DE2011608A1 - Thermoplastic polymer mixture - Google Patents

Description

PATENT LAWYERS DR.-ING. H. FINCXE 1 i DIPL-ING. H. BOHU ■,, ' ^L DIPL-ING. S. STAEGER

MOHCHEN5 STR. 31

Imperial Chemical Industries Limited Great Britain

Thermoplastic polymer mixture

The invention relates to thermoplastic polymer mixtures, in particular mixtures of polyamides and certain ethylene copolymers.

According to the invention is a thermoplastic Polymerisatmischuag created, which consists of a ' Polyamide and an ethylene copolymer that

a) 40 to 95 (preferably 60 to 93 -> in particular 60 to 8 ^) percent by weight of ethylene,

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b) 2 to *> Ο (preferably 5 bin ^ u, in particular 7 to 50) percent by weight of a hydroxy- or epojysubstituted aliphatic or alicjctischen ester of an α, ß-unsaturated acid with 3 to 6 carbon atoms, the hydroxy or . Epoxy-substituted aliphatic or cycloaliphatic radical in the ester contains 2 to 10 carbon atoms, and

c) 0 to 55 percent by weight of one with ethylene copolymerizable olefinically unsaturated Monomer

contains polymerized, the sum from components b) and c) 5 to 60 (preferably 7 to 40, in particular 15 to 40) percent by weight of the copolymer, and where the mixture ratio ~ ratio of polyamide to Äthylencopoiymer in the thermoplastic polymer mixture selected in such a way is that the melting point or softening range of the mixture is not significantly lower than that of the polyamide is alone.

When the thermoplastic polymer mixtures according to the invention are heated to softening and are cooled again, the polyamide presumably forms a continuous phase and the ethylene copolymer a disperse phase. In some cases

00984.0 / 2236 bad original

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this can be demonstrated microscopically on appropriately colored sections, whereby the Ethylene copolymer appears as discrete particles, which are separated from each other by the polyamide, above the softening point the oil fine polymer be completely or partially dissolved in the polyamide. In the case of a crystallizable polyamide with a relatively sharp melting point may be the presence a continuous phase made of polyamide is obvious can be derived therefrom that the melting point of the Mixture is not significantly lower than that of the unmixed polyamide »Also in the case of non-crystallizable polyamides that do not have any

have sharp melting points but in one Soften the temperature range, however, the softening range of the mixture is not essential lower than that of the neat polyamide.

In certain cases, the proportion of polyamide in of the mixture are below 50 #. However, they contain Polymer mixtures according to the invention usually 50 to 99% by weight of polyamide and correspondingly 50 to 1% by weight Ethylene copolymer. The preferred proportions are 60 up to 99, especially? 0 to 99% by weight of polyamide and correspondingly 40 to 1, especially 50 to 1% by weight of ethylene copolymer, because in these areas the production

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of blending using conventional methods is.

Under a polyamide or a condensation product be understood that contains repeating amide groups as components of the polymer main chain. Such products are known under the generic name "nylon". They can be produced in that a monoamino-monocarboxylic acid or an internal lactam thereof having at least two carbon atoms is polymerized between the amino group and the carboxyl group, or that essentially Equal molar proportions of a diamine that has at least two carbon atoms between the amino groups contains, and a dicarboxylic acid are polymerized, or that a monoaminocarboxylic acid or an inner Lactam thereof as defined above along with substantially equal molar proportions of one Diamine and a dicarboxylic acid are polymerized. The dicarboxylic acid can be functional in Fprm Derivative such as an ester can be used.

Ib for the purposes of the invention, the expression "substantially equal molar proportions" (of the diamine and the dicarboxylic acid) includes both precisely equal molar proportions and the small »deviations therefrom, the

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occur in the usual methods to stabilize the viscosity of the polyamides obtained «

As examples of the monoamino-monocarboxylic acids mentioned or their lactams, one can mention those compounds which contain 2 to 16 carbon atoms between the amino group and the carbon group, these carbon atoms in a lactam forming a ring together with the -ΟΟ.ΪίϊΗ- Form a group. Examples of the aminocarboxylic acids that may be mentioned are lactams - aminocaproic acid, butyro -, pivalo, capro -, oapryl -, oenantho-, ühd # - \ * ^ - o «- and dodeeanolactam.

Examples of the diamines mentioned include diamines of the general formula H ₂ N (CH ₂ ) ^ HH ₂ , in which η is an integer from 2 to 16, such as trimethylenediamine, tetramethylenediamine, pentamethylenediamine, octamethylenediamine, decamethylenediamine, dodecamethylenediamine _s hexadecamethylenediamine and especially hexamethylenediamine.

C1-4 alkylated diamines, e.B. 2,2-dimethylpentamethylenediamine and 2 £, 4- and 2,4,4-irimethylhe3tame thy lenediamine are further examples. Aromatic diamines such as e.g.

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00 9 8 AO / 2 236 BAD original

p-Phes / leailamin, and cycloaliphatic diamines, such as diaminodiojclohexylmethane mentioned.

The dicarboxylic acids mentioned can be aromatic, e.g. isophthalic acid and terephthalic acid. The preferred dicarboxylic acids have the formula HOOC.Y.COOK, where Y is a divalent aliphatic ^ Represents radical with Mindeateas 2 carbon atoms. AIa Examples of such acids can be sebacic acid, Octadecßrdiäure, Suberic acid, Azelaic acid, Undecanedioic acid, glutaric acid, pimelic acid and especially mention adipic acid. Oxalic acid is one another preferred acid.

In detail kciPiea. the following polyamides into the thermoplastic Polymeriaatmi loops are incorporated according to the invention.!

Polyha.TcamethyIiiGadip8ini.d (NyXoa 6.6)

Polypyrrolido-9 (Nyio.o «u

Polyeaprolaataia (nylon 6)

Polyundecanolactam (nylon 11)

Polydodecanolactam (nylon 12)

Polyheacamethylene azel amide (nylon 6.9)

Polyhexamethylene sebacinamide (nylon 6.10)

Polyhexamethylene isophthalamide (nylon 6.iP)

Polymetaiqylylene adipamide (nylon MD.6)

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? ■ -

Nylon copolymers are also suitable, for example, certain copolymers other than the following *. ■

Hexamethylene adipamide Caprolactam

Hexamethylene adipamide Hexamethylene isophthalamide

Hexamethylene adipamide hexamethylene terephthalamide

Trime thy! Herame thy 1 enoxami d Hexamethylene oxamide

Heicnnwi thy lenadipamid Hexamethylimazelainamide

Hexaine thy lenadipamide hexamethylene azelainamide Caprolactam

6.6 / 6

Nylon 6.6 / 6.IP

6.6 / 6T

Nylon Trime thy Ιο.2 / 6.2

Nylon 6.6 / 6.9

Nylon 6.6 / 6.9 / 6

As the crystallizable polyamides in general have the most favorable mechanical properties, such polyamides are preferably used in the mixtures according to the invention.

As mentioned at the beginning, the ethylene copolymers contain of the thermoplastic polymer materials according to the invention copolymerized a) ethylene, t) one According to definition, esters and c) if applicable an olefinically unsaturated monomer.

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The ester t>) has an acid component and a hydroxy * or epoxy-substituted β radical. The acid content can e.g. a methacryl, propaeryl, oroton or preferably Be acrylic or methacrylic acid. The hydrosy- or epoxy-substituted radical can be derived from, for example, an alkyl or cycloalkyl radical with 2 to 10 C atoms, e.g. an ethyl, propyl, butyl, octyl or decyl radical. However, it can contain ether bonds and it can be one or more Contain hydroxyl or epoxy groups. By droxy alky radicals, in particular By droaty ethyl radicals, are preferred. Preferred examples of the ester b) are the hydroxyethyl esters of acrylic and methacrylic acid mention. Glycidyl acrylate, for example, is used as epic acrylate and methacrylate in question.

The optionally used olefinically unsaturated monomer c) which can be copolymerized with ethylene must be, for example, another olefin, styrene or a vinyl ether. Ee can also be an unsaturated one Amide, e.g. methacrylamide, amine, e.g. dimethylaminoethyl methacrylate or vinyl pyridine, nitrile, e.g. Acrylonitrile, an H-vinyl compound, e.g. N-vinyl carbazole, or a vinyl halide, e.g. vinyl chloride, be. Preferably, however, the monomer c) is an unsaturated ester (e.g. a lower alkyl ester) up to 2U 16 C atoms. Examples of such esters are

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Methyl acrylate, lthyl methaerylate, S-lthylhea ^ isorylate, 2 ~ $ ethylhe3tyl methacrylate-and in particular Methyl methacrylate. Vinyl esters of -saturated »acids a can also be used, e.g. vinyl formate » Vinyl propionate, vinyl likewiseate and especially vinyl acetate.

They found "that te impact resistance ⁵ thermoplastic polymer mixture ©» according to the invention always big? * 1 ^ d ₅ ^ e more ester b) in the copolymer v © s? * 'J & ßd © fc will. It is therefore preferred to use Xfchyleneopolysiere with 3 to 40 wt # ester b), and in practice maa mostly achieves with copolymers with? up to 30% by weight ester b) excellent results.

Is an olefinically unsaturated monomer e) concomitantly in Äthylencppolymer _t so less than 40 wt% is generally used preferably, though the redeemable for practical amount of the monomers used in each case and depends on the Sthylencopolymer to be mixed polyamide.

