Note: Descriptions are shown in the official language in which they were submitted.
~23~ 3
-- 1 --
COOKWARE FORMED FROM A LAMINATE
BACKGROUND OF THE I VENT I ON
This invention is directed to cookware
formed from a laminate, said laminate comprifiing at
least three sheets made from a thermoplastic resin,
the inside sheet made from a thermoplastic resin
having a higher use temperature than the
thermoplastic resin the two outside sheets are made
from. Allah, this invention it directed to a
laminate suitable for molding into cookware.
Cookware utilized in conventional ovens
should have the capability of withstanding the great
temperature variations existing between the
temperature jetting devices and the actual
temperatures within the oven. Though the cookware
is only exposed to the oven's actual temperature,
the usury expectations of the cookware's capacity
to withstand heat it a critical factor in the use of
that cookware. Putting cookware that deforms at
e.g. 200F into an oven set for 325F is clearly
illogical. Equally illogical would be the use of
the tame cookware in an oven whose temperature
jetting device fails to accurately control the
ovine temperature. Thus a low temperature setting
could result in a high oven temperature, and the
cookware would still deform. The realities of life
are that few commercially available gas and electric
ovens have accurate temperature controls and in most
caves the ovens run hotter than the temperature
setting. In a number of cases, an oven temperature
jetting of 400F resulted in an oven temperature a
D-14,362
~23~ 3
high as 475-500F. This it the basis for the first
sentence of this paragraph.
Plastics are typically termed thermoplastic
or thermosetting. Thermoplastics are deformable
with application of sufficient heat. Because
thermosettinq plastic (resins) are cross linked,
they are fairly resistant to heat deformation,
certainly more so than thermoplastics.
Consequently, thermosetting resins have been
extensively used for cookware. Pro example,
cookware have been made from melamine-formaldehyde
resins, unsaturated polyester resin, and the like
Such plastics have excellent heat resistance.
However, they do suffer from a number of significant
deficiencies. Because they crosslin~ during their
curing processes when molded, they shrink and pull
away from the mold surfaces. Unless they are
properly filled with small particulate fillers, the
molded objects have very uneven surfaces, and they
are subject to significant crazing and/or cracking.
High filler loading adversely affects the physical
properties of the molded object and precludes the
direct obtaining of a glossy surface. Thermosetting
resins are difficult to mold. They generally have
to be compression or transfer-molded. Such
processes require much material handling, large
equipment, complicated and relatively expensive
molds, and significant energy c06ts.
Thermoplastics have been used for coating
paper dicier and some of them have been used a
cookware. However, their use as cookware is
severely restricted, certainly to low temperature or
D-14,362
~2~(~8~3
-- 3
microwave oven applications. Thermoplastics, such
as UdelTM polysulfone (made by Union Carbide
Corporation), have been sold for use in making
cookware designed for microwave oven applications.
One would expect that some of such cookware has been
generally employed in conventional ovens as well.
However, UdelT poly6ulfone has not proven to be
suitable for the wide temperatures used in
conventional oven cooking and hence, its usage in
such applications has not been recommended.
Thermoformed polyethylene terphthalate is
used for cookware in microwave and conventional oven
units, but is generally limited in use to about
350F. Above this temperature, the modulus of the
material drops rapidly 80 that cookware will sag and
distort and will be unstable from a handling
standpoint when removing from the oven with a food
load present in the container. In the 400F range,
the polyethylene terephthalate containers will
distort severely and lose their shape.
Though the physical properties of a
thermoplastic might be considered at first blush to
be the basis for its use as generally employable
cookware, i.e., cookware usable in any kind of oven
up to a temperature of 500F, such is clearly not
the cave. Since cookware is in contact with the
food placed therein, the plastic it it made from
must be safe to use and not contaminate the food it
contacts. Temperature gradients exist within
conventional ovens and such a variable requires
actual working information about a plastic's
performance a cookware under a wide variety of
D-~4,362
.;
lZ3(~P813
-- 4
conditions. Further, unless the cookware it
intended to be disposable after the first use, it
should have the capacity of withstanding repeated
washings, by hand or by machine. It should be
detergent re6i6tant and not absorb food, oil and
fit. It should be able to withstand warping on
usage. If it it intended for household use, then it
should meet the aesthetic typically favored, such
as high gloss and smooth surfaces. Further, it it
desirable that the thermoplastic be moldable into a
variety of cookware configurations by a simple
molding process such as vacuum forming or injection
molding. Moreover, since tube use conditions are
guile severe, necessitating the use of a high
performance plastic that tend to be more c06tly,
then all of such performance capabilities are
desirably achievable with tube minimum amount of
plastic usage.
U.S. Patent Application, Serial No. 498,049
wiled in the name of T. I. Hurting on May 25, 1983,
titled "Cookware Made prom Polyarylether6ulfone"
(commonly assigned) describe cookware made from a
composition comprising a polyarylethersulfone as the
sole polymeric component, or when blended with other
polymer the polyarylethersulfone constitutes
greater than 30 weight percent, said weight percent
based on the weight of tube polymeric materials in
the ox~osltion. Also, said Cowan Patent Application
Serial No. 454,758 describes owe } from a
composition containing the polyarylether6ulfone as
having a good combination of physical properties,
* corresponds to Canadian application serial number
454,758 filed May 18, 1984.
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lZ3~313
In the present invention it has been found
that a particular laminate possesses the necessary
combination of properties that a thermoplastic
material need possess to be acceptable for
cookware. Allah the laminate provides extremely
attractive and useful cookware which can be used in
essentially all cooking oven applications.
DESCRIPTION OX THE INVENTION
Cookware made from a laminate, said
laminate comprising at least three sheets made from
a thermoplastic resin, an inside sheet made from a
thermoplastic resin having a higher use temperature
than the thermoplastic resin the two outside sheets
are made from, said thermoplastic resin selected
from a polyarylether~ulfone, a poly(aryl ether),
polyarylatè, polyetherimide, polyester, aromatic
polycarbonate, styrenes resin, poly(aryl acrylate),
polyhydroxylether, poly(arylene suffice) or
polyamide,
A preferred laminate comprises at least
three sheets, an inside sheet made from a
thermoplastic resin selected from a
polyarylether6ulfone, a paltrily ether) or a
polyetherimide with both outside eta being made
from a thermoplastic polyester, preferably,
polyethylene terephthalate.
Cookware made from the laminate of this
invention meets toe key requirements needed or
cookware molded from plastic materials described
above. The cookware ox this invention it suitable
for use in conventional as well as microwave ovens.
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123C~3
THE THERMOPLASTIC POLYMERS
A Polvarvlethersulfones
The polyarylethersulfones of this invention
are amorphous thermoplastic polymers containing
units of toe formula:
(I) 2 n ' and
(II)
and/or
R R
(III)
wherein R is independently hydrogen, Of to C6
alkyd or C4 to C8 cycloalkyl, X' is independently
R 2
wherein Al and R2 are independently hydrogen or
Of to Cog alkyd, or
I
( IRK)
( to)
R4
D-14,3S2
lZ3~813
-- 7
wherein R3 and R4 are independently hydrogen or
Of to CUB alkyd, and at it an integer of 3 to
8: -S-. -0-, or . a is an integer of 0 to 4
and n it independently an integer of 1 to 3 and
wherein the ratio of unit (I) to the sum of units
(II) and/or (III) is greater than 1. The units are
attached to each other by an -0- bond.
A preferred polymer of this invention
contains unit of the formula:
, and
~S02~
Another preferred polyarylethersulfone of
this invention contain units of the formula:
2 and
SHEA
SHEA
These unit are attached to each other by
an -0- bond.
The polyarylethersulfone may be random or
Jay have an orderer structure.
Tube polyarylether6ulfone~ of this invention
have a reduced viscosity of from about 0.4 to
D-lq,362
1~3~8~3
greater than about 2.5. as measured in
N-methylpyrolidone, or other suitable solvent, at
25C.
The polyarylether~ulfones of this invention
are prepared by reacting the monomers represented by
the following formulae:
(IV) 52 X
(V) ~,~S02~
Jo
VOW) X
HO n
(VII) and/or HO OH
wherein I, a, I' and n are as previously defined,
and and Y are independently selected from Of, Bra
F, NO or OH and at least 50 percent of the Yes
are OH.
D-14,3~2
1;~36~ 3
The ratio of the concentration of OR groups
to Of, Bra F and/or No groups used to form the
polyarylethersulfone is from about 0.90 to about
lo preferably from about 0.98 to about 1.02.
The monomers, represented by formulas (IV),
(V), (VI) and (VII), include the following:
2,2-bis(4-hydroxyphenyl)propane,
bis(4-hydroxyphenyl)methane,
4,4'-dihydroxydiphenyl sulfide,
4,4'-dihydroxydiphenyl ether,
4,4'-dihydroxydiphenyl cellophane,
2,4'-dihydroxydiphenyl cellophane,
4,4'-dichlorodiphenyl cellophane,
4,4'-dinitrodiphenyl cellophane,
4-chloro-9'-hydroxydiphenyl cellophane,
4,4'-biphenol, hydroquinone, and the like.
