HU226636B1 - Flame retarded, broad frequency range micro- and nano composition with vibration- and noise reducing effect and products thereof - Google Patents

Abstract

A vibration and noise reducing composition contains additive consisting of nano- or micro-sized grains intercalated or covered with liquid elastomer, in addition to pre-used noise absorbing barium sulfate and flame retarding metal hydroxide or phosphorus compound additive and additives of polymer composition. The additive is montmorillonite intercalated with polybutene or micro-grained milled rubber covered with polybutene.

Description

FIELD OF THE INVENTION

FIELD OF THE INVENTION The present invention relates to flame retardant, vibration and noise reduction thermoplastic polymer compositions and products thereof which, in addition to conventional sound absorbing and flame retardant additives, also have intercalated / coated, organophilic nano and / or microparticles with a broad range of properties. the frequency range in which the compositions and products made thereof exhibit vibration and noise reduction effects.

History

A patent for the production of vibration and noise reduction discs is disclosed in steel and steel. with synthetic rubber and plastic laminated with plywood and foamed combination thereof (JP 2116655, 1990-05-01). An example is provided using foamed crosslinked elastomers for similar purposes (JP 2002317067, 200210-31). To enhance vibration and noise reduction, heterogeneous polymer powders such as polyamide, polyester, polyurea, polyurethane, etc. have been proposed. incorporation of powder into the polymer matrix (JP 2004143324, 2004-05-20), the resulting noise reduction composite is characterized by low density. A known method for increasing the efficiency of vibration and noise reduction is the incorporation of barium sulfate into a high density, and consequently high inert, additive into an elastomeric matrix or without separate surface treatment (U.S. Pat. No. 5,959,039), respectively. surface treatment to improve mechanical properties (U.S. Pat. No. 6,274,662). The descriptions described so far are suitable for damping vibrations of various characteristics in the wavelength range and do not meet the often indispensable requirement of flame retardancy. There is a description which discloses a flame retardant sound reduction composition consisting of polyvinyl chloride plastisol and antimony trioxide (U.S. Pat. No. 6,129,175), which however has the disadvantage of releasing toxic, corrosive gases into the environment when forced to burn. A process is known which describes a flame retardant composition with metal hydroxides for cable coating and which is also recommended for the manufacture of a vibration reduction plate (U.S. Pat. No. 6,667,358) which does not provide vibration reduction characteristics which are estimated to be below its barium sulphate-containing system. . There is a need for flame retardant, vibration and noise reduction compositions that do not produce harmful by-products when burned and have an effective vibration and noise reduction effect over a wide range of vibrations. The present invention relates to the surprising discovery that a conventional flame retardant additive for vibration and noise absorbing compositions consisting of a thermoplastic polymer blend and barium sulfate, e.g. in addition to metal hydroxide or phosphorus containing additives intercalated / coated with an organic elastomeric, nano and / or microparticulate fluid elastomer, effective vibration and noise reduction, flame retardant compositions or these can be used to obtain products with similar properties.

Brief Description of the Invention

This patent relates to flame retardant vibration and noise reduction, thermoplastic, optionally vulcanizable polymer compositions and products thereof, which, in addition to conventional sound absorption and flame retardant additives, contain intercalated / coated, nanoparticulate and / or micromolar, among other properties, they significantly widen the frequency range in which the composition and products made of it exert their vibration and noise reduction effects. The increased vibration and noise reduction effect is provided by the high viscosity liquid elastomer around the additive particles in vibration and noise. it reacts to deformation created by sound vibration by a viscous flow whose heat of friction is radiated to the environment, thus reducing the recovery of deformation energy. The fluid elastomer may be applied in the interparticle layer or through the introducing the surface layer into the composition prevents the liquid elastomeric cold flow, thereby allowing the composition to be formed into products of various shapes. The present invention also relates to various shapes, belts, conveyor belts, shoe parts, treads, etc., which may be manufactured from the polymer, if desired, by vulcanization or foaming, characterized by increased vibration and noise damping, while retaining other properties.

