CN103571181A - Noise damping thermoplastic composition - Google Patents
Noise damping thermoplastic composition Download PDFInfo
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- CN103571181A CN103571181A CN201210251294.6A CN201210251294A CN103571181A CN 103571181 A CN103571181 A CN 103571181A CN 201210251294 A CN201210251294 A CN 201210251294A CN 103571181 A CN103571181 A CN 103571181A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The present invention discloses a thermoplastic composition with characteristics of excellent vibration damping and noise inhibition, and a molding product prepared from the thermoplastic composition in a low cost manner. The noise damping thermoplastic composition contains (a) 75-98.9 wt% of fiber reinforcement agent-containing polyamide,; (b) 0.5-10 wt% of an impact modifier, (c) 0.5-5 wt% of nanometer clay, (d) 0.1-10 wt% of polyolefin, and (e) 0-15 wt% of other additives, wherein the component (d) polyolefin is not polyethylene.
Description
Technical field
The present invention relates to have the thermoplastic compounds of improved noise and vibration damping and amortization.Composition of the present invention is especially suitable for use as the parts of the noise that damping transport facility medium power transmission system inner part produces.The invention still further relates to the noise damping goods that obtained by described composition molding.
Background technology
When needing the material of the high rigidity of tool, high strength and low bulk, thermoplastic composite has become the strong lightweight substitute of metal.These matrix materials are especially effectively as the parts in for example automotive, business aircraft, aviation, household electrical appliance, computer hardware, leisure and motion, machine, energy device, buildings or mechanism.
Although the lightweight of thermoplastic composite and custom-made provide effective way for meeting the design optimization of the parts of tight hot system of carving and mechanical system requirement, these parts still present desirable not to the utmost vibration and noise level.For example, engine noise can reach in the main cabin/compartment of the vehicles passenger is done not feel like oneself.Conventionally the vibrational frequency that the power drive system in commercial transportation system produces is in low-frequency range, general about 500Hz-3,100Hz.People's ear can be heard frequency 20Hz to 20, the sound between 000Hz, and wherein the sensitiveest response frequency is about 2,500-3,000Hz.
The quantification of the vibration damping of material conventionally can be by the numerical value statement that is called tangent δ (also referred to as tan δ, loss tangent value or dissipation factor), it is (relevant to the viscous behavior of material that it is defined as out-of-phase modulus, the energy dissipation capability that shows material) than the ratio of the storage modulus of material (relevant to the elastic behavior of material, to show the energy storage capacity of material).Tan δ can be according to dynamic mechanical analysis (DMA) test determination, and what the complex modulus of DMA experimental measurement material dissipated as outer vibrational energy measures.Storage modulus and dissipation factor that typical viscoelastic material changes along with frequency show, intensification on the impact of storage modulus to by temperature-frequency superposition theorem, controlled to fall low-frequency impact similar, this principle can be used to material character to be converted to frequency field from temperature field, and vice versa.The thermoplastic material that presents more effective vibration damping show vibrational energy to other form of energy as the higher conversion of heat energy, they have higher tan δ.
The material of various damping vibrations and noise reducing has been described in the literature.For example, the thermoplastic resin mixing with visco-elasticity elastomerics provides good damping and amortization, but they do not have enough rigidity, modulus intensity or high thermal resistance conventionally, thereby hinder them, be applied to parts such as the power drive system in transport facility etc.
US2007/004842 discloses polymer nanocomposites, the nano-dispersed layer silicate of the polypropylene of its polymeric amide that comprises 55 % by weight-95 % by weight, 4 % by weight-40 % by weight, 1 % by weight-9 % by weight, and not higher than the carboxylation polyolefine of 10 % by weight.The montmorillonite (MMT) that PA6/PP/ that the nano composite material of example comprises the about 55-80/15-40/3-5 of weight ratio is organically-modified and/or the ionomer of <2%, this material has high rigidity and heatproof oxidation performance.
US2004/0225066 discloses the mixture of polymeric amide, polyolefine and Nano filling, and it provides good barrier property in the application of pipeline that comprises the air-conditioning fluid of HFA class and HFC class such as food product pack or for circulating.The polymeric amide that an embodiment of this mixture comprises 60 % by weight-70 % by weight (being PA6 nano composite material), the PP of 20%-30% and the compatilizer of 3%-10%, wherein said compatilizer is preferably the PP/PA multipolymer of maleic anhydride graft.
The people such as Kusmono disclose the nano composite material based on polyamide 6/polypropylene miser, the styrene-ethylene/butylene-styrene (SEBS-g-MA) that it comprises dissimilar close Organic montmorillonite (MMT) and maleic anhydride graft, the fixed weight ratio of wherein said PA6/PP/ parent Organic MMT/SEBS-g-MA mixture is 70/30/4/5.The conclusion that they draw is in PA6/PP/OMMT nano composite material, to add SEBS-g-MA and obtain improved stretching and breaking property.Details is wherein referring to Kusmono et al., Polymer Engineering & Science2010,50 (8), 1493-1504; Composites, Part A:Applied Science and Manufacturing2008,39A (12), 1802-1814; With European Polymer Journal 2008,44 (4), 1023-1039.
Above document, no matter independent or with array configuration, all unexposed the present invention.
In a word, people still need to have good vibration damping and applicable mechanical property and the thermoplastic compounds of high thermal resistance.Such material can be widely used in the field relevant to vibration and noise, and the working temperature of the goods/parts that made by described material can be approximately 150 ° of C or higher.
Summary of the invention
The invention provides noise damping thermoplastic compounds, it comprises mixture or its substantially by compositions of mixtures, or it makes by mixture, and described mixture comprises:
(a) polymeric amide that contains fiber enhancer of approximately 75 % by weight-98.9 % by weight;
(b) impact modifying agent of approximately 0.5 % by weight-10 % by weight;
(c) nanoclay that is selected from montmorillonite, sepiolite and their mixture of approximately 0.5 % by weight-5 % by weight;
(d) polyolefine of approximately 0.1 % by weight-10 % by weight; With
(e) other additive of approximately 0 % by weight-15 % by weight;
Wherein the polyolefine of component (d) is not polyethylene, and described % by weight is the gross weight with respect to described noise damping thermoplastic compounds.
In one embodiment, in noise damping thermoplastic compounds of the present invention, the polymeric amide of component (a) is to be selected from nylon 6,6, nylon 6,6/6, nylon 4,6, nylon 10,10, nylon 10, nylon 12, nylon 12,12, nylon 6,10, nylon 6,12, nylon 6,6/6T, nylon 6T/DT, nylon MXD-6 and their mixture.
In another embodiment, in noise damping thermoplastic compounds of the present invention, the polymeric amide of component (a) is nylon 6,6, nylon 6,6/6, or their mixture.
In another embodiment, in noise damping thermoplastic compounds of the present invention, the polymeric amide of component (a) is nylon 6,6.
In one embodiment, in noise damping thermoplastic compounds of the present invention, the fiber enhancer of component (a) is glass fibre, carbon fiber or contraposition-Kevlar.
In another embodiment, in noise damping thermoplastic compounds of the present invention, the fiber enhancer of component (a) is glass fibre.
