NL8600970A - METHOD FOR MANUFACTURING MOLDED PARTS FROM MODIFIED THERMOPLASTIC POLYAMIDES AND MOLDED ARTICLES THEREFROM. - Google Patents

Description

VO 8082

Titles Method of manufacturing moldings from modified thermoplastic polyamides and moldings obtained therefrom.

Polyamides are known as very versatile construction materials. Several polyamide main groups are currently known, each of which has certain interesting properties. This concerns polyamide 6 and 6.6 as standard construction materials; products with a relatively high softening point but also with a relatively high equilibrium water content; polyamide 11 and 12 with a lower melting point, but with clearly reduced equilibrium water content and therefore better dimensional stability.

Polyamides 6.9, 6.10, 6.12 and 6.13 occupy a middle position.

Later the pure amorphous polyamides, e.g. from trimethyl hexanediamine and terephthalic acid, then polyamides which, although having a crystalline melting point, also have a high glass transition point, such as e.g. the polyamide from metaxylylenediamine and adipic acid. In addition, many types of blending and copolyamides exist today, for the preparation of which straight monomers are preferably used and which have found multiple uses, e.g. as textile adhesives or mounting adhesives. Despite the multitude of applications that have been made possible by these numerous polyamide types, applications are still emerging that the present polyamide mixtures also do not meet. Thus, e.g. the stiffness and tensile strength of a polyamide modified by a foreign polymer impact-resistant; when heated above the melting point, e.g. the cable insulation or a cover made of pure linear polyamide is quickly removed: with longer frictional contact with a rough surface, a polyamide utensil 25 undergoes considerable wear.

German Offenlegungsschrift 3,339,981 now generally describes a process which relates to the chemical coupling of a silane to the polyamide chain, the silane structure subsequently leading to the formation of a crosslinking site of the polymer chain by the action of moisture. Depending on the structure of the polyamide as well as the type and the concentration of the silane, a chain extension is preferably found, respectively, v λ a v.

- * · X -V U J V

ί <ί - 2 - formation of cross-linking sites takes place.

It has thus been successful to improve properties such as toughness, heat resistance and wear resistance considerably.

Moldings with markedly improved properties are obtained by this general method, but no method is available for the rational, safe and large-scale preparation thereof.

According to the examples known from this publication, the polyamide granulate is first coated with a silane layer, the whole losing its dosability. This is again restored by adding a considerable amount of polyamide powder, which forms a coating layer on the granulate surface by adhesion. Grinding the tough polyamide into the necessary powder is laborious and succeeds at low temperatures, e.g. in the presence of liquid nitrogen. The dust must then be removed and dried completely. Since polyamide in powder form has a very large surface area, moisture is absorbed even with a short contact time with the normal ambient atmosphere, so that there is finally a risk that the silane is already cross-linked in the melting machine.

Also foreign powders, such as e.g. powdery process aids, which in principle can be used for regrowability, present essentially the same problems, i.e. the danger of entraining of moisture and interfering materials in the reactive mixture. Also, the amount of the silane which adheres to the granulate surface and can be distributed homogeneously is limited. In total, this two-step pre-treatment method is cumbersome, uneconomical and there is always the risk of moisture acting.

Although the process by which the silane is injected into the polyamide melt provides good results, insofar as technical equipment is present and in extrusion applications, it is not suitable for injection molding processing. Moreover, during extrusion processing it is disadvantageous that cumbersome technical devices are necessary. For example, the silane must be injected very constantly against a high counter-pressure of the melt. In addition, high demands are made on the mixer between the injection point and the tool to compensate for as many concentration fluctuations as possible and the silane to be sufficient - C Λ. "" 7 · Λ - · «-" ^; ·. 1 ί v · "-w * .j - s - 3.- * -ί to be homogeneously distributed. It was thus found that a simple method of silane addition generally suitable for injection molding and extrusion would represent a substantial technical advance for the successful implementation of the process. mean.

It has now been found that the process of the polyamide modification by silanes can be solved in an almost ideal manner by using suitable master mixtures ("master batches"). The invention thus relates to a process for the production of moldings from thermoplastic polyamides, which have improved mechanical properties and an increased heat-mold stability compared to the polyamide starting material, characterized in that a main mixture is added to the dry polyamide before processing. containing at least 5% by weight of a silane of formula 1 of the formula sheet, wherein: 15 n 0, 1 or 2, Z * an inert organic residue, Y = a divalent organic residue linked to the silicon, which contains a functional group which reacts with amino groups and / or the carboxyl groups and / or the amide groups of the polyamide chain to form a chemical bond and A = a residue which can be hydrolysable when moisture enters it, wherein multiple residues may also be mutually connected, melts with the mixture of polyamide and main mixture, intensively homogenises (mixes) the melt and uses converts the conventional methods of thermoplastic processing into moldings and brings this <5dr use into contact with the natural ambient humidity or conditions it briefly in water.

High demands are placed on the main mixture carrier for a simple, practical implementation of the method according to the invention.

For example, should this silane be able to absorb well, exhibit sufficient compatibility with the polyamide in the concentrations used and be divisible into the polyamide when incorporated without substantial adverse influence on the polyamide properties? the loaded silane must not destabilize with respect to hydrolysis sensitivity, as well as generally water-repellent properties

, i V

£ <s - 4 - so that there is no danger of attracting moisture.

