WO2010091232A2 - Vulcanisats thermoplastiques ignifuges - Google Patents

Vulcanisats thermoplastiques ignifuges Download PDF

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Publication number
WO2010091232A2
WO2010091232A2 PCT/US2010/023293 US2010023293W WO2010091232A2 WO 2010091232 A2 WO2010091232 A2 WO 2010091232A2 US 2010023293 W US2010023293 W US 2010023293W WO 2010091232 A2 WO2010091232 A2 WO 2010091232A2
Authority
WO
WIPO (PCT)
Prior art keywords
compound
agents
flame retardant
tpv
thermoplastic
Prior art date
Application number
PCT/US2010/023293
Other languages
English (en)
Other versions
WO2010091232A3 (fr
Inventor
Vanessa Fever
Charles Page
Original Assignee
Polyone Corporation
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 Polyone Corporation filed Critical Polyone Corporation
Priority to DE112010000865.5T priority Critical patent/DE112010000865B4/de
Publication of WO2010091232A2 publication Critical patent/WO2010091232A2/fr
Publication of WO2010091232A3 publication Critical patent/WO2010091232A3/fr

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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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016—Flame-proofing or flame-retarding additives
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • 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
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08K5/01—Hydrocarbons

Definitions

  • thermoplastic vulcanizates polymer compounds which exhibit elasticity while remaining thermoplastic, which are also flame retardant.
  • thermoplastic elastomers combine the benefits of elastomeric properties of thermoset polymers, such as vulcanized rubber, with the processing properties of thermoplastic polymers.
  • thermoplastic elastomers should be flame retardant. There is customer demand for essentially non-halogen flame retardant thermoplastic elastomers.
  • thermoplastic elastomer is a thermoplastic vulcanizate (also called "TPV") in which the elastomer component is vulcanized or crosslinked.
  • TPV thermoplastic vulcanizate
  • thermoplastic vulcanizate that is flame retardant without the use of brominated flame retardants or chlorinated polyethylene flame retardants or other halogen-containing flame retardants.
  • TPV TPV compound using only essentially halogen-free flame retardant
  • Essentially halogen-free means that there is no intention to include any halogen moieties in any of the flame retardants or other additives to the TPV, but that one cannot control trace amounts of impurities that may exist in such ingredients.
  • the TPV concentrate used in the present invention has a very small content of halogen in the commercially available but proprietary product. For that reason, the TPV compounds of the present invention are considered "low halogen," not
  • the present invention solves the problem by formulating a HFFR
  • TPV that utilizes ammonium polyphosphate as an essentially halogen-free flame retardant.
  • thermoplastic vulcanizate compound comprising (a) thermoplastic vulcanizate; (b) an ammonium polyphosphate-containing flame retardant; and optionally (c) plasticizer.
  • Another aspect of the invention is a plastic article made from the compound.
  • TPVs of the present invention are based on the use of concentrates of TPV commercially available from companies such as ExxonMobil Corporation and are then compounded with other ingredients, such as plasticizers, antioxidants, thermal stabilizers, and one or more secondary polymers.
  • the TPV concentrate is a blend of a continuous phase of a polyolefin such as polypropylene and a discontinuous phase of a vulcanized rubber such as crosslinked EPDM.
  • TPV concentrates are commercially available from ExxonMobil Corporation in a number of grades marketed under the SantopreneTM brand, particularly the SantopreneTM 8000 series grades. It was reported by the manufacturer that SantopreneTM 8000 series grades have a halogen content of less than 200 parts per million. Of the SantopreneTM 8000 grades, SantopreneTM RC8001 TPV concentrate is presently preferred.
  • SantopreneTM RC8001 TPV concentrate has the advantage that, as a ready- vulcanized concentrate, there is no risk of the flame retardants interfering with the vulcanization system, or of vulcanization chemicals deactivating the flame retardants.
  • the compound of the present invention can include conventional plastics additives in an amount that is sufficient to obtain a desired processing or performance property for the compound.
  • the amount should not be wasteful of the additive, nor detrimental to the processing or performance of the compound.
  • Those skilled in the art of thermoplastics compounding without undue experimentation but with reference to such treatises as Plastics Additives Database (2004) from Plastics Design Library (www.williamandrew.com), can select from many different types of additives for inclusion into the compounds of the present invention.
