Note: Descriptions are shown in the official language in which they were submitted.
2~~~1~~
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R D-21060
~Q!LYMERS OF ETHYLENICAL Y
N ATURATED CYCLIC ORTHO ESTERS
This invention relates to new polymers of ethylenically
unsaturated monomers, and more particularly to polymers containing
cyclic ortho ester functionality.
In recent years, there has been considerable interest in
developing polymer compositions which include normally incom-
patible polymers. Examples are compositions comprising linear
polyesters such as p~oly(eth.ylene terephthalate) and poly(butylene
terephthalate) in combinatian with olefin and olefin-diene polymers.
It might be expected that various properties of the linear
polyesters, such as i;ensile strength, tensile elongation and impact
1 5 strength, would be improved by the addition of olefin or olefin-diene
polymers. However, the resulting blends exhibit incompatibility as
evidenced by gross phase separation and frequently degradation,
rather than improvement, of physical properties.
One method of compatibilizing otherwise incompatible
polymer blends is to incorporate therein a copolymer, typically a
block copolymer, of irhe otherwise incompatible polymers.
Copolymers of this type can be formed by incorporating in one poly-
mer structural units which are chemically reactive with the other
polymer. Thus, for example, linear polyesters or polyamides having
2 5 terminal carboxylic acrid groups can undergo reaction with olefin or
olefin-diene copolymers containing epoxy groups, either as sub-
stituents on the polymer chain or as grafted units. Reference is
made, for example, to U.S. Patent 4,965,111. Similarly, amine-ter-
minated polyamides c:an undergo reaction with olefin or olefin-diene
3 0 polymers containing integral or grafted malefic anhydride moieties.
The resulting block copolymers do not exhibit the indicia of incom-
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R D-21060
patibility which are found in simple blends. Moreover, they are often
useful as compatibili~:ers for blends of the otherwise incompatible
forms of the two pol~rmers.
While polymers containing reactive substituents or
grafted units such as epoxy and anhydride groups are known, many of
them have not met with wide commercial acceptance. One possible
reason is the relative chemical inactivity of such polymers, where-
upon it is difficult to promote the copolymer-forming reaction to
any substantial extent.
1 0 The present invention provides a wide variety of poly-
mers, particularly copolymers, of ethylenically unsaturated
monomers. These polymers contain highly reactive cyclic ortho es-
ter groups as substituents. Said cyclic ortho ester groups can un-
dergo reaction with numerous other polymers, forming copolymer-
containing compositions with excellent properties.
Accordingly, the invention includes polymers comprising
structural units of the formula
R5
( CHZ ) ~-O
-CH-C-
(I) .0R1
6 ~ 4 33
R X-O f R ~ C-R C
R
( CHy ) m-O
wherein:
R 1 is C~ _ 1 o primary or secondary alkyl or aralkyl or a
C6-~ o aromatic radical, and R2 is C~ _~ p primary or secondary alkyl
or aralkyl or a C6_~ o aromatic radical, or R~ and R2 together with
2 5 the atoms connecting them form a 5-, 6- or 7-membered ring;
R3 is hydrogen or C~ _4 primary or secondary alkyl;
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R D-21060
R4 is an unsubstituted or substituted C1 _6 alkylene or
C6_~o arylene radical;
RS is hydrogen or methyl;
R6 is hydrogen, C~_6 alkyl or a C6_io aromatic radical;
X is a substantially inert linking group;
m is 0 or 1;
n is from 1 to 2-m; and
p is 0 or 1.
An essential feature of the polymers of this invention is
the presence of cyclic; ortho ester moieties. The R~ value therein
may be a C1 _4 primary or secondary alkyl radical such as methyl,
ethyl, n-propyl, isopropyl, n-butyl, isobutyl or secondary butyl, or an
aralkyl or aromatic radical as defined above. Any substituents
should be non-reactive under the conditions of the invention; exam-
pies are halo, vitro and alkoxy. Unsubstituted primary radicals and
especially the methyl radical are generally preferred.
