CA1115023A - Solution polymerization of chlorophosphazene with sulfur modifier - Google Patents
Solution polymerization of chlorophosphazene with sulfur modifierInfo
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- CA1115023A CA1115023A CA301,866A CA301866A CA1115023A CA 1115023 A CA1115023 A CA 1115023A CA 301866 A CA301866 A CA 301866A CA 1115023 A CA1115023 A CA 1115023A
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Abstract
SOLUTION POLYMERIZATION OF
CHLOROPHOSPHAZENE WITH SULFUR MODIFIER
Abstract Solution polymerization of cyclic dichlorophosphazenes represented by the general formula (NPCl2)n in which "n" is less than 15 to essentially linear polydichlorophosphazenes in which the degree or polymerization is within the range of 20 to 50,000 is improved by the use of selected solvents and by the presence of elemental sulfur or sulfur donating compounds in the polymerization mixture.
CHLOROPHOSPHAZENE WITH SULFUR MODIFIER
Abstract Solution polymerization of cyclic dichlorophosphazenes represented by the general formula (NPCl2)n in which "n" is less than 15 to essentially linear polydichlorophosphazenes in which the degree or polymerization is within the range of 20 to 50,000 is improved by the use of selected solvents and by the presence of elemental sulfur or sulfur donating compounds in the polymerization mixture.
Description
2~
This inven-tion relates -to the solution polymerization of cyclic polychlorophosphazenes represented by the general for-mula (NPCl2)n in which n is 15 o~ less, usually 3 or 4~ to pro-duce essentially linear polydichlorophosphazenes in which the degree of polymerization is selectively controlled within the range of 20 to 50,000.
The bulk polymerization of low molecular weight cyclic polydichlorophosphazenes is described i.n United States Patent
This inven-tion relates -to the solution polymerization of cyclic polychlorophosphazenes represented by the general for-mula (NPCl2)n in which n is 15 o~ less, usually 3 or 4~ to pro-duce essentially linear polydichlorophosphazenes in which the degree of polymerization is selectively controlled within the range of 20 to 50,000.
The bulk polymerization of low molecular weight cyclic polydichlorophosphazenes is described i.n United States Patent
3,370,020 issued February 20, 1968 and elsewhere in the lite-rature. .
.It is also known that the thermal polymerization of hexachlorocyclophosphazene and octachlorocyclophosphazene can be effected in the presence of various catalysts as reported in "phosphorus-Nitrogen Compounds" published 1973 by Interscience Publishers, New ~ork.
Previous attempts to polymerize cyclic dichlorophos- :
phazenes in solution have resulted in excessive gelation and the production of unusable products.
It has now been found that instead of controlling the temperature and other reaction conditions in order to obtain polymer of a desired molecular weight, it is now possible to ob-tain products with a desired molecular weight by choice of a suitable solvent as the reaction medium.
It has also been found that the presence of a small amount of sulfur either as elemental sulfur or as a sulfur com- `
pound in the solution in the polvmerization mixtures appears to overcom~ a tendency of the solvents to react with cyclochloro- ~ :
phosphazenes at high tempera-tures Eorming an intractable gel.
It has further been found that the choice o~ solvent or mixture of solvents significantly affects the molecular weight of the resulting polymer and that as a consequence polymer of a desired molecular weight is produced by selecting an appropriate :
.:' B ~ ~:
~ ~ ~ 5f~
solvent and suitable reaction conditions.
A princip~l object of the present invention is there-fore to provide a new and improved process for the solution poly-merization of cyclic dichlorophosphazenes which yields essen~
tially linear polydichlorophosphazene polymers.
Another object of the invention is to provide a solu~
tion polymerization process which can be con~ucted at atmosphe-ric pressure and at comparatively moderate temperatures and under a relatively inert and easilY controlled atmosphere.
