BRPI0820979B1 - TWO-CURABLE PRECURSING COMPOSITION FOR PREPARATION OF A VIBRATION DAMPING COMPOSITION AND VIBRATION DAMPING COMPOSITION - Google Patents

Description

(54) Title: CURABLE TWO-PART PRECURSING COMPOSITION FOR PREPARING A VIBRATION DAMPING COMPOSITION AND VIBRATION DAMPING COMPOSITION (51) lnt.CI .: C08L 63/00; C08G 59/00 (30) Unionist Priority: 12/14/2007 GB 0724378.5 (73) Owner (s): 3M INNOVATIVE PROPERTIES COMPANY (72) Inventor (s): SOHAIB ELGIMIABI (85) National Phase Start Date: 14 / 06/2010

1/26 “CURSIBLE TWO-PART PRECURSING COMPOSITION FOR PREPARING A VIBRATION DAMPING COMPOSITION AND VIBRATION DAMPING COMPOSITION”

Technical Field [001] The compositions and methods for producing these compositions provided here refer to compositions for dampening vibrations based on epoxy resins.

Background [002] Various transport vehicles, electronic device mechanisms, and machines are subjected to noise and vibration, due to the environments within which they are placed or used. Such noises and vibrations can present problems in their use or function, and can be irritating or harmful to the users of such devices or devices. Therefore, there is a need to reduce the impact of such noises and vibrations on devices, devices and users. In various applications, noise and vibration are reduced by placing on or attaching to such vehicles or extension shock absorbers. Extension shock absorbers are, in general, composite blocks that have pressure sensitive or hot-melt adhesive on one side. These are applied to the shaking substrate. Such plates are difficult to affix to or shape around uniquely shaped parts.

[003] Thermo-adjustable resin compositions have been used as an alternative to blocks. In WO 99/16840 an epoxy resin composition has been described as having good vibration damping properties. However, according to WO 02/50184, good vibration damping values are observed only within a very small temperature window. To increase the temperature window, specific charges that have a high aspect ratio or a plate-like structure had to be used. To increase the temperature window, WO 02/50184 describes the use of alternative resin compositions comprising epoxy resins and a thermoplastic interpolymer.

Summary [004] There is still a need for compositions that have vibration dampening properties not only at a temperature window greater than 30 ° C, but that also have good mechanical resistance at a lower temperature window

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2/26 wide, for example, from room temperature to about 100 ° C. Such good mechanical properties are particularly desirable in the application of vibration damping compositions in the transport industry, such as aircraft, motor vehicle or water vehicle industries, where the components to which the damping compositions have been applied can be subject to various temperatures and / or mechanical forces.

[005] In addition, particularly in the transport industry, but also in other applications, there is a continuing need for weight reduction to save energy costs. Therefore, vibration damping compositions that have a low density but still have good vibration damping and mechanical strength over a wide comparative temperature window are desired.

[006] Therefore, there is a need for vibration damping compositions that are injectable or extrusable, or that can be prepared from injectable or extrusable precursor compositions that have good vibration dampening properties over a comparatively temperature window sufficient strength and / or mechanical resistance over temperatures higher than room temperature and which, in addition, have a low density.

[007] It has now been found that compositions for effective vibration damping with low density, preferably a density less than 0.9 g / cm ³ , but which still have good vibration damping properties and mechanical strength (for example, Young modules greater than 10 MPa) over a wide temperature window, preferably from room temperature to at least about 100 ° C, can be prepared with compositions that comprise a mixture of flexible and rigid epoxy resins, curing for crosslinking epoxy resins and a combination of hollow spherical particles.

[008] Therefore, below is provided a curable precursor composition for the preparation of a vibration damping composition having a density less than 0.9 g / cm ³ , said precursor composition comprising (i) one or more epoxy resins rigid, (ii) one or more flexible epoxy resins,

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3/26 (iii) a first set of hollow microspheres, (iv) a second set of hollow microspheres, the microspheres of the first set being different in composition from the microspheres of the second set, and a curing agent capable of crosslinking both resins rigid and flexible epoxy.

[009] A vibration dampening composition obtainable by curing the precursor composition described above is also provided.

[010] Additionally, a method for preparing a vibration damping composition comprising

a) provide a precursor composition,

b) placing the precursor composition in contact with a surface,

c) cure the precursor composition.

[011] Additionally, an article is provided which comprises a composition for dampening vibrations.

[012] In yet another aspect it is provided the use of compositions to dampen vibrations from shaking components, such as, for example, a motor vehicle, a vehicle with jet propulsion, or a fan or its compartment.

Detailed Description [013] The vibration damping properties of a polymer composition can be measured by dynamic thermal analysis (ATD). An oscillating force is applied to a given sample at various temperatures and the resulting displacement and / or energy absorption by the sample is measured. By measuring the time interval in displacement compared to the applied force, it is possible to determine the damping properties of the material. The time interval is recorded as a tangent of the interval phase and expressed as a ‘loss factor’ or ‘Delta tangent’. The loss factor depends on the temperature. When the loss versus temperature graph is plotted, the plot reaches the glass transition temperature (tg) of the polymer composition. Therefore, the ‘peak loss factor’ was introduced, which is the loss factor in the Tg of the polymer composition. By varying the reasons for the ingredients or the addition of plasticizers, the Tg of the composition can be influenced, that is, the composition can be precisely adjusted to the temperature in

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4/26 that the composition achieves the highest vibration damping. The maximum point in a loss factor versus temperature plot can be a sharp, narrow peak. This means that the damping properties can be satisfactory only within a narrow temperature window. However, if good vibration dampening properties over a wide temperature range are desired, a plot of the loss versus temperature factor should reveal a broad peak rather than a sharp one. The “width” of such a peak is called the temperature range at the peak of the loss factor. A loss factor greater than 0.2 is considered to represent good vibration damping properties. Therefore, it is desired to provide compositions that have a wide temperature range around the peak of the loss factor where the loss factor still reaches a value of 0.2 or more. The greater the temperature range, the greater the temperature range over which the sample has sufficient damping performance. Preferably, the temperature range at the peak of the loss factor where the loss factor still reaches a value of 0.2 or more is greater than 40 ° C.

