EP0334942A1 - Composes ignifuges a base de resine pvc - Google Patents

Composes ignifuges a base de resine pvc

Info

Publication number
EP0334942A1
EP0334942A1 EP88909413A EP88909413A EP0334942A1 EP 0334942 A1 EP0334942 A1 EP 0334942A1 EP 88909413 A EP88909413 A EP 88909413A EP 88909413 A EP88909413 A EP 88909413A EP 0334942 A1 EP0334942 A1 EP 0334942A1
Authority
EP
European Patent Office
Prior art keywords
composition
flame retardant
polybrominated
alkylbenzene
percent
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Withdrawn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
EP88909413A
Other languages
German (de)
English (en)
Other versions
EP0334942A4 (en
Inventor
Nicolai Alexander Favstritsky
Robert John Nulph
Dennis Michael Borden
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.)
Great Lakes Chemical Corp
Original Assignee
Great Lakes Chemical Corp
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 Great Lakes Chemical Corp filed Critical Great Lakes Chemical Corp
Publication of EP0334942A1 publication Critical patent/EP0334942A1/fr
Publication of EP0334942A4 publication Critical patent/EP0334942A4/en
Withdrawn legal-status Critical Current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
    • 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
    • C08K5/02—Halogenated hydrocarbons
    • C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl

Definitions

  • the present invention relates to flame retardant polyvinyl chloride (“PVC") resin compositions and more particularly to PVC resin compositions incorporating polybrominated higher alkylbenzenes.
  • PVC polyvinyl chloride
  • a flame retardant agent be specifically tailored to the resin system so that, in addition to its role as a flame retardant, the agent will additionally enhance the desirable characteristics of the resin composition.
  • the selection of such an application-specific flame retardant is unpredictable at best. Thus, even though a given agent may exhibit utility -in a particular resin system, that is no guarantee that this agent will have any use at all with other resins.
  • U.S. Patent No. 3,850,882 discloses a three component flame retardant additive system for polyolefins, especially polypropylene, consisting of
  • Polyester compositions based on such agents contain 0.5 - 10% by weight of bromine and 0.1 - 2% by weight of phosphorus.
  • phosphorus a nuclear brominated alkylbenzene
  • x 2 to 5
  • y and z each are zero or an integer from 1 to 17 and sum of y + z is an integer between 7 and 17 or a mixture thereof.
  • a primary objective of this invention is to provide halogenated resin compositions incorporating superior flame retardant plasticizing agents.
  • a further object is to provide flame retardant plasticizers for PVC resin compositions that are flame resistant, non-volatile, thermally stable and which do not migrate.
  • Yet a further object is to utilize polybrominated higher alkylbenzenes as flame retardant plasticizers for PVC resin compositions.
  • flame retardant PVC resin compositions comprising a PVC resin; a non-flame retardant primary plasticizer; an effective amount of a polybrominated higher (C 6-18 ) mono- or di-alkylbenzene or mixtures thereof; a stabilizer; and an enhancing agent.
  • the polybrominated higher alkylbenzenes utilized in accordance with this invention include tetra- and penta-bromo secondary and tertiary alkyl benzenes, wherein the alkyl group contains 6-18 carbon atoms, and tri- and tetra-bromo. secondary and tertiary dialkylbenzenes, wherein the alkyl groups contain 6-18 carbon atoms.
  • These polybrominated higher alkyl benzenes preferably contain about 30 - 70 percent by weight bromine.
  • compositions of this invention preferably comprise about 50 to 90 percent PVC thermoplastic resin, about 5 - 40 percent primary plasticizer, about 5 - 40 percent polybrominated higher alkylbenzene, about 1 to 10 percent stabilizer and about 1.0 to 15 percent enhancing agent, all by weight of the composition.
  • polybrominated higher alkylbenzenes can be used partially to replace the primary plasticizer in a PVC resin formulation.
  • the term "higher” as used herein with respect to polybrominated alkylbenzenes is intended to encompass secondary and tertiary alkylbenzenes and mixtures thereof.
  • polybrominated higher alkylbenzenes are useful in the preparation of flame retardant thermoplastic PVC resins in accordance with procedures known in the art.
  • novel compositions of this invention are distinguished from known flame retardant PVC compositions by improved properties.
  • the preferred novel flame retardant PVC compositions may be further optimized by admixing from about 50% to about 70% by weight thermoplastic PVC resin; from about 15 to 25 % primary plasticizer, from about 5% to about 25% by weight polybrominated higher alkylbenzene; from about 3 to 10 % stabilizer and 1% to about 15% enhancing agent, where the percentages are based on the total weight of the resulting admixture of these five components.
  • the PVC resins utilized in accordance with this invention are homo- and co-polymer polyvinyl chloride resins of the type exemplified by "GEON 31", a product of B.F. Goodrich.
  • polybrominated higher alkyl benzene flame retardant additives utilized in accordance with the present invention are nuclear halogenated aromatic compounds of the generalized structures (I) and (II):
  • R 1 and R 4 are hydrogen or methyl
  • R 2 , R 3 , R 5 , R 6 are alkyl ranging independently from 1 to 16 carbon atoms. Also, numerically combining R 1 , R 2 and R 3 or R 4 , R 5 and R 6 , the total number of carbon atoms ranges from 5 to 17. Mixtures of such compounds may be produced and are especially preferred.
  • Compounds of structure ( I ) are tetra- and penta-halo secondary or tertiary alkylbenzenes, wherein the alkyl group is of 6 to 18 carbon atoms.
  • Compounds of structure (II) are tri- and tetra-halo secondary or tertiary dialkylbenzenes wherein the alkyl group has 6 to 18 carbon atoms.
  • Preferred compounds produced in accordance with this invention are secondary and tertiary octyl, nonyl, decyl, undecyl and dodecyl benzenes containing 4 to 5 bromines on the benzene nucleus. In place of individual compounds, it is especially preferred to employ mixtures of such compounds.
  • pure brominated primary alkylbenzenes are solids.
  • mixtures of brominated secondary and tertiary alkylbenzenes are liquids having a a broader range of uses due to their liquid state.
  • the polybrominated, predominantly secondary and tertiary, alkyl- and dialkyl-benzenes produced in accordance with this invention generally have a bromine content between 30% and 70% and a chlorine content between 0% and 10%, by weight.
  • the polybrominated alkyl benzenes of this invention are produced by the direct bromination of the corresponding unbrominated material using an excess of liquid bromine as the reaction medium, using bromine chloride as the brominating agent, and using an antimony halide catalysts described in Favstritsky, et al. copending United States Patent Application entitled "Process for Producing Polybrominated Higher Alkylbenzenes, filed herewith.
  • the mixtures of individual polybrominated alkyl benzenes that are most preferred are so-preferred for the additional reason that the corresponding hydrocarbon mixtures are readily available intermediates in the detergent industry.
  • Especially preferred polybrominated alkylbenzenes in accordance with this invention are the tetra- and penta-bromo derivatives of secondary, straight chain alkylbenzenes of the structure(III):
  • R 7 and R 8 are independently linear alkyl groups containing 1 to 12 carbon atoms and where, when numerically combined, R 7 and R 8 contain between 9 and 13 carbon atoms, primarily 9 and 11 carbon atoms and where R 7 is about 25 to 35% methyl.
  • R 7 and R 8 are independently linear alkyl groups containing 1 to 12 carbon atoms and where, when numerically combined, R 7 and R 8 contain between 9 and 13 carbon atoms, primarily 9 and 11 carbon atoms and where R 7 is about 25 to 35% methyl.
  • DODANE S is a mixture of secondary monoalkylbenzenes, wherein the alkyl is primarily undecyl and dodecyl.
  • Another preferred polybrominated alkylbenzene is derived from a secondary, straight chain alkylbenzene of formula (III), wherein the numerical combination of R 7 and R 8 is between 9 and 11 carbon atoms and where R 7 is about 10 to 15% methyl.
