CA1196146A - Plastic ovenware - Google Patents
Plastic ovenwareInfo
- Publication number
- CA1196146A CA1196146A CA000357731A CA357731A CA1196146A CA 1196146 A CA1196146 A CA 1196146A CA 000357731 A CA000357731 A CA 000357731A CA 357731 A CA357731 A CA 357731A CA 1196146 A CA1196146 A CA 1196146A
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
- C08G63/605—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds the hydroxy and carboxylic groups being bound to aromatic rings
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47J—KITCHEN EQUIPMENT; COFFEE MILLS; SPICE MILLS; APPARATUS FOR MAKING BEVERAGES
- A47J27/00—Cooking-vessels
- A47J27/06—Steam-heated kettles for domestic use
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Polyesters Or Polycarbonates (AREA)
- Table Devices Or Equipment (AREA)
- Cookers (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Ovenware capable of use in both conventional thermal and microwave ovens fabricated from wholly aromatic polyesters, and, more particularly from oxybenzoyl polyesters.
Ovenware capable of use in both conventional thermal and microwave ovens fabricated from wholly aromatic polyesters, and, more particularly from oxybenzoyl polyesters.
Description
BA~KGROUND OF THE INVENTION
It is known that certain plastic materials have found some application in the ovenware field. For e~ample, polymethyl-pentene has been used for injection molded trays which can be used in the preparation of foods. Polysulfone has also been employed in food handling applications. However, no satisfactory material has been found possessing utility over the wide ranges of condi-tions and of demands which are encountered in the provision of cook-in containers, or ovenware, which can be used in either thermal ovens or microwave ovens.
In addition to the obvious necessity for a material which can withstand the temperatures met in the heat source used for cooking, a material must provide a unique combination of a number of other characteristics before ovenware fabricated from the material can be successfully employed in the preparation of food. The material must have good electrical properties. It must be able to undergo severe thermal shocks in that ovenware prepared from it must be capable of going from conditions of extreme cold to high temperatures in relatively brief periods of time. The material must have good hardness and impact strength and possess high tensile and flexural trength. It must also be resistant to boiling water and to ad~erse e~fects from immersion in detergents.
In the area of food related properties the material must impart to the ovenware fabricated from it resistance to staining by a wide variety of foodstuffs. It must provide a surface affording good antistick properties, ready releasability for the food which it contains. It must not emit or give off any volatile matter and it must not have any extractable constituent~
And in addition to meeting all of the foregoing requirernents, articles prepared from it must present a pleasing appearance~
'iS ;r SUMMARY OF THE PRESENT INVENTION
Ovenware meeting the stringent demands of the cook-in container market is provided by fabrica~ing the ovenware articles from a plastic material based upon wholly aromatic polyesters, more particularly, upon oxybenzoyl polyesters.
The wholly aromatic polyesters employed in accordance with the present invention consist of combinations of repeating units of one or more of the following formulae:
~ ~X~n ~/ c __oc~3 (Xln ~ ~\ co~
P--q I II
10 ~ ~ ~X)n ~ ~ ~ ~ ~ co -- - r - - s III IV
oc ~ ~ co _o ~3 o t u O VI
where x is O, S,~c-, NH, or SO2 and n is o or 1 and the total of the integers p+q+r~stt~u, in the moieties present is from about 3 to about 800.
Combinations of the above units include union of the carbonyl group of Formulae I, II, IV and V with the oxy group of Fo.rmulae I/ III, IV and VI. In the most general combi.nation all units of the above formulae can be present in a single co-polymer. The simplest embodiment would be homopolymers of units I or IVo Other combinations include mixtures of unlts Il and III, II and VI, III and V, V and VI, and I and IY.
The location of the functional groups are preferably in the parar (l,4~ positions. They can also be located in ortho (l,2) position to each other. With respect -to the napthalene moiety the most desirable locations of the functional groups are l,4; l~5 and 2,6. Such groups can also be in the ortho position to each other.
The symbols p, q, r, s, t and u are integers and indicate the number of moieties present in -the polymer. The total (p+q+r+s~t~u) can vary from 30-~00 and, when present, the ratio of q/r, q/u, t/r, t/u, q~t/r. q+t/r+u and t/r+u can vary from about lO/ll to about ll/lO with most prefèrable ratio being lO/lO.
Exemplary of materials from which the moieties of Formula I may be obtained are p-hydroxybenzoic acid, phenyl-p-hydroxybenzoate, p-acetoxybenzoic acid and isobutyl-p-acetoxy-benzoate. Those from which the moie~y of Formula II is derivableinclude terephthalic acid, isophthalic acid, diphenyl tere~
phthalate, diethyl isophthalate, methylethyl terephthalate and the isobutyl half ester of terephthalic acid. Among the compounds from which the moiety of Formula III results are p,p'-bisphenol;
p,p'-oxybisphenol; 4,4'-dihydroxybenzophenone; resorcinol, and hydro~uinone. Inspection will show which of these materials are also suitable for supplyiny the moieties of Formulas VI-VIII.
Example of monomers represented by Formula IV are 6-hydroxy-l-naphthoic acid, 5-acetoxy-l-napthoic acid and phenyl 5-hydroxy-l-naphthoate. Monomers representing ~ormula V include l,4-napthalenedicarboxylic acid, l,5-napthalenedicarboxylic acid and 2,6-napthalenedicarboxylic acid. The diphenyl esters or dicarbonyl chlorides of these acids can also be used. Examples of monomers representative of Formula VI are, l,4~dihydroxy~
naphthalene, 2,6-diacetoxynaphthalene, and 1,5-dihydroxynaphtha-lene.
Particularly preferred for use in the practice of the present invention are plastic materials based upon oxybenzoyl polyesters.
The oxybenzoyl polyesters useful in the present invention are generally those repeating units of Formula VI:.
O ~= C ~
where p is an integer of from about 3 to about 600.
One preferred class of oxybenzoyl polyesters are those of Formula VII:
(VII) ._ Rl o ~) 11 ~ o~2 P
wherein Rl is a member selected from the group consisting of benzoyl, lower alkanoyl, or preferably hydrogen, wherein R2 is hydrogen, henzyl, lower alkyl, or preferably phenyl and p is an integer from 3 to 600 and preferably 30 to 200. These values of ~ correspond to a molecular weight of about 1,000 to 72,000 and preferably 3,500 to 25,000.
Another preferred class of oxybenzoyl polyesters are copolyesters of recurring units of Formulas VII, VIII and IX:
(VIII) o ~ o ~C - I J C
_ ~ q __ _ (IX) _ o ~ ( (X) ~ ~ O
n _ r wherein X is - O or - SO2 - m is 0 or 1: n is 0 or 1: q:r =
10:15 to 15:10; p:q = 1:100 to 100:1; p + q -~ r = 3 to 600 and preferably 20 to 200. The carbonyl groups of the moiety of Formula I or III are linked to the oxy groups of a moiety of Formula I or IV; the oxy groups of the moiety of Formula I or IV
are linked to the carbonyl groups of the moiety of Formula I or III.
The preferred copolyesters are those of recurring units of Formula X;
(X) ~
C ~ C-O ~C -O ~ ~ O
The synthesis of these polyesters is described in detail in U.S. Paten-t 3,637~595 entitled "P-Oxybenzoyl Copolyesters".
The polyesters useful in the present invention can also be chemically modified by various means such as by inclusion in the ~olyester of monofunctional reactant~ such as benZoic acid or tri - or hi~her functional reactant5 such as trlmesic acid o~
cyanuric chloride. The benzene ring3 in the~e polyeste~s a~e p~~
ferably unsubstitu~ed ~ut can be substituted with non~interferrin~
substituen~.s,examples of which include among othe~ halogen ~uch as chlorine or bromine, lower alkoxy such a.s methoxy and low~
alkyl such as methyl.
The oxybenzoyl polyesters useful in the present invention can be employed with various fillers of types and in amounts which do no-t ma~erially affect -th desired properties. ~xamples of suitable fillers include among others glass fibers,polytetra-fluoroethylene, pigments,fillers and polyimides.