In another embodiment, in noise damping thermoplastic compounds of the present invention, with respect to the gross weight of component (a), the amount of the fiber enhancer of component (a) is approximately 20 % by weight-Yue 45 % by weight.
In one embodiment, in noise damping thermoplastic compounds of the present invention, the impact modifying agent of component (b) is styrene-ethylene/butylene-styrene (SEBS-g-MA) multipolymer, ethylene-propylene (EPM-g-MA) multipolymer of maleic anhydride graft, ethylene-propylene-diene (EPDM-g-MA) multipolymer of maleic anhydride graft that is selected from maleic anhydride graft, and their mixture.
In another embodiment, in noise damping thermoplastic compounds of the present invention, the impact modifying agent of component (b) is SEBS-g-MA multipolymer.
In one embodiment, in noise damping thermoplastic compounds of the present invention, the alkyl quaternary ammonium ion that the nanoclay of component (c) comprises 20 % by weight-50 % by weight, described alkyl quaternary ammonium ion contains at least one substituting group, described substituting group is that carbon chain lengths is C12 or longer saturated or undersaturated aliphatic group, and the % by weight of described alkyl quaternary ammonium ion is the gross weight with respect to component (c).
In another embodiment, in noise damping thermoplastic compounds of the present invention, alkyl quaternary ammonium ion is to be selected from: trimethylammonium tallow ammonium, trimethylammonium hydrogenated tallow ammonium, two (hydrogenated tallow) Dimethyl Ammonium, two (2-hydroxyethyl) methyl tallow ammonium, two (2-hydroxyethyl) methyl cocoa ammonium, two (2-hydroxyethyl) methyl vegetable seeds ammonium and their mixtures.
In one embodiment, in noise damping thermoplastic compounds of the present invention, the polyolefine of component (d) be selected from polypropylene (PP), poly-(4-methyl-1-pentene) (PMP), poly 1-butene (PB-1) and their mixture.
In another embodiment, in noise damping thermoplastic compounds of the present invention, the polyolefine of component (d) is homopolymer polypropylene or polypropylene copolymer.
In one embodiment, in noise damping thermoplastic compounds of the present invention, other additive of component (e) is to be selected from antioxidant, thermo-stabilizer, UV light stabilizing agent, ultraviolet absorbers, the tinting material that comprises dyestuff and pigment, lubricant, hydrolysis-resisting agent, releasing agent, mica, flow ability modifying agent, chain propagation agent, fire retardant, and their mixture.
The present invention also provides moulded parts, and it comprises noise damping thermoplastic compounds of the present invention or is made by noise damping thermoplastic compounds of the present invention.
In one embodiment, moulded parts of the present invention is the noise damping parts of transport facility, and wherein said transport facility is automobile, aircraft, train or boats and ships.
In another embodiment, moulded parts of the present invention is the noise damping parts of automobile, and described parts are selected from: for the parts of transmission system, for the parts of air inlet and gas barrier, for the parts of cooling system, for the parts of engine system, for the parts of electronic fuel injection system with for the parts of vehicle body.
In another embodiment, moulded parts of the present invention is the noise damping parts of electric equipment products, described electric equipment products are to be selected from power tool, electro-motor, and household electronic products comprises washing machine, air-conditioning, blower fan, moisture trap, microwave oven, refrigerator and refrigerator-freezer.
The present invention also provides the purposes of moulded parts of the present invention as the noise damping parts in transport facility, and wherein said transport facility is automobile, aircraft, train, or boats and ships.
Noise damping thermoplastic compounds of the present invention has unexpected improvement aspect vibration damping, and can low cost production.In addition, composition of the present invention also has at least 75% the mechanical strength of its resinous substrates (being component (a) itself) and makes them be suitable for working temperature higher than the high thermal resistance of the application of 150 ° of C.By composition molding of the present invention noise damping goods, using its parts as the power drive system in transport facility particularly useful.
With reference to the following description, embodiment and the claims of enclosing, various further features of the present invention, to consider with advantage will be clearer.
Accompanying drawing explanation
Fig. 1 is presented at 150 ° of C, and the damping loss factor of the matrix material of C1-C7 (tan δ) is at the chart of 50-3100Hz range of frequency.
Fig. 2 is presented at 150 ° of C, and the damping loss factor of the matrix material of C1 and E1-E10 (tan δ) is at the chart of 50-3100Hz range of frequency.
Embodiment
Unless otherwise indicated, herein mentioned all publications, patent application, patent and other reference all quoted and added herein with its integral body, at this as it is set forth in full.
Unless otherwise defined, all technology used herein and scientific terminology have the identical meanings that those skilled in the art of the invention understand conventionally.In the situation that conflicting, with this specification sheets and the definition comprising in it, be as the criterion.
Unless otherwise indicated, all per-cent, umber, ratio etc. are all by weight.
In this article, term " by ... make " be equal to " comprise/draw together ".Term used herein " comprises ", " comprising ", " containing ", " having ", " having " or its any other variant are intended to contain nonexcludability and comprise.For example, the composition, technique, method, goods or the equipment that comprise/draw together a series of key elements might not only limit to those key elements, but can also comprise these compositions, technique, method, goods or equipment other key element that clearly do not enumerate or intrinsic.
Term " by ... form " do not comprise any key element of clearly not enumerating, step or composition.If there is in the claims, such term will make claim be limited to described material and not comprise the material of not describing, but still comprises the impurity relevant to described material conventionally.When term " by ... form " appear at the characteristic of claim, but not immediately during preamble, the key element that it only limits to set forth in characteristic; Other key element is not got rid of from this claim integral body.
Term " substantially by ... form " for also comprising/draw together composition, method or the device of other material, step, feature, component or key element outside literal the above those materials, step, feature, component or the key element of definite division, prerequisite is essential characteristic and the novel feature that these other materials, step, feature, component or key element substantially do not affect invention required for protection.Term " substantially by ... form " in " comprise/draw together " and " by ... form " between a rank.
Term " substantially do not comprise/draw together " or " being substantially devoid of " certain/a little components represent composition of the present invention, with respect to the gross weight of described noise damping thermoplastic compounds, should comprise lower than 1 % by weight, preferably this component of 0 % by weight.
Term " comprise/draw together " intention comprise term " substantially by ... form " and " by ... composition " embodiment of containing.Similarly, term " substantially by ... form " intention comprise term " by ... form " embodiment that contains.
When providing quantity, concentration or other numerical value or parameter with scope, preferable range or a series of upper limit preferred value and lower limit preferred value, should understand it and specifically disclose the formed all scopes of any logarithmic value by any larger scope limit value or preferred value and any less scope limit value or preferred value, and no matter whether scope is disclosed respectively.For example, when describing the scope of " 1 to 5 ", described scope is understood to include the scopes such as " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to 5 ", " 1 to 3 and 5 ".Unless otherwise indicated, describe numerical range part herein, described scope intention comprises all integers and the mark in scope end value and scope.
When term " about " is used for describing the endpoint value of numerical value or scope, disclosed content is understood to include occurrence or the end value of indication.
In addition, unless clearly represented contrary, " or (or) " refers to " or (or) " of pardon, but not exclusive " or (or) ".For example, below arbitrary condition all applicable elements A "or" B:A be that true (or existence) and B are false (or not existing), A is that false (or not existing) and B are true (or existence), and A and B are very (or existence).
