DE1694139A1 - Use of hardened epoxy resins as vibration-damping material - Google Patents

Description

FARBWERKE HOECHST AG.

Frankfurt (M) -Hoechst

Appendix I ^. March 1967

to the patent application Fw Dr * Eg / Dr

5320 .-

Use of cured epoxy resins as sohwlngungsdämpfende s material '

The invention relates to the use of hardened Epoxy resin compounds, coatings and coatings, which in addition to dimensional and temperature resistance and impact resistance have a high vibration damping effect.

It is known to harden epoxy resins aliphatic polyamines, e.g. to use diethylenetriamine or triethylenetetramine. The epoxy resin compounds hardened in this way, -over Trains and * coatings are characterized by a high degree of hardness and adhesion to metal »but also by a considerable brittleness and insufficient shock resistance. Even slight mechanical stresses lead to cracks and destruction of the resin structure.

On the other hand, it is known to use plastics with special viscoelastic properties Properties, especially those with high κ internal damping as vibration-damping layers, e.g.

to be used in sheet metal constructions. They are used as one-sided spray, spatula or adhesive layers of the covering, mostly provided with fillers and often combined with other substances. They are also used as intermediate layers in so-called Composite sheet metal or sandwich constructions are used. Their purpose is primarily to alleviate the annoyance Roaring of sheet metal structures in machines, devices and vehicles, as well as improving the sound insulation of Sheet metal walls, e.g. for the encapsulation of noisy machines, and the suppression of structure-borne noise through sheet metal constructions, e.g. in large vehicles or ships, which can lead to airborne sound radiation at distant locations. Depending on the application, high attenuation is achieved in certain Frequency and temperature ranges required. The frequency range generally corresponds to that of the audio frequency, for example between 20 and 1600 Hz.

It is now known to use damping materials that meet these requirements, to be produced in such a way that either = amorphous thermoplastics with a suitable distribution of the freezing temperatures mixed or monomers, the homopolymers of which have suitable positions at the glass transition temperature, copolymerized with one another What all these substances have in common is that they only have a little Have adhesion to metal and thus either only with the help of an adhesive or in the form of sandwich panels in the Metal structure must be attached.

Surprisingly, it has now been found that form and temperature-resistant and shock-resistant hardened epoxy resins in an excellent way as a material for vibration damping suitable. ,

The invention relates to the use of glycidylamines and / or glycidylamines with polyether amines, preferably polypropylene oxide amines, cured epoxy resins produced alone or in a mixture with aliphatic polyamines as a vibration-damping material.

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1694133

Pw 5520

Polypropylene oxide amines are particularly suitable as polyether amines from the molecular weight of 350 to 5OOO of the formulas I and / or II

\ ⁷

X-CH ₂ CH-

CH

> 1

OCH ₂ CH

CH,

OCH ₂ CH

OCH ₂ CH

OCH ₂ CH

(II) CH ^ -CHpC-CHp-

CH ₀ -

where X is an amino or hydroxyl group, m is an integer from 4 to 32 and y *, y ^ and y * are integers from 1 to 15 and where at most 50 percent of all amino groups can be replaced by terminal hydroxyl groups, alone or in a mixture with aliphatic polyamines of the amine equivalent I5 to 6o.

As glycidyl ethers and / or glycidylamines are preferred those with epoxy equivalents of 120 to 4000 were used; as glycidyl ethers are in particular diglycldyl ethers

Formula ΙΪΙ
0

CH ₀ -CH-CH ₀ -

OCH ₂ CH-CH ₀ -OH

(in)

T09830 / 1506

.4-

suitable, where η denotes integers from 0 to 10. as have been particularly beneficial. Diglycidyl ether Formula III with epoxy equivalents of 190 to 250 has been proven. Furthermore, diglycidylamines can preferably be used as epoxy components with epoxy equivalents of 120 to 250 can be used.