A further object of the invention is to polymerize cy- ;
clic dich~orophosphazene oligomers to produce linear polydichlo-rophosphazene polymers exhibiting a unique, very narrow range or molecular weights, heretofore unobtainable in previously prac ticed bulk polymerizations.
In accordance with the invention, these and other ob-jects are achieved by polymerizing solutions comprising cyclic dichlorophosphazene oligomers dissolved in a liquid solventCha-Ying a dielectric constant o~ at least two~ in the presence of about 1 to up to 20 millimoles of elemental sulfur-or sulfur donating compound per mol of cyclic dichlorophosphazene oligomer.
The solvent is selected so as to be solvent for both the oli-gomers and the sulfur or sulfur donating compound~and the poly~
merization is conducted'for up to 300 hours at a temperature between about 140C and 225C in a reactor which may be either glass lined stainless steel vessels or unlined stainless steel vessels, or galss vessels. Preferably, the oligomers are dissol-ved in between about 10% and up to 80% by weight of selected solvent.
As solvent medium in which the thermal polymerization of low molecular weight cyclic polydichloroPhosphazenes is con- ~
ducted, use can be made of aromatic hydrocarbon or cyclo-alipha- ~ .
tic hydrocarbon solvent.
' 'B , . . : : ' ~5~2~ ~
Suitable hydrocarbon solvents include decalin, tetra-lin, naphthalene, cyclohexane, toluene, dimethylbenzene, dihy-droanthracene, tetramethylbenzene, cumene, cymen, mono-, di-, tri-, tetra- substituted aromatic compounds where the substi-tuents are straight cahin or branched chain hydrocarbons with up ~o 10 carbon atoms.
As other solvents, use can also be made of liquids ha- -ving a dielectric constant of at least two, and which are sol-vents for both the cyclic dichlorophosphazene starting materials and for the sulfur or sulfur-donating compound presentas catalysts.
A further solvents suitable for such polymerizations, use can be made of aromatic compounds carrying polar groups such as methoxy, N, N-disubstituted amino, halogens particularly mono-, di-, tri- or tetra-halogen substituents on the aromatic nucleus, and mixtures of said solvents or other hydrocarbon solvents of a similar nature.
Still other solvents which have been used-include aro-matic compounds including those which are monocyclic or polycyclic and which are either unsubstituted or substituted, especially ~ with polar substituents such as halogen, N,N ' -diakylamino, alkoxy, and other polar groups. Aromatic solvents with up to four polar substituents on the aromatic ring have been employed. These polar substituents can be on the ring or on a side-chain. For example, the aromatic ring can have either electron withdrawing groups or electron supplying groups. Examples of such solvents are 2-chloro toluene; 2,3-dichlorotoluene; 2,3-dichloroethyl- ~ ~
benzene; and 2,3,4-trichloroethylbenzene. ~ ;
In accordance with the invention, use must also be made of small but significant amounts of elemental sulfur or sulfur donating compounds such as tri- or tetra-sulfides o~ organic compounds or tri- or tetra-sulfides o~ inorganic compounds in inorganic sulfides and organic sulfides. Sulfur donor compounds -- 4 ~
,~
f~ 3 which are suitable are compounds which release sulfur at the --temperatures at which the solution polymerization is conducted.
Such compounds are commonly used in the vulcanization of rubbers include tetramethylthiuram tetrasulfides, and other tetraalkyl thiuram tetrasulfides; the reaction products of alkylene chlo-rides and sodium polysulfides, amine disulfides such as 4,4'-dithio dimorpholine and other compounds which release sulfur when heated to about 200C.
Briefly the present invention includes polymerization of cyclic dichlorophos~hazenes in aromatic or cycloaliphatic hydrocarbon solvents by proceeding as follows.
All of the constituents, i.e. solvent, cyclic dichlo-rophosphazene oligomers and sulfur or sulfur donating compounds were charged into the reaction vessel. The sulfur was added as a solution in the hydrocarbon solvent, for ease in handling.
