Polyamines with acetylene groups

19. G.I. KUDRYAVTSEV, T. A. MATYASH, M. A. ZHARKOVA and V. S. KLIMEMKOV, Khimich. volokna, No. 4, 13, 1961 20. M. NEGISI, Senzi Gakkaisi 17: 66, 1961 21. L. ODRIT and B. OGG, Hydrazine Chemistry, 1954 22. K. P. SHEN and F. K. EIRICH, Internat. Symposium on Macromolecular Chemistry, Section I, Moscow, 323, 1960 23. G. MINO and S. KAISERMAN, J. Polymer Sci. 31, 242, 1960 24. R. M. LIVSHITS, D. A. PREDVODITELEV and Z. A. ROGOVIN, Cellulose and its Derivatives, A N SSSR, 60, 1963 25. R. M. LIVSHITS, R. MARUPOV, R. G. ZHBANKOV and Z. A. ROGOVIN, lbidem, p. 65 26. R. M. LIVSHITS, L. M. LEVITES and Z. A. ROGOVIN, Vysokomol. soyed. 6: 1624, 1964 (Translated in Polymer Sci. U.S.S.R. 6: 9, 1798, 1964) 27. A. A. GULINA, R. M. LIVSHITS and Z. A. ROGOVIN, Vysokomol. soyed. 7: 1529, 1965 (Translated in Polymer Sci. U.S.S.R. 7: 9, 1963, 1965) 28. R. SAKAMOTO, NIPPON KAGAKU RASSKU, J. Chem. Soe. J a p a n 83: 386, 1962; Chem. Abstrs 59: 13160, 1963 29. Yu. G. KRYAZHEV, Thesis, 1963 30. M. I. KABACHNIK and T. Ya. MEDVED', Izv. A N SSSR, Chem. section, No. 6, 635, 1950

POLYAMINES WITH ACETYLENE GROUPS* A. G. SHABAlqOTCA,A. M. SLADKOV and V. V. KORSHAK Heteroorganic Compounds Institute, U.S.S.R. Academy of Sciences

(Received 14 March 1967)

COlVTI~IVlNG our investigation of polyconjugated acetylene compounds we decided upon the synthesis of acetylene polyamines in order to determine how the properties of the polymers are affected by the nitrogen atom. This paper describes the synthesis of polyamines; a separate report will be made regarding the electrophysical properties of the polyamines. In view of the possible oxidation of ~aines under oxidizing polydehydrocondensation reaction conditions we decided to utilize the alkylizability of amines to synthesize acetylene polyamines by means of the polycondensation of amines with polyfunctional acetylene halides. Very little information about the production of acetylene polyamines has been published. In the production of 1,4-diaminobutyne-2 from 1,4-dichlorobutyne-2 and an alcoholic solution of ammonia or liquid ammonia Johnson [1] synthesized the polymer - - H N - - C H ~ - - C - C--CH~-- which characterized only the melting point. * Vysokomol. soyed. A10: No. 2, 373-378, 1968.

The present authors obtained polyamines through the polycondensation of 1,4-dichlorobutyne-2 (DCB) and 1,6-dichlorohexadiyne-2,4 (DCHD) with aniline, a-naphthylamine p-phenylenediamine, benzidine, and hydrazobenzene, e.g.:

CeH~NH2+CI_CH~_C_C_CH2_C

1 A~,co,, H[N(C6Hs)CH2_C=C_CH~]~CI"

The conditions of the nonequilibrium polycondensation of DCB with amines were studied by the authors using the reaction with aniline as an example. The TABLE 1. EFFECT OF ~ATIO REACTIVE COMPONEI~ITSON MOLECULAR WEIGHT

Molar ratio aniline : DCB

Yield, ~o

1:0"5 1:1 1:1.2 1:1"5

56 74 88 quantitative

Mol.wt. (by ebullioscopy ] Softening inchloroform) point, °C 105-127 125-135 125-135 105-129