The preferred monomer include
hydroquinone, 4,4-biphenol, 2,2-bis(4-hydroxyphenyl)
propane, 4,4'-dichlorodiphenyl cellophane, and
4,4'-dihydroxydiphenyl cellophane or 4 sheller I
hydroxydiphenyl cellophane.
The polymers of this invention are prepared
by contacting substantially equimolar amounts of the
hydroxy containing compounds (depicted in formulas
(IV) to (VII) swooper) and halo and/or vitro
containing compounds (depicted in formula (IV) and
(V) swooper) with from about 0.5 to about 1.0 mole of
an alkali metal carbonate per mole of hydroxyl group
in a solvent mixture comprising a solvent which
form an azeotrope with water in order to maintain
the reaction medium at 6ub~tantially Andre
conditions during the polymerization.
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lZ3C~13
- 10 --
The temperature of the reaction mixture it
kept at from about 120 to about 180C, for about 1
to about 5 hour and then raised and kept at from
about 200 to about 250C, preferably from about 210
to about 230C, for about 1 to 10 hours.
The reaction is carried out in an inert
atmosphere, e.g., nitrogen, at atmospheric pressure,
although higher or lower pressures may also be used.
The polyarylethersulfone is then recovered
by conventional techniques such as coagulation,
solvent evaporation, and the live.
The solvent mixture comprises a solvent
which forms an azeotrope with water and a polar
aprotic solvent. The solvent which forms an
azeotrope with water includes an aromatic
hydrocarbon such a Bunsen, Tulane, zillion,
ethylbenzene, chlorobenzene, and the like.
The polar aprotic solvent employed in this
invention are those generally known in the art for
the manufacture of polyarylether cellophane and
include sulfur containing solvent such as those of
the formula:
R5- 5(0)b R5
in which each R5 represent a monovalent lower
hydrocarbon group free of aliphatic unsaturation,
which preferably contains lets than about B carbon
atoms or when connected together represents a
diva lent alkaline group with b being an integer from
1 to 2 inclusive. Thus, in all of these solvents
all ox~gens and two carbon atoms are bonded to the
sulfur atom. Contemplated for use in this invention
are such solvents as those having the formula:
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-- 11 --
o o
If 11
R6 S R6 and I R6
where the R6 groups are independently lower alkyd,
such as methyl, ethyl, propel, bottle, and like
groups, and aureole groups such as phenol and
alkylphenyl groups such as the toll group, as well
as those where the R6 groups are interconnected as
in 3 diva lent alkaline bridge such as:
C2~4\
2______ Ho
S I
in tetrahydrothiophene oxides and dioxides.
Specifically, these solvents include
dimethylsulfoxide, dimetbylsulfone, diphenylsulfone,
diethylsulfoxide, diethylsulfone,
diisopropyl~ulfone, tetrahydrothiophene l,l-dioxide
(commonly called tetramethylene cellophane or
sulfolane) and tetrahydrothiophene-l monoxide.
Additionally, nitrogen containing solvents
may be used. These include dim ethyl acetamide,
dim ethyl formamide and N-methylpyrolidone.
The azeotrope forming solvent and polar
aprotic solvent are used in a weight ratio of from
about ~0:1 to about 1:1, preferably from about 7:1
to about 5:1.
In the reaction, the hydroxy containing
compound is slowly converted, in situ, to the alkali
silt thereof by reacting with the alkali metal
carbonate. The alkali metal carbonate is preferably
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- 12 -
potassium carbonate. Mixtures of carbonates such as
potassium end sodium carbonate may also be used.
Water is continuously removed from the
reaction mass as an azeotrope with the azeotrope
forming solvent I that substantially an hydrous
conditions are maintained during the polymerization.
It is essential that the reaction medium be
maintained substantially an hydrous during the
polycondensation. While amounts of water up to
about one percent can be tolerated, and are somewhat
beneficial when employed with fluorinated
dihalobenzenoid compounds, amounts ox water
substantially greater Han this are desirably
avoided as the reaction of water wick the halo
Andre vitro compound leads to formation of finlike
species and only low molecular weight products are
secured. Consequently, in order to secure the high
polymers, the system should be substantially
an hydrous, and preferably contain less than OHS
percent by weight water during tube reaction.
Preferably, after the desired molecular
weight has been attained, the polymer is treated
with an ~ctiYated aromatic halide or an aliphatic
halide such as methyl chloride or bouncily chloride,
and the like. such treatment of the polymer
converts tubs terminal hydroxyl groups into ether
groups which stabilize the polymer. The polymer so
treated has good melt and oxidative stability.
B. PolYarYlether resin
The poly(aryl ether) resin suitable for
blending with the polyarylether6ulfone, it different
from the ~olyaryletner~ulfone and is a linear,
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- 13 -
thermoplastic polyarylene polyether containing
recurring units of the following formula:
-OWE-
wherein E it the residuum of a dihydric phenol, and
En is the residuum of a benzenoid compound having an
inert electron withdrawing group in at least one of
the positions ortho and pane to the valence bonds;
both of said Rudy are violently bonded to the
ether oxygen through aromatic carbon atoms. Such
aromatic polyethers are included within the clays of
polyarylene polyester resins described in, for
example, U.S. Patents 3,264,536 and 4,175,175. It
is preferred that the dihydric phenol be a weakly
acidic dinuclear phenol such as, for example, the
dihydroxyl diphenyl alikeness or the nuclear
halogenated derivatives thereof, such as, for
example, the 2,2-bis(4-hydroxyphenyl)propane,
1,1-bis(q-hydroxphenyl)2-phenyl ethanes
bis(4-hydroxyphenyl)methane, or their chlorinated
derivatives containing one or two chlorines on each
aromatic ring. Other materials also termed
appropriately bisphenol6 are Allah highly valuable
and preferred. These material are the bisphenols
of a symmetrical or unsymmetrical joining group, as,
o
for example, ether oxygen (-O-), carbonyl (-C-),
o
~ulfone (-S-), or hydrocarbon residue in which the
o
two finlike nuclei are joined to the same or
different carbon atom of tube residue.
D-14,362
123(:~8~3
Such dinuclear phenol can be characterized
as having the structure:
(17)c (I 7)c
Hurrier -Awry
wherein An is an aromatic group and preferably is a
phenylene group, R7 and R'7 can be the same or
different inert ~ubstituent groups such as alkyd
groups having from 1 to 4 carbons atoms, aureole,
halogen atoms, i.e., fluorine, chlorine, bromide or
iodine, or alkoxyl radicals having from 1 to 4
carbon atom, the I are independently integers
having a value of from O to 4, inclusive, and RUB
is representative of a bond between aromatic carbon
atoms as in dihydroxyl-diphenyl, or is a diva lent
radical,
o
if
including for example, radicals such as -C-, -O-,
-S-, -SO-, -S-S-, -52' and diva lent hydrocarbon
radical such as alkaline, alkylidene,
cycloalkylene, cycloalkylidene, or the halogen,
alkyd, aureole or like ~ub6tituted alkaline, alkylidene
and cycloaliphatic radicals as well as aromatic
radicals and rings fused to both An groups.
Examples of specific dihydric polynuclear
phenols including among others: the
bi~-~hydroxyphenyl) alikeness such as
2,2-bis-(4-hydroxyphenyl)propane,
2,4'-dihydroxydiphenylmethane,
D-14,362
123(~8~3
bis-(2-~ydroxyphenyl)methane,
bis-(4-hydroxyphenyl)methane,
bis~4-hydroxy-2,6-dimethyl-3-methoxyphenyl)methanee,
1,1-bis-(4-hydroxy-phenyl)ethane,
1,2-bis-(4-hydroxyphenyl)ethane,
1,1-bis-(4-hydroxy-2-chlorophenyl)ethane,
1,1-bis-(3-methyl-4-hydroxyphenyl)propane,
1,3-bis-(3-methyl-4-hydroxyphenyl)propane,
2,2-bis-(3-phenyl-4-hydroxyphenyl)propane,
2,2-bis-(3-i~opropyl-4-hydroxyphenyl)propane,
2,2-bis-(2-isopropyl-9-hydroxyphenyl)propane,
2,2-bis-(4-hydroxy-naphthyl)propane,
2,2-bis-(4-hydroxyphenyl)pentane,
3,3-bis-(4-hydroxyphenyl)pentane,
2,2-bis-(4-hydroxyphenyl)heptane,
bis-(4-hydroxyphenyl)phenylmethane,
~,2-bis-(4-hydroxypheny~)-1-phenyl-propane,
2,2-bis-(4-hydroxyphenyl)1,1,1,3,3,3,-hexafluoro-
propane, and the like;
di(hydroxyphenyl)sulfones such as
bis-(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenyl
~ulfone, 5-chloro-2,4'-dihydroxydiphenyl cellophane,
5'-chloro-4,4'-dihydroxydiphenyl cellophane, and the
like;
di(hydroxyphenyl)ethers such as
bis-(4-hydroxyphenyl)ether, the go
4,2'-2,2'-2,3-,dihydroxyphenyl ethers,
4,4'-dihydroxyl-2,6-dimethyldiphenyl
ether,bi6-(4-hydroxy-3-isobutylphenyl)ether,
bis-(4-hydroxy-3-isopropylphenyl)ether,
bis-(4-hydroxy-3-chlorophenyl)ether,
bis-(4-hydroxy-3-fluorophenyl)ether,
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bis-(4-hydroxy-3-bromophenyl)ether,
bis-(4-hydroxynaphthyl)ether,
bis-(g-hydroxy-3-chloronaphthyl)ether, and
4,4'-di~ydroxyl-3,6-dimethoxydiphenyl ether.