The invention is further illustrated by the following examples in which all parts and percen~ages are by weight unless otherwise indicated. These nonlimi~ing examples are illustrative of certain embodiments designed to teach those skilled in th~ art how to practice the invention and to represent the best mode contemplated for carrying out the inven-tion.
EXAMPLE I
250 ~ of a mixture consisting of 40~ o-terphenyl and 60~ m-terphenyl i5 ~harged il~tO a four-neclced, round bottom flask fitted with a stirrer, a nitrogen inlet, a thermometer and a dis-tilling head leading to a condenser. The distilling head is ex-ternally wound with electrical resistance heating wire in order that it may ~e heated and a hea~ing mantle is provided ~o heat the f~ask and its contentsO Tl~e contents of the flask are melted by heating to dbout 60C.~ whereupon 68 g of ~acetoxybenzoic acid are added with stirring. ~`he entire condensation is carried out with constant stirring and with a slow flow of nitroyen through the flask to provide a non-oxidizing atmosphere. The distilling head is heated to about 120C and the mixture in the flask is heated to about 340C, polyester preci~itation startinc3 to occur at about 3P0C. The distilling head ~emperature is then raised ~o about 18QC to avoid refluxing of the distillata and/ox ~olid~
ification thereof in the distilling head, and the mixtu~ th~
flask is held at about 340~C for about 12 hour~. A total O~
25.5 g of distillate is collected, consisting primarily ~f aCetic acid, the remainder being primarily terphenyl liquid heat t~ans~er medium. It is observed tha-t 25 g of this distillate are coll~cted within 35 minutes after the temperature of 340C h~ bee~ reached, indicating that the polym~ri2ation is already approaching com-pletion within this time.
The resulting mix~ure is cooled to 80~, becoming qui-te viscous. ~out 200 ml of acetone are added slowing and ~he mixture is filtered to recover the polyester precipitate. The polyester is extracted overnight with acetone in a Soxhlet extractor to remove any residual ter~henyl liquid hea~ transfer medium and is then dried in vacuu~ for 3 hours at 110C. A yield of 43 g (96%
of theory) of p-oxybenzoyl polyester powder is obtained.
~he product was infusible and upon being held at 400C
in air it exhibited a weight loss of only 0.83~ per hour. Differ-ential thermal analysi~ revealed an endotherm, during heatinc~, at 329-343C, with a peak at 336C and a corresponding exo~herm ~urinc~
cooling, evidencing a reversible crystalline tran~ition, ~hi~
~eve~sible tran~ition was also evidenced by a marked change ~hich occurred in the X-ray ~owder diffraction pattern u~on heating the product to about 340C, the original ~attern ~ein~ resumed upon coolill~J.
In the X-ray ~owder diffraction pattern of the product at roon~ temperature, usincJ monochromatic co~per K alpha radiation, the large numbe.r and the sharpness of the diffrac-tion lines indi-cates that the polyes~er is hi~hly crystalline.
The use of a liquld heat transfer.medium is esserltial to the method employed. *he liquid must be inert, i.e it mu~t ~e non-reactive with the p-acetoxybenzoic acid monomer and th~ conden-sation products ther~of under the condition~ ~mployed. ~h~ liq~id must also be high boiling, having a boiling point unde~ th~ condi-tions employed which is at least as high a~ the hig~e~t temp~tu~
to which the reaction mixture iB heated, and convenl~ntly ~mewhat higher so that refluxing may be avoided. It will be appa~ent ~ha$
the heat transfer medium need no~ be liquid at room tempe~ature, but it should preferably have a melting point below that o~ the monomer (about 180C). A wide variety of materials has ~een found to be suitable as liquid hea~ transfer media including, for example o-terphenyl, m-terphenyl, p-terphenyl and mixtures oE two or msre thereof 5uch dS employed in the example; partially hydrogenated terphenyls SUc}l as th~se commercially available under ~he trade mark Therminol~ 66; and a eutectic mixture of 73O5% diphenyl oxide and 26.5% dip}lenyl suc}l as that which is co~nercially available as ~owthermR A heat tr~nsfer medium. O~her suitable liquid heat ransfer media include diphenoxybip}lenyls and mixtures thereof uch as those disclosed in U. S. Pat. 3,406,207-~X~MPI.E 2 This example illustrates the synthesis of a copolyesteruseful in the present invention.
The following quantities of the following ingredients are combined as indicated.
Quantity I~em Ingredient Grams Moles A P-hydroxybenzoic Acid 138 B Phenyl acetate 170 1.25 C Therminol 77 500 __ D Diphenyl Terephthalate 318 E llydrogen Chloride F ~3ydroquinone 111 1.~1 G Therminol 77 500 --Items A - D are char~3ed to a four-necked, round bottom flask fitted with a ~hermometer, a stirrer, a combined ni-trogen and HCl inlet ~nd an outlet connected to a condenser. Nitrogen is passed slowly through the inlet. The flask and its contents are heated to 180C whereupon ~Cl is bubbl~d through the reaction mi~-ture. The outlet head t~mperature i5 kept at 110 - 120C by external heating during the p-hydroxy~enzoic acid, phenyl acetate ester exchange reaction.
The flask and its contents are stirred a-t 180C ior 6 hours whereupon the HCl is shut off, the outlet head tempe~ature rai~ed to 180 - 190C and the nlixture ~ irred at 220C for 3,5 hGurs. Up to this point, 159 grams of dis~illate are collected in the ~ondenser. Item F is then added and the temperature gradually increased from 220C to 320C over a period of 10 hours ~10C/hr)~
~tirring is continu~d at 320C or 16 hours and then for three additional hours at 340C to form a slurry~ The total amount o~
distillate, consisting of phenol, acetic acid and phenyl acetate, amounts to 384 g. Item G is added and the r~acti~n mixture per-5 mitted to cool to 70C. Acetone (750 ml~ is added and the slurryfiltered, the solids are extrac~ed in a Soxhlet with acetone to remove i~ems C and ~. The solids are dried in vacuo at 110C
overnight wher~upon the resultant copolyester 1320 y/ 89.2 percent of theory) is ~ecoYered ~ a granular powder.
The oxybenzoyl polyesters~ discussed generally in the earlier part o~ thi~ specification and specifically illust~ated in Examples 1 to 5, can be molded according to conventional techniques to p.roduce the ovenware articles of the present inve~-tion. Additives ~uch a~ are conventionally employed in moldi~
compositions can be incorporated p~ior to mo~ding ~or th~ir ~co~
nized purpose. UnSo Pat~. No. 3,884,876 and 399~0~7~9 di~cl~emolding procedures for oxybenzoyl polye~ers Which CDUld be a~aPted for the fabrication of ovenware.
20 518 parts of isophthallc acid, 1,557 ~)arts of tereph-thalic acid, 5,175 parts of para-hydroxybenzoic acid, 6,885 parts of acetic anhydride and 2,325 ~arts of p,p'-bis~)henol are mixed together and refluxed ~or 17 hours, dt a temperatllre of about 180 C, after which the reflux condenqer is replaced with a distilling head and the temperature is raised to 345C over a period of 1 and 1/4 hours. The reaction mixture is stirred ~hroughout the heatin~
period, being particularly actlvely mixed during the period in which the temperature is being raise~ to 345C. I'h~ yield of polyn~er is 8,020 parts and 8,010 parts of distillate are recovered.
The contents of the reaction vessel are removed, cooled and ground to pa~ticle si~es in the 20 to 160 mesh range, U~S. Standard Sieve S Seri~S. ~he resin made is of a molecular weight in -the 5,030 -20,000 rang , with an average weight in about the middle of Ruch range. The product is estimated to b~ about 50% crystalline.
~ he resin particles are held unde~ vacuum illu~ra~ively at an elevatPd tempexature ak an absolute pres~ure of abou~ 100 mm 10 o;f mercury for eigh~ hs:~urs and recove:re~ a~ a ~:rarlula~ powde~ .
The following quantities of the following ingredi0nt~
are comhined as indicated.
Quantity It~m Ingrèdient ~rams Moles A Terephthalic Acid 291 1.75 B P-Hydroxybe~zoic Acid 483 3.50 C p,p'-biphenol 325 1~75 D Acetic Anhydride 755 7.40 Items.A~D are heated to 145C and refluxed overnight.
