CA1230813A - Cookware formed from a laminate - Google Patents

Abstract

COOKWARE FORMED FROM A LAMINATE

ABSTRACT OF THE DISCLOSURE

Described herein is cookware formed from a laminate, said laminate comprising three sheets made from a thermoplastic resin, the inside sheet made from a thermoplastic resin having a higher use temperature than the two outside sheets.

S P C I F I C A T I _ N

Description

~23~ 3 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 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 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.

D-14,362 .. . .

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.

D-14,362 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 wherein Al and R2 are independently hydrogen or Of to Cog alkyd, or I
( IRK) ( to) D-14,3S2 lZ3~813 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.

D-14,362 lZ3C~13 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:

D~14,362 ~3~3 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 D-14,362 123~ 3 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, D-14,362 ~Z3~13 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, D-14,362 ~23~313 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, D-14,362 ~23(}813 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.

D-14,362 ! 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 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.

D-14,362 123(~;~313 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 D-14,362 ..

lZ~(~813 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 (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

D-14,362 ~Z3~813 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.

D-14,362 1~3~

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 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 (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 , 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 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 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

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

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 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 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 --_ 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 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 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 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 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 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~

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 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\

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 --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 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 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(~8~3 466 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 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

Claims (45)

WHAT IS CLAIMED IS:

1. 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 two outside sheets, said thermoplastic resin selected from a polyarylethersulfone, a poly(aryl ether), polyarylate, polyetherimide, polyester, aromatic polycarbonate, styrene resin, poly(alkyl acrylate), polyhydroxyether, poly(arylene sulfide) and polyamide.

2. Cookware as defined in claim 1 wherein the inside sheet is made from a thermoplastic resin selected from a polyarylethersulfone, a poly(aryl ether) or a polyetherimide and wherein both outside sheets are a polyester.

3. Cookware as defined in claim 1 wherein the thermoplastic resin is a polyarylethersulfone.

4. Cookware as defined in claim 3 wherein the polyarylethersulfone contains units of the following formula:

(I) , and (II) and/or (III) wherein R is independently hydrogen, C1 to C6 alkyl or C4 to C8 cycloalkyl, X' is independently wherein R1 and R2 are independently hydrogen or C1 to C9 alkyl, or wherein R3 and R4 are independently hydrogen or C1 to C8 alkyl, and a1 is an integer of 3 to 8: -S-, -O-, or , a is an integer of 0 to 4 and n is 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, wherein the units are attached to each other by an -O- bond.

5. Cookware as defined in claim 4 wherein in the polyarylethersulfone, unit (I) has the formula:

6. Cookware as defined in claim 4, wherein in the polyarylethersulfone, unit (II) has the formula:

7. Cookware as defined in claim 4, wherein in the polyarylethersulfone, unit (III) has the formula:

8. Cookware as defined in claim 4, wherein the polyarylethersulfone contains recurring units of the formula:
said units being attached to each other or by an -O-bond.

9. Cookware as defined in claim 1, wherein the polyarylethersulfone contains recurring units of the formula:

(I) (II)

10. Cookware as defined in claim 1 wherein the poly(aryl ether) contains recurring units of the following formula:
-O-E-O-E'-wherein E is the residuum of a dihydric phenol, and E' is the residuum of a benzenoid compound having an inert electron withdrawing group in at least one of the positions ortho and para to the valence bonds;
both of said residua are valently bonded to the ether oxygens through aromatic carbon atoms.

11. Cookware as defined in claim 10 wherein the poly(aryl ether) has repeating units of the formula:

12. Cookware as defined in claim 10 wherein the poly(aryl ether) has repeating units of the formula:

13. Cookware as defined in claim 8 wherien the poly(aryl ether) contains units of the following formula:

14. Cookware as defined in claim 1 wherein the thermoplastic polymer is a polyarylate.

15. Cookware as defined in claim 14 wherein the polyarylate is derived from a dihydric phenol and at least one aromatic dicarboxylic acid.

16. Cookware as defined in claim 15 wherein the dihydric phenol is of the following formula:

wherein Y is independently selected from, hydrogen, alkyl groups of 1 to 4 carbon atoms, chlorine or bromine, each d, independently, has a value of from 0 to 4, inclusive, and R11 is a divalent saturated or unsaturated aliphatic hydrocarbon radical, particularly an alkylene or alkylidene radical having from 1 to 6 carbon atoms, or a cycloalkylidene or cycloalkylene radical having up to and including 9 carbon atoms, O, CO, SO2, or S.

17. Cookware as defined in claim 15 wherein the aromatic dicarboxylic acid is terephthalic acid, isophthalic acid, any of the naphthalene dicarboxylic acids and mixtures thereof, as well as alkyl substituted homologs of these carboxylic acids, wherein the alkyl group contains from 1 to about 4 carbon atoms, and acids containing other inert substituents. such as halides, alkyl or aryl ethers.

18. Cookware as defined in claims 14 or 15 or 16, or 17 wherein the polyarylate is derived from bisphenol A and terephthalic acid or isophthalic acid, or mixtures thereof.

