WO2014067948A2 - Mousses particulaires à finition anticorrosion - Google Patents

Mousses particulaires à finition anticorrosion Download PDF

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Publication number
WO2014067948A2
WO2014067948A2 PCT/EP2013/072614 EP2013072614W WO2014067948A2 WO 2014067948 A2 WO2014067948 A2 WO 2014067948A2 EP 2013072614 W EP2013072614 W EP 2013072614W WO 2014067948 A2 WO2014067948 A2 WO 2014067948A2
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WO
WIPO (PCT)
Prior art keywords
expandable
weight
styrene
prefoamed
foam
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.)
Ceased
Application number
PCT/EP2013/072614
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German (de)
English (en)
Other versions
WO2014067948A3 (fr
Inventor
Dietrich Scherzer
Klaus Hahn
Anita KRÖNER
Joachim Ruch
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BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP13783600.3A priority Critical patent/EP2917270A2/fr
Publication of WO2014067948A2 publication Critical patent/WO2014067948A2/fr
Anticipated expiration legal-status Critical
Publication of WO2014067948A3 publication Critical patent/WO2014067948A3/fr
Ceased legal-status Critical Current

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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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0004—Use of compounding ingredients, the chemical constitution of which is unknown, broadly defined, or irrelevant
    • 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
    • C08J9/16—Making expandable particles
    • 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
    • C08J2325/00—Characterised by the use of homopolymers or copolymers 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; Derivatives of such polymers
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • 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
    • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes

Definitions

  • the present invention relates to a particle foam containing corrosion inhibitors, as well as methods for its production and use for packaging of corrosive metal objects.
  • VCI Volatile Corrosion Inhibitor
  • EP 2 184 162 A1 describes a packaging material for articles susceptible to corrosion of metal.
  • the outer side of the packaging is formed by a plastic film, for example a thin polypropylene film, which is coated with an adhesive layer, for example a 1-pack
  • Polyurethane adhesive is connected to a plastic fleece.
  • a small amount of a VCI active substance was introduced, which ensures a rapid build-up of complete protection against corrosion via the gas phase and also a long-term protection.
  • US 2009/01 1 1901 describes an open or closed cell foam structure, preferably of a polyolefin, in which an effective amount of a volatile corrosion inhibitor is incorporated in the polymer and released by controlled migration on the surface of the foam.
  • the object of the present invention was to provide an elastic packaging material with corrosion-inhibiting equipment as well as processes for its production, which ensures a sufficient corrosion protection effect over a longer period of time.
  • the object has been achieved by a particle foam which contains 0.5 to 8% by weight of one or more corrosion inhibitors selected from amines, triazoles, carboxylic acid esters, carboxylic acid salts, nitrites, alcohols or mixtures thereof.
  • the particle foam contains in total preferably 0.5 to 8 wt .-%, particularly preferably 1 to 6 wt .-% of the preferably volatile corrosion inhibitors.
  • Suitable corrosion inhibitors are the commercially available VC I active substances (volatile corrosion inhibitor), for example nitrite compounds, amines, ammonium salts or carboxylic acid salts. Table 1 shows suitable substances which, individually or in combination, are effective as corrosion inhibitors for metals.
  • Triazoles such as benzotriazole, 2-mercaptobenzotriazole, methylbenzotriazole and derivatives, aminobenzotriazoles, 4-amino-5-mercaptopropyl-triazole
  • Immidazoles such as benzimidazole, 2-benzimidazole-thiol,
  • amines such as dodecylamines, tridodeclamine, polyamines, ethylenediamine, diaminohexane and their salts,
  • Quaternary ammonium salts such as ammonium lactates, ammonium formate, ammonium acetate, ammonium oxalate, ammonium benzoate, diammonium citrate,
  • Ammonium Phosphate Ammonium Dihydrogen Phosphate, Ammonium Amidosulphate, Ammonium Sulfate, Diammonium Hydrogen Phosphates, Ammonium Hydrogen Sulfates, Ammonium Sulfite, Ammonium Tartrate, Ammonium Succinate, Ammonium Adipate, Diammonium Ethylenediaminetetraacetate, Ammonium Borate,
  • Nitrites such as sodium nitrite, ammonium nitrite, nitrite esters and organic nitro compounds
  • Carboxylic acids and their salts such as sodium benzoate, sodium salicylate, sodium macropate, nitrobenzoates
  • Benzotriazole, sodium nitrite, sodium benzoate or mixtures thereof are particularly preferably used as corrosion inhibitors.
  • the density of the particle foam is generally in the range of 10 to 100 kg / m 3 .
  • the particle foam according to the invention is formed by thermoplastic foam particles, preferably foam particles of prefoamed, expandable styrene polymers, in particular expandable polystyrene (EPS), prefoamed expandable polystyrene / polyethylene mixtures or expanded polyolefins.
  • EPS expandable polystyrene
  • Particular preference is given to using elastic particle foams made from expandable polystyrene / polyethylene mixtures, as described, for example, in WO 2004/085527, WO 2004/085528 or WO 2009/1 12549.
  • Preferred foam particles P are obtained by prefoaming expandable, thermoplastic polymer particles which
  • the expandable thermoplastic polymer particles, from which the foam particles P are obtained by prefoaming consist of the components A) to E).
  • the blowing agent (component D) has essentially escaped during the pre-foaming.
  • the expandable thermoplastic polymer particles contain 45 to 97.9 wt .-%, preferably 55 to 78.1 wt .-% of a styrene polymer A), such as standard (GPPS) - or impact polystyrene (HIPS) or styrene-acrylonitrile copolymers (SAN ) or acrylonitrile-butadiene-styrene copolymers (ABS) or mixtures thereof.
  • GPPS standard
  • HIPS impact polystyrene
  • SAN styrene-acrylonitrile copolymers
  • ABS acrylonitrile-butadiene-styrene copolymers
  • the expandable, thermoplastic polymer particles used to produce the foam particles P1 preferably contain styrene polymer A) as standard polystyrene (GPPS).
  • polystyrene types having weight average molecular weights in the range of 120,000 to 300,000 g / mol, in particular 190,000 to 280,000 g / mol, determined by gel permeation chromatography; and a melt volume rate MVR (200 ° C / 5 kg) according to ISO 1 13 used in the range of 1 to 10 cm 3/10 min, for example PS 158 K, 168 N or 148 G of BASF SE.
  • easily flowing types for example Empera® 156L (Innovene) can be added
  • the expandable thermoplastic polymer particles comprise polyolefins B1) having a melting point in the range from 105 to 140 ° C. and polyolefins B2) having a melting point below 105 ° C.
  • the melting point is the melting peak determined by DSC (Dynamic Scanning Calorimetry) at a heating rate of 10 ° C./minute.
  • the expandable, thermoplastic polymer particles contain 1 to 45 weight percent, in particular 7 to 15 wt .-% of a polyolefin B1).
