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WO2006039462A2 - Polyolefines fonctionnalisees contenant de l'acide carboxylique alicyclique et emulsions polyeolefiniques fonctionnalisees - Google Patents

Polyolefines fonctionnalisees contenant de l'acide carboxylique alicyclique et emulsions polyeolefiniques fonctionnalisees Download PDF

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Publication number
WO2006039462A2
WO2006039462A2 PCT/US2005/035141 US2005035141W WO2006039462A2 WO 2006039462 A2 WO2006039462 A2 WO 2006039462A2 US 2005035141 W US2005035141 W US 2005035141W WO 2006039462 A2 WO2006039462 A2 WO 2006039462A2
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WIPO (PCT)
Prior art keywords
functionalized polyolefin
carboxylic acid
surfactant
functionalized
emulsion
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PCT/US2005/035141
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English (en)
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WO2006039462A3 (fr
Inventor
Daniel William Klosiewicz
Stephen Wayne Coe
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Eastman Chemical Company
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Priority claimed from US11/034,362 external-priority patent/US20060069188A1/en
Priority claimed from US11/031,727 external-priority patent/US20060069209A1/en
Priority claimed from US11/235,433 external-priority patent/US20060100356A1/en
Application filed by Eastman Chemical Company filed Critical Eastman Chemical Company
Priority to JP2007534789A priority Critical patent/JP2008514797A/ja
Priority to EP05799634A priority patent/EP1805259A2/fr
Publication of WO2006039462A2 publication Critical patent/WO2006039462A2/fr
Publication of WO2006039462A3 publication Critical patent/WO2006039462A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment

Definitions

  • the present invention relates to alicyclic carboxylic acid-containing functionalized polyolefins.
  • the present invention also relates to functionalized polyolefin emulsions comprising at least one alicyclic carboxylic acid-containing functionalized polyolefin, at least one non-ionic surfactant, at least one neutralizing base, optionally, at least one carboxylic acid co-surfactant, and water.
  • the present invention also relates to processes for producing alicyclic carboxylic acid-containing functionalized polyolefins, functional polyolefin emulsions, and to articles comprising alicyclic carboxylic acid- containing functionalized polyolefins and/or functionalized polyolefin emulsions.
  • Aqueous emulsions of various types of functionalized polyolefins have been used commercially since the late 1950s.
  • Various methods for emulsifying low molecular weight polyolefins have been described by Force, in U.S. Pat. No. 3,912,673, von Bramer et a!., "Polish Emulsion by Pressure Method," Soap and Chemical Specialties, December, 1966, and Nalley et al., U.S. Patent No. 3,655,353.
  • Emulsions of functionalized polyolefins have a variety of uses.
  • emulsions of functionalized polyolefins are used in floor and car polishes, temporary metal coatings, corrugated and paper coatings, textile softener and lubricants, fiberglass sizing, and paper calendaring lubricants and citrus fruit coatings.
  • the use of low molecular weight polyolefins in functionalized polyolefin emulsions can yield coatings having insufficient properties, such as, hardness.
  • higher graft levels can increase color bodies in the functionalized polyolefins.
  • improved emulsions of high molecular weight functionalized polyolefins in particular, emulsions of maleated polypropylene in order to improve, for example, mechanical properties and color.
  • sizing formulations for fibers especially glass fibers to produce polymer/fiber composite materials.
  • sizing formulations based on emulsions of low molecular weight maleated polypropylene, such as Epolene E-43 maleated polypropylene produced by Eastman Chemical Company have been used for a number of years to size glass fibers used to produce, for example, polypropylene/glass composite blends.
  • sizing formulations have been used in the fiber industry to maximize the fiber-polymer interaction. These sizing formulations include ingredients that collectively form an interphase between the fibers and the polymer.
  • the sizing formulation typically include a polymer, a silane, a lubricant, an antistatic agent, a functionalized polyolefin emulsion, for example, a maleated polypropylene emulsion, and other chemical ingredients.
  • the use of the low molecular weight polypropylene emulsions can cause the polypropylene/glass composite not to be strong enough to meet specifications.
  • a high molecular weight functionalized polypropylene as a coupling agent
  • emulsions of low molecular weight maleated polypropylene are effective for the sizing function, they can also interact with an aminosilane coupling agent applied with the glass fibers. This interaction can interfere with the interaction of - the higher molecular maleated polypropylene coupling agent additionally added to the polypropylene/glass composite.
  • the size coating does not suffer from the drawback described above. Since the maleated polypropylene emulsion used in the size coating is similar in character to the maleated polypropylene serving as a coupling agent, the interaction of the size coating with the aminosilane glass surface does not produce the same negative interaction as when the maleated polypropylene size has very low molecular weight. The result is that the mechanical properties of the polypropylene/glass composite can be improved in this way.
  • an alicyclic carboxylic acid-containing functionalized polyolefin comprising at least one alicyclic organic carboxylic acid and at least one functionalized polyolefin.
  • a functionalized polyolefin emulsion comprising at least one alicyclic carboxylic acid-containing functionalized polyolefin, at least one non-ionic surfactant, optionally, at least one carboxylic acid co-surfactant, at least one neutralizing base, and water.
  • a process for producing an alicyclic carboxylic acid-containing functionalized polyolefin comprising contacting a polyolefin, a functionalizing agent, at least one alicyclic carboxylic acid, and at least one initiator to produce the alicyclic carboxylic acid-containing functionalized polyolefin.
  • an article comprising the alicyclic carboxylic acid-containing functionalized polyolefin.
  • an article comprising the functionalized polyolefin emulsion.
  • a functionalized polyolefin emulsion comprising at least one functionalized polyolefin, at least one non-ionic surfactant, at least one neutralizing base, optionally, at least one carboxylic acid co-surfactant, and water; wherein the functionalized polyolefin has a grafting level ranging from about 0.5% by weight grafted functionalizing agent to about 2.5% by weight grafted functionalizing agent based on the weight of the functionalized polyolefin; and wherein the non-ionic surfactant has a HLB ranging from about 4 to about 10; and wherein the carboxylic acid co- surfactant comprises at least one linear organic carboxylic acid in an amount less than or equal to 16 parts per hundred parts of the functionalized polyolefin.
  • a functionalized polyolefin emulsion comprising at least one functionalized polyolefin, at least one non-ionic surfactant, at least one neutralizing base, optionally, at least one carboxylic acid co-surfactant, and water; wherein the functionalized polyolefin has a grafting level ranging from about 0.5% by weight grafted functionalizing agent to about 2.5% by weight grafted functionalizing agent based on the weight of the functionalized polyolefin; wherein the non-ionic surfactant has a HLB ranging from about 4 to about 10; wherein the carboxylic acid co-surfactant comprises at least one linear organic carboxylic acid and at least one alicyclic organic carboxylic acid; and wherein the total amount of the carboxylic acid co-surfactant is greater than 16 parts per hundred parts of the functionalized polyolefin.
  • a functionalized polyolefin emulsion comprising at least one functionalized polyolefin, at least one non-ionic surfactant, at least one neutralizing base, optionally, at least one carboxylic acid co-surfactant, and water; wherein the carboxylic acid co-surfactant comprises at least one alicyclic organic carboxylic acid.
  • a functional ized polyolefin emulsion comprising at least one functionalized polyolefin, at least one non-ionic surfactant, at least one neutralizing base, optionally, at least one carboxylic acid co-surfactant, and water wherein the functionalized polyolefin has a grafting level from about 0.5% by weight grafted functionalizing agent to about 2.5% by weight grafted functionalizing agent; and wherein the functionalized polyolefin emulsion has a % transmittance of at least 5%.
  • compositions comprising at least one functionalized polyolefin emulsion are provided.
  • articles comprising at least one functionalized polyolefin emulsion.
  • Embodiments of this invention provide functionalized polyolefin emulsions comprising a functionalized polyolefin having a higher molecular weight and lower grafting level that has been previously thought of as being difficult or impossible to emulsify.
  • the functionalized polyolefin emulsions of this invention exhibit at least one of the following advantages: 1 ) little residue after emulsification, 2) a small particle size thereby producing good transmittance for the diluted emulsion, 3) very fast filtration characteristics indicating minimal particles to clog filters, 4) high degree of reproducibility in the process for producing the functionalized polyolefin emulsions, 5) excellent coating characteristics, and 6) good color and color retention after heat aging.
  • Figure 1 shows the particle size distribution of Comparative Example 1.
  • Figure 2 shows the particle size distribution of Comparative Example 2.
