Vulcanised thermoplastic-modified rubbers

(12) PATENT

NORWAY (19) NO (11) 312552 (5i) Int Cl⁷ C 08 L 19/00, 9/02 (13) Pg

Patent Office (21) Application no. (22) Start day (24) Running day (41) Alm. avail.

(45) Date announced

19965482

1996.12.19

1996.04.23

1996.12.19

2002.05.27 (86) Int. Entry date and application number (85) Continuation day (30) Priority

1996.04.23, PCT / FR96 / 00618

1996.12.19

1995.04.28. FR. 9505125

1995.12.21, FR, 9515244

<td>(71) Patent holder (72) Inventor</td><td>Elf Atochem SA, 4/8, Cours Michelet, F-92800 Puteaux, FR Isabelle Betremieux, Beaumontel, FR Patrick Alex, Limours-Pecqueuse, FR Philippe Marcq, Bemay, FR Christian Dousson, Bemay, FR</td>

<td>(74) Agent</td><td>Bryns Zacco AS, 0106 Oslo</td>

<td>(54) Designation</td><td>Thermoplastic-modified, vulcanized rubbers and their manufacture</td>

<td>(56) Cited publications</td><td>US 4661563, EP A 364859, EP A 251791</td>

<td>(57) Summary</td><td>A vulcanized mixture consisting of: (i) at least one functionalized rubber, and (ii) - at least one thermoplastic in an amount sufficient to increase the modulus at small extensions but so that the breaking load is not reduced by more than 10%. The thermoplastic can be selected from polyamides and copolymers containing polyamide blocks and polyether blocks. The mixture is prepared by incorporating the thermoplastic in the molten state in the rubber until a dispersion is achieved in the gununi matrix.</td>

in

BACKGROUND OF THE INVENTION

More specifically, the present invention relates to vulcanized rubbers modified with thermoplastics and more particularly to vulcanized blends of (i) functionalized rubbers and (ii) thermoplastics. They can be prepared by incorporating the thermoplastic in the molten state into the rubber after which the vulcanization is carried out.

In the case of rubber, for special applications such as tires, conveyor belts and the like, it may be of interest to be able to increase the load with small extensions without taking into account the problems of heating the vulcanized components in use and bringing them under dynamic loading or aging. which is formed by the conventional solutions, such as reinforcement with soot or with a considerable degree of fouling.

US 5,239,004 explains that natural SBR (styrene-butadiene), X-NBR (carboxylated nitrile butadiene) or EPDM (ethylene-propylene-diene) rubbers can be modified with dithiodo acids and copolymers containing polyether blocks and polyamide blocks. These modifications increase the module by 50,100 and 300% load. The examples concern only natural gums which were mixed in 1% by weight of dithio-dipropionic acid. 4 % by weight, either of various copolymers containing polyether blocks and polyamide blocks or of polyamide 12, is then added to the rubber after which the vulcanization is performed. An increase of the modules at 50,100 and 300% elongation is observed, on the other hand a decrease of 20 to 35% in the breaking strength is noted.

The compositions of the invention also have markedly increased modulus at 50,100 and 300% but show a better fracture load.

The present invention describes the improvements of certain properties of the rubber (reinforcement, tear strength and the like) without the use of dithiodoic acid while at the same time having a very fine and homogeneous dispersion of the thermoplastic in the rubber network.

EP 40060 discloses a thermoplastic blend of polyamide-6 and polyamide-66 or polyamide-6, polyamide-66 and polyamide-610 with epichlorohydrin gums. These are polyamide matrices containing epichlorohydrin rubber nodules. The examples compare mixtures with vulcanized nodules and mixtures with non-vulcanized nodules.

The products of the invention are not thermoplastic. The present invention relates to the modification of rubbers with one or a number of thermoplastics. The thermoplastics work to be compatible with the rubber. This modification makes it possible to improve certain properties of the rubber while maintaining the elastomeric properties (compression set, elongation at break) and the resistance to oils:

Increase in raw strength or modulus by small extensions for raw rubber, ie before vulcanization.

Increase of the module by small extensions of the vulcanized rubber or reinforcing effect.

Increase in tear strength and fracture strength.

Increase in hardness.

In addition, and in some cases, particularly in the case of XNBR, the incorporation of thermoplastic of the copolymer containing blocks of the polyamide and polyether type, in addition to the above improvements, contributes to a marked improvement in the behavior of the low temperature, such as the extension. .

The present invention thus relates to a vulcanized composition comprising:

(i) at least one functionalized rubber selected from nitrile butadiene (NBR), hydrogenated nitrile butadiene (H-NBRjj carboxyl pea nitrile butadiene (X-NBR), and epichlorohydrin gums, and the composition is characterized by containing (ii) at least one thermoplastic in a amount of at least 5 parts per weight. 100 parts by weight of rubber, sufficient to increase modulus at small extensions but so that the breaking load is not reduced by more than 10%, the gums (i) forming the matrix in which the thermoplastic (ii) is dispersed in the form of nodules.

As mentioned initially, the invention also relates to a process for preparing mixtures as described above and this process is characterized by incorporating the thermoplastic in the molten state in the non-vulcanized rubber until a dispersion in the rubber matrix is ​​achieved and then a static vulcanization is carried out. .

The functionalized rubber and thermoplastic are mixed before vulcanization. The vulcanizer and any catalysts are then introduced and the vulcanization performed. The agents and catalyst may also be introduced during mixing with the thermoplastic provided that they are not active at the temperature reached during mixing.

<img file="NO312552B1_D0001.tif" />

Mixtures of one of the above gums may also be used with a non-functionalized rubber such as styrene butadiene (SBR), natural rubber or ethylene propylenediene (EPDM).

As mentioned, acrylic rubbers nitrile butadiene (NBR) and hydrogenated nitrile butadiene (HNBR) can be used. Epichlorohydrin gums are described in KIRK-OTHMER Encyclopedia of Chemical Technology 3rd edition, vol. 8, chapter Elastomers pages 568 et seq.

These are polymers containing epichlorohydrin units which may also contain ethylene oxide, propylene oxide or substituted propylene oxide units. As mentioned, the grafted rubber carboxylated nitrile butadiene (X-NBR) can be used.

The amount of functional groups in the rubber is preferably between 0.3 and 10% by weight of the weight of the functionalized rubber or of the combination functionalized rubber. Non-functionalized rubber.

The thermoplastic is defined as the product which increases the modulus of the functionalized rubber at small extensions, that is, the modulus of the vulcanized mixture of the invention is larger than the modulus of a vulcanized, functionalized rubber (i). This increase can be on the order of 10 and up to 300%.