The R2 value may be a C~ _4 primary or secondary alkyl,
aralkyl or aromatic radical as defined above for R~ . It is also pos-
sible for R~ and R2 together to form a 5-, 6- or 7-membered ring
with the atoms connecting them. Thus, the invention includes com
positions prepared from certain spiro ortho ester compounds.
The R3 radical may be hydrogen or an alkyl radical simi-
lar to R~ and R2. It is preferably hydrogen.
The R4 radical is an unsubstituted or substituted C~ _6
2 5 alkylene radical, any substituents being inert to ortho ester forma-
tion and reaction with aryl chlorides; e.g., alkoxy. Preferably, R4 is
methylene.
The Rs radical may be hydrogen, alkyl or aryl as previ-
ously defined. It is preferably hydrogen.
3 0 The X value may be any linking group which is substan-
tially inert under the conditions of formation and polymerization of
the cyclic ortho ester, of the invention and copolymer formation
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R D-21060
from polymers thereof. Those skilled in the art will understand that
a wide variety of groups fit this description, and the invention is not
limited in that respect. Suitable X groups include unsubstituted and
substituted divalent aliphatic, alicyclic and aromatic radicals and
combinations thereof, any substituents being of the type previously
described. Said radicals may be attached to other divalent radicals
such as carbonyl, sulfone, carbamoyl, disubstituted silicon and
alkyl- and arylphosphoryl. The preferred X groups have the formulas
0
1 0 ( I I ) -IC- and
CH2-
( I I I ) ___,~~ .
1 5 The polymers of this invention include those of the type
which may be preparE~d from acrylic and methacrylic acid esters,
wherein X has formula II, as well as vinylbenzyl ethers, wherein X
has formula III. Both vinyl-derived (RS is hydrogen) and isopropenyl-
derived (R5 is methyl) polymers are included; for example, polymers
20 of acrylic and methacrylic acid esters. For the most part, R5 is
preferably hydrogen when X has formula III.
The values of m and n depend on whether the cyclic ortho
ester moiety is a 5-membered or 6-membered ring. In general, 5-
membered rings are preferred; that is, m is 0 and n is 1. However,
2 5 the invention also includes polymers in which a 6-membered ring is
present, which requires either that m and n both be 1 or that m be 0
and n be 2.
20 68 182
RD-21060
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Also included are polymers in which p is 0; that is,
compounds not containing an R4 value. Most often, p will be 0 when the
ortho ester ring is a 6-membered ring.
Many of i:he ethylenically unsaturated cyclic ortho esters
s which may be converl:ed to the polymers of this invention are disclosed
and claimed in commonly owned Canadian Patent application Serial No.
2,056,510 filed Novernber 11, 1991. Esters of this type may be prepared
by the reaction of a h~ydroxy-substituted ortho ester of the formula
( CHI ) "-O OR1
(IV) EIO"'tR4~----C-R3
' C
( CHZ ) m-O RZ
wherein R'-4, m, n and p are as previously defined, with a suitable
reagent such as acryl~oyl chloride, methacryloyl chloride or a vinylbenzyl
chloride. Said reaction takes place under conventional conditions. In
the case of acryloyl chloride or methacryloyl chloride~it typically occurs
in the presence of a tE~rtiary amine as acid acceptor and in solution in a
relatively non-polar organic solvent. The hydroxy-substituted ortho ester
and acryloyl or methy~~cryloyl chloride may be employed in
approximately equimolar amounts, or the chloride may be employed in
slight excess. The amine is generally present in excess, to ensure
neutralization of all the acidic by-product formed.
zo Reaction between the hydroxy-substituted ortho ester
and vinylbenzyl chloride is also conducted under conventional
conditions, typically in the presence of an alkaline reagent such as
sodium hydroxide. Again, the hydroxy-substituted ortho ester and
vinylbenzyl chloride may be employed in roughly equimolar amounts,
25 Or, in this case, an e:KCess of the ortho ester may be employed. The
molar proportion of base is generally about equal to that of ortho
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ester. No solvent is generally necessary, although one may be em-
ployed if desired.
