WO2000037552A1 - Concentrats d'additifs pour des polymeres olefiniques - Google Patents

Concentrats d'additifs pour des polymeres olefiniques Download PDF

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Publication number
WO2000037552A1
WO2000037552A1 PCT/US1999/030764 US9930764W WO0037552A1 WO 2000037552 A1 WO2000037552 A1 WO 2000037552A1 US 9930764 W US9930764 W US 9930764W WO 0037552 A1 WO0037552 A1 WO 0037552A1
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Prior art keywords
flame retardant
additives
polar
master batch
additive
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PCT/US1999/030764
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English (en)
Inventor
Charles A. Tennesen
Shaun R. Seibel
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Great Lakes Chemical Corporation
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Publication of WO2000037552A1 publication Critical patent/WO2000037552A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins

Definitions

  • This invention relates to flame resistant polyolefin compositions. More particularly, this invention relates to master batches for flame resistant polyolefin comprising an elastomeric carrier resin and one or more polar flame retardant additives.
  • the UL (Underwriters Laboratory) 94 test is commonly used to measure the flame retardancy of a polymer.
  • a test specimen of polymer (either 5" x 1/8" or 5" x 1/16") is exposed vertically to the flame from a Bunsen burner for 10 seconds. The specimen is ignited at the bottom and burns up. If the specimen self-extinguishes within 30 seconds, a second 20 second application of the flame is made. Flaming droplets are allowed to fall on dry absorbent surgical cotton located 12 inches below the sample. If the average burn time is less than 5 seconds and the drips do not ignite the cotton, the polymer is classified as V-0 in the UL94 test. If the time is less than 25 seconds and the drips do not ignite the cotton, the polymer is classified as V-l. If the sample is self- extinguishing but the cotton is ignited, the material is classified as V-2.
  • Polyolefins such as polypropylene and copolymers of propylene and ethylene, are useful in a variety of applications. In many of these applications it is preferred or mandatory to incorporate an additive into the polyolefin to improve its flame resistance or retardance.
  • addition of flame retardant additives improves the flame retardant properties of polyolefins
  • addition of additives particularly in amounts necessary to provide a V-0 rated composition in the UL94 test, can detract significantly from the physical properties of the poly- olefin.
  • the use of flame retardant additives is usually a compromise between the desire for a particular degree of flame retardancy and the need to detract as little as possible from the desirable properties of the polyolefin.
  • Blooming is the separation of the additive from the polyolefin matrix as evidenced by a surface film on a molded specimen of polyolefin that contains the additive. Blooming may occur during cooling of the article in the mold, or may be induced via heat aging at elevated temperatures and/or extended times. The blooming problem is particularly pronounced and difficult to overcome at relatively high heat aging temperatures, that is at heat aging temperatures above approximately 70°C. Because blooming is believed caused the fact that the additive is more polar than the polymer to which it has been added, blooming is a function of both the additive and the polymer to which it is added. Blooming of polar additives is an especially severe problem in polypropylene, a highly non-polar polymer.
  • Blooming of the flame retardant additive not only mars the appearance of the final product but may also reduce the flame resistant properties of the polymer over time due to loss of the flame retardant additive.
  • Many electrical applications for flame retardant polymers require RTI (Relative Thermal Index) ratings that involve 18 months heat aging without a loss of physical properties and flame retardant performance. If the additive blooms from the polymer, the polymer can not achieve the required RTI rating.
  • Tris- (trihaloneopentyl) phosphates especially tris-
  • 09/189,259 filed 11/10/98, incorporated herein by reference, discloses flame resistant polyolefins containing one or more polar flame retardant additives that are made bloom resistant by adding a bloom inhibiting amount of an elastomer.
  • the preferred elastomers are substantially linear ethylene/C 3 -C 20 ⁇ -olefin copolymers, especially substantially linear ethylene/C 5 -C 10 ⁇ -olefin copolymers, prepared by constrained geometry catalysis using metallocene catalysts. Substantially linear ⁇ -octene/- ethylene copolymers are more preferred.
  • Preferred polyolefins are polypropylene and propylene/ethylene copolymers.