At the same time, the thermoplastic does not affect the breaking strength by more than 10%, that is, the breaking load for the vulcanized composition according to the invention is no more than 10% worse than the breaking load for the vulcanized, functionalized rubber (i). Most often, this load is even improved.

Copolyether esters may be mentioned as examples of thermoplastics. These are copolymers with polyether units derived from polyether diols such as polyethylene glycol (PEG), polypropylene glycol (PPG) or polytetramethylene glycol (PTMG), dicarboxylic acid units such as terephthalic acid, glycol (ethanediol) or 1,4-butanediol units. The bonding of the polyethers and diacids forms flexible segments while the bonding of glycol or butanediol with the diacids forms rigid segments of copolyether ester.

Such copolyether esters are described in EP 402 883 and 405 227.

Also mentioned as thermoplastics are polyether urethanes, such as those comprising diisocyanate units, units derived from polyether diols and units derived from ethanediol or 1,4-butanediol.

One may also mention polyester urethanes, such as those comprising diisocyanate units, units derived from amorphous polyester diols and units derived from ethanediol or 1,4-butanediol.

The thermoplastic can also be a polyamide. By polyamide is meant the condensation products of:

one or a number of amino acids such as aminocaprone, 7-amino-heptane, 11-aminodecane or 12-aminododecanoic acid, from one or a number of lactams such as caprolactam, oenantolactam and lauryllactam;

one or a number of salts or mixtures of diamines such as hexamethylenediamine, dodecamethylenediamine, methaxylylenediamine, bis-p-aminocyclohexylmethane and trimethylhexamethylene diamine, with diacids such as isophthalic, terephthalic, adipic, azalic acid, suberic, suberic, suberin, suberin or mixtures of some of these monomers resulting in copolyamides.

Polyamide-b landings can be used. Preferably, PA-11, PA-12 and the copolyamide containing 6 units and 12 units (PA-6/12) are used.

The thermoplastic may also be a mixture of polyamide and of polyolefms. The polyamide may be selected from the above.

By polyolefins is meant polymers comprising olefin units such as ethylene, propylene or 1butene units or the like.

An example is:

polyethylene, polypropylene, or copolymers of ethylene with α-olefins, as it is possible that these products are seeded with unsaturated carboxylic anhydrides such as maleic anhydride, or unsaturated epoxides such as glycidyl methacrylate, copolymers of ethylene with at least one product selected from (i) unsaturated carboxylic acid salts or esters, (ii) vinyl esters of saturated carboxylic acid, (iii) unsaturated dicarboxylic acids, their salts, esters, semesters or anhydrides, or (iv) unsaturated epoxides, as it is possible that these copolymers of ethylene are seeded with unsaturated dicarboxylic acid anhydrides or unsaturated epoxides, the styrene / ethylene butylene / styrene (SEBS) copolymers optionally maleized.

Mixtures of two or a number of these polyolefins can be used.

Preferably used:

polyethylene, copolymers of ethylene and an α-olefin, copolymers of ethylene / of an alkyl (meth) acrylate, copolymers of ethylene / an alkyl (meth) acrylate / maleic anhydride, the maleic anhydride being grafted or copolymerized, copolymers of ethylene / alkyl (meth) ) acrylate / glycidyl methacrylate, the glycidyl methacrylate being grafted or copolymerized, polypropylene.

To facilitate the formation of the polyamide matrix and if the polyolefins have few or no functional groups which can facilitate compatibility, it may be advisable to add a compatibilizer.

The compatibilizer is a product known per se for the compatibility of polyamides and polyolefins.

For example:

polyethylene, polypropylene, ethylene / propylene copolymers or ethylene / butene copolymers, all of which are grafted with maleic anhydride or glycidylmethacrylate, ethylene / alkyl (meth) acrylate / maleic anhydride copolymer wherein the maleic anhydride / ethylene anhydride / copolymer is grafted or copolymer. are inoculated or copolymerized, the two copolymers listed above wherein the maleic anhydride is replaced by glycidyl methacrylate, ethylene / (meth) acrylic acid copolymers, optionally salts thereof,

-. polyethylene, polypropylene or ethylene propylene copolymers as these polymers are seeded with a product which shows a site that reacts with amines; these grafted copolymers can then be condensed with polyamides or polyamide oligomers with a single amine end.

These products are described in FR 2 291 225 and EP 342 066.

The amount of polyamide forming the matrix can be between 55 and 95 parts per unit. 5 to 45 parts of polyolefins.

The amount of compatibilizer is the amount sufficient for dispersing the polyolefin in the form of nodules in the polyamide matrix. It can make up to 20% of the weight of the polyolefin. These polymers are prepared by blending polyamide, polyolefin and optionally according to conventional melt blending techniques (double screw, bus or single screw mixers).

The mixture preferably comprises a polyamide-6 (PA-6) or polyamide-66 (PA-66) matrix in which are dispersed nodules of a mixture of low-density polyethylene and copolymer of ethylene, alkyl (meth) acrylate and maleic anhydride, or of glycidyl (meth) ) acrylate or polypropylene nodules.

Such products are disclosed in US 5 070 145 and EP 564 338.

In the case of polypropylene, a compatibilizer is added which is preferably an ethylene / propylene copolymer, the majority of the propylene units being seeded with maleic anhydride and then condensed with monoamino-caprolactam oligomers.

These polyamide and polyolefin mixtures can be softened and optionally contain fillers such as soot and the like.

Such polyamide and polyolefin mixtures are described in US 5,342,886.

As thermoplastics, polymers containing polyamide blocks and polyether blocks can be mentioned.

The polymers containing polyamide blocks and polyether blocks are the result of copolymer condensation of polyamide sequences containing reactive ends with polyether sequences containing reactive ends such as:

1) polyamide sequences containing diamide chain ends with polyoxyalkylene sequences containing dicarboxylic acid chain ends;

2) polyamide sequences containing dicarboxyl chain ends with polyoxyalkylene sequences containing diamide chain ends obtained by cyanoethylation and hydrogenation of α, ω-dihydroxylated aliphatic polyoxyalkylene sequences known as polyether diols,

3) polyamide sequences containing dicarboxylic acid chain ends with polyether diols, the products obtained in this specific case being polyether ester amides.

The polyamide sequences containing dicarboxylic chain ends arise, for example, from the condensation of α, ω-amino carboxylic acids from lactams or of dicarboxylic acids and diamines in the presence of a chain-limiting dicarboxylic acid. The polyamide blocks preferably comprise polyamide-12 or polyamide-6.

