WO1988001503A1 - Polymeric carriers for liquid additives for use in plastic polymers - Google Patents

Polymeric carriers for liquid additives for use in plastic polymers Download PDF

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Publication number
WO1988001503A1
WO1988001503A1 PCT/US1986/001753 US8601753W WO8801503A1 WO 1988001503 A1 WO1988001503 A1 WO 1988001503A1 US 8601753 W US8601753 W US 8601753W WO 8801503 A1 WO8801503 A1 WO 8801503A1
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WO
WIPO (PCT)
Prior art keywords
composition
polymer
liquid additive
functional
ionomer
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Application number
PCT/US1986/001753
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French (fr)
Inventor
Paul J. Albee, Jr.
Original Assignee
Albee Paul J Jr
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Publication date
Application filed by Albee Paul J Jr filed Critical Albee Paul J Jr
Priority to PCT/US1986/001753 priority Critical patent/WO1988001503A1/en
Publication of WO1988001503A1 publication Critical patent/WO1988001503A1/en

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00Disinfection, sterilisation or deodorisation of air
    • A61L9/015Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone
    • A61L9/04Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone using substances evaporated in the air without heating
    • A61L9/042Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone using substances evaporated in the air without heating with the help of a macromolecular compound as a carrier or diluent
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/0008Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59

Definitions

  • This invention involves polymer carrier compositions to carry liquid additives through processing steps and to cause them to be retained with improved stability in polymeric plastic compositions.
  • this invention includes the preparation of handleable concentrates of liquid additives capable of being processed into common polymeric plastic compositions.
  • This invention is particularly useful as a carrier for fragrance and flavor compositions to be blended into plastic compositions, but other additives such as liquid catalysts, deodorizers, fungicides, insecticides, germicides, and any other class of chemical compound characterized by improved performance in plastic compounds in some way may enjoy the benefits of the present invention.
  • additives such as liquid catalysts, deodorizers, fungicides, insecticides, germicides, and any other class of chemical compound characterized by improved performance in plastic compounds in some way may enjoy the benefits of the present invention.
  • all these additives will be referred to as
  • fragrance/flavors in plastic compositions, although highly desirable, has been extremely limited.
  • attempts to encapsulate the liquid fragrance/flavors within paraffin waxes, inorganic compounds and polymeric compounds in the form of spheres or micelles have enjoyed only modest success.
  • Present compositions and methods suffer from massive losses of fragrance/flavor during the processing steps including the steps added to produce a concentrate.
  • the fragrance/flavor is usually a mixture of chemical compounds having differing volatilities
  • the balance of the fragrance/flavor is upset during processing.
  • extremely inconsistent results are obtained.
  • the use of encapsulation techniques retards liquid additive loss to a degree, the very nature of the technique yields inconsistent and limited results particularly with long term stability.
  • Few of fragrance/flavors are compatible to even a slight degree in those common base polymeric compounds that have a balance of physical characteristics that allow them to be used in a wide range of in uses.
  • the liquid additive is constantly exuding out and escaping the plastic part or sheet.
  • fragrance/flavor industry offers great skill and versatility and can provide a fragrance compound to match or simulate essentially almost any odor or flavor.
  • subtle and complicated mixtures of chemicals both natural and synthetic, include a wide range of volatility characteristics.
  • Fragrance/flavor compositions also generally include a diluent which does not change the average physical characteristics of the fragrance composition but may well affect the compatability of the composition with the plastic.
  • the tolerance level for the fragrance may be as high as nine to even fifteen percent on the weight of a composition.
  • Many compositions use physical entrapment of the additive and even fine dispersion of the liquid additive but the results are inferior and inconsistent.
  • This invention involves the use of low to medium molecular weight functional polymers to develop concentrates and compounds containing liquid additives.
  • This liquid additive concentrate is later added by the plastic processor into plastics compounded for coatings, injection moldings, extrusions, foams and other polymer applications or used directly as air fresheners or like products.
  • the term "functional” is intended to be synonymous with "polar” and includes but is not limited to carboxyl groups. alpha-methyl groups, hydroxyl groups, anhydride groups, amide groups, ester groups, and the like.
  • the carboxyl, amide and ester groups are preferred.
  • the term "soluble" is intended to include mixtures of the liquid additive and the functional polymer that either form a single phase or approach forming a single phase such that the physical characteristics of the components is difficult to separate in that the viscosity and the flash point of the mixture is increased drastically. Upon microscopic examination, the "soluble" mixtures are either a single phase or are composed of extremely fine micelles.
  • the preferred solubility of the functional compound in the liquid additive is preferably at least 0.1 part compound to one part liquid additive.
  • the solubility is more preferably at least 0.2 parts and even more preferably at least 0.5 part compound to one part liquid additive. It is most preferably capable of solubility of at least one part functional compound in one part liquid additive.
  • the method of this invention includes intermixing in melt conditions the liquid additive and the functional polymer to form a "soluble" phase, which may be extremely fine micelles in a homogenous mix. It is preferred to add an additional polymeric compound or two to the carrying composition. It is preferred to add a high molecular weight polymer that is completely compatible in the base polymer. This high molecular weight polymer improves the hot strength and physical characteristic of the composition so that it can easily be processed and handled into the final application. In some situations, the choice of the base polymer or the choice of the fragrance involves high molecular weight polymers that are not compatible with the additive composition. In those situations, it is preferred to add an ionomer to the composition again in a melt condition.
  • This ionomer is characterized by compatibility with the mixture of the functional polymeric compound and the liquid additive and essentially forms a bridge of compatibility to the high molecular weight polymer and/or the base polymer.
  • the ionomer is preferably added to improve the processing in the melt condition and the high molecular weight polymer is added to improve the physical characteristics of the polymeric carrier composition at ambient conditions.
  • the functional polymeric chemical compound characterized as having high solubility in the liquid additive is preferably "soluble" in the ratio range of about one half to about two parts of the compound to one part of the liquid additive. It is more preferred that the "solubility" be at least one part in one part liquid.
  • This functional polymer characterized as having high solubility is referred to hereinafter as P1 polymer.
