WO2017117077A1 - A chlorinated polyethylene composition, an impact modifier comprising the same and a polymer composition comprising the impact modifier - Google Patents

A chlorinated polyethylene composition, an impact modifier comprising the same and a polymer composition comprising the impact modifier Download PDF

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Publication number
WO2017117077A1
WO2017117077A1 PCT/US2016/068616 US2016068616W WO2017117077A1 WO 2017117077 A1 WO2017117077 A1 WO 2017117077A1 US 2016068616 W US2016068616 W US 2016068616W WO 2017117077 A1 WO2017117077 A1 WO 2017117077A1
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Prior art keywords
chlorinated polyethylene
composition according
ethylenically unsaturated
group
polyethylene resin
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PCT/US2016/068616
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French (fr)
Inventor
Carlos A. Cruz
Morris C. WILLIS
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Rohm And Haas Company
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Publication of WO2017117077A1 publication Critical patent/WO2017117077A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C08F255/023—On to modified polymers, e.g. chlorinated polymers
    • 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
    • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/08—Homopolymers or copolymers of vinylidene chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/22—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L27/24—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers modified by chemical after-treatment halogenated

Definitions

  • the disclosure relates to a chlorinated polyethylene composition, an impact modifier comprising the same and a polymer composition comprising the impact modifier.
  • Chlorinated polyethylene is currently the modifier of choice to produce vinyl siding. This modifier, although less efficient than core//shell impact additives, is valued because of its low- cost. Improving its performance, while maintaining its economics would make CPE more attractive for the siding market and even help it compete in areas where it is rarely used today, such as in profiles for windows and fences.
  • CPE with a chlorination level below 30% by weight and grafted with acrylic monomers can used as a basis to produce high performance impact modifiers.
  • a CPE with 25 % chlorine level we have specifically used a CPE with 25 % chlorine level.
  • the CPE-grafted acrylic copolymers (CPE-g-A) enhance the performance of CPE when used as impact modifiers for poly (vinyl chloride), PVC, when tested by the standard ASTM D256 Notched Izod Impact test.
  • grafting acrylic monomers at low levels (7.5 %) produces high impact performance.
  • Yet another aspect of the invention is that, using a sequential addition of monomers, that is, grafting one monomer first, finalizing its polymerization, adding another monomer next and graft-polymerizing it provides a distinct performance not observed if the two monomers are added and polymerized together.
  • monomers that is, grafting one monomer first, finalizing its polymerization, adding another monomer next and graft-polymerizing it provides a distinct performance not observed if the two monomers are added and polymerized together.
  • CPE's with the same level of chlorination do not necessarily lead to the same level of performance when grafted with acrylic monomers.
  • the disclosure provides a chlorinated polyethylene composition
  • a chlorinated polyethylene composition comprising a chlorinated polyethylene resin having a chlorine content of less than 30wt% based on the total weight of the chlorinated polyethylene resin, graft polymerized with one or more ethyl enically unsaturated monomer selected from the group consisting of an ethylenically unsaturated carboxylic acid ester monomer, a monovinyl aromatic monomer and mixtures thereof.
  • the disclosure provides an impact modifier comprising the inventive chlorinated polyethylene composition.
  • the disclosure provides a polymer composition comprising one or more inventive impact modifier and one or more base polymers.
  • the disclosure provides an article of manufacture comprising the inventive polymer composition.
  • chlorinated polyethylene refers to an ethylene-based polymer comprising one or more chlorine-containing comonomers; and/or an ethylene-based polymer which is subject to a chlorination reaction, for example see chlorination reactions described in US Patent 7763692, US Patent 5446064, US Patent 4767823 and WO2008/002952, the disclosures of which are incorporated herein by reference.
  • Polyethylene or ethylene-based polymer means a polymer having greater than 50 wt% units derived from ethylene monomer and may include ethylene homopolymers, ethylene/alpha-olefin copolymers (having units derived from ethylene and an alpha-olefin monomer) and ethylene interpolymers (having units derived from ethylene and two or more comonomers).
  • the disclosure further provides a chlorinated polyethylene composition according to any embodiment disclosed herein except that the ethylene-based polymer has a melt index, I2, in the range of 0.1 g/10 min to 8 g/10 min. All individual values and subranges from 0.1 to 8 g/10 min are included and disclosed herein.
  • the I2 may range from a lower limit of 0.1, 1, 3, 5 or 7 g/10 min to an upper limit of 0.5, 2, 4, 6, or 8 g/10 min.
  • the I2 of the ethylene-based polymer may be from 0.1 to 8 g/10 min, or in the alternative, from 0.25 to 2 g/10 min.
  • the ethylene-based polymer has a density from 0.90 to 0.96 g/cm 3 . All individual values and subranges from 0.90 to 0.96 g/cm 3 are included and disclosed herein; for example, the density can range from a lower limit of 0.90, 0.92, or 0.94 g/cm 3 to an upper limit of 0.91, 0.93, 0.95 or 0.96 g/cm 3 .