  • Figure 3 shows the particle size distribution of Example 1.
  • Figure 4 shows the particle size distribution of Example 3.
  • Figure 5 shows the particle size distribution of Example 4.
  • Figure 6 shows the particle size distribution of Example 12.
  • Figure 7 shows the particle size distribution of Example 14.
  • Ranges may be expressed herein as from about one particular value, and/or to about another particular value. When such a range is expressed, it is to be understood that another embodiment is from the one particular value and/or to the other particular value, along, with all combinations within said range.
  • “Functional polyolefin emulsion” as used in this disclosure means that a functional polyolefin or an alicyclic carboxylic acid-containing functionalized polyolefin is used to produce the emulsion.
  • an alicyclic carboxylic acid- containing functionalized polyolefin is provided comprising at least one alicyclic carboxylic acid and a functionalized polyolefin.
  • the alicyclic organic carboxylic acid can be any known in the art that can emulsify the functionalized polyolefin to produce a stable functionalized polyolefin emulsion.
  • a stable functionalized polyolefin emulsion is one where the ingredients do not separate or the particles do not agglomerate.
  • Examples of alicyclic organic carboxylic acid include, but are not limited to, rosin acids. Hydrogenated rosin acids, such as Foral AX-E rosin acid produced by Eastman Chemical Company, are particularly well suited for this invention because of the light color and stability imparted by hydrogenation.
  • a functionalized polyolefin emulsion comprising at least one functionalized polyolefin, at least one non-ionic surfactant, at least one neutralizing base, at least one carboxylic acid co-surfactant, and water wherein the functionalized polyolefin has a grafting level ranging from about 0.5% by weight grafted functionalizing agent to about 2.5% by weight grafted functionalizing agent based on the weight of the functionalized polyolefin; wherein the non-ionic surfactant has a HLB ranging from about 4 to about 10; and wherein the carboxylic acid co-surfactant comprises at least one linear organic carboxylic acid in an amount less than or equal to 16 parts per hundred parts of the functionalized polyolefin.
  • a functionalized polyolefin emulsion comprising at least one alicyclic carboxylic acid- containing functionalized polyolefin, at least one non-ionic surfactant, at least one carboxylic acid cosurfactant, at least one neutralizing base, and water.
  • the alicyclic carboxylic acid co-surfactant can be contained in the functionalized polyolefin or added in the emulsification process.
  • the alicyclic carboxylic acid co-surfactant can be contained in the functionalized polyolefin and an additional amount of the alicyclic carboxylic acid co-surfactant can be added in the emulsification process.
  • the functionalized polyolefin can be any functionalized polyolefin that is known in the art.
  • functionalization of polyolefins refers to the addition of acid groups to the polyolefin by a functionalizing agent. Functionalization can be achieved by any method known in the art. For example, thermal oxidation and grafting are processes that can be utilized.
  • the polyolefins to be functionalized comprise at least one olefin monomer having from 2 to about 8 carbon atoms, preferably from 2 to about 6 carbon atoms.
  • examples of such polyolefins include, but are not limited to, polyethylene, polypropylene, polybutene, and polyhexene.
  • the polyolefins to be functionalized can be . homopolymers, copolymers, or terpolymers.
  • Preferred polyolefins are homopolymers and copolymers of low, medium, and high density polyethylene and homopolymers and copolymers of crystalline and amorphous polypropylenes.
  • crystalline homopolymers or copolymers of propylene More preferred are crystalline homopolymers or copolymers of propylene.
  • suitable polyolefins include, but are riot limited to, thermoplastic elastomers such as ethylene-propylene rubber (EPR) and ethylene-propylene-diene rubber (EPDM).
  • EPR ethylene-propylene rubber
  • EPDM ethylene-propylene-diene rubber
  • the functionalizing agent can be any that are known in the art.
  • the functionalizing agent can be any unsaturated monomer containing one or more carboxylic acid or acid anhydride groups that can functionalize the polyolefin.
  • suitable functionalizing agents are carboxylic acids, such as, acrylic acid and methacrylic acid, and acid anhydrides, such as, maleic anhydride.
  • Further functionalizing agents include, but are not limited to, unsaturated monocarboxylic acids, polycarboxylic acids, and cyclic acid anhydrides.
  • acids such as, maleic acid, flumaric acid, himic acid, itaconic acid , citraconic acid, mesaconic acid, acrylic acid, methacrylic acid, crotonic acid , isocrotonic acid, and acid anhydrides, such as, maleic anhydride and himic anhydride.
  • the use of maleic anhydride is preferred for the functionalization of polypropylene. Mixtures of functionalizing agents may be utilized in the present invention.
  • Polyolefins having a grafting level of about 0.5% by weight to about 2.5% by weight grafted functionalizing agent based on the weight of the functionalized polyolefin can be emulsified in this invention.
  • the grafting level can range from about 1.2% by weight to about 2% by weight grafted functionalizing agent based on the weight of the functionalized polyolefin.
  • the grafting level can range from about 0.5% by weight to about 2.5% by weight grafted maleic anhydride, preferably from about 1% by weight to about 2.5% by weight, and most preferably from 1.3% by weight to 2.0% by weight of grafted maleic anhydride based on the weight of the maleated polypropylene.
  • the graft level (% by weight grafted functionalizing agent based on the weight of the functionalized polyolefin) is calculated from the acid number.
  • Lower graft levels result in maleated polypropylene having lighter color, which can be advantageous in certain applications. In addition, lower graft levels can also minimize polymer degradation.
  • the graft distribution of the functionalized polyolefin should be with good uniformity in order to produce high quality functionalized polyolefin emulsions.
  • the functionalized polyolefin can be difficult or impossible to emulsify even though the graft level, calculated from the acid number, may indicate maleic anhydride content in the desired range.
  • the grafting level is calculated from the acid number of the functionalized polyolefin.
  • the acid number of a functionalized polyolefin is the number of mill ⁇ grams of potassium hydroxide that is required to neutralize the functional group present in 1 gram of the functionalized polyolefin where the test is designed to consume 1 millimole of potassium hydroxide for every millimole of functional group present.
  • methanolic potassium hydroxide is used so that each maleic functionality consumes only one potassium hydroxide even though maleic anhydride can form a diacid.
  • the acid number is obtained by titrating weighed samples of functionalized ⁇ polyolefin dissolved in refluxing xylene with methanolic potassium hydroxide using phenolphthalein as an indicator.
  • the acid number is distinguished from the saponification number which is measured in an aqueous system while the acid number is measured in a water-free system.
  • the functionalizing agent is hydrolyzed, and twice the amount of potassium hydroxide is needed for neutralization. Therefore, the saponification number is twice as high as the acid number.
  • the acid number of the functionalized polyolefin can range from about 4 to about 14, preferably from 6 to 12.
  • Acid numbers for maleated polypropylene can range from about 4 to about 14, preferably from 7 to 12.
  • Polymer strength is positively correlated with molecular weight; therefore, higher molecular weight functionalized polyolefins generally can have more desirable physical properties than lower molecular weight functionalized polyolefins.
  • the weight average molecular weight of the functionalized polyolefin can range from about 30,000 to about 90,000, preferably ranging from 40,000 to . 70,000 for most of the uses described previously.
  • the weight average molecular weight for maleated polypropylene can range from about 30,000 to about 90,000, preferably from 40,000 to 70,000.
  • the melt viscosity at 190 0 C of the functionalized polyolefin is that which is sufficient to obtain properties useful in the application for the functionalized polyolefin emulsion.
  • the melt viscosity at 190 0 C was measured using a Thermosel viscometer manufactured by the Brookfield Instrument Company.
  • the melt viscosity at 19O 0 C is greater than 10,000 centipoise, preferably ranging from about 20,000 centipoise to about 150,000 centipoise, and most preferably ranging from 40,000 centipoise to 100,000 centipoise.
  • the melt viscosity for maleated polypropylene can range from about 20,000 to about 150,000, preferably from 40,000 to 100,000.
  • the peak melt point measured by differential scanning calorimetry of the functionalized polyolefin is that which is sufficient to obtain properties useful in the particular application for the functionalized polyolefin emulsion.
  • the peak melt point of the functionalized polyolefin is greater than about 135 0 C, preferably greater than 15O 0 C.
  • the peak melt point for maleated polypropylene can range from about 135 0 C to about 165°C, preferably from 155 0 C to 165 0 C.
  • the amount of the functionalized polyolefin contained in the functionalized polyolefin emulsion is that which is sufficient to obtain properties useful in the particular application of the functionalized polyolefin emulsion.