The reflux conden~er is removed an~ a distilling head put i~ placeO
The mixture is heated with stirring at a rate of 20C/hour t~
300C and the contents oE the reac~or removed. ~t ~hi~ point about 92-94~ of the theoretical ace~ic aci~ i8 collec~ed. The pr~p~lyme~
is ground up and advanced as in Example 3. employing a tempe~ature of about 250-350C.
EXAMPL~ 5 ~uantity Item Ingredient Grams Moles A p~ droxybenæoic Acid 276. (2.00) B Terephthaloyl Chloride 203 l.0 C Trimesic Acid 8~4 0.040 D Therminol 66 1274 E p,p'-~iphenol 186 l.0 F Acetic Anhydride 224.6 2.2 Items A-~ are heated to 130C and h~ld one hou~, Th~
reaction is exothermic and care i5 ~a~en to maintain t~mperature at 130C. The contents are then he~ted at 155C for one hour and 180C f or 4 hours . The mixture is then cooled to 150C and item E added whereby the temperature is ~urther reduced to 140C. Item :IS F is then added. ~his Inixture is then refluxed one hour at 155C
ancl t:he reflux condenser replaced by ~ di~tlllation cQl~nn. While distilling the ac~ic acid formed, the contents of the reactor are heated to 3~0C and h~l~ 3 hours. Tlle suspended polymer is cooled to 250C and the mix-ture passed th~ou~Jh a filter. The solid m~ter-ial is work~d with trichloroethylene to remove the heat transferfluid. The dried Jowder is advancPd further in vacuum as in Example 3.
In order to demonstrate the un.ique suitabllity of oxy-bPn~oyl polyester~ for ~he fabrication of ovenware, -~h~ ~ollowin~
tests were carri~d out on various ltems of pla~tlc ove~wa~e~ such as bowls, cups, etcO0 which we~e ~abricated from oxy~enæoyl poly-esters, polysulfone, polybutylene terephthal~te, polyp~opylene polycarbonate alld a therrno~et polyester.
-12~
EXAM~L~ 6 q'hermal (Electric) Oven "No Load" Test ~he plastic article was placed in a glass container on the sh~lf 5 1/~ inches from bottom of the oven. The oven ~empera-ture was s~t and the ov~n allowed to heat up from room temperature.
The plastic article was allowed to ~tay 1/2 hour in the oven or to failure, if sooner.
~he following results were ~oted. A cup cut ~rom a muffin pan fabricated from a thermoset polyester resin emitted an odor within 15 minutes and began to smoke in 30 minu~es at an oven ternperature of 410F. A 2-inch strip cut from a bacon tray fabricated from a polysulfone resin softened in 15 minute3 and became totally distorted at an oven temperature of 410Fo
It is known that certain plastic materials have found some application in the ovenware field. For e~ample, polymethyl-pentene has been used for injection molded trays which can be used in the preparation of foods. Polysulfone has also been employed in food handling applications. However, no satisfactory material has been found possessing utility over the wide ranges of condi-tions and of demands which are encountered in the provision of cook-in containers, or ovenware, which can be used in either thermal ovens or microwave ovens.
In addition to the obvious necessity for a material which can withstand the temperatures met in the heat source used for cooking, a material must provide a unique combination of a number of other characteristics before ovenware fabricated from the material can be successfully employed in the preparation of food. The material must have good electrical properties. It must be able to undergo severe thermal shocks in that ovenware prepared from it must be capable of going from conditions of extreme cold to high temperatures in relatively brief periods of time. The material must have good hardness and impact strength and possess high tensile and flexural trength. It must also be resistant to boiling water and to ad~erse e~fects from immersion in detergents.
In the area of food related properties the material must impart to the ovenware fabricated from it resistance to staining by a wide variety of foodstuffs. It must provide a surface affording good antistick properties, ready releasability for the food which it contains. It must not emit or give off any volatile matter and it must not have any extractable constituent~
And in addition to meeting all of the foregoing requirernents, articles prepared from it must present a pleasing appearance~
'iS ;r SUMMARY OF THE PRESENT INVENTION
Ovenware meeting the stringent demands of the cook-in container market is provided by fabrica~ing the ovenware articles from a plastic material based upon wholly aromatic polyesters, more particularly, upon oxybenzoyl polyesters.
The wholly aromatic polyesters employed in accordance with the present invention consist of combinations of repeating units of one or more of the following formulae:
~ ~X~n ~/ c __oc~3 (Xln ~ ~\ co~
P--q I II
10 ~ ~ ~X)n ~ ~ ~ ~ ~ co -- - r - - s III IV
oc ~ ~ co _o ~3 o t u O VI
where x is O, S,~c-, NH, or SO2 and n is o or 1 and the total of the integers p+q+r~stt~u, in the moieties present is from about 3 to about 800.
Combinations of the above units include union of the carbonyl group of Formulae I, II, IV and V with the oxy group of Fo.rmulae I/ III, IV and VI. In the most general combi.nation all units of the above formulae can be present in a single co-polymer. The simplest embodiment would be homopolymers of units I or IVo Other combinations include mixtures of unlts Il and III, II and VI, III and V, V and VI, and I and IY.
The location of the functional groups are preferably in the parar (l,4~ positions. They can also be located in ortho (l,2) position to each other. With respect -to the napthalene moiety the most desirable locations of the functional groups are l,4; l~5 and 2,6. Such groups can also be in the ortho position to each other.
The symbols p, q, r, s, t and u are integers and indicate the number of moieties present in -the polymer. The total (p+q+r+s~t~u) can vary from 30-~00 and, when present, the ratio of q/r, q/u, t/r, t/u, q~t/r. q+t/r+u and t/r+u can vary from about lO/ll to about ll/lO with most prefèrable ratio being lO/lO.
Exemplary of materials from which the moieties of Formula I may be obtained are p-hydroxybenzoic acid, phenyl-p-hydroxybenzoate, p-acetoxybenzoic acid and isobutyl-p-acetoxy-benzoate. Those from which the moie~y of Formula II is derivableinclude terephthalic acid, isophthalic acid, diphenyl tere~
phthalate, diethyl isophthalate, methylethyl terephthalate and the isobutyl half ester of terephthalic acid. Among the compounds from which the moiety of Formula III results are p,p'-bisphenol;
p,p'-oxybisphenol; 4,4'-dihydroxybenzophenone; resorcinol, and hydro~uinone. Inspection will show which of these materials are also suitable for supplyiny the moieties of Formulas VI-VIII.
Example of monomers represented by Formula IV are 6-hydroxy-l-naphthoic acid, 5-acetoxy-l-napthoic acid and phenyl 5-hydroxy-l-naphthoate. Monomers representing ~ormula V include l,4-napthalenedicarboxylic acid, l,5-napthalenedicarboxylic acid and 2,6-napthalenedicarboxylic acid. The diphenyl esters or dicarbonyl chlorides of these acids can also be used. Examples of monomers representative of Formula VI are, l,4~dihydroxy~
naphthalene, 2,6-diacetoxynaphthalene, and 1,5-dihydroxynaphtha-lene.
Particularly preferred for use in the practice of the present invention are plastic materials based upon oxybenzoyl polyesters.
The oxybenzoyl polyesters useful in the present invention are generally those repeating units of Formula VI:.
O ~= C ~
where p is an integer of from about 3 to about 600.
One preferred class of oxybenzoyl polyesters are those of Formula VII:
(VII) ._ Rl o ~) 11 ~ o~2 P
wherein Rl is a member selected from the group consisting of benzoyl, lower alkanoyl, or preferably hydrogen, wherein R2 is hydrogen, henzyl, lower alkyl, or preferably phenyl and p is an integer from 3 to 600 and preferably 30 to 200. These values of ~ correspond to a molecular weight of about 1,000 to 72,000 and preferably 3,500 to 25,000.
Another preferred class of oxybenzoyl polyesters are copolyesters of recurring units of Formulas VII, VIII and IX:
(VIII) o ~ o ~C - I J C
_ ~ q __ _ (IX) _ o ~ ( (X) ~ ~ O
n _ r wherein X is - O or - SO2 - m is 0 or 1: n is 0 or 1: q:r =
10:15 to 15:10; p:q = 1:100 to 100:1; p + q -~ r = 3 to 600 and preferably 20 to 200. The carbonyl groups of the moiety of Formula I or III are linked to the oxy groups of a moiety of Formula I or IV; the oxy groups of the moiety of Formula I or IV
are linked to the carbonyl groups of the moiety of Formula I or III.
