CH270745A - Process for the preparation of a high polymer, linear ester. - Google Patents
Process for the preparation of a high polymer, linear ester.Info
- Publication number
- CH270745A CH270745A CH270745DA CH270745A CH 270745 A CH270745 A CH 270745A CH 270745D A CH270745D A CH 270745DA CH 270745 A CH270745 A CH 270745A
- Authority
- CH
- Switzerland
- Prior art keywords
- ester
- terephthalic acid
- ethylene glycol
- heated
- high polymer
- Prior art date
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
- C08G63/78—Preparation processes
-
- 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
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- 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
- C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
-
- 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
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
- Artificial Filaments (AREA)
Description
Verfahren zur Herstellung eines hochpolymeren, linearen Esters. Gegenstand der Erfindung ist ein Ver fahren zur Herstellung von hochpolymeren, linearen Estern, gemäss welchen Äthylen- glykol derart mit einem Halbester der Tere- phtlialsäure erhitzt wird, dass der Ät.hylen- glykolester der Tereplithalsäure gebildet wird, und dass hierauf der so entstandene Ät.hylen- glykolester so lange auf eine über seinem Schmelzpunkt liegende Temperatur erhitzt wird, bis ein Zustand erreicht wird, welcher Fäden bilden lässt,
welche nach dem Heraus ziehen oder Ausstossen aus der Schmelze sich kalt strecken lassen.
Beispiele von Halbestern der Tereplithal- säure sind Terephtlialsäure-monomethylester und Terephthalsäure-monoätliylester.
Zur Bildung des Glykolesters der Tere- phthalsä.ure wird zweckmässig auf eine Tem peratur erhitzt, welche über dem Schmelz punkt des Gemisches, ferner über dem Siede punkt des in Freiheit zu setzenden Alkohols, jedoch unterhalb des Siedepunktes des Äthy- lenglykols liegt, und zwar unter solchen Be dingungen, dass der in Freiheit gesetzte Al kohol aus der Reaktionszone entweichen kann, was gewöhnlich mittels einer üblichen Destil- lationsvorrichtung erfolgt.
Tritt keine weitere Destillation des in Freiheit gesetzten Alkohols mehr ein, so kann die Bildung des Glykol- esters als beendet betrachtet werden. Vor teilhafterweise wird man zur Erleichterung der Bildung des Glykolesters einen Esteraus- tauseh-Katalysator oder ein Gemisch solcher Katalysatoren verwenden.
Beispiele hierfür sind Lithium, Natrium, Kalium, Calcium, Beryllium, Magnesium, Zink, Cadmium, Alu minium, Chrom, Molybdän, Mangan, Eisen, Kobalt, Nickel, Kupfer, Silber, Quecksilber, Zinn, Blei, Wismut, Antimon, Platin und Palladium. Geeigliete Mengen sind 0,025 bis 0,1 Gew-Prozent, bezogen auf den Ester der Tereplithalsäure. Der Esteraustausch-Kataly- sator bzw. die Esteraustausch-Katalysatoren können als solche in Form von Pulver, Schnit zeln, Spänen, Bändern, Draht oder in anderer beliebiger Form zugesetzt werden.
Die Alkali metalle, die Erdalkalimetalle oder Magnesium werden vorzugsweise in Form von Alkohola- ten, welche durch Lösen derselben im Glykol oder in einem einwertigen Alkohol, z. B. Methanol oder Äthanol gebildet werden, ver wendet. Die Alkalimetalle lassen sich auch in Form ihrer Carbonate oder anderer alkalisch reagierender Salze, z. B. Borate, verwenden. Magnesium kann in Form seines Oxydes zur Anwendung gelangen.
Die ]Überführung des Produktes der ersten Phase der Umsetzung, das heisst des Glykol- esters der Terephthalsäure, in ein hochmole kulares, faserbildendes Produkt, erfolgt zw eek- mässig durch Erhitzen auf über den Siede punkt des Glykols liegende Temperaturen unter solchen Bedingungen, dass das Glykol aus der Reaktionszone entfernt werden kann. Während dieses Erhitzungsvorganges oder während eines Teils davon ist es zweckmässig, den Druck zu vermindern, um ein rascheres Entfernen des Glykols zu erleichtern.