The area of application of the vibration-damping hardened

Epoxies preferably extend to the area

the listening frequencies and the temperature range between

-50 ⁰ C and +150 ⁰ C. - ·.

It is possible to produce vibration-damping, hardened epoxy resin compounds with a targeted position of the maximum loss factor, the temperature of which is defined as the dynamic freezing temperature T dyn, in the temperature range from -50 to + 1 ^ 0 ⁰ C, depending on the chain length of the polyether amine used for hardening. The manufacturing process also allows the range of maximum attenuation to be broadened, depending on the proportion of terminal hydroxyl groups in the folyetheramine. It also allows the setting of a certain dynamic modulus of elasticity E ^{1, which is} dependent on the mesh size of the resin, in the rubber-elastic range (equilibrium modulus, see "Elastic and viscous properties of materials, principles and terms", published by the German Association for Material Testing (DVM), Beutli-Ver trieb GmbH, Berlin, 1963);

Compared to the previously customary, by mixing amorphous thermoplastics with a suitable position of the freezing temperatures or by copolymerization of monomers, their homopolymers have suitable positions of the freezing temperature, the damping masses generated by polyaddition of glycidyl ethers Polyether amines produced damping compounds have significant advantages on. On the one hand, they allow due to the great adhesive strength of epoxy resins on metals the production of one-sided coated Sheet metal structures with a high damping effect

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by simply spraying or brushing on the reaction mixture, which is thinly liquid at room temperature, which is then replaced by thermal Post-treatment hardens, on the other hand, the production of sandwich constructions is made much easier, as this is the case Room temperature, low viscosity mixture of polyetheramine and epoxy resin not only has a long steaming time that can be adjusted by the outside temperature, but also because of its low viscosity Filled through a small opening in the finished sandwich construction and flat without any disruptive shrinkage or expansion can be thermally cured there.

Figure 1 shows the range of variation of the use according to the invention of cured epoxy resins with regard to the temperature. In the flexural vibration test, the dependence of the dynamic modulus of elasticity E ^f and the loss factor d on the temperature was measured at a frequency of 100 Hz. It was found, surprisingly, that the maximum of the loss factor d, the temperature of which is also known as the dynamic glass transition temperature T. _d , depending on the choice of the chain length of the polyether amine, can be precisely determined within the temperature range from -50 C to +130 C. It was also found that when using polyether amines, -bei

through which only part of the terminal hydroxyl groups are primary

is
Amino groups substituted "v" not only the location of the dynamic Einfriertemperatür T_ _ _d is shifted to lower temperatures, but the Temperaturbahdbreite maximum vibration damping can be increased. A shift from T. at higher temperatures with a simultaneous increase in the temperature range of maximum vibration damping is carried out by adding polyamines with a low equivalent weight, for example triethylenetetramine. For example, a hardening product made from equivalent amounts of a diglycidyl ether of the formula I with an epoxy equivalent of 200 and a linear polypropylene oxide amine of the formula I with a molecular weight of 400, which is 23.4 percent,

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drew on the reactive end groups containing hydroxyl groups, a dynamic glass transition temperature of 52 ^° C. For a linear polypropylene oxide amine of the formula I "of the same molecular weight, but which contains only 1.1 percent, based on the reactive end groups, hydroxyl groups

T, a value of 70 ⁰ C. An analogous behavior is with g dyn

linear and branched pcilypropylene oxide amines with molecular weights 700, 750 and 1000. On the other hand shows a curing ■ product of the same diglycidyl ether with a curing agent mixture of one equivalent of triethylenetetramine and Polypropylenoxidamin of molecular weight 2000 containing 5.6 percent terminal hydroxyl groups, a dynamic glass transition temperature of only -10 ⁰ C while a pure Polypropylenoxidamin of molecular weight 2000 cured product should have a dynamic glass transition temperature of about -5O ⁰ C, as can be determined by extrapolation. By varying the chain length of the Polyätheramins, the content of terminal hydroxyl groups and addition of a polyamine with a lower equivalent weight so that each desired attenuation peak between -50 and +130 ⁰ C can be set. Curves V and VIII show that this can also be used to broaden the temperature range in the manner indicated.

