DE1570790A1 - Process for the production of polyamide condensation products - Google Patents

Description

The priority of filings in Great Britain on May 12, 1964, August 10, 1964 and March 15, 1965 is claimed.

The invention relates to polyamide condensation products, in particular those which are used to form elastic molded parts how threads are suitable.

According to the invention, condensation products are created which of a dicarboxylic acid and a mixture of a diaminopolyalkyleneoxy compound and an aliphatic, cyeloaliphatisohen or alkylcycloaliphatic amino acid and / or such a lactam, and optionally also an aliphatic, cycloaliphatic or aromatic diamine.

The compounds: dicarboxylic acid, diaminopolyalkyleneoxy compound, amino acid or lactam, or diamine can each used individually; or mixtures of these compounds can be used in each case.

All dicarboxylic acids are preferably aliphatic ^ dicarboxylic acids of the formula «

New Unterlaoen ^ j. jy ftf / ygf &

you changes *, v. 4.8.1967}

used, where η is zero or a positive whole Number is from 1 to 10. Adipic acid is particularly suitable. Oxalic acid, succinic acid, glutaric acid, sebacic acid and decanedicarboxylic acid can be mentioned as further suitable aliphatic dicarboxylic acids.

As suitable dicarboxylic acids there are also cycloaliphatic, alkylcycloaliphatic, aromatic and alkylaromatic dicarboxylic acids. Among cycloaliphatic dicarboxylic acids are meant Acids are understood that have an alkylene ring structure of the Formula:

r ^ n-i

contains, where η is equal to an integer from 5 to 16, and wherein two hydrogen atoms that are not on the same carbon atom and also not on adjacent carbon atoms are attached, are each substituted by a carboxyl group to form the corresponding dicarboxylic acids. at Use of aromatic acids should not remove the carboxyl groups on adjacent carbon atoms of a ring system lie. Examples of such dicarboxylic acids include hexahydroterephthalic acid, hexahydro-p-xylylenedicarboxylic acid, p-Itylylene dicarboxylic acid, terephthalic acid and isophthalic acid mention.

Aliphatic amino acids should in particular include ι * -aminocarboxylic acids of the aliphatic type and those derived therefrom Lactams are understood. One can find certain compounds of this genus by one of the formulas:

NH ₂ (GH ₂ ) _n CO ₂ H or [

L-NH-OO-J

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where η is equal to a positive integer from 2 to 11. Caprolaotam is particularly suitable. Further, for example, laurinolactam (dodecanolactain), oenantholactam and capryllactaia are suitable

Amino acids such as cycloaliphatic amino acids should be understood as meaning amino acids Ren are understood to have an alkylene ring structure of the formula;

where η is an integer from 5 to 16 and where two hydrogen atoms that are not bonded to the same carbon atom and also not to adjacent carbon atoms are _{substituted by an amino · bKw P} a carboxyl group

In the case of alkylcycloaliphatic aromatic acids, the amino and carboxyl groups attached to carbon atoms of the ring or the side chain.

As examples of the cycloaliphatic !! and alkylcycloaliphatic amino acids can include ^ -aminocyclohexanecarboxylic acid, 4-A: nino: nethylcycloherancarboniiäure and A- aminocyclohexyl acetic acid,

Under a Diaminopolyalkylenoxyverbindwng is to be understood a linear compound containing the _t SWEi terminal amino groups, one is either connected directly or through suitable linking groups to a polyalkylenoxy β can sweokmässig such compounds by the formula:

NH ₂ X (alkylene-0) _n Y NH ₂
represent where'oei X is a direct bond or a bond

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group and Y represents a bonding group, and where η is a is positive integer. The alkylene groups of a given polyalkyleneoxy chain can be the same as or from each other to be different; in the latter case the chain can contain, for example, a mixture of ethylene and propylene groups. The alkylene groups can contain 2 to 12 carbon atoms and also carry substituents such as alkyl groups. You can do that Diaminopolyalkylonoxyverbindungen, for example from a Polyalkyleneoxyglycol of the formula:

