[go: up one dir, main page]

WO2009140169A1 - Polyéthylènes chlorés, leur procédé de fabrication, et articles obtenus à partir de ceux-ci - Google Patents

Polyéthylènes chlorés, leur procédé de fabrication, et articles obtenus à partir de ceux-ci Download PDF

Info

Publication number
WO2009140169A1
WO2009140169A1 PCT/US2009/043334 US2009043334W WO2009140169A1 WO 2009140169 A1 WO2009140169 A1 WO 2009140169A1 US 2009043334 W US2009043334 W US 2009043334W WO 2009140169 A1 WO2009140169 A1 WO 2009140169A1
Authority
WO
WIPO (PCT)
Prior art keywords
density polyethylene
range
less
chlorinated
weight
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.)
Ceased
Application number
PCT/US2009/043334
Other languages
English (en)
Inventor
Gregory Johnson
William Michie
Stephanie Whited
Laakso, Jr.
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Global Technologies LLC
Original Assignee
Dow Global Technologies LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Global Technologies LLC filed Critical Dow Global Technologies LLC
Publication of WO2009140169A1 publication Critical patent/WO2009140169A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C08F8/18—Introducing halogen atoms or halogen-containing groups
    • C08F8/20—Halogenation
    • C08F8/22—Halogenation by reaction with free halogens
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • 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
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
    • C08L23/286—Chlorinated polyethene

