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EP0000765B1 - Procédé de préparation de polyoxyméthylènes granulés de propriétés mécaniques améliorées - Google Patents

Procédé de préparation de polyoxyméthylènes granulés de propriétés mécaniques améliorées Download PDF

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Publication number
EP0000765B1
EP0000765B1 EP78100565A EP78100565A EP0000765B1 EP 0000765 B1 EP0000765 B1 EP 0000765B1 EP 78100565 A EP78100565 A EP 78100565A EP 78100565 A EP78100565 A EP 78100565A EP 0000765 B1 EP0000765 B1 EP 0000765B1
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EP
European Patent Office
Prior art keywords
weight
oxymethylene
polymer
temperature
oxymethylene polymer
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
Application number
EP78100565A
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German (de)
English (en)
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EP0000765A1 (fr
Inventor
Karlheinz Dr. Burg
Alwin Heller
Hans-Dieter Dr. Sabel
Helmut Dr. Schlaf
Günter Dr. Sextro
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Hoechst AG
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Hoechst AG
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Classifications

    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • 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
    • C08J2359/00—Characterised by the use of polyacetals containing polyoxymethylene sequences only
    • C08J2359/02—Copolyoxymethylenes

Definitions

  • POM oxymethylene polymers
  • the present invention now relates to a further embodiment of the latter method and is characterized in that the granular oxymethylene polymer particles obtained by precipitation with a grain diameter of more than 70 ⁇ m are separated off and dried.
  • the invention further relates to granular oxymethylene polymers which are produced by the aforementioned process.
  • a process for the production of granular oxymethylene polymers was likewise already known from German laid-open documents 2 504 482 and 2 509 924. However, the process is cooled in two stages, namely first from 5 to 65 ° C. above the sintering temperature of the polymer to 0 to 10 ° C. above the sintering temperature and then to 1 to 10 ° C. below the sintering temperature. In addition, there is no separation of the particle fraction with a particle size above 70 ⁇ m . It was not to be expected that due to the separation according to the invention and the use of only the coarse grain fraction with particle diameters of more than 70 in order to increase the impact strength and that this effect would be so pronounced (cf. the table below with the therein included comparison values).
  • Oxymethylene polymers in the context of the invention are understood to mean poly (oxymethylenes) which, in addition to oxymethylene units, also have 0.1 to 20, preferably 0.5 to 10 percent by weight oxyalkylene units with 2 to 8, preferably 2, 3 or 4 adjacent carbon atoms in the main valence chain; Oxymethylene polymers whose proportion of oxyalkylene units is 0.7 to 5 percent by weight are particularly suitable.
  • the oxymethylene polymers are prepared in a known manner by polymerizing the monomers in bulk, suspension or solution in the presence of cationically active catalysts, e.g. at a temperature of 0 to 100 ° C, preferably 50 to 90 ° C (see e.g. U.S. Patent 30 20 352).
  • cationically active catalysts (1) protonic acids, e.g. Perchloric acid, (2) esters of protonic acids, especially esters of perchloric acid with lower aliphatic alcohols, e.g. Perchloric acid tert. butyl ester, (3) anhydrides of protonic acids, especially mixed anhydrides of perchloric acid and a lower aliphatic carboxylic acid, e.g.
  • Acetyl perchlorate (4) Lewis acids, especially halides of boron, tin, titanium, phosphorus, arsenic and antimony, e.g. Boron trifluoride, tin tetrachloride, titanium tetrachloride, phosphorus pentachloride, phosphorus pentafluoride, arsenic pentafluoride and antimony pentafluoride and (5) complex compounds or salt-like compounds of Lewis acids, preferably etherates or onium salts, e.g.
  • the amount of the catalysts used in the copolymerization depends primarily on the strength of their effectiveness; in general, the catalysts are used in an amount by weight of 0.1 to 2000, preferably 0.2 to 500 ppm, based on the total amount of the compounds to be polymerized.
  • Highly effective catalysts such as boron trifluoride are advantageously used in an amount by weight of 10 to 150, preferably 20 to 100 ppm, based on the total amount of the compounds to be polymerized.
