Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
llO~SZ9
This invention relates to the manufacture of cel-
lular polymeric materials. More particularly, the invention
involves the application of certain compounds as expanding
agents for rubbers and plastics. Specifically, the invention
resides in the discovery that certain hydrocarbyl sulfonyl
carbohydrazide compounds are valuable blowing agents in the
manufacture of cellular polymeric materials. Furthermore it
relates to some novel compounds suitable for these uses.
The application of heat sensitive organic nitrogen
compounds as expanding agents for cellular polyers is well
known. For example, azodicarbonamide~decomposition point
about 200C) has been widely employed as a blowing agent for
rubbers and plastics. Other organic nitrogen compounds which '~
have been used include the following:
oxybis(benzenesulfonyl hydrazide) (dec. 160C)
(U.S. Patent 2,552,065)
p-toluenesulfonyl semicarbazide (dec. 235C)
(U.S. Patent 2,491,709)
N,N'-~initroso-N,N'-dimethylterephthalamide (dec.
90C) (Fuller, M.R., Ind. ~. Chem. 491 722 (1957)
As can be seen, the temperatures at which these
various compounds produce gas varies over a wide range and,
as may be expected, the applications in which each type may
be used are restricted to the particular processing temper-
atures of particular polymers. Further restrictions on the
application of specific blowing agents are imposed by the
nature of the decomposition products, gaseous and otherwise.
For example, polyester polymers are adversely affected by
ammonia gas which is formed in the decomposition of azodi-
carbonamide and by p-toluene sulfonyl semicarbazide. Odorous
decomposition products are formed during the decomposition of
-- 1 --
,
::~
S29
dinitroso pentamethylene tetramine restricting the use of
this compound to the e~pansion of certain rubbery polymers
whereln the odor is not a critical factor.
An object of the present invention is to provide
superior expanding agents for polymers which are normally
processed at temperatures above 210C. A further object is
to provide high temperature blowing agents which do not cause
adverse effects on the stability or utility of the expanded
polymer. A specific object is to provide expanding agents
for polyester polymers.
The simple hydrocarbylsulfonyl carbohydrazide
blowing agents of this invention can be illustrated by the
structure:
HH HH
R-S02NN-C-NN-S02R
wherein R is a hydrocarbyl radical and preferably is an
alkyl radical having 1 to 12 carbon atoms, most preferably
1 to 4 carbon atoms, an aryl radical having 6 to 12 carbon
atoms, most preferably 6 to lO carbon atoms; an aralkyl or
alkaryl radical having 7 to 12 carbon atoms, most prefer-
ably aralkyl having 7 to 9 carbon atoms and alkaryl having
7 to 10 carbon atoms; a cycloalkyl radical having 5 to 9
carbon atoms, most preferably 5 to 6 carbon atoms.
The compounds wherein R is an alkyl radical are
novel compounds. These alkyl derivatives are shown by ex-
ample below to produce 50 to 100% more gas upon decomposition
than the corresponding known aryl derivatives.
These compounds can be readily prepared by either
of two methods:
PSZ9
2NN C-N-NH2 + 2RSo Cl base > RSO2NN-C-NN-SO2R +2HCl
O o
or
HH HH HH
(2) 2RSo2NNH + COC12 > RSO2NN-C-NNSO2R + 2HC~
Method (1) has been employed by Cremlyn and Turner
(J. Chem. Soc. 1970 C, 2629) to prepare several of these
compounds wherein R is phenyl, p-tolyl or p-acetaminophenyl
for testing as potential herbicides, but no suggestion as
to the utility of the compounds as blowing agents is given.
Method (2) is novel.
A variation of the invention is found in the reac-
tion products of bis(sulfonyl chlorides) with carbohydrazide
to yield oligomeric products wherein n is from 2 to 50 or
even higher:
(3) ClSO - Y - SO2Cl + H2NN-C-N-Nb2 >
H H H H
~ -502N-N-C-N-N-502~ _
The resulting products are oligomers. An
alternate procedure for producing these substances is given
in equation (4)
(4) H N-N-SO2-Y-SO2NNH2 + COC12
H H H H
-Y-SO2N-N-C-N-N-SO2-
n
llQ~S29
In both cases, Y is a difunctional organic moiety selected
from arylene, preferably phenylene, alkarylene, preferably
having 7 to 10 carbon atoms, and the structure -Rl-A-R2-
wherein A is a single bond connecting Rl and R2 or is -O-,
-S-, -SO-, -SO2-, usually a single bond or -O-; or A is
an alkylene radical having from 1 to 6 carbon atoms such as
methylene, ethylene, propylene, tetramethylene and hexa-
methylene, or an alkylidene radical having 2 to 3 carbon
atoms such as ethylidene and isopropylidene; and Rl and R
are the same or different and are alkylene having 1 to 4
carbon atoms or phenylene.