The preferred copolyesters are those of recurring units of Formula X;
(X) ~
C ~ C-O ~C -O ~ ~ O
The synthesis of these polyesters is described in detail in U.S. Paten-t 3,637~595 entitled "P-Oxybenzoyl Copolyesters".
The polyesters useful in the present invention can also be chemically modified by various means such as by inclusion in the ~olyester of monofunctional reactant~ such as benZoic acid or tri - or hi~her functional reactant5 such as trlmesic acid o~
cyanuric chloride. The benzene ring3 in the~e polyeste~s a~e p~~
ferably unsubstitu~ed ~ut can be substituted with non~interferrin~
substituen~.s,examples of which include among othe~ halogen ~uch as chlorine or bromine, lower alkoxy such a.s methoxy and low~
alkyl such as methyl.
The oxybenzoyl polyesters useful in the present invention can be employed with various fillers of types and in amounts which do no-t ma~erially affect -th desired properties. ~xamples of suitable fillers include among others glass fibers,polytetra-fluoroethylene, pigments,fillers and polyimides.
The invention is further illustrated by the following examples in which all parts and percen~ages are by weight unless otherwise indicated. These nonlimi~ing examples are illustrative of certain embodiments designed to teach those skilled in th~ art how to practice the invention and to represent the best mode contemplated for carrying out the inven-tion.
EXAMPLE I
250 ~ of a mixture consisting of 40~ o-terphenyl and 60~ m-terphenyl i5 ~harged il~tO a four-neclced, round bottom flask fitted with a stirrer, a nitrogen inlet, a thermometer and a dis-tilling head leading to a condenser. The distilling head is ex-ternally wound with electrical resistance heating wire in order that it may ~e heated and a hea~ing mantle is provided ~o heat the f~ask and its contentsO Tl~e contents of the flask are melted by heating to dbout 60C.~ whereupon 68 g of ~acetoxybenzoic acid are added with stirring. ~`he entire condensation is carried out with constant stirring and with a slow flow of nitroyen through the flask to provide a non-oxidizing atmosphere. The distilling head is heated to about 120C and the mixture in the flask is heated to about 340C, polyester preci~itation startinc3 to occur at about 3P0C. The distilling head ~emperature is then raised ~o about 18QC to avoid refluxing of the distillata and/ox ~olid~
ification thereof in the distilling head, and the mixtu~ th~
flask is held at about 340~C for about 12 hour~. A total O~
25.5 g of distillate is collected, consisting primarily ~f aCetic acid, the remainder being primarily terphenyl liquid heat t~ans~er medium. It is observed tha-t 25 g of this distillate are coll~cted within 35 minutes after the temperature of 340C h~ bee~ reached, indicating that the polym~ri2ation is already approaching com-pletion within this time.
The resulting mix~ure is cooled to 80~, becoming qui-te viscous. ~out 200 ml of acetone are added slowing and ~he mixture is filtered to recover the polyester precipitate. The polyester is extracted overnight with acetone in a Soxhlet extractor to remove any residual ter~henyl liquid hea~ transfer medium and is then dried in vacuu~ for 3 hours at 110C. A yield of 43 g (96%
of theory) of p-oxybenzoyl polyester powder is obtained.
~he product was infusible and upon being held at 400C
in air it exhibited a weight loss of only 0.83~ per hour. Differ-ential thermal analysi~ revealed an endotherm, during heatinc~, at 329-343C, with a peak at 336C and a corresponding exo~herm ~urinc~
cooling, evidencing a reversible crystalline tran~ition, ~hi~
~eve~sible tran~ition was also evidenced by a marked change ~hich occurred in the X-ray ~owder diffraction pattern u~on heating the product to about 340C, the original ~attern ~ein~ resumed upon coolill~J.
In the X-ray ~owder diffraction pattern of the product at roon~ temperature, usincJ monochromatic co~per K alpha radiation, the large numbe.r and the sharpness of the diffrac-tion lines indi-cates that the polyes~er is hi~hly crystalline.
The use of a liquld heat transfer.medium is esserltial to the method employed. *he liquid must be inert, i.e it mu~t ~e non-reactive with the p-acetoxybenzoic acid monomer and th~ conden-sation products ther~of under the condition~ ~mployed. ~h~ liq~id must also be high boiling, having a boiling point unde~ th~ condi-tions employed which is at least as high a~ the hig~e~t temp~tu~
to which the reaction mixture iB heated, and convenl~ntly ~mewhat higher so that refluxing may be avoided. It will be appa~ent ~ha$
the heat transfer medium need no~ be liquid at room tempe~ature, but it should preferably have a melting point below that o~ the monomer (about 180C). A wide variety of materials has ~een found to be suitable as liquid hea~ transfer media including, for example o-terphenyl, m-terphenyl, p-terphenyl and mixtures oE two or msre thereof 5uch dS employed in the example; partially hydrogenated terphenyls SUc}l as th~se commercially available under ~he trade mark Therminol~ 66; and a eutectic mixture of 73O5% diphenyl oxide and 26.5% dip}lenyl suc}l as that which is co~nercially available as ~owthermR A heat tr~nsfer medium. O~her suitable liquid heat ransfer media include diphenoxybip}lenyls and mixtures thereof uch as those disclosed in U. S. Pat. 3,406,207-~X~MPI.E 2 This example illustrates the synthesis of a copolyesteruseful in the present invention.
The following quantities of the following ingredients are combined as indicated.
Quantity I~em Ingredient Grams Moles A P-hydroxybenzoic Acid 138 B Phenyl acetate 170 1.25 C Therminol 77 500 __ D Diphenyl Terephthalate 318 E llydrogen Chloride F ~3ydroquinone 111 1.~1 G Therminol 77 500 --Items A - D are char~3ed to a four-necked, round bottom flask fitted with a ~hermometer, a stirrer, a combined ni-trogen and HCl inlet ~nd an outlet connected to a condenser. Nitrogen is passed slowly through the inlet. The flask and its contents are heated to 180C whereupon ~Cl is bubbl~d through the reaction mi~-ture. The outlet head t~mperature i5 kept at 110 - 120C by external heating during the p-hydroxy~enzoic acid, phenyl acetate ester exchange reaction.
The flask and its contents are stirred a-t 180C ior 6 hours whereupon the HCl is shut off, the outlet head tempe~ature rai~ed to 180 - 190C and the nlixture ~ irred at 220C for 3,5 hGurs. Up to this point, 159 grams of dis~illate are collected in the ~ondenser. Item F is then added and the temperature gradually increased from 220C to 320C over a period of 10 hours ~10C/hr)~
~tirring is continu~d at 320C or 16 hours and then for three additional hours at 340C to form a slurry~ The total amount o~
distillate, consisting of phenol, acetic acid and phenyl acetate, amounts to 384 g. Item G is added and the r~acti~n mixture per-5 mitted to cool to 70C. Acetone (750 ml~ is added and the slurryfiltered, the solids are extrac~ed in a Soxhlet with acetone to remove i~ems C and ~. The solids are dried in vacuo at 110C
overnight wher~upon the resultant copolyester 1320 y/ 89.2 percent of theory) is ~ecoYered ~ a granular powder.
The oxybenzoyl polyesters~ discussed generally in the earlier part o~ thi~ specification and specifically illust~ated in Examples 1 to 5, can be molded according to conventional techniques to p.roduce the ovenware articles of the present inve~-tion. Additives ~uch a~ are conventionally employed in moldi~
compositions can be incorporated p~ior to mo~ding ~or th~ir ~co~
nized purpose. UnSo Pat~. No. 3,884,876 and 399~0~7~9 di~cl~emolding procedures for oxybenzoyl polye~ers Which CDUld be a~aPted for the fabrication of ovenware.