The composition is prepared by admixing a nano- and / or microparticle admixture intercalated / coated with a liquid elastomer into a mixture of the thermoplastic polymer melt that serves as the matrix of the composition, conventional silencing additives, flame retardant additives, and conventional additives to polymer compositions. Intercalation is when a few nanometers thick, sheet-like, organophilized nanoparticles, e.g. the liquid elastomer covering the organophilized montmorillonite flakes is laminated together so that a significant portion of the liquid elastomer is embedded between the flakes.

Additives intercalated / coated with the liquid elastomer can be prepared by pre-organophilized nano- or microparticles, or organophilic particles in the absence of organophilization, and the liquid elastomer by thermomechanical treatment, combined with heat and mechanical shear. homogenize in an internal mixer. If the nanoparticles or microparticles have not been previously organophilized, their organophilization can be accomplished in the intercalation / coating step by adding a sufficient amount of low HLB surfactant together with the liquid elastomer, and the organophilization occurs spontaneously in the thermomechanical homogenization step.

Preferred thermoplastic polymers as matrices of the composition are ethylene-vinyl acetate copolymer ethylene-acrylate copolymers, ethylene-α-olefin copolymers, ethylene-propylene copolymer, ethylene / propylene / diene elastomer (EPDM) styrene-butadiene copolymer, -styrene elastomer, thermoplastic polyurethane, and mixtures thereof.

HU 226 636 Β1

Further, to modify the properties of said polymers, optionally, polyurethane oils, oligophosphates, other extender oils, etc. may be used. employed.

Conventional barrier sulfate is a natural or precipitated barium sulfate additive.

Suitable flame retardant additives are metal hydroxides, e.g. magnesium hydroxide, aluminum hydroxide, magnesium bicarbonate, hydrotalcite, etc. or expandable flame retardant additives such as ammonium, ethylenediamine and melamine salts of phosphoric and polyphosphoric acids, other flame retardant additives containing phosphorus, and carbonising agents such as polyols and the like. oxygen and / or nitrogen-containing polymers, e.g. recycled polyurethane, polyamide.

Nanoparticles include clay minerals, illite, kaolinite, bentonite montmorillonite fractions, various degrees of processing of sepiolite, and natural and synthetic hydrotalcite. By nanoparticle is meant that one dimension of the three-dimensional particles has a size of up to 10 nm.

Suitable microparticles are calcium, magnesium carbonate, talc, magnesium, aluminum hydroxide, short basalt fiber, glass fiber, other mineral or organic fibers, fractions of used tire milling powder in the range of 50-300 pm, powdered polyurethane powder in the range 50-200 pm , short staple fibers of polypropylene (PP), polyamide (PA), polyethylene terephthalate (PET), poly (acrylonitrile) (PAN), length 1-6 mm.

Commonly used additives in polymer compositions are those used to influence the mechanical, rheological, stability characteristics and color of the composition.

Other conventional fillers and reinforcing materials, such as carbon black, silica types, calcium, magnesium, aluminum silicates, e.g. zeolite, clay minerals, talc, calcium, magnesium carbonate, diatomaceous earth, titanium dioxide, fly ash, wood flour, conventional fiber reinforcing materials, etc.

Low HLB surfactant modifying surfactants, reactive surfactants, maleinated polyolefins can be used to promote the homogeneity and incorporation of inorganic charge-strengthening components. glycerol monostearate, maleinated unsaturated fatty acid derivatives, maleinated polyethylene, etc.

Testing methods

The vibration-damping effect of the compositions can be characterized by two methods of dynamic mechanical analysis, the dynamic bending modulus and the dynamic torsional modulus. Measurement of dynamic bending modulus by elastic vibration-resonance curve according to ISO 6721-3: 1994, in the frequency range of 10-1100 Hz, dynamic torsional modulus test with AR 2000 Thermal Scanning Rheometer (TA Instruments; USA), 10-100 Hz, at room temperature.

