SU860485A1 - Polyheteroarylenes for making heat resistant materials and process for producing the same - Google Patents

Description

The invention relates to the field of synthesis of polymers with a [polyphenylene structure of the main chain, in particular polyheteroarylenes, and can be used in the chemical industry, and polymers for the manufacture of heat-resistant materials.

Known polymers with a polyphenylene structure of the main chain containing phthalide groups [11.

The polymers are prepared by polycondensation of pseudochlorohydrides of β-ketocarboxylic or 0-di-carboxylic acids by the electrophilic substitution of aromatic compounds.

The resulting polyheteroarylenes have high heat resistance, but have a relatively low reactivity, which limits their scope.

These properties are determined by the new chemical structure of polyheteroarylenes having the general formula

-D ---- s- R - --- 1 t a

YU

. where R is a radical

-R

>

aromatic bivalent formula or

R ^ is the radical of the formula —CH _E : —C ^ H $; -CgH ^; -CHt £ -CH = ^c, l -C _r H ₄ 0H 'or

The aim of the invention is to increase the reactivity of polyheteroarylenes.

p "0.5-95; p 5-99.5

- reduced viscosity measured in sym. tetrachloroethane at 25 ° C, 0.15-0, ’40 dl / g.

The polyheteroarylenes of the indicated formula are prepared by the process consisting in 5 that the polyheteroarylenes of the general formula

where k is similar to the above, they are condensed with primary aliphatic and fatty aromatic amines of the general formula R ή ΝΗζ., where R '15 is similar to the above Rj, in the presence of their hydrochlorides or their hydrochlorides in the presence of water, or in the presence of triethylamine hydrochloride.

120

The proof of the structure of the obtained polymers is the presence in the IR spectra of chloroform solutions of these polymers of the absorption band C = 0 of the 1650 cm ¹ group, characteristic of the _2J vibrational vibrations of the carbonyl group of the phthalimidine cycle, as well as the complete

Depending on the type of aliphatic amine, with which the initial polyheteroarylene was condensed, and also depending on the ratio (P: p synthesized

soluble in methylene chloride, chloroform, sym.-tetrachloroethane, DMF, N-methylpyrrolidone, 1, 4-dioxane, 'benzonitrile, nitrobenzene and other solvents), or only in a number of organic solvents (for example, polyheteroarylene with R ‘

and R ι, - C ^ NdOP dissolves in DMF, cresol, pyridine), or does not dissolve at all (for example, polyhetero disappearance with practically quantitative conversion of the initial polyheteroarylene absorption band C = 0 of the group 1780 cm “ ⁴ -) characteristic of stretching vibrations of the carboxyl corpse , py of the phthalide cycle in the initial polyheteroarylene, which, with the existing accuracy in determining the polymer composition using IR, corresponds to m <: о, 5.

In the case of copolymers, the spectrum contains absorption bands of the carbonyl group, characteristic as. for the phthalide and phthalimidine cycles, 'the ratio m · was determined from the ratio of optical densities and from the calibration graph constructed from the spectra of model compounds. R . The structure of the synthesized polymers ⁴⁵ is also confirmed by the elemental analysis data given in the examples.

The reduced viscosity of the obtained polyheteroarylenes, measured in a ⁵⁰ solution in sym, tetrachloroethane at 25 ° C, is 0.15 “0.4θ dl / g. The reduced viscosity of polyheteroarylenes obtained by condensation of the starting polyheteroarylene with monoethanol- ⁵⁵ amine, measured in N, N-dimethylformamide (DMF) at 25, is 0.21 dl / g. * arylene with

R ^ -CHi-CH-CHq)

The obtained polyheteroarylenes have a temperature of onset of decomposition in argon of 230-35 (GS, and a temperature of onset of softening of 180-350 ° C.

Thus, the obtained polyheteroarylenes compared with the initial ones in the case of aliphatic substituents at R ^ -C ^ R ^ OH or -CH ^ -CHs. > -C due to the presence of chemically active functional groups in them: hydroxyl or allyl, respectively, they can be used for further chemical transformations, including in finished products with modified properties. Example 1. In a 10 ml ampoule purged with argon, load 0.5 g of the initial polyheteroarylene

acid methylamine and 3 ml with R g salt

25% aqueous solution of methylamine and heated at 270 ° C for 12 hours with vigorous stirring.