20 518 parts of isophthallc acid, 1,557 ~)arts of tereph-thalic acid, 5,175 parts of para-hydroxybenzoic acid, 6,885 parts of acetic anhydride and 2,325 ~arts of p,p'-bis~)henol are mixed together and refluxed ~or 17 hours, dt a temperatllre of about 180 C, after which the reflux condenqer is replaced with a distilling head and the temperature is raised to 345C over a period of 1 and 1/4 hours. The reaction mixture is stirred ~hroughout the heatin~
period, being particularly actlvely mixed during the period in which the temperature is being raise~ to 345C. I'h~ yield of polyn~er is 8,020 parts and 8,010 parts of distillate are recovered.
The contents of the reaction vessel are removed, cooled and ground to pa~ticle si~es in the 20 to 160 mesh range, U~S. Standard Sieve S Seri~S. ~he resin made is of a molecular weight in -the 5,030 -20,000 rang , with an average weight in about the middle of Ruch range. The product is estimated to b~ about 50% crystalline.
~ he resin particles are held unde~ vacuum illu~ra~ively at an elevatPd tempexature ak an absolute pres~ure of abou~ 100 mm 10 o;f mercury for eigh~ hs:~urs and recove:re~ a~ a ~:rarlula~ powde~ .
The following quantities of the following ingredi0nt~
are comhined as indicated.
Quantity It~m Ingrèdient ~rams Moles A Terephthalic Acid 291 1.75 B P-Hydroxybe~zoic Acid 483 3.50 C p,p'-biphenol 325 1~75 D Acetic Anhydride 755 7.40 Items.A~D are heated to 145C and refluxed overnight.
The reflux conden~er is removed an~ a distilling head put i~ placeO
The mixture is heated with stirring at a rate of 20C/hour t~
300C and the contents oE the reac~or removed. ~t ~hi~ point about 92-94~ of the theoretical ace~ic aci~ i8 collec~ed. The pr~p~lyme~
is ground up and advanced as in Example 3. employing a tempe~ature of about 250-350C.
EXAMPL~ 5 ~uantity Item Ingredient Grams Moles A p~ droxybenæoic Acid 276. (2.00) B Terephthaloyl Chloride 203 l.0 C Trimesic Acid 8~4 0.040 D Therminol 66 1274 E p,p'-~iphenol 186 l.0 F Acetic Anhydride 224.6 2.2 Items A-~ are heated to 130C and h~ld one hou~, Th~
reaction is exothermic and care i5 ~a~en to maintain t~mperature at 130C. The contents are then he~ted at 155C for one hour and 180C f or 4 hours . The mixture is then cooled to 150C and item E added whereby the temperature is ~urther reduced to 140C. Item :IS F is then added. ~his Inixture is then refluxed one hour at 155C
ancl t:he reflux condenser replaced by ~ di~tlllation cQl~nn. While distilling the ac~ic acid formed, the contents of the reactor are heated to 3~0C and h~l~ 3 hours. Tlle suspended polymer is cooled to 250C and the mix-ture passed th~ou~Jh a filter. The solid m~ter-ial is work~d with trichloroethylene to remove the heat transferfluid. The dried Jowder is advancPd further in vacuum as in Example 3.
In order to demonstrate the un.ique suitabllity of oxy-bPn~oyl polyester~ for ~he fabrication of ovenware, -~h~ ~ollowin~
tests were carri~d out on various ltems of pla~tlc ove~wa~e~ such as bowls, cups, etcO0 which we~e ~abricated from oxy~enæoyl poly-esters, polysulfone, polybutylene terephthal~te, polyp~opylene polycarbonate alld a therrno~et polyester.
-12~
EXAM~L~ 6 q'hermal (Electric) Oven "No Load" Test ~he plastic article was placed in a glass container on the sh~lf 5 1/~ inches from bottom of the oven. The oven ~empera-ture was s~t and the ov~n allowed to heat up from room temperature.
The plastic article was allowed to ~tay 1/2 hour in the oven or to failure, if sooner.
~he following results were ~oted. A cup cut ~rom a muffin pan fabricated from a thermoset polyester resin emitted an odor within 15 minutes and began to smoke in 30 minu~es at an oven ternperature of 410F. A 2-inch strip cut from a bacon tray fabricated from a polysulfone resin softened in 15 minute3 and became totally distorted at an oven temperature of 410Fo
2-inch strip from a roasting tray fabricated from a ~olycarbona~e resin softened, sagged and became totally distorted in 1~ minutes at an oven tem~erature ~f 410F. ~ bowl made fxom polypr~pylene resin melted flat within 10 rninutes at an oven temperature of 410F. A casserole dish fabrlca~ed ~rom polybu~ylene terephthalate ~egan to smoke in 5 n~inutes and emitted detectable odor but did not become distorted in 30 nlislutes at a temperature of 410~. A
bowl fa~ricated from an oxyb~nzoyl polyester, in accordance with the present invelltion, showed no sign of damage after 1 hour at an oven temperature of 500~
EXA~IPLE 7 Microwave Oven - "No I.oad" Test In conducting this test, the plas-tic object was placed in ~he center of the rnicrowav~ oven directly on the gLass tray.
The plastic article was hea~ed at full power for 20 minut2s or to failure, if sooner.
The followlng results were noted. A cup cut from a muf~in ~an fabricated from a filled thermo5et polyester emitted a sligh~ odor wi~hin 17 minutes, but otherwise showed no sign 4f damage. A 9-~nch cake pan fdbric~ted from polypropylene ~how~d no damage other than a ~oftening O~ the bottom where the rim con tacted the hot glasq tray. A cup cut from a muffin pan fabricate~
from poly~utylene terephthalate had a hole burned in the 8ide and bottom within 11 minute~ roastin~ rack fabricated f~om polycarbonate resin showed a di~torted ~p~t, 1 inch in diameter i~
the middle of the rack. A bacon roaster ~abricated ~om ~ poly-sulfone udel resin ~howed no damage O~ any kind. A ~owl ~abrlc-ated from a clear polysulfone udel ~esin exhibited a di~coloration within the surface at the bottom of the bowl. A bowl ~abr~cated from an oxybenzoyl polyester showed no sign of damag~ of any kind.
Oil Resistance - Microwave Oven Test In conducting this test, a layer of Wesson oil was poured in the plastic vesselO The vessel was centered on the glass tray in the microwave oven. After varying periods at high power, the vessel was removed and examined.
The following resul~s were noted~ ~ bowl fabricated from a polypropylene resin showed s~reaking below ~he oil line within 6 minutes (severe at 9 minutes). After washing these were shown to be blister~ which readily peeled away in ~lbrous ~txands A bowl f~brica~ed from a polysulfone resin exhibited s ~eaking below the oil within 6 minute~ whirh wa~ readily seen. ~ter washing, blister~, cracks and a "~u~n" ~pot in ~he bottom o~ the howl were observed. A cup cut from a muffin pan ~ab~icat~d ~o~
polybutylene terephthalate at 5 mi~tes' exposure showed the ~ide
bowl fa~ricated from an oxyb~nzoyl polyester, in accordance with the present invelltion, showed no sign of damage after 1 hour at an oven temperature of 500~
EXA~IPLE 7 Microwave Oven - "No I.oad" Test In conducting this test, the plas-tic object was placed in ~he center of the rnicrowav~ oven directly on the gLass tray.
The plastic article was hea~ed at full power for 20 minut2s or to failure, if sooner.
The followlng results were noted. A cup cut from a muf~in ~an fabricated from a filled thermo5et polyester emitted a sligh~ odor wi~hin 17 minutes, but otherwise showed no sign 4f damage. A 9-~nch cake pan fdbric~ted from polypropylene ~how~d no damage other than a ~oftening O~ the bottom where the rim con tacted the hot glasq tray. A cup cut from a muffin pan fabricate~
from poly~utylene terephthalate had a hole burned in the 8ide and bottom within 11 minute~ roastin~ rack fabricated f~om polycarbonate resin showed a di~torted ~p~t, 1 inch in diameter i~
the middle of the rack. A bacon roaster ~abricated ~om ~ poly-sulfone udel resin ~howed no damage O~ any kind. A ~owl ~abrlc-ated from a clear polysulfone udel ~esin exhibited a di~coloration within the surface at the bottom of the bowl. A bowl ~abr~cated from an oxybenzoyl polyester showed no sign of damag~ of any kind.