When silane is referred to hereinafter, this refers to polyamide-reactive silanes according to this invention, in particular, however, the silane types: epoxy silane of formula 2. of the formula sheet, as well as isocyanate silane of formula 3 of the formula sheet.

Extensive tests have shown that there are several methods for preparing a suitable main mixture.

Method 1:

The melt of a polyolefin is directly charged with silane and the silane-containing melt is extruded as a strand, ground to granulate and finally carefully dried.

Method 2:

If a silane-swellable support material is available, then. this is e.g. in the form of crumbs, granules or coarse powder directly contacted with an amount of silane which is immediately taken up. The carrier must of course remain spreadable, i.e. there must be no adhesion.

Method 3:

A thermoplastic, which is present as an open-pore sponge, but which must not have swellability with respect to silane, is mixed with a maximum of the same amount of silane, so that the filling of the pores is guaranteed, but the spreading ability of the product is not significantly affected .

Method 1 is generally used when the thermo-25 plast does not spontaneously absorb silane. For this method, e.g. suitably the so-called LLDPE (linear low-density polyethylene), ethylene-propylene copolymer (EP-rubber), elastomers known as EPDM, copolyole-fins with a low glass transition point, which in a small amount e.g. may be grafted with maleic anhydride or mixtures of these polymers. Furthermore, good spreadable products are suitable, e.g. with a so-called melt index according to ISOR 292 of 5 and more.

For the practical implementation of the method, the products are sold e.g. in a double screw kneader, such as in a so-called twin-kneader, e.g. a ZK-30 from Werner and Pfleiderer, Stuttgart, melted. The silane is continuously introduced into the polymer melt in a predetermined amount by weight through a gas removal pipe.

5 The maximum silane absorption suitability of the melt must be evidenced by a preview. Electronically controlled, e.g. 6- or 8-articulated peristaltic pumps are suitable, in which the silane is pressurelessly applied to the surface of the polymer melt, then kneaded and dissolved.

The obtained extrusion strand can be cooled in a water bath so that it can be continuously crushed into a granulate. However, the contact time with water must be limited to such an extent that only the necessary cooling function is obtained and the water evaporates again between the moment the strand leaves the cooling drum and the cutting device.

The transport from the extruder to the granulator can also be done via a cooling belt, e.g. a water-coiled steel strip.

Method 2 is suitable insofar as the thermoplastic spontaneously absorbs silane. The method is extremely simple and is suitable for practical application of the method. It represents a significant technical simplification that themoplasts have been found which spontaneously and in a short time absorb significant amounts of silane without sticking; which in the silane-loaded form are easy to process in the polyamide, thereby releasing the silane so that it can react with the polyamide, so that the processability and the mechanical behavior of the polyamide are hardly affected.

Block polymers from a hard block and an elastomer segment are suitable as polymers that can be used according to method 2. The hard block exists e.g. from polystyrene and the elastomeric segment e.g. from polybutadiene, polyisoprene or a saturated block, i.e. without double bonds, e.g. from ethylene-butene or ethylene-propylene copolymers. The elastomeric block can also represent a mixture of different block structures. The behavior of the hard block to the elastomeric block can be varied within wide limits. Preferably, however, triblock polymers with an elastomer block fraction of at least 50%, in particular 60-75%, are used, since the elastomer block is

^. * XJ

- 6 - r * the uptake of the silane is responsible. A styrene-ethylene-butene block polymer with 70% by weight of ethylene-butene fraction absorbs more than its own weight of silane without adhesion. These block polymers can be in the form of. crumbs, granulates, granules or powders are used.

5 Granules with an average diameter of about 0.1-0.2 mm are well suited. These do not form dust, absorb the silane in a short time and adhere well to the surface of the polyamide granulate, with homogeneous mixing between such a main mixture and the polyamide already being present after a mixing time of a few minutes. Generally, this type of main mix carrier is loaded with more than e.g. 20 wt% silane.

Main mixtures containing about 50% by weight of silane are particularly suitable. When the polyamide is processed together with such a main mixture, the finished article of use contains only very little foreign polymer and the basic properties of the polyamide are largely retained. The general approach according to method 2 also appears to be very simple and is no longer specifically described later in the examples.

Stirring the main mixture particles, e.g. granules of poly (styrene-ethylene-buty-styrene) triblock polymer, silane is added and the mixture is briefly homogenized by shaking. After standing briefly, e.g. For 10 minutes, the silane is taken up. A predetermined amount of main mixture, e.g. 2-3 wt.% Is now added to the dry PA granulate and mixed so long that the main mixture is distributed homogeneously over the granulate. This is already the case after a few minutes. The granules 25 thereby adhere well to the surface of the granulate. The mixture can now be stored in the interim or processed immediately.

The only condition is the exclusion of moisture.

Method 3 is based on the targeted use of open-pore "polymer sponges" capable of spontaneously absorbing liquids by capillary forces. Such polymer systems are e.g. described in Kunststoffe Ti., band 3, pp. 183-134 and German et al., 27 37 745.

Polymers with such microporous structures are e.g. made of various types of polyethylene, of polypropylene, of polycarbonate, but also of polyamide 11, 12, 6 and 6.6. The pore volume is 50-85% and the diameter of the pores is in the range 0.1 - 10 * Γ- ».>. - ^

v J: i; YOU

* 5 - 7 micrometres. The 2nd microporous polymers can absorb up to 3 times their own weight of silane. As a result, the relative influence of any residual moisture is also relatively small.

