EP0734412A1 - Flammhemmende styrolpolymerzusammensetzung - Google Patents

Flammhemmende styrolpolymerzusammensetzung

Info

Publication number
EP0734412A1
EP0734412A1 EP95904228A EP95904228A EP0734412A1 EP 0734412 A1 EP0734412 A1 EP 0734412A1 EP 95904228 A EP95904228 A EP 95904228A EP 95904228 A EP95904228 A EP 95904228A EP 0734412 A1 EP0734412 A1 EP 0734412A1
Authority
EP
European Patent Office
Prior art keywords
flame retardant
tpp
tpr
composition
additives
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.)
Withdrawn
Application number
EP95904228A
Other languages
English (en)
French (fr)
Inventor
Claude T. E. Van Nuffel
Rik G. Vaneeckhoutte
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.)
Dow Chemical Co
Original Assignee
Dow Chemical Co
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 Dow Chemical Co filed Critical Dow Chemical Co
Publication of EP0734412A1 publication Critical patent/EP0734412A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives

Definitions

  • LAM E RETARDAN X STYREN IC POLYMER COMPOSIT ONS ⁇ n ⁇ s invention relates to stvrenic polymer comoositions, tnat is compositions comprising polymers of styrene and optionally one or more comonomers
  • polystyrene compositions including so called ' hign impact polystyrene (HIPS), containing various polymeric additives such as rubbers to improve mechanical properties, and acryionit ⁇ le/ butadiene/styrene (ABS)-tvpe compositions
  • HIPS ' hign impact polystyrene
  • ABS acryionit ⁇ le/ butadiene/styrene
  • Styrenic resins are widely used for many purposes, because of their excellent mechanical properties, and ease of processing
  • rubber-reinforced styrenic polymers such as high impact polystyrene (HIPS) are commonly used to produce molded consumer goods,
  • fire retardant additives which have been employed are red phosphorus, polyphosphates such as ammonium polyphosphate, melaminephosphate, and various inorganic compounds such as magnesium hydroxide Red phosphorus-containing compositions are disclosed, for example, in U S Patent 3,546, 160
  • TPP Triphenylphosphate
  • U S Patent 4,526,917 U S Patent 4,684,682
  • U S Patent 5,206,276 the use of TPP as a flame retardant additive has hitherto been understood to depend either upon the presence of oxygen in the polymer chain, or else the simultaneous use of halogen-
  • Patent 3,879,345 and U.S Patent 4, 172,858) a nalogen-containing flame retardant additive is also believed to be essential.
  • a nalogen-containing flame retardant additive is also believed to be essential.
  • an equimolar amount of tetrabromobisphenol-A is required to be used with tncresol and/or triphenyl phosphate.
  • TPP has also been proposed as a plasticizer for polystyrene, for example in U.S. Patent 2,493,965.
  • the amount of TPP required for such a purpose is very large (between 20 and 50 percent), and no mention is made of any flame retardant effect of TPP.
  • a styrenic polymer composition having a polymeric component and flame retardant component, wherein the polymeric component is substantially oxygen-
  • the flame retardant component is substantially halogen-free and comprises from 2 to 10 percent by weight (based on the composition) of triphenyl phosphate (TPP), and, optionally, one or more of flame retardant additives (a) to (h) a. red phosphorus (P); b. ammonium polyphosphate (APP); c. meiaminephosphate (MP); d. melaminecyanurate (MC); e. melam ⁇ nepyrophosphate (MPP); f. resorcinol bis(diphenylphosphate) (RDP); g. magnesium hydroxide (MG); h. a thermoplastic rubber (TPR) wherein the concentration expressed as weight percent of the total composition of flame retardant additives satisfy the following conditions:
  • the preferred amounts of the fire retardant (FR) additives to be employed depend upon the specific FR agents which are used. In general terms, the preferred amount of TPP employed is in the range of from 7 to 9 percent. When the FR agents TPP, P, and TPR, are employed (the others being absent), the preferred ranges (as percent by weight of the composition) are as follows: TPP: 2.5 - 5 P: 3 - 6 TPR: 1 - 4
  • TPP 2.5 - 5 ?: 2.5 - 5 TPR: 3 - 7
  • the preferred amounts of FR agents are TPP, P, TPR, and MP.
  • TPP 2.5 - 5 P: 2.5 - 5 TPR: 2 - 6 MP : 3 - 8
  • compositions contain just the FR agents TPP, P, TPR, and MPP (the others being absent), the preferred amounts are:
  • the styrenic polymers of the present invention are prepared from one or more monoalkenyl aromatic compounds.
  • Representative monoalkenyl aromatic compounds include styrene, alkyl substituted styrenes such as alpha-alkyl-styrenes (for example, alpha-methyl- -styrene and alpha-ethyl-styrene) and ring substituted styrenes (for example, o-ethyl-styrere, 2,4-dimethyl-styrene, and vinyltoluene, particularly, p-vinyl-toluene); vinyl anthracene; and mixtures thereof.
