CA1050194A - Terpolymers containing ester and amide linkages - Google Patents
Terpolymers containing ester and amide linkagesInfo
- Publication number
- CA1050194A CA1050194A CA194,878A CA194878A CA1050194A CA 1050194 A CA1050194 A CA 1050194A CA 194878 A CA194878 A CA 194878A CA 1050194 A CA1050194 A CA 1050194A
- Authority
- CA
- Canada
- Prior art keywords
- lactam
- polyol
- alkylene
- terpolymer
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
Abstract
ABSTRACT OF THE DISCLOSURE
Lactam-polyol-polyacyl lactam or lactam-acyl-polylactam terpolymers having both ester linkages and amide linkages between the monomeric segments and optionally alcohol modified or ester terminated end groups are disclosed.
Also disclosed is a process for preparing the above terpolymer comprising reacting together a lactam, polyol, polyacyl lactam or acyl polylactam, and optionally an alcohol in the presence of a basic lactam polymerization catalyst. The lactam-polyol-polyacyl lactam or acyl polylactam terpolymers of this invention have characteristic properties which make them especially suitable for use as fibers, fabrics, films and molded articles under a wide range of conditions.
Lactam-polyol-polyacyl lactam or lactam-acyl-polylactam terpolymers having both ester linkages and amide linkages between the monomeric segments and optionally alcohol modified or ester terminated end groups are disclosed.
Also disclosed is a process for preparing the above terpolymer comprising reacting together a lactam, polyol, polyacyl lactam or acyl polylactam, and optionally an alcohol in the presence of a basic lactam polymerization catalyst. The lactam-polyol-polyacyl lactam or acyl polylactam terpolymers of this invention have characteristic properties which make them especially suitable for use as fibers, fabrics, films and molded articles under a wide range of conditions.
Description
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:
~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.
,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 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 - where 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,~
U
a ~ ~
a p ?C
A
_ _.
~~~_ __.-_.«
A
~~r~
i ' ~~
' v1 1 .
:i ' ' i .._ .:I ~ I ' ~ x-:!
t .'~, . ...
,/'~ '~ .
' ,:
.;
_.~
_~_ 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 n1. ~'.
~ 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.
_ __-_ __ ~__. ______ _._._____.
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:
~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.
,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 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 - where 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,~
U
a ~ ~
a p ?C
A
_ _.
~~~_ __.-_.«
A
~~r~
i ' ~~
' v1 1 .
:i ' ' i .._ .:I ~ I ' ~ x-:!
t .'~, . ...
,/'~ '~ .
' ,:
.;
_.~
_~_ 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 n1. ~'.
~ 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 AB AA qA sA
-. _ C ~ ~ P C '' p ~ _' ~~. _ P .-.
-_.
~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~.~
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_
-. _ C ~ ~ P C '' p ~ _' ~~. _ P .-.
-_.
~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~.~
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 ' ~ .. ,. ~ ..
.
~-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
~ '' f~ N
~
''~
"J
i ~
r--1 ~ -N
~
~
s-I r- Q ,4 ili1c O U 1 I
'~ 9~
: ti ~
J
.
'r13 ~ N
r-1 '; ~ ~ a m '~ ~ ~ O
U ~ ''d ~ N ~ W ~
~ ~ r N
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
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~.
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 .
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.tea ' ~
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. . .
-;'l . . .
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, .
.
' 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 . ,~, .
: ~ , , .
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~ .:~.
, -, ~ . ~
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;
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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 , ~
''. 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 -~ '~.
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N ~ U ~
H H x L'.
U
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O l9 lfl l9 tO tn l0 tn O
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H~M~ltnhNOCIN
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ro o~ .~~
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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.
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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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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 ' ~ .. ,. ~ ..
.
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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.
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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.
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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 , ~
''. 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
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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.
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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. .
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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 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.
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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.
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 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.
. ,.,.; 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
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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 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.
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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.
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 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.
. ,.,.; 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 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.
Table 19 Effect of Decyl Alcohol Tensile Run ~ Decyl M1 Decyl Strength 250°C
No. Alcohol Alcohol Fail $ Elon- Modulus Melt 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 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~~
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 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.
