CH345157A - Process for the production of polyesters - Google Patents
Process for the production of polyestersInfo
- Publication number
- CH345157A CH345157A CH345157DA CH345157A CH 345157 A CH345157 A CH 345157A CH 345157D A CH345157D A CH 345157DA CH 345157 A CH345157 A CH 345157A
- Authority
- CH
- Switzerland
- Prior art keywords
- polyesters
- polyester
- groups
- optionally substituted
- acid
- Prior art date
Links
- 229920000728 polyester Polymers 0.000 title claims description 46
- 238000000034 method Methods 0.000 title claims description 19
- 238000004519 manufacturing process Methods 0.000 title description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical group OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 20
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 10
- 150000001993 dienes Chemical class 0.000 claims description 10
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- 239000001530 fumaric acid Chemical class 0.000 claims description 8
- 239000011976 maleic acid Substances 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 150000007513 acids Chemical class 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 150000002688 maleic acid derivatives Chemical class 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 230000001419 dependent effect Effects 0.000 claims 5
- 238000007259 addition reaction Methods 0.000 claims 3
- 150000002689 maleic acids Chemical class 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 6
- 238000007792 addition Methods 0.000 description 6
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- ORTVZLZNOYNASJ-UPHRSURJSA-N (z)-but-2-ene-1,4-diol Chemical compound OC\C=C/CO ORTVZLZNOYNASJ-UPHRSURJSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- -1 2-ethyl-2,4-hexadiene-1-ol ester Chemical class 0.000 description 2
- HABHUTWTLGRDDU-UHFFFAOYSA-N 2-oxopimelic acid Chemical compound OC(=O)CCCCC(=O)C(O)=O HABHUTWTLGRDDU-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229920003232 aliphatic polyester Polymers 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- OXTNCQMOKLOUAM-UHFFFAOYSA-N 3-Oxoglutaric acid Chemical compound OC(=O)CC(=O)CC(O)=O OXTNCQMOKLOUAM-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 150000002237 fumaric acid derivatives Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63H—TOYS, e.g. TOPS, DOLLS, HOOPS OR BUILDING BLOCKS
- A63H29/00—Drive mechanisms for toys in general
- A63H29/24—Details or accessories for drive mechanisms, e.g. means for winding-up or starting toy engines
-
- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63H—TOYS, e.g. TOPS, DOLLS, HOOPS OR BUILDING BLOCKS
- A63H17/00—Toy vehicles, e.g. with self-drive; ; Cranes, winches or the like; Accessories therefor
-
- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63H—TOYS, e.g. TOPS, DOLLS, HOOPS OR BUILDING BLOCKS
- A63H18/00—Highways or trackways for toys; Propulsion by special interaction between vehicle and track
- A63H18/02—Construction or arrangement of the trackway
- A63H18/026—Start-finish mechanisms; Stop arrangements; Traffic lights; Barriers, or the like
-
- 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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
- H01M50/204—Racks, modules or packs for multiple batteries or multiple cells
- H01M50/207—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape
- H01M50/213—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape adapted for cells having curved cross-section, e.g. round or elliptic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Toys (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
Verfahren zur Herstellung von Polyestern
Die Erfindung betrifft ein Verfahren zur Herstellung von Polyestern, die unsubstituierte oder substituierte zl4-Tetrahydrophthalatgruppen enthalten, durch Diensynthese. Das Verfahren ist dadurch gekennzeichnet, dass man in mehr als 10 Estergruppen aufweisenden polymeren Maleinat- oder Fumaratgruppen, die gegebenenfalls substituiert sind, durch Anlagerung von Verbindungen mit konjugierten Kohlenstoff-Kohlenstoff-Doppelbindungen in gegebenenfalls substituierte /14-Tetrahydrophthalatgruppen umwandelt.