[014] The glass transition temperature, and thus the maximum damping effect, can be adjusted by changing the ratio between components, in particular the ratio between flexible and rigid epoxy resins and / or by adding other polymers, so-called plasticizers. The vibration dampening composition can typically have a glass transition temperature (as determined by the ATD) greater than about 20 ° C. The glass transition temperature can be less than 120 ° C or less than 100 ° C. Typically, the glass transition temperature is within about 40 and about 90 ° C.

[015] The compositions provided here have a comparatively wide window, which provide good vibration dampening and can therefore be suitable for vibrating substrates subjected to operating temperatures, for example, from about 15 to about 150 ° C, or from about 20 to about 120 ° C.

[016] Despite their low density, the compositions can have sufficient mechanical strength, as expressed by a Young modulus at least above 10 MPa, as measured by the ATD, preferably over a temperature range of at least about 20 ° C to about 100 ° C.

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5/26 [017] Compositions for dampening vibrations are obtained by curing a precursor composition.

[018] Precursor compositions are typically extrusable or injectable. They can have an extrusion speed of at least about 30, preferably 40 g / min, through an opening of 4 mm at a pressure of 0.5 MPa (5 bar). The precursor compositions, or each part of the precursor composition in the case of a two-component composition, can, for example, have a Brookfield viscosity at 25 ° C between about 40 and about 700 Pa.s.

[019] The precursor compositions are based on curable epoxy resins. They comprise at least one rigid epoxy resin and at least one flexible epoxy resin, a combination of hollow spherical particles (microspheres) of different chemical types and a curing agent for crosslinking the epoxy resins to form the composition for dampening vibrations. Flexible and rigid epoxy resins are typically two separate resins, which can be cross-linked with each other by curing. However, it is also considered that the flexible and rigid epoxy resins in the precursor composition may be comprised of a resin, that is, such a resin may have flexible and rigid epoxy components.

[020] Compositions have been found to have improved vibration dampening properties (which have a peak loss factor greater than 0.5 and a temperature span at the peak of the loss factor where the loss factor is at least 0.2 of at least 30 ° C, preferably at least 40 ° C) can be prepared by curing curable precursor compositions (term adjustable) provided here.

[021] It has also been found that compositions that have improved vibration damping properties (that have a peak loss factor greater than 0.5 and a temperature range at the peak of the loss factor where the loss factor is at least minus 0.2 of at least 30 ° C, preferably at least 40 ° C) and having a density less than 0.9 g / cm ³ or less than 0.7 g / cm ³ , preferably less than 0, 6 g / cm ³ , can be prepared by curing curable precursor compositions (term adjustable) provided here.

[022] Additionally, it has been found that compositions that have enhanced vibration damping properties (that have a higher peak loss factor

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6/26 than 0.5 and a temperature range at the peak of the loss factor where the loss factor is at least 0.2 of at least 30 ° C, preferably at least 40 ° C) and which have a density less than 0.9 g / cm ³ or less than 0.7 g / cm ³ , preferably less than 0.6 g / cm ³ and having a Young's modulus of at least 10 MPa at a temperature of 100 ° C , can be prepared by curing curable precursor compositions (term adjustable) provided here.

[023] The precursor composition can be a two-part composition or a single-part composition. In a two-part composition, the first part typically comprises a curing agent, and the second part typically comprises epoxy resin, the second part being separated from the first part. The ratios between the first part and the second part are chosen in such a way that molar amounts of curing agent and epoxy resins are in a range in which crosslinking of the epoxy resin occurs. Combining the two components, the healing process begins. Preferably, the curing agent is capable of initiating curing at room temperature. In a single component composition, curing is initiated by subjecting the formulation to elevated temperatures, the curing agent being selected in such a way that, essentially, no crosslinking occurs at the storage temperature, which is typically at room temperature (25 ° C).

[024] Preferably, the precursor composition is a two-part composition.

[025] The ingredients of the precursor compositions and, consequently, the vibration damping compositions obtainable from the precursor compositions are described in more detail below.

Epoxy resins [026] Epoxy resins are polymers derived from the polymerization, through a ring opening reaction, of an organic compound that has an oxirane ring (epoxides). These materials include aliphatic, cycloaliphatic, aromatic or heterocyclic polymeric epoxides. Suitable materials have at least two reactants, that is, polymerizable or crosslinkable epoxy groups, preferably terminal, per molecule. Typically, epoxy resins are prepared by polymerizing monomers containing epoxy groups. Suitable monomers are typically the

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7/26 reaction products of an epihalohydrin with a polyhydroxyhydrocarbon that produces mono-, bi- or poly-glycidyl ethers.

Rigid epoxy resins [027] For use in the present invention, rigid epoxy resins are epoxy resins that comprise repeating units derived from phenolic glycidyl ethers or polynuclear phenols, including their derivatives. Examples include mono, di- or poly glycidyl ethers of ρ, ρ'-dihydroxy dibenzyl, ρ, ρ'-dihydroxy phenylsulfone, ρ, ρ'-dihydroxy benzophenone, 2,2'-dihydroxy phenylsulfone, ρ, ρ'- benzophenone dihydroxy, 2,2-dihydroxy-1,1 dinafty methane, and the 2,2 ', 2,3', 2,4 ', 3,3', 3,4 'and 4,4' diphenyl dihydroxy isomers methane, difenildimetil dihydroxy methane, difeniletilmetil dihydroxy methane, difenilmetilpropil dihydroxy methane, difeniletilfenil dihydroxy methane, difenilpropilenofenil dihydroxy methane, difenilbutilfenil dihydroxy methane, difeniltolil dihydroxy ethane, dihydroxy difeniltolilmetil methane, difenildiciclohexil dihydroxy methane, dihydroxy diphenyl cyclohexane, and mixtures or combinations thereof. Preferred examples include glycidyl or diglycidyl ethers of bisphenol A, bisphenol F, and mixtures or combinations thereof.

