Compositions containing hydrogenation block copolymer and polyamide

The invention relates to a composition based on a partially hydrogenated block copolymer comprising at least two end polymer segments A of a monoalkenyl arene having an average molecular weight of from 5,000 to 125,000 and at least one intermediate polymer segment B of a conjugated diene having an average molecular weight of from 10,000 to to 300,000, wherein the proportion of the end polymer segments A constitutes between 8 and 55% by weight of the block copolymer and at most 25% of the arena double bonds in the polymer segments A and at least 80% of the aliphatic double bonds in the polymer segments B are reduced by hydrogenation.

Block copolymers comprising at least two end-polymer blocks of a monoalkenylarene and at least one intermediate-polymer block of a conjugated diene are known. A block copolymer of this type is represented by the polystyrene-polybutadiene-polystyrene (SBS) structure. When the monoalkenylene segments constitute less than 55% by weight of the block copolymer, the product may be termed thermoplastic elastomer. By this is meant a polymer which in the molten state can be processed in ordinary equipment for processing thermoplastics but which in the solid state behaves like a chemical

7706572-0 vulcanized rubber without any chemical vulcanization. Such block copolymers are not compatible with polar polymers, such as polyamides. According to British Pat. , VI B, VII B or VIII with an aliphatic carboxylic acid, hydrofluoric acid or phosphoric acid. Example 8 of the specification discloses a composition containing 75 parts of a three-block copolymer of butadiene and 30% by weight of styrene (1,2-vinyl content 10%, 1,4-cic content 35%), 25 parts of polycaprolactam and 2 parts of lanthanum (III) fluoride. It has been found that an interpenetrating network can be obtained by mixing a partially hydrogenated block copolymer and a polyamide. An interpenetrating network of two polymers is a mixture in which one of the polymers is intended to fill the gaps of one form of the other polymer. The interpenetrating network is not a mixture in which there is a molecular mixture. Although the polymers form separate and distinct phases, they are not in a form that can lead to any more significant phase separation leading to delamination.

According to the invention there is obtained a composition based on a partially hydrogenated block copolymer comprising at least two end polymer segments A of a monoalkenyl arene having an average molecular weight of from 5,000 to 125,000 and at least one intermediate polymer segment having an average molecular weight of from 10,000 to 300,000, the proportion of the end polymer blocks A constitute between 8 and 55% by weight of the block copolymer, and at most 25% of the diene double bonds in the polymer segments A and at least 80% of the aliphatic double bonds in the polymer segments B are reduced by hydrogenation, which composition is characterized in that it comprises (a) 100 parts by weight of the partially hydrogenated block copolymer and (b) 5-200 parts by weight of a polyamide of the formula

<img file="SE418299B_D0001.tif" />

!

<img file="SE418299B_D0002.tif" />

7706572-0 where a, b and c each vary from 4 to 12 and n and m are whole numbers corresponding to a number average molecular weight of between 10,000 and 30,000.

The block copolymer can be linear, radial or branched. Methods for preparing such polymers are known. The structure of the block copolymers is determined by the polymerization methods. So e.g. linear polymers are obtained by sequentially introducing the desired monomers into the reaction vessel and using such initiators as lithium alkyls or dilithiostilbene or by coupling a two-segment copolymer with a bifunctional coupling agent. Branched structures, on the other hand, can be obtained by using suitable coupling agents having a functionality of three or more with respect to the starting polymers. Coupling can be accomplished by multifunctional coupling agents, such as dihaloalkanes or alkenes, as well as with certain polar compounds such as silicon halides, siloxanes, or esters of polyhydric alcohols with carboxylic acids. The presence of any coupling residues in the polymer can be ignored for adequate description of the polymers which form part of the compositions according to the invention. Likewise, in a generic sense, the specific structures can also be ignored. The invention relates in particular to the use of selectively hydrogenated copolymers which, prior to hydrogenation, have the configuration of the following typical types of polymer:

polystyrene-polybutadiene-polystyrene (SBS) polyethylene-polyisoprene-polystyrene (SIS) poly (alpha-methylstyrene) -polybutadiene-poly (alpha-methylstyrene) (alpha-MeSBalfa-MeS) and poly (alpha-methylstyrene) -polyisoprene-poly ( alpha-methylstyrene) (alpha-MeSIalpha-MeS).