  • the corresponding molar amounts apply to complex compounds or salt-like compounds of the catalysts mentioned.
  • Very powerful catalysts such as perchloric acid are used in an amount of 0.2 to 10 ppm, preferably 0.3 to 5 ppm.
  • catalysts are diluted with an inert gas, for example nitrogen or a noble gas such as argon, while liquid or solid catalysts are dissolved in an inert solvent.
  • an inert gas for example nitrogen or a noble gas such as argon
  • aliphatic or cycloaliphatic hydrocarbons and nitrated aliphatic or aromatic hydrocarbons are suitable. Examples include: cyclohexane, methylene chloride, ethylene chloride, nitromethane and nitrobenzene.
  • the weight ratio of catalyst to diluent is usually 1: 5 to 1: 10000, preferably 1:10 to 1: 100.
  • Very potent catalysts are advantageously diluted in a ratio of 1: 5,000 to 1:20,000.
  • the polymerization process is preferably carried out under an inert gas atmosphere and in the absence of moisture; inert gases are preferably inert gases, e.g. Argon, and nitrogen suitable.
  • Suitable compounds which are copolymerizable with trioxane are, in particular, a) cyclic ethers with 3, 4 or 5 ring members, preferably epoxides, b) cyclic acetals, preferably formals, with 5 to 11, preferably 5, 6, 7 or 8 ring members and c) linear polyacetals, preferably polyformals.
  • R 'and R 2 are identical or different and each represent a hydrogen atom, an aliphatic alkyl radical having 1 to 6, preferably 1, 2, 3 or 4 carbon atoms or a phenyl radical and a) x is 1, 2 or 3 and y is zero or b) x is zero, y is 1,2 or 3 and z is 2 or c) x is zero, y is 1 and z is 3, 4, 5 or 6, or ( B) R 'is an alkyloxymethyl radical having 2 to 6, preferably 2, 3 or 4, carbon atoms or a phenoxymethyl radical, where x is 1 and y is zero and R 2 is as defined above.
  • cyclic ethers e.g. Ethylene oxide, propylene oxide, styrene oxide, cyclohexene oxide, oxacyclobutane and phenylglycidyl ether are used, while 1,3-dioxolane, 1,3-dioxane, 1,3-dioxepane and 1,3,6-trioxocane and 4-methyl-1, 3-dioxolane, 4-phenyl-1,3-dioxolane, 1,3-dioxonane and 1,3-dioxacycloheptene (5) can be used.
  • Poly (1,3-dioxolane) and poly (1,3-dioxepane) are particularly suitable as linear polyformals.
  • a regulator for the production of oxymethylene polymers with certain molecular weight ranges, it is expedient to carry out the polymerization in the presence of a regulator.
  • a regulator Formaldehyde dialkyl acetals having 3 to 9, preferably 3, 4 or 5 carbon atoms, e.g. Formaldehyde dimethyl acetal, diethyl acetal, dipropylacetal and di-butyl acetal, as well as lower aliphatic alcohols, preferably alkanols with 1 to 4 carbon atoms, e.g. Methanol, ethanol, propanol and butanol.
  • the regulator is usually used in an amount of up to 0.5 percent by weight, preferably from 0.005 to 0.1 percent by weight, based on the total amount of the compounds to be polymerized.
  • the oxymethylene polymers are expediently subjected to a thermal, controlled, partial degradation down to primary alcohol end groups in order to remove unstable fractions (cf. US Pat. Nos. 31,74948, 32,19623 and 36,66,714).
  • the thermal treatment is carried out at a temperature of 130 to 200 ° C, preferably 140 to 190 ° C, especially under non-acidic conditions in aqueous / methanolic solution, advantageously in the manner of a basic reacting compound, e.g. a lower tertiary aliphatic amine such as triethyl or triethanolamine or a secondary alkali phosphate such as disodium hydrogen phosphate.
  • a temperature of 150 to 180 ° C is particularly favorable.
  • the duration of the thermal treatment is 10 seconds to 2 hours, preferably 1 minute to 60 minutes, depending on the temperature. The higher the temperature, the shorter the residence time can be measured. At 180 ° C approximately 1 to 2 minutes are sufficient, at 160 ° C approximately 5 to 10 minutes, at 150 ° C approximately 10 to 30 minutes and at 140 ° C approximately 20 to 60 minutes.
  • the treatment is preferably carried out with the substantial exclusion of oxygen.
  • a solution or a dispersion of an oxymethylene polymer, the polymer content of which is 3 to 35, preferably 5 to 30, percent by weight is used as the starting material for the process according to the invention. Very good results are obtained with a polymer solution or dispersion which contains 10 to 20 percent by weight of oxymethylene polymers.
