DE1256887B - Molding compositions based on olefin polymers and bis-carboxylic acid amides - Google Patents

Description

GERMAN 4f9mw PATENT OFFICE

German class: 39 b -22/06

EDITORIAL ™

File number: B 84533IV c / 39 b

J 256 887 filing date: November 17, 1965

Opened on: December 21, 1967

Films made from polyolefins, in particular from polyethylene having a density of about 0.92, sometimes have the blocking property, which interferes with further processing. This is what blocking means Gluing several foils on top of each other. The blocking of foils, for example, leads to The manufacture of packaging, such as pouches, creates difficulties as it causes the pouch to lift off Stack as well as its opening and filling difficult. The disadvantage of blocking is all the more apparent, the faster the films are produced, for example by the blow molding process.

The block value, which is determined as follows, serves as a measure for blocking:

Two films made of the same polyolefin are pressed at 70 ° C. for at least 24 hours with a pressure of 80 g / cm ^2. Strips 15 mm wide are cut from the films that then adhere together. The non-glued ends of these strips are stretched in a tearing machine and the film strips are detached from one another at a take-off speed of 80 mm / min. The block value indicates the force in grams required ^{to separate each cm 2 of the glued strips.}

It is known that you can add polyolefins, such as polyethylene, fatty acid amides, whereby the The sliding behavior of films produced therefrom and / or their blocking behavior is improved. For example can improve the sliding behavior of polyethylene films by adding oleic acid amide or stearic acid amide can be greatly improved. However, the blocking behavior of the Slides not improved. For example, polyethylene films contain oleic acid amide or stearic acid amide contain, block values (24 hours at 70 ° C) of well over 150. Also polyethylene films, the erucic acid amide, Ν, Ν'-distearyl ethylenediamide or alkylene-bis-erucic acid amides, alkylolamides or fatty acid esters according to British patents 752,820,818,728, U.S. patents 2,770,608, 2 921 048, 2 956 979, 2 991 263 and 2 991 265, French patents 1 236 729 and 1295 282, contained in Belgian patent 585 077 and German patent 1,159,636 have block values (24 hours at 70 ° C.) over 150. In addition The block values of films made from the known molding compounds often increase during storage.

It has now been found that molding compounds based on olefin polymers and 0.02 to 5 percent by weight - based on the amount of olefin polymers - bis-carboxamides, the mono-molding compounds containing 6 to 30 carbon atoms, based on olefin polymers
and bis-carboxamides

Applicant:

Aniline & Soda Factory in Baden

Corporation,

Ludwigshafen / Rhine

Named as inventor:
Dr. Walter Hensel,

Dr. Oskar Büchner, Ludwigshafen / Rhine

Derive carboxylic acids, have particularly low block values if they are bis-carboxamides from aromatic Diamines and optionally also contain oleic acid amide. The block values from slides the new molding compositions do not deteriorate even after storage at 50 ° C. for several weeks. Only after several weeks If the films are stored at 70 ° C., there is a slight deterioration in the block values, however the block values remain below 150 even then.

The olefin polymers used for the molding compositions are those according to the customary high and low pressure polymerization processes produced polyethylene, polypropylene and polybutene (I) as well as copolymers from predominant quantities Monoolefins, such as ethylene, propylene and butene- (I), in question. Examples of suitable copolymers are those made of ethylene and up to about 20 percent by weight vinyl esters, such as vinyl acetate or acrylic esters, such as ethyl and butyl acrylate. Such olefin polymers generally have molecular weights from 20,000 to 100,000 (determined according to D e s r e u χ, Bull. Soc. Chim. Belg., Vol. 59, p. 476 [1950]). Of particular interest are molding compositions which contain olefin polymers, which at pressures above 1000 atmospheres are made, such as in particular polyethylene with a density of 0.915 to 0.935 and a melt index from 1 to 20, preferably from 1.5 to 5.