The copolymers can be prepared by the known process for polymerization under high pressure

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be, the mixture of comonomers under a pressure of more than 500 atmospheres at elevated temperature & tuj ?, sveökmässig at 120 to 30O ⁰ C, in the presence of free radical polymerization initiators, «.Β. organic peroxides, B ^ droperoxides or AsoverMacUingen, is polymerized. The amounts of the monomers used are such that the desired proportions of monomeric units are polymerized into the copolymer under the reaction conditions. The movement is usually carried out continuously in a stirred vessel or a tubular reactor »although it can also be carried out in batches.

Gemma a further feature of the thermoplastic-polymer mixture according to the invention may contain an amine- "ödendes polyamide.

An amine endea.leot polyamide should be understood to mean a polyamide which contains repeating amide groups as a component of the polymer backbone, including one (tberschuaa bxl amic end groups over carbostyl end groups. The preferred amine-end polyamides are those which have an excess of 10 g of polymer Amine end groups have from 20 to 140 gram equivalents compared to the number of gram equivalents of carboxyl end groups.

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Suitable polyamides for this execution form the Invention are those of the above type, which, however, using the necessary excess of Dlamin compared to dicarboxylic acid to achieve a predominant number of amine end groups, what in the case of lactam polymers by termination of the Polymerization in the presence of an amine, in particular a diamine, or by polymerizing an ester of iminocarboxylic acid.

A special class of thermoplastic polymer mixtures consists of mixtures with at least 50 By weight (preferably 60% by weight) amine-terminated polyamide of the above type and 1 to 50% by weight (preferably 1 to GeW%) on a copolymer of ethylene and a HydroTcyalkyleeter an α, ^ - unsaturated carboxylic acid, E.B. a copolymer of ethylene and hydroxyethyl methacrylate, optionally with, for example, up to 5% w / w methyl methacrylate.

According to a further feature, the thermoplastic polymer mixtures according to the invention can contain a nucleated polyamide.

Under a nucleated polyamide a polyamide should be understood in which a

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nucleating agent has been incorporated to increase the rate of crystallization. Through this the work cycles can be shortened if the polyamides are used in the injection molding process

As examples of nucleating agents, nan talc, Calcium fluoride, graphite, sodium phenylphosphinate, clay, high-melting polyamides such as polyhexenetbylene terephthalamide, and finely divided β Mention polytetrafluoroethylene.

The core-forming agents can be used in the polyamide in amounts of 0.001 to 10 wt #, preferably 0.01 to 5 wt%, and they can be included in the polyamides be incorporated before or during the polymerization.

A second special class of thermoplastic polymer mixtures consists of mixtures with at least 50% by weight of a nucleated polyamide of the above type and 1 to 50% by weight, preferably 1 to 40 wt #, of a copolymer Ethylene and a hydroxyethyl ester of an α, unsaturated carboxylic acid with 3 to 6 carbon atoms, 2 B. a copolymer of ethylene and ß-hydroxyethyl

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009840/2238 BAD original

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methacrylate optionally with, for example up to 5% by weight of methyl methacrylate.

The production of the thermoplastic polymer Mixtures according to the invention can ζ.Β. by Niches of the polyamide with the ethylene copolymer in the melt, expediently by screw extrusion, take place. ,

According to the thermoplastic polymer mixtures of the invention is an inexpensive group of products given that have better properties than the polyamides or the ethylene copolymers themselves »polyamides generally have low melt viscosities and are not very suitable for processing For example, filming or drilling using melt extrusion processes. On the other hand, there are polyethylenes Although suitable for such processing with less effort than with polyamides, they are lacking some of the beneficial physical properties of polyamides in solid form. It would be because of that desirable to produce mixtures of a thermoplastic type from polyamides and polyethylenes alone However, in practice, polyethylenes may not be compatible with polyamides because of the crystal structure of both polyethylenes and polyamides · Probable is that

■ 00984Ö / 2236 * bad original

reduced crystallinity of the ethylene copolymers, which are used according to the invention, partly responsible for the increased compatibility of these ethylene copolymers with polyamides. However not all ethylene copolymers with reduced crystallinity are sufficiently compatible with polyamides, and the copolymers used according to the invention are characterized by such compatibility.

The properties of the thermoplastic polymer mixtures according to the invention are dependent on the The viscosity of the polyamide and that of the ethylene copolymer. In the separate development of the Technology in the polyamide «* and polyethylene areas, it has become customary, due to the inherent polyamides To identify viscosity (I.V.) and polyethylene by the melt index.

The inherent viscosity of a polyamide, e.g.

from Iff lon 6.6, by comparing the variety a 0.5% solution of the polyamide in 90%

Formic acid with a viscosity of 90% Formic acid alone (each with an Ostwald Normal viscometer measured) can be determined,

being the IV. from the relationship

I.V.

log _e t (solution ) / C * t (solvent)

"· 15 ~ ·

009840/2236 ^BAD or'g / nal

is derived, where t (solution) is the flow time (see.) for a given volume of polyamide suspension Hessen means with the viscometer; t (solvent) is the outlet side (in sec.) for the same volume of 90% formic acid and G the concentration of the polyamide in the solution in g / 100 csr solution means.

The Sehmels index of a polyethylene or ethylene copolymer is according to BS 2782; Part 1i 1965, method 1050,

Procedure A measured. The Sctraelz Index of Invention

Appropriate ethylene copolymers can be used during

the beer β division according to the methods of Faehaana

are known to be controlled »taking into account must have some gomoncmere that are used like s.B. Bydroxyäthyimetfaacrylat), chain transfer properties can have.

The ßchmel "However the erfindungsgemaasen mixtures can be determined analogously, with a temperature of 280 ⁰ C and a Düsendurchaesser of 0.0465 inches ▼ is erwendet ·

The inherent thickness of the polyamides can vary depending on the desired properties of the product in sizeable limits. Preferably

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however, polyamides become polyamides with an inherent viscosity from about 0.7 to about 2.4 are used. It will particularly preferred, polyamides with an inherent viscosity of 1.0 to 1.9, typically HyIon 6.6 with an inherent viscosity of approximately 1.0. Such polyamides can be used in generally easy in injection molding but heavier than products with a higher inherent Process fe viscosity in the melt extrusion process. Mixing with the ethylene copolymers with a corresponding Sehmel index increases the melt viscosity increased, so that injection-moldable polyamides are converted into extrusion polyamides by mixing can be.

The melt index of the ethylene copolymers should be have such a value that the mixtures in the molten state are sufficient in their manufacture and processing can flow. The melt index can be, for example, 0.3 to 100, ethylene copolymers with a Melt indexes from 0.3 to 10, especially from 0.5 to 4, are preferred. »

You thermoplastic polymer mixtures according to the Invention can be through machining, extrusion, injection molding, or blow molding Rotational casting process for objects such as

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. e.g. fibers) Biafädem, films, foils, Rohrea, bottles and articles, with sehaumstrufctur can be processed. The mixes are special suitable there, w © flexible or bottom layer-tough products are necessary, e.g. for petrol pipes and hydraulic lines for automobiles, water lines for central heating systems, and drawn Threads and foils. Threads from the inventive Mixtures are not as stiff as unmixed® Polyamide threads, however, is their melting point or softening point not much lower so they are for the production of MHb-- xmsn, which are proportionally need slack threads, are particularly well suited. Films made from the mixtures according to the invention have a higher impact strength and Seissfestigke.it im Comparison with slides from the corresponding not mixed polyamides »..

The thermoplastic polymer mixtures with amine-terminated polyamides are particularly suitable for the production of hot water pipes e.g. for Heating systems.

The thermoplastic polymer mixes with Polyamides that have been nucleated are processable and have good mechanical properties

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Properties. They are particularly suitable for Injection molding process for the manufacture of articles with high impact strength.

According to elmm another feature of the invention can the thermoplastic Polyaierisabmischuiigen after Invention 0.5 to 10, preferably 1 to 5, percent by weight Dip-bicarbonate

A third special class of thermoplastic polymer mixtures consists of mixtures of at least 3> 0% by weight of a polyamide and 1 to 25% of a copolymer of iithyene and a hydroxyethyl ester of an oc, {3 ~ ungas " saturated carboxylic acid, e.g. a copolymer of oil and hydroxyethyl methacrylate, this polymer containing from 0.5 to 10 percent diphenyl carbonate.

Diphenyl carbonate is a well-known crosslinking agent for polyamides. It can be used to increase the melt viscosity. The polymer obtained in this way, however, does not have sufficiently high impact strength for many applications. In the present invention, the impact strength is increased or maintained by blending the polyamide with other polymers; and the beneficial effect of diphenyl carbonate on the melting

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viscoBity can be used if desired, without the impact strength being impaired. Diphenyl carbonate eats special in such cases favorable, in which the ethylene copolymer used greatly increases the impact strength but only slightly improves the melt viscosity »

The polyamide, diphenyl carbonate and ethyl copolymer

"'■"' ■■■ ί

can be mixed in different ways. So I

the diphenyl carbonate at spie Is we ist ^{1 can be} applied to nylon shavings as a solution in a nutritious organic solvent such as methanol and the coated shavings are then mixed with the ethylene copolymer in the melt, conveniently by means of tendon extrusion; or the nylon shavings can be mixed with pulverfö.rmigem diphenyl carbonate and the ethylene polymer and then the mixture by stirring and mixing, j

Appropriately by screw extrusion, homogenized will.

