EP0000513B1 - Méthode de réutilisation des matériaux de décantation produits lors du traitement des eaux résiduaires de la production du polystyrène - Google Patents
Méthode de réutilisation des matériaux de décantation produits lors du traitement des eaux résiduaires de la production du polystyrène Download PDFInfo
- Publication number
- EP0000513B1 EP0000513B1 EP78100384A EP78100384A EP0000513B1 EP 0000513 B1 EP0000513 B1 EP 0000513B1 EP 78100384 A EP78100384 A EP 78100384A EP 78100384 A EP78100384 A EP 78100384A EP 0000513 B1 EP0000513 B1 EP 0000513B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- styrene
- parts
- water
- decanter
- 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.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
Definitions
- Polystyrene in particular expandable polystyrene, is produced on an industrial scale by polymerizing styrene in an aqueous suspension. After the polymerization has ended, the majority of the polystyrene particles are separated from the aqueous phase by centrifuging. Part of the polymer, generally about 2 to 4% by weight, based on the styrene used, remains in the form of very fine beads in the waste water. If the suspension polymerization was controlled in such a way that fine-particle polymer particles are preferably obtained, the amount of polymer remaining in the waste water increases to 5% or more. These finest particles are recovered from the wastewater by decanting, primarily for environmental reasons.
- the so-called decanter material obtained consists largely of very fine-particle polystyrene, which may contain blowing agent, and which contains relatively large amounts of emulsion polymer and other hydrophilic impurities. It is not directly for further processing, e.g. suitable for the production of foams.
- GB-A 1 416 405 describes a process for the preparation of polystyrene particles with a particle size in which pre-formed polystyrene particles with a diameter of greater than 0.4 mm are suspended in water, monomeric styrene is added to the suspension and this is present in the presence is polymerized by polymerization catalysts and retarders.
- the patent also states that attempts have been made to dissolve smaller polystyrene particles in styrene and to polymerize them. However, no useful results were obtained.
- the object of the invention was to economically process the decanter material and to reuse it.
- the invention accordingly relates to a process for the reuse of decanter material, which is obtained in the form of fine polystyrene beads with an average particle diameter of at least 0.05 mm and at most 0.3 mm, if the processing of the waste water from the production of polystyrene by suspension polymerization Solids separated, by dissolving the particles in monomeric styrene in the weight ratio of styrene to decanter material from 100: 1 to 1: 1, and polymerizing the styrene in aqueous suspension in the presence of radical initiators and optionally other polymerization aids at elevated temperature.
- the decanter material was treated with water in a weight ratio of 1:50 to 1: 1 at temperatures between 10 ° C. and 100 ° C., but in the event that the treatment in the presence of Styrene and radical initiators is made, the temperature must not exceed 80 ° C.
- the decanter material is obtained by separating the solids from the wastewater from the production of expandable polystyrene. This separation is conveniently done by decanting, e.g. by centrifuging with a solid bowl centrifuge. This produces fine polystyrene beads with an average particle diameter of at least 0.05 and at most 0.3 mm.
- the decanter material is suspended in water, the water: decanter material weight ratio being able to vary within wide limits between 50: 1 and 1: 1 and preferably between 20: 1 and 2: 1.
- Dispersing aids e.g. Polyvinyl alcohol or polyvinyl pyrrolidone are added, furthermore buffer substances which may be required in a later suspension polymerization.
- the decanter material can be cleaned with water in various ways: In a preferred procedure, the aqueous suspension of the decanter material is at temperatures between 10 ° and 100 °, preferably between 20 ° and 50 ° C, for 5 to 90 minutes, preferably 15 to 45 minutes touched. The cleaned material is then separated from the water again by decanting. This may be followed by another washing operation. The moist powder obtained is then dissolved in monomeric styrene, the weight ratio of monomer: decanter material here preferably being between 50: 1 and 5: 1. This organic phase is then suspended in water together with polymerization aids, such as, for example, polymerization initiators and suspending aids, and polymerized in a conventional manner at elevated temperature. But you can also add the cleaned wet powder with stirring a suspension of styrene in water, whereby it is detached from the styrene, and then carry out the suspension polymerization.
- polymerization aids such as, for example, polymerization initiators and suspending aids
- monomeric styrene is added to the aqueous suspension of the decanter material, the weight ratio of monomer: decanter material here preferably being between 10: 1 and 2: 1.
- the aqueous phase and the organic phase are then stirred together at temperatures between 10 and 100 ° C., preferably between 50 and 90 ° C.
- the stirring time depends on the temperature and the ratio of monomer; Decanter material. The higher the temperature and the higher the monomer: decanter material ratio, the shorter the stirring times required. In any case, stirring should be carried out here for at least one hour in order to extract the polystyrene in the decanter material sufficiently by the monomer.
- the stirring time is generally between 2 hours and 2 days. With a styrene: decanter material ratio of 1: 1, one has to stir at 20 ° C. for about 60 hours to extract essentially all of the styrene; after 18 hours, only 20% are released.
- a particular advantage of this method is that. there is no need to separate organic and aqueous phases after the extraction, but rather that the organic phase can be polymerized directly in the presence of the aqueous phase, giving uniformly round, clear pearls with a low internal water content. It is advantageous if the extraction is already carried out in the polymerization kettle. After the extraction has ended, all that is required is to add to the styrene phase the auxiliaries and free radical initiators required for the preparation of a particular bead polymer, and the polymerization can then be carried out at elevated temperature without further intermediate operations.
