CH649566A5 - Multiphase, thermoplastic composition and process for the preparation thereof - Google Patents

Description

This invention relates to a multi-phase thermoplastic composition and a method for producing the same. 20 Unmodified thermoplastic polyamides are generally considered to be “solid” or “tough”. For example, the polyamides have good elongation at break, high breaking energy determined by tensile tests, high impact tensile strength and high energy absorption, ascertained by falling body tests, e.g. the impact test according to Gardner. In one respect, however, the polyamides are quite inadequate in terms of their strength, namely in terms of their resistance to crack propagation. This lack is reflected in the notch sensitivity, the 3o brittleness break and occasionally in the catastrophic failure of molded or extruded parts. The tendency of polyamides to break, not ductile but brittle, significantly limits their commercial utility. A resin can be tested for its tendency to ductility 35 by the Izod impact strength test (ASTM test standard D-256-56). At the normal notch radius of 0.254 mm, polyhexa-methylene adipamide (nylon 66) shows an Izod-40 notched impact strength of about 0.5 J / cm in the dry form (i.e. dry, as obtained when deforming).

There is extensive prior art on improving the impact resistance of polyamides. A wide variety of additives have been added to polyamides, with some improvement in strength being achieved. 45 In GB-PS 998 439 e.g. describes a thermoplastic composition which contains a mixture of 50 to 99% linear polyamide and 1 to 50% olefin copolymer particles, the olefin copolymer having 0.1 to 10 mole percent acid groups. The patent describes many olefin co-50 polymers, but does not require that the olefin copolymers have a tensile modulus of 34 470 N / cm 2 or less. When the proportion of the copolymer is increased to 40 percent by weight, the notch sensitivity increases to about 55 2.5 J / cm, as described in Example 1 of the patent.

US Pat. No. 3,845,163 describes mixtures of 60 to 85 percent by weight of polyamide and an acidic olefin polymer in which the acid groups are derived from an α, β-ethylenically unsaturated carboxylic acid and at least 10% 60 of the acid groups have been neutralized by metal ions . The patent primarily relates to the strength of the weld seam, which has no particular relationship to the toughness of the mixture. The mixture described in the patent also exhibits an improvement in toughness with respect to the mass described in GB-PS 998 439. US Pat. No. 3,845,163 does not recognize that when mixtures with polyamides are added at lower concentrations

649566

Polymers can achieve improved strength, provided that at least one polymer with a tensile modulus of 34,470 N / cm 2 or less is present and the ratio of the tensile modulus of the polyamide to the tensile modulus of the polymer in question is greater than 10: 1.

US Pat. Nos. 3,388,186 and 3,465,059 describe polyamide compositions of high impact strength, which are sometimes higher than about 5.3 J / cm. These masses are graft copolymers which are produced from copolymers of ethylene. These copolymers have no sites that adhere to the polyamide via sites of the polyamide. Nor is it recognized that the tensile modulus of the ethylene copolymer is not higher than 34 470 N / cm 2 or that the particle size is important. Izod impact strength is also determined on samples held 3 days prior to testing in an atmosphere of 50% relative humidity as described in U.S. Patent No. 3,388,186. For some compositions, the moisture causes a sharp increase in the Izod impact value. This is shown in Table 1 on page 6 of GB-PS 998 439.

US Pat. No. 3,668,274 reports a moderately improved impact resistance of polycarbonamides, which is characterized by (A) a first elastomer phase made from copolymers or terpolymers and (B) a last thermoplastic stage in the form of a rigid phase, the residues reactive with amine, preferably carboxyl groups, are modified. The soft modifier is coated with a rigid layer, thereby negating the significant improvement in the strength of the polyamide that could be achieved by a copolymer as a modifier.

The invention now provides a multi-phase thermoplastic composition which no longer has the above disadvantages; said mass is characterized in the preceding claims 1 to 22.

The expression “essentially consisting of” means that in addition to the required polyamide base resin and the at least one polymer, other components may also be present in the solidified mass, provided that the essential properties of the solidified mass are not significantly impaired thereby.

The term "branched and straight-chain polymers" means that the polymers are not so strongly cross-linked that their modulus is higher than 34 470 N / cm2 or their melt index is so low that they cannot be distributed effectively.

The invention also provides a method for producing the solidified multiphase thermoplastic composition; said method is characterized in the preceding claim 23.

The polyamide base resin of the solidified compositions according to the invention is known per se and comprises the semi-crystalline and amorphous resins with molecular weights of at least 5000, which are commonly referred to as nylon. Such polyamides are described in U.S. Patents 2,071,250,2,071,251.

2 130 523.2 130 948.2 241 322.2 312 966.2 512 606 and

3,393,210. The polyamide resin can be made by condensing equimolecular amounts of a saturated dicarboxylic acid having 4 to 12 carbon atoms with a diamine having 4 to 14 carbon atoms. To achieve an excess of terminal amine groups over the terminal carboxyl groups in the polyamide, the diamine can be used in excess. Examples of polyamides are polyhexamethylene adipic acid amide (nylon 66), polyhexamethylene azelaic acid amide (nylon 69), polyhexamethylene sebacic acid amide (nylon 610), poly-hexamethylene dodecanedioic acid amide (nylon 612), the polyamides obtained by ring opening of lactams, such as polycaprolactam, polylauric acid, and polylauric acid ami-

noundecanoic acid and bis (p-aminocyclohexyl) methanode candic acid amide. It is also possible according to the invention to use polyamides which have been prepared by copolymerization of two of the abovementioned polymers or by terpolymerization s of the abovementioned polymers or their components, e.g. the copolymer of adipic acid, isophthalic acid and hexamethylenediamine. The polyamides are preferably linear and have melting points of more than 200 ° C. The mass can consist of 99 percent by weight of polyamide io; however, preferred compositions contain 60 to 99 percent by weight or a narrower range of 80 to 95 percent by weight of polyamide.

The mass can be solidified by mixing at least one polymer with the polyamide. The expression "at least one polymer" means a polymer or several polymers which are present together in the form of individual parts with sizes in the range from 0.01 to 3 n, preferably 0.02 to 1 (i, in the basic composition, see above) that the mixture of the polymers or at least one of the polymers 20 in the mixture meets the following requirements:

(a) it has spots attached to the polyamide matrix;

(b) it has, in the form in which it is added, a tensile modulus in the range from about 0.69 to 34,470 N / cm 2, preferably

25 from about 3.45 to 13 788 N / cm 2, and the ratio of the tensile modulus of the polyamide base resin to the tensile modulus of the at least one polymer is greater than 10: 1, preferably greater than 20: 1.

The polyamide is the coherent phase in the 3o mass, and the polymer acts as a white disperse phase that adheres to the polyamide base mass. The polymer can be an elastomer; however, it has been found that thermoplastic polymers that are not elastomers are also effective in the compositions according to the invention. 35 The polymers are branched or straight-chain and have a composition such that a crosslinking other than that which is brought about by reaction with the polyamide matrix is not necessary for their action; excessive networking can even be harmful 40.

Branched and straight-chain polymers which are suitable as a soft phase in particle form in the mixture correspond to the general formula (I)

45

A (a) B (b) e (c) D (d) E (e) F (f) G (g) H (h)

(I)

contain,

whose units selected from A to H can be arranged as desired, and whose tensile modulus is in the range from 0.69 to 34 470 N / cm2 and is less than one tenth of the tensile modulus of the polyamide resin P, the symbols A to H in the formula I mean the following units, of which only the unit D contains epoxy:

55 A a unit of the monomer ethylene,

B the unit CO,

C is a unit of monounsaturated monomer from the group consisting of

C]) a, ß-ethylenically unsaturated carboxylic acids with 3 to 60 8 C atoms, which are monounsaturated,

c2) monoesters of dicarboxylic acids belonging to the acids mentioned under Ci) with saturated alcohols having 1 to 29 C atoms,

c3) internal anhydrides of dicarboxylic acids belonging to the 65 acids mentioned under c,) and c4) vinylbenzoic acid and vinyl phthalic acid, units C of mono- and dicarboxylic acids belonging to acids mentioned under q) and of dicarboxylic acids mentioned under c2)

bonic acid monoesters can be in metal salt form, and units C of dicarboxylic acids belonging to the acids mentioned under q) and of dicarboxylic acid monoesters mentioned under c2) can be neutralized with caprolactam oligomers with amine end groups and a degree of polymerization of 6 to 24,

D is a unit of monounsaturated epoxy with 4 to 11 carbon atoms,

E is a unit as it results when a molecule of an aromatic sulfonyl azide from the group consisting of e) aromatic sulfonyl azides which are mono- or dicarboxylic acids having 7 to 12 carbon atoms,

e2) monoesters of dicarboxylic acids with 1 to 29 C atoms belonging to the acids mentioned under e ^ and e3) internal anhydrides of dicarboxylic acids belonging to the acids mentioned under e ^, azide nitrogen is removed, carboxyl groups of units E being in metal salt form can,

F is a unit of monounsaturated monomer from the group consisting of the monounsaturated acrylic and methacrylic esters with 4 to 22 C atoms, the monounsaturated vinyl esters of 1 to 20 C atoms, the monounsaturated vinyl ethers with 3 to 20 C atoms, the vinyl and vinylidene halides and the monounsaturated nitriles with 3 to 6 C atoms,

G is a unit of monounsaturated monomer from the group consisting of ethylene in which hydrogen is replaced by optionally substituted aryl which is free from acid groups or alkyl having 1 to 12 carbon atoms, vinylpyridine and vinylpyrrolidone,

H is a unit of straight-chain or branched-chain or cyclic monomer which has 4 to 14 C atoms and at least two unsaturated carbon-carbon bonds in the molecule, and the mole fractions (a) to (h) in which the units A to H are in the following areas:

(a) 0 to 0.95

(b) 0 to 0.3

(c) 0 to 0.5

(d) 0 to 0.5

(e) 0 to 0.5

(f) 0 to 0.99

(g) 0 to 0.99

(h) 0 to 0.99

and wherein the polymer of formula I contains at least one of components B, C, D and E, with the proviso that

that if A is present in addition to at least one of components B, C, D and E, at least one of components F, G and H is also present.

Components (a) to (h) are preferably present in the following mole fraction:

(a) 0 to 0.9,

(b) 0 to 0.2, in particular 0.1 to 0.2,

(c) 0.0002 to 0.2, in particular 0.002 to 0.05,

(d) 0.005 to 0.2, in particular 0.01 to 0.1,

(e) 0.0002 to 0.1, in particular 0.002 to 0.01,

(f) 0 to 0.98,

(g) 0 to 0.98 and

(h) 0 to 0.98.

At least one of components B, C, D and E is contained in all polymer systems. If A is present in addition to at least one of components B, C, D and E, min5 is 649566

at least one of the components F, G and H is available. A mixture of several polymers can also be used, provided that at least one of the components B, C, D and E is present in at least one of the polymers. 5 Since I and J are polymers that contain traps, the presence of B, C, D and E is not necessary in this case.

The polymer component of the solidified mass can be prepared by conventional copolymerization reaction or by a grafting reaction. Thus, B, C, D and E can be copolymerized with A, F, G and H, and C, D and E can be attached by a grafting reaction.

Examples of monomers C to H of the above general formula are:

15 C maleic acid, maleic anhydride, maleic acid monoethyl ester, metal salts of acidic monoethyl ester, fumaric acid, fumaric acid monoethyl ester, itaconic acid, vinyl benzoic acid, vinyl salts of fumaric acid monoethyl ester, with monoesters of maleic acid and fumaric acid to fumaric acid, e.g. Methyl, propyl, isopropyl, butyl, isobutyl, hexyl, cyclohexyl, octyl, 2-ethylhexyl, decyl, stearyl, methoxyethyl, ethoxyethyl, hydroxyethyl, etc .;

D methacrylic acid glycidyl ester, acrylic acid glycidyl ester, 25 allyl glycidyl ether, vinyl glycidyl ether, itaconic acid glycidyl ester, etc .;

EPthalic anhydride sulfonyl azide, methyl ester and monooctadecyl ester of phthalic anhydride sulfonyl azide, benzoic acid sulfonyl azide, naphthoic acid sulfonyl azide;

F methacrylic acid methyl ester, acrylic acid butyl ester, 35 acrylic acid ethyl ester, vinyl acetate, methyl vinyl ether, zinc methacrylate, acrylonitrile, R ester of acrylic acid and methacrylic acid, R vinyl ether, vinyl benzoate, vinyl naphthoate, vinyl ester of R acids, where R has up to 18 carbon atoms, where R has up to 18 carbon atoms, Vinyl chloride, vinylidene fluoride, etc .; 40 G styrene, propylene, isobutylene, vinyl naphthalene, vinyl pyridine, vinyl pyrrolidone, mono-, di- and trichlorostyrene, R'-styrene, where R 'has 1 to 10 carbon atoms, butene, hexene, octene, decene, etc .; and

H hexadiene, norbornadiene, butadiene, isoprene, divinyl, 45 allyl styrene etc.

Polymers suitable for solidifying the polyamide compositions are the following polymers with alternately or predominantly randomly distributed monomer units:

Zinc salt of ethylene / isobutyl acrylate / meth-50 acrylic acid; Ethylene / acrylic acid methyl ester / monoethyl ester of maleic anhydride and 0 to 100% neutralized zinc, sodium, calcium, lithium, antimony and potassium salts thereof; Ethylene / acrylic acid methyl ester / mono-ethyl ester of maleic anhydride, partially neutralized with an oligomer of caprolactam with terminal amine groups; Mixtures of ethylene / acrylic acid isobutyl ester / methacrylic acid and ethylene / acrylic acid methyl ester / monoethyl ester of maleic anhydride and zinc salts thereof; Ethylene / acrylic acid methyl ester / methacrylic acid 60 and zinc salts thereof; Ethylene / vinyl acetate / methacrylic acid and zinc salts thereof; Ethylene / methacrylic acid methyl ester / methacrylic acid and zinc salts thereof; Ethylene / vinyl acetate / carbon monoxide; Mixtures of ethylene / vinyl acetate / carbon monoxide and a zinc salt of ethyl-65 len / acrylic acid isobutyl ester / methacrylic acid;, Mixtures of ethylene, vinyl acetate and a zinc salt of ethylene / acrylic acid isobutyl ester / methacrylic acid; Mixtures of ethylene / isobutyl acrylate and a zinc salt of

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Ethylene / isobutyl acrylate / methacrylic acid; Mixed, optionally added polymers were mixed in.

cal of ethylene / acrylic acid and ethylene / vinyl acetate; that are. For polymers made of ethylene, propylene and an ethylene / isobutyl acrylate / carbon monoxide; Ethylene diene are effective molecular weights that a melting

/ Stearyl methacrylic acid / carbon monoxide; Ethylene / dex from 0.5 to 400 g / 10 min and more correspond

N-butyl acrylic acid / carbon monoxide; Ethylene / meth- 5 according to ASTM test standard D 1238, but at 280 ° C and a

2-ethylhexyl acrylate / carbon monoxide; Ethylene / ner total load with 2160 g. The multitude of used

Methyl vinyl ether / carbon monoxide; Ethylene / vinyl acetate / baren polymers can have a melt index of more than

Maleic anhydride; Have ethylene / vinyl acetate / monoethyl 0.1 to 1000; preferably the melt index is ester of maleic anhydride; Ethylene / vinyl acetate / but in the range of 0.5 to 100.

