Note: Descriptions are shown in the official language in which they were submitted.
STATE OF THE ART
__
A number of polyphosphazene copolymers are known
in the art, but they are all characterized by the presence
of rando~ repeating units which can be characterized by the
random structures
~ r t B ~ B T
where ~ and B are different. A number of such copolymers
are described in U. S. Patents 3,271,330; 3,370,020, 3,370,026;
3,443,913; 3,515,6g8; 3,700,629; 3,702,833; 3,732,175;
3,~44,9~3; 3,856,712; 3,856,713; 3,869,058; 3,883,451; 3,888,799
and 3,888,800.
Attempts have been made in the prior art to
polymerize the cyclic compounds N3P3(OC6H5)6 and N3P3(C6H5)6
w~thout success (see Allcock, "Phosphorous-Nitrogen Compounds",
Academic Press, 1972, pgs. 323-328). The polymerization of
of N3P3FsC6Hs has been accomplished (see Allcock et al,
Maeromolecules, 8 337 (1975).
The polymers (I) of the present invention vary
markedly from the polymer [NPC12]n (see Allcock et al U. S.
3,370,020), in that one out of every three repeating units
is a ~NPCl(ORl)~ unit rather than a ~NPC12~ unit. Likewise,
the polymer (II) has a regularly oeeurring ~NP(ORl)(OR2)~
unit, as opposed to the totally random distribution in the
prior art copolyrners.
DI~SCRIPTIOM OF THE INVENTIOM
It has now been discovered that cyclic polyphos-
- 2 -
77
phazenes of the formula:
Cl Cl
C1~ ~ N ~ \ O
where Rl is
~ ~ _ R 3 X
when R3s, when present, are loca~ed in the meta or para positions
on the phenoxy ring, where x is 0 to 3; preferably 0 to 1
(where x is 1, R3 preferably is in the para position); and
where R3 is independently, lower (e.g. Cl-C10) linear or
branched alkyl, such as methyl, ethyl, n-butyl, sec. butyl
or tert. butyl, 2-ethyl hexyl and n-nonyl; lower (e.g.,
Cl-C4) linear or branched alkoxy, such as methoxy, ethoxy,
butoxy; halo te.g., chloro, bromo or fluoro), cyano, or
nitro, or substitu-ted alkyl or alkoxy (e.g., nitro, cyano,
halo or lower alkoxy) can be polymerized to form polymers
lS having repeating units corresponding to the formula:
~N3P3(cl)s(OR )~n (I)
where n is greater than about 2 to about 600 or higher and
where Rl is defined as above.
The polymers (I) can be further reacted to form r~
homopolymers or copolymers having repeating unlts corres-
ponding to the formula:
~N3P3(ORl)(OR2)5~n (II)
where n and Rl are defined as above and where R2 is the same
as Rl or is different than Rl and is lower ~e.g., Cl-C10)
linear or branched alkyl, lower alkaryl, substituted lower
alkyl, such as lower alkoxy, halo, cyano or nitro substituted
alkyl or
~ r! ) ~ ,R4z
where R~s, when present, are-substituted on any sterically
permissible position on the phenoxy ring, preferably meta
and para, where z is 0 to 3; preferably 0 to 1; (where z is
1, R4 preferably is in the para posi-tion) and where R4 is
independently, lower linear or branched alkyl, lower linear
or branched alkoxy, halo (e.g., chlorine, bromine or fluorine),
nitro, cyano or substituted alkyl or alkoxyl (e.g., nitro,
cyano, halo or lower alkoxy substitu-ted).
Examples of oR2 include methoxy, ethoxy, propoxy
n-butoxy, sec. butoxy, tert. butoxy, octyl, phenoxy, tolyloxy,
xylyloxy, benzyl, phenet}lyloxy, chloro, bromo, methoxyphenoxy,
propoxyphenoxy, p-nitrophenoxy, OCH2CF3, OCH2C3F7, OCH2C3F6CF2H,
2,2,33-te-trafluoropropoxy, 3,4-dichlorophenoxy, 4~bromophenoxy,
2-chloroethylphenoxy, 2 chloroethoxyphenoxy and the like.
It is to be understood that while it is presently
preferrecl that all Rls are the same and all R2s are the same
the Rl can be mixed and the R2 can be mixed. The mixtures
may be mixtures of different substituents or mixtures of F
differen-t positional isomers. In preparing specific polymers
steric hindrance must be considered. For example, one
- skilled in the art readily will recognize that steric
hindrance will dictate the propriety of using relatively
bulky groups in the orthoposi.tion on the phenoxy rincJ since
as set fortil hereinafter t~le R2 is provided by reacting
a substituted metal phenoxide with a chlorine a-tom on a
phosphorus atom. Desira~ly, g.roups which sterically in-
hibit such a subs-titution reaction should be avoided. Absent
the foregoing proviso, the selection of the various R2s will
be apparent to anyone skilled in the art based upon this dis-
closure.
