SE180031C1

SE180031C1 -

Info

Publication number: SE180031C1
Authority: SE
Publication date: 1962-01-01

Description

Uppfinnare: 11 Schnell och G Fritz Prioritet begdrd f rein den 21 december 1955 (F5rbundsrepubliken Tyskiand) Genom Overforing av di-monooxiarylalkaner eller blandningar av di-monooxiarylalkaner med alifatiska, eykloalifatiska eller aromatiska dioxoforeningar eller av di-monooxiaryl-sulfoner till hogmolekylara polykarbonat enligt svenska patentet 165 187, de tyska patenten 971 777 och 1 031 512 kan man erhalla hogmolekylara, hogsmaltande polyestrar av kolsyra, varur man kan framstdlla formade foremal sasom filmer, fibrer, Overdrag, lacker, sprutgjutna foremal, osv. av materialet i smalt tillstand eller i lOsning. Dessa forernal utmarka sig genom goda mekaniska egenskaper, hog mjukningspunkt, ringa vattenabsorption och goda elektriska egenskaper, hog hallbarhet vid forhojda temperaturer, aven i narvaro av luft eller syre avensom gentemot kemiska fOreningar, dessutom kunna de orienteras genom strackning. Inventors: 11 Schnell and G Fritz Priority requested before 21 December 1955 (Federal Republic of Germany) By Transferring di-monooxiarylalkanes or mixtures of di-monooxiarylalkanes with aliphatic, eykloaliphatic or aromatic dioxo compounds or of di-monooxiaryl-polycarbonate sulphones to U.S. Pat. of the material in the narrow state or in solution. These forernal are distinguished by good mechanical properties, high softening point, low water absorption and good electrical properties, high durability at elevated temperatures, even in the presence of air or oxygen as well as against chemical compounds, in addition they can be oriented by stretching.

Sattet att framstalla dessa polykarbonat be-star dari att namnda dioxiforeningar omestras i smalt tillstand med kolsyradiestrar med monofunktionella alifatiska, cykloalifatiska eller aromatiska oxiforeningar under avsondring av monofunktionella alifatiska, cykloalifatiska eller aromatiska oxiforeningar. Detta forfarande, som pa enkelt satt leder till hogmolekyldra film- och fiberbildande produkter, liar den nackdelen, alt man vid omestringen maste anvanda ett overskott av kolsyradiestern, enar en forlust av en del av denna diester i praktiken endazt med svarighet kan undvikas med de avsondrade monofunktionella alifatiska, cykloalifatiska eller aromatiska mono oxiforeningarna. The method of preparing these polycarbonates consists in that said dioxy compounds are transesterified in the narrow state with carbonic acid diesters with monofunctional aliphatic, cycloaliphatic or aromatic oxy compounds while secreting monofunctional aliphatic, cycloaliphatic or aromatic oxy compounds. This process, which easily leads to high-molecular-weight film and fiber-forming products, suffers from the disadvantage that a excess of the carbon dioxide diester must be used in the transesterification. the monofunctional aliphatic, cycloaliphatic or aromatic monooxy compounds.

Man liar kunnat faststalla att man kan undvika derma nackdel, cm man for framstallning av hogmolekylara termoplastiska polykarbonat efter omestringen anvander ett eller flera bis-aryl-, -alkyl-, eller cykloalkylkarbonat av di-monooxiarylalkaner enbart eller i blandning med di-monooxiaryl-alkaner. It has been found that this disadvantage can be avoided by using one or more bis-aryl, -alkyl-, or cycloalkylcarbonate of di-monooxiarylalkanes alone or in admixture with di-monooxiaryl-alkanes to produce high molecular weight thermoplastic polycarbonate after transesterification. .

De som utgangsmaterial anvanda dikarbonaten av di-monooxialkaner dro lotta att erhalla, exem pelvis genom omsattning av natriumsalt av en di-monooxiarylalkan med 2 mol av en alkyleykloalkyl- eller aryl-klor-kolsyraester. SO. erhaller man exempelvis genom omsattning av natriumsaltet av 2,2-(4,4'-dioxidifeny1)-propan med fenylklorkolsyraester i vattenhaltigt alkaliskt medium i praktiskt taget kvantitativt utbyte bisfenyl-karbonat av 2,2-(4,4'-dioxidifeny1)-propan med smaltpunkten 102-104°. The starting materials using the dicarbonates of dimonooxyalkanes were obtained by lotta, for example by reacting the sodium salt of a dimonooxyarylalkane with 2 moles of an alkylcycloalkyl or aryl-chloro-carbonic acid ester. SO. for example, by reacting the sodium salt of 2,2- (4,4'-dioxyphenyl) -propane with phenylchloric acid ester in aqueous alkaline medium in a practically quantitative yield of bisphenyl carbonate of 2,2- (4,4'-dioxyphenyl) - propane with a melting point of 102-104 °.