  • Non-limiting examples of optional additives include adhesion promoters; biocides (antibacterials, fungicides, and mildewcides), anti-fogging agents; anti-static agents; bonding, blowing and foaming agents; dispersants; fillers and extenders; smoke suppresants; expandable char formers; impact modifiers; initiators; lubricants; micas; pigments, colorants and dyes; plasticizers; processing aids; other polymers; release agents; silanes, titanates and zirconates; slip and anti-blocking agents; stabilizers; stearates; ultraviolet light absorbers; viscosity regulators; waxes; and combinations of them.
  • adhesion promoters include adhesion promoters; biocides (antibacterials, fungicides, and mildewcides), anti-fogging agents; anti-static agents; bonding, blowing and foaming agents; dispersants; fillers and extenders; smoke suppresants; expandable char former
  • Any conventional plasticizer preferably a paraffinic oil, is suitable for use the present invention.
  • a preferred secondary polymer for the present invention is polypropylene homopolymer or copolymer.
  • a preferred anti-oxidant is a tetrakismethylene antioxidant (CAS
  • a preferred thermal stabilizer an Irganox brand thiodipropionate compound identified as CAS 123-28-4.
  • An expandable graphite filler can serve as an expandable char former in formulations of the compound in those instances when the article formed from the compound should expand as it is heated.
  • the expandable graphite filler should have an onset of expansion temperature greater than the processing temperature of the compound, but low enough and with a high enough activity to provide a suitable expansion. Suitable expansion could be as much as 300%, in an embodiment of a door seal where the gap during normal operation becomes sealed upon onset of exposure to heat or flame.
  • Preferred expandable graphite filler products are commercially available as Nord-Min branded products from Nordmann Rassmann of Germany.
  • Table 1 shows the acceptable, desirable, and preferable ranges of ingredients for the HFFR-TPV of the present invention.
  • Mixing in a continuous process typically occurs in an extruder that is elevated to a temperature that is sufficient to melt the polymer matrix with addition of all additives at the feed-throat, or by injection or side-feeders downstream.
  • Extruder speeds can range from about 50 to about 500 revolutions per minute (rpm), and preferably from about 100 to about 350 rpm.
  • the output from the extruder is pelletized for later extrusion or molding into polymeric articles.
  • Mixing in a batch process typically occurs in a Banbury mixer that is also elevated to a temperature that is sufficient to melt the polymer matrix to permit homogenization of the compound components.
  • the mixing speeds range from 60 to 1000 rpm and temperature of mixing can be ambient.
  • the output from the mixer is chopped into smaller sizes for later extrusion or molding into polymeric articles.
  • TPV of the present invention has an excellent versatility because of its elastomeric performance, its thermoplastic processing, its performance at higher temperatures such as at 100 0 C and above, and its durability in the presence of oils and oil-based fuels.
  • the addition of anti-oxidant properties, thermal stabilization, and essentially halogen-free flame retardancy by those respective functional additives makes the HFFR TPV of the present invention an excellent compound for molding into plastic articles which need flame retardancy when in use in enclosed spaces of higher temperatures and possible exposure to oils and oil-based fuels.
  • Use in motor vehicle engine compartments and industrial products requiring high temperature performance are two of many ways the compounds of the present invention can benefit people around the world. Other uses include wire and cable sheathing and insulation, electrical distribution seals and multigates, particularly in automotive or industrial applications where elevated temperatures could be expected.
  • Table 2 shows a TPV example of the present invention and a comparative example of a thermoplastic elastomer (TPE) compound based on Styrene-Ethylene/Butylene-Styrene (SEBS) block copolymer, their formulations, sources of ingredients, and processing conditions.
  • TPE thermoplastic elastomer
  • SEBS Styrene-Ethylene/Butylene-Styrene
  • Example 1 as compared with a SEBS-TPE of Comparative
  • Example A showed excellent physical performance, especially a V-O flame test.
  • compression set at elevated temperatures particularly at 100 0 C.
  • a test reference oil used to simulate most aggressive motor oils for tests such as ASTM D 2000, for 24 hours at 7O 0 C
  • the TPV of Example 1 exhibited a change in volume of only 40%
  • the Comparative Example A exhibited a significantly higher change in volume of 63%.
  • the TPV compound has superior durability in the presence of a most aggressive oil.
  • This flame retardant TPV technology allows end product manufacturers to produce flame retardant products, suitable for use at elevated temperatures and with improved resistance to oils and oil-based fuels which avoid halogens without sacrificing performance.