Granules with medium and low-viscous microporous nylon-11 and -12 are particularly suitable as main mixture carriers for the processing of polyamides. These types have the least moisture absorption under the straight polyamides, but melt well during processing and dissolve well in all polyamides at the usual application concentration, so that in the final product a homogeneous polyamide phase is present in practically all cases.

Method 3 as a whole represents a particularly favorable application form of the method. The only drawback is a relatively cumbersome manufacturing process of the microporous polymer systems. Macroporous polypropylene and polyamide 12 spontaneously absorb about three times their own weight of silane. The principal application of this main mixture type complies with the method according to method 2. For a processing in accordance with the method of the invention, all thermoplastic processable polyamides can be used. In particular, it has proven advantageous to use polyamides with clearly defined and known reactive groups. The amino groups are particularly preferred.

If one strives for a largely linear chain extension with as few so-called cross-linking sites as possible, polymer chains with the groups PA-NH.R at the chain end are especially preferred. These types of chain terminations can only react with one silane, which means that cross-linking sites at the end of 2 polyamide chains are preferably formed during the conditioning. If it is intended to form 3-dimensional networks, polymer chains with end groups and, depending on the desired degree of cross-linking, 30 (-NH) groups are also used in the chain. The concentration of the -N ^ and (NH) groups, expressed as e.g. micro eq / g (-NH - ^ - NH ^) in the polyamide melt is a direct measure of the optional crosslink density when an amine reactive silane is used. When the polyamide chains are structured in such a way that the amine functionalities occur only at the chain end in the form of -NH 2 -groups. If a short chain polyamide can thus be used to achieve a specifically higher crosslinking density than with medium and high viscous polyamides.

The cross-linking is essentially based on the fact that almost 2 epoxide or isocyanate groups can be attached to the -NH2 group 5, whereby the structure according to formula 8 of the formula sheet is formed first in the case of silane according to formula 1 of the formula sheet. Formula 9 of the formula sheet shows a cross-linking region of polyamide chains, with different types of chain cross-links and branches 10 being schematically represented.

R means between member (-0 (CH2) 3 “).

The following applies to this formula: (A) are chain branches, which are created by coupling 2 silane molecules to a -NH 2 group.

IS (B) shows the rarer case of chain branching to silicon.

(C) shows the case where only one silane was available for the reaction with the -NH2 group.

(D) is the structure that arises when a secondary amine group is present at the chain end 20. The chain branching according to (A) is clearly preferable compared to (B).

Since the type and concentration of the amino groups in the polyamide has been given by the polymerization recipe (type and concentration of the chain regulator) and can also be easily checked analytically, suitable silane concentrations can easily be calculated in the case of an amine-reactive silane. . Therefore, the chemical modification of polyamides can be highly targeted and adapted to practical needs.

For example, the maximum reactive silane amount for a 30-NH 2 chain-terminated polyamide with e.g. 40 micro-eq / g (NH2) and the use of silane of formula I (Mg = 236.4) 40.2.0.2364.1 = 18.9 g of silane per kg of polyamide.

The method is not only limited to pure polyamide, but is also suitable in many cases for polyamide mixtures or alloys, at least one component being polyamide and the further components - λ «λ '7 τ' '^. ; · 4 * - 9 - are inert to silane, but may also have silane-reactive sites.

Examples for alloy components are; the known polyethylene types, polyethylene copolymers, e.g. ethylene copolymers from ethylene and with butyl acrylate 5 and vinyl acetate, but also relatively inoculated (e.g. with a maleic anhydride). Silane reactive alloy components include thermoplastic polyesters, ethylene-acrylic acid copolymers, hydroxy-terminated polyethers or ethylene-vinyl alcohol copolymers. However, so-called PEX (chemically cross-linkable polyethylene) 10 can also be processed together with polyamide and main mixture. Polyamide and polyethylene are crosslinked as separate phases during the action of moisture. In addition, chemical bonding also occurs at the interface by reacting the silane on the polyamide surface with the silane on the polyethylene surface to form -Si-O-Si bridges. The poly-15 amide matrix thereby facilitates the transport of moisture to the dispersed PE phase.

Depending on the type of processing of the starting materials, different requirements are imposed on the machines and different molding compositions, i.e. finished products, are accessible. Since in general the granulation and main mixture must be premixed for processing in the main mixture method, this is suitable for all thermoplastic processing methods of polyamide and thermoplastic processable polyamide mixtures. It is a condition, however, that in the melting state of the molding process, an intensive mixing of the melt takes place and the silane can spread homogeneously.

The delivery device, e.g. the inlet funnel, must be formed in all processing equipment in such a way that the polyamide main mixture mixture present therein can no longer absorb moisture. This can be done with simple means, e.g. with a tight-fitting cover combined with a drying gas purge. A slight heating of the filling mass also means an active protective measure. The injection molding process thus requires screw injection molding machines with an active 3-zone worm. Under certain conditions, a gas-removing plasticizing unit can be used, for which piston injection molding machines are not suitable.

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When melting, the mixture of polyamide and main mixture must be intensively homogenized. As usual, no melting of the granulate main mixture is effected during the injection, post-cooling and cooling time. In a silane injection, the injection treatment should be absolutely synchronous with the granulate incorporation step, so that no fluctuations in the finished part, e.g. in the degree of cross-linking. A corresponding troubleshooting would essentially be technically expensive. However, such problems do not arise in the main blend method of the present invention. The 10 problems with blow molding to hollow bodies are basically of the same order. In the extrusion and in the extrusion blow molding method, the granulate is melted continuously. Suitable for this are both the main mixture process and the way of directly injecting silane into the polymer melt. In both cases an effective mixing device is necessary. For direct injection, however, extensive technical devices and control devices are required, which are completely omitted from the main mixture concept. Thus, for universal application, the main mixture process is also advantageous in extrusion applications.

