Organosilane- and/or organosiloxane-containing agent used in filled polyamide

The present invention relates to the use of organosilane-containing agent for modifying the surface of fillers which are used in the manufacture of filled polyamide compounds. the present invention provides surface-modified fillers, hereby filled polyamides and products based thereon also relates.

It is known to incorporate fillers into polymers. A motive for this is the cost savings. A portion of the expensive polymer can be replaced by low cost extending. Another reason is the controlled modification of mechanical properties of the polymer . The filler is then added to a functional filler. The mechanical properties such as tensile strength and flexural strength, filled by z. B. polyamide compounds (hereinafter referred to as PA-Compound) can be permanently improved.

To achieve higher degrees of filling long aminosilanes such. B. DYNASYLAN®^® AMEO used (<patcit id="pcit0001" dnum="US3843591A"><text>US 3843591</text></patcit>. <patcit id="pcit0002" dnum="EP0136540B1"><text>EP 136 540 B1 0</text></patcit>). A disadvantage is the poor toughness of a prepared using a aminopropyltrialkoxysilane PA compound. A typical PA compound contains two completely different basic components: an inorganic mineral and an organic polymer. The inorganic mineral is generally hydrophilic and has an ionic structure. The organic polymer is generally rather hydrophobic and has a covalent structure. Both base components have different expansion coefficients, surface tensions, bending strength, etc. The largest incompatibility is present at the interface of the inorganic and organic components. This is usually the weak point of a filled PA compounds. A modification of the interface with aminoalkoxysilanes leads to an adhesion bridge and thereby increase the strength of the PA compounds. Although many mechanical properties are improved by the aminosilane, this is not true for impact properties.

<patcit id="pcit0003" dnum="EP0997469A2"><text>EP 0997469 A2</text></patcit> discloses specific aminopropyl functional siloxane oligomer and their use.

From the <patcit id="pcit0004" dnum="DE19908636"><text>German patent application 199 08 636.2</text></patcit> are water-based compositions of specific amino-functional silicon compounds, "bis-aminosilanes" refer, among other things, so-called, that you can use, for example, for the modification of glass and mineral fiber surfaces, as well as for surface modification and treatment of pigments.

<patcit id="pcit0005" dnum="EP0518057B1"><text>EP 518 057 B1 0</text></patcit> discloses blends vinyl / alkyl / alkoxy groups-containing siloxanes which are used as crosslinking agents for thermoplastic polyolefins. Mixtures aminopropyl / alkoxy- / alkyl-functional siloxane oligomers go from the<patcit id="pcit0006" dnum="DE19849308"><text>German patent application 198 49 308.8</text></patcit> produce, wherein the mixtures of, inter alia, as an adhesion promoter in filled thermoplastic compounds, in the coating of glass fibers, for silanizing fillers and pigments are used.

The <patcit id="pcit0007" dnum="EP0716127A2"><text>European Patent Application EP 0716127 A2</text></patcit>. <patcit id="pcit0008" dnum="EP0716128A2"><text>EP 0716128 A2</text></patcit> and <patcit id="pcit0009" dnum="EP0832911A1"><text>EP 0832911 A1</text></patcit> are water-based organopolysiloxane-containing compositions can be seen, which are substantially obtainable by mixing water-soluble aminoalkylalkoxysilanes optionally glycidyl ether and Methacryloxyalkylalkoxysilanen with water-insoluble alkyl silanes and subsequent acid-catalyzed hydrolysis or co-condensation with removal of the hydrolysis alcohol. Also, such compositions can be used for coating glass fibers, for silanizing fillers and pigments.

The <patcit id="pcit0010" dnum="DE19818923"><text>German Patent Application 198 18 923.0</text></patcit> relates to stable compositions of water-soluble amino- and alkenyl-functional organosiloxanes, their preparation and use to modify the properties of pigments and fillers, such as alumina, magnesia, silica, chalk, gypsum, heavy Saves, glass fibers, glass beads, carbon black, wollastonite, kaolin, mica, talc - to name just a few.

