Note: Descriptions are shown in the official language in which they were submitted.
~:~3~
Field of the Invention
-
This in~ention relates to thermoplastic poly-
amide compositions, and more particularly to such composi-
tions having improved ductility or toughness, and to the
processes for prepa~ing such compositions~
Unmodified thermoplastic polyamides are
generally regarded as "tough"~ For example, the po]yamides
have good elongation; high energy to break, as dernonstrated
in tensile tests; high tensile impact strength and high
energy absorption as demonstrated in falling dart tests,
e~g., the Gardner impact test. In one aspect of toughness
the po~yamide materials are quite deficien~; namely,
resistance to crack propagation. This de~iciency is
reflected in notch sensitivity~ bri-ttle breaks and
occasional catastrophic failure of molded or extruded
parts. The tendency of polyamides to break in a brittle
rakher than ductile fashion is a significant limitation
of utili-ty. A resin may be characterized in its tendency
toward ductility by the notched Izod test ~Sl~I D~256 56.
With the normal notch radius of 10 mils,
polyhexamethylene adipamide (66 nylon), dry as molded~
will have a notched Izod value of about 1 fto lb./inch
of' notch~
There is much prior ~rt concerned with improving
the impact strength Or polyamides~ ~ variety of additives
have been added to polyamides with some impro~ement in
toughness being obtained. British Patent 99~4399 for
example~ discloses a thermoplastic co.rnposition comprising
" .
. .
~ 3 ~ ~6 ~
a mixture of 50 to 99 percent linear polyamide and 1 to
50 percent of olefin copolymer particles) the olefin
copolymer containing from 0.1 to 10 mole percent of acid
groups. Many olefin copolymers are disclosed, but it is
not required that the olefin copolymers have a tensile
modulus of 50,000 or less. The dry as molded notch
sensitivity increases ko 4.6 fto lbsO/inch as the copolymer
is increased to ~0 percent by weight as described in
Example 1.
Murch U. S. Patent 3,~5,163 discloses blends of
60 to ~5 percent by weight polyamide and an acid-
containing olefin polymer in which the acid is derived
from an ~ ethylenically unsaturated carboxylic acid
and in which at least 10 percent of the acid groups have
been neutralized with metal ions~ Murch is concerned
primarily with weld-line toughness which does not have a
specific relation with blend toughness. The Murch blend,
however, also demonstrates impro~ement over the composi-
- tion of British Patent 99~9~39 with respect to blend
toughness. Murch did not recognize that improved blend
toughness of polyamide compositions can be achieved at
lower concentration levels of polymer addition provided
that at least one polymer present has a tensile modulus
o 50,000 or less and the ratio of the tensile modulus
of the polyamide to the tensile modulus of said polymer
is greater than 10 to 1.
Two U. S. Patents, Kray et al. 3~3g~91g6 and
Seven et al. 3,~65jo59 disclose polyamide compositions
~hich possess high impact strength~ some values being
greater than 10 ft~ lbs./inch~ The disclosed compositions
--3--
~-~3.,~
are graft copolymers prepared from an ethylene containing
copolymer. The disclosed copolymers do not contain sites
which adhere to the polyamide through sites of the poly-
amide. There is also no recognition that the tensile
modulus of the ethylene containing copolymer is no
greater than 50,000 p.s.i. or that particle size is
importantO Furthermore, the Izod impact strength is
determined with samples held at 50 percent relative
humidity for 3 days prior to testing as disclosed in
UO S. Patent 3,3g~ 6~ In some composition$ moisture
causes sharp increases in the notched Izod value. This
is shown in Table 1J page 6 of British Patent 99~439
Owens et al~ U. S~ Patent 3,66~,274 teaches
modestly improved impact strength of polycarbonamides
modified with ~A) a first elastomer phase of copolymers or
terpolymers and (B) a final rigid phase thermoplastic
stage containing amine-reactive moieties9 preferably
carboxylic acid groups. The soft modifier is coated ~ith
a rigid layer thus negating a large impro~ement in poly~
amide toughness that could be achieved with a copolymer
rnodifier.
SU~,~
According to this invention, there is provided
a toughened multi-phase thermoplastic composition consisting
essentially of one phase containing ~0 to 99 percent by
~Jeight of a polyamide matrix resin of number average
molecular weight of at least 5000, and 1 to ~0 percent by
weight of at least one other phase containing particles of
at least one polymer taken from the class consisting of
branched and straight chain polyrners having a particle
~3~
CYL~
size in the range of 0.01 to ~. n -~1~3~and being
adhered to the polyamide matrix resin, and said at least
one polymer having a tensile modulus in the range of about
1.0 to 50,000 psi, the ratio of the tensile modulus of
the polyamide matrix resin to tensile modulus of said at
least one polymer beiny greater than 10 to 1.
The term "consisting essentially of" means that
in addition to the required polyamide matrix resin and
the at least one polymer other components can be present
in the toughened composition provided that the basic and
essential characteristics of the toughened composition
are not materially affected thereby.
The term "branched and straight chain polymers"
means that -the polymers are not crosslinked to a degree
which will increase their modulus to greater than 50,000
psi or decrease their melt flow to a level which prevents
effective dispersion.
According to another aspect of this invention,
there is provided a process for the preparation of a
toughened multi-phase thermoplastic composition which
comprises, in a closed system, (a) admi~ing (1) 60 to
99 percent by weight of a polyamide matrix resin of
number average molecular weight of at least 5000, and
(2) 1 to 40 percent by weight of at least one polymer
at a temperature in the range of about 5 to 100C above
the melting point of sa.id polyamide matrix resin and (b)
shearing to disperse the polymer in said matrix to a
particle size in the range of 0.01 to 3.0 micron, said
at least one polymer being adhered to said matrix and
having a tensile modulus in the range of 1.0 to 50,000
~'~
, ....
p-Soi~ ~ the ratio of the tensile modulus of` said matrix
to tensile modulus of said at least one polymer being
greater than 10 to 1.
~=~ .
The polyamide matrix resin of the tou~hcned
compositions of this invention is well known in the art
and embraces those semi-crystalline and arnorphous resins
having a mo]ecular weight of at least 5000 and commonly
ref`erred to as nylons. Suitable polyamides include those
described in U. S. Patents 2~0719250; 2,071,251; 2,130~5239
29130,9~; 2,241~322; 2,3129966; 29512,606; and 39393,210D
me polyamide resin can be produced by condensation of
equimolar amounts of a sat~rated dicarboxylic acid con-
taining from 4 to 12 carbon atoms with a diamine, in
which the diamine contains from L~ to 14 carbon atomsO
~xcess diamine can be employed to provide an excess of
amine end groups over carboxyl end groups in the polyamide.
~xamples of polyamides include polyhexamethylene adipamide
(66 nylon)~ polyhexamethylene azelaamide (69 nylon)~
polyhexamethylene sebacamide (610 nylon)~ and polyhexa-
methylene dodecanoamlde (~12 nylon)~ the polyamide
produced by ring opening of lactams~ i~e. 7 polycaprolac-tam7
polylauric lactam, poly~ amino~undecanoic acid 9 bis(para-
aminocyclohexyl) methane dodecanoami~e. It is also possible
to use in this inven~ion polyamides prepared by thc
copolymeriæation of two of the above polymers or ter-
polymerization of the above polymers or their components9
e.g~y for example, an adipic~ isophthalic acid hexa-
methylene diamine copolyrner~ Preferably the poly~nides
~ are linear with a melting point in excess o~ 200C. As
~6--
great as 99 percent by weight of the composition can be
composed of polyamide; however, preferred compositions
contain from 60 to 99 percent, and more narrowly 80 to
95 percent, by weight oi polyamide.
The composition is toughened by the combination
of at least one polymer with the polyamide. The term
"at least one polymer" means one or more polymers which
co-exist in single discrete particles having a particle
size ranging from 0.01 to 3.0 microns, preferably 0.02 to
1 micron, within the matrix, so that either the mixture
of polymers or at least one of the polymers in the mixture
meets the following criteria:
(a) sites which adhere to the polyamide matrix;
(b) tensile modulus, as added, in the range
of about 1.0 to 20,000 psi, preferably
about 5 to 20,000 psi, the ratio of
tensile modulus of the polyarnide matrix
resin to tensile modulus of said at least
one polymer being greater than 10 to 1,
preferably greater than 20 to 1.
The polyamide is the continuous phase in the
composition and the polymer performs the function of a
soft dispersed phase which is adhered to the polyamide
matrix. The polymer may be elastomeric, but it has
been found that thermoplastic polymers which are not
elastomeric are also effective in the compositions.
The polymers are branched or straight chain
and are of such composition that crosslinking other than
by reaction with the polyamide matrix is not necessary to
their function and excessive crosslinking ~ay, in fact,
, . ~ . . .
3:3~6i~
be harmful.
Branched and straight chain polymers useful as
the soft phase of the composition are represented by the
formula:
A(a~ B(b)-C(C)-D(d3~E(~) F(f~ G(g)-H(h)
derived in any order9 e~g~, random9 from monomers A ~o
H where
A is ethylene~
: B is C0;
, C is an unsaturated monomer taken from the class
consisting of ~ ethylenically unsaturated
carboxylic acids having from 3 to ~ carbon
atoms, and derivatives thereof taken from ~he
class consisting of monoesters of alcohol.s of
1 to 29 carbon atoms and the,dicarboxylic acids '
- and anhydrides of the dicarboxylic acid~ and
the metal salts of the monocarboxylic, di-
; carboxylic acids and the monoester of the di-
carboxylic acid having from 0 to 100 percent
of the carboxylic acid groups ionized by
neutralization with metal ions and dicarboxylic
acids and monoesters of the dicarboxylic acid
neutralized by amine-ended caprolactam oligomers
having a DP of 6 to-24;
D is an unsa.turated epoxide of 4 to 11 carbon
atoms;
E is the residue derived by the loss of nitrogen from
an aromatic sulfonyl azide substituted by
carboxyli.c acids taken from the clas,s consisting
of monocarhoxyl,ic and dicarboxylic acids having
from 7 to 12 carbon atoms and derivatlves
~3~
thereof taken from the class consisting of
monoeskers of alcohols of 1 to 29 carbon atoms
and the dicarboxylic acids and-anhydrides of the
dicarboxylic acids and the metal salts of the
monocarboxylic~ dicarboxylic acids and the
monoester of the dicarboxylic acid having
from 0. to lO0 percent of the carboxylic acid
groups ioni~ed by neutralization with metal
ions;
F is an unsaturated monomer taken from the class
consisting of acrylate esters having ~rom 4
to 2~ carbon atoms~ vinyl esters of acids
ha~i~g from l to 20 carbon atoms (substantially
no residual acid)~ vinyl ethers of 3 to 20 carbon
atoms, and vinyl and vinylidene halides,and
nitriles having from 3 to 6 carbon atoms;
G is an unsaturated monomer having pendant hydro-
carbon chains of l to 12 carbon a-tom~ capable
of being graf~ed with monomers having at least
one reactive group of the type defined in C9
D and ~, and pendant aroma~ic groups which may
have l to 6 substituent groups having a total
o~ 14 carbon atoms9 and
H is an unsaturated monomer taken from the class
consisting of branched~ straight chain and
cyclic compounds having from 4 to 14 carbon
atoms and at least one additional nonconjugated
unsaturated carbon-carbon bond capable of being
grafted with a monomer having at least one
reactive group of the type defined in C, D and E.