  • the solubility characteristics as measured on the mixture of P1 and liquid additive is determined by stirring polymer P1 in a heated flask sufficient to melt the polymer and the liquid additive while stirring.
  • the mixture After mixing for about five minutes the mixture is allowed to cool in a slab on aluminum foil in a plastic bag. The mass is observed over a period of days at ambient conditions to determine any spew, bloom or migration of the liquid out of the mass to the surface. In addition, the quality of the scent given off by the mass is compared with the original scent before it was processed into the plastic composition. Other tests include observing the physical characteristics of the mix, such as hardness and hot strength.
  • liquid additives covers essentially every type of chemical that has or will be added to base plastic compositions.
  • fragrances may be further classified as flavors, although it should be understood that only the odor is of interest and the term refers to the type of fragrance that is normally associated with an edible product.
  • the actual flavor may be compounded into the base polymer in order to obtain esthetic consumer appeal and to counter-balance any absorption of the flavor by the plastic wrapping from the food packaged inside.
  • fragrances and flavors are heavily guarded trade secrets of the highly specialized "industry. Little of the art of creating fragrances is published and each fragrance or flavor is merely given a code without disclosing the composition at any time except for FDA approval under secrecy agreements. As a result of this situation, each fragrance must be evaluated on an individual basis in order to determine the best polymer P1 for that particular fragrance. Solubility tests as described above must be generally carried out with each and every new fragrance composition.
  • Typical fragrances include leather, cedar, oak, rose, walnut, teak, balsam, dog repellent, baby powder, sandlewood, fresh sawed wood, and any number of floral scents both natural and synthetic as well as any other scent or scent blocking chemical.
  • flavor scents which may be the actual flavor used in food, natural or synthetic. They may merely synthesize the odor associated with that particular food including but not limited to chocolate, strawberry, pound cake, bread, popcorn, potatoe, coffee, lemon, orange, cocoa, vanilla, and the like. Although most of the above flavor fragrances are chosen as pleasant tactile sensations, there are also some applications where objectionable odors are desired to continuously omit from the plastic compositions. For all of these liquid additives, it is desired to be able to control the release and limit the losses during processing.
  • ELVAX 240, 260, 360, 460, and 660 are all ethylene vinyl acetate copolymers available commercially from E. I. DuPont de Nemours Company, Wilmington, Delaware.
  • the grades of ELVAX have varying amounts of vinyl acetate in the copolymer of 28%, 28%, 25%, 18%, and 12% respectively and have varying melt indexes of 43, 6, 2, 2.2 and 2.2 respectively.
  • AC-540. 580 and 5120 are all ethylene acrylic acid copolymers of low to medium molecular weight available commercially from Allied Corporation, Morris Township, New Jersey. They contain 9%, 11%, and 18% acrylic acid respectively.
  • AC-201 is a low molecular weight ionomer based on ethylene acrylic acid copolymer cross-linked with calcium and other similar compositions described inUnited States Patent No. 4,381,376 to Paul J. Albee, Jr. et al, incorporated herein by reference.
  • SURLYN is an ionomer supplied by Dupont, including SURLYN 9970.
  • NA-250 is a low density polyethylene of 250 melt index supplied commercially by U.S.I.
  • PVPK90 is a polyvinyl pyrrolidons supplied commercially by GAF Corporation.
  • G3350 is a polyethylene glycol supplied commercially by Union Carbide, Bound Brook, New Jersey.
  • ACRAWAX-C is a. amide wax (NN'- ethylenebisstearamide) supplied commercially by Glycol Chemical Company.
  • AC400 is a low molecular weight ethylene vinyl acetate copolymer supplied commercially by Allied Corporation.
  • OP Wax is a ester wax partially saponified and supplied commercially by Hoechst of Fed. Republic of Germany.
  • Wax E is an ester wax, supplied commerciallyby Hoechst.
  • PE WAX is a polyethylene wax.
  • EMA 2207 is an ethylene methacrylic acid copolymer with a 5 melt index from Gulf Oil Company.
  • PRIMACOR 5980 (P 5980) is an ethylene acrylicacid copolymer (20%) with a 300 melt index, Dow Chemical, Midland, Michigan.
  • the Polymer P1 is preferably of low molecular weight to facilitate blending with the liquid additive at relatively low temperatures and to reduce volatilization of the liquid additive during this process.
  • soluble homogenous
  • the viscosity and the flash point of the liquid additive/polymer P1 mixture is increased to a point where release of the fragrance is highly controlled.
  • the molecular weight of polymer P1 is preferably in the range of 500 to 2500.
  • Polymer P1 is preferably chosen from the group consisting of ethylene acrylic acid copolymer, ethylene vinyl acetate copolymer, ionomer, polyamide, ester wax, amide wax, montan wax, maleic anhydride grafted polyethylene, polyethylene glycol, hydroxystearamide wax, hydroxywax, carnuba wax, alphamethylstyrene, and a mixture of any two of more of these compounds.
  • polymer P1 is more preferably chosen from the group consisting of ethylene acrylic acid copolymers, ethylene methacrylic acid copolymers, ethylene vinyl acetate copolymers, low molecular weight ionomers, polyamides, ester waxes (oxidated low molecular weight polyethylene polymers), and amide waxes. Mixtures of two or more of these compounds are also effective. With the wide variety of chemical compounds found in the liquid additives and in particular in fragrances and flavors, the choice of polymer P1 will be chosen to obtain maximum solubility and physical characteristics and will vary from fragrance to fragrance.
  • the fragrance compositions are almost always trade secrets and are in any case generally complicated mixtures with a large number of minor components, it is usually necessary to determine the solubility of polymer P1 by trial and error as above.
  • the mixture of P1 and the liquid additive is too low in viscosity and the composition is too soft for easy further processing. It is a great aid to the plastics molder or extruder to receive the additives as concentrates in the same form as the bulk of the base polymeric composition to be processed, such as powder, granules or molding powder pellets. These can be easily added by weight and can be easily intermixed into the base polymer composition to attain high uniformity.
  • the polymeric carrier composition of the present invention is preferably supplied in a powder form since PVC is usually handled in that form. For that application, it is necessary the polymeric carrying composition be able to be ground into a powder, but it need not have the integrity to be extruded and chopped into pellets. For other applications such as for use in packaging base polymers, the polymeric carrying composition of the present invention must be able to be extruded and chopped into pellets.
