DE2722270A1 - MIX OF POLYAMIDE AND MODIFIED POLYAETHYLENE - Google Patents

Description

Mixture of polyamide and modified polyethylene

The invention relates to mixtures of polyamide and modified polyethylene with improved impact resistance, the modified polyethylene component of the blends contains an active -GO-0-CO group which has been introduced into the ethylene polymer by graft or copolymerization techniques that effectively bind ethylenically unsaturated polycarboxylic anhydrides or polycarboxylic acids to or into the polymer backbone.

There has been a great deal of experience with mixtures in the art made of polyamides with modified polyolefins, however became the unpredictable stoichiometry of mixtures made of polyamide and modified polyethylene not recognized, which leads to a significant improvement in notched Izod impact strength and Gardner impact strength.

In JA-AS 30 943 (Senmura et al., Published on October 7, 1970) it is described that the addition of a with an inter- or intramolecular acid anhydride modified olefin polymerisation products, e.g. a dispersant in the form of a polyolefin modified with maleic anhydride, such as polypropylene or polyethylene

HD-8516

If polyamide / polyolefin compositions are correct, the degree of diaperation in polyamide and polyolefin membrane hangers is improved. This JA-AS essentially teaches the addition of one percent (1 #) or nominal or very small amounts of one modified polyethylene, i.e. a dispersant, on polyamide and polyolefins is efforts to improve the Degree of dispersion.

Although this JA-AS recognized the ability to improve the dispersion properties of completely unmodified polymer blends of polyamides and polyolefins, i.e. blends with less than 1 ^ of modified polyolefin, in this JA-AS the importance of the stoehiometry of Mixtures of polyamides and modified polyethylenes not recognized in terms of impact resistance.

The invention relates to polymer blends of polyamide and modified polyethylene with unexpected and improved Impact resistance properties, with the modified polyethylene component of the mixtures .. active -CO-O-CO-Gruppa which have been incorporated into the ethylene polymer by graft or copolymerization techniques which are effective Ethylenically unsaturated polyarboxylic anhydrides or polycarboxylic acids bind to or in the polymer structure.

Another embodiment of the invention relates to mixtures of polyamides and modified polyethylenes as "ach from smaller amounts of modified thermoplastic polymer materials and, if necessary, customary fillers or ingredients, such as plasticizers, plasticizers, stabilizers, surface-active agents, pigments, dyes, Reinforcing agents, flame retardants, thinners and their mixtures.

The term "polyamide" includes in the present context Polymeric materials commonly referred to as nylon that are known to be long chain synthetic polymer with regularly recurring amide groups as a component of the main polymer chain; the term includes

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Speaking amide / ester copolymers, amide / polyether copolymers and / or their block copolymers.

Examples of polyamides that can be used, among others, are polyamides obtained by polymerizing a difunctional moiety Monomers or, in an equivalent manner, their cyclic lactams (such as epsilon-aminocaproic acid or caprolactam) or by Reaction of a pair of matching monomers, for example a diamine and a dicarboxylic acid (e.g. hexamethylenediamine and adipic acid).

For example, the polylactam by polymerization of Lactam monomers of the formula

where R _{1 is} an alkylene group having 3 to 12 or more carbon atoms, preferably 5 to 12 carbon atoms. A preferred monomer is epsilon-caprolactam with 5 carbon atoms in the alkylene group. Examples of lactam monomers are, in addition to epsilon-caprolactam, pyrrolidone, piperidone, valerolactam, CaprsELactam and lauryllactam. furthermore, mixed polymers of two or more of the abovementioned or of corresponding lactam monomers are included. Suitable polyamines which are useful for polymerizing polyamides include, for example, propane diamine, hexamethylene diamine and octamethylene diamine. Suitable polycarboxylic acids include, for example, adipic acid, pimelic acid, suberic acid, sebacic acid and dodecanedioic acid. This also includes mixed polymers or polymer blends of polyamides from two of the categories listed above.

The polyamides used according to the invention, preferably Polyhexamethylene adipic acid amide (nylon 66) or poly-6-aalnocaproic acid (nylon 6), can have a molecular weight with elnea

Number average of 4000 and preferably 10,000 to 40,000 or

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own even more. It can be any polyamide under that The prerequisite is that the polyamide has a number average molecular weight of at least 4,000, which is determined by any known method including the methods of Encyclopedia of Polymer Science and Technology, Vol. 10, Title Polyamides, pp.483-597, Intersoi · PaM, (I9 * 9), on Aijfcfci · * fully incorporated by reference, may be used in the practice of the invention.