Oil Resistance - Microwave Oven Test In conducting this test, a layer of Wesson oil was poured in the plastic vesselO The vessel was centered on the glass tray in the microwave oven. After varying periods at high power, the vessel was removed and examined.
The following resul~s were noted~ ~ bowl fabricated from a polypropylene resin showed s~reaking below ~he oil line within 6 minutes (severe at 9 minutes). After washing these were shown to be blister~ which readily peeled away in ~lbrous ~txands A bowl f~brica~ed from a polysulfone resin exhibited s ~eaking below the oil within 6 minute~ whirh wa~ readily seen. ~ter washing, blister~, cracks and a "~u~n" ~pot in ~he bottom o~ the howl were observed. A cup cut from a muffin pan ~ab~icat~d ~o~
polybutylene terephthalate at 5 mi~tes' exposure showed the ~ide
3~ wall at its juncti.on wi~h the bo~tom bursting and allowing oil to flow o~t. A slight darkening ~elow the oll was re5istant to soap and water. A bowl fabricated from an oxybenzoyl polyester exhibited no observable damage after 20 minutes. The bowl washed clean without stain.
Freezer To Oven-Thawing-Warming Test In carrying out this test the plastic containers were loaded with approximately 100 g of Chili (Shop-Ri~e~ canned chili con carne~ and frozen overnight in the freezer section of a refrigerator. The plastic containers were then placed in a tray in a 425F preheated oven and allowed to remain until the contents were bubbling. If the container failed, it was removed sooner.
The following results were noted. A bowl fabricated from a polypropylene resin had melted to the level of the food after 8 minutes. No thawing had taken place. A bowl fabricated from a polysulfone resin after 27 minutes had a distortion at the lip. At 33 minutes the bowl was soft and distorted. The food was warm, not hot. The bowl cleaned well with no staining. A
cook pan fabricated from polybutylene terephthalate had distorted sides after 12 minutes. At 20 minutes the article was cornpletely out of shape and the food was not warm. The pan was fairly easy to clean but showed slight staining. A cook pan fabricated from a thermoset polyester took 35 minutes' time to heat the food. The pan was hard to clean. There was a slight stain. A bowl fabricated from an oxybenzoyl polyester showed no damage after 40 minutes to bubbling. The bowl cleaned easily with no staining.
Stain And After-Odor Test (Barbecue Sauce) In conducting this test barbecue sauce (Kraft) was placed in a 1/2 inch layer on the bottom of the plastic containerO
The container was then placed in a 400F preheated oven for 1/2 hour. At this time the sauce was thick, dark, and crusty. After cooling the container was washed with soap and water using a Dobie pad. The container was examined for a stain line and was .~.
Freezer To Oven-Thawing-Warming Test In carrying out this test the plastic containers were loaded with approximately 100 g of Chili (Shop-Ri~e~ canned chili con carne~ and frozen overnight in the freezer section of a refrigerator. The plastic containers were then placed in a tray in a 425F preheated oven and allowed to remain until the contents were bubbling. If the container failed, it was removed sooner.
The following results were noted. A bowl fabricated from a polypropylene resin had melted to the level of the food after 8 minutes. No thawing had taken place. A bowl fabricated from a polysulfone resin after 27 minutes had a distortion at the lip. At 33 minutes the bowl was soft and distorted. The food was warm, not hot. The bowl cleaned well with no staining. A
cook pan fabricated from polybutylene terephthalate had distorted sides after 12 minutes. At 20 minutes the article was cornpletely out of shape and the food was not warm. The pan was fairly easy to clean but showed slight staining. A cook pan fabricated from a thermoset polyester took 35 minutes' time to heat the food. The pan was hard to clean. There was a slight stain. A bowl fabricated from an oxybenzoyl polyester showed no damage after 40 minutes to bubbling. The bowl cleaned easily with no staining.
Stain And After-Odor Test (Barbecue Sauce) In conducting this test barbecue sauce (Kraft) was placed in a 1/2 inch layer on the bottom of the plastic containerO
The container was then placed in a 400F preheated oven for 1/2 hour. At this time the sauce was thick, dark, and crusty. After cooling the container was washed with soap and water using a Dobie pad. The container was examined for a stain line and was .~.
4~
judged to be stained i~ 15 minutes ~urther washing could no remove evidence of the stain. The container wa~ then returnea to the oven for 15 minu~e~, removed and smelled while hot~ any unusual odor was noted.
s The follow.ing r~sults were noted. A cup cut ~rom a mu~fin pan ~abricat~d from a thermo~et polyester exhibit~d a severe yellow stain. ~n after~odor of barbecue sauce wa~ detected.
A cup cu~ ~rom a ~uffin pan fabricated ~rom polybutylene terephthalate exhi~ited a severe yellow stain. An after-odor was present, although no~ identified, which could be polymer. A bowl fabricated from a polysuLfone resin emitted a slight deteetable odor. A bowl fabricate.l from an oxybenzoyl polye~ter showed no stain nor after-odor.
The polyes~er Ltems employed in the tests ~et forth in Examples 6 to 10 wexe fal)ricat~d from the polyester o~ Exampl~ 3.
Similar tests ~arr.i~d out on the items ~abricat~d from ~he polyesters of Examples 1l 2, 4 and 5 gave compa~abl~ ~xcellent results.
judged to be stained i~ 15 minutes ~urther washing could no remove evidence of the stain. The container wa~ then returnea to the oven for 15 minu~e~, removed and smelled while hot~ any unusual odor was noted.
s The follow.ing r~sults were noted. A cup cut ~rom a mu~fin pan ~abricat~d from a thermo~et polyester exhibit~d a severe yellow stain. ~n after~odor of barbecue sauce wa~ detected.
A cup cu~ ~rom a ~uffin pan fabricated ~rom polybutylene terephthalate exhi~ited a severe yellow stain. An after-odor was present, although no~ identified, which could be polymer. A bowl fabricated from a polysuLfone resin emitted a slight deteetable odor. A bowl fabricate.l from an oxybenzoyl polye~ter showed no stain nor after-odor.
The polyes~er Ltems employed in the tests ~et forth in Examples 6 to 10 wexe fal)ricat~d from the polyester o~ Exampl~ 3.
Similar tests ~arr.i~d out on the items ~abricat~d from ~he polyesters of Examples 1l 2, 4 and 5 gave compa~abl~ ~xcellent results.
Claims (25)
1. As a permanent article of manufactured ovenware capable of repeated usage comprising a molded polyester, said poly-ester containing recurrent moieties selected from the group consisting of one or more of the following formulae:
I II
III IV
V VI
where x is O, S,, NH, or SO2 and n is o or 1 and the total of the integers p+q+r+s+t+u, in the moieties present is from about 3 to about 800.
I II
III IV
V VI
where x is O, S,, NH, or SO2 and n is o or 1 and the total of the integers p+q+r+s+t+u, in the moieties present is from about 3 to about 800.
2. The article of claim 1 in which the ratios of q/r, q/u, t/r, t/u, q+t/r, q+t/r+u and t/t+u is from about 10/11 to about 11/10.
3. The article of claim 2 in which the ratio is 10 to 10.
4. As a permanent article of manufactured ovenware capable of repeated usage comprising a molded polyester, said polyester containing recurrent moieties of the following formulae:
wherein p is an integer of from about 3 to about 600.
wherein p is an integer of from about 3 to about 600.
5. The article of claim 1 in which the polyester has the formula:
wherein R' is a member selected from the group consisting of benzoyl, lower alkanoyl and hydrogen; R2 is a member selected from the group consisting of hydrogen, benzyl, lower alkyl, and phenyl and p is an integer of from about 3 to about 600.
wherein R' is a member selected from the group consisting of benzoyl, lower alkanoyl and hydrogen; R2 is a member selected from the group consisting of hydrogen, benzyl, lower alkyl, and phenyl and p is an integer of from about 3 to about 600.
