WO2010017554A1 - Polyolefin compositions with grafted flame-retardants - Google Patents
Polyolefin compositions with grafted flame-retardants Download PDFInfo
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- WO2010017554A1 WO2010017554A1 PCT/US2009/053297 US2009053297W WO2010017554A1 WO 2010017554 A1 WO2010017554 A1 WO 2010017554A1 US 2009053297 W US2009053297 W US 2009053297W WO 2010017554 A1 WO2010017554 A1 WO 2010017554A1
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- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/40—Introducing phosphorus atoms or phosphorus-containing groups
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- Polyolefins are flammable and require flame-retardant additives to be suitable in flame-retardant applications. Many of the additives, particularly those that are halogen-free, are somewhat incompatible with polyolefins and lead to deterioration in mechanical properties.
- flame-retardant compositions in which the additive does not need to be dispersed, but instead is bound to the polymer. It is particularly desirable to provide improved intumescent flame-retardant compositions in combination with nitrogen and carbon sources.
- the composition would be useful in various industries, including wire and cable, automotive, building solutions, and others.
- the present invention provides a flame-retardant composition
- a flame-retardant composition comprising (a) a polyolefin and (b) a graftable, phosphorus-containing coagent present in an amount greater than about 1.0 weight percent up to about 20.0 weight percent.
- the composition can further comprise a free-radical inducing species.
- useful polyolefins include ethylene polymers, ethylene/styrene interpolymers, ethylene/unsaturated ester copolymers, halogenated ethylene polymers, and propylene polymers.
- suitable ethylene polymers they generally fall into four main classifications: (1) highly -branched; (2) heterogeneous linear; (3) homogeneously branched linear; and (4) homogeneously branched substantially linear.
- These polymers can be prepared with Ziegler-Natta catalysts, metallocene or vanadium-based single-site catalysts, or constrained geometry single- site catalysts.
- Highly branched ethylene polymers include low density polyethylene (LDPE). These polymers can be prepared with a free-radical initiator at high temperatures and high pressure. Alternatively, they can be prepared with a coordination catalyst at high temperatures and relatively low pressures. These polymers have a density between about 0.910 grams per cubic centimeter and about 0.940 grams per cubic centimeter as measured by ASTM D-792.
- LDPE low density polyethylene
- Heterogeneous linear ethylene polymers include linear low density polyethylene (LLDPE), ultra-low density polyethylene (ULDPE), very low density polyethylene (VLDPE), and high density polyethylene (HDPE).
- Linear low density ethylene polymers have a density between about 0.850 grams per cubic centimeter and about 0.940 grams per cubic centimeter.
- the LLDPE is an interpolymer of ethylene and one or more other alpha-olefins having from 3 to 18 carbon atoms, more preferably from 3 to 8 carbon atoms.
- comonomers include 1-butene, 4-methyl-l-pentene, 1-hexene, and 1-octene.
- Ultra-low density polyethylene and very low density polyethylene are known interchangeably. These polymers have a density between about 0.870 grams per cubic centimeter and about 0.910 grams per cubic centimeter. High density ethylene polymers are generally homopolymers with a density between about 0.941 grams per cubic centimeter and about 0.965 grams per cubic centimeter.
- Homogeneously branched linear ethylene polymers include homogeneous LLDPE.
- the uniformly branched/homogeneous polymers are those polymers in which the comonomer is randomly distributed within a given interpolymer molecule and wherein the interpolymer molecules have a similar ethylene/comonomer ratio within that interpolymer.
- Homogeneously-branched substantially linear ethylene polymers include (a) homopolymers of C 2 -C 20 olefins, such as ethylene, propylene, and 4-methyl-l- pentene, (b) interpolymers of ethylene with at least one C3-C 2 0 alpha-olefin, C 2 -C 2 0 acetylenically unsaturated monomer, C 4 -C 18 diolefin, or combinations of the monomers, and (c) interpolymers of ethylene with at least one of the C 3 -C 20 alpha- olefins, diolefins, or acetylenically unsaturated monomers in combination with other unsaturated monomers.
- C 2 -C 20 olefins such as ethylene, propylene, and 4-methyl-l- pentene
- These polymers generally have a density between about 0.850 grams per cubic centimeter and about 0.970 grams per cubic centimeter. Preferably, the density is between about 0.85 grams per cubic centimeter and about 0.955 grams per cubic centimeter, more preferably, between about 0.850 grams per cubic centimeter and 0.920 grams per cubic centimeter.
- Ethylene/styrene interpolymers useful in the present invention include substantially random interpolymers prepared by polymerizing an olefin monomer (i.e., ethylene, propylene, or alpha-olefin monomer) with an aromatic vinylidene monomer, hindered aliphatic vinylidene monomer, or cycloaliphatic vinylidene monomer.
- Suitable olefin monomers contain from 2 to 20, preferably from 2 to 12, more preferably from 2 to 8 carbon atoms.
- such monomers include ethylene, propylene, 1-butene, 4-methyl-l-pentene, 1-hexene, and 1-octene.
- such monomers include a combination of ethylene with propylene or C 4 - 8 alpha-olefins.
- the ethylene/styrene interpolymers polymerization components can also include ethylenically unsaturated monomers such as strained ring olefins.
- strained ring olefins include norbornene and Ci-io alkyl- or C ⁇ -io aiyl- substituted norbornenes.
- Ethylene/unsaturated ester copolymers useful in the present invention can be prepared by conventional high-pressure techniques.
- the unsaturated esters can be alkyl acrylates, alkyl methacrylates, or vinyl carboxylates.
- the alkyl groups can have 1 to 8 carbon atoms and preferably have 1 to 4 carbon atoms.
- the carboxylate groups can have 2 to 8 carbon atoms and preferably have 2 to 5 carbon atoms.
- the portion of the copolymer attributed to the ester comonomer can be in the range of about 5 to about 50 percent by weight based on the weight of the copolymer, and is preferably in the range of about 15 to about 40 percent by weight.