PUr coatings and coverings of sheet metal constructions preferably hardening products from diglycidyl ethers Formula III with an epoxy equivalent of 200 and linear and / or branched polypropylene oxide amines of the formulas I and II with A molecular weight of up to 950 is used, which, in addition to dimensional stability, temperature stability and impact resistance, has a high level of vibration dampening Have an effect. The maximum of the loss factor can be determined when using a polyether amine of the formula I on the molecular weight Set 700 to room temperature.

For sandwich constructions, it has proven to be useful Polyether amines of the formula I and II with a molecular weight of 900 to 2500 with or without the addition of lower aliphatic poly-

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to use amines such as triethylenetetramine. The relative soft masses allow high damping of the composite body, which is given additional strength and rigidity due to the still noticeable adhesion to the metal.

All resins used according to the invention have a very low swellability in water. The polypropylene oxide amines in question of formulas I and II, in which 0.1 to 50 percent, based on the terminal amino groups, unreacted hydroxyl groups may be contained, according to the Belgian patent 677,124 by aminolysis of polypropylene oxides made with ammonia in the presence of hydrogenation catalysts.

The resins used according to the invention can be unfilled or be used filled. Solid fillers such as graphite, clay, wood flour, vermiculite or Sand or liquid such as tar or bitumen.

example 1

32.35 g diglycidyl ether of the formula III with one epoxide equivalent of 192 are with 17.65 g of a linear polypropylene oxide amine of the formula I with an average molecular weight of 400 und.einem Amine equivalent 104 (1.1 percent hydroxyl end groups, based on reactive end groups) well mixed and for 5 minutes degassed under reduced pressure. Test specimens are made from the above mixture of 8 mm wide and 3 mm thick and various lengths poured and cured for 2 hours at 110 ° C. In the flexural vibration test the dynamic modulus of elasticity E 'and loss factor dj as a function of the temperature at 100 Hz measured (see Figure 1). It's going to be dynamic Freezing temperature of 7 ° G measured, ftas the same mixture standard bars are produced and the mechanical values are measured. In addition to the values given in Table 1, a flexural strength of 1020 kg / efir and an impact strength of Measured 132.5 cm kg / cm.

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Example 2

24.5 g diglycidyl ether of the formula ΙΙΪ with an "epoxy equivalent of 192 are mixed well with 25/5 g of a linear polypropylene oxide amine with an average molecular weight of 700 and an amine equivalent of 193 (16> 5 percent hydroxyl end groups, based on reactive end groups) and 5 Minutes at reduced pressure. To produce the test specimens, the procedure is as in Example 1 and the dynamic modulus of elasticity E '^^ and loss factor djj are measured as a function of the temperature at 100 Hz (see FIG. 1). A dynamic freezing temperature of 30 ^{° is used} C. Test specimens for measuring the mechanical parameters are made from the same mixture (cf. Table 1). The viscoplastic masses have high strength, and varnishes and coatings on iron and aluminum sheet produced from them also have high adhesive strength. They are not swollen by water.

Example 3

21.7 g of diglycidyl ether of the formula III with an epoxide equivalent of 192 are mixed thoroughly with 28.3 g of a linear polypropylene oxide amine with an average molecular weight of 950 and an amine equivalent of 250 (2.5 percent hydroxyl end groups, based on reactive end groups) and mixed for 5 minutes degassed at reduced pressure. The procedure is as in Example 1, but hardened at 90 ° C. for 8 hours. The dynamic modulus of elasticity ^Ε 'ηΐ ^ ^{10 and} the loss factor d _{Ii; c are} measured as a function of the temperature and a dynamic glass transition temperature of 4 ° C is determined (see Figure 1). Test specimens for measuring the mechanical parameters are made from the same mixture (see Table 1).