  • the density may range from 0.90 to 0.96 g/cm 3 , or in the alternative, from 0.90 to 0.93 g/cm 3 , or in the alternative, from 0.93 to 0.96 g/cm 3 .
  • the chlorinated polyethylene resin has a chlorine content of less than 30 weight percent (wt%) based on the total weight of the chlorinated polyethylene resin. All individual values and subranges of less than 30 wt% are included and disclosed herein.
  • the chlorine content of the chlorinated polyethylene resin may range from less than 30, 25, 20, or 15 wt%.
  • the chlorine content of the chlorinated polyethylene resin is from greater than 0 to less than 30 wt%, or in the alternative, from 1 to less than 30 wt%, or in the alternative, from 2 to less than 30 wt%, or in the alternative, from 5 to less than 30 wt%, or in the alternative, from greater than 0 to 25 wt%, or in the alternative, from greater than 0 to 20 wt%, or in the alternative, from 5 to 25 wt%.
  • the disclosure further provides the chlorinated polyethylene composition according to any embodiment disclosed herein except that the chlorine content of the chlorinated polyethylene resin is from 5 to 28 wt%.
  • the disclosure further provides the chlorinated polyethylene composition according to any embodiment disclosed herein except that the chlorine content of the chlorinated polyethylene resin is from 20 to 26 wt%.
  • the chlorinated polyethylene resin may optionally contain chlorosulfonyl groups.
  • the polymer chain of the chlorinated polyethylene reins will have pendant chlorine groups and chlorosulfonyl groups.
  • Such polymers are known as chlorosulfonated olefin polymers.
  • Representative chlorinated and chlorosulfonated ethylene polymers include (a) chlorinated and chlorosulfonated homopolymers of ethylene and (b) chlorinated and chlorosulfonated copolymers of ethylene and at least one or more ethylenically unsaturated monomer selected from the group consisting of C 3 to Cio alpha-olefin comonomer; Ci to C12 alkyl esters of C 3 to C20 monocarboxylic acids; unsaturated C 3 to Cio mono- or dicarboxylic acids; anhydrides of unsaturated C 4 to C 8 dicarboxylic acids; and vinyl esters of saturated C2 to Ci 8 , carboxylic acids.
  • Chlorinated and chlorosulfonated graft copolymers are included as well.
  • suitable polymers include chlorinated polyethylene; chlorosulfonated polyethylene; chlorinated ethylene vinyl acetate copolymers; chlorosulfonated ethylene vinyl acetate copolymers; chlorinated ethylene acrylic acid copolymers; chlorosulfonated ethylene acrylic acid copolymers; chlorinated ethylene methacrylic acid copolymers; chlorosulfonated ethylene methacrylic acid copolymers; chlorinated ethylene methyl acrylate copolymers; chlorinated ethylene methyl methacrylate copolymers; chlorinated ethylene n-butyl methacrylate copolymers; chlorinated ethylene glycidyl methacrylate copolymers; chlorinated graft copolymers of ethylene and maleic acid anhydride; chlorinated copolymers of ethylene with propylene, butene, 3 -
  • the chlorinated polyethylene composition comprises a chlorinated polyethylene resin which is graft polymerized with one or more ethylenically unsaturated monomer selected from the group consisting of an ethylenically unsaturated carboxylic acid ester monomer, a monovinyl aromatic monomer and mixtures of any two or more thereof.
  • Exemplary one or more ethylenically unsaturated monomers include (meth)acrylic acid, (meth)acrylamides, alkyl(meth)acrylates, alkenyl(meth)acrylates, aromatic(meth)acrylates, vinyl aromatic monomers, nitrogen-containing compounds and their thio-analogs, substituted ethylene monomers, divinyl benzene, trivinylbenzene, divinyltoluene, divinylpyridine, divinylnaphthalene divinylxylene, ethyleneglycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate,
  • diethyleneglycol divinyl ether trivinylcyclohexane
  • allyl(meth)acrylate diethyleneglycol di(meth)acrylate, propyleneglycol di(meth)acrylate, 2,2-dimethylpropane-l,3-di(meth)acrylate, 1,3- butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylates, such as polyethylene glycol 200
  • (meth)acrylic includes both acrylic and methacrylic and the term “(meth)acrylate” includes both acrylate and methacrylate.
  • Alkyl includes straight chain, branched and cyclic alkyl groups.
  • methyl(meth)acrylate may mean solely methyl methacrylate, solely methyl acrylate or a combination of methyl methacrylate and methyl acrylate.
  • the disclosure provides the chlorinated polyethylene composition according to any embodiment disclosed herein, except that the one or more ethylenically unsaturated monomer is selected from the group consisting of alkyl (meth)acrylates.
  • the alkyl of the alkyl (meth)acrylate may be, in certain embodiments, be selected from the group of alkyls having from 3 to 20 carbon atoms. All individual values and subranges from 3 to 20 carbons in the alkyl group are included and disclosed herein; for example, the alkyl group may have a number of carbon atoms from a lower limit of 3, 8, 13, or 18 carbons to an upper limit of 5, 10, 15 or 20 carbon atoms.