19. Cookware as defined in claim 1 wherein the thermoplastic polymer is a polyetherimide.

20. Cookware as defined in claim 19 wherein the polyetherimide polymers is of the following formula:

wherein e is an integer greater than 1, preferably from about 10 to about 10,000 or more, -O-R12-O-is attached to the 3 or 4 and 3' or 4' positions and R12 is selected from (a) a substituted or unsubstituted aromatic radical such as (b) a divalent radical of the formula:

wherein R14 is independently C1 to C6 alkyl, aryl or halogen and R15 is selected from -O-, -S-, . -SO2-, -SO-, alkylene of 1 to 6 carbon atoms, cycloalkylene of 4 to 8 carbon atoms, alkylidene of 1 to 6 carbon atoms or cycloalkylidene of 4 to 8 carbon atoms, R13 is selected from an aromatic hydrocarbon radical having from 6 to 20 carbon atoms and halogenated derivatives thereof. or alkyl substituted derivatives thereof, wherein the alkyl group contains 1 to 6 carbon atoms, alkylene and cycloalkylene radicals having from 2 to 20 carbon atoms and C2 to C8 alkylene terminated polydiorganosiloxane or a divalent radical of the formula wherein R14 and R15 are as previously defined.

21. A composition as defined in claim 20 wherein the polyetherimide is of the following formula:

wherein -O-Z is a member selected from wherein R16 is independently hydrogen, lower alkyl or lower alkoxy wherein the oxygen may be attached to either ring and located ortho or para to one of the bonds of the imide carbonyl groups, R12 and R13 and e are as defined in claim 22.

22. Cookware as defined in claim 19 wherein the polyetherimide has repeating units of the following formula:

23. Cookware as defined in claim 1 wherein the thermoplastic polymer is a polyester.

24. Cookware as defined in claim 23 wherein the polyester has repeating units of the general formula:

wherein n is an integer of from 2 to 10.

25. Cookware as defined in claims 1 or 2 wherein the polyester is poly(ethylene terephthalate).

26. Cookware as defined in claim 1 wherein the thermoplastic polymer is an aromatic polycarbonate,

27. Cookware as defined in claim 26 wherein the aromatic polycarbonate is the reaction product of a dihydric phenol and a carbonate precursor.

28. Cookware as defined in claim 27 wherein the dihydric phenol is bisphenol-A and the carbonate precursor is carbonyl chloride.

29. Cookware as defined in claim 26 wherein the polycarbonate is poly(ester carbonate).

30. Cookware as defined in claim 1 wherein the thermoplastic polymer is a styrene polymer.

31. Cookware as defined in claim 30 wherein the styrene polymer is prepared by polymerizing a conjugated diene monomer, or a conjugated diene monomer and monomer copolymerizable therewith, or an acrylic acid ester, to provide an elastomeric backbone, and thereafter grafting at least one grafting monomer onto said backbone.

32. Cookware as defined in claim 31 wherein the conjugated diene monomer is butadiene and the grafting monomer is selected from styrene, an acrylonitrile, an acrylic acid ester, or mixtures thereof.

33. Cookware as defined in claim 32 wherein the styrene resin is a butadiene/styrene/acrylonitrile resin.

34. Cookware as defined in claim 1 wherein the thermoplastic polymer is a poly(alkyl acrylate) polymer.

35. Cookware as defined in claim 34 wherein the poly(alkyl acrylate) is poly(methyl methacrylate).

36. Cookware as defined as in claim 35 wherein the poly(alkyl acrylate) is a copolymer of methyl methacrylate and a vinyl monomer wherein the amount of methyl methacrylate is greater than about 70 percent of weight of the copolymer.

37. Cookware as defined in claim 36 wherein the vinyl monomer is selected from acrylonitrile, N-allylmaleimide, vinyl chloride, N-vinylmaleimide or an alkyl acrylate or methacrylate, wherein the alkyl group contains from 1 to 8 carbon atoms.

38. Cookware as defined in claim 1 wherein the thermoplastic polymer is a polyhydroxyether.

39. Cookware as defined in claim 38 wherein the polyhydroxyether has the following general formula:
where F is the radical, residuum of a dihydric phenol, F' is a radical residuum of an epoxide selected from mono- and diepoxides and which contain from 1 to 2 hydroxyl groups, and j is an integer which represents the degree of polymerization and is at least about 30.

40. Cookware as defined in claim 1 wherein the thermoplastic polymer is a polyamide.

41. Cookware as defined in claim 40 wherein the polyamide is selected from nylon 6,6, nylon 6, or nylon 6,10.

42. Cookware as defined in claim 1 wherein the thermoplastic polymer is poly(arylene sulfide).

43. Cookware as defined in claim 42 wherein the poly(arylene sulfide) is of the following formula:

wherein p has a value of at least about 50

44. A 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 two outside sheets, said thermoplastic resin selected from a from a polyarylethersulfone, a poly(aryl ether), polyarylate, polyetherimide, polyester, aromatic polycarbonate, styrene resin, poly(aryl acrylate), polyhydroxylether, poly(arylene sulfide) or polyamide.

45. A laminate as defined in claim 44 wherein the inside sheet is made from a thermoplastic resin selected from a polyarylethersulfone, a poly(aryl ether) or a polyetherimide and wherein both outside sheets are a polyester.