6. As a permanent article of manufactured ovenware capable of repeated usage comprising a molded polyester, said poly-ester having recurring units of each of Formulas I, II and III
I
II
III
wherein x is --O-- or SO2-; m is 0 or 1; n is 0 or 1; q:r=10:15 to 15:10; p:q=1.100 to 100:1; p+q+r=3 to 600; the carbonyl groups of the moiety of Formula I or II are linked to the oxy groups of the moiety of Formula. I or III; and the oxy groups of the moiety of Formulas I or III are linked to the carbonyl groups of the moiety of Formula I or II.
I
II
III
wherein x is --O-- or SO2-; m is 0 or 1; n is 0 or 1; q:r=10:15 to 15:10; p:q=1.100 to 100:1; p+q+r=3 to 600; the carbonyl groups of the moiety of Formula I or II are linked to the oxy groups of the moiety of Formula. I or III; and the oxy groups of the moiety of Formulas I or III are linked to the carbonyl groups of the moiety of Formula I or II.
7. As a permanent article of manufactured ovenware capable of repeated usage comprising a molded polyester said polyester having recurring units of the formula::
~IMAGE~
~IMAGE~
8. The article of claim 6 wherein m is o.
9. The article of claim 6 wherein n is o.
10. The article of c.Laim 6 wherein p+q+r-20 to 200.
11. In the process of preparing food in a cook-in container wherein the food in the cook-in container is heated to serving temperature the i.mprovement which comprises placing the food into a molded article fabricated from a polyester containing recurrent moieties selected from the group con-sisting of one or more of the following formulae:
~IMAGE~ ~IMAGE~
II
~IMAGE~ ~IMAGE~
III .. v V
VI
where x is O, S,, NH, or SO2 and n is o or 1 and the total of the integers p+q+r+s+t+u, in the moieties present is from about 3 to about 800; and thereafter exposing the food containing article to a heat source at a temperature and for a time sufficient to bring the food to the desired serving temperature.
~IMAGE~ ~IMAGE~
II
~IMAGE~ ~IMAGE~
III .. v V
VI
where x is O, S,, NH, or SO2 and n is o or 1 and the total of the integers p+q+r+s+t+u, in the moieties present is from about 3 to about 800; and thereafter exposing the food containing article to a heat source at a temperature and for a time sufficient to bring the food to the desired serving temperature.
12. The process according to claim 11 in which the article of claim 1 in which the ratios of q/r, q/u, t/t, t/u, q+t/r, q+t/r+u and t/t+u is from about 11/10.
13. A process according to claim 12 in which the ratio is 10 to 10.
14. In the process of preparing food in a cook-in container wherein the food in the cook-in container is heated to serving temperature the improvement which comprises placing the food into a molded article fabricated from a polyester containing recurrent moieties of the formula:
wherein p is an integer of from about 3 to about 600 p, and thereafter exposing the food-containing article to a heat source at a temperature and for a time sufficient to bring the food to the desired serving temperature.
wherein p is an integer of from about 3 to about 600 p, and thereafter exposing the food-containing article to a heat source at a temperature and for a time sufficient to bring the food to the desired serving temperature.
15. In the process of preparing food in a cook-in container wherein the food in the cook-in container is heated to serving temperature, the improvement which comprises placing the food into a molded article fabricated from a polyester having recurring units of each of Formulas I, II and III:
I
II
III
wherein x is --O-- or SO2?; m is 0 or 1; n is 0 or 1; q:r=10:15 to 15:10; p:q-1:100 to 100:1; p+q+r=3 to 600; the carbonyl groups of the moiety of Formula I or II are linked to the oxy groups of the moiety of Formula I or III, the oxy groups of the moiety of Formula I or III are linked to the carbonyl groups of the moiety of Formula I or II, and thereafter exposing the food-containing article to a temperature and for a time sufficient to bring the food to the desired temperature.
I
II
III
wherein x is --O-- or SO2?; m is 0 or 1; n is 0 or 1; q:r=10:15 to 15:10; p:q-1:100 to 100:1; p+q+r=3 to 600; the carbonyl groups of the moiety of Formula I or II are linked to the oxy groups of the moiety of Formula I or III, the oxy groups of the moiety of Formula I or III are linked to the carbonyl groups of the moiety of Formula I or II, and thereafter exposing the food-containing article to a temperature and for a time sufficient to bring the food to the desired temperature.
16. In the process of preparing food in a cook-in container wherein the food in the cook-in container is heated to serving temperature the improvement which comprises placing the food into a molded article fabricated from a polyester containing recurrent moieties of the formula:
wherein R' is a member selected from a group consisting of hydrogen, benzoyl, and lower alkanoyl, R2 is a member selected from the group consisting of hydrogen, benzyl, lower alkyl, and phenyl, and p is an integer of from about 3 to about 600 and thereafter exposing the food-containing article to a temperature and for a time sufficient to bring the food to the desired serving temperature.
wherein R' is a member selected from a group consisting of hydrogen, benzoyl, and lower alkanoyl, R2 is a member selected from the group consisting of hydrogen, benzyl, lower alkyl, and phenyl, and p is an integer of from about 3 to about 600 and thereafter exposing the food-containing article to a temperature and for a time sufficient to bring the food to the desired serving temperature.
17. In the process of preparing food in a cook-in container wherein the food in the cook-in container is heated to serving temperature, the improvement which comprises placing the food into a molded article fabricated from a polyester having recurring units of the formula:
and thereafter exposing the food containing article to a temperature and for a time sufficient to bring the food to the desired serving temperature.
and thereafter exposing the food containing article to a temperature and for a time sufficient to bring the food to the desired serving temperature.