  • the disclosure further provides the chlorinated polyethylene composition according to any embodiment disclosed herein, except that the one or more ethylenically unsaturated monomers are selected from the group consisting of butyl acrylate, methyl methacrylate, and combinations thereof.
  • the disclosure further provides the chlorinated polyethylene composition according to any embodiment disclosed herein, except that the chlorinated polyethylene resin is first grafted with an alkyl acrylate and subsequently grafted with an alkyl methacrylate.
  • the disclosure further provides the chlorinated polyethylene composition according to any embodiment disclosed herein, except that the chlorinated polyethylene resin is first grafted with butyl acrylate and subsequently grafted with methyl methacrylate.
  • the disclosure further provides an impact modifier comprising the chlorinated polyethylene composition according to any embodiment disclosed herein.
  • the disclosure further provides a polymer composition comprising a base polymer and an impact modifier according to any embodiment disclosed herein, wherein the base polymer is selected from the group consisting of poly(vinylhalides), poly(methyl methacrylate), and styrenic polymers.
  • exemplary polyvinyl halides include poly(vinylchloride) (“PVC") and poly(vinyl fluoride) (“PVF”).
  • Exemplary commercially available PVCs include those available from Formosa Plastics Corporation USA under the tradename FORMOLON.
  • Exemplary poly(vinylhalides) include cPVC (chlorinated PVC) and PVDC (polyvinylidene chloride).
  • Exemplary styrenic polymers include, SAN (styrene acrylonitrile), ABS (acrylonitrile butadiene styrene), ASA (acrylonitrile styrene acrylic), polystyrene, SMMA (styrene methyl methacrylate), and SMA (styrene maleic anhydride).
  • SAN styrene acrylonitrile
  • ABS acrylonitrile butadiene styrene
  • ASA acrylonitrile styrene acrylic
  • polystyrene polystyrene
  • SMMA styrene methyl methacrylate
  • SMA styrene maleic anhydride
  • the disclosure further provides a polymer composition according to any embodiment disclosed herein, except that the base polymer is poly(vinyl chloride).
  • the disclosure further provides a polymer composition according to any embodiment disclosed herein, except that the impact modifier is present in the base polymer at a level from 5 to 15 phr. All individual values and subranges from 5 to 15 phr (per hundred resin) are included and disclosed herein; for example, the amount of impact modifier in the base polymer can range from a lower limit of 5, 7, 9, 11, or 13 phr to an upper limit of 6, 8, 10, 12, 14 or 15 phr. For example, the amount of impact modifier in the base polymer may range from 5 to 15 phr, or in the alternative, from 5 to 10 phr, or in the alternative, from 10 to 15 phr, or in the alternative, from 6 to 10 phr.
  • the disclosure further provides an article of manufacture comprising the polymer
  • composition according to any embodiment disclosed herein.
  • Exemplary articles of manufacture include vinyl siding and construction profiles.
  • Comparative Examples are tested to examine the effect of chlorine on the impact resistance of impact modified poly(vinylchloride) ("PVC”).
  • the comparative examples were made using three ungrafted chlorinated polyethylene (“CPE") impact modifiers.
  • Comparative CPE Example 1 has a chlorine content of 36 wt%.
  • Comparative CPE Example 2 has a chlorine content of 25 wt%.
  • Comparative CPE Example 3 also has a chlorine content of 25 wt%.
  • Table 1 The molecular weight profiles for each of the Comparative CPE Examples is shown in Table 1.
  • Each Comparative Impact Modified PVC Example (1-3) is made using 8 phr impact modifier (Comp. CPE Ex. 1-3, respectfully) in FORMOLON 622S which is a medium-low molecular weight poly(vinylchloride) homopolymer commercially available from Formosa Plastics Corporation, U.S.A. (Livingston, New Jersey, USA).
  • FORMOLON 622S which is a medium-low molecular weight poly(vinylchloride) homopolymer commercially available from Formosa Plastics Corporation, U.S.A. (Livingston, New Jersey, USA).
  • Each Impact Modified CPE Example was then tested according to ASTM Method D256 (Notched Izod and % hinged) and the results are shown in Table 2.
  • Table 2 Table 2
  • Comparative CPE Example 2 was grafted first with 7.5 wt% butyl acrylate and second with 7.5 wt% methyl methacrylate.
  • Comparative CPE Example 3 was grafted first with 7.5 wt% butyl acrylate and second with 7.5 wt% methyl methacrylate.
  • Comparative CPE Example 3 Comparative CPE Example 2 was grafted first with 7.5 wt% methyl methacrylate and second with 7.5 wt% butyl acrylate.
  • the ungrafted chlorinated polyethylene is first swelled in t-butyl peroctoate in the presence of the first ethylenically unsaturated monomer to be grafted and water at 25 °C for about one hour.
  • the mixture is then heated to 85 °C for about one hour and the temperature then raised to 95 °C for about one hour.