  • a methanol / water mixture with a methanol content of at least 75 percent by weight is used as the solvent or dispersant; preferably a mixture is used which consists of 99.9 to 80 percent by weight of methanol and 0.1 to 20 percent by weight of water.
  • a mixture of 99.5 to 85 percent by weight of methanol and 0.5 to 15 percent by weight of water is particularly advantageous, the best results being obtained with a mixture of 99 to 90 percent by weight of methanol and 1 to 10 percent by weight of water.
  • the temperature of the solution or dispersion is 5 to 65 ° C., preferably 10 to 60 ° C. above the sintering temperature of the oxymethylene polymer, the temperature range from 25 to 55 ° C. above the sintering temperature being particularly advantageous.
  • the coolant has a temperature of 1 to 10 ° C, preferably 1 to 5 ° C, in particular 2 to 4 ° C below the sintering temperature of the oxymethylene polymer.
  • the amount of the precipitated oxymethylene polymer in the suspension resulting from the introduction of the polymer solution or dispersion is at most 25, preferably 5 to 15 percent by weight.
  • the methanol used in the context of this invention may contain up to 30, preferably up to 10 percent by weight of methanol-soluble organic impurities which are usually formed as by-products in the synthesis of oxymethylene polymers, e.g. Formaldehyde, cyclic oligomers of formaldehyde, methylal, glycol, glycol formal, glycol monomethyl ether, glycol dimethyl ether and lower aliphatic alcohols, lower aliphatic esters and acetone.
  • oxymethylene polymers e.g. Formaldehyde, cyclic oligomers of formaldehyde, methylal, glycol, glycol formal, glycol monomethyl ether, glycol dimethyl ether and lower aliphatic alcohols, lower aliphatic esters and acetone.
  • the sintering temperature (T s ) is the temperature at which the solid polymer particles suspended in the methanol / water mixtures soften and adhere to the surface without completely melting.
  • the sintering temperature depends on the composition and molecular weight of the polymer and also on the type of solvent or dispersant.
  • the sintering temperature of the oxymethylene polymers used according to the invention is in the range from 100 to 140 ° C., in particular from 125 to 135 ° C.
  • the process according to the invention is carried out, for example, in an autoclave provided with a stirrer.
  • the coolant and precipitant are placed in this autoclave, and the solution or dispersion of the oxymethylene polymer is expediently introduced into the precipitant through a heated immersion tube or a nozzle, the latter being kept in turbulent motion by stirring.
  • the process can be carried out batchwise or continuously; in the case of continuous operation, the polymer suspension obtained is removed at the bottom of the autoclave to the extent that the solution or dispersion and, if appropriate, additional precipitant are added.
  • the average residence time of the oxymethylene polymer in the precipitation vessel is 1 minute to 12 hours, preferably 2 to 120 minutes.
  • the pressure is 5 to 40, preferably 8 to 30 bar.
  • solid polymer particles with different grain sizes are formed by precipitation or agglomeration.
  • the majority of the POM particles obtained consist of granular particles with a grain diameter of more than 70 ⁇ m, while a small amount consists of fine-grain particles with a grain diameter of preferably less than 50 ⁇ m (sieve analysis).
  • the granular particles preferably have grain diameters of 100 to 1000 ⁇ m and in particular of 150 to 400 ⁇ m.
  • the amount of fine-grained product to be separated off is generally less than 20 percent by weight, based on the total amount of solid polymer particles; the fine grain fraction is preferably less than 15 and in particular 3 to 10 percent by weight.
  • the POM particles with a particle diameter of above 70 are separated by conventional separation processes, e.g. by filtration, centrifugation or decanting. From the remaining mixture, the POM particles with a particle diameter of less than 70 ⁇ m can be removed by means of a separator, and the solvent can be reused as a liquid coolant.
  • the separated oxymethylene polymer is finally dried at a temperature of 20 to 135 ° C, preferably 50 to 120 ° C. Drying under an inert gas atmosphere, e.g. in an inert gas or nitrogen atmosphere is recommended.
  • the granular oxymethylene polymers obtained according to the invention are macromolecular; the values of their reduced specific viscosity (RSV) are 0.3 to 2.0, preferably 0.5 to 1.5 dl / g (measured on a 0.5 percent by weight solution of the polymer in y-butyrolactone which contains 2 percent by weight diphenylamine Stabilizer contains, at a temperature of 140 ° C).
