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Phosphonitrilic chloride—XXII
J. inorg,nucl, Chem., 1975,Vol. 37, pp. 29-33. Pergamon Press. Printed in Great Britain.
PHOSPHONITRILIC CHLORIDE--XXII THE SUBSTITUTION REACTION OF DICHLOROCYCLOTRIPHOSPHAZENE WITH SODIUM-BIS(HYDROXYMETHYL) BENZENES AND THE PROPERTIES OF POLYMERS MEISETSU KAJIWARA and HAJIME SAITO Department of Applied Chemistry, Faculty of Engineering, Nagoya University, Nagoya, Japan
(First received 14 November 1973; in final form 1 April 1974)
Abstract--The substitution reaction of dichlorocyclotriphosphazene with sodium-bis(hydroxymethyl)benzenes yield products of the types N3P3(OH2CC~H4CH2OH)6 and N3P3(OH2CC6H4CH20)3. N3Pa(2-OH2CC6H4CH2OH)6(I), N3P3(3-OH2CC6H4CH2OH)6(II), N3P3(4-OH2CC6H4CH2OH)~(III) and NaP3(2-OH2CC6H4CH20)3(IV ) all gave a singlet peak in the 3XP-NMR spectra. Water vapor and formaldehyde were detected by gas chromatography, and thermoplastic polymers were obtained when (I)-(III) were heated in the temperature range 150°C-250°C. The resulting polymers were stable toward water, dilute H2SO4, HNO3, or NaOH. Thermal degradation of the polymers yielded xylene, water and formaldehyde at 320"C. When (IV) was heated at about 200°C, thermal decomposition occurred rather than ring cleavage.
INTRODUCTION
an exchange reaction between EtONa and the bis(hydroxymethyl)benzenes.
D! CHLOROCYCLOTRIPHOSPHAZENE (NPCI2) 3 forms linear polymers at elevated temperatures. Cyclolinear polymers, and cross-linked polymers with a cyclomatrix are prepared by linking together cyclic oligometric ring systems by means ofdifunctional reagents. For example, the interaction of 1,5-dichloro-l,3,3,5,6,6-hexaphenylcyclotetraphosphazene with 4,4'-dihydroxybiphenyl[1], hydroxyphosphazenes with diphenyldichlorosilane[2], aminophosphazenes with diols[3], alkoxyphosphazenes with aromatic diols[4], bisazidophosphazenes with diphosphines[5], and hexachlorocyclotriphosphazene with aromatic diols[6-11]. This report describes a synthesis of cyclotriphosphazene derivatives with dichlorocyclotriphosphazene and sodium-bis(hydroxymethyl)benzenes, and cyclomatrix or cyclolinear phosphazene polymers from a condensation reaction with - C H 2 O H groups.
The substitution reaction of dichlorocyclotriphosphazen with sodium-bis(hydroxymethyl)benzenes The reactions between dichlorocyclotriphosphazene and the different sodium-bis(hydroxymethyl)benzenes were carried out in dioxan solution at various reaction temperature. After completion of the reaction mixture was separated by filtration, and the filtrate distilled under vacuum. The product was purified by recrystallization from dioxan solution containing active carbon. In this reaction, no hydrogen chloride gas was evolved. The degree of conversion was calculated from the quantity of sodium chloride determined with 0.01N AgNO 3 .
Polycondensation, separation and purification of the polymers The substitution products were heated in a glass tube (120 m m x 200 ram), using an electric furnace, at 150°C or 200~C in air for various periods of time. The heat treated materials were separated into soluble (A) and insoluble products (B) using dioxan as solvent, and the compositions of the products were determined by elemental analysis.