- acrylates and methacrylates are ethyl acrylate, methyl acrylate, methyl methacrylate, t-butyl acrylate, n-butyl acrylate, n-butyl methacrylate, and 2-ethylhexyl acrylate.
- vinyl carboxylates are vinyl acetate, vinyl propionate, and vinyl butanoate.
- the melt index of the ethylene/unsaturated ester copolymers can be in the range of about 0.5 to about 50 grams per 10 minutes.
- Halogenated ethylene polymers useful in the present invention include fluorinated, chlorinated, and brominated olefin polymers.
- the base olefin polymer can be a homopolymer or an interpolymer of olefins having from 2 to 18 carbon atoms.
- the olefin polymer will be an interpolymer of ethylene with propylene or an alpha-olefin monomer having 4 to 8 carbon atoms.
- Preferred alpha- olefin comonomers include 1-butene, 4-methyl-l-pentene, 1-hexene, and 1-octene.
- the halogenated olefin polymer is a chlorinated polyethylene.
- propylene polymers useful in the present invention include propylene homopolymers and copolymers of propylene with ethylene or another unsaturated comonomer. Copolymers also include terpolymers, tetrapolymers, etc.
- the polypropylene copolymers comprise units derived from propylene in an amount of at least about 60 weight percent.
- the propylene monomer is at least about 70 weight percent of the copolymer, more preferably at least about 80 weight percent.
- the polyolefin can be an olefin multi-block interpolymer.
- Olefin multi-block interpolymers may be made with two catalysts incorporating differing quantities of comonomer and a chain shuttling agent.
- Preferred olefin multi-block interpolymers are ethylene/ ⁇ -olefin multi-block interpolymers.
- An ethylene/ ⁇ -olefin multi-block interpolymer has one or more of the following characteristics:
- ⁇ T 48 degrees Celsius for ⁇ H greater than 130 J/g , wherein the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30 degrees Celsius; or
- an elastic recovery, Re in percent at 300 percent strain and 1 cycle measured with a compression-molded film of the ethylene/ ⁇ -olefin interpolymer, and has a density, d, in grams/cubic centimeter, wherein the numerical values of Re and d satisfy the following relationship when ethylene/ ⁇ -olefin interpolymer is substantially free of a cross-linked phase: Re >1481-1629(d); or
- (6) a molecular fraction which elutes between 40 degrees Celsius and 130 degrees Celsius when fractionated using TREF, characterized in that the fraction has a molar comonomer content of at least 5 percent higher than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, wherein said comparable random ethylene interpolymer has the same comonomer(s) and has a melt index, density, and molar comonomer content (based on the whole polymer) within 10 percent of that of the ethylene/ ⁇ -olefin interpolymer; or
- the ethylene/ ⁇ -olefin interpolymers can be ethylene/ ⁇ -olefin copolymers made in a continuous, solution polymerization reactor, and possess a most probable distribution of block lengths.
- the copolymers contain 4 or more blocks or segments including terminal blocks.
- the ethylene/ ⁇ -olefin multi-block interpolymers typically comprise ethylene and one or more copolymerizable ⁇ -olefin comonomers in polymerized form, characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical or physical properties. That is, the ethylene/ ⁇ -olefin interpolymers are block interpolymers, preferably multi-block interpolymers or copolymers.
- the multi-block copolymer can be represented by the following formula:
- n is at least 1, preferably an integer greater than 1, such as 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, or higher
- A represents a hard block or segment
- B represents a soft block or segment.
- the As and Bs are linked in a substantially linear fashion, as opposed to a substantially branched or substantially star-shaped fashion.
- a blocks and B blocks are randomly distributed along the polymer chain.
- the block copolymers usually do not have a structure as follows.
- the block copolymers do not usually have a third type of block, which comprises different comonomer(s).
- each of block A and block B has monomers or comonomers substantially randomly distributed within the block.
- neither block A nor block B comprises two or more sub-segments (or sub-blocks) of distinct composition, such as a tip segment, which has a substantially different composition than the rest of the block.
- the ethylene multi-block polymers typically comprise various amounts of “hard” and “soft” segments.
- “Hard” segments refer to blocks of polymerized units in which ethylene is present in an amount greater than about 95 weight percent, and preferably greater than about 98 weight percent based on the weight of the polymer.
- the comonomer content (content of monomers other than ethylene) in the hard segments is less than about 5 weight percent, and preferably less than about 2 weight percent based on the weight of the polymer.
- the hard segments comprise all or substantially all ethylene.
- Soft segments refer to blocks of polymerized units in which the comonomer content (content of monomers other than ethylene) is greater than about 5 weight percent, preferably greater than about 8 weight percent, greater than about 10 weight percent, or greater than about 15 weight percent based on the weight of the polymer.
- the comonomer content in the soft segments can be greater than about 20 weight percent, greater than about 25 weight percent, greater than about 30 weight percent, greater than about 35 weight percent, greater than about 40 weight percent, greater than about 45 weight percent, greater than about 50 weight percent, or greater than about 60 weight percent.
- the soft segments can often be present in a block interpolymer from about 1 weight percent to about 99 weight percent of the total weight of the block interpolymer, preferably from about 5 weight percent to about 95 weight percent, from about 10 weight percent to about 90 weight percent, from about 15 weight percent to about 85 weight percent, from about 20 weight percent to about 80 weight percent, from about 25 weight percent to about 75 weight percent, from about 30 weight percent to about 70 weight percent, from about 35 weight percent to about 65 weight percent, from about 40 weight percent to about 60 weight percent, or from about 45 weight percent to about 55 weight percent of the total weight of the block interpolymer.
- the hard segments can be present in similar ranges.
- the soft segment weight percentage and the hard segment weight percentage can be calculated based on data obtained from DSC or NMR. Such methods and calculations are disclosed in U.S. Patent Application Serial No. 11/376,835, incorporated by reference herein in its entirety.