Methacrylic acid glycidyl ester; Ethylene / propylene / hexadiene 10 possible embodiments of the inventive

(1,4) graft maleic anhydride; Mixtures of ethylene / mass are the following 18 formulations:

Propylene / hexadiene (1.4) and ethylene / maleic acid - multiphase, thermoplastic mass in which the part

drid; Ethylene / propylene / norbornadiene / hexadiene (1.4) - T have a size in the range of 0.02 to 1 (in.

graft-benzoic acid sulfonyl azide; Ethylene / Propylene / Hexa- - Multi-phase, thermoplastic mass, thereby

diene (1,4) graft phthalic anhydride sulfonyl azide; Gemi- 15 indicates that the tensile modulus of the polymer of formula I

see from ethylene / propylene / hexadiene (1.4) and ethylene / from 3.45 to 13 788 N / cm2.

Propylene / hexadiene (1,4) graft maleic anhydride; - Multi-phase, thermoplastic mass, thereby ethylene / propylene / hexadiene- (1,4) -graft-maleic acid- indicates that the melting point of the polyamide resin P hydride, neutralized with an oligomer of caprolactam, is above 200 ° C.

with terminal amine groups; Ethylene / Propylene / Hexa- 20 - Multi-phase, thermoplastic mass, thereby ge- dien- (1, 4) / Maleic anhydride, neutralized with Zinkabie- indicates that the polyamide resin P is a straight or vert; Ethylene / propylene / hexadiene (1,4) graft fumaric acid; is two-chain polyamide.

Ethylene / propylene / hexadiene (1.4) / norbornadiene graft - multiphase, thermoplastic mass, thereby

Maleic anhydride; Ethylene / propylene / hexadiene- (1.4 / indicates that the polyamide resin P is a polyamide made of a

Norbornadiene graft monoethyl ester of maleic acid dicarboxylic acid with 4 to 12 carbon atoms and a

hydride; Ethylene / propylene / hexadiene (1,4) / norbornadiene diamine with 4 to 14 carbon atoms.

graft fumaric acid; Ethylene / Propylene / Hexadiene-1,4) / - Multi-phase, thermoplastic mass, thereby

Methacrylic acid glycidyl ester; Ethylene / propylene / hexa- indicates that the polyamide resin is polycaprolactam.

dien- (1, 4) / norbornadiene-graft-phthalic anhydride sulfide - multiphase, thermoplastic mass, thereby

fonylazide; Mixtures of ethylene / propylene / hexadiene- (1,4) 30 indicates that they contain at least one colorant in one and ethylene / monoethyl ester of maleic anhydride; Concentration up to 5.0 percent by weight, based on the

Mixtures of ethylene / propylene / hexadiene (1.4) and ethyl mass contains.

len / maleic acid monobutyl ester; Mixtures of ethylene / - multi-phase, thermoplastic mass, thereby ge-propylene / hexadiene (1,4) and ethylene / maleic acid characterizes that they glass fibers in a concentration up to drid; Mixtures of butadiene / acrylonitrile and styrene / 35 50 weight percent, based on the mass, contains. Maleic anhydride; Mixtures of styrene / butadiene and - Multi-phase, thermoplastic mass, thereby ethylene / maleic anhydride; Isobutylene / Isoprene- indicates that they are fibrous or powdery mineral filler-graft-phthalic anhydride-sulfonyl azide; Poly (iso and reinforcing agents in a concentration of up to 50 Ge-butylene) graft phthalic anhydride sulfonyl azide; Percentage by weight, based on the mass, contains.

see from ethylene / propylene / hexadiene (1,4 / norbornadiene 40 - multiphase, thermoplastic mass, thereby

and styrene / maleic anhydride; Isoprene / phthalic acid indicates that it is a stabilizing agent in an amount of hydride; Mixtures of natural rubber and ethylene / mono to 1.0 percent by weight, based on the polyamide resin,

ethyl ester of maleic anhydride; Acrylic acid butyl ester / contains.

Fumaric acid monoethyl ester; Acrylätäthylester / Fumar- - Multi-phase, thermoplastic mass, thereby

acid; Epichlorohydrin / ethylene oxide; Mixtures of ethylene / 45 indicates that the polymer of formula I is a copolyme

Propylene and ethylene / monoethyl ester of maleic acid anise- rate from ethylene, propylene and hexadiene- (1,4), which is

hydride; Ethylene / propylene graft phthalic anhydride sol monomers from the group fumaric acid, maleic acid,

fonylazide; Ethylene / propylene / 5-ethylidene norbornene (2) - maleic anhydride and fumaric acid and maleic acid

graft fumaric acid; Ethylene / propylene / dicy monoalkyl esters with 1 to 3 carbon atoms in the alkyl

clopentadiene graft maleic acid monoethyl ester; Ethylene / so group is grafted and after grafting one

Propylene / 5-propenylnorbornene (2) graft maleic acid melt index from 0.1 to 100 g / 10 min, determined according to the hydride; Ethylene / propylene / tetrahydroinden graft fumar ASTM test standard D 1238 at 280 ° C and a total load

acid; Ethylene / propylene / hexadiene (1,4) / 5-Ethylene standard of 2160 g.

boron- (2) graft fumaric acid. - Multi-phase, thermoplastic mass, thereby

The improvement in the ductility of a mass, 55 characterizes that the polymer of the formula I is a tetrapoly

is characterized by a higher value of the Izod impact impact meter made of ethylene, propylene, hexadiene (1,4) and norborna-

ability, is approximately proportional to the concentration of the diene- (2.5), which is formed with a monomer from the group Fu

Adhesion points in the polymer component as well as the melt viscosic acid, maleic acid, maleic anhydride and fumarate

cosity, which is a measure of the molecular weight, and the acid and maleic acid monoalkyl esters with 1 to 3 carbon

Molecular weight distribution within the limits of an ef- 60 atoms of the alkyl group is grafted and after the fective dispersion. If the sticking points in high concentration plugs have a melt index of 0.1 to 100 g / 10 min.

in general, it is generally possible to use two poly-tunings according to ASTM test standard D 1238 at 280 ° C and a

to mix with each other, namely one with a total load of 2160 g.

oil carrier and the other as a diluent. The Mi- - Multi-phase, thermoplastic mass according to

can be done by the polymers separately 65 g formulation, characterized in that the polymer

or mixed together with the polyamide with which the amide resin P is polyhexamethylene adipic acid amide, or that there would be that the polymer containing the adhesion points with which the polyamide resin P is polycaprolactam.

Polyamide base resin must not be mixed before - Multi-phase, thermoplastic mass, thereby

7 649 566

characterizes that the polymer of formula I is a copolyme-multi-phase, thermoplastic mass is characterized by res with random distribution of the monomer units, which is characterized in that in a closed system from units of ethylene, units of acrylic acid methyl- 60 to 99 weight percent polyamide resin with a Zah- or ethyl ester in a concentration of 0.0025 to len average molecular weight of at least 5000 and

0.077 mol per 100 g of the polymer units present, 5-40 to 1 percent by weight of the monoalkyl ester of an ethene-1,2-dicarboxylic acid defined in claim 1, the straight or branched chain polymer of formula I in the alkyl group of which has 1 to 6 carbon atoms , and at a temperature which is 5 to 100 ° C. above the melt concentration of 0.64 to 0.80 mol per 100 g of the copolyme point of the polyamide resin, and the CO units present, the Ethene-1,2- the polymer of formula I in the polyamide resin by dicarboxylic acid monoalkyl ester units to 0 to 100% lithium shear in a particle size in the range from 0.01 to um, sodium, potassium, calcium or zinc salt neutral 3.0 (distributed and adhered to the polyamide resin and which brings a total load of at 190 ° C.

2160 g, according to ASTM test standard D 1238, Condition G, bes- In the present text, various unified melt index for the non-neutralized copolymer units for the physical sizes of the thermoplastics are in the range from 0.3 to 100 g / 100 min and for the neutralized 15 turns; the conversion between the sizes per copolymer is in the range of 0.04 to 100 g / 10 min. but always according to the following equations:

- Multi-phase, thermoplastic mass according to the previous formulation, characterized in that the Mo- 1 kg or kp = 9.81 N;

noalkyl ester essentially from maleic acid monoethyl ester 1 N • m = 1 J.

consists. 20th

- From the above description it follows that the past formulation, characterized in that the most diverse polymer for solidifying polyamides amide resin P is polyhexamethylene adipic acid, or that this can be used, and a very large number of polyamide resin P is polycaprolactam. Combinations are suitable for this purpose. It is therefore

- Multi-phase, thermoplastic mass with a concentration not surprising that the limits of the effectiveness of a concentration of the particles T of 2 to 40 percent by weight, especially components of the mass, are subtracted from other components on the polyamide resin P and the particles T, as a result hangs. For example, the lower concentration limit indicates that the numerical value of the effective detention point expressed in J / cm, e.g. Maleic anhydride, according to ASTM D 256, the Izod impact strength, apparently, is lower than that of a less effective mass in the dry state, such as that at the point of adhesion, such as methacrylic acid. Likewise, the ratio mung is obtained, at least between terminal amine groups and carboxyl groups in the base mass, the relative effectiveness of various i) influence the value 0.533 • (B + 0.2 Q) adhesion sites of the at least one polymer. Po-

or ii) the value 0.533 • (B + 2 + 0.5 (C2-10)) polymers and polymer mixtures of lower modulus are generally more effective than polymers or polymer mixtures in or iii) the value 0.533 ■ (B +12) 35 of higher modulus and may have lower detention points, the minimum value i) in the event that the concentration concentrations are valuable. The equation for the relationship of the particles T is in the range of 2 to 10 weight percent between the Izod impact strength and the concentration, the minimum value ii) in the event that the concentration of the polymer is only on polymers with the concentration of the particles T in the range from 10 to 30 percent by weight combination of adhesion, modulus and partial percentage and the minimum value iii) in the event that the cone size is applicable. It should also be noted that the ratio of the particles T here in the range from 30 to 40% by weight of the mixtures described are only effective if their concentration is that components in the same individual particles in the polymer

B the numerical value of the Izod notch amide base mass expressed in J / cm is jointly available. The strengthened ther impact strength of the polyamide resin means P, and Q and 45 moplastic mass, however, more than such a poly-C2 can contain the numerical value in percent by weight, based on the merge mixture.

Polyamide resin P and the particles T, expressed concentration of the particles T, mean. The masses according to the invention can be

- Multi-phase, thermoplastic composition according to conventional additives, such as stabilizers and oxidation-retardant formulation, characterized in that the Izod so gerer, means against heat decomposition and decomposition by impact strength of the mass of the particles T higher than ultraviolet light, lubricants and mold release agents , Dye with-4.22 J / cm when the concentration is 5 to 20 percent by weight, such as dyes and pigments, is fibrous and powdery. Fillers and reinforcing agents, nucleating agents, plasticizers

It is believed that the polymer of the plasticizers, etc., are modified.

Phase only at the interface or surface of the two ss. The stabilizers can adhere to the masses phases at any stage on the polyamide matrix. The mechanism of this adherence added to the production of the thermoplastic compositions has not yet been elucidated; the. Preferably, the stabilizers are added at an early stage, possibly due to bonding, to prevent the decomposition that begins in energy between the hydrogen bonding from occurring before the mass can be protected. Sol and the covalent bond vary. 60 stabilizers must be compatible with the mass.

Oxidation retarders and heat stabilizers,

The melt index of the thermoplastic composition is in the range from 0.01 to 200 g / min, which can be set for the thermoplastic compositions according to the invention, determined according to the ASTM, are those which generally belong to test standard D-1238 at 280 ° C and one Load with 2160 g. Polymers are added, e.g. Halides of metal-Preferably the melt index is 0.1 to 150 g / min. Since 65 oils from group I of the periodic table, e.g. Sodium, Ka - the viscosity is highly sensitive to shear, the lium, lithium, with copper (I) halides, e.g. Chloride, Bro masses according to the invention good for extrusion. mid, iodide, sterically hindered phenols, hydroquinones,

The process for the preparation of the various substituted representatives of these groups and combinations according to the invention

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Nations of the same in concentrations up to 1% by weight, the molecular weight either in the melt or at 1%, based on the weight of the polyamide. ner elevated temperature below the melting point of the

UV stabilizers can also be those which increase polyamides (in the solid phase). For example, those generally added to polymers will be used in amounts up to 2.0 mass after melt blending either (1) for a time weight percent based on the polyamide. At room for up to one hour at temperatures around 10 to 10 ° C for UV stabilizers are various substituted 40 ° C above the melting point, under pressure of resorcinols, salicylates, benzotriazoles, benzophenones and the like - about 1 to 25 mm Hg abs. kept in the melt or (2) the same. for a period of at least 2 hours after the

Suitable lubricants and mold release agents, e.g. Stearic acid, stearic alcohol, stearic acid and polyamide are more solid in cutting, cooling and drying at an increased temperature of up to 1.0% by weight of the thermoplastic composition, which are set at least 15 ° C below the melting temperature Phase reamide in an inert gas stream; the following can also be added: organic color retention. Solid phase polymerization is used in U.S. Patents such as nigrosine, etc., pigments, e.g. Titanium dioxide, Cadmi-3 821 171.

sulfide, cadmium sulfide selenide, phthalocyanines, ultramarine blue, carbon black, etc .; Fibrous and powdery fillers and 15 The solidified thermoplastic materials can after reinforcing agents such as carbon fibers, glass fibers, amor- conventional deformation methods, such as those for the manufacture of silica, asbestos, calcium silicate, aluminum silicate, thermoplastic products such as molded parts, magnesium carbonate, kaolin , Chalk, powdered quartz, extrusions, e.g. Pipes, foils, skins, fibers and mica, feldspar etc. in quantities of up to 50% by weight oriented fibers, laminates and wire coatings, other mass, nucleating agents such as talcum, calcium fluoride, etc. are used for a wide variety of consumer goods, sodium phenylphosphinate, aluminum oxide and fine parts are deformed.

total polytetrafluoroethylene etc., plasticizers in amounts up to. The masses according to the invention are characterized by about 20 percent by weight of the mass, e.g. Phthalic acid dioctyl - through an extraordinary combination of property esters, phthalic acid dibenzyl esters, phthalic acid butylbenzyl esters, among which the excellent toughness hydrocarbon oils, Nn-butylbenzenesulfonamide, o- and 25 shafts in view of the amount of at least one polyme-p-toluamidethenesulfonate ( , which is contained in the polyamide matrix, especially pigments) can be remarkable in amounts up to about 5.0% by weight. The unusually high tenacity, based on the mass, can be added. leads to greater ductility, less sensitivity