The repeating units of the polymer (II~ can be
represented by the formulas:
r ORl ¦ (VI) ~ oR2
¦ (V)
._ _ p =N I - and - _ p =N
oR2 oR2
_ _ n _ 2n
where the ratio of unit IV to unit V is 1:2, since the
repeating unit is derived from ring opening of the tri-
phosphazene (III). For e~ample, typical polymer segments would
be one or more of
IORl ~oR2 loR2
__ - P =N ~ P =N - P -N- .
.oR2 oR2 OR2 ~ n
~- IR2 IORl IR2
_ ~ P =N - IP =N P =N - - , or
oR2 oR2 OR
.= n
._
loR2 oR2 IORl
! 1 2 1 2
oR2 OR OR r.
__ 11
The above ~escribed polymers (II), as well as
those containing reactive sites designated as w below, may
be crosslinked and/or cured at moderate temperatures (for
example, 200-350F.) by the use of free radical initiators,
for example, peroxides, using conventional amounts,
techniques and processing equipment.
The copolymers of this invention may con-tain small
amounts of substituents W, which randomly replace a portion
of the -oR2 groups, i.e. units such as
ORl 1 1 oR2
- l P = N ~ and - P + r
where W represents a group capable of a crosslinking chemical
reaction such as an olefinically unsaturated, preferably
ethylenically unsaturated monovalent radical containing a
group capable of further reaction at relatively moderate
temperatures, -the ratio of W:Rl~R2 being less than about
1:5. Examples of W are -OCH=CH2; -OR5CH=CH1; -O-IC=CH2;
R6
-OR5CF=CF2 and similar groups wnich contain unsaturation,
where R5 and R6 are alipha-tic or aromatic radical, prefer-
abl`y R6 is -CH2-. These groups are capable of further re-
action ak moderate temperatures (for example, 200 350F.)
in the presence of free radical initiators, conventional
sul~ur curing or vulcanizing additi~es known in the rubber
art or other reagents, often even in the absence of accelerators,
using conventional techniques and processing equipment.
Exàmples of free radical ini-tia-tions include benzoyl peroxide,
bis ( 2, 4-dichlorobenzoyl peroxide~, di-tert-hutyl pexoxide,
dicumyl peroxide, 2,5-dimethyl(2,5-di-tert-butylperoxy)hexane,
t-butyl perbenzoate, 2,5-dimethyl~2,5-di~tert-butylperoxy)
hepyne-3, and 1,1-bis(ter~-butylperoxy)-3,3,5-trimethylcyclo-
hexane. Thus, the general peroxide classes which may be used
for crosslinking include diacyl peroxides, peroxyesters,
and dialkyl peroxides.
Examples of sulfur-type curing systems include vul-
canizing agents such as sulfur, sulfur monochloride, selenium,
tellurium, thiuram disulfides, p-quinone dioximes, poly-
sulfide polymers, and alkyl phenol sulfides. The above
vulcanizing agents may be used in conjunction with accelerators,
such as aldehyde amines, thio carbamates, thiuram sulfides,
guanidines, and thiazols, and accelerator activa~ors, such
as zinc oxide or fatty acids, e.g., stearic acid.
It is also possible to use as W in the above
formulas, monovalent raaicals represented by the formulas
~ oSi(oR7)2R8 and other similar radicals which contain
one or more reactive groups attached to silicon; (2) -OR9NR9H
and other radicals which contain reactive -NH linkages. In
these radicals R7, R8 a~d R9 each represent aliphatic,
aromatic and acyl radicals. Like the groups above, these
groups are capable of further reaction at moderate temperatures
in the presence of compounds which effect crosslinking. The
presence of a catalyst to achieve a cure is oftern desirable.
The introduction of groups such as W into polyphosphazene
polymers is shown in U. S. Patents 3,888,799; 3,702,833
and 3,844,983
The amount of W present in the copolymer, affects
.-~.. c,
the process~bility, smoke production, glass transition tem-
perature and a numher of other properties of the copolymers.
These ratios also affect the copolymer's ability to be
foamed and the properties, such as the rigidity, of the
resulting foams.
The cyclic polyphosphazenes (III) can be prepared,
for e~ample, by following the general reaction scheme taught
by Dell et al, "Phosphorus l~itrogen Compounds Part XIII
Phenoxy and p-sromophenoxy-chlorocyclotriphosphazatrienes",
J. Chem. Soc. (1965) 4070-4073.
Generally, the procedure comprises forming the
sodiunl salt of the desired phenolic compound (HORl , where
is defined as above) in a suitable solvent such as tetra-
hydrofuran or dioxane. This phenoxide is then slowly added
to the trimer, hexachlorocyclotriphosphazene in a suit-
able solvent, as above, the reaction being conducted at low
temperatures to retard side reactions. The use of significant
amounts of solvent also promotes a uniform product. The
product is then isolated. In a preferred isolation technique,
a water immiscible solvent is substituted for the reaction
solvent and the solution is washed seriatim with dilute acid,
dilute base and water to remove unreacted starting materials
and by-products. The organic layer is then vacuum distilled.