Suitable bis-carboxamides are derived from monocarboxylic acids with 6 to 30 carbon atoms, preferably from aliphatic monocarboxylic acids having 10 to 20 carbon atoms. Suitable monocarboxylic acids are z. B. lauric acid, stearic acid, palmitic acid, oleic acid, caproic acid, caprylic acid

709 709/476

and myristic acid. The aromatic diamines can have one or more aromatic radicals. They preferably have 1 or 2, optionally fused benzene nuclei, the amino groups can be arranged as desired. In addition, the aromatic radicals can have other substituents, z. B. alkyl groups, e.g. B. methyl, ethyl or butyl groups and / or alkoxy groups, e.g. B. methoxy and carry ethoxy groups. Examples of aromatic diamines include o-, m- and p-phenylenediamine, 1,4-diamino-2-methyl-benzene, 1,4-diamino-2-methoxybenzene, 1,4-diaminonaphthalene, 1,6-diaminonaphthalene. 1,8-diaminonaphthalene, p.p'-diamino - diphenyl, ρ, ρ '- diamino - diphenylmethane, m, m'-diaminobenzophenone, ρ, ρ'-diaminobenzophenone, diamino-diphenyl sulfide, diamino-diphenyl ether, such as ρ, ρ'-diamino-diphenyl ether and diaminodiphenyl sulfones, such as ρ, ρ'-diamino-diphenyl sulfone, in Question. The particularly suitable aromatic diamines preferably have the general formula

NH,

H ₂ N

H, N

NH ₂
NH,

H, N

15th

25th

3 °

35

40

45

in which X stands for an alkylene radical having 1 to 8 carbon atoms. - CO -, - S -, - O - or - SO ₂ -.

Examples of particularly suitable bis-carboxamides are N, N'-di - lauroyl - ρ - phenylene - diamine, N, N '- dipalmitoyl - ρ - phenylene - diamine, N, N'-distearoyl-p-phenylene-diamine, N , N'-dilauroylp, p '- diamino - diphenylmethane, N ₅ N' - distearoylp, p '- diaminodiphenylmethane, N, N' - dilauroyl-ρ, ρ'-diaminobenzophenone and N, N'-dilauroyl-benzidine.

The aromatic bis-carboxamides are added to the olefin polymers in amounts of 0.02 to 5, preferably from 0.04 to 0.2 percent by weight, based on the amount of olefin polymers, added. They can be mixed with the olefin polymers in a customary manner.

In addition to the aromatic bis-carboxamides, the molding compositions can also contain other customary ones Additives, e.g. B. stabilizers, antistatic agents, flame retardants, fillers and especially lubricants included in the usual quantities.

As a lubricant, for. B. fatty acid amides, such as oleic acid amide and its substitution products, erucic acid amide and hexamethylene-bis-erucic acid amide and alkylene diurethanes, such as hexamethylene diurethane, in question. An additional content of 0.02 to 5, preferably, of the molding compositions has proven useful from 0.04 to 0.2 percent by weight, based on the amount of polymer, oleic acid amide. Molding compounds that contain oleic acid amide in addition to the aromatic bis-carboxamides, stand out in addition to a very good block behavior

55

60 has particularly good sliding properties and very good printability. It is surprising that the aromatic bis-carboxamides do not impair the effect of such lubricants, as is the case with other antiblocking agents, e.g. B. in bis-stearoyläthylendiamid (applies particularly to Example 4 with a higher addition) is the case.

The parts mentioned in the following examples are parts by weight.

example 1

A mixture of 2000 parts of polyethylene with a density of 0.924 and a melt index of 1.4, 0.8 parts of N, N'-dilauroyl-p, p'-diamino-diphenylmethane and 0.8 parts of oleic acid amide is poured into a commercially available extruder at 160 for 5 minutes ⁰ C kneaded and then granulated. The granulate is fed to a film blowing apparatus and a film is blown therefrom at a blowing temperature of 140 ° C. and a take-off speed of 7 m / min using an annular nozzle with a diameter of 50 cm and a nozzle gap of 0.5 mm.