  • the amount of the functionalized polyolefin can range from about 10% by weight to about 35% by weight based on the weight of the functionalized polyolefin emulsion, preferably from 20% by weight to 30% by weight.
  • the amount of maleated polypropylene can range from about 10% by weight to about 35% by weight based on the weight of the maleated polypropylene emulsion, preferably from 20% by weight to 30% by weight.
  • the functionalized polyolefin can be prod uced by any process known in the art.
  • the process can be either batch or continuous.
  • a batch process generally, all of the reactants and prod ucts are maintained in the reaction vessel for the entire batch preparation time.
  • a continuous process the ingredients are feed at a continuous rate to the process.
  • Typical processes for producing functionalized polyolefins include, but are not limited to, solid phase, solvent, or extrusion processes.
  • a solid phase process the polyolefin is heated to a temperature below the melting point of the polyolefin. Then, the functionalizing agent and initiator are added to the heated polyolefin to produce the functionalized polyolefin.
  • the polyolefin, functionalizing agent, and at least one initiator are fed to an extrusion zone where grafting takes place.
  • the extrusion zone comprises at least one extruder.
  • the functionalized polyolefins can also be characterized into two product types as a function of whether or not solvent is utilized, either as a solvent during reaction or in workup of the functionalized polyolefins.
  • solvent either as a solvent during reaction or in workup of the functionalized polyolefins.
  • the workup of the functionalized polyolefin involves dissolving the functionalized polyolefin in a solvent followed by precipitation, or washing with solvent. This treatment removes soluble components and thus varies both the 'apparent' molecular weight and acid number.
  • the maleated polypropylene is prepared by an extrusion process utilizing a polypropylene having a peak melt point greater than 135°C.
  • the polypropylene is combined in the melt with maleic anhydride that is added at a level between about 1.0 parts to about 2.5 parts per 100 parts of polypropylene, and the peroxide initiator is added at a level up to about 2.0% by weight based on weight of the polypropylene.
  • the polypropylene, maleic anhydride, and peroxide initiator are mixed in the extruder at a temperature in the range of about 160 0 C to about 250 0 C.
  • a functionalized polyolefin emulsion comprising at least one functionalized polyolefin, at least one non-ionic surfactant, at least one neutralizing base, optionally, at least one carboxylic acid co-surfactant, and water wherein the functionalized polyolefin has a grafting level ranging from about 0.5% by weight grafted functionalizing agent to about 2.5% by weight grafted functionalizing agent based on the weight of the functionalized polyolefin; wherein the non-ionic surfactant has a HLB ranging from about 4 to about 10; and wherein the carboxylic acid co-surfactant comprises at least one linear organic carboxylic acid in an amount less than or equal to 16 parts per hundred parts of the functionalized polyolefin.
  • the non-ionic surfactant used should have the proper HLB characteristics based on the graft level of the functionalized polyolefin to produce a stable functionalized polyolefin emulsion.
  • a stable functionalized polyolefin emulsion was defined previously in this disclosure.
  • the functionalized polyolefin emulsion has a transmittance greater than 5%. The method of measuring transmittance is described subsequently in the examples section of this disclosure.
  • HLB is an indicator of the relative amounts of hydrophillic and hydrophobic segments in the surfactant.
  • the percentage of hydrophillic groups in the surfactant is roughly equal to (HLB / 20) x 100 .
  • a non-ionic surfactant with a HLB equal to 10 has about 50% of its molecules consisting of polar ethylene oxide groups while a non-ionic surfactant with a HLB equal to 15 has about 75% of its structure as polar ethylene oxide units.
  • a non-ionic surfactant with a HLB value of about 11 to about 15 is typically used.
  • Functionalized polyolefins having lower grafting level and higher molecular weight are more difficult to emulsify.
  • a graft level less than or equal to about 2.5% by weight functionalizing agent based on the weight of the functionalized polyolefin, it would be expected that non-ionic surfactants having higher HLB values should be utilized, but this is surprisingly not the case as discussed subsequently and as shown in the examples in this disclosure.
  • Epolene G-3003 maleated polypropylene produced by Eastman Chemical Company with about 1.4 weight % grafted maleic anhydride based on the weight of the maleated polypropylene emulsifies well using non-ionic surfactants or mixtures of non-ionic surfactants having an average HLB value of between about 8 and about 9.
  • the optimum HLB of the non-ionic surfactant increases with the increasing graft level in order to produce the optimum functionalized polyolefin emulsion as indicated by good transmittance and filterability.
  • Good transmittance and filterability are defined in the Examples Section of this disclosure.
  • the optimum HLB for the non-ionic surfactant to emulsify Epolene G-3015 maleated polypropylene produced by Eastman Chemical Company with about 3% grafted maleic anhydride ranges from about 11 to about 14.
  • these same non-ionic surfactants fail to produce a stable functionalized polyolefin emulsion when used with Epolene G-3003 maleated polypropylene having a 1.4% grafting level.
  • the non-ionic surfactant can be any non-ionic surfactant or mixture of non-ionic surfactants known in the art having a HLB ranging from about 4 to about 10.
  • optimal functionalized polyolefin emulsions are obtained by choosing the appropriate HLB range based on the grafting level of the functionalized polyolefin.
  • the HLB value of the non-ionic surfactant can range from about 6 to about 10, and most preferably from 7 to 10.
  • non-ionic surfactants or non-ionic surfactant mixtures with a HLB value in the range of about 8 to about 9 tend to be most effective when emulsifying Epolene G-3003 maleated polypropylene.
  • the non-ionic surfactant for producing emulsions of Epolene G- 3003 maleated polypropylene (1.4 wt% maleic anhydride based on the weight of the maleated polypropylene) produced by Eastman Chemical Company is a roughly 70/30 mixture of Brij 30 and Brij 72 obtained from Uniquema Chemical Company where the calculated HLB of the blend is about 8.5.
  • Non-ionic surfactants include, but are not limited to, compounds based on ethylene oxide and alkyl phenols.
  • non-ionic surfactants include, but are not limited to, ethoxylated derivatives of Cg to C 20 synthetic linear alcohols, ethoxylated Cg to Ci 8 synthetic branched alcohols, ethoxylated alkyl phenol derivatives, mono esters of aliphatic carboxylic acids and polyethylene oxide oligomers of varying molecular weight, and similar mono- or di- esters of polyhydroxy material, such as, sorbitol-monolaurate.
  • non-ionic surfactants based on the reaction of alcohols or alkyl phenols with ethylene oxide, propylene oxide, or mixtures of the two are most preferred because of the stability of the ether linkage joining the hydrophilic and hydrophobic ends.
  • non-ionic surfactants can also be used.
  • combinations of non-ionic surfactants having high and low HLB values can be utilized to arrive at the HLB necessary to emulsify a particular functionalized polyolefin.
  • the amount of non-ionic surfactant present in the functionalized polyolefin emulsion is that which is sufficient to obtain a stable functionalized polyolefin emulsion.
  • a stable functionalized polyolefin emulsion was previously defined in this disclosure.
  • the amount of the non-ionic surfactant present in the functionalized polyolefin emulsion is that which is sufficient to obtain an acceptable emulsion as indicated by a transmittance of at least 5%.
  • the amount of non- surfactant can range from about 6 parts by weight per 100 parts by weight of functionalized polyolefin to about 25 parts by weight per 100 parts by weight of functionalized polyolefin, preferably from about 10 to about 20, and most preferably from 12 to 18.
  • the carboxylic acid co-surfactant is at least one selected from the group consisting of linear organic carboxylic acids and alicyclic organic carboxylic acids.
  • linear organic carboxylic acid means any carboxylic acid structure which contains no cyclic or multi-cyclic groups and can include branched structures with no cyclic units. While not intended to be bound by any particular theory, the carboxylic acid co-surfactant is neutralized by the neutralizing base to form an anionic surfactant species.
  • the linear organic carboxylic acid can be any known in the art that can emulsify the functionalized polyolefin to produce a stable functionalized polyolefin emulsion.
  • a stable functionalized polyolefin emulsion was previously defined in this disclosure.
  • Preferred examples of linear organic carboxylic acids include, but are not limited to, linear C-i ⁇ to Ci 8 fatty acids, such as, for example, oleic, stearic, or palmitoleic acid.