Drücke von 20 mm bis hinunter auf 0,5 mm Hg haben sich als besonders geeignet erwiesen, doch kann man gewünschtenfalls auch zu höheren oder niedrigeren Drücken greifen. Esteraustausch-Katalysatoren können wäh rend dieser Phase des Erhitzens zugesetzt sein.
Das Erhitzen erfolgt vorzugsweise in Ab wesenheit von Sauerstoff und .zweckmässig in Anwesenheit eines Stromes eines sauerstoff freien Gases, wie z. B, Stickstoff, welches durch und/oder über die Reaktionsmasse ge leitet wird. Gewünschtenfalls kann man die Reaktionsmasse während des Erhitzens mecha nisch in Bewegung halten.
Obzwar die Bildung der hochpolymeren, linearen Ester aus Zweckmässigkeitsgründen als zweistufige Methode beschrieben wurde, so können diese beiden Stufen in der Praxis ineinander übergehen.
Nach beendetem Erhitzen lässt sich das Produkt in geschmolzener Form aus dem Ge fäss, in welchem es gebildet und anschliessend gekühlt wurde, ausziehen oder in anderer Weise herausnehmen.
<I>Beispiel:</I> 1,4 Teile Terephthalsäure-monoäthylester und 2,7 Teile Äthylenglykol werden zusam men gemischt und in einem mit einem Dampf auslass- und einem Gaseinlassrohr versehenen Gefäss auf 200 C erhitzt, wobei man einen sauerstofffreien Stickstoffstrom durch die Reaktionsteilnehmer streichen lässt.
Nach 4 Stunden trägt man 0,0006 Teile Lithium und 0,001 Teile Magnesium ein -und erhitzt während weiteren 2 Stunden auf 200 C, worauf die Temperatur bei Atmosphärendruck während 1 Stunde auf 285 C gehalten wird. Dann wird der Druck auf etwa 0,5 mm Hg gesenkt und während weiterer 3 Stunden er hitzt. Die aus oder so erhaltenen Schmelze ge bildeten Fäden lassen sich zu Fasern kalt ziehen.
Das so erhaltene Produkt, nämlich hoch polymeres Äthylenterephthalat, ist eine kri stalline Substanz vom Schmelzpunkt von etwa 255 C. Es kann aus der Schmelze zu Fäden gesponnen werden, welche um ihre mehrfache ursprüngliche Länge gestreckt werden können und dabei geschmeidige kräftige Fasern er geben, welche in charakteristischen Röntgen- strahleninterferenzbildern eine Orientierung längs der Faserachse zeigen. Die Fasern eignen sich in hervorragender Weise für tex- tilistische Zwecke.
Process for the preparation of a high polymer, linear ester. The invention relates to a process for the production of highly polymeric, linear esters, according to which ethylene glycol is heated with a half ester of terephthalic acid in such a way that the ethylene glycol ester of terephthalic acid is formed, and that the resulting ether is then formed .hylene glycol ester is heated to a temperature above its melting point until a state is reached which allows threads to form,
which can be cold stretched after being drawn out or expelled from the melt.
Examples of half-esters of terephthalic acid are terephthalic acid monomethyl ester and terephthalic acid monoethyl ester.
To form the glycol ester of terephthalic acid, it is expedient to heat to a temperature which is above the melting point of the mixture, further above the boiling point of the alcohol to be liberated, but below the boiling point of the ethylene glycol, namely under such conditions that the alcohol set free can escape from the reaction zone, which is usually done by means of a conventional distillation device.
If no further distillation of the liberated alcohol occurs, the formation of the glycol ester can be regarded as complete. Advantageously, an ester exchange catalyst or a mixture of such catalysts will be used to facilitate the formation of the glycol ester.
Examples include lithium, sodium, potassium, calcium, beryllium, magnesium, zinc, cadmium, aluminum, chromium, molybdenum, manganese, iron, cobalt, nickel, copper, silver, mercury, tin, lead, bismuth, antimony, and platinum Palladium. Appropriate amounts are 0.025 to 0.1 percent by weight, based on the ester of terephthalic acid. The ester exchange catalyst or the ester exchange catalysts can be added as such in the form of powder, chips, chips, tapes, wire or in any other form.