  • the crystallite melting points of the oxymethylene polymers are in the range from 140 to 180 ° C, their melt index values (MFI 190/2) are 0.1 to 50, preferably 1 to 30 g / 10 min (measured according to DIN 53 735 at a temperature of 190 ° C and a load of 2.16 kg).
  • the bulk density of the granular oxymethylene polymers obtained according to the invention is generally more than 300, preferably 350 to 550 g / l (determined on the polymer dried under nitrogen at a temperature of 70 ° C. after two minutes of homogeneous mixing in a laboratory fluid mixer at a speed of 3000 rpm).
  • the RSV values of the separated fine-grained products are below 0.3 dl / g and are preferably 0.05 to 0.25 and in particular 0.1 to 0.2 dl / g.
  • the oxymethylene copolymers obtained according to the invention can additionally be stabilized by homogeneously mixing them with stabilizers against the influence of heat, oxygen and / or light.
  • the homogenization is usually carried out in a commercially available mixing device, e.g. an extruder, at a temperature above the melting point of the polymer up to 250 ° C, preferably at 180 to 210 ° C.
  • the total amount of stabilizers added is 0.1 to 10, preferably 0.5 to 5 percent by weight, based on the total mixture.
  • Bisphenol compounds, alkaline earth metal salts of carboxylic acids, are particularly suitable as stabilizers as well as guanidine compounds.
  • alkaline earth metal salts of carboxylic acids used are, in particular, alkaline earth metal salts of aliphatic, preferably hydroxyl-containing, mono-, di- or tri-base carboxylic acids having 2 to 20, preferably 3 to 9 carbon atoms, e.g. the calcium or magnesium salts of stearic acid, ricinoleic acid, lactic acid, mandelic acid, malic acid or citric acid.
  • guanidine compounds used in which R represents a hydrogen atom, a cyano group or an alkyl radical having 1 to 6 carbon atoms, for example cyanoguanidine, N-cyano-N'-methyl-guanidine, N-cyano-N'-ethyl-guanidine, N-cyano-N '-iso-propylguanidine, N-cyano-N'-tert-butyl-guanidine or N, N'-dicyanoguanidine.
  • the guanidine compound is optionally used in an amount of 0.01 to 1, preferably 0.02 to 0.5 percent by weight, based on the total mixture.
  • Known light stabilizers such as benzophenone, acetophenone or triazine derivatives can also be added to the oxymethylene polymers prepared according to the invention.
  • Other conventional additives such as dyes, pigments, reinforcing and filling agents or nucleating agents can also be added.
  • the oxymethylene polymers obtained according to the invention are characterized in that they have improved mechanical properties, in particular toughness properties, compared to known oxymethylene polymers. They can be processed by all the usual methods for thermoplastics, e.g. by injection molding, extrusion, extrusion blow molding, melt spinning and deep drawing. They are suitable as a material for the production of semi-finished and finished parts such as moldings, e.g. Ingots, rods, plates, tapes, bristles, threads, fibers, films, foils, pipes and hoses, as well as household items, e.g. Bowls and cups, and machine parts, e.g. Housings and gears. They can be used primarily as a technical material for the manufacture of dimensionally stable and dimensionally stable molded parts.
  • This solution is introduced within 30 min through an immersion tube into 30 parts of a methanol / water mixture of the same composition, which is in a turbulent movement in an autoclave and has a temperature of 125 ° C. (Example 2: 129 ° C.).
  • a sintering temperature of the polymer of 127 ° C (Example 2: 131 ° C)
  • the temperature of the precipitant is 2 ° C below the sintering temperature.
  • the suspension obtained is cooled to room temperature.
  • Products A and B are dried at 70 ° C under nitrogen. The bulk weights and RSV values are then determined on the dried products. Part of the products are then mixed with stabilizers (0.1% dicyandiamide; 0.5% bis (2-hydroxy-3-tert.butyl-5-methylphenyl) methane) and processed into test specimens by injection molding.
  • the impact behavior is tested in accordance with DIN 53 443 in a dart bolt test.
  • square plates with an edge length of 60 mm and a thickness of 2 mm as well as a drop bolt with a weight of 100 g are used; the ring opening of the contact surface is - in deviation from the norm - 25 mm.
  • the determined head is a measure of the toughness of the material.

