WO2009140169A1

WO2009140169A1 - Chlorinated polyethylenes, method of producing the same, and articles made therefrom

Info

Publication number: WO2009140169A1
Application number: PCT/US2009/043334
Authority: WO
Inventors: Gregory Johnson; William Michie; Stephanie Whited; Laakso, Jr.
Original assignee: Dow Global Technologies LLC
Current assignee: Dow Global Technologies LLC
Priority date: 2008-05-12
Filing date: 2009-05-08
Publication date: 2009-11-19
Anticipated expiration: 2010-11-12

Abstract

The instant invention relates to chlorinated poly ethylenes, 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/cm³, a melt index I₂ in the range of less than 15 g/10 minutes, a melt flow rate I₁₀ 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 poly ethylenes according to the instant invention 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/cm³, a melt index I₂ in the range of less than 15 g/10 minutes, a melt flow rate I10 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 polyethylene while agitating the mixture; (7) optionally adding an anti-agglomeration agent; (8) thereby chlorinating the high-density polyethylene. The articles according to the instant invention comprise 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/cm³, a melt index I₂ in the range of less than 15 g/10 minutes, a melt flow rate I₁₀ 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.

Description

CHLORINATED POLYETHYLENES, METHOD OF PRODUCING THE SAME, AND ARTICLES MADE THEREFROM

Cross-Reference to Related Applications

This application is a non-provisional application claiming priority from the U.S. Provisional Patent Application No. 61/052,433, filed on May 12, 2008, entitled "CHLORINATED POLYETHYLENES, METHOD OF PRODUCING THE SAME, AND ARTICLES MADE THEREFROM," the teachings of which are incorporated by reference herein, as if reproduced in full hereinbelow.

Field of Invention

The instant invention relates to chlorinated polyethylenes, method of producing the same, and articles made therefrom.

Background of the Invention

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 70⁰C. for a time sufficient to afford a chlorinated polyethylene wax containing up to about 75 percent by weight of chlorine; (c) after chlorination of the wax has commenced, contacting the wax with from about 0.05 percent to about 0.75 percent by weight of oxygen based on un-chlorinated wax, the contacting with oxygen being substantially completed before the wax reaches a chlorine content of greater than about 45 percent by weight; and (d) separating the thus chlorinated polyethylene wax from the slurry.

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. 3,607,855 describes a continuous process for the chlorination of polyolefins in the presence of chlorohydrocarbons.

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 100⁰C. to a line-out chlorination temperature of from 116⁰C. to 128⁰C. in the first stage and remains at the line-out temperature in the second stage.

In attempts to improve the rate of chlorination, different methods have been suggested. However, there is still a need for a method for chlorination of polyethylene at improved chlorination rates. Furthermore, there is a need for chlorinated polyethylene polymers produced via a method with improved chlorination rates.

Summary of the Invention

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/cm³, 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 according to the instant invention 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/cm³, 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 polyethylene while agitating the mixture; (7) optionally adding an anti-agglomeration agent; (8) thereby chlorinating the high-density polyethylene. The articles according to the instant invention comprise 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/cm³, 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.

In one embodiment, the instant invention provides 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/cm³, 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.

In an alternative embodiment, 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/cm³, a melt index I₂ 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 peak melting point temperature of the high-density polyethylene while agitating the mixture; (7) optionally adding an anti-agglomeration agent; (8) thereby chlorinating the high-density polyethylene. In another alternative embodiment, the instant invention further provides an article comprising 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/cm³, a melt index I₂ in the range of less than 15 g/10 minutes, a melt flow rate I₁0 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.

In an alternative embodiment, 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.

In an alternative embodiment, 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.

In an alternative embodiment, 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.

In an alternative embodiment, 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.

In an alternative embodiment, 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.

In an alternative embodiment, 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. In an alternative embodiment, 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. In an alternative embodiment, 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.

Brief Description of the Drawings

For the purpose of illustrating the instant invention, there is shown in the drawings a form that is presently preferred; it being understood, however, that this invention is not limited to the precise arrangements and instrumentalities shown.

Fig. 1 is a graph illustrating the relationship between chlorine content in weight percent and average particle size measured in μm 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 μm 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 μm 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 μm 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 μm 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 μm of the Inventive Example 4; and

Fig. 7 is a graph illustrating the relationship between chlorine content in weight percent and average particle size measured in μm of the Inventive Example 5.