Definitions

  • the instant invention relates to chlorinated polyethylenes, method of producing the same, and articles made therefrom.
  • Chlorinated polyethylenes are generally produced in a slurry process via chlorination of high-density polyethylene polymers. Such chlorination processes are generally known and available to person of ordinary skill in the art. The degree of reactivity between the high- density polyethylene and chlorine leads to different degrees of chlorination and distribution thereof. In addition to the importance of the degree of chlorination, it is also important to have a high rate of chlorination where the chlorination is achieved at a relatively high speed.
  • U.S. Patent No. 3, 167,535 describes a process for the halogenation of synthetic vinyl resins, and more particularly pertains to a method for rapidly chlorinating polyvinyl chloride resins comprising conducting the chlorination reaction in the presence of a reducing agent.
  • U.S. Patent No. 3,424,556 describes a process for chlorinating polyethylene. The process includes the steps of: (a) preparing an aqueous slurry containing up to about 22 percent by weight of a particulate polyethylene wax having a molecular weight of no greater than about 18,000 and an average particle size of no greater than about 600 microns; (b) contacting the slurry with up to 1 part by weight of chlorine per part of un-chlorinated wax per hour at a temperature of up to about 70 0 C.
  • U.S. Patent No. 3,547,866 describes a process for chlorinating polyethylene in which polymer particles having a relatively large specific surface are chlorinated.
  • U.S. Patent No. 3,790,548 describes a process for chlorination of polyethylene in which particulate high-pressure polyethylene is suspended in a chlorohydrocarbon and treated with chlorine.
  • U.S. Patent No. 4,767,823 describes halogenated polyethylene resins and halogenated ethylene polymer resins having a reduced tendency to block are provided.
  • the halogenated resins are prepared respectively from polyethylene and ethylene polymer starting materials which have a weight-based median particle size of from about 120 to about 600 microns and a weight-based particle size distribution such that more than 60 percent of the particles have a particle size of from about 130 to about 850 microns.
  • the halogenated resins also have a weight-based median particle size of from about 200 to about 900 microns.
  • the halogenated polyethylene resins have a chemically combined halogen content of from about 26 to about 42 weight percent whereas the halogenated ethylene polymer resins have a chemically combined halogen content of from about 15 to about 28 weight percent.
  • the halogenated ethylene polymer resins are prepared from ethylene polymer starting materials which have polymerized therein up to five weight percent of 1 -olefin monomer copolymerizable with ethylene.
  • U.S. Patent No. 5,068,489 describes continuous ethylene polymerization in a fluidized bed in the presence of a dialkylzinc compound.
  • the International Publication No. WO 2006/023057 Al describes a Ziegler-Natta procatalyst composition in the form of solid particles and comprising magnesium, halide and transition metal moieties.
  • European Patent Publication No. 0 343 657 describes a two-stage aqueous slurry chlorination process which employs a constant gaseous chlorine flow rate and a temperature which increases from an initial chlorination temperature of 100 0 C. to a line-out chlorination temperature of from 116 0 C. to 128 0 C. in the first stage and remains at the line-out temperature in the second stage.
  • the instant invention is a chlorinated polyethylene, method of producing the same, and articles made therefrom.
  • the chlorinated polyethylene composition according to the instant invention comprises the reaction product of (a) 55 to 90 percent by weight of a gas- phase high-density polyethylene, based on the total weight of the chlorinated high-density polyethylene, wherein the high-density polyethylene has a density in the range of 0.940 to 0.970 g/cm 3 , a melt index h in the range of less than 15 g/10 minutes, a melt flow rate I ]0 in the range of less than 200 g/10 minutes; and an average particle size in the range of less than 800 microns; (b) 10 to 45 percent by weight of chlorine, based on the total weight of the chlorinated high-density polyethylene; and (c) optionally less than 15 percent by weight of a surfactant, based on the total weight of the chlorinated polyethylene.
  • the method of producing chlorinated high-density polyethylenes comprises the steps of (1) selecting a gas-phase high-density polyethylene, wherein the high- density polyethylene has a density in the range of 0.940 to 0.970 g/cm 3 , a melt index h in the range of less than 15 g/10 minutes, a melt flow rate Iio in the range of less than 200 g/10 minutes, and an average particle size in the range of less than 800 microns; (2) selecting chlorine; (3) optionally selecting a surfactant; (4) forming an aqueous slurry of the high- density polyethylene optionally in the presence of the surfactant; (5) increasing the temperature of the slurry to a temperature of less than peak melting point temperature of the high-density polyethylene while agitating the high-density polyethylene; (6) admixing the chlorine with the slurry while maintaining the temperature of the mixture of chlorine and slurry at a temperature of less than peak melting point temperature of the high-density
  • the articles according to the instant invention comprise a chlorinated polyethylene composition
  • a chlorinated polyethylene composition comprising the reaction product of (a) 55 to 90 percent by weight of a gas-phase high-density polyethylene, based on the total weight of the chlorinated high-density polyethylene, wherein the high-density polyethylene has a density in the range of 0.940 to 0.970 g/cm 3 , a melt index h in the range of less than 15 g/10 minutes, a melt flow rate Iio in the range of less than 200 g/10 minutes, and an average particle size in the range of less than 800 microns; (b) 10 to 45 percent by weight of chlorine, based on the total weight of the chlorinated high-density polyethylene; and (c) optionally less than 15 percent by weight of a surfactant, based on the total weight of the chlorinated polyethylene.
  • the instant invention provides a chlorinated polyethylene composition
  • a chlorinated polyethylene composition comprising the reaction product of (a) 55 to 90 percent by weight of a gas-phase high-density polyethylene, based on the total weight of the chlorinated high-density polyethylene, wherein the high-density polyethylene has a density in the range of 0.940 to 0.970 g/cm 3 , a melt index h in the range of less than 15 g/10 minutes, a melt flow rate Iioin the range of less than 200 g/10 minutes; and an average particle size in the range of less than 800 microns; (b) 10 to 45 percent by weight of chlorine, based on the total weight of the chlorinated high-density polyethylene; and (c) optionally less than 15 percent by weight of a surfactant, based on the total weight of the chlorinated polyethylene.
  • the instant invention further provides a method for producing chlorinated high-density polyethylenes comprising the steps of (1) selecting a gas- phase high-density polyethylene, wherein the high-density polyethylene has a density in the range of 0.940 to 0.970 g/cm 3 , a melt index I 2 in the range of less than 15 g/10 minutes, a melt flow rate Iioin the range of less than 200 g/10 minutes, and an average particle size in the range of less than 800 microns; (2) selecting chlorine; (3) optionally selecting a surfactant; (4) forming an aqueous slurry of the high-density polyethylene optionally in the presence of the surfactant; (5) increasing the temperature of the slurry to a temperature of less than peak melting point temperature of the high-density polyethylene while agitating the high-density polyethylene; (6) admixing the chlorine with the slurry while maintaining the temperature of the mixture of chlorine and slurry at a temperature of less than
  • the instant invention further provides an article comprising a chlorinated polyethylene composition
  • a chlorinated polyethylene composition comprising the reaction product of (a) 55 to 90 percent by weight of a gas-phase high-density polyethylene, based on the total weight of the chlorinated high-density polyethylene, wherein the high-density polyethylene has a density in the range of 0.940 to 0.970 g/cm 3 , a melt index I 2 in the range of less than 15 g/10 minutes, a melt flow rate I 1 0 in the range of less than 200 g/10 minutes, and an average particle size in the range of less than 800 microns; (b) 10 to 45 percent by weight of chlorine, based on the total weight of the chlorinated high-density polyethylene; and (c) optionally less than 15 percent by weight of a surfactant, based on the total weight of the chlorinated polyethylene.
  • the instant invention provides a composition, method of producing the same, and articles made therefrom in accordance with any of the preceding embodiments, except that the high-density polyethylene has an average particle size in the range of less than 750 microns.
  • the instant invention provides a composition, method of producing the same, and articles made therefrom in accordance with any of the preceding embodiments, except that the high-density polyethylene has an average particle size in the range of less than 550 microns.
  • the instant invention provides a composition, method of producing the same, and articles made therefrom in accordance with any of the preceding embodiments, except that the high-density polyethylene has an average particle size in the range of less than 450 microns.
  • the instant invention provides a composition, method of producing the same, and articles made therefrom in accordance with any of the preceding embodiments, except that the high-density polyethylene has an average particle size in the range of less than 400 microns.
  • the instant invention provides a composition, method of producing the same, and articles made therefrom in accordance with any of the preceding embodiments, except that the high-density polyethylene has an average particle size in the range of less than 300 microns.
  • the instant invention provides a composition, method of producing the same, and articles made therefrom in accordance with any of the preceding embodiments, except that the chlorinated polyethylene comprises 15 to 45 percent by weight of chlorine, based on the total weight of the chlorinated high-density polyethylene.
