Note: Descriptions are shown in the official language in which they were submitted.
ll~B167
--1--
TITLE: ARYL AMINE TERMINATED POLYSULFIDE POLYMERS, RELATED
COMPOUNDS AND PROCESSES FOR THEIR PREPARATION
BACKGROUND O~ THE INVENTION
_
This invention relates to the art of polysulfide and
urethane polymers, processes for their preparation and cure
and methods for their use.
The high molecular weight polysulfide polymers prepared
in the known commerical polysulfide polymer synthesis bear
hydroxyl chain terminals. When these high molecular weight
polymers are chemcially split to form lower molecular weight
solids or liquid polysulfide polymers, the resultant macro-
molecules are thiol terminated. These materials, using
presently available cure methods, are quite satisfactory and
are commercially successful. Alternative cure methods con-
tinue to be of interest because such alternative cures holdthe potential for even better properties and new uses for the
novel products produced thereby. The introduction during the
initial polysulfide polymer condensation of variously function-
ized monomers so as to produce moderate molecular weight pro-
ducts amendable to alternative cures has been explored previous-
ly. The introduction of unsaturation, hydroxyl, carboxyl,
alkylamino, amide and aldehyde functions has been examined.
The cure of the hydroxyl or unsaturation containing polymers
has not proven commerically practical. The other groups are
reactive with sodium polysulfide and the conditions of the
initial polysulfide condensation reaction cause their loss.
No direct method of splitting the initially formed, very
high molecular weight polysulfide polymers to lower molecular
- weight products having other than thiol terminals has pre-
viously been demonstrated as practical.
Several methods of converting hydroxyl or thiol term-
inated polysulfide polymers to amine terminated polysulfide
polymers which may then be reacted with epoxy polymers to
~k
.~ qP
.
-2-
form cured solid resins have been proposed. U.S. Patent
3,221,851 illustrates the preparation of compounds of the
formula
R~-L-(Rss)x-R-L-R~l
wherein L is -O- or -S-; R' and R" are the specific alkyl-
amino groups
iv Riii H~ Riv Riii
~CH- CH - N ~ CH CH NH2
z being selected from 0, 1, 2, 3 or 4; Riii and RiV being
the same or different and being radicals selected from
hydrogen, normal and branched alXyl and substituted or
unsubstituted aromatic radicals; x is a positive number
greater than l; and R is an intervening polyvalent organic
radical. Here the alkyl amine functionality is introduced
subsequent to the polysulfide condensation reaction and any
desired molecular weight adjustments.
U.S. Patent 3,331,816 illustrate~ the preparation of
alkylamino terminated polysulfide polymers of the formula:
(Ri-L~RSS~R-L-R ) z
wherein L is -O- or -S- and wherein Ri and Rii are the
azomethino amino groups
R IRb H
-CH CH C=N ( RC-NH ~ Rc N 2
wherein Rc is an alkylene group having up to 6 carbon atoms,
d is an integer selected from 0, 1, 2, 3, 4 and 5; y and z
are selected from 1, 2, 3 and 4; Ra and Rb are the same or
different and are radicals chosen from the group hydrogen,
normal and branched alkyl having up to 6 carbon atoms and
substituted to unsubstituted alkylene-aromatic, aromatic
1148167
--3--
and alicyclic radical, R is an intervening group selected from
the class of intervening groups shown in U.S. Patent 3,335,201,
Tables I and II; and x is a positive number greater than 1.
Here again, the amino terminals are introduced subsequent to
g the_initial polysulfide synthesis and desired molecular
weight adjustment.
U.S. Patent 3,335,201 also illustrates amino terminated
polysulfides of the structure:
(Ri-L~RS~) X (R-L-Rii) Z
wherein L is -O- or -S- and wherein Ri and Rii are the phenol
amino groups:
OH
-CH2 ~ CH -NH--tRiii NH )WRiv NH2
M N* Q
and/or
OH
-CH2~L CH2_NH~Riii NH,~WRiv NH2
M N*
wherein M, N* and Q may be hydrogen, lower alkyl, and lower
alkyl ether or thio ether groups, w is an integer that is one
of 0, 1, 2, 3, 4, 5, and 6; y and z being one of 1, 2, 3 and
4; Riii and RiV are the same or different and are chosen from
the group consisting of normal and branched alkyl radicals,
alkyl ether or thio ether radicals, and substituted and unsub-
stituted aromatic and alicyclic radicals; x is a positive
number greater than 1 and R is an intervening polyvalent
organic radical. The teachings of the specification indicate
that benzyl or phenyl alkylene amines are intended by including
aromatic moieties among the possible identities of Riii and
RiV. In this patent, also, introduction of the amine terminals
is after the polysulfide condensation and any desired molecular
11~8~67
--4--
weight adjustments. It will be noted that the structure of
all the above suggested amine terminals is significantly
different from those of Applicant's instant invention. In
addition, it is noted that all the above compositions are
cured with epoxy type cures. As~the above compositions are
all alkyl amine terminated, they would not suggest themselves
as useful curing agents in the urethane art. While alkyl
amine compounds are useful catalysts in urethane cures, their
high reactivity and consequent short "pot life" renders them
generally not useful as urethane cure agents per se.
The reaction of liuqid thiol terminated polysulfide
polymers with isocyanates is well known. Australian Patent
1,475,115 and the publication Modification of Urethane Thermo
Elastomers by Polysulfide Polymers by Cherkasova et al in
lS Sintez i Fiziko-Khimiya Polimerov, Vol. 19, pages 72-76,
1976 are recent examples. Other patents concerning mercaptan
containing polyurethane compositions and curable liquid
polythiopolymercaptanpolyurethane polymers are U.S. Patents
3,446,780 and 3,440,273.
The present invention provides methods of producing
aryl amine terminated polysulfide polymers in either liquid
or solid form either by direct synthesis or by conversion of
a previously synthesized hydroxyl terminated high molecular
weight polysulfide polymer without requiring a separate
molecular weight adjustment step.
SUMMARY OF THE INVENTION
The invention provides in a composition aspect a compound
of the formula I:
(H2N) -Ar-S ( x)n (I)
wherein Y is -SH or Sx-Ar-(NH2)a; Ar is an a + 1 valent
radical derived by removal of a + 1 nuclear hydrogens from
a substituted or unsubstituted aryl moiety either carbocyclic
or heterocyclic and having 1 or 2 aromatic rings; R is a
hydrocarbon, oxahydrocarbon or thiahydrocarbon radical; a is
1~8167
--5--
1 or 2; n is about 4 to k x 103 wherein k is 1 to about 10;
and x is from about 1.8 to about 4.