~9-
~3~
The aforementioned monomers may be present in
the polymer in the following mole fraction:
(a) 0 to 0095;
(b) 0 to 0.3;
~c) 0 to 0.5;
(d) 0 to 0~59
(ej 0 to 0~5,
(f) 0 to 0~99;
(g) to 0O~9; and
(h) 0 to 0~99
so that the total of all components is a mole fraction of
l~Oo
Pre~erably ~a) to (h~ are present in the
following mole fraction:
(a) 0 to 0.9;
~b) 0 to 0.2~ most pr~ferably O.l to 0.2
- (c~ 0.0002 to 0~2, most pre~erably 0.002
to 0O05;
(d~ 0~005 to 002, most preferably OoOl
~0 to O.l;
(e) 0.0002 to O.l, most preferably 0~002
to 0,Ol;
(f) 0 ~o 0.9~,
(g~ 0 to 0~9g; and.
(h~ 0 to 0~9~ .
In place of the aforementi.oned polymers can be
used either:
I apolyurethane which is the reaction product
~ of at least one glycol taken from the class
cons-isting of' polyester glycol ha~ing an average
molecular weight of' 300 to 6,000 and a polyether
--:LO--
~33~
g1YGO1 having an a~erage molecular weight of
300 to 6~ooo and optionally at least one diol
having a molecular weight of less than 3009
and at least one diisocyanate having 4 to
21 carbon atoms; or
J a polymer containing polyether repeat uni-ts taken
from the class consisting of the reaction product -~
of epoxide~containing monomers having 2 to 3
carbon atoms~ an epoxide-containing monomer
having pendant groups taken from the class
consisting of methyl or chloromethyl groups,
and mixtures of said epo~ide monomersO
Each of polymers I or J; when present, replace the polymer
containing components A to H. Preferably Polymer I is
used with polya~ides which melt at temperatures below
200C~ whereas preferably Polymer J is used with poly-
amides which melt at tempera~ures below 225C.
At least one of Bt Cp D and E is present in all
polymeric systems wi~h the exception of I and J. When A
is present9 in addition to at least one of B9 C~ D and
E being present7 at least one of F9 G and H is also
present. A mixture of two or more polymers can be used
with the proviso that at least one of B, C9 D and E is
present in at least one of the polymersO Since I and J
are polymers which contain adherent sites9 the presence
Of BJ C~ D and E is not necessary.
The polymeric component of the toughened
composition may be prepared by standard copolymerization
reaction or by a grafting reacti.on. Thus B, C~ D and E
may be copolymerized with A, F7 G and H and C, D and E
may be added by a grafting reacti.on,
~ 3~
Illustratire of monomers C to H of the above
formula are:
C is maleic acid~ maleic anhydride~ maleic acid
monoethyl esterJ metal salts of acid monoethyl
ester7 fumarlc acid, fumaric acid monoethyl
ester, itaconic acid9 vinyl benzoic acid, vinyl
phthalic acid~ metal salts of fumaric
acid monoethyl ester7 monoesters of maleic,
~umaric~ itaconic acids with R
where R is up to 29 carbon atoms~ e.g~, methyl,
propyl, isopropylS butyl, isobutyl, hexyl9
cyclohexyl~ octyl, 2-ethyl hexyl, decyl9
stearyl9 methoxy ethyl, ethoxy ethyl, hydroxy
ethyl~ etc a
D is glycidyl methacrrlate9 glycidyl acrylate9
allyl glycidyl ether, vinyl glycidyl ether,
glycidyl itaconate9 etcO
E is phthalic anhydride sulfonyl azide~ methyl
ester and monooctadecyl ester of phthalîc
~ - anhydride sulfonyl azide, benzoic acid sulfonyl
a~ide, naphthoic acid sulfonyl azide~ naphthoic
- diacid sulfonyl azide~ R-monoesters (and metal
salts thereof) of phthalic acid and naphthoic
diacid sulfonyl azide, ~here R is up to 29
carbon atoms9 etc.;
. F is methyl methacrylate~ butyl acrylate, ethyl
acrylateg vinyl acetate9 methyl vinyl ether,
zinc methacrylate, acr~lonitrile, R - esters
~ of acrylic, methacrylic acids; ~ - vinyl
ethers9 vinyl benzoate, vinyl naphthoate,
~12-
vinyl esters of R acids, where R is up to l~
carbon atoms, vinyl chlorideS vinylidene
fluoride, etc O;
G is styrene, propylene9 isobutylene9 vinyl
naph~halene 9 vinyl pyridine, vinyl pyrrolidone,
mono-, di-, ~richloro styrene9 R'-styrene where
R' is 1 to lO carbon atoms~ butene, hexene~
octene~ decene, etc.; and
X is hexadiene~ norbornadiene, butadiene~ iso~
~0 prene, divinyl, allyl styrene9 etc.
Polymer I includes: reaction products of diiso-
cyanates, e~g., 2,4- or 2~6-toluene diisocyanate
and mixtures, ~ methylene bis phenyl isocyanate, hexa- -
methylene diisocyanate, 4g~'-methylene bis cyclohexyliso-
cyanatej glycols, e~g~, di(betaoxyethyl~ ether of
hydroquinone~ poly~ethylene adipate) ~lycol9 poly~l9~-
butylene adipate glycolS polypropylene ether glycol~
polytetramethylene ether glycol; diols~ e.g., ethylene
gl~col, l~-butanediol, etcO Polymer J includes~0 ethylene oxide, propylene oxide, epichlorohydrin, etcO
Useful polymers for toughening polyamide
compositions are the following alternating or primarily
random polymers:
zinc salt of ethylene/isobutyl acrylate/methacrylic
acid; ethylene/methyl acrylate/monoethyl ester of maleic
anhydride and 0 to 100 percent neutralized zinc, sodium,
calcium, lithium7 antimony, and potassium salts thereof;
ethylene/methyl acrylate/monoethyl ester of maleic
anhydride partially neutralized with an amine ended
oligomer of caprolactam; mixture of ethylene/isobutyl
~13-
~ 33 ~
acrylate/methacrylic acid and ethylene/methyl acrylate/
monoethyl ester of maleic anhydride and zinc salts thereof;
~thylene/methyl acrylate/methacrylic acid and zinc salts
thereof; ethylene/vinyl acetate/methacrylic acid and zinc
salts thereof; ethylene/methyl methacrylate/methacrylic
acid and zinc salts thereof; ethylene/vinyl acetate/
carbon monoxide; mixtures of ethylene/vinyl acetate/
carbon monoxide and a zinc salt of ethylene/isobutyl
acrylate/methacrylic acid; mixtures of ethylene/vinyl
acetate and a zinc salt of ethylene/isobutyl acrylate/
methacrylic acid; mixtures o~ ethylene/isob~tyl acrylate
and a zinc salt of ethylene/isobutyl acrylate/methacrylic
acid; mixtures of ethylene/acrylic acid and'ethylene/
vinyl acetate; ethylene/isobutyl acrylate/carbon monoxide;
ethylene/stearyl methacrylate/car'bon monoxide; ethylene/
n butyl acrylate/carbon monoxide; ethylene/2-ethyl hexyl
methacrylate/carbon monoxide; ethylene/methyl vinyl ether/
carbon monoxide; ethylene/vinyl acetate/maleic anhydride?
ethylene/vinyl acetate monoethyl ester of maleic
anhydride; ethylene/~inyl acetate/glycidyl methacrylate;
ethylene/propylene/],4 hexadiene-g~maleic anhydride;
mixtures of ethylene/propylene/1,4 hexadiene and ethylene/
maleic anhydride; ethylene/propylene/norbornadiene/
1,4 hexadiene-g-benæoic acid sulfonyl azide; ethylene/
propylene/1~1~ hexadiene-g~phthalic anhydride sulfonyl
azide; mixtures o~ ethylene/propy].ene/1,4 hexadiene and
ethylene/propylene/1,4 hexadiene-g-maleic anhydride;
ethylene/propylene/194 hexadiene-g~maleic anhydride
neutraliz.ed with amine ended oligomer of caprolactam;
3 ethylene/propylene/1~4 hexadiene/maleic anhydride
~ ~3~
neutralized with zinc rosinake; ethylene/propylene/
1,4 hexadiene-g-fumaric acid; ethylene/propylene/
194 hexadiene/norbornadiene~g maleic anhydride; ethylene/
propylene/1,4 hexadiene/norbornadiene-g-monoethyl ester of
maleic anhydride; ethylene/propyl.ene/194 hexadiene/
norbornadiene-g-fumaric acid; ethylene/propylene/
1,~ hexadiene/glycidyl methacrylate; ethylene/propylene/
19~ hexadiene/norbornadiene-g-phthalic anhydride sulfonyl
azide; mixtures of ethylene/propylene/194 hexadiene and
ethylene/monoethyl ester of maleic anhydride; mixtures.
of ethylene/propylene/1,4 hexadiene and ethylene/butyl.
hydrogen maleate; mixtures of ethylene/propylene/
1,4 hexadiene and ethylene/maleic anhydride9 mixtures of
butadiene/acrylonitrile and styrene/maleic anhydride;
mixtures of styrene/~utadiene and ethylene/maleic
anhydride; isobutylene/isoprene-g-phthalic anhydride
sulfonyl azide; poly(isobutylene)-g-phthalic anhydride
sulfonyl azide; mixtures of ethylene/propylene/1,4-hexadiene/
norbornadiene and styrene/maleic anhydride; isoprene/
ph~halic anhydride; mixture~ of natural rubber and
ethylene/monoethyl ester o~ maleic anhydride; butyl
acrylate/monoethyl ester of fumaric acid~ ethyl acrylate/
fumaric acid; epichlorohydrin/ethylene oxide; mixtures
of ethylene/propylene and ethylene/monoethyl ester of
maleic anhydride; ethylene/propylene-g-phthalic anhydride
sulfonyl azi.de; ethylene/propylene/5~ethylidene~2-
norbornene-g fumaric acid, ethylene/propylene/dicyclo
pen~adiene-g monoethyl ester of maleic acid~ ethylene/
propylene/5-propenyl-2~norbornene-g-maleic anhydride,
ethylene/propylene/tetrahydroindene-g-f~maric acid,
-15-
~ 33 ~
ethylene/propylene/1,4-hexadiene/5-ethylidene~-
norbornene-g-fumaric acid.
The improvement in ductility of a compssi~ion
characterized by a higher notched Izod value is
approximately proportiona] to the concentration of
adherent sites in the polymeric component as well as
to the melt viscosity which is a measure of the molecular
weight9 and molecular weight distribution within the
limits of effective dispersion. ~Jhere high concentrations
of adherent sites are utilized, it ls generally possible
to mix two polymers together, i e., one as the source
of adherent sites~ and the other as a diluent. Mixing
may be accomplished by combining the polymers with the
polyamide separately or in combination with the proviso
that the polymer containing the adherent sites must not
be combined with the polyamide matrix resin prior to
combination of any other pol~ners~ In ethylene/
propy].ene/diene polymers molecular weights equivalent
to melt flow of 0.5 to ~00 g./10 mins. and more by-ASI~
D 123~ but at 2~0C. and a total l.oad of 2160 g~ are
effective~ In the variety of polymers employed a melt
flow range of more than 0.1 to 1~000 may be employed but
a range of 0~5 to 100 is preferredO
While not being limited to any theory, it is
believed that t~e soft phase polymer only has to adhere
with the polyamide matrix at the interface or sur~ace of
the two phases. The mechanism of adhesion is not fully
understood and may be achieved by bonds which vary in
energy from hydrogen bonding to covalent bonding.
The notched Izod test further characterizes
-lG~
~ ~ 3~
the composition with regard to its ductility~ Expressed
in fta lb./inch Or notch, notched Izod values in the
dry as molded condition for preferred polymers are at
least the values represented by the *ormula:
B ~ 0~2 C
~ ~ 2.0 ~ 0.5 (C2-lO~
B ~ 12.0
where B is the notched I~od of the polyamide
matrix polymer, CI is 2 to lO percent by
weight of the at least one polymer, and C2
is lO to 30 percent by weight of the at
least one pol~merO B ~ 12cO applies
between 30 and 40 percent9
It has been found generally that dry as molded
notched Izod ~alues of at least ~ ftD lbs./inch are
readily achieved at lower concentration values than is
achieved by prior art materials.
