EP0652283B1 - Nettoyage de plastique - Google Patents

Nettoyage de plastique Download PDF

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Publication number
EP0652283B1
EP0652283B1 EP94117320A EP94117320A EP0652283B1 EP 0652283 B1 EP0652283 B1 EP 0652283B1 EP 94117320 A EP94117320 A EP 94117320A EP 94117320 A EP94117320 A EP 94117320A EP 0652283 B1 EP0652283 B1 EP 0652283B1
Authority
EP
European Patent Office
Prior art keywords
solution
plastic
cleaning
complexing agent
peroxide
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
Application number
EP94117320A
Other languages
German (de)
English (en)
Other versions
EP0652283A1 (fr
Inventor
Heinz Jörg Dr. Rath
Peter Di Stamprech
Michael Prof. Dr. Schuster
Stefan Dipl.-Chem. Ringmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoechst AG
Original Assignee
Hoechst AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Publication of EP0652283A1 publication Critical patent/EP0652283A1/fr
Application granted granted Critical
Publication of EP0652283B1 publication Critical patent/EP0652283B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3218—Alkanolamines or alkanolimines

Definitions

  • the invention relates to a method and means for cleaning plastics in unprocessed and processed form, in particular plastics that come into contact with chemically highly pure liquids.
  • plastics in unprocessed and processed form, in particular plastics that come into contact with chemically highly pure liquids.
  • contaminants can get into the liquids from the container surfaces, so that they become noticeably contaminated, especially after prolonged contact and especially at higher temperatures, even if only special methods such as neutron activation are used in the container walls Impurities are detectable.
  • High-purity liquids for analytical, diagnostic and therapeutic purposes as well as in semiconductor manufacturing are increasingly being processed and stored in plastic containers and conveyed in plastic lines, with some of the valuable high-purity liquid generally being used to rinse out the line or the container and then cleaned or discarded again must become. This method is therefore very unsatisfactory.
  • a method for cleaning plastic contact lenses by treatment with a basic aqueous solution of an active oxygen-releasing per compound is known, which is characterized in that the contact lenses are additionally treated with an acidic aqueous solution of an active oxygen releasing per compound treated and after removal from the second aqueous solution treated with a nonionic detergent and then rinsed with water.
  • additional chelating agents can be added to the first and / or second solution, namely preferably aminocarboxylic acid compounds, and the acidic groups can also be used in the form of their water-soluble salts.
  • Other chelating agents mentioned are citric acid or citrates and polyphosphates. But even with this known method, the problem underlying the invention could not be solved satisfactorily.
  • an aqueous-liquid, builder-containing detergent which contains at least one synthetic, detergent-active compound, an alkali metal fatty acid soap, mono-, di- or triethanol- or isopropanolamine, a hydrotrope and, as a builder, sodium tripolyphosphate and tetrapotassium pyrophosphate and optionally contains hydrogen peroxide.
  • This detergent is stable for at least one month at both 0 ° C and 52 ° C. As a washing bleach, it is comparable to a high-performance powder with 17% perborate content.
  • the complexing agent is an alkanolamine, although this - as mentioned above - by itself does not produce a satisfactory effect. This is because it was also found that the extrusion tool is a possible source of the contaminants introduced. The presence of an oxidizing agent is therefore required to bring the traces of heavy metals, in particular iron, into ionic form so that the complexing agent can develop its effect. Iron is treated here and in the following as a "leading impurity" because it is by far the highest concentration compared to other heavy metals and is also difficult to remove. Experiments have shown that removal of the iron usually also removes the other heavy metal contaminants.
  • the hydroxyl groups appear more important than the nitrogen atom (which appears to be more important for other heavy metals such as chromium).
  • two hydroxyl groups on the same nitrogen atom which are bound via "spacer” groups are required.
  • the "spacer” can be an alkylene group with up to 6 carbon atoms, which can be interrupted by oxygen atoms and nitrogen functions, which should be understood to mean, for example, compounds of the type of ethylenediamine tetra (hydroxyalkyl) compounds.
  • alkanolamines such as the adducts of ethylene and propylene oxide with ammonia, primary alkylamines with 1 to 4 carbon atoms and ethylenediamine are preferred.
  • the alkanolamines have the further advantage that they not only do not adhere to the organic substrates, but also detach inorganic and organic impurities adhering to them. In addition, their "dirt-carrying capacity" prevents recontamination of the surfaces that have already been cleaned.
  • the preferred alkanolamine is triethanolamine. It is a mild alkali (a 0.1 N aqueous solution shows a pH of 10.5) and does not cause any skin irritation.
  • Alkali peroxides can be used as inorganic peroxide compounds, but - as with the alkanolamines - the addition of a base is not necessary.
  • hydrogen peroxide is advantageously used. The easiest way to determine the amount of hydrogen peroxide is to carry out preliminary tests under the conditions of use, since this compound is known to be temperature sensitive.
  • the alkanolamines used preferably as complexing agents have a stabilizing effect.