The preparation of ethylenically unsaturated cyclic ortho
esters is illustrated by the following examples. Molecular struc-
tures of all products in Examples 1-4 were confirmed by proton and
carbon-13 nuclear magnetic resonance spectroscopy.
Exam lio a 1
A 5-liter 3-necked flask fitted with a mechanical stir-
rer, pressure equalizing addition funnel and nitrogen inlet was
charged with 301 grams (2.03 moles) of 4-hydroxymethyl-2-
methoxy-2-methyl-1,3-dioxolane, 514 grams (5.08 moles) of tri-
ethylamine and 2 liters of methylene chloride. The flask was im-
1 5 mersed in an ice-water bath and 193.1 grams (2.13 moles) of
acryloyl chloride was added over 50 minutes under nitrogen, with
stirring. The mixture was stirred at room temperature overnight
and the filtrate was washed twice with 2-liter portions of water,
dried over magnesium sulfate, filtered and vacuum stripped. A free
radical inhibitor, 3-t-butyl-4-hydroxy-5-methylphenyl sulfide, was
added in the amount of 200 ppm. to the residue which was then dis-
tilled under vacuum. The desired 4-acryloyloxymethyl-2-methoxy-
2-methyl-1,3-dioxolane distilled at 80-85°C/0.5-1.0 torr.
2 5 Examl to a 2
The procedure of Example 1 was repeated, employing 281
grams (1.9 moles) of 4-hydroxymethyl-2-methoxy-2-methyl-1,3-
dioxolane, 481 grams (4.76 moles) of triethylamine and 199 grams
3 0 (1.9 moles) of methacryloyl chloride. The product, 4-methacryloyl-
oxymethyl-2-methoxy-2-methyl-1,3-dioxolane, was collected at
80°C/0.4 torr.
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R D-21060
Example 3 .
The procedure of Example 1 was repeated, employing 21
grams (100 mmol.) of 4-hydroxymethyl-2-methoxy-2-phenyl-1,3-
dioxolane, 25.3 gram.; (250 mmol.) of triethylamine, 9.5 grams (105
mmol.) of acryloyl chloride and 150 ml. of methylene chloride. The
crude product was purified by column chromatography over basic
alumina, using 15% (by volume) ethyl acetate in hexane as an eluant,
1 0 to yield the desired 4-acryloyloxymethyl-2-methoxy-2-phenyl-1,3-
dioxolane.
Exam Ip a 4
A 4-neckE~d 250-ml. round-bottomed flask equipped with
a mechanical stirrer, a pressure equalizing addition funnel, a con-
denser and a thermonneter was charged with 51.9 grams (350 ml.) of
4-hydroxymethyl-2-m~~thoxy-2-methyl-1,3-dioxolane and 14.01
grams (350 mmol.) of powdered sodium hydroxide. The slurry was
stirred for 15 minute:. under nitrogen, after which 41.1 grams (270
mmol.) of vinylbenzyl chloride (isomeric mixture) was added drop-
wise over 10 minutes. The mixture was heated to 80°C, whereupon
an exothermic reaction took place which caused the temperature to
rise to 140°C. The rnixture was stirred overnight under nitrogen,
diluted with 400 ml. of methylene chloride and 5 ml. of triethyl-
amine and washed twice with 250 ml. of aqueous sodium chloride
solution. The organic; layer was dried over magnesium sulfate, fil-
tered and vacuum stripped, and the residue was purified by column
chromatography over basic alumina using a 2:1 (by volume) mixture
3 0 of hexane and methylf~ne chloride as eluant. There was obtained the
desired isomeric mixture of 4-(2-methoxy-2-methyl-1,3-dioxo-
lanyl)methyl vinylbenzyl ethers.
~o~~~~
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The polymers of this invention may be prepared by poly-
merization of the ethylenically unsaturated cyclic ortho esters un-
der free radical conditions, either alone or in the presence of other
monomers. The term "polymer", as used herein, includes addition
homopolymers and, especially, copolymers with one or more other
monomers.
Polymerization by the free radical method may be ef-
fected in bulk, solution, suspension or emulsion, by contacting the
monomer or monomers with a polymerization initiator either in the
1 0 absence or presence of a diluent at a temperature of about 0°-
200°C.