The melt flow of the thermoplastic composition
is in the range of 0.01 to 200 grams per minute by
20 ASTM D-123~ at 2~0~Co and 2160 g. load, preferably 0.1 to
lS0 grams per minute. Since the viscosity is highly shear
sensitive the compositions of the invention are well suited
for extrusion applications~
It is apparent from the above description that
a variety of polymers are effective in toughening
polyamides and a substantially large nl~ber of combina-
tions are usefulO It is therefore not surprising that
the limits of effectiveness of some components of the
compositions depend on the other components~ For
-17-
~ 3~
example, th~ lower limit of concentration of an effective
adhering site, e.g., maleic anhydride9 will probably
be lower than a less effective adhering sitej e.g.,
methacrylic acid. Similarly the balance between amine
and carboY~yl end groups in a matrix will influence the
comparative effecti~eness of different adherent sites of
the at least one polymer. Polymers or polymeric mixtures
in the lower modulus range tend to be more effecti~e than
those polymers or polymeric mixtures in the hi~her
modulus range and may be useful at lower concentrations
of adherent site. The equation describing the relation-
ship between notched Izod and concentration of pol-ymer is
applicable only for polymers ~ith an optirnum combina-
tion of adherence, modulus9 and particle size~ It is
also understood that the mixtures described herein
are effective only when the components of -the mixture
co-exist in the same discrete particles in the polyamide
matrix~ Howe~erD more than one such polymeric mixture
can be present in the toughaned thermoplastic composition.
The compositions of the invention may be modi-
fied by one or more conventional additives such as
stabilizers and inhibitors of oxidati~e, thermal, and
ultraviolet light degradation; lubricants and mold
release agents~ colorants including dyes and pigments,
fibrous and particulate fillers and rein~orcemen~s,
nucleating agents, plasticizers~ etc.
The stabilizers can be incorporated into the
composltion at any stage in -the preparation of the
thermoplastic cornposition. Preferably the stabilizers
are included early to preclude the initiation of
~L~l3~L6~
degradation before the composition can be protected.
Such stabilizers must be compatible with the compositionO
The oxidati~e and thermal stabilizers useful
in the materials of the present invention include those
used in addition polymers generally. They include, for
example~ up to 1 percent by weight9 based on the weight
of polyamide of Group I metal halides, e.g~, sodium,
potassium, lithium with cuprous halides9 eOg~, chloride,
bromide, iodide~ hindered phenols, hydroquinones,
and varieties of substi~uted members of those groups
and combinations thereof~
The ultraviolet light stabilizers7 e~g~, up to
2.0 percent~ based on the weight of polyamide~ can also be
those used in addition pol~ners generally. Examples of
ultra~iolet light stabilizers include various substituted
resorcinols, salicylates, benzotriazoles~ benzophenonesg
and the like.
Suitable lubricants and mold release agents9
e.g.~ up to loO percent~ based on the weight o~ the
composition; are stearic acid, stearic alcohol, stearamides;
organic dyes such as nigrosine2 etc.; pigments, e.gO 9
titanium dioxide9 cadmium sulfide9 cadmium sulfide
selenide, phthalocyanines9 ultramarine blue~ carbon
black, etc.; up-to 50 percent9 based on the weight of the
composition, of fibrous and particulate fillers and rein-
forcernents, e~g., carbon fibers~ glass fibers~ amorphous
silica9 asbestos9 calci~ silicate~ aluminum silicate,
magnesium carbonate~ kaolin~ chalk, powdered quartz7
micaJ feldspar, etc.; nucleating agents~ eOg~, talc,
calcium fluoride9 sodlum phenyl phosphinate~ alumina,
and finely divided polytetrafluoroekhylene, etc.;
-19~
~ 33 ~ ~ ~
plasticizers9 up to about 20 percent9 based on the weight
of the composition~ e~g.~ dioctyl phthalate, dibenzyl
phthalate~ butyl benz~l phthalate~ hydrocarbon-oils,
N-normal butyl benzene sulfonamide t ortho and para
toluene ethyl sulfonamide~ etc. The colorants (dyes
and pigments) can be present in an amount of up to about
590 percent by weight, based on the weight o~ the composi
tion,
The toughened compositions of ~his invention
can be prepared by melt blending, in a closed systemD a
polyamide and at ~east one polymer into a uniform mixture
in a multi-screw extruder such as a Werner ~fleiderer
extruder having generally 2-5 kneading blocks and at
l~ast one reverse pitch to generate high shear, or other
conventional plasticating devices such as a Brabender,.
- Banbury mill, or the like. Alternatively~ the blends
may be made by coprecipitation from solution9 blending.or
~y dry mixing together of the components followed by melt
fabrication of the dry mixture by extrusion~
The compositions described in the examples
are prepared with a Werner Pfleiderer twin screw
eY.truder. The constituents are dry blended and extruded
under vacuum 5 to lOO~C~ above the melting point of the
matrix resin~ preferably 310~C. or belowO Higher
temperatures have been used successfully~ The extrudate,
hich is opaque at temperatures less than 20~C. above
the melting point, denotin.g a two phase system, is
cooled in a water bath, cut, vacuum dried and molded into
*est pieces~ Of course9 many process variations are
possib].e~
~20
~ ~ 3~
It may be desirable to f'orm a concentrate of the
toughened thermoplastic composition. This is accomplished
by admixing the polyamide in higher concentrations based
on the weight Or total composition~ e.g.~ up to about 50
percent by weight9 with the at leask one polymer.
Additional polyamide is admixed with the composition to
yield the desired concentrate, such as a toughened
composition containing 1 to 20 percent by weight of at
least one polymerO
It has been found useful to increase the
molecular weight o~ the toughened thermoplastic composi-
tions during the preparation of the composition. By
way of illustration~ an admixture of low molecular wPight
polyamide~ eOg.~ 5,000 to 15,000~ and at least one
polymer is prepared in a plasticating device as
described above and the molecular weight is increased
either in tha melt or at an elevated temperature below the
melting point (solid phase) of the polyamide~ By way of
illustration5 after melt blending the composition is either
~1) held in the melt a~ a temperature about 10 to ~0C~
above the melting point a~ a pressure of about 1 to 25 mm
Hg absolute for up to one hour, or (2) in the solid phase,
after cuttingp quenching and drying7 at an elevated
temperature at least 15C~ below the melt temperature of
the polyamide in an inert gas stream for at least two
hours. Beaton U. S~ Patent 3~21S171 describes solid
phase polymerization~
The toughened thermoplastic compositions can be
~ made into a wide range of useful articles by conventional
moldlng methods employed in the fabrication of` thermo-
-21-
L33~&~
plastic articles9 iOe~, as molde~ parts, extruded
shapes~ e.gO~ tubing, films~ sheets9 fibers and oriented
fibers, laminates and wire coating. "Molding" means
forming an ar-ticle by deforming the blend in the heated
plastic stateO
The compositions of this invention are
characterized by an outsta~ding combination of properties~
foremost of ~hich is outstanding toughness properties in
~iew of the quantity of at least one polymer present with
the polyamidc matrix~ The unusually high toughness pro~
vides greater ductility, less sensitivity to scratches
and molded in notches, and vastly reduced susceptibility
to catastrophic failure when compared with previously
~nown compositions in molded parts~ Injection molded
parts often are of varying thicknesses and may have
s~ratches9 molded-in notches of varying radii, and
molded in stresses. In addition9 orientation effects
may cause varied ductility throughout a molded part~
The maintenance of high uniform values of notched I~od
toughness throughout such molded parts characterizes
the improved compositions resistance to brittle breaks.
The compositions are of suff cient toughness that the
effect of minor changes in processing conditions will
not cause significant variations in toughness from lot
to lot quantities of compositionO
~XAMPLES OF T~ INV~NTION
The followjng examples illustrate the invention
wherein the percentages are by weight unless indicated.
The toughened polyamide compositions are pre~
pared as follows: -
The polyamide matriY~ and pol~mer(s) in dry form~22~
~3~4
are mixed after weighin~ in the proper proportions by
tumbling in a polyethylene bag. The mixture is then
blended in a 2~ mm Werner Pfleiderer extruder in ~hich
the hopper is blanketed with nitrogen and the vacuum
port main~ained at about 25 to 30 inches vacuumO
Ex~ruder barrel temperatures are set at about
the melting point of the polyamide matrix (~ 10Co~ level
condition~ yielding melt temperatures in the range of 5
to about lOO~C. abo~e the melt mg point of the matrixO
The beading exiting the extruder is water
quenched 9 cut and vacuum dried overnight at ~0CO prior
to molding~ Test bars~ 1/2 x 5 x 1/~ inch are molded
; in 3 oz. and 6 oz~ injection molcling machines at melt
temperatures 10 to 30C. above the melting point of the
polyamide matrix. The mold temperature is about 90C.
with fast injection and a 20/20 or 20/30 molding cycle ~;~
(seconds r~m ~orward/second ho3cl). The molded bars
are tested using the follo~ng test procedures in
the dry-as~molded state:
Notched Izod toughness: at each end ASTM D-256-56
- Tensile Strength: ASTM ~-63~-5~T
Elongation: ASTM D-63~5~T
Flexural Modulus: ASTM D-790-5~T
Tensile Modulus of the matrices~ ASTM D~63~-5~T (dry)
Tensile Modulus o~ the pol~aers: ASTM D-~2 ~50% RH)
Mel~ Flow: ASTM D~123~73 Condition G (except where
noted~0
Particle Size: Electron micrographs of microtomed
or fractured surfacesO
Information relatlng to the poly~aide ma~rix and
~23~
~3~
pol,~ers u~ed in con~unei;ior~ wlth the polyamide matrlx
are ~et for~h in Table~ l-A and l-B, respecti:vely~ The
a~ron~n~ used herel~a~ter are ~t :eorth in Table 2.
TABIE 1-~
1. 66 Pol~ramld~ inher~nt vi.~eosit~ about 1.25
~ 0.10 me~ured ~s 0.5 g. per 100 ml. o~
m-cr~sol at 25C.~ C00~: 65-73 ~q./~6 g.;
~2 47; 53 ~q./10 g.
2... 66 Polya~i~e lnherent visco~ ty about 0 . 86
measured ~s 0.5 g. per 100 ml. o~ m cre~ol
at 25c", COOH: ea 110 e~./10~ g.; ~H2:
ca 85 ~ o6g~
3. 75 per~ent 66 Polyamide descrlbed in 1
abov~
25 percent 66 Poly~mide l~here:nt viscosity
about 1.95 ~ OD1O me~æur~d a~ 0.5 g. per
100 ml. Or m-cresol at 25C.
4. 50 p~rce~t 66 Poly~mlde described in 1
above
50 pore~nt 66 Poly~mide described in 3
above
5. 100 percent 66 polyamid~ inherent visc9si~g
about 1.95 + 0.10 mea~ured as 0.5 g. p~r
1~0 m10 Q~ m-cresol at 25~. :
6. 66 Pol~mide inherent vlscosity about 1.25
+ 0.10 mea~ured as 0,5 g. per 1OO mlr of
m cres01 at 25C.~; C00~: 34-46 eq.,/106g.;
2- 73~93 eq.~/10 g.
7. 66 Poly~mid~ inhorent vl~;c08ity about 0.98
measur~ 0.5 g. per 100 ml" o~ m-cresol
at 25C., COOH: ca 44 eq./106g.; ~H2: ca
94 eq./106g,
8., 612 P~lyamid~ rent vlscosity ~bout
0.95 ~ 0,10 measured a5 0~5 g, p~r 100
ml. o~ m-cresol ~t 25C.