Diensynthesen an niedermolekularen Verbindungen mit den verschiedensten Dienen sind bekannt, insbesondere Additionen an Maleinsäure und Malein- und Fumarsäurederivate, z. B. Ester und Chloride. Die Synthese von Polyestern mit ungesättigten Gruppierungen ist ebenfalls bekannt, z. B. die Herstellung von Polyestern der Fumarsäure und der Maleinsäure. Es ist auch schon versucht worden, Polyester der d4-Tetra- hydrophthalsäure herzustellen. Bekanntlich erschwert jedoch die Konfiguration der o-Phthalsäure die Reaktion zu Polymeren derart, dass man selbst bei extremen Reaktionsbedingungen nicht über ein Molekulargewicht von etwa 2000 hinauskommt.
Das erfindungsgemässe Verfahren ist ein einfaches und wirtschaftliches Verfahren zur Herstellung von Polyestern, welche unsubstituierte oder substituierte d4-Tetrahydrophthalsäure gebunden enthalten und hohe Molekulargewichte aufweisen können. Solche Polyester sind z. B. aus Polyalkoholen und aus unsubstituierter oder substituierter S4-Tetrahydrophthal- säure und gegebenenfalls andern gesättigten oder ungesättigten Polycarbonsäuren aufgebaut. Sie können lineare oder verzweigte Ketten enthalten.
Zur Durchführung des erfindungsgemässen Verfahrens verwendet man vorzugsweise Polyester, wie sie durch Polykondensieren von Diolen (z. B. Äthylenglykol, Hexandiol, Butylenglykol, Butendiol, Diglykol) gegebenenfalls unter Mitverwendung von höherwertigen Alkoholen, wie Glycerin, Pentaerythrit, Hexantriol usw., mit gegebenenfalls substituierter Fumarsäure oder Maleinsäure und gegebenenfalls andern Polycarbonsäuren, z. B. Bernsteinsäure, Glutarsäure, Adipinsäure, Sebacinsäure, Weinsäure, Citronensäure, Ketopimelinsäure, Acetondicarbonsäure, Terephthalsäure usw., erhältlich sind.
Für die Dienaddition nach Diels-Mder eignen sich alle Verbindungen mit konjugierten Kohlenstoff Kohlenstoff-Doppelbindungen, z. B. Butadien, Cyclopentadien, Cyclohexadien, 2-Äthyl-2,4-hexadien- 1 -ol- ester usw. Die Dienaddition erfolgt vorzugsweise bei Temperaturen unter 120oC.
Das erfindungsgemässe Verfahren gestattet es, Polyester herzustellen, deren Molekulargewicht in weiten Grenzen variierbar ist. So sind Polyester mit Molekulargewichten bis über 60000, vorzugsweise über 2000, herstellbar. Die Höhe des Molekulargewichtes der erfindungsgemäss hergestellten Polyester wird durch das Molekulargewicht des Ausgangspolyesters bedingt.
Beispiel 1
Ein Polyester aus Maleinsäure und 1,6-Hexandiol, dessen Herstellung unten beschrieben wird und der ein mittleres Molekulargewicht von etwa 3000 besitzt, wird unter Rühren bei Zimmertemperatur mit Cyclopentadien langsam versetzt. Die angewandte Menge Cyclopentadien entspricht der Anzahl im Polyester vorhandener Doppelbindungen. Anschlie ssend wird bei etwa 60 C erhitzt und der Ansatz unter Rühren 3 Stunden bei dieser Temperatur belassen.
Man erhält einen klaren, leicht gelblich gefärbten Polyester der 3,6-Endomethylen-d 4-Te trahydrophthal- säure mit 1,6-Hexandiol.
Der oben verwendete Polyester wurde folgendermassen hergestellt (die Herstellung der Ausgangs polyester ist nicht Gegenstand der Erfindung):1 Mol Maleinsäureanhydrid und 1 Mol 1,6-Hexandiol werden in der Schmelze bei etwa 90"C etwa 2 Stunden belassen. Das dabei entstandene Wasser wird im Vakuum abgezogen. Anschliessend wird die Temperatur auf etwa 120-130 C gesteigert und unter Rühren weiter verestert; das dabei weiter entstehende Wasser wird von Zeit zu Zeit abgezogen. Um die Veresterung abzubrechen, werden nach etwa 20 Stunden 0,1 Mol Octanol zugesetzt und so lange verestert, bis die Säurezahl unter 5 gesunken ist. Die Veresterung kann mit Vorteil in Gegenwart eines Katalysators, wie p-Toluolsulfonsäure, durchgeführt werden.