600 1100 900 700

effect of the ratio of the reacting components upon molecular weight is shown in Table 1. Anhydrous potassium carbonate was used as hydrogen chloride accepter, the amount being 1.1 mole per mole of the amine. The reaction was carried out in ethyl alcohol, r£tio of alcohol to reaction components 5 : 1, at 60-70 ° for 15 hr. The reaction does not proceed with an accepter. When potassium hydroxide is used there is dehydrochlorination of DCB [2]. A rise in the concentration of the reactive components in solution is accompanied by increase in molecular weight (see Table 2). TABLE

2. E F F E C T

OF

CONCENTRATION

ON

MOLECULAR

WEIGHT

Ratio of alcohol : reactive components 20:1 10:1 5:1 2.5:1

Yield, %

Mol.wt.

Softening point, °C

73 75 74 74

800 800 1100 1400

103-124 120-130 125--135 137-145

A rise in the reaction temperature leads to a rise in molecular weight; the same result is observed when the time of synthesis is extended. Other solvents used in the experiments apart from ethyl alcohol were butyl alcohol, tetrahydrofuran and benzene. The polycondensation does not procee d in

benzene. In tetrahydrofuran N-phenyl-N-(butyne-2-chloro-1)aminewas obtained; the structure of the latter was confirmed by the results of elementary analysis (Table 3). The Table shows that the molecular weights of the oligomers calculated on the results of elementary analysis are in good agreement with the values found. Thus oligomers in the form of bright-coloured powders with m.p. 100-150 ° and m.w. up to 2000 were obtained. The optimum conditions for the polycondensation of DCB and aniline were adopted for production of the other polyamines, the properties of which are given in Table 4. In the reaction of a-naphthylamine and DCB an oligomer was obtained with m.w. 600 (determined by ebullioscopy in benzene); the molecular weight calculated from the end groups is 1000. From p-phenylenediamine and benzidine solid, infusible and insoluble oligomers were obtained which probably had three-dimensional structure. The optimal conditions for obtaining the oligomer from aniline and DCB were used in the production of oligomers based on DCHD, the properties of which are given in Table 5. The oligomer of aniline is an insoluble powder differing from the analogous oligomer of the butyne-2 series. The same was also observed in the case of anaphthylamine, where the oligomer with a softening point of 200 ° and m.w. 420 was soluble (m.w. by ebullioseopy in chloroform). An increase in the number of elementary units reduced the solubility of the oligomer and raised the softening point--the oligomer did not melt at 400 °. A fragment of the oligomer --N(CetIs)--CH2--C=C--C-C--CH 2 - was built up from Stuart models of atoms. The oligomer chain is rigid and in zig-zag form, the oligomer fragments being at an angle depending on the direction of the valency bonds of the nitrogen atom, while the phenyl rings cannot be in the same plane as the diyne group. The limited solubiJity of the hexadiyne oligomers is probably due to the rigidity of the oligomer chains. The authors attempted to synthesize a saturated polyamine by the polycondensation of aniline with 1,6-dichlorohexane. Under conditions similar to those for the synthesis of acetylene polyamines the reaction did not proceed, as was found by gas chromatographic analysis of the reaction mixture in which only unreacted components were detected. The IR spectroscopic data for the synthesized polyamines showed that the spectra of the butyne-2 series of oligomers have more bands and overtones than the spectra of oligomers of the hexadiyne-2,4 series. The impoverishment and obliteration of the spectra of the latter is probably also due to chain rigidity impeding the vibrations. The spectra have absorption bands characteristic of mono- and disubstituted benzene rings (690, 760, 820, 1550, 1600 cm-1), NI-Igroups (1600, 3400 cm-1), CH-aliphatic (2820, 2950 cm-1), CH-aliphatic (2850, 2950 em -1) CH-aromatic (3030, 3060 cm-1). There is no band of C = - C bond vibrations. Proof of the presence of triple bonds in polyamines [3] is provided by bands

