US3231543A - Process for the formation of shaped trioxane structures and polymerization thereof - Google Patents
Process for the formation of shaped trioxane structures and polymerization thereof Download PDFInfo
- Publication number
- US3231543A US3231543A US62534A US6253460A US3231543A US 3231543 A US3231543 A US 3231543A US 62534 A US62534 A US 62534A US 6253460 A US6253460 A US 6253460A US 3231543 A US3231543 A US 3231543A
- Authority
- US
- United States
- Prior art keywords
- trioxane
- polymerization
- shaped
- formation
- structures
- 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.)
- Expired - Lifetime
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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
- C08G2/08—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
- C08G2/06—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
- C08G2/10—Polymerisation of cyclic oligomers 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
-
- 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
- C08G2/38—Block or graft polymers prepared by polymerisation of aldehydes or ketones on to macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
-
- 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
- D01F6/66—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyethers
Definitions
- the object of this invention is achieved by a process for the formation of shaped, self-supporting structures extended in no more than two dimensions which comprises polymerizing a solid phase monomer in the form -of said shaped, self-supporting structure in the presence of a fluid catalyst.
- This invention is particularly applicable to the polymerization of trioxane and for convenience will be described with reference thereto.
- trioxane is admixed uniformly with a resinous binder, extruded through a spinning orifice to form a stream and then polymerized in the presence of gasiform boron fluoride after solidification of the stream. solidification of the stream to a self-supporting structure makes the invention applicable to monomers which cannot be polymerized instantaneously.
- the resinous binder serves the dual function of increasing the viscosity of the trioxane-to permit it to be extruded in a fine stream and of maintaining the trioxane in a fibrous structure while polymerization takes place.
- the resinous binder is blended with trioxane in proportions between about 5 and 50 weight percent, based on the weight of trioxane.
- the binder is preferably dissolved in molten trioxane before extrusion thereof through the spinning orifice. If desired, both the trioxane and the binder may be dissolved in a common solvent to form a viscous solution and the solution may be extruded through the spinning orifice.
- Solidification of the extruded stream is by cooling in the case where no solvent is used and usually by cooling and evaporation where a solvent is used. Volatile solvents and mild evaporative conditions are used with tri- "ice oxane to control the trioxane loss which would otherwise occur because of the high volatility of the trioxane.
- wet spinning methods may be used wherein the solution is extruded into a non-solvent liquid, such as n-octane, as a coagulant.
- a non-solvent liquid such as n-octane
- the filaments may be polymerized in the presence of a liquid phase catalyst, such as boron trifluoride in solution in the coagulant liquid.
- the filaments may be removed from their liquid coagulant environment before polymerization in the presence of a gasiform catalyst takes place.
- Suitable resinous binders for trioxane include thermoplastic vinyl polymers such as polyvinyl acetate, polystyrene, polyvinyl chloride, polymethyl methacrylate, polyvinyl pyrrolidone, polyethyl acrylate and polyvinyl caprolactam; thermoplastic condensation polymers, such as relatively low melting polyamides and polyesters; and thermoplastic cellulosic derivatives, such as cellulose acetate and ethyl cellulose.
- Polyacetaldehyde prepared by acid-catalyzed polymerization of acetaldehyde at its freezing point and of the formula is a useful binder since it depolyrnerizes readily when exposed to a trioxane polymerization catalyst under polymerization conditions.
- trioxane solvents such as methylene chloride or acetone are suitable.
- Suitable spinning compositions of this type include from 10 to weight percent of binder and from 50 to 500 Weight percent of solvent per unit weight of trioxane.
- Spinning conditions depend upon the nature and proportion of the resinous binder and the nature and proportion of solvent if any.
- the spinning orifice diameter may vary as desired according to the product desired. Spinning temperatures from about 0 C. to about 100 C. are suitable for most spinning compositions.
- the extruded stream is solidified, preferably byvcooling or by cooling and evaporation.
- the atmosphere into which the spinning composition is extruded is preferably maintained at a temperature between about 50 C. and 50 C.