The term "polyethylene" in the present context includes ethylene homopolymers and copolymers of ethylene and Propylene, butenes or other unsaturated aliphatic hydrocarbons.

The preferred copolymers of ethylene contain up to 40 wt .- ^ of a higher olefin, such as propylene, 1-butene, 1-helene, ie acyclic 1-monoolefins with 3 to 8 carbon atoms per molecule, or mixtures thereof. Furthermore (although not so much preferred) the copolymers contain up to 5% such di- or trolefins as used in the theory of ethylene / propylene terpolymers, such as ethylidene norbornene, methylene norbornene, 1,4-hexadiene and yinylnorbornene . The term "polyethylene" also includes mixtures of homo-, mixed- or terpolyethylene, which includes mixtures of two or more of the polymers listed above. It may be any of polyethylene with the proviso that the polyethylene toq a density at least about 0.85, and-preferably 0.915 to O _t 97O or "ore has that by any known method einsohlleelich of the methods of the Encyclopedia of Polymer Solenoe" ad Technology, Vol 6, title: Ethylene Polymers, pp. 275-454t Interscience Publishers (1969), to which reference is expressly made here, has been prepared by dtr Auftftih tion of the invention can be used. It can ethylene polymers, which are produced by Niederdruck- or Hochdruckteohnlken, which are generally used in the production toq linear or high density polyethylenes and verswelgteo or low-density polyethylenes are used and known are used to carry out the invention.

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The term "modified polyethylene" includes polyethylene with w. active -CO-O-CO-groups bound in or to the ethylene polymer by graft or Mlpolymerlsations-Technlken eiai.

The modification of the polyethylene can thereby be carried out be that one äthylenlech unsaturated polycarboxylic acid or your anhydride, i.e. a modifier, old ethylene oil Unsealed on the polyethylene framework or In the polyethylene framework βInpolymerleiert.

Currently preferred module agents are, for example, derivatives of unsaturated cyclic polycarboxylic acid anhydrides, ethylenically unsaturated polycarboxylic acids which form anhydrides at elevated temperatures, and also esters of polycarboxylic acids. Examples of polycarboxylic acid anhydrides, polycarboxylic acids and polycarboxylic acid esters which are suitable polyethylene modulants are the following: maleic acid, itaoonic acid, citraconic acid, mesaconic acid, maleic anhydride ₉ , cltraconic anhydride / ^ -oot-5- · !! - 2,3-dicarboxylic acid anhydride, 1,2,3,4,5,8,9,10-octahydronaphthalene-2 ', 3-dicarboxylic acid anhydride, 2-0xa-1, J-dlketosplro -Zif ^ Z-non-T-en, Blcyclo - / ^. 2.i7-hept-5-en-2,3-dicarboxylic acid anhydride, 4- (2-cyclopentenyl) -benzene-1,2-dicarboxylic acid anhydride, x- Methyl cyclo- / 2.2.17-hept-5-en-2,3-dicarboxylic acid anhydride or maleoprimaric acid / maleo-priuaric aoid7, dimethyl maleate, dipropyl maleate, di-butyl maleate, di-cyclopentyl maleate, di-hexyl maleate, methyl-chloro maleate and phenyl maleate, di-benzyl maleate. Particularly preferred modifiers include malelic anhydride compounds of the formula

In which R is a hydrogen atom, a halogen atom or a Is methyl group. Specific examples are maleic anhydride,

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Monochloromaleic anhydride, dichloromaleic anhydride, Orraconic anhydride and dimethyl maleic anhydride. Of that Maleic anhydride is currently most preferred for economic reasons such as easy availability and low material cost.