--N-CH~-C~-C-CH 2P Cell4 I Coil4 t --N-CH2-C--- C-CH~--

--N-CH2-C_= C--CH=-

I Celia

--N--CH=--C-=C CH=--

CH 2 -

75'72

69.18

77"98

5.51

5.57

5.82

5"77

84.51

[l~ (CloHT) CHuC~CCH2] 5 C|

H 6.12

tt IN (C6ttb)--N (Cetta) --C ~ C-CH2]a C1

N 8"61 9"79 9"23

-4"11 1"99

C1 ClO~IzoNC1 CloHgNClo.~ CloHgNClo.o9

9.79

11.76

12.82

7.6

9.23

N

3.32

4.62

66"8 80"0 82"0

C

5.76

11.5

7.06

9.56

N

3.65

2.5

2.29

C1

Three-dimensional structure

Three-dimensional structure

79.0

5.55

84.7

1.18

3.06

6.15

82.0

H

1.99

C1

calculated

Elemental composition, % found

81.73

C

6"04 6"3 6"12

H

empirical formula of unit

A~D

5"56 6"0 6"15

H

84

92

12

66

72

%

Yield,

I -4"72 2"29

C1

DCB

Does not dissolve

Chloroform Chloroform, benzene Sulphur ie e t h e r Does not dissolve

Solubility

7"8 9"35 9"56

N

calculated

TABLE 4. P R O P E R T I E S OF P O L Y A M I N E S B A S E D O1Q" D C B

66"32 79"39 81"73

C

found

Elemental composition, %

3. i ~ O L E C U L A R W E I G H T OF P R O D U C T S OF C O N D E N S A T I O I ~ OF AI',,rILII~E

H [N (CeH~) C H 2 C ~ C - C H 2 ] n CI

w

Polyamine

H N (Cell~) CH2C~-C--CH~C1 H IN (C,Hb) CH:C---CCH2]~CI l~ [N (C,HD CH~C=-CCH..], Cl

P o b -amine

TABLE

Does not melt

Does not melt

50-55

138-144

146-155

Softening p o i n t , °C

-800 1550

found

Black

Dark brown Black

Bright cream Ditto

Colour

180 700 1600

calculated

Mol.wt.

c.H, I C6H~ t -N--CH~--C_= C--C_-- C - C H ~ - -

I

- N - - C H z - - C - : C - C ~_C - CH~--

--~,--Ctt=--C-~C-C-:C-CHI-69"88

65.85

--I~-CHI-C_--CI CeHa I

- CH2], Cl

4.77

4.93

5.44

84.69

H [N (C1oH?) CH~CF-C--C~-C--

C_-- C - C H 2 -

5.32

-- CH2Js CI

77'02

tt N

6.94

5.97

7"38

8.4

found

5.28

4-89-

5"68

6.95

C1

4-9

5.2

H

6.1

7.8

N

Three-dimensional structure

Three-dimensional structure

83.8

80.4

C

calculated

5.1

6.6

C1

Ditto

titarive

Quan

65

95

~o

Y~ld,

OF P O L Y A M I ~ E S B A S E D O N D C H D

E l e m e n t a l composition, %

5. PROPERTIES

H [N (C~HDCH~C---C-C-=C-

Polyamine

TABLE

Does n o t melt

Does n o t melt

Does not melt 2O0

Softening point, °C

Insoluble

Chloroform Insoluble

Insoluble

Solubility

Black

Dark brown Black

Bl~k

Colour of sample

characteristic of C - - C - C group vibrations in the region of 915-960 cm -1, and b y the bands of CH absorption in the C H ~ - - C - C group in the region of 14201440 cm -1. A s t u d y was also made of the chemical properties of the synthesized polyamines. In the bromination of the oligomer H[N(CsHs)CH~C- C--CH2]sC1 the bromination of the benzene ring into the para-position was observed as well as the broruination of triple bonds to double bonds. This is confirmed b y the results of elementary analysis and also b y the I R spectrum of the product of bromination and b y the results of bromination of N-propargylaniline described b y Wolf [4] who nosed the bromination of the benzene ring. In the I R spectrum of the product of bromination there are the intense absorption band of the para-substituted benzene ring in the region of 810 cm -1 and absorption bands in the region of 530-580 cm -~ which m a y probably be attributed to C - - B r bond vibrations [5]. The band of C - - C - C group absorption disappears. The softening point of the product of bromination is raised to 152-153 ° compared with the softening of the initial monomer which is 125-135 °. Increase in the amount of bromine and in the boiling time is accompanied b y complete bromination of the triple bond and b y bromination of the benzene ring not only into the para- b u t also into ortho-position. The I R spectra are characterized b y bands at 700,745,775 and 865 cm -1 indicating the presence of a mixture of isomers in the product'of bromination, and changes similar to those observed in the first case. The softening point oi the polymer in the case under consideration is 192-193 o. In the bromine of polyamine H IN (C6H5)--- CH~-- C - C-- C-- C-- CH~]3C1 the bromine went into para- and ortho-positions of the benzene ring; we also observed the bromination of one triple bond to a