Preferably Y is a radical such as phenylene, tolyl-
j ene, xylylene, biphenylene, oxydiphenylene, 1,3-dimethyl-
j3 benzene, and methylenebisphenylene. Other preferred species
of Y include such as ethylene, butylene and hexamethylene.
vl Illustrative of the hydrocarbylsulfonyl carbo-
hydrazides useful in the practice of this invention are the ;
I following:
; 1,5-bis(benzenesulfonyl) carbohydrazide
1,5-bis(p-toluenesulfonyl) carbohydrazide
1,5-bis(p-chlorobenzenesulfonyl) carbohydrazide
l,S-bis(methanesulfonyl) carbohydrazide
l,S-bis(ethanesulfonyl) carbohydrazide
1,5-bis(n-propanesulfonyl) carbohydrazide
1,5-bis(n-butanesulfonyl) carbohydrazide
1,5-bis(n-hexanesulfonyl) carbohydrazide
1,5-bis(isopropanesulfonyl) carbohydrazide
1,5-bis(tert-butanesulfonyl) carbohydrazide
Also useful for the purposes of the invention are
the reaction products of difunctional organic sulfonyl
chlorides with carbohydrazide. Thus, carbohydrazide may
.. . . .
:.' : .
;529
be reacted with bis(sulfonyl chlorides~ such as the fol-
lowing:
Benzene-1,3-bis(sulfonyl chloride)
Benzene-1,4-bis(sulfonyl chloride)
l-Methylbenzene-2,4-bis(sulfonyl chloride)
1~3-Dimethylbenzene-4~6-bis(sulfonyl chloride)
p,p'-Oxybis(benzenesulfonyl chloride)
1,2-Ethanebis(sulfonyl chloride)
-Butanebis(sulfonyl chloride)
Method 1 referred to above lnvolves reacting carbo-
hydrazide with a sulfonyl chloride in the presence of a base,
at a temperature of from about room temperature up to about
100C, and for a period of up to about 10 hours.
Preferably the sulfonyl chloride is added to a
suspension of the carbohydrazide in the presence of the
base. However, the order of addition may be reversed. Ex-
amples of suitable solvents include alcohols (i.e. methanol,
ethanol, isopropanol) water, tetrahydrofuran, dimethylform-
amide, acetonitrile, ethylene dichloride, trichloroethylene,
dibutyl ether, and the like. Examples of suitable bases
include sodium bicarbonate, potassium bicarbonate, sodium
or potassium carbonates or hydroxydes, as well as amines.
~ethod 2 referred to above involves reacting a
sulfonyl hydrazide with phosgene (COCl2) in the presence
of a base, at a temperature of about 15 to 100C, and for
a period up to about 10 hours.
Preferably the phosgene is added to a suspension
of the sulfonyl hydrazide in the presence of a base, and
the temperature is maintained from about 15~ to 50C.
However, the order of addition may be reversed. The sol-
vents referred to for Method l are applicable for use herein.
- ~ .
S2~
Preferably a water-alcohol mixture is used. The bases used for
Method 1 are also suitable for use herein.
Each of the above methods may readily be conducted
at atmospheric pressure, and higher or lower pressures are
not necessary though they may be used.
In the aspect of the invention forming the subject
matter of this divisional application there is provided an
oligomeric(hydrocarbylsulfonyl) carbohydrazide of the formula
_ _
- - Y-SO2NHNH-C-NHNHSO2 - - .
~I ..
