US20160075855A1 - Polymeric compositions with improved noise suppression - Google Patents
Polymeric compositions with improved noise suppression Download PDFInfo
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- US20160075855A1 US20160075855A1 US14/852,681 US201514852681A US2016075855A1 US 20160075855 A1 US20160075855 A1 US 20160075855A1 US 201514852681 A US201514852681 A US 201514852681A US 2016075855 A1 US2016075855 A1 US 2016075855A1
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- plastisol
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- weight percent
- plasticizer
- substrate
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- SLCVBVWXLSEKPL-UHFFFAOYSA-N CC(C)(CO)CO Chemical compound CC(C)(CO)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 11
- 0 [1*]C(=O)OCC(C)(C)COC([2*])=O Chemical compound [1*]C(=O)OCC(C)(C)COC([2*])=O 0.000 description 6
- NTJIXQIWOUPKIF-UHFFFAOYSA-N CC(C)(COC(N)=O)COC(N)=O Chemical compound CC(C)(COC(N)=O)COC(N)=O NTJIXQIWOUPKIF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
- C07C63/04—Monocyclic monocarboxylic acids
- C07C63/06—Benzoic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/003—Esters of saturated alcohols having the esterified hydroxy group bound to an acyclic carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C69/75—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of acids with a six-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/78—Benzoic acid 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- 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
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic 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
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16F—SPRINGS; SHOCK-ABSORBERS; MEANS FOR DAMPING VIBRATION
- F16F15/00—Suppression of vibrations in systems; Means or arrangements for avoiding or reducing out-of-balance forces, e.g. due to motion
- F16F15/02—Suppression of vibrations of non-rotating, e.g. reciprocating systems; Suppression of vibrations of rotating systems by use of members not moving with the rotating systems
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2518/00—Other type of polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
Definitions
- the invention relates to improving vibration damping on a substrate. More specifically, the invention relates to the use of plastisols to improve vibration damping on a substrate, such as the underbody of a vehicle. The invention also relates to novel plastisols and plasticizers for improving vibration damping.
- the objective of this invention is to provide improved vibration damping performance to metallic substrates.
- substrates include, but are not limited to, those used for the construction of vehicles.
- the objective of this invention is to provide improved vibration damping within the range of temperatures frequently encountered during driving, namely from ⁇ 30° to 50° C. and most frequently from ⁇ 10° C. to 40° C.
- Another objective of this invention is to provide improved vibration damping within this temperature range across the frequencies audible to humans, particularly in the low frequency range of 10 to 200 Hz as described in “Low Frequency Noise. What we know, what we do not know, and what we would like to know”, Leventhall, Geoff, Journal of Low Frequency Noise, Vibration and Active Control 28, 2, pp. 79-104 (2009).
- NVH noise, vibration, and harshness
- laminated safety glass can be comprised of acoustic interlayers which suppress sound transmission. Applications of such acoustic interlayers can include glass panes in commercial and residential buildings and automotive glazing.
- Other sources of NVH in vehicles include engine noise, road noise, springs and suspensions, braking, and chassis vibration.
- Noise suppression techniques include component design to reduce vibration and sound transmission; use of composite materials instead of metals; elastomeric sleeves or guards; nonwoven fabrics; carpet or other materials applied to the vehicle interior; foam; liquid-applied damping formulations; and objects produced from viscoelastic materials, such as bitumen or asphaltic pads.
- asphaltic pads cannot easily be placed and conformed to some locations on a vehicle body, require manual application, are subject to embrittlement, and must continue to adhere to the metal substrate in order to be effective.
- Some materials contribute undesired weight to the vehicle, contrary to weight reduction goals designed to improve fuel mileage. Materials which require high temperature and/or long times to cure can slow production, add cost, and result in higher energy usage.
- NVH One mode of NVH is through vibration.
- Polymeric materials can damp, or reduce oscillations of, a substrate by dissipating the oscillation energy with their viscoelastic behavior.
- a standard measurement of damping utilizes the Oberst method and apparatus. In this method, a material engineered to confer damping behavior is affixed to a stainless steel bar which has negligible damping itself. The effect of the damping material is deduced from the behavior of the sample bar compared to an untreated reference bar. Damping behavior may also be measured using Dynamic Mechanical Thermal Analysis, or DMTA. In this technique, a sample is exposed to a sinusoidal force, generally over a range of temperatures or frequencies.
- DMTA Dynamic Mechanical Thermal Analysis
- the modulus of a viscoelastic polymeric substance When heated, the modulus of a viscoelastic polymeric substance varies greatly from the glassy state at low temperatures, through the glass transition to a rubbery state, and finally to a lower viscosity molten state.
- the ratio of the storage modulus to the loss modulus a value known as the tan ⁇ , is a measure of the material's ability to damp vibrations. Higher tan ⁇ values signify more effective damping behavior.
- the DMTA tan ⁇ has been shown to correlate well with the Oberst bar testing.
- Plasticized polyvinyl chloride is well known in the automotive industry. Plasticized PVC applied as a plastisol in automotive underbody coatings and sealants, after thermal curing, can protect the vehicle from chipping by stones and other materials on the road surface. Such coatings also offer protection against corrosion, for example from salted roads. Plasticized PVC coatings can also provide a low level of reduction of the transmission of vibrations from metallic substrates. However, the performance of plasticized PVC coatings is inadequate to confer satisfactory vibration damping across the range of temperatures and noise frequencies typically encountered without the incorporation of additional damping techniques. These performance deficiencies are exacerbated when the desire to reduce NVH to vehicle passengers over traditional levels is considered. Despite these deficiencies, the ease of application and economy of PVC plastisols make them an appealing potential solution to the reduction of NVH should performance improvements be realized.
- An embodiment of the present invention is a plasticizer comprising the esterification product formed by the reaction of formula (I)
- R 1 is selected from the group consisting of phenyl, tolyl, and cyclohexyl and R 2 is selected from the group consisting of methyl, ethyl, n-propyl, and i-propyl.
- Another embodiment of the present invention is a plastisol comprising a polymeric component and a plasticizer.
- the plasticizer comprises the esterification product formed by the reaction of formula (I)
- R 1 and R 2 are independently selected from the group consisting of an aromatic or an alkyl-substituted aromatic group having 4 to 10 carbon atoms and a linear, branched, or cycloaliphatic alkyl group having 1 to 9 carbon atoms.
- Yet another embodiment is a method of improving vibration damping of a substrate comprising affixing a plastisol onto a substrate.
- the plastisol comprises a polymeric component and a plasticizer.
- the plasticizer comprises the esterification product formed by the reaction of formula (I)
- R 1 and R 2 are independently selected from the group consisting of an aromatic or an alkyl-substituted aromatic group having 4 to 10 carbon atoms and a linear, branched, or cycloaliphatic alkyl group having 1 to 9 carbon atoms.
- the term “and/or,” when used in a list of two or more items, means that any one of the listed items can be employed by itself, or any combination of two or more of the listed items can be employed.
- the composition can contain A alone; B alone; C alone; A and B in combination; A and C in combination; B and C in combination; or A, B, and C in combination.
- affixing refers to providing continuous and intimate contact between the plastisol and the substrate such that the fused plastisol remains on the substrate.
- a plastisol can be affixed to a car underbody via spray coating the plastisol onto a car underbody and subjecting the coated car underbody to conditions to fuse the plastisol.
- adhered refers to using an adhesive to affix a fused plastisol sheet to a substrate.
- estersification product refers to the blend of “partial esters”, “mixed esters”, and “diesters” produced from the reaction of one or more carboxylic acids with a diol.