Both polymer segments A and B can be either homopolymer or random copolymer segments as long as each segment predominates in at least one class of the monomers that characterize the segments defined above. Thus, segments A may comprise styrene / alpha-methylstyrene copolymer segments or randomly constructed styrene / butadiene copolymer segments as long as individual monoalkenyl arenes are predominant in the segments. The term monoalkenylarene is intended to include styrene and its analogs and homologues, including alpha-methylstyrene and ring-substituted styrenes, especially ring-methylated styrenes · Preferred monoalkenylarenes

7706572-0 is styrene and alpha-methylstyrene, and styrene is especially preferred. Segments B may comprise homopolymers of butadiene or isoprene, copolymers of butadiene with isoprene and copolymers of one of these two dienes with a monoalkenyl arene 'as long as diene units conjugated to segments B are predominant. Since the monomer used is butadiene, it is preferred that between 35 and 55 mole percent of the fused butadiene units in the butadiene polymer segment have 1,2-configuration. When such a segment is hydrogenated, the resulting product is or is similar to a regular copolymer segment of ethylene and butene-1 (EB). If the conjugated diene used is isoprene, the resulting hydrogenated product is or is a regular copolymer segment with alternating ethylene and propylene (EP).

Hydrogenation of the starting block copolymers preferably takes place using a catalyst comprising the reaction products of an aluminum alkyl compound with nickel or cobalt carboxylate or alkoxides under such conditions that at least 80% of the aliphatic double bonds but only about 25% of the aromatic alkenyl arene compounds the double bonds are hydrogenated. Preferred block copolymers are those in which at least 99% of the aliphatic double bonds and less than 5% of the aromatic double bonds are hydrogenated.

·. The average molecular weight of the individual segments may vary within certain limits. The block copolymer included in the composition of the invention has at least two end polymer blocks A of a monoalkenylarene having an average molecular weight of from 5,000 to 125,000 and at least one intermediate polymer block B of a conjugated diene having an average molecular weight of from 10,000 to 300,000. These molecular weights is most accurately determined by tritium counting methods or osmotic pressure measurements. The proportions of the polymer blocks A of the monoalkenyl arene should be between 8 and 55% by weight of the block copolymer, preferably between 10 and 30% by weight thereof.

The polyamide present in the composition according to the invention - hereinafter referred to as nylon - is represented by the following formulas:

^CΊ

--ö - L chU ------ NH *

IT V 2ja 'J n eller

<img file="SE418299B_D0003.tif" />

7706572-0 where a, b and c respectively can vary from 4 to 12. The nylons may be those which have pendant hydrocarbon groups instead of a hydrogen atom attached to the nitrogen atom or the methylene carbon atoms in the polymer chain. The molecular weights (Mn = the numerical average value of the molecular weight) used in the polyamides according to the invention are between 10,000 and 30,000, preferably between 15,000 and 25,000.

Preferred nylons are nylon 6 (polymer of epsilon-aminocaprolactam), nylon 6,6 (polymer of hexamethylenediamine and adipic acid), nylon 6,10 (polymer of hexamethylenediamine and sebacic acid), nylon 11 (polymer of tu-amino-undecanoic acid), nylon 4 (polymer of pyrrolidone), nylon 7 (polymer of aminoheptanoic acid), nylon 9 (polymer of 9-aminononanoic acid). Nylon 6 and nylon 6,6 are especially preferred.

The amount of polyamide used varies from 5 to 200 phr, preferably from 5 to 75 phr, or more preferably from 10 to 40 phr. By "phr" is meant parts by weight per 100 parts by weight of the partially hydrogenated block copolymer.

There are at least two means (safer than the observation of the absence of delamination) by which the presence of interpenetrating networks can be demonstrated. According to one method, an interpenetrating network is shown in which cast or extruded articles made from blends of the invention are introduced into a solvent which releases the block copolymer, and the remaining polymer structure (including the polyamide) still has the shape of the cast or extruded article. If the remaining structure exhibits continuity, an interpenetrating network has been formed.

The second method for detecting the presence of an interpenetrating network consists in measuring the tensile strength of the mixture. This simply follows from the fact that an applied tensile stress is distributed over the available network elements. The number of elements that absorb a force is reduced in the presence of a non-contributing filler. At low concentrations of the secondary heterophase (polyamide), where an interpenetrating network is lacking, islands of polyamide crystallites dilute the number of stressed block copolymer elements. If the concentration of polyamide is increased to a point where a continuous crystalline structure is present in the whole segment of the copolymer, then the other network is able to absorb some of the tensile stress and the presence of interpenetrating networks manifests itself as an increased tensile modulus and strength.

