Classifications

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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0016—Plasticisers
• • 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
  • C08K5/10—Esters; Ether-esters
  • C08K5/101—Esters; Ether-esters of monocarboxylic acids
  • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
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  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
• • 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
  • C08K5/10—Esters; Ether-esters
  • C08K5/101—Esters; Ether-esters of monocarboxylic acids
• • 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
  • C08K5/10—Esters; Ether-esters
  • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/63—Additives non-macromolecular organic
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  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J131/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
  • C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
  • C09J131/04—Homopolymers or copolymers of vinyl acetate
• • 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
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
  • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
  • C08L31/04—Homopolymers or copolymers of vinyl acetate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
  • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09J133/08—Homopolymers or copolymers of acrylic acid esters
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
  • C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined

Definitions

• This invention is directed to a non-phthaiate monobenzoate useful as a plasticizer in a variety of polymer applications, including but not limited to p!astisols. adhesives, caulks, architectural coatings, industrial coatings, OEM coatings, paints, inks, overprint varnishes ("OPV's"), other coatings, polishes and the like,
• this invention is directed to the use of a monobenzoate ester, 3-phenyl propyl benzoate, to improve the performance properties of polymers in pSastiso! applications.
• the inventive monobenzoate has comparable or better rheology, viscosity stability, and processabilify, among other advantages, over traditional high solvating or specialty plasticizers used in plastisol applications.
• the invention is also directed to plastisol compositions comprising the inventive monobenzoate and blends of the inventive monobenzoate with other plasticizers for use in plastisol compositions.
• Plasticizers as polymer additives, have been known for more than a century. Most high volume plasticizers have been developed in the last seventy years, primarily for use with vinyl and other polymeric substances, Plasticizers are used more than any other type of polymer additives, particularly in polyvinyl chloride (PVC) applications. Hundreds of plasticizers have been produced, but only a few remain having acceptable performance properties " When combined with vinyl or other polymeric materials..
• a typical plasticizer is defined as an organic liquid that will soften a polymer and make it more workable, as long as the polymer and plasticizer are at least partially compatible.
• the function of a plasticizer in any polymer system requires compatibility, Plasticizers are used to adjust hardness (or softness) of a polymer, impart stain resistance, alter tensile properties (such as strength, elongation or flexibility) and to facilitate prooessabiiity, as required, for a mu!titude of applications, including without limitation flexible vinyl applications..
• Piasticizers also serve as a vehicle for the dispersion of resin (polymer) particles, such as PVC.
• the dispersion is initially a two-phase, heterogeneous system.
• Piasticizers promote the formation of homogeneous systems and polymer fusion occurs upon heating. The higher the solvating power, the lower the temperature at which a homogeneous system is fused, which, in turn, decreases the residence time and increases the speed at which polymeric compositions can be processed into an end product, resulting in a faster, more efficient and economical process.
• Piasticizers are available in a wide variety of alternative chemistries and include: 1) general purpose, 2 ⁇ specialty types and 3) secondary and diluent types, more fully described herein. Piasticizers are also distinguished based on their ability to solvate dispersed solid polymers and/or their gelation and fusion temperatures in plastiso!s. Gelation and fusion temperatures dictate the speed of production and are influenced by the solvating power of the plasticizer. By way of example only, the gelation and fusion temperatures- of a piastisoi containing a diberizoate plasticizer will be lower than a piastisoi containing a general purpose phthalate, thus enabling speed of processing in that particular application.
• General purpose piasticizers provide an excellent compromise between performance characteristics and economy for most applications.
• Some examples include: bis (2-ethyihexyl phthalate) (DEHP or DOP), diisononyl phthalate (DINP), dioctyl phthalate (DnQP), diisodecyl phthalate (DIDP), dip ropy! heptyl phthalate (DPHP), di-2-ethyihexyl terephthalate (DOTP or DEHT), and d.iisononyl-1 , 2 cycSohexane d!carboxySate (DIDC, BASF's HexamoilTM, or PINCH ⁇ ).