Measurement of Bending Wave Loss Factor

Thin sheets depend on the sound insulation effect

- the bending stiffness of the baseplate,

the weight of the soundproofing sheet, and

- the loss of the sheet due to bending waves.

This complex effect is, in most cases, achieved by multilayer combined systems. In vehicle constructions, these structures often have a relatively small specific surface area and a thin wall thickness. The acoustic parameters of such thin flexible structures can be measured on a small sample by measuring the sound insulation, i.e. the propagation loss and the bending wave loss factor.

The bending loss factor is measured on a small, narrow belt with bending wave excitation. The sample dimensions are as follows:

Length: 300 mm

Width 20 mm

Thickness: 0.68 mm

This sample size covers the most important range of the acoustic frequency. The sample is excited with an electrodynamic vibrator. The sample is attached to the exciter with a thin layer of adhesive. The damping layer was fixed to the steel strip base with "Pálmatex" (HENKEL Magyarország Kft.) Adhesive.

The measurement of the bending loss factor is based on the measurement of the intrinsic frequency of the samples, and the bending wave loss factor can be calculated from the following equation:

ξ (/) = ί / (2 * Π * ^ · * τ) where

Z, (f) = frequency dependent value of bending loss factor f ^ is the i-th eigenfrequency of the sample

T = vibration decay time constant in the sample [time of dB decrease of vibration amplitude (-8.7)] Higher bending loss factor means greater vibration and noise reduction effect.

Measurement of dynamic torsional modulus

The results of the dynamic torsional modulus tests are the storage E, the loss modulus E and a loss factor of two quotients, E "/ E '= tan value. According to the definition of ISO 6721, the storage modulus E 'is characterized by the stiffness of a viscoelastic material and is proportional to the energy stored in the material during a strain stress cycle and is used to completely eliminate the deformation after the deformation has ceased. The loss modulus E, in turn, is proportional to the amount of energy applied to the deformation, which, as a result of internal friction, is converted into heat and dispersed into the environment. This part of the vibration energy invested is lost, the vibration energy is reduced by this amount and ultimately the vibration dampens. The absolute value of the loss modulus is suitable for comparing samples of the same size. Usually this loss of energy is the loss modulus E and the elastic modulus E '

EN 226 636 Β1, which is by definition called the loss factor and is denoted by tan5. This is a dimensionless number and its value is more independent of the substances tested. It is suitable for characterizing the vibration damping effect when examining samples of different size. This method and the resulting loss modulus or. loss factor allows direct measurement of the damping effect, which allows a good comparison of the damping effect of different compositions. The higher this value, the stronger the damping effect.

For flammability characterization, the Limiting Oxygen Index (LÓI) determination method (ASTM D-2863) and UL 94 (Underwriters Laboratories, USA) are commonly used.

When measuring the LÓI, the volume of oxygen-nitrogen in a suitable apparatus is determined in which the rod-shaped, vertically captured specimen of the test substance is lit for more than a specified period of time, 180 seconds or less. Larger HORSE means stronger flame retardant.

A rod-shaped specimen of the size specified in UL 94 is first fired horizontally. When the sample is complete, it is rated HB and is characterized by its flame spread rate. If the sample does not burn horizontally, a new vertical sample shall be ignited at the lower end for a specified period of time. If the sample does not burn, you may be classified as V2, V1, V0, depending on how long the flame is removed after burning, and burning droplets drop from the sample to ignite the cotton wool underneath the sample. The V0 rating is the strongest flame retardant.

comparative and embodiment examples

The invention is illustrated, without limiting the scope of the invention, by examples of the formulations shown in Table 1, of which Examples 1, 2 and 4 serve as comparative examples, while Examples 3, 5, 6 and 7 are intended to illustrate the advantages of the compositions of the invention. The numerical values given for the compositions in the examples are by weight.