7706572-0

The nylon and the hydrogenated block copolymer can be mixed in any manner that produces the interpenetrating network. So e.g. For example, the two polymers can be dissolved in a solvent common to both and coagulated by mixing in a solvent in which neither polymer is soluble. However, a preferred and particularly useful procedure is to intimately mix the two polymers as melts of small rods and / or powder in a device in which shear takes place. -215 ° C for 12-15 minutes to obtain a suitable mixture but this is not enough to mix nylon 6 or nylon 66. However, good results are obtained with nylon 6 when using a Banbury mixer, Laboratory Model B. In order to obtain the mixture required for an interpenetrating network with nylon 66, it is necessary to use both the mixture obtained with the Banbury mixer, Laboratory Model B , and passing the material through an Ankerwerk 3-ounce ”injection molding machine with reciprocating piston. A practical way to safely provide the interpenetrating network is to mix the polymers in the form of small rods and / or powders in a Banbury mixer at a temperature of 10-30 ° C above the melting point of the highest temperature melting polymer with subsequent processing steps. i.e. extruder by means of an extruder with a twin screw or injection molding in a machine with a reciprocating piston.

The mixing and processing temperature used varies from 200 ° C to 300 ° C.

The blend of nylon with the partially hydrogenated block copolymer can be provided with an extender oil commonly used in the processing of rubber and plastics. Particularly preferred are the types of oil that are compatible with the elastomeric segments of the block copolymer. Although oils with a higher aromatic content are satisfactory, petroleum-based white oils with low volatility and less than 50% aromatic content determined according to the clay-gel method (ASTM test method D 2007) are particularly preferred. In addition, the oils should have a low volatility and preferably have an initial boiling point in excess of 260 ° C.

The amount of oil used can vary from 0 to 50 phr (phr = parts by weight per 100 parts by weight of block copolymer), preferably from 50 to 30 phr.

7706572-0

The mixture of nylon with the partially hydrogenated block copolymer can be further added with a resin. The added resin may be a polymeric alpha-olefin or a flow enhancing resin such as an alpha-methylstyrene resin, a vinyltolucine / alpha-methylstyrene resin and a softening end block resin. The polymers of alpha-olefins include both high and low density polyethylene, isotactic and atactic polypropylene and polybutene-1. The preferred poly-alpha-olefin is isotactic polypropylene which is a crystalline polypropylene.

The amount of resin added may vary from 0 to 100 phr, preferably from 5 to 25 phr.

Furthermore, the composition may contain fillers, antioxidants, stabilizers and other components.

Elastomer compositions prepared in accordance with this invention are suitable for most purposes for which rubbers and flexible thermoplastics, such as polyurethanes, are used, e.g. mechanical parts, thermoformed articles, insulations, etc. The compositions can be injection molded, blow molded or extruded. Other shaped objects as well as films, sheets and covers on textiles can be produced. The compositions can be cast as a solution to form films or spun into fibers or applied as a coating to other articles. Casting compositions for common end uses of plastics can be prepared, especially when the monoalkenylarene copolymer segments constitute a high percentage by weight of the block polymer. Intended plastic end uses include molds or compacts, mechanical parts, extruded articles such as films, sheets and fibers. The present invention is of particular use in such cases when manufactured articles are exposed to oxidative environments at high temperatures such as under the hood of cars or in electrical engineering.

The invention is elucidated in the following by some examples. Example 1 The following tables relate to blends of block copolymers of polystyrene / hydrogenated polybutadiene / polystyrene and low and medium viscosity nylon 6 and low viscosity nylon 66. These mixtures were prepared from the components of a laboratory type Model B Banbury mixer at about 400 ° C for 7 minutes until a homogeneous mixture was formed. Then injection molding was carried out at 260 ° C in an Ankerwerk^Minjection molding machine with reciprocating screw.

7706572-0

The block copolymer A had the block molecular weights 25,000 - 100,000 - 25,000, the block copolymer B the block molecular weights 9,000 - 47,000 - 9,000 and the block copolymer C the block molecular weights 6,000 - 35,000 - 6,000.

The compositions and results are summarized in Tables 1, 2 and 3 below.