  • the amount of linear organic carboxylic acid is less than or equal to about 16 parts per 100 parts of functionalized polyolefin. Addition of an alicyclic organic carboxylic acid is not needed to obtain a stable functionalized polyolefin emulsion when the amount of the linear organic carboxylic acid is less than or equal to 16 parts per 100 parts of functionalized polyolefin.
  • the amount of linear organic carboxylic acid can range from about 2 to about 16 parts per hundred parts of functionalized polyolefin, most preferably from 8 to 12. It was surprising that the use of levels of linear organic carboxylic acid greater than 16 parts per 100 parts of functionalized polyolefin hindered emulsification and produced poorer quality emulsions as shown in the examples section.
  • emulsifying functionalized polyolefins having a grafting level ranging from about 0.5% by weight to about 2.5% by weight grafted functionalizing agent based on the weight of the functionalized polyolefin and using a linear organic carboxylic acid in an amount less than or equal to 16 parts per hundred parts of functionalized polyolefin improved emulsion properties, such as transmittance, can be obtained when at least one alicyclic organic carboxylic acid is also utilized in combination with the linear organic carboxylic acid. It is preferred to use mixtures of alicylic organic carboxylic acids with linear organic carboxylic acids when the total level of carboxylic acid co-surfactant in the emulsion is greater than 8 parts per hundred parts of functionalized polyolefin.
  • the total amount of carboxylic acid co-surfactant in the functionalized polyolefin emulsion is preferably in the range from about 8 parts to about 25 parts per hundred parts of functionalized polyolefin, most preferably, from 10 to 16.
  • the amount of the alicyclic organic carboxylic acid can range from about 1% by weight to about 99% by weight of the total amount of carboxylic acid co-surfactant, preferably from 25% by weight to 75% by weight.
  • the maximum amount of linear organic carboxylic acid should be 16 parts per hundred parts functionaiized polyolefin and the remainder of the carboxylic acid co-surfactant should be alicylic organic carboxylic acid.
  • the carboxylic acid co- surfactant is at least one alicyclic organic carboxylic acid.
  • the amount of the alicyclic organic carboxylic acid is that which is sufficient to produce a stable functionaiized polyolefin emulsion.
  • a stable functionaiized polyolefin emulsion was previously defined in this disclosure.
  • the amount of the alicyclic organic carboxylic acid can range from about 5 parts to 25 parts per hundred parts of functionaiized polyolefin, preferably from 10 parts to 16 parts.
  • the alicyclic organic carboxylic acid can be contained in the functionaiized polyolefin, added in the emulsification process, or both contained in the functionaiized polyolefin and additional alicyclic organic carboxylic acid added during the emulsification process.
  • a neutralizing base is also used. While not intended to be bound by any particular theory, it is believed that the neutralizing base neutralizes the carboxylic acid co-surfactant to form a soap which acts as an emulsifier. It is also believed that the neutralizing base neutralizes functional groups on the functionaiized polyolefin.
  • Preferred bases are organic compounds having 1 to about 10 carbon atoms, an amino group, and a hydroxyl group.
  • Preferred bases include, but are not limited to, N,N-diethylethanolamine, N,N-dimethyl ethanolamine, 2-dimethy!amino-2 ⁇ methyl-1 propanol, 2-dimethylamino-1- propanol, or combinations thereof.
  • the neutralizing base when a maleated polypropylene emulsion is dried, the neutralizing base can be volatile enough that it evaporates, which can allow the anhydride group in the maleated polypropylene to reform at higher temperatures. This behavior can be important in fiberglass sizing applications because the emulsion size can be reconverted to the
  • the amount of neutralizing base is that which is sufficient to convert a portion of the carboxylic acid co-surfactant to an anionic surfactant and to neutralize a portion of the acid groups of the functionalized polyolefin.
  • the amount of the neutralizing base in the functionalized polyolefin emulsion is not a fixed amount but depends on the total acidity of the functionalized polyolefin emulsion where the acidity is the combination of the carboxylic acid co-surfactant and the acidity of the grafted functional groups and the acidity of any emulsion additives. It is preferred that enough neutralizing base be used to neutralize about 80% to 100% of the total acidity in the functionalized polyolefin emulsion.
  • the remainder of the functionalized polyolefin emulsion is water.
  • a functionalized poiyolefin emulsion comprising at least one functionalized polyolefin or at least one alicyclic carboxylic acid-containing functionalized polyolefin, at least one non-ionic surfactant, at least one neutralizing base, optionally, at least one carboxylic acid co-surfactant, and water; wherein the functionalized polyolefin has a grafting level from about 0.5% by weight to about 2.5% by weight grafted functionalizing agent based on the weight of the functionalized polyolefin; and wherein the carboxylic acid co-surfactant comprises at least one alicyclic carboxylic acid.
  • the functionalized polyolefin and at least one neutralizing base were previously discussed in this disclosure.
  • the non-ionic surfactant was also previously discussed in this disclosure and is selected based on the graft level of the functionalized polyolefin.
  • the carboxylic acid co-surfactant is at least one alicyclic organic carboxylic acid. Alicyclic organic carboxylic acids were discussed previously in this disclosure. In another embodiment of this invention, the carboxylic acid co-surfactant is at least one linear organic carboxylic acid and at least one alicyclic organic carboxylic acid.
  • a functionalized polyolefin emulsion comprising at least one functionalized polyolefin or at least one alicyclic carboxylic acid-containing functionalized polyolefin , at least one non-ionic surfactant, at least one neutralizing base, optionally, at least one carboxylic acid co-surfactant, and water; wherein the functionalized polyolefin has a grafting level from about 0.5% by weight to about 2.5% by weight grafted functionalizing agent based on the weight of the functionalized polyolefin; and wherein the functionalized polyolefin emulsion has a % transmittance of at least 5%.
  • the functionalized polyolefin emulsion can also have good filterability. Good filterability is defined subsequently in the examples section of this disclosure.
  • the size of the emulsion particles is so fine that the functionalized polyolefin emulsion can be filtered easily to produce a very clean product for making fine coatings. Particles larger than the pores of a filter element cause the filter to become clogged, making filtration very difficult.
  • the functionalized polyolefin emulsion has good filterability if it passes the filterability test described subsequently in this disclosure.
  • the functionalized polyolefin emulsions have a transmittance value greater than 5%, preferably greater than 15%, and most preferably greater than 30%.
  • maleated polypropylene emulsions exhibit transmittance values greater than 5%, preferably greater than 10%, more preferred are maleated polypropylene emulsions with a transmittance greater than 20%, while the most desirable maleated polypropylene emulsions exhibit transmittance values greater than 30%.
  • Emulsions of maleated polypropylene can be made which exhibit transmittance values of 60% or greater, particularly if the polypropylene is maleated to a higher degree usually having a grafting level of greater than 2%.
  • Maleated polypropylene emulsions with transmittance values ranging from about 20% to about 35% or higher typically exhibit the coating and filtration behavior desired for emulsions of this type.
  • the alicylic carboxylic acid-containing functionalized polyolefin can be produced by any method known in the art.
  • a process is provided for producing an alicyclic carboxylic acid- containing functionalized polyolefin comprising contacting at least one polyolefin, at least one functionalizing agent, at least one alicyclic carboxylic acid, and at least one initiator to produce the alicyclic carboxylic acid- containing functionalized polyolefin.
  • a process for producing alicyclic carboxylic acid-containing functionalized polyolefins comprising: 1) heating at least one polyolefin and optionally, at least one alicyclic carboxylic acid, in a melting zone to produce a molten polyolefin; 2) contacting the molten polyolefin with at least one functionalizing agent and optionally, at least one alicyclic carboxylic acid, in a first mixing zone to produce a functionalizing agent/polyolefin mixture; 3) contacting the functionalizing agent/polyolefin mixture with at least one initiator and optionally, at least one alicyclic carboxylic acid in a second mixing/reaction zone to produce the alicyclic carboxylic acid-containing functionalized polyolefin.
  • the alicylic carboxylic acid can be added in either step a), step b), or step c).
  • the alicyclic carboxylic acid is rosin acid, more preferably, hydrogenated
  • a process for producing alicyclic carboxylic acid-containing maleated polypropylene comprising contacting polypropylene, maleic anhydride, at least one alicyclic carboxylic acid, and at least one initiator in an extrusion zone to produce the alicyclic carboxylic acid-containing maleated polypropylene.
  • the alicyclic carboxylic acid can be added at any time during the process.
  • the alicyclic carboxylic acid is rosin acid, more preferably, hydrogenated rosin acid.