Moreover teaches <patcit id="pcit0011" dnum="DE19818924"><text>German Patent Application 198 18 924.9</text></patcit> a process for preparing surface-modified fillers by treatment with an organosiloxane-containing composition, wherein the organosiloxane next to OH groups carries at least one amino-functional group and optionally further functional groups selected from alkyl, haloalkyl, alkenyl, Glycidyletheralkyl, acryloxyalkyl and methacryloxyalkyl. Such fillers are used in adhesives, sealants, polymer compositions, paints and varnishes.

The <patcit id="pcit0012" dnum="DE19830128"><text>German Patent Application 198 30 128.6</text></patcit> relates to flame retardant, the surface of which is modified by treatment with organosilanes or organosiloxanes. Such flame retardants can find, among other applications in polyamides.

Out <patcit id="pcit0013" dnum="DE19929021"><text>DE 199 29 021.0</text></patcit> is the use of functional organyloranyloxysilanes or co-condensates of these on carriers in cable compounds.

The invention was based on the object to provide a further opportunity to provide filled, solid and impact-resistant polyamides.

This object is achieved according to the claims.

It has been found that in particular fillers with an agent B (hereinafter also briefly referred to agents) treated, which is specified in more detail below, good strength properties combined with good impact properties in filled, and in particular kaolin, provide PA compounds.

The simultaneous modification of the interface between the filler and polyamide (PA) with a component having adhesion-promoting properties, for example an aminosilane, and a component with lubricating properties, for example, an alkylsilane, a polyether silane or a wax on the basis of polyethylene (PE), polypropylene or silicone , effected in a surprising and advantageous way, good or improved impact resistance while largely retaining good strength properties of the filled polyamide.

An agglomerate-free dispersion of the filler in the PA polymer matrix is ​​essential and is achieved when fillers that have been treated with one of the present compositions in an excellent manner.

Moreover, said PA compounds have improved rheology and can be compounded so easily. This means an additional cost saving for the compounder.

The present invention is therefore the use of an organosilane-containing agent for modifying the surface of fillers which are used in preparing filled polyamide, where the agent<ol><li>i) at least one amino-functional silicon compound of the general formula a)         R-Si (CH₃)_x(Z)_3-x     a) </li></ol> wherein the groups Z are identical or different and Z represents an alkoxy group having 1 to 3 carbon atoms or a chlorine atom, x is 0 or 1 and R is an amino group of formula H₂N - [(CH₂)₂NH]_y- (CH₂)₃- Y represents 0 or 1 or 2, preferably 3-aminopropyltrimethoxysilane (AMMO): [H₂N (CH₂)₃Si (OCH₃)₃], 3-aminopropyltriethoxysilane (AMEO): [H₂N (CH₂)₃Si (OC₂H₅)₃], N-aminoethyl-3-aminopropyltrimethoxysilane (DAMO): [H₂N (CH₂)₂NH (CH₂)₃Si (OCH₃)₃] As well as N-aminoethyl-N'-aminoethyl-3-aminopropyltrimethoxysilane (TRIAMO): [H₂N (CH₂)₂NH (CH₂)₂NH (CH₂)₃Si (OCH₃)₃], And / or at least one secondary aminosilane, and / or at least one tertiary aminosilane, and ii) at least one alkyl-functional silicon compound of the general formula b)         R'-Si {CH₃)_x(Z)_3-x     b) wherein the groups Z are identical or different and Z represents an alkoxy group having 1 to 3 carbon atoms or a chlorine atom, x is 0 or 1 and R represents a linear or branched or cyclic, optionally fluorine-substituted alkyl group having 1 to 16 C-atoms . and / or iii) if appropriate, a content of siloxanes which are obtainable by hydrolysis, condensation or cocondensation of compounds of the general formula b), wherein the average degree of oligomerization of the siloxanes is from 2 to 20, contains.

A special series of secondary amines are the so-called bis-aminosilanes, for example bis-AMMO and bis-AMEO, and the N-alkylated amino silanes of the general formula R-NH- (CH₂)₃-Themselves₃)_x(Z)_3-x represents, wherein the groups Z are identical or different and Z represents an alkoxy group having 1 to 3 carbon atoms or a hydroxy group or a chlorine atom, x is 0 or 1 and R is a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group with 5 to 12 C atoms or an aryl group having 6 to 12 carbon atoms, preferably 3- [N-butylamino] propyltrimethoxysilane, 3- [N-butylamino] propyltriethoxysilane, 3- [N-cyclohexylamino] propyltrimethoxysilane, or so-called "bis-aminosilane", preferably "bis-AMEO": [(H₅C₂O)₃Themselves₂)₃NH (CH₂)₃Si (OC₂H₅)₃] Or "bis-AMMO": [(H₃CO)₃Themselves₂)₃NH (CH₂)₃Si (OCH₃)₃]. An example of a tertiary amine silane is the so-called "Tris-AMEO" [(H₃CO)₃Themselves₂)₃]₃N.