HO (alkylene-O) _{n + 1H}

by converting the hydroxyl groups into halogen atoms - e.g. into chlorine atoms by reaction with thionyl chloride - and the resulting dihalogen compound with ammonia reacts to form the corresponding diamino compound. In the Bern case, X represents a direct bond and Ϊ represents an alkylene group. 12s is also possible, however, the Diaminopolyalkyleneoxy compounds from a polyalkyleneoxyglycol of the formula:

HO (alkylene-O) _n H

by reacting this (glycol with acrylonitrile to form the bis-ß-cyanoether and reducing the latter to the corresponding bis-Y-aminopropylether. In this case X represents the group: -CH ₂ CH ₂ CH ₂ ⁰ * ' ^{and Y represents the} group: -CH ₂ CH ₂ CH ₂ * -. Again, the compounds mentioned can be obtained from a polyalkyleneoxyglycol of the formula

HO (alkylene-O) _n H

also produce by reacting the glycol with a 2-aminomethyl-3f4-dihydro-2H-pyran, such as this is described in the applicant's British patent application 5173/65. In this case, X represents a 2-methylenetetrahydropyran-6-yloxy group and Ϊ represents a 2-methylenetetrahydropyran-6-yl group.

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The diaminopolyelkyleneoxy compounds also include the diamines, those in a manner known per se from alkylene oxide condensation products can be made with two hydroxyl groups. Such alkylene oxide condensation products can be carried out Reaction of an alkylene oxide or an alkylene oxide mixture with a compound which is opposite to the alkylene oxide contains reactive hydrogen atoms. the The said compound can, for example, be water, a glycol, a dihydric phenol, a primary amine, a primary amide be a secondary amine or a dicarboxylic acid. Such Alkylene oxide condensation products include:

1.) Condensation products from alkylene oxide and Q-lycoles, in particular from glycols with more than 4 carbon atoms, such as 1,6-hexane glycol;

2.) Condensation products of alkylene oxide and primary amines, such as, for example, Methylamine, ethylamine and hexad cylamine; and

3o) condensation products of alkylene oxide and dihydric phenols, such as, for example, Diphenylol propane ₀

The alkylene oxides used are, in particular, ethylene oxide and propylene oxide preferred, although other alkylene oxides such as 1,2- or 2,3-butylene oxide can also be used »The reaction of the alkylene oxide condensation products with two hydroxyl groups in the diaminooolyalkyleneoxy compounds can ZoB ^ with the methods already described for converting polyalkyleneoxyglycols into diaminopolyalkyleneoxy compounds be effected.

Particularly preferred diaminopolyalkyleneoxy compounds are diaminopoly (propylene oxide), diarainopoly (hexamethylene oxide), Mention should be made of diaminopoly (actamethylene oxide) and diaminopoly (decamethylene oxide). Preferably the diaminopolyalkylenocytes have a molecular weight in the range of 300 to 6000.

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- ο *

All aliphatic, cycloaliphatic or aromatic diamines, which are optionally all constituent parts of the condensation products can be used according to the invention, all aliphatic, cycloaliphatic or aromatic, also alkyloyoloaliphatic and alkylaromatic diamines can be used · especially however, aliphatic diamines of the formula »

HH ₂ (CHg) _n NH ₂

where η is a positive integer from 2 to 12. Hexamethylenediamine is particularly suitable. Further are s.B. Ethylenediamine, nonamethylenediamine, decamethylenediamine, Dodecamethylenediamine and ß-methylhexamethylenediamine should be mentioned as suitable aliphatic diamines. Cycloaliphatic diamines are to be understood as meaning those diamines which an alkylene ring structure of the formula:

Γ ^(β 2>

included, where η is equal to a number from 5 to 16, and being two hydrogen atoms that are not on the same O atom and are also not bonded to adjacent carbon atoms, are each substituted by an amino group to form the corresponding diamines. When using aromatic In diamines, the amino groups should not be on neighboring atoms. Examples of suitable cycloaliphatic and aromatic diamines are 1,3- and 1,4-diaminocyclohexane, Mention p-xyIy1enediamine, p-phenylenediamine and p-tolylenediamine · The diamine can be in the form of one of the dioarboxylic acids derived salt can be used.