EXPERIMENTAL
Preparation of dichlorocyclotriphosphazene, bis(hydroxymethyl)benzenes and sodium-bis(hydroxymethyl)benzenes
Analytical data
Dichlorocyclotriphosphazene (NPC12)3 was obtained by the modified method of Saito and Kajiwara[12]. 1,2-, 1,3- and 1,4-bis(hydroxymethyl)benzenes were synthesized from anhydrous phthalic acid, isophthalic methyl ester and terephthalic methyl ester, respectively, by reductions involving LiAIH4113-15 ]. Sodium-bis(hydroxymethyl)benzenes were obtained using
Molecular weights were measured by the cryoscopic method, or GPC using dioxan solvent. Water and formaldehyde were determined by gravimetric analysis or oxidation-reduction titrations using 12 . 1H-NMR spectra were measured with a Nihon Denshi JNMC-60 type spectrometer for 60 MHz at 20°C using TMS as the internal standard. 3Xp-NMR spectra were measured 29
30
MEISETSU KAJIWARA a n d HAJ1ME SAITO
with a Nihon Denshi JNMC-60 HL type spectrometer using chloroform or DMSO solvent and H 3 P O 4 as the reference. X-ray powder diffraction photographs was measured using Shimazu Co., VDF-1 camera. I.R. absorption spectra were measured with a Shimazu Co., IRG-2 type using the KBr disc technique. The gas chromatography used was a Shimazu Co., GC-5A type.
/ mole 14
-I.5
9 I0 6
t~ o I -2-0
RESULTS AND DISCUSSION The products obtained are shown in Table 1 together with the solubilities of the benzenes. NaPs (2-OH2CC6H4CH2OH6(I) (&p = - 3.2 ppm), NaP3 (3-OH2CC6H4CH2OH)6(II) (~o = + 1'9 ppm), N3P 3 (4-OH2CC6H4CH2OH)6(III) (c~p= +0-7 ppm) and NaP s (2-OH2CC6H4CH2OH)a(IV) (&o = - 3 ' 9 ppm) show only one peak in their 31p-NMR spectra. Bands characteristic of P=N or P - O - R appeared in the region 1200 cm- 1, and 980 to 1100 cm- l, respectively. Accordingly, the structures of the products are postulated as (X) and (Y), respectively.
I
I
I
I
I
2.7
2-8
2.9
3'0
3.1
-2.5 2.6
I/T
x
3,2
I0 3
Fig. 1. The relationship log k and 1/T
x 10 3.
Reaction systems : I. (NPCI2)3 + 2-NaOH2CC6H4CHzOH II. (NPC12)3 + 3-NaOH2CC6H4CH2OH II1. (NPCI2)3 + 4-NaOH2CC6H4CH2OH IV. (NPCI2)3 + 2-NaOH2CC6H4CH2ONa. n 2 CO
HOHzCH4C6CH20"~)
N
~//OH2CC6H4CH2OH
HOHzCH4C6CH20 / : ' ~ P ~ o H 2 C C 6 H 4 C H 2 0
N
P N
OH 2
H 0
/ N
H O H 2CH4C6CH2O /
O
OH2C.
0
\ O H 2CC 6H 4CH 2OH (x) (Y)
Activation energy o f the substitution reaction
The extent of reaction was measured by the amount of sodium chloride formed under various experimental conditions, and the velocity constant determined using Eqn (1), K = 1/(n - t ) t ( I / C " - 1 _ 1/C~o- 1)
(1)
in which n is the reaction order, t is the time, Co is the total sodium chloride when the reaction is complete, C is the amount of sodium chloride when the reaction time is t, and k is the velocity constant. The reaction is second order. Arrhenius plots, shown in Fig. I, were made to determine the activation energy. The high solubility of 2-NaOH2CC6H4CH2ONa may explain why it has the lowest value.
Polycondensation reaction o f the products
(I)-(III) were examined by differential thermal analysis (D.T.A.). Peaks for exothermic reactions appeared at 170°C, 41(YC, 630°C (I): 160°C, 510°C (II): 180°C, 320°C, 360°C, 510°C (III), and peaks for endothermic reactions appeared at 300°C, 450~C (I): 350°C (II): 30(I'C, 340"C, 4500C (III). It is proposed that the exothermic reaction at 160180°C is the polycondensation of-CH2OH. On heating (I)--fill) from room temperature to 200°C, water vapor and formaldehyde gas was detected (Table 2).