Detailed Description of the Invention

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/cm³, 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. The term "polyethylene," as used herein, refers to ethylene homopolymers and/or ethylene and one or more α-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/cm³. All individual values and subranges from 0.940 to 0.970 g/cm³ 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/cm³ to an upper limit of 0.950, 0.960, 0.965, or 0.975 g/cm³. For example, the polyethylene composition may have a density in the range of 0.942 to 0.970 g/cm³; or in the alternative, the polyethylene composition may have a density in the range of 0.940 to 0.965 g/cm³; or in the alternative, the polyethylene composition may have a density in the range of 0.940 to 0.960 g/cm³; or in the alternative, the polyethylene composition may have a density in the range of 0.940 to 0.950 g/cm³; or in the alternative, the polyethylene composition may have a density in the range of 0.950 to 0.965 g/cm³; or in the alternative, the polyethylene composition may have a density in the range of 0.945 to 0.965 g/cm³.

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. For example, 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.

The high-density polyethylene composition has a melt index (I₂) 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 (I₂) 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. For example, the high-density polyethylene composition may have a melt index (I₂) 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 (I₂) 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 (I₂) 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 (I₂) 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 (I₂) 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 (I₂) 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 (I₂) in the range of 0.5 to 14 g/10 minutes; or in the alternative, the high-density polyethylene composition may have a melt index (I₂) in the range of 0.5 to 10 g/10 minutes.

The high-density polyethylene composition has a melt flow rate (I₁₀) 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. For example, the high- density polyethylene composition may have a melt flow rate (I₁₀) 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 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 5 to 110 g/10 minutes.

The high-density polyethylene composition has a melt flow ratio (I₁0/I₂) 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 (I₁₀/I₂) 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. For example, 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 (I₁0/I₂) in the range of 5 to 20; or in the alternative, the high-density polyethylene composition may have a melt flow ratio (I₁₀/I₂) in the range of 7 to 20; or in the alternative, the high-density polyethylene composition may have a melt flow ratio (I₁0/I₂) 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 (I₁₀/I₂) in the range of 7 to 18; or in the alternative, the high-density polyethylene composition may have a melt flow ratio (I₁₀/I₂) in the range of 9 to 18. 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. For example, 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. For example, 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 α-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 α-olefϊn 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 α-olefϊn 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 α-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 α-olefin comonomers; or in the alternative, the high-density polyethylene composition may comprise less than 5 percent by weight of units derived from one or more α-olefϊn comonomers; or in the alternative, the high-density polyethylene composition may comprise less than 3 percent by weight of units derived from one or more α-olefϊn comonomers; or in the alternative, the high-density polyethylene composition may comprise less than 1 percent by weight of units derived from one or more α-olefϊn comonomers; or in the alternative, the high-density polyethylene composition may comprise less than 0.5 percent by weight of units derived from one or more α-olefin comonomers.

The α-olefϊn comonomers typically have no more than 20 carbon atoms. For example, the α-olefϊn comonomers may preferably have 3 to 10 carbon atoms, and more preferably 3 to 8 carbon atoms. Exemplary α-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 α-olefϊn 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 derived from ethylene comonomers; or in the alternative, the high-density polyethylene composition may comprise at least 99 percent by weight of units derived from ethylene comonomers; or in the alternative, the high-density polyethylene composition may comprise at least 99.5 percent by weight of units derived from ethylene comonomers.

The high-density polyethylene composition may have an average particle size in the range of less than or equal to 2000 μm. All individual values and subranges from less than or equal to 2000 μm 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 μm to an upper limit of 150, 200, 250, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 1000, 1500, or 2000 μm. For example, the high-density polyethylene composition may have an average particle size in the range of 250 to 2000 μm; or in the alternative, the high-density polyethylene composition may have an average particle size in the range of 50 to 1000 μm; or in the alternative, the high-density polyethylene composition may have an average particle size in the range of 250 to 800 μm; or in the alternative, the high-density polyethylene composition may have an average particle size in the range of 50 to 750 μm; or in the alternative, the high-density polyethylene composition may have an average particle size in the range of 50 to 700 μm; or in the alternative, the high-density polyethylene composition may have an average particle size in the range of 50 to 650 μm; or in the alternative, the high- density polyethylene composition may have an average particle size in the range of 50 to 600 μm; or in the alternative, the high-density polyethylene composition may have an average particle size in the range of 50 to 550 μm; or in the alternative, the high-density polyethylene composition may have an average particle size in the range of 50 to 500 μm; or in the alternative, the high-density polyethylene composition may have an average particle size in the range of 50 to 450 μm; or in the alternative, the high-density polyethylene composition may have an average particle size in the range of 50 to 400 μm; or in the alternative, the high- density polyethylene composition may have an average particle size in the range of 50 to 300 μm; or in the alternative, the high-density polyethylene composition may have an average particle size in the range of 50 to 300 μm; or in the alternative, the high-density polyethylene composition may have an average particle size in the range of 50 to 200 μm; or in the alternative, the high-density polyethylene composition may have an average particle size in the range of 50 to 150 μm; or in the alternative, the high-density polyethylene composition may have an average particle size in the range of 100 to 700 μm; or in the alternative, the high-density polyethylene composition may have an average particle size in the range of 300 to 650 μm; or in the alternative, the high-density polyethylene composition may have an average particle size in the range of 100 to 600 μm; or in the alternative, the high-density polyethylene composition may have an average particle size in the range of 100 to 550 μm; or in the alternative, the high-density polyethylene composition may have an average particle size in the range of 100 to 500 μm; or in the alternative, the high-density polyethylene composition may have an average particle size in the range of 100 to 450 μm; or in the alternative, the high-density polyethylene composition may have an average particle size in the range of 100 to 400 μm.

