DE1301467B - Process for the production of rubber vulcanizates reinforced with silica and / or calcium or aluminum silicates - Google Patents

Description

1 2

From U.S. Pat. No. 2,733,160 and which has 300 m ^a / g. The specific surface area is known from French patent specification 1166 558, for example by the BET method (according to Brunauer that silicas that are superficially esterified Emmet, Teller) can be used as rubber fillers by nitrogen adsorption. it's correct.

This pretreatment of the fillers is to achieve 5 The fillers may be moisture contents that such fillers easier in 0.5 to 20, preferably 3 to 10 weight percent, be plastomers and elastomers when incorporated true as a weight loss at 110 ⁰ C, have to distribute. An increase in the reinforcing effect In addition to adsorbed water, the silica contained practically does not occur. and silicates still bound.es water in the form of It has now been found that particularly good io silanol groups. A sharp distinction between results in the production of "free" and "bound" water with silicic acid is not possible and / or calcium and aluminum silicates reinforced. The treatment with the present invention rubber vulcanizates with the addition of filler compounds used can be obtained activators at temperatures when disposed of as filler between 5 and 100 ⁰ C, preferably 15 to 70 ⁰ C, Erdie esters of unsaturated 4 carbon atoms followed by 15 °. The additives used according to the invention containing dicarboxylic acids with mono- or polyvalent can add to the fillers, for. B. used in amounts of alcohols. Particularly favorable results 0.5 to 15 percent by weight, preferably 2 to 8 percent, are obtained if the additives according to the invention are not added as such when mixing on the roller or in the fabric, percentages by weight, based on the dry filler. Higher additions can be incorporated into internal mixers, but are initially * © possible, but filler has been added due to excessive deformation and, with this, after the rubber mixture has been tightened, it is usually not recommended for the methods described below.

be mixed. But you can first produce a more concentrated unge mixture containing less than 4 carbon atoms and use this z. B. when mixing Saturated dicarboxylic acids are preferably fumarics in the rubber in such amounts as the pure filler acid and maleic acid understood. In the case of the esters, add substance that the given concentration can both the half-esters and the proportions to be achieved. You can also do it in one Act diester. The alcohol component of the ester second step the concentrate with another can be chosen arbitrarily. So esters are both with amount of filler to the desired loading level Mix short- as well as long-chain aliphatic 30 tration.

Alcohol components active up to approximately As rubber are generally diolefin-18 Carbon atoms, preferably 2 to 6 carbon polymers, e.g. B. butadiene polymers containing iso-atoms, z. B. methanol, ethanol, propene, dimethylbutadiene or their homologues or panol, hexanol, dodecanol or stearyl alcohol. Copolymers of these diolefins with polymerizing also aromatic alcohols can be used, 35 baren vinyl compounds such as styrene, methyl styrene, like benzyl alcohol. The alcohols can also be non-divinylbenzene or acrylonitrile. The amount be saturated, like allyl alcohol. Instead of one of the vinyl compounds, for. B. 10 to 40%, Valuable alcohols can also be polyvalent Aiko- Particularly good effects through the invention hole can be used, such as glycol, glycerine, hexane-like processes for butadiene-styrene rubber triol, pentaerythritol, butenediol or butynediol. The 40 scored.

Esters can be produced by any known method

can be obtained. If you work either on a mixing roller or in an indoor

of polyhydric alcohols at a molar ratio mixer at temperatures up to 200 ⁰ C. Particularly

from acid to alcohol as 1: 1, favorable results are obtained when the temperature

esterification conaenation products with polymer character 45 temperature during the mixing process between 120

obtain. As long as these in the amounts as, preferably up to 18O ⁰ C, lies in the 200 ⁰ C and 140th It is

Rubber mixtures are used, still advantageously in this case the mixture of rubber

If rubber is soluble, such polyesters and fillers used according to the invention can also be used

esters can be used. also a stabilizer, e.g. B. an aging

As already mentioned, after an esterification process, protective agents can be added. Zinc oxide, stearic acid and

known methods. In the case of the mono- the other usual mixture components are

ester of maleic acid, it is sufficient in many cases, the stoichio- advantageously at temperatures below 110 ⁰ C.

metric mixture of maleic anhydride and added.