  • the polyolefin B1) used is preferably a homo- or copolymer of ethylene and / or propylene having a density in the range from 0.91 to 0.98 g / l (determined according to ASTM D792), in particular polyethylene.
  • ASTM D792 As a polypropylene In particular injection molding grades come into consideration.
  • Suitable polyethylenes are commercially available homopolymers of ethylene, such as PE-LD (injection molding types), LLD, -HD, or copolymers of ethylene and propylene (for example Moplen® RP220 and Moplen® RP320 from Basell or Verify®). Dow types), ethylene and vinyl acetate (EVA), ethylene acrylates (EA) or ethylene-butylene acrylates (EBA).
  • the melt volume index MVI (190 ° C / 2.16 kg) of the polyethylenes is usually in the range of 0.5 to 40 g / 10 min, the density in the range of 0.91 to 0.95 g / cm 3 .
  • blends with polyisobutene (PIB) (eg Oppanol® B150 from BASF Akten GmbH) can be used.
  • PIB polyisobutene
  • olefin block copolymers which are composed of a polyolefin block PB1 (hard block) and a polyolefin block PB2 (soft block), as described, for example, in WO 2006/099631.
  • the polyolefin block PB1 preferably consists of 95 to 100% by weight of ethylene.
  • the PB2 block is preferably composed of ethylene and ⁇ -olefin, where as ⁇ -olefins styrene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, norbornene, 1-decene, 1, 5-hexadiene or mixtures thereof.
  • PB2 block is an ethylene- ⁇ -olefin copolymer block with 5 to 60 wt .-% ⁇ -olefin, in particular an ethylene-octene copolymer block.
  • the blocks PB1 and PB2 essentially form a linear chain and are preferably distributed alternately or statistically.
  • the proportion of the PB2 blocks is preferably 40 to 60% by weight, based on the olefin block copolymer.
  • Particularly preferred are olefin block copolymers with alternating, hard PB1 blocks and soft, elastomeric PB2 blocks, which are commercially available under the name INFUSE®.
  • the expandable, thermoplastic polymer particles contain 0 to 25 percent by weight, in particular 1 to 10 wt .-% of a polyolefin B2) having a melting point below 105 ° C.
  • the polyolefin B2) preferably has a density in the range of 0.86 to 0.90 g / L (determined according to ASTM D792).
  • thermoplastic elastomers based on olefins (TPO) are suitable.
  • TPO olefins
  • Engage® 841 1 from the company Dow.
  • Expandable, thermoplastic polymer particles containing the component B2) show a significant improvement in the bending work and tear resistance after processing into foam moldings.
  • compatibilizers components C
  • a further improvement in compatibility is achieved by using a mixture of styrene-butadiene or styrene-isoprene block copolymers as component C1) and styrene-ethylene-butylene block copolymers (SEBS) as component C2).
  • the expandable thermoplastic polymer particles contain as component C1) 0.1 to 25 percent by weight, in particular 6 to 15 wt .-% of a styrene-butadiene or styrene-isoprene block copolymers.
  • styrene-butadiene or styrene-isoprene block copolymers are suitable for this purpose.
  • the total diene content is preferably in the range from 20 to 60% by weight, particularly preferably in the range from 30 to 50% by weight, the total styrene content is correspondingly preferably in the range from 40 to 80% by weight, particularly preferably in the region of 50 to 70% by weight.
  • Preferred compatibilizers are styrene-butadiene-styrene (SBS) triblock copolymers having a butadiene content of from 20 to 60% by weight, preferably from 30 to 50% by weight, which may be partially hydrogenated or unhydrogenated.
  • SBS styrene-butadiene-styrene
  • These are for example under the name Styroflex® 2G66, Styrolux® 3G55, Styroclear® GH62, Kraton® D 1 101, Kraton® D 1 155, Tuftec® H1043 or Europren® SOL T6414 commercially.
  • SBS block copolymers with sharp transitions between B and S blocks.
  • the expandable, thermoplastic polymer particles contain 0 to 10 percent by weight, in particular 0.8 to 3 percent by weight, of a styrene-ethylene-butylene block copolymer (SEBS).
  • SEBS styrene-ethylene-butylene block copolymers
  • Suitable styrene-ethylene-butylene block copolymers (SEBS) are, for example, those obtainable by hydrogenation of the olefinic double bonds of the block copolymers C1).
  • Suitable styrene-ethylene-butylene block copolymers are, for example, the commercially available Kraton® G types, in particular Kraton® G 1650.
  • the multiphase polymer mixture may contain additives, nucleating agents, plasticizers, halogen-containing or halogen-free flame retardants, soluble and insoluble inorganic and / or organic compounds Dyes and pigments, fillers or Cotreibstoff be added in amounts that do not affect the domain formation and resulting foam structure.
  • the expandable, thermoplastic polymer particles contain 0 to 5 percent by weight, preferably 0.3 to 2 percent by weight of a nucleating agent or nucleating agent, for example talc.
  • the expandable, thermoplastic polymer particles contain 1 to 15 percent by weight, preferably 3 to 10 percent by weight, based on the sum of all components A) to E) of a physical blowing agent.
  • the propellants can at Room temperature (20 to 30 ° C) and atmospheric pressure gaseous or liquid. They should have a boiling point below the softening temperature of the polymer blend, usually in the range of -40 to 80 ° C, preferably in the range of -10 to 40 ° C.
  • Suitable blowing agents are, for example, halogenated or halogen-free aliphatic hydrocarbons, alcohols, ketones or ethers.