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. For example, 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.

In one embodiment, the gas phase polymerization reactor is a continuous polymerization reactor comprising one or more feed streams. In the polymerization reactor, 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 α-olefϊns, 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 α-olefins, may be fed up through a distributor plate to fluidize the bed in a continuous fluidization process.

In production, 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. N₂, 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. 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 ⁰C, preferably 75 to 110⁰C, more preferably 75 to 100⁰C, 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, a vertical cylindrical reactor, 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. Once the residual hydrocarbons are removed, and the resin is transported under N₂ to a purge bin, moisture may be introduced to reduce the presence of any residual catalyzed reactions with O₂ 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 μm. 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. For example, 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 chlorinated high-density polyethylene. In one embodiment 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/cm³, a melt index I₂ in the range of less than 15 g/10 minutes, a melt flow rate I₁₀ 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. All individual values and subranges from less than 15 weight percent are included herein and disclosed herein; for example, 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. For example, 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.

In production of the chlorinated polyethylene, the high-density polyethylene may be chlorinated via an aqueous slurry process. In one embodiment, no additional catalyst is added to promote the chlorination reaction. Optionally, acceleration of the chlorination rate may be assisted by employing 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.'

In one embodiment, 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 ⁰C. to 105 ⁰C. to a final temperature in the range of 116⁰C. to 135 ⁰C, while adding gaseous chlorine to attain a chlorine content of 10 to 50 percent based on the weight of the chlorinated polyethylene.

In one embodiment, no more gaseous chlorine is added to the reactor when the temperature of the slurry reaches the final temperature in the range of 116⁰C. 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.

In another embodiment, 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.

Subsequent to the chlorination process, 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 according to the instant invention 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 point temperature of the high-density polyethylene while agitating the mixture; (7) optionally adding an anti- agglomeration agent; (8) thereby chlorinating the high-density polyethylene.

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.

Examples

It is understood that the present invention is operable in the absence of any component, which has not been specifically disclosed. The following examples are provided in order to further illustrate the invention, i.e. that selective use of gas phase high-density polyethylene particles in a slurry chlorination process yields a chlorinated polyethylene that exhibits a more efficient chlorination (faster chlorine uptake), and they are not to be construed as limiting. These examples further illustrate the faster potential production rate in the aqueous slurry chlorination process to produce chlorinated polyethylenes having improved tensile and tear strength properties.

Comparative Example 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/cm³, a melt index h of approximately 0.03 grams/10 minutes, a melt flow rate I₁Q 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 ⁰C, and gaseous chlorination addition began at a controlled rate of 0.40 lbs/minute for 39 minutes until a peak reactor temperature of 130⁰C. was attained. Chlorine flow rate of 0.36 lbs/minute were sustained for another 35 minutes at the peak reactor temperature. After the chlorination was completed, the slurry was transferred to another agitated vessel, in which the slurry was rinsed and washed in a caustic batch at 90⁰C. 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 50⁰C. 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 Example 2

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/cm³, 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 ⁰C, 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 ⁰C. was attained. Chlorine flow rate of 0.36 lbs/minute were sustained for another 19 minutes at the peak reactor temperature. After the chlorination was completed, the slurry was transferred to another agitated vessel, in which the slurry was rinsed and washed in a caustic batch at 90⁰C. 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 50⁰C. 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 Example 1