  • the instant invention provides a composition, method of producing the same, and articles made therefrom in accordance with any of the preceding embodiments, except that the chlorinated polyethylene comprises 18 to 45 percent by weight of chlorine, based on the total weight of the chlorinated high-density polyethylene.
  • the instant invention provides a composition, method of producing the same, and articles made therefrom in accordance with any of the preceding embodiments, except that the chlorinated polyethylene comprises 20 to 45 percent by weight of chlorine, based on the total weight of the chlorinated high-density polyethylene.
  • Fig. 1 is a graph illustrating the relationship between chlorine content in weight percent and average particle size measured in ⁇ m of the Comparative Example 1
  • Fig. 2 is a graph illustrating the relationship between chlorine content in weight percent and average particle size measured in ⁇ m of the Comparative Example 2;
  • Fig. 3 is a graph illustrating the relationship between chlorine content in weight percent and average particle size measured in ⁇ m of the Inventive Example 1 ;
  • Fig. 4 is a graph illustrating the relationship between chlorine content in weight percent and average particle size measured in ⁇ m of the Inventive Example 2;
  • Fig. 5 is a graph illustrating the relationship between chlorine content in weight percent and average particle size measured in ⁇ m of the Inventive Example 3;
  • Fig. 6 is a graph illustrating the relationship between chlorine content in weight percent and average particle size measured in ⁇ m of the Inventive Example 4.
  • Fig. 7 is a graph illustrating the relationship between chlorine content in weight percent and average particle size measured in ⁇ m of the Inventive Example 5.
  • the instant invention is a chlorinated polyethylene, method of producing the same, and articles made therefrom.
  • the chlorinated polyethylene composition comprising the reaction product of (a) 55 to 90 percent by weight of a gas-phase high-density polyethylene, based on the total weight of the chlorinated high-density polyethylene, wherein the high- density polyethylene has a density in the range of 0.940 to 0.970 g/cm 3 , a melt index h in the range of less than 15 g/10 minutes, a melt flow rate Iioin the range of less than 200 g/10 minutes; and an average particle size in the range of less than 800 microns; (b) 10 to 45 percent by weight of chlorine, based on the total weight of the chlorinated high-density polyethylene; and (c) optionally less than 15 percent by weight of a surfactant, based on the total weight of the chlorinated polyethylene.
  • the chlorinated polyethylene compositions according to the instant invention typically exhibit unexpected improved tear and tensile strength.
  • polyethylene refers to ethylene homopolymers and/or ethylene and one or more ⁇ -olefins copolymers.
  • the high-density polyethylene may be a gas phase polyethylene, and it may have a density in the range of 0.940 to 0.970 g/cm 3 . All individual values and subranges from 0.940 to 0.970 g/cm 3 are included herein and disclosed herein; for example, the density can be from a lower limit of 0.940, 0.942, 0.945, 0.946, or 0.950 g/cm 3 to an upper limit of 0.950, 0.960, 0.965, or 0.975 g/cm 3 .
  • the polyethylene composition may have a density in the range of 0.942 to 0.970 g/cm 3 ; or in the alternative, the polyethylene composition may have a density in the range of 0.940 to 0.965 g/cm 3 ; or in the alternative, the polyethylene composition may have a density in the range of 0.940 to 0.960 g/cm 3 ; or in the alternative, the polyethylene composition may have a density in the range of 0.940 to 0.950 g/cm 3 ; or in the alternative, the polyethylene composition may have a density in the range of 0.950 to 0.965 g/cm 3 ; or in the alternative, the polyethylene composition may have a density in the range of 0.945 to 0.965 g/cm 3 .
  • the high-density polyethylene composition has a molecular weight distribution (M w /M n ) in the range of less than or equal to 5. All individual values and subranges from less than or equal to 5 are included herein and disclosed herein; for example, the molecular weight distribution (M w /M n ) can be from a lower limit of 1.70, 1.80, 1.90, 2.10, 2.30, 2.50, 2.70, 2.90, 3.00, 3.10, 3.30, 3.40 or 3.50 to an upper limit of 3.55, 3.60, 3.70, 4.10, 4.30, 4.40, 4.50, or 4.60.
  • the high-density polyethylene composition may have a molecular weight distribution (M w /M n ) in the range of 1.70 to 4.60; or in the alternative, the high- density polyethylene composition may have a molecular weight distribution (M w /M n ) in the range of 2.10 to 4.60; or in the alternative, the high-density polyethylene composition may have a molecular weight distribution (M w /M n ) in the range of 3.10 to 4.60; or in the alternative, the high-density polyethylene composition may have a molecular weight distribution (M w /M n ) in the range of 3.40 to 4.60.
  • M w /M n molecular weight distribution in the range of 1.70 to 4.60
  • the high- density polyethylene composition may have a molecular weight distribution (M w /M n ) in the range of 2.10 to 4.60; or in the alternative, the high-density polyethylene composition may have a molecular weight
  • the high-density polyethylene composition has a melt index (I 2 ) in the range of less than or equal to 20 g/10 minutes. All individual values and subranges from less than 20 g/10 minutes are included herein and disclosed herein; for example, the melt index (I 2 ) can be from a lower limit of 0.01, 0.03, 0.05, 01, 0.3, 0.5, 1, 3, 5, or 7 g/10 minutes, to an upper limit of 8, 10, 14, 16, 18, or 20 g/10 minutes.
  • the high-density polyethylene composition may have a melt index (I 2 ) in the range of 0.01 to 20 g/10 minutes; or in the alternative, the high-density polyethylene composition may have a melt index (I 2 ) in the range of 0.01 to 18 g/10 minutes; or in the alternative, the high-density polyethylene composition may have a melt index (I 2 ) in the range of 0.01 to 16 g/10 minutes; or in the alternative, the high-density polyethylene composition may have a melt index (I 2 ) in the range of 0.01 to 14 g/10 minutes; or in the alternative, the high-density polyethylene composition may have a melt index (I 2 ) in the range of 0.01 to 10 g/10 minutes; or in the alternative, the high-density polyethylene composition may have a melt index (I 2 ) in the range of 0.5 to 20 g/10 minutes; or in the alternative, the high-density polyethylene composition may have a melt index (I 2 ) in the range of 0.5
  • the high-density polyethylene composition has a melt flow rate (I 10 ) in the range of less than or equal to 200 g/10 minutes. All individual values and subranges from less than 20 g/10 minutes are included herein and disclosed herein; for example, the melt flow rate (Iio) can be from a lower limit of 0.1, 0.3, 0.5, 1, 3, 5, 7, or 10 g/10 minutes, to an upper limit of 20, 30, 40, 50, 60, 80, 100, 110, 130, 150, or 200 g/10 minutes.
  • the high- density polyethylene composition may have a melt flow rate (I 10 ) in the range of 0.1 to 200 g/10 minutes; or in the alternative, the high-density polyethylene composition may have a melt flow rate (Iio) in the range of 0.5 to 200 g/10 minutes; or in the alternative, the high- density polyethylene composition may have a melt flow rate (Iio) in the range of 0.1 to 150 g/10 minutes; or in the alternative, the high-density polyethylene composition may have a melt flow rate (I )0 ) in the range of 0.1 to 130 g/10 minutes; or in the alternative, the high- density polyethylene composition may have a melt flow rate (Iio) in the range of 0.1 to 110 g/10 minutes; or in the alternative, the high-density polyethylene composition may have a melt flow rate (Iio) in the range of 0.5 to 110 g/10 minutes; or in the alternative, the high- density polyethylene composition may have a melt flow rate (Iio) in the range of
  • the high-density polyethylene composition has a melt flow ratio (I 1 0/I 2 ) in the range of 1 to 20. All individual values and subranges from 1 to 20 minutes are included herein and disclosed herein; for example, the melt flow ratio (I 10 /I 2 ) can be from a lower limit of 1, 3, 5, 7, 9, or 11 to an upper limit of 10, 13, 15, 17, 18, or 20.
  • the high-density polyethylene composition may have a melt flow ratio (I10/I2) in the range of 3 to 20; or in the alternative, the high-density polyethylene composition may have a melt flow ratio (I 1 0/I 2 ) in the range of 5 to 20; or in the alternative, the high-density polyethylene composition may have a melt flow ratio (I 10 /I 2 ) in the range of 7 to 20; or in the alternative, the high-density polyethylene composition may have a melt flow ratio (I 1 0/I 2 ) in the range of 9 to 20; or in the alternative, the high-density polyethylene composition may have a melt flow ratio (I10/I2) in the range of 5 to 18; or in the alternative, the high-density polyethylene composition may have a melt flow ratio (I 10 /I 2 ) in the range of 7 to 18; or in the alternative, the high-density polyethylene composition may have a melt flow ratio (I 10 /I 2 ) in the range of 3
  • the high-density polyethylene composition has a molecular weight (M w ) in the range of 50,000 to 300,000 daltons. All individual values and subranges from 50,000 to 300,000 daltons are included herein and disclosed herein; for example, the molecular weight (M w ) can be from a lower limit of 50,000, 60,000, 70,000, 80,000, 90,000, 95,000, 100,000, 150,000, or 200,000 daltons to an upper limit of 200,000, 220,000, 225,000, 250,000, 275,000, or 300,000 daltons.
  • the high-density polyethylene composition may have a molecular weight (M w ) in the range of 80,000 to 300,000 daltons; or in the alternative, the high-density polyethylene composition may have a molecular weight (M w ) in the range of 150,000 to 300,000 daltons; or in the alternative, the high-density polyethylene composition may have a molecular weight (M w ) in the range of 200,000 to 300,000 daltons; or in the alternative, the high-density polyethylene composition may have a molecular weight (M w ) in the range of 200,000 to 275,000 daltons; or in the alternative, the high-density polyethylene composition may have a molecular weight (M w ) in the range of 200,000 to 250,000 daltons; or in the alternative, the high-density polyethylene composition may have a molecular weight (Mw) in the range of 200,000 to 225,000 daltons.