The alkali metals, the alkaline earth metals or magnesium are preferably in the form of alcohols th, which by dissolving them in glycol or in a monohydric alcohol, z. B. methanol or ethanol are formed, ver used. The alkali metals can also be used in the form of their carbonates or other alkaline salts, e.g. B. borates, use. Magnesium can be used in the form of its oxide.
The] conversion of the product of the first phase of the reaction, that is to say the glycol ester of terephthalic acid, into a high molecular weight, fiber-forming product, takes place by heating to temperatures above the boiling point of the glycol under conditions such that the Glycol can be removed from the reaction zone. During this heating process or during part of it, it is advisable to reduce the pressure in order to facilitate faster removal of the glycol.
Pressures of 20 mm down to 0.5 mm Hg have been found to be particularly suitable, but higher or lower pressures can be used if desired. Ester exchange catalysts can be added during this phase of heating.
The heating is preferably carried out in the absence of oxygen and. Expediently in the presence of a stream of an oxygen-free gas, such as. B, nitrogen, which is passed through and / or over the reaction mass. If desired, the reaction mass can be kept in motion mechanically during the heating.
Although the formation of the high-polymer, linear esters has been described as a two-step method for reasons of convenience, these two steps can merge into one another in practice.
After the end of the heating process, the product can be drawn out in molten form from the vessel in which it was formed and then cooled, or removed in some other way.
<I> Example: </I> 1.4 parts of terephthalic acid monoethyl ester and 2.7 parts of ethylene glycol are mixed together and heated to 200 ° C. in a vessel equipped with a steam outlet and a gas inlet tube, with an oxygen-free nitrogen stream flowing through it delete the respondents.
After 4 hours, 0.0006 part of lithium and 0.001 part of magnesium are introduced and heated to 200 ° C. for a further 2 hours, whereupon the temperature is maintained at 285 ° C. for 1 hour at atmospheric pressure. Then the pressure is lowered to about 0.5 mm Hg and heated for a further 3 hours. The threads formed from or obtained in this way can be cold-drawn into fibers.
The product thus obtained, namely highly polymeric ethylene terephthalate, is a crystalline substance with a melting point of about 255 C. It can be spun from the melt into threads, which can be stretched several times their original length and thereby give supple, strong fibers which show an orientation along the fiber axis in characteristic X-ray interference images. The fibers are ideally suited for textile purposes.
Claims (1)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB930904X | 1945-07-20 |
Publications (1)
Publication Number | Publication Date |
---|---|
CH270745A true CH270745A (en) | 1950-09-15 |
Family
ID=10734804
Family Applications (4)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CH254542D CH254542A (en) | 1945-07-20 | 1946-07-19 | Process for the preparation of a high polymer, linear ester. |
CH270746D CH270746A (en) | 1945-07-20 | 1946-07-19 | Process for the preparation of a high polymer, linear ester. |
CH270747D CH270747A (en) | 1945-07-20 | 1946-07-19 | Process for the preparation of a high polymer, linear ester. |
CH270745D CH270745A (en) | 1945-07-20 | 1946-07-19 | Process for the preparation of a high polymer, linear ester. |
Family Applications Before (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CH254542D CH254542A (en) | 1945-07-20 | 1946-07-19 | Process for the preparation of a high polymer, linear ester. |
CH270746D CH270746A (en) | 1945-07-20 | 1946-07-19 | Process for the preparation of a high polymer, linear ester. |
CH270747D CH270747A (en) | 1945-07-20 | 1946-07-19 | Process for the preparation of a high polymer, linear ester. |
Country Status (6)
Country | Link |
---|---|
BE (1) | BE466774A (en) |
CH (4) | CH254542A (en) |