Dadurch werden sowohl die Reaktionstemperaturen als auch die Reaktionszeiten herabgesetzt.
Eine andere Darstellungsweise für Ausgangspolyester, vor allen Dingen für Polyester mit erhöhtem Erweichungspunkt, ist die folgende:
1 Mol Fumarsäure und 1 Mol 1,4-Butandiol werden bei 120-130 C zusammengeschmolzen. Anschliessend wird 1,5% p-Toluolsulfonsäure zugesetzt und der Ansatz in Chlorbenzol gelöst, so dass eine 20%ige Lösung entsteht. Durch Destillation des Chlorbenzols wird das entstandene Reaktionswasser abgeführt. Durch Zugabe von trockenem Chlorbenzol wird die Konzentration aufrechterhalten. Nach 20 Stunden wird die Reaktion abgebrochen.
Beispiel2
Ein Polyester vom mittleren Molekulargewicht 4000 aus l/2 Mol Maleinsäure, 1/2 Mol Sebacinsäure und 1 Mol 1,4-Butandiol wird mit 2-Äthyl-2,4-hexa- dien-l-ol-ester der Essigsäure gemäss Beispiel 1 behandelt. Es entsteht eine zähflüssige, klare, leicht gelblich gefärbte Substanz.
Beispiel 3
Eine 20%ige Lösung in Chlorbenzol eines Polyesters vom mittleren Molekulargewicht 5000, welcher durch die in Beispiel 1 erwähnte Methode aus 1 Mol Fumarsäure, 1/2 Mol Hexandiol und l/2 Mol Diglykol erhalten wurde, wird mit Butadien im Verhältnis von 1 Mol Butadien pro Mol Fumarsäure im Polyester in Gegenwart eines Polymerisationsinhibitors (z. B. Dinitrobenzol oder Hydrochinon), der in einer Menge von 0,3%, bezogen auf das Polyestertrockengewicht, angewandt wird, unter Druck zunächst bei Zimmertemperatur und anschliessend bei erhöhter Temperatur behandelt. Nach Abziehen des Lösungsmittels, z. B. durch Abdestillieren, wird ein viskoser Polyester erhalten.
Beispiel 4
Ein Polyester aus 1 Mol Maleinsäure, 0,5 Mol 1,6-Hexandiol und 0,5 Mol 1,2,4-Butantriol vom mittleren Molekulargewicht 5000 wird mit 2-Äthyl 2,Phexadien-l-ol-ester der Essigsäure im Verhältnis von 1 Mol des letzteren Esters pro Mol Maleinsäure im Polyester umgesetzt. Es entsteht ein zähelastischer Polyester.
Beispiel 5
Ein Polyester, der l/2 Mol Fumarsäure,/2 Mol Bernsteinsäure und 1 Mol 1,6-Hexandiol enthält, wird bei etwa 80" C unter Rühren mit 1/4 Mol Cyclopentadien umgesetzt. Es entsteht dabei ein Polyester, der 1/4 Mol Fumarsäure, ¸ Mol Bernsteinsäure, 1/4 Mol 3,6-Endo methylen-d4-Tetrahydrophthalsäure und 1 Mol 1,6 Hexandiol enthält und bei einem mittlerenMolekulargewicht von 2500 eine wachsartige Konsistenz und einen Erweichungspunkt von 48" aufweist.
Beispiel 6
Es wird ein Polyester als Ausgangssubstanz verwendet, der dem Ausgangspolyester des Beispiels 5 entspricht, wobei anstelle der Bernsteinsäure Ketopimelinsäure eingesetzt und gemäss Beispiel 5 gearbeitet wird.
Beispiel 7
Es wird als Ausgangssubstanz ein Polyester verwendet, der dem Ausgangspolyester des Beispiels 4 entspricht, welcher aber anstelle des 1,2,4-Butantriols Butendiol enthält. Es wird nach Beispiel 4 gearbeitet.