For solvents with boiling points below 150C pressu-rized systems were utilized with pressure from 0-1000 psig and ~a preferred range of 0'-200 psig.
For solvents with boiling points between 150C and 250C reactions were carried out at atmospheric pressure. Dry Argon gas was passed over the reaction mixture. Care was taken at all points to prevent oXyqen or moisture from being introduced : : , . . . .
,':' " ' " ~ : . ': ' .: , :
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l ~ ~
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into reaction mi~ture. Apparatus wa~ preheated ln 140C oven for 24 hour~ be~ore use~ , Stirring was by means o~ magneti~ bars. Polymeri~a~
tions were conducted ~or rrom 40-300 hours preferably at 200-~20C bath temperature. The polymerizatlon reaction mlxture wasusually solid at completion of reaction. Unreacted cyclics and hydrocarbon solvent were s~ripped by repeated washing with dry ~exane in inert, dry atmosphere. RecoYered polymer was dissol-~ed in benzene yieldln~ a mostly soluble polymer, eXhibiting dilute ~olution ~iscosi~ies between from about 0.09 to,1.2 - (DSV 1~ equivaient to inherent vlscosity stated in decal1ter~
ram~.
Volatile material ~wept ~rom the reaction mixture ino-luded H~S and HCl.
The same polymerizat,ion reaction carried out under the ; l ame reaction conditions to converslons Or 60% or more except hat lt was conducted ln the absence o~ sul~ur or sulrur dona-ting compound~ produced products which were usually ~eiled and in~oluble ln benzene. The exact nature Or the effect o~ the Z0 ~ul~ur on ~he pol~merization is not rully understood.
The inventlon will be further described in the follow-ing ~x~mple~ given by way o~ illu~tration and not intended to llmit the inventlon. The data in Table I was obtained by pro-ceeding as ~ollowa: .
'''-; ''"''" ~ ' ''' "' ~'' ''-' .'. ',' . .
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: E~ample The lndicated number mllllmole~ Or elemental sulfur dissolved in te~ralin or other solvent was added to a solution Or cycllc dlchlorophosphazene trimer in the indlcated solvent . in a glass or stainless steel reaction vessel. An ~rgon rlow of 1 to ~ ml/minute was maintained across the ~ur~ace of the ~olution. Temperature wa~ maintained ~or the indicated tl~e~
. ~ and yields o~ 25-60% C0AVer~lOn tO polymer uere ob~ain~d.
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Xt ~an be seen rrom Table I that the phosphonitrlle trimer can be polymerized usin~ decalin as the solvent producln~
hlgh molecular weigh~ polymers,~while various solvents 3uch as tetralin, naphthalene, decalin/tetralin mixture7 prehnltene . pro~uced polymerq o~ somewha~ di~erent molecular wei~hts.
' ... ~ .
. :' . '~:~ ' .
. . . .
~or solven~s wlth boillng points below 190C~ ~uch . ~ as toluene it was necessary ~o use a pressurlzed sy~tem. An : . Argon blanket was maintained over the polymerization solution 10 : at 10-~00 psig. Every 2-6 hours the system was ~lushed by low- ~:
. ering the pressure and repre~suring with rresh Argon. Other .
i conditiona were a~ indicated in Table ~. ~ .
". ' ...... , :. . , . ' ' : . .
''.' '..... . . . . ' . , . '.
. . TABL~' II
. ~ , . . Milllmoles o~
.X (NPC12)n Sul~ur per Temp. Time % Conv-Sol~ent in Solventmol (NPC12) C Hrs ersion --3 _ _ ., . ' `' . ~ ., '. :~, Toluene 49 2. 5 205 93 76 Toluene ~ 60 3 . 205 46 33 . ' .. , , . . . , . . ,:
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Example 1 was repeated employing the solvents ~hown ln Table III, resultlng in 90-96% converslon Or phosphonitrilic chlorlde oligomer~ to hlgh molecular weight polymer. The .
