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Патент USA US3074999

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United States Patent 0
Patented Jan. 22, 1963
?uorobutoxy phosphorus nitrite with sodium thiocyanate
is shown:
\ /
Rudi F. W. Riitz, Hamden, ‘Conn, assignor to Olin
Mathieson Chemicalicorporation, a corporation of
No Drawing.2 giled‘ July 11, 1961, Ser. No. 123,089
0 F30 FrC F2CH2O
lainls. (Cl. 260-454)
This invention relates to trimeric isothiocyano poly
?uoroalkoxy phosphorus nitriles and to their preparation.
It has now been found that trimeric isothiocyano poly
?uoroalkoxy phosphorus nitriles can vbe prepared by re
+ 3NaCl
action of an alkali metal thiocyanate with a trimeric halo
poly?uoroalkoxy phosphorus nitrile. The novel com 15 The novel trimeric isothiocyano polyiluoroalkoxy phos
pounds of this invention are sufficiently thermally stable
phorus nitriles are prepared in good yields by admixing the
that they can be subjected to vacuum distillation for puri?
trimeric halo poly?uoroalkoxy phosphorus nitrile with the
cation purposes, if desired.
alkali metal thiocyanate. In carrying out the reaction ap
‘ Trimeric halo poly?uoroalkoxy phosphorus nitriles use
proximately theoretical quantities of the starting reactants
ful as starting materials have the formula:
are employed as set forth in the preceding equation al
though, if desired, an excess of alkali metal thlocyanate can
be employed to insure completion of the reaction. Prefer
ably the reaction is carried out in the presence of a com
25 mon solvent for both of the reactants which can be ace
tone, acetonitrile etc. The reaction proceeds in general
at temperatures between about -—20° C. and about +80°
C. When a solvent is employed, the reaction is preferably
conducted at the re?ux temperature of the solvent. The
30 reaction time will vary from about 2 minutes to about 1
hour or more depending upon the reaction temperature,
the particular solvent employed and the particular react
ants utilized. The alkali metal halide formed during the
reaction is generally insoluble in the applied solvent. The
wherein R1, R2, R3, R4, R5 and R6 are selected from the
group consisting of chlorine, bromine, ?uorine, or
~—OCH2(CF2)mY, wherein Y is selected from the group
salt can be removed by ?ltration or by washing with
consisting of hydrogen or ?uorine, m is an integer of from
1 to 20, wherein in the said nitrile at least one of the
The new trimeric isothiocyano poly?uoroalkoxy phos~
phorus nitriles are useful in the ?eld of resins and plastics.
and at least one of the R1, R2, R3, R4, R5 and R6 sub
When heated with bifunctional aliphatic amines of the
stituents is chlorine, bromine or ?uorine. Suitable halo 40 general formula NH2(CH2),,NH2 where n is an integer
poly?uoroalkoxy phosphorus nitriles for the novel reac
of from 2 to 8 inclusive solid polymeric materials with
the retained -—P=N—~ ring structure are obtained. Suit
tion of this invention include trimeric 1-chloro-l,3,3,5,5
pentakis-alpha, alpha-H,H-tri?uoroethoxy phosphorus ni
able bifunctional aliphatic amines include ethylene di
R1, R2, R3, R4, R5 and R6 substituents is —-OCH2(CF2)mY
trile, trirneric l,3,5~trichloro-1,3,5-tris-alpha, alpha-HH
tri?uoroethoxy phosphorus nitrile, trimeric 1,3-dichloro
amine, 1,3-diaminopropane, 1,4-diaminopropane, 1,6-di
45 aminohexane, etc. The powdery, polymeric materials ob
phosphorus nitrile, 1,1,3,3-tetrachloro-5,Sebis-alpha, alpha,
tained by the reaction of the trimeric isothiocyano poly
?uoroalkoxy phosphorus nitriles with hifunctional ali
omega-H,H,H~hexa?uorobutoxy phosphorus nitrile, 1
phatic amines can be further subjected to a thermal treat
1,3,5,5-tetrakis - alpha, alpha - H,H - penta?uoropropoxy
chloro-1,3,3,5,5-pentakis-alpha, alpha, omega-H,H,H-do
deca?uoroheptoxy phosphorus nitrile, 1,1-dichloro-3,3,5,5
tetrakis-alpha, alpha, omega-H,H,H-eicosa?uoroundecan
ment yielding glass-like, polymeric materials which are
non-in?ammable and practically non-combustible. These
glass-like, polymeric materials can be utilized as protec
oxy phosphorus nitrile, etc. and the corresponding bromine
and ?uorine derivatives. The above-mentioned com
pounds can be conveniently prepared by the general
tive coatings for metals. Such coated metal products can
be formed by dipping the metal article into the molten
method described in Ritz et al. United States Patent
Trimeric 1 ,1 -B is-lsothi0cyan0-3,3,5 ,5 ~Tetrakis-A lpha,
2,876,247. For example, trimeric 1,3-dichloro-1,3,5,5~
tetrakis-alpha, alpha-H,H-hepta?uorobutoxy phosphorus
nitrile can be prepared by reacting 1 mole of trimeric
phosphonitrilic chloride with 4 moles of the sodium salt
of 1,l-H,H-hepta?uorobutanol in toluene at a temperature 60
of about 100° C.