Table 1

Composition of the specimens

Resin

<td colspan="3" rowspan="2">SegmentProv copolymer</td><td colspan="2">Polyamide</td><td colspan="2" rowspan="3">Polypropylene med.sf high sf</td><td rowspan="3">Acrylic resin</td><td rowspan="3">Polyvinyltoluene resin</td><td rowspan="3">Etenvi-⁴new acetate copolymer</td>

<td rowspan="2">Nylon € low whisk.</td><td rowspan="2">) Nylon 6 Nylon 6,6 with · low whisk. whisk.</td>

<td>no</td><td>A</td><td>B.C</td>

<td> 1131</td><td> 50</td><td> - 50</td><td> -</td><td> * —</td><td> —</td><td> 10</td><td> —</td><td> -</td><td> -</td>

<td> 1132</td><td> —</td><td> 50 50</td><td> -</td><td></td><td> —</td><td> 10</td><td> -</td><td> —</td><td> —</td>

<td> 1136</td><td> -</td><td> 50 50</td><td> 30</td><td> — —</td><td> —</td><td> 10</td><td> -</td><td> —</td><td> —</td>

<td> 1149</td><td> 50</td><td> 50 -</td><td> 45</td><td> - —</td><td> 15</td><td> —</td><td> —</td><td> -</td><td> --</td>

<td> 1150</td><td> 50</td><td> 50 -</td><td> 30</td><td> — _M</td><td> 15</td><td> —</td><td> 30</td><td> —</td><td> —</td>

<td> 1151</td><td> 50</td><td> 50 -</td><td> 60</td><td> - _M</td><td> 15</td><td> —</td><td> —</td><td> —</td><td> -</td>

<td> 1152</td><td> -</td><td> 100 -</td><td> 45</td><td> - -</td><td> 15</td><td> —</td><td> —</td><td> —</td><td> -</td>

<td> 1153</td><td> —</td><td> 100 -</td><td> 30</td><td> — —</td><td> 10</td><td> —</td><td> —</td><td> —</td><td> —</td>

<td> 1154</td><td> 25</td><td> 75 -</td><td> 45</td><td></td><td> 15</td><td> —</td><td> —</td><td> —</td><td> —</td>

<td> 1155</td><td> —</td><td> 100 -</td><td> 30</td><td> — —</td><td> 15</td><td> —</td><td> 15*</td><td> —</td><td> -</td>

<td> 1156</td><td> —</td><td> - 100</td><td> 30</td><td> — —</td><td> 10</td><td> —</td><td> —</td><td> —</td><td> —</td>

<td> 1157</td><td> —</td><td> - 100</td><td> 30</td><td> — -</td><td> —</td><td> 10</td><td> —</td><td> -</td><td> —</td>

<td> 1158</td><td> -</td><td> - 100</td><td> 30</td><td> - —</td><td> —</td><td> -</td><td> -</td><td> 10</td><td> -</td>

<td></td><td></td><td></td><td></td><td colspan="2">Table 1 (continued)</td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td colspan="3">Composition of the specimens</td><td></td><td></td><td></td><td></td>

<td>Sample</td><td></td><td colspan="2">, · 4) Softening</td><td>Stabilizer</td><td colspan="2">«· 6) Pigment</td><td></td><td></td><td></td>

<td>nr__</td><td></td><td>oil</td><td></td><td>AO, UV</td><td colspan="2">Carbon black</td><td></td><td></td><td></td>

<td> 1131</td><td></td><td colspan="2"> 20**</td><td> 2</td><td> 5</td><td></td><td></td><td></td><td></td>

<td> 1132</td><td></td><td> —</td><td></td><td> 2</td><td> 5</td><td></td><td></td><td></td><td></td>

<td> 1136</td><td></td><td> —</td><td></td><td> 2</td><td> 5</td><td></td><td></td><td></td><td></td>

<td> 1149</td><td></td><td> 20</td><td></td><td> 2</td><td> 5</td><td></td><td></td><td></td><td></td>

<td> 1150</td><td></td><td> 20</td><td></td><td> 2</td><td> 5</td><td></td><td></td><td></td><td></td>

<td> 1151</td><td></td><td> 20</td><td></td><td> 2</td><td> 5</td><td></td><td></td><td></td><td></td>

<td> 1152</td><td></td><td> —</td><td></td><td> 2</td><td> 5</td><td></td><td></td><td></td><td></td>

<td> 1153</td><td></td><td> —</td><td></td><td> 2</td><td> 5</td><td></td><td></td><td></td><td></td>

<td> 1154</td><td></td><td> 10</td><td></td><td> 2</td><td> 5</td><td></td><td></td><td></td><td></td>

