DE1190189B - Process for the preparation of copolymers of trioxane - Google Patents
Process for the preparation of copolymers of trioxaneInfo
- Publication number
- DE1190189B DE1190189B DED43889A DED0043889A DE1190189B DE 1190189 B DE1190189 B DE 1190189B DE D43889 A DED43889 A DE D43889A DE D0043889 A DED0043889 A DE D0043889A DE 1190189 B DE1190189 B DE 1190189B
- Authority
- DE
- Germany
- Prior art keywords
- trioxane
- copolymers
- preparation
- propiolactone
- polymerization
- 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
Links
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 title claims description 16
- 229920001577 copolymer Polymers 0.000 title claims description 7
- 238000000034 method Methods 0.000 title claims description 7
- 229960000380 propiolactone Drugs 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000012442 inert solvent Substances 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 8
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- -1 polyoxymethylenes Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000019256 formaldehyde Nutrition 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- ODNBVEIAQAZNNM-UHFFFAOYSA-N 1-(6-chloroimidazo[1,2-b]pyridazin-3-yl)ethanone Chemical compound C1=CC(Cl)=NN2C(C(=O)C)=CN=C21 ODNBVEIAQAZNNM-UHFFFAOYSA-N 0.000 description 1
- YCHXNMPJFFEIJG-UHFFFAOYSA-N 3-methyloxiran-2-one Chemical compound CC1OC1=O YCHXNMPJFFEIJG-UHFFFAOYSA-N 0.000 description 1
- GUNJVIDCYZYFGV-UHFFFAOYSA-K Antimony trifluoride Inorganic materials F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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
- C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
- C08G2/06—Catalysts
-
- 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
- C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
-
- 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
- C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
- C08G2/18—Copolymerisation of aldehydes or ketones
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Description
DEUTSCHESGERMAN
PATENTAMTPATENT OFFICE
AUSLEGESCHRIFTEDITORIAL
Int. α.:Int. α .:
Nummer:
Aktenzeichen:
Anmeldetag:
Auslegetag:Number:
File number:
Registration date:
Display day:
C08gC08g
Deutsche Kl.: 39 c-19German class: 39 c-19
D43889IVd/39c
29. August 1959
1. April 1965D43889IVd / 39c
August 29, 1959
April 1, 1965
Aus der USA.-Patentschrift 2 795 571 ist es bekannt, Trioxan mit ionischen Katalysatoren, wie Antimontrifluorid, Zinkfluorid, Fluorwasserstoffsäure u. a., in hochmolekulare Polyoxymethylene zu überführen.From US Pat. No. 2,795,571 it is known to use trioxane with ionic catalysts, such as Antimony trifluoride, zinc fluoride, hydrofluoric acid inter alia, to convert into high molecular weight polyoxymethylenes.
Die dabei erhaltenen Polymeren sind aber sowohl thermisch als auch chemisch instabil, da offensichtlich die nach diesen Methoden in die Polymerketten eingeführten Endgruppen den Makromolekülen nur eine ungenügende Stabilität zu geben vermögen.The polymers obtained in this way are, however, both thermally and chemically unstable, since obviously the end groups introduced into the polymer chains according to these methods only belong to the macromolecules able to give insufficient stability.
Weiter ist es nach der britischen Patentschrift 796 863 bekannt, wasserfreien Formaldehyd mit z. B. Aralkyläthern, Carbonsäureanhydriden, Estern oder Sulfiden in Gegenwart eines Polymerisationsinitiators, wie z. B. einem quartären Ammoniumsalz, zu polymerisieren. Die Aralkyläther, Carbonsäureanhydride, Ester oder Sulfide dienen als Überträger, dabei entstehen Polyoxymethylene, die an mindestens einer Endgruppe stabilisiert sind.It is also known from British Patent 796 863 to use anhydrous formaldehyde z. B. aralkyl ethers, carboxylic anhydrides, esters or sulfides in the presence of a polymerization initiator, such as. B. a quaternary ammonium salt, to polymerize. The aralkyl ethers, carboxylic acid anhydrides, esters or sulfides serve as carriers, this results in polyoxymethylenes which are stabilized at at least one end group.
Es wurde nun gefunden, daß man endgruppenstabile Copolymerisate des Trioxans durch Polymerisation von wasserfreiem Trioxan mit einer sauerstoffhaltigen Verbindung mittels ionischer Katalysatoren, gegebenenfalls in inerten Lösungsmitteln, herstellen kann, wenn man als sauerstoffhaltige Verbindung /i-Propiolacton verwendet.It has now been found that end-group-stable copolymers of trioxane can be obtained by polymerization of anhydrous trioxane with an oxygen-containing compound by means of ionic catalysts, optionally in inert solvents, can be prepared if the oxygen-containing compound / i-propiolactone used.
