TLRPOLY~dBRS CONTAINING ESTEE AND AMIDL LINKAGES
_ __-_ __ ~__. ______ _._._____.
Background of the Invention
This invention pertains to lactam-polyol-polyacyl lactam or
lactam-polyol-acyl polylactam terpolymers and optionally -terpolymers
having up to 100% ester end group -termination and their process
of preparation.
Polyamides comprise a large class of polymers Iaaving a wide
range of properties. Iwlany polyamides have excellent combinations
of properties for particular applications. One important class of
polyamides are the polylactams prepared by the polymerization of
lactams such as caprolaetam and the like, folycaprolactam, more
commonly known as nylon 6, is the most widely used of the polylactams
because of its excellent mechanical and physical properties and its
low cost. Because of the many desirable properties of polylactams,
polylactams other than polycaprolactam have been used to a consi-
derable extant when nylon 6 is unsuited to some specific end use.
Idylon 12, manufactured from lauryllactam or 12-aminododecanoic acid,
is an example of such a polymer. The foregoing polymer is charac-
terized by lower water absorption and consequently better dimensional
stability and electrical properties than nylon 6. Nylon 12 is also
more flexible and lower melting than nylon 6.
For still other applications, a polyamide having a higher water
absorption coupled with a higher elasticity than nylon 6 would be
useful for a number of applications. Some nylon copolymers are known
to provide the characteristics just mentioned. polyamide-polyehter
copolymers are known to have a combination of properties making them
suitable for use as fibers, fabrics, films and molded articles. It
is also known that lactam-polyol~eopolymers can be prepared by the
base catalysis of lactams in the presence.of polyalkylene glycols
or other polymerizable polyol intermediates using .iswCy~,late
ini-tiatorso 'Phil method of polymerization yields a block copolymer
with a number of food progertl.es at a reasonable cost. One of the
principal d3.sadv~rntages of the polylactam-polyether copolymers
prepared by this method has been the poor heat~stability of the
ccspolymers .
I
~~
The present invention pertains to lactam-polyol-
polyacyl lactam or lactam-polyol-aryl polylactam terpolymers
having both ester linkages and amide linkages between the
monomeric segments of the terpolymer, and optionally, alcohol
modified or ester terminated end groups. The invention also
pertains to a process~for preparing 'the above polymers com-
prising reacting together a lactam monomer, a polyol, an acyl
polylactam or polyacyl lactam, and optionally an alcohol in
the presence of a base catalyst for the anhydrous polymeriza-
Lion of a lactam.
In a preferred embodiment of the present invention,
there is provided a terpolymer having both ester linkages and
amide linkages between monomeric segments comprised of lactam,
polyol, and a polyacyl lactam or acyl polylactam of the
formulas O ~ O
~~ N - A - R - A' - N C/
~y~ . .h \Y/ y
where A and A° are acyl group selected from
O S O O O
n n em a
- C -, - .C -, - S -, - S -, or - p -
n ,
Y is an alkylene i~xoup having at least three carbon atoms; R
is a hydrocarbon group; y is an integer equal to one or more,
and n is an in,tegex equal to zero or one; said terpolymers
being comprised of from at least 10% to about 90% by weight of
polyol segments, and optionally aid terpolymer having alcohol
modified, 0.1%. or more ester erminated end groups.
In ~ f~rt,hex preferred embodiment of the present
invention, there is provided a process fox preparing terpoly- w
~0 mere having both ester linkages and amide linkages between
monomeric segments comprising miacing together lactam monomer,
3 w
~.~ J~~.~
polyol, basic lactam polymerization catalyst, a polyacyl
lactam or acyl polylactam; of the formula
O
C N -. ~-I2 -A' .- C
~Y~ n ~y~
Y
where A and A' are ac~l groups selected from
O S O O
91 It 11 11
_ _ _ C or - or - P -
C _ S
-
~ s ,
e, ,
O
Y is an alkylene group having at least about three carbon
atoms, R is a hydrocarbon group and n 9.s an integer equal to
zero or one, y is an integer equal to one or more and option-
ally an alcohol and polymerizing said lactam, polyol, polyacyl
lactam or aryl polylactam, and optionally alcohol to form the
terpolymer comprised of at least 10~ to about 90% by weight
of poly'ol segments and optionally having 0.15 or more ester
end group texminationo
A still further preferred embodiment of this
invention provides a lactam-polyol-aryl polylactam block ter-
2d polymer having the general formula:
O
n O
~'~ n O
N- C-Y-NH x-X- NH-Y-C x, -- O-Z ~ z-O w
a O
C"'Y"NH X"-X'" NH-Y°C x, a , -I'T
wherein EO-Z)Z is a palymeric-moiety and Z is a hydrocarbon
30 or substituted hydrocarbon gr~up said group being alkylene,
arylene, alkyl~ne carbonyl, arylene carbonyl, and mixtures
thereof;
X is an acyl group selected from _C-, or -P-
3a _
Y is an alkylene or substituted alkylene having from about 3
to about 14 carbon atoms;
x, x', x " and x° " are integers and the total number of x's
equal to 2w+2; and
z and w are integers equal to one or more.
Tn a still further pref erred embodiment of the
present invention, there is provided a process for preparing
lactam-polyol acyl polylactam terpolymers having the general
formula:
to 0
,a
~o 0
\ 11 11
N C-YNH x X- NH X-C xo-(O-Z),Z -0 w
Y al
Q O ! ,G
11 la
C Y-~1H x" X-- NH Y-C xa"~T
~Y
Wherein (O-~)z is a polymeric moiety and ~ is a hydrocarbon or
substituted hydrocarbon group said group being alkylene,.
arylene, alkylene carbonyl, arylene carbonyl, and mixtures
20 thereof;
X is an aryl group selected from
o S O o
la rs n 1e
-C-~ -C-, -S-, Or -:P_
n 1
C
Y is an alkylene ar substituted alkylene having ~rom about 3
to about 14 caxbon atoms;
x; x', x'' and x'°' are integers and vthe total number of x°s
equal to 2w+2; and
z and w are integers equal to one or more; comprising mixing .
30 together lactam monomers polyol, basic lactam polymerization
catalyst,; and a polyacyl~lactam; and polymerizing the lactam,
polyol and acyl polylactam to form the block terpolymer.
A still further preferred embodiment of the present
invention provides a lactam-polyol-polyacyl lactam terpolymer
having the general formula:
000
0 0
~N- C Y N~ x A R A- NH Y-~X , -.EO-Z ) ~--0
w
Y p
C
o .O
-C Y~1H ~" A-R-A NH Y-C x,A N
~Y
wherein (O-Z)L is a polyol segment and Z is a Hydrocarbon or
substituted hydrocarbon group said group being alkylene,
i
arylene, alkylene carbonyl, arylene carbonyl, arid mixtures !
thereof;
A is a carbonyl group;
R is a divalent or polyvalent hydrocarbon group;
Y is an aikylene ax substituted alkylene having from about 3
to about lib carbon atoms ;
x, x', x°' and x'°° are integers and the total number of
x's
is equal to 2w-~2;
z and w are integers of equal to one or more;
and.saad lactam--polyal-polyacyl lactam block terpolymers are
comprised of at least about 1g to abaut 90 percent by weight
of palyol blocks.
In ~x still further preferred embodiment of the
present invention; there is provided a process for preparing
lactam-polyol-lactate block terpolymers having the general
formula:
- 3c
,,... ,~
O\C
O ~ O
- CC Y N A R A- NH Y-C , - ( O--°Ir ) -O
X X Z
Y
i
~ ~ ~.~
It 9t
C Y-i~lH Xm A R-~A NH Y-~ X,lo N
~Y
Wherein (O-Z)z is a polyol segment;
Z is a hydrocarbon or substituted.hydrocarbon group said
group being alkylene, arylene, alkylene carbonyl, arylene
carbonyl, and mixtures thereof;
A is a carbonyl group;
R is a divalent or polyvalent hydrocarbon graup;
Y is an alkylene or substituted alkylene having from about 3
to about 1~ carbon atoms;
x, x°, x " and x " ' are integers and the tptal number of x's
equal. to 2w-~2;
z and w are integers eq~xal to one or more;
and said lactam-polyol-polyacyl lactam block terpolymers are
20 comprised of at least abaut l8 to about 90 percent by weight
of polyol blocks; comprising mixing together lactam monomer,
polynl, basic lactam polymerization catalyst and a polyacyl
7.actam; and polymerizing the lactam, polyo3 and polyacyl
lactam to farm the block terpolymer:
Zn a still further preferred embodiment of the
present invention, theta is provided a l~ctam-polyol-polyacyl
lactam block terpolymer or a lactam-polyol-acyl polylactam
block terpolymer having a't least about,5% ester end group
termia2ation and the general formula:
~d
_.
O O
.. ..
E-- C Y N X A R n A°- NH 5t--C x,-(O-Z z-.~
.. or
- O~y-NH ..- A I2 A' ~NH Y-C~x", E
x C ~n
Wherein (0-Z)z is a polymeric moiety and Z is a hydrocarbon
or substituted hydrocarbon group said group being alkylene,
arylene, alkylene carbonyl, arylene carbonyl, and mixtures
thereof; A and A' are acyl groups selected from
O S O O
.. .. .. ..