  • the carrier composition of the present invention preferably includes blends of various additional polymers to achieve handling and physical property characteristics.
  • polymer P3 is a thermoplastic polymer or low molecular weight wax and imparts improved physical modifications to the carrier composition. Polymer P3 develops better hardness, hot strength and increased softing points to the formulation.
  • Typical polymer P3 compositions include low density polyethylene, high density polyethylene, polyethylene wax, polypropylene, polyvinyl chloride, high molecular weight ethylene vinyl acetate copolymer, ethylene acrylic acid copolymer, ethylene methacrylic acid copolymer, ionomer such as SURLYN, polymethyl methacrylate, polystyrene and other like polymers.
  • an ionomer is preferably included in the composition. It is preferred that the ionomer be compatible with the high molecular weight polymer and provide a bridge of compatibility between the polymer P1/liquid additive "phase" and the base polymer or to polymer P3.
  • polymer P2 For convenience, this ionomer is referred to as polymer P2.
  • the polymer P2 chemical compositions may be low to high molecular weight ionomer, high molecular weight ethylene acrylic acid copolymers, high molecular weight ethylene vinyl acetate copolymers and high molecular weight ethylene methacrylic acid copolymers. The ionomers are preferred.
  • the chemical composition of the polymer P2 ionomer is a copolymer of acrylic or methacrylic acid and ethylene or propylene or some other olefin. This copolymer is crosslinked with a monovalent or divalent metal or compound such as zinc, sodium, calcium, ammonium, or magnesium or the like.
  • polymer P2 modifies the melt properties of the formulation and generally acts as a compatibilizing agent into the base polymer or polymer P3.
  • the mixture of polymer P1 and the liquid additive is generally incompatible with the base polymer.
  • Polymer P2 acts a compatibilizing bridge between that mixture and the base polymer.
  • Polymer P2 improves process compatibility because of its broad melting point range and its compatibility with waxes and thermoplastics.
  • Polymer P2 not only improves processing characteristics but also increases the hardness and the strength properties of the carrier compositions at ambient conditions.
  • Polymer P2 is compatible with a wide range of base plastic polymers.
  • a typical carrier composition of the present invention contains twelve to ninety-seven percent by weight of polymer P1 and three to eighty-eight percent of polymer P2. More preferably the composition contains sixty to ninety-six percent polymer P1 and four to forty percent polymer P2. This composition is typically mixed with about twenty to forty percent by weight of the liquid additive. This composition may, in turn, be mixed and processed into base plastic polymers to obtain a level of a fraction, a few percent or a high concentration liquid additive by weight of the final molded part. This level is effective for fragrances and flavors, and smaller concentrations may be used for catalysts, fungicides and the like. For solid air freshening devices the concentration of the fragrance and odor absorbing liquid additives may be as high as in the composition itself.
  • the various relationships between the polymers are important, particularly in some fragrance formulations.
  • the liquid additive and polymer P1 must be soluble and form a uniform phase.
  • the increased viscosity and flash point of the fragrance/polymer P1 mixture protects the fragrance during processing.
  • Polymer P2 must be compatible with the fragrance/polymer P1 mixture.
  • compatible is intended to mean substantially compatible and approaching but not necessarily attaining the formation of single phase. It is sufficient that the compatibility be partial and may well leave substantial P2 polymer partially in the phase of fragrance/polymer P1 but also free to some extent to intermix only with the base polymer or with polymer P3 and the base polymer.
  • the mixture of polymer P2 and the fragrance/polymer P1 mix must be phase compatible with the base polymer or polymer P3 and the base polymer and it is preferred that the mixture of polymer P2 and the fragrance/polymer P1 combination be compatible in the end application with the base polymer. It is important that polymer P3 be compatible with the base polymer system in the end application.
  • "Compatibility" is best illustrated by microscopic examination at, for example, 400 power magnification. At that magnification, poor chemical compatibility is illustrated by large globules of liquid additive in various sizes and shapes entrained in the polymer. With satisfactory compatibility, small micelles of P1 polymer/liquid additive are evenly dispersed throughout the polymer with virtually no visible liquid phase in the compound.
  • Figure 1 illustrates poor chemical compatibility of a composition containing 25% of a fragrance liquid additive in a base polymer.
  • Figure 2 illustrates poor to limited compatibility of a base polymer containing 15% of a fragrance liquid additive.
  • figure 3 illustrates the good to excellent chemical compatibility of a composition of the present invention containing 25% of the same fragrance liquid additive used in Figures 1 and 2. It is preferred that the composition include forty to ninety-seven percent polymer P1, three to sixty percent polymer P2 and zero to fifty percent polymer P3.
  • composition include forty-five to seventy-five percent polymer P1, four to twenty percent polymer P2 and five to fifty percent polymer P3. This composition is mixed with about twenty to forty percent by weight by the total composition of a liquid fragrance additive to form a fragrance concentrate.
  • Polymer compositions are prepared in a batch melt process. All of the polymers are blended in a heated jacketed kettle at 130 to 150°C. As the polymers melt, they are mixed with a stirrer. Once the polymers are melted, the liquid additive is added. After mixing for about five minutes, the polymer is poured on aluminum foil and stored in plastic bag. Where applicable, it is preferred to melt polymer P1 first and drop in the liquid additive. When the mixture has formed a single phase or after about five minutes, the other polymers are added and again heated for about five minutes or until they become homogenous. Microscopic examination is made by placing a small quantity of the composition on a glass slide and heating the glass slide until the composition melts.
  • a second slide is placed over the polymer and pressed to form a thin film.
  • the slide may then be examined under the microscope.
  • the bulk of composition is cooled in a slab stored in a bag and observed over a period of time to determine any incompatibility of the liquid in the form of exudation. Hardness is tested as well as hot strength.
  • Thermogravimetric analysis is conducted determining the weight loss vs. time as the temperature is increased 40°C. per minute.
  • the quality of the fragrance is tested by comparing the fragrance of the composition with the fragrance in the liquid form. The intensity of the fragrance is not only analyzed but also the quality of the fragrance to determine the amount of lower end volitiles that have been lost in the processing stage.