Inventive Sample A ("Inventive Polyethylene A") ("HDPE-IA") is a high-density polyethylene produced via a catalyst system including a catalyst, i.e. UCAT™ 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. UCAT™ 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. Inert gases, nitrogen and isopentane, made up the remaining pressure in the fluidized bed reactor. The high-density polyethylene composition is continuously removed, purged, and transferred where it is cooled to ambient temperature. 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 ⁰C, 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 ⁰C. was attained. Chlorine flow rate of 0.36 lbs/minute were sustained for another 35 minutes at the peak reactor temperature. After the chlorination was completed, the slurry was transferred to another agitated vessel, in which the slurry was rinsed and washed in a caustic batch at 90⁰C. 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 50⁰C. 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. Referring to Figure 3, a linear interpolation of the Inventive Example 1 data points that straddled reference line set by the Comparative Example 1 ; thus, generating a slope of -0.0292 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 1 average particle size of 571 microns. 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 Example 2

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 ⁰C, 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 ⁰C. was attained. Chlorine flow rate of 0.36 lbs/minute were sustained for another 19 minutes at the peak reactor temperature. After the chlorination was completed, the slurry was transferred to another agitated vessel, in which the slurry was rinsed and washed in a caustic batch at 90⁰C. 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 50⁰C. 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 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. The intersection of this slope to a reference value set at the average Comparative Example 2 chlorine content yields an equivalent Inventive Example 2 average particle size of 564 microns. Figure 4 further indicates that Inventive Example 2 particles having an average particle size of less than 564 microns exhibit higher chlorination levels. Figure 4 further indicates that within the same average particle size, i.e. less than 300 micron, Inventive Example 2 exhibited improved chlorination relative to the Comparative Example 2.

Inventive Example 3

Inventive Sample B ("Inventive Polyethylene B") ("HDPE-IB") is a high-density polyethylene produced via a catalyst system including a catalyst, i.e. UCAT™ 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. UCAT™ 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. Inert gases, nitrogen and isopentane, made up the remaining pressure in the fluidized bed reactor. The high-density polyethylene composition is continuously removed, purged, and transferred where it is cooled to ambient temperature. This inventive high-density polyethylene composition was designated as the Inventive Sample B, and it had a density of approximately 0.951 g/cm³, a melt index I₂ 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 ⁰C. was attained. Chlorine flow rate of 0.36 lbs/minute were sustained for another 35 minutes at the peak reactor temperature. After the chlorination was completed, the slurry was transferred to another agitated vessel, in which the slurry was rinsed and washed in a caustic batch at 90⁰C. 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 50⁰C. 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. Referring to Figure 5, a linear interpolation of the Inventive Example 3 data points that straddled reference line set by the Comparative Example 1; thus, generating a slope of -0.0179 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 3 average particle size of 750 microns. 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 Example 4

Inventive Sample C ("Inventive Polyethylene C") ("HDPE-IC") is a high-density polyethylene produced via a catalyst system including a catalyst, i.e. UCAT™ 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. UCAT™ 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. Inert gases, nitrogen and isopentane, made up the remaining pressure in the fluidized bed reactor. The high-density polyethylene composition is continuously removed, purged, and transferred where it is cooled to ambient temperature. This inventive high-density polyethylene composition was designated as the Inventive Sample C, and it had a density of approximately 0.952 g/cm³, 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 ⁰C, 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. After the chlorination was completed, the slurry was transferred to another agitated vessel, in which the slurry was rinsed and washed in a caustic batch at 90⁰C. 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 Example 5

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 ⁰C, 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 ⁰C. was attained. Chlorine flow rate of 0.36 lbs/minute were sustained for another 19 minutes at the peak reactor temperature. After the chlorination was completed, 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 50⁰C. 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 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). The intersection of this slope to a reference value set at the average Comparative Example 2 ("CPE-C2") chlorine content yields an equivalent Inventive Sample 5 average particle size of 433 microns. Figure 6 further indicates that Inventive Example 5 ("CPE-I5") particles having an average particle size of less than 433 microns exhibit higher chlorination levels. Figure 7 further indicates that within the same average particle size, i.e. less than 300 micron, Inventive Example 5 ("CPE-I5") exhibited improved chlorination relative to the Comparative Example 2 ("CPE-C2").

Formulations 1-3

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.

TYRIN™ 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.

N-744 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].

These components for 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

Test methods include the following:

Density (g/cm³) 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 (I₂) was measured at 190⁰C under a load of 2.16 kg according to ASTM D- 1238-03. Melt flow rate (Iio) was measured at 19O⁰C under a load of 10.0 kg according to ASTM D- 1238-03.

Approximately 2000 ppm by weight of Irganox B215 was added to each HDPE polymer as a stabilization aid prior to measuring melt index.