The thermoplastic polymer mixtures according to the invention can also contain small amounts, e.g. up to 30% by weight, based on the weight of the body the hate, contained in an olefin polymer. as Examples of such polymers kane. one bono or Copolymers of ethylene, propylene, or butadiene

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ORiGlMAL BATHROOM

Mention styrene. Although such olefin polymers Bit polyamides are not compatible, it has been found that they are up to the specified limit in the mixtures according to the invention are dispersible.

If necessary, other components, such as fillers, reinforcing agents, pigments such as lamp black, Heat and light stabilizers, regulating substances, chain extenders, matting agents and antioxidants commonly incorporated into polyamides into the thermoplastic Polymer! Admixtures incorporated according to the invention will.

The invention is based on execution below beiepiel purely for example explained in more detail, the specified parts and percentages being based on weight are related.

In Examples 42 to 58 and 104 to 112 are the following abbreviations are used for the components of ethylene copolymers:

Ae «xethylene

HAeKA «2-hydroxyethyl methacrylate KHA · methyl methacrylate HPKA «Bydro propyl methacrylate VA - vinyl acetate

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- 21 - Styrene 2011608 2 ~ ethylhexyl acrylate st « Glyeidyl methacrylate AeHA - GMA

The following standardized test methods for determination the properties of the products according to the invention were used:

Impact strength (according to Charpy) ASTM D, 256 Impact strength (Izod) BS 2782

Impact strength (films) BS 2782 method

30β F

Impact strength (Hohre). ASßW B.2444-65T ...

Flexural modulus and flexural strength ASfM B.79O

Tensile strength ASUM D.638

it '■ Tensile strength (Filmö) ASfM B.643 «43

Tensile Strength (Films) BS 2782 Method

308 B

Stiffness factor (tubes) ASTM D.2412 * 65T

Hot length and elongation (fibers) BS 3 * 11/1961

Module (fibers) according to J.Text, Inst.

i6 Έ107

The flexural modulus was not always the same

Facility measured. The flexural modulus was

Compressible nylon 6.6 after the measurement with

the device according to Examples 1 to 24 and

35 to 91. (5 * 2. I 0.1) χ 10 " ⁵ psi while he at

the measurement with the device according to the examples

to 34 and 104 to 112 (3.6 £ 0.1) χ 10 "^" psi.

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. 009840/2238

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example 1

1. Polymerisatmi loops were produced by extrusion mixing of polyhexamethylene adipamide with an ethylene / Sördroxyäthylmethacrjrlat / Methylaethacrylat terpolymer containing 20% hydroxyl methacrylate and 4 # methyl methacrylate. The extrudate with a milky white color was shredded, dried and processed into test rods in an injection molding process to determine the mechanical properties. Table I shows the properties of the mixtures with different proportions of fine © polymer oils.

ORIGIfNiAL BATHROOM

009840/2236

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Example 2 Comparative bite game.

Ifylon 6.6 and an ethylene / methyl methacrylate copolymer containing 29% methyl methacrylate were mixed by extrusion, shredded, dried and injected into test tubes. processed. ! They notched Schlagzäbitfkeit a 70:30 (ylon copolymer mixture was O ₁ ^ ft.lb/in notch, while the 97.5 a: 2.5 Miechung was 0.58 ft.lb/in notch "Am. A comparison of these results with those in Table Z for mixtures with corresponding compositions, in which, however, the copolymer is an ethylene / hydrate ethyl methyla1; copolymer, clearly shows the better notch toughness of the latter mixtures.

Example 3

TO parts of polyoaprolactam (nylon 6) were mixed by extrusion with 30 parts of ethylene /% draxyät; hyilmethacrylat-Copolymers (Ae? IAelU) according to Beiex <iel 1. The properties of the mixture in comparison with unmixed Hylon 6 boiled as follows:

Notch toughness "O7iT ~ 1, öö HAh / iu Flexural Strength 14.8 x 10 ⁵ 10.3 10 ⁵ psi Flexural modulus 3 _t > χ 10 ⁵ 3.2 χ 10 ⁵ i

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Example 4

Poly dodecanol ac tarn (% lon 12) was made by extrusion with different amounts of the ethylene / Bördraa ^ ithyl » methacrylate Copclymera (AeBAeM) according to Example 1 veralischt- The properties of the Mischriagen are see table II au «

II

Polymerization Resistance Bending Bending 12 ^AeHAeMA strength strength modulus

(ft.lVin) (pai χ 1O "* ⁵ ) (psi χ 10"" ⁵ )

100 3 2.5 0.63 • 9 .4-- • 2 , 0 30th 0.82 8th ,8th 2 , 3 p7, Example 5 1.6 * 6th , 0 1 "8th 70 Comparative example

There were 97.5 parts of folyhexamethylene adipamide (Hylon 6.6) by extrusion with an ethylene / ethyl acrylate copolymer (2.5 parts), the 50 6ew $ Xtbsylacrylat contained, mixed. The noticeability of this Mixture was 0.35 ft.lb / in versus notch 0.55 ft.lb / in notch for the appropriate mix with the ethylene / hydroxyethyl methacrylate copolymer.

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Example 6

70 parts Polyhexaaethylenadipamid (KZlern 6.6) ait an excess of amine end groups over carboxyl end groups of $ 0 urammäqulvalentexi per 10 g of polymer were prepared by extrusion with 30 parts of a JCthylen / - ^ ydro ^ äthylmethaci ^ lat / HethylBiethacrylat terpolymers containing 28 $ ^ srdroaqrätbylnethacrylat and 3% Methyl methacrylate contained (AeHAeHA), mixed. This terpolymer has a melt index of 3 * 1. The polymer mixture was processed into test bars by injection molding to determine the mechanical properties.

The test bars underwent the following hydrolysis / oxidation

ti

Subject to conditions:

67 hours under water in a bomb at 142 ^ C ₄ contained the air; afterward
16 hours in air saturated with water vapor

After drying, the mechanical properties were determined in the usual way. The results are the See Table III.

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009840/2236

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Example 7

97 »5 parts of polyethyleneadipamide with 0.15 parts of fienverted talc were mixed by extrusion with 2.5 parts of an ethylene / hydroxyethyl ethacrylate / methyl methacrylate terpolymer (AeHAeMA,), which contained 28% hydroxyethyl methacrylate and 3% methyl methacrylate. The extrudate obtained in this way was shredded, dried and processed into test bars by injection molding to determine the mechanical properties. The results are shown in Table IV.

Table i.V Egg
module c-
psi χ IC ' * DTA-
Freeze
Point
(° C) Together- K * rb ~
eetzung toughness
ft.lb/iu atreck
psi. χ 10 * ' 5.3 222 Hylon 66 0.37 16.6 5.6 236 Iforlon 66 + _rv
0.15% talc ~ ⁱ²⁶ 18.1 236 Nylon 66 +
0.15% TaXk, 34
+ 2 _t S # AeHAeMA

• DTA · differential thermal analysis. I ¹ f ο Ieser egg rierpunkt serves as the standard for the k * timbildsnae V3rk £ "iakeit additive, the higher the better Elnffierpmkt deßto the nucleating agent.

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Z0116O8

Example 8 '· .

97.5 parts Poa ^ hexametlagrlenadiparaid with 0.1 part Colloidal calcium fluoride was extruded 2.5 parts of the oil interpolymer described in Example 7 mixed »The properties of the mixture are sin can be found in table T.

Table Ί

■ i

Together- notch- bending- bending IHDA- '

Settlement of tough-stretch-modulus ^ ₁ . Freezing

speed limit _x psi x 10 "" ⁷ point

ft.lb/in psi χ Λ0 "* ( ⁰ C)

66 +

0.3 *. 16.8 5.3 240.5

Examples 9-11

These examples illustrate the effect of different concentrations of diphenylene carbonate solely on the properties of a polyamide.

Polyhexamethylene adipamide (Bylon 66) with an inherent Viscosity of 0.98 in the form of cubes Particles about 0.1 inch (2.54 mm) on a side (MARANTL A100 e.Wz.) were coated with diphenylene carbonate (BDH laboratory reagent quality) from methanol solution in different concentrations according to Table VI

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201ΤβΟβ

overdrawn. The schnitzel coated in this way was through a 5A inch (diameter) screw extruder headed, at a vacuum of 50 cm Hg column on a Ventilation above the melting zone and at barrel temperatures of 285 to 295 ° C, a screw speed of 54 rpm, a throughput of 15 to 20 g / min and a residence time of 2.5 to 3.5 seconds became.

The Eactrudat was quenched in water, cut and dried, and the inherent viscosity and the melt viscosity of the product was measured (using a Davenport melt viscosity integrated Indexer - Model III - at 280 ⁰ C). Test bars were produced in the injection molding process, and the notch toughness was determined using a Hounsfleld impact tester (according to Charpy). The tensile and flexural properties were determined using test bars produced in the injection-P molding process using conventional methods. Table VI shows the results in comparison with the properties of a high molecular weight nylon 6.6 (MARAHYL Ά150) with an inherent viscosity of 1.75 »which was produced by polymerization in the solid phase.