The number average molecular weight Mn for the polyamide sequences is between 300 and 15000, preferably between 600 and 5000. The weight average molecular weight Mn for the polyether sequences is between 100 and 6000 and preferably between 200 and 3000.

The polymers containing polyamide blocks and polyether blocks may also comprise randomly distributed units. These polymers can be prepared by simultaneous reaction of polyether and of the precursors of the polyamide blocks.

For example, a polyether diol, a lactam (or an α, ω-amino acid) and a chain-limiting diacid may be reacted in the presence of a small amount of water. A polymer is obtained which has substantially polyether blocks and polyamide blocks of very variable length but also the various reactants which are arbitrarily reacted which are statistically distributed along the polymer chain.

These polymers containing polyamide blocks and polyether blocks show whether they originate from copolymer condensation of polyamide and polyether sequences prepared in advance or from a single-step reaction, for example Shore D hardnesses which may range from 20 to 75 and preferably lay between and 70, and an intrinsic viscosity between 0.8 and 2.5, measured in metacresol at 250 ° C for an initial concentration of 0.8 / 100 ml.

Whether the polyether blocks are derived from polyethylene glycol, from polyoxypropylene glycol or from polyoxytetramethylene glycol, they are either used as they are or copolymerized with polyamide blocks containing carboxyl ends or aminated to convert to polyether diamines and condensed with polyamide blocks containing. They can also be mixed with polyamide precursors and a chain limiter to form polymers containing polyamide blocks and polyether blocks with units distributed statistically.

The polymers containing the polyamide blocks and the polyether blocks are described in US 4,311,786, US 4,115,475, US 4,195,015, US 4,839,441, US 4,84,014, US 4,230,838 and US 4,332,920.

For example, the polyether may be a polyethylene glycol (PEG), a polypropylene glycol (PPG), or a polytetramethylene glycol (PTMG). The latter is also known as polytetrahydrofuran (PTHF).

Whether the blocks are in the chain of the polymer containing polyamide blocks and polyether blocks in the form of diols or in the form of diamines, they are known for simplicity as PEG blocks or PPG blocks or alternatively PTMG blocks and polymers containing PA-6 blocks and PTMG blocks.

It will not be beyond the scope of the invention if the polyether blocks contain various units as units derived from ethylene glycol (-OC2H4-), from propylene glycol -O- (H) -CH3-, or alternatively from tetramethylene glycol (-O- (CH2) 4- ).

The polymer with polyamide blocks and polyether blocks preferably comprises a single type of polyamide block and a single type of polyether block. Generally, polymers containing PA-12 blocks and PTMG blocks and copolymers containing PA-6 blocks and PTMG blocks are used.

A mixture of these two polymers containing polyamide blocks and polyether blocks can also be used.

The polymer containing polyamide blocks and polyether blocks is preferably such that the polyamide is the main component of weight, i.e., the amount of polyamide present in the form of blocks and optionally distributed statistically in the chain constitutes 50% by weight or more of the polymer containing polyamide blocks and polyether blocks. . The amount of polyamide and the amount of polyether are preferably within the ratio polyamide: polyether 1: 1 -3: 1.

This thermoplastic may also include plasticizers, antioxidants or agents to fight UV radiation.

The thermoplastic may also be a mixture of at least one polymer containing polyamide blocks and polyether blocks and at least one polyolefin. This polyolefin and optionally a compatibilizer may be selected from the above as regards mixtures of polyamides and polyolefins.

The thermoplastic may also be a mixture of polyamide and polymer containing polyamide blocks and polyether blocks as it is possible that these products may be selected from the products already mentioned.

The thermoplastic may also be a polymer containing polyamide and amorphous polyester blocks. It can be prepared by condensing polyamide blocks containing carboxylic acid ends, with polyester diols.

For example, the amount of thermoplastic may be up to 60 parts per unit. 100 parts of non-formulated rubber, ie 100 parts of, for example, XNBR or HNBR.

Significant effects have already been observed for only a few parts. The increase in the module varies with the increase in the amount of thermoplastic. This amount is usually between 5 and 50 parts, depending on the intended effect.

Within the scope of the invention, small extensions are of less than 350% and preferably between 50 and 300%.

The breaking load (for the vulcanized blend of the invention) may fall by less than 10% for amounts of thermoplastic in the range of 5 parts / 100 parts of non-formulated rubber and then increases for increasing values ​​of the thermoplastics and exceeds the breaking load of the thermoplastic rubber. This fall, followed by an increase and a decrease with respect to the thermoplastic rubber, is observed for thermoplastics such as polymers containing PA-12 blocks and PTMG blocks. For other thermoplastics and especially polymers containing PA-6 blocks and PTMG blocks, PA-11 and PA-12, there is always an increase in fracture load relative to the rubber that does not contain thermoplastics.

The composition of the invention is provided in the form of a rubber matrix and of thermoplastic nodules. These nodules preferably have a size less than 1 µm.

The tear strength is an increasing function of the amount of thermoplastic while, if doping is carried out with soot instead of thermoplastic, the tear strength increases with the amount of soot, then goes through a maximum and always falls back with increasing amounts of soot.

The compositions of the invention also exhibit good dynamic properties, as compared to doping with soot, thus reducing the percentage of hysteresis.

Thus, a slight internal heating of the composition of the invention is observed which is subjected to dynamic and especially compressive loads while this does not apply to soot.

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The compositions of the invention subjected to dynamic strain tests according to NFT 46.045 show a smaller tang δ than the thermoplastic-free gums and gums doped with soot.

Another advantage of the invention is the good resistance to oil and in particular, the swelling in oil is less than that of rubber which does not contain thermoplastic as a filler included for HNBR and XNBR rubbers.

This is all the more remarkable because these gums are considered to be the most resistant to oils.

The modified rubber according to the invention can be manufactured in one or two steps and in particular the incorporation of the thermoplastic can be carried out before or during the formation of the rubber.

The thermoplastic is incorporated at a temperature sufficient to be in the molten state. The mixture is carried out until a dispersion in the rubber matrix is ​​obtained. The thermoplate is preferably selected such that its melting temperature corresponds to that of the unformulated rubber or to the compounding temperature of the formulated rubber. It is also possible to work via an intermediate rubber / thermoplastic, non-vulcanized master batch step where the master batch is finally incorporated into the remaining rubber.

The mixing time is between 10 minutes and preferably between 5 and 8 minutes.

The mixture obtained has a rubber matrix and can then be formulated on rollers as a conventional rubber with the advantage, with a view to the starting rubber, that it is easier to use as a result of an increase in the raw strength or modulus of small extensions due to the incorporation of the thermoplastics.