/2-Propiolacton wird in Mengen von 0,001 bis 50 Gewichtsprozent, bezogen auf Trioxan, verwendet. Trioxan wird sowohl in geschmolzenem wie in gelöstem Zustand eingesetzt. Als Lösungsmittel dienen organische Lösungsmittel. Sämtliche Reaktionsteilnehmer, d. h. Trioxan, /3-Propiolacton, organische Lösungsmittel und Katalysatoren müssen weitgehend wasserfrei sein./ 2-propiolactone is used in amounts of 0.001 to 50 percent by weight, based on trioxane, used. Trioxane is found in both molten and dissolved State used. Organic solvents are used as solvents. All respondents, d. H. Trioxane, / 3-propiolactone, organic solvents and catalysts must be largely anhydrous.
Die Polymerisation kann bei normaler oder schwach erhöhter Temperatur durchgeführt werden.The polymerization can be carried out at normal or slightly elevated temperature.
Das sich ausscheidende Polymere wird durch Waschen mit Methanal und Extraktion mit verdünnter Natronlauge von geringen niedrigmolekularen Anteilen bzw. von Initiatorresten befreit.The excreted polymer is diluted by washing with methanal and extraction with Sodium hydroxide solution freed from small, low molecular weight fractions or initiator residues.
Die Ausbeuten sind bei entsprechender Versuchsführung nahezu quantitativ. Die Molekulargewichte der Polymerisate können durch geeignete Dosierung der Kettenüberträger in weiten Grenzen variiert und damit kann der Erweichungspunkt nach Wunsch eingestellt werden.When the experiment is carried out accordingly, the yields are almost quantitative. The molecular weights the polymers can be varied within wide limits by suitable metering of the chain transfer agents thus the softening point can be adjusted as desired.
Es ist auch möglich, den Polymerisaten bekannte Weichmacher, Stabilisatoren, Antioxydantien zuzusetzen, ebenso Füll- und/oder Farbstoffe, wie Glasfasern, Schlackenwolle oder vorteilhaft hochdisperse aktive Füllstoffe, wie alkalischer Ruß, Oxyde von Metallen oder Metalloiden, wie Aluminiumoxyd, Verfahren zur Herstellung von Copolymerisate!! des TrioxansIt is also possible to add known plasticizers, stabilizers, antioxidants to the polymers, likewise fillers and / or dyes, such as glass fibers, slag wool or, advantageously, highly disperse ones active fillers, such as alkaline soot, oxides of metals or metalloids, such as aluminum oxide, Process for the production of copolymers !! of trioxane
Anmelder:Applicant:
Deutsche Gold- und Silber-ScheideanstaltGerman gold and silver refinery
vormals Roessler,formerly Roessler,
Frankfurt/M., Weißfrauenstr. 9Frankfurt / M., Weißfrauenstr. 9
Als Erfinder benannt:Named as inventor:
Dr. Werner Kern,Dr. Werner Kern,
Dr. Volker Jaacks, MainzDr. Volker Jaacks, Mainz
Titanoxyd, Zirkonoxyd oder Siliciumoxyd, die durch Umsetzung flüchtiger Verbindungen dieser Stoffe bei höheren Temperaturen in einem oxydierenden oder hydrolisierenden Medium erhalten werden.Titanium oxide, zirconium oxide or silicon oxide, which by converting volatile compounds of these substances higher temperatures can be obtained in an oxidizing or hydrolyzing medium.
Auf diese Weise werden Formkörper erhalten, die zäh und elastisch sind, durch Alkalien nicht ab-, gebaut werden, gegen Säure recht beständig sind, beim Erwärmen auf 180° C während 1 Stunde nur geringfügig depolymerisieren.In this way, moldings are obtained which are tough and elastic, do not wear off with alkalis, are quite resistant to acid, when heated to 180 ° C for 1 hour only depolymerize slightly.
Die erfindungsgemäß hergestellten Copolymerisate werden nach den für Thermoplasten üblichen Verfahren zu Formkörpern durch Spritzgießen, Walzen, Pressen u. a. verarbeitet und zum Überziehen von Gegenständen verwendet.The copolymers produced according to the invention are made by the processes customary for thermoplastics to moldings by injection molding, rolling, pressing and others. processed and for coating Objects used.
Der technische Fortschritt des erfindungsgemäßen Verfahrens gegenüber dem Verfahren der britischen Patentschrift 796 863 liegt darin, daß die Polymeren, die bei der Polymerisation von Trioxan mit der erfindungsgemäß verwendeten Verbindung erhalten werden, thermisch vollkommen stabil sind. Die durch Polymerisation von Formaldehyd mit Überträgern erhaltenen Polymeren sind aber — durch den gegenüber von Trioxan völlig verschieden ablaufenden Polymerisationsvorgang — thermisch nicht in dem Maße stabil.The technical progress of the process according to the invention over the process of the British Patent 796 863 is that the polymers in the polymerization of trioxane with the invention Compound used are obtained, are thermally completely stable. By Polymerization of formaldehyde with carriers are obtained but - by the opposite of trioxane completely different running polymerization process - not thermally in that Dimensions stable.