The solidified compositions according to the invention can, in terms of scratching and molded notches, form a closed system by melt mixing a polymer and to a significantly reduced susceptibility to catalytic and at least one polymer to a uniformly strophic failure compared to the previous ones known mixture in a multi-screw extruder, such as masses, from which moldings are made. Injection molding of a Werner & Pfleiderer extrusion press, which generally consists of 2 parts, often fluctuate in thickness and can have up to 5 kneading sections and at least one section with scratches, molded notches of varying radius and reversed thread pitch, formed around a high shear 35 Have tensions. Furthermore, orienting or other conventional plasticizing effects can cause a ductility variation within the device, such as a Brabender mill, a Banbury molded article. Maintaining high mill or the like can be made. The mixture of uniform values of the Izod impact strength through the can, but also through joint precipitation from solution of the whole molded body, characterizes the improved or by mixing or dry mixing of the components - resistance of the compositions according to the invention and subsequent melt extrusion of the dry against brittle fracture . The masses have such toughness, can be mixed. that little changes in processing conditions

The masses described in the examples will not result in any significant fluctuations in the toughness of a Werner & Pfleiderer twin-screw extruder.

poses. The constituents are mixed dry and in the “In the examples below, if nothing is stated in vacuum at temperatures from 5 to 100 ° C. above the melting point, the percentages relate to the weight, point of the base resin, preferably at 310 ° C or the polyamide matrix and the polymer or poter, extruded. Even higher temperatures are mixed with dryers after they have been used in the following. The extrudate, which has been weighed at the appropriate amounts at temperatures and circulated in an opaque polyethylene bag less than 20 ° C above the melting point. The mixture is what is an indication of the presence of two phases is then in a 28 mm Werner & Pfleiderer extrusion press, is cooled in a water bath, cut, mixed in vacuo, in the hopper under nitrogen and the Va -dry and deformed into test pieces. You can use natural vacuum opening under a vacuum of about 63 to 75 cm with many process changes. It can be held up. The extrusion cylinder temperatures will be partial, to produce a concentrate of the solidified thermoplastic mass approximately at the melting point of the polyamide base material. This is done by mixing the (± 10 ° C) so that temperatures of the melt polyamide in higher concentrations, based on the obtained, which are 5 to about 100 ° C above the melting point of the weight of the total mass, e.g. up to about 50% by weight.

percent with the at least one polymer. Further poly- The bead emerging from the extrusion press is mixed with amide, the mass is cooled to the desired water, chopped and over-concentrated before shaping, e.g. to obtain a solidified mass, which dried 1 to night at 80 ° C in a vacuum. Contains at least one polymer with the aid of 20 percent by weight. 85 cm3 and 170 cm3 injection molding machines are

It has proven to be expedient to increase the molecular temperature of the melt, which is 10 to 30 ° C. above the weight of the solidified thermoplastic mass at its melting point of the polyamide base mass. For example, a blend of 65 by 12.7mm x 12.7cm x 3.18mm is molded. The Verfor-a low molecular weight polyamide, e.g. 5000 mung temperature is about 90 ° C with rapid injection up to 15,000, and at least one polymer in one of the tongues and a deformation cycle of 20/20 or 20/30 (Se-

plasticizers described above are manufactured and announce forward movement of the die / second breastfeeding

9

649 566

was standing). The shaped rods are examined in the dry form using the following test methods:

Izod impact strength: ASTM test standard D-256-56 at each end

Tensile strength: ASTM test standard D-638-58T Elongation at break: ASTM test standard D-638-58T Bending module: ASTM test standard D-790-58T Tensile modulus of the base materials: ASTM test standard D-638-58T (dry)

Tensile modulus of the polymers: ASTM test standard D-882 (at 50% relative humidity)

Melt index: ASTM test standard D-1238-73, Condition G (unless otherwise stated)

Particle size: electron micrographs of surfaces cut or broken with the microtome.

Details of the polyamide matrix and the polymers used with the polyamide matrix can be found in Tables I-A and I-B, respectively. The abbreviations used below are explained in Table II.

Table I-A polyamide matrix

1. polyamide 66; inherent viscosity about 1.25 ± 0.10, determined on 0.5 g per 100 ml of m-cresol at 25 ° C; COOH: 65-73 eq / 106 g; NH2: 47-53 eq. / 106 g.

2. polyamide 66; inherent viscosity about 0.68, determined on 0.5 g per 100 ml m-cresol at 25 ° C .; COOH: about

110 eq / 106 g; NH2: about 85 eq / 106 g.

3.60% polyamide 66 according to 1

20% polyamide 66; inherent viscosity about 1.95 ± 0.10, determined on 0.5 g per 100 ml m-cresol at 25 ° C. 4.40% polyamide 66 according to 1 40% polyamide 66 according to 3.

5,100% polyamide 66; inherent viscosity about 1.95 ± 0.10, determined on 0.5 g per 100 ml m-cresol at 25 ° C.

6. polyamide 66; inherent viscosity about 1.25 ± 0.10, determined on 0.5 g per 100 ml of m-cresol at 25 ° C; COOH:

5 34-46 eq / 106 g; NH2: 73-93 eq./ lO6 g.

7. polyamide 66; inherent viscosity about 0.98, determined on 0.5 g per 100 ml m-cresol at 25 ° C; COOH: about

44 eq / 106 g; NH2: about 94 eq / 106 g.

8. polyamide 612; inherent viscosity about 0.95 ± 0.10,

io determined at 0.5 g per 100 ml m-cresol at 25 ° C.

9. polyamide 612; inherent viscosity about 1.17 ± 0.10, determined on 0.5 g per 100 ml m-cresol at 25 ° C.

10. "Plaskon 8200" - polycaprolactam from Allied Chemical Co.

15 11. "Hüls" nylon 12; inherent viscosity about 1.20, determined on 0.5 g per 100 ml m-cresol at 25 "C.

12. "Rilsan" nylon 11; inherent viscosity about 1.17, determined on 0.5 g per 100 ml m-cresol at 25 ° C., available from Aquitane Chemicals, Inc.

2o 13. Copolyamide made of 80% nylon 66 and 20% polycaprolactam; inherent viscosity about 1.33, determined on 0.5 g per 100 ml m-cresol.

14. "Trogamid T" poly (trimethylhexamethylene terephthalic acid amide) (Dynamite Nobel); inherent viscosity, for example

25 0.95, determined on 0.5 g per 100 ml of m-cresol at 25 ° C; COOH: about 59 eq / 106 g; NH2: about 57 eq / 106 g.

15. PACM-12 polyamide from bis (p-aminocyclohexyl) methane and dodecanedioic acid; inherent viscosity about 0.95, determined on 0.5 g per 100 ml m-cresol at 25 ° C; COOH: about

30 57 eq. 106 g; NH2: about 60 eq / 106 g.

16. "Plaskon 8252" (modified polycaprolactam), available from Allied Chemical Co.

Table I-B polymers

example

Poly-chemical meres composition, weight ratio

Melt index, g / 10 min before® after neutralization

1-12.16,

1

E / IBA / MAA

35

about 1

115-118,123

78/12/10

Comparison B-G

2nd

E / MAA 90/10

approximately ]

Comparison H, I

3rd

E / MA 63/67

4.9

Comparison J

4th

E / MA 45/55

1.8

13 (a)

5

E / MA / MAME 42/54/4

4.0

14.15, 17-22.36

5

E / MA / MAME 42/54/4

4.0

23

5

E / MA / MAME 42/54/4

4th

24 <a>

5

E / MA / MAME 42/54/4

4th

0.17

25 (a)

5

E / MA / MAME 42/54/4

4th

0.14

26 (a)

5

E / MA / MAME 42/54/4

4th

0.41

27th

5

E / MA / MAME 42/54/4

4th

16.2

28

1

E / IBA / MAA 78/12/10

35

29

1

E / IBA / MAA 78/12/10

35

(a) Contains tris (mixed. mono- and dinonylphenyl) phosphite ["Polyguard"] and 4,4'-bis (a, a'-diphenylamine) ["Naugard 445"] manufactured by Uniroyal.

(b) ASTM test standard D 1238, Condition E.

649 566 10

Table I-B (continued)

Neutralization data

Example% neutra-neutrali method Temp., Time,

sation- ° C min medium

1-12.16,

115-118.123 Comparison B-G Comparison H, I Comparison J 13 (a)

14.15, 17-22.36 23 24 «

25 «

26 «

27th

28

29

* Degree of polymerization 7.5

72 72

Zn Zn

100

Zn (OAc) 2

12

HMD

15.2 cm grinder

170

20th

100

Zn (OAc) 2

15.2 cm grinder

170

18th

100

Zn (OAc) 2

15.2 cm grinder

170

13

50

Zn (OAc) 2

15.2 cm grinder

170

13

25th

OHgomeres *

15.2 cm grinder

225

20th

25th

Zn (OAc) 2

15.2 cm grinder

170

20th

Table I-B (continued)

example

Poly-chemical

Melt index, g / 10 min before (b) after

meres

Composition,

neutralization

Weight ratio

30th

1

E / IBA / MAA 78/12/10

35

31

1

E / IBA / MAA 78/12/10

35

32

1

E / IBA / MAA 78/12/10

35

33

1A

E / IBA / MAA 74/20/6

41

39.4

34

1A

E / IBA / MAA 74/20/6

41

12.4

35

1A

E / IBA / MAA 74/20/6

41

3.2

Comparison K

1A

E / IBA / MAA 74/20/6

41

0.8

36

5

E / MA / MAME 42/54/4

4th

-

37

5

E / MA / MAME 42/54/4

4th

3.4

38

5

E / MA / MAME 42/54/4

4th

0.6

39

5

E / MA / MAME 42/54/4

4th

0.2

40

5

E / MA / MAME 42/54/4

4th

0.08

41

5

E / MA / MAME 42/54/4

4th

0.04

Comparison L

5

E / MA / MAME 42/54/4

4th

0.02

42

5

E / MA / MAME 42/54/4

4th

43 (a)

5

E / MA / MAME 42/54/4

7.1

0.18

Table I-B (continued)

Neutralization data Example% neutral-neutralization method

Temp., Time, ° C min

30th

50

Zn (OAc) 2

15.2 cm grinder

170

20th

31

71

ZnO conc.

Extrusion press

280

3rd

32

100

Zn (OAc) 2

15.2 cm grinder

170

20th

33

50

Zn (OAc) 2

15.2 cm grinder

150

20-

34

75

Zn (OAc) 2

15.2 cm grinder

150

10th

35

100

Zn (OAc) 2

15.2 cm grinder

150

15

Comparison K

125

Zn (Oac) 2

. 15.2 cm grinder

150

20th

36

0

-

-

37

10th

Zn (OAc) 2

15.2 cm grinder

170

20th

38

25th

Zn (OAc) 2

15.2 cm grinder

170

20th

39

50

Zn (OAc) 2

15.2 cm grinder

170

15

40

75

Zn (OAc) 2

15.2 cm grinder

170

10th

41

100

Zn (OAc) 2

15.2 cm grinder

170

10th

Comparison L

a.i.

125

Zn (OAc) 2

15.2 cm grinder

170

7

HZ

43 «

100

LiOAc

15.2 cm grinder

150

15

11

649 566

Table I-B (continued)

Example poly-chemical meres composition, weight ratio

Melt index, g / 10 min before (b) after neutralization

44 <a)

5

E / MA / MAME 42/54/4

7.1

2.44

45 (a)

5

E / MA / MAME 42/54/4

4th

46 «

5

E / MA / MAME 42/54/4

5.5

18.64

47 <a>

5

E / MA / MAME 42/54/4

7.6

41.5

48 (a)

5

E / MA / MAME 42/54/4

3.4

49 «and

1

(see 1)

3.4

0

50 «

5

(see 5)

51

5

3.4

52

5

53

5

54

6

E / IBA / MAA 60/37/3

3rd

55 (a)

7

E / MA / MAA 47/48/5

13

56

8th

E / MA / MAA 70/25/5

57

9

E / VA / MAA 66/29/5

102

58 «

10th

E / MA / MAA 60/36/4

5.1

59

11

E / MA / MAA 80/10/10

29

3.34

60

11

E / MA / MAA 80/10/10

10th

0.86

61

12

E / VA / MAA 75/18/7

30th

Table I-B (continued) Example

44 «

4500 460 »

47 (a)

48 «

49 wound 50 «

51

52

53

54 55 «

56

57 58 «

59

60

61

Neutralization data% neutral- neutralized method

100 100 100

-20

100

75 75 75 75 100 75 75 75

station medium

KOH

NaOH

Sb203

K stearate

Zn abietat

Zn (OAc) 2

Zn (OAc) 2 Zn (OAc) 2 Zn (OAc) 2 Zn (OAc) 2 Ca (OAc) 2 Zn (OAc) 2 Zn (OAc) 2 Zn (OAc) 2

15.2 cm mill 15.2 cm mill 15.2 cm mill 15.2 cm mill

15.2 cm mill 15.2 cm mill 15.2 cm mill 15.2 cm mill 15.2 cm mill 15.2 cm mill 15.2 cm mill Extruder 1 pass

Temp., Time, ° C min

150

150 80

15.2 cm mill 150

150 150 150

150 150 150

15

15 10

10th

15 5 15

15 15 15

649 566

12

Table I-B (continued)

Melt index, g / 10 min

Example poly-chemical before meres composition, neutralization

Weight ratio

62

12

E / VA / MAA 75/18/7

30th

63

13

E / MMA / MAA 74/20/6

64

13

E / MMA / MAA 74/20/6

Comparison M

14

E / VA 67/33

38-48

Comparison N

15

E / VA 60/40

45-70

65,67,68

16

E / VA / CO 66/24/10

35

66

17th

E / VA / CO 61/28/11

25th

69

1

(see 1)

18th

E / VA / CO 66/24/10

-

70

1

(see 1)

19th

E / VA 60/40

-

71

1

(see 1)

20th

E / IBA 80/20

-

72

1

(see 1)

21st

E / VA (67/33

-

73

15

(see 15)

22

E / AA 80/20

-

74

23

E / IBA / CO 57/34/9

-

75

24th

E / SMA / CO 67/20/13

5

Table I-B (continued)

example

62

63

64

Comparison M comparison N 65.67.68 66

69

70

71

72 Ti

74

75

Neutralization data% neutra- neutral- method temp., Time,

lized

75 75

station medium

Zn (OAc) 2

Zn (OAc) 2

15.2 cm mill 150

Extrusion press 1 pass min

15

13

649566

Table I-B (continued)