• Specialty type plasticizers were developed, in past, to fulfil! the need for high solvators, the most popular being lower molecular weight phthalates.
• An example of such a plasticizer is butyl benzyl phthalate (BBP), which is often employed as a high solvating .plasticizer.
• BBP butyl benzyl phthalate
• DPF di-n-buty! phthalate
• DSBP diisobutyl phthalate
• non-phthalate, high solvating plasticizers include dibenzoate esters, some citric acid esters, a!ky! sulfonic acid esters, and certain phosphates.
• Dibutyl terephtha!ate (DBTP) and N ⁇ a!kyS pyrrolidines have also been proposed as a specialty type, high soivator plasticizers.
• Some high solvating plasticizers are limited in their usefulness due to high viscosity or poor rheology characteristics.
• An ideal plasticizer possesses a good balance between solvation and rheology characteristics.
• Benzoate plasticizers include dibenzoates and rnonobenzoat.es, such as dieihy!ene glycol dibenzoate (DEGDB) and dipropylene glycol dibenzoate (DPGDB) esters thai have been used in a wide variety of polymer applications, including in the vinyl industry.
• DEGDB dieihy!ene glycol dibenzoate
• DPGDB dipropylene glycol dibenzoate
• This triblend comprising DEGDB, DPGDB and 1 , 2 propylene glycol dibenzoate (PGDB) in various ratios and sold as K-FLEX* 975P, has been found to be very versatile for a variety of applications, based on its broad range of compatibilities with polymers utilized in the coatings industry (for example, in vinyl acrylic, acrylic and styrene acrylic types) and possesses good solvating properties and low volatility. Its performance properties compare favorably to traditional high solvating phthaiate plasticizers as well as traditional benzoate ester plasticizers.
• Monobenzoate -eaters known to be useful as plasticizers include: isodecyi benzoate, isononyl benzoate, and 2 ⁇ ethylhexyS benzoate.
• isodecyi benzoate has been described as useful coalescent agent for paint compositions and for use in the preparation of plastisols in U.S. Patent No, 5,236,987 to Arendt
• isodecyi benzoate has also been described in U,S, Patent No. 7,629,413 to Godwin et ai. as a useful secondary plasticizer in combination with phthaiate plasticizers to provide lower viscosity and lower volatility in PVC plastisols.
• Half ester monobenzoates include cf (propylene glycol monobenzoate and diethylene glycol monobenzoate, which are byproducts of the production of dibenzoates, but which, most of the time, are not objects of production.
• Half esters are not known for being high solvators, although they may be used in conjunction therewith.
• Half esters are also not as useful as dibenzoate plasticizers, because they are less compatible than the corresponding dibenzoate with PVC, However, the half esters are compatible with emulsions polymers, such as acryli and/or vinyl ester polymers.
• Examples of secondary and diluent type plasticizers used primarily to reduce plastisol viscosity, include those based on castor oil and soybean oil. Isodecyi benzoate, a monobenzoate, is also a useful diluent type plasticizer,
• the monobenzoate, 3-PPB has been used in the past in flavoring and fragrance applications, but not in polymeric applications of the type discussed herein. It continues to be used in flavoring and fragrance applications. It has also been used as a solubiiizer for certain active or functional organic compounds in personal care products, such as topical sunscreens, as described in U.S. Patent Publication 2005/0152858.
• inventive plasticizer in plastisol compositions
• inventive monobenzoate include a variety of coatings, including without limitation overprint varnishes, polishes, inks, paints, adhesives, sealants, and caulk, which are the subject of co-pending applications.
• plasticizer having excellent compatibility with a wide variety of polymers and lower VOC content than traditional diluent type plasticizers used to control plastisol viscosities, for use alone or in blends with other plasticizers, in piastisols and other polymeric applications where plasticizers are traditionally required.
• Still a further object of the invention is to provide piasticizer blends comprising the inventive monobenzoate of the invention.
• Yet another object of the invention is to provide a plastiso! formulation utilizing a non-phtha!ate piasticizer, 3-PPB, which allows faster processing and economic efficiencies to be achieved and provides comparable or better tensile strength properties over traditional diluent type plasticizers.