Table 19 Effect of Decyl Alcohol Tensile Run ~ Decyl M1 Decyl Strength 250°C
No. Alcohol Alcohol Fail $ Elon- Modulus Melt 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 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~~
Claims (41)
1. A terpolymer having both ester linkages and amide link-ages between monomeric segments comprised of lactam, polyol, and a polyacyl lactam or acyl polylactam of the formula:
where A and A' are acyl group selected from Y is an alkylene group having at least three carbon atoms, R is a hydrocarbon group, y is an integer equal to one or more, and n is an integer equal to zero or one; said terpolymers being com-prised of from at least 10% to about 90% by weight of polyol segments, and optionally said terpolymer having alcohol modified, 0.1% or more ester terminated end groups.
where A and A' are acyl group selected from Y is an alkylene group having at least three carbon atoms, R is a hydrocarbon group, y is an integer equal to one or more, and n is an integer equal to zero or one; said terpolymers being com-prised of from at least 10% to about 90% by weight of polyol segments, and optionally said terpolymer having alcohol modified, 0.1% or more ester terminated end groups.
2. A terpolymer according to claim 1 wherein the lactam portion of the terpolymer is formed from a lactam of the formula where Y is an alkylene group having at least about 3 carbon atoms.
3. A terpolymer according to claim 2 wherein the lactam is .epsilon.-caprolactam.
4. A terpolymer according to claim 1 wherein the polyol portion of the terpolymer as formed from alkylene glycol.
5. A terpolymer according to claim 4 wherein said alkylene glycol is a polyalkylene glycol having a molecular weight of at least about 1000.
6. A terpolymer according to claim 5 wherein said poly-alkylene glycol is polyethylene glycol.
7. A terpolymer according to claim 6 wherein said poly-alkylene glycol is polypropylene glycol.
8. A terpolymer according to claim 5 wherein said poly-alkylene glycol is polytetramethylene glycol.
9. A terpolymer according to claim 1 wherein the polyol portion of the terpolymer is formed from polybutadiene diol.
10. A terpolymer according to claim 1 wherein the polyol portion of the terpolymer is formed from a polyester.
11. A terpolymer according to claim 10 wherein said poly-ester is polycaprolactone diol.
12. A terpolymer according to claim 1 wherein the acyl groups of all of said ester and amide linkages are carbonyl groups.
13. A copolymer according to claim 1 wherein said terpoly-mer is a block polymer.
14. A copolymer according to claim 3 wherein said block terpolymer is of the repeating AB block structure.
15. A copolymer according to claim 1 wherein said terpoly-mer is a caprolactam-polyalkylene glycol block polymer with phthaloyl linkages between the blocks.
16. A process for preparing terpolymers having both ester linkages and amide linkages between monomeric segments comprising mixing together lactam monomer, polyol, basic lactam polymeri-zation catalyst, a polyacyl lactam or acyl polylactam; of the formula where A and A' are acyl groups selected from Y is an alkylene group having at least about three carbon atoms, R is a hydrocarbon group arid n is an integer equal to zero or one, y is an integer equal to one or more and optionally an alcohol and polymerizing said lactam, polyol, polyacyl lactam or acyl polylactam, and optionally alcohol to form the terpoly-mer comprised of at least 10% to about 90% by weight of polyol segments and optionally having 0.1% or more ester end group termination.
17. A process according to claim 16 wherein said polyol, alcohol, and polyacyl lactam or acyl polylactam are reacted before said lactam is added to the polymerization mixture.
18. A process according to claim 16 wherein said polyol, alcohol, and polyacyl lactam or acyl polylactam are reacted before said lactam polymerization catalyst is added to the polymerization mixture.
19. A process according to claim 16 wherein said polymer-ization catalyst is an alkali metal or alkaline earth metal lactam or a halogenated alkaline earth metal lactam.
20. A process according to claim 19 wherein said polymer-ization catalyst is a bromomagnesium lactam.
21 A process according to claim 16 wherein said alcohol is functionally monohydric.
22. A process according to claim 21 wherein said mono-hydric functional alcohol has the formula ROH where R is an aliphatic or substituted aliphatic hydrocarbon.
23. A process according to claim 21 wherein said func-tionally monohydric alcohol having the formula ROH is comprised of polymeric R groups which are soluble in lactam.
24. A process according to claim 21 wherein said alcohol presence is from about 0.1% to about 150% of the molar equiva-lents of excess imide groups from acyl polylactam or polyacy-lactam based on the molar equivalents of hydroxyl from polyol present.