-C-, -C-, -S-, or -P-;
n
O
R is a divalent hydrocarbon group;
n is an integer equal to zero or one; O
/'~
E is an imide group of the formula
N )
~Y~
or an ester group of the formula -O-R"
where the -O-R' is the residual of a monohydric functional
alcohol; .
5~ is an alkylene or substituted alkylene having from about 3
to about l4 carbon atoms;
R' is an aliphatic or subs~titut~d aliphatic hydroearban
wherein the ester group is attached to other than a cyclic
or aramatic radical;
x, x', x'' and x''° are integers and the total number of x°s
is equal to 2w+2; and z and w are integers equal to one or
more.
Tn a still further preferred embodiment of the
present invention; there is provided a process for preparing
a lactam-polyol-polyacyl lactam block terpr~lymer or a lactam-
polxol-acyl polylactam block terpolymer or a lactam-polyol-
acyl polylactam block terpolymer having the general'formula:
_ 3e _ . .
O O
E- C X NH - A-R~ A'- NH-Y--C~ ,-(O-Z)z-O
~xn ~ n x
w
O O
..
-~C Y -~ NH ..--. A R A ° ~NH Y-C ,~~ E
x n x
Wherein (O-Z)z is a polymeric moiety and Z is a hydrocarbon
or substituted hydrocarbon group said group being alkylene,
arylene, alkylene carbonyl, arylene carbonyl, and mixtures
thereof;
A and A' are acyl groups selected from
O O O O
r. e. n ..
_C_. _C_. _S- or -P_
n ~
O
R is a divalent hydrocarbon group;
n is an integer equal to. zero or one;
O
F is an imide group of the formula ~C ~
N
or an ester gxoup of the formula -O-R',
where fihe -O-R' is the'residual of a monohydric unctional
alcohol;
Y is an alkylene or substituted, alkylene having f'~om about 3
to about l4 carbon atoms;
R° is an aliphatic or substituted aliphatic hydrocarbon
wherein the ester group is attached to other than a cyclic or
aromatic radical;
x, x', x " and x°" are integers and the total number of x's
is equal to 2w+2; and z and w are integers equal to one or
more, comprising mixing together lactam monomer, polyol,
monohydric alcohol; basic lactam'polymerization catalyst and
3~ polyacyl lactam or acyl polylactam and polymerizing the
lactam; polyol and polyacyl lactam or acyl polylactam to form
block terpolymer, having at lest 5% ester group termination.
- 3 -
,A° ~~ f
the polymerized lactam component of the above
polymers is formed from cyclic monomeric lactams of the for-
mula
~O
Y. C
NH
where Y is an alkylene group having at least about
three carbon atoms, preferably from about 3 to 12
or 14, and more preferably from about 5 to about 11,
carbon atoms.
d~ preferred monomer is E-caprolactam. Lactam monomers in
addition to ~-caprolactam include aC-pyrrolidinone, piperidone,
valerolactam, capryllactam, lauryllactam and the like. 7Cn
addition to lactams unsubstituted an their carbon chains,
lactams having substituents an the carbon chain which do not
inhibit or otherwise adversely affect the polymerization of
the lactam are also included within the scope of this invention.
During polymerization the cyclic lactam ring is
opened to provide the following monomeric unit
-C- Y- NH-
which, together with other lactam molecules produces a
polymeric block of the formula
a
'" -C- Y - NH _
where x is an integer greater than one:
The monomeric lactam unit can also react with the polyacyl .
lactam. .
3g -
__;imilarly, a polylactam block, which joined with a polyacyl lactam,
forms a polymer segment of the formula
- C - Y - IdH - A - R - ~ A'
x ;\ Y
where R is a hydrocarbon group described
hereinbelow, A and A' are acyl groups,
x is an integer greater than one and y is
an integer equal to or greater than one.
l~ The monomeric lactam unit can also react with the aryl polylactam.
Similarly, a polylactam block, when joined with an acyl polylactam,
forms a polymer segment of the formula
a re
c-Y-u~ --x- rr~-Y-a
x . Y
where X is an acyl group, x is an integer
greater than one and y is an integer equal
to ox' greater than one.
Thirdl. in the course of the
y, polymerization of the components
- 2U
described above, a polyol can react with the polymerizable lactam
unit or bloc7c to produce a polymer segment of the formula
t~
n
o-z1 -o- c-Y-~aH -
.JZ x
where x and ~ are integers equal to at least
one and where ? is a hydrocarbon, substituted
hydrocarbon or acyl~ted hydrocarbon group
which, together with the oxygen atom attached W
-thereto, :corms a polyether or polyester seg-
went of a polymer molecule.
The ~ hydracarbon, substituted hydrocarbon and acylated
hydrocarbon groups can be of any size but are preferably limited
~to about six carbon atoms. Even more preferred are unsubstitu-
ted aliphatic groups such as metliylene, ethylene, propylene,
butadienyl and the like. Other suitable ~ groups include pheny-
lene chlorophenylene, tolylene, isobutylene,~isopropylene, ethyl-
carbonyl, propylcarbonyl, ethylsulfonyl, propylthiocarbonyl and
the like .
The preference indicated above for unsubstituted ali-
phatic Z groups means that terpolymers of this invention which
contain polyether segments are preferred over other embodiments
which contain po7.yester segments. Optionally, the fourth pro-
cess reagent is a monofunctional alcohol which can be added any
time prior to or simultaneously with the lactam polymerization
catalyst. Typical alcohols which are operable according to the
inventive process for the preparation of at least a partially
ester terminated terpolymer are monohydrie aliphatic end substi-
tuted aliphatic alcohols, e.g,, methanol, ethanol, 1-propanol,
~-propanol, 1-butanol, 2-ethyl-hexanol, 1-dodecanol, 1-octadeca-
nol, 2-octanol, 1-decanol, and the like, and admixtures of iso-
mers thereof. Unsaturated alcohols, for example, allyl alco~l,
methyl alcohol, nitxo alcohols, amino alcahols, far example, di- '
'methyl aminoethanol, and the like are considered to be operable.
Other operable monofunctional.alcohols can be selected from
monohydric polymers, for example tridecanolethylene oxide con- w .
densates (polyoxyethylene). In addition to the exemplary lis- ~ ~ ,
t~.ng above, monohydric alcohols which do not dehydrate readily
are also desirable: Aromatic alcohols such as phenol and/or
cresol are not suited for the invention, however, aromatic radi-
cals can be included in the hydrocarbon R groups of the mono-
hydric alcohol ROIL wherein the OH is not connected directly to
the aromatic grouping.
Preferably, the monohydric alcohol is one which is
soluble in the ~.actam polymerization system and the use of the
alcohol varies considerably depending upon the nature of the end
product desired. Alcohol presence may vary from about 0.1~ to
- ~ -
r .
j.~ou-t 15u~ of the molar equivalents of imide from excess aryl poly-
lactam or polyacyl lactam based on the molar equivalenvs of hyroxyl
from polyol present in the reaction admixture, fhe number of aryl
laetam groups, i.e. imide groups, in excess of poly~1 contributed
hydroxy groups determines the number of terpolymer end groups, thus
determining the amount of monahydric alcohol required. Depending upon
trie presence of alooHol in the reaction admixture, the terpolymer will
be comprised of from about 0.1~ to about 100 ester end groups. The
presence of alcohol in the reaction admixture provides conditions
wherein the alcohol reacts with tine imide in the formation of ester
groups, however, this reaction proceeds very slowly without the pre-
sence of the basic Iactam polymerization catalyst. In order to
achieve the at least partially ester terminated terpolymer according
t~ the invention, the presence of the lactam polymerization catalyst
is necessary for the ester formation as. well as the terpolymer for--
mation. for example, the preferred polymerization temperatures of
w this system are from about 90 to about 190°C and more preferably from
about 12o to about 180°C. Under these temperature conditons the
moa~ofunctiona:L alcohol reacts very slowly with the imide in the for-
oration of ester groups, however in the presence of the lactam poly-
,ci ~merizati.on catalyst ties ester formation proceeds rapidly and
according to tine invention.
..In preferred aspects of this invention, it is theorized
that the lactam is present in the polymer in the form of polylactam
blac.~cs wlaicl~ are alternated with blocks of polyal to form the polymer.
The polylactam blocks when present can be of any size but customarily
have molecular weights n~ at least a:aout 500, preferaL~ly at least
abcaut 1000.