In addition, the indefinite article before key element of the present invention or component " " and " a kind of " intention represent that appearance (the occurring) number of times of described key element or component does not have restricted.Therefore " one " or " a kind of " be understood to include a kind of or at least one, unless clearly represented that quantity is odd number, otherwise the described key element of singulative or component also comprise plural situation.
In specification sheets of the present invention and/or claims, term " homopolymer " refers to the polymkeric substance being obtained by a kind of monomer polymerization; " multipolymer " refer to by two or more monomer polymerizations and polymkeric substance.Described multipolymer comprises copolymer, terpolymer or multiple copolymer.
When describing some polymkeric substance, should understand applicant sometimes and describe described polymkeric substance by the monomer for the preparation of polymkeric substance or for the preparation of the amount of monomer of polymkeric substance.Yet, this description may not comprise for describing the concrete name of final polymkeric substance, or may not comprise the term of method-restriction-product, any this type of statement for monomer and amount thereof, be interpreted as representing the polymkeric substance comprise those monomers (being the copolymerization units of those monomers) or amount of monomer, with and corresponding polymkeric substance and composition.
Embodiment of the present invention, be included in any other embodiment of embodiment of the present invention described in summary of the invention part and the following stated herein, can at random combine, and the moulded parts that in embodiment, the statement of variable is applicable to noise damping thermoplastic compounds of the present invention and is made by it.
Unless otherwise indicated, material of the present invention, method and embodiment are only illustrative, and not restrictive.Only described applicable method and material herein, but can use and those similar or equivalent method and materials described herein when implementing or test is of the present invention.
The present invention is below described in detail in detail.
component (a) polymeric amide and fiber enhancer
Polymeric amide is the base resin as noise damping thermoplastic compounds of the present invention.
Coming from the polymeric amide of monoreactant (as lactan, aminocarboxylic acid ester) and the multipolymer of these compositions (being called as AB type polymeric amide) can be referring to Nylon Plastics (Melvin L.Kohan volume, 1973, John Wiley and Sons, Inc.), and can comprise that fatty polyamide is as nylon 11 (poly--ω-undecanoyl amine), nylon 12 (poly--ω-12 carboxamide), and composition thereof or multipolymer.The known polymeric amide of another kind being made by diamines and diacid condensation is called as AABB type polymeric amide, comprise that fatty polyamide is as nylon 6,6, nylon 6,10 (polyhexamethylene sebacamide), nylon 6,12 (poly-12 carbon two acyl hexanediamines), nylon 4,6 (nylon 46s) and nylon 12,12 (poly-12 carbon two acyl 12 carbon diamines).Other non-fatty polyamide, comprises that nylon MXD-6 (poly-(hexanedioyl m-xylene diamine)), poly-hexamethylene terephthalamide (nylon 6T), poly-paraphenylene terephthalamide's 2 methyl pentamethylenediamine (nylon DT), poly-(paraphenylene terephthalamide-2 methyl pentamethylenediamine) (nylon MST), poly-6I hexamethylene isoterephalamide (nylon 6I) and poly-(isophthaloyl-2 methyl pentamethylenediamine) (nylon M5I) can be applicable to.
The example of polyamide copolymer comprises: nylon 6,6/6, nylon 6,6/6,10, nylon 6,6/6T, nylon 6,6/6I, nylon 6T/DT, nylon 6T/6I/6,6, nylon 6T/6I/6,10, nylon 6T/6I and nylon 6T/MST.
Because polymeric amide and technique thereof are well known to a person skilled in the art, for style of writing is omitted its associated description for purpose of brevity herein.
In one embodiment, be applicable to polymeric amide of the present invention and comprise nylon 6,6, nylon 6,6/6, nylon 4,6, nylon 10,10, nylon 10, nylon 12, nylon 12,12, nylon 6,10, nylon 6,12, nylon 6,6/6T, nylon 6T/DT, nylon MXD-6, and composition thereof.
In another embodiment, polymeric amide of the present invention is nylon 6,6, nylon 6,6/6, or its mixture.
In above-mentioned polyamide resin, number-average molecular weight is approximately 7,000-30, and those of 000 are preferred in the present invention.
With respect to the gross weight of component (a), in the component (a) in noise damping thermoplastic compounds of the present invention, the consumption of polymeric amide is approximately 55 % by weight-Yue 80 % by weight, or approximately 60 % by weight-Yue 75 % by weight.
To noise damping thermoplastic compounds of the present invention, adding fiber enhancer is to improve its mechanical strength (as tensile strength, flexural strength), and in order to suppress the contraction of layered product.
The example of fiber enhancer comprises: inorganic fibre, and for example glass fibre, carbon fiber, graphite fibre, silicon-aluminum fiber, Zirconium oxide fibre, ceramic fiber, steel fiber are as the fiber of stainless steel, aluminium, titanium, copper or brass; And organic fibre, for example contraposition-Kevlar, position-Kevlar, fluororesin fiber or liquid crystal aromatics fiber.Can use the one or two or more in them, or its combination.With regard to reinforced effects, described fiber enhancer be preferably glass fibre, carbon fiber or contraposition-Kevlar as
fiber (being prepared by du pont company).In view of commercially available property and cost, glass fibre is preferred.
In one embodiment, in noise damping thermoplastic compounds of the present invention, the fiber enhancer of component (a) is glass fibre, carbon fiber, or contraposition-Kevlar.In another embodiment, in noise damping thermoplastic compounds of the present invention, the fiber enhancer of component (a) is glass fibre.
For described glass fibre, can use conventional those glass fibre for thermoplastic resin.In these glass fibre, the chopped strand preferably being made by E-glass (non-alkali glass) (chopped strand).The fiber diameter of described fiber enhancer is not particularly limited, and for example 1-100 μ m, is preferably about 3-30 μ m, and is more preferably about 5-15 μ m.The average fiber length of described fiber enhancer is also not particularly limited, and is about 2-4mm for example.
The example of applicable glass fibre comprises NEG275H (Nippon Electric Glass Co., Ltd. produce); Produce with ChopVantageTM(PPG Industries Fiber Glass).In addition, described fiber enhancer can be as required for example, by (being used surface treatment agent, with the functional group classification of compound, comprise compound containing epoxy group(ing), containing acrylic acid compound, compound containing isocyanic ester, silane compound or containing the compound of titanate (ester)) carry out surface treatment.Described fiber enhancer can carry out preliminary surface treatment by above-mentioned surface treatment agent, or can be by adding surface treatment agent to carry out surface treatment when preparing material.Described glass fibre preferably uses silane compound (also referred to as silane coupling agent) to carry out surface treatment, to strengthen the cementability to described polyamide resin.
The fiber enhancer of component (a) can any stage to its molding be mixed into described polyamide resin in the preparation from described polyamide resin (polycondensation phase).Described fiber enhancer is preferably added in forcing machine in the process of polyamide resin described in molding, and integrates with described polyamide resin melting therein.
With respect to the gross weight of component (a), in the component (a) of noise damping thermoplastic compounds of the present invention, the consumption of fiber enhancer is approximately 20 % by weight-Yue 45 % by weight, or approximately 25 % by weight-Yue 40 % by weight.