There follows several e~amples showing the preparation
~5 of cyclic phosphazenes (III).
~X~MPL~ 1
N3p3cl5 (OC6M5)
. . . _
Sodium phenoxide was formed hy reacting ~.0 parts
'7~
' :
of sodium with 44.0 par-ts of phenol in 1800 parts of tetra-
hydrofuran.
120.0 parts of hexachlorocyclotriphosphazene
was charged into a reactor together with 1000 parts of tetra-
hydro~uran and the mixture cooled to -78C. To the stirred
r~actor, there was then added dropwise, over a three hour
period, the previously prepared so~ium phenoxide solution,
while maintaining the temperature at -78C. until the
addition was complete~ The reaction mixture was then allowed
to warm to room temperature.
The reaction mixture was then worked up in the
following manner: The solvent was evaporated and the re-
sultant oil was dissolved in petroleum ether. The ether
solution was wasiled with 5% aclueous hydrochloric acid, then
1~ 5~ aqueous sodium bicarbonate, followed by several washings
wi-th water. The petroleum ether was then evaporated and the
resultant oil was vacuum distilled to obtain phenoxypenta-
chlorocyclotriphosphazene (b.p. 74C. at .07 Torr).
Elemental Analysis: Theoretical - C 17.78, H 1.24, N 10.37,
P 22.93; Found - C 17.65, ~1 1.24, N 10.44, P 22.88.
EXAMPLE 2
N3P3C15(OC6E14-P-F)
. . . _ .
Sodium p-fluorophenoxide was formed by reacting
4 parts of sodium with 26.9 parts of p-fluorophenol in 900
~5 parts of tetrahydrofuran.
60 parts of hexachlorocyclotriphosphazene were
charc3ed into a reactor together with 500 parts of tetra-
hydrofuran and the mixture cooled at -78C. The previous-
ly prepared sodium p-fluorophenoxide solution was added
5~r~7
dropwise and reac~ed as in ~ample 1. The resultant product
was worked up as in Example 1 to yield p-fluorophenoxypenta-
chlorocyclotriphosphazene (b.p. 107c. at .02 Torr).
Elemental Analysls: Theoretical - C 17.02, Il 0.95, N 9.93,
P 21.94; Found - C 17.3~ 1.00, N 9.86, P 21.85
~XAM~L~ 3
N3P3C15(OC6~l5-P-Cl)
Usin~3 sodium p-chlorophenoxide, p-chlorophenoxy-
pentachlorocyclotripllosphazene was prepared following the
procedure of Example 1 (b.p. 126C. at 0.25 Torr).
Elemental ~nalysis: Theoretical - C 16.39, i~ 0.90, N 9.56,
P 21.13; Found - C 16.34, H 0.82, N-9.42, P 2].05.
EX~MPLE 4
N3P3Cl5 ~OC6H4-p-CH3)
Using sodium p-methylphenoxide, p-methylphenoxy-
pentaclllorocyclotriphosphazene is prepared following the
procedure of Example 1 (b.p. 130C. at .05 Torr).
Elemental Analysis: Theoretical - C 20.05, H 1.68, N 10.02
P 22.16; Found - C 20.18, H 1.69, N 10.08, P 22.09.
EXAMPLE 5
N3P3C15 (OC61:14-p-OC1~3)
Using sodium p-methoxyphenoxide, p-methoxyphenoxy~
pentachlorocyclotriphosphazene was prepared following
the procedure of Example 1 (b.p. 121C. at .025 Torr)
Elemelltal Analysis: Theoretical - C 19.31, H 1.62, N 9.65,
P 21.3~; Found - C 19.58, H 1.79, N 9.67, P 21.43.
In a manner similar to the above teachings or
using varian-ts obvious to those skilled in the art, other
cyclic trimers (III) can be prepared.
-' 10 -
The polymers (I) are prepared by thermally polymer-
izing the cyclic tripllosphazenes by heating them at a
temperature and for a length of time ranging from about 200C.
for 72 hours to 300C. for 30 minutes. That is to say the
compounds are heated to a teMperature ranging from a~out
200C. to about 3Q0C. for from about 30 minutes to 72
hours, the higher temperatures necessitating shorter contact
times and the lower temperatures necessitating longer con-
tact times. The compounds must be heated for such a iength
of time that only a minor amount of unreacted charge material
remains and a major amount of high polymer has been produced.
Such a result is generally achie~ed by following the con-
ditions of temperature and contact time specified above.
It is preferred that the thermal polymerization
be carried out in the presence of an inert gas such as
nitrogen, neon, argon or a vacuum, for example, about 10-2
~orr, inasmuch as the reaction proceeds very slowly in the
presence of air. The use of such a gas, however, is not
critical. The presence of moisture is also preferahly
avoided.