  • a preferred polar flame retardant additive is tris- (tribromoneopentyl) phosphate .
  • master batches concentrated batches, known as "master batches,” of polyolefin and additive and subsequent letting down (dilution) of this concentrate with polyolefin is a route to achieving a well-mixed product of polyolefin and polar additives. Because of the low compatibility between polypropylene and its ethylene copolymers with polar additives, master batches for these materials are typically prepared using a carrier resin, such as a polyolefin, rather than the polymer into which the flame retardant additive or additives is to be incorporated.
  • the master batch typically comprises only about 5 to 20%, preferably from 10 to 20%, of the polar flame retardant additive or additives.
  • a master batch comprising more than 25% of polar additives would allow economies in the manufacture of flame retardant polymers.
  • the invention is mater batch for flame and bloom resistant polymers comprising:
  • At least one elastomeric carrier resin wherein at least one polar additive is a polar flame retardant additive.
  • Preferred elastomeric carrier resins are ⁇ -octene/- ethylene elastomers.
  • a preferred polar flame retardant additive is tris- (tribromoneopentyl) phosphate .
  • a preferred polar additive is hydrotalcite.
  • the master batch comprises a total of at least 25% by weight, preferably at least 50% by weight, more preferably at least 60% by weight, and even more preferably at least 70% by weight, of one or more additives selected from the group consisting of polar additives and flame retardant synergists.
  • At least 70% by weight polar additives may be processed into the elastomeric carrier resin of the invention, whereas extreme difficulty was observed while processing these additives into polypropylene homopolymer at levels of 25% by weight.
  • the elastomeric carrier resins also have been shown to be effective antibloom agents for polar additives in polyolefins, especially polypropylene and ethylene/- propylene copolymers.
  • the master batches offer a combination of good processability during master batch compounding, economy, and reduced additive blooming in the final flame retardant polymer.
  • the invention is a method for preparing a flame resistant polymer, the method comprising adding the master batch to a polyolefin.
  • the polymer into which the master batch is to be added may be present in the master batch in addition to the elastomeric carrier resin
  • the elastomeric carrier resin should comprise at least 70%, preferably 80%, and more preferably 90%, of the total amount of elastomeric carrier resin and polymer to which the master batch is to be added present in the master batch.
  • Any elastomer that is compatible with the selected polyolefin is useful as an elastomeric carrier resin. Preferably it does not degrade the properties of the polyolefin. These materials typically have an ultimate elongation of 700% or greater.
  • the preferred elastomers are substantially linear ethylene/C 3 -C 20 ⁇ -olefin copolymers, especially substantially linear ethylene/C 5 -C 10 ⁇ -olefin copolymers, prepared by constrained geometry catalysis using metallocene catalysts. These copolymers are disclosed in McKay, U.S. Patent No. 5,747,580, and Chum, U.S. Patent 5,677,383, incorporated herein by reference. These copolymers are sometimes known as "metallocene elastomers.”
  • More preferred elastomers are substantially linear ⁇ - octene/ethylene copolymers available as the Engage ® polyolefin elastomers from DuPont Dow Elastomers, Wilmington, DE . These materials have: densities of about 0.863 g/cm 3 to about 0.913 g/cm 3 ; melt flow indices of about 0.5 dg/min to about 30 dg/min; differential thermal analysis melting peaks of about 49°C to about 107°C; ultimate tensile strengths of about 4.1 MPa to about 33.8 MPa; and ultimate elongations of about 700% to greater than 1000%.
  • the amount of elastomer used in the final polymer should be an amount effective to yield an improvement in the bloom resistance of the polymer. Typically, such amounts are about 2 to 5 parts by weight of the elastomer per 100 parts by weight of polyolefin. However, up to about 20 parts by weight of elastomer, preferably up to 15 parts by weight of elastomer, may be added to reduce blooming under severe conditions, such as heating at 100°C for seven days .
  • any particular elastomer may vary depending upon the polyolefin and flame retardant additive or additives selected. In addition, the selection of a specific elastomer will also depend upon the particular application specifications. Elastomers having the requisite properties for optimization of bloom inhibition and good physical performance may be selected by routine testing.