Suitable initiators include benzoyl peroxide, hydrogen peroxide,
azobisisobutyronitrile, persulfate-bisulfite, persulfate-sodium
formaldehyde sulfoxylate, chlorate-sulfite and the like.
Alternatively, polymerization may be effected by irradiation tech-
piques, as by ultraviolet, electron beam or plasma irradiation.
A large variety of polymerizable compounds can be used
to form copolymers of this invention. They include the following:
(1 ) Unsaturated alcohols and esters thereof: Allyl,
methallyl, crotyl, 1-chloroallyl, 2-chloroallyl, cinnamyl, vinyl,
2 0 methylvinyl, 1-phenallyl and butenyl alcohols and esters of such al-
cohols with saturated acids such as acetic, phenylacetic, propionic,
butyric, valeric, caproiic and stearic; with unsaturated acids such as
acrylic, a-substituted acrylic (including alkylacrylic, e.g.,
methacrylic, ethylacrylic, propylacrylic, etc. and arylacrylic such as
phenylacrylic), crotonic, oleic, linolenic and linolenic; with polyba-
sic acids such as oxalic, malonic, succinic, glutaric, adipic, pimelic,
suberic, azelaic and :~ebacic; with unsaturated polybasic acids such
as malefic, fumaric, citraconic, mesaconic, itaconic, methylene-
malonic, acetylenedicarobxylic and aconitic; and with aromatic
3 0 acids, e.g., benzoic, phthalic, terephthalic and benzoylphthalic acids.
(2) Unsaturated acids (examples of which appear above)
and esters thereof with lower saturated alcohols, such as methyl,
20~~1~~
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R D-21060
ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, 2-
ethylhexyl and cyclohexyl alcohols and with saturated lower poly-
hydric alcohols such as ethylene glycol, propylene glycol, tetra-
methylene glycol, neopentyl glycol and trimethylopropane.
(3) Unsaturated lower polyhydric aicohols, e.g., butene-
diol, and esters therE~of with saturated and unsaturated aliphatic and
aromatic, monobasic and polybasic acids, examples of which appear
above.
(4) Esters of the above-described unsaturated acids, es-
pecially acrylic and methacrylic acids, with higher molecular weight
monohydroxy and polyhydroxy materials such as decyl alcohol, iso-
decyl alochol, oleyl alcohol, stearyl alcohol, epoxy resins and
polybutadiene-derived polyols.
(5) Vinyl ~~yclic compounds including styrene, o-, m-, p-
chlorostyrenes, bromostyrenes, fluorostyrenes, methylstyrenes,
ethylstyrenes. and cyanostyrenes; di-, tri- and tetrachlorostyrenes,
bromostyrenes, fluorostyrenes, methylstyrenes, ethylstyrenes,
cyanostyrenes; vinylnaphthalene, vinylcyclohexane, divinylbenzene,
trivinylbenzene, allylbenzene and heterocycles such as vinylfuran,
vinylpridine, vinylben;zofuran, N-vinyl carbazole, N-vinylpyrrolidone
and N-vinyloxazolidone.
(6) Unsaturated ethers such as methyl vinyl ether, ethyl
vinyl ether, cyclohexyl vinyl ether, octyl vinyl ether, diallyl ether,
ethyl methallyl ether and allyl ethyl ether.
(7) Unsaturated ketones, e.g., methyl vinyl ketone and
ethyl vinyl ketone.
(8) Unsaturated amides, such as acrylamide, meth-
acrylamide, N-phenylacrylamide, N-allylacrylamide, N-methylol-
acrylamide, N-allylcap~rolactam and diacetone acrylamide.
3 0 (g) Unsaturated aliphatic hydrocarbons, for instance,
ethylene, propylene, butenes, butadiene, isoprene, 2-chlorobutadiene
and a-olefins in general.
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R D-21060
(10) Unsaturated alkyl halides, e.g., vinyl fluoride, vinyl
chloride, vinyl bromicje, vinylidene chloride, vinylidene bromide,
allyl chloride and allyl bromide.