- multi-block copolymer or “segmented copolymer” refers to a polymer comprising two or more chemically distinct regions or segments (referred to as “blocks”) preferably joined in a linear manner, that is, a polymer comprising chemically differentiated units which are joined end-to-end with respect to polymerized ethylenic functionality, rather than in pendent or grafted fashion.
- the blocks differ in the amount or type of comonomer incorporated therein, the density, the amount of crystallinity, the crystallite size attributable to a polymer of such composition, the type or degree of tacticity (isotactic or syndiotactic), regio-regularity or regio-irregularity, the amount of branching, including long chain branching or hyper-branching, the homogeneity, or any other chemical or physical property.
- the multi-block copolymers are characterized by unique distributions of both polydispersity index (PDI or Mw/Mn), block length distribution, and/or block number distribution due to the unique process making of the copolymers.
- the polymers when produced in a continuous process, desirably possess PDI from 1.7 to 2.9, preferably from 1.8 to 2.5, more preferably from 1.8 to 2.2, and most preferably from 1.8 to 2.1.
- the polymers When produced in a batch or semi-batch process, the polymers possess PDI from 1.0 to 2.9, preferably from 1.3 to 2.5, more preferably from 1.4 to 2.0, and most preferably from 1.4 to 1.8.
- an ethylene/ ⁇ -olefin multi-block interpolymer has an ethylene content of from 60 to 90 percent, a diene content of from 0 to 10 percent, and an ⁇ -olefin content of from 10 to 40 percent, based on the total weight of the polymer.
- such polymers are high molecular weight polymers, having a weight average molecular weight (Mw) from 10,000 to about 2,500,000, preferably from 20,000 to 500,000, more preferably from 20,000 to 350,000; a polydispersity less than 3.5, more preferably less than 3 and as low as about 2; and a Mooney viscosity (ML (1+4) at 125 degrees Celsius) from 1 to 250.
- the ethylene multi-block interpolymers have a density of less than about 0.90 grams per cubic centimeter, preferably less than about 0.89 grams per cubic centimeter, more preferably less than about 0.885 grams per cubic centimeter, even more preferably less than about 0.88 grams per cubic centimeter and even more preferably less than about 0.875 grams per cubic centimeter. In one embodiment, the ethylene multi-block interpolymers have a density greater than about 0.85 grams per cubic centimeter, and more preferably greater than about 0.86 grams per cubic centimeter. Density is measured by the procedure of ASTM D-792. Low density ethylene multi-block copolymers are generally characterized as amorphous, flexible, and have good optical properties, for example, high transmission of visible and UV-light and low haze.
- the ethylene multi-block interpolymers have a melting point of less than about 125 degrees Celsius.
- the melting point is measured by the differential scanning calorimetry (DSC) method described in U.S. Publication 2006/0199930 (WO 2005/090427), incorporated herein by reference.
- ethylene multi-block interpolymers and their preparation and use are more fully described in WO 2005/090427, US2006/0199931, US2006/0199930, US2006/0199914, US2006/0199912, US2006/0199911, US2006/0199910, US2006/0199908, US2006/0199907, US2006/0199906, US2006/0199905, US2006/0199897, US2006/0199896, US2006/0199887, US2006/0199884, US2006/0199872, US2006/0199744, US2006/0199030, US2006/0199006 and US2006/0199983; each publication is fully incorporated herein by reference.
- the olefin multi-block interpolymer can be based on polypropylene whereby the crystalline segment of the chain is isotactic polypropylene. Also preferably, the elastomeric segment could be based on any alpha olefin copolymer system.
- the polymer may be one or a mixture of the above polymers.
- the melt index of the polymers is between about 0.01 to about 1000 grams per 10 minutes as measured by ASTM 1238, condition I.
- the melt index is between about 0.1 to about 500 grams per 10 minutes.
- the melt index is between about 1 to about 100 grams per 10 minutes.
- the graftable, phosphorus-containing coagent is present in an amount greater than about 1.0 weight percent up to about 20.0 weight percent; preferably, between about2.0 weight percent to about 15.0 weight percent; and more preferably, between about 3.0 weight percent to about 10.0 weight percent.
- Suitable examples of graftable, phosphorus-containing coagents include, but are not limited to, triallyl phosphate, triallyl phosphoric triamide, N-hydroxymethyl-3- dimethylphosphonopropionamide, 2-ethyl methacrylate phosphoric acid, phosphate esters of hydroxyl ethyl methacrylate, and vinyl phosphonic acid.
- Suitable graftable phosphorus containing coagents can simultaneously contain phosphorus, nitrogen, and silicon elements. These flame-retardants may provide synergistic flame-retardant properties.
- these graftable phosphorus containing coagents can further contain other flame-retardant groups (for example, halogens, sulfur, or boron).
- flame-retardant groups for example, halogens, sulfur, or boron
- Free-radicals can be produced for use in the present invention in a variety of ways known to persons skilled in the art.
- Useful free-radical inducing species include organic peroxides, Azo free-radical initiators, and bicumene.
- the free- radical inducing species is an organic peroxide.
- oxygen-rich environments can initiate useful free-radicals.
- Preferable organic peroxides include dicumyl peroxide and Vulcup R.
- Vulcup R is a highly active bisperoxide. It is a mixture of para and meta isomers of bis(tert-butyl peroxy)-diisopropylbenzene available from GEO Specialty Chemicals, Gibbstown, NJ, USA.
- the organic peroxide can be added via direct injection.
- the peroxide is preferably present in the reactive composition in an amount of about 0.01 weight percent to about 3 weight percent, more preferably about 0.02 weight percent to about 2.5 weight percent, and most preferably about 0.03 weight percent to about 2 weight percent.
- the present composition may further comprise other polymers and additives.
- Suitable additional additives can include antioxidants, other flame-retardants, and synergists.