9~ 612 Polyamlde inhere~t ~iscosit~ about
1.,17 ~ 0.10 measured as 0~5 g. per 100
- ml. ~F m-cre~ol ~t 25C.
-Z4-
.J.
~:~3~
10. Plasko~ 8200 - 6 nylon sold by All~ed
Chemical Co.
11.. Hul~ nylon 12 inherent viscosity about
1. 20 measured as O . 5 g. per 100 ml . of
m-cresol at 25~C.
12. ~ILSA~ nylon 11 lnher~nt ~lscosity
about 1.17 measured as O ~, 5 g. per 100
ml. of m-cresol at 25~C. sold by
Aquitane Chemicals, Inc.
13. 66/6 (80/20)copolymer inherent ~i~cosity
about 1~ 33 m~asur~d as O . 5 g. per 100
ml. o~ m creqol.
14. Trogami~ T poly(trimethyl he~came~hylene
terephthalam:Lde) sold by Dynamlt Nobel
inherent viscoslty about 0.95 measured as
0.5 g. per 100 ml. of m-cre~ol at 25C.,
COOH: ~a 59 eq./106g~; ~2: ca 57 eq./106g.
15. PACM-12 polyamide containlng bis(para-
aminocyc~ohexyl) m~thane and dodecane-
dloic ~cid lnherent ~lscosity about 0.95
measured as 0.5 g. per 100 ml, o~
:: cr~sol at 25C., COOH: ca 57 ~3q./106g.;
~I2: ca 60 eq./106g.
16. Pla~or~ 8252 ~modlfied 6 nylon) ~old
by Allied Chem ~al Co.
:
* denotes trade mark
~25
~L~3~3~.6~
~,~il o ~ ~ ~ co~ o~l o~J
' 1 ~ ~
-~o ~o
a a A ~ ~3 y Yy ~U Y~ ~
. . ~
o000
~C i ' '`~
~ ~o~
'~,
--I ` h o o ,~ ~ R ~ ~ ~ ~ u ~, o
~6
3L~3~39L~
~ ~ v I ,, ,o~
a
~' 1 ' ~ o~ , U~
~
Q ~ ~ rl ~ rl
O V ~
K ~-o ~o ~o ~o ~o ~oW ~O ~ ~ ~ ~
~J O CV C~l CV CV NCV N N CV N CV
, Y;~ ~ O ¢ ¢ ~ O
. N
~ t I C`J ~ o U~ o
: ~ ~Ic ~ ~cv co ~ ~D CV ' Cc~ ~ CV ~ : ~
E ~IS cs~ c~ ~ o 11~ o o o o o o
~Q :~ 1~ ~,
h L L .
p~ .
~o
~ r~ ~ m ~ ~ ~ m ~ m ~ Lr~ ~ L ~ L'~ ~ ~
~ rl r/ ~i 'r'S rl r~i L~ 10 Lr~ Lr~ U~
.
r~ ~4
rc~ r~
~i h ' J~ ~J
r~ N ~1 .-.t L'~ C; ~ 0 cr~ O r-l O CV t~l
--27--
~33~4
' 1 ~ ' ~ ~ U~
I S~
.. I ~ .
h d C C~ N N N N N
, ~ Z u~ ~ N N C C C N ~, C C:
~1 o o o o o It~ O 1~ ~
... .
~u ~ ~
,.
, 0 d 0 ~J 0 0 0 ~ ' 0
--2~--
~13~ 4
C~ -
~-~i , ~ .
. ~U
1 ~
0 ~ 5~ h
51 Ul ~ ~ U~ ~ S
~1 ~`
N ~ ~o r~
::S ' ~( N N N
. ~ t~3 M
.~
~ ~ u~
. . æ t- ~ , ~_ I , , , , , , , . . , , ,
~; ~ , . ' ~
~ _ h ~ N
~lU ~ ~ . ~
~ ~ ~ ~ ~ u o~ o o y~ ~
~ 8
.~
,, o ~ ~ o o
V P
/J ~1 0 ;~ ; O N ~t O n ~o ~ ~0
N N ~ ~ \ID ~ CO~ O r( ~N ~1 ~ If ~ W t~
p~ ~1 rl r-1~1 ~Ir(r-lr~l r-(rl r~r/ ~-1 N r(N r1N ~J N N 0J tU CU
co
~ ~ O ~ '
h ht--
N r~ O~ O~O
-29-
~33~
~ .
' ~ . ' "'
V ¦
O
r1
:~ ~
: ~ -
' .
. .
h h
i~ ~ L
~ ~ a _
E~ ~ s. æ rl ~ r~ r~ ~ rl m
O . p:l CU o
~ S~ . ' o W
V~ r ~ N O ~ ~ . 5
D _ CO a~ C ~ ~--N _ t O
¢~ ~ ~ ¢ ~ ~ ~ tD Cl bD P~ ~ ~ bD ~ R
rl Cl~ Q rl ~UI 1 ~. In ~ t-- CO ~ Q r~ N t 0 1-- ~I cr~
t~
.,
o ~1 ~ ~ ~ In '~D i- ~ .cr, ~ ~U ~ .~ c~ ~1
co ~ a~ o co co ~o ~ ~ ~ cr. a~ c~ o~ c,l ol
.-3o -
:3L13~
~1 ~ . .
~1
0 I r~
N¦~ ~ N
~'~ ~0~ '
W ~ N
~ o , p c~
~ N o -$ C: 1~ o r- :) o ~
31-
~:L33~6
~1
~c ~1 a
~ .~ ~
~ ~ a
r~l o l .
~ ~I ~
, ~ R
a
æ
~ ~ a O
O ~ 8 ~
h
N C~ ~0 ~ ~ o$
_y o
o
0 ~ ~
~i N ~olnr~ a ~ .~ ~ ~
~1 N N 0 ~o~o ~r) 0 0~ ! O O ~ ~¢
i N N Co C\l ~ N (~ ~ ~ ~ r~ ~ ~
--32-
,
~3~
Polymers 1, 2, 6to 13, 28 t4 31 are prepared as
described in Rees U. S. Pa~ent 3 ,264,272 .
Polymer 5 is prepared as described in Greene
Belgian Patent 818~609 with the neutralizations using the
procedure described in Rees [J.S. Pater~t 3~264,272 ~rlth -the
exception of the ~D neutralization (Example 23) whlch is
described in Rees U~,S. Patent 3,471/460.
Polymers 3" 49 14J 15, 19, 20, 21 are made by
high preæsure, free radical polymerization,
Polymers 16 to 183 23 ~o 27 are p:repared as
described in EIammer U.S. Patent 3,780,140.
Pol~mer 22 is COMER~ 9300 ~ade by UN on Car~ide.
Polymers 32, 51 are the ind cated base polymer
gra~ted aceording ~o Example 13B o~ Caywood Canadian
P~tent 1~032J688~ which issued 1978 June o6.
1'he base polymers o:~ the indicated polymers are
~ollows:
Polymer 33 ethylene/propyle~e/1~4-he~adiene
(64/32/~ ~ooney vlscoslty ASTM D-1646 ~ML-1~4~121C.)
o~ about 45.
Polymers 34, 35 ethylene/propylene/194~hexadiene/
2~5-norb~die~e (54/40/6/0.35) Mooney viscosity about 25.
Polymers 36-38, 46-49, 70~ 71 ethylene/
propylene/1~4-hexadiene (62/32/6) Mooney viscosity abou~
Polymers 399 41-45~ 50~ 57~ 66, 73, 77 ethylene~
propylene/1~4-hexadiene/2~5-norbornadiene (68/26/6~0.15)
Mooney viscosity about 33.
Pol~mer 40 e~hylene/propylene/1,4-hexadlene/
~ ~ 33 ~ ~
295-norbornadiene ~71/23/6/0.5) Mooney viscosity about
. 2S.
All the above base polymers are prepared by co-
polymerizing the monomers in the presence of a coordina-
tion catalys~ system such as diisobu-~ylaluminu~ chloride.
and vanadium oxytrichloride~ Copolymerization may be con~
duc~ed in an inert solvent or in a slurry or particle
form reactorO Details of their preparation are given,
for exam~le ? in U~ S. Patents 2,933,4~0; 2 7 962 9 451;
3~000,~; 3,093~620; 3,093 7 621; 3 9 063p973; 3p1~7~230,
3,154,52~; 3~260,70~; and in M. Sittig; "Stereo Rubber
and Other Elastomer Processes", Noyes DeYelopment Cor-
portion~ Park Ride, N~J. 9 1967~ as well as U.S. 3,~199591.
Polymer 33 is a mixture of the above base
pol~mer and ethylene/maleic anhydride (~9/11) made by
high pressure9 free radical polyrnerization.
Polymer 34 is tumbled overnight with 7 weight
p~rcent of MAME on 1/4 inch cubes of base polymer and ~:
extruded on a 2~ mm Werner Pfleiderer extruder fitted
~ith a vacuum port and 4 kneading blocksO The melt
temperature is about 315C. and hold~up time 2 to 4
minutes. The product is quenched~ cut and driedO
Polymer 35 is a mixture of 9~2 grams of m-
carboxy benzene sulfonyl azide and 3600 grams of blanc
fixe added to 350 grams of the base polymer and 0~7 gram
of 173,5-tri.methyl 2~4,6-tris~395~di tert-butyl-l~
hydroxybenzyl) benzene (~thy~ Antioxidant 330~ on an
unheated rubber roll mill at ambi.ent temperature~ Sixty-
gram portions of the resulting composit.ion are sheared
for 10 minutes at 145C~ and then ~or 10 minutes at
~'~ 3~
170C. in a ~rabender plastograph.
Polymer 36 is prepared as follows: A 5-gram
portion of phthalic anhydride sulfonyl azide and ~ grams
of 1~ 3 9 5-trimethyl-2~L~ 9 6-tris(3,5-di-tert-butyl-4~
hydroxybenzyl) ~enzene 9 (Ethy~Antioxidant 330) are
added to 499 grams of the base polymer on an unheated
rubber roll mill at ambient temperature. Sixty-gr~n
portions of the resulting composition are sheared for
10 minutes at 170Co in a Brabender plastographO
Polymer 37 is prepared by the procedure
described below for polymer 3~ using 150 grams of the
base polymer of ~olymer 36 and 120 grams of maleic
anhydride. Note: Polymer 37 varies between Examples
and 90 as follows: Example ~ - 40 perce~t ungrafted,
60 percent grafted ~ 1 percent graft; Example 90 - 60
percent ungrafted, ~0 percent grafted - 1.5 percent graft.
Polymer 3~ is prepared as follows: A Werner
Pfleiclerer 53-mm twin screw extruder is assembled by end~
to-end attachmen~ o~ 16 barrel sections of 0~5-inch
diameker~ Follo~ng a short feed section are four reaction
sec-tions (zones 1-4)p one vacuum extraction section
(zone 5)g a cooling section (zone 6), and a die section.
Provisions are made for the metering of molten maleic
anhydride at the forward part of zone 1. The screws are
composed of kneading bloc~;s9 reverse pitch screws; and
transport screws arranged to generate 100~200 p.s.1~
pressure in zones 1-4~ no pressure in zone 5, and 500~700
p.s~i. die pressure. The free volume of zones 1-5 is
equivalent to two pounds of polymer at the operating
temperature. Zones 1-l~ are preheated to 300C~, zone 5
~3~
to 250Co and zon~ 6, the ero~-h~adg and th~ die to
165~C~
Th~3 Qla~to~r 1~ ~ed to the extru~r in the
~orm o~ chip~ whlch ?aS~ a 0.5~1nch screen. Maleic
ar~dride i~ ~et~r~ to th~ extruder ak ~n average f'eed
rate o~ 2~1~4015% of the polymer weight. For e~rery 1~0
:~ part~ o~ reac~ant~, 6.,1; part~ of a 1~,5~ ~olutiorl o~
1, 3 ~ 5 ~imeth yl-2, 4, 6 -txiæ ( 3, 5-di ~tert 4-bydro~benzyl
benzen~ th;yl@}~ntiox~dant 330) in a¢etone t ~ p~mped
1~ ~nto a mlx~nEs ~eeti~ Ju~t ahead o~ the exl;ra~tion
æectlon. m~ extruder ~rew ~p~e~ iæ 12.5 rpm a~d the
~racuu~n ~ection i~ operated at about 25 inch~ Or H~.
