WO1995008589A1 - Polymeres expansibles de styrene en perles contenant des phenols steriquement inhibes - Google Patents

Polymeres expansibles de styrene en perles contenant des phenols steriquement inhibes Download PDF

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Publication number
WO1995008589A1
WO1995008589A1 PCT/EP1994/002987 EP9402987W WO9508589A1 WO 1995008589 A1 WO1995008589 A1 WO 1995008589A1 EP 9402987 W EP9402987 W EP 9402987W WO 9508589 A1 WO9508589 A1 WO 9508589A1
Authority
WO
WIPO (PCT)
Prior art keywords
styrene
weight
sterically hindered
expandable
styrene polymers
Prior art date
Application number
PCT/EP1994/002987
Other languages
German (de)
English (en)
Inventor
Dietrich Scherzer
Rolf Henn
Michael Witt
Klaus Hahn
Michael Riethues
Original Assignee
Basf Aktiengesellschaft
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 Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to JP7509528A priority Critical patent/JPH09504814A/ja
Priority to EP94927578A priority patent/EP0719298A1/fr
Priority to AU76949/94A priority patent/AU7694994A/en
Priority to KR1019960701394A priority patent/KR960704968A/ko
Publication of WO1995008589A1 publication Critical patent/WO1995008589A1/fr

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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
    • 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
    • C08J9/20—Making expandable particles by suspension polymerisation in the presence of the blowing agent
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/224—Surface treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • 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
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene

Definitions

  • the invention relates to bead-shaped, expandable styrene polymers containing sterically hindered phenols and processes for their preparation.
  • EPS expandable polystyrene
  • the styrene polymer can be impregnated with a blowing agent in the extruder, so that, for example, extruded styrene polymer foam can be produced.
  • the melted styrene polymer can first be extruded and the granules obtained therefrom can be impregnated with a blowing agent in a subsequent step. This is generally carried out in aqueous suspension.
  • the thermal treatment in this recycling of EPS foam materials basically means a thermal, but also a mechanical load on the styrene polymer, which can lead to considerable degradation of the polymer.
  • the degradation of the polymer is promoted by residual initiator, heavy metals and / or atmospheric oxygen that may still be present in the foam.
  • the thermal degradation can be reduced by adding stabilizers or antioxidants.
  • a method for stabilizing recycled plastic mixtures is known from EP-A-0 506 614. Here, recycled plastic mixtures from household and commercial waste are stabilized against the addition of a combination of a sterically hindered phenol with a phosphite or phosphonite against thermal-oxidative degradation.
  • ÜS-A-4 839 396 describes expandable and expanded alkenyl aromatic polymer particles and methods for their preparation.
  • the expandable polymer particles disclosed therein can be used to produce expanded polymer particles otherwise having the same density using reduced amounts of blowing agent. This is done by using a density controller in an amount of 0.005 to 0.5% by weight based on the total weight of the Mix reached.
  • a density controller z.
  • B the sterically hindered phenol octadecyl-3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl propionate (Irganox® 1076 from CIBA-GEIGY AG) is used.
  • the particles are produced by mixing the alkenyl aromatic polymer with a blowing agent and the sterically hindered phenol in the melt and then extruding it. In this way, however, no pearl-shaped expandable styrene polymers are obtained.
  • the object of the present invention was to provide bead-shaped, expandable styrene polymers which are suitable for the production of moldings which tend to reduce the decomposition reactions of the styrene polymers as little as possible during recycling in the melt.
  • the invention also relates to a process for the preparation of these sterically hindered phenols-containing, expandable styrene polymers by styrene, optionally with the use of further comonomers, in aqueous suspension in the presence of suspension stabilizers and customary styrene-soluble polymerization catalysts and with Zu ⁇ set of a blowing agent or blowing agent mixture and, if appropriate, conventional additives in effective amounts and, if appropriate, up to 1.5% by weight, based on styrene and comonomers, of polymerized sterically hindered phenols, and the pearly, expandable styrene polymers obtained in this way are coated with up to 1.5% by weight, based on the blowing agent-free styrene polymer a), of sterically hindered phenols, with the proviso that the expandable styrene polymers are coated in homogeneous distribution in the styrene polymer
  • the pearly, expandable styrene polymers generally contain polystyrene and / or a styrene copolymer with at least 50% by weight, preferably at least 80% by weight, of copolymerized styrene as styrene polymer a).
  • Comonomers such. B. in question ⁇ -methyl styrene, nuclear halogenated styrenes, nuclear alkylated styrenes, acrylonitrile, esters of acrylic or methacrylic acid of alcohols with 1 to 8 carbon atoms, N-vinyl carbazole and maleic acid (anhydride).
  • Sterically hindered phenols b) according to the invention are, for example, 3,5-dialkyl-4-hydroxyphenyl compounds.
  • octa-decyl-3, 5-bis (1, 1-dimethylethyl) -4-hydroxy-phenyl-propionate is used very particularly preferably.
  • the bead-like, expandable styrene polymers contain a blowing agent or blowing agent mixture c) which is generally used in an amount of 2 to 10% by weight, preferably 3 to 8% by weight, based on the sum of a) and b) becomes.
  • the blowing agents should not dissolve the styrene polymer, but should be soluble in the styrene polymer.
  • the boiling point should be below the softening point of the styrene polymer.
  • Suitable blowing agents are, for example, propane, butane, pentane, hexane, cyclohexane and octane. Pentane is preferably used.
  • the expandable styrene polymers can furthermore contain customary additives d) in effective amounts, such as flame retardants, dyes, fillers, stabilizers, synergists, nucleating agents, lubricants, antistatic agents, substances which have an anti-adhesive action when foaming and agents for reducing the mold release time when foaming .
  • customary additives d) such as flame retardants, dyes, fillers, stabilizers, synergists, nucleating agents, lubricants, antistatic agents, substances which have an anti-adhesive action when foaming and agents for reducing the mold release time when foaming .
  • Organic bromine and / or chlorine compounds are generally used as flame retardants.
  • the organic bromine compounds used are the bromine compounds usually used as flame retardants, which generally contain at least 2 bromine atoms and have a bromine content of at least 40% by weight.
  • Suitable bromine compounds are 1,2,3,4-tetrabromobutane, 1,2,4-tribromobutane, tetrabromopentane, bromine-substituted cycloalkanes, such as l-chloro-2,3,4,4,5,6-pentabromocyclohexane, 1,2,3 , 4,5, 6-hexabromocyclohexane, 1,2,5, 6, 9, 10-hexabromocyclododecane, octabromocyclohexadecane, dibromomethylbenzene, pentabromodiphenyl ether, esters and acetals of dibromopropanol, such as tris (2, 3-d
  • the bead-like, expandable styrene polymers additionally contain 0.05 to 1.0, preferably 0.1 to 0.8, particularly preferably 0.2 to 0.6% by weight, based on a), of phosphites e).
  • phosphites e preferably triaryl phosphites, particularly preferably trisnonylphenyl phosphite, are preferably used as phosphites.
  • the pearl-shaped, expandable styrene polymers generally have a diameter of 0.1 to 6 mm, in particular 0.4 to 3 mm.
  • the bead-like, expandable styrene polymers according to the invention are generally prepared by polymerizing styrene and, if appropriate, further comonomers in aqueous suspension.
  • the sterically hindered phenol b) is added to the suspension before or during the polymerization and / or applied to the beads as a coating component, with the proviso that the expandable styrene polymers are obtained in homogeneous distribution in the styrene polymer and / or as a surface coating on the styrene polymer a), 0.03 to 1.5, preferably 0.05 to 1.2 and particularly preferably 0.1 to 1.0% by weight of sterically hindered phenols b).
  • the blowing agent can be included in the polymerization or added in the course of the polymerization. It can also be added to the batch only after the polymerization has ended.
  • the bead-like, expandable styrene polymers obtained in the suspension polymerization are separated from the aqueous phase, washed and dried.
  • the surface coating of the expandable styrene polymers can be carried out in a conventional manner.
  • 0.05 to 1.2% by weight, particularly preferably 0.1 to 1.0% by weight, in each case based on styrene and comonomers are sterically hindered in the suspension polymerization Phenols and up to 1.15% by weight, particularly preferably up to 0.9% by weight, in each case based on the styrene polymer a), as surface coating on the beads obtained in the suspension polymerization, sterically hindered phenols applied.
  • the sterically hindered phenol is added to the suspension before or during the polymerization, it is particularly surprising that the sterically hindered phenols used according to the invention as free radical scavengers do not impair the suspension polymerization which proceeds via free radicals.
  • the expandable styrene polymers are expanded in a known manner by heating to temperatures above their softening point, for example using hot air or preferably using steam.
  • the foam particles obtained can be foamed further by cooling and, if appropriate, intermediate storage by heating again. They can then be welded in a known manner into moldings in non-gastight forms.
  • the stirred kettle was closed, a nitrogen pressure of 1 bar was set, and the temperature was raised from 25 to 100 ° C. in 2 hours. The mixture was then heated to 130 ° C. in 5 hours and left at this temperature for 3 hours. 55 minutes after the start of heating, 478 g of polyvinylpyrrolidone and 3 hours after the start of heating, 1300 g of pentane were added.
  • the bead polymer obtained was separated from the aqueous phase, washed, dried and coated with 0.1% by weight, based on the bead polymer, of ethylene-bis-stearic acid amide.
  • the viscosity number VZ (0.5% by weight at 25 ° C. in toluene) was determined in accordance with DIN 53 726 on part of the beads obtained.
  • Example 2 The procedure was as in Example 1. However, the sterically hindered phenol was not initially introduced into the suspension polymerization, but only in an amount of 0.5% by weight, based on the bead polymer, in a mixture with ethylene bis-stearic acid amide applied as a coating to the beads obtained in suspension polymerization.
  • Example 2 The procedure was as in Example 2, with an additional 0.5% by weight, based on the bead polymer, of tris-nonylphenyl phosphite being used in the coating mixture.