Depending on the intended applications, the rubber can advantageously be formulated with soot or light colored fillers, with tackifying resins, processing additives such as polyethylene glycol, stearic acid, zinc oxide and the like.

These formulations may be vulcanized by sulfur-containing systems in the presence or absence of accelerators, of peroxides, with or without co-agents, or alternatively by phenol formaldehyde resins. The choice of vulcanization system depends on the nature of the rubber and the vulcanization kinetics desired at the temperature used.

If the vulcanization temperature is either substantially the same as the rubber and thermoplastic mixing temperature (before vulcanization) or above, accelerators such as peroxides may be incorporated during this mixture or during the formulation of the rubber prior to incorporation of the thermoplastic resin.

If the vulcanization temperature is substantially lower than that of mixing the rubber and thermoplastic, it is preferable to incorporate the accelerators upon cooling of the formulated mixture of rubber and thermoplastic. This incorporation can be carried out over rollers and then vulcanization can be carried out.

Once the vulcanization is completed, a significant increase in the modulus is observed at small extensions for the modified rubber. The reinforcing effect of the thermoplastic can be advantageous in the case of car tires, conveyor belts and the like, where high material strengths are sought.

The vulcanization systems are known per se and can be used, for example, as described in EP 550.346.

The invention will be described in more detail by way of examples.

examples

In the following examples, the ECO rubber is a GECO type terpolymer containing ethylene oxide, epichlorohydrin and allyl glycidyl ether units. It is Hydrin T70X1 from Nippon Zeon.

The HNBR used is ZETPOL 2000 from Nippon Zeon.

The XNBR used is CHEMIGUM PX 7439, powder grade NX775 from Good Year, containing 10% calcium carbonate.

The Pebax 1 used (polyamide block ether 1) consists of 50% polyamide 12 sequences (Mn = 1000) and 50% polytetramethylene glycol sequences (Mn = 1000) and is characterized by a melting point of 147 ° C and a limit viscosity of 1, 60, measured at a concentration of 0.5 g / 100 g of metacresol at 25 ° C.

The used Pebax 2 (polyamide block ether 2) consists of 80% polyamide 12 sequences (Mn = 4000) and 20% polytetramethylene glycol sequences (Mn = 1000) and is characterized by a melting point of 170 ° C and a limit viscosity of 1, 40, measured at a concentration of 0.5 g / 100 g of metacresol at 25 ° C.

The used Pebax 3 (polyamide block ether 3) consists of 66% polyamide 6 sequences (Mn = 1300) and 34% polytetramethylene glycol sequences (Mn = 650) and is characterized by a melting point of 195 ° C and a limit viscosity of 1. 55, measured at a concentration of 0.5 g / 100 g of metacresol at 25 ° C.

The used Pebax 4 (polyamide block ether 4) consists of 80% polyamide 6 sequences (Mn = 2600) and 20% polytetramethylene glycol sequences (Mn = 650) and is characterized by a melting point of 207 ° C and a limit viscosity of 1, 52, measured at a concentration of 0.5 g / 100 g of metacresol at 25 ° C.

Mechanical properties.

Example 1% HNBR rubber and 10% polyamide block ether 1 are mixed for 7 to 8 minutes at 165 ° C in a Brabender mixer. The modified rubber is then formulated at 30 ° C on a rolling mill according to the following composition in parts :

<td>Zetpol 2000</td><td> 100</td>

<td>Pebax 1</td><td> 11.1</td>

<td>Calcined kaolin</td><td> 30</td>

<td>SilanA187</td><td> 1</td>

<td>PEG 4000</td><td> 1</td>

<td>stearic acid</td><td> 0.55</td>

<td>Zinc oxide</td><td> 3.33</td>

<td>Perkadox 1440</td><td> 6.7</td>

<td>TiO₂</td><td> 5.</td>

Example 2

The preparation is carried out in the same way as in Example 1.20% Pebax 1 is incorporated into HNBR during the first step and the composition below is followed for the second formulation step:

<td>Zetpol 2000</td><td> 100</td>

<td>Pebax 1</td><td> 25</td>

<td>Calcined kaolin</td><td> 30</td>

<td>Silan Al 87</td><td> 1</td>

<td>PEG 4000</td><td> 1</td>

<td>stearic acid</td><td> 0.65</td>

<td>Zinc oxide</td><td> 3.75</td>

<td>Perkadox 1440</td><td> 7.5</td>

<td>TiO₂</td><td> 5.</td>

The compositions of Examples 1 and 2 as well as a control mixture which does not contain

Pebax 1, was vulcanized under static conditions on a press at 180 ° C below 90 bar for 12 minutes to obtain blocks of 2 mm thickness. The mechanical properties were measured at 23 ° C on the specimens prepared from these blocks.

<td>Try</td><td>Module 50% MPa</td><td>Module 100% MPa</td><td>Module 300% MPa</td><td>Breakage load MPa</td><td>Tear strength N / mm</td><td>Breakage Extension%</td>

<td>Control 1 without Pebax 1</td><td> 1.0</td><td> 1.3</td><td> 3.7</td><td> 12.4</td><td> 28.7</td><td> 742</td>

<td>Example 1</td><td> 1.3</td><td> 1.8</td><td> 4.9</td><td> 13.1</td><td> 31.8</td><td> 726</td>

<td>Example 2</td><td> 1.8</td><td> 2.4</td><td> 5.5</td><td> 14.8</td><td> 38.4</td><td> 733</td>

Table 1: HNBR properties, modified with Pebax 1.

Example 3% XNBR rubber and 10% polyamide block ether 1 are mixed for 7 to 8 minutes at 165 ° C in a Brabender mixer. The modified rubber is then formulated at 30 ° C on a rolling mill according to the following composition in parts:

<td>Zetpol 2000</td><td> 110</td>

<td>Pebax 1</td><td> 11.1</td>

<td>Calcined kaolin</td><td> 30</td>

<td>Silan Al 87</td><td> 1</td>

<td>PEG 4000</td><td> 1</td>

<td>stearic acid</td><td> 0.55</td>

<td>Zinc oxide</td><td> 3.33</td>

<td>Perkadox 1440</td><td> 0.83</td>

<td>TiO₂</td><td> 5.</td>

Example 4

The preparation is carried out in the same way as in Example 3.20% Pebax 1 is incorporated into XNBR in the first step and the composition below is followed for the second formulation step:

<td>Zetpol 2000</td><td> 110</td>

<td>Pebax 1</td><td> 25</td>

<td>Calcined kaolin</td><td> 30</td>

<td>Silan Al 87</td><td> 1</td>

<td>PEG 4000</td><td> 1</td>

<td>stearic acid</td><td> 0.65</td>

<td>Zinc oxide</td><td> 3.75</td>

<td>Perkadox 1440</td><td> 0.94</td>

<td>TiO₂</td><td> 5.</td>

The mixtures of Examples 3 and 4, as well as a control mixture not containing Pebax 1, were vulcanized under static conditions on a press at 180 ° C below 90 bar for 12 minutes to obtain blocks having a thickness of 2 mm. The mechanical properties were measured at 23 ° C and -35 ° C on specimens made from these blocks.