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Table VI

ro ι

E.g. Concentration Inherent Snow. » Notch- bending- tensile- tensile «

of diphenyl viscosity viscosity toughness modul feet ig- elongation carbonate (%) (Poiee) ft.lb/in (psi χ keit (*)

O '«'
CP
OO
O MAEANiL
A100
MARANTL
A15O 1.0 0.98
1.75 1
12th 860
450 fo 9 3.0 1.27 3 180 co 10 5.0 1.42 6th 470 1.80 25th 100

0.37 5.27 10.13 37 vii

0.46 * 5.26 10.06 82

Examples 12-14

These examples illustrate the effect of various concentrations of olefin copolymer solely on the properties of a polyamide.

Polyhexamethylene adipamide (Ifylon 6.6) with a inherent viscosity of 0.98 in the form of cubic particles with a side dimension of 2.54 mm (MARANTL A1OC) was used with different Portions of a terpolymer made from ethylene, 2-hydroxyethyl methacrylate and methyl methacrylate (AeHAeMA) in the proportions 69; 28: 3 mixed. The mixing was carried out on a 3/4 inch screw extruder as in Examples 9-11. The extrudate was quenched in water, cut up and dried, and the inherent viscosity, melt viscosity, Notch toughness and tensile and flexural properties of the products were as in Examples 9 to 11 measured. The results are shown in Table VII.

Examples 15-18

Polyhexamethylene adipamide was coated with 3.0% diphenyl carbonate as in Examples 9-11 and then mixed by extrusion with various proportions of AeHAeMA as in Examples 12-14.

-33-

009840/2236

BAD ORiQJNAL

The properties of the products are given in Table VIX refer to.

Example 19

Polyhexamethylene adipamide was coated with 1.5% diphenyl carbonate as in Examples 9-11 and then by extrusion with 2.4 $ AeHAeHA as with Examples 12-14 mixed. The properties

of the product can be found in table VXI.

-34 "

te

Il Γ S ¹ «Λ r · icv <M tS CU CVJ K \ UN vO

5 S-Rl Ρ Λ 8 O ^ O O O * <Γ> O ^

IN UN OJ

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KN

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t "^ UN T- Jt VD IN C ^ UN UN O ^ IO CD KN oooooooo

t I

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O O O O UN ΟΟΟΚΝΝΝΚΝΚΝ5Γ

0098A0 / 2236

2011808

Examples 20-22

Polyhexamethylonadipamide chips were mixed with 2 »45% AeHAeMA and with various proportions of powdered diphenyl carbonate, and the mixture was homogenized by stirring. The mixture was then extruded, and the properties of the products were as "in the examples ^" to ΛΛ

certainly. The results are shown in Table VIII

remove.

BATHROOM - 36

0Q98A0 / 2236

Table "Till

Bepl. Concentration concentration of AeHAeHA on gemah- / vv lenea Di ^v 'phenyl carfconate (%) Inherent melting- Serb- bending- tensile- tensile-yisooeit & t viecosity tough- modulus strength- elongation

ability psi ζ ability ft.lD / in 10-5 pei x

(Poise)

10

"* ⁵

O
CD
CO
00
JO-
CD 20th
21 2.4
2.4 1.0
2.0 1.29
1.90 3,080
15 360 0 44
0 /} ^ | 5.09
5.28 10 • 7 58 \
IS) 22nd 2 4 3.0 2.07 100 800 0.43 10 , 3 46 co
CD •

Example 23 Thermoplastic Polyiierisatmischungen were through Mixing 1 kg of PölyajaidschnitBel and ethylene

copolymer chips in the drum mill and anechliesBend in a 2 inch extruder (vented) * drying the

Brudate under vacuum for about 18 hours at 110 ° C

and deformation of the dry product into test discs and bars eur determination of the mechanical properties

manufactured. a

Ala polyamide, polyhexamethylene adipaaiid was used with a ßcheels index of 4.6 g / 10 min (measured with a Davenport HeIt Indexer - Model II - at 280 * 0), and the copolymer consisted of 68 parts of ethylene (M), 28 parts] 5-hydroxyethyl methacrylate (HAeMl) and 4 parts Methyl methacrylate (MMA).

Properties of blends with various proportions of ethylene copolymer are shown in Table II remove.

BATH

IX

Folymore mix

Polyamide ethylene copolymer

Pubic toamx

g / iOmln

Tensile strength speed

g / cm ² χ 10 "" ⁶

Flexural modulus g / cm2 χ

10 " ⁸

Blow toughness (aft. Charpy)

cm.kg/cm

Softening temperature

100 - 90 10 80 20th 70 30th

4.6 5.6 2.9 2.2

0.86 0.72 0.57 0.49

0.25 0.22 0.17 0.15

5.14 10.07 16.29 18.43

248 248 248 248

This information shows how the impact strength and Flexibility without degradation can be increased when JCthyleaeopolymsre in increasing Hate to be mixed with polyhexamethyleaadipaaid » The softening temperature of a polymer is a rabbit for his pimples and the temperature is one heated keseing block with one on the surface the block of striped polymer straight on the block adheres.

Example 24

The behavioral catfish geaass Beiapi @ l 25 was repeated, With the atomicity, the® as a ethylene copolymer is such It has 72 ropes Ithjlen, 17 parts% droxyatl ^ lHie1: hacrylat and 1 part of ifethyl methacrylate was used.

The properties of marriage with different Proportions of XthyleBeopolyiaer are given in Table I. remove. -,

BADORiGINAL

0098 * 0/2236

Table χ

Polymeric odor

Polyamide / ethylene copolymer W.

tensile strenght

100 90 80 70

10 20 30

0.86 0.74 0.62 0.53

Flexural modulus impact strength

g / cm χ ΙΟ * ^{8 according to Cha} * Py

csukg / em

0.25 0.22 0.18 0.15

5.14-

5.35

8.78

10.72

Again, the data shows the increased flexibility and Impact strength of the polymer coating »after Invention compared to non-rented nylon.

The procedure according to Example 23 was again » fetches, with the exception that besides polyhexamethylene adipamid (Hylon 66) a ethylene copolymer was used, the 77 parts of ethylene, 8 parts of Bydrosyäthylmefchaerylat and contained 15 parts vinyl acetate.

The properties of the polymer mixture with various proportions of ethylene copolymer are shown in Table ZI.

- 0.86 XI Impact strength
na @ h Sharpy
cm.kg/em 10 0.69 Bieg®-
module
10 "" ⁸ 5.14 Tabel 20th α, 55 0.25 7.71, Polymer! Satmisöhung train ~
Polyamide ethylene solid
© opolymer
^(%) ^ g / aa ² χ
; ίο " ⁶ 30th 0.48 0.21 9.86 100 0.17 10.28 90 0.14 80 70

0W84 0/2236

- 42 -

BAD OBiG (NAL

Example 26

Comparative example, using an ethylene copolymer that does not contain any Estor component b).

The procedure according to Example 23 was repeated repeated, with the difference that apart from polyhexamethylene adipainide (MFflon 6.6) an ethylene copolymer was used, the 82 parts of ethylene and 18 parts

Vinyl acetate contained.

The properties of Polymericatmisehungen with different proportions of the ethylene copolymer are the Table XII, the poor impact strength of the mixtures in comparison with Example is particularly evident.

- 0.86 XII Impact strength
according to Charpy
p
cm.kg/cm 10 0.78 Tabel 20th 0.65 Bending
g / cm ² x
ΙΟ " ⁸ 4.07 Polymer mixture tensile
Polyamide ethylene- £ |; f £ ^ig ""
copolymer «
(#) 1%) g / cm χ
ίο- ⁶ 50 0.52 O ₁ 4.50 100 0, 3.64 90 O, 80 O, 70 , 25 »23 , 19th , 15

RAn 009840 / 2-2 36

Example 27

Another comparison example in which an ethylene copolymer without ester component b) is used.

The procedure according to Example 23 was repeated catches up, with the exception that apart from nylon 6.6 Xthylene / vinyl acetate copolymer was used, the Contained 72 parts of ethylene and 28 parts of vinyl acetate.

The properties of polymeric breath mixtures with different proportions of the ethylene copolymer are the Table XIII, where the bad blow Toughness of the mixtures compared to Example 25 again are clearly visible.

Table XIII

Polymer mixture tensile polyamide ethylene strength copolymer

Bending module

10

Charpy impact strength

cm.kg/cm

100 ■ - 0.86 0.25 90 10 0.74 0.22 80 20th 0.60 0.18 70 30th 0.48 0.14

6.00 6.64 6.00

0098 ^, 0/2236

BAD OBSGlNAL

At ^ ie3 ^ 28

This example illustrates the effect of blending an ethylene copolymer with a "filled" Ifylon, the filler being finely divided calcium carbonate (SNOUCAL 6ML from Cement Marketing Company Limited) is.

The procedure according to Example 23 was repeated, where as ÄtUyler / copolymer a copolymer from 68 parts of ethylene, 28 parts of Hydroatyäthylmethacrylat and 4 parts of methyl methacrylate used and the filler was added while mixing by extrusion.