- the preferred gasiform. catalyst is boron trifiuoride. It is preferably maintained in the atmosphere surrounding the solidified trioxane-binder filament at a concentration of from about 1 to 100 weight percent. Vaporizable acidic boron trifiuoride complexes may also be used. A suitable catalyst environment may be maintained by passing nitrogen through a normally liquid boron trifluoride complex and thereafter into the polymerization zone.
- Suitable liquid phase catalysts include solutions of boron trifiuoride or of acidic complexes of boron trifiuori-de in liquids, which are non-solvents for the trioxane and resinous binder under the polymerization conditions.
- Polymerization temperatures are suitably between about -50 and 60 C. and the period of reaction may vary from about 12 hours to 1 minute. In most cases the catalytic environment is maintained just beyond the spinning orifice so that polymerization proceeds as soon as the extruded stream is solidified to a self-supporting structure. It is possible that polymerization is initiated to a minor extent before solidification but by far the greater portion of the trioxane solidifies before being polymerized.
- filamentary material having characteristics intermediate between those of the oxymethylene polymer and those of the resinous binder.
- the resinous binder is not removed after polymerization and the amount used depends upon the desired characteristics of the final product.
- a cross-linked polymeric structure may be prepared by the copolymerization of trioxane with a polyfunctional comonomer and particularly a polycyclic ether, such as a polyepoxide.
- polyepoxides which may be used are the diepoxides of hydrocarbon dienes, such as vinyl cyclohexene dioxide and dicyclopentadiene dioxide; and diepoxides of substituted hydrocarbon dienes, such as 3,4-epoxy-6-methylcyclohexylmethyl 3,4-epoxy-6-methylcyclohexanecarboxylate.
- polymeric epoxides such as the epoxy resins produced by the reaction of epichlorohydrin with a bisphenol may also be copolymerized with trioxane by the method of this invention.
- polycyclic ethers include diketals and diacetals of pentaerythitol and dioxetanes formed from pentaerythitol and its derivatives. It may be noted that polyvinyl pyrrolidone and polyvinyl caprolactam, mentioned above as resinous binders are also polyfunctional comonomers capable of interaction with trioxane in a copolymerization.
- the polycyclic ethers are suitably blended into the spinning compositions in proportions between about 10 and 50 weight percent, based on the weight of trioxane. Spinning and polymerization conditions are as described above.
- trioxane rings open to produce short chains of three oxymethylene units and the epoxy rings open to produce substituted oxyethylene units. These units link up to form a space polymer comprising chains of oxymethylene units interspersed with oxyethylene units said chain being cross linked across carbon atoms of said oxyethylene units.
- filaments may be prepared by drawing the viscous mixture from a softened and sticky melt thereof.
- Fibrous trioxane strands may also be prepared by sublimation under carefully controlled conditions, as described below in Example I. While it is preferred to polymerize filamentary monomer other fibrous forms of monomer may be polymerized. Fibrous monomers having an extended dimension of at least 100 times the other two dimensions are suitable. Similarly monomers in film structures wherein each extended dimension is at least 100 times the thickness are suitable. 1 r
- the trioxane may be copolymerized with from 0.4 to 40 weight percent of ethylene oxide or dioxolane.
- Such copolymers have greater thermal stability than homopolymers. Since the shaping of the polymer after its formation is not required, in accordance with this invention, high thermal stability is often not essential. But where it is desired such copolymers may be prepared by forming filaments from a mixture of trioxane, comonomer and binder and polymerizing as described above.
- the general technique is also applicable to other normally solid or s-olidifiable monomers.
- the technique is particularly applicable to cationically catalyzed vinyl monomers and to cyclic compounds in which at least one ring bond is highly polarizable because of the presence of an electro-negative heteroatom.
- the cyclic compounds include other cyclic ethers, lactones, acetals, ketals, sulfides, imines and lactams.
- vinyl monomers include olefins, cycloefins, vinyl ethers and acrylic acid derivatives. It is preferred that the monomer have a molecular weight not higher than about 300.