In noise damping thermoplastic compounds of the present invention, the weight ratio between described polymeric amide and described fiber enhancer is that about 55:45 is to about 80:20; Be more preferably that about 60:40 is to about 75:25.When the amount of described fiber enhancer is greater than the amount (being >50 % by weight) of described polymeric amide, it is bad that the mobility of resulting composition often becomes.
Gross weight with respect to noise damping thermoplastic compounds, in noise damping thermoplastic compounds of the present invention, the consumption of component (a) is approximately 75 % by weight-Yue 98.9 % by weight, or approximately 80 % by weight-Yue 98 % by weight, or approximately 83 % by weight-Yue 97 % by weight, or approximately 85 % by weight-Yue 96 % by weight.
component (b) impact modifying agent
To adding impact modifying agent in noise damping thermoplastic compounds of the present invention, be to improve its shock-resistance and fracture toughness property and ductility.
Applicable impact modifying agent is functionalized segmented copolymer, also referred to as reactive modifier.The example of known segmented copolymer (being elastomerics) comprises styrene-ethylene/butylene-styrene (SEBS) multipolymer, styrene-butadiene-styrene (SBS) multipolymer, ethylene-propylene (EPM) multipolymer and ethylene-propylene-diene (EPDM) multipolymer.Functional group can be introduced into segmented copolymer by graft reaction as maleic anhydride (MA) and/or methyl propenoic acid glycidyl base ester (GMA), and this is by increasing term " g-MA " after the segmented copolymer name in abbreviation or " g-GMA " represents.For example, " SEBS-g-MA " represents the SEBS multipolymer of maleic anhydride graft; " EPM-g-GMA " represents the EPM multipolymer of methyl propenoic acid glycidyl base ester grafting.These reactive modifiers can make by any applicable method well known by persons skilled in the art, or can buy from commercial source.
Be not limited to theory, think that elastomeric reactive functional groups maleinization or that methyl propenoic acid glycidyl base is ester modified can interact with the terminal amino group of polymeric amide and give thermoplastic compounds of the present invention better consistency.
Preferably, in composition of the present invention, impact modifying agent used is the impact modifying agent (being the impact modifying agent of maleic anhydride graft) of maleinization, include but not limited to SEBS (SEBS-g-MA) multipolymer of maleic anhydride graft, EPDM (EPDM-g-MA) multipolymer of EPM (EPM-g-MA) multipolymer of maleic anhydride graft, maleic anhydride graft, and composition thereof.
In one embodiment, in noise damping thermoplastic compounds of the present invention, the impact modifying agent of component (b) is styrene-ethylene/butylene-styrene (SEBS-g-MA) multipolymer of maleic anhydride graft.
For example, one of reactive impact modifying agent (b) being applicable to is SEBS-g-MA, can be from Kraton Polymer US LLC with trade(brand)name
fG1901G is commercially available.
Gross weight with respect to described noise damping thermoplastic compounds, in noise damping thermoplastic compounds of the present invention, the consumption of the impact modifying agent of component (b) is approximately 0.5 % by weight-Yue 10 % by weight, or approximately 0.5 % by weight-Yue 5 % by weight, or approximately 0.5 % by weight-Yue 2.5 % by weight.
component (c) nanoclay
In order to improve the mechanical property of described noise damping thermoplastic compounds, in noise damping thermoplastic compounds, use the nanoclay of component (c).
The form of nanoclay can be fine-fibered, platelet, or other shape, and diameter is about 1-5000nm or about 10-3000nm.Layer thickness is less than about 10nm conventionally, or is less than about 5nm, or is less than about 2nm.Described nanoclay can be natural, or synthetic making.Described nanoclay comprises interlayer cation as alkali and alkaline earth metal ions positively charged ion.
Natural nanoclay comprises sepiolite class and smectite class clay.While using herein, term " sepiolite class " comprises attapulgite and sepiolite itself.
Sepiolite (Mg
4si
6o
15(OH)
26 (H
2o)) be because of its filamentary structure, to present the hydrated magnesium silicate filler of high length-diameter ratio.Sepiolite unique in silicate consists of the crystal grain like long slab, and wherein silicon-dioxide chain is the major axis that is parallel to fiber.
Attapulgite (also referred to as polygorskite) is in structure with chemically almost identical with sepiolite, and just attapulgite has a little less structure cell.
Representational smectite class clay comprises montmorillonite, hectorite, bentonite, Bei Baoshi, volkonskoite, saponite, sauconite, rich magnesium montmorillonite etc.
Montmorillonite ((Na, Ca)
0.33(Al, Mg)
2(Si
4o
10) (OH)
2nH
2o) being the hydrated sodium silicate calcium magnalium oxyhydroxide with the adjacent bonding coat of multilayer, is the gathering of each platelet-like particle.Montmorillonitic clay generally can be processed swelling to increase the interval between its platelet-like particle by swelling agent.
The preferred nanoclay of particular form not, i.e. fine-fibered or platelet form, as long as it can easily be scattered in thermoplastic melt.If desired, granularity can be passed through at hammer mill, supper micron mill, wet wheeling machine, or pulverizes and obtain in other shredding unit.
Preferably, in noise damping thermoplastic compounds as herein described, the nanoclay of contained component (c) is to be selected from sepiolite, montmorillonite and composition thereof.More preferably, in noise damping thermoplastic compounds as herein described, the nanoclay of contained component (c) is montmorillonite.
In noise damping thermoplastic compounds of the present invention, particularly preferably use through organically-modified nanoclay.The surface that term " modification " refers to nanoclay by organic compound for example, as ammonium compound or other compound treatment (, so that its surface polarity diminish) thus replace the original metallic cation of its interlayer.
In one embodiment of the invention, in composition of the present invention, nanoclay (c) used is organically-modified clay (being sometimes referred to as " organic clay ").In a preferred embodiment of the invention, the alkyl quaternary ammonium ion that described nanoclay (c) comprises approximately 20 % by weight-50 % by weight, it contains at least one substituting group, and described substituting group is that carbon chain lengths is C12 or longer saturated or undersaturated aliphatic group.
Be applicable to for modified Nano clay season alkyl ammonium compound example comprise without limitation trimethylammonium tallow ammonium halide, trimethylammonium hydrogenated tallow ammonium halide, two (hydrogenated tallow) dimethyl ammonium halide, two (2-hydroxyethyl) methyl tallow ammonium halide, two (2-hydroxyethyl) methyl cocoa ammonium halide, two (2-hydroxyethyl) methyl vegetable seeds ammonium halide etc.
In one embodiment, in noise damping thermoplastic compounds of the present invention, the nanoclay of component (c) is the montmorillonite through season alkyl ammonium compound modification.
The nanoclay that can obtain has different forms, for example, and nanoclay itself, or in polymeric matrix, be mixed with the enriched material of nanoclay or the form of masterbatch of relative high density.The organically-modified nanoclay of commercially available acquisition includes but not limited to the Pangel from Tolsa Group
tMb20 sepiolite clay (through the modification of dimethyl benzyl alkyl ammomium chloride) and
i.44P montmorillonitic clay Nanocor Inc (IL, USA) (through the modification of dimethyl dialkyl (C14-18) ammonium halide).Nanocor Inc also provides nanoclay-polyolefin resin masterbatch product, comprises nano-Max
tM-PP, nanoMax
tM-PE etc.
