion of the following structure:
-O-N=C(CH3)-C6H4-O-C6H4-C(CH3)=N-O-C6H4-CO-C6H4-O-N=C(CH3)-C6H4-O-C6H4-C(CH3)=N-O-,
on the second final stage of the process, add a mixture of 4,4'-diftorbenzofenon, 4,4'-dichlorobenzophenone and crushed and calcined To2CO3in a molar ratio of 0.5:0,005:0.15 in terms of 1 mol of the original digitoxin 4,4'-diacetyldiphenylurea in anhydrous DMSO, and the additional volume of anhydrous DMSO is taken from the calculation that the concentration Rast is the PR for each of the monomers in the second oligoprimers the synthesis phase will be equal to 0.5 mol/l, the total time of the reaction for 6 hours at a temperature of 165°C.



 

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