  • a process for producing rosin acid-containing maleated polypropylene comprising: 1) heating polypropylene and optionally, at least one rosin acid, in a melting zone to produce molten polypropylene; 2) contacting the molten polypropylene with maleic anhydride and optionally, at least one rosin acid, in a first mixing zone to produce a maleic anhydride/polypropylene mixture; 3) contacting the maleic anhydride/polypropylene mixture with at least one initiator and optionally, at least one rosin acid in a second mixing/reaction zone to produce the rosin acid-containing maleated polypropylene.
  • the rosin acid can be added in either step a), step b), or step c).
  • the rosin acid is hydrogenated.
  • the functionalized polyolefin emulsion of this invention can be produced by any method known in the art.
  • the alicyclic carboxylic acid can be contained in the functionalized polyolefin, can be added in the emulsification process, or can be contained in the functionalized polyolefin and additional alicyclic carboxylic acid can be added in the emulsification process.
  • a process to produce a functionalized polyolefin emulsion comprising heating at least one functionalized polyolefin, at least one non-ionic surfactant, at least one neutralizing base, optionally, at least one carboxylic acid co-surfactant, and water to produce the functionalized polyolefin emulsion; wherein the functionalized polyolefin has a grafting level ranging from about 0.5% by weight grafted functionalizing agent to about 2.5% by weight functionalizing agent based on the weight of the functionalized polyolefin; wherein the non- ionic surfactant has a HLB ranging from about 4 to about 10; and wherein the carboxylic acid co-surfactant comprises at least one linear organic carboxylic acid in an amount less than or equal to 16 parts per hundred parts of the functionalized polyolefin.
  • a process is provided to produce a functionalized polyolefin emulsion comprising heating at least one functionalized polyolefin, at least one non-ionic surfactant, at least one neutralizing base, optionally, at least one carboxylic acid co-surfactant, and water to produce the functionalized polyolefin emulsion; wherein the functionalized polyolefin has a grafting level ranging from about 0.5% by weight grafted functionalizing agent to about 2.5% by weight functionalizing agent based on the weight of the functionalized polyolefin; wherein the non- ionic surfactant has a HLB ranging from about 4 to about 10; wherein the carboxylic acid co-surfactant comprises at least one linear organic carboxylic acid and at least one alicyclic organic carboxylic acid; and wherein the total amount of the carboxylic acid co-surfactant is in an amount greater than 16 parts per hundred parts of the functionalized polyolefin.
  • a process is provided to produce a functionalized polyolefin emulsion comprising heating at least one functionalized polyolefin, at least one non-ionic surfactant, at least one neutralizing base, optionally, at least one carboxylic acid co-surfactant, and water to produce the functionalized polyolefin emulsion, wherein the carboxylic acid co-surfactant comprises at least one alicyclic carboxylic acid.
  • a process is provided to produce a functionalized polyolefin emulsion comprising heating at least one functionalized polyolefin, at least one non-ionic surfactant, at least one neutralizing base, optionally, at least one carboxylic acid co-surfactant, and water to produce the functionalized polyolefin emulsion; wherein the functionalized polyolefin has a grafting level from about 0.5% by weight grafted functionalizing agent to about 2.5% by weight grafted functional onalizing agent based on the weight of the functionalizing polyolefin; and wherein the functionalized polyolefin emulsion has a % transmittance of at least 5%.
  • the emulsion can be produced by either a direct or indirect method.
  • a direct or batch method the functionalized polyolefin, at least one non-ionic surfactant, at least one neutralizing base, optionally, at least one carboxylic acid co-surfactant, and water are added to an emulsification vessel at the start of the batch to produce an emulsification mixture.
  • the emulsification vessel is then heated to the desired emulsification temperature under the vapor pressure of the water.
  • the temperature of the emulsification mixture is generally above the melting point of the functionalized polyolefin.
  • the temperature of the emul sification mixture can range from about 14O 0 C to about 185°C depending on the melting point of the functionalized polyolefin, prefererably from 165°C to 18O 0 C.
  • An advantage of the direct method is there is no need to ch arge materials to the emulsification vessel in separate steps while it is under pressure. In addition, it is simple process that eliminates additional steps that add cost to the production of the functionalized polyolefin emulsion.
  • the functionalized polyolefin and a portion of at least one of the other emulsion ingredients are heated above the melting point of the functionalized polyolefin, then the remaining emulsion ingredients are added in any order or combination at elevated temperatures.
  • Filterability was measured by filtering the functionalized polyolefin emulsion through a fine paint strainer, having a 48 x 64 mesh filtration area such as Product # ST-9014 sold by Paul Gardner Company, Inc. Acceptable filterability was found if the functionalized polyolefin emulsion flowed completely through the strainer within about 1-2 seconds after the amount of functionalized polyolefin emulsion (approx. 22Og) was poured into the strainer. Poor filterability was found if the functionalized polyolefin emulsion (approx. 22Og) required greater than about 10 seconds to drain through the filter, and the rate could be noted to slow as agglomerates or gels caused the porous screen to clog.
  • Transmittance of the functionalized polyolefin emulsion was measured by diluting the functionalized polyolefin emulsion to 1 % in deionized water by mixing 1 gram of functionalized polyolefin emulsion with 99 grams of deionized water to produce a diluted emulsion. The diluted .
  • emulsion was transferred into a 13 x 100 mm test tube, and the % transmittance was measured using a laboratory spectrophotometer such as a Sequoia Turner Model 340 spectrophotometer obtained from Sequoia Turner or Spectronic 21 D spectrophotometer obtained from Milton Roy operating at a wavelength of 600 nm. Samples were tested using calibration and test procedures documented in the manufacturer operating literature supplied with the instruments. These test instruments measure the amount of light of a specific wavelength which passes through the 13 mm sample path as compared to pure water with nominal 100% transmittance.
  • a laboratory spectrophotometer such as a Sequoia Turner Model 340 spectrophotometer obtained from Sequoia Turner or Spectronic 21 D spectrophotometer obtained from Milton Roy operating at a wavelength of 600 nm. Samples were tested using calibration and test procedures documented in the manufacturer operating literature supplied with the instruments. These test instruments measure the amount of light of a specific wavelength which passes through the 13 mm sample path as compared to pure water with nominal 100%
  • the functionalized polyolefin emulsion becomes more translucent in appearance and the % transmittance increases.
  • Functionalized polyolefin emulsions with % transmittance values less than about 10% tend to be very coarse emulsions which typically exhibit poorer filtration characteristics and give a rough coating suggesting the presence of gels or grit when a glass slide is coated with the emulsion and allowed to dry in an inverted position to form a thin film.
  • Recovered Emulsion Yield (%) was calculated by weighing the functionalized polyolefin emulsion produced after filtration in grams and dividing by 216 grams. 220 grams of material were added to the reactor, and 4 grams were assumed to have accumulated in the equipment and filter when transferring and filtering the functionalized polyolefin emulsion.
  • Residue was determined by removing and weighing the solids in the emulsification vessel before and after drying.
  • Emulsion Quality was determined qualitatively by considering the amount of residue, transmittance, and filterability of the functionalized polyolefin emulsion.
  • a direct or batch process was used in all the examples.
  • the maleated polypropylene, non-ionic surfactant, carboxylic acid co-surfactant, neutralizing base, water, and at least one additive were charged to an emulsification vessel to produce an emulsification mixture.
  • Maleated polypropylene was present in the charge at a concentration of about 26% to about 27% based on the weight of the emulsification mixture.
  • the non-ionic surfactant was added at levels based on the amount of maleated polypropylene charged.
  • the carboxylic acid co-surfactant was added to the emulsification vessel at a level based on the amount of maleated polypropylene used.
  • the amount of the non-ionic surfactant and carboxylic acid co-surfactant are expressed in terms of parts of ingredient per 100 parts of maleated polypropylene (phr) charged to the emulsification vessel.
  • the amounts of each ingredient are shown in the data tables.
  • the neutralizing base was dimethylamino-2-methylpropanol (DMAMP-80) used as an 80% by weight solution (20% water).
  • the remainder of the batch charge was water, and various low levels of additives for stabilizing the color and pH of the maleated polypropylene emulsion.
  • hypophosphorous acid neutralized with potassium hydroxide was added to the emulsion charge at an amount equal to 0.15% by weight hypophosphorous acid and 0.13% potassium hydroxide based on the total emulsion charge.
  • the basic emulsification formula used in these examples is shown in Table 1.
  • the water was charged first to the reactor, followed by ail the emulsification ingredients, and the maleated polypropylene was charged last.