  • the polymer matrix preferably utilizes styrene and/or aipha-methyl-styrene as the monoalkenyl aromatic monomer, with styrene being the most preferred monoalkenyl aromatic compound.
  • one or more additional comonomers, _ preferably in an amount of up to 40 percent by weight of the polyme ⁇ zable monomer mixture optionally nay be employed.
  • Suitable comonomers include, for example, unsaturated nit ⁇ les, for example acrylonit ⁇ le.
  • the styrenic polymer is the maior component of the composition of the invention.
  • ⁇ ne stvrenic polymer empioye ⁇ OD ⁇ ionailv can D ⁇ ruDber-mo ⁇ iTied Diene- co ⁇ taining ruobery poivmers are preTerre ⁇ as the ruooer _ ne ⁇ iere-containing ru obe r y polymer preterably employed is a rubbery polymer having at least one diene-containmg block
  • said poiymer is a homoooiymer or copoiymer or an alkaoiene
  • the r ubber is a homopolymer of a
  • diene-containmg rubbery polymer is advantageously employed in amounts such that the rubber-reinforced polymer product contains from about 5 to about 25 percent, preferably from about 6 to about 20 percent, more preferably from about 7 to about 16 weight percent rubber (expressed as rubber or rubber equivalent)
  • Rubbery polymers can be employed for example, mixtures of rubbery polymers prepared by emulsion ana mass polymerization processes can oe employed The preparation of ABS using such mixtures is disclosed in U S Patent 4,713,420 These emulsion/mass mixtures are preferred for use in the preparation of ABS
  • thermoplastic rubber which is preferably employed can oe a thermoplastic elastome ⁇ c olock copoiymer compatible with the styrenic polymer
  • thermoplastic elastome ⁇ c block copolymers are well known, and several are commercially available Additionally, the general type and preparation of some of these block copolymers are described in U S Patent Re 28,246, and in many other patents
  • the diene-containmg rubbery polymer may contain a small amount of a crosslinking agent, excessive crosslinking can result in loss of the rubbery characteristics and/or render the rubber insoluble in the monomer
  • the rubber preferably employed in the preparation of the disperse rubber particles exhibits a second order glass transition temperature not higher than about 0°C and preferably not higher than aoout -20°C
  • the styrenic polymer component of the present invention can be selected from a wide variety of compositions comprising a styrenic polymer and, optionally, rubber These materials are commercially available and their composition is well known to those skilled in the art
  • the methods for preparing styrenic polymers are well known to those skilled i n the art and include, for example, emulsion, suspension, mass, and mass-susoension polymerization methods
  • a mass type polymerization is preferred when preparing polystyrene, HIPS or SAN
  • the techniques of mass polymerization, and the conditions needed for producing desired average rubber particle sizes are well known to those skilled in the art
  • continuous methods are preferred for mass polymerizing the monoalkenyl aromatic compound in the reaction mixture
  • a stratified, linear flow, stirreo tower-type reactor also referred to as a plug flow-type reactor wnen preparing polystyrene or HIPS
  • Such reactors are well known See ⁇ or example U S Patent 2
  • a suitable initiator may be employed in the preparation of the styrenic polymer
  • initiators include the peroxide initiators such as the peresters, for example, tertiary butyl peroxybenzoate and tertiary butyl peroxyacetate, ⁇ ibenzoyi peroxide, dilauroyl peroxide, 1 , 1 -bis tertiary butyl peroxycyclohexane, 1-3-b ⁇ s tertiary butyl peroxy- -3,3,5-t ⁇ methyl cyclohexane, dicumyl peroxide and photochemical initiation techniques
  • Preferred initiators include dibenzoyl peroxide, tertiary butyl peroxy benzoate, 1 , 1 -bis tertiary butyl peroxy cyclohexane and tertiary butyl peroxy acetate
  • initiators o may be employed in a range of concentrations dependent on a variety of factors
  • reaction diluents advantageously employed include normally liquid organic materials which form a solution with the rubber reinforcing polymer, the polymerizable monomers and the polymer prepared therefrom
  • 0 organic liquid diluents include aromatic and substituted aromatic hydrocarbons such as benzene, ethyl benzene, toluene and xylene, saturated, substituted or unsubstituted, straight or branched, aliphatics having 5 or more carbon atoms, such as heptane, hexane or octane, and a cyclic or substituted ahcyclic hydrocarbons having 5 or 6 carbon atoms such as cyclohexane and the like
  • Preferred organic liquid diluents employed herein are the substituted aromatics, 5 with ethylbenzene and xylene being most preferred If employed, the
  • the polymerization mixture used in preparing the styrenic polymer may also contain other materials such as one or more flow promoters, catalysts, lubricants, plasticizers or antioxidants