The polymerized polyol components of ties polymers of
this invewtion are formed from polyol intermediates having at least
'fin hydroxy.~roups. Included-within the scope of the above class
ire a large number of suitable compounds ranga.ng from the simple diols
such as ethylene, gl;~col to' complex polynceri~ polya~ls sucr~ as poly
f~ E-caprolactone) diol. Utter polyol cornpounds include al.kylene
:: ~ s ~ ,:.::
~~c~, ~~~~
glyeols such as dietnylene .glycol, triethylene glycol, tetra-
ethylene glycol, tetramethy~.ene glycol, propylene glycol, di-
propylene glycol, hexylene glyco1,1,2-propanediol, 1,3-propane-
diol, 1,3-hexaned~.ol,~ l,S-pentenediol, butylene glycol, 1,4-
butanediol, dicyclopentadiene glycol, heptaethy lene glycol, and
isopropylidene bis (p-phenyleneoxypropanol-2); diol other than
al.Jsylene glycols such as hydroxyethyl acrylate and hydroxypropyl
methacrylate; polyols raving more -titan two hydroxy functions such
as glycerol, pentaerythritol, 1,2,6-hexanetriol, and 1--trimethyldl
propane; polymeric polyols such as pohrethylene glycols, poly-
propylene glycols, polyxoypropyleiae diols and triols, polytetra-
methylerae glycols, castor oils, polybutadiene glycols and polyester
~lycols, and a large number of compounds containing substituents
other than hydroxy groups such as 294-dicnlorobutylene glycol. In
addition to all the hydroxy compounds set forth above, the thio
.compounds analogous to the above compounds having sulfur atoms in
place of oxygen are also included within the scope of 'the invention.
A few examples include hydroxyethyl thioglycolate, ethylene glycol
bis-(thio-glyco~.ate), pentaerythritol tetrakis-(fihioglycolate)
~d ~thiodiglycol::
If the polyol intermediate is a polyaner, the molecular
weight of Erie polyol can be any amount. Commercially available
polymeric polyol compounds have molecular weights from 200 to 5000,
but polymers with araolecular,weights outside that range are also
1.~~1.9~ ' .
The R group can be any hydrocarbon group having at least two
~ralence bonds for attachment to the aryl groups shown in the
above formula. Rxamples include functional groups obtained by
the removal of hydrogen atoms from methane, ethane, propane,
hexane, dodecane, benzene, toluene, cyciolZexane and the like.
The R group can be of any size but is preferably limited to
. about twenty carbon atoms, and more preferably about eight
carbon atoms. If the in-teg~:r ''y" is one' the linkage will be a
diacyl group. The A groups can be any acyl group and grefer-
ably are '
~ s o ~ .
11 At tt At
m~.e' o~~ 9 ~.~°e 9 or ~~~~.
groups. Most preferred among the above groups is the carbonyl
groups.
,. Values for the integer "y" have a direct relationship
to the -thermoplasticity of the terpolymer. The higher tile value
of '°y'', the more highly crosslinked will be the finished polymer.
Values for °'y" can be as High as six or eight, but more preferably
do not exceed two or three. however, wizen n is equal to zero,
aid A' i.s an aryl group, for example, a phsophor°,~l group,
~~w . ,.
there will Ue another group attached to the phosphorus atom in
addivion to the two amide, groups. ~fhe additional group can be
either another~amide group or some other group such as hydrogen,
halogen, or monovalerat hydrocarbon. uJhen A° represents a
carbonyl group,
30 _~~' ,
ti~ex°ewill be only two amide groups attac~ied to the carbonyl
group.
~ :.
_, ... .... ...~.
The polymerized product comprising the aforementioned
components can have a number of different structures depending
upon the process conditions and the relative proportions of in-
gradients used in the reaction system. Polymers can be prepared
having relatively small segments of lactam units joined to similar-
ly short segraents of polyo~. units through the polyacyl linkage
described above. Or large segments of one polymeric component
can be combined with a larger number of comparatively small segments
of another polymeric unit, which small segments are joined to
one another through the polyacyl or aryl linkages as well as to
the other type of polymeric component. Or segments of varying
sizes of both the lactam and the polyol polymeric units can be
combined through the polyacyl components to form a highly random
terpolymer. Another form of polymer within the scope of this
invention are block polymers, where moderately large size blocks
or segments of the lactam and polyol polymeric units are positioned
alternately in the polymer chain and joined through the polyacyl
or acyl groups described above. Tf the polyacyl or acyl link-
ages are, for purposes of simplification, considered to be a part
of either a lactam or polyol block, then the block polymers of
this invention can be discussed in terms of two alternating blocks
designated as A and B blocks, instead of in terms of complicated
patterns of 'three blocks designated as A, B and C blocks. Block
polymers of this invention can have three general structural con-
figurations, AB, ABA and a repeating pattern of AB segments.
following a genera. characterization of a block copolymer within
the scope of this invention as AB, ABA or repeating AB, it should
be recognized -that the exact structural configuration may vary
somewhat from the general characterization of the polymer: As
an illustration, one tha~retical formula for a lactam-polyol-
polyacyl lactam or lactam-polyol-acyl polylactam block ter-
polymer of the repeating AB type could be
~. g -
Imagewhere x, x', x", z and w are all integers
equal to one or more, R and Z are divalent
hydrocarbon groups, Y is an alkylene group
having at least three carbon atoms, and A and
A' are acyi groups.
As an illustration, one theoretical formula for a lactam-polyol-
acyl polylactam block terpolymer of the repeating A~3 type
could be
.
. O
as
9,~
1
U
a
~ ~
a
p
?C
A
_ _.
~~~_ __.-_.«
A
1
~~r~
1
i '
~~
' v1
1 .
:i ' '
i .._
.:I ~ I '
~ x-
:!
t .'~, . ...
,/'~ '~ .
'
,:
.;
1
_.~
_~_
1 . .
y .
~.~..~ - ~i
. ~~
'; ' _12_
where x, x', x", z and w are all integers
equal to one or more, Z is a divalent
hydrocarbon group, Y is an alkylene group
having at least three carbon atoms,
and X is an acyl group.
Optionally, as an illustration, another theoretical formula for
a lactam-polyol-polyacyl lactam or lactam-polyol-aryl polylactam
block terpolymer of ~tl~e repeating A~3 type 'could be
- 13 -
Imagen1. ~'.
~ where x, x', x", z and w are all integers
equal to one or more; n is an integer equal
to zero or one; R and Z are divalent hydro-
carbon groups; Y is an alkylene group having
'at least three carbon atoms; A and A' are
aryl groups; and R' is an aliphatic or
substituted aliphatic hydrocarbon wherein
the ester group is attached to other than a
cyclic or aromatic radical with RP corres-
1.0 ponding to the R of'the monohydic alcohol,
R OH utilized according to -the optional inventive
process.
If for instance Y is a straight chained amylene group, A and A'
are carbonyl groups, Z is ethylene, -CH~CHZ-, and R is phenylene,
the terpolymer would be,a caprolactam-ethylene glycol polymer
where the daprolactam segments of the polymer are joined to one
another and to the ethylene glycol segments through terephthaloyl
., linkages. Other'lactam-polyol po~.yiners, both of the AB, ABA as
well ~s the repeating AB type, will become immediately apparewt
20 to those skilled in the art in view of this disclosure. It
should thera.fore be noted that the above structural formula is
set forth for illustrative purpose only, and as not intended as
a l~im,itation of the polymers within.the scope of the invention.
den the polymers of this a.nvention are of the ABA
~tyPe, where one block of one type of polymer segment is located
~gtween two blocks of..the other type of polymer segment, the
polymers can be of either the polyol-lactam-polyol type or the
:i la~~t~n-polyol-lactam type: Of the two hypes, the latter is a pre-
gerired tYPe of ABA polymer.
~. ~0 If~the,lac~tarn-polyol-polyaeyl lactam,or lactam-
polyol-acyl golylactam polymer is a Mock polymer the polyol
bucks sans like: the polylac-tarn.' blocks, be of, eny sire but
~1~ ~ ,, ,, ,.
'"~ D~~.~
customarily have molecular weight of at least about 500, pre-
ferably a-t least about 1000. The ratio of the number of lactam
'to polyol blocks can also vary. Since -the block polymers can be
of either the type designated as AB, ABA or repeating AB, the
ratio of lactam blocks to polyol blocks can vary from 2:1 to 1:1
to 1:2. Piixtures of two or more block polymers having different
ratios of the lactam and polyol blocks will produce ratios of
polymer blocks intermediate between. the above stated ratios.
In the above theoretical formula'for a lactam-polyol
block terpolymer, the polyacyl linkage is represented as located
between two lactam polyiaer segments as well as between a poly-
ether segment and a lactam polymer segment. As a practical
i~natter9 the polyacyl or acyl linkages will also be located
;.. -occasionally between two polyol blocks. It should be noted, more-
mver, that the polyacyl acyl linkages need not invariably be
positioned between lactam and polyol blocks since the necessary
! ester ,or amide linkage can be provided invt'he form. of an ester
linkage by the oxygen atom of the polyether segment and the car-
bo~hyl group of a polylactam segment.
!C- As anentioned earlier, the terpolymers of this invention
are characterized by the presence of both ester and amide linkages
between the monomeric segments of the polymer. The term
''monomeric segraent" is intended to apply to the polymerized
extraction product of a monomer, whether the reaction product
is'a single unit such as . . ..
' o~ n t
C - ~C~I2 ~5 - NH -, or _ C _ Ng _
or a block df several units such as.
C -,~CH2 ~5 - NH -
Regarding the breadth of lthe terms °rester linkage°' and.
''amide
.'!~ linkage", -the linkage C~ of couxse~be composed og acyl group
~' other than carbonyl groups since the p~lyacyl .or acyl linkages
a ~.~ 6~
..
described above includes thiocarbonyl, sulfonyl, and phosphoryl .
groups as well as the more conventional carbonyl groups.
