CA2003488A1 - Process for the preparation of expandable styrene polymers - Google Patents

Process for the preparation of expandable styrene polymers

Info

Publication number
CA2003488A1
CA2003488A1 CA002003488A CA2003488A CA2003488A1 CA 2003488 A1 CA2003488 A1 CA 2003488A1 CA 002003488 A CA002003488 A CA 002003488A CA 2003488 A CA2003488 A CA 2003488A CA 2003488 A1 CA2003488 A1 CA 2003488A1
Authority
CA
Canada
Prior art keywords
extrudate
styrene polymers
section
preparation
set forth
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.)
Abandoned
Application number
CA002003488A
Other languages
French (fr)
Inventor
Klaus Hahn
Uwe Guhr
Herbert Naarmann
Georg Ruppert
Wolf-Dieter Back
Gerhard Dembek
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.)
BASF SE
Original Assignee
Individual
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 Individual filed Critical Individual
Publication of CA2003488A1 publication Critical patent/CA2003488A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16Making expandable particles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00Making granules
    • B29B9/02Making granules by dividing preformed material
    • B29B9/06Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34Auxiliary operations
    • B29C44/3461Making or treating expandable particles
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/01Hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/02Halogenated hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00Characterised 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
    • C08J2325/02Homopolymers or copolymers of hydrocarbons
    • C08J2325/04Homopolymers or copolymers of styrene

Landscapes

  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Graft Or Block Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

PROCESS FOR THE PREPARATION OF
EXPANDABLE STYRENE POLYMERS

Abstract Of The Disclosoure A process for preparing expandable styrene polymers by extruding a mixture of a styrene polymer, blowing agent, organic bromine compound and dicumyl as a synergist, cooling the extrudate so that it does not foam and while the inside of the extrudate is still plastic deforming it by stretching and/or milling, then reducing the extrudate in size.

Description

Z~

PROCESS FOR THE PREPARATION O~
EXPANDABLE STYRENE POLYMERS
Background f The Invention l. Field of the Invention The present invention relates to an improved process for the preparation of expandable styrene polymers by extrusion.
2. Description of Related Art Federal Republic of Germany 21 54 754 discloses a process for the preparation of expandable styrene polymers by extrusion in which cylindrical extrudate is deformed by milling and/or stretching into extrudate having an oval cross section and then said extrudate is cut into slices in the direction of the smaller axis of the oval cross section. The styrene polymers can contain bromine compounds together with synergistic additives as flame retardants.
In the commercial preparation of expandable styrene polymers which contain organic bromine compounds as flame retardants, one observes considerable corrosion in the extruder screw when extruding" As a result of bubble formation, the foam particles obtained by foaming have an inhomogeneous foam structure and in turn they have an increased particle break rate when used as loose fill packing materialO
U.S. Patent 3,441,524 discloses self-extinguishing styrene polymers comprising organic bromine compounds and su~stituted dipherlyl ethanes. However, this patent offers no solution for the extruder corrosion problem when extruding expandable styrene polymers containing bromine compounds.
An object of the present invention is to overcome these disadvantages. This object was surprisingly met by using dicumyl as a synergistic additive.

Summary Of The Invention A process for the preparation of expandable styrene polymers, having an organic bromine compound as a fire retardant and a synergistic additive in which a mixture of a styrene polymer, blowing agent, flame retardant and additive are extruded; the extrudate is quickly cooled so that it does not foam and while the inside of said extrudate is still plastic it is deformed by stretching and/or milling and then reduced in size, wherein dicumyl is used as said synergistic additive.

Detailed Description Styrene polymers are understood to be polystyrene and mixed polymers of styrene which contain polymerized in situ at least 50 weight percent, more preferably at least 75 weight percent of styrene. Typical mixed polymerization components are ethylenically unsaturated copolymerizable compounds such Z(~03 ~

as, for example, a-methylstyrene, ring halogenated styrenes, ring alkylated styrenes having 1 to 4 carbon atoms in the alkyl group, acrylonitrile, methacrylonitrile; esters of acrylic acid, methacrylic acid or fumaric acid from alcohols having 1 to 10 carbon atoms; also butadiene or ~-vinyl compounds, such as, for example, N-vinylcarbazole, N-vinylpyridine; or smaller quantities, that i5 less than 0.5 weight percent, of divinyl compounds, such as, for example, butanevinyl diacrylate or divinylbenzene.
The expandable styrene polymers contain a blowing agent. Conventional blowing agents are used, that is aliphatic or cycloaliphatic hydrocarbons or halogenated hydrocarbons having a maximum boiling point of about 90C which do not dissolve the styrene polymers but can be homogeneously distributed in them. Typical blowing agents used in quantities of from about 2.5 to 3 weight percent are, for example, n-, iso-, or neopentane, hexane, cyclohexane, n- or iso-butane, propane, difluorodichloromethane or mixtures thereof.
The blowing agents can be added in any fashion and at any time to the styrene polymers, for example, even when polymerizing the monomers or ri~ht in the extruder which forms the cylindrical extrudate.
Typical bromine compounds used as flame retardants are used as the organic compounds. Moreover, they generally ~0(334~