  • temperatures at which mass polymerization is most advantageously conducted are dependent on the specific components, particularly the initiator, employed, but will generally vary from about 60°C to about 190°C
  • Tne polymer composition of the present invention can include commonly 5 employed additives such as, for example, fillers, pigments, stabilizers, lubricants and mold release agents
  • common additives include, carbon black, polyethylene wax, glass fibers, . ass beads, talc, T ⁇ 0 2 , phenolic antioxidants and mineral oil
  • the ruobery ooiymers of the invention may oe on ex ⁇ ende ⁇ These a ⁇ itives are employed in amounts .vnicn are well Known to those s ⁇ n le ⁇ in the an
  • the polymer composition of the invention may oe prepared by batch or conti nuous olending of the individual components, with or without using a masteroatch, according to methods well known to those skil led in the art
  • the blending can be accomplished by extrusion.
  • MFR Melt Flow Rate
  • HOSTAFLAM AP422 Hammoniumpolyphosphate HOSTAFLAM AP422 (Hoechst) MP : melammephosphate AMGARD N H (Albright & Wilson) MPP: melaminepyrophosphate (Chemie Linz)
  • TPP triphenylphosphate REOMOL TPP (FMC Corp)
  • TPR thermoplastic rubber
  • RDP resorcinol b ⁇ s(di- ohenyl phosphate) FYROLFLEX
  • RDP (Akzo)
  • Comparative Example 1 A hign impact polystyrene was oreoare ⁇ usi ng 8.5 weignt percent o ⁇ low cis poiyDuta ⁇ iene Rubber 1 HX528 pro ⁇ uce ⁇ by Bayer; in a mass ooiyme ⁇ zation process
  • the HIPS material was injection moided into test bars for evaluation of physical properties and flammability. Injection molding was done on an Engel ES 330/80 injection molding machine. The processing conditions used were:
  • Flammability was determined according to IEC-65 and UL-94 V-2 on specimens naving a thickness of 2.0 mm. Prior to testing, samples were conditioned at 50 percent relative humidity at 23°C for 48 hours.
  • This HIPS resin has the following properties: M FR 4.5 g/10 m ⁇ n
  • the HIPS resin therefore does not pass the flammability ratings.
  • the HIPS resin from Comparative Example 1 was melt blended with the following additives:
  • TPP 5 weight percent on a Buss Ko-Kneader model MDK E 46B, having an L D of 1 1 and a screw diameter of 46 mm, at a speed of 220 rpm, with the following zone temperatures: Z1 200°C, Z2 190°C, die 200°C.
  • the discharge extruder was used at 400 rpm. Vacuum was applied and the througnout was 15 kg/hr.
  • Example 1 and having the following composition: HIPS : 87.5 weight percent P : 5 weight percent TPR . 5 weight percent
  • IR-HIPS resin was prepared according to the procedure as described for Example 1 and having the following composition: HIPS : 82.5 weignt percent P : 5 weight percent
  • the material was evaluated according to the test procedures as desc ⁇ oed for Comparative Example 1 and has the following properties:
  • Example 1 and having the following composition: HIPS : 78.5 weight percent P : 5 weight percent MP : 7.5 weight percent
  • Example 5 An IR-HIPS resin was orepare ⁇ accor ⁇ i ⁇ g to the proce ⁇ ure as ⁇ esc ⁇ ped for Example i ana having tne followi ng corriDOSition HIPS : 76.5 weight percent P : 5 weight percent APP : 10 weight percent
  • IR-HIPS resin was prepared according to the procedure as described for Example 1 and having the following composition: HIPS : 95 weight percent P : 5 weight percent
  • composition is not in accordance with the invention, as there is no TPP present. Furthermore, condition IV is also not satisfied.
  • Comparative Example 1 has the following properties: MFR . 4.3 g/10 m ⁇ n Vicat : 105°C
  • IR-HIPS resin was prepared according to the procedure as descri bed for Example 1 and having the following composition: HIPS : 95 weight percent
  • IR-HIPS resin was prepared according to the procedure as described for Example 1 and having the following composition: HIPS : 85 weight percent TPP : 15 weight percent
  • Example 1 and having the following composition: P : 5 weight percent TPP : 2 weight percent TPR : 6 weight percent RDP : 5 weignt percent
  • IR-HIPS resin was prepared according to the procedure as described for Example 1 and having the following composition: MG : 10 weight percent P : 5 weight percent TPP : 5 weignt percent TPR : 7 weight percent HIPS: 73 weight percent
  • IEC-65 28 mm/mm UL-94: V-2 All requirements on flammability and physical properties are met.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP95904228A 1993-12-14 1994-11-28 Flammhemmende styrolpolymerzusammensetzung Withdrawn EP0734412A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9325575 1993-12-14
GB939325575A GB9325575D0 (en) 1993-12-14 1993-12-14 Flame retardant styrenic polymer compositions
PCT/US1994/013941 WO1995016736A1 (en) 1993-12-14 1994-11-28 Flame retardant styrenic polymer compositions