- This invention permits the utilization of V Example I
- a fibrous sublimate of trioxane was prepared by a sequence of two condensation operations.
- molten trioxane was heated in a vessel covered with a watch-glass in such a manner that the trioxane vaporized in the vessel and condensed as a closely packed snow on the under surface (convex) of the watch glass.
- the temperature of the watch glass could not rise above the melting point of trioxane (64 C.) for the condensation.
- the watch glass was cooled, by directing a cool air stream on the upper (concave) surface of the watch glass. Satisfactory rates of collection were maintained without boiling the trioxane (heating range -100 C.).
- the watch glass with the trioxane snow attached to its lower (convex) surface was placed over another vessel which was kept cool (room emperature).
- a stream of warm air (55-60 C.) was directed at the upper (concave) surface of the watch glass so as to heat the trioxane without melting it.
- the trioxane then sublimed downward into the vessel where it formed a voluminous fibrous network.
- a portion of the above-described fibrous mass was inserted into a stoppered test tube and sufficient boron tri fiuoride to provide a concentration in the test tube of 3 volume percent was thereafter introduced.
- the tube was maintained at 25 C. for a period of 150 minutes.
- the contents of the tube were then washed with acetone to remove unreacted trioxane and boron trifiuoride.
- the polyoxymethylene fibers corresponded in weight to 71% of the trioxane starting material.
- Example II 25% solution of polyvinyl acetate in trioxane was extruded at C. through a 2.0 mm. orifice into a chamber held at 50 C. from which it was taken up at room temperature on glass tube.
- Example III Polyacetaldehyde was obtained by polymerizing acetaldehyde at its freezing point (123.5 C.). Acetaldehyde 392 parts by weight) was distilled into a cold trap maintained at its freezing point and containing 0.22 part of boric acid. Upon completion of the distillation, 1.45 parts of polymer was recovered having an inherent viscosity of 3.0 (0.1% solution in acetone at 25 C.).
- Example IV Strands were drawn with a glass rod from a solution (at 75-80" C.) consisting of 10 parts of trioxane, 2.5 parts of' polyvinyl acetate and 1 part of a diepoxide of the group listed below. The strands were exposed at: room temperature to boron trifluoride in concentrations: ranging from 13% to 100% by volume (in nitrogen) for riods of two hours at room temperature. The mate-- rial was then Washed with boiling dimethylformarnide to remove all material other than the crosslinked polymer- The results are shown in Table 1, below.
- a process for the formation of a shaped, self-supporting structure selected from the group consisting of filaments and films which comprises forming a solid phase monomer comprising at least 50% of trioxane into said shaped, self-supporting structure, and polymerizing said monomer in the presence of a fluid trioxane polymerization catalyst.
- a process for the formation of fibrous material from a monomer comprising at least 50% of trioxane which comprises forming said monomer into a solid structure in filamentary form and polymerizing said monomer in said structure in the presence of a gasiform trioxane polymerization catalyst.