Bis-aminosilanes in the present invention are also those described in <patcit id="pcit0014" dnum="DE19908636"><text>DE 199 08 636.2</text></patcit> are to be taken. Further, it can also store a method of hydrolysis, condensation or co-condensation of primary and secondary amino silanes can be seen. Out<patcit id="pcit0015" dnum="DE19908636"><text>DE 199 08 636.2</text></patcit> are also apparent examples of Aminosiloxanes, it is expressly pointed out that the entire contents of this or citations listed below are to be seen at the same time as the disclosure of the present application.

As primary aminosilanes useful in the present invention, for example, 3-aminopropyltrimethoxysilane (AMMO), 3-aminopropyltriethoxysilane (AMEO), N-aminoethyl-3-aminopropyltrimethoxysilane (DAMO).

Further, as an example of a tertiary aminosilane [(H₃CO)₃Themselves₂)₃]₃N (tris-AMEO) led.

Mixtures of primary and secondary and / or tertiary amino silanes and / or aminosiloxanes can be prepared in general by respectively mixing the individual components with thorough mixing.

As alkylsilanes of the formula b), for example, the following compounds may be mentioned: methyl trimethoxysilane (MTMS), methyltriethoxysilane (MTES), ethyltrimethoxysilane (ETMS), ethyltriethoxysilane (ETES), n-propyltrimethoxysilane (PTMO), n-propyltriethoxysilane (PTEO) octyltriethoxysilane (OCTEO) ,

Examples of other siloxanes within the meaning of the present invention which are generally available by hydrolysis, condensation or cocondensation of compounds of the formula a) and compounds of the general formula b), including methods for the preparation of corresponding siloxanes can in particular the European patents <patcit id="pcit0016" dnum="EP0518057B1"><text>EP 518 057 B1 0</text></patcit>. <patcit id="pcit0017" dnum="EP0716127A2"><text>EP 0716127 A2</text></patcit>. <patcit id="pcit0018" dnum="EP0716128A2"><text>EP 0716128 A2</text></patcit>. <patcit id="pcit0019" dnum="EP0832911A1"><text>EP 0832911 A1</text></patcit> and the <patcit id="pcit0020" dnum="DE19849308"><text>German patent application 198 49 308.8</text></patcit> be removed. For example, include oligomeric propyltriethoxysilane (VPS 9892) and cooligomeres alkyl / vinylsilane (DYNASYLAN®^® 6598) for this product group.

Suitably used in the present invention means B which an aminosilane of the general formula a) and ii) as component i) at least one alkylsilane of the general formula b), particularly preferably a mixture of AMEO and MTES.

Preferably also means that an aminosilane of the general formula a) and ii) as component i) oligomers of at least one alkylsilane of the general formula b), for example a mixture of AMEO and a condensate based on PTEO are.

In the present invention, agents are preferred which contain as component i) an aminosilane of the general formula a) and ii) co-oligomers of at least one aminosilane of the general formula a) and at least one alkylsilane of the general formula b).

According to the invention one uses means B for the treatment of fillers, which are used in particular for the production of PA compounds.

In general, one can treat the fillers with the agent, by adding up outputs the fillers and, optionally left to act under the increase in temperature and thus treated fillers optionally aftertreated thermally additionally after separation. One can in particular procedures such as<patcit id="pcit0021" dnum="DE19818924"><text>DE 198 18 924.9</text></patcit> It can be seen, see. Also <patcit id="pcit0022" dnum="DE19818923"><text>DE 198 18 923.0</text></patcit> as <patcit id="pcit0023" dnum="DE19830128"><text>DE 198 30 128.6</text></patcit>,

Preferably used as a filler for polyamides in the present invention, glass fiber, glass beads, wollastonite, calcined kaolin, mica, talc, magnesium hydroxide, melamine cyanurate and montmorillonite Nanocomsites.

