DE1230570B - Process for the production of linear, unsaturated polyesters - Google Patents

Process for the production of linear, unsaturated polyesters

Info

Publication number
DE1230570B
DE1230570B DEC24930A DEC0024930A DE1230570B DE 1230570 B DE1230570 B DE 1230570B DE C24930 A DEC24930 A DE C24930A DE C0024930 A DEC0024930 A DE C0024930A DE 1230570 B DE1230570 B DE 1230570B
Authority
DE
Germany
Prior art keywords
linear
parts
production
dicarboxylic acids
anhydrides
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
DEC24930A
Other languages
German (de)
Inventor
Dr Walter Gumlich
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huels AG
Original Assignee
Chemische Werke Huels AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to DEC24273A priority Critical patent/DE1222256B/en
Application filed by Chemische Werke Huels AG filed Critical Chemische Werke Huels AG
Priority to DEC24930A priority patent/DE1230570B/en
Priority to FR898704A priority patent/FR1323354A/en
Priority to GB2115562A priority patent/GB1000534A/en
Publication of DE1230570B publication Critical patent/DE1230570B/en
Pending legal-status Critical Current

Links

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
    • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/553—Acids or hydroxy compounds containing cycloaliphatic rings, e.g. Diels-Alder adducts
    • 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
    • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C08G63/56—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds other than from esters thereof
    • C08G63/58—Cyclic ethers; Cyclic carbonates; Cyclic sulfites ; Cyclic orthoesters
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Description

BUNDESREPUBLIK DEUTSCHLANDFEDERAL REPUBLIC OF GERMANY

DEUTSCHESGERMAN

PATENTAMTPATENT OFFICE

AUSLEGESCHRIFTEDITORIAL

Int. α.:Int. α .:

C08gC08g

Deutsche Kl.: 39 c -16 German class: 39 c -16

Nummer: 1230570 Number: 1230570

Aktenzeichen: C 24930IV d/39 cFile number: C 24930IV d / 39 c

Anmeldetag: 23. August 1961Filing date: August 23, 1961

Auslegetag: 15. Dezember 1966Opening day: December 15, 1966

Gegenstand der Patentanmeldung C 24273 IVd/39c (deutsche Auslegeschrift 1 222 256) ist ein Verfahren zur Herstellung linearer, ungesättigter Polyester durch Umsetzen von Anhydriden «,/S-ungesättigter Dicarbonsäuren, gegebenenfalls im Gemisch mit Anhydriden gesättigter Dicarbonsäuren, mit Alkylenoxyden bei erhöhter Temperatur in Gegenwart geringer Mengen von Alkoholen, das dadurch gekennzeichnet ist, daß man ein- und/oder zweiwertige Alkohole verwendet.Subject of patent application C 24273 IVd / 39c (German Auslegeschrift 1 222 256) is a process for the production of linear, unsaturated polyester by Conversion of anhydrides, / S-unsaturated dicarboxylic acids, optionally in a mixture with anhydrides of saturated dicarboxylic acids, with alkylene oxides at elevated temperature in the presence of small amounts of alcohols, which is characterized is that one uses monohydric and / or dihydric alcohols.

Die Erfindung betrifft ein Verfahren zur Herstellung von linearen, ungesättigten Polyestern durch Umsetzen von Anhydriden «,^-ungesättigter Dicarbonsäuren, gegebenenfalls im Gemisch mit Anhydriden gesättigter Dicarbonsäuren, mit Alkylenoxyden bei erhöhter Temperatur in Gegenwart geringer Mengen ein- und/oder zweiwertiger Alkohole nach Patentanmeldung C 24 273 IV d/39 c (deutsche Auslegeschrift 1 222 256), das dadurch gekennzeichnet ist, daß man Diene mitverwendet.The invention relates to a process for the production of linear, unsaturated polyesters by reaction of anhydrides «, ^ - unsaturated dicarboxylic acids, optionally in a mixture with anhydrides of saturated dicarboxylic acids, with alkylene oxides elevated temperature in the presence of small amounts of monohydric and / or dihydric alcohols according to patent application C 24 273 IV d / 39 c (German Auslegeschrift 1 222 256), which is characterized by that one uses service.

Die USA.-Patentschrift 2 966 479 beschreibt ein Verfahren zur Herstellung hochmolekularer linearer Polyester durch Umsetzen von Anhydriden von Dicarbonsäuren mit Epoxyden in Gegenwart basischer Katalysatoren. Bei der Aufzählung der Anhydride werden auch Addukte aus Maleinsäureanhydrid und trocknenden Ölen, wie Leinöl, genannt. Derartige hochungesättigte Produkte ergeben jedoch wegen der zahlreichen vorhandenen Doppelbindungen vernetzte Produkte.U.S. Patent 2,966,479 describes a process for making high molecular weight linear Polyester by reacting anhydrides of dicarboxylic acids with epoxides in the presence of basic Catalysts. When listing the anhydrides, adducts of maleic anhydride and drying oils, such as linseed oil. However, such highly unsaturated products result because of numerous existing double bond crosslinked products.