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Example 4

12.0 g of diglyeidyl ether of the formula III with an epoxide equivalent of 192 are good with 32.8 g of a linear polypropylene oxide amine with an average molecular weight of 2.000 and an amine equivalent of 525 (5.6 percent hydroxyl end groups, based on reactive end groups). mixed and degassed for 5 minutes at reduced pressure. The mixture is poured into molds and ^{cured for 12 hours at HO 0} C. A very soft mass is formed which is sticky at room temperature and which no longer shows any epoxide groups free from the IR spectrum and which has a freezing temperature of -52 ° C. Despite its low dimensional stability, the product shows a swellability of only 2.3 percent when stored in water for 50 hours. and can be used for sound insulation at temperatures below -20 ⁰ C.

Example 5

28.8 g of diglyeidyl ether of the formula ΊII with an epoxide equivalent of 192 are mixed thoroughly with 19 »5 g of a linear polypropylene oxide amine with an average molecular weight of 400 and an amine equivalent of 130 (23.4 percent hydroxyl end groups, based on reactive end groups) and mixed for 5 minutes degassed at reduced pressure. Test specimens according to Example 1 are made from the above mixture and cured at 110 ° C. for 2 hours. From the tough-elastisehen product which has a ". Having glass transition temperature of 24 ⁰ C, the dynamic elastic modulus E'Y be and the loss factor dy as a function of temperature at 100 Hz measured It is concluded a dynamic glass transition temperature of 52 ° C. . the transition area from the solid to gummielastisehen state 1st here broader than the produced according to example 1 product, characterized it 1st for vibration damping in a larger Temperaturbereieh suitable (35 bie 7O ⁰ C), Aujs de "same Gemiaeh be prepared standard rods and the mechanical values From the values listed in Table 1, a wear resistance * of 177 kg / cm ^{2 was obtained}

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BATH ORIGINAL

established. Also remarkable is the extraordinary high elongation of 110.4 percent, which in combination with a Brinell hardness of 3507 kg / cm and low swellability in water makes the material particularly suitable for one-sided vibration-damping coatings with high durability.

example 6th

28.8 g Dlglyoidylather the formula III with an epoxy equivalent of 192 are mit.l8.0 g of a branched polypropylene oxide amine with an average molecular weight of 418 and an amine equivalent of 120 (59.6 percent hydroxyl end groups, based on reactive end groups) and thoroughly mixed Degassed for 5 minutes at reduced pressure. The mixture is poured into molds and cured at 110 ° C. for 12 hours. The result is a tough, hard casting resin with a glass transition temperature of 39 C, the mechanical constants of which can be found in Table 1. The product, which gives tough hard coatings and paints is suitable for vibration damping from 6O ⁰ C.

Example 7

25.4 g of diglycidyl ether of the formula III with an epoxy equivalent of 192 are mixed thoroughly with 24.6 g of a branched polypropylene oxide amine with an average molecular weight of 7JO and an amine equivalent of 187 (35 * 0 percent hydroxyl end groups, based on reactive end groups) and mixed for 5 minutes degassed at reduced pressure. The Gemjaoh is poured into molds and annealed 12 hours at 110 ⁰ C ._. The result is a tough, elastic resin which, in addition to good hardness (see Table 1), has an extraordinary elongation of 90.4 percent and, in the form of one-sided coatings and cracks, is excellently suited to dampening vibrations.

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Example 8 '

24.0 g of diglyeidyl ether of the formula III with an epoxy equivalent of 192 are mixed with a 1 ϊ 1 mixture of 52.8 g of linear polypropylene oxide amine with an average molecular weight of 2000 and an amine equivalent of 525 (5 * 6 percent hydroxyl end groups) and 1, 03 g of triethylenetetramine mixed well. The solution is initially clear and, after degassing, is poured into molds and cured at 110 ° C. for 6 hours. During curing, clouding occurs due to segregation. A soft, plastic material is obtained which no longer has any free epoxy groups in the IR spectrum. As in Example 1, the temperature dependence of the dynamic modulus of elasticity is. E ¹ ^ -J ₁₁ UQd. of the loss factor dyjjj measured at 100 Hz (see Figure 1). A dynamic freezing temperature of -10 ° C is measured. The material is therefore particularly suitable for damping vibrations at low temperatures, for example below 0 ^° C, in sandwich forms.