  • concentrations of at least about 5% by weight, based on the finished cleaning solution are expedient. Lower concentrations often require a long exposure time, higher concentrations are generally only required if the substrate is heavily contaminated.
  • the alkaline cleaning solution advantageously has a pH in the range from 7.5 to 12, preferably 8 to 10.
  • alkanolamines react alkaline, the addition of another base is not always necessary when they are used. However, it is often useful to add aqueous ammonia solution, and the amount of the more expensive alkanolamine can be reduced. The cheapest in individual cases The combination can be determined by simple preliminary tests.
  • a preferred embodiment of the invention is that the plastic is used in finely divided form so that the contaminants are extracted by the cleaning solution according to the invention.
  • the cleaning method according to the invention can be used over a wide temperature range.
  • the temperature sensitivity of this molded article will be used and, for example, working in a range from room temperature to approximately 120 ° C., preferably approximately 50 ° C. If a finely divided plastic is extracted, it is advantageous to choose a higher temperature, suitably about 80 to 120 ° C. In general, shorter treatment times are sufficient at higher temperatures.
  • the increased decomposition of the peroxide compound must be taken into account, that is, if necessary, metered in or used in sufficient concentration right from the start.
  • the cleaning method according to the invention is generally applicable to all plastics. It also has an excellent effect on hydrophobic plastics that are used in the packaging sector, such as polyethylenes, polypropylenes, polyvinyl chlorides and polyesters. However, it can also be used with advantage for the so-called high-performance plastics such as polyacetals, polyphenylene sulfides, polyether ketones and, above all, fluoropolymers.
  • a one-stage treatment is generally sufficient.
  • Pretreatment or, if necessary, post-treatment with acidic solutions should not be ruled out. So come for example, a hydrofluoric acid aftertreatment may be considered, it being possible to add peroxides and optionally auxiliaries such as surfactants to the HF solution.
  • a mixture of the composition (in% by weight) has proven itself: 89.5% water 10.0% H2O2, 30% 0.5% HF, 50% Such an aftertreatment can, if necessary, remove residual iron impurities.
  • further additives such as further complexing agents, surfactants, buffers or the like, can also be added to the alkaline solution.
  • Nonionic surfactants such as adducts of ethylene and / or propylene oxide with long-chain alcohols, alkylphenols and the like are particularly suitable as surfactants.
  • multiple treatment of the substrates can also be considered if significant migration of contaminants from the depth of the plastic can be determined, for example after the substrate has been heated.
  • Table 1 contains comparative examples V1 to V3 in which one of the components of the cleaning solution according to the invention is missing.
  • composition of the cleaning solution is defined as follows: "parts" are parts by weight, the hydrogen peroxide being used as a 30% aqueous solution and the ammonia as a 25% aqueous solution.
  • concentration of triethanolamine (TEA) is given in ppm.
  • the extraction result is given in ng iron / g plastic.
  • Table 1 example Parts TEA [ppm] Fe [ng / g] H2O H2O2 NH3 30 min 60 min V1 4th - 1 500 0.56 0.69 V2 4th - 1 1000 0.49 0.62 V3 3rd 1 1 --- 0.82 1.07 1 3rd 1 1 500 1.04 1.29 2nd 3rd 1 1 1000 1.10 1.41 3rd 3rd 1 0.5 1000 1.02 1.39 4th 4th 1 1 1000 0.91 1.32 5 4th 1 1 10,000 1.58 2.01 6 5 1 1 1000 0.82 1.21 7 6 1 1 1000 0.92 0.96
  • Comparative examples V1 and V2 show that an ammoniacal TEA solution shows only a relatively low extraction effect.
  • Comparative example C3 shows that an ammoniacal hydrogen peroxide solution produces significantly poorer extraction results than the cleaning solutions according to the invention.
  • Example 3 The procedure of Example 3 is followed, but extraction is carried out for 75 minutes, a final concentration of extracted iron of 1.5 ng / g of plastic being achieved. By re-using a fresh solution, 0.47 ng / g is extracted after 60 minutes.
  • Example 4 is repeated, but the sample is shaken at about 100 Hz during the extraction. After 30 minutes, 3.59 ng Fe / g plastic are extracted.
  • Vials with a capacity of 50 ml formed from the copolymer are filled with the cleaning solution used in Example 4 and stored at different temperatures for 30 or 60 minutes.
  • Table 2 shows the extraction results. Table 2 example Temperature [° C] Fe [ng / g] 30 min 60 min 10th Room temperature 0.73 1.47 11 50 1.30 1.81 12th 80 1.83 2.35
  • Example 11 is repeated, but the vial is immersed at 3/4 its height in an ultrasonic bath. After 30 minutes 1.58 and after 60 minutes 2.31 ng Fe / g plastic are extracted.
  • Example 3 is repeated, but increasing amounts of a nonionic surfactant (commercial product ®TRITON X 100) are added. The results are shown in Table 3.
  • Table 3 example Surfactant [ppm] Fe [ng / g] 30 min 60 min 3rd 0 1.02 1.39 14 100 1.51 1.59 15 200 1.40 1.67 16 400 1.83 2.42
  • Example 16 With increasing addition of surfactant, foaming increases. In addition, a faster decomposition of the hydrogen peroxide is observed in Example 16.
  • the vials used in Examples 10 to 12 are filled at room temperature with 25 ml of the cleaning solution shown in Table 4 and stored for 30 or 60 minutes.
  • Table 4 shows the extracted chromium content [ng (Cr)], based on the amount of plastic used [g].
  • V4 is a comparative example with water.
  • Table 4 example Parts TEA [ppm] Cr [ng / g] H2O H2O2 NH3 30 min 60 min 17th 3rd 1 1 1000 0.70 0.95 18th 3rd 1 0.25 1000 0.40 0.59 19th 4th 1 1 1000 0.54 0.72 20th 5 1 1 1000 0.45 0.65 V4 1 - - --- 0.031 ---