contain at least two bromine atoms and have a bromine content of at least 40 weight percent. Typical bromine compounds are 1,2,3,4-tetrabromobutane, 1,2,~~tribromobutane, tetrabromopentane; bromine substituted cycloalkanes, such as 1-chloro-2,3,4,5,6-pentabromocyclohexane, 1,2,3,4,5,6-hexabromocyclohexane, 1,2,5,6,9,10-hexabromocyclodecane, octabromocyclohexadecane, dibromoethylbenzene, pentabromodiphenylether, es~ers and acetals of dibromopropanol, such as tris-(2,3-dibromopropyl) phosphate.
Hexabromocyclodecane is preferably used.
The organic bromine compound is used in conventional effective quantities. The molding composition should have a bromine content between 0.3 and 5 weight percent, more preferably 0.5 and 4 weight percent and most preferably between 0.8 and 3 weight percent of brornine.
The styrene polymers contain dicumyl (2,3-diphenyl-2,3-dimethylbutane) as the synergistic additive and typically in an amount of from 0.05 to 1 weight percent, more preferably 0.1 to 0.5 weight percent, and most preferably 0.1 to 0.3 weight percent based on the styrene polymer.
In addition, the expandable styrene polymers can contain other typical additives, such as, for example, dyes, fillers, nucleating agents, stabilizers, etc. in effective quantities.

2i~034~

When preparing the expandable styrene polymers the styrene polymer, blowing agent, flame retardant and additives are mixed in an extruder, melted and extruded. In addition, nozzles having any cross section can be used depending on the desired cross section of ~he extrudate. Preferably extrudate having a cylindrical cross section is prepared which has a diameter of from 3 to 15, more preferably 5 to 10 mm. The material temperature when discharged from the nozzles generally is ~0 to 150C, more preferably 110 to 130C. The extrudate is cooled quickly in a cooling bath so that it does not, or p-ractically does not foam. Cooling the extrudate is done on the surface while the inside of the extrudate remains hot and plastic. In this condition the ex~rudate can be further stretched and~or deformed. To do this it is fed generally via guide rollers from the cooling bath and through a pair of rollers. A combination of one elastic and one non-elastic roller, for example, rubber and steel has proven useful here.
The roller speed can be adjusted so that the extrudate can be stretched more or less, or not stretched at all. The cross section of the extrudate can be reduced by 5 to 60% by stretchin~ or drawing. The roller pressure can be adjusted so that the extrudate is deformed more or less, and so that it assumes an oval and/or elliptical cross section, ~or example, having an axis ratio of 1:1.3 to 1:2. ~or stretching and/or z~

deforming the extrudate several roller pairs can be arranged in sequence. The rollers are generally smooth but even profilated are suitable. Conventional rollers can be used to feed granulating units.
Efficaciously the extrudate is cut directly behind the rollers, thus, practically at the same temperature and in a state where the inside of the extrudate is still plastic. Said extrudate is preferably cut by a sharp rotating knife in the direction of the smaller axis of the oval cross section into slices. The oval slices obtained generally have a thickness whose ratio to the smaller axis of the extrudate cross section is 1:1.5 to 1:10, more preferably 1:2 to 1:6.
The deformation and/or stretching by milling and cutting the extrudate generally occurs at an average temperature between 50 and 90C, more preferably 60 and 80C.
The temperature can easily be measured by measuring the temperature of the granulate cut immediately after its preparation.
By deforming and/or stretching and cutting the extrudate while its interior is still plastic, the granulate retains its inner tension. The net result is that the discs curl easily before and especially after foaming. By foaming oval discs of expandable material, one obtains convex-concave or saddle-shaped foam discs which interlock with one another 2(103~

under pressure and accordingly are excellently suited as flowable and shakable cushioning material and packaging material.
Foaming is done in a conventional fashion in commercially available equipment, for example, using steam at from 100 to 150C. Generally the particles are foamed up to a bulk density of from 4 to 15 grams per liter. When using dicumyl as an additive according to the present invention, unlike conventional synergists, such as dicumylperoxide, the amount of organic bromine compounds required for good self extinguishing p.operties can be drastically reduced. At the same time usually prevented for the most part is extruder corrosion. Surprisingly, when using dic~myl, bubble formation is reduced which brings about a noticeable increase in the density of the expandable particles and at the same time the break rate of the foam particles prepared is reduced.
The parts in the examples refer to parts by weight.