As herein used the E' term defined as being
the "residuum of the dihydric phenol" of course
refer to the residue of the dihydric phenol after
the removal of the two aromatic hydroxyl groups.
Thus as is readily seen these polyarylene polyethers
contain recurring group of the residuum of the
dihydric phenol and the residuum of the benzenoid
compound bonded through aromatic ether oxygen atom.
Any dihalobenzenoid or dinitrobenzenoid
compound or mixtures thereof can be employed in this
invention which compound or compounds has the two
halogens or nitro-groups bonded to Bunsen rings
having an electron withdrawing group in at least one
of the position ortho and pane to the halogen or
vitro group. The dihalobenzenoid or
dinitrobenzenoid compound can be either mononuclear
where the halogen or vitro group are attached to
the same benzenoid rings or polynuclear where they
are attached to different benzenoid rings, as tong
as there is an activating electron withdrawing group
in the ortho or pane position of that benzenoid
nuclear. Fluorine and chlorine substituted
benzenoid reactants are preferred; the fluorine
compound for fat reactivity and the chlorine
compound for their inexpensiveness. Fluorine
substituted benzenoid compound are most preferred,
particularly when there it a trace of water present
in the polymerization reaction system. However,
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this water content should be maintained below about
I and preferably below 0.5~ for best results.
An electron withdrawing group can be
employed as the activator group in these compounds.
It should be, of course, inert under the reaction
condition, but otherwise it structure it not
critical. Preferred are the strong activating
o
groups such as the cellophane group I bonding two
o
halogen or vitro substituted benzenoid nuclei as in
the 4,4'-dichlorodiphenyl cellophane and
4,4'-difluorodiphenyl 6ulfone, although such other
strong withdrawing group hereinafter mentioned can
also be used with equal ease.
The more powerful of the electron
withdrawing groups give the fastest reactions and
hence are preferred. It is further preferred that
the ring contain no electron supplying groups on the
same benzenoid nucleus as the halogen or vitro
group: however, the presence of other groups on the
nucleus or in the residuum of the compound can be
tolerated.
The activating group can be basically
either of two types:
(a) monovalent groups that activate one or
more halogens or nitro-group6 on the same ring such
as another vitro or halo group, phenylsulfone, or
al~ylsulfone, cyan, trifluoromethyl, nutrias, and
hotter nitrogen, a in pardon.
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! I_
lZ3(~13
(b) diva lent group which can activate
displacement of halogens on two different rings,
o
such as the cellophane group -S-; the carbonyl group
o
O
-C-; the vinylene group -C=C-; the sulfoxide group
o
.,
-S-; the ago group -N-N-; the saturated fluorocarbon
,CF3
groups -C-, -CF2 -CF2CP2-; organic phosphine
CF3
oxides -P-;
Rug
where Rug it a hydrocarbon group, and the
ethylidene group A-C-A where A can be
--C--
hydrogen or halogen.
If desired, the polymers may be made with
mixture of two or more dihalobenzenoid or
dinitrobenzenoid compounds. Thus, the E' residuum
ox the benzenoid compounds in the polymer structure
may be toe same or different.
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It is teen also that as used herein, the
term defined as being the residuum of the benzenoid
compound refers to the aromatic or benzenoid
residue of the compound after the removal of the
halogen atom or vitro group on the benzenoid nucleus.
The polyarylene polyethers of this
invention are prepared by methods well known in the
art as for instance the substantially equimolar
one-step reaction of a double alkali metal salt of
dihydric phenol with a dihalobenzenoid compound in
the presence of specific liquid organic sulfoxide or
cellophane solvent under substantially an hydrous
conditions. Catalysts are not necessary for this
reaction.
The polymers may also be prepared in a
two-step process in which a dihydric phenol is first
converted in situ in the primary reaction solvent to
the alkali metal salt of the reaction with the
alkali metal, the alkali metal hydrides alkali metal
hydroxide, alkali metal alkoxide or the alkali metal
alkyd compounds. Preferably, the alkali metal
hydroxide is employed. After removing the water
which is present or formed, in order to secure
substantially an hydrous conditions, the dialkali
metal salt of the dihydric phenol are admixed and
reacted with about stoichiometric quantities of the
dihalobenzenoid or dinitrobenzenoid compound.
Additionally, the polyethers may be
prepared by the procedure described in, for example,
U.S. Patent 4,176,222 in which a substantially
equimolar mixture of at least one bisphenol and at
least one dihalobenzenoid are heated at a
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-- 20 --
temperature of from about 100 to about 400C with a
mixture of dummy carbonate or bicarbonate and a
second alkali metal carbonate or bicarbonate having
a higher atomic number than that of sodium.
Further. the polyethers may be prepared by
the procedure described in Canadian Patent 847,963
wherein the bisphenol and dihalobenzenoid compound
are heated in the presence of potassium carbonate
using a high boiling solvent such as diphenylsulfone.
Preferred polyarylene polyethers of this
invention are those prepared using the dihydric
polynuclear phenols of the following four types,
including the derivatives thereof which are
substituted with inert substituent groups
110
(a) HO C OH
Rio
in which the Rio groups represent independently
hydrogen, lower alkyd. aureole and the halogen
substituted groups thereof, which can be the same or
different:
(b) HO Jo OH
(C) HO OH
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~Z3~813
- 21 -
Ed) JO OH
and substituted derivatives thereof.
It is also contemplated in this invention
to use a mixture of two or more different dihydric
phenols to accomplish the same ends as above. Thus
when referred to above the -I- residuum in the
polymer structure can actually be the same or
different aromatic residue.
The poly(aryl ethers have a reduced
viscosity of from about 0.35 to about 1.5 as
measured in an appropriate solvent at an appropriate
temperature depending on the particular polyether,
such as in ethylene chloride at 25C.
The preferred poly(aryl ethers have
repeating units of the formula:
OOZE
owe
O C , and
0~52
C. PolYarYlates
Tube thermoplastic polymers which may be
blended with the polyarylethersulfone or blend of
D-14,362
Z3~813
polyarylethersulfone and poly(aryl ether) include
polyarylates, polyetherimides, polyesters, aromatic
polycarbonates, Turin resins, poly(alkyl
acrylates), polyhydroxyether~, poly(arylene sulfide)
and polyamides.
A. Polvarvlatec
The polyarylates which are suitable for use
in this invention are derived from a dihydric phenol
and at least one aromatic dicarboxylic acid and have
a reduced viscosity of from about 0.4 to greater
than about 1.0, preferably from about 0.6 to about
0.8 dl/gm, as measured in chloroform (0.5 glumly
chloroform) or other suitable solvent at 25C.
A particularly desirable dihydric phenol is
of the following formula:
do do
HO ~11)0-1 I
wherein Y is independently selected from, hydrogen,
alkyd groups of 1 to 4 carbon atoms, chlorine or
bromide, each d, independently, has a value of from
O to 4, inclusive, and ~11 is a diva lent saturated
or unsaturated aliphatic hydrocarbon radical,
particularly an alkaline or alkylidene radical
having from 1 to 6 carbon atoms, or a
cycloalkylidene or cycloalkylene radicals having up
to and including 9 carbon atoms, O, CO, S02, or
S. The dibydric phenols may be used individually or
in combination.
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- 23 -
The dihydric phenols that may be used in
this invention include the following:
2,2-bis-4(4-hydroxyphenyl)propane;
bis-(2-hydroxyphenyl)methane,
bis-(4-hydroxyphenyl)methane,
bis-(4-hydroxy-2,6-dimethyl-3-methoxyphenyl)
methane,
1,1-bis-(4-hydroxyphenyl)ethane,
1,2-bis-(4-hydroxyphenyl~ethane,
1,1-bis-(4-hydroxy-2-chlorophenyl)ethane,
1,3-bis-(3-methyl-4-hydroxyphenyl)ethane,
1,3-bis-(3-methyl-4-hydroxyphenyl)propane,
2,2-bi~-(3-phenyl-4-hydroxyphenyl)propane,
2,2-bis-(3-isopropyl-4-hydroxyphenyl~
propane,
2,2-bis-(2-isopropyl-4-hydroxyphenyl)
propane,
2,2-bis-(4-hydroxyphenyl)pentane,
3,3-bis-(4-hydroxyphenyl)pentane,
2,2-bis-(9-hydroxyphenyl)heptane,
1,2-bi6-(4-hydroxyphenyl)1,2-bis-(phenyl)-
propane,
4,4'-(dihydroxyphenyl)ether,
4,4'-(dihydroxyphenyl)sulfide,
4,4'-(dihydroxyphenyl)sulfone,
4,4'-(dihydroxyphenyl)~ulfoxide,
4,4'-(dihydroxybenzophenone), and
naphthalene dills
The aromatic dicarboxylic acids that may be
used in this invention include terephthalic acid,
i60phthalic acid, any of the naphthalene
dicarboxylic acid and mixtures thereof, as well as
D-14,362
1~3(?~13
- 24 -
alkyd substituted homology of these carboxylic
acids, wherein the alkyd group contains from 1 to
about 4 carbon atoms, and acids containing other
inert ~ubstituent~, such as halides, alkyd or aureole
ethers, and the like. Acetoxybenzoic acid can also
be used. Preferably, mixtures of isophthalic and
terephthalic acids are used. The isophthalic acid
to terephthalic acid ratio in the mixture it about
0:100 to about 100:0, while the most preferred acid
ratio is about 75:25 to about 50:50. Also, from
about 0.5 to about 20 percent of aliphatic dissuades
containing from 2 eon about 10 carbon atoms, such as
adipic acid, sebacic acid, and the like may be
additionally used in the polymerization reaction.
