DE1189273B - Process for the preparation of polyoxymethylenes - Google Patents
Process for the preparation of polyoxymethylenesInfo
- Publication number
- DE1189273B DE1189273B DED44108A DED0044108A DE1189273B DE 1189273 B DE1189273 B DE 1189273B DE D44108 A DED44108 A DE D44108A DE D0044108 A DED0044108 A DE D0044108A DE 1189273 B DE1189273 B DE 1189273B
- Authority
- DE
- Germany
- Prior art keywords
- polyoxymethylenes
- molecular weight
- preparation
- low molecular
- formaldehyde
- 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
- 238000000034 method Methods 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title claims description 4
- -1 polyoxymethylenes Polymers 0.000 title description 11
- 229920006324 polyoxymethylene Polymers 0.000 title description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 150000001241 acetals Chemical class 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000012442 inert solvent Substances 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Natural products CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 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
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000007788 liquid Substances 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
- 238000000465 moulding Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- AJBKKGJMKYBIIR-UHFFFAOYSA-M triethyl(propan-2-yl)azanium iodide Chemical compound [I-].C(C)[N+](C(C)C)(CC)CC AJBKKGJMKYBIIR-UHFFFAOYSA-M 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
- C08G2/08—Polymerisation of formaldehyde
-
- 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
- C08G2/24—Copolymerisation of aldehydes or ketones with acetals
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
BUNDESREPUBLIK DEUTSCHLAND Int. Cl.:FEDERAL REPUBLIC OF GERMANY Int. Cl .:
DEUTSCHESGERMAN
PATENTAMTPATENT OFFICE
AUSLEGESCHRIFTEDITORIAL
uusguusg
Deutsche Kl.: 39 c-18German class: 39 c-18
Nummer: 1189 273Number: 1189 273
Aktenzeichen: D 44108IV d/39 cFile number: D 44108IV d / 39 c
Anmeldetag: 29. August 1959 Filing date: August 29, 1959
Auslegetag: 18. März 1965Opening day: March 18, 1965
Es ist bekannt, daß man monomeren Formaldehyd in einem indifferenten, flüssigen Medium in Abwesenheit von Wasser mit ionischen Initiatoren, wie z. B. aliphatischen oder aromatischen Aminen (vgl. USA.-Patentschrift 2 768 994 und H. Staudinger und W. Kern, »Die hochmolekularen organischen Verbindungen«, 1932, S. 280 bis 287) oder z. B. quartäre Ammoniumsalze bzw. Triphenylphosphin (vgl. britische Patentschrift 796 863) zu hochmolekularen Polyoxymethylenen polymerisieren kann.It is known that monomeric formaldehyde can be used in an inert, liquid medium in the absence of water with ionic initiators, such as. B. aliphatic or aromatic amines (see. USA. Patent 2,768,994 and H. Staudinger and W. Kern, "Die hochmolekularenorganischenverbindungen", 1932, pp. 280 to 287) or z. B. quaternary ammonium salts or triphenylphosphine (cf. British patent 796 863) to high molecular weight Can polymerize polyoxymethylenes.
Ferner ist aus den britischen Patentschriften 796 863 und 796 862 bekannt, Formaldehyd in Gegenwart von Überträgern, wie z. B. Aralkyläthern, Estern, Carbonsäureanhydriden und Sulfiden oder Wasser, Methanol und Ameisensäure zu polymerisieren. It is also known from British patents 796 863 and 796 862 to use formaldehyde in Presence of carriers, such as B. aralkyl ethers, esters, carboxylic anhydrides and sulfides or Polymerize water, methanol and formic acid.
Es ist ferner vorgeschlagen worden, zur Herstellung von Polyoxymethylenen den monomeren Formaldehyd in Gegenwart einer Schwefelverbindung mit dem Strukturelement =N — CSS— zu polymerisieren. Ein weiterer Vorschlag hat die Polymerisation von wasserfreiem Formaldehyd in Gegenwart von in trockenen, gesättigten Chlorkohlenwasserstoffen suspendiertem oder gelöstem Schwefel zum Gegenstand. .It has also been proposed for the preparation of polyoxymethylenes the monomeric Formaldehyde in the presence of a sulfur compound with the structural element = N - CSS- polymerize. Another suggestion is the polymerization of anhydrous formaldehyde in the presence of sulfur suspended or dissolved in dry, saturated chlorinated hydrocarbons to the subject. .
Es wurde nun gefunden, daß man endgruppenstabile Polyoxymethylene durch Polymerisation von wasserfreiem Formaldehyd mittels ionischer Katalysatoren in Gegenwart von sauerstoffhaltigen Verbindungen, gegebenenfalls in inerten Lösungsmitteln, herstellen kann,, wenn man. als sauerstoffhaltige Verbindungen Acetale der allgemeinen FormelIt has now been found that end-group stable polyoxymethylenes can be obtained by polymerizing anhydrous formaldehyde using ionic catalysts in the presence of oxygen-containing compounds, optionally in inert solvents, can produce, if one. than oxygenated Compounds acetals of the general formula
ORiORi
R —HC<R -HC <
verwendet, in der R ein Wasserstoifatom oder einen niedermolekularen Alkylrest und Ri einen niedermolekularen Alkylrest bedeutet.used, in which R is a hydrogen atom or a low molecular weight alkyl radical and Ri is a low molecular weight Means alkyl radical.
Als besonders geeignet erwiesen sich Dimethylformal, Diäthylformal, Diäthylacetal.Dimethyl formal, diethyl formal, diethylacetal have proven to be particularly suitable.