. resultin~ product arter recovery was derivatlzed as described .
. in United States Patent 3,970~533 issued July 20, 1976 using C2 and C5 ~luorinated alcohols and with o-allyl phenol for cura-. tive sites~ Table III gives the rlnal derivatl~ed phosphonitrl-lic chloride polymer with tri~luoro ethanol and octafluoro- . .,.
~entanol with comple~e molecular weight determinations. The .
~ho~phonitrilio chloride polymer obtained rrom the examples dis- .
. ~u3sed in Table I can be derlvatized to useful f1uoroallcoxlde f ~ ~ ff ~la9tor rs, In the ~am- manner.
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.
.It is also known that the thermal polymerization of hexachlorocyclophosphazene and octachlorocyclophosphazene can be effected in the presence of various catalysts as reported in "phosphorus-Nitrogen Compounds" published 1973 by Interscience Publishers, New ~ork.
Previous attempts to polymerize cyclic dichlorophos- :
phazenes in solution have resulted in excessive gelation and the production of unusable products.
It has now been found that instead of controlling the temperature and other reaction conditions in order to obtain polymer of a desired molecular weight, it is now possible to ob-tain products with a desired molecular weight by choice of a suitable solvent as the reaction medium.
It has also been found that the presence of a small amount of sulfur either as elemental sulfur or as a sulfur com- `
pound in the solution in the polvmerization mixtures appears to overcom~ a tendency of the solvents to react with cyclochloro- ~ :
phosphazenes at high tempera-tures Eorming an intractable gel.
It has further been found that the choice o~ solvent or mixture of solvents significantly affects the molecular weight of the resulting polymer and that as a consequence polymer of a desired molecular weight is produced by selecting an appropriate :
.:' B ~ ~:
~ ~ ~ 5f~
solvent and suitable reaction conditions.
A princip~l object of the present invention is there-fore to provide a new and improved process for the solution poly-merization of cyclic dichlorophosphazenes which yields essen~
tially linear polydichlorophosphazene polymers.
Another object of the invention is to provide a solu~
tion polymerization process which can be con~ucted at atmosphe-ric pressure and at comparatively moderate temperatures and under a relatively inert and easilY controlled atmosphere.
A further object of the invention is to polymerize cy- ;
clic dich~orophosphazene oligomers to produce linear polydichlo-rophosphazene polymers exhibiting a unique, very narrow range or molecular weights, heretofore unobtainable in previously prac ticed bulk polymerizations.
In accordance with the invention, these and other ob-jects are achieved by polymerizing solutions comprising cyclic dichlorophosphazene oligomers dissolved in a liquid solventCha-Ying a dielectric constant o~ at least two~ in the presence of about 1 to up to 20 millimoles of elemental sulfur-or sulfur donating compound per mol of cyclic dichlorophosphazene oligomer.
The solvent is selected so as to be solvent for both the oli-gomers and the sulfur or sulfur donating compound~and the poly~
merization is conducted'for up to 300 hours at a temperature between about 140C and 225C in a reactor which may be either glass lined stainless steel vessels or unlined stainless steel vessels, or galss vessels. Preferably, the oligomers are dissol-ved in between about 10% and up to 80% by weight of selected solvent.
As solvent medium in which the thermal polymerization of low molecular weight cyclic polydichloroPhosphazenes is con- ~
ducted, use can be made of aromatic hydrocarbon or cyclo-alipha- ~ .
tic hydrocarbon solvent.
' 'B , . . : : ' ~5~2~ ~
Suitable hydrocarbon solvents include decalin, tetra-lin, naphthalene, cyclohexane, toluene, dimethylbenzene, dihy-droanthracene, tetramethylbenzene, cumene, cymen, mono-, di-, tri-, tetra- substituted aromatic compounds where the substi-tuents are straight cahin or branched chain hydrocarbons with up ~o 10 carbon atoms.