The present invention is thus the use of an agent B for the treatment of fillers, in particular those which are used in preparing filled polyamide.

Further, according to the invention available, surface-modified fillers are the subject matter of the present invention.

In addition, products that are based on polyamide and containing at least one filler treated according to the invention, the subject of the present invention, particularly so-called filled polyamide.

For example - but not exclusively - in the present invention may be polyamides of the type PA 6 (poly-ε-caprolactam), 12 use PA 6.6 (polycondensate of hexamethylenediamine and adipic acid) or PA (poly-12-dodecalactam). An example of commercially available PA 6.6 is the product group ZYTEL®^® by DuPont. But you can also fill other polyamides with fillers according to the invention.

Suitably, one uses 0.1 to 70 wt .-%, preferably 10 to 40 wt .-%, of a filler according to the invention in the manufacture of a filled PA compounds.

In general, A filled PA compound by mixing the polyamide and the coated filler in a compounding kneader. For this purpose, as given over two dosing devices on the one hand polyamide granules and on the other hand, the filler in the heated to a temperature above the melting temperature of the polyamide mixer that the desired degree of filling can be maintained. Generally, filling ratio is the mass ratio of polyamide and filler such. As at 60 parts by weight of polyamide and 40 parts by weight filler in the compound of the degree of filling 40%. In general, the coming out of the mixer PA compound is then granulated and can z. B. are processed with an injection molding machine to semifinished or finished products.

Ready, z. B. produced by injection molding are a wide variety of housings for example, electronic devices and components for motor vehicles, z. B. hubcaps, fan housings, to name just a few.

The available inventively filled PA compounds are characterized generally by both good strength and good impact toughness.

The present invention also provides polyamide filled according and products that are based on such a polyamide.

The present invention is further illustrated by the following examples.

example 1

Preparation of silanized kaolin samples (General Procedure)

7000 g calcined kaolin are in a laboratory plowshare mixer, LÖDIGE M20, with a capacity of about 20 liters (POLESTAR 200 R. supplied by ECC / GB), and set the mixer into motion. The speed of the mixing tool is set at 400 rpm and temperature of the kaolin through the jacket of the mixing vessel by means of thermostat and thermal oil to about 80 ° C. After about 30 minutes preheating is metered via the metering of the mixer, the silane or the silane mixture: approx. 35 g per minute, 70 g If the full amount of silane is added, is mixed even 120 minutes after turning off the heat of which 90 minutes under reduced pressure.

example 2

Preparation of polyamide compounds kaolin

In a co-kneader, manufactured by BUSS, type PR46-11 D, via the first collection, the polyamide (ZYTEL® 101L, available from DuPont, 12 hours at 80 ° C dried) is metered by means of a screw with 6.5 kg / h. About the second collection the silanized kaolin is added in an amount of 4.33 kg / h with a twin-screw. The polyamide ratio to kaolin is characterized 60: 40, that the filling level is 40%. The rotational speed of the kneader is approximately 150 rpm, the cylinder temperature of 290 ° C, throughput 15 kg / h. The filling level is controlled by the determination of the ash content.

The final compound is granulated and for preparing test specimens with an injection molding machine manufacturer ENGEL, Type ES 240/65, further processed. The injection takes place at a pressure of 2 150 and a temperature of about 267 ° C. be squirted Normzugstäbe (multipurpose rods # 84). the following material combinations:<tables id="tabl0001" num="0001"><table frame="all"><tgroup cols="2"><colspec colnum="1" colname="col1" colwidth="21mm" /><colspec colnum="2" colname="col2" colwidth="145mm" /><thead><row><entry valign="top">Approach no.</entry><entry valign="top">Polyamide and kaolin coated with 1 wt .-% silane / siloxane (based on kaolin)</entry></row></thead><tbody><row><entry align="center">1¹⁾</entry><entry>γ-aminopropyltrimethoxysilane, (DYNASYLAN®^® AMEO)</entry></row><row><entry align="center">2¹⁾</entry><entry>γ-aminopropyltrimethoxysilane, technical quality, (DYNASYLAN®^® AMEO-T)</entry></row><row><entry align="center">4</entry><entry>Physical mixture of 60 parts by weight DYNASYLAN^® AMEO-T and 40 parts by weight of the oligomer PTEO VPS 9892</entry></row><row><entry align="center">5</entry><entry>Physical mixture of 2 parts of DYNASYLAN^® AMEO and 1 part DYNASYLAN®^® MTES, (DYNASYLAN®^® 1291)</entry></row></tbody></tgroup><tgroup cols="2" rowsep="0"><colspec colnum="1" colname="col1" colwidth="21mm" /><colspec colnum="2" colname="col2" colwidth="145mm" /><tbody><row><entry namest="col1" nameend="col2" align="justify">¹⁾ Comparative Examples</entry></row></tbody></tgroup></table></tables>