  • compositions of the present invention illustrate compositions of the present invention as well as compositions determined to be unsuitable in quality and performance.
  • the satisfactory formulations will perform satisfactorily with many but not all fragrances.
  • solubility of fragrances varies widely with various polymer P1 compositions, thus, a composition found entirely satisfactory for a leather fragrance may be wholly unsatisfactory for a strawberry flavor. Since each liquid additive fragrance and flavor varies from supplier to supplier, the formula suitable for one leather fragrance may be unsuitable for a second leather fragrance. Solubility of polymer P1 with the liquid additive must be first determined.
  • Carrier compositions are provided in Table II and observations are provided. The numbers in each column are the weight percent of the total composition of which the component is present.

Abstract

A polymeric composition capable of carrying liquid additives such as flavors, scents, deodorizers and alike which are to be blended into base plastic polymers, the composition including a functional polar polymeric compound characterized as having high solubility in the liquid additive capable of forming a single phase or at least a homogeneous blend and an ionomer characterized by compatibility with the mixture of the functional polymer and the liquid additive and a high molecular weight polymer that is completely compatible in the base polymer, where the ionomer is compatible with the high molecular weight polymer, offering an extremely stable and durable composition which retains the liquid additive in the molded plastic under a variety of conditions.

Description

POLYMERIC CARRIERS FOR LIQUID ADDITIVES FOR USE IN
PLASTIC POLYMERS BACKGROUND OF THE INVENTION
This invention involves polymer carrier compositions to carry liquid additives through processing steps and to cause them to be retained with improved stability in polymeric plastic compositions. In particular, this invention includes the preparation of handleable concentrates of liquid additives capable of being processed into common polymeric plastic compositions.
This invention is particularly useful as a carrier for fragrance and flavor compositions to be blended into plastic compositions, but other additives such as liquid catalysts, deodorizers, fungicides, insecticides, germicides, and any other class of chemical compound characterized by improved performance in plastic compounds in some way may enjoy the benefits of the present invention. For purpose of brevity, all these additives will be referred to as
"fragrance/flavors" or as "liquid additives" throughout the balance of the specification and claims.
The use of fragrance/flavors in plastic compositions, although highly desirable, has been extremely limited. The advantage of having simulated leather having a permanent leather odor, the inclusion of a chocolate odor in packaging materials to encourage the consumer and to resist loss of odor from food, and increased performance time for solid air room deodorizers are all needs that have yet to be filled. Heretofor, attempts to encapsulate the liquid fragrance/flavors within paraffin waxes, inorganic compounds and polymeric compounds in the form of spheres or micelles have enjoyed only modest success. Present compositions and methods suffer from massive losses of fragrance/flavor during the processing steps including the steps added to produce a concentrate. Further, because the fragrance/flavor is usually a mixture of chemical compounds having differing volatilities, the balance of the fragrance/flavor is upset during processing. Depending upon the variations in handling during the processing, extremely inconsistent results are obtained. While the use of encapsulation techniques retards liquid additive loss to a degree, the very nature of the technique yields inconsistent and limited results particularly with long term stability. Few of fragrance/flavors are compatible to even a slight degree in those common base polymeric compounds that have a balance of physical characteristics that allow them to be used in a wide range of in uses. Thus, the liquid additive is constantly exuding out and escaping the plastic part or sheet.
The fragrance/flavor industry offers great skill and versatility and can provide a fragrance compound to match or simulate essentially almost any odor or flavor. However, by the very nature of the needs, subtle and complicated mixtures of chemicals, both natural and synthetic, include a wide range of volatility characteristics. Almost all fragrance compositions include a portisn of low end volatiles which if lost during the processing, will cause the scent to be unbalanced and the effect so laboriously attained will be lost. Fragrance/flavor compositions also generally include a diluent which does not change the average physical characteristics of the fragrance composition but may well affect the compatability of the composition with the plastic.
Polymeric compositions and carrier compositions for fragrance compounds and other liquid compositions are described in the following United States Patents: 3,120,670 to P.J. Amodeo, 3,505,432 to A. A. Neuwald, 3,553,296 to B. L. Gaeckel, 3,609,102 to M. L. Schlossman, 3,661,838 to F. Enomoto, 3,775,227 to G. Wilbert, 3,804,796 to P. Alexandre, 4,051,159 to M. Tsoucalas, 4,095,031 to E. J. Engle, 4,110,261 to J. W. Newland, and 4,226,944 to H. Stone. The foreign patents are Japan, Kokai 77 47,855 to T. Miyamoto, Japan, Kokai 77 99,980 to K. Ushiyama, Japan, Kokai Tokkyo Koho 80 94,945 to K. K. Kyoshin, and Ger. Offen. 2,521,265 to M. Dahm. None to these compositions and techniques satisfy the needs described above nor attain the objects listed herein below. For some plastics , the tolerance level for the fragrance may be as high as nine to even fifteen percent on the weight of a composition. Many compositions use physical entrapment of the additive and even fine dispersion of the liquid additive but the results are inferior and inconsistent.