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) 150⁰C 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 140⁰C and the column compartment was operated at 150⁰C. The columns used were four Shodex HT 806M 300 mm, 13 μm columns and one Shodex HT8O3M 150 mm, 12 μm 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 μg/g of butylated hydroxytoluene (BHT). Both solvent sources were nitrogen sparged. Polyethylene samples were stirred gently at 160⁰C 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 80⁰C 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). Molecular weight calculations were performed using in-house software. The calculation of the number-average molecular weight, weight-average molecular weight, and z-average molecular weight were made according to the following equations, assuming that the refractometer signal is directly proportional to weight fraction. The baseline- subtracted refractometer signal can be directly substituted for weight fraction in the equations below. Note that the molecular weight can be from the conventional calibration curve or the absolute molecular weight from the light scattering to refractometer ratio. An improved estimation of z-average molecular weight, the baseline-subtracted light scattering signal can be substituted for the product of weight average molecular weight and weight fraction in equation (2) below:

a) ' - Mn = ∑^W/' b) ' - Mw = ∑tø ^*"'*

∑(%) ∑w.

The present invention may be embodied in other forms without departing from the spirit and the essential attributes thereof, and, accordingly, reference should be made to the appended claims, rather than to the foregoing specification, as indicating the scope of the invention.

Table I

Table II Recipes shown in phr (parts per hundred parts rubber)

Table III

Claims

We Claim:

1. A chlorinated polyethylene composition comprising the reaction product of: 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 said high-density polyethylene has a density in the range of 0.940 to 0.970 g/cm³, a melt index I₂ in the range of less than 15 g/10 minutes, a melt flow rate I₁₀ in the range of less than 200 g/10 minutes; and an average particle size in the range of less than 800 microns;

10 to 45 percent by weight of chlorine, based on the total weight of the chlorinated high-density polyethylene; and optionally less than 15 percent by weight of a surfactant, based on the total weight of the chlorinated polyethylene.

2. A method of producing a chlorinated high-density polyethylene composition comprising the steps of: selecting a gas-phase high-density polyethylene, wherein said high- density polyethylene has a density in the range of 0.940 to 0.970 g/cm³, a melt index I₂ in the range of less than 15 g/10 minutes, a melt flow rate I_1O in the range of less than 200 g/10 minutes; and an average particle size in the range of less than 800 microns; selecting chlorine; optionally selecting a surfactant; forming an aqueous slurry of said high-density polyethylene optionally in the presence of said surfactant; increasing the temperature of said slurry to a temperature of less than peak melting point temperature of said high-density polyethylene while agitating said high- density polyethylene; admixing said chlorine with said slurry while maintaining the temperature of said mixture of chlorine and slurry at a temperature of less than peak melting point temperature of said high-density polyethylene while agitating said mixture; optionally adding anti-agglomeration agent; thereby chlorinating said high-density polyethylene.

3. An article comprising: a chlorinated polyethylene composition comprising the reaction product of;

55 to 90 percent by weight a gas-phase high-density polyethylene, based on the total weight of the chlorinated high-density polyethylene, wherein said high- density polyethylene has a density in the range of 0.940 to 0.970 g/cm³, a melt index I₂ in the range of less than 15 g/10 minutes, a melt flow rate I₁₀ in the range of less than 200 g/10 minutes; and an average particle size in the range of less than 800 microns;

4. An impact modified composition comprising: polyvinyl chloride; and a chlorinated polyethylene composition comprising the reaction product of;

55 to 90 percent by weight a gas-phase high-density polyethylene, based on the total weight of the chlorinated high-density polyethylene, wherein said high- density polyethylene has a density in the range of 0.940 to 0.970 g/cm³, a melt index I₂ in the range of less than 15 g/10 minutes, a melt flow rate I_1O in the range of less than 200 g/10 minutes; and an average particle size in the range of less than 800 microns;

5. An article comprising: polyvinyl chloride; and a chlorinated polyethylene composition comprising the reaction product of;

6. The chlorinated polyethylene composition according to any of the preceding Claims 1-5, wherein said high-density polyethylene has an average particle size in the range of less than 750 microns.

7. The chlorinated polyethylene composition according to any of the preceding Claims 1-5, wherein said high-density polyethylene has an average particle size in the range of less than 550 microns.

8. The chlorinated polyethylene composition according to any of the preceding Claims 1-5, wherein said chlorinated polyethylene comprises 15 to 45 percent by weight of chlorine, based on the total weight of the chlorinated high-density polyethylene.