The molecular structure of the finished polyamide part is substantially influenced by the method according to the invention. If one starts from a linear chain structure, one attains fully cross-linked structures via higher molecular, branched chains. The modification of the properties in terms of mechanical and thermal load capacity and therefore the application possibilities are closely linked.

Parts of the polyamide modified according to the invention are also used where better mechanical values, higher hardness and better wear resistance, as well as dimensional stability above the polyamide melting point are required. Interesting applications are also obtained by the appearance of the so-called memory effect, i.e. sprayed and cross-linked parts can take on a different shape after heating above their melting point and the new shape can be frozen below the melting point on cooling. After reheating above the melting point, the material returns to its original shape. Therefore, e.g. well-sealing pipes or cable connectors are manufactured, which are crimped onto the pipe / cable connectors and thus provide an effective seal.

'λ 1' Λ. ; ^ .- 11 - * *

The following examples serve to further illustrate the invention. First, under 1, 2 and 3, the different methods for preparing the main mixture are described. The accompanying tables A, Ben C concern compositions of the corresponding main mixtures.

The polymers used for carrying out the process of the invention are listed in Table D. The preparation of the test bodies necessary for checking the process is then outlined. The test results are summarized in Tables E-N.

1. Preparation of main mixture via silane dosing in a thermoplastic melt.

10 A double screw kneader, ZSK-30, from Wemer &

Pfleiderer, D-Stuttgart, is loaded with the main mixture carrier granulate via a shaking chute. In the area where a homogeneous melt is present, silane is directed to the melt in a continuous liquid jet via an open degassing tap and absorbed by the moving melt. The main mixture melt is discharged as a strand and briefly passed through a water bath for cooling. The strand, which is still warm and no longer containing surface water, is then granulated and stored in a tightly closed container.

2. Preparation of main mixture by direct incorporation of silane by the thermoplastic.

Immediate absorption means that the thermoplastic spontaneously absorbs the latter on contact with liquid silane. In this type of main mix preparation, the silane is first distributed as finely as possible on the surface of the support. This can e.g. take place by spraying on silane and then mixing. The first moist, sticky mixture generally becomes good again after the suction has ended. For example, based on the weight of the polymer, a finely powdered core jacket polymer of the MBS type with about 58 wt% polybutadiene 50% and with about 46 wt% polybutadiene 33%, takes a finely powdered core jacket polymer of the ABS type with 42% by weight of polybutadiene 33%, as well as a fine powdered kernel-shell polymer of the pure acrylate type 50% silane each of type I.

P V

- 12 - 3. Preparation of the main mixture via silane incorporation of open-pore polymer sponge.

For example, to prepare the corresponding main mixture, proceed as follows: 5 The silane is sprayed homogeneously under continuous mixing into the granular, easily spreadable, porous polymer. The silane is absorbed even after a short contact time and the polymerisate can be spread again. The polymer systems used for the tests have a free pore volume of 50-85% at a pore diameter of 0.1-10 micrometers and they are generally capable of 50-75 wt% silane (based on the sum) of the products).

To control the method of the invention, master blends as described in Tables A, B and C were mixed with various polyamides with the exclusion of moisture and tested as test bodies or tubes. The polyamides used are compiled in the following Table D.

Polyamide 12 was prepared according to the prior art while maintaining a pressure phase with the aim of opening the lactam ring. The preparation of polyamide 6 is also part of the prior art. Polyamide 6/1 was prepared in a so-called closed VK tube via chain stabilization with water, polyamide 6/2 in a 50 1 test autoclave with addition of diaminohexane as chain regulator. The transparent polyamide, Grilamid TR 55, was prepared according to German Patent 2642244, Example 10. The preparation of polyamide MXD 6 is described in European application 71QQQ, but it can, however, also take place by mixing all monomers in one step while maintaining a pressure phase.

The further process steps then correspond to the known step of the art, as also for the preparation of e.g. polyamide 30 6.9 or 6.12 are common.

- 13 - TABLE ft.

Preparation of main mixture by direct silane dosing in a thermoplast melt. All copolymers mixed with silane in the amounts described do not exhibit a silane deposit and are easy to spread.

Assembly lay-. Recovery parameters Comments w * '1 —... · ι.ι. »Ιι ... yy,, .p - - betr. carrier— S Carrier material Silane ~ 50 «·» -Turn- 24at.- Fast- Mteriaai ° * - —- moment pressure point

ji% tp »Ha Bar. "C

1 XMW, «.X. - 25 2 5 ISO 20 11 ISO 1 copolymer from 2 * * 2 ® iso 27.S 10 153> ethylene> octene 2 2 10 ISO 25 6 ISO j *> *, M.X. 6 2 7.5 150 33.5. IS 149 5 * 2 10 150 30.0 14 169} t * 6 “_" __ 2- i2> 5 I50 28.5 14 170 _? Ϊί * r MX * 6 2 3 ISO 32 IS 170 Copolymer off • '2 3 is «» ui »TSSS & L '

18% BA

9 Day. from 50% LLDPg 2 10 150 38 10 176 EP Copolymer.

(as trial 1) + inoculated with ca.