• This invention is directed to the use of a non-phfha!ate monobenzoate ester useful as a piasticizer for polymeric dispersions, such as p!astisols.
• the inventive monobenzoate comprises 3-pbe.nyl propyl benzoate (3-PPB), a component not previously known or used as a piasticizer for plastiso! compositions.
• the invention is piasticizer comprising 3-PPB useful to provide improved solvation and rbeology in polymeric applications such as p!astisols, melt compounding, injection molding, extrusion and calendaring, among others..
• the invention in a second embodiment, is a piastisol composition
• the invention is a piastisol composition
• the. inventive monobenzoate piasticizer including but not limited to PVC and acrylics.
• the invention is a blend of 3-PPB with traditional plasticizers.
• the invention is a blend of 3-PPB with solid plasticizers.
• the invention relates to the use of the inventive plasticizer in compositions used in applications such as resilient flooring, toys, gloves, wall covering, leather, textiles and the like,
• FIG. 1 shows initial viscosity data obtained for the inventive monobenzoate as compared to a dibenzoate triblend and a general purpose phthalate plasticizer, DINP.
• FIG, 2 shows the gel/fusion curves for the inventive monobenzoate, a dibenzoate triblend and a general purpose phthalate plasticizer, DINP.
• FIG. 3 shows thermogravimetric data for neat plasticizers, including the inventive monobenzoate, DINP, IDS and Eastman's TXIBTM.
• FIG, 4 reflects volatility data from the AST D-1203 Extended Test at 70°C for the inventive monobenzoate, DINP, and IDB.
• FIG, 5 reflects initial, one-day and 7-day viscosities obtained using Brookfield RVT Viscosity, 20 RPM, 23°C for the inventive monobenzoate, DINP and IDB.
• FIG. 6 (a) shows rheology data: 1 day scan obtained for a basic plastisol composition comprising the inventive monobenzoate as compared to a dibenzoate triblend (X20, K-FLEX® 975P), BBP, DOTP, DINP and !DB.
• FIG. 6 (b) shows gel fusion curves for a basic plastisol composition comprising the inventive monobenzoate as compared to a dibenzoate triblend (X20, K ⁇ FLEX®.975P), BBP, DOTP, DINP and IDB.
• FIGS. 7 (a), (b) and (c) reflect tensile strength, modulus, and elongation values, respectively, for a plastisol comprising the inventive monobenzoate as compared to DINP and JDB.
• FIG. 8 shows Rrookfie!d viscosities obtained for various plastisol formulations at initial, 1 day, 3 day and 7 day as compared to a control formulation comprising 50 phr D!NP,
• FIG. 9 shows ge!/fusion curves for various plastisol formulations as compared to a control formulation comprising 50 phr D!NP,
• FIG. 10 shows Initial Shear data for various plastisol formulations as compared to a control formulation comprising 50 phr DINP,
• FIG, 11 shows data from the Brabender heat rise experiment for the inve tive m o n o b en z o ate.
• FIG. 12 shows heat rise experiment data comparing the inventive monobenzoat to DINP.
• the present invention is directed to a monobenzoate piasticizer useful for a variety of applications as a primary or secondary piasticizer, including but not limited to plastisols.
• the benz crystal piasticizer comprises a unique monobenzoate, 3-phenyl propyl benztate (3-PPB), not previously known or used as a piasticizer in polymeric applications.
• Th preferred embodiment of the invention is 3-PPB in combination with a polymeric dispersion.
• the present invention is not restricted to any particular polymer, although the invention may be described in terms of vinyl polymers.
• the inventive monobenzoate piasticizer can generally be utilized as a primary piasticizer or a secondary piasticizer in blends with other piasticizers with numerous polymeric dispersions, often as a substitute or alternative for conventional diluent piasticizers having a higher VOC content or piasticizers that do not provide advantageous solvation and rheology.
• Any of the known polymers that can be formulated into a plastisol, melt compound, injection molding, extrusion, or calendaring polymer can be used in combinatio with novel monobenzoate to prepare a low VOC content composition in accordance with the present invention.