  • Suitable aliphatic blowing agents are, for example, aliphatic C3 to C5 hydrocarbons, such as n-propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, neopentane, cycloaliphatic hydrocarbons, such as cyclobutane and cyclopentane, halogenated hydrocarbons, such as methyl chloride, ethyl chloride, methylene chloride, trichlorofluoromethane, dichlorofluoromethane, dichlorodifluoromethane, chlorodifluoromethane, dichlorotetrafluoroethane and mixtures thereof.
  • the halogen-free blowing agents are preferably isobutane, n
  • Suitable co-blowing agents are those having a lower selectivity of solubility for the domain-forming phase, for example gases such as CO 2, N 2, fluorohydrocarbons or noble gases. These are preferably used in amounts of 0 to 10 wt .-%, based on the expandable thermoplastic polymer particles.
  • the final expandable thermoplastic polymer particles may be coated by glycerol esters, antistatic agents or anticaking agents.
  • the resulting round or oval particles are foamed to a diameter in the range of 0.2 to 10 mm.
  • Their bulk density is preferably in the range of 10 to 100 kg / m 3 .
  • the expandable, thermoplastic polymer particles can be prefoamed by means of hot air or steam to foam particles having a density in the range of 10 to 100 kg / m 3 , preferably in the range of 15 to 80 kg / m 3 and then welded in a closed mold into foam moldings.
  • the foam particles P may also contain additives, nucleating agents, plasticizers, Halogenhalti- ge or halogen-free flame retardants, soluble and insoluble inorganic and / or organic dyes and pigments or fillers in conventional amounts.
  • the particle foam according to the invention can be prepared, for example, by reacting expandable styrene polymers or expandable polystyrene / polyethylene
  • prefoamed, expandable styrene polymers, prefoamed expandable polystyrene / polyethylene mixtures or expanded polyolefins can be coated during or after prefoaming with one or more, preferably volatile, corrosion inhibitors.
  • a further possibility consists in homogeneously mixing the, preferably volatile, corrosion inhibitors with the molten polymers during the preparation of the expandable styrene polymerates, of the expandable polystyrene / polyethylene mixtures or of the expanded polyolefins.
  • the particle foam according to the invention can be used for the packaging of corrosive metal objects. It is particularly suitable for the packaging of high-priced goods, for example engine parts, for overseas shipments, for in-house transport or for the storage of spare parts.
  • Expandable PS / PE granules
  • Expandable polystyrene / polyethylene blends (PS / PE), obtainable according to Example 2 of WO 2009/1 12549, were used for the following examples.
  • the propellant-containing PS / PE granules were prefoamed in a commercially available EPS-DruckvorCumer (Kurtz) to foam beads.
  • the foam beads were processed after 24 hours storage in a molding machine to block-shaped packaging molded parts (container).
  • the density of the packaging moldings was about 20 kg / m 3 .
  • Standard steel plates were placed in two-part packaging moldings and sealed with adhesive tape. This was followed by a 35-day storage in the climate change cabinet (6 hours 25 ° C / 98% relative humidity, 6 hours 55 ° C / 95% relative humidity, VW / Audi test standard).
  • Example 1 a 3 wt .-% (Example 1 a) and 6 wt .-% (Example 1 b), based on the foam bead, a mixture consisting of 20 wt .-% benzotriazole, 30 wt .-% sodium nitrite and 50 wt .-% Sodium benzoate was incorporated into the polymer matrix during the preparation of the expandable PS / PE granules. From the material thus produced, the containers described above were foamed, which were used for storing the steel plates in the climatic chamber. The containers subjected to the environmental change test were opened weekly and the steel samples were evaluated. In the assessment, the percentage area of the corroded surfaces was given in percent (Table 2).
  • a mixture consisting of 20 g of benzotriazole, 30 g of sodium nitrite and 50 g of sodium benzoate was intimately mixed together with 20 g of glycerol monostearate and 30 g of glycerol tristearate in a laboratory mixer.
  • Example 2a In a Lödige mixer system, 2% by weight (based on the pure corrosion inhibitor mixture (powder)) was applied to the expandable PS / PE granules (Example 2a). From the material thus produced, the containers described above were foamed, which were used for storing the steel plates in the climatic chamber. The containers subjected to the environmental change test were opened weekly and the steel samples were evaluated. In the assessment, the percentage area of the corroded surfaces was reported (Table 3).
  • Example 2b correspondingly 4% by weight (Example 2b) and 6% by weight (Example 2c) of this mixture were applied.
  • the density of the foam was 20 g / l.
  • Table 3 The density of the foam was 20 g / l.
  • a mixture consisting of 20 g of benzotriazole, 30 g of sodium nitrite and 50 g of sodium benzoate was stirred into 100 ml of water.
  • an aqueous solution of the corrosion inhibitor was injected by means of a nozzle into the stirred pressure prefoamer (Kurtz company).
  • the intumescent beads were coated with in each case 1% by weight (Example 3a), 3% by weight (Example 3b) and 6% by weight (Example 3c), based on the foam bead, of the pure corrosion inhibitor.
  • the density of the foam was 20 g / l.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Wrappers (AREA)