  • the high-density polyethylene composition may have molecular weight distribution (M z /Mw) in the range of less than or equal to 5. All individual values and subranges from less than or equal to 5 are included herein and disclosed herein; for example, the molecular weight distribution (M z /M w ) can be from a lower limit of 1.70, 1.80, 1.90, 2.10, 2.30, 2.40, 2.50, or 2.60 to an upper limit of 2.70, 2.80 2.90, 3.10, 3.50, 4.10, 4.70, or 4.90.
  • the high-density polyethylene composition may have a molecular weight distribution (M w /M n ) in the range of 1.70 to 4.90; or in the alternative, the high-density polyethylene composition may have a molecular weight distribution (M w /M n ) in the range of 1.70 to 4.10; or in the alternative, the high-density polyethylene composition may have a molecular weight distribution (M w /M n ) in the range of 2.10 to 3.10; or in the alternative, the high-density polyethylene composition may have a molecular weight distribution (M w /M n ) in the range of 2.30 to 2.80.
  • the high-density polyethylene composition may comprise less than 15 percent by weight of units derived from one or more ⁇ -olefin comonomers. AU individual values and subranges from less than 15 weight percent are included herein and disclosed herein; for example, the high-density polyethylene composition may comprise less than 12 percent by weight of units derived from one or more ⁇ -olef ⁇ n comonomers; or in the alternative, the high-density polyethylene composition may comprise less than 11 percent by weight of units derived from one or more ⁇ -olef ⁇ n comonomers; or in the alternative, the high-density polyethylene composition may comprise less than 9 percent by weight of units derived from one or more ⁇ -olefin comonomers; or in the alternative, the high-density polyethylene composition may comprise less than 7 percent by weight of units derived from one or more ⁇ -olefin comonomers; or in the alternative, the high-density polyethylene composition may comprise less than 5 percent by
  • the ⁇ -olef ⁇ n comonomers typically have no more than 20 carbon atoms.
  • the ⁇ -olef ⁇ n comonomers may preferably have 3 to 10 carbon atoms, and more preferably 3 to 8 carbon atoms.
  • Exemplary ⁇ -olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-l-pentene.
  • the one or more ⁇ -olef ⁇ n comonomers may, for example, be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene; or in the alternative, from the group consisting of 1-hexene and 1-octene.
  • the high-density polyethylene composition may comprise at least 85 percent by weight of units derived from ethylene comonomers. All individual values and subranges from at least 85 weight percent are included herein and disclosed herein; for example, the high-density polyethylene composition may comprise at least 88 percent by weight of units derived from ethylene comonomers; or in the alternative, the high-density polyethylene composition may comprise at least 89 percent by weight of units derived from ethylene comonomers; or in the alternative, the high-density polyethylene composition may comprise at least 91 percent by weight of units derived from ethylene comonomers; or in the alternative, the high-density polyethylene composition may comprise at least 93 percent by weight of units derived from ethylene comonomers; or in the alternative, the high-density polyethylene composition may comprise at least 95 percent by weight of units derived from ethylene comonomers; or in the alternative, the high-density polyethylene composition may comprise at least 97 percent by weight of units
  • the high-density polyethylene composition may have an average particle size in the range of less than or equal to 2000 ⁇ m. All individual values and subranges from less than or equal to 2000 ⁇ m are included herein and disclosed herein; for example, the average particle size can be from a lower limit of 50, 100, 150, 200, 250, 275, 300, 325, 350, 375, or 400 ⁇ m to an upper limit of 150, 200, 250, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 1000, 1500, or 2000 ⁇ m.
  • the high-density polyethylene composition may have an average particle size in the range of 250 to 2000 ⁇ m; or in the alternative, the high-density polyethylene composition may have an average particle size in the range of 50 to 1000 ⁇ m; or in the alternative, the high-density polyethylene composition may have an average particle size in the range of 250 to 800 ⁇ m; or in the alternative, the high-density polyethylene composition may have an average particle size in the range of 50 to 750 ⁇ m; or in the alternative, the high-density polyethylene composition may have an average particle size in the range of 50 to 700 ⁇ m; or in the alternative, the high-density polyethylene composition may have an average particle size in the range of 50 to 650 ⁇ m; or in the alternative, the high- density polyethylene composition may have an average particle size in the range of 50 to 600 ⁇ m; or in the alternative, the high-density polyethylene composition may have an average particle size in the range of 50 to 550 ⁇ m; or in the alternative, the high-dens
  • the chlorinated polyethylene according to the instant invention may comprise 50 to 90 percent by weight of a gas-phase high-density polyethylene, based on the total weight of the chlorinated high-density polyethylene. All individual values and subranges from 55 to 90 weight percent are included herein and disclosed herein; for example, the weight percent of the high-density polyethylene can be from a lower limit of 50, 55, 60, 70, or 80 to an upper limit of 60, 70, 75, 80, 85, or 90.
  • the chlorinated polyethylene may comprise 50 to 85 percent by weight of a gas-phase high-density polyethylene, based on the total weight of the chlorinated high-density polyethylene; or in the alternative, the chlorinated polyethylene may comprise 50 to 80 percent by weight of a gas-phase high-density polyethylene, based on the total weight of the chlorinated high-density polyethylene; or in the alternative, the chlorinated polyethylene may comprise 50 to 75 percent by weight of a gas- phase high-density polyethylene, based on the total weight of the chlorinated high-density polyethylene; or in the alternative, the chlorinated polyethylene may comprise 50 to 70 percent by weight of a gas-phase high-density polyethylene, based on the total weight of the chlorinated high-density polyethylene.
  • the high-density polyethylene composition may be produced via gas phase polymerization process employing, for example, one or more fluidized bed gas phase reactors, in parallel, series, and/or in combinations thereof.
  • the gas phase polymerization reactor is a continuous polymerization reactor comprising one or more feed streams.
  • the one or more feed streams are combined together, and the gas comprising ethylene and optionally one or more comonomers, e.g. one or more ⁇ -olef ⁇ ns, are flowed or cycled continuously through the polymerization reactor by any suitable means.
  • the gas comprising ethylene and optionally one or more comonomers, e.g. one or more ⁇ -olefins may be fed up through a distributor plate to fluidize the bed in a continuous fluidization process.
  • a suitable catalyst system such as those catalyst systems described in the U.S. Patent No. 5.068,489 and International Publication No. WO 2006/023057, which are incorporated herein by reference in their entirety, ethylene, optionally one or more alpha- olefin comonomers, hydrogen, optionally one or more inert gases and/or liquids, e.g. N 2 , isopentane, and hexane, and one or more continuity additive, e.g. ethoxylated stearyl amine or aluminum distearate or combinations thereof, are continuously fed into a reactor, e.g. a fluidized bed gas phase reactor.
  • a reactor e.g. a fluidized bed gas phase reactor.
  • the reactor may be in fluid communication with one or more discharge tanks, surge tanks, purge tanks, and/or recycle compressors.
  • the temperature in the reactor is typically in the range of 70 to 115 0 C, preferably 75 to 110 0 C, more preferably 75 to 100 0 C, and the pressure is in the range of 15 to 30 atm, preferably 17 to 26 atm.
  • a distributor plate at the bottom of the polymer bed provides a uniform flow of the upflowing monomer, comonomer, and inert gases stream.
  • a mechanical agitator may also be provided to provide contact between the solid particles and the comonomer gas stream.
  • the fluidized bed may have a bulb shape at the top to facilitate the reduction of gas velocity; thus, permitting the granular polymer to separate from the upflowing gases.
  • the unreacted gases are then cooled to remove the heat of polymerization, recompressed, and then recycled to the bottom of the reactor.
  • moisture may be introduced to reduce the presence of any residual catalyzed reactions with O 2 before the high-density polyethylene composition is exposed to oxygen.
  • the high-density polyethylene composition may be preferably be in the granular form.
  • the high-density polyethylene composition may further be subject to grinding process and/or screening process to ensure average particle size in the range of less than or equal to 2000 ⁇ m.
  • the grinding process may, for example, be achieved the use of ball-mills or other grinding and comminuting equipments.
  • the chlorinated polyethylene according to the instant invention may comprise 10 to 50 percent by weight of chlorine, based on the total weight of the chlorinated high-density polyethylene. All individual values and subranges from 10 to 50 weight percent are included herein and disclosed herein; for example, the weight percent of the chlorine can be from a lower limit of 10, 15, 20, 25, 30, 35, 40, 42, or 45 to an upper limit of 20, 30, 35, 40, 45, 48 or 50.
  • chlorinated polyethylene according to the instant invention may comprise 15 to 50 percent by weight of chlorine, based on the total weight of the chlorinated high-density polyethylene; or in the alternative, chlorinated polyethylene according to the instant invention may comprise 20 to 50 percent by weight of chlorine, based on the total weight of the chlorinated high-density polyethylene; or in the alternative, chlorinated polyethylene according to the instant invention may comprise 25 to 50 percent by weight of chlorine, based on the total weight of the chlorinated high-density polyethylene; or in the alternative, chlorinated polyethylene according to the instant invention may comprise 10 to 45 percent by weight of chlorine, based on the total weight of the chlorinated high-density polyethylene; or in the alternative, chlorinated polyethylene according to the instant invention may comprise 20 to 45 percent by weight of chlorine, based on the total weight of the chlorinated high-density polyethylene; or in the alternative, chlorinated polyethylene according to the instant invention may comprise 20 to 42 percent by weight of chlorine, based on the total weight of the