The tangible embodiments of this composition aspect
of ~he invention possess the inherent applied use character-
istic of being curable or cross-linkable through the use of
poly valent compounds reactive with aryl amine functions such
as epoxy compounds, polybasic acid anhydrides and poly-
isocyanates or through a combination of these compounds and
conventional polysulfide curing agents to high molecular
weight solids having excellent resistance to oils and greases
and to hydrolysis. This evidences their usefulness in the
formation of films, cast or extruded objects and in the
formulation of sealants having high water and solvent
resistance.
Preferred embodiments of the compositions of formula I
are those wherein Ar is a xadical derived from benzene
or alkyl substituted benzene, a is 1 and n is about 4 to
about 23. Special mention is also made of those embodiments
of formula I wherein Y is -Sx-Ar-(NH2)a and of those embodi-
ments wherein Y is -SH most particularly in both cases wherein
n i9 4 to about 23.
The invention further provides a composition of the
formula II:
lo)
(CN-R'-NHC-NH)a~Ar~Sx~~~R-SX ~ R-Z
(II)
wherein Ar; R; a; n and x are as defined for formula I; Z is
O o
-S-C-NH-R'-NCO or -Sx-Ar-(NHCNH-R'-NCO)aand R' is a polyvalent
aliphatic, aromatic, or aliphatic aromatic radical or when
1O,
taken together with the -CNH- and -NCO moieties is the residue
of an isocyanate terminated polyurethane prepolymer.
.
~.
~14~3167
--6--
The compositions of this aspect of the invention
possess the inherent applied use characteristic of being
curable with standard Zerewitinoff active hydrogen contain-
ing polyurethane prepolymer curing agents thereby evidencing
the;r usefulness in preparing filmsj cast and extruded
objects and in formulating sealants having high water and
solvent resistance.
The invention also provides compositions of formula III:
O O
,, ..
HS-R-~~~Sx~R )nSx~R~Sx- Ar-NH-C-NH-R'-NHC-INH
Ar
I
HS-R (SX-R )mSx- R- Sx
(III)
wherein Ar; R; R'; n and x are as defined for formulas I and
II and m is about 4 to about k x 103 wherein k is 1 to about
10 .
The tangible embodiments of this composition aspect of
the invention possess the inherent applied use characteris-
tics of being curable to solids by standard polysulfide poly-
mer oxidative cure agents thereby evidencing their usefulness
in forming films, cast and extruded objects as well as in
the formulation of sealants.
The invention also provides in a composition aspect
an article of manufacture which comprises a cured object
comprising the reaction products of a polyurethane prepolymer
curing agent and a compound of formula I or a compound of
formula II.
The invention also provides a process for the prepara-
tion of a compound of formula I which comprises treating a
compound of the formula IV:
(02N) a-Ar-Hal
(IV)
11~8167
--7--
wherein Hal is Cl, Br or I; and Ar and a are as defined for
formula I; together with a compound of the formula V:
Hal-R-Hal
~V)
wherein R is as defined for formula I and Hal is as defined
for formula IV; with sodium polysulfide in a substantially
aqueous medium to produce a compound of formula I wherein
Y is -Sx-Ar-(NH2)a. If a compound of formula I wherein Y
is -SH is desired, the product of formula I wherein Y is
Sx-Ar-(NH2)a so formed may be treated either with SH
in the presence of SO3 or with a conventional thiol
terminated liquid polysulfide polymer.
The invention also provides a process for the prepara-
tion of a compound of formula I which comprises treating a
compound of the formula V with sodium polysulfide in a substan-
tially aqueous medium to prepare compound of formula VI:
HO-RtSX-R~n, SX-R-OH
(VI)
wherein n' is sufficient to give molecular weight values of
from about 1 x 104 to k x 105 wherein k is 1 to about 10;
and R and x are as defined for formula I hereinabove; and
treating a compound of formula VI so produced with a com-
pound of formula VII:
(H2N)a-Ar-S-S-Ar(NH2)a
(VII)
wherein Ar and a are as defined for formula I hereinabove.
The invention also provides in a process aspect a
process for the preparation of compounds of formula II which
comrpises treating a compound of formula I with a compound
of formula VIII:
OCN-R'-NCO
(VIII)
wherein R' is as defined for formula II.
1~ 48167
--8--
The invention also provides a process for the preparation
of compounds of formula III which comrpises treating a compound
of the formula I wherein y is a thiol terminal with the correct
stoichiometric amount of a compound of formula VIII.
- The invention also provides a curable composition which
comrpises a compound of formula VIII and compound of formula I
wherein Y is -Sx-Ar-(NH2)a.
The invention also provides a curable composiiton which
comprises a compound of formula II and a poly (Zerewitinoff
active hydrogen containing) organic compound.
The invention also provides a cured elastomer which
comprises the reaction product of a compound of formula I and
a compound of formula VIII.
The invention also provides a cured elastomeric product
which comprises the reaction product of a compound of formula
II and an organic compound having a plurality of Zerewitinoff
active hydrogens.
The invention also provides a cured elastomer which
comprises the reaction products of a compound of formula III
and a known polysulfide polymer oxidative curing agent.
The invention also provides a curable composition which
comprises a compound of formula III and a conventional poly-
sulfide polymer oxidative curing agent.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The manner of making and using the compositions of the
invention will now be described with reference to specific
embodiments thereof, namely, a liquid aminophenyl terminated
polysulfide polymer based on bis-(2-chloroethyl) formal, having
an average sulfur linkage rank of 2.25 and an average molecular
weight exclusive of arylamine terminals of about 2000 (IX), a
compound of formula I wherein Y is -Sx-Ar-(NH2)a; a liquid
thiol terminated polysulfide urethane block copolymer (X) of
the formula:
8~67
CH3
HS (R''-Sx, ~ R'-Sx, ~ ~ ~ _ _
-S ,-R" (Sx,-R"~kSH
(X)
wherein x' is about 2.25; j and k together are sufficient to
give the polysulfide portion of the molecule outside the
bracketed portion a molecular weight of about 4000; bonding
to the tolylene moiety is at the 2, 4 or 2, 6 position; and
R" is -CH2CH2-OCH2O-CH2CH2-, a compound of formula III; and
a compound of the formula XI:
~H 3 o , CH3
OCN{~NHCNI~--Sx I ~R -SX I tlR SX~ NHCNH{~3}NCo
(XI)
wherein x' is about 2.25; 1 is sufficient to give an average
weight of about 2000 atomic weight units to the molecular
backbone portion between the terminal units which commence
with the phenylene moieties; bonding to the tolylene moieties
is at the 2, 4 or 2, 6 positions; and R" is -CH2CH2-OCH2O-CH2CH2-,
a compound of formula II.