Gross weight with respect to described noise damping thermoplastic compounds, the consumption of the nanoclay of component (c) in noise damping thermoplastic compounds of the present invention is approximately 0.5 % by weight-Yue 5 % by weight, or approximately 1 % by weight-Yue 4.5 % by weight, or approximately 2 % by weight-Yue 4 % by weight.
component (d) polyolefine
In noise damping thermoplastic compounds of the present invention, add a small amount of polyolefine and unexpectedly can improve significantly the damping capacity under high temperature.
While using in this article, term " polyolefine " refers to the polymkeric substance being obtained by the olefinic monomer of at least 80 % by weight.The polyolefinic example being applicable to comprise without limitation polypropylene (PP), poly-(4-methyl-1-pentene) (PMP), poly 1-butene (PB-1), and composition thereof.
Implementing when of the present invention, to tend to use commercially available polyolefine, be preferably homopolymer polypropylene or polypropylene copolymer (be referred to as " PP ＂).
Alpha-olefin comonomer that polypropylene copolymer can comprise the ethene of approximately 1 % by weight-20 % by weight or contain 4-16 carbon atom and composition thereof.The example of alpha-olefin comprises butylene, amylene, hexene, octene and 4 methyl 1 pentene copolymer.In addition, polypropylene copolymer also can comprise polar monomer as maleic acid ester, acrylate and methacrylic ester.
In one embodiment, in noise damping thermoplastic compounds of the present invention, described polyolefine (d) is homopolymer polypropylene and polypropylene copolymer.
In another embodiment, in noise damping thermoplastic compounds of the present invention, the polyolefine of described component (d) is not polyethylene (PE).
PP can prepare to produce the different PP of stereo-sequence by typical Ziegler-Natta or metallocene catalyst.Applicable PP comprises the crystalline polymers amount solid phase prod that the propylene of at least 80 % by weight obtains by high pressure or low pressure process polymerization.This type of polyacrylic example is isotactic polyprophlene and syndiotactic polypropylene.The chain rule of isotactic polyprophlene contributes to its high melting temperature (Tm) and degree of crystallinity, makes them ideally for noise damping thermoplastic compounds of the present invention.
The polyacrylic commercially available example being applicable to comprises that Total polypropylene 3365, SABIC that Total Petrochemicals USA, Inc produce produce
the ExxonMobil that PP570P and Exxon Chemical produce
tMpP2252E1.
Gross weight with respect to described noise damping thermoplastic compounds, in noise damping thermoplastic compounds of the present invention, the polyolefinic consumption of component (d) is approximately 0.1 % by weight-Yue 10 % by weight, or approximately 0.3 % by weight-Yue 8 % by weight, or approximately 0.5 % by weight-Yue 5 % by weight, or approximately 0.8 % by weight-Yue 3.6 % by weight.
other additive of component (e)
Noise damping thermoplastic compounds of the present invention can also comprise a small amount of additive of optional existence, and described additive is commonly used and known in polymer arts.The example of additive comprises without limitation: antioxidant, thermo-stabilizer, UV light stabilizing agent, the tinting material that comprises dyestuff and pigment, lubricant, hydrolysis-resisting agent, releasing agent, mineral, mica, flow ability modifying agent and chain propagation agent.The content of these additives in described composition is generally approximately 0.01 % by weight-Yue 15 % by weight, or approximately 0.01 % by weight-Yue 10 % by weight, basic and the novel feature of described composition as long as they do not detract, and the performance of described composition is not had to significant disadvantageous effect.
Noise damping thermoplastic compounds of the present invention is the mixture of consolute, in wherein all polymeric constituents are scattered in each other fully, and all non-polymeric ingredients are scattered in polymeric matrix well and with its combination, thereby this mixture forms the integral body of homogeneous.Can adopt any consolute method to mix polymeric constituent of the present invention and non-polymeric ingredients.For example, polymeric constituent and non-polymeric ingredients can be added in consolute machine at the mode with disposable single addition step or Multistep feeding, for example, single screw rod or twin screw extruder; Mixing machine; Single screw rod or twin screw kneader; Haake mixing machine, Brabender mixing machine, Banbury mixing machine, or mixing roll mill, then consolute.When adding polymeric constituent and non-polymeric ingredients in substep mode, first add a part of polymeric constituent and/or non-polymeric ingredients consolute, then add remaining polymeric constituent and non-polymeric ingredients, then consolute is until obtain well-mixed composition.
Also described the method for preparing goods herein, it comprises the step that makes noise damping thermoplastic compounds of the present invention moulding.The example of goods is vibration damping and noise reducing structure." moulding " refers to any forming technique, for example, extrusion molding well known by persons skilled in the art or any molding methods, comprise for example injection moulding, injection moulding altogether, compression moulding, cross molding (overmolding), profile extrusion (profile extrusion), blowing, vacuum forming and moulding molding (form molding).For example, noise damping thermoplastic compounds of the present invention can be in layered product, and this product is the parts of trolley part and other transport facility.
The specific examples of the application of noise damping thermoplastic compounds of the present invention can comprise and automobile and parts or the product as relevant in aircraft, train and boats and ships of other transport facility.More specifically, the molded parts for automobile comprises: for the parts of transmission system for example bearing support pedestal, variator shade assembly and case of transmission; For the parts of air inlet and outlet device for example air inlet-outlet pipe, air filter housing, intake manifold, exhaust manifold, exhaust snubber, exhaust gas recirculation housing, vapor pipe and three unique catalytic converter housing; For the parts of cooling system for example guard shield, container cover, scatterer end water tank, side cooler case, charged air-cooler and thermostat housing; For the parts of engine system for example hood, engine support, machine oil storage tank, oil pan, machine oil snubber, oil strainer, cylinder cover cap, timing belt cover, hinge clip, splicing tpae and support of motor or housing; For the parts of electronic fuel injection system for example fuel tank, auxiliary fuel tank, fuel reserve tank, fuel feeding assembly, oil feed pipe, purolator, hay tank, terminal box, resonator, relay box, junctor, sinuflo tube and shield cap; For the parts of vehicle body for example engine shield and luggage-boot lid.
In addition, the present invention can be applied to following product, as steering knuckle (steering knuckle), control arm, mold support (cast cradle), mold instrument plate-girder (cast instrument panel beam), or mold any structure or sealing.And the present invention is useful for following application: for the Traction Drive engine of hybrid electrically and pure electric propulsion system, and for the sealer/outer cover of high voltage connector.
In addition, noise damping thermoplastic compounds of the present invention also can comprise and power tool as electric equipment products, electro-motor, and household electronic products comprises washing machine, air-conditioning, blower fan, moisture trap, microwave oven, the relevant parts such as refrigerator and refrigerator-freezer.
The application of other tool potentiality comprise be applied in use produce can hear and any structure of undesirable noise, for example, manufacturing machine, railway equipment, passenger plane, boats and ships etc.But the present invention is particularly suitable for following molded parts, it holds or seals the turning unit of one or more generation noises of transportation means.