Die durch die Diensynthese erhaltenen Polyester können in einfacher Weise modifiziert werden, indem die Doppelbindung der cycloaliphatischen Gruppierung z. B. epoxydiert wird oder durch Anlagerung von Halogenen oder Halogen-Wasserstoff oder durch Hydrierung aufgehoben wird. Sie eignen sich je nach ihrer Art als Weichmacher für z. B. Vinyl- bzw. Acrylhochpolymere sowie für die verschiedenen Cellulosederivate. Sie zeichnen sich durch gute Gelierfähigkeit, sehr grosse Migrationsfestigkeit und ihre stabilisierende Wirkung aus.
Die erfindungsgemäss hergestellten Polyester eignen sich auch zur Mischpolymerisation mit Vinyl- und Acrylmonomeren. Man kann beispielsweise 65 Teile Polyester mit 35 Teilen Styrol lösen und unter Zugabe von 0,5% Methyläthylketonperoxyd und 9,01% Kobaltnaphthenat oder Dimethylanilin bei etwa 40 in 5 Minuten aushärten. Gegenüber den üblichen Kombinationen mit linearen aliphatischen Polyestern sind Gemische von Monomeren und Polyestern der beschriebenen Art relativ niederviskos und damit leicht verarbeitbar. Das erhaltene gehärtete Harz besitzt geringe Sprödigkeit und ist elastischer als Harze aus aliphatischen Polyestern.
Process for the production of polyesters
The invention relates to a process for the production of polyesters which contain unsubstituted or substituted z14-tetrahydrophthalate groups by diene synthesis. The process is characterized in that polymeric maleate or fumarate groups which have more than 10 ester groups and are optionally substituted are converted into optionally substituted / 14-tetrahydrophthalate groups by addition of compounds with conjugated carbon-carbon double bonds.
Diene syntheses of low molecular weight compounds with a wide variety of dienes are known, in particular additions of maleic acid and maleic and fumaric acid derivatives, e.g. B. Esters and Chlorides. The synthesis of polyesters with unsaturated groups is also known, e.g. B. the production of polyesters of fumaric acid and maleic acid. Attempts have also been made to produce polyesters of d4-tetraphthalic acid. However, it is known that the configuration of o-phthalic acid makes the reaction to polymers so difficult that a molecular weight of about 2000 cannot be exceeded even under extreme reaction conditions.
The process according to the invention is a simple and economical process for the production of polyesters which contain unsubstituted or substituted d4-tetrahydrophthalic acid in bonded form and can have high molecular weights. Such polyesters are e.g. B. composed of polyalcohols and of unsubstituted or substituted S4-tetrahydrophthalic acid and optionally other saturated or unsaturated polycarboxylic acids. They can contain linear or branched chains.
To carry out the process according to the invention, polyesters are preferably used, such as those obtained by polycondensing diols (e.g. ethylene glycol, hexanediol, butylene glycol, butenediol, diglycol), optionally with the use of higher alcohols such as glycerol, pentaerythritol, hexanetriol, etc., with optionally substituted Fumaric acid or maleic acid and optionally other polycarboxylic acids, e.g. B. succinic acid, glutaric acid, adipic acid, sebacic acid, tartaric acid, citric acid, ketopimelic acid, acetone dicarboxylic acid, terephthalic acid, etc. are available.
All compounds with conjugated carbon-carbon double bonds are suitable for the Diels-Mder diene addition, e.g. B. butadiene, cyclopentadiene, cyclohexadiene, 2-ethyl-2,4-hexadiene-1-ol ester, etc. The diene addition is preferably carried out at temperatures below 120 ° C.
The process according to the invention makes it possible to produce polyesters whose molecular weight can be varied within wide limits. For example, polyesters with molecular weights of up to over 60,000, preferably over 2,000, can be produced. The level of the molecular weight of the polyesters produced according to the invention is determined by the molecular weight of the starting polyester.
example 1
A polyester made from maleic acid and 1,6-hexanediol, the preparation of which is described below and which has an average molecular weight of about 3000, is slowly admixed with cyclopentadiene while stirring at room temperature. The amount of cyclopentadiene used corresponds to the number of double bonds present in the polyester. The mixture is then heated at about 60 ° C. and the batch is left at this temperature for 3 hours while stirring.