- partial esters refers to the reaction product wherein not all of the hydroxyls of a diol have fully reacted with a carboxylic acid.
- mixed ester refers to the reaction product wherein each of the hydroxyls of a diol has reacted with different carboxylic acids.
- diester refers to the reaction product wherein each hydroxyl of a diol has reacted with the same carboxylic acid.
- the esterification product can comprise the partial esters 1,3-pentanediol monobenzoate and 1,3-pentanediol monotoluate, the mixed ester 1,3-pentanediol benzoate/toluate, and the diesters 1,3-pentanediol dibenzoate and 1,3-pentanediol ditoluate.
- reaction product of formula (a) and/or formula (b) with formula (c) is intended to include carboxylic acids and the corresponding esters, anhydrides, and/or acid chlorides of formula (a) and/or formula (b) as explicitly set forth in the claims.
- plastisol refers to a liquid dispersion of polymeric resin particles, optionally with other ingredients, in a plasticizer.
- fused plastisol refers to the solid plastic material that is formed upon fusing the plastisol and subsequently cooling to a desired temperature.
- fusing refers to heating of the plastisol to a temperature sufficient to yield a solid structure with mechanical integrity.
- substrate refers to the material that provides the surface onto which the plastisol is affixed.
- An embodiment of the present invention is a plasticizer comprising the esterification product formed by the reaction of formula (I)
- R 2 is selected from the group consisting of n-propyl and i-propyl.
- plasticizers can readily make the above-identified plasticizers starting from commercially available chemicals for Formulas (I), (II), and (III) and using process conditions well known in the art.
- the proportions of mixed esters formed when two carboxylic acids are used may be adjusted by varying the ratios of the two carboxylic acids.
- the esterification product formed by the reactions of the carboxylic acids of formula (I) and formula (II) with the diol of formula (III) can contain several reaction products including (1) partial esters formed when not all of the of the hydroxyls of formula (III) are fully reacted with either formula (I) or formula (II), (2) mixed esters formed by the reaction of formula (I) with one hydroxyl of formula (III) and formula (II) with the other hydroxyl of formula (III) when R 1 and R 2 are different, and (3) diesters formed by the reaction of either formula (I) or formula (II) with both of the hydroxyls of formula (III).
- the plasticizer comprises the esterification product formula (IV)
- the esterification product comprises at least 10 weight percent of a mixed ester based on the total weight of the esterification product.
- Other examples of the amount of mixed ester based on the total weight of the esterification product include at least 15 weight percent, at least 20 weight percent, at least 25 weight percent, at least 30 weight percent, at least 40 weight percent, or at least 50 weight percent of a mixed ester.
- the amount of mixed ester ranges from 10 weight percent to 80 weight percent, 10 weight percent to 50 weight percent, 10 weight percent to 40 weight percent, 20 weight percent to 80 weight percent, 20 weight percent to 50 weight percent, or 20 weight percent to 50 weight percent, based on the total weight of the esterification product.
- Another embodiment of the present invention is a plastisol comprising a polymeric component and a plasticizer.
- the plasticizer comprises the esterification product formed by the reaction of formula (I)
- R 1 and R 2 are independently selected from the group consisting of an aromatic or an alkyl-substituted aromatic group having 4 to 10 carbon atoms and a linear, branched, or cycloaliphatic alkyl group having 1 to 9 carbon atoms.
- R 1 is selected from the group consisting of phenyl, tolyl, and cyclohexyl and R 2 is selected from the group consisting of n-propyl, i-propyl, and cyclohexyl. In one aspect, R 1 and R 2 are both cyclohexyl.
- R 1 is phenyl and R 2 is tolyl and the ratio of phenyl to tolyl ranges from 0.05:20 to 20:0.05 based on the total amount of the esterification product. In other aspects, the ratio of phenyl to tolyl ranges from 0.1:10 to 10:0.1 or 0.1:5 to 5:0.1 or 0.5:1.5 to 1.5:0.5.
- the plasticizer comprises the esterification product formula (IV)
- the esterification product comprises at least 10 weight percent of a mixed ester, based on the total weight of the esterification product.
- Other examples of the amount of mixed ester based on the total weight of the esterification product include at least 15 weight percent, at least 20 weight percent, at least 25 weight percent, at least 30 weight percent, at least 40 weight percent or at least 50 weight percent of a mixed ester.
- the amount of mixed ester ranges from 10 weight percent to 80 weight percent, 10 weight percent to 50 weight percent, 10 weight percent to 40 weight percent, 20 weight percent to 80 weight percent, 20 weight percent to 50 weight percent, or 20 weight percent to 40 weight percent, based on the total weight of the esterification product.
- the plastisol comprises a polymeric component.
- the polymeric component comprises polyvinyl chloride, polyvinyl acetate, an acrylic polymer, and/or a vinyl chloride-containing copolymer.
- the polymeric component comprises polyvinyl chloride and/or an acrylic polymer.
- the polymeric component comprises polyvinyl chloride and/or polyvinyl acetate.
- the polymeric component comprises polyvinyl chloride and/or vinyl chloride-containing copolymers comprising vinyl acetate.
- the polymeric component comprises polyvinyl chloride and vinyl chloride-containing copolymers comprising acrylic.
- the polymeric component comprises polyvinyl chloride.
- the plastisol comprises plasticizer, polymeric component, and other components.
- other components include, but are not limited to, a second plasticizer, fillers, pigments, stabilizers, foaming agents, hollow materials, elastomeric materials, rheology control additives, and adhesion promoters.
- the amounts of plasticizer, polymeric component, and other components can vary widely.
- the plastisol comprises 10 weight percent to 70 weight percent plasticizer, 10 weight percent to 70 weight percent polymeric component, and 10 weight percent to 80 weight percent other components, each based on the total weight of the plastisol.
- Other examples include, 15 weight percent to 60 weight percent plasticizer, 15 weight percent to 60 weight percent polymeric component, and 10 weight percent to 60 weight percent other components; or 20 weight percent to 45 weight percent plasticizer, 20 weight percent to 45 weight percent polymeric component, and 10 weight percent to 50 weight percent other components.
- the viscosity of the plastisol can vary over a wide range.
- the plastisol has a viscosity ranging from 5,000 centipoise (cP) to 200,000 cP using Brookfield viscosity measurement at 23° C.
- the plastisol has a viscosity ranging from 30,000 cP to 120,000 cP or from 40,000 cP to 90,000 cP.
- the plastisol comprises a second plasticizer.
- the second plasticizer comprises phthalates; terephthalates; isophthalates; trimellitates; adipates; cyclohexanedicarboxylates; benzoates; phosphates; diesters of ethylene glycol, propylene glycol, their oligomers, and mixtures thereof; citrates; succinates; alkyl sulfonates; fatty acid esters and epoxidized fatty acid esters; triglycerides and epoxidized triglycerides, optionally substituted; dianhydrohexitol diesters; pentaerythritol-based tetraesters; furan-based esters; other esters; ketals; and/or polymeric plasticizers.
- the second plasticizer comprises dioctyl terephthalate, diisooctyl phthalate, di-2-ethylhexyl phthalate, di-2-ethylhexyl terephthalate, tri-2-ethylhexyl trimellitate, di-2-propylheptyl phthalate, diisononyl phthalate, diisodecyl phthalate, diisoundecyl phthalate, ditridecyl phthalate, trioctyl trimellitate, triisononyl trimellitate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, isononyl benzoate, isodecyl benzoate, diisononyl 1,2-cyclohexanedicarboxylate, dioctyl adipate, di-2-ethylhexyl adipate, triethylene glycol di-2-ethyl
- the second plasticizer comprises dioctyl terephthalate, di-2-ethylhexyl terephthalate, dioctyl adipate, di-2-ethylhexyl adipate, and/or triethylene glycol di-2-ethylhexanoate.