- FIG. 1 is a set of two graphs, which illustrates the evolution of complex viscosity ( ⁇ *) with time for a series of LUPEROXTM 130 2,5-dimethyl-2,5-di(t- butylperoxy)hex-3-yne ("L-130,” 0.2 weight percent, 0.08 g) initiated crosslinking reactions with coagent at 90 ⁇ mole/g.
- L-130 2,5-dimethyl-2,5-di(t- butylperoxy)hex-3-yne
- FIG. 2 is a graph, illustrating the effect of cure temperature on crosslink yield for L-130 (0.2 weight percent, 0.08 g), coagent at 90 ⁇ mole/g, and 10 minutes.
- FIG. 3 is a set of two graphs, which illustrates the evolution of complex viscosity ( ⁇ *) with time for a series of L-130 (0.5 weight percent) initiated crosslinking reactions with coagent at 90 ⁇ mole/g.
- FIG. 4 is a graph, illustrating the effect of a peroxide on the evolution of Moving Die Rheometer torque (modulus) at 140 degrees Celsius of a blend of ethylene vinyl acetate copolymer and triallyl phosphate.
- FIG. 5 is a graph, illustrating the effect of a peroxide on the temperature- dependent weight loss of a blend of ethylene vinyl acetate copolymer and triallyl phosphate, measured by thermogravimetric analysis (TGA).
- FIG. 6 is a graph, illustrating the effect of triallyl phosphate on the peak heat release rate of a blend of ethylene vinyl acetate copolymer and a peroxide, measured by a cone calorimeter.
- TEP Triallyl Phosphate
- TAM Triallyl trimesate
- TPM Monomer Polymer Inc., Feasterville, PA, USA
- TCP triallyl phosphate
- TCPTA trimethylolpropane triacrylate
- L- 130 2,5-dimethyl-2,5-di(t-butylperoxy)hex-3-yne
- PE 40 g was mixed with L- 130 and the desired amount of coagent at 100 degrees Celsius using a Haake Polylab R600 internal batch mixer. An aliquot of the resulting masterbatch (5 g) was reacted in the cavity of an Alpha Technologies Advanced Polymer Analyzer at 200 degrees Celsius using an oscillation arc of 3 degrees and a frequency of 100 cpm. On-line measurements of dynamic storage (G') and loss (G") moduli provided the information needed to report the rate of G' evolution with time as well as changes to complex viscosity.
- G' dynamic storage
- G" moduli On-line measurements of dynamic storage (G') and loss (G") moduli provided the information needed to report the rate of G' evolution with time as well as changes to complex viscosity.
- FIG. 1 illustrates the evolution of complex viscosity ( ⁇ *) with time for a series of L- 130 (0.2 weight percent, 0.08 g) initiated crosslinking reactions.
- ⁇ * complex viscosity
- L- 130 0.2 weight percent, 0.08 g
- TBP Triallyl Phosphate
- MP Monomer Polymer
- TEP triallyl phosphate
- Liuperox 231 peroxide
- the blend testing involved (a) Moving Die Rheometer (MDR) experiments at a temperature of 140 degrees Celsius for 10 minutes, (b) thermogravimetric analysis (TGA) under nitrogen from ambient temperature to 900 degrees Celsius at a rate of 10 degrees Celsius/min, on specimens out of MDR, and (c) Cone Calorimeter (75 mil, 4" x 4" plaque, 35 kW/m 2 , no grid). The plaque was prepared by compression molding at 140 degrees Celsius for 10 minutes.
- MDR Moving Die Rheometer
- TGA thermogravimetric analysis
- the temperature-dependent weight loss of the specimens out of MDR is plotted in FIG. 5. Without any peroxide, the weight loss of the TAP compositions started around 100 degrees Celsius, which is believed to indicate that the unbound TAP was volatile and leaching from the polymer at elevated temperatures. Thermogravimetric analysis (TGA) of TAP by itself showed weight loss starting at about the same temperature.
- compositions contained peroxide in addition to TAP, the onset of weight loss was shifted to around 220 degrees Celsius, indicating grafting of TAP to the polymer.
- FIG. 6 presents the results of cone calorimeter experiments. Grafting of 9 weight percent TAP reduced the peak heat release rate by about 31 percent. There was also an upward shift in the corresponding time to peak heat release. These results indicate that grafted TAP imparts significantly improved fire performance.
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Abstract
The present invention provides a flame-retardant composition made from or containing (a) a polyolefin and (b) a graftable, phosphorus-containing coagent. The invention yields a polyolefin having a grafted flame retardant bonded thereto. Suitable graftable, phosphorus-containing coagent can simultaneously contain phosphorus, nitrogen, and silicon elements.
Description
POLYOLEFIN COMPOSITIONS WITH GRAFTED FLAME-RETARDANTS
Polyolefins are flammable and require flame-retardant additives to be suitable in flame-retardant applications. Many of the additives, particularly those that are halogen-free, are somewhat incompatible with polyolefins and lead to deterioration in mechanical properties.
It is desirable to have flame-retardant compositions in which the additive does not need to be dispersed, but instead is bound to the polymer. It is particularly desirable to provide improved intumescent flame-retardant compositions in combination with nitrogen and carbon sources. The composition would be useful in various industries, including wire and cable, automotive, building solutions, and others.
The present invention provides a flame-retardant composition comprising (a) a polyolefin and (b) a graftable, phosphorus-containing coagent present in an amount greater than about 1.0 weight percent up to about 20.0 weight percent. The composition can further comprise a free-radical inducing species.
Examples of useful polyolefins include ethylene polymers, ethylene/styrene interpolymers, ethylene/unsaturated ester copolymers, halogenated ethylene polymers, and propylene polymers. With regard to the suitable ethylene polymers, they generally fall into four main classifications: (1) highly -branched; (2) heterogeneous linear; (3) homogeneously branched linear; and (4) homogeneously branched substantially linear. These polymers can be prepared with Ziegler-Natta catalysts, metallocene or vanadium-based single-site catalysts, or constrained geometry single- site catalysts.
