IL28879A - Catalytically active composition and process utilizing the same - Google Patents

Description

n AT ACTIVE CGSIPOSITION AND THE The FIRESTONE TIRE RUBBER COMPANY of USA This iaveatiea relates te a eatalytically active a teraimated a eatalytically active metallic fer example aatiaeay The iaveatiea alse relates te a preeess which utilizes a ceyered te exist these te yield higher melecular weight pelyester pelyners amd pelyester haviag better heat The eatalytically active is particularly useful the preductiea ef havimg a aelecula weight abeve abeut haviag am inpreved heat The art is replete with exaaples ef limear amd fer predueiag such Fer the nest are based phthalic phthalie sueciaic er sebacic The sters by reactiea ef such dibasic acids with a dihydric such as prepyleme glyeel7 er the aetallie catalysts have beem utilized the preparatiea ef these aaterials which are eeaaercially iapertamt ia view ef their ability te be drawa iate Fateat teaches the preductiea ef utiliziag berate as a Fateat 2 teaches the use ef litharge as a catalyst te preduce this Fateat teaches the use ef aa alkali Geraaaiua aad geraaaiua exide are eatalytie aaterials ia Cebalteus er ia eeabiaatiea with litharge er aatiaeay are utilized as materials im of as a material is taught im Pateat Varieus eempeumds diselesed as materials im eus eraaemstallie varieus mum amd various ergamometalli eempeumds are as eatalytie materials im Patemts 27 amd 2 Basie ferric acetate is diselesed as a eatalytie material im amd cadmium of phatic dibasic acids are taught im formate is diselesed im Patemt 2 a catalytic rial for polyesters such acetate is diselesed im Patemt diethyl is disclosed im Patemt a catalytic is diselesed im Patemt as a catalytic phosphide is im Patemt 7 Amtimemy trifluoride is disclosed as a catalyst im temt Zime acetate im cembimatiom with various metallic poumds7 such as metal or im with arsemie pemtoxide or triexide7 diselesed im Patemt amd 20 Various germaaium eempeumds are diselesed as tic materials im Patemt amy other examples of polyester eatalysts7 imeludimg free may he im the prior All useful as eempomemts of the The pri cipal difficulty with the foregoing metallie active materials is that high of metal which are meeossary im order to effect polymerizatiom of the esters amoumts above weight percent based the weight of aad iastability ef the te It dth respeot te weight heat stability the iaveatiea larly It has beea that aa iapreved high aelecular weight iapreved stability te be obtained by deaslag aa er a eeapesitxea ia the preseaee ef a aaeua ef a catalytic ing frea abeut 1 te parts by preferably abeut parts by ef aa eeapeund having the general wherein is a bivaleat organic taining frea abeut 6 te abeut 100 carbon ateas er haviag a molecular weigh from abeut 100 te abeu aad a capability ef withstanding ceadeasatiea temperature ef frea abeu 200 C abeut aad frea te 8 parts by weight7 preferably abeut parts by a The eatalytie aaeuat ef the feregeiag catalytic coapesitiea lized ia th ceadeasatiea is that is suffieieat te previde fre abeut te abeut weight preferably abeut weight percent ef aad abeut te abeut weight preferabl abeut weight ef based ea the weight ef er As iadieated a bivaleat ergaaie It has beea deteraiaed that the e the radical is ef little er eeasequeace se leag as the aelecular weight is withia the aferesaid aelecular weight aad se leag as the material at ceadeasatiea The functional greups ia this aaterial appear te the terminal results have where the ergaaie ceataias aitregea as part aa aoiae group which is either er earn he er er er various combinations Examples ef which the bivalent ergaaie radical R may he composed radicals as hexaaethyleae7 aryl radicals such as radicals such as ethyl radicals such as ethylene aad aad radicals such as hydrocarbon radicals may eontain such as aethexy7 As aature ef the ergaaie ef the terminated ceapeaeat is ef little consequence ia respect ef the utility ef the bread class ef It is accessary onl that the ergaaie ceapeaeat be heat stable under the conditions ef the be uareactive with the lic be except ia a catalytic with the pelyaerizable Materials from which the catalytic ageat may be include diearbexlie thyleae polyethylene methyl benzoic and the Ia ergaaie with respect te a maternal eapable ef taching at least primary greup at the point ef ality en the ergaaie may be used te the ceapenents Correspondingl an rimar amine rovidin such as may be used te with the ergaaie material te yield the ef the catalytic may supplied by amy reactive as ethyleae ammeaia7 er the aad may be This material ceabiaes the ef the eatalytie material form ef aaiaes useful ia the preseat ethyleae triethyleae aad the preferred example ef which is ethylene A preferred example ef the eeapeaea the catalyst the preseat is by reacting diaaiae with a ia a rati sueh that eae ef ethyleae diaaiae is previded 2 te 10 ef the eaprelaetam Exaaples ef the preferred lytie materials will be gives The eeapeaeat ef the catalyst ef th preseat iaveatiea may ceasist ef the metllic aad these wh ch are as el iadicated