SUMMARY OF THE INVENTION This invention involves the use of low to medium molecular weight functional polymers to develop concentrates and compounds containing liquid additives. This liquid additive concentrate is later added by the plastic processor into plastics compounded for coatings, injection moldings, extrusions, foams and other polymer applications or used directly as air fresheners or like products. The addition of a functional polymeric chemical compound that is characterized as having high solubility in the liquid additive that approaches forming a single phase thus modifying the viscosity and flash point characteristics of the mixture. The term "functional" is intended to be synonymous with "polar" and includes but is not limited to carboxyl groups. alpha-methyl groups, hydroxyl groups, anhydride groups, amide groups, ester groups, and the like. The carboxyl, amide and ester groups are preferred. The term "soluble" is intended to include mixtures of the liquid additive and the functional polymer that either form a single phase or approach forming a single phase such that the physical characteristics of the components is difficult to separate in that the viscosity and the flash point of the mixture is increased drastically. Upon microscopic examination, the "soluble" mixtures are either a single phase or are composed of extremely fine micelles. The preferred solubility of the functional compound in the liquid additive is preferably at least 0.1 part compound to one part liquid additive. The solubility is more preferably at least 0.2 parts and even more preferably at least 0.5 part compound to one part liquid additive. It is most preferably capable of solubility of at least one part functional compound in one part liquid additive. The method of this invention includes intermixing in melt conditions the liquid additive and the functional polymer to form a "soluble" phase, which may be extremely fine micelles in a homogenous mix. It is preferred to add an additional polymeric compound or two to the carrying composition. it is preferred to add a high molecular weight polymer that is completely compatible in the base polymer. This high molecular weight polymer improves the hot strength and physical characteristic of the composition so that it can easily be processed and handled into the final application. In some situations, the choice of the base polymer or the choice of the fragrance involves high molecular weight polymers that are not compatible with the additive composition. In those situations, it is preferred to add an ionomer to the composition again in a melt condition. This ionomer is characterized by compatibility with the mixture of the functional polymeric compound and the liquid additive and essentially forms a bridge of compatibility to the high molecular weight polymer and/or the base polymer. Thus, the ionomer is preferably added to improve the processing in the melt condition and the high molecular weight polymer is added to improve the physical characteristics of the polymeric carrier composition at ambient conditions.
It is an object of this invention to provide a polymeric carrier capable of introducing liquid additives into plastic compositions in a form that will have improved stability and physical characteristics of the final product.
It is further object of this invention to provide a method and a polymeric carrier which offers greatly improved release properties such that the fragrance/flavor remains essentially permanently entrained in the base polymer during processing and in the final application.
It is an additional object to provide a polymeric carrier for liquid additives that substantially reduces the loss of the liquid additive during the processing of the plastic to the final product.
It is an additional object of this invention to provide a method and a polymeric carrier that modifies the single phase containing the liquid additive by increasing its viscosity and flash point characteristics.
It is a particular object of this invention to provide a method and polymeric carrier for liquid additives that entrains extremely small micelles of a relatively high viscosity and flash point containing the liquid additive.
It is a further object of this invention to provide a liquid additive concentrate which is easily blended and is compatible with the base polymer in standard processing conditions. DESCRIPTION OF THE PREFERRED EMBODIMENTS The functional polymeric chemical compound characterized as having high solubility in the liquid additive is preferably "soluble" in the ratio range of about one half to about two parts of the compound to one part of the liquid additive. It is more preferred that the "solubility" be at least one part in one part liquid. This functional polymer characterized as having high solubility is referred to hereinafter as P1 polymer. The solubility characteristics as measured on the mixture of P1 and liquid additive is determined by stirring polymer P1 in a heated flask sufficient to melt the polymer and the liquid additive while stirring. After mixing for about five minutes the mixture is allowed to cool in a slab on aluminum foil in a plastic bag. The mass is observed over a period of days at ambient conditions to determine any spew, bloom or migration of the liquid out of the mass to the surface. In addition, the quality of the scent given off by the mass is compared with the original scent before it was processed into the plastic composition. Other tests include observing the physical characteristics of the mix, such as hardness and hot strength.
The characteristic of liquid additives covers essentially every type of chemical that has or will be added to base plastic compositions. Of particular interest is the addition of fragrances to the base polymer. The types of fragrances may be further classified as flavors, although it should be understood that only the odor is of interest and the term refers to the type of fragrance that is normally associated with an edible product. Here, the actual flavor may be compounded into the base polymer in order to obtain esthetic consumer appeal and to counter-balance any absorption of the flavor by the plastic wrapping from the food packaged inside.
The chemical compositions of the fragrances and flavors are heavily guarded trade secrets of the highly specialized "industry. Little of the art of creating fragrances is published and each fragrance or flavor is merely given a code without disclosing the composition at any time except for FDA approval under secrecy agreements. As a result of this situation, each fragrance must be evaluated on an individual basis in order to determine the best polymer P1 for that particular fragrance. Solubility tests as described above must be generally carried out with each and every new fragrance composition. Typical fragrances include leather, cedar, oak, rose, walnut, teak, balsam, dog repellent, baby powder, sandlewood, fresh sawed wood, and any number of floral scents both natural and synthetic as well as any other scent or scent blocking chemical. In addition, there are all the flavor scents which may be the actual flavor used in food, natural or synthetic. They may merely synthesize the odor associated with that particular food including but not limited to chocolate, strawberry, pound cake, bread, popcorn, potatoe, coffee, lemon, orange, cocoa, vanilla, and the like. Although most of the above flavor fragrances are chosen as pleasant tactile sensations, there are also some applications where objectionable odors are desired to continuously omit from the plastic compositions. For all of these liquid additives, it is desired to be able to control the release and limit the losses during processing.
To demonstrate the solubility characteristics with certain fragrance liquid additives the following polymers compositions are tested:
ELVAX 240, 260, 360, 460, and 660 (E-240 etc.) are all ethylene vinyl acetate copolymers available commercially from E. I. DuPont de Nemours Company, Wilmington, Delaware. The grades of ELVAX have varying amounts of vinyl acetate in the copolymer of 28%, 28%, 25%, 18%, and 12% respectively and have varying melt indexes of 43, 6, 2, 2.2 and 2.2 respectively.
AC-540. 580 and 5120 are all ethylene acrylic acid copolymers of low to medium molecular weight available commercially from Allied Corporation, Morris Township, New Jersey. They contain 9%, 11%, and 18% acrylic acid respectively.
AC-201 is a low molecular weight ionomer based on ethylene acrylic acid copolymer cross-linked with calcium and other similar compositions described inUnited States Patent No. 4,381,376 to Paul J. Albee, Jr. et al, incorporated herein by reference.
SURLYN is an ionomer supplied by Dupont, including SURLYN 9970.
NA-250 is a low density polyethylene of 250 melt index supplied commercially by U.S.I.
PVPK90 is a polyvinyl pyrrolidons supplied commercially by GAF Corporation.
G3350 is a polyethylene glycol supplied commercially by Union Carbide, Bound Brook, New Jersey. ACRAWAX-C is a. amide wax (NN'- ethylenebisstearamide) supplied commercially by Glycol Chemical Company.
AC400 is a low molecular weight ethylene vinyl acetate copolymer supplied commercially by Allied Corporation.