- a process for the formation of fibrous material from trioxane which comprises forming trioxane into a solid 6 trioxane in said structure in the presence of gaseous boron trifluoride.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Biological Depolymerization Polymers (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US62534A US3231543A (en) | 1960-10-14 | 1960-10-14 | Process for the formation of shaped trioxane structures and polymerization thereof |
DE19611445310 DE1445310B2 (de) | 1960-10-14 | 1961-10-07 | Verfahren zur herstellung von vernetzten copolymerisaten des trioxans |
GB36459/61A GB1010711A (en) | 1960-10-14 | 1961-10-11 | Polymers and articles made therefrom |
GB26985/65A GB1010712A (en) | 1960-10-14 | 1961-10-11 | Filaments or films of oxymethylene homopolymers |
FR875811A FR1303439A (fr) | 1960-10-14 | 1961-10-12 | Procédé de fabrication de polymères d'oxyméthylène et d'objets à partir de ces derniers |
US759791A US3600458A (en) | 1960-10-14 | 1968-09-13 | Shaped structures |
US863767A US3681488A (en) | 1960-10-14 | 1969-10-02 | A melt extruding process comprising a trioxane monomer and a polymeric binder |
US123016A US3681472A (en) | 1960-10-14 | 1971-03-10 | Shaped structures |
US00235842A US3763105A (en) | 1960-10-14 | 1972-03-17 | Shaped structure of trioxane and polyacetaldehyde |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US62534A US3231543A (en) | 1960-10-14 | 1960-10-14 | Process for the formation of shaped trioxane structures and polymerization thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
US3231543A true US3231543A (en) | 1966-01-25 |
Family
ID=22043127
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US62534A Expired - Lifetime US3231543A (en) | 1960-10-14 | 1960-10-14 | Process for the formation of shaped trioxane structures and polymerization thereof |
Country Status (4)
Country | Link |
---|---|
US (1) | US3231543A (de) |
DE (1) | DE1445310B2 (de) |
FR (1) | FR1303439A (de) |
GB (2) | GB1010711A (de) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3350489A (en) * | 1963-05-03 | 1967-10-31 | Celanese Corp | Polyvinylidene cyanide composition and method of producing fibers and films |
US3752624A (en) * | 1967-10-17 | 1973-08-14 | Houilleres Bassin Du Nord | Apparatus for the production of solidified trioxan |
US3872182A (en) * | 1972-02-22 | 1975-03-18 | Hoechst Ag | Thermoplastic moulding composition on the basis of polyoxymethylene |
US4977021A (en) * | 1988-08-05 | 1990-12-11 | Hoechst Celanese Corporation | Methods for forming magnetic coatings using trioxane recording media having such coatings |
Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2170439A (en) * | 1936-04-02 | 1939-08-22 | Standard Oil Dev Co | Elastic fiber |
US2519550A (en) * | 1948-11-08 | 1950-08-22 | Du Pont | Formaldehyde polymers |
US2806015A (en) * | 1953-05-27 | 1957-09-10 | Monsanto Chemicals | Homogeneous polymer blends |
US2822237A (en) * | 1955-02-21 | 1958-02-04 | Iwamae Hiroshi | Process for producing filament of vinyl chloride polymer |
US2840447A (en) * | 1954-04-28 | 1958-06-24 | Du Pont | Process for preparing filaments from dispersions containing graft polymers obtained from ethylenically unsaturated monomers |
US2864827A (en) * | 1954-11-15 | 1958-12-16 | Phillips Petroleum Co | Process for polymerizing aldehydes |
US2883361A (en) * | 1956-09-28 | 1959-04-21 | Du Pont | Light stable composition containing a blend of a synthetic rubber and a salicylate polymer |
US2890191A (en) * | 1952-11-26 | 1959-06-09 | Phillips Petroleum Co | Rubber plasticized with a condensation product of alkene oxides and hydroxylated polymers of conjugated dienes, vulcanizates thereof, and method of making |
US2891837A (en) * | 1956-10-24 | 1959-06-23 | Du Pont | Process for forming continuous shaped structure by direct chemical spinning |
US2913430A (en) * | 1957-04-09 | 1959-11-17 | American Marietta Co | Vinyl chloride-vinyl acetate copolymer dissolved in solvent mixture containing aromatic hydrocarbon and lactone component |