the catalyst may be added te the separately er ia er they may be added siaultaaeeusly er ia a The ef the pelyesters the ef pelyester fer example lie er a lew molecular weight diester with er pelyhydrie Although pelyesters have been prepared by the use ef free acid the pel it is prepare the long pelyesters by a series ester interchange lew molecular esters ef aeid are the result is the the a lev weight Per the reaction ef ethylene displaces the relatively lew e the aad the in the preparation ef these displacement ef the lew weight aleehel in which when removed frea the a residue is identiied as a By further heating the in the ef the catalytic eaterials ef the present there is obtained high molecular weight pelyeste having an proved stability This reaction proceeds with the ef glycol te the high weight In the preparation of aers and pelyaers7 there be used esters ef terephthalie isephthalis phthalic with a er pelyhydrie aleehel ef frea 1 te sueh as aleehel ethyl propyl ethylene propylene and hexanethyleae The ef the acid and aleehel be as disclosed in Fateat These esters nay be converted oraiag pelyeste products by a preeess such The the from the practise this may employed ia ef fabries ef all such as oleth aad seat eevers7 as as the ef duced As iadieated pelyCethyleae is the preferred Other polyesters iaelude these above as well those speeifieally described ia Patemt aad Ia sueh it is te duet the pelymerizatiea ia am iaert substaatially aahydreus at elevated teaperaturo is increased the of the u te a temperature of from about to stages of the are high The detailed of ia order to meet the deaaads of the physical aad these are the prior examples of art have beea to It is te be that the eatalyst of the sent iaveatiem is mot limited to the catalysis particular or amy process The polyesters as prepared by method of are of the liaear type aad hav a molecula weight that is above or above viscosity of about measured ia a solutioa of the polyeste in a at It at this to furthe illustrate as illustrative ef set liaitiag the iaveatiea te the preeise ef These ia the art will by the illustrated ia these t eut the iaveatiea with ether specific Aa is readily prepared reactiag a ef ef 2 te with eae at a temperature ef fes te a eeataiaer r a psried 10 te 20 resultant nay Trashed aad then greuad a Wiley used directly the catalyst A As was prepared by reactiag three ef aad mele ef aaiae fer a ef 16 heurs at ia a elesed The resultant polymer was aad ia a This preduct is useful as a catalytic as he shewa ia the aaaexed Table The total yield was approximately This is what is identified as this aa dieatiea ef the degree ef This product is approximately aad as a Other catalytie ef type nay be prepared by reactiag uader the same five aeles ef with eae ef diaaiaej eaprelactaa with ethyleae Such produce identified as aad The material has a ef approximately aad the material has a ef The Table 1 illustrates the treatment varieus with varieus eatalytie shcwiag the effect ef the catalytic em molecular alse upea the heat stability characteristics as heat at EX was pared hy five melee ef eae ef ia a with a ef at a ef a The resultant pelyae greuad ia a Wiley This may he used directly eae ef the ef the catalyst eempesitiea ef this C was prepared hy reactiag tea aees ef aad eae aele ef ethyleae diaaiae fe a peried ef 16 heurs a temperature ef ia The pelyaer was aad greuad ia a Wiley This may he used directly as eae ef the aeats ef a catalyst eempesitiea ia accordance with Ia the Table is had te a fer A typical precedure fer such a is as EXAMPIE D a Hobart sixer equipped with stainless bowl added 1992 grams ef terephthalie 1116 ef ethylene ef calcium acetate The mixture was beaten fer a peried ef at high awl te a one stainless steel auteclave equipped with heating means with the column After purging the system with grade the reaeter was heated a Heating to this temperature required a peried two aad the reaction vessel pressure was build to 140 At this the pressure was vented down te 100 by bleeding eff the water produced ia the Water was vented at this pressure fer a two aad thereafter the pressure was slewly lowered te 24 during the next a total ef ef liquid was having a density ef which is equivalent te ethylene This represents a total ef 425 grans ef with a ef only 84 grams ethylene glycol The preduct was reaoved through the bottom valve ia the clave as a clear liquid upon gave a brittle white weighing 2511 This was found to have a molecular weight in the range from 800 to In the annexed Table the procedure producing lyester has been substantially constant for the particular the following example may be as typical the production of polesters ia accordance with the present When condensation is as evidenced by the lution of water or alcohol or as the ease stay the zation reaction is basically a E a pelyiethyleae having a duced there added te 200 equipped with a water 100 ef lev ia with Example ef lew weight as prepared ia Exaaple A to gram ef aatiaeay ingredients were with to ture is a and the ethylene glyeel feraed ia the course ef the reactions