- the second plasticizer comprises, di-2-ethylhexyl terephthalate, diisononyl phthalate, and/or diisononyl 1,2-cyclohexanedicarboxylate.
- the plastisol comprises fillers.
- fillers include calcium carbonate, magnesium carbonate, silica, clay, mica, graphite, zinc oxide, and/or calcium oxide.
- the fillers comprise calcium carbonate.
- the plastisol in one aspect, can comprise stabilizers.
- stabilizers include metal soaps, epoxidized oils and epoxidized fatty acid esters, and/or organotin compounds.
- the plastisol can be formulated or produced in a manner which incorporates more free volume into the fused plastisol.
- mechanical frothing may be applied to produce a foamed plastisol.
- a chemical foaming agent which results in a foamed structure after fusing is completed.
- a foaming agent is azodicarbonamide.
- a catalyst is used along with the chemical foaming agent.
- foam stabilizers are used.
- hollow materials are incorporated into the plastisol.
- Nonlimiting examples of hollow materials include glass beads, microbeads, and/or microspheres, which can be produced from either inorganic or polymeric organic substances.
- the hollow materials are thermoplastic microspheres.
- the plastisol comprises elastomeric materials.
- elastomeric materials include nitrile-butadiene rubber, natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, butyl rubber, ethylene-propylene-diene monomer (EPDM) rubber, chloroprene rubber, styrenated block copolymers, ethylene-vinyl acetate copolymers, olefinic elastomers, olefinic copolymer elastomers, silicone elastomers, polysulfide elastomers, and/or polyurethane elastomers.
- additives to control rheology can be incorporated into the plastisols.
- These may include secondary plasticizers or diluents.
- additives include petroleum distillates; hydrocarbon oils such as, for example, mineral oil and mineral spirits; fatty acid esters; polyphenyl oligomers, optionally partially hydrogenated; and organic solvents.
- thickeners may be added to boost viscosity as desired. Materials and techniques for adjusting plastisol rheology are well known in the art.
- the plastisol comprises adhesion promoters.
- adhesion promoters include polyamidoamines, blocked isocyanates and isocyanurates, silanes, and/or epoxy resins.
- the fused plastisol has a maximum Tan Delta (Tan ⁇ max ) occurring between 20° C. and 50° C. and has Tan Delta at 30° C. (Tan ⁇ 30C ) ranging from 0.5 to 2.0, when measured on a sample nominally 0.6-0.7 mm thick, 3.2 mm wide, and 10-12 mm long using a Q800 Dynamic Mechanical Analyzer with a Tension Clamp at a strain of 0.1% and at a frequency of 1 Hz and a temperature ramp rate of 3° C./min.
- Tan Delta at 30° C. ranges from 0.5 to 1.8 or 0.5 to 1.6 or 0.5 to 1.4 or 0.6 to 2.0 or 0.6 to 1.8 or 0.6 to 1.6 or 0.6 to 1.4 or 0.7 to 2.0 or 0.7 to 1.8 or 0.7 to 1.6 or 0.7 to 1.4.
- the maximum Tan Delta occurs between 20° C. and 40° C. or 30° C. and 50° C.
- Another embodiment of the present invention is a method of improving vibration damping of a substrate comprising affixing a plastisol to the substrate, wherein the plastisol comprises a polymeric component and a plasticizer.
- the plasticizer comprises the esterification product formed by the reaction of formula (I)
- R 1 and R 2 are independently selected from the group consisting of an aromatic or an alkyl-substituted aromatic group having 4 to 10 carbon atoms and a linear, branched, or cycloaliphatic alkyl group having 1 to 9 carbon atoms.
- All of the aspects of the plastisol described herein above can apply to the method of improving vibration damping of a substrate.
- These aspects include the options for R 1 and R 2 groups, plasticizer, the amount of mixed esters, polymeric component, the amounts of plasticizer, polymeric component, and other components in the plastisol, plastisol viscosity ranges, second plasticizers, fillers, stabilizers, foaming agents, hollow materials, elastomeric materials, rheology control additives, adhesion promoters, maximum Tan Delta and Tan Delta at 30° C.
- the substrate is not particularly limited. In one aspect, the substrate is metal. In one aspect, the substrate comprises steel. In one aspect, the substrate comprises aluminum. In one aspect, the substrate is part of a wheeled vehicle. In another aspect, the substrate is on the underbody of a wheeled vehicle.
- the method of affixing the plastisol onto the substrate comprises (a) applying the plastisol onto the substrate, (b) fusing the plastisol to produce a plastisol-covered substrate, and (c) cooling the plastisol-covered substrate to ambient temperatures.
- the method for applying the plastisol onto the substrate is not particularly limited.
- applying the plastisol onto the substrate comprises coating the substrate with the plastisol. Nonlimiting examples of coating include spray coating and/or extrusion coating.
- the method of affixing the plastisol to the substrate comprises (a) fusing the plastisol into a sheet and (b) adhering the sheet to the substrate.
- the fusing occurs at a temperature ranging from 100° C. to 220° C. for a time period ranging from 1 min to 2 hours. In another aspect, the fusing occurs at a temperature ranging from 140° C. to 180° C. for a time period ranging from 15 min. to 40 min.
- said esterification product comprises at least 10 weight percent of a mixed ester, based on the total weight of said esterification product; wherein said esterification product comprises at least 15 weight percent, at least 20 weight percent, at least 25 weight percent, at least 30 weight percent, at least 40 weight percent, or at least 50 weight percent of a mixed ester.
- R 1 and R 2 are independently selected from the group consisting of an aromatic or an alkyl-substituted aromatic group having 4 to 10 carbon atoms and linear, branched, or cycloaliphatic alkyl group having 1 to 9 carbon atoms.
- said esterification product comprises at least 10 weight percent of a mixed ester, based on the total weight of said esterification product; wherein said esterification product comprises at least 15 weight percent, at least 20 weight percent, at least 25 weight percent, at least 30 weight percent, at least 40 weight percent, or at least 50 weight percent of a mixed ester.
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- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Acoustics & Sound (AREA)
- Aviation & Aerospace Engineering (AREA)
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Abstract
Disclosed is a method for improving vibration damping of a substrate, such as the underbody of an automobile. The method comprises applying a plastisol which comprises a polymeric component and a plasticizer. The fused plastisol has improved damping behavior as determined using Dynamic Mechanical Thermal Analysis. Novel plastisols and novel plasticizers are also disclosed.
Description
- This application claims priority to U.S. Provisional Application No. 62/050942 filed Sep. 16, 2014, the disclosure of which is incorporated herein by reference in its entirety.
- The invention relates to improving vibration damping on a substrate. More specifically, the invention relates to the use of plastisols to improve vibration damping on a substrate, such as the underbody of a vehicle. The invention also relates to novel plastisols and plasticizers for improving vibration damping.
- The objective of this invention is to provide improved vibration damping performance to metallic substrates. Examples of such substrates include, but are not limited to, those used for the construction of vehicles. More specifically, the objective of this invention is to provide improved vibration damping within the range of temperatures frequently encountered during driving, namely from −30° to 50° C. and most frequently from −10° C. to 40° C. Another objective of this invention is to provide improved vibration damping within this temperature range across the frequencies audible to humans, particularly in the low frequency range of 10 to 200 Hz as described in “Low Frequency Noise. What we know, what we do not know, and what we would like to know”, Leventhall, Geoff, Journal of Low Frequency Noise, Vibration and Active Control 28, 2, pp. 79-104 (2009).