<td> 1155</td><td></td><td> —</td><td></td><td> 2</td><td> 5</td><td></td><td></td><td></td><td></td>

<td> 1156</td><td></td><td> —</td><td></td><td> 2</td><td> —</td><td></td><td></td><td></td><td></td>

<td> 1157</td><td></td><td> —</td><td></td><td> 2</td><td> —</td><td></td><td></td><td></td><td></td>

<td> 1158</td><td></td><td> —</td><td></td><td> 2</td><td> —</td><td></td><td></td><td></td><td></td>

7706572-0

Table 1 (continued) Composition of the specimens

<td rowspan="3">Sample no</td><td colspan="2" rowspan="2">Copolymer segment</td><td colspan="4">Nylon 6 Nylon 6 Nylon 6,6 1'oly-</td><td colspan="2" rowspan="3">Acrylic-) high sf resin</td><td rowspan="3">„1, 2) Polyvinyl toluene resin</td><td rowspan="3">El envinyl ar.i tatHampolymcr</td>

<td rowspan="2">low whisk.</td><td rowspan="2">with. whisk.</td><td rowspan="2">make whisk.</td><td rowspan="2">propylene with sf</td>

<td>AU</td><td>C</td>

<td> 1163</td><td> - 50</td><td> 50</td><td></td><td> -</td><td> 30</td><td> -</td><td> 10</td><td> -</td><td> -</td><td></td>

<td> 1165</td><td> - 100</td><td> —</td><td> 30</td><td> —</td><td> —</td><td> —</td><td> —</td><td> —</td><td> 10</td><td> -</td>

<td> 1166</td><td> - 100</td><td> -</td><td> 30</td><td> -</td><td> —</td><td> -</td><td> -</td><td> —</td><td> 10</td><td> 10</td>

<td> 1168</td><td> - 50</td><td> 50</td><td> —</td><td> 30</td><td> —</td><td> 10</td><td> —</td><td> —</td><td> —</td><td> —</td>

<td> 1169</td><td> - 100</td><td> —</td><td> —</td><td> 30</td><td> —</td><td> 10</td><td> —</td><td> -</td><td> —</td><td> —</td>

1) Acryloid KM-611 and^xAcryloid K-120N resins, Rohm &amp; Haas

2) Piccotex 120 resin PICCO

3) Ultrathene 641 resin, USI Chemical

Table 1 (continued)

Sample Softening-4) Stabilizer Pigment no oil AO, UV Carbon black

1163 -2

1165 -2

1166 -2

1168 -2

1169 -2

4) Indopol H-50 oil, Amoco Chemical and^xx SIIELEEEEX® 790-ol ja, filad I chrniiral

5) 0.5 phr of each hindered phenol, oeh di lauryl l: lodiproplond-πηΐτίοκidaorei, boiniotriazole- oeh hydroxy-UV-alnbi I hintorer

6) 1I-diapcralone of SFR-avart in atun-vinyl-acetate-HainpoJ ymer with hops, af (nm'lltllyh ning)

7706572-0

Table 2 • · 1) 2)

Physical properties of specimens⁷

Hard- Gardner Impact Stiffness ^ Ross Flex

Sample has cm / 0.45 kp kp / cm²/ 2 notches. Oven stability no Shore D 50 50 ~ 125 225 rad. 0.5 Kc 10 Kc Shrinkage Distortion (~ 30 ° C) (23 ° C) (23 ° C)

<td> 1131 1132</td><td> 18 26</td><td>m.god m.god</td><td>good</td><td>1002 cut.</td><td></td><td></td><td></td><td>m.stor m.stor</td><td>serious serious</td>

<td> 1136</td><td> 38</td><td>burst</td><td>good</td><td>1 »skarn, deform.</td><td> 401/548</td><td> —</td><td> —</td><td>No</td><td>No</td>

<td> 1149</td><td> 35</td><td>burst</td><td>quite good</td><td>1.skårn. deform.</td><td></td><td> —</td><td> —</td><td> —</td><td> —</td>

<td> 1150</td><td> 32</td><td>burst</td><td>quite good</td><td>1.skårn. deform.</td><td> -</td><td> —</td><td> —</td><td> —</td><td> —</td>

<td> 1151</td><td> 40</td><td>burst</td><td>quite good</td><td>1.skårn. deform.</td><td> —·</td><td> 600</td><td> 900</td><td> -</td><td> —</td>