The polyarylates of the present invention
can be prepared by any of the well known prior art
polyester forming reactions, such as the reaction of
the acid chlorides of the aromatic dicarboxylic
acids with the dihydric phenols; the reaction of the
diary esters of the aromatic dicarboxylic acids
with the dihydric phenols; or the reaction of the
aromatic dissuades with dieter derivatives of the
dihydric phenol. These processes are described in,
for example, U.S. Patents 3,317,464; 3,948,856;
3,780,148; 3,824,213: and 3,133,898.
The polyarylates are preferably prepared by
the process as set forth in U.S. Patent 4,321,355.
This process comprises the following step:
tax reacting an acid android
derived from an acid containing from 2 to 8 carbon
atoms with at least one dihydric phenol to form the
corresponding divester: and
D-14,362
~Z3(~ 3
- 25 -
(b) reacting said divester with at
least one aromatic dicarboxylic acid at a
temperature sufficient to form the polyarylate,
wherein the improvement comprises removing residual
acid android after formation of the dihydric
phenol divester so that its concentration is less
than about 1500 parts per million.
The acid android suitable is derived from
an acid containing from 2 to 8 carbon atoms. The
preferred acid android is acetic android.
The dihydric phenol is described above.
Generally, the dihydric phenol reacts with
the acid android under conventional esterification
conditions to form the dihydric phenol divester. The
reaction may take place in the presence or absence
of a solvent. Additionally, the reaction may be
conducted in the presence of a conventional
esterification catalyst or in the absence thereof.
D. PolYetherimides
The polyetherimides suitable for use in
this invention are well known in the art and are
described in, for example, U.S. Patents 3,847,867,
3,838,097 and 4,107,147.
The polyetherimides are of the following
formula:
_ _
O O
11 if
(VIII) \ C I /
0 -R12- 0 e
D-14,362
3~313
wherein e it an integer greater than 1, preferably
from about 10 to about 10,000 or more, -0-R12-0-
it attached to the 3 or 4 and 3' or I position and
R12 it selected from (a) a substituted or
unsubstituted aromatic radical such as
0-4
, or
I
by a diva lent radical or the formula:
(R14) (R14)
wherein R14 it independently Of to C6 alkyd,
aureole or halogen and
~15 it selected from -0-, -So S02-, -So-,
alkaline of 1 to 6 carbon atom, cycloalkylene of 4
to 8 carbon atom, al~ylidene of 1 to 6 carbon atom
or cycloalkylidene of 4 to 3 carbon atoms, R13 it
selected from an aromatic hydrocarbon radical having
from 6 to 20 carbon atoms and halogenated
derivatives thereof, or alkyd 6ub6tituted
D-14,362
1.'~3~3
derivatives thereof, wherein the alkyd group
contains 1 to 6 carbon atoms, alkaline and
cycloalkylene radicals having from 2 to 20 carbon
atoms and C2 Jo C8 alkaline terminated
polydiorganosiloxane or a diva lent radical of the
formula
(R14) (R14)
~R15~
wherein R14 and R15 are as previously defined.
The polyetherimides may also be of the
following formula:
O O
IT ~Z N-R12 -N ~Z-0-R13 -
O O
_ e
wherein -0-Z is a member selected from
Roy
,,~
--I my
wherein R16 it independently hydrogen, lower alkyd
or lower alkoxy
and,
Jo
I
D-14,362
lZ3(~13
wherein the oxygen may be attached to either ring
and located ortho or pane to one of the bonds of the
imide carbonyl groups, Rl2 and Rl3 and e are as
previously defined.
These polyetherimides are prepared by
methods well known in the art as set forth in, for
example, U.S. Patents 3,833,544, 3,887,588,
4,017,511, 3,965,125 and 4,024,110.
The polyetherimide~ of Formula (VIII) can,
for example, be obtained by any of the methods
well-known to those skilled in the art including the
reaction of any aromatic bis(ether androids of
the formula
O O
If 11 .
( X) o -R12-~C~o
If 11
O O
where R12 it as defined hsreinbefore, with a
Damon compound of the formula
(XI) 2 13 2
where R13 it a defined herein before. In general,
the reactions can be advantageously carried out
employing well-known vents, e.g., o-dichloro-
Bunsen, m-cresol/toluene, N,N-dimethylacetamide,
etc., in which to effect interaction between the
dianhydrides and Damon, at temperature of from
about 20 to about 250C. Alternatively, the
polyetherimide6 can be prepared by melt
polymerization of any dianhydride~ of Formula (~)
D 14,362
813
- 29 -
with any Damon compound of Formula (XI) while
heating the mixture of the ingredients at elevated
temperatures with concurrent intermixing.
Generally, melt polymerization temperatures between
about 200~ to 400C and preferably 230 to 300C can
be employed. Any order of addition of chain
stoppers ordinarily employed in melt polymerizations
can be employed. The conditions of the reaction and
the proportions of ingredients can be varied widely
depending on the desired molecular weight, intrinsic
viscosity, and solvent resistance. In general,
equimolar amounts of Damon and dianhydride are
employed for high molecular weight polyetherimides,
however, in certain instances, a slight molar excess
(about 1 to 5 mole percent) of Damon can be
employed resulting in the production of
polyetherimides of Formula I have an intrinsic
viscosity greater than 0.2 deciliters per gram,
preferably 0.35 to 0.60, or 0.7 deciliters per gram
or even higher when measured in m-cresol at 25C.
The aromatic bistether androids of
Formula (X) include, for example,
2,2-bis~4-(2,3-dicarboxyphenoxy)phenyl~-
propane dianhydride:
4,4'-bis(2,3-dicarboxyphenoxy)diphenyl
ether dianhydride;
1,3-bis(Z,3-dicarboxyphenoxy)benzene
dianhydride;
4,4'-bi~(2,3-dicdrboxyphenoxy)diphenyl
sulfide dianhydride;
1,4-bis(2,3-aicarboxyphenoxy)benzene
d~anhydride:
D-14,362
l ~3~313
- 30 -
4,4~-bis(2,3-dicarboxyphenoxy)benzophenone
dianhydride;
4~4~-bis(2~3-dicarbox~phenoxy)diphen
cellophane dianhydride:
2,2-bi~[4-(3,4-dicarboxyphenoxy)phenyl]-
propane dianhydride;
4,g'-bis(3,4-dicarboxyphenoxy)diphenyl
ether dianhydride;
9,4' bis(3,4-dicarboxyphenoxy)diphenyl
6ul five dianhydride;
1,3-bi~(3,4-dicarboxyphenoxy)benzene
dianhydride;
1,4-bis(3,4-dicarboxyphenoxy)benzene
dianhydride;
4,4'-bis(3,4-dicarboxyphenoxy)benzophenone
dianhydride;
4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxy-
phenoxy)diphenyl-2,2-propane dianhydride; etc.
and mixtures of such dianhydrides.
The organic dominoes of Formula (XI)
include, for example, m-phenylenediamine,
p-phenylenediamine, 2,2-bi~(p-aminophenyl)propane,
4,4'-diaminodiphenyl-methane, 4,4'-diaminodiphenyl
sulfide, 4,4'-diamino-diphenyl cellophane,
4,4'-diaminodiphenyl ether, l,S-diaminonaphthalene,
3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine,
The polyetherimides of formula (%) may, for
example, be prepared by effecting reaction in the
presence of a bipolar aprotic solvent of a mixture
of ingredients comprising, for instance, (1) a
bls(nitrophthalimide) of the general formula:
D-14,36~
~z3(~ 3
o o
If 11
(XII) I ON R13--N I
N2 N02
O O
wherein R13 is defined as hereinabove, and (2) an
alkali metal salt of an organic compound of the
general formula:
(XIII) 12
wherein M is an alkali metal and R12 is defined as
hereinabove.
The bis(nitrophthalimide) used in preparing
the polymer is formed by reacting a Damon of the
formula described above, NH2-R13-NH2, with a
nitro-sub~tituted aromatic android of the formula:
(IVY) C
N2 11
The molar ratio of Damon to android should
ideally be about 1:2 respectively. The initial
reaction product is a bis(amide-acid) which is
subsequently dehydrated to the corresponding
bis(nitrophthalimide).
The dominoes are described, upper.