The modified polyethylene polymers can be prepared by any method which provides -CO-O-CO groups active in the polymer chain. Such active groups are readily introduced by procedures known as "graft polymerization techniques". Examples of such suitable techniques include heating polyethylene to a temperature at or above the melting point of the polyethylene, preferably in the absence of an inert solvent, the mixture being subjected to high energy ionizing radiation, e.g. gamma rays, x-rays, in the presence of a modifier or strongly accelerated electrons; the polyethylene can also be contacted with a free radical generating material such as a peroxide or a hydroperoxide. At present, modified polyethylene is preferably made by heating a mixture of polyethylene and a modifier above the melting point of the polyethylene in the presence of a free radical catalyst such as a peroxide or hydroperoxide, preferably under high shear mixing conditions. Any known peroxide with the general formula RO — OH or ROOR, where R is an organic radical, with a half-life of at least 2 to 60 seconds at 200 ^° C. can be used. Examples of usable peroxides include dicumyl peroxide, di-t-butyl hydroperoxide, p-menthane hydroperoxide and cumene hydroperoxide. Generally, the mixture in the absence of a solvent is heated to a temperature above 100 ⁰ C and below 300 ⁰ C for sufficient heating and for preventing a substantial decomposition of the resulting modified polyethylene. The presently preferred graft polymerization temperatures are, for example, temperatures in the range of about 145 ble

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260 ⁰ C, in particular from about 160 to 210 ⁰ O.

In general, the reaction time is that required to modify of the polyethylene substrate is required, is relatively short and takes a few seconds to about 20 minutes, although longer Heating times do not modify the polyethylene can significantly influence and, if necessary, be applied.

As for the amount of modifier used in the manufacture of modified polyethylene is used, it is Any amount that is sufficient to produce a modified polyethylene, In the polymer backbone about 5 x 10 ~ ^ to about 1 χ 10, preferably about

-. "= 5-2-1

1 χ 10 ^J to about 5 χ 10 and in particular about 5 x 10 ^J to about 1.5 χ 10 "Molecular equivalents of the

/ aktlven-CO-O-CO groups per 100 g of polyethylene have been incorporated. For example, a currently preferred unmodified polyethylene, ie a lower polyethylene, is mixed with a currently preferred modifier, ie maleic anhydride, in an amount of about 0.1 to 1.25 (rew.- ^c / o based on the weight of the polyethylene under the reaction conditions in Brought contact, which are suitable for a chemical incorporation of maleic anhydride into the polyethylene skeleton by graft copolymerization techniques.

It can be any amount of the modified polyethylene be used provided that the polyethylene has at least a minimum effective amount of -CO-O-CO units as defined below, the amount being sufficient to

(1) the Garduer impact strength (measured in in-lb = 2.54 cm χ 0.45 kg) of the mixtures of polyamide and modified poly ethylene by 50 "/>, preferably 100 $> _t, in particular 200 ° / o particularly preferred 300 %, compared to the Gardner impact strength of mixtures of polyamide and unmodified polyethylene with comparable amounts of polyamide / poly

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to increase ethylene constituents, or where (2) the amount is preferably sufficient to obtain the notched Izod impact strength (i.e. the impact strength according to the notched Izod impact strength according to ASTM D-256, method A (measured in ft-lbs / in notch = 0.3 m χ 0.45 kg / 2.54 cm notch)) of the mixtures of polyamide / modified polyethylene by at least 50 5t, preferably $ 500 and especially $ 1000, versus the Notched Izod impact strength of blends of polyamide and unmodified polyethylene with comparable amounts of To improve polyamide / polyethylene components.

The increase in the impact resistance of the mixtures of polyamide and modified polyethylene according to the invention is with the molar equivalents of the active -rCO-O-CO groups of the modified polyethylene in relation to the -NHg group content of the Polyamide related provided that the ratio of polyamide to modified polyethylene Im Range from about 90:10 to about 40:60, preferably 85:15 up to 50:50 and in particular 80:20 to 60:40.

In general, the molar ratio -CO-O-CO-Z-NB ^, for optimal Gardner impact strength and Izod is required, in the range from 0.02 to 3.0, preferably in the range from 0.05 to 2.5 and in particular in the range of 0.10 to 1.5.

On the basis of the -CO-O-CO- / -NH ₂ ratio given above and the relative amount of the polyamide in relation to the modified polyethylene (as indicated above), the person skilled in the art can produce mixtures of polyamide and modified polyethylene with considerably improved impact strength properties, by using the optimal, preferred or particularly preferred ratio of the -CO-O-CO group to the amine group in practicing the invention.