The molecular weight of 'the terpolymers can vary widely
from a number average molecular weight of just a few thousand to
one million or higher. For thermoplastic uncrosslinked polymers,
a preferred range for number average molecular weight is from
about 10 or 20,000 to about 300,000 to 200,000. if the polymers
are crosslinked, the molecular weights of -the polymers can be
much higher in the range of 100,000 to several million.
When block polymers are formed, the molecular weight
of the polyol blocks is an important consideration in selecting
preferred polymers within the scope of this invention. Polyol
blocks having a number average molecular weight of about 500
or 600 generally tt:nd to have particularly good low temperature
properties. Thus minimum level of molecular weight for the
polyol blocks is subject to some variation insofar as low
temperature properties can also be affected by the'degree of
block palymexizata.on, the nature of the block polymer, i.e. AB,
AsA or repeating AB, the ratio of the lactam content to the
~0 palyol content, and the particular lactam and polyol present in
the polymer. Regarding a maximum molecular weight of the polyol
blocks, preferred polymers have polyol blocks with a maximum
number average molecular weight of about 6000, and mare prefer-
,;ably about 4000. Above these levels 'the polyol prepolymer tends
tp exhibit a reduced hydroxyl functionality, thereby making
more difficult the incorporation of polyol into the polymer.
7Cn addition to the three principal monomeric can-
stituents which together produce 'the terpolymers of 'this in-
vent~.on, other pvlymeri~able monomers can also be used -to prepare
30 polymers having four or more golymeri~able constituents. As
an example, if the polyo~. constituent of a terpolymer of this
invention is polybutadiene diol, the resultant terpolymer could
-lay
_. . ....~ _.-.._ .__ .____ ._._
,' 1.D~~.~~ . ..
be, aft er the lacta.~t-polyol-polyacyl lactam or lactam-polyol-
acyl polylactam polymerization, subsequently reacted with a
vinyl compoundvsuch as styrene to crosslink the polymer through
its vinyl unsaturation. Still other monomers could be chosen
Which could be polymerized diirectly into a linear polymer chair..
fhe quantity of such additional monomers could be very large;
even as great as 50~ or more of the total polymerizable con-
stituents but preferably is limited to quantities of 25$ or less
of the total monomer content.
The polymers of this invention exhibit a broad range of
properties which can be adjusted to provide compositions particu-
larly well adapted for a specified end use. Tn addition to cross-
la.nking, adjustment of polymer structure, and molecular weight
adjustment of polymer bloeks; other means of varying the pro-
parties of the polymers can also be employed. Crystallinity of
the polymers, which can be present in the laetam segments of
the polycner;~, can be increased or decreased by variation of
polymerization temperatures. Since any crys-~allinity in the
yaolymers of this ~.nvention is ~.argely~present in the lactam
'20 segments of the polymer, variation of the lactam content of the
polymer can. also result in a variation of polymer crystallinity.
vPolymers with relatively high degrees of crystallinity tend to be
strong, rigid polymers whereas -those.with little or. no crysta,llin-
ity are more elastomeria in nature.
~~ m~,ntio~ed earlier, the type of lactam, polyol and pJIS~acyl
lactam or acyl rolylactam can also aff~et the properties of
.the finished polymer: As an example, polyethylene glycol .
~yolymer segments tend to produce polymers,with a,high water ab-
sorp~ivity whereas ~olYPraPYlenc glYCOl or polytetramethylene
3~ glycol polymer segments produce polymers with comparatively low
grater absoxp~ivi,ties. As another example, caprolactam polymer
~~ - v
F
segments in the polymers of this invention produce polymers
which are stronger and more rigid than homologous polymers.
containing segments of a higher lactam such as caprylactam or
dodecanolactam. With respect to the polyacyl lactam or acyl
polylactam, an aromatic hyda~ocarbon group between the acyl
lactam groups will produce a more rigid terpolymer than will a
polyacyl lactam or aryl polylactam with a long-chain aliphatic
group. Even more significantly, use of a lactam will yield an
essentially linear polymer whereas use of a tris or tetrakislactam
l~ will result in a branched or crosslinked terpolymer. Similarly
bis-lactams can be employed to produce a branched ox' crosslinked
golymer. ~Iighly crosslinked polymer can be made thraugh the
use of polyols having more than two hydroxy groups.
With all of the foregoing techniques available for modi-
Eying and adjusting the properties of the polymers of this in-
. venfiion, it can be appreciated that the polymers can be used in a
number of end use'applications. One such use is as textile fiber.
Throughout the entire range of ratios of polymeric components,
from polymerscontaining very little polyether component
~2p to those containing ~ large amount, the polymers have properties
which make them useful as textile fibers. Tn addition to being.
the sole constituent of a textile fiber, the terpolymers can also
be used as one component in a composite or conjugate fiber. It
is contemplated that conjugate fibers of nylon and the terpolymers
~f this invention will be particularly useful in a number of tex--
tile artd other appl:i:cations. Other textile applications for the
terpolymers include 'their use in the manufacture of non-woven
fabrics and as high moisture regain fibers. The terpolymems can
als~ be manufactured into foamed articles, either during or after
-heir polymerixat3.pn, to pxoduce rigid and flexible foams.
Because. of their method of, preparation directly from the mono-
~e~,$,c components, the polymers can be prepared in large shapes
x,19-
': . _ .. ._...,.~
4.-
"u
, .
~~~~~~
such as furniture and furniture components.and automobile parts.
The terpolymers can also be produced in the farm of molding resins
which can subsequently be molded by injection molding, extruding,
thermoforming or other techniques to produce products of vir~tualay
any shape. The more highly elastomeric compositions can be used
in the manufacture of automobile tires and tire components. The
polymers can also be modified with fillers, fibers, pigments,
s~yes, stabilizers, plastieizers, flame retardant and other poly-
meric modifiers to alter their properties and thereby enlarge
even further the scope of their applicability. One such modifi-
.ration comprises reinforcing the ps~lymers with fillers or fibers
r~ahich have been treated with coupling agents capable of increas-
ing the bonding of the fillers oa~ fibers to the polymer molecules.
~ large number of organosilane compounds have been found to be
especially capable of performing this task of improving adhesion
between polymer and filler or fiber. Examples of some. suitable
organosflane~cauplers for use with the polymers of this invention
include 3-aminopropyl triettaoxysilane, glycidoxypropyl trimethoxy-
.silane and N-trimethoxysilylpropyl-N-,~'-aminoethyl)-amine.
2~ Preferred fillers and fibers include quartz, wollastonite, feld-
spar, calcined kaolin clay, glass fibers and other high perform-
ance fibers such as graph~ae, boron, steel and the like. The
where A is an acyl group selected preferably
from
0 S 0 0
AB AA qA sA
-. _ C ~ ~ P C '' p ~ _' ~~. _ P .-.
1A
-_.
~rhere Y is an alkylene group having at least
about three carbon atoms, where R is a hydro-
carbon group, where y is an integer equal to
~~ at leapt ane, and n is an integer equal to
zero or one
and conducting the palymerization of the lactam, polyol, polyacyl
lactam or acyl polylactam, and alcohol under conditions which
~ail1 cause the lactam to polymerize.
Polymer~.zation temperatures can vary from the melting
point ~f the lac~tam or less up to the melting point of the
~cesul-tant polymer or more. Defending upon the particular ingred-
~.eri~ts being useds this can encompass a range .from 70 to 230QC or
more. Preferred palymeri.zation 'temperatures are from about 90
20 to abowt 190°C, and more preferably from about 120 to about
1~0°C fdr c~~rolactam terpolymers'.~ Even more preferred is a
polymerization where the temperature is increased during the
polymerization from an initial temperature of from about~70. to
about 100°C at °the beginning of the polymerization to a final -
t~naperature of abou~c 1S0 to 190°C. Such a technique produces a
rapid polymeri~ata.on of a terpolymer having high'strength and
modullls .
.)..
' . ~.21~.~
J 1
f
Times required for complete polymerization will vary
considerably depending upon polymerization temperatures and the
specific ingredients used in the polymerization system. Total
polymerization tame can he as little as 30 seconds or less,
preferably from 1 to 1U minutes, and car, be extended to arty
duration u1: to several. days or more. Generally, polymerization
times of from 1 to 10 minutes are preferred for most Polymeriza-
tion systems.
The lactam monomer and Iiolyol used in the ~olymeriza-
1~ tion have both been described in ample detail above. The lactam
polymerization catalyst useful herein includes that class of
compounds commonly recognized as suitable basic catalysts for
the anhydrous polymerization of lactams. In general, all alkali
or alkaline earth metals are effective catalysts either in the
metallic form or in the form of hydrides, ?~alohydrides, alkyl-
halides, oxides,, hydroxides, carbonates and the like.