OP Wax is a ester wax partially saponified and supplied commercially by Hoechst of Fed. Republic of Germany.
Wax E is an ester wax, supplied commerciallyby Hoechst.
PE WAX is a polyethylene wax. EMA 2207 is an ethylene methacrylic acid copolymer with a 5 melt index from Gulf Oil Company.
PRIMACOR 5980 (P 5980) is an ethylene acrylicacid copolymer (20%) with a 300 melt index, Dow Chemical, Midland, Michigan.
Using the above solubility procedure the
Figure imgf000011_0001
Polymer P1 is preferably of low molecular weight to facilitate blending with the liquid additive at relatively low temperatures and to reduce volatilization of the liquid additive during this process. Once a single phase or homogenous ("soluble") blend is obtained, the viscosity and the flash point of the liquid additive/polymer P1 mixture is increased to a point where release of the fragrance is highly controlled. This increase in viscosity and the flash point by the inclusion of polymer P1 retains the bulk of the fragrance in the carrier composition during the compounding of this composition during latter processing of the composition into the base polymer, and the final molding or extruding of the commercial application. The molecular weight of polymer P1 is preferably in the range of 500 to 2500. Higher molecular weight polymers that are highly polar are also preferred. Polymer P1 is preferably chosen from the group consisting of ethylene acrylic acid copolymer, ethylene vinyl acetate copolymer, ionomer, polyamide, ester wax, amide wax, montan wax, maleic anhydride grafted polyethylene, polyethylene glycol, hydroxystearamide wax, hydroxywax, carnuba wax, alphamethylstyrene, and a mixture of any two of more of these compounds. In order to obtain the ultimate in compatibility and physical characteristic, polymer P1 is more preferably chosen from the group consisting of ethylene acrylic acid copolymers, ethylene methacrylic acid copolymers, ethylene vinyl acetate copolymers, low molecular weight ionomers, polyamides, ester waxes (oxidated low molecular weight polyethylene polymers), and amide waxes. Mixtures of two or more of these compounds are also effective. With the wide variety of chemical compounds found in the liquid additives and in particular in fragrances and flavors, the choice of polymer P1 will be chosen to obtain maximum solubility and physical characteristics and will vary from fragrance to fragrance. Since the fragrance compositions are almost always trade secrets and are in any case generally complicated mixtures with a large number of minor components, it is usually necessary to determine the solubility of polymer P1 by trial and error as above. For many applications, the mixture of P1 and the liquid additive is too low in viscosity and the composition is too soft for easy further processing. It is a great aid to the plastics molder or extruder to receive the additives as concentrates in the same form as the bulk of the base polymeric composition to be processed, such as powder, granules or molding powder pellets. These can be easily added by weight and can be easily intermixed into the base polymer composition to attain high uniformity. For example, for polyvinyl chloride base polymer applications, the polymeric carrier composition of the present invention is preferably supplied in a powder form since PVC is usually handled in that form. For that application, it is necessary the polymeric carrying composition be able to be ground into a powder, but it need not have the integrity to be extruded and chopped into pellets. For other applications such as for use in packaging base polymers, the polymeric carrying composition of the present invention must be able to be extruded and chopped into pellets. Thus, for most in use applications, the carrier composition of the present invention preferably includes blends of various additional polymers to achieve handling and physical property characteristics. In order to improve the physical properties and in particular to form an extrudable and pelletable carrier composition it preferably includes a polymer of high molecular weight characterized by being completely miscible in the base polymer and may be the same composition as the base polymer. This high molecular weight polymer is referred to as polymer P3. Polymer P3 is a thermoplastic polymer or low molecular weight wax and imparts improved physical modifications to the carrier composition. Polymer P3 develops better hardness, hot strength and increased softing points to the formulation. Typical polymer P3 compositions include low density polyethylene, high density polyethylene, polyethylene wax, polypropylene, polyvinyl chloride, high molecular weight ethylene vinyl acetate copolymer, ethylene acrylic acid copolymer, ethylene methacrylic acid copolymer, ionomer such as SURLYN, polymethyl methacrylate, polystyrene and other like polymers. In order to achieve satisfactory melt processing characteristics an ionomer is preferably included in the composition. It is preferred that the ionomer be compatible with the high molecular weight polymer and provide a bridge of compatibility between the polymer P1/liquid additive "phase" and the base polymer or to polymer P3. For convenience, this ionomer is referred to as polymer P2. The polymer P2 chemical compositions may be low to high molecular weight ionomer, high molecular weight ethylene acrylic acid copolymers, high molecular weight ethylene vinyl acetate copolymers and high molecular weight ethylene methacrylic acid copolymers. The ionomers are preferred. The chemical composition of the polymer P2 ionomer is a copolymer of acrylic or methacrylic acid and ethylene or propylene or some other olefin. This copolymer is crosslinked with a monovalent or divalent metal or compound such as zinc, sodium, calcium, ammonium, or magnesium or the like. The ionomer compositions are described in U.S. 3,264,272 to Richard W. Rees assigned to DuPont, incorporated herein by reference and U. S. 4,381,376 to Albee incorporated herein before. Typical commercial products are SURLYN from DuPont and AC-201 from Allied Corporation. The use of polymer P2 modifies the melt properties of the formulation and generally acts as a compatibilizing agent into the base polymer or polymer P3. The mixture of polymer P1 and the liquid additive is generally incompatible with the base polymer. Polymer P2 acts a compatibilizing bridge between that mixture and the base polymer. Polymer P2 improves process compatibility because of its broad melting point range and its compatibility with waxes and thermoplastics. Polymer P2 not only improves processing characteristics but also increases the hardness and the strength properties of the carrier compositions at ambient conditions. Polymer P2 is compatible with a wide range of base plastic polymers.
A typical carrier composition of the present invention contains twelve to ninety-seven percent by weight of polymer P1 and three to eighty-eight percent of polymer P2. More preferably the composition contains sixty to ninety-six percent polymer P1 and four to forty percent polymer P2. This composition is typically mixed with about twenty to forty percent by weight of the liquid additive. This composition may, in turn, be mixed and processed into base plastic polymers to obtain a level of a fraction, a few percent or a high concentration liquid additive by weight of the final molded part. This level is effective for fragrances and flavors, and smaller concentrations may be used for catalysts, fungicides and the like. For solid air freshening devices the concentration of the fragrance and odor absorbing liquid additives may be as high as in the composition itself.