The polymerization process follows that taught
for the polymerization of -~Npcl2t3~ as described in U. S.
3,370,020.
The polymers resulting from the thermal polymeriza-
tion process are in the form of a polymeric mixture of
different polymers of different chain-lengths. That is to
say, the product of the thermal polymerization is a mixture
of polymers having the formula (I)
~3P3(cl)s(oRl)~n
-- 11 --
~,'
.,, , :
s~
where n ranges from about 2 to about 600 or higher. For
e~ample, ~he recovered media may con-tain minor amounts of
polymer wllere n is 2 and major amounts of polymer where
n is 600 or higher. The media may also contain polymers
composed o~ from 3-599 or higher recurring units, the com-
plete mixture of polymers may constitute the starting ma-
terial for forming the polymer (II).
The polymers (I) exhibit excellent elastomeric
properties b~t display instability to atmospheric mois-ture.
1~ There follows several exarnples of the preparation
of polymers (I). These examples, as is true of all the r
e~amples herein, are exemplary and are not to be construed
as limiting.
EX~MPL~ 6
L5 ~3P3cls(oc6Hs)~n
__ .__ r
A quantity of the trimer of Example 1 was de-
oxygenated with inert gas and sealed in a suitable, thick-
walled reaction vessel at 10-2 Torr and heated at 250C.
for 15 hours. Polymerization was terminated at this time
since a glass ball,one-half inch in diameter, ceased to flow
due to the increased viscosity of the molten mass, when the
vessel was inverted termination was effected by cooling
the vessel to room temperature. The resultant polymer had
a Tg of -49.1C.
Elemental Analysis: E'ound (%) - C 17.62, H 1.20, N 10.28,
P 23.12.
EX~IPLE 7
~3P3cls(oc6ll4-p-F)~n
In the same manner as Example 6, the trimer of
- 12 -
_. _ ~ .. . ~. . ____ - _ .. .. . ...
~ ~ ~ 5~- 7~
Example 2 was thermally poly~erized at 250C. for 8 hours.
The resultant polymer had a Tg of -~7.6~C.
E~.'IPLE: 8
~N3P3c15(oc6lI4-p-cl)~n
In the same manner as Example 6, the krimer of
~xample 3 was therMally polymerized at 250C. for 10 hours. r
The resultant polymer had a Tg of -39.3~C.
Elemental Analysis: Found - C 16.29, EI 0.82, N 9.49,
EXAMPLE 9
-~N3P3Cls(Oc6El4-p-cH3)~n
In the same manner as Example 6, the trimer of
Example 4 was thermally polymerized at 250C. for 18 hours.
The resultant polymer had a Tg of -44.2C.
EXAMPLE 10
~N3P3Cl5(Oc6~I~-p-ocH3)~n
In the same manner as Example 6, the trimer of
Example 5 was thermally polymerized at 250C. for 6 hours.
The resultant polymer had a Tg of -43.7~C.
The polymers (II) are formed in a process which
comprises treating the polymer mixture (I) resulting from
the thermal polymerization step with a mixture of compounds
having the formulas
r~ (OR2)V and if desired,
~S M(W)V,
wllerein M is lithium, sodium, potassium, magnesium or cal-
cium, v is equal to the valence of metal M, and -oR2 and W
are as specified above.
The polymer mixture is reacted with the mixture
- 13 -
s~7
of met~l compounds at a temperature and a lenyth of time
ranging from about 25C. for 7 days to about 200C. for 3
hours.
Again, as in regard to the polymerization step
mentioned above, the polymer mixture is reacted with the
alkali or alkaline earth metal compounds at a temperature F
ranging from about 25C. to about 200C. for from about
3 hours to 7 days, the lower temperatures necessitatiny
the longer reaction times and the lligher temperatures
allowing shorter reaction times. These conditions are,
of course, utilized in order to obtain the most complete
reaction possible, i.e., in order to insure the complete
conversion o~ the chlorine atoms in the polymer mixture to
the corresponding ester of the alkali or alkaline earth
starting materials.
The above esterification step is carried out in
the presence of a solvent. The solvent employed in the
esterification step must have a relatively high boiling
point (e.g., about llSC. or higher) and should be a
solvent for both the polymer and the alkali or alkaline earth
metal compounds. In addition, the solvent must be sub-
stantially anhydrous, i.e., there must be no more water in
the solvent or metal compounds than will result in more than
1%, by weight, of water in the reaction mixture. The pre-
vention of water in the system is necessary in order to in-
hibit the reaction of the available chlorine atoms in the
polymer therewith. Examples of suitable solvents include
diglyme, triglyme, tetraglyme, toluene and xylene. The
.
amount of solvent emplo~ed is not critical and any amount
sufficient to solubilize the chloricle polymer mixture
can be employed. Either the polymer mixture or the alkaline
earth (or alkali) metal compounds may be used as a solvent
solution thereof in an inert, organic solvent. It is
preferred, however, that at least one of the charge ma-terials
be used as a solu~ion in a compound which is a solvent for the
polymeric mixture.