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Claims (8)

  1. Procédé pour le nettoyage de matières plastiques, caractérisé en ce que l'on met en contact la matière plastique avec une solution aqueuse alcaline qui contient un composé de peroxyde minéral et un agent complexant sans groupes acides libres ou sous forme de sel, et si nécessaire, une base.
  2. Procédé selon la revendication 1, caractérisé en ce que l'on utilise la matière plastique sous forme d'objet façonné que l'on nettoie à la surface.
  3. Procédé selon la revendication 1, caractérisé en ce que l'on utilise la matière plastique sous forme finement divisée et on extrait les impuretés.
  4. Solution de nettoyage aqueuse, alcaline, sans adjuvants actifs, caractérisée par une teneur en
    a) un peroxyde minéral,
    b) un agent complexant sans groupes acides libres ou sous forme de sel et, si nécessaire,
    c) une base.
  5. Solution selon la revendication 4, caractérisée en ce que l'agent complexant est une alcanolamine.
  6. Solution selon la revendication 4 ou 5, caractérisée en ce que l'agent complexant est la triéthanolamine.
  7. Solution selon une ou plusieurs des revendications 4 à 6 caractérisée, en ce que le peroxyde est le peroxyde d'hydrogène.
  8. Solution selon une ou plusieurs des revendications 4 à 7, caractérisée en ce que la solution contient un agent tensio-actif.
EP94117320A 1993-11-08 1994-11-03 Nettoyage de plastique Expired - Lifetime EP0652283B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4338021A DE4338021A1 (de) 1993-11-08 1993-11-08 Reinigung von Kunststoffen
DE4338021 1993-11-08

Publications (2)

Publication Number Publication Date
EP0652283A1 EP0652283A1 (fr) 1995-05-10
EP0652283B1 true EP0652283B1 (fr) 1996-03-20

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ID=6502022

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EP94117320A Expired - Lifetime EP0652283B1 (fr) 1993-11-08 1994-11-03 Nettoyage de plastique

Country Status (3)

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EP (1) EP0652283B1 (fr)
JP (1) JPH07207299A (fr)
DE (2) DE4338021A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1193045C (zh) 2000-06-01 2005-03-16 3M创新有限公司 高纯度氟聚合物的制造方法
CN105251732B (zh) * 2015-11-09 2018-05-11 奉化市旭日鸿宇有限公司 一种塑料颗粒原料的清洗方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3908680A (en) * 1973-10-12 1975-09-30 Flow Pharma Inc Methods for cleaning and bleaching plastic articles
US4298492A (en) * 1979-06-21 1981-11-03 Lever Brothers Company Built liquid detergent composition
DE4117972A1 (de) * 1991-05-31 1992-12-03 Hildegard John Haushaltsreiniger

Also Published As

Publication number Publication date
JPH07207299A (ja) 1995-08-08
DE4338021A1 (de) 1995-05-11
DE59400166D1 (de) 1996-04-25
EP0652283A1 (fr) 1995-05-10

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