The polymer is unloaded, washed with methanol (Seely or ethanol) and dissolved in 10 ml of chloroform. The solution is precipitated in 8-10 times the amount of me10 i

tanola. The precipitated polymer flakes are filtered off, washed on the filter with alcohol, acetone and dried in vacuum at 100 ° C for 10 hours. The polymer yield is 0.47 g (90% of theory). The synthesized polymer has a reduced viscosity measured in sim.-tetrachloroethane at 25 ° C 0.4 dl / g. According to the IR spectrum, the absorption band of the carbonyl group of the phthalide cycle disappears completely, which indicates an almost 100% conversion of the phthalide ¹ cycle in phthalimidine and allows us to assume that with the existing exact- * ⁵ method mi mi 0,5.

Found%: C 85.01; H 5.25; N 4.68 1 (C ^ H ₁₅ MO) _P

Calculated,%: C 84.85; H 5.05; N 4.71.

The polymer is soluble in methylene chloride, chloroform, sim.-tetrachloroethane, 1,4-dioxane, DMF, and other solvents from the solutions of which gives transparent films. The temperature of the onset of rutra 300 ° C;

Etc .

heating the ampoule with the reaction mixture for ³⁰ hours for 12 hours at 230 ° C. According to the IR spectrum, polymer conversion. is 50% (t: p = 50:50).

Example 3. Into a 10 ml ampoule, purged with argon ’, load 00.5 g of initial softening> 350 ° С, the decomposition rate in argon and MER 2. The example of polyheteroarylene is repeated.

g of hydrochloric butylamine and 3 ml of acidic and heated at 270 ° C for 12 hours with vigorous stirring.

The polymer is unloaded, washed with J methanol (or ethanol) 'and dissolved in 10 ml of chloroform. A solution in 100 ml of alcohol is planted. The precipitated polymer flakes are filtered off, washed on the filter with alcohol, acetone and dried in vacuum at 100 ° C for 12 hours. The polymer yield is 0.5 g (83.3% of theory). According to the IR spectrum, the polymer is completely converted (hl 0.5). Found%: C 85.69; And 6.61; N, 4.12. (C _and H ^ MO) _n ,

Calculated%: C 84.96; H, 6.19; N, 4.13.

The polymer is soluble in chloroform, sym.-tetrachloroethane, N-methylpyrro50

860485 ⁶ lidone, benzonitrile, DMF to other solvents, from the solutions of which it forms transparent films.

The temperature of the onset of softening is 280 ° C, the temperature of the onset of decomposition in argon is 340 ° C.,

Example 4. Repeat example 3, heating the ampoule with the reaction mass at 230 ° C for 12 hours. According to the IR spectrum, the polymer conversion is 70% (L: p = 30:70).

Example 5. In a 5 ml ampoule, 0.2 of the initial polyheteroarylene with R CHO ^ <and m-100, 1 g of butylamine hydrochloride and 2 ml of butylamine are charged and heated at 270 ° C for 12 hours with vigorous stirring.

The polymer is unloaded, washed with methanol (or ethanol) and dissolved in 5 ml of chloroform. A polymer solution in 100 ml of methanol or ethanol is planted. The precipitated flakes are filtered off, washed on the filter with alcohol, acetone and dried in vacuum at 100 ° C for 10 hours. The polymer yield is 0.25 g (83.3% of theory).

The viscosity of the synthesized polyheteroarylene in solution in sim.-tetrachloroethane at 25 ° C is 0.15 dl / g.

According to the IR spectrum, the polymer underwent transformation (m Example 6. In a vial filled with argon purged, load 0.5 starting polyheteroarylene with R

gender 0.51.

ml

G IS ”butylamine

and m 100, 0.5 g of allylamine hydrochloride and 3 ml of allylamine and heated at 230 ° C for 12 hours with vigorous stirring.

The polymer is unloaded, washed with methanol (or ethanol), crushed, washed with acetone and dried in vacuum at 100 ° C for 10 hours. The polymer yield is 0.5 g (87.7% of theory). According to the IR spectrum, there is a complete absence of the absorption band of the carbonyl group of the phthalide cycle, i.e. undergoes polymer conversion (m £ 0.5). '

The synthesized polyheteroarylene does not dissolve in any organic solvent.