The various relationships between the polymers are important, particularly in some fragrance formulations. The liquid additive and polymer P1 must be soluble and form a uniform phase. The increased viscosity and flash point of the fragrance/polymer P1 mixture protects the fragrance during processing. Polymer P2 must be compatible with the fragrance/polymer P1 mixture. The term "compatible" is intended to mean substantially compatible and approaching but not necessarily attaining the formation of single phase. It is sufficient that the compatibility be partial and may well leave substantial P2 polymer partially in the phase of fragrance/polymer P1 but also free to some extent to intermix only with the base polymer or with polymer P3 and the base polymer. The mixture of polymer P2 and the fragrance/polymer P1 mix must be phase compatible with the base polymer or polymer P3 and the base polymer and it is preferred that the mixture of polymer P2 and the fragrance/polymer P1 combination be compatible in the end application with the base polymer. It is important that polymer P3 be compatible with the base polymer system in the end application. "Compatibility" is best illustrated by microscopic examination at, for example, 400 power magnification. At that magnification, poor chemical compatibility is illustrated by large globules of liquid additive in various sizes and shapes entrained in the polymer. With satisfactory compatibility, small micelles of P1 polymer/liquid additive are evenly dispersed throughout the polymer with virtually no visible liquid phase in the compound.
The following is a brief description of the Figures illustrating the degrees of compatibility: All of the Figures are photomicrograph diagrams at 400X magnification of slides prepared using the procedure hereinbelow. Figure 1 illustrates poor chemical compatibility of a composition containing 25% of a fragrance liquid additive in a base polymer. Figure 2 illustrates poor to limited compatibility of a base polymer containing 15% of a fragrance liquid additive. figure 3 illustrates the good to excellent chemical compatibility of a composition of the present invention containing 25% of the same fragrance liquid additive used in Figures 1 and 2. It is preferred that the composition include forty to ninety-seven percent polymer P1, three to sixty percent polymer P2 and zero to fifty percent polymer P3. It is more preferred that composition include forty-five to seventy-five percent polymer P1, four to twenty percent polymer P2 and five to fifty percent polymer P3. This composition is mixed with about twenty to forty percent by weight by the total composition of a liquid fragrance additive to form a fragrance concentrate.
The following examples are provided to illustrate the present invention.
Polymer compositions are prepared in a batch melt process. All of the polymers are blended in a heated jacketed kettle at 130 to 150°C. As the polymers melt, they are mixed with a stirrer. Once the polymers are melted, the liquid additive is added. After mixing for about five minutes, the polymer is poured on aluminum foil and stored in plastic bag. Where applicable, it is preferred to melt polymer P1 first and drop in the liquid additive. When the mixture has formed a single phase or after about five minutes, the other polymers are added and again heated for about five minutes or until they become homogenous. Microscopic examination is made by placing a small quantity of the composition on a glass slide and heating the glass slide until the composition melts. A second slide is placed over the polymer and pressed to form a thin film. The slide may then be examined under the microscope. The bulk of composition is cooled in a slab stored in a bag and observed over a period of time to determine any incompatibility of the liquid in the form of exudation. Hardness is tested as well as hot strength. Thermogravimetric analysis is conducted determining the weight loss vs. time as the temperature is increased 40°C. per minute. The quality of the fragrance is tested by comparing the fragrance of the composition with the fragrance in the liquid form. The intensity of the fragrance is not only analyzed but also the quality of the fragrance to determine the amount of lower end volitiles that have been lost in the processing stage. The following compositions illustrate compositions of the present invention as well as compositions determined to be unsuitable in quality and performance. The satisfactory formulations will perform satisfactorily with many but not all fragrances. As referred to above, solubility of fragrances varies widely with various polymer P1 compositions, thus, a composition found entirely satisfactory for a leather fragrance may be wholly unsatisfactory for a strawberry flavor. Since each liquid additive fragrance and flavor varies from supplier to supplier, the formula suitable for one leather fragrance may be unsuitable for a second leather fragrance. Solubility of polymer P1 with the liquid additive must be first determined.
Carrier compositions are provided in Table II and observations are provided. The numbers in each column are the weight percent of the total composition of which the component is present.
Figure imgf000018_0001
Figure imgf000019_0001
Figure imgf000020_0001
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000023_0001
Figure imgf000024_0001
Figure imgf000025_0001
Code for Table II: s1. = slight, v. = very, v. s1. = very slight, exc. = excellent, def. = definite, migr. = migration, olefin = in olefin compositions, general = in general polymer compositions, foam = in foam compositions, PVC = in PVC compositions, flavor = in flavor compositions, air freshener = in air freshener compositions, LDPE = low density polyethylene polymer, HDPE - high density polyethylene wax, CAB-M-5 is aerated silica from CAB-O-Si1 series supplied by Cabot Corporation. While this invention has been described with reference to the specific embodiments disclosed herein, it is not confined to the details set forth and the patent is intended to include modifications and changes which may come within and extend from are following claims .

Claims

C L A I M S
1. A polymeric composition for carrying (melt entrainment) of liquid additives to be blended into base plastic polymers comprising:
(a) a low to medium range molecular weight functional polymer characterized by high solubility in the liquid additive.
2. The composition of claim 1, wherein the functional polymer is a copolymer having a functional monomer component.
3. The composition of claim 1, wherein the functional polymer is characterized as having a solubility in the liquid additive at a ratio of at least 0.1 part compound to 1 part of the liquid additive.
4. The composition of claim 1, wherein the functional polymer is characterized as having a solubility in the liquid additive at a ratio of at least 0.2 part compound to 1 part of the liquid additive.
5. The composition of claim 1, wherein the functional polymer is characterized as having a solubility in the liquid additive at a ratio of at least 0.5 part compound to 1 part of the liquid additive.
6. The composition of claim 1, wherein the functional polymer is characterized as having a solubility in the liquid additive at a ratio of at least 1 part compound to 1 part of the liquid additive.