The amount of alkali metal or alkaline earth
metal compound or compounds employed should be at least about
stoichiometrically equivalent to the number of available
chlorine atoms in the polymer mixture. However, it is
preferred that an excess of the metal compound be employed
in order to assure complete reaction of all the available
1~ chlorine atoms. Where a mixture ol metal compounds is em-
ployed, generally, the ratio of the individual alkali metal
or alkaline eartll metal compounds in the combined mix-ture
governs the ratio of the groups attached to the polymer
backbone. However, those skilled in the art readily will
appreciate that the nature and, more particularly, the
steric configuration of the metal compounds employed may
effect their relative reactivity. Accordingly, the ratio
mixed R2s in the esterified product, if necessary may be
controlled by employing a stoichiometric excess of the
slower reacting metal compound.
~xamples of alkali or al]caline earth metal compounds
which are useful in the process of the present invention in-
clude
sodium phenoxide
potassium phenoxide
sodium p-methoxyphenoxide
sodium o-methoxyphenoxide
. sodium m-methoxyphenoxide
lithium p-methoxyphenoxide
lithium o-methoxyphenoxide
lithium m-methoxyphenoxide
potassium p-methoxyphenoxide
potassium o-methoxyphenoxide
potassium m-methoxyphenoxide
magnesium p-methoxyphenoxide
magnesium o-methoxyphenoxide
magnesium m-methoxyphenoxide
calcium p-methoxyphenoxide
calcium o-methoxyphenoxide
calcium m-methoxyphenoxide
sodium p-ethoxyphenoxide
sodium o~ethoxhphenoxide
sodium m-ethoxyphenoxide
potassium p-ethoxyphenoxide r
potassium o-ethoxyphenoxide
potassium m-ethoxyphenoxide
sodium p-n-butoxyphenxoide
sodium m-n-butoxyphenoxide
lithium p-n-butoxyphenoxide
lithium m-n-butoxyphenoxide
potassium p-n-butoxyphenoxide
potassium m-n-butoxyphenoxide
magnesium p-n-butoxyphenoxide
rnagensium m-n-butoxyphenoxide
calcium p-n-butoxyphenoxide
calcium m-n-butoxyphenoxide .
sodium p-n-propoxyphenoxide
sodium o-n-propoxyphenoxide
sodium m-n-propoxyphenoxide
potassium p-n-propoxyphenoxide
potassium o-n-propoxyphenoxide
potassium m-n-propoxyphenoxide
sodium p-rnethylphenoxide
sodium o-methylphenoxide
sodium m-methylphenoxide
l.ithium p-methylphenoxide
` . lithium o-methylphenoxide
lithium m-me-thylphenoxide
sodium p-ethylphenoxide
sodium o-ethylphenoxide
sodium m-ethylphenoxide
potassium p-n-propylphenoxide
potassium o-n-propylphenoxide
potassium m-n-propylphenoxide
magnesium p-n-propylphenoxide
sodium p-isopropylphenoxide
sodium o-isopropylphenoxide
sodium m-isopropylphenoxide
- calcium p-isopropylphenoxide
calcium o-isopropylphenoxide
- 16 -
calcium m-isopropylphenoxide
sodium p-sec ~utylphenoxide
sodium m-sec butylphenoxide
li-thium p-sec butylphenoxide
li-thium m-sec butylphenoxide
lithium p-tert. butylphenoxide
lithium m-tert. bu~ylphenoxide
potassium p-tert. ~u-tylphenoxide
potassium m-tert. butylphenoxide
sodium p-tert. butylphenoxide
sodium m-tert. butylphenoxide
sodium propeneo~idè
sodium p-nonylphenoxide
sodium m-nonylphenoxide
sodium o-nonylphenoxide
sodium 2-methyl-2-propeneoxide
potassium buteneoxide
and the like.
This process resul-ts in the production of a polymer
mixture havinc3 the formula (II).
The polymexic reaction mixture resulting from
this reaction or esterification step is then treated to
remove the salt which results upon reaction of the chlorine
atoms of the starting polymer mixture with the metal of the
alkali or alkaline earth metal compounds. The salt can be
removed by merely precipitating it out and filtering, or it
may be removed by any other applicable method, such as by
washin~ the reac-tion mixture with water after neutralization
thereof with, for example, an acid such as hydrochloric acid.
The next step in the process comprises fractionally
precipitating the polymeric material to separate out the
high polymer from the low polymer and any unreacted trimer. r
The fractional precipitation is achieved by the,~prefera~ly
dropwise, addition of the esterified polymer mixture to a
material which is a non-solvent for the high polymer and a
solvent for the low polymer and unreac-ted trimer. That is
to say, any material which is a nonsolvent for the polymers
wherein n ls higher than 350 and a solvent ~or the remaining
low polymers may be used to fractionally precipitate -the
- 17 -
desired polylners. Examples of materials which can be used
for this purpose include hexane, diethyl ether, carbon
tetrachloride, chloroform, dioxane methanol, ~ater and the
like. The fractional precipltation of the esterified polymeric
mixture generally shoulcl be carried out at least twice and
preferably at least four times in order to remove as much
of the low polymer from the polymer mixture as possible
The precipitation may be conducted at any temperature,
however, it is preferred that room temperature be employed.