Embodiment
Abbreviation " E " expression " embodiment ", " C " expression " comparative example ", numeral has been prepared described composition in which embodiment thereafter.All embodiment and comparative example are all prepared in a similar manner and test.Except as otherwise noted, per-cent is weight percent.
material
(a) PA/GF: the commodity of being produced by DuPont Co. are by name
the polyamide 6 of the reinforcing glass fiber that comprises 35 % by weight of PLS95G35,6.The general processing temperature of its melt extrusion molding and density are respectively 280-300 ° of C and 1.42g/cm
3.
(b) SEBS-g-MA:Kraton Polymer, USA produce, and commodity are by name
fG1901G.
fG1901G is the transparent line style ternary block polymer of styrene-based and ethylene/butylene, and wherein polystyrene content is 30%, passes through the maleic anhydride modified of approximately 1.4 % by weight ~ 2.0 % by weight.Its MFI and density are respectively 14-28g/10min (under 230 ° of C and 5Kg load) and 0.91g/cm
3.Melting mixing
the high processing temperature that FG1901G Shi， manufacturer is recommended should be no more than 280 ° of C.
(c) OMMT: the commodity purchased from Nanocor Inc., USA are by name
i.44P organically-modified montmorillonite.The montmorillonite that this nanoclay comprises 60-70 % by weight, and the dimethyl dialkyl in order to modification of 30 % by weight-40 % by weight (C14-18) ammonium ion.Nanomer density is I.44P about 1.4g/cm
3, on average dry granularity is 15-25 micron, and can be scattered in twin screw compounding machine nano level.
(d1) commodity that PP:Total Petrochemicals USA.Inc. produces are by name
3365 polypropylene.General processing temperature, MFI and the density of its melt extrusion molding is respectively 204-260 ° of C, 3.80g/10min (under 230 ° of C and 2.16Kg load) and 0.905g/cm
3.
(d2) polyethylene of the commodity LB7000 by name that PE:LG Chem Ltd. produces.General processing temperature, MFI and the density of melt extrusion molding is respectively 280-330 ° of C, 7.0g/10min (under 190 ° of C and 2.16Kg load) and 0.917g/cm
3.
the general blend method of embodiment and comparative example
By PA/GF and OMMT oven drying 12 hours under 80 ° of C.The amount of the component of each embodiment and comparative example (a)-(e) is clearly listed in table 1-4.
Utilize twin screw extruder (Eurolab 16, Thermo Prism, England) by the thermoplastic composite of the melt blended embodiment of making and comparative example, to obtain granular respective mixtures.
For the forcing machine with 10 heating module structures, by the Temperature Setting of forcing machine, be 220/280/280/280/280/280/280/280/280/280 ° of C.Die head temperature is 265-275 ° of C, and screw speed is 300-430rpm.Feeder speed is set as 1 ~ 5Kg/ hour.
general molding step
Before molding, by the particle drying of extruding to moisture content lower than 40ppm.In order to test mechanical property, according to ISO3167, at Sumitomo100Ton molding forming machine (screw diameter 32mm; Nozzle diameter 5mm) the upper multiduty specimen of molding.Machine barrel temperature is set as 280 ° of C and die temperature is 100 ° of C.Multi-usage specimen has basic dumbbell shape, long 150mm, the wide 10mm of interlude, thick 4mm, long 80mm.
testing method
(i) damping loss factor (tan δ): the dynamic mechanical analyzer (DMA) that uses PerkinElmer, Inc. to produce, in some fixed frequencies (0.5,1,2,5 and 10Hz), with frequency multichannel pattern (frequency multiplexing mode), analyze rectangle specimen 17.5mmx12.8mmx0.76mm (length x width x thickness), its temperature range is between 0 ° of C-200 ° of C, and rate of heating is 5 ° of C/min.Utilize single-cantilever flexural deformation mode treatment specimen.Then by Time-temperature-stack (TTS) algorithm, data reduction measured under 150 ° of C is predicted in the range of frequency of not directly measuring as the acoustics in 50Hz-3100Hz or vibration damping character.
(ii) damping improves (Δ Tan δ): by following equation, calculate damping and improve:
Damping improves (Δ Tan δ) %=[(T
n-T
0)/T
0] x100
T wherein
0the Tan δ of reference example under CF, and
T
nthis routine Tan δ relatively under same frequency.
(iii), according to ISO527:1993 (E), on general purpose material test machine Instron5567, measure tensile modulus.
(iv) according to ISO178:2001 (E), tested for flexural modulus on general purpose material test machine Instron5567.
In following examples, further limit embodiment of the present invention.The composition of embodiment and comparative example and evaluation result are shown in table 1-4.
table 1
| Unit | C1 | C2 | C3 | C4 | C5 | C6 | C7 | |
| (a)PA/GF(65/35) | % | 100.0 | 97.8 | 99.1 | 96.9 | 97.5 | 96.6 | 95.3 |
| (b)SEB S-g-MA | % | - | - | 0.9 | 0.9 | - | 0.9 | - |
| (c)OMMT | % | - | - | - | - | 2.5 | 2.5 | 2.5 |
| (d1)PP | % | - | 2.2 | - | 2.2 | - | - | 2.2 |
| Amount to | % | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Tanδ2500Hz | x10 -2 | 2.2 | 2.6 | 2.6 | 3.2 | 3.2 | 3.2 | 3.3 |
| ΔTanδ2500Hz | % | - | 18.2 | 18.2 | 45.5 | 45.5 | 45.5 | 50.0 |
| Tensile modulus | Mpa | 9100 | 9197 | 9302 | 8973 | 10042 | 9594 | 9546 |
| Modulus in flexure | Mpa | 8428 | 8488 | 8488 | 8299 | 9019 | 8843 | 8918 |
By the result of table 1, to draw a conclusion, be obvious.
C2-C4 and C1 are contrasted at the Tan of 2500Hz δ (being damping loss factor), and the vibration damping that the polyolefinic compositions table of the impact modifying agent that comprises component (b) or component (d) reveals is slightly improved (being <20%); And the compositions table of the polyolefinic C4 of the impact modifying agent that comprises component (b) and component (d) reveals approximately 50% damping improvement.
C5-C7 and C1 are contrasted at the Tan of 2500Hz δ, composition only comprises component (c) nanoclay, or except the nanoclay of component (c), also comprise the similar damping improvement that component (b) impact modifying agent or the polyolefinic composition of component (d) can obtain about 45%-50%.The Tan δ of C1-C7 is shown in Fig. 1 the figure of the frequency of TTS conversion.
