DE1570403A1 - Process for the production of solid lactam-catalyst-cocatalyst mixtures which can be stored and shipped at temperatures below 50 ° C - Google Patents

Description

Lactam kata that can be stored and shipped below 50 C. lyser-cocatalyst mixtures

Addition to patent application P 14 95 360.7

The invention relates to an improved process for the production of solid, at temperatures below 50 C storage and Shippable lactam-catalyst-cocatalyst mixtures.

The subject of patent application P 14 95 360.7 is a process for the production of solid materials at temperatures below 50.degree storable and dispatchable lactam-catalyst-cocatalyst-mixtures, with which one

(1) a lactam,

(2) a catalyst or its mixture with lactam and

(3) a cocatalyst or its mixture with lactam

in the solid state at temperatures below 50 C, preferably intensively mixed together under the exclusion of moisture, the catalyst and cocatalyst concentration is preferably 0.1 to 2 mol%, based on the total mixture, is in each case 0 _# 0L to 5 mol%, . Solid lactam-catalyst-cocatalyst mixtures are obtained, "which can be polymerized to high-molecular polyamides at elevated temperature without further additives.

It has now been found that, in a further development of the method according to patent application P 14 95 360.7, the storage stability improve the lactam-catalyst-cocatalyst mixtures considerably leaves, if the catalysts are neutral or

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weakly basic salts used at the polymerization temperature with lactams with the formation of metal lactamates react. These catalysts are said to be at temperatures at which the activated lactam powders can be stored (ν 50 C), react neutrally or weakly basic, while they react at elevated temperature, e.g. at a polymerization temperature of 200 C, are able to form metallactamates from lactams with elimination of a proton.

Such compounds, which are referred to below as "latent" catalysts because of their initially undetectable catalytic activity, are, for example, neutral or weakly basic salts of volatile, weak acids or compounds containing carboxyl groups, which convert into strong bases _{at the polymerization temperature with CO 2 elimination,} such as, for example, alkali or alkaline earth salts of decarboxylable carboxylic acids, carbonic acid half-esters, carboxylated amines or lactams.

Some formula schemes are given below:, COOR COOR

1) CH ₂

• COOMe

Me = metal

0
OR OR

2) OC '- · " ^C0 2 ->

OMe Me

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-ro ®

3) QC - ^ - COOWe - 2-> OQ-J! Me

Alkali salts of - substituted carboxylic acids of the formula I are particularly suitable as "latent" catalysts

C - COOH I, R ¹

in which R and R ^{1 are} identical or different alkyl or aryl radicals or hydrogen and X is a radical, such as, for example, the aryl, cyano or ester radical, which facilitates decarboxylation by attracting electrons.

The alkyl radicals can have 1 to 16 carbon atoms, the aryl radicals 6 to carbon atoms.

R and R 'have no decisive influence on the effectiveness of the catalysts as long as they are inert to the reaction melt, i.e. do not contain any halogen atoms, for example.

Examples of such salts are sodium phenyl acetate, sodium cyanoacetate, the potassium salt of malonic acid monoethyl ester, in whose Decarboxylation in each case strongly basic carbon anions develop.

Salts of half an inch of carbonic acid are also suitable, e.g. Sodium ethyl carbonate, potassium methyl carbonate, lithium butyl carbonate. Since these salts are converted into alcoholates during decarboxylation, i.e. they supply oxygen anions, they can also be used refer to as "disguised alcoholates".

Such compounds also come as "latent" catalysts into consideration, in their decarboxylation nitrogen anions develop. - Examples are salts of carboxylated Lactams, e.g. I-tatrium-I ^ -carboxy-caprolactam or Kaliurn-N-carbpxylaur in lactam or salts carboxy-

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lated amines, i.e. salts of carbamic acids, e.g. sodium N-phenylcarbaminate.

Finally, "latent" catalysts are suitable, too Salts of volatile weak acids, e.g. sodium cyanide, potassium cyanide, which at polymerization temperature with lactam with elimination of the free acids to give the metal lactamates react.

The "latent" catalysts are used in the same way and in the same amounts as the catalysts according to patent application P 14 95 360.7. Because of the risk of premature reaction concentrates are of "deferred ¹¹ catalysts and lactams not preferred over the SchxoBlmmn, βοά-. Countries by mixing in solid form below 50 C, especially at room temperature was prepared. On the other hand one can often due to the insensitivity of the most" latent "catalysts against moisture in the production and storage of the lactam-catalyst-co-catalyst frameworks do not exclude moisture and work in the air. Before the polymerization, however, the activated powders are advantageously vented to avoid discoloration or temperature. Another advantage is" latent "catalysts" lies in the fact that they cause w * n £ f *? side reactions and result in lighter-colored polyamides

The polymerization is carried out under nitrogen at between 140 and 300 C, preferably between 180 tUld 26O C, carried out. Sales are made by extraction. Ä # r crushed Polymers determined with hot methanol, Di © using the "latent * catalysts according to the invention obtained lactam-catalyst-cocatalyst-quirK mixtures can be discontinuous, but especially kimtinu-

_{Λ Λ A Λ A} BAD QRJßJNAL

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ierlich, e.g. in a screw press / polymerize. Included It is recommended to use an extruder with one or more degassing zones, which allows the from the To remove volatile components derived from "latent" catalyst.

The preparation of these compounds and their use as catalysts in anionic lactam polymerization are described in the literature (O. Wichterle et al., Chem. Listy, Praha, J52, pages 636 to 639/1958 /).