Ldmpliga vid genomforandet av forfarandet enligt uppfinningen aro bis-alkyl, exempelvis hisetyl, propyl- eller butyl-, biscykloalkyl, t. ex. bis-cyldohexyl- och metylcyklohexyl- samt bisaryl-, t. ex. bis-fenyl-, kresyl- och cyklohexylf enyl-karbonat av monooxiarylaLkaner, exempelvis 2,2- [difenyl- (4,4'-difenylen)- dikarbonat]-propan. Man kan a.ven anvanda blandade bis-kolsyraestrar av di-monooxiarylalkaner med monofunktionella oxifOreningar. Examples of carrying out the process according to the invention are bis-alkyl, for example hisethyl, propyl or butyl, biscycloalkyl, e.g. bis-cyldohexyl and methylcyclohexyl and bisaryl, e.g. bis-phenyl, cresyl and cyclohexylphenyl carbonate of monooxyarylalkanes, for example 2,2- [diphenyl- (4,4'-diphenylene) -dicarbonate] -propane. It is also possible to use mixed bis-carbonic acid esters of dimonooxyarylalkanes with monofunctional oxy compounds.

Upphettar man dessa bis-alkyl-, cykloalkyleller arylkarbonat av di-monowdarylalkaner, foretradesvis under forminskat tryck, sa erhaller man under avspaltning av neutralt alkyl-, cykloalkyleller arylester av kolsyra ett hogmolekylart polykarbonat. Later man namnda forening reagera i blandning med en di-monooxiaryl-alkan, sa erhäller man vid omestringen avensa hOgmolekylara polykarbonat. Omestras exempelvis 1 mol av bisfenylkarbonatet av 2,2-(4,4'-dioxidifeny1)-propan med 1 mol 2,2-(4,4'-dioxidifeny1)-propan, sa erhailer man polykarbonatet av 2,2-(4,4'-dimddifeny1)-propan under avsondring av fenol. Detta forfarande har den fOrdelen, att den avsondrade fenolmangden per viktsenhet bildat polykarbonat Or mindre an vid de andra omestringsforfarandena. If these bis-alkyl, cycloalkyl or aryl carbonates of dimonowdaryl alkanes are heated, preferably under reduced pressure, a high molecular weight polycarbonate is obtained during the decomposition of neutral alkyl, cycloalkyl or aryl ester. If the said compound is reacted in admixture with a dimonooxyaryl alkane, the transesterification of high molecular weight polycarbonate is obtained. For example, transesterify 1 mole of the bisphenyl carbonate of 2,2- (4,4'-dioxyphenyl) -propane with 1 mole of 2,2- (4,4'-dioxyphenyl) -propane to obtain the polycarbonate of 2,2- (4 , 4'-dimddiphenyl) -propane while secreting phenol. This process has the advantage that the amount of phenol secreted per unit weight forms polycarbonate Or less than in the other transesterification processes.

Omestringen genomf ores for det mesta vid temperaturer mellan 50 och 350°, fiiretradesvis mellan 120 och 280° och i narvaro av en inert gas, sasom kvave under forminskat tryck. Omestringen kan paskyndas genom tillsats ay katalysatorer. Sarskilt lampligt as att anvanda basiska omest- 2— ringskatalysatorer, som lampligen mot slutet av omestringen neutraliseras med basbindande dmnen, i synnerhet flyktiga basbindande dinnen. The transesterification is carried out mostly at temperatures between 50 and 350 °, preferably between 120 and 280 ° and in the presence of an inert gas, such as nitrogen under reduced pressure. The transesterification can be accelerated by the addition of catalysts. Particularly appropriate is to use basic transesterification catalysts, which are suitably neutralized towards the end of the transesterification with base-bonding compounds, in particular volatile base-bonding moieties.

Exempel 1. En blandning av 46,8 viktdelar bisfenylkarbonat av 2,2-(4,4'-dioxidifeny1)-propan, 0,008 viktdelar kalciumhydrid och 0,008 viktdelar natriumbenzoat smaltes under omrorning i kvaveatmosfar. Det avsondrade difenylkarbonatet avdestillerar vid 2000 och 2 Torr. Efter ytterligare upphettning vid 280° och 0,2 Torr. neutraliseras den alkaliska katalysatoren genom inrorfling av 0,05 viktdelar dimetylsulfat. Man fort-salter omrorningen 1/2 timme vid 280° och 0,2 Torr., varvid dimetylsulfatoverskottet avlagsnas, och man erhaller sa ett farglost, hagmolekylart, termoplastiskt polykarbonat, som mjuknar vid cirka 230', har ett K-varde av 52, matt i m-kresol och kan bearbetas ur losningar, t. ex. metylenkloridlosningar, eller smalta till strackbara Elmer, fibrer och kroppar framstallda genom sprutgjutning osv. Example 1. A mixture of 46.8 parts by weight of bisphenyl carbonate of 2,2- (4,4'-dioxyphenyl) -propane, 0.008 parts by weight of calcium hydride and 0.008 parts by weight of sodium benzoate was melted with stirring in a nitrogen atmosphere. The secreted diphenyl carbonate distills off at 2000 and 2 Torr. After further heating at 280 ° and 0.2 Torr. the alkaline catalyst is neutralized by stirring 0.05 parts by weight of dimethyl sulphate. The stirring is continued for 1/2 hour at 280 DEG C. and 0.2 DEG C., the excess dimethyl sulphate being removed, and a colorless, hail molecule-like, thermoplastic polycarbonate, which softens at about 230 DEG C., has a K value of 52. matt in m-cresol and can be processed from solutions, e.g. methylene chloride solutions, or melt into stretchable elms, fibers and bodies made by injection molding, etc.