  • the polyolefin into which the master batch is incorporated may be derived from a variety of monomers especially propylene, ethylene, butene, iso-butylene, pentene, hexene, heptene, octene, 2 -methyl propene, 2- methyl butene, 4-methylpentene, 4 -methyl hexene, 5- methylhexene, bicyclo- (2, 2, 1) -2-heptene, butadiene, pentadiene, hexadiene, isoprene, 2, 3 -dimethyl butadiene, 3,1-methyl pentadiene, 1, 3 , 4-vinylcyclohexene, vinyl- cyclohexene, cyclopentadiene, styrene and methyl styrene.
  • the polyolefins include copolymers produced from two or more of any of the foregoing monomers and the like, and further include homopolymer blends, copolymer blends, and homopolymer-copolymer blends.
  • the preferred polyolefins are polypropylene and polyethylene, including atactic, syndiotactic and isotactic polypropylene and polyethylene, low density polyethylene, high density polyethylene, linear low density polyethylene, block copolymers of ethylene and propylene, and random copolymers of ethylene and propylene. Polypropylene, propylene/ethylene copolymers, and mixtures and blends thereof are more preferred.
  • the term " mixtures" includes blends.
  • These polyolefins may be produced using a variety of catalytic processes.
  • the polyolefins useful in this invention may be produced by any of these processes including metallocene catalyzed processes.
  • the polymers may have a range of melt indexes (MI) but will typically have MI values in the range 4 to 30.
  • the flame retardant additive or additives may be any polar flame retardant additives described in the literature. A useful review of flame retardant additives is included in Thermoplastic Polymer Addi ives - Theory and Practice, John T. Lutz, Jr., ed. , Marcel Dekker, Inc., 270 Madison Avenue, New York (1989) .
  • a polar additive is an additive that is polar relative to the polyolefin.
  • a polar flame retardant additive is a flame retardant additive (also called a flame retardant) that is polar relative to the polyolefin.
  • the term polar additive includes polar flame retardant additives as well as other polar additives, such as polar photostabilizers, polar thermal stabilizers, polar pigments, etc.
  • Polar flame retardant additive does not refer to the various flame retardant synergists for halogenated flame retardant additives, such as antimony trioxide and zinc borate .
  • polar flame retardant additives examples include: decabromodiphenyl oxide, available from Great Lakes Chemicals under the designation Decabrom; tetrabromo is-phenol-A-jis- (2 , 3-dibromopropyl ether), available from Great Lakes Chemical Corporation under the designation PE-68; tetrabromo- is-phenol-S-Jbis- (2 , 3- dibromopropyl ether) , available as under the designation Non-Nen-52 from Manac Inc.
  • the total amount of polar flame retardant additive or additives present in the final product typically does not exceed about 15 parts by weight of polar flame retardant additive or additives per 100 parts by weight of polyo
  • polar flame retardant additives include tris-
  • trihaloneopentyl hosphates, aromatic and aliphatic halogenated phosphate esters, and other halogenated phosphates, and combinations thereof.
  • Preferred tris- (tri- haloneopentyl) phosphates are tris- (trichloroneopentyl) - phosphate, tris- (chlorodibromoneopentyl) phosphate, tris-
  • tris- (tribromoneo- pentyl) phosphate tris- (tribromoneo- pentyl) phosphate, and combinations thereof.
  • the most preferred tris- (trihaloneopentyl) phosphate is tris- (tri- bromoneopentyl) phosphate [tris- (3-bromo-2 , 2-bis (bromo- methyDpropyl) phosphate] .
  • various flame retardant synergists for halogenated flame retardant additives may be used in the final flame retardant polymer.
  • synergists include antimony trioxide, sodium antimonate, antimony pentoxide, zinc stannate, zinc hydroxystannate, zinc borate, and any mixtures of two or more thereof.
  • Preferred synergists are antimony trioxide and zinc borate.
  • Flame retardant synergists are may be incorporated into the master batch, or added during processing of the final flame retardant polymer.