Highly branched ethylene polymers include low density polyethylene (LDPE). These polymers can be prepared with a free-radical initiator at high temperatures and high pressure. Alternatively, they can be prepared with a coordination catalyst at high temperatures and relatively low pressures. These polymers have a density between about 0.910 grams per cubic centimeter and about 0.940 grams per cubic centimeter as measured by ASTM D-792.
Heterogeneous linear ethylene polymers include linear low density polyethylene (LLDPE), ultra-low density polyethylene (ULDPE), very low density polyethylene (VLDPE), and high density polyethylene (HDPE). Linear low density ethylene polymers have a density between about 0.850 grams per cubic centimeter
and about 0.940 grams per cubic centimeter. Also, preferably, the LLDPE is an interpolymer of ethylene and one or more other alpha-olefins having from 3 to 18 carbon atoms, more preferably from 3 to 8 carbon atoms. In certain embodiments, comonomers include 1-butene, 4-methyl-l-pentene, 1-hexene, and 1-octene.
Ultra-low density polyethylene and very low density polyethylene are known interchangeably. These polymers have a density between about 0.870 grams per cubic centimeter and about 0.910 grams per cubic centimeter. High density ethylene polymers are generally homopolymers with a density between about 0.941 grams per cubic centimeter and about 0.965 grams per cubic centimeter.
Homogeneously branched linear ethylene polymers include homogeneous LLDPE. The uniformly branched/homogeneous polymers are those polymers in which the comonomer is randomly distributed within a given interpolymer molecule and wherein the interpolymer molecules have a similar ethylene/comonomer ratio within that interpolymer.
Homogeneously-branched substantially linear ethylene polymers include (a) homopolymers of C2-C20 olefins, such as ethylene, propylene, and 4-methyl-l- pentene, (b) interpolymers of ethylene with at least one C3-C20 alpha-olefin, C2-C20 acetylenically unsaturated monomer, C4-C18 diolefin, or combinations of the monomers, and (c) interpolymers of ethylene with at least one of the C3-C20 alpha- olefins, diolefins, or acetylenically unsaturated monomers in combination with other unsaturated monomers. These polymers generally have a density between about 0.850 grams per cubic centimeter and about 0.970 grams per cubic centimeter. Preferably, the density is between about 0.85 grams per cubic centimeter and about 0.955 grams per cubic centimeter, more preferably, between about 0.850 grams per cubic centimeter and 0.920 grams per cubic centimeter.
Ethylene/styrene interpolymers useful in the present invention include substantially random interpolymers prepared by polymerizing an olefin monomer (i.e., ethylene, propylene, or alpha-olefin monomer) with an aromatic vinylidene monomer, hindered aliphatic vinylidene monomer, or cycloaliphatic vinylidene monomer. Suitable olefin monomers contain from 2 to 20, preferably from 2 to 12, more preferably from 2 to 8 carbon atoms. In certain embodiments, such monomers include ethylene, propylene, 1-butene, 4-methyl-l-pentene, 1-hexene, and 1-octene. In other embodiments, such monomers include a combination of ethylene with propylene or C4-8 alpha-olefins. Optionally, the ethylene/styrene interpolymers
polymerization components can also include ethylenically unsaturated monomers such as strained ring olefins. Examples of strained ring olefins include norbornene and Ci-io alkyl- or Cβ-io aiyl- substituted norbornenes.
Ethylene/unsaturated ester copolymers useful in the present invention can be prepared by conventional high-pressure techniques. The unsaturated esters can be alkyl acrylates, alkyl methacrylates, or vinyl carboxylates. The alkyl groups can have 1 to 8 carbon atoms and preferably have 1 to 4 carbon atoms. The carboxylate groups can have 2 to 8 carbon atoms and preferably have 2 to 5 carbon atoms. The portion of the copolymer attributed to the ester comonomer can be in the range of about 5 to about 50 percent by weight based on the weight of the copolymer, and is preferably in the range of about 15 to about 40 percent by weight. Examples of the acrylates and methacrylates are ethyl acrylate, methyl acrylate, methyl methacrylate, t-butyl acrylate, n-butyl acrylate, n-butyl methacrylate, and 2-ethylhexyl acrylate. Examples of the vinyl carboxylates are vinyl acetate, vinyl propionate, and vinyl butanoate. The melt index of the ethylene/unsaturated ester copolymers can be in the range of about 0.5 to about 50 grams per 10 minutes.
Halogenated ethylene polymers useful in the present invention include fluorinated, chlorinated, and brominated olefin polymers. The base olefin polymer can be a homopolymer or an interpolymer of olefins having from 2 to 18 carbon atoms. Preferably, the olefin polymer will be an interpolymer of ethylene with propylene or an alpha-olefin monomer having 4 to 8 carbon atoms. Preferred alpha- olefin comonomers include 1-butene, 4-methyl-l-pentene, 1-hexene, and 1-octene. Preferably, the halogenated olefin polymer is a chlorinated polyethylene.
Examples of propylene polymers useful in the present invention include propylene homopolymers and copolymers of propylene with ethylene or another unsaturated comonomer. Copolymers also include terpolymers, tetrapolymers, etc. Typically, the polypropylene copolymers comprise units derived from propylene in an amount of at least about 60 weight percent. Preferably, the propylene monomer is at least about 70 weight percent of the copolymer, more preferably at least about 80 weight percent.