I

800

I

I

I

I

I

1000 lz~O0 f600

i

B

1800

)), 0171-I

IR spectra od polyaminc H[N(C6Hs)-- CH2-- C - C-- C - C-- CH2],C1 (1) and product of its bromination (2). double bond, as well as what appeared to be allene regrouping of the remaining triple bond. This follows from the results of elementary analysis and from the I R spectrum of the product of bromination, and is in agreement with data regarding the bromination of conjugated triple bonds published in [6]. As also in the I R spectrum of the product of bromination there is the intense band in the region

o f 1730 c m -1 (see F i g u r e ) . T h e l a t t e r m a y p o s s i b l y b e d u e t o t h e a b s o r p t i o n o f t h e allene group of an allene oligomer of type --H~C--CBr----CBr--CH----C-----CH-p r e s e n t i n t h e p r o d u c t o f b r o m i n a t i o n [7]. T h e s p e c t r u m h a s n o b a n d s c h a r a c teristic of C--C=C and Ctt in the CH2--C-C group. F u r t h e r b r o m i n a t i o n o f t h e s a m e p r o d u c t f o r a n o t h e r 28 h r p r o d u c e d n o c h a n g e s . T h e h y d r a t i o n o f o l i g o m e r H [N ( C 6 H 5 ) - - C H 2 - - C - C - - CH,]11C1 p r o c e e d e d quantitatively under normal conditions in dimethylformamide with Raney nickel. The IR spectrum of the product of bromination contains no bands of CIt and C--C=C group absorption in CH~--C-C. Attempts to hydrolyze an oligomer of aniline and DCHD in alcohol with R a n e y n i c k e l a t 100 ° a n d 200 a r m , a s w e l l a s i n i c e d a c e t i c a c i d w i t h a P t - c a t a lyst, proved unsuccessful under normal conditions, apparently because of the limited solubility of the oligomer. Iodomethylate was obtained from oligomer H[N(C6Hs)--CH2--C-C---CH~]6C1.