Dagegen werden nach dem erfindungsgemäßen Verfahren lineare, ungesättigte Polyester mit überraschend niedrigen Viskositäten erhalten.In contrast, the process according to the invention results in linear, unsaturated Obtained polyester with surprisingly low viscosities.

Die verwendeten Diene reagieren mit den Anhydriden der «,^-ungesättigten Dicarbonsäuren nach dem Diels-Alder-Prinzip.The dienes used react with the anhydrides of the «, ^ - unsaturated dicarboxylic acids the Diels-Alder principle.

Geeignete Diene sind Cyclopentadien, zweckmäßig in seiner dimeren Form, Hexachlorcyclopentadien und Terpene. Die Diene können auch als Gemische eingesetzt werden. Die Diene werden in Mengen von 10 bis 60, vorzugsweise von 50 Molprozent, bezogen auf die eingesetzten Säureanhydride, verwendet. Als Katalysatoren eignen sich z. B. Zinkoxyd, Zinkcarbonat, Magnesiumcarbonat, Bleicarbonat, besonders Zinkstearat oder mit Zink behandelte Ionenaustauscher. Die Umsetzung wird bei Temperaturen von 100 bis 1600C, vorzugsweise von 120 bis 13O0C, ausgeführt.Suitable dienes are cyclopentadiene, expediently in its dimeric form, hexachlorocyclopentadiene and terpenes. The dienes can also be used as mixtures. The dienes are used in amounts of 10 to 60, preferably 50, mol percent, based on the acid anhydrides used. Suitable catalysts are, for. B. zinc oxide, zinc carbonate, magnesium carbonate, lead carbonate, especially zinc stearate or ion exchangers treated with zinc. The reaction is performed at temperatures of 100 to 160 0 C, preferably from 120 to 13O 0 C is performed.

Die erfindungsgemäß hergestellten ungesättigten Polyester können durch Anpolymerisieren mit Vinylverbindungen ausgehärtet werden.The unsaturated polyesters produced according to the invention can be polymerized with vinyl compounds to be cured.

Verfahren zur Herstellung von linearen,
ungesättigten PolyesternProcess for the production of linear,
unsaturated polyesters

Zusatz zur Anmeldung: C 24273IV d/39 c Auslegeschrift 1222 256Addition to registration: C 24273IV d / 39 c Auslegeschrift 1222 256

Anmelder:Applicant:

Chemische Werke Hüls Aktiengesellschaft, Mari Chemical works Hüls Aktiengesellschaft, Mari

Als Erfinder benannt:
Dr. Walter Gumlich, MariNamed as inventor:
Dr. Walter Gumlich, Mari

Beispiel 1example 1

392 Teile Maleinsäureanhydrid, 30,4 Teile 1,2-Propylenglykol und 66,1 Teile Dicyclopentadien werden nach Zusatz von 3,92 Teilen Zinkstearat unter Rühren auf 120° C erhitzt. Man gibt im Verlauf von 5 Stunden 255,2 Teile Propylenoxyd zu, rührt 1 Stunde bei dieser Temperatur nach und erhält in mehr als 99 %iger Ausbeute einen Polyester mit der Säurezahl 28,5.392 parts of maleic anhydride, 30.4 parts of 1,2-propylene glycol and 66.1 parts of dicyclopentadiene are added after adding 3.92 parts of zinc stearate with stirring heated to 120 ° C. 255.2 parts of propylene oxide are added in the course of 5 hours and the mixture is stirred for 1 hour after this temperature and receives a polyester with an acid number of 28.5 in more than 99% yield.

Seine Viskosität, gemessen bei 100° C, beträgt 300OcP.Its viscosity, measured at 100 ° C, is 300OcP.

Beispiel 2Example 2

392 Teile Maleinsäureanhydrid, 30,4 Teile 1,2-Propylenglykol und 132,2 Teile Dicyclopentadien werden nach Zusatz von 3,92 Teilen Zinkstearat unter Rühren auf 12O0C erhitzt. Man gibt im Verlauf von 5 Stunden 255,2 Teile Propylenoxyd zu, rührt 1 Stunde bei dieser Temperatur nach und erhält in mehr als 99 %iger Ausbeute einen Polyester mit der Säurezahl 25,8.392 parts of maleic anhydride, 30.4 parts of 1,2-propylene glycol and 132.2 parts of dicyclopentadiene are heated after addition of 3.92 parts of zinc stearate with stirring to 12O 0 C. 255.2 parts of propylene oxide are added in the course of 5 hours, the mixture is stirred at this temperature for 1 hour and a polyester with an acid number of 25.8 is obtained in a yield of more than 99%.

Seine Viskosität, gemessen bei 1000C, beträgt 340OcP.Its viscosity measured at 100 0 C, is 340OcP.