The preferred nitrophthalic androids
useful in the prevent invention are 3-nitrophthalic
android, 4-nitrophthalic android and mixture
thereof. These reactants are commercially available
in reagent grade. They may also be prepared by the
nitration of phthalic android using procedures
D-14,362
~LZ3(~3
described in Organic Syntheses, Collective Vol. I,
Wiley (194~). page 408. Certain other closely
related nitroaromatic androids may also be used in
the reaction and are illustrated for example by
2-nitronaphthalic android, 1-nitro-2,3-naphthalene-
dicarboxylic android and 3-methoxy-6-nitrophthalic
android, and the like.
With reference to the alkali metal salts of
formula (XIII) among the diva lent carbocyclic
aromatic radicals which R12 may represent
(mixtures of such radicals are also included) are,
for instance, diva lent aromatic hydrocarbon radicals
of from 6 to 20 carbon atoms, such a phenylene,
biphenylene, naphthylene, etc. Included are
residue of, e.g. hydroquinone, resorcinol,
chlorohydroquinone, etc. In addition, R12 may ye
a residue of a dihydroxyl Darlene compound in
which the aureole nuclei are joined by either an
aliphatic group, a sulfoxide group, sulfonyl group,
sulfur, carbonyl group, oxygen, etc. typical of
such Darlene compounds are the following:
2,4-dihydroxydiphenylmethane;
bis(2-hydroxyphenyl)methane;
2,2-bis(4-hydroxyphenyl)propane;
bis(4-hydroxyphenyl)methane;
bis(4-hydroxy-5-nitrophenyl)methane;
bis(4-hydroxy-2,6-dimethyl-1-methoxy-
phenyl)methane;
1,1-bis(4-hydroxyphenyl)ethane;
1,2-bis(4-hydroxyphenyl)ethane;
1,1-bis(4-hydroxy-2-chlorophenyl)ethane;
l,l-bis(2,5-dimethyl-4-hydroxyphenyl)2thane;
D-14,362
~Z3(~8~3
- 33 -
1,3-bis(~-methyl-4-hydroxyphenyl)propane;
2,2-bis(3-phenyl-4-hydroxyphenyl)propane;
2,2-bis(3-isopropyl-4-hydroxyphenyl)propane;
2,2-bis(4-hydroxynaphthyl~propane;
hydroquinone;
naphthalene dills;
bis(4-hydroxyphenyl~ether:
bis(4-hydroxyphenyl)sulfide:
bis(4-hydroxyphenyl)sulfone: and the like.
When dialkali metal salts of formula Tao)
are used with the compound illustrated by formula
(XII), the ingredients are advantageously present in
an equal molar ratio for optimum molecular weight
and properties of the polymer. Slight molar
excesses, e.g., about 0.001 to 0.10 molar excess of
either the dinitro-substituted organic compound or
of the dialkali metal salt of formula (XIII) may be
employed. When the molar ratios are approximately
equal, the polymer it substantially terminated by
a , Z-N02 at one end and a finlike group at the
other end. If there it a molar excess of one
compound, that particular terminal group will
predominate.
The conditions of reaction whereby the
alkali-metal Walt of formula (~III) is reacted with
the dinitro-substituted organic compound of formula
IT can be varied widely. Generally, temperatures
of the order of about 25 to about 150C are
advantage employed, although it is possible to
employ lower or higher temperature conditions
dèpendinq on the ingredient used, the reaction
product Utah, time of reaction, yenta employed,
D-14,3~2
~3(~813
etc. In addition to atmospheric pressure,
6uperatmospheric pressures and sub atmospheric
pressures may be employed depending upon the other
conditions of reaction, the ingredients used, the
speed at which it is desired to effect reaction, etc.
The time of reaction also can be varied
widely depending on the ingredient used, the
temperature, the desired yield, etc. It has been
found that times varying from about 5 minutes to as
much a 30 to 40 hours are advantageously employed
to obtain the maximum yield and desired molecular
weight. Thereafter the reaction product can be
treated in the appropriate manner required to effect
precipitation and/or separation of the desired
polymeric reaction product. Generally, common
solvents such as alcohols (e.g. methanol, ethanol,
isopropyl alcohol, etc.) and aliphatic hydrocarbons
ego. pontoon, hexane, octane, cyclohexane, etc.)
may be employed as precipitant for this purpose.
It it important that the reaction between
the dinitro-6ubstituted organic compound of formula
V and the alkali-metal Walt of formula VI (mixtures
of such alkali-metal salt can also be used) be
carried out in the presence of a bipolar aprotic
solvent.
The polymerization it performed under
Andre conditions usually using bipolar aprotic
solvent such as dimethylsulfoxide which are added
in varying amounts depending upon the particular
polymerization. A total quantity of vent,
bipolar aprotic solvent or mixture of such solvent
with an aromatic solvent sufficient to give a final
D-14,362
lZ3(3~3
- 35 -
6clution containing lo to 20~ by weight of polymer
if preferably employed.
The preferred polyetherimides include those
having repeating unit of the following formula:
O O --
11 11
_ C~3 C H 3 I \ _
_ 11 IT
E. Polyesters
The polyesters which are suitable for use
herein are derived from an aliphatic ox
cyloaliphati~ dill, or mixtures thereof, containing
from 2 to about 10 carbon atoms and at least one
aromatic dicarboxylic acid. The polyester which
are derived from an aliphatic dill and an aromatic
dicarboxylic acid have repeating units of the
following general formula:
O O
XV I (SHEA) okay
n
wherein n it an integer of from 2 to 10.
The preferred polyester it polyethylene
terephthalate).
Also contemplated herein are the above
polyesters with minor amount, e.g., from 0.5 to
about 2 percent by weight, of units derived from
D-14,362
sty
aliphatic acids and/or aliphatic polyols, to form
copolyesters. The aliphatic polyols include
glycols, such as polyethylene glycol). These can
be made following the teachings of, for example,
U.S. Patents 2,465,319 and 3,047,539.
The polyester which are derived from a
cycloaliphatic dill and an aromatic dicarboxylic
acid are prepared by condensing either the is - or
triune omen (or mixtures thereof) of, for example,
1,4-cyclohexanedimethanol with an aromatic
dicarboxylic acid 80 as to produce a polyester
having recurring unit of the following formula:
(XVI) 0-CH2CH \ CH-cH2-o-c-Rl7
C~32-CH2
wherein the cyclohexane ring is selected from the
Sue- and trays- isomer thereof and R17 represents
an aureole radical containing 6 to 20 carbon atoms and
which it the decarboxylated residue derived from an
aromatic dicarboxylic acid.
Examples of aromatic dicarboxylic acid
indicated by R17 in formula I%, are isophthalic or
terephthalic acid, 1,2-di~p-carboxyphenyl)e~hane,
4,q'-dicarboxydiphenyl ether, etc., and mixture of
these. All of these acids contain at least one
dramatic nucleus. Fused rings can also be prevent,
such a in 1,4-or l,S-naphthalenedicarboxylic
acids. The preferred dicarboxylic acid are
terephthalic acid or a mixture of terephthalic and
i60phthalic acid.
D-14,362
A preferred polyester may be derived Prom
the reaction of either the Syria trans-isomer ion a
mixture thereof) of l,4-cyclohexanedimethanol with a
mixture of isophthalic and terephthalic acids.
These polyesters have repeating units of the formula:
(XVII) -0-CH2CH CN2 OH / C~-CH2--C C
Another preferred polyester is a
copolyester derived from a cyclohaxane dim ethanol,
an alkaline glycol and an aromatic dicarboxylic
acid. These copolyesters are prepared by condensing
either the is- or trans-isomer (or mixtures
thereof) of, for example, 1,4-cyclohexaneaimethanol
and an alkaline glycol with an aromatic dicarboxylic
acid so as to produce a copolyes~er having repeating
units of the following formula:
O O
OH I- OH I
~XVIII) t OUCH \ f H-CH20-C-Rl~C t
SCHICK
11 1l
oceanic R
D-14,3h2
- 123t~3
- 3B -
wherein the cyclohexane ring is selected from the
is- and trance isomers thereof, Rl7 is as
previously defined, n it an integer of 2 to 10, the
f units comprise from about 10 to about 90 percent
by weight and the g unit comprise from about 10 to
about 90 percent by weight.
The preferred copulatory may be derived
from the reaction of either the is- or trans-isomer
(or mixtures thereof) of 1,4-cyclohexanedimethanol
and ethylene glycol with terephthalic acid in a
molar ratio of 1:2:3. These copolyesters have
repeating unit of the following formula:
SIX CH2CH\ SHEA SCHICK
OKAY H2~0C~ C
wherein h can be 10 to 10,000. Block as well as
random copolymers are possible.
Thy polyester a described herein are
either commercially available or can be produced by
methods well known in the art, such as those set
forth in, for example, U.S. Patent 2,901,466.
The polyesters used herein have an
intrinsic viscosity of from about 0.4 to about 2.0
dug as measured in a 60:40 phenol/tetrachloro-
ethanes mixture or similar solvent at 23 to 30C.
D-14,~62
,
lz3a~3
- 39 -
F Aromatic Pol~carbonate
The thermoplastic aromatic polycarbonates
that can be employed herein are homopolymers and
copolymers and mixtures thereof, which have an
intrinsic viscosity of from about 0.4 to about 1.0
dug as measured in ethylene chloride at 25C.