The pro~t, extruded at the rate o~ 5.8-6.1 lbs./
~. ha~ a maloi~ anl~d;rid~ ccsn1;ent o~ a~out 1.,5% b~
weight, Four ba~¢he~ totallllig 117.0 gram~ o~ monoamlnQ-
t~rminated pol~rcaprolacta~ ~ith an aver~3;e degree o~
poX~merizatlvn o~ 15.3 are added (a~ a powder) to ~our
bat¢hes o~ th~ a~ove produet totalling 45~.,8 gram3 on a
ru~ber roll m~ll a~ 110C. The~e m~tur~s are then trar~-
20 ~rred to an ~l~ctri~all~ heated roll mill and ~orm~d i~toa ~mooth band ~y milling at 225a~Co :E~or 10 minute~"
J?olyner~ 39, 41-45 are 3?repared b~ th~ method Or
the a~orem~ntior~ed CaIladian Pater}t 1 032 688 Or Ca~wood
but usi~g a varie~y o~ un~aturated ~on~mer~ al; peak
reaction ~e~era~ure o~ 325-400~C~ and u~ing a ~tatle mlx~r
~uch as tho~e marketed b~ the Kenic~ Co~apany between the
extruder ~crew( 8) and the di.e .
Polymer 40 is prepaxed a~ ln Polg~mer 34 uælng
2~ ~marie acid on the ba~3e pol~mer o~ Polymer 40~e me
- 36 -
~L3~
extruder has 5 kneading blocks and melt temperature was
about 350C.
Polymer ~6 is prepared as rOllOws:
Ao Ethylene/Ethyl Hydrogen Maleate Copolymer
The random ethylene/ethyl hydrogen maleate
copolymer analyzes for 7~2 weight percent incorporated
ethyl hydrogen maleate9 007 weigl~ percent incorporated
maleic anhydride~ and 0.4 weight percent incorporated
maleic acid made by high pressure free radical polymeriza-
tionO
B. Blend of Base Polymer and Ethylene/~thyl
Hydrogen Maleake
A blend is prepared by mixing 12~ grams of the
; ethylene/ethyl hydrogen maleate copolymer of A with 192
- grams of the base polymer on a rubber roli mill at 150C~
for about 5-10 minutes.
Polymer 47 is prepared as follows.
A~ ~thylene/~thyl Hydrogen Maleate Copolymer
The random ethylene/ethyl hydrogen maleate
copolymer analyzes for 7.0 weight percent ineorporated
ethyl hydrogen maleate, 0.~ weight percen~ incorporated
maleic anhydride, and 0~4 weight percent incorporated
maleic acid made by hi~h pressure free radical polymeriza-
tion.
B 2 Blend of Base Polymer and Ethylene/~thyl
Hydrogen Maleate
A blend is prepared by mi~lng 64 grams of the
e~hylene/ethyl hydrogen maleate copolymer of A with 256
grams of the base polymer on a rubber roll mill at 150C.
for abou~ 5~10 minutes.
~37
~ 3~
Polymer 4~ Blend of Base l'olymer and Ethylene/
Ethyl Hydrogen Maleate Copolymer
The general procedure of Example 99 is repeated
using 12~ ~rams of the copolymer and 192 grams of the base
polymerO
Polymer ~9 is prepared as follows:
A. Ethylene/n-Butyl Hydrogen Maleate Copolymer
~ The random ethylene/n-butyl hydrogen maleate
; copol~ner analyzes for 11~ weight percent incorporated
n-butyl hydrogen maleate, 1~2 weight percent incorporated
maleic anhydride9 and 0.3 weight percent incorporated
maleic acid made by high pressure ~ree radical polymeriza-
tionO
B. Blend Or Base Polymer and Ethylene/n-Butyl
Hydrogen Maleate
A blend is prepared by mixing 64 gra~s of the
ethylene/n~butyl hydrogen maleate copolymer of A with 256
gr~ns of the base polymer on a rubber roll mill at 150Co
for about 5-10 minutes~
Polymer 50 Base polymer grafted by the method of
Polymer 39~ .
Polymer 52 is a mixture of two commercial
polymers butadiene/acrylonitrile (BAN) is Firestone FRN
606 and styrene/maleic anhydride made by ARC0 SMA-30009
mixed on a 6" roll mill-
Polymer 53 is the BAN described as Polymer 52
Polymer 54 is a blend of styrene butadiene
rubber FRS 211 sold by Firestone and ethylene/maleic
anhydride (~9/11) made as described :in Polymer 33
Polymer 55 is prepared as follows:
A~ Isobutylene/Isoprene Copol~er~ ~njay ~utyl
3~5
-3
~3~
The butyl rubber employed is an isobutylene
copolymer con~aining about 200 mole percent isoprene uni~s7
The Mooney ~iscosity (ML~ /100C.) is about 45. A.non-
- staining antioxidant is present, 000S~0.15% zinc dibutyl-
dithiocarbamateO
B~ Phthalic Anhydride Sulfonyl Azide Modified
Isobutylene/Isoprene Copolymer
Six grams of phthalic anhydride sulfonyl azide
are added to 300 grams of the isobutylene/isoprene copolymer
of A on an unheated rubber roll mill at ambient temperature.
Grafting is accomplished by heating the resulting composi-
tion on a 200Co mill for 10 minutes.
Polymer 56 is prepared as follows:
A~ Polyisobutylene9 Enjay Vistane~ L-~0
The polyisobutylene employed has a Staudinger
molecular weight of 709000 and contains a non-staining
antioxidant, butylated hydroxyto].ueneO
B~ Phthalic Anhydride Sulfonyl Azide Modified
Polyisobutylene
Six grams of phthalic anhydride sulfonyl azide
: are added to 300 grams of the polyisobutylene of A on an
unheated rubber roll mill at ambient temperature. Graft
ing is accomplished by heating the resulting composition
on a 200C. mill for 10 minutes.
Polymer 57 is a mixture of the base polymer
and styrene/maleic anhydride (5/1~ Lytron~ g20 made by
Monsanto prepared on a 6" roll millO
Polymer 5~ is a mixture of cis-1,4~polyisoprene
having a Mooney viscosity (ML-~/100C.) of about ~59
3 Natsy~ 410 sold by Goodyear Tire & Rubber CoO, and
-39-
~1 3~
ethylene/maleis anhydride (90/lO) copolymer made by high
pressure, free radical pol~nerization~
Polymer 59 is a mixture of natural rubber
Harte~ ~0 sold by ~irestone and ethylene/maleic anhydride
described in Polymer 5~0
Polymer 60 is a control of natural rubber used
in the blend of Pol~mer 59.
Polymer 61 is prepared as follows: A one-liter
4-neck round-bottom glass flask is charged at room
temperature with 375 ml of water~ 300 ml of etllyl ac~late,
12 grams of f~naric acid, 6 ml of a 3Q% of sodium lauryl
sulfate in water, 002 gram of sodium hydrosulfite5 and
0~1 ml of dodecyl mercaptan. After the resulting mixture
has been sparged with nitrogen, it is heated to 600C.
Copolymeriæation is initiated and rnaintained for two hours
at 600C. by gradual addition of a 2% solution of kert-butyl
hydroperoxide in water frorn a syringe pump. The emulsion
obtained is strained to remove coagulum (35 gra~s) and
then coagulated with acetone. Afker the copolymer c~umbs
havebeen washed with water three times, they are squeezed
and dried in a vacuum oven at ~0C. for 20 hours. A 2~5
gram yield of white copolymer is obtained displaying an
inherent viscosity of 4006 deciliters/gram at 30C~
(measured on a solution of 0.1 gram of copolymer in lO0
milliliters of chloroform)0
Pvlymer 62 is prepared as follows^ A one-liter,
four-neck round-bottom glass flask is charged at room
temperature with 450 ml of water, 360 ml of ethyl
acrylate, 144 gr~ms of ethyl hydrogen fumarate? 3.6
ml of ethylene dimethacrylate, 7.2 ml of 30% sodium laurrl
sulfate in ~Jater9 0~24 gram of sod:ium hydrosulfite~ and 102
1~0-
~ ~ 3~
ml of dodecylmercaptan. After the resulting mixture has
been sparged with nitrogen for a half-hour9 it is heated
to 43C. Copolymerization is initiated and maintained
for six hours at about ~3C~ by gradual addition of about
lo 5 ml of a 2~ solution of tert-butyl hydroperoxide in
water from a syringe pumpO Heat evolution lessensO
After the mixture has been heated to 40C.~ a one-
milliliter portion of the hydroperoxide is added over a
one-hour period. There is only a trace of coagulum to
remove~ The latex is coagulated with acetone and the
crumbs of terpolymer obtained are rinsed three times
wikh water and dried in a vacuum oven at ~0C0 for three
da~s. The yield: 296~5 grams. Inherent viscosity
(measured on a solution of 0.1 gram of terpolymer in
chloroform at 30C~) 0.7~ Composition: ethyl acrylate,
95 weight percent; ethyl hydrogen fumarate, 4 weight
percent; ethylene dimethacrylate~ 1 weight percentO
Polymer 63 is prepared as follows: A one~
liter four neck round-bottom glass ~lask is charged at
room temperature with 450 ml of water, 360 ml of n-
butyl acrylateg 1404 gram~ of ethyl hydrogen fumarate,
702 ml of a 30~o solution of sodium lauryl sulfate in
watex9 0024 gram of sodium hydrosulfite, and 0.1 ml of
dodecyl mercaptanO After the resulting mi~ture has been
sparged with nitrogen for a half-hour7 it is heated to
43C. and 2 ml of a 2% solution of tert-butyl hydro~
peroxide are addedO During the next four hours 2 ml
Or a lO~o solution of tert~bu-tyl h~droperoxide are
introduced. After addition of 0~2~ gram of sodium
hydrosulfite and one more milliliter of tert-butyl
hydroperoxide~ the mixture is heated to ~0C0 and stirred
~41-
~:~3~
30 minu~es longer~ The mixture is once again heatèd
to 40~C~; during the final hour at 40Co still another
millili~er of te~t-butyl hydroperoxide is addedO After
the latex thus prepared has been strained free from 15
grams of coagulum~ the copolymer is obtained by treating .
~he latex with acetone~ The copol~mer crwnbs obtained
are ~ashed three times with water and dried in a vacuum
oven at ~0C~ The white product weighs 2~3~5 grams and
has an i.nherent viscosity of 3.60 (measured at 30Co
on a solution of 0.1 gram of copolymer in chloroform)0
It contains 4 weight percent ethyl hydrogen fumarate .
monomer unitsO
Polymer 64 is prepared as follows:
Ao Ethylene/Ethyl Hydrogen Maleate Copol~ner
The random copolymer contains about 90 weight
percent ethylene monomer units and 10 weight percent
ethyl hydrogen maleate monomer units~
B. Ethylene/Propylene Copolymer
The random elastomeric ethylene/propylene
20 monomer units and has a Mooney (Ml~ /121Co ) viscosity ~ .
of 51~ It is made in solution in hexane at about 50 Co
in an evaporatively cooled continuous reactor in the
presence of a coordination catalyst made in situ by
introducing VCl~ and dii.sobutyl-aluminum monochloride
~Al:V atomic ratio = 6),
C. Preparation of Blend of Ethylene/~thyl
Hydrogen Maleate Copolymer and Ethylene/Propylene Copolymer
A blend is prepared on a 150Co roll mill using
64 grams of the ethylene/ethyl hydrogen maleate copolymer
of' A and 256 grams of the ethylene/propylene copolymcr of
B~ Mixing takes about 5 to 10 minutes~ Analysis
~42~
3~6~
indicates that the blend contains lu2 weight percent
ethyl hydrogen maleate monomer units~ 0036 weight percent
of maleic anhydride monomer units, and less th~n 0.1
weight percent of maleic acid monomer units.