50% Etbeeasropene 0.3% Maleic Acid *.

10 Copolyme «2 IS ISO 40.5 10 187 anhydride 11 Leg. 50% UDEB 2 IS 150 45.5 12 208 EP-Copolymer (as test 4) + is inoculated with ca. pO * ethylene propylene 0.3% MaleXneic acid

Copolymer anhydride - M.I. - melt index, determined at 190 ° C and at a load of 2.16 kg according to ISO R-292 'T £ - 14 - TABEE 3:

Preparation of main mixture by direct silane uptake by the carrier.

______...___ g _._________ ____________ - »______________, w” Composition Time lapse At the latest «_ until incorporation of main mixture> ö Carrier material Silane silane ·, ..................... ....... .......... i ....... (hours) 'a Type Per *. Type *% '12 BVA-Terpolyaeer, ca 1025 S' 2. 10 ea. 2.5 strcoible 13 * * G "2 20 c *. 4.0 · "- 14 - · * G 3 10 ea. 3.0 · - · (Om Pont) 13 * _ * _ * G 3 20 approx. 5.0 -_ 16 _ SBS-Triblok polymer, S-Kr 2 20 ea. 1.5» * ·· fraction 28% / 17 V Kr / 4 15 ea. 0.5 "* 18 tsasap KR-3__is ea. 0.5. "* ig S / EB / S-Trülokpodymeer, S-Ka 2" 50 approx. 2 Min. »Fraction 28% 20 S / EB / S-Triblok polymer, S-XO 2 50 approx. 10 Min. · «Fraction 33% * 21 S / SB / S Triblock polymer» S- * ®. 2 50 ea. 10 Min. »Fraction 29% 22 S / EB / S Triblock polymer, S-XO '3 50 10 Min. »Fraction 29% 23" XO · 4 50 10 Min.

24 ”« 5 5 S0 · 10 Min.

25 Xd 6 50 10 Μ1Λ.

26 "XO 7 50 10 Min." / 27 · Ko 2 60 10 Mln. Tendency to stick 28 _ * (SHSEL) XQ 2__65 10 Min. fan ^ lkaar ^ "- in the form of the carrier material: G = granulate / KR = crumbs, 0 approx. 2 - 10 mm / KO * crumbly soft granules, 95% by weight, 0 0.2-3 mm - spreadable * = after silane incorporation, pulverizing with, for example, 1% microtalk is advantageous - S = styrene, EB = ethylene butene, EVA = ethylene vinyl acetate 0.25%. * S% * -,: '_ *' j - 15 - * 3 TABLE C;

Preparation of main mixture by silane charge of a polymeric open-pore support.

Composition Time- Appearance Φ 1 "walk to. Main mix §. Carrier material 'silane' intake sel. Silane £ __type% __-___ c t 29 mikroporeua polypropylene- 2 50 φ ^ φ

Powder § * * § $ • H J4 O Λ 30 ii ii 2 75 ® O * Ή

U +> H C

31 '* »4 50 ft JZ 0 <d

^ 3U W ü 0 H

. ft * -H "O O"

0 t r-4 M

O id C.

U · <(»(5 nj 32" "5 50% § £ Ό Λ - · id * O’

id «D Λ t C

32 n i «p and CO * W Ή · <!

° 3υ Λ 0 O -U

M oer ^ C n o> o

34 i »i» 2 and d) <U -U —I IU

5 ^ y o n 5, ca m a £ c

O.

35 n "3 75 e § clumps' H $ as with 36 microporous, medium 2 viscous 2 50 § * o 29-34 PA 12 powder g .§ <uc <w 37" ”3 50 o1 -H clumps § c as with ( d O 2Q-34 38 "" 2 60 Cj c ca -η

In Tables A-C, silane types 2-7 mean formulas 2-7 of the formula sheet.

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? ς - 16 - TABLE. Ώΐ

Composition of the polymerisates used.

'-..........-............. ^ __ rX-Kr. PA-KAKMTERTERING1 OPKEKklNGHf PA-Typ, nrel. M c Type of amino groups. Λ (1) (2) (3) <4>

Pe 1 SA 12 1.57 120 16 “NHj Injection molded type, very fishy. cegs- * I.

So 2 PA 12 1.69 90 12 -NHj Injection molded type, medium viscous

* Po 3 * PA 12 1.67 104 -NBA

Po 4 PA 12 1.50 390 -NB— Injection molding type # .very.visceus PO 5 PA 12 1.93 68 14 -NHj Injection molding and extruding type ^

Po 6 PA 12 1.95 256 11 -NH-

Po 7 PA 12 1.91 166 .16 -NH- PO 8 PA 12 2.07 109 21 -NB-

Po 9 PA 12 2.00 100 35 -NBB * -NB- ""

Po 10 PA 12 1.94 63 31 -NB »

PA-NS. PA CHARACTERIZATION - - COMMENTS

PA-Type nrel. N c nseha.

(1) (21 (3> (4) Pa-s (S)

Po 11 PA 6 1.61 120 20 30 270 highly viscous PAs Injection molding compound (PA 6/2)

Po 12 PA 6 1.84 53 57 200 270 saturated viscous PA 6 injection molding material (PA 6/1)

Po 13 PA 6 1.90 -50 50 300 270 moderately viscous PA-6 injection molding compound (PA 6/1)

Po 14 7 »55 1-55 70 50 1700 270 transparent injection molded polyamide with glass transition point of

15S * C

Po 15 NXSA * 6 1.60 89 62 100 270 Polyamide primer from the amine.