The dioarboxylic acid is preferably used for the condensation product according to the invention in an amount which is approximately the stoichiometric equivalent of that used

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· » Π · ■

Amount of Diamina, be it a Diainino polyalkyleneoxy compound or an i-table of the same with another slide set, is equivalent to.

The amount of the diaminopolyalkyleneoxy compound used can be very different. Preferably, however, the ratio is from the weight of the diaminopolyalkyleneoxy compound to the total weight of the amino acid or aminolactara of any further diamines IO j 90 bis used 95: 5.

The condensation products can be conveniently produced in that the components mixed and heated to 150 to 3Ou ⁰ C for 30 min to 5 hours. Additives such as antioxidants, heat stabilizers, pigments and fillers, which are still stable under the polymerization conditions, can be added to the reaction equipment, or they can be mixed with the finished polymer.

Instead of the dicarboxylic acids as such, one can use in the production of the condensation products, certain derivatives, such as the esters, especially the lower alkyl esters, and the halides, the dicarboxylic acids use

If an amino acid is used instead of a lactam, it may be necessary to add a "flux" to the reaction mixture. to add »The term" flux "is to be understood here as meaning an agent that is able to dissolve the components at the reaction temperature and after the reaction has ended removed, z-B »by reducing the pressure and distilling off or by extraction with a solvent, fcany>. An example of such a flux agent is c-phenylphenol-Be can be advantageous, the condensation in an Atmos · « sphere aua an inert sas like nitrogen or in o

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from a solvent such as water in a sealed vessel under pressure.

The condensation products according to the invention are randomly constructed polyamide condensation products mostly in the form of pests, which are often rubbery. Some of these Condensation products can be processed into threads of high stretchability by melt spinning, while foils, films or molded parts can be produced from others by heating can be. Depending on the amount of the diaminopolyalkyleneoxy compound in the condensation product, the polyamides show the can be made into fibers, various strength and stretchability; e.g. if the amount of polyether is large, however, the objects have a high degree of stretchability has a low strength, and if this amount is small, the strength is relatively high if it is reduced Dispersibility.

The invention is explained below purely by way of example with the aid of exemplary embodiments, all quantities being based on weight:

example 1

There are heated 50 parts Diaminopolypropylenglykol having a molecular weight of 2060, 3.3 parts of adipic acid and 50 parts of caprolactam, 4.5 hours at 224 ⁰ C while stirring under a nitrogen atom. The pressure is then brought to 15 mm for 1 hour and then kept at 15 mm for 10 minutes. The product is then cooled, cut into pieces, extracted with boiling water and then dried. Daa polymer has to Endgruppenbeetimmung a molecular weight of 9000 · Sa can be pressed through a spinneret at 22O ⁰ C, wherein highly elastic Paden be formed.

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Example 2

70 parts of a, 4Ju]) ianiinopolytetramethylene oxide with a molecular weight of 3,000, 3.3 parts of adipic acid and 30 parts of caprolactam are treated as in Example 1. It gives a translucent tough gumraiartigss product with a molecular weight of 24 000 dae at 220 ⁰ C m steyksu ρΙ **: be schmelssgeßponr.en · -bischen fibers AIM κ:; '£ cm V: ■■:. ^: tT-cnI ¹ ?:; ·; dia .- "se F & iiej ^ el ^ i; re ^ /: · ■ r.".;: "[■; · Youthfulness of 60Ü J ^ ₁

Room temperature is the product. blaBsgell> - = r, · uxirmscK- :. elastic, gummy, water-soluble solid *

Example 4

50 parts of aminopolyoxyethylene with a ninais M ^ kuiar weight of 1,464, 50 parts of oaprolactaia and 5% oil
Adipic acid 1 hour and 45 minutes treated as in Boiopisl 3 "The cooled" product is an almost Faroiosey -, - Guininiartiger Opaxlcsatstoff _f which the product #; Q: rtiv: i Biispii 3 compared to what is water-soluble.