Exempel 2. En blandning av 38 viktdelar bisfenylkarbonat av 2,2-(4,4'-dioxidifeny1)-propan, 8 viktdelar bisetylkarbonat av 2,2-(4,4'-dioxidifeny1)-propan och 0,01 viktdelar natriumsalt av 2,2-(4,4'-dioxidifeny1)-propan smdltes i kvaveatmosfar under omrorning. De avsandrade neutrala karbonaten avdestillera yid 2000 och 5 Torr. Uenom ytterligare upphettning vid 260-2800 under ett tryck av 0,2 Torr. erhaller man en hogviskos smalta, vari for neutralisation av alkalit inrores 0,05 viktdelar klorkolsyrafenylester. Overskottet pa klorkolsyrafenylester avlagsnas genom. omrorning 1/2 timme vid 280° och. 0,2 Torr. Den sa erhallna farglosa, hogmolekylara plasten med en mjukningspunkt av cirka 230° och ett K-varde av 51, matt i m-kresol, liknar till sina egenskaper det i exempel 1 beskrivna polykarbonatet. Example 2. A mixture of 38 parts by weight of bisphenyl carbonate of 2,2- (4,4'-dioxyphenyl) -propane, 8 parts by weight of bisethyl carbonate of 2,2- (4,4'-dioxyphenyl) -propane and 0.01 part by weight of sodium salt of 2,2- (4,4'-Dioxydiphenyl) -propane was melted in a nitrogen atmosphere with stirring. The emitted neutral carbonates distill off yid 2000 and 5 Torr. By further heating at 260-2800 under a pressure of 0.2 Torr. a high-viscosity melt is obtained, in which 0.05 parts by weight of chlorocarbonic acid phenyl ester are stirred in for the neutralization of alkali. The excess chloric acid phenyl ester is deposited through. stirring 1/2 hour at 280 ° and. 0.2 Torr. The resulting colorless, high molecular weight plastic with a softening point of about 230 ° and a K-value of 51, matt in m-cresol, is similar in its properties to the polycarbonate described in Example 1.

Exempel 3. En blandning av 550 viktdelar bisfenylkarbonat av 2,2-(4,4'-dimddifeny1)-propan, 228 viktdelar 2,2-(4,4'-dioxidifeny1)-propan och 0,015 viktdelar natriumsalt av 2,2-(4,4'-dioxidifeny1)-propan smaltes under omrorning i kvaveatmosfar. Vid temperaturer mellan 150 och 200' avdestillerar den avsondrade fenolen i vattenstralvakuum. Efter ytterligare tre timmars upphettning vid 280° under eft tryck av 0,5 Torr. erhalles en segviskos smalta. Efter kondensationens avslutning neutraliseras del i katalysatom ingdende alkalit genom tillsats av 0,3 viktdelar dimetylsulfat och overskottet av dimetylsulfat avlagsnas i hogvakuum. Man erhaller en plast, vars egenskaper motsvara plastens i exempel 1 och som utan sOnderdelning kan bearbetas i smalta vid temp eraturer upp Over 300°. Example 3. A mixture of 550 parts by weight of bisphenyl carbonate of 2,2- (4,4'-dimethiphenyl) -propane, 228 parts by weight of 2,2- (4,4'-dioxydiphenyl) -propane and 0.015 parts by weight of sodium salt of 2,2- (4,4'-Dioxydiphenyl) -propane was melted with stirring in a nitrogen atmosphere. At temperatures between 150 and 200 ', the secreted phenol distills off in a water jet vacuum. After heating for a further three hours at 280 ° under a pressure of 0.5 Torr. obtained a viscous smalta. After completion of the condensation, part of the alkali-containing catalyst is neutralized by the addition of 0.3 parts by weight of dimethyl sulphate and the excess dimethyl sulphate is removed in a high vacuum. A plastic is obtained, the properties of which correspond to the plastic in Example 1 and which can be processed without decomposition in melt at temperatures above 300 °.

Claims

1. Patent application: A method of preparing high molecular weight thermoplastic polycarbonates on the basis of dimonooxiaryl alkanes according to the transesterification process, characterized in that one or more his-aryl, alkyl or cycloalkyl carbonates of dimonooxiaryl alkanes are heated alone or in admixture -monooxiaryl-alkanes. Request publications: Stockholm 1962. Iiungl. Boktr. P. A. Norstedt & Sorter. 620089