The novel high molecular weight copolymer mixture may then
be recovered by filtration, centrifuga-tion, decantation
or tlle like.
There follows several examples of the preparation
of polymers (II).
1~ E~MPLE 11
~NP(OC6Els)2~n
An anhydrous toluene solution of the polymer
formed in Example 6, containing 31.2 parts of the polymer,
was added to an anhydrous diglyme-benzene solution of 53.9
parts of sodium phenoxide at a tempera-ture of 95C. with
constant stirring. After the addition, ben~ene was dis-
tilled from the reaction mixture until a temperature of
115-116C. was attained. The reaction was then heated to
reflux for 60-65 hours. At the end of this time, the
2S resultant polymer was precipitated by pouring the reaction
mixture into an excess of methyl alcohol. The polymer was
stirred in tlle methyl alcohol for 24 hours. Next, -the
polymer was added to a large quantity of water and s-tirred
an additional 24 hours. The polymer was then separated and
-- 1~ --
dried. The resultant hornopolymer was a semicrystallille
solid having a glass transition temperature (Tg) of -4.76C.
The polyMer wcIs soluble in benzene, -tetrahydrofuran (THF)
and dimethylformamide (DMF). Films cast from THF were
tough and opaque. The films did not burn and were water
repellent.
Elemental ~nalysis: ~heoretical - C 62.34, H 4.36, N 6.06,
P 13.40; Found - C 62.10, ~I 4.36, N 5.97, P 13.69.
EX~PLE 12
~NP(OC6EI4~P-cl)2~n
.
The procadure of Example 11 was Eollowecl except
that 15.0 parts of the polymer of Example 8 were reacted r
with 30.8 par-ts of sodium p-chlorophenoxide. The resultant
homopolymer (79~ yield) was a semicrystalline solid having
1~ a Tg of -1.54C. The polymer was soluble in benzene,
THF, D~ and chloroform. Films cast from the TE~F were
tough and opaque. The films did not burn and were water
repellent.
Elemental Analysis: Theoretica] - C 48.18, H 2.70, N 4.68,
P lC.36; Found - C 47.90, H 2.63, N 4.49, P 10.28.
EXAMPLE 13
~N3P3(OC6lI 5 ) ( OC 61~ 4 ~p~C 1 ) 5~ ~
The procedure of Example 11 was followed, except
tllàt 16. 5 parts of the polymer of Example 6 were reac-ted
~5 with 37.1 parts of sodium p-chlorophenoxide. The resultant
copolymer (56~o yield) was a solid soluhle in benzene, T~F
and D~IF. Films cast from THF were tough and opaque.
The films dicl not burn and were water repellent.
Elemental Analysis: - Theore-tical - C 64.48~ H 5.28,
N 5.50~ P 12.17; Found - C 64.34, II 5.22, N 5.42, P 12.30.
-- 19 --
rp~
~XAMPLE 1~
~ 3p3(oc6El5)(oc6~ p-cH3)_~n
The procedure of Example 11 was followed,except
that 14.1 parts of ~he polymer of Example 6 were reacted
with 27.3 parts of sodium p-methylphenoxide. The resultant
polymer (40~ yield) was a solid, soluble in benzene, TEIF
and D~I~. Films cast from THF were tough an~ transparent.
TIle films did not burn and were water repellent.
Elemental ~nalysis: Theoretical - C 64.48, H 5.28, N 5.50,
P 12.17; Found - C 64.34, H 5.22, N 5.42, P 12.30.
EXAMPLE 15
~N3P3(OC6H4-p-F)(OC6H4-p-CH3)5~n
The procedure of Example 11 was followed, except
that 18.9 parts of the polymer of Example 7 were reacted
with 35.3 parts of sodium p~methylphenoxide. The resultant
polymer (70% yield) was a solid with a Tg of +0.08r'C,
soluble in benzene, TEIF and U~F. Films, cast from TEIF,
were tough and transparent, did not burn, and were water
repellent.
Elemental Analysis: Theoretical ~ C 63.00, H 5.03, N 5.37,
P 11.89; Found - C 62.91, H 5.18, N 5.26, P 12.01.
EXA~qP1E 16
~3p3(oc6H4-p-cl)(oc6H4-p-cH3)5~n
The procedure of Example 11 was followed, except
~5 that 15.0 parts of-the polymer of Example 8 were reacted
with 26.6 parts of sodium p-methylphenoxide. The resultant
polymer (72~o yield) was a solid with a Tg of -3.65C.,
soluble in benzene, THF and DMF. Films, cast ~rom rrlHF~
were tough and transparent, did not burn and were water
repellent.