The formulations of Examples 1, 2 and 4 were prepared by adding the polymer components listed below in Table 1, in the order of weight ratio, to the Plasti-Corder PL 2000 internal pre-heated internal unit at the same weight ratio. mixer (Brabender Measurement and Controlled Systems, Germany). The components were melted there at 50 rpm. The powdery noise-absorbing barium sulphate and the flame retardant component (or components) were pre-physically homogenized and added in several portions to the polymer melt. The mixture was homogenized for ten minutes, forming small sheets from the melt and, after solidification, in a knife grinder for approx. Cut into 3 mm grinder. 3 and 5, respectively. The components of the composition of Examples 6 and 7 were homogenized in a similar manner to the comparative samples except that the liquid elastomer and nanosilicate components, such as Hyvis 20 polybutene (BP Petrochemicals, Britannia) and Benton SD2 organophilized montmorillonite (RHEOX Inc. USA), Hyvis 20 polybutene and Pangel IB20 organophilized sepiolite (TOLSA SA Spain) in Examples 6 and 7 were also pre-coated with an internal blender and added to the flame retardant polymer additive already in the inner mixing chamber. Hereinafter, polybutene-iterated organophilic montmorillonite is designated by the letters IMM, and polybutene-coated organophilic sepiolite is designated by the letters ISEP. Compounds of the exemplary embodiments were prepared in a manner similar to that of the comparative samples. Sheets of 100 * 100 * 2 mm were pressed from the grinder of the polymer compositions at 170 ° C and the test specimens were cut from them.

In Table 1, the flammability data of the comparative and embodiment examples with LOI and UL 94 are given. It is found that the sample of Embodiment 3 of APP + PER, which is polymer-intercalated with IMM, has a flame-retardant similar to that of comparative sample 2 without IMM. A similar statement can be made with ATH - flame retardant

Comparison of Embodiment 5 and Comparative Example 4 and Comparative Examples 2 and 4 and Embodiment 6 and 7.

Figure 1 shows the change in bending loss coefficient of flame retardant compositions with APP / PER additive system as a function of its own frequency.

Figure 1 shows the bending loss coefficient of three different sound reduction plates of Comparative Examples 1 and 2 and of Example 3. Sample 1 does not contain a conventional flame retardant additive, only a conventional barrier sulfate addition to the polymer matrix. Sample 2 also contains an expandable APP / PER flame retardant additive system. Example 3 already includes montmorillonite intercalated with a liquid elastomer to enhance vibration absorption. Comparison of the bending loss factor for samples 1 and 2 shows that the flame retardant additive system alone increases the loss factor, but only in the two narrower frequency ranges of 20-30 to 600-700 Hz. However, the value of the bending loss coefficient of the composition of Example 3 containing the anti-vibration enhancer is always higher than that of the two comparative samples, i.e., the montmorillonite intercalated with the liquid elastomer increases the broad frequency range. noise-absorbing efficiency.

Fig. 2 shows the change in the bending loss coefficient of ATH flame retardant compositions as a function of their own frequency.

Figure 2 shows a comparison of non-flame retardant 1 with comparative examples of flame retardant with aluminum trihydrate 4;

The laminate shows the bending loss modulus of the compositions of Example 5, which also include montmorillonite intercalated with a liquid elastomer in addition to ATH. In this case, it can be observed that the flame retardant in itself increases the noise absorbing capacity, but here again only in two narrow frequency ranges. IMM additive intercalated with liquid elastomer to enhance vibration absorption,

Improves vibration absorption in the frequency range of 20-500 Hz.

Given that vibration absorbing compositions are primarily used to absorb low frequency vibrations, we have now investigated the loss factor and the fine tuning of the dynamic torsional modulus in a frequency range of 1-100 Hz. module.

