NL7902972A - POLYAMIDE AND POLYALKENE MODIFIED THEREFOR. - Google Patents

Description

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Ref .: UE (K) 214

Unilever-Emery N.V. in Gouda "Polyamide and polyolefin modified therewith" v

The Applicants mention as inventors: Adriën George HINZE, Abraham Oan MEULENBERG and Robert Pieter ROGGEVEEN.

The application relates to polyamides of a particular construction and to polyolefins in which these polyamides are included in small quantities, thereby improving the dyeability of this polyolefin for acid dyes.

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It is known that polyolefins are generally difficult to dye due to the lack of polar groups which can function as an attachment site for dye molecules. Hence, much attention has been paid heretofore to the development of polyolefin in which the desired polar groups are present and which therefore exhibit good dyeability. Good dyeability is a collective term for good color intensity, good homogeneity and good color fastness of the dyed modified polyolefin.

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Various polyolefins modified with basic polyamides have been described in the literature. For example, Dutch Patent No. 151895 polyolefin modified with a basic compound, for example a polyamide, of which 7902972

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-2- UE (K) 214 the basic nitrogen groups have been converted into a salt at least partly by means of a strong acid. The polyamide thus used is composed of aliphatic polyamines, preferably of the formulas: 5 H2N-R1-N-R2-NH2 and H ^ -Rj-NR ^ NR ^ NH ^ R3 R3 R5 in which R ^, R2 and R ^ alkylene groups , preferably C 1 -C 8, and. R3 and Rg a hydrogen atom or a C 1 -C 8 alkyl group. Aliphatic, aromatic, cycloalkyl and alkylaryl diamines can also be used. Furthermore, the polyamide as a carboxylic acid component contains aliphatic acids such as succinic acid, glutaric acid, adipic acid, 2,2,4-trimethyl adipic acid, turmeric acid, azelaic acid, sebacic acid and dodecanedioic acid, as well as alkyl-substituted aliphatic dicarboxylic acids, dimer unsaturated fatty acids, aromatic, cyclo-15 alkyl and alkyl aryl dicarboxylic acids can be used. Neutralization of the basic polyamides with a strong acid is considered necessary for a good dyeing result.

Dutch patent application 6707121 describes polyolefin modified with basic polyamide, the polyamide being composed of a polyamine containing no more than two primary amino groups and one or more tertiary amino groups, as well as a dicarboxylic acid. For suitable polyamines, a number of general formulas are listed, including R 1 -NH-Rg-N-R-NHRg, R 3, as well as a number of dicarboxylic acids, while diamine, especially aliphatic diamine, can replace part of the polyamine. The Examples describe polyamides based on hexamethylenediamine, N, N'-bis (3-amino propyl) -methyl amine and either azelaic acid or sebacic acid (Example I and Example II (1), respectively.

However, the known modified polyolefins, as described in said patent / application, are not entirely satisfactory in terms of dyeability.

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It has now been found that by modifying polyolefin with certain new polyamides, excellent dyeing properties such as color intensity, color homogeneity and color fastness could be obtained.

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The new polyamide compositions according to the invention make it possible to obtain excellent dyeing results at low addition percentages, and in addition, no neutralization step is required. A low addition percentage is important, because it avoids as much as possible negative influence on the polyolefin properties by the additive.

These new polyamides have an acid number below 15, preferably below 10, an amine number of 75-200, preferably 15 of 100-150 (all in mg KOH / gram) and are composed of groups derived from A. An aliphatic diamine with 2 -3 carbon atoms between the nitrogen atoms; B. A tri amine of the formula HgN-Rj-N-Rg-N 11 R 2 wherein R 1 and R 3 represent alkylene groups and R 2 represents an alkyl group, which groups may contain 1 to 6 carbon atoms; C. An aliphatic dicarboxylic acid containing 6 to 19 carbon atoms; and optionally D. A polymerized fatty acid containing 0-25, preferably 3-25 mol. percent of the total dicarboxylic acids. The best results are obtained when this mol percentage is 7-12.

Ethylene diamine is preferably used as aliphatic diamine, but propanediamine-1,2 can also be used; propanediamine-1.3; 2-methyl-propanediamine-1,3 and 2,2-dimethyl-35-propanediamine-1,3. It therefore concerns diamines in which 2 or 3 carbon atoms are in a straight chain between the two nitrogen atoms of the two primary amine groups, while lower alkyl branches, preferably methyl, may also be present.