To prepare IX, bis-(2-chloroethyl) formal may be treated
with sodium polysulfide at elevated temperatures, conveniently
from slightly above room temperature to about 90C, preferably
about 85C, in a polar solvent, conveniently water, in the
presence of strong base, conveniently sodium hydroxide, and
in the presence of sufficient soluble magnesium salt to precipi-
tate magnesium hydroxide for nucleating curd formation in the
- polysulfide latex and an alkyl aryl sulfonate dispersing agent,
over a short period of time, conveniently about one hour, to
form a latex. The latex so formed may then be coagulated and
solids separated from the liquid reaciton medium by settling
and decantation of the supernatant liquid. The solid residue
may be then washed with portions of water until free of sulfide
reaction with lead acetate test paper. The washed latex sus-
'` '' ' ' ' - ,
~1~8~7
--10--
pended in a suitable reaction medium, conveniently water, may
be treated with diamino diphenyl disulfide (VIIa), conveniently
with the aid of a miscible solvent in which the diamino diphenyl
disulfide is dissolved, such as methanol, and addition of such
solution to the latex suspension at temperatures which may vary
from room temperature to about 80C during the mixing process
and then, conventiently, at about 80C, although one skilled
in the art will recognize that the exact temperature is not
particularly critical, until a sample of the reaction mixture
shows the separation of a second liquid phase with no residual
solid upon acidification, conveniently with acetic acid. If
desired, the aryl amine terminated polymer (IX) may be treated
with a stoichiometric quantity of toluene diisocyanate (VIIIa),
that is, 1 isocyanate to l amine to prepare a high molecular
weight chain extended polymer which may then be split at the
disulfide linkages in the usual fashion by treatment with NaSH
and Na2SO3 to prepare X. If desired, X may also be prepared
starting from a liquid thiol terminated polysulfide polymer
(XII) having the dichloroethyl formal based backbone. XII may
be treated with (VIIa) in a fashion s$milar to that described
for the preparation of IX, conveniently in this instance, the
ratio of diamino diphenyl disulfide to thiol groups wiil be
l:2, although it may be greater whole number multiples, if
lower molecular weight fragments are desired. The resultant
product of this treatment (XIII) will be a compound of formula
I wherein Y is SH. XIII may be treated with VIIIa at a 1:1
isocyanate to amine ratio to prepare X.
To prepare XI, IX may be treated with VIIIa at about a
2:1 isocyanate to amine group ratio. The reactions herein,
unless otherwise specified, may be performed neat or in the
presence of suitable inert solvents or suspending agents for
one or more of the reactants. The temperature in most cases
is also not especially critical and unless otherwise specified,
they may be performed at room temperature or at temperatures
slightly elevated above that point. In most illustrative
~ . , . - .. . . . .. .
~148167
examples, it will be understood that solvents, temperatures
and reaction times are illustrative and that their variation
wiLl be well within the skilI of the ordinary chemist.
One-of skill in the art will also recognize that in addition
to the diamino diphenyl disulfide illustrated for the prepara-
tion of IX and the various reaction products thereof, one
may substitute other amino substituted diaryl disulfides and
obtain analogous compounds of formula I. These compounds
obviously may then be converted by processes analogous to those
described herein to prepare compounds of formula II or III.
Similarly, one skilled in the art will recognize that in the
reaction of initially formed high molecular weight polysulfide
polymer with diamino diphenyl disulfide varying the relative
proportions of diamino diphenyl disulfide, or, for that matter,
any of the diaryl amino disulfides to that of the polysulfide
polymer, will permit control of the molecular weight of the
aryl amine terminated polysulfide polymer so produced.
It will also be obvious to one of skill in the art that
in addition to the toluene diisocyanate VIIIa illustrated
for the preparation of compounds X and XI, other monomeric
isocyanates or polyurethane prepolymers having at least 2 free
isocyanate functionalities may be employed to prepare analogous
compound formulas II and III.
Similarly, it will be obvious that compounds of formula
O
II wherein Z is -S-CNH-R'NCO may be prepared by treating
compounds of formula I wherein Y is SH with a suitable diiso-
cyanate with a proportion of about 2-NCO groups to the total
-NH2 and -SH group content.
An alternative synthesis of compounds of formula I wherein
Y is -Sx-Ar~NH2)a is to introduce a compound of the formula IV
in a standard polysulfide polymer synthesis. It is readily
apparent that IV will act as a chain stopper. Surprisingly
:
~1~8~G7
-12-
the excess inorganic polysulfide always present in such
synthesis as it is required to attain high molecular weight
appears to serve as a reductant to the nitro chain terminals,
reducing them to amino groups. That reduction does not
occur prior to introduction of the residue of IV as a
chain terminal is further evidenced by the observati~n that
p-chloroaniline does not introduce aminophenyl terminals
if employed in analogous fashion to IV. Control of the ratio
of compound IV to compound V will obviously allow statis-
tical control of the molecular weight of the polymerformed. Obviously, in a variant of this synthesis, the
aryl amine terminated polysulfide polymer so formed may
be split with NaSH and Na2SO3, or their equivalents, to
produce compounds of formula I wherein Y is -SH.
One skilled in the art will also recognize that in
another variant of this synthesis; the aryl amine terminated
polymer so formed may be treated, conveniently at elevated
temperature, preferably, but not critically, at about
90C, with a conventional liquid thiol terminated polysulfide
polymer, conveniently of about the same average molecular
weight, to prepare compounds of Formula I wherein Y is -SH.
In the processes for the use of the compounds of the
invention, standard methods of compounding, if desired, and
of application and cure are contemplated. If desired,
sealant compositions, either 2 part using separately packaged
curing agents, or 1 part using blocked, dormant, sequestered
or encapsulated curing agents may be compounded employing
known fillers, plasticizers, adhesive additives, U.V.
stabilizers and the like. Application of the sealant to the
desired substrate may be by standard methods as by extrusion
from an applicator gun after mixing of the 2 part sealant
with curing agent or activation of cure agent if necessary
for the 1 part sealant. Or, if desired, the l'part sealant
cure may be activated after or during application as by
known heat and/or moisture cures. Cast or molded objects may
, . . .
. ~. .. ,; . .
~8167
-13-
obviously be formed by pouring or injecting the co~posi-
tion including any desired fillers, plasticizers or other
adjuvants and allowing cure to take place. Conventional
polysulfide and/or urethane processing techniques may be
employed to produce rigid or flexible foams as well as
rigid or elastomeric solids. Reaction injection molding
and linear injection molding as conventionally understood
are contemplated among the processes which may be employed.