Table 1

Composition and flammability characteristics of vibration and noise reduction compositions

components Pattern sign Percentage of components,% Example 1 Example 2 Example 3 Example 4 Example 5. Example 6 Example 7 MDPE QAMAR 12.25 12.25 12.25 12.25 12.25 12.25 12.25 Ibucell [ethylene vinyl acetate jacket] 23.75 23.75 23.75 23.75 23.75 23.75 23.75 B (barium sulphate) 63.3 48.4 43.4 25.7 23.2 43.4 23.2 APP (ammonium polyphosphate) 11 11 11 PER (pentaerythritol) 3.7 3.7 3.7 ATH (aluminum trihydrate) 37.6 35.1 35.1 OMM Benton SD2 Organophilized Montmorillonite 2.5 2.5 PangelB20 is an organophilized sepiolite 2.5 2.5 Hyvis 20 polybutene 2.5 2.5 2.5 2.5 GMS glycerol monostearate 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Properties UL94 HB VO VO VO VO VO VO Horse% 19.5 30 31 30 31 32 30

Figures 3 and 4 show the elastic loss coefficient, tg δ, respectively, of the same systems by dynamic torsion analysis. the loss modulus shows G as a function of torsion frequency.

Figure 3 is a sample of Comparative Example 1 (B) without the flame retardant, Comparison 2 (B + APP / PER) with the flame retardant and polymer intercalated montmorillonite enhancing the flame retardant and vibration damping (Figure 3). The loss factor of B + APP / PER + IMM) is plotted against the torsion frequency.

Figure 3 shows that the addition of the APP / PER flame retardant additive system, with the exception of the frequency range below 40 Hz, significantly reduces the sample loss rate compared to the non-additive sample. As a result of the montmorillonite intercalated with the polymer, the loss factor again reaches the loss factor of the unadditioned system, i.e., the vibration absorption tendency of the composition is recovered by the additive.

Figure 4 shows a sample of Comparative Example 1 (B) without flame retardant, Comparative 4 with ATH flame retardant (B + ATH) and Montmorillonite intercalated with flame retardant and vibration absorption enhancing polymer (B + ATH). + IMM) loss! plotted against torsional frequency.

Figure 4 shows that the ATH 40 flame retardant additive does not significantly affect the elastic loss modulus of the assay, whereas the polymer-intercalated montmorillonite causes a significant increase in the elastic loss modulus over the range of 50 Hz, thereby improving the vibration absorption propensity of the composition.

Figure 5: Example of Comparative Example 1 (B) without flame retardant, Comparative Flame Retardant 2 with APP / PER system (B + APP / PER) and Example 6 containing flame retardant and polymer-intercalated sepiol50 lake to enhance vibration damping The loss modulus of (B + APP / PER + ISEP) versus torsion frequency is plotted.

Figure 5 shows that, with the APP / PER flame retardant additive system, the polymer-coated sepiolite additive has no effect on the vibration absorption propensity measured by the loss modulus. However, as shown in Figure 6, the polymer-coated sepiolite additive can also significantly increase the propensity to vibrate when used with another type of APP / PER flame retardant additive system.

HU 226 636 Β1

Figure 6 is a sample of Comparative Example 1 (B) without flame retardant, Comparative 4 with ATH flame retardant (B + ATH) and Example 7 (B + ATH + ISEP) also containing sepiolite intercalated with flame retardant and vibration damping polymer. is plotted as a function of torsional frequency.

It can be seen from Figure 6 that, besides the ATH flame retardant additive, the polybutene coated sepiolite significantly increases the loss modulus of the polymer composition, i.e., the vibration absorption tendency of the composition.