- The reduction of noise, vibration, and harshness (often abbreviated as NVH) to humans is a goal of many industrial processes. Exposure to NVH comes from numerous sources, and can be mitigated by various means. For example, laminated safety glass can be comprised of acoustic interlayers which suppress sound transmission. Applications of such acoustic interlayers can include glass panes in commercial and residential buildings and automotive glazing. Other sources of NVH in vehicles include engine noise, road noise, springs and suspensions, braking, and chassis vibration. Noise suppression techniques include component design to reduce vibration and sound transmission; use of composite materials instead of metals; elastomeric sleeves or guards; nonwoven fabrics; carpet or other materials applied to the vehicle interior; foam; liquid-applied damping formulations; and objects produced from viscoelastic materials, such as bitumen or asphaltic pads. Although effective to varying extents depending on the source of the noise, these techniques suffer from limitations. For example, asphaltic pads cannot easily be placed and conformed to some locations on a vehicle body, require manual application, are subject to embrittlement, and must continue to adhere to the metal substrate in order to be effective. Some materials contribute undesired weight to the vehicle, contrary to weight reduction goals designed to improve fuel mileage. Materials which require high temperature and/or long times to cure can slow production, add cost, and result in higher energy usage.
- One mode of NVH is through vibration. Polymeric materials can damp, or reduce oscillations of, a substrate by dissipating the oscillation energy with their viscoelastic behavior. A standard measurement of damping utilizes the Oberst method and apparatus. In this method, a material engineered to confer damping behavior is affixed to a stainless steel bar which has negligible damping itself. The effect of the damping material is deduced from the behavior of the sample bar compared to an untreated reference bar. Damping behavior may also be measured using Dynamic Mechanical Thermal Analysis, or DMTA. In this technique, a sample is exposed to a sinusoidal force, generally over a range of temperatures or frequencies. When heated, the modulus of a viscoelastic polymeric substance varies greatly from the glassy state at low temperatures, through the glass transition to a rubbery state, and finally to a lower viscosity molten state. The ratio of the storage modulus to the loss modulus, a value known as the tan δ, is a measure of the material's ability to damp vibrations. Higher tan δ values signify more effective damping behavior. The DMTA tan δ has been shown to correlate well with the Oberst bar testing.
- Plasticized polyvinyl chloride (PVC) is well known in the automotive industry. Plasticized PVC applied as a plastisol in automotive underbody coatings and sealants, after thermal curing, can protect the vehicle from chipping by stones and other materials on the road surface. Such coatings also offer protection against corrosion, for example from salted roads. Plasticized PVC coatings can also provide a low level of reduction of the transmission of vibrations from metallic substrates. However, the performance of plasticized PVC coatings is inadequate to confer satisfactory vibration damping across the range of temperatures and noise frequencies typically encountered without the incorporation of additional damping techniques. These performance deficiencies are exacerbated when the desire to reduce NVH to vehicle passengers over traditional levels is considered. Despite these deficiencies, the ease of application and economy of PVC plastisols make them an appealing potential solution to the reduction of NVH should performance improvements be realized.
- An embodiment of the present invention is a plasticizer comprising the esterification product formed by the reaction of formula (I)
-
- R1COOH (I)
and formula (II) - R2COOH (II)
or the corresponding esters, anhydrides, and/or acid chlorides of formula (I) and/or formula (II), with formula (III)
- R1COOH (I)
- R1 is selected from the group consisting of phenyl, tolyl, and cyclohexyl and R2 is selected from the group consisting of methyl, ethyl, n-propyl, and i-propyl.
- Another embodiment of the present invention is a plastisol comprising a polymeric component and a plasticizer. The plasticizer comprises the esterification product formed by the reaction of formula (I)
-
- R1COOH (I)
and formula (II) - R2COOH (II)
or the corresponding esters, anhydrides, and/or acid chlorides of formula (I) and/or formula (II), with formula (III)
- R1COOH (I)
- R1 and R2 are independently selected from the group consisting of an aromatic or an alkyl-substituted aromatic group having 4 to 10 carbon atoms and a linear, branched, or cycloaliphatic alkyl group having 1 to 9 carbon atoms.
- Yet another embodiment is a method of improving vibration damping of a substrate comprising affixing a plastisol onto a substrate. The plastisol comprises a polymeric component and a plasticizer. The plasticizer comprises the esterification product formed by the reaction of formula (I)
-
- R1COOH (I)
and formula (II) - R2COOH (II)
or the corresponding esters, anhydrides, and/or acid chlorides of formula (I) and/or formula (II), with formula (III)
- R1COOH (I)
- R1 and R2 are independently selected from the group consisting of an aromatic or an alkyl-substituted aromatic group having 4 to 10 carbon atoms and a linear, branched, or cycloaliphatic alkyl group having 1 to 9 carbon atoms.
- As used herein the term “and/or,” when used in a list of two or more items, means that any one of the listed items can be employed by itself, or any combination of two or more of the listed items can be employed. For example, if a composition is described as containing components A, B, and/or C, the composition can contain A alone; B alone; C alone; A and B in combination; A and C in combination; B and C in combination; or A, B, and C in combination.
- The term “affixing”, as used herein, refers to providing continuous and intimate contact between the plastisol and the substrate such that the fused plastisol remains on the substrate. For example, a plastisol can be affixed to a car underbody via spray coating the plastisol onto a car underbody and subjecting the coated car underbody to conditions to fuse the plastisol. The term “adhering” as used herein, refers to using an adhesive to affix a fused plastisol sheet to a substrate.
- The term “esterification product”, as used herein, refers to the blend of “partial esters”, “mixed esters”, and “diesters” produced from the reaction of one or more carboxylic acids with a diol. The term “partial esters”, as used herein, refers to the reaction product wherein not all of the hydroxyls of a diol have fully reacted with a carboxylic acid. The term “mixed ester”, as used herein, refers to the reaction product wherein each of the hydroxyls of a diol has reacted with different carboxylic acids. The term “diester”, as used herein, refers to the reaction product wherein each hydroxyl of a diol has reacted with the same carboxylic acid. For example, if benzoic acid and toluic acid are reacted with 1-3-pentanediol, the esterification product can comprise the partial esters 1,3-pentanediol monobenzoate and 1,3-pentanediol monotoluate, the mixed ester 1,3-pentanediol benzoate/toluate, and the diesters 1,3-pentanediol dibenzoate and 1,3-pentanediol ditoluate. The term “the reaction product of formula (a) and/or formula (b) with formula (c)”, as used herein, is intended to include carboxylic acids and the corresponding esters, anhydrides, and/or acid chlorides of formula (a) and/or formula (b) as explicitly set forth in the claims.
- The term “plastisol”, as used herein, refers to a liquid dispersion of polymeric resin particles, optionally with other ingredients, in a plasticizer. The term “fused plastisol”, as used herein, refers to the solid plastic material that is formed upon fusing the plastisol and subsequently cooling to a desired temperature. The term “fusing”, as used herein, refers to heating of the plastisol to a temperature sufficient to yield a solid structure with mechanical integrity.
- The term “substrate”, as used herein, refers to the material that provides the surface onto which the plastisol is affixed.
- An embodiment of the present invention is a plasticizer comprising the esterification product formed by the reaction of formula (I)
-
- R1COOH (I)
and formula (II) - R2COOH (II)
or the corresponding esters, anhydrides, and/or acid chlorides of formula (I) and/or formula (II), with formula (III)
- R1COOH (I)
-
- R1 is selected from the group consisting of phenyl, tolyl, and cyclohexyl and R2 is selected from the group consisting of methyl, ethyl, n-propyl, and i-propyl.