Also useful are a number of organometallic compounds
of the metals mentioned shove such as metal 11?~yls, metal pheny3s.
metal aides and the like. Fxamolas i:nclurle sodium hydride,
ZO potassium,hy=droxi:de, lithium oxa.de, ethyl magnesium bromzdc,
calcium ~luorohydride, strontium carbonate, barium hydroxide,
methyl sodium buthyl lithium, potassium phenyl, Biphenyl barium,
podium amide and magnesium diethyl. 1111 of the foregoing com-
pounds reactvrith the la~tam monomer to form the metal lactam,
~rhach is the active catalytic agent in the lactam polymerization
mechanism. The metal lactam catalyst can'therefore he formed
in situ by reaction of one of the foregoing metals or metal
'compounds with lactam monomer in.the polymerization medium or by
prior reaction of the metal or metal compound with a stoichio_
3~ ~eetracquantity,:of lactam monomer. 'Examples of metal lactam
catalysts include sodium cdprolactam; magnesium capro.lactam,
bromamagnesium pyrrolidinone, chl;orecalcium ca~rolzctam and the'
..~ 2 ..
- o ;.' , , ,, .. ;. . ,...,:.~,.,~
n
like. Catalyst concentrations can range from a fraction of one
mole percent to 15 or 2n or more mole Percent of the lactam
monomer to be polymerized.
The polyacyl or aryl linkages, as well as the ester
and amide linkages, are incorporated into the polymer chain
through the reaction of the pol,Tacyl Iactam or acyl polylactam
with the lactam and polyol constituents. Tn the formula set
forth above for the polyacyl Iactams useful :herein, the R group
can be any hydrocarbon group having the necessary number of
~? available valences to bond to itself all of the acyl groups in-
eluded in the compound. The hydrocarbon group can be of any
size but preferably contains a maximum of eight or ten carbon
atoms. .Examples of suitable It groups include phenylene, bi-
' phenylene, metlxylene, hexylene, tolylene, and analogous hydro-
~arbons having more than two sites available foal bonding to
a,~yl groups. The integer "y" preferably is from one to about
three. The A gxoup can be carbonyl, thiocarbony7,
or suifonyl; and the A' group can.be the same as A'as,well as
phosphoryl. The Y group pan represent any alkylene chain having
~p fr~m 3 to 14 or more,carbon atoms, preferably from about 3 to,
about 10 carbon atoms. (referred among the class of polyacyl
lactams. included within the scope of the ~ormula'given above
axe those where the A and A' groups axe carbonyl groups. par-
ticularly preferred aro those .compounds where A and A' are car-
'bonyl, ~aher~ It is either alkylene or phenylend, Y is a five-
membered alkylene group and the integer ''y"'' is one:
Fxamples include terephthaloyl bis-caprolactam, i.e.
~ o ~
a ~ ~~ ~
~_,~_ (~: ,~_.~
~~~ ~y ~ MZ
23 .-
adipoyl bis-caprolactam; malonyl bis~-pyrrolidinone; succinoyl
bis-pyrrolidinone; glutaroyl bis-piperidane; glutaconoyl bis-
peperidane; 2-ethyl-2-phenyl glutaroyl bis-valerolactam; 2,3-
diethylsuccinoyl bis-caprolactam; pimeloyl bis-capryllactam;
sebacoyl bis-caprolactam phthaloyl bis-peperidone; isophthaloyl
bis-dodecanolactam; 1,3,5-benzene tricarbonyl- tris-capralactam;
1,2,3,5-benzenetetracarbonyl tetrakiscapralactam; 1,2,3,4-
naphthalenetetracarbonyl-tetrakis-piperidone and 1,4-cyclohex-
aned.icarbonyl bis-caprolactam; 1,3-benzene disulfonyl caprolac-
tam; 3-(sulfonya caprolactam)-benzoyl caprolactam; phosphoryl
tris~caprolactam; benzene phospharyl bis-caprolactam; and di-
thioterephthaloyl bis-caprolactam.
The amount of polyacyl lactam or aryl polylactam use-
ful in the preparation of the terpolymers of this invention de-
pends upon the quantities of lactam and polyol being used. For
preferred polymerizatians, it is desirable that the polyacyl
lactam or acyl polylactam be present in an amount from 100 to
...,. . .
about~500, preferably from about 100 to about 200, equivalent
percent of the polyol. Tf the polyacyl lactam or acyl poly-
.,:i
lactam is present in an amount less -than a molecularly equiva-
lent amount based on the polyol, polyc~l prepolymer formation
occurs, but the subsequent lactam polymerization is very slow.
In those preferred polymerization systems where the polyacyl
lactam or aryl polylactam concentration exceeds the amount stoi-
chiornetrically equivalent to the polyol, the excess can be from
0.01 to about 30 or more mole percent of the lactam monomer. A
preferred range is from about 0.1 to about 10 mole percent of the
lactam monomer, and more preferably from about 0.2 to about 5
angle percent of the lactam monomer.
The lactam and polyol can be present in any relative
proportions ranging up to 99 parts of either component to 1 part
of the other. Preferred ratios of the two polymer-forming mat-
erials depend upon the end use to which the finished polymer is
- 24 -
' ~ .. ,. ~ ..
.
~-I O M ie
U° I r1 N r.. O
M r1
M
N O 00 l~
Qp
- GziI V'M N O r1
'l0t~ r1
N
M O M l~
O
W t~~ OA O N
I
OiM r1
N
1nO O O ' .
A lg01 ef~r1 M . ..
I
0 M '.
.
r N ,
-I .
lflO M 1~
UI M ~ ~ o ~
m n N ",
r1r1 ,~
O Q
O N
N ~
r-1
U
!'1 r1O Iw O Q ~
~
u~l rio, rn ra ~n -a ra
H ' N ~
~
~
~rO u) o r1 .L~
'
" Q; 0(9cH r1 r1 1a U to
i I
. N O tn Q ~....
M . ,-.1
r1
N
~ ''
-1
f~ N
~
''~
"J
i
~
r--1 ~ -N
~
~
s-I r- Q ,4
1
ili1c O U 1
I
'~ 9~
: ti
~
J
.
'r13 ~ N
r-1
'; ~ ~ a
m
'~ ~ ~ O
U ~ ''d
~ N ~ W ~
~ ~ r N
1
O U ~ H ~
N ;r ~
.,
~ ~ ~ ~ p ~ ~
~ ~ fa aAo
~ ~ ~ ~
E. pry ~ .x ie
,,
_ _
z&
, !\
zn each of the above runs, the polypropylene glycol, caprolac-
tam, Santowhite ~R Powder and terephthaloyl bis-caprolactam are
mixed together at 100°C. To the resultant solution, bromomag-
nesium pyrrolidinone is added in a concentration which provides
8 millimoles of the bromomagnesium pyrrolidinone per mole of
capxolactam. The reaction mixture is then poured into a sheet
mold heated to 100oC and having a thickness varying between 3
and 13 millimeters. The mold is heated to 160°C over a 12
minwte period. After a 30 minute period, the mold is opened
and the finaahedypolymerized composition removed. Samples of
each composition are tested to determine their mechanical prop-
erties, which are reported in Table 2 below.
"\ ~
U
G p iD .
O
W'
i-t
H
54
o~
p sn N ~- ~ N ~
p ~ aan~cv so m cn cca
O r-t
O
~ ~
.(~ .. ~,Qtf?C~ N N Cn
E-~ tf1~ to ~ e.r~t~ as
~
. , ~
O
- U
~
o~ ~ M t&~u7 ~ ri
.~.mr~
IJ~ fr? CO r-1m tn p
N
a
!'1C~ ~' C~ OO
~ n a~ pa c~ p nt ~
F-s .
'm
. ~ M N Cn ~'S. ~ ~ .. .
~ ~
' Hcnx
N ~N ~
PI ~ ,
~
n Pt
~
ai ~
x
. ' .. ...
~
.
' .
O N m n c p capm O
~
N L'~N p 65ftf> tm M tn
e~I
f11
~ M sf9u? ~' ~' N '
W
r-( ,~
~
e-) \ . . .
do
~
~ ~
H . '
.~
A-t
~ . .
~ C~ 6Cit~ IfsN N ,~"~,fy
I~
~
~ r-VN M ~ ~ u> m.n
W
-; i
(~} O GO
a
,'1~ ,~'s8 L~
,,.f
;
O I ~
. . ~ a ~ . . t ...
,
~--t ~
~ ~
'. ~ '.
;. ,~ 00 to t~ t~ QO OD do (Q ' '
'I ~ 6D u9 ~' . N e~tm ~
M
o o a o 0 o s o
6 oa r~ ~a w W c~ c~.
28
Example 2
Seven different caprolactam-polytetramethylene
glycol-terephthaloyl bis-caprolactam terpolymers are prepared
using the quantities of ingredients specified in the following
table.
Table 3
Material A B C D E F G
Polymeg * 229.0 196.0 163.0130.0 97.0 64.0 31.0
Caprolactam 79.0 117.0 156.0195.0 234.0 273.0 311.0
T B C ** 42.5 36.7 30.9 25.1 19.3 13.4 7.6
Santowhite 0.7 0.7 0.7 0.7 0.7 0.7 0.7
~R Powder
Wt $ glycol 65 56 47 37 28 18 9
in copolymer
* polytetramethylene glycolwith a
molecular weight of t
abou 2000
** terephthaloyl bis- caprolactam
In each of the above runs, the polytetramethylene glycol,
caprolactam, Santowhite ~ Powder and terephthaloyl bis-capro-
lactam are mixed together at 100oC. As in Example 1, bromo-
magnesium pyrrolidinone is added and the resultant mixture is
heated to 120°C and asst into the mold which has been pre-
heated to 100°C. The mold is then heated to 160°C as in
,;
Example l and held at that temperature for 30 minutes, after
;.
which time it.is opened and the samples removed. Table 4
below is a report o~ the mechanical properties of the compo-
sitions prepared.