Melt index, g / 10 min

example

Poly

Chemical before® after

mères

Composition,

neutralization

Weight ratio

76

25th

E / nBA / CO 71/19/11

30th

77

26

E / 2EHMA / CO 57/33/9

100

78

27th

E / MVE / CO 62/23/15

345

79

28

E / VA / MAnh 62/33/5

290

80

29

E / VA / MAME 70/28/2

40

81

30th

E / VA / GMA 67/28/5

37

82

31

E / EA / MAME / EDMA

21/76/2 / 0.2

-

83

32

E / P / hexadiene- (1,4) / norbornadiene- (2,5) -g-l, 7% MAnh

(70/23 / 6.75 / 0.25

84

33

EPDM-A + E / MAnh 89 / 111.7% MAnh in a mixture

85

34

MAME-g-EPDM-C 7% MAME in the extrusion press

set

86

35

BASA-g-EPDM-C 2.2% BASA

87

36

PASA-g-EPDM-B 1.0% PASA

88.90

37

MAnh-g-EPDM-B + EPDM-B0.6% MAnh im

mixture

89

38

Caprolactam-Oligomeres-j

-MAnh-g-EPDM-B, 1.5%

MAnh

91

39

MAME-g-EPDM-E + Zn-abietate, 0.7% MAnh

92

40

FA-g-EPDM-D, extruded with 2% FA

93

41

FA-g-EPDM-E 1% FA

94

42

MAnh-g-EPDM-E 1.1% MAnh

Table I-B (continued)

Melt index,

example

Poly

Chemical before® after

mères

Composition, neutralization

Weight ratio

95

43

MAnh-g-EPDM-E 1.4% MAnh

96

44

2% norbornadiene anhydride-g-EPDM-E (2% to the strand

press added)

97

45

4% norbornadiene anhydride-g-EPDM-E (4% to the strand

press added

98

46

EPDM-B + E / MAME (92/8) 3% MAME in a mixture

99

47

EPDM-B + E / MAME (91.5 / 8.5) 1.5% MAME in

mixture

100

48

EPDM-B + E / MAME (92/8) 3% MAME in a mixture

101

49

EPDM-B + E / BuH maleate (87/13) 3% BuH maleate

mixture

102 **

50

MAnh-g-EPDM-E * 1.3% MAnh

103

51

E / P / Hexadiene- (1.4) / Norbornadiene- (2.5) -g-l, 7% MAnh

(70/23 / 6.75 / 0.25)

104

52

BAN + S / MAnh3 / l 1% MAnh in a mixture

Comparison 0

53

BAN

105

54

SBR + E / MAnh (89/11) 1.1% MAnh in the mixture

106

55

2% PASA-g-butyl rubber

107

56

2% PASA-g isobutylene rubber

108

57

EPDM-E + SMAnh (5/1) 1.7% MAnh in the mixture

109

58

Isoprene rubber + E / MAME (90/10) 1% MAME in

mixture

110

59

Natural rubber + E / MAME (90/10) 1% MAME in

mixture

* 1% sterically hindered phenol as an antioxidant («Ethyl 330»).

** See page !

? .

649 566

14

Table I-B (continued)

Melt index,

g / 10 min

example

Poly

Chemical before® after

mères

Composition, neutralization

Weight ratio

Comparison P

60

Natural rubber

111

61

EA / FA 96/4

Comparison Q

62

EA / FAME / EDMA 95/4/1

112

63

nBA / FAME 96/4

113

64

EP + E / MAME (90/10) 2% MAME in a mixture

114

65

1% PASA-g-EP

115-118

1

(see 1)

Comparison R, S

119

66

FA-g-EPDM-E about 1.4% FA

120-122 **

67

E / MA / MAME 43/53/4

123

1

(see 1)

124

68

Polyurethane elastomer

125-126.128,

66

FA-g-EPDM-E about 1.4% FA

132,135,137-141,

Comparison CC,

152-163

127

69

Ethylene oxide / epichlorohydrin rubber + Fe203 (5%)

129

70

EPDM-B 1% g monoethyl PASA

130

71

EPDM-B 2% g monooctadecyl PASA

131.134

1

(see above)

133.136

5

(see above)

142

22

72

E / MA 46/54

143

66

73

EPDM-E

** See page 8.

Table I-B (continued)

Melt index, g / 10 min

Example poly-chemical before meres composition, neutralization

Weight ratio

Comparison Z,

AA,

66

145.146

74

Polyethylene

1.2

144,147,148

66

149, Vergi. BB

75

Polyethylene

1.9

Comparison DD

76

FA-g polyethylene, 0.6% FA

150

77

FA-g-EPDM-E, 0.5% FA

151

66 78

Butadiene rubber

Table I-B (continued)

example

% neutralized

Neutralization data Neutralization method

Temp., Time, "C min

102

120-122

100 Zn (OAc) 2 15.2 cm mill 150 15

100 Zn (OAc) 2

15

649566

The polymers 1, 2, 6 to 13 and 28 to 31 are produced according to US Pat. No. 3,264,272.

Polymer 5 is produced according to BE-PS 818 609, the neutralization being carried out according to the process of US Pat. No. 3,264,272, with the exception of neutralization with HDM (Example 23), which is carried out according to US Pat. No. 3,471,460 .

The polymers 3, 4, 14, 15, 19, 20 and 21 are produced by high-pressure radical chain polymerization.

The polymers 16 to 18 and 23 to 27 are produced according to US Pat. No. 3,780,140.

Polymer 22 is "COMER 9300" manufactured by Union Carbide.

The polymers 31 and 51 are the stated base polymers, grafted according to Example 13B of the USA patent application Serial No. 322 360.

The basic polymers of the stated polymers are the following:

Polymer 33: Ethylene / Propylene / Hexadiene (1,4) (64/32/4); Mooney viscosity according to ASTM test standard D-1646 (ML-1 + 4/131 ° C) about 45.

Polymers 34 and 35: ethylene / propylene / hexadiene (1.4) / norbornadiene (2.5) (54/40/6 / 0.35); Mooney viscosity about 25.

Polymers 36 to 38.46 to 49.70 and 71: ethylene / propylene / hexadiene- (1.4) (62/32/6); Mooney viscosity around 35.

Polymers 39.41 to 45.50, 57, 66.73 and 77: ethylene / propylene / hexadiene (1.4) / norbornadiene (2.5) (68/26/6/0.15); Mooney viscosity about 33.

Polymer 40: ethylene / propylene / hexadiene (1.4) / nor-bornadiene (2.5) (71/23/6 / 0.5); Mooney viscosity about 25.

All of the above base polymers are prepared by copolymerizing the monomers in the presence of a coordination catalyst such as diisobutyl aluminum chloride and vanadium oxytrichloride. The copolymerization can be carried out in an inert solvent or in a slurry or in particulate form. Details can be found e.g. in U.S. Patents 2,933,480.2,962,451.3,000,866, 3,093,620.3,093,621.3,063,973.3,147,230,354,528, 3,260,708 and M. Sittig: "Stereo Rubber and Other Elastomer Processes », Noyes Development Corporation, Park Ride, NJ, 1967, and in U.S. Patent 3,819,591.

Polymer 33: Mixture of the above-mentioned base polymer with ethylene / maleic anhydride copolymer (89/11), produced by high-pressure radical chain polymerization.

Polymer 34: 7 weight percent MAME are circulated overnight on 6.4 mm cubes of the base polymer and extruded by means of a 28 mm Werner & Pfleiderer extrusion press equipped with a vacuum opening and 4 kneading sections. The temperature of the melt is approximately 315 ° C. and the residence time is 2 to 4 minutes. The product is cooled, cut and dried.

Polymer 35: A mixture of 9.2 g of m-carboxybenzene sulfonyl azide and 36.0 g of barium sulfate is converted into 350 g of base polymers and 0.7 g of 3,5-trimethyl-2,4, in an unheated rubber roller mill at room temperature. 6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene ("Ethyl Antioxidant 330") added. 60 g portions of the mixture are subjected to shear in a Brabender plastograph at 145 ° C. for 10 minutes and then at 170 ° C. for 10 minutes.

The polymer 36 is produced as follows: 5 g of phthalic anhydride sulfonyl azide and 5 g of 1,3,5-trimethyl-2,4,6-tris (3,5-ditert.butyl-4-hydroxybenzyl) benzene ("Ethyl Antioxidant 330") are added to 499 g of base polymer in an unheated rubber roller mill at room temperature. 60 g portions of the mixture are subjected to shear in Brabender plastographs at 170 ° C. for 10 minutes.

Polymer 37 is produced by the process described below for polymer 38 using 5150 g of base polymer 36 and 120 g of maleic anhydride. Note: In Examples 88 and 90, the composition of polymer 37 varies as follows: Example 88: 40% ungrafted, 60% grafted, 1 percent grafting; Example 90: 60% ungrafted, 40% grafted, io 1.5 percent grafting.

The polymer 38 is produced as follows: a 53 mm Werner & Pfleiderer twin-screw extrusion press is assembled by joining the ends of 16 piston sections with a diameter of 12.7 mm. A short feed section is followed by four reaction sections (zones 1 to 4), a vacuum section (zone 5), a cooling section (zone 6) and a die section. It is ensured that molten maleic anhydride can be added to the front part of Zone 1. The screws consist of kneading sections, screws with opposite threads and screw conveyors, which are arranged so that they have a pressure of 7 to 14 kg / cm2 in zones 1 to 4, no pressure in zone 5 and pressure on the mold produce from 35 to 49 kg / cm2. The free space 25 in zones 1 to 5 corresponds to 0.9 kg of polymer at the working temperature. Zones 1 to 4 are preheated to 300 ° C, zone 5 to 250 ° C and zone 6, the crosshead and die to 165 ° C.

The elastomer is fed to the extruder in the form of 30 chips, which pass through a sieve with mesh openings of 1.27 mm. Maleic anhydride is metered into the extruder at an average rate of 2.1 to 4.6%, based on the weight of the polymer. For every 100 parts of reactants, 6.6 parts of a 35 1.5 percent solution of 1,3,5-trimethyl-2,4,6-tris (3,5-ditert. 4-hydroxybenzyl) benzene (" Ethyl Antioxidant 330 ») in acetone is pumped into the mixing section immediately before the vacuum section. The extruder screw speed is 12.5 rpm and the vacuum section 40 operates at 63.5 cm of mercury.

The product, extruded at a rate of 2.63 to 2.77 kg / h, has a maleic anhydrite content of 1.5 percent by weight. Four batches of a total of 117.0 g of poly-45 caprolactam with terminal monoamino group and an average degree of polymerization of 15.3 (as powder) are added to four batches of the above product on a rubber roller mill at 110 ° C., so that the total amount is 455.8 g is. These mixtures are then transferred to an electrically heated roll mill and kneaded for 10 minutes to 50 minutes at 225 ° C. to form a smooth belt.

Polymers 39 and 41 to 45 are prepared by the process of U.S. Patent Application Serial No. 322 360, but made with various unsaturated monomers at a peak reaction temperature of 325 to 400 ° C, 55 being a static mixer (available from Kenics Company) between the extrusion screw or screws and the mold.

Like the polymer 34, the polymer 40 is produced using 2% fumaric acid, based on the base polymer 60 of the polymer 40. The extrusion press has five kneading sections and the temperature of the melt is about 350 ° C.

The polymer 46 is produced as follows:

A. Ethylene / maleic acid monoethyl copolymer. 65 The copolymer of ethylene and maleic acid monoethyl ester has randomly distributed monomer units, contains 7.2 percent by weight of polymerized maleic acid monoethyl ester, 0.7 percent by weight of polymerized maleic acid

649 566

acid anhydride and 0.4 weight percent copolymerized maleic acid and is produced by high pressure radical chain polymerization.

B. Mixture of base polymer and ethylene / maleic acid monoethyl ester.

The mixture is prepared by mixing 128 g of ethylene / maleic acid monoethyl copolymer according to A for 5 to 10 minutes at 150 ° C. on a rubber roller mill with 192 g of base polymer.

The polymer 47 is produced as follows:

A. Ethylene / maleic acid monoethyl copolymer.

The copolymer of ethylene and maleic acid mono-

Ethyl ester has randomly distributed monomer units, contains 7.0 percent by weight of polymerized maleic acid mono-ethyl ester, 0.8 percent by weight of polymerized maleic anhydride and 0.4 percent by weight of polymerized maleic acid, and is produced by high-pressure radical chain polymerization.

B. Mixture of base polymer and ethylene / maleic acid monoethyl copolymer.

The mixture is prepared by mixing 64 g of ethylene / maleic acid monoethyl copolymer according to A for 5 to 10 minutes at 150 ° C. on a rubber roller mill with 256 g of base polymer.

Polymer 48: mixture of base polymer and ethylene / maleic acid monoethyl copolymer.

The general procedure of Example 99 is followed using 128 g of copolymer and 192 g of base polymer.

The polymer 49 is produced as follows:

A. Ethylene / maleic acid mono-n-butyl ester copolymer.

The copolymer of ethylene and maleic acid mono-n-butyl ester has a random distribution of the monomer units, contains 11.8 percent by weight of polymerized maleic acid mono-n-butyl ester, 1.2 percent by weight of polymerized maleic anhydride and 0.3 percent by weight of polymerized maleic acid, and is produced by high-pressure radical chain polymerization .

B. Mixture of base polymer and ethylene / maleic acid mono-n-butyl ester copolymer.

The mixture is prepared by mixing 64 g of ethylene / maleic acid mono-n-butyl ester copolymer. A with 256 g of base polymer on the rubber roller mill at 150 ° C in the course of 5 to 10 minutes.

Polymer 50: base polymer, grafted according to the process described for polymer 39.

Polymer 52 is a blend of two commercially available polymers, butadiene / acrylonitrile (BAN) ("FRN 606" from Firestone) and styrene / maleic anhydride ("SMA-3000" from ARCO); mixing takes place in a 15.2 cm roller mill.

Polymer 53 is the BAN described for polymer 52.

Polymer 54 is a blend of styrene-butadiene rubber ("FRS 211" from Firestone) and ethylene / maleic anhydride (89/11), prepared as described for polymer 33.

The polymer 55 is produced as follows:

A. Isobutylene / isoprene copolymer ("Butyl 365" from Enjay).

The butyl rubber is an isobutylene copolymer containing 2.0 mole percent isoprene units. The Mooney viscosity (ML-1 + 8/100 ° C) is 45. As a non-staining oxidation retardant, this rubber contains 0.05 to 0.15% zinc dibutyldithiocarbamate.

B. Isobutylene / isoprene copolymer modified with phthalic anhydride sulfonyl azide.

16

6 g of phthalic anhydride sulfonyl azide are added to 300 g of isobutylene / isoprene copolymer according to A in an unheated roller mill at room temperature. The grafting is carried out by heating the mixture in a mill at 200 ° C. for 10 minutes.

