Method of obtaining polychlorphosphazenes

专利摘要:
METHOD FOR OBTAINING POPYCHLOROPHIPHPHASENES by condensation of the initial monomer under heating and atmospheric pressure: characterized by the fact that, for the purpose of polunen linear polymers with adjustable chain length, P-trichloro-H-dichlorophospho is used as the starting monomer at 240-280 C for 8 8, 5 h. CO with (
公开号:SU1131471A3
申请号:SU802985051
申请日:1980-09-23
公开日:1984-12-23
发明作者:Де Жаежер Роже；Элиуи Монсеф；Пюскарик Эмиль
申请人:Энститю Мондьяль Дю Фосфат (Фирма)；
IPC主号:

专利说明:

The invention relates to the preparation of linear polychlorophosphazenes. . Methods of cyclic polychlorophosphazenes are known, based on the tendency of cyclization of the lower compounds of the chlorophosphazene series. However, linear polychlorophosphazene is of much greater economic interest than cyclic ones, due to the wide possibilities of their use as materials such as silicones, plastics, natural and synthetic elastomers, as non-grill and non-flammable materials or additives that give fireproof materials. anti-flammable properties of the materials and substances to which they are added, as a lining, in particular waterproof coating in the biomedical field, in particular as fertilizer and lubricants. In addition, some elastomers obtained by various substitutions. Linear polychlorophosphazenes exhibit excellent resistance to both low temperatures and reagents that cause corrosion. The obvious fact of the use of polychlorophosphazenes is that the latter is the optimal starting point for obtaining polyorganophosphazene polymers with remarkable properties. There is a known method of preparing linear papichlor 4) osphazenes according to the scheme. PCH5 + NH, CL- (PNCL2) H + fHCL in symmetric tetrachloroethane, taken as solvent 11. However, this scheme requires a large number of reaction steps and is a long and painstaking process, as the resulting raw product is It is a mixture of cyclic components up to 90% and linear compounds such as RS () and, where n does not exceed 20, up to 10%. In order to obtain longer Nyc polymers, cyclic compounds are treated with solvents to separate the trimer and tetramer, from which they are extracted with appropriate, pure 1 (NPCl2i) 3 solvents, which are subjected to thermal polymerization under pressure and for 2 days to obtain a linear polymer () with an optimal percentage of 70% L2X. Dichlorophospharyl pentachloride diphosphazene CHg (0) p {RSCTP is prepared by reacting SOj to an ionic compound (CL3P N-PCL2 N-PCLj) PCLg obtained by reacting phosphorus pentachloride with ammonium chloride in a solvent with a weak dielectric constant 3J. However, it is not possible to obtain higher homologs in this way, where n is greater than 2, due to the formation of cyclic polyphosphazenes by reacting the ionic compound with ammonium chloride. A known method for the preparation of dichlorophosphorylheptahlortriophosphazene CLi (0)) - 5CL by breaking the hexachlorocyclotriophosphazene core with PCLj and the reaction of the breaking product c. There is also known a method according to which the first members of a series of linear phosphorylchlorophosphazenes are synthesized by gradually removing the PNN chain from the reaction of POCCj or phosphorylchlorophosphazenes with a short chain with hexamethyldisilazane and phosphorus pentachloride C5}. However, this method only produces triphosphazene, corresponding to forK1ule CL (0).) 3CL, which is also an unstable compound that decomposes when heated above 100 ° C with the release of POCb and the formation of high-polymeric compounds (Pbc), and about 20% hexychlorotrifaspase, while diphosphazene also tends to condense with strong heating, releasing POCB and forming high polymer compounds (PNCL2) n. , - The closest to the present invention is a method for producing a chlorphos phesenov floor by condensation of a phosphonitrile chlorine; REIDES of the formula CKPNCl) POC12 and POCl3 (HPC12) n when heated to 130-140 ° C and an atmospheric pressure of 6Jo. However, the known method does not allow the production of linear polyslor-, phosphazenes, but only low-molecular opigomers, the industrial use of which is limited. 5P31471 The purpose of the invention is to obtain linear polymers with adjustable chain length. The goal is achieved by the method of producing poly-5 chlorophosphazenes by condensing the initial monomer under heating and atmospheric pressure as the starting monomer using P-trichloro-N-dichlorophosphoryl-monophosphazene 10 of the formula
about C1
m i
с1-р-к р-сг I I
C1 C1
while controlling the injection of POCCj to quantitatively produce substantially pure polychlorophosphazene with a controlled degree of condensation.
Polycondensation of P-trichloro-N-dichlorophosphoryl monophosphazene is carried out at a temperature equal to or greater than 20-280 s for 8-8.5 hours at atmospheric pressure. It is advantageous to control the reaction of controlled polycondensation to almost complete - - O
removal, as well as in an inert gas atmosphere such as dehydrated nitrogen, which, in particular, favors the removal of POCt} and thus shortens the reaction time. 35
The degree of condensation obtained is dependent on various parameters, in particular, the temperatures used, the duration of heating, the working volume, 40 pressures used, the reaction conditions, such as stirring, the atmosphere in which the reaction takes place, etc., which can be programmed for
get an optimal result. 45