EXPERIMENTAL ])CB was synthesized b y the Johnson method [1] and a product with 60% yield was obtained; b.p. 51-53°/10 min. 2,4-Hexadiyndiol-l,6 was obtained b y the oxidative dehydrocondensation of propargylic alcohol b y the method described in [8], after which it was treated with thionyl chloride and separated with DCHD as recommended b y Cook [9], with a 50% yield; b.p. 70-71°/2-4 mm. 1,6-Diehlorohexane was obtained from hexanediol-l,6 with a 30% yield; b.p. 73-76°/5-6 ram. Aniline was vacuum-distilled at 103-105°/55 ram. a-Naphthylamine was vacuum-distilled at 112-115°/3 mm, m.p. 50 °. p-Phenylenediamino was sublimated i n vacuo (3 mm); m.p. 140 °. Benzidino was vacuum-distilled a t 204-205°/ /2 ram; m.p. 128-129 °. S y n t h e s i s of polyamines. 1. B a s e d on D C B a n d aniline. 1-86 g of aniline was placed in a three-necked flask and dissolved in 11.0 ml of alcohol; 2.46 g of DCB and 1.52 g of anhydrous potassium carbonate were added. The contents were k e p t at 60-70 ° for 32 hr in a stream of argon, after which the reaction mass was t r e a t e d with water; the precipitate was washed with hot water, alcohol and ether. 2.6 g of product were obtained (72% yield on theoretical) and reprecipitated with hexane from chloroform solution and vacuum-dried a t 50-60 °. 2. B a s e d on D C B and a-naphthylamine. The oligomer was obtained from 7.86 g o f a-naphthylamine, 6.15 g of DCB and 8.25 g of anhydrous potassium carbonate in 25.0 ml o f alcohol. The reaction mass was k e p t at 60-70 ° for 26 hr in a stream of argon and t r e a t e d as described above. 3. Based on D C B a n d hydrazobenzene. 10'0 g of hydrazobenzene were placed in a flask together with 25.0 ml of alcohol, 6-15 g of DCB and 8.25 g of potassium carbonate. The contents were k e p t for 26 hr at 60-70 °. 4. B a s e d on D C B a n d p - p h e n y l e n e d i a m i n e . The oligomer was obtained from 1.08 g o f lo-phenylenediamine in 15 ml of ethyl alcohol, 2.46 g of DCB and 3.04 g of anhydrous potassium carbonate in the same way as for method 1. Potassium carbonate was removed from the product b y washing with water and the unreacted initial components were removed b y extraction with alcohol. 5. Based on D C B a n d benzidine. The oligomer was obtained from 1-84 g of benzidino in 20-0 ml of alcohol, 2.46 g of DCB and 3.04 g of anhydrous potassium carbonate. Treatm e n t of the reaction mass and of the resulting product were carried out as for 4. 6. B a s e d on D C H D a n d aniline. 0"93 g of aniline were placed in a flask together with

10.0 ml of alcohol, 1.47 g of D C H D and 1.52 g of anhydrous potassium carbonate, and kept for 20.5 hr at 60-70 °. The reaction mixture was treated with water and the precipitate was filtered off and again washed with water, alcohol and ether, and dried at 100-120 °

(3-4 mm). 7. Based on D C H D a n d ~-naphthylamine. 1.43 g of ~-naphthylamine were placed in a flask together with 10.0 ml of alcohol, 1.47 g of D C H D and 1.52 g of anhydrous potassium carbonate, and kept for 21.5 hr at 60-70 °. 8. B a s e d on D C H D a n d p - p h e n y l e n e d i a m i n e . The oligomer was obtained from 1"08 g of p-phenylenediamine in 15.0 ml of alcohol, 2.94 g of D C H D and 3.04 g of anhydrous potassium carbonate at 67-70 ° for 25.5 hr in a stream of argon. The reaction mass was treated in the same w a y as the corresponding oligomer of the butyne-2 series. 9. Based on D C H D a n d benzidine. The oligomer was obtained from 1.84 g of benzidine in 24.0 ml of alcohol, 2.94 g of I)CHD and 3.04 g of anhydrous potassium carbonate at 60-70 ° for 24.5 hr. B r o m i n a t i o n of H[N(CeHs)CH,-- C - C -- CH~] 8CI.

1. 0.4 g of the oligomer (m.w. 1100) were dissolved in 50 ml of chloroform, 0.6 ml of bromine dissolved in 15 ml of chloroform were added and heated for 8 hr. The precipitate was filtered off, washed with chloroform and hexane and dried a t 120°/5-6 ram; yield 0.7 g. Found, ~ :

C 29.62;

H 2.04;

N 4.32.

H[Iq(C~HdBr)--CH~--CBr=CBr--CH~]sC1. Calculated, ~ :

C 31.1;

H 2.07;

N

3-62.

2. 0"2 g of the same oligomer were dissolved in 15.0 ml of chloroform and 0"6 ml of bromine dissolved in 15 ml of chloroform were added and heated for 25 hr; 0.4 g of product were obtained. Found, ~ : C 21.97; H 1"44; N 3.84. H[N(CeHdBr)--CH~--CBr,--CBr~--CH~],C1. Calculated, ~ :

C 22.0;

H 1-46;

1~ 2.56.