[028] Such glycidyl ethers can be prepared, for example, by reacting the corresponding hydroxyl-functionalized arenes with an excess of epichlorohydrin.

[029] Typical examples of rigid epoxy resins include those presented by general formula (I):

R t ch-.cch ₂ o \ z

OCHiCCH; 0

I \ OH

I

OCHjC CH ·, V O where

R represents an H, or a C1-C4 alkyl, such as methyl, ethyl, propyl, butyl, isopropyl,

R ¹ is independently, at each occurrence, a C1 - C3 alkylene (for example, propylene, 1-methylethylene or 1,1-dimethylmethylene), a direct bond or a carbonyl,

R ² is independently, at each occurrence, an H, or an alkyl, such as a C1 - C3 alkylene,

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8/26 m is, separately, in each occurrence, an integer from 0 to 3 r can be 0 or an integer> 0, and chosen in such a way that the molecular weight of the resin can be reached.

[030] Examples of commercially available rigid epoxy resins based on bisphenol A diglycidyl ether include those available under the trade names EPON 828, EPON 1001, EPON 1310 and EPON 1510, from Hexion Specialty Chemicals GmbH, Rosbach, Germany, and DER-331, DER-332 and DER334, available from Dow Chemical Co. Commercial resins based on bisphenol F diglycidyl ether include, for example, EPICLON 830, available from Dainippon Ink and Chemicals, Inc. Resins based on blends of bisphenol A and F are commercially available, for example, under the trade name EPIKOTE 232, from Resolution Performance Products.

[031] Rigid epoxy resins typically have a molecular weight in the range of about 170 to about 10,000, preferably from about 200 to about 3,000 g / mol.

[032] The rigid epoxy resin can be a solid, paste, or liquid at room temperature (25 ° C), or it can be a solid or paste dispersed in a liquid epoxy resin.

[033] Rigid epoxy resins are typically present in the composition in an amount of about 20 to about 40% by weight, based on the total weight of the precursor composition or for dampening vibrations.

Flexible epoxy resins [034] For use in the present invention, flexible epoxy resins are epoxy resins that comprise repeating units derived from monomers that have two epoxide portions separated from each other by at least one spacer group. The spacer group can be an alkyl, alkoxy or alkyl polyoxy chain, which has at least 6 or at least 7 linear catenary atoms. The chain may be unsubstituted or substituted with one or more identical, different, linear, branched or cyclic alkyl, alkoxy or alkyl polyoxy groups. Preferably, the number of substituents is less than the number of catenary atoms.

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9/26 [035] The chain is along at least parts of its length, preferably along its entire length, freely rotating, that is, flexible. Therefore, epoxy resins are called "flexible" epoxy resins.

[036] Flexible epoxy resins can be aliphatic or aromatic.

[037] Flexible aliphatic epoxy resins comprise repeating units derived from monomers comprising at least two epoxy groups or glycidyl ether groups, separated by an alkyl, alkoxy or alkyl polyoxy chain, which have at least 6 or at least 7 catenary atoms (linear ). In some embodiments, the spacer group may contain less than 30 or less than 20 or less than 15 linear catenary atoms. Alkoxy or alkyl polyoxy chains are preferred. Typical examples include glycidyl ethers or diglycidyl ethers of polyoxy polyols such as, for example, polyoxy alkylene glycols or alkane diols, etc.

[038] Flexible aliphatic epoxy resins can be described, in general, by formula (II):

E1-R-E2 (II), where

E1 and E2 represent, independently of one another, an epoxide or a glycidyl ether, and R represents a spacer group which is an alkyl, alkoxy or alkyl polyoxy chain, which has at least 6 or at least 7 (linear) catenary atoms.

[039] Preferably, R is an alkoxy or polyoxy alkylene such as, for example, a group comprising one or more ethylene-oxy or propylene-oxy units, or combinations thereof.

[040] Flexible aromatic epoxy resins comprise repeating units derived from monomers containing at least two aromatic glycidyl ethers or at least one aromatic glycidyl ether and a glycidyl ether group separated by a spacer group, the spacer group being an alkyl, alkoxy or chain alkyl polyoxy, which has at least 6, or at least 7 catenary (linear) atoms.

Flexible aromatic epoxy resins can be described, in general, by the formula (III):

E3-R-E4 (III), where

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10/26

Ε3 and E4 represent, independently of each other, an epoxy group, a glycidyl ether group or an aromatic group containing an epoxy or glycidyl ether moiety, and at least one of E3 and E4, preferably both, represents an aromatic group containing an epoxy portion, such as a glycidyl ether group.

[041] Aromatic groups containing epoxy moieties, such as etherglycidyl groups, include, for example, phenyl ether glycidyl groups, which may or may not be substituted, such as, but not limited to, ρ, ρ'-dihydroxy glycidyl ethers dibenzyl, ρ, ρ'-dihydroxy phenylsulfone, ρ, ρ'-dihydroxy benzophenone, 2,2'-dihydroxy phenylsulfone, ρ, ρ'dihhydroxy benzophenone, 2,2-dihydroxy-1,1-dinafty methane, and the isomers 2 , 2 ', 2,3', 2,4 ', 3,3', 3,4 'and 4,4' of diphenyl methane dihydroxy, diphenyldimethyl methane dihydroxy, diphenylethylmethyl methane, diphenylmethylpropyl methane dihydroxy, diphenylethylphenyl methane dihydroxy, dihydroxy diphenylpropylenophenyl methane, dihydroxy diphenylbutylphenyl methane, dihydroxy diphenyltolyl ethane, dihydroxy diphenyltolylmethyl methane, dihydroxy diphenyldicyclohexyl methane, dihydroxy diphenyl cyclohexane, or combinations thereof.