Properties of the filled pole /, "lerisatmischunge" are the table II.IV to entne

- SNOWCAL x ^ XTV Bj. Ego-
nodule
B / cm ² a Blow
toughness
. ("after Izod - firm
speed cm.kg/cm ² Polymer mixture
Polyamide d ethylene
copolvmer
/ Ο * \ /.l/N 3 g / nm χ Notch 10 - io " ^fv 0.25 4.35 20th 0.29 3.37 100 SO 0.26 4.46 80 20th 0.22 75 0.69 70

00984 0/2236

BAD ORiGiNAL

This example shows the effect of mixing . of an ethylene polymer with a "filled" Bylon, with finely divided AlumisiluBisilat as filler (SlJPHEM kaolin from English Clays Lovering Poehin & Company Limited) is used.

The procedure from Example 23 was repeated fetches, where a copolymer of 68 parts Ithylsn, 28 parts of Hydroacyäthylmethacrylat -and 4 parts of Methylmethaerylät used and the filler during the Mix? was added by extrusion.

Properties of the filled polymers are unacceptable

can be found in Table XV.

Table XV

Polymerization mixture SUPREME tensile-bending "Kgrb-Polyamid Ethylene kaolin strength modulus ability

copolymer _(%) speed - g / _approx 2- _x (naeh.! iodine)

polymer _(%) ke

₁₀ -6

100 - 80 75 70 10

0.86 0.25 4.55

20 0.78 '0.36 2.72

20 0.72 0 _t 29 -3i27

20 ö, 66 Ö, .25 '5.4-4

τ; · λγ y <iT * i ¹ TfT ^ y "'-τ * ~ ** η

- 46 - 'BAD OFUölliAL 009840/2236

. Dienes T ei ep ·: ·· (, be: ^ΊΜ χ ΐ; di-j ife .. ⁱ £: tüllmig of Einfadtm from ilen ther'.t (-, - l'ial: LiJfihon Poijiifc.visatuiachuiiGea by the Erii

A mixture was produced by puncturing the holes and vacuum drying vio "boi BöispiöX 25, whereupon the product only": Uiöl $ enliiüf 'ceten 2 inch extruder to a single thread uib ü! Neai Durühiaoaefer of 0, tiäj5 rjü eactr udi cr tw 11: - d ö.

As polyamide vui'do Po? .7 *.>ÜJtaMfi!;Hylii> iud · oawld in.ig ai Mo'LekuliiL'gs-Ifihv "V5a 3 ^? 7 & 1 ^r> CCö and .η.ί. /: ΓομΟ .Ι, / ιη «/. · A 30.1c ^! .Ϊöw ύΐ ^; ϊί 6 · '* ffi ^ i-lin ΙΰΙι, / ίβκ ,? H '!. · ■ · L> .e« IK '

The EijC'.v-iBCh-L · ^ ri -In? Produ ^ l; «iiind άόχ * ^f L '?>« ELlr · JTI. au remove.

PolymerisatraischUD · ";. 'ΊαχΛ- Bfihuiüjg £ ^ _=;! I Ov .;.

Polyamid ät; b; -ii; n '£ «£;!; L§- · _{fj t} . <,. ,,? ... _{1 (}

Α, Ληΐ * "tr

Ό.

1CO -;>, 51 'fO 1.03

00 93 40/2 236 ' ^4? "

BATH ORIGINAL

The reduction in stiffness caused by aa & T of Ätliyloßööpolj'iijerß with the polyamide eats -Special favorable for the production of sewing thread _'t bei'denen a relatively limp thread "is needed"

Example 31

This example illustrates the production of foils avis follows the thermoplastic polymer! satiai seams

the invention. I.

The procedure was repeated, with the exception that the product is extruded from a film with a degree of voxi 0, C = OSJ cm.

AIa Poüyaraid 'became Pol ^ hexam ^ thyjeiiadiparaid.iait einora Molecular weight of «about T? 000 υικί as- <7cpol; yraer became eitiß eue fcO Tiiilßii iCthvXon, 28 part «iJi Hydrax.yäthyl" ■

a «'"! ^ ι at uud M share Iluthylnrn-iisrT - ;. ·. · at ver'K? Jidet. g

Some Eigcfnnohafton dos P ^ odul - ts ai «jel der ■ Cab'-le X ^- VlX tu h

98 ^ 0/2 236

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4- \ (Χ3

■ tH C) «)

φ η -η

A4. O- ^

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^ β g Oj

C co 4-> Γ

υ W

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W I V g ft β

Λί - H '■

η xf ftV .. • η +3 σ

■ ρ us

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f ^ ti

h ti β 1

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«

0098ΑΟ / 2236

BATH ORIGINAL

Films from the Polyiaerisatmi views according to the invention show a remarkable increase in impact strength and tear resistance compared to pollen from unmisehtiui Polyamides.

Example 32

This example illustrates the preparation of polymer blends consisting of a polyamide Polyhexamethylene adipamide with a molecular weight of contain about 42,000 (inherent visoosibate «1.9).

The procedure gessr'eö Example 23 was repeated, wherein the copolymer of 68 parts of ethylene, 28 parts of Hydroxyäthylmethaerylat and 4 parts of methyl methacrylate duration.

Some properties of the mixes with different The proportions of the copolymer are shown in Table XVIXI au.

Table XVIII

Polymer mixture tensile polyamide, ethylene-resistant «
copolymer ability

g / cm ** jr

Until gemodul

g / cm ² 10 "*

100

95
90

5
10

8.23 0.26 7.87 0.25 7.45 0.22

ΤΠΓ1 "δ * ΠΓ7ΤΤΤδ"

Sshlagf e 8 'cigkeit (according to Izod) cm.kg/cm notch

5.99

8.16

10.88

BATH ORIGINAL

From this information iöfc t / ieder how ο I the impact strength with an increasing proportion of ethylene copolymer increased in the mixture.

Examples 33 through 40 illustrate thermoplastics Poiymerisatmixat from different Polyamides and copolyamides

Example 3?

700 parts of PoiyheKamethyiensebaeamid (ifylon 6.10; MARANYL B1OO e.Wa.) and 300 parts of the ethylene terpolymer used in Example 6 were mixed and homogenized by extrusion by means of a screw extruder with a diameter of 3/4 inch, the screw speed being and the feed and barrel temperatures were 235 to 278 ° C so that a throughput of 15 to 20 g / min was achieved. The extrudate was quenched with water, cut Lb and dried in vacuo. The srhaibenen Schnlbsni. were then deformed in the injection molding process, and the products were dried 18 hours in vacuo at 70 ⁰ C, Some properties of the blend are in Bestowed in neat nylon 6.10 of Table ILX be seen,

- 51 -

BATH ORIGINAL

009840/2236

Table XIX

Nylon 6.10 Nylon 6.10 / Terpolymer Mie'chiing

Hit ähiglce it (Charpy)

(ft.lb/in notch) 0.345 0.82

Flexural yield strength (pai) 11 9 χ ίο ' 7, 92 X 10 * Flexural modulus (psi) 3, 2 χ 10 ⁵ . 2, 16 X 10 ⁵ Tensile strength (pai) > » 89 χ io ' :% 28 X K) ' Elongation at break (%) '"- 124 14th / |

Dan Polyhexfimethyleneebacamid gemäafi Beiapiel 33 was PoXyundeoanoaactam (N ^ lon.ii;. RIL8A1T BMNO ".Wa) eraetEit xma on was as in Example Z3 fionrbeiiiei ;," with the AbveichuüE, the Eitruder DnaE with cylinder temperatures of 1 ° A 219 ⁰ bie C was operated to achieve a rate of 10 to 1 1/2 g / min. Thus, a mixture was obtained with the characteristics from the table, which is also shown in comparison with the figure of unexplained llylott 11.

0098A0 / 2.236 BAD

Table ZX KyI on 11 lfylon 11 / Copolymer

mixture

Impact strength (Charpy) _{Λ ft} , -. » (ft.lBVin lerb) ° '* ^{3 1} · ¹⁵

Yeast limit (pai) 7.42 χ 1O ⁵ 5f27 χ 1O ⁵ Flexural modulus (pai) 1.99 x 1O ^ 1.41 x 1O ⁵

Tensile strength (pai) 5t76 χ 1O ⁵ 4,11 χ 1O ⁵ Elongation at break (£) 170 221

Beiapial 35

The polyhexaaethylene aebacamide according to Example 33 was by Polyhaxamethyleiiieophthalaaid (Ifylon 6.1P) »it a relative viability of 10.98 (measured in 8.4% solution in 90% formic acid at 25 ° C) and it was worked as in Example 33, with the exception that the extruder with barrel temperatures of j260 to 267 ° C with a Throughput of 16 to 15 g / ain was operated. Consequently you got a mixture with those from the table ΧΣΧ ar visible properties, which also indicate the properties of unpolluted Fjrlon 6 * iP.

- 53 -

BAD ORiGINAL

009840/2236

^ J - ■ - ■ ·

Table XXI Nylon 6 O .iP Ifylon 6.iP / Co-
p olymer misery CVJ , 37 χ . O,. 10 ⁵ Notch toughness (after Charpy)
ft.lb/in notch 18 , 89 χ
, 95 χ 1O ⁵ 12.66 χ 10 ⁵
10 ³ Flexural yield strength (psi) 5
9, O 1O ³ 3, ^ 9 x
9 * 19 x Flexural modulus (psi)
Tensile strength (psi) ) until * 5 166 ° C Elongation at break {%) 13C 166 ° 0 130 to Softening area (Vicat) Example 36

700 parts Polyhexamethylenazeiainamid (ifylon 6.9) having a relative Viscositat of 28.6 (measured in 8.4% solution in 90% formic acid at 25 ° C) and with an excess of amine end groups over carboxyl end groups of 119 gram against equivalents per 1 ü 10 g of polymer were mixed with 300 parts of the

■■■■■■ "-. ■■■ '■"■'. ■ · '-.'-' mixed ethylene terpolymer and mixed by extrusion as in Example 33, with the difference that the cylinder temperatures 235 to 278 ° G The exudate was quenched with vaseer, crushed and dried in vacuum. I? He obtained ¹ sur chips were in Sprittguesverfahren into test determining the

mechanical properties processed, the

Syringe tongue before testing 18 hours at 70 ° C in vacuum

were dried.