Coated objects may also be prepared by standard techniques
as, for example, through the use of a roller coater, a
curtain coater or application by brush. The choice of
curing agent will obviously depend on the nature of the
terminal groups. NH2 and SH terminated polymers may be
cured using polyfunctional compounds reactive with Zere-
witinoff active hydrogen, such as epoxy compounds, poly-
isocyanates, poly basic acids or poly basic acid anhydrides or
poly basic aryl halides and the like, polymers with isocyanate
functionality will obviously be curable with standard poly-
urethane prepolymer cures employing commonly polyols and/or
polyamines with or without catalysis. Polymers with -SH
terminals may be cured employing standard oxidative poly-
sulfide polymer cure systems as, for example, PbO2 or
Zn2 and the like.
As used herein and the appended claims unless the
context clearly requires otherwise the term substituted
or unsubstituted aryl moiety carbocyclic and having l or 2
aromatic rings contemplates aromatic nucleii containing
compounds such as benzene, naphthalene, indene, diphenyl,
acenaphthene, fluorene either unsubstituted or substituted
with such substituents as alkyl, alkenyl, alkynyl, aralkyl,
aralkenyl, aralkynyl, fluorinechlorine, bromine, acyl,
alkylcarbonylalkyl, which may be exemplified by toluene,
methylnaphthalene, dibenzyl, stilbene, indane, ethyl benzene,
acetophenone, benzophenone, cumene, cyclohexylbenzene,
styrene, diphenylmethane, chlorobenzene and the like.
The term subsituted or unsubstituted aryl moiety hetero-
~'
1141~1fà7
cyclic and having one or two aromatic rings contemplatesaromatic nucleii containing heterocyclic compounds 6uch as
pyridine, quinoline, isoquinoline, indole, thiophene,
furan, pyrrole, thiazole, oxazole, pyrazole; imidazole,
benzimidazole, triazole, triazine, thiophthene, thia-
napththene, benzofuran, indazole, pyridazine, pyrimidine,
pyrazine, cinnoline, phthalazine, quinazoline, quinoxaline,
chroman, coumarone either unsubstituted or substituted with
such substitutents as alkyl, alkenyl, alkynyl, aralkyl,
aralkenyl, aralkynyl, fluorine, chlorine, bromine, acyl,
alkylcarbonylalkyl, or carbonyl which may be exemplified by
acetothiophene, dimethylpyrrole, dimethyloxazole, picoline,
stilbazole, lepidine, furfural, ethyltriazine and the like.
The term hydrocarbon, oxahydrocarbon or thiahydrocarbon
radicals as set forth for compounds of formulas I, II, III,
V, and VI contemplates those well known in the literature
as suitable for the preparation of polysulfide polymers.
U.S. Patents 1,890,191 and 2,014,166 sets forth numerous
examples of the type of bifunctional organic compounds
which m~y be employed to provide these radicals in a
typical polysulfide polymer reaction process. The term
polyvalent aliphatic, aromatic, or aliphatic aromatic
radical as set forth for compounds of formula II, III and
VIII contemplates those at least difunction radicals
commonly understood to be employed in low molecular weight
organic polyisocyanates. Illustrative of these polyisocyanates
and hence of R' are: isophorone diisocyanate, l-methoxyphenyl-2,
4-diisocyanate, 1-methyl-4-methoxyphenyl-2,5-diisocyanate,
l-ethoxyphenyl-2,4-diisocyanate, 1,3-dimethoxyphenyl-4,6-
diisocyanate, 1,4-dimethoxyphenyl-2,5-diisocyanate,
l-propoxyphenyl-2,4-diisocyanate, 1-isobutoxy-2,4-
diisocyanate, 1,4-diethoxyphenyl-2,5-diisocyanate
toluene-2,4-diisocyanate, toluene-2,6-diisocyanate,
diphenylether-2,4-diisocyanate, naphthalene-1,4-diisocyanate,
`'~ .Ji
~81~7
-15-
1,1'-dinaphthalene-2,2'-diisocyanate, biphenyl-2,4-
diisocyanate 3,3'-dimethylbiphenyl-4,4'-diisocyanate,
3,3'-dimethoxybiphenyl-4,4'-diisocyanate, diphenylmethane-
4,4~-diisocyanate, diphenylmethane-2,4'-diisocyanate, di-
phenylmethane-2,2'-diisocyanate, 3,3'-dimethoxy diphenyl-
methane-4,4'-diisocyanate, benzophenone-3,3'-diisocyanate,
ethylene diisocyanate, propylene diisocyanate, butylene
diisocyanate, pentylene diisocyanate, methylbutylene
diisocyanate, tetramethylene diisocyanate, pentamethylene di-
isocyanate, hexamethylene diisocyanate, dipropyl diisocyanateether, heptamethylene diisocyanate, 2,2-dimethylpentylene
diisocyanate, 3-methoxy-hexamethylene diisocyanate,
octamethylene diisocyanate, 2,2,4-triemthylpentylene
diisocyanate, 3-butoxyhexamethylene diisocyanate, 1,3-
dimethylbenzene diisocyanate, 1,4-dimethylbenzene diiso-
cyanate, 1,2-dimethylcyclohexane diisocyanate, 1,4-
dimethylcyclohexane diisocyanate, 1,4-diethylbenzene
diisocyanate, 1,4-dimethylnaphthalene diisocyanate,
1,5-dimethylnaphthalene diisocyanate, cyclohexane-1,3-
diisocyanate, cyclohexane-1.4-diisocyanate, l-methyl-
cyclohexane-2,4-diisocyanate, l-methylcyclohexane,
2.2-diisocyanate, 1-ethylcyclohexane-2,4-diisocyanate,
dicyclohexylmethane-4,4'-diisocyanate, dicyclohexyl-
methylmethane-4,4'-diisocyanate, dicyclohexyldimethyl-
methane-4,4'-diisocyanate, 2,2-dimethyldicyclohexyl-
methane-4,4'-diisocyanate, 3,3',5,5'-tetramethyldicyclohexyl-
methane-4,4'-diisocyanate,4,4'-methylenebis (cyclohexyliso-
cyanate), ethylidene diisocyanate, 4,4'-diphenyl diisocyanate,
- dianisidine diisocyanate, 1,5-naphthalene diisocyanate,
m-phenylene diisocyanate, isopropylidene bis(phenyl
or cyclohexyl isocyanate), 1,3-cyclopentylene diisocyanate,
1,2-cyclohexylene diisocyanate, 1,4-cyclohexylene diiso-
cyanate, 4,4',4"-triphenylmethane triisocyanate, 1,3,5-
.
~'
.. . . ~ ~ . . , . ... . , ,. , ~ .
~48~L67
-16-
trisocyanatobenzene, phenylethylene diisocyanate, l-
chlorophenyl-2,4-diisocyanate, l-nitrophenyl-2,4-diisocyanate,
1,3-dichlorophenyl-4,6-diisocyanate, 1,4-dichlorophenyl-
2,5-diisocyanate, l-chloro-4-methoxyphenyl-2,5-diisocyanate,
3,~ -dichlorodiphenyldimethylmethane-4,4'-diisocyanate,
3-nitrotriphenylmethane-4,4'-diisocyanate, pyrene-3,8-
diisocyanate,chrysene-2,8-diisocyanate, and the like.