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As tri amines, compounds of the formula H 2 N-RrN "R 3 -NH 2 come in ammonium, wherein R 1, R 2 and R 3 preferably contain 1-6 carbon atoms.

Preferably R 1 and R 2 contain 2-4 carbon atoms and R 3 represents a methyl group. It is not necessary that R 1 and R 2 contain the same number of carbon atoms. For example, N, N'-bis (3-aminopropyl) methylamine may be used, which is particularly preferred, but may also be used: N, N'-bis (2-aminoethyl) methylamine, N, N ' bis (4-aminobutyl) methylamine, and N, N'-bis (3-aminopropyl) -ethyl amine.

The molar ratio of aliphatic diamine to triamine 15 is generally 0.4-0.6: 1.

As dicarboxylic acid can be used adipic acid, 2,2,4-trimethyl adipic acid, turmeric acid, azelaic acid, sebacic acid, dodecanedioic acid generally aliphatic dicarboxylic acids containing 6-19 carbon atoms, preferably 6-12 carbon atoms, those with 9 or 10 carbon atoms. dust atoms give the best results overall.

As polymerized fatty acids, the known thermally or catalytically polymerized unsaturated fatty acids containing 16-22 carbon atoms, preferably 18 carbon atoms, can be used. The polymerized fatty acids should consist of at least 75% by weight of dimeric fatty acids, the remainder consisting largely of trimeric fatty acids; the polymerized fatty acids used preferably contain least 90 wt% dimer.

Also, there is a preference for the use of hydrogenated polymeric fatty acids.

Sometimes it is desirable for the viscosity control of the polyamide to also include a small percentage of a monocarboxylic acid or monoamine. This percentage partly depends on the monomer content of the polymerized fatty acids and is generally less than 10 mol. percent of the total carboxylic acid, resp. amine component. These compounds contain 7902972-5 UE (K) 214 as a rule 6-20 carbon atoms.

The new basic polyamides are prepared from the amines and carboxylic acids by methods well known. As a rule, there is a very small molar excess of amine or carboxylic acid. In addition to amine and carboxylic acid, one can also convert their functional derivatives, e.g. lower alkyl esters of the carboxylic acids or some salts of the amines. The ingredients are usually brought together in a four-necked flask with cooler, stirrer, thermometer and gas inlet pipe (N2) and the reaction mixture is heated to 170-250 ° C - usually 200-210 ° C - and kept at that temperature for four hours. reaction water distills off. In this way a light yellow liquid is obtained, which is poured, cooled to a hard brittle, crushed and ground, and the indicated constants are determined.

According to the invention, the new polyamide thus obtained can be used to modify polyolefin by incorporating 0.5 to 10% by weight, based on the polyolefin, of the said polyamide and distributing it homogeneously therein. Preferably, 3-8 weight percent of the polyamide is included.

Polypropylene, in particular isotactic, can also be used as polyolefin, also linear polyethylene or copolymers thereof and furthermore steroidal 4-methylpentene-1.

The incorporation of the polyamide into the polyolefin can be effected by melt mixing, extruding or rolling together and the like. From the polyolefin thus modified, threads, films and other articles can be made which have an improved dyeability over dyes with acid groups. The invention thus provides painted or unpainted articles which consist wholly or partly of modified polyolefin.

The invention is now further illustrated by the following Examples 7902972-6-US (K) 214 <;

Examples 1-5

A series of polyamides were prepared as described above, 5 from the raw materials in mill indicated below in the table.

For comparison, a polyamide according to Example (I) of Dutch patent application 6707121 was also prepared, as well as comparative example (2), in which the relative amounts of amines were changed. Amine number, acid number, softening point (Bullet + 10 Ring), as well as viscosity at 190 ° C were determined (Compare Table 1).