The mixtures of polyamide and modified polyethylene can be prepared in any known manner, preferably at a temperature above the

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Melting point of the polyamide, generally at a temperature in the range from about 220 to about 400 ⁰ C works. Preferably the mixing is carried out in the absence of a solvent and by mechanical processing. Accordingly, mixtures can be produced in, for example, extruders, Banbury mixers or roller mills, a currently preferred mixer has a twin screw extruder, such as a 28 mm twin screw (Werner & P ^, unfortunately, type ZDS-K28), which is attached to mechanical processing and Kc -pounding of thermoplastic materials at elevated temperatures is adapted and has vacuum or ventilation openings, whereby unreacted and entrained substances can be easily removed from the materials to be mixed. In general, any time in which a homogeneous dispersion is formed can be selected as the mixing time, for example times from 1 second to 10 hours or even more.

The invention thus relates to polymer compositions made from polyamide and modified ethylene polymers with improved impact resistance properties. The modified polyethylene as a component of the blends contains active -CO-O-CO groups which have been incorporated into the ithylenpolymers by grafting or interpolymerization techniques which effectively bind ethylenically unsaturated polycarboxylic anhydrides or acids to or into the polymer backbone . The polymer blends can be pressed or molded into films, sheets, fibers, laminates, or other molded articles including reinforced articles by conventional molding techniques.

In all examples the given mechanical Values on the standards given below; all parts are expressed on a weight basis unless otherwise is specified. The invention is explained in more detail below by means of examples. The following Teats were used for the examples applied unless otherwise stated.

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At 211121 ^

Elongation value (psi = 0.07 kg / cm) ASTM D633 Elongation at break (<; ') ASTH D639

Flexural Strength (psi = 0.07 kg / ^cm2) ASTM D790 Flexural Modulus (psi = 0.07 kg / ^cm2) ASTM D79O

Izod impact strength (ft-lbs / in = ASTM D256A 0.3 m χ 0.45 kg / 2.54 cm)

notched

un, notched

Gardner - ;; ohl'j (; fixed (in-lbs = 2.54 cm χ 0.45 kg) using a variable Gardner high-performance impact tester3 (see ASTM D2794-69 for device description). Test procedure: _{3 2x} 25 4x25 4mm The injection molded test plate (1/8 χ 2.5 x 2.5) in or / is placed on the support surface with the test tip touching the surface. The weight is lifted to a specified height and released. The test plate is removed and the struck area inspected for cracks. If no cracks are observed, the process is repeated at a higher elevation until cracks appear in the test panel, then additional Teot panels are tested at heights slightly less than the height at which the test panel was first tested Cracks were observed in the first test panel to determine an average impact strength.

Note (test sample pre-treatment): All test samples were pre-treated 30 minutes in boiling water and then aged for 3 days at 23 ⁰ C (73 ⁰ P) and a relative humidity of 50 ia prior to testing.

Examples 1 to 3 . Manufacture of blends of nylon 66 /

Low density polyethylene.

It was a mixture of 2450 g of nylon 66 and 1,050 g of polyethyl len low density at 271 ⁰ C and 200 rev / min at a rate of 113 g / min with a 28 mm twin screw extruder (ZDS-K28 from Werner & Pfleiderer) extrudert. Using the same procedure , a mixture of 2450 g nylon 66 and 1050 g. \) Ly- (ethylene-g-maleic anhydride) was extruded. That

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The extrudate of each mixture was crushed into pellets, dried

Cylinder _on net and on test samples injection molded (J 282 C = 540 F, form 54 ⁰ G = 130 ⁰ P). Unblended nylon 66 was also injection molded. The test results are shown in Table I. (Poly- (ethylene-g-maleic anhydride) - polyethylene ■ with grafted maleic anhydride)

Table I. Examples 1

Nylon 66 (wt%) ^ 70 70 100

Low density polyethylene (wt .- ^) ' ^b ' 30 30 0

Maleic anhydride on polyethylene.

grafted (w / w) 0 1.25

Gardner impact strength (2.54 cm 0.45 kg = in-lb)

23 ⁰ C (73 ⁰ F)
-1S ° C (0 ⁰ F)

Notched Izod impact strength (0.3 m 0.45 kg / 2.54 cm = ft-lbs / in)

Elongation value ^ ^c '(0.07 kg / cm = psi)

Elongation glue break ' ^c ' (0.07 kg / cm = psi)

16 > 320 > 320 , 4 3 210 7th 1 , 0 19 , 4 1 3550 3250 5150 2850 4200 4300 , 74 90 140 160 1 , 77 1 , 35 2

Attrition (

Flexural modulus (0.07 x 10 ~ ⁵ kg / cm ² = 10 " ⁵ pei)

(a) Nylon 66 = DuPont Zytel 101

(b) Low density polyethylene = Exxon XP80-8

(c) sample according to ASTM D1322 Type L; Thickness 3.2 mm (0.125 in); Cross head speed 0.13 cm / min (0.05 in / min); Distance between clamps 2.54 cm

= 1.0 in.