The polyolefin can be an olefin multi-block interpolymer. Olefin multi-block interpolymers may be made with two catalysts incorporating differing quantities of comonomer and a chain shuttling agent. Preferred olefin multi-block interpolymers
are ethylene/α-olefin multi-block interpolymers. An ethylene/α-olefin multi-block interpolymer has one or more of the following characteristics:
(1) an average block index greater than zero and up to about 1.0 and a molecular weight distribution, Mw/Mn, greater than about 1.3; or
(2) at least one molecular fraction which elutes between 40 degrees Celsius and 130 degrees Celsius when fractionated using TREF, characterized in that the fraction has a block index of at least 0.5 and up to about 1 ; or
(3) an Mw/Mn from about 1.7 to about 3.5, at least one melting point, Tm, in degrees Celsius, and a density, d, in grams/cubic centimeter, wherein the numerical values of Tm and d correspond to the relationship:
T1n > -6553.3 + 13735(d) - 7051.7(d)2; or
(4) an Mw/Mn from about 1.7 to about 3.5, and is characterized by a heat of fusion, ΔH in J/g, and a delta quantity, ΔT, in degrees Celsius defined as the temperature difference between the tallest DSC peak and the tallest CRYSTAF peak, wherein the numerical values of ΔT and ΔH have the following relationships:
ΔT > -0.1299(ΔH) + 62.81 for ΔH greater than zero and up to 130 J/g,
ΔT > 48 degrees Celsius for ΔH greater than 130 J/g , wherein the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30 degrees Celsius; or
(5) an elastic recovery, Re, in percent at 300 percent strain and 1 cycle measured with a compression-molded film of the ethylene/α-olefin interpolymer, and has a density, d, in grams/cubic centimeter, wherein the numerical values of Re and d satisfy the following relationship when ethylene/α-olefin interpolymer is substantially free of a cross-linked phase: Re >1481-1629(d); or
(6) a molecular fraction which elutes between 40 degrees Celsius and 130 degrees Celsius when fractionated using TREF, characterized in that the fraction has a molar comonomer content of at least 5 percent higher than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, wherein said comparable random ethylene interpolymer has the same comonomer(s) and has a melt index, density, and molar comonomer content (based on the whole polymer) within 10 percent of that of the ethylene/α-olefin interpolymer; or
(7) a storage modulus at 25 degrees Celsius, G' (25 degrees Celsius), and a storage modulus at 100 degrees Celsius, G' (100 degrees Celsius), wherein the ratio of
G' (25 degrees Celsius) to G' (100 degrees Celsius) is in the range of about 1:1 to about 9:1.
The ethylene/α-olefin interpolymers can be ethylene/ α-olefin copolymers made in a continuous, solution polymerization reactor, and possess a most probable distribution of block lengths. In one embodiment, the copolymers contain 4 or more blocks or segments including terminal blocks.
The ethylene/α-olefin multi-block interpolymers typically comprise ethylene and one or more copolymerizable α-olefin comonomers in polymerized form, characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical or physical properties. That is, the ethylene/α-olefin interpolymers are block interpolymers, preferably multi-block interpolymers or copolymers. In some embodiments, the multi-block copolymer can be represented by the following formula:
(AB)n where n is at least 1, preferably an integer greater than 1, such as 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, or higher, "A" represents a hard block or segment and "B" represents a soft block or segment. Preferably, the As and Bs are linked in a substantially linear fashion, as opposed to a substantially branched or substantially star-shaped fashion. In other embodiments, A blocks and B blocks are randomly distributed along the polymer chain. In other words, the block copolymers usually do not have a structure as follows.
AAA- AA-BBB- BB
In still other embodiments, the block copolymers do not usually have a third type of block, which comprises different comonomer(s). In yet other embodiments, each of block A and block B has monomers or comonomers substantially randomly distributed within the block. In other words, neither block A nor block B comprises two or more sub-segments (or sub-blocks) of distinct composition, such as a tip segment, which has a substantially different composition than the rest of the block.
The ethylene multi-block polymers typically comprise various amounts of "hard" and "soft" segments. "Hard" segments refer to blocks of polymerized units in which ethylene is present in an amount greater than about 95 weight percent, and preferably greater than about 98 weight percent based on the weight of the polymer. In other words, the comonomer content (content of monomers other than ethylene) in the hard segments is less than about 5 weight percent, and preferably less than about 2
weight percent based on the weight of the polymer. In some embodiments, the hard segments comprise all or substantially all ethylene. "Soft" segments, on the other hand, refer to blocks of polymerized units in which the comonomer content (content of monomers other than ethylene) is greater than about 5 weight percent, preferably greater than about 8 weight percent, greater than about 10 weight percent, or greater than about 15 weight percent based on the weight of the polymer. In some embodiments, the comonomer content in the soft segments can be greater than about 20 weight percent, greater than about 25 weight percent, greater than about 30 weight percent, greater than about 35 weight percent, greater than about 40 weight percent, greater than about 45 weight percent, greater than about 50 weight percent, or greater than about 60 weight percent.
The soft segments can often be present in a block interpolymer from about 1 weight percent to about 99 weight percent of the total weight of the block interpolymer, preferably from about 5 weight percent to about 95 weight percent, from about 10 weight percent to about 90 weight percent, from about 15 weight percent to about 85 weight percent, from about 20 weight percent to about 80 weight percent, from about 25 weight percent to about 75 weight percent, from about 30 weight percent to about 70 weight percent, from about 35 weight percent to about 65 weight percent, from about 40 weight percent to about 60 weight percent, or from about 45 weight percent to about 55 weight percent of the total weight of the block interpolymer. Conversely, the hard segments can be present in similar ranges. The soft segment weight percentage and the hard segment weight percentage can be calculated based on data obtained from DSC or NMR. Such methods and calculations are disclosed in U.S. Patent Application Serial No. 11/376,835, incorporated by reference herein in its entirety.
The term "multi-block copolymer" or "segmented copolymer" refers to a polymer comprising two or more chemically distinct regions or segments (referred to as "blocks") preferably joined in a linear manner, that is, a polymer comprising chemically differentiated units which are joined end-to-end with respect to polymerized ethylenic functionality, rather than in pendent or grafted fashion. In a preferred embodiment, the blocks differ in the amount or type of comonomer incorporated therein, the density, the amount of crystallinity, the crystallite size attributable to a polymer of such composition, the type or degree of tacticity (isotactic or syndiotactic), regio-regularity or regio-irregularity, the amount of branching,
including long chain branching or hyper-branching, the homogeneity, or any other chemical or physical property. The multi-block copolymers are characterized by unique distributions of both polydispersity index (PDI or Mw/Mn), block length distribution, and/or block number distribution due to the unique process making of the copolymers. More specifically, when produced in a continuous process, the polymers desirably possess PDI from 1.7 to 2.9, preferably from 1.8 to 2.5, more preferably from 1.8 to 2.2, and most preferably from 1.8 to 2.1. When produced in a batch or semi-batch process, the polymers possess PDI from 1.0 to 2.9, preferably from 1.3 to 2.5, more preferably from 1.4 to 2.0, and most preferably from 1.4 to 1.8.