<td> 1152</td><td> 43</td><td>burst</td><td>quite good</td><td>1.skårn. deform.</td><td> —</td><td> —</td><td> —</td><td> —</td><td> —</td>

<td> 1153</td><td> 37</td><td>burst</td><td>quite good</td><td>1st cut. deform.</td><td></td><td> 200</td><td> 900</td><td> —</td><td> —</td>

<td> 1154</td><td> 39</td><td>burst</td><td>quite good</td><td>1.cut, deform.</td><td> —</td><td> —</td><td> —</td><td> — ₍</td><td> —</td>

<td> 1155</td><td> 42</td><td>burst</td><td>quite good</td><td>1.skårn. deform.</td><td> -</td><td> —</td><td> —</td><td> —</td><td> —</td>

<td> 1156</td><td> 41</td><td>burst</td><td>quite good</td><td>deform.</td><td> —</td><td> —</td><td> —</td><td>No</td><td>No</td>

<td> 1157</td><td> 38</td><td>burst</td><td>steering wheel good</td><td>deform.</td><td></td><td> ··</td><td> —</td><td>No</td><td>No</td>

<td colspan="6">Table 2 (continued) 1) 2) Physical properties of specimens</td>

<td rowspan="2">Sample no</td><td rowspan="2">Tear strength) cp / 2.5 cm</td><td rowspan="2">Modulus of elasticity during bending, kp / cni</td><td colspan="3">Tensile strength properties</td>

<td>^M100, kp / cm²</td><td>^Tb, kp / cm²</td><td>^Ε· '* Λ</td>

<td> 1131</td><td> 133/128</td><td>(70 ° C) (23 ° C) (-30 ° C)</td><td> —</td><td> —</td><td> —</td>

<td> 1132</td><td> 149/135</td><td> — — —</td><td> —</td><td> —</td><td> -</td>

<td> 1136</td><td> 149/158</td><td> 352 1280 -</td><td> 77</td><td> 172</td><td> 500</td>

<td> 1149</td><td> —</td><td> - 654 -</td><td> 70</td><td> 70</td><td> 250</td>

<td> 1150</td><td> —</td><td> - 478 -</td><td> —</td><td> —</td><td> —</td>

<td> 1151</td><td> 1267117</td><td> - 1266 -</td><td> 77</td><td> 81</td><td> 110</td>

<td> 1152</td><td> —</td><td> - 1195 -</td><td> 91</td><td> 134</td><td> 380</td>

<td> 1153</td><td> 180/158</td><td> - 1055 -</td><td> -</td><td> -</td><td> -</td>

<td> 1154</td><td> —</td><td> - 886 -</td><td> —</td><td> —</td><td> —</td>

<td> 1155</td><td> —</td><td> - 1814 -</td><td> 84</td><td> 84</td><td> 500</td>

<td> 1156</td><td></td><td> - 1308 -</td><td> -</td><td> —</td><td> —</td>

<td> 1157</td><td> —</td><td> 352 1694 -</td><td> -</td><td> -</td><td> -</td>

7706572-0

Table 2 (continued). . * ---- Π ---------- 2Ί

Physical properties of specimens'

<td rowspan="2">HardTest hot</td><td colspan="2">Gardner Impact Stiffness ^</td><td rowspan="2">Ross Flex X swath production.</td><td rowspan="2">Oven stability</td>

<td>cm / 0.45 kp</td><td>kp / cnr /</td>

<td>No. _ Shore D</td><td> . 50 50-125 225</td><td>row.</td><td>0.5 Kc 10 Kc</td><td>Krympii ing D iat □ rs</td>

<td></td><td>(-30 ° C) (23 ° C) (23 ° C)</td><td></td><td></td><td></td>

<td> 1158 38</td><td>m.god god deform.</td><td> -</td><td> - -</td><td>no no no</td>

<td> 1163 40</td><td>- right -</td><td> -</td><td> 0 400</td><td>no no no</td>

<td></td><td>good</td><td></td><td></td><td></td>

<td> 1165 40</td><td>- right -</td><td> -</td><td> 200 900</td><td>no no no</td>

<td></td><td>good</td><td></td><td></td><td></td>

<td> 1166 43</td><td>- right -</td><td> —</td><td> — —</td><td>no no no</td>

<td></td><td>good</td><td></td><td></td><td></td>

<td> 1168 -</td><td>- right -</td><td> *·</td><td> 0 700</td><td> — —</td>

<td></td><td>good</td><td></td><td></td><td></td>

<td> 1169 -</td><td>- steering wheel -</td><td> —</td><td> — —</td><td> — —</td>

<td></td><td>good</td><td></td><td></td><td></td>

1) All properties measured on injection molded specimens at 23 ° C unless otherwise stated