Example 5

3a, 70 parts of a, (^]) iaminopolyoxyäthy.le »Kit one eio! kulargewich * of 1,464, 30 should caprolactam _; 7 TsIIe AdIpic acid and 50 parts V / acmer 1 hour at 23 (. ⁰ C in 6> ί: ΐ3 ·; _Ε
Autoclave heated, the pressure ai'-f IT ₁ 5 A.tii üvrzh- Ab? ^)

fsa is held by W'asfcardäiiapf ».Oiβ Tfiap ^^ - etur wi ^ cl (t;>: brought to ^ 40 ⁰ O during 1 hour, ana. dm i'ru -h. τ * ν ■ .-. ■ ; '' · ■ i-U'ü.nk ßlsiüfi gensacht. 0s ,; ^r /:,υtnicl/··'·.- fly? Dar;

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-ΙΟΙ hour at 25O ⁰ C heated under atmospheric pressure. The polymer is similar to Example 3 in its IDi properties.

Example 6

Us are α 25 parts β-Diaminopolyoxyäthylen stirred with a molecular weight of 1 532, 2.4 parts of adipic acid, 15 parts of caprolactam and 10 parts of the salt of hexamethylenediamine and adipic acid, 3.5 hours at 259 ⁰ C under a nitrogen stream sanexstoffreien. After cooling to room temperature, the product is a pale yellow, translucent, rubbery solid.

Example 7

There are 40 parts α, ^ - Diaminopolyoxyäthylen having a molecular weight of 1540, 4.0 parts of adipic acid, 24 parts of caprolactam and 36 parts of the salt is stirred from hexamethylenediamine and adipic acid, 1 hour and 45 minutes at 259 ⁰ C under an oxygen-free nitrogen stream. The product is a pale yellow, rubbery, melt-spinnable pesticide that is soluble in a water-ethyl alcohol mixture.

Example 8

30 parts of a ^ -diaminopolyoxyethylene with a molecular weight of 1,454, 3 parts of adipic acid, 28 parts of caprolactam and 42 parts of the salt of hexamethylenediamine and are us Adipic acid treated as in Example 7. The product is a pale yellow, translucent, rubbery pesticide soluble in aqueous ethyl alcohol,

Example 9

60 parts of a ^ -Diaainopolyoxyäthyiea with a molecular weight of 1,540, 40 parts of caprolactam and 5.7 parts of adipic acid are stirred for 2 hours at 259 ⁰ C under an oxygen-free nitrogen stream. The product will be in a

Thoroughly stirred _r ready mixture, heated to 60 ⁰ U, of 900 parts of water and 400 parts of isopropanol poured in _o The result is a clear solution which turns into a gel on cooling

Example 10

25 parts of a polyoxyethylene with terminal aminomethyltetrohydropyranylgrupfien, since from ν Iyoxyäthylenglykol with a molecular weight before X 540 aw, .. \\ Reiiktiöii with Aniiiiomsthylii ihydropyj un hor ^ etellt was _; 2 ¹ ',': '■ -i *, e Oaprolactara and 2.6' JC-EILCs Aaip ^ r ^ me ^ ')') ^ '' üJIcn fc-.j ·· * 90 ^c G under.. an aaucrctof free);. Jtic ^ ntvf / etrosn j: J.telni :: v _; -: v ^ iu ¹ brought reaction, Vi'oy.mf Ua ?. J; ^^ ';: tionegcri.; "ch b-: 19O ^c C and 3 ¹ J ram]) j'uok währciid 3 _; - ^; '. ^f 5 b``U''t ' ^r . <m be ^ auael \ ^: Vvirii The product is; ΐΐ- hard, sth ^ ·; gprö-ies polymer *

Patent entitlement:

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Claims (1)

1570710 . - 12 - Claim Process for the production of Polyami icon denaation products by adding a dicarboxylic acid or a carbonic acid derivative with an amine component and a mixture of characterized by that the amine component is a mixture of an iJianinopolyalkylenoxyver bond and an aliphatic, cycloaliphatic or alkylcycloaliphatic Amino acid and / or such an Lnctati and optionally an aliphatic, cycloaliphatic or aromatic;) ianln represents « MTtNlASWSlIl Mf ItICK ;, OIPl -li «i AiOMt MPL-INO LtIAIOW Documents (Art. 7 11 At ». Ζ tit. L sentence 3 d ·· Är> d« aing «ea- ν. 4.9. 909885/1570 BATH ORIGINAL