As other solvents, use can also be made of liquids ha- -ving a dielectric constant of at least two, and which are sol-vents for both the cyclic dichlorophosphazene starting materials and for the sulfur or sulfur-donating compound presentas catalysts.
A further solvents suitable for such polymerizations, use can be made of aromatic compounds carrying polar groups such as methoxy, N, N-disubstituted amino, halogens particularly mono-, di-, tri- or tetra-halogen substituents on the aromatic nucleus, and mixtures of said solvents or other hydrocarbon solvents of a similar nature.
Still other solvents which have been used-include aro-matic compounds including those which are monocyclic or polycyclic and which are either unsubstituted or substituted, especially ~ with polar substituents such as halogen, N,N ' -diakylamino, alkoxy, and other polar groups. Aromatic solvents with up to four polar substituents on the aromatic ring have been employed. These polar substituents can be on the ring or on a side-chain. For example, the aromatic ring can have either electron withdrawing groups or electron supplying groups. Examples of such solvents are 2-chloro toluene; 2,3-dichlorotoluene; 2,3-dichloroethyl- ~ ~
benzene; and 2,3,4-trichloroethylbenzene. ~ ;
In accordance with the invention, use must also be made of small but significant amounts of elemental sulfur or sulfur donating compounds such as tri- or tetra-sulfides o~ organic compounds or tri- or tetra-sulfides o~ inorganic compounds in inorganic sulfides and organic sulfides. Sulfur donor compounds -- 4 ~
,~
f~ 3 which are suitable are compounds which release sulfur at the --temperatures at which the solution polymerization is conducted.
Such compounds are commonly used in the vulcanization of rubbers include tetramethylthiuram tetrasulfides, and other tetraalkyl thiuram tetrasulfides; the reaction products of alkylene chlo-rides and sodium polysulfides, amine disulfides such as 4,4'-dithio dimorpholine and other compounds which release sulfur when heated to about 200C.
Briefly the present invention includes polymerization of cyclic dichlorophos~hazenes in aromatic or cycloaliphatic hydrocarbon solvents by proceeding as follows.
All of the constituents, i.e. solvent, cyclic dichlo-rophosphazene oligomers and sulfur or sulfur donating compounds were charged into the reaction vessel. The sulfur was added as a solution in the hydrocarbon solvent, for ease in handling.
For solvents with boiling points below 150C pressu-rized systems were utilized with pressure from 0-1000 psig and ~a preferred range of 0'-200 psig.
For solvents with boiling points between 150C and 250C reactions were carried out at atmospheric pressure. Dry Argon gas was passed over the reaction mixture. Care was taken at all points to prevent oXyqen or moisture from being introduced : : , . . . .
,':' " ' " ~ : . ': ' .: , :
5~23 ~ :
l ~ ~
~ ~l~
into reaction mi~ture. Apparatus wa~ preheated ln 140C oven for 24 hour~ be~ore use~ , Stirring was by means o~ magneti~ bars. Polymeri~a~
tions were conducted ~or rrom 40-300 hours preferably at 200-~20C bath temperature. The polymerizatlon reaction mlxture wasusually solid at completion of reaction. Unreacted cyclics and hydrocarbon solvent were s~ripped by repeated washing with dry ~exane in inert, dry atmosphere. RecoYered polymer was dissol-~ed in benzene yieldln~ a mostly soluble polymer, eXhibiting dilute ~olution ~iscosi~ies between from about 0.09 to,1.2 - (DSV 1~ equivaient to inherent vlscosity stated in decal1ter~
ram~.
Volatile material ~wept ~rom the reaction mixture ino-luded H~S and HCl.
The same polymerizat,ion reaction carried out under the ; l ame reaction conditions to converslons Or 60% or more except hat lt was conducted ln the absence o~ sul~ur or sulrur dona-ting compound~ produced products which were usually ~eiled and in~oluble ln benzene. The exact nature Or the effect o~ the Z0 ~ul~ur on ~he pol~merization is not rully understood.