[042] R represents a spacer group which is an alkyl, alkoxy or alkyl polyoxy chain, which has at least 6 or at least 7 catenary (linear) atoms.

[043] Flexible epoxy resins can be prepared, for example, by reacting corresponding aliphatic hydroxy compounds with an excess of epichlorohydrin, as described, for example, in U.S. Patent No. 5,308,895.

[044] Flexible aromatic epoxy resins are commercially available, for example, from Cardolite Corporation, Newark, NJ, USA, as, for example, under the trade name Cardolite NC 514.

[045] Flexible resins can typically be present in the compositions in amounts of about 5 to about 25% by weight, based on the weight of the precursor or damping composition.

Curing agents (hardeners) [046] The formulation additionally comprises a curing agent capable of curing (crosslinking) epoxy resins. The curing agent can be any curing agent capable of crosslinking (curing) epoxy resins and which is known to those skilled in the art. Preferably, the curing agent is capable of crosslinking at room temperature or at temperatures above room temperature (25 ° C).

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11/26

Examples include amine-curing agents (primary amines), but also secondary amines. Such amines include straight or branched alkyls, polyethers, alkylamines containing primary and / or secondary amine groups, and also amine-terminated polymers containing aromatic groups in their main chain. Preferably, the curing agent has a molecular weight greater than about 150 g / mol, for example, between 200 and 700 g / mol. Typically, the curing agent has a molecular weight of less than 3,000 g / mol.

[047] Anhydrides, including dianhydrides, and cyandiamides or dicyandiamides and derivatives of these substances can also be used as curing agents. The choice of curing agent can determine whether the composition is a single-part or two-part composition, and the optimal curing temperature of the composition.

[048] For a two-component composition, curing agents with primary or secondary amines, or with anhydride are typically used. For a single component formulation, a cyanamide or dicyanamide curing agent can be used.

[049] Examples of suitable curing agents include those according to the general formula

R ¹ R ² NR ³ -NR ⁴ H (IV) where R ¹ , R ² and R ⁴ represent, independently of each other, hydrogen, a linear or branched alkyl, or a linear or branched alkyl polyoxy moiety.

[050] Residues R ¹ , R ² , R ⁴ can contain a hydrocarbon that has about 1 to 25 carbon atoms, or a polyether that has 3 to 25 carbon atoms. Preferably one, more preferably two, and most preferably all R ¹ , R ² and R ⁴ are hydrogens.

[051] R ³ represents a linear, branched alkyl, alkylamine, polyaminoalkylene, polyamidoalkylene, alkyl ether or polyoxy alkylene group. Preferably, R ³ is a polyether and the curing agent is a polyether amine or a polyether diamine, including those polyether amines that can be derived from polypropylene oxide or polyethylene oxide. R ³ can also be a polyamido amine or a polyamido diamine, including those that can be derived from the reaction of a dimer or trimer of carboxylic acid with a polyether amine.

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12/26 [052] Suitable polyether amines include, but are not limited to, those corresponding to the general formula

H2N-C3H6-O- [C2H4-O-] nC3H6-NH2,

H2N-C3H6-O- [C3H6-O-] nC3H6-NH2, (IVa) (IVb)

H2N-C (CH3) H-CH2- [O-CH2-C (CH3) H] nO-CH2-CH (CH3) -NH2 (IVc) with n being between 1 and 34 (inclusive), such as, for example, 1,2, 3, 4, 5, between and 2 (such as, for example, 1.5 or 1.7), between 2 and 3 (such as, for example, 2.5 or 2.7), between 3 and 4 (for example, 3.5 or 3.7), between 4 and 5 (for example, 4.5 or 4.7), or n is 31.32, 33, or is between 31 and 33.

[053] Combinations of curing agents, such as a combination of two or more polyether diamines may also be suitable.

[054] Examples of suitable commercial curing agents include (but are not limited to) those available under the trade name PC AMINE DA, from Nitroil, Germany, or JEFFAMINE, from Huntsman, Belgium.

[055] Typically, the one or more curing agents can be present in an amount of about 10 to about 25% by weight, based on the total amount of the precursor composition or the vibration dampening composition.

Curing Catalysts [056] The composition may additionally comprise a catalyst for the reaction of an epoxy resin with an epoxy curing compound to accelerate the curing process. Such catalysts are well known to those skilled in the art, and include organic catalysts, such as urea, imidazoles, and inorganic catalysts such as boron trialides (for example boron trifluoride) or metal salt catalysts. Metal salt catalysts are preferred. Suitable metal salt catalysts include group I metals, group II metals or lanthanoid salts, the anion being selected from nitrates, iodides, thiocyanates, triflates, alkoxides, perchlorates and sulfonates. Nitrates, iodides, thiocyanates, triflates and sulfonates, including their hydrates, are preferred, and nitrates, including their hydrates, such as calcium nitrates, are particularly preferred.

[057] The preferred group I metal (cation) is lithium, and the preferred group II metals (cations) are calcium and magnesium, with calcium being especially

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Preferred 13/26. Consequently, preferred catalyst salts are lanthanum nitrate, lanthanum triflate, lithium iodide, lithium nitrate, calcium nitrate and their corresponding hydrates.

[058] The amount of catalyst used can vary depending on the desired reactivity (cure speed) and stability during storage. Preferably, the catalyst is present in an amount of 0.1 to 5 weight percent, based on the weight of the vibration damping composition, or the total weight of the precursor formulation.

[059] For most applications, the metal catalyst will be used from about 0.05 to less than 15 parts by weight, based on the total weight of the total composition. Non-metallic catalysts can generally be used in amounts of 0.1 to 5% by weight, based on the total weight of the total composition.

[060] The catalyst can be present in part A or part B, or both, of a two-component precursor composition.