The block and slip values of the film are given in Table 1 below. The sliding values were determined according to the information in German patent specification 1,159,636.

Table 1

Bloekwert
(70 Ό

80 after 24 hours

90 after 7 days

80 after 3 weeks

Sliding value
(Inside film)

20th
22nd
24

If the amount of the additives is increased from 0.8 parts each to 1.2 parts each, the result is under otherwise identical conditions, a film with a blocking value when stored for 24 hours to 3 weeks at 70 ° C is 20 and which has a sliding value of 15 to 20 under these conditions.

Example 2

As indicated in Example 1, a molding composition of 2000 parts of polyethylene becomes 0.8 parts N, N'-di-stearoyl-p, p'-diamino-diphenylmethane and 0.8 parts of oleic acid amide blown a film. the Foil has good printability. Their blocking and sliding values are compiled in Table 2 below.

Table 2

Block value Sliding value (70 Q (Inside film) 120 28 140 after 7 days 28 120 after 3 weeks 30th

Example 3

The procedure described in Example 2 is followed, but the aromatic bis-carboxamide is used N, N'-dipalmitoyl-p, p'-diamino-diphenylmethane. He-

Claims (1)

What we hold is a film, the blocking and slip values of which are given in Table 3 below. Table 3 Block value j floating value (70 C)! (Inside film) 90 after 24 hours | 30th 130 after 7 days! 38 120 after 3 weeks \ 38 Example 4 As indicated in Example 1, a molding compound made of 2000 parts of polyethylene with a density of 0.934 and the melt index 4, 1.5 parts of N, N'-dilauroyl-ρ, ρ'-diamino-diphenylmethane and 1.5 parts of oleic acid amide blown a film. A film is obtained which is easy to print on. Your block and glide values are compiled in the following table 4. Table 4 1 Block value j floating value (70 C) j (inside of film) 0 after 24 hours ¹ 30 i 60 after 7 days 36 80 after 3 weeks | 38 Example 5 The procedure is as indicated in Example 4, but the aromatic bis-carboxamide is used N, N'-dilauroyl-p-phenylenediamine. A film is obtained, the blocking and sliding values of which are shown in the following Table 5 are compiled. Table 5 Block value I sliding value (70 C) j (inside of film) 80 after 24 hours | 29 100 after 7 days j 35 120 after 3 weeks j 30 Example 6 The procedure is as indicated in Example 4, but used as the aromatic bis-carboxamide N, N'-stearoyl-p, p'-diamino-diphenylmethane. What is obtained is a film that is easy to print and whose block and Sliding values are summarized in the following table 6. Table 6 Block value Sliding value (70 C) (Inside film) 80 after 24 hours 29 100 after 7 days 35 120 after 3 weeks 30th Example 7 A mixture of 2000 parts of polybutene (I) and 2 parts of N, N'-dioctyl-p, p'-diamino-diphenyl sulfone is kneaded in a commercial extruder for 5 minutes at 160 ° C and then granulated. That As indicated in Example 1, granules are blown to form a film. The following table shows the blocking and slip values of the film. Table 7 Block value Sliding value (70 C) (Inside film) 98 after 24 hours 186 108 after 7 days 188 110 after 3 weeks 190 Example 8 The procedure is as indicated in Example 1, but instead of 0.8 parts N, N'-dilauroyl-p, p'-diamino-diphenylmethane is used 2 parts of N, N'-dioctoyl-p, p'-diamino-diphenyl sulfone; furthermore, the addition is omitted of oleic acid amide. A film is obtained whose blocking and slip values are given in the table below. Table 8 Block value Sliding value (70-Q (Inside film) 110 after 24 hours 195 120 after 7 days 199 110 after 3 weeks 200 Claim: Molding compositions based on olefin polymers and 0.02 to 5 percent by weight - based on the amount of olefin polymers - bis-carboxamides, which are from 6 to 30 carbon atoms derive containing monocarboxylic acids, characterized in that they are bis-carboxamides from aromatic diamines and optionally also contain oleic acid amide.