The product of the polycondensation reaction can be purified by treating it with cyclic phosphazene solvent and, at the same time, dissolving linear polychlorofas (phasic) with a short chain, less than 4 or 5, petroleum ether.
The proposed method allows to obtain linear / polychlorophosphazenes having a low percentage of- $ 5
impurities, below 5%, are removed (by treatment by the above purification). These impurities consist of
C1
(p-1-1I
- ChP-t -) C1
II
C1 C1
polychlorophosphazen i and linear polyphosphazenes with a short chain: 95% of the product precipitated during processing by purification were identified as high polymer substances chlorine | ophazenes by following methods.
IR spectrum of polychlorophosphazenes: intense and wide absorption in the 1300 stretch region — bond (decomposed into thin components in the case of thin films at 1310 and 1240 cm), two absorption of average intensity at 755 and 470 cm, corresponding to deformation of the bridges NPN and PNP, two absorbances, strong at 585 average intensity at 535 cm, corresponding to the stretching of the bond, a thin band of about 680 cm, corresponding to sedimentary benzene (the latter being a solvent of linear polychlorophosphazenes).
The NMR spectrum of phosphorus 31 has a peak at +18.8 ppm / 85% HjPO, the UV spectrum is subject to absorption in the region of 370 with the formation of linear phosphazine.
Thin-layer chromatography of the raw product of the reaction about: out near the complete absence of cyclic phosphazenes. The temperature measurement of the glass transition, carried out by differential enthalpy analysis on polymers of various lengths, is in the range of -60 ° C, while the number of elementary structures has a very small effect on the analysis.
PRI me R 1. Preparation of P trichloro-N-dichlorophosphoryl-monophosphazene. 0C1 II I Cl-P-N P-Cl 1I C1 C1 share is carried out at 240-280 ° C, 8-8.5 parts, the reaction is carried out according to the equation
P-trichloro-N-dichlorophosphoryl-monophosphazene is obtained by reacting RSZ with (NH) S0l in symmetric tetrachloroethane or chlorobenzene at their boiling points according to 5 with the two following options.
A. Ready t PrGNOClg in symmetric tetrachloroethane, starting from 25.43 g of 3.59, g (NH,) 2SO in 55 ml of symmetric .. The reaction is continued for 1 h at 146 ° С and 14.55 g of Pj NOClg are obtained .
B, Prepare Pj NOClg in chlorobenzene at 132 ° C, starting from 28.82 g
. and 4.07 g (Shd.) S0 (in 62 ml. 15 The reaction is carried out for 2 hours and 14.55 g of pure crystalline P2NOC15 are obtained.
2, Preparation of linear polychlorophosphazene Clji (0) p (NPCl2) r, Cl. ; 20
14.55 g of P2IOS15 n ° of radionuclide — But Example 1 is heated at 240 ° C. for 8 hours at atmospheric pressure. Clj (OPCNPClj Cl with an average molecular weight of 3500-25 (determined by vapor pressure osmometry)) is obtained, which corresponds to n = 29.
In the course of the reaction, ROSE is released, and if we assume that the loss corresponding to: molecular weight 3500, then i 30, it is equal to 8.0 g.
Example 2. 20.82 g of P2NOCl5 prepared according to Example 1.1) are heated for 8.5 hours at 280 ° C with moderate stirring during the whole heating.
The total mass of the collected POCtj is 160 g, attributable to 1 mol of the original. The difference with respect to 15.35 g (the mass of 1 mol of POCtj corresponds to obtaining (NPCl) is due to the distillation of a small amount of Pz NOST. This proves that at the end of the experiment the measurement of the volume POCtj
not enough to determine the number of basic elementary groups. The resulting raw, colorless product is completely soluble in benzene, which proves the absence of branched polychlorophosphazenes.
The results of the product analysis are as follows.
Calculated for (NPClj),%: C 61.21; N 12.07; R 26.72.
Found %: CE 61.52; N 11.90; R 26.81.
This product is treated with petroleum ether at 40-60 ° C, which is a precipitant of high-polymer compounds (NPClj) and a solvent for cyclic phosphazenes, as well as phosphazenes of type Cl OP-fNPCl) - C1, where n is very small.
In the same way, translated into growth:.
A thief fraction of 5% by weight of the treated product. Chromatographic control (thin-layer chromatography on SiOj plates, eluant-hexane) of the insoluble fraction proves the absence of sedimentary P.j. NOCl5 and cyclic phosphazenes. Determination of the average molecular weight carried out using a Knauer vapor pressure osmometer shows that it exceeds 20000.
The NMR spectrum of P-31 of this soluble phase suggests that the amount of cyclic phosphazene (NPC12). Where the raw product is almost insignificant; The molecular weight of the polymer obtained is in the order of 28,000-29,000, and n is in the order of 240-250.
In this way, linear polychlorophosphazenes i with a long chain are obtained, which provide great potential for their industrial use.

权利要求:
Claims (1)
[1]
METHOD FOR PRODUCING POLYCHLOROPHOSPHASENES by condensation of the starting monomer under heating and atmospheric pressure, characterized in that, in order to obtain linear polymers with an adjustable chain length, P-trichloro-N- 'dichlorophospho.ryl-monophosphazene is used and the reaction is carried out at 240 -280 C for 8 -
8.5 hours
SU <. „1131471
1 1131471

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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FR7924037A|FR2466435B1|1979-09-27|1979-09-27|

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