In one embodiment, an ethylene/α-olefin multi-block interpolymer has an ethylene content of from 60 to 90 percent, a diene content of from 0 to 10 percent, and an α-olefin content of from 10 to 40 percent, based on the total weight of the polymer. In one embodiment, such polymers are high molecular weight polymers, having a weight average molecular weight (Mw) from 10,000 to about 2,500,000, preferably from 20,000 to 500,000, more preferably from 20,000 to 350,000; a polydispersity less than 3.5, more preferably less than 3 and as low as about 2; and a Mooney viscosity (ML (1+4) at 125 degrees Celsius) from 1 to 250.
In one embodiment, the ethylene multi-block interpolymers have a density of less than about 0.90 grams per cubic centimeter, preferably less than about 0.89 grams per cubic centimeter, more preferably less than about 0.885 grams per cubic centimeter, even more preferably less than about 0.88 grams per cubic centimeter and even more preferably less than about 0.875 grams per cubic centimeter. In one embodiment, the ethylene multi-block interpolymers have a density greater than about 0.85 grams per cubic centimeter, and more preferably greater than about 0.86 grams per cubic centimeter. Density is measured by the procedure of ASTM D-792. Low density ethylene multi-block copolymers are generally characterized as amorphous, flexible, and have good optical properties, for example, high transmission of visible and UV-light and low haze.
In one embodiment, the ethylene multi-block interpolymers have a melting point of less than about 125 degrees Celsius. The melting point is measured by the differential scanning calorimetry (DSC) method described in U.S. Publication 2006/0199930 (WO 2005/090427), incorporated herein by reference.
The ethylene multi-block interpolymers and their preparation and use, are more fully described in WO 2005/090427, US2006/0199931, US2006/0199930,
US2006/0199914, US2006/0199912, US2006/0199911, US2006/0199910, US2006/0199908, US2006/0199907, US2006/0199906, US2006/0199905, US2006/0199897, US2006/0199896, US2006/0199887, US2006/0199884, US2006/0199872, US2006/0199744, US2006/0199030, US2006/0199006 and US2006/0199983; each publication is fully incorporated herein by reference.
The olefin multi-block interpolymer can be based on polypropylene whereby the crystalline segment of the chain is isotactic polypropylene. Also preferably, the elastomeric segment could be based on any alpha olefin copolymer system.
The polymer may be one or a mixture of the above polymers.
The melt index of the polymers is between about 0.01 to about 1000 grams per 10 minutes as measured by ASTM 1238, condition I. Preferably, the melt index is between about 0.1 to about 500 grams per 10 minutes. Most preferably, the melt index is between about 1 to about 100 grams per 10 minutes.
The graftable, phosphorus-containing coagent is present in an amount greater than about 1.0 weight percent up to about 20.0 weight percent; preferably, between about2.0 weight percent to about 15.0 weight percent; and more preferably, between about 3.0 weight percent to about 10.0 weight percent.
Suitable examples of graftable, phosphorus-containing coagents include, but are not limited to, triallyl phosphate, triallyl phosphoric triamide, N-hydroxymethyl-3- dimethylphosphonopropionamide, 2-ethyl methacrylate phosphoric acid, phosphate esters of hydroxyl ethyl methacrylate, and vinyl phosphonic acid.
Suitable graftable phosphorus containing coagents can simultaneously contain phosphorus, nitrogen, and silicon elements. These flame-retardants may provide synergistic flame-retardant properties.
Moreover, these graftable phosphorus containing coagents can further contain other flame-retardant groups (for example, halogens, sulfur, or boron).
Free-radicals can be produced for use in the present invention in a variety of ways known to persons skilled in the art. Useful free-radical inducing species include organic peroxides, Azo free-radical initiators, and bicumene. Preferably, the free- radical inducing species is an organic peroxide. Also, oxygen-rich environments can initiate useful free-radicals. Preferable organic peroxides include dicumyl peroxide and Vulcup R.
Vulcup R is a highly active bisperoxide. It is a mixture of para and meta isomers of bis(tert-butyl peroxy)-diisopropylbenzene available from GEO Specialty Chemicals, Gibbstown, NJ, USA.
The organic peroxide can be added via direct injection. When a peroxide is used to generate free-radicals, the peroxide is preferably present in the reactive composition in an amount of about 0.01 weight percent to about 3 weight percent, more preferably about 0.02 weight percent to about 2.5 weight percent, and most preferably about 0.03 weight percent to about 2 weight percent.
The present composition may further comprise other polymers and additives. Suitable additional additives can include antioxidants, other flame-retardants, and synergists.
FIG. 1 is a set of two graphs, which illustrates the evolution of complex viscosity (η*) with time for a series of LUPEROX™ 130 2,5-dimethyl-2,5-di(t- butylperoxy)hex-3-yne ("L-130," 0.2 weight percent, 0.08 g) initiated crosslinking reactions with coagent at 90 μmole/g.
FIG. 2 is a graph, illustrating the effect of cure temperature on crosslink yield for L-130 (0.2 weight percent, 0.08 g), coagent at 90 μmole/g, and 10 minutes.
FIG. 3 is a set of two graphs, which illustrates the evolution of complex viscosity (η*) with time for a series of L-130 (0.5 weight percent) initiated crosslinking reactions with coagent at 90 μmole/g.