201)348~

_amples 1 throuyh _ Polystyrene prepared by suspension polymerization containing 6 weight percent oE pentane as a blowing agent was plasticated in a heated twin sha~t extruder (Type ZSK 120) while using the amounts of hexabromocyclododecane (HBCD) cited in the table as the flame retardant additive; then extruded at a mass temperature of 130~C through a breaker plate having nozzle diameters of 8 mm into a water bath at 20C; and the extrudate following a residency time of 15 seconds was fed via guide rollers through a pair of rollers which contained one steel and one rubber roller. By simultaneous stretching and deformation of the cylindrical extrudate, it was shaped into material having an oval cross section with a diameter of 5 mm/8.5 mm and subsequently cut into 2 mm thick pieces via a rotating knife. Immediately after its preparation the granulate had a temperature of 72C.
Oval foam particles were obtained by foaming with flowing steam. The particles were slightly bent and had a bulk density of about 8 grams per liter. The foam product was well suited as loose shakable packaging material. The extinguish times cited were measured by filling a wire mesh cage (100x150x150 mm) with the foam particles after 72 hours of intermediate storage and by igniting the foam with a natural gas flame. The time to extinguish the flame was reported as a ~0034~

mean value of 20 individual measurements. The results of the e~periments are compiled in table 1.

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Claims (6)

we claim:
1. A process for the preparation of expandable styrene copolymers comprising the steps of mixing a styrene polymer, a blowing agent, an organic bromine flame retardant and dicumyl to form a mixture; extruding said mixture; cooling the extrudate so that foaming is substantially prevented;
deforming the extrudate while the inside is still plastic; and thereafter reducing the extrudate in size.
2. A process as set forth in claim 1 wherein dicumyl is used in a quantity of from 0.05 to 1.0 weight percent, based on the styrene polymer.
3. A process as set forth claims 1 wherein the extrudate is deformed into an oval cross section, and cut into slices in the direction of the smaller axis of the oval cross section.
4. A process as set forth in claim 2 wherein the extrudate is deformed into an oval cross section, and cut into slices in the direction of the smaller axis of the oval cross section.
5. A process as set forth in claim 1 wherein said step of deforming comprises stretching said extrudate.
6. A process as set forth in claim 1 wherein said step of deforming comprises milling said extrudate.
CA002003488A 1988-12-23 1989-11-21 Process for the preparation of expandable styrene polymers Abandoned CA2003488A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3843536A DE3843536A1 (en) 1988-12-23 1988-12-23 METHOD FOR PRODUCING EXPANDABLE STYRENE POLYMERS
DEP3843536.5 1988-12-23

Publications (1)

Publication Number Publication Date
CA2003488A1 true CA2003488A1 (en) 1990-06-23

Family

ID=6370047

Family Applications (1)

Application Number Title Priority Date Filing Date
CA002003488A Abandoned CA2003488A1 (en) 1988-12-23 1989-11-21 Process for the preparation of expandable styrene polymers

Country Status (5)

Country Link
EP (1) EP0374812B1 (en)
AT (1) ATE71876T1 (en)
CA (1) CA2003488A1 (en)
DE (2) DE3843536A1 (en)
ES (1) ES2028431T3 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3825353A1 (en) * 2019-11-20 2021-05-26 Storopack Hans Reichenecker GmbH A product made of an expanded plastic material, extruded expandable plastic particles, and method for producing a plurality of expandable plastic particles

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19819058C5 (en) * 1998-04-29 2015-06-25 Basf Se Process for the production of prefoamed EPS particles with coarse foam structure from particulate, slightly foamed, expanded styrene polymers
AT505735A1 (en) 2007-09-14 2009-03-15 Sunpor Kunststoff Gmbh METHOD FOR THE PRODUCTION OF EXPANDABLE STYROLOPLYMERISES
AT510311B1 (en) 2010-08-27 2013-02-15 Sunpor Kunststoff Gmbh FLAME-PROTECTED, HEAT-DAMPING POLYMERISATES AND METHOD FOR THE PRODUCTION THEREOF
DE102012011636A1 (en) * 2012-06-12 2013-12-12 Automatik Plastics Machinery Gmbh Feed roller for strand pelletizers

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL127714C (en) * 1965-04-01
DE2154754C3 (en) * 1971-11-04 1978-08-31 Basf Ag, 6700 Ludwigshafen Process for the production of expandable styrene polymers

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3825353A1 (en) * 2019-11-20 2021-05-26 Storopack Hans Reichenecker GmbH A product made of an expanded plastic material, extruded expandable plastic particles, and method for producing a plurality of expandable plastic particles

Also Published As

Publication number Publication date
DE58900766D1 (en) 1992-03-05
ES2028431T3 (en) 1992-07-01
DE3843536A1 (en) 1990-06-28
ATE71876T1 (en) 1992-02-15
EP0374812B1 (en) 1992-01-22
EP0374812A1 (en) 1990-06-27

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Legal Events

Date Code Title Description
FZDE Discontinued
FZDE Discontinued

Effective date: 19960521

FZDE Discontinued

Effective date: 19960521