7. The composition of claim 1, wherein the functional polymer has a molecular weight less than 20,000.
8. The composition of claim 1, wherein the functional polymer has a molecular weight less than 10,000.
9. The composition of claim 1, further comprising an ionomer characterized by compatibility with the mixture of the functional polymer and the liquid additive.
10. The composition of claim 9, wherein the ionomer is an acrylic acid or methacrylic acid copolymer reacted with a divalent metal.
11. The composition of claim 9, wherein the ionomer is further characterized by compatibility with the base polymer.
12. The composition of claim 9, wherein the composition comprises twelve to ninety-seven percent by weight of the functional compound, and three to eighty-eight percent by weight of the ionomer.
13. The composition of claim 9, wherein the composition comprises sixty to ninety-six percent of the functional compound, and four to forty percent by weight of the ionomer.
14. The composition of claim 1, wherein the functional polymer has functional groups chosen from groups consisting of carboxyl, hydroxyl, amide, ester, alpha-methyl, and anhydride.
15. The composition of claim 1, wherein the functional compound is chosen from the group consisting of ethylene acrylic acid copolymer, ethylene vinyl acetate copolymer, ionomer, polyamide, ester wax, amide wax, montan wax, maleic anhydride grafted polyethylene, polyethylene glycol, hydroxystearamide wax, hydroxywax, carnuba wax, alphamethylstyrene, and a mixture of any two or more of these compounds.
16. The composition of claim 1, wherein twenty to forty percent by weight of the liquid additive is blended into the composition.
17. The composition of claim 1, wherein it further comprises a high molecular weight polymer completely compatible in the base polymer and wherein the ionomer is compatible with this high molecular weight polymer.
18. A polymeric composition for carrying liquid additives to be blended into base plastic polymers comprising:
(a) a functional polymeric chemical compound characterized as having high solubility in the liquid additives, and
(b) an ionomer characterized by compatibility with the mixture of the functional compound and the liquid additive.
19. The composition of claim 18, wherein it further comprises a high molecular weight polymer completely compatible in the base polymer and wherein the ionomer is compatible with this high molecular weight polymer.
20. The composition of claim 18, wherein the functional compound is characterized as having solubility in the liquid additive of ratios of at least 0.1 part compound to 1 part of liquid additive.
21. The composition of claim 18, wherein the functional compound is characterized as having solubility in the liquid additive of ratios of at least 0.2 part compound to 1 part of liquid additive.
22. The composition of claim 18, wherein the functional compound is chosen from the group consisting of ethylene acrylic acid copolymer, ethylene vinyl acetate copolymer, ionomer, polyamide, ester wax, amide wax and a mixture of any two or more of these compounds.
23. The composition of claim 18, wherein the functional compound is chosen from the group consisting of ethylene acrylic acid copolymer, ethylene vinyl acetate copolymer, low molecular weight ionomer, amide wax, and a mixture of any two or more of these compounds.
24. The composition of claim 18, wherein the ionomer is an acrylic acid or methacrylic acid copolymer reacted with a divalent metal.
25. The composition of claim 18, wherein the ionomer is further characterized by compatibility with the base polymer.
26. The composition of claim 18, wherein twenty to forty percent by weight of the liquid additive is blended into the composition.
27. The composition of claim 18, wherein the composition comprises twelve to ninety-seven percent by weight of the functional compound, and three to eighty-eight percent by weight of the ionomer.
28. The composition of claim 18, wherein the composition comprises sixty to ninety-six percent of the functional compound, and four to forty percent by weight of the ionomer.
29. The composition of claim 19, wherein it further comprises up to fifty percent by weight of the composition of the high molecular weight polymer.
30. The composition of claim 29, wherein the composition comprises five to forty percent by weight of the total composition of the high molecular weight polymer.
31. A polymeric composition for carrying liquid additives to be blended into base plastic polymers comprising:
(a) a liquid additive that imparts useful characteristics to the base plastic polymer, but the presence of which is a limited durability when entrained in the polymer and,
(b) a functional polymeric chemical compound characterized as having high solubility in the liquid additive.
32. The composition of claim 31, wherein it further comprises an ionomer characterized by compatibility with the mixture of the functional compound and the liquid additive.
33. The composition of claim 31, wherein it further comprises a high molecular weight polymer completely compatible in the base polymer and wherein the ionomer is compatible with this high molecular weight polymer.
34. The composition of claim 31, wherein the functional compound is characterized as having solubility in the liquid additive in at least 0.1 part compound to 1 part of liquid additive.
35. The composition of claim 1, wherein the functional compound is chosen from the group consisting of ethylene acrylic acid copolymer, ethylene vinyl acetate copolymer, ionomer, polyamide, ester wax, amide wax, montan wax, maleic anhydride grafted polyethylene, polyethylene glycol, hydroxystearamide wax, hydroxywax, carnuba wax, alphamethylstyrene, and a mixture of any two or more of these compounds.
36. A method of stabilizing and containment of a liquid additive in a base plastic polymer comprising:
(a) mixing under melt condition the liquid additive into a functional polymeric chemical compound characterized as having high solubility in the liquid additive to form a single phase, and
(b) intermixing in a melt condition a high molecular weight polymer characterized as being completely compatible in the base polymer and at least partially compatible with the mixture of the liquid additive and the functional compound.
37. The method of claim 36, wherein it further comprises intermixing in a melt condition an ionomer characterized by compatibility with the mixture of the functional compound and the liquid additive.
PCT/US1986/001753 1986-08-25 1986-08-25 Polymeric carriers for liquid additives for use in plastic polymers WO1988001503A1 (en)

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WO1994006480A1 (en) * 1992-09-22 1994-03-31 Reckitt & Colman Products Limited Emanator for volatile liquids
WO2004020004A1 (en) * 2002-08-09 2004-03-11 Henkel Kommanditgesellschaft Auf Aktien Fragrance release system
WO2006023858A1 (en) * 2004-08-19 2006-03-02 The Procter & Gamble Company Volatile material-containing compositions having a consistent release profile
US7528102B2 (en) 2002-08-09 2009-05-05 Henkel Kgaa Fragrance release system
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