(11 ) Unsaturated acid anhydrides, e.g., malefic, citraconic,
itaconic, bis-4-cyclohexane-1,2-dicarboxylic and bicyclo(2.2.1.)-5-
heptene-2,3-dicarboxylic anhydrides.
(12) Uns~~turated nitrites, e.g., acrylonitrile, meth-
acrylonitrile and other substituted acrylonitriles.
Random addition polymers are within the scope of the in-
vention, and copolymers with vinylaromatic compounds such as
styrene are preferred. Also preferred are graft copolymers prepared
by grafting the ethylenically unsaturated cyclic ortho esters on
previously formed polymers. More preferably, said graft copolymers
are copolymers comF~rising ethylene and propylene structural units;
and still more preferably, copolymers also comprising structural
units derived from at least one non-conjugated diene, said copoly-
mers frequently beincl identified hereinafter as "EPDM copolymers".
Such graft copolymer:; may be conveniently prepared by absorption
of the ethylenically unsaturated ortho ester and a free radical
polymerization cataly:;t on the EPDM copolymer followed by grafting,
frequently effected by extrusion at a temperatures in the range of
about 150-300°C.
The preparation of the copolymers of this invention is
illustrated by the following examples. Molecular weights, when
2 5 given, are weight average and were determined by ge! permeation
chromatography relative to polystyrene.
Examples 5-9
3 0 Mixtures of various ethylenically unsaturated ortho
esters and 1 gram of 2,5-dimethyl-2,5-di(t-butylperoxy)hexane
were premixed and combined with 1 kilogram of a commercially
~~~~16~
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R D-21060
available EPDM copolymer containing about 83 mole percent ethylene
and about 5.4 mole percent norbornene units. .The blends were stored
for about 16 hours at 20°C to enable the ortho ester and polymer-
ization initiator to be completely absorbed by the EPDM pellets, and
were then extruded on a twin-screw extruder with zone set tem-
peratures ranging frorn 120° to 205°C. The extrudates were
cooled
in a water bath, pelletized and dried in vacuum.
The proportion of the ethylenically unsaturated ortho
ester grafted on the E:PDM copolymer was determined by dissolving a
1 0 sample of the graft copolymer in xylene at about 130°C, pouring the
resulting solution inta~ acetone and filtering and drying the purified
copolymer, which was then analyzed by Fourier transform infrared
spectroscopy. Gel content was determined by continuous extraction
with hot xylene for 4f3 hours followed by drying and weighing of the
insoluble residue. The results are given in Table I, with all percent-
ages being by weight.
2 0 Example
5 6 7 8 9
Ortho ester:
Example 1 1 1 2 3
Percent based on EPDM copolymer 0.3 1.0 3.0 1.0 1.3
Amount grafted, % >90 >90 >90 50 - -
Gel, % 0 4 0 4 0 0 - -
A 5-liter 3-necked flask equipped with a reflux con-
denser and nitrogen purge means, a mechanical stirrer and a ther-
mometer was charged with 936 grams (9 moles) of styrene,. 960 ml.
of methyl ethyl ketone, 960 mg. of azobisisobutyronitrile and 31
grams (150 mmol.) of the product of Example 1. The solution was
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R D-21060
purged with nitrogen for 30 minutes, after which it was heated at
70°C under nitrogen for 15 hours. An additional 600 mt. of methyl
ethyl ketone and 500 mg. of azobisisobutyronitrile were added and
stirring and heating were continued at 70°C for 4 hours. The solu-
tion was cooled to room temperature and poured into twice its vol-
ume of methanol, with rapid stirring. The precipitated product was
filtered, slurried several times in methanol and refiltered, and
vacuum dried at 60°C for 48 hours. It was shown by nuclear mag-
netic resonance and Fourier transform infrared spectroscopy to be
1 0 the desired copolymer of styrene and the ortho ester acrylate, con-
taining 2.2 mole percent ortho ester groups. Its molecular weight
was 102,000. .