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)

Abstract

L'invention concerne un vulcanisat thermoplastique (VTP) qui n'emploie qu'un ignifuge essentiellement sans halogène. En option, une charge de graphite expansible est également incluse dans le composé de VTP.
PCT/US2010/023293 2009-02-06 2010-02-05 Vulcanisats thermoplastiques ignifuges WO2010091232A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE112010000865.5T DE112010000865B4 (de) 2009-02-06 2010-02-05 Flammhemmende thermoplastische Vulkanisate sowie daraus hergestellte Artikel

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US15035209P 2009-02-06 2009-02-06
US61/150,352 2009-02-06

Publications (2)

Publication Number Publication Date
WO2010091232A2 true WO2010091232A2 (fr) 2010-08-12
WO2010091232A3 WO2010091232A3 (fr) 2011-02-17

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2010/023293 WO2010091232A2 (fr) 2009-02-06 2010-02-05 Vulcanisats thermoplastiques ignifuges

Country Status (2)

Country Link
DE (1) DE112010000865B4 (fr)
WO (1) WO2010091232A2 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8354463B2 (en) 2007-09-02 2013-01-15 Polyone Corporation Flame retardant thermoplastic elastomers
US20140011898A1 (en) * 2012-07-06 2014-01-09 Polyone Corporation Thermoplastic elastomers with silky feel
WO2016073210A1 (fr) * 2014-11-06 2016-05-12 Hubbell Incorporated Couvercle isolant pour consoles de transformateur
CN106977813A (zh) * 2017-04-20 2017-07-25 贵州省材料产业技术研究院 一种动态硫化有卤阻燃tpv复合材料及其制备方法
US10190706B2 (en) 2015-03-20 2019-01-29 Kongsberg Actuation System II, Inc. Flame resistant hose assembly and method therefore
EP3733397A1 (fr) * 2019-04-17 2020-11-04 KA Group AG Ensemble tuyau résistant aux flammes et procédé associé

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20070087116A (ko) * 2004-12-17 2007-08-27 제너럴 일렉트릭 캄파니 다심 케이블 조립체 및 다심 케이블 조립체의 제조 방법

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JP4436194B2 (ja) * 2004-06-18 2010-03-24 リケンテクノス株式会社 熱可塑性エラストマー組成物
US7882671B2 (en) * 2006-02-21 2011-02-08 Bfs Diversified Products, Llc Multi-layer co-extruded roofing membrane
WO2008076264A2 (fr) * 2006-12-13 2008-06-26 Gupta Laxmi C Corps ignifuge et ses procédés d'utilisation

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
KR20070087116A (ko) * 2004-12-17 2007-08-27 제너럴 일렉트릭 캄파니 다심 케이블 조립체 및 다심 케이블 조립체의 제조 방법

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
KIRAN PAL ET AL.: 'Development of Halogen-Free Flame Retardant Thermoplastic E lastomer Polymer Blend' JOURNAL OF APPLIED POLYMER SCIENCE vol. 94, 2004, pages 407 - 415 *
SZ. MATKO ET AL.: 'Fire retardancy and environment assessment of rubbery blend s of recycled polymers' EXPRESS POLYMER LETTERS vol. 2, no. 2, 2008, pages 126 - 132 *
YIBING CAI ET AL.: 'Preparation and properties studies of halogne-free flame retardant form-stable phase change materials, ScienceDirect' APPLED ENERGY vol. 8, no. 5, 2008, pages 765 - 775 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8354463B2 (en) 2007-09-02 2013-01-15 Polyone Corporation Flame retardant thermoplastic elastomers
US20140011898A1 (en) * 2012-07-06 2014-01-09 Polyone Corporation Thermoplastic elastomers with silky feel
US9249291B2 (en) * 2012-07-06 2016-02-02 Polyone Corporation Thermoplastic elastomers with silky feel
WO2016073210A1 (fr) * 2014-11-06 2016-05-12 Hubbell Incorporated Couvercle isolant pour consoles de transformateur
US9847633B2 (en) 2014-11-06 2017-12-19 Hubbell Incorporated Insulating cover for transformer brackets
US10190706B2 (en) 2015-03-20 2019-01-29 Kongsberg Actuation System II, Inc. Flame resistant hose assembly and method therefore
CN106977813A (zh) * 2017-04-20 2017-07-25 贵州省材料产业技术研究院 一种动态硫化有卤阻燃tpv复合材料及其制备方法
EP3733397A1 (fr) * 2019-04-17 2020-11-04 KA Group AG Ensemble tuyau résistant aux flammes et procédé associé

Also Published As

Publication number Publication date
DE112010000865B4 (de) 2017-05-18
WO2010091232A3 (fr) 2011-02-17
DE112010000865T5 (de) 2012-11-15

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