  • the inventive chlorinated polyethylene composition comprises the reaction product of (1) 55 to 90 percent by weight of a gas-phase high-density polyethylene, based on the total weight of the chlorinated high-density polyethylene, wherein the high- density polyethylene has a density in the range of 0.940 to 0.970 g/cm 3 , a melt index I 2 in the range of less than 15 g/10 minutes, a melt flow rate I 10 in the range of less than 200 g/10 minutes; and an average particle size in the range of less than 800 microns; (2) 10 to 45 percent by weight of chlorine, based on the total weight of the chlorinated high-density polyethylene; and (3) optionally less than 15 percent by weight of a surfactant, based on the total weight of the chlorinated polyethylene.
  • the optional weight percent of the surfactant can be from a lower limit of 0.001, 0.01, 0.1, 0.2,0.5,1, 2, or 5 weight percent to an upper limit of 0.01, 0.1, 0.2,0.5,1, 2, 5, 10, or 15 weight percent.
  • the chlorinated polyethylene according to the instant invention may comprise 0.1 to 5 percent by weight of surfactant, based on the total weight of the chlorinated high-density polyethylene; or in the alternative, the chlorinated polyethylene according to the instant invention may comprise 0.1 to 2 percent by weight of surfactant, based on the total weight of the chlorinated high-density polyethylene; or in the alternative, the chlorinated polyethylene according to the instant invention may comprise 0.1 to 1 percent by weight of surfactant, based on the total weight of the chlorinated high-density polyethylene; or in the alternative, the chlorinated polyethylene according to the instant invention may comprise 0.1 to 0.5 percent by weight of surfactant, based on the total weight of the chlorinated high-density polyethylene.
  • the high-density polyethylene may be chlorinated via an aqueous slurry process.
  • no additional catalyst is added to promote the chlorination reaction.
  • acceleration of the chlorination rate may be assisted by employing catalysts, such as free-radical types and/or ultraviolet light.
  • catalysts such as free-radical types and/or ultraviolet light.
  • Potential azo-type compounds and peroxides may be selected from a group of free-radical catalysts, such as tertiary butyl peroxide or tertiary butyl hydroperoxide.
  • Such catalysts may be added in a single step, intermittently or continuously depending on the reaction conditions and catalyst(s) used.'
  • a suspension of the high-density polyethylene starting material, a dispersant such as talc and a surfactant are heated, preferably while being stirred, from an initial temperature of about 95 0 C. to 105 0 C. to a final temperature in the range of 116 0 C. to 135 0 C, while adding gaseous chlorine to attain a chlorine content of 10 to 50 percent based on the weight of the chlorinated polyethylene.
  • no more gaseous chlorine is added to the reactor when the temperature of the slurry reaches the final temperature in the range of 116 0 C. to 135 °C; provided however, the chlorine content has reached the optimum level, i.e. 10 to 50 percent based on the weight of the chlorinated polyethylene.
  • gaseous chlorine is continued to be added to the reactor after the slurry reaches the final temperature in the range of 116 °C. to 135 °C. in order to reach the optimum level of chlorine content, i.e. 10 to 50 percent based on the weight of the chlorinated polyethylene, and/or to adjust chlorine distribution within the chlorinated polyethylene.
  • the slurry may further be rinsed, washed, and/or caustic treated, e.g. neutralized via sodium hydroxide, to remove the residual hydrochloric acid.
  • the neutralized slurry may then be dewatered, e.g. via a centrifuge and/or filter/screen system, to form a cake, and the cake may, then, be dried, e.g. via a hot-air fluid bed dryer. Additional additives and/or dispersants may be added to the chlorinated polyethylene in the drying step, for example in the hot-air bed dryer.
  • the method of producing chlorinated high-density polyethylenes comprises the steps of (1) selecting a gas-phase high-density polyethylene, wherein the high-density polyethylene has a density in the range of 0.940 to 0.970 g/cm ⁇ a melt index h in the range of less than 15 g/10 minutes, a melt flow rate I ]0 in the range of less than 200 g/10 minutes, and an average particle size in the range of less than 800 microns; (2) selecting chlorine; (3) optionally selecting a surfactant; (4) forming an aqueous slurry of the high-density polyethylene optionally in the presence of the surfactant; (5) increasing the temperature of the slurry to a temperature in the range of less than peak melting point temperature of the high-density polyethylene while agitating the high-density polyethylene; (6) admixing the chlorine with the slurry while maintaining the temperature of the mixture of chlorine and slurry at a temperature in the range of less than peak melting
  • the articles according to the instant invention comprise the inventive chlorinated polyethylene.
  • Such articles include, but are not limited to, polyvinyl chloride impact modifier, thermoset end-use applications such as wire and cable, automotive hoses, cross- linked rubber articles.
  • the chlorinated polyethylene compositions according to the instant invention may, for example, be used in elstomeric formulations.
  • Comparative Sample A (“Comparative Polyethylene A”) is a high-density polyethylene produced via a Ziegler-type catalyst in a slurry polymerization process, having a density of approximately 0.954 g/cm 3 , a melt index h of approximately 0.03 grams/10 minutes, a melt flow rate I 1 Q of approximately 0.50 grams/10 minutes, and an average particle size of approximately 120 microns.
  • Comparative Polyethylene A was chlorinated via aqueous slurry process in an enclosed, agitated vessel. 25 pounds of the Comparative Polyethylene A was slurried with 189 pounds of water. The slurry also contained 12 milliliters of a commercially available nonylphenol ethoxylate surfactant. 80 grams of talc was added to the starting slurry. Additional 200 grams of talc was added to the slurry during the reaction as a process aid control. The temperature of the slurry was increased to approximately 95 0 C, and gaseous chlorination addition began at a controlled rate of 0.40 lbs/minute for 39 minutes until a peak reactor temperature of 130 0 C. was attained.
  • Chlorine flow rate of 0.36 lbs/minute were sustained for another 35 minutes at the peak reactor temperature.
  • the slurry was transferred to another agitated vessel, in which the slurry was rinsed and washed in a caustic batch at 90 0 C. to neutralize residual HCL.
  • the neutralized slurry was passed through a centrifuge to produce a wet polymer cake.
  • the cake was transferred into a hot-air fluid bed dryer.
  • the cake was dried at approximately 50 0 C. until residual moisture of less than 0.4 weight percent was attained.
  • An anti-agglomerate aid 250 grams of talc, was added to the fluid bed dryer.
  • the chlorinated polyethylene composition was designated as Comparative Example 1 ("CPE-Cl"), having a bulk chlorine content of approximately 37.1 weigh percent.
  • the Comparative Example 1 was sieved into different fractions based on their size distribution. The different fractions were analyzed for their chlorine content, and the results are displayed in Figure 1.
  • Comparative Sample A (“Comparative Polyethylene A”) is a high-density polyethylene produced via a Ziegler-type catalyst in a slurry polymerization process, having a density of approximately 0.954 g/cm 3 , a melt index h of approximately 0.03 grams/10 minutes, a melt flow rate Iio of approximately 0.50 grams/10 minutes, and an average particle size of approximately 120 microns.
  • Comparative Polyethylene A was chlorinated via aqueous slurry process in an enclosed, agitated vessel. 25 pounds of the Comparative Polyethylene A was slurried with 189 pounds of water. The slurry also contained 12 milliliters of a commercially available nonylphenol ethoxylate surfactant. 80 grams of talc was added to the starting slurry. Additional 160 grams of talc was added to the slurry during the reaction as a process aid control. The temperature of the slurry was increased to approximately 95 0 C, and gaseous chlorination addition began at a controlled rate of 0.40 lbs/minute for 53 minutes until a peak reactor temperature of 131.5 0 C. was attained.
  • Chlorine flow rate of 0.36 lbs/minute were sustained for another 19 minutes at the peak reactor temperature.
  • the slurry was transferred to another agitated vessel, in which the slurry was rinsed and washed in a caustic batch at 90 0 C. to neutralize residual HCL.
  • the neutralized slurry was passed through a centrifuge to produce a wet polymer cake.
  • the cake was transferred into a hot-air fluid bed dryer.
  • the cake was dried at approximately 50 0 C. until residual moisture of less than 0.4 weight percent was attained.
  • An anti-agglomerate aid 250 grams of talc, was added to the fluid bed dryer.
  • the chlorinated polyethylene composition was designated as Comparative Example 2 ("CPE-C2"), having a bulk chlorine content of approximately 37.5 weigh percent.
  • the Comparative Example 2 was sieved into different fractions based on their size distribution. The different fractions were analyzed for their chlorine content, and the results are displayed in Figure 2.
  • Inventive Sample A (“Inventive Polyethylene A”) (“HDPE-IA”) is a high-density polyethylene produced via a catalyst system including a catalyst, i.e. UCATTM J, and a cocatalyst, i.e. trialkyl aluminum (tri ethyl aluminum or TEAL) in a gas phase polymerization process.
  • the polymerization conditions are shown in Table I.
  • the polymerization was initiated by continuously feeding the catalyst system including a catalyst, i.e. UCATTM J, and a cocatalyst, i.e. trialkyl aluminum (tri ethyl aluminum or TEAL), into a fluidized bed of polyethylene granules, together with ethylene and hydrogen.
  • This inventive high-density polyethylene composition was designated as the Inventive Sample A, and it had a density of approximately 0.949 g/cm , a melt index h of approximately 0.04 grams/10 minutes, a melt flow rate Iio of approximately . 0.30 grams/10 minutes, a molecular weight distribution of 3.6, and an average particle size of approximately 1000 microns.