QCHJNB2 and adipic acid CH2MH2 - - 17 -

In table D mean? (1) = the relative solution viscosity, measured as 0.5% solution of the polymerisate in m-cresol at 20 ° C according to DIN 51'562.

(2) = the analytically determined concentration of amine groups, expressed as microequivalent total amino groups per gram of polymer. This determination can e.g. potentiometrically with perchloric acid in an m-cresol-isopropanol mixture (see Bulletin No. A68d from Metrohm, Herisau CH).

(3) = the analytically determined concentration of carboxyl groups, expressed as microequivalent carboxyl groups per gram of polymer. The determination can e.g. in benzyl alcohol at 100 ° C with a benzyl alcoholic KOH solution under visual determination of the phenolphthalein reversal point (4) = the type of the amine-functional groups present in the polymer. This is determined by polymerization additives and the mode of chain length control.

In particular, -NH1-diaminohexane, -NH: diethylene triamine or dihexamethylene triamine were chosen, each combined with azelaic acid, -NHR: 4-amino-2,2,6,6-tetramethylpiperidine combined with azelaic acid.

All tables mean: PA = polyamide, 25 Po = polymerisate, MB = main mixture (Masterbatch) 3. Production and evaluation of test pieces.

To test the process, test pieces, generally so-called standardized tensile rods (KDB) according to DIN 533453 were prepared from the polymerisates Pol-PolS- in combination with selected main mixtures and these were subject to their notched impact strength as well as their dimensional stability. the normal polyamide melting point was examined. For a further assessment of the process, a knife extruder of the f * '' Λ

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- 18 - y v Schwabenthan, Berlin, type SM30U manufactured at mass temperatures of 1S0-220 ° C tubes of the dimensions listed in the tables and judged in particular for their dimensional stability in the molten state. The results are presented with a brief comment in Tables E-N 5. The standardized tensile rods (KDB) with a size of 60 x 6 x 4 mm were manufactured on an injection molding machine from the company Netstal, CH-Niederurnen of the type Neomat Nl10-565. The machine is equipped with a melt-active homogenizing melt extruder. The melting parameters, such as the temperature profile of the melting worm, the speed, etc., were always adapted as much as possible to the polyamide used.

To test the molding stability above the normal melting point of the polyamide, the KDB on a metal sheet were exposed to the corresponding temperature load for the period of time mentioned in the tables under the test, e.g. in Table E for 15 minutes at a temperature of 230 ° C. In the subsequent column "assessment" means -: no dimensional stability, material liquefies into a melting pool £: basic shape of the test body is retained; corners and 20 sides are rounded +: the. shape of the test body is maintained; corners and edges are rounded to a very small extent at most.

The following intermediate stages are also important: - +: more distorted KDB, tendency to flow, 25 ++ -: with well-preserved basic shape, the corners and edges are slightly rounded.

Table E shows tests based on low and medium viscous polyamide 12 types. The main mixtures used each contained type 2 silane and were added such that the mixture of Run 40, 41, 43 and 44 each contained 1.2 wt% silane and from Run 42, 1.0 wt% silane. The molding stability is improved in all these cases compared to Test 39 (no silane addition). The notched impact strength is in all cases clearly above the value for the unmodified reference material 39.

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Highly viscous polyamide 12 types were used for the tests according to Table F, in which polymerisate 6 and 7 have -NH-functional groups in the polymer chain in addition to -N 2 -end groups, Nos. 45 and 43 are comparative examples corresponding to polymerizate without main mixture addition.

In all tests the molten stability is clearly improved. The notch impact strength also increases very markedly. An asterisk (*) means that only part of the test pieces is still broken.

For the tests according to Table G, a low-viscosity starting material was again used and combined with the main mixtures types 10 and 11. Comparative tests are No. 58 corresponding to the pure starting material, as well as No. 65.

Two asterisks (**) here means that to the base material the 15 base components of main mixture 10, but without silane loading, were added. The results of the shape stability tests, as well as the measured impact strengths, again clearly show the influence of the chain crosslinking reactions.

In the tests according to Table H, various poly-20 merisates of polyamide 12 base material were each processed with main mixture 10. All materials except Po3 are highly viscous. At the main mixture concentration used, only test 67 gives insufficient shape stability and little increase in notch impact toughness. All other tests show very high notched impact strength values in the evaluation ± in shape stability. O.B. means no breakage, i.e. none of the moldings examined are broken. Tests 72-77 show that from 7% by weight of the addition of main mixture 9, there is no more relevant change in shape stability and notch impact strength.

Tests 76 and 77 show that different polyamide 12-30 types can also be processed as granulate mixtures with success according to the method of the invention. The tests of Table I are again based on the low-viscous polymerisate 1. Main mixtures were added such that the moldings for tests 78-83 each were ca.

1 wt.% And for experiments 84-87 each contain 1.5 wt.% Silane type II.

35 There appears to be a clear correlation between the shape stability. and the amount of added silane. Also notched impact strength 3 -> '., -1 Λ

v ^.! - V

Becomes considerably higher, but fluctuates simultaneously, which can be traced back to side effects of the main mixture base material.