  • a 300 ml pressure reactor from Parr Equipment Company was used for the emulsifications.
  • the reactor was sealed and heated to about 178°C while agitating at about 400 rpm.
  • the heating rate from 15O 0 C to about 178°C was controlled at a rate between 1°C - 2 0 C per minute.
  • the emulsification. mixture was typically stirred for 1 hour at 178°C before cooling at a rate of typically 2°C - 3°C per minute.
  • Emulsion properties were found to be fairly insensitive to the emulsion cooling rate. Below about 140°C, after the maleated polypropylene re-crystallized, even faster cooling rates were typically used. It is highly desirable to be able to use fast cooling rates since this decreases the batch cycle time needed to make the maleated polypropylene emulsion.
  • maleated polypropylene emulsions were prepared from Eastman Epolene G-3003 maleated polypropylene using the emulsification process previously described.
  • the amount of carboxylic acid co-surfactant was held constant at 17.8 phr level, and the same non-ionic surfactant type and level was used.
  • the non-ionic surfactant was a 68/32 mixture of Brij 30 and Brij 72 surfactants manufactured by Uniquema Chemical Company.
  • the carboxylic acid co-surfactant was only oleic acid.
  • the maleated polypropylene emulsion was very poor with a low transmittance value of 2.8%, and it filtered slowly, clogging the filter mesh before the entire batch passed through.
  • Example 1 about 40% of the oleic acid used in Comparative Ex. 1 was replaced by Eastman Foral AX-E hydrogenated rosin acid.
  • the maleated polypropylene emulsion exhibited excellent properties, minimal residue, a much higher % transmittance (30%), and very rapid filtration characteristics.
  • Example 2 about 60% of the oleic acid used in Comparative Example 1 was replaced by an equal amount of Foral AX-E rosin acid, and a maleated polypropylene emulsion similar in character to Example 1 was made, which exhibited marginally higher transmittance (33%) than the emulsion of Example 1.
  • carboxylic acid co-surfactant When higher levels of carboxylic acid co-surfactant are used in the emulsion formula, typically greater than 16 phr, there are very distinct advantages to using alicyclic type carboxylic acids, in particular Foral AX-E hydrogen ated rosin acid, to replace part of the carboxylic acid co-surfactant which is characterized by a linear molecular structure.
  • Example Comp. 1 Ex. 1 Ex. 2 Epolene G-3003 parts 100 100 100 (typical 26% by weight in emulsion)
  • Example 3 a maleated polypropylene emulsion was prepared using only oleic acid as the carboxylic acid co-surfactant, in the same manner as Comparative Example 1 , but at a lower level of 11.6 phr oleic acid.
  • the non-ionic surfactant in Example 3 was a 68/32 mixture of Brij 30 and Brij 70 surfactants obtained from Uniquema Chemical Company.
  • Example 4 a maleated polypropylene emulsion was produced in a similar manner as in Example 3 except the level of oleic acid co- surfactant was further reduced to 7.8 phr.
  • the non-ionic surfactant used in Example 4 was a 74/26 mixture of Brij 30 and Brij 72 surfactant.
  • Example 5 a similar maleated polypropylene emulsion was made as in Examples 3 and 4 except that the oleic acid level was further reduced to 6.8 phr.
  • the emulsion characteristics are listed in Table 3 and compared to the results for Comparative Example 1.
  • the first reduction in the oleic acid level in Example 3 caused a significant improvement in emulsion quality compared to Comparative Example 1, with the transmittance increasing from 2.8% to about 18%.
  • the further reduction in oleic acid level in Example 4 further improved the emulsion quality, with the transmittance of the emulsion increasing to an optimal value of about 27%.
  • Example 5 a further reduction, in oleic acid level deteriorated the quality of the emulsion compared to Example 4 because at this level of oleic acid, there was no longer sufficient carboxylic acid co-surfactant to completely emulsify the maleated polypropylene charge using the emuisification procedure described earlier, and therefore, the amount of non-emulsified residue increased.
  • the carboxylic acid co-surfactant is an essential emuisification ingredient for use in making emulsions of high molecular weight maleated polypropylene such as Epolene G-3003 maleated polypropylene produced by Eastman Chemical Company. From these Examples, it is evident that when linear organic carboxylic acid is used alone at levels greater than 16 phr, it serves to deteriorate the quality of the emulsion formed.
  • Examples 1 and 2 further illustrate that the required level of carboxylic acid co-surfactant to achieve complete emuisification of the high molecular weight maleated polypropylene can be added without negatively affecting emulsion quality if an alicyclic carboxylic acid, such as Eastman Foral AX-E hydrogenated rosin acid, is used to replace a portion of the linear organic carboxylic acid co-surfactant used in the emulsion formula.
  • an alicyclic carboxylic acid such as Eastman Foral AX-E hydrogenated rosin acid
  • Example 4 maleated polypropylene emulsions were made from Epolene G-3003 maleated polypropylene produced by Eastman Chemical Company using the same procedure as in Example 3 where 11.6 phr oleic acid were used as the carboxylic acid co-surfactant, but the non-ionic surfactant composition was varied in these two examples.
  • the non-ionic surfactant was a 68/32 mixture of Brij
  • the non-ionic surfactant was a 68/32 mixture of Brij 30 and Genapol UD-50 surfactants having a calculated HLB value of 10.4.
  • Genapol UD-50 surfactant is a product of Clariant Inc.
  • the non-ionic surfactant was a 47/53 mixture of Brij 30 and Brij 72 having a calculated HLB value of about 7.4.
  • Example 3 where the HLB value was 8.5, the emulsion quality was good due to the desirable non-ionic surfactant choice.
  • Example 6 where the HLB of the non-ionic surfactant was further reduced to 7.4, little change was noted relative to Example 3.
  • the most preferred range of HLB for the non-ionic surfactant HLB ranges from about 7 to about 10 for making emulsions of high molecular weight, maleated polypropylene when an alicylic carboxylic acid is not used.
  • Emulsion quality deteriorated when using non-ionic surfactants with HLB values greater than 10, and although not intending to be bound by theory, if the HLB of the non-ionic surfactant is not high enough, it can become insufficiently polar to cause emulsification unless the amount of carboxylic acid co-surfactant is modified to overcome this deficiency.
  • Example 4 in Comparative Example 3, in Table 4, a maleated polypropylene emulsion was made from Epolene G-3003 maleated polypropylene according to the procedure of Example 4 using the desirable low 7.8 phr level of oleic acid co-surfactant, but with a non-ionic surfactant mixture having a higher HLB of 10.7 produced by adding a 53/47 mixture of Brij 30 surfactant and Genapol UD-50 surfactant to the charge. In previous Example 4, a very good maleated polypropylene emulsion was obtained which had a transmittance value of 27%.
  • Example Comp. 2 Ex. 3 Ex. 6 Comp. 3 Ex. 4 Ex. 7 Epolene G-3003 (parts) 100 100 100 100 100 100 (typical 26 wt% in emulsion)
  • Non-Ionic Surfactant HLB 10.4 8.5 7.4 10.7 8.8 7.4 Amount (phr) 17 17 17 17 17 17 17
  • Examples 8, 9, and 10 were made according to the same procedure as Example 3 using 11.6 phr of carboxylic acid co-surfactant but with different proportions of Foral AX-E hydrogenated rosin acid and oleic acid.
  • the use of Foral AX-E rosin acid again significantly improved emulsion quality, but the effect was not as dramatic as in the previous examples.
  • the best maleated polypropylene emulsion was prepared in Example 10 using the highest proportion of Forai AX-E rosin acid in the carboxylic acid co-surfactant mix, and the preferred 8.5 HLB of the non-ionic surfactant mixture.
  • Example 11 a series of rnaleated polypropylene emulsions were made from Epolene G-3003 rnaleated polypropylene using only 9.5 phr of carboxylic acid co-surfactant.
  • carboxylic acid co-surfactant loading was reduced to this level, the maleated polypropylene emulsion of Example 11 , where oleic acid was used alone as the co- surfactant, exhibited excellent emulsion characteristics.
  • the maleated polypropylene emulsions of Examples 12 and 13 where 55% and 73% of the oleic acid was replaced by Foral AX-E hydrogenated rosin acid were nonetheless superior to the emulsion of Example 11 , exhibiting high % transmittance values of about 34%.
  • replacing part of the linear organic carboxylic acid by Foral AX-E hydrogenated rosin acid improved emulsion quality.