The polymer 56 is produced as follows:

A. Polyisobutylene ("Vistanex L-80" from Enjay).

This polyisobutylene has a molecular weight by

Staudinger of 70,000 and contains butylated hydroxytoluene io as a non-staining oxidation retarder.

B. Polyisobutylene modified with phthalic anhydride sulfonyl azide.

6 g of phthalic anhydride sulfonyl azide are added to 300 g of the 15 polyisobutylene according to A in an unheated roller mill at room temperature. The grafting is carried out by heating the mixture in a mill at 200 ° C. for 10 minutes.

Polymer 57 is a mixture of the base polymer and styrene / maleic anhydride (5/1) ("Lytron 820" 2o from Monsanto), produced in a 15.2 cm roller mill.

Polymer 58 is a mixture of cis-1,4-polyisoprene with a Mooney viscosity (ML-4/100 ° C) of 85 ("Natsyn 410" from Goodyear Tire & Rubber Company) and an ethylene / maleic acid copolymer ( 90/10), produced 25 by high pressure radical chain polymerization.

Polymer 59 is a mixture of natural rubber (“Hartex 20” from Firestone) and the ethylene / maleic anhydride copolymer described for polymer 58.

Polymer 60 is a natural rubber used for comparison in the blend of polymer 59.

The polymer 61 is produced as follows: A 1 liter four-necked glass round bottom flask is mixed with 375 ml of water, 300 ml of ethyl acrylate, 12 g of fumaric acid, 6 ml of 30% sodium lauryl sulfate in water, 35 0.2 g of sodium hydrosulfite and 0.1 ml of dodecyl mercaptan at room temperature loaded. Nitrogen is bubbled through the mixture and then heated to 60 ° C. The copolymerization is initiated by gradually adding a 2% solution of tert-butyl hydroperoxide in water from an injection syringe 40 and continued for 2 hours at 60 ° C. 35 g of coagulate are sieved off from the emulsion, whereupon the emulsion is coagulated with acetone. After the copolymer crumbs have been washed three times with water, the crumbs are squeezed out and dried in a vacuum oven at 80 ° C. for 20 hours. A yield of 245 g of a white copolymer with an inherent viscosity of 4.06 dl / g at 30 ° C. is obtained (determined on a solution of 0.1 g copolymer in 100 ml of chloroform).

The polymer 62 is produced as follows: A 1-liter four-necked glass round-bottom flask is mixed at room temperature with 450 ml of water, 360 ml of ethyl acrylate, 144 g of mono-fu-marsonate, 3.6 ml of ethylenedimethacrylate, 7.2 ml of 30% sodium lauryl sulfate solution in water, 0 , 24 g sodium hydrosulfite and 1.2 ml didecyl mercaptan. After nitrogen has been bubbled through the mixture for 1/2 hour, the mixture is heated to 43 ° C. The copolymerization is initiated by gradually adding 1.5 ml of a 2% solution of tert-butyl hydroperoxide in water from an injection syringe and continued for 6 hours at 43 ° C. Then the heat development subsides. After the mixture has been heated to 40 ° C., 1 ml of the same hydroperoxide is added over the course of an hour. Only a trace of coagulum needs to be removed. The latex is agulated with acetone ko-65, and the crumbs of the terpolymer are washed three times with water and then dried in a vacuum oven at 80 ° C. for 3 days. Yield: 296.5 g. Inherent viscosity (determined on a solution of 0.1 g terpolymer in chloro-

17 649566

shape at 30 ° C): 0.74. Composition: 95 weight-free distribution of the monomer units and a percent acrylic acid ethyl ester, 4 weight percent fumaric acid melt index of 10.0 g / 10 min.

monoethyl ester, 1 weight percent ethylene dimethacrylate. The polymer 68 is a polyurethane elastomer, manufactured

The polymer 63 is produced as follows: A sets according to US Pat. No. 2,729,618 ("Texin 480" from Mobay). 1 liter four-necked glass round-bottomed flask is at room temperature 5 Polymer 69 contains "Herchlor C" from Hercules Inc. with 450 ml of water, 360 ml of n-butyl acrylate, 14.4 g. Polymer 70 is prepared as follows: 3.54 g

Fumaric acid monoethyl ester, 7.2 ml of a 30 percent Lö monoethyl ester of phthalic anhydride sulfonyl azide, sodium lauryl sulfate in water, 0.24 g sodium hyde on an unheated chewing roller with room drosulfite and 0.1 ml dodecyl mercaptan. Due to the temperature added to 300 g of base polymer. This Mi mixture is bubbled with nitrogen for an hour, and the mixture is heated in portions of 150 g each for 10 minutes at 200 ° C. and the mixture is heated to 43 ° C. and subjected to shear with 2 ml.

2 percent solution of tert. Butyl hydroperoxide added. The polymer 71 is produced as follows: 6.21 g

Over the next 4 hours, 2 ml of a 10-per-monooctadecyl ester of phthalic anhydride sulfonyl azide, a cent solution of tert-butyl hydroperoxide are added. After are added to 300 g of base polymer on an unheated chewing roller mill with the addition of 0.24 g of sodium hydrosulfite and 1 ml of tert-butyl 15 room temperature. The hydroperoxide is heated to 40 ° C. and the mixture is stirred in portions of 150 g for 10 minutes at 200 ° C. for 30 minutes. Then the mixture is subjected to shear again.

Heated to 40 ° C; during the last hour of heating to Polymer 72 is by high pressure radical chain

At 40 ° C, 1 ml of tert-butyl hydroperoxide is added. Made by polymerisation.

15 g of coagulate are sieved off from the dispersion obtained in this way, 20 polymer 73 is the base polymer.

and the copolymer is precipitated with acetone from the dispersion. Polymer 74 is an ethylene / butene copolymer. The copolymer crumbs are made three times by Du Pont using the low pressure process; Washed dense water and dried in a vacuum oven at 80 ° C. 0.937 g / cm3.

The white product weighs 283.5 g and has an inherent viscosity. The polymer 75 is a homopolymer of ethylene, cosity of 3.60 (determined at 30 ° C. on a solution of 25 prepared by high-pressure radical chain polymerization; 0.1 g copolymer) in chloroform). It contains 4 weight density of the polymer 0.920 g / cm3.

percent of fumaric acid monoethyl units. The polymer 76 is a homopolymer of ethylene,

Polymer 64 is made as follows: made by Du Pont using the low pressure process;

A. Ethylene / maleic acid monoethyl copolymer. Density before grafting 0.957 g / cm 3 and melt index The copolymer contains 90% by weight of ethylene 30 (Condition E) 2.8. The grafting is carried out according to the method described for the units and 10 weight percent maleic acid monoethyl polymer 39.

random distribution of ester units. The polymer 77 is used according to the

B. ethylene / propylene copolymer. grafted method.

The elastomeric copolymer of ethylene and propylene The polymer 78 is «Diene 35» from Firestone Rubber has an irregular distribution of the monomer units and 35 Co.

has a Mooney viscosity (ML-1 + 4/121 ° C) of 51. It is in solution in hexane at 50 ° C in an evaporation-cooled continuous reactor in the presence of a reaction mixture itself by the addition of VCl4 and Dii Table II sobutylaluminium monochloride (atomic ratio ALV = 6) 40 Meaning of the abbreviations produced coordination catalyst. E

C. Preparation of a Mixture of Ethylene / Maleic Acid IBA Remonoethyl Ester Copolymer and Ethylene / Propylene MAA Copolymer. MA

The mixture is produced at 150 ° C. in a roller mill from 45 MAME 64 g ethylene / maleic acid monoethyl copolymer HMD according to A and 256 g ethylene / propylene copolymer VA according to B. Mixing takes 5 to 10 minutes. The MMA analysis shows that the mixture contains 1.2% by weight of maleic acid monoethyl ester units, 0.36% by weight of maleic acid AA anhydride units and less than 0.15% by weight of maleic acid units. SMA

The polymer 65 is produced as follows: 3 g of nBA phthalic anhydride sulfonyl azide are mixed on a rubber chewing roller at room temperature with 300 ml of the elastomeric ethylene / propylene copolymer according to Part B of the description of polymer 64 at room temperature. GMA The mixture is transferred to a roller mill at 200 ° C., EDMA and subjected to shear at 200 ° C. for 10 minutes, EA to graft phthalic anhydride sulfonyl groups onto the ethylene / so FA propylene copolymer. BOHM

The polymer 66 is produced as follows: About 1.4% fumaric acid is grafted onto PASA the base polymer according to the SMA process for the polymer 39. The (3000)

Melt index of the graft polymer, determined in accordance with 65 ASTM test standard D-1238 at 280 ° C. with a load of FAME 2160 g, is 3 g / 10 min. P

Polymer 67 is an elastomeric copolymer with BASA

Ethylene

Acrylic acid isobutyl ester

Methacrylic acid

Acrylic acid methyl ester

Monoethyl ester of maleic anhydride

Hexamethylenediamine

Vinyl acetate

Methyl methacrylate

Carbon monoxide

Acrylic acid

Hydroxyethyl methacrylate

Methacrylic acid stearyl ester

Acrylic acid n-butyl ester

2-ethylhexyl methacrylic acid

Methyl vinyl ether

Maleic anhydride

Methacrylic acid glycidyl ester

Ethylene glycol dimethacrylate

Acrylic acid ethyl ester

Fumaric acid

Maleic acid monobutyl ester phthalic anhydride sulfonyl azide

Copolymer of styrene and maleic anhydride

Fumaric acid monoethyl propylene

Benzoic acid sulfonyl azide

649566

BAN SBR

Copolymer of butadiene and acrylonitrile

Styrene-butadiene rubber graft

Examples 1 to 163

Details of these examples, the samples of which are prepared by the method described above, can be found in Table III.

Comparative Sample A is molded from a medium molecular weight nylon 66. Examples 1 to 5 are a series of concentrations using a terpolymer, partially neutralized with zinc, of ethylene, isobutyl acrylate and methacrylic acid. At a concentration of 30%, the Izod impact strength of a shaped rod is above 0.54 mkg / cm both at the gate end and at the other end. At a concentration of 20%, the material is tough at one end of the shaped rod, and at lower concentrations the toughness is in the range in which it is at higher concentrations in the known thermoplastic compositions. Comparative examples B to E relate to the prior art and show that a copolymer of ethylene and methacrylic acid of a higher modulus solidifies the polyamide matrix 1 less effectively than the terionomer of a low modulus. _

Example 6, in comparison with Example 5, shows that the reduction in the molecular weight of the matrix leads to a reduced Izod impact strength of the composite. Examples 7 to 10 show the influence of the increase in the molecular weight of the basic mass solidified by 20% terionomer. In Example 10 a solidification of the basic mass with the highest molecular weight is obtained by the ionomeric ethylene terpolymer, so that at a concentration of the terpolymer of 20% the strength is approximately as great as that which is found in the basic mass 1 at a concentration of Receives 30%.

Examples 11 and 12 are compared to Examples 4 and 5 to show the range of reproducibility for samples that were considered identical. A comparison of comparative examples F and G with comparative examples D and E shows a similar reproducibility with known thermoplastic compositions.

Comparative examples H, I and J show that polymers. (Low ethylene content and low modulus are not effective strengthening agents if there are no adhesion sites. In comparison, in Example 13, where there is an adhesion site, very high toughness is obtained. Note that the only essential difference between the polymers of Examples 13 and 14 is that in Example 13 the ionomeric group is present.

Examples 14 and 15 show the strong strengthening effect of the non-neutralized maleic acid monoethyl ester terpolymer both in a polyamide of medium molecular weight with balanced end groups (Example 14) and in a polyamide matrix with a high content of terminal amine groups (Example 15). The high content of terminal amine groups apparently results in a more effective interaction with the dispersed acid reinforcing agent than with the polyamide with a normal balance of the end groups. When an ionomeric polymer is used, there is generally less benefit in solidifying a polyamide with a high amine end group content. Compare Example 16 with Example 4.

Examples 17 to 20 represent a series of concentrations of the solidifying agent present in the form of the free acid.

18th

in a polyamide with a high content of amine end groups. At a concentration of 5%, considerable solidification is achieved. The toughness of the thermoplastic composition of Example 18 comes very close to that of the known thermoplastic composition (Comparative Example C), although the concentration of the strengthening agent in it is only 1/4 that of the known thermoplastic composition, so that it has a considerably better tensile strength and a better module can be achieved. Examples 19 and 21 illustrate the influence of the difference in the concentration of the terminal amine groups of the polyamide. With a concentration of the strengthening agent of 10%, the effect is much more noticeable than at a concentration of 20%, at which the highest ductility, characterized by the Izod notch-15 impact strength, is achieved.

Example 23 shows that the acidic polymer neutralized to a small extent with hexa-methylenediamine is an effective strengthening agent for nylon.

Examples 22, 25 and 26 show the influence of various degrees of neutralization in the preparation of ionomers for the solidification of polyamides with balanced end groups. In a polyamide matrix with balanced end groups, the zinc ionomer is a more effective polymer than the free acid polymer. Examples 24 and 25 differ mainly from one another in the details of the neutralization process carried out on the two-roll mill and show that the neutralization must be carried out correctly in order to achieve the best reinforcement effect. The conditions of neutralization are given in Table I. Of course, you have to choose the most favorable process conditions for the best results for each combination of polymer and matrix.

The examples from Example 28 to Comparative Example L-35 contain three further test series in which the neutralization with zinc was carried out with three different reinforcing agents in the range from 0 to 100% or more. In all three cases where a polyamide with balanced end groups was used, the preferred degree of neutralization is in the range of 100% or less. Example 36 and Comparative Example L show that a neutralization of 125% can lead to a decrease in toughness, so that for practical purposes a neutralization in the range of 100% or less for strengthening agents to be used for a balanced polyamide 45, is preferred.

Examples 42 to 45 show that calcium, lithium, potassium and sodium ionomers can also be effective strengthening agents if, together with them, a wise rather organic residue, e.g. Ethylene / acrylic acid methyl ester / monoethyl ester of maleic anhydride (E / MA / MAME), is used. Example 46 shows that the antimony ionomer has a certain solidifying effect. Most ionomerization attempts have used the metal hydroxide or metal acetate as the neutralizing agent; however, other salts are also effective. Examples 47 and 48 show that organic salts of metal ions can also be used.

Examples 49 and 50 show in comparison with the examples 6 and 3 that 4 and 4 show that by mixing small amounts of ethylene / methyl acrylate / maleic anhydride ester ionomers with ethylene / isobutyl acrylate / methacrylic acid ionomers, the uniformity of the thermoplastic compositions in comparison with mixtures from the last-65 named ionomer and the polyamide is considerably improved.