The molded parts were subjected to the following hydrolysis / oxidation test:

64 hours under water and air in a Cariua Bomb tube at 142 ° C, and then 16 hours at 142 ° C in air, previously with water was passed through at 85 ° C. They were then molded at 70 ° C. for 48 hours dried in vacuum before determining the mechanical properties. The mechanical properties the mixture before and after the hydrolysis / oxidation treatment can be found in Table ZXII, which also indicates the properties of the unmixed HyIon 6.9.

. Bathroom original

- 55 -

009840/2236

ο κ »

IS »(U)

Table XXII Checkout notch toughness, flexural modulus, tensile strength, elongation at break

(according to Charpy) limit · ~ speed »

it.lb/ia Notch pei χ ΙΟ "" ⁵ psi χ 10 ^? pel χ 10 %

before amch before aaeh before aach before aach before aach

! iylon ', ■' ''. '■. ■ ■ '' ■

6.9- 0.58 0.56 7.58 9.06 2.23 2.5? 5.59 5.04 28 6

Hiechung

CD

6 ".9 0 * 275 0.22 14.12 12.59 4.105 4.39 8.92 · 8.82 17 0 vg

S - · ■

.2 '

Example 37

A mixture of 700 files of a copolymer of polyhexamethylene adipamide and folycaprolactam (molar ratio 90:10) (Hflon 6.6 / 6) with a relative Viscosities of 4-2.5 (measured in 8.4 # solution in 90 # formic acid) and 300 parts of dee in The ethylene terpolymer used in Example 6 was extruded on a 3/4 inch screw extruder, wherein the cylinder temperatures were 275 oils and 290 ° C the screw speed was 30 rpm with a throughput of 16 to 20 g / min. The extrudate was quenched in water, shredded, dried and shaped by injection molding. The saplings were dried as in Example 35 before testing. Some properties of the mixture are in comparison with unmixed Hylcn 6.6 / 6 of Table XXIII remove.

Tabel ΧΣΙΙΙ .6 / 6 Nylon 6.6 / 6-
mixture m Hylon 6 0.63 Heredity (Charpy)
(ft.lb/in notch) 0.34 10 ⁵ 8.97 a t 10 ⁵ Bending yield strength (psi) 16.31 x 10 ⁵ 2.85 3 c 10 ⁵ Flexural modulus (psi) 4.83 x 1O ⁵ 6.32 3 c 10 ⁵ Tensile strength (psi) 11.03 x 71 Elongation at break (^) 54 • 57 - 009840 / 2236 BATH c

Example 58

If the Ifylon 6.6 / 6 in Example 37 is made by a copolymer made of polyhexamethylene adipamide and polynexamethylene isophthalamide (molar ratio «80:20) (Hylon 6.6 / 6.iP) Bit with an inherent viscosity of 1.01 replaced, and the procedure according to Example 37 is repeated, with the difference that the cylinder temperatures from 266 to 284 ° C and a throughput of 16 to 20 g / min were used, a mixture is obtained with the properties shown in Table ZXIV. the Properties of the unmixed lfylon 6.6 / 6.iP are for Comparison also indicated. '

Tabel XXIV .6 / 6.iP 198 11
3 Ifylon 6 »35 7th Notch Ability (Chaipy)
(ft, lb / in notch) j 10 * Flexural yield strength (psi)
Flexural modulus (psi) 19.25 χ
5 * 06 χ 10 * Tensile strength (psi) 12.31 x Elongation at break (%) lon 6.6 / 6.iP
mixture Example 39 i
0.80 , 56x10 *
, 51 χ 10 ⁵ .20 χ 10 * 80

The nylon 6.6 / 6 in Example 37 is replaced by a copolymer from polyhexamethylene adipamide and polyhexamethylene terephthalamide (molar ratio - 80:20) (% ion 6.6 / 6.T)

009840 / 223β

with a relative viscosity of 31.5 (measured in 8.4 # solution in 90% formic acid at 25 ° C) replaced, and the procedure is as in Example 37, but with the difference that cylinder temperatures of 280 to 296 ° C and a throughput of 20 to 22 g / min are used, a mixture is obtained with the properties evident from Table XXV, which also include the properties of unmixed Kylon 6.6 / 6.T indicating for comparison.

Table XXV

tijlon 6.6 / 6.T ftylon 6.6 / 6.T

mixture

Notch toughness (Charpy)
(ft.lb/in notch) 0.14

Flexural yield strength (psi) 17i74 χ 10 * Flexural modulus (psi) 4.85 x 10 ⁵ Tensile strength (psi) 10.74 x 10 ⁵ Elongation at break {%) 21

51 O , 56 9, 76 χ 10 ⁵ 2, 31 χ 10 ⁵ 6, χ 10 ³
27

Example 40

If the SFflon 6.6 / 6 in Example 37 by a copolymer 'of Polytrimethylbexamethylenoxamid and PolyhexamethylenoxaMid (molar ratio »55 * 45) (Ifylon trimethyl 6.2 / 6.2, the trimethylhexamethylene diamine used for preparing the copolymer is a 50: 50 mixture of

- 59 00984Q / 2236

2,4,4- uad 2,2,4-trimethylenediamine) with a inherent viscosity of 0.96 (measured in sulfur * säureloeuag), and is like "in Example 37 worked, but with the difference that cylinder temperatures from 20 to 289 ° C and a throughput of 14 to 16 g / min are used, one obtains a Mixture with the properties shown in Table XXVI, which also include properties I for comparison from UEVera! indicates real »Kylon Trimethyl 6.2 / 6.2.

Sabelle XXVl EFflon trimethyl
6.2 / 6.2 0 % lon trimetfeyl
6, .2 / 6.2 - mix 0.20 0, Notchable
(Charpy) ft.lb/in 14.29 x 10 ⁵ 7.42 χ Flex «yield point 5.54 x *> ⁵ 2.29 3ε Flexural modulus (pai) Tensile strength (pel) 9.97 x 1O ⁵ 5.51 χ Elongation at break (%) 296 10 ³ 10 ⁵ 10 ⁵

Di * examples ij.1 to 58 illustrate thermo-. plastic mixtures of nylon 6.6 and various other ethylene polymers in various proportions 2-B (hydroxyethyl * ethacrylate and possibly various Termonoeeren. -,

- 60 009840/2236

BATH ORIGINAL

Example 41

700 parts of polyhexamethylene adipamide (nylon 6.6 - KARAHTIi A100) and 500 parts of a terpolymer of ethylene, 2-hydroxyethyl methacrylate (8%) and 2-ethylhexyl acrylate (22%) were intimately mixed with one another. The mixture was then mixed by extrusion with a 3A inch screw extruder at barrel temperatures of 280 to 295 ° C. and a screw speed of 50 rpm and a throughput of 16 to 20 g / min. The milchweiese extrudate was quenched in water, cut and vacuum dried at 70 ⁰ C. The chips thus obtained were molded by injection molding and the fuel were tongue 18 hours in vacuum at 7O ° C-dried. The moldings had the following properties.

Charpy Impact Strength 0.46 ft.lb / in notch bending yield strength 10.29 x 10 ^ psi

Flexural Modulus 3.25 X 10 ^ psi Tensile strength 7.2 χ 10 ⁵ pel Elongation at break '21% Examples 42 to 58

Aue of Table XXVII are properties of others Mixtures can be seen that were obtained by replacing the terpolymer in Example 41 with 300 parts of that in the 2nd column of the Ethylene ter- or copolymers listed in Table XXVII can be obtained. The components of the ter- or copolymer

009840/2236 " ⁶¹ " _BAD original

are given in abbreviated form, with the percentages by weight of the components are given in brackets "

■■ '■ .λ - 6g -, 00984072236

Table IXVTI

Bepl. Ithylenter or mechanical properties of the 1 ^ y ion 6.6 / Ät hy lent er or -copolymer- copolymer mixture

Zusanaen- Schneie- Kerbsahig- Tensile Strength- Bending Stretch- Bending-Settlement index speed (Charpy) speed »limit _x modulus g / 10 min ft.lh.in notch psi χ ΙΟ"" ³ pei χ 1Ο ~ *