The starting materials for the practice of the
invention are commerically available, well known in the
chemical literature or easily synthesized by methods well
known to one skilled in the art of chemistry.
One skilled in the art would also recognize that, in
addition to compounds of the general the formula VII illustrated
hereinabove for the practice of the inventions, one may
employ compounds capable of generating equivalent chemical
structures which may conveniently be illustrated as
[(H2N)a-Ar-S] under the conditions of the processes
of the invention. Benzothiazole is typical of this
class of compound, although many others will be readily
apparent to a skilled organic chemist. As used herein
and in the appended claims, compounds of the general formula
VII comprehend the use of such compounds capable of gen-
erating equivalent structures as precursors in the processes
of the invention.
The following examples further illustrate the best
mode contemplated by the inventor for the practice of his
invention.
,~
. .. .
~1481~7
-17-
EXAMPLE I
Preparation of Polysulfide Polymer Latex With
~ Sulfur_Rank of about 2.25
Neutral sodium polysulfide solution (2.43 molar,
2139.~ ml, 5.2 moles), sodium hydroxide solution (50% wt/wt,
25.6g, 0.32 mole) and Nekal~ BK (alkyl sulfonate, 5% aqueous
solution, 20.0g) are heated to about 85C under a nitrogen
atmosphere. Aqueous magnesium chloride (25% MgC12'6H2O, 0.16
mole, 130g) is added and bis-(2-chloroethyl) formal (720.0g,
4.0 moles) is added over a period of 1 hour while the temper-
ature is held at about 84C to about 87C after which the
mixutre is held at about 100C for an additional hour while
the N2 blanket is maintained. The reaction mixture is then
allowed to cool to room temperature, and the solids permitted
to settle. After decantation of the supernatant liquid,
the solids are washed by decantation until the wash water
gives a negative lead acetate test to give the title
product 668 grams. A dried filter cake of the latex gives
the following results:
Analysis for Sulfur = 38.76%
Sulfur Rank = 2.16
ASTM D2240 Hardness (Shore A) = 27 reaching 20
in 2 seconds
~8~67
-18-
EXAMPLE 2
Reaction of Polysulfide Polymer Latex of ~xample 1
_ with Diaminodiphenyl Disulfide and Subsequent
Reaction with Toluene Diisocyanate
A. To the latex product of Example 1 (36.1% Solids,
277.0g [lOOg dry]) is added 6.23g diamino diphenyl disulfide
as a powder. The mixture is heated under nitrogen at about
95C for about 7 hours, allowed to stand overnight at room
temperature and then treated for an additional 8 hours at
about 95C, then allowed to cool and stand at room temp-
erature for about 72 hours. An aliquot sample is taken and
made acid by addition of acetic acid. A second liquid phase
separates indicating that splitting of the high molecular
weight polymer chains has occurred. Toluene diisocyanate
(4.36g) is added to the reaction mixture and the reaction
allowed to proceed 4 hours at room temperature. During this
time an exotherm from 23 to 26.5C occurs. Acidification
of a sample produces a crumb-like solid precipitate indicating
reaction back to a high molecular weight polymer. Durometer
readings on solid material are variable but over 60 Shore A.
B. To the product latex from Example 1 (36.1% Solids,
277.0g [lOO.Og dry]? is added diamino diphenyl disulfide
(6.23g) in toluene (50g). The mixture is heated under a
nitrogen blanket at about 78C for about 6 hours, allowed to
cool and stand at room temperature overnight, heated for an
additional 8 hours at about 80C, allowed to cool and sampled.
Acidification of the sample with acetic acid causes separation
of a second liquid phase indicating that the original high
molecular weight polymer has been split to a lower molecular
weight. Toluene diisocyanate (Hylene~ TM, Du Pont) is added
to the remaining reaction mixture. Reaction is allowed to
proceed for about 4 hours. During this time, a slow exotherm
from 24C to 26C occurs. Acidification of a sample gives
a solid crumb precipitate indicating chain extension to a high
molecular weight. After removing the majority of toluene
( ~ 8167
- --19--
by distillation and washing the solid latex with water, a
durometer reading is made on a cake held at lOO~C overniqht.
The cake.has a ~hore A hardness of 55 drop~iny to 50 in 2
seconds.
.''-' " '', '' '' ''''' '' .
,
.
.. . .
.~. .. .
r ~ . .
~,, ' . ' .
~ ' . ~ .
~ .
,
.. . .
~, . . . .
'. .
.. . . . . .
.`' '';
1148167
-20-
EXAMPLE 3
Preparation of and Splitting of Polysulfide Latex with
- Diamino Diphenyl Disulfide and Reaction of the Low
- Molecular Wei ht Product with Toluene Diisocyanate
g
Following a procedure analogous to that of Example 1
but adding additional free sulfur to adjust the rank of the
starting polysulfide solution to 2.25, there is prepared a
rank 2.14 polysulfide latex which is held at 100C to "toughen"
the polymer. The durometer hardness of a sample prepared
from the latex is 50 Shore A.
To this latex (33.6% Solids, 2381g [800g dry]) there is
added diaminophenyl disulfide (49.84g, 1 mole per 22 segment
weights of polymer so as to split to average 4000 M. Wt. seg-
ments) in absolute methanol (720g) over a 32 minute period
during which time the reaction mixture is heated from an ini-
tial 25C up to reflux temperature. The reaction is held at
reflux for about 4 hours, allowed to cool and settle and the
residue washed with water 5 times by decantation. A sample
(115.05g dry) is washed 10 additional times by the same tech-
nique, then treated with toluene diisocyanate (4.66g). After
4 hours, hardness on a sample of the reaction is 68 (Shore A).
The remaining latex from the diamino diphenyl disulfide re-
action is acidified with acetic acid and washed to about
neutrality. The product obtained is a liquid (719.2g) viscosity =
2220.0 poises.
.
~L48~67
-21-
EXAMPLE 4
Preparation of Rank 2.25 Latex, Stripping to Rank 2.0
_ Followed by Conversion to Amine Terminated Liquid Polymer
- Following a procedure analogous to that of Examples 1
and 3, a 2.18 rank polysulfide latex is prepared from Na2S
2.25 ~4.2 moles) Na2S (2.3 moles) Sulfur (2.9 moles) and bis
(dichloroethyl) formal (5.0 moles) and washed free of sulfide
ion to lead acetate. To the latex at 85C is added 200g Na2SO3
and the mixture is held at 85C for 1 hour. The stripped
latex is then washed by decantation. The sulfur rank found
is 1.90. Hardness of cakes prepared from the latex both
before and after stripping is 50 Shore A. The latex itself
is 33.6% solids.