  • Inventive Polyethylene A was chlorinated via aqueous slurry process in an enclosed, agitated vessel. 25 pounds of the Inventive Polyethylene A powder was slurried with 189 pounds of water. The slurry also contained 12 milliliters of a commercially available nonylphenol ethoxylate surfactant. 80 grams of talc was added to the starting slurry. Additional 240 grams of talc was added to the slurry during the reaction as a process aid control. The temperature of the slurry was increased to approximately 95 0 C, and gaseous chlorination addition began at a controlled rate of 0.40 lbs/minute for 39 minutes until a peak reactor temperature of 133.5 0 C. was attained.
  • Chlorine flow rate of 0.36 lbs/minute were sustained for another 35 minutes at the peak reactor temperature.
  • the slurry was transferred to another agitated vessel, in which the slurry was rinsed and washed in a caustic batch at 90 0 C. to neutralize residual HCL.
  • the neutralized slurry was passed through a centrifuge to produce a wet polymer cake.
  • the cake was transferred into a hot-air fluid bed dryer.
  • the cake was dried at approximately 50 0 C. until residual moisture of less than 0.4 weight percent was attained.
  • An anti-agglomerate aid 250 grams of talc, was added to the fluid bed dryer.
  • the chlorinated polyethylene composition was designated as Inventive Example 1 ("CPE-Il"), having a bulk chlorine content of approximately 33.5 weigh percent.
  • the Inventive Example 1 was sieved into different fractions based on their size distribution. The different fractions were analyzed for their chlorine content, and the results are displayed in Figure 3.
  • Figure 3 further indicates that Inventive Example 1 particles having an average particle size of less than 571 microns exhibit higher chlorination levels. Figure 3 further indicates that within the same average particle size, i.e. less than 300 micron, Inventive Example 1 exhibited improved chlorination relative to the Comparative Example 1.
  • Inventive Sample A (“Inventive Polyethylene A”) (“HDPE-IA”), as described in Inventive Example 1, was chlorinated via aqueous slurry process in an enclosed, agitated vessel. 25 pounds of the Inventive Polyethylene A powder was slurried with 189 pounds of water. The slurry also contained 12 milliliters of a commercially available nonylphenol ethoxylate surfactant. 80 grams of talc was added to the starting slurry. Additional 240 grams of talc was added to the slurry during the reaction as a process aid control.
  • the temperature of the slurry was increased to approximately 95 0 C, and gaseous chlorination addition began at a controlled rate of 0.40 lbs/minute for 53 minutes until a peak reactor temperature of 133.5 0 C. was attained. Chlorine flow rate of 0.36 lbs/minute were sustained for another 19 minutes at the peak reactor temperature.
  • the slurry was transferred to another agitated vessel, in which the slurry was rinsed and washed in a caustic batch at 90 0 C. to neutralize residual HCL.
  • the neutralized slurry was passed through a centrifuge to produce a wet polymer cake.
  • the cake was transferred into a hot-air fluid bed dryer.
  • the cake was dried at approximately 50 0 C.
  • the chlorinated polyethylene composition was designated as Inventive Example 2("CPE-I2"), having a bulk chlorine content of approximately 34.3 weigh percent.
  • the Inventive Example 2 was sieved into different fractions based on their size distribution. The different fractions were analyzed for their chlorine content, and the results are displayed in Figure 4. Referring to Figure 4, a linear interpolation of the Inventive Example 2 data points that straddled the reference line set by the Comparative Example 2; thus, generating a slope of -0.0218 chlorine content in weight percent per average particle size in micron.
  • Inventive Sample B (“Inventive Polyethylene B”) (“HDPE-IB”) is a high-density polyethylene produced via a catalyst system including a catalyst, i.e. UCATTM J, and a cocatalyst, i.e. trialkyl aluminum (tri ethyl aluminum or TEAL) in a gas phase polymerization process.
  • the polymerization conditions are shown in Table I.
  • the polymerization was initiated by continuously feeding the catalyst system including a catalyst, i.e. UCATTM J, and a cocatalyst, i.e. trialkyl aluminum (tri ethyl aluminum or TEAL), into a fluidized bed of polyethylene granules, together with ethylene and hydrogen.
  • This inventive high-density polyethylene composition was designated as the Inventive Sample B, and it had a density of approximately 0.951 g/cm 3 , a melt index I 2 of approximately 0.03 grams/10 minutes, a melt flow rate Iio of approximately 0.40 grams/10 minutes, a molecular weight distribution of 3.5, and an average particle size of approximately 1110 microns.
  • Inventive Polyethylene B was chlorinated via aqueous slurry process in an enclosed, agitated vessel. 25 pounds of the Inventive Polyethylene B powder was slurried with 189 pounds of water. The slurry also contained 12 milliliters of a commercially available nonylphenol ethoxylate surfactant. 80 grams of talc was added to the starting slurry. Additional 240 grams of talc was added to the slurry during the reaction as a process aid control. The temperature of the slurry was increased to approximately 95 °C, and gaseous chlorination addition began at a controlled rate of 0.40 lbs/minute for 39 minutes until a peak reactor temperature of 133.5 0 C. was attained.
  • Chlorine flow rate of 0.36 lbs/minute were sustained for another 35 minutes at the peak reactor temperature.
  • the slurry was transferred to another agitated vessel, in which the slurry was rinsed and washed in a caustic batch at 90 0 C. to neutralize residual HCL.
  • the neutralized slurry was passed through a centrifuge to produce a wet polymer cake.
  • the cake was transferred into a hot-air fluid bed dryer.
  • the cake was dried at approximately 50 0 C. until residual moisture of less than 0.4 weight percent was attained.
  • An anti-agglomerate aid 250 grams of talc, was added to the fluid bed dryer.
  • the chlorinated polyethylene composition was designated as Inventive Example 3 ("CPE-I3"), having a bulk chlorine content of approximately 36.6 weigh percent.
  • the Inventive Example 3 was sieved into different fractions based on their size distribution. The different fractions were analyzed for their chlorine content, and the results are displayed in Figure 5.
  • Figure 5 further indicates that Inventive Example 3 particles having an average particle size of less than 750 microns exhibit higher chlorination levels. Figure 5 further indicates that within the same average particle size, i.e. less than 300 micron, Inventive Example 5 exhibited improved chlorination relative to the Comparative Example 1.
  • Inventive Sample C (“Inventive Polyethylene C”) (“HDPE-IC”) is a high-density polyethylene produced via a catalyst system including a catalyst, i.e. UCATTM J, and a cocatalyst, i.e. trialkyl aluminum (tri ethyl aluminum or TEAL) in a gas phase polymerization process.
  • the polymerization conditions are shown in Table I.
  • the polymerization was initiated by continuously feeding the catalyst system including a catalyst, i.e. UCATTM A, and a cocatalyst, i.e. trialkyl aluminum (tri ethyl aluminum or TEAL), into a fluidized bed of polyethylene granules, together with ethylene and hydrogen.
  • This inventive high-density polyethylene composition was designated as the Inventive Sample C, and it had a density of approximately 0.952 g/cm 3 , a melt index h of approximately 0.04 grams/ 10 minutes, a melt flow rate Iio of approximately . 0.40 grams/10 minutes, a molecular weight distribution of 3.7, and an average particle size of approximately 520 microns.
  • Inventive Polyethylene C was chlorinated via aqueous slurry process in an enclosed, agitated vessel. 25 pounds of the Inventive Polyethylene C powder was slurried with 189 pounds of water. The slurry also contained 12 milliliters of a commercially available nonylphenol ethoxylate surfactant. 80 grams of talc was added to the starting slurry. Additional 240 grams of talc was added to the slurry during the reaction as a process aid control. The temperature of the slurry was increased to approximately 95 0 C, and gaseous chlorination addition began at a controlled rate of 0.40 lbs/minute for 39 minutes until a peak reactor temperature of 133.5 °C. was attained.
  • Chlorine flow rate of 0.36 lbs/minute were sustained for another 35 minutes at the peak reactor temperature.
  • the slurry was transferred to another agitated vessel, in which the slurry was rinsed and washed in a caustic batch at 90 0 C. to neutralize residual HCL.
  • the neutralized slurry was passed through a centrifuge to produce a wet polymer cake.
  • the cake was transferred into a hot-air fluid bed dryer.
  • the cake was dried at approximately 50 °C. until residual moisture of less than 0.4 weight percent was attained.
  • An anti-agglomerate aid 250 grams of talc, was added to the fluid bed dryer.
  • the chlorinated polyethylene composition was designated as Inventive Example 4 ("CPE-I4"), having a bulk chlorine content of approximately 35.8 weigh percent.
  • the Inventive Example 4 was sieved into different fractions based on their size distribution. The different fractions were analyzed for their chlorine content, and the results are displayed in Figure 6. Referring to Figure 6, a linear interpolation of the Inventive Example 4 data points that straddled reference line set by the Comparative Example 1; thus, generating a slope of -0.0312 (chlorine content in weight percent per average particle size in micron). The intersection of this slope to a reference value set at the average Comparative Example 1 chlorine content yields an equivalent Inventive Sample 4 average particle size of 465 microns.
  • Figure 6 further indicates that Inventive Example 4 particles having an average particle size of less than 465 microns exhibit higher chlorination levels. Figure 6 further indicates that within the same average particle size, i.e. less than 300 micron, Inventive Example 4 exhibited improved chlorination relative to the Comparative Example 1.
  • Inventive Sample C (“Inventive Polyethylene C”) (“HDPE-IC”), as described in Inventive Example 4, was chlorinated via aqueous slurry process in an enclosed, agitated vessel. 25 pounds of the Inventive Polyethylene C powder was slurried with 189 pounds of water. The slurry also contained 12 milliliters of a commercially available nonylphenol ethoxylate surfactant. 80 grams of talc was added to the starting slurry. Additional 240 grams of talc was added to the slurry during the reaction as a process aid control.