Phosphonitrilic chloride--XXlI
666~
0000 0
dddd ffffffff 5~
0000 ZZ
0
0
0
~
0
0
0
u.. 0
¢'~ I
0
~f 0
0000 e~
0000 m ~ m ~
ffffffff
31
32
MEISETSUKAJIWARAand HAJIMESAITO
Table 2. The amounts of products formed during the polymerization of one mole of raw materials at 200°C and yields,of insoluble polymer (A) and soluble polymer (B) Products formed (mole) H20 HCHO
Raw material (I)
NaP 3 (2-OH2CC6H4.CH2OH)6 N3P 3 (3-OH2CC6H4CH2OH)6 (III) N3P 3 (4-OH2CC6H4CH2OH) 6
(II)
1.5 2"0 4"0
Time* (hr)
0.03 0'02 0"03
Yield (~)t (A) (B)
2.0 1"5 1"0
5.73 9"32 5"76
94.27 90"68 94"24
Mol. wt. (B) 3500 9500 14500
* At the steady state. t The polymers were obtained by heating the materials at 200°C for 5"0 hr, and separated by dissolving them in dioxan.
From the D.T.A. and gas chromatography data, it appears that polycondensation reaction occurrs both intermolecularly or intramolecularly. It can be seen (Table 2) that much larger amounts of water are formed when (III) is heated at 200°C. Furthermore, the yields of(A) and (B) and the molecular weight of (/3) from (III) indicated that it had the highest molecular weight. Thus, polycondensation of (III) occurs most readily. This may be attributed to a symmetrical -CH2OH in (III). Molecular weights of products (A) obtained from (I}-{III) could not be measured because they were insoluble in most organic solvents. The i.r. absorption spectra of (A) and (B) obtained from (I)-(III) by heating at 200°C for 1"0 hr were recorded. The P=N fi'equency of (A) and (B) appeared at 1200 cm-1. On the other hand, the P=N frequency of the rubber-like polymer formed by heating is at 1365 cm-1-1380 cm-1 whereas for the trimer the P=N frequency is at 1218 cm -1. Also, the band due to 42H2OCH 2- formed by the polycondensation reaction of-CHEOH groups appeared at 1150cm- 1_1060 cm- t, but that of the -C6H4CH2C6H 4- group formed by polycondensation o f - C H 2 O C H 2- or -CH2OH is no longer distinguished from the other - C H 2- groups. The structures of the products (A) or (B) could be deduced from the analytical data as follows :
Ring cleavage polymerization reaction of N3P3 (2-OH2CC6H4CH20)3 (IV) The onset of ring cleavage was investigated by D.T.A. The exothermic reaction peaks appeared at 150°C, 250°C and 52&C, whilst endothermic reactions took place 200°C with one at 100°C due to melting. The nature of the reaction taking place at the other peaks was studied using gas chromatography. It was found that CO, CO2, water vapour, CHaC6Hs, C6H6, o-CH3C6H4CH a were formed when the temperature was raised to 150°C. Thus, decomposition occurred rather than cleavage of the NaP a ring, although the mechanism of decomposition cannot be explained.
The properties of the polymers The degree of hydrolysis of polymers (A) and (B) formed from (I)-(III) was estimated by treatment in water at 100° C for 30 min. The extent of hydrolysis was about 0.1-0.6 per cent; by comparison dichlorocyclotriphosphazene and dichlorophosphazene polymer are completely hydrolyzed to phosphoric acid, hydrogen chloride and ammonium. The polymers were stable towards dilute H2SO4, HNO 3 or NaOH solution. The weight loss on heating in air was measured on a thermo-
- - N-)p~OH 2CC6H4CH2 OH
HOH2CC6H4CH20
N--
=N
HOH2CC6H,CH20
N=
OH2CC6HgCH2OH
-2H20
zN
OH2CC6H4CH2OH2CH4C6CH20
N---
-2HCHO
CC6H,CH2C6H,CH20>/ OH =N
OH2CC6H4CH2C6H,CH20
N---
Phosphonitrilic chloride--XXll
balance (Fig. 2). The most stable polymer is obtained from (III), and the stability is related to the degree of condensation. The products formed at the onset of thermal decomposition were examined by gas chromatography. H20, CH3C6Hs, CH3C6H4CH3, CH20, CO2, C2H4 and C 6 H 6 were detected at 320"C.
Q.