25. A process according to claim 22 wherein said alcohol is at least one of decyl, 2-octano, and 1-propanol.
26. A process according to claim 16 wherein said acyl polylactam is an acyl bis-lactam.
27. A process according to claim 16 wherein said polyacyl lactam is a bis-acyl lactam.
28. A process according to claim 27 wherein said bis-acyl lactam is terephthaloyl bis-caprolactam.
29. A process according to claim 27 wherein said bis-acyl lactam is isophthaloyl bis-caprolactam.
30. A process according to claim 16 wherein the polymer-ization reaction of the lactam, polyol and polyacyl lactam is carried out at a temperature from about 90 to about 190°C.
31. A process according to claim 16 wherein the polymeriz-ing is carried out at an initial temperature of about 70 to about 100°C and is increased to about 150 to about 180°C during the polymerization reaction.
32. A lactam-polyol-polyacyl lactam terpolymer having both ester linkages and amide linkages between monomeric segments of the terpolymer and optionally from 0.1% or more ester end group termination.
33. A lactam-polyol-acyl polylactam terpolymer having bath ester linkages and amide linkages between monomeric segments of the terpolymer, and optionally from 0.1% or more ester end group termination.
34. A lactam-polyol-acyl polylactam block terpolymer having the general formula:
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, X is an aryl group selected from Y is an alkylene or substituted alkylene having from about 3 to about 14 carbon atoms:
x, x', x" arid 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.
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, X is an aryl group selected from Y is an alkylene or substituted alkylene having from about 3 to about 14 carbon atoms:
x, x', x" arid 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.
35. A process for preparing lactam-polyol aryl polylactam terpolymers having the general formula:
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;
X is an acyl group selected from 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; comprising mixing to-gather lactam monomer, polyol, basic lactam polymerization cata-lyst, and a polyacyl lactam; and polymerizing the lactam, polyol and acyl polylactam to form the block terpolymer.
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;
X is an acyl group selected from 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; comprising mixing to-gather lactam monomer, polyol, basic lactam polymerization cata-lyst, and a polyacyl lactam; and polymerizing the lactam, polyol and acyl polylactam to form the block terpolymer.
36. A lactam-polyol-polyacyl lactam terpolymer having the general formula:
wherein (O-Z)Z is a polyol segment and 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 group;
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 is equal to 2w+2;
z and w are integers of equal to one or more;
and said lactam-polyol-polyacyl lactam block terpolymers are comprised of at least about 18 to about 90 percent by weight of polyol blocks.
wherein (O-Z)Z is a polyol segment and 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 group;
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 is equal to 2w+2;
z and w are integers of equal to one or more;
and said lactam-polyol-polyacyl lactam block terpolymers are comprised of at least about 18 to about 90 percent by weight of polyol blocks.
37. A process for preparing lactam-polyol-lactam block terpolymers having the general formula:
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 ar polyvalent hydrocarbon group;
Y is an alkylene ox 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;
z and w are integers equal to one or more;
and said lactam-polyol-polyacyl lactam block terpolymers are comprised of at least about 18 to about 90 per cent by weight of polyol blocks; comprising mixing together lactam monomer, polyol, basic lactam polymerization catalyst and a polyacyl lactam; and polymerizing the lactam, polyol and polyacyl lactam to form the block terpolymer.
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 ar polyvalent hydrocarbon group;
Y is an alkylene ox 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;
z and w are integers equal to one or more;
and said lactam-polyol-polyacyl lactam block terpolymers are comprised of at least about 18 to about 90 per cent by weight of polyol blocks; comprising mixing together lactam monomer, polyol, basic lactam polymerization catalyst and a polyacyl lactam; and polymerizing the lactam, polyol and polyacyl lactam to form the block terpolymer.
38. The polymer according to claim 36 in which the propor-tion of polyol blocks is about 28 per cent or more by weight of the polymer.