Claims (11)

PATENT CLAIMS 1. A flame retardant, vibration and noise reduction, thermoplastic polymer composition comprising the following components, based on the total weight of the composition: (a) 20 to 40% by weight of a thermoplastic polymer or a mixture of thermoplastic polymers, b) conventional low molecular weight or oligomeric additives which modify the rheology of thermoplastic polymers, 0-15%, (c) barium sulphate of known high density which contributes to vibration and noise absorption of between 5% and 65%, (d) 5-65% conventional additive or additive system based on metal hydroxide or phosphorus compound to reduce flammability, e) from 1% to 20% by weight of the liquid elastomer and the nano / microparticles in weight ratio between the liquid elastomer and the nano- and microparticles, intercalated / coated with a liquid elastomer, f) fillers and reinforcing materials customary for modifying mechanical properties, 0-30%, g) 0-5% additive to improve interaction between polar additives and polymer matrix, h) customary stabilizers and coloring agents of polymer compositions of 0.1 to 2%. The thermoplastic polymer composition according to claim 1, wherein the matrix is a thermoplastic polymer or a mixture of thermoplastic polymers, preferably ethylene (vinyl acetate), ethylene acrylate copolymers, ethylene-aolefin copolymers, ethylene-propylene copolymer, EPDM, styrene copolymer, styrene-butadiene-styrene elastomer, thermoplastic polyurethane, and mixtures thereof. The polymer composition of claim 1, wherein, if desired, small molecule additives or oligomers that modify the rheology of thermoplastic polymers are urethan oils, oligophosphates, extender oils. The polymer composition of claim 1, wherein the barium sulfate additive to assist in sound absorption is natural or precipitated barium sulfate. 5. A polymer composition according to claim 1, wherein the conventional flammable additives are metal hydroxides or phosphorous compound-based expandable additives, the metal hydroxides preferably being magnesium hydroxide, aluminum hydroxide, magnesium bicarbonate, hydrotalcite, and the foaming agent. or salts of polyphosphoric acid with ammonia, ethylenediamine or melamine, other phosphorus-containing flame retardant additives and, if desired, carbonization enhancing components such as polyols, oxygen and / or nitrogen containing polymers, recycled polyurethane, polyamide. The polymer composition of claim 1, wherein the liquid elastomer is intercalated / coated with additives containing organophilic nano and / or microparticles. (a) Nanoparticulate clay minerals, illite, kaolinite, bentonite montmorillonite fractions, varying degrees of processing of sepiolite, and natural and synthetic hydrotalcite, microparticles of calcium carbonate, magnesium hydroxide, aluminum hydroxide, organo-mineral, short basalt fibers, or inorganic forms thereof, and fractions of a powder derived from the tires used for grinding, in the range of 50 to 300 µm, in the range of 50 to 200 µm of ground polyurethane powder, synthetic staple fibers of ΡΡ, PA, PET, PAN of 1-6 mm, b) the liquid elastomer component is preferably polybutene, polyisobutylene, polybutadiene, maleinized polybutadiene, polybutadiene diluted styrene butadiene, silicone elastomer, c) additives containing intercalated / coated liquid elastomer containing thermophilic mechanical homogenization of the liquid elastomer and the organophilic nano and / or microparticles prior to forming the composition or, if there are unorganophilized nano or microparticles in the elastomer, the particles are prepared in the same step by the addition of low HLB surfactants, reactive surfactants, maleinated polyolefins. The polymer composition according to claim 1, further comprising, if desired, mechanical fillers such as various types of silica, calcium, magnesium, aluminum silicates, preferably zeolite, clay minerals, talc, calcium, to modify the mechanical properties. Contains magnesium carbonate, diatomaceous earth, titanium dioxide, carbon black, fly ash, wood flour, common fiber reinforcing materials in compositions. 8. A polymer composition according to claim 1, wherein, if desired, additives that enhance the interaction between the polar additives and the polymer matrix are low HLB surfactants, reactive surfactants, maleinated polyolefins. Use of an elastomer composition according to claim 1 for the manufacture of vibration and noise reduction products. Vibration, noise reduction products comprising the elastomeric composition of claim 1. Vibration, noise reduction products comprising the elastomeric composition of claim 1, which products are vulcanized or foamed to provide improved formability.