~9
,.:. . w .; ~~ -.' ~. ..,..' ' ,.~ ~~, y.. ~~ . , y~ ~. ., .. ... . ~~ , ..'
.;., w ~ ' .. . ." . .,.. ._.. . '
.-~ ~
i
~ ill.
r n
U o 0
~ ~'d'
N
U eke fv 'x .. ~ ~
~
O .
~
H
,Y,
M
O
a--~
c.~ ~
. Ifa ~aM tA tn M CeiM Ce6
~' ~ ~ ,~ ua ca ttp
O ~
O a ,
a~
U .~- ~ c-dcv .-iC~ ~ ~ ~o
a
csa
' C/a N c0 r-d ri Ch M nt r--)
. r-! N M iiD~. r(
U
fn . ~' ' N
~ 6E? Lt)
\
. G~ aA ~ ~ .
.
.~d .
C/~
.tea
' ~
. . 1
~
. . .
-;'l . . .
~~ .
,
.
.
'
v! ~ .
~ ,
~ ~ ,
'
! ' H mD
ao
~ 0 v '~ p g
~
t o ~e u ~ a
a c s o
. ~ ~ Q.'. ~'.ya .~ M
.i
~ ..
~ ~p -
~j
~
~ ~ ~ ~
U
:, H bD
.
,,. . ~a , r-1
.1
e~~l
'~ ~" M ts>N ~ f~
'e-1
~ N ~ ~ ~
t . c . ~ ~c 3.
i o
a0 . ,~,
.
: ~ , ,
.
:I ~
~ . ~~
:i
~~
~ ~ ~
~ .:~.
,
-,
~ . ~
_
~
~ .
- ~
~ .. _ _ ..
. ~
;
~
O ~ ~ ~ ~ ~ ~,
. ~ 0 a a A 1 B B .
~ r.4 ea ~a c~ H ~
w ~
.-.1
~.~a~~~~
Example 3
Seven different caprolactam-crosslinked polypropy-
lene glycol terephthaloyl bis-caprolactam terpolymers are pre-
pared using the quantities of ingredients specified in Table 5,
Table 5
Material ~ B C D E F C
Niax 61-58 R~* 2 29.5 196.4 163.3 130.3 ~ 98.164.1 31.0
Caprolactam 79.0 118.0 157.0 195.0 233.0 273.0 312Ø
T B C 41.2 35.6 30.0 24.3 18.7 13.1 7.5
Santowhite
0.7 0.7 0.7 0.7 0.7 0.? 0.7
~ Powder
B M P ** 5.0 5.0 5.0 5.0 5.0 5.0 4.4
G~t.~ glycol 66 56 47 37 ' 28 18 9
solution temp. 160 140 120 120 120 120 120
initial mold , ~
160 140 110 110 120 120
''. 110
temp .
* mult~,func~tional 2000
polypropylene glycol mol.
of wt.
** bromomagnesium pyrrolidinone
Each of the seven runs .is carried accor ding the
out to proce-
dure set forth in Examples l and temperature
2 except that
the
and catalyst concentration as the
are varied shown above
in
,;;
table. Properties are below.
reported in Table 6
..
.v
-~ '~.
~ U ~
N ~ U ~
H H x L'.
U
O l0 i0 t0 l~ M l0 ~O
O l9 lfl l9 tO tn l0 tn
O
~r1
~ ~ I
H~M~ltnhNOCIN
~tJa ~INMN~~ptntp
p
U
i.~ ow t~ ~r ao ~o O u1 ~r
-1~ Ln ~ h ~ ~ u1 °d' O
~ N r-1 N d~ h
N
y-i r1 N M W O1 N
H V1 x
.: .
-;,'a
~ '
1D ~N
i r-1
ro
~ ~°x
i ~ .~ , .
~ a~
U ~i N N o N h w N
~r ,cf M o N o xn o ~.n
N W ~ N M ~N <t' In M
~, dp (d
U
U ~
x
H~ ~~~~rI~NOOO~oa~n
~ w ~ ~r ~, ~r ~n
a~ .
ro
o~ .~~
U N tn
!~
:~ _ _ _ _ _
z
~w
~ ~o ~o h h o0 00 ow
o ~o ~n .~ M N .~ o,
~ r a s r s r r
H ~ a~ U A W w c.~
32
w
Example 4
Two caprolactam-polybutadiene dio~.-isophthaloyl bis-
caprolactam terpolymers are prepared using the quantities of
ingredients specified in Table 7.
Table 7
Material, gms. A B
Arco R-45 M* 165.3 131'.8
Capxolactam 155.0 193.0
IBC** 24.6 20.1
l0 Santowhite ~ Powder 0.8 0.8
Wt o glycol 48 38
Solution Temp: C 90 90
Tnitial Mold temp. 100 100
Final mold temp. 170 170
* polybutadiene diol of 2000 wt.
m1
** isophthaloyl bis-caprolactam
The two terpolymers are prepared according to the
procedure set forth in Examples1 and 2
using
the solution
temper~tures'and mold temgeratures'specified
in Table
?. The
20 catal st bromoma nesium
y . g pyrroli dinone, used in a concen-
is
.
tration of 5 mi:llimoles per of caprolactam.
mole Properties
are reported in Table 8.
:.. ,
;,
Example 5
Eight caprolactam-polyethylene glycol-terephthalo~rl-
bis-caprolactam terpolymers are prepared using the quantities
of ingredients and the solution temperatures and mold temper-
atures specified in Table 9. Properties of the compositions
1 are reported in Table 10.
- 33 -
..,'.. , , ..~ .' , :;.. .~' . ;~....' '. r. . ~.., , ~., ' ~ . '~ , ~., '-
'~.. .., ', _ '. ,;,.,, '
N ~ N O
'-'.,
. x ~ r1 ~,
U o
~
.s,
w
.
U
U
~
O
TJ
0.i
U
O
Ra
N
~
Ln~
H ,
H
x
U
, ~
O N OD O
t~
l 0
~
U
o -rl
0
oe o m o
~, . . , ~,
p
.
N .
. H N tl1 r1
~ ~ ~ N M !"'I CO
Aa U~ &~ N
:J ~
..
~ l0 O l0 M ~
~
W~ l0l'~ M N ~~
~
UlN de cH
r1
f~a
N O
o i.n~n ~r u~
~
o
Hcnx aIa N N O d~ M ~
t0 N r1 O
~ x
N . .~
.
' ~ ,
~
'.;:<i ~ M CO
~
O N ~
r
rl h O r1 t0O ~
,:; r'~ ~y ~
I r,~i
U fvr-~ 0 00 ~ ~
I
ra
! H N N . M N
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:
35
Example 6
Two caprolactam-caprolactone dial-terephthaloyl
bis-caprolactam terpolymers are prepared using the quantities
of ingredients and the solution temperatures and mold temper-
atures specified in Table 11.. The catalyst, bromomagnesium
pyrrolidinone, is used in a concentration of 7:7 millimoles
per mole of caprolactam. Properties of the compositions are
reported in Table 12.
Table l1
Material A B
I~Iiax PCP-0240 ~R * 195.0 175.0
Caprolactam 69.0 141.0
TIC 36.3 33.6
Santowhite ~R Powder 0.6 0.7
Solution Temp. .C 90 100
Tnitial Mold Temp. 90 90
.,
~i Final Mold Temp. 160 160
,j Wt ~ Polycaprolactone
; 65 50
,, dial
* polycaprolactone d.iol
20. Example 7
The purpose of this example is to ascertain the
effect on mechanical properties of varying the molecular weight
"i
i of the pol,yol segment of the terpolymers. The last three
samples prepared, Compositions D, E and E', demonstrate the
effect of crosslinking on the same properties. The terpoly-
''I mars are prepared using the ingrediewts and the process con-
..
i
dxtions set forth in Table 13. The catalyst, bromo-magnesium
pyrrolidinone, is used in a concentration of 5 millimoles of
catalyst per mole of caprolactam. Properties are reported in
30 Table 14. .
V
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37
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sra~
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i: .,.,, ' .:.. .. .:: .':'. . ~. . ,.~. .: . : : ...;.. ,; ..
.,, :, ., ~ ..: :, .
._
E3tA1~1PbE ~
A reactor vessel was charged with 106.3 grams of
caprolactam, 131..1 ml of triethylamine, and 300 ml of chlorofox°m.
Over a 45 minute period, 45.8 grams of phosphoryl chloride was
added to the other reaetawts at a temperature of from 25-30°C.