Beispiel 3Example 3

392 Teile Maleinsäureanhydrid, 30,4 Teile 1,2-Propylenglykol und 273 Teile Hexachlorcyclopentadien werden nach Zusatz von 3,92 Teilen Zinkcarbonat unter Rühren auf 145 0C erhitzt. Man gibt im Verlauf von 5 Stunden 255,2 Teile Propylenoxyd zu, rührt 2 Stunden bei 1600C nach und erhält in mehr als 99°/oiger Ausbeute einen Polyester mit der Säurezahl 16,7. Sein Erweichungspunkt liegt bei 73° C. Die Viskosität ließ sich bei 100° C noch nicht messen.392 parts of maleic anhydride, 30.4 parts of 1,2-propylene glycol and 273 parts of hexachlorocyclopentadiene are heated to 145 ° C. with stirring after adding 3.92 parts of zinc carbonate. One gives 255.2 parts of propylene oxide in the course of 5 hours, stirred for 2 hours at 160 0 C and obtains more than 99 ° / cent yield a polyester having an acid number of 16.7. Its softening point is 73 ° C. The viscosity could not yet be measured at 100 ° C.

609 747/534609 747/534

Claims (1)

3 43 4 Patentanspruch: und/oder zweiwertiger Alkohole nach Patent-Verfahren zur Herstellung von linearen, unge- anmeldung C 24 273 IV d/39c (deutsche Auslegesättigten Polyestern durch Umsetzen von Anhy- schrift 1 222 256j, dadurch gekennzeichdriden oi,/?-ungesättigter Dicarbonsäuren, gege- net, daß man Diene mitverwendet.Claim: and / or dihydric alcohols according to patent processes for the production of linear, unregistered C 24 273 IV d / 39c (German Auslegesaturated Polyesters by transposing the anchoring 1 222 256j, thereby marked driden oi, /? - unsaturated dicarboxylic acids, if dienes are also used. benenfalls im Gemisch mit Anhydriden gesättigter 5 if necessary in a mixture with anhydrides of saturated 5 Dicarbonsäuren, mit Alkylenoxyden bei erhöhter In Betracht gezogene Druckschriften:Dicarboxylic acids, with alkylene oxides at increased Publications considered: Temperatur in Gegenwart geringer Mengen ein- USA.-Patentschrift Nr. 2 966 479.Temperature in the presence of small amounts in U.S. Patent No. 2,966,479. 609 747/334 12.66 © Bundesdruckerei Berlin609 747/334 12.66 © Bundesdruckerei Berlin
DEC24930A 1961-06-02 1961-08-23 Process for the production of linear, unsaturated polyesters Pending DE1230570B (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
DEC24273A DE1222256B (en) 1961-06-02 1961-06-02 Process for the production of linear, unsaturated polyesters
DEC24930A DE1230570B (en) 1961-06-02 1961-08-23 Process for the production of linear, unsaturated polyesters
FR898704A FR1323354A (en) 1961-06-02 1962-05-25 Process for the preparation of linear unsaturated polyesters
GB2115562A GB1000534A (en) 1961-06-02 1962-06-01 Production of linear unsaturated polyesters

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEC24273A DE1222256B (en) 1961-06-02 1961-06-02 Process for the production of linear, unsaturated polyesters
DEC24930A DE1230570B (en) 1961-06-02 1961-08-23 Process for the production of linear, unsaturated polyesters

Publications (1)

Publication Number Publication Date
DE1230570B true DE1230570B (en) 1966-12-15

Family

ID=25969412

Family Applications (2)

Application Number Title Priority Date Filing Date
DEC24273A Pending DE1222256B (en) 1961-06-02 1961-06-02 Process for the production of linear, unsaturated polyesters
DEC24930A Pending DE1230570B (en) 1961-06-02 1961-08-23 Process for the production of linear, unsaturated polyesters

Family Applications Before (1)

Application Number Title Priority Date Filing Date
DEC24273A Pending DE1222256B (en) 1961-06-02 1961-06-02 Process for the production of linear, unsaturated polyesters

Country Status (2)

Country Link
DE (2) DE1222256B (en)
GB (1) GB1000534A (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS531293A (en) * 1976-06-25 1978-01-09 Hitachi Chem Co Ltd Preparation of unsaturated polyesters

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2966479A (en) * 1957-09-27 1960-12-27 Shell Oil Co Process for preparing high molecular weight polyesters from monoepoxides

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2779783A (en) * 1954-09-29 1957-01-29 Firestone Tire & Rubber Co Production of linear polyesters of alkylene dicarboxylic acids

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2966479A (en) * 1957-09-27 1960-12-27 Shell Oil Co Process for preparing high molecular weight polyesters from monoepoxides

Also Published As

Publication number Publication date
GB1000534A (en) 1965-08-04
DE1222256B (en) 1966-08-04

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