39. The polymer according to claim 36 wherein the lactam blocks are formed from a lactam monomer of the formula , the polyol blocks are formed from a polyalkylene glycol of number average molecular weight of about 500 to 4000, and the polyacyl linkages are formed from polyacyl lactam of the formula
40. A lactam-polyol -polyacyl lactam block terpolymer or a lactam-polyol-acyl polylactam block terpolymer having at least about 5% ester end group termination and the general formula:
Wherein (O-Z)2 is a polymeric moiety and Z is a hydrocarbon or substituted hydrocarbon group said group being alkylene, ary-lene, alkylene carbonyl, arylene carbonyl, and, mixtures thereof;
A and A' are acyl groups selected from R is a divalent hydrocarbon group;
n is an integer equal to zero or one;
E is an imide group of the formula or an ester group of the formula -O-R' where the -O-R' is the residual of a monohydric functional alcohol;
Y is an alkylene or substituted alkylene having from about 3 to about 14 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.
Wherein (O-Z)2 is a polymeric moiety and Z is a hydrocarbon or substituted hydrocarbon group said group being alkylene, ary-lene, alkylene carbonyl, arylene carbonyl, and, mixtures thereof;
A and A' are acyl groups selected from R is a divalent hydrocarbon group;
n is an integer equal to zero or one;
E is an imide group of the formula or an ester group of the formula -O-R' where the -O-R' is the residual of a monohydric functional alcohol;
Y is an alkylene or substituted alkylene having from about 3 to about 14 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.
41. A process for preparing a lactam-polyol-polyacyl lactam block terpolymer or a lactam-polyol-acyl polylactam block ter-polymer or a lactam-polyol-acyl polylactam block terpolymer having the general formula:
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 R is a divalent hydrocarbon group;
n is an integer equal to zero or one;
E is an imide group of the formula or an ester group of the formula -O-R', where the -O-R' is the residual of a monohydric functional alcohol;
y is an alkylene or substituted alkylene having from 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 off x' is equal to 2w+2; and z and w are integers equal to one or more, com-prising mixing together lactam monomer, polyol, monohydric alcohol, basic lactam polymerization catalyst and polyacyl lactam or acyl polylactam and polymerizing the lactam, polyol and poly-acyl lactam or acyl polylactam to dorm block terpolymer, having at least 5% ester group termination.
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 R is a divalent hydrocarbon group;
n is an integer equal to zero or one;
E is an imide group of the formula or an ester group of the formula -O-R', where the -O-R' is the residual of a monohydric functional alcohol;
y is an alkylene or substituted alkylene having from 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 off x' is equal to 2w+2; and z and w are integers equal to one or more, com-prising mixing together lactam monomer, polyol, monohydric alcohol, basic lactam polymerization catalyst and polyacyl lactam or acyl polylactam and polymerizing the lactam, polyol and poly-acyl lactam or acyl polylactam to dorm block terpolymer, having at least 5% ester group termination.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE7502055A SE402832B (en) | 1974-03-13 | 1975-02-24 | ELONG, NARROW NUCLEAR REACTOR FUEL ELEMENT |
| FR7507855A FR2264365A1 (en) | 1974-03-13 | 1975-03-13 | Metal sheath for nuclear fuel tablets - with low strength lining |
| DE2511054A DE2511054C2 (en) | 1974-03-13 | 1975-03-13 | Nuclear fuel rod for nuclear reactors |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US34121573A | 1973-03-14 | 1973-03-14 | |
| US42363973A | 1973-12-10 | 1973-12-10 | |
| US423591A US3862262A (en) | 1973-12-10 | 1973-12-10 | Lactam-polyol-acyl polyactam terpolymers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1050194A true CA1050194A (en) | 1979-03-06 |