  • Zinc borate can be used to substitute for 40 to 60% of an antimony containing synergist on a weight basis. This produces a lighter product due to the specific gravity difference between zinc borate and the antimony containing synergist.
  • Zinc borate is commercially available under the designation Firebrake ® 415 flame retardant synergist.
  • the hydrotalcite is a compound that satisfies the formula Mg 6 Al 2 (OH) 16 C0 3 .4H 2 0 or the formula Mg 4 Al 2 (OH) 12 C0 3 .3H 2 0 (sometimes written as
  • hydrotalcite may be written as [Mg 6 Al 2 (OH) 16 ] 2+ [C03] " .
  • the hydrotalcite is preferably dispersed evenly through the polymer.
  • hydrotalcite having an average particle size in the range of 1 to 10 microns, more preferably 1 to 5 microns, is used.
  • Hydrotalcites may be purchased from J.M. Huber under the name Hysafe 539 or from Reheis under the name of L- 55RII.
  • the amount of hydrotalcite incorporated into the final flame retardant polymer may vary through a wide range, from 0.001 to 5.0, and more preferably from 0.001 to 1.0 parts by weight.
  • the amount of hydrotalcite used is generally proportional to the amount of phosphate ester present.
  • the ratio of the weight of phosphate ester to the weight of hydrotalcite is normally in the range 40 : 1 to 3 : 1 and preferably in the range 20:1 to 6:1.
  • the amount of hydrotalcite in the master batch will be the amount required to produce the desired hydrotalcite concentration in the final flame retardant polymer.
  • compositions may also comprise an anti-oxidant .
  • an anti-oxidant A wide variety of anti-oxidants are known and used in the art. These anti-oxidants are described, for example, in Thermoplastic Polymers and Additives - Theory and Practice edited by John T Lutz Jr. and published by Marcel Dekker Inc. in 1989.
  • hydrotalcite reduces or eliminates the noxious odors formed during the processing of polymers with a tris- (trihaloneopentyl) phosphate flame retardant additive
  • the polymers may become discolored during processing. Discoloration is reduced by incorporating an anti-oxidant, preferably a phenolic anti-oxidant, such as 2, 6-di- t-butyl -4 -methyl phenol, 2 , 6-di- t-butyl-4-sec-butyl- phenol, octadecyl 3 , 5-di- t-butyl-4-hydroxycinnamate, 2,2- ethylidene-bis- (4, 6-di- t-butylphenol) , 2, 2-methylene-bis (4- methyl-6- -butylphenol) , 4 , 4-butylidine-bis (6- t-butyl-zn- cresol) , 4 , 4-methylene-bis (2 , 6-di- t-butyl
  • the final flame retardant polymer may also comprise various other additives, such as photostabilizers, thermal stabilizers, antistatic and nucleating agents, pigments, fillers, glass, and other materials known in the art.
  • Photostabilizers and thermal stabilizers include, for example, those available from Ciba-Geigy as Irganox ® stabilizers and Tinuvin ® stabilizers. Synergists, hydrotalcite, anti-oxidants, and other additives may be incorporated into the master batch in appropriate amounts or added to the final polymer during processing.
  • the amount of polar flame retardant additive used in the final flame retardant polymer should be an amount effective to yield the desired flame resistance of the polymer. Amounts will vary depending upon the particular flame retardant additives and polyolefin used and on the UL94 rating desired. The combination of additives may optimized using routine experimentation to achieve the particular goals desired. The nature of the polymer, the degree of flame retardancy required, the cost of the polymer, the costs of the various additives, the intended use for the flame retardant polymer, and the value in use of the flame retardant polymer are all factors that may influence the combination of additives selected.
  • a preferred combination of additives for use in flame retardant polyolefins, especially in polypropylene, propylene/ethylene copolymers, and mixtures and blends thereof, is disclosed in Papazoglou, WO 98/17718 [U.S. Appln. Ser. No. 08/951,931], incorporated herein by reference.