O _ n
wherein Y is a difunctional organic moiety selected from the group
consisting of phenylene, alkarylene having 7 to 10 carbon atoms
and a group of the structure -Rl-A-R2- wherein A is selected
from a single bond connecting Rl and R2, -O-, -S-, -SO-, -SO2-,
alkylene with 1 to 6 carbon atoms, and alkylidene with 2 to 3
carbon atoms, wherein Rl and R2 are the same or dlfferent and
are alkylene having 1 to 4 çarbon atoms or phenylene, and
wherein n is an integer of from 2 to about 50.
In another aspect of the invention forming the subject
matter of this divisional application there is provided a method
of expanding a gas-expandable polymeric material comprising
heating a composition comprising a gas-expandable polymeric
material and an oligomeric (hydrocarbylsulfonyl) carbohydrazide,
as set out above, to a temperature in excess of the decomposition
temperature of the oligomeric (hydrocarbylsulfonyl)
carbohydrazide.
In one aspect the method is provided wherein the
temperature is in excess of 200C.
r' ~_ J
,
11¢~i~529
The chemicals of this invention are useful in the
expansion of polymeric gas-expandable materials. They are
characterized by xelatively high decomposition points (well
in escess of 200C) and thus are particularly valuable in the
formation of cellular plastic articles which are expandable
at these relatively high temperatures. The quantity of gas
produced by the compounds varies considerably with the nature
of the various substituents. Usually the compounds producing
the largest amount of gas are the most valuable. However,
the decomposition temperature and the nature of the decompos-
ition residue are also factors in the utility of the compounds
as blowing agents.
One outstanding feature of these compounds is the
absence of ammonia in the decomposition gases. Ammonia is
known to produce deleterious effects in some expandable
plastics. In any case, the bis(hydrocarbylsulfonyl)
carbohydrazides of this invention are particularly valuable
in the expansion of plastics requiring processing temperature
well in excess of 200C.
The polymeric materials which may be expanded by
these blowing agents include homopolymers, interpolymers,
graft polymers, and mixtures and blends of two or more of
these, and include thermoplastic, thermosetting, and rubbery
polymers. The new blowing agents are useful for expanding
polymers that have high processing temperatures such as the
polycarbonates, phenylene oxide-based resins, polyaryl sul-
- 6(a) -
llQ~5zg
fones, the various nylons, polyesters, certain polystyrenes,
polypropylene, poly(styrene-acrylonitrile), polyacetals,
poly(vinyl chloride), poly(vinyl acetate), poly(phenylene
sulfide), poly(~ethylpentene), low and high density poly-
ethylenes, polyimides, polyaryl ethers, ABS polymers, poly-
acrylics, cellulosic polymerics, halogenated polymers,
especially the fluoroplastics, poly(ethylen~vinyl acetate),
etc. Other polymers include poly(butadienestyrene), polyiso-
prene (including natural rubber), cis- or trans-polybutadiene,
butyl rubber, ethylene-propylene copolymers, ethylene-
propylene-non-conjugated diene terpolymers, and poly-
(butadiene-acrylonitrile).
Generally, the amount of blowing agent used will
depend on the nature of the polymer to be expanded, and
the desired density of the foam to be produced. Usually,
0.05 to 15, and most often, 0.2 to 5.0 parts of blowing
agent are employed, based on 100 parts of polymer by weight.
The blowing agents can be used alone, or in combination with
other blowing agents. Activating substances can be used to
increase the efficiency of gas evolution, or to lower the
normal decomposition temperature of the blowing agents of
the invention. Other additives such as plasticizers, fillers,
nucleating agents, and the like can also be added to the
polymer to be expanded.
The following examples illustrate the preparation
of some of the bis~hydrocarbylsulfonyl) carbohydrazides of
the invention, their efficiency as gas producing agents upon
deco~position, and their use as blowing agents for producing
expanded materials.
ll(~'~SZ9
Example I. Preparation of 1,5-bis(benzenesulfonyl) carbo
zide
175.6 g (1.0 mole) of benzenesulfonyl chloride
was added to a stirred mixture of 45 g tO.5 mole) carbohydra-
zide and lO0 g sodium bicarbonate in lO00 ml ethanol in a 3
liter 3 neck flask. The mixture was heated to gentle reflux
for six hours. The cooled mixture was filtered and the
solid precipitate (containing the desired product along with
sodium chloride) was washed with ethanol and dried. Yield:
207 g. This mixture was then suspended in water and stirred
for 10 minutes. The insoluble solid was filtered off and
washed well with water and dried.