<td>Try</td><td>Module 50% MPa</td><td>Module 100% MPa</td><td>Module 300% MPa</td><td>Breakage load MPa</td><td>Tear strength N / mm</td><td>Elongation at break,% at -35 ° C</td><td>Elongation at break,% at 23 ° C</td>

<td>Control 1 without Pebax 1</td><td> 1.8</td><td> 2.9</td><td> 3.7</td><td> 14.5</td><td> 33.8</td><td> 25</td><td> 492</td>

<td>Example 1</td><td> 2.1</td><td> 3.4</td><td> 4.9</td><td> 13.8</td><td> 34.2</td><td> 34</td><td> 428</td>

<td>Example 2</td><td> 2.8</td><td> 4.2</td><td> 10.6</td><td> 15.7</td><td> 38.3</td><td> 64</td><td> 498</td>

Table 2: Properties of XNBR, modified with Pebax 1.

Example 5

The formulation in this example was prepared directly on a rolling mill according to the following composition in parts, corresponding to a content of 95% HNBR per mill. 5% Pebax 2:

<td>Zetpol 2000</td><td> 100</td>

<td>Pebax 1</td><td> 5.5</td>

<td>Calcined kaolin</td><td> 30</td>

<td>Silan Al 87</td><td> 1</td>

PEG 40001

Naugard 4452

Stearinsyre0.5

Sinkoksyd3

Perkadox 14406 ^Tl025.

Example 6

The preparation is carried out in the same manner as in Example 5, the composition below (90% HNBR / 10% Pebax 2) is followed:

<td>Zetpol 2000</td><td> 100</td>

<td>Pebax 1</td><td> 11.1</td>

<td>Calcined kaolin</td><td> 30</td>

<td>Silan Al 87</td><td> 1</td>

<td>PEG 4000</td><td> 1</td>

<td>Naugard 445</td><td> 2</td>

<td>stearic acid</td><td> 0.55</td>

<td>Zinc oxide</td><td> 3.3</td>

<td>Perkadox 1440</td><td> 6.7</td>

<td>TiO₂</td><td> 5.</td>

Example 7

The preparation is carried out in the same manner as in Example 5, the composition below (80% HNBR / 20% Pebax 2) is followed:

<td>Zetpol 2000</td><td> 100</td>

<td>Pebax 1</td><td> 25</td>

<td>Calcined kaolin</td><td> 30</td>

<td>Silan A187</td><td> 1</td>

<td>PEG 4000</td><td> 1</td>

<td>Naugard 445</td><td> 2</td>

<td>stearic acid</td><td> 0.65</td>

<td>Zinc oxide</td><td> 3.75</td>

<td>Perkadox 1440</td><td> 7.5</td>

<td>TiO₂</td><td> 5.</td>

The increase in raw strength and the appearance of machining aids were demonstrated for the formulations of Examples 5, 6 and 7 by means of modular measurements at small extensions before vulcanization.

<td>Try</td><td>Module 50% MPa</td><td>Module 100% MPa</td><td>Module 300% MPa</td>

<td>Control 3 without Pebax 2</td><td> 0.82</td><td> 0.85</td><td> 1.06</td>

<td>Example 5</td><td> 0.89</td><td> 0.87</td><td> 0.90</td>

<td>Example 6</td><td> 1.13</td><td> 1.21</td><td> 1.58</td>

<td>Example 7</td><td> 2.43</td><td> 2.84</td><td> 3.03</td>

Table 3: Raw properties for HNBR modified with Pebax 2.

The mixtures of Examples 5,6 and 7, as well as a control mixture not containing Pebax ίο 1, were vulcanized under static conditions on a press at 180 ° C below 90 bar for 12 minutes to obtain blocks of 2 mm thickness. The mechanical properties were measured at 23 ° C on the specimens prepared from these blocks.

<td>Try</td><td>Module 50% MPa</td><td>Module 100% MPa</td><td>Module 300% MPa</td><td>Breakage load MPa</td><td>Breakage Extension%</td><td>Shore Hardness</td><td>CS 221.100 ° C</td>

<td>Control 3 without Pebax 2</td><td> 1.06</td><td> 1.32</td><td> 3.63</td><td> 12.92</td><td> 641</td><td> 56</td><td> 32</td>

<td>Example 5</td><td> 2.21</td><td> 1.64</td><td> 5.85</td><td> 12.55</td><td> 592</td><td> 60</td><td> 31.5</td>

<td>Example 6</td><td> 1.47</td><td> 2.09</td><td> 7.16</td><td> 14.23</td><td> 541</td><td> 65</td><td> 30.5</td>

<td>Example 7</td><td> 2.35</td><td> 3.41</td><td> 9.53</td><td> 13.90</td><td> 442</td><td> 75</td><td> 32</td>

Table 4: HNBR properties, modified with Pebax 2.

Example 8

The formulation in this example was prepared directly on a rolling mill according to the following composition in parts, which is equivalent to 95% XNBR per liter. 5% Pebax 2:

<td>XNBRPX7439</td><td> 110</td>

<td>Pebax 2</td><td> 5.5</td>

<td>Calcined kaolin</td><td> 20</td>

<td>Silan A187</td><td> 1</td>

<td>PEG 4000</td><td> 1</td>

<td>Naugard 445</td><td> 2</td>

<td>stearic acid</td><td> 0.5</td>

<td>Zinc oxide</td><td> 3</td>

<td>Perkadox 1440</td><td> 0.8</td>

<td>TiO₂</td><td> 5.</td>

Example 9

The preparation is carried out in the same manner as in Example 8, following the composition below (90% XNBR per 10% Pebax 2):