  • the composition comprises: the polyolefin, preferably polypropylene; 3 to 10% by weight of at least one tris- (trihaloneopentyl) phosphate flame retardant additive, preferably tris- (tribromoneopentyl) phosphate; 0.5 to 5% of a co-additive halogenated flame retardant additive having at least one halogen atom attached to an aliphatic carbon atom as part of its molecular structure, preferably tetrabromobisphenol-A-bis (2, 3-dibromopropyl) ether or tetra- bromobisphenol-S-bis (2, 3-dibromopropyl) ether; and a flame retardant synergist selected from the group consisting of antimony trioxide, antimony pentoxide, zinc stannate, sodium antimonate, zinc hydroxystannate, and zinc borate, preferably antimony trioxide in which the ratio of the weight of antimony trioxide to the total weight of the tri
  • the master batches may be compounded using techniques well known in the art. It is desirable to achieve uniformity of the formulation if the optimum performance is to be obtained. The use of a twin screw extruder is preferred to the use of a single screw extruder. It is also desirable to keep the extrusion temperature above the melting points of the elastomeric carrier resin, the flame retardant additives, and any other additives. The extrusion temperature should not be so high as to accentuate the difference between the viscosities of the polyolefin and the additives. Extrusion temperatures below
  • the master batch may be prepared in one step or in several steps. When the master batch is prepared in one step, all the additives are incorporated into the carrier resin in the same processing step. When several steps are used, the flame retardant additive or additives are typically incorporated into the carrier resin in the first processing step. Additional additives are incorporated into the flame retardant additive containing master batch in an additional processing step or steps. By this procedure, final master batches containing different additive packages may be formulated for specific applications from an initial flame retardant containing master batch.
  • the master batches are useful in the preparation of flame retardant polymers, especially polyolefins.
  • the master batch comprises one or more flame retardant additives and may comprise additional flame retardant synergists and/or other additives, such as hydrotalcite and anti-oxidants. It may be comprise the complete " additive package" so that it is unnecessary to add additional additives during processing of the final.
  • the master batch may be "letdown," i.e., incorporated into the final flame retardant polymer, by procedures well known to those skilled in the art.
  • a physical mixture of mater batch and polymer can be prepared by, for example, using a tumble mixer and fed an extruder.
  • the master batch and the polymer can be fed simultaneously into an extruder using loss-in weight feeders.
  • the relative amounts of master batch and polymer used will depend on the level of additives in the master batch and the additive level desired in the final polymer. Additional additives, such as flame retardant synergists, hydrotalcite, and anti-oxidants, may be added at this time, if desired.
  • the use of a twin screw extruder is preferred to the use of a single screw extruder. It is also desirable to keep the extrusion temperature above the melting points of the polymer, the flame retardant additives, the elastomer and any other additives. The extrusion temperature should not be so high as to accentuate the difference between the viscosities of the polyolefin and the additives. Extrusion temperatures below 230°C are generally preferable. The final flame retardant polymer is typically quenched in a water and pelletized following extrusion.
  • Flame retardant polyolefins especially bloom retardant and bloom retardant polypropylene, are especially useful for articles fabricated by molding processes, particularly for molded products used in the electrical industry.
  • the advantageous properties of this invention can be observed by reference to the following examples which illustrate, but do not limit, the invention.
  • DLPDP Dilauryl thio dipropionate Engage ® 8180 Elastomer (density, 0.863 g/cm 3 ; Mooney viscosity at 121°C, 35; melt flow index, 30 dg/min; shore hardness, 66; DSC melting peak, 49°C; ultimate elongation, >800%) (DuPont Dow, Wilmington, DE)
  • Engage ® 8403 Elastomer (density, 0.913 g/cm 3 ; Mooney viscosity at 121°C, 1.5; melt flow index, 0.5 dg/min; shore hardness, 96; DSC melting peak, 107°C; ultimate elongation, 700%) (DuPont Dow, Wilmington, DE)
  • T(die) 220°C
  • the extruded strands were quenched in a 6 ' water bath and then pelletized.