  • the resulting slurry is filtered and washed with water.
  • the filtered solids are dried to yield the chlorinated polyethylene grafted with the first ethylenically unsaturated monomer.
  • To prepare a grafted chlorinated polyethylene grafted with more than one ethylenically unsaturated monomer the process is repeated with additional monomers.
  • Test methods include the following:
  • Notched Izod and % Hinged are measured according to ASTM D256.
  • Melt index, h is measured in accordance with ASTM D-1238 (190. degree. C; 2.16 kg).
  • Molecular weights and molecular weight distributions/ratios are determined as follows: A PolymerChar (Valencia, Spain) high temperature Gel Permeation Chromatography system consisting of an Infra-red concentration/composition detector (IR-5) was used for MW/MWD and composition determination.
  • the carrier solvent was 1,2,4-trichlorobenzene (TCB).
  • the solvent delivery pump, the on-line solvent degasser, auto-sampler, and column oven were from Agilent Technologies (Santa Clara, CA, USA).
  • the auto-sampler and detector compartments are operated at 160°C, and the column compartment is operated at 150°C.
  • the columns are three Mixed-B 10 um columns (Agilent Technologies).
  • the chromatographic solvent and the sample preparation solvent contain 250 ppm of butylated hydroxytoluene (BHT) and both solvent sources are nitrogen sparged.
  • BHT butylated hydroxytoluene
  • Polyethylene samples are prepared at targeted concentrations of 2.0 mg/mL by weighing samples by a computer controlled balance, and delivering calculated amount of solvent by the auto-sampler needle. Samples are dissolved at 160°C for 1 hour with gentle agitation. The injection volume is 200 ⁇ , and the flow rate is 1.0 mL/minute.
  • Calibration of the GPC column set is performed with 21 narrow molecular weight distribution polystyrene standards.
  • the molecular weights of the standards ranges from 580 to 8,400,000 g/mol, and are arranged in 6 "cocktail" mixtures, with at least a decade of separation between individual molecular weights.
  • the polystyrene standard peak molecular weights are converted to polyethylene molecular weights using the following equation:

Abstract

A chlorinated polyethylene composition comprising a chlorinated polyethylene resin having a chlorine content of less than 30 wt% based on the total weight of the chlorinated polyethylene resin, graft polymerized with one or more ethylenically unsaturated monomer selected from the group consisting of an ethylenically unsaturated carboxylic acid ester monomer, a monovinyl aromatic monomer and mixtures thereof is provided.

Description

A CHLORINATED POLYETHYLENE COMPOSITION, AN IMPACT MODIFIER COMPRISING THE SAME AND A POLYMER COMPOSITION COMPRISING THE
IMPACT MODIFIER
Field of Invention
The disclosure relates to a chlorinated polyethylene composition, an impact modifier comprising the same and a polymer composition comprising the impact modifier.
Background of the Invention
Chlorinated polyethylene (CPE) is currently the modifier of choice to produce vinyl siding. This modifier, although less efficient than core//shell impact additives, is valued because of its low- cost. Improving its performance, while maintaining its economics would make CPE more attractive for the siding market and even help it compete in areas where it is rarely used today, such as in profiles for windows and fences.
CPE with a chlorination level below 30% by weight and grafted with acrylic monomers, can used as a basis to produce high performance impact modifiers. We have specifically used a CPE with 25 % chlorine level. The CPE-grafted acrylic copolymers (CPE-g-A) enhance the performance of CPE when used as impact modifiers for poly (vinyl chloride), PVC, when tested by the standard ASTM D256 Notched Izod Impact test. Furthermore, we have discovered that grafting acrylic monomers at low levels (7.5 %) produces high impact performance. Yet another aspect of the invention is that, using a sequential addition of monomers, that is, grafting one monomer first, finalizing its polymerization, adding another monomer next and graft-polymerizing it provides a distinct performance not observed if the two monomers are added and polymerized together. We have also discovered that CPE's with the same level of chlorination do not necessarily lead to the same level of performance when grafted with acrylic monomers.
Summary of the Invention
In a first embodiment, the disclosure provides a chlorinated polyethylene composition comprising a chlorinated polyethylene resin having a chlorine content of less than 30wt% based on the total weight of the chlorinated polyethylene resin, graft polymerized with one or more ethyl enically unsaturated monomer selected from the group consisting of an ethylenically unsaturated carboxylic acid ester monomer, a monovinyl aromatic monomer and mixtures thereof.
In a second embodiment, the disclosure provides an impact modifier comprising the inventive chlorinated polyethylene composition.
In a third embodiment, the disclosure provides a polymer composition comprising one or more inventive impact modifier and one or more base polymers.
In a fourth embodiment, the disclosure provides an article of manufacture comprising the inventive polymer composition.
Detailed Description of the Invention
As used herein, the term "chlorinated polyethylene", refers to an ethylene-based polymer comprising one or more chlorine-containing comonomers; and/or an ethylene-based polymer which is subject to a chlorination reaction, for example see chlorination reactions described in US Patent 7763692, US Patent 5446064, US Patent 4767823 and WO2008/002952, the disclosures of which are incorporated herein by reference.