Examples 3 to 7

Test results of the produced according to Examples 1 and 2 Polyamide-kaolin Compounds:

example 3

Determination of tensile strength according to DIN EN ISO 527

<tables id="tabl0002" num="0002"><table frame="all"><tgroup cols="5"><colspec colnum="1" colname="col1" colwidth="20mm" /><colspec colnum="2" colname="col2" colwidth="38mm" /><colspec colnum="3" colname="col3" colwidth="38mm" /><colspec colnum="4" colname="col4" colwidth="39mm" /><colspec colnum="5" colname="col5" colwidth="33mm" /><thead><row><entry align="center" valign="top">Approach no.</entry><entry align="center" valign="top">E modulus after 24 h 23 ° C / 50% rel. Wet [N / mm²]</entry><entry align="center" valign="top">Modulus of elasticity in% of sample 1 (AMEO)</entry><entry align="center" valign="top">Modulus after 7 days immersion in water at 90 ° C [N / mm²]</entry><entry align="center" valign="top">Modulus-waste in%</entry></row></thead><tbody><row><entry align="center">1</entry><entry align="center">6050.5</entry><entry align="center">100.0</entry><entry align="center">1523.1</entry><entry align="center">25.2</entry></row><row><entry align="center">2</entry><entry align="center">6232.1</entry><entry align="center">103.0</entry><entry align="center">1 634.0</entry><entry align="center">26.2</entry></row><row><entry align="center">4</entry><entry align="center">6388.6</entry><entry align="center">105.6</entry><entry align="center">1628.0</entry><entry align="center">25.5</entry></row><row><entry align="center">5</entry><entry align="center">6058.4</entry><entry align="center">100.1</entry><entry align="center">1 636.0</entry><entry align="center">27.0</entry></row></tbody></tgroup></table></tables>

example 4

Determination of flexural strength according to DIN EN ISO 178

<tables id="tabl0003" num="0003"><table frame="all"><tgroup cols="3"><colspec colnum="1" colname="col1" colwidth="20mm" /><colspec colnum="2" colname="col2" colwidth="85mm" /><colspec colnum="3" colname="col3" colwidth="61mm" /><thead><row><entry align="center" valign="top">Approach no.</entry><entry align="center" valign="top">Flexural strength after 24 hours at 23 ° C / 50% rel. Humidity [kJ / m²]</entry><entry align="center" valign="top">Flexural strength in% of sample 1 (AMEO)</entry></row></thead><tbody><row><entry align="center">1</entry><entry align="center">131.3</entry><entry align="center">100.0</entry></row><row><entry align="center">2</entry><entry align="center">127.6</entry><entry align="center">97.2</entry></row><row><entry align="center">4</entry><entry align="center">124.9</entry><entry align="center">95.1</entry></row><row><entry align="center">5</entry><entry align="center">132.5</entry><entry align="center">100.9</entry></row></tbody></tgroup></table></tables>

example 5

Determination of impact resistance according to DIN EN ISO 179 (Charpy) and DIN EN ISO 180 (Izod)