The polycarbonates are prepared by reacting a
dihydric phenol with a carbonate precursor. Typical
of some of the dihydric phenols that may be employed
are bisphenol-A, bis(4-hydroxyphenyl)methane,
2,2-bis(4-hydroxy-3-me~hylphenyl)propane,
4,4-bis(4-hydroxyphenyl)heptane, 2-2-(3,5,3~,
5'tetrabromo-4,4'-dihydroxydiphenyl)propane,
(3,3'dichloro-4,4'dihydroxydiphenyl)methane, and the
like. Other dihydric phenol of the bisphenol type
are described in, for example, U.S. Patents,
Z,999,~35, 3,028,365 and 3,334,154.
It is, of course, possible to employ two or
more different dihydric phenols or a copolymer of a
dihydric phenol with a glycol Dry with hydroxy or
acid terminated polyesters.
The carbonate precursor may be either a
carbonyl halide, a carbonate ester, or a
haloform ate. The carbonyl halides which can be
employed herein are carbonyl bromide, carbonyl
chloride and mixtures thereof. Typical of the
carbonate esters which may be employed herein are
dip~enyl carbonate, di-~halophenyl)carbonates, such
as di-(chlorophenyl)carbonate or
at- beomophenyl)carbonate, etc.,
di-(alkylphenyl)carbonates such as
di(tolyl)carbonate, di(naphtbyl)carbonate,
D-14,362
lZ3~13
- 40 -
di(chloronaphthyl)carbonate, etc. or mixtures
thereof. The haloformates suitable for use herein
include bis-haloformate of dihydric phenols for
example, bischloroformates of bisphenol-A, of
hydroquinone, etc. or glycols for example,
bishaloformates of ethylene glycol, neopentyl
glycol, polyethylene glycol, etc. While other
carbonate precursor will be apparent to those
skilled in the art, carbonyl chloride, also known as
phosgene, is preferred.
The aromatic polycarbonate polymers may be
prepared by methods well known in the art by using
phosgene or a haloform ate and by employing a
molecular weight regulator, an acid acceptor and a
catalyst. the molecular weight regulators which can
be employed in carrying out the process include
mandrake phenols, such as phenol,
para-tertiary-butylphenol, para-bromophenol, primary
and secondary amine, etc. Preferably, a phenol is
employed as the molecular weight regulator.
A suitable acid acceptor may be either an
organic or an inorganic acid acceptor. A suitable
organic acid acceptor is a tertiary amine and
includes materials, such as pardon, triethylamine,
dimethylaniline, tributylamine, etc. The inorganic
acid acceptor may be one which can be either a
hydroxide, a carbonate, a bicarbonate, or a
phosphate of an alkali or alkaline earth metal.
he catalysts which are employed herein can
be any of the suitable cataly6t6 that aid the
polymerization of, for example, bisphenol-A with
phosgene. Suitable catalysts include tertiary
D-14,~62
amine, such a triethylamine, tripropylamine,
N,N-d;methylaniline, qua ternary ammonium compounds,
ouch a tetraethylammonium bromide. Seattle triethyl
Amman bromide, tetra-n-heptylammonium iodide. and
qua ternary pho~phonium compounds, such as
n-butyltriphenyl-phosphonium bromide and
methyl-triphenyl phosphonium bromide.
The polycarbonates can be prepared in a
one-phase (homogeneous 601ution) or a two-phase
(interracial) systems when phosgene, or a
haloform ate are used. sulk reactions are possible
when the diarylcarbonate precursors are used.
Also, aromatic polyester carbonates may be
used. These are described in, for example, U.S.
Patent 3,169,121. The preferred polyester carbonate
results from the condensation of phosgene,
terephthaloyl chloride, isophthaloyl chloride with
bi6phenol-A and a small amount of p-tertbutylphenol.
G Stvrene Resin
The styrenes resins suitable for use herein
include AS type polymer, the molecules of which
contain two or more polymeric parts of different
compositions that are bonded chemically. The
polymer is preferably prepared by polymerizing a
conjugated dine, such as butadiene or a conjugated
dine with a monomer copolymerizable therewith, such
a Turin, to provide a polymeric backbone. After
formation of the backbone, at least one grafting
monomer, and preferably two, are polymerized in the
presence of the prepolymerized backbone to obtain
the graft polymer. These resins are prepared by
methods well known in the art.
D-14,362
, .,_
isle
The backbone polymer, as mentioned, is
preferably a conjugated dine polymer such as
polybutadiene, polyisoprene, or a copolymer, such as
butadiene-~tyrene, butadiene-acrylonitrile, or the
like.
The specific conjugated dine monomers
normally utilized in preparing the backbone of the
graft polymer are generically described by the
following formula:
A A
A \ I I / A
I = C - C = C\
A A
wherein A it selected from the group consisting of
hydrogen, alkyd groups containing from one to five
carbon atoms, chlorine or bromide. Examples of
Dunn that may be used are butadiene, i60prene,
1,3-heptadiene, methyl-1,3-pentadieneO
2,3-dimethyl-1,3,-butadiene, 2-ethyl -
1,3-pentadiene: 1,3- and 2,4-hexadienes, sheller and
broom substituted butadienes such as
dichlorobutadiene, bromobutadiene, dibromobutadiene,
mixtures thereof, and the like. A preferred
conjugated dine is butadiene.
One monomer or group of monomer that may
be polymerized in the presence of the prepolymerized
backbone are monovinylaromatic hydrocarbons. The
monovinylaromatic monomers utilized are generically
described by the following formula:
D-14,362
Z3(~13
- 43 -
A A A
A ¦ A
A A
wherein A is as previously defined. examples of the
monovinylaromatic compounds and alkyd-, cycloalkyl-,
aureole-, alkaryl-, aralkyl-, alkoxy-, airlocks-, and
other substituted vinyl aromatic compounds include
Turin, 3-methylstyrene; 3,5-diethylstyrene,
4-n-propylstyrene, ~-bromostyrene,
dichlorostyrene, dibromostyrene,
tetra-chlorostyrene, mixtures thereof, and the
like. The preferred monovinylaromatic hydrocarbons
used are Saturn and/or a ~-methylstyrene.
A second group of monomers that may be
polymerized in the presence of the prepolymerized
backbone are acrylic monomers such as acrylonitrile,
substituted acrylonitrile and/or acrylic acid
esters, exemplified by acrylonitrile, and alkyd
acrylates such as ethyl acrylate and methyl
methacrylate.
The acrylonitrile, substituted
acrylonitrile, or acrylic acid eater are described
generically by the following formula:
A \
/ C~C B
A
wherein A is as previously defined and B is selected
from the group consisting of cyan and carbalkoxy
D-14,~62
23~13
wherein the alkoxy group of the carbalkoxy contain
from one to about twelve carbon atoms. Examples of
such monomers include acrylonitrile,
ethacrylonitrile, methacrylonitrile,
~-chloroacrylonitrile, ~-chloroacrylonitrile,
~-bromoacrylonitrile, and ~-bromoacrylonitrile,
methyl acrylate, methyl methacrylate, ethyl
acrylate, bottle acrylate, propel acrylate, isopropyl
acrylate, dud mixtures thereof. The preferred
acrylic monomer is acrylonitrile and the preferred
acrylic acid esters are ethyl acrylate and methyl
methacrylate.
In the preparation of the graft polymer,
the conjugated dolphin polymer or copolymer
exemplified by a 1,3-butadiene polymer or copolymer
comprises about 50~ by weight of the total graft
polymer composition. The monomers polymerized in
the presence of the backbone, exemplified by styrenes
and acrylonitrile, comprise from about 40 to about
95% by weight of the total graft polymer composition.
The second group of grafting monomers,
exemplified by acrylonitrile, ethyl acrylate or
methyl methacrylate, of the graft polymer
composition, preferably comprise from about 10~ to
about 40~ by weight of the total graft copolymer
composition. The monovinylaromatic hydrocarbon
exemplified by Turin comprise from about 30 to
about 70~ by weight of the total graft polymer
composition.
n preparing the polymer, it is normal to
have a certain percentage of the polymerizing
monomers that are grafted on the backbone combine
D-14,362
-lZ3(~13
-- us --
with each other an occur as free copolymer. If
styrenes is utilized a one of the grafting monomers
and acrylonitrile as the second grafting monomer, a
certain portion of the composition will copolymerize
as free styrene-acrylonitrile copolymer. In the
case where ~-methylstyrene (or other monomer) it
substituted for the styrenes in the composition used
in preparing the graft polymer, a certain percentage
of the composition may be an ~-methyl~tyrene-
acrylonitrile copolymer. Also, there are occasions
where a copolymer, such as ~-methylstyrene-
acrylonitrile, it added to the graft polymer
copolymer blend. When the graft polymer-copolymer
blend is referred to herein, it is meant optionally
to include at least one copolymer blended with the
graft polymer composition and which may contain up
to 90~ of free copolymer.
Optionally, the elastomeric backbone may be
an acrylate rubber, such as one based on n-butyl
assort, ethylacrylate, 2-ethylhexylacrylate, and
the like. Additionally, minor amounts of a dine
may be copolymerized in the acrylate rubber backbone
to yield improved grafting with the matrix polymer.
These resins are well known in the art and
many are commercially available.