To the latex (2244.0g, 754.0g dry) is added diamino
diphenyl disulfide (47.0g) in methanol (679g) over a period
of 30 minutes while the reaction mixture is being warmed to
reflux. Reflux is maintained for 4 hours. At the end of
this time, the reaction mixture is allowed to cool and is divided
into 2 portions. The first portion, part A, is washed
twice by decantation then acidified with acetic acid. The
lower layer organic phase which separates is washed 10 times
with about equal volume portions of water. Following washing
the organic phase is heated in a rotary evaporator at about
85C until a constant 1-2mm Hg vacuum is reached. Viscosity =
2300 poises at 25C, %N = 0.44% 500g removed from the original
stripped latex, part B, is wahsed 10 times by decantation with
approximately equal volumes of water. Dry solids at this
point = 127.7g.
The washed latex is treated at 23 to 26C with 5.2g
toluene diisocyanate. Hardness of a sample "cake" from the
reaction is 70 Shore "A". % Sulfur found is 34.33~.
`' ' ' ' ' `
~148167
-22-
EXAMPLE 5
Introduction of Aryl Amine Terminals Simultaneously
With Polysulfide Polymer Synthesis
To a mixture of Na2S 9H2O (1372.8g), sulfur (228.6g) and
water (llOg) which has been warmed to 75C and held at that
temperature for about 1/2 hour under a nitrogen blanket is
added NaOH (50% w/w in water, 25.6g) and a sodium alkyl
sulfonate (Neka ~BX, 20.0g) after which the mixture is
warmed to 85C and MgC12 6H2O (130.lg) and _-chloronitro-
benzene (54.2g) are added. A slight warming to 95C occurs.
When the reaction mixutre has again been stabilized at 85C
bis-(2 chloroethyl) formal (720.0g) is added over a period of
one hour. After all the formal has been added the reaction
is held at 100C for 7 hours while sampling every hour including
0 time for 3 hours then at 5 and 7 hours. Each sample
and the final batch of latex is washed clean of sulfide (lead
acetate test) a portion of the final washed latex is reserved
for reaction with toluene diisocyanate. Each sample and
the remainder of the main batch of latex are acidified with
50% aqueous acetic acid then washed free of acid by decanta-
tion and dried under vacuum. Viscosity at ~5C = 4700 poise.
The portion of the latex reserved for reaction with
toluene diisocyanate (60.7g dry solids) is treated with toluene
diisocyanate (2.4g) for 4 hours at about 22 to 24C. A
durometer hardness cake is then prepared and dried overnight
at 70C. A solid tough rubber is obtained of 60 Shore A
hardness. ~ Sulfur = 35.5%.
The washed liquid polymer (20.0g) from the major portion
of the latex is treated with toluene diisocyanate (0.824g) at
room temperature then the mixture is divided into 2 parts.
1 part is cured at room temperature (23C), the other is held
at 100C. The room temperature sample is soft cured at 1 hour
with a durometer of 35 Shore A falling to 26 in 2 seconds
after 24 hours and 52 Shore A falling to 47 after 7 days at
,
,, .~
.. . . . . . .
~148~67
-23-
room temperature. After 16 hours a~ 100C that sample has
a hardness of 67 Shore A.
Analysis of the reaction samples gives the following
results.
Time %C %H %N ~Amine N
0 hr. 36.52 5.86 0.37 0.34
1 hr. 36.53 5.78 0.37 0.38
2 hrs. 36.78 5.79 0.37 0.45
3 hrs. 36.40 5.67 0.41 0.41
5 hrs. 36.17 5.79 0.35 0.42
7 hrs. -- -- 0.62 0.50
(Final)
.
: .
, .
~'-, .' ' '' ' .
.
. ' ' .
, : , .
., ' .
.
.
.
1148~67
-24-
EXAMPLE 6
Reaction of Amino Terminated Polysulfide Polymer
With Liquid Epoxy Polymer
The amine terminated liquid polymer of Example 3 is
treated with the proportions by weight of Epoxy polymer (Epon~
828, Shell Chemical Co.) at the temperatures indicated for
the time indicated or until cure is obtained.
Ratio Amine Term Cured Hardness
Polymer to Epon 828 Temp. Time to Cure (Shore A)
2/1 23C None in 10 days --
2/1 70C None in 10 days --
2/1 100C 54 to 70 hours soft, slightly
tacky
2/1 150C partial 6-1/2 hrs. ~60
full 7 hrs.
4/1 23C None in 10 days --
4/1 70C Cure in 22 days --
4/1 100C 48 hours 10
4/1 150C 6-1/4 hours 42
.. . . .
~48167
-25-
EXAMPLE 7
Cure of Amine Terminated Polysulfide Polymer with
An Isocyanate Endcapped Polyether
Two portions of the amine terminated polymer from Example
3 (56.0g, 0.01 mole) are treated with portions of an iso-
cyanate (toluene diisocyanate) endcapped poly(propylene glycol)
(3.485% NCO, 2410 Mol.Wt.) (24.1g, 0.01 mole) at 100C and
150C. At 150C cure Qf the major portion to a solid occurs
within 1 hour some residual liquid polymer remains on surface.
Treatment at 150C overnight gives a dark brown, soft, tacky
material with an H2S odor.
At 100C cure is obtained between 4 and 19 hours to a
solid with a tacky surface and a hardness of about 35 Shore A.
1~48167
-26-
EXAMPLE 8
Aryl Amine Terminated Liquid Polysulfide Polymers
of about 4000 M.Wt. by Direct Synthesis
To s ~ um polysulfide (Na2S2 25) (1.94 molar, 1608.0 mls,
3.02 moles) and Nekal~ BX (20.0g) at 85C under nitrogen is
added MgC12 6H2O (0.12 moles, 98.1g) and _-chloronitrobenzene
(0.345 moles, 54.5g). The reaction mixture is cooled to 85C
and bis-(2-chloroethyl) formal (2.0 moles, 360.0g) is added
over a 1 hour period while the temperature is maintained at
85-90C. After all the bis-(2-chloroethyl) formal has been
added, the reaction mixture is warmed to 100C and held at
that temperature for about 6 hours. After cooling, the latex
is allowed to settle and the precipitate is washed 6 times
with about 2 liter portions of fresh water by decantation.
The wash water on the 5th wash is acidified with 50% acetic
acid to a pH of between 5 and 6. After washing, the pre-
cipitate is dried on a rotary evaporator at 0.25mm Hg and
90C max temperature to give a liquid residue 360.4g,
viscosity 1512.0 poises, N ~as amine N) = 0.78% - M.Wt.
4102.6. N (by nicro analysis) = 0.83%, S= 37.83%.
41.03g residue is treated with 1.74g toluene diisocyanate.