To warm alcohol for a short time at 6O ⁰ C In the following examples, the following complete esterification were to achieve. Acid 55 test methods applied: Catalysts, especially those based on ion exchangers, have proven to be particularly effective. Since the resulting 1. tensile strength, elongation at break, tension at 300 esters are partly not very volatile and so _and 500% elongation according to DIN 53504; measured with no further purified by distillation _at standard ring RI and 4 mm thickness, can be offered by using the fixed 60

Ion exchanger a simple way of increasing the 2nd structural strength (in kg) of a standard ring RII

to separate liquid ester from the catalyst. and 4 mm thickness, the one with 2x5 incisions

Pure silicic acid or (1 mm deep) come as light-colored fillers. Calcium and aluminum silicates in question, in particular

Special highly active silica, which is obtained according to the known 6 ₅ ^{3 hardness according to Shore A DIN 53505} process by reacting alkali silicate solutions 4 impact elasticity according to DIN 53512 with acids and a specific surface area of more than 100 m * / g, preferably 100 to 5 Abrasion according to DIN 53516.

example 1

The following mixtures were prepared in an internal mixer at a temperature of 105 ° C:

1500 g butadiene-styrene rubber,

22.5 g of 2,2'-methylene-bis (4-meth ^ -6-teit.butylphenol),

900 g filler,

150 g naphthenic mineral oil softener.

The mixing time was uniformly minutes in each case. The winds on a conventional rolling mill mixtures thus obtained at a water temperature from 40 ° C the following additives are added:

75 g zinc oxide, 225 g stearic acid, 9 g paraffin, 54 g dicyclohexylamine, 18 g dibenzothiazyl disulfide, 18 g diphenylguanidine, 27 g of sulfur.

To further test the mixtures were cured in the usual way 30 minutes in the press at a temperature of 151 ⁰ C.

Finely divided silica with about 19OmVg BET surface area used with the additives according to the invention was loaded. The amount of additives was chosen so that in each case the same vide MoI additive per filler unit were used. The loading took place through ίο Mixing the ester to the filler and homogenizing by grinding in a high-speed running Pin mill. The results of the investigations are shown in Table 1. In it means

is A = filler without load,

B = per 100 parts by weight of filler loaded with

4.4 parts by weight of maleic acid monoethyl ester,

C = per 100 parts by weight of filler loaded with so 6.8 parts by weight of maleic acid monooctyl ester,

D = per 100 parts by weight of filler loaded with 4.9 parts by weight of maleic acid monoglycol ester,

_{> s} E = per 100 parts by weight of filler loaded with

6.8 parts by weight of maleic acid diglycol ester,

F = per 100 parts by weight of filler loaded with 6.8 parts by weight of fumaric acid diglycol ester.

Table 1 Tensile strength (kg / cm ^a ) Elongation at break (%)

Tension at 300% (kg / cm ⁸ ). Tension at 500% (kg / cm *).

Hardness (Shore A) Impact resilience (%) Structure (kg)

Abrasion (mm ³ )

A. B. C. D. E. 207 191 218 228 226 60S 525 540 485 515 50 79 90 112 90 131 181 197 - 216 63 62 63 66 64 33 40 46 42 47 20th 28 30th 26th 23 128 97 87 92 90

221 460 108

Example 2

The following mixtures were prepared in an internal mixer at a temperature of 105 ° C:

1500 g butadiene-styrene rubber, 22.5 g 2,2'-methylene-bis (4-methyl-6-tert-butylphenol),

900 g filler (see below),

150 g of naphthenic mineral oil plasticizer.

The mixing time was uniformly minutes in each case. Were on a usual rolling mill the mixture obtained in this way, at a roller temperature of 40 ° C, also admixed the following additives:

75 g zinc oxide, 225 g stearic acid, 9 g paraffin, 54 g dicyclohexylamine, 18 g dibenzothiazyl disulfide, 18 g diphenylguanidine, 27 g of sulfur.

For further testing, the mixtures were in the known manner for 30 minutes in a press Vulcanized temperature of 151 ° C. From maleic anhydride and hexanetriol (Molver ratio 1: 1) became a polyester of honey-like Consistency made as follows:

Maleic anhydride and hexanetriol were initially heated to 120 ° C until the anhydride had solved. The polycondensation was through The temperature was increased to 160 ^° C. and a vacuum of about 11 mm Hg was applied. When 0.75 to 0.85 moles of water per mole of maleic anhydride or per mole of hexanetriol were distilled out of the system, the reaction was terminated broke.