Plasticizers [061] The compositions can also comprise plasticizers to modify the glass transition temperature of the formulation. Plasticizers can be used in this way to change the peak loss factor for temperature ranges where maximum vibration damping is desired. Suitable plasticizers are polymeric compounds that are compatible with epoxy resins. Typical examples include polyester polyols, polyolefins such as ethylenepropylene copolymers, etc. Plasticizers typically have a viscosity greater than about 1,000 cps at 25 ° C. Plasticizers can have viscosity values at 25 ° C of about 1,000 cps to values that are typical for pastes. Plasticizers can be present in an amount of 1 to 15% by weight, based on the total amount of total composition.

Spherical charges [062] The compositions additionally comprise a combination of spherical or essentially spherical charges (microspheres). Essentially spherical means that particles are not perfect spheres, but they can still be well described as spheres. Spherical loads are hollow. They can be inorganic or organic. “Hollow” means that the spheres are not solid. The spheres

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Hollow 14/26 may, for example, contain a vacuum, a gas or a mixture of gases, or a liquid or a mixture of liquids, or a mixture of one or more gases and one or more liquids.

Inorganic microspheres:

[063] Spherical charges can be inorganic microspheres.

[064] The housing of such inorganic microspheres can be selected from a variety of inorganic materials, such as metal oxides or carbon, including, for example, glass or ceramics, etc.

[065] Inorganic microspheres preferably form free flowing powders. Preferably, they have a relatively homogeneous particle size. The average particle size is typically between about 1 and about 300 pm, preferably from about 5 to about 200 pm, and more preferably between about 10 and about 100 pm. Inorganic microspheres preferably have a density of less than about 0.5 g / cm ³ , more preferably between about 0.1 and about 0.45 g / cm ³ , and most preferably between about 0 , 1 and about 0.4 g / cm ³ .

[066] Inorganic microspheres are preferably selected to obtain an advantageous crush resistance, so that they essentially survive the processing of the precursor composition, including mixing and extrusion. They are selected, preferably, so that at least 85% and, more preferably, at least 90% of an amount of such microspheres included in the precursor composition survive the application of a pressure of at least 2,500 and, more preferably, of at least 27.6 MPa (4,000 psi) (pounds per square inch) to the precursor composition.

[067] The inorganic microspheres useful in the present invention preferably have a smooth outer surface rather than a rough outer surface.

[068] Especially preferred hollow inorganic microspheres include glassy microspheres. Hollow glass microspheres are commercially available, for example, from 3M Company, of St. Paul, MN, USA, under the trade name SCOTCHLITE.

Organic microspheres:

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15/26 [069] The compositions provided here may also contain organic microspheres. Microspheres are preferably hollow, with “hollow” having the same meaning as described above.

[070] Organic microspheres are polymeric microspheres. Polymeric microspheres are produced from organic polymers, that is, materials that comprise repeating units derived from monomers that contain at least one unsaturated carbon-carbon bond. Typical examples of suitable polymers include, but are not limited to, acrylonitrile polymers or copolymers, acrylate polymers or copolymers, vinylidene polymers or copolymers, polyacetate polymers or copolymers, polyester polymers / vinyl chloride copolymers / chloride vinyl copolymers , acrylate / acrylonitrile copolymers, or combinations thereof.

[071] The average diameter of the organic microspheres is preferably between 15 and 200 pm, and more preferably between 20 and 180 pm. Typically, organic microspheres have a low density, typically a density between 0.01 and 0.3 g / cm ³ .

[072] Preferably, organic microspheres are compressible. This means that the volume of the compressible organic microspheres decreases when they are subjected to a pressure of, for example, 0.5 MPa (5 bar). Preferably, they are elastically compressible, that is, they essentially return to their original shape and / or dimension when the pressure is removed.

[073] Microspheres can be either non-expanded or pre-expanded. An example of suitable organic microspheres are pre-expanded microspheres. The pre-expanded organic microspheres can comprise a polymeric housing comprising, for example, acrylonitrile / acrylate copolymers, or vinylidene chloride / acrylonitrile copolymers. The carcass may encapsulate a core comprising, by way of example, but without limitation, vacuum, air, nitrogen, or one or more essentially gaseous hydrocarbons (at room temperature).

[074] Pre-expanded hollow organic microspheres are commercially available, for example, from Lehmann & Voss, in Hamburg, Germany, under the trade name DUALITE.

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16/26 [075] Spherical fillers may be present in an amount of about 10 weight percent or more, and more preferably about 15 weight percent or more, based on the total weight of the parent composition or the composition for dampening vibrations. Preferably, the spherical charge is present in an amount of about 10 to about 35% by weight, based on the total weight of the precursor composition or the composition for dampening vibrations.

[076] The composition comprises a combination of chemically different microspheres, preferably a combination of inorganic and organic microspheres. Typically, the composition comprises a larger amount (as determined in%, by weight) of inorganic than organic microspheres.

[077] Typically, inorganic microspheres are present in an amount of about 8 to about 30% by weight, and organic microspheres can be present in an amount of at least 1% by weight, or at least 2% , by weight, and are typically comprised in an amount of about 1 to about 10%, by weight, based on the total amount of the total composition.

[078] The microspheres can be the same or different sizes. For example, a first set of microspheres can have an average particle diameter of about 5 pm to about 105 pm, and a second set of microspheres can have an average particle size of about 90 to 200 pm.

[079] Typically, the compositions comprise a combination of inorganic and organic microspheres. In these combinations, organic microspheres can have a larger diameter (for example, from about 90 to about 200 pm, but not limited to them) than inorganic spheres (for example, from about 5 to about 105 pm, but not limited to them).