The tensile modulus that it should be noted that C2-C7 is similar to those data of C1 with flexural modulus data, and this is attributable to the component (a) that thermoplastic compounds comprises relative high-content, the polymeric amide strengthening through glass fibre.
table 2
| Unit | C1 | E1 | E2 | E3 | E4 | E5 | |
| (a)PA/GF(65/35) | % | 100.0 | 94.4 | 91.0 | 89.0 | 87.5 | 85.5 |
| (b)SEBS-g-MA | % | - | 0.9 | 3.5 | 3.5 | 3.5 | 3.5 |
| (c)OMMT | % | - | 2.5 | 2.0 | 4.0 | 2.0 | 4.0 |
| (d1)PP | % | - | 2.2 | 3.5 | 3.5 | 7.0 | 7.0 |
| Amount to | % | 100 | 100 | 100 | 100 | 100 | 100 |
| Tanδ2500Hz | x10 -2 | 2.2 | 6.2 | 5.8 | 4.6 | 4.7 | 4.4 |
| ΔTanδ2500Hz | % | - | 181.8 | 163.6 | 109.1 | 113.6 | 100.0 |
| Tensile modulus | Mpa | 9100 | 9428 | 8421 | 8595 | 7513 | 8975 |
| Modulus in flexure | Mpa | 8428 | 8137 | 6806 | 7225 | 6488 | 7707 |
table 3
| Unit | C-1 | E6 | E7 | E8 | E9 | E10 | |
| (a)PA/GF(65/35) | % | 100.0 | 93.5 | 95.9 | 94.5 | 98.0 | 96.9 |
| (b)SEB S-g-MA | % | - | 1.0 | 1.8 | 4.4 | 0.9 | 0.9 |
| (c)OMMT | % | - | 2.0 | 1.4 | 0.7 | 0.7 | 1.8 |
| (d1)PP | % | - | 3.5 | 0.9 | 0.4 | 0.4 | 0.4 |
| Amount to | % | 100 | 100 | 100 | 100 | 100 | 100 |
| Tanδ2500Hz | x10 -2 | 2.2 | 4.8 | 4.6 | 4.4 | 4.2 | 6.4 |
| ΔTanδ2500Hz | % | - | 118.2 | 109.1 | 100.0 | 90.9 | 190.9 |
| Tensile modulus | Mpa | 9100 | 7965 | 9660 | 8399 | 9284 | 9401 |
| Modulus in flexure | Mpa | 8428 | 6855 | 7893 | 7322 | 8085 | 8138 |
By the result of table 2-3, to draw a conclusion, be obvious.
Tan δ at 2500Hz and damping improvement data are contrasted, the noise damping thermoplastic compounds of E1-E10 of the present invention, the PP (being the polyolefine of component (d)) that wherein comprises the SEBS-g-MA (being the impact modifying agent of component (b)) of 0.9 % by weight-4.4 % by weight, the OMMT (being the nanoclay of component (c)) of 0.7 % by weight-4 % by weight and 0.4 % by weight-7 % by weight, compare with C1, effectively provide the damping of about 90%-190% to improve.The Tan δ of E1-E10 and C1 is shown in Fig. 2 the figure of the frequency of TTS conversion.
The tensile modulus of E1-E10 and C1 and flexural modulus data are contrasted, in noise damping thermoplastic compounds, comprise OMMT, SEBS-g-MA and PP and show some impacts on mechanical property.But noise damping thermoplastic compounds of the present invention is compared with C1, still retain the tensile modulus of about 82%-106% and the modulus in flexure of about 77%-97%.
Along with the amount decline of component (a), the mechanical property expection of damping and amortization thermoplastic compounds of the present invention can reduce.Therefore, damping and amortization thermoplastic compounds of the present invention unexpectedly has significant damping improvement and expection is applied to acceptable mechanical property.
In one embodiment, noise damping thermoplastic compounds of the present invention comprise, comprise, substantially composed of the following components:
(a) polymeric amide that contains glass fibre of 80 % by weight-98 % by weight;
(b) impact modifying agent of 0.5 % by weight-5 % by weight;
(c) the organically-modified nanoclay of 0.5 % by weight-5 % by weight;
(d) polyolefine of 0.3 % by weight-8 % by weight; With
(e) other additive of 0 % by weight-15 % by weight;
Wherein the polyolefine of component (d) is to be selected from polypropylene, poly-(4-methyl-1-pentene), poly 1-butene, and their mixture, and described % by weight is the gross weight with respect to described noise damping thermoplastic compounds.
table 4
| Unit | C-5 | C-6 | C-7 | E-1 | C-8 | |
| (a)PA/GF(65/35) | % | 97.5 | 96.6 | 95.3 | 94.4 | 94.4 |
| (b)SEB S-g-MA | % | - | 0.9 | - | 0.9 | 0.9 |
| (c)OMMT | % | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 |
| (d1)PP | % | - | - | 2.2 | 2.2 | - |
| (d2)PE | % | - | - | - | - | 2.2 |
| Amount to | % | 100 | 100 | 100 | 100 | 100 |
| η1500Hz | x10 -2 | 3.6 | 3.7 | 3.7 | 5.7 | 3.7 |
| η2500Hz | x10 -2 | 3.2 | 3.2 | 3.3 | 6.2 | 3.3 |
| η3100Hz | x10 -2 | 5.2 | 5.4 | 5.5 | 6.2 | 5.4 |
By the result of table 4, to draw a conclusion, be obvious.
The Tan δ value of C5-C7 and E1 is contrasted, and the damping and amortization thermoplastic compounds of E1 of the present invention shows respectively at least 54%, 88% and 13% damping improvement at 1500Hz, 2500Hz and 3100Hz.
What is interesting is, when during with the PP of polyethylene (PE) alternative compositions (d) of same amount, not observing damping and improve as shown in C8.
In another embodiment, noise damping thermoplastic compounds of the present invention comprise, comprise, substantially composed of the following components:
(a) nylon that contains glass fibre 6,6 of 80 % by weight-98 % by weight, nylon 6,6/6, or its mixture;
(b) the styrene-ethylene/butylene-styrene multipolymer (SEBS-g-MA) of the maleic anhydride graft of 0.5 % by weight-5 % by weight;
(c) the organically-modified nanoclay that is selected from sepiolite, montmorillonite and composition thereof of 0.5 % by weight-5 % by weight;
(d) homopolymer polypropylene of 0.3 % by weight-8 % by weight and polypropylene copolymer; With
(e) other additive of 0 % by weight-15 % by weight;
Wherein wt % is the gross weight with respect to described noise damping thermoplastic compounds.
In another embodiment, noise damping thermoplastic compounds of the present invention comprise, comprise, substantially composed of the following components:
(a) nylon that contains glass fibre 6,6 of 85 % by weight-96 % by weight, nylon 6,6/6, or its mixture;
(b) the styrene-ethylene/butylene-styrene multipolymer (SEBS-g-MA) of the maleic anhydride graft of 0.5 % by weight-5 % by weight;
(c) the organically-modified nanoclay that is selected from sepiolite, montmorillonite and composition thereof of 1 % by weight-4.5 % by weight;
(d) homopolymer polypropylene of 0.8 % by weight-3.6 % by weight and polypropylene copolymer; With
(e) other additive of 0 % by weight-10 % by weight;
Wherein wt % is the gross weight with respect to described noise damping thermoplastic compounds.
Noise damping thermoplastic compounds of the present invention, although its mechanical property is lower, improves because it has significant damping, is still suitable as moulded parts or the parts of transport facility, power tool, electro-motor, household electrical appliance etc.
Although with typical embodiment example and described the present invention, its intention is not to limit the invention in shown details, may there is multiple modification and alternative not deviating under spirit of the present invention.Thus, when those skilled in the art can be only just obtained with the improvement of open invention herein and are equal to by normal experiment, be sure of all these improvement and be equal in the spirit and scope of the present invention that are included in defined in claim.