  • Such a preferred alkylbenzene is commercially available from Monsanto Co. under the trademark "ALKYLATE 215,” which is a mixture of secondary monoalkylbenzenes similar to "DODANE S.”
  • Still another preferred polybrominated alkyl benzene is derived from a tertiary, branched chain alkylbenzene of the formula (IV):
  • R 9 and R 10 are independently alkyl groups containing 1 to 9 carbon atoms and where the numerical combination of R 9 and R 10 is primarily 8 to 11 carbon atoms.
  • a tertiary alkyl benzene in which R 9 and R 10 are typically nonlinear alkyl groups, is commercially available from Monsanto Co. under the trademark "DODANE H, " which is a mixture of tertiary branched chain, monoalkylbenzenes, wherein alkyl is primarily dodecyl.
  • Still another preferred polybrominated alkylbenzene is derived from a secondary, straight chain dialkylbenzene of the formula (V)
  • R 11 , R 12 , R 13 , and R 14 are independently linear alkyl groups containing 1 to 10 carbon atoms and where, when numerically combined, R 11 and R 12 or R 13 and R 14 contain primarily 11 carbon atoms.
  • R 11 and R 12 or R 13 and R 14 contain primarily 11 carbon atoms.
  • ARISTOL E is a mixture of secondary dialkyl benzenes wherein alkyl is primarily dodecyl.
  • Other commercially available alkybenzenes may of coarse also be brominated and then employed in accordance with the present invention.
  • the brominated alkylbenzenes of the present invention are high boiling liquids, nonvolatile, thermally stable, hydrolytically stable and flame resistant. They may be incorporated in the PVC composition of this invention during compounding as is known to those skilled in the art.
  • the components are first combined in a high- speed mixer after which the blended mass is charged to a heated, two-roll mill for fusion and further mixing.
  • the discharged sheet may be compression molded or calendered to a desired use thickness, as is known to those skilled in the art.
  • compositions of this invention also desirably incorporate one or more enhancing agents.
  • Enhancing agents useful in accordance with this invention comprise the oxides and halides of groups IV-A and V-A of the periodic table; organic or inorganic compounds of phosphorous, nitrogen, boron, or sulfur; and oxides and halides of, for example, zinc, magnesium and titanium, all as disclosed in U.S. Patent No.
  • Preferred enhancing agents in accordance with this invention are the oxides of antimony, arsenic and bismuth, with the oxides of antimony being especially preferred.
  • Antimony trioxide is the most preferred enhancing agent used in the compositions of this invention.
  • the enhancing agent is supplied at the level of about 1 - 15 percent by weight. Optimallly, the enhancing agent is used at a level of about 1 - 5 percent by weight.
  • the compositions of this invention also comprise non-flame retardant primary plasticizers. Suitable primary plasticizers include tri-2-ethylhexyl trimellitate and di-2-ethylhexyl phthalate hexyl phthalate. The primary plasticizer is employed in the composition at a level of about 5 to 40 percent by weight, preferably about 5 to 25 percent by weight.
  • additives include, without limitation, other flame retardants, heat stabilizers, light stabilizers, plasticizers, pigments, preservatives, ultraviolet stabilizers, fillers, antioxidants, antistatic agents, and other materials well known to those skilled in the art, for example, as described in Modern Plastic Encyclopedia, Vol. 63, No. 10A, McGraw-Hill, Inc. (1986).
  • Stabilizers should be employed at a level of about 1 to 10 per cent by weight of the composition.
  • Specific stabilizers which may be employed in accordance with this invention include dibasic lead phthalate, and basic lead silicate, for example.
  • additive materials which may be employed in the composition of this invention can be utilized in any amounts which will not substantially adversely affect the properties of the composition. In general, such amount will be from about 0% to about 80%, based on the total weight of the composition.
  • Polybrominated higher alkylbenzenes specifically polybrominated DODANE S (a polybrominated primarily dodecylbenzene), were prepared by the procedure described in copending Favstritsky, et al. United States Patent Application entitled “Process for Producing Polybrominated Higher Alkylbenzenes” filed herewith.
  • Table I shows the bromine content, viscosity and thermal properties (as measured by thermogravimetric analysis (“TGA”)) of the series of polybrominated DODANE S dodecylbenzenes.
  • EXAMPLE 4 By the same procedure as Example 1 were combined 500 g of PVC resin, 153.8 g of TOTM, 25.g of stabilizer, 7.5 g of antimony trioxide and 96.2 g of Sample 4 (Table I).
  • EXAMPLE 5 By the same procedure as Example 1 were combined 500 g.of PVC resin, 125 g of TOTM, 25 g of stabilizer, 7.5 g of antimony oxide and 125 g of Sample 5 (Table I).
  • EXAMPLE 6 By the same procedure as Example 1 were combined 500 g of PVC resin, 161.5 g of TOTM, 25 g of stabilizer, 7.5 g of antimony oxide and 88.5 g of Sample 6 (Table I).
  • COMPARATIVE EXAMPLE 7 (CONTROL) By the same procedure as Example 1 were combined 500 g of PVC resin, 250 g of TOTM, 25 g of DYTHAL stabilizer, 7.5 g of antimony trioxide. This composition served as a Control sample.
  • Example 7 From the compression molded sheets of Examples 1 through 6 and Comparative Example 7 (Control) were stamped a variety of testing specimens. These samples were tested for flammability using the oxygen index procedure of ASTM D2683.
  • the oxygen index index test is a measure of ease of extinction of a burning specimen in a controlled nitrogen/oxygen atmosphere. For this test, a specimen of the dimensions 0.063 inches in thickness by 0.250 inches in width by 3.5 inches in length is clamped vertically at one end in a holder which is placed in a test column. A mixture of nitrogen and oxygen is introduced through the column. The nitrogen/oxygen ratio is adjusted so the specimen can be ignited at the top by a small pilot flame.
  • the percentage of oxygen is adjusted until the level is reached where a specimen will just burn for a three-minute period or for a length of 50 millimeters. That minimum oxygen concentration is reported as the Oxygen Index ("OI"). The greater the 01 value, the more flame retardant the specimen tested.
  • OI Oxygen Index
  • E662 This procedure utilizes a prescribed test chamber fitted with a radiant heat furnace, a multiple flamelet burner and a photometric system. A sample is heated either by the furnace alone (smoldering mode) or by the furnace and the flamelets (flaming mode). The progressive loss of light transmission is plotted and the minimum point of transmission converted to maximum specific optical density, corrected, Dmc. The lower the Dmc, the lower the smoke density value for the sample.