85.42; H 5.27; N, 4.29.

C 85.45; H 5.26; N, 4.33. p 7. In a 5 ml ampoule,

Found%: C (C N0), fl

Calculated,%:

For example, purged with argon, load · 0.2 g of the original polyheteroarylene with

and m = 100, 0.4 g solyan1.

The reduced viscosity of the synthesized polyheteroarylene measured in sym. Tetrachloroethane at 25 ^tf C, 0.36 dl / g. The temperature of the onset of softening is 180 ° C; the temperature of the onset of decomposition in argon is 350 ° C.

With blown acid triethylamine and 2 ml of allylamine, it is heated with stirring at 16 ° C for 12 hours. The polymer is discharged, washed with methyl (or ethyl) alcohol, and dissolved in 5 ml of chloroform. A polymer solution in 100 ml of methanol (or ethanol) is planted. The precipitated flakes of the polymer are filtered off, washed on the filter with alcohol, acetone and dried in vacuum at 100 ° C for 10 hours

According to the IR spectrum, the polymer conversion is 75% (m: P = 25: 75). The spectrum of the polymer is present strip 990 cm ^4, characteristic of double bonds, which also is confirmed by the structure ³⁵ of the synthesized polymer.

Example 8 .. In an ampoule of 10 purged ar.gonsm, load 0.5 g of ligeteroarylene with R

and m 100, 2 g of solyankis15

ch = 100, 1.5 g of octylamine hydrochloride and 3 ml of octylamine was heated at 270 C for ⁶ h 12 with vigorous mixing of nepej _5. The polymer is discharged, washed with alcohol and dissolved in 15 ml. chloroform. The polymer solution is planted in 8-10 times the amount of alcohol. The precipitated flakes of the polymer are filtered off, washed on the filter with alcohol, acetone and dried in vacuum at 100 ° C for 10 hours

According to the IR spectrum, there is a complete absence of the absorption band of the carbonyl group of the phthalide cycle of measures 9. In a 20 ml ampoule, 1 g of isopolyheteroarylene from the logo of monoethanolamine and 6 ml of monoethanolamine are loaded and heated for 3 hours at 230 ° C with vigorous stirring.

The polymer is unloaded, washed with alcohol, dissolved in 50 ml of DMF and 8-10 times the amount of methanol (or ethanol) is planted. The precipitated polymer flakes are filtered on the filter with alcohol, acetone and dried in vacuum at 100 ° C for 10 hours.

The polymer yield of 0.55 g (95.5% of "theoretical"). According to the IR spectrum, a complete conversion of the measure (m'i0.5) takes place.

Found% ·. C 81.80; H 5.70; (SadH ^ ΝΟρΙ η

Calculated ^: C, 80.73; H 5.2;

The polymer is soluble in DMF, poly4,28.

those. complete polymer conversion (hl 0.5). The yield of synthesized v polyheteroarylene is 0.66 g (95.5% of theoretical). Found%: C 86.80; H 7.53; N 3.53. (C _ig H _Q9 N0) _n

Calculated,%: C 85.06; P, 7.34; N 3.54. The polymer is soluble in chloroform, sim.-tetrachloroethane, 1,4-dioxane, DMF, benzonitrile, nitrobenzene and other solvents, from the solutions of which it gives transparent films.

N cresol, pyridine, from the solutions of which forms transparent films. The reduced viscosity of the synthesized polyheteroarylene measured in DNFA at 25 ° C, 0.21 dl / g The softening temperature is 350 ° C, and the temperature of the onset of decomposition in argon is 230 ° C,

Example 10. Repeat example 9, by heating the ampoule with the reaction ”mass at 180 ° C for 12 hours. According to the IR spectrum, the polymer conversion is 25% (those: P = 75: 25). The synthesized polyheteroarylene is soluble in DMF, cresol, 'pyridine.

Example 11. Example 9 is repeated, heating the ampoule with the reaction mass at 180 ° С for 1 h. According to the IR spectrum, the polymer conversion is 5% (W: P = 95: 5). The polymer is soluble in DMF, cresol, pyridine.

Example 12. Repeat example

9, heating the ampoule with the reaction mass at 200 ° C for 25 hours

According to the IR spectrum, the polymer conversion is 100% (i.e., η ^ 0.5).