Polymer 65 is prepared as follows~ A 3 gram
portion of phthalic anhydride sulfonyl azide is mixed
with 300 grams of the el.as~omeric ethylene/propylene
copolymer of Part B of Polymer 64 on an unheated rubber
roll mill at ambient temperature~ The resulting
compositio~ is transferred to 200C~ roll mill and
sheared at 200CO for 10 minutes to engraft phthalic
anhydride sulfonyl groups onto the ethylene/propylene
dipolymer.
Polymer 66 is prepared as follows: The
base polymer grafted to ca~ o fumaric acid by method.
of Polymer 39~ The melt flow rate of the grafted
polymer is ca. 3 grams/10 minutes by the method of
ASTM D~123~ at 2~0C. with a 2160 gram load.
Polymer 67 is a random elastomeric copolymer
having a melt index of 10.0 grams/10 minutes4
Polymer 6~ is polyurethan.e elastomer prepared
as described in U~ S. Patent 2J729p61~ Texin~ 4gO sold
by Mobay.
Polymer 69 contains Herchlo~ C sold by
Hercules Inc.
Polymer 70 is prepared as follows~ A 3~54
gram portion of.the monoethyl ester of phthalic anhydride
sulfonyl. azide was added to 300 grams of the base polymer
on an unhea-ted rubber roll mill at ambient temperature~
One hundred fiI'ty gram portions of the resulting
composition are sheared for 10 minu-tes at 200C~
~l~3
Polymer 71 is prepared as Pollow~: A 6.21
gram portion o~ th~ n~nooctadecyl ester of phthalic
anhydr~ de sul~onyl azlde was add~d to 300 grams of the
ba~e polymer of an unheated rubber roll mill at ambi ent
~emperature. One hundred fifty gram portlons o~ the
resulk~rlg compo~ition ~re sheared for 10 minutes at
200 C .
Polymer r2 ls prepared by:~:hi~h pressure :Eree
radical polymerization~
Polymer 73 ls the ba~e polymer.
Polymer 74 i~ an ethylene-butene copolymer made
by the Du Pont high der~slty lo~ pressure process;
polymer d~nsity 0.937 gms/cc.
Polymer 75 is an ethylene homopolymer made by
high pre~sure ~ree rad~cal polymeriz~.tion, polymer
denslty O, 920 g;m~/cc .
Polymer 76 is an ethylene homopolymer ~ade by .
the Du Pont h~gh density low presæure process3 polymer
den~ity 0.957 gms/cc and melt index (Condition E) o~
20 ~.8 before graftlng~ Grafted by the me~od of Poly~er
39.
Polymer 77 is grafted by method o~ Polymer 39.
Polymer 78 iæ DIENE* 35 sold by Firestone
Rubber Co.
* denotes trade mark
-44-
3)?164
TABI.E ~
_ABLE OF ACRONYMS
E ethylene
IBA i.sobutyl acrylate
MAA methacrylic acid
MA methyl acrylate
MAME monoethyl ester of maleic anhydride
HMD hexarnethylene diamine
VA vinyl acetate
MMA methyl methacrylate
CO carbon monoxide
AA acrylic acid
HEMA hydroxyeth~L methacrylate
SMA stearyl methacrylate
nBA normal butyl acrylate
2EHMA 2--ethyl hexy1.methacrylate
MVE methyl vinyl ether
P~Anh maleic anhydride
G~ glycidyl methacrylate
EDM~ ethylene glycol dimethacrylate
EA ethyl acryla.te
~A fumaric acid
BuHM butyl hydrogen maleate
PASA phthalic anhydricle sulfonyl azide
SMA (3000) styrene maleic anhydride copolymer
FA~E monoethyl ester of furnaric acid
P propylene
BASA benzoic acid sulfonyl azide
BAN butadiene acl~lonitrile
3 SBR styrene butadiene rubber
-g- graft
These Examples prepared according to the
procedure described above.are set forth in Table 30
~l45-
~ 33 ~ ~ ~
Control A is molded of an inter~ediate
molecular weight 66 nylon. Examples l through 5 are a
concentration series using a terpol~mer of ethylene7
isobutyl acrylate and methacrylic acid partially
neutralized wi~h zinc~ At the 30~ concentration the
notched Izod of a molded bar is over lO ft. lbs./inch
at the gate end and the far endO At 20~o the material is
tough at one end of the molded bar and at lower concentra-
tions toughness is in the range of prior art materials at
higher concentrations. Controls B through E are from
the prior art and show that the higher modulus copolymer
of ethylene and methacrylic acid is less effective in
toughening polyamide matrix l than is the lower modulus
terionomer O
Example 6 in comparison with Example 5 shows that
reduction in molecular weight of` the matrix causes reduced
notched Izod in a composite structure. F.xamples 7 to lO
show the e~fect of increasing molecular weight of the
. .
matrix toughened with 20 weight percent Or the terionomer.
EY.ample lO with the highest molecular weight matrix pro-
vides toughening with the ethylene terpolymer ionomer
so that at the 20~o level toughness is approximately
e~uivalent to that obtained at the 30~ level in matrix l.
Examples ll and l2 should be compared with
Examples 4 and 5 to show the range of reproducibility
in what were supposed to be identical materials. Comparing
Controls F and G with Controls D and E show similar
reproducibility in prior art materials.
Controls H, I and J show that low ethylene,
low modulus materials are not eff'ective toughening
~1~6~
~.~ 33~
agents when no adherent site is present. In comparison9
Example 13 where an adherent site is present, gives very
high toughness. Note that in comparison with Example lk
the only major difference between the polymers is the
presence of the ionomer group in Example 13.
Examples 14 and 15 show the strong toughening
effect of the unneutralized maleic acid monoethyl ester
terpol~mer in both an intermediate molecular weight
polyamide with balanced end groups (Example 14) and in
~xample 15 a polyamide matrix with high amine ends. The
high amine ends apparently ~rovide more effective
interactisn with the dispersed acid toughening agent
than the polyamide with a normal balance o~ end groups.
. When an ionomeric pol.ymer is used there is generally less
advantage in toughening a high amine ended nylon~
Compare Example 16 with Example 4~
Examples 17 through 20 comprise a concentration
series of the free acid toughening agent in high amine
ended polyamideO ~t a concentration of 5% significant
toughening is obtained. In fact, the material of Example
1~ achieves ~ery close to the toughness of prior art
material (Control C) at 1/4 the toughener concentration
and with consequently substantially better tensile
strength and modulus~ Examples 19 and 21 illustrate
the effect of the difference in concentration of amine
ends in the polyamide~ The effect at the 10% toughener
concentration le~el is more dramatic than at the 20%
level where the maximum in ductility as characteriæed
by notched Izod is attained~
~xample 23 shows thak the acid polymer slightly
-~7--
~ 3~
neutralized with hexamethylene diamine is an effective
toughening agent for nylon.
Examples 229 25 and 26 show the effect of
various degrees of neutralization to prepare ionomers
used for toughening polyamides with balanced end groups.
In a nylon rnatrix with balanced ends the zinc ionomer
is a more effective pol~ner than the free acid polymer.
Examples 2~ and 2S differ primarily in details of the
neutralization procedure which was carried out on a two
roll mill and show that proper neutralizakion must be
obtained in order to develop the most effective toughen~
ing. Conditions fo~ neutralization are given in Table lo
Xt will be obvious to those skilled in the art that for
any particular combination of pol~ner and matrix~
optimization of processing conditions must be used to
- obtain the best resultO
Examples 2~ through Control L include three
additional series where zinc neutralization was carried
out from O to 100% or higher for three different
toughening systems. In all three cases where a nylon
with balanced ends was used preferred neutralization is
in the range of lOO~ or below. Example 36 and Control L
illustrate that neutralization at 125% can give reduced
toughness, so that for practical purposes neutralization
in the range of 100% or below for toughening agents used
in an amide with balanced ends is preferred~
Examples ~2 through ~5 show that calcium,
lithi~nJ potassiurn and sodium ionomers can also be
effective toughening agents whcn a soft organic moieky~
e.g., ethy]ene/methyl acrylate/monoethyl ester of maleic
~3~ 4
anhydride (E/MA/MA~ is used with them. Example ~6
illustrates that the antimony ionomer has some toughening
effect~ In most of the ionomerization experiments either
the metal hydroxide or ace~ate was used as the neutrali~ing
agent but other salts would also be effective. Examples
~7 and 4~ illustrate that organic salts of the metal
ions may also.be used.
Examples 49 and 50 in comparison with Examples
3 and 4 show that mixing small amounts of ethylene/methyl
acrylate/maleic anhydride ester ionomers with ethylene/
; isobutylacrylate/methacrylic acid ionomers substantially
improve the uniformity of compositions of the latter
ionomer and polyamide aloneO
Examples 51 and 52 illustrate that lower
molecular weight polyamide can be effectively toughenecl
by the E/MA/MAME system. The improvement in notched
I~od above the base resin shown in Example 53 suggests
that moderately greater concentration of polymer would
give substa~tial toughness in nylon of this low molecular
20 - weigh~.
Examples 5~ through 5~ illustrate the potential
of several different ethylene terpolymer ionomers ~or
toughening polyamides4 The results of Examples 59 and
60 suggest that higher molecular weight polymers are
more effective than lower molecular weight materials.
A broad range of molecular weights can be employed~
Example 61 iIl comparison with Example 62 demons~rates
the effectiveness of an ethylene/vinyl acetate/methacrylic
- acid terpolymer ionomer in a high amine end nylon in
comparison with the same polymer in a nylon with balanced
~ 3
amine ends~
Examples 63 and 61~ demonstrate the effectiveness
o~ an aclditional ethylene terpolymerg the free acid in high
amine end nylon and the ionomer in nylon with ~alanced
end groups.