  • the only difference is that the quality of the maleated polypropylene emulsion made using linear organic carboxylic acid alone as the carboxylic acid co-surfactant improved substantially as the level of the linear organic carboxylic acid in the emulsion formula is reduced to an optimal level of about 8 - 12 phr.
  • Residue (grams ) 1-2 g Trace ⁇ i g ⁇ 1 g. Trace Trace ⁇ i g. Trace 2.5 g. ⁇ 1 g.
  • Comparative Examples 4 and 5 are listed in Table 6 where emulsions using high levels of carboxylic acid co-surfactant and non-ionic surfactants with high HLB values. Comparative Examples 4 and 5 were produced using direct emulsification procedures run in the same manner in a 300 ml pressure reactor from Parr Equipment Company as the other examples in this application. In Comparative Examples 4 and 5, Epolene G-3003 maleated polypropylene was added to the charge at a 21% by weight level, lower than the 26% - 27% used in all the previous examples The maleated polypropylene, non-ionic surfactant, carboxylic acid co-surfactant, and water were added to the reactor to produce an emulsification mixture.
  • the emulsification mixture was heated under pressure to 178°C followed by cooling at a rate of just below 1 0 C per minute.
  • the maleated polypropylene failed to emulsify, and the product found upon opening the reactor was a solid powdery type material with little liquid.
  • the liquid ingredients were absorbed into or encapsulated by the maleated polypropylene which solidified on cooling to form a low strength material which was ground up by the agitator.
  • the emulsion ingredients totally failed to cause the maleated polypropylene to invert during the emulsification procedure to form a stable functionalized polyolefin emulsion.
  • Example 14 was conducted using the same procedure as Comparative Examples 4 and 5 except the HLB of the non- ionic surfactant was 8.5, the carboxylic acid co-surfactant was added at a much lower 11.6 phr level, and 70% of the carboxylic acid co-surfactant charge consisted of Foral AX-E hydrogenated rosin acid with the remainder being oleic acid.
  • the composition in Example 14 of the emulsification ingredients reflect what the inventor has found to be a desired range for causing the emulsification of high molecular weight maleated polypropylene with lower grafting levels.
  • Example 14 The maleated polypropylene emulsion of Example 14 was excellent, exhibiting very fast filtration, minimal residue, and a high % transmittance of 33%. Comparative Examples 4 and 5 and Example 14 show that the logic of using high levels of carboxylic acid co- surfactant in combination with non-ionic surfactants having high HLB values is clearly flawed, and the best emulsification agents are those selected according to the teachings disclosed in this specification.
  • Example Ex. 4 Ex. 5 Ex. 14 Epolene G-3003 parts 100 100 100 (typical 26 wt% in emulsion) 21% 21% 26%
  • Figures 1-7 show the particle size distributions for Comparative Examples 1 and 2 and Examples 1 , 3, 4, 12, and 14.
  • Table 7 shows the particle size data for Comparative Examples 1 and 2 and Examples 1, 3, 4, 11, 12, and 14.
  • Particle size quality as shown in Table 7 was determined qualitatively by coating a glass slide with the emulsion and allowing it to dry in an inverted position to form a thin film.
  • a rough coating suggested the presence of gels or grit and therefore poor quality while a smooth coating suggested small particle size leading to good transmittance and therefore an excellent quality.
  • Example 15 a maleated polypropylene product was made by the procedure used to manufacture Epolene G-3003 maleated polypropylene where the reactant flows (maleic anhydride and peroxide) were increased by 15% to produce a material having a graft level nominally 15% greater than the level present in standard Epolene G-3003 maleated polypropylene manufactured by Eastman Chemical Co. and characterized by an acid number value of 10.5 mg KOH/g.
  • This maleated polypropylene made by this procedure is listed as G-3003X in Table 8.
  • maleated polypropylene emulsions were made from conventional Epolene G-3003 maleated polypropylene produced by Eastman Chemical Company having a nominal 9 mg KOH / g. acid number where the maleated polypropylene emulsion was made by a direct method with stirring at 172°C.
  • the ingredients used to emulsify the maleated polypropylene are listed in Table 8.
  • the emulsion formulations were very similar, the only difference being that Example 16 contained no hypophosphorous acid (HPA) and potassium hydroxide (KOH) .
  • Example 17 contained low levels of hypophosphorous acid and sodium metabisulfite.
  • Example 18 contained two times the amount of HPA + KOH as Example 17, and Example 19 contained three times the amount of additive as Example 17.
  • Eastman Chemical Company can be effectively emulsified according to the procedures described herein.
  • the addition of low levels of potassium hydroxide neutralized hypophosphorous acid or hypophosphorous acid alone to the emulsion formulation can serve both as a stabilizer to improve the heat aged color of the maleated polypropylene emulsion and also to improve the quality of the emulsion, increasing the transmittance of the emulsion.
  • the maleated polypropylene of Example 15 was emulsified by a direct method using the ingredients listed in Table 8. In Example 20, no hypophosphorous acid was added to the emulsion charge while in Example 21 hypophosphorous acid and KOH were added at the levels indicated. There was no significant increase in transmittance values for the maleated polypropylene emulsions of Examples 20 and 21 due to the addition of the hypophosphorous acid color stabilizer.
  • Commercial Epolene G-3003 maleated polypropylene can be emulsified well according to the procedures described herein, but increasing the maleation of the maleated product by only about 15% to 25% can improve emulsification characteristics further and make the emulsification procedure less sensitive to small changes in formulation or additional ingredients.
  • Non-ionic Surfactant 4.3% 4.3% 4.3% 4.3% 4.3% 4.3% HLB 9.0 9.0 9.0 9.0 9.5 9.5
  • Example 18 a maleated polypropylene emulsion was made from standard Eastman Epolene G-3003 maleated polypropylene using both Foral AX-E rosin acid and oleic acid as carboxylic acid co-surfactants.
  • Example 22 a similar maleated polypropylene emulsion was prepared where the unsaturated oleic acid was replaced by stearic acid. An excellent emulsion resulted with transmittance values even higher than for Example 18 using oleic acid.
  • Example 23 a maleated polypropylene emulsion was prepared in the same manner as in Example 22 but where 1/3 of the Forai AX-E rosin acid in the charge was also replaced by an equal amount of stearic acid.
  • Example 15 similar to Eastman Epolene G-3003 but having a 15% higher graft level, was emulsified using both Foral AX-E rosin acid and oleic acid as carboxylic acid co-surfactants.
  • Example 24 a similar maleated polypropylene emulsion was prepared as in Example 21 where the amount of Foral AX-E rosin acid was reduced and the oleic acid was replaced by a mixture of stearic acid and Prisorine 3501 isostearic acid obtained from Uniqema. An excellent emulsion resulted with similar properties as Example 21.
  • Example 25 a maleated polypropylene emulsion was prepared in the same manner as Example 24 except the amounts of stearic and isostearic acid were reversed so that 78% of the Ci 8 saturated fatty acid was isostearic acid. Again, an excellent emulsion resulted with similar properties as in Examples 21 and 24.
  • lsostearic acid is a branched fatty acid and non-crystallizing. It can be advantageous to use saturated fatty acids which are non-crystallizing in this invention, and it has been demonstrated that they are effective carboxylic acid co-surfactants when used at the levels and according to the limitations of this invention.
  • Non-ionic Surfactant 4.3% 4.3% 4.3% 4.3% 4.3% 4.3% HLB 9.0 9.0 9.0 9.5 9.5 9.5 9.5
  • Rosin acid-containing maleated polypropylene was produced utilizing a Berstorff ZE25mm x 63 L/D twin screw extruder.
  • the extruder had 1 chilled glycol cooled feed barrel followed in series by 12 additional barrels that were electrically heated and air cooled.
  • the barrels were numbered such that barrel number 1 was the first heated barrel unit following the cooled feed barrel; barrel number 2 was the second barrel after the feed barrel and so on.
  • Standard temperature controllers were used to control the set point temperature of the 12 heated barrels.
  • Barrels 1 through 12 were set at a flat 177 degree centigrade temperature profile.
  • a Prorate volumetric feeder was used to feed the polypropylene to the extruder.
  • other additives e.g. Foral AX rosin acid
  • a tumble blend was made ahead of time with the polypropylene pellets and the volumetric feeder was used to feed the solid mix. Care was taken to minimize vibration of the hopper to minimize segregation of the feed components.
  • the peroxide used as the initiator was 2,5- dimethyl-2,5-Di(tert-Butyl peroxy) hexane.
  • the peroxide was fed via a high pressure pump through a spring loaded injector into heated barrel number 5.