Exam I~e 11
Following the procedure of Example 10, a polymer con-
taining about 2.5 molE; percent ortho ester groups was prepared by
the reaction of 498 grams (4.79 moles) of styrene with 21.8 grams
(108 mmol.) of the product of Example 1 in 346 ml. of toluene, using
5.2 grams of azobisisobutyronitrile. The reaction mixture was di-
luted with an additional 500 ml. of toluene prior to isolation of the
product, which had a molecular weight of about 50,000.
Exam IR a 12
Following irhe procedure of Example 11, a product con-
taining 1.6 mole percent ortho ester groups was prepared by the re-
action of 359 grams (3.45 moles) of styrene, 20 grams (76 mmol.) of
the product of Example 4, 252 ml. of toluene and 3.79 grams of azo-
bisisobutyronitrile. It, molecular weight was 58,000.
Certain polymers of this invention react with other
polymers containing reactive groups, particularly those capable of
CA 02068162 2002-05-30
RD-21060
-13-
nucleophilic substitution such as amine, hydroxy, thio and carboxy
groups and functional derivatives thereof, to form copolymer-containing
compositions. Included are copolymer-containing compositions with
polymers otherwise incompatible with EPDM copolymers, including
s linear polyesters and polyamides. Such copolymer-containing
compositions and the method for their preparation are disclosed and
claimed in commonly owned U.S. Patent 5,132,361.
By reason of the presence of the copolymer, said
compositions are compatible and may be molded into articles having
to excellent physical properties. They are also useful for further
compatibilizing blends of the two polymers to form molding compositions
having similar excellent properties.
Polyesters suitable for preparing copolymer-containing
compositions include those comprising structural units of the formula
O O
II 1l
15 (v) -O-R6-O-C-A1-C-
wherein each R6 is independently a divalent aliphatic, alicyclic or
aromatic hydrocarbon or polyoxyalkylene radical and A' is a divalent
aromatic radical. Such polyesters include thermoplastic polyesters
illustrated by poly(alkylene dicarboxylates), elastomeric polyesters,
ao polyarylates, and polyester copolymers such as copolyestercarbonates.
Because the principal reaction which occurs with the ortho ester groups
involves a carboxylic acid group of the polyester, it is highly preferred
that said polyester have a relatively high carboxylic end group
concentration. Concentrations in the range of about 5-250
is microequivalents per gram are generally suitable, with 20-150
microequivalents per gram being preferable and 20-80 being particularly
desirable.
20~~~.~~
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R D-21060
The polyester may include structural units of the for-
mula
\ ~ /~\ z II
(VI) -O-R6-O-C-AZ N-R -N A -C-
~C~ \C~
10
5
wherein R6 is as previously defined, R~ is a polyoxyalkylene radical
and A2 is a trivalent aromatic radical. The A~ radical in formula V
is most often p- or m-phenylene or a mixture thereof, and A2 in for-
mula VI is usually derived from trimellitic acid and has the struc-
10 ture
The R6 radical may be, for example, a C2-~ p alkylene
1 5 radical, a C6_~ o alicyc:lic radical, a C6_2o aromatic radical or a
polyoxyalkylene radical in which the alkylene groups contain about
2-6 and most often 4 carbon atoms. As previously noted, this class
of polyesters includes the poly(alkylene terephthalates) and the
polyarylates. Poly(alkylene terephthalates) are frequently pre-
ferred, with polyethylene terephthalate) and poly(butylene tere-
phthalate) being most preferred.
The preferred polyesters are polyethylene terephtha-
late) and poly(butylenis terephthalate), generally having a number
average molecular weight in the range of about 20,000-70,000, as
~0~~1~~
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R D-21060
determined by intrinsic viscosity (IV) at 30°C in a mixture of 60%
(by weight) phenol and 40% 1,1,2,2-tetrachloroethane.
Polyamide~s may also be employed for the formation of
copolymer-containing compositions. Included are those prepared by
the polymerization of a monoamino-monocarboxylic acid or a lactam
thereof having at least 2 carbon atoms between the amino and car-
boxylic acid group, of substantially equimolar proportions of a di-
amine which contains at least 2 carbon atoms between the amino
groups and a dicarbo.xylic acid, or of a monoaminocarboxylic acid or
a lactam thereof as defined above together with substantially
equimolar proportions of a diamine and a dicarboxylie acid. (The
term "substantially equimolar"- proportions includes both strictly
equimolar proportions and slight departures therefrom which are in-
volved in conventional techniques for stabilizing the viscosity of the
1 5 resultant polyamides.) The dicarboxylic acid may be used in the
form of a functional cjerivative thereof, for example, an ester or acid
chloride.