The yield of synthesized polyheteroarylene 0.52 g (90.3% of theoretical. The polymer is soluble in DMF, pyridine, cresol.

Example 13., In a 10 ml ampoule, purged with argon, load 0.3 g of the initial polyheteroarylene with

R

ish100.1.5 g of hydrochloric acid •. ω of benzylamine and 2 ml of benzylamine and heated at 230 ° C for 25 hours with thorough stirring.

The polymer is discharged, washed with alcohol and dissolved in 10 ml of chloroform. ¹⁵ Plant the polymer in 100 ml of alcohol. The precipitated polymer flakes are filtered off, washed with alcohol, acetone and dried in vacuum at 100 ° C for 10 hours.

According to the IR spectrum, the polymer conversion is 20% (w: P = 80:20).

As follows from the examples, the resulting polymers combine high heat resistance with increased reactivity.

Claims (2)

 reduced viscosity measured in sym.-tetrachloroethane at 0.15-0; 0 dl / g. Polyheterrarilenes of this formula are obtained by a method that concludes that polyheteroarylenes of the general formula where k is similar to the above, are condensed with primary aliphatic and fatty-aromatic aminagars and. General formula R-NHi, where R. similar to the above Rjj, in the presence of their chlorohydrates or their chlorine hydrates in the presence of water, or in the presence of triethylamine hydrochloride. Evidence of the structure of the polymers obtained is the presence of the e-IR spectra of chloroform solutions of these polymers of the 1650 cm C band of absorption characteristic of the carbonyl groups of the phthalimidine cycle for the vibrations of the carbonyl group, as well as the disappearance of the CGO band of the 1780 characteristic of the initial polyheteroarylen stretching vibrations of the carboxyl group of the phthalamide cycle in the original polyheteroarylene, with the existing accuracy of determining the composition of the polymer with with an ICS corresponds to rp: 0.5. in the case of copolymers, the absorption spectra of the carbonyl group are characteristic of. for phthalidium and phthalimidine cycles, and according to the ratio of optical densities and the calibration graph, constructed from the spectra of model compounds, the ratio ni was determined. R . The structure of the synthesized polymers is also confirmed by the elemental analysis data given in the examples. The reduced viscosity of the polyheteroarylenes obtained is measured in:. solution in symm.-tetrachloroethane at, is 0.15-0, dl / g. The combined viscosity of polyheteroarynes obtained by condensation of the starting polyheteroarylene with monoethanolamine, measured in N, N-dimethylformamide (DOPA) at, is 0.21 dl / g. Depending on the type of aliphatic amine with which the starting polyheteroarylene was condensed, and also depending on the ratio rti; p synthesized-, polyheteroarylenes differ greatly in solubility. So they can be dissolved either in a wide range of solvents (for example, polyheterrarylen R / 1 - dissolves in methylene chloride, chloroform, symm.-tetrachloroethane, DMF, N-methylpyrrolidone, 1, diRxane, benznenitrile, nitrobenzene and other solvents), or only in a number of organic solvents (nanpv, polygethe with R and R i, dissolves in DMF, cresol, pyridine) or does not dissolve at all (for example, polyheteroVy 4 / arylene s. The polyheteroarylenes obtained have a decomposition start temperature in argon of 230-350 ° C, and a softening start temperature of 180- 350 C. Thus, the obtained polyheteroarylenes as compared with the initial ones in the case of aliphatic substituents at R or: gCHd, due to the presence of reactive functional groups in them: hydroxyl or allyl, respectively, can be used for further chemical transformations including finished products with modified properties. Example 1.8 a 10 ml ampoule purged with argon was charged with 0.5 g of the initial polyheteroarylene with R - / y-4/100, 1 g of salt 3 ml of 25-acidic methylamine and an aqueous solution of methylamine and heated for 12 hours with intensive stirring. The polymer is discharged, washed with methanol (Sealy, ethanol) and dissolved in 10 ml of chloroform. The solution is precipitated in 8-10 times the amount of methanol. Polymer floes are filtered off, washed on the filter with alcohol, acetone and dried under vacuum at 100 ° C for 10 hours Polymer output is O, "7 g (90% of theoretical; synthesized polymer has viscosity measured in sym. Tetrachloroethane at 0.4 dl. According to the IR spectrum, you observe the complete disappearance of the absorption field of the carbonyl group of the phthalide cycle which is indicative of n Actually, the lOOll-HOM transformation of the phthaline cycle into the phthalimidine cycle allows us to assume that with the current exact method, the method was 0.5%. Found: C 85.01; H 5.25; N "4.68) Calculated,%: C 8i, 85; H 5.05; MCH, 71. The polymer is soluble in methylene chloride, chloroform, sym-. Tetrachloroethane, 1, -dioxane, DMF, and other solvents, from the solutions of which gives transparent films. The softening onset temperature is 350 ° C, the temperature of the onset of decomposition in argon is 300 ° C; Example 2. Example 1 was repeated, heating the vial with the reaction mixture for 12 hours at 230 ° C. According to the IR spectrum, the polymer conversion is 50 (t: p 50:50). Example 3. A 1B ml vial, purged with argon, was charged with 0.5 g of the starting polyheteroarylene with R Tft 100, 2 g of hydrochloric acid butylamine and 3 ml of butylamine and heated at 270 ° C for 12 hours with vigorous stirring. The polymer is discharged, washed with methanol (or ethanol) and dissolved in 10 ml of chloroform. Planted solution in 100 ml of alcohol. The precipitated polymer flakes are filtered off, washed on the filter with alcohol, acetone, and dried under vacuum at 100 ° C for 12 hours. The polymer yield is 0.5 g (183.3% of the theoretical). According to the IR spectrum, the polymer is completely transformed (n 0.5). Found%: C 85.69; H 6.61; N, 12. () Calculated%: C 84.96; And 6.19; N4.13 The polymer is dissolved in chloroform sym, tetrachloroethane, N-methyl pyrroidone, benzonitrile, DMF to other solvent, from the solutions of which forms transparent films. The softening onset temperature is 280 s, the onset temperature of decomposition in argon., Example k. Example 3 is repeated, heating the vial with a reactive mass at a for 12 hours. According to the IR-spectrum data, the conversion of the polymer is 70% {W: p 30:70). Example 5. 0.2 initial polyheteroarylene with R CHO and 100, 1 g of hydrochloric butylamine and 2 ml of butylamine are loaded into a 5 ml ampoule and heated at 12 h with vigorous stirring. The polymer is discharged, washed with methanol (or ethanol) and dissolved in 5 ml of chloroform. Planted polymer solution in 100 ml of methanol or ethanol. The precipitated flakes are filtered, washed on the filter with alcohol. acetone and dried under vacuum for 10 hours. The polymer yield is 0.25 g (83.3% of theory). The viscosity of the synthesized polyheteroaryl in solution in symm.-tetrachloroethane at 0.15 DL / g. According to the IR spectrum, the polymer was completely converted (m 0.5i. Example 6. 0.5 g of the original polyheteroarylea with R / g: m 100, 0.5 g of allylamine hydrochloride and 3 g ml of allylamine and heated under stirring for 12 hours. The polymer is discharged, washed with methanol (or ethanol), crushed, washed with acetone and dried under vacuum at 8 for 10 hours. Polymer yield 0.5 g (87.7% of theoretical). According to the IR spectrum, there is a complete absence of the absorption band of the carbonyl group of the chicle, t, e, about Odita polymer conversion {t 0.5). The synthesized polyheteroarylene does not dissolve ki in the same organic solvent. Found%: C "5.2; H 5.27; N, 29. (, NO) Calculated: С 85, «5; H 5.26; Ni +, 33. Example 7. A 5 ml ampoule, purged with argon, was charged with 0.2 g of the initial polyheteroarylene with, 0.4 g SOLYAN01 “Ll of acid triethylamine and 2 ml with allyls and heated with stirring at 160 ° C for 12 hours. Unload the polymer, wash its methyl Sealy ethyl alcohol is dissolved in 5 ml of chloroforDa. Polymer solution is precipitated in 100 ml of methanol (or ethanol). The precipitated polymer floc is filtered off, washed on the filter with alcohol with acetone and dried under vacuum at 100 ° C for 10 hours. According to the IR spectrum, the polymer conversion is 75 (t: p 25: 75). The spectrum of the polymer contains a band of 990 cm, characteristic of double bonds, which is also confirmed by the structure of the synthesized