- In one aspect, R2 is selected from the group consisting of n-propyl and i-propyl.
- One skilled in the art can readily make the above-identified plasticizers starting from commercially available chemicals for Formulas (I), (II), and (III) and using process conditions well known in the art. For example, the proportions of mixed esters formed when two carboxylic acids are used may be adjusted by varying the ratios of the two carboxylic acids.
- The esterification product formed by the reactions of the carboxylic acids of formula (I) and formula (II) with the diol of formula (III) can contain several reaction products including (1) partial esters formed when not all of the of the hydroxyls of formula (III) are fully reacted with either formula (I) or formula (II), (2) mixed esters formed by the reaction of formula (I) with one hydroxyl of formula (III) and formula (II) with the other hydroxyl of formula (III) when R1 and R2 are different, and (3) diesters formed by the reaction of either formula (I) or formula (II) with both of the hydroxyls of formula (III).
- In one aspect, the plasticizer comprises the esterification product formula (IV)
- The esterification product comprises at least 10 weight percent of a mixed ester based on the total weight of the esterification product. Other examples of the amount of mixed ester based on the total weight of the esterification product include at least 15 weight percent, at least 20 weight percent, at least 25 weight percent, at least 30 weight percent, at least 40 weight percent, or at least 50 weight percent of a mixed ester. In one aspect, the amount of mixed ester ranges from 10 weight percent to 80 weight percent, 10 weight percent to 50 weight percent, 10 weight percent to 40 weight percent, 20 weight percent to 80 weight percent, 20 weight percent to 50 weight percent, or 20 weight percent to 50 weight percent, based on the total weight of the esterification product.
- Another embodiment of the present invention is a plastisol comprising a polymeric component and a plasticizer. The plasticizer comprises the esterification product formed by the reaction of formula (I)
-
- R1COOH (I)
and formula (II) - R2COOH (II)
or the corresponding esters, anhydrides, and/or acid chlorides of formula (I) and/or formula (II), with formula (III)
- R1COOH (I)
- wherein R1 and R2 are independently selected from the group consisting of an aromatic or an alkyl-substituted aromatic group having 4 to 10 carbon atoms and a linear, branched, or cycloaliphatic alkyl group having 1 to 9 carbon atoms.
- In one aspect, R1 is selected from the group consisting of phenyl, tolyl, and cyclohexyl and R2 is selected from the group consisting of n-propyl, i-propyl, and cyclohexyl. In one aspect, R1 and R2 are both cyclohexyl.
- In one aspect, R1 is phenyl and R2 is tolyl and the ratio of phenyl to tolyl ranges from 0.05:20 to 20:0.05 based on the total amount of the esterification product. In other aspects, the ratio of phenyl to tolyl ranges from 0.1:10 to 10:0.1 or 0.1:5 to 5:0.1 or 0.5:1.5 to 1.5:0.5.
- In one aspect, the plasticizer comprises the esterification product formula (IV)
- wherein the esterification product comprises at least 10 weight percent of a mixed ester, based on the total weight of the esterification product. Other examples of the amount of mixed ester based on the total weight of the esterification product include at least 15 weight percent, at least 20 weight percent, at least 25 weight percent, at least 30 weight percent, at least 40 weight percent or at least 50 weight percent of a mixed ester. In one aspect, the amount of mixed ester ranges from 10 weight percent to 80 weight percent, 10 weight percent to 50 weight percent, 10 weight percent to 40 weight percent, 20 weight percent to 80 weight percent, 20 weight percent to 50 weight percent, or 20 weight percent to 40 weight percent, based on the total weight of the esterification product.
- In addition to the plasticizer, the plastisol comprises a polymeric component. In one aspect, the polymeric component comprises polyvinyl chloride, polyvinyl acetate, an acrylic polymer, and/or a vinyl chloride-containing copolymer. In one aspect, the polymeric component comprises polyvinyl chloride and/or an acrylic polymer. In one aspect, the polymeric component comprises polyvinyl chloride and/or polyvinyl acetate. In one aspect, the polymeric component comprises polyvinyl chloride and/or vinyl chloride-containing copolymers comprising vinyl acetate. In one aspect, the polymeric component comprises polyvinyl chloride and vinyl chloride-containing copolymers comprising acrylic. In one aspect, the polymeric component comprises polyvinyl chloride.
- The plastisol comprises plasticizer, polymeric component, and other components. Examples of other components include, but are not limited to, a second plasticizer, fillers, pigments, stabilizers, foaming agents, hollow materials, elastomeric materials, rheology control additives, and adhesion promoters. The amounts of plasticizer, polymeric component, and other components can vary widely. For example, in one aspect the plastisol comprises 10 weight percent to 70 weight percent plasticizer, 10 weight percent to 70 weight percent polymeric component, and 10 weight percent to 80 weight percent other components, each based on the total weight of the plastisol. Other examples include, 15 weight percent to 60 weight percent plasticizer, 15 weight percent to 60 weight percent polymeric component, and 10 weight percent to 60 weight percent other components; or 20 weight percent to 45 weight percent plasticizer, 20 weight percent to 45 weight percent polymeric component, and 10 weight percent to 50 weight percent other components.
- The viscosity of the plastisol can vary over a wide range. In one aspect, the plastisol has a viscosity ranging from 5,000 centipoise (cP) to 200,000 cP using Brookfield viscosity measurement at 23° C. In other examples, the plastisol has a viscosity ranging from 30,000 cP to 120,000 cP or from 40,000 cP to 90,000 cP.
- In one aspect, the plastisol comprises a second plasticizer. In one aspect the second plasticizer comprises phthalates; terephthalates; isophthalates; trimellitates; adipates; cyclohexanedicarboxylates; benzoates; phosphates; diesters of ethylene glycol, propylene glycol, their oligomers, and mixtures thereof; citrates; succinates; alkyl sulfonates; fatty acid esters and epoxidized fatty acid esters; triglycerides and epoxidized triglycerides, optionally substituted; dianhydrohexitol diesters; pentaerythritol-based tetraesters; furan-based esters; other esters; ketals; and/or polymeric plasticizers. In another aspect, the second plasticizer comprises dioctyl terephthalate, diisooctyl phthalate, di-2-ethylhexyl phthalate, di-2-ethylhexyl terephthalate, tri-2-ethylhexyl trimellitate, di-2-propylheptyl phthalate, diisononyl phthalate, diisodecyl phthalate, diisoundecyl phthalate, ditridecyl phthalate, trioctyl trimellitate, triisononyl trimellitate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, isononyl benzoate, isodecyl benzoate, diisononyl 1,2-cyclohexanedicarboxylate, dioctyl adipate, di-2-ethylhexyl adipate, triethylene glycol di-2-ethylhexanoate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, and/or dibenzoates produced from mixtures of diethylene glycol and dipropylene glycol. In one aspect, the second plasticizer comprises dioctyl terephthalate, di-2-ethylhexyl terephthalate, dioctyl adipate, di-2-ethylhexyl adipate, and/or triethylene glycol di-2-ethylhexanoate. In one aspect, the second plasticizer comprises, di-2-ethylhexyl terephthalate, diisononyl phthalate, and/or diisononyl 1,2-cyclohexanedicarboxylate.
- In one aspect, the plastisol comprises fillers. Nonlimiting examples of fillers include calcium carbonate, magnesium carbonate, silica, clay, mica, graphite, zinc oxide, and/or calcium oxide. In one aspect, the fillers comprise calcium carbonate.