ceased distill the pressure ia the system was gradually reduced the an additional three heurs at der pressure ef aa a taa was which had the relative This duet was by titratiea te have which represents carbexyl groups per Referriag te Table it will be observed whea the ef Exaaple D is treated with a catalyst aatiaeay without the ef the present there is ebtaiaed a relatively lew eular weight preduct ia which the heat as measured by the is ia the upper ead ef the Exaaple 2 shews with the catalyst ef the present aad ia the absence ef aetallie the lar weight ef the preduct is as Examples and the lyst ef the iaveatiea is used is with the catalyst the develeaeat is shews that a im with trlexide as the tic shews very peer development ef Example 6 shews that used the very lew which be used ia this invention and the absence the weight is quite Example 3 shew the use ef the ef am aad zinc acetate as the catalytic wherein beth ef these products develop weights withim the desired Example 9 threugh 11 utilize Example A as the aated catalytie is three different with the triexide at a level aad illustrating the development ef very high molecular The heat stability is excepionally as illustrated by the relatively lew fer Exaaples 9 it will be with Example 11 that the is relatively quite is indicative ef the that tee auch ef the agent was Exaaples 12 threugh 14 utilize aylea talyst im the same as fer Examples 9 threugh amd shew the development ef molecular amd Examples 12 heat erne proaches the higher concentration ef the the heat stability falls although the weight is exceptionally Examples amd shew the utilization ef am ted catalyst prepared ia accordance with Example C and utilised ia the two preferred the molecular weight development is very good im the lower ef the stability is With the higher the est stability is shiag the upper liait ef satisfactery heat Examples 17 through 20 shew the use different eaded catalytic aad illsutrate the sad heat at the upper end ef the desired Heat as aeasured by the slope which are the range ef factory fer the purposes of this The preferred are these are less than The weight sheuld be abave preferably frea make the deteraiaatieas fer the heat there ha eapleyed a is rua ia the felleaiag A graa sample is dried at a rotary a pressure Eg before beiag loaded iate heated chaaber ef the The sample is allowed to stand fer aiautes at befere the is pressurized ef grade aitregea aad the rate im grams per through a x die is The pressure is aad at 45 6 the abeve procedure is The legaritha ef the rate for each saaple is them plotted agaiast yieldiag a straight the ef which represents the first rate ef the Table I slopes as by the The flatter the the better the stabilizer the product upea leag expesure elevated insufficientOCRQuality

Claims (1)

1. HATING NOW particularly described and ascertained the nature of our said and in what manner the same is to be we declare that what we claim A Catalyst composition useful for the preparation of high molecular weight polyesters characterized by improved stability to heat ad comprising from about to parts by weight of an compound of the general formula having a molecular weight of from about 100 to 1500 and capable of withstanding condensation temperatures from about to wherein is a bivalent organic con ining from about 6 to 100 carbon and about to 8 parts by weight of a The catalytic composition of Claim 1 wherein is present in an amount of about 50 parts by and is sent in an amount of about 5 parts by The catalytic composition of Claim 2 wherein R tains The catalytic composition of Claim wherein the metal is used in elemental The catalytic composition of Claim 2 wherein the metal is used combined The catalytic composition of Claim 5 wherein the metal is antimony The catalytic composition of Claim 6 wherein R The ef Claim the degree ef ef the 2 te A catalyst eeapesitiea useful fer ef high aelecular weight pelyesters eharacteriaed by stability to heat csaprisiag frea abeut 1 te abeut parts by weight ef the product ef with a 2 te 1C lactam 8 parts by weight ef a The ef 9 the is ethylene The catalytic ef Claim ereia the eatalyst is The catalytic eeapesitiea Claim 9 the is ethylene the number of lactua uaits is the catalyst is a process for the preparation ef a high lar weight limear characterized by imp stability te and cemprisiag stops ef pelyaerizable te a polyester about Θ250 weight per based ester of an ef the geaeral a aelecular t ef frea 400 te 1500 s capable ef withstaadiag temperatures ef abeut te The process of Claim is added in amounts of about weight in amounts of about weight R is ol having a degree of polymerization of from 2 to and is antimony The method for the preparation of a high molecular weight polyester comprising reacting a acid an alcohol and a catalytic composition comprising from about to weight based on ester of an terminated compound the general formula having a molecular weight of about 100 to wherein R is a bivalent organic radical of from about 6 to 100 carbon atoms and to weight percent a metal containing insufficientOCRQuality