H. PolY~Alkvl AcrYlate) Resin
The poly(alkyl acrylate) resin which may be
used herein include a homopolymer of methyl
m~thacrylate (i.e., polymethyl methacrylate) or a
copolymer of methyl methacrylate with a vinyl
monomer (e.g., acrylonitrile, N-allylmaleimide,
vinyl chloride or N-vinyl maleimide), or an alkyd
D-14,362
l.Z3~313
- 46 -
acrylate or methacrylate in which the alkyd group
contains from 1 to 8 carbon atoms, such a methyl
acrylate, ethyl acrylate, bottle acrylate, ethyl
methacrylate and bottle methacrylate. The amount of
methyl methacrylate is greater than about 70% by
weight of this copolymer resin.
The alkyd acrylate resin may be grafted
onto an unsaturated elastomeric backbone, such as
polybutadiene, polyi~oprene, and/or butadiene or
isoprene copolymers. In the case of the graft
copolymer, the alkyd acrylate resin comprises
greater than about 50 weight percent of the graft
copolymers.
These resins are well known in the art and
are commercially available.
The methyl methacrylate resins have a
reduced viscosity of from 0.1 to about 2.0 dug in a
one percent chloroform solution at 25~C.
I. PolYhvdroxvethers
The thermoplastic polyhydroxyethers which
may be used herein have the following general
formula:
JCF O P' 0
j
where F is the radical residuum of a dihydric
phenol, F' it a radical residuum of an epoxide
selected from moo- and diepoxides and which contain
from 1 to 2 hydroxyl groups, and j is an integer
D-14,362
1'~3(~3
- I _
which represents the degree of polymerization and it
at least about 30 and preferably is above about 80.
In general, thermoplastic polyhydroxyethers
are prepared by contacting, under polymerization
conditions, a dihydric phenol and an epoxide
containing from 1 to 2 epoxide groups in
substantially equimolar amounts by methods well
known in the art,
Any dihydric phenol can be used in forming
polyhydroxyethers. Illustrative dihydric phenols
are mononuclear dihydric phenols such as
hydroquinone, resorcinol, and the like as well as
the polynuclear phenol. The dihydric polynuclear
phenol have the general formula:
--En G Jo Jo It L
HO R Rig Al OH
wherein the R14 ' 6 are independently an aromatic
diva lent hydrocarbon radical, such as naphthylene
and phenylene with phenylene being preferred, the
G's may be the tame or different and are selected
from alkyd radicals, such a methyl, n-propyl,
n-butyl, n-hexyl, n-octyl and the like, preferably
alkyd radical having 1 to q carbon atoms; halogen
atoms, i.e., chlorine, bromide, iodine, or fluorine;
or alkoxy radicals suck as methoxy, methoxymethyl,
ethics, ethoxyethyl, n-butyloxy, amyloxy and the
like, preferably an alkoxy radical having 1 to 4
carbon atoms, the so are independently integer of
O to 4, Al is independently selected from a
delineate 6aturat~d aliphatic hydrocarbon radical
~-14,362
~.Z3~
- 48 -
particularly al~ylene or alkylidene radicals having
from 1 to carbons atoms, especially C(CH3)2,
cycloalkylene, cycloalkylidene or any other diva lent
group such as O, S, SO, SO, CO, a chemical bond,
etc. Particularly preferred are dihydric
polynuclear phenols having the general formula:
k Go
R20 OH
wherein G and k are as previously defined, and R20
is an alkaline or alkylidene group, preferably
having from 1 to 3 carbon atoms, cycloalkylene or
cycloalkylidene having 6 to 12 carbon atoms.
Diepoxides useful for the preparation of
polyhydroxyethers may be represented by repeating
unit of the following formula:
O O
/\ i\
H C C R21 C C H
wherein R21 ill representative of a bond between
adjacent carbon atoms or a diva lent organic radical
such as an aliphatic, aromatic, alicyclic,
hsterocyclic or cyclic arrangement of atoms.
Other diepoxides which can be mentioned
include those wherein two oxirane groups are linked
through an aromatic ether, i.e., compounds having
the grouping:
D-14,362
lZ3(~8~3
-- 49 --
--C OX 0------{R220~m C
wherein R22 is a diva lent organic radical, J is a
diva lent aromatic radical residuum of a dihydric
phenol, such as those listed above in the
description of dihydric phenols, and m is an integer
from o to 1 inclusive.
Still other diepoxides include ethers
wherein the oxirane groups are connected to vicinal
carbon atoms at least one pair of which is a part of
a cycloaliphatic hydrocarbon.
These polyhydroxy ethers are prepared by
methods well known in the art, such as those
described in, for example, U.S. Patents ~,238,087;
3,305,528; 3,924,747; and 2,777,051.
J. Polyamides
The polyamide polymers which may be used
herein are well known in the art. The polyamide
polymers include homopolymers as well as
copolymers. These polymers may be formed by
conventional methods from the condensation of
bifunctional monomers, by the condensation of
dominoes and dibasic acids, as well as by addition
polymerization. Numerous combinations of dissuades,
such all carbonic acid, oxalic acid, glutaric acid,
adipic acid, pimelic acid, sub Eric acid, azelaic
acid, sebacic acid, dodecanedioic acid, isophthalic
aria, terephthalic acid, and the like, dominoes,
such as hydrazine, ethylenediamine,
hexamethylenediamine, 1,8-octanedia~ine, piperazine,
and the lye, and amino acids are possible. The
chain between functional groups in the reactant
D-1~,362
~Z3(~3
- 50 -
may comprise linear or branched aliphatic
hydrocarbon, or alicyclic or aromatic rings. They
may also contain hotter atoms such as oxygen,
sulfur, and nitrogen. Secondary dominoes lead to
the formation of N-substituted polyamides
Also, included herein are the aromatic
polyamide polymers which are aromatic in both the
Damon and the dibasic acid. Tube dibasic acids
include terephthalic acid, isophthalic acid,
phthalic acid, and the live. The aromatic dominoes
include o-phenylenediamine, 2,4-diaminotoluene,
4,4'-methylenedianiline, and the live.
The polyamide polymers are prepared by
methods well known in the art, such as by direct
amidation which is the reaction of amine groups with
carboxyl6 accompanied by elimination of water; low
temperature polyconden~ation of dominoes and dozed
chloride, ring-opening polymerization, addition of
amine to activated double bonds, polymerization of
isocyanates and reaction of formaldehyde with
denaturalize.
The polyamide polymer include
polyhexamethy~ene-adipamide, i.e., nylon 6,6;
poly(t-caprolactam), i.e., nylon-6;
polypropiolactam, i.e., nylon-3;
poly(pyrrolidin-2-one), ire., nylon-4;
poly(~-enanthamide), i.e., nylon-7;
polycapryllactam, i.e., nylon-8;
poly(~-pelargonamide), i.e., nylon-9
poly(ll-aminodecanoic acid), i.e., nylon-10;
poly(~-undecaneamide), i.e., nylon-ll;
D-14,362
lZ3(~8~3
polyhexamethyleneterepht~alamide, i.e., nylon-6,T,
nylon 6,10, and the like
K. PolY(arYlene sulfide)
The poly(arylene sulfides which are
suitable for use herein are solid, have a melting
point of at least about 150~. and are insoluble in
common solvents. Such resins can be conveniently
prepared by the process disclosed in, log example,
U.S. Pat. No. 3,354,129. Briefly, tube process
comprises the reaction of an alkali metal sulfide
and a polyhalo ring-substituted aromatic compound in
the presence of a suitable polar organic compound.
as for example, the reaction of sodium sulfide with
dichlorobenzene in the presence of
N-methyl-2-pyrrolidone to form poly(phenylene-
sulfide).
The resulting polymer contains the aromatic
nucleus of the polyhalo-substituted monomer coupled
in repeating units predominantly through a sulfur
atom. The polymers which are preferred for use
according to this invention are those polymers
having the repeating unit -~23-S- where R23 is
phenylene, biphenylene, naphthylene, or a lower
alkyl-sub6tituted derivative thereof. my lower
alkyd it meant alkyd groups having one to six carbon
atom such as methyl, propel, isobutyl, n-hexyl and
the like.
The preferred poly(arylene sulfide) it
polytphenylene sulfide), a crystalline polymer with
a repeating structural unit comprising a
para-sub6tiSuted Bunsen ring and a sulfur atom
D-14,362
~Z30~3
which may be described by the following formula,
where p has a value of at least about 50.
So
Suitable poly(phenylene sulfide) compositions are
available commercially under the trade name WriteNow of
the Phillips Petroleum Company. Preferably, the
poly(phenylene sulfide) component has a melt flow
index, measured at 600F. using a 5 Kg. weight and a
standard orifice, within the range of from about 10
to about 7000 dg./min..
The term poly(arylene sulfide) it meant to
include not only homopolymer~ but also Arlene
sulfide copolymers, terpolymers and the like.