The reaction proceeds as set forth in the following equa
tion in which, by way of illustration, the reaction between
trimeric 1,3,34trichloro-1,5,5-tris-alpha, alpha-I-LH-hepta
Alpha-H,H-Hepta?uorobutoxy Phosphorus N itrile
\ /
II / \}II
0 F30 F20 memo-4e
P——() CI-IzC F2CF2C Fa
To 8.062 grams of trimeric 1,l-dichloro-3,3,5,S-tetrakis
gram of ethylenediamine (98 percent, 0.00412 mole). An
exothermic reaction was observed with solidi?cation of
the mixture. The slightly yellowish material so obtained
was extracted with 50 ml. of hexane and ?nally with the
same amount of dry ether. The crude, polymeric, pow
dery material thus obtained melted between 122° and
alpha, alpha-H,H-hepta?uorobutoxy phosphorus nitrile
(0.0082 mole) dissolved in 15 ml. of dry acetone there was
added in one portion a solution of 1.72 grams of potas
sium thiocyanate (0.165 mole) in 35 ml. of the same sol
vent. The resulting reaction mixture was then re?uxed
for lO'minutes. On standing overnight the. theoreticalv
amount of potassium chloride (1.2 grams), which had
precipitated from the reaction mixture, was removed by
124° C.
A sample of the polymeric material obtained in the
preceding paragraph was subjected to extended heating
?ltration- From the clear ?ltrate the solvent was then 10 at 170° C. in a nitrogen atmosphere. After 3 hours no
recovered by distillation and a yellowish, oily residue ad
further weight-loss was observed and a glass-like poly
mixed with some excess potassium thiocyanate remained.
meric material, which was non-inflammable and practi
Separation of the oil from the solid was'e?'ected by the
cally non-combustible, was obtained.
addition of 25 ml. of ether ‘followed by ?ltration. After
What is claimed is:
removal of the ether in vacuo, the remaining oil was 15
l. Trimeric isothiocyano poly?uoroalkoxy phosphorus
purified by vacuum distillation yielding 6.9 grams (782
nitriles of the formula:
percent of the theoretical yield)‘ of trimeric 1,1-bis-iso
' thiocyano-3,3,5,5-tetrakis-alpha,
alpha-H,H - hepta?uoro
butoxy phosphorus nitrile; BP. 149/ 15 1° C. (0.9 mm.),
7192!: 1.3847.
The puri?ed product so obtained was. a 20
slightly yellowish, clear oil.
The product was analyzed for carbon, hydrogen, nitro~
gen, phosphorus, and sulphur and the following results
were obtained:
wherein RDVRZ, R3, R4, R5, and R5 are selected from the
group consisting of —-—NCS'and --OC_H2(CF2)mY, where:
in Y is selected from thegroup consisting of hydrogen and
fluorine, is an integer of from 1 to 20, wherein at leastv
one of the R1, R2, R3, R4, R5, and R6 substituents is--NCS,
and wherein at least one of the R1, R2, R3, R4, R5, and_RB_
Calcd.lorC1sHsFasN5P3S2O4 ________ ._ 20.61
0. 77
'Found_'_ ____________________________ -_ 21.94
30 substituents is ——OCH2(CF2)mY.
-”Anfamount-of 4.31 ‘grams of trimeric 1,1-bis-isothio-.
alpha-H,H-hepta?uorobutoxy phosphorusnitrile.
cyano-3,3,5,5-tetrakis-alpha, alpha-H,H-hepta?uorobutoxy~
phosphorus nitrile (0.00412 mole) was mixed with 0.248
2; Trimeric 1,1 - bis-isothiocyano-3,3,5,5-tetralcis-alpha,
No references cited.
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