The admixture was then stirred at room temperature for about ?
hours with slightly exothermic conditions resulting during the
first 30 minutes of stirring. A portion of the reaction admixture
was filtered and t-he filtrate evaporated yielding 67 grams of
a dark semi solid product. The product-was treated Further by
slurring with benzenep filtering, and evaporating the filtrate;
again slurring with benzene, and washing with water followed by.
evaporation which yielded 17.3 grams of an amber viscous product.
The product (phosphoryl tris-caprolactam) was utilized as an
initiator an the following lactam-polyol-acyl polylactam
formation.
A reactor vessel was charged with 30 grams of Voranol ~R
2000 (polyoxypropylene polyols having a molecular weight of 2011),
65.5 grams of caprolactam, and 4.48 grams of t:~e phosphoryl tris-
caprolactam initiator which was 0.67 grams in excess of the molecu-
lar equivalence required by 30 grams of foranol~'2f.OJJ. Twenty four
millimoles of the polymerization catalyst, brorno magnesium pyrro-
lidone, was added in 3 p~irtions at a reaction mixture temperature
of from 160 to 165°C. After 20 minutes the viscosity increased
and the bottom part of the rea.c-tion admixture became opaque and
set to solid polymer.
RYnMnt r.
A reactor vessel was charged with 56.5 grams of (0.5
mo~.e) caprolactam, 71.7 ml. triethylamine, and 400 ml. benzene.
Twenty-four grams of phosgene Was bubbled into the reaction ad-
mixture for twenty minutes at a temperature of frown 25°C to
35°C.
The admixture was stirredfor_3 hours a~t a temperatureof from
,.40-60C, filtered, and product containing filtratewas washed
the
twice with 100 ml water and evaporated y~.eldix~g a ma.xture of semi--
viscous liquid and crystals. Recrystallization of the product with
isogropoinol resulted in 33.2 grams of product (carbonyl bis-capro--
lactam). The product was utilized as an initiator in the follow-
ing lactam polyol-acyl polylactam formation.
A reactor vessel was~charged with 3 grams (1.52 milli-
moles) of Voranol~-2000(polyoxypropylene polyols) and 6,5 grams of
eaprolactam. The charged vessel was heated at 150°C for 15 minutes
with bubbling nitrogen in order to remove water. The charge was
cooled to 70°C under nitrogen and 0..53 grams (2.1 millimoles)
of carbonyl bis-caprolaetam was added. The reaction mixture was
heated to 100°C to dissolve the initiator and cooled to 70°C
before 0.3 millimoles of bromomagnesium pyrrolidone catalyst
was added represen°ting 10 millimoles of catalyst per mole of capro-
laetam. The catalyst was admixed w~.~th the reaction mixture and
' the admixture was heated to 160°C under nitrogen atmosphere.
Viscosity increase was noted after 5 minutes and the nitrogen
;; bubble system removed. The lactam-polyol-aryl polylactam terpolymer
had set firm but was penetrable at 30 minutes. Complete set
occurred at 1.2 minutes.
EXAI~fPLE 1p
A reactor vessel charge of 75 grams Voranol ~R 2000
(polypropylene polyols having a malecular weight of 1974), 194
grams.af caprolactam, and 1.25.grams Flectol H ~ (.polymerized ,.
1,2-dil-aydro-2,2,4-trimethylquinoline) was heated under a vacuum
to remove water. 7CSOphthaloyl bis-caprolactam (17.1 grams) was
added to the charge and the admixture was heated main 'to remove
water. A total of 50 grams of caprolactam was distilled during
3p the tw~ drying stages. The admixture was cooled to 65°C and
13.95 m1 of catalyst (brom~ magnesium caprolactam -0.4 molar in
caprolactam) was added and degassed for 1 minute. The reaction
mixture was poured anfio a 100°C sheet mold, resulting in a
- 40 -
thickness varying between 3 and 13 millimeters. The mold was
heated to 160°C over a 20 minute period and held at 160°C for
an additional 30 minute period. The lactamwpolyol-polyacyl
lactam terpolymer set in 6 minutes after introduction to the
... press. The mold was opened after the 30 minute period and
the finished polymerized composition was removed.
The compositions of Example 10 and the following
Examples 11 and 12 were tested to determine their mechanical
properties, which are reported in Table 15 following Example
12. The process and product of Example 10 are not according
to the invention and are presented for comparative purposes.
. .,:,
Examples 11 and 12 as well as Examples 8 and 9 are in accord-
ance with the invention.
Example 1l
A reactor vessel was charged with 37.5 grams of
Voranol UR 2000 (polyoxypropylene polyols having a molecular
weight of 1975), 104 grams of caprolactam, and 0.62 grams
~'lec~tol ~ H (polymerized 1,2-dihydro-2,2,4-trimethylquinoline)
i
and heated to a temperature of 125°C with 25 grams of capro
lactam being distilled under vacuum. Phenylphosphorodi (2
ketohexamethyleneimino) amide initiator (8,35 grams) was
i added to the mixture and stirred until dissolved. A eat~~
lyst sowtion, 8.39 ml. of 2 molar bromo magnesium pyrrolidone
in N-methyl-pyrroli,done representing 24 millimoles of cats-
lyst per mole of caprolactam was added to the reaction mixture
at a temperature of 120°C. The reaction mixture was poured
into a sheet mold which was at 160°C. The lactam-polyol-acyl
polylactam terpolymer set in 5 to 6 minutes after introduction
to the mold. The mold was opened 30 minutes after set and
the finished polymerized composition was removed for testing
as reported in'~he table following Example 12.
Example 12
A reactor vessel was charged with 37.5 grams of
Voranol ~ 2000 (polyoxypropylene polyols having a molecular
weight of 1975), 103.8 grams of caprolactam, andØ62 grams
of Flectol ~ H (polymerized 1,2-dihydro-2,2,4-trimethylc~uin-
oline) and was heated to 125°C for 2 to 3 minutes with 25
grams of caprolactam being distilled under vacuum. Phenyl--
phosphoro di(2-k.etohepamethyleneamino) amide initiator (8.35
ml) was added to the mixture. t~i catalyst solution, 8.35 ml
of 2 molar bromo magnesium pyrrolidone in N-methylpyrrolidone
was added to the reactive mixture under the conditions of
Example 11. The product was poured into the same mold as
was used in Examples 3 and 4 which-was at a temperature of
160°C. The lactam-polyol-acyl polylactam t,erpolymer set in
about 9 minutes. The mold was opened 30 minutes after set
and the finished polymerized composition was removed for
testing as reported in the following table.
- 42 -
~~~ ~
_
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0
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x .~ O .~ ~ N
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,-I (~ U dD ~-I N O ~-I
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~ '~I rt1 47 ~ ~,' N ~.' ~w' ~
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Of the related terpolymer of Example 10 and Examples
11 and 12, a distinguishing feature as present in the above
Table 15 is the catalyst requirements of 4 millimoles per mole
of caprolactam (Example ZO) as compared to the 24 mill.imoles
per mole of caprolactam (Examples l1 and 12). This difference
is attributable to the polyacyl lactam initiator of Example 10
and the aryl polylactam initiator of the invention as presented
by Examples 1l and 12. The remaining comparison of physical
properties indicates similar, yet different terpolymers which is
in agreement vuith the discussions and formulations of the
invention.
Example 13
A charge of 325 grams Voranol ~R 2000 (pdlyoxypropylene
polyol having a molecular weight of about 2000), l18 grams cap-
rolactam, 60.9 grams isophthaloyl-bis -caprolactam, and 2.5 grams
Flectol ~g' If:',(polymerized 1,2-dehydro-2,2,4-trimethylquinoline)
stabilizer was intraduced into a reaction chamber equipped with
stirrer, thermal controller, nitrogen inlet, and vacuum distil-
". ling head. The mixture. was heated under vacuum tClmm) to re-' .
''~ 20 move moisture b d~a.stillation of 50
y grams of caprolactam. The
vacuum was released to nitrogen atmosphere and the solution
1 cooled to 100°C. ISissolved nitrogen was removed under vacuum
a L-~i
;;
followed by the addition of 2.3 ml decyl alcohol and mixing of
;.
the resulting solution by stirring under nitrogen. The solu-
tion was catalyzed and cast into a stainless steel vertical
sheet press maintained at 100°C by means of gear pumps. The
solution was delivered into the
press at a rate of 876 ml/min.
The catalyst solution (0.4 molar bromomagnesium caprolactam) was
injected into the solution strum by a second gear pump at a
30 rate of 103 mI/min. resulting in a catalyst concentration .of 12
mallimoles catalyst per mole of capralactam.. After casting
.i the press was heated to 160°C.
44
Seven lactam-polyol-polyacyl lactam terpolymers were
prepared and cast using the process of Example 1, however the
alcohol, and alcohol concentration were varied.as indicated in ..
Table 16 below. The results of Example 13 are recorded as run
number. 1 of Table 16 wherein the decyl alcohol presence was 90~
molar equivalence of excess imide based on the molar equival-
ence of hydroxy present. The aforementioned ~ of alcohol
presence is also representative of the ~ ester termination con-
tamed in the resulting terpolymer.~
Table 16
Effect of Decyl Alcohol -
molar equivalence Tensile
alcohol of excess 230°C
imide based on strength Melt
Run molar equivalence f ail Elongation Modules Index**
No. of polyol hydroxyl ICg/cm2 at break Rg/cm2 dg/min w
. ...