Examples 4 to 3 30 . Manufacture of blends of nylon 66

and low density polyethylene.

Using the procedure of Example 1, a * range of mixtures with 10 to 60 wt .- $ of polyethylene was prepared dna containing from 0 to 1.25 weight .-% of grafted maleic anhydride. The extrudate of each mixture was pelletized ^/ ^ y ^l ii'ncier ^rt 'L' ⁶ '' ^{1 "00} ^ ¹¹⁶ * ^and test samples injection molded ^(A:> 'J2 ° t: = 540 ^ü tf, form 63 ⁰ C = 145 ⁰ F). In addition, were

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-Ar

Injection molded unmixed nylon 66 and unmixed low density polyethylene containing zero and 1.25 weight grafted maleic anhydride . The test results are summarized in Table 2.

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Table II (Examples 4 to

ITylon 66 (wt .- $) (a) Polyethylene (wt .- $) (b)

"sl ^ insäureanhydrid grafted to polyethylene (weight-To) O

Ratio -COC- / -NH ₂ (c)

Gardner impact strength (2.54 cm 0.45 feg = in-lb,

23 ⁰ C m 730 p

"Indestimprovement (fo) compared to control values (CV.) Tzod notched impact strength (0.3 m 0.45 kg / 2.54 cm

= ft-lb / in)

Minimum improvement (#) compared to control values (C.7.) Elongation value (Tensile Yield; psi = 0.07 kg / cm)

Elongation at break (Tensile Break; psi «0.07 kg / cm) Elongation at break ($>)

Flexural modulus (psi χ 10 "^ = 0.07 x 10" ^ kg / cm)

__4 5_ 6 7 8 9 10

100 90 90 90 90 80 80 0 10 10 10 10 20 20

O 0.1 0 _; 5 1 _; 25th

0 ^ 020 ^ 10 ^ 25 0 ^ 045 > 320 230 320> 32O> 320 135> 320

1.1 1.3

1.9 2.2

- CV. 40> 40> 40 CV. > 140 ^

- CV. 90 50 70 CV. 40

9200 7800 7800 7900 7800 6500 6600 7500 7200 6900 6800 7200 6300 6300 210 75 65 70 75 70 85 1.84 1.56 1.60 1.51 1.51 1.35 1.20 IsJ

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(a) Nylon 66 = DuPont Zytel 101

(b) Low Density Polyethylene = Cities Service EH497

(c) Assumption: (1) Hn of nylon 66 = 18,000; half of

Polyamide end groups are -NHp groups.

Examples 31 and 32 . Manufacture of blends of nylon 66

and high density polyethylene.

Using the procedure of Example 1, blends were made Made of nylon 66 with 30 wt .- # high density polyethylene which is zero or 1.25 wt .- ^ grafted maleic anhydride contained. The extrudate of each blend was chopped into pellets, dried, and injection molded into test samples. The results are shown in Table III.

Table III (a)

Examples 31 32_

Nylon 66 (wt .- ^) (b) 70 70

High density polyethylene (G ₆ W .- #) (b) 30 30

Maleic anhydride on polyethylene

grafted (wt .- $) 0 1.25

Gardner impact strength (2.54 cm 0.45 kg

= in-lb) 12 320

Notched Izod impact strength (0.3 m χ 0.45 kg / 2.54 cm = ft-lbs / in)

Elongation value (c) (0.07 kg / cm = jlsi) Elongation at break (c) (0.07 kg / cm = psi) Elongation at break (} *) (c) Flexural modulus (0.07 x 10 ~ ⁵ kg / cm ² = 10 ~ ^ pei)

(a) Nylon 66 = DuPont Zytel 161

(b) High density polyethylene = Chemplex 6060

(c) sample according to ASTM D1822 Type I; Thickness 3.2 mm (0.125 in); Cross head speed 0.13 cm / win (0.05 in / min); Clamp spacing 2.54 cm = 1.0 in.