Examples 51 and 52 show that a lower molecular weight polyamide is effective by the E / MA /

19 649 566

MAME polymers can solidify. The improvement in len could; however, the cross-linking effect of the ether

Izod impact strength beyond that of the base resin ylenglycol dimethacrylate (comparative example Q), which results from example 53, indicates that its.

by moderately higher concentrations of the polymer Examples 83 to 103 illustrate a wide range of the strengthening capacity of ethylene / propylene / copolyme- with a polyamide of such low molecular weight.

achieved considerable toughness. risks, the small amounts of for the storage of

Examples 54 to 58 illustrate the solidification of suitable service units. As the beige of several different ionomeric ethylene terpolymer games shows, different polymers can be used for polyamides. The results of Examples 59 and 60 have different molecular weights and different promises that polymers with a higher molecular ratio of ethylene to propylene units and are more effective than those with a lower molecular weight content of diene units. You can in weight. Polymers with a wide range of polyamides with balanced end groups or in poly molecular weights can be used. A comparison of the examples of amides of high amine end groups used shows the effectiveness of an ionomeric ethylene and the most diverse adhesive groups can be grafted onto them vinyl acetate / methacrylic acid terpolymers in a poly 15. Example 86 shows, in comparison to the amide with a high amine end group content in comparison to game 87, that at low trap concentrations, the same polymer in a polyamide with balanced monocarboxylic acid is less effective than the dicarene amine end groups. bonic.

Examples 63 and 64 demonstrate the effectiveness of another ethylene terpolymer, the free acid, at 20. Example 102 shows that an ionomer of this copolymer, a high amine end group polyamide, is active, and Example 103 shows that the copolymer solidify the effectiveness of the ionomer in a polyamide with selected polyamides of low molecular weight, matched end groups. Examples 104-112 demonstrate that a wide variety of comparative examples M and N, in turn, demonstrate that low modulus polymers can be used to create a poly-bond point. In example 65, the ethylene has 25 amides to solidify, provided that there is an adhesive group. / Vinyl Acetate / CO Terpolymers A Moderate Solidification- The examples include most of the generally under-acting polyamide with balanced end groups. Inexpensive synthetic and natural chewing. In comparison, Examples 66 and 67 show effective protection including butadiene-acrylonitrile rubber, styrene-based solidification, the polyamide with amine end-group butadiene rubber, Buna rubber, isobutylene rubber, pen probably a more effective interaction with the 30th Isoprene rubber, natural rubber, acrylic acid ethyl ester carbonyl groups of the terpolymer is used as the polyamide rubber, acrylic acid butyl ester rubber etc. The Ver-with balanced end groups. (The results with E / VA-like examples O and P for examples 104 and 110 illustrative polymers were less reproducible than those with the importance of an adhesion point for adhering to the other polymers, apparently because these polymers differ in terms of their basic mass.

the processing temperatures for nylon 66 already at 35. Examples 113 and 114 show that their stability range lies with a Co limit.) Example 69 polymerizate from ethylene and propylene similar results can achieve the effect of a mixture of two previously used as with a terpolymer made of ethylene, polymer, the mixture providing good uniformity of propylene and a diene (Examples 83 to 103), and pre-strength and toughness. Example 70 explains the setting that a polymer with adhesion points for the matrix of two polymers, namely the one in Comparative Example 40 is admixed (Example 113), or that a suitable adhesive N and the polymers used in Examples 3 and 4, where is grafted onto the copolymer (Example 114). when one achieves a much better toughness than when the concentration series of the ethylene / acrylic acid isobutene - only one of these polymers is used. Similar active esters / methacrylic acid ionomers in the basic composition 1 obtained from mixtures of two polymers result from Examples 3, 5, 115, Comparative Example R and Verden Examples 71 and 72. 45 same example S shows that at high polymer contents a

A comparison of Example 73 with the comparative example Izod impact strength of more than 1.1 mkg / cm can be achieved

N shows that one is attached by adding a small amount. At high polymer contents, however, there is a tendency for a polymer to become a non-adherent polymer, a decrease in tensile strength and rigidity, and with a low modulus of solidification, the content of which is greater than 50%, a very sharp decrease can be improved. 50 these properties, probably due to one

Examples 74-78 illustrate a number of ethylene phase reversals.

Terpolymers with CO as a reactant for the polyamide Examples 116,117 and 118 show that nylon is also great. Some of these examples show toughness, 612 which can be strengthened by an ionomer. In the example

which have an Izod notch 119 and 120 on both ends of the test rod and in Comparative Example T are

impact strength of 0.54 approximates, and suggest 55 judged results.

that many of these polymers, when optimizing the composite nylon 6, can be consolidated very effectively by the ionomer of E / MA / MAME neutralized with settlement and processing or with a zinc; know increase in the concentration of the hardening agent cf. Comparative Example U and Example 121. This can be said to have a uniform Izod impact strength of 0.54 hardening agent even in lower concentrations. _ 60 turn.

The samples of Examples 79, 80 and 81 are ethylene / Vin- “Hüls nylon 12” (see Comparative Example V). Ylacetate terpolymers with different functional groups can also be effectively processed by the E / MA / MAME ion

pen, all of which have better strengthening properties (example 122) and by E / IBA / MAA (example 123)

sen than it results from comparative example N. Solidify example. Urethane rubbers are used in the melting

82 illustrates a polymer that has four different monomerics of nylon 12 resistant enough to be effective units, and again shows that opti polymers can be used; see. Example 124.

Izod impact strength values of more than 0.54 nylon 11 are strengthened by E / P / diene-g-FA; see. -

125 and 126 formed over the entire length of the shaped test rod.

649 566 20

Example 127 is an example of solidifying a night; (3) a comparison with the control sample BB, which

lon copolymers. was created by first the soft, adhesive polymer

Example 128 explains the solidification of nylon 66 mixed with the base material and the mixture was then extruded again with balanced end groups by an ethylene / propylene / addition of polyethylene,

Hexadiene (1,4) / norbornadiene polymer, which shows about 1.4 Ge 5 that the components of the mixture together contain in the weight percent fumaric acid. Similar results must be contained in the same particles in order to achieve an effective holding according to Examples 129 and 130 with similar solidification. The comparative sample CC shows that

Polymers made with esters of phthalic anhydride sulfonyl- this polymer by itself in a concentration of 5%

are grafted azide. not sufficient to give the matrix a very high toughness. The solidification of an amorphous polyamide by early i0 keit (a comparison with Example 141 shows the

polymer disclosed is in Examples 131 to 133 on the terminal amine groups of the matrix),

shown. A comparison of control sample DD with example 150 reveals

The same polymers also solidify a polyamide, clarifying the effect of the difference in the module of the polymer.

which contains a cyclic aliphatic structure (Examples 134 ren with approximately the same degree of adherence.

to 136). 15 Example 151 illustrates an effective mixture of buta-

Examples 137-141 compare to the diene rubber in an adhesive material. Comparative Example Y the strengthening effect of an ethylene / propylene / hexadiene (1,4) / which was grafted with fars in Examples 153 and 154 in comparison with Example 152 and Examples 156 to 160 in comparison with Example 155 norbornadiene polymers at low concentrations. show that a solidified thermoplastic mass Example 142 shows the effectiveness of a mixture of egg-20 various additives, e.g. in amounts up to about 4.5% by weight of soft polymers (ethylene / methacrylate 46/54) and percent by weight, without the mechanical an adhesive polymer (ethylene / acrylic acid 80/20). Properties are significantly affected. The sample Examples 144 to 149 and comparative examples Z of example 153 contain a lubricant, the sample of the example and AA explain the effect of mixing example 154 of a heat stabilizer, and the samples of the two-chain polyethylenes of different densities 25 games 156 to 160 contain colorants. In these experiments on an ethylene / propylene / He- grafted with fumaric acid, the additives with the samples of Examples 152 to 155 were xadiene (1,4) / norbornadiene polymers. The samples of the in a double screw game 144 provided with a vacuum opening and of the comparative example Z are mixed by a dry extrusion press.

mixing all ingredients and feeding to them. The sample of Example 162 was prepared by making 33 twin screw extruders; the comparative 30% by weight of stacked glass silk in a single-screw extruder equipped with vacuum sample AA and the samples from Examples 145 to 149 are finally mixed into the product by comminuting the hydrocarbon poly of Example 161. The merisate thus obtained, before being fed to the extrusion press, together with the product, produced almost twice the Izod impact strength of the polyamide. Despite some fluctuations in how a commercially available glass fiber reinforced result, the examples show the following: (1) Blend 35 nylon 66, and showed almost strength and stiffness with a softer polyethylene are more effective than solute unsolidified material. Example 163 illustrates che with a higher modulus polyethylene; (2) Another similar improvement by adding a mineral filler, adhesive polymer can be a mixture of effective material to the polyamide.

21st

Table III

example

polyamide

Polymer

Neutrali

polymer

Izod,

reason or station concentration mkg / cm *

mass no.

mixture

tration,%

Comparison A

1

-

0

0.054

1

1

1

Zn 72%

10th

0.076 / 0.12

2nd

1

1

do.

15

0.114 / 0.19

3rd

1

1

do.

20th

0.131 / 0.909

4th

1

1

do.

20th

0.131 / 0.925

5

1

1

do.

30th

1,089 / 1,257

Comparison B

1

2nd

do.

20th

0.131 / 0.196

Comparison C

1

2nd

do.

20th

0.087 / 0.18

Comparison D

1

2nd

do.

30th

0.158 / 1.089

Comparison E

1

2nd

do.

40

1.404 / 1.546

6

2nd

1

do.

30th

0.267 / 0.958

7

1

1

do.

20th

0.131 / 0.196

8th

3rd

1

do.

20th

0.136 / 0.844

9

4th

1

do.

20th

0.163 / 0.92

10th

5

1

do.

20th

0.773 / 1.029

11

1

1

do.

20th

0.12 / 0.332

12

1

1

do.

30th

0.79 / 1.442

Comparison F

1

2nd

do.

30th

0.125 / 1.208

Comparison G

1

2nd

do.

40

1.312 / 1.53

Comparison H

1

3rd

-

30th

0.087 / 0.163

Comparison I

1

3rd

-

40

0.087 / 0.071

Comparison J

1

4th

-

20th

0.06 / 0.087

13

1

5

Zn 100%

20th

1.05 / 1.029

14

1

5

0

20th

0.936 / 0.865

15

6

5

0

20th

1.159 / 1.203

* See page 29

example

Tensile

fracture

Bend

tensile strenght

Size of c

speed,

strain,

module of poly pergier

1cg / mm2

%

kg / mm2

meren,

ten poly

kg / cm2

particles

(in the

Comparison A

8.79

40

289

1

7.59

28

252

1195

2nd

6.68

36

228

1195

0.2-1

3rd

5.98

43

197

1195

0.1-1

4th

6.4

40

204

1195

5

4.99

77

168

1195

Comparison B

6.26

61

216

4850

0.2-1

Comparison C

6.68

43

215

4850

Comparison D

5.48

70

180

4850

0.1-2

Comparison E

4.92

120

153

4850

6

5.27

62

179

1195

7

6.47

40

215

1195

8th

6.18

46

200

1195

9

6.26

46

200

1195

10th

6.12

47

200

1195

11

6.47

37

191

1195

12

5.48

47

160

1195

Comparison F

5.83

77

186

4850

Comparison G

5.27

56

156

4850

Comparison H

6.18

20th

211

42

Comparison I

4.29

34

136

42

Comparison J

6.05

17th

232

5.6

13

5.83

131

176

17th

0.1-0.5

14

5.83

46

202

17th

0.05-0.3

15

6.05

53

223

17th

649566

22

Table III (continued)

example

polyamide

Polymer

Neutrali

polymer

Izod,

reason or station concentration mkg / cm *

mass no.

mixture

tration,%

16

6

1

Zn 72%

20th

0.158 / 0.849

17th

6

5

0

2nd

0.06 / 0.065

18th

6

5

0

5

0.136 / 0.147

19th

6

5

0

10th

0.816 / 0.958

20th

6

5

0

15

1,083 / 1,181

21st

1

5

0

10th

0.158 / 0.223

22

1

5

0

15

0.452 / 0.724

.23

5.

HMD 12%

15

0.642 / 0.724

24th

1

5

Zn 100%

15

0.229 / 0.468

25th

1

5

Zn 100%

15

1.002 / 0.98

26

1

5

Zn 50%

15

0.893 / 0.914

27th

5

(a)

15

0.719 / 0.697

28

1

0

20th

0.125 / 0.18

29

1

Zn 25%

20th

0.131 / 0.74

30th

1

Zn 50%

20th

0.185 / 0.991

31

1

1

Zn 71%

20th

0.174 / 1.012

32

1

1

Zn 100%

20th

0.185 / 0.299

33

1

1A

Zn 50%

20th

0.114 / 0.675

34

1A

Zn 75%

20th

0.136 / 0.953

35

1A

Zn 100%

20th

0.229 / 0.958

Comparison K

1

1A

Zn 125%

20th

0.212 / 0.229

36

1

5

0

20th

0.936 / 0.865

* See page 29

Annotation:

The sample of Example 17 is prepared by diluting the sample of Example 19 with the matrix 6; the sample of Example 18 is prepared by diluting a mixture of the samples of Examples 19 and 20 with the matrix 6.

(a) 25% neutralized with oligomer (degree of polymerization 7.5).

Example-

Tensile

fracture

Bend

tensile strenght

Size of dis-

speed,

strain,

module,

of poly pergier

kg / mm2

%

kg / mm2

meren,

polymer

kg / cm2

particles,

Around

16

6.4

49

212

1195

17th

8.79

26

288

17th

18th

8.01

37

267

17th

19th

6.96

48

245

17th

0.1-0.4

20th

6.47

71

240

17th

21st

7.03

31

160

17th

22

6.47

34

226

17th

23

6.82

43

216

24th

6.26

45

216

17th

25th

6.82

73

206

26

6.96

72

205

12

0.02-0.5

27th

7.03

38

224

13

0.05-1

28

6.4

23

204

29

6.89

30th

205

30th

6.75

36

205

31

-

-

32

6.96

43

205

33

-

-

34

6.12

30th

207

306

35

Comparison K

36

5.83

46

202

23

649566

Table III (continued)

example

polyamide

Polymer

Neutrali

polymer

Izod,

reason or station concentration mkg / cm *

mass no.

mixture

tration,%

37

1

5

Zn 10%

20th

0.844 / 0.931

38

1

5

Zn 25%

20th

0.936 / 1.029

39

1

5

Zn 50%

20th

1.018 / 1.056

40

1

5

Zn 75%

20th

1.149 / 1.121

41

1

5

Zn 100%

20th

1.127 / 1.181

Comparison L

1

5

Zn 125%

20th

0.158 / 0.196

42

1

5

Approx. 100%

15

0.207 / 0.702

43

1

5

Li 100%

15

0.947 / 1.018

44

1

5

K 100%

15

0.925 / 0.958

45

5

Na 100%

20th

0.762 / 0.773

46

1

5

(b)

15

0.169 / 0.294

47

1

5

(c)

15

0.675 / 0.914

48

1

5

(d)

20th

0.816 / 0.931

49

6

5

Zn 100%

5

1 "

0.838 / 1.1

50

6

5

Zn 100%

1y

2.5

0.653 / 1.105

1

17.5

51

7

5

0

20th

0.844 / 0.936

52

7

5

0

20th

0.762 / 0.855

53

2nd

5

0

20th

0.169 / 0.201

54

1

6

Zn 75%

20th

0.838 / 0.952

55

1

7

do.