Yield: 120.5 g, m.p. 227C (dec.)
A portion (30 g) of the product was taken up in
concentrated ammonium hydroxide, diluted some with water
and filtered. The solution was then acidified with dilute
sulfuric acid. The resulting white solid was filtered,
washed with water and dried. Yield: 28 g, m.p. 230C
(dec.)
20 Analysis:
Calc- for C13H14N4O5S2Found
-
% C 42.1 41.65
H 3.80 3.78
N 15.1 14.89
Example II. Preparation of 1,5-bis(p~toluene sulfonyl)
carbohydrazide
- 190.5 g (1.0 mole) p-toluene sulfonyl chloride,
45 g (0.5 mole) carbohydrazide, 84 g (1.0 mole) sodium
bicarbonate and 1000 ml methanol were placed in a 2 llter
flask. The mixture was stirred and heated to reflux (65C)
for 90 mlnutes. Carbon dioxide evolution was complete at
this point. The solid product and sodium chloride were
SZ9
filtered off. The material was suspended in water to dis-
solve the sodium chloride and the residual solid product
was filtered off, washed well with water, and dried at
60C.
Yield: 139 g Dec. temp~ 232C
A portion was dissolved in dioxane and reprecipi-
tated by added an equal volume of 50% ethanol. The result-
ing product (after drying) decomposed at 235C.
Analysis:
10Calc. for C H N O S
15 18 5 5 2 Found
% C 45.27 45.47
H 4.52 4.59
N 14.07 13.67
Example III. Preparation of 1,5-bis(p-chlorobenzenesulfonyl)
carbohvdrazide.
.. .. ~
211 g (1.0 mole) p-chlorobenzenesulfonyl chloride
was added to a suspension of 45 g (0.5 mole) carbohydrazide
and 100 g sodium bicarbonate in 1000 ml ethanol in a 3 liter
reaction flask. ~he mixture was stirred and heated grad-
ually to gentle reflux (80C) as carbon dioxide was evolved.
Heating was continued until CO2 no longer evolved (3 hours).
The mix was cooled to 20C and filtered. The mlxture of pro-
duct and sodium chloride was dried at 60C. Yield = 227 g.
The solid mixture was suspended in 2000 ml water, stirred
to dissolve the sodium chloride, and then the insoluble pro-
duct was filtered, washed and dried. Yield = 129 g, m.p
239-240C (dec.)
A portion was purified by solution in ammonium
hydroxide, followed by filtration and acidification of the
filtrate with dilute sulfuric acid. The washed and dried
product had the following analysis:
g _
Calc- for C13H12N45C1252Found
% C 35.53
H 2.73
N 12.76
Example IV. Preparation of 1,5-bis(methanesulfonyl) carbo-
hvdrazide
_ . _ _
A mixture of 45 g (0.5 mole) carbohydrazide, 84 g
NaHCO3 (1.0 mole) and 50 ml methanol was stirred as 114.5 g
(1.0 mole) methane sulfonyl chloride was added over 30
minutes. The temperature rose from 25C to 40C. The
stirring was continued for 15 minutes (temp. 44C). The
mixture was then heated to 65C for two hours, and was then
cooled to 25C and the solid product (including sodium
chloride) was ~iltered and washed with methanol and dried.
Yield: 146 g. The material was first suspended in water
to remove sodium chloride and then filtered, washed with
water and dried. Yield: 81 g, m.p. = 207C dec.
A portion of the product was recrystallized from
water and had a melting point of 210C.
Analysis:
CalC- for C3HlON4O5S2Found
% C 14.60 14.99
H 4.07 4.15
N 22.7 22.03
S 26.0 25.59
Example V. Preparation of 1,5-bis(ethanesulfonyl) carbo-
hydrazide
A mixture of 45 g (O.S mole) carbohydrazide,
85 g NaHCO3 (1.0 mole) and 250 ml methanol was stirred and
128.5 g (1.0 mole) ethane sulfonyl chloride was dropped in.
The temperature rose from 25C to 45C during the reaction
-- 10 --
110~52~
which took 1 hour. Stirring was continued for two hours.