FIG. 4 is a graph, illustrating the effect of a peroxide on the evolution of Moving Die Rheometer torque (modulus) at 140 degrees Celsius of a blend of ethylene vinyl acetate copolymer and triallyl phosphate.
FIG. 5 is a graph, illustrating the effect of a peroxide on the temperature- dependent weight loss of a blend of ethylene vinyl acetate copolymer and triallyl phosphate, measured by thermogravimetric analysis (TGA).
FIG. 6 is a graph, illustrating the effect of triallyl phosphate on the peak heat release rate of a blend of ethylene vinyl acetate copolymer and a peroxide, measured by a cone calorimeter.
EXAMPLE
Grafting of Triallyl Phosphate (TAP) to Polyethylene in Comparison with Other Coagents
A metallocene-catalyzed ethylene-octene copolymer (PE, octene content = 7.3 mole percent, MFI = 1.6 g/10 min) was used as received from DuPont-Dow Elastomers, predecessor-in-interest to The Dow Chemical Company, Midland, Michigan, USA. Triallyl trimesate (TAM, Monomer Polymer Inc., Feasterville, PA, USA), triallyl phosphate (TAP, 98%, TCI America, Portland, Oregon, USA), trimethylolpropane triacrylate (TMPTA, tech grade, Sigma-Aldrich, Oakville, Ontario, Canada), and 2,5-dimethyl-2,5-di(t-butylperoxy)hex-3-yne (L- 130, Atofina Chemicals, Philadelphia, Pennsylvania, USA) were also used as received.
PE (40 g) was mixed with L- 130 and the desired amount of coagent at 100 degrees Celsius using a Haake Polylab R600 internal batch mixer. An aliquot of the resulting masterbatch (5 g) was reacted in the cavity of an Alpha Technologies Advanced Polymer Analyzer at 200 degrees Celsius using an oscillation arc of 3 degrees and a frequency of 100 cpm. On-line measurements of dynamic storage (G') and loss (G") moduli provided the information needed to report the rate of G' evolution with time as well as changes to complex viscosity.
FIG. 1 illustrates the evolution of complex viscosity (η*) with time for a series of L- 130 (0.2 weight percent, 0.08 g) initiated crosslinking reactions. In the absence of coagent, η* progressed from an initial value of 2.5 kPa s to a stable plateau of 8.0 kPa s after 7 minutes. Crosslinking dynamics paralleled those of initiator decomposition.
The effect of cure temperature on crosslink yield is illustrated in FIG. 2, for L- 130 (0.2 weight percent, 0.08 g), coagent at 90 μmole/g, and 10 minutes. Higher cure temperatures were observed to accelerate the reaction rate while not compromising crosslink yields.
Experiments were also conducted at higher peroxide loading of 0.5 weight percent in order to assess the ultimate crosslink density generated as illustrated in FIG. 3. Without wishing to be bound by any theory, it is believed that TMPTA provided higher viscosity very early in the cure process because of its high kinetic reactivity and the large number of radicals introduced at this high initiator loading. It is further believed that TAM can outperform TMPTA when the free-radical population is sufficient to consume TAM's unactivated C=C bonds. TAP yielded the highest final crosslinking (i.e., end of reaction) of all the coagents.
Grafting of Triallyl Phosphate (TAP) to Ethylene Vinyl Acetate Copolymer
The triallyl phosphate (TAP) was obtained from Monomer Polymer (MP). The blend was prepared in a "40 cm3" Brabender mixing bowl to make batches of each formulation at a setting of 40 rpm, using the following procedure:
(1) weigh ingredients;
(2) do not purge mixing bowl with nitrogen;
(3) add ELVAX 265 ethylene vinyl acetate resin separately and flux (i.e., melt-mix) at 90 degrees Celsius for 2 minutes;
(4) inject triallyl phosphate (TAP) and/or peroxide (Luperox 231); and
(5) mix for additional 5 minutes at 90 degrees Celsius.
The blend testing involved (a) Moving Die Rheometer (MDR) experiments at a temperature of 140 degrees Celsius for 10 minutes, (b) thermogravimetric analysis (TGA) under nitrogen from ambient temperature to 900 degrees Celsius at a rate of 10 degrees Celsius/min, on specimens out of MDR, and (c) Cone Calorimeter (75 mil, 4" x 4" plaque, 35 kW/m2, no grid). The plaque was prepared by compression molding at 140 degrees Celsius for 10 minutes.
Considering FIG. 4, it is believed that the increased torque (modulus) with TAP and peroxide blend as compared with the TAP only blend during the MDR experiments indicates that TAP was grafted to the polymer.
The temperature-dependent weight loss of the specimens out of MDR is plotted in FIG. 5. Without any peroxide, the weight loss of the TAP compositions started around 100 degrees Celsius, which is believed to indicate that the unbound TAP was volatile and leaching from the polymer at elevated temperatures. Thermogravimetric analysis (TGA) of TAP by itself showed weight loss starting at about the same temperature.
When the compositions contained peroxide in addition to TAP, the onset of weight loss was shifted to around 220 degrees Celsius, indicating grafting of TAP to the polymer.
FIG. 6 presents the results of cone calorimeter experiments. Grafting of 9 weight percent TAP reduced the peak heat release rate by about 31 percent. There was also an upward shift in the corresponding time to peak heat release. These results indicate that grafted TAP imparts significantly improved fire performance.
Claims
1. A free-radical reactive polymer composition comprising:
(a) a polyolefin and
(b) a graftable, phosphorus-containing coagent in an amount greater than about 1.0 weight percent up to about 20.0 weight percent.
2. The composition of Claim 1 further comprising a free-radical inducing species.
3. The composition of Claim 1 or 2 wherein the graftable, phosphorus-containing coagent is selected from the group consisting of triallyl phosphate, triallyl phosphoric triamide, N-hydroxymethyl-3-dimethylphosphonopropionamide, 2-ethyl methacrylate phosphoric acid, phosphate esters of hydroxyl ethyl methacrylate, and vinyl phosphonic acid.
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