US2934528A (en) * | 1956-11-21 | 1960-04-26 | American Cyanamid Co | Water-soluble polymers of nu, nu'-ethylene-bis-acrylamide |
US2947728A (en) * | 1957-10-21 | 1960-08-02 | Celanese Corp | Catalytic polymerization of trioxane |
US2947727A (en) * | 1957-10-21 | 1960-08-02 | Celanese Corp | Catalytic polymerization process |
US2947736A (en) * | 1956-12-31 | 1960-08-02 | American Cyanamid Co | Resin compositions |
US2989510A (en) * | 1958-06-20 | 1961-06-20 | Celanese Corp | High molecular weight polymer and process therefor |
US2989511A (en) * | 1958-12-23 | 1961-06-20 | Celanese Corp | Catalytic polymerization of trioxane |
US2989506A (en) * | 1957-10-21 | 1961-06-20 | Celanese Corp | Catalytic polymerization |
-
1960
- 1960-10-14 US US62534A patent/US3231543A/en not_active Expired - Lifetime
-
1961
- 1961-10-07 DE DE19611445310 patent/DE1445310B2/de active Pending
- 1961-10-11 GB GB36459/61A patent/GB1010711A/en not_active Expired
- 1961-10-11 GB GB26985/65A patent/GB1010712A/en not_active Expired
- 1961-10-12 FR FR875811A patent/FR1303439A/fr not_active Expired
Patent Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2170439A (en) * | 1936-04-02 | 1939-08-22 | Standard Oil Dev Co | Elastic fiber |
US2519550A (en) * | 1948-11-08 | 1950-08-22 | Du Pont | Formaldehyde polymers |
US2890191A (en) * | 1952-11-26 | 1959-06-09 | Phillips Petroleum Co | Rubber plasticized with a condensation product of alkene oxides and hydroxylated polymers of conjugated dienes, vulcanizates thereof, and method of making |
US2806015A (en) * | 1953-05-27 | 1957-09-10 | Monsanto Chemicals | Homogeneous polymer blends |
US2840447A (en) * | 1954-04-28 | 1958-06-24 | Du Pont | Process for preparing filaments from dispersions containing graft polymers obtained from ethylenically unsaturated monomers |
US2864827A (en) * | 1954-11-15 | 1958-12-16 | Phillips Petroleum Co | Process for polymerizing aldehydes |
US2822237A (en) * | 1955-02-21 | 1958-02-04 | Iwamae Hiroshi | Process for producing filament of vinyl chloride polymer |
US2883361A (en) * | 1956-09-28 | 1959-04-21 | Du Pont | Light stable composition containing a blend of a synthetic rubber and a salicylate polymer |
US2891837A (en) * | 1956-10-24 | 1959-06-23 | Du Pont | Process for forming continuous shaped structure by direct chemical spinning |
US2934528A (en) * | 1956-11-21 | 1960-04-26 | American Cyanamid Co | Water-soluble polymers of nu, nu'-ethylene-bis-acrylamide |
US2947736A (en) * | 1956-12-31 | 1960-08-02 | American Cyanamid Co | Resin compositions |
US2913430A (en) * | 1957-04-09 | 1959-11-17 | American Marietta Co | Vinyl chloride-vinyl acetate copolymer dissolved in solvent mixture containing aromatic hydrocarbon and lactone component |
US2947728A (en) * | 1957-10-21 | 1960-08-02 | Celanese Corp | Catalytic polymerization of trioxane |
US2947727A (en) * | 1957-10-21 | 1960-08-02 | Celanese Corp | Catalytic polymerization process |
US2989506A (en) * | 1957-10-21 | 1961-06-20 | Celanese Corp | Catalytic polymerization |
US2989510A (en) * | 1958-06-20 | 1961-06-20 | Celanese Corp | High molecular weight polymer and process therefor |
US2989511A (en) * | 1958-12-23 | 1961-06-20 | Celanese Corp | Catalytic polymerization of trioxane |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3350489A (en) * | 1963-05-03 | 1967-10-31 | Celanese Corp | Polyvinylidene cyanide composition and method of producing fibers and films |
US3752624A (en) * | 1967-10-17 | 1973-08-14 | Houilleres Bassin Du Nord | Apparatus for the production of solidified trioxan |
US3872182A (en) * | 1972-02-22 | 1975-03-18 | Hoechst Ag | Thermoplastic moulding composition on the basis of polyoxymethylene |
US4977021A (en) * | 1988-08-05 | 1990-12-11 | Hoechst Celanese Corporation | Methods for forming magnetic coatings using trioxane recording media having such coatings |
Also Published As
Publication number | Publication date |
---|---|
DE1445310A1 (de) | 1968-11-14 |
GB1010711A (en) | 1965-11-24 |
DE1445310B2 (de) | 1971-04-22 |
GB1010712A (en) | 1965-11-24 |
FR1303439A (fr) | 1962-09-07 |
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