The inventlon will be further described in the follow-ing ~x~mple~ given by way o~ illu~tration and not intended to llmit the inventlon. The data in Table I was obtained by pro-ceeding as ~ollowa: .
'''-; ''"''" ~ ' ''' "' ~'' ''-' .'. ',' . .
. . ' ,. ' .
:~15'~'Æ:~ I
: E~ample The lndicated number mllllmole~ Or elemental sulfur dissolved in te~ralin or other solvent was added to a solution Or cycllc dlchlorophosphazene trimer in the indlcated solvent . in a glass or stainless steel reaction vessel. An ~rgon rlow of 1 to ~ ml/minute was maintained across the ~ur~ace of the ~olution. Temperature wa~ maintained ~or the indicated tl~e~
. ~ and yields o~ 25-60% C0AVer~lOn tO polymer uere ob~ain~d.
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. . P t~ 1 0 ~ ~ td h h S ~ h h h h 4 .~ .C
. ' O ~) Q> ~L) ql a) a3 a) c~ Q) ~) C) ~) ~I) Q) a) a~ a~ ~ rl . ' , U~ ~1~ ~ Q ~1~ ~ Q E~ E-J ~ E-~ E~ ; Z ~ .
. . . ~ .
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., , _~_ . ' . '::
1 5'~23 . .....
;` ' ' ', .
~o . ` . . .
. ~ ~ ,.~,,~,,,, . . . .
J~ c~ -.. , ...... -.
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.' . , . , ,.'. ': . . ., .
., . ~ 000000000' 00 ' . ' ' . ~ ~ ,,' '' .
~. O ~D N N N ~1 (~J N ~ .. . ..
,' . , '" . ' , '~ ' ' : ' , , ., . ',: , ' . . , ., -',:' , . ~C: . .. ',' ,',','. ,, .
O rl O O~ D N ~::S' t-- :J' ' h ~ 1nJ ~N OC) U~ ~ ' .j E~ ¦ a) o ~ ~1 o o o o o ~ ~ ,,, .
" . -, . a) , ., . ~ , :1 , ', . ~, ' ,' , "
; '' ' ~ ' ' ' ' ~: : ., .
,, . ~ ~ I~Lt~ooOooOo 11~0 ' ''. .' ~ ' . ' . ' ' ~: E~ O o o N ~ J N N O O O ~ :
O O ~J N ~U N N N ~J ~ N ~1 , , .
, '. ~_ ~ , , H . . . . . .
. . . . ., ' . ~ . ' ,.,. . .' . ~7 ~ h~ .
~ ' ~ ~ ' ~' . .
'' ~ . ,,. , . .
rt `~ ~ . . .
. . ~ h ; . ; .
N p ~
. ' ~ 000000000 OI~J ' ' " .
, .,' ' ~ ~: ~ , " ",, ,,, ~,", , . " , :. . . . . . ' , ' , :, . , ' ' . : ' ~ ., . . ' ' ' ' , ' '' ,, ' , ',' ~ '' ', ' ,", '" ,: ' ., . ~
. ~1~1~ 1~ ' ' ' - ' ^ ' ' . h h h ~ h h h h h ` . :
, ' '' ' ~ ' . . . 0 ~ ~ a~ q) a) a~ a) .
a) a ' . ~ ~ ' . ~ ~ ~ . .: .
' ~ ~1 ~ ~/ ~ ,~ . , . , . ~ ~ ~ ,C ' ' '' '' . ~ c~ . . . . ' O a) a) C) ~) al a) a) a) a) ~- h , , .
. .. ~ C~ ~ a Q ~ a Q ~ Q ~ P~ . .
~ ~ ' . 9,. ''.
, ,, ' . .