<td> 20</td><td>XNBRPX7439</td><td> 110</td>

<td></td><td>Pebax 2</td><td> 11.1</td>

<td></td><td>Calcined kaolin</td><td> 20</td>

<td></td><td>Silan A187</td><td> 1</td>

<td></td><td>PEG 4000</td><td> 1</td>

<td> 25</td><td>Naugard 445</td><td> 2</td>

<td></td><td>stearic acid</td><td> 0.5</td>

<td></td><td>Zinc oxide</td><td> 3.3</td>

<td></td><td>Perkadox 1440</td><td> 0.83</td>

<td></td><td>TiO₂</td><td> 5.</td>

Example 10

The preparation is carried out in the same manner as in Example 8, following the composition below (80% XNBR per 20% Pebax 2):

<td>XNBRPX7439</td><td> 110</td>

<td>Pebax 2</td><td> 25</td>

<td>Calcined kaolin</td><td> 20</td>

<td>SilanA187</td><td> 1</td>

<td>PEG 4000</td><td> 1</td>

<td>Naugard 445</td><td> 2</td>

<td>stearic acid</td><td> 0.65</td>

<td>Zinc oxide</td><td> 3.75</td>

<td>Perkadox 1440</td><td> 0.94</td>

<td>TiO₂</td><td> 5.</td>

The mixtures of Examples 5, 6 and 7, as well as a control mixture not containing Pebax 1, were vulcanized under static conditions on a press at 180 ° C below 90 bar for 12 minutes to obtain blocks having a thickness of 2 mm. The mechanical properties were measured at 23 ° C on the specimens prepared from these blocks.

<td>Try</td><td>Module 50% MPa</td><td>Module 100% MPa</td><td>Module 300% MPa</td><td>Breakage load MPa</td><td>Extension at break %</td><td>Shore Hardness</td><td>CS 221.100 ° C</td>

<td>Control 4 without Pebax 2</td><td> 1.08</td><td> 1.51</td><td> 4.36</td><td> 11.51</td><td> 611</td><td> 65</td><td> 27.5</td>

<td>Example 8</td><td> 1.33</td><td> 1.99</td><td> 6.00</td><td> 12.74</td><td> 566</td><td> 68</td><td> 30</td>

<td>Example 9</td><td> 1.77</td><td> 2.84</td><td> 8.30</td><td> 15.05</td><td> 534</td><td> 70</td><td> 34</td>

<td>Example 10</td><td> 2.85</td><td> 4.63</td><td> 10.87</td><td> 17.58</td><td> 492</td><td> 75</td><td> 36</td>

Table 5: Properties of XNBR, modified with Pebax 2.

Example 11

The formulation in this example was prepared directly on a roller mill according to the following composition in parts, which is equivalent to 95% ECOT per mill. 5% Pebax 2:

<td>HYDRIN T70X1</td><td> 100</td>

<td>Pebax 2</td><td> 5.5</td>

<td>Calcined kaolin</td><td> 30</td>

<td>SilanA187</td><td> 1</td>

<td>PEG 4000</td><td> 1</td>

<td>Naugard 445</td><td> 2</td>

Stearinsyre1

Maglite D3

Zisnet GF1,2

CaCO₃5 ^Ti025.

Example 12

The preparation is carried out in the same manner as in Example 11, following the composition below (90% ECOT per 10% Pebax 2):

<td>HYDRIN T70X1</td><td> 100</td>

<td>Pebax 2</td><td> 11.1</td>

<td>Calcined kaolin</td><td> 30</td>

<td>Silan Al 87</td><td> 1</td>

<td>PEG 4000</td><td> 1</td>

<td>Naugard 445</td><td> 2</td>

<td>stearic acid</td><td> 1</td>

<td>Maglite D</td><td> 3</td>

<td>Zisnet F</td><td> 1.5</td>

<td>CaCO₃</td><td> 5</td>

<td>TiO₂</td><td> 5.</td>

Example 13

The preparation is carried out in the same manner as in Example 11, following the composition below (80% ECOT per 20% Pebax 2):

<td>HYDRIN T70X1</td><td> 110</td>

<td>Pebax 2</td><td> 25</td>

<td>Calcined kaolin</td><td> 30</td>

<td>Silan Al 87</td><td> 1</td>

<td>PEG 4000</td><td> 1</td>

<td>Naugard 445</td><td> 2</td>

<td>stearic acid</td><td> 1</td>

<td>Maglite D</td><td> 3</td>

<td>Zisnet F</td><td> 1.7</td>

<td>TiO₂</td><td> 5.</td>

The mixtures of Examples 11, 12 and 13, as well as a control mixture not containing Pebax 1, were vulcanized under static conditions on a press at 180 ° C below 90 bar for 12 minutes to obtain blocks having a thickness of 2 mm. The mechanical properties were measured at 23 ° C on the specimens prepared from these blocks.

<td>Try</td><td>Module 50% MPa</td><td>Module 100% MPa</td><td>Module 300% MPa</td><td>Breakage load MPa</td><td>Breakage Extension%</td><td>Shore Hardness</td><td>CS 221.100 ° C</td>

<td>Control 5 without Pebax 2</td><td> 0.89</td><td> 1.50</td><td> 4.97</td><td> 5.74</td><td> 337</td><td> 49</td><td> 8</td>

<td>Example 11</td><td> 1.23</td><td> 2.29</td><td> -</td><td> 5.54</td><td> 225</td><td> 57</td><td> 13</td>

<td>Example 12</td><td> 2.00</td><td> 3.80</td><td> -</td><td> 6.59</td><td> 183</td><td> 65</td><td> 23</td>

<td>Example 13</td><td> 3.05</td><td> 5.27</td><td> -</td><td> 7.62</td><td> 166</td><td> 77</td><td> 32.5</td>

Table 6: ECOT properties, modified with Pebax 2.

Example 14 in XNBR is formulated on rollers according to the following composition in parts:

XNBRPX7439 110

CaCO₃30

PEG 40003 is Naugard 4452

Stearinsyre0.5

Zinkoksyd3.

88.7% of the formulated XNBR and 10% Pebax 3 are mixed for 7 to 8 minutes at 200 ° C in a

Brabender mixer. Cooling is performed and 1.3% Peroxymon F40 is added on rollers.

Example 15

78.9% XNBR formulated according to Example 14 and 20% Pebax 3 are mixed for 7 to 8 minutes at 200 ° C in a Brabender mixer. Cooling is performed and 1.1% Peroxymon F40 is added on 25 rolls.

Example 16% XNBR formulated according to Example 14 and 30% Pebax 3 are mixed for 7 to 8 minutes at 200 ° C in a Brabender mixer. Cooling is performed and 1% Peroxymon F40 is added on rollers.

The mixtures of Examples 14,15 and 16, as well as a control mixture not containing Pebax 3, were vulcanized under static conditions on a press at 180 ° C below 90 bar for 12 minutes to obtain blocks having a thickness of 2 mm. The mechanical properties were measured at 23 ° C on the specimens prepared from these blocks.