50 --
O
r ioo o
I00
I
I
J
I
200
300
400
500
Temperature~
°C
Fig. 2. TG curves of polymers in air, at rate of 5°C/min. Raw materials : I. N3Pa(2-OH2CC6H4CH2OH) 6 II, NaP3(3-OH2CC6H4CH2OH)6 III. N3P3(4-OH2CC6H4CH2OH) 6 .
600
33 REFERENCES
1, A. J. Bilbo, C. M. Douglas, N. R. Fetter and D. L. Herring, J. Polym. Sci. A-l, 1671 (1968). 2. S. I. Belkyh, S, M. Zhivukhin, V. V. Kireyev and H. S. Kolesnikov, Vysokomol Soedin. Ser. A l l , 625 (1969). 3. M. V. Lenton and B. Lewis, J. chem. Soc. 665 (1966). 4. A. J. Bilbo and C. M. Sharts, J. Polym. Sci. A-I, 2891 (1967). 5. C. A. Redfarn, U.S. Patent 2, 866, 773 (1958). 6. R. G. Rice, B. H. Geib and L. A. Kaplan, U.S. Patent 3, 121,704 (1964). 7. S.M. Zhivukhin, B. V. Tolstoguzov and A. N. Zelenskii, Zh. prikl. Khim. Leningrad 39, 234 (1966). 8. S. M. Zhivukhin, V. V. Kireev and A. N. Zelenskii, Soy. Plast. 24 (1963). 9. M. Yokoyama, H. Cho and K. Kono, Kogyo Kagaku Zasshi 67, 1378 (1964). 10. S. M. Zhivunkhin, V. B. Tolstoguzov and F. J, Yakobson, Vysokomol. Soedin. 8, 727 (1966). 11. W. R. Grace and Co., British Patent 981,821 (1965). 12. H. Saito and M. Kajiwara, J. chem. Soc. Japan, Ind. Chem. Sect. 66, 618 (1963). 13. R. F. Niston and W. G. Brown, J. Am. chem. Soc. 69, [ 197 (1947). 14. S, W. Chaikin and W. G. Brown, J. Am. chem, Soc. 71, 122 (1949). 15. V. Porrin, Gazz. chim, ital. 87, 1147 (1957).
PHOSPHONITRILIC CHLORIDE--XXII THE SUBSTITUTION REACTION OF DICHLOROCYCLOTRIPHOSPHAZENE WITH SODIUM-BIS(HYDROXYMETHYL) BENZENES AND THE PROPERTIES OF POLYMERS MEISETSU KAJIWARA and HAJIME SAITO Department of Applied Chemistry, Faculty of Engineering, Nagoya University, Nagoya, Japan
(First received 14 November 1973; in final form 1 April 1974)
Abstract--The substitution reaction of dichlorocyclotriphosphazene with sodium-bis(hydroxymethyl)benzenes yield products of the types N3P3(OH2CC~H4CH2OH)6 and N3P3(OH2CC6H4CH20)3. N3Pa(2-OH2CC6H4CH2OH)6(I), N3P3(3-OH2CC6H4CH2OH)6(II), N3P3(4-OH2CC6H4CH2OH)~(III) and NaP3(2-OH2CC6H4CH20)3(IV ) all gave a singlet peak in the 3XP-NMR spectra. Water vapor and formaldehyde were detected by gas chromatography, and thermoplastic polymers were obtained when (I)-(III) were heated in the temperature range 150°C-250°C. The resulting polymers were stable toward water, dilute H2SO4, HNO3, or NaOH. Thermal degradation of the polymers yielded xylene, water and formaldehyde at 320"C. When (IV) was heated at about 200°C, thermal decomposition occurred rather than ring cleavage.
INTRODUCTION
an exchange reaction between EtONa and the bis(hydroxymethyl)benzenes.