20th

0.245 / 0.876

56

1

8th

do.

20th

0.67 / 0.952

* See page 29

(b) Sb +++ 100%

(c) K stearate

(d) 100% zinc abietate ("Pexate" from Hercules Inc.)

example

Tensile

fracture

Bending module,

tensile strenght

speed,

strain,

kg / mm2

of the poly

kg / mm2

%

meren,

kg / cm2

37

6.12

46

204

38

-

39

5.83

62

201

40

-

41

5.48

121

185

Comparison L

-

-

-

42

6.89

37

224

43

6.6

53

219

17.5

44

6.12

60

224

45

6.05

74

185

46

-

33

47

6.75

36

230

48

6.19

56

214

49

6.19

51

207

50

6.4

40

51

5.62

14

190

24th

52

5.62

43

184

53

6.12

48

231

8.4

54

-

-

-

55

-

-

56

-

-

Size of the dispersed polymer particles, | im

24th

Table III (continued)

example

polyamide

Polymer

Neutrali

polymer

Izod,

reason or station concentration mkg / cm *

mass no.

mixture

tration,%

57

1

9

Zn 75%

20th

0.234 / 0.931

58

1

10th

Approx. 100%

20th

0.25 / 0.61

59

1

11

Zn 75%

20th

0.152 / 0.272

60

1

11

do.

20th

0.201 / 0.778

61

12

do.

20th

0.795 / 0.991

62

1

12

do.

20th

0.191 / 0.332

63

13

0

20th

0.729 / 1.002

64

1

13

Zn 75%

20th

0.729 / 1.083

Comparison M

1

14

-

20th

0.12 / 0.163

Comparison N

1

15

-

20th

0.158 / 0.158

65

1

16

-

20th

0.136 / 0.386

66

17th

-

20th

0.61 / 0.729

67

16

-

20th

0.523 / 0.767

68

1

16

-

20th

0.25 / 0.435

69

1

1

Zn 72%

10th

0.637 / 0.784

18th

10th

70

1

1

Zn 72%

10th

0.65 / 0.98

19th

10th

71

1

1

Zn 72%

15

0.65 / 0.93

20th

5

72

1

1

Zn 72%

15

0.65 / 0.87

21st

-

5

73

6

22

-

5

0.18 / 0.708

15

-

15

74

1

23

-

20th

0.256 / 0.642

75

6

24th

-

20th

0.191 / 0.615

76

6

25th

-

20th

0.152 / 0.604

77

6

26

-

20th

0.49 / 0.773

* See page 29

example

57

58

59

60

61

62

63

64

Comparison M Comparison N

65

66

67

68

69

70

71

72

73

74

75

76

77

Tensile strength, kg / mm2

5.83

5.91

5.98

6.05

5.9

5.83

5.9

6.47

6.68

6.33

6.61 6.68

6.75

5.76 6.75

5.62 5.83

Elongation at break,%

15

19th

20th

27th

33

34 23

28 20 34 33 19 26 38 31 26

Bending module, kg / mm2

214

204

200

210

201 195 199

204 207

205

216

217 227 194 217 207

211

Tensile strength size of the polymer

kg / cm2 particles,

(in the

105

590

66 32

423

169 618

0.05-0.6

0.1-0.5

0.1-0.5

0.1-0.5

25th

649566

Table III (continued)

example

polyamide

Polymer

Neutrali

polymer

Izod,

grand or station conc. mkg / cm *

mass no.

mixture

tration,%

78

6

27th

_

20th

0.425 / 0.528

79

1

28

0

20th

0.757 / 0.457

80

6

29

0

10th

0.196 / 0.539

81

6

30th

0

20th

0.55 / 0.8

82

6

31

0

20th

0.316 / 0.691

83

1

32

0

20th

0.909 / 0.985

84

6

33

0

20th

0.577 / 0.751

85

6

34

0

20th

0.691 / 0.914

86

6

35

0

20th

0.191 / 0.24

87

1

36

0

20th

1.002 / 1.121

88

1

37

0

20th

0.675 / 0.735

89

6

38

0

20th

0.86 / 1.029

90

6

37

0

20th

1.045 / 1.165

91

1

(d)

0

5

0.833 / 0.953

39

20th

92

1

40

0

20th

0.648 / 0.849

93

1

41

0

20th

0.517 / 0.604

94

1

42

0

20th

0.659 / 0.67

95

1

43

0

20th

0.621 / 0.68

96

1

44

0

20th

0.506 / 0.691

97

1

45

0

20th

0.61 / 0.691

98

1

46

0

20th

0.572 / 0.751

99

1

47

0

20th

0.631 / 0.827

100

1

48

0

20th

0.615 / 0.8

101

1

49

0

20th

0.724 / 0.816

102

1

50

Zn 100%

20th

0.767 / 0.876

See page 29

(d) 100% zinc abietate («Pexate 511»)

example

Tensile

fracture

Bending module

tensile strenght

Size of

speed,

strain, %

kg / mm2

of the poly dispersing

kg / mm2

meren,

ten poly

kg / cm2

mer particles,

| xm

78

5.69

55

207

18th

79

5.41

29

194

29

0.02-0.3

80

7.31

39

245

77

81

5.83

45

188

0.1-1

82

5.91

81

206

3.5

0.2-1

83

5.2

46

180

84

0.1-1

84

5.98

21st

227

0.05-1

85

5.62

25th

198

0.1-1

86

5.83

36

207

87

4.99

62

188

88

5.13

43

181

89

4.5

40

188

90

5.69

45

183

91

5.06

41

196

92

5.48

35

214

93

5.34

22

189

94

5.48

37

186

95

5.41

28

183

96

5.76

18th

202

97

5.62

29

193

98

5.76

27th

204

99

5.69

25th

201

100

5.91

29

208

101

5.69

39

202

102

5.34

48

179

649566

26

Table III (continued) Example of polyamide large composition no.

Polymeric neutralization mixture

Polymer izod,

concentrated - kg / cm *

tration,

%

103

2nd

51

0

20th

0.740 / 0.719

104

6

52

0

20th

0.593 / 0.626

Comparison O

6

53

-

20th

0.158 / 0.158

105

6

54

0

20th

0.414 / 0.92

106

6

55

0

20th

0.294 / 0.25

107

6

56

0

20th

1.187 / 1.236

108

1

57

0

20th

0.321 / 0.201

109

6

58

0

20th

0.24 / 0.757

110

1

59

0

20th

0.539 / 0.702

Comparison P

1

60

-

20th

0.065 / 0.082

111

6

61

0

20th

1.236 / 1.17

Comparison Q

6

62

0

10th

0.131 / 0.125

112

6

63

0

20th

1.208 / 1.208

113

1

64

-

20th

0.626 / 0.827

114

1

65

0

20th

1,056 / 1,094

115

1

1

Zn 72%

40

1.546 / 1.562

Comparison R

1

1

do.

50

1.47 / 1.6

Comparison p

1

1

do.

70

NB

116

8th

1

do.

30th

0.245 / 0.87

117

8th

1

do.

20th

0.152

118

8th

1

do.

10th

0.087

Comparison T

9

-

0

0.033 / 0.038

119

9

66

0

20th

0.697 / 0.833

* See page 29

example

103

104

Comparison O

105

106

107

108

109

110

Comparison P

111

Comparison Q

112

113

114

115

Comparison R Comparison S

116

117

118

Comparison T

119

Tensile strength, kg / mm2

4.71 5.83 5.41 5.34 4.71 5.06 5.98 5.69 5.76 5.48 6.4

5.91 5.55 4.85 4.34 4.71 2.81 4.15 4.78 5.55 4.78 4.01

Elongation at break,%

65

47 39

48 45 55 50 37 31 19

124

104 29 65 160 120 170 114 86 61 22 55

Bending module, kg / mm2

159 211 218 198 187 185 208 191

195 231 205

194 194 167 130 143 25 138 165

196 223 136

Tensile strength of the polymer, kg / cm2

8.4

1.7-2.8 1.34 74 28 1195 1195 1195 1195 1195 1195 1195

Size of the dispersed polymer particles, um

0.05-0.6 0.02-0.6

27th

649566

Table III (continued)

example

polyamide

Polymer

Neutrali

polymer

Izod,

reason or station concentration mkg / cm *

mass no.

mixture

tration,%

120

9

67

Zn 100%

20th

0.773 / 0.86

Comparison U

10th

-

0

0.044 / 0.044

121

10th

67

Zn 100%

20th

1.486 / 1.464

Comparison V

11

-

0

0.044 / 0.038

122

11

67

Zn 100%

20th

1.236 / 1.121

123

11

1

Zn 72%

20th

1.09 / 1.143

124

11

68

-

20th

0.952 / 0.914

125

12

66

0

20th

0.54 / 0.54

126

12

66

0

10th

0.5 / 0.44

127

13

69

-

30th

0.751 / 0.849

128

1

66

0

15

0.882 / 0.958

129

1

70

0

20th

1,078 / 1,149

130

1

71

0

20th

0.985 / 1.089

Comparison W

14

-

0

0.098 / 0.087

131

14

1

Zn 72%

20th

1.176 / 1.165

132

14

66

0

10th

0.925 / 1.045

133

14

5

0

10th

0.931 / 1.154

Comparison X

15

-

0

0.082 / 0.093

134

15

1

0

20th

1.018 / 1.105

135

15

66

0

5

0.719 / 0.463

136

15

5

0

10th

0.931 / 0.898

Comparison Y

6

-

0

0.049 / 0.046

137

6

66

0

1

0.055 / 0.064

* See page 29

example

Tensile

fracture

Bend

tensile strenght

Size of

speed,

strain, %

module,

of the poly dispersing

kg / mm2

kg / mm2

meren,

ten poly

kg / cm2

particles.

(at the

120

4.43

50

153

Comparison U

8.15

43

259

121

6.26

> 160

179

Comparison V

4.78

> 200

150

122.

4.08

> 160

100

123

3.66

272

114

124

3.37

> 190

110

246

0.1-0.3

125

3.3

202

88

126

3.94

265

109

127

4.71

132

146

6.3

128

5.98

92

204

129

4.92

62

184

130

5.06

27th

192

Comparison W

8.86

120

247

131

5.98

128

212

132

7.38

142

225

133

7.8

97

253

Comparison X

6.19

153

151

134

4.92

155

121

135

5.48

130

147

136

5.2

143

136

Comparison Y

8.15

32

296

137

8.72

43

299

649 566 28

Table III (continued)

example

polyamide

Polymer

Neutrali

polymer

Izod,

reason or station concentration mkg / cm *

mass no.

mixture

tration,%

138

6

66

0

2nd

0.068 / 0.095

139

6

66

0

3rd

0.091 / 0.125

140

6

66

0

4th

0.114 / 0.152

141

6

66

0

5

0.129 / 0.179

142

6

22

0

6.7

0.8 / 0.637

72

-

13.3

143

1

66

0

5

0.664 / 0.811

73

10th

Comparison Z

1

66

0

5

0.131 / 0.626

74

-

20th

144

1

66

0

5

0.593 / 0.735

75

-

20th

Comparison AA

6

66

0

5

0.12 / 0.131

74

-

20th

145

6 -

66

0

5

0.468 / 0.713

74

-

15

146

6

66

0

5

0.882 / 0.871

74

-

10th

147

6

66

0

5

0.245 / 0.49

75

-

20th

148

6

66

0

5

0.963 / 0.969

75

-

15

149

6

66

0

5

0.855 / 0.659

75

-

10th

Comparison BB

6

66

0

5

0.109 / 0.131

75

20th

CC comparison

6

66

0

5

0.098 / 0.076

* See page 29

example

138

139

140

141

142

143

Comparison Z

144

Comparison AA

145

146

147

148

149

Comparison BB Comparison CC

Tensile strength, kg / mm2

8.51 8.23 8.01 7.87 5.98 6.19 5.76 5.41

Elongation at break,%

38 34 34 32 66

32 38

33

Bending module kg / mm2

291 276 269 257 214 212 186 176

Tensile strength of the polymer, kg / cm2

3895 3782 3121 1265 1216 984

Size of the dispersed polymer particles, um

29

649566

Table III (continued)

example

polyamide

Polymer

Neutrali

polymer

Izod,

reason or station concentration mkg / cm *

mass no.

mixture

tration,%

Comparison DD

1

76

0

20th

0.098 / 0.098

150

1

77

0

15

0.604 / 0.751

151

6

66

0

5

0.762 / 0.855

78

-

15

152 (I)

1

66

0

15

0.702 / 0.865

153 (2)

1

66

0

15

0.735 / 0.822

154®

1

66

0

15

0.719 / 0.806

1550

1

66

0

15

0.762 / 0.855

156 (4>

1

66

0

15

0.822 / 0.047

157 <5>

1

66

0

15

0.827 / 0.898

158®

1

66

0

15

0.757 / 0.871

159 (7)

1

66

0

14.3

0.751 / 0.882

160®

1

66

0

14.3

0.827 / 0.942

161 (1)

1

66

0

15

0.8 / 0.876

162 <9>

1

66

0

10th

0.229

163 (I0>

1

66

0

9.6

0.076

* Samples with Izod impact strength values in the range of 0.54 mkg / cm or more do not break completely. The values in front of the slash refer to the end of the sprue, the values behind the slash to the other end of the test rod.

(1) Without addition

(2) 0.1% aluminum stearate

(3) 0.41% mixture of potassium and copper (I) iodide, 0.09% aluminum stearate

(4) 0.65% ultramarine blue, 0.18% titanium dioxide, 0.003% "BlackV-302" from Ferro Corp., 0.1% ethylene bis-stearic acid amide

(5) o, 79% cadmium red, 0.007% "Black V-302", 0.1% ethylene bis-stearic acid amide

example

Tensile strength, kg / mm2

Elongation at break,%

Bending module, tensile strength size of kg / mm2

of the polymer, kg / cm2

dispersed

Polymer particles,

(in the

Comparison DD

150

151

152 (1>

5.83

49

207

153®

5.76

45

202

154 <3>

5.98

40

208

155 «)

5.98

43

207

156 <4>

6.12

42

209

157 <5>

6.05

49

204

158®

5.91

51

194

159 (7>

6.12

42

219

160 <8>

5.76

55

200

161 (1>

5.91

47

202

162 (9>

17.15

3.5

794

163 (10)

7.24

4.4

612

(6) 0.65% cadmium yellow, 0.05% titanium dioxide, 0.1% ethylene bis-stearic acid amide

(7) 2.35 titanium dioxide, 2.25% ultramarine blue, 0.07% "Violet 6-6270" from Ferro Corp., 0.1% ethylene-bis-stearic acid amide

(8) 4.5% "Ampacet Black Concentrate 19238" by Ampacet Corp. - contains 45% dispersed soot

(9) 33% glass staple silk "PPG 3531" from Pittsburgh Plate Comp.