• the plasticizer of the present invention can generally be utilized with numerous thermoplastic, thermoset, or elastomeric polymers often as an alternative for conventional plasticizers.
• the inventive monobenzoate may be used to prepare a reduced viscosity PVC, PVC copolymer or acrylic-based plastisol in accordance with the present invention.
• Acrylic polymer compositions for various applications may also be used with the inventive monobenzoate and include various po!yalkyl methacryiaies, such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyi methacrylate, or ally! methacrylate; or various aromatic methacryiaies, such as benzyl methacrylate; or various alky! acrylates, such as methyl acrylate, ethyl acrylate, butyl acrylate, or 2 - ethylhexyi acrylate; or various acrylic acids, such as methacry!ic acid and styrenated acrylics.
• various po!yalkyl methacryiaies such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyi methacrylate, or ally! methacrylate
• inventive monobenzoate may be useful in other polymeric compositions, including but not limited to various vinyl polymers comprising polyvinyl chloride and copolymers thereof, vinyl acetate, viny!idene chloride, diethyl fumarate, diethyl maleate, or polyvinyl butyra!; various poiyurethanes and copolymers thereof; various polysuifides; cellulose nitrate; poiyvinyi acetate and copolymers thereof; and various polyaerylaies and copolymers thereof.
• various vinyl polymers comprising polyvinyl chloride and copolymers thereof, vinyl acetate, viny!idene chloride, diethyl fumarate, diethyl maleate, or polyvinyl butyra!
• various poiyurethanes and copolymers thereof various polysuifides
• cellulose nitrate poiyvinyi acetate and copolymers thereof
• plastisol means a liquid polymer composition comprising a particulate form of at least one non-crosslinked organic polymer dispersed in a liquid phase comprising a plasticizer for the polymer.
• plastisoi also means and includes an "organosol” that is a plastisol in which solvents, such as liquid hydrocarbons, ketones, or other organic liquids, are used in amounts greater than about 5 wt% to control viscosity and other properties of a plastisol,
• high soSvator or ''high, solvating is a term that describes the plasticizer's efficiency in penetrating, thickening, and gelling solid plastisol before full physical properties are developed. All the plasticizer is absorbed into the PVG of a plastisol at lower temperatures than general purpose plasticizers, thus facilitating a faster formation of a homogenous phase.
• novel monobenzoate of the present invention may be used as a low VOC substitute for other diluent plasticizers, such as isodecyl benzoate, o as an alternative plasticizer for various traditional polymer dispersions, including without limitation vinyl applications.
• plasticizers such as isodecyl benzoate
• the total amount of the inventive monobenzoate used in any particular polymeric dispersion would range broadly depending on the particular polymer, the characteristics of the polymer and other components, the process, the application or use and th results desired.
• the total, amount of the inventive monobenzoate would range broadly depending on the application, generally from about 1 to about 300, desirably from about TO to about 100, and preferably from about 20 to about 80 parts by weight for every 100 total parts by weight of the one or more thermoplastic, thermoset, o elastomeric polymers, including without limitation those identified above.
• a particularly preferred embodiment for a plastisol from about 5 to about 20 parts by weight for every 100 total parts by weight of the plasticizer, resulting in a total plasticizer content ranging from 30 to 120 phr.
• the inventive monobenzoate may be, but is not required to be, blended with various other conventional plasticizers to enhance or augment properties of polymeric compositions, including but not limited to improving compatibility and processability in a plastisol and enhancing solvating power
• Conventional plasticizers have been described herein and include, but are not limited to, various phthalate esters, phosphate esters, adipate, azelate, oleate, succinate and sehacate compounds, citrates, trimellitates, terephthalate esters such as DOTP, 1 ,2-cyc!ohexane dicarboxylate esters, epoxy plasticizers, fatty acid esters, glycol derivatives, sulfonamides, sulfonic acid esters, benzoates, bioplasticizers, such as PG disoyate and PG monosoyate, chloroparaifins, polyesters, and various other hydrocarbons and hydrocarbon derivatives that are often utilized as secondary plasticizers, such as
• Monobenzoates such as isononyl benzoate, isodecyl benzoate, and 2- ethylhexyl benzoate, as well as 2,2,4-thmethyi ⁇ 3-penianecisoi diisob.utyrate (TXiBTM, an Eastman trademark) can also be blended with the inventive monobenzoate, or the 3- PPB can replace any of these with the advantage that less is needed to achieve solvation and maintain processable viscosity and rheology.