- The plastisol, in one aspect, can comprise stabilizers. Nonlimiting examples of stabilizers include metal soaps, epoxidized oils and epoxidized fatty acid esters, and/or organotin compounds.
- In one aspect, the plastisol can be formulated or produced in a manner which incorporates more free volume into the fused plastisol. In one such technique, mechanical frothing may be applied to produce a foamed plastisol. In another aspect, a chemical foaming agent which results in a foamed structure after fusing is completed. One non-limiting example of such a foaming agent is azodicarbonamide. In one aspect, a catalyst is used along with the chemical foaming agent. In another aspect, foam stabilizers are used. In another aspect, hollow materials are incorporated into the plastisol. Nonlimiting examples of hollow materials include glass beads, microbeads, and/or microspheres, which can be produced from either inorganic or polymeric organic substances. In one aspect, the hollow materials are thermoplastic microspheres.
- In one aspect, the plastisol comprises elastomeric materials. Nonlimiting examples of elastomeric materials include nitrile-butadiene rubber, natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, butyl rubber, ethylene-propylene-diene monomer (EPDM) rubber, chloroprene rubber, styrenated block copolymers, ethylene-vinyl acetate copolymers, olefinic elastomers, olefinic copolymer elastomers, silicone elastomers, polysulfide elastomers, and/or polyurethane elastomers.
- In another aspect, additives to control rheology can be incorporated into the plastisols. These may include secondary plasticizers or diluents. Examples of such additives include petroleum distillates; hydrocarbon oils such as, for example, mineral oil and mineral spirits; fatty acid esters; polyphenyl oligomers, optionally partially hydrogenated; and organic solvents. Conversely, thickeners may be added to boost viscosity as desired. Materials and techniques for adjusting plastisol rheology are well known in the art.
- In one aspect, the plastisol comprises adhesion promoters. Nonlimiting examples of adhesion promoters include polyamidoamines, blocked isocyanates and isocyanurates, silanes, and/or epoxy resins.
- In one aspect, the fused plastisol has a maximum Tan Delta (Tan δmax) occurring between 20° C. and 50° C. and has Tan Delta at 30° C. (Tan δ30C) ranging from 0.5 to 2.0, when measured on a sample nominally 0.6-0.7 mm thick, 3.2 mm wide, and 10-12 mm long using a Q800 Dynamic Mechanical Analyzer with a Tension Clamp at a strain of 0.1% and at a frequency of 1 Hz and a temperature ramp rate of 3° C./min.
- In one aspect, Tan Delta at 30° C. (Tan δ30C) ranges from 0.5 to 1.8 or 0.5 to 1.6 or 0.5 to 1.4 or 0.6 to 2.0 or 0.6 to 1.8 or 0.6 to 1.6 or 0.6 to 1.4 or 0.7 to 2.0 or 0.7 to 1.8 or 0.7 to 1.6 or 0.7 to 1.4. In one aspect, the maximum Tan Delta (Tan δmax) occurs between 20° C. and 40° C. or 30° C. and 50° C.
- Another embodiment of the present invention is a method of improving vibration damping of a substrate comprising affixing a plastisol to the substrate, wherein the plastisol comprises a polymeric component and a plasticizer. The plasticizer comprises the esterification product formed by the reaction of formula (I)
-
- R1COOH (I)
and formula (II) - R2COOH (II)
or the corresponding esters, anhydrides, and/or acid chlorides of formula (I) and/or formula (II), with formula (III)
- R1COOH (I)
- wherein R1 and R2 are independently selected from the group consisting of an aromatic or an alkyl-substituted aromatic group having 4 to 10 carbon atoms and a linear, branched, or cycloaliphatic alkyl group having 1 to 9 carbon atoms.
- All of the aspects of the plastisol described herein above can apply to the method of improving vibration damping of a substrate. These aspects include the options for R1 and R2 groups, plasticizer, the amount of mixed esters, polymeric component, the amounts of plasticizer, polymeric component, and other components in the plastisol, plastisol viscosity ranges, second plasticizers, fillers, stabilizers, foaming agents, hollow materials, elastomeric materials, rheology control additives, adhesion promoters, maximum Tan Delta and Tan Delta at 30° C.
- The substrate is not particularly limited. In one aspect, the substrate is metal. In one aspect, the substrate comprises steel. In one aspect, the substrate comprises aluminum. In one aspect, the substrate is part of a wheeled vehicle. In another aspect, the substrate is on the underbody of a wheeled vehicle.
- In one aspect, the method of affixing the plastisol onto the substrate comprises (a) applying the plastisol onto the substrate, (b) fusing the plastisol to produce a plastisol-covered substrate, and (c) cooling the plastisol-covered substrate to ambient temperatures. The method for applying the plastisol onto the substrate is not particularly limited. In one aspect, applying the plastisol onto the substrate comprises coating the substrate with the plastisol. Nonlimiting examples of coating include spray coating and/or extrusion coating.
- In one aspect, the method of affixing the plastisol to the substrate comprises (a) fusing the plastisol into a sheet and (b) adhering the sheet to the substrate.
- In one aspect, the fusing occurs at a temperature ranging from 100° C. to 220° C. for a time period ranging from 1 min to 2 hours. In another aspect, the fusing occurs at a temperature ranging from 140° C. to 180° C. for a time period ranging from 15 min. to 40 min.
- Listed below are non-limiting embodiments.
-
- A1. A plasticizer comprising the esterification product formed by the reaction of formula (I)
- R1COOH (I)
and formula (II) - R2COOH (II)
or the corresponding esters, anhydrides, and/or acid chlorides of formula (I) and/or formula (II), with formula (III)
-
- R1 is selected from the group consisting of phenyl, tolyl, and cyclohexyl and R2 is selected from the group consisting of methyl, ethyl, n-propyl, and i-propyl.
- A2. The plasticizer according to embodiment A1, wherein R2 is selected from the group consisting of n-propyl and i-propyl.
- A3. The plasticizer according to any of embodiments A1-A2, wherein said plasticizer comprises said esterification product formula (X)
- and wherein said esterification product comprises at least 10 weight percent of a mixed ester, based on the total weight of said esterification product; wherein said esterification product comprises at least 15 weight percent, at least 20 weight percent, at least 25 weight percent, at least 30 weight percent, at least 40 weight percent, or at least 50 weight percent of a mixed ester.
-
- B1. A plastisol comprising a polymeric component and a plasticizer. The plasticizer comprises the esterification product formed by the reaction of formula (I)
- R1COOH (I)
and formula (II) - R2COOH (II)
or the corresponding esters, anhydrides, and/or acid chlorides of formula (I) and/or formula (II), with formula (III)
- R1 and R2 are independently selected from the group consisting of an aromatic or an alkyl-substituted aromatic group having 4 to 10 carbon atoms and linear, branched, or cycloaliphatic alkyl group having 1 to 9 carbon atoms.
-
- B2. A plastisol according to embodiment B1, wherein R1 is selected from the group consisting of phenyl, tolyl, and cyclohexyl and R2 is selected from the group consisting of n-propyl, i-propyl, and cyclohexyl.
- B3. A plastisol according to embodiment B2, wherein R1 is phenyl, and R2 is tolyl and the ratio of phenyl to tolyl ranges from 0.05:20 to 20:0.05 based on the total amount of said esterification product; or wherein the ratio of phenyl to tolyl ranges from 0.1:10 to 10:0.1 or 0.1:5 to 5:0.1 or 0.5:1.5 to 1.5:0.5.