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

Composés ignifuges à base de résine PVC (chlorure de polyvinyle) comprenant un plastifiant principal non ignifuge, une quantité efficace d'un alkylbenzène supérieur polybromé ou d'un mélange de ce composant, un agent stabilisateur et un adjuvant.
EP19880909413 1987-10-09 1988-10-06 Flame retardant pvc resin compositions Withdrawn EP0334942A4 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US10723687A 1987-10-09 1987-10-09
US107236 1987-10-09

Publications (2)

Publication Number Publication Date
EP0334942A1 true EP0334942A1 (fr) 1989-10-04
EP0334942A4 EP0334942A4 (en) 1991-07-24

Family

ID=22315586

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19880909413 Withdrawn EP0334942A4 (en) 1987-10-09 1988-10-06 Flame retardant pvc resin compositions

Country Status (4)

Country Link
EP (1) EP0334942A4 (fr)
JP (1) JPH02501663A (fr)
KR (1) KR890701677A (fr)
WO (1) WO1989003409A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MX348660B (es) 2011-11-04 2017-05-29 Servicios Condumex Sa Composicion para aislamientos termoplasticos libres de halogenos, retardantes a la flama, con baja emision de humos obscuros y buenas propiedades electricas en agua.

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL130221C (fr) * 1964-03-02 1900-01-01
FR1486273A (fr) * 1965-07-09 1967-10-05
GB1298880A (en) * 1970-03-03 1972-12-06 Berk Ltd Improvements in or relating to polymer compositions
DE2547498A1 (de) * 1975-10-23 1977-04-28 Huels Chemische Werke Ag Flammwidrige formmasse
US4388429A (en) * 1981-04-24 1983-06-14 Occidental Chemical Corporation Flame retardant polymer compositions

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
No further relevant documents have been disclosed. *
See also references of WO8903409A1 *

Also Published As

Publication number Publication date
EP0334942A4 (en) 1991-07-24
KR890701677A (ko) 1989-12-21
WO1989003409A1 (fr) 1989-04-20
JPH02501663A (ja) 1990-06-07

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