Polyethylene or ethylene-based polymer means a polymer having greater than 50 wt% units derived from ethylene monomer and may include ethylene homopolymers, ethylene/alpha-olefin copolymers (having units derived from ethylene and an alpha-olefin monomer) and ethylene interpolymers (having units derived from ethylene and two or more comonomers).
The disclosure further provides a chlorinated polyethylene composition according to any embodiment disclosed herein except that the ethylene-based polymer has a melt index, I2, in the range of 0.1 g/10 min to 8 g/10 min. All individual values and subranges from 0.1 to 8 g/10 min are included and disclosed herein. For example, the I2 may range from a lower limit of 0.1, 1, 3, 5 or 7 g/10 min to an upper limit of 0.5, 2, 4, 6, or 8 g/10 min. For example, the I2 of the ethylene-based polymer may be from 0.1 to 8 g/10 min, or in the alternative, from 0.25 to 2 g/10 min.
In a particular embodiment, the ethylene-based polymer has a density from 0.90 to 0.96 g/cm3. All individual values and subranges from 0.90 to 0.96 g/cm3 are included and disclosed herein; for example, the density can range from a lower limit of 0.90, 0.92, or 0.94 g/cm3 to an upper limit of 0.91, 0.93, 0.95 or 0.96 g/cm3. The density may range from 0.90 to 0.96 g/cm3, or in the alternative, from 0.90 to 0.93 g/cm3, or in the alternative, from 0.93 to 0.96 g/cm3.
The chlorinated polyethylene resin has a chlorine content of less than 30 weight percent (wt%) based on the total weight of the chlorinated polyethylene resin. All individual values and subranges of less than 30 wt% are included and disclosed herein. For example, the chlorine content of the chlorinated polyethylene resin may range from less than 30, 25, 20, or 15 wt%. In a particular embodiment, the chlorine content of the chlorinated polyethylene resin is from greater than 0 to less than 30 wt%, or in the alternative, from 1 to less than 30 wt%, or in the alternative, from 2 to less than 30 wt%, or in the alternative, from 5 to less than 30 wt%, or in the alternative, from greater than 0 to 25 wt%, or in the alternative, from greater than 0 to 20 wt%, or in the alternative, from 5 to 25 wt%. The disclosure further provides the chlorinated polyethylene composition according to any embodiment disclosed herein except that the chlorine content of the chlorinated polyethylene resin is from 5 to 28 wt%. The disclosure further provides the chlorinated polyethylene composition according to any embodiment disclosed herein except that the chlorine content of the chlorinated polyethylene resin is from 20 to 26 wt%.
The chlorinated polyethylene resin may optionally contain chlorosulfonyl groups. In such instance, the polymer chain of the chlorinated polyethylene reins will have pendant chlorine groups and chlorosulfonyl groups. Such polymers are known as chlorosulfonated olefin polymers.
Representative chlorinated and chlorosulfonated ethylene polymers include (a) chlorinated and chlorosulfonated homopolymers of ethylene and (b) chlorinated and chlorosulfonated copolymers of ethylene and at least one or more ethylenically unsaturated monomer selected from the group consisting of C3 to Cio alpha-olefin comonomer; Ci to C12 alkyl esters of C3 to C20 monocarboxylic acids; unsaturated C3 to Cio mono- or dicarboxylic acids; anhydrides of unsaturated C4 to C8 dicarboxylic acids; and vinyl esters of saturated C2 to Ci8, carboxylic acids. Chlorinated and chlorosulfonated graft copolymers are included as well. Specific examples of suitable polymers include chlorinated polyethylene; chlorosulfonated polyethylene; chlorinated ethylene vinyl acetate copolymers; chlorosulfonated ethylene vinyl acetate copolymers; chlorinated ethylene acrylic acid copolymers; chlorosulfonated ethylene acrylic acid copolymers; chlorinated ethylene methacrylic acid copolymers; chlorosulfonated ethylene methacrylic acid copolymers; chlorinated ethylene methyl acrylate copolymers; chlorinated ethylene methyl methacrylate copolymers; chlorinated ethylene n-butyl methacrylate copolymers; chlorinated ethylene glycidyl methacrylate copolymers; chlorinated graft copolymers of ethylene and maleic acid anhydride; chlorinated copolymers of ethylene with propylene, butene, 3 -methyl- 1-pentene, or octene and chlorosulfonated copolymers of ethylene with propylene, butene, 3 -methyl- 1-pentene or octene. The copolymers may be dipolymers, terpolymers, or higher order copolymers. Preferred chlorinated olefin polymers are-chlorinated polyethylene and chlorinated copolymers of ethylene vinyl acetate.
The chlorinated polyethylene composition comprises a chlorinated polyethylene resin which is graft polymerized with one or more ethylenically unsaturated monomer selected from the group consisting of an ethylenically unsaturated carboxylic acid ester monomer, a monovinyl aromatic monomer and mixtures of any two or more thereof.