Examples of the aforementioned monoamino-mono-
carboxylic acids or lactams thereof which are useful in preparing
the polyamides include those compounds containing from 2 to 16 car-
bon atoms between the amino and carboxylic acid groups, said carbon
atoms forming a ring .containing the -CO-NH- group in the case of a
lactam. As particular examples of aminocarboxylic acids and lac-
tams there may be mentioned e-aminocaproic acid, butyrolactam,
pivalolactam, e-caprolactam, capryllactam, enantholactam, un-
decanolactam, dodecanolactam and 3- and 4-aminobenzoic acids.
Diamines suitable for use in the preparation of the
polyamides include the straight chain and branched chain alkyl, aryl
and alkaryl diamines. Illustrative diamines are trimethylene-
diamine, tetramethyle~nediamine, pentamethylenediamine, octa-
methylenediamine, hexamethylenediamine (which is often pre-
~~6~~~~
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R D-21060
ferred), trimethylhexamethylenediamine, m-phenylenediamine and
m-xylylenediamine. .
The dicarboxylic acids may be represented by the formula
HOOC-Y-COOH
wherein Y is a divalent aliphatic or aromatic group containing at
least 2 carbon atoms. Examples of aliphatic acids are sebacic acid,
octadecanedioic acid, suberic acid, glutaric acid, pimelic acid and
adipic acid.
Both crystalline and amorphous polyamides may be em-
ployed, with the crysl:alline species often being preferred by reason
of their solvent resistance. Typical examples of the polyamides or
nylons, as these are often called, include, for example, polyamide-6
(polycaprolactam), 66 (polyhexamethylene adipamide), II, 12, 63, 64,
6/10 and 6/12 as well as polyamides from terephthalic acid and/or
isophthalic acid and trimethylhexamethylenediamine; from adipic
acid and m-xylylenediamines; from adipic acid, azelaic acid and 2,2-
bis(p-aminophenyl)propane or 2,2-bis-(p-aminocyclohexyl)propane
and from terephthalic acid and 4,4'-diaminodicyclohexylmethane.
Mixtures and/or copolymers of two or more of the foregoing
polyamides or prepolymers thereof, respectively, are also within the
scope of the present invention. Preferred polyamides are polyamide-
6, 46, 66, II and 12, most preferably polyamide-66.
For the preparation of copolymer-containing composi-
tions, a blending method which results in the formation of an inti-
mate blend is preferred. Suitable procedures include solution
blending, although such procedures are of limited applicability to
many polyesters and polyamides by reason of their insolubility in
3 0 most common solvent;. For this reason and because of the availa-
bility of melt blending equipment in commercial polymer processing
facilities, melt reaction procedures are generally preferred.
Conventional melt blending procedures and equipment may be em-
206~.~.6~
- 17 -
R D-21060
ployed, with extrusion often preferred because of its relative con-
venience and particular suitability. Typical reaction temperatures
are in the range of about 175-350°C.
Those skilled in the art will be familiar with blending
methods and apparatus capable of intimately blending resinous
constituents, especially by kneading. They are exemplified by disc-
pack processors and various types of extrusion equipment.
Illustrations of the I<~tter are continuous mixers; single screw
kneading extruders; counterrotating, non-intermeshing twin screw
extruders having screws which include forward-flighted com-
pounders, cylindrical bushings and/or left-handed screw elements;
corotating, intermeshing twin screw extruders; and extruders having
screws which include at least one and preferably at least two sec-
tions of kneading block elements.
In addition to copolymer, the copolymer-containing com-
positions may also c~~ntain unreacted polyester, polyamide or the
like. In any event, molded parts produced from said compositions
are generally ductile and have higher impact strengths, tensile
strengths and/or tensile elongations than those produced from sim-
ple blends, which are incompatible and often exhibit brittleness or
delamination.