polymer. Example of an ampoule per TO ml of ventilated argon, load 0.5 g of lyheteroarylene with R / / hl 100, 1.5 g of hydrochloric octylamine and 3 ml of octylamine are heated at 270 s for 12 h with intensive mixing. The polymer is discharged, washed with alcohol and dissolved in 15 ml. chloroform. Planted polymer solution in 8-10 times the amount of alcohol. The precipitated polymer flakes are filtered off, washed on the filter with alcohol with acetone, and dried in vacuum at 100 ° C for 10 hours. According to the IR spectrum, there is a complete absence of the absorption band of the carbonyl group of the phthalide cycle. passed the complete transformation of the polymer (th 0.5). The yield of the synthesized polyheteroarylene is 0.66 g (.95.5 of the theoretical). Found I: C, 86.80; H 7.53; 53 (C gHoaNO) n Calculated: С 85.06; P 7. N3.5. The polymer is soluble in chloroform, simm-tetrachloroethane, 1, -dioxane, DMF, benzonitrile, nitrobenzene, and other solvents, from the solutions of which gives transparent films. The reduced viscosity of the synthesized polyheteroarylene, measured in symm.-tetrachloroethane at, O, -36 dl / g. The temperature of onset of softening, the temperature of onset of decomposition in argon. Example 9. A 20 ml ampoule purged with argon was charged with 1 g of the initial polyheteroarylene with g m 100, 2 g of hydrochloric acid / g // monoethanolamine and 6 ml of monoethanolamine and heated for 3 hours at 230 ° C with vigorous stirring. The polymer is discharged, washed with alcohol, dissolved in 50 ml of DMF and planted in an 8-to-fold amount of methanol (or ethanol). The precipitated polymer flakes are filtered on the filter with alcohol, acetone and dried under vacuum for 10 hours. The polymer yield is 0.55 g (95.5% of theoretical). According to the IR spectrum, the polymer is completely transformed (, 5). Found%: C 81.80; H 5.70; N C, 26. (.) Calculated,%: C 80.73; H 5.2; N f, 28. The polymer is soluble in DMF, cresol, pyridine, from the solutions of which forms transparent films. The reduced viscosity of the synthesized polyheteroarylene, measured in DMF at 25 ° C, 0.21 dl / g. The softening point and the temperature of onset of decomposition in argon, Example 10. Example 9 is repeated, heating the vial with the reaction mass at 180 ° C for 12 hours. According to the IR spectrum, the polymer conversion is 251 tw: 75:25 . The synthesized polyheteroarylemia is dissolved in DNFA, cresol, pyridine. Example 11 Example 9 is repeated, heating the vial with the reaction mass for a for 1 hour. According to the IR spectrum, the conversion of the polymer is 5 (W: P 95: 5). The polymer is soluble in DMF, cresol, pyridine. Example 12. Example 9 is repeated, heating the vial with the reaction mass at 200 ° C for 25 hours. According to the IR spectrum, the conversion of the polymer is 100 St. l.hg 0.5). The yield of the synthesized polyhero roylene is 0.52 g (EO, 3% of the theoretical. The polymer is soluble in DMF, pyridine, cresol. Particular 13, 0.3 g of the original polyheteroarylene are loaded into a 10 ml ampoule with V / II and 100.1.5 g of hydrochloric acid (benzyl amine) and 2 ml of benzylamine and heated under stirring for 25 hours. The polymer is discharged, washed with alcohol and dissolved in 10 ml of chloroform. The polymer is precipitated in 100 ml of alcohol. The precipitated polymer flakes are filtered off, washed with alcohol, acetone and dried under vacuum for 10 m. According to IR Spectrum conversion of the polymer is 20% (t: p 80:20). As follows from the examples, the resulting polymers combine high thermal stability with increased reactivity. Claim 1. Polyheteroarylenes of the general formula 5 where R is a radical of the formula -CHjj-СфН "; -CH, -C, or, G II TtiO, 5-95; C /., 5, with reduced viscosity, measured in symm-tetrachloroethane at 0.15-0.40 dl / g, for the manufacture of heat-resistant materials. 2. A process for the preparation of polyheteroarylenes, which consists in the fact that Polyheteroarylenes of the general formula where R is an aromatic divalent radical of the formula / G is condensed with primary aliphatic and fatty aromatic amines of the general formula INH, where R j is a radical of the formula-CHg; ,; -CHt2: CH CH, .C ,, or