A clear, slightly yellowish polyester of 3,6-endomethylene-d 4-tetrahydrophthalic acid with 1,6-hexanediol is obtained.
The polyester used above was produced as follows (the production of the starting polyester is not the subject of the invention): 1 mol of maleic anhydride and 1 mol of 1,6-hexanediol are left in the melt at about 90 ° C. for about 2 hours The temperature is then increased to about 120-130 ° C. and esterification is continued while stirring; the water which is further formed is drawn off from time to time. To stop the esterification, 0.1 mol of octanol is added after about 20 hours and Esterified until the acid number has fallen below 5. The esterification can advantageously be carried out in the presence of a catalyst, such as p-toluenesulphonic acid.
This reduces both the reaction temperatures and the reaction times.
Another way of representing the starting polyester, especially polyester with a higher softening point, is the following:
1 mole of fumaric acid and 1 mole of 1,4-butanediol are melted together at 120-130.degree. Then 1.5% p-toluenesulfonic acid is added and the batch is dissolved in chlorobenzene so that a 20% solution is formed. The water of reaction formed is removed by distilling the chlorobenzene. The concentration is maintained by adding dry chlorobenzene. The reaction is terminated after 20 hours.
Example2
A polyester with an average molecular weight of 4000 made from 1/2 mol of maleic acid, 1/2 mol of sebacic acid and 1 mol of 1,4-butanediol is treated with 2-ethyl-2,4-hexadien-1-ol ester of acetic acid according to Example 1 treated. A viscous, clear, slightly yellowish colored substance is produced.
Example 3
A 20% solution in chlorobenzene of a polyester with an average molecular weight of 5000, which was obtained by the method mentioned in Example 1 from 1 mol of fumaric acid, 1/2 mol of hexanediol and 1/2 mol of diglycol, is mixed with butadiene in a ratio of 1 mol of butadiene per mole of fumaric acid in the polyester in the presence of a polymerization inhibitor (e.g. dinitrobenzene or hydroquinone), which is used in an amount of 0.3%, based on the dry polyester weight, treated under pressure initially at room temperature and then at elevated temperature. After removing the solvent, e.g. B. by distilling off, a viscous polyester is obtained.
Example 4
A polyester made from 1 mol of maleic acid, 0.5 mol of 1,6-hexanediol and 0.5 mol of 1,2,4-butanetriol with an average molecular weight of 5000 is mixed with 2-ethyl-2, Phexadien-1-ol ester of acetic acid in the ratio of 1 mole of the latter ester per mole of maleic acid reacted in the polyester. A tough elastic polyester is produced.
Example 5
A polyester containing 1/2 mole of fumaric acid, / 2 mole of succinic acid and 1 mole of 1,6-hexanediol is reacted with 1/4 mole of cyclopentadiene at about 80 ° C. with stirring. A polyester that is 1/4 Mole of fumaric acid, ¸ mole of succinic acid, 1/4 mole of 3,6-endomethylene-d4-tetrahydrophthalic acid and 1 mole of 1,6 hexanediol and has a waxy consistency and a softening point of 48 "with an average molecular weight of 2500.
Example 6
A polyester is used as the starting substance which corresponds to the starting polyester of Example 5, with ketopimelic acid being used instead of succinic acid and the procedure being carried out according to Example 5.
Example 7
The starting substance used is a polyester which corresponds to the starting polyester of Example 4, but which contains butenediol instead of the 1,2,4-butanetriol. Example 4 is used.
The polyesters obtained by the diene synthesis can be modified in a simple manner by removing the double bond of the cycloaliphatic grouping, for. B. is epoxidized or abolished by addition of halogens or halogen-hydrogen or by hydrogenation. Depending on their type, they are suitable as plasticizers for z. B. vinyl or acrylic high polymers and for the various cellulose derivatives. They are characterized by good gelability, very high migration resistance and their stabilizing effect.