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  • 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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Claims (2)

1. Procédé de préparation d'un poly-(oxyméthylène) grenu qui renferme, en plus de motifs oxymé- thylènes, de 0,1 à 20% en poids de motifs oxy-alkylènes contenant de 2 à 8 atomes de carbone voisins dans la chaîne principale, par introduction d'une dispersion ou solution à 3-35% en poids du poly-(oxyméthylène) dans un mélange de méthanol et d'eau dont la teneur en méthanol est d'au moins 75% en poids et dont la température est supérieure de 5 à 65°C à la température de frittage du poly-(oxyméthylène), dans un mélange de méthanol et d'eau en mouvement turbulent dont la teneur en méthanol est d'au moins 75% en poids et qui est maintenu à une température inférieure de 1 à 10°C à la température de frittage de poly-(oxyméthylène), et précipitation du poly-(oxyméthylène), la quantité du poly-(oxyméthylène) précipité dans la suspension formée étant d'au plus 25% en poids, puis séparation et séchage du poly-(oxyméthylène) grenu obtenu, procédé caractérisé en ce qu'on sépare et sèche celles des particules de poly-(oxyméthylène) qui ont un diamètre de grain supérieur à 70 µm.
2. Procédé selon la revendication 1, caractérisé en ce que les particules séparées et séchées ont un diamètre de grain de 100 à 1000 ,um.
EP78100565A 1977-08-10 1978-08-01 Procédé de préparation de polyoxyméthylènes granulés de propriétés mécaniques améliorées Expired EP0000765B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2735946A DE2735946C3 (de) 1977-08-10 1977-08-10 Körniges Oxymethylenpolymer mit verbesserten mechanischen Eigenschaften und Verfahren zu dessen Herstellung
DE2735946 1977-08-10

Publications (2)

Publication Number Publication Date
EP0000765A1 EP0000765A1 (fr) 1979-02-21
EP0000765B1 true EP0000765B1 (fr) 1981-06-17

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EP78100565A Expired EP0000765B1 (fr) 1977-08-10 1978-08-01 Procédé de préparation de polyoxyméthylènes granulés de propriétés mécaniques améliorées

Country Status (8)