A solid is obtained in 25 minutes at room temperature.
Hardness = 75 Shore A. After 8 days - 80 Shore A.
~.`,.~
. .
8~67
-2~-
. .
EXAMPLE 9
.. Preparation of about 1,000 MoleculaF Weight ~mine
. Terminated Polysulfide Polymer by Direct.Synthesis
Following a.procedure analogous to that of Example 8,there i5 obtained from 1928.0 ml of 1.94 molar Na2S2 25
409.0g of the title product às a liquid residue viscosity
450.0 poises
N as amine N = 1.79~ . -
N total = 1.83~ .
Sulfur = 37.43%
Toluene diisocyanate (3.5g) and the residue (35.8g)
are mixed. The mixture becomes warm and cures in about
6 minutes. Hardness after 24 hours at room temperature =
90 5hore.A.
.
.
, . . . ' ' "
.
.: , .
. .
.
, . . . . . .
~ , , - , . .
,~ .
.
.. . .
. . . . . .
.
~148167
-28-
EXAMPLE 10
Preparation of an Aryl Amine Terminated Liquid
Polymer of about 3000 Molecular Weight Followed
by Cleavage to Lower Molecular Weight Polymer
Having Both Thiol and Aryl Amine Terminals
To Na2S2 25 solution (1.94 molar, 2.93 moles, 1510 ml)
and Neka BX (20.0g) heated to 85C under N2 is added
MgC12-6H2O (92.1g) and _-chloronitrobenzene (35.2g) followed
by bis-(2-chloroethyl) formal (360.0g) over a period of about
1 hour. After heating at 100C for 6 hours the reaction is
allowed to cool and washed by decantation until a negative
lead acetate sulfide test is obtained from the wash water.
To the washed latex (20-25% solids) is then added NaSH (8.0g)
and Na2SO3 150.0g and the mixture warmed to 85C for about
1.5 hours. NaHSO3 (50g) is then added to bring the pH of the
mixture to about 7 and the mixture is heated a further 0.5
hour. The reaction is then allowed to cool and settle. The
precipitate is washed by decantation until the wash water is
free of SO3 by iodine test and then acidified with acetic
acid to about pH 5. The residue which separates as a lower
layer is partitioned from the aqueous layer and dried in a
rotary evaporator at 90C and 0 5mm Hg 302.0g, viscosity
420.0 poises.
Amine nitrogen = 0.52%
Total nitrogen = 0.54
Sulfur = 34.70%
SH = 1.49%
Sulfur rank = 1.81%
Treatment of this residue with PbO2 powder in fashion
sufficient to cure usual all thiol terminated liquid poly-
sulfide polymers does not effect cure. A mixture of residue
(30.8g) and toluene diisocyanate (0.87g) warms slightly when
mixed at room temperature but does not cure to a s~lid in
one hour.
.. .
r `
8~67
--29--
A mixture of residue (30.8g), toluene diisocyanate
(0.87g) and PbO2 powder (2.0g) warms slightly and cures to
a solid in 18 minutes. Hardness after 2 hours at room temp-
erature is 25 Shore.A with flow. Hardness after 8 days at
room temperature is 60 Shore A with slight flow.
.
" ' ' ' ' ' , ' , '
' ' ' ~ .
"
.
~, . . . .
.' . " ' ' ' ' ,'
.:. . . .
.
~, . , , - , ,
.
$
.
11~8~6'7
-30-
EXAMPLE 11
Preparation of a Li~uid Polysulfide Polymer with
Hydroxyl Terminals, its Endcapping with Toluene
Diisocyanate and Use of the Isocyanate Capped
Prepolymer to Cure an Amine Terminated Polysulfide
Polymer
. .
A liquid thiol terminated polysulfide polymer based on
bis-(2-chloroethyl) formal with 2% crosslinking, of about
1000 molecular weight is dried for 1 hour at 91C and 0.2mm
Hg. After cooling to about 67C H2SO4 (l.Og) is added and
the mixture stirred for about one hour at a temperature range
of 62 to 80C. When the temperature of the mixture is at
62C toluene diisocyanate (Hylene~ TM 435.4g) is added. The
temperature is maintained at about 90 to 95C for about 5
hours. The product on cooling contains 8.01% NCO. It is
stored in closed containers under nitrogen.
The amine terminated polymer of Example 9 (14.9g) and
the above product (lO.Og) are mixed at room temperature.
Cure to a solid occurs in 8 minutes.
Hardness after 2 hours = 72 falling to 68 in 2 seconds.
After 3 days at room temperature hardness = 74 Shore A.
After 3 days in 100C oven, darkened, hardness = 78 Shore A.
` ~3
..,.. - ~
~; .
r~
8167
31 -
x~MrL~3 12
Aryl amine terminated liquid polymers prepared a~alocJou$1yto those described in Examples 9 and 10 with llle ~ all~ne6
shown are cured using a 1:1 NCO/amine ratio with P~1']~135
ta polymeric ~4 isocyanate phenyl] methane having a function-
S ality of about 2.7 and a molecular weight of 135 sold by -
Upjohn and Co.) using the quantities indicated to obtain
cured products within the time shown having the pro~ertles
shown:
Amine ter~inated polymer A 23.55g - -
(0.94% Amine)
.
Amine terminated polymer B - 21.79g
(2.03~ Amine)
Amine terminated polymer C - 20.5g
(3.24% Amine)
PAPI 135 2.0g 4.09 6.0g
Cure Time Rm. Temp. ~min.) 4.D 1.0 0.5
Hardness (Shore A)
3 hrs. Rm. Temp. 75 95 100
3 days Rm. Temp. 82 95 lOO
. . .
. ,
, ,
_. ' . .
:,-' ` ' : ' '
.~ . .
~, .
~, .
.~. . . .
. ~ . .
L6~7 i
~2~
EX~51~L~ 13
The aryl amine terminated polymers employed in Examplc
12 are treated at the temperature indicated with a toluene
diisocyanate endcapped polyethylene adipate prepolymer having
3.05~ NC0 using the quantities shown to obtain cu~ed products
with the properties shown:
.
Amine terminated
polymer A 123.6g - -
Amine terminated
polymer B - 57.2g
Amine terminated
polymer C - - 35.9g
Isocyanate terminated
prepolymer lOO.Og lOO.Og lOO.Og
Cure Time at Rm. Temp. -4 hrs. 1 hr. 10 min. 1 hr.
Cure Time at 70C 1 hr. 50min. 25 min. 25 min.
24 hour Shore ~ llardnes5
Rm. Temp. Cure 35 to 25 53 58
~2 sec) (sl tack) (sl tack)
70C Cure 55 55 62
'' ' '
.
.
,' , ' . ' , ' ,
,
,
,
.