Adjuvants [080] Compositions can contain one or more adjuvants. Adjuvants can be known materials used in the preparation of compositions containing epoxy. Typical adjuvants additionally include fillers, that is, non-spherical fillers, reactive diluents, adhesion promoters, pigments (inorganic or organic pigments, including, but not limited to, ferric oxide, dust

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17/26 brick, carbon black, titanium oxide and the like), flame retardants, antioxidants, etc.

Methods of preparing vibration damping compositions and their precursors [081] Vibration damping compositions are prepared by curing a precursor composition. Preferably, the precursor compositions are curable at room temperature or at temperatures higher than room temperature (25 ° C).

[082] The precursor compositions contain the ingredients described above. Preferably, the precursor composition is a two-part composition containing a part A comprising the hardener (curing agent) and a separate component B comprising the flexible and rigid epoxy resins. Spherical loads can be included in part A or part B, or both.

[083] The components are present in amounts effective to produce extrudable precursor compositions. In a two-part system, both parts are preferably extrusable, to allow dispensing and mixing in double Pac cartridges. The extrusion speed of each part can be measured using a 300 mL Semco cartridge (available from PPG Industries, Hamburg, Germany) through a nozzle with a 4 mm opening and a pressure of 0.5 MPa (5 bar) at room temperature (25 ° C). The resulting extrusion rate is preferably above 40 g / min, more preferably at least 45 g / min.

[084] In addition, the components, in particular the first and second epoxy resins, the curing agent and spherical fillers, are present in effective amounts such that a vibration-dampening composition with a peak hair loss factor at least 0.4, preferably at least 0.5 is produced.

[085] The peak composition loss factor for vibration damping is preferably at a temperature between 30 and 100 ° C, more preferably between 55 and 85 ° C.

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18/26 [086] The temperature range, where the loss factor is greater than 0.2, is preferably at least 30 ° C, preferably 40 ° C, and more preferably at least 45 ° C.

[087] Preferably, the vibration dampening composition has a Young modulus at the peak of the loss factor of about 70 to 150 MPa.

[088] Preferably, the ingredients and their amounts are chosen in such a way that the vibration damping compositions have a density less than about 0.90, less than about 0.70, or less than about 0, 60 g / cm ³ , preferably less than about 0.50 g / cm ³ , and more preferably less than about 0.45 g / cm ³ .

[089] Additionally, the components, in particular flexible and rigid epoxy resins, the curing agent and spherical fillers, can be present in quantities such that the vibration damping compositions have a Young module at room temperature (25 ° C) at least about 450, preferably at least about 600 MPa and, typically, less than about 1,500 MPa.

[090] The quantities of the components, in particular the flexible and rigid epoxy resins, the curing agent and the spherical fillers, can be chosen in such a way that the vibration damping compositions have a Young modulus at 100 ° C greater than about 10 MPa.

[091] The loss factor, the temperature range at the peak of the loss factor, the Young modulus, etc., can be determined by ATD.

[092] In a typical embodiment of a composition for dampening vibrations or their precursor composition, as described in the present invention, rigid epoxy resins are present in an amount of about 25 to about 35%, by weight, based on in the total weight of the composition. Flexible epoxy resins may be present in a lesser amount than rigid epoxy resins. Typical amounts of flexible resins are in the range of 9 to about 20% by weight, based on the total weight of the compositions. Curing agents can be present in amounts of about 12 to about 18% by weight, based on the total weight of the compositions.

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19/26 [093] Spherical fillers can be present in an amount of about 18 to about 32% by weight, based on the total weight of the composition, preferably from about 2 to 8% by weight, of organic microspheres, and about 6 to 30% inorganic microspheres. In addition, the composition can contain about 3 to 10% plasticizers.

[094] The process of preparing the composition for dampening vibrations involves contacting the precursor formulation with a substrate, which is typically a vibrating substrate under operating conditions. The substrate can be any substrate where damping or sound reduction is desired. Such substrate can be metal, wood, plastic, or fiber-reinforced plastic.

[095] The formulation can be used in a wide variety of industries, including the automotive industry, the home appliance industry and the construction industry. Therefore, the use of the compositions described here in damping vibrations, such as, for example, motor vehicles, jet engines, or fans, is also provided. The formulation is particularly advantageous due to its low density and low viscosity, in such a way that it can be extruded or injected into irregularly shaped objects such as the structures or components of automobiles, aircraft or naval vehicles, or in engine compartments or connected parts (directly or indirectly) to the engines or their compartments, fans, such as screen fans and their compartments, including components connected to the fans and / or their compartments, for example, screeners of external aircraft guides. Typical engines include combustion engines, pumps, electric engines, jet engines, and air-powered engines.

[096] Therefore, the vibration damping composition and its precursor composition are particularly suitable for vibration damping in aircraft, naval vehicles and motor vehicles such as automobiles, trucks, motorcycles, trains, ships, airplanes, etc.

[097] The formulation of the invention can be brought into contact with the substrate by any means known in the art, such as, for example, by coating, painting or spreading it, or by injecting it onto the substrate. Application tools known in the art can be used for this purpose.

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20/26 [098] Once the formulation is placed in contact with the substrate, the formulation is left to cure, which can occur at room temperature or by applying heat.

[099] The following examples are provided to further illustrate the invention, without the intention of limiting the invention to them.

Example and methods

1. Measurements of dynamic thermomechanical analysis (ATP) [100] ATD measurements were taken from 5 mm x 10 mm samples that have a thickness of about 1.5 mm.

1.1. Sample preparation:

[101] The precursor composition was extruded from a 400 ml Mixpac cartridge fitted with a mixing nozzle type MC 13-18, available from MIXPAC (Mixpac Systems, AG, Rotkreuz, Switzerland). The product was then spread to a thickness of about 1.5 mm using a laboratory coating.

[102] The samples were cured for 24 h at room temperature, followed by 2 h at 100 ° C in an oven with forced air circulation. After cooling, 5 mm x 10 mm samples were cut from the cured samples and subjected to ATD measurements using an ATD V (available from Rheometric Scientific Inc., Piscataway, NJ 08854, USA).