D! CHLOROCYCLOTRIPHOSPHAZENE (NPCI2) 3 forms linear polymers at elevated temperatures. Cyclolinear polymers, and cross-linked polymers with a cyclomatrix are prepared by linking together cyclic oligometric ring systems by means ofdifunctional reagents. For example, the interaction of 1,5-dichloro-l,3,3,5,6,6-hexaphenylcyclotetraphosphazene with 4,4'-dihydroxybiphenyl[1], hydroxyphosphazenes with diphenyldichlorosilane[2], aminophosphazenes with diols[3], alkoxyphosphazenes with aromatic diols[4], bisazidophosphazenes with diphosphines[5], and hexachlorocyclotriphosphazene with aromatic diols[6-11]. This report describes a synthesis of cyclotriphosphazene derivatives with dichlorocyclotriphosphazene and sodium-bis(hydroxymethyl)benzenes, and cyclomatrix or cyclolinear phosphazene polymers from a condensation reaction with - C H 2 O H groups.
The substitution reaction of dichlorocyclotriphosphazen with sodium-bis(hydroxymethyl)benzenes The reactions between dichlorocyclotriphosphazene and the different sodium-bis(hydroxymethyl)benzenes were carried out in dioxan solution at various reaction temperature. After completion of the reaction mixture was separated by filtration, and the filtrate distilled under vacuum. The product was purified by recrystallization from dioxan solution containing active carbon. In this reaction, no hydrogen chloride gas was evolved. The degree of conversion was calculated from the quantity of sodium chloride determined with 0.01N AgNO 3 .
Polycondensation, separation and purification of the polymers The substitution products were heated in a glass tube (120 m m x 200 ram), using an electric furnace, at 150°C or 200~C in air for various periods of time. The heat treated materials were separated into soluble (A) and insoluble products (B) using dioxan as solvent, and the compositions of the products were determined by elemental analysis.
EXPERIMENTAL
Preparation of dichlorocyclotriphosphazene, bis(hydroxymethyl)benzenes and sodium-bis(hydroxymethyl)benzenes
Analytical data
Dichlorocyclotriphosphazene (NPC12)3 was obtained by the modified method of Saito and Kajiwara[12]. 1,2-, 1,3- and 1,4-bis(hydroxymethyl)benzenes were synthesized from anhydrous phthalic acid, isophthalic methyl ester and terephthalic methyl ester, respectively, by reductions involving LiAIH4113-15 ]. Sodium-bis(hydroxymethyl)benzenes were obtained using
Molecular weights were measured by the cryoscopic method, or GPC using dioxan solvent. Water and formaldehyde were determined by gravimetric analysis or oxidation-reduction titrations using 12 . 1H-NMR spectra were measured with a Nihon Denshi JNMC-60 type spectrometer for 60 MHz at 20°C using TMS as the internal standard. 3Xp-NMR spectra were measured 29
30
MEISETSU KAJIWARA a n d HAJ1ME SAITO
with a Nihon Denshi JNMC-60 HL type spectrometer using chloroform or DMSO solvent and H 3 P O 4 as the reference. X-ray powder diffraction photographs was measured using Shimazu Co., VDF-1 camera. I.R. absorption spectra were measured with a Shimazu Co., IRG-2 type using the KBr disc technique. The gas chromatography used was a Shimazu Co., GC-5A type.
/ mole 14
-I.5
9 I0 6
t~ o I -2-0
RESULTS AND DISCUSSION The products obtained are shown in Table 1 together with the solubilities of the benzenes. NaPs (2-OH2CC6H4CH2OH6(I) (&p = - 3.2 ppm), NaP3 (3-OH2CC6H4CH2OH)6(II) (~o = + 1'9 ppm), N3P 3 (4-OH2CC6H4CH2OH)6(III) (c~p= +0-7 ppm) and NaP s (2-OH2CC6H4CH2OH)a(IV) (&o = - 3 ' 9 ppm) show only one peak in their 31p-NMR spectra. Bands characteristic of P=N or P - O - R appeared in the region 1200 cm- 1, and 980 to 1100 cm- l, respectively. Accordingly, the structures of the products are postulated as (X) and (Y), respectively.
I
I
I
I
I
2.7
2-8
2.9
3'0
3.1
-2.5 2.6
I/T
x
3,2
I0 3
Fig. 1. The relationship log k and 1/T
x 10 3.