1 ~ 90 ~ 129 1100 302 54
2 65 160 1200 211 37
3 0 115 800 134 0.09
Effect of 2-Octanol ~R
4 ~ 90 155 .793 ~91 3Z.2
,y 5 50 . 96 667 352 16.2
a 6 40 126 923 309 2.4
7 ~ 0 111 828 56 0.14
** 250°C, 6800 gm wt. 1.3 millimeter orifice
Example 14
A charge of 150 grams of Voranol ~ 2000, 119 grams of
caprolactam, 29.2 grams isophthaloyl-bis-caprolactam and 1.5
'i
grams of Flectol ~ H stabilizer was introduced into a reaction
chamber equipped with stirrer, thermal controller, nitrogen in-
let, and vacuum distilling head. The mixture was heated under'
vacuum (< 1mm) to remove moisture by distillation of 25 grams of
caprolactam. The resulting solution was cooled to 100°C and
dissolved nitrogen was removed under vacuum, followed by the
addition of ~..7 ml decyl alcohol and mixing of the solution.
- 45 -
. ,.,.; v: ' .
The solution was catalyzed arid cast into a stainless steel ver-
tical sheet press by means of gear pumps. The solution was
delivered into the press at a rate of 876 mljmin, The catalyst
solution (0.4 molar bromomagnesium caprolactam) was injected in-
to the solution stream by a second gear pump at a rate of 99 ml/
min. resulting in a catalyst concentration of 8 millimoles cat-
alyst per mole caprolactam. Six lactam-polyol-polyacyl lactam
terpolymers were prepared and cast using the process of Example
13 however the decyl alcohol presence was varied between 0 and
75~ as defined in Table 16 as well as the solution and mold tem-
peratures as presewted in Table 17 below. The results of Ex-
ample 14 are recorded as run 2 of Table 17.
Table 17
Effects of Decyl Alcohol,
solution Temp. and Mold Temp..
* Solu.- Mold Tensile .
Run Decyl ~tion Temp. Strength ~ 250°C
No. Alcohol Temp. °C Fail Elong- Modulus Melt
_ °C TCg/cm2 ation K~/cm2 Index
1 0 100 100- 273 730 1469 0.09
160**
2 , 75 " °' 337 720 1174 3.4
'. 3 0 100 ~ 160 164 470 352 0.3
4 75 " °° ' 337 770 1983 3.8
ai
5 0 160 160 181 470 527 0.2
6 75 160 l60 3l6 745 1329 3.9
* As defined in Example 13 and Table 16
i
** 100°C.. Initial temperature-increased to 160°C
Example 15
yf
A reactor vessel equipped with stirrer, thermal con-
i
trolley, nitrogen-inlet, arid vacuum distilling head was charged
with 90 grams of a polyethylene glycol having a mole weight of
about 3000, 219 grams caprolactam, 15.7 isophthaloyl-bis-capro-
lactam and 0.6 grams Flectol ~ Vii. The mixture was-heated
under vacuum (<1mm) 'to remove moisture by distillation of 25
grams of caprolactam. The vacuum eras released to nitrogen
- 46 -
atmosphere and the resulting solution was cooled to 70°C and
degassed of dissolved nitrogen present. The cooling and de-
gassing was followed by the addition of from 0 to 4.8 ml decyl
alcohol and mixing of the solution. Catalyst, 3.3 ml of 2
molar bromornagnesium pyrrolidone in N-methyl pyrrolidone was
mixed with the solution and the resulting mixture was poured
into a stainless steel vertical press. The press was main-
tained at 100°C during the introduction of the polymer solution
and was then heated to~160°C during a 15 minute period followed
by an additional 15 minute period at 160°C.
Table 18 presents the physical profiles of four ter-
polymers produced by the method of Example 15 with the concen-
trations of decyl alcohol varying from 0 through 90°, again
alcohol percent presencra defined as in Example 13.
Table 18
Effect of Decyl Alcohol
;:;i Tensile
.:f ml of Strength ~ Elong-
Run ~ Decyl Dec~xl fail ation at Modulu2 Melt
No. Alcohol Alcohol ICg/cm2 break Kg/cm Index
1 0 0 527 O.Ol
2 40 2.0 450 497 5343 0.3
3 67 3.3 443 497 6820 0.83
4 90 4.8 422 467 5625 2.S
Example 16
The same procedure as in Example 15 was followed
. .I
I
:'~~. ~.n produca.ng the following terpolymers as described in Table 19
below, however, the following concentrations of reagents were
utilized: 90.0 grams polyethyleneglycol of molecular weight
about 3000, 219 grams c~prolactam, 0.6 grams Flectol ~ H, 15.7
grams isophthaloyl-bis-caprolactam, from 0. to 2.0 ml of decyl
alcohol, and 3.3 m1s of 2 molar bromomagnesium pyrrolidone in
N-methyl pyrrolidone.
- 47 -
Table 19
Effect of Decyl Alcohol
Tensile
Run ~ Decyl M1 Decyl Strength 250°C
No. Alcohol Alcohol Fail $ Elon- Modulus Melt
2
Kg/cm gation Kg/cm2 Index
1 0 0 464 523 8437 1.5
2 5 0.4 415 410 9140 2.7
3 11 0.8 387 400 8437 3.0
. 10 4 20 1.05 394 410 7734 3.4
40 2.0 330 333 8015 4.5
Example 17
A reactor vessel equipped as in Examples 13 through 15
was charged with 75 grams Voranol ~R 2000 180 grams caprolactam.
1.25 grams Flectol ~R H and 17.1 grams isophthaloyl-bis-caprolac-
tam. The mixture was heated under vacuum (<1/mm) to remove
moisture by distillation of 50 ml caprolactam. The resulting
solution was cooled to 65°C and from 0.7,7 ml to 1.5 ml 1-propa-
nol, or from 1.1 to 1.37 rnl.of 2-propanal added with stirring.
20 Catalyst, 27:9 m1 (0.4~molar bromomagnesium caprolactam in
caprolactam) was added to the solution and stirred for 1 min.,
then. the polymer solution was poured into the press of Example
1 (press temp. 100°C). The press was heated from 100°C to
'i 160'°C over a 20 minute period and held at 160°C for 1 hour.
The physical profxle,s of these terpolymers are compared in Table '
20 wherein the effect of l-propanol and 2-propanol are demon-
stratea:
,:
Physical profiles as illustrated in Tables 16 through
20 demonstrate the effects of several monohydric alcohals upon
30' the t~erpalymers of the invention. improved melt index resulted
with increasing alcohol cancentration.thus indicating a decrease
of melt viscosity of the terpolymers in all runs. Both
- 48 -
improved strength as well as improved melt flow characteristics
were achieved with, for example, the higher concentration pdly-
propylene glycals. The temperature-alcohol presence study pre-
sented in Table 17 demonstrates the flexibility of alcohol modi-
fied, ester terminated terpolymers, for example, in the elimin-
ation of the requirements of two temperature stage polymerization.
The mole a alcohol of all examples and tables is based on the
excess imide concentration and corresponds approximately with
the ~ of prepolymer imide end groups which are replaced by ester
groups, and according to the invention the corresponding ~ of
ester end group termination of the lactam polyol-polyacyl or lac--
tam-polyol-acyl polylactam terpolymers.
Table 20
Effect of l~Pro~anol
Tensile
$ Strength 250°C
Run 1-pro- Mlwl- Fail ~ Elon- Modulus Melt
No, panol ,propario~. Kg/cm2 gation Kg/cm2 Tndex
1 50 0.77 342 472 7523 0.1
2 75 1.1 313 173 6960 0.2
~.'3 90 1.35 352 505 5695 0.8
4 100 1.5 309 176 4359 1.4
Effect of 2--Propanol
1 75 1.1 311 425 6328 0.14
ii 2 90 1.37 317 175 7101 0.7
~.a~~~~~
Physical profiles as illustrated in Tables 16 through
20 demonstrate the effects of several mononydric alco.~ols upon
. the terpolymers of tzxe invention. Improved melt, index resulted
with increasing alcohol concentration thus indicating a decrease
of melt viscosity of tlae terpolymers in all runs. ~otn improved
strength as well as improved melt.flow characteristics were
achieved with, for example, the higher et~ncentration poly-
propylene. glycols. Td~ae temperature-alcohol presence study
presented in Table l~ demonstrates the flexibility of alcohol.
modified, ester terminated terpolymers, for example, in tale
elimination of the reguirements of 'two temperature stage poly-
merization: The mole '~ alcohol of all examples and tables is
based on the excess amide coneentration.and corresponds
approximately with t:-~e ~ of prepolymer imide end groups whieit
are replaced by ester groups, and according to the invention
tine corresponding $ of ester enct group termination of ttie
l.actam polyol-polyacyl lactam or lac-tam-polyol-acyZ polylactam
terpolymers ,
'~ ~
'.' r; ~ ,....
. .. '
...' .. , .... , .; . ' . . . y : . : , ; ::. . ' .' . .. ': : , . .:. . ....
.., ,:... rw~~