[103] The ATD V test settings for the peak loss factor, Young modulus and glass transition temperature were:

single cantilever bending mode steering set orientation: horizontal dynamic temperature ramp test temperature range: -50 ° C / + 200 ° C heating rate: 2 ° C / min frequencies: 1 Hz, 10 Hz elongation: 0.05%

1.2. Measurement of the peak loss factor and glass transition temperature [104] The Delta tangent, the ratio of the loss module to the storage module (loss factor), is measured in flexion mode under the conditions described above.

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1.3. Determination of the temperature range at the peak of the loss factor [105] The temperature range was obtained by recording the Delta tangent versus the applied temperature, measuring the peak of the loss factor and measuring the surrounding temperature window the peak of the loss factor where a Delta tangent of 0.2 or more was still measured.

1.4. Determination of the Younq module [106] The Young module (the ratio between the stress amplitude and the elongation measured in the ATD traction or in the flexion mode, as described above) was determined at the indicated temperatures.

2. Compressive strength [107] The compressive strength of the cured epoxy-based composition was measured according to ASTM D695. A 400 mL cartridge obtained from the “Mixpac” suitable for a 2/1 B / A mixing ratio was filled manually to 400 mL with parts A and B at a ratio of 1: 2 by volume. A mixing nozzle type MC 13-18 available from MIXPAC (Mixpac Systems, AG, Rotkreuz, Switzerland) was fitted to the cartridge. About 50 g were then extruded in a Teflon-coated mold having the dimensions of 12.7 mm (height) x 12.7 mm (width) x 25 mm (length) and being opened on one main side.

[108] The mold was placed in an oven with forced air circulation and subjected to a curing program. The oven temperature was maintained at 23 ° C for 24 hours, and then the temperature was maintained at 100 ° C for 2 hours, in order to cure the epoxy-based composition. After the curing for 2 hours at 100 ° C was completed, the cured epoxy composition was cooled to 23 ° C over a period of 45 minutes.

[109] The test samples were compressed along their 25 mm axis at a crosshead speed of a constant tensometer of 1 mm / min, using a Zwick Model Z030 tensile tester (Zwick GmbH & CO., Ulm, Germany), equipped with heating capabilities.

[110] Compressive strength was measured at 23 ° C (room temperature) and 100 ° C. The test samples were pre-conditioned in the heated equipment for at least 30 minutes before testing at 100 ° C.

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22/26 [111] At least three samples were measured for each epoxy composition, and the results were averaged and noted in MPa.

3. Brookfield viscosity [112] Viscosity can be measured using an RVF model equipped with a No. 7 spindle rotating at 2 RPM and 25 +/- 2 ° C.

4. Density [113] The density of cured epoxy compositions was measured according to ASTM D1622. Samples of the epoxy-based composition were prepared by casting the corresponding precursors in the mold and curing in an oven with forced air circulation, using the temperature program as described under the “compression resistance” test method. The cured samples of the epoxy-based composition were removed from the molds, and their exact dimensions were noted. Each sample was weighed and the density was calculated and noted in grams per cm ³ .

5. Extrusion speed [114] The extrusion speed was determined by measuring the extruded quantity 60 s after applying a pressure of 0.5 MPa (5 bar) through a 4 mm nozzle.

[115] A 400 mL cartridge obtained from the “Mixpac” suitable for a 2/1 B / A mixing ratio was filled manually to 400 mL with parts A and B at a ratio of 1: 2 by volume. A mixing nozzle type MC 13-18 available from MIXPAC (Mixpac Systems, AG, Rotkreuz, Switzerland) was fitted to the cartridge. The product was extruded from the cartridge using a pneumatic dispensing gun at a pressure of 0.5 MPa (5 bar) for 60 seconds. Measurements were made under ambient conditions (25 ° C). Each precursor was evaluated 3 times, and the average results were expressed in g / min.

6. Materials

EPIKOTE 232 Rigid epoxy resin, a blend of bisphenol A and bisphenol F resins, available from Resolution Performance Products, Houston, TX 77002, USA CARDOLITE NC514 Flexible epoxy resin, available from Cardolite Europe N.V, Belgium

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CARDOLITE NC513 Alkyl phenol glycidyl ether, reactive diluent, available from Cardolite Europe N.V, Belgium SCOTCHLITE D32 / 4500 (called “glass bubbles”) Hollow glass spheres, average particle size 85 pm, available from 3M, St. Paul, Minnesota, USA DUALITE E065-135D (called “Dualite”) pre-expanded polymer spheres, produced from acrylonitrile copolymer, average particle size 130 pm, density: 0.065 g / cm ³ , available from Lehmann & Voss Co., Germany LICOCENE PPA 330 Ethylene-1-propene copolymer as a translucent, plasticizer paste, available from Clariant, Germany JEFFAMINE D230 Polyether amine with a molecular weight of 230, curing agent, available from Huntsman Corporation, USA ANCAMINE K54 Tris- (dimethylamino methyl) phenol, available from Air Product Chemicals Europe, the Netherlands 1 -H imidazole available from BASF, Germany Calcium nitrate tetrahydrate Called "calcium nitrate" catalyst, available from Merck, Germany APYRAL 24 Aluminum hydroxide spheres, particle size (Dõo = 8 pm) available from Nabletc AG, Schwandorf, Germany.

7. Examples 1 and 2 [116] Preparation of a precursor composition with two components

Preparation of part A [117] JEFFAMINE D230 was placed in a 2-I mechanical mixer in which EPIKOTE 232 was added in portions at room temperature and under mixing. The mixing continued for 60 min at room temperature. The mixture was then heated to 80 ° C and maintained at this temperature for another 60 min. Calcium nitrate and imidazole were added and mixed until both materials were completely dissolved. The mixture was then cooled to room temperature, followed by the addition of ANCAMINE K54. The glassy bubbles were added to the homogeneous mixture and mixed for about 30 min. Then, the DUALITE microspheres were added and mixed for 15 minutes to produce a homogeneous white paste. The ingredients were used in the quantities shown in table 1.