8 g wasserfreies Trioxan und 2 g ß-Propiolacton wurden bei 20° C in 10 ml Methylenchlorid gelöst. In diese Lösung wurde langsam eine verdünnte Lösung von Borfluoridätherat in Methylenchlorid so lange eingetropft, bis sich der Beginn der Polymerisation durch die Trübung des Gemisches bemerkbar machte. Nach Beendigung der Reaktion wurde das abgenutschte Polymere durch Kochen mit8 g of anhydrous trioxane and 2 g of ß-propiolactone were dissolved in 10 ml of methylene chloride at 20 ° C. A diluted solution was slowly added to this solution Solution of Borfluoridätherat in methylene chloride added dropwise until the beginning of the polymerization made noticeable by the turbidity of the mixture. After completion of the reaction, the sucked off polymer was boiled with
509 557/475509 557/475
Diäthyläther von anhaftendem Borfiuorid befreit. Der Schmelzpunkt des so erhaltenen Copolymeren beträgt etwa 120° C. Es besitzt selbst bei weit höheren Temperaturen eine sehr gute thermische Stabilität. Nach rascher Zersetzung von 5 Gewichtsprozent instabilen Anteils zeigte das Copolymere aus Trioxan und Propiolacton (mit 1 Gewichtsprozent Phenyl-yS-naphthylamin als Antioxydans versetzt) bei 180° C an der Luft nur einen Gewichtsverlust von 0,05 % je Minute.Diethyl ether freed from adhering boron fluoride. The melting point of the copolymer thus obtained is about 120 ° C. It has very good thermal stability even at much higher temperatures. After rapid decomposition of 5 percent by weight of the unstable fraction, the copolymer of trioxane showed and propiolactone (with 1 percent by weight phenyl-yS-naphthylamine added as an antioxidant) at 180 ° C in air only a weight loss of 0.05% per minute.
Zu einer Lösung von 6,2 g Trioxan und 0,16 g /J-Propiolacton in 20 ml Nitrobenzol werden bei 35° C 28 mg Bortrifluoridätherat (gelöst in 0,25 ml Nitrobenzol) gegeben. Nach 15 Minuten wird die Polymerisation mit Methanol abgebrochen, das ausgefallene Polymerisat abgesaugt und zur Entfernung der Initiatorreste und des Lösungsmittels nochmals mit Methanol behandelt und getrocknet. Man erhält ao 6 g eines weißen pulvrigen Polymeren mit einem Schmelzbereich von 162 bis 165° C. Der thermisch stabile Anteil beträgt nach 1 Stunde bei 190° C unter Stickstoff 75%.To a solution of 6.2 g of trioxane and 0.16 g / I-propiolactone in 20 ml of nitrobenzene are at 35 ° C given 28 mg boron trifluoride etherate (dissolved in 0.25 ml nitrobenzene). After 15 minutes the The polymerization with methanol was terminated, and the polymer which had precipitated was filtered off with suction and removed the initiator residues and the solvent treated again with methanol and dried. One obtains ao 6 g of a white powdery polymer with a melting range of 162 to 165 ° C. The thermal stable proportion is 75% after 1 hour at 190 ° C under nitrogen.
Zu einer Lösung von 6,2 g Trioxan und 0,62 g ytf-Propiolacton in 20 ml Nitrobenzol werden bei 35° C 56 mg Bortrifluoridätherat (gelöst in 0,5 ml Nitrobenzol) gegeben. Nach 25 Minuten wird die Polymerisation mit Methanol abgebrochen und das Polymerisat wie im Beispiel 2 aufgebarbeitet. Man erhält 5,9 g eines weißen Polymeren, dessen thermisch stabiler Anteil nach 1 Stunde bei 190° C unter Stickstoff 98.1 °/o beträgt.To a solution of 6.2 g of trioxane and 0.62 g of ytf-propiolactone in 20 ml of nitrobenzene are at 35 ° C given 56 mg boron trifluoride etherate (dissolved in 0.5 ml nitrobenzene). After 25 minutes the The polymerization was terminated with methanol and the polymer was worked up as in Example 2. Man receives 5.9 g of a white polymer, the thermally stable portion of which after 1 hour at 190.degree under nitrogen is 98.1%.
Claims (1)
Britische Patentschrift Nr. 796 863.Considered publications:
British Patent No. 796,863.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED43889A DE1190189B (en) | 1959-08-29 | 1959-08-29 | Process for the preparation of copolymers of trioxane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED43889A DE1190189B (en) | 1959-08-29 | 1959-08-29 | Process for the preparation of copolymers of trioxane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1190189B true DE1190189B (en) | 1965-04-01 |
Family
ID=7047928
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DED43889A Pending DE1190189B (en) | 1959-08-29 | 1959-08-29 | Process for the preparation of copolymers of trioxane |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1190189B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB796863A (en) * | 1955-03-18 | 1958-06-18 | Du Pont | Improvements in or relating to the preparation of high molecular weight linear polymers of formaldehyde |
-
1959
- 1959-08-29 DE DED43889A patent/DE1190189B/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB796863A (en) * | 1955-03-18 | 1958-06-18 | Du Pont | Improvements in or relating to the preparation of high molecular weight linear polymers of formaldehyde |
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