Abstract

La présente invention concerne une mousse particulaire qui contient 0,5 à 8% en poids d'un ou plusieurs inhibiteurs de corrosion choisis parmi les amines, les triazoles, les esters d'acide carboxylique, les sels d'acide carboxylique, les nitrites, les alcools ou des mélanges de ceux-ci, ainsi que des procédés de production de cette mousse et son utilisation pour emballer des objets métalliques sensibles à la corrosion.
PCT/EP2013/072614 2012-11-05 2013-10-29 Mousses particulaires à finition anticorrosion Ceased WO2014067948A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP13783600.3A EP2917270A2 (fr) 2012-11-05 2013-10-29 Mousses particulaires à additif anticorrosion

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP12191229.9 2012-11-05
EP12191229 2012-11-05

Publications (2)

Publication Number Publication Date
WO2014067948A2 true WO2014067948A2 (fr) 2014-05-08
WO2014067948A3 WO2014067948A3 (fr) 2015-05-28

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EP (1) EP2917270A2 (fr)
TW (1) TW201431918A (fr)
WO (1) WO2014067948A2 (fr)

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TR202014638A2 (tr) 2020-09-15 2021-04-21 Sun Tekstil San Ve Tic A S Bi̇r koruyucu teksti̇l yapisi ve üreti̇m yöntemi̇

Family Cites Families (6)

* Cited by examiner, † Cited by third party
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JPS6328888A (ja) * 1986-07-21 1988-02-06 Sekisui Plastics Co Ltd 防錆性能を有する発泡性熱可塑性樹脂粒子の製造方法
US5258415A (en) * 1991-11-14 1993-11-02 Basf Aktiengesellschaft Expandable styrene polymers containing carbon dioxide as blowing agent
US5593624A (en) * 1995-05-24 1997-01-14 Lewis; Eugene R. Method for making cellular packaging board with inhibitor
AT406477B (de) * 1999-01-25 2000-05-25 Sunpor Kunststoff Gmbh Teilchenförmige, expandierbare styrolpolymerisate und verfahren zu ihrer herstellung
WO2010100101A1 (fr) * 2009-03-05 2010-09-10 Basf Se Produit mousse élastique en particules, à base de mélanges de polymères de polyoléfine/styrène
JP5713909B2 (ja) * 2009-09-08 2015-05-07 積水化成品工業株式会社 発泡成形体及びその製造方法

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TW201431918A (zh) 2014-08-16
WO2014067948A3 (fr) 2015-05-28
EP2917270A2 (fr) 2015-09-16

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