- 20 -
C~
Element~l Analysis: Theoretical - C ~1.93, H ~.56, N 5.28,
P 11.69; Found - C 61.83, II 4.72, ~J 5.18, P 11.52.
EXAMPLE 17
-
_N3p3(oc6H4-p-cH3)(oc6Il4-p-cl)s~n
The procedure of Example 11 was followed, except
that 20. 6 parts of the polymer of Example g were reacted
Witil 44.1 parts of sodium p~chlorophenoxide. The resultant
polymer ~41~ yield) was a solid with a Tg of ~2.06C.,
soluble in benzene, THE' and DMF. Films, cast from THF,
did not burn and were water repellant.
Elemental Analysis: Theoretical - C 50.51, H 3.09, N 4.7$
P 10.56; Found - C 50.32, ~l 3.05, N 4.77~ P 10.78. r
E~AMPLE 18
~N3P3(oc6Hs)(oc6~l4-4-oc~l 3)5~n
lS A solution of 15.5 parts of [N3p3cls(oc6H5)]n
polymer in 200 parts of anhydrous toluene was added over a F
1.5 hour period to a stirred solution of sodium p-methoxy-
phenoxide at 90C. The sodium aryloxide solution was
prepared by the reaction of 28.3 parts of p-methoxyphenol
with 5.1 parts of sodium in 300 parts of anhydrous bis-(2
methoxyethyl)ether and 100 parts of dry benzene. After
the addition, benzene was distilled until a temperature
of 115-116C. was attained. The reaction mixture was then
heated at 115-116C. for 60-70 hours with constant stirring.
~5 The polymer was precipitated into a large excess of methanol
and washed in methanol for 24 hours. It was removed from
the Methanol, exhaustively washed with distilled water, and
dried. The product is a colorless, s-tiff elastomer.
- 21 -
}.~A~PLE 19
~3p3(~c6~l5)(oc6H4-~-cl)5~n
A solution o~ lG.5 ~ (~.205 e~uiv.) of [N3P3C15(OC6H5)]n
polymer in 300 rnl of anhydrous toluene was added over a 1.5
S hour period to a stirred solution of sodium p-chlorophenoxide
at 90C. The sodium aryloxide solution was prepared by the
reaction of 31.6 ~ (0.246 mole) of p-chlorophenol with
5.6 g (~.241 mole) of sodium in 300 ml of anhydrous
bis-(2-metho~yethyl)et~ler and 100 ml of dry benzene. ~fter
the addition, benzene was distilled until a temperature of
115-116C. was attained. The reaction mixture was then
heated at 115-116C. for 60-70 hours with constant stirring.
The polymer was precipitated into a large excess of methanol
and washed in methanol for 2~ hours. It was removed from
the methanol, exhaustively washed with distilled water, and
dried. The product is a colorless, fibrous material.
Following similar procedures, other homopolymers
and copolymers, such as described above, can be prepared.
The novel polymers (II) of this invention, as
mentioned above, are very thermally stable. The mixtures
are soluble in specific organic solvents such as tetrahydrofuran,
benzene, xylene,toluene, dimethylformamide and the like
and can be formed into films from solutions of the copolymers
by evaporation of the solvent. The polymers are water
~5 resistant at room temperature and do not undergo hydrolysis F
at high temperatures. The polymers may be used to prepare
films, fibers,coatinys, molding compositions and the like.
They rnay be blended with such additives as antioxidants, ultra-
violet light absorbers, lubricants, plasticizers, dyes,
- 22 -
piqments, fillers such as litharge, magnesia, calcium carbonate,
furnace black, alumina trihydrate and hydrated silicas, other
resins, etc., ~ithout detrac-ting from the scope of the present
invention.
The polymers may be used to prepare foamed products
which exhibit excellent fire retardance and in some cases
produce low smoke levels, or essentially no smoke when heated
in an open flame. The foamed products may be prepared from
filled or unfilled formulations usin~ conventional ~oam
techniques with chemical blowing agents, i.e. chemical
compounds stable at original room tempera-ture which decompose
or interact at elevated temperatures to provide a cellular
foam. Suitable chemical blowing agents include:
BlowincJ ~gentEffective Temperature
Ran~e C.
Azobisisobutyronitrile 105-120
Azo dicarbonamide(l,l-azobisform~
amide) 100-200
Benzenesulfonyl hydrazide95-100
N,N'-dinitroso-N,i~'-dimethyl tere-
phthalamide
Dinitrosopentamethylenetetramine 130-150
Ammonium carbonate 58
p,p'-oxybis-(benzenesulfonyl-
hydrazide) 100-200
Diazoaminobenzene ~4
~rea-biuret mixture 90-140
2,2'-azo-isobuty ronitrile 90-140
~zohexahydrobenzonitrile 90-140
Diisobutylene 103
4,4'-diphenyl disulfonylazide110-130.
