DE2146162A1 - Multiple polyamide resins and processes for their preparation - Google Patents

Description

Clayton, Manchester Ik, September 1971 ENGLAND Zo / Nie - Io 658 Multiple polyamide resins and processes for their Manufacturing

The invention relates to polyamide resins as a condensation product of a mixture of an aliphatic diamine and an aliphatic ether amine with a fractionated polymeric fatty acid and another polybasic fatty acid.

It is the object of the present invention to provide resinous mixtures with high molecular weight, in particular mixed polyamides with improved hardness, which have a high Have tensile strength and great extensibility, which makes them particularly suitable for the formation of high-melting point adhesives are suitable.

This object is achieved in that the aliphatic atheramine a split at its end

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is primary bi- or triamine, which is structurally of is derived from a polypropylene glycol.

The aliphatic diamine is preferably an alpha-omega primary aliphatic diamine, such as, for example, ethylene diamine, 1,2-propane diamine, 1,3-P * "opane diamine, tetramethylene diamine and hexamethylenediamine. Small proportions of aromatic, secondary amine groups can be included such as phenylenediamine, xylenediamine, isophoronediamine (l-amino-3-aminomethyl-3 · 5 »5-trimethylcyclohexane) and diethylenetriamine. The preferred diamine is ethylenediarain.

The aliphatic ether diamine is a polyoxypropylene amine known type, which is a mixture of compounds of the general formula

H ₀ N-CH.CH ₀ - (OCH ₀ -CH) -NH ₀

in which η has a mean value of 2.6 or a value of about 5 »6.

Another known amine is a mixture of compounds gene of the formula

₂ - [OCH ₂ . ₃

CH ₃ .CH ₂ -C CH ₂ - [OCH ₂ .CH (CH ₃ ) -] _y -NH ₂

CH ₂ - [OCH ₂ .CH (CH ₃ ) -] _z -NH ₂

in which χ + y + ζ is about 5t3.

The polymerized fatty acid can be any polymerizable unsaturated fatty acid or its base. Suitable acids can be obtained by dimerizing dry or semi-dry oil fatty acids, tall oil fatty acids or their esters «

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2H6162 "

The acids can be prepared by means of known methods by ionic radical polymerization or simple thermal polymerization obtained from natural or synthetic mono- or polyethylene acids and, if so desired the polymeric fatty acids can be hydrogenated.

The dine acids obtained in this way contain, in addition to the fatty acid, different amounts of monomeric and trimeric acids. These products are distilled for use in the present process, so that the proportion of dimer acid _{r is} preferably at least 80% but more than 9o% weight. The distillation can, for example, be a molecular distillation.

The other basic acid is preferably one

dibasic fatty acids, such as glutaric, adipic,

Pimelic, submeric and azelaic acids, but adipic acid is preferred.

The aliphatic diamine advantageously forms the major part the diamine mixture and the fractionated polybasic Fatty acid is the main part of the acids.

A monocarboxylic acid is also added to the reactants to terminate the chain. Comes as a monocarboxylic acid any kind in question, aliphatic or aromatic, straight-chain or branched jets or substituted if so desired. Suitable acids are aliphatic acids with 2 to 22 carbon atoms, such as acetic acid, Propionic acid, tall oil fatty acid, vegetable fatty acid mixtures, Stearic acid! the aromatic acids are, for example, benzoic acid, 4-tert-butylbenzoic acids with branched chains, for example isooctanoic acid, 2-ethylcaproic acid, 2-methylpentanoic acid and hydroxy acids, such as for example lactic acid and glycolic acid.

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BATH ORIGINAL

The amounts of the starting materials are chosen so that approximately the same number of area and carboxyl groups are present in the reaction mixture. The proportions are preferably taken so that the end product is low has free acid content and low free amine content. The reaction can take place at temperatures from iAo ° to 28o C, preferably from 200 to 22o ° C. The reaction time depends on the temperature, however approximately 4 hours in the preferred temperature range have been found to be suitable. The reaction becomes advantageous carried out in an inert atmosphere such as nitrogen, and the final stages are carried out at reduced pressure run through to remove volatile material.

The invention is explained in more detail below with the aid of examples.

example 1

In a reaction flask with several necks, which is equipped with a stirrer, a thermometer and a distillation head, 300 g (1.04 equivalents) of distilled dimeric acid from tall oil fatty acid (5.9 % monomer, 89.1 % dimer, 5 % polymer , Saponification equivalent 195), 4.6 g of stearic acid (0.0148 equivalents), 24 g of adipic acid (0.329 equivalents) and 3715 g of 1.2 diamine ethane (1.25 equivalents) plus 16 g of a known polyoxypropylene amine (0.139 Equivalents). The mixture is filled in at 2o5 to 215 ° C. for 4 hours at atmospheric pressure under a stream of inert gas and then for 2 hours under a vacuum of about 20 mm of mercury.