Exemplary one or more ethylenically unsaturated monomers include (meth)acrylic acid, (meth)acrylamides, alkyl(meth)acrylates, alkenyl(meth)acrylates, aromatic(meth)acrylates, vinyl aromatic monomers, nitrogen-containing compounds and their thio-analogs, substituted ethylene monomers, divinyl benzene, trivinylbenzene, divinyltoluene, divinylpyridine, divinylnaphthalene divinylxylene, ethyleneglycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate,
diethyleneglycol divinyl ether, trivinylcyclohexane, allyl(meth)acrylate, diethyleneglycol di(meth)acrylate, propyleneglycol di(meth)acrylate, 2,2-dimethylpropane-l,3-di(meth)acrylate, 1,3- butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylates, such as polyethylene glycol 200
di(meth)acrylate and polyethylene glycol 600 di(meth)acrylate, ethoxylated bisphenol A
di(meth)acrylate, poly(butanediol) di(meth)acrylate, pentaerythritol tri(meth)acrylate,
trimethylolpropane triethoxy tri(meth)acrylate, glyceryl propoxy tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, divinyl silane, trivinyl silane, dimethyl divinyl silane, divinyl methyl silane, methyl trivinyl silane, diphenyl divinyl silane, divinyl phenyl silane, trivinyl phenyl silane, divinyl methyl phenyl silane, tetravinyl silane, dimethyl vinyl disiloxane, poly(methyl vinyl siloxane), poly(vinyl hydro siloxane), poly(phenyl vinyl siloxane), and mixtures thereof.
The term "(meth)acrylic" includes both acrylic and methacrylic and the term "(meth)acrylate" includes both acrylate and methacrylate. "Alkyl" includes straight chain, branched and cyclic alkyl groups. For example, the term "methyl(meth)acrylate" may mean solely methyl methacrylate, solely methyl acrylate or a combination of methyl methacrylate and methyl acrylate.
In another embodiment, the disclosure provides the chlorinated polyethylene composition according to any embodiment disclosed herein, except that the one or more ethylenically unsaturated monomer is selected from the group consisting of alkyl (meth)acrylates. The alkyl of the alkyl (meth)acrylate may be, in certain embodiments, be selected from the group of alkyls having from 3 to 20 carbon atoms. All individual values and subranges from 3 to 20 carbons in the alkyl group are included and disclosed herein; for example, the alkyl group may have a number of carbon atoms from a lower limit of 3, 8, 13, or 18 carbons to an upper limit of 5, 10, 15 or 20 carbon atoms.
The disclosure further provides the chlorinated polyethylene composition according to any embodiment disclosed herein, except that the one or more ethylenically unsaturated monomers are selected from the group consisting of butyl acrylate, methyl methacrylate, and combinations thereof.
The disclosure further provides the chlorinated polyethylene composition according to any embodiment disclosed herein, except that the chlorinated polyethylene resin is first grafted with an alkyl acrylate and subsequently grafted with an alkyl methacrylate.
The disclosure further provides the chlorinated polyethylene composition according to any embodiment disclosed herein, except that the chlorinated polyethylene resin is first grafted with butyl acrylate and subsequently grafted with methyl methacrylate.
The disclosure further provides an impact modifier comprising the chlorinated polyethylene composition according to any embodiment disclosed herein.
The disclosure further provides a polymer composition comprising a base polymer and an impact modifier according to any embodiment disclosed herein, wherein the base polymer is selected from the group consisting of poly(vinylhalides), poly(methyl methacrylate), and styrenic polymers. Exemplary polyvinyl halides include poly(vinylchloride) ("PVC") and poly(vinyl fluoride) ("PVF"). Exemplary commercially available PVCs include those available from Formosa Plastics Corporation USA under the tradename FORMOLON.
Exemplary poly(vinylhalides) include cPVC (chlorinated PVC) and PVDC (polyvinylidene chloride).
Exemplary styrenic polymers include, SAN (styrene acrylonitrile), ABS (acrylonitrile butadiene styrene), ASA (acrylonitrile styrene acrylic), polystyrene, SMMA (styrene methyl methacrylate), and SMA (styrene maleic anhydride).
The disclosure further provides a polymer composition according to any embodiment disclosed herein, except that the base polymer is poly(vinyl chloride).
The disclosure further provides a polymer composition according to any embodiment disclosed herein, except that the impact modifier is present in the base polymer at a level from 5 to 15 phr. All individual values and subranges from 5 to 15 phr (per hundred resin) are included and disclosed herein; for example, the amount of impact modifier in the base polymer can range from a lower limit of 5, 7, 9, 11, or 13 phr to an upper limit of 6, 8, 10, 12, 14 or 15 phr. For example, the amount of impact modifier in the base polymer may range from 5 to 15 phr, or in the alternative, from 5 to 10 phr, or in the alternative, from 10 to 15 phr, or in the alternative, from 6 to 10 phr.