Controls M and N again show the need for an
: adherenk siteO In ~xample 6~ ethylene/vinyl acetate/C0
terpGlymer has modest toughening effect on nylon with
balanced end groupsO In comparison~ Examples 66 and 67
illustrate more effective toughening where amine ended
nylon is believed to offer more effective interaction.
than balanced nylon with the carbonyl groups in the ter~
polymer. (Results with E/VA polymers have been less
reproducible than with other pol~nersa apparently because
o~ marginal stability at processing temperatures for 6~
nylonO) Example 69 illustrates the effect of a blend of
two previously used polymers with the mixture providing
good uni~ormity of toughness. ~xarnple 70 illustrates
mixing two pol~ners, the polymers used in Control N and
Examples 3 and ~ t~ provide substantially better tough~
ness than when either pol~er is used alone~ Similar
effects of the mixtures of two pol~ners are shown in
Examples 71 and 720
Cornparison of Example 73 with Control N shows
that addition Or a small arnount of an adherent polymer
with a low ~odulus nonadherent polymer can substan-tially
increase its toughening capaci~y~
~ xamples 74 to 7~ cornprise a variety of ethylene
terpolymers with C0 as the reactive agent for the polyamide
matriY~. Several of' these examples illustra-te toughness
~5o
~ 3~
approaching notched I~od of 10 at both ends of the bar
and suggest that many of these materials could achieve
10 ~otched ~zod uniformly with optimization of composition
and processing, or some increase in toughener concentra-
tionO
Examples 79$ ~0 and ~1 are ethylene/vinylacetate terpolymers with a variety of functional groups
all of which show improvement in toughening compared
with Control No Example ~2 is a polymer containing ~
monomeric en-tities which also indicates that optimiza-
tion would yield notched Izods over 10 throughout the
length of the molded bar9 though the cross-linking effect
Or ethylene glycol dimethacrylate ~Control Q) may be
deleterious~
Examples ~3 through 103 illustrate the wide
toughening capability of ethylene~propylene copolymers
which contain small amounts of dienes suitable for
attaching adherent sites. As the examples show a
variety of these polymers of various molecular weight and
ratios o~ ethyiene to propylene and diene content may be
employed. mey may be used in polyamide with balanced
end groups or high amine ends and a wide variety of
adherent groups may be grafted thereto. Example ~69 in
comparison with Example ~79 illustrates that at low
concentrations of adherent sites, the monoacid is
less effective than the dicarboxylic acid~
Example 102 illustrates that an ionomer Or
said copolymer is effective9 and Example 103 illustrates
that said copolymers toughen low molecular weight nylon.
ExampleslO4 through 112 illustrate that a wide variety
-51-
- ~33~64
of low modulus polymers can be used to toughen nylon as
long as an adherent group is present. The examples
include most of the commonly available low cost synthetic
and natural rubbers including butadiene/acrylonitrile
rubberS styrene/butadiene rubber, buna rubber, isobutylene,
isoprene9 natural rubber9 ethyl acrylate9 butyl acrylate
rubbers, etc~ Controls 0 and P for Examples 104 and 1109
respectively9 show the importance of a site for adhesion
to the matrix.
Examples 113 and 114 illustrate that ethylene/
propylene copolymer can produce results similar to
ethylene/propylene/diene terpolymer (~xamples ~3 to 103)
provided that polymer with sites for adherence to the
matrix are mixed in (~xample 113) or the appropriate ! ,:
site is grafted onto the copolymer ~Example 11~) by
appropriate means~
The concentration serles of the ethylene/
isobutyl acrylate/methacrylic acid ionomer in matrix 1
comprising Examples 3~ 5~ 115$ Control R and Control S
discloses that notched Izod well over 20 ft. lbs./inch
can be obtained at high loadings of polymer~ Significant
loss in tensile strength and stiffness occur at high
loadings with drastic loss over 50%p presumably because
of phase inversion.
Examples 1169 117 and 11~ show that 612 nylon
can also be toughened with an ionomeric system~
Consisten~ results are obtained in Samples 119 and
120 and Control T.
Nylon 6 is very effectively toughened by the
zinc neutralized ionomer of E/MA/~AME~ Control U and
-52-
Example 121~ Lower levels of tou~hener can be used.
Huls nylon 129 Control V is also effectively
toughened by E/MA/MAME ionomer9 Exarnple 122~ and E/IBA/
MAA9 Example 123. Urethane rubbers are sufficiently
stable at the melt temperature of nylon 12 to be
ef*ec~ive polymers~ Example 124
: ~ylon 11 is toughened by E/P/diene-g-FA~
Examples 125 and 126.
Example 127 is an example of toughening a
nylon copolyrnerO
~xample 12~ illustrates toughening of 66 nylon
with balanced ends by an ethylene/propylene/1,4-hexadiene/
norbornadiene polymer which contains approximately 1D4
weight percent fumaric acid. Similar results, Examples
129 and 130, are ob~ained with similar type polymers
which are grafted with esters of phthalic anhydride
sulfonyl azide~
Toughening of an amorphous pol~amide with
previously disclosed polymers is shown in Examples 131~133.
The same polymers toughen a polyamide contain-
ing a cyclic aliphatic structure (Examples 134-136).
Examples 137-141 in comparison with Control Y
illustrate the toughening effectiveness of fumaric
acid grafted ethylene/propylene/1,4~hexadiene/norborna-
diene pol~ner at low concentrations~
Example 142 shows the effectiveness of a
mixture of a soft (ethylene/methacrylate 46/54) and an
adherent polymer (ethylene/acrylic acid ~0/20).
Examples 144 to 149 and Controls Z and AA
illustrate the effect of mixing branched pol.yethylenes
-~3-
~ ~ ~ 3 ~;4
of varying density wikh fumaric acid gra~ted e-thylene/
propylene/l~ hexadiene/norbornadiene polymer. Examples
14~ and Control Z were prepared by dry blending all the
components and feeding to the twin screw extruder; Con~rol
AA and Examples 145 to 149 were prepared by milling the
hy~rocarbon polymers together before feeding to the
extruder with the polyamideO Despite some variability
in results9 the examples illustrate the following points.
1~ mixtures with softer polyethylene are more effective
thall those with higher modulus polyethylene~ (2) a soft
adherent polymer can render a mixture effecti~eg (3)
comparisonwith Control BBp which was prepared by first
extruding the soft adherent polymer with the matrix and
then reextruding to add the polyethylene~ shows -thak the
materials of the mixture must coexisk in the same
particles to provide ef`~ective toughening~ Control CC
shows that S~o of this polymer alone is not enough to
confer very high levels o~ toughening on the matrix
(comparison with Example 141 reflects the influence
of amine ends on the matrix~
Comparison of Control DD and Example 150
illustrates the effect of difference in polymer modulus
when degree of adherence is about identical.
Example 151 illustrates an effective mixture of
butadiene rubber and an adherent material.
Examples 15~ and 154, in comparison with
Example 152, and F~amples 156 through 160; in comparison
with Example 1559 illustrate that a variety of additives,
eOg~ up to about 405~0 by weight, can be compounded into a
toughPned composition without materially affecting
~51,-
~ 6 ~
mechanical propertiesO Example 153 contains a lubricant,
~xample 154 a heat stabilizer and ~xamples 156~160 contain
colorants~ In these experiments the additives were com-
pounded into ~xamples 152 and 155 in a twin screw
extruder with a vacuum port~ .
~ xample 162 was prepared by compounding 33 weight
percent chopped glass fiber into the product of Example 161,
on a single screw extruder with a vacuum port. The
resultant product has a notched Izod nearly twice that of
commercially available glass reinforced 66 nylon while -
reta.ining strength and stiffness approaching that of
untoughened materiaI~ ~xample 163 illustrates similar
improvement when mineral filler is added to polyamideO
, . . . .
-55~
~s ~ ~ ~
:
h q~ ~D n h
1 ~ t~ r~rl ~ C~l . tD
rl P~ . l U CU s CU r(
~ , ' .s:
~q X . O O O O h
h ~ 0 8 88 8 8 8 o 8 8 8 8 8 8 8 g o
g ~ ~D . ~ CS~
~ rlrl rl rl rl ~ 0 ~I r~ ~ rl rl rs rl ~0 tq
X ~ ~ CU 0 u~ o o cr~ co ~ ~o ~ u~ CU CO ;~; ~
SD ~ sq 3 ~n~ c~ou CU CU sY~ U~r~ O C~u C~U C~U ~U ~U ~ P~
:. ~ . ' ~ '
~1 g~ 3 NIr) 3 3 ~ ~0 f3~ Cy ~No 3 3 J 3~ ~ t_ ~ tJ .o
h ~
, ~0 s
. ~ CO It~ rl r~ cr~ U~ CO O L~ Cll CO a~ ~ CU CO
tn urs rl O~ c;~ cr~ co co co C~ e-- cô O ~D
. _ :
~ . ~ o ~ tr~ C~ C~
.~: i. ~1 :i ;~ N t ~ CD
ri rlCU N N N N ri N N 3 N CU ~ rs CUrl N ~ X ~ :
: h ~ Ss
C: ` ~ O O ~ O O O O O O O O O O O o O O O ~ ~D
rl50~-- rSrt N CU ~ CU N ~ 3 tll N N CU ~NCU ~ t~
~
~D l ~ = = = = _ = = O ~
,~ ~ . æ : ~ :
~ U~
h t
I rl rt rt rt rt N CU N N ~t rl rl rt rt rt rS CU St ~
h ~ O t : .
~s . ~D q~ -: . .
d~l r1 rtrl r1 rl rl rt rt rtrt CU rl Irl 3 ~ ri rt rt 7;
rhl t~
~ ~ o
~ F~ c~ n ~ h t7 ~
~D rt rt rt rt ~t ~-t rt C~D
n s~ rtCU ~) 3. U) ~ s~ ~ ~O ~ 0 Cl~ O rt N
. -~6-
~' ' .
. .
~33
9 3 3 9 ~
~ ~ ~ o ~ ~ M ~
~ ~ ~ 1~ OJ N N ~; N N U~ ri rl U ~ ~ y ~ ~
~¦ a ~ ~ ~ a ~ ~ a ~
~d ~ n
~ ~æ ~
~_ rl U rl rl rl rl ~0 ~ ~ 0 rl rl ~0 rl ~ Y Y.
NO I ~ N C~
,, ~
--57~
h D C~ o~ u~
N h O O O
_ . h
~.i
~C~p ~jO
,,~
c~ 0
. ' ~ .
~ ~ 0~ O ~1 0 ~ t-- O ,0
.cr~ o~ 0 ~ ~
~ O ~ 1 ~I N N 2 2 N C~l 2 2 2 2 2 ~ ~c
o ~
~4 Ch
~1 ~ 03 o ~ ~ ~ ~ 1 o
&, h
h ~ ~ .
- U ~
~I ~ ~ 'J ,a 3~ h,
~ ¦ ~ o a
~5g--
~3~
0
V~ ~
Q ' D~
N 3~ ~,
~, ~
o , ~ ~
~ ~ a) 0 ~ D CO 0
.~ cb I c~ O ~ ~
O c~ '
G ~ ~ o t~ h
8 ~a NC~ J N rl rl rt æ ,1 ~ æ ,, ~ ~ ~
. ~ O ~ h
: ~ u~ 8 ~q
~e; ~
- - O *~ h
~ ~ . .C~
n n n n n n n n n n n ~l n .~
- $~
;~ ~ ;~ ~ ~3Q h
~ ~ x~ h ~ o ~ o ~ v~
Di ~ J J t ~ *~ O c~ ~
~59--
~3;~
h ~ ~ h
h ~ S~;
. , ,~
_ . ~
~ w ~ h
P~ . ~ ,
W ~ U ~ -W ~
ou ,; , :.,
o. o. t~ I cc~ ~ COu> ,~
'-- ~ N . ~ W o , ,;~
X ~ j t CU (n ~ I W w ~ 0
~ o ~ CU N N æ N N C13 CU æ N CU N ~ C~ a ~ ~7
~1 o o o t- P t- 1-- ~ t~ C- O t~
a c~
~- Y
h ~ . ,~
P1 hU~ 0t-- co G\
.' ' ' ~J
N ~1~1.~ 1 ~1 U ~
hl x e; ~7 rd
U~o t- ~ ~ o o
60~ .
~-~L3~
o o a
. . . ~.
8~
~ ~ ~ N N N ~ ~ 0 C~
, ~
N ~ ~ N N N P') ~ ~ N ~ ~ N ,~
tO ~ O :~ U~ ~ N ~0 O ~ V P
CO 0 ~O 0~ CO ~ CO 0
P o
~ co (t) r! N "~
N r~ O~ ~) N ~ ~ ~
0~ gj O NO co~ o o~ ~o~ ~o~ C~l æ ~ N ~ y
$~ :
~l a a a a ~
~ - 0~
0 ': .
a ~
r~ u
-61
~L~L3~6~
,, :
~U W ~4
o o
N h ~ I ~ I $
O r l CU ~1 o ~
Q ~ O O O O O O
_
h ~ Ul
. o o o o o tq
~_ ~9 ~ N
O ~ ~1 ~ 0
E~ o P
:~
_ :~ :
i ~ 0 ~ ~O ~ ~ g ~
CJ N N ro ~ N N N !J C~
V ,O
~ .