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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)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Des polymères expansibles de styrène en perles contienent (a) un polymère de styrène; (b) 0,03 à 1,5 % en poids, par rapport à (a), d'un phénol stériquement inhibé, uniformément réparti dans le polymère de styrène et/ou sous forme d'un revêtement de surface; (c) un agent gonflant ou un mélange d'agents gonflants, et, le cas échéant, (d) des quantités efficaces d'additifs usuels. Selon un procédé de préparation de ces polymères, on polymérise du styrène, le cas échéant avec d'autres comonomères, dans une suspension aqueuse en présence de stabilisateurs de la suspension et de catalyseurs usuels de la polymérisation solubles dans du styrène, avec addition d'un agent gonflant ou d'un mélange d'agents gonflants, de même que, le cas échéant, de quantités efficaces d'additifs usuels et de jusqu'à 1,5 % en poids, par rapport au styrène et aux comonomères, de phénols stériquement inhibés. On enduit ensuite les polymères expansibles de styrène en perles ainsi obtenus avec au maximum 1,5 % en poids, par rapport au polymère exempt d'agent gonflant, de phénols stériquement inhibés, à condition que les polymères expansibles de styrène uniformément répartis dans le polymère de styrène et/ou présents sous forme de revêtement de surface contiennent en tout 0,03 % à 1,5 % en poids de phénols stériquement inhibés, par rapport au polymère de styrène.
PCT/EP1994/002987 1993-09-18 1994-09-07 Polymeres expansibles de styrene en perles contenant des phenols steriquement inhibes WO1995008589A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP7509528A JPH09504814A (ja) 1993-09-18 1994-09-07 立体障害フェノールを含有するパール状の発泡性スチレン重合体
EP94927578A EP0719298A1 (fr) 1993-09-18 1994-09-07 Polymeres expansibles de styrene en perles contenant des phenols steriquement inhibes
AU76949/94A AU7694994A (en) 1993-09-18 1994-09-07 Pearl-shaped, expandable styrene polymers containing sterically hinhibited phenols
KR1019960701394A KR960704968A (ko) 1993-09-18 1994-09-07 입체장애된 페놀을 포함하는 발포성 스티렌 중합체 비이드 및 이것의 제조 방법(peral-shaped, expandable styrene polymers containing sterically inhibited phenols)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4331808A DE4331808A1 (de) 1993-09-18 1993-09-18 Perlförmige, expandierbare Styrolpolymerisate, enthaltend sterisch gehinderte Phenole und Verfahren zu ihrer Herstellung
DEP4331808.8 1993-09-18

Publications (1)

Publication Number Publication Date
WO1995008589A1 true WO1995008589A1 (fr) 1995-03-30

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ID=6498059

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1994/002987 WO1995008589A1 (fr) 1993-09-18 1994-09-07 Polymeres expansibles de styrene en perles contenant des phenols steriquement inhibes

Country Status (7)

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EP (1) EP0719298A1 (fr)
JP (1) JPH09504814A (fr)
KR (1) KR960704968A (fr)
AU (1) AU7694994A (fr)
CA (1) CA2171867A1 (fr)
DE (1) DE4331808A1 (fr)
WO (1) WO1995008589A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6588245B2 (ja) * 2015-06-15 2019-10-09 株式会社ジェイエスピー ポリスチレン系樹脂発泡体の製造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2352858A1 (fr) * 1976-05-24 1977-12-23 Arco Polymers Inc Anti-oxydants phenoliques pour composes halogenes non-polymeres durant l'impregnation de particules de polymeres de styrene
GB2137213A (en) * 1983-03-23 1984-10-03 Polysar Ltd Process for producing stabilized polystyrene compositions
US4839396A (en) * 1988-08-22 1989-06-13 The Dow Chemical Company Expandable and expanded alkenyl aromatic polymer particles and methods of making the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2352858A1 (fr) * 1976-05-24 1977-12-23 Arco Polymers Inc Anti-oxydants phenoliques pour composes halogenes non-polymeres durant l'impregnation de particules de polymeres de styrene
GB2137213A (en) * 1983-03-23 1984-10-03 Polysar Ltd Process for producing stabilized polystyrene compositions
US4839396A (en) * 1988-08-22 1989-06-13 The Dow Chemical Company Expandable and expanded alkenyl aromatic polymer particles and methods of making the same

Also Published As

Publication number Publication date
DE4331808A1 (de) 1995-03-23
KR960704968A (ko) 1996-10-09
AU7694994A (en) 1995-04-10
CA2171867A1 (fr) 1995-03-30
EP0719298A1 (fr) 1996-07-03
JPH09504814A (ja) 1997-05-13

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