  • the pellets were air dried overnight to remove surface moisture, and subsequently injection molded in a Battenfeld 800/315CDC injection molding machine, operating at the following conditions:
  • the mold used was a simple cavity mold producing a square plaque (2" x 2" x 1/8"), two 1/8" UL bars (1/2" x 5" x 1/8"), one 1/16" UL bar (1/2" x 5" x 1/16"), one 3/16" UL bar (1/2" x 5" x 3/16"), one ASTM tensile specimen (3/4" x 6" x 1/8"), one ASTM Izod specimen (1/2" x 2" x 1/8"), and one Oxygen Index specimen (1/4" x 5" x 1/8").
  • Molded plaques of the desired formulations were (2" x 2" x 1/8") were oven aged at 100°C in a recirculating oven for either 8 days or 28 days. The plaques were then placed into a 400 mL beaker containing approximately 50 mL of dichloromethane for 3 min with continuous stirring. The solvent was transferred into a pre-weighed cup and allowed to evaporate. The residue was assumed to be bloomed flame retardant material .
  • Oxygen index is defined as the minimum concentration of oxygen, expressed in volume percent, that will just support combustion. Oxygen index measurements were made following ASTM D-2863 as described in Papazoglou, WO 98/17718,. UL94 measurements were carried out using standard procedures.
  • Example 16 17 18 19 20 Profax ® 6523 87% 85% 82% 85% 82% PE-68 9% 9% 9% 9% 9% 9% 9% 9% 9% 9% 9% 9% 9% 9%
  • Example 23-24 These examples illustrate bloom inhibition and flame retardance in a composition that contains a mixture flame retardant materials similar to that disclosed in WO 98/17718. Results are given in Table 6.
  • a master batch was prepared using a ZSK 30 mm co- rotating intermeshing twin screw extruder.
  • the elastomer and the additives were metered in using loss-in weight feeders.
  • Elastomer pellets were fed into the main feed throat using a Acrison loss-in weight feeder.
  • the flame retardant additive or additives was fed into the main feed throat using a K-tron loss-in weight feeder.
  • Engage ® 8180 elastomer can be extruded by a barrel temperature of 150°C and a screw speed of 250 rpm with a 70% torque requirement.
  • a master batch was formed by extruding tris (3-bromo-
  • a master batch was formed by extruding a 5:3 mixture of tris (3-bromo-2 , 2-bis (bromomethyl) propyl) phosphate flame retardant additive and PE-68 flame retardant additive into Engage ® 8180 elastomeric carrier using the procedure described in Example 31.
  • a barrel temperature of 80°C was used. Recorded melt temperature was 95°C. Screw speed varied between 150-250 rpm. The extruder overtorqued at temperatures below 80°C.
  • a series of master batches was prepared using Haake 19" conical, partially intermeshing, counter rotating, twin screw extruder.
  • step (b) A mixture of 79.4% of the master batch from step (a), 4.5% tris (3 -bromo-2, 2-bis (bromomethyl) propyl) phosphate flame retardant additive, 7.5% PE-68 flame retardant additive, and 8.60% antimony trioxide flame retardant synergist concentrate (70% antimony trioxide and 30% polypropylene) were extruded to produce a master batch containing 34.15% of additives in the elastomeric carrier.
  • step (c) The procedure of step (b) was repeated using 79.4% of the master batch from step (b) in place of the master batch of step (a) to produce a master batch containing 45.4% of additives in the elastomeric carrier.
  • step (d) The procedure of step (b) was repeated using 79.4% of the master batch from step (c) in place of the master batch of step (a) to produce a master batch containing 54.7% of additives in the elastomeric carrier.
  • step (e) The procedure of step (b) was repeated using 79.4% of the master batch from step (d) in place of the master batch of step (a) to produce a master batch containing 62.4% of additives in the elastomeric carrier.

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Abstract

L'invention concerne un mélange maître pour des compositions de polymères résistantes à l'efflorescence et non inflammables. Ce mélange contient au moins 25 % en poids d'additifs non inflammables polaires et au moins une résine véhicule élastomère et éventuellement des antioxydants, des composés synergiques non inflammables et d'autres additifs. Les résines véhicules élastomères préférées sont sensiblement des copolymères linéaires d'éthylène/C5-C10 α-oléfine préparés par catalyse à géométrie contrainte à l'aide de catalyseurs de métallocène, en particulier, d'élastomères d'α-octène/éthylène. Un additif non inflammable polaire préféré est le tris-(tribromonéopentyl)-phosphate. Il est possible de préparer des mélanges maîtres contenant jusqu'à 70 % en poids d'additifs polaires.