  • the temperature of the slurry was increased to approximately 95 0 C, and gaseous chlorination addition began at a controlled rate of 0.40 lbs/minute for 53 minutes until a peak reactor temperature of 133.5 0 C. was attained. Chlorine flow rate of 0.36 lbs/minute were sustained for another 19 minutes at the peak reactor temperature.
  • the slurry was transferred to another agitated vessel, in which the slurry was rinsed and washed in a caustic batch at 90 °C. to neutralize residual HCL.
  • the neutralized slurry was passed through a centrifuge to produce a wet polymer cake.
  • the cake was transferred into a hot-air fluid bed dryer.
  • the cake was dried at approximately 50 0 C.
  • the chlorinated polyethylene composition was designated as Inventive Example 5 ("CPE-I5"), having a bulk chlorine content of approximately 37.2 weigh percent.
  • the Inventive Example 4 was sieved into different fractions based on their size distribution. The different fractions were analyzed for their chlorine content, and the results are displayed in Figure 7. Referring to Figure 7, a linear interpolation of the Inventive Example 5 ("CPE-I5") data points that straddled reference line set by the Comparative Example 2 ("CPE-C2"); thus, generating a slope of -0.0258 (chlorine content in weight percent per average particle size in micron).
  • Formulation 1 and 2 are comparative formulations utilizing commercially available chlorinated polyethylenes, Tyrin CM 0836 and TYR CM 9934, respectively.
  • Formulation 3 is an inventive formulation utilizing the chlorinated polyethylene of Inventive Example 5 ("CPE-I5"), as described hereinabove.
  • TYRINTM CM 0836 is a chlorinated polyethylene elastomer commercially available from The Dow Chemical Company.
  • TYR CM 9934 is a chlorinated polyethylene commercially available from the Dow Chemical Company.
  • Carbon black is [] commercially available from [Sid Richardson], [LA, USA
  • DINP is [a plasticizer] commercially available from [HallStar], [USA].
  • VULCUP ® 40KE is [a peroxide] commercially available from GEO Specialty Chemicals, [USA].
  • SARET(r) SR 517 is [a coagent for peroxide cure] commercially available from Sartomer, Inc., [USA].
  • Comparative formulations 1-2 and inventive formulation 3 are shown in Table II. Comparative formulations 1-2, and inventive formulation 3 were tested for their physical properties, and the results are reported in Table III.
  • Test methods include the following:
  • Density (g/cm 3 ) was measured according to ASTM-D 792-03, Method B, in isopropanol. Specimens were measured within 1 hour of molding after conditioning in the isopropanol bath at 23 ° C for 8 min to achieve thermal equilibrium prior to measurement. The specimens were compression molded according to ASTM D-4703-00 Annex A with a 5 min initial heating period at about 190 ° C and a 15 ° C/min cooling rate per Procedure C. The specimen was cooled to 45 ° C in the press with continued cooling until "cool to the touch.”
  • Melt index (I 2 ) was measured at 190 0 C under a load of 2.16 kg according to ASTM D- 1238-03.
  • Melt flow rate (Iio) was measured at 19O 0 C under a load of 10.0 kg according to ASTM D- 1238-03.
  • Weight average molecular weight (M w ) and number average molecular weight (M n ) were determined according to methods known in the art using conventional GPC, as described herein below.
  • the molecular weight distributions of ethylene polymers were determined by gel permeation chromatography (GPC).
  • the chromatographic system consisted of a Waters (Millford, MA) 150 0 C high temperature gel permeation chromatograph, equipped with a Precision Detectors (Amherst, MA) 2-angle laser light scattering detector Model 2040. The 15° angle of the light scattering detector was used for calculation purposes. Data collection was performed using Viscotek TriSEC software version 3 and a 4-channel Viscotek Data Manager DM400. The system was equipped with an on-line solvent degas device from Polymer Laboratories. The carousel compartment was operated at 140 0 C and the column compartment was operated at 150 0 C.
  • the columns used were four Shodex HT 806M 300 mm, 13 ⁇ m columns and one Shodex HT8O3M 150 mm, 12 ⁇ m column.
  • the solvent used was 1,2,4 trichlorobenzene.
  • the samples were prepared at a concentration of 0.1 grams of polymer in 50 milliliters of solvent.
  • the chromatographic solvent and the sample preparation solvent contained 200 ⁇ g/g of butylated hydroxytoluene (BHT). Both solvent sources were nitrogen sparged. Polyethylene samples were stirred gently at 160 0 C for 4 hours.
  • the injection volume used was 200 microliters, and the flow rate was 0.67 milliliters/min.
  • Calibration of the GPC column set was performed with 21 narrow molecular weight distribution polystyrene standards, with molecular weights ranging from 580 to 8,400,000 g/mol, which were arranged in 6 "cocktail" mixtures with at least a decade of separation between individual molecular weights.
  • the standards were purchased from Polymer Laboratories (Shropshire, UK).
  • the polystyrene standards were prepared at 0.025 grams in 50 milliliters of solvent for molecular weights equal to, or greater than, 1,000,000 g/mol, and 0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000 g/mol.
  • the polystyrene standards were dissolved at 80 0 C with gentle agitation for 30 minutes.
  • the narrow standards mixtures were run first, and in order of decreasing highest molecular weight component, to minimize degradation.
  • the polystyrene standard peak molecular weights were converted to polyethylene molecular weights using the following equation (as described in Williams and Ward, J. Polvm. Sci.. Polvm. Let., 6, 621 (1968)):
  • Mpolyethylene A x (Mpolystyrene) B , where M is the molecular weight, A has a value of 0.41 and B is equal to 1.0.
  • the Systematic Approach for the determination of multi-detector offsets was done in a manner consistent with that published by Balke, Mourey, et al. (Mourey and Balke, Chromatography Polvm. Chpt 12, (1992) and Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polvm. Chpt 13, (1992)), optimizing dual detector log results from Dow broad polystyrene 1683 to the narrow standard column calibration results from the narrow standards calibration curve using in-house software.
  • the molecular weight data for off-set determination was obtained in a manner consistent with that published by Zimm (Zimm.B.H., J.Chem. Phys.. 16, 1099 (1948)) and Kratochvil (Kratochvil, P., Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, NY (1987)).
  • the overall injected concentration used for the determination of the molecular weight was obtained from the sample refractive index area and the refractive index detector calibration from a linear polyethylene homopolymer of 115,000 g/mol molecular weight, which was measured in reference to NIST polyethylene homopolymer standard 1475.
  • the chromatographic concentrations were assumed low enough to eliminate addressing 2 nd Virial coefficient effects (concentration effects on molecular weight).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention porte sur des polyéthylènes chlorés, sur un procédé de fabrication de ceux-ci, et sur des articles obtenus à partir de ceux-ci. La composition de polyéthylène chloré comprenant le produit de réaction de (a) 55 à 90 pour cent en poids d'un polyéthylène haute densité en phase gazeuse, à base du poids total du polyéthylène haute densité chloré, le polyéthylène haute densité ayant une masse volumique dans la plage de 0,940 à 0,970 g/cm3, un indice de fusion I2 dans la plage de moins de 15 g/10 minutes, un indice de fluidité I10 dans la plage de moins de 200 g/10 minutes, et une dimension moyenne de particule dans la plage de moins de 800 microns ; (b) 10 à 45 pour cent en poids de chlore, sur la base du poids total du polyéthylène haute densité chloré ; et (c) facultativement moins de 15 pour cent en poids d'un agent tensio-actif, sur la base du poids total du polyéthylène chloré. Le procédé de fabrication de polyéthylènes haute densité chloré selon la présente invention comprend les étapes consistant à (1) prendre un polyéthylène haute densité en phase gazeuse, le polyéthylène haute densité ayant une masse volumique dans la plage de 0,940 à 0,970 g/cm3, un indice de fusion I2 dans la plage de moins de 15 g/10 minutes, un indice de fluidité I10 dans la plage de moins de 200 g/10 minutes, et une dimension moyenne de particule dans la plage de moins de 800 microns ; (2) prendre du chlore ; (3) facultativement prendre un agent tensio-actif ; (4) former une bouillie aqueuse du polyéthylène haute densité facultativement en présence de l'agent tensio-actif ; (5) augmenter la température de la bouillie à une température inférieure à la température de point de fusion de pic du polyéthylène haute densité tout en agitant le polyéthylène haute densité ; (6) mélanger le chlore avec la bouillie tout en maintenant la température du mélange de chlore et de bouillie à une température inférieure à la température de point de fusion de pic du polyéthylène haute densité tout en agitant le mélange ; (7) facultativement ajouter un agent anti-agglomération ; (8) permettant ainsi de chlorer le polyéthylène haute densité. Les articles selon la présente invention comprennent une composition de polyéthylène chloré comprenant le produit de réaction de (a) 55 à 90 pour cent en poids d'un polyéthylène haute densité en phase gazeuse, sur la base du poids total du polyéthylène haute densité chloré, le polyéthylène haute densité ayant une masse volumique dans la plage de 0,940 à 0,970 g/cm3, un indice de fusion I2 dans la plage de moins de 15 g/10 minutes, un indice de fluidité I10 dans la plage de moins de 200 g/10 minutes, et a une dimension moyenne de particule dans la plage de moins de 800 microns ; (b) 10 à 45 pour cent en poids de chlore, sur la base du poids total du polyéthylène haute densité chloré ; et (c) facultativement moins de 15 pour cent en poids d'un agent tensio-actif, sur la base du poids total du polyéthylène chloré.
PCT/US2009/043334 2008-05-12 2009-05-08 Polyéthylènes chlorés, leur procédé de fabrication, et articles obtenus à partir de ceux-ci Ceased WO2009140169A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US5243308P 2008-05-12 2008-05-12
US61/052,433 2008-05-12