There may also be present in the copolymer-containing
compositions conveni:ional ingredients such as fillers, flame retar-
dants, pigments, dyes, stabilizers, anti-static agents, crystalliza-
2 5 tion aids, mold release agents and the like, as well as resinous com-
ponents not previously discussed including auxiliary impact modify-
ing polymers.
The proportions of ortho ester polymer, other polymer
and other resinous materials are not critical; they may be widely
3 0 varied to provide compositions having the desired properties. Most
often, the ortho ester polymer is employed in an amount in the range
I ~I
CA 02068162 2002-05-30
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_18_
of about 5-95%, preferably about 5-65%, of the composition by weight.
In addition to forming copolymer-containing compositions
that act as compatibilizers in the manner described hereinabove, various
copolymers of this invention and especially random copolymers with
s styrene can compatibilize blends of other, largely dissimilar polymers in
which they are incorporated, as disclosed and claimed in, commonly
owned U.S. Patent 5,231,132.
The preparation of copolymer-containing compositions from
the polymers of this invention is illustrated by the following examples.
~o All percentages are by weight.
Dry blends comprising ortho ester-grafted EPDM
copolymers and poly(butylene terephthalate) were prepared and
extruded at temperatures in the range of 250°C. The extrudates were
desired copolymer-containing compositions; they were pelletized, dried
and molded into test specimens which were tested for tensile strength
and elongation (ASTM procedure D638) and notched Izod impact
strength (ASTM procedure D256).
The results are given in Tables II and III, in comparison with
ao five controls employing (A-D) a blend prepared from unfunctionalized
EPDM copolymer, and (E) a blend prepared from EPDM copolymer
similarly grafted with 3% glycidyl methacrylate.
Example Control Control
13 14 15 A E
Polyester, parts 50 50 50 50 50
Ortho ester- grafted EPDM:
- 19 -
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Example 5 6 8 - - - -
Parts 50 50 50 50 50
Tensile strength, MPa. 16.9 24.2 17.3 13.9 18.5
Tensile elongation, %~ 240 370 290 65 230
TABLE III
Example Control
~s ~7 ~8 ~9 2o a C o
Polyester, parts 9 5 9 0 80 9 5 9 0 9 5 9 0 8 0
Ortho ester-grafted
EPDM:
Example 6 6 6 9 9 - - - - - -
Parts 5 1 0 20 5 1 0 5 1 0 2 0
Impact strength,
joules/m. 64 641 849 264 844 27 32 53
From Table II, it is apparent that copolymer-containing
compositions prepared from the EPDM copolymers of this invention
have substantially higher tensile strengths and tensile elongations
than the control empl~~ying an unfunctionalized EPDM copolymer.
They also have tensile strengths and elongations which are compa-
rable to or greater than those of the control employing an EPDM
copolymer grafted with a substantially higher proportion of glycidyl
1 5 methacrylate. From fable III, it is apparent that each of the com-
positions prepared from the polymers of this invention has a higher
impact strength, and the products of Examples 17-20 a substantially
higher impact strength, than those of the controls.
2 0 Exam to a 21
Following the procedure of Example 14, a similar blend
was prepared in which the poly(butylene terephthalate) was replaced
by a copolyester prepared from 1,4-butanediol and a 0.91:1 (by
25 weight) mixture of dimethyl terephthalate and a dimide-diacid re-
action product of trimellitic acid and a polyoxypropylenediamine
20~~I ~
- 20 -
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having an average molecular weight of about 200. Said blend had a
tensile strength of 10.5 MPa. and a tensile elongation of 435%. A
control in which the ortho ester-grafted EPDM copolymer was re-
placed by an EPDM copolymer grafted with 3% glycidyl methacrylate
had a tensile strength of 7.7 MPa. and a tensile elongation of 505%.
Again, it is apparent that the graft copolymers of this invention may
be employed at substantially lower levels of functionalization than
corresponding glycidyl methacrylate graft copolymers, to obtain
properties of the same order of magnitude.