• TXiBTM 2,2,4-thmethyi ⁇ 3-penianecisoi diisob.utyrate
• inventive monobenzoate may also be biended with solid plasticizers such as sucrose benzoate, dicyclohexyi phthalafe, triphenyj phosphate, glycerol tribenzoate, 1 ,4-cyc!ohexane dimethano! (CHD ) dibenzoate, pentaerythhtol tetrabenzoate, and alky I glycol esters.
• solid plasticizers such as sucrose benzoate, dicyclohexyi phthalafe, triphenyj phosphate, glycerol tribenzoate, 1 ,4-cyc!ohexane dimethano! (CHD ) dibenzoate, pentaerythhtol tetrabenzoate, and alky I glycol esters.
• inventive monobenzoate may also be combined with or include various amounts of conventional additives such as oils, diluents, antioxidants, surfactants, heat stabilizers, flame retardants, surfactants, blending resins, waxes, solvents and the like, depending on the particular application or polymeric dispersion.
• additives such as oils, diluents, antioxidants, surfactants, heat stabilizers, flame retardants, surfactants, blending resins, waxes, solvents and the like, depending on the particular application or polymeric dispersion.
• Additives amounts can generally vary widely and often range from about 0.1 to about 75 parts by weight for every 100 parts by weight of the plasiisol composition.
• a plastisol is a liquid dispersion of PVC ⁇ or other polymer) in plasticizer, which may be heated as a spread coating, fused in slush molding, dip molding or rotationalfy molded.
• the plastisols of the invention may be compounded by simple mixing or blending, followed by de-aerating in most instances.
• Melt compounding is a process that uses heat and pressure while mixing to fuse vinyl (or other polymer). Its overall purpose is to combine the polymer and plasticizer into a homogeneous material which can be formed through a calendar, extruder or injection mold.
• Exemplary formulations for simple basic starting plastisols and melt compounds are set forth in the examples; however, the invention is not limited to these formulations.
• the inventive monobenzoate provides a lower VOC content alternative over secondary and diluent type pSasticizers and, depending on the application, provides comparable or better compatibility, viscosity stability, and rheology, among other advantages, in many instances, the inventive monobenzoate outperforms industry standard plasticizers, including traditional and newer dibenzoate blends.
• Man traditional plasticizers have either high solvating propertie or low viscosity, but not both.
• the inventive monobenzoate strikes a good balance: between high solvating power, better rheology and lower viscosity even when used alone.
• the plastisols were prepared in a Hobart Modei N-50 mixer. A ten minute mix at speed one (1) was used. A high speed disperser was also used to prepare other plastisols evaluated employing a ten minute mix at 1000 PI s, All of the plastisols were degassed at 1 mmHg until as completely air free as possible.
• Viscosity and Rheology Low shear Viscosity measurements were made using a Brookfieid RVT at 20 RPI s for 10 revolutions at 23 ⁇ 2°C. ASTM D1823. High shear -- TA AR2000ex used, Parallel plates were set at appropriate gap (350 microns). Shear to 1000 sec-1. Viscosity Response: Both the initial and 24 hour viscosities were measured.
• inventive monobenzoate was compared to X-20 (K-FLEX ® 975P, a new dibenzoate triblend comprising 20 wt. % 1 , 2 ⁇ propylene glycol dibenzoate and 80 wt % of an 80/20 DEG/DPG dibenzoate blend) and DI ' P.
• Figure 1 shows initial viscosity data obtained for the inventive monobenzoate, which compares favorably to a genera!
• Table 1 reflects gel fusion values obtained for 3-PPB, X-20, and DINP (a general purpose phihaSate p!asiicizer).