<tables id="tabl0004" num="0004"><table frame="all"><tgroup cols="3"><colspec colnum="1" colname="col1" colwidth="20mm" /><colspec colnum="2" colname="col2" colwidth="61mm" /><colspec colnum="3" colname="col3" colwidth="40mm" /><thead><row><entry align="center" valign="top" /><entry namest="col2" nameend="col3" align="center" valign="top">Impact resistance according to DIN EN ISO 179</entry></row><row><entry align="center" valign="top">Approach no.</entry><entry align="center" valign="top">After 24 h at 23 ° C / 50% rel. Humidity [kJ / m²]</entry><entry align="center" valign="top">In% of Sample 1 (AMEO)</entry></row></thead><tbody><row><entry align="center">1</entry><entry align="center">38,60</entry><entry align="center">100.0</entry></row><row><entry align="center">2</entry><entry align="center">32,21</entry><entry align="center">83.4</entry></row><row><entry align="center">4</entry><entry align="center">42,16</entry><entry align="center">109.2</entry></row><row><entry align="center">5</entry><entry align="center">37,13</entry><entry align="center">96.2</entry></row></tbody></tgroup><tgroup cols="3"><colspec colnum="1" colname="col1" colwidth="20mm" /><colspec colnum="2" colname="col2" colwidth="61mm" /><colspec colnum="3" colname="col3" colwidth="40mm" /><thead><row><entry align="center" valign="top" /><entry namest="col2" nameend="col3" align="center" valign="top">Impact resistance according to DIN EN ISO 180</entry></row><row><entry align="center" valign="top">Approach no.</entry><entry align="center" valign="top">After 24 h at 23 ° C / 50% rel. Humidity [kJ / m²]</entry><entry align="center" valign="top">In% of Sample 1 (AMEO)</entry></row></thead><tbody><row><entry align="center">1</entry><entry align="center">20,83</entry><entry align="center">100.0</entry></row><row><entry align="center">2</entry><entry align="center">19,50</entry><entry align="center">93.6</entry></row><row><entry align="center">4</entry><entry align="center">27.69</entry><entry align="center">132.9</entry></row><row><entry align="center">5</entry><entry align="center">32,90</entry><entry align="center">157.9</entry></row></tbody></tgroup></table></tables>

example 6

Determination of Vicat temperature resistance according to DIN EN ISO 306

<tables id="tabl0005" num="0005"><table frame="all"><tgroup cols="2"><colspec colnum="1" colname="col1" colwidth="20mm" /><colspec colnum="2" colname="col2" colwidth="50mm" /><thead><row><entry align="center" valign="top">Approach no.</entry><entry align="center" valign="top">Vicat softening temperature</entry></row></thead><tbody><row><entry align="center">1</entry><entry align="center">261.7</entry></row><row><entry align="center">2</entry><entry align="center">261.3</entry></row><row><entry align="center">4</entry><entry align="center">259.2</entry></row><row><entry align="center">5</entry><entry align="center">260.7</entry></row></tbody></tgroup></table></tables>

example 7

Determination of the volume flow index MVR according to ISO 1133 at 275 ° C and 5 kg load

<tables id="tabl0006" num="0006"><table frame="all"><tgroup cols="2"><colspec colnum="1" colname="col1" colwidth="20mm" /><colspec colnum="2" colname="col2" colwidth="31mm" /><thead><row><entry align="center" valign="top">Approach no.</entry><entry align="center">MVR in ccm / 10 min</entry></row></thead><tbody><row><entry align="center">1</entry><entry align="center">49.17</entry></row><row><entry align="center">2</entry><entry align="center">49,43</entry></row><row><entry align="center">4</entry><entry align="center">45,62</entry></row><row><entry align="center">5</entry><entry align="center">51,41</entry></row></tbody></tgroup></table></tables>

Summary of test results:

The examples show that inventive agents. See the lugs 4 and 5, compared to the standard surface modification with DYNASYLAN®^® AMEO or AMEO-T, see. The batches 1 and 2, an improvement in the properties and processability of the thus silanized kaolin in polyamide effect.

Example 5 shows the significant increase in the impact strength of the polyamide compounds, - especially the increase in the impact strength according to DIN EN ISO 180 (Izod impact strength). This impact modifier is an improvement in the performance characteristics of the finished products produced using the polyamide compounds of the invention.

From Example 7 it can be seen that the processing of the polyamide compounds according to the invention due to the higher flowability is facilitated.

Examples 3 and 4 also show that the surface-modified fillers according to the invention affect the tensile and flexural strength of the polyamide compounds as good as not.

The thermal properties, here represented by the softening temperature are not significantly affected in Example 6 by the inventive surface modification of the filler.