Elongation at break

module,. psi χ 10 " ⁵

42 Ae.EAeHA. AeHA 1.7 0.57 (70:15:15) 45 Ae. HAeMA 0.4 1.08 (60:40) 1.5 44 Ae.HAeMA
(75:25)
Ae.HAeMA.YA 0.63 45 (69: 25: 6) 2.5 0.61 O Ae.HAeMA. VA CO 46 (67: 24: 9) 5.7 0.59 α> Ae. HAeMA. St. * · » 47 (68.26: 6) 8.5 0.72 ο Ae.HAeMA.St 48 (75: 21: 4) 1.7 0.69 to
ΙΌ Ae.HAeMA.St Ο » 49 (66: 32: 2) 5.0 0.77 Ae.HAeMA.VA 50 (80: 8: 11) 4.2 0.44 Ae.HAeMA.VA 51 (78:12:10) 8.1 0.62 Ae. HAeMA. VA 52 (75: 8: 17) 14.9 0.49 • Ae. HAeMA. VA ι 53 (71: 7: 22) 7.3 0.49 Φ
IU Ae.HAeMA.MMA 54 (68: 25: 7) 5.0 0.58 I. Ae.HAeMA.MMA 55 (76: 15: 9) 5.2 0.58 Ae.HAeMA.MMA 56 (77: 9: 14) 2.7 0.64 Ae. HAeMA. MMA- * 5.9 57 Ae.HAeMA.MMA * 0.48 58 0.47

7.29

6.08

6.72 6.48

5.89

6.67

10.9 10.8 10.2 9.74 9.64 9.87 9.52 10.3 10.3

3.16 3.28 3.0 3.0 3.12 3.6 3.2 2.99 3.34 3.19 3.22 3.2 3.2 3.5 3.2 3.7 3.34

26th

39 19 33 36

35

- 63 (71t8: 2i)

Examples 59 to 70

These examples show the effects; in the event of changes in the amine end group content of the polyamide component of the thermoplastic polymer mixture. Various samples from% lon 6.6, each with an excess of amine end groups compared to carboxy end groups. I in de »from the 2nd column of Table XXYIII had hatred, were mixed with 300 parts of the terpolymer used in Example 6, whereupon the mixture was mixed by extrusion as in Example 41. The Eättrudate wurdmabgeschreckt _f shredded, dried, molded by injection molding and the moldings were dried, even after the procedure recovered "Example ^{41": ·;} ■ ·::. · ■: ■: ■ ' ^Λ ■■■■ ■■■' A

The moldings were subjected to a glandular / oxidation test as in * ■ subject to example 36 and then as there dried.

The Bechaniscben properties of the mixtures in each case and after the ▼ or ^ fdrolyse / Cbcydationa treatment are shown in Table XXYIII.

Examples 69 and 70 use samples made from Hylon 6.6

"." ■■ '. ^: . - ■ '- "** ?. ■■' ■■■

with a higher content of carboxy end groups ^ al «s

009S40 / 2236 - 64 -

BATH

Amine end groups. They were listed in the table to show how a mixture with such a HyIon 6.6 is less stable to the Efordrolee / oxidation treatment than a mixture "with a Hjlon 6.6" with an excess of amine end groups compared to carboxyl end groups.

BATH ORIGINAL

- 65 -

009860/2236

O Ssj ft. fiylon 6.6 in mixture 0.66 Tabel XXVIII after before after before after ■■ after Bru
■ 1 - 39 - 36 ch- -. 17th I. CD Excess of IV des
Amine end groups * polymers 0.71 0.38 9.14 9.86 2.87 5.2 6.49 before 3.4 29 13.5 11 VtI OO 0.78 0.48 9.45 9.69 2.84 5.2 • 6 / £ thylenterpoXymer-r 6.81 18.5 - ■ 19th after - 4,, I. · * - ·
O 59 146 0.85 mechanical properties of nylon 6
Mixtures 0.61 9.54 10.29 2.80 5.45 Tensile strength
ability,
psi χ 10 """ 6.99 26th 10 10.6 15.6 0 it) 60 112.5 0.81 Notch-resistant, flexurally elongated, flexural
ability (Charpy) limit _x module _c
ft.lb/in notch psi χ 10- ° psi χ 10 " ⁵ 0.66 9.11 9.67 2.65 5.24 15th 22nd - S.
1 χ 10 g polymer.
* IO 61 77.6 0.8 before 0.64 10.07 10.77 5.07 4.17 6.54 6.86 19th Ca)
O> 62 72 0.94 0.48 0 * 58 9.55 9.27 2.74 5.09 6.45 - 63 62 0.95 0.55 0.8 9.16 10.29 5.07 3.12 6.25 6.7 64 53 0.81 0.64 0.865 10.37 10.55 2.93 3.31 - - 65 45 0.89 0.78 0.68 9.65 10.07 3.16 3.41 7.03 6.79 2011608 66 36.5 0.92 0.78 0.74 9.77 10.43 3.02 5.76 - 7.19 I.
S. 67 29 0.84. 0.52 0.44 9.64 10.88 5.04 5.84 6.29 6.64 68 10.5 0.87 0.25 9.61 10.41 5.04 3.94 - 5.59 69 -52.5 0.87 "Excess compared to carboxy end groups in gram equivalents per 6.82 70 - 8Q, 5 0.78 6.96 0.9 7.06 0.9 6.56 ro
6th
ο
Q
■ ζ. 0.64

Examples 71 through 76 illustrate stability versus the hydrolysis / oxidation treatment of thermoplastics Blends made by blending nylon with an excess of amine end groups compared to carboxyl " end groups and ethylene terpolymers with various termonomer substituents and various proportions of 2-Bydro: xyäthylmethacrylat. be obtained.

Example 71

700 parts of Ifylon 6.6 according to Example 65 were mixed with 300 Blended parts of the ethylene terpolymer according to Example 50, and the mixture was mixed by extrusion as in Example 41. The extrudate was quenched shredded, dried and injection molded deformed, whereupon the injection molded parts as in Example 41 were dried.

The moldings were subjected to the hydrolysis / oxidation test and then dried as described in Example 36.

The mechanical properties of the mixture before and after the bytoolysis / oxidation treatment are the Refer to Table XXIX.

BATH ORIGINAL

- 67 -

0098AÜ / 2236

2011Ö08

Table XXIX Before Afterward 0.6 0.55 Notch ability (Charpy)
ft.lb/in notch 9.24 10.6Y Bending yield strength (psi χ 10 "*) . 3.13 4.12 Flexural modulus (psi χ 10 " ⁵ ) 7Λ7 6.48 Tensile strength (pel χ ΙΟ "* ⁵ ) 9 O Elongation at break (%) Examples 72 to 76

In Table XXX are further examples of the Mixtures listed according to the invention, the ethylene terpolymer used in Example 71 by the specified in the 2nd column of the table Xthylene terpolymer is replaced. The mechanical properties of the mixtures before and after the hydrolysis / oxidation test are also included in the. Table listed.

BATHROOM ORIGINAL 68 -

009840/2236

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BATH ORIGINAL

- 69 -

1011608 -

Examples 77 big 80

These examples show the effect of Changes in the proportions of polyamide and ethylene copolymer in thermoplastic blends.

Thermoplastic polymer blends were prepared by intimately blending various amounts of nylon 6.6 and the ethylene terpolymer used in Example 6. The blended chips were then extruded using a 3/4 inch screw extruder at a speed of 40 rpm, barrel temperatures from 275 to 290 ⁰ O and a throughput of 13 to i? g / mia mixed. The & ctrtidat was quenched, dried and processed into test bars by injection molding, and the latter were dried as in Example 53 »

■ ■■ '■ ■ ■ I

The moldings underwent a hydrolysis / oxidation treatment Subjected as in Example 36 and then dried in vacuo at 65.degree. C. for 18 hours.

The mechanical properties of the mixtures before and possibly after the% drolyae / Ö * ydatiöns «treatment are the Table XXXI can be found »

Table XXXI

E.g. Polymer mixture, notch-resistant, flexural elongation, flexural tensile strength, elongation at break

Mylon 6.6 ethylene limit, modulus, - keit,

ι terpolymer ft.lb/in psi χ ΙΟ "- ⁷ psi χ ΙΟ""-'10 psi χ" ^3%%% Impact

before after before after after before after before after

10 0.41 - 11.64 -

20 0.69 - 11.42 -

40 1.14 1.12 7.58 8.13

50 3.68 4.24 5.75 6.22

77 90 00984 78
79 80
60 ο
■ »>. 80 50 Κ>
Κ> to
CD

4.42 2, 45 9 , 86 , 58 - 18th 33 - 3.36 1, 98 7.96 , 71 - 12th 25th - 2.54 5 6, 67 31 1.75 4th 5, 92 100

Examples 81 to 85

These examples illustrate thermoplastisch® polymer mixtures that contain small amounts of a Contain olafins (polyethylene).

Thermoplastic polymer mixtures were produced by using * ssPolyhexamethylene adipamide (Bylon 6.6 -HAHARfL A10O) with low-density polyethylene and λ

with the ethylene terpolymer used in Example 6 Intimately mixed and as in Examples 77 to 80 was mixed. The mixes were extruding quenched shredded and dried, whereupon the Schnitzel were processed into test rods by injection molding.

Aue of Table XXXlI are the properties of the

Ingredients with various proportions of polyethylene

and ethylene terpolymer can be seen. *

.. BAD ORIGINAL

- 72 0.0 9 8 40/2 236

Table XXXII

E.g. Polymer mixture

Nylon 6.6 poly ae

ether

len

σ co οο

mer

Properties of the polymer mixture

Bending

Tensile tensile notch bending

strength- modulus tough- stretch-

speed limit

psi χ psi χ ft.lb/in psi χ

_r 5 notch _n -3

module psi χ

10

81 70 30th O 6.7 2.85 0.26 11.2 3.58 6th I. 82 70 25th 5 * 7.4 3.3 0.32 10.08 3.47 12th Po 83 70 20th 10 7.3 2.83 0.5 11.1 3.78 . 19th i 84 70 15th 15th 6.8 2.78 0.6 10.4 3.74 31 85 70 10 20th 7.0 2.92 0.81 10.1 3.41 12th

cn ο oo

Example 86

This example "relates to the manufacture of pipelines from the thermoplastic mixtures according to the invention.