OTHER ADDITIVES
Other additives which may be used in
combination with the thermoplastic polymers include
mineral filler such a carbonate including chalk,
calcite and dolomite; silicate including mica,
talc, wollastonite; silicon dioxide; glass spheres;
glass powders; aluminum; clay: quartz; and the
like. Additional additives include glass fibers;
pigments, such as titanium dioxide; thermal
stabilizers suck as zinc oxide; ultraviolet light
stabilizers, plasticizer, and the live,
The mineral filler may be used in amounts
of up to about 30, preferably up to about 25 weight
percent. The pigments are generally used in amounts
of up to about 10 weight percent. The stabilizers
D-14,362
-` 23~ 3
are used in stabilizing amounts to stabilize the
composition for the effect desired.
FABRICATION
The thermoplastic polymer, and one or more
optional additives is generally compounded in an
extrude. The compounding it carried out at
temperatures of from about 200C to about 400C.
The compounded material may be poulticed by
conventional techniques.
The compounded material is extruded into a
sheet and then thermoformed into the desired article
by methods well known in the art.
The thermoplastic polymer either alone or
in combination with other materials may be fed in
particulate form (such do pellet, granule,
particles, powders, and the like) into an extrude
which extrudes the material into a laminate. The
extruder6 which are used to form the laminate are
well known in the art. Typically, the extrude may
be a 2 1/2 inch Davis standard extrude containing
an extrude screw with a length to diameter ratio of
24 to 1.
The laminate may be prepared by the
procedure and using the apparatus as described in
U.S. Patent 3,557,265. In the method of said
patent, film or sheet having a plurality of layers
i& formed by deforming a flowing stream having
layer of diverse thermoplastic material wherein the
cross-sectional configuration of the plurality of
flowing stream it altered by reducing the dimension
Or the stream in a direction generally perpendicular
to the interface between the individual stream and
D-14,362
~.23~813
by increasing the dimension of the stream in a
direction generally parallel to the interface to
provide a sheet having a luminary structure.
The laminate of this invention are
generally from about 20 to about 40 miss, preferably
about 30 miss thick. The inner layer ranges from
about 5 to about 15 mill in thickness.
The laminate is then thermoformed into the
shape of the desired article. Thermoforming may be
accomplished by methods well known in the art such
as those described in, for example, Engineering
Polymer Science and Technology, Volume 13, 1971,
pages 832-8g3. Generally, the laminate is vacuum
formed into a female mold. In this process, the
laminate it locked in a frame around its periphery
only, it heated to a predetermined temperature for a
predetermined time and then brought into contact
with the edge of the mold. This contact creates a
seal so that it is possible to remove the air
between the hot laminate and the mold, allowing
atmospheric pressure to force the hot laminate
against the mold. Also, the laminate may be draped
manually to the required contour of a female mold,
such as to make a seal possible. Positive air
pressure may also be applied against the top of the
laminate to force it into a female mold as an
alternative to vacuum forming.
To promote uniformity of distribution in
cookware of particular shapes such as a box shape, a
plug asset may be use. This may be any type of
mechanical helper which carries extra material
toward an area which would otherwise be too thin.
D-14,362
lZ3(~813
Usually the plug is made of metal, and heated to a
temperature slightly below that of the hot plastic,
so as not to cool the laminate before it can reach
its final shape. Instead of metal, a smooth gained
wood can be used or a thermo6et plastic, such as
finlike or epoxy. These materials are poor
conductors of heat and hence do not withdraw much
heat from the sheet. Plug desists are adaptable
both to vacuum forming and pressure forming
techniques.
Another method which can be used to
thermoform the laminate is matched mold forming. In
this method, the laminate is locked into a clamping
frame and heated to the proper forming temperature.
A male mold is positioned on the top or bottom
platen with a matched female mold mounted on the
other platen. The mold is then closed, forcing the
laminate to the contours Ox both molds. The
clearance between the male and female molds
determines the wall thickness. Trapped air is
allowed to escape through both mold faces. Molds
are bold in place until the laminate cools.
In a preferred embodiment, the laminate is
locked into a frame around its periphery only. The
laminate it then heated in an oven to a temperature
above the glass transition of the polymer(s) in the
laminate, which is generally between about 530 and
about 600F. The laminate is heated a this
temperature for about 15 to about 20 seconds 60 that
the laminate flags under it own weight. The
laminate it then brought into contact wit the edge
of a female mold 80 as to create a seal between the
D-1~,362
~Z3(~813
- 56 -
hot plastic and the mold. The female mold it
positioned in the top platen. A vacuum is then
started so that the laminate it pulled into the
confine of the female mold. The mold temperature
it generally from about 240 to about 380~. The
material is allowed to remain in the mold for about
30 seconds 60 that it cools from its initial
temperature of between 530 and 600F to the mold
temperature which it from about 240 to about 3~0F.
The formed laminate at ibis point it rigid and can
be removed from the mold. The preferred molding
procedure result in a better distribution of
thickness of material in the molded article. Allah,
the molded articles is generally free of pin holes
when this procedure, it used. In a variation of the
preferred procedure, the laminate is forced into the
female mold with a plug assist. The plug it 80
positioned that it carries the laminate into the
female mold but does not touch any part of the
mold. The vacuum it then turned on 60 that the
laminate forms to the contours of the female mold.
The formed laminate it allowed to cool as described
above and then removed from the mold.
COOKWARE
The cookware of this invention may be any
type of container or tray which it used to heat or
cook food. The cookware may be of any shape or
design with dimensions dependent upon the desired
end use. Representative cookware is found in, for
exile, U.S. Patents 3,938,730: 3,743,077 and
3,955,170. Aye, representative designs of cookware
are described in, for example. Dew. 236.574; 194,277
and 236,132. The cookware may be used to beat and
D-lq,362
~..Z3g'~813
- 57 _
bake all type of food, including frozen ford in a
conventional or microwave oven.
EXAMPLES
The following examples serve to give
specific illu6tration6 of the practice of ibis
invention but they are not intended in any way to
limit the scope of thy invention.
The following designations used in tube
Examples have the following meaning:
Pol~arvlethersulfone: A polymer having the
following repeating unit:
~o~S02~S02~SO~
The polymer has a reduced viscosity of 0.61
dug as measured in N-methyl-pyrrolidinone (0.2
g/100 ml) at 25C,
Pol~ethvlene tereDhthalate (PET): Vituf
Lola obtained loom Goodyear Chemicals. This
polymer ha an intrinsic viscosity of 1.04 dug as
measured in 60/40 phenol/tetrachloroethane at 25C.
PREPARATION OX POLyARyLETHERsuLFoNE
A four neck 1000 ml round-bottom flask was
equipped with a mechanical stirrer, thermometer,
addition funnel, dry nitrogen inlet, and vacuum
jacketed vigreux column with Dean Stark trap and
condenser. Into the flask were charged 143.53 q
(0.50 moles) of 4,4'-dichlorodiphenyl cellophane, 62.58
9 (0.25 moles) of 4,4'-dihydroxydiphenyl cellophane,
27,56 9 (0.25 moles) of hydroquinone, 76.02 g (0.55
Poles] of potassium carbonate. 100 ml of Tulane and
D-14,362
~l23(~8~3
- 58 -
466 ml of 6ulfolane. The mixture was purged with
nitrogen for 1 hour at room temperature (about Z50C)
and then heated to reflex (141C). After 1 hour at
reflex, the temperature of the reaction was
increased to about 200C by slowly removing the
Tulane. After about 5 hours at 200C, the reaction
way terminated by adding methyl chloride. The
polymer 80 produced way recovered by coagulation in
water followed by washing the polymer several time
with hot water (80C).
The polyarylether6ulfone product had a
reduced viscosity of 0.61 dug a measured in
N-methyl-pyrrolidinone (0.2 g~100 ml) at 25C. The
polymer way made up of the following repeating unit:
~O~S2~so2~so2~
PREPARATION OX LAMINATES
A Reed Color Matter Batch of titanium
dioxide in polyethylene terephthalate which
contained 40~ by weight of titanium dioxide was
diluted with PET to a contained level of I by
weight ox titanium dioxide by dry tumbling. This
composition was dried at 300F for about 6 hours.
This composition was then fed into a 2 1/2 inch,
24:1 (LID) Davis standard extrude. At the tame
time Polyarylethersulfone was fed into a 1 1/4
Satellite Extrude. The die way 35 inches. A 30 Gil
co-extruded laminate was produced having 12 miss of
PUT as the outside layer and a 6 mix core layer of
Polyarylethersulfo~e.
D-14,362
. Jo
13
59
GENERAL PROCEDURE OF FABRICATION
OF COOKWARE FRY LAMINATES
The laminates made above were thermoformed
into cookware which way a tray 7 lJ4 inches long, 5
1/9 inches long and 1 inch deep. The laminate was
first placed into a frame and clamped. The frame
was placed between two heaters which were at about
1200F for about 25 seconds until the laminate began
to "sag" under its own weight. The temperature of
the laminate at this point was between 530 and
600~F. The laminate was then placed into contact
with a female mold which was in the bottom platen of
a press. The female mold was raised into contact
with the laminate 60 as to form a tight seal with
the laminate. A vacuum was started and the laminate
contacted the female mold. The mold temperature was
about 275 to 350P. The laminate was in contact
with the female mold for about 30 seconds. The mold
was retracted and the tray formed was released.
Total cycle time was about 90 seconds. Tube tray was
then trimmed. The average gauge thickness of the
tray was 30 miss.
D-14,362