- B4. A plastisol according to any of embodiments B1-B3, wherein said plasticizer comprises said esterification product formula (X)
- and wherein said esterification product comprises at least 10 weight percent of a mixed ester, based on the total weight of said esterification product; wherein said esterification product comprises at least 15 weight percent, at least 20 weight percent, at least 25 weight percent, at least 30 weight percent, at least 40 weight percent, or at least 50 weight percent of a mixed ester.
-
- B5. The plastisol according to any of embodiments B1-B2, wherein R1 and R2 are each cyclohexyl.
- B6. The plastisol according to any of embodiments B1-B5, comprising 10 weight percent to 70 weight percent of said plasticizer, 10 weight percent to 70 weight percent of said polymeric component, and 10 weight percent to 80 weight percent of other components, each based on the total weight of said plastisol, and wherein said other components comprise a second plasticizer, fillers, pigments, stabilizers, foaming agents, hollow materials, elastomeric materials, rheology control additives, and/or adhesion promoters; or 15 weight percent to 60 weight percent of said plasticizer, 15 weight percent to 60 weight percent of said polymeric component, and 10 weight percent to 60 weight percent of other components; or 20 weight percent to 45 weight percent of said plasticizer, 20 weight percent to 45 weight percent of said polymeric component, and 10 weight percent to 50 weight percent of other components.
- B7. The plastisol according to any of embodiments B1-B6, wherein the polymeric component comprises polyvinyl chloride, polyvinyl acetate, acrylic polymers, and/or vinyl chloride-containing copolymers; or wherein the polymeric component comprises polyvinyl chloride.
- B8. The plastisol according to embodiment B7, wherein the polymeric component comprises the polyvinyl chloride and the acrylic polymer; the polyvinyl chloride and the polyvinyl acetate; the polyvinyl chloride and the vinyl chloride-containing copolymers comprising acetate; or the polyvinyl chloride and the vinyl chloride-containing copolymers comprising acrylic.
- B9. The plastisol according to any of embodiments B1-B8, wherein the plastisol has a viscosity ranging from 5,000 to 200,000 cP using Brookfield viscosity measurement at 23° C.; wherein the plastisol has a viscosity ranging from 30,000 to 120,000 cP; or wherein the plastisol has a viscosity ranging from 40,000 to 90,000 cP.
- B10. The plastisol according to any of embodiments B6-B9, wherein the second plasticizer comprises phthalates; terephthalates; isophthalates; trimellitates; adipates; cyclohexanedicarboxylates; benzoates; phosphates; diesters of ethylene glycol, propylene glycol, their oligomers, and mixtures thereof; citrates; succinates; alkyl sulfonates; fatty acid esters and epoxidized fatty acid esters; triglycerides and epoxidized triglycerides, optionally substituted; dianhydrohexitol diesters; pentaerythritol-based tetraesters; furan-based esters; other esters; ketals; and/or polymeric plasticizers; or wherein the second plasticizer comprises dioctyl terephthalate, diisooctyl phthalate, di-2-ethylhexyl phthalate, di-2-ethylhexyl terephthalate, tri-2-ethylhexyl trimellitate, di-2-propylheptyl phthalate, diisononyl phthalate, diisodecyl phthalate, diisoundecyl phthalate, ditridecyl phthalate, trioctyl trimellitate, triisononyl trimellitate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, isononyl benzoate, isodecyl benzoate, diisononyl 1,2-cyclohexanedicarboxylate, dioctyl adipate, di-2-ethylhexyl adipate, triethylene glycol di-2-ethylhexanoate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, and/or dibenzoates produced from mixtures of diethylene glycol and dipropylene glycol.
- B11. The plastisol according to any of embodiments B6-B10, wherein the fillers comprise calcium carbonate, magnesium carbonate, silica, clay, mica, graphite, zinc oxide, and/or calcium oxide; or the fillers comprise calcium carbonate.
- B12. The plastisol according to any of embodiments B6-B11, wherein the stabilizers comprise metal soaps, epoxidized oils and epoxidized fatty acid esters, and/or organotin compounds.
- B13. The plastisol according to any of embodiments B6-B12, wherein the foaming agents comprise azodicarbonamide.
- B14. The plastisol according to any of embodiments B6-B13, wherein the hollow materials comprise inorganic or organic glass beads, microbeads, and/or microspheres.
- B15. The plastisol according to any of embodiments B6-B14, wherein the elastomeric materials comprise nitrile-butadiene rubber, natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, butyl rubber, ethylene-propylene-diene monomer (EPDM) rubber, chloroprene rubber, styrenated block copolymers, ethylene-vinyl acetate copolymers, olefinic elastomers, olefinic copolymer elastomers, silicone elastomers, polysulfide elastomers, and/or polyurethane elastomers.
- B16. The plastisol according to any of embodiments B6-B15, wherein the rheology control additives comprise petroleum distillates; mineral oil and/or mineral spirits; fatty acid esters; polyphenyl oligomers; and/or organic solvents.
- B17. The plastisol according to any of embodiments B6-B16, wherein the adhesion promoters comprise polyamidoamines, blocked isocyanates and isocyanurates, silanes, and/or epoxy resins.
- B18. The plastisol according to any of embodiments B1-B17, wherein the fused plastisol has a maximum Tan Delta (Tan δmax) occurring between 20° C. and 50° C. and has Tan Delta at 30° C. (Tan δ30C) ranging from 0.5 to 2.0, when measured on a sample nominally 0.6-0.7 mm thick, 3.2 mm wide, and 10-12 mm long using a Dynamic Mechanical Analyzer with a Tension Clamp at a strain of 0.1% and at a frequency of 1 Hz and a temperature ramp rate of 3° C./min.
- B19. The plastisol according to embodiment B18, wherein the Tan Delta at 30° C. (Tan δ30C) ranges from 0.5 to 1.8 or 0.5 to 1.6 or 0.5 to 1.4 or 0.6 to 2.0 or 0.6 to 1.8 or 0.6 to 1.6 or 0.6 to 1.4 or 0.7 to 2.0 or 0.7 to 1.8 or 0.7 to 1.6 or 0.7 to 1.4.
- B20. The plastisol according to any of embodiments B18-B19, wherein the maximum Tan Delta (Tan δmax) occurs between 20° C. and 40° C. or 30° C. and 50° C.
- C1. A method of improving vibration damping of a substrate comprising affixing a plastisol according to any of claims B1-B20 onto a substrate.
- C2. The method according to embodiment C1, wherein said affixing comprises (a) applying said plastisol onto said substrate; (b) fusing said plastisol to produce a plastisol-covered substrate; and (c) cooling said plastisol-covered substrate to ambient temperatures.
- C3. The method according to embodiments C2, wherein said applying said plastisol onto said substrate comprises coating said substrate with said plastisol.
- C4. The method according to embodiment C3, wherein said coating comprises spray coating and/or extrusion coating.
- C5. The method according to embodiments C1, wherein said affixing comprises (a) fusing said plastisol into a sheet; and (b) adhering said sheet to said substrate.
- C6. The method according to any of embodiments C2-C5, wherein said fusing occurs at a temperature ranging from 100° C. to 220° C. for a time period ranging from 1 min to 2 hours; or at a temperature ranging from 140° C. to 180° C. for a time period ranging from 15 min. to 40 min.
- C7. The method according to any of embodiments C1-C6, wherein said substrate is part of a wheeled vehicle.
- C8. The method according to embodiment C7, wherein said substrate is on the underbody of said wheeled vehicle
- Other embodiments will be apparent to those skilled in the art from consideration of the specification and practice of the embodiments disclosed herein. It will be understood that variations and modifications can be effected within the spirit and scope of the disclosed embodiments. It is further intended that the specification be considered as exemplary only, with a true scope and spirit of the disclosed embodiments being indicated by the following.