This ester, which is practically odorless even at temperatures of 180 ^° C., was applied to the filler, as described in Example 1, to be precise, each 100 parts by weight of filler were mixed with 6.0 parts by weight of the poly

Cs esters loaded. The results are shown in Table 2. The mixture used with unloaded filler is listed under A and the mixture used with loaded filler under B:

Table 2

Tensile strength (kg / cm ¹ )

Elongation at break (· / *)

Tension at 300 * / «(kg / cm»)

Hardness (Shore A)

Impact elasticity (· /.)

Structure (kg)

Abrasion (mm *)

Example 3

205

600

63

64

37

29

120

175 530 taken. In place of the loaded fillers were However, the additives according to the invention together with the unloaded filling clay "in the internal mixer mixed with the rubber. The following additives were added to the mixtures:

64

38

30 ίο 100

In the same way as described in Example 1, the hybrid and sample production was pre-A = without addition according to the invention,

B = 1.8 parts of maleic acid monoglycol ester per 60 parts of filler,

C = 1.8 parts of maleic acid diglycol ester per 60 parts of filler,

D = 1.8 parts of maleic acid monoethyl ester per 60 parts of filler.

The results can be seen in Table 3.

Tabel

A. B. C. 167 222 177 575 605 550 62 79 68 127 167 145 65 70 65 35 37 34 23 22nd 21 143 129 127

Tensile strength (kg / cm *)

Elongation at break (· / ·)

Tension at 300 · / · (kg / cm ¹ ) .. Tension at 500 * / «(kg / cm ¹ ).

Hardness (Shore A)

Impact elasticity (· /,).

Structure (kg)

Abrasion (mm ¹ ),

209

545 93

177 72 39 24

107

Example 4

In the same way as described in Example 3, the mixture and sample preparation for the following series of experiments was carried out. Been there The following additives are added to the rubber in the internal mixer:

A = without addition according to the invention, ^4S

B = 1.8 parts by weight of maleic acid monoglycic ester for every 60 parts by weight of filler,

C = 1.8 parts by weight of monomethyl malemate for every 60 parts by weight of filler, D = 1.8 parts by weight of maleic acid monostearyl ester for every 60 parts by weight of filler,

E = 1.8 parts by weight of maleic acid monophenyl methyl ester for every 60 parts by weight of filler,

F = 1.8 parts by weight of maleic acid monoallyl ester per 60 parts by weight of filler,

G = 1.8 parts by weight of maleic acid monobutene diol ester per 60 parts by weight of filler,

H = 1.8 parts by weight of maleic acid monobutynediol ester for every 60 parts by weight of filler.

The results are shown in Table 4.

Tabel

A. B. C. D. E. F. G 164 177 220 182 201 182 197 680 504 590 615 585 605 615 31 72 79 54 69 63 62 76 151 172 121 152 128 133 67 71 65 62 66 67 67 36 38 43 42 42 37 38 28 32 27 24 28 34 27 180 125 101 114 110 129 122

Tensile strength (kg / cm ¹ )

Elongation at break (%)

Tension at 300% (kg / cm *)
Tension at 500 · / "(kg / cm *)

Hardness (Shore A)

Impact elasticity (· / ,,)

Structure (kg)

Abrasion (mm *)

197

615 62

131 69 38 30

126

Claims (4)

Patent claims: 1. Process for the production of silicic acid and / or calcium or aluminum silicates reinforced rubber vulcanizates with the addition of filler activators, characterized in that the filler activators are the Esters of unsaturated dicarboxylic acids with 4 carbon atoms with mono- or polyvalent ones Alcohols used. 2. The method according to claim 1, characterized in that esters are used whose alcohol component has 2 to 6 carbon atoms. 3. The method according to claim 1 and 2, characterized in that the ester first the filler added and mixed intensively with this. 4. The method according to claim 1 to 3, characterized in that the filler is ^{mixed with the dicarboxylic acid ester at temperatures up to 200 0} C with the rubber in the internal mixer. 909534/383