2) The compositions are given in Table 1

3) Txnius-Olsen stiffness values ​​measured perpendicular to resp, parallel to the flow direction

4) 1 hour at 149 ° C '. Table 2 (continued). 1) 2)

Physical properties of specimens Tear strength-) Tensile strengthHogrimlr np »&gt;।

<td>Sample no</td><td>firmness kp / 2.5 cm</td><td>Modulus of elasticity during bending, bp / cm</td><td>^M100, kp / cm²</td><td>T. -, 7 b, kp / &lt;· ιιι</td><td></td>

<td></td><td></td><td>(70 ° C) (23 ° C) (-30 ° C)</td><td></td><td></td><td></td>

<td>U5B</td><td> »»</td><td> 260 - -</td><td> »</td><td> -</td><td>take</td>

<td> 1163</td><td> 225/180</td><td> - 1076 -</td><td> 112</td><td> 190</td><td> 460</td>

<td> 1165</td><td> 180/135</td><td> - 1514 -</td><td> 70</td><td> 162</td><td> 4 70</td>

<td> 1166</td><td> —</td><td>take take take</td><td> 70</td><td> 190</td><td> 5 50</td>

<td> 1168</td><td> —</td><td>take take take</td><td> —</td><td> -</td><td></td>

<td> 1169</td><td> -</td><td>take take take</td><td> -</td><td> -</td><td></td>

5) "Die C Angle tear" measured perpendicular to the respective, parallel to the flow »direction

6) Micro dumbbells measured parallel to the flow direction

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<td rowspan="3">Sample no</td><td rowspan="3">Segment ampoly mer</td><td colspan="4">Table 3</td><td colspan="3" rowspan="2">Properties at 23 ° C</td>

<td rowspan="2">Nylon 6 ^</td><td rowspan="2">Nylon 6,6 ^</td><td rowspan="2">Stabilis ^ y tor '</td><td rowspan="2">Hardness Shore D</td>

<td>Styvhgt kp / 'cm rad.</td><td>X 10³</td><td>Hardener strength 125 cm / 0.45 k;</td>

<td> 1228</td><td> 100</td><td> -</td><td> 50</td><td> 1,7</td><td> 41</td><td>(N) 0.56</td><td>(P) 0.59</td><td>excellent</td>

<td> 1229</td><td> 100</td><td> —</td><td> 100</td><td> 1,7</td><td> 60</td><td> 1’1</td><td> 1,5</td><td>very good</td>

<td> 1230</td><td> 100</td><td> -</td><td> 150</td><td> 1,7</td><td> 65</td><td> 1,7</td><td> 1,9</td><td>then 1 ig</td>

<td> 1231</td><td> 100</td><td> —</td><td> 200</td><td> 1,7</td><td> 68</td><td> 2,1</td><td> 2,6</td><td>bad</td>

<td> 1232</td><td> 100</td><td> 100</td><td> —</td><td> 1,7</td><td> 52</td><td> 0,8</td><td> 0,9</td><td>excellent</td>

<td> 1233</td><td> -</td><td> 100</td><td> —</td><td> -</td><td> 77</td><td> -</td><td> -</td><td>bad</td>

1) Hydrogenated SBS, nominal weight 65 M, approx. 28Z styrene

2) Medium viscosity type 6 resin, low viscosity type 6.6 resin

8) 0.2 phr hindered phenol antioxidant, 0.5 phr of each dilaurylthiodipropional antioxidant, benzotriazole and hydroxybenzoate UV stabilizers

4) Tinius-Olsen stiffness measured perpendicular to (N) and parallel to (P) the flow direction when injection molding

Example 2

A 112.5 kg sample of a mixture of a nylon 6 and a hydrogenated polybutadiene / polystyrene block copolymer having the composition and properties specified below was prepared by placing in a Werner-Pfleiderer twin-screw extruder, model ZSK 83/700, at zone temperatures from 200 ° C to 240 ° C and subsequent injection molding of specimens using the Stokes injection molding machine with a reciprocating screw at 230-275 ° C.