Publications (1)

Publication Number Publication Date
WO2009140169A1 true WO2009140169A1 (fr) 2009-11-19

Family

ID=40746926

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2009/043334 Ceased WO2009140169A1 (fr) 2008-05-12 2009-05-08 Polyéthylènes chlorés, leur procédé de fabrication, et articles obtenus à partir de ceux-ci

Country Status (1)

Country Link
WO (1) WO2009140169A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3784382B1 (fr) * 2018-04-24 2024-07-17 SABIC Global Technologies B.V. Procédé de séchage de composition polymère humide

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4113805A (en) * 1974-11-28 1978-09-12 Hoechst Aktiengesellschaft Thermoplastic compositions comprising PVC and chlorinated polyethylene
US4303771A (en) * 1978-12-14 1981-12-01 Union Carbide Corporation Process for the preparation of high density ethylene polymers in fluid bed reactor
US4767823A (en) * 1984-12-05 1988-08-30 The Dow Chemical Company Halogenated ethylene polymers with improved resistance to agglomeration
WO2008002952A2 (fr) * 2006-06-28 2008-01-03 Dow Global Technologies Inc. Polymères à base d'éthylène chloré et compositions et articles préparés à partir d'eux

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4113805A (en) * 1974-11-28 1978-09-12 Hoechst Aktiengesellschaft Thermoplastic compositions comprising PVC and chlorinated polyethylene
US4303771A (en) * 1978-12-14 1981-12-01 Union Carbide Corporation Process for the preparation of high density ethylene polymers in fluid bed reactor
US4767823A (en) * 1984-12-05 1988-08-30 The Dow Chemical Company Halogenated ethylene polymers with improved resistance to agglomeration
WO2008002952A2 (fr) * 2006-06-28 2008-01-03 Dow Global Technologies Inc. Polymères à base d'éthylène chloré et compositions et articles préparés à partir d'eux

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3784382B1 (fr) * 2018-04-24 2024-07-17 SABIC Global Technologies B.V. Procédé de séchage de composition polymère humide

Similar Documents

Publication Publication Date Title
US7576166B2 (en) Process for the production of linear low-density polyethylene composition
EP2999742B1 (fr) Compositions contenant des polymères à base d'éthylène de faible densité à résistance élevée à l'état fondu, et films formés à partir de celles-ci
JP5727467B2 (ja) 架橋されたポリマー組成物から成る架橋されたパイプ
US10287423B2 (en) Low density ethylene-based compositions with improved melt strength, output, and mechanical properties
EP2300529B1 (fr) Compositions de polyéthylène
EP2227491B1 (fr) Compositions de polymères à base d'éthylène, leurs procédés de fabrication, et articles préparés à partir de celles-ci
CA2576155C (fr) Compositions de polyethylene bimodal de resistance elevee
AU747084B2 (en) Process for the manufacture of a composition comprising ethylene polymers
RU2439085C2 (ru) Порошок полиолефина
EP2164897A1 (fr) Composition de résine de copolymère de polyéthylène multimodal, son procédé de préparation et produit polymère la comprenant
CN102449057A (zh) 用于交联管的聚合物组合物
RU2428433C2 (ru) Полимерная композиция
EP2588506B1 (fr) Composition de catalyseur autolimitant pour la polymérisation de l'éthylène
WO2009140169A1 (fr) Polyéthylènes chlorés, leur procédé de fabrication, et articles obtenus à partir de ceux-ci
WO2022139885A1 (fr) Résines de polyéthylène modifiées et leur procédé de fabrication

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09747254

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09747254

Country of ref document: EP

Kind code of ref document: A1