Country Link
US (1) US4195158A (fr)
EP (1) EP0000765B1 (fr)
JP (1) JPS5430254A (fr)
CA (1) CA1106097A (fr)
DE (2) DE2735946C3 (fr)
DK (1) DK351578A (fr)
IE (1) IE47171B1 (fr)
IT (1) IT1098363B (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4668761A (en) * 1984-02-29 1987-05-26 Asahi Kasei Kogyo Kabushiki Kaisha High strength, high modulus polymeric material in continuous length, process for production thereof and device therefor
EP0708123A3 (fr) 1994-10-10 1997-10-08 Hoechst Ag Composition à mouler à base de polyacétal ayant une basse viscosité à l'état fondu
US6755678B2 (en) 2002-04-22 2004-06-29 Tyco Electronics Corporation Wire retaining connector block
DE102008018967A1 (de) * 2008-04-16 2009-10-22 Ticona Gmbh Oxymethylenpolymere, Verfahren zu deren Herstellung und deren Verwendung
DE102008018965A1 (de) 2008-04-16 2009-10-22 Ticona Gmbh Oxymethylen-Copolymere und deren Verwendung sowie Verfahren zur Herstellung von Oxymethylen-Copolymeren
DE102008018966A1 (de) 2008-04-16 2009-10-22 Ticona Gmbh Verfahren zur Herstellung von Oxymethylen-Polymeren und dafür geeignete Vorrichtung
US8840976B2 (en) 2010-10-14 2014-09-23 Ticona Llc VOC or compressed gas containment device made from a polyoxymethylene polymer
EP2505609B1 (fr) 2011-04-01 2015-01-21 Ticona GmbH Polyoxyméthylène avec une grande résistance aux chocs pour moulage par soufflage-extrusion
US8968858B2 (en) 2011-12-30 2015-03-03 Ticona Llc Printable molded articles made from a polyoxymethylene polymer composition
WO2014105670A1 (fr) 2012-12-27 2014-07-03 Ticona Llc Composition de polyoxyméthylène à résistance au choc modifiée et articles, fabriqués avec celle-ci, stables lors d'une exposition à une lumière ultraviolette

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3505292A (en) * 1964-09-30 1970-04-07 Celanese Corp Stabilization of oxymethylene polymers by hydrolysis
DE2504482B2 (de) * 1975-02-04 1977-05-18 Hoechst Ag, 6000 Frankfurt Verfahren zur herstellung von oxymethylenpolymeren in koerniger form
DE2452737B2 (de) * 1974-11-07 1976-10-07 Verfahren zur Herstellung von Verfahren zur herstellung von oxymethylenpolymeren in koerniger form
DE2509924C3 (de) * 1975-03-07 1978-03-16 Hoechst Ag, 6000 Frankfurt Verfahren zur Herstellung von Oxymethylenpolymeren in körniger Form
NL181204C (nl) * 1974-11-07 1987-07-01 Hoechst Ag Werkwijze voor het bereiden van korrelvormige oxymethyleenpolymeren.
DE2508886C3 (de) * 1975-02-28 1979-10-25 Hoechst Ag, 6000 Frankfurt Verfahren zur Herstellung von Oxymethylenpolymeren in körniger Form
DE2620017C3 (de) * 1976-05-06 1979-05-31 Hoechst Ag, 6000 Frankfurt Verfahren zur Herstellung von grobkörnigen Oxymethylenpolymeren

Also Published As

Publication number Publication date
DE2860773D1 (en) 1981-09-24
EP0000765A1 (fr) 1979-02-21
DE2735946A1 (de) 1979-02-15
JPS5430254A (en) 1979-03-06
DE2735946B2 (de) 1979-06-28
IE781620L (en) 1979-02-10
IT7826604A0 (it) 1978-08-08
CA1106097A (fr) 1981-07-28
IE47171B1 (en) 1984-01-11
DK351578A (da) 1979-02-11
US4195158A (en) 1980-03-25
DE2735946C3 (de) 1980-03-06
IT1098363B (it) 1985-09-07

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