The product was filtered, washed and dried. Yield: 145.9 g
m.p. 195C.
A portion was recrystallized from water and had a
melting point of 191-192C.
Analysis:
Calc- for C5H14N45S2Found
% C 21.8 21.32
H 5.1 5.01
N 20.4 19.76
S 23.3 23.17
Example VI. Preparation 1,5-bis(n-propanesulfonyl) carbo-
hydrazide _ _
Into a l-liter reaction flask was charged 29.5 g
(0.2 mole) n-propane sulfonyl chloride, 200 ml ethanol, 9 g
(0.1 mole) carbohydrazide and 16.8 g (0.2 mole) sodium
bicarbonate. The mix was stirred and heated gradually to
80C over a one hour period and was then allowed to reflux
for four hours. The separated sodium chloride was filtered
off (hot). The filtrate was cooled whereupon the crystal-
line product separated (17 g) m.p. 191-194C.
Upon recrystallization from methanol the product
melted at 194-196C.
Analysis:
CalC- for C7H18N4O5S2Found
C 27.81 27.13
H 5.96 6.04
N 18.54 18.33
Example VII. Preparation of 1,5-bis(n-butanesulfonyl) carbo-
hydrazide
A mixture of 11.25 g (0.125 mole) carbohydrazide,
~ . -: ,. .
lla~}szs
25 g sodium bicarbonate, 200 ml methanol and 37 g (0.25
mole) l-butanesulfonyl chloride was heated to 60C until
evolution of CO2 ceased. The mix was cooled and water was
added to precîpitate the product. The initial precipitate
weighed 12 g (dry). This melted with decomposition at
195-197C.
Analysis:
or CgH22N4O5S2 Found
% C 32.60 32.12
H 6.67 6.83
N 16.95 16.97
The filtrate deposited 8.0 g more product on
standing.
Example VIII. Reaction product of carbohydrazide with p,p'
_ oxybis(benzenesulfonyl chloride) (l:l)
77.4 g (0.2 mole) p,p'-oxybis(benzenesulfonyl
chloride), 18 g (0.2 mole) carbohydrazide, 33.6 g (0.4
mole) sodium bicarbonate in a mixture of 100 ml water and
300 ml ethanol was stirred for two hours while carbon di-
oxide was evolved. The temperature was then raised to 70C
(reflux temperature) for one hour. Then 500 ml water was
added to the mix and the separate solid was filtered off,
washed with water, and dried (60C). Yield: 66 g dec.:
223C.
This material was completely soluble in ammonium
hydroxide. Reprecipitation of the compound from the clear
filtrate by addition of dilute acid gave material which
decomposed at 230C.
Example IX. Reaction product of Carbohydrazide with 4,4'
biphenylenebis(sulfonyl chloride) (1:1)
A mixture of 70.2 g (0.2 mole) 4,4'-bisphenylene-
- 12 -
: 1111 OS29
bis(sulfon~l chloride), 18 g (0.2 mole) carbohydrazide,
33.6 g (0.4 mole) sodium bicarbonate in a mixture of 300
ml ethanol and 100 ml water was stirred for two hours.
Carbon dioxide was evolved. The mix was then warmed to
reflux temperature (70) for one hour. Water (500 ml) was
then added and the product was filtered off, washed well
with water, and dried. Yield: 62 g, dec. 235C.
This product was completely soluble in ammonium
hydroxide solution. When reprecipitated from the ammoniacal
solution with acid, the product (washed and dried) decomposed
at 240C.
Example X. Reaction Product of Carbohydrazide and 1,3 di-
meth~lbenzene-4,6-disulfonyl chloride
A mixture of 18.0 g carbohydrazide (0.2 mole),
40.0 g sodium bicarbonate, 400 ml methanol and 60.6 g (0.2
mole) 1,3-dimethylbenzene-4,6-disulfonyl chloride was heated
to reflux for two hours. Evolution of carbon dioxide occur-
red during the first 1/2 hour. The mixture was cooled to
20C and 1 liter of water was added with stirring for 1/2
hour. The product was filtered off, washed with water and
dried. Yield: 40 g.
The resultant product was polymeric.
Example XI. Preparation of 1,5-bis(benzenesulfonyl) carbo-
hydrazide from benzenesulfonyl hydrazide and
_ phosgene.