,
.
6~7
. ~3
X~Ml7LE 14
Reaction of a Commercial Thiol Terminated Liquicl
Polysulfide Polymer Based on Bis-(2-chloroc~llyl)
' Formal Having About 4000 MolecUlar Weight, And About
, 2~ Crosslinking With 4,4'-diaminodiphenyl disulfide,
Reaction of Aryl Amine Thiol Terminated Polymer'With
Toluene Diisocyanate And Cure Of The'Resulting Thiol
Terminated'Urethane Polysulfide Polymer
The liquid polysulfide polymer (400.09) and ~,4'-dia-
' ' minodiphenyl disulfide (24.8g) are.warmed at 90 to 95C
.. ~nder N2 for about 4 hours. This material so formed when
treated with PbO2 gives a soft solid that reverts to liquid
overnight. After cooling, to a portion'of the reaction mix-
. ture (212.4g) is added toluene diisocyanate (8.71g), the
, ' temperature climbs from 25C to about 60C in 1 hour. ~p-
' ' plication of slight heat raises the temperature to about
~ . 77C. The reaction mixture becomes very viscuous a,nd gells
i 10 on cooling A portion cured with P,bO2 before complete gel-
i , lation gives a hardness ,of about 55 Shore A.
!1 . . . .
'h,
.. . . .
~ ' . : , ' ' ' .
.~, . . . . . . .
~'~'' ' ; ' ' , ' . ..
, . .
.. . .
~., ' . . ' .
'- ,
~` . ' ' ' ' ' ' ' '.
.
~, .
.~ .: . .
."`' , ' , .
t '
., . .
~1~8167
-34-
EXAMPLE 15
Preparation of Aryl Amine Thiol Terminated Liquid
Polysulfide Polymer From Diaminodiphenyl Disulfide
and 2% Crosslinked, 4000 Molecular Weight Bis-(2-
chloroethyl) Formal Thiol Terminated Polysulfide Polymer
4,4'-diaminodiphenyl disulfide (99.7g) and the thiol term-
inated polysulfide polymer (1600.0g) are warmed at 91 to 95C
for 4 hours under N2. The product obtained on cooling has
SH = 1.71%, N = 0.49%.
.. . . .
c '
~8~L67
-35-
~X~MPL~ 16
Reac tiOIl of Aryl Amine Thiol l'erminat(~d Li~uid
Polysulfide Polymer With hiquid Isocyanate
Terminated Po~yether Polymer
The aryl amine thiol terminated liquid polysulfide
polymer of Example 15 (849.6g) and a liquid polymer prepared
by endcapping a 2000 M.Wt. poly(propylene glycol) with tol~lcnc
diisocyanate (llylen ~T~l, Du Pont Co.) to a ~ al NC~) con~clll
of 3.43'~ (490.0g) are held at 85 to 95QC of 2.5 hours.
Upon cooling the product is a brown paste. Treatment of a
sample with PbO2 results in a solid having 45 Shore A hard-
ness in less then 15 minutes.
Analysis of the product:
NCO = 0.035%
5H = 1.09
S = 22.8%
.. . .
. .
.. . . .
, . .. . .
.~ .
--
. . ' .
~ . .
.
~ ' , ' . . . .
~ . . . . .
., ,
.
~ .
.. . .
167 '--
--iG- ~'
EX~lrLE 17
Preparation of Sealant Compositions from the Thiol
Termin'ated Urethane Polysulfide ~'olymer o Exam~le 16
Sealant compositions are prepared by b'lending the
ingredien'ts listed in the quantities shown in parts by
' weight. The work life and physical properties obtained
are also listed,.
Formulation No.
.
1 2 3 4 5 6 7 8 9
Polymer (Ex 16) 100 100 100 100 100 100 100 100 100
CaCO3 65 50 65 38 45 55 55 65'65
Regency #7 = (?) - - - 27 20 20 20 - ~
Flx 0012 = (?) 60 60 70 60 60 70 70 60 60
Silane A-1870.7 0.70.7 0.7 0.70.7 0.7 0.70.7
Tio2 10 10 10 10 10 10 10 1010
Thixcin GR 10 10 10 10 10 10 10 1010
PbO2(7j/Flx
0012 (6.5)/Pb 14 14 14 14 14 14 14 14, 14
Stearate (6.5) , '
Pb Stearate - - - - ' - - - 0.25 0.5
Toluene 5 - -, - - 5 _ 5 5
Work Life Mins 35 25 28 ~30 25 30 ' 45 70
Hardness Shore A
1 day 25 22 20 23 24 21 2221
7 days'32 30 25 31 32 30 3032
Vertical Sag(ins) 0 0 03/16 0 0
Tensile (psi? 75 80 90 80 80 70 80 80
,~ ,Elongation (%)
(Est.)400 800400 700 500 500 700700
' . ' , , .
,
.
.
t
~ .
;.'~ ' .
1~8167
-37-
EXAMPLE 18
Preparation of Aryl Amine Terminated Liquid Polymer
of About 4000 Molecular Weight followed by Disulfide-
Mercaptan Group Interchange Resulting in Polymer
Having both Thiol and Aryl Amine Terminals
A 100 grams of aryl amine liquid polymer made by the
process described in example 8 is mixed with 100 grams of
4000 molecular weight polysulfide liquid polymer with all
thiol terminals and having 0.5~ crosslinking. This results
in a homogeneous solution of one polymer in the other which
then is heated to 90C and is held at that temperature for
10 hours. This treatment results in an interchange of
terminal thiol groups with polysulfide groups along the
chain forming new polymeric molecules with an average of
one thiol terminal and one aryl amine terminal. About 200
grams of product is obtained.
When a sample of this product is treated with PbO2
the liquid polymer becomes more viscous but does not cure.
Analysis for thiol and aryl amine groups shows that practi-
cally no thiol groups are present and that the calculatedamount of aryl amine groups are still substantially present
as the only polymer terminals. When a stoichiometric
quantity of toluene diisocyanate is added corresponding
to the aryl amine groups the polymer solidifies to a
soft solid in about two hours at room temperature.
8~67
38-
EXAMPLE 19
.
Preparation of Amine Terminated Polysulfide Polymers
. ploying Benzothiazole as a Precur~or ~or the Terminals
Following a procedure analogous to that of Example 5theré is obtained from 1.30 moles of 2.0 molar aqueous
Na2S2 25 solution, 0.10 moles benzothiazole and l.0 mole
bis-~2-chloroethyl) formal (added at 95C to 100C) the
title product as a clear liquid havin~ about 1.4% nitr~e-
content and having an amino content closely corres~ondill~3
to the total nitrogen content.
,
,. . .
~' ' ' '
.
. .
.
,
~ , ' .
,~ " ,., .. .. .. .. ' !