In the tests according to Table J, the polymerisates 9 and 10 are processed with minor additions of the main mix 19 and 20. Tests 88, 89 and 94 are again comparison variants. Runs 88 and 94 correspond to the pure polymerisate. In Run 89, 2% of the main blend base stock, loaded without silane, is added. The evaluation again demonstrates increased dimensional stability when heated, as well as improvements in notch impact strength.

Table K includes tests with Po 14 (= transparent polyamide) as well as polyamide 6 and polyamide MXD-6. From a defined main mixture and thus silane concentration, the shape stability in the heat is again improved. The impact strength of these products, which are in themselves rigid and not very impact-resistant, is also increased by the chain crosslinking reactions. Table L shows tests in which a granulate mixture of a high-r, as well as a low-viscous polyamide 12 type with a so-called HDPEX, type 71.21-10, from the company Asea Kabel, Stockholm, directly with the addition of a main mixture according to the the invention into test pieces. The notched impact strength after conditioning in water and drying 20 (column 1) as well as after conditioning in water and subsequent storage in the air for one day was determined (column 2).

The variants marked with * are comparison tests. The polyethylene is present in finely divided form in the test pieces. While sharp bending results immediately after spraying, delamination effects occur, but after conditioning in water with subsequent drying, these are only weakly detectable. It may therefore be assumed that a chemical bond has also been formed at the phase interfaces in the form of o -Si {'' Si bridges. The notch impact strength has clearly increased again compared to the silane-free products.

Table M summarizes tests for the manufacture of pipes measuring 8 x 1 mm. For this purpose, the -NH 2 -end polymerisate 5 and the -NH functionality-containing polymerisate 8 were used. The tubes were manufactured on the Schwabenthan knife extruder. In the column tubes: 35 0 means the outer diameter of the tube and d its wall thickness.

· \ • 'Λ ^ ^: ¾ •, - · u - 21 - in the column t manufacture 1 means the speed of the extruder worm, 2 the first and 3 the last (on the nozzle side) 5 setting temperature of the cylinder heating zones , as well as 4 the discharge speed of the tube.

An open, unheated one-stage funnel was used for this test so that the polyamide could absorb some moisture before processing. In addition, part of the Si-O-Si bridging already took place in the melt during the manufacture of the tube.

During the pipe extrusion, smooth pipes were formed from the polymerate 5 (pure N 2 end groups), which were absolutely dimensionally stable when heated above the polyamide melting point. Tubes with a rough surface were formed from the polymerisate 8, which, while having a corresponding heating 15, did not generate a melting puddle, but nevertheless experienced a marked shrinkage (L-shrinkage). This is closely related to the so-called memory effect. The polyamide melt, which already has many cross-linking sites, is stretched between the spray head and the tool, and this sprayed condition is finally frozen during cooling. In the re-melting the unstretched form is then again assumed. This effect is almost completely absent in polyamide with NH 2 end groups, where chain extension reactions occur earlier with silane.

Runs 129 and 130 concern the manufacture of tubes from a polymerisate similar to Po 5, but with a slightly shorter chain length 25 (93 mAe / kg yyHg) * With addition of a main mixture base of silane II

and silane III, it is possible to manufacture pipes with good dimensional stability and without contraction effect without heating when heated above the normal polyamide melting point without problems.

For the tests according to table N, carefully dried polymerisate Po 5 (amino end groups), Po 9 (N in the chain and at the end of the chain) and Po 10 (N at the end of the chain) were used and the Provide extruder with closed funnel with dry nitrogen purge. Thanks to the careful exclusion of moisture, pipes with a clean smooth surface were always obtained.

The result of the dimensional stability tests at 230 ° C can be easily explained from the different chain structure of the polyamide. Cross-linking sites between the polymer chains automatically occur at N 2 chain ends, as well as particularly at chains with -NH members.

In polymer chains with preferably only one reactive H at the end of the chain (-NHR), the silane crosslinking reaction largely leads to a linear chain extension, in which substantially at most the melt viscosity increases. The length shrinkage (L-shrinkage) did not occur since completely dry granulate was processed and therefore no partial reaction took place in the extruder.

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Claims (2)