A mixture of 86 g (0.5 mole of benzenesulfonyl
hydrazide, 270 ml ethanol, 30 ml water and 42.5 g (0.5 mole)
of sodium bicarbonate was stirred in a l-liter 3-necked
flask as 27 g (0.25 mole + 10% excess) of phosgene was
bubbled into the mix. The temperature rose to 45C and
the mix was cooled to prevent further temperature rise.
- 13 -
: :`
~10~5;z9
The stirring was continued for one hour and the mix was
then cooled to 20C. The white crystalline product was
filtered off, washed well with water, and dried at 60C.
Yield: 57 g (61.6%)
This product decomposed at 242C.
Analysis:
CalC for C13H14N4O5S2 Found
.
% C 42.16 41.98
H 3.78 3.70
N 15.14 14.58
10 g of the above product was dissolved in conc.
ammonium h~droxide (completely soluble) and reprecipitated
with dilute acid. Yield: 9.0 g, Dec. pt. 235C.
Example XII. Preparation of 1,5-bis(p-toluenesulfonyl) carbo-
hydrazide from p-toluenesulfonyl hydrazide and
phosgene.
In a manner similar to that described in Example XI,
a mixture of 93 g (0.5 mole) of p-toluenesulfonyl hydrazide,
360 ml ethanol, 40 ml water and 42 g (O.S mole) sodium bi-
carbonate was stirred in a l-liter 3-necked flask as 27 g
(0.25 mole plus 10% excess) of phosgene was bubbled through
the stirred mixture. The product was filtered off, washed
with water and dried. Yield: 62 g, dec. 237C.
A portion of the product was dissolved in concen-
trated ammonium hydroxide (completely soluble) and re-
precipitated with acid. The washed and dried product de-
composed at 234C.
Analysis:
Calc- for C15H18N45 2 Found
30~ C 45.23 45.00
H 4.57 4~44
N 14.07 13.54
- 14 -
?S29
Example XIII. Preparation of 1,5-bis(p-chlorobenzene sul-
fonyl) carbohydrazide from the corresponding
sulfonyl hydrazide and phosgene
A mixture of 51.5 g (0.25 mole~ of p-chlorobenzene
sulfonyl hydrazide, 1~0 ml ethanol, 20 ml water and 21 g
(0.25 mole~ of sodium bicarbonate was stirred in a l-liter
three necked flask as 13.5 g (0.125 mole plus 5% excess)
of phosgene was bubbled through. After one hour the product
was filtered off, washed with water and dried. Yield
1034 g, dec. 254C.
Analysis:
Calc- for C13H12N4O5S2C12 Found
% C 35.54 3~.82
H 2.73 2.71
N 12.76 12.15
Example XIV. Preparation of 1,5-bis(3,4-dichlorobenzene-
sulfonyl) carbohydrazide from the correspond-
ing sulfonyl hydrazide and phosgene.
A mixture of 24.1 g (0.1 mole) 3,4-dichlorobenzene
sulfonyl hydrazide, 180 ml ethanol, 20 ml water and 8.4 g
(0.1 mole) sodium bicarbonate was stirred in a l-liter
three necked flast as 5.5 g (0.055 mole) of phosgene was
bubbled in. After one hour the product was filtered off,
washed with water and dried. Yield: 16.0 g, dec. 232C.
This product was recrystallized from a 90-10 mix of ethanol
and acetonitrile. Recovered 11 g, dec. 235C.
Analysis:
Calc for C12HloN45S2C14 Found
r
% C 30.71 30.45
H 1.97 1.99
N 11.02 10.63
- 15 -
~10~529
Example XV. Preparation of 1,5-bis(t-butylbenzenesulfonyl)
carbohvdrazide.
. . . ~
A mixture of 45.6 g (0.2 mole) of p-t-butyl benzene
sulfonyl hydrazide, 180 ml ethanol, 20 ml water and 16.2 g
(0.2 mole) sodium bicarbonate was stirred in a l-liter 3~
necked flask as 10.9 g (0.11 mole) of phosgene was bubbled
in. The mix was stirred for one hour and the product filter-
ed off, washed with water and dried. Yield: 36 g, melting
range: 172-185C, dec. 180-240C.