`~1 , . ., i ~ ~ ~
Xt ~an be seen rrom Table I that the phosphonitrlle trimer can be polymerized usin~ decalin as the solvent producln~
hlgh molecular weigh~ polymers,~while various solvents 3uch as tetralin, naphthalene, decalin/tetralin mixture7 prehnltene . pro~uced polymerq o~ somewha~ di~erent molecular wei~hts.
' ... ~ .
. :' . '~:~ ' .
. . . .
~or solven~s wlth boillng points below 190C~ ~uch . ~ as toluene it was necessary ~o use a pressurlzed sy~tem. An : . Argon blanket was maintained over the polymerization solution 10 : at 10-~00 psig. Every 2-6 hours the system was ~lushed by low- ~:
. ering the pressure and repre~suring with rresh Argon. Other .
i conditiona were a~ indicated in Table ~. ~ .
". ' ...... , :. . , . ' ' : . .
''.' '..... . . . . ' . , . '.
. . TABL~' II
. ~ , . . Milllmoles o~
.X (NPC12)n Sul~ur per Temp. Time % Conv-Sol~ent in Solventmol (NPC12) C Hrs ersion --3 _ _ ., . ' `' . ~ ., '. :~, Toluene 49 2. 5 205 93 76 Toluene ~ 60 3 . 205 46 33 . ' .. , , . . . , . . ,:
;; ' : ' . . ' . ' , : . , ' :, . . ' s~ , . ' ' . ~ , , ", , . , . : :: : . .
. ~
'. ', ".. ` ~ ^` ' ' '', , ''' ~ .' ' .. ,'' ' ' :" ' ''' ' , , , .' ' . . .,~
' , ' -10-JJ ~
. , , .
E~
.
Example 1 was repeated employing the solvents ~hown ln Table III, resultlng in 90-96% converslon Or phosphonitrilic chlorlde oligomer~ to hlgh molecular weight polymer. The .
. resultin~ product arter recovery was derivatlzed as described .
. in United States Patent 3,970~533 issued July 20, 1976 using C2 and C5 ~luorinated alcohols and with o-allyl phenol for cura-. tive sites~ Table III gives the rlnal derivatl~ed phosphonitrl-lic chloride polymer with tri~luoro ethanol and octafluoro- . .,.
~entanol with comple~e molecular weight determinations. The .
~ho~phonitrilio chloride polymer obtained rrom the examples dis- .
. ~u3sed in Table I can be derlvatized to useful f1uoroallcoxlde f ~ ~ ff ~la9tor rs, In the ~am- manner.
~`
I . I f ' - ., ' ' ' ' .: '. .' ' '~ " ' ' '.
. ~ - ~ .
~ ~ .
~ : :
h ¦ ~ ~ ) -. . . :, ¦ ~: N N ~ .
. . . o l ,, . ' -.
o U~ '' . N CO CJ~ ~ :
. ' , ~ ~ ~
. : h .
.- ;; 'd~ Q ~I . o C~ O ~ ., .. C N ~
' . i - ' , . ~ P . , ` . ' . . ~ ' . ~ P~ ~ ': o C3 ' ~, ~ . . H l ` ~ ¢ ~ . ~ .
.. . , ~,~ V ^ o C) . , ... . , . .
. , a:l :z~ ~ ~ . ., .. . .
,: . . ¢ ~ ~ ~ :~ ., ,. . .
~ _~ h rl ?~ ~ : . . ;. .
. a~ o . 1~ ~D O ' ' "'- ' ,, ., ~.,. ". , .~. ~o oo c~ C~ . ` .': '.'.' '- ,: ', -'~ VJ~ ,,' ' '' .'' , ; ,' , ' . ' ~ d ' ' ' '' : ' ' ' ' . ' . ~ h ~ O ~
, ; P ~ V : . , ~ ' ~ : .
~4~0 1: b~ t-e E! a~ t-- ~o ~ . .
.` ~ V~ ~o 5r~ . .