Method for the production of moldings from thermoplastic polyamides, which have improved mechanical properties and an increased heat distortion stability compared to the polyamide starting material, characterized in that a main mixture is added to the dry polyamide before processing. containing at least 5% by weight of a silane of the formula 1, wherein: n = 0, 1 or 2 Z = an inert organic residue, Y - a divalent organic silicon-linked residue containing a functional group, which reacts with the amino groups and / or the carboxyl groups and / or the amide groups of the polyamide chain to form a chemical bond and A = a hydrolysable residue when moisture is added, and in which polyvidid residues may also be linked together, the mixture of polyamide and main mixture melts, the melt intensively homogenises (mixes) and then according to conventional methods of thermoplastic processing into moldings and expose them to natural ambient humidity before use or condition them briefly in water. Method according to claim 1, characterized in that a thermoplastic containing open pores is used as the main mixture carrier. Process according to claim 2, characterized in that an open-pored polyamide is used as the thermoplastic. 4. Process according to claim 2, characterized in that an open-pore polyolefin is used as the thermoplastic. Method according to claim 3, characterized in that a polyamide 12 or 11 with open pores is used as the main mixture carrier. Process according to claim 1, characterized in that a thermoplastic copolyolefin is used as the main mixture carrier. Process according to claim 6, characterized in that a polybutadiene-containing block copolymer is used as the main mixture carrier. Process according to Claim 7, characterized in that a polymer containing styrene and butadiene blocks is used as the main mixture carrier. Process according to Claim 8, characterized in that a styrene-butadiene triblock polymer is used as the main mixture carrier. Method according to claim 1, characterized in that a mixture designated as ABS or MABS is used as the main mixture carrier. Process according to claim 6, characterized in that a styrene / ethylene-butene / styrene block polymer is used as the main mixture carrier. 12. Process according to claim 6, characterized in that the main mixture carrier is a thermoplastic copolyolefin with the composition ethylene-propylene, ethylene-butene, ethylene-hexene, ethylene-octene, ethylene-butyl acrylate, ethylene-ethyl acrylate, ethylene-vinyl acetate ethylene-propylene-diene monomer (EPDM) or a mixture of these copolyolefins is used. 13. Method according to claim 1, characterized in that a core jacket polymer with a cross-linked core is used as the main mixture carrier. 14. Process according to claim 13, characterized in that a core jacket polymer with a cross-linked butadiene and / or (meth) acrylic acid ester and / or styrene and / or acrylic nitrile-containing core is used as the main mixture carrier. Process according to claim 14, characterized in that a core jacket polymer with a coating of and on grafted methyl (meth) acrylate and / or styrene and / or acrylonitrile is used as the main mixture carrier. 16. A process according to claim 14, characterized in that a core-jacket polymer which further contains olefinic comonomers in the core and / or the jacket is used as the main mixture carrier. 17. Process according to claim 14, characterized in that the main mixture carrier is a commercially available methacrylate-butadiene-styrene (MBS), methacrylate-acrylonitrile-butadiene-styrene (MABS), acrylonitrile-butadiene-styrene (ABS) or pure acrylic denoted core jacket polymer is used. Method according to claims 6 and 13, characterized in that the polymer is present in finely divided form (powder, granules, particles with a diameter smaller than 1 mm). ? % = * - - 35 - 19. Process according to claim 1, characterized in that a silane is used which contains an epoxide, an isocyanate, an aromatic ester or an anhydride group on the organic residue Y. 20. Process according to claim 19, characterized in that the silane 5 as hydrolysable groups contains the residues -OCH ^, -OCH ^ .CH ^, -OC ^ H ^ .OCH3 or -O.CO. ^ S3. Process according to claim 1, characterized in that silane is used in a concentration of 0.1-5% by weight, based on the polyamide. Process according to claim 1, characterized in that as a polyamide a linear, aliphatic homopolyamide, such as PA 12, PA 11, PA 6, PA 6.9, PA 6.12, PA 6.6, an elastomeric polyamide or an amorphous polyamide, e.g. a polyamide from trimethylhexamethylenediamine or terephthalic acid, a partially crystalline homo- or copolyamide, e.g. metaxylylene-15 diamine with adipic acid or a further thermoplastic processable polyamide from aliphatic, cycloaliphatic, aromatic or heteroatoms containing monomers. Method according to claim 1, characterized in that the polyamide is at least 10, but preferably at least 30 amino groups. · contains in the form of the functionalities -NH- or -NE ^. The process according to claim 1, characterized in that the polyamide is dried to a water content of less than 0.03% by weight, added to a melting or homogenizing unit, excluding moisture, with mixing with the main mixture before feeding At the melting unit, immediately in the addition funnel or first in the melt, the polyamide and the main mixture melt and intensively mix, the group Y reacting with the polyamide and subsequently the melt in a molding process, eg injection molding or extrusion and subsequently contacting the obtained molding with the normal ambient atmosphere or, if it is to be used very quickly, subjected to a brief conditioning in water. The method according to claim 24, characterized in that the polyamide / main mixture is melted in an extruder and processing is subsequently effected by injection molding or extrusion. A method according to claim 24, characterized in that the polyamide is melted and the main mixture is continuously melted in the dry polyamide -N * ». * i '1 - 36 - is metered in, after which homogenization and reaction takes place between the polyamide and the silane. A method according to claim 24, characterized in that the polyamide is dried to a water content below 0.02% by weight. Moldings obtained according to any one of claims 1-27. -x X. '\ v -; ; V Y-Si- (A), „I 3-n Z n 2 H2C-CH'CH2-0- (CH2) 3Si (OCH3) 3 o 3 OCNMCH2) 3Si (OC2H5) 3 5 CH2 = C-C0 * 0 (CH2) 3Si (OCH3) 3 5 CH = C * CO * Q (CH -) - Si (OC_H.OCH-), 2 | 2 3 2 4 3 3 CH3 7 H2N (CH2) 3Si (OC2H5) 3 EMS-Inventa AG 8 CH2-CH-CH2 * 0 · (CH2) 3 * Si (OCH3) 3 / OH Polyamide chain —yy NSS ^ CH2-CH -CH2'0 (CH2) 3 * Si (OCH3) 3 OH 9? H OH OH II! CH * CH-R * Si Si * R-CH.CH- / 1 \ / 1 2 \ Polyamide-1 __ (.HO O OR (A) Polyamide chain J ^ chain CH, CH. II 2 CH-OH CH -OH I i RRI i (HO), - Si HO- Si-O-Si-R-CH-OH 2. I 1 0 O (B) CH, 1 I 'I 2 (HO), - Si Si- (OH), HN> ^ -> II (CM RR 1 t - ~ CH'OH CH-OH Polyamxde- I 1 chain ch2 ch2 ^ ») '(«, olyanide_ r chain * EMS-Inventa AG