Publications (1)

Publication Number Publication Date
EP0734412A1 true EP0734412A1 (de) 1996-10-02

Family

ID=10746584

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95904228A Withdrawn EP0734412A1 (de) 1993-12-14 1994-11-28 Flammhemmende styrolpolymerzusammensetzung

Country Status (8)

Country Link
EP (1) EP0734412A1 (de)
AU (1) AU1300395A (de)
BR (1) BR9408200A (de)
CA (1) CA2178211A1 (de)
CO (1) CO4440436A1 (de)
GB (1) GB9325575D0 (de)
MY (1) MY131694A (de)
WO (1) WO1995016736A1 (de)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19547078A1 (de) * 1995-12-18 1997-06-19 Bayer Ag Flammgeschützte thermoplastische kautschukhaltige Formmassen
DE19640886A1 (de) * 1996-10-04 1998-04-09 Basf Ag Halogenfreie Flammschutzmittel enthaltende expandierbare Styrolpolymerisate
WO1998035970A1 (en) * 1997-02-14 1998-08-20 Great Lakes Chemical Corporation Process for making and using bisaryl diphosphates
JP3340946B2 (ja) 1997-07-18 2002-11-05 キョーワ株式会社 メッシュシート用難燃剤とこれを用いた防炎メッシュシート
FR2783833B1 (fr) * 1998-09-29 2000-12-08 Bp Chem Int Ltd Composition thermoplastique ignifugeante de (co-)polymere vinylaromatique
US6797200B2 (en) 2000-03-30 2004-09-28 Pirelli Cavi E Sistemi S.P.A. Self-extinguishing cable and fire retardant composition used therein
US6689825B1 (en) * 2002-11-27 2004-02-10 General Electric Company Additive for thermoplastic resins and flame retardant resin compositions
US7417083B2 (en) 2004-04-01 2008-08-26 Sabic Innovative Plastics Ip B.V. Flame retardant composition
JP4478715B2 (ja) * 2004-04-01 2010-06-09 サビック・イノベーティブ・プラスチックス・アイピー・ベスローテン・フェンノートシャップ 難燃剤組成物
US7582692B2 (en) 2004-04-01 2009-09-01 Sabic Innovative Plastics Ip B.V. Flame retardant thermoplastic composition and articles comprising the same
US7799854B2 (en) 2004-04-01 2010-09-21 Sabic Innovative Plastics Ip B.V. Flame retardant thermoplastic composition and articles comprising the same
AT511090B1 (de) * 2011-04-18 2012-09-15 Sunpor Kunststoff Gmbh Flammgeschützte expandierbare polymerisate

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3628577A1 (de) * 1986-08-22 1988-03-03 Basf Ag Halogenfreie, selbstverloeschende, schlagfeste, thermoplastische formmasse

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9516736A1 *

Also Published As

Publication number Publication date
CO4440436A1 (es) 1997-05-07
WO1995016736A1 (en) 1995-06-22
CA2178211A1 (en) 1995-06-22
AU1300395A (en) 1995-07-03
BR9408200A (pt) 1997-08-26
MY131694A (en) 2007-08-30
GB9325575D0 (en) 1994-02-16

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