• Figure 2 shows the gel/fusion curves for 3-PPB, X20, and DINP.
• 3-PPB is a viable alternative for use in plastisol compositions and is an acceptable partial substitute for general purpose phthalates traditionally used in this type of application.
• 3-PPB has low viscosity, better rheology, and higher solvating properties when used in plastisol applications over more traditional plasticizers.
• the 3-PPB also achieved a lower fusion temperature as shown in Table 1 and Figure 2, which facilitates faster processing times and/or lower energy costs in plastisol applications.
• Example 2 Basic Plastisol EvaluationsTM Processability,. Permanence 10086]
• the basic plastisol formulation of Example 1 was utilized in this example.
• the inventive monobenzoate (X-613) was compared to DINP, IDB (isodecyi benzoate), and 2,2,4-trirnethyl.
• Example 1 The basic plastisoi formulation of Example 1 was utilized in this example.
• Gel fusion data illustrates the relative solvation characteristics of various plasticizers.
• Figure 6 (b) shows the results of the gel/fusion evaluation, which reflected better results for 3-PPB as compared to X20 and unexpectedly better than the BBP control that is considered an industry standard.
• DOTP, DINP, and IDB demonstrated much poorer solvation properties than 3-PPB.
• 3-PPB is at least twice as efficient as IDB as a solvator, yet viscosity and rheoiogy are not sacrificed.
• Figure 8 shows Brookfie!d viscosities obtained for the various formulations: initial 1 day, 3 day and 7 day as compared to the control formulation comprising 50 phr DiNP. The results show that 3-PPB had higher viscosity initially than IDB, but lower than DINP.
• Torque rheometry is a method for measuring real processing conditions of a compound. Heat rise experiments illustrate the differences between when fusion occurs with different plastidzers. The measured torque and temperature curves, along with the physical changes of the compound taking place can be studied. Another point of interest is the reiative fusion temperature, which occurs when the stock tefTiperature initially rapidly increases. This temperature indicates the point at which the surface solvation begins to take place, resulting in a considerable increase in torqued leadin to the generation of fusion in the melt compound. The relative fusion temperature is helpful in determining the soivating characteristics of the plasticizers used in plasticized PVC. From there, an analysis of how different plasticizers affect the processing ability of a PVC melt compound or plastisol can be conducted, demonstrating how the processing factors of one plastldze may be more favorable than the other.
• Brabender Heat Rise The general heat rise formula show in Table 4 below was weighed out and mixed using a metal spatula, forming a white cake-iike powder.
• a C.W. Brabender Intellitorque® mixer was used for the study, ' The Brabender was equilibrated at a starting temperature of 4Q and after being charged with 50 cc of sample, the temperature was ramped at a rate of 3°G/rninute up to 200°G. Number 6 roller heads mixed the compound at a speed of 83 rpm with 1 second damping. After loading the chule was closed using a press and a 5 kg weight. Each sample was run until degradation began to occur.
• Table 5 illustrates the torque, time and temperature for each sample and indicated when the melt flow of the compound was reached. Overall, the. benzoates showed faster fusion times than the general purpose plastiGizers. Shorter fusion times indicate superior solvating properties of the pfasticizer.
• Heat rise results of Table 6 indicate the time, torque, and temperature where degradation began to occur for each sample.
• the time, torque and temperature at which relative fusion occurs are also represented, DINP, DOTP and DIDC had the highest temperaiures for relative fusion, indicating lower solvating ability.
• FIG. 1 shows Brabender heat rise data for 3-PPB
• Figure 12 shows Brabender data for 3-PPB compared to DINP.
• Figure 12 represents a good demonstration of the high solvating properties of 3-PPB versus genera! purpose plasticizers. Both compounds were run using the same starting temperatures and the same temperature ramp rate, The difference in their torque values was due to the differences in fusion characteristics that each sample produced.
• Figure 12 shows unequivocally that 3-PPB fused quicker than the DINP melt compound.
• the 3-PPB compound began fusing within the first 5 minutes of starting the run.
• the DINP compound required a higher temperature and more energy in order to start fusing..

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