DE (1) | DE818117C (en) |
FR (1) | FR930904A (en) |
GB (1) | GB590451A (en) |
NL (1) | NL60842C (en) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2518283A (en) * | 1948-07-29 | 1950-08-08 | Du Pont | Production of polyethylene terephthalate |
DE948086C (en) * | 1951-07-01 | 1956-08-30 | Basf Ag | Process for the production of covering materials |
DE974160C (en) * | 1952-02-16 | 1960-09-29 | Bayer Ag | Process for the production of high molecular weight polyesters of terephthalic acid |
DE1135660B (en) * | 1955-02-09 | 1962-08-30 | Ici Ltd | Process for the production of high molecular weight polyethylene or polytetramethylene terephthalates |
GB863704A (en) * | 1956-05-18 | 1900-01-01 | ||
GB799059A (en) * | 1956-06-08 | 1958-07-30 | Distillers Co Yeast Ltd | Preparation of di-(2-hydroxyethyl) terephthalate |
CH370243A (en) * | 1957-07-19 | 1963-06-30 | Schweizerische Isolawerke | Process for the production of polyester coating resins |
ES252134A1 (en) * | 1958-09-29 | 1960-06-16 | Kunoshima Kagaku Kogyo Kabushi | A procedure to obtain polycarbonates (Machine-translation by Google Translate, not legally binding) |
NL121070C (en) * | 1958-10-30 |
-
0
- BE BE466774D patent/BE466774A/xx unknown
- DE DENDAT818117D patent/DE818117C/en not_active Expired
- NL NL60842D patent/NL60842C/xx active
-
1945
- 1945-07-20 GB GB18632/45A patent/GB590451A/en not_active Expired
-
1946
- 1946-07-19 CH CH254542D patent/CH254542A/en unknown
- 1946-07-19 CH CH270746D patent/CH270746A/en unknown
- 1946-07-19 CH CH270747D patent/CH270747A/en unknown
- 1946-07-19 CH CH270745D patent/CH270745A/en unknown
- 1946-07-20 FR FR930904D patent/FR930904A/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
BE466774A (en) | |
CH270747A (en) | 1950-09-15 |
GB590451A (en) | 1947-07-17 |
CH254542A (en) | 1948-05-15 |
FR930904A (en) | 1948-02-09 |
DE818117C (en) | 1951-08-30 |
NL60842C (en) | |
CH270746A (en) | 1950-09-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE805641C (en) | Process for the production of ª ‡, ª ‰ -unsaturated carboxylic acids and their derivatives | |
CH270745A (en) | Process for the preparation of a high polymer, linear ester. | |
DE1301306C2 (en) | PROCESS FOR THE MANUFACTURING OF CARBONIC ACID VINYLESTERS | |
DE2940751A1 (en) | METHOD FOR PURIFYING CARBONYLATION PRODUCTS OF METHYL ACETATE | |
DE1210772B (en) | Process for the preparation of hexafluoroisopropyl alcohol | |
DE1593227A1 (en) | Process for the preparation of 1-bromo-1,1-difluoroethane | |
AT165047B (en) | Process for the production of organic fluorine compounds | |
DE867243C (en) | Process for the production of ªÏ-halocarboxylic acids | |
DE68907900T2 (en) | METHOD FOR PRODUCING OXYACETIC ACID / HYDROXYETHYL ETHER COMPOUND. | |
CH264201A (en) | Process for the preparation of a new high polymer linear ester. | |
CH616415A5 (en) | ||
DE924928C (en) | Process for the production of formamide | |
DE755524C (en) | Process for the production of propionaldehyde from acrolein | |
DE857194C (en) | Process for the preparation of dinitriles from aliphatic ª ‡, ªÏ-dicarboxylic acids | |
DE897554C (en) | Process for the production of acetyl chloride | |
DE809553C (en) | Process for the production of p-tert. Butyl phenol | |
CH264819A (en) | Process for the preparation of a new high polymer linear ester. | |
DE892893C (en) | Process for the production of carboxylic acid esters | |
AT218516B (en) | Process for increasing the yield of isomeric terphenyls in the pyrolysis of benzene | |
DE564436C (en) | Process for the preparation of aromatic amines from phenols of the benzene series | |
DE1956629B2 (en) | Process for the preparation of 1,1333-hexafluoropropan-2-ol | |
DE185837C (en) | ||
DE1618150C3 (en) | Process for the production of alpha-nitratolactic acid | |
DE929128C (en) | Process for the production of acetic acid from carbon dioxide and methanol | |
DE2002884C3 (en) | Process for the preparation of reaction, settlement mixtures containing 1,1,1-trichloroethane, vinyl chloride, vinylidene chloride and hydrogen chloride |