TABLE 1

Vergl. Vergl. 12345 (1) (2) _____ 15 Azelaic Acid 4.0 4.0 4.0 t 3.6 3.6 2.0

Adipic acid 2.0

Sebacic acid 4.0

Stearic acid 0.2 0.2 0.2 Γ V 21

Dimer fatty acid 0.4 J 0.4 '0.4' • 20 BAPMA 2.28 2.57 2.57 2.57 2.57 2.57 2.57 HMDA 2.30 1.76 EDA 1.76 1 .76 1.76 PDA 1.2 1.76 PDA 1.3 1.76 25 Amine value mgKOH / g 113 115 123 119 134 140 122

Acid value mgKOH / g 0.7 3.8 3.3 2.8 4.0 8.3 4.1

Softening point ÖC, 17.1 157 185 171 159 152 130 30 Viscosity (Pa.s) (190 ° C) 5.3 4.6 5.2 5.2 1.15 0.75 2.85

The abbreviations used in the table have the following meanings: BAPMA is N, N'-bis (3-aminopropyl) methylamine HMDA is hexamethylenediamine 35 EDA is ethylenediamine PDA is propanediamine 7902972 * 1 -7-UE (K) 214 1) in the commercially available fractionated and hydrogenated polymeric fatty acids Empol 1010 ex Unilever-Emery NV D: T: M = 95: 5: 0.1.

2) here a non-hydrogenated polymeric fatty acid Empol 1022 5 with a dimer-trimer ratio of 80:20 was used.

The polyamides described above were added to isotactic polypropylene in amounts of 5%, based on the polyolefin, and homogeneously distributed therein for 8-10 minutes by rolling at 175 ° C. A film of about 2 mn thickness was taken from the roller and test strips of about 2.5 x 4.0 cm were cut from it. These test strips were dyed with the dye. Lissamine Blue B (ex I.C.I.). To this end, a 0.1% by weight solution in distilled water was made from the dye. 0.1% by weight of formic acid was added to this solution and the whole was diluted to 0.075% dye. The solution was brought to 100 ° C, after which the test strips were kept in the bath at this temperature for 4 hours. At the end of that period, they were removed from the dye solution, rinsed and washed with soap.

The dyeing result was visually assessed for color intensity, color homogeneity and color fastness. The results appeared to vary widely, from barely colored to streaky, light blue and glossy deep blue. The overall impression was expressed in four grades, ranging from -, 0, '+ to +++ 25 The rating was as follows:

Verg !. Verg !. Ex 1 2 3 4 5 (1) (2) _ _ _ _ _ - 0 + 1H "++ ++ ++ 7902972

Claims (16)

1. Polyamide with an acid number below 15 and an amine number of 75-200, which is composed of groups derived from: A) an aliphatic diamine with 2 or 3 carbon atoms between the nitrogen atoms; . B) a tri amine of the formula H 2 N - R 1 - N - R 3 - NH 2 r 2 wherein R 2 R 2 and R 8 represent C 1 -C 8 alkyl (en) groups; C) a C8 -C18 g aliphatic dicarboxylic acid. 10 Polyamide according to claim 1, characterized in that the polyamide also contains groups derived from polymerized fatty acids. Polyamide according to claim 1 or 2, characterized in that the acid number is less than 10 and the amine number is 100-150. 4. Polyamide according to claim 3, characterized in that the carboxylic acid component of the polyamide consists for less than 25 mol% of dimer fatty acids. Polyamide according to any one of claims 1 to 4, characterized in that the aliphatic diamine is ethylenediamine. 25 Polyamide according to any one of claims 1 to 5, characterized in that in the triamine R 1 and R 5 represent propylene. 7. Polyamide according to any one of claims 1 to 6, characterized in that R2 represents a methyl group. Polyamide according to any one of claims 1 to 7, characterized in that the dicarboxylic acid represents an unbranched Cg-Cl 2 aC-ia dicarboxylic acid. 7902972 -jf - UE (K) 214 * Polyamide according to claim 8, characterized in that the dicarboxylic acid contains from 9 to 10 carbon atoms. Process for preparing polyamides according to any one of claims 1 to 9, characterized in that the diamine, triamine and carboxylic acid or functional derivatives thereof are reacted at temperatures between 170 ° and 250 ° C. 11. A process for modifying polyolefin, characterized in that 0.5 to 10% by weight, based on the polyolefin, of a polyamide according to any one of claims 1 to 9 is incorporated therein. 12. Method according to claim 11, characterized in that polypropylene is used as polyolefin. Polyolefin which has been modified by incorporating 0.5 to 10% by weight of a basic polyamide therein, characterized in that a polyamide according to any one of claims 1 to 9 is used as the polyamide. Polyolefin according to claim 13, characterized in that polypropylene is modified as polyalkylene. Shaped articles consisting wholly or partly of polyolefin according to any one of claims 13 or 14. 16. Articles and methods as described above, particularly described in the Examples. 7902972