<td>Try</td><td>Module 50% MPa</td><td>Module 100% MPa</td><td>Module 300% MPa</td><td>Breakage load MPa</td><td>Extension at break %</td><td>Tear strength N / mm</td><td>Shore Hardness</td><td>CS 221, 100 ° C</td>

<td>Control 6 without Pebax 3</td><td> 1.04</td><td> 1.46</td><td> 3.14</td><td> 12.10</td><td> 500</td><td> 21.6</td><td> 53</td><td> 10</td>

<td>Example 14</td><td> 1.75</td><td> 2.63</td><td> 6.81</td><td> 14.60</td><td> 450</td><td> 30.2</td><td> 60</td><td> 18</td>

<td>Example 15</td><td> 2.58</td><td> 4.36</td><td> 7.82</td><td> 19.90</td><td> 430</td><td> 42.4</td><td> 66</td><td> 26</td>

<td>Example 16</td><td> 4.03</td><td> 6.66</td><td> 17.10</td><td> 22.10</td><td> 390</td><td> 53.8</td><td> 74</td><td> 34</td>

Table 7: Properties of XNBR, modified with Pebax 3.

Example 17

89.7% XNBR formulated according to Example 14 and 10% Pebax 4 are mixed for 7 to 8 minutes at 200 ° C in a Brabender mixer. Cooling is performed and 1.3% Peroxymon F40 is added on rollers.

Example 18

78.9% XNBR formulated according to Example 14 and 20% Pebax 4 are mixed for 7 to 8 minutes at 200 ° C in a Brabender mixer. Cooling is performed and 1.1% Peroxymon F40 is added on rollers.

Example 19% XNBR formulated according to Example 14 and 30% Pebax 4 are mixed for 7 to 8 minutes at 200 ° C in a Brabender mixer. Cooling is performed and 1% Peroxymon F40 is added on rollers.

The compositions of Examples 17, 18 and 19 as well as a control composition which does not contain

Pebax 4, was vulcanized under static conditions on a press at 180 ° C below 90 bar for 12 minutes to obtain blocks of 2 mm thickness. The mechanical properties were measured at 23 ° C on the specimens prepared from these blocks.

<td>Try</td><td>Module 50% MPa</td><td>Module 100% MPa</td><td>Module 300% MPa</td><td>Breakage load MPa</td><td>Extension at break %</td><td>tear N / mm</td><td>Shore Hardness</td><td>CS 221, 100 ° C</td>

<td>Control 6 without Pebax 4</td><td> 1.04</td><td> 1.46</td><td> 3.14</td><td> 12.10</td><td> 500</td><td> 21.6</td><td> 53</td><td> 10</td>

<td>Example 17</td><td> 1.98</td><td> 3.50</td><td> 11.9</td><td> 17.80</td><td> 380</td><td> 30.9</td><td> 61</td><td> 13</td>

<td>Example 18</td><td> 3.59</td><td> 6.87</td><td> 19.30</td><td> 21.50</td><td> 330</td><td> 42.5</td><td> 70</td><td> 17</td>

<td>Example 19</td><td> 6.76</td><td> 13.02</td><td> 22.40</td><td> 27.00</td><td> 260</td><td> • 54.8</td><td> 80</td><td> 20</td>

Table 8: Properties of XNBR, modified with Pebax 4.

Example 20

89.7% XNBR formulated according to Example 14 and 10% PAI 1 are mixed for 7 to 8 minutes at 190 ° C in a Brabender mixer. Cooling is performed and 1.3% Peroxymon F40 is added on rollers.

Example 21

78.9% XNBR formulated according to Example 14 and 20% PAI 1 are mixed for 7 to 8 minutes at 190 ° C in a Brabender mixer. Cooling is performed and 1.1% Peroxymon F40 is added on rollers.

Example 22% XNBR formulated according to Example 14 and 30% PAI 1 are mixed for 7 to 8 minutes at 190 ° C in a Brabender mixer. Cooling is performed and 1% Peroxymon F40 is added on rollers.

The mixtures of Examples 20, 21 and 22, as well as a control mixture not containing PAI 1, were vulcanized under static conditions on a press at 180 ° C below 90 bar for 12 minutes to obtain blocks having a thickness of 2 mm. The mechanical properties were measured at 23 ° C on the specimens prepared from these blocks.

<td>Try</td><td>Module 50% MPa</td><td>Module 100% MPa</td><td>Module 300% MPa</td><td>Breakage load MPa</td><td>Breakage Extension%</td><td>Tear strength N / mm</td><td>Shore- A- hardness</td><td>CS 221, 100 ° C</td>

<td>Control 6 without PA11</td><td> 1.04</td><td> 1.46</td><td> 3.14</td><td> 12.10</td><td> 500</td><td> 21.6</td><td> 53</td><td> 10</td>

<td>Example 20</td><td> 2.08</td><td> 3.39</td><td> 10.1</td><td> 17.1</td><td> 410</td><td> 35.0</td><td> 63</td><td> 14</td>

<td>Example 21</td><td> 4.57</td><td> 7.74</td><td> 18.90</td><td> 21.60</td><td> 340</td><td> 47,0</td><td> 77</td><td> 18</td>

<td>Example 22</td><td> 13.33</td><td> 22.2</td><td> -</td><td> 27.60</td><td> 150</td><td> 54.8</td><td> 88</td><td> 34</td>

Table 9: Properties of XNBR, modified with PAI 1,

Example 23

89.7% XNBR formulated according to Example 14 and 10% PA12 are mixed for 7 to 8 minutes at 190 ° C in a Brabender mixer. Cooling is performed and 1.3% Peroxymon F40 is added on rollers.

Example 24

78.9% XNBR formulated according to Example 14 and 20% PAI2 are mixed for 7 to 8 minutes at 190 ° C in a Brabender mixer. Cooling is performed and 1.1% Peroxymon F40 is added on rollers.

Example 25% XNBR formulated according to Example 14 and 30% PA12 are mixed for 7 to 8 minutes at 190 ° C in a Brabender mixer. Cooling is performed and 1% Peroxymon F40 is added on rollers.

The mixtures of Examples 23, 24 and 25, as well as a control mixture not containing PA12, were vulcanized under static conditions on a press at 180 ° C below 90 bar for 12 minutes to obtain blocks having a thickness of 2 mm. The mechanical properties were measured at 23 ° C on the specimens prepared from these blocks.