18. A process according to claim 11 wherein the heat source is thermal.
19. A process according to claim 11 wherein the heat source is microwave.
20. A process according to claim 14 wherein the heat source is thermal.
21. A process according to claim 14 wherein the heat source is microwave.
22. A process according to claim 15 wherein the heat source is thermal.
23. A process according to claim 15 wherein the heat source is microwave.
24. A process according to claim 17 wherein the heat source is thermal.
25. A process according to claim 17 wherein the heat source is microwave.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US7397879A | 1979-09-10 | 1979-09-10 | |
| US073,978 | 1979-09-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1196146A true CA1196146A (en) | 1985-10-29 |
Family
ID=22116966
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000357731A Expired CA1196146A (en) | 1979-09-10 | 1980-08-06 | Plastic ovenware |
Country Status (30)
| Country | Link |
|---|---|
| JP (1) | JPS5643319A (en) |
| KR (1) | KR860001372B1 (en) |
| AU (1) | AU528537B2 (en) |
| BE (1) | BE884391A (en) |
| BR (1) | BR8005198A (en) |
| CA (1) | CA1196146A (en) |
| CH (1) | CH650392A5 (en) |
| DE (1) | DE3034041C2 (en) |
| DK (1) | DK382980A (en) |
| FI (1) | FI75351C (en) |
| FR (1) | FR2464683A1 (en) |
| GB (1) | GB2058102B (en) |
| GR (1) | GR68477B (en) |
| HK (1) | HK78384A (en) |
| IE (1) | IE50008B1 (en) |
| IT (1) | IT1132717B (en) |
| KE (1) | KE3431A (en) |
| LU (1) | LU82666A1 (en) |
| MA (1) | MA18944A1 (en) |
| MX (1) | MX160058A (en) |
| MY (1) | MY8500678A (en) |
| NL (1) | NL190100C (en) |
| NO (1) | NO802407L (en) |
| NZ (1) | NZ194443A (en) |
| PH (1) | PH19274A (en) |
| PL (1) | PL226655A1 (en) |
| PT (1) | PT71783B (en) |
| SE (1) | SE8006290L (en) |
| SG (1) | SG44384G (en) |
| ZA (1) | ZA804425B (en) |
Families Citing this family (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4318841A (en) * | 1980-10-06 | 1982-03-09 | Celanese Corporation | Polyester of 6-hydroxy-2-naphthoic acid, para-hydroxy benzoic acid, terephthalic acid, and resorcinol capable of readily undergoing melt processing to form shaped articles having increased impact strength |
| EP0088546B1 (en) * | 1982-03-08 | 1986-09-03 | Celanese Corporation | Preparation of aromatic polyesters by direct polycondensation |
| US4639504A (en) * | 1982-06-08 | 1987-01-27 | Dart Industries Inc. | Production of thermally stabilized aromatic polyesters |
| CA1220889A (en) * | 1982-06-08 | 1987-04-21 | Dart Industries Inc. | Process for the production of aromatic polyesters |
| US4626557A (en) * | 1982-07-26 | 1986-12-02 | Dart Industries, Inc. | Plastic ovenware containing talc |
| JPS5962630A (en) * | 1982-07-26 | 1984-04-10 | セラニ−ズ・コ−ポレイシヨン | Anisotropic melt-processable polyester containing relativelylow concentration 6-oxy-2-naphthoyl portion |
| IE54564B1 (en) * | 1982-07-26 | 1989-11-22 | Dart Ind Inc | Polyester moulding compositions and ovenware therefrom |
| US4399270A (en) * | 1982-07-29 | 1983-08-16 | E. I. Du Pont De Nemours & Co. | Fiber-forming polyesters of ketodiols |
| JPS5951915A (en) * | 1982-07-29 | 1984-03-26 | セラニ−ズ・コ−ポレ−シヨン | Fully aromatic polyester comprising 6-oxy-2-naphthoyl component and 4-oxy-4'-carboxybiphenyl component |
| US4431770A (en) * | 1982-07-29 | 1984-02-14 | Celanese Corporation | Wholly aromatic polyester comprising 4-oxy-4'-carboxybiphenyl moiety which is capable of forming an anisotropic melt phase |
| US4398015A (en) * | 1982-08-03 | 1983-08-09 | E. I. Du Pont De Nemours & Company | Fiber-forming polyesters of aromatic ketohydroxy acids |
| US4447592A (en) * | 1983-06-13 | 1984-05-08 | E. I. Du Pont De Nemours And Company | Anisotropic melt polyesters of 6-hydroxy-2-naphthoic acid |
| DE3325705A1 (en) * | 1983-07-16 | 1985-01-24 | Bayer Ag, 5090 Leverkusen | MESOMORPHIC AROMATIC POLYESTERS WITH HIGH TOUGHNESS AND IMPROVED MELT VISCOSITY, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR THE PRODUCTION OF MOLDED BODIES, FILAMENTS, FIBERS AND FILMS |
| US4694061A (en) * | 1983-10-12 | 1987-09-15 | Ciba-Geigy Corporation | Radiation-sensitive polycondensates, processes for their preparation coated material and its use |
| DE3338805A1 (en) * | 1983-10-26 | 1985-05-15 | Basf Ag, 6700 Ludwigshafen | FULLY FLAVORED POLYESTER |
| JPS60188421A (en) * | 1984-03-09 | 1985-09-25 | Agency Of Ind Science & Technol | Copolyester |
| JPS61316A (en) * | 1984-06-13 | 1986-01-06 | 住友化学工業株式会社 | Oven wear |
| DE3427886A1 (en) * | 1984-07-28 | 1986-01-30 | Bayer Ag, 5090 Leverkusen | THERMOTROPE AROMATIC POLYESTER WITH HIGH STIFFNESS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR THE PRODUCTION OF MOLDED BODIES, FILAMENTS, FIBERS AND FILMS |
| JPS61199821A (en) * | 1985-03-01 | 1986-09-04 | 住友化学工業株式会社 | Plastic oven wear having non-stickiness |
| DE3534730A1 (en) * | 1985-09-28 | 1987-04-09 | Bayer Ag | THERMOTROPE FULLY FLAVORED POLYESTER WITH EXCELLENT STIFFNESS AND TOUGHNESS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR THE PRODUCTION OF MOLDED BODIES, FILAMENTS, FIBERS AND FILMS |
| JPH07106595B2 (en) * | 1987-04-24 | 1995-11-15 | 呉羽化学工業株式会社 | Thermoformed poly arylene sulfide container and method of making same |
| ATE88205T1 (en) * | 1987-06-09 | 1993-04-15 | Amoco Corp | MOLDING FROM MIXTURES OF FULLY AROMATIC POLYESTER AND FILLERS. |
| US4851480A (en) * | 1987-06-09 | 1989-07-25 | Amoco Corporation | Extrusion-grade compositions comprising mixtures of wholly aromatic polyesters |
| US4952663A (en) * | 1988-06-17 | 1990-08-28 | Amoco Corporation | Wholly aromatic polyesters with reduced char content |
| US4849499A (en) * | 1988-08-01 | 1989-07-18 | Eastman Kodak Company | Melt processable, liquid crystalline polyesters |
| IT1227902B (en) * | 1988-12-23 | 1991-05-14 | Enichem Spa | THERMOTROPIC LIQUID-AROMATIC CRYSTALLINE COPOLYMERS |
| FR2653436A1 (en) * | 1989-10-24 | 1991-04-26 | Atochem | THERMOTROPIC AROMATIC COPOLYESTERS AND PROCESS FOR THEIR PREPARATION. |
| EP0656385A4 (en) * | 1993-06-15 | 1997-10-22 | Nippon Petrochemicals Co Ltd | Wholly aromatic polyester, composition thereof, and molded article made therefrom. |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3637595A (en) * | 1969-05-28 | 1972-01-25 | Steve G Cottis | P-oxybenzoyl copolyesters |
| BE789542A (en) * | 1971-10-01 | 1973-03-29 | Carborundum Co | PRODUCTION OF INFUSIBLE AND FORMABLE PARA-OXYBENZOYL POLYESTER |
| US3980749A (en) * | 1973-08-31 | 1976-09-14 | The Carborundum Company | Partially crosslinked linear aromatic polyesters |
| US3884876A (en) * | 1973-08-31 | 1975-05-20 | Carborundum Co | Partially crosslinked linear aromatic polyesters |
-
1980
- 1980-07-15 IE IE1468/80A patent/IE50008B1/en unknown
- 1980-07-17 FI FI802261A patent/FI75351C/en not_active IP Right Cessation
- 1980-07-18 BE BE0/201464A patent/BE884391A/en not_active IP Right Cessation
- 1980-07-21 GR GR62517A patent/GR68477B/el unknown
- 1980-07-22 ZA ZA00804425A patent/ZA804425B/en unknown
- 1980-07-22 AU AU60688/80A patent/AU528537B2/en not_active Ceased
- 1980-07-25 NZ NZ194443A patent/NZ194443A/en unknown
- 1980-07-29 LU LU82666A patent/LU82666A1/en unknown
- 1980-07-29 PH PH24363A patent/PH19274A/en unknown
- 1980-07-29 MX MX183340A patent/MX160058A/en unknown
- 1980-08-06 CA CA000357731A patent/CA1196146A/en not_active Expired
- 1980-08-08 FR FR8017614A patent/FR2464683A1/en active Granted
- 1980-08-12 NO NO802407A patent/NO802407L/en unknown
- 1980-08-18 BR BR8005198A patent/BR8005198A/en unknown
- 1980-08-26 JP JP11763480A patent/JPS5643319A/en active Granted
- 1980-08-28 NL NLAANVRAGE8004863,A patent/NL190100C/en not_active IP Right Cessation
- 1980-09-04 MA MA19145A patent/MA18944A1/en unknown
- 1980-09-05 KR KR1019800003507A patent/KR860001372B1/en active
- 1980-09-09 DK DK382980A patent/DK382980A/en not_active Application Discontinuation
- 1980-09-09 GB GB8029092A patent/GB2058102B/en not_active Expired
- 1980-09-09 IT IT24554/80A patent/IT1132717B/en active
- 1980-09-09 PT PT71783A patent/PT71783B/en unknown
- 1980-09-09 PL PL22665580A patent/PL226655A1/xx unknown
- 1980-09-09 SE SE8006290A patent/SE8006290L/en unknown
- 1980-09-09 CH CH6781/80A patent/CH650392A5/en not_active IP Right Cessation
- 1980-09-10 DE DE3034041A patent/DE3034041C2/en not_active Expired
-
1984
- 1984-06-19 SG SG44384A patent/SG44384G/en unknown
- 1984-07-20 KE KE3431A patent/KE3431A/en unknown
- 1984-10-18 HK HK783/84A patent/HK78384A/en not_active IP Right Cessation
-
1985
- 1985-12-30 MY MY678/85A patent/MY8500678A/en unknown
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| MKEX | Expiry |