- styrene instead of styrene alone, a mixture of styrene with up to 50% by weight of other copolymerizable monomers, such as e.g. l1'-methylstyrene, nuclear halogenated styrenes, divinylbenzene, acrylonitrile, esters of acrylic or methacrylic acid, N-vinyl compounds or 1,3-diolefins can be used.
- other copolymerizable monomers such as e.g. l1'-methylstyrene, nuclear halogenated styrenes, divinylbenzene, acrylonitrile, esters of acrylic or methacrylic acid, N-vinyl compounds or 1,3-diolefins.
- the suspension polymerization of the styrene or of the monomer mixture is carried out under customary conditions.
- the decanter material dissolved in the monomer does not interfere.
- the polymerization is generally carried out at temperatures between 80 and 130 ° C., in particular between 100 and 120 ° C.
- the usual polymerization initiators such as peroxides or azo compounds, are used to start the polymerization.
- Either organic protective colloids, such as polymers of vinylpyrrolidone, polyvinyl alcohol or cellulose ether, or sparingly soluble inorganic salts, such as calcium phosphate, are used as suspension stabilizers. They can be added before or during the polymerization.
- the bead spectrum can be regulated by varying the time at which the suspension stabilizers are added.
- volatile hydrocarbons or halogenated hydrocarbons are added as blowing agents in a known manner.
- organic halogen compounds can be added to the suspension as flame retardants.
- the blowing agent-containing styrene polymers obtained in the suspension polymerization are suitable for the production of foams.
- the process according to the invention is particularly suitable for the production of fine-pearled polymers which are used in the porosity of bricks.
- the starting point was the waste water from a suspension polymerization of styrene, from which polymer beads had been removed by centrifuging.
- This wastewater contained 2% by weight of fine polystyrene beads with an average diameter of less than 0.3 mm. It was fed to a decanter (Westfalia SDA 230) and a polymer material with a moisture content of 3 to 8% was separated off by centrifuging.
- the mixture was polymerized with stirring in a closed vessel for 4 hours at 90 ° C., 2 hours at 105 ° C. and then for 3 hours at 120 ° C.
- 3.5 parts of a 10% strength polyvinylpyrroldione solution in water were metered in as suspension stabilizer after 130 minutes, so that an average size of 1.2 to 1.6 mm was formed.
- 3 hours after reaching 90 ° C., 7 parts of pentane were added over the course of 10 to 15 minutes.
- a sample (pearl fraction from 1.25 to 2.0 mm) was treated with methanol for 2 minutes to remove the external water, then suctioned off on a suction filter and blown dry with air at 20 ° C. in countercurrent for 5 minutes.
- the internal water content was determined using the Karl Fischer method. It was 0.61%.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Claims (4)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19772733471 DE2733471A1 (de) | 1977-07-25 | 1977-07-25 | Verfahren zur wiederverwendung von dekantermaterial, das bei der aufarbeitung des abwassers aus der produktion von polystyrol anfaellt |
DE2733471 | 1977-07-25 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0000513A1 EP0000513A1 (fr) | 1979-02-07 |
EP0000513B1 true EP0000513B1 (fr) | 1980-07-23 |
Family
ID=6014773
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP78100384A Expired EP0000513B1 (fr) | 1977-07-25 | 1978-07-12 | Méthode de réutilisation des matériaux de décantation produits lors du traitement des eaux résiduaires de la production du polystyrène |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0000513B1 (fr) |
JP (1) | JPS5423692A (fr) |
DE (2) | DE2733471A1 (fr) |
IT (1) | IT1106054B (fr) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3319457C1 (de) * | 1983-05-28 | 1984-02-09 | Degussa Ag, 6000 Frankfurt | Kobaltlegierungen zur Herstellung von Zahnersatz |
WO1992007025A1 (fr) * | 1990-10-22 | 1992-04-30 | Mobil Oil Corporation | Decontamination de polystyrene |
DE4438376A1 (de) * | 1994-10-27 | 1996-05-02 | Basf Ag | Recyclat enthaltende, expandierbare Styrolpolymerisate |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1165270B (de) * | 1962-09-06 | 1964-03-12 | Basf Ag | Verfahren zur Herstellung von feinteiligen verschaeumbaren Styrolpolymerisaten |
DE2150056A1 (de) * | 1971-10-07 | 1973-04-12 | Basf Ag | Verfahren zur reinigung von abwasser bei der herstellung von styrol-perlpolymerisaten |
GB1416405A (en) * | 1973-07-27 | 1975-12-03 | Sekisui Chemical Co Ltd | Process for preparing styrenic polymer particles |
DE2628761C2 (de) * | 1976-06-26 | 1983-01-13 | Hoechst Ag, 6000 Frankfurt | Suspensionspolymerisationsverfahren |
-
1977
- 1977-07-25 DE DE19772733471 patent/DE2733471A1/de not_active Withdrawn
-
1978
- 1978-07-12 EP EP78100384A patent/EP0000513B1/fr not_active Expired
- 1978-07-12 DE DE7878100384T patent/DE2860059D1/de not_active Expired
- 1978-07-17 IT IT50332/78A patent/IT1106054B/it active
- 1978-07-25 JP JP9003278A patent/JPS5423692A/ja active Pending
Also Published As
Publication number | Publication date |
---|---|
JPS5423692A (en) | 1979-02-22 |
DE2733471A1 (de) | 1979-02-15 |
IT1106054B (it) | 1985-11-11 |
DE2860059D1 (en) | 1980-11-13 |
IT7850332A0 (it) | 1978-07-17 |
EP0000513A1 (fr) | 1979-02-07 |
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