Reaction systems : I. (NPCI2)3 + 2-NaOH2CC6H4CHzOH II. (NPC12)3 + 3-NaOH2CC6H4CH2OH II1. (NPCI2)3 + 4-NaOH2CC6H4CH2OH IV. (NPCI2)3 + 2-NaOH2CC6H4CH2ONa. n 2 CO
HOHzCH4C6CH20"~)
N
~//OH2CC6H4CH2OH
HOHzCH4C6CH20 / : ' ~ P ~ o H 2 C C 6 H 4 C H 2 0
N
P N
OH 2
H 0
/ N
H O H 2CH4C6CH2O /
O
OH2C.
0
\ O H 2CC 6H 4CH 2OH (x) (Y)
Activation energy o f the substitution reaction
The extent of reaction was measured by the amount of sodium chloride formed under various experimental conditions, and the velocity constant determined using Eqn (1), K = 1/(n - t ) t ( I / C " - 1 _ 1/C~o- 1)
(1)
in which n is the reaction order, t is the time, Co is the total sodium chloride when the reaction is complete, C is the amount of sodium chloride when the reaction time is t, and k is the velocity constant. The reaction is second order. Arrhenius plots, shown in Fig. I, were made to determine the activation energy. The high solubility of 2-NaOH2CC6H4CH2ONa may explain why it has the lowest value.
Polycondensation reaction o f the products
(I)-(III) were examined by differential thermal analysis (D.T.A.). Peaks for exothermic reactions appeared at 170°C, 41(YC, 630°C (I): 160°C, 510°C (II): 180°C, 320°C, 360°C, 510°C (III), and peaks for endothermic reactions appeared at 300°C, 450~C (I): 350°C (II): 30(I'C, 340"C, 4500C (III). It is proposed that the exothermic reaction at 160180°C is the polycondensation of-CH2OH. On heating (I)--fill) from room temperature to 200°C, water vapor and formaldehyde gas was detected (Table 2).
Phosphonitrilic chloride--XXlI
666~
0000 0
dddd ffffffff 5~
0000 ZZ
0
0
0
~
0
0
0
u.. 0
¢'~ I
0
~f 0
0000 e~
0000 m ~ m ~
ffffffff
31
32
MEISETSUKAJIWARAand HAJIMESAITO
Table 2. The amounts of products formed during the polymerization of one mole of raw materials at 200°C and yields,of insoluble polymer (A) and soluble polymer (B) Products formed (mole) H20 HCHO
Raw material (I)
NaP 3 (2-OH2CC6H4.CH2OH)6 N3P 3 (3-OH2CC6H4CH2OH)6 (III) N3P 3 (4-OH2CC6H4CH2OH) 6
(II)
1.5 2"0 4"0
Time* (hr)
0.03 0'02 0"03
Yield (~)t (A) (B)
2.0 1"5 1"0
5.73 9"32 5"76
94.27 90"68 94"24
Mol. wt. (B) 3500 9500 14500
* At the steady state. t The polymers were obtained by heating the materials at 200°C for 5"0 hr, and separated by dissolving them in dioxan.
From the D.T.A. and gas chromatography data, it appears that polycondensation reaction occurrs both intermolecularly or intramolecularly. It can be seen (Table 2) that much larger amounts of water are formed when (III) is heated at 200°C. Furthermore, the yields of(A) and (B) and the molecular weight of (/3) from (III) indicated that it had the highest molecular weight. Thus, polycondensation of (III) occurs most readily. This may be attributed to a symmetrical -CH2OH in (III). Molecular weights of products (A) obtained from (I}-{III) could not be measured because they were insoluble in most organic solvents. The i.r. absorption spectra of (A) and (B) obtained from (I)-(III) by heating at 200°C for 1"0 hr were recorded. The P=N fi'equency of (A) and (B) appeared at 1200 cm-1. On the other hand, the P=N frequency of the rubber-like polymer formed by heating is at 1365 cm-1-1380 cm-1 whereas for the trimer the P=N frequency is at 1218 cm -1. Also, the band due to 42H2OCH 2- formed by the polycondensation reaction of-CHEOH groups appeared at 1150cm- 1_1060 cm- t, but that of the -C6H4CH2C6H 4- group formed by polycondensation o f - C H 2 O C H 2- or -CH2OH is no longer distinguished from the other - C H 2- groups. The structures of the products (A) or (B) could be deduced from the analytical data as follows :
Ring cleavage polymerization reaction of N3P3 (2-OH2CC6H4CH20)3 (IV) The onset of ring cleavage was investigated by D.T.A. The exothermic reaction peaks appeared at 150°C, 250°C and 52&C, whilst endothermic reactions took place 200°C with one at 100°C due to melting. The nature of the reaction taking place at the other peaks was studied using gas chromatography. It was found that CO, CO2, water vapour, CHaC6Hs, C6H6, o-CH3C6H4CH a were formed when the temperature was raised to 150°C. Thus, decomposition occurred rather than cleavage of the NaP a ring, although the mechanism of decomposition cannot be explained.