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Table 1 ; Properties of the cured resins (12 hours, HO ⁰ C) from equivalent amounts of diglycidyl
■ ether of the formula I from epoxy equivalent 192 and polypropylene oxide amine

Belsp. Polypropylene oxide amih AmIn ^
Equiva
lent % OH end
groups Hardened resin Sinfrier
Pempera-
tur _n
Tg (° C) Bullet
printing hardness,
10 sec λ
(kg / em ^) 307 Tear
firm
speed ρ
(kg / W) Strain , Swelling in "water
(50 hours)
* Mole
ge
weight 104 1.1 Exterior
Behavior
th + 4o 535 479 8.7 1.2 1 400 193 "16.5 tough, ;'
hard -10 32.5 $ 21 19.2 47.7 ' 2.3 2. 2 700 250 2.5 tough, ■
elast. -22 3 ^, 8 10.4 26.8 ? 2.5, 3 950 525 5.6 soft,
elast. -52 - 2.3 * fc 4->
O
cc
OO 2000 130 23.4 what
evil
lig +24 125.5 110.4 0.9 = <*>
D ο 400, 120 39.6 tough,
elast. +39 405 9.1 2.8 O 418 187 35.0 uh,
hard 90.4 3.8
i! i σ>
7th 730 tough,
elast.

Claims (10)

1. Use of by hardening glycidyl ethers and / or glycidyl amines with polyether amines alone or in a mixture with cured epoxy resins produced from aliphatic polyamines as a vibration-damping material. 2. Use of glycidyl ethers and / or glycidylamines caused by hardening cured epoxy resins produced with polypropylene oxide amines alone or in admixture with aliphatic polyamines as a vibration-damping material. 3. Use of glycidyl ethers and / or glycidylamines caused by hardening with polypropylene oxide amines with a molecular weight of 350 to 3000 of the formulas I and / or II X-CH ₂ CH r f; OCH ₂ CH- CH CH ₃ -CH ₂ C-CH ₂ C-C CH where X is an amino or hydroxyl group, m is an integer from 4 to 32 and y «, y ₂ and y denote integers from 1 to 15 and where at most 50 percent of all amino groups can be replaced by terminal hydroxyl groups, alone or as a mixture cured epoxy resins made with aliphatic polyamines of amine equivalent 15 to 60 as vibration damping material. 10 9 8 3 0/1506 Fw 5320 4. Use of cured epoxy resins according to Claims 1 to 3, characterized in that the glycidyl ethers used and / or glycidylamines have epoxide equivalents of 120 to 4000. 5. Use of cured epoxy resins according to Claims 1 to 4, characterized in that diglycidyl ether ' of "Formula III CH ₂ -CH-CH ₂ - OCH ₂ CH-CH ₂ -OH 0-ACA- OCH ₀ CH-CH ₀ I Χ · - / 2, η CH. (in) where η means integers from 0 to 10, »» are used. 6. Use of cured epoxy resins according to claims
1 to 5, characterized in that the glycidyl ether
Diglycidyl ethers with epoxy equivalents from 190 to 250
be used. 7. Use of cured epoxy resins according to Claims 1 to 6, »characterized in that diglycldylamines as glycidylamines
with epoxy equivalents of 120 to 250 can be used. 8. Use of cured epoxy resins according to Claims 1 to 7, characterized in that the cured epoxy resins as
-vibration-dampening material in the area of the audio frequencies and used at temperatures between -50 ° C and + lj50 ° C, 109830/1508