Claims (19)
1. noise damping thermoplastic compounds, it comprises:
(a) polymeric amide that contains fiber enhancer of 75 % by weight-98.9 % by weight;
(b) impact modifying agent of 0.5 % by weight-10 % by weight;
(c) nanoclay that is selected from montmorillonite, sepiolite and their mixture of 0.5 % by weight-5 % by weight;
(d) polyolefine of 0.1 % by weight-10 % by weight; With
(e) other additive of 0 % by weight-15 % by weight;
Wherein the polyolefine of component (d) is not polyethylene, and described % by weight is the gross weight with respect to described noise damping thermoplastic compounds.
2. the noise damping thermoplastic compounds of claim 1, wherein the polymeric amide of component (a) is to be selected from nylon 6,6, nylon 6,6/6, nylon 4,6, nylon 10,10, nylon 10, nylon 12, nylon 12,12, nylon 6,10, nylon 6,12, nylon 6,6/6T, nylon 6T/DT, nylon MXD-6, and their mixture.
3. the noise damping thermoplastic compounds of claim 2, wherein the polymeric amide of component (a) is nylon 6,6, nylon 6,6/6, or their mixture.
4. the noise damping thermoplastic compounds of claim 3, wherein the polymeric amide of component (a) is nylon 6,6.
5. the noise damping thermoplastic compounds of claim 1, wherein the fiber enhancer of component (a) is glass fibre, carbon fiber, or contraposition-Kevlar.
6. the noise damping thermoplastic compounds of claim 4, wherein the fiber enhancer of component (a) is glass fibre.
7. the noise damping thermoplastic compounds of claim 1, wherein, with respect to the gross weight of component (a), the amount of the fiber enhancer of component (a) is 20 % by weight-45 % by weight.
8. the noise damping thermoplastic compounds of claim 1, wherein the impact modifying agent of component (b) is styrene-ethylene/butylene-styrene multipolymer, the ethylene-propylene copolymer of maleic anhydride graft, the ethylene-propylene-diene copolymer of maleic anhydride graft that is selected from maleic anhydride graft, and their mixture.
9. the noise damping thermoplastic compounds of claim 8, wherein the impact modifying agent of component (b) is the styrene-ethylene/butylene-styrene multipolymer of maleic anhydride graft.
10. the noise damping thermoplastic compounds of claim 1, the alkyl quaternary ammonium ion that wherein nanoclay of component (c) comprises 20 % by weight-50 % by weight, described alkyl quaternary ammonium ion contains at least one substituting group, described substituting group is that carbon chain lengths is C12 or longer saturated or undersaturated aliphatic group, and the % by weight of described alkyl quaternary ammonium ion is the gross weight with respect to component (c).
The noise damping thermoplastic compounds of 11. claims 10, wherein said alkyl quaternary ammonium ion is to be selected from trimethylammonium tallow ammonium, trimethylammonium hydrogenated tallow ammonium, two (hydrogenated tallow) Dimethyl Ammonium, two (2-hydroxyethyl) methyl tallow ammonium, two (2-hydroxyethyl) methyl cocoa ammonium, two (2-hydroxyethyl) methyl vegetable seeds ammonium and their mixtures.
The noise damping thermoplastic compounds of 12. claims 1, wherein the polyolefine of component (d) is to be selected from polypropylene, poly-(4-methyl-1-pentene), poly 1-butene, and their mixture.
The noise damping thermoplastic compounds of 13. claims 12, wherein the polyolefine of component (d) is homopolymer polypropylene or polypropylene copolymer.
The noise damping thermoplastic compounds of 14. claims 1, wherein other additive of component (e) is to be selected from antioxidant, thermo-stabilizer, UV light stabilizing agent, ultraviolet absorbers, the tinting material that comprises dyestuff and pigment, lubricant, hydrolysis-resisting agent, releasing agent, mica, flow ability modifying agent, chain propagation agent, fire retardant and their mixture.
15. moulded partss, the noise damping thermoplastic compounds that it comprises claim 1 or made by the noise damping thermoplastic compounds of claim 1.
The moulded parts of 16. claims 15, it is the noise damping parts of transport facility, wherein said transport facility is automobile, aircraft, train or boats and ships.
The moulded parts of 17. claims 16, it is the noise damping parts of automobile, and described parts are to be selected from: for the parts of transmission system, for the parts of air inlet and gas barrier, for the parts of cooling system, for the parts of engine system, for the parts of electronic fuel injection system with for the parts of vehicle body.
The moulded parts of 18. claims 15, it is the noise damping parts of electric equipment products, described electric equipment products are to be selected from power tool, electro-motor, and household electronic products comprises washing machine, air-conditioning, blower fan, moisture trap, microwave oven, refrigerator and refrigerator-freezer.
The moulded parts of 19. claims 15 is as the purposes of the noise damping parts in transport facility, and wherein said transport facility is automobile, aircraft, train or boats and ships.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327503A (en) * | 2014-11-10 | 2015-02-04 | 浙江品诺新材料有限公司 | Low-temperature-resistant high-flow nylon composition for ribbon and preparation method of low-temperature-resistant high-flow nylon composition |
| WO2015135114A1 (en) * | 2014-03-10 | 2015-09-17 | Henkel (China) Company Limited | Acoustic damping composition |
| CN105199374A (en) * | 2015-09-25 | 2015-12-30 | 金发科技股份有限公司 | Heat-aging-resistant hydrolysis-resistant polyamide/polypropylene alloy |
| CN115028991A (en) * | 2022-07-21 | 2022-09-09 | 巴斯夫欧洲公司 | Thermoplastic compositions and articles made therefrom |
| WO2024127052A1 (en) * | 2022-12-14 | 2024-06-20 | Arkema France | Compositions comprising clays and their use for the preparation of a tubular structure to reduce oligomer extraction |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1274379A (en) * | 1998-07-30 | 2000-11-22 | 东丽株式会社 | Polyamide resin compsn. and process for producing same |
| CN1301278A (en) * | 1998-02-13 | 2001-06-27 | 索罗蒂亚公司 | Polymer nanocomposite composition |
| US20070004842A1 (en) * | 2003-05-05 | 2007-01-04 | Daniela Tomova | Polymer nanocomposite blends |
| CN101146866A (en) * | 2005-03-24 | 2008-03-19 | 宇部兴产株式会社 | Material for fuel system components |
| CN100523086C (en) * | 2003-03-17 | 2009-08-05 | 阿托菲纳公司 | Polyamide and polyolefine blend containing nanometer filler and with polyamide as matrix |
| CN101796136A (en) * | 2007-09-03 | 2010-08-04 | 尤尼吉可株式会社 | Resin composition and molded body using the same |
-
2012
- 2012-07-19 CN CN201210251294.6A patent/CN103571181A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1301278A (en) * | 1998-02-13 | 2001-06-27 | 索罗蒂亚公司 | Polymer nanocomposite composition |
| CN1274379A (en) * | 1998-07-30 | 2000-11-22 | 东丽株式会社 | Polyamide resin compsn. and process for producing same |
| CN100523086C (en) * | 2003-03-17 | 2009-08-05 | 阿托菲纳公司 | Polyamide and polyolefine blend containing nanometer filler and with polyamide as matrix |
| US20070004842A1 (en) * | 2003-05-05 | 2007-01-04 | Daniela Tomova | Polymer nanocomposite blends |
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