Family
ID=27407446
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA194,878A Expired CA1050194A (en) | 1973-03-14 | 1974-03-13 | Terpolymers containing ester and amide linkages |
Country Status (15)
| Country | Link |
|---|---|
| JP (1) | JPS5440120B2 (en) |
| AR (1) | AR199246A1 (en) |
| BR (1) | BR7401912D0 (en) |
| CA (1) | CA1050194A (en) |
| CH (1) | CH628360A5 (en) |
| DE (1) | DE2412106A1 (en) |
| ES (1) | ES424226A1 (en) |
| FR (1) | FR2221478B1 (en) |
| GB (1) | GB1472463A (en) |
| IL (1) | IL44416A (en) |
| IT (1) | IT1007674B (en) |
| LU (1) | LU69633A1 (en) |
| NL (1) | NL180758C (en) |
| SE (1) | SE422582B (en) |
| SU (1) | SU843759A3 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS521038B2 (en) * | 1974-04-11 | 1977-01-12 | ||
| JPS53103080A (en) * | 1977-02-17 | 1978-09-07 | Sachiko Aono | Cloth coloring composition |
| JPH0116086Y2 (en) * | 1979-01-24 | 1989-05-12 | ||
| JPS63291921A (en) * | 1987-05-22 | 1988-11-29 | Sumitomo Chem Co Ltd | Polyether polyamide copolymer having ethylenically unsaturated group |
| US5223335A (en) * | 1991-03-18 | 1993-06-29 | Teijin Limited | Fiber-reinforced composite material and process for the production thereof |
| WO2011162333A1 (en) | 2010-06-23 | 2011-12-29 | ナガセケムテックス株式会社 | Impact-resistant polyamide composition and process for production of same |
| KR102275688B1 (en) * | 2017-11-28 | 2021-07-12 | 한화솔루션 주식회사 | Process for producing end-capped polyamides via anionic ring-opening polymerization |
| KR102262504B1 (en) * | 2017-11-28 | 2021-06-08 | 한화솔루션 주식회사 | Process for producing polyamides including double activated group via anionic ring-opening polymerization |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD36943A (en) * | ||||
| DE1495661A1 (en) * | 1961-12-23 | 1969-08-07 | Bayer Ag | Process for the production of polyamides |
| GB1067153A (en) * | 1963-05-17 | 1967-05-03 | Ici Ltd | Grafted polyamides |
| US3366608A (en) * | 1965-04-15 | 1968-01-30 | British Celanese | Anionic polymerization of caprolactam |
| DE1745238A1 (en) * | 1967-03-25 | 1971-08-12 | Plate Gmbh Chem Fab Dr | Polyamide-forming, storable mixtures of lactams and catalysts |
| NL6908380A (en) * | 1969-06-03 | 1970-12-07 |
-
1974
- 1974-03-13 BR BR1912/74A patent/BR7401912D0/en unknown
- 1974-03-13 IL IL44416A patent/IL44416A/en unknown
- 1974-03-13 GB GB1121474A patent/GB1472463A/en not_active Expired
- 1974-03-13 LU LU69633A patent/LU69633A1/xx unknown
- 1974-03-13 CH CH348274A patent/CH628360A5/en not_active IP Right Cessation
- 1974-03-13 JP JP2894774A patent/JPS5440120B2/ja not_active Expired
- 1974-03-13 SU SU742012459A patent/SU843759A3/en active
- 1974-03-13 ES ES424226A patent/ES424226A1/en not_active Expired
- 1974-03-13 CA CA194,878A patent/CA1050194A/en not_active Expired
- 1974-03-13 FR FR7408456A patent/FR2221478B1/fr not_active Expired
- 1974-03-13 SE SE7403331A patent/SE422582B/en not_active IP Right Cessation
- 1974-03-13 DE DE2412106A patent/DE2412106A1/en active Granted
- 1974-03-13 NL NLAANVRAGE7403367,A patent/NL180758C/en not_active IP Right Cessation
- 1974-04-08 IT IT20881/74A patent/IT1007674B/en active
- 1974-05-13 AR AR252751A patent/AR199246A1/en active
Also Published As
| Publication number | Publication date |
|---|---|
| NL180758C (en) | 1987-04-16 |
| LU69633A1 (en) | 1974-10-17 |
| GB1472463A (en) | 1977-05-04 |
| DE2412106C2 (en) | 1988-12-01 |
| IL44416A0 (en) | 1974-06-30 |
| BR7401912D0 (en) | 1974-12-03 |
| JPS5440120B2 (en) | 1979-12-01 |
| JPS5029553A (en) | 1975-03-25 |
| DE2412106A1 (en) | 1974-09-19 |
| AR199246A1 (en) | 1974-08-14 |
| AU6662074A (en) | 1975-09-18 |
| NL180758B (en) | 1986-11-17 |
| SU843759A3 (en) | 1981-06-30 |
| IL44416A (en) | 1976-12-31 |
| SE422582B (en) | 1982-03-15 |
| FR2221478B1 (en) | 1977-09-30 |
| ES424226A1 (en) | 1977-01-01 |
| IT1007674B (en) | 1976-10-30 |
| NL7403367A (en) | 1974-09-17 |
| FR2221478A1 (en) | 1974-10-11 |
| CH628360A5 (en) | 1982-02-26 |
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