. .- ~ ~:
:, .. . ~ h ;
:`. ' ~ ~ 3 ~ .
. P h~` h I - -.. . . , .. , O ~ ~ ~) ^ ' . ' ' - .
. ~ . E~1 rl d N ;
. . ~ ' ' . , .
., . ' ' ' '' ' . ' ~
-12- .
.
Claims (12)
1. In a process for producing substantially linear polydichlorophosphazenes in which the degree of polymerization is between about 20 and 50,000, from cyclic dichlorophosphazene oligomers represented by the general formula (NPCl2)n in which n is an integer from 3 to about 15, the improvement which com-prises conducting the polymerization in solution in a solvent for said dichlorophosphazene oligomers, for up to about 300 hours and at a temperature between 140 and 225°C, in the presen-ce of an amount ranging from 1 to about 20 millimoles of sulfur or sulfur-donating compounds per mole of cyclic oligomer, said amount of sulfur or sulfur-donating compounds being effective to prevent the formation of appreciable amount of gel, said sol-vent being a liquid having a dielectric constant of at least two and being a solvent for both said sulfur or sulfur-containing compounds and said dichlorophosphazene oligomers.
2. The process of claim 1 in which the sulfur material is elemental sulfur.
3. The process of claim 1 in which the solvent is an aromatic hydrocarbon.
4. The process of claim 3 in which the solvent is selected from the group consisting of decalin, tetralin, naphtha-lene, cumene and cymene.
5. The process of claim 3 in which the solvent is a substituted aromatic hydrocarbon.
6. The process of claim 5 in which the substituents are polar groups.
7. The process of claim 5 in which the substitutents are halogens.
8. The process of claim 1 in which the sulfur-dona-ting compound is selected from the group consisting of the orga-nic and inorganic tri- and tetra-sulfides.
9. The process of claim 1 in which the solvent has a boiling point below 150°C and the polymerization is carried out under a superatmospheric pressure up to 1000 psig.
10. The process of claim 1 in which the solvent initially present comprises 20 to 80% of the mixture being polymerized.
11. The process of claim 1 in which polymerization is carried out at a temperature between 200°C and 220°C.
12. The process of claim 1 in which polymerization is carried out at atmospheric pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA301,866A CA1115023A (en) | 1978-04-25 | 1978-04-25 | Solution polymerization of chlorophosphazene with sulfur modifier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA301,866A CA1115023A (en) | 1978-04-25 | 1978-04-25 | Solution polymerization of chlorophosphazene with sulfur modifier |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1115023A true CA1115023A (en) | 1981-12-29 |
Family
ID=4111328
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA301,866A Expired CA1115023A (en) | 1978-04-25 | 1978-04-25 | Solution polymerization of chlorophosphazene with sulfur modifier |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1115023A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112739228A (en) * | 2018-09-25 | 2021-04-30 | 菲利普莫里斯生产公司 | Heating assembly and method for inductively heating an aerosol-forming substrate |
| US12063970B2 (en) | 2018-09-25 | 2024-08-20 | Philip Morris Products S.A. | Inductive heating assembly for inductive heating of an aerosol-forming substrate |
-
1978
- 1978-04-25 CA CA301,866A patent/CA1115023A/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112739228A (en) * | 2018-09-25 | 2021-04-30 | 菲利普莫里斯生产公司 | Heating assembly and method for inductively heating an aerosol-forming substrate |
| CN112739228B (en) * | 2018-09-25 | 2024-04-26 | 菲利普莫里斯生产公司 | Heating assembly and method for inductively heating an aerosol-forming substrate |
| US12016392B2 (en) | 2018-09-25 | 2024-06-25 | Philip Morris Products S.A. | Heating assembly and method for inductively heating an aerosol-forming substrate |
| US12063970B2 (en) | 2018-09-25 | 2024-08-20 | Philip Morris Products S.A. | Inductive heating assembly for inductive heating of an aerosol-forming substrate |
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