The polyamide obtained has an acid value of 4.4, an amine value of 4.5 and a softening value of 184 ° C the "ball and ring method" (ASTM E28-5OT) and a Schmelsviskoeität at 2o5 ° C of 43 poiee.

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2146182

Example 2

Following the method of Example 1, 1,3oo g (I, o4 equivalents) of distilled polymeric fatty acid, 4.6 g of stearic acid (0.0143 equivalents), 2k g of adipic acid (o, 329 equivalents) with 32.1 g (I, o7 Equivalents) of 1,2 diaminoethane and reacted with 36.7 g (0.319 equivalents) of the known polyoxypropyleneamine used in the example.

The product has an acid value of 2.9 and an amine value of 3.7 »a softening point of 163 ° C according to the" ball and Ring method "and the melt viscosity of 33 poise at 2o5 ° C.

Examples 3 to 12

The procedure of Example 1 was repeated using the reactants listed in the table below. The same dimer acid as in Example 1 was used. The properties obtained in the final products are also listed in the table

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Examples Aquival. Monomeric primary game d. least. Dicarbon diamine no. polymeric acid equivalents. ^ _ _.._. _w

Fatty acid valente (ethylene and ball- 25o ° C

diamine) method "

Multiple Softening Melting Vx Acid Value Amine Value diamine point in viscosity in mgKOH / g mg KOH / g equivalent. after "Ring Poise at

o.9o o.8o o, 7o o.6o o.9o o.8o o.7o o.95 o.9o 0.85

ti

<3 ■ Η Ό Λ

«3 <Η

5 /

Ο.1 179 ο C. ο.2 168 O C. ο.3 156 O C. ο.4 142 O C. ο. Io 148 O C. ο.2ο 14ο O C. ο. 3ο 129 O C. ο.ο5 169 O C. ο. Io 154 O C. ο.15 148 O C.

28

32

24

42

30th
18th
32

41
21

2.4 4.2

7.8 3.4

4.8 6.4 7.9 3.9 4.8

2.9

3.2

1.9

4.2

2.6

3.2

1.2

2.4

1.9

3.4

3.8

-F-CD

2U6162

The flexible polyamides according to the invention with high molecular weights are particularly suitable as adhesives, for example for use in the footwear industry, and show excellent properties as a control resin when without the ether diamine can be produced.

Expectations:

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Claims (12)

"- 8 claims 1. Polyamide resins as a condensation product of a mixture of an aliphatic diamine and an aliphatic Etheramine with a fractionated polymeric fatty acid and another polybasic fatty acid, thereby characterized in that the aliphatic ether arain is a primary di- or split at its end Triamine is which structurally is from a polypropylene glycol is derived. 2. Multiple polyamide resin according to claim 1, characterized characterized in that the aliphatic diet is an alpha-omega-diprimary aliphatic diamine such as ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, tetramethylenediamine and is hexamethylenediamine. 3. Multiple polyamide resins according to claim 1 or 2, characterized in that a small proportion an aromatic diamine, cycloaliphatic diamine and / or polyamines which contain secondary araine groups are additionally provided. k, in that the fractionated polymeric fatty acid is multiple polyamide resins according to claims 1 to 3, characterized in that a distilled dimerized fatty acid with at least 3o% of dimeric acid. 5. polyamide resins according to claims 1 to 4, characterized in that the polybasic Acid a dibasic fatty acid such as adipic acid is. 6. polyamide resins according to claims 1 to 5, characterized in that the alipha- 20981 3/1595 ■ '2U6162 table diamine forms the main part of the diamine mixture and the fractionated polymeric fatty acid represents the main proportion of acids. 7 «Mehrfachpolyaniidharze according to claims 1 to 6, characterized in that the ether amine a mixture of the compounds according to the formula H ₀ N-CH.CH ₀ - (OCH ₀ -CH) -NH_ s <2 <J ι η ^ in which η has an average value of 2.6. 8. A process for the manufacture of multiple polyamide resins which comprises condensing a mixture of an aliphatic Diamines and an aliphatic ether with a fractionated polymeric fatty acid and another polybasic acid, characterized in that the aliphatic ether amine is an is a branched primary diamine or triamine, which is structurally derived from a polypropylene glycol. 9. The method according to claim 8, characterized in that the reactants of the process the components specified in claims 2 to 7 are 10. The method according to claims 8 and 9i, characterized in that an equivalent number of amine and carboxyl groups are present in the reaction mixture , 11. The method according to claims 8 to Io, characterized in that the reaction is carried out at a temperature between 14o and 28o ° C, where 22o ° C predominates at a temperature of 2oo ° bin. 209813/1595 - Io - 12. The method according to claims Ö to 11, characterized in that the reaction in one inert atmosphere and at a reduced pressure in the final stages of the process for the removal of volatile matter Material is carried out. 13 · Process according to Claims 8 to 12, characterized in that a monocarboxylic acid is added as a chain closure. 209813/159 6