A mixture of 70% polyhexamethylene adipamide (Kylon 6.6 - MARAKiL A100) and 30% of the ethylene terpolymer used in Example 6 was prepared as in Example 6. -j The product was then extruded into a tube using a 35 mm screw extruder with an annular nozzle at cylinder temperatures of up to 295 ° C. and a throughput of 25 lb / h. The soft extrudate was placed in a quench tank with water, the interior ^. des (thanks was under vacuum to prevent the pipe from collapsing.

The properties of the pipeline before and after a hydrolysis / oxidation treatment according to Example 6 can be found in Table XXXIII. The properties of the pipes made of polyhexamethylene adipaaid (Ifylpn 6.6 -. ΜΔ1ΑΚΓΙ / Al50) and PQlyun4ecanQlact? Am (% lcm 11 - ■ RIIiSAH BMNO) are listed for comparison and clearly show the superiority of the pipe »vis, the mixture with regard to the stiffness factor urid

the% dr ply ^ e / Oxydst long treatment; »

Dimensions

Table XXXIII

Inner diameter wall thickness stiffness yield strength impact tester (in) (in) factor _{± χ} ^ ₀ -? ability (ft.Ib)

before after before after after before after before after

ο φΐοη 6.6 / ethylene- <x> terpolymer blend

Mylon 6.6 (MARANTL A15O)

Bylon 11 (RILSAH BMKO)

0.57 0.58 0.06 0.06 2.1 2.2 4.0 4-, O held up to

60 ft.Ib from

0.40 0.41 0.05 0.055 3.5 * 8.2 2.1

0.39 0.41 0.06 0.06 1.7 * 3.9 1.0

withstood up to 60 ft.Ib.

vn

♦ Collapse below $ 5 rash

CD O € 0

'■' -75 -

Examples 87 to 91

These examples illustrate the use of Jtylon 6 »6 bit stabilizers in the thermoplastic polymer blends according to the invention.

Thermoplaetiectae polymer mixtures were thereby manufactured that TOO parts polyhexamethylene adipaffiid- (I ^ lon 6.6) samples which contain the additives according to the '~ ϊ 2. Column of Table XXXIV contained, with 300 parts of the ethylene terpolymer used in Example 6 such as in Example 41 were mixed. You additives were in the polyamide during the polymerization

incorporated.

The molded parts were subjected to a hydrolysis / oxidation treatment as in Example 6, and the properties of the mixtures before and after this treatment are shown in Table XXIV. Λ

- 76 0098 ^ 0 /2.23.6

Table ΧΣΧΙΤ E.g. HyI on in the mongrel

Additive AEG I.V. in Hylon 6.6 of nylon

Properties of the mixture

Notch- bending- bending- tensile strength- fracture toughness modulus of elongation

psi χ psi χ ^

1O ~ ⁵ 1O " ⁵

(Charpy) border ft.lb/in psi χ * -3

«Γ

CO87

89 ι

Hatriurah hypophosphite (0.1) Carbon (0.3)

Sodium hypo-

phosphite (0.1)

1.1.3 _T Tris (2- methyl 4-hydroxy 5-tert-butyl-93.6 1.03

henyl) butane 0.1) carbon (0.3)

Carbon (0.3) condensation product of diphenylamine and 106.6 0.92 Acetone in the presence of EI (0.1)

before after before after after before after before after

0.88 1.0 9.37 10.40-3.08 3.24 7.41 7.81 33 20

0.98 1.12 9.84 10.56 3.08 3.25 7.4-9 7.23 47 68

0.82 0.86 9.31 10.6 2.97 3.30 7.23 7.66 30 22

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00.9840 / 223: ©

BeIaT) IeIe 92 to 105 These examples relate to the manufacture of fibers

from the thermoplastic mixtures according to the Invention.

The polymer mixtures listed in Table XXXV were analogous to the example described manufactured. The blends were made by melt spinning See below fibers with the specified properties processed

BATH ORIGINAL

- 79 -00984 0/2236

Table XXXY

Bepl. Composition of the mixture

Nylon 6.6 ethylene

terpolyner

Properties of the fibers

denier

92 100 A. 0 93 99.5 A. 0.5 94 99.0 A. 1.0 95 98.0 B. 2.0 96 99.0 0 1.0 97 98.0 D. 2.0 98 99.0 D. 1 * 0 99 98.0 Ξ 2.0 100 99.5 E. 0.5 10 ' F. 2.0 1 98.0 P. 0.5 102 99.5 2.0 103 98.0 »■ Ethylene terpolymer g A »
T * ■ I » £ 3 *
C - «· * ι Β · " H co E ' ■ " ο F -
I.

116.1 118.5

119.5

116.3 117.9 103.7 112.3 117.9

115.4

115.9 117.9 115.2

n ti i ^

"· '50

. ·· "52

H H CO

Range long strain module g / denier % g / denier 4.5 29.3 55.9 4.7 22.0 54.9 4.7 29.8 59.1 4.7 34.9 58.7 4.6 32.8 38.9 5.1 '20 .1 40.9 5.3 22.6 41.2 4.8 24.5 38.9 4 ^, 8 25.5 42.1 4.7 26.2 39.9 4.9 28.7 39.4 4.7 25.5 38.4

Examples 104 to 112

From Table XXXVI are further examples of the Mixtures according to the invention can be seen, which are analogous to Example 23 but by replacing the one in Example 23 ethylene copolymer used by the one in the 3 «column Ethylene copolymers listed in the table were produced. The components of the ethylene copolymers are abbreviated given, the respective percentages by weight being given in brackets.

- 81 -

009840/2236

E.g. Pölyiaerisatverbindungen Properties of the mixture

Polyamide ethylene copolymer tensile, bending, notch, stretching, melting, expansion
% Together V In melting ί!?! ¹⁶ * "^ i ä? I ^S " ^{nune index} ^

aenset mix index * ** * ^si * *** g / 10 min. P
zung g / 10 min. ^psl , ^x 10 ~ ^{5 581} J * % ' ⁰ C

1Ö " ⁵ 10" ⁷

104 70 Ae.HAeMA.VA
(82: 4: 14) 30th - 7.4 2.1 3.0 37 - - O 105 70 Ae. HAeMA. MMA
(82: 6: 12) 30th 4.4 7.85 2.2 2.33 40 3.8 - co
co 106 70 Ae.HPMA.MMA
(74: 18: 8) 30th 3.0 7.1 1.97 5.1 32 3.1 - ö 107 70 Ae.GMA.HMA
(73: 9: 18) 30th 1.6 8.3 2.25 8.52 70 0.18 - NJ
CaJ 108 70 Ae.HAeMA.St
(64: 32: 4) 30th 5.8 8.2 2.28 7.76 25th 2.6 248 109 60 Ae. HAeMA. MMA
(68: 28: 4) 40 3.4 5.91 1.73 7.6 50 1.7 . 248 110 50 Ae. HAeMA.MMA
(68: 28: 4) 50 3.4 5.17 1.29 9.4 58 1.1 - 111 95 Ae .HAeMA .MMA
(68: 28: 4) 5 3.4 11.5 2.9 3.1 20th 4.2 -, H12 70 Ae.HAeMA 30th 2.35 6.7 1.7 11.0 76 -

cn ο oo

Claims (1)

Claims Thermoplastic polymer mixture made of a polyamide, which may be an amine-terminated polyamide or a nucleated polyamide, and a Ethylene copolymer, the a) 40 to 95 (preferably 60 to 85) wt # of ethylene, b) 2 to 50 (preferably 5 to 40, especially 7 to 30% by weight of a hydroxy- or epoxy-substituted aliphatic or alicyclic Esters of an α, ß-unsaturated acid with 3 to 6 carbon atoms, the hydroxy or epoxy substituted aliphatic or cycloaliphatic radical in this ester 2 to 10 Contains carbon atoms, e.g. hydroxyethyl methacrylate, c) 0 to 55 wt. of an olefinically unsaturated one Monomer that is polymerizable with the olefin a) c © 1st, Contains copolymerized, the sum of b) and c) 5 to 60, preferably 7 to 40, percent by weight of the Polymer represents, and where the mixing ratios of polyamide and ethylene copolymer in the thermoplastic Polymer mixture are chosen such that the melting point or softening range of the mixture is not significantly lower than that of the neat polyamide, and wherein the polyamide mixture from 8 * about 0 to 10% of their weight of diphenyl carbon, - 83 - 0098A0 / 2236 ORIGINAL BATHROOM 0 to 43 # of their weight of an olefin polymer and optionally a filler _t a reinforcing agent, a pigment, a heat or light stabilizer,
contains a lust substance, a chain lengthening agent, a matting agent or an antioxidant. PATCMTAHWJU.H
rt HWCKE DIPL-WO.W to> ■: -
DlPL-ING S. tTAKB 00984.0 / 2 2 36