It is. however surprising that those using this "Latent" catalysts produced solid lactam-catalyst-cocatalyst mixtures compared to those using conventional catalysts according to. Patent application P 14 95 360.7 analogy mixtures obtained not only have a significantly improved shelf life under the exclusion of air and moisture but can also be stored in the open air. The technical progress thus achieved is based on the following examples are explained in more detail.

Example A provides a comparative example for the preparation of a lactam catalyst / cocatalyst mixture according to the patent application P 14 95 360.7. The parts mentioned in the examples are parts by weight.

As a measure of the shelf life of the lactam / catalyst / cocatalyst mixtures according to the invention the drop in polymerization activity is given here.

This can be printed out by the basic rate, which under certain constant polymerization conditions is achieved. If this turnover for a product falls after a

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know is storage time more strongly than in another, the former less stable in storage.

Example Λ

ISO parts of dry laurolactam, 13 parts (1 mol-90) of a sodium laurolactam concentrate in laurolactam (0.82 mmol / g), 2.5 parts (0.0 mol- ^) II- (N ¹ -phenyl- carbanoyl) -laurinlactam and 1.0 part (0.1 lAol-%) of a hexamethylene-1,6-bis (carbamido-laurinlactam) concentrate in laurolactam (1 mHol / g) are 3 to 5 minutes while blowing in dried Nitrogen mixed intensively at room temperature (e.g. in a household mixer).

If polymerization is carried out immediately after mixing, the conversion is, for example - depending on the temperature and residence time - 98 %, after four weeks of storage under nitrogen at OC 75 %, after four weeks of storage at room temperature 57 %, after one week of storage at 50 G 80 %. If stored in the air, the activated powder can no longer be polymerized after a few hours.

example 1

100 parts of dry laurolactam, 0.45 parts (0.5 mol%) of the potassium salt of malonic acid monoethyl ester and 2.75 parts (0.05 mol%) of an N- (N ¹ -phenyl-carbamoyl) -laurolactam concentrate in Laurolactam (0.9 mmol / g) are intensively mixed with one another as in Example A. With immediate polymerization, the conversion is, for example, 98 % and remains unchanged at 97% to 98 % after storage in air at room temperature for two weeks.

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Example 2

, Me: n mixed at room temperature without protective gas 200 parts of dry laurolactam, 0.85 parts (0.5 mol%) of the potassium salt of malonic acid monoethyl ester, 1.26 parts (0.4 mol-; N- (N '- Phenyl-carbamoyl) -laurinlactam and 2.81 parts (0.05 l'xOl-%) of a concentrate of laurinlactam with 10 weight percent hexamethylene-1,6-bis- (ca'rbamido-laurinlactam).

Before polymerization, the samples must be deaerated by evacuation. Polymerisiert.man immediately after mixing, · the conversion is, for example, 97 %, after four weeks of storage at 50 C in air 96 %, after six weeks of storage at 50 ° C in air also 96 %.

Example 3

200 parts of dry laurolactam, 1.6 parts (1 mol%) of sodium phenyl acetate and 2.4 parts (1 ΙΊοΙ%) of N- (N ¹ -phenylcarbaraoyl) -caprolactam are intensively mixed with one another as in Example A.

The immediate polymerization produces a turnover of example 94 Vo, which does not change after vitrv / öchiger storage at 50 C under _N2 to drop to 89% after twelve weeks storage at 50 C under _Ν Λ.

Example 4

As in Example A, 200 parts of dry laurolactam are mixed with 1.12 parts (1 Μ0Ι- / 0) sodium lithium carbonate and 2.5 parts (0.25 mol%) of a hexamethylene-1,6-bis (carbamido-laurin lactam) -Concentrates (1 mmol / g) "

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With immediate polymerization, for example, a conversion of 94 % is achieved, after two weeks of storage at room temperature under nitrogen, of 77 %, and after 24 hours of storage at 50 ° C. in air, likewise 77%.

ORIGINAL BATH 909885/1669

Claims (3)

1 = 70403 -9- July 17, 1969 Claims 1 * Method of making solid, at temperatures below 50 C, preferably at room temperature, more storable and dispatchable, more polymerizable without further additives Lactam catalyst cocatalyst mixtures according to patent application P 14 95 '360.7 by intensive mixing (1) a lactam (2) a catalyst or a mixture of the catalyst with lactam and (3) a cocatalyst or a mixture of the cocatalyst with lactam in solid state at room temperature, preferably with the exclusion of moisture, the catalyst and cocatalyst concentration in each case from 0.01 to Mol%, preferably 0.1 to 2 mol%, based on the total mixture, amounts to, characterized in that the catalysts used are neutral or weakly basic salts used, which at Polymerisätion Temperatur.mit Lactamen react with the formation of metallactamates. 2. The method according to claim 1, characterized in that the catalysts used are neutral or weakly basic salts containing carboxyl groups which _{react at polymerization temperature with elimination of CO 2} with lactams to form metal lactamates. 3. The method according to claim 1 and 2, characterized in that the catalysts used are alkali metal salts of C ^ -substituted carbon New documents (Art. 7 "τ Ab", 2 nm sentence 3 of the amendment "wflse" a. V. 4,9. 909885/1669 BAD 1670403 - 10 - PC 2025 . 17.7.19G9 acids of the formula I are used ir Xi , C - COOH I. where R and R 'are identical or different alkyl or aryl radicals or hydrogen and X is an aryl, cyano or ester radical. BATH ORIGINAL 909885/1663