0 , 3 4, 9 8000 7100 6700 8500 50 145 2 , 69 2, 26th

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Examples 33 and 34 . Manufacture of blends of nylon 6

and polyethylene lower and higher

Density.

Using the procedure of Example 1, blends of nylon 6 (foster Grant Fosta nylon 525) at 30 wt Low-density polyethylene (Citlee Service EH497) or high-density polyethylene (Chemplex 6060) manufactured because «zero and 1.25% by weight of grafted maleic anhydride. The extrudate of each mixture was chopped into pellets, dried and injection molded. When molding the mixture with a content of unmodified polyethylene, difficulties arose because a separation occurred in such a AuemaS, that the molded articles hardly held together mechanically, so that they were not mechanically tested. No difficulty was encountered in molding the mixtures with Contained maleic anhydride modified polyethylene; selected mechanical properties of the mixtures are In Table IV compiled.

Table IT

Examples . 33 34

Nylon 6 (wt .- ^) (a)

Low density polyethylene (wt .- ^) (b) High Density Polyethylene (Weight #) (c)

Maleic anhydride grafted onto polyethylene (wt .-? S)

Gardner Impact Strength (2.54 cm 0.45 kg »in-lb)

Isod notched impact strength (0.3 m χ 0.45 kg / 2.54 cm »ft-lbs / ln)

Elongation value (d) (0.07 kg / om "pel) Elongation at break (d) (0.07 kg / om ■ pel) elongation at break (#) Flexural modulus (0.07 x 10 ⁵ kg / cm ² - ⁵ 10Γ

70 70 , 25 30th , 0 0 30th , 5 1f 25 1 320 320 4, 3 1 6250 7600 , 53 9200 8500 240 165 2, 17 2

(a) Nylon 6 = Foster Grant Foeta Nylon 525

(b) Low density polyethylene ■ 01tle · Service EH497

(c) high density polyethylene * Chemplex 6060

(d) sample according to ASTM D1822 Type 2; Thickness x 3.2 mm (0.125 in);

Crosshead diameter 0.13 cm / ain (0.05 ln / mln);

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Clamp spacing 2.54 cm = 1.0 in. Examples 35 to 39 «Preparation of mixtures from filled Nylon and low density polyethylene.

Using the procedure of Example 1, blends of Example 16 were prepared containing 10 and 30 weight percent glass fiber and silica, respectively. The extrudate of each mixture was chopped into pellets, dried, injection molded ui. ¹ The results are shown in Table V.

Table V

Examples 35 36 37 33 39

Example 16 (wt .- ^) 100 90 70 90 70 Glass fiber (a) O 10 30 0 0 Silica (b) 0 0 0 10 30 Gardner impact strength (2.54 cm

x 0.45 kg = in-lbs)> 320 175 25 195 175

Notched Izod impact strength (0.3 m

x 0.45 kg / 2.54 cm = ft-lbs / in) 20.3 4.6 2.7 2.8 1.5

Iodine impact strength unnotched (0.3 ι

x 0-5 kg / 2.54 cm - ft-lbe / in) NB NB 17 NB 49

Flexural modulus (0.07 x 10 " ⁵ kg / cm ²

β 10-5 psi) 0.93 1.26 3.06 1.45 2.15

(a) Glass fiber = OC 219A

(b) silicon dioxide = Minusil (5 jub)

Example 40 . Production of poly (ethylene-g-maleic anhydride)

A mixture of 1000 g of high-density polyethylene (Chemplex 6060), 12.50 g of maleic anhydride and 0.75 g of dicunyl peroxide in a glass vessel on a roller mill or the like. Moved for 15 min and then extruded with a 28 mm double flask extruder (ZDS-K2 * 8 Werner & Pfleiderer). The screw speed was 200 r / min, the feed rate of 2.7 kg (6 lb) / h and the temperatures (zone fixed values) were: (1) 130 ⁰ C; (2) HO ⁰ C; (3) HO ⁰ C; (4) 190 ⁰ C;

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(5) 190 ^° C; (6; press tool) 135 ^° C. The extrudate was comminuted into pellets. IR analysis of the extrudate showed carbonyl bands at 1855 and 1780 cm. Oxygen analysis of the extrudate indicated 0.52 # oxygen, which corresponds to 1.03% by weight grafted maleic anhydride. Similarly, poly (ethylene-g-maleic anhydride) of Examples 2, 6 to 8, 10 to 12, H to 16, 18 to 20, 22 to 24, 26 to 23, 30, 32 to 33 and 35 to 39 prepared, wherein the specified low and high Polyethylenes Jnchte with maleic anhydride Pfropfwerten from 0.1 to 5 wt .- ^ _t 0 were used.