Claims (20)
1. A plasticizer comprising the esterification product formed by the reaction of formula (I)
R1COOH (I)
and formula (II)
R2COOH (II)
or the corresponding esters, anhydrides, and/or acid chlorides of formula (I) and/or formula (II), with formula (III)
wherein R1 is selected from the group consisting of phenyl, tolyl, and cyclohexyl and R2 is selected from the group consisting of methyl, ethyl, n-propyl, and i-propyl.
3. A plastisol comprising a polymeric component and a plasticizer wherein said plasticizer comprises the esterification product formed by the reaction of formula (I)
R1COOH (I)
and/or formula (II)
R2COOH (II)
or the corresponding esters, anhydrides, and/or acid chlorides of formula (I) and/or formula (II), with formula (III)
wherein R1 and R2 are independently selected from the group consisting of an aromatic or an alkyl-substituted aromatic group having 4 to 10 carbon atoms and a linear, branched, or cycloaliphatic alkyl group having 1 to 9 carbon atoms.
4. The plastisol according to claim 3 , wherein R1 is selected from the group consisting of phenyl, tolyl, and cyclohexyl and R2 is selected from the group consisting of n-propyl, i-propyl, and cyclohexyl or wherein R1 and R2 are both cyclohexyl.
5. The plastisol according to claim 3 , wherein R1 is phenyl and R2 is tolyl and the ratio of phenyl to tolyl ranges from 0.05:20 to 20:0.05 based on the total amount of said esterification product.
7. The plastisol according to claim 3 , comprising 10 weight percent to 70 weight percent of said plasticizer, 10 weight percent to 70 weight percent of said polymeric component, and 10 weight percent to 80 weight percent of other components, each based on the total weight of said plastisol, and wherein said other components comprise a second plasticizer, fillers, pigments, stabilizers, foaming agents, hollow materials, elastomeric materials, rheology control additives, and/or adhesion promoters.
8. The plastisol according to claim 3 , wherein said polymeric component comprises polyvinyl chloride, polyvinyl acetate, an acrylic polymer, and/or vinyl chloride-containing copolymers.
9. The plastisol according to claim 3 , wherein said second plasticizer comprises of phthalates; terephthalates; isophthalates; trimellitates; adipates; cyclohexanedicarboxylates; benzoates; phosphates; diesters of ethylene glycol, propylene glycol, their oligomers, and mixtures thereof; citrates; succinates; alkyl sulfonates; fatty acid esters and epoxidized fatty acid esters; triglycerides and epoxidized triglycerides, optionally substituted; dianhydrohexitol diesters; pentaerythritol-based tetraesters; furan-based esters; other esters; ketals; and/or polymeric plasticizers.
10. The plastisol according to claim 7 , wherein said fillers comprise calcium carbonate, magnesium carbonate, silica, clay, mica, graphite, zinc oxide, and/or calcium oxide.
11. The plastisol according to claim 7 , wherein said rheology control additives comprise petroleum distillates; mineral oil and/or mineral spirits;
fatty acid esters; polyphenyl oligomers; and/or organic solvents.
12. The plastisol according to claim 3 , wherein said fused plastisol has a maximum Tan Delta (Tan δmax) occurring between 20° C. and 50° C. and has Tan Delta at 30° C. (Tan δ30C) ranging from 0.5 to 2.0, when measured on a sample nominally 0.6-0.7 mm thick, 3.2 mm wide, and 10-12 mm long using a Dynamic Mechanical Analyzer with a Tension Clamp at a strain of 0.1% and at a frequency of 1 Hz and a temperature ramp rate of 3° C./min.
13. The plastisol according to claim 12 , wherein said maximum Tan Delta (Tan δmax) occurs between 20° C. and 40° C.
14. A method of improving vibration damping of a substrate comprising affixing a plastisol onto said substrate, wherein said plastisol comprises a polymeric component and a plasticizer, wherein said plasticizer comprises the esterification product formed by the reaction of formula (I)
R1 COOH (I)
and formula (II)
R2COOH (II)
or the corresponding esters, anhydrides, and/or acid chlorides of formula (I) and/or formula (II), with formula (III)
wherein R1 and R2 are independently selected from the group consisting of an aromatic or an alkyl-substituted aromatic group having 4 to 10 carbon atoms and a linear, branched, or cycloaliphatic alkyl group having 1 to 9 carbon atoms.
15. The method according to claim 14 , wherein said affixing comprises
a. applying said plastisol onto said substrate;
b. fusing said plastisol to produce a plastisol-covered substrate; and
c. cooling said plastisol-covered substrate to ambient temperatures.
16. The method according to claim 15 , wherein said applying said plastisol onto said substrate comprises coating said substrate with said plastisol.
17. The method according to claim 16 , wherein said coating comprises spray coating and/or extrusion coating.
18. The method according to claim 14 , wherein said affixing comprises
a. fusing said plastisol into a sheet; and
b. adhering said sheet to said substrate.
19. The method according to claim 15 , wherein said fusing occurs at a temperature ranging from 100° C. to 220° C. for a time period ranging from 1 min to 2 hours.
20. The method according to claim 14 , wherein said substrate is part of a wheeled vehicle.
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US14/852,681 US20160075855A1 (en) | 2014-09-16 | 2015-09-14 | Polymeric compositions with improved noise suppression |
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US201462050942P | 2014-09-16 | 2014-09-16 | |
US14/852,681 US20160075855A1 (en) | 2014-09-16 | 2015-09-14 | Polymeric compositions with improved noise suppression |
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Family
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US14/852,681 Abandoned US20160075855A1 (en) | 2014-09-16 | 2015-09-14 | Polymeric compositions with improved noise suppression |
US14/852,675 Active 2037-01-08 US10077352B2 (en) | 2014-09-16 | 2015-09-14 | Polymeric compositions with improved noise suppression |
US14/852,662 Abandoned US20160075857A1 (en) | 2014-09-16 | 2015-09-14 | Polymeric compositions with improved noise suppression |
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US14/852,670 Abandoned US20160075858A1 (en) | 2014-09-16 | 2015-09-14 | Polymeric compositions with improved noise suppression |
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US14/852,662 Abandoned US20160075857A1 (en) | 2014-09-16 | 2015-09-14 | Polymeric compositions with improved noise suppression |
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EP (2) | EP3194484B1 (en) |
JP (2) | JP2017528587A (en) |
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CN106687513B (en) | 2020-02-07 |
KR20170055529A (en) | 2017-05-19 |
US10077352B2 (en) | 2018-09-18 |
US20160075856A1 (en) | 2016-03-17 |
EP3194483A1 (en) | 2017-07-26 |
CN106715558B (en) | 2019-06-21 |
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WO2016044238A1 (en) | 2016-03-24 |
EP3194484B1 (en) | 2018-07-25 |
KR102489787B1 (en) | 2023-01-17 |
JP2017534739A (en) | 2017-11-24 |
WO2016044236A1 (en) | 2016-03-24 |
US20160075857A1 (en) | 2016-03-17 |
CN106715558A (en) | 2017-05-24 |
JP2017528587A (en) | 2017-09-28 |
CN106687513A (en) | 2017-05-17 |
KR102479318B1 (en) | 2022-12-19 |
EP3194484A1 (en) | 2017-07-26 |
EP3194483B1 (en) | 2018-12-19 |
US20160075858A1 (en) | 2016-03-17 |
WO2016044238A8 (en) | 2017-04-27 |
WO2016044230A1 (en) | 2016-03-24 |
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