The polyesters prepared according to the invention are also suitable for copolymerization with vinyl and acrylic monomers. For example, 65 parts of polyester can be dissolved with 35 parts of styrene and, with the addition of 0.5% methyl ethyl ketone peroxide and 9.01% cobalt naphthenate or dimethyl aniline, cure at about 40 in 5 minutes. Compared to the usual combinations with linear aliphatic polyesters, mixtures of monomers and polyesters of the type described have a relatively low viscosity and are therefore easy to process. The cured resin obtained has little brittleness and is more elastic than resins made from aliphatic polyesters.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE335114X | 1954-12-16 | ||
| DE250255X | 1955-02-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH345157A true CH345157A (en) | 1960-03-15 |
Family
ID=25768380
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH335114D CH335114A (en) | 1954-12-16 | 1955-03-17 | Driving play system with toys and charging point |
| CH345157D CH345157A (en) | 1954-12-16 | 1955-12-21 | Process for the production of polyesters |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH335114D CH335114A (en) | 1954-12-16 | 1955-03-17 | Driving play system with toys and charging point |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US2832177A (en) |
| CH (2) | CH335114A (en) |
| FR (1) | FR1128493A (en) |
| GB (1) | GB770078A (en) |
Families Citing this family (44)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3115724A (en) * | 1961-04-06 | 1963-12-31 | Robert E Clarke | Toy vehicle starter and timer |
| US3223417A (en) * | 1962-08-23 | 1965-12-14 | Nicholas P Riso | Racing game |
| US3229421A (en) * | 1963-02-20 | 1966-01-18 | Robert K Ostrander | Power operated dolls |
| US3243917A (en) * | 1963-02-27 | 1966-04-05 | Aurora Plastics Corp | Electrical motor operated toy vehicle |
| US3503151A (en) * | 1965-11-26 | 1970-03-31 | Gen Electric | Sealed fuel cell power pack in combination with a toy vehicle |
| US3471963A (en) * | 1967-05-29 | 1969-10-14 | F E White Co Inc | Toy automobile and starting device therefor |
| US3628284A (en) * | 1970-02-02 | 1971-12-21 | Mattel Inc | Miniature high-speed electric toy racing vehicle with rechargeable battery |
| US3629680A (en) * | 1970-04-17 | 1971-12-21 | Mattel Inc | Toy battery charger |
| US3707805A (en) * | 1970-11-02 | 1973-01-02 | Mattel Inc | Toy vehicle remote winding apparatus |
| US3708913A (en) * | 1971-02-08 | 1973-01-09 | Marvin Glass & Associates | Toy motorcycle |
| US3665643A (en) * | 1971-04-01 | 1972-05-30 | Ronald B Colgrove | Toy vehicle |
| US3675108A (en) * | 1971-10-12 | 1972-07-04 | Thomas H Nicholl | Induction charging device |
| US3735525A (en) * | 1971-12-06 | 1973-05-29 | M Freed | Motor-actuated toys |
| JPS5464B2 (en) * | 1974-08-30 | 1979-01-05 | ||
| US3970309A (en) * | 1975-03-07 | 1976-07-20 | Tomy Kogyo Co., Inc. | Racing game |
| US4078798A (en) * | 1976-12-06 | 1978-03-14 | Ideal Toy Corporation | Toy vehicle |
| JPS5630398Y2 (en) * | 1978-02-17 | 1981-07-20 | ||
| JPS5920317Y2 (en) * | 1979-10-23 | 1984-06-12 | 株式会社トミー | lace toy |
| US4347683A (en) * | 1980-09-03 | 1982-09-07 | John Maxim | Conductive fluid activated devices |
| US4476648A (en) * | 1983-02-04 | 1984-10-16 | John Maxim | Float activated toy vehicle |
| US4636178A (en) * | 1983-02-09 | 1987-01-13 | Takara Co., Ltd. | Rechargeable toy electric vehicle set |