As can be seen from the fourth of the examples, the blends of polyamide and modified polyethylene according to the invention have a considerably improved impact strength when compared with the impact strength of comparative samples made of polyamide and unmodified polyethylene. The use of other polyamides or other modified polyethylenes, ie modified polyethylene with modifiers other than maleic anhydride and / or polyethylene as a graft polymer or copolymer, instead of the polyamides or modified polyethylenes of the examples provides corresponding improvements in the impact strength of the mixtures of polyamide and modified polyethylene. The blends of polyamide and modified polyethylene provide thermoplastic compositions that can be pressed or molded into a wide variety of articles used in the automotive, plant and equipment arts . and aviation technology and also for decorative and protective purposes as well as, for example, as containers and container linings, whereby they can be used, for example, in washing machines, garbage compactors and dishwashers or for other purposes, or which can be pressed or molded into all other possible thermoplastic objects, in which the improved impact resistance properties of the mixtures offer advantages.

709848/1037

Claims (7)

Dr. rer. not. Horst Schüler nn 6 ^ 00 Frankfurt / Mainι ie, May 1977 2 7 2 2 2 7 g srsri "Dr" α / - / Telex: 04-16759 mopot d Postschedc account> 282420-602 Frankfurt / M. Bank account: 22S / 0389 DwitsdM Bank AG. Frankfurt / M. 4270-REKÖ516 General Electric Company 1 River Road Schenectady, N, Yf USA claims 1. Mixture of polyamide and modified polyethylene, characterized in that the modified polyethylene - A active -CO-O-CO-Qruppen in an amount of about 5 ι 10 to about 1 χ 10 molar equivalents per 100 g of polyethylene ent holds that the mixture has at least 50 i » improved Gardner impact strength and that the weight ratio from polyamide to modified polyethylene is in the range of about 90:10 to about 4-0: 60. 2. Mixture according to claim 1, characterized by a notched Izod impact strength improved by at least 50 %. 3. Mixture according to claim 1 or 2 »characterized by polyamide and modified polyethylene as essential. Polymer components. 4. Mixture according to one of the preceding claims, characterized in that the modified polyethylene contains about 1 χ 10 ~ ⁵ to about 5 x 10 " ² molar equivalents of groups per 100 g of polyethylene. 1 χ 10 ~ ⁵ to about 5 x 10 " ² molar equivalents of active -CO-O-CO- 5. Mixture according to one of the preceding claims, characterized by a weight ratio of polyamide to modified polyethylene in the range from about 85:15 to about 50:50. 709848/1037 ORIGINAL INSPECTED 6. Mixture according to claim 5, characterized by a weight ratio of polyamide to modified Polyäthy len in the range of about 80:20 to about 60:40. 7. Mixture according to one of the preceding claims, characterized by maleic acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, C itraconsäure anhydride, itaconic anhydride, 4-methylcyclohex-4-en-1, 2-dicarboxylic anhydride, bicyclo / 2. 2 . 2 / -oct-5-en-2,3-d! Carboxylic acid anhydride, 1 ^^^^, SjiJiiO-octahydronaphthalene ^^ - dicarboxylic acid anhydride, 2-0xa-1 , 3-d iketospiro- / 4,4 / -non-7-en, bicyclo- / 2.2.1 / -hept-5-en-2,3-dioarboxylic anhydride, 4- (2-cyclopentenjl) -benzene-1,2- dicarboxylic anhydride, i-methyl bicyclo- / 2.2.1 / -hept-5-en-2,3- dicarboxylic anhydride or maleoprimaric acid, dimethyl maleate, dipropyl maleate, diisobutyl maleate, dicyclopentyl maleate, dihexyl maleate, dibenzyl maleate, p-chlorophenylmethyl maleate or phenylethyl maleate as polyethylene modifiers. 709848/1037