The disclosure further provides an article of manufacture comprising the polymer
composition according to any embodiment disclosed herein. Exemplary articles of manufacture include vinyl siding and construction profiles.
Examples
The following examples illustrate the present invention but are not intended to limit the scope of the invention.
Several Comparative Examples are tested to examine the effect of chlorine on the impact resistance of impact modified poly(vinylchloride) ("PVC"). The comparative examples were made using three ungrafted chlorinated polyethylene ("CPE") impact modifiers. Comparative CPE Example 1 has a chlorine content of 36 wt%. Comparative CPE Example 2 has a chlorine content of 25 wt%. Comparative CPE Example 3 also has a chlorine content of 25 wt%. The molecular weight profiles for each of the Comparative CPE Examples is shown in Table 1.
Table 1
Figure imgf000007_0001
An impact modified PVC resin was made with each of these Comparative CPE ExamplesThe impact modified PVC resins. Each Comparative Impact Modified PVC Example (1-3) is made using 8 phr impact modifier (Comp. CPE Ex. 1-3, respectfully) in FORMOLON 622S which is a medium-low molecular weight poly(vinylchloride) homopolymer commercially available from Formosa Plastics Corporation, U.S.A. (Livingston, New Jersey, USA). Each Impact Modified CPE Example was then tested according to ASTM Method D256 (Notched Izod and % hinged) and the results are shown in Table 2. Table 2
Figure imgf000008_0001
To make Inventive Grafted Chlorinated Polyethylene (g-CPE) Example 1, Comparative CPE Example 2 was grafted first with 7.5 wt% butyl acrylate and second with 7.5 wt% methyl methacrylate. To make Inventive g-CPE Example 2, Comparative CPE Example 3 was grafted first with 7.5 wt% butyl acrylate and second with 7.5 wt% methyl methacrylate. To make Inventive g- CPE Example 3 Comparative CPE Example 2 was grafted first with 7.5 wt% methyl methacrylate and second with 7.5 wt% butyl acrylate. To make Inventive g-CPE Example 4 Comparative CPE Example 3 was grafted first with 7.5 wt% methyl methacrylate and second with 7.5 wt% butyl acrylate. Thus, each of the Inventive g-CPE Examples contain 85wt% chlorinated polyethylene and a total of 15 wt% combined butyl acrylate and methyl methacrylate. The grafting process followed the following general procedure:
Grafting
The ungrafted chlorinated polyethylene is first swelled in t-butyl peroctoate in the presence of the first ethylenically unsaturated monomer to be grafted and water at 25 °C for about one hour. The mixture is then heated to 85 °C for about one hour and the temperature then raised to 95 °C for about one hour. The resulting slurry is filtered and washed with water. The filtered solids are dried to yield the chlorinated polyethylene grafted with the first ethylenically unsaturated monomer. To prepare a grafted chlorinated polyethylene grafted with more than one ethylenically unsaturated monomer, the process is repeated with additional monomers.
Each of the Inventive g-CPE Examples 1-4 were then added at a level of 8 phr to
FORMOLON 622S to produce Inventive Impact Modified PVC Examples 1-4, respectively. The Inventive Impact Modified PVC Examples are tested for impact resistance by ASTM D256 and the results are shown in Table 3. Table 3
Figure imgf000009_0001
Test Methods
Test methods include the following:
Notched Izod and % Hinged are measured according to ASTM D256.
Melt index, h, is measured in accordance with ASTM D-1238 (190. degree. C; 2.16 kg).
Molecular weights and molecular weight distributions/ratios are determined as follows: A PolymerChar (Valencia, Spain) high temperature Gel Permeation Chromatography system consisting of an Infra-red concentration/composition detector (IR-5) was used for MW/MWD and composition determination. The carrier solvent was 1,2,4-trichlorobenzene (TCB). The solvent delivery pump, the on-line solvent degasser, auto-sampler, and column oven were from Agilent Technologies (Santa Clara, CA, USA). The auto-sampler and detector compartments are operated at 160°C, and the column compartment is operated at 150°C. The columns are three Mixed-B 10 um columns (Agilent Technologies). The chromatographic solvent and the sample preparation solvent contain 250 ppm of butylated hydroxytoluene (BHT) and both solvent sources are nitrogen sparged. Polyethylene samples are prepared at targeted concentrations of 2.0 mg/mL by weighing samples by a computer controlled balance, and delivering calculated amount of solvent by the auto-sampler needle. Samples are dissolved at 160°C for 1 hour with gentle agitation. The injection volume is 200 μΐ, and the flow rate is 1.0 mL/minute.
Calibration of the GPC column set is performed with 21 narrow molecular weight distribution polystyrene standards. The molecular weights of the standards ranges from 580 to 8,400,000 g/mol, and are arranged in 6 "cocktail" mixtures, with at least a decade of separation between individual molecular weights. The polystyrene standard peak molecular weights are converted to polyethylene molecular weights using the following equation:
Figure imgf000010_0001
Here B has a value of 1.0, and the experimentally determined value of A is around 0.41.