(i °) 3go / 0 "Wollastonite F-l" from Interpace and 0.3% "Silane A1100" from Union Carbide.

Note: The particle size of the polymer is 3.0 or less in all examples.

649 566

Examples 164-167

These examples show the uniformity of toughness of a 3.2 mm thick molded sheet with an area of 7.6 cm x 12.7 cm. Samples are cut out of this plate in such a way that the Izod impact strength can be determined on the side facing the gate end (gate) in the flow direction and in the transverse direction. Thermoplastic compositions of the composition given in Table IV are produced by the process described above. Comparative examples 1 and 3 relate to solidified polyamide compositions of the prior art. Examples 164 to 167 relate to thermoplastic compositions according to the invention. In particular, the samples of Examples 166 and 167 show a uniformly high toughness with a polymer addition of 20 percent by weight to the polyamide matrix.

Table V shows the influence of the reduction in the notch radius on the one hand on certain known thermoplastic compositions and on the other hand on the preferred thermoplastic Mas30

sen according to the invention. The results show that the known compositions are more sensitive to this than the preferred thermoplastic compositions according to the invention.

A further experiment, which explains the influence of the notch radius on the toughness, is carried out as follows: Each of the two masses specified below is incised to a depth of 0.5 mm with a razor blade which gives a notch radius of approximately 5 (i) and with the impact tester according to Gardner IG-1115, manufactured by Gard-10ner Laboratories, Inc., Bethesda, Maryland, V.St.A. The fracture occurs under the following loads:

Base mass comparison mass B

6.9 cm-kg 9.2 cm-kg

15

A thermoplastic composition according to the invention, as described in Example 5, breaks under the same method at a load of 79.5 cm-kg.

Table IV

Izod impact strength as a function of the notch

Izod impact strength, mkg / cm - flow direction cross direction

Example thermoplastic mass facing away facing away facing

Comparison 1

Polyamide 16

0.495

0.354 0.163

0.403

Comparison 2

Polyamide 1

0.046

0.048 0.054

0.052

Comparison 3

Comparison B

0.142

0.142 0.098

0.174

164

20% polymer 1 in polyamide 1 0.479

0.218 0.201

0.299

165

30% polymer 1 in polyamide 1 1,214

1,334 1,061

1.383

166

20% polymer 43 in polyamide 1 0.697

0.713 0.659

0.833

167

20% polymer 5 in polyamide 1 0.642

0.713 0.637

0.806

Table V

Influence of the notch radius on the Izod impact strength

Izod impact strength, mkg / cm

example

Thermoplastic mass at 50 µm notch

- at 250 (in the notch

radius*

radius*

Comparison 1

Polyamide 1

0.03

0.053.

Comparison 2

Polyamide 7

0.067

0.121

Comparison 3

Polyamide 14

0.063

0.816

Comparison 4

Polyamide 15

0.142 / 0.822

0.174 / 0.92

14

Polyamide 1 + 20%

0.996 / 1.018

0.898 / 0.98

114 84 112 81

69

105 111

70

44

Polymer 5 polyamide 1 + 20% polymer 65 polyamide 6 + 20% polymer 33 polyamide 6 + 20% polymer 63 polyamide 6 + 20% polymer 30 polyamide 6 + 10% polymer 1 + 10% polymer 18 polyamide 6 + 20% polymer 52 polyamide 6 + 20% polymer 61 polyamide 1 + 10% polymer 1 + 10% polymer 19 polyamide 1 + 15% polymer 5

0.729 / 0.969 0.561 / 0.751 1.132 / 1.165 0.604 / 0.838 0.517 / 0.659

0.582 / 0.621 0.816 / 0.419 0.637 / 0.561

0.865 / 0.974

0.767 / 1.04

0.577 / 0.751

1.208 / 1.208

0.55 / 0.8

0.637 / 0.784

0.593 / 0.626

1.236 / 1.17

0.653 / 0.98

0.942

* Gate end / other end.

Example 168

A mixture of 85 percent by weight of base 1 and 15 percent by weight of polymer 66, which contains the additives specified in Example 154, is extruded into a melt film. The mixture is extruded at a temperature in the range of 280 to 285 ° C in a sterling extrusion press through a 20.32 cm wide Johnson press mold kept at about 290 to 295 ° C. The melt film is extruded onto the surface of a cooling roll rotating at 4.572 m / min, which is kept at about 70 ° C. In order to be able to cool the 250 µm thick cast film evenly, it is electrostatically adhered to the drum. Samples of 10.16 cm x 10.16 cm cut out of the rolled-up film are simultaneously placed on the 2.5fa31 649 566 in two mutually perpendicular directions at 230 ° C

stretched out. The cast film can be stretched out evenly in all directions. The base 1 is very difficult to cast into a film, which is why the base 5 is used as a control. A film cast from the base material 5 5 without the polymer 66 is difficult to stretch uniformly and suffers streaking.

Another sample of the cast film is processed by thermoforming after preheating for about 40 seconds in an oven at 210 ° C. to form a 3.81 cm deep bowl io with a diameter of 12.7 cm. The male mold of the bowl mold is heated to 200 ° C and the female mold to 160 ° C.

The multiphase thermoplastic composition according to the invention is advantageously used for the production of films.

C.

Claims (15)

649566 PATENT CLAIMS 1. Multi-phase, thermoplastic mass with a phase of a number average molecular weight of at least 5000 polyamide resin P as a matrix, in which particles T of straight or branched chain polymer with a particle size in the range of 0.01 to 3 µm in a concentration of 1 to 40% by weight, based on the polyamide resin P and the particles T, are dispersed and bonded to the polyamide resin P, which particles are straight-chain or branched-chain polymer of the formula I. A (a) B (b) C (C) D (d) E (e) F (f) G (g) H (! I) (I) included, the unit selected from A to H can be arranged as desired, and the tensile modulus is in the range of 0.69 to 34470 N / cm2 and is less than one tenth of the tensile modulus of the polyamide resin P, with the symbols A to H in the formula I mean the following units, of which only the unit D contains epoxidal: A is a unit of the monomer ethylene, B the unit CO, C is a unit of monounsaturated monomer from the group consisting of C]) a, β-ethylenically unsaturated carboxylic acids with 3 to 8 C atoms, which are monounsaturated, C2) monoesters of dicarboxylic acids belonging to the acids mentioned under Ci) with saturated alcohols having 1 to 29 C atoms, c3) internal anhydrides of dicarboxylic acids belonging to the acids mentioned under C]) and c4) vinylbenzoic acid and vinyl phthalic acid, units C of mono- and dicarboxylic acids belonging to the acids mentioned under Cj) and of dicarboxylic acid monoesters mentioned under c2) being in metal salt form and units C of dicarboxylic acids belonging to the acids mentioned under Ci) and of dicarboxylic acid monoesters mentioned under c2) can be neutralized with caprolactam oligomers with amine end groups and a degree of polymerization of 6 to 24, D is a unit of monounsaturated epoxy with 4 to 11 carbon atoms, E is a unit as it results when one molecule of an aromatic sulfonyl azide from the group consisting of ej aromatic sulfonyl azides, which are mono- or dicarboxylic acids having 7 to 12 carbon atoms, e2) monoesters of dicarboxylic acids with 1 to 29 carbon atoms belonging to the acids mentioned under e ^ and e3) internal anhydrides of dicarboxylic acids belonging to the acids mentioned under ei), azide nitrogen is removed, carboxyl groups of units E being present in the form of metal salts can, F is a unit of monounsaturated monomer from the group consisting of the monounsaturated acrylic and methacrylic esters with 4 to 22 C atoms, the monounsaturated vinyl esters with 1 to 20 C atoms, the monounsaturated vinyl ethers with 3 to 20 C atoms, the vinyl and vinylidene halides and the monounsaturated nitriles with 3 to 6 C atoms, G is a unit of monounsaturated monomer from the group consisting of ethylene in which hydrogen is replaced by optionally substituted aryl which is free from acid groups or alkyl having 1 to 12 carbon atoms, vinylpyridine and vinylpyrrolidone, H is a unit of straight-chain or branched-chain or cyclic monomer which has 4 to 14 C atoms and at least two unsaturated carbon-carbon bonds in the molecule, and the mole fractions (a) to (h) in which the units A to H are present are in the following ranges: (a) 0 to 0.95 (b) 0 to 0.3 (c) 0 to 0.5 (d) 0 to 0.5 (e) 0 to 0.5 (f) 0 to 0.99 (g) 0 to 0.99, and wherein the polymer of formula I contains at least one of components B, C, D and E, with the proviso that that if A is present in addition to at least one of components B, C, D and E, at least one of components F, G and H is also present. 2. Multi-phase, thermoplastic composition according to claim 1, in which the particles T have a size in the range from 0.02 to 1 µm. 3,649,566 22. Multi-phase, thermoplastic composition according to claim 1 in the form of a film. 23. A method for producing a multi-phase, thermoplastic composition according to claim 1, thereby 3. Multi-phase, thermoplastic composition according to claim 1, characterized in that the tensile modulus of the polymer of formula I is in the range from 3.45 to 13788 N / cm2. 4. Multi-phase, thermoplastic composition according to claim 1, characterized in that the melting point of the polyamide resin P is above 200 ° C. 5 indicates that in a closed system 60 to 99 percent by weight of polyamide resin with a number average molecular weight of at least 5000 and 40 to 1 percent by weight of straight-chain or branched-chain polymer of the formula I defined in claim 1 at a temperature which is around 5 is up to 100 ° C. above the melting point of the polyamide resin, mixed and the polymer of the formula I is distributed in the polyamide resin by shearing in a particle size in the range from 0.01 to 3.0 μm and causes it to adhere to the polyamide resin. 5 5. Multi-phase, thermoplastic composition according to claim 4, characterized in that the polyamide resin P is a straight or branched chain polyamide. 6. Multi-phase, thermoplastic composition according to claim 1, characterized in that the polyamide resin P is a polyamide made of a dicarboxylic acid with 4 to 12 carbon atoms and a diamine with 4 to 14 carbon atoms. 7. Multi-phase, thermoplastic composition according to claim 1, characterized in that the polyamide resin is polycaprolactam. 8. Multi-phase, thermoplastic composition according to claim 1, characterized in that it contains at least one colorant in a concentration of up to 5.0 percent by weight, based on the composition. 9. Multi-phase, thermoplastic composition according to claim 1, characterized in that it contains glass fibers in a concentration up to 50 percent by weight, based on the mass. 10th 15 20th 25th 30th 35 40 45 50 55 60 65 mer from the group fumaric acid, maleic acid, maleic anhydride and fumaric acid and maleic acid monoalkyl esters with 1 to 3 carbon atoms in the alkyl group and after the grafting has a melt index of 0.1 to 100 g / 10 min, determined according to the ASTM Test standard D 1238 at 280 ° C and a total load of 2160 g. 10. Multi-phase, thermoplastic composition according to claim 1, characterized in that it contains fibrous or pulverulent mineral fillers and reinforcing agents in a concentration of up to 50 percent by weight, based on the composition. 11. Multi-phase, thermoplastic composition according to claim 1, characterized in that it contains a stabilizing agent in an amount of up to 1.0 percent by weight, based on the polyamide resin. 12. Multi-phase, thermoplastic composition according to claim 1, characterized in that the polymer of formula I is a copolymer of ethylene, propylene and He-xadien- (1,4), with a monomer from the group fumaric acid, maleic acid, maleic anhydride and Fumaric acid and maleic acid monoalkyl esters with 1 to 3 carbon atoms in the alkyl group and after grafting a melt index of 0.1 to 100 g / 10 min, determined according to ASTM test standard D 1238 at 280 ° C and a total load of 2160 g. 13. Multi-phase, thermoplastic composition according to claim 1, characterized in that the polymer of formula I is a tetrapolymer made of ethylene, propylene, hexadiene (1,4) and norbornadiene (2,5), which with a Mono2 14. Multi-phase, thermoplastic composition according to claim 13, characterized in that the polyamide resin P is polyhexamethylene adipamide. 15. Multi-phase, thermoplastic composition according to claim 13, characterized in that the polyamide resin P is polycaprolactam. 16. Multi-phase, thermoplastic composition according to claim 1, characterized in that the polymer of formula I is a copolymer with random distribution of the monomer units, consisting of units of ethylene, units of methyl or ethyl acrylate, in a concentration of 0.0025 to 0.077 Mol per 100 g of the polymer units present in a monoalkyl ester of an ethene-1,2-di-carboxylic acid, the alkyl group of which has 1 to 6 carbon atoms, and CO in a concentration of 0.64 to 0.80 mol per 100 g of the copolymer. Units exist, the ethene-1,2-dicarboxylic acid monoalkyl ester units being 0 to 100% neutralized to lithium, sodium, potassium, calcium or zinc salt and at 190 ° C. under a total load of 2160 g, in accordance with the ASTM test standard D 1238, Condition G, the melt index determined for the non-neutralized copolymer is in the range from 0.3 to 100 g / 10 min and for the neutralized copolymer in the range of 0.04 to 100 g / 10 min. 17. Multi-phase, thermoplastic composition according to claim 16, characterized in that the monoalkyl ester consists essentially of maleic acid monoethyl ester. 18. Multi-phase, thermoplastic composition according to claim 17, characterized in that the polyamide resin P is polyhexamethylene adipamide. 19. Multi-phase, thermoplastic composition according to claim 17, characterized in that the polyamide resin P is polycaprolactam. 20. Multi-phase, thermoplastic composition according to claim 1 with a concentration of particles T of 2 to 40 wt .-%, based on the polyamide resin P and the particles T, characterized in that the numerical value expressed in J / cm, according to ASTM D 256 determined Izod impact strength of the mass in the dry state, as obtained in the deformation, at least i) the value 0.533- (B + 0.2 CO or ii) the value 0.533- (B + 2 + 0.5 ( C2-10)) or iii) the value 0.533- (B +12) has, the minimum value i) in the event that the concentration of the particles T is in the range from 2 to 10% by weight, the minimum value ii) in the event that the concentration of the particles T is in the range from 10 to 30% by weight .-%, and the minimum value iii) applies in the event that the concentration of the particles T is in the range from 30 to 40% by weight, B denotes the numerical value of the Izod impact strength of the polyamide resin P expressed in J / cm, and Q and C2 denote the numerical value of the concentration of the particles T expressed in% by weight, based on the polyamide resin P and the particles T. 21. Multi-phase, thermoplastic composition according to claim 5, characterized in that the Izod impact strength of the composition is higher than 4.22 J / cm when the concentration of the particles is 5 to 20 percent by weight. 15