The properties of the polymers The degree of hydrolysis of polymers (A) and (B) formed from (I)-(III) was estimated by treatment in water at 100° C for 30 min. The extent of hydrolysis was about 0.1-0.6 per cent; by comparison dichlorocyclotriphosphazene and dichlorophosphazene polymer are completely hydrolyzed to phosphoric acid, hydrogen chloride and ammonium. The polymers were stable towards dilute H2SO4, HNO 3 or NaOH solution. The weight loss on heating in air was measured on a thermo-
- - N-)p~OH 2CC6H4CH2 OH
HOH2CC6H4CH20
N--
=N
HOH2CC6H,CH20
N=
OH2CC6HgCH2OH
-2H20
zN
OH2CC6H4CH2OH2CH4C6CH20
N---
-2HCHO
CC6H,CH2C6H,CH20>/ OH =N
OH2CC6H4CH2C6H,CH20
N---
Phosphonitrilic chloride--XXll
balance (Fig. 2). The most stable polymer is obtained from (III), and the stability is related to the degree of condensation. The products formed at the onset of thermal decomposition were examined by gas chromatography. H20, CH3C6Hs, CH3C6H4CH3, CH20, CO2, C2H4 and C 6 H 6 were detected at 320"C.
Q.
50 --
O
r ioo o
I00
I
I
J
I
200
300
400
500
Temperature~
°C
Fig. 2. TG curves of polymers in air, at rate of 5°C/min. Raw materials : I. N3Pa(2-OH2CC6H4CH2OH) 6 II, NaP3(3-OH2CC6H4CH2OH)6 III. N3P3(4-OH2CC6H4CH2OH) 6 .
600
33 REFERENCES
1, A. J. Bilbo, C. M. Douglas, N. R. Fetter and D. L. Herring, J. Polym. Sci. A-l, 1671 (1968). 2. S. I. Belkyh, S, M. Zhivukhin, V. V. Kireyev and H. S. Kolesnikov, Vysokomol Soedin. Ser. A l l , 625 (1969). 3. M. V. Lenton and B. Lewis, J. chem. Soc. 665 (1966). 4. A. J. Bilbo and C. M. Sharts, J. Polym. Sci. A-I, 2891 (1967). 5. C. A. Redfarn, U.S. Patent 2, 866, 773 (1958). 6. R. G. Rice, B. H. Geib and L. A. Kaplan, U.S. Patent 3, 121,704 (1964). 7. S.M. Zhivukhin, B. V. Tolstoguzov and A. N. Zelenskii, Zh. prikl. Khim. Leningrad 39, 234 (1966). 8. S. M. Zhivukhin, V. V. Kireev and A. N. Zelenskii, Soy. Plast. 24 (1963). 9. M. Yokoyama, H. Cho and K. Kono, Kogyo Kagaku Zasshi 67, 1378 (1964). 10. S. M. Zhivunkhin, V. B. Tolstoguzov and F. J, Yakobson, Vysokomol. Soedin. 8, 727 (1966). 11. W. R. Grace and Co., British Patent 981,821 (1965). 12. H. Saito and M. Kajiwara, J. chem. Soc. Japan, Ind. Chem. Sect. 66, 618 (1963). 13. R. F. Niston and W. G. Brown, J. Am. chem. Soc. 69, [ 197 (1947). 14. S, W. Chaikin and W. G. Brown, J. Am. chem, Soc. 71, 122 (1949). 15. V. Porrin, Gazz. chim, ital. 87, 1147 (1957).