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.

Claims

We Claim:
1. A chlorinated polyethylene composition comprising a chlorinated polyethylene resin having a chlorine content of less than 30 wt% based on the total weight of the chlorinated polyethylene resin, graft polymerized with one or more ethylenically unsaturated monomer selected from the group consisting of an ethylenically unsaturated carboxylic acid ester monomer, a monovinyl aromatic monomer and mixtures thereof.
2. The chlorinated polyethylene composition according to claim 1, wherein the chlorinated polyethylene resin comprises from 5 to 45 wt% units derived from the one or more ethylenically unsaturated monomer.
3. The chlorinated polyethylene composition according to any one of the preceding claims, wherein the chlorine content of the chlorinated polyethylene resin is from 5 to 28 wt%.
4. The chlorinated polyethylene composition according to any one of the preceding claims, wherein the chlorine content of the chlorinated polyethylene resin is from 20 to 26 wt%.
5. The chlorinated polyethylene composition according to any one of the preceding claims, wherein the one or more ethylenically unsaturated monomer selected from the group consisting of an ethylenically unsaturated carboxylic acid ester monomer, a monovinyl aromatic monomer and mixtures thereof are selected from the group consisting of alkyl (meth)acrylates.
6. The chlorinated polyethylene composition according to any one of the preceding claims, wherein the one or more ethylenically unsaturated monomer selected from the group consisting of an ethylenically unsaturated carboxylic acid ester monomer, a monovinyl aromatic monomer and mixtures thereof are selected from the group consisting of butyl acrylate, methyl methacrylate, and combinations thereof.
7. The chlorinated polyethylene composition according to any one of the preceding claims, wherein the chlorinated polyethylene resin is first grafted with an alkyl acrylate and subsequently grafted with an alkyl methacrylate.
8. The chlorinated polyethylene composition according to any one of the preceding claims, wherein the chlorinated polyethylene resin is first grafted with butyl acrylate and subsequently grafted with methyl methacrylate.
9. An impact modifier comprising the chlorinated polyethylene composition according to any one of the preceding claims.
10. A polymer composition comprising a base polymer and an impact modifier according to claim 9, wherein the base polymer is selected from the group consisting of poly(vinylhalides), poly(methyl methacrylate), styrenic polymers, and combinations of two or more thereof.
11. The polymer composition according to claim 10, wherein the base polymer is selected from the group consisting of PVC, cPVC, PVDC, and combinations of two or more thereof.
12. The polymer composition according to claim 10, wherein the base polymer is selected from the group consisting of SAN, ABS, ASA, polystyrene, SMMA, SMA, and any combination of two or more thereof.
13. The polymer composition according to claim 10, wherein the base polymer is
poly(vinylchloride).
14. An article of manufacture comprising the polymer composition according to any one of claims 10 -14.
15. The article of manufacture according to claim 12 wherein the article is a vinyl siding.
16. The article of manufacture according to claim 12 wherein the article is a construction profile.
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Citations (8)

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US4767823A (en) 1984-12-05 1988-08-30 The Dow Chemical Company Halogenated ethylene polymers with improved resistance to agglomeration
EP0330272A2 (en) * 1988-02-19 1989-08-30 Avery International Corporation Thermoplastic, plasticizer-resistant film, and pressuresensitive film comprising the plasticizer-resistant film
US5338803A (en) * 1992-04-16 1994-08-16 The Dow Chemical Company Modified CPE for PVC impact modification
US5446064A (en) 1993-03-30 1995-08-29 Mitsubishi Chemical Mkv Company Thermoplastic elastomer composition
WO2008002952A2 (en) 2006-06-28 2008-01-03 Dow Global Technologies Inc. Chlorinated ethylene-based polymers and compositions and articles prepared therefrom
US7763692B2 (en) 2003-11-06 2010-07-27 Toyo Kasei Kogyo Company Limited Ultraviolet-curing resin composition, paint, ink, adhesive, sealing agent and primer
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Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3819763A (en) * 1971-10-04 1974-06-25 Showa Denko Kk Impact resistant resinous compositions containing acrylonitrile-chlorinated polyethylene-styrene resin or methyl methacrylate-chlorinated polyethylene-styrene resin and an elastomer
US4767823A (en) 1984-12-05 1988-08-30 The Dow Chemical Company Halogenated ethylene polymers with improved resistance to agglomeration
EP0330272A2 (en) * 1988-02-19 1989-08-30 Avery International Corporation Thermoplastic, plasticizer-resistant film, and pressuresensitive film comprising the plasticizer-resistant film
US5338803A (en) * 1992-04-16 1994-08-16 The Dow Chemical Company Modified CPE for PVC impact modification
US5446064A (en) 1993-03-30 1995-08-29 Mitsubishi Chemical Mkv Company Thermoplastic elastomer composition
US7763692B2 (en) 2003-11-06 2010-07-27 Toyo Kasei Kogyo Company Limited Ultraviolet-curing resin composition, paint, ink, adhesive, sealing agent and primer
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