Composition

Ingredients Phr

Segment copolymer^{1 2 3 4 5 6 7}5 0

2)

Segment copolymer50

Nylon 6-resin * ^ 30

4)

Polypropylene10

Carbon black concentrate ^) 5

Antioxidants ^ 1

UV stabilizers ^ 1

1) Nominal molecular weight 65m, about 28% by weight polystyrene

2) Nominal molecular weight 47m, about 28% by weight polystyrene

3) Nylon 6 resin with low viscosity

4) Polypropylene rods with medium melt flow

5) 1/1 dispersion of SRF black in EVA

6) Equal amounts of hindered phenol and dilauryl thiodipropionate

7) Equal amounts of a benzotriazole and a hydroxybenzoate

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<td colspan="3">Physical properties ^ -.</td>

<td>Property</td><td colspan="2">ASTM Method Result</td>

<td>Spec. Weight Strength and hardness properties</td><td> —</td><td> 0,96</td>

<td>Hardness, Shore A score</td><td> -</td><td> 91</td>

<td>Hardness, Shore D points</td><td> —</td><td> 36</td>

<td>Traction breaking limit, kp / cm²23 ° C</td><td>D-412</td><td> 155</td>

<td>Elongation at break,%, 23 ° C</td><td>D-412</td><td> 350</td>

<td>Module at 100% elongation, bp / cm²23 ° C</td><td>D-412</td><td> 91</td>

<td>Module at 300% elongation, bp / cm²23 ° C</td><td>D-412</td><td> 141</td>

<td>Bending properties 2 Module of elasticity, bp / cm</td><td></td><td></td>

<td>23 ° C</td><td>D-790</td><td> 1266</td>

<td>70 ° C</td><td></td><td> 352</td>

<td>-30 ° C</td><td></td><td> 3164</td>

<td>2 Tinius-Olsen stiffness, kg / cm / row</td><td>D-747</td><td> 422-562</td>

<td>Tear strength "Die Angle Tear", bp / linear 2.5 cm</td><td>D-624</td><td> 144-247,5</td>

<td>Abrasion resistance Tabor H-18, cm³/1000.varv</td><td>D-1044</td><td> 1,90</td>

<td>Impact strength Gardner 50 cm / 0.45 kp</td><td> -</td><td>good</td>

<td>125 cm / 0.45 kp</td><td></td><td>good</td>

<td>200 cm / 0.45 kp</td><td></td><td>quite good</td>

<td>(-30 ° C) 50 cm / 0.45 kp</td><td></td><td>quite good</td>

<td>Elastic nature Elongation hysteresis, 100% Elongation Loss, 1st cycle,%</td><td> —</td><td> 70</td>

<td>Loss, equilibrium,%</td><td></td><td> 40</td>

<td>1) The properties were determined with ASTM plates</td><td>or “Ross</td><td>Flex bars ”</td>

injection molded using Stokes injection molding machine with reciprocating screw at 7.2-274 ° C.

Example 3

100 parts of a hydrogenated SBS resin comprising polystyrene segments having a number average molecular weight of 10,000 and a hydrogenated butadiene segment having a number average molecular weight of 50,000 containing 0/2 phr IONOL® were mixed with 50 parts of a nylon 11 (Rilson BMNO from Aquitaine Chemical ) on a 2 ”Farrell roller 7706572-0 grinder for 10-15 minutes at 195-215 ° C. The mixture was carefully processed on the mill. Molded test rods for tensile strength determination did not show any delamination. A satisfactory interpenetrating mixture was obtained. The physical properties were:

Traction breaking limit 74.5 kp / cm

Elongation at break 400%

Module at 300% elongation 54.8 kp / cm

Permanent change of shape at break 15%

Example 4 Example 2 was repeated but a poly (alpha-methylstyrene) / hydrogenated butadiene / poly (alpha-methylstyrene) block copolymer was used instead of SEBS. A satisfactory interpenetrating mixture was obtained.

Example 5

Example 2 was repeated except that a polystyrene / hydrogenated polyisoprene / polystyrene block copolymer was allowed to replace SEBS. A satisfactory interpenetrating mixture was obtained.

Example 6

Example 2 was repeated except that a poly (alpha-methylstyrene) / hydrogenated polyisoprene / poly (alpha-methylstyrene) block copolymer was used instead of SEBS. A satisfactory interpenetrating mixture was obtained.

The examples show that the impact strength, elasticity and flexibility are significantly reduced at nylon contents significantly above 50% on the whole blend and that nylon / hydrogenated ABA blends are very superior in terms of resistance to heat distortion at high temperatures compared to the selectively hydrogenated block copolymers. of ABA type.