PCT/US1999/030764 1998-12-22 1999-12-22 Concentrats d'additifs pour des polymeres olefiniques WO2000037552A1 (fr)

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US7442742B1 (en) 2007-04-04 2008-10-28 Carolina Color Corporation Masterbatch composition
EP2061831B1 (fr) 2006-09-14 2012-03-28 Ingenia Polymers Inc. Procédé de préparation de concentrés d'additifs en granulés à concentration élevée pour polymère
US20170152368A1 (en) * 2015-11-27 2017-06-01 Ricoh Company, Ltd. Resin composition, molded body, electronic component, electronic apparatus, and electronic office apparatus
US9969881B2 (en) 2014-07-18 2018-05-15 Carolina Color Corporation Process and composition for well-dispersed, highly loaded color masterbatch
US10428189B2 (en) 2014-07-18 2019-10-01 Chroma Color Corporation Process and composition for well dispersed, highly loaded color masterbatch
US11186711B2 (en) 2016-11-02 2021-11-30 Dow Global Technologies Llc Semi-crystalline polyolefin-based additive masterbatch composition
US11370891B2 (en) 2016-11-02 2022-06-28 Dow Global Technologies Llc Semi-crystalline polyolefin-based additive masterbatch composition

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3324205A (en) * 1963-03-05 1967-06-06 Celanese Corp Halogenated phosphates and phosphonates and method of preparation
US4203882A (en) * 1977-10-27 1980-05-20 Montedison S.P.A. Self-extinguishing polymeric compositions based on modified polypropylene
US4699734A (en) * 1985-11-06 1987-10-13 A. Schulman, Inc. Flame-retardant polyolefin compositions containing exudation inhibitor and process for producing same
US5391618A (en) * 1992-10-15 1995-02-21 Mitsubishi Petrochemical Company Limited Propylene resin compositions
US5608008A (en) * 1995-02-03 1997-03-04 Tosoh Corporation Polypropylene resin composition and molded product

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3324205A (en) * 1963-03-05 1967-06-06 Celanese Corp Halogenated phosphates and phosphonates and method of preparation
US4203882A (en) * 1977-10-27 1980-05-20 Montedison S.P.A. Self-extinguishing polymeric compositions based on modified polypropylene
US4699734A (en) * 1985-11-06 1987-10-13 A. Schulman, Inc. Flame-retardant polyolefin compositions containing exudation inhibitor and process for producing same
US5391618A (en) * 1992-10-15 1995-02-21 Mitsubishi Petrochemical Company Limited Propylene resin compositions
US5608008A (en) * 1995-02-03 1997-03-04 Tosoh Corporation Polypropylene resin composition and molded product

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2061831B1 (fr) 2006-09-14 2012-03-28 Ingenia Polymers Inc. Procédé de préparation de concentrés d'additifs en granulés à concentration élevée pour polymère
US9193838B2 (en) 2006-09-14 2015-11-24 Ingenia Polymers, Inc. High concentration pelletized additive concentrates for polymer
US7442742B1 (en) 2007-04-04 2008-10-28 Carolina Color Corporation Masterbatch composition
US9969881B2 (en) 2014-07-18 2018-05-15 Carolina Color Corporation Process and composition for well-dispersed, highly loaded color masterbatch
US10428189B2 (en) 2014-07-18 2019-10-01 Chroma Color Corporation Process and composition for well dispersed, highly loaded color masterbatch
US20170152368A1 (en) * 2015-11-27 2017-06-01 Ricoh Company, Ltd. Resin composition, molded body, electronic component, electronic apparatus, and electronic office apparatus
US11186711B2 (en) 2016-11-02 2021-11-30 Dow Global Technologies Llc Semi-crystalline polyolefin-based additive masterbatch composition
US11370891B2 (en) 2016-11-02 2022-06-28 Dow Global Technologies Llc Semi-crystalline polyolefin-based additive masterbatch composition

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