  • the rnaleic anhydride was manufactured by Huntsman Corporation and was melted from solid briquettes and injected as a molten liquid into the extruder via a heated high pressure injection pump and heated line through a spring loaded injector into heated Barrel number 3.
  • the solid feeds whether 100% polypropylene or polypropylene together with various other components (e.g. Foral AX rosin acid), were fed into the cooled feed barrel and melted in a melting zone using standard kneading blocks.
  • the screw elements used for the melting zone also acted as a dynamic melt seal to prevent the molten maleic acid being injected under pressure into barrel 3 from escaping out the feed throat.
  • the solid polypropylene feed or feed mixture (polypropylene and additives) was fed to the cooled feed barrel and conveyed forward and melted in the melting zone.
  • the resulting molten polypropylene was then conveyed to a subsequent first mixing zone where molten maleic acid was injected and mixed to produce a maleic/polypropylene mixture.
  • the maleic/polypropylene mixture was then conveyed forward to a second mixing/reaction zone where the peroxide initiator was injected and mixed with sufficient stirring for a sufficient time to allow the reaction to proceed to produce the maleated polypropylene or rosin acid-containing maleated polypropylene.
  • Total time in the extruder was on the order of 2 to 5 minutes average residence time.
  • the two mixing zones were separated by a dynamic melt seal formed by using reverse conveying and blister ring screw elements at the end of the first mixing zone.
  • the second mixing/reaction zone was similarly sealed at the end using reverse conveying and blister ring elements to prevent the maleic/polypropylene mixture from prematurely escaping the reaction zone.
  • the molten maleated polypropylene or rosin . acid-containing maleated polypropylene product was vacuum vented to remove volatiles in barrels 9 and 10 using a standard laboratory vacuum pump and dry ice trap system.
  • Vacuum was 28 inches of mercury in for both vents in Comparative Example 6, 27 inches of mercury in both barrels 9 and 10 for Inventive Example 26, 28.5 inches in both barrels 9 and 10 in Inventive Example 27, 26.5 inches of mercury on both barrels 9 and 10 in Inventive Example 28, and 25 inches of mercury in both barrels 9 and 10 in Inventive Example 29.
  • Molten maleated polypropylene or rosin acid- containing maleated polypropylene product was removed from the extruder through a standard 2 hole die heated to 205C, followed by a standard stranding water bath and strand cutter. The strand cut pellets are cylindrical in shape. In Comparative Example 6, no rosin acid or antioxidant was utilized.
  • Inventive Example 26 polypropylene pellets having a melt flow rate of 1.2 g/10 min was utilized in addition to 0.15% by weight Westin 619 antioxidant and 5% by weight Foral AX rosin acid produced by Eastman Chemical Company.
  • Inventive Example 27-29 the same amounts of Foral AX rosin acid were used, but the amounts of Westin 619 antioxidant were changed to 0.25% by weight in Inventive Example 27 and 0.3% by weight in Inventive Examples 28 and 29.
  • Table 10 summarizes the examples giving the feed composition, feed rates, and the acid number, Brookfield viscosity, and yellowness index of the maleated polypropylene or rosin acid-containing maleated polypropylene. It should be noted that the color as shown by the yellowness index of the rosin acid-containing maleated polypropylene in Examples 26-29 ranged from 19.5 to 23.8 while the color of Comparative Example 6 without the rosin acid was 50.1.
  • a direct or batch process was used in these examples to produce the maleated polypropylene emulsions.
  • the maleated polypropylene, non-ionic surfactant, neutralizing base, water, additives, and rosin acid were charged to a 300 ml Parr reactor to produce an emulsification mixture.
  • Table 11 gives the amounts charged to the reactor.
  • the amount of the non-ionic surfactant and carboxylic acid co-surfactant are expressed in terms of parts of ingredient per 100 parts of maleated polypropylene (phr) charged to the reactor.
  • the neutralizing base was dimethylamino-2-methylpropanol (DMAMP-80) used as an 80% solution (20% water).
  • the remainder of the batch charge was water, and various low levels of additives for stabil izing the color and pH of the maleated polypropylene emulsion.
  • the color additives included hypophosphorous acid and sodium metabisulfite (SMB). Potassium hydroxide (KOH) was also added.
  • Brij 30 and Brij 72 no ⁇ -ionic surfactants obtained from Uniquema Chemical Company were utilized in these experiments. The reactor was heated quickly to 140 0 C and then heated at about
  • Emulsification Time 60 60 60 60 60 60 60
  • Emulsion Yield ( g. out of 22Og start ) 213.5 214.3 214.4 215 215.9

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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  • Processes Of Treating Macromolecular Substances (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

L'invention concerne des polyoléfines fonctionnalisées contenant de l'acide carboxylique alicyclique ainsi que des émulsions polyoléfiniques fonctionnalisées. Par ailleurs, l'invention concerne des procédés de préparation de ces polyoléfines fonctionnalisées contenant de l'acide carboxylique alicyclique, et de ces émulsions polyoléfiniques fonctionnalisées.
PCT/US2005/035141 2004-09-29 2005-09-28 Polyolefines fonctionnalisees contenant de l'acide carboxylique alicyclique et emulsions polyeolefiniques fonctionnalisees WO2006039462A2 (fr)

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JP2007534789A JP2008514797A (ja) 2004-09-29 2005-09-28 脂環式カルボン酸含有官能化ポリオレフィン及び官能化ポリオレフィンエマルジョン
EP05799634A EP1805259A2 (fr) 2004-09-29 2005-09-28 Polyolefines fonctionnalisees contenant de l'acide carboxylique alicyclique et emulsions polyeolefiniques fonctionnalisees

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US61413804P 2004-09-29 2004-09-29
US61409704P 2004-09-29 2004-09-29
US61415604P 2004-09-29 2004-09-29
US61408704P 2004-09-29 2004-09-29
US60/614,156 2004-09-29
US60/614,087 2004-09-29
US60/614,097 2004-09-29
US60/614,138 2004-09-29
US11/031,920 2005-01-07
US11/034,362 US20060069188A1 (en) 2004-09-29 2005-01-07 Processes for producing functionalized polyolefin emulsions
US11/031,727 2005-01-07
US11/031,920 US20060069187A1 (en) 2004-09-29 2005-01-07 Functionalized polyolefin emulsions
US11/031,727 US20060069209A1 (en) 2004-09-29 2005-01-07 Heat stable functionalized polyolefin emulsions
US11/034,362 2005-01-07
US11/235,433 US20060100356A1 (en) 2004-09-29 2005-09-26 Alicyclic carboxylic acid-containing functionalized polyolefins and emulsions prepared therefrom
US11/235,433 2005-09-26

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Cited By (3)

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WO2007124049A3 (fr) * 2006-04-21 2008-04-24 Eastman Chem Co Dispersions d'agent poisseux à propriétés améliorées de vieillissement en milieu humide
CN111073401A (zh) * 2018-10-22 2020-04-28 陶氏环球技术有限责任公司 涂层组合物
WO2020212129A1 (fr) * 2019-04-16 2020-10-22 Sabic Global Technologies B.V. Capteur basé sur une matrice de polyoléfine et un composé de détection

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EP2207857B1 (fr) * 2007-10-26 2012-11-28 3M Innovative Properties Company Composition aqueuse de liant ou de colle
JP5924848B1 (ja) * 2015-09-30 2016-05-25 竹本油脂株式会社 強化繊維用サイジング剤の水性液、強化繊維及び繊維強化複合材料

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US4861676A (en) * 1988-08-29 1989-08-29 E. I. Du Pont De Nemours And Company Improved coextrudable adhesive and products therefrom
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007124049A3 (fr) * 2006-04-21 2008-04-24 Eastman Chem Co Dispersions d'agent poisseux à propriétés améliorées de vieillissement en milieu humide
CN111073401A (zh) * 2018-10-22 2020-04-28 陶氏环球技术有限责任公司 涂层组合物
US11401425B2 (en) 2018-10-22 2022-08-02 Dow Global Technologies Llc Coating compositions
WO2020212129A1 (fr) * 2019-04-16 2020-10-22 Sabic Global Technologies B.V. Capteur basé sur une matrice de polyoléfine et un composé de détection

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EP1799622A1 (fr) 2007-06-27
JP2008514798A (ja) 2008-05-08
JP2008514797A (ja) 2008-05-08
EP1805259A2 (fr) 2007-07-11
WO2006039462A3 (fr) 2006-06-01

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