This product was treated with boiling hexene, and
the insoluble material was filtered from the hot solution.
Recovered 26 g, m.p. 212-214C, dec. 214-240C.
Analysis:
Calc- for C21H30N4O5S2Found
% C 52.28 51.87
H 6.22 6.24
N 11.62 11.11
Example XVI. Preparation of 1,5-bis(n-butanesulfonyl) carbo-
hydrazide
A mixture of 76 g (0.5 mole) of butane sulfonyl
hydrazide, 180 ml ethanol, 20 ml water and 42 g (0.5 mole)
sodium bicarbonate was stirred as 27 g (0.275 mole) of
phosgene was passed in. The mix was stirred for one hour,
and the product was filtered, washed with water and dried.
Yield 47 g, m.p. 205-207C, dec. 207-240C. This
material was completely soluble in concentrated ammonium
hydroY~ide. When recrystallized from aqueous ethanol (50/S0)
the product melted at 205-207C.
Analysis:
9 22 4 5 2Found
% C 32.73 32.05
- 16 -
i29
H 6.67 6.66
N 16.97 16.16
Example XVII. Gas Evolution Data on Bis(hydrocarbylsulfonyl)
Carbohydra z ides
The gas evolution of several of these compounds
was determined according to standard procedures. The re-
sults were as follows:
Temp. CC/G
C STP
1,5-Bis(benzenesulfonyl) carbohydrazide 240-300 164
1,5-Bis(p-toluenesulfonyl) carbohydrazide 235-300 148
1,5-Bis(p-chlorobenzenesulfonyl) carbohydra-
zide 2S5-310 147
l,S-Bis(methanesulfonyl) carbohydrazide 225-260 297
1,5-Bis(ethanesulfonyl) carbohydrazide 235-280 255
Example XVIII. Expansion of Polysulfone Polymer
Polysulfone pellets were pre-dried by heating at
250F for three hours. The pellets were then coated with
1% by weight of blowing agent by thoroughly mixing the resin
and the blowing agent in a glass jar. The uniformly coated
pellets were introduced into a pre-heated laboratory ex-
truder where the temperatures in F were: rear - 520,
front - 580, die - 520; the screw speed was 30 RPM at the
stock temperature shown below. The specific gravity of
the unexpanded polysulfone resin was 1,19898. The tempera-
ture profile varied depending upon the blowing agent used.
Specific
Blowing AgentStock Temp. F. Gravity
1,5-Bis(methanesulfonyl)530 0.71747
carbohydrazide
1,5-Bis(ethanesulfonyl)520 0.84019
car~ohydrazide
- 110~?529
Specific
Blowing A~ent Stock Temp~ F. Gravit~
1,5-Bis(n-propanesulfonyl) 530 0.79952
carbohydrazide
1,5-Bis(n-~utanesulfonyl) 530 0.93845
carbohydrazide
1,5-Bis(benzenesulfonyl) 525 0.82189
carbohydrazide
1,5-Bis(p-chlorobenzene- 520 0.74316
sulfonyl) carbohydrazide
R.P. p,p'-oxybis(benzenesulfonyl
chloride) and carbohydrazide
(1:1) 520 0.76361
R.P. 4,4'-biphenylene bis
(sulfonyl chloride) and
carbohydrazide 530 0.80201
Control (no blowing agent) 525 1.19999
Example XIX. Expansion of Thermoplastic Polyester with
1,5-bis(~-toluenesulfonyl) carbohydrazide
-
Valox (trademark) thermoplastic polyester was
coated with 0.3% by weight of 1.5 bis(p-toluenesulfonyl)
carbohydrazide in a drum tumbler. The coated pellets were
introduced into a commercial Beloit Siemag Structural St
6000/115 120 ton clamp extruder under the following operat-
ing conditions:
Zone Temperatures, F
Zone 1 430
2 465
3 480
4 475
6 460
7 440
- 18 -
5Z9
Mold temperature 180F
Melt temperature 470-490F
Injection pressure 11,000 psl
Back pressure 400 psi
Injection speed 0.8 sec.
Screw speed 30 rpm
Cycle 1.5 min.
Mold 1" x 1" x 3/8"
plaque
Density measurements on the expanded plaque
showed a 40~ reduction when compared to the unexpanded
polymer.
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