| FR2540738B3 (en) * | 1983-02-10 | 1985-10-25 | Joustra Sa | RANGE OF TOYS |
| US4501567A (en) * | 1983-05-03 | 1985-02-26 | Cathell Philip W | Elongated wand-type wind-up and trigger-released separable actuator for motorized toy |
| JPS6076995U (en) * | 1983-11-02 | 1985-05-29 | 株式会社ニツコー | rechargeable radio controlled toy |
| US4695267A (en) * | 1985-02-08 | 1987-09-22 | Robert S. McDarren | Battery-powered small-scale toy vehicle |
| GB2196870A (en) * | 1986-10-06 | 1988-05-11 | Synergistics Research | A toy vehicle remote control unit |
| EP0313675A1 (en) * | 1987-10-27 | 1989-05-03 | Kurt Hesse | Track section for toy vehicles |
| GB2270850B (en) * | 1992-09-29 | 1995-06-21 | John Hine Limited | Ornamental model dwelling having an electrically operated device |
| US5334076A (en) * | 1993-07-22 | 1994-08-02 | Sawara Co., Ltd. | Radio control car |
| JP3463344B2 (en) * | 1994-05-16 | 2003-11-05 | 株式会社セガ | Rechargeable traveling toy, charging device for traveling toy, and traveling path for traveling toy |
| US5916007A (en) * | 1997-07-08 | 1999-06-29 | Maxim; John G. | Magnetically tripped spring wound vehicles |
| US5941754A (en) * | 1997-11-17 | 1999-08-24 | Maxim; John G. | Electrically powered miniature vehicle with water drain activation timing module and rear wheel lift mechanism |
| US6033285A (en) * | 1998-02-06 | 2000-03-07 | Marvel Enterprises, Inc. | Vibrating toy car with special effects |
| JP3588086B2 (en) | 2002-04-17 | 2004-11-10 | 株式会社タカラ | Remote control top toy |
| AU153060S (en) * | 2003-01-03 | 2003-09-25 | Halsall International Ltd | A toy |
| JP2005185548A (en) * | 2003-12-25 | 2005-07-14 | Takara Co Ltd | Remote control top toy |
| US7377295B2 (en) * | 2005-04-07 | 2008-05-27 | Traxxas Lp | Fuel filler cap for a model vehicle |
| US20070049160A1 (en) * | 2005-06-06 | 2007-03-01 | Robert Matthes | Toy vehicle playset and target game |
| US20120028538A1 (en) * | 2010-07-30 | 2012-02-02 | Silverlit Limited | Electrical charger for rechargeable electrical wireless unit |
| US8764511B2 (en) | 2011-04-29 | 2014-07-01 | Mattel, Inc. | Toy vehicle |
| US20140057522A1 (en) * | 2012-03-30 | 2014-02-27 | Vincent Leslie Stewart | Vehicular Toys With Multimedia Related Features |
| EP2806480B1 (en) * | 2013-05-20 | 2017-08-09 | Nintendo Co., Ltd. | Battery accomodation structure and battery accomodation method |
| JP6294903B2 (en) * | 2016-03-22 | 2018-03-14 | 株式会社Ｓｕｂａｒｕ | vehicle |
| JP7016901B2 (en) * | 2020-03-19 | 2022-02-07 | 任天堂株式会社 | Running toys and game systems |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1610005A (en) * | 1925-05-14 | 1926-12-07 | Philip C Haag | Toy |
| US2160738A (en) * | 1938-04-29 | 1939-05-30 | Horn Ernst | Device for winding up spring-driven clockworks of toy vehicles |
| US2298431A (en) * | 1939-11-14 | 1942-10-13 | Charles J Sullivan | Toy |
| FR1003384A (en) * | 1949-12-20 | 1952-03-17 | Automatic winder for mechanical toys |
-
1955
- 1955-03-17 CH CH335114D patent/CH335114A/en unknown
- 1955-03-30 GB GB9316/55A patent/GB770078A/en not_active Expired
- 1955-04-04 FR FR1128493D patent/FR1128493A/en not_active Expired
- 1955-05-25 US US510975A patent/US2832177A/en not_active Expired - Lifetime
- 1955-12-21 CH CH345157D patent/CH345157A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| US2832177A (en) | 1958-04-29 |
| FR1128493A (en) | 1957-01-07 |
| GB770078A (en) | 1957-03-13 |
| CH335114A (en) | 1958-12-31 |
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