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Preparation of part B [118] The base resin (part B) of the present invention was prepared by combining the ingredients mentioned in table 2 in a 2 liter mechanical mixer. A temperature below 35 ° C was maintained during the mixing process, using water-based cooling. The epoxy resins EPIKOTE 232, CARDOLITE NC 514 and CARDOLITE NC 513 were mixed with ethylene propene copolymer (plasticizer) for about 30 minutes. After achieving a homogeneous mixture, the glassy microspheres were added and mixed for 15 minutes. In a final step, the polymeric microspheres were added to the mixture and mixed until homogeneity was achieved. These mixtures were pastes with a smooth and uniform consistency. The ingredients were used in the quantities shown in table 2 (B1 and B2).

Preparation of the vibration dampening composition (A + B) [119] Parts A and B were combined in an A: B ratio of 1: 2 v / v, using a 400 mL cartridge, suitable for a ratio 2/1 B / A mixer, available from “Mixpac”. A mixing nozzle type MC 13-18 available from MIXPAC (Mixpac Systems, AG, Rotkreuz, Switzerland) was fitted to the cartridge.

[120] The precursor compositions were extruded (the extrusion speed was 40 g / min) in a carrier (a polytetrafluoroethylene (PTFE) slide) and were then spread to a thickness of about 1.5 mm, using laboratory coating. The samples were cured for 24 h at room temperature, followed by 2 h at 100 ° C in an oven. After cooling to room temperature, the samples were subjected to the ATD test procedure described above. The results are shown in table 3 (example 1).

8. Comparative example 1 (C1) [121] Part A, part B and the cured composition of A + B were prepared as described above for example 1, with the exception that the glass bubbles or polymeric microspheres were replaced by aluminum hydroxide spheres (APYRAL 24).

[122] The composition of parts A and B is shown in tables 1 (A2) and 2 (B3), and the mechanical properties of the cured composition are shown in table 3 (C1).

Table 1: Composition of part A

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A1 (%, by weight) A2 (% by weight) JEFFAMINE D230 44 44 EPIKOTE 232 11 11 ANCAMINE K54 12 12 Calcium nitrate 6 6 1 H-imidazole 1 1 “Glassy bubbles” 22 "Dualite" 4 APYRAL 24 26 Total 100 100

Table 2: Composition of part B

B1 (%, by weight) B2 (% by weight) B3 (%, by weight) (%, by weight, active) EPIKOTE 232 42 42 42 CARDOLITE NC514 20 20 20 CARDOLITE NC513 6 6 6 Glassy bubbles 20 22 Ethylenepropylene copolymer 8 8 8 Dualite 4 2 APYRAL 24 24 Total 100 100 100

Table 3: Mechanical properties of cured compositions

Example 1 Example 2. C1 Composition A1 + B1 A1 + B2 A2 + B3 peak loss factor > 0.45 > 0.45 > 0.45 Tg (° C) 69 80 75 Young Module at 25 ° C (MPa) > 900 > 900 > 900 Young Module at 100 ° C (MPa) 14 26 7 Young modulus at peak loss factor (MPa) 75 88 48

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Temperature range with a loss factor greater than 0.2 (° C) 46 40 <40 Density (g / cm ³ ) 0.5 0.6 1.1 Compressive strength at 25 ° C (MPa) 15 Table 4: ComDOsicão in Dorcentaaem, in Deso, for example d 1 above Feedstock Parties % by weight EPIKOTE 232 94.88 31.63 CARDOLITE NC514 40 13.33 CARDOLITE NC513 12 4.00 “Glassy bubbles” 61.95 20.65 Ethylene propylene copolymer 16 5.33 "Dualite" 12 4.00 JEFFAMINE D230 44.33 14.78 ANCAMINE K54 11.8 3.93 Calcium nitrate 6.04 2.01 1 H-imidazole 1 0.33 Total 300 100

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Claims (8)

1. Curable two-part precursor composition for preparing a vibration damping composition having a density of less than 0.9 g / cm ³ , said precursor composition CHARACTERIZED by the fact that it comprises: (I) part A comprising: (i) a curing agent capable of crosslinking both rigid and flexible part B epoxy resins; and (II) part B comprising: (i) one or more rigid epoxy resins; (ii) one or more flexible epoxy resins; (iii) a first set of hollow microspheres, which are pre-expanded compressible organic microspheres and have an average diameter from 90 pm to 200 pm, and (iv) a second set of hollow microspheres which are inorganic microspheres. 2. Precursor composition, according to claim 1, CHARACTERIZED by the fact that the flexible resin is an aromatic resin. 3. Precursor composition, according to claim 1 or 2, CHARACTERIZED by the fact that the microspheres of the first set have an average diameter from 90 pm to 200 pm. Precursor composition according to any one of claims 1 to 3, CHARACTERIZED by the fact that the microspheres of the second set have an average particle diameter from 5 pm to 105 pm. Precursor composition according to any one of claims 1 to 4, CHARACTERIZED by the fact that the rigid epoxy resin is derived from bisphenol A, epoxy-functionalized bisphenol F or a combination thereof. 6. Precursor composition according to any one of claims 1 to 5, CHARACTERIZED by the fact that the microspheres of the first set are organic and are present in an amount of 2 to 8% by weight. 7. Precursor composition according to any one of claims 1 to 6, CHARACTERIZED by the fact that the microspheres of the second set are inorganic and are present in an amount of 18 to 32% by weight. Petition 870180052347, of 06/18/2018, p. 39/41 2/2 8. Vibration damping composition CHARACTERIZED by the fact that it is obtained by curing the precursor composition as defined in any one of claims 1 to 7. Petition 870180052347, of 06/18/2018, p. 40/41