<td>Try</td><td>Module 50% MPa</td><td>Module 100% MPa</td><td>Module 300% MPa</td><td>Breakage load MPa</td><td>Extension at break %</td><td>tear N / mm</td><td>Shore Hardness</td><td>CS 22 t, 100 ° C</td>

<td>Control 6 without PAI2</td><td> 1.04</td><td> 1.46</td><td> 3.14</td><td> 12.10</td><td> 500</td><td> 21.6</td><td> 53</td><td> 10</td>

<td>Example 23</td><td> 1.92</td><td> 3.08</td><td> 8.30</td><td> 16.70</td><td> 430</td><td> 31.4</td><td> 62</td><td> 15</td>

<td>Example 24</td><td> 4.17</td><td> 6.49</td><td> 13.60</td><td> 20.10</td><td> 400</td><td> 41.8</td><td> 75</td><td> 21</td>

<td>Example 25</td><td> 8.41</td><td> 11.95</td><td> -</td><td> 22.10</td><td> 300</td><td> 52.4</td><td> 86</td><td> 27</td>

Table 10: Properties of XNBR, modified with PA12.

The following examples are conducted for the sake of comparison. Thus, different levels of soot FEF N550 were added to the XNBR formulation of Example 14 to compare the reinforcing effect of the thermoplastic with that of soot.

Example 26

XNBR is formulated on rollers according to the following composition in parts:

<td>XNBRPX7439</td><td> 110</td>

<td>CaCO₃</td><td> 30</td>

<td>N550</td><td> 10</td>

<td>PEG 4000</td><td> 3</td>

<td>Naugard 4452</td><td></td>

<td>stearic acid</td><td> 0.5</td>

<td>zinc oxide</td><td> 3</td>

<td>Peroxymon F40</td><td> 2.</td>

Example 27

The same formulation as in Example 26 is prepared and 20 parts of FEF N550 soot are introduced instead of 10 parts.

Example 28

The same formulation as in Example 26 is prepared and 30 parts of FEF N550 soot are introduced instead of 10 parts.

The compositions of Examples 26, 27 and 28 as well as a control composition which does not contain

Pebax 4, was vulcanized under static conditions on a press at 180 ° C below 90 bar for 12 minutes to obtain blocks of 2 mm thickness. The mechanical properties were measured by

23 ° C on the specimens prepared from these blocks.

<td>Try</td><td>Module 50% MPa</td><td>Module 100% MPa</td><td>Module 300% MPa</td><td>Tear strength N / mm</td><td>Shore Hardness</td>

<td>Control 6 without soot</td><td> 1.04</td><td> 1.46</td><td> 3.14</td><td> 21.6</td><td> 53</td>

<td>Example 26</td><td> 1.71</td><td> 2.58</td><td> 7.61</td><td> 29.1</td><td> 62</td>

<td>Example 27</td><td> 2.14</td><td> 3.42</td><td> 11.70</td><td> 33.0</td><td> 67</td>

<td>Example 28</td><td> 3.00</td><td> 5.14</td><td> 18.19</td><td> 28.1</td><td> 72</td>

Table 11: Properties of XNBR, reinforced with FEF N550 soot.

DYNAMIC PROPERTIES

In this section, attempts were made to compare dynamic properties of the XNBR mixtures, reinforced with Pebax 3 and prepared in Examples 14,15 and 16, with the dynamic properties of the XNBR mixtures reinforced with different amounts of soot and prepared in according to Examples 26,27 and 28.

For these examples, the amounts of reinforcement (see Tables 7 and 11) and the hardnesses are equivalent for the mixtures containing thermoplastics as fillers and those containing soot as fillers.

In a first sample, the developed hysteresis ranges were compared between soot-containing filler mixtures and rubber reinforced with Pebax 3 during a tensile test that went up to 90% deformation for the specimens (130 mm x 2 mm).

<td colspan="2">Blends containing soot</td><td colspan="2">Mixtures with Pebax 3</td>

<td>Try</td><td>% Hysteria 1</td><td>Try</td><td>% Hysteria 1</td>

<td>Example 26</td><td> 35</td><td>Example 14</td><td> 26</td>

<td>Example 27</td><td> 38</td><td>Example 15</td><td> 28</td>

<td>Example 28</td><td> 42</td><td>Example 16</td><td> 29</td>

Table 12: Comparative hysteresis values ​​for mixtures containing soot as filler and rubber modified with thermoplastics.

In all samples, the hysteresis values ​​were measured after 5 deformation cycles.

A second comparison test between the same mixtures was conducted according to NFT standard 46.045. Cylindrical segments (d = 17.8 mm, h = 25 mm) were subjected to a compressive dynamic load (compression 250 N, deformation with an amplitude of 1 mm, frequency scanning from 0 to 50 Hz). The change in the tang δ, called the loss factor, was observed as a function of frequency and a large increase in the tang δ for the mixture modified with thermoplastic was observed, which is characteristic of weaker internal heating.

<img file="NO312552B1_D0002.tif" />

<img file="NO312552B1_D0003.tif" />

Control 6

Example 26

Example 27

Example 28

Example 14

Example 15

Frequency (Hz)

<img file="NO312552B1_D0004.tif" />

<img file="NO312552B1_D0005.tif" />

Resistance to oil

The resistance to oils is measured according to the principles enshrined in ASTM Standard D 471 by lowering samples from Examples 5,6,7, 8, 9,10,11,12,13 as well as their control, in ASTM Oil 3 in 7 days at 100 ° C and by measuring their swelling in%.

<td>Reference</td><td>Composition</td><td>% swelling</td>

<td>Control 3</td><td>100% HNBR</td><td> 21</td>

<td>Example 5</td><td>95% HNBR / 5% Pebax 2</td><td> 20</td>

<td>Example 6</td><td>90% HNBR / 10% Pebax2</td><td> 19</td>

<td>Control 4</td><td>100% XNBR</td><td> 18</td>

<td>Example 8</td><td>95% XNBR / 5% Pebax 2</td><td> 17.5</td>

<td>Example 9</td><td>90% XNBR / 10% Pebax 2</td><td> 16</td>

<td>Example 10</td><td>80% XNBR / 20% Pebax 2</td><td> 15</td>

<td>Control 5</td><td>100% ECOT</td><td> 11</td>

<td>Example 11</td><td>95% ECOT / 5% Pebax 2</td><td> 10.5</td>

<td>Example 12</td><td>90% ECOT / 10% Pebax2</td><td> 10</td>

<td>Example 13</td><td>80% ECOT / 10% Pebax2</td><td> 9</td>

Table 13: Resistance to oils for the modified rubber.