Die Acetale werden in Mengen von 0,001 bis 50 Gewichtsprozent, bezogen auf Formaldehyd, verwendet. Als Lösungsmittel dienen organische Lösungsmittel. Sämtliche Reaktionsteilnehmer, d. h. Formaldehyd, Acetale, organische Lösungsmittel und Katalysatoren, müssen weitgehend wasserfrei sein. Auch kann sowohl der Formaldehyd wie der Katalysator mit Hilfe eines Trägergases in das Reaktionsgemisch eingeleitet werden. The acetals are used in amounts of 0.001 to 50 percent by weight, based on formaldehyde. Organic solvents are used as solvents. All respondents, d. H. Formaldehyde, Acetals, organic solvents and catalysts must be largely anhydrous. Both the formaldehyde and the catalyst can also be introduced into the reaction mixture with the aid of a carrier gas.
Die Polymerisation kann bei normaler oder schwach erhöhter Temperatur durchgeführt werden.The polymerization can be carried out at normal or slightly elevated temperature.
Verfahren zur Herstellung von Polyoxymethylenen Process for the preparation of polyoxymethylenes
Anmelder:Applicant:
Deutsche Gold- und Silber-Scheideanstalt
vormals Roessler,
Frankfurt/M., Weißfrauenstr. 9German gold and silver separator
formerly Roessler,
Frankfurt / M., Weißfrauenstr. 9
Als Erfinder benannt:Named as inventor:
Dr. Werner Kern,Dr. Werner Kern,
Dr. Volker Jaacks, MainzDr. Volker Jaacks, Mainz
Das sich ausscheidende Polymere wird durch Waschen mit Methanol und Extraktion mit verdünnter Natronlauge von geringen Mengen niedrigmolekularer Anteile bzw. von Initi'atorresten befreit. 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.The precipitating polymer is diluted by washing with methanol and extraction with Sodium hydroxide solution freed from small amounts of low molecular weight fractions or from initiator residues. 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 and 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, Titanoxyd, Zirkonoxyd oder Siliciumdioxyd, die durch Umsetzung flüchtiger Verbindungen dieser Stoffe bei höheren Temperaturen in einem oxydierenden oder hydrolysierenden Medium erhalten werden. Auf diese Weise werden Formkörper erhalten, die zäh und elastisch sind, durch Alkalien nicht abgebaut werden, gegen Säure recht beständig sind, beim Erwärmen auf 1800C während einer Stunde nur geringfügig depolymerisieren.It is also possible to add known plasticizers, stabilizers, and antioxidants to the polymers, as well as fillers and / or dyes such as glass fibers, slag wool or, advantageously, highly dispersed active fillers such as alkaline carbon black, oxides of metals or metalloids such as aluminum oxide, titanium oxide, zirconium oxide or Silicon dioxide, which is obtained by reacting volatile compounds of these substances at higher temperatures in an oxidizing or hydrolyzing medium. In this way, moldings are obtained which are tough and elastic, are not degraded by alkalis, are quite resistant to acids, and only slightly depolymerize when heated to 180 ° C. for one hour.
Die erfindungsgemäß hergestellten Polyoxymethylene werden nach den für Thermoplasten üblichen Verfahren zu Formkörpern durch Spritzgießen, Walzen, Pressen u. a. verarbeitet und zum überziehen von Gegenständen verwendet.The polyoxymethylenes produced according to the invention are made according to those customary for thermoplastics Process for molded bodies by injection molding, rolling, pressing, and others. processed and to cover used by objects.
Den bekannten Überträgern gegenüber besitzen die erfindungsgemäß zu verwendenden Acetale eine wesentlich größere übertragungsgeschwindigkeit. Diese äußert sich in größeren Anteilen an endgruppen-Compared to the known carriers, the acetals to be used according to the invention have a much higher transmission speed. This is expressed in larger proportions of end-group
509 519/445509 519/445
stabilisierten Polyoxymethylenen in dem Endpolymerisat. stabilized polyoxymethylenes in the final polymer.
In eine wasserfreie Lösung von 3 Gewichtsprozent Dimethylformal und 0,5 Gewichtsprozent Triäthyl-isopropyl-ammoniumjodid in Hexan wird gasförmiger, wasserfreier Formaldehyd eingeleitet. Das ausfallende Polyoxymethylen hat eine solche thermische Stabilität daß es nach dem Aufarbeiten >° stündlich weniger als 1 Promille bei einer Temperatur von 1800C verliert.Gaseous, anhydrous formaldehyde is introduced into an anhydrous solution of 3 percent by weight of dimethyl formal and 0.5 percent by weight of triethyl isopropyl ammonium iodide in hexane. The precipitating polyoxymethylene has such a thermal stability that it loses hour after workup> ° less than 1 per thousand at a temperature of 180 0 C.
Claims (1)
ORiORi
ORi
Britische Patentschrift Nr. 796 863.Considered publications:
British Patent No. 796,863.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED44108A DE1189273B (en) | 1959-08-29 | 1959-08-29 | Process for the preparation of polyoxymethylenes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED44108A DE1189273B (en) | 1959-08-29 | 1959-08-29 | Process for the preparation of polyoxymethylenes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1189273B true DE1189273B (en) | 1965-03-18 |
Family
ID=7048089
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DED44108A Pending DE1189273B (en) | 1959-08-29 | 1959-08-29 | Process for the preparation of polyoxymethylenes |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1189273B (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 DED44108A patent/DE1189273B/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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