Bromination of H [ N ( C e H s ) - - C H ~ - - C - C - - C - C - - C H 2 ] 3 C 1 . 0.3 g of oligomer was synthesized in 20 ml of chloroform, 10 ml of bromine in 20 ml of chloroform were added and heated for 21.5 hr. The precipitate was filtered off, washed with acetone and vacuum-dried. Found, ~ :

C 34"79;

i

1"77;

N 3.1

H [ N ( C s H a B r ) - - C H a - - C B r = C B r - - C I - I = C = C H - - ] a C 1 . Calculated, ~ : C 34"6; H 1.92; N 3"36. I o d o m e t h y l a t i o n of I-I[N(CJ-Is)CH~--C--C--CI-Is]sC1. 0"3 g of oligomer with m.w. 850 and softening point I20-130 ° was dissolved in 40 ml of m e t h y l iodide. The contents were cold stored for 12 hr and then heated at ~ 4 0 ° for 2-3 hr. The precipitate was filtered off and dried off i n vacuo. Softening point of product, 72-76 °. Found, ~ : C 48"28; H 4.27; N 5"47. + H[N(CeHs)--CH~--C--C--CH2]5--N(C6Hs)--CH2--C--C--CH2C1. Calculated, ~ : I CH3I-. H 4"3;

C 48.6; N 5"23.

CONCLUSIONS (l) P o l y a m i n e s w i t h a c e t y l e n e groups h a v e been synthesized b y nonequilibr i u m p o l y c o n d e n s a t i o n o f 1 , 4 - d i c h l o r o b u t y n e - 2 a n d 1,6 d i c h l o r o h e x a d i y n e - 2 , 4 with aniline, a-naphthylamine, p-phenylenediamine, zene.

benzidine and hydrazoben-

(2) The structure of the oligomers has been confirmed by IR spectroscopy and by the reactions of bromination, hydration and iodomethylation. Translated by R. J. A. I-IENDB,Y

REFERENCES 1. A. W. JOHNSOI~, J. Chem. Soc. 1009, 1946

2. J. B. ARMITAGE, E. R. H. JONES and M. C. WHITING, J. Chem. Soc. 44, 1951 3. H. A. SZYMANSKI, Interpreted Infrared Spectra, vol. 2, 5, 1966; Plenum Press, New York 4. V. WOLF, Liebig's Arm. Chem. 592: 222, 1955 5. V. WEST (Ed.), Use of Spectroscopy in Chemistry, 1959 6. Yu. I. PORFIR'EVA, E. S. TURBANOVA and A. A. PETROV, Zh. organ, khim. 2: 772, 777, 1966 7. J. H. WOTIZ, F. A. MILLER and R. J. PALCHAK, J. Amer. Chem. Soe. 72: 5055, 1950 8. C. L. COOK, E. R. H. JONES and M. C. WHITING, J. Chem. Soc. 2888, 1952 9. H. A. STANSBURY and W. R. PROOPS, J. Organ. Chem. 27: 320, 1962

THERMODYNAMIC STUDY OF SOLUBILITY OF GRAFT COPOLYMERS OF PERCHLOROVINYL AND POLYVINYLACETATE OBTAINED BY THE RADIATION METHOD* S. A. TASHMUKHAMEDOV, K m U. Us~A~ov, R. S. TILLAYEV a n d L. L. KIS'VYAI~TSEVA V. I. Lenin State University, Tashkent

(Received 16 March 1967)

THERE is at present a definite lack of published information in connection with thermodynamic studies of the solubility of graft copolymers obtained by the radiation method. However investigations of this type are important as the method adopted for radiation initiation of the graft copolymerization reaction (irradiation dose and dose rate, presence or absence of air) determines the mechanical properties of the product obtained, including its solubility. In an earlier paper we showed that the reduced solubility of the graft copolymer compared with the initial polymer is due either to a reduction in the negative value of the enthalpy component (AH1) of the thermodynamic potential of the solvent (for the system cellulose acetate-polyvinylpyrrolidone [1]), or to a reduction in the * Vysokomol. soyed. AI0: No. 2, 379-383, 1968.