8_ u~ o N ~r) o L~ N ,D ~ .
In N ~ ~ CO ::1 N CUIr) ~ ~ ~ Cll O
P~
- ~ 0 ~ ~ 0 0 ~a~ 0 co t-- ~ ~ tr~
~ h
:~ ~ 0
r~ 0 0 ~O U~
* ~_ ~ ~ cOr~ ~ ~tn co ~ ~ u~
~ .~ . co . ~ . æ
H I ~ ~ ~ ; ~ ~ C~
E-l~ rl ~ ~ O ~O C~i C0 N U~ CJ~ 15~ r i .
~ ~ o o o o o u~ o o $
,~a_ ~ ~ ~3 æ 2 ~ æ ~ æ ~ N
1~ qO~
~ I O O O O O O O O O O O O O I O O ~ ~ ~
~ ~
0
:~ ~ W
P- h ~ CO ~ 0~ ~1 C~ 0
O ~
0~ a ~ ~4
O ~D ~ rl ~O ~ ~O ~ ~ U) æ~
O
p~ ~ ~ ~ o ~ ~
CO O~ rl C~l ~ ;~g U~ U> ~ CO ~ 0
I t- t- a~ oo co CO OD C~ CO ~ O~
-~2-
.,~'''~.
.1,
~ ~33~
h ~ 0 ~
~, h ~ 0 0
h U:l
.i . ~ ,
C,~ O t--
. ~ h
.. ~ , . ~ CO t~ ~ O C~
v ~ ~ ~ co co co a~ ~ co t-- t-- ~ ~ co co
,_( ~ N ~ ~O ~ $ ~ ~O t
~¦ ~ -- 2 æ ,~ , ,o~ ,
~¦oooooooo~oo~ooooo~
Q) . ' ,~
,_ , '~ ~
~, h ~ O
O
o~ ~ ~ ~ ~ ~ ~ V '
--63-
~13~164
V~
N ~ N N ~ ~ ~ æ ~ N N t~
O
o~ ~ ~ o v~ aJ t~
U J N ~ 1 N ~ ~ N 'i ( ~ ~ a
2 N NO~NO NO NO ~o S~ NO O O N
~¦ ~ ~ a ~ s r ~ ~ ~ O
o~ .
~o tq
~ ~ ` ~ ~D o ~) ~U~ ,~ a ~
P~ o~ oc ~ a '
--61~--
~331~4
. ..
o ,~ n,
ho
,~ . p
N c~ N N.~ ~ N N ~1 0 ~ lV~ N
gl g ~ O ,~ ~ O ~ a~ N ~ ~ ~
N~0t-- ~ t~ O N ~ OD 'J P
. _ O
; ~ N ~ .r~ ri O ~O ~ N N
otN-- o ~ NO r~ rl O~ ~r¦ ~j Cr~ ~ rl N ~; ~; rl 13
~¦ ~ g ~¦ N NO O ~O N æNO r~ I a æ N rl r l
o o 1 o o o ~ r- O o
a a ~
. ~
~
O ~ ~ t-- rl ~ O ~ ~O C~ U~
:
O P
rl rr¦ rl r~
N ~ N N N N ~ N 0N ~ ~ g ~ P
- -65~
~3~
_
h ~ V o
~ '
. ~ " . . ~, .
. . , ~
rl N r1 ~ ~ .:J 1~1 ~r) ~ f'l N N
g~ ' ~ N W ~, ~!,
~ E~ N
-- * ~ N ~ N . ,, ~ ", ,~
~ ~ ~ ~ N ~I h
_ ~ ~ rl O r-i~I vt N N ~i rl N rl N ~ ,~
N 11~ ~ ~I N ~ rl ~ NO U~ NO V~ NO iP.
h
~ ¦ ' ' ' ' ' '
",,;~ .
- ~D hV
h ~ ,~
O r~ o ~o ~ Do N t~
o ~o ~ o ~ a
"~ ~ r
-66~
1~33~
g b ~ ~, O
a ~ 8 8 8
` ~ ~
'~ ., ~ ;
~,
~ .
H ~ t CO ,~ ~ C '~
S ~ ;~ N ~ ~i ~i
U ~ U~ O U~ O1~ ,01 U~ ON N rl r~
~¦ ' ' ~,
C~
~' ' '
H
~ ~C
~ ~ ~0 ~0 ~ 0 ~0 ~0 rl rl ~0
S~ ~ ~ ~ a~d
--~7--
~13
. ~ ~ cUo~
c~o `8~ ON~ a
h~ O ~ ,o ~ P N
~1 ~ N V~ 0 3 t-- O ~
ao CC) CO ~O ~O CO CO ~
O~ ~I CO t~ O N ~ hh
*;~ ~ o~
~ Yo~ 9 S 3
~¦ ~o ~ ~ d
Y Y Y ~ ~ 3 a
} ~ ,r ~ ~
t-- CO 1,~ *, ,~
~6~3-
r~ ~ ~ 33 ~ ~
a) o
~ Ql ~ N
r~
O rl ~ l
~ r~ 4~
a) u, r~ .
~, _, ~1 ~,Q
: i r-i ~ r-l ~)
,: o ~ a) (U
:~ ~ O ~ ~ t~
~ r~
1 o s-l~1 a
u~ I~ o o c
~-1 o Ql a) r~
rl 00 ~ 4 a) Q
t l r-l a) c
.4 5
rd Lt~
. ~
O o\ L~ ~ O r~r~ rl U~
O rl ~ Lr~
~) o~O
O a)Ltl ~ J
Q h
rl rl U?
_~ ~ O
1 ~ ~ ~ O
:, u~ u~ ~ ~ 4
~ . ~ o o o o ~
E~ ~ ) OD ~ r~ o ~1
_ ' .S
U ~
o
~: ~ Q~ , . s 4
~c ~ ~ u~ ~ o ,~
,) ~I r~l ,~
H ~ ~ ~ r-l ~) ~rl
~ ~1 N r~ I rd ~ ,~, r-l U~
c~ z 4~ ~
~_ _, Ln ~r ~ r~l
r-l r~l ~ r-l ~1 a)Qi
rr) ~ E~ ,4 o\ E~
O ~
p:l ~-I r l ~ ~ X
1:1 O L~ ) O a
m ~ o 4~
,¢ ~ ~: ~ o a.~ ~:,, rc~ r-l
E-l r-l O o\ ~D ~ rC5 1 r-l
O C~~ ~r Ln o
4 rl r-lr-lC5~ 10
r~ O ~ U~
~) O ~ U~
~ O O O O ,~
a) ~) or-lr~
Z ~ ~
~ rda.) Lt ) H --1
rl ~ O
o a)
~ ~ V Q
a
-IJ r~ r
;~ X ~ ~ ~ r-l
r~-rl ~ ~ O
o~ ~ ~ a) tn 4-1
d ~O Q O
h O ~ r~ r-l
O N U~ ~1 1 a)
H O,!~ ~ N
5-10 U~ r~
rd l:~i ral ~ $
a) o ~ s~ m r~lrl a~
rd z O ~ ~ r-l
rl~ ~ (U ~ O ~
E? 0 ~ rl
~d ~C Z
~1 --1 r-l r-lr-l r-l ~1 ~rl 1~
O ~ ~ ~ rlEl O
~d ~ O
3 ~ rd
(D Q ~ o
Ln o\ o\ E-~
~ ~ ~ ~ ~ O ~ ~D
,~ ~ _~ ~ o ,~
Q. ~ ,-1a~ ,-1 Ql h ~) '
~; -- ~ --
O r-l ~
~C ~ ~ D ~ O Or~ CO Ci~ O O
r-l r-lr-l r-l * `~~ `~ ---I Z
6 9 -
.~
~3316~ -
'.
These ~xamples illustrate uniformity o~
toughness in a 3 inch by five inch by 1/~ inch thick
molded plaque. Samples are cut from this plaque so that
notched Izod may be determined near and far from the gate
in the flow and transvers~ directions. Utilizing the
procedure described previously above thermoplastic compo-
sitions are prepared having the composition set f orth in
Table 40 Controls 1 and 3 represent toughened prior art
10 polya~lide compositionsc E~.amples 164 to 167 represent
composi~ions of this invention. Examples 166 and 1679 in
particular, have uniformly high toughness with 20 percent
by weight polymer added to the polyamide matrixO
The data in Table 5 illustrate the effect of
- decreasing notch radius on certain prior art compositions
and preferred compositions of the invention. The results
show that the prior art materials are more sensitive to
this effect than the pre~erred compositions of this
invention.
A further test which demonstrates the effec~ of
notched radius on toughness is as follGws~ Each of the
following materials was scra~ched to a depth of 20 mils
with a raæox blade which gives a notch radius of about
0.~ mil and was tested using a Gardner Impact Tester
IG~1115 manufactured by Gardner Laboratories9 IncO,
Bethesda, Maryland~ The break occurred at the following
loadings.
Matrix 1 6 inch pounds
Control B ~ inch pounds
Using the same procedure a material as described
in Example 5 of the present invention broke at 69 inch
pvunds.
-70-
~ ~ c~ oo ~ co
~ ' h 1~ O C~
: ,_ ~,
. ~ ~1 o o Co ~ U~
E~ ~ t~ ~ N~ ~
, ~ ~ ~ ~ O O
~ i H ~. ~ 1~ O ~U ~ . ^1
Y~~ O ~ \D cO tf) CO CO
~ o N CC~
rl
~1 ~ ~ ..
¢ ~1 ~ ,1 r~l r-¦ r~l
F~ C~ rd ~ rd
O ~ ~ ,h ~
li3 ~ O O O O O O O O O O O
~i P~ ~4 V~ P~
. ~J) N ~ NC~l ~
::
~1 N t~
rJ
~ ~ ~ ~ O ~O
~71-
~33
8 ~ a
, b~
l ~ 3
72
~33~
~XAMPLE 16~
A blend of ~5 weight percent of Matrix 1 and
15 weight percent of Polymer 66 containing additives of
Example 15L~ was melt extruded into the form of a film.
The blend was extruded at a temperature in the range of
2~0-2~5C. in a Sterling extruder through an ~-inch
(20~32 centimeters~ wide Johnson die maintained at a
temperature of about 290-295C. The molten film was
extruded onto the surface of a rotating (at about 15 feet
(4.57~ meters) per minute) quench drum maintained at a
temperature of.about 70Co Full wire electros-tatic
pinning was used to insure uniform quenching of the cast
film which was 10 mils (250 microns) in thickness~ Sheets9
~ inc~es by 4 inches (10.16 centimeters by 10.16 centi~-
meters)9 cut from the roll of cast film were stretched
simultaneousiy ~in a T. M. Long Co. stretcher) 2.5X in
mutually perpendicular directions at a tempera~ure of
about 230C~ The cast film stretched uniformly in all
directions. Matrix 1 is extremely difficult to cast
into a film hence a control of Matxix 5 was utilized. A
cast film of Matrix 5 without Polymer 66 was difficult,
to stretch uniformly and tended to exhihit line drawingO
Another sample of` the cast f'ilm was thermo~
formed7 after being preheated for about ~0 seconds in
an oven heated to about 210C., into the shape of a dish
1~5 inches (3.~1 centimeters) deep by 5 inches (12.7
centimeters) in diameter. The male portion of the dish
mold was heated to about ~00C. and the female portion.
was at about 160C~
-^73-
., ~