Typical foamable formulations include:
Phospllazene copolymer (e.g., [N3p3(oc6H5)(oc6H4-p-ocE~3)5]n
- 23 -
5~
100 parts
Filler (e:g., alumina trihydrate) 0-100 phr
Stabilizer (e.g., magnesium oxide) 2.5-10 phr
Processing aid (e~g., zinc stearate)~ 2.5-10 phr
Plasticizer resin (e.g., cumar P-10 ~
coumarone indene resin) 0-50 phr
Blowing a~ent (e.g., l,l'-azobisfor~amide) 10-50 phr
Activator (e.g., oil-treated urea)10-40 phr
Peroxide curing agent (e.g., 2,5-
dimethyl-2,5-di(t-butylperoxy)
hexane~ 2.5-10 phr
,Peroxide curing agent (e.g., benzoyl
! peroxide 2.5-10 phr
~Yhile tlle above are preferred formulation guidelines, obviously
some or all of the adjuvants may be omitted, replaced by other
functionally equivalent materials, or the proportions varied,
within the skill of the art of the foam formulator.
In one sùitable process, the foamable ingredients
are blended together to form a homogeneous mass; for example,
a homogeneous film or sheet can be formed on a 2-roller mill,
preferably with one roll at ambient temperature and the other
at moderately elevated temperature, for example, 100-120F.
The homogeneous foamable mass can then be heated, to provide
a foamed structure; for example, by using a mixture of a
curing agent having a relatively low initiating temperature,
such as benzoyl peroxide, and a curing agent having a
relative~y hi~h initiating temperature, such as 2,5-dimethyl-
2,5-di(t-butylperoxy) heY~ane, and partially pre-curing in
a closed mold for about 6-30 minutes at 200-250F., followed
by free expansion for 30-60 minutes at 300-350F. In the
alternative, the foaming may be accomplished by heating the
foamable mass for 30-60 minutes at 300-350F. using a high
temperature or low temperature curing agent, either singly
or in combination. One benefit of utilizing the "partial
- 24 -
~ . ,
.
'
pre-cure" foaming technique is that an increase in th~
molecular weight of the foamable polymer prior to the
foaming step enables better control of pore size and pore
uniformity in the foaming step. The extent of "pre-cure"
desired is dependent upon the ultimate foam characteristics
desired. The desired foaming temperature is dependent on
~he nature of the blowing agent and the crosslinkers present.
The time of heating is dependent on the size and shape of
the mass being foamed. The resultant foams are generally
light tan to yellowish in appearancej and vary from flexi-
ble to semirigid, depending upon the glass transition
temperature of the copolymer employed in the foam formu-
lation, that is to say, the lower the glass transition of
the polymer the more flexible will be the foam produced
therefrom. As indicated, inert, reinforcing or other
fillers such as alumina trihydrate, hydrated silicas or
calcium carbonate can be added to the polymer foams and the
presence of these and other conventional additives should in
no way be construed as falling ou~side the scope of this
invention.
EXAMPLE 20
Preparation of Foamed
P3(OC6Hs)(OC6H4~P~Oc~3)5~n
... . .. _ _
To 100 parts of the copolymer ~N3P3(oc6Hs)(oc6~4-p-ocH3)5~n
prepared in accordance with ~xample 20, there werè added
100 parts of alumina trihydrate, 5 parts of magnesium o~cide,
S paxts of zinc stearate, 3 parts of CUMAR P-l (a coumarone-
indene resin~, 30 parts of Celogen AZ (l,l'azohisfor~amide), -
23 parts of BI~-OT (an oil-treated urea), S parts of
- ~5 -
~'~i
., .,.,.~:
5~77
2,5-dimethyl-2,5-di(tert.-butylperox~)hexane, and 5 parts
of benzoyl peroxide (78% active, wet wlth water). The
above in~redients were milled to insure homogeneous mixing
of all materials~ This mix was then free blown at 325-350F.
for 10 minutes. The resultant flexible foam was light -tan
in color with a uniform small cellular structure. There was
no ~vidence of delamination or side splits. A piece of the
foamed material when lleated in a Bunsen burner flame evolved
only a very slight trace of smoke. The sample did not burn
when removed from the burner flame. Thus, it would not
support combustion and was rated as non-burning.
~lso, as mentioned above, the polymers of this
invention can be crosslinked at moderate temperatures by
conventional free radical and/or sulfur curing techniques
when minor amounts of unsaturated groups W are present in
the polymer backbone. The ability of these polymers to
be cured at temperatures below about 350F. makes them
particularly useful as potting and encapsulation compounds,
sealants, coatings and the like. These polymers are also
useful for preparing crosslinked foams which exhibit signifi-
cantly increased tensile streng-ths over uncured foams. These
polymers are often crosslinked